Available online at www.sciencedirect.com

Environmental Pollution 151 (2008) 231e242www.elsevier.com/locate/envpol

Molecular indicators for pollution source identification in marine andterrestrial water of the industrial area of Kavala city, North Greece

A. Grigoriadou a, J. Schwarzbauer b,*, A. Georgakopoulos a

a Department of Mineralogy-Petrology-Economic Geology, School of Geology, Aristotle University of Thessaloniki, 54124 Thessaloniki, Greeceb Institute of Geology and Geochemistry of Petroleum and Coal, Aachen University of Technology, Lochnerstraße 4-20, 52056 Aachen, Germany

Received 22 August 2006; received in revised form 9 January 2007; accepted 26 January 2007

Organic contaminants were used to estimate the state of the pollution and to identify sources in an area impacted bynumerous anthropogenic activities.

Abstract

Eight terrestrial and four marine water samples were collected from the industrial section of the city of Kavala in northern Greece to determinethe occurrence and distribution of organic contaminants, as well as to identify the molecular markers of different emission sources. The sampleswere analyzed by means of non-target screening analyses. The analytical procedure included a sequential extraction of the samples, GC-FID, GC/MS analyses, and additional quantitative analyses of selected pollutants. The results show a wide variety of compounds including halogenatedcompounds, technical additives and metabolites, phosphates, phthalates, benzothiazoles, etc. A close relationship between many of the contam-inants and their emission sources was determined based on their molecular structures and information on technical applications.� 2007 Elsevier Ltd. All rights reserved.

Keywords: Coastal area; Organic contaminants; GC/MS screening analyses; Industrial emissions; Source identification

1. Introduction

Analytical investigations of anthropogenic organic contam-ination in the Greek environment began only recently, and thefield is still in its early stages. Several studies have been per-formed on surface water systems of Northern Greece, e.g. lakesand rivers, to characterize the pollution by organic contami-nants with particular consideration of volatile and semivolatileorganic compounds, organochlorine insecticides, and herbi-cides. These studies revealed contamination levels similar toor below the quality standards set by the European Union(E.U.) and other European countries (e.g. EC, 2001; Golfino-poulos et al., 2003; Kostopoulou et al., 2000; Lekkas et al.,2004; Manoli et al., 2000; Nikolaou et al., 2002).

* Corresponding author. Tel.: þ49 241 809 5750.

E-mail addresses: grigoriadou@lek.rwth-aachen.de (A. Grigoriadou),

schwarzbauer@lek.rwth-aachen.de (J. Schwarzbauer), ageorgak@geo.auth.gr

(A. Georgakopoulos).

0269-7491/$ - see front matter � 2007 Elsevier Ltd. All rights reserved.

doi:10.1016/j.envpol.2007.01.053

The information on organic pollutants or anthropogenicmarker compounds in the Greek aquatic environment is cur-rently limited to only a few priority pollutants and commoncontaminants. A comprehensive description of individual mo-lecular indicators for pollution source identification has yet tobe reported, hence, detailed studies of aquatic pollution thatlink specific pollutants to their emission source (e.g., munici-pal sewage effluents, industrial effluents, etc.) are rare.

This research focused on very detailed organic-geochemicalinvestigation of water samples derived from a coastal-industrialzone in the northern Aegean Sea (see chapter 2.1) suspected tobe influenced by several types of anthropogenic activities. Theresearch objective was to identify organic molecular indicatorsappropriate for pollution source identification and to determinethe spectrum of contaminants in the area. Previous studies inthe area reported high values for marine water concentrationsof the trace elements iron, phosphorous and manganese in sam-ples from the coastline close to a fertilizer plant (Georgakopou-los et al., 2002; Papastergios et al, 2004); however, they did not

232 A. Grigoriadou et al. / Environmental Pollution 151 (2008) 231e242

analyze the organic pollution. More recently, the Coastal Pro-tection and Restoration Division (CPR) of National Oceanicand Atmospheric Administration (NOAA) of USA presentedscreening concentrations for inorganic and organic contami-nants in various environmental media, but these are only usefulfor preliminary screening purposes (NOAA, 2006). The indus-trial activities in this area generate emissions that have led toa possible damage to the aquatic ecosystem. Therefore, it isnecessary to understand the full extent of contamination in or-der to determine possible long-term detrimental effects to theenvironment, to the people nearby, etc.

This paper presents a detailed screening analysis of lowmolecular weight organic pollutants in marine and terrestrialwater samples in the coastal industrial area of Kavala. GC/MS non-target screening analyses were performed not onlyto evaluate the level of organic pollution, but also to revealspecific markers characterizing the different emission sources.Furthermore, emission sources, pathways and the spatial dis-tribution of individual organic contaminants are discussed.

2. Materials and methods

2.1. Area description and sampling

The industrial zone of Kavala is located in a coastal zone 15 km to the east

of Kavala, in Northeast Greece. The main industrial activities of the area are

related to the petrochemical industry, fertilizer industry and fishery trade.

