Chemosphere 92 (2013) 309–316

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Chemosphere

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Occurrence of hydrophobic organic pollutants (BFRs and UV-filters) insediments from South America

0045-6535/$ - see front matter � 2013 Elsevier Ltd. All rights reserved.http://dx.doi.org/10.1016/j.chemosphere.2013.03.032

⇑ Corresponding author. Tel.: +34 93 4006100; fax: +34 93 2045904.E-mail address: eeeqam@cid.csic.es (E. Eljarrat).

1 Tel.: +34 93 4006100; fax: +34 93 2045904.

Enrique Barón a,1, Pablo Gago-Ferrero a,1, Marina Gorga a,1, Ignacio Rudolph b, Gonzalo Mendoza b,Andrés Mauricio Zapata c, Sílvia Díaz-Cruz a,1, Ricardo Barra b, William Ocampo-Duque c, Martha Páez d,Rosa María Darbra e, Ethel Eljarrat a,⇑, Damià Barceló a,f,1

a Department of Environmental Chemistry, IDAEA, CSIC, Jordi Girona 18-26, 08034 Barcelona, Spainb Aquatic Systems Research Unit, Environmental Sciences Centre EULA-Chile, University of Concepción, Concepción, Chilec Faculty of Engineering, Pontificia Universidad Javeriana Seccional, Cali, Colombiad Department of Chemistry, Universidad del Valle, Cali, Colombiae CERTEC, Department of Chemical Engineering, Universitat Politècnica de Catalunya, ETSEIB, Barcelona, Spainf Catalan Institute for Water Research (ICRA), Parc Científic i Tecnològic de la Universitat de Girona, Girona, Spain

h i g h l i g h t s

� BFRs and UV-F levels were comparable to those reported in other regions of the world.� The contamination was greater in Colombian sites.� Contribution of BFRs was higher than that of UV-F for almost all sediments.� Deca-BDE was the formulation used in Colombia, whereas Penta-BDE was also applied in Chile.� DBDPE was detected only in Chilean samples.

a r t i c l e i n f o

Article history:Received 24 October 2012Received in revised form 26 February 2013Accepted 16 March 2013Available online 18 April 2013

Keywords:BFRChileColombiaSedimentsSouth AmericaUV filter

a b s t r a c t

In the present study the occurrence of emerging hydrophobic organic pollutants in sediment samplesfrom South America (Chile and Colombia) was investigated for the first time. Nineteen Chilean and thir-teen Colombian sediment samples were analyzed in order to determine their content of brominatedflame retardants (BFRs) (including PBDEs and emerging BFRs) as well as UV filters (UV-F). Samples werecollected from neighboring aquatic ecosystems highly urbanized and industrialized in Colombia (Magda-lena River area) and Chile (Biobio region). Different analytical procedures were applied depending on theselected analytes, based on chromatographic and mass spectrometric methodologies (GC–MS and LC–MS–MS). In general, concentration levels of both BFRs (up to 2.43 and 143 ng g�1 dw of PBDEs in Chileand Colombia, respectively) and UV-F (nd–2.96 and nd–54.4 ng g�1 dw in Chile and Colombia, respec-tively) were in the low range of published data, and the contribution of BFRs was higher than that ofUV-F for almost all the sampled sediments.

� 2013 Elsevier Ltd. All rights reserved.

1. Introduction

Many studies have arrived to the conclusion that sedimentsconstitute a sink for chemical compounds that are hydrophobic.The contamination of sediments may pose an unacceptable riskto aquatic organisms, which tend to bioaccumulate persistent or-ganic pollutants (POPs), and to wildlife and humans through theingestion of contaminated fish and shellfish.

Brominated flame retardants (BFRs) are a structurally diversegroup of chemicals that are added to polymers which are used inplastics, textiles, electronic circuitry and other materials to reducethe risk of fire. Some of them are ubiquitous, and many have beendetected in biota, sediments, air, water, marine mammals and evenin human milk (Law et al., 2006). Most of the research conductedhas been focused on the study of polybrominated diphenyl ethers(PBDEs) due to their persistence and hydrophobicity, two charac-teristics that make them amenable to bioaccumulation and bio-magnifications (Eljarrat et al., 2004a). Due to their toxicologicaleffect, the production and use of PBDE formulations have beenbanned in Europe, and Penta- and Octa-BDE formulations arenow banned in North America.

310 E. Barón et al. / Chemosphere 92 (2013) 309–316

In response to the increasing international regulations on BFRformulations, alternative additive flame retardants for achievingcommercial product fire safety standards are being developedand used. Some of these non-BDE BFRs are tetrabromobisphenola (TBBPA), hexabromocyclododecane (HBCD), pentabromoethyl-benzene (PBEB), hexabromobenzene (HBB) and decabromodiphen-ylethane (DBDPE). These compounds have been detected inenvironmental samples from Europe and North America, includingsediment, sludge and dust (Eljarrat et al., 2005; Hoh et al., 2005;Stapleton et al., 2008), biota (Fernie and Letcher, 2010) and hu-mans (Eljarrat et al., 2009).

