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Distribution of Potentially Toxic Elements in Sediments of anIndustrialized Coastal Zone of the Northern Aegean SeaGeorgios Papastergiosa; Anestis Filippidisa; Jose-Luis Fernandez-Turielb; Domingo Gimenoc;Constadinos Sikalidisd

a Department of Mineralogy-Petrology-Economic Geology, Aristotle University of Thessaloniki,Thessaloniki, Greece b Institute of Earth Sciences “Jaume Almera”, Consejo Superior de InvestigacionesCientíficas (CSIC), Barcelona, Spain c Faculty of Geology, University of Barcelona, Zona Universitàriade Pedralbes, Barcelona, Spain d Department of Chemical Engineering, Aristotle University ofThessaloniki, Thessaloniki, Greece

First published on: 16 September 2010

To cite this Article Papastergios, Georgios , Filippidis, Anestis , Fernandez-Turiel, Jose-Luis , Gimeno, Domingo andSikalidis, Constadinos(2010) 'Distribution of Potentially Toxic Elements in Sediments of an Industrialized Coastal Zoneof the Northern Aegean Sea', Environmental Forensics, 11: 3, 282 — 292, First published on: 16 September 2010 (iFirst)To link to this Article: DOI: 10.1080/15275922.2010.494992URL: http://dx.doi.org/10.1080/15275922.2010.494992

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Environmental Forensics, 11:282–292, 2010Copyright C© Taylor & Francis Group, LLCISSN: 1527–5922 print / 1527–5930 onlineDOI: 10.1080/15275922.2010.494992

Distribution of Potentially Toxic Elements in Sediments of anIndustrialized Coastal Zone of the Northern Aegean Sea

Georgios Papastergios1, Anestis Filippidis1, Jose-Luis Fernandez–Turiel2, Domingo Gimeno3, andConstadinos Sikalidis4

1Department of Mineralogy-Petrology-Economic Geology, Aristotle University of Thessaloniki, Thessaloniki, Greece2Institute of Earth Sciences “Jaume Almera”, Consejo Superior de Investigaciones Cientıficas (CSIC), Lluıs Sole i Sabarıs,Barcelona, Spain3Faculty of Geology, University of Barcelona, Zona Universitaria de Pedralbes, Barcelona, Spain4Department of Chemical Engineering, Aristotle University of Thessaloniki, Thessaloniki, Greece

Nine sediment samples from Filippos B port, Kavala, northern Greece, were collected and analyzed for their content of 42 elements.The results indicate that both major and trace elements can be divided into two groups according to their anthropogenic source. Thefirst group includes Al, Cl, Fe, K, Mg, Na, P, S, Ag, As, Cd, Ce, Hg, La, Mo, Pb, Sb, Se, U, and Y, which come from a phosphoricfertilizer industry, while the rest of the elements (B, Ba, Co, Cr, Cs, Cu, Ga, Ge, Li, Mn, Ni, Rb, Sn, Th, Ti, V, W, Zn, and Zr) belong tothe second group and can be traced to the other local industrial activities, as well. Bivariate analysis indicated that among the elementswithin each group high positive correlation coefficients exist.

Keywords: geochemistry, environment, potentially toxic elements, sea sediment, Kavala, Greece

Monitoring the geochemical status of sea sediments is an im-portant, and, at the same time, complex task since these envi-ronments often receive several kinds of potentially toxic traceelements generated either naturally, through the weathering ofparent rocks, or through various human activities. Fine-grainedparticles may also act as effective carriers of metals from thewater column to the sediments and thus elevate the concentra-tions of heavy metals in the sediments (Casado-Martinez et al.,2006; Lu et al., 2005; McReady et al., 2006). In such aquatic en-vironments, many contaminants—especially trace elements—discharged from a variety of sources may accumulate in bottomsediment and trigger toxic effects on organisms living in the ad-jacent area (Michel and Zengel 1998; Valette-Silver et al., 1999;Fattorini et al., 2004). Subsequently, the concentrations of theseelements in sediments near cities or industrial areas are oftenhigher than those located far from such contamination sources.