The petrochemical’s mainland facilities accommodate a crude oil treatment fa-

cility, sulfur and natural gas liquids (NGL) extraction facilities as well as stor-

age of these products (Georgakopoulos et al., 1995; Speel, 1982). The fertilizer

plant facilities include a liquid ammonia storage tank, installations for the stor-

age, bagging, palletizing, in-plant handling and loading of fertilizers on ships

and trucks and a company-owned harbor for receiving deliveries of raw mate-

rials and for the loading of intermediate goods and fertilizers. The plant pro-

duces nitrogenous fertilizers, which are based on various combinations of

nitrogen, phosphorous and potassium, and uses ammonia as well as phosphoric,

sulfuric, and nitric acids. The fishery’s accommodations include production and

storage areas, freezing compartments, and automatic tin ware production units.

In addition, the industrial zone is also affected by extended agricultural activ-

ities of the surrounding area and, furthermore, by uncontrolled dumping of

household wastes.

In January 2003, 12 water samples were collected from the industrial zone

of Kavala (Fig. 1). Four marine water samples (M1, M2, M3 and M4) were

collected between 500 and 1000 m offshore, the industrial plants at a depth

of approximately 50 cm. The total volume of the marine water samples col-

lected was 2 L. Eight terrestrial water samples (S1, S2, S3, S4, S5, S6, S7

and S8) were taken from canals and marshes (water accumulations) located

between the petrochemical plant and the fishery factory at a depth of 20 cm.

Three of the canal samples (S2, S4 and S6) were taken directly from the canal

where the petrochemical industry discharges its effluents. One sample (S7)

was collected from the canal where the fishery discharges its effluents. The

rest of the terrestrial water samples (S1, S3, S5 and S8) were collected from

water accumulations, in which the uncontrolled dumping of solid waste was

observed. The total volume of the terrestrial water samples collected was 1 L.

All samples were collected free of air bubbles in dark glass flasks that were

intensively pre-cleaned with twice-distilled water, acetone and hexane. The

samples were stored in the dark at a temperature of approx. 4 �C and were

extracted within two weeks of sampling.

2.2. Analyses

A sequential liquid/liquid extraction procedure was applied to approxi-

mately 1 L of the canal and marsh water samples and 2 L of marine water

samples using dichloromethane (DCM). The analytical procedure is illustrated

in Fig. 2. Each extraction step was carried out in a separating funnel with

50 mL of DCM. The second extraction was applied to the pre-extracted water

samples after the addition of 2 mL of concentrated hydrochloric acid, pre-

cleaned by an intense extraction with n-hexane. Next, the organic layers

were dried separately by filtration over 1 g of anhydrous granulated sodium

sulfate and were added to 50 mL of internal standard solution containing

5.1 ng/mL of d10-anthracene (m/z 188). Prior to gas chromatographic (GC)

and gas chromatographic e mass spectrometric (GC/MS) analyses the extracts

were reduced to a final volume of approximately 20 mL by rotary evaporation

at room temperature. Acidic compounds in the second extract were methylated

with diazomethane.

The GC analysis was carried out on a GC6000 gas chromatograph (Carlo

Erba, Vega Series 2, Milano, Italy) equipped with a 30 m � 0.25 mm

i.d. � 0.25 mm film DB1 fused silica capillary column (SGE, Germany). The

end of the capillary column was split to lead the eluate separately to a flame

ionization detector (FID) and an electron capture detector (ECD). Chromato-

graphic conditions consisted of a 1 mL split/splitless injection at 60 �C oven

temperature (injector temperature 270 �C, splitless time 60 s), a 3 min hold,

and a programmed temperature increase of 3 �C/min to 300 �C. The hydrogen

carrier gas velocity was 40 cm/s.

GC/MS analysis was performed on a Finnigan Trace MS, ThermoQuest

(Egelsbach, Germany) linked to a Carlo Erba, HRGC 5160 gas chromatograph

equipped with a 25 m � 0.22 mm i.d. � 0.25 mm film BPX5 (SGE, Germany).

The chromatographic conditions were the same as in GC analysis. The helium

carrier gas velocity was 2 cm/s at a source temperature of 200 �C. The MS was

operated in electron impact ionization mode (EIþ, 70 eV) scanning from 35 to

500 Da at a rate of 1 s/decade and an inter-scan time of 0.1 s.

Identification of individual compounds was based on the comparison of

EIþ-mass spectra and GC retention times with those of reference compounds.

The first evidence of identification was derived from the comparison of mass

spectra with mass spectral data bases (NIST/EPA/NIH Mass Spectral Library

NIST02, Wiley/NBS Registry of Mass Spectral Data, 7th Ed., electronic ver-

sions). The small disagreements between compound retention times were cor-

rected by the retention times of the internal standard.

Quantitative data of selected target compounds were obtained by integra-

tion of specific ion chromatograms extracted from the Total Ion Chromato-

gram (TIC). Dry masses, injection volume and analysis volume were taken

into account and corrected by comparing the internal standard abundances

with those in the calibration mixture. An external four-point-calibration, gen-

erated from a mixture of reference compounds, was used for quantification.

