Distribution and risk assessment of hydrocarbons (aliphatic and PAHs), polychlorinated biphenyls (PCBs), and pesticides in surface sediments from an agricultural river (Durance) and an industrialized urban lagoon (Berre lagoon), France

  • Fehmi Kanzari
  • Laurence Asia
  • Agung Dhamar Syakti
  • Anne Piram
  • Laure Malleret
  • Gilbert Mille
  • Pierre Doumenq
Article

DOI: 10.1007/s10661-015-4823-9

Cite this article as:
Kanzari, F., Asia, L., Syakti, A.D. et al. Environ Monit Assess (2015) 187: 591. doi:10.1007/s10661-015-4823-9

Abstract

The distributions of organic pollutants (like hydrocarbons, polychlorinated biphenyls (PCBs), and pesticides) and the risks on the ecosystem were studied in the Durance River and the Berre lagoon (France). High levels of aliphatic hydrocarbons were observed in all stations (1399 to 11,202 μg kg−1 dw). The n-alkanes were mainly from terrigenous origin confirmed by the values of different ratios calculated (carbon preference index (CPI), natural n-alkanes ratio (NAR), terrigenous/aquatic ratio (TAR), and ratio of low molecular weight to high molecular weight (LMW/HMW)). Total polycyclic aromatic hydrocarbon (PAH) concentrations in the surface sediments of the Durance River and Berre lagoon are 57–1528 and 512–863 μg kg−1 dw, respectively. Several ratios between parent polycyclic aromatic hydrocarbons showed that the sources of hydrocarbons in the sediments were generally more pyrolytic than petrogenic. The sum of seven PCB contents ranged from 0.03 to 13.13 μg kg−1 dw. Higher levels of PCBs were detected in sediments from the northern parts of the Berre lagoon (stations B1 and B3). Total pesticides contents ranged from 0.02 to 7.15 μg kg−1 dw. Among these compounds, ∑DDE and ∑DDT contents ranged, respectively, from 0.35 to 1.65 and from 0.37 to 1.52 μg kg−1 dw. However, PAH and PCB levels are not high enough to be a threat to aquatic organisms and human beings. Total PAH levels were below the effects range low (ERL) of 3500 μg kg−1 dw. For PCBs, only two stations (B1 and B3) are higher than the effect range median (ERM) of 180 μg kg−1 dw. For endrin (pesticide), the concentrations are between the ERL (0.02 μg kg−1 dw) and the ERM (45 μg kg−1 dw).

Keywords

Hydrocarbons PCBs Pesticides Risk assessment River and lagoon Sediments 

Introduction

The Durance River Basin, located in the South East of France, covers an area of 14,250 km2. The Durance river, 323.8 km length, extends from Montgenevre to south west of Avignon. The catchment area supports a population of over 450,000 inhabitants distributed in a very heteregenous way. There are more than 30 sewage treatment plants located on both sides of the Durance River within this area. The waste water discharge from these treatment units ranges from 174 to 6230 m3 per day, with the highest discharge from the North River Plant at Sisteron.

This work was carried out using guidelines set by European Directives such as 76/464/CEE concerning the analysis toxic and persistent compounds in environmental matrix (Directive 76/464/CEE 1976), the Water Framework Directive (Directive 60/2000/EC 2000), and Directive 2001/42/EC, which aimed at improving the ecological quality of surface waters and protecting the environment from toxic compounds (Directive 2001/42/EC 2001). According to these directives and to resolve the problem of sediment contamination and availability of hazardous compounds to biota, the present work tries to determine the evaluation of the vulnerability of the Durance River Basin which has been impacted by multiple human activities.

The three main objectives of this study are :
  1. (a)

    To know the distribution of organic pollutants in the sediment along the Durance river and the Berre lagoon. Hydrocarbons (n-alkanes and polycyclic aromatic hydrocarbons (PAHs)), polychlorinated biphenyls (PCBs), and pesticides.