More recently, the research on new hydrophobic organic pollu-tants, the UV filters (UV-F), has raised the scientific interest. UV-Fare considered as environmental contaminants of increasing con-cern since the most commonly used are known to cause endocrinedisrupting effects, to interfere with the thyroid axis, and with thedevelopment of reproductive organs and brain in both aquaticand terrestrial organisms (Fent et al., 2008; Brausch and Rand,2011). As a consequence of the raised concern about the harmfuleffects of solar radiation, these compounds have been increasinglyused from last decades. UV-F are extensively used in personal careproducts to protect the skin and hair from the deleterious effect ofsunlight and, as well as BFRs, are present in a wide variety of indus-trial goods such as paints, plastics or textiles in this case to preventdegradation of polymers and pigments (Zenker et al., 2008). Resi-dues of more polar organic UV-F have been found in all kind ofwater matrices (Balmer et al., 2005; Rodil et al., 2008; Tarazonaet al., 2010). Like BFRs, more lipophilic compounds tend to accu-mulate in sediments (Gago-Ferrero et al., 2011a) and sewagesludge (Gago-Ferrero et al., 2011b), and bioaccumulate in aquaticorganisms (Fent et al., 2010; Gago-Ferrero et al., 2012) and hu-mans, being detected in human breast milk (Schlumpf et al., 2010).

Information on levels, trends and effects of persistent andemerging organic contaminants is quite scarce in South America.In this sense, the BROMACUA project aims to gather baseline infor-mation on levels of BFRs and UV-F in aquatic ecosystems as a wayto contribute to the knowledge of the levels of these pollutants indeveloping countries. The present study investigated the occur-rence of emerging BFRs including TBBPA, HBCD, PBEB, HBB andDBDPE together with PBDE congeners, as well as eight differentUV-F compounds (Benzophenone 3 (BP3), 4-methylbenzylidenecamphor (4-MBC), octocrylene (OCT), ethylhexyl methoxycinnamate(EHMC), octyl dimethyl PABA (OD-PABA), 4-hydroxybenzophe-none (4HB), 2,4-dihydroxybenzophenone (BP1), and 4,40-dihydroxybenzophenone (4DHB)) in sediments. The samples weretaken from neighboring aquatic ecosystems of highly urbanizedand industrialized areas in Colombia and Chile. As far as theauthors know, this is the first time that BFRs as well as UV-F havebeen analyzed in sediment samples from South America.

2. Experimental

2.1. Area of study

The selected areas of study were neighboring aquatic ecosys-tems of Colombia and Chile that were highly urbanized and indus-trialized. Nineteen sampling stations were selected in Chile(Fig. 1a), including river areas, estuary and coastal bays in the Bio-bio region (South Central Chile). Sampling sites were selectedaccording to different criteria such as being located close to someimportant discharges of chemicals, food processing and urban dis-charges. Along the Biobio river basin a total of 326 populated local-ities are located, of which 17 are cities (INE-Chile, 2012). Theeconomic sectors that predominate in this river basin are relatedto forestry, agriculture and industry (mainly represented by metal-lurgical, chemical, oil refining, textiles, pulp industries, among oth-

ers). As it can be seen in Fig. 1a, the study was divided in fourdifferent areas. Coronel Bay area is highly intervened and affectedby human activities, ranging from the impact of wastewater fromthe town of Coronel to the presence of a large concentration of fish-ing industries (fish meal production) and a power generation sta-tion (thermal coal) that discharge their wastes through pipelinesinto the Bay. San Vicente Bay concentrates an important industrialcomplex, whose main activities are related to fish production, steeland petrochemicals. The river sediments were collected at sam-pling sites in the Biobio river located at the mouth of the river,downstream suspected sources of pollution such as urban sewage,oil refinery and a paper mill.

In the case of Colombia, 13 sampling stations were selected inthe area of influence of the Magdalena River in its intersection withthe Caribbean Sea (Fig. 1b). Sampling sites included natural and ur-ban areas from the river-city boundary. Barranquilla city, locatedon the west bank of the river, has an industrial district and a majorsea-river port. Chemical, petrochemical, pharmaceutical, metalmechanical, agrochemical, and fishing are common activities inthis area. Moreover, the Magdalena river basin is the largest riversystem in Colombia being an important fluvial stream for eco-nomic purposes. It has the highest sediment yield of any otherlarge river in South America (Restrepo et al., 2006). The main citiesof the country, including Bogotá, Medellín, Cali and Barranquilla,are located into the basin. Inadequate municipal wastewater treat-ment infrastructure is a pervasive problem in Colombia (Blackman,2009). Consequently, water and sediment pollution problems thatprobably affect ecosystems and biodiversity are present. A sitecalled ‘‘Caño Clarín’’ was monitored to detect the probability ofmigration of pollutants from the river to the ‘‘Ciénaga Grande deSanta Marta’’, a special Ramsar site. Other selected sites were lo-cated in the river mouth itself (Bocas de Ceniza), in a coastal wet-land (Mallorquin swamp) and across the west coastal line wherewind and water flows facilitate the movement of pollutants.

The sample campaign was done in December 2009 and April 2010in Chile and Colombia, respectively (Table 1). Samples were takenwith a petit-ponar type dredge, stored in aluminum foil, sealed inplastic bags and conserved on ice until the arrival into the laboratory.Sediment samples were freeze dried, and lyophilized material wasground, homogenized, and stored in sealed containers at�20 �C untilchemical analysis. Moreover, a sediment characterization was per-formed according to the methodology proposed by Byers et al.(1978), and textural classification according to Wentworth (1922).