Although the contamination of the sea may be less visibleand direct than other types of contamination, its effects on ma-rine ecosystems and humans are intensive and very extensive(Kucuksezgin et al., 2006). As both sink and source, depend-ing on local physicochemical parameters, sediments constitutea reservoir of bioavailable trace elements and play an important

Address correspondence to Georgios Papastergios, Depart-ment of Mineralogy-Petrology-Economic Geology, Aristotle Uni-versity of Thessaloniki, 54124, Thessaloniki, Greece. E-mail: gpa-paste@geo.auth.gr

role in geochemical cycles. Changes in environmental condi-tions, such as acidification, redox potential or organic ligandconcentrations, can cause mobilization of elements from a solidto a liquid phase and cause the contamination of surroundingwaters (Yuan et al., 2004; Lu et al., 2005). In fact, the accumula-tion of potentially toxic and persistent substances in the coastalenvironment continuously increases due to anthropogenic activ-ities as estuaries and their nearby coastal areas have become thefocus of numerous economic activities (Ramessur 2004). More-over, high levels of sediment-associated contaminants have beendetermined in coastal areas influenced by point sources of pol-lution, primarily from municipal and industrial sources (Grigo-riadou et al., 2008a; 2008b).

Recently developed research has reported that the prefectureof Kavala, northern Greece, has a higher rate of mortality (per1000) compared with the national average. Approximately 20%of these deaths are due to cancer, cardiac, and pulmonary dis-eases. This observation could be linked to local environmentalcontamination activities (Theophanides, M., et al., 2002; 2007;Theophanides T., et al., 2002). The negative influence of an-thropogenic activities on the local environment in the study areahas been demonstrated by other studies conducted in the KavalaPrefecture (Grigoriadou et al., 2008a; 2008b; Christoforidis andStamatis 2009; Papastergios et al., 2009c). The purpose of thepresent research was to study the distribution of several po-tentially toxic elements in the surface sediments of the east-ern Kavala coastal area (Filippos B port) and and make a first

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Figure 1. 1a) Simplified geological map of the study area (UTM Zone 35N); 1b) map showing the Filippos B port, the sea sediment sampling locations,the industrial activities and the land use/cover types of the study area.

assessment on the contribution of the local industrial activitieson the distribution of the studied potentially toxic elements.

Study Area

The study area is located in northern Greece and includesthe coastal part of the industrial zone of the city of Kavala(Figure 1). The main rock types in the area are (Figure 1a):

� gneisses, schists and amphibolites,;� marbles and limestones;

� granitic and granodioritic rocks; and� sedimentary deposits (Christofides et al., 1998; 2001; Kilias

and Mountrakis 1998; Kilias et al., 1999; Pe-Piper and Piper,2002).

In addition, several Pyrite-Blende-Galena (PBG), Mn, andFe mineralizations exist in the adjacent area (Filippidis et al.,1996; Vavelidis et al., 1996; 1997).

The mineral characteristics of the surface sea sediments ofthe study area could be attributed to the delta of the Nestos

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284 G. Papastergios et al.

Table 1. Concentrations (in g kg−1) of major elements in the sea sediments from Filippos B port, Kavala, Northern Greece

Sample # Ca Mg K Fe Na Si S Al P Cl Distance to coastline (m) Depth (m)

S100 51.2 7.2 3.0 10.4 3.4 0.2 1.3 6.0 2.6 2.3 550 15S101 28.8 2.4 0.5 1.4 2.0 0.2 0.2 0.9 0.4 0.5 120 13S102 3.6 1.8 0.7 2.2 2.8 0.2 0.4 1.3 0.7 0.5 170 3S103 6.9 6.6 4.0 12.3 5.1 0.2 0.9 7.0 0.5 2.3 440 11S104 13.4 9.2 5.5 15.3 6.6 0.1 1.3 9.9 0.6 3.6 800 15S105 13.3 9.2 5.4 15.2 6.6 0.1 1.2 9.8 0.6 1.4 220 4S106 23.1 4.4 1.0 3.4 2.1 0.1 0.4 2.0 0.6 0.7 430 12S107 25.7 4.6 1.4 4.7 3.9 0.1 0.8 2.7 1.0 1.3 210 10S108 35.7 5.7 2.3 10.6 4.7 0.2 1.5 5.4 1.8 2.7 420 6