     
  2. (b)

    To identify the different sources of hydrocarbons by using the diagnostic ratios like carbon preference index (CPI), natural n-alkanes ratio (NAR), terrigenous/aquatic ratio (TAR), and the ratio of low molecular weight to high molecular weight (LMW/HMW) for n-alkanes, Fl/(Fl + Pyr), Ant/(Ant + Phe), B[a]A/(B[a]A + Chry) and IPyr/(IPyr + B[ghi]P) for PAHs.

     
  3. (c)

    To evaluate ecotoxicological risk and to predict adverse biological effects in benthic organisms in compared sediment chemical data to numerical, effect-based Sediment Quality Guidelines (SQGs). In particular, two different approaches have been applied: the threshold effect level (TEL)–probable effect level (PEL) weight-of-evidence approach and the effect range low (ERL)–effect range median (ERM) weight-of-evidence approach (Long and Morgan 1990; MacDonald et al. 2000).

     

To accomplish these three major objectives, composite sediment samples were collected along the Durance River and the Berre lagoon.

Materials and methods

Sampling

Sampling of sediments of the Durance river (15 stations) and Berre Lagoon (two stations) was carried out from 3 June 2010 to 14 June 2010 (Fig. 1 and Table 1). Sampling was generally conducted on the bed of river. Sampling sites in the inner river were targeted by the Geographic Information Systems (GIS, MapInfo Professional 7.5, Boulogne-Billancourt, France), using predetermined global positioning system (GPS, Garmin Etrex summit HC, Kansas City, USA) coordinates to accurately locate each position. Each sample was collected using a stainless steel shovel, where the surface sediments were carefully placed in aluminum container. Samples were freeze dried at −80 °C, then ground to a powder with a mortar, pestle, and sieved with a stainless steel sieve at 200 μm. More details can be found in Kanzari et al. (2012 and 2014).
Fig. 1

Location of sampling sites of Durance river (D1 to D15) and Berre lagoon (B1 and B3)

Table 1

Detailed location and characteristics of sampling sites

Stations

Localisation

Type of sediment

D1

Tallard

44° 25ʹ 19.90ʺ N/6° 1ʹ 25.34ʺ E

Oozy, muddy sediment

D2

Upstream from Sisteron

44° 12ʹ 35.50ʺ N/5° 56ʹ 31.21ʺ E

Oozy, muddy sediment

D3

Confluence of Durance and Jabron

44° 12ʹ 6.43ʺ N/5° 56ʹ 39.15ʺ E

Fine-grained sand

D4

Downstream from confluence

44° 11ʹ 31.50ʺ N/5° 57ʹ 11.16ʺ E

Fine-grained sand

D5

Volonne

44° 6ʹ 30.18ʺ N/6° 0ʹ 31.67ʺ E

Oozy, muddy sediment

D6

Downstream from reservoir of Château-Arnoux

44° 5ʹ 2.42ʺ N/6° 0ʹ 40.33ʺ E

Oozy, muddy sediment

D7

Bridge of Mées

44° 2ʹ 9.09ʺ N/5° 57ʹ 51ʺ E

Oozy, muddy sediment

D8

South of Ganagobie

43° 58ʹ 26.04ʺ N/5° 54ʹ 52.92ʺ E

Oozy, muddy sediment

D9

Vinon sur Verdon-Verdon river

43° 43ʹ 40.98ʺ N/5° 48ʹ 36.78ʺ E

Oozy sediment

D10

Bridge of Mirabeau

43° 41ʹ 28.21ʺ N/5° 40ʹ 5.39ʺ E

Oozy, muddy sediment

D11

Pertuis

43° 40ʹ 31.06ʺ N/5° 27ʹ 37.17ʺ E

Oozy, muddy sediment

D12

Mallemort

43° 45ʹ 11.19ʺ N/5° 8ʹ 0.52ʺ E

Oozy, muddy sediment

D13

Cavaillon

43° 48ʹ 23.54ʺ N/5° 2ʹ 43.36ʺ E

Oozy, muddy sediment

D14

Cabannes

43° 53ʹ 54.87ʺ N/4° 54ʹ 54.87ʺ E

Oozy, muddy sediment

D15

Bridge of Avignon

43° 54ʹ 46.52ʺ N/4° 48ʹ 40.64ʺ E

Oozy, muddy sediment

B1

Berre lagoon

43° 28ʹ 22.88ʺ N/5° 3ʹ 58.16ʺ E

Oozy, muddy sediment

B3

North Berre lagoon

43° 31ʹ 5.65ʺ N/5° 4ʹ 20.59ʺ E

Oozy, muddy sediment

Chemicals analysis

Reference compounds were obtained from Dr. Ehrenstorfer (Augsburg, Germany). Every compound had a purity of 98–99 %. A primary solution containing all compounds and working solutions were prepared from a solution of 10 μg mL−1 in ethyl acetate (Kanzari et al. 2012).

