www.elsevier.com/locate/envint

Environment International 30 (2004) 995–1007

Evaluation of the pollution of the surface waters of Greece from the

priority compounds of List II, 76/464/EEC Directive,

and other toxic compounds

Themistokles Lekkasa, George Kolokythasa, Anastasia Nikolaoua,*, Maria Kostopouloub,Anna Kotriklaa, Georgia Gatidoua, Nikolaos S. Thomaidisc, Spyros Golfinopoulosd,

Christina Makria, Damianos Babosa, Maria Vagia, Athanasios Stasinakisa,Andreas Petsasa, Demetris F. Lekkasa

aWater and Air Quality Laboratory, Department of Environmental Studies, University of the Aegean, Karadoni 17, 81100, Mytilene, GreecebDepartment of Marine Science, University of the Aegean, University Hill, 81100 Mytilene, Greece

cLaboratory of Analytical Chemistry, Department of Chemistry, National and Kapodistrian University of Athens, Panepistimioupolis,

15771 Zografou, Athens, GreecedDepartment of Financial and Management Engineering, University of the Aegean, Fostini 31, 82100, Chios, Greece

Received 5 February 2004; accepted 6 April 2004

Available online 21 July 2004

Abstract

The pollution of the surface waters of Greece from the priority compounds of 76/464/EEC Directive was evaluated. The occurrence of 92

toxic compounds, 64 of which belong to priority compounds of List II, candidates for List I, of 76/464/EEC Directive, was studied in surface

waters and wastewater through the developed network of 62 sampling stations, which covers the whole Greek territory. The analytical

determination was performed by Purge and Trap-Gas chromatography-Mass spectrometry for volatile and semivolatile organic compounds

(VOCs), Gas Chromatography-Electron Capture Detection for organochlorine insecticides, Gas Chromatography-Nitrogen Phosphorous

Detection for organophosphorous insecticides, High Performance Liquid Chromatography-Photodiode Array Detection for herbicides, and

Electrothermal Atomic Absorption Spectrophotometry and Inductively Coupled Plasma-Atomic Emission Spectrometry (ICP-AES) for

metals and the toluene extractable organotin compounds. The concentrations of VOCs and insecticides detected in the surface waters of

Greece were very low, whereas the concentrations of herbicides and metals ranged generally at moderate levels. VOCs were detected almost

exclusively in the rivers and very rarely in the lakes, while the frequency of occurrence of insecticides, herbicides and metals was similar for

rivers and lakes. Water quality objectives (WQO) and emission limit values (ELV) have been laid down in national legal framework for a

number of compounds detected in the samples, in order to safeguard the quality of surface waters from any future deterioration.

D 2004 Elsevier Ltd. All rights reserved.

Keywords: Pollution; Surface waters; Greece

1. Introduction caused by substances belonging to List II of the Directive

Substances posing health risks to human and to the

aquatic environment are divided, according to 76/464/EEC

Directive, in two Lists. Member States of the European

Community are required to eliminate pollution caused by

substances belonging to List I, and to reduce pollution

0160-4120/$ - see front matter D 2004 Elsevier Ltd. All rights reserved.

doi:10.1016/j.envint.2004.04.001

* Corresponding author. Tel.: +30-251-03-6227; fax: +30-251-03-

6226.

E-mail address: nnikol@aegean.gr (A. Nikolaou).

(EEC, 1982). In Greece, determination of the substances

of List I of 76/464/EEC Directive in the surface waters

has been performed and reported in previous studies

(Kostopoulou et al., 2000; Golfinopoulos et al., 2003;

Lekkas et al., 2003a). The aim of the present investigation

was to evaluate the pollution of the Greek surface waters

from the compounds of List II, 76/464/EEC Directive, and

assist the safeguarding of their quality through legislative

measures.

The selection of the investigated compounds followed a

study for the possible existence in the Greek surface waters

Table 1

Priority compounds of List II, candidate compounds for List I, selected for

analysis

(A) Volatile and Semivolatile Organic Compounds

1. 1,1-Dichloroethylene (60)

2. Dichloromethane (62)

3. trans-1,2-Dichloroethene (61)

4. 1,1-Dichloroethane (58)

5. cis-1,2-Dichloroethene (61)

6. 1,1,1-Trichloroethane (119)

7. Benzene (7)

8. 1,2-Dichloropropane (65)

9. Toluene (112)

10. 1,1,2-Trichloroethane (120)

11. 1,2-Dibromoethane (48)

12. Chlorobenzene (20)

13. Ethylbenzene (79)

14. (m+ p)-Xylenes (129)

15. o-Xylene (129)

16. Isopropylbenzene (87)

17. 2-Chlorotoluene (38)

18. 4-Chlorotoluene (40)

19. 1,3-Dichlorobenzene (54)

20. 1,4-Dichlorobenzene (55)

21. 1,2-Dichlorobenzene (53)

22. Napthalene (96)

(B) Organochlorine insecticides

23. Heptachlor (82)

24. Heptachlor epoxide (82)

25. a-Endosulfan (76)

26. h-Endosulfan (76)

27. Endosulfan sulfate (76)

(C) Organophosphorous, nitrogen, sulfur insecticides

28. Methamidophos (93)

29. Mevinphos (94)

30. Omethoate (97)

31. Demeton (O +S) (47)

32. Demeton-S-methyl (47)

33. Dimethoate (73)

34. Disulfoton (75)

35. Parathion methyl (100)

36. Fenitrothion (80)

37. Malathion (89)

38. Fenthion (81)

39. Parathion ethyl (100)

40. Triazophos (113)

41. Azinphos methyl (6)

42. Azinphos ethyl (5)

43. Coumaphos (43)

44. Phoxim (103)

(D) Herbicides (Triazines and substituted ureas)

45. Simazine (106)

46. Atrazine (131)

47. Monolinuron (135)

48. Linuron (88)

(E) Metals

49–62. As, Pb, Cr, Ni, Co, Cu, Zn, Fe, Mn, V, Mo, Ba, Ti, Al

(F) Organotin compounds

63. Dibutyltin (49)

64. Tributyltin (126)

The numbers in parenthesis are those of List II of 76/464/EEC Directive.