Median 23.1 5.7 2.3 10.4 3.9 0.2 0.9 5.4 0.6 1.4 — —Mean 22.4 5.7 2.6 8.4 4.1 0.2 0.9 5.0 1.0 1.7 — —Minimum 3.6 1.8 0.5 1.4 2.0 0.1 0.2 0.9 0.4 0.5 — —Maximum 51.2 9.2 5.5 15.3 6.6 0.2 1.5 9.9 2.6 3.6 — —SD 14.2 2.5 1.8 5.2 1.7 0.0 0.4 3.3 0.7 1.0 — —

River and to local sources. According to Conispoliatis and Lyk-ousis (1986), the mineralogical composition of the sand fractionis >60% quartz-feldspars, >20% micas, 4%–8% amphiboles,0–15% biogenic carbonate and 0–3% pyroxenes, while therespective composition of the clay fraction is >70% illite,5%–16% kaolinite, 0–14% smectite and 0–10% chlorite. Thepredominant source of the clay minerals is the Nestos River.

The climate of the area shows the general southern Europecharacteristics with mild winters and warm summers. Averageannual rainfall ranges from 500–700 mm. The mean temperatureis 4.0◦ C in January and 24.5◦ C in July, while the prevailing windis from the SE (Hellenic National Meteorological Service, 1978;Petalas et al., 2004). Land uses in the area can be divided intofour categories: 1) agricultural, 2) uncultivated, 3) industrial, and4) residential (Figure 1b). The main industrial activities are thephosphoric fertilizer industry (PFI) and the Kavala Oil land fa-cilities. The former produces phosphoric fertilizers, pesticides,and other similar products, and its main byproduct is phosph-ogypsum, while oil desulphurization takes place in the latter.Some contaminants associated with the production of phospho-ric fertilizers and similar products (i.e., pesticides), as well asphosphogypsum, are Ba, Cd, Cu, P, Pb, Th, U, and Y (Rutherfordet al., 1996; Komnitsas et al., 1999; Chen et al., 2001; Kabata-Pendias and Pendias 2001; Carbonell-Barrachina et al., 2002;Villa et al., 2009); contaminants associated with the oil industryare Co, S, Th, and V (Kabata-Pendias and Pendias 2001). Otheractivities include some small enterprises that exploit and marketlocal marbles and the Xifias Fishery, which terminated its activ-ities while the present research was underway. Furthermore, inthe study area, near the Kavala Oil land facilities and the XifiasFishery, there are several uncontrolled landfill sites.

Materials and Methods

Sampling and Sample Preparation

Nine sampling sites were selected at variable distances fromthe coastline in the Filippos B port and adjoining areas to theeast and west (Figure 1 and Table 1). Surface sediment samples

were collected, using a sediment grab sampler, in January 2003.Samples were collected both in front of the major industrialactivities taking place in the area (S100, S102, S104, S105,S106, S107, S108) and farther away from them (S101, S103)(Figure 1). Samples S100, S106, S107, and S108 were collectedin front of the PFI facilities and the phosphogypsum dumps,while samples S102, S104 and S105 were taken in front of theKavala Oil land facilities and the Xifias Fishery. Sample S103was collected away from the industrial activities, at a point wherea water canal connects the aquacultures of the Xifias Fisherywith the Aegean Sea; therefore, it should not be considered as areference sample.

All samples were dried in an oven at 40◦C and fractionated us-ing a 200-µm sieve. The elements of interest were extracted fromthe <200-µm fraction because environmentally available traceelements mainly remain in this fraction (Fernandez-Turiel et al.,2001; Kabata-Pendias and Pendias 2001; Lucho-Constantinoet al., 2005; Papastergios et al., 2009a, c). The present researchwould have benefited from the collection of more samples overa longer period of time but unfortunately this was not possi-ble due to various limitations (i.e., accessibility of the area andothers). However, the study of these samples provides valuableinformation regarding the status of the sediments in the FilipposB port, as well as of the influence that the local industries haveon the surrounding environment.