Detailed descriptions of extraction steps for organic pollutants in sediments can be found in Kanzari et al. (2012 and 2014). For hydrocarbons, dried sediment samples were extracted in a mixture of dichloromethane/hexane by Soxhlet extractor and subjected to an open-column alumina/silica cleanup procedure followed by analysis.

For PCBs and pesticides, 10 g of dried sediments were spiked with Mirex as surrogate standard and extracted by HEX/ACE (1:1, v/v) using an accelerated solvent extraction system ASE 200 (Dionex, USA) at 100 °C and under 1500 psi.

Instrumental analysis

Hydrocarbon fractions (F1 and F2), PCBs, and pesticide fractions were analyzed by capillary gas chromatography coupled to mass spectrometry (GC-MS; Autosystem XL GC and TurboMass from PerkinElmer, USA). Chromatographic conditions were as follows: splitless injection (30 s), Elite 5MS column (30 m × 0.25 mm i.d. × 0.25-μm film thickness). Detailed descriptions of analysis for organic pollutants in sediments can be found in Kanzari et al. (2012 and 2014). Every sample was analyzed by selected ion monitoring (SIM) mode using the base peak to quantify each compound.

Quality control and assurance

All data were subject to quality and control procedures. Procedural blanks were carried out between each batch of four samples and no contamination was found. A certified reference material CNS391-050 “PAHs, PCBs and pesticides on Fresh Water Sediment” purchased from Sigma-Aldrich (Molsheim, France) was analyzed to evaluate the extraction accuracy. The recoveries for PAHs, PCBs, and pesticides range from 69 to 125, 81 to 112, and 78 to 114 %, respectively. For n-alkanes, we obtained the same results as the study on the Arc and Huveaune rivers (Kanzari et al. 2012 and 2014).

The mass of each individual PAHs, PCBs, and pesticides in the blanks were insignificant relative to that of the sediment samples. The relative standard deviations (RSD) were between 1.3 and 4.5 % for PAHs and 3 and 22 % for PCBs and pesticides. The detection limits of PAHs, PCBs, and pesticides at a signal to noise ratio (S/N) of 3 were 0.01–0.26, 0.01–0.06, and 0.006–1 μg kg−1 dw, respectively.

Results and discussion

Gravimetric data are given in Table 2. Extractable organic matter (EOM) content in sediments varied from 210 to 2370 mg kg−1 sed dw. The lowest values was observed in station D4 and the highest values were found at B1 and B3 stations. Total hydrocarbon contents (THC) vary significantly from 70 mg kg−1 (station D2) to 1960 mg kg−1 dw (station B1).
Table 2

Gravimetric data (mg kg−1 dw) and concentrations of alkanes and PAHs in sediment samples of Durance River (Stations D1 to D15) and Berre lagoon (B1 and B3) (μg kg−1 dw)

