# Polychlorinated Biphenyls, Polybrominated Diphenyl Ethers, and Phthalates in Roach from the Seine River Basin (France): Impact of Densely Urbanized Areas

Marie-Jeanne Teil, Khawla Tlili, Martine Blanchard, Pierre Labadie, Fabrice Alliot, Marc Chevreuil

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Marie-Jeanne Teil, Khawla Tlili, Martine Blanchard, Pierre Labadie, Fabrice Alliot, et al., Polychlorinated Biphenyls, Polybrominated Diphenyl Ethers, and Phthalates in Roach from the Seine River Basin (France): Impact of Densely Urbanized Areas. Archives of Environmental Contamination and Toxicology, 2013, 66 (1), pp.41-57. 10.1007/s00244-013-9955-8. hal-05354272

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# Polychlorinated Biphenyls, Polybrominated Diphenyl Ethers, and Phthalates in Roach from the Seine River Basin (France): Impact of Densely Urbanized Areas

Marie-Jeanne Teil · Khawla Tlili · Martine Blanchard · Pierre Labadie · Fabrice Alliot · Marc Chevreuil

**Abstract** Endocrine disruptors (EDs) from three chemical classes—polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs), and phthalates—were investigated in the Seine River and one tributary, the Orge River, upstream and downstream of urban areas. The impact of urban areas was characterized by a concentration increase of all compounds in the Seine River and for phthalates and PBDEs in the Orge River. In the Seine River, from upstream (Marnay) to downstream (Triel) of urban areas, water concentration increases were greater for diethylhexyl phthalate (DEHP) (6 times, *p* < 0.05) and Σtri-hexa BDE (5 times [*p* < 0.05]) than for Σ7PCBi (2.6 times). Simultaneously, sediments displayed a strong accumulation of contaminants downstream and compared with upstream values, their concentrations increased greatly: 202-fold for DEHP, 69-fold for BDE209, 25-fold for Σtri-hexa-BDE, and 11-fold for Σ7PCBi. Variations of fish ED concentrations gave an indication of their habitat contamination increase observed downstream of densely urbanized areas of the Seine River, especially for PBDEs (Σtri-hexa-PBDEs = 14-fold increase ≤15.7 ± 6.9 ng g⁻¹ dry weight [dw;

*p* < 0.001]) and for PCBs (Σ7PCBi eightfold increase ≤211 ± 55 ng g⁻¹ dw [*p* < 0.01]). PCA results highlighted relationships between the different ED classes. A correlation (*p* < 0.05) was observed between PCB and PBDE fish concentrations, suggesting common sources and similar absorption mechanisms. For PCBs, which were poorly biodegraded, the bioaccumulation factor was strongly correlated (*p* < 0.001) to molecular hydrophobicity, whereas for PBDEs a negative correlation (*p* < 0.05) was observed related active debromination processes. This multichemical study investigates for the first time the occurrence of a wide range of EDs in roach, which was chosen as a sentinel species for this survey of surface water contamination.

A growing list of substances—including polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs), and phthalates—are suspected of having endocrine-disrupting properties (Sharpe and Irvine 2004; Birnbaum and Staskal 2004; Uren-Webster et al. 2010). PCBs have been produced since 1930, and their worldwide amount during the last 60 years ranged from 1.2 to 2 million tons. Despite the restriction legislation in effect since the 1970s in the USA and Europe and since 1993 in Russia, PCBs are still persist in the environment (Breivik et al. 2004). PCBs have been involved in thyroid and estrogenic disturbances (Cheek et al. 1999; Sharpe and Irvine 2004).

PBDEs constitute a major class of flame retardants used in many manufactured goods to decrease their flammability (De Wit et al. 2010). Historically, three major commercial formulations were used: penta-, octa-, and deca-BDE. Only the latter is still authorized in the European Union after the other formulations were phased out. PBDEs decrease plasma levels of thyroxine in fish and rodents and exert

M. J. Teil (✉) · K. Tlili · M. Blanchard · F. Alliot · M. Chevreuil
Unité mixte de recherche UMR 7619 SISYPHE, CNRS/ Université Pierre et Marie Curie, Paris, France
e mail: marie.jeanne.teil@upmc.fr

M. J. Teil · K. Tlili · M. Blanchard · F. Alliot · M. Chevreuil
Laboratoire Hydrologie Environnement LHE, Ecole Pratique des Hautes Etudes EPHE, Tour 46/56, 4 place Jussieu, 75252 Paris Cedex 05, France

P. Labadie
Laboratoire de Physico et Toxico Chimie de l'environnement LPTC, UMR 5805 EPOC, CNRS/Université Bordeaux 1, 351 cours de la Libération, 33405 Talence, France
estrogenic potencies by acting as estrogen-receptor agonists, suggesting possible effects on gonad development and sex differentiation (Hallgren et al. 2001; Meerts et al. 2001; Lema et al. 2007).

Phthalates have been synthesized since the 1930s as plasticizers, mainly for polyvinyl chloride (PVC). Because they are extensively used in common life products, their worldwide production reached 4.3 million tons in 2006, representing one half by DEHP (Peijnenburg and Struijs 2006). In 2000, this compound was listed among the 33 hazardous substances of the Water European Framework Directive (DCE 2000/60/CE). Consequently, the plasticizer industry evolved toward a progressive shift from DEHP to higher molecular-weight phthalates. However, PVC recycling activity increased by four times in Europe during the last decade, reaching 260,000 tons of treated product in 2010, and might tend to become a new potent input source of DEHP to the environment (Vinyl 2010). Phthalates have been involved in toxic processes, namely endocrine disruption, in rodents, fish, and invertebrates (Scarano et al. 2009; Uren-Webster et al. 2010; Planelló et al. 2011).

