Abstracts Theme A

Resources and Environment

Theme  Convener:      Manfred  Grasserbauer,  Austria  

Oral Presentations  

 Plenary  Lecture           page  2,  abstract  number  1922    Keynotes,  Contributed  Lectures     pages  3  –  96  

abstract  numbers  0103  –  1999    

Poster  Presentations         pages  98  –  175                 abstract  numbers  0136  –  1878    

 

2

1922  

 

WATER-FOOD-ENERGY NEXUS: IMPACT ON WATER QUANTITY AND QUALITY

A.J.B. Zehnder

Alberta Innovates – Energy and Environment Solutions, Alberta Canada Nanyang Technological University, Singapore

TripleZ Ltd. Switzerland alexander.zehnder@triplez.biz

One percent or less of the Earth’s water is usable for humans, the rest is in the oceans, locked up in polar ice caps, glaciers or in deep groundwater. Large parts of the usable water is annually recycled through the global water cycle, leaving the earth surface as vapor and returning as rain, though rarely at the same place. Seasonally and spatially variable precipitation patterns and river transporting the run-offs govern the local and regional availability of water. Water ending up in its liquid form in rivers, lakes and aquifers is called blue water. Water responsible for soil humidity has been termed green water. The literature also talks about grey and black water. Grey is polluted water and black is water contaminated by human excreta. They can both be converted into blue water again by wastewater treatment technologies. Green water is stationary, cannot be transported and is exclusively used by plants for their growth. Plant material and crops in terms of water is named virtual water which means the amount of water needed to grow the crop or plant. That water is locally lost as evapo-transpiration to the atmosphere. About 1,500 cubic meter of water is what each person needs annually for a decent life, roughly 2 cubic meter of highest quality for drinking, 20 cubic meter for hygiene and cooking, and 250 for services and industrial needs, all of it, blue water The rest is for growing food, mainly green water. A shortage of water is compensated by food import. Food contains all the nutrients which will be excreted after consumption. Together with the fertilizers applied at the production site, these nutrients are the major polluters of rivers, lakes groundwater and coastal oceans. Water treatment to remove these pollutants requires energy. In larger cities the major part of the communities’ electricity bills is for handling water. Electricity typically originates from hydropower, coal, oil and gas firing. For hydropower rivers have to be dammed, altering flow regimes. Oil and gas are produced increasingly unconventionally and water intensive (oil sand, fracking, etc.). Two to three cubic meters of water are needed for one barrel of oil from oil sands, leaving behind highly contaminated and difficult to treat water. In semi-arid areas where currently much shale oil and gas deposits are mined, fracking activities increasingly compete for water with irrigation agriculture and larger communities. Innovations in water management focusing on pollution prevention or multiple uses of the same water through recycling and treating complex chemistries will be in demand. These challenges will be presented based on specific cases, the vulnerabilities and weaknesses of certain links exemplified, and the needs for specific process and technology related innovative solutions identified.

 

3

0103  

 

DIFFERENT COMPOSITIONS OF PHARMACEUTICALS IN DUTCH AND BELGIAN

RIVERS EXPLAINED BY CONSUMPTION PATTERNS

AND TREATMENT EFFICIENCY

T. L. ter Laak1,2 P. J.F. Kooij1, H. Tolkamp1,3, J. Hofman1

KWR Watercycle Research Institute, P.O. Box 1072, 3430 BB, Nieuwegein, The Netherlands

Department of Environmental Technology, Wageningen University, P.O. Box 8129, 6700 EV Wageningen, The Netherlands

Roer en Overmaas Regional Water Authority, P.O. Box 185, 6130 AD Sittard, The Netherlands

Presenting author: thomas.ter.laak@kwrwater.nl

In the current study 45 pharmaceuticals and 18 transformation products were studied in the river Meuse at the Belgian-Dutch border and four tributaries of the river Meuse in the southern part of the Netherlands. The tributaries originate from Belgian, Dutch and mixed Dutch and Belgian catchments. In total, 24 pharmaceuticals and 13 transformation products were observed in samples of river water collected from these rivers. Observed summed concentrations of pharmaceuticals and transformation products in river water ranged from 3.5 to 37.8 µg/L. Metformin and its transformation product guanylurea contributed with 53 to 80 % to this concentration, illustrating its importance on a mass basis. Data on the flow rate of different rivers and demographics of the catchments enabled us to calculate daily per capita loads of pharmaceuticals and transformation products. These loads were linked to sales data of pharmaceuticals in the catchment. Simple mass balance modelling accounting for human excretion and removal by sewage treatment plants revealed that sales could predict actual loads within a factor three for most pharmaceuticals. Rivers that originated from Belgian and mixed Dutch and Belgian catchments revealed significantly higher per capita loads of pharmaceuticals (16.0 ±2.3 and 15.7 ±2.1 mg/inhabitant/day, respectively) than the Dutch catchment (8.7 ±1.8 mg/inhabitant/day). Furthermore, the guanylurea /metformin ratio was significantly lower in waters originating from Belgium (and France) than in those from the Netherlands, illustrating that sewage treatment in Belgium is less efficient in transforming metformin into guanylurea. In summary, the current study shows that consumption based modelling is suitable to predict environmental loads and concentrations. Furthermore, different consumption patterns and treatment efficiency are clearly reflected in the occurrence and loads of pharmaceuticals in regional rivers.

 

4

0162  

COMBINED OZONE BASED CATALYTIC PROCESSES FOR THE DEGRADATION OF

ORGANIC MICROPOLLUTANTS

F.J. Beltrán

Departamento de Ingeniería Química y Química Física. Universidad de Extremadura. 06006 Badajoz. Spain

fbeltran@unex.es In this work a review of, possibly, the last ozone involving advanced oxidation processes (O3AOP), combination of ozone and catalysts and radiation to remove contaminants from water, is presented. Research on ozone processes increased after the 1990s with the application of catalysts which constituted other new O3AOP that took the name of catalytic ozonation. Heterogeneous catalytic ozonation can be classified according to the presence or absence of another important agent: UV radiation. Thus, the process is then called photocatalytic ozonation. Figure 1 is a bar graph with the variation of the number of research articles on catalytic and photocatalytic ozone processes between 2000 and 2013.

Figure 1: Number of research articles on ozone catalytic processes published between 2000 and 2013

Non-photolytic processes can also be classified according to the nature of catalysts: those with metals in any form and those using activated carbons [1]. Photocatalytic ozonation is a synergistic process involving photocatalytic oxidation [2] and ozonation. Fundamentals and examples of these O3AOP are presented. Acknowledgement The author thanks the Spanish CICYT and Feder funds for the economic support through project CTQ2012-35789-C02-01. References 1. F.J. Beltrán, Ozone and solid catalysts for the treatment of water pollutants in Recent research developments in Environmental Technology (A. Gil y S.A. Korill: editors), Transworld Research Network, (Kerala, India, pp1-30, 2008). 2. D.S. Bhatkhande, V.G. Pagarkar, A.C.M. Beenackers, J. Chem. Technol. Biotechnol., 77, 102-116, 2001.

 

5

0204  

 

POLLUTION CHARACTERIZATION OF ORGANIC ATMOSPHERIC EMISSION IN

THE ARCTIC BY COMBINING QUANTITATIVE TRACE ANALYSIS WITH SCANNING

ELECTRON MICROSCOPY

K. Schütze3, R. Kallenborn1,2, S. Weinbruch3 1Institute for Chemistry, Biotechnology and Food Sciences, Norwegian University of Life Sciences

(NMBU), NO-1432 Ås, Norway 2University Centre in Svalbard (UNIS), Department of Arctic Technology,

NO-9171 Longyearbyen, Svalbard, Norway 3Institute for Applied Geosciences, Technical University of Darmstadt,

DE-64287 Germany Presenting author: roland.kallenborn@nmbu.no

During two subsequent sampling campaigns in 2011 and 2012, simultaneous sampling for aerosol characterization and the polycyclic aromatic hydrocarbons (PAH) and polychlorinated biphenyls (PCB) quantification was conducted in the vicinities of the power plants and from Arctic background samples in Longyearbyen and Barentsburg (Svalbard; Norwegian Arctic). The particle/ aerosol characterization was performed using Environmental Scanning Electron microscope (ESEM) at the Technical University Darmstadt (Germany). The trace analytical quantification of the air samples was done at the analytical laboratories of the Norwegian University of Life Sciences (UMB), Dept. of Chemistry, Biotechnology and Food Sciences (IKBM) using gas chromatography coupled to a low-resolution mass spectrometer in Electron impact mode. During the 2012 campaign (01. – 14.03.2012), air samples were taken at 7 different locations in Barentsburg and Longyearbyen in distinct differences from the local electric power plants identified as significant local contamination source for the emission of organic pollutation to the nearby settlements. The highest levels for PAHs were found for the direct gas phase emissions from the Longyearbyen power plant (74 mg/m3 total PAH, around 90% of the emissions via the gas phase). The major contributions in the direct emitted air samples are associated with Benzo[a]pyrene and Benzo[a]flouranthene. The distribution of PAH in the background stations is mainly influenced by a combination of direct local emissions and PAHs reemitted from secondary sources. The particle composition and characterization of the emitted aerosols were performed by environmental scanning electron microscope (ESEM). Particle distribution as well as mineral composition testing was done and combined with the PAH concentration data. The results of the here presented study confirm that PAH level distribution is obviously directly associated with the particle fractions identified in the emission samples.

 

6

0253  

 

ENVIRONMENTAL ELECTROANALYSIS OF EMERGING POLLUTANTS

J. Barek

Charles University in Prague, Faculty of Science, University Research Centre UNCE ”Supramolecular chemistry”,

Department of Analytical Chemistry, UNESCO Laboratory of Environmental Electrochemistry, Albertov 6, CZ 12843 Prague 2, Czech Republic

barek@natur.cuni.cz The aim of this presentation is to show that even in the age of fascinating possibilities of modern spectrometric and separation methods, modern electroanalytical methods, especially in combination with non-traditional electrode materials and arrangements, can play useful role in environmental monitoring because of low running and investment cost, easy miniaturization, portability, and sufficient selectivity and sensitivity enabling detection of submicromolar to nanomolar concentrations of electrochemically active organic compounds. Attention will be paid to the use of mercury electrodes, which are up to now the best available sensors for detection of electrochemically reducible organic compounds (chemical carcinogens, endocrine disruptors, pesticides, etc.) enabling limits of detection of environmental pollutants down to nanomolar concentrations if coupled with adsorptive stripping voltammetry [1]. In many cases they can be successfully substituted by silver solid amalgam electrodes [2], which are more robust, non/toxic and compatible with measurements in flowing systems. The advantages of carbon paste electrodes [3] will be shown on detection of submicromolar concentrations of electrochemically oxidizable pollutants (chemical carcinogens, pesticides, nitro phenols and other priority pollutants). Extreme usefulness of boron doped diamond film electrodes [4] in environmental electroanalysis will be demonstrated on determination of submicromolar concentrations of environmental carcinogens, endocrine disruptors, and of biomarkers of their exposition in biological fluids. The presentation will be concluded with possible outlooks of modern electroanalytical methods in environmental analysis of emerging pollutants. Acknowledgement Financial support of this research by the Grant Agency of the Czech Republic (project PG206/12/G151) is gratefully acknowledged. References 1. J. Barek, K. Peckova, and V. Vyskocil, Curr. Anal. Chem. 4, 242 (2008). 2. A. Danhel and J. Barek, Curr. Org. Chem. 15, 2957 (2011). 3. H. Dejmkova, J. Zima, J. Barek, and J. Mika, Electroanalysis 24, 1766 (2012). 4. K. Peckova and J. Barek, Curr. Org. Chem, 15, 3014 (2011).

 

7

0286  

 

POLYCATIONIC RESINS FOR ANIONIC DRUGS CAPTURE AND RELEASE.

CASE OF NALIDIXIC ACID AND PENICILLIN V

F. Lemée, I. Clarot, B.S. Nguyen, P. Lemiere, M. Mourer, J.-B. Regnouf-de-Vains

MOBAT team, SRSMC, UMR 7565, CNRS-Université de Lorraine Boulevard des Aiguillettes, 54506 VANDOEUVRE-LES-NANCY, France

Presenting author: frederic.lemee@univ-lorraine.fr Polymers may play an important role in the capture and release processes for depolluting waste waters, notably in urban areas with very strong density of population. Poisoning of waste waters by drugs or metabolites imply heavy treatments before obtaining tap water. Among drugs, antibacterial agents are problematic as they are widely used and susceptible to interfere with microorganisms used in water treatment plants. In this sense, we have studied some commercial and homemade cationic polymers, one of them being the well-known cholestyramine (QUESTRAN®). Two antibacterial models which are a quinolone (nalidixic acid, sodium and potassium salt) and a β-lactam (penicillin V, potassium salt) have been chosen for this study. We present here the results obtained by means of reversed phase CLHP1. Very interesting results were obtained with one of our homemade polymers in terms of capture-release capacities and recyclability.

Figure 1: Example of capture and release of Nalidixic acid using a cationic polymer Anions have been omitted for clarity

References 1. H. Massimba Dibama, I. Clarot, S. Fontanay, A. Ben Salem, M. Mourer, C. Finance, R. E. Duval,

J.-B. Regnouf-de-Vains, Bioorg. Med. Chem. Lett. 19, 2679-2682 (2004).  

 

8

0315  

SUSPECT AND NON-TARGET SCREENING OF ORGANIC MICROPOLLUTANTS IN

WASTEWATER THROUGH THE DEVELOPMENT OF A LC-HRMS BASED

WORKFLOW

P.Gago-Ferrero*, A.A. Bletsouª, R. Aalizadeh, N.S. Thomaidis

Laboratory of Analytical Chemistry, Department of Chemistry, University of Athens, Panepistimiopolis Zographou, 15771 Athens, Greece

ªBoth authors contributed equally to this work Presenting author: pablo.gago.ferrero@gmail.com

A large number of organic contaminants and related transformation products (TPs) are present in wastewaters. Target analysis only allows the detection of a very small fraction of these substances, due to the inability to obtain standards for all that substances and the ignorance of the existence of many of them. Recent advances in high resolution mass spectrometry (HRMS) have opened up new windows of opportunity in the field of complex samples analysis [1]. The application of suspect and non-target screening methods allows the tentative identification of a much larger amount of pollutants and focus efforts on the most relevance substances in terms of environmental concern. However, a balance between extensive target analysis and screening methods is needed. The aim of the present work is the development and application of an integrated workflow based on liquid chromatography coupled to a quadrupole-time-of-flight mass spectrometer (LC–QToF-MS) to detect suspected and formerly unknown organic contaminants in wastewater. Suspect screening was carried out through the set-up of a large in-house data base including the molecular formula of more than 7000 relevant organic pollutants and TPs (which were not present in our existing target methods). The tentative identification of these compounds was based in the evaluation of criteria such as blank signal presence, mass accuracy or isotopic pattern. Moreover, the chromatographic retention time plausibility (using prediction models) and MS spectra comparisons were also considered. According with the aforementioned criteria, few suspect compounds were tentatively identified in wastewater samples from the wastewater treatment plant (WWTP) of Athens, the largest in Greece. Full identification of unknown compounds is often difficult and there is no guarantee of a successful outcome. After optimizing the peak peaking procedure using molecular features algorithm, relevant peaks were selected based on the intensity and the presence of distinctive isotopic patterns (the most relevant substances with reasonable identification possibilities). For the selected peaks the most plausible molecular formula(s) were determined by applying thresholds of mass accuracy, isotopic pattern and even commercial importance through the use of the Seven Golden Rules software [1]. A deep evaluation of the MS spectra was performed for these peaks, using both data bases (e.g. mass bank) and in silico fragmentation software (e.g. Metfrag) to find candidates. Chromatographic retention time prediction models were also applied to assess the plausibility of the candidates. This approach allows the obtaining of plausible candidates for most of the selected peaks and the tentative identification for some of them in the evaluated samples.

References [1] E. Schymanski et al., Environ. Sci. Technol 48, 1811 (2014). [2] T. Kind and O. Fiehn, BMC Bioinformatics 8, 105 (2007). Acknowledgment This project was implemented under the Operational Program «Education and Lifelong Learning» and funded by the European Union (European Social Fund) and National Resources – ARISTEIA 624 (TREMEPOL project).  

 

9

0346  

INVESTIGATION OF THE PARTITIONING BEHAVIOR OF VOLATILE ORGANIC

COMPOUNDS BETWEEN AIR AND AIRBORNE DUST BY MEANS OF SELECTED ION

FLOW TUBE MASS SPECTROMETRY

C. Walgraeve, K. Demeestere, J. Dewulf, H. van Langenhove Department of Sustainable Organic Chemistry and Technology, Ghent University, Belgium

Presenting author: christophe.walgraeve@ugent.be

The investigation of the complex fate and behavior of pollutants in the environment is of paramount

importance. In this respect, our research focuses on the study of the partitioning behavior of a selected set of

volatile organic compounds (VOCs) between the free air phase and the airborne particulate matter. In order to

quantify the partitioning coefficients of the VOCs, a state-of-the art analytical technique is used, namely

Selected Ion Flow Tube Mass Spectrometry or SIFT-MS. The SIFT-MS is a new analytical technique for the

real-time measurement of trace-gases and Volatile Organic Compounds (VOCs) concentrations. Detection

limits in the lower ppbv level are obtained. By this technology, target molecules are ionized by chemical

ionization using H3O+, NO+ and O2+ precursor ions, produced by a microwave discharge source. Product ions

are formed and unreacted precursor ions are analyzed by a downstream quadrupole mass filter and allow for a

direct calculation of the concentration of the VOCs. It is proven by our results that the SIFT-MS real-time

measurement offers unique and new opportunities to study the interaction of VOCs with particulate matter.

The partitioning coefficients for a selected set of volatile organic compounds (having different physical

chemical properties) are determined. This was accomplished by the measurement of breakthrough curves of

the VOCs through a column packed with airborne particulate matter. A step function of the target VOCs was

applied to a column and the response was registered by means of SIFT-MS. Data obtained will be

quantitatively discussed and the relevance of these determined partitioning coefficients with respect to odor

nuisance caused by agricultural activities will be explained.

     

 

10

0349  

 

INTENSIFICATION OF THE CHEMICAL TREATMENT OF PHARMACEUTICAL

PROCESS WASTEWATERS: CATALYTIC WET OXIDATION WITH DOE AND

IRRADIATION COMBINED WITH WET OXIDATION

E. Szabados1, A. Tungler1, S. Kemény2 1Centre for Energy Research, Hungarian Academy of Sciences, H-1121 Budapest, Hungary 2Department of Chemical and Environmental Process Engineering, Budapest University of

Technology and Economics, H-1111 Budapest, Hungary Presenting author: szabados.erika@energia.mta.hu

The tested process wastewaters (PWW) were aqueous solutions generated by the fine chemical, mainly by pharmaceutical companies. Because of their high organic content they cannot be discharged directly into the domestic treatment plants. Significant part of them is sent to incineration, but it isn’t a sustainable solution. These PWWs could be utilized as carbon source for denitrification process, their volatile content could be separated and utilized also. The organic content of PWWs is partly easily biodegradable, most of them can be introduced into activated sludge treatment after mixing with domestic wastewater (in high ratio), but their minority inhibit the functioning of the activated sludge even in very small concentrations [1,2]. Chemical oxidation could be an effective method for treating these wastes in order to detoxify them. The appropriate oxidation processes are wet (air) oxidation (WAO), advanced oxidation processes (AOP’s). In this research model and real process wastewaters were tested with CWO (catalytic wet oxidation) and irradiation combined wet oxidation, in order to reduce their COD value and toxicity [3]. In the first part of the research work the effect of the main parameters on reaction rate has been determined by design of experiments (DOE) technique. The intensification, namely further decrease the temperature and the pressure of the oxidation could be possible by enhancement of the generation of OH radicals. For this purpose electron beam irradiation has been applied from a linear electron accelerator, through a titanium window into the reaction mixture being in the autoclave under oxygen pressure. The reaction rate was determined with COD and TOC conversion measurements. Our research had triple aim: optimization of the process, increase the reaction rate and moreover to deduce some mechanistic conclusions. References 1. A. M. Hosseini, V. Bakos, A. Jobbágy, G. Tardy, P. Mizsey, M. Makó, A. Tungler, Per. Pol. Chem. Eng., 55/1 3-10 (2011) 2. A. M. Hosseini, A. Tungler, V. Bakos, Reac. Kinet. Mech. Cat. 103 251-260 (2011) 3. M. Chamam, Cs. M. Földváry, A. M. Hosseini, A. Tungler, E. Takács, L. Wojnárovits, Rad. Phys. Chem, 81 1484-1488 (2012)

 

11

0351  

A NEW TRICHLORAMINE ANALYSIS METHOD, FACTORS INFLUENCING ITS

CONCENTRATION IN POOL WATER AND THE EFFECT OF UV TREATMENT

F. Soltermann1,2, T. Widler1, S. Canonica1 and U. von Gunten1,2,3 1Eawag, Swiss Federal Institute of Aquatic Science and Technology,

8600 Dübendorf, Switzerland 2Institute of Biogeochemistry and Pollutant Dynamics, ETH Zürich, 8092 Zürich, Switzerland

3School of Architecture, Civil and Environmental Engineering, EPF Lausanne, 1015 Lausanne, Switzerland

Presenting author: Fabian.soltermann@eawag.ch Trichloramine is a problematic disinfection by-product in indoor pool facilities representing a health risk for visitors and employees. Adverse health effects related to trichloramine are skin and eye irritations, inflammations of the respiratory tract and asthma. Up to date, trichloramine in pool water has been measured only in few studies due to the lack of an appropriate analytical method. A fast, sensitive, easy applicable and low cost colorimetric method was developed and validated with membrane inlet mass spectrometry (MIMS). This allowed for the measurement of 30 samples from different pools which revealed that trichloramine concentrations are strongly correlated with free chlorine concentrations. Combined chlorine and pH are weakly correlated with trichloramine while urea showed no correlation with trichloramine. A field study confirmed that the trichloramine concentration responds quickly to changes of the free chlorine concentration. Furthermore, trichloramine concentration in a wading pool increased with the number of bathers. The most common technique to mitigate combined chloramines (inclusive trichloramine) is UV treatment. Laboratory experiments showed that the trichloramine quantum yield in purified water is 2.1 ± 0.1 mol einstein-1. Quantum yields in pool water were in a similar range and they were influenced by the free chlorine concentration. From laboratory experiments it can be concluded that standard UV reactors in Swiss swimming pools degrade 30-50% of the trichloramine per treatment cycle. This was confirmed by an on-site measurement. However, the effect of UV treatment on trichloramine concentrations in the pools (wading and swimming pool) was less pronounced (20% and 10% reduction, respectively) because of the long residence time of the water in the pools (Figure 1).

Figure 1: Effect of UV treatment on NCl3 concentration in a wading pool.

 

12

0407  

 

ASSESSMENT OF THE REACTIVITY OF ORGANIC COMPOUNDS WITH OZONE IN

AQUEOUS SOLUTION BY QUANTUM CHEMICAL CALCULATIONS: ROLE OF

DELOCALIZED AND LOCALIZED MOLECULAR ORBITALS

M. Lee1, S. Zimmermann-Steffens1, J. S. Arey1,2, K. Fenner2,3, U. von Gunten1,2,3 1School of Architecture, Civil and Environmental Engineering (ENAC), École Polytechnique

Fédérale de Lausanne (EPFL), CH-1015, Lausanne, Switzerland 2 Eawag, Swiss Federal Institute of Aquatic Science and Technology, Ueberlandstrasse 133, CH-

8600 Duebendorf, Switzerland 3Institute of Biogeochemistry and Pollutant Dynamics, ETH Zurich,

CH-8092 Zurich, Switzerland Presenting author: minju.lee@epfl.ch

Ozonation is a promising tertiary wastewater treatment option to eliminate micropollutants such as pharmaceuticals and personal care products present in wastewater effluents prior to its discharge into the aquatic environment. Second-order rate constants (kO3) for the reaction of ozone with micropollutants are essential parameters to determine the optimal ozone dose to achieve a desired elimination efficiency of target micropollutants. A few hundred kO3-values determined experimentally are available in literature [1]. However, there are a number of emerging micropollutants for which kO3-values have not been measured yet and therefore it is difficult to assess the efficiency of ozonation for these compounds. In this study, kO3 prediction models were developed for aromatic compounds, olefins, and amines by correlating logkO3 with quantum molecular descriptors such as the Highest Occupied Molecular Orbital (HOMO) and the Natural Bond Orbital (NBO). Those quantum descriptors were obtained from quantum chemical calculations using the electronic structure software Gaussian 09.C01. Four different levels of theory (HF and B3LYP method coupled with the 6-31G and 6-311++G** basis set) were used for all individual compounds and the polarizable continuum model (PCM) was used as the implicit solvation method throughout the whole calculations. The energy of the HOMO or a MO lower than the HOMO (HOMO-n, n≥0) of aromatic compounds showed good correlations with the corresponding kO3 by dividing them into five different groups, i) phenol derivatives (R2=0.94-~0.95, n=35), ii) benzene dervatives (R2=0.67-~0.78, n=50), iii) aniline derivatives (R2=0.82-~0.86, n=16), iv) mono- and di-alkoxybenzenes (R2=0.80-~0.90, n=17), v) trimethoxybenzenes (R2=0.98-~0.99, n=4). An unsatisfactory correlation was observed for olefins using their HOMO energies. Instead, the kO3-values of olefins turned out to correlate well with the natural bond orbital (NBO) energy of the π bond of the carbon-carbon double bond of olefins calculated by the NBO 3.1 program (R2=0.80-~0.88, n=45). kO3-values of amines were found to be correlating well with the NBO energy of the nitrogen lone-pair electrons (R2=0.81-~0.82, n=59). The performance of the quantum calculation models developed in this study overall turned out to be similar to or better than the quantatitive structure-actitivty relationship (QSAR) models previsouly developed [2] for aromatic compounds (nphenols=28, nbenzenes=21, nanilines=14), olefins (n=40), and amines (n=48).

References 1. C. von Sonntag and U. von Gunten. Chemistry of ozone in water and wastewater treatment: From

basic principles to applications (IWA, London 2012).

 

13

0411  

INTERPLAY BETWEEN OXIDANT STABILITY AND EFFICIENCY OF

MICROPOLLUTANT ABATEMENT IN CONVENTIONAL AND ADVANCED

OXIDATION PROCESSES

Yunho Lee1, Urs von Gunten2 1School of Environment Science and Engineering, GIST-Gwangju Institute of Science and

Technology, 500-712, Gwangju, Republic of Korea 2School of Architecture, Civil and Environmental Engineering (ENAC), Ecole Polytechnique

Fédérale de Lausanne (EPFL), CH-1015, Lausanne, Switzerland Presenting author: yhlee42@gist.ac.kr

Oxidation processes are widely applied in water treatment for disinfection and oxidation purposes. Possible chemical oxidants in water treatment are chlorine, chlorine dioxide, ferrate, ozone, and permanganate as selective oxidants and hydroxyl radical as a less selective oxidant. In recent years, oxidation processes have received increasing attention as potential tools to eliminate various organic micropollutants in enhanced wastewater or drinking water treatment. The efficiency of micropollutant elimination depends on the following aspects: 1) reactivity of an oxidant with a target micropollutant and water matrices-kinetics, 2) removal of undesirable effects of a micropollutant after structural transformation, and 3) possible formation of undesirable byproducts from the reaction of an oxidant with water matrix components. In this talk, the kinetic aspects of micropollutant transformation efficiency will be mainly discussed. The transformation efficiency of micropollutants can be assessed or predicted by the integrated form of the second-order kinetic equation for the reaction of an oxidant (Ox) with a micropollutant (P), i.e., [P]/[P]0 = exp(−k∫[Ox]dt) in which k is the second-order rate constant and ∫[Ox]dt is the time-integrated oxidant concentration (oxidant exposure that represents the oxidant stability). Many second-order rate constants are available in literature for the reaction of the aforementioned oxidants with various organic compounds including micropollutants. The kinetic information indicates that the selective oxidants react only with some electron-rich organic moieties (ERMs), such as phenols, anilines, olefins, organic sulfur, and deprotonated-amines. Hydroxyl radicals (•OH), in contrast, show a nearly diffusion-controlled reactivity with almost all organic moieties (k ≥ 109 M-1 s-1). Quantitative structure-activity relationships (QSARs) based on Hammett or Taft Sigma constants were developed for the selective oxidants and could be used to predict the second-order rate constants for various micropollutants containing ERMs. For •OH, the group contribution method has been developed for the prediction of second-order rate constants. Due to a competition for oxidants between a target micropollutant and water matrix (i.e. dissolved organic matter-DOM), a higher reaction rate constant with a micropollutant does not necessarily mean a more efficient transformation. In addition, the competition disappears rapidly for the selective oxidants after the ERMs present in DOM are consumed. In contrast, for •OH, the competition is practically the same during the entire oxidation. This explains why selective oxidants can be more efficient than •OH for transforming micropollutants with ERMs, while •OH are effective for transforming micropollutants even without ERMs.

 

14

The chemical kinetics approach described above was applied to predict the transformation efficiency of various micropollutants during ozonation of municipal wastewater effluents (10 municipal wastewater effluents + one hospital wastewater effluent). Consistent eliminations as a function of the DOC-normalized specific ozone dose (gO3/gDOC) were observed for micropollutants with similar ozone and •OH rate constants. Micropollutants could be classified into five groups having characteristic elimination patterns accordingly to their ozone and hydroxyl radical rate constants. The transformation efficiencies of the selected micropollutants could be predicted based on their ozone and •OH rate constants (predicted or taken from literature) and the determined ozone and •OH exposures. Consistent molar •OH yields were observed for the same gO3/gDOC (e.g., 21±3% for gO3/gDOC = 1.0). In addition, the rate constant for the reaction of •OH with effluent organic matter were found to be quite constant ((2.1±0.6)×104 (mgC/L)-1 s-1). Reasonable agreements between the measured and predicted transformation levels of micropollutants were found. These data clearly demonstrate that the proposed chemical kinetics method can be used for a generalized prediction of micropollutant transformation during wastewater ozonation. Keywords: oxidation, ozone, chlorine, hydroxyl radicals, ferrate, kinetics, micropollutant

References Lee, Y., von Gunten, U. (2010) Oxidative transformation of micropollutants during municipal wastewater treatment: comparison of kinetic aspects of selective (chlorine, chlorine dioxide, ferrateVI, and ozone) and non-selective oxidants (hydroxyl radicals). Water Research, 44, 555-566. Lee, Y., von Gunten, U. (2012) Quantitative Structure-Activity Relationships (QSARs) for the Transformation of organic micropollutants during oxidative water treatment. Water Research, 46, 6177-6195. Lee, Y., Gerrity, D., Lee, M., Bogeat, A.E., Salhi, E., Gamage, S., Trenholm, R.A., Wert, E.C., Snyder, S.A., von Gunten, U. (2013) Prediction of micropollutant elimination during ozonation of municipal wastewater effluents: Use of kinetic and water specific information. Environmental Science & Technology, 47, 5872-5881. Lee, Y., Koalova, L., McArdell, C.S., von Gunten, U. Prediction of micropollutant elimination during ozonation of a hospital wastewater effluent. Water Research, submitted Acknowledgements The Basic Science Research Program through the National Research Foundation of Korea (NRF-2012R1A1A1010985) is acknowledged for supporting this presentation.    

 

15

0433  

CARBON DIOXIDE TRIGGERED METAL(LOID) MOBILISATION IN A MOFETTE

J. Mehlhorn1, F. Beulig2, K. Küsel2,3, B. Planer-Friedrich1

1University of Bayreuth, Environmental Geochemistry, Bayreuth Center for Ecology and Environmental Research (BayCEER), 95440 Bayreuth, Germany

2Friedrich Schiller University Jena, Aquatic Geomicrobiology, Institute of Ecology, 07743 Jena, Germany

3German Centre for Integrative Biodiversity Research (iDiv) Halle-Jena-Leipzig, 04103 Leipzig, Germany

Presenting author: judith.mehlhorn@uni-bayreuth.de Carbon capture and geologic storage is a frequently discussed option to reduce atmospheric CO2 concentrations with the long-term risk of leakage from storage sites to overlying aquifers and soils [1]. As natural analogues to such leakages, we chose cold volcanic CO2 exhalations, so-called mofettes, in a wetland area in the Czech Republic to follow the fate of metal(loid)s under CO2-saturated conditions. Compared to reference fluvisols at the study site, mofette soils were characterised by decreased pH (by 0.5 to 4.9 ± 0.05) and redox potential (by 80 mV to 300 ± 40 mV), as well as accumulation of organic carbon. Poorly and well-crystalline Fe (hydr)oxides, the most important metal(loid) sorbents in the CO2-unaffected soils (7.9 ± 5.9 g kg-1), showed significantly lower concentrations under the acidic and reducing conditions in the mofettes (1.2 ± 0.4 g kg-1). In turn, this increased the mobility of adsorbed As with up to 2.5 times higher concentrations in mofette pore waters (58 ± 18 µg L-1). Arsenic methylation (up to 11 % of total As) and thiolation (up to 9 %) contributed to its net-mobilisation. Dissolved Mn (131 ± 53 µg L-1), Ni (9.1 ± 3.1 µg L-1) and especially Cu (2.2 ± 1.0 µg L-1) remained low, likely

due to complexation and/or adsorption to organic matter and remaining Fe (hydr)oxides. A one-month in situ mobilisation experiment showed mobilisation of all considered elements to the aqueous phase suggesting that desorption is the faster and initially dominating process while resorption is a secondary, slower process. We conclude that the CO2-induced mobilisation of toxic As and net-immobilisation of essential micro-nutrients (Mn, Ni, Cu) (Figure 1) constitute serious risks and should be tested for transferability and relevance at geologic carbon storage sites. Reference 1. Y.-S. Jun, D. E. Giammar, C. J. Werth, and D. A. Dzombak, Environ. Sci. Technol. 47, 1-2 (2013)

Figure 1: Graphical summary of mobilisation and immobilisation processes in a mofette soil (right)

compared to a CO2-unaffected reference soil (left).

Corg

Fe

As

Mn

Ni Cu

Cu Ni

partlyoxicCO2

O2

Reference

NiCu

Mn

As

Fe

As

Mn

Ni Cu

Cu Ni

Mofette

NiCu

Mn

As

Fe

anoxicCH4CO2 CO2

CO2 CO2O2

CH4

Fe

Corg

Fe (hydr)oxides

Organic matter

Solid phase/in solution

As/As Net-mobilisation

Net-immobilisation

pH

Fe

Corg

 

16

0446  

SOURCE APPORTIONMENT OF ORGANIC AEROSOL IN AMAZON REGION

P.C. Vasconcellos1, N. de Oliveira Alves2, J. Brito3, A. Arana4, S. E. Caumo1, P. Artaxo3,

S. Hacon5, R. Hillamo6, S. R. Batistuzzo de Medeiros7 1 Institute of Chemistry, University of São Paulo, São Paulo, Brazil

2 Biochemistry Department, Federal University of Rio Grande do Norte, Natal, Brazil 3 Institute of Physics, University of São Paulo, São Paulo, Brazil

4 National Institute for Amazonia Research, Manaus, Brazil 5National School of Public Health at Oswaldo Cruz Foundation, Rio de Janeiro, Brazil

6Finnish Meteorological Institute, Atmospheric Composition Research, Helsinki, Finland 7 Cellular Biology and Genetics Department, Federal University of Rio Grande do Norte, Natal,

Brazil Presenting author email: perola@iq.usp.br

The Brazilian Amazon contains about 40% of the world's remaining tropical rainforest, corresponding to 61% of the area of Brazil [1]. The appropriate source identification is fundamental as guidance of public health policies and providing foundations for health intervention. The aim this work is to evaluate the origin of organic compounds using a Principal Component Analysis (PCA) near Porto Velho, southwest of Brazilian Amazon region. The results show a three-factor solution was resolved by PCA analysis (Table 1). The first factor clearly showed that the source apportionment of OC (76%), EC (72%), levoglucosan (100%), and retene (100%) were

dominated by biomass burning. The second factor depicts an important contribution of several PAHs without a single source class and therefore was considered as mixed sources factor. The third factor was characterized by more than 65% of each of dibenz[a,h]anthracene, indene[1,2,3-c,d]pyrene and benz[g,h,i]pyrene. Also, about 20% of OC and EC were associated with this factor. Therefore, this factor was considered as diesel emissions that are higher during the dry season because there is a great demand for energy supply. This is also a critical period for the human health implications. This work enhances the knowledge of aerosol sources on an Amazon region highly impacted by anthropogenic activities with significant contribution on climate and potential risks to human health, especially for the most vulnerable groups. Acknowledgements This work was supported by CNPq and Brazilian National Institute of Science and Technology (INCT) for Climate Change funded by CNPq Grant Number 573797/2008-0 and FAPESP Grant Number 2008/57719-9. Reference [1] Davidson, E. a, De Araújo, A. C., Artaxo, P. et al. (2012). The Amazon basin in transition. Nature, 481(7381).

Table 1: Results of PCA analysis .

Compounds Biomass Burning Mix Diesel

F1 F2 F3 Levoglucosan 0.93 0.23 0.12

Organic carbon 0.92 0.14 0.11 Retene 0.87 0.23 0.04 PM10 0.86 0.14 0.21

Elementar Carbon 0.85 0.27 0.33 Benz[e]Pyrene 0.76 0.54 0.22

Anthracene 0.23 0.89 0.25 Chrysene 0.29 0.82 0.49

Pyrene 0.33 0.77 0.53 Benz[a]anthracene 0.31 0.75 0.57

Benz[a]pyrene 0.40 0.71 0.57 Benz[b]fluoranthene 0.42 0.67 0.60

Benz[g,h,i]pyrene 0.20 0.30 0.93 Dibenz[a,h]anthracene 0.21 0.30 0.93

Indene[1,2,3-c,d]pyrene 0.12 0.41 0.89

Benz[k]fluoranthene 0.33 0.62 0.69

 

17

0462  

VIRUS DISINFECTION BY ADVANCED OXIDATION –

CAN WE KILL THEM ALL?

T. Kohn

Ecole Polytechnique Fédérale de Lausanne, School of Architecture, Civil and Environmental Engineering, Laboratory of Environmental Chemistry, Lausanne 1015, Switzerland

tamar.kohn@epfl.ch Despite the remarkable progress accomplished in water and wastewater treatment over the past decades, pathogens in drinking and recreational water continue to pose a threat to public health in both industrialized and developing nations. Pathogenic viruses present a particular challenge for microbial water quality because they are excreted in very high numbers from infected patients, while their infectious dose can be very low. Both conventional disinfection processes as well as advanced oxidation technologies (AOTs) have proven useful in reducing the number of infectious viruses, though the disinfection success varies greatly between disinfectants. For example, human adenovirus is relatively resistant to UV, but is readily inactivated by oxidants, including those encountered in AOTs. This indicates that UV and oxidants inactivate viruses by different modes of action, though the details of these processes are not understood. In this presentation, new insights into the mechanism of action of UV and oxidants on enteric viruses are discussed. Enteric viruses consist of a single or double strand of RNA or DNA encapsulated in a protein capsid, and each of these components can serve as a disinfectant’s main target. Protein mass spectrometry and quantitative PCR were employed to monitor the effect of disinfection on these viral components. The observed damage was then linked to losses in vital virus functions, such as host cell entry or genome replication. Results show that for UV, the viral genome is the main target, while most oxidants target both viral genome and proteins. Genome damage readily led to inactivation by inhibiting the virus’ ability to replicate inside the host. In contrast, protein damage was often found to be inconsequential, unless it occurred in regions directly involved in host attachment. This detailed insight into disinfection mechanisms allows us to understand instances of disinfection failure: partial resistance to disinfection by oxidants can be achieved by either forming large viral aggregates, or by deposition of shielding disinfection products onto the virus surface, thus preventing access of the oxidants to crucial protein sites. Viral aggregation also offers some protection against UV, by facilitating recombination of damaged genome segments. Finally, repeated exposure to UV or oxidants leads to resistant virus populations. This could be related to few mutations, which had important consequences on the stability of vitally important regions in the viral genome or proteins. Ultimately, the outcomes of this work allow us to assess potential pitfalls associated with virus disinfection by AOTs, and enables us to design optimal treatment strategies to achieve the best possible virus disinfection.

 

18

0488  

 

ASSESSMENT OF VOLATILE ORGANIC COMPOUNDS EXPOSURE AMONG

DIFFERENT TRANSPORTATION MODES IN GHENT, BELGIUM

D. H. Do, H. Van Langenhove, S. I. Chigbo, A. N. Amare, K. Demeestere, C. Walgraeve Department of Sustainable Organic Chemistry and Technology, Ghent University, Belgium

Presenting author: do.hoaiduc@ugent.be People spend up to 85-90% of their time indoors (houses, offices, bars), and a significant amount of time (5%) in traffic while commuting to and from work. Real life exposure to volatile organic compounds (VOCs) could be higher than estimated from concentration data obtained from fixed air quality stations. Increasing efforts of the government to promote public transportation (bus tram, metro, train) and healthy non-motorized alternatives (walking, cycling) as substitutes for cars makes it valuable to assess the exposure levels to which commuters, using different transportation modes, are exposed. Therefore, three transportation modes including tram, car and bicycle are selected and concentration levels of 84 volatile organic compounds were measured along a route in Ghent, Belgium. Concentration levels were obtained by active sampling on Tenax TA sorbent tubes followed by thermal desorption gas chromatography mass spectrometry (TD-GC-MS). It is observed that aromatic hydrocarbons account for a significant proportion in the total VOCs concentration (TVOCs) being as high as 41-57%, 59-72% and 58-72% for the tram, car and bicycle respectively. Commuters using the tram experience the highest TVOCs concentration levels. However, the physical activity level involving the mode of transportation is important to assess the exposure to toxic VOCs. It is proven that the commuter using a bicycle (4.3 ±1.5 µg) inhales seven and nine times more benzene compared to the commuter using the car and tram respectively, when the same route is followed. Key words: VOC, active sampling, commuter exposure, inhalation dose, traffic air, transportation modes, tram, car, bicycle, Ghent, Belgium

 

19

0493  

 

QUALITY OF MONITORING MEASUREMENTS UNDER THE WATER

FRAMEWORK DIRECTIVE: TECHNICAL CHALLENGES CREATED BY THE

REGULATORY REQUIREMENTS

M. Ricci, B. Koleva, R. Lava, I. Dosis, S. Elordui-Zapatarietxe,

H. Emteborg, A. Held, H. Emons

European Commission, Joint Research Centre, Institute for Reference Materials and Measurements (IRMM), 2440, Geel, Belgium

Presenting author: Marina.RICCI@ec.europa.eu Forty-five priority substances (PSs) are regulated by the recently approved Directive 2013/39/EU [1], which introduced twelve new organic pollutants supplementing the first list of thirty-three given in the Directive 2008/108/EC [2]. This Directive also establishes Environmental Quality Standards (EQS) in biota for some of the PSs. Directive 2009/90/EC [3] lays down stringent technical specifications for chemical analysis and monitoring of water status. The laboratories appointed by the Member States as responsible for the chemical water monitoring should apply quality management system practices accepted at international level and demonstrate their competence by participation in proficiency testing (PT) programs and analysis of available reference materials (RMs). For many of the PSs there is a significant lack of appropriate quality assurance/quality control (QA/QC) tools to support and validate the monitoring measurements according to the performance criteria imposed by the legislation [3], in terms of validated methods of analysis, PT schemes and certified reference materials (CRMs). An overview of the present status with respect to the availability of these QA/QC tools for the Water Framework Directive (WFD) relevant matrices (water, biota and sediment) will be presented, highlighting the gaps and indicating some on-going developments. In specific, the choice of the proper CRM can be critical for the laboratory responsible of reporting monitoring data in the context of the WFD. The CRMs should be fit-for-purpose e.g. with certified values close to the EQS (and sufficiently small uncertainty), mimicking the real environmental sample matrices and accompanied by appropriate information for optimal use [4]. All of the latter can considerably improve the quality of the measurement results. Examples of (C)RMs for the analysis of some PSs in fish and water under production at JRC-IRMM will be illustrated. References 1. European Commission, Directive 2013/39/EU of the European Parliament and of the Council

of 13 August 2013, Off. J. Eur. Union L 226, 119 (2013). 2. European Commission, Directive 2008/105/EC on environmental quality standards in the field

of water policy Off. J. Eur. Union L 201 (2009) 36. 3. European Commission, Directive 2009/90/EC of the European Parliament and of the Council

of 31 July 2009, Off. J. Eur. Union L 201, 36 (2009). 4. M. Ricci, I. Kourtchev and H. Emons, Trends Anal. Chem. 36, 47 (2012)    

 

20

0467  

IDENTIFICATION OF TRANSFORMATION PRODUCTS FORMED DURING

ELECTROLYSIS AND OZONATION

T.A. Ternes, C. Prasse, C. Lütke Eversloh

Federal Institute of Hydrology, Department Aquatic Chemistry, 56068, Koblenz, Germany Presenting author: ternes@bafg.de

Oxidative processes such as ozonation and electrolysis have been shown to eliminate a wide spectrum of micropollutants from wastewater. Even though a complete mineralization is often not feasible due to the high energy consumption, oxidation of bio-recalcitrant moieties might lead to further degradation in subsequent biodegradation. In the current studies the transformation of selected contrast media and tramadol was investigated during oxidative processes such as ozonation and electrolysis. The transformation products (TPs) formed were elucidated by high-resolution mass spectrometry and NMR. In the past the elucidation of TP formation was extremely time consuming or even impossible for chemical processes due to the limited analytical capabilities. This situation changed in the last 15 years. Modern hybrid mass spectrometry systems (e.g. FT-MS, ion trap MS, SF-MS, Q-MS, TOF-MS) provide the accurate masses of TPs and deliver information of mass fragments which can be used to identify the chemical structure. One possibility to confirm the chemical structure of a TP is the nuclear magnetic resonance spectroscopy (NMR). However, a drawback of NMR today is still the elevated quantity needed of a relative pure isolated standard. Electrochemical treatment using boron-doped diamond electrodes provides a way to generate highly reactive hydroxyl radicals and therefore facilitate degradation of various micropollutants such as iopromide. Although cathodic reduction of the latter easily leads to dehalogenated derivatives, it was found that mineralization takes place almost exclusively via anodic reactions without formation of significant amounts of oxidation products.[1] In contrast to that, electrolysis of tramadol furnished a series of anodically formed TPs. Besides typical oxidation and hydroxylation reactions, chlorination of tramadol was observed due to in-situ generation of active chlorine. Other transformations, such as demethylations were found to occur in analogy to previous studies using ferrate(VI) or ozone as oxidants.[2] The German BMBF project TransRisk (www.transrisk-projekt.de) investigates the suitability of ozonation and subsequent biofiltration and activated carbon filtration for the elimination of organic micropollutants from conventional treated wastewater. Special emphasis is placed on the elucidation of TPs formed during an ozonation step and their removal during subsequent treatment. Tramadol-N-oxide, the main TP being formed during ozonation of tramadol has also been observed in the effluent of the ozonation pilot plant with concentrations in the low ng/L range. In contrast to activated carbon filtration, tramadol-N-oxide was not completely eliminated in subsequent treatment by biofiltration indicating its biological stability. In addition, the increased polarities of oxidative TPs might also result in a lower sorption affinity to activated carbon. One example is COFA, a TP formed during ozonation of carboxy-acyclovir, a biological TP of the antiviral drug acyclovir [3], which was detected in ozonated waters as well as biofilter and activated carbon filter effluents in concentrations up to 5 µg L-1.

References 1. C. Lütke Eversloh, N. Henning, M. Schulz, T.A. Ternes, Water Res. 48, 237 (2014). 2. S.G. Zimmermann, A. Schmukat, M. Schulz, J. Benner, U. von Gunten, T.A. Ternes, Environ. Sci.

Technol. 46, 876 (2012). 3. C. Prasse, M. Wagner, R. Schulz, T.A. Ternes, Environ. Sci. Technol. 46, 2169 (2012).

 

21

0552  

MULTI-ELEMENTS ATMOSPHERIC DEPOSITION STUDY IN ALBANIA

P. Lazo1, F. Qarri2, L. Bekteshi3, T. Stafilov4, M. Frontasyeva5, H. Harmens6 1 Department of Chemistry, Faculty of Natural Sciences, University of Tirana, 10,

Tirana, Albania 2 Department of Chemistry, University of Vlora, 13, Vlora, Albania

3 Department of Chemistry, Faculty of Natural Sciences, University of Elbasan, 23, Elbasan, Albania

4 Institute of Chemistry, Faculty of Science, Sts. Cyril and Methodius University, 1000, Skopje, Macedonia

5 Frank Laboratory of Neutron Physics, Joint Institute for Nuclear Research, 141980, Dubna, Russia

6 Centre for Ecology & Hydrology, BT20, Bangor, United Kingdom Presenting author: pranveralazo@gmail.com

Air quality can be monitored by measuring the concentration of pollutants in the air or directly on deposits by building models that describe the transport of pollutants or by using biomonitors [1]. Through the use of different types of vegetation, the levels of atmospheric trace metal deposition have been successfully monitored [2]. The use of native terrestrial ectohydric mosses as biomonitors is now a well-recognized technique in studies of atmospheric contamination [3] and is applied as a practical mode in establishing and characterizing deposition sources. For the first time, the moss biomonitoring technique and ICP-AES analysis were applied to study the multi-element atmospheric deposition in Albania. Moss samples (Hypnum cupressiforme) were collected during the summer of 2011 and autumn 2010 from 44 sites, evenly distributed over the country. The sampling was performed in accordance with the LRTAP Convention–ICP Vegetation protocol and the strategy of the European Programme on Biomonitoring of Heavy Metal Atmospheric Deposition. This study was conducted in the framework of ICP Vegetation in order to provide a reliable assessment of air quality throughout Albania and to produce information needed for better identification of contamination sources and improving the potential for assessing environmental and health risks in Albania, associated with toxic metals. The spatial distribution of 19 elements throughout the Albanian territory was explored in this research. For comparison, the Albanian data were compared with neighboring countries [3] and with Norwegian moss data from a pristine area [4]. For better interpretation of the results, the contamination factor (CF) scales [5] were used to interpret the results of CFs values obtained in this study and to distinguish the contamination level caused by each element. Cluster and factor analysis with varimax rotation were applied to distinguish elements mainly of anthropogenic origin from those originating from natural sources. The geographical distribution maps of the elements over the sampled territory were constructed using GIS technology. The median values of the elements in moss samples of Albania were high for Al, Cr, Ni, Fe, and V and mediate for Cd, Cu, and Pb compared to other European countries, but generally were of a similar level as some of the neighboring countries such as Bulgaria, Croatia, Kosovo, Macedonia, and Romania. References 1 B. Markert, A.M. Breure, H.G. Zechmeister (2003) Bioindicators and biomonitors. Elsevier, Oxford, pp 3–39 2 J. Schilling, M. Lehman (2002) Atmospheric Environment 36:1611–1618 3 Harmens H, Norris D, Mills G. and the participants of the moss survey, (2013), Heavy metals and nitrogen in mosses: spatial patterns in 2010/2011 and long-termtemporal trends in Europe, 63 p. http://icpvegetation.ceh.ac.uk 4 E. Steinnes, T. Berg, H.Uggerud, M. Vadset (2007) State Program for Pollution Monitoring, Report 980/2007, Norwegian State Pollution Control Authority, Oslo 2007, 36 pp. (In Norwegian) 5 J.A. Fernandez and A. Carballeira (2001). Arch Environ Contam Toxicol 40:461–468. doi:10.1007/s002440010198

 

22

 0582  

 

THE IMPACT OF AEROSOLS ON GLOBAL HORIZONTAL IRRADIANCE OVER

SOUTHEASTERN ANATOLIA OF TURKEY

B. Öztaner1, C. Kahya2, S. Incecik2

1Istanbul Technical University, Eurasia Institute of Earth Science, Climate and Marine Science, Maslak Istanbul Turkey

2Istanbul Technical University, Department of Meteorology, Maslak Istanbul Turkey Presenting author: oztaner@itu.edu.tr

The present study deals with the impact of aerosols on global horizontal irradiation which are assessed during the periods April 2011 and April 2012 over Southeastern Anatolia in Turkey using ground-based measurements, WRF model and satellite data. Aerosols affect the earth’s atmosphere through interactions with solar and terrestrial radiation as well as clouds. Solar energy utilization in various applications has increased seriously considered for satisfying a significant part of the energy demand in Turkey due to its geographical position. Specifically Southeastern Anatolia (SEA) of Turkey present a significant potential of solar energy. A photovoltaic power production is significantly dependent on Global Horizontal Irradiance (GHI), cloudiness and aerosols. The aim of the study is to understand the impact of aerosols on GHI over the SEA region. For this purpose daily MODIS Level-2 aerosol optical depth (AOD) data obtained from MODIS Terra platform products are used. MODIS at 550 nm have a spatial resolution of 500m. In addition to AOD data, PM10 data measured at ground level air quality stations in SEA, is used for the air quality stations of SEA (Kilis, Bozova, Mardin and Sırnak). The relationship of AOD and GHI are examined for spring (MAM) and summer (JJA) seasons. The time series of GHI data with AOD for spring and summer of 2011 and 2012 are compared. We found a significant negative relationship between AOD and GHI data for all sites (Level of significance is less than 0.001). Similarly, AOD and PM10 data are compared for both seasons. The scatter plots reveal that there exists a relationship between PM10 and AOD 550 nm in both season. The mean AOD levels in summer are higher than in the spring season. Furthermore, the Cloud-Aerosol Lidar and Infrared Pathfinder Satellite Observations (CALIPSO) data is used to provide continuous high resolution vertical profiles of aerosol properties. Finally, back trajectories have been used to infer source regions of the investigated region via an integrated WRF/HYSPLIT modeling approach. The model is run for the selected episode periods (exceeding air quality standard level) 14-21 April 2011 and 6 -12 April 2012. Modeling results show that aerosols, which have effect on GHI, transport from Saharan, Egyptian and Syrian deserts. The results show that the satellite measurements are able to measure and observe the increase of the dust concentrations over the SAE region of Turkey. Keywords: Aerosol, AOD, dust transport, global horizontal irradiance, CALIPSO

 

23

0653  

 

OCCURRENCE AND REMOVAL OF PHARMACEUTICALS, PESTICIDES AND

FLUORO-SURFACTANTS FROM DRINKING WATER RESOURCES

S. Maeng1, Y. Lee2, C. Jaewon3 1Department of Civil and Environmental Engineering, Sejong University,

143-747, Seoul, Republic of Korea 2 School of Environment Science and Engineering, GIST-Gwangju Institute of Science and

Technology, 500-712, Gwangju, Republic of Korea 3Water Quality Center, Kwater Institute, 305-730, Daejeon, Republic of Korea

Presenting author: smaeng@sejong.ac.kr Environmental contaminants of emerging concern, including pharmaceuticals and pesticides and endocrine disrupting compounds, represent a major concern in drinking water treatment and indirect wastewater portable reuse. The use of chemicals in each country depends on many factors such as type of industries, agricultural practices and living conditions, which also varies within a country depending on geographical location. Surface water is the major source of drinking water and has often been impacted by wastewater discharges or agriculture runoffs, raising the issue of possible occurrence of organic micropollutants in drinking waters. In this study, the occurrence and removal of seven pharmaceuticals (carbamazepine, ibuprofen, caffeine, iopromide, sulfamethazin, sulfathiazole, and, sulfamethoxazole), ten pesticides (carbendazim, isoprothiolane, hexaconazole, phosphamidon, simazine, kitazine, tebuconazole, metolachlor, butachlor, and atrazine), and two fluoro-surfactants (perfluorooctanesulfonic acid and perfluorooctane sulfonate) in ten drinking water treatment plants were investigated for more than a year of monitoring campaigns conducted every month. The removal efficiency of the selected micropollutants in conventional and advanced drinking water treatments were measured and compared. The occurrence of pesticides in the raw drinking waters was more influenced by season, and pesticides are often detected at a certain time of the year, usually in the spring. The occurrence pattern of the selected pesticides and pharmaceuticals in the source waters were different across the investigated drinking water treatment plants. The removal efficiencies of the investigated pharmaceuticals and pesticides varied significantly depending on their physicochemical properties such as log Kow. Most pesticides were efficiently removed by drinking water treatments, but metolachlor was poorly removed. Among the pharmaceuticals, carbamazepine was not effectively removed. Iopromide was the most frequently detected and showed the highest concentration in the investigated source waters. This suggests that iopromide can be served as an indicator for anthropogenic contamination (e.g., wastewater effluent discharge). This study reports the intensive monitoring results for the occurrence and removal efficiencies of various organic micropollutants indrinking waters, which is currently poorly understood. The selected organic micropollutants were determined at concentrations of a few ng/L to µg/L in the investigated source waters, which clearly supports the continuous future monitoring activities. Acknowledgements This study was supported by the Korea Ministry of Environment as a part of “The Eco-Innovation project” (Global Top Project) GT-SWS-11-01-006-0    

 

24

0655  

ZERO VALENT IRON-BASED ADVANCED OXIDATION PROCESSES AS

POTENTIAL ALTERNATIVES TO THE CLASSICAL HOMOGENOUS FENTON

TREATMENT OF INDUSTRIAL MICROPOLLUTANTS: A CASE STUDY WITH

DIMETHYL PHYTHALATE AND OCTYLPHENOL POLYETHOXYLATE

I. Arslan-Alaton, T. Olmez-Hanci, K. Temiz, C. Bihter Yazici

Istanbul Technical University, School of Civil Engineering, Department of Environmental Engineering, 34469 Maslak, Istanbul, Turkey

Presenting author: arslanid@itu.edu.tr Intensive industrial and urban activities have led to increased pollutant concentrations in water and wastewater, causing serious health-related and ecotoxicological problems in the environment. In the last three decades, Advanced oxidation processes (AOPs) have been developed to treat problematic (toxic, biorefractory) pollutants found in effluent streams. More recently, the use of sulfate radical (SO4•

-)-based AOPs (S2O82-/UV-C, S2O8

2-/Fen+, etc.) and zero-valent iron (ZVI; Fe0) has received global interest and promising treatment efficiencies have been reported so far in the scientific literature. ZVI-based treatment systems have already been applied as alternatives to the more conventional Fenton and Fenton-like processes for the removal of chlorinated organics, nitroaromatic compounds, arsenic, heavy metals, nitrate, industrial dyes, and phenols. ZVI is reactive (RP=-0.44 eV), non-toxic, abundant, cheap, relatively easy to produce and its treatment applications require little maintenance. ZVI is capable of oxidizing pollutants by an electron transfer mechanism; however, for harsher conditions, ZVI treatment has to be enhanced chemical or thermally. In the present study, two industrial micropollutants (dimethyl phthalate-DMP; octylphenol polythoxylate-OPPE) were chosen as model contaminants and subjected to nano-sized ZVI treatment under varying reaction conditions for 20 mg/L aqueous pollutant. DMP is a common representative of di-alkyl phthalate esters being classified as an endocrine-disrupting and priority pollutant by various environmental agencies, whereas the nonionic surfactant OPPE has been widely used in the formulations of detergents, emulsifiers, wetting agents, solubilizers and dispersants. The fate of OPPE metabolites is of main concern since they can mimic natural hormones in aquatic organisms, wildlife and even humans. Our treatment results have indicated that (i) no removal of DMP/TOC was observed with 1 g/L ZVI at different treatment pH’s (3-5-7-9); (ii) no DMP/TOC removal was observed at pH 5 and different ZVI concentrations (0.25-0.5-1.0-2.5 g/L); (iii) 29% TOC removal occurred after 40 min treatment levelling off until 120 min in the presence of 2.5 mM persulfate-PS (1 g/L ZVI at pH 5). In the case of OPPE, (i) highest OPEO/TOC removal (10%) in the absence of PS was achieved at pH 5 with 1 g/L ZVI among 0.25-0.5-1.0-2.5 g/L after 60 min; (ii) OPEO/TOC removal decreased only at pH’s above 7 (from 19-22% at pH 3-7 to 3% at pH 9), in the presence of 2.5 mM PS after 60 min treatment; (iii) highest OPEO/TOC removal (33%) was obtained in the presence of 2.5 mM PS and 1 g/L ZVI at pH 5 after 60 min. In the absence of ZVI, 17% TOC removal was obtained for 20 mg/L OPEO with 2.5 mM PS after 60 min treatment at pH 5. Changes in acute toxicity will be examined for the selected ZVI-based treatment processes by two different bioassay protocols employing the photobacteria Vibrio fischeri and the freshwater algae Pseudokirchneriella subcapitata.