Stations

D1

D2

D3

D4

D5

D6

D7

D8

D9

D10

D11

D12

D13

D14

D15

B1

B3

EOM

370

370

340

210

660

400

330

390

550

320

350

520

550

330

540

2370

880

THC

110

70

80

100

170

130

80

110

170

80

90

120

120

80

130

1960

240

∑alk

2937

4238

2313

2342

10,825

2598

2962

8178

11,202

3018

4430

3773

4541

3388

4498

1398

1985

 n-C17/Pr

1.1

3.3

1.2

0.9

1.2

1.3

1.3

1.0

1.2

0.9

1.0

1.2

3.7

1.2

1.5

1.4

2.6

 n-C18/Phy

0.9

2.4

1.1

1.0

1.1

1.1

1.4

1.3

0.8

0.9

0.9

1.1

1.3

1.1

1.1

1.1

1.2

 Pr/Phy

0.4

0.6

0.7

0.8

0.5

0.8

1.0

0.5

0.3

0.3

0.4

0.3

0.4

0.3

0.3

0.0

0.8

 CPI(24–32)a

9.3

2.6

3.2

3.1

6.6

5.5

5.3

6.2

8.2

5.7

6.5

6.1

9.3

7.0

7.3

5.7

6.0

 TAR

26.1

2.0

4.5

9.3

37.7

10.9

8.1

>50

>50

30.8

35.7

22.4

27.1

27.3

27.0

32.1

6.4

 NAR

0.7

0.3

0.4

0.4

0.7

0.6

0.5

0.6

0.7

0.5

0.6

0.6

0.7

0.6

0.6

0.6

0.6

 LMW/HMWb

0.1

0.5

0.3

0.2

0.1

0.2

0.2

0.0

0.0

0.1

0.1

0.1

0.1

0.1

0.1

0.1

0.2

∑16PAH

57

272

172

339

112

1103

1025

791

537

561

805

563

150

1528

679

863

512

 Ant/(Ant + Phe)

0.16

0.16

0.13

0.11

0.10

0.12

0.10

0.16

0.20

0.28

0.36

0.21

0.14

0.47

0.16

0.12

0.14

 Fl/(Fl + Pyr)

0.54

0.49

0.56

0.55

0.52

0.55

0.49

0.49

0.55

0.80

0.75

0.90

0.84

0.80

0.85

0.56

0.54

 BaA/(BaA + Chry)

0.61

0.47

0.51

0.47

0.29

0.32

0.22

0.32

0.40

0.50

0.43

0.37

0.41

0.45

0.35

0.28

0.36

 IPyr/(IPyr + BghiP)

0.46

0.49

0.47

0.51

0.26

0.45

0.31

0.41

0.53

0.46

0.49

0.39

0.42

0.51

0.44

0.29

0.29

 LMW/HMWc

0.72

0.68

0.18

0.08

0.24

0.08

0.54

0.17

0.11

0.13

0.10

0.22

0.08

0.12

0.20

0.34

0.51

TAR terrigenous/aquatic ratio, NAR natural n-alkanes ratio

aCarbon index preference calculated as 2 (C25 + C27 + C29)/(C24 + 2 (C26 + C28 + C30) + C32)

bRatio sum of low molecular weight (nC14 to nC20) to high molecular weight (nC21 to nC34) n-alkanes

cSum of 2 and 3-ring PAH divided by the sum of 4 to 6-ring PAH

Distribution and sources of alkanes

GC patterns of saturated hydrocarbons comprise a series of resolved peaks (n-alkanes and some branched alkanes such as pristane and phytane) and an “unresolved complex mixture” (UCM). The UCM, ranging from nC14 to nC34, is unimodal (Fig. 2).
Fig. 2

Capillary column gas chromatograms of the saturated hydrocarbons fractions (stations D3, D6, D10 and B3). Numbers indicate n-alkanes (carbon chain length); UCM “Unresolved Complex Mixture”, IS internal standard (nonadecane-d40)

Alkanes concentrations in surface sediments varied from 1399 to 11,202 μg kg−1 dw. High levels of alkanes (>3000 μg kg−1 dw) are found at stations D2, D5, D8, D9, D10, D11, D12, D13, D14, and D15 (Table 2). For the other sites, concentrations are lower, ranging from 1399 to 2961 μg kg−1 dw. The most dominant compounds found in the sediments are nC27, nC29, nC31, and nC33 (Fig. 2). Light n-alkanes nC14-20 are often less abundant than heavier n-alkanes nC21-34.

To describe the n-alkane distributions in the samples, the ratio low- to high-molecular-weight compounds, n-C17/Pr, n-C18/Phy, Pr/Phy, carbon preference index (CPI), natural n-alkanes ratio (NAR), and terrigenous/aquatic ratio (TAR) were calculated (Table 2).