These three chemical endocrine-disruptor (ED) classes are commonly encountered in surface water and sediment of European rivers. PCB concentrations have been reported in the Ebro River (Spain) at average values of 76 ng L⁻¹ for surface water and 10–50 ng g⁻¹ dry weight (dw) for sediment (Fernandez et al. 1999). In the Seine River (France), concentrations from 11 to 33 ng L⁻¹ for surface water and 67–6,970 ng g⁻¹ dw for sediment were recorded (Teil et al. 1996; Chevreuil et al. 1998). For PBDEs, sediment concentrations in 22 European rivers ranged from <0.17 to 6.2 ng g⁻¹ dw for BDE47, <0.19–7 for BDE99, and from <0.51 to 1,800 for BDE209 (De Wit 2002). DEHP levels in Europe varied from 0.08 to 10 µg L⁻¹ in surface water (Fromme et al. 2002; Peijnenburg and Struijs 2006) and 2–55 µg kg⁻¹ dw in sediment (Vethaak et al. 2005).

The three groups of chemicals suspected of endocrine disruption were detected in a number of fish species and other aquatic organisms from different trophic levels (Law et al. 2008). Hecker et al. (2002) reported endocrine disruption in Cyprinidae (*Abramis brama*) from the Elbe River (Germany). In addition, roach (*Rutilus rutilus*) from streams receiving discharges of domestic sewage in Denmark showed intersex feature in males at the effluent-impacted sites (Bjerregaarda et al. 2006). Moreover, roach from the Seine River showed primary oocytes in testes with the incidence ranging from 9 to 21 % of males (Minier et al. 2000).

Our aim was to investigate the distribution of the three classes of contaminants suspected of endocrine-disrupting effects—PCBs, PBDEs, and phthalates—in a ubiquitous Cyprinidae, the roach (*Rutilus rutilus*), from two rivers

flowing through densely populated areas and affected by urban runoff and sewage discharge in the Ile-de-France district: the Seine River and one suburban tributary, the Orge River. First, contamination levels of water and sediment from sites upstream and downstream of urbanized areas were determined. Simultaneously, concentrations and molecular patterns of the three ED classes in roach living in areas with contrasted urbanization levels were investigated. Then contaminant bioaccumulation in roach was estimated by means of bioaccumulation factors (BAFs), and their variations were considered in relation with molecular properties.

## Materials and Methods

### Chemicals

Silica gel (40–63 µm, 200 m² g⁻¹), neutral alumina (32–63 µm, 200 m² g⁻¹), and C18 sorbents (40–63 µm, 500 m² g⁻¹, carbon load 18 %, end capped) were supplied by Interchim (Montluçon, 03, France). Florisil (150–250 µm, 300 m² g⁻¹), sulphuric acid (>98 %, nitrogen-analysis grade) and gas chromatography–quality solvents (Merck-Suprasolv) were supplied by VWR International (Fontenay-sous-Bois, 94, France). Helium and nitrogen (99.999 %) were supplied by Air-Liquide (Paris, 75, France). Acidic silica (44 % sulphuric acid [w/w]) was prepared by mixing neutral silica gel (previously baked at 400 °C) with sulphuric acid (98 %). Sorbents used for column cleanup were baked at 400 °C (4 h) and stored at 150 °C before use.

Mixed native PBDE standard solutions were purchased from Wellington Laboratories (by way of BCP Instruments, Irigny, 69, France). BDE mixture contained 17 28, 47, 49, 99 100, 119, and 126 each at 1 ng L⁻¹; BDE153 and 154, each at 2 ng L⁻¹; and BDE209 at 5 ng L⁻¹. ¹³C₁₂BDE47, ¹³C₁₂BDE153, BDE181 (each at 50 ng L⁻¹ in nonane), and ¹³C₁₂BDE209 (50 ng L⁻¹ in toluene) (Wellington Laboratories) were used as internal standards (ISs). The working solution in toluene contained each IS at 0.5 ng L⁻¹, except for ¹³C₁₂BDE209, which was at 1.25 ng L⁻¹. ¹³C₁₂BDE47 was used as IS for tri- to penta-BDEs, ¹³C₁₂BDE153 for hexa-BDEs, and ¹³C₁₂BDE209 for BDE209. BDE77 (Sigma-Aldrich, St Quentin Fallavier, 38, France) and bromobiphenyl 209 (Wellington Laboratories) were used as syringe standards (SrSs) to determine IS recoveries: ¹³C₁₂BDE47 and ¹³C₁₂BDE153 with BDE77 and ¹³C₁₂BDE209 with bromobiphenyl-209.

Mixed native PCB standard solutions and individual congeners were purchased from LGC Standards (Molsheim, France) and included a seven key-isomer mix containing CB28, 52, 101, 118, 138, 153, and 180, each at 10 µg mL⁻¹, in isooctane and a World Health Organisation
<figure><img src="image_3.png" /><figcaption>**Fig. 1** Location of the sampling points for water, sediment, and fish on the Orge River (Roinville and Viry Châtillon) and the Seine River upstream (Marnay sur Seine) and downstream of Paris (Epinay sur Seine and Triel sur Seine)</figcaption></figure>

(WHO) coplanar and mono-ortho-PCB mix containing CB77, 81, 126, and 169, for nonortho PCBs and CB105, 114, 118, 123, 156, 157, 167, and 189 for mono-ortho PCBs, each at 10 µg mL⁻¹, in isooctane. CB30 and CB107 were used as ISs. A working solution was prepared at 100 pg µL⁻¹ each in isooctane (CB30 IS for CB28, 52, 101, 105, and 110 quantifications; CB107 IS for the other PCBs). ¹³C₁₂CB194 was used as SrS for IS recovery determination.