 

25

0660  

 

OXIDATION OF ENROFLOXACIN WITH PERMANGANATE: KINETICS, IDENTIFICATION OF OXIDATION PRODUCTS AND DETERMINATION OF

RESIDUAL ANTIBACTERIAL ACTIVITY

Y. Xu1,2, S. Liu1,2, F. Cui1,2 1State Key Laboratory of Urban Water Resource and Environment,

Harbin Institute of Technology, 150090, Harbin, China 2School of Municipal and Environmental Engineering, Harbin Institute of Technology, 150090, Harbin, China

Presenting author: shiyao0715@163.com Potassium permanganate [Mn(VII)] Chemistry Oxidation of fluoroquinolone antibiotic enrofloxacin in water is investigated with respect to the kinetics, the mechanisms on the oxidation and the evaluation of residual antibacterial activity after oxidative treatment. High-resolution and high-accuracy Accurate-Mass Quadrupole Time-of-Flight mass spectrometry coupled to high performance liquid chromatograph was used to determine the accurate mass of the measured degradation products. Four main and four minor oxidation products were identified at neutral pH. An oxidation with Mn(VII) pathway for enrofloxacin is proposed. The oxidation took place at the piperazine ring, at which the C-H adjacent to the amine group was attacked by Mn(VII) [1]. Structural changes to the piperazine ring include N-dealkylation, hydroxylation and hydrolysis. The quinolone core remained intact and, defluorination and structural changes to cyclopropyl group were not observed [2]. Residual antibacterial activity of the oxidative reaction solutions against nonresistant Escherichia coli (G-) reference strain DH5ɑ is evaluated by means of quantifying bacterial colonies. It is noticed that the oxidation products exhibited reduction in antibacterial activity comparing to their precursor. The relationship between antibacterial activity and chemical substituent on quinolone ring was assayed, the substituent at carbon-7 is the binding site to enzyme, which significantly affected the activity against Gram negative bacteria [3].

References 1. E. T. Denisov and I. B. Afanas’ev, Oxidation and Antioxidants in Organic Chemistry and

Biology (Taylor & Francis Group, U.S., 2005). 2. X. V. Doorslaer, K. Demeestere et al, Applied Catalysis B: Environmental 138-139, 333-341

(2013). 3. P. C. Sharma, A. Jain, and S. Jain, Acta. Pol. Pharm 66, 587-604 (2009).

 

26

0685    

ROLE OF BROMIDE FOR N-NITROSAMINE FORMATION FROM NITROGEN-

CONTAINING PRECURSORS DURING OZONATION

S.G. Zimmermann-Steffens1, U. von Gunten1,2 1School of Architecture, Civil and Environmental Engineering (ENAC), Ecole Polytechnique

Fédérale de Lausanne (EPFL), 1015 Lausanne, Switzerland 2 Eawag, Swiss Federal Institute of Aquatic Science and Technology,

8600 Dübendorf, Switzerland Presenting author: saskia.zimmermann@epfl.ch

N-nitrosamines are a toxic class of nitrogenous disinfection by-products (N-DBPs) which can form during oxidative water treatment. Most research has focused on N-nitrosodimethylamine (NDMA) as prominent member of the class of N-nitrosamines. Bromide catalysis is an important NDMA formation mechanism from the precursor dimethylsulfamide (DMS) during ozonation [1]. The present study focuses on the role of bromide for the formation of N-nitros-amines from N-containing precursors during ozonation. The structure of the potential sulfamide- and hydrazine-type precursors was systematically varied. Reaction solutions were screened after ozonation by means of a HPLC - post-column UV photolysis/Griess reaction method that detects nitroso- and nitro-moieties adjacent to C- or N- atoms [2]. N,N-methylethylsulfamide (MES) and N,N-diethylsulfamide (DES) could be confirmed to be precursors for the corresponding N-nitrosomethylethylamine (NMEA) and N-nitrosodiethyl-amine (NDEA), respectively. In analogy to DMS/NDMA [1], the formation pathway is bromide-catalyzed. In contrast, ozonation of the monosubstituted methylsulfamide did not lead to the corresponding N-nitrosomethylamine. This might be due to an additional site of HOBr attack at the monomethylated N-amine as compared to the dialkylated sulfamides DMS, MES, or DES. Substituting the primary N’-amine of DMS with one or two methyl groups prevented the formation of any N-nitrosamine since the methyl groups cannot be cleaved from the sulfamide structure by ozone or HOBr attack. In contrast, substitution with one phenyl group led to the formation of NDMA, a reaction which was bromide-catalyzed. Further sulfamide precursors tested contained a differently substituted phenyl ring at the N’-amine (tolylfluanide (TF) and five TF biometabolites). NDMA was the only N-nitrosamine forming, with bromide catalysis being confirmed for TF so far. It is hypothesized that the phenyl ring is the first site of oxidant attack, yielding DMS and subsequently enabling NDMA formation. Other precursors investigated contained a preformed N-N bond as building block for potential N-nitrosamines. Exclusive NDMA formation was confirmed for two hydrazines with the preformed dimethylamine group: unsymmetrical dimethylhydrazine and daminozide, for which bromide catalysis was excluded. Micropollutants containing a triazenyl or hydrazine moiety showed signals in the Griess method. However, the structure of these products still has to be elucidated by high resolution mass spectrometry. The results from the present study will further deepen our understanding of N-nitrosamine formation and potentially allow a mitigation of this toxic class of N-DBPs. 1. U. von Gunten, E. Salhi, C.K. Schmidt, W.A. Arnold, Environ. Sci. Technol. 44 (15), 5762 –

5768 (2010). 2. M. Lee, Y. Lee, F. Soltermann, U. von Gunten, Water Res., 47, 4893 – 4903 (2013).    

 

27

0707    

EFFECTS OF THE WATER MATRIX

ON SULFATE RADICAL BASED OXIDATION

H. V. Lutze1,2, N. Kerlin1, R. Bakkour1, C. von Sonntag1,3, T.C. Schmidt1,3,4

1 University Duisburg-Essen, Instrumental Analytical Chemistry, Universitätsstr. 5, D-45141 Essen, Germany

2 IWW Water Centre, Moritzstr. 26, D-45476 Mülheim an der Ruhr, Germany 3Max-Planck-Institut für Bioanorganische Chemie,

Stiftstrasse 34-36, P.O. Box 101365, D-45470 Mülheim an der Ruhr 4University Duisburg-Essen, Centre for Water and Environmental Research (ZWU),

Universitätsstr. 5 D-45141 Essen Presenting author: holger.lutze@uni-due.de

The sulfate radical (SO4

●─) finds increasing interest in oxidative water treatment since it is capable of degrading a large number of recalcitrant pollutants [1]. SO4

●─ is formed in the photolysis of persulfate (UV/S2O8

2─) in analogy to the photolysis of hydrogen peroxide (UV/H2O2) which is yielding ●OH (advanced oxidation process (AOP)). SO4

●─ displays different reaction mechanisms compared to ●OH and its unique features may complement AOPs. In oxidative processes the influence of main matrix components such as natural organic matter (NOM), bicarbonate and chloride is very important. In that regard, the reaction of chloride plus SO4

●─ is of particular importance since it can significantly influence the oxidation system. This was investigated by comparing the degradation of two model compounds with very different reactions rates towards SO4

●─ (4-nitrobenzoic acid (pNBA k < 106 M-1 s-1 [2]) and 4 chlorobenzoic acid (pCBA, k = 3.6 × 108 M-1 s-1 [2]). However, if UV/S2O8

2─ is applied to river water pNBA and pCBA are degraded at comparable rates (Figure 1), indicating that another reactive species than SO4

●─ prevails. McElroy has shown, that ●OH are formed in the reaction of SO4

●─ plus Cl─ at neutral pH [3]. This may also apply for natural waters containing Cl─ in the mM range. The influence of NOM was also investigated, revealing that UV/S2O8

2─ is more efficient in pollutant degradation than UV/H2O2, since scavenging of SO4

●─ by NOM is weaker compared with ●OH. Furthermore NOM inhibits the formation of the potential carcinogen bromate in UV/S2O8

2─.

Figure 1: Degradation of pCBA and pNBA in UV/S2O82─, River water (1 mM chloride, 2.45 mg L-1 DOC, 1 mM

HCO3─, pH 7.2)

References 1. R. L. Siegrist, M. Crimi, T. J. Simpkin, York Heidelberg Dordrecht London, 2011. 2. P. Neta; V. Madhavan, H. Zemel, R. W. Fessenden,. J. Am. Chem. Soc. 99, 1, 163-164 (1977). 3. W. J. McElroy, J. Phys. Chem. 94, (6), 2435-2441 (1990).

 

28

0708  

 

OCCURRENCE OF DRUGS OF ABUSE IN THE AQUATIC AND ATMOSPHERIC

COMPARTMENTS AND ITS SIGNIFICANCE FOR THE ENVIRONMENT AND THE

SOCIETY

N. Mastroianni1, C. Postigo1, M. López de Alda1, D. Barceló1,2 1Water and Soil Quality Research Group, Department of Environmental Chemistry, Institute of

Environmental Assessment and Water Research, IDAEA-CSIC, Jordi Girona 18-26, 08034, Barcelona, Spain

2 Catalan Institute for Water Research (ICRA), Parc Científic i Tecnològic de la Universitat de Girona, Edifici H2O, Emili Grahit 101, 17003, Girona, Spain

Presenting author: mlaqam@cid.csic.es Drugs of abuse have been recently recognized as emerging environmental pollutants. These substances, either as the parent compounds or as the corresponding human metabolites, have been detected in both the aquatic and the atmospheric compartments. This presentation outlines the analytical methodologies developed by our group for their determination in water [1], sludge [2] and air [3], the results of their application in various different studies performed in Spain [1-9], and the significance of these results from the ecotoxicological point of view [6] and for the society, since their environmental occurrence can be used to evaluate consumption patterns [10,11] and/or to point out potential manufacture, traffic and/or consumption hot sites. Substances tracked in these studies include parent compounds and metabolites belonging to the classes of cocainics, amphetamine-like stimulants, opioids/opiates, LSD, cannabinoids, benzodiazepines, and alcohol. Investigated matrices include raw and treated wastewater [1,4,8], surface water [4,5,6], ground water [7], drinking water [6], sludge [2], and air particles [3,9].

Acknowledgements - This work has been financially supported by the EU (FP7 project SOLUTIONS), the Spanish Ministry of Economy and Competitiveness (SCARCE project) and the Generalitat de Catalunya (2014 SGR 418 and 2014 SGR 291). Nicola Mastroianni acknowledges the JAE Program (CSIC-European Social Funds). References 1. C. Postigo, M. J. López de Alda, D. Barceló, Anal. Chem. 80, 3123-3134 (2008). 2. N. Mastroianni, C. Postigo, M. Lopez de Alda, D. Barceló, J. Chromatogr. A 1322, 29– 37

(2013). 3. C. Postigo, M. J. Lopez de Alda, M. Viana, X. Querol. A. Alastuey, B. Artiñano, D. Barceló,

Anal. Chem. 81, 4382-4388 (2009). 4. C. Postigo, M. López de Alda, D. Barceló, Environ. Int. 36, 75-84 (2010). 5. A. Mendoza, S. González-Alonso, N. Mastroianni, M. López de Alda, D. Barceló, Y.

Valcárcel, Chemosphere 95, 247-255 (2014). 6. A. Mendoza, J.L. Rodriguez-Gil, S. González-Alonso, N. Mastroianni, M. López de Alda, D.

Barceló, Y. Valcárcel, Environ. Int. (submitted) 7. A. Jurado, N. Mastroianni, E. Vazquez-Suñe, J. Carrera, I. Tubau, E. Pujades, C. Postigo, M.

Lopez de Alda, D. Barceló, Sci. Total Environ. 424, 280–288 (2012). 8. C. Postigo, M.J. Lopez de Alda, D. Barceló, Environ. Int. 37, 49–55 (2011).

 

29

0728  

 

ELECTROCHEMISTRY MASS SPECTROMETRY TO STUDY TRANSFORMATION

OF EMERGING CONTAMINANTS – SIMULATING CARBAMAZEPINE

TRANSFORMATION BY WHITE-ROT FUNGI

B. Seiwert1, C. Weidauer1, N. Golan-Rozen2, Y. Hadar2, B. Chefetz2, T. Reemtsma1 1Helmholtz Centre for Environmental Research - UFZ , 04318, Leipzig, Germany

2Hebrew University of Jerusalem, 76100, Rehovot, Israel Presenting author: thorsten.reemtsma@ufz.de

The elucidation of transformation processes of contaminants in organisms, biological treatment systems or the environment can be difficult as such systems consist of a multitude of (natural) compounds that may disturb the determination, recognition or identification of the transformation products (TP) of interest. The simulation of transformation reactions in the laboratory, starting with a pure solution of the test compound, makes the determination and recognition of TP a much easier task. Electrochemistry coupled to liquid chromatography-mass spectrometry (EC-LC-MS) is a method to study oxidative transformation processes. If the electrochemical cell is coupled directly to LC-MS even reaction intermediates of limited stability may be detected. This helps to understand the mechanisms of transformation. EC-MS has been proposed as an instrumental approach to study phase I metabolism in higher organisms1. However electrochemical transformations with boron doped diamond electrodes (BDD electrode) are one-electron transitions and involve also OH radicals. The spectrum of TP is therefore more complex than that formed by microsomes or liver cell homogenates. White-rot fungi, however, provide a diversity of peroxidase enzymes that are capable of one-electron transfer. Therefore we have studied whether EC-LC-MS is suited to simulate the oxidation of emerging pollutants by white-rot fungi. An LC-QTOF mass spectrometer provides separation of transformation products and identification by mass spectrometry without sample pretreatment. High resolution mass spectrometry provides molecular formula information whereas the product ion spectrum is a good basis for structure elucidation. Product ion spectra can be used to establish a library of possible TP to search for in the environment. When EC is coupled on-line to LC-MS also short-lived oxidation intermediates may be detected that help to understand the mechanism of transformation. Finally such a laboratory test systems is quite productive and allows studying the oxidative transformation of a large number of contaminants with limited experimental effort. This concept was validated with carbamazepine (CBZ) as test compound, one of the frequently found pharmaceuticals in wastewater and the aquatic environment. Transformation by EC and by a white rot fungus (Pleurotus oestroatus) was compared. Both systems effectively transformed CBZ. The EC-LC-MS approach generated a large number of TP, their molecular formula and possible structure. Many of these TP were then also detected in culture of P. oestroatus grown with CBZ. Laboratory test systems simulating environmental transformation processes can be favourably coupled to LC-MS to study transformation reactions of emerging contaminants and to elucidate their transformation pathways in natural systems. References 1. Jahn S, Karst U (2012) J. Chromatogr. A 1259, 16-49.

 

30

0740  

DEVELOPMENT OF GREEN ALTERNATIVES TO PHTHALATE PLASTICIZERS

H.C. Erythropel1, T. Brown1, S. Shipley1, J.A. Nicell2, M. Maric, R.L1. Leask1 1McGill University, Dept. of Chemical Engineering, Montreal, Canada

2McGill University, Dept. of Civil Engineering and Applied Mechanics, Montreal, Canada Presenting author: hanno.erythropel@mail.mcgill.ca

Plasticizers are widely used additives to hard and brittle polymers such as poly(vinyl chloride) (PVC). Plasticizers are only loosely bound to the polymer matrix and therefore leach out over time, ending up in the environment. One of the most used plasticizers is di(2-ethylhexyl phthalate) (DEHP), yet it has come under scrutiny in the past due to its slow biodegradation and subsequent build-up in the environment. Moreover, it produces problematic breakdown products, specially its monoester MEHP. This has led to efforts to design new, green plasticizers. This project investigated compounds with the potential to replace phthalates. These were diester compounds based on maleic and succinic acid, esterified with straight-carbon alcohols. These were then tested for their plasticizer properties in rigid unplasticized PVC, as well as for their biodegradation rates when the pure compounds were exposed to the common soil bacterium Rhodococcus rhodocrous. In cross-disciplinary cooperation, these new green compounds are also being tested for toxicity and androgenic activity. Plasticizing properties of these blends were assessed using DSC, mechanical testing, as well as rheology. Results indicate that both groups of green plasticizers seem suitable candidates for replacing DEHP. Biodegradation experiments showed that a substantial difference in hydrolysis rates of one ester bond between the cis-structured maleates, which structurally resemble DEHP, and the saturated succinate compounds [1]. While hydrolysis rates for the maleates were slow, the succinate compounds were removed from the broth in a matter of days [2]. This could help to explain the slow hydrolysis of DEHP in the environment. However, the maleate compounds could be rendered more biodegradable by using straight carbon chains. Combining the results of these tests, we have shown the dramatic influence of the structure of these diester compounds on biodegradation rates, as well as demonstrated ways of rendering the maleate compounds more biodegradable, while maintaining good plasticizer properties. References 1. H.C. Erythropel et al., Chemosphere 86 (8) (2012). 2. H.C. Erythropel et al., Chemosphere 91 (3) (2013).

 

31

0741  

 

A NEW METRIC TO ASSESS SINK LIMITATION OF

REGIONAL MATERIAL FLOWS

U. Kral, P. H. Brunner

Vienna University of Technology, Institute for Water Quality, Resource and Waste Management, Karlsplatz 13/226, A-1040, Vienna, Austria Presenting author: ulrich.kral@tuwien.ac.at

The objective of this paper is to present a new indicator for the assessment of substance flows into sinks. The indicator quantifies the environmentally acceptable mass share of a substance in waste and emission flows to sinks, ranging from 0% as worst case to 100% as best case. First, the indicator is defined. Second, a methodology to determine the indicator score is presented, including (i) inventory analysis based on substance flows analysis, and (ii) impact assessment based on a distance-to-target weighting approach. Finally, the metric developed is applied in three case studies including copper (Cu) and lead (Pb) in the city of Vienna, and Perfluorooctane Sulfonate (PFOS) in Switzerland. The following results are obtained: In Vienna, 99% of Cu flows to geogenic and man-made sinks are in accordance with accepted standards. However, the 0.7% of Cu entering urban soils and the 0.3% entering receiving waters surpass the acceptable level. In the case of Pb, 92% of all flows into sinks prove to be acceptable, but 8% are disposed of in local landfills with limited capacity. For PFOS, 96% of all flows into sinks are acceptable. 4% cannot be evaluated due to a lack of normative criteria, despite posing a risk for human health and the environment. The examples demonstrate the need for appropriate data of good quality to calculate the sink indicator, and for standards needed for the assessment of substance flows to urban soils and receiving waters. The case studies corroborate that the new indicator is of relevance for (i) managing and controlling waste and emission flows on a regional scale, (ii) monitoring the effectiveness of waste and environmental management for directing flows into appropriate sinks, (iii) comparing different regions, and (iv) for communicating scientific results to decision makers and the public.

 

32

0747  

 

INDIVIDUAL AND MIXTURE TOXICITY OF PHARMACEUTICALS AND PHENOLS

ON FRESHWATER ALGAE Chlorella vulgaris

E. Geiger1, M. Türker Saçan2, R. Hornek-Gausterer3 1FH-Technikum Wien (University of Applied Sciences), Höchstädtplatz, 1200 Vienna, Austria

2Bogaziçi University, Institute of Environmental Sciences, Hisar Campus, Bebek 34342, Istanbul, Turkey

3Environment Agency Austria, Spittelauer Lände 5, 1090 Vienna, Austria Presenting author: elisabeth.geiger@technikum-wien.at

Aquatic ecosystems have been severely threatened by discharges of toxic compounds. Increasing chemical usage for domestic, agricultural and industrial purposes, such as phenols and pharmaceuticals, need to be evaluated for potential threat, as they can be detected in water bodies throughout the world. Pharmaceuticals are designed to have a biological therapeutic effect, but may also cause similar effects in non-target organisms. Thus, pharmaceutical pollutants have become an emerging area of concern. The chemicals legislation, spearheaded by REACH and CLP, aims to ensure a high level of protection of human health and the environment, but it is rarely based on the assessment of combination effects of chemicals. The current used regulatory approaches are based on the evaluation and risk assessment of individual chemicals. Since human beings and their environment are exposed to a wide variety of substances, there is an increasing concern about the potential adverse combination effects of chemicals. In this study, the toxicity experiments have been carried out based on the algal growth inhibition test OECD No. 201 (OECD 2006) criteria prepared by the Organization for Economic Cooperation and Development. Individual and binary mixture toxicity experiments of selected pharmaceuticals (ibuprofen and ciprofloxacin) and phenolic compounds (2.4-dichlorophenol and 3-chlorophenol) have been performed with freshwater algae Chlorella vulgaris. Nominal concentration of test solution of each chemical was measured at the end of the experiment by instrumental analytic devices. Inhibition of growth was used as the test endpoint, expressed as the logarithmic increase in biomass (average specific growth rate) during an exposure period of 96 hours determined by daily measurements of optical density at 680 nm. All substances tested had a significant effect on Chlorella vulgaris population density and revealed IC50 values < 100 mg/L. After determination of the single toxicity for each substance, binary mixture tests were conducted using proportions of the respective EC50s (=1 toxic unit (TU)). When a 50% effect occurs at less than 1 TU, the mixture was considered to be greater than additive, or synergistic. The mixture dose-response curve was compared to predicted effects based on both the concentration addition and the independent action model as suggested in regulatory risk assessment. It could be demonstrated that the combined toxicity of pharmaceuticals and phenols can lead to synergistic effects. The potential impacts of pharmaceuticals on aquatic organisms could lead to the inclusion among new priority candidates in the current or future revision of the EU List of Priority Substances relevant to the Water Framework Directive 2000/60/EC [1]. References 1. P. Bottoni, S. Caroli, A. Barra Caracciolo. Pharmaceutical as priority water contaminants.

Environ. Toxicol. Chem. 92, 549-565 (2010).

 

33

0752  

 

DEGRADATION OF ATRAZINE DURING ADVANCED OXIDATION PROCESSES

AND FORMATION OF TOXIC TRANSFORMATION PRODUCTS

S. Allard1, F. Busetti1, J. Y.M. Tang2, J. W.A. Charrois1, B. I. Escher2,3 1Curtin University, CWQRC, GPO Box U1987, Perth WA 6845, Australia

2The University of Queensland, National Research Centre for Environmental Toxicology (Entox), 39 Kessels Rd, Brisbane Qld 4108, Australia

3 Helmholtz Centre for Environmental Research GmbH – UFZ, Permoserstraße 15, 04318 Leipzig, Germany Presenting author: s.allard@curtin.edu.au

Advanced oxidation processes are designed to efficiently remove micropollutants that are refractory to usual drinking water treatment. Even by advanced oxidation, full mineralisation to carbon dioxide is not realistic and transformation products (TPs) are formed. To date, little is known on the identity of the TPs and their relative toxicity. In this study, water sampled post reverse osmosis in an advanced water treatment plant was spiked with atrazine and treated by UV/H2O2 as well as other common tertiary treatments (UV, ozone and ozone with t-BuOH to quench the OH radical for comparison). The main TPs were identified by liquid chromatography high-resolution mass spectrometry (Orbitrap) and the degradation of atrazine quantified in parallel with a bioanalytical assessment of the reaction mixture using a battery of toxicity tests. The bioassays applied were the Microtox assay for cytotoxicity, the chlorophyll fluorescence assay (IPAM) for photosynthesis inhibition and the AREc32 assay for oxidative stress response. Results showed that atrazine was efficiently degraded by OH radicals as confirmed by the UV/H2O2 and ozone experiments (Figure 1). Degradation of atrazine led to the formation of multiple TPs. They were identified through high resolution MS2 and MS3 and molecular

structure were proposed. The photosynthesis inhibition in green algae was assessed as target effect for herbicides. As expected the inhibitory effect on photosynthesis decreased with the degradation of the atrazine. In contrast, the cytotoxicity and the oxidative stress response remained constant or even increased in the case of UV/H2O2 despite disappearance of atrazine (Figure 1), indicating that the transformation products mixtures exhibit equal or higher toxicity compared to atrazine. The identified TPs have similar structure as atrazine, therefore the mixture effect on the toxicity results are easily justified. This study demonstrated the relevance of toxicity related to the

formation of TPs which suggests that the TPs have to be included in the risk assessment of advanced oxidation processes.

O 3 + OH O 3 UV

UV/H 2O 20.0

0.5

1.0

0.00.51.01.52.02.5

fract

ion of

parent

Microtox

relative mixture effect ECP /ECmixture

AREc32

 

34

0763  

 

DARK FORMATION OF •OH RADICALS IN ANOXIC LAKE WATER

D. Vione, M. Minella, E. De Laurentiis, V. Maurino, C. Minero

Dipartimento di Chimica, Università di Torino, Via Pietro Giuria 5, 10125 Torino, Italy Presenting author: davide.vione@unito.it

The hydroxyl radical (·OH) is a highly reactive transient, causing the degradation of most dissolved organic and inorganic substrates [1] and affecting the cycling of carbon and other nutrients. It is formed photochemically in surface waters, by irradiation of photosensitisers such as chromophoric dissolved organic matter (CDOM), nitrite and nitrate [2-3]. Here we report for the first time that ·OH can also be produced in the dark by aeration of anoxic lake water. Many lakes located in temperate environments are stratified during summer, as the warmer and oxygenated surface layer (epilimnion) floats above the colder and often anoxic deep water (hypolimnion). Lake overturn in late summer – early autumn ensures oxygenation of the water column. Dark formation of ·OH was assessed in anoxic water (taken from the hypolimnion during summer stratification) after exposure to the atmosphere, using terephtalic acid (TA) transformation into hydroxyterephtalic acid (TAOH) as ·OH probe reaction. The possible ·OH formation pathways are Fenton and Fenton-like reactions, induced by FeII and most notably by hydroquinones or semiquinone radicals [4]. The importance of the process can be assessed by comparing dark ·OH formation with photochemical processes taking place in the sunlit epilimnion. The cumulated ·OH production of hypolimnion samples exposed to air for a few hours is equivalent to about one-half of the year-round photochemical ·OH generation in the epilimnion. The dark reaction, here described for the first time, is thus a new environmental process that could be very important in the yearly ·OH budget of lake environments. It could play a key role in the self-depollution potential of the lakes and in carbon biogeochemical cycles. This is an exciting new discovery that could deeply modify the current understanding of the processes taking place in lake water and leading to the transformation of natural organic matter and of xenobiotics.

Fig. 1. Time trend of TAOH formed from 1 mM TA in hypolimnion samples exposed to the atmosphere. Insert: highest TAOH concentration reached in the experiments (Surf: surface samples; B1, B2: anoxic samples from the hypolimnion). AV: Lake Avigliana; CA: Lake Candia; SdS: Lake Sottano della Sella; VI: Lake Viverone. References 1. G.V. Buxton, C.L. Greenstock, W.P. Helman, A.B. Ross, J. Phys. Chem. Ref. Data 17, 513

(1988). 2. J.V. Goldstone, M.J. Pullin, S. Bertilsson, B.M. Voelker, Environ. Sci. Technol. 36, 364 (2002). 3. M.A. Tarr, W. Wang, T.S. Bianchi, E. Engelhaupt, Wat. Res. 35, 3688 (2001). 4. S.E. Page, M. Sander, W.A. Arnold, K. McNeill, Environ. Sci. Technol. 46, 1590 (2012).

 

35

0767  

 

COMPARATIVE STUDY OF DIFFERENT UV TYPES (UV-C, UV-B, AND UV-A)

INDUCED PHOTOLYSIS OF A NEW Β-BLOCKER (NEBIVOLOL)

IN AQUEOUS SOLUTION

A. Salma1, T.C. Schmidt2, J. Tuerk1 1 Institute of Energy and Environmental Technology e.V. (IUTA), 47229 Duisburg, Germany

2 Instrumental Analytical Chemistry, University of Duisburg-Essen, Universitätsstr. 5, 45141 Essen, Germany

Presenting author: Salma@iuta.de

Advanced oxidation processes (AOPs) using ultraviolet (UV) light alone or in combination with other oxidizing agents (e.g. TiO2, hydrogen peroxide, Fenton’s reagent etc.) have recently emerged as an important class of technologies for water treatment [1]. Such processes involve the in-situ generation of powerful oxidants such as the hydroxyl radical (HO•) which accelerate the degradation of a wide range of organic contaminants in polluted water [2]. In UV direct photolysis the pollutant to be destroyed will absorb the incident radiation and undergo degradation after excitation from the ground state to its excited state. The efficiency of photodissociation strongly depends on the light absorption event, thus limiting the industrial application of the UV photolytic process compared to the hydroxyl radical driven technologies, where the light absorption by the target pollutant is not required. However, there are many cases where the target pollutants are strong absorbers of UV radiation, and therefore their UV photolysis may become a significant component during the treatment by UV-driven AOP. There are cases when the pollutant can be treated by both direct photolysis and (HO•) radical induced processes. In such cases, the optimization of the treatment process is driven by economic considerations. The overlap of the UV radiation range with the target pollutant absorption range and the electrical energy efficiency of the different UV lamps play a crucial role in the usage of AOPs [3]. Therefore, the main aim of this work is to provide insight into the effectiveness of different types of ultraviolet radiation (UV-C, UV-B and UV-A) on the photodissociation of Nebivolol, a new pharmaceutical compound from the β -blocker group. The understanding of the overall kinetic behavior of Nebivolol degradation (i.e. zero or first order) is necessary for describing meaningfully the degradation mechanism in a wastewater stream. The photochemical degradation reaction of Nebivolol was examined and compared based on the fluence-based kinetic and electrical energy efficiency per order of magnitude of removal (EEO). The degradation rates and efficiencies were compared in the presence and absence of (HO•) radical scavengers in order to propose the main photodegradation pathway, namely direct UV photolysis or (HO•) radical oxidation reaction. The photolytic reactions were also conducted with Nebivolol containing wastewater treatment plant effluent in order to have an overview of the wastewater matrix effect on the degradation rate. Liquid chromatography tandem mass spectrometry and high resolution mass spectrometry were used to identify transformation products at specific degradation times. References 1. A. Vogelpohl, S. M. Kim, J. Ind. Eng. Chem.10, 33-40 (2004). 2. I. H. Kim, N. Yamashita, Y. Kato, H. Tanaka, Water Sci. Technol. 59, 945-955 (2009). 3. Z. Q. Shu, J. R. Bolton, M. Belosevic, M. G. El Din, Water Res.47, 2881-2889 (2013).

 

36

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COMPREHENSIVE TWO-DIMENSIONAL LIQUID CHROMATOGRAPHY APPLIED

TO NATURAL ORGANIC MATTER FROM URBAN ATMOSPHERIC AEROSOLS

A.S. Paula, C.A.D. Loureiro, S.M.S.C. Freire, R.M.B.O. Duarte, A.C.Duarte

Department of Chemistry & CESAM, University of Aveiro, 3810 - 193 Aveiro, Portugal Presenting Author: andreia.paula@ua.pt

The interest of studying natural organic matter (NOM) in atmospheric aerosols has become an emergent topic in Atmospheric Chemistry. Indeed, its chemical composition, structural characteristics, and effects on climate and health are far from being known in detail. For the purpose of resolving the chemical heterogeneity of such complex organic mixtures, comprehensive two-dimensional liquid chromatography (LC×LC) was employed to map the hydrophobicity versus molecular weight (MW) distribution of NOM from atmospheric aerosols collected during different seasons in an urban location at the Western European Coast (Aveiro, Portugal). The LC×LC method employed a mixed-mode hydrophilic interaction column operating under aqueous reversed-phase mode in the first dimension, and a size-exclusion column in the second dimension. The LC×LC fractions were screened on-line by a photodiode array and fluorescence detectors. Findings suggest that the combination of two independent separation mechanisms is promising in extend the range of NOM separation. The applied LC×LC method also indicate that the aerosol NOM samples collected in different seasons exhibit dissimilar profiles in terms of average MW and hydrophobicity. Acknowledgements: Centre for Environmental and Marine Studies (PEsT-c/MAR/LA0017/2013, University of Aveiro, Portugal) and the Portuguese Science and Technology Foundation (FCT), through the European Social Fund and “Programa Operacional Potencial Humano – POPH”, are acknowledged for financial support. This work was also funded by FEDER under the Operational Program for Competitiveness Factors – COMPETE and by National funds via FCT within the framework of research projects ORGANOSOL (PTDC/CTE-ATM/118551/2010) and CN-linkAIR (PTDC/AAG-MAA/2584/2012).

 

37

0811  

 

LIGAND SIZE POLYDISPERSITY EFFECT ON SSCP SIGNAL INTERPRETATION

L. S. Rocha 1, W. G. Botero 2, N. G. Alves 3, J. Moreira 3, A. R. Costa3, J.P. Pinheiro1

1 IBB/CBME, DQF/FCT, University of Algarve, 8005-139 Faro, Portugal. 2 Federal University of Alagoas, 57160000, Arapiraca-Alagoas, Brazil 3 CIQA, DQF/FCT,Universidade do Algarve, 8005-139 Faro, Portugal

Presenting author: lsrocha@ualg.pt In natural waters only a small portion of the total dissolved metal exists as free hydrated cations, because metal ions form stable complexes with a large variety of dissolved inorganic and organic ligands and also adsorbs onto colloids and suspended matter. Most of these ligands have a polyfunctional and polyelectrolytic character and, thus, have a broad range of free energies of complex formation, formation/dissociation rate constants and sizes [1]. Therefore, to establish the relationship between metal ion speciation, bioavailability and biouptake and consequently, the foundations for dynamic risk assessment, it is fundamental to understand the interaction of trace metals with heterogeneous samples and their kinetic characteristics. The knowledge of dynamics factors remains a challenging problem since very few techniques combine the potential to perform dynamic speciation analysis and high sensitivity. Scanning stripping chronopotentiometry (SSCP) fulfils these requirements and the capacity of this technique to obtain dynamic information and to evaluate the chemical heterogeneity has already been investigated and it is well understood [2]. Nevertheless, very little information is known regarding the effect of ligand size polydispersity on metal binding studies using stripping electroanalytical techniques. The main goal of the present work is to investigate the effect of size polydispersity of metal ions binding to mixtures of polymers by SSCP signal. The binding of Cd(II) and Pb(II) to individual charged carboxyl terminated polystyrene sulfonate ((PSS)n-COOH) polymers of different sizes (4, 10 and 30 KDa) was investigated, followed by the metal binding to binary and ternary mixtures of these polymers. The experiments performed showed, as expected, that the stability constants K’ obtained from the shift of the half-wave potential of the SSCP curves were additive according with DeFord and Hume [3] formalism. It was demonstrated for the first time that the metal-ligand diffusion coefficient DML, calculated from the decrease of transition time of the SSCP waves, were also additive for multiple complexes (MLi) simultaneously present in solution, i.e., the sum of the individual contributions from each bound metal with a differently sized polymer. The results demonstrate that the average diffusion coefficient (Davg) concept can be used in mixtures of complexing ligands of different sizes. It can also be stated that the information contained in the binding studies of different metals with the same polymer mixture might be useful to elucidate the nature of the said mixture. References 1. J. Buffle, Complexation reactions in aqueous systems. An analytical approach. Ellis Horwood Pub., Chichester (1988). 2. J. P. Pinheiro, H. P. van Leeuwen, J. Electroanal. Chem. 570, 69 (2004). 3. D.D. DeFord, D. N. Hume, J. Am. Chem. Soc., 73 (11), 5321 (1951). The authors thank Fundação para a Ciência e a Tecnologia (FCTANR/AAG-MAA/0065/2012) and Faculdade de Ciências e Tecnologia (Pest-OE/EQB/LA0023/2013 and PEst-OE/QUI/UI4023/2014) for funding support. L.S. Rocha,and N. G. Alves also thank their grants (FCT project FCTANR/AAG-MAA/0065/2012) and the University of Algarve/CBME and University of Algarve/CIQA, respectively. Wander G. Botero thanks Capes (9813/13-6).

 

38

0822  

 

ACTIVATED CARBON FOR ENHANCING MICROPOLLUTANTS REMOVAL

IN UASB REACTOR

A. Butkovskyi1,2, L. Hernandez Leal2, H.H.M. Rijnaarts1, G. Zeeman1 1Wageningen University, P.O. Box 17, 6700 AA Wageningen, The Netherlands

2 Wetsus, P.O. Box 1113, 8900 CC Leeuwarden, The Netherlands Presenting author: andrii.butkovskyi@wetsus.nl

Up-flow anaerobic sludge blanket (UASB) reactor is a core technology within “New Sanitation” concepts, aimed at maximal recovery of resources from source separated domestic wastewater streams [1]. An important drawback of the anaerobic process is a low removal of persistent micropollutants [2, 3]. Addition of activated carbon to the reactor may improve the environmental quality of the effluent. The aim of this study was to investigate the potential of activated carbon for enhancing micropollutants removal in a UASB reactor treating a mixture of black water and grey water. UASB sludge was incubated in 100 ml Erlenmeyer flasks in a batch mode. To determine the impact of biomass growth on the adsorption capacity activated carbon (Norit, type C) was either incubated together with UASB sludge for 1, 3, 5 and 7 weeks prior to spiking or added directly after spiking of sludge with micropollutants. Blank samples were incubated without addition of activated carbon. Micropollutants (galaxolide, tonalide, triclosan, ibuprofen, diclofenac, gemfibrozil, estrone) were spiked to all batches 20 hours prior to sampling. Liquid phase, sludge and activated carbon were separated by centrifugation at 3750 rpm, followed by extraction of micropollutants from liquid and sludge and detection by GC-MS and LC-MS. The removal of micropollutants from the liquid phase with both fresh and incubated carbon was higher than 98%. Removal of micropollutants was significantly lower in control experiments without carbon addition, ranging from 86% for tonalide to 6% for ibuprofen. It was mostly attributed to sorption, not to biodegradation. Removal of micropollutants from sludge exceeded 80% for all compounds, except for galaxolide and tonalide. Lower concentrations of the spiked micropollutants were observed in sludge samples with addition of the fresh carbon as compared to incubated carbon. The increased partitioning of micropollutants towards the fresh carbon is a possible explanation. However methodological biases related to improper separation of carbon from sludge cannot be excluded. The obtained results indicate that addition of activated carbon to sludge phase of a UASB reactor can result in significant adsorption of micropollutants to the activated carbon. Thus, improved quality of the liquid effluent and organic sludge of a UASB reactor treating a mixture of black water and grey water is expected with addition of activated carbon. The observed, micropollutants removal from the UASB sludge increases possibilities for reuse, providing that adequate separation of activated carbon from sludge would be achieved.

References 1. G. Zeeman, K. Kujawa-Roeleveld. Water Sci. Technol. 64, 1987-1992 (2011) 2. M. S. de Graaff, N. M. Vieno, K. Kujawa-Roeleveld, G. Zeeman, H. Temmink, C. J. N.

Buisman. Water Res. 45, 375-383 (2011) 3. L. Hernandez Leal, N. M. Vieno, H. Temmink, G. Zeeman, C. J. N. Buisman. Environ. Sci.

Technol. 44, 6835-6842 (2010)

 

39

0828  

 

CONTAMINATION OF SETTLED INDOOR DUST WITH POLYCYCLIC AROMATIC

HYDROCARBONS IN THE UK: SOURCES AND SIGNIFICANCE AS AN EXPOSURE

PATHWAY

Y. Ma, S. Harrad

School of Geography, Earth & Environmental Sciences, University of Birmingham, Birmingham, B15 2TT, UK

Presenting author: y.ma.3@bham.ac.uk Polycyclic aromatic hydrocarbons (PAH), a group of pollutants with reported adverse health impacts including cancer, are emitted inadvertently from a wide range of combustion activities (e.g. cooking, heating, vehicle exhausts, etc.) in indoor environments.1 While human exposure to these chemicals via the diet and inhalation of indoor air has been widely studied; very little is known about exposure via contact with indoor dust present on surfaces such as floors, soft furnishings and tables etc.2 Indeed to date, concentrations of PAH have been reported in only 1 sample of indoor dust from the UK.3 Thus, our study (by investigating more than 50 UK homes and collecting more than 200 samples) provides a valuable base-line evaluation of the range of exposure of the UK population to PAH received via ingestion of indoor dust. We will also examine potential putative sources of contamination with PAH in indoor dust. Our findings will both aid risk assessment, and by improving our understanding of the sources of such contamination, will inform strategies to reduce such contamination. References 1. K. Srogi, Environ. Chem. Lett. 5, 169–195, (2007). 2. C. A. Menzie, B. B. Potocki, and J. Santodonato, Environ. Sci. Technol. 26, 1278–1284 (1992). 3. N. Anders, M. Abb, E. Sorkau, R. Kubinec, and W. Lorenz, Fresen. Environ. Bull. 21, 372–379 (2012).

 

40

0865  

 

AIR-SEA EXCHANGE OF PAHs, PCBs, OCPs AND PBDEs IN THE AEGEAN 2012

G. Lammel1,2, C. Samara3, D. Voutsa3, B. Vrana1, A. Besis3, C. Efstathiou1, F. X. Meixner2, P.

Přibylová1, R. Prokeš1, T. Rusina1, G. Z. Song2 1 Masaryk University, Research Centre for Toxic Compounds in the Environment,

62500 Brno, Czech Republic 2 Max Planck Institute for Chemistry, 55128 Mainz, Germany

3Aristoteles University, Dept. of Chemistry, 54124 Thessaloniki, Greece Presenting author: lammel@recetox.muni.cz

Seawater is storing persistent organic substances following atmospheric transport from land-based sources and deposition as well as riverine input. Following accumulation the direction of mass flux may reverse (net-volatilisation) turning the sea surface into a secondary source of pollutants (e.g. [1]). Organic trace substances in air were collected by passive (PAS, polyurethane foam disk deployed in protective chamber [2]) and active (high, medium and low volume) sampling (AAS) at sites in the Thessaloniki area / Thermaikos Gulf (5 locations) and at a remote site on Crete (2 locations) in July 2012. The effective sampling volume of PAS was ‘calibrated’ based on side-by-side PAS and high volume AAS (1 location). Silicone rubber (SR) sheets were applied as passive samplers of free dissolved contaminants in seawater [3]. From these measurements the direction of diffusive air sea exchange was determined (3 locations). Based on AAS from 2 heights above ground and measurement of the turbulent exchange coefficient by an Eddy covariance system [4] the vertical flux of several PAHs and OCPs could be determined (1 location). Vertical gradients were derived for sampling intervals with replica concentrations determined [5]. Chemical analysis of 28 3-6-ring PAHs, 13 OCPs, 7 indicator PCBs and 8 PBDEs was by organic solvent extraction from sampling media, followed by extract fractionation and instrumental analysis by GC-MS. All results were corrected for field blanks. Surrogate recovery standards were spiked prior to extraction. The results are discussed in the context of local processes (air-sea exchange), sources and long-range transport of the pollutants in and to the Aegean.

References 1. I. Stemmler and G. Lammel G, 2009, Geophys. Res. Lett. 36, L24602 (2009). 2. J. Klánová, P. Cupr, J. Kohoutek and T. Harner, Environ. Sci. Technol. 42, 550-555 (2008). 3. T. Rusina, F. Smedes, M. Kobližková and J. Klánová, Environ. Sci. Technol. 44, 362-367

(2010). 4. V. Wolff, I. Trebs, C. Ammann and F.X. Meixner, Atmos. Meas. Techn. 3, 187-208 (2010). 5. G. Lammel, J. Klánová, L. Erić, P. Ilić, J. Kohoutek and I. Kovacić, J. Environ. Monit. 13,

3358 – 3364 (2011).

 

41

0871  

 

PARTICLE-SIZE DISTRIBUTION OF POLYBROMINATED DIPHENYL ETHERS

(PBDES) IN THE URBAN AGGLOMERATION OF THESSALONIKI, NORTHERN

GREECE

A. Besis, E. Botsaropoulou, D. Voutsa, C. Samara

Environmental Pollution Control Laboratory, Department of Chemistry, Aristotle University of Thessaloniki, GR-54124 Thessaloniki Greece

Presenting author: tbesis@gmail.com Particle-size distribution (<0.49, 0.49-0.97, 0.97-1.5, 1.5-3.0, 3.0-7.2 and >7.2µm) of Polybrominated Diphenyl Ethers (PBDEs) was measured during the cold and the warm period of the year 2013 using a cascade impactor at two sites in the urban agglomeration of Thessaloniki, northern Greece (traffic and urban background). Mean aggregate concentrations (sum of six fractions) of the sum of 12 PBDE congeners (∑12PBDE) were 20.3 pg m-3 and 2.1 pg m-3 for the traffic and the urban background site, respectively in the cold period. The corresponding concentrations in the warm period were 27.1 pg m-3 and 2.4 pg m-3, respectively. Higher concentrations of PBDEs were observed in warm seasons at both sites. The most abundant PBDE congeners were BDE-47 and BDE-99. At both sampling sites, more than 58% of ∑12PBDE was associated with particles of <0.49 µm in diameter. Our results imply that particulate PBDEs may have long atmospheric residence time and they may be capable of reaching the deeper parts of the human respiratory system. Acknowledgements This research has been co-financed by the European Union (European Social Fund – ESF) and the Greek Ministry of Education through the Research Funding Program THALES (Project code/Title: MIS 377304/"Bioactivity of airborne particulates in relation with their size, morphology and chemical composition". We thank Dr. Apostolos Kelesis, Municipality of Thessaloniki, for providing meteorological data and on-site support.

 

42

0885  

 

FORMATION AND REACTIVITY OF (ORGANIC) BROMAMINES AND THEIR

RELEVANCE IN OXIDATIVE WATER TREATMENT

M. B. Heeb1, U. von Gunten1,2 1School of Architecture, Civil and Environmental Engineering (ENAC), École Polytechnique

Fédérale de Lausanne (EPFL), CH-1015, Lausanne, Switzerland 2 Eawag, Swiss Federal Institute of Aquatic Science and Technology, Ueberlandstrasse 133, CH-

8600 Duebendorf, Switzerland Presenting author: michele.heeb@epfl.ch

Oxidative water treatment such as chlorination or ozonation is widely applied for disinfection, removal of taste and odor compounds and the elimination of (anthropogenic) micropollutants. Bromide (Br-) has, besides natural organic matter (NOM), been identified as one of the key components of the water matrix relevant in oxidation processes. It is present in all freshwaters in concentrations ranging from a few µgL-1 to several mgL-1 and is non-toxic at these concen-trations. During oxidative water treatment bromide can be oxidized to bromine (hypobromous acid, HOBr). Even though bromide concentrations in source waters and thus also HOBr concentrations are small compared to the primary oxidants, it can have a significant impact on the formation of disinfection by-products and transformation products as well as on the degradation of micropollutants [1]. This is due to its high reactivity, especially towards phenolic (apparent second-order rate constants in the order of 103 to 105 M-1s-1 at pH 7), amine and sulfamide moieties (apparent second-order rate constants in the order of 105 to 106 M-1s-1 at pH 7) but also with inorganic compounds such as ammonia, iodine, sulfite and cyanide (apparent second-order rate constants in the order of 103 to 109 M-1s-1 at pH 7) [1]. Only limited data is available on the kinetics of bromine with amines. These reactions lead to the formation of bromamines, which are considered to be reactive themselves. However, data on their reactivity is scarce as well. Our goal is thus on one hand to determine the kinetics of bromamine formation and on the other hand, to investigate their reactivity with components of the water matrix. Stopped-Flow measurements were performed to determine rate constants of the reaction of HOBr with methylamine, dimethylamine and N,N-dimethylsulfamide, while the reactivity of bromamines (inorganic bromamine, bromomethylamine, dibromomethylamine, and bromodimethylamine) with phenol was assessed using DPD, a colorimetric assay, and HPLC analysis. Phenol was chosen as a surrogate for organic matter in the water matrix. Bromamines are formed rapidly with species-specific rate constants of around 108 M-1s-1 and apparent second-order rate constants in the order of 104 to 105 M-1s-1 at pH 7. Furthermore, the selected bromamines react with phenols with apparent second-order rate constants in the order of 102 M-

1s-1 at pH 7, forming bromophenols with a yield of around 30 %. This data (which will be supplemented with further experiments) will allow for kinetic modeling of the various competing reactions during oxidative water treatment, i.e. the formation of HOBr in the first place, the reaction of the oxidant with the amine, the reaction of HOBr with the amine and the further reaction of the bromamine (but also of HOBr and the oxidant itself) with organic matter. This study is an important step towards a quantitative understanding of the fate of bromine during oxidative water treatment processes in presence of amine- and phenol-type moieties in terms of oxidation and by-product formation. Reference: [1] Heeb, MB, Criquet, J, Zimmermann-Steffens, SG, von Gunten, U, Water Res. 48, 15-42 (2014).

 

43

0895  

 

OZONATION OF RANITIDINE UNDER VARIOUS PHYSICOCHEMICAL

CONDITIONS. DEGRADATION KINETICS AND INTERMEDIATE BY-PRODUCTS

C. Christophoridis, N. Thomaidis

Laboratory of Analytical Chemistry, Department of Chemistry, National and Kapodistrian University of Athens, Zografou, Athens 15771, Greece Presenting author: cchrist@chem.demokritos.auth.gr

Ranitidine is pharmaceutical compound, widely used for the treatment of ulcer and other gastrointestinal conditions. Its occurrence in surface waters and wastewater has been established. Ozonation can be a useful technique for the degradation of ranitidine in water, since molecular ozone selectively attacks organic compounds with high electron density functional groups, such as double bonds, activated aromatic rings or deprotonated amines. The objectives of this study was to assess the effects of various operational parameters (pH, ozone concentration, presence of hydroxyl radical scavengers, matrix effects and natural organic matter) on the kinetics of the ozonation process and to identify and elucidate the structure of intermediate oxidation by-products of ranitidine in aqueous solutions during the ozonation process. Results proved the high reactivity of ranitidine with molecular aqueous ozone with half-life times ranging 0.3-0.5 min. Reaction kinetics are greatly influenced by the initial ozone concentration, with ranitidine removal higher than 80% observed at initial ozone concentrations above 5 mg L-1. As expected, pH was a significant process parameter, with increased values enhancing degradation kinetics and overall percentage of mineralization. Pseudo-first-order reaction constants ranged 0.19-6.06 min-1 and the highest values were observed at lower initial ranitidine concentrations and alkaline solutions. At low pH mineralization was limited, while at pH 10, mineralization reached 68%. Water that included cations and ions such as chlorides, bicarbonates, sodium and calcium, tended to decrease the overall ranitidine removal. NOM acted antagonistically, consuming ozone and limiting its overall degradation. Hydrolysis of ranitidine at different pH was limited and this minimal degradation occurred only in extended time periods (>2 days). Furthermore, the main intermediate byproducts of ozonation degradation were identified and structurally elucidated using liquid chromatography coupled to quadrupole-time-of-flight tandem mass spectrometry (HPLC-QqTOF-MS/MS). After background subtraction, selected chromatographic peaks were analyzed and possible molecular formulas based on their exact m/z values were proposed. MS/MS data in relation to various databases were employed in order to tentatively identify intermediate by-products. Proposed by-products showing lowest error (ppm) and highest identification score (including isotopic pattern), along with their chemical structures, include sulfoxide C13H22N4O4S, imine C13H21N3O2S and nitrocompound C4H10N3O2 indicating a direct attack of the molecular ozone to the sulfur and amine group of the compound. Acknowledgments This research has been co-financed by the European Union and Greek national funds through the

Operational Program "Education and Lifelong Learning" of the National Strategic Reference Framework (NSRF) – ARISTEIA 624 (TREMEPOL project).

 

44

0899  

 

SURFACE WATER TREATMENT BY O3 OR AOP O3/H2O2:

IS A COMPROMISE BETWEEN MICROPOLLUTANTS REMOVAL AND

MITIGATION OF OXIDATION PRODUCTS

AND BY-PRODUCTS POSSIBLE?