2.2. Chemicals

The PBDE native compounds stock solution BFR-PAR, BDE-77,BDE-181 and 13C12-BDE-209 were purchased from Wellington Lab-oratories (Guelph, Ontario, Canada). The components of BFR-PARsolution include different PBDE congeners (from di- to deca-bromi-nated) as well as PBEB, HBB and DBDPE. TBBPA, 13C-TBBPA, d18-a-,d18-b-, and d18-c-HBCD were also obtained from Wellington Labo-ratories Inc. BPA and d16-BPA were from Aldrich Chemical Co. (WI,USA). a-, b-, and c-HBCD were obtained from Cambridge IsotopeLaboratories Inc. (WI, USA). MonoBBPA, DiBBPA, and TriBBPA werea kind of gift from Dr. Göran Marsh (Dep. of Environmental Chem-istry, Stockholm University, Sweden). Analytical standards of BP3,OC, OD-PABA, BP1, 4HB, 4DHB and the isotopically labeled com-pound BP-d10, used as internal standard (IS), were obtained fromSigma–Aldrich (Steinheim, Germany). 4MBC was supplied by Dr.Ehrenstorfer (Augsburg, Germany) and EHMC by Merck (Darms-tadt, Germany).

Individual stock standard solutions were prepared on a weightbasis and stored at �20 �C. A mixture of all selected standards wasprepared by appropriate dilution of individual stock solutions.Stock solutions of internal standards were also prepared and stored

Fig. 1. Sediment sampling locations in (a) Chile: 1, Concepción Bay; 2, San Vicente Bay and Lenga Estuary; 3, Biobio river; 4, Coronel Bay; and (b) Colombia: 1, West coastalline; 2, River mouth; 3, Magdalena river-city boundary.

E. Barón et al. / Chemosphere 92 (2013) 309–316 311

at �20 �C. A mixture of these standards, used for internal standardcalibration, was also prepared by diluting the individual stocksolutions.

All solvents and other reagents were provided by Merk (Darms-tadt, Germany). N2 and Ar purchased from Air Liquide (Barcelona,Spain) were of 99.995% purity. Syringe filters (0.45 lm) were ob-tained from Whatman (London, UK). Pressurized liquid extractioncellulose filters were purchased from Dionex Corporation (Sunny-vale, CA, USA).

2.3. Analytical methodology for BFRs

BFR determinations were carried out using two different analyt-ical approaches. First of all, PBDEs together with PBEB, HBB and

DBDPE were analyzed by gas chromatography (GC) coupled tomass spectrometry (MS) working with negative ion chemical ioni-zation (NICI). On the other hand, HBCD isomers, TBBPA and relatedcompounds (BPA, MonoBBPA, DiBBPA and TriBBPA) were deter-mined by means of liquid chromatography (LC) coupled to tandemmass spectrometry (MS–MS).

2.3.1. Analysis by GC–MSOne gram dry weight (dw) of sediment sample was spiked with

internal standards (10 ng BDE-77, 10 ng BDE-181 and 500 ng 13C12-BDE-209). Spiked samples were kept overnight to equilibrate. Inorder to reduce time of analysis, a selective pressurized liquidextraction (SPLE) method that automatically and rapidly achievesquantitative and selective extraction of BFRs was used (De la Cal

Table 1Information related with the location and physico-chemical parameters of sediment samples collected in this study.

Matrix Location Samplecode

Latitude–longitude Sediment parameters

% Clay % Sand % Gravel Texture classification(Wentworth, 1922)

% TOC

Samples collected in ChileCoastal sediment Concepción Bay CH-TC-01 S36�4301300 W73�0604100 29 71 0 Sandy clay loam 5.7

CH-TC-02 S36�4301400 W73�0501800 31 69 0 Sandy clay loam 4.4CH-TC-03 S36�4301600 W73�0501600 11 89 0 Loamy sand 2.9

Coastal sediment San Vicente Bay CH-SV-01 S36�4303200 W73�0705000 75 25 0 Clay 10.3CH-SV-02 S36�4303200 W73�0704900 83 17 0 Clay 12.4CH-SV-03 S36�4303800 W73�0704300 73 27 0 Clay 12.1CH-SV-04 S36�4401800 W73�0705300 21 79 0 Sandy clay loam 3.7

Estuarine sediment Lenga Estuary CH-LE-01 S36�46009.000 W73�09046.300 42 58 0 Sandy clay 8.7CH-LE-02 S36�46006.500 W73�10017.000 45 55 0 Sandy clay 6.1

River sediment Biobio River CH-BB-01 S36�49039.400 W73�05047.500 1 99 0 Sand 1.3CH-BB-02 S36�46010.600 W73�06024.200 0 100 0 Sand <1.0CH-BB-03 S36�46010.400 W73�06028.000 0 100 0 Sand <1.0CH-BB-04 S36�46006.200 W73�07014.200 0 100 0 Sand <1.0CH-BB-05 S36�46006.500 W73�03020.500 0 100 0 Sand <1.0CH-BB-06 S36�46017.700 W73�10009.700 0 100 0 Sand <1.0