The detection limit was approximately 1 ng/L; however, no attempt was

made to quantify components at concentrations less than 5 ng/L.

3. Results and discussion

The organic-geochemical analyses of 12 water samples de-rived from the coastal area near Kavala (Fig. 1) provided com-prehensive spectra of contaminants and allowed for a detaileddescription of the organic pollution in the area. Two groups ofanthropogenic compounds were distinguished: (a) compoundsshowing widespread distribution showing no specific source;and (b) compounds implicating specific sources. Many ofthe substances are well known contaminants of surface andwaste waters and their associated sediments (e.g. Labunskaet al., 2000; Oros and David, 2002; Ricking et al., 2003;Schwarzbauer et al., 2000). All could be attributed to thechemical classes of halogenated aromatics and aliphatics,phosphates, phthalates, benzothiazoles, esters, polycyclic aro-matic hydrocarbons, alcohols, phenols and ethers. Severalcompounds belong to specific groups of technical additivesor agents, e.g. plasticizers, pesticides or personal care prod-ucts. Individual compounds were selected for further quantita-tive analyses (Tables 1 and 2) based on their potential to

233A. Grigoriadou et al. / Environmental Pollution 151 (2008) 231e242

N

City

M1

M3

M4

M2

AEGEAN

N

Nea KarvaliCity

S6

S3

S4

M4

M3

0 500m

1000m0

PetrochemicalIndustryFertilizer

IndustryFishery

N

KavalaCity

NeaKarvali

M1

M3

M4

M2

AEGEAN SEA

N

PetrochemicalInd. Fishery

M4

M3

Old HighwayKavala-Xanthi

AEGEAN SEA0 500m

1000m0

National HighwayKavala - Xanthi

S1

S2

S7

S5

S8

Fig. 1. Sampling locations of water samples in the industrial area of Kavala city.

identify specific sources of the contaminants. In order to com-pare compounds found near Kavala to those reported for otherregions, all the identified compounds are presented in detailedin Table 3.

The compounds identified are discussed with respect totheir emission sources and pathways. Additionally, a compari-son with limit values of quality standards of European Union(EC, 2001) and/or maximum limits by Environmental Protec-tion Agency of United States (US EPA) was made in order togive a first risk assessment.

3.1. Point source indicators

The most important group of contaminants included thesource indicators. The corresponding source specificity wasbased on significant maxima of concentration profiles or onthe unique appearance of those compounds in water samples

1 L surface water samples2 L marine water samples

Sequential liquid-liquid extraction

a) 50 mL dichloromethaneb) 50 mL dichloromethane (pH 2, conc. HCl)

Addition of internal standard (Anthracene)Concentration up to analysis volume (20 - 50 µL)

Derivatisation of acidous little bit with TMSH/MSTFA

Gas chromatographic analysis

with simultaneous FID/ECD - detection

Gas chromatography / mass spectrometry (GC / MS)

EI+ fullscan mode

Fig. 2. Analytical procedure used for non-target screening analyses of water

samples.

directly linked to known local emission sources as describedabove.

Sample S4 was collected in front of the petrochemical plantand was the first sample that directly corresponded with a localindustrial emission source. Tribromomethane (bromoform)was identified solely in this sample with an extremely highconcentration of 98 mg/L. The US EPA has set a MaximumContaminant Level (MCL) of 1 mg/L for bromoform for chlo-rinated drinking water. Hence, our results exceeded this valueby a factor of approx. 100 (A.T.S.D.R., 2006). Historically,bromoform was used as solvent, flame retardant, or synthesismaterial, but today is used mainly as laboratory reagent. Addi-tionally, bromoform is known to be a bromination by-productduring drinking water treatment. The occurrence of bromo-form cannot be directly linked to the chemical processes inuse by the oil plant, but its restricted local appearance in thesamples indicates a local source discharge. Bromoform hasbeen detected as a contaminant linked to petrochemical plantemissions in Taiwan (Kuo et al., 1996).

A second local emission source, the fishery plant, was asso-ciated with terrestrial water sample S3, which was collectedfrom the canal directly in front of the industrial site. Severalsulfur and nitrogen containing compounds were identified ex-clusively in sample S3. The chromatogram of the first fractionfrom sample S3 is illustrated in Fig. 3 and the correspondingmolecular structures in Fig. 4. The nitrogen compound indolewas determined at its highest concentration in this sample(Fig. 3, peak number 8). Indole is described as a degradationproduct of nitrogen-containing amino acids under anaerobicconditions (Higashio and Shoji, 2003). It is used as a constitu-ent of artificial fragrances and flavors and is naturally formedunder conditions of oxygen depletion and organic nitrogen en-richment. Previous environmental studies have detected indolein urban wastewater in Copenhagen (Denmark) and in leakageand seepage water samples from a German waste deposit land-fill (Eriksson et al., 2003; Schwarzbauer et al., 2002).