M. Bourgin1, E. Borowska1,2, J. Helbing3, H.-P. Kaiser3,

J. Hollender1,4, C. S. McArdell1, U. von Gunten1,4,5 1Eawag, Swiss Federal Institute of Aquatic Science and Technology, CH-8600 Dübendorf, Switzerland

2Silesian University of Technology, Environmental Biotechnology Department, PL-44100 Gliwice, Poland

3Zurich Water Works, CH-8021 Zurich, Switzerland 4Institute of Biogeochemistry and Pollutant Dynamics (IBP),

ETH Zurich, CH-8092 Zurich, Switzerland 5School of Architecture, Civil and Environmental Engineering (ENAC),

Ecole Polytechnique Fédérale de Lausanne (EPFL), CH-1015 Lausanne, Switzerland Presenting author: urs.vongunten@eawag.ch

The combination of O3 and H2O2 is a widely applied advanced ozonation process (AOP), producing highly reactive •OH radicals, to improve water quality at moderate cost compared to other AOPs but more expensive than conventional ozonation. In the present study, Lake Zürich water was spiked with 1 000 ng L-1 of various organic micropollutants presenting wide ranges of applications (pharmaceuticals, pesticides, X-Ray contrast media, artificial sweeteners and industrial chemicals) and ozone reactivity (kO3 <<1 (sucralose) – 106 (tramadol) M-1 s-1)1. The oxidation of micropollutants by either conventional ozonation or the AOP O3/H2O2 was investigated in two pilot plants, a conventional system and an alternative reactor design with a flow of 4 – 5 m3/h. The following parameters were studied: ozone dose (0.5 – 3 mg/L), initial bromide concentration (16 – 200 µg/L), pH (6.5 – 8.5) and O3:H2O2 mass ratio (1:0.35 – 1:3). Water treatment efficiency was evaluated in particular by following the removal of parent compounds as well as the fate of selected transformation products formed during oxidation with online SPE-LC-HRMS analysis2. At optimized conditions, the addition of H2O2 enables to achieve an elimination of chemicals greater than 90% even for the most persistent compounds like sucralose. Simultaneously, the transformation products were significantly abated under these conditions. The production of bromate, a potentially carcinogenic ozonation by-product1, was also followed and could be substantially reduced by more than a factor of 5 by addition of H2O2. This reduction depended on the O3:H2O2 mass ratio. Therefore, though the costs to implement an AOP with O3/H2O2 and a post-treatment step to remove H2O2 residual are significant, the addition of H2O2 in ozone-based oxidation processes was demonstrated to be very beneficial for an enhanced micropollutant removal in drinking water. References 1. C. von Sonntag and U. von Gunten, Chemistry of ozone in water and wastewater treatment (IWA Publishing,

London, 2012). 2. H. Singer, S. Jaus, I. Hanke, A. Lück, J. Hollender, A.C. Alder, Environ. Poll. 158 (2010) 3054-3064. 3. J. L. Acero, K. Stemmler, U. von Gunten, Environ. Sci. Technol. 34 (2000) 591-597. 4. S. G. Zimmermann, A. Schmukat, M. Schulz, J. Benner, U. von Gunten, T. A. Ternes, Environ. Sci. Technol. 46

(2011) 876-884.

 

45

0904  

 

SUSTAINABLE DESIGN OF DYE SENSITISED SOLAR CELLS:

ISSUES AND OPPORTUNITIES

R. G. Charles1,2, M. L. Davies3, P. Douglas2

1COATED Engineering Doctorate, Swansea University, SA2 8PP, Swansea, UK 2Chemistry Group, College of Engineering, Swansea University, SA2 8PP, Swansea, UK

3SPECIFIC, Swansea University, SA2 8PP, Swansea, UK Presenting author: 290952@swansea.ac.uk / rhys.charles@hotmail.com

Ten million tonnes of Waste Electrical and Electronic Equipment, WEEE, is generated in the EU per year. Globally, WEEE accounts for 5% of all municipal solid waste, and it is one of the fastest growing waste streams.[1,2] It is a complex heterogeneous mixture of materials including economically and strategically important metals and a variety of toxic heavy metals and persistent organic pollutants. The negative impacts upon human health and the environment resulting from improper treatment of WEEE are wide ranging and can be severe.[3] The rate of WEEE generation also contributes to global resource depletion. In light of this, it is becoming increasingly important to incorporate sustainability considerations in the design of future electrical/electronic products to support cradle-to-cradle (C2C) ‘circular economy’ product lifecycles, rather than the current ‘linear economy’ cradle-to-grave approach. Such an approach requires sustainable design, incorporating materials substitution and planning for end of life processing, to enhance potential for reuse, upgrade, refurbishment, repair, and suitability for available or new, customised, recycling processes. PV products will ultimately become WEEE. Here, we consider the C2C lifecycle approach to the various emerging dye sensitised solar cell (DSC) technologies, which typically use ruthenium complexes, organic dyes, or lead perovskites, to absorb solar radiation.[4-6] Proposed uses of DSCs include both low energy/area applications in consumer products and large scale energy production, such as energy generating cladding for buildings. These different applications create significantly different sustainability demands on product design. For all three types of cell, life-cycle issues include the use of EU14 critical materials such as indium and platinum group metals in conducting layers and contacts, issues which may be resolved by ‘materials substitution’. In addition the different materials used in the DSCs create different waste problems which may require different recycling strategies. Specific life-cycle issues associated with ruthenium based DSCs include critical material supply risk and losses; while for lead perovskite sensitisers environmental issues may well be paramount. There can be significant environmental impacts even for ‘green energy’ technologies. Given the stage of development of DSC technology there is now a window of opportunity to minimise these by C2C design, and consideration of sustainability throughout the entire product life-cycle. References 1. F. O. Ongondo, I.D. Williams, and T.J. Cherrett, Waste Manag. 31, 714 (2011). 2. R. Widmer, H. Oswald-Krapf, D. Sinha-Khetriwal et al., Environ. Impact Assess. Rev. 25, 436 (2005). 3. B. H. Robinson, Sci. Total Environ. 408, 183 (2009). 4. M.K. Nazeeruddin, F. De Angelis, et al., J. Amer. Chem. Soc. 127, 16835 (2005). 5. A. Mishra, M. K. R. Fischer, and P. Bäuerle, Angew. Chem. Int. Ed. Engl. 48, 2474 (2009). 6. N.-G. Park, J. Phys. Chem. Lett. 4, 2423 (2013).

 

46

0945  

 

MONITORING OF HUMAN EXPOSURE TO CONTAMINANTS

OF EMERGING CONCERN

A. Covaci

Toxicological Center, University of Antwerp, Universiteitsplein 1, 2610 Wilrijk, Belgium Presenting author: adrian.covaci@uantwerpen.be

Contaminants of emerging concern are a broad category of chemicals, previously unknown or unrecognized as being of concern, but which, because of their potential toxic effects associated with human exposure, are under increasing scrutiny. We present the most relevant contaminants of emerging concern, together with an overview of the available analytical methods, toxicity data and biomonitoring studies in humans (1). Such contaminants include various brominated and phosphorous/chlorinated flame retardants, phthalate substitutes (e.g. diiso-nonyl cyclohexane-1,2-dicarboxylate-DINCH or O-acetyl tributyl citrate-ATBC, and tri-2-ethylhexyl trimellitate-TETM), bisphenols (e.g. bisphenol-S, -F, -B and others), personal care products or polysiloxanes. Current understanding of these emerging contaminants often contains significant gaps, including their toxicity, occurrence, human exposure, bioaccumulation, and biotransformation mechanisms. Critical issues and challenges are discussed, together with recommendations for further improvement in particular cases (e.g. metabolites of phthalate substitutes, bisphenol-S). The rather limited availability of analytical standards, of labeled internal standards, and of certified reference materials constitutes a major impediment in the widespread biomonitoring of these contaminants. For the discussed contaminants, chromatography and mass spectrometry are the analytical techniques of choice, because of their selectivity and sensitivity for measurements at (sub) ng/g levels. There is also an immediate need for interlaboratory comparison exercises which should include newer contaminants. An important issue during the setup of a biomonitoring study is the selection of appropriate biomarkers of exposure for each contaminant of interest. In the absence of knowledge regarding the biotransformation pathways in humans, various in vitro and in vivo models can be used to determine the relevant metabolites to be monitored as key aspects of further development of this field of research. There is also missing information regarding the relative importance of various exposure pathways and the multiple factors which influence the magnitude of these exposures. By far, there is a lack of standardized testing of endpoint toxicity for different groups of chemicals which makes the comparison of toxic effects and health issues for various chemicals very difficult, if not impossible. References 1. A.C. Dirtu, N. Van den Eede, G. Malarvannan, A.C. Ionas, A. Covaci A (2012) Analytical methods for emerging organic contaminants in human matrices. Anal Bioanal Chem 404, 2555-2581 (2012).

 

47

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 1H NMR STUDIES OF ALKALINE-SOLUBLE ORGANIC MATTER FROM URBAN

ATMOSPHERIC AEROSOLS

S.P. Lopes1, C.A.D. Loureiro1, S.M.S.C. Freire1,

R.M.B.O. Duarte1, A.M.S. Silva2, A.C. Duarte1

1Department of Chemistry & CESAM, University of Aveiro, 3810-193, Aveiro, Portugal 2Department of Chemistry & QOPNA, University of Aveiro, 3810-193, Aveiro, Portugal

Presenting author: sonialopes@ua.pt

Over the last two decades, understanding the water-soluble organic matter in atmospheric particles has been the focus of the majority of environmental researchers, mostly because it represents the major fraction (~20-70%) of particulate matter in the atmosphere, and it could be involved in several atmospheric processes. Nowadays, an emerging topic has been the organic particulate matter that is water-insoluble, in particular the alkaline-soluble organic matter (ASOM), which could account for up to 14% of the organic aerosol carbon. Taking into account that this organic fraction still is poorly understood, a new extraction methodology was developed to isolate the ASOM from fine atmospheric aerosols collected over different seasons in an urban location - Aveiro, Portugal. Solution-state proton nuclear magnetic resonance (1H NMR) was used for the first time to characterize the structural features of the ASOM extracted from fine atmospheric aerosols. Aliphatic structures are the dominant moieties, followed by oxygenated and unsaturated aliphatic groups, and only a minor contribution from aromatic groups. The most striking feature is that the ASOM samples from colder seasons show a higher aromatic content and a lower amount of aliphatic structures than samples from the warmer period. The winter samples also appear to have lignin-like compounds probably due to wood-burning processes for house heating in domestic fireplaces. Acknowledgments Central for Environmental and Marine Studies (PEsT-c/MAR/LA0017/2013, University of Aveiro, Portugal) and the Portuguese Science and Technology Foundation (FCT), through the European Social Fund and “Programa Operacional Potencial Humano – POPH”, are acknowledged for financial support. This work was also funded by FEDER under the Operational Program for Competitiveness Factors – COMPETE and by National funds via FCT within the framework of research projects ORGANOSOL (PTDC/CTE-ATM/118551/2010) and CN-linkAIR (PTDC/AAG-MAA/2584/2012).

 

48

0958  

 

UNFOLDING THE STRUCTURAL FEATURES OF ORGANIC AEROSOLS BY NMR

SPECTROSCOPY

R.M.B.O. Duarte1, A.M.S. Silva2, A.C. Duarte1 1Department of Chemistry & CESAM, University of Aveiro, 3810-193 Aveiro, Portugal

2Department of Chemistry & QOPNA, University of Aveiro, 3810-193 Aveiro, Portugal Presenting author: regina.duarte@ua.pt

Organic aerosols (OA) encompass a multitude of molecular structures, physical properties, and sources. This complexity constitutes a major obstacle to an improved understanding of OA chemistry and composition, but also on how OA affect the climate system, atmospheric processes, and human health. Unfolding the detailed composition and structure of such complex atmospheric organic mixtures is a truly exciting challenge that offers unparalleled rewards toward a better understanding of their role in various atmospheric processes. This study highlights the potential and limitations of nuclear magnetic resonance (NMR) spectroscopy to deliver new qualitative information on the substructures present in natural organic matter (NOM) from fine atmospheric aerosols collected at different locations during different seasons. The emphasis is given on the wealth of information that is obtainable with solid-state 13C NMR and one- and two-dimensional solution-state NMR methods and on how these data can be employed for assessing aerosol source fingerprints in different areas with disparate levels of pollution. By combining the information provided by all these NMR experiments, it was possible to identify a set of organic structures, which are likely to be representative of the whole NOM mass in the studied aerosol samples.

Acknowledgments Centre for Environmental and Marine Studies (PEsT-c/MAR/LA0017/2013, University of Aveiro, Portugal) and the Portuguese Science and Technology Foundation (FCT), through the European Social Fund and “Programa Operacional Potencial Humano – POPH”, are acknowledged for financial support. This work was also funded by FEDER under the Operational Program for Competitiveness Factors – COMPETE and by National funds via FCT within the framework of research projects ORGANOSOL (PTDC/CTE-ATM/118551/2010) and CN-linkAIR (PTDC/AAG-MAA/2584/2012).

 

49

0961  

 

CARBON SEQUESTRATION IN THE UNITED STATES:

USING BIOGEOCHEMISTRY TO IMPROVE OUR

UNDERSTANDING OF THE ENVIRONMENTAL RISKS

G. Lowry, A. Karamalidis, K. Gregory, A. Burant, D. Gulliver

Civil & Environmental Engineering, Carnegie Mellon University, Pittsburgh, PA, USA Presenting author: glowry@cmu.edu

Carbon capture, utilization, and sequestration (CCUS) technology is proposed as a means to help mitigate climate change and impacts from increasing rates of CO2 release from emission point sources. CCUS has been studied in the United States and globally for several decades, but only recently plausible paths for CCUS have emerged. This includes the capture of CO2 from stationary point sources, compression, transport, and storage in deep underground saline formations, un-minable coal seams, basalt formations, organic-rich shale basins, and oil and gas reservoirs. Eight demonstration projects in the United States are ongoing or scheduled to sequester at least 1MM tones CO2 each. In addition, a large oxy-fired coal plant with CO2capture and sequestration has been proposed. The risks associated with long-term subsurface storage of CO2are currently poorly understood. In particular, the biogeochemical processes controlling risks, such as CO2 or CO2-saturated brine leakage, CO2 impacts on deep subsurface microbiology or induced release of contaminants, are not fully elucidated. In the US, the National Risk Assessment Partnership (NRAP) has been formed to determine and to quantify these risks. This includes the formation of national network of models to predict risks at all steps of the sequestration process and into the next 1000 years, including leakage from abandoned wells, through proposed seal rocks, and the risks of migration of inorganic and organic contaminants to overlying water bodies and groundwater wells. The effects of CO2 injection on the native microbial communities and the associated effects on water quality are also currently being explored. Finally, methods to offset the costs associated with carbon capture and storage through storage in depleted oil reservoirs coupled with tertiary oil recovery are being considered. The most significant remaining challenges include ensuring the long-term storage capacity and security under the influence of dynamic (bio)geochemistry, stimulated biotic and abiotic mineralization to maximize storage volumes and security, robust monitoring technology, and repair and mitigation strategies for various leakage scenarios

 

50

0991  

 

OXIDATION OF ALGAL-DERIVED TASTE AND ODOR COMPOUNDS BY

FERRATE(VI): REACTION KINETICS AND ELIMINATION EFFICIENCY

J. Shin, D. Lee, Y. Lee

Department of Environmental Science and Engineering, Gwangju Institute of Science and Technology (GIST), 500-712, Gwangju, Republic of Korea

Presenting author: jayden@gist.ac.kr Blooms of cyanobacteria in water resources can generate taste and odor (T&O) compounds, cyanotoxins, and disinfection byproduct precursors, which have been a significant concern to drinking water utilities. T&O compounds can be detected by consumers at very low concentrations (ng/L range) and affect the public’s perception of the safety of drinking water. Thus, effective eliminations of T&O compounds during drinking water treatment are necessary. Chemical oxidation processes such as ozonation or permanganate treatment have been applied to eliminate T&O compounds [1]. In this study, the potential of ferrate(VI) to oxidize T&O compounds during water treatment was assessed by determining rate constants for the reaction of ferrate(VI) with selected T&O compounds. Ferrate(VI) is an emerging water treatment chemical which can be used as both an oxidant and a coagulant [2]. Apparent second-order rate constants (k) were determined in the pH range of 6 to 9 by measuring the decrease of ferrate(VI) concentration in presence of excess T&O compound (i.e., [T&O] >> [Fe(VI)]). The selected T&O compounds containing olefins showed an appreciable reactivity to ferrate(VI). At pH 7, the kapp values were: k1-penten-3-one = 599 M-1 s-1, ktrans,cis-2,6-nonadienal = 160 M-1 s-1, kcis-3-hexen-1-ol = 33 M-1

s-1, kβ-cyclocitral = 46 M-1 s-1, kβ-ionone = 1115 M-1 s-1. Other T&O compounds such as geosmin, MIB, and 2-isopropyl-3-methoxypyrazine showed low reactivity to ferrate(VI) (k < 1 M-1 s-1) due to the absence of electron-rich moieties. Kinetic studies were also performed by measuring the decrease of T&O compound in presence of excess ferrate(VI). Interestingly, the apparent second-order rate constants determined in the ferrate(VI) excess condition increased with increasing ferrate(VI) concentration. For example, the kapp values for cis-3-hexen-1-ol were 71, 298, and 662 M-1 s-1 for the ferrate(VI) concentration of 40, 80, and 120 µM, respectively. The observed enhanced elimination rate of olefinic T&O compounds at higher ferrate(VI) concentration might be attributable to the reaction of perferryl(V) or ferryl(IV) species. These high-valent iron species are produced during ferrate(VI) self-decay and known to be several orders of magnitude more reactive than Fe(VI) [3]. Nevertheless, more in depth studies are necessary to understand the mechanisms. Overall, the kinetic study shows that ferrate(VI) oxidation can be effective to eliminate T&O compounds with olefin moiety. The elimination efficiency of selected T&O compounds during real water treatment with ferrate(VI) will also be presented. References 1. Peter, A. and U. Von Gunten, Oxidation kinetics of selected taste and odor compounds during

ozonation of drinking water. Environmental science & technology, 2007. 41(2): p. 626-631. 2. Lee, Y., Zimmermann, S.G., Kieu, A.T., and U. Von Gunten, Ferrate (Fe(VI)) application for

municipal wastewater treatment: a novel process for simultaneous micropollutant oxidation and phosphate removal. Environmental science & technology, 2009. 43: p. 3831-3838.

3. Lee, Y., Kissner, R., U. Von Gunten, Reaction of ferrate(VI) with ABTS and self-decay of ferrate(VI): Kinetics and Mechanisms. Environmental science & technology, 2014. 48: p. 5154-5162.

 

51

1002  

 

SIMULTANEOUS DETERMINATION OF PHARMACEUTICALS IN

ENVIRONMENTAL SOLID SAMPLES BY ULTRASONIC-ASSISTED EXTRACTION

(UAE) – AN EXPERIMENTAL DESIGN APPROACH

S. Ferhi1, M. Bourdat-Deschamps1, J.J. Daudin2, S. Nélieu3

1 INRA-AgroParisTech, UMR 1091 EGC, 78850, Thiverval-Grignon, France

2 AgroParisTech-INRA, UMR 518 MIA, 75231, Paris, France 3 INRA, UR 251 PESSAC, 78026, Versailles, France

Presenting author: sferhi@grignon.inra.fr Administration of pharmaceuticals is the most common practice for human and animal disease control and treatments. Large fractions of administrated pharmaceuticals are not assimilated or metabolised but excreted and therefore transferred to wastewater and manure, respectively. Sewage sludge and manure are recycled in agriculture for their fertilising values and thus contribute to the dissemination of pharmaceuticals into the environment (soil, surface and ground water). Little is known about the potential toxic effects of these pharmaceutical residues in the environment. It is therefore necessary to develop analytical methods for their quantification. It is a real challenge due to the complexity of the solid matrices and the low level contents of many pharmaceuticals. We optimised the analysis of sixteen pharmaceuticals including eight antibiotics in soil and sewage sludge. The samples were extracted by Ultrasonic-Assisted Extraction (UAE), purified according to an adapted QuEChERS method and analysed by online solid-phase extraction coupled to ultra-high performance liquid chromatography with tandem mass spectrometry (online SPE-UHPLC-MS-MS) [1]. Two successive experimental design approaches were performed, in order to evaluate a large number of parameters and to optimise experimental conditions.  Literature data described various experimental conditions for pharmaceutical extraction from solid matrices. According to the compound properties, four parameters appeared to be crucial for UAE efficiency: the nature of the organic solvent and its proportion, the nature of the aqueous phase (buffers, modifying agents) and its pH. For each matrix, a screening experimental design was performed to identify the factors and/or their interactions that had a statistical influence on the recovery. A response surface design was then performed to find the best extraction conditions. In sewage sludge, even if the pharmaceuticals presented various behaviours that could be explained by their physicochemical properties, a compromise between the optimal conditions was possible. We thus proposed a single condition allowing efficient extraction. In the case of soil, a selection of two successive extraction conditions was done due to opposite behaviour of compounds: fluoroquinolones and sulfonamides presented contrasted optima in terms of pH and chelating agent abundance. In the presentation, the approach will be described, focussing on two compounds of these families. References [1] M. Bourdat-Deschamps, S. Leang, N. Bernet, J.J. Daudin, S. Nélieu, J. Chromatogr. A (2014) in press, DOI 10.1016/j.chroma.2014.05.006

 

52

1023  

 

SIMULTANEOUS DETECTION OF NEW PSYCHOACTIVE SUBSTANCES (NPSs) IN

WASTEWATER OF GREECE

V. L. Borova1, N. S. Thomaidis1, C. Pistos2 1Department of Chemistry, National and Kapodistrian University of Athens, Panepistimiopolis

15771, Athens, Greece 2 School of Medicine, National and Kapodistrian University of Athens, Athens, Greece

Presenting author: vborova@chem.uoa.gr In recent years, new psychoactive molecules have appeared worldwide, often under “innocent” appearances (house scents, bath salts, incenses, etc.), finding a wide and efficient distribution through the “e-commerce” or specialized shops. These products are claimed to contain only natural “non-illegal” compounds and consequently have no limitations in their commercial distribution, although exhibiting important psychoactive effects similar to that obtained with illegal stimulants, such as methamphetamine, MDMA, cocaine or cannabis. This heterogeneous class of products are called “New Psychoactive Substances” (NPSs) and are undesirable, as very little is known about their effects and long term risks [1-3]. Among these substances, JWH-018, mephedrone, benzylpiperazine, and a-PVP have been detected in Greece [4]. The analysis of these compounds in wastewater samples provides valuable information about their consumption back in the community. The selected NPSs of this study comprise a broad range of substances, including synthetic cannabinoids (JWH-018, JWH-073, JWH-122, JWH-210, JWH-250, CP47,497), cathinones (mephedrone), piperazines (benzylpiperazine) and pyrrolidinophenones (a-Pyrrolidinopentiophenone, 4’-methylpyrrolidinobutyrophenone). A novel ultra performance liquid chromatography tandem mass spectrometry (UHPLC-MS/MS) method was developed for their determination in wastewater samples. Comparison of various columns, mobile phases and SPE sorbents was performed. The final method employed solid phase extraction with PolyClean 2H sorbents for all the compounds, except BZP which was extracted using Strata XC and subsequent LC-MS/MS analysis in positive and negative electospray ionization, using a pentafluorophenyl (PFP) column. The new method was successfully applied in influents and effluents of six WWTPs of Santorini Island (a highly touristic resort in central Aegean Sea), and of the WWTP of Athens. Acknowledgments This research has been co-financed by the European Union and Greek national funds through the

Operational Program "Education and Lifelong Learning" of the National Strategic Reference Framework (NSRF) – ARISTEIA 624 (TREMEPOL project).

References 1. I. Vardakou, C. Pistos, and Ch. Spiliopoulou, Toxicol. Letters, 197 (3), 157-162 (2010). 2. Ch. L. German, A. E. Fleckenstein, and G. R. Hanson, Life Sciences, 97 (1), 2-8 (2014). 3. J. Van Amsterdam, D. Nutt, and W. Van den Brink, J Psychopharmacol, 27 (3), 317-324

(2013). 4. Press announcement regarding EKTEPN meeting for “New dubstances, new challenges…“

(http://www.ektepn.gr/index.php; Greek Monitoring Centre for Drugs (EKTEPN).

 

53

1050  

 

INDOOR PSYCHOTROPIC SUBSTANCES IN ROME: LEVELS AND BEHAVIORS

C. Balducci, P. Romagnoli, M. Perilli, A. Cecinato

CNR Institute of Atmospheric Pollution Research (CNR-IIA), 00015, Monterotondo Stazione RM, Italy Presenting author: balducci@iia.cnr.it

Among the thousands of compounds comprised in the organic fraction of airborne particulate, a special group is formed by psychotropic substances. Nicotine and caffeine, as licit drugs, were identified in aerosols since long time, whereas more recent is the discovery of illicit drugs occurrence. Cocaine and cannabinoids were first detected in the atmosphere of Rome and Taranto in 2006. Ever since, many studies have been conducted in Italy, and the illicit drugs presence in the open atmosphere has been confirmed in several regions of the world. As for aquatic systems, illicit drugs have been definitively indicated as new contaminants, and potential harmful effects on the environment have been listed. By contrast, till now this facet has been neglected in the atmospheric compartment because of the low concentrations usually detected for psychotropic substances. Nevertheless, illicit substances are often abused indoors. Noticeably, the phenomenon of toxicant intake through “passive consumption” or “passive ingestion” is recognized as capable of leading to adverse effects in the case of heavily contaminated environments [1].     The first investigation aimed at assessing the pathways followed by drugs of abuse in indoor environments was conducted between 2011 and 2013. Atmospheric particulate samples were collected in Rome at homes and schools plus one office and one coffee bar [2]. The drug levels indoors and the respective relationships with outdoor atmosphere were investigated. The monitoring procedure optimized allowed to determine cocaine and cannabinoids, as well as the particulate fractions of nicotine and caffeine. Although covering different year seasons and living place types, this investigation can be considered as preliminary to further investigations. In fact, all sites were not frequented by consumers, especially with regards to illicit substances, and only one home hosted cigarette smokers. However, the results show that both licit and illicit psychotropic substances affect all indoor environments, where citizens spend most of their life. The high levels detected randomly indoors, combined with the fact that psychotropic substances were more abundant at our target sites than at regional stations, suggest that these substances can have an environmental relevance. Anyway, more extensive studies are needed at new site categories to estimate the exposure of citizens (or particular classes of citizens) to drugs. Besides, the indoor drugs behavior was different from both outdoor drugs and regulated toxicants. As an example, the Δ9-tetrahydrocannabinol (main psychotropic constituent of the cannabis) seemed to decompose easily at the open air, while it appeared much more persistent indoors. References 1. F. De Giorgio, S. Strano Rossi, J. Rainio, M. Chiarotti, Int. J. Legal. Med. 118, 310 (2004). 2. A. Cecinato, C. Balducci, P. Romagnoli, M. Perilli, Environ. Sci. Pollut. Res. Article in Press

DOI 10.1007/s11356-014-2839-2.

 

54

1059  

 

FATE OF NATURAL ORGANIC MATTER AT A FULL-SCALE DRINKING WATER

TREATMENT PLANT

A.Papageorgiou1, N. Papadakis2, D. Voutsa1 1Environmental Pollution Control Laboratory, Department of Chemistry,

Aristotle University of Thessaloniki, GR-54124, Thessaloniki, Greece 2Laboratory of Hygiene, Faculty of Medicine, Aristotle University of Thessaloniki, GR-54124,

Thessaloniki, Greece Presenting author: apapage@chem.auth.gr  

Natural Organic Matter (NOM) is a complex mixture of organic compounds present in surface waters. NOM in aqueous environments originate from plants and soil (allochtonous sources) and from biological activities within the water body (autochtonous sources) [1]. The amount and characteristics of NOM depends on climate, geology and topography. The presence of NOM in drinking water concerns aesthetic problems, such as odor, taste and colour. Upon drinking water treatment, NOM is of major concern, since it is precursor parameter of ozonation and chlorination disinfection by-products (DBPs) [2,3]. Finally, biodegradable organic carbon in finished water can enhance the bacterial regrowth in distribution system [4]. The aim of this study was to investigate the occurrence of NOM as dissolved organic carbon (DOC) and its characteristics (UV absorbance, SUVA, fluorescence intensity, hydrophobic and hydrophilic fractions and biodegradable fraction) in the Drinking Water Treatment Plant of Thessaloniki, Greece. This plant receives surface water from Aliakmonas river and employs various treatment steps (pH correction, pre-ozonation, flocculation/coagulation, sand filtration, ozonation, filtration through activated carbon and chlorination) in order to provide 150000 m3/d of drinking water. Water samples have been collected after each treatment step every month for a period of one year. Temporal variation of DOC concentration and characteristics of raw water are presented. The contribution of each treatment process in removal of DOC and changes in its characteristics are discussed as well as potential relationships with ozonation-DBPs (carbonyl compounds) and chlorination-DBPs (THMs, HAAs). Acknowledgement This study was conducted under the cooperation and financially support of Thessaloniki Water Supply and Sewerage Co S.A. (EYATH).  References 1. Matilainen, Chemosphere 83, 1431-1442 (2011). 2. A.Papageorgiou, D. Voutsa and N. Papadakis, Sci. Total Environ. 481, 392-400 (2014). 3. R. Gough, Sci. Total Environ. 468-469, 228-239 (2014). 4. M.K. Ramseier, A. Peter, J. Traber and U. von Gunten, Water Res. 45, 2002-2010 (2011).

 

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1085      

GEOTEXTILES FOR THE HEAVY METALS REMOVAL FROM MARINE WATER

BASED ON FUNCTIONALIZED BIO-POLYMERS

Jalal Isaad1, Ahmida El Achari1 1ENSAIT, GEMTEX laboratory. F-59056 Roubaix. France

Presenting author: jalal.isaad@ensait.fr

Heavy metals are commonly found in industrial wastewater. For environmental and/or process concerns, it is often important to be able to detect and remove these before disposing or recycling the water. When this removal is carried out selectively, the burden of wastewater treatment can be transformed into an opportunity for metal recovery.

Biopolymers such as Chitosan (CTS) and alginate (Alg) can be used as ion exchange material for the removal of heavy metal ions from industrial wastewaters [1,2]. They present hydroxyl, amine and carboxylic groups respectively that can be modified to prepare CTS and Alg derivatives.

Chemical grafting of new functional groups improves the adsorption selectivity, as well as the sorption capacities of these biopolymers. In this sense, functionalized azathia crown ethers have good selectivity for its particular molecular structure and variety of ring cavities during chelation with metal ions. The chemical grafting of the functionalized azathia crown ethers onto a high molecular CTS and Alg backbone yield the CTS and Alg – functionalized azathia crown ethers (figure 1) containing the double structures and properties of CTS, Alg and functionalized azathia crown ethers. These novel CTS and Alg derivatives were synthesized by using the ultrasound technology in order to reduce the ecological impact of the classical organic synthesis methods.

In this conference, we will present our recent and the most significant results about the capture of different heavy metals, revealing the saturation level, kinetics of capture as well as the behavior of the geotextiles towards the calcium and magnesium..

S

N

S

O

OO

HNOH

O

O

O

O

S

SS

NS

OO

HN

OH

O

O

O

O

Chitosan + Azathia crown ether 1 Chitosan + Azathia

crown ether 2

Figure 1: General structure of the modified chitosan- azathia crown ethers References 1. Isaad, J, El Acharit, A. EUCHIS 2013 - International Conference of the European Chitin

Society. Porto (Portugal). Mai, 05-08. 2013. Book Abstract – p 171. 2. Julie Druet, Ahmida El Achari. Jalal Isaad. RSC Advances, 2014, Submitted    

 

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1102  

 

SUSTAINABLE AND SAFE RESOURCE MANAGEMENT:

SINKS AS LIMITED RESOURCES?

P. H. Brunner, D. Vyzinkarova

Vienna University of Technology, A-1040 Vienna, Austria Presenting author: paul.h.brunner@tuwien.ac.at

During the so called Anthropocene, the per capita as well as the global material turnover provided to satisfy human demand have risen to previously inconceivable amounts. While the supply of materials has been studied, optimized, and managed by different disciplines such as mining, engineering, and economics for centuries, little attention has been paid to the safe disposal of these materials in a comprehensive way. Materials are “lost” from the anthroposphere by several pathways: As off-products such as off-gas from vehicles or industrial processes, as products of wear, corrosion and erosion from surfaces, and as wastes from households, industry, and agriculture. After treatment, a certain fraction of these material flows inevitably ends up in water, air, or soil. There are several examples that show that these flows may exceed the capacity of regional as well as global sinks. Most prominent - but not the only - cases are greenhouse gases and the resulting climate change, and CFCs and the decrease of the ozone layer. In this paper, we advocate to investigate comprehensively into the back end of the anthropogenic metabolism, and to link resources to sinks in an all-embracing manner. Such an assessment is necessary for early recognition of overloading of sinks, for setting priorities in waste and environmental management, and for giving guidance for resource extraction and the material design of human activities. Without comprehensively linking resource extraction, stock of materials in the anthroposphere, and losses/disposal of materials into sinks, it may well be that sinks will become a limiting resource for the long-term development of the anthroposphere. There are many challenges in this new field of research. From a methodological point of view, the following questions arise: How can “sinks” and “final sinks” - as antonyms to “sources” - be defined? What are appropriate sinks for the various classes of substances, and how can the carrying capacities of sinks be determined? What kind of metric allows measuring the flows to appropriate/inappropriate sinks, are “sink indicators” feasible? For materials management in view of sink constraints, key questions are: Which sink capacities are necessary for accommodating all off-flows from human activities? What are todays sink requirements on a regional and global scale, and how will they change in the future when today’s large stock of hazardous substances has to be disposed of? Is general sink overloading to be expected, or will this be an individual phenomenon for a few single substances? How can potential sink constraints be overcome (prevention, design for final sinks, new waste disposal technologies)? Answers to these questions will be crucial for sustainable resource management and environmental management. They are an essential base for planning and operating cities and regions. Particularly waste management, which is a key filter between human activities and the environment, will benefit from this research. The paper will address these questions on a general level as well as by specific case studies.

 

57

1108  

 

METAL NANOPARTICLES FOR COLORIMETRIC AND FLUORESCENT BIO-

SENSING APPLICATIONS IN ENVIRONMENTAL MEDIUMS

J. Isaad, A. El Achari

ENSAIT, GEMTEX laboratory. F-59056 Roubaix. France Presenting author: jalal.isaad@ensait.fr

There is interest in finding better and more efficient ways of detecting the bioanalytes that can be potentially harmful to the environment or human health. Among the anions and the heavy metals, cyanides, mercury and copper are the most dangerous which are lethal to humans at micromolar concentrations. Consequently, the presence of these anions in drinking water can give rise to a very serious risk to human health. For this purpose, we developed in our laboratory efficient colorimetric and fluorescent water soluble molecular and polymeric chemosensors for the detection of cyanide [1-7], mercury [8,9] and cupper [10] ions about 10-7 M in biological systems with high selectivity over other ions. However, in the last decade the use of nanomaterials has been having a great impact in bio-sensing. In particular, the unique properties of metal / metal oxyde nanoparticles have allowed for the development of new biosensing platforms with enhanced capabilities in the specific detection of bioanalytes. In this sense, we developed recently a large biosensing platform to detect the heavy metals in biological mediums by synthesizing fluorescent functionalized nanoparticles based on Nobel metals, silica [9] and silica coated magnetite [10] nanoparticles doped by an adequate fluorophore for the Hg (II) and Cu (II) colorimetric and fluorescent titrations. In this conference, we will present our recent and the most significant results about the use of metal / metal oxide nanomaterials for the bioanalyte detection in environmental medium. References 3. J Isaad, A Perwuelz. Tetrahedron Letters. 51, 5810-5814 (2010). 4. J Isaad, A El achari. Analytica chimica acta. 694, 120-127 (2011) 5. J Isaad, A El Achari. Tetrahedron. 67, 4196-4201 (2011). 6. J Isaad, A El achari. Tetrahedron. 67, 5678-5685 (2011). 7. J Isaad, F salaun. Sensors and Actualitors B. 157, 26-33 (2011) 8. J Isaad, A El Achari. Tetrahedron. 67, 4939-4947 (2011) 9. J Isaad, A El Achari. Dyes and pigments. 97, 134-140 (2013) 10. J Isaad, A El Achari. The Analyst.,138, 3809-3819 (2013) 11. J Isaad, A El Achari. Tetrahedron., 69 (24), 4866 – 4874 (2013) 12. J Isaad, A El Achari. Dyes and pigments. 99 (3), 878 – 886 (2013).

 

58

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CONVERSION OF SEAWEED DIGESTATE FROM WASTE TO A POTENT BIO-

BASED FERTILIZER: SELECTIVE CD2+ REMOVAL USING CRYOGEL-

SUPPORTED TITANATE NANOTUBES L. Önnby, I.A. Nge1, B. Mattiasson, H. Kirsebom

Department of Biotechnology, P.O.Box 124, Lund University, Sweden Presenting author: Linda.Onnby@biotek.lu.se

Marine biomass, e.g. seaweed, is a valuable substrate because it is rich in PO43-, NO3

- and NH4+,

in some trace elements (e.g. K+), in valuable cations Mg2+ and Ca2+), but also in heavy metals such as Cd2+ [1]. The Cd content in seaweed however, renders this biomass as a risky product to use, especially as an end-product as bio-fertilizer for the agricultural sector [2]. To enable seaweed as a bio-based fertilizer, metal ions should ideally be (i) mobilized and thereafter (ii) adsorbed or removed in connection to e.g. biogas production. In this work, we demonstrate cadmium abatement from a leachate derived from a hydrolysis of seaweed using hydrothermally modified TiO2 particles or titanate nanotubes (TNTs) supported in cryogels [3]. TNTs have been demonstrated to be successful adsorbents for cadmium, but few reports are based on real waste streams. In this study, we focus on the removal of Cd2+ once it is mobilized from the seaweed, and we demonstrate a facile way of implementing TNTs in real systems. The produced TNTs were incorporated in cryogels (TNT-cryo) and in detail characterized. Cryogels is a hydrogel produced at sub-zero temperatures and with a highly interconnected channel system [4], providing an efficient support. In Figure 1, removal of cadmium by TNT-cryo in a particulate-containing leachate derived from hydrolysis of seaweed is shown. In this continuous flow-through process, nearly 1000 ml of leachate by a 0.5 ml monolithic-shaped TNT-cryo, holding 2% (w/v) TNTs, is treated and Cd2+ was removed to more than 95%. Other co-ions were also removed at varied extent. To a lesser degree, valuable cations Ca2+ (14%), NH4

+ (3%), K+ (~10%) whereas NO3- and SO4

2- were removed to a higher extent (~50%). By this process, the seaweed biomass can be further used as a bio-based fertilizer, provided cadmium is reduced in a remediation process providing a selective adsorption similar to what is shown here.

Figure 1. Continuous Cd2+ removal for TNT-cryo in spiked leachate water of 1 mg Cd L-1 at a flow rate of 0.5 ml min-1 in a leachate with total solids of 3.4±0.4%, total suspended solids 7.8±0.2 mg L-1, and volatile solids of 21%. (pH =7.8±0.01, T = 22ºC). References [1] V.N. Nkemka and M. Murto, Process Biochem. 47(12): p. 2523-2526 (2012). [2] C.. van Netten, et al., Sci Total Environ. 255(1–3): p. 169-175 (2000). [3] A.J. Du, D.D., Sun, J.O., Leckie, J Hazard Mater. 187(1-3):p. 96-100 (2011). [4] H. Kirsebom and B. Mattiasson, Polym Chem. 2(5): p. 1059-1062 (2011).

 

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DETERMINATION OF PBDEs BY VALIDATED GC-IDMS METHOD IN WATER

WITH LOW DETECTION LIMIT

B. Binici1, M. Bilsel1, A. C. Gören1, C. Swart2, R. Philipp3 1TÜBİTAK National Metrology Institute, 54 41470 Gebze/Kocaeli, Turkey

2Physikalisch-Technische Bundesanstalt, Bundesallee 100, 38116 Braunschweig, Germany 3BAM Federal Institute for Materials Research and Testing,

Richard-Willstaetter-Str., 11, 12489 Berlin, Germany Presenting author: burcu.binici@tubitak.gov.tr

Water is the mainstay of the environment and its degradation has serious consequences. The European Union performed European Water Frame Directive (WFD) to improve water quality, in the year 2000. The purpose of this directive is to establish a protective framework for all inland surface waters in order to prevent deterioration and promote their sustainable use through protection in the medium and long term. The WFD is a highly complex legal and technical document and the quantification limits required are extremely low [1]. Regarding this purpose, in this study, method development includes development and validation of extraction, preconcentration and isotope dilution mass spectrometry (IDMS) detection technique. Liquid/liquid extraction is used as an extraction technique and preconcentration is necessary to achieve the required LOQ. A GC-IDMS method was developed and validated to determine BDE-28, BDE-47, BDE-99, BDE-100, BDE-153 and BDE-154 in water with 0.15 ngL-1 LOQ value for Ʃ PBDEs. In method validation, identification, LOD and LOQ and trueness were evaluated and uncertainty of the method was determined according to GUM. The recovery, LOD and LOQ and relative uncertainty values of the method are presented in Table 1. Table 1. Recovery, LOD and LOQ and relative uncertainty values of the method

Compound Recovery (%) LOD LOQ Relative uncertainty (%) BDE-28 81,75 0,0069 0,0232 5,53 BDE-47 94,6 0,0063 0,0211 5,26 BDE-99 93,3 0,0132 0,0441 6,98 BDE-100 96,24 0,0133 0,0442 8,69 BDE-153 92,49 0,0241 0,0805 14,79 BDE-154 93,87 0,0467 0,1558 27,49

This work is part of EMRP-project “ENV08 WFD-Traceable measurements for monitoring critical pollutants under the European Water Framework Directive (WFD-2000/60/EC)”. The EMRP is jointly funded by the EMRP participating countries within EURAMET and the European Union. References 1. European Commission, Directive 2000/60/EC of the European Parliament and of the Council

of 23 October 2000 establishing a framework for Community action in the field of water policy, OJ Eur. Comm. L 327

 

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THE ROLE OF CLIMATIC FACTORS IN GLOBAL SELENIUM CYCLING

G. D. Jones1, B. Vriens1,2, T. Blazina1,2, M. Lenz3,4, L. H.E. Winkel1,2 1Eawag Swiss Federal Institute of Aquatic Science and Technology,

8600 Dübendorf, Switzerland 2 Swiss Federal Institute of Technology (ETH) Zurich, 8092 Zurich, Switzerland

3University of Applied Sciences and Arts Northwestern Switzerland, School of Life Science, Institute for Ecopreneurship, CH-4132 Muttenz, Switzerlan

4Department of Environmental Technology, Wageningen University, 6708 WG Wageningen, The Netherlands

Presenting author: Gerrad.Jones@eawag.ch Selenium (Se) is an essential element for human health but has a relatively narrow range of recommended daily intake. Globally, Se shows a very irregular distribution in agricultural soils, which is a main factor in widespread Se deficiency: it is estimated that 0.5 to 1 billion people worldwide have too low Se intake [1]. In spite of this major environmental health threat, the processes that control the global distribution of Se are still largely unknown. Even though bedrock is locally an important source of Se into soils it has failed to explain the more widespread low to medium Se levels in soils. Hypothetically, atmospheric input of Se could be an important source of terrestrial Se and help explaining the large-scale spatial distributions of Se in soils [2]. Here we will present new insights into the sources and atmospheric pathways that control these distributions. The atmosphere is an important transient reservoir for Se, which is fed by volatile Se compounds formed via bioalkylation in both marine [2] and terrestrial [3] environments. In a study conducted in a natural wetland in Switzerland we showed that the average volatile flux of Se from the surface of the peatland is considerable (up to 0.12 µg m-2 day-1) and increases with temperature, which implies that emissions will increase with global warming [3]. The atmosphere can also function as a source of terrestrial Se via atmospheric deposition of which wet deposition is the most important [2]. Using a loess-paleosol sequence from the Chinese Loess Plateau, which is a unique record for continental climate change, we reconstructed atmospheric deposition of Se over the last 7 million years and we could show that in the paleosols, variations in Se concentrations correlate to variability in East Asian monsoon-derived precipitation [4]. This relationship indicates that the intensity of precipitation is an important controlling factor of the terrestrial Se distribution in monsoonal China, where diseases related to severe selenium deficiency occur. Insights in the role that climate plays on the abundance of Se in the terrestrial environment will pave the way for future predictions of Se distribution patterns based on climate data. These predictions are crucial in the prevention of future health hazards resulting from uneven distributions of Se in the environment. References 1. A. Haug, R.D. Graham, O.A. Christophersen, G.H. Lyons, Microb. Ecol. Health Dis. 19, 209−228 (2007). 2. H. Wen, J. Carignan, Atmos. Environ. 41, 7151−7165 (2007). 3. B. Vriens, M. Lenz, L. Charlet, M. Berg and L.H.E. Winkel, Nat. Commun. DOI: 10.1038/ncomms4035 (2014). 4. T. Blazina, Y. Sun, A. Voegelin, M. Lenz, M. Berg, and L.H.E. Winkel, Nat. Commun. (in press).

 

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EMERGING CONTAMINANTS IN WATER RESOURCES: FATE STUDIES AND

ASSESSMENT FOR DRINKING WATER SUPPLY

H.-J. Brauch, F. Sacher

DVGW Water Technology Center, 76139 Karlsruhe, Germany Presenting author: heinz-juergen.brauch@tzw.de

The occurrence of emerging contaminants in water resources used for drinking water production and the respective handling of information and assessment of analytical data are of major concern for environmental and health institutions as well as for water suppliers. Reasons for their presence in the water cycle are the increasing production and usage of man-made chemicals within the past 50 years as well as the inadequate waste disposal and removal in waste water treatment plants and inefficient measures to prevent their inputs in the aquatic environment. Moreover, the enormous progress of analytical equipment and methods led to findings of a huge number of emerging contaminants in low concentrations (ng/l) in wastewater, surface water, groundwater and even drinking water. A management approach will be presented that combines the results of monitoring activities and lab-scale experiments with general information on physical, chemical and biological properties of individual chemicals under investigation. Toxicity data are also needed which are provided by WHO as well as by national health organizations. The main objective of this approach is to provide water suppliers with reliable information to predict the fate of emerging contaminants during natural and technical steps of drinking water treatment. Within the past years, fate studies have been performed for various pharmaceuticals, pesticides, perfluoro compounds, artificial sweeteners etc. [1-4]. As for most of this compounds no individual threshold values or maximum contaminant levels exist, the Federal Environmental Agency (UBA) in Germany supports water supplier on request. It gives recommendations by setting health-related indication values (HRIV) for emerging contaminants in drinking water. These HRIV are often in the range between 0.1 - 3 µg/l. The UBA recommendations fit well with the well-known TTC (threshold of toxicological concern) concept which is applied in many countries worldwide. Furthermore water suppliers and their international associations advocate for comprehensive monitoring programs, precautionary measures for the protection of the aquatic environment as well as for up-grade of wastewater treatment plants. References 1. M. Scheurer, A. Michel, H.-J. Brauch, and W. Ruck, Water Res. 46, 4790 (2012) 2. F. Th. Lange, M. Scheurer, and H.-J. Brauch, Anal Bioanal Chem 40, 2503 (2012) 3. H.-J. Brauch, and F. Sacher, Water Res. 1, 17 (2011) 4. F. R. Storck, C. K. Schmidt, F. Th. Lange, J. Henson, and K. Hahn, Journ. AWWA 104, 35 (2012)

 

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QUANTIFICATION OF MICROPOLLUTANT DEGRADATION IN THE

RIVERBANK USING A LC-HRMS/MS SCREENING METHOD

J. Rothardt1, D. Radny2, H. P. Singer1, J. Hollender1 1Department of Environmental Chemistry, Swiss Federal Institute of Aquatic Science and

Technology EAWAG, 8600 Dübendorf, Switzerland 2Department Water Resources and Drinking Water, Swiss Federal Institute of Aquatic Science

and Technology EAWAG, 8600 Dübendorf, Switzerland Presenting author: judith.rothardt@eawag.ch

Riverbank filtration (RBF) is a commonly applied method to produce high quality drinking water in Europe [1]. The increasing load of organic micropollutants (MP) cause considerable conflicts with regard to maintaining drinking water quality criterias. Thus, contamination of shallow groundwater is a substantial concern, especially in effluent-dominated streams and underlines the need for an improved understanding of fate and transport of organic micropollutants [2]. Surface-water to shallow-groundwater, to drinking water well transport of a broad setup of 528 emerging contaminants (log Dow (pH 7) between -5.7 and +5.6) was investigated at three different river sites in the western part of Switzerland. The obtained samples were spiked with 163 internal standards (IS) and enriched by offline solid phase extraction using a multi-layer extraction cartridge with five different adsorber materials to enable the enrichment of micropollutants with a broad spectra of chemical-and physical properties. After elution and evaporation the sample extracts were analyzed by liquid chromatography coupled to a high resolution mass spectrometry (Q-Exactive) operated with an electrospray ionization probe [3]. Overall, 134 of the 526 MPs were detected in the sampled surface, ground, and drinking water well samples, including 70 pharmaceuticals (including 14 metabolites), 4 anaesthetic (including 2 metabolites), 32 pesticides (including 11 metabolites), 3 biocides (including 1 metabolite), 9 per-and polyfluorinated compounds, 5 food additives, 3 anti-corrosion agents (including 1 metabolite), 3 industrial chemicals, 3 personal care products, one additive and one tracer above the limit of quantification (LOQ). The LOQ varied only slightly for the two different surface waters, where additional spiking was carried out, i.e. the LOQ was below 10 ng/L for 80% and below 1 ng/L for 20% of the compounds. Riverbank filtration with varying MP removal potential ranging from 22, over 41, to 60% of the detected compounds, was observed at the three sampled sites with different retention times in the groundwater body to the sampling wells. Out of the 134 detected MPs, concentrations of 37, 40, and 42 MPs, respectively, were removed during RBF at the three investigated sites. 24 compounds were present in all analysed samples, whereof no, or only slight elimination was observed for sulfamethoxazole, lamotrigin, and carbamazepine. However, the observed MP removal cannot solely be attributed to biodegradation or retardation. First results of numerical flow and transport modeling - as part of this ongoing interdisciplinary investigation - indicate that dilution with other groundwater components need to be considered. References 1. Ray, C., Clean Technol. Environ. Policy, 10, 223 (2008). 2. Storck, F.R., Schmidt C.K., Lange F.T. et al., J. Am. Water Works Asso. 104, 35 (2012). 3. Vogler, B., Masterthesis in EAWAG, Environmental Chemistry. (2013).

 

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X-RAY DIFFRACTION STUDY OF ASBESTOS FIBERS IN URBAN ATMOSPHERE

OF CITY OF PILSEN (WEST BOHEMIA, CZECH REPUBLIC)

D. Havlíček1, O. Vik1,3, M. Klán2, J. Plocek3 1Dept. of Inorg. Chem., Faculty of Science, Charles University in Prague,

128 40, Praha 2 , Czech Republic 2Institute for Environmental Studies, Faculty of Science, Charles University in Prague,

128 40, Praha , Czech Republic 3Inst. of Inorg. Chem. of the ASCR, v.v.i., 250 68 Řež u Prahy, Czech Republic

Presenting author: havlicek@natur.cuni.cz Our work deals with actinolite occurrence in solid fraction of ambient aerosol in Pilsen basin, and its source apportionment. Such type of study can be successfully done when solving four basic problems: 1) sample collection, 2) measurement 3) way of evaluation and calculation, 4) deduction of the results. Ad 1: Our technology consists of collection dust particles on glass fibre (non-diffracting) filters in different places around the city and at different meteorological conditions. Ad 2: The filters were worked up directly by X-ray powder diffraction using parallel-beam geometry (like thin layer) and by electron microscopy. Ad 3: Semiquantitative analysis were done by “Reference Intensity Ratio” (RIR) method [1], used previously i.e. for XRD analysis of atmospheric dust in several other places [2], [3]. Ad 4: The origin of dust and source apportionment was studied with use of direct mineralogical analysis of potential dust sources (transport – engines, tyres, brakes, local burning places, heat plants ashes, building industry, quarries etc.) by X-ray diffraction. The minerals significant for each source were identified and searched on filters collecting atmospheric dust. Great surprise was high content of actinolite in some samples. We have clarified the origin of this mineral in atmospheric dust and identified its resources. References 1. B.L. Davis, Reference Intensity Method of Quantitative X-Ray Diffraction Analysis (Davis Consulting, Rapid City, 1988) 2. B. L. Davis, Atmospheric Environment 18, 2197 (1984). 3. B. L. Davis and Jixiang Guo, Atmospheric Environment 34, 2703 (2000).

 

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CHEMICAL STRATEGIES FOR SURFACE MODIFICATION OF MAGNETIC

NANOSORBENTS

A. L. Daniel-da-Silva, T. Trindade

Department of Chemistry-CICECO, Aveiro Institute of Nanotechnology, University of Aveiro, 3810-193 Aveiro, Portugal

Presenting author: tito@ua.pt Water pollution is a global problem that has raised the attention of the scientific community for the need of more effective solutions in this field. Nanotechnology related approaches have appeared in recent years with very promising possibilities, that include the development of new materials for water treatment and innovative methods of contaminants detection and monitoring. Among these topics, the development of efficient nanosorbents has been particularly investigated due to their high impact, namelly in water treatment technologies.[1] In this context, our research group has been interested in the development of magnetic nanomaterials as new sorbents for the magnetic uptake of water pollutants. This communication gives a brief overview of chemical strategies that have been employed by our group to achieve efficient magnetic nanosorbents for pollutants of diverse origin. Iron oxides have been mainly used in this context because they exhibit high magnetic susceptibility to facilitate fast separation in a moderate magnetic field and, are relatively inexpensive and do not pose major toxicity concerns. However the strategies reviewed here can be extended to other magnetic nanostructures and illustrative examples will be presented. Two selected types of nanosorbents will be discussed in more detail in which the chemistry of the surfaces has a determinant role in the removal process. Interestingly these materials have been designed by merging simple concepts typically found in inorganic chemistry and colloidal science. Thus a first example will focus on colloidal core/shell nanoparticles comprising a magnetic core (Fe3O4) coated with siliceous shells, that were functionalized with S donor ligands to achieve efficient capture of soft acids, such as Hg(II). As an alternative and distinct surface modification strategy, magnetic iron oxides have been coated with polysaccharides and their use in the magnetic removal of organic water pollutants has been investigated. The role of the biopolymer on the sorption capacity will be discussed together with chemical modifications introduced in the nanomaterials in order to improve the versatility of the purification process. References [1] M. Khajeh, S. Laurent, K. Dastafkan, Chem. Rev. 113, 7728 (2013). Acknowledgments This research was financed by the national funding from FCT (Fundação para a Ciência e a Tecnologia) through the project PTDC/CTM-NAN/120668/2010, by FEDER funding through program COMPETE and by national funding through FCT in the frame of project CICECO - FCOMP-01-0124-FEDER-037271 (FCT Pest-C/CTM/LA0011/2013).