A solution of six standards of phthalates in isooctane (dimethyl phthalate [DMP], diethyl phthalate [DEP], di-n-butyl phthalate [DnBP], butylbenzyl phthalate [BBP], DEHP, di-n-octyl phthalate [DnOP]) was purchased from Supelco (by way of Sigma-Aldrich, St. Quentin Fallavier, France). Dipentyl phthalate (DPP; Supelco) was used as IS and benzyl benzoate (Supelco) as SrS.

## Sample Collection and Treatment

Sample collections were performed first in the Orge River at a rural site (Roinville [48°N 2°2′E]) and at an urban site at the sub-basin outlet (Viry-Châtillon [48°40′23″N; 2°21′30″E]). They were secondly performed in the Seine River upstream at Marnay-sur-Seine (48°30′N, 3°33′E) and downstream of the discharges from the densely populated areas of Paris at Epinay-sur-Seine (48°57′N 2°18′E) and Triel-sur-Seine (48°58′N 2° 00′E) (Fig. 1).

Effluent loading estimated as population equivalents (equal to a 5-day biochemical oxygen demand of 57 g of oxygen/d) were 6.5 × 10³ at the outlet of the Orge River

(Viry-Châtillon) compared with 10.2 × 10⁶ at Triel-sur-Seine downstream of the Seine-Aval treatment plant, which collected 70 % of the Parisian area discharges. Sample characteristics are listed in Table 1.

Roaches (165–230 mm length) were collected outside of the reproductive period to avoid physiological disturbances (Crimmins et al. 2002). Electro-fishing operations were performed by The French National Agency for Water and Aquatic Environments (ONEMA). Fish were anesthetized with tricaine methane sulphonate (MS222; 1 g L⁻¹) and killed. Fillets without skin were taken and stored on ice for carrying and then stored at –20 °C. In addition, surface sediment was collected with a stainless steel grab and stored at –20 °C. Surface water was collected with a stainless steel disposal, stored at 4 °C in amber glass flasks with Teflon stoppers, and treated after addition of ISs as described by Teil et al. (2012).

Sediment and fish fillet, 2 g dw, were spiked with ISs in a 40-mL centrifuge glass tube and extracted with 20 mL of hexane/acetone (80/20 [v/v]) in a Branson ultrasonic bath during 20 min (USEPA method 3550B for ultrasonic extraction 1996). Extracts were centrifuged (5 min at 970 g), and supernatants were kept. This procedure was performed twice, and both extracts were combined before concentration under a nitrogen stream.

The clean-up procedure, derived from USEPA method 3620B (for phthalate ester and PCB fraction cleanup), consisted of partitioning on a Florisil cartridge (Supelco [1 g]). A multiresidue fractionation method was developed. After loading, PBDEs and PCBs were eluted with 10 mL
<table><caption>**Table 1** Sampling schedule</caption><thead><tr><th>Sampling site</th><th>Population density (inhabitants/km<sup>-2</sup>)</th><th>Effluent loading (population equivalent)</th><th>River flow (m<sup>3</sup> s<sup>-1</sup>)</th><th>Collection date</th><th>Fish samples (n)</th><th>Mean (± SD) fish length (mm)</th><th>Mean (± SD) fish body weight (g)</th><th>Mass collected (g)</th><th>Sediment samples (n)</th><th>Water samples (n)</th><th>Volume collected (L)</th></tr></thead><tbody><tr><td>Orge, Roinville</td><td>50</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>Orge, Viry-Châtillon</td><td>5,211</td><td>65 × 10<sup>3</sup></td><td>3.9</td><td>September 2008</td><td>7</td><td>208 ± 19</td><td>108 ± 26</td><td>100</td><td>2</td><td>2</td><td>3.5</td></tr><tr><td>Seine, Marnay-sur-Seine</td><td>27.4</td><td></td><td></td><td>October 2009</td><td>8</td><td>219 ± 29</td><td>153 ± 54</td><td>500</td><td>2</td><td>8</td><td>3.5</td></tr><tr><td>Seine, Epinay-sur-Seine</td><td>11,383</td><td></td><td></td><td>August 2009</td><td>8</td><td>179 ± 47</td><td>93 ± 82</td><td>500</td><td>2</td><td>8</td><td>3.5</td></tr><tr><td>Seine, Triel-sur-Seine</td><td>817</td><td>10.2 × 10<sup>6</sup></td><td>495</td><td>August 2008</td><td>9</td><td>165 ± 17</td><td>56 ± 18</td><td>200</td><td>2</td><td>2</td><td>3.5</td></tr><tr><td></td><td></td><td></td><td></td><td>November 2009</td><td>12</td><td>230 ± 40</td><td>186 ± 111</td><td>200</td><td>2</td><td>9</td><td>3.5</td></tr></tbody></table>

of hexane/dichloromethane (80/20 [v/v]) and phthalates were eluted with 10 mL of hexane/diethylether (80/20 [v/v]). The different fractions were concentrated (500 µL) under a nitrogen stream.

PBDE-PCB fractions were purified on a multilayer column, consisting (from bottom to top) of 1 g of neutral alumina (activated at 150 °C for 12 h), 1 g of silica (activated at 150 °C for 12 h), and 1 g of $H_2SO_4$-impregnated silica (40 % [w/w]). Columns were conditioned with 20 mL of hexane/dichloromethane (80/20 [v/v]) followed by 20 mL of hexane. After extract loading 20–30 %, PCBs were eluted with 20 mL of hexane (fraction A) and PBDEs, and the rest of the PCBs (70–80 %) were eluted with 15 mL of hexane/dichloromethane (80/20 [v/v]) (fraction B). Fraction A was kept at –20 °C until analysis. Fraction B was concentrated to <1 mL and transferred to an injection vial with 25 µL of iso-octane as solvent keeper. Finally, fraction B was concentrated to approximately 40 µL for PBDE analysis. Then fractions A and B were combined for PCB analysis.