Coastal sediment Coronel Bay CH-CO-01 S37�0103600 W73�0902000 100 0.0 0 Clay 15.4CH-CO-02 S37�0104200 W73�0903600 5 95 0 Sand 11.6CH-CO-03 S37�0104200 W73�0905200 88 12 0 Clay 17.4CH-CO-04 S37�02010,500 W73�0901200 81 19 0 Clay 14.2

Samples collected in ColombiaCoastal sediment West Coastal Line CO-WC-01 N11�03023.200 W74�50034.000 0 100 0 Sand <1.0

CO-WC-02 N11�00028.800 W74�57016.300 0 100 0 Sand <1.0CO-WC-03 N10�59029.500 W74�57037.300 0 100 0 Sand 1.1CO-WC-04 N10�56051.600 W75�01041.200 0 100 0 Sand <1.0

Estuarine sediment Bocas de Ceniza andMallorquin Swamp

CO-BC-01 N11�05‘38.000 W74�50‘45.100 0 100 0 Sand 1.2CO-MS-01 N11�02047.500 W74�51011.900 0 100 0 Sand 1.0CO-MS-02 N11�03023.400 W74�51012.100 0 100 0 Sand <1.0

Estuarine sediment Magdalena River CO-MR-01 N11�02‘34.900 W74�49‘23.500 0 100 0 Sand 1.0CO-MR-02 N11�02‘08.100 W74�48‘43.300 0 100 0 Sand 1.0CO-MR-03 N11�00035.500 W74�46044.700 0 100 0 Sand <1.0CO-MR-04 N10�59041.500 W74�46000.100 0 100 0 Sand 1.1CO-MR-05 N10�56046.600 W74�45030.900 0 100 0 Sand 2.1CO-MR-06 N10�5703.1200 W74�44053.300 0 100 0 Sand 1.3

312 E. Barón et al. / Chemosphere 92 (2013) 309–316

et al., 2003). Two grams copper were added to the cell to removesulfur interferences. SPLE was carried out using a fully automatedASE 200 system (Dionex, Sunnyvale, CA, USA) using aluminumoxide neutral and Hydromatrix (Varian Inc., Palo Alto, USA). Theextraction cell was heated to 100 �C and extraction was carriedout using a mixture of hexane:CH2Cl2 (1:1). The volume of theresulting extract was about 35 mL. Extracts were finally concen-trated to incipient dryness and re-dissolved with 50 lL of tolueneprior to analysis by GC-NICI–MS. GC-NICI–MS analyses were per-formed on a trace GC ultra gas chromatograph connected to a dualstage quadrupole mass spectrometer (Thermo Electron, Texas,USA). A DB–5MS capillary column (15 m � 0.25 mm i.d., 0.1 lmfilm thickness) was used with ammonia as the carrier gas at anion source pressure of 1.9 � 10�4 Torr. The temperature programwas from 140 �C (held for 2 min) to 325 �C (held for 10 min) at10 �C min�1. Injection was carried out by splitless mode for 1 minwith an injector temperature of 250 �C (Eljarrat et al., 2004b).Experiments were carried out monitoring the two most abundantisotope peaks from the mass spectra corresponding to m/z = 79and 81 [Br]� for di- to nona-BDEs, PBEB, HBB and DBDPE, m/z = 487 and 489 for BDE-209 and m/z = 497 and 498 for 13C12-BDE-209. The identification of selected analytes was based on thefollowing restrictive criteria: (i) retention time for all monitoredions for a given analyte should maximize simultaneously ± 1s, withsignal to noise ratio >3 for each; and (ii) the ratio between the twomonitored ions should be within 15% of the theoretical value (cal-culated upon standards). The quantification of di- to penta-BDEs,

PBEB and HBB was carried out by internal standard procedureusing BDE-77, whereas for hexa- to hepta-BDEs, BDE-181 standardwas used. In the case of deca-BDE and DBDPE, the quantificationwas carried out using 13C12-BDE-209 as internal standard.

2.3.2. Analysis by LC–MS–MSSediment sample of 0.5 g dw was spiked with 50 lL of a mix-

ture of d18-a-HBCD and d18-c-HBCD, and 50 lL of 13C-TBBPA, bothsolutions at concentrations of 5 ng lL�1. Spiked samples were keptovernight to equilibrate and extracted by sonication with 10 mL ofdichloromethane:methanol (1:9, v/v). The obtained extracts werecleaned with SPE C18 cartridges. Finally, extracts were concen-trated to incipient dryness and re-dissolved with 50 lL of d18-b-HBCD and 50 lL of d16-BPA at 5 ng lL�1, and 150 lL of methanolprior to analysis by LC–MS–MS. The LC system used was an Symbi-osis Pico (Spark Holland, Emmen, The Netherlands) with a Symme-try C18 column (2.1 mm � 150 mm, 5 lm) preceded by a C18guard column (2.1 � 10 mm) supplied by Waters (Massachusetts,USA). Experiments were carried out in negative ionization modeusing H2O:methanol (3:1 v/v) as eluent A and methanol as eluentB, at a flow rate of 0.25 mL min�1. The injection volume was setat 10 lL. The elution program started at an initial composition of100% A and was ramped to 0% eluent A in 8 min, then eluent A in-creased to 10% in 17 min and initial conditions were reached againin 3 min and returned to the starting conditions in 15 min. Massspectrometric analysis was performed with a hybrid triple quadru-pole/linear ion trap Applied Biosystem MSD Sciex 4000QTRAP™

Table 2Recoveries, relative standard deviations (RSDs) and method limits of detection (LOD)and quantification (LOQ) of analysis of BFRs and UV-F in sediment samples.