 

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POLYCHLORINATED BIPHENYLS IN URBAN ATMOSPHERIC PARTICLES OF

THESSALONIKI, GREECE

A. Tsolakidou, D. Voutsa, C. Samara

Environmental Pollution Laboratory, Department of Chemistry, Aristotle University of Thessaloniki, 54 124 Thessaloniki, Greece

Presenting author: a.tsolakidou@chem.auth.gr Polychlorinated biphenyls are environmental contaminants regulated by the Stockholm Convention of Persistent Organic Pollutants due to their persistence, potential to bioaccumulate and toxicity. PCBs are among the organic pollutants usually found in airborne particles and contribute to their toxicity [1, 2, ]. In this study size segregated samples (<0.49µm, 0.49-0.97µm, 0.97-1.5µm, 1.5-3.0µm, 3.0-7.2µm and <7.2µm) of airborne particles were collected at an urban traffic and an urban background site in Thessaloniki, Northern Greece. Sampling was conducted during winter and summertime. Microwave assisted extraction with a 3:2 dichloromethane/hexane solution was employed for the extraction of the PCBs. The extracts were further cleaned up and fractionated on a silica gel/alumina column. The final extracts containing PCBs were analysed by employing GC-MS. Fifteen congenerss were determined: six dioxin-like polychlorinated biphenyls (PCB77, PCB105, PCB118 PCB126, PCB156 and PCB169), the Dutch-seven congeners (PCB28, PCB52, PCB101, PCB118, PCB138, PCB153, PCB180) together with PCB31, PCB128 and PCB170. This study presents the particle size distribution of PCBs and their occurrence in the alveolar fraction. Spatial and temporal variations are discussed. References 1. Breivik K., Sweetman A., Pacyna JM, Jones KC (2002) Sci Total Environ 290:181-198 2. Heal MR, Kumar P, Harrison RM (2012). Chem Soc Rev 41:6606–6630 3. Landlová L., Čupr P., Franců J., Klánová J., G. Lammel (2014) Environ Sci Pollut Res (DOI10.1007/s11356-014-2571-y) Acknowledgements This research has been co-financed by the European Union (European Social Fund – ESF) and Greek national funds through the Operational Program "Education and Lifelong Learning" of the National Strategic Reference Framework (NSRF) - Research Funding Program: Thales. Investing in knowledge society through the European Social Fund. Project code/Title: MIS 377304/"Bioactivity of airborne particulates in relation with their size, morphology and chemical composition".

 

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TOXIC EFFECTS OF SILVER NANOPARTICLES ON PSEUDOKIRCHNERIELLA SUBCAPITATA

(CHLOROPHYTA) ANALYZED IN A DROPLET BASED MICROFLUIDIC SYSTEM

J. Teuber, A.Knauer, J. M. Köhler

Technische Universität Ilmenau, Institute of Chemistry and Biotechnology, Department of Physical Chemistry and Microreaction Technology, Germany

Presenting author: Jessika.Teuber@TU-Ilmenau.de The Nanotechnology has become, in the meantime, an important economic factor with enormous revenues. Because of the different application fields of silver nanoparticles (AgNPs), AgNPs make a significant contribution towards this development. This leads to an increasing release of AgNPs into the environment with unforeseeable consequences for aquatic ecosystems. Despite the environmental risk, the investigation of the toxicity of AgNPs is still in the initial phase. In contrast to commercial particularly small AgNPs which are stabilized with chemicals like functionalized alkanes [2], the stabilizer used in this work is citrate, in order to avoid toxic by-effects on the indicator organisms. The usage of droplet based microfluidic systems allows both, the synthesis of triangular silver nanoprisms and colloidal silver nanoparticles with a narrow size distribution (Fig. 1), and comprehensive toxicity measurements. In the micro-droplet based systems, segments are generated by co-injection of an aqueous phase into the carrier solution PP9. The fluid segments were analyzed with an optical detector unit and stored either in Eppendorf cups (AgNPs synthesis) or in tube coils (toxicity examinations). After incubation, the segments in the tube coils are analyzed again by pumping the PP9 inside and passing the segments through the optical detector unit again. The toxicity investigations of AgNPs to Pseudokirchneriella subcapitata (Chlorophyta) show a significant dependence on the size and the culture media (Fig. 2; Fig. 3). Acknowledgment: Founding from the DBU (80012/740) is gratefully acknowledged. [1] www.bmbf.de/pub/nanoDE-Report_2011.pdf [2] F. Ribeiro et al.; Sci. Environment., 2014, 232–241.

Fig. 3 Figure 1: DCS spectra of the used citrate stabilized AgNPs Figure 2: Toxicity of 10.3nm-AgNPs to Pseudokirchneriella subcapitata in EPA and OECD medium Figure 3: Toxicity of 3.7nm- and 4.7nm-AgNPs to Pseudokirchneriella subcapitata in ISO medium

Fig. 1 Fig. 2

 

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EVALUATION OF OZONATION AND PHOTO-FENTON OXIDATION AS POST-

TREATMENT FOR TEXTILE WASTEWATER DEGRADATION

M. Punzi1, F. Nilsson2, B.-M. Svensson3, M. Jonstrup4 and B. Mattiasson1 1Biotechnology, Department of Chemistry, Lund University, 22100, Lund, Sweden

2Chemical Engineering, Department of Chemistry, Lund University, 22100, Lund, Sweden 3School of Education and Environment, Kristianstad University, Kristianstad, Sweden

4Sweco Environment AB, 20122, Malmö, Sweden Presenting author: marisa.punzi@biotek.lu.se

Treatment of textile wastewater is challenging because the water contains low- or non-biodegradable compounds such as dyes, detergents, surfactants, biocides and more that are used to improve the textile process and to make the clothes resistant to physical, chemical and biological agents. New technologies have been developed in the last decades and in particular Advanced Oxidation Processes (AOPs) have shown considerable potential for treatment of industrial effluents [1]. In our study, photo-Fenton oxidation and ozonation have been investigated as post-treatment after the anaerobic degradation of raw textile wastewater. The biological treatment consisted of two anaerobic biofilm reactors operated in continuous mode. The average COD reduction in the biological step was 30%, which is in line with the performance of the anaerobic treatment carried on at the full scale plant in Nijverdal, Holland [2]. The performance of the post-treatments has been compared based on their ability to reduce organic content, as COD, and acute toxicity, which was measured using Microtox® and a toxicity test targeting the brine shrimp Artemia salina. The reduction of absorbance at 254 nm was also measured to monitor the degradation of aromatic compounds. The best results were obtained using the anaerobic/photo-Fenton process with an overall 82% reduction in COD compared with an average of 70% reduction achieved using the anaerobic/ozonation process. The ozonation was carried on in batch mode and 4 ozone concentrations were tested by increasing the length of the ozonation from 1 to 6 minutes. No significant correlation was observed between ozone dose and COD reduction, which was unexpected. However, when looking at the amount of ozone actually consumed, it becomes clear that only a fraction of the ozone fed into the reactor could dissolve in the water and contribute to the oxidation of the contaminants. The final COD was 300 mg/L after photo-Fenton and 530 mg/L after ozonation, which underlines the importance of adding an additional polishing step, such as sand filtration or biological activated carbons. The final effluents had lower toxicity than the untreated wastewater, but, interestingly, the effluent treated with photo-Fenton oxidation was more toxic (EC20 33%) than that treated with ozone (EC20 64%) according to the Microtox test, even though the COD removal would suggest the opposite. In contrast, the toxicity test based on Artemia salina showed no toxicity of the treated effluents. The mutagenicity of the untreated and treated wastewater will be measured using Ames test and costs and environmental impact of the two processes will be evaluated. This study shows that physical-chemical processes, such as ozonation and photo-Fenton oxidation, can improve significantly the treatment of textile wastewater by reducing both organic content and toxicity. References 1. I. Oller, S. Malato and J.A. Sánchez-Pérez, Sci Total Environ 409, 4141-4166 (2011). 2. C.T.M.J. Frijters, R.H. Vos, G. Scheffer, R. Mulder, Water Res 40, 1249–1257 (2006).

 

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IMPACTS OF THE ORIGIN AND THE TREATMENT OF ORGANIC WASTE

RECYCLED IN AGRICULTURE ON THE FATE AND THE AVAILABILITY

OF ANTIBIOTICS IN CULTIVATED SOILS

A. Goulas1, V. Bergheaud1, S. Fehri1, V. Dumény1, S. Nélieu2, M. Deschamps1,

C.S. Haudin1, P. Benoit1

1UMR 1091 INRA-AgroParisTech Environnement and Arable Crops, 78850, Thiverval-Grignon, France

2UR 251 INRA Physicochimie et Ecotoxicologie des Sols d’Agrosystèmes Contaminés, 78000, Versailles, France

Presenting author: agoulas@grignon.inra.fr Veterinary and human antibiotics are found in manures and biosolids used in agriculture as organic amendments. The repeated introduction in cultivated soils of small amounts of antibiotics and by-products with organic waste may have an impact on microbial functions and communities, in particular by contributing to the acquisition of resistance against antibiotics. The effects of antibiotics on microorganisms are in theory linked to the bioavailable fraction of compounds in soil, which could be influenced by the treatment of organic waste (e.g. composting). The objective of this study was to follow the evolution of the (bio)available fraction of two antibiotics (sulfamethoxazole, SMX; ciprofloxacin, CIP) in soil after the application of two types of organic waste (compost of sewage sludge with green waste, bovine manure) currently used on the long-term field experiment QualiAgro (INRA–Veolia partnership 1998–2013). Soft chemical extractants were selected for this purpose and compared. Mixtures of soil (5 g dry mass, DM) and organic waste (0.15 g DM of either compost or manure) initially enriched with of a 14C-labelled antibiotic (14C-SMX: 0.74 mg.kg-1 DM; 14C-CIP: 4.97 mg.kg-1 DM) were incubated under controlled aerated conditions for 28 days. The mineralization of the 14C-antibiotic and the organic matter was followed over the incubation period. At 0, 7 and 28 days, the (bio)availability of each 14C-antibiotic in mixtures was assessed through a soft chemical extraction with different aqueous solutions. A second extraction with an acetonitrile/water mixture was performed and solid residues were then dried and burnt in order to quantify the fraction of non-extractable 14C-SMX and 14C-CIP residues. The fractions of extracted 14C-antibiotic residues differed according to the type of aqueous solution in both types of organic waste-soil mixtures. The availability of 14C-SMX decreased rapidly over time. The availability of 14C-CIP was very low at the start of the incubation but it slightly increased at 7 days for the manure treatment. Regardless of the choice of the aqueous solution, significant amounts of non-extractable residues (NER) were formed after 28 days. The choice of the aqueous solution impacted more the relative proportions of 14C-antibiotic residues extracted by the aqueous solutions and the acetonitrile/water mixture than the amounts of NER. Less than 1% of the initially added 14C-CIP was mineralized after 28 days, against 2-3% for 14C-SMX. The mineralization of organic matter was more important with manure. We hypothesize that the stimulation of microbial activity may explain the greater formation of NER of 14C-SMX residues for the manure treatment.

 

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SIMULTANEOUS DETERMINATION OF CYANOTOXINS CYLINDROSPERMOPSIN

AND ANATOXIN-A IN WATER USING LC-MS/MS. OPTIMIZATION OF

EXTRACTION WITH EXPERIMENTAL DESIGN

C. Christophoridis, A. Droungou, S.-K. Zervou, T. Triantis, T. Kaloudis, A. Hiskia

National Center for Scientific Research “Demokritos”, IAMPPNM, 15310 Athens, Greece Presenting author: cchrist@chem.demokritos.gr

Cyanobacteria are considered a rising environmental problem, since under favorable conditions, they can form extensive algal blooms and produce a wide range of cyanotoxins, which pose a significant risk to aquatic habitats and human health. Anatoxin-a (ANA) and Cylindrospermopsin (CYN), are two important cyanotoxins, often found in water bodies worldwide at increasing frequency and rising concentrations. The objective of this study were: a) the development and validation of a chromatographic method for the simultaneous determination of CYN and ANA in water, using LC-MS/MS and b) the development and optimization of an extraction-preconcentration procedure using Solid Phase Extraction (SPE) and experimental design approach. For the chromatographic separation of the compounds a reversed phase column was used (Atlantis T3 C18, 100x 2.1 mm, Waters) with an isocratic elution program - ACN (0.5% HCOOH) : H2O (0.5% HCOOH), 5% : 95%, ESI ionization and analysis time of 10 min. Quantification of CYN was based on the product ion 416 -> 194 m/z and verification on product ions 416 -> 274 and 336 m/z. For ANA, quantification was based on product ion 166->149 and verification on 166->131. Under those chromatographic conditions retention times were: CYN Rt=2,7 min and ANA tR=3,6 min. ESI operating conditions were optimized for both compounds, and deuterated phenylalanine PHE-d5 was used as a surrogate standard. SPE cartridges with porous graphitic carbon, (Hyper PGC, 200mg,Thermo) were used for the extraction of CYN and ANA from water. The effect of various factors (initial sample pH, sample volume, ratio of MeOH:CH2Cl2 as eluent, %formic acid in eluent, eluent volume, % MeOH in initial sample) on the recovery was studied, using an experimental design approach. Initially, the three most important factors were selected using a Plackett-Burman design, in order to determine the parameters with the highest impact on the selected response (recovery). Subsequently a Central Composite Design (CCD) was used for the detailed analysis of the main effects and the interactions between factors. The use of an organic mixture of MeOH:CH2Cl2 is improving recovery values for CYN, as opposed to the use of pure MeOH (increase from 5-8% to 105-135%). Further addition of formic acid on the elution mixture is enhancing the recovery. Increasing sample pH (higher than 10), is significantly improving the recovery of ANA from (1.2-5.4%) to (57.7-76.5%). The three factors with the highest impact on the response were initial sample pH, ratio of MeOH:CH2Cl2 as eluent and % formic acid in eluent. The significance of the proposed CCD model was acceptable and validated statistically by the F-test (Fisher variation ratio), while model terms were estimated based on probability (P-value) with 95% confidence level. The correlation of the experimental data with the theoretically predicted ones were generally high with R2>0.980. Acknowledgments This research has been co-financed by the European Union and Greek national funds through the Operational Program "Education and Lifelong Learning" of the National Strategic Reference Framework (NSRF) – ARISTEIA (CYANOWATER project - Cyanotoxins in Fresh Waters, Advances in Analysis, Occurrence and Treatment).

 

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STRATEGIES TO CHARACTERIZE POLAR ORGANIC CONTAMINATION IN THE

AQUATIC ENVIRONMENT– EXPLORING THE CAPABILITY OF HIGH-

RESOLUTION MASS SPECTROMETRY

J. Hollender

Eawag, Swiss Federal Institute of Aquatic Science and Technology, 8600 Dübendorf, Switzerland Juliane.hollender@eawag.ch

Polar organic micropollutants such as pharmaceuticals have moved increasingly into the focus of environmental scientists, regulatory agencies, and politicians. To meet the analytical challenges of a mixture of many known and unknown compounds at low concentrations in complex matrices such as wastewater or sediment, the coupling of LC to high resolution mass spectrometry (HRMS) with high mass accuracy following appropriate ionization (ESI, APCI, APPI) is becoming a powerful method. In this presentation, the features, advantages, and limitations of LC coupled to HRMS for three conceptually different approaches are illustrated using selected studies in the field of the natural as well as engineered aquatic environment. These approaches include: (i) quantitative target analysis with reference standards; (ii) suspects screening without reference standards; and (iii) non target screening for unknowns using tailor-made software and workflows [1]. References 1. M. Krauss, H. Singer, and J. Hollender. LC-high resoluton MS in environmental analysis: from target screening to the identification of unknowns. Anal. Bioanal. Chem. 397: 943-951 (2010).

 

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1279  

OZONATION OF CETIRIZINE - KINETICS AND DETERMINATION

OF TRANSFORMATION PRODUCTS

E. Borowska1,2, M. Bourgin1, J. Hollender1,3, C. S. McArdell1, U. von Gunten1,3,4 1Eawag, Swiss Federal Institute of Aquatic Science and Technology,

CH-8600 Dübendorf, Switzerland 2Silesian University of Technology, Environmental Biotechnology Department,

PL-44100 Gliwice, Poland 3Institute of Biogeochemistry and Pollutant Dynamics (IBP), ETH Zurich,

CH-8092 Zurich, Switzerland 4School of Architecture, Civil and Environmental Engineering (ENAC), Ecole Polytechnique

Fédérale de Lausanne (EPFL), CH-1015 Lausanne, Switzerland Presenting author: ewa.borowska@eawag.ch

The efficiency of ozonation for the removal of many micropollutants from water is already proven. However, the list of emerging contaminants is growing and their fate during ozonation is still unknown. The development of analytical tools like HR-MS/MS made the detection and identification of these substances as well as their transformation products more efficient. Cetirizine, an antihistamine drug, is usually not completely removed by conventional wastewater treatment and significant concentrations were observed in aquatic environment- up to 220 ng/L in the wastewater effluent and up to 9 ng/L in the river [1]. The aims of this study are (i) to measure the ozone reactivity of cetirizine and (ii) to identify the ozonation products (OPs) formed during the reaction with ozone using both suspect and non-target approaches. The ozone reactivity of the compound was assessed by determining the ozonation rate constant. Considering the structure of cetirizine, a competition kinetic method was chosen [2]. By comparison of the decay of both cetirizine and a competitor (here carbamazepine) under different ozonation conditions, the second-order rate constant was calculated to be 2.1x105 M-1s-1 at pH 7. For the determination of ozonation products, aqueous solutions of cetirizine were ozonated under different compound-to-ozone molar ratios, ranging from an excess of compound (2:1) to an excess of ozone (1:10) in presence of tertiary butanol as a hydroxyl radical scavenger at pH 7 to guarantee only direct ozone reactions. Subsequently the OPs were detected by Liquid Chromatography coupled with a Q-Exactive High-Resolution Mass Spectrometer (ThermoScientificTM). MS data were collected using full scan mode (60-700 m/z) at 70,000 resolution and data-dependent MS2 mode at 17,500 resolution, with both positive and negative electrospray ionization. By comparison of treated samples (spiked and ozonated) with control samples (spiked and non-ozonated) using the SIEVETM software (ThermoScientificTM), the peaks potentially corresponding to OPs can be selected. The MS2 spectra of detected peaks were subsequently analyzed to propose the structure of OPs, including expert knowledge on ozone reaction mechanisms. So far, 14 cetirizine ozonation products have been detected and 3 of them could be confirmed with commercial standards. For the others, structures can be proposed and a general cetirizine ozonation pathway can be formulated. References 1. J. Kosonen and L. Kronberg, Environ. Sci. Pollut. Res. 16, 555-564 (2009). 2. C. von Sonntag and U. von Gunten, Chemistry of ozone in water and wastewater treatment (IWA Publishing, London, 2012).

 

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1296  

 

KINETIC AND PRODUCT STUDIES OF THE FERRATE(VI) INDUCED OXIDATION

OF MICROCYSTIN-LR

K. E. O’Shea1, D. D. Dionysiou2, W. Jiang1, L. Chen3,

S. R. Batchu1, P. R. Gardinali1, V. K. Sharma3 1Department of Chemistry and Biochemistry, Florida International University,

11200 SW 8th St. Miami, Florida 33199, USA 2Environmental Engineering and Science Program, University of Cincinnati

705 Engineering Research Center, Cincinnati, OH 45221-0012, USA 3Department of Environmental and Occupational Health, School of Rural Public Health,

Texas A&M University, 1266 TAMU, College Station, Texas 77843-1266, USA Presenting author: osheak@fiu.edu

The presence of microcystin-LR (MC-LR) a potent hepatotoxin produced by blue green algae in drinking water sources, is a serious threat to human health. The consumption of MC contaminated water can lead to serious liver damage and related disorders. We have demonstrated a number of hydroxyl radical mediated processes can effectively decompose and detoxify microcystins (1-4). The current study involves the use of ferrate, Fe(VI), an environmental friendly oxidant, as a potential biocide and coagulating agent for MC producing cultures and as an effective oxidant for MC. The addition of ferrate (K2FeVIO4, Fe(VI)) to a MC-LR producing culture kills the culture, which can result in the release of MC-LR from the cells. The levels of MC following Fe(VI) treatment were measured at different growth stages after treatment. The chemical kinetics for the ferrate(VI) (FeVIO4

2-, Fe(VI)) oxidation of MC-LR and model compounds (sorbic acid, sorbic alcohol, and glycine anhydride) were measured over a range of solution pH. The second-order rate constants (k) for oxidation of MC-LR decreased with increase in pH in basic medium as follows from 1.35±0.10 ×102 M-1s-1 at pH 7.5 to 8.08 ±0.08 M-1s-1 at pH 10.0. Product studies using LC/HR-MS/MS indicate the oxidation products involve primarily hydroxylation likely of the benzene ring and olefinic and diene double bonds. Hydrolysis of peptide bond of MC-LR is also proposed. While a number of the Fe(VI) mediated products are analogous to those produced by hydroxyl radical mediated oxidation we have demonstrated hydroxyl radical is not produced during Fe(VI) treatment. The protein phosphatase (PP1) activity of the treated MC-LR solution demonstrates the MC-LR biological activity is readily eliminated by ferrate treatment. Environmental factors can have negative impacts of the effectiveness of oxidative treatments. The presence of carbonate ions in water has minimal effect on the degradation efficiency under our experimental conditions. However the presence of fulvic acids(≥ 0.4 mg L-1) decreases the removal efficiency and higher Fe(VI) dosages would likely be required to effectively treat MC-LR in natural waters. References 1) Virender K. Sharma, Theodoros M.Triantis, Maria G. Antoniou, Xuexiang He, Miguel Pelaez, Changseok Han, Weihua Song, Kevin E. O'Shea, Armah A. de la Cruz, Triantafyllos Kaloudis, et al Separation and Purification Technology 91, 3-17, 2012. 2) J Andersen, C Han, K O'Shea, DD Dionysiou, Applied Catalysis B: Environmental 154, 259-266, 2014. 3) Weihua Song, Tielian Xu, William J. Cooper, Dionysios D. Dionysiou, Armah A.de la Cruz, Kevin E. O'Shea, (Environ. Sci. Technol. 43(5), 1487-1492, 2009. 4) Weihua Song, Kevin E. O’Shea and Patrick Walsh, (Toxicology and Applied Pharmacology 220, 357-363, 2007.

 

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PAH IN PM10 COLLECTED IN SÃO PAULO, BRAZIL (2003-2013)

P.Vasconcellos, S. E. Caumo, G. Pereira, S. Soares, J. B. De Andrade

Institute of Chemistry, University of São Paulo, São Paulo, Brazil Presenting author email: perola@iq.usp.br

Aerosols were collected from 2003 to 2013 at an urban site in São Paulo city, Brazil (n=152 samples). Samples were collected during the winter and during 3 extensive campaigns (spring, summer and autumn) in the campus of the University. This site is a green area, ~ 2 km from the road with intense traffic of heavy and light vehicles, and with influence of long-range transport of pollutants. Organic compounds were extracted in Soxhlet apparatus with dichloromethane and the different fractions were obtained with a silica gel column and different solvents of increasing polarity following the procedure proposed by Gogou et al. (1998). The results show that in the wintertime total PAH average concentrations were circa of 7 times higher than in the other seasons. In the wintertime, the lighter PAH presented the higher concentrations than the heavier PAH and fluoranthene and pyrene were the most abundant compounds. On the other hand, chrysene and Benzo(ghi)perilene were more abundant in the samples collected in warmer seasons. Ratios between some PAH showed that in situ emissions are predominant, and the presence of retene in the winter samples indicate the mass transport from sugarcane region contributes to air pollution (Vasconcellos et al., 2010).

Figure 1: PAH concentrations collected during winter (intensive) and extensive campaigns. Benzo(a)pyrene equivalent values show higher risk of cancer in samples collected during the winter campaigns than in extensive campaigns. References 1. Gogou, A., Apostolaki, M. et al., J. Chrom. 799, 215 (1998). 2. P. Vasconcellos, Souza, D. et al., 408, 5836 (2005).

0.0  

1.0  

2.0  

3.0  

4.0  

5.0  

6.0  

Phe   Ant   Flu   Pyr   BaA   Chr   BbF   BkF   BeP   BaP   INP   DBA  BPE  

ng  m

-­‐3  

winter  campaings  

 

74

1337  

 

BIOACCUMULATION OF SELECTED HALOGENATED ORGANIC FLAME

RETARDANTS IN THE LAKE ONTARIO FOOD WEB

B. de Jourdan1, D.C.G. Muir2, C. Teixeira2, X. Wang2, M. Keir3, S. Backus3 1University of Guelph, School of Environmental Sciences, Guelph, Canada

2Environment Canada, Aquatic Contaminants Research Div., Burlington ON L7R 4A6, Canada

3Environment Canada, Water Quality Monitoring and Surveillance, Burlington ON, Canada Presenting author: derek.muir@ec.gc.ca

Studies of persistent and bioaccumulative commercial chemicals and byproducts in aquatic food webs of remote lakes and in open waters of large lakes, such as the North American Great Lakes, have the potential to distinguish truly “bad actors”. These chemicals must have phys-chemical properties and characteristics which make them persistent and bioaccumulative in top predators. In this study the bioaccumulation and concentrations in surface waters of a wide range of non-legacy halogenated organic compounds (HOCs) was determined in the Lake Ontario food web. The same HOCs were also determined in lake waters and zooplankton from Lake Erie and a large, remote, inland lake (Lake Opeongo in Algonquin Park, ON). Large volume samples of surface waters (100 L; 4 m depth) were collected over the period 2006-2010 at mid-lake sites in each lake by direct pumping through a glass fiber cartridge followed by primary and secondary XAD-2 resin columns. Zooplankton (>100 um) and mysids were obtained by vertical hauls at the same sites as water while forage fish and lake trout from Lake Ontario were obtained in fall collections. Extracts were screened for 27 individual BDEs (Br3-Br10) and 30 other HOCs (Br3-Br6 compounds/ PBDE replacements and chlorinated flame retardants) using GC-electron capture negative ion mass spectrometry (GC-EC NIMS) with a HP-5MS and RTX-1614 capillary columns. DecaBDE was the predominant HOC present in Lake Ontario water with concentrations in the “dissolved” phase (i.e. passed through a 1.2 µm filter cartridge and extracted by XAD resin) averaging 109 pg/L. Particulate phase concentrations of DecaBDE averaged 650 pg/L, indicating that about 85% was on filtered particles. The predicted water solubility of decaBDE is 0.03 pg/L using the WSKOW QSPR in EPISuite [1]; therefore it is likely that decaBDE is associated with nano-particles (< ~ 1 µm) that pass through the filter rather than being truly dissolved. Other HOCs detectable in Lakes Ontario and Erie included Dechlorane Plus, 1,3,5-tribromo-2-methoxy-4-methylbenzene (Br3MeBz), pentabromo-ethylbenzene (PBEB), and 2,3-dibromopropyl- 2,4,6-tribromophenyl ether (DPTE), although concentrations were in the low or sub-pg/L range and near or at MDLs. A wide range of Br3-Br6 compounds were detected in zooplankton and mysis from Lake Ontario including Br3MeBz, 1,3,5-tribromobenzene (TBB), tetrabromoxylene (TBX), bis(tribromophenoxy)-ethane (BTBPE), PBEB, DPTE, pentabromocyclododecene (PBCDD), undecachloro-pentacyclooctadecadiene (aCl11DP). BDE47, BDE153, Br3MeBz and PBCDD had the highest trophic magnification factors in the Lake Ontario food web based on the slope of the log (lipid wt) concentrations versus trophic level. TBX, 1,3,5-TBB and BTBPE showed trophic dilution while other compounds e.g. BDE202 (and other hepta- and octaBDEs) were detectable in most samples but showed limited increases with trophic level. [1] US EPA. Exposure Assessment Tools and Models, Estimation Program Interface (EPI) Suite Ver 4.1. (US Environmental Protection Agency, Office of Pollution Prevention and Toxics. Washington, DC, 2011).

 

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1338  

SPATIAL AND TEMPORAL VARIATION OF POLYCYCLIC AROMATIC

COMPOUNDS IN THE ATHABASCA OIL SANDS REGION RECONSTRUCTED

FROM DATED LAKE SEDIMENT CORES

D. Muir,1, J. Kurek2, J. Kirk1, C. Manzano1, M. Evans3,

X. Wang1, J. Keating3, J. Smol2 1Environment Canada, Aquatic Contaminants Research Div., Burlington, ON, Canada

2Department of Biology, Queen’s University, Kingston, ON, Canada

3Environment Canada, Aquatic Contaminants Research Div., Saskatoon SK Canada Presenting author: derek.muir@ec.gc.ca

The Canadian oil sands region contains an estimated 168.6 billion barrels of recoverable bitumen [1], which accounts for 97% of Canada’s petroleum reserves and ranks Canada third globally in terms of domestic oil reserves [2]. In 2013, Canadian oil sands development produced 1.9 million barrels (308,000 m3) per day, consisting of about 50% marketable bitumen and 50% synthetic crude oil. Assessments of the environmental impacts of the Athabasca oil sands development in northeastern Alberta have noted the lack of long-term data and very limited information on pre-impact conditions. In this study, conducted under the Joint Oil Sands Monitoring Program, we have used paleolimnological techniques to reconstruct loadings of Polycyclic Aromatic Compounds (PACs) over the last 50 to 100 years. Dated sediment cores from 19 lakes were analysed; 11 were within about 50 km (near field) of the bitumen upgrading facilities in the development area north of Ft McMurray and 8 at 75-185 km distance (far field). Sixteen lakes were remote, undisturbed and received only atmospheric inputs, while 3 larger far-field lakes, had small communities within their catchments. Total (Σ)PAC (46 analytes) concentrations increased in all near-field lakes, beginning at the early 1970s, particularly C1-C4-alkylated PACs and C1-C4-dibenzothiophenes (DBTs). Maximum post-2000 ΣPAC fluxes were 1.8 to 24-times greater than pre-1960 background levels. Increasing ΣPAC was also evident in far-field lakes although post-2000/pre-1960 enrichment factors were generally much lower (1.0-3.9-fold). C1-C4 alkylated PACs and DBTs, which are prominent PACs in oil sands bitumen, predominated in all samples, representing 55 to 89% and 1.8 to 17% of the ΣPACs, respectively. C3-DBT/C3-phenanthrene and C2-DBT/C2-chrysene ratios, along with other indicators of combustion sources, suggest a shift to petrogenic and unweathered alkylated PAC sources in the modern sediments of near-field cores. Ratios of retene to total unsubstituted PACs were higher in pre-1960 sediments than in the modern sediments in all near-field lakes indicating a greater proportion of wood combustion and terrestrial plant inputs compared with recent times. While Σ PAC have increased markedly since the ∼1960–1970s, coinciding with over four decades of oil sands development, concentrations of unsubstituted PAC concentrations in sediments remain well below sediment quality guidelines except in one lake near the development. References 1. Energy Resources Conservation Board, 2012. ST98-2012 Alberta's Energy Reserves 2011 and Supply/Demand Outlook 2012-2021. http://www.ercb.ca/sts/ST98/ST98-2012.pdf. pp. 290. 2. Canadian Association of Petroleum Producers, 2014. Upstream Dialogue - The Facts on Oil Sands. http://issuu.com/capp/docs/oilsands-fact-book/. 68 pp.

 

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APPLICATION OF AUTOMATED SURFACE WATER QUALITY MONITORING

SYSTEM ON RIVER BASIN AND CONNECTED FOR EXPERT SYSTEM

Z. Kovács1, Z. Zsilák2, I. Cretescu3, L. Simon4, T. Yuzhakova1, Á. Rédey1

1University of Pannonia, Institute of Environmental Engineering, H-8200, Veszprém, Hungary

2University of Pannonia, Department of General and Inorganic Chemistry, H-8200, Veszprém, Hungary

3”Gheorghe Asachi” Technical University of Iasi, Faculty of Chemical Engineering and Environmental Protection, Department of Environmental Engineering and Management,

700050, Iasi Romania 4Combit IT Share of Company, H-, Budapest, Hungary Presenting author: zsofiakovacs@almos.uni-pannon.hu

According to the Directive 2000/60/EC our waters have to reach the water quality category of good quality. In order to elaborate the required programs information are needed. The main priority is to build up the network of monitoring system of water catchment area. Remote-controlled automatic on-line monitoring systems provide more useful and continuous monitoring capabilities by providing accurate data on change in water quality in real time. In our functional terms, the network includes three principal subsystems: the monitoring station, communication system and remote station. Main aspect of integrated river basin monitoring (Fig.1):- background information of catchment area, - identification of pollution sources and environmental experts able to select indicator parameters, - optimization of sustainable and maintenance cost.

Figure 1: Network monitoring in River Basin

The aim of the project is that the load on the Veszprém Séd stream can be determined on the basis of comprehensive physical-chemical measurements. The mobile station is able to analyze continuously, such as a temperature, pH value, conductivity, turbidity, nitrate-N, nitrite-N, ammonium-N and orthophosphate-P concentrations. Data transfer was provided via GPRS to database server and following the data processing and modelling the results were put on WEB surfer. Acknowledgement: This work was supported by the European Union and co-financed by the European Social Fund in the frame of the TÁMOP-4.1.1.C-12/1/KONV-2012-0015. This work was supported by the European Union and co-financed by the European Social Fund in the frame of the TÁMOP-4.2.2.A-11/1/KONV-2012-0064.

 

77

1364  

 

EFFECTS OF SALTS ON THE DESTRUCTION OF CONTAMINANTS IN SALINE

WATERS BY ADVANCED OXIDATION PROCESSES AND SUNLIGHT PHOTOLYSIS

W. A. Mitch

Department of Civil and Environmental Engineering, Stanford University, USA wamitch@stanford.edu

Saline wastewaters include produced waters from oil and gas operations, and brines produced from reverse osmosis treatment of municipal wastewaters during potable wastewater recycling operations. In some cases, the organic contaminants in these brines are a higher concern than the salts for limiting discharges to surface waters or beneficial reuse options. Hydroxyl radical or sulfate radical-based Advanced Oxidation Processes (AOPs) may enable broad-screen removal of organic contaminants in these brines, but the effects of radical scavenging by salts on contaminant degradation efficiency must be evaluated. The talk will discuss the effects of salts on these processes, with a particular focus on the implications of the transformation of hydroxyl or sulfate radicals to more selective halogen or carbonate radicals produced in the presence of high halide or carbonate concentrations. As most fresh surface waters eventually discharge their contaminants to estuaries, the natural photochemical fate of contaminants in estuarines is also a concern. The talk will also discuss the importance of ionic strength and seawater-relevant concentrations of halides on the indirect photochemical degradation of contaminants.

 

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FORMATION OF SECONDARY ORGANIC AEROSOL ON AQUATED HAZE-

AEROSOL WATER: ISOPRENE OXIDATION AND POLYMERIZATION

M. R. Hoffmann

Environmental Science & Engineering Linde-Robinson Labs, California Institute of Technology

Pasadena, California 91125, USA mrh@caltech.edu

The fate of isoprene (2-methyl-1,3-butadiene, ISO) emissions into the atmosphere is not fully understood. Increasing awareness that ISO is only partially processed in the gas-phase has refocused attention on its reactive uptake by fog, cloud, and aerosol droplets. A hydrophobic gas, ISO should preferentially partition to the surface rather than the bulk of aqueous aerosols such as haze, fogs, or clouds. These aquated aerosol phases are saturated with dissolved O2 and water-soluble unsaturated organics; they also support OH radical generation rates primarily from the solar photolysis of dissolved H2O2 that are several orders of magnitude larger than in the gas-phase. Similar results are obtained using TiO2 and Fe2O3 in suspension without the addition of added H2O2. ISO is converted therein to heavier products rather than into the C4 to C5 volatile compounds produced in the gas-phase. At λ >305 nm, photolysis of H2O2 in dilute aqueous ISO solutions yields C10H15OH species as primary products, whose formation both requires and is inhibited by O2. A minimum of seven C10H15OH isomers are resolved by reverse-phase high-performance liquid chromatography and detected as MH+ (m/z = 153) and MH+-8 (m/z = 135) signals by electrospray ionization mass spectrometry. Our findings are consistent with the addition of center OH radical to ISO, followed by HO-ISO radical reactions with ISO in competition with O2, leading to second generation HO(ISO)2 radicals that terminate as C10H15OH via beta-H abstraction by O2. We have shown that a significant fraction of gas-phase olefins should be converted into less volatile species via this process on wet airborne particles. In addition, to hydroxyl radical generated via hydrogen peroxide photolysis, Fenton’s reaction involving H2O2 and Fe(II)/Fe(IV) species also take place. In these reactions interfacial Fe(II) ions react with H2O2 and O3 > 103 times faster than Fe(H2O)6

2+ in bulk water via a process that favors inner-sphere two-electron O-atom transfer over outer-sphere one-electron transfers. The higher reactivity of di-iron ferryl ions vs. O=Fe(IV) as O-atom donors indicates that electronic coupling of mixed-valence iron centers in the weakening of the Fe(IV)-O bond in polymeric-iron ferryl species.

 

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DEVELOPMENT OF A SELF-CONTAINED, PV-POWERED DOMESTIC TOILET

AND ELECTROCHEMICAL WASTEWATER TREATMENT SYSTEM

M. R. Hoffmann

Environmental Science & Engineering Linde-Robinson Labs, California Institute of Technology

Pasadena, California 91125, USA mrh@caltech.edu

The Hoffmann research group has developed a transportable prototype designed for the treatment of raw domestic wastewater, human urine, human feces, and synthetic human waste analogues. After several hours of PV-powered electrochemical treatment, the turbid, black-water influent can be clarified with the elimination of the suspended particles along with the reduction or total elimination of the chemical oxygen demand (COD), total enteric coliform disinfection via in situ reactive chlorine species generation, and the elimination of measurable protein after 3 to 4 hours of PV-powered treatment. Our advanced prototype incorporates additional features such as a residual sludge handling unit, a hydrogen purification and filter system, and a closed-loop water reuse system for flushing water. We have packaged our second-generation prototypes into modified shipping containers are ready for field-testing in remote locations that lack traditional urban infrastructure. Extensive field-testing in India began in April 2014.

Figure 1: Caltech pre-alpha prototype on display in New Delhi, India. The unit combines a toilet room and an integrated, self-contained, PV-powered-electrochemical treatment system in which the treated water is used as flushing water.

 

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ELECTROCHEMICAL AND QUANTUM CHEMICAL STUDIES ON

NITROBENZANTHRONES, EXTREMELY MUTAGENIC ENVIRONMENTAL

POLLUTANTS

I. Linhart1, A. Králík1, J. Ludvík2, M. Himl1

1 Department of Organic Chemistry, Faculty of Chemical Technology, Institute of Chemical Technology, Prague, Technická 1905, CZ-166 28 Prague,Czech Republic

2 J. Heyrovský Institute of Physical Chemistry, Dolejškova 3, CZ-182 00 Prague, Czech Republic

Presenting author: linharti@vscht.cz

Nitrobenzanthrones (NBAs) are important environmental pollutants emitted mainly from diesel engines. Differences by 5 orders of magnitude were observed in the mutagenicity of NBA isomers, the most mutagenic one being 3-NBA [1]. Mutagenicity of NBAs was found to be closely linked to their reductive biotransformation leading to arylnitrenium ions, which are capable of binding to the DNA [2]. Electrochemical analysis in dry DMF showed that 3-NBA undergoes two subsequent fully reversible one-electron reduction steps at E1 = - 0.64 V and E2 = - 0.95 V. In contrast, in the case of 2-NBA the first reversible one-electron reduction at E1 = - 0.88 V was followed by an irreversible three-electron process at E2 = - 1.38 V. These results indicate a resonance stabilisation of the dianion derived from 3-NBA but not that derived from 2-NBA. Analogically, 3-NBA was much more readily reduced than its 2-isomer under the conditions of catalytic hydrogenation on Pd/C.

O

N+

O

O

O

N+

O

O

O

N+

O

O

3-NBA

+ e- + e-

.

Figure 1: Electrochemical reduction of 3-nitrobenzanthrone

Quantum chemical calculations (DFT, PBE1PBE/6-31G) of the potential energies for dianions of 1-, 2-, 3-, 9- and 11-NBA showed that these energies closely correlate (R = 0.989) with published values of mutagenicity in Salmonella typhimurium1 except for 11-NBA, which is virtually non-mutagenic. Although dianions formed by two-electron reduction of NBAs can arise only in aprotic solvents and certainly not in vivo, their formation by electrochemical processes as well as their resonance stabilisation might be indirectly linked to the formation and stability of benzanthronyl-nitrenium ions and to the mutagenic and carcinogenic potential of NBA isomers. Acknowledgement. This study was supported from the institutional sources of ICT Prague. References 1. T. Enya, H. Suzuki, T. Watanabe, Y. Hirayama and Y Hisamatsu. Environ. Sci. Technol. 31, 2772 (1997). 2. V. M. Arlt, Mutagenesis 20, 399 (2005).  

 

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THE OCCURRENCE AND REMOVAL OF CYTOSTATICS

CYCLOPHOSPHAMIDE AND IFOSFAMIDE IN WASTEWATERS

M. Česen1,2, T. Kosjek1,2, B. Kompare3, E. Heath1,2 1Jozef Stefan Institute, 1000, Ljubljana, Slovenia

2Jozef Stefan International Postgraduate School, 1000, Ljubljana, Slovenia 3Faculty of Civil and Geodetic Engineering, University of Ljubljana, Ljubljana, Slovenia

Presenting author: marjeta.cesen@ijs.si The trend towards the increasing use of chemotherapy among cancer patients raises questions concerning the presence of cytostatic drug residues in the environment and the impact they have on ecosystems. In the present study, we quantify cyclophosphamide (CP) and ifosfamide (IF) in hospital wastewaters, where both drugs are routinely administered to treat various types of cancers. The quality of our results regarding our analytical methodology was confirmed by an interlaboratory study, the first such study of its kind involving cytostatic residues in aqueous samples. The results will be presented at the EuCheMS separately. This paper reports the detection of CP and IF in Slovene hospital effluents in concentrations from 0.01 - 12.1 µg L-1 and 0.13 - 10.5 µg L-1, respectively. Further, we investigated the biodegradation of CP and IF (initial concentration 10 µg L-1) in a laboratory scale flow-through moving bed bioreactors with attached-growth biomass on Mutag BioChip™ carriers. The average removal efficiencies of CP and IF during the first month of a five month sampling campaign were 37 ± 8 % and 20 ± 6 %, respectively. To achieve higher removal efficiencies, the following advanced oxidation processes were investigated: UV, ozone, UV/ozone, UV/hydrogen peroxide (H2O2), ozone/H2O2 and UV/ozone/H2O2. The optimal conditions for removal were determined regarding the duration of the UV treatment and/or ozonation process (20 to 120 mins) and the amount of added H2O2 (2.5 g L-1 – 5 g L-1). The most effective treatment was UV/ozone/H2O2 (5 g L-1) treatment, which gave removal efficiencies of 99 % (CP) and 94 % (IF). The results showed that degradation fits the pseudo-first order kinetic model for both compounds with rate constants at 0.037 min-1 and 0.026 min-1 and half-lives (t½) of 18.8 min and 26.3 min for CP and IF, respectively. Actual hospital wastewater was also included in this study, where chemical analysis had revealed concentrations of CP and IF at 5.34 µg L-1 and 6.83 µg L-1, respectively. It was confirmed that the degradation kinetics followed the same order resulting in similar rate constants (CP: 0.038 min-1 and IF: 0.034 min-1) and t½ (CP: 18.0 min, IF: 20.3 min). These results indicate the potential of using UV/ozone/H2O2 treatment for removing both compounds from wastewaters. Future work will include coupling the attached-growth biomass biological treatment with selected AOP treatment (UV/ozone/H2O2) as pre- and post-treatment. Further, ecotoxicity will be evaluated in all treated samples. Acknowledgements: We would like to thank Institute of Oncology Ljubljana, Slovenia and University Medical Centre Ljubljana, Slovenia for their collaboration.

 

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APPLICATION OF ADVANCED OXIDATION PROCESSES IN THE

TRANSFORMATION OF ENDOCRIN DISRUPTING PHENYLUREA HERBICIDES -

TOXICOLOGY ASPECTS

G. Simon1, K. Kovács2, T. Alapi1,3, J. Farkas, G. Veréb1, K. Gajda-Schrantz1,

A. Dombi1 K. Hernádi1 M. Radács4, Zs. Molnár4, M. Gálfi4 1University of Szeged, Institute of Material Sciences and Engineering,

H-6725 Szeged, Tisza Lajos Krt. 103, Hungary 2Institute of Isotopes of the Hungarian Academy of Sciences,

H-1525 Budapest, P.O.Box 77, Hungary 3University of Szeged, Department of Inorganic and Analytical Chemistry

H-6701 Szeged, P.O.Box 440 Hungary 4University of Szeged, Faculty of Juhász Gyula Education, Department of Environmental

Biology and Education, H-6725 Szeged, Boldogasszony sgt. 6., Hungary Presenting author: gsimon@hem.u-szeged.hu

We live in a world in which man-made chemicals have become a part of everyday life. Some of these chemical pollutants can affect the endocrine (hormonal) system and interfere with important developmental processes in humans and wildlife. Close to 800 chemicals are known or suspected to be capable of interfering with hormone receptors, hormone synthesis or hormone conversion. The effects of EDC are not detectable in subtoxic dose in acute experiments. However, these changes can already notice by the chronic treatment with extreme low doses of EDC. Endocrine disrupting chemicals (EDCs) are groups of emerging contaminants that have been detected at trace concentrations in waters around the world. The convencional water treatment technologies are not able to eliminate these trace compounds from waters, thus additional technologies are suitable. Advanced oxidation processes (AOPs) are technologies with significant importance in environmental restoration applications. The AOPs are defined as processes involving the generation of highly reactive oxidizing species able to attack and degrade organic substances. In this work, the efficiency of the various advanced oxidation processes (UV-induced photolysis, heterogeneous photocatalysis, ozonation) and their combinations were investigated an compared in several aspects (initial rate of transformation, rate of mineralization, dehalgenization, and toxicocogy aspects) in the decomposition of diuron, monuron and phenuron, which are suspected endocrin disrupting chemicals and widely used pesticides. In our work toxicology measurements were carried out by different ways. The ecotoxicity tests were done on Selenastrum capricornutum microalgae culture, Daphnia magna zooplankton and bioluminescence inhibition assay using the marine bacterium Vihrio fischeri as the test organism. Another aim of this work was to investigate the neuroendocrine homeostatic effects of EDC agents on in vitro neuroendocrine cell culture modell systems. Our results showed that these EDC agents alone are ineffective on the monoamine activated hormone release (arginine-vasopressin). If the EDC agents were applied with monoamine active compounds together, these effects were significantly. Acknowledgements This research was supported by the European Union and the State of Hungary, co-financed by the European Social Fund in the framework of TÁMOP-4.2.4.A/ 2-11/1-2012-0001 ‘National Excellence Program’. Financial help of the Társadalmi Megújulás Operatív Program (TÁMOP-4.2.2.A-11/1/KONV-2012-0047) also highly appreciated.

 

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CONCENTRATIONS AND TRENDS OF NOVEL BROMINATED HYDROCARBONS

IN THE WATER COLUMN AND SEDIMENTS OF LAKE GENEVA (SWITZERLAND):

DETECTION AND QUANTIFICATION

USING GC×GC-µECD AND GC×GC-ENCI-TOFMS

S. Samanipour1, J. S. Arey 1,2 1Environmental Chemistry Modeling Laboratory

Swiss Federal Institute of Technology in Lausanne (EPFL), 1015, Lausanne, Switzerland

2 Department of Environmnetal Chemistry Swiss Federal Institute of Aquatic Science and Technology (EAWAG),

Dubendurf, Switzerland Presenting author: saer.samanipour@epfl.ch

The so-called novel brominated frame-retardants (NBFRs) have been introduced due to the ban on the polybrominated diphenyl ethers (PBDEs). While PBDEs have been studied extensively in different environmental compartments, the NBFRs and the degradation products of legacy BFRs have been less investigated in the environment. Using GC×GC-µECD and GC×GC-ENCI-TOFMS, we analyzed the water column of Lake Geneva (Switzerland) near the outfall of the municipal wastewater treatment plant (WWTP) of Lausanne for several brominated hydrocarbons. We also analyzed sediment samples from four different locations in the lake for these brominated hydrocarbons. We detected and quantified 2,3,4,5,6-pentabromoethylbenzene (PBEB), 4-bromobiphenyl (4BBP), and 1,3,5-tribromobenzene (TBB) in both the middle and deep water column of Lake Geneva, and we also detected 4BBP and PBEB in several sediment samples. Whereas PBEB is an NBFR, both TBB and 4BBP have other industrial uses not as flame retardants. However TBB is also a potential degradation product of the NBFR hexabromobenzene, and 4BBP is a potential degradation product of higher brominated biphenyls (legacy BFRs). All three of these brominated hydrocarbons were found in elevated concentrations in the middle water column (70 m) compared to the deep water column (170 m) of Lake Geneva. Additionally, for all three compounds, higher concentrations were observed in the sediment samples obtained from the middle deep lake and from a coastal bay containing a major WWTP outfall. Lower sediment concentrations were observed in the western lake basin near the Rhône River inflow. The observed spatial and temporal trends provide insight into potential inputs (i.e., urbanized areas, atmosphere, tributaries, and WWTP) for these brominated hydrocarbons. As a basis for comparison, we also report concentrations of five legacy BFRs (four PBDEs and hexabromobiphenyl) in these same samples. We estimated eleven environmentally relevant partitioning properties of the three brominated hydrocarbons based on their GC×GC retention times, using a recently developed estimation method. These estimated properties were used to make inferences about the environmental fate and behavior of these brominated hydrocarbons. We also report high resolution accurate m/z values of the fragments of our target analytes with a mass accuracy of ± 5 mmu produced using GC×GC-ENCI-TOFMS. This is the first study to report the environmental occurrence of 4BBP and to provide environmental partitioning property estimations, their accurate m/z values, and the ENCI-TOFMS fragmentation patterns for 4BBP, TBB, and PBEB.

 

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PHOTOCATALYTIC DEGRADATION OF PESTICIDES BY DECATUNGSTATE

ANION INTERCALATED IN LAYERED DOUBLE HYDROXIDES

PREPARED AS AEROGELS

E. S. Da Silva1,2, C. Forano2, H. D. Burrows1, M. Sarakha2,

P. Wong-Wah-Chung3, V. Prevot2 1Department of Chemistry, University of Coimbra, Rua Larga, 3004-535, Coimbra, Portugal

2Clermont Université, Université Blaise Pascal, Institut de Chimie de Clermont-Ferrand, BP 10448, F-63000 Clermont-Ferrande, France

3Aix-Marseille Université, Laboratoire Chimie de l`Environnement, Équipe Micropolluants Organiques, Campus Arbois,13006 Marseille, France

Presenting author: eliana@ci.uc.pt Water pollution originating from pesticides is a global threat, with its magnitude increasing day-by-day due to their large-scale use in intensive agriculture. In view of this, providing clean water and a clean environment is a challenging task. The advanced oxidation processes (AOPs) [1], and the branch of heterogeneous photocatalysis in particular, are very promising methods for the elimination of these pollutants due to their oxidizing efficiency even towards traces of the target compounds, leading to total mineralization, or at least to their transformation into more harmless products, allowing also the recovery of the catalyst. Several materials have been used as catalysts, as is the case of the polyoxometalate decatungstate anion (W10O32

4-), which exhibit excellent photocatalytic properties [2]. Layered double hydroxides (LDHs), a class of mineral clays displaying unique anion exchange properties, have application in various different fields, including photocatalysis [3]. In the present work we report the synthesis of LDHs aerogels trough a new simple and ecofriendly strategy, implying a fast coprecipitation combined with CO2 supercritical drying, followed by the intercalation of W10O32

4- into the layered structure through anionic exchange reaction. The photocatalytic activity of this W10O32

4--LDH heterogeneous catalyst was assessed towards photodegradation of the pesticide 2-(1-naphthyl) acetamide (NAD). NAD is a plant growth regulator that has been widely used in agriculture for more than 60 years as a component in many commercial plant rooting and horticultural formulations [4]. The photocatalyst as-prepared was carefully characterized using a large panel of solid state characterization techniques (X-ray diffraction, FTIR, TGA, SEM, etc.) and the influence of different parameters such as amount of catalyst, pH and oxygen concentration on the photocatalytic behavior of NAD were investigated. Under our experimental conditions, NAD was mineralized and the photocatalyst was recycled and reused without any loss of photocatalytic activity over four cycles of degradation, making it a promising catalyst for water treatment.

Acknowledgements Eliana S. Da Silva acknowledges Portuguese FCT (Fundação Ciência e Tecnologia) for PhD grant (SFRH/BD/43171/2008).

References 1. R. Andreozzi, V. Caprio, A. Insola, R. Marotta, Catal. Today 53, 51-59 (1999). 2. C. Tanielian, Coord. Chem. Rev. 178-180, 1165-1181(1998). 3. E. S. Da Silva, V. Prevot, C. Forano, P. Wong-Wah-Chung, H. D. Burrows, M. Sarakha, Environ. Sci Poll. Res., DOI:10.1007/s11356-014-2971-z (2014). 4. F. E. Gardner, Proc. Fla. State Hort. Soc. 54, 20-26 (1941).

 

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ON THE ADSORPTION OF HYDROCARBONS ON MICRO AND MESOPOROUS

HIGH SILICA MATERIALS: A COMBINED EXPERIMENTAL AND

COMPUTATIONAL STUDY

C. Bisio1, V. Sacchetto1, M. Cossi1, G. Gatti1, G. Paul1, I. Braschi1,2, G. Berlier3, L. Marchese1

1Department of Scienze e Innovazione Tecnologica and Centro Nano-SiSTeMI, University of Piemonte Orientale, Alessandria, Italy

2Department of Scienze Agrarie, University of Bologna, Bologna, Italy 3Department of Chimica and NIS Centre of Excellence, University of Torino, Italy

Presenting author: leonardo.marchese@mfn.unipmn.it Fuel-based compounds are pollutants generally coming from industrial waste and usually present in water and soil from areas where oil refineries and gas stations are situated. Among all contaminants, methyl tertiary butyl ether (MtBE), toluene and n-hexane were selected as model molecules representative of the most common classes of pollutants. The use of sorbent materials as micro and mesoporous silicas to adsorb these contaminants from polluted areas is receiving increasing attention [1]. The sorption capacity of silicas, with different nature and number of surface OH sites and pore size architecture, were studied. High silica ZSM-5 (SiO2/Al2O3= 280), mordenite (MOR) and Y zeolites (both with a SiO2/Al2O3 ratio of 200) [2] were indeed chosen for their peculiar physico-chemical properties. Results obtained on microporous solids were compared with those of ordered mesoporous MCM-41 silicas. The interactions of the three pollutants on the zeolites and MCM-41 silicas were studied by means of both experimental and computational approaches (Fig.1). FTIR and SS-NMR spectroscopy were used to elucidate the host/guest interactions between surface of sorbents and model molecules. H-bonding and van der Waals interactions occurring between the surface of solids and molecules were modeled by DFT calculations. Gravimetric analysis allowed to quantify the different sorption capacities of the materials. The adsorption of contaminants - as single pollutants or in binary mixtures - on the three zeolites was not reduced when it was conducted in the presence of water sorbed onto zeolites, thus suggesting reasonable performances under wet working conditions. On the contrary, water affects the structure and surface adsorption sites of MCM-41 by lowering the retention capacity of the three fuel-based pollutants. The sorbent was hence modified by grafting with hexamethyldisilazane to enhance the hydrophobicity of the silica surface.

References 1. R.S. Bowman, Micropor. Mesopor. Mater., 61, 43 (2003). 2. V. Sacchetto, G. Gatti, G. Paul, I. Braschi, G. Berlier, M. Cossi, L. Marchese, R. Bagatin, C. Bisio, Phys.Chem. Chem. Phys., 15, 13275 (2013).