The elements analyzed were extracted by using analyticalgrade HNO3 (Merck Suprapur [Darmstadt, Germany]). TheHNO3 extraction procedure is a very strong acid digestion thatdissolves metals that can be put into solution and thus allowsmeasurement of almost all elements that may become “environ-mentally available” (Pickering 1986; Walsh et al., 1997; Sastreet al., 2002). Analytical grade concentrated (65%) HNO3 wasselected in order to work with extreme analytical conditions andmaintain, at the same time, the compatibility of the leachate withthe input solution in inductively coupled plasma mass spectrom-etry (ICP-MS) and inductively coupled plasma optical emissionspectroscopy (ICP-OES) (direct determination after dilution).In the present work, a 0.1-g aliquot of each sample was placedin 14-mm diameter polyethylene tubes. Then, 2 mL of HNO3

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were added. All samples were placed in a rotary shaker for 24hours. This extraction avoids the polyatomic interferences pro-duced on analytes by other extraction agents commonly used(e.g., the Cl of aqua regia [3:1, HCl:HNO3] interferes withelements such as As and V). After the extraction procedure,the solution was filtered in 100-mL volume flasks. The vol-ume flasks were then filled with Milli-Q type deionized waterof 18.2 M�/cm. The final solution was placed in high-densitypolyethylene bottles, labeled, and stored in the dark at 4◦C untilanalysis.

Analytical Methods

Ten major element (Al, Ca, Cl, Fe, K, Mg, Na, P, S, and Si) and32 trace element (Ag, As, B, Ba, Cd, Ce, Co, Cr, Cs, Cu, Ga, Ge,Hg, La, Li, Mn, Mo, Ni, Pb, Rb, Sb, Se, Sn, Sr, Th, Ti, U, V, W,Y, Zn, and Zr) concentrations were determined in all samplesby ICP–OES and ICP–MS. A Perkin Elmer Optima 3200RLwith a Perkin Elmer Autosampler AS-90+ was used for theICP-OES analyses, while a Perkin Elmer Sciex Elan 6000 witha Perkin Elmer AS-91 automatic sampler (ICP-OES: Waltham,Massachusetts, USA; ICP-MS: Boston, Massachusetts, USA)was used for the ICP-MS analyses. The analyses were per-formed at the Scientific Technical Services of the University

Table 2. Concentrations (in mg kg−1) of trace elements in the seasediments from Filippos B port, Kavala, Northern Greece

Sample # Ag As B Ba Cd Ce Co Cr

S100 0.7 39.9 13.3 61.4 7.8 35.8 6.6 61.3S101 0.1 2.8 3.6 11.4 0.3 6.9 1.1 7.2S102 0.1 2.2 4.5 12.2 0.1 9.9 1.1 5.2S103 0.1 7.4 7.8 46.7 0.2 18.0 6.8 33.6S104 0.1 7.3 21.0 63.6 0.3 22.3 8.6 76.3S105 0.1 4.7 20.8 37.9 0.4 10.3 4.5 50.8S106 0.1 10.9 6.6 23.3 3.2 10.1 2.7 20.0S107 0.2 18.0 7.3 32.3 12.3 16.8 3.6 27.7S108 0.9 44.8 11.4 121.5 39.2 52.0 8.2 59.9

Median 0.1 7.4 7.8 37.9 0.4 16.8 4.5 33.6Mean 0.3 15.3 10.7 45.6 7.1 20.2 4.8 38.0Minimum 0.1 2.2 3.6 11.4 0.1 6.9 1.1 5.2Maximum 0.9 44.8 21.0 121.5 39.2 52.0 8.6 76.3SD 0.3 15.2 6.2 32.2 12.1 14.0 2.7 23.9

Sample # Cs Cu Ga Ge Hg La Li Mn

S100 2.1 103.2 3.0 0.1 0.3 21.7 13.1 172.8S101 0.4 3.7 0.4 0.01 0.04 3.7 2.1 71.1S102 0.6 2.3 0.7 0.02 0.03 5.4 3.7 45.6S103 3.4 18.9 4.0 0.1 0.1 8.2 21.5 229.2S104 4.2 67.9 5.2 0.1 0.1 10.7 25.6 264.2S105 2.4 9.9 2.4 0.02 0.04 5.4 12.0 123.7S106 0.8 12.4 1.0 0.02 0.03 5.6 4.4 130.1S107 1.1 30.6 1.4 0.03 0.2 10.0 6.1 110.3S108 1.7 119.1 2.8 0.1 0.4 34.1 10.9 148.2Median 1.7 18.9 2.4 0.03 0.1 8.2 10.9 130.1Mean 1.9 40.9 2.3 0.03 0.1 11.7 11.0 143.9Minimum 0.4 2.3 0.4 0.01 0.03 3.7 2.1 45.6Maximum 4.2 119.1 5.2 0.1 0.4 34.1 25.6 264.2SD 1.2 42.1 1.5 0.03 0.1 9.4 7.7 66.1