T. Lekkas et al. / Environment International 30 (2004) 995–1007996

of compounds belonging to List II of 76/464/EEC Directive

(Lekkas, 1998). The initial identification of compounds

covered the examination of the possible discharges of the

Greek chemical industries and the use of toxic compounds

which are imported. Based on the data of this study, the

compounds listed in Table 1 were selected for further

investigation. In addition, the compounds listed in Table 2

were investigated, although not included in the priority

compounds of List II, 76/464/EEC Directive, due to their

importance for water quality (USEPA, 1979, 1998; Rober-

son et al., 1995; WHO, 1995; Voulvoulis et al., 2002;

Konstantinou and Albanis, 2004).

The investigation for the above compounds was imple-

mented by establishing a monitoring network throughout

the whole country, covering the most significant water

bodies where representative sampling stations were locat-

ed. The location of these sampling stations took into

account the possible emission sources of the relevant

compounds. Sampling campaigns were executed seasonal-

ly, and the analysis of samples was conducted in the Water

and Air Quality Laboratory, Department of Environmental

Studies, University of the Aegean, where analytical meth-

Table 2

Compounds not included in the priority compounds of List II, selected for

analysis

(A) Volatile and Semivolatile Organic compounds

1. Bromochloromethane

2. Dibromomethane

3. Dichlorobromomethane

4. Dibromochloromethane

5. 2,2-Dichloropropane

6. 1,1-Dichloropropene

7. 1,3-Dichloropropane

8. Bromoform

9. Bromobenzene

10. n-Propylbenzene

11. tert-Butylbenzene

12. sec-Butylbenzene

13. 1,3,5-Trimethylbenzene

Organochlorine insecticides

14. Endrin aldehyde

15. Methoxychlor

16. Endrin ketone

Herbicides (Triazines and substituted ureas)

17. Diuron

18. Metobromuron

19. Terbuthylazine

20. Prometryn

21. Cyanazine

22. Chlorotoluron

23. Deisopropyl-Atrazine

24. Metamitron

25. Chloridazon

26. Desethyl-Atrazine

Organotin compounds

27. Triphenyltin

T. Lekkas et al. / Environment Inter

ods for the determination of volatile and semivolatile

organic compounds (VOCs), insecticides, herbicides, met-

als and organotins have been developed and optimized

(Lekkas et al., 2003b). Several compounds belonging to all

chemical categories studied were detected in the samples.

Although their concentration levels were generally low,

their presence in the waters revealed the need to safeguard

their quality from future deterioration through legislative

measures.

2. Experimental

2.1. Design of monitoring network

The monitoring network for priority compounds of List

II, candidate compounds for List I, of 76/464/EEC Direc-

tive in the surface waters of Greece includes 53 sampling

stations in 11 rivers (total catchment area 78,390 km2), 7

lakes (total surface area 286.095 km2) and 4 seawater

areas (Table 3). Two sampling stations were established in

each river, the first near the springs and the second at the

estuary region (Nikolaou et al., 2000). Two sampling

stations were also established for each lake—in order to

sufficiently cover the catchment area—except Doirani (one

sampling station) and Large Prespa (four sampling sta-

tions, two 1 m under the surface and two under the

stratification zone). Sampling was performed seasonally,

four times per year, giving a number of 1520 samples for

surface water, during from October 1998 to September

1999.

For wastewater, the influents and effluents of three

municipal wastewater treatment plants (Metamorfosi, Psy-

ttalia and Volos) and the effluents of wastewater treatment

plants at three industries (a paint industry, a pharmaceutical

industry and a gold mine) were monitored. Sampling was

also in this case performed seasonally, giving a number of

260 samples per year (for wastewater). The annual total

samples from the established network amount to 1780.

Table 3

Monitoring network in the surface waters of Greece

Rivers Samples per year Lakes

Evros (EB) 80 Volvi (VO)

Nestos (NE) 80 Vegoritida (VE)

Strymonas (ST) 80 Vistonida (VI)

Axios (AX) 80 Small Prespa (SP)

Aliakmonas (AL) 80 Large Prespa (LP)

Pinios (PIN) 80 Pamvotida (PAM)

Asopos (AS) 80 Doirani (DO)

Pinios Peloponese (PINPEL) 40

Evrotas (EVR) 40

Alphios (ALF) 40

Acheloos (ACH) 80

Total 760 Total

2.2. Analytical methods

2.2.1. Volatile and semivolatile organic compounds (VOCs)

2.2.1.1. Samples. Water samples were collected in 40-ml

glass vials and were capped with PTFE-faced silica septum

(Pierce 13075), after addition of 4 drops of 6 N HCl solution

as preservative.

2.2.1.2. Analytical. The determination of VOCs was car-

ried out by a modification of purge and trap (PAT) gas

chromatographic (GC) method (APHA, 1992), with a Hew-

lett Packard Purge and Trap Concentrator 7695 with a 30-

cm absorbent trap (VOCARB3000), a Hewlett Packard Gas

Chromatograph 5890 Series II and a Hewlett Packard Mass

Spectrometer HP5971 MSD. A fused silica capillary column

HP VOC, 60 m� 0.32 mm i.d.� 1.8 Am i.d. film thickness,

was used, and the carrier gas was helium. The analytical

conditions and the recoveries of the method have been

reported elsewhere (Lekkas et al., 2003b). The range of

the detection limits (DL) was 0.01–0.25 Ag/l and the range

of the recoveries 46–160% for tested concentration range

0.5–10 Ag/l.