Figure 1. FTIR spectroscopy of MTBE adsorbed on MOR and a DFT model of MTBE in the zeolite channel

 

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HIGHLY EFFICIENT AND COMPLETE REDUCTION OF P-NITROPHENOLS BY

HETEROSTRUCTURED AU-FE3O4 NANOCATALYSTS

R.-A. Doong, F.-H. Lin

Department of Biomedical Engineering and Environmental Sciences, National Tsing Hua University, 30013, Hsinchu, Taiwan

Presenting author: radoong@mx.nthu.edu.tw

Nitrophenols are one of the most often used chemicals in production of explosives and are easily released to the environment through the improper disposal. The Au-Fe3O4 heterostructures (Fig. 1) are novel nanomaterials with high magnetic property and excellent catalytic activity because of their unique physicochemical and catalytic properties. However, the role of electronic behaviors at the interface between Au and Fe3O4 nanoparticles in the catalytic activity of Au-Fe3O4 nanocatalysts remains unclear and the influence of environmental parameters on the catalytic reduction of p-nitrophenol by Au-Fe3O4 in aqueous solutions has received less attention. This gives a great impetus to develop a systematic study on structure characterization to elucidate the reaction mechanism for p-nitrophenol reduction by Au-Fe3O4 heterostructures in aqueous solutions. In this study, the catalytic reduction of p-nitrophenol by heterostructured Au-Fe3O4 nanocatalysts using NaBH4 as the reducing agent was investigated in aqueous solutions under various environmental conditions. The electron behaviors at the interface of Au and Fe3O4 nanoparticles were also examined to elucidate the reaction mechanisms for p-nitrophenol reduction. XPS and NEXAS results show that electrons flow is from Au seeds to Fe3O4, and lead to the formation of positively charged Au surface to accelerate the catalytic reduction efficiency and rate of p-nitrophenol. The reduction of p-nitrophenol is a surface-mediated reaction and complete reduction of p-nitrophenol by Au-Fe3O4 heterostructures is oberved under various environmental conditions. The kobs for nitrophenl reduction are in the range 0.61-1.51 min-1. The increase in pH lowers the reduction efficiency and rate of p-nitrophenol and a 2.4-fold decrease in the pseudo-first-order rate constant is observed when pH increases from 5 to 9. In addition, the Au-Fe3O4 nanocatalysts show a good separation ability and reusability which can be repeatedly applied for complete reduction of nitrophenol for at least 6 successive cycles without the loss of saturation magnetization. The possible reaction mechanism for p-nitrophenol reduction by Au-Fe3O4 heterostructures in the presence of NaBH4 is proposed (Fig. 2). Results obtained in this study clearly demonstrate that the Au-Fe3O4 heterostructures are excellent nanocatalysts which can be applied in heterogeneous catalysis, water treatment, and green chemistry.

e-e-

e-e-

e-

e-electron flow

δ+

δ+

δ+δ+

Fe3O4

AuBH4-

H2 + BO3- e-

H+ +

e-

Fe2+Fe(II)

Fe3+

H2O2

•OH

end products,CO2

Fe(II)

Fe(II)

: Au atom : O atom

: Fe atom

: Surface bound ferrous ion

4-NP 4-AP

Fig. 1. HRTEM images ofAu-Fe3O4 Fig. 2. The Regone plot for as-prepared heterostructures. and CO2-activated HPCMs.

 

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ADSORPTION OF SULFONAMIDE ANTIBIOTICS ONTO HIGH SILICA ZEOLITES:

FROM MULTIDISCIPLINARY MODEL STUDIES

TO APPLICATIONS TO REAL WATERS

I. Braschi1,3, S. Blasioli1, E. Buscaroli1, A. Martucci2, M. Cossi3, L. Marchese3

1Dipartimento di Scienze Agrarie, Università di Bologna, Bologna, Italy 2Dipartimento di Fisica e Scienze della Terra, Università di Ferrara, Ferrara, Italy

3Dipartimento di Scienze e Innovazione Tecnologica and Centro Nano-SiSTeMI, Università del Piemonte Orientale, Alessandria, Italy

Presenting author: ilaria.braschi@unibo.it

Owing to their environmental diffusion and persistence, sulfonamide antibiotics (sulfa drugs) are responsible to induce high level of resistance in bacteria. The sulfonamide anionic nature makes them highly mobile along soil profile and is responsible for their accumulation into water bodies. In order to limit the diffusion of resistance determinants, it is of utmost importance to identify adsorbents for this antibiotic family to be adopted for water cleanup purpose. Three high silica zeolites (Y, MOR, ZSM-5) have been tested for their capability to extract sulfonamides from water. Kinetics, capacity and reversibility of the adsorption have been studied along with sulfonamide arrangement into the porosities of each zeolite [1-3]. The sulfa drugs irreversibly adsorbed onto zeolite Y at ca. 26% on average and with the process equilibrium reached in less than 1 min [1,3]. The favorable adsorption kinetics was confirmed when zeolite Y was applied to both fresh and sea waters although the dissolved organic matter occurring in natural water compartments can be retained as well but with a kinetics less favorable than that shown by sulfa drugs. The main host-guest & guest-guest interactions between zeolites and sulfa drugs were defined by IR and SS-NMR analysis, and augmented by computational studies. H-bonds and van der Waals type interactions between single molecules and zeolite Y or ZSM-5 were responsible for the irreversible extraction of sulfa drugs from water [1,3]. The occurrence of intramolecular medium strength H-bond in small sized sulfa drugs upon adsorption inside zeolite Y cage revealed the formation of dimeric species whose amidic or imidic tautomeric form were identified [1,3]. Rietveld refinement and IR analysis revealed that sulfa drugs incorporation into MOR caused a close vicinity of the heterocycle ring to the side pocket oxygens [2,3]. At 65°C, MOR gave rise to a sulfachloropyridazine reaction product with a 100% selectivity and SNAr mechanism [2]. Among the regeneration strategies approached, the thermal treatment and solvent extraction gave the best results.

References [1] I. Braschi, G. Paul, G. Gatti, M. Cossi, L. Marchese. RSC Advances, 3, 7427 (2013). [2] A. Martucci, M.A. Cremonini, S. Blasioli, L. Gigli, G. Gatti, L. Marchese, I. Braschi. Micropor. Mesopor. Mat. 170, 274 (2013). [3] S. Blasioli, A. Martucci, G. Paul, L. Gigli, M. Cossi, C.T Johnston, L. Marchese. J. Coll. Interface. Sci., 419, 148 (2014).

sulfamethoxazole (SMX)

Y-SMX MOR-SMX ZSM-5-SMX

 

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PHOTOCATALYTIC DEGRADATION OF MICROCYSTIN-LR UNDER VISIBLE

LIGHT USING DOPED TIO2

T. Fotiou 1, T. Triantis 1, T. Kaloudis 2, A. Hiskia 1 1 NCSR ‘‘Demokritos’’, 15341, Athens, Greece

2 EYDAP SA, 11146, Athens, Greece Presenting author: hiskia@chem.demokritos.gr

Microcystins ( MCs) are a group of cyclic heptapeptide hepatotoxins that are produced by various cyanobacteria genera. MCs contain three D-amino acids, alanine (Ala), methylaspartic acid (MeAsp), and glutamic acid (Glu), two unusual amino acids, N-methyldehydroalanine (Mdha) and 3-amino-9-methoxy-2,6,8-trimethyl-10-phenyldeca-4,6-dienoic acid (Adda), and two variable L-amino acids (X and Y). The Adda is the amino acid responsible for their toxicity. Microcystin-LR (MC-LR) is the most studied derivative of MCs due to its frequent appearance in water resources and toxicity. Photocatalysis in the presence of TiO2/UVA appears to effectively degrade MC-LR through the formation and decay of several intermediates prior to mineralization [1]. Degradation pathways have been presented [2, 3] with hydroxyl radical (HO•) being the main oxidative species. Even though TiO2 exhibit high efficiency under UVA light, its activation to visible light can facilitate the development of remediation processes replacing the costly facilities for UV light generation. In this study, the photocatalytic degradation of MC-LR is reported using C-doped TiO2 (Kronos vlp-7000) under visible light. C-doping involves substitution of oxygen by carbon atoms producing new energy states deep in the TiO2 band gap, which are responsible for the visible light absorption. Upon TiO2 photocatalysis, excitation of electrons (e-) from the valence to the conduction band leads to the formation mainly of holes (h+), HO• and superoxide radicals (O2

•−). Although the mechanism followed under UV light is well studied, limited information is available concerning the mechanism under visible light photocatalysis [4]. Contribution of those reactive oxygen species (ROS) in the process of photodegradation under visible light was defined using a variety of scavengers (superoxide dismutase, catalase, KBr, MeOH, p-Benzoquinone) specific for different radicals. The transformation products were found to be m/z 795, m/z 835, m/z 1011.5 and m/z 1029. Product with m/z 1029 is a dihydroxylation product (possibly formed though reaction with O2

•−) with the most intense peak. Formation of m/z 1011.5 intermediate (monohydroxylation, from HO• attack) is evidenced after an induction period. Also products with m/z 795 and m/z 835 could be formed after O2

•− addition followed on either of the double bonds of Adda amino acid and by cleavage and formation of carbonyl compounds. Results showed that O2

•− seems to play a key role in the process. References 1. T. Triantis, T. Fotiou, T. Kaloudis, A. Kontos, P. Falaras, D. Dionysiou, M. Pelaez and A.

Hiskia, J. Haz. Mat. 211, 196 (2012). 2. T. Fotiou, T. Triantis, T. Kaloudis and A. Hiskia, Ind. Eng. Chem. Res. 52, 13991 (2013). 3. A. Hiskia, T. M. Triantis, M.G. Antoniou, A. De La Cruz, K. O’Shea, W. Song, T. Fotiou, T.

Kaloudis, X. He, J. Andersen and D.D. Dionysiou, Transformation Products of Emerging Contaminants in the Environment: Analysis, Processes, Occurrence, Effects and Risks, Chapter 23 p.687 (Wiley, 2013).

4. J. Andersen, C. Han, K. O'Shea and D. Dionysiou, App. Catal. B: Envir. 259, 154–155 (2014).

 

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THE IMPORTANCE OF QUALITY CRITERIA DURING INVESTIGATION OF

MICROPOLLUTANTS IN THE COMPLEX MATRIX URINE

BY A LC-MS/MS MULTIMETHOD

L. Schlittenbauer, B. Seiwert, T. Reemtsma

Helmholtz-Centre for Environmental Research, Dept. Analytical Chemistry, Permoserstrasse 15, 04318 Leipzig, Germany

Presenting author: linda.schlittenbauer@ufz.de An increasing number of so-called multiresidue-methods employing LC-MS/MS have been developed for water samples during the last years. Analogously we have developed a multimethod for human urine to study the human exposure to organic micropollutants. Quantification of 90 micropollutants is possible by UPLC – QqQ-MS (Xevo TQ-S). Analyte selection considers the relevance of the contaminant to the water cycle and was extended by metabolites (environmental as well as human). Limits of detection (LOD) were in water samples in the lower ng/L range from pure water for most analytes. In urine, however, LODs were 1 to 2 orders of magnitude higher due to matrix effects. Another critical aspect in this complex matrix is the avoidance of false positive results. For this purpose three often proposed criteria [1] had to been met:

i) detection of two MRM transitions (quantifier and qualifier), ii) correctness of the retention time (≤ 0.02 min compared to standard), iii) ion ratio of Q and q (within 80 - 120% compared to standard).

One critical example is the determination of the corrosion inhibitor benzotriazole in urine [2]. In our analyses there was a significant disturbance at that retention time which seemed to indicate the widespread human exposure to benzotriazole. However the wrong ion ratio (Q/q) proved this to be a false positive finding. During the development of multimethods less attention is usually directed to chromatographic separation. For benzotriazole it is shown that an optimized LC separation is favorable despite the longer measuring time. No cleanup was found that helped to remove the disturbing urine constituents. References 1. F. Hernandez, J.V. Sancho, O.J. Pozo, Anal Bioanal Chem 382, 934 (2005). 2. A.G. Asimakopoulos, A.A. Bletsou, Q. Wu, N.S. Thomaidis, K. Kannan, Anal Chem 85, 441 (2013).

 

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UNDERSTANDING RISKS OF FISH ON PROZAC AND OTHER HARBINGERS

OF AN URBANIZING WATER CYCLE

B. W. Brooks

Baylor University, Waco, Texas , USA Bryan_Brooks@baylor.edu

Footprints of expanding metropolitan areas extend throughout watersheds and ultimately encompass smaller order tributaries. Such population densities dictate new water reclamation plants, which discharge effluents to headwater streams, dramatically modifying instream hydrology, particularly where ephemeral streams are normative. An urbanizing water cycle is often realized in these regions. Our research has focused on effluent-dominated and dependent systems, which may result in worst case environmental risks to pharmaceuticals and other industrial chemicals. A decade ago, we reported observations of common antidepressants accumulating in fish from an effluent-dominated stream. This study was termed "Fish on Prozac". Here I present some scientific lessons learned from our studies of urban aquatic ecosystems, and pharmaceuticals in the environment, including opportunities for research, management, environmental education and public outreach. Using probabilistic hazard assessment and fish plasma modeling analyses, I further predict selective serotonin reuptake inhibitors and tricyclic antidepressants to result in therapeutic hazard to fish (e.g., internal fish plasma levels of a drug equaling a mammalian therapeutic dose) when exposed to surface water concentrations well below 1 ug/L, a common trigger value for regulatory environmental assessments.

 

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HUMAN METABOLITES OF PHARMACEUTICALS – DO THEY EMERGE AGAIN IN THE AQUATIC ENVIRONMENT AS POTENTIAL HAZARDOUS

CONTAMINANTS ?

Despina Athanasiadou1, V.Linnemann1, J. Pinnekamp1 1Institute of Environmental Engineering, Environmental Analytical Laboratory, RWTH Aachen

University, Germany Presenting author: athanasiadou@isa.rwth-aachen.de

Emerging pollutants are increasingly detected in aqueous environmental samples and among them human pharmaceuticals and related compounds consist a large category with many diverse groups, due to the advances in organic synthesis and their intensive use. They can reach the environment through excretion in the original chemical structure or as metabolites and through improper elimination or disposal [2] additionally as transformation products. Since several years scientists worldwide have performed significant research regarding occurrence, fate and health effects of the parent drugs [4,3]. However, very little attention has been given to the potential contribution that human metabolites excreted into the environment or microbial metabolites formed during environmental biodegradation of pharmaceutical residues "bio-transformation products" - may have. The scarcity of available environmental data on such substances can be attributed to the difficulty in analyzing trace amounts of previously unknown compounds in complex sample matrices without reference materials. Similar degradation reactions like those in human metabolism follow in the environment and in biological wastewater treatment by microorganisms as well and cause the emergence of these substances. In this context, the present work indicates how human metabolites are rebuilt after biological treatment (figure 1 and 2) as emerging compounds with potential hazardous impact on the aquatic organisms. Table 1: Metabolization and Transformation pathways of Metoprolol

Figure 1: Human metabolization of Metoprolol

Figure 2: Transformation of Metoprolol in the biological wastewater treatment

Investigations on aqueous environmental samples have been performed via high performance liquid chromatography (HPLC) followed by high resolution mass spectrometric (MSn) detection combined with a sample preparation procedure, in order to designate the exact molecular mass and thus to facilitate biodegradation products identification in environmental samples of 3 β-

 

92

Blockers. The present study illustrates the results of the one of them – Metoprolol – and indicates the re-formation of Metoprolol human metabolites along together with other new biotransformation products after biological treatment. Furthermore, residues of the identified compounds were detected in wastewater effluent samples in low concentrations ranging from the ng/L up to the µg/L level.

Moreover the parent compound (Metoprolol) was examined with regard on its toxicological significance via established ecotoxicological tests. On the top of that, the mixture toxicity of it and its bio-products was estimated based on the determined environmental concentrations and two different concepts that are in use for the prediction of mixture toxicity: concentration addition and independent action [1]. The ultimate aim of this study is to contribute to this challenging task of enhancing the available data on the fate, behavior, and ecotoxicity of pharmaceutical metabolites and emerging transformation products in the environment.

References 1. Cleuvers M.: Initial risk assessment for three β-blockers found in the aquatic environment. Volume 59,

Issue 2, April 2005, Pages 199–205 DOI: 10.1016/j.chemosphere.2004.11.090 2. Corcoran J.; Winter M.J.; Tyler C.R.: Pharmaceuticals in the aquatic environment: A critical review of

the evidence for health effects in fish. Critical reviews in toxicology. Volume 40, Issue 4, Pages 287-304, Published April 2010

3. Daughton CG.: Emerging pollutants, and communicating the science of environmental chemistry and mass spectrometry: Pharmaceuticals in the environment. Journal of the American society for mass spectrometry. Volume 12, Issue 10, Pages 1067-1076, Published October 2001

4. Kümmerer K.: The presence of pharmaceuticals in the environment due to human use - present knowledge and future challenges. Journal of environmental management. Volume 90, Issue 8, Pages 2354-2366, Published June 2009

   

 

93

1749  

 

PHYSICAL AND CHEMICAL PROPERTIES OF AEROSOLS IN THE

MEDITERRANEAN AND THEIR IMPACT ON REGIONAL CLIMATE

G. Kallos, J. Kushta, C. Spyrou, C. Kalogeri, N. Bartsotas

University of Athens, School of Physics, Atmospheric Modeling and Weather Forecasting Group – AM&WFG, Greece

Presenting author: kallos@mg.uoa.gr Airborne particles of anthropogenic and/or natural origin have certain direct and indirect effects in the atmosphere. Aerosols interact strongly with solar and terrestrial radiation in several ways. By absorbing and scattering the solar radiation aerosols reduce the amount of energy reaching the surface. Aerosols enhance the greenhouse effect by absorbing and emitting outgoing long wave radiation. Forcing by dust and other natural aerosols exhibit large spatial and temporal variability due to their lifetime and diverse optical properties. In this presentation we discuss the complex direct, semi-direct and indirect links and feedbacks between natural aerosols, radiation budget and the meteorological and chemical state of the atmosphere. The results of a fully coupled atmospheric modeling system (RAMS/ICLAMS) are discussed. The capabilities of this modeling system include the online coupling between chemical and meteorological processes, as well as the explicit treatment of cloud condensation, giant and ice nuclei (CCN, GCCN, IN), and size and humidity dependent optical properties for aerosols. The results from this work show that the presence of mineral dust leads to a linear reduction in solar radiation and nonlinear increase in net downward longwave radiation that is larger during daytime than nighttime. The magnitude of change in the radiation budget is determined by the vertical structure of the dust cloud and mainly its height. The perturbations in the radiation budget affect the air temperature and moisture vertical profile, leading to a cloud base lifting and redistribution of condensates. The explicit activation of aerosols as CCN and IN causes changes in the spatiotemporal patterns of the precipitation field during and after the event. These influences are caused more by the indirect rather than the direct and semi-direct effects. The changes in the diffuse and direct components of the radiation budget lead to a net negative effect on the photolysis rates that, in turn, alter the pollutants distribution. Ozone concentration, in particular, is affected by dust in a non-monotonous way determined by the availability of ozone precursors.

 

94

1771  

 

PERSISTENT ORGANICS IN THE ENVIRONMENT:ANALYSES METHODOLOGIES

AND CONCENTRATION LEVELS IN TURKEY

S. G. Tuncel

Middle East Technical University, Chemistry Department , 06531 Ankara-Turkey semratun@metu.edu.tr

Persistent organic pollutants (POPs) including PAHs (Poly Aromatic Hydrocarbons),PCBs( Poly Chlorinated bi Phenyls) and pesticides had became a threat for enviroment in turn to human health in recent two decades.It is important to understand the chemistry of these pollutants in order to develop control strategies and policy framework. Our group in the Middle East Technical University has been studying POPs composition in various environmental matricies in Turkey since 1994. The extraction procedures for the determination of moderate level polycyclic aromatic hydrocarbons (PAH) and pesticides in soil, water, plant and sediment samples had been optimized and validated . The methods optimized were soxhlet extraction, ultrasonic bath extraction, solid phase extraction and solid phase micro extraction (SPME). In order to search out the main factors affecting extraction efficiencies of the methods, factorial design was used. The best extraction method was chosen and optimum values for main factors were selected for the development of the extraction methods used for PAH and pesticides determination in different sample matrix. As an analytical tool GC_MASS or GC_flame ionization detectors. Optimized and validated methodologies are used to determine POPs in the air of capital city Ankara, sediments of Mediterranean, well water, soil and lastly in the exported agricultural products. Concentration levels in the above cases will be presented, compared with other countries and discussed considering their sources and effects on the natural environment and human health. Various conclusions we derived from 20 years of our research in the major parts of the country will be presented in this talk.

 

95

1868  

 

SOURCES AND TRANSFER OF EMERGING HALOGENATED CONTAMINANTS

ACROSS THE FOOD CHAIN

J. Hajslova, J. Pulkrabova, D. Lankova

Institute of Chemical Technology, 16628 Prague, Czech Republic Presenting author: jana.hajslova@vscht.cz

Continuous industrial development has resulted in an increasing production of various types of chemicals and their subsequent release into the environment. While most of the earlier monitoring studies focused on various chlorinated persistent organic pollutants (POPs), in the recent decades, toxicological concerns emerged on the ubiquitous occurrence of fluorine and bromine containing com pounds that may also accumulate in food chains. The high volume production of perfluoro alkylsubstances (PFASs) and brominated flame retardants (BFRs), the latter represented mainly by polybrominated diphenylethers (PBDEs), hexabromo cyclododecanes (HBCDs) and tetrabromobisphenol A (TBBPA), have led to their widespread distribution in the environment. As regards to PFASs, due to their unique characteristics such as chemical inertness, stability, hydrophobicity and lipophobicity, they are used in a variety of industrial and consumer applications while BFRs are used to reduce the flammability of treated materials. Non-occupational human exposure to PFASs and BFRs, that may occur through a variety of pathways including inhalation of contaminated dust particles or food drinking water ingestion, has been clearly documented by findings of these chemicals and their (bio)transformation products in human tissues and fluids including plasma and breast milk. The latter matrix is a widely used bioindicator that can be used to assess the body burden of these environmental pollutants especially with regard to its importance as the first food for the new born. To enable assessment of the health risks for humans, European Food Safety Authority (EFSA) launched at the end of last decade the call for providing more information on these ´emerging´ contaminants. In the first part of this presentation, the overview of advanced analytical strategies (mainly based on hybride high resolution mass spectrometry, HRMS/MS) applicable for multi-analyte/ multi-matrix analyses will be provided. In the next phase, a number of case studies focused on the transport of a wide range of PFASs, BFRs and their metabolites across food chain will be presented. Worth to notice that dietary intake has been documented to be the major source of humans´ exposure to these hazardous chemicals; regarding the contamination level in the analyzed food commodities following order decreasing was observed within EU PERFOOD project (http://www.perfood.eu): seafood > pig/bovine liver >> freshwater/marine fish > hen egg > meat >> butter.

 

96

1999  

 

CHEMODIVERSITY OF ORGANIC XENOBIOTICS IN THE ENVIRONMENT:

A NAMING AND SCIENTIFIC NIGHTMARE?

Philippe Garrigues

Institute of Molecular Sciences (ISM) University of Bordeaux / CNRS, Talence, France p.garrigues@ism.u-bordeaux1.fr

Since the first discovery of organochlorine pesticides in the 60’s, each following decade has shown new discoveries of organic environmental contaminants. Hydrocarbons (HCs, PAHs) in the 70s related to oil pollution, chlorinated compounds ( PCBs revisited, PCDD, PCDF) in the 80s related to waste incineration and combustion sources, 2nd and 3rd generation pesticides (N-, S-, P-containing compounds) in the 90s linked to agriculture practices and finally nowadays the cloudy PPCPs used by everybody on the planet. In parallel, the toxicity knowledge of organic compounds has strongly increased. In environmen-tal monitoring studies, molecular markers of toxicity are now strongly associated with the detection level of contaminants. As a consequence, a confusing puzzle of acronyms is associated with either chemical family names (PFOs, PBBs), physico-chemical properties (PBT), toxicity end-points (ED), or intended usage (PPCPs). These acronyms are used by many environmental stake holders industry, research, regulatory agencies, NGOs) expanding the confusion. This presentation will focus on organic contaminants on research, toxicity and regulation aspects. It will attempt to clarify all these concepts and to show how some of them have been developed. HC : Hydrocarbon ; PAH : Polycyclic aromatic hydrocarbon ; PCB, PCDD, PCDF : poly-chlorobiphenyl, - dibenzodioxine, - dibenzofurane ; PPCP : pharmaceuticals and personnal care products ; PFOS : Perfluorooctane sulfonate ; PBB : Polybromobiphenyl; PBT : Persistent, bioaccumulative, toxic ; ED : endocrine disruptor

 

97

Abstracts Theme A

Resources and Environment

Poster Presentations

 Poster  Presentations         pages  98  –  175                 abstract  numbers  0136  –  1878      

 

98

0136  

PHARMACEUTICAL RESIDUES IN WASTEWATERS FROM VARIOUS HOSPITALS

IN GALICIA (SPAIN)

M. J. Vázquez1, L. S. Juan2, M. Gómez1, J. Llorca2 1Labaqua,15702 Santiago de Compostela, Spain

2Labaqua, 03114, Alicante, Spain Presenting author: mariano.gomez@labaqua.com

1Labaqua,15702 Santiago de Compostela, Spain 2Labaqua, 03114, Alicante, Spain

Presenting author: mariano.gomez@labaqua.com Objective: To monitor the presence of 15 pharmaceuticals belonging to several therapeutic classes in wastewaters from various hospitals of Galicia.The discharges from three hospitals of Galicia were selected and sampled at hospital discharge to the sewer system of the city. To carry out the study eleven pharmaceuticals and four hormones or derivatives were chosen. Also, tap water samples from public and private spaces were taken in selected cities. In all the samples of water analyzed the greater concentrations that found corresponded to the group of the anti-inflammatories and also appeared some antibiotic. Wastewater from the selected hospitals is treated in municipal sewage plants and shed various rivers. Several of these compounds were also detected in the waters of these rivers. Conclusions: This study demonstrates the presence of drugs in wastewater from hospitals studied and the inability of traditional wastewater treatment plants to prevent them from reaching the rivers. It also shows the need for increase environmental monitoring of watersheds and improves processes for treatment of wastewater to eliminate these drugs The choice of compound studied is based on a compilation of papers previous To carry out this work we have developed a rapid, simple and selective multi-residue analytical method based on LLE technique followed by separation and identification by liquid chromatography / mass spectrometry mode selective ion recording (GC/MS/S1R). Its efficiency is shown in the analysis of different types of matrices, establishing quality parameters of the method and discussing their potential for improvement. The results of analyzes of samples of natural and hospital wastewater confirm the presence of these compounds, contrasting these results with those obtained in the literatures

References 1. Carballa M, Omil F, Lema JM. Comparison of predicted and measured concentrations of

selected pharmaceuticals, fragrances and hormones in Spanish sewage. Chemosphere. 72, 1118–23.(2008)

2. Daughton CG. Illicit drugs: contaminants in the environment and utility in forensic epidemiology. Rev Environ Contam Toxicol. 210, 59–110. (2011)

3 Jordi Romero, Mariano Gómez, María José Vázquez, Determinación de fármacos y productos químicos de cuidado personal (ppcps) en aguas naturales y residuales Tecnología del agua. 253, 30-41 (2004).

 

99

0143  

INTERACTION BETWEEN HUMIC SUBSTANCES AND XENOBIOTICS: IS THE

ORIGIN AND STRUCTURE OF HUMIC MATTER BE OF IMPORTANCE

M. Klavins, D. Dudare, L. Ansone

Department of Environmental Science, University of Latvia, Raina blvd 19, LV 1586, Riga, Latvia

Presenting author: maris.klavins@lu.lv Humic substances (HS) form most of the organic matter in soils and waters, and they play a principal role in the turnover of organic carbon. The interaction of humic substances with xenobiotics may modify the uptake and toxicity of these compounds by aquatic and soil organisms, and affect the fate of pollutants in the environment. The interaction between humic matter and trace elements or persistent organic pollutants has been demonstrated on many examples, but the question about significance of such interactions remains of considering emerging pollutants – pharmaceuticals and nanomaterials. Another important aspect of the interaction between humic substances and xenobiotica can be related to the impact of structure of humic substances (their origin, age etc) on the interaction character. To study the impact of origin of humic substances on their interaction with xenobiotics on example of known (trace elements) and emerging (pharmaceuticakls and nanomaterials) substances humic substances from in-depth characterized peat profiles, with known composition of precursor living material, age and humification conditions were used as well as reference and synthetic models of humic substances with known major structural elements. It has been demonstrated ability of humic substances to stabilise fullerenes in the aquatic phase. In this study the interaction between fullerenes, carbon nanotubes and humic substances has been studied using fluorescence spectroscopy. Humic substances demonstrate appreciable impact on the fate of carbon containing nanoparticles xenobiotics in natural environments. Acknowledgement Support from the National Research program is acknowledged

 

100

0144  

PEAT AS SORBENT IN NATURE AND INDUSTRY

M. Klavins, L. Ansone, A.Robalds

Department of Environmental Science, University of Latvia, Raina blvd 19, LV 1586, Riga, Latvia

Presenting author: maris.klavins@lu.lv A strong natural sorbent is peat affecting development of geochemical barriers for element flows and supporting development of natural trace element archives. Peat is characterised by a developed, complex pore system due to its main component – partially decomposed moss organic debris. We have studied natural pollutant accumulation process: concentrations of major and trace element concentration changes in profiles of raised and low moor peat and impacts of human induced element accumulation as well as dominance of naturally ongoing processes are evident. Peat hydrophobisation by means of thermal treatment (at higher temperatures yielding peat active carbon) or chemical modification with organosilanes with following thermal treatment can be used to synthesize peat based sorbents for removal of oil hydrocarbons. We have demonstrated the possible areas of use of peat and its modification products for sorption of heavy metals. Peat is a prospective sorbent because it has such advantages as low cost, biodegradability and relatively high binding capacity as well as large surface area and porosity. Sorption capacity however can be increased using graft polymerization of functional monomers onto peat. Peat sorption capacity in respect to anionic species is low. To develop peat based sorbents for removal of anionic species (such as As (III), As (V), (Sb (V), Te (IV), PO4

-3 and others) we have suggested modification of peat with Fe, Mn oxohydroxides. Such composite materials have sorption capacities in respect to anionic species more than 10 times higher than natural peat. The elaborated approaches can be applied for other types of biomaterials. Acknowledgement Support from a project 2014/0009/1DP/1.1.1.2.0/13/APIA/VIAA/044

 

101

0168  

INVESTIGATION INTO PERSULFATE OXIDATION OF BENZENE IN DIFFERENT

AQUEOUS MATRICES:

EFFECT OF CHLORIDE AND BROMIDE IONS

G. Ayoub1, T. Bruton2, A. Tuqan1, D. Sedlak2, A. Ghauch1 1American University of Beirut, Faculty of Arts and Sciences, Department of Chemistry

P.O. Box 11-0236 Riad El Solh, 1107-2020 Beirut, Lebanon 2University of California Berkeley, Department of Civil and Environmental Engineering

631 Davis Hall, Berkeley, California 94720-1710, USA Presenting author: antoine.ghauch@aub.edu.lb

Strong oxidants have been used for the remediation of recalcitrant contaminants at hazardous waste sites. Sodium persulfate, a strong oxidant, is activated by ferrihydrite to generate sulfate radicals and degrade the industrial component, benzene. Hence, greater concerns were raised to clean water from this substance. We are further interested in studying the effect of additives, such as chloride, bromide and bicarbonate, on the benzene degradation by monitoring phenol, the primary product, using HPLC. We show that phenol concentration decreases with increasing chloride concentration. The same result was achieved with the bromide system. Furthermore, it was noticed that in chloride systems, there is a continuous increase in phenol concentration over 30 days. In contrast, bromide systems depicted an increase in phenol concentration up to day 20 followed by a significant decrease. Such results expand our understanding of the chloride and bromide systems. Also, we expect bromophenol and chlorophenol to be formed within the reactor. If proved, it will be a milestone from the environmental perspective, as these byproducts too are toxic. It is worth noting that solid phase extraction was done on another long term experiments (45 days) in order to concentrate the treated solution; thereby, detect smallest amount of transformation product not possible for non-extracted sample due to detection limit issues. Henceforth, with the help of the GC/MS, we will be able to elucidate the feasibility of the mechanism and the identity of the exact byproducts formed. Keywords: Benzene, Ferrihydrite, Persulfate, Phenol, Remediation.

 

102

0180  

INVESTIGATION INTO THE REMOVAL MECHANISM OF IBUPROFEN AND

PHENACETIN USING IRON-SAND / PERSULFATE MIXTURE:

A COLUMN STUDY

A.Ghauch, N. Abou Hatab, A. El Akkawi

American University of Beirut, Faculty of Arts and Sciences, Department of Chemistry P.O. Box 11-0236 Riad El Solh, 1107-2020 Beirut, Lebanon

Presenting author: antoine.ghauch@aub.edu.lb Two pharmaceutical active ingredients Ibuprofen (Ibu) and Phenacetin (Phe) were investigated in columns study. Columns were filled with different amounts of industrial iron waste and natural sand (iron:sand 0:100; 50:50; 75:25 and 100:0). This was designed in order to find the ideal mixture proportion to reach the highest performance in removing pharmaceutical compounds from effluents and to use such mixed material for water filtration making the device sustainable and affordable to produce drinking water. 500 mL of Ibu and Phe (microM) was percolating through each column (in triplicate) every 1-3 days over a period of 25 days. Parameters like the outgoing flow, iron content and concentration of pharmaceuticals in the effluents were monitored over time. SEM analyses were also performed so as to check the iron surface morphology and composition changes due to the formation of iron corrosion products (ICPs) upon oxidation. The results showed that Ibu and Phe are removed at different extents due to their different adsorptive properties and affinity to the in-situ formed ICPs. Column clogging was observed as iron content increases from 25 to 100% and in persulfate containing systems. This was attributed to the quick formation of ICPs whose volume is much greater than metallic iron before oxidation causing thereby porosity loss that affected water percolation. Ibu was much more retained into columns on iron oxides than Phe reaching 100% removal in columns containing more iron scrub. However, adsorption of pharmaceuticals showed in some cases desorption phenomenon at later stage attributed to the expulsion of organic molecules and their transformation products from iron oxides of expansion/regression properties. The developed system showed clearly that water filtration on iron:sand filters is an excellent choice for removing pharmaceutical compounds taking advantage of the formation of in-situ nascent ICPs having unique adsorptive properties not available within synthetic or aged iron oxides.

Keywords: Ibuprofen, Phenacetin, Iron scrub, sand, filtration.

 

103

0259  

VISIBLE-LIGHT-DRIVEN PHOTODEGRADATION OF BISPHENOL A BY COPPER-

DOPED HOLLOW SPHERE TITANATE NANOTUBES

S. Chang1, H.M. Tsai2, R. Doong2 1Institute of Environmental Engineering, National Chiao Tung University,

30010, Hsinchu, Taiwan 2Department of Biomedical Engineering and Environmental Sciences,

National Tsing Hua University, 30013, Hsinchu, Taiwan Presenting author: chang@mail.nctu.edu.tw

Bisphenol A (BPA) has recently attracted increasing public concern in water treatment due to its leakage from various daily used products including baby bottles, lining of food cans and thermal papers. One-dimensional titanate nanotubes (1-D TNTs) have been widely used in the environmental fields due to their high cationic adsorption and photocatalytic abilities. To enable photo-excitation of TiO2-base materials under solar irradiation, doping with copper ions in 1-D TNTs is an effective approach to extend the spectral response to visible-light region. Herein, we report a facile route to synthesize the Cu-doped hollow spheres-assembled titanate nanotubes (HS-TNTs) for photocatalytic degradation of BPA under visible light irradiation. Effect of several parameters including doped amounts of Cu(II), pH value, and initial concentration of BPA on the photodegradation of BPA by Cu-doped HS-TNTs at 465 nm were examined. The recyclability of nanomaterials towards BPA photodegradation was tested. In addition, the production of radical was determined and reaction mechanism for BPA photodegradation under visible-light illumination was proposed. The TNTs were first synthesized by hydrothermal method in 0.1 M NaOH solution at 120-180 °C for 10-24 h. The Cu2+ doped HS-TNTs were prepared by adding various Cu2+ ions into HS-TNTs synthesized in 0.1 N NaOH solution, and then the 0.7-6.9 wt% Cu-doped HS-TNTs were prepared via microwave-assisted wet-chemical reaction. Results showed that the photocatalytic activity towards BPA photodegradation by 0.7-6.9 wt% Cu2O/TiO2-TNT nanocomposites were examined under visible lightirradiation at 465 nm. Results showed that the photodegradation efficiency and rate of BPA by Cu2O/TiO2-TNTs is superior to that of Degussa P-25 TiO2 and 3.7 wt% Cu2O/TiO2-TNTs was optimal for degradation of BPA under 465 nm visible light illumination. The pseudo-fist-order rate constant (kobs) for BPA photodegradation by 3.7 wt% Cu2O/TiO2-TN was 24 and 5.7 times higher than those of pure anatase TiO2 and Degussa P25 TiO2, respectively. The photodegradation behaviours of BPA by Cu2O/TiO2-TNT nanocomposites could be well-described by the Langmuir-Hinshelwood kinetics, indicating the surface-mediated reaction of BPA by Cu2O/TiO2-TNT. The photodegradation efficiency and rate of BPA increased with the increase in pH, and the kobs for BPA photodegradation at pH 9.1 was 3 times higher than that at pH 3.9. In addition, the 3.7wt% Cu2O/TiO2-TNTs nanocomposites had a good recyclability and can be reused for at least 5 times. The electron paramagnetic resonance spectra indicated the generation of different radicals between Cu2O/TiO2-TNTs and anatase TiO2. The hydroxyl radical (•OH) was produced in the presence of anatase and Dugussa P25 TiO2, while singlet oxygen (1O2) excited state was observed after the irradiation of Cu2O/TiO2-TNTs, indicating that p-n junction between n-type TiO2 and p-type Cu2O enhanced the photocatalytic activity of Cu2O/TiO2-TNTs towards BPA photodegradation.

 

104

0287  

BACTERIA CAPTURE BY NEW CATIONIC RESINS:

SYNTHESIS, EVALUATION BY CAPILLARY ELECTROPHORESIS

F. Lemée, L. Ronin, G. Sautrey, M. Mourer, J.-B. Regnouf-de-Vains, I. Clarot

MOBAT team, SRSMC, UMR 7565, CNRS-Université de Lorraine Boulevard des Aiguillettes, 54506 Vandoeuvre-les-Nancy, France

Presenting author: frederic.lemee@univ-lorraine.fr Bacterial contaminations of food and drinking waters are serious worldwide issues. Capture and elimination of pathogenic agents leading to disinfection is a major challenge in our secured environment. In our team, we develop polycationic compounds designed to interact specifically with negatively charged bacterial surface. Some of them have previously proved their antibacterial efficiency against gram positive and gram negative bacteria in solution1,2. The transfer of their properties on solid support (grafting) may result in materials that should exhibit bacterial retention behavior. The bacterial capture capacities of different cationic solid resins (homemade and commercial anion exchange) have been evaluated against aqueous E. coli suspensions using capillary electrophoresis as quantification method. Retention results of our best synthesized resin are illustrated in Figure 1. The developed quantification method was primarily validated and is demonstrated as a fast and reliable tool to quantify bacteria3.

Figure 1: Bacterial suspensions quantification by capillary electrophoresis over time.

References 1. M. Mourer, R. E. Duval, C. Finance, J.-B. Regnouf-de-Vains, Bioorg. Med. Chem. Lett. 16,

2960-2963 (2006). 2. M. Mourer, H. Massimba Dibama, P. Constant, M. Daffé, J.-B.Regnouf-de-Vains, Bioorg.

Med. Chem. 20, 2035-2041 (2012). 3. G. Sautrey, R.E. Duval, A. Chevalley, S. Fontanay, I. Clarot, Rapid quantification of bacterial

populations by capillary isotachophoresis. On submission.

8.5  0  

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105

0307  

BIOAVAILABILITY OF METALS FROM DIESEL EXHAUST USING LUNG

SIMULATED FLUIDS

P. Mikuška1, P. Coufalík1, K. Křůmal1, M. Vojtíšek2, Z. Večeřa1

1 Institute of Analytical Chemistry, Academy of Sciences of the Czech Republic, v.v.i., Veveří 97, 602 00 Brno, Czech Republic

2 Faculty of Mechanical Engineering, Czech Technical University in Prague Technická 4, 166 07 Prague, Czech Republic

Presenting author: mikuska@iach.cz Increasing pollution of urban environment with heavy traffic constitutes a health risk associated with an inhalation of particulate matter. Vehicle exhaust emissions incorporate large amounts of metals which are contained directly in fuels or are used as engine oil additives. Deposition of inhaled particles in lungs was proved to cause toxic effects on human health. Toxicological studies on particles have suggested that it is the soluble content instead of the total trace element content that has more direct links to harmful effects. This research was aimed at the bioavailability of Cr, Cu, Mn, Pb, V and Zn in exhaust emissions from diesel engine operated on 30 % biodiesel in diesel fuel (B-30) during WHTC. Exhaust samples collected on nitratecellulose filters were extracted in the following reagents: Gamble solution [1], Gamble solution with dipalmitoyl phosphatidylcholine (DPPC) [2], artificial lysosomal fluid (ALF) [3], phosphate-buffered saline, deionized water, and the newly proposed solution with DPPC simulating the extraction in alveoli (SEA). The highest bioavailability of metals was obtained with the ALF, Gamble solution was considerably weaker extractant. The newly designed simulator of lung fluid had surprisingly lower extraction ability than deionized water. Results suggest, that SEA has a different extraction power than simulated lung fluids commonly used. Acknowledgement This work was supported by Grant Agency of the Czech Republic under grant No. P503/13/1438S and No. P503/14/25558S and by Institute of Analytical Chemistry of the Academy of Sciences of the Czech Republic under an institutional support RVO: 68081715. References 1. O. R. Moss, Health Phys. 36, 448-452 (1979). 2. M. R. Davies and N.M. Feddah, Int. J. Pharm. 255, 175–187 (2003). 3. W. Stopford, J. Turner, D. Cappellini and T. Brock, J. Environ. Monit. 5, 675–680 (2003).    

 

106

0352  

 

PREPARATION OF A WOODY BIOMASS FUNCTIONAL MATERIAL AND

ADSORPTION BEHAVIOR OF METAL IONS

Y. Mizuno, T. Suzuki, M. Suzuki, T. Sugiura, K. Kawano, T. Miyauchi

Chubu University, 4878501, Kasugai, Japan Presenting author: tk13009-9173@sti.chubu.ac.jp

Introduction The functional materials of woody biomass with chemical modification were prepared and characteristics of their adsorption for metal ions were study. Woody biomass is a biopolymer that possesses a carbon framework microstructure. Through the introduction of various functional groups with chemical processing, woody biomass can be converted into chemical materials possessing novel characteristics. The functional group to introduce into woody biomass is polyamine, phosphoric acid group and carboxyl group. Adsorption behavior of metal ions of their functional materials were studied. Experimental Pre-processing of kenaf sawdust Kenaf sawdust was first strengthened with acid or alkali in the following manner. Concentrated hydrochloric acid was gradually added kenaf sawdust. The mixture was heated with stirring, and then the mixture was washed with water and acetone. After drying, acid-treated kenaf sawdust (KSH) was obtained. For alkali processing of kenaf sawdust, 4 mol L-1 sodium hydroxide solution was gradually added kenaf sawdust with stirring. The mixtures were heated and then neutralised with acetic acid solution. After washing with water and acetone, alkali-treated kenaf sawdust (KSOH) was obtained. Introduction of polyamine to kenaf sawdust KSH was introduced polyamine using Triethyleneteramine (TETA). Acid-pretreated TETA-type kenaf sawdust (KSH-TETA) was obtained. Introduction of polyamine to phosphoric acid KSOH was reacted with phosphoryl chloride in ether. Alkali-pretreated phosphoric acid-type kenaf sawdust (KSOH-PO4H2) was obtained. Introduction of polyamine to carboxyl group KSH was oxidized with potassium permanganate. Acid-pretreated carboxyl group-type kenaf sawdust (KSH-COOH) was obtained. Result and Discussion Hg2+ and Cu2+ were adsorbed on KSH-TETA to other metal ions. The maximum adsorption capacity was 0.3 meq g-1-R. When 20 L of tap water containing 0.01~10 mg of Cu2+ and Hg2+ in the presence of several metal ions was developed by the column method, Cu2+ and Hg2+ could be recovered in about 100 w/w%. KSOH-PO4H2 was adsorbed for Mg2+ and alkaline earth metal ions. The adsorption capacity of KSOH was 1.0 meq g-1-R. KSOH-PO4H2 could be utilized for the mutual separation of Ca2+-Mg2+ and Ba2+-Sr2+. The adsorption capacity of KSH-COOH was 2.7 meq g-1 –R. KSH-COOH was adsorbed for precious metal ions. Separation of precious metal ions was possible to adjust the pH.

0

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Figure 1 Elution curves for alkaline earth metals.

Eluent / mL

Column: 8 φ ×400 mm; Flow rate: 2.5 mL min-1;KS-OH: 1g; Eluent: tartaric acid- 2,6 pyridine dicarboxylic acid- boric acid buffer solution (pH≒2.7); ↓: change of eluent: hydrochloric acid solution (pH≒1.8);

〇: Mg2+, □: Ca2+, ◇: Sr2+, △: Ba2+.

 

107

0389  

A SUB–MICRON MESOPOURS SILICA FOR THE DETERMINATION OF

SULPHUR IN SEA WATER

Awad Aqeel Al-rashdi 1 1Assisstant Professor, 21962, Alqunfudah, Kingdom of Saudi Arabia

aarashdi@uqu.edu.sa

Organosulphur compounds were determined in seawater samples by gas chromatography using a pulse flame detection method. The analytical method involved the use of Octyl-diol mesoporous silica as a replacement for organic solvents in the extraction and pre-concentration of organosulphur compounds from seawater samples based on the solid phase dispersion extraction technique. The idea of this method is based on the partitioning of the analyte between a sub-micron solid and a liquid phase as a colloidal sol. By tailoring the size of the particles to approximately 250 nm diameter, they can be easily dispersed in aqueous solution, without the need for any mechanical or hand shaking and the solid can then be readily recovered, together with the analytes, by simple filtration or centrifugation. The detection limits were in the range of 0.6–2 ng S/L, while the repeatability and reproducibility were 7–12% and 13–16% respectively. Relative standard deviations (%) for recovery of n-ethanthiol (n-EtSH), di-n-ethyl sulphide (n-Et2S) and di-n-ethyl disulphide (n-Et2S2) in spiked water samples range from 2.2–6.6% (at 0.5 µg/L level). Under the experimental conditions used, quantitative extraction of n-EtSH, n-Et2S and n-Et2S2 was achieved with recoveries ranging from 90–96%. The procedure has been successfully applied to organosulphur determination in seawater samples collected from Jeddah peach (West of Saudi Arabia).      

 

108

0394  

SOLID PHASE EXTRACTION STRATEGIES FOR THE ENRICHMENT AND

ISOLATION OF MICROPOLLUTANTS AND THEIR TRANSFORMATION PRODUCTS

FROM DIFFERENT WATER MATRICES

A. A. Deeb, T. C. Schmidt

University of Duisburg-Essen, 45141 Essen, Germany Presenting author: ahmad.deeb@stud.uni-due.de

The occurrence of a large spectrum of pharmaceuticals and personal care products in the environment clearly shows that conventional wastewater treatment plants are not capable of fully eliminating these compounds. Therefore, advanced treatment using ozonation is discussed intensively. A main drawback of ozonation is that it does not lead to a complete mineralization of organic compounds but to the formation of oxidation products (transformation products), which might be potentially toxic [1]. For example, 2,6-dichloroaniline, a toxic and carcinogenic transformation product, has been shown to be formed during ozonation of diclofenac in an aqueous matrix [2]. The need for proper sample preparation techniques is a challenging task. Up to date, there is no suitable sample preparation method available for isolation of transformation products produced during wastewater treatment. Sample preparation is a very important and essential step in environmental analysis. The basic concept of sample preparation methods is to convert a real matrix into a sample suitable for analysis. Even the best analytical techniques cannot rectify problems generated by sloppy sample pretreatment. The main goals of sample preparation include (a) removing of potential interferences, (b) increasing the concentration of target analytes in the meaning of enrichment, (c) producing a sample aliquot that will not damage the column or instrument and (d) providing a robust, reproducible method that is independent of variations in the sample matrix [3]. Within this contribution, enhanced solid phase extraction (SPE) procedures that are highly effective for the simultaneous isolation and concentration of acidic, basic and neutral compounds (pharmaceuticals/personal care products and their transformation products following ozonation during water treatment) from different environmental water matrices have been developed. The best configuration for separation of cationic, anionic and neutral (hydrophilic and lipophilic) chosen compounds was developed using a tandem of mixed-mode strong anionic exchanger (Oasis® MAX) in combination with mixed-mode strong cationic exchanger (Oasis® MCX) sorbents without any need for pH adjustment, while mixed-mode strong anionic exchanger sorbent (Oasis® MAX) was used for the isolation of small chain polar acids. High recoveries were obtained in both procedures for all tested compounds.The SPE extraction efficiency of used procedures was examined based on developed and optimized analytical methods. References [1] U. Von Gunten, Water Res., 37 (7), 1443 (2003). [2] M.M. Sein, M. Zedda, J. Tuerk, T.C. Schmidt and C. Von Sonntag, Environ. Sci. Technol.,

42, 6656-6662 (2008). [3] R.M. Smith, J. Chromatogr. A, 3, 1000 (2003).

 

109

0424  

REMOVAL OF COLURED COMPUNDS FROM INTERMEDIATE PRODUCTS OF

SUGAR PRODUCTION BY ULTRAFILTRATION AND ECONOMIC ANALYSIS

Z. Šereš1, I. Nikolić1, D. Šoronja Simović1, Lj. Dokić1, B. Pajin1, V. Tamaš1, I. Peter Szabo2 1Faculty of Technology, University of Novi Sad, 21000, Novi Sad, Serbia

2Faculty of engineering, University of Szeged, 6700, Szeged, Hungary Presenting author: ivananikolic@tf.uns.ac.rs

This industry is also well known as one of the most energy-intensive in the field of food and chemical industry. In 1999, it was reported that the production reached 16 700 000 tones, while the total value of the produced sugar was 8924 million EUR. Despite the fact that the sugar industry is one of the causes of the environmental pollution, not enough has been done on its improvement. Recent research in the sugar industry has been focused on the development and implementation of new technologies and/or the particular unit operations, which would replace the traditional ones. The separation operation deserves special attention because of its significant consumption of water end energy. Cross-flow micro- and ultrafiltration membranes can be used to remove non-sucrose compounds, or to fractionate the retentate rich in colourants. Also, it is possible to recover the expensive ingredients for re-use as well as to recover water for re-use. For implementation the membrane separation in the sugar industry, it can be expected that the molar mass of colourants increases while the density of sugar juice increases due to the polycondensation reactions favored at low water contents. According to the gel chromatography measurements (Anyos, 1984; Godshall et al., 2002), approximately 35% of all colourants, present in the initial sugar juice, have the molar mass higher than 4000 g/mol, while 51% and 81% of colourants, with the mentioned molar mass, are present in solution of the 2nd and the 3rd sugar. It can be concluded that elimination of colourants by ultrafiltration would be more efficient in the case of the raw sugar solutions of the 2nd or 3rd crystallization then in the case of the thick juice. The problems may arise from the fouling of membranes and gel polarization. In this investigations row sugar syrup with 60% dray matter content is used for coloured matter separation. The cross-flow ultrafiltration was realized on ceramic single channel membrane with 20 nm pore sizes. By ultrafiltration, in the presence of ceramic membrane with pore size of 20 nm, permeate colour decreased approximately 35% - 40%. These values could be reached, while pressure was held at 6 bar and flow rate has value lower than 250 L h-1. If we do an economical analysis of implementing this technique to the sugar factory with capacity of cca. 5000 tones of sugar beet/day, the capital costs (membrane cost, other equipment, amortisation, working hours) would be 44 EUR/m3 permeate and the operational costs (pump energy, pressure drop, electrical energy) would be 14 EUR/m3 permeate. All these calculations are made if we suppose that we will got 450 m3/day row sugar syrup with 60% dry matter content and permetae flux are cca. 0,48 m3/ membrane m2 /day.

 

110

0426  

INFLUENCE OF LECITHINS ON PHYSICAL PROPERTIES OF NON TRANS FAT

B. Pajin1, I. Lončarević1, Z. Šereš1, J. Maksimović1, D. Zarić2,

D. Šoronja Simović1, D. Šubarić3, I. Nikolić1 1Faculty of Technology, University of Novi Sad, 21000 Novi Sad, Serbia

2IHIS Tehno Experts d.o.o., Rresearch Development Center, 11000 Beograd, Serbia 3Josip JurajStrossmayer University of Osijek, 31000 Osijek, Croatia

Presenting author: ivananikolic@tf.uns.ac.rs Soybean seeds are the main source of lecithin in confectionery industry in Serbia and elsewhere. The extensive production of sunflower and rapeseed oil opens the possibility of using lecithin from these sources, as an alternative. Also, the development of functional foods dictates the use of edible fats with no undesirable trans fatty acids, obtained by fractionation and transesterification instead of common hydrogenation process. Physical properties of non trans vegetable fat with the addition of soybean, sunflower and rapeseed lecithin were investigated in this paper. Rheological measurements have confirmed that concentration of 0.5% improves the homogeneity and spread ability of the fat system. On the other hand, the addition of all three examined lecithin in concentration of 0.7% causes the opposite effect and increases the viscosity and complexity of the system. DSC measurements showed the presence of three fractions in fat with different melting properties. The addition of lecithin from different sources has significant effect on energy required for melting and some effect on other thermal properties of non trans edible fat. Keywords: non trans fat, lecithin, rheology, DSC

 

111

0427  

INTERLABORATORY EXERCISE ON ANTICANCER DRUGS

IN AQUEOUS SAMPLES

E. Heath1,2, M. Česen1,2 N. Negreira3, M. Lopez deAlda3, L. Ferrando-Climent4, L. Blahova5,

T. V. Nguyen6, M. Adahchour7, A. Ruebel8, N. Llewellyn9, J. Ščančar1,2, S. Novaković10, V.

Mislej11, D. Barcelo3,4, T. Kosjek1

1Jožef Stefan Institute, Jamova 39, Ljubljana, Slovenia 2International postgraduate School Jožef Stefan, Jamova 39, Ljubljana, Slovenia

3IDAEA-CSIC, Carrer de Jordi Girona, 18, Barcelona, Spain 4Catalan Institute for Water Research, Carrer Emili Grahit 101, Girona, Spain

5Masaryk University, Faculty of Science, RECETOX, Kamenice 5, Brno, Czech Republic 6National University of Singapore, 21 Lower Kent Ridge Rd, Singapore, Singapore

7Omegam Laboratoria, H.J.E. Wenckebachweg 120, 1114 AD, Amsterdam-Duivendrecht, The Netherlands

8IWW Water Centre, Moritzstrasse 26, 45476 Muelheim, Germany 9CEH Lancaster, Lancaster Environment Centre, Library Avenue, Bailrigg, Lancaster, UK

10Institute of Oncology Ljubljana, Zaloška cesta 2, 1000 Ljubljana, Slovenia 11Central Wastewater Treatment plant Ljubljana VO-KA,

Cesta v prod 100, 1000 Ljubljana, Slovenia Presenting author: ester.heath@ijs.si

In the absence of certified reference materials, interlaboratory comparisons are necessary if laboratories are to have confidence in their analytical abilities. The objective of this study, carried out within the EU FP7 project CytoThreat, was to perform an interlaboratory comparison on the determination of cytostatic drug residues in surface water, hospital wastewater and wastewater treatment plant effluent. To obtain the critical number of participants, an invitation to participate was offered to all laboratories identified to have the knowledge and instrumentation to analyse trace levels of cytostatics. Nine laboratories worldwide confirmed their participation in the exercise. The compounds selected included cyclophosphamide, ifosphamide, 5-fluorouracil, gemcitabine, etoposide, methotrexate and cisplatinum. The analytical methods included solid phase extraction (SPE), either on-line or off-line for sample preconcentration and the use of surrogate/internal standards for quantification. Chemical analysis was performed by either liquid or gas chromatography (LC or GC) coupled to mass (MS) and most frequently tandem mass (MS/MS) spectrometry, except for cisplatinum that was determined by inductively coupled plasma (ICP-MS). Laboratory performances were evaluated using z-score values, mean and median values, standard deviations, repeatability and reproducibility. According to submitted results only cyclophosphamide, ifosfamide, methotrexate and etoposide were included in the statistical evaluation. Overall, sample preparation was shown satisfactory. The smallest absolute differences between spiked values and the participant results were observed in surface waters. Repeatability was highest for methotrexate in all matrices and for three laboratories using LC-MS/MS (CV ≤ 12 %). Overall reproducibility was poor (CV: 27 % - 143 %) with the exception of methotrexate in a spiked hospital waste water (CV: 8 %), where compounds of interest were present in the highest concentrations.