Compound Recovery (%) RSD (%) LODa (ng g�1 dw) LOQa (ng g�1 dw)

Brominated flame retardantsDi-BDEs 87–105 0.7–4 20–41 67–136Tri-BDEs 57–101 3–5 15–19 50–63Tetra-BDEs 64–88 0.8–8 4.7–11 15–36Penta-BDEs 96–110 0.8–7 7.7–24 25–81Hexa-BDEs 74–105 2–8 8.4–22 28–74Hepta- 82–102 0.6–8 1.0–13 29–43

E. Barón et al. / Chemosphere 92 (2013) 309–316 313

(Applied Biosystems, Foster City, CA, USA) instrument equippedwith an electrospray (ESI) Turbo spray interface. All data were ac-quired and processed using Analyst 1.4.2 Software. For targetquantitative analyses, data acquisition was performed in selectedreaction monitoring (SRM). The MS–MS detection conditions wereoptimized previously to afford the highest relative intensity: cur-tain gas (CUR) at 50 psi, collision gas (CAD) at 4.5 � 10�5 Torr, tem-perature of the turbo gas in the TurboIonSpray™ source (TEM) at350 �C, ion source gas 1 (GS1) and ion source gas 2 (GS2) at50 psi (Guerra et al., 2008).

BDEsOcta-BDEs 66–102 2–6 21–36 70–120Nona-BDEs 56–71 2–8 13–18 43–61Deca-BDE 83 6 25 37PBEB 58 3 18 60HBB 62 5 9.1 30DBDPE 102 6 86 288BPA 106 7 3.7 9.5Mono-

BBPA88 8 0.6 1.9

Di-BBPA 105 6 2.0 6.7Tri-BBPA 126 7 28 92TBBPA 110 9 2.7 8.9a-HBCD 53 11 1.6 5.3b-HBCD 57 13 1.4 4.6c-HBCD 89 3 2.2 8.2

UV-filters4MBC 89 6 1.1 3.6OCT 85 7 9.9 33EHMC 90 6 4.1 14OD PABA 120 4 0.7 2.5BP3 125 10 0.4 1.3BP1 58 16 4.6 154HB 80 8 0.7 2.34DHB 120 9 0.8 2.7

a Italic values corresponded to LODs and LOQs expressed in pg g�1 dw.

2.4. Analytical methodology for UV-F

Background contamination in the laboratory is a common prob-lem observed in the determination of UV-F at environmental tracelevels. As precautionary measures all glassware used was previ-ously washed and heated overnight at 380 �C and further sequen-tially rinsed with HPLC grade water, ethanol and acetone, andimmediately used. Furthermore, gloves were worn during samplepreparation; separate solvents and only previously unopenedpackages of solvents, chemicals and other supplies, and glasswarewere used. Since many of the compounds analyzed undergo photo-degradation and the samples may suffer the exposure to light dur-ing the procedure, all samples and stock standard solutions werealways covered with aluminum foil and stored in the dark.

Similarly to BFR analysis, sediment samples were extracted andpurified by SPLE. Aliquots of 1 g of alumina (previously heated at130 �C overnight, and then allowed to cool down in a desiccator be-fore use) were placed at the outflow side of each cell onto two cel-lulose filters. Under optimized conditions, aliquots of 1 g dwsediment were mixed in the PLE extraction cells with alumina inorder to perform the in-cell purification. Finally, the PLE extractwas brought to 25 mL with methanol. A 2 mL aliquot of this solu-tion was passed through 0.45 lm syringe filter to a LC-vial, andevaporated to dryness under a gentle stream of nitrogen in a Turb-oVap LV evaporator from Zymark (Zymark, Hopkin, MA). The driedextracts were reconstituted in 250 lL of acetonitrile containing theIS.

Chromatographic separations were performed on a Hibar Puro-spher� STAR� HR R-18 ec. (50 mm � 2.0 mm, 2 lm) LC columnsupplied by Merck with an Acquity UPLC chromatograph (Waters).The column temperature was kept at 50 �C. Separation was per-formed with a binary mobile phase at a flow rate of 0.4 mL min�1.The optimized separation conditions were as follows: solvent Aconsisted of H2O and solvent B acetonitrile, both with 0.3% formicacid. The gradient elution started with 5% eluent B, increasing to80% in 2 min. and raising to 100% in the following 9 min kept con-stant for 2 min, then return to initial conditions in 2 min, and final-ly three additional min to allow the equilibration of the column.The sample volume injected was 10 lL.