2.2.2. Insecticides

2.2.2.1. Samples. Water samples were collected in 1-

l amber glass vials, pre-filtered through 0.45-Am glass fiber

and acidified with 6 N HCl solution to pH 2, in order to

inhibit biological activity.

2.2.2.2. Analytical. A Gas Chromatography method was

applied for the analysis of insecticides, using a Hewlett

Packard Gas Chromatograph 5890 Series II, supported by a

Nitrogen Phosphorus Detector (NPD) for the organophos-

phorus insecticides and an Electron Capture Detector (ECD)

for the organochlorine insecticides. The fused silica capil-

lary columns used were a DB-5 30 m� 0.32 mm i.d.� 0.25

Am film thickness for the organophosphorus insecticides

national 30 (2004) 995–1007 997

Samples per year Seawater areas Samples per year

80 Saronikos Gulf 48

80 Thermaikos Gulf 48

80 Pagasitikos Gulf 32

80 Olympiada Bay 32

160

80

40

600 Total 160

T. Lekkas et al. / Environment International 30 (2004) 995–1007998

and a HP-608 30 m� 0.53 mm i.d.� 0.5 Am film thickness

for the organochlorine insecticides.

Solid-phase extraction procedure (SPE) was applied prior

to analysis, with addition of methanol modifier (10 ml) to

1-l water sample to allow better extraction (Albanis et al.,

1998). SPE disks with diameter of 47 mm and thickness of

0.5 mm, containing 500 mg of the bonded phase (octadecyl-

C18-bonded silica), were used. They were conditioned with

10-ml acetone for 30 min, placed in the conventional

Millipore apparatus and washed with 10 ml of ethyl acetate

followed by 10 ml of dichloromethane under vacuum, and

with 10 ml of methanol with the vacuum off. The SPE disks

were not allowed to become dry, as recommended (Albanis

et al., 1998). The water samples were mixed well and

allowed to percolate through the disks with a flow rate of

30 ml/min under vacuum. The insecticides trapped in the

disk were collected by using 2� 5 ml of ethyl acetate as

eluting solvent. The eluted fractions were evaporated to 0.5

ml in a gentle stream of nitrogen.

The analytical conditions and the recoveries of the

method have been presented elsewhere (Lekkas et al.,

2003b). The recoveries ranged from 40% to 132% for

concentration levels 0.02–0.4 Ag/l. The DL for the organ-

ochlorine insecticides was 0.002 Ag/l. For the organophos-

phorus insecticides, the DL ranged from 0.003 to 0.05 Ag/l.

2.2.3. Triazine (TRIA), phenylurea herbicides (PU) and

Phoxim

2.2.3.1. Samples. Water samples were collected in 1-

l amber glass vials and filtered through 0.7-Am glass micro-

fiber filter.

2.2.3.2. Analytical. A High Performance Liquid Chroma-

tography (HPLC) method was applied. The HPLC system

consisted of a 9012 pump, associated with a Polychrom 9065

diode-array detector (Varian, USA) and a Rheodyne 7161,

100 Al, loop injector (Rheodyne, USA). The column was a

Zorbax SB-C18 4.6 mm� 15 cm (5 Am) connected with a

Zorbax SB-C18 precolumn (Hewlett Packard, USA). Jones

Chromatography, England supplied a 7980 column block

heater. The temperature of the column was set at 40 jC.The solid-phase extraction was based on the method of

Hewlett-Packard (Hewlett-Packard, 1994), with some mod-

ifications. The sample (500 ml) was filtered through a GF/F

0.7-Am glass microfiber filter (Whatman, England). C18

cartridges (Waters, USA) were conditioned with 10 ml of

methanol and 10 ml of ultrapure water and the sample was

loaded with an approximate flow rate of 20 ml/min. The

sorbent was washed with 5 ml of water, and the herbicides

were eluted with 6 ml of acetonitrile. The acetonitrile was

removed under a gentle stream of nitrogen, at 35 jC, and theherbicides were reconstituted with 1 ml of the initial mobile

phase.

The analytical conditions of the method have been

reported elsewhere (Lekkas et al., 2003a,b). The average

recoveries for tested concentration levels 0.1, 0.5 and 1.0

Ag/l ranged from 65% to 105%, whereas lower recoveries

were observed for deisopropyl atrazine, metamitron, chlor-

idazon and desethyl atrazine (13–49%) (Lekkas et al.,

2003a,b). The DL ranged from 0.025 to 0.5 Ag/l.

2.2.4. Metals

2.2.4.1. Samples. Two samples were collected from each

sampling site: one for the total determination and one for the

dissolved fraction of metals. Water samples for total metals

determination were collected in 500-ml polyethylene vials

and were acidified with HNO3 to pH 1. Another aliquot

(200 ml) was filtered on site through a 0.45-Am membrane

filter and the filtrate was collected in polyethylene vials and

was acidified with HNO3 to pH 1.

2.2.4.2. Analytical. The determination of As, Pb, Cr, Ni,

Co, Cu, Zn, Fe, Mn, V, Mo (dissolved and total acid

extractable) was made using an atomic absorption spec-

trometer equipped with a Zeeman THGA graphite furnace

(Perkin Elmer 5000ZL) and an autosampler (Perkin Elmer

AS-70). The total acid extractable matter of metals was

determined after digestion of samples with concentrated

HNO3 for 12 h in 70 jC (Haswell, 1991). One microgram

of Pd for As determination and 1 Ag of Pt for Pb determi-

nation were used as chemical modifiers. The DL ranged

from 0.13 (Mo) to 1.0 (As) Ag/l (Lekkas et al., 2003b).