Other compounds found were related to a group of oligo-sulfides (dimethyltrisulfide and dimethyltetrasulfide) (Fig. 3,peak numbers 2 and 6). This group generally appears under

Table 1

Quantitative data of selected contaminants in terrestrial water samples (ng/L)

S6 S7 S8

25

150

760

21

21 21

14 14

1600 410 570

710 91 700

65 63

6

67 560 460

410

1200

210

1100

350 300

360 33 150

480

1200

150 130 460

1700 3400 56,000

10 85 280

65 1700

77

54 96 130

52

73

23

4A

.G

rigoriadouet

al./

Environm

entalP

ollution151

(2008)231

e242

S1 S2 S3 S4 S5

Halogenated compoundsTrichloropropenea 68

1,1,2,2-Tetrabromoethane

2-Iodophenol

4-Chlorobenzoic acidb

Tribromomethane 98,400

Technical additives and metabolites

Methyl diethyldithiocarbamateb 27 34 58 38 12

Methyl dimethyldithiocarbamateb 59 62 28

(1-Hydroxycyclohexyl)phenylmethanone 1700 2100 470 400 450

2,4,7,9-Tetramethyl-5-decine-4,7-diol 460 120 170 150 300

2,6,6-Trimethyl-2-cyclohexen-1,4-dione 110 39 48 78

Phosphates

Tris(chloropropyl)phosphates 1650

Diphenylphosphatec

Tri-n-butylphosphate 5 510 21 1500

Benzothiazoles

Benzothiazole 690 50 180

2-Methylthiobenzothiazole 1300 330

2-Hydroxybenzothiazole 60,900

Sulfides, sulfones,

sulfonic acids and sulfonamides

Dimethyltrisulfided 10,700

Dimethyltetrasulfided 6400

Dimethylsulfone 6600

Di-p-tolylsulfone

4-Hydroxybenzenesulfonic acide 150

N-Butylbenzenesulfonamide 63 550

o-Toluenesulfonamide

PAHsNaphthalene 32 42

Esters

Di-iso-butyl adipate 1200 670 290 120 1000

Ethyl cinnamate

4-Methylbenzoic acid methylester

Hexanedioic acid bis(2-ethylhexyl) ester 130 490 870

2-Ethylhexanoic acid 2-hydroxypropyl esterf 1700 550 7700 700 1300

2,4,4-Trimethylpentan-1,3-dioldi-iso-butyrateg 72 25 88 7 34

Isopropyl myristate 35 17

Nitrogen containing compounds

a-Phthalimidoacetoneh

Indole 162,000

2-Indolinone 2400

Ketones

2,6-Di-tert-butyl-4-hydroxy-4-methyl-2,5-cyclohexadienonei 160 110 14 64 220

1-Phenyl-2-butanonej

1-Phenyl-2-pentanonei

235A. Grigoriadou et al. / Environmental Pollution 151 (2008) 231e242

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natural conditions with depleted oxygen content and highamounts of hydrogen sulfide. For example, these compoundswere identified during the Peridinium algae bloom season inthe lake of Galilee in Israel, indicating an indirect role inthe algal bloom radiation of malodors (Ginzburg et al.,1999). The oxidized sulfur compound dimethylsulfone(Fig. 3, peak number 1), was also identified in the sampleS3. Dimethylsulfone is produced in the atmosphere by oxida-tion of the corresponding sulfide, and it occurs naturally in thehuman body and in some common foods. However, it is alsoused in industry. Another sulfur-containing compound is 4-hy-droxybenzenesulfonic acid (Fig. 3, peak number 3). Informa-tion on its environmental occurrence generation, or technicalapplication is rarely reported, but it has been described asa degradation product of the dye compound tropaeoline(Roy et al., 2003). The last specific contaminant, 2-hydroxy-benzothiazole (Fig. 3, peak number 12), appeared in severalwater samples investigated but exhibited an elevated concen-tration for sample S3. This compound is known as an oxida-tion product of benzothiazoles, which is widely used in therubber industry and other technical processes.

Although the nitrogen and sulfur compounds appeared onlyin the sample derived near the fishery plant (sample S3), it wasnot possible to attribute them to the technical applications oractivities of the fishery plant based on their structural proper-ties alone. Hence, it was not possible to unambiguously iden-tify the origin of emitted contaminants. The anaerobicconditions of this part of the aquatic environment, possiblycaused by the high amounts of organic contamination, are in-dicated by the appearance of specific compounds, e.g. indole.Additionally, oligosulfides are frequently produced underanoxic conditions or in hypertrophic aquatic systems. The occur-rence of nitrogen and sulfur compounds might reflect a secondaryeffect of fish plant derived emissions of high organic pollutants,leading to oxygen depletion and intensive algae growth. Allthese effects are harmful to the aquatic environment.