The ultra performance LC (UPLC) instrument was coupled to atriple quadrupole mass spectrometer (Waters). Acquisition wasachieved in electrospray positive mode (ESI(+)) using SRM moderecording two transitions for each compound for enhanced sensi-tivity and selectivity. For each compound, two characteristic frag-ments of the protonated molecule [M + H]+ were monitored. Themost abundant transition was used for quantification, whereasthe second most abundant one was used for confirmation. Thisprocedure was in compliance with the European Council Directive2002/657/EC, that although it was initially conceived for food res-idue analysis, it has been accepted by the scientific community forenvironmental analysis. More information about the analyticalmethod can be found in a previous work from Gago-Ferrero et al.(2011a).

2.5. Quality assurance/quality control

Method blank samples were performed to check for interfer-ences or contamination from solvents and glassware. No presenceof analytes of interest was observed. Quality assurances of the de-scribed methods were evaluated by measuring parameters as line-arity, sensitivity, recoveries, and reproducibility. The limits ofdetection (LOD) defined as three times the noise level, and the limitof quantification (LOQ), defined as 10 times the noise level, werecalculated and presented in Table 2.

3. Results and discussion

3.1. BFR contamination levels

The levels of BFRs in sediment samples collected for this studyare presented in Table 3. PBDEs were detected in all the sedimentsamples from Chile at concentrations ranging from 0.03 to2.43 ng g�1 dw. The Lenga estuary and Coronel bay were the mostcontaminated zones, with mean values of 1.84 ng g�1 dw and1.57 ng g�1 dw, respectively. After them San Vicente and Concep-cion bays presenting a similar level of contamination (mean valuesof 1.01 and 0.95 ng g�1 dw, respectively), and finally, the less con-taminated area corresponded to Biobio river (mean value of0.31 ng g�1 dw) (Fig. 2). This pattern of contamination was alsopreviously observed with other pollutants in these areas, such asPAHs, with the highest values found in the Lenga estuary (Pozoet al., 2011).

With regard to the sediments from Colombia, PBDEs were de-tected in five out of 13 analyzed samples. However, in these sam-ples, PBDE contamination was greater than that observed for

Table 3Concentration levels of BFRs and UV-F in sediment samples collected in Chile and Colombia. Results expressed as range of concentrations in ng g�1 dw.

Chile Colombia

ConcepciónBay (n = 3)

San VicenteBay (n = 4)

LengaEstuary (n = 2)

Biobio River(n = 6)

Coronel Bay(n = 4)

West CoastalLine (n = 4)

Bocas de Ceniza andMallorquin Swamp (n = 3)

MagdalenaRiver (n = 6)

Brominated flame retardantsBDE-47 nd nd–0.33 nd nd 0.15–0.63 nd nd ndBDE-100 nd–0.09 nd 0.19–0.30 nd–0.03 nd–0.21 nd nd ndBDE-99 nd–0.17 nd–0.53 0.75–0.83 nd 0.19–0.73 nd nd ndBDE-154 nd nd nd–0.59 nd nd nd nd ndBDE-183 nd nd–0.32 nd nd nd nd nd ndBDE-209 nd–1.72 0.73–0.93 0.50–0.51 nd–0.39 nd–0.85 nq nq–143 nq–55.8PBEB nd–0.08 nd nd nd–0.15 nd–0.11 nd nd ndDBDPE 1.62–2.26 nd–2.16 1.12–1.96 nd–2.23 nd–1.91 nd nd ndDi-BBPA nq–210 1230–1328 7.83–51.3 nd–164 21.7–685 nd nd ndTri-BBPA 4.50–8.40 nd–6.63 nq 3.33–7.03 nd–4.25 nd nd nd–0.27TBBPA nd nd nd nd nd nd nd–0.58 ndc-HBCD nd nd nd nd nd nd nd nd–0.33

UV filtersBP3 nd nd–1.42 nd–2.96 nd–1.05 nd nd–2.52 nd–4.85 nd–5.384MBC nd nd nd nd nd nd–7.90 nd–17.2 ndEHMC nd nd nd nd nd nd–17.8 nd–39.0 nd–47.1

Fig. 2. Median values of BFRs and UV-F in each selected area of study (Chile andColombia).

314 E. Barón et al. / Chemosphere 92 (2013) 309–316

Chilean sediments, with levels ranging up to 143 ng g�1 dw. Thehigher contamination was observed for estuarine sediments fromBocas de Ceniza and Mallorquin swamp (mean value of 47.8 ng g�1

dw), followed by the sediments from Magdalena river (mean valueof 10.6 ng g�1 dw). Finally, the sediment collected at the westcoastal line does not presented PBDE contamination, probably

due to the high plume dispersion and sediment transport (Fig. 2).There are important differences in terms of circulation of water,fluxes, and amount of particles between the Magdalena rivermouth and the estuary. Strong littoral currents predominantly flowtoward the west and are the result of open ocean swells generatedby NE trade winds, and the muddy plume of the river spans morethan 90 km in length which could explain the high dispersion ofBFRs and the consequent lower detection in the respective sam-ples. Likewise, high rates of total solids are present in the waterat the river mouth meaning high sediment yields which also helpdisperse organic pollutants. The highest value (143 ng g�1 dw) ap-peared in the sediment sample collected at the center of the Mal-lorquin swamp. This area has historically received discharges withnon treated domestic wastes from Barranquilla. Very quiet watersand the high sedimentation processes suffered in this wetland maycontribute to explain such levels. Another high level of contamina-tion (55.8 ng g�1 dw) was found in one of the Magdalena river sed-iments, downstream an industrial free zone. In general, thepresence of BFRs in Colombian river systems could be probablydue to poor e-waste management since many toxic electronicwastes are commonly disposed in landfills.