Inductively Coupled Plasma-Atomic Emission Spectrome-

try (ICP-AES, a GBC Integra XM instrument) was used for

the determination of Ba, Ti and Al, with DL of 11, 15 and

16 Ag/l, respectively. Accuracy was assessed using the

certified reference material SRM 1643 (Trace elements in

Water) and quantitative recoveries (94–105%) were ob-

tained for all the studied metals.

2.2.5. Toluene extractable organotins

2.2.5.1. Samples. Water samples were collected in 2-

l amber glass bottles and immediately acidified with HCl

to pH 2. Some wastewater samples, due to the high

suspended solids concentration, were filtered at the labora-

tory before extraction.

2.2.5.2. Analytical. The water samples were acidified with

50-ml glacial acetic acid to a final concentration of 2.5%

(v/v) and 24 g of sodium chloride was added giving a final

concentration of 1.2% (w/v). Then, the samples were

extracted with 10 ml toluene. The solvent layer was then

transferred in a glass bottle and preconcentrated under a

gentle air flow to 1 ml. With this procedure, all tributyltin

(TBT) and triphenyltin (TPhT) and 67% of dibutyltins

(DBT) are extracted, but not monobutyltin (MBT) or

inorganic tin (Sn) (Thomaidis et al., submitted for publica-

tion). A Perkin Elmer atomic absorption spectrophotometer,

model 5100PC, equipped with a Zeeman THGA graphite

T. Lekkas et al. / Environment International 30 (2004) 995–1007 999

furnace (Perkin Elmer 5100ZL) and a Perkin Elmer auto-

sampler (AS-70) was used. Rhenium (5 Ag) was chosen as

chemical modifier and the hot-injection technique was

applied, which resulted in a low DL of 0.001 Ag/l. Thedetailed analytical conditions have been reported elsewhere

(Thomaidis et al., submitted for publication; Lekkas et al.,

2003b).

3. Results and discussion

The annual mean concentrations determined in the Greek

surface waters during October 1998–September 1999 are

presented in Figs. 1–3 for VOCs, insecticides and herbi-

cides and in Fig. 4a and b for metals. During calculation of

the annual mean values, wherever the concentration of a

compound was not detectable, it was assigned the value of

the DL for this compound. The range of concentrations

detected in samples from rivers, lakes and wastewater

treatment plants is presented in Table 4.

3.1. Surface water samples

3.1.1. Volatile and semivolatile organic compounds (VOCs)

The concentrations of VOCs detected in the surface

waters were very low. In the rivers, the highest annual mean

concentrations of VOCs detected were 0.15 Ag/l for 1,1,2-trichloroethane in AX and PIN, 1.71 Ag/l for toluene in PIN,

0.87 Ag/l for chlorotoluene in ST, 0.86 Ag/l for 1,3,5-

trimethylbenzene in EB, 0.43 Ag/l for dichlorobenzene in

ST, 0.84 Ag/l for naphthalene in EB and 0.16 Ag/l for

trichlorobenzene in ST. The largest number of priority

VOCs occurred in rivers AX (1,1,2-trichloroethane, toluene,

dichlorobenzene and naphthalene) and ST (chlorotoluene,

dichlorobenzene, naphthalene and trichlorobenzene) (Fig.

1). In the lakes, the only VOC detected was 1,1,2-trichloro-

ethane in LP (0.13 Ag/l) and in VO (0.13 Ag/l) (Fig. 3). Inthe seawater areas no VOCs occurred, except for toluene

(0.68 Ag/l) in Thermaikos gulf only at one sampling period

Fig. 1. Concentrations of VOC

(October 1998). The occurrence of VOCs in the surface

waters, with annual mean concentrations ranging from not

detectable to 1.71 Ag/l, is attributed to agricultural and

industrial activity, especially in the area of northern Greece,

which also contributed to the occurrence of substances of

List I, 76/464/EEC Directive, in the surface waters of this

area (Kostopoulou et al., 2000; Golfinopoulos et al., 2003).

The concentrations of VOCs determined during this study

were comparable to those reported by Miermans et al.

(2000), using a PAT-GC-MS method, for Dutch surface

waters.

3.1.2. Insecticides

The obtained results have shown that the most commonly

encountered organochlorine insecticides in surface waters

are a-endosulfan, h-endosulfan and endosulfan sulfate.

Heptachlor and heptachlor epoxide were detected in rivers

ST and AX and in lakes VO and VE. Heptachlor was also

detected in lake DO.

The concentrations of organochlorine insecticides in the

surface waters were very low. The highest annual mean

concentrations in rivers were 0.009 Ag/l for endosulfan in

EB and ST, 0.008 Ag/l for heptachlor in PIN and 0.007 Ag/l for heptachlor epoxide in ST. In the lakes, the highest

annual mean concentrations of insecticides were 0.007 Ag/l for endosulfan in VO and 0.005 Ag/l for heptachlor in DO.

The water bodies where all priority organochlorine insecti-

cides studied were detected were rivers AX and ST and

lakes DO and VE (Figs. 2 and 3).

As regards organophosphorus insecticides, the most

frequently detected compounds are fenthion, triazophos,

azinphos methyl, azinphos ethyl, coumaphos, parathion

ethyl. Furthermore, several organophosphorous insecticides

were detected, mainly in rivers EB, NE, ST, AL and PIN

and in most of the lakes, as follows: parathion methyl (in

rivers EB, NE, ST, AL, ACH and PIN, as well as in all the

lakes), fenitrothion (in rivers NE, ST, ACH and EVR as well

as in all the lakes except for SP), dimethoate (in rivers EB,

NE, AX, AL, ACH, ALF and in lakes VO, LP, VE and VI),

s in the rivers of Greece.