## Analytical Conditions

Analyses were performed by gas chromatography–mass spectrometry (GC–MS) with a 7890 A gas chromatograph coupled to a 5975 A mass spectrometer (Agilent Technologies, Massy, France) for PCBs (column ZB-5MS, 30 m 250 µm ID × 0.25-µm film thickness, detector negative chemical ionization) and for phthalates (column ZB-7HG, 30 m 250 µm ID × 0.25-µm film thickness, detector electronic impact—EI) (Teil et al. 2012). PBDE analyses were performed by GC triple quadrupole mass tandem (GC–MS–MS; EI 70 eV) with an Agilent 7890A gas chromatograph coupled to a 7000B triple quadrupole mass spectrometer (Agilent) equipped with a J&W HP-5MS analytical column (15 m 250 µm ID × 0.25-µm film thickness) (Labadie et al. 2010b). GC–MS analytical parameters for PCBs, phthalates, and PBDEs are listed in Table 2.

Instrument detection limits (IDLs) were considered for the standard solutions as the concentration for a signal-to-noise ratio (SNR; peak to peak) of 3 (Table 3). Method detection limits (MDLs) for river water, sediment, and fish corresponded to the concentration for a SNR (peak to peak) of 9 (Table 3). Recoveries for the entire procedure were estimated by the determination of recovery rates (RRs) for standards in spiked matrix (Table 3). Simultaneously to each set of analyses (n = 6), analytical blanks were performed and then subtracted from sample quantifications.

The different chemicals were detected in blanks at levels as follows: BDEs = BDE28 (≤6 pg), BDE47 (≤30 pg), BDE99 (≤6 pg), BDE100 (≤7 pg) and BDE209 (≤400 pg); PCBs = CB28 (≤2.2 ng), CB52 (≤1.43 ng),
<table><caption>**Table 2** Analytical GC-MS parameters for PCBs and phthalates and GC-MS parameters for PBDEs</caption><thead><tr><th>Compound</th><th>Samples</th><th>Injector</th><th>Guard column</th><th>Column</th><th>Oven</th><th>Helium</th><th>Detector</th><th>Quantification (bold), qualification (normal), and daughter ions (italic)</th><th>References</th></tr></thead><tbody><tr><td>PBDEs</td><td>Water, sediment, fish</td><td>Splitless, 285 °C, 1 µL</td><td>1 m, 530-µm ID, deactivated silica (Restek, France)</td><td>J&W HP-5MS 15 m × 250 µm ID × 0.25-µm film thickness (Agilent)</td><td>100 °C (0.1 min) to 25 °C/min to 185 °C 15 °C/min to 275 °C then 45 °C/min to 315 °C and held for 4 min</td><td>1.8 MI min<sup>-1</sup></td><td>EI 70 eV</td><td><b>408</b> 248–<b>248</b> 139 (Tri-BDEs); <b>486</b>, 326–<b>26</b> 138 (tetra-BDEs); <b>566</b>, 404–<b>406</b> 137; (penta-BDEs) <b>644</b>, 484–<b>484</b>, 377 (hexa-BDEs); <b>800</b>, 798–<b>640</b>, 638 (deca-BDEs); quadrupole 150 °C, interface 300 °C, source 275 °C</td><td>Labadie et al (2010a)</td></tr><tr><td>PCBs</td><td>Water, sediment</td><td>Splitless, 250 °C, 1 µL</td><td>1 m, 530-µm ID, deactivated silica (Restek, France)</td><td>ZB-5MS 30 m × 250 µm ID × 0.25-µm film thickness (Phenomenex, France)</td><td>100 °C (5 min) then 10 °C/min to 310 °C and held for 5 min</td><td>1 mL min<sup>-1</sup></td><td>Negative chemical ionization-constant methane flow</td><td><b>35</b>, 37 (di-, tri-, and tetra-CBs); <b>292</b> 294 (CB 77); <b>326</b>, 328 (penta-CBs); <b>360</b>, 362 (hexa-CBs); <b>394</b>, 396 (hepta-CBs); <b>430</b>, 432 (octa-CBs); <b>464</b>, 466 (nona-CBs) and <b>498</b>, 500; (deca-CBs); quadrupole 150 °C, interface 250 °C, source 200 °C</td><td>Wellington Laboratories for standard EC9605-PAR (native PCB mixture)</td></tr><tr><td>Phthalates</td><td>Water sediment fish</td><td>Splitless, 280 °C, 1 µL</td><td>1 m, 530-µm ID, deactivated silica (Restek, France)</td><td>HT8 50 m × 220 µm × 0.25 µm (SGE, France)</td><td>80 °C for 2 min, 30 °C/min to 170 °C, then 3 °C/min to 300 °C, held for 3 min</td><td>40 psi</td><td></td><td></td><td>SGE Analytical Science (Courtaboeuf, France) for Aroclor 1254</td></tr><tr><td></td><td></td><td>Splitless, 290 °C volume 1 µL</td><td>1 m, 530-µm ID, deactivated silica (Restek, France)</td><td>ZB-7HG 30 m × 250 µm ID × 0.25-µm film thickness (Phenomenex)</td><td>50 °C (1 min), 30 °C/min to 280 °C then 15 °C/min to 310 °C, held for 4 min</td><td>1 mL min<sup>-1</sup></td><td>EI 70 eV</td><td><b>163</b>, 194 (DMP); <b>149</b> 177/105 (DEP); <b>149</b> 104/223 (DiBP); <b>149</b> 223 (DnBP); <b>149</b>, 104 (DPP); <b>149</b> 104/206 (BBP); <b>149</b> 279/293 (DEHP); <b>149</b> 279 (DnOP); <b>293</b> 149/307 (DINP); <b>307</b> 149/203 (DiDP); quadrupole 150 °C, interface 200 °C, source 230 °C</td><td>US CPSC-CH-C1001-09 02 method (Sablayrolles et al 2005)</td></tr></tbody></table>
CB101 (≤0.42 ng), CB118 (≤0.32 ng), CB153 (≤0.48 ng), CB138 (≤0.13 ng), and CB180 (≤0.22 ng); and phthalates = DMP (≤11 ng), DEP (≤24 ng), DnBP (≤11 ng), BBP (≤52 ng), DEHP (≤10 ng), and DnOP (≤4 ng).