Pristane and phytane are the products of the geological alteration of phytol and are often used as indicators of petroleum contamination (Readman et al. 2002; Guo et al. 2011). Low values of these indexes generally suggest the presence of degraded oils. For all stations except D2, D13, B1, and B3, low ratio values of n-C17/Pr are found, which indicates a preferential degradation of linear n-alkanes rather than branched ones. The n-C18/Phy ratio is <1 for stations D1, D9, D10, and D11 (Table 2), thus confirming the presence of degraded oil residues already indicated by the existence of the UCM. Concerning Pr/Phy ratio, a low value reflects a petroleum contamination. For all stations, the CPI ratio is markedly higher than 1, which is an evidence of recent terrigenous inputs (Table 2).

To improve the sensitivity of the CPI, the LMW/HMW ratios calculated for the Durance River and the Berre lagoon samples are markedly less than 1 (0.0 to 0.5) and thus confirm that n-alkanes in the Durance River and the Berre lagoon sediments essentially resulted from terrigenous inputs (Kanzari et al. 2012).

For the Durance River and Berre lagoon sediments, the NAR ranged between 0.3 and 0.7, in accordance with CPI results. The influence of a terrestrial inputs is well marked in stations D1, D5, D6, D8, D9, D11, D12, D13, D14, D15, B1, and B3 (Kanzari et al. 2012).

The terrigenous/aquatic ratio (TAR) is very high for all stations (Table 2) and confirms that terrestrial inputs in the Durance River and the Berre lagoon are important.

Distribution and sources of PAHs

All sediment samples contain significant levels of PAHs. The total PAHs content, defined as the sum of the contents of all 16 EPA PAHs, range from 57 to 1528 μg kg−1 dw (Table 2). Total PAHs content was relatively high in sediments collected from stations D6, D7, D8, D11, D14, D15, and B1 (679 to 1528 μg kg−1 dw). Furthermore, the latter stations present high amounts of 4- to 6-ring PAHs (58–93 %). The highest PAHs content was found at station D14, which is located in an urbanized area between Cavaillon and Avignon. According to Molvær et al. (1997), all stations are classified in class II “moderately polluted” except station D1.

PAH diagnostic ratios have been used to identify the different pollution emission sources like diesel and gasoline combustion emissions (Westerholm et al. 2001; De La Torre-Roche et al. 2009), different crude oil processing, and biomass burning processes (Yunker et al. 2002; Akyüz and Çabuk 2010). In Table 3, we have tried, on the basis of the different criteria, to classify the stations according to hydrocarbon origins.
Table 3

Classification of sampling stations according to different ratio

PAH ratio

Petrogenic

Mixed origin

Pyrogenic

Ant/(Ant + Phe)a

<0.1

 

>0.1

 

D5-7

D1-2-3-4-6-8-9-10-11-12-13-14-15/B1-3

Fl/(Fl + Pyr)b

<0.4

0.4–0.5 (fossil fuel combustion)

>0.5

 

D2, D7, D8

D1-3-4-5-6-9-10-11-12-13-14-15/B1-3

BaA/(BaA + Chry)c,d

<0.2

0.2–0.35 (coal combustion)

>0.35

 

D5-6-7-8/B1

D1-2-3-4-9-10-11-12-13-14-15/B3

IP/(IP + BghiP)d

<0.2

0.2–0.5 (fuel combustion)

>0.5

 

D1-2-3-5-6-7-8-10-11-12-13-15/B1-3

D4-9-14

BaA/Chryd

<0.4

 

> 0.4

D7

 

D1-2-3-4-5-6-8-9-10-11-12-13-14-15/B1-3

IPyr/BghiPd

<0.2

 

>0.2

  

All stations

ƩLMWƩ/HMWe

>1

 

<1

  

All stations

aPies et al. 2008

bDe La Torre-Roche et al. 2009

cAkyüz and Çabuk 2010

dYunker et al. 2002

eZhang et al. 2008

At all stations, the ratio Ant/(Ant + Phe) is above 0.1 (between 0.10 and 0.47) which shows the pyrogenic origin of PAHs. Stations D1, D2, D3, D4, D5, D6, D7, D8, D9, B1, and B3 have values Fl/(Fl + Pyr) ratio between 0.4 and 0.5 which indicates a pyrolytic source and more specifically automobile emission due to the presence of industrial areas (Château-Arnoux and Etang de Berre). Stations D10, D11, D12, D13, D14, and D15, where the values are over 0.5, reflect more of a coal/grass/wood combustion origin which is explained by the important urbanization of this area (Avignon).