SD, standard deviation

Table 2. (Continued)

Sample # Mo Ni Pb Rb Sb Se Sn Sr

S100 0.5 26.6 147.3 32.4 0.3 2.7 1.0 90.1S101 0.1 3.5 34.1 5.1 0.05 0.6 0.4 48.8S102 0.1 3.7 8.5 6.6 0.04 0.6 0.3 6.8S103 0.2 22.3 29.2 44.6 0.04 0.6 0.9 23.3S104 0.2 40.9 37.3 60.6 0.1 0.6 1.1 34.0S105 0.2 25.8 121.3 28.2 0.04 0.6 0.5 33.8S106 0.1 9.8 49.0 11.5 0.1 0.6 0.4 29.2S107 0.2 12.6 274.5 15.4 0.1 1.2 0.5 39.8S108 0.9 23.0 93.7 25.7 0.9 3.1 1.1 77.3

Median 0.2 22.3 49.0 25.7 0.1 0.6 0.5 34.0Mean 0.3 18.7 88.3 25.6 0.2 1.2 0.7 42.6Minimum 0.1 3.5 8.5 5.1 0.04 0.6 0.3 6.8Maximum 0.9 40.9 274.5 60.6 0.9 3.1 1.1 90.1SD 0.3 11.6 79.0 17.4 0.3 1.0 0.3 24.7

Sample # Th Ti U V W Y Zn Zr

S100 5.1 204.8 4.9 24.4 0.1 25.5 219.1 2.2S101 1.9 49.6 0.3 4.0 0.05 3.3 15.4 0.5S102 6.4 77.4 0.3 5.7 0.05 4.0 11.8 0.4S103 6.3 495.5 0.5 28.2 0.1 5.7 59.8 1.3S104 7.1 503.3 1.0 36.5 0.3 7.1 100.5 2.3S105 3.8 235.1 0.4 18.8 0.1 3.7 37.4 0.6S106 2.5 102.9 0.3 9.0 0.1 5.5 57.5 0.7S107 2.9 129.8 0.6 11.0 0.2 11.3 165.1 1.1S108 4.7 232.2 2.5 20.3 0.2 45.7 538.2 2.7

Median 4.7 204.8 0.5 18.8 0.1 5.7 59.8 1.1Mean 4.5 225.6 1.2 17.5 0.1 12.4 133.9 1.3Minimum 1.9 49.6 0.3 4.0 0.05 3.3 11.8 0.4Maximum 7.1 503.3 4.9 36.5 0.3 45.7 538.2 2.7SD 1.8 159.1 1.5 10.4 0.1 13.5 157.2 0.8

SD, standard deviation

of Barcelona (SCT–UB), Spain. Details on ICP–MS analysiscan be found in Fernandez-Turiel et al. (2000). To confirm thequality of the results, the same procedure was applied to thereference material CANMET NRCC-MESS-2 as well as to ablank sample and four replicates of a randomly selected sample.The method used achieved analyses that were very satisfactoryfor the work objectives. Many elements exhibited relative stan-dard deviations (RSD) (percent relative deviation, n = 3) lessthan 3%, and some approximately 1% (e.g., Ca, Fe, Al, Mn,Pb, Sr). Exceptions were Cl, Ge, Hg, and Se, probably due totheir low concentrations (close to the quantification limits) inthe reference material. Regarding the extraction procedure’s re-peatability, many elements exhibited RSD values less than 5%.Similarly, some of the lowest RSD values (e.g., Se, Hg) could beattributed to the low concentrations of these elements. The re-covery percentage of the extraction procedure ranged from lessthan 10% (for elements such as Al, Si, and Sb, among others)to greater than 85% (for elements such as S, As, Cd, Co Cu, andZn, among others). Details are given in Papastergios (2008).

Results and Discussion

Major Elements

Concentrations and summary statistics regarding the major el-ements are given in Table 1. The elements Al, Cl, Fe, K,

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286 G. Papastergios et al.