A third emission source was identified in sample S7,collected from a water accumulation in the area between thepetrochemical industry and the fishery plant. In this wateraccumulation a large and uncontrolled discharge of householdrubbish was evident. This contamination was reflected by avariety of individual compounds known to be rubbish cons-tituents like common technical additives, constituents ofpersonal care products and plasticizers (and their degrada-tion products). An uncommon phthalate-derived compound,mono-n-butylphthalate, is the first hydrolysis product ofdibutylphthalate and dominated the extract. Ethyl cinnamate,a known UV-inhibitor in sun creams and other cosmeticswas also found. The xenobiotic compound diphenylphosphateand the technical solvent 1,1,2,2-tetrabromoethane appearedin low concentrations. A further group of specific compoundscan be partially attributed to the preparation of pesticides, e.g.o-toluenesulfonamide, o-phenylphenol, 4-chlorobenzoic acidand diphenyl ether (Kacprzak, 1978; Schwarzbauer et al.,2002).

A final group of substances was found in sample S7 andincluded compounds such as di-p-tolylsulfone, 2-iodophenol,

236 A. Grigoriadou et al. / Environmental Pollution 151 (2008) 231e242

Table 2

Quantitative data of selected contaminants in marine water samples (ng/L)

M1 M2 M3 M4

Halogenated compounds

Trichloropropenea 6 7

Technical additives and metabolites(1-Hydroxycyclohexyl)phenylmethanone 160 110 440 120

2,4,7,9-Tetramethyl-5-decine-4,7-diol 16 17 23 18

2,6,6-Trimethyl-2-cyclohexen-1,4-dione 8 8 7

PhosphatesTris(chloropropyl)phosphates 36

Tri-n-butylphosphate 26 17 16 10

BenzothiazolesBenzothiazole 21 35 10

Sulfides, sulfones, sulfonic acids and sulfonamides

N-Butylbenzenesulfonamide 20

EstersDi-iso-butyl adipate 6

Hexanedioic acid bis(2-ethylhexyl) ester 80 49

2-Ethylhexanoic acid 2-hydroxypropyl esterb 160 200 5 250

2,4,4-Trimethylpentan-1,3-dioldi-iso-butyratec 82 30 5 43

Isopropyl myristate 9 15 130 5

Nitrogen containing compounds

Indole 350

Ketones2,6-Di-tert-butyl-4-hydroxy-4-methyl-2,5-cyclohexadienoned 10 6 5 7

Alcohols, phenols and ethers

Phenol 7900 1600

3-tert-Butyl-4-hydroxyanisole 32 11 170 16

Phthalates

Di-iso-butylphthalate 300 120 170 54

Di-n-butylphthalate 700 430 370 510

Benzylbutylphthalate 6000 290 300

Bis(2-ethylhexyl)phthalate (DEHP) 830 1300 650 600

a Calibration based on response factor of 1,1,2,2-tetrabromoethane.b Calibration based on response factor of hexanedioic acid bis(2-ethylhexyl) ester.c Calibration based on response factor of isopropyl myristate.d Calibration based on response factor of 1-hydroxycyclohexyl phenyl ketone.

1-phenyl-2-pentanone, 1-phenyl-2-butanone, a-phthalimidoa-cetone and 4-methylbenzoic acid methylester, for which themolecular structure indicated a possible anthropogenic origin.However, reports on their environmental occurrence is limitedand, therefore, information on their environmental relevance islacking.

Finally, the herbicide S-ethyl-N,N-hexamethylenethiocarba-mate (Molinate), characterized the typically diffuse impactfrom surrounding agricultural activities. However, the occur-rence of this source specific marker compound is restrictedto samples S7 and S8. The concentrations detected in S7and S8 were high (2.3 mg/L) yet no further samples were con-taminated indicating only a local and restricted application ofthe pesticide. This concentration level is comparable to datareported for Lake Biwa (Japan) and for surface and groundwater in Portugal (Sudo et al., 2002; Cerejeira et al., 2003).

3.2. Specific compounds for non-point source emissions

In contrast to the previous group of source specific com-pounds, many anthropogenic contaminants with wider spatialdistribution were identified. This group includes several com-pounds of high environmental interest that are important

indicators for the state of pollution in the aquatic environmentaround Kavala.

Phthalate based plasticizers, well-known and ubiquitous pol-lutants resulting from their persistence and long range transport,were frequently detected. Bis(2-ethylhexyl)phthalate (DEHP)showed a widespread distribution with the highest concentrationobserved in sample S2. The compounds di-iso-butylphthalate,di-n-butylphthalate and 2-ethylhexanoic acid 2-hydroxypropylester appeared in all of the samples investigated with the highestconcentrations in samples S3 and S8. The compound 3-tert-butyl-4-hydroxyanisole had a similar widespread distributionwith the highest concentrations in sample S8. The concentra-tions of the phthalates are comparable to reported data in otherpolluted aquatic systems, e.g. in water samples from the Nether-lands (Peijnenburg and Struijs, 2005).