Table 4

Range of concentrations (Ag/l) of the studied substances during October 1998–September 1999

Substance DL Rivers Lakes Seawater Wastewater

1,1-Dichloroethene 0.10 nd nd nd nd-5.3

Dichloromethane 0.05 nd nd nd nd-23.8

trans-1,2-Dichloroethene 0.25 nd nd nd nd-3.1

1,1-Dichloroethane 0.10 nd nd nd nd-2.4

cis-1,2-Dichloroethene 0.25 nd nd nd nd-1.6

2,2-Dichloropropane 0.05 nd nd nd nd

Bromochloromethane 0.25 nd nd nd nd

1,1,1-Trichloroethane 0.10 nd nd nd nd-663.8

Benzene 0.10 nd nd nd nd-5.9

1,2-Dichloropropane 0.25 nd nd nd nd

Dibromomethane 0.25 nd nd nd nd

Dichlorobromomethane 0.05 nd nd nd nd-5.8

1,1-Dichloropropene 0.25 nd nd nd nd-5.8

Toluene 0.05 nd-6.7 nd nd-0.63 nd-13.7

1,1,2-Trichloroethane 0.10 nd-0.3 nd-0.2 nd nd-1.59

1,3-Dichloropropane 0.05 nd nd nd nd-0.6

Dibromochloromethane 0.10 nd nd nd nd-9.7

1,2-Dibromoethane 0.10 nd nd nd nd

Chlorobenzene 0.05 nd nd nd nd-20.9

Ethylbenzene 0.05 nd nd nd nd-19.8

(m + p)-Xylenes 0.05 nd nd nd nd-36.4

o-Xylene 0.05 nd nd nd nd-5.8

Bromoform 0.10 nd nd nd nd-1.2

Isopropylbenzene 0.05 nd nd nd nd

Bromobenzene 0.10 nd nd nd nd

n-Propylbenzene 0.05 nd nd nd nd-0.6

2-Chlorotoluene 0.25 nd-0.8 nd nd nd-0.8

4-Chlorotoluene 0.25 nd-1.6 nd nd nd-1.6

tert-Butylbenzene 0.25 nd nd nd nd

1,3,5-Trimethylbenzene 0.25 nd-2.7 nd nd nd-64.8

sec-Butylbenzene 0.25 nd nd nd nd-1.4

1,3-Dichlorobenzene 0.05 nd-0.9 nd nd nd-0.2

1,4-Dichlorobenzene 0.05 nd-0.2 nd 0.1 nd-0.3

1,2-Dichlorobenzene 0.10 nd-0.3 nd nd nd-18.1

Napthalene 0.05 nd-1.4 nd nd nd-22.2

1,2,3-Trichlorobenzene 0.01 nd-0.6 nd nd nd-5.7

Heptachlor 0.002 nd-0.025 nd-0.013 + +

Heptachlor epoxide 0.002 nd-0.020 nd-0.012 + +

a-Endosulfan 0.002 nd-0.043 nd-0.035 + +

h-Endosulfan 0.002 nd-0.015 nd-0.023 + +

Endosulfan sulfate 0.002 nd-0.028 nd-0.019 + +

Endrin aldehyde 0.002 nd-0.098 nd-0.012 + +

Methoxychlor 0.002 nd nd + +

Endrin ketone 0.002 nd nd + +

Methamidophos 0.005 nd-0.025 nd-0.078 + +

Mevinphos 0.005 nd-0.013 nd-0.016 + +

Omethoate 0.050 nd nd + +

Demeton (O +S) 0.005 nd-0.006 nd-0.019 + +

Demeton-S-methyl 0.005 nd-0.021 nd-0.131 + +

Dimethoate 0.005 nd-0.08 nd-0.023 + +

Disulfoton 0.003 nd-0.096 nd-0.061 + +

Parathion methyl 0.003 nd-0.042 nd-0.025 + +

Fenitrothion 0.003 nd-0.007 nd-0.039 + +

Malathion 0.003 nd-0.005 nd-0.005 + +

Fenthion 0.003 nd-0.005 nd-0.004 + +

Parathion ethyl 0.003 nd-0.014 nd-0.077 + +

Triazophos 0.003 nd-0.158 nd-0.031 + +

Azinphos methyl 0.003 nd-0.031 nd-0.016 + +

Azinphos ethyl 0.003 nd-0.011 nd-0.008 + +

Coumaphos 0.003 nd-0.040 nd-0.020 + +

Deisopropyl-Atrazine 0.200 nd nd + +

Metamitron 0.200 nd nd-0.658 + +

T. Lekkas et al. / Environment International 30 (2004) 995–10071000

Table 4 (continued )

Substance DL Rivers Lakes Seawater Wastewater

Chloridazon 0.200 nd nd + +

Desethyl-Atrazine 0.200 nd nd + +

Simazine 0.025 nd-0.640 nd-0.032 + +

Cyanazine 0.025 nd-0.083 nd-0.108 + +

Chlorotoluron 0.040 nd-0.113 nd-0.098 + +

Atrazine 0.025 nd-0.330 nd-0.500 + +

Monolinuron 0.040 nd-0.067 nd + +

Diuron 0.040 nd nd-0.085 + +

Metobromuron 0.040 nd-0.144 nd-0.090 + +

Terbuthylazine 0.025 nd-0.037 nd-0.030 + +

Linuron 0.040 nd-0.100 nd-0.047 + +

Prometryn 0.025 nd-0.780 nd-0.1 + +

Phoxim 0.050 nd nd + +

Arsenic 1 nd-11.04 nd-74.5 + nd-6.4

Barium 11 17.7-110 12.4-114 + 3.9-13.8

Chromium 0.18 0.5-137 nd-37.6 + 4.9-1012

Cobalt 0.8 nd-16.3 nd-3.4 + nd-16.3

Copper 0.36 0.9-80.4 0.7-59.6 + 6.9-74.6

Lead 0.8 nd-12.9 nd-16.5 + nd-104

Nickel 0.4 1.4-147.8 nd-9.1 + 5.8-147.8

Aluminum 16 nd-1669 nd-840 + 30-979

Iron 1 81-20355 14.3-15755 + 317-20355

Manganese 0.27 3.9-455 2.9-431 + 24.7-512

Molybdenum 0.13 nd-18.4 nd-14.2 + 0.6-3.7

Vanadium 1 nd-113 nd-41.4 + nd-113

Titanium 15 nd-62.5 nd-30.2 + nd-53.1

Zinc 0.35 3.1-143 0.5-57.2 + 12.4-323

Toluene extractable organotins 0.001 nd-0.009 nd-0.018 0.005-0.023 0.005-0.090

nd: not detectable concentration; +: analysis was not performed for this compound.