For stations D5, D6, D7, D8, D12, D15, B1, and B3, the BaA/(BaA + Chry) ratio is between 0.2 and 0.35 and indicates a mixed source. For the other stations, the ratio >0.35 implies a combustion source. This is confirmed by the IPyr/(IPyr + BghiP) ratio which is between 0.2 and 0.5 for all stations and suggests a liquid fossil fuel (vehicle and crude oil) combustion, except for stations D4, D9, and D14.

At all stations, the ratios Ant/(Ant + Phe), BaA/(BaA + Chry), and IPyr/(IPyr + BghiP) confirm the pyrogenic origin of PAHs. Studies have shown that low LMW/HMW (sum of two and three rings PAHs to the sum of more than three rings PAHs) ratios (<1) often indicates PAHs that derived mainly from pyrogenic sources (Table 2).

Distribution and sources of PCBs

Sediment samples from the Durance River show a low content of PCBs ranging from 0.03 (station D1) to 13.13 μg kg−1 dw (station D2) (Table 4). Except station D9, average levels of PCBs in sediments of the Durance River is near 1 μg kg−1 dw. On the other hand, very high values of PCBs are found in the Berre lagoon (Table 6). These results show that there is a principal source of PCBs in the Berre lagoon which lies close to petrochemical (LyondellBasell), industrial, and hydroelectric (EDF, Electricité De France) plants. Among the hexachloro-congeners (CB 138 and CB153) are the most abundant (~ 50 % of total PCBs). Stations B1 and B3 are classified as class IV “strongly polluted” and the other stations of Durance River are class II “insignificantly polluted” (Molvær et al. 1997; Cardellicchio et al. 2007).
Table 4

Concentrations of PCBs and pesticides in sediment samples of Durance river (Stations D1 to D15) and Berre lagoon (B1 and B3) (μg kg−1 dw)