Figure 2. 2a) Diagram showing the distribution of Al, Cl, Fe, K, Mg, Na and S in the study area (samples have been placed from east to west); 3b)diagram showing the distribution of Ca and P in the study area (samples have been placed from east to west).

Mg, Na and S show a similar distribution in the study area.Samples S101 and S102 have the lowest concentrations, whereasthe samples with the highest concentrations are S100, S104,S105, and S108, which are located in front of the industrial ac-tivities. In fact, Al, Cl, Fe, K, Mg, Na, and S have their highestconcentrations in front of all the industrial sources of the studyarea. (Figure 2a). In contrast, Ca and P have their highest con-centrations only in front of the PFI (Figure 2b). The distributionof the major elements, together with the type of activities of thelocal industries (i.e., production of phosphoric fertilizers by thePFI, desulphurization of crude oil by the Kavala Oil, aquacul-tures of the Xifias Fishery), strongly suggest that the elevatedconcentrations are associated with these anthropogenic activi-ties. However, Ca may be regarded as an exception because thesamples with the highest values are located near a large mar-ble outcrop (Figure 1a) or it could even be associated with thepresence of gypsum.

Trace Elements

Table 2 shows the concentrations and descriptive statistics forthe trace elements determined in the present study. For the cal-

culation of the descriptive statistics, values that were less thanthe detection limit, for each element, were substituted by halfits detection limit. All trace elements bear one common feature:They have their lowest concentrations in either sample S101 orsample S102, similar to the major elements. In contrast, the sam-ples with the highest concentrations are S108 and S104, takenin front of the PFI and the Kavala Oil facilities, respectively.

The trace elements determined in the present research canbe separated into two groups, according to their anthropogenicactivity source. The first group (Al, Cl, Fe, K, Mg, Na, P, S,Ag, As, Cd, Ce, Hg, La, Mo, Pb, Sb, Se, U, and Y) containsthose elements whose concentrations seem to be influenced bythe activities of the PFI and the presence of the phosphogypsumdumps. Examples of the distribution of the latter elements (Ag,As, Cd, Ce, Hg, La, Mo, Pb, Sb, Se, U, and Y) are presentedin Figures 3 and 4. The distribution of Pb is somewhat differ-ent (Figure 3b). Lead has its largest concentration (S107) infront of the area where the phosphogypsum dumps are located(Figures 1b). This behavior should probably be attributed to theformation of pyromorphite [Pb5(PO4)3Cl], because this min-eral is a typical precipitation product when both Pb and P arefound in a solution. Pyromorphite is a very stable phosphate

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Figure 3. 3a) Diagram showing the distribution of Cd and Se in the study area (Samples have been placed from east to west); 3b) diagram showing thedistribution of Sr and Pb in the study area (samples have been placed from east to west).

mineral that acts as an important buffer mechanism controllingthe migration and fixation of Pb in water, soils, sediments andwastes (Ryan et al., 2001; Manecki et al., 2006; Miretzky andFernandez-Cirelli 2008).

The rest of the elements (B, Ba, Co, Cr, Cs, Cu, Ga, Ge, Li,Mn, Ni, Rb, Sn, Th, Ti, V, W, Zn, and Zr) seem to be influencedby all the industrial activities taking place in the study area, thusforming a second group. These elements exhibit three peaks,one in front of each industrial activity of the Filippos B port.Examples of the distribution of the latter elements are given inFigure 5 (Figure 5a: Cs, Ga, Sn, and Zr; Figure 5b: B, Li, Ni, V,and Rb) and Figure 6 (Figure 6a: Ba, Cr, and Cu; Figure 6b: Mn,Ti, and Zn). Research conducted recently in the area of Kavalareveals the influence of the local anthropogenic activities regard-ing organic contaminants in the soils, sediments and sea waterof the study area (Grigoriadou et al., 2008a; 2008b), as wellas several potentially toxic elements in dust and roadside soils(Christoforidis and Stamatis 2009) and arsenic in uncultivatedsurface soils (Papastergios et al., 2009c).

The distribution of Sr differs from the rest of the trace ele-ments, but is similar to the distribution of Ca, which would sug-

gest that its distribution is probably affected by the same factorsinfluencing the distribution of Ca. Furthermore, together withCa and S, Sr is a typical component of gypsum.