Results were expressed as ng L⁻¹ for water, ng g⁻¹ dw for sediment and as ng g⁻¹ dw for fish. PBDEs were expressed as BDE209 and Σtri-hexa congeners. PCBs were expressed as Σ7PCB indicators of the European Norm: 28, 52, 101, 118, 138, 153, and 180 (Σ7PCBi) as Σdioxin-like PCBs (ΣDL-PCBs) and Σ21PCBs. WHO toxic-equivalency factors (Vanden Berg et al. 1998) were used for the determination of toxic equivalents (TEQs). Phthalates were expressed as DEHP and Σ6 phthalates. BAF was calculated as follows: $BAF = C_{biota}/C_{water}$ (L kg⁻¹), $C_{biota}$ expressed as ng kg⁻¹ dw, and $C_{water}$ expressed as ng L⁻¹ (Gobas et al. 2003).

Statistical differences were evaluated by Mann-Whitney/Kruskall-Wallis test, and correlation significances were expressed by Spearman's *r* coefficient (XLSTAT PRO software; Copyright holder CC-BY-SA-3.0, Addinsoft, Paris, France). Principal component analysis (PCA) was used to allow comparisons by way of a diagram underlining the main trends for the three chemical classes.

## Results and Discussion

### River Contamination

In the Seine River basin, contamination of water and sediment by the three classes of endocrine disruptors—phthalates, PBDEs, and PCBs—was poorly documented until now. All of them were detected in both the Seine and the Orge rivers (Fig. 2a, b; Table 4).

Phthalates were the most abundant chemicals in raw water from the Seine and the Orge rivers, with a prevalence of DEHP, followed by DEP, at all sites due to their intense production and varied applications as well as use restrictions for the two other chemical classes (Fig. 2a). Concentrations were similar to the greatest values encountered in the Western European surface waters (Peijnenburg and Struijs 2006). PBDE contamination levels in the two rivers were greater than those reported in the literature for similar environments (Oros et al. 2005; Carroll et al. 2008). BDE209 prevailed (from 0.42 to 3.0 ng L⁻¹) accounting for approximately 90 % of the total PBDEs. Σtri-hexa BDE (dominated by BDE47 then BDE99) ranged from 0.08 to 0.35 ng L⁻¹. PCB concentrations ranged from 2.6 to 4.8 ng L⁻¹ as Σ7PCBi and from 4.3 to 8.7 ng L⁻¹ as Σ21PCBs. They were in the same range as the Detroit River (Detroit, Michigan, USA) (0.11–3.01 ng L⁻¹) (Gewurtz et al. 2003).

The European directive of December 16 2008 (2008/105/CE) recommended for DEHP a Norm of Environmental Quality (NEQ) of 1.3 µg L⁻¹ as an acceptable

annual mean and 0.5 ng L⁻¹ for BDE (28, 47, 99 100 153 and 154) in surface water. At all sites, DEHP and BDE concentrations remained lower than that limit.

DEHP concentrations were increased by 6 times in the Seine River (*p* < 0.05) from Marnay-sur-Seine (*n* = 8) to Triel-sur-Seine (*n* = 9) and by ≤20 times (*p* < 0.05) in the Orge River from Roinville (*n* = 2) to Viry-Châtillon (*n* = 8) (Table 5; Fig. 2a). The BDE increases were 4.9 times for BDE209 and Σtri-hexa BDE in the Orge River and 2.4 and 1.7 times, respectively, in the Seine River. In the same trend, a 2 times increase for PCBs was observed along the Seine River. Indeed, phthalate release by a number of automobile manufacturing plants and plastic industries located in this area, namely DEP and DnBP, might account for river water quality. Globally, the impact of urban areas on surface water quality was of similar importance in the Seine and the Orge rivers and was related to low flow of the latest, although lower effluent loading.

Phthalate sediment concentrations ranged from 66 to 28,800 ng g⁻¹ dw (Fig. 2b; Table 4). DEHP (50–93 %) prevailed, followed by DnBP (<1–39 %), which is consistent with the production pattern and their adsorption ability on settling particles. According to Peijnenburg and Struijs (2006), phthalate concentration in sediment is ruled by the net balance between supply through settling of suspended material and biodegradation.

PBDE concentrations ranged from 0.18 to 10.8 ng g⁻¹ dw for Σtri-hexa BDE (dominated by BDE99, then BDE47, and then BDE100) and from less than the limit of quantification (LQ) to 297 ng g⁻¹ dw for BDE209, which prevailed, except for the rural site of the Orge River (Fig. 2b; Table 4). Similar distribution was observed in surface sediment from the Elbe River in Germany (Stachel et al. 2005). Σtri-hexa BDE concentrations were in accordance with those reported in sediment from the Hadley Lake (IN, USA) of 5 to 38 ng g⁻¹ dw, whereas BDE209 concentrations were greater compared with 19–36 ng g⁻¹ dw in the lake (Dodder et al. 2002).