 

112

0449  

DETERMINATION OF POLYCHLORINATED BYPHENILS AND

ORGANOCHLORINE PESTICIDES IN EUROPEAN DATE MUSSEL (LITHOPHAGA

LITHOPHAGA L., 1758) FROM THE NEUM BAY,

BOSNIA AND HERZEGOVINA

E. Makarevic, A. Marjanovic, J. Djedjibegovic, A. Dobraca, S. Muratovic, M. Sober

Faculty of Pharmacy, University of Sarajevo, 71 000, Sarajevo, Bosnia and Herzegovina Presenting author: elma_mak@yahoo.com

Persistent organic pollutants (POPs) are chemicals of global concern due to their potential for long-range transport, persistence in environment, ability to biomagnify and bioaccumulate in ecosystems, as well as their significant negative effects on human health and the environment. The most commonly encountered POPs are organochlorine pesticides, such as DDT, industrial chemicals, most notably polychlorinated biphenyls (PCB), as well as unintentional by-products of many industrial processes, especially polychlorinated dibenzo p-dioxins (PCDD) and dibenzofurans (PCDF), commonly known as ‘dioxins’ and polycyclic aromatic hydrocarbons (PAH). In this study, seven targeted polychlorinated byphenils (PCBs, IUPAC Nos. 28, 52, 101, 118, 138, 153, and 180) and the organochlorine pesticides (OCPs) aldrin, dieldrin, endrin, cis-chlordane, trans-chlordane and oxy-chlordane were quantified in European date mussel (Lithophaga lithophaga L., 1758.) from the Neum bay in the Adriatic sea (Bosnia and Herzegovina). This slow-growing species is widespread along the whole Mediterranean rocky coastline where it is frequently harvested. Our samples (n=61) were 4.5-8.0 cm in length (assessed age >17.5 years). Total OCPs in the analyzed samples were low (range from non detectable to 0.419 µg/kg w.w.), while Σ7 PCBs ranged from 20.26 to 135.37 µg/kg w.w., suggesting high level of contamination. PCBs 101, 118, 138 and 153 were dominant congeners in all samples. Results of this investigation will represent a baseline for the evaluation of long-term exposure to POPs of pericoastal area of Bosnia and Herzegovina.

 

113

0455  

STRUCTURED CATALYSTS WITH DEPOSITED MIXED OXIDES ACTIVE IN TOTAL

OXIDATION OF VOLATILE ORGANIC COMPOUNDS

F. Kovanda1, K. Jirátová2, J. Ludvíková2, J. Balabánová2, S. Krejčová1 1Institute of Chemical Technology, Prague, Technická 5, 166 28 Prague, Czech Republic

2Institute of Chemical Process Fundamentals of the AS CR, Rozvojová 135, 165 02 Prague, Czech Republic

Presenting author: mikuska@iach.cz

Volatile organic compounds (VOC) emitted in industrial gases can be eliminated applying the catalytic total oxidation. We found high catalytic activity of the Co-Mn-Al mixed oxide, obtained from layered double hydroxide (LDH) precursor, in ethanol total oxidation [1]. Recently we reported analogous catalysts deposited on anodized aluminum foils [2]. In the present study we prepared Co-Mn-Al mixed oxides over anodized aluminum sieves (intended as a part of metal monoliths) or cordierite monoliths covered by thin alumina layers deposited by sol-gel technique. The LDH precursors were formed on alumina surface during hydrothermal reaction in aqueous solutions containing Co and Mn nitrates. Alternatively, the common impregnation method was used for adding active components. The structured catalysts, obtained after heating at 500 °C, were tested in the total oxidation of ethanol, which was chosen as a model VOC. The catalytic measurements were carried out under unsteady-state conditions with heating rate of 2.27 °C min-1 (100–400 °C), at ethanol concentration in air of 1.5 g m-3 and GHSV 20 000 l lcat

-1 h-1. For comparison, the pelletized catalyst, prepared by heating the coprecipitated Co-Mn-Al LDH, and commercial Pt-Pd catalyst (monolith) were also examined. Temperatures T50 VOC, at which 50% conversion of all organic compounds was observed, are summarized in Table 1. The most active catalysts, even more active than the commercial catalyst with noble metals and the pelletized LDH-related Co-Mn-Al mixed oxide, were the aluminum sieves covered with active mixed oxides. The cordierite monoliths with deposited mixed oxides were less active; the lowest activity of monolith with LDH-related mixed oxides formed over alumina layer can be explained by low content and non-uniform distribution of active components (Co and Mn) in the monolith channels.Table 1: Activity of the mixed oxide catalysts in ethanol total oxidation Catalyst Support Co+Mn

/ wt.% T50VOC / °C

Envicat 5022-HC Monolitha (Pt-Pd) 265 LDH-rel. pellets None 67.8 245 LDH-related Al Sieveb 7.89 226 LDH-related Al Sievec 1.31 179 LDH-related Monolitha 1.71 318 Impregnated Monolitha 3.83 296

aCPSI=400; bwire 0.1 mm, open area 27%; cwire 0.25 mm, open area 37%

References 1. K. Jirátová, J. Mikulová, J. Klempa, T.

Grygar, Z. Bastl, and F. Kovanda, Appl. Catal. A 361, 106-116 (2009).

2. F. Kovanda, K. Jirátová, J. Ludvíková, and H. Raabová, Appl. Catal. A 464-465, 181-190 (2013).

Acknowledgements

The authors thank the Czech Science Foundation for the financial support (project P106/14-13750S).

 

114

0523

ISOLATION AND CHARACTERIZATION OF DENITRIFYING BACTERIA FROM

ACTIVATED SLUDGE COLLECTED FROM THE WASTEWATER TREATMENT

PLANT FOR NITRATE REMOVAL

M.K.Aouati 1, B.Kebabi 1, H.Ouled Haddar 2

1Laboratory Pollution and Water Treatment (ETPL). Constantine1 University of Ageria. 2Laboratory of Molecular Toxicology (LMT), Jijel University of Ageria

aouati.mk@gmail.com Abstract

The intensive use of fertilizers has led to an accumulation of nitrate in water reserves, which causes the deterioration of their quality. Over the years, this situation is growing more and more. Far exceeding the 50 mg / L set by the standards of the World Health Organization (WHO). High concentrations of nitrates in rivers lead their eutrophication and drinking water use will result in the occurrence of methemoglobinemia in humans. The work presented here is a study of the degradation reaction of nitrates in drinking water using a biological process that seems to be the most suitable means as it is economical and does not require great technological expertise compared to physicochemical techniques already known. However, the isolation of microorganisms that have a story that could eliminate nitrates. It has the potential of degradation, substance harmful to our environment. Samples were taken from the wastewater treatment plant (WWTP) el hamma Constantine Algeria. However, the isolation of microorganisms for a single colony was done by the method of serial dilution and streaking method The identification of several microorganisms identifications of biochemical methods such as Gram staining. The isolated bacterial strains have been identified by molecular typing method. The denitrification process requires the use of a final electron acceptor, it is often a hydrocarbon such as methanol, glucose, fructose. In our case, we tested at 35 ° C in a appropriate nutrient medium, the methanol as a sole source of carbon and energy as well as the influence of various parameters influencing the denitrification (the C / N ratio, the initial concentration of the carbon source and pH). Keywords: bacteria, carbon source, identification, nitrate, denitrification. Aslan. S (2002). Groundwater pollution problems in turky, groundwater and human developement. In: proceedings of the IHA-ALHSUD Congress in Mardel plata, Argentina, 21-25 october; 2002. Gomez. MA et al (2000). Influnce of carbon source on nitrate removal of contaminated groundwater in a denitrifying submerged filter; B80 : 69-80. Wehbe.N(2008). Dénitrification de l'eau potable en réacteur catalytique membranaire et photocatalytique. Thèse de doctorat. Université Claude bernard Lyon. Katz .I et al. (2000).Simultaneous removal of nitrate and atrazinc from groundwater. Water Sci Technol; 41(4/5) : 49-56. Tiiedje, J. M. (1988). Ecology of Denitrification and dissimilatory nitrate reduction to ammonium. In A.J.B. Zehnder (Eds.), Biology of anaerobic Microorganisms (pp. 179-­‐ 244). New-­‐York, John Weiley and sons.. Patureau, D (1995). Etude cinétique et physiologique d’une bactérie dénitrifiant en conditions anaérobies. Thèse de doctorat, université. Toulouse. WHO. Guidelines for drinking water quality. Vol.1.Recommendation. World Health Organization. Jeneva; 1984. Holt et al (1994). Bergey’s Manual of Determinative Bacteriology, 9th ed. Williams and Wilkins, Baltimore, Maryland. 1994.

 

115

 

0554  

THE EFFECT OF SAMPLING SCHEME IN THE SURVEY OF ATMOSPHERIC DEPOSITION OF HEAVY METALS IN ALBANIA BY USING MOSS

BIOMONITORING F. Qarri1, P. Lazo2, L. Bekteshi3, T. Stafilov4, M. Frontasyeva5, H. Harmens6

1 Department of Chemistry, University of Vlora,13, Vlora, Albania 2 Department of Chemistry, Faculty of Natural Sciences, University of Tirana, 10, Tirana, Albania

3 Department of Chemistry, Faculty of Natural Sciences, University of Elbasan, 23, Elbasan, Albania 4 Institute of Chemistry, Faculty of Science, Sts. Cyril and Methodius University, 1000, Skopje,

Macedonia 5 Frank Laboratory of Neutron Physics, Joint Institute for Nuclear Research, 141980, Dubna, Russia

6 Centre for Ecology & Hydrology, BT20, Bangor, United Kingdom Presenting author: flora.qarri@gmail.com

Albania is a small country (28 000 km2) with a complex geographic relief and geologic setting, and characterized by high anthropogenic influence. The first study of moss biomonitoring atmospheric deposition of metals in Albania was performed under the framework of the International Cooperative Programme on Effects of Air Pollution on Natural Vegetation and Crops with heavy metals in Europe (UNECE ICP Vegetation). 12 elements , such as conservative elements (Al, Fe), and trace elements, such as As, Cd, Cr, Cu, Ni, Pb, V and Zn, are discussed in this work. The moss samples were collected in whole territory of Albania during the the dry autumn and summer period of 2010 and 2011 [1]. The results obtained in this study have been compared with those from the investigations obtained in similar studies in some neighbouring and European countries [1]. The distribution of the elements in each sampling site identified the sites of the country with higher levels of these elements and also the main anthropogenic and geological sources. The purpose of this article is to examine and to interpret the effect of sampling design and density in long-scale environmental study. The sampling design is a fundamental part of data collection for scientifically based decision making [2]. There is no survey investigating how important the homogeneity assumptions are regarding to the practical applications of the reliability parameters [3]. The design and density of sampling scheme can significantly influence the interpretation of the survey [4]. Systematic sampling is often used in environmental applications because it is practical and convenient to implement in the field. It often provides better precision (i.e., smaller confidence intervals, smaller standard errors of population estimates) and more complete coverage of the target population than random sampling [2]. The effects of sampling density are considered and related to the quality of data interpretation and environmental assessment. Our finding shows that the spatial distributions of these elements do not depend in sampling scheme. In both cases (systematic sampling scheme, or heterogeneously distributed sampling sites) the statistical parameters are object of high variability. It is proved that the sampling scheme regarding the homogeneity and density of sampling sites has a strong effect on the statistical results of the analytical data set and the level of the pollution in the studied area. It is proved that the systematic sampling scheme with an accepted sampling homogeneity and density level provided more reliable results. References 1 F. Qarri, P. Lazo, T. Stafilov, M. Frontasyeva, H. Harmens, L. Bekteshi, K. Baceva, Z. Goryainova (2014) Environmental Science and Pollution Research, 21: 2506–2518, DOI 10.1007/s11356-013-2091-1  

 

116

0569  

 

BIOTA AS STRATEGIC TOOL FOR THE MONITORING OF THE GOOD CHEMICAL

STATUS REQUIRED BY THE WATER FRAMEWORK DIRECTIVE

R. Lava1, I Dosis1, L.I. Majoros2, M. Ricci1, A. Held1, H. Emons1. 1European Commission, Joint Research Centre, Institute for Reference Materials and

Measurements (IRMM), 2440 Geel, Belgium 2 European Chemicals Agency, 00121 Helsinki, Finland

Presenting author: Roberto.LAVA@ec.europa.eu The strategy for the protection of all European waters, set by the Water Framework Directive 2000/60/EC [1], is of primary importance and requires specific measures for pollution control. The good chemical status is one of the targets in terms of compliance with the Environmental Quality Standards (EQSs). The aim of the recent Daughter Directive 2013/39/EU [2] is the continuous review of these standards and also the establishment of a prioritisation mechanism for new Priority Substances (PS). Among the novelties introduced, the use of biota monitoring for achieving cost-effective water monitoring is further encouraged and biota EQSs are consequently set for several PS. European Member States still have the opportunity to opt for different matrix for the monitoring of a specific substance, providing that the minimal analytical performance criteria are fulfilled [3]. A discussion on issues concerning the modus operandi and biota monitoring strategies is presented considering data from Wels catfish (Silurus glanis) caught between April and June 2011. These fish are benthic top predators exhibiting biomagnification effects for organic pollutants, which also bioaccumulate due to the high level of fat content. The analyses of two organochlorine priority pollutants, hexachlorobenzene (HCB) and hexachlorobutadiene (HCBD), were carried out following a fully validated method [4]. Results show very high variability, even when considering fish of the same size, collected in the same area and period. The part of the specimen selected for the analyses (tail vs. head) also plays an important role. The data were evaluated against the EQSs; some results, considering the measurement uncertainty associated, could be interpreted either as compliant or non-compliant with the EQSs. Even from a long-term perspective and taking into account that the Directive recommends sampling frequency for biota as once per year, the conclusions are unclear. The study proposed contributes as a practical example to the on-going discussion [5] on how biota should be used for an effective implementation of the Water Framework Directive requirements. A harmonisation at European level is of primary importance to help Member States in fulfilling their obligation with regard to monitoring and control of water quality. References

1. European Commission Directive 2000/60/EC of the European Parliament and of the Council of 23 October 2000, Off. J. Eur. Union L 327, 1 (2000).

2. European Commission Directive 2013/39/EU of the European Parliament and of the Council of 13 August 2013, Off. J. Eur. Union L 226, 119 (2013).

3. European Commission Directive 2009/90/EC of the European Parliament and of the Council of 31 July 2009, Off. J. Eur. Union L 201, 36 (2009).

4. L.I. Majoros, R. Lava, M. Ricci, B. Binici, F. Sandor, A. Held and H. Emons, Talanta 116, 251 (2013).

5. M. Carere, V. Dulio, G. Hanke and S. Polesello, Trends Anal. Chem. 36, 15 (2012).

 

117

0585  

A NEW SUBSTRATE FOR THE ACTIVE DETERMINATION

OF HYDROGEN SULFIDE IN AIR

R. Cucciniello1, O. Motta2, F. Esposito1, F. Rossi1, A. Proto1 1 Department of Chemistry and Biology, University of Salerno,

Via Giovanni Paolo II 132 , 84084, Fisciano (SA),Italy 2 DISUFF, University of Salerno, Via Giovanni Paolo II 132 , 84084, Fisciano (SA),Italy

Presenting author: rcucciniello@unisa.it

Hydrogen sulfide is an undesirable air pollutant because of its malodor and toxicity even at low concentrations[1]. The standard method for environmental H2S determination involves collection of H2S on Cd(OH)2 suspension followed by reaction with p-amino-N,N-dimethylaniline to produce the dye methylene blue which is then evaluated colorimetrically[2]. Moreover, OSHA method[3] describes the collection of airborne hydrogen sulfide (H2S) in the workplace on a silver nitrate (AgNO3)-impregnated filter and analysis by differential pulse polarography (DPP) while NIOSH method[4] use activated charcoal as adsorbent for H2S followed by the quantification of the sulphate obtained by oxidation with hydrogen peroxide. A novel device for the hydrogen sulfide determination in air was developed based on the collection on zinc acetate impregnated silica substrate in glass tubes, followed by ion chromatographic quantification after sulfide oxidation to sulfate in an alkaline solution of H2O2. The reaction mechanism can be summarized as follows:

H2S + Zn(CH3COO)2 = ZnS + 2CH3COOH

S2- + 4H2O2 = SO42- + 4H2O

Laboratory tests were conducted in controlled atmosphere to evaluate uptake rate, linearity, sample stability, influence of relative humidity and interfering gases for this substrate. A pilot study was also conducted in the field in order to assess the applicability of the substrate and to understand the effect that gases such NO2 and CH4 can have on the efficiency of collection of H2S[5].

Figure 1: Sorbent tube filled with zinc acetate impregnated silica substrate for H2S determination by active sampling.

References 1 B. Tvedt, K. Skyberg, O. Aaserud, A. Hobbesland, T. Mathiesen, Am. J. Ind. Med. 20(1), 91-

101 (1991). 2. M. B. Jacobs, J. Air. Pol. Contr. As. 15(7), 314-315 (1965). 3. Occupational Safety &Health Administration Sampling and Analytical Methods: Hydrogen Sulfide. OSHA. 200 Consitution Ave, NW, Washington, DC 20210. (2006). 4. M. E. Cassinelli, Manual of Analytical Methods (NMAM). Hydrogen Sulfide: method 6013, issue 1, National Institute of Occupational Safety and Health (NIOSH) Cincinnati, OH. 5. O Motta, R. Cucciniello, C. Scicali, A. Proto, Talanta in press (2014).

 

118

0600  

AEROBIC BIODEGRADABILITY ASSESSMENT OF CEFAZOLIN

AND ITS PHOTOTRANSFORMATION PRODUCTS

W. M. M. Mahmoud1,2, K. Kümmerer1 1Sustainable Chemistry and Material Resources, Institute of Sustainable and Environmental Chemistry, Leuphana University Lüneburg, Scharnhorststr. 1, 21335 Lüneburg, Germany

2 Analytical Chemistry Department, Faculty of Pharmacy, Suez Canal University, Ismailia 41522, Egypt

Presenting author: Waleed.ahmed@uni.leuphana.de The presence of antibiotics in the environment has attracted the interest of the scientific community especially because of the possible contribution to the incresing prevalence of antibiotic resistance. Development of infectious diseases caused by multiple resistant pathogens is a serious threat to society and requires urgent action. Cefazolin (CFZ) a first-generation cephalosporin antibiotic and it is one of the essential medicines for surgical prophylaxis [1]. A recent study showed that cephalosporin underwent photolysis leading to increased toxicity against the Gram negative bacterium Vibrio fisheri in the Microtox acute toxicity test. CFZ exerted the highest acute effect in comparison to other cephalosporins, namely cephapirin, cephradine, cephalexin and cefotaxime [2]. Therefore it is important to assess the environmental fate of the cocktail of CFZ and its phototransformation products (PTPs). Photolytic degradation of CFZ was tested with two different light sources (medium-pressure mercury lamp (UV) and a xenon lamp (simulating sun light)). Aerobic biodegradability of CFZ and the mixtures resulting after 1, 2, 4, 64 min of UV-photolysis were investigated employing two OECD tests: (Closed Bottle test (CBT) and Manometric Respirometry test (MRT)). The primary elimination of CFZ was monitored and the possible formation of stable products by microbial or photolytical transformation was investigated by LC-MS/MS. Furthermore, elimination of dissolved organic carbon (DOC) as a measure for mineralization was monitored. LC-MS revealed that new PTPs were formed. CFZ underwent photolysis with both xenon and UV lamp. CFZ was completely transformed after 4 min of UV photolysis. However, mineralization was 7% only after 128 min. Under treatment by the xenon light source 56% CFZ only was transformed after 128 min without any mineralization. CFZ was not readily biodegradable in CBT and MRT. No biodegradation was observed for CFZ samples after 1, 2, and 4 min of UV photolysis in CBT and CFZ sample after 64 min of UV photolysis had partial biodegradation in CBT about 12%. The results demonstrate that CFZ and its PTPs were not biodegradable at low bacterial density and not fully mineralized by phototreatment and may pose a risk to the environment. Further assessment of the PTPs is recommended. References: 1- World Health Organization. WHO Model List of Essential Medicines ADULTS -- 18th edition (April 2013) -- Rev. Oct.2013. http://apps.who.int/iris/bitstream/10665/93142/1/EML_18_eng.pdf?ua=1 (accessed May 02, 2014). 2- Wang X, Lin AY. Environ. Sci. Technol. 46(22):12417–26 (2012).

 

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PREPARATION AND EVALUATION OF NEW URANYL SELECTIVE ELECTRODES

FOR URANYL ION DETERMINATION IN ENVIRONMENTAL SAMPLES

M. Abu-Dalo1, N. Nassory1, I. Al-mheidat1 1Jordan University of Science and Technology, Faculty of Science and Arts, Department of

Chemistry, P.O. Box 3030, Irbid 22110, Jordan Presenting author: maabudalo@just.edu.jo

Uranium contamination can be introduced to the environment naturally form certain types of soils and rocks. It also results from mining, manufacturing activities, coal and other fuel combustion and nuclear power production. The presence of uranium in both water and soil environment and the limitations associated with measuring uranium by available techniques create a need to develop a fast, sensitive and reliable method for uranium determination in various environmental samples. In this study new liquid and graphite coated ion selective electrodes were prepared for uranyl ion determination in environmental samples based on a new complex of uranyl and carboxybenzotriazole (CBT) in PVC matrix and uranyl ion-imprinted polymer. The membranes were prepared under different conditions including different polymer concentrations, plasticzers, and conditioning solution and used in electodes fabrication. Electrode parameters including slopes, concentration range, detection limit, pH and selectivity coefficients were determined and evaluated. The study is also carried out for determination the best ratio of uranyl ion and CBT concentrations. The Nernstian slopes of around 28 mV/decade were obtained for all tested electrodes. Measured concentration range from 6.0x10-2 to 3.0x10-5 and detection limit of 4.0 x10-4 M were obtained with response time of less than 30 seconds. Interferences of Cr3+ , La3+ , Ba2+ , Ca2+ Cu2+ , Na+ and K+ on the electrode response were evaluated using separate solution method. Di- and tri-valent cations were found to interfere less than monovalent cations which was attributed to high diffusion and exchange rate between monovalent ions and internal UO2

2+

solution. The electrodes were used to determine the concentration of the uranyl ion concentration in synthetic sample and real environmental sample by standard addition method. The results obtained by electrodes were compared with spectrophotometric method using arsenazo (III). The results were satisfactory with errors less than 7%. FTIR and scanning electron microscope (SEM) were used to characterize the membranes. The developed electrode was found to be fast, sensitive and reliable indicated its potential use in measuring the instantaneous uranyl ion concentration in the field

 

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DEGRADATION OF SULFAMETHAZINE IN A NOVEL SONOPHOTOCHEMICAL

FE3O4/OXALATE FENTON-LIKE SYSTEM

T. Zhou1, X.H. Wu1, G.M. Wu2, Q.B. Wu2, J. Mao1, J.B. Sheng2, S.C. Chen 2 1School of Environmental Science and Engineering,

Huazhong University of Science and Technology, 430074, Wuhan, P.R. China 2 Wuhan Iron and Steel (Group) Corp., 430080, Wuhan, P.R. China

Presenting author: zhoutao@hust.edu.cn 1 2 A novel sonophotochemical Fenton-like system was investigated for degradation of antibiotic

sulfamethazine (SMZ). It was demonstrated that the heterogeneous Fe3O4-catalyzed system (US/UV/Fe3O4/Ox) could induce in-situ generation of H2O2 and also Fenton-like reaction. Significant synergistic SMZ degradation was achieved in the system as compared to its corresponding individual systems (Fig. 1). US could eliminate the initial SMZ degradation lag period appeared in UV/Fe3O4/Ox system without the pre-dissolution phase, evidenced by great enhancements in the initial dissolution rate of the iron oxides as well as the production rate of reactive oxygen species (ROS). The promotional role of US could be mostly ascribed to the sonochemcial cavitation effect in both heterogeneous solid-liquid interphase reactions and homogenous radical reactions (Fig. 2).

0 10 20 30 40 50 600.0

0.2

0.4

0.6

0.8

1.0

 

 

[SMZ]/[S

MZ] 0

T ime  (m in)

 US /UV/Ox  US /F e

3O

4

 UV/F e3O

4

 US /UV/F e3O

4

 US /F e3O

4/Ox

 UV/F e3O

4/Ox

 US /UV/F e3O

4/Ox

Fe3O4

H2O(g)O2(g)

OH

OHO2

cavitation interior Gas-­‐liquid

interface

H2O2

OH

HO2

bulk solution

attacking

SMZ

Volatile IntermediatesCO2,H2ONH4

+,NO3-

Collidial Fe(OH)2 & Fe(OH)3

* ))) ---- Ultrasound

)))

α−FeOOH

Caviation bubbles

H2O

Fe3O4

Collapse

Microjets

The Radical Reactions

hydrolysis

Liquid Phase

fracture

S-L interphase

imporve masstransfer

Fe(II)-Ox

Fe(III)-Ox

Iron cycle

Fe3O4

(Smaller particles)

O2

)))

+(nanoparticles)Solid-Liquid Phase

Figure 1 Degradation of SMZ in different systems Figure 2 Scheme of US promotional role Acknowledgement: The authors thank for the financial support by China Key Project in the National Science &  Technology Pillar Program during the Twelfth Five-year Plan Period (No. 2012BAC02B04),  RFDPHEC (No. 201201420087),  the FRF for the Central Universities (No. 2014QN144), and SRF for ROCS and SEM.

 

121

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PRODUCTION OF A CERTIFIED REFERENCE MATERIAL FOR MERCURY

DETERMINATION IN SEAWATER: PRELIMINARY RESULTS

R. Sánchez, H. Leys, A. Oostra, H. Emteborg and A. Held

European Commission – Joint Research Centre - Institute for Reference Materials and Measurements (IRMM), Retieseweg 111, B-2440 Geel, Belgium

Presenting author: raquel.sanchez-romero@ec.europa.eu The Water Framework Directive (WFD) 2000/60/EC [1] established a protection of the aquatic environment and constitutes a strategy against the chemical pollution of water bodies. The WFD provided a list of priority substances that present a risk for the good chemical status of the aquatic environment defined in terms of compliance with all the environmental quality standards (EQS) established in the daughter Directive 2013/39/EU [2]. According to both directives, the mercury concentration must be monitored to assess the chemical status of the aquatic environment. The EQS for mercury expressed as a maximum allowable concentration (MAC) is 0.07 µg/L. In response to the European directives, a certified reference material (CRM) for the determination of mercury in seawater is under development at the Institute for Reference Materials and Measurements (IRMM), with the aim of producing a suitable quality assurance standard for trace mercury analysis. Seawater was collected from the North Sea (NL), filtered, acidified, mixed and spiked and finally filled in borosilicate ampoules under very stringent conditions. Since the target concentration was substantially below the MAC of 0.07 µg/L any point-contamination from the ampoules at the time of filling must be avoided. Thus, the use of borosilicate ampoules and the efficiency of four cleaning protocols were evaluated. Moreover, more specific studies are being carried out to ensure the homogeneity and stability of the final certified reference material. The material will be released in the near future in the form of a kit containing 3 x 100 ml. References [1] Directive 2000/60/EC establishing a framework for Community action in the field of water policy Off. J. Eur. Union L 327 (2000) 1. [2] Directive 2013/39/EU on environmental quality standards in the field of water policy Off. J. Eur. Union L 226 (2013) 1.

 

 

122

0719  

ELECTRODEGRADATION OF OXYTETRACYCLINE ON BDD ANODE

A. Fernandes, M.J. Pacheco, L. Ciríaco, A. Lopes

UMTP and Dep. of Chemistry, University of Beira Interior, 6200-001, Covilhã, Portugal Presenting author: annabelf@ubi.pt

The increasing use of drugs has become a new environmental problem, which has aroused great concern in recent years. Among these drugs, tetracyclines are one of the widely used in the prophylaxis and therapy of human and animal infections and the evidence of their existence in environmental matrices has been reported [1,2]. Its potential biological activity can lead to adverse environmental effects, including the contamination of soil and water resources [3]. Biological or physical-chemical conventional treatments have shown to be inefficient in the treatment of this kind of wastewaters and thus, the application of advanced technologies is required. Due to their effectiveness and ease in operation, electrochemical methods have received significant attention for wastewater treatment and several studies have reported the application of these methods in the treatment of effluents containing refractory and toxic organic pollutants, namely tetracycline [4-6]. In this study, the electrochemical degradation of oxytetracycline, an antibiotic from the tetracycline family, widely used in intensive agriculture to treat enteric and respiratory diseases, was carried out using a BDD anode. Experiments were conducted in an up-flow reactor, operating in batch mode with recirculation at an imposed current density of 200 A m-2. A volume of 250 mL of oxytetracycline aqueous solution 100 mg L-1, using as electrolyte sodium sulfate 5 g L-1, was used in each experiment. The influence of the recirculation flow rate on the oxidation of oxyetracycline was investigated. Assays were followed by chemical oxygen demand (COD), total nitrogen (TN) and UV-Visible spectrophotometry. According to the obtained results, the removal of the organic load, measured as COD and TN increased with the recirculation flow rate. At the highest recirculation flow rate tested, complete absorbance (measured at 275 and 354 nm) removal was attained. Acknowledgements The financial support of Fundação para a Ciência e a Tecnologia, FCT, for the project PEst-OE/CTM/UI0195/2011 of the MTP Unit, and the grant awarded to A. Fernandes SFRH/BD/81368/2011, are gratefully acknowledged.

References 1. I. Chopra and M. Roberts, Microbiol. Mol. Biol. R. 65, 232-260 (2001). 2. H. Kim, Y. Hong, J. Park, V. K. Sharma, and S. Cho, Chemosphere 91, 888-894 (2013). 3. L. Migliore, F. Godeas, S. P. De Filippis, P. Mantovi, D. Barchi, C. Testa, N. Rubattu, and G.

Brambilla, Environ. Pollut. 158, 129-134 (2010). 4. M. Panizza and G. Cerisola, Chem. Rev. 109, 6541-6569 (2009). 5. C. I. Brinzila, M. J. Pacheco, L. Ciríaco, R. C. Ciobanu, and A. Lopes, Chem. Eng. J. 209, 54-

61 (2012). 6. C. I. Brinzila, N. Monteiro, M. J. Pacheco, L. Ciríaco, I. Siminiceanu, and A. Lopes, Environ.

Sci. Pollut. Res. in press, DOI 10.1007/s11356-014-2778-y.

 

123

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INFLUENCE OF THE ATMOSPHERIC ORGANIC AEROSOLS ON THE SURFACES

IN THE ENVIRONMENT

K. Vidović1, S. Frka2, P. Orlović-Leko1

1Mining, Geology and Petrology Engineering Department, University of Zagreb, Croatia

2Division for marine and environmental research, Ruđer Bošković Institute, Zagreb, Croatia Preseting author: vidovic.kristijan88@gmail.com

Organic particles are either emitted directly into the atmosphere by fossil fuel or biomass combustion thus forming primary organic aerosols or are formed by gas-to-particle conversion from gaseous precursors leading to secondary organic aerosols. Surface active substances (SAS) as atmospheric organic compounds contribute significantly their water soluble organic carbon (WSOC) pool [1,2]. Atmospheric composition is of unquestionable importance in the study of the damage produced on building materials of artistic interest [3]. Thus, atmospheric aerosols are known to accumulate on the stone surfaces of the historical buildings forming black crusts. Newly formed layers tend to have higher concentrations of organic carbon (OC) than elemental carbon (EC) as a result of recent atmospheric increase in organics [4].This work is focused on investigation of organic carbon (OC) present in the black crust of historic buildings from two urban sites: Zagreb (Croatia) and Jajce (Bosnia and Herzegovina). The black crusts were analyzed for total organic carbon (TOC), and the sub–fractions: WSOC and SAS. Characterization of water soluble organic surfactants was carried out by adsorption study at the mercury electrode/solution interface using electrochemical methods (phase sensitive alternating current voltammetry). For quantification of the SAS content a calibration plot of the non-ionic surfactant Triton-X-100 was used. The results will be supported by data showing the temporal distributions of organic aerosols (PM10) over the urban site of Zagreb, Croatia during one year (2011-2012) were estimated. We found that the mean organic carbon (OC) concentrations in autumn, winter, spring and summer, were 11.29 ± 8.2, 9.10±.4.40, 4.03 ±1.58, and 3.41±1.42 µg C m−3, respectively. The average OC/EC ratio was 6.6. Results show that humic-like matter (HULIS) may be an important surface active matter in atmospheric aerosols during warm seasons. Moreover, the presence of HULIS was also detected in the investigated samples of the black crust. References 1. S. Frka, J. Dautović, Z. Kozarac, B. Ćosović, A. Hoffer, and G. Kiss, Chemical and physical

meteorology 64, 18490-1-18490-12 (2012). 2. P. Orlović-Leko, Z. Kozarac, B.Ćosović, S. Strmečki, and M. Plavšić, J. Atmos. Chem. 66,

11-26 (2011). 3. N. Ghedini, G. Gobbi, C. Sabbioni, and G. Zappia, Atmos. Environ. 34, 4383–4391 (2000). 4. A. Bonazza, P. Brimblecombe, C.M . Gross, and C. Sabbioni, Environ. Sci. Technol. 41 (12),

4199-4204 (2007).

 

124

0749  

CAN A LARGE SUITE OF TARGET MICROPOLLUTANTS EXPLAIN THE

BIOLOGICAL EFFECTS OBSERVED

IN WASTEWATER AND IN RECYCLED WATER?

F. Busetti1, J.Y.M. Tang2, J.W.A. Charrois1, B.I. Escher2,3 1Curtin University, Curtin Water Quality Research Centre,

GPO Box U1987, 6845, Perth, Australia 2The University of Queensland, National Research Centre for Environmental Toxicology,

39 Kessels Rd, 4108, Brisbane, Australia 3Helmholtz Centre for Environmental Research GmbH – UFZ,

Permoserstraße 15, 04318 Leipzig, Germany Presenting author: f.busetti@curtin.edu.au Removal of 299 organic micropollutants from a Western Australia advanced water recycling plant (AWRP) treating secondary wastewater (WW) through ultrafiltration (UF), reverse osmosis (RO) and UV disinfection was investigated by complementary chemical analysis and in-vitro cell-based bioassays. Chemical analyses were accomplished through gas chromatography-mass spectrometry (GC-MS) and liquid chromatography-mass spectrometryLC-MS based analytical methods and targeted a wide range of micropollutants including pesticides, pharmaceuticals and personal care products, hormones, industrial chemicals, household chemicals. Four in-vitro cell-based bioassays were used targeting non-specific toxicity (i.e., Microtox assay for cytotoxicity), specific toxicity (i.e., IPAM assay for photosynthesis inhibition) and reactive toxicity (umuC assay for genotoxicity; AREc32 assay for oxidative stress response). Although low levels of the anticorrosive compound tolutriazole, the plasticizer bisphenol A, the pharmaceutical triclosan and the pesticides 2-methyl-4-chlorophenoxyacetic acid (MCPA) and 3,4-dichloraniline were detected in the water samples post RO treatment, concentrations of detected micropollutants were well below the Australian Guidelines for Water Recycling implying that detected chemicals were considered to pose negligible health risk. No micropollutants were detected post UV treatment, demonstrating a high degree of safety for the re-use of RO/UV-treated WW for groundwater replenishment. In order to quantitatively link the results from chemical analysis and bioassays, the detected chemicals were mixed in the concentration ratios detected and their effects assessed. The effects caused by these designed mixtures were compared to the effects of the corresponding water samples along the treatment train of the AWRP to assess, which of the detected chemicals drive the biological effect and which fraction of effect remains unexplained by detected chemicals. The pesticides detected in secondary treated WW explained all observed effects on photosynthesis inhibition. In contrast, mixture toxicity experiments with designed mixtures containing all detected chemicals at their detected concentrations demonstrated that the known chemicals explained less than 3% of the cytotoxicity and less than 1% of the oxidative stress response. Pesticides followed by pharmaceuticals and personal care products were found to dominate the observed mixture effects. The detected chemicals could not be related to the observed genotoxicity. In conclusion, given the large proportion of unknown toxicity observed in the water samples (i.e., non-specific toxicity and oxidative stress), routine effect monitoring through in-vitro cell-based bioassays should be used in conjunction to chemical monitoring to ensure the safety of recycled water.

 

125

0769  

PHOTODEGRADATION OF CHLORPROTHIXENE IN AQUEOUS MEDIUM:

IDENTIFICATION, BIODEGRADATION, AND TOXICITY ASSESSMENT OF THE

FORMED TRANSFORMATION PRODUCTS

N. D. H. Khaleel1,2, W. M. M. Mahmoud1,2, C. Leder1, O. Olsson1, K. Kümmerer1 1Sustainable Chemistry and Material Resources, Institute of Sustainable and Environmental Chemistry, Leuphana University Lüneburg, Scharnhorststr. 1, 21335 Lüneburg, Germany

2Pharmaceutical Analytical Chemistry Department, Faculty of Pharmacy, Suez Canal University, Ismailia 41522, Egypt

Presenting author: Nareman.khaleel@uni.leuphana.de

RATIONALE: The environmental fate of the organic pollutants such as drugs and their transformation products has received an increasing interest as a new research area over the last years. Psychiatric drugs are among the most important prescription drugs worldwide, therefore environmental fate and persistence of these pharmaceuticals and their degradation products is of high relevance and it is, yet, scarcely elucidated. Chlorprothixene (CPTX) is an antipsychotic drug of the thioxanthene class. METHODS: The photodegradation of CPTX was conducted using 150 W medium-pressures Hg-lamp and Xenon lamp in Ultra-pure water. The elimination process was continuously monitored to follow the transformation and mineralization rate of the parent compound using Liquid Chromatography combined with UV-Vis detection (LC–UV-Vis) and total organic carbon (TOC), respectively. Liquid chromatography coupled to ion-trap mass spectrometry (ESI–LC–MS/MS (ion-trap)) was employed to monitor and identify the newly formed photo-transformation products (PTPs). Biodegradation testing of CPTX itself and samples from photolysis was assessed employing standardized OECD tests: Closed Bottle test (CBT; OECD 301 D) and Manometric Respirometry test (MRT; OECD 301 F). Environmentally relevant properties and selected toxicity endpoints of CPTX and its PTPs were predicted using different QSAR software: Oasis Catalogic software V.5.11.6 TB, Case Ultra V 1.4.5.1, OECD QSAR toolbox V 3.2 and Leadscope software V.3.0.11-1. RESULTS: It was found that CPTX underwent complete transformation after 64 min with 13% mineralization under UV irradiation. The mineralization reached 33% after 128 min irradiation time. In case of xenon lamp, CPTX was partially transformed to its geometric isomer without any mineralization. Moreover, according to mass data, the putative molecular formulae for twenty different PTPs for CPTX could be established, most of them unprecedented. Thus, a pathway for the photo-transformation of CPTX in aqueous medium could be proposed. Neither the CPTX nor its PTPs were biodegradable in the OECD tests. There was a good correlation between the experimental findings for the PTPs and the modelled environmental relevant properties from the QSAR applications. Finally, in silico toxicity analysis of CPTX and its PTPs provided evidence for carcinogenicity, ecotoxicity and mutagenicity. CONCLUSIONS: These results indicate the importance of identification of the PTPs arising from photolysis treatment as these PTPs can be more hazardous to the environment than their parent compounds. ACKNOWLEDGEMENTS: The authors wish to thank MultiCASE Inc. and Leadscope Inc. for providing CASE Ultra software and Leadscope software. This work was supported by the German Federal Ministry of Education and Research (Project SAUBER+ [02WRS1280A-J]).

 

126

0789  

APPLICATION OF HOLLOW FIBRE MEMBRANE MBR SEPARATION PROCESSES

INSTEAD OF GAC FILTRATION IN THE PHYSICAL-CHEMICAL INDUSTRIAL

WASTEWATER TREATMENT

M. Ghimpusan1, G.D. Nechifor1, A. C. Nechifor1, P. Passeri2 1Politehnica University of Bucharest, Faculty of Applied Chemistry and Material Science,

Analytical Chemistry and Environmental Engineering Department, str. Gheorghe POLIZU, no. 1-7, District 1, ZIP 011061, Bucharest, Romania

2G.O.S.T. Srl, Via Romana, 31, 06081 Assisi (PG), Italy Presenting author: maghimpusan@gmail.com

Nowadays, membrane technologies are becoming more frequently used for separation of wide varying mixtures result from a lot of industries and can compete successfully with traditional schemes. The aim of this paper was to analyse the use of ultra filtration with polypropylene hollow fibre membrane in the chemical physical systems instead of GAC filtration. A process data collection was performed and integrated with a characterization of the process effluents in terms of treatability and reusability. In order to evaluate properly the wastewater loading, an analysis course was set. The samples have been gathered for two years; instantaneous samples were drawn from the influent and treated wastewater. Based on daily average values, a general average has obtained. The experimental data were statistically analysed and the average values of the investigated parameters. It was found that ultrafiltration is a good process solution before discharge of the effluent. Keywords: hollow fibre, membrane MBR, GAC filtration, wastewater treatment References 1. APAT, IRSA – CNR, Metodi analitici per le acque, ISBN 88-448-0083-7, (2004). 2. J. Lee, W.Y. Ahn, Comparison of the filtration characteristics between attached and suspended growth microorganisms in submerged membrane bioreactor, Water Res. 35, 2435–2445, (2001). 3. American Water Works Association, and American Society of Civil Engineers. Water Treatment Plant Design. Ed. Edward E. Baruth. Fourth ed. New York: McGraw-Hill Handbooks, (2005). 4. Corbitt, Robert A. Standard Handbook of Environmental Engineering. Second ed. New York: McGraw-Hill Handbooks, (1999). 5. Perry, Robert H., Don W. Green, and James O. Maloney. Perry's Chemical Engineers Handbook. Seventh ed. New York: McGraw-Hill, (1997). 6. Soo-Jin Park, and Ki-Dong Kim. Influence of activation temperature on adsorption characteristics of activated carbon fiber composites. 7. H. Stefan, T. Walter, Treatment of urban wastewater in a membrane bioreactor at high organic loading rates, J. Biotechnol. 9295–101, (2001). 8. Y. Lee, J. Cho, Y. Sea, J.W. Lee, K.H. Ahn, Modeling of submerged membrane bioreactor process for wastewater treatment, Desalination 146, 451–457, (2002).

 

127

0820  

STUDY OF HEAVY METALS ACCUMULATION IN SEVERAL MEDICINAL PLANTS

USED IN DISEASE THERAPY

C. Radulescu1, C. Stihi1, I. V. Popescu1, I.D. Dulama2, A. Pohoata1 1 Valahia University of Targoviste, Faculty of Sciences and Arts, Department of Sciences and

Advanced Technologies, 130082, Targoviste, Romania 2 Valahia University of Targoviste, Multidisciplinary Science and Technology Research Institute,

130082, Targoviste, Romania Presenting author: radulescucristiana@yahoo.com

Products based on natural medicinal plants enjoy an increasing economic importance in different domains, such as food, pharmaceutical and cosmetic industry. Herbal medicines have been used for treatment of diseases for many thousands of years and are recognized as valuable, readily available resources for health care. Therefore it should be stressed that the use of medicinal plants has to respect the potential hazard connected with environmental contamination, mainly with toxic metals. Thanks its geographical position, a varied landscape and favorable climate for development of rich vegetation, in Romania grow over 3000 species of superior plants, from which over 200 have become medicinal plants. Most of these plants, even today, are collected and used by population from Romanian villages for treatment of different diseases. But it is true that the continued commercial exploitation and particular anthropogenic pollution led to the disappearance of many species from their natural habitat. Sometimes in polluted sites the plants, with well therapeutically properties mostly used by peoples but are often ruderal plants, accumulate heavy metals from the soil as well as intercept the pollutants from atmospheric deposition. This study assessed the level of heavy metal accumulation by several medicinal plants (i.e. Taraxacum officinale, Matricaria recutita, Achillea millefolium, Hypericum perforatum and Carduus nutans L.) which are growing naturally, without specific requirements, alongside the roads, disturbed sites, on strongly polluted places such as smelters, railway tracks, coal mines, and other industrial plants from Romania. Seven heavy metals including Cd, Cr, Cu, Pb, Ni, and Zn in plant and soil samples were selected on the basis of their effects upon health. The amount of heavy metals in soil and plants can vary seasonally due to the environmental factors which play an important role to uptake the elements by these plants. Absorption of heavy metal in medicinal plant is governed by soil characteristics such as pH, salinity, conductivity and organic matter content as well. The possible chemical forms of heavy metals in a natural system are hydrated metal ions, metal precipitates, soluble metal complexes, metal ions adsorbed to organic matter and bacterial residues and metal ions adsorbed to the surface and interstices of minerals. In analytical procedures, the concentrations of trace metals in plants require processing a large numbers of samples, to accurately characterize their abundance and to reach reliable conclusions. Generally, in these types of studies, knowledge on the total trace element content is sufficient, without the necessity of speciation. In order to determinate the heavy metals amount from different plants, some widely analytical techniques such as GFAAS (Graphite Furnace Atomic Absorption Spectrometry) and FAAS (Flame Atomic Absorption Spectrometry) were used. The bioaccumulation factors have been calculated as well. This investigation has shown that some medicinal plants (i.e. Taraxacum Officinale L. and Cardus Nutans L.) accumulate high levels of Pb (BF > 1 depending the sampling period) as well as Cu, from soil to leaves, and from this reason it is expected that these plants could be potentially dangerous for humans who used the plants. Finally, a mathematic modeling was performed using the obtained experimental data.

 

128

0823  

OPTIMIZATION AND VALIDATION OF A METHOD FOR SCREENING AND

CONFIRMATORY ANALYSIS OF PDE-5 INHIBITOR ANALOGUES IN

COUNTERFEIT HERBAL DIETARY SUPPLEMENTS

C. Bortolini, S. Bogialli, P. Pastore

Department of Chemical Science, University of Padua, 35131, Padova, Italy Presenting author: claudio.bortolini@studenti.unipd.it

Food supplements and Herbal products for treating erectile dysfunction and increasing sexual performance are getting more and more widespread [1]. Notwithstanding these products are perceived as “natural”, the main health-related concern is the frequent counterfeit with synthetic Phosphodiesterase type 5 (PDE-5) inhibitors not permitted and not declared on the label. For this purpose, the use of not registered PDE-5 pharmacological analogues is well established. In order to control their illegal marketing, a reliable analytical method for identification and quantification of PDE-5 inhibitor analogues is required. A high sensitive and selective method for simultaneous screening and confirming the presence of PDE-5 inhibitor analogues in counterfeit herbal products, based on one-shot solvent extraction and high-resolution tandem mass spectrometry (MSMS) has been developed. The detection with Auto MSMS mode allows to record both molecular and product ions, able to structurally characterize about 75 compounds included in a fit-for-purpose library. The optimization of the instrumental parameters was carried out on seven selected compounds (Vardenafil, Pseudovardenafil, Sildenafil, Homosildenafil, Tadalafil, Hydroxyhomosildenafil, Yohimbine). A relevant carry-over of Vardenafil experimented with traditional C-18 columns and leading to possible false positive has been overcome with a polymeric stationary phase. The extraction procedure was tested and validated in terms of specificity, linearity, accuracy and reproducibility, using different commercial formulations of the three registered PDE-5 inhibitors (Vardenafil, Sildenafil, Tadalafil). Different herbal dietary supplements bulk (gel, herbal dry power, pills, capsules and tablets) were employed for evaluating matrix effects and recoveries. Estimated LODs for the target compounds ranged between 1.75 and 7.75pg injected, so that this method is suitable to detect even trace residues that could be an evidence of illegal production processes. In collaboration with the Italian National Institute of Health, Italian Medicines Agency, police forces, an interlab surveillance campaign was accomplished with the aim of proposing a validated analytical protocol, thus having a snapshot of the market scenario of counterfeit herbal dietary supplements. References 1. B.J. Venhuis  and  D. de Kaste, J. Pharm. Biomed. Anal. 69, 196 (2012).

 

129

0845  

DEGRADATION AND BY-PRODUCTS IDENTIFICATION OF BENZOTHIAZOLES

AND BENZOTRIAZOLES DURING CHLORINATION BY LC-HR-MS/MS

M.-C. Nika1, A. A. Bletsou1, E. Gikas2, N. S. Thomaidis1

1Laboratory of Analytical Chemistry, Department of Chemistry, University of Athens, Panepistimiopolis Zographou, 15771, Athens, Greece

2Division of Pharmaceutical Chemistry, Department of Pharmacy, University of Athens, Panepistimiopolis Zographou, 15771, Athens, Greece

Presenting author: maristinanika@hotmail.com Nowadays, chlorination is the most prevalent disinfection method applied for water treatment in Europe. Chlorine can be supplied as sodium hypochlorite (NaOCl) which reacts in water to produce the disinfectants hypochlorous acid (HOCl) and hypochlorite ion (OCl-), otherwise known as free chlorine [1]. Although the primary purpose of chlorination is the elimination of micropollutants via oxidation, several investigations have shown that chlorine reacts with micropollutants leading in the production of undesired by-products. 1,3-benzothiazoles (BTHs) and 1,2,3-benzotriazoles (BTRs) are classified as high production volume emerging environmental pollutants due to their broad industrial and domestic application [2], and even though recently several analytical methods have been applied for their determination [2,3], there is still a lack of research for their by-products’ identification. 3 Initially, the degradation of three BTHs (BTH, 2-OH-BTH and 2-amino-BTH) and four BTRs (1-H-BTRi, TTRi, XTRi and 1-OH-BTRi) during chlorination was investigated by UHPLC-MS/MS (QqQ). Although chlorination appeared to be an insufficient degradation process for BTH and 1-H-BTRi, all their examined substituted derivatives seem to be significantly degraded when the molar ratio of sodium hypochlorite and the target analytes was between 5000:1 – 1000:1. Then, LC high resolution MS/MS (q-TOFMS) was used to investigate the formation of by-products in the chlorinated samples. Two suspect by-products of 2-amino-BTH and one of XTRi were tentatively identified based on their probable structure, mass accuracy, retention time and fragmentation and isotopic pattern. An interesting observation was the formation of 1-H-BTRi as a degradation product of 1-OH-BTRi during chlorination. Moreover, post-acquisition non-target treatment of the MS data revealed several unknown by-products of the tested analytes and their structure elucidation is still in progress. Acknowledgments This research has been co-financed by the European Union and Greek national funds through the Operational Program "Education and Lifelong Learning" of the National Strategic Reference Framework (NSRF) – ARISTEIA 624 (TREMEPOL project). References 1. U.S. Environmental Protection Agency. Office of Water. Washington. DC, EPA 832-F-99-062

(1999). 2. J. A. van Leerdam, A. C. Hogenboom, M. M. E. van der Kooi and P. de Voogt, Int. J. Mass

Spectrom., 282 (2009), p. 99-107. 3. A. G. Asimakopoulos, A. Ajibola, K. Kannan and N. S. Thomaidis, Sci. Total Environ., 452–

453 (2013), p. 163-171 .

 

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WORKFLOW FOR THE IDENTIFICATION OF BIOTRANSFORMATION

PRODUCTS OF AMINE-CONTAINING PSYCHOTROPIC DRUGS IN THE

AQUATIC ENVIRONMENT

A. K. Psoma, A. A. Bletsou, N. S. Thomaidis

National and Kapodistrian University of Athens, Department of Chemistry, Laboratory of Analytical Chemistry, Panepistimiopolis Zografou, 15771 Athens, Greece

Presenting author: katpsoma@chem.uoa.gr

Pharmaceuticals are continuously discarded into the aquatic system through wastewater treatment plants (WWTPs). The microbial degradation of these organic micropollutants and formation of transformation products (TPs) under aerobic conditions is the fundamental process for their elimination. It is of paramount importance to understand the microbial metabolic pathways so as to obtain knowledge of how fast micropollutants degraded and to assess the exposure to their potential TPs as they can be more polar and consequently environmentally persistent [1]. In this study, batch reactors seeded with activated sludge from the WWTP of Athens were set up to assess biotic, abiotic and sorption losses of selective psychotropic drugs, containing amine moieties. Biodegradation and transformation products were identified using liquid chromatography quadrupole-time-of-flight mass spectrometry (LC-QToF-MS). Data were acquired through broad-band collision induced dissociation (bbCID) mode, providing MS and MS/MS spectra simultaneously under positive and negative electrospray ionization (two separate runs). A workflow for target, suspect and non-target screening was developed. Data treatment was performed by using metabolite tools accompanying Bruker’s maxis impact ESI-QToF-MS and the structure elucidation of the candidate transformation products was based on accurate mass and isotopic pattern measurements by HRMS and tentative interpretation of MS/MS spectra. Finally a biodegradation pathway was proposed based on the TP structures identified. Despite the structure similarities, different degradation constants were calculated for each compound. Demethylation was noticed as common reaction among the compounds which led further to the formation of more polar TPs. Acknowledgments This research has been co-financed by the European Union and Greek national funds through the Operational Program "Education and Lifelong Learning" of the National Strategic Reference Framework (NSRF) – ARISTEIA 624 (TREMEPOL project). References 1. B. O. Clarke and S.R. Smith, Environ. Int. 37, (2011) p. 226-247.

 

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MONITORING OF PERSISTENT ORGANIC POLLUTANTS IN THE AEGEAN

– A SNAPSHOT IN JULY 2012

G. Lammel1,2, A. Besis3, C. Efstathiou1, K. Eleftheriadis4, J. Klánová1, J. Kohoutek1, P.

Kukučka1, P. Přibylová1, R. Prokeš1, C. Samara3, A. Sofuoglu5, S. C. Sofuoglu5,

Y. Tasdemir6, V. Vassilatou4, D. Voutsa3 1Masaryk University, Research Centre for Toxic Compounds in the Environment,

62500 Brno, Czech Republic 2 Max Planck Institute for Chemistry, 55128 Mainz, Germany

3Aristoteles University, Dept. of Chemistry, 54124 Thessaloniki, Greece 4NCSR Demokritos Institute, Institute of Nuclear Technology and Radiation Protection, 15310

Athens, Greece 5Izmir Institute of Technology, Chemical Engineering Dept., 35430 Urla, Turkey

6Uludağ University, Environmental Engineering Dept., 16059 Görükle, Turkey Presenting author: lammel@recetox.muni.cz

Persistent organic pollutants (POPs) are often found elevated in urban air, but are ubiquitous in the atmospheric environment including remote areas. Passive air sampling (PAS) is a suitable tool for monitoring and, hence, assessment of POPs in air [1]. A snapshot of the spatial (or geographical) distribution of a wide range of POPs across the Aegean was performed in July 2012. Organic trace substances in air were collected by passive (PAS, polyurethane foam disk deployed in protective chambers [2]) at 5 sites around the Aegean, i.e. in the urban areas of Thessaloniki and Athens, semi-rural, rural and remote areas near Thessaloniki, Bursa and Urla (western Turkey) and the islands Euboea and Crete. The effective sampling volume of PAS was ‘calibrated’ based on side-by-side PAS and active (high volume) sampling (AAS). This way 5 3-4-ring PAHs, 9 OCPs, 7 indicator PCBs and 5 PBDEs could be included. Chemical analysis was done in one laboratory using GC-MS following DCM extraction and fractionation. All results were corrected for field blanks. The results are discussed in the context of possible sources including long-range transport within and towards the Aegean. References 1. United Nations Environment Programme, Guidance on the Global Monitoring Plan for Persistent Organic Pollutants, Preliminary version (UNEP, Geneva, 2007). 2. J. Klánová, P. Cupr, J. Kohoutek and T. Harner, Environ. Sci. Technol. 42, 550-555 (2008).