Stations

D1

D2

D3

D4

D5

D6

D7

D8

D9

D10

D11

D12

D13

D14

D15

B1

B3

Polychlorobiphenyls

PCB28

dl

0.08

0.04

0.04

0.37

0.07

0.08

0.06

0.04

0.03

0.10

0.13

0.02

0.07

0.53

50.80

59.06

PCB52

dl

dl

dl

0.04

0.25

0.02

0.01

0.01

0.23

0.02

0.03

0.02

0.02

0.02

0.21

35.38

15.79

PCB101

dl

0.03

0.01

0.03

0.17

0.05

0.02

0.17

1.69

0.02

0.11

0.09

0.02

0.14

0.28

29.97

35.50

PCB118

dl

0.01

0.01

0.03

0.09

0.01

dl

0.05

2.63

0.05

0.18

0.16

0.02

0.16

0.34

52.12

52.31

PCB153

0.01

0.03

0.04

0.03

0.43

0.07

0.16

0.52

3.81

0.12

0.34

0.42

0.12

0.41

0.63

141.63

115.14

PCB138

0.01

0.01

dl

0.05

1.02

0.06

0.24

0.39

3.66

0.16

0.35

0.39

0.09

0.39

0.59

143.99

83.37

PCB180

0.01

0.03

0.13

0.10

0.33

0.04

0.05

0.33

1.08

0.10

0.18

0.33

0.03

0.21

0.36

87.52

49.01

PCBa

0.03

0.19

0.23

0.32

2.66

0.32

0.57

1.53

13.13

0.50

1.29

1.54

0.32

1.40

2.93

514.4

410.2

Pesticides

Chlopyrifos

dl

dl

dl

dl

dl

dl

dl

dl

dl

dl

dl

dl

dl

dl

dl

Chlorfenvinphos

0.01

1.79

0.16

1.38

dl

0.40

0.35

0.14

0.35

0.36

0.23

1.22

0.49

1.66

0.26

0.02

0.08

Endrin

0.17

0.37

0.10

0.10

0.10

0.48

0.39

0.63

0.04

0.10

0.53

0.45

0.51

0.17

0.05

0.12

∑OC-OPb

0.18

2.16

0.27

1.38

0.10

0.50

0.83

0.53

0.98

0.40

0.33

1.75

0.95

2.11

0.43

0.07

0.20

o,pʹ-DDE

0.35

0.45

0.37

0.36

0.36

0.36

1.65

0.36

0.40

0.35

0.36

p,pʹ-DDE

0.75

1.07

0.83

0.61

0.59

0.76

0.63

0.61

0.59

0.62

0.59

0.62

0.59

0.99

o,pʹ-DDT

1.52

0.57

p,pʹ-DDT

0.37

0.40

0.39

0.38

0.90

0.38

0.38

0.41

0.40

0.38

0.43

∑DDEc

0.35

1.20

1.07

1.20

0.97

0.59

1.12

0.99

1.65

0.97

0.59

1.02

0.94

0.62

0.95

0.99

∑DDTd

0.37

0.40

1.52

0.39

0.38

1.47

0.38

0.38

0.41

0.40

0.38

0.43

dl detection limit

aSum of the seven US EPA PCB

b∑OC-OP = (trifluraline + α-HCH + lindane + chlopyrifos + aldrine + isodrine + chlorfenvinphos + endosulfan I + dieldrin + endrin + endosulfan II)

c∑DDE = (o,pʹ-DDE + p,pʹ-DDE)

d∑DDT = (o,pʹ-DDT + p,pʹ-DDT)

The proportions of the various PCB congeners in the sediment samples differed significantly. Congeners containing 5–7 chlorine atoms accounted for more than 84 % of the total PCBs with the penta- (CB101 and CB118), hexachloro- (CB153 and CB138), and heptachloro- (CB180) congeners much more prominent than the trichloro- (CB28) and tetrachloro-(CB52) congeners. The presence of tetrachloro- (CB52), pentachloro- (CB101 and CB118), and hexachloro- (CB 138 and CB153) congeners is consistent with a contribution from the commercial mixtures, which have been widely used in transformers, electrical equipments, and other industries in several countries (Barakat et al. 2002). In France, PCBs in sediments are mainly derived from commercial mixture congeners, DP-6 which is rather close to US Aroclor1260 (Wafo et al. 2006).

Distribution and source of pesticides

On the 15 ban-use pesticides analyzed, only 7 pesticides were detected. Chlorfenvinphos, an insecticide, was detected in every sample and at the highest concentration (1.79 μg kg−1 dw). Chlorpyrifos (detected in 88 % of samples) and Endrin (94 %) were quantified in more than half the samples. The historically used p,pʹ-DDT and its degradation products were also detected in about 60 % of samples. Banned in 1970, this could be explained by the presence in the vicinity of a chemical site, formerly used as a factory for commercial pesticide formulation. The pesticide concentrations are summarized in Table 4.

The total concentration of organochlorine (endrin) and organophosphorus (chlorpyrifos and chlorfenvinphos) pesticides in surface sediments revealed a wide range of fluctuation, from 0.07 to 2.16 μg kg−1 dw (Table 4). The highest concentrations were found at stations D2 and D14 (2.16 ng/g and 2.11 μg kg−1 dw, respectively), while the lowest concentrations were found at stations B1 and D5 (0.07 and 0.10 μg.kg-1 dw, respectively). The results may suggest that the high concentrations of pesticides in the surface sediments are caused by inputs from urban activities, the large amount of discharged soil runoff and sewage.

Among the individual components of pesticides, DDTs (sum of DDT and its metabolites), which ranged from 0.43 (station B1) to 3.12 (station D9) μg kg−1 dw were found to be the most abundant ones, and account for 43-93 % of the total pesticides. Chlorfenvinphos, which ranged from <dl (station D5) to 1.79 (station D2) μg kg-1 dw accounted for about 0.1-52 % of the total pesticides. Endrin, which ranged from not detected (station D4) to 0.63 (station D9) μg kg−1 dw accounted for about 0–26 % of the total pesticides. Chlorpyrifos is present practically in all stations but at very low concentrations. This characteristic distribution of pesticides is similar to previous observations and is also similar to those found in sediments from Pau Lagoon, France (Leaute 2008) and Albufera Lake, Spain (Peris et al. 2005).