Our findings might be related to the use of penta- and deca-BDE formulations in France (Ineris 2005). The penta-BDE formulation consists of approximately 50 % penta-BDEs (predominantly BDE99 and BDE100) and approximately 40 % tetra-BDEs (mainly BDE47), whereas the deca-BDE formulation consists mainly of BDE209 (98 %) (Siddiqi et al. 2003). However, concentrations remained lower than the threshold value of 6 µg kg⁻¹ dw recommended by the European Directive (2005/12/CE) for penta-BDE. The highest levels of total BDEs, ranging from 4,434 to 16,088 ng g⁻¹ dw, were found by Luo et al. (2007) in sediment from the Nanyang River (Hong Kong) and were related to electronic waste recycling activity settled there, thus highlighting a prevailing source of these compounds.
<table><caption>**Table 3** IDLs, RR (italic), and MDLs (bold) for river water, sediment, and fish</caption><thead><tr><th>PBDEs</th><th></th><th>BDE28</th><th>BDE47</th><th>BDE99</th><th>BDE100</th><th>BDE153</th><th>BDE154</th><th>BDE209</th></tr></thead><tbody><tr><td rowspan="3">River water</td><td>IDL (pg)</td><td>0.4</td><td>0.2</td><td>0.2</td><td>0.2</td><td>0.6</td><td>0.3</td><td>0.5</td></tr><tr><td>RR (%)</td><td>94.5</td><td>100.8</td><td>83.3</td><td>89.1</td><td>73.1</td><td>76.2</td><td>56.6</td></tr><tr><td>MDL (pg L<sup>-1</sup>)</td><td><strong>15</strong></td><td><strong>12</strong></td><td><strong>13</strong></td><td><strong>4</strong></td><td><strong>6</strong></td><td><strong>4</strong></td><td><strong>150</strong></td></tr><tr><td rowspan="2">River bed sediment</td><td>RR (%)</td><td>86.1</td><td>94</td><td>76.1</td><td>99.5</td><td>99.8</td><td>80.7</td><td>100.3</td></tr><tr><td>MDL (pg L<sup>-1</sup>)</td><td><strong>25</strong></td><td><strong>10</strong></td><td><strong>10</strong></td><td><strong>5</strong></td><td><strong>9</strong></td><td><strong>6</strong></td><td><strong>145</strong></td></tr><tr><td rowspan="2">Fish muscle</td><td>RR (%)</td><td>70.5</td><td>76.1</td><td>73.2</td><td>72.8</td><td>98</td><td>104.5</td><td>75.2</td></tr><tr><td>MDL (pg L<sup>-1</sup>)</td><td><strong>8</strong></td><td><strong>36</strong></td><td><strong>24</strong></td><td><strong>16</strong></td><td><strong>32</strong></td><td><strong>24</strong></td><td><strong>580</strong></td></tr><tr><td>PCBs</td><td></td><td>CB28</td><td>CB52</td><td>CB101</td><td>CB118</td><td>CB138</td><td>CB153</td><td>CB180</td></tr><tr><td rowspan="3">River water</td><td>IDL (pg)</td><td>0.03</td><td>0.07</td><td>0.05</td><td>0.16</td><td>0.24</td><td>0.1</td><td>0.015</td></tr><tr><td>RR (%)</td><td>80</td><td>105</td><td>103</td><td>87</td><td>100</td><td>98</td><td>88</td></tr><tr><td>MDL (pg L<sup>-1</sup>)</td><td><strong>129</strong></td><td><strong>41</strong></td><td><strong>138</strong></td><td><strong>16</strong></td><td><strong>23</strong></td><td><strong>10</strong></td><td><strong>12</strong></td></tr><tr><td rowspan="2">River bed sediment</td><td>RR (%)</td><td>74.7</td><td>78.7</td><td>81.3</td><td>92.7</td><td>102.6</td><td>101.4</td><td>95</td></tr><tr><td>MDL (pg L<sup>-1</sup>)</td><td><strong>42</strong></td><td><strong>67</strong></td><td><strong>46</strong></td><td><strong>114</strong></td><td><strong>136</strong></td><td><strong>53</strong></td><td><strong>35</strong></td></tr><tr><td rowspan="2">Fish muscle</td><td>RR (%)</td><td>81.4</td><td>81.7</td><td>84.5</td><td>90.2</td><td>98.7</td><td>98.7</td><td>94.7</td></tr><tr><td>MDL (pg L<sup>-1</sup>)</td><td><strong>55</strong></td><td><strong>133</strong></td><td><strong>58</strong></td><td><strong>351</strong></td><td><strong>300</strong></td><td><strong>114</strong></td><td><strong>116</strong></td></tr><tr><td>Phthalates</td><td></td><td>DMP</td><td>DEP</td><td>DnBP</td><td>BBP</td><td>DEHP</td><td>DnOP</td><td></td></tr><tr><td rowspan="3">River water</td><td>IDL (pg)</td><td>20</td><td>37.5</td><td>3.6</td><td>4.1</td><td>4.5</td><td>17</td><td></td></tr><tr><td>RR (%)</td><td>76.5</td><td>68.5</td><td>91.5</td><td>82.5</td><td>92.5</td><td>78.5</td><td></td></tr><tr><td>MDL (pg L<sup>-1</sup>)</td><td><strong>15</strong></td><td><strong>29</strong></td><td><strong>54</strong></td><td><strong>28</strong></td><td><strong>50</strong></td><td><strong>53</strong></td><td></td></tr><tr><td rowspan="2">River bed sediment</td><td>RR (%)</td><td>55.4</td><td>51.8</td><td>51.9</td><td>86.2</td><td>59.2</td><td>41.8</td><td></td></tr><tr><td>MDL (pg L<sup>-1</sup>)</td><td><strong>1.6</strong></td><td><strong>1.6</strong></td><td><strong>6.0</strong></td><td><strong>13.4</strong></td><td><strong>15.0</strong></td><td><strong>16.2</strong></td><td></td></tr><tr><td rowspan="2">Fish muscle</td><td>RR (%)</td><td>58.1</td><td>60.1</td><td>80.8</td><td>109.1</td><td>65.0</td><td>72</td><td></td></tr><tr><td>MDL (pg L<sup>-1</sup>)</td><td><strong>0.6</strong></td><td><strong>0.4</strong></td><td><strong>2.2</strong></td><td><strong>8.8</strong></td><td><strong>10.5</strong></td><td><strong>7.6</strong></td><td></td></tr></tbody></table>