 

132

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AIR-TO-SOIL-TO-PLANT TRANSFER OF HEAVY METALS FROM ATMOSPHERE

TO VEGETABLES OF LISBON’S URBAN GARDENS –

RISK ASSESSMENT

M.J. Matos1, Hugo F. Silva1, N.A. Silva1, S. Oliveira1, D. Freitas1,

P. Cantinho1, C. M. Oliveira2 1 ISEL-DEQ,CIEQB, 1959-007 Lisboa, Portugal

2 CCMM, Faculdade de Ciências, Universidade de Lisboa, Campo Grande, 1749-016 Lisboa, Lisboa, Portugal

Presenting author: mmatos@deq.isel.ipl.pt More than half of the world's population lives in cities and this number is expected to increase, at least, to 60% in 2030 and to 70% in 2050 [1]. With high population density in cities there are a lot of pollution sources resulting from human activities, like vehicle traffic. The urban soils are often polluted by heavy metals and other pollutants. Nowadays urban agriculture is part of a strategy of urban development and urban sustainability in many cities, such as Lisbon, in Portugal. Two types of vegetable gardens co-exist in Lisbon: official and non-official. The first type consisting of organized urban gardens is developed by the city authority. The non-official plots spread in the free lands of the town are mostly cultivated by old or retired people as well as persons with low income, such as emigrants and unemployed. For these people the relationship with the land and economic survival prevails over other factors like urban pollution and food safety considerations. The development of urban gardens presents several challenges in terms of the farmers’ and consumers’ health due the pollution of soil and air by heavy metals such as cadmium, copper, lead and chromium. The absorption, by vegetables, of these heavy metals from soil and polluted air leads to a cultivation of contaminated species. In fact, the transfer of metals from vegetables to population by means of the food chain is a major concern in the practice of urban gardening. This ingestion route of metals trough eating vegetables is, in case of Cd, approximately 70% of the total daily intake [2]. In the urban plots of Lisbon the cultivation of cabbage (brassica oleracea, acephala group) and lettuce (lactuca sativa) is in significant quantities. The first is eaten after washing and cooking and the lettuce is eaten after washing, generally in salads. These two species were chosen for this study as representatives of the major practices of vegetal consumption, to evaluate risk analysis and air-to-soil-to-plants transfer system. Lisbon, the biggest city of Portugal, and where the pollutions problems are more acute, is the obvious choice for the development of this study. In this communication we present the data analysis of metals in eight urban plots, in the vegetables produced in these plots (cabbage and lettuce) and in the content of metals in the aerosol particles in the atmosphere. The risk analysis, based on the pollution data of air, soils and vegetables, will allow the definition of the best local for urban gardening in the city with the minor risk for health. A survey on soil and air pollutants can act as a basis for the planning of control strategies in order to achieve an effective management of soil usage, namely in the practice of urban gardening. Consequently, the results of this study will be a valuable tool to safely plan and develop urban agriculture in Lisbon and in other cities. References 1. WHO, Situation and trends in key indicators, Annual report 2013. 2. G. Nabulo, S.D. Young, C.R. Black, Sci. Tot. Environ. 408 (2010) 5338–5351.

 

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APPLICATION OF TWO-DIMENSIONAL NMR SPECTROSCOPY TO

COMPOSITIONAL STUDIES OF HUMIC ACIDS FROM A MEDITERRANEAN

FOREST SOIL

R.M.B.O. Duarte1, A.P. Fernández-Getino2, A.M.S. Silva3, A.C. Duarte1 1Department of Chemistry & CESAM, University of Aveiro, 3810-193 Aveiro, Portugal 2Instituto Nacional de Investigación y Tecnología Agraria y Alimentaria (INIA). Dpto. Medio Ambiente.

Ctra de la Coruña, Km 7.5 - 28040 – Madrid, Spain 3Department of Chemistry & QOPNA, University of Aveiro, 3810-193 Aveiro, Portugal

Presenting author: regina.duarte@ua.pt In the study of complex organic mixtures from different environmental matrices (e.g., soil, water, atmospheric particles, and bulk precipitation), NMR spectroscopy has been crucial for extracting information on the structures present, and to develop an understanding of their origins and fate in the environment. This study presents the application of two-dimensional (2D) NMR spectroscopy to structural studies of humic acids from a forest soil under pine vegetation at Central Spain. The increased spectral dispersion provided by the additional dimension is proven to be highly advantageous for partially resolving the spectral information that is superimposed in one-dimensional spectra of such complex organic mixtures. Assignments of the major aliphatic, heteroatom, and aromatic structures likely present in the forest soil humic acids are provided. The 2D-NMR spectra suggest that the aliphatic moieties are highly functionalized with carboxylic functional groups, while lignin signatures are likely to be identified among the aromatic species.

Acknowledgments Centre for Environmental and Marine Studies (PEsT-c/MAR/LA0017/2013) and the Portuguese Science and Technology Foundation, through the European Social Fund (ESF) and “Programa Operacional Potencial Humano – POPH”, are acknowledged for financial support.

 

134

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ACID-BASE CHEMISTRY OF NATURAL ORGANIC MATTER, HUMIC ACIDS, AND FULVIC ACIDS

Shamus J. Driver, E. Michael Perdue

Ball State University, Department of Chemistry, Muncie, Indiana,

USA Presenting author: sjdriver@bsu.edu

Samples of natural organic matter, humic acids, and fulvic acids from the Suwannee River in southeastern Georgia and Pony Lake, Antarctica were titrated with NaOH on a Mettler-Toledo autotitrator to characterize the samples in terms of carboxylic acid and phenolic functional groups. Ascertaining the composition of acidic functional groups would provide valuable information about how dissolved organics would be affected by water purification products. An average of 1500 data points were collected for each titration. Charge densities were corrected for the concentrations of inorganic anions and cations in the original samples. The pH 8 and 10 method, the modified Henderson-Hasselbalch model, and the Gaussian distribution model were fit to the titration data, and fitting parameters were compared with fitting parameters from earlier manual titrations of the same samples. A timeline of acid-base chemistry analytical techniques used on dissolved organic matter will be discussed along with future research goals dealing with problems associated with direct titrations of complex aqueous organic mixtures.

   

 

135

1022  

KINETICS OF THE REACTION BETWEEN 2,5-DICHLORO-1,4-BENZOQUINONE

AND SULFITE ION

V. Kiss, É. Józsa, K. Ősz

University of Debrecen, Department of Physical Chemistry, Egyetem tér 1.,H-4032, Debrecen, Hungary

Presenting author: osz.katalin@science.unideb.hu Benzoquinones are known to be photosensitive substances in aqueous solutions forming hydroxyl-quinones, hydroquinones and dioxygen in their photoreaction. The photo-disproportion can even be induced by the light of a diode array spectrophotometer [1,2].

Halobenzoquinones are also known as a group of emerging disinfection byproducts in drinking water and swimming pool waters [3]. Displacement of halides in some substituted quinones can be performed by using sulfite [4]. However, sodium sulfite plays several different roles in these systems:

• it is a reducing agent, • a buffer or weak base depending on the active form we use, • and/or a reactant of the ketone-bisulfite addition reaction [5].

Moreover, photosubstitution of the sulfo group for hydrogen (or chlorine) is also observed under irradiation of sulfonated derivatives of hydroquinone formed upon dissolving p-benzoquinones in aqueous solutions of sodium sulfite. The first step of the reaction, i.e. the formation of an orange intermediate is so fast that it cannot be followed even on a stopped-flow time scale. The decomposition of this intermediate shows a complex kinetic pattern.

Figure 1: Kinetic traces in the 2,5-dichloro-1,4-benzoquinone sulfite system at 25 °C; c(sodium sulfite) = 0,15 mol dm–3. c(2,5-dichloro-1,4-benzoquinone, mmol dm–3) values are in in the legend.

The research was supported by the EU and co-financed by the European Social Fund under the project ENVIKUT (TÁMOP-4.2.2.A-11/1/KONV-2012-0043).

References 1. I. Fábián and G. Lente, Pure Appl. Chem. 82, 1957 (2010). 2. G. Lente and J.H. Espenson, J. Photochem. Photobiol. A, Chem. 163, 249 (2004). 3. Y. Qian, W. Wang, J.M. Boyd, M. Wu, S.E. Hrudey and X.-F. Li, Environ. Sci. Technol. 47,

4426 (2013); W. Wang, Y. Qian, J.M. Boyd, M. Wu, S.E. Hrudey and X.- F. Li, Environ. Sci. Technol. 47, 3275 (2013).

4. C.A. Bishop, R.F. Porter and L.K.J. Tong, J. Am. Chem. Soc. 85, 3991 (1963). 5. T.S. Rao and S.B. Salunke, React. Kinet. Catal. Lett. 26, 273 (1984).

 

136

1025  

SCHIFF BASE METALLOPOLYMERS FOR GREEN CO2 REDUCTION

S. Realista, P. N. Martinho, A. I. Melato, M. José Calhorda

Centro de Química e Bioquímica, Faculdade de Ciências, Universidade de Lisboa, Campo Grande, 1749-016 Lisboa, Portugal

Presenting author: smrealista@fc.ul.pt Hydrocarbon fuels are currently the most important source of energy because of their ready availability, stability, and high energy density. Unfortunately, combustion of this source of energy carries a significant issue to the environment and environmental pollution, for which carbon dioxide emissions are responsible [1]. Recent reports of reaction of pressurised CO2 with epoxides to form polycarbonates [2] or cyclic carbonates [3] have attracted both academic and industrial interest, but the recycling of CO2 to produce high value products via low-cost catalysts has not been much exploited. Among others, transition metal complexes with salen derived ligands have shown to have good catalytic activity for CO2 conversion to either cyclic or acyclic carbonates [4]. In addition, the development of modified electrodes with conducting polymers containing metal centres along the polymer backbone has been a very active area of research [5]. Salphen-type metallopolymers are attractive, because extra synthetic steps to attach electropolymerisable groups can be avoided as Schiff base complexes can be directly electropolymerised. Here we present the synthesis of both mononuclear and binuclear Schiff base complexes with first row transition metal ions, such as Cu(II) or Zn(II) (figure 1), which can be electropolymerised on an inert substrate by potentiostatic and/or potentiodynamic modes. The so-formed films are characterized by cyclic voltammetry, atomic force microscopy and spectroscopic techniques. The electrocatalytic potential of these modified electrodes for CO2 recycling is investigated using different experimental conditions and the products formed determined by standard analytical techniques.

Figure 1: Salphen-type mononuclear complexes (left) and topographic AFM image of a polymer film grown from a complex solution. References 1. D.T. Whipple, P.J.A. Kenis, J. Phys. Chem. Lett., 1, 3451-3458, (2010). 2. G.W. Coates, D.R. Moore, Angew. Chem. Int. Ed., 43, 6618-6639, (2004). 3. J. Meléndez, M. North, R. Pasquale, Eur. J. Inor. Chem., 21, 3323-3326, (2007). 4. Y. Shen, W. Duan, M. Shi, J. Org. Chem., 68, 1559–1562, (2003). 5. P.H. Aubert, P. Aubert, M. Roche, P. Capedevielle, M. Maumy, G. Ricart, Chem. Mater., 13,

2223-2230, (2001).

 

137

1047  

EUROPIUM – SENSITISED LUMINISCENCE DETERMINATION OF

OXYTETRACYCLINE IN SURFACE WATER

E. Becic1, S. Omerovic2, B. Imamovic1, L. Alagic-Dzambic3, M. Dedic1, M. Šober1 1Department of Pharmaceutical Analysis, Faculty of Pharmacy,

Zmaja od Bosne 8, 71000 Sarajevo, Bosnia and Herzegovina 2  Quality Control Department, Bosnalijek d.d. Sarajevo, Jukićeva 53, 71000 Sarajevo, Bosnia and Herzegovina

3Development Department, Bosnalijek d.d. Sarajevo, Jukićeva 53, 71000 Sarajevo, Bosnia and Herzegovina

Presenting author: ervina.becic@ffsa.unsa.ba Because of its wide antibacterial spectrum and high potency, oxytetracycline is routinely used in veterinary medicine for prevention and control of desease[1]. Their residues can be founded in wastewater, soils and surfacewater [2]. For the determination of oxytetracycline are mainly used UV/VIS spectrophotometry [3], spectrofluorimetry [4], thin layer chromatography [5], liquid chromatography [6, 7] and microbiological techniques [8]. A new analytical method for oxytetracycline in surface water was developed using HPLC post –column europium sensitised fluorescence. The mobile phase was composed of 10mM oxalic acid pH 2,50 and acetonitrile 95:5 (v/v). Europium post-column reagent was developed with EDTA and Tris buffer. This reagent provided optimized fluorescence detection and was found to be compatible with acidic mobile phases used in reversed phase chromatography of oxytetracycline. The procedure involves the extraction and preconcentration of the analytes by solid-phase extraction (SPE) and subsequent liquid chromatography separation with post column derivatisation and fluorescence detection. Post-column derivatization using europium sensitised fluorescence increased the fuorescence of chelates by a factor up to 3 compared uncomplexed tetracycline. Peak areas were linear with concentration from 50 – 1500 ng/ml with correlation coefficient 0.999. Subnanogram limit of detection and limit of quantification were obtained. The proposed method can be applied to the residue analysis for oxytetracycline in surface water. References [1]. El Korchi G.I., Prats C., Arboix M., Pérez B. J. Vet. Pharmacol. Therap. 24, (2000). [2]. O_Connor S., Aga D.S. Anal. Chim. Acta 562, (2006). [3]. Prasad, A. R. G, Rao, V. S. Science World Journal 5, (2010). [4]. Fernandez-Gonzalez, R., Garca-Falcon M.S., Simal-Gandara, J. Anal. Chim. Acta. 455 (2002) [5].Jankrzeka A., Magorzata S., Kiersznuewska A., Rzeszutko W. J. AOAC Int. 83, (2000). [6] Senyuva H., Ozden T., Sarica Yurtsever D. Turk. J. Chem. 24, (2000). [7]. Thiex NJ, Larson R. J AOAC Int. 92, (2009). [8]. Myllyniemi A.L., Rannikko R., Lindfors E., Niemi A., Bäckman C. Food Addit. Contam.,12, (2000).

 

138

1065  

 

INVESTIGATION OF SELENIUM ACCUMULATION IN SOME FISH TISSUES WITH

BY HYDRIDE GENERATION ATOMIC ABSORPTION SPECTROMETRY

G. Seren1, H. Kurnaz2, Y. Kalebaşı3

1Department of Analytical Chemistry, Faculty of Pharmacy, Trakya University, Turkey 2Department of Chemistry, Institute of Natural Sciences, Trakya University, Turkey

3Department of Chemistry, Trakya University, Edirne, Turkey Presenting author: gulayseren@trakya.edu.tr

In this study, selenium contents of in the fish tissues samples were determined by Hydride Generation Atomic Absorption Spectrometry (HGAAS) at Lake of Gala, Enez. Atomic absorption spectrometry (AAS) has been widely used for selenium determination at trace levels, including techniques such as electro thermal atomic absorption spectrometry (ETAAS) and hydride-generation atomic absorption spectrometry (HGAAS) [1]. Studies have been conducted on fish species, Carassius gibelio. This research has been aimed to determine the selenium contents in Carassius gibelio samples in the Lake of Gala. Fish samples were taken fresh from the Cooperative of Gala Lake. 1 gram samples of fishes various organs (intestine, gill, muscle, skin) were dissolved with 6 mL HNO3 and 2 mL H2O2. Preparation of samples for acid fragmentation analysis system was used to solve CEM microwave MARSXpress 5. The advantages of microwave digestion against the classical methods are shorter time, less consumption of acid and keeping volatile compounds in the solutions. Samples were filtration by filter paper. They were complete with distilled water to 20 mL and they were kept -85ºC until analysis in HDPE containers. Samples were analyzed by HGAAS. Measurements were performed with a Perkin Elmer AAnalyst 800 atomic absorption spectrometer equipped with an MHS-15 (mercury hydride system) hydride generator. All measurements were carried out using high-purity argon. An electrodeless discharge lamp for Se (EDL System, Perkin Elmer) was used as the radiation source. According to these results, the amount of selenium: 0.504 µg/g for intestinal samples, 0.489 µg/g for gill samples, 0.437 µg/g for muscle samples, 0.376 µg/g for skin samples. The precision of the technique, expressed as relative standard deviation, was less than 8% for HGAAS. In general, the selenium content in meat and seafood is range from 0.4 to 1.5 mg / g [2]. In our study, content of selenium in fish tissues is in this range. References 1. J.C. Ricardo, D.A. Otoniel, E.S. Ricardo, Spectrochimica Acta Part B 57, 1967–1978, (2002). 2. Trace elements in human nutrition and health, World Health Organization, Geneva, (1996).

 

139

1072  

INVESTIGATION OF ARSENIC ACCUMULATION IN SOME FISH SAMPLES OF

THE GULF OF SAROS WITH BY HYDRIDE GENERATION ATOMIC ABSORPTION

SPECTROMETRY

M.Şentürk1, G. Seren2 Y. Kalebaşı3

1Department of Chemistry, Institute of Natural Sciences, Trakya University,, Edirne, Turkey 2Department of Analytical Chemistry, Faculty of Pharmacy, Trakya University, Turkey

3Department of Chemistry, Faculty of Science, Trakya University, Edirne, Turkey Presenting author: gulayseren@trakya.edu.tr

Arsenic (As) is an environmental and food chain contaminant, and inorganic As is a class 1 carcinogen [1]; drinking water and foodstuffs are the two main common sources of inorganic As [2]. In this study, arsenic contents of in fish tissues samples were determined by HGAAS at Gulf of Saros, Enez. Studies have been conducted on fish species, Chelidonichthys lucerna. However, until now, in the Gulf of Saros, Chelidonichthys lucerna have not been investigated heavy metal content. To fill this gap in the literature, this research was planned in the Gulf of Saros to determine the arsenic content in Chelidonichthys lucerna. Enez samples to be analyzed at a predetermined fisherman fresh fish which was taken as. Then the samples were brought to the laboratory for the preparation of fish samples analyzed samples. Fishes various organs (intestine, kidney, lung, and muscle, skin) samples taken on 1 g of H2O2 and 6 mL of 2 mL of HNO3 was added. Then put in a microwave tube was subjected to various steps implemented solubilization. Preparation of samples for acid fragmentation analysis system was used to solve CEM microwave MARSXpress 5. Decomposed samples were completed to 20 mL with distilled water. Samples for analyses were taken up for storage and freezer storage containers HDPE at -25 °C. Samples were analyzed by Hydride Generation Atomic Absorption Spectrometry (HGAAS). According to these results, the amount of arsenic: for intestinal samples 0.058 µg/g; for kidney samples 0.104 µg/g; for gill samples 0.053 µg/g; for muscle samples 0.064 µg/g; for skin samples 0.048 µg/g. The precision of the technique, expressed as relative standard deviation, was less than 8% for HGAAS. The results were in agreement with literature values [3, 4]. References 1. F. Zhao, J. L. Stroud, T. Eagling, S. J. Dunham, S. P. Mcgrath and P. R. Shewry, Environmental Science & Technology 44,5464–5468, (2010). 2. J. S. Tsuji, L. J. Yost, L. M. Barraj, C. G. Scrafford, P. J. Mink, Regulatory Toxicology and Pharmacology 48, 59–68, (2007). 3. A. Q. Shah, T. G. Kazi, M. B. Arain, J. A. Baig, H. I. Afridi, G. A. Kandhro, S. Khan ve M. K. Jamalş, Journal of Hazardous Materials, 167, 511-515, (2009). 4. S. Rosemond, Q. Xie ve K. Liber, Environment Moniter Assess, 10, 1007, 10661-007-0112, 2008.

 

140

1079  

REMOVAL OF HIGH-CONCENTRATION AMMONIUM AND HYDROGEN

PEROXIDE WITH HYDROGEN REDUCTION FOLLOWED BY SUBCRITICAL

HYDROTHERMAL REACTION

H. Yamasaki1, M. Negoro1, A. Miyakoshi2, K. Fukunaga3 1Ube National College of Technology, 2-14-1 Tokiwadai, Ube 755-8555, Japan

2Asahikawa Nation. Col. of Tech., 2-1-6 2Jyo, Syunkodai, Asahikawa 071-8142, Japan 3Yamaguchi University, 2-16-1 Tokiwadai, Ube 755-8611, Japan

Presenting author: yamasaki@ube-k.ac.jp Prepared polymeric spherical hydrogels immobilized nitrite bacteria reacted to form NO2

- of ca. 3,000 NO2-N mg/L from the model wastewater containing NH4

+ of 5,300 NH4-N mg/L (eq. 1) [1]. The removal of decomposed NH4

+ and NO2- could be accomplished by subcritical

hydrothermal reaction without the use of a catalyst (eq. 2) [2]. In this work, wastewater containing high concentration of both NH4

+ and H2O2 by hydrogen reduction and subcritical hydrothermal reaction was carried out (eq. 3). NH4

+ + 1.5O2 → NO2- + 2H+ (eq. 1)

NH4+ + NO2

- → N2 + 2H2O (eq. 2) NH4

+ + NO2- + H2O2 + H2 → N2 + 4H2O (eq. 3)

The total extraction ratio was gradually decreased with the increase of H2O2 concentration without hydrogen reduction (Runs 1 to 4 in Table). These results suggested that the oxidized reaction obtained NO3

- from NO2- by H2O2 progressed preferentially in this system.

The hydrogen component for hydrogen reduction was safely provided as the hydrogen water obtained from electrolysis of H2O usage of platinum plating electrode (GINSUI, Shinwa Co. Ltd, Tokyo). Two kinds of process were performed to study for this reaction. When hydrogen reduction followed by subcritical hydrothermal reaction for model wastewater containing of NH4

+, NO2- and H2O2 was carried out, the result of the total extraction ratio was extremely low:

ca. 50% (Run 5). On the other hands, the results of total extraction ratio was high to over 93% (Runs 6 and 7), when the subcritical hydrothermal reaction carried out after addition of NO2

- wastewater to the pretreated water with hydrogen reduction.

References 1. H. Yamasaki, I. Yoshiya, M. Negoro, and K. Fukunaga, Journal of Environmental

Conservation Engineering (Japanese), 42(6), pp.362-369 (2013). 2. H. Yamasaki, I. Yoshiya, M. Negoro, and A. Miyakoshi, The 4th International IUPAC

Conference on Green Chemistry, p.370[P272], Foz do Iguaçu(Brazil), Aug.25-29 (2012).

 

141

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LICIT AND ILLICIT DRUG SUBSTANCES IN THE AIR OF AMSTERDAM (NL)

C. Balducci1, A. Cecinato1, P. Romagnoli1, M. Perilli1, P. Panteliadis2 1CNR, Institute of Atmospheric Pollution Research, I-00015 Monterotondo Stazione RM, Italy

2Municipal Health Service (GGD) Amsterdam, Department of Air Quality, 1018WT, Amsterdam, The Netherlands Presenting author: balducci@iia.cnr.it

Illicit drugs have been included in the list of the emerging contaminants, whose presence in the environment represents an ascertained or potential risk for population. Most concern is focused on water contamination, whilst scarce attention is paid to air, which is the principal pathway of diffusion of toxicants to the other environmental compartments. Extensive studies have been carried out in Italy with regard to cocaine and cannabinoid occurrence in urban, suburban and rural areas [1]; in addition, the presence of heroin and amphetamines in the air has been observed in Spanish cities [2]. Spotty monitoring campaigns were conducted in different regions of the world, nonetheless the lack of information remains important. In order to increase knowledge about the drug contamination of city atmosphere in Europe two monitoring campaigns were carried out in Amsterdam, NL, during March 2011 and 2013. According to data published by the European Monitoring Centre for Drugs and Drug Addition in 2013 [3], Netherland is the 4th country in Europe for the lifetime prevalence of cocaine abuse (5.2%, adult 15-64); on the other hand, Government Authorities designed a drug policy allowing cannabis consumption under strict terms and conditions. Our investigation was focused on cocaine and the three most important cannabinoids detectable in the air, namely cannabinol, cannabidiol and Δ9-tetrahydrocannabinol. Nicotine and caffeine were also monitored, to detect the impact of licit drug use. Finally, polycyclic aromatic hydrocarbons (PAHs) and PM were measured in parallel, to elucidate how much each of psychotropic substances modulated according to air pollution.  Three sites were investigated in Amsterdam, which belong to Air Quality Network of the city. Namely, an urban background station in the vicinity of Vondelpark, Einsteinweg, i.e. a highway station close to residencies, and Jan van Galenstraat, a roadside station next to a bus stop. Atmospheric particulate was collected daily onto quartz fiber filters (Pall Tissuquartz, 2500 QAT-UP), by using low volume samplers (2.3 m3/h) (Comde-Derenda GmbH, LVS 3.1). During the 2011 campaign the daily filters were gathered in weekly pools in order to securely reach the LOQ of the analytical procedure adopted. The results obtained allowed us to investigate the weekday/weekend modulation during 2013. Similarly to other important cities, the concentrations of cocaine showed noticeable differences, depending on the site; moreover, cannabinol was the predominant compound among cannabinoids. The concentration levels of the target compounds were comparable to those detected in the European Capitals of London and Rome in similar year periods. References 1. A. Cecinato, C. Balducci, V. Budetta, A. Pasini, Atmos. Environ. 44, 2358 (2010). 2. M. Viana, X. Querol, A. Alastuey, C. Postigo, M.J. López de Alda, D. Barceló, et al. Environ. Int. 36, 527 (2010). 3. EMCDDA. European Drug Report 2013. Trends and developments. (EMCDDA, Lisbon 2013)

 

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ESTIMATING ATMOSPHERIC DEPOSITION OF NITROGEN AND HEAVY METALS FROM CONCENTRATIONS IN MOSS: LONG-TERM MONITORING COVERING

THREE SPATIAL SCALES

W. Schröder1, M. Kluge1, S. Nickel1, E. Steinnes2, H. T. Uggerud.3 1Chair of Landscape Ecology, University of Vechta, POB 15 53, D-49364 Vechta, Germany

2Department of Chemistry, Norwegian University of Science and Technology, NO-7491 Trondheim, Norway

3Norwegian Institute for Air Research, PO Box 100, NO-2027 Kjeller, Norway Presenting author: winfried.schroeder@uni-vechta.de

Background. To map atmospheric deposition of nitrogen (N) and heavy metals (HM) and to validate measured and modelled deposition values and risk evaluations, the use of estimates from element concentrations in moss is well established [1-2]. Moss surveys provide complementary and time-integrated data at high spatial resolution. Since 1990, the moss technique was used for surveys encompassing up to 7000 sites across Europe every 5 years. Aim. The paper introduces into the moss technique and demonstrates by case studies trends of N and HM deposition across spatial scales. Starting with trends of HM and N deposition throughout Europe, the focus is then on correlations between HM concentrations in moss and soil specimen collected between 1990 and 2010 across Norway. Finally, complementing the investigations at the continental and national level, by example of northwestern Germany site-specific canopy drip effects are demonstrated for atmospheric N deposition loads as estimated from N concentrations in moss. Results. The decline in emission and subsequent atmospheric deposition of HM across Europe has resulted in decreasing HM concentrations in moss between 1990 and 2010 (Cd -51%, Pb -77%, Hg -23%). Contrary to that, hardly any changes were observed for N in moss between 2005, when N was included firstly into the survey, and 2010 [1]. On the national level, both, the moss and the soil survey data sets indicate a decrease of HM concentrations in moss and soil specimen collected across Norway. However, in case of moss samples the decrease is more pronounced and statistically significant. The spatial patterns of Cd and Pb concentrations in moss and soil specimens 1995 and 2005 are similar. Thereby, the spatial differentiation of concentrations in moss is higher than in soil, while the opposite holds true for Hg concentrations [3]. At the site level, compared to the average N deposition in open fields 2012 (7.4 kg N /ha*a as estimated from N concentrations in moss), the average N deposition within adjacent forests was almost four times higher (26.6 kg N / ha*a), and the maximum deposition within the stands accounted for approximately 56 kg N /ha*a. Compared to 2005, there was a decline of the average N deposition by 2.4 kg N /ha*a in open fields. However, the average N deposition within forests stands in 2012 remained nearly the same since 2004 (29 kg N /ha*a) [4]. References 1. Harmens, H. et al., Heavy metals and nitrogen in mosses: spatial patterns in 2010/2011 and long-term temporal trends in Europe (ICP Vegetation Programme Coordination Centre, Bangor, UK, 2013). 2. Steinnes E. et al., Sci. Total Environ. 412-413:351-358 (2011). 3. Kluge et al., submitted to Env. Sci Europe (2014). 4. Kluge et al., Env. Sci Europe 25(26):1-13 (2013).

 

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KINETIC STUDIES ON THE DECOMPOSITION OF GLYCINE CHLORAMINES

M. Szabó, I. Fábián

Department of Inorganic and Analytical Chemistry, University of Debrecen, H-4032 Debrecen, Egyetem tér 1, Hungary

Presenting author: szabo.maria@science.unideb.hu In recent years, physiological processes have generated immense interest in the redox reactions of chlorine and hypochlorous acid with amino acids, peptides and proteins. These reactions lead to the formation of various N-chlorinated chloramines under in vivo conditions and provide effective defensive mechanisms against foreign cells. The very same reactions also play important role in water treatment technologies, quite often leading to adverse environmental effects. Systematic studies are sporadic on such systems, literature data are reported mainly on the formation chloramines of amino acids and only limited information is available on the decomposition kinetics and mechanism of these species. Now we report a detailed study on the decomposition kinetics of glycine chloramines. It is shown that the stability of these species is highly pH dependent. Under basic conditions, the mono-chloramine is stable for an extended period of time its life-time goes through a maximum as a function of pH. At pH 9.68, the decomposition is less than 10 % over a period of 2 hours. Upon acidification, the decomposition of this species is accelerated and occurs on the stopped-flow time-scale. The results of the pH and concentration dependencies of the reaction rate will be reported and interpreted in terms of an appropriate kinetic model in this contribution. A comparison of the results with the decomposition of NH2Cl reveals similarities between the two systems. In both cases, the kinetic patterns show significant pH dependence and considerable complexities. Mono-chloramines prepared under alkaline conditions are converted into dichloramines upon acidification. When the corresponding amines are mixed with HOCl under acidic conditions, completely different kinetic features are observed. The formation of mono-chloramines are not observed, the spectral observations are consistent with direct formation of higher order chloramines. Eventually break-point chlorination occurs. Acknowledgement The authors thank the Hungarian Science Foundation for financial support under grant No. NK 105156. The research was supported by the EU and co-financed by the European Social Fund under the project ENVIKUT (TÁMOP-4.2.2.A-11/1/KONV-2012-0043).

 

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DISTRIBUTION AND TEMPORAL EVOLUTION OF CADMIUM COPPER AND

LEAD IN THE VENICE LAGOON. RELATION OF THE SPECIATION WITH THE

DISSOLVED/PARTICULATE PARTITION

E. Morabito1, M, Radaelli2, E. Scalabrin2, G. Toscano2, G. Capodaglio1,2 1CNR-IDPA, 30125, Venice, Italy

2DAIS, Ca’ Foscari University, 30125, Venice, Italy Presenting author: elisa.scalabrin@unive.it

The Lagoon of Venice has been subjected to substantial changes due to human needs, principally to maintain certain hydraulic characteristics and to stop the silting up. The industrial and agricultural activities together with the increasing of population in the last century are liable for serious problems of chemical pollution, that have considerably reduced the environmental quality [1]. Many processes such as changes of salinity, biological processes and physical phenomena, control the cycling, the mobility and the fate of metals in Venice Lagoon. Many of these processes involve, directly or indirectly, the organic matter in both dissolved and colloidal forms. It is well known that speciation of elements is an essential study to evaluate the mobility, the biogeochemical reactivity and in general the interaction of elements with other components in complex systems as well marine environments and transition systems [2] The speciation of trace metals (Cd, Cu and Pb) was measured in samples collected in the Venice lagoon during several campaigns, from 1992 to 2006 focusing on metal portion between dissolved and particulate phase. An increment of cadmium and lead concentration in dissolved phase results in the central and northern basin linked principally to some important alteration inside the Lagoon, as well as because of industrial and urban contributes. The salinity for all the lagoon samples ranged from 28.2 to 35.6 psu; hence, the effects of variations of ionic strength on the partition dissolved-particulate were quite limited. Experiments carried out in different areas showed that the metal complexation by organic ligands shifts the heterogeneous equilibrium dissolved/particulate metal toward the dissolved phase, then increasing the mobility of metals. Although that could seem correct in interface areas where there is a high salinity gradient, the results highlight that organic complexation may have an opposite effect: when the salinity variability is limited, the role of organic matter in the sedimentation process is much more complex than the simple desorption due to complexation. The metal trends concentration observed in this study can be related to the sediment resuspension, due to the calm fishing, but also to the simultaneous decrease of organic carbon concentration in sediments. The dissolved cadmium concentration was negatively correlated with the tide level and in the same measure with the salinity, furthermore the concentration in sediment is correlated with the organic matter. The lead behavior is different, the particulate concentration is related only to the dissolved concentration, while in the case of copper, the role of organic complexation do not seem totally clear. References 1. G.Capodaglio , A Gambaro, WRL Cairns, G Toscano, C Turetta.. In: Fletcher A, Spencer T, editors. Flooding and Environmental Challenges for Venice and its Lagoon: State of Knowledge. (University Press; 2005). 2. Zago C, Capodaglio G, Barbante C, Giani M, Moret I, Scarponi G, et al. Heavy metal distribution and speciation in the Northern Adriatic Sea. Chem Ecol 2002;18(1).

 

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QSPR MODELS FOR ENVIRONMENTAL FATE ASSESSMENT AND PRODUCT

DEVELOPMENT IN SMALL AND MEDIUM SIZED CHEMICAL COMPANIES

W. M. M. Mahmoud1,2, C. Leder1, C. Rücker1, K. Kümmerer1, D. Schwartz3 1Sustainable Chemistry and Material Resources, Institute of Sustainable and Environmental Chemistry, Leuphana University Lüneburg, Scharnhorststr. 1, 21335 Lüneburg, Germany.

2 Analytical Chemistry Department, Faculty of Pharmacy, Suez Canal University, Ismailia 41522, Egypt.

3Bruno Bock GmbH, 21436 Marschacht, Germany Presenting author: waleed.ahmed@inkubator.leuphana.de

REACH (Registration, Evaluation, Authorisation and Restriction of Chemicals) is a regulation of the European Union, adopted to improve the protection of human health and the environment from risks that can be posed by chemicals, while enhancing the competitiveness of the EU chemical industry [1]. Often information on compound properties available to small companies is insufficient for REACH registration. Experimental testing of compounds is expensive and time consuming. Alternative methods for hazard assessment such as QSPR/QSAR (Quantitative structure ̶ property/activity relationships) are expressly recommended by regulatory authorities. However, there are at least two problems with this approach: i) Available computer programs for compound property prediction may be not appropriate for the particular compounds of interest. ii) Small chemical companies may not have personal sufficiently familiar with such programs to realistically estimate their limitations. Our project "Use of Cheminformatics models for the development and optimization of chemical products" is intended to alleviate this situation by supporting small companies in using appropriate computer programs. For example, a compound property of fundamental importance is biodegradability or not so. If a compound is readily biodegraded in the environment, there will be no major concern on bioaccumulation or long-term toxicity. Biodegradability is often predicted using the Biowin models of the U. S. EPA. However, the Biowin models are primarily based on the presence of certain substructures in molecules that are recognized by the program, for each such substructure a certain numerical contribution is added to a predicting function. If a compound structure is devoid of these substructures, and perhaps contains other substructures important for biodegradation, the Biowin predictions are based on the molecular mass only. A user unfamiliar with the programs may take such predictions literally, not realizing that his compounds are outside the domain of applicability of the programs. The approach will be to use a variety of biodegradability prediction software on particular classes of compounds containing less familiar functional groups, and to generate experimental biodegradation data for certain compounds with the aim to use these in establishing “local” biodegradation models for these compound classes in contrast to existing models that claim “global” applicability but were trained on compound classes containing the most fundamental functional groups only. This is a joint research project of Leuphana University Innovation Incubator and Bruno Bock GmbH, a leading producer of organosulfur compounds. Biodegradation tests for selected compounds will be performed according to OECD guidelines such as the Closed Bottle test (CBT). Reference: (1) http://echa.europa.eu/web/guest/regulations/reach/ (accessed May 13, 2014).

 

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BIOLOGICAL AND OXIDATIVE TRANSFORMATION PRODUCTS OF ANTIVIRAL

DRUGS – SIMILARITIES AND DIFFERENCES

4 IN REACTIVITIES AND PATHWAYS

J. Funke, C. Prasse, T. A. Ternes

Federal Institute of Hydrology, Am Mainzer Tor 1, 56068, Koblenz, Germany Presenting author: funke@bafg.de

In the last decades several pharmaceutical classes, such as antibiotics, betablocker and analgesic drugs have been detected in the aquatic environment, due to their incomplete removal in wastewater treatment plants (WWTP).[1] For the antiviral drug acyclovir, used for treatment of herpes infections, it was shown that its elimination leads to the formation of the transformation product (TP) carboxy-acyclovir.[2] Due to its recalcitrance and polarity carboxy-acyclovir could be detected in surface waters and groundwater in concentrations up to 3.2 and 0.3 µg L-1, respectively. Even though ozonation is able to remove this TP, it leads to another TP, named COFA, which was even detected in ozonated drinking water after activated carbon filtration.[3] The aim of this study was to investigate the fate of the antiviral drugs abacavir, zidovudine, emtricitabine and lamivudine in biological and advanced treatment (ozonation). These nucleosidic reverse-transcriptase-inhibitors (NRTI) are administered to treat human immunodeficiency-, herpes simplex- or hepatitis-B-virus infections and have been found in raw and treated wastewater.[4] To this end, degradation experiments with activated sludge were conducted. Furthermore ozonation experiments were performed with the original antivirals as well as their biochemical TPs. Chemical structures of TPs were elucidated using high-resolution mass-spectrometry (LTQ Orbitrap Velos). In addition TPs were isolated using semi-preparative HPLC to generate reference standards for quantification and to confirm the proposed chemical structure using NMR. Lab-scale experiments with activated sludge revealed carboxylation, sulfur-oxidation and hydroxylation as main biotransformation reactions. Elucidation of ozonation products (OPs) and their pathways were elucidated using different ozone-analyte-ratios, by the addition of t-BuOH to differentiate between O3 and OH-radical reactions and by comparison of OPs being formed in purified water and treated wastewater. The formation of TPs and OPs was confirmed by analysis of samples from a conventional WWTP equipped with an ozonation pilot-plant. This three step degradation of the original compounds to biological TPs and further to oxidative TPs may allow for the evaluation of combining conventional WWTPs and advanced oxidative treatments. References 1. Y. Luo, W. Guo, H. H. Ngo, L. D. Nghiem, F. I. Hai, J. Zhang, S. Liang, X. C. Wang, Sci.

Total Environ. 473-474, 619-641 (2014). 2. C. Prasse, M. Wagner, R. Schulz, T. A. Ternes, Environ. Sci. Technol. 45, 2761 – 2769,

(2011). 3. C. Prasse, M. Wagner, R. Schulz, T. A. Ternes, Environ. Sci. Technol. 45, 2761 – 2769,

(2012). 4. C.Prasse, M. P. Schlüsener, R. Schulz, T. A. Ternes, Environ. Sci. Technol. 44, 1728 – 1735

(2010).

 

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KINETICS AND MECHANISM OF THE OXIDATION OF FE(II)-

BISTERPYRIDINE BY PEROXOMONOSULFATE ION

G. Bellér1, Z. Antal2, J. Kurucz2, G. Lente2, I. Fábián2 1MTA-DE Homogeneous Catalysis and Reaction Mechanisms Research Group,

University of Debrecen, H-4032 Debrecen, Egyetem tér 1, Hungary 2Department of Inorganic and Analytical Chemistry, University of Debrecen,

H-4032 Debrecen, Egyetem tér 1, Hungary Presenting author: beller.gabor@science.unideb.hu

Peroxomonosulfate (HSO5

–) is commercially available in the form of a triple salt, named Oxone (2 KHSO5 · KHSO4 · K2SO4). It is considered an inexpensive and environmentally friendly replacement of other peroxo compounds (such as H2O2 or S2O8

2–) in oxidation methods. It is a powerful non-chlorine oxidizer for a wide variety of industrial and consumer uses. Its applications include microetching in metallurgy, odor controlling in wastewater treatment, bleaching in dentistry, disinfection of swimming pools and spas etc. Experiments involving Oxone provide valuable information on the study of reactive intermediates and may explore important aspects of industrial applications. We report a kinetic study on the redox reactions of Oxone with the bis-2,2';6',2"-terpyridine complex of iron(II) (abbreviated by Fe(tpy)2

2+), which has been utilized considerably in analytical procedures and is enjoying popularity in supramolecular chemistry as a building block for multinuclear systems. The reaction was studied by UV-Vis spectrophotometric method. Similarly to the previously investigated oxidation of analogous iron(II) complexes (phenanthroline and bipyridine) [1] the reaction shows complex kinetic behavior: ion pair formation of the reactants and autocatalysis are also involved in the overall mechanism. The oxidation was studied in slightly and strongly acidic media. In both cases, detailed concentration dependence was measured, the autocatalytic behavior was proved and an attempt was made to identify the catalyst. Based on the kinetic observations, a three-term rate equation was proposed that involves the proton-assisted dissociation of the complex and the non-catalytic and catalytic pathways of the oxidation. The non-catalyzed reaction is likely to proceed via the formation of an adduct from the two reactants. The rate constants of the three paths and the association constant of the adduct were determined by non-linear least squares fittings. The oxidation of the ligand was also studied, since terpyridine-mono-N-oxide was identified among the oxidation products of the complex by ESI-MS method and it was shown earlier that phenanthroline-mono-N-oxide significantly influences unusual kinetic curves in the reactions of the phenanthroline complexes of Fe(II) and Fe(III) [2]. Acknowledgement The authors thank the Hungarian Science Foundation for financial support under grant No. NK 105156. The research was supported by the EU and co-financed by the European Social Fund under the project ENVIKUT (TÁMOP-4.2.2.A-11/1/KONV-2012-0043). References 1. G. Bellér, G. Bátki, G. Lente, I. Fábián, J. Coord. Chem. 63, 2586 (2010) 2. G. Bellér, G. Lente, I. Fábián, Inorg. Chem. 49, 3968 (2010)

 

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GREEN CHEMISTRY IN OXIDATION: CATALYTIC ACTIVATION OF HYDROGEN

PEROXIDE BY TRANSITION METALS FOR OXIDATION REACTIONS

A. M. Al-Ajlouni

Basic Sciences Department, College of Science and Health Professions, King Saud bin Abdulaziz University for Health Sciences, Riyadh 11481, Kingdom of Saudi Arabia

ajlounia@ksau-hs.edu.sa Catalytic activation of hydrogen peroxide in water is of greatest environmental importance. We have been working on the catalytic activation of peroxides by transition metal catalysts toward oxidation of organic and inorganic substrates. Different Mo(VI), W(VI) and Re(VII) complexes are under investigation in our laboratory. We have prepared and design series of Mo(VI) and W(VI) catalysts and studied their activity in oxidation of organic substrates by peroxides, such as epoxidation. Detail kinetic and mechanistic studies are all carried out in order to understand the role of the catalyst and the effect other variables, such as concentrations, solvent and temperature, on the reaction. We have found that the metal activates the peroxide by forming a metal-peroxo species, which is able to transfer an O atom to the organic substrate, as shown below. It has been demonstrated that the presence of electron-withdrawal group(s) on the metal catalyst enhances its activity. References 1. Al-Ajlouni, A. M.; Günyar, A.; Baxter, P. N. W.; Kühn, F. E. Euro. J. of Inorg. Chem., 2013, 1019-1026. 2. Al-Ajlouni, A. M.; Zhao, J.; Veljanovski, D.; Capape Miralles, A.; Herdtweck, E.; Kühn, F. E. Organometallics 2009, 28, 639-645. 3. Al-Ajlouni, A. M.; Saglam, O; Diafla, T.; Kuhn, F. E. J. Mol. Cat. A Chem. 2008, 287, 159. 4. Al-Ajlouni, A. M.; Daiafla, T. M.; M. El-khateeb, M. J. Mol. Cat. A Chem. 2007, 275, 139.

 

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NANOPOROUS CARBON XEROGELS

FOR CAPACITIVE WATER DESALINATION

G. Hristea, Paraschiv, A. Cucos

National Institute for R&D in Electrical Engineering ICPE-CA, INCDIE ICPE CA, 5 0303138, Bucharest, Romania

Nanoporous carbon aerogels/xerogels are promising materials as electrodes for capacitive deionization (CDI) units and electrical double layer capacitors (EDLCs) [1-3]. An optimum process is presented for synthesis of nanoporous carbon xerogels via pyrolyzing resorcinol-formaldehyde (RF) organic aerogels, which could be cost-effectively manufactured from wet RF gels by a modified drying method technique using acetone exchange/controlled evaporation instead of conventional supercritical drying. The effects of the initial pH of the RF solutions on the physical/electrochemical properties of the synthesized carbon electrodes based RF xerogels designed for mentioned application have been experimentally tested. Surface area measurements by BET method and capacitance evaluation of the obtained carbon xerogels by cyclic voltammetry and impedance spectroscopy have been performed. Chronoamperometry was used also to characterize the carbon xerogels as electrodes designed for water desalination based on capacitive principles. Obtained carbon xerogels are mainly microporous (average main pore diameter: 1.73-2 nm) Preliminary tests in regard of sorption capacity have been based on carbon xerogels electrochemical behaviour in the presence of nitrates, nitrites, sodium chloride and sulphates. References 1. T. J. Welgemoeda, C. F. Schutteb, Desalination 183, 327–340 (2005) 2. Hae-Hyun Junga, Sung-Woo Hwanga, Sang-Hoon Hyuna, Kang-Ho Leeb, Gye-Tai Kim, Desalination, 216, 377–385 (2007) 3. M. Inagaki, H. Konno, O. Tanaike, J Power Sources, 195(24):7880(2010)

 

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INFLUENCE OF CHLORIDE CONCENTRATION ON THE ANODIC OXIDATION OF

TETRACYCLINE

C. I. Brinzila1,2, A. Fernandes1, M.J. Pacheco1, L. Ciríaco1, R. Ciobanu2, A. Lopes1

1UMTP, Dep. of Chemistry, University of Beira Interior, 6201-001 Covilhã, Portugal 2The “Gheorghe Asachi” Technical University of Iasi, RO-700050, Iasi, Romania

Presenting author: carmenbrinzila@gmail.com The intensive use in the past decades of antibiotics in concentrates of animal feed, to prevent disease and promote growth of livestock, has led to serious environmental problems. In fact, part of the ingested antibiotics may go directly to the environment, promoting the growth of multi-resistant bacteria in the animals themselves, in humans and in wildlife. Tetracycline family is among the most used veterinary antibiotics and residues of tetracycline have already been detected in surface waters that received discharges from municipal wastewater treatment plants and agricultural drained [1,2,3]. In this study, the influence of chloride ion on the electrochemical degradation of tetracycline was evaluated. Tetracycline degradation experiments were conducted in batch mode, with different anode materials, using as electrolyte NaCl or Na2SO4. Different compositions of the electrolyte solution, using simultaneously both electrolytes and keeping constant the ionic strength, were also used. The samples collected during the electrochemical assays were analyzed for the following parameters: Chemical oxygen demand (COD), total organic carbon (TOC), nitrogen (total Kjeldhal, organic and inorganic), and UV-Visible absorption spectrophotometry. It was observed that the increase in the NaCl content in the electrolyte mixture leads to higher COD removals with lower TOC removals, thus decreasing the degree of mineralization. Acknowledgments Project "Development and support of multidisciplinary postdoctoral programs in major technical areas of national strategy of Research - Development - Innovation" 4D-POSTDOC, contract no. POSDRU/89/1.5/S/52603, project co-funded by the European Social Fund through Sectorial Operational Program Human Resources Development 2007-2013. The authors also want to thank Fundação para a Ciência e a Tecnologia for the project PEst-OE/CTM/UI0195/2011 of the MTP Unit and for the grant awarded to A. Fernandes SFRH/BD/81368/2011. References 1. R. Hirsch, T. Ternes, K. Haberer, K.L. Kratz, Sci. Total Environ. 225, 109 (1999). 2. R. Hirsch, E.T. Furlong, M.T. Meyer, E.M. Thurman, S.D. Zaugg, L.B. Barber, H.T. Buxton,

Environm. Sci. & Technol., 36, 1202 (2002). 3. A. Pena, M. Paulo, L.J.G. Silva, M. Seifrtová, C.M. Lino, P. Solich, Anal. Bioanal. Chem.

396, 2929 (2010).      

 

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DEEP EUTECTIC SOLVENTS AS REACTION MEDIA IN ORGANIC SYNTHESIS

A. Kolb, B. Koenig

University of Regensburg, 93053, Regensburg, Germany Presenting author: anika.kolb@ur.de

There is a pressing need to replace hazardous and harmful solvents with “green” or “sustainable” media. Natural compounds have recently been used to produce deep eutectic solvents, sugar melts, or ionic liquids.1,2,3 We are developing biodegradable deep eutectic solvents based on inexpensive sugars and organic acids made from renewable resources. The melts provide reaction media for organic synthesis and biotransformations. The research group of Prof. B. Koenig already portrayed several examples for organic C-C-coupling reactions, e.g. Diels-Alder reaction and metal-catalyzed Suzuki, Heck and Sonogashira reactions.4 Also the physicochemical properties like polarity, viscosity, density, molar heat capacity and conductivity of these solvents are well studied.5 Further, we are investigating the solubility power of deep eutectic solvents for organic and even inorganic compounds. Nockemann et al. and Abbot et al. already used ionic liquids for solubilizing metal salts, including metal oxides.6,7 This solubilizing power is of high interest especially for electrochemical applications and for applications in solvent extraction technology.

Figure 1: Metal salt solutions with different deep eutectic solvents.

References 1. A. P. Abbott, G. Capper, D. L. Davies, R. K. Rasheed, V. Tambyrajah, Chem. Commun., 70 (2003). 2. F. Ilgen, B. Konig, Green Chem. 11, 848 (2009). 3. P. Nockemann, B. Thijs, K. Driesen, C. R. Janssen, K. Van Hecke, L. Van Meervelt, S. Kossmann, B. Kirchner, K. Binnemans, J. Phys. Chem. B 111, 5254 (2007). 4. C. Russ, B. Konig, Green Chem. 14, 2969 (2012). 5. G. Imperato, S. Hoger, D. Lenoir, B. Konig, Green Chem. 8, 1051 (2006). 6. P. Nockemann, B. Thijs, S. Pittois, J. Thoen, C. Glorieux, K. Van Hecke, L. Van Meervelt, B. Kirchner, K. Binnemans, The Journal of Physical Chemistry B 110, 20978 (2006). 7. A. P. Abbott, G. Capper, D. L. Davies, R. K. Rasheed, P. Shikotra, Inorg. Chem. 44, 6497 (2005).

 

 

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ELECTROOXIDATION OF EMERGING POLLUTANTS USING MODIFIED CARBON

NANOTUBE ELECTRODES IN AQUEOUS SOLUTION

I. Kuźniarska-Biernacka1, M. Fereira1, O.S.G.P. Soares2, J.J.M. Órfão2, M.F.R. Pereira2, J.L

Figueiredo2, I.C. Neves1, A.M. Fonseca1, P. Parpot1 1 Departamento de Química, Centro de Química, Universidade do Minho, Campus Gualtar,

4710-057, Braga Portugal 2Laboratório de Catálise e Materiais (LCM), Laboratório Associado LSRE/LCM, Departamento

de Engenharia Química, Faculdade de Engenharia, Universidade do Porto, Rua Dr. Roberto Frias, 4200-465 Porto, Portugal

Presenting author: iwona@quimica.uminho.pt Groundwater pollution by harmful organic compounds is a growing concern everywhere in the world. Emerging pollutants, as pharmaceutical compounds and pesticides are the most problematic and widespread among the vast number of potential groundwater contaminants. Their improper discharge leads to contamination of the environment and must be prevented. In this context, monitoring and removal of the organic pollutants is of the highest importance. Electrochemical oxidation of these compounds has attracted growing interest in the last years [1]. The importance of electrochemical technologies in wastewater treatment, due to their versatility, high efficiency, easy control, environment compatibility and cost effectiveness, became more relevant in the last decades considering the increasing concern related to the drinking water supply and the rigorous environmental guidelines related to wastewater discharge [2,3]. There has been increasing interest in multiwalled carbon nanotubes (CNTs) as heterogeneous catalyst supports [3,4] owing to their high surface area and high electrical conductivity. In this context, the electrochemical oxidation of organic pollutants was investigated using bimetallic catalysts supported on multiwalled carbon nanotubes (CNTs). Modified electrodes were prepared and dispersed onto Toray carbon (CT) using a Nafion/water solution, aiming at the transformation of pollutants to less hazardous compounds. Long-term electrolyses were carried out in a membrane separated electrochemical cell in order to determine the conditions that allow efficient electrooxidation. The reaction products were identified and quantified using chromatographic methods.

Acknowledgements: The authors thank the FCT and the European Fund for Regional Development (FEDER)-COMPETE-QREN-EU for financial support to the Research Centres, (CQ/UM, PEst-C/QUI/UI0686/2011, FCOMP-01-0124-FEDER-022716) and the project “n-STeP - Nanostructured systems for Tail”, a NORTE-07-0124-FEDER-000039 supported by Programa Operacional Regional do Norte (ON.2) and IKB thanks for the contract under the project NORTE-07-0124-FEDER-000039.

References [1] S. Garcia-Segura, E. Brillas, Water Research 45, 2975 (2011). [2] M. Panizza, A. Kapalka, Ch. Comninellis, Electrochim. Acta 53, 2289 (2008); M. Ferreira, M.F. Pinto, O.S.G.P. Soares, M.F.R. Pereira, J.J.M. Órfão, J.L. Figueiredo, I.C. Neves, A.M. Fonseca, P. Parpot, Chem. Eng. J. 228, 374 (2013). [3] M. Ferreira, M.F. Pinto, O.S.G.P. Soares, M.F.R. Pereira, J.J.M. Órfão, J.L. Figueiredo, I.C. Neves, A.M. Fonseca, P. Parpot, Electrochim. Acta 60, 278 (2012). [4] M.F.R. Pereira, J.L. Figueiredo, J.J.M. Orfão, P. Serp, P. Kalck, Y. Kihn, Carbon 42, 2807 (2004).

 

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ENVIRONMENTAL APPLICATIONS OF Ti/Pt/SnO2-Sb ELECTRODES:

DICLOFENAC ANODIC OXIDATION

D. Santos1, A.D. Barbosa1,2, M.J. Pacheco1, L. Ciríaco1, A. Lopes1 1UMTP, Dep. of Chemistry, University of Beira Interior, 6201-001 Covilhã, Portugal

2Dep. Química, Campus Catalão, Univ. Federal de Goiás, GO - Brasil, 75.704-020 Presenting author: analopes@ubi.pt

Effluents from hospitals and pharmaceutical industry may be contaminated with several types of drugs or macropollutants, such as analgesics, antibiotics, antidepressants, etc., or micropollutants, as well as their degradation metabolites resulting from its metabolization by the human body [1,2]. Aware of this reality, the European Union has included, for the first time, three drugs in the "watch list" (diclofenac, 17-beta-estradiol and 17-alpha-ethinylestradiol), with the possibility of being also included in the "priority list". Thus, end-of-pipe effective treatments are necessary in order to avoid contamination of water resources. Advanced oxidation processes (AOPs), based on the indirect oxidation of pollutants by hydroxyl radicals, like anodic oxidation, have been shown to be efficient in the mineralization of organic pollutants, including pharmaceuticals [3,4]. The objective of this work was to perform the anodic oxidation of diclofenac, using as anode material a Sn/Sb composite, with Sn and Sb simultaneously electrodeposited over a platinized titanium substrate - Ti/Pt/SnO2-Sb. Diclofenac degradation experiments were conducted in batch mode, using as electrolyte Na2SO4 solutions. The geometric area of the anode was 10 cm2 and the applied current density was 30 mA cm-2. The samples collected during the electrochemical assays were analysed for the following parameters: Chemical oxygen demand (COD), total organic carbon (TOC) and UV-Visible absorption spectrophotometry. COD and TOC removals higher than 50 % were obtained after 4 h assay. The similarity between COD and TOC removal rates points to a high degree of mineralization of the diclofenac molecule that is corroborated by the gradual decay of the UV-Visible spectra along the wavelength scale. Acknowledgments Fundação para a Ciência e a Tecnologia, for the project PEst-OE/CTM/UI0195/2011 of the MTP Unit, and FCUBI/ICI/Santander Totta, for the grant awarded to D. Santos. References 1. K. Kümmerer, J. Environm. Manag. 90, 2354 (2009). 2. P. Verlicchi, A. Galletti, M. Petrovic, D. Barceló, J. Hydrology 389, 416 (2010). 3. I. Sirés, E. Brillas, Environ. International 40, 212 (2012). 4. D. Santos, M.J. Pacheco, A. Gomes, A. Lopes, L. Ciríaco, J. Appl. Electrochem. 43, 407

(2013).