T. Lekkas et al. / Environment International 30 (2004) 995–1007 1001

disulfoton (in rivers ST, AX, ACH, PIN, ALF and in all

lakes except for LP), demeton (O + S) (in river EB and lakes

VO, LP, PAM and DO), demeton-S-methyl (in rivers EB,

NE, AL, ACH and ALF and in lakes DO and VI), meth-

amidophos (in rivers EB and ACH and in lakes SP, DO and

VE), mevinphos (in rivers ST, AL, PIN and ALF), malathi-

on (in river EB and in lakes LP and DO), and omethoate

(only in ST river).

The concentrations of the insecticides measured in this

study are comparable to those reported by other authors in

several studies (Angelidis et al., 1996; Angelidis and Alba-

nis, 1996; Albanis et al., 1995a,b; Albanis and Hela, 1998).

Fig. 2. Concentrations of insecticides and

Chlorinated insecticides belonging to List I, 76/464/EEC

Directive, measured in the water bodies of Northern Greece

(Kostopoulou et al., 2000; Golfinopoulos et al., 2003),

occurred in slightly higher concentrations than chlorinated

insecticides belonging to List II, 76/464/EEC Directive,

measured in the same water bodies during the present study.

3.1.3. Triazine (TRIA), phenylurea herbicides (PU)

The herbicide with the highest frequency of detection

was atrazine followed by simazine and prometryne. This

dominance of atrazine is in agreement with several reports

from different rivers and lakes in Greece (Albanis, 1991,

herbicides in the rivers of Greece.

T. Lekkas et al. / Environment International 30 (2004) 995–10071002

1992) and is due to its intensive use (NSBG, 1988–89) and

physicochemical properties (Matolcsy et al., 1998).

Linuron was detected in river Ax and lake LP, mono-

linuron in rivers EB and PIN, terbuthylazine in rivers EB

and Ax and in lake PAM, chlorotoluron in rivers EB, ST,

PIN and in lake VI, metobromuron in rivers NE, ST and

ACH and in lakes PAM and VE. Cyanazine was detected in

rivers EB, NE, ST, AX, AL, PIN, ALF and in lakes LP,

PAM, VE and VI. Prometryn was detected in rivers EB, NE,

ST, AL, AS, ACH, PIN and in lakes LP, DO and VI. Diuron

was detected only in VI lake.

The concentration levels of herbicides detected in the

surface waters were moderate. In the rivers, the highest

annual mean concentrations of herbicides were 0.099 Ag/l for atrazine in PINPEL, 0.117 Ag/l for simazine in ST and

0.063 Ag/l for cyanazine in ST. In the lakes, the highest

annual mean concentrations were 0.091 Ag/l for atrazine in

VO, 0.027 Ag/l for simazine in VI and 0.044 Ag/l for

cyanazine in LP. The water bodies with the largest number

of herbicides (atrazine, simazine and cyanazine) were rivers

ST, EB, NE and PIN and lake VI (Figs. 2 and 3).

In general, the concentrations found in the surface

waters tested are not very high. Occasional peaks, such

as Prometryne in EB and PIN, Atrazine in VO and

Simazine in ST, correspond to intense agricultural applica-

tions and meteorological events. In the majority of cases,

the annual average concentrations of the individual com-

pounds were less than 0.1 Ag/l. In all cases, the total

concentration of the compounds in every sampling point

was less than 0.5 Ag/l, which is the limit set by the

European Union for the presence of insecticides in drinking

water (EEC, 1980). The range of concentrations found is

similar to that reported from several studies in different

locations (Albanis, 1991, 1992).

3.1.4. Metals

The metal burden of the aquatic environment of Greece is

generally low (Fig. 4). Higher levels of toxic metals were

observed in the rivers ST, EB, AX and PIN. The highest

Fig. 3. Concentrations of VOCs, insecticides

concentration of total As was observed in lake DO. High

concentrations of As in lakes DO and VO have already been

reported (Grimanis, 1990) and are probably due to the

geological background of these lakes. High levels of Cr,

Ni, Co and Fe were observed in some water bodies during

winter sampling campaign, probably due to the run off

waters. Specifically, in the rivers the highest annual mean

concentrations of metals were 6.67 Ag/l for As in ST; 6.39

Ag/l for Pb, 9.17 Ag/l for Mo and 74.3 Ag/l for Ba in EB;

40.3 Ag/l for Cr, 51.1 Ag/l for Ni, 5.35 Ag/l for Co, 22.4 Ag/l for Cu and 23.7 Ag/l for V in PIN; 43.6 Ag/l for Zn and

1151 Ag/l for Al in AX; 5707 Ag/l for Fe and 262 Ag/l forMn in ALF; 51.6 Ag/l for Ti in NE. In the lakes, the highest

annual mean concentrations of most metals were observed

in DO: 51.5 Ag/l for As, 14.8 Ag/l for Cr, 3.38 Ag/l for Co,6157 Ag/l for Fe, 173 Ag/l for Mn, 20.6 Ag/l for V, 8.65 Ag/l for Mo, 83.0 Ag/l for Ba, 30.2 Ag/l for Ti and 840 Ag/l forAl. For Ni and Cu the highest annual mean concentrations

occurred in lake VE, 5.70 and 11.6 Ag/l, respectively, for Pbin VO (1.47 Ag/l) and for Zn in PAM (13.8 Ag/l).