Of 38 PBDEs congeners included in our analytical work, only sixdifferent PBDEs were detected: tetra-BDE-47, penta-BDE-99, pen-ta-BDE-100, hexa-BDE-154, hepta-BDE-183 and deca-BDE-209.The dominance of BDE-209 in the total PBDEs is unquestionable,similar to findings in reported studies with sediments fromdifferent geographical areas (Eljarrat et al., 2004b). In this study,BDE-209 constituted between 24% and 100% of the total PBDEcontamination. It is important to note that in all sediment samplesfrom Colombia with detectable PBDE levels, the pollution is due toexclusively the BDE-209. The presence of BDE-209 indicates theuse of commercial formulations of deca-BDE in the studied area.The presence of BDE-47, BDE-99 and BDE-100 in Chileansediments was attributed to the use of penta-formulations.

Unfortunately, there are no data on PBDE levels in sediments ofSouth America. However, there are a lot of studies reporting levelsin other geographical areas. In order to compare the levels found inthis study with those of other areas, the comparison will be madewith data published during this year (2012). Levels of PBDEs weredetermined in sediments from the Scheldt estuary (the Nether-lands-Belgium), with an average concentration of 115 ng g�1 dw.The total amount of PBDEs was mainly coming from BDE-209, ina 99% of the cases (van Ael et al., 2012). These findings are in

E. Barón et al. / Chemosphere 92 (2013) 309–316 315

agreement with the results of the present study in Colombia.PBDEs were also measured in sediments from Southern CaliforniaBight, with a geometric mean and maximum levels of 4.7 and560 ng g�1 dw (Dodder et al., 2012). Although these maximum lev-els are higher than those found in this study, the average concen-tration is of the same order as in the Chilean samples. Severalrecent studies were focused on China. PBDEs of sediment samplesfrom the coastal East China Sea were measured, with levels ofBDE-209 and RPBDEs (sum of BDE-28, -47, -99, -100, -153, -154and -183) between 0.3–44.6 and nd–8.0 ng g�1 dw, respectively(Li et al., 2012). In another study, sediment samples from riversof Shanghai were analyzed (Wu et al., 2013). PBDEs were detectedat concentrations from 11.0 to 64.1 ng g�1 dw, with an average va-lue of 29.7 ng g�1 dw. BDE-209 was the predominant congeneraccounting for more than 97% of total PBDEs. Once again, theseresults are in accordance with Colombian data.

As expected due to the lower industrial use, the presence of thenon-BDE BFRs (PBEB, HBB, DBDPE, HBCD and TBBPA) is lower thanthat of PBDEs. HBB was not detected in any sample, HBCD was de-tected only in two samples from Colombia at concentration levelslower than 0.33 ng g�1 dw, and PBEB was detected only in foursamples from Chile and at concentration levels lower than0.15 ng g�1 dw. DBDPE was detected in 12 of 19 analyzed sedi-ments from Chile (from nd to 2.26 ng g�1 dw), but it was not de-tected in Colombian sediments indicating their lack of use in thatcountry. DBDPE applications are similar as for BDE-209 with theadvantage of no production of dibenzo-p-dioxins and no formationof furans under pyrolysis conditions (Jakab et al., 2003;Kierkegaard et al., 2004). Generally, the reported levels of DBDPEwere lower than those of BDE-209 (Kierkegaard et al., 2009). Inthe present study it is observed that in 58% of Chilean samples,DBDPE concentrations are higher than BDE-209, with ratios be-tween 2.2 and 6.2. This could indicate a higher input in the useof DBDPE in this area.

With reference to TBBPA, this BFR was detected only in twoColombian samples. However, high levels of their related com-pounds were detected in Chilean sediments, with values betweennd to 1328 ng g�1 dw and nd to 8.40 ng g�1 dw for Di-BBPA andTri-BBPA respectively. The presence of these related compoundsmay be due to the TBBPA degradation. Debromination of TBBPAcould occur during the wastewater treatment, or other abioticdebromination processes (Chu et al., 2005).

3.2. UV-F contamination levels

UV-F concentrations in sediment samples analyzed are summa-rized in Table 3. Just one out to eight compounds, BP3, was de-tected in the sediment samples from Chile in a range ofconcentration from 1.05 to 2.96 ng g�1 dw. This compound is usedin personal care products or as an additive in materials that have tobe protected from sunlight-initiated disrupting (FDA, 1999; Coun-cil Directive, 1976) and have been detected previously in river sed-iment samples of Spain (Gago-Ferrero et al., 2011a) and China(Zhang et al., 2011) in the same range of concentration.