 

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MAGNETIC REMOVAL OF LANTHANIDE IONS USING SURFACE MODIFIED

MAGNETITE NANOPARTICLES

R. S. Carvalho1, D. Tavares2, A. L. Daniel-da-Silva1, T. Trindade1 1 CICECO-Chemistry Department, Aveiro Institute of Nanotechnology, University of Aveiro,

3800-193 Aveiro, Portugal 2 CESAM-Chemistry Department, University of Aveiro,

3800-193 Aveiro, Portugal Presenting author: ruisilvacarvalho@ua.pt

In the last years, nanoengineered materials have been investigated as efficient sorbents for the uptake of metal ions, with important consequences for future technologies of water decontamination and metal extraction.[1] Our interest in this research topic led us to develop magnetic sorbents composed by colloidal magnetite (Fe3O4) cores coated with silica shells enriched in dithiocarbamate (DTC) groups at the surfaces.[2] Noteworthy, these materials have shown a remarkable efficiency for the magnetic capture of aqueous Hg(II) from waters with vestigial but realistic concentrations in this metal ion.

Lanthanides and their compounds are of great relevance in current technologies but the increasing demand for these metals also poses new economical and environmental challenges. The present communication describes preliminary research on the use of the sorbents mentioned above for the capture of aqueous lanthanide ions. Thus ferrimagnetic Fe3O4 nanoparticles were first modified using a one-step procedure that produces core/shell particles enriched in dithiocarbamate groups at the surfaces. These particles were then evaluated as sorbents for the magnetically assisted removal of Eu(III) and Tb(III) ions from aqueous solutions. The lanthanide concentration in function of the contact time was monitored by fluorescence

emission measurements and ICP analysis. [3] Under the experimental conditions used (CLn,t=0 =1x10-4 M, pH=10), about 90 % of the lanthanide was removed from water in less

than 30 minutes (Figure 1). The observed performance of these materials will be interpreted by taking in consideration the chemical functionalization of the particles’ surfaces. Additionally, several operational parameters were varied in a series of experiments and their effect on the lanthanide removal efficiency will be analyzed. Acknowledgments: This work was financed by national funding from FCT (Fundação para a Ciência e a Tecnologia) through the project PTDC/CTM-NAN/120668/2010, by FEDER fundings through program COMPETE and by national fundings through FCT in the frame of project CICECO - FCOMP-01-0124-FEDER-037271 (Ref. FCT Pest-C/CTM/LA0011/2013) 1. T. A. Kurniawan, M. E.T. Sillanpää, M. Sillanpää, Crit. Rev. Environ. Sci. Tech. 42, 1233–

1295, (2012). 2. D. S. Tavares, A. L. Daniel-da-Silva, C. B. Lopes, N. J. O. Silva, V. S. Amaral, J. Rocha, E.

Pereira and T. Trindade, J. Mater. Chem. A 1, 8134–8143 (2013). 3. A. L. Jenkins, G. M. Murray, Anal. Chem. 68, 2974-2980 (1996).

Figure 1 – Removal percentage of Eu(III) and Tb(III) from aqueous solutions in function of the contact time with the sorbents.

 

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PHENOL ANODIC OXIDATION ON Ti/SnO2-Sb AND Ti/Pt/SnO2-Sb ELECTRODES

D. Santos1, L.Q. Tavares1,2, M.J. Pacheco1, L. Ciríaco1, A. Lopes1 1UMTP, Dep. of Chemistry, University of Beira Interior, 6201-001 Covilhã, Portugal

2Dep. Química, Campus Catalão, Univ. Federal de Goiás, GO - Brasil, 75.704-020 Presenting author: dalia@ubi.pt

Phenol is a well-known pollutant, toxic even at low concentrations that during oxidation or disinfection processes can react to form substituted compounds [1]. Because the metabolites formed during its oxidation are well studied, phenol is frequently used as model compound in environmental research, namely in advanced oxidation processes (AOPs) studies where hydroxyl radicals are the main responsible for the indirect oxidation of the pollutants. Among the AOPs, the anodic oxidation with different electrode materials has been shown to be very efficient in the phenol mineralization [2,3]. The objective of this work was to perform the anodic oxidation of phenol, using as anode material a Sn/Sb composite, with Sn and Sb simultaneously electrodeposited over a titanium substrate, Ti/SnO2-Sb, or a platinized titanium substrate, Ti/Pt/SnO2-Sb, being the oxides formed after a thermic treatment. The Sn/Sb electrodes (with 10 cm2) were used as anode and stainless steel plates (with similar geometric area) were used as cathodes in the degradation assays of phenol. The model solutions used in the degradation assays contained 100 ppm of phenol, in the presence of 0,035 M Na2SO4, and the assays were run at different current densities. The degradation tests were followed by chemical oxygen demand (COD), total organic carbon (TOC) determinations and UV-Vis spectrophotometry analysis. The best results were obtained with Ti/SnO2-Sb electrodes, although its lifetime is much lower than that of Ti/Pt/SnO2-Sb. At a current density of 30 mA cm-2, after 8 h assay, COD removals were 94% and 23% and TOC removals were 85% and 23%, respectively, for Ti/SnO2-Sb and Ti/Pt/SnO2-Sb. Acknowledgments Fundação para a Ciência e a Tecnologia, for the project PEst-OE/CTM/UI0195/2011 of the MTP Unit, and FCUBI/ICI/Santander Totta, for the grant awarded to D. Santos. References 5. G. Busca, S. Berardinelli, C. Resini, L. Arrighi, J. Hazard.Mater. 160, 265 (2008). 6. A. Morão, A. Lopes, M.T. Pessoa de Amorim, I.C. Gonçalves, Electrochimica Acta 49, 1587

(2004). 7. D. Santos, M.J. Pacheco, A. Lopes, L. Ciríaco, J. Appl. Electrochem. 41, 577 (2011).

 

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PRESENCE OF BACTERIA Legionella spp. IN WARM TAP WATER IN RELATION TO

HEAVY METALS

A. Rakić1, L. Foglar2 1Public Health Institute of Split, Vukovarska 46, Split, Croatia

2Division of Industrial Ecology, Faculty of Chemical Engineering and Technology, University of Zagreb, Marulićev trg 20, Zagreb, Croatia

Presenting author: anita.rakic@st.t-com.hr The aim of this paper is to assess whether heavy metals influence the presence of Legionella spp. in water supply. Legionary disease has public health significance because of hard clinical picture and possible lethal issue. Important factors for survival Legionella spp. are physical chemical properties of the water (pH and mineral content, heavy metals), materials of the system, design of the system, furring, corrosion and dead-ends. A biofilm is result from colonization of mineral and organic deposits on surfaces in contact with by microorganisms present in the water. Human activities and natural causes influence the formation of the bio-aerosols which when inhaled, create preconditions for infection. Technical measures, such as flushing pipelines, have been devised to limit the infection risks in hot water. These measures have to be carried out at those high-risk facilities (saunas, swimming pools, jacuzzis). By performing research we can conclude whether the intervention to protect or improve the human health is necessary or whether the previous interventions have been successful. Hot water samples (121) were taken from three hotels in the Split-Dalmatia County, Croatia in the period from January 2011 to December 2011. The chemical analysis included concentrations of iron, zinc, copper and manganese. Cultivation and identification Legionella spp. followed the ISO 11731 standard. Final results are obtained by detailed statistical analysis of available data. The results were analyzed by the chi-square test, followed by statistical analysis at confidence levels p<0.05 with the aim of identification of possible connection of heavy metals concentrations with the Legionella spp. counts. Legionella spp. was confirmed in 13.2% analyzed samples. A statistically significant relation between iron (ρ = 0.271, p = 0.002), copper (ρ = 0.309, p = 0.005), manganese (ρ = 0.391, p = 0.001) and the presence of Legionella spp. was proven. No statistically significant correlation between microbiological findings and the zinc (ρ = 0.094, p = 0.129) in the samples. Higher concentrations of Fe, Cu and Mn were in accordance with the corrosion of the metal piping system and with reduced water flow, which favoured conditions for the growth and breeding of Legionella spp. obtained results indicated that further interventions are required for the protection of the human health. Furthermore this investigation provides the basis for design and subsequent scrutiny of pertinent chemical water treatment technologies. Key words: tap water, heavy metals, biofilm, Legionella spp.

 

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SILVER CELLULOSE NANOCOMPOSITES: A ROUTE TO WASTEWATER

TREATMENT

N. S. Alahmadi, J. D. Wadhawan, S. M. Kelly

HU6 7RX, Kingston upon Hull, United Kingdom

1Presenting author: nsmalahmadi@gmail.com The use of nano-scale materials in electroanalysis has attracted a lot of attention since the combination of two research areas could lead to a number of applications in cleaning the environment, energy generation, bio-sensing and wastewater treatment. 1, 2 Electroanalysis techniques are a facile, low cost and sensitive technique for providing information about a certain species.1, 3 Nanomaterials possess unique physical and chemical properties. Therefore, using this kind of materials in electroanalysis has many advantages in comparison to using other materials, i.e., a good performance, the higher catalytic efficiency, mass transport and great surface area than bulky materials.1, 4 The electro-behaviour of silver cellulose nanocomposites was done with investigation of different parameters, i.e., the concentration of silver nanoparticles, electrolytes and concentration of electrolyte. The stripping of silver cellulose nanocomposites may depend on the size of the nanoparticles and the coverage of silver nanoparticles in the sample. Small nanoparticles showed a very sharp oxidation peak. However, polydispersed nanoparticles had slow and complex redox. The peak potential varied with changing the electrolyte. The oxidation of silver nanoparticles was very sensitive to chloride ions. PXRD patterns confirmed the formation of silver chloride and silver nitrate. Silver cellulose nanocomposites have great potentials in water purification. References

1. Welch, C. W.; Compton, R. G., Anal. Bioanal. Chem. 2006, 384 (3), 601-619. 2. Campbell, F. W.; Compton, R. G., Anal. Bioanal. Chem. 2010, 396 (1), 241-259. 3. Ozkan, S. A., Curr. Pharm. Anal. 2009, 5 (2), 127-143. 4. Goyal, R. N.; Bishnoi, S., Indian. J. Chem. A 2012, 51 (1-2), 205-225.

 

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INFLUENCE OF NANOPARTICLES ON THE CORROSION PROTECTION

PROPERTIES OF SOL-GEL SILANE BASED COATINGS ON MILD STEEL

O. Fronoiu, I. Maior, C. Andronescu, S. Stoleriu

University Politehnica of Bucharest, Faculty of Applied Chemistry and Materials Science, 011061, Bucharest, Romania

Presenting author: oana.fronoiu@yahoo.com According to the EU, environmental legislation has imposed a drastic reduction in the use of chromium containing anticorrosive systems due to their toxicity and especially due to their negative effects on the environment. The anticorrosive properties of sol-gel solutions of various trialkoxysilanes and of trialkoxysilanes reinforced with nanoparticles deposited on mild steel during exposure to corrosive media were investigated. Nanoparticles were used as reinforcing agents for the silane solutions. The electrochemical behavior of coated steel was evaluated by electrochemical impedance spectroscopy (EIS) and potentiostatic polarization curves. FTIR-RA has been successfully used to monitor the structural changes in silane coated metal surface. The surfaces of the samples

were evaluated by XPS technique and the morphology of the films by SEM analysis. Sol–gel protective coatings on steel can improve the corrosion resistance in various corrosive medium and practical applications. Figure 1: The XPS spectra for OL blank, OL treated with OTES 5%_SiC 3000 μg/L and OL treated with VTES 5%_SiC 3000 μg/L.

References 1. D. Wang, G. P. Bierwagen, Progress in Organic Coatings, 64, 327-338 (2009). 2. J. Flis, M. Kanoza, Electrochimica Acta, 51, 2338-2345 (2006). 3. W. J. van Ooij, D. Zhu, M. Stacy, A. Seth, T. Mugada, J. Gandhi, P. Puomi, Tsinghua Sicence

and Technology, 10, 639-664 (2005).

 

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PHOTODEGRADATION OF IODINATED X-RAY CONTRAST MEDIA, IOPAMIDOL, BY

FE3+/OXALATE/PHOTOCHEMICAL PROCESS

K. E. O’Shea1, C. Zhao1, D. D. Dionysiou2, L. Arroyo1, A. DeCaprio1 V. K. Sharma3

1Department of Chemistry and Biochemistry, Florida International University, 11200 SW 8th St. Miami, Florida 33199, USA

2Environmental Engineering and Science Program, University of Cincinnati 705 Engineering Research Center, Cincinnati, OH 45221-0012, USA

3Department of Environmental and Occupational Health, School of Rural Public Health, Texas A&M University, 1266 TAMU, College Station, Texas 77843-1266, USA

Presenting author: osheak@fiu.edu Iodinated X-ray contrast media (ICM) are heavily used intravascular pharmaceuticals to enhance diagnostic X-ray imagines. The presence of ICM in wastewater effluents, surface water and even in drinking water supplies as well as high concentrations of these compounds in hospital wastewater has been reported [1, 2]. Although ICM have not shown any specific health effects on humans, precaution is necessary because of its contribution to organic halogen compound adsorbable on activated carbon (AOX). While ozonation and filtration with granular activated carbon have been used for the removal of ICM contaminated water, it is important to explore alternative more cost effective treatment methods. Iron based treatment and advanced oxidative processes have received considerable attention for the remediation of a wide variety of pollutants. We report herein the Fe3+/oxalate/hv system leads to the rapid degradation of iopamidol, a model ICM compound, under UV and visible light irradiation. The treatment appears to follow photo-Fenton type generation of reactive oxygen species, including hydroxyl radicals [3, 4]. Addition of H2O2 to the reaction enhances the degradation, presumably the result of increased production of hydroxyl radicals. Degradation of iopamidol by the Fe3+/oxalate/hv system was studied under different conditions, including varying Fe3+, oxalate and H2O2 concentrations, influence of light intensity and the effect of solution pH. Detailed product studies were run to elucidate the reaction pathways and demonstrate both oxidation and reduction processes contribute to the degradation of the target compound. The results indicate that the Fe3+/oxalate/hv has the potential to degrade a variety of compounds used as ICM under visible or UV irradiation. References 1. Schulz, M., et al., Environ. Sci. Technol., 42. 7207-7217, 2008. 2. Ternes, T.A. and R. Hirsch, Environ. Sci. Technol., 34, 2741-2748, 2000. 3. Balmer, M.E. and B. Sulzberger, Environ. Sci. Technol., 1999. 33. 2418-2424. 4. Zuo, Y. and J. Hoigne,. Environ. Sci. Technol., 26, 1014-22, 1992.

 

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The Effect of Ozone Concentration on Catalytic Ozonation of Humic Acid with

Granular Activated Carbon

D. Gümüş1, F. Akbal2 1Sinop University, Construction and Technical Department, 57000 Sinop-Turkey

2Ondokuz Mayıs University, Engineering Faculty, Environmental Engineering Department 55139 Kurupelit, Samsun-Turkey

e-mail: fakbal@omu.edu.tr

Humic substances (HS), which are an important component of natural organic matter (NOM) are high molecular weight compounds of complex nature, and are commonly present in natural waters. [1]. Most importantly, the reaction of humic substances with chlorine causes the formation of a variety of harmful disinfection by-products (DBPs) [2]. These compounds are classified as probable or possible human carcinogens by the US Environment Protection Agency [3]. Increasingly stringent limit of disinfection by-products suggests that the removal of humic substances prior to disinfection in water treatment plant is imperative. Thus, the control and removal of NOM is one of the most important approaches typically applied in water treatment utilities to reduce the formation of chlorinated DBPs. Heterogeneous catalytic ozonation is a novel advanced oxidation process (AOP), and based on the generation of highly reactive hydroxyl radicals. This process promotes ozone decomposition, ozonation reactions, otherwise be too low [4]. In this study the effect of ozone concentration on catalytic ozonation of humic acid with granular activated carbon (GAC) was examined. The effect of ozone concentration on HA removal was investigated between 5 to 20 mg/l at HA concentration of 30 mg/l and pH 6.5. The results were evaluated UV254, SUVA (Specific Ultraviole Absorbance at 254 nm), DOC that specify organic matter and Color436. It was obtained that DOC removal was 18.27%, 21.39%, 26.86 and 29.90% at oxidation time of 60 min when ozone concentration as 5 mg/l, 10 mg/l, 15 mg/l and 20 mg/l respectively. Also it was obtained that UV254 and SUVA254 removal efficiencies were 55.71%, 72.78%, 82.09%, 85.33% and 45.81%, 65.37%, 75.51%, 79.07% respectively when ozone concentration was 5mg/l, 10mg/l, 15mg/l and 20mg/l. In the catalytic ozonation experiments, it was obtained that DOC removal was 52.72%, 56.86 and 58.12% at oxidation time of 60 min when ozone concentration as 10 mg/l, 15 mg/l and 20 mg/l respectively. Also it was obtained that UV254 and SUVA254 removal efficiencies were 90.69%, 92.38%, 94.22% and 82.07%, 83.89%, 86.19% respectively when ozone concentration was 10mg/l, 15mg/l and 20mg/l. The results indicated that catalytic ozonation with GAC increased both the DOC and UV254 removal, when compared to ozonation alone. But increasing ozone concentrations did not increase removal efficiencies significantly in the catalytic ozonation processes. References [1] Kasprzyk-Hordern B., Raczyk-Stanisławiak U., Wietlik J. S´, Nawrocki J., Applied Catalysis B: Environmental 62:345–358 (2006). [2] Sadiq, R., Rodriguez, M. J., Science of The Total Environment, 321:21-46 (2004). [3] USEPA, National Primary Drinking Water Regulations; Disinfectants and Disinfection By-Products; Final rule, Fed.Regist. 63:69389-69476 (1998). [4] Molnar J.J., Agbaba J.R., Dalmacija B.D., Klasnja M.T., Dalmacija M.B., Kragulj M.M., Science of the Total Environment 425:169-175 (2012).

 

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CARBAMAZEPINE METABOLITES DETERMINED IN TOMATO AND CUCUMBER

PLANTS IRRIGATED WITH TREATED WASTEWATER

C. Riemenschneider1, M. Goldstein2, M. Shenker2, B. Chefetz2, T. Reemtsma1 1Helmholtz Centre for Environmental Research - UFZ,

Permoserstrasse 15, 04318 Leipzig, Germany 2The Hebrew University Center of Excellence in Agriculture and Environmental Health,

P.O. Box 12, Rehovot 7610001, Israel Presenting author: christina.riemenschneider@ufz.de

Due to the shortage of fresh water in arid and semiarid regions, such as the Middle-East, the use of treated wastewater (TWW) for crop irrigation is a necessity. In Israel, about 50% of the total irrigation water is TWW. As a consequence, pollutants of emerging concern (PEC) such as pharmaceuticals or endocrine disrupting compounds are introduced into the agro-ecosystem. In the last years, growing number of publications have shown that pharmaceutical compounds will be transferred from TWW into edible plants and may finally enter the food chain [1-3]. Carbamazepine, an antiepileptic drug with low removal efficiency in municipal wastewater-treatment plants, is a commonly detected pharmaceutical in wastewater as well as in surface water. Furthermore, some of its main human metabolites have also been found in reclaimed wastewater [4]. Both the uptake of carbamazepine and the occurrence of two metabolites (10,11-dihydro-10,11-dihydroxy carbamazepine and carbamazepine 10,11-epoxide) in plants has already been reported [1]. In our study we developed an analytical method to determine carbamazepine and eight of its metabolites (2-hydroxy carbamazepine, 3-hydroxy carbamazepine, 10,11-dihydro-10-hydroxy carbamazepine, carbamazepine 10,11-epoxide, cis and trans-10,11-dihydro-10,11-dihydroxy carbamazepine, oxcarbazepine) in tomato. A recovery between 75 and 97% with a relative standard deviation of less than 10% could be achieved from spiked tomatoes. Subsequently, the fate of carbamazepine in tomato and cucumber plants (leaves and fruits) irrigated with treated wastewater which was spiked with carbamazepine, was investigated. Eight metabolites of carbamazepine could be quantified using an LC-Q-Trap mass spectrometer. The concentration of carbamazepine and its metabolites differed considerably between tomato and cucumber and in their respective plant organs. Uptake of carbamazepine and its metabolites was about 70-fold (for tomato fruits) and 3-fold (for cucumber fruits) higher than that of carbamazepine alone. References 1. M. Goldstein, M. Shenker, B. Chefetz, Environ. Sci. Technol. 48, 5593-5600 (2014). 2. A. Macherius, T. Eggen, W. Lorenz, M. Moeder, J. Ondruschka, T. Reemtsma, Environ. Sci. Technol. 46, 10797- 10804 (2012). 3. M. Shenker, D. Harush, J. Ben-Ari and B. Chefetz. Chemosphere 82, 905-910 (2011). 4. M. Leclercq, O. Mathieu, E. Gomez, C. Casellas, H. Fenet, D. Hillaire-Buys, Arch. Environ. Contam. Toxicol. 56, 408-415 (2009).

 

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EFFECT OF SOUS VIDE TREATMENT ON BIOGENIC AMINE CONTENT

OF DIFFERENT MEAT DURING STORAGE

E. Őri-Korompai1, L. Simon-Sarkadi1, Z. Mednyánszky1,

G. Kiskó2, G. Kenesei3, L. Friedrich3

1 Department of Food Chemistry and Nutrition, CUB, 1118 Budapest, Hungary 2 Department of Microbiology and Biotechnology, CUB, 1118 Budapest, Hungary

3Department of Refrigeration and Livestocks’ Products Technology, CUB, 1118 Budapest, Hungary

Presenting author: livia.sarkadi@uni-corvinus.hu Sous vide technology is an advanced method of cooking in vacuumed plastic pouches at precisely controlled temperatures. Sous vide treatment improves shelf-life and can enhance taste and nutrition of the food. Regarding meat product scientific literature on sous vide method mainly focused on microbial safety, but there are other potential hazards e.g. biogenic amine formation in meat. High amounts of biogenic amines (BAs) may cause food related pseudo-allergic reactions in sensitive individuals, therefore several efforts have been made to reduce BA content of food. The aim of this work was to study the effect of sous vide technology on biogenic amine formation in different meat (beef, pork and turkey) during storage. According to our knowledge this is the first trial to investigate biogenic amine formation in meat treated with sous vide technology. Samples were treated at 60 oC for 90 minutes, total viable cell count (TVC) was determined on plate count agar and biogenic amine analysis was carried out by an automatic amino acid analyser. All samples were stored at 6 oC for 4 weeks. The initial TVC of control meat samples varied between 104-106 CFU/g depending on the types of meat and increased 1-2 log cycles during 4 weeks of storage. The sous vide treatment reduced the level of TVC by 3-4 log cycles compared to the controls and then the level increased continuously during storage. Biogenic amine content of meat samples increased during the 4 weeks of storage. The total biogenic amine (BA) content ranged between 16-411 µg/g, 68-442 µg/g and 24-644 µg/g in beef, pork and turkey control samples. Cadaverine, tyramine and putrescine were the major amines in all control samples. Histamine concentration was also high in turkey. Sous vide (SV) technology reduced the level of biogenic amines by 90% in beef, 80% in pork and 90% in turkey samples compared to that of untreated samples. The dominant biogenic amine profile in the SV samples was different and showed significantly lower levels than in control samples. Only cadaverine was detected among biogenic amines in beef and turkey while cadaverine and putrescine in pork meat. Sous-vide treatment improved the microbial quality of meat samples, and was effective in the reduction of biogenic amine content of these products.

 

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AROMA COMPOSITION OF RED PEPPER PRODUCTS

FROM DIFFERENT ORIGIN

M. Csóka, M. Amtmann, L. Simon Sarkadi, K. Korány

Corvinus University of Budapest, Department of Food Chemistry and Nutrition, 1118, Budapest, Hungary

Presenting author: livia.sarkadi@uni-corvinus.hu

Red pepper (Capsicum annuum L.) is a significant spice plant and the members of the Capsicum genus are cultivated all over the world [1]. In addition to its colour, the aroma of red pepper powder is a relevant organoleptic property and plays an important role in the choice of consumers as well. In this study, the fragrance constituents of Hungarian, Spanish, Turkish and Peruvian red pepper products were compared. Simultaneous distillation extraction (SDE) was applied for the extraction of volatiles and the measurements were accomplished with GC-MS. The examined red pepper samples proved to be quite fragrant: more than 140 aroma constituents were detected in the volatile fraction of the spices. Individual fragrance components indicating the provenance different from Hungary were identified in every other red peppers. These volatiles were mostly monoterpenes and bi- and tricyclic sesquiterpenes. The highest peak intensities of terpenes were experienced in some Hungarian varieties, while the lowest ones were detected in Turkish red pepper flakes. In Hungarian ground peppers, the number and ratio of pyrazine constituents were much higher than in the spice products from other habitats. This result can be explained by the different processing conditions: in Hungary, the drying of red pepper fruits is performed artificially, so the raw material gets higher heat load. In countries with warmer climate – like Spain, Turkey and Peru – red peppers are dried naturally by the sun that is why the volatile fractions of these products contained less pyrazines due to the milder drying conditions. In Spanish hot red pepper powder some aroma compounds referring to the special drying procedure – smoking – were detected. Besides, the characteristic odour, this processing method were indicated by these volatiles with woody, spicy and smoky aroma. In one of the Peruvian products, some particular mono- and sesquiterpenes regarded as characteristic turmeric odorants [2-3] were identified. In case of Capsicum genus these compounds can mark rather the effects of provenance or divergent species than mixing with the other kind of spice. Several characteristic terpene odorants were identified in the volatile fraction of Turkish red pepper products too. These constituents can be the markers of the different habitat and the processing of miscellaneous red pepper species like C. annuum, C. frutescens and C. baccatum. Consequently the knowledge of the fragrance composition of ground paprika products can be especially important in verifying the origin of species processed. Moreover, it may be of great help in the breeding process to select red pepper species with outstanding fragrance character. References 1. Basu, S. K. and De, A. K., Capsicum (Taylor & Francis, London, 2003) 2. Chempakam, B. and Parthasarathy, V. A., Chemistry of spices (CAB International, Oxfordshire, 2008) 3. Belitz, H-D., Grosch, W. and Schieberle, P., Food Chemistry (Springer-Verlag, Heidelberg, 2009)

 

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ENHANCING OF PHENOL DEGRADATION USING MODIFIED AND PHOTO-

MODIFIED FENTON PROCESS AT NEAR NEUTRAL pH

A. H. Mady*, F.Z. Yehia, Gh. Eshaq, A. M. Rabie, Asmaa A. Roshdey

Department of Petrochemicals, Egyptian Petroleum research Institute, 11727, Nasr City, Cairo, Egypt

Corresponding Author: amr_mady2005@yahoo.com

Combination of Modified Fenton and UV oxidation process has been used for the treatment of an aqueous solution of phenol. The aim of this work was to evaluate the effect of organic chelating agents by using Modified Fenton only and with UV process for phenol oxidation. Three chelating agents were used {Glutamic acid (Glu), Citric acid (CIT) and Sodium Citrate (SC)} [1-4].

Figure 1: Effect of different chelating agents on degradation of phenol in long term experiment Conditions: [ Phenol] =100ppm, [H2O2]=30mM, [Fe2+] =1mM, Glu= 2 mM, SC=25 mM, CIT=10 mM.

It has been demonstrated that combination of two process can significantly improve the hydroxyl radical production. The increasing of hydroxyl radical production increased the efficiency of phenol degradation unlike using Modified Fenton only. Phenol degradation by using Photo-Modified Fenton (PMF) in presence of Glu, CIT and SC was improved to (98% ,75% and 78%), respectively at short term experiment (3h). The degradation rate in long term (24h) was more effective than short term experiment (100%, 81%, 100%) respectively. References [1] F. Z. Yehia, N.G. Kandile, A. M. Badawi and A. H. Mady, Clean – Soil, Air and Water, 40

(7): 692–697 (2012). [2] O. B. Ayodele, J. K. Lim and B. H. Hameed, Chem. Eng. J., 197: 181–192 (2012). [3] G. M. S. Elshafei, F. Z. Yehia, O. I. Dimitry, A. M. Badawi and Gh. Eshaq, Appl Catal B

Environ., 99: 242-47 (2010).    

 

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FIXED-BED COLUMN STUDY FOR BORON REMOVAL USING

SPECIFIC ION-EXCHANGE RESINS

Y. Kunahong1, E. Bilgin Simsek2, U. Beker1, B.F. Senkal3 1Yıldız Technical University, Chemical Engineering Department, 34220, Istanbul, Turkey

2Yalova University, Chemical and Process Engineering Department, 77100, Yalova, Turkey 3Istanbul Technical University, Department of Chemistry, 34469, Istanbul, Turkey

Presenting author: esrabilgin622@gmail.com; ebilgin.simsek@yalova.edu.tr

In the present study, two different kind of sorbents were synthesized: (i) N-methyl-D-glucamine modified poly (styrene) based core-shell type sorbent (VBC-NMG) and (ii) iminodipropylene glycol functionalized polymer (GMA-PVC). Fixed bed column experiments were conducted at different flow rates. The breakthrough curves obtained were sharper with increasing flow rate due to increasing rate constant (Figure 1). When the flow rate increased from 0.3 to 0.7 mL/min, the breakthrough time for VBC–NMG and GMA–PVC samples decreased from 23 to 3 h and 40 to 15 h, respectively. This could be attributed to the increase in speed of adsorption zone at increased flow rate, which resulted in decrease in the time required to reach the specific breakthrough concentration [1]. Thomas and Yoon–Nelson models were applied to the experimental data to predict the breakthrough curves. Thomas model provided good fit to the experimental data with higher R2 values ranging from 0.96 to 0.97 for both samples. The kinetics constant, KT, tends to increase as the flow rate increases, while the qe,cal became smaller as obtained by other researchers. Moreover, the maximum column capacities calculated from Thomas model (qe,cal, mg/g) are very close to the experimental column capacities (qe,exp, mg/g). The experimental results are not adequately reproduced for Yoon-Nelson model owing to the lower R2 values.

Figure 1: Breakthrough curves of resins at different flow rates The iminodipropylene glycol (GMA-PVC) and N-methyl-glucamine (VBC-NMG) modified sorbents were found as an alternative adsorbents for removal of boron. Taking into account the fast kinetics of novel ion-exchange resins, boron removal can be efficient in the column-mode adsorption process. This will be the goal of our future studies.

References 1. B. Kiran and A. Kaushik, Chem. Eng. J. 144, 391–399 (2008).

 

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THE EFFECT OF ORGANOPHOSPHATE AND SYNTHETIC PYRETHROID

PESTICIDES ON ANTIOXIDANT DEFENCE SYSTEM ENZYMES (IN VITRO) AND

THE REACTIVATION OF THESE ENZYMES BY 2-PAM

Hatice Paluzar*1, Ayten Sagiroglu2

1Trakya University, Arda Vocational High School, Edirne, Turkey,

Email: hatice_paluzar@hotmail.com 2Department of Chemistry, Faculty of Science, Trakya University, Edirne, Turkey,

Email: aytensa@trakya.edu.tr

In this study, we focused on in vitro effects of som0049e organophosphates (OPs) and synthetic pyrethroids (SPs) on Antioxidant defence system enzymes [catalase (CAT), superoxide dismutase (SOD), glutation peroxidase (GSH-Px)] activity and the regeneration of these effects by pyridine-2-aldoxime (2-PAM). For this purpose, some pesticides commonly used in region of Thrace, Turkey, were selected. The OPs and the SPs commonly used in agricultural protection were reported to be malathion, dichlorvos, The SPs commonly used in agricultural protection were reported to be deltamethrin, lambda cyhalotrin (Edirne Province Food, Agriculture and Livestock Management). It is known that, OPs pesticides inhibit acetylcholinesterase (AChE) (Eddleston M. et al, 2002). 2-PAM reactivate AChE by removing the phosphoryl group (Bismuth C., 1992). The reactivation of the AChE can be performed through a treatment with 2-PAM. In this study, we aimed to determine that “Do 2-PAM reactivate or not-reactivate Antioxidant defence system enzymes inhibited by pesticides?”. Therefore, we determined the reactivate effects of various doses of 2-PAM on CAT, SOD and GSH-Px inhibited by these pesticides. In the present experiment, malathion, dichlorvos, deltamethrin and lambda cyhalothrin with increasing of its concentrations inhibited all of the enzymes. For reactivation of the inhibition of CAT, 2-PAM is not suitable for treatment of CAT by dichlorvos, malathion and deltamethrin. As shown from the results, 2-PAM is more suitable for reactivation of CAT treatment with lambda cyhalothrin. And as seen from the results 1mM 2-PAM is enough for reactivation. On the other hand, 2-PAM is not suitable for reactivation of GSH-Px and SOD inhibited by the pesticides.

Keywords: Catalase, Glutation peroxidase, Pesticides, Superoxide dismutase    

 

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POLISHING OF TREATED MUNICIPAL WASTEWATER FOR AGRICULTURAL

USE: MICROPOLLUTANTS IN THE ZARQA RIVER, JORDAN

C. Riemenschneider1, M. Al-Raggad2, T. Reemtsma1, E. Salameh2 1Helmholtz Centre for Environmental Research, Department of Analytical Chemistry,

04318 Leipzig, Germany 2University of Jordan, Amman 11942, Jordan

Presenting author: christina.riemenschneider@ufz.de Zarqa River is the major river in Jordan, with the effluent of the As Samra wastewater treatment plant being its major source water. The Zarqa River discharging flood and base flows and treated wastewater is stored in King Talal Dam from where water is released downstream to King Abdullah Canal in the Jordan valley area, where it is mixed with freshwater. The water is used for irrigation of crops along the river and in Jordan valley. The suitability of treated municipal wastewater for irrigation in agriculture in Jordan is based on the compliance with quality standards defined in the “Reclaimed Domestic Wastewater Standard No. 893/2006”, and additional guideline values. Polar and poorly degradable micropollutants may be present in treated reclaimed wastewater, among them pharmaceuticals and other chemicals originating from household and industry. Polishing steps may further improve the quality of treated municipal wastewater and remove micropollutants. We are investigating the occurrence of approx. 60 micropollutants in the Zarqa River water from As Samra wastewater treatment plant area to the Jordan Valley by liquid-chromatography-mass spectrometry (LC-MS/MS). This will provide information on the changes in water quality and the polishing (self-purification) effect along its flow path. The King Talal Reservoir, with a storage capacity of 75 million m3 of water may be of special importance for self-purification. Repeated sampling will be performed to determine seasonal effects. In the first sampling concentrations in the µg/L-range were determined for about 10 micropollutants in the Zarqa River, among them pharmaceuticals like carbamazepine and its metabolites, gemfibrozil and several x-ray contrast agents. While the concentration of the artificial sweetener acesulfame did not indicate much dilution along the flow from As Samra wastewater treatment plant to the Jordan valley, the concentration of some of the micropollutants decreased anyhow. This may indeed indicate polishing (self-purification) processes. The effect of water storage in the King Talal Dam may be studied closer to better understand these processes. Acknowledgement This work is funded by the German Research Council (DFG, Bonn, Germany) through the porject PECtake (Re1290/7-1).

 

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THE INFLUENCE OF CHEMICAL AND PHYSICAL FACTORS IN DETERMINING

SOIL WATER REPELLENCY

H. M. Balshaw1, S. Ahn2, S.H. Doerr2, P. Douglas1, C. Gowenlock2, I. L. Hallin1,

I. Mabbett3, K.A. Mainwaring1, C.P. Morley4 1Chemistry Group, College of Engineering; 2Department of Geography; 3College of Engineering; Swansea University, SA2 8PP, Swansea, UK.

4School of Chemistry, Cardiff University, Park Place, Cardiff, CF10 3AT, UK. Presenting author: 329371@swansea.ac.uk / hbalshaw@hotmail.co.uk

Food security and production is one of the key global issues faced by society. It has become essential to work the land efficiently, through better soil management and agronomy whilst protecting the environment from air and water pollution. The failure of soil to become wetted and absorb water - soil water repellency, causes environmental problems such as soil erosion, increased overland flow, poor uptake of agricultural chemicals, and increased risk of groundwater pollution due to the rapid transfer of contaminants and nutrient leaching through uneven wetting and preferential flow pathways.[1] Organic compounds deposited on soil mineral or aggregate surfaces[1] have long been recognised as a major factor in causing soil water repellency.[2-4] Studies[2,3] have found that the main groups of organic compounds involved are long chain acids, alkanes, amides, aldehydes/ketones and sterols. The degree of water repellency induced by these compounds and mixtures, when reapplied to sands and soils, varies widely with compound type, amount, and mixture, in a complex way.[4] In addition to these chemical effects, surface structure and roughness also influence the severity and extent of soil water repellency. The wettability of non-planar surfaces is determined by the balance of interfacial tensions between the three phases; solid, liquid and vapour, and the resulting water drop contact angle is widely interpreted by the Cassie-Baxter equation.[5,6] Here we discuss the chemical and physical origins of soil water repellency and present our most recent studies on the effect of surface structure on water contact angles. We are using 3D-printed templates to fix in place a variety of model particles, such as surface modified glass beads and rods, sand grains, and metal ball bearing, to give us arrays of precisely positioned close-packed or separated particles, to give well controlled surfaces for water contact angle measurements. Preliminary results show contact angles significantly higher than predicted by the Cassie-Baxter equation, which translates into greater than expected water repellency and we are currently exploring reasons for this. References 1. S.H. Doerr, R.A. Shakesby, R.P.D. Walsh. Earth-Sci. Reviews. 51, 33-65. (2000) 2. S.H. Doerr, C.T. Llewellyn, P. Douglas, C.P. Morley, K.A. Mainwaring, C. Haskins. Aust. J.

Soil Res. 43, 225-237. (2005). 3. C.P. Morley, K.A. Mainwaring, S.H. Doerr, P. Douglas, C.T. Llewellyn, L.W. Dekker. Aust.

J. Soil Res. 43: 239-249. (2005). 4. K. Mainwaring, I.L. Hallin, P. Douglas, S.H. Doerr, C.P. Morley. Eur. J. Soil Sci. 64: 667-

680. (2013). 5. A.B.D. Cassie, S. Baxter. Trans. of the Faraday Soc. 44: 11-6. (1944). 6. G. McHale, M.I. Newton, N.J. Shirtcliffe. Eur. J. Soil Sci. 56: 445-452. (2005).

 

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Predicting of transformations products in the environment – a High Throughput System of Photolyse using a Flow-System

C. Weidauer1, B. Seiwert1, T. Heyner2, T. Reemtsma1

1 Helmholtz-Centre for Environmental Research, Department of Analytical Chemistry 04318 Leipzig, Germany

2 Fachhochschule Lübeck, Lübeck,Germany Presenting author: cindy.weidauer@ufz.de

The chemical fate of a vast number of organic chemicals with diverse molecular structures in the environment is not yet known. Searching for transformation products in environmental samples and assigning them to their parent chemicals is a difficult process. Therefore we are aiming at the simulation of transformation processes in our laboratory. Knowledge on transformation products from such studies eases their subsequent detection in the environment.

For this purpose we are developing a degradation simulator for various compounds in aqueous solution. At the current stage a flow system incorporating photolysis is established. Photochemical reactions (direct and indirect) were studied applying a xenon lamp (sun simulator) as light source. With this application four several substances can measured successively and directly with LC-MS.

Figure 1: Scheme of the flow system to study sunlight photolysis

On-line coupling of the flow system to high resolution mass spectrometry combined with multivariate data analysis (a non-target screening approach) provides a fast and comprehensive tool allowing for structure elucidation of transformation products formed under different reaction conditions. The impact of flow rate, pH, irradiation intensity and the addition of different sensitizers (such as DOM [1]) for indirect photodegradation were studied to obtain a mechanistic understanding of the respective transformation pathways.

The useful capabilities of the applied method are demonstrated for different pharmaceuticals (carbamazepine, triclosan and diclofenac). References 1. L. Carlos, D.O. Martire, M.C. Ganzalez, J. Gomis, A. Bernabeu, A.M. Amat, A. Arques,

Water research 46 (15), 4732-4740 (2012).

 

 

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SUBSTITUTED DIPHENYLAMINE ANTIOXIDANTS AND BENZOTRIAZOLE UV

STABILIZERS IN WATER AND SEDIMENT IN ONTARIO, CANADA

A. De Silva, T. Peart, D. Muir

Water Science Technology Directorate, Environment Canada, L7R 4A6, Burlington, Canada Presenting author: amila.desilva@ec.gc.ca

Substituted diphenylamines (SDPA) are used for their antioxidant properties in applications such as lubricating oil and grease, electronics, foams, and plastic [1]. The SDPAs contain a diphenylamine with alkyl substitutent(s) on the benzene ring(s). A draft screening assessment is underway for some SDPAs in Canada due to potential ecological effects such as persistence and bioaccumulation and for potential alignment with other international activity on SDPAs[1]. Benzotriazole (BZT) UV stabilizers are used in applications such as building materials, personal care products, plastics and paints to improve product’s lifetime by reducing degradation in sunlight such as the yellowing of plastic. BZTs possess the benzotriazole ring structure and a phenol group with structures varying in alkyl substitutents on the phenol ring. A multi-residue method was developed for the analysis of SDPAs and BZTs in aqueous media, sediment and biosolids. Liquid samples were extracted using solid phase extraction cartridges similar to previous methods for BZTs [2]. The cartridges were eluted with 90/10 methyl tertiary butyl ether/methanol. Sediments and biosolids were extracted using a matrix solid phase dispersion technique adapted from Casado et al. [3], wherein the dried solid sample was ground with diatomaceous earth and extracted using 90/10 methyl tert butyl ether/methanol and clean up using primary secondary amine sorbent. Extracts were concentrated to dryness and reconstituted in 1 ml acetonitrile for analysis by liquid chromatography tandem mass spectrometry (LCMSMS). Instrument parameters were optimized with commercially available standards or industry donations. Nine SDPAs and 5 BZTs were analyzed. Resolution of analytes was achieved on a C8 column and acetonitrile-water gradient elution. Extraction efficiency was >80% and determined by comparing the detector response in a sample spiked before extraction to that of a post-extraction sample spike. Matrix effect was calculated using (matrix spike – solvent spike)/solvent spike x 100. Matrix effect ranged from +7.9% for alpha methyl styrene diphenylamine to -13% for UV-234 in a 50 ml wastewater effluent sample. Matrix suppression was evident with increasing sample volume wherein matrix effect ranged from -39% for dioctyldiphenylamine to -8.0 for UV-329 in a 300 ml effluent sample. The hydrophobicity of SDPAs and BZTs resulted in greater detection in sediment and biosolids compared to aqueous samples. Of the SDPAs, diooctyldiphenyl amine and monooctyldiphenylamine were most prevalent. References 1. Government of Canada, Profile for the Substituted Diphenylamine Substance Grouping.http://www.chemicalsubstanceschimiques.gc.ca/group/phenyl/index-eng.php (2014). 2. S.Montesdeoca-Esponda, Z. Sosa-Ferrera, J. Santana-Rodriguez, Anal. Bio. Chem. 403, 867 (2012). 3. J. Casado, I. Rodgriguez, I. Carpinteiro, M. Ramil, R. Cela, J. Chrom. A 1293, 126 (2013).

 

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FAST WAY FOR ESTABLISHING FATTY ACID COMPOSITION OF FATS,

FROM VARIOUS FOODS, USING 1H-NMR SPECTROSCOPY

C. Todasca1, N. Chira1, M. Mihalache1, A. Bratu1, A. Hanganu2, F. Manolache3, S. Rosca1 1Depatment of Organic Chemistry ”C. Nenitescu”, Faculty of Applied Chemistry and Material

Sciences, University Politehnica of Bucharest, 011061, Bucharest, Romania 2Romanian Academy, Center of Organic Chemistry “C. D. Nenitescu”,

060023, Bucharest, Romania 3National Research & Development Institute for Food Bioresources – IBA,

Bucharest, Romania Presenting author: todascacristina@yahoo.com

The use of 1H-NMR spectroscopy in authentication studies for various food products proved to be a very valuable tool [1-3]. Combined with other spectral methods and/or with the help of chemometrical techniques, NMR showed an important potential for discrimination among fats extracted from various foods [4-5]. In this study is presented the potential for compositional characterization of fats by NMR method combined with chemometrical computation. The fats extracted from various sources is directly analyzed by NMR spectroscopy. Variations of the necessary computation for each class of food products is underlined. The food products subjected to this study are: vegetable oils, cheese and fish. The fatty acid composition present some particular aspects for each of the studied food sources. The particularities of each class of food products needs to be considered, when the fatty acid composition of various fats is established based on NMR spectral information. References 1. Hanganu, A., Todașcă, M.C., Chira, N.A., Roșca, S., Revista de Chimie, 62 (7), 689-692,

(2011). 2. Todașcă, M.C., Fotescu, L., Chira, N.A., Deleanu, C., Roșca, S., Revista de Chimie, 62 (2),

2011, 131-134, (2011). 3. Rodrigues, S.M., Otero, M., Alves, A.A., Coimbra, J., Coimbra, M.A., Pereira, E., Duarte,

A.C., Journal of Food Composition and Analysis, 24 (4-5), 548-562. (2011). 4. Hanganu, A., Todaşca, M.-C., Chira, N.-A., Maganu, M., Roşca, S., Food Chemistry, 134 (4),

2453-2458, (2012). 5. Mihalache, M., Bratu, A. , Hanganu, A., Chira, N.-A., Todasca, M.-C., Rosca, S., Revista de

Chimie, 63(9), 877-882, (2012).

 

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STABILITY OF 4-TERT-BUTYL-4'-METHOXYDIBENZOYLMETHANE (BMDM) IN

CHLORINATED WATER

B. Imamović1, S. Trifunović3, E. Bečić1, S.Omerović2, M. Dedić1, M. Šober1 1Department of Pharmaceutical Analysis, Faculty of Pharmacy, Zmaja od Bosne 8,

71000 Sarajevo, Bosnia and Herzegovina 2 Quality Control Department, Bosnalijek d.d., Jukićeva 53,

71 000 Sarajevo, Bosnia and Herzegovina 3Department of Organic Chemistry, Faculty of Chemistry, University of Belgrade,

Studenski trg 12-16, 11000 Belgrade, Serbia Presenting author: ervinafarmacy@gmail.com

Increased production and consumption of products containing organic UV filters cause their presence in the environment in significant concentration, especially in water. Recently, there is increasing public concern regarding secondary effects of personal care products. Therefore, UV filters belong to a new class of organic pollutants [1]. Secondary pollutants are created when primary pollutants (UV filters) react with other active substances, present in the environment. The new compound may be more toxic than the starting primary compound. Many studies have shown that UV filters absorb UV light and decompose under solar irradiation, due to their unstable properties. This may lead to the formation of certain by-products with harmful effects. Their decomposition products can cause allergic and toxic reactions to the human skin. It had been found that UV filters react slowly with chlorine, which is the most commonly used chemical oxidant for drinking water disinfection. Therefore it was necessary to examine not only the presence of UV filters in the water, but also the presence and realistic estimation of by products that may occur, with particular attention paid to the small water areas, such as swimming pools [2-4]. In this paper, stability of the UV filter 4-tert-butyl-4-methoxydibenzoylmethane (BMDM) in chlorinated water was studied. UV/VIS spectroscopy was used to follow the reaction of BMDM in presence of free chlorine. Gas chromatography with mass spectrometry was used to tentatively identify the major transformation by-products. Under the experimental conditions used in this work BMDM reacted with chlorine following pseudo-first order kinetics. Its half-lives ranged from 77,21 to 59,04 sec, depending on the chlorine concentration. The chemical transformation of the BMDM in chlorinated water led to the formation of chlorinated by products that was tenatatively identified as mono and dichloro-substitution of the hydrogen atoms in the benzene rings by one or two chlorine atoms. References 1.Diaz-Cruz MS, Barcelo D, Trends Analyt Chem. 28, (2009). 2.Gago-Ferrero P, Diaz-Cruz MS, Barcelo D., Anal Bioanal Chem. 404, (2012). 3.Stephen Duirk E., David Bridenstine R., Daniel Leslie C., Water research. (2012). 4.Santos AJM, Miranda MS, Esteves da Silva JCG., Water Res. 46, (2012) .

 

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PREPARATION OF GLUTARALDEHYDE-CROSSLINKED GRAPE-WASTE AND ITS

RECOVERY ABILITY OF PRECIOUS METALS

M. Inoue, A. Yamasaki

Seikei University 180-8633, 3-3-1, Kichijoji-Kitamachi, Musashino, Tokyo, Japan Presenting author: inoue.motoki@st.seikei.ac.jp

Grape waste-derived tannin was crosslinked by glutaraldehyde, and its separation and recovery

capabilities for precious metals were investigated. The glutaraldehyde-crosslinked tannin recovered Au and separated Pt and Pd from precious metal mixtures. Here, we report the development of a novel insoluble chemically crosslinked Gravinol, termed

Gravinol-GA, with separation and recovery abilities for precious metals. Gravinol (Gravinol-SE), which consists of more than 83 % proanthocyanidins derived from grape seeds, was provided by the Kikkoman Biochemifa Company (Tokyo, Japan). Gravinol (1.0 g) was dissolved into a solution of 4.0 mL of sodium hydrate (100 mM) and 25 % GA, such that the final GA concentrations were 280, 560 and 1120 mM. Each mixture was stirred and poured into a mold with a 1 mm silicone rubber spacer between two glass plates for 24 h at 25 °C. The resulting Gravinol mixtures are hereafter abbreviated as 280 mM of GA Gravinol-GA is abbreviated as Gravinol-GA280, hereafter Gravinol-GA560, and Gravinol-GA1120, produced using a similar procedure to that described above. The acid resistances of Gravinol-GA with different GA concentrations were investigated by

retaining them in 1.0 M hydrochloric acid solution after 24 h. The water content of Gravinol-GA560 was determined using the following equation:

Water content = (Ww − Wd) / Ww × 100, where Ww and Wd are the weights of Gravinol-GA when immersed in water and after drying, respectively. The water content of Gravinol-GA560 was 75 %. The theoretical water content of Gravinol-GA560 is 68 %, indicating that Gravinol-GA560 exhibits minimal swelling in water. To investigate the precious metal adsorption properties of Gravinol-GA, 0.10 g samples of Gravinol-GA with different GA concentrations were immersed into 1.0 mL precious metal solutions (each precious metal mixture concentration was adjusted to 1000 ppm). The amount of Pt adsorbed to Gravinol-GA560 was slight. In contrast, approximately 20 % of the dissolved Ag and Pd were adsorbed to Gravinol-GA560, and more than 99 % of Au was absorbed to Gravinol-GA560. These results indicate that Gravinol-GA560 possesses high adsorption ability for Au and that Pt and Pd can be separated from solution despite their similar properties. The detailed mechanisms of precious metal separation and recovery by Gravinol-GA are currently under investigation. This work demonstrates that Gravinol-GA can recover Au from precious metal solutions. Gravinol-GA has great potential for use in the separation and recovery of materials from wastewater, such as in plating waste and in urban mining.

 

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ELIMINATION OF ORGANIC CONTAMINANTS OF THERMAL WATERS BY

ADVANCED OXIDATION PROCESSES AND BY

COAGULATION-FLOCCULATION METHODS

G. Veréb1,2, E. Szabó1, G. Simon1,2, T. Alapi1,2, G. Nagy3, T. Medvegy3, I. Ábrahám3, A.

Dombi1, K. Hernádi1

1University of Szeged, Research Group of Environmental Chemistry, H-6720 Szeged, Tisza Lajos Krt. 103, Hungary

2University of Szeged, Department of Inorganic and Analytical Chemistry, H-6701 Szeged, P.O.Box 440 Hungary

3Unichem kft., H-6760 Kistelek, Tanya 491, Hungary Presenting author: verebg@chem.u-szeged.hu

Nowadays the utilization of thermal waters is intensively increasing in energetic utilization and also in social utilization (thermal spas). The reinjection of thermal waters after energetic utilization is strongly recommended (in some countries required by law), but in case of social utilization the reinjection is unallowed because of the potential additional pollutants. In this case the purification of used thermal waters is necessary before the discharging into natural waters. In the recent study advanced oxidation processes like UV photolysis, heterogeneous photocatalysis and ozonation (AOPs - defined as processes involving the generation of highly reactive oxidizing species) and coagulation/flocculation methods were investigated for the elimination of organic contaminants of thermal waters. Combinations of AOPs and coagulation/flocculation methods were also investigated. Model thermal waters (containing humic acid and phenol type contaminants) and real thermal waters were purified by the described methods in laboratory scale, and the scale-up was also demonstrated in the recent work. Heterogeneous photocatalysis (applying immobilized photocatalysts) and UV photolysis combined with ozonation were also carried out in pilot scale reactors. Results confirmed out that humic acid can be easily eliminated by coagulation/flocculation methods, but the elimination of phenol type contaminants is not effective enough by these methods. These compounds can be degraded by advanced oxidation processes, so combined treatments are highly recommended for effective purification of thermal waters. Acknowledgements This research was supported by the European Union and the State of Hungary, co-financed by the European Social Fund in the framework of TÁMOP-4.2.4.A/ 2-11/1-2012-0001 ‘National Excellence Program’. Financial help of the Társadalmi Megújulás Operatív Program (TÁMOP-4.2.2.A-11/1/KONV-2012-0047) also highly appreciated.

 

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PLASMONIC CAPSULES FOR LABEL FREE SERS DETECTION OF ANTIBIOTICS IN WASTE WATER

Javier Pérez-Piñeiro,4 Laura Rodríguez-Lorenzo,2 Alke Petri-Fink,2,3 Moisés Pérez-Lorenzo,1 Mariano Gómez-López4 and

Miguel A. Correa-Duarte1 1Department of Physical Chemistry, Center of Biomedical Research (CINBIO) and Institute of Biomedical Research of Vigo

(IBIV), Universidade de Vigo, 36310 Vigo, Spain 2 Adolphe Merkle Institute, University of Fribourg, Route de l'Ancienne Papeterie, P.O. Box 209, Marly 1723, Switzerland

3 Department of Chemistry, University of Fribourg, Fribourg 1700, Switzerland 4 LABAQUA, S.A., Spain

Currently, only about half of the prescription drugs and other newly emerging contaminants in sewage are removed by treatment plants. In this regard, this type of contaminants are of particular concern given its global distribution, environmental persistency, bioaccumulation and potential harm. Herein, we report the design and synthesis of porous silica-based nanocapsules containing gold nanoparticles (AuNPs) for the detection of trimethoprim, one of the main antibacterial agents used in human and veterinary medicine worldwide. In this case, results show that trimethoprim enters the capsule by diffusion through the pores of the silica shell. At this point, it remains confined given its chemical affinity for the surface of the AuNPs deposited on the silica inner wall. AuNPs may then act as optical sensors to detect this contaminant given their ability to concentrate light at the nanometer scale. In this way, it is possible to reveal the presence of trimethoprim by using these hybrid nanostructures as surface-enhanced Raman scattering (SERS) platforms, achieving thus a detection limit of 3.0 ppm.

Figure 1. Transmission electron microscopy (TEM) image of porous silica-based Au-containing plasmonic nanocapsules (left); SERS spectrum of trimethoprim when excited with a 785 nm laser line (right) . Acknowledgement  Support from a project DEMAGUA (EXP 00064970 / ITC-20133107) funded in the call FEDER-INNTERCONECTA by CDTI and Xunta de Galicia