Although the relationship between the industrial activitiesand the elevated concentrations of the elements analyzed seemsstrong, it must not be forgotten that in the inland part of thestudy area, ore occurrences (i.e., PBG, Mn, Fe) are widespreadand could contribute to the observed high metal concentrations(Figure 1). However, because the predominant source of min-erals is the Nestos River and to a lesser extent local sources(Conispoliatis and Lykousis 1986), the ore association seemsunlikely, especially since the elemental content of the NestosRiver sediments and of the surrounding rocks are found to bewithin normal ranges (Papastergios et al., 2009a; 2009b; 2010).

Nonetheless, the observed elevated concentrations seem tobe restricted to a small section, in front of the coastal industrialactivities. The reason for this constraint could be attributed tothe physicochemical parameters of the area. Filippos B port issituated between two large estuarine sites, those of the NestosRiver to the east and the Strymonas River to the west. Thus, pHchanges that take place during estuarine water mixing could lead

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288 G. Papastergios et al.

Figure 4. 4a) Diagram showing the distribution of Ag, Hg, Mo, and Sb in the study area (samples have been placed from east to west); 4b) diagramshowing the distribution of As, Ce, La, and Y in the study area (samples have been placed from east to west).

to coagulation, flocculation, and coprecipitation of the elementcompounds (Lu et al., 2005). Furthermore, because of waveaction, there is a longshore transportation of sand from east towest that could contribute to the constraint of the elevated val-ues within the Filippos B port (Papastergios et al., 2006). Thelatter phenomenon has also been observed for trace elementdistribution in the seawater of the study area (Georgakopouloset al., 2002), as well as for the distribution of organic contami-nants (Grigoriadou et al., 2008a; 2008b).

Bivariate Analysis

Bivariate analyses were conducted by studying the Pearson prod-uct moment correlation coefficients (PMCCs) (r), which are ameasure of the correlation (linear dependence) between twovariables X and Y , giving a value between +1 and −1 inclusive.The calculation of the PMCCs, at a significance level of p =0.01, revealed that none of the determined elements show signif-icant negative correlation with the other elements. Aluminum,Fe, K, Mg, Na, and S have high positive coefficients (0.81 <

r < 0.99). Chlorine is also correlated with Al, Fe, K, Mg, Na,

and S at a significance level of 5% (p = 0.05). Finally, a strongpositive correlation is also noted between Ca and P (r = 0.81).

Bivariate analyses confirmed that Ag, As, Ce, Cd, Hg, La,Mo, Sb, Se, U, and Y are positively correlated (0.82 < r <

0.99), reaffirming the common distribution of these elements inthe study area (Figures 3 and 4). All the latter elements (Ag,As, Cd, Ce, Hg, La, Mo, Pb, Sb, Se, U, and Y) belong to thefirst group of trace elements. On the contrary, Pb has no signifi-cant correlation, neither with the previously mentioned elementsnor with the trace elements or with the major elements, whichsuggests that the Pb distribution in the study area (Figure 3b)is controlled by different factors than those controlling the dis-tribution of the others. Most probably this feature has to do withthe presence of pyromorphite. The only other element that hasno major correlation with the rest of the elements is Si. How-ever, this behavior may be attributed to the extraction methodselected because HNO3 extraction is not designed to attack alu-minosilicate structures.

As noted in the first group, most elements in the second groupexhibit high, positive correlation coefficients among them, in-dicating that their distribution is controlled by common factors,which probably have to do with the activities of all the local,

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Figure 5. 5a) Diagram showing the distribution of Cs, Ga, Sn and Zr in the study area (samples have been placed from east to west); 5b) diagram showingthe distribution of B, Li, Ni, Rb, and V in the study area (samples have been placed from east to west).

coastal industries. Due to the restricted number of samples, theresults of the bivariate analysis can only be suggestive. However,an attempt was made to explain the elements with a commonorigin and to identify their sources.