Higher levels of UV-F were detected in several sites of Colombia.In this case three out to eight compounds, BP3, 4MBC and EHMC,were present in the samples. EHMC was detected at a frequencyof 38% and with the highest concentrations in the analyzed sam-ples, above 47 ng g�1 dw in some cases. 4MBC was present in the23% of the samples in the range from 7.9 to 17.2 ng g�1 dw. BP3was the most ubiquitous compound and its levels were higher thanin Chilean samples, 77% frequency of detection at concentrationsfrom <LOQ to 5.38 ng g�1 dw. It is noteworthy that the highly lipo-philic UV-F OC, which usually is the most ubiquitous UV-F com-pound in solid environmental matrices, was not present in any

studied sediment. This fact suggests that the production and usageprofiles of UV-F are different among countries.

All these compounds have been found to have estrogenic hor-monal activity and multiple endocrine-disrupting activities (Fentet al., 2008; Christen et al., 2011). Adverse effects on fecundityand reproduction have also been observed for BP3 (Coronadoet al., 2008). 4MBC has also shown high estrogenic potency andits use in cosmetic products is not allowed in the USA or Japan leg-islation. However, these adverse effects take place at higher con-centrations than those detected in the published environmentalstudies.

The presence of such substances is influenced by the extendeduse of solar protection creams since sun rays are very strong in thisarea. Aquatic tourist activities, which are frequent in this area, arealso a factor to take into account and may play an important role inthe determined levels. However, a possibly even more importantfactor could be wastewater treatment plants (WWTPs) discharges,from urban and industrial areas. Monitoring data of WWTPs indi-cates that current techniques are not effective at all removingUV-F. Several of them, including BP3, EHMC and 4MBC, were foundin untreated and treated wastewater in different countries (Li et al.,2007; Negreira et al., 2009a), as well as in sewage sludge(Gago-Ferrero et al., 2011b). Measurable values of these com-pounds have been determined at relatively high values in rawand treated water. This effect could be more important if, ascommented in the area of study section, historically urban andindustrial effluents have been released to the river withoutcleaning treatment, which multiplies the presence of organicanthropogenic pollutants in the water and sediments.

High differences between the low levels found in Chile versusthe levels in Colombia can be explained because the second is atropical country with high solar radiation levels, and the use of per-sonal care products containing UV-F is probably much higher thanin Chile. Moreover, the tourism activity in Caribbean Colombianbeaches could be responsible by the higher UV-F concentrationsin water compared to the Chilean case.

4. Conclusions

The occurrence of emerging hydrophobic organic pollutants insediment samples from Chile (Biobio region) and Colombia (Mag-dalena River area) was investigated for the first time. DifferentBFRs were analyzed, showing the presence of PBDEs in both se-lected areas at concentration levels up to 2.43 and 143 ng g�1 dwin Chile and Colombia, respectively. These results are comparableto those reported recently in other regions of the world. DifferentPBDE patterns were observed, with Deca-BDE formulation beingthe unique used in Colombia, whereas Chilean samples showedalso the use of Penta-BDE formulations. As regards the non-PBDEBFRs, their presence was less frequent and at low concentrationlevels, with the exception of DBDPE. This replacement of Deca-BDE was detected in Chilean samples, but not in Colombian sedi-ments indicating their lack of use in that country.

As regards UV-F presence, only three out of the total of com-pounds included in the analytical work where detected at concen-tration levels ranging between nd to 2.96 and nd–54.4 ng g�1 dw inChile and Colombia, respectively. Similarly to BFRs, the contamina-tion was greater in Colombian sites. It is also important to noticethat in almost all of the samples, UV-F levels were lower than thosefound for BFRs for the same site (Fig. 2).

The present findings provide evidence that currently, emergingcontaminants such as non-PBDE BFRs and UV-F are present in theSouth American environment. Further measurements are requiredto better understand their fate and occurrence of these com-pounds. Moreover, although the levels found in this study were

316 E. Barón et al. / Chemosphere 92 (2013) 309–316

not extremely high, it is expected that in the future the concentra-tion levels may increase. Due to the toxicological effect of PBDEs,their production and use has been banned in Europe and NorthAmerica. One would expect that this will be the same situationin the near future in South American countries, in particular con-sidering that Penta-BDE and Octa-BDE mixtures have been alreadyincluded in the Stockholm Convention and that parties should en-force their gradual elimination. And, in order to meet the commer-cial product fire safety standards, non-PBDE formulations, such asDBDPE, HBB and PBEB, are likely to be used more frequently.Therefore, it will be necessary to continue these monitoring pro-grammes in order to detect a possible raise in pollution levelsdue to increased use and application.

Acknowledgements

This research project was founded by the Fundación BBVA un-der the BROMACUA project, and by the Spanish Ministry of Econ-omy and Competitiveness through the projects CEMAGUA(CGL2007-64551/HID) and SCARCE (Consolider Ingenio2010 CSD2009-00065). This work was partly supported by theGeneralitat de Catalunya (Consolidated Research Group: Waterand Soil Quality Unit 2009-SGR-965). The authors would like tothank Dr. Göran Marsh (Department of Environmental Chemistry,Stockholm University, Sweden) for MonoBBPA, DiBBPA, and TriB-BPA standards. Waters Corporation (USA) and Isolute (Sweden)are gratefully acknowledged for providing the solid-phase extrac-tion cartridges. The authors want also to express their gratitudeto Biotage and Merck for the gift of SPE cartridges and UPLC col-umns, respectively.

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