Some compounds were observed in roughly equal con-centrations in nearly all of the samples implying a wide-spread, homogenous distribution. For example, hexanedioicacid bis(2-ethylhexyl) ester was observed in almost all ofthe samples without any accumulation tendency. This com-pound is widely used as a plasticizer and a constituent incommercial products such as lubricants and cosmetics. An-other technical additive identified in all of the water samples

237A. Grigoriadou et al. / Environmental Pollution 151 (2008) 231e242

Table 3

Usage or formation of the compounds identified in Kavala area in comparison with other reported cases (country, concentration, type of sample and bibliography)

Compound Usage/Formation Highest concentration

and sample identified

in Kavala area

Country, concentration,

sample type

Reference

Trichloropropene e 68 ng/L, S1 e e1,1,2,2-Tetrabromoethane Technical solvent 150 ng/L, S7 e Chemicalland21, 2006

2-Iodophenol e 760 ng/L, S7 e

4-Chlorobenzoic acid Widespread usage 21 ng/L, S7 e Vargas, 2002;

Chemicalland21, 2006

Tribromomethane Widespread usage 98.4 mg/L, S4 Taiwan, 2.07 mg/L, river

water

Kuo et al., 1996

Methyl diethyldithiocarbamate Degradation products of

xenobioticals

58 ng/L, S3 e Dalvi et al., 2003;

Pike et al., 2001; Loo and Clarke,

2000; Rannug and Rannug, 1984

Methyl dimethyldithiocarbamate Degradation products of

xenobioticals

62 ng/L, S3 e Dalvi et al., 2003;

Pike et al., 2001; Loo et al., 2000;

Rannug and Rannug, 1984

(1-Hydroxycyclohexyl)

phenylmethanone

Initiator 2.1 mg/L, S2 e Kim et al., 1999

2,4,7,9-Tetramethyl-5-decine-

4,7-diol

Dye compound 710 ng/L, S6 Germany, 1.5 mg/L, river

water

Dsikowitzky et al., 2004

2,6,6-Trimethyl-2-cyclohexen-

1,4-dione

Personal care products 110 ng/L, S1 Germany, 90 ng/g, river

sediment

Kronimus et al., 2004

Tris(chloropropyl)phosphates Widespread usage 1.7 mg/L, S1 Germany, 54 ng/L, river

water

Andresen and Bester, 2006;

Diphenylphosphate Widespread usage 150 ng/L, S7 e e

Tri-n-butylphosphate Widespread usage 1.5 mg/L, S5 Germany, 1.5 mg/L, river

water

Schwarzbauer and Heim, 2005

Benzothiazole Widespread usage 690 ng/L, S1 Germany, 2.27 ng/L, marine

water

Bester et al., 1997

2-Methylthiobenzothiazole Degradation product of

benzothiazoles

1.3 mg/L, S1 Germany, 50 ng/L, river

water

Dsikowitzky et al., 2004

2-Hydroxybenzothiazole Oxidation product of

benzothiazoles

61 mg/L, S3 e Azizian et al., 2003

Dimethyltrisulfide Oxygen depletion and

enrichment of hydrogen sulfide

11 mg/L, S3 Israel, 55 ng/L, lake water Ginzburg et al., 1998

Dimethyltetrasulfide Oxygen depletion and

enrichment of hydrogen sulfide

6 mg/L, S3 Israel, 0.52 ng/L, lake water Ginzburg et al., 1998

Dimethylsulfone Widespread usage 6.6 mg/L, S3 e Bentley and Chasteen, 2004

Di-p-tolylsulfone e 6.6 mg/L, S7 e e

4-Hydroxybenzenesulfonic acid Technical additive 150 ng/L, S3 e e

N-Butylbenzenesulfonamide Plasticizer 550 ng/L, S5 Germany, 140 ng/L, river

water

Dsikowitzky et al., 2004

o-Toluenesulfonamide Widespread usage 1 mg/L, S7 e Chemicalland21, 2006

Naphthalene Widespread usage 350 ng/L, S7 Norway, 0.53 mg/L, water

from offshore oil production

platform

Utvik, 1999

Di-iso-butyl adipate Widespread usage 1.2 mg/L, S1 e Chemicalland21, 2006

Ethyl cinnamate Personal care products 480 ng/L, S7 e Demetzos et al., 2002

4-Methylbenzoic acid

methylester

e 1.2 mg/L, S7 e e

Hexanedioic acid bis

(2-ethylhexyl) ester

Widespread usage mainly

plasticizer

870 ng/L, S5 Canada, 14 mg/L, river water Horn et al., 2004

2-Ethylhexanoic acid

2-hydroxypropyl ester

e 56 mg/L, S8 e e

2,4,4-Trimethylpentan-

1,3-dioldi-iso-butyrate

Widespread usage 280 ng/L, S8 Denmark, 0.5 mg/L, urban

waste water

Eriksson et al., 2003

Isopropyl myristate Widespread usage 1.7 mg/L, S8 Denmark, 3.8 mg/L, urban

waste water

Eriksson et al., 2003

a-Phthalimidoacetone e 77 ng/L, S7 e

Indole Fragrance/Flavour 162 mg/L, S3 Denmark, 3.8 mg/L, urban

waste water; Germany,

1400 mg/L, leakage water

from a waste deposit

Eriksson et al., 2003;

Schwarzbauer et al., 2002

2-Indolinone Oxidation product of indole 2 mg/L, S3 e Gu et al., 2002

(continued on next page)

238 A. Grigoriadou et al. / Environmental Pollution 151 (2008) 231e242

Table 3 (continued)