3.1.5. Toluene extractable organotins

The concentrations of the toluene extractable fraction of

the organotin compounds were in the range of 0.005–0.020

Ag/l for seawater, < 0.002–0.020 Ag/l for surface water and0.005–0.090 Ag/l for wastewater.

Concentrations of organotin compounds in coastal areas

decreased significantly with increasing distance from the

harbors. This pattern was consistent with that reported in the

literature (Dirkx et al., 1993) suggesting that the main

source of these compounds was antifouling paints.

Comparison of organotin concentrations in river and lake

waters examined with those reported in literature shows that

the values reported in this study are slightly lower than those

found in European surface waters (Fent and Hunn, 1995).

The highest concentrations were detected in lake Pamvotida

(annual mean concentration 0.009 Ag/l), where shipping

activity with small boats is observed. The existence of these

compounds in Pinios, Axios, Aliakmonas and Evros river,

and herbicides in the lakes of Greece.

Fig. 4. Concentrations of metals in the surface waters of Greece.

T. Lekkas et al. / Environment International 30 (2004) 995–1007 1003

even at low concentrations, is attributed to use of agro-

chemicals and effluents of wastewater treatment plants.

The total results indicate low levels of pollution of the

surface waters of Greece from the priority compounds of

List II of 76/464/EEC Directive. Further than priority

substances, a number of non-priority substances, mostly

herbicides, were present in the waters studied, at low

concentrations (Table 4). In order to reassure that good

water quality will be maintained, legislative measures have

been adopted at national level, as presented below.

3.2. Wastewater samples

3.2.1. Volatile and semivolatile organic compounds (VOCs)

A large number of VOCs occurred in wastewater samples

(Fig. 5), where the range of the annual mean concentrations

was 0.06 Ag/l (xylenes)–162.0 Ag/l (1,1,1-trichloroethane).Regarding samples from municipal wastewater treatment

plants, several VOCs occurred in Metamorfosi and Psyttalia:

cis-1,2-dichloroethene, 1,1-dichloroethylene toluene, dibro-

mochloromethane, trans-1,2-dichloroethene, 1,1-dichlo-

Table 5

WQO for VOCs, insecticides, herbicides and metals

Substance WQO

(Ag/l)Substance WQO

(Ag/l)Substance WQO

(Ag/l)

VOCs Insecticides Herbicides

1,3-Dichlorobenzene 10 a-Endosulfan 0.01 Atrazine 1

1,4-Dichlorobenzene 10 h-Endosulfan 0.01 Simazine 1

1,2-Dichlorobenzene 10 Endosulfan

Sulfate

0.01 Linuron 1

2-Chlorotoluene 1 Fenthion 0.01 Metals

4-Chlorotoluene 1 Azinphos

methyl

0.01 Arsenic 10

Toluene 10 Azinphos

ethyl

0.01 Barium 100

Naphthalene 1 Parathion 0.01 Chromium 50

cis-1,2-

Dichloroethene

10 Mevinphos 0.01 Cobalt 20

trans-1,2-

Dichloroethene

10 Demeton

(O +S)

0.1 Copper 50

Benzene 10 Demeton-S-

methyl

0.01 Lead 20

Dichloromethane 10 Parathion

methyl

0.01 Nickel 50

Ethylbenzene 10 Fenitrothion 0.01 Aluminum 400

(m+ p)-Xylenes 10 Malathion 0.01 Iron 200

o-Xylene 10 Manganese 100

Chlorobenzene 1 Zinc 1000

The concentration values mentioned correspond to the annual mean values.

Fig. 5. Concentrations of VOCs in wastewater treatment plants.

T. Lekkas et al. / Environment International 30 (2004) 995–10071004

roethane, dichloromethane and benzene. In industrial waste-

water samples, the known chlorination by-products dichlor-

obromomethane and dibromochloromethane, (USEPA, 1979,

1998; Roberson et al., 1995; WHO, 1995) were the major

VOCs occurring in the paint manufacturing industry, where

also benzene, ethylbenzene, xylenes, dichlorobenzene, chlor-

otoluene, chlorobenzene, 1,3,5-trimethylbenzene, sec-butyl-

benzene and naphthalene were detected. In wastewater from

the pharmaceutical industry, 1,1,2-trichloroethane and 1,3-

dichloropropane were detected.

3.2.2. Metals

All the investigated metals were detected in the waste-

water samples. The metals showing the highest concen-

trations were Fe (445–7265 Ag/l) and Al (523–979 Ag/l),followed by Cr (11.7–580 Ag/l) and Mn (45.4–225 Ag/l).The metals occurring in the lowest concentrations were

Mo (1.2–1.8 Ag/l), As (2.3–3.3 Ag/l) and Co ( < 0.80–

7.04 Ag/l).

3.3. Toluene extractable organotins

The highest concentrations of organotin compounds in

wastewater were observed in wastewater treatment plant of

Metamorfosis, in Athens (annual mean concentration 0.081

Ag/l). Input of these compounds into the municipal plants

could originate from their industrial uses or from the

leaching of PVC drain pipes (Fent, 1996).

3.4. Water quality objectives (WQO)

Water quality objectives (WQO) have been laid down in

national legal framework for a number of compounds

detected in the samples. These compounds were selected

on the base of the occurrence in the samples (concentration

and frequency) and the importance they have on water

quality (Van Leeuwen et al., 1996; Lekkas et al., 1999).