PCB sediment concentrations ranged from 12 to 134 ng g⁻¹dw as ∑7PCBi and from 16 to 199 ng g⁻¹dw as ∑21PCB, respectively, corresponding to high contamination levels compared with other river sediment concentrations reported in Europe (Fig. 2b; Table 4). The main compounds were CB153 (12.2–20.1 % of ∑21PCBs), CB110 (3.4–28.3 %), CB138 (10.8–18.9 %), and CB101 (6.3–17.2 %). In this way, in the Ebro River (Spain) in 1995–1996, concentrations were only 14 ± 7.5 ng g⁻¹dw as ∑13 PCB (Fernandez et al. 1999).

In the Seine River, from upstream (Marnay-sur-Seine) to downstream (Triel-sur-Seine) of urbanized areas, sediment concentration increases were 202-fold for DEHP and 176-fold for ∑6phthalates. They were 69- and 25-fold for BDE209 and ∑tri-hexa BDE, respectively, and only approximately 12-fold for PCBs with the highest level encountered at Epinay-sur-Seine. This minor increase compared with those observed for phthalates and PBDEs was likely due to the ban of PCBs in France since 1987. In 2000, a global annual PCB flux of 3 kg as ∑7PCBi was determined from the French inventory of PCB emissions to the aquatic environment in Ile-de-France, whereas downstream of Paris the treatment plant discharge to the Seine

River was approximately 7 kg y⁻¹ as ∑7PCBi (Blanchard et al. 2004).

The decrease of river PCB concentrations between Epinay and Triel might be related to dilution processes arising from the confluence with the Oise River. As a matter of fact, in the Oise River, PCB concentrations for water and sediment were reported to be, respectively, 2 and 17 times lower than in the Seine River (Chevreuil et al. 1998). In contrast, phthalate concentrations presented low variation between the two sites of Epinay and Triel. Similar water concentrations for the Seine and Oise rivers were previously found, thus preventing any dilution scenario (Dargnat 2008).

## Fish Contamination

Chemical from the three classes were encountered in roach muscle at all sites of the Seine River and at the outlet of the Orge River (Table 4; Fig. 2c). Muscle concentrations varied significantly according toitelocations from upstream to downstream of the urbanized areas as well in the Orge River for PBDEs (*p* < 0.05) and phthalates (*p* < 0.01) similar to the Seine River for PBDEs and PCBs (*p* < 0.001) and phthalates (*p* < 0.01).
<figure><img src="image_4.png" /><figcaption>**Fig. 2** PCB, PBDE, and phthalate distribution (mean ± SD) in surface water (a) sediment (b) and muscle tissue of roach (c) from the Seine River (Marnay sur Seine, Epinay sur Seine, Triel sur Seine) and the Orge River (Roinville, Viry Châtillon)</figcaption></figure>

Mann-Whitney test significances are listed in Table 5. The largest increases in the Seine River from Marnay-sur-Seine to Triel-sur-Seine were, respectively, eightfold for PCBs, three-fold for BDE209, 14-fold for Σtri-hexa BDE, and threefold for phthalates.

Considering all sites, Σ7PCBi represented 80.3–85 % of total PCBs analyzed. Aquatic organisms incorporate