Compound Usage/Formation Highest concentration

and sample identified

in Kavala area

Country, concentration,

sample type

Reference

2,6-Di-tert-butyl-4-hydroxy-4-

methyl-2,5-cyclohexadienone

e 220 ng/L, S5 e e

1-Phenyl-2-butanone e 52 ng/L, S7 e e1-Phenyl-2-pentanone e 73 ng/L, S7 e e

o-Phenylphenol Fungicide 48 ng/L, S7 e Blasco et al., 2002

Phenol Widespread usage 126 mg/L, S8 Norway, 7.01 mg/L, water

from offshore oil production

platform

Utvik, 1999

2,4-Di-tert-butylphenol Degradation product of

antioxidants

9 ng/L, S2 Norway, 5 mg/L, pipe

drinking water

Skjevrak et al., 2003

3-tert-Butyl-4-hydroxyanisole Widespread usage 4.2 mg/L, S8 Germany, 11.7 ng/L, stream

water

Bolz et al., 2001

Diphenyl ether Herbicide 330 ng/L, S7 Italy, 12 mg/L, drinking water Rella et al., 2003

Di-iso-butylphthalate Plasticizer 3.2 mg/L, S3 Germany, 2.3 mg/L, river

water

Schwarzbauer and Heim, 2005

Di-n-butylphthalate Plasticizer 16 mg/L, S3 Netherlands, 1.88 mg/L,

freshwater

Peijnenburg and Struijs, 2005

Benzylbutylphthalate Plasticizer 58 mg/L, S7 Italy, 10 mg/L, Leachate

water from a landfill

Jonsson et al., 2003

Mono-n-butylphthalate Hydrolysis product of

dibutylphthalate

260 ng/L, S7 Italy, 16 mg/L, leachate water

from a landfill

Jonsson et al., 2003

Bis(2-ethylhexyl)phthalate

(DEHP)

Plasticizer 1.5 mg/L, S2 Netherlands, 2.35 mg/L,

freshwater

Peijnenburg and Struijs, 2005

S-Ethyl-N,N-

hexamethylenethiocarbamate

Herbicide 2.3 mg/L, S7 and S8 Japan, 1.1 mg/L, river water;

1.5 mg/L, surface and ground

water

Sudo et al., 2002;

Cerejeira et al., 2003

include was (1-hydroxycyclohexyl)phenylmethanone (tradename: Irgacure 184), a highly efficient non-yellowing photoinitiator and the dispersing and stabilizing agent for dyes2,4,7,9-tetramethyl-5-decine-4,7-diol. Finally, benzothiazolesappeared in nearly all of the samples. Benzthiazole is themajor leachate compound of rubber, e.g. used to make tires,but is also directly used as flavoring agent and as anadditive in fungicides (Suwanchaichinda and Brattsten,2002). Moreover, 2-(methylthio)benzothiazole is a dominantdegradation product of several benzothiazole-based fungicide

vulcanization additives (Castillo et al., 1999; Pedersen et al.,2003). Both benzothiazoles can be associated with automobiletire residues. Therefore, their occurrence may be partiallyattributed to street runoff or rubber waste discharge from thenational road of the area.

Other compounds appeared exclusively or in elevated concen-trations in specific samples, but a close correlation with localemission sources was not possible. For example, the widelyused compound tris(chloropropyl)phosphate (2 isomers) showedhigh concentrations in the sample from a water accumulation next

SAMPLE S3CH2Cl2 extract

(1)

(2)

(3)

(5) (21)

(9)

(10)(7)

(8)

(4)

6

(11)

(12)(13) (15)

(16)

(17)

(19)(14)

(20)

(18)

(22)

Retention time

Fig. 3. Total ion chromatogram of first fraction of sample S3. Numbers correspond to the chemical structures of Fig. 4.

239A. Grigoriadou et al. / Environmental Pollution 151 (2008) 231e242

1 2 3 4

O

O

7

NS

S85 6

9 10 11 12

13 14 15 16

17 18SN

OO19 20

21 22

OO

O

O

23 24

25 26 27 28

29 30

OOH

O

O

O

O

OH

O O

O O OO

O

O

OH

O

OHO

OO

O

O

OO

O

O

OH

O

Cl ClClO

OO

O

O

O

N

S

P OO

OO

NOH

N

S OHSN

S OH

OH

NSS

SS

SS

SSO

OOHHOS

O

O

OHOO

O

O

Fig. 4. Chemical structures of identified compounds in samples according to numbers in Figs. 3 and 5.

to the old national road of Kavala e Xanthi (sample S1). Thiscompound is a common xenobiotic, used mainly as a flame retar-dant and as a plastic additive. Due to its environmental stabilityand broad application it has been frequently measured and found,e.g. the low concentrations in untreated surface water samples ofthe Ruhr basin (Germany) (Andresen and Bester, 2006).