Overall Assessment of Sediment Quality

It is a well known fact that, in Europe, the Netherlands has takenthe lead over most countries in that the Netherlands has clear,

comprehensive legislation regarding contaminated land and theenvironment (United Kingdom Quality Ash Association, 2003;Barbiroli et al., 2004; Boekhold 2008; Breure et al., 2008). As aresult, many researchers use the values suggested by the DutchList as guidelines for comparisons with their own datasets (i.e.,Schulze et al., 1997; Wilcke et al., 1998; Sepulveda et al., 2010).According to the List, optimum levels are those in which thevalue of the contaminant falls below the listed value, implying itdoes not pose a risk to the environment; action level values are

Table 3. Comparison between the concentrations (in mg kg−1) suggested as optimum or action level of the elements included in the Dutch List and theconcentrations that these elements have in the present study

Dutch ListElement Optimum Action Values > optimum level Sample #s Values > action level Sample #s

As 29 55 2 S100, S108 1 S108Ba 200 625 0 — 0 —Cd 0,8 12 4 S100, S108, S107, S106 2 S108, S107Co 20 240 0 — 0 —Cr 100 380 0 — 0 —Cu 36 190 5 S100, S108, S107, S106, S104 0 —Hg 0,3 10 1 S100 0 —Mo 10 200 0 — 0 —Ni 35 210 1 S104 0 —Pb 85 530 5 S100, S108, S107, S106, S105 0 —Zn 140 720 3 S100, S108, S107 0 —

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290 G. Papastergios et al.

Figure 6. 6a) Diagram showing the distribution of Ba, Cr and Cu in the study area (samples have been placed from east to west); 6b): diagram showingthe distribution of Mn, Ti, and Zn in the study area (samples have been placed from east to west).

those that exceed the listed value and require further investiga-tion and some form of remediation. When mean concentrationsof two elements exceed the listed value, corrective action isrequired. A comparison between the guideline levels on theDutch List and the concentrations at Filippos B port showshigher values than the optimum levels for As, Cd, Cu, Hg, Ni,Pb, and Zn; whereas action levels are exceeded for As and Cd.Only four elements (Ba, Co, Cr, and Mo) have all concentrationslower than the proposed limits (Table 3). The two samples (S107and S108) with Cd concentrations higher than the suggestedaction level are located in front of the PFI facilities (Figure 1b).

Conclusions

The study of the sediments of Filippos B port indicates thatalmost all the elements determined display elevated concentra-tions in front of the coastal anthropogenic activities. All ele-ments can be divided into two groups according to their anthro-pogenic activity source. The first group includes Al, Cl, Fe, K,Mg, Na, P, S, Ag, As, Cd, Ce, Hg, La, Mo, Pb, Sb, Se, U, and Y.This group of elements exhibits the highest concentrations, butonly close to the PFI facilities and the phosphogypsum dumps.The distribution of Pb is probably influenced by the presence

of pyromorphite. In contrast, the elevated concentrations of theelements belonging to the second group (B, Ba, Co, Cr, Cs, Cu,Ga, Ge, Li, Mn, Ni, Rb, Sn, Th, Ti, V, W, Zn, and Zr) are influ-enced by the activities of all the coastal industries of the studyarea. The distribution of Ca and Sr is, possibly, influenced bythe nearby presence of marble outcrops and the presence of gyp-sum. Bivariate analysis has revealed that among the elements ofeach group high correlation coefficients exist. Although the el-evated concentrations seem to be restricted to an area directly infront of the coastal industrial facilities, a periodical monitoringof this area is recommended in order to control the evolutionof all elemental concentrations in the sediments of this area ofAegean Sea. Further monitoring data with sampling at greaterdistances from the coastline, mineralogy of the sediments, pH,redox potential, etc. would contribute in the elucidation of thefactors controlling the distribution of the studied contaminants.

Acknowledgments

The authors would like to acknowledge the technical assistanceprovided by the personnel of the Faculty of Geology of the Uni-versity of Barcelona, the SCT–UB and ICTJA–CSIC, Barcelona(Spain). During the research Georgios Papastergios was holding

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a scholarship from the Greek State Scholarships Foundation(IKY). This work was partially carried out in the framework ofPEGEFA Research Consolidated Group (Ref. 2009 SGR 972),funded by AGAUR-DURSI, Generalitat de Catalunya. The PFIprovided a small vessel to assist with the collection of samples.The authors gratefully acknowledge the comments of the anony-mous reviewers that helped to improve the original manuscript.The English of the final draft of the manuscript was improvedby Frances Luttikhuizen.

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