Taking into account the literature regarding the toxicity

and the potential health hazards associated with the 31

selected compounds, the WQO presented in Table 5 were

established for them, with the help of the recommended

values which were based on CSTE data. Quality standards

have been established in France by use of a similar

procedure (Babut et al., 2003), for priority compounds of

Table 7

Number of compounds detected in the water bodies

Water bodies Total number of

compounds

detected

Number of compounds

for which WQO have

been established

Strymonas 44 27

Axios 39 24

Evros 37 21

Pinios 36 22

Doirani 33 23

Nestos 33 19

Volvi 32 21

Aliakmonas 30 19

Pamvotida 27 16

Acheloos 26 17

Small Prespa 21 14

Alphios 21 14

Large Prespa 19 9

Asopos 18 11

Vegoritida 18 8

Vistonida 18 8

Evrotas 17 13

Pinios Peloponese 14 11

Pagasitikos 2 0

Saronikos 2 0

Thermaikos 1 0

Olympiada 0 0

T. Lekkas et al. / Environment International 30 (2004) 995–1007 1005

particular interest for French surface waters, different from

those investigated during the present study.

3.5. Emission limit values (ELV)

Emission limit values have been laid down at national

level regarding industrial discharges of substances of List II

of 76/464/EEC Directive (Table 6). The ELV are adopted as

average of the waste discharges by industrial processes.

These are not specific ELV adopted for specific processes

(Patterson, 1985). The relation between the WQO and the

corresponding ELV used in the Directives 83/513, 84/156,

84/491, 86/280, 88/347 and 90/415 was taken into account

for the establishment of ELV.

The total number of compounds detected in all water

bodies is presented in Table 7.

The water body where the largest total number of com-

pounds was detected was ST, followed by AX, EB and PIN,

while the one with the lowest was PINPEL. The lake with the

largest number of compounds was DO, followed by VO and

PAM, while the one with the lowest was VI. The total number

of compounds detected ranged from 14 to 44 for rivers, from

18 to 33 for lakes and from 0 to 2 for seawater (in seawater

only organotins were present). The number of detected

compounds for which WQO have been established ranged

from 11 to 27 for rivers and from 8 to 23 for lakes, which

denotes that legislative measures adopted cover a significant

number of toxic compounds detected in surface waters, thus

contributing to the protection of water quality in Greece.

Table 6

Emission Limit Values (ELV) (Ag/l) for the studied substances in

wastewater

Substance Month Day Substance Month Day

VOCs Insecticides

1,3-Dichlorobenzene 0.25 0.50 Endosulfan (total) 0.05 0.20

1,4-Dichlorobenzene 0.20 0.40 Fenthion 0.05 0.20

1,2-Dichlorobenzene 0.25 0.50 Azinphos methyl 0.05 0.20

2-Chlorotoluene 0.30 0.60 Azinphos ethyl 0.05 0.20

4-Chlorotoluene 0.25 0.50 Parathion (total) 0.05 0.20

Toluene 0.50 0.90 Mevinphos 0.05 0.20

Naphthalene 0.50 0.90 Demeton (total) 0.05 0.20

1,2-Dichloroethene 0.15 0.30 Fenitrothion 0.05 0.20

(cis and trans isomers) Malathion 0.05 0.20

Benzene 0.50 1.00 Metalsa

Dichloromethane 0.20 0.40 Arsenic 0.125 0.250

Ethylbenzene 0.30 0.60 Barium 2.5 5.0

Xylenes 0.50 0.90 Chromium 0.6 1.2

Chlorobenzene 0.30 0.60 Cobalt 0.25 0.50

Herbicides Copper 0.25 0.50

Atrazine 0.10 0.50 Lead 0.1 0.2

Simazine 0.05 0.20 Nickel 0.2 0.4

Linuron 0.05 0.20 Aluminum 2.5 5.0

Iron (total) 7.5 15.0

Manganese 1.0 2.0

Zinc 2.5 5.0

a The ELV reported here refer to discharges into lake water.

4. Conclusions

The pollution of the Greek surface waters from com-

pounds of List II, 76/464/EEC Directive, and other toxic

compounds was evaluated by sampling and analysis from

a monitoring network covering the most important water

bodies and municipal wastewater treatment plants of the

Greek territory.

The concentrations of VOCs and insecticides detected

in the surface waters of Greece were very low, whereas

the concentrations of herbicides and metals ranged gen-

erally at moderate levels and were elevated in a limited

number of cases, due to intense agricultural applications

or meteorological events and due to geological back-

ground of particular water bodies, respectively.

VOCs were detected almost exclusively in the rivers and

very rarely in the lakes, while the frequency of occurrence

of insecticides, herbicides and metals was similar for rivers

and lakes.

Regarding VOCs and organochlorine insecticides, the

rivers with the largest number of compounds detected

were Strymonas and Axios, while for organophosphorous

insecticides, herbicides and metals, Strymonas, Evros,

Nestos and Pinios. The lakes with the largest number of

compounds were Doirani and Vegoritida for organochlo-

rine insecticides, Doirani for metals and organophospho-

rous insecticides, and Vistonida for herbicides. Overall,

rivers Strymonas and Axios and lakes Doirani and Volvi

were the water bodies with the largest number of priority

substances.

T. Lekkas et al. / Environment International 30 (2004) 995–10071006

In municipal and industrial wastewater samples, a large

number of compounds were detected, at relatively high

concentrations in some cases.

The monitoring results and the relevant data have been

used for the establishment of legal measures, which will

have a direct effect on the reduction of pollution of the

compounds of interest as they will be used by the competent

authorities for deciding the emission limit values when

permits are issued. In this way, a control is adopted for

the discharges of these compounds. The operation of the

monitoring network is continuing and new legislative meas-

ures will be enforced if the results show that such additional

measures should be taken.

Acknowledgements

Financial support of this research by the Greek Ministry

of Environment is acknowledged.

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