Sample S8, taken from the water accumulation near the fish-ery plant and a cultivated field, exhibited high concentrations ofisopropyl myristate, mainly used in cosmetics and pesticideformulations (Connock, 1998). The occurrence of this com-pound can probably be attributed to the usage of pesticides inthe surrounding agricultural area. The maximum concentrationof phenol was visible in sample S8, however, this concentrationwas lower than the level of phenol proposed by the US EPA forsurface water (3.5 mg/L) (U.S.EPA, 2005).

Notably, two previously unknown compounds, methyldiethyldithiocarbamate and methyl dimethyldithiocarbamate,were commonly observed at low concentrations in terrestrialwater samples, but were not detected in the marine water sam-ples. Both compounds are known as degradation products ofseveral xenobioticals, e.g. of tetraethylthiuram disulfide (disul-firam), a known alcohol deterrent, as well as of several dithio-carbamate based fungicides such as thiram. The compoundsdisulfiram and thiram are pharmaceuticals used in cancerchemotherapy and related applications, although several toxiceffects are reported for thiram and disulfiram e.g. mutagenic-ity. Both compounds could: (i) reflect agricultural emissionsthat include a widespread application of fungicides; or (ii)be related to vulcanisation accelerators associated with streetrunoff or another rubber related discharge. To our knowledge

240 A. Grigoriadou et al. / Environmental Pollution 151 (2008) 231e242

(28)(4)

(7)

(29)

(9)

(10)(20)

(22)(16)(24)

(25)

(11)

(13)

(17)

(15)(30)

(26)

(4)

(25) (17)

(15)(9) (13)

(11)

(21)(26)

(24) (19)

(20)

(27)

(22)

Retention time Retention time

Fattyacids

Fattyacids

Fattyacids

Fattyacids

(22)(20)(11)

Fattyacids

SAMPLE M2 CH2Cl2 extract (pH=2)

SAMPLE M2 CH2Cl2 extract

SAMPLE S2 CH2Cl2 extract

Retention time

SAMPLE S2CH2Cl2 extract (pH=2)

(28)

(16) (22)

(19) (20)

(31)(17)

FattyacidsFatty

acids

Fatty acids

(23)

Retention Time

Fig. 5. Total ion chromatograms of first and second fraction of sample M2 (marine water sample) and S2 (terrestrial water sample). Numbers correspond to the

chemical structures of Fig. 4.

these compounds have not been formerly reported as contam-inants of the aquatic environment.

3.3. Comparison of marine water samples andterrestrial water samples

When comparing the quantitative results obtained from themarine water samples with those from the terrestrial watersamples, results showed a significantly lower concentrationor absence of pollutants in the marine environment. Thiswas observed in several compounds whose concentrationsdropped below the detection limit in the marine samples.

The first comparison between marine water samples andterrestrial water samples was done by using the total ionchromatograms of a marine water sample (M2) and a terres-trial water sample (S2) (Fig. 5). The lower concentrationlevels of the marine water samples suggest dilution effectsdue to the increased volume of water present. Additionally,rigorous water exchange arising from fast water flow alongthis coastal area causes an interchange of freshwater and con-taminated water; this fast water flow is temporarily supportedby the inflow of uncontaminated freshwater of the NestosRiver, whose estuary is situated 10 km east of the area inves-tigated. However, numerous indicative substances identifiedin the terrestrial aquatic environment were also detected inthe marine water samples, indicating significant input into

the coastal system from the contaminated freshwater of theKavala industrial zone.

4. Conclusion

In this study a wide variety of organic compounds weremeasured in water samples collected from the industrial areanear Kavala using detailed screening analyses. In general,both the coastal area and the upper level of the terrestrialaquatic systems are strongly affected by anthropogenic com-pounds. Specific organic markers were isolated and character-ized in terms of their spatial distribution indicating thecontribution of emissions derived from different anthropo-genic activities and corresponding sources. There are individ-ual compounds identified solely in point source relatedsamples reflecting specific emissions derived from a petro-chemical plant, a fishery plant, diffuse agricultural activitiesand the uncontrolled discharge of solid wastes.

Extensive contamination in the area dominated by solidwaste discharges was pointed out by different molecularmarkers including technical additives and constituents of per-sonal care products. The overall contamination level of thesecompounds varied between a few ng/L up to several mg/L,which characterizes a significant contamination level, espe-cially in the fresh water samples. The attenuation observedfor the marine water samples can be attributed to a dynamicdilution as the result of an active water flow along the coastal

241A. Grigoriadou et al. / Environmental Pollution 151 (2008) 231e242

area. However, a significant impact of the terrestrial contami-nation to the marine environment is indicated by our results.

These influences may become more apparent by further inves-tigations of the corresponding sediments. Additionally, seasonalsampling and multiple sampling at different depths in this regionshould be undertaken in order to reveal the geochronology of theorganic pollution in this area. This study demonstrates the useful-ness of organic contaminants to serve as molecular indicators fordifferent anthropogenic emissions to reveal a comprehensiveview on the state of pollution in an aquatic system, and it servesas a model for future work to be done in this area.

Acknowledgments

The authors would like to express their gratitude for thefinancial support provided by the Greek State ScholarshipsFoundation (I.K.Y.).

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