Evaluation of ecotoxicological risk

The sediment quality guidelines (SQGs) have been used in numerous applications, for sediment quality and ecological risk assessments, and developing sediment quality remediation objectives (Long 1998). Specifically, the previously published SQGs for the protection of sediment-dwelling organisms in freshwater ecosystems were grouped into different categories: threshold effect levels (TELs), effect range low values (ERLs), probable effect levels (PELs), and effect range median values (ERMs) (Long 1998; Long and MacDonald 2006).

Based on the sediment quality guideline of threshold effect level (TEL <870 μg kg−1 dw) and effects range low (ERL >3500 μg kg−1 dw) (Burton 2002), PAHs levels in the Durance River sediments were under the TEL for total PAHs (870 μg kg−1 dw) except in the industrial area of Chateau-Arnoux (D6 and D7) and an urbanized area near Avignon (D14). PAH concentrations in Durance River are expected to rarely cause adverse biological effects (Fig. 3a).
Fig. 3

Spatial contour maps of ecotoxicological risk of Ʃ16PAH (a), of ƩPCBi (b), and of ƩDDT (c)

For PCBs, all stations of Durance river are below the ERL (22.7 μg kg−1), and stations of Berre Lagoon (B1 and B3) are higher than the ERM (180 μg kg−1) (Fig. 3b).

The effects range low (ERL) and the effects range median (ERM) only refer to endrin, ∑DDE and ∑DDT (Smith et al. 1996). In this study, all stations, except station D4, are between the ERL and the ERM (0.02-45 μg kg−1 dw), but all stations are below the TEL (2.67 μg kg−1 dw) for endrin. ∑DDT concentrations at stations D3 and D9 are between the ERL and the ERM (1-7 μg kg-1 dw) and all stations were below the ERL (2 μg kg−1 dw) for ∑DDE. But ∑DDE concentrations at station D9 are between the TEL and the PEL (1.42-6.75 μg kg−1 dw) (Fig. 3c).

Conclusions

For all stations, the presence of terrigenous hydrocarbons is very clear. The study of polycyclic aromatic hydrocarbons shows that the sources are generally much more pyrolytic than petrogenic. There are multiple sources of hydrocarbons in the Durance River and in the Berre lagoon, linked to the specificities of the sites: several industrial activities, steel and iron industries, refineries, heavy traffic of trucks and cars, and important atmospheric emissions due to the oil industry. The Durance River and the Berre lagoon were contaminated by a variety of organochlorine and organophosphorous pesticides, some of which have been banned for years. The content of pesticides varied between geographical areas and locations. Locations with vineyards, wheat culture, and market gardening had higher contents of lindane, chlorfenvinphos, and chlopyrifos, while the content of endrin is due to its persistence and the degradation of aldrin, dieldrin, and isodrin in the environment. This study provides baseline study data for in the context of an integrated river basin management program with emphasis on the biodiversity, freshwater reserve, as well as economic activities of the Provence region.

The content of total PAHs and total PCBs in studied samples are similar or substantially lower, to those found in many other aquatic systems and significantly less than current sediment quality criteria (ERL and ERM).

Acknowledgments

The authors specially thank Mr. Max Bresson and Mr. Michel Guiliano for their help during sampling trips.

Copyright information

© Springer International Publishing Switzerland 2015

Authors and Affiliations

  • Fehmi Kanzari
    • 1
  • Laurence Asia
    • 1
  • Agung Dhamar Syakti
    • 1
    • 2
  • Anne Piram
    • 1
  • Laure Malleret
    • 1
  • Gilbert Mille
    • 1
  • Pierre Doumenq
    • 1
  1. 1.Aix Marseille UniversitéAix-en-Provence Cedex4France
  2. 2.Fisheries and Marine Sciences Department-Jenderal Soedirman UniversityKampus Perikanan Unsoed KarangwangkalPurwokertoIndonesia

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