organic pollutants either directly from the water column and the sediment or indirectly through the food chain (Veltman et al. 2005; Sloan et al. 2010). The highest PCB concentrations were found at Epinay-sur-Seine as well in water as sediment, which confirms that roach muscle is a relevant indicator of PCB contamination. An important decrease was noticed in the Seine River from 1993 when
<table><caption>**Table 4** Compound concentrations (mean ± SD) in water, sediment, and fish from the Orge River (Roinville and Viry-Châtillon) and the Seine River (Marnay-sur-Seine, Epinay-sur-Seine, and Triel-sur-Seine)</caption><thead><tr><th rowspan="3"></th><th colspan="2">Raw water (ng L<sup>-1</sup>)</th><th colspan="4">Sediment (ng g<sup>-1</sup> dw)</th><th colspan="4">Fish (ng g<sup>-1</sup> dw)</th><th rowspan="3">Seine river</th><th rowspan="3">Triel (n = 12)</th></tr><tr><th rowspan="2">Orge river</th><th rowspan="2">Seine river</th><th rowspan="2">Orge river</th><th rowspan="2">Seine river</th><th rowspan="2">Orge river</th><th rowspan="2">Seine river</th><th rowspan="2">Orge river</th><th rowspan="2">Seine river</th><th rowspan="2">Orge river</th><th rowspan="2">Seine river</th></tr><tr><th>Roinville (n = 2)</th><th>Viry-Châtillon (n = 8)</th><th>Marnay (n = 8)</th><th>Epinay (n = 2)</th><th>Triel (n = 2)</th><th>Roinville (n = 7)</th><th>Viry-Châtillon (n = 8)</th><th>Marnay (n = 8)</th><th>Epinay (n = 9)</th></tr></thead><tbody><tr><td>DMP</td><td>0</td><td>42 ± 44</td><td>11 ± 4</td><td>23</td><td>112 ± 245</td><td>&lt;LQ</td><td>36</td><td>8</td><td>51</td><td>229 ± 125</td><td>8 ± 10</td><td>7 ± 27</td><td>78 ± 112</td><td>32 ± 22</td></tr><tr><td>DEP</td><td>0</td><td>528 ± 904</td><td>152 ± 66</td><td>384</td><td>225 ± 249</td><td>1</td><td>33</td><td>9</td><td>134</td><td>287 ± 188</td><td>265 ± 397</td><td>309 ± 165</td><td>226 ± 314</td><td>247 ± 152</td></tr><tr><td>DnBP</td><td>10</td><td>120 ± 80</td><td>49 ± 21</td><td>101</td><td>134 ± 140</td><td>3</td><td>105</td><td>64</td><td>1,104</td><td>92 ± 165</td><td>477 ± 272</td><td>185 ± 359</td><td>210 ± 208</td><td>1,110 ± 573</td></tr><tr><td>BBP</td><td>0</td><td>59 ± 82</td><td>40 ± 5</td><td>119</td><td>55 ± 110</td><td>&lt;LQ</td><td>52</td><td>203</td><td>11,538</td><td>10 ± 0.017</td><td>136 ± 20</td><td>101 ± 112</td><td>175 ± 289</td><td>161 ± 375</td></tr><tr><td>DEHP</td><td>49</td><td>981 ± 1,101</td><td>106 ± 54</td><td>484</td><td>665 ± 864</td><td>62</td><td>983</td><td>82</td><td>2,152</td><td>16,546</td><td>106 ± 42</td><td>376 ± 113</td><td>273 ± 177</td><td>966 ± 657</td><td>1,461 ± 1,462</td></tr><tr><td>DnOP</td><td>0</td><td>11 ± 12</td><td>22 ± 20</td><td>26</td><td>18 ± 20</td><td>65</td><td></td><td></td><td></td><td></td><td>3 ± 2</td><td>149 ± 151</td><td>105 ± 154</td><td>112 ± 187</td><td>145 ± 58</td></tr><tr><td>Σ6 phthal</td><td>59</td><td>1,741 ± 2,353</td><td>379 ± 170</td><td>1,137</td><td>1,208 ± 1,627</td><td>66</td><td>1,230</td><td>163</td><td>3,643</td><td>28,782</td><td>718 ± 215</td><td>1,411 ± 518</td><td>979 ± 356</td><td>1,767 ± 1,317</td><td>3,156 ± 1,958</td></tr><tr><td>CB28</td><td>nd</td><td>0.11 ± 0.141</td><td>0.09 ± 0.14</td><td>0.50</td><td>0.65 ± 0.21</td><td>nd</td><td>0.1</td><td>0.1</td><td>10.7</td><td>1.8</td><td>nd</td><td>0.00 ± 0.00</td><td>0.4 ± 0.3</td><td>3.2 ± 1.7</td><td>4.1 ± 1.8</td></tr><tr><td>CB52</td><td>nd</td><td>0.75 ± 0.67</td><td>1.9 ± 2.2</td><td>1.9</td><td>2.18 ± 2.18</td><td>nd</td><td>0.4</td><td>1.3</td><td>24.2</td><td>7.2</td><td>nd</td><td>4.8 ± 0.9</td><td>2.5 ± 0.8</td><td>12.1 ± 5.3</td><td>15.7 ± 5.1</td></tr><tr><td>CB77</td><td>nd</td><td>0.26 ± 0.39</td><td>0.20 ± 0.32</td><td>2.0</td><td>0.25 ± 0.35</td><td>nd</td><td>11.7</td><td>0.1</td><td>1.5</td><td>0.4</td><td>nd</td><td>0.29 ± 0.21</td><td>&lt;LQ</td><td>0.2 ± 0.2</td><td>0.2 ± 0.1</td></tr><tr><td>CB101</td><td>nd</td><td>0.48 ± 0.52</td><td>0.39 ± 0.44</td><td>0.86</td><td>0.50 ± 0.54</td><td>nd</td><td>4.7</td><td>2.7</td><td>25.2</td><td>9.8</td><td>nd</td><td>23.1 ± 5.9</td><td>4.2 ± 1.3</td><td>26.0 ± 11.7</td><td>23.8 ± 8.7</td></tr><tr><td>CB105</td><td>nd</td><td>0.12 ± 0.15</td><td>0.022 ± 0.018</td><td>0.13</td><td>0.052 ± 0.035</td><td>nd</td><td>0.1</td><td>0.7</td><td>3.6</td><td>3.1</td><td>nd</td><td>3.9 ± 1.3</td><td>1.4 ± 0.5</td><td>4.8 ± 1.6</td><td>4.1 ± 1.0</td></tr><tr><td>CB110</td><td>nd</td><td>0.41 ± 0.49</td><td>0.18 ± 0.28</td><td>0.016</td><td>0.54 ± 0.40</td><td>nd</td><td>2.5</td><td>2.6</td><td>56.4</td><td>18.1</td><td>nd</td><td>26.5 ± 10.1</td><td>3.9 ± 1.3</td><td>24.3 ± 13.7</td><td>18.8 ± 9.4</td></tr><tr><td>CB118</td><td>nd</td><td>0.54 ± 0.92</td><td>0.10 ± 0.12</td><td>0.48</td><td>0.18 ± 1.38</td><td>nd</td><td>1.4</td><td>2.1</td><td>13.4</td><td>10.7</td><td>nd</td><td>12.7 ± 1.9</td><td>5.6 ± 1.6</td><td>17.1 ± 10.0</td><td>17.0 ± 2.3</td></tr><tr><td>CB138</td><td>nd</td><td>1.14 ± 0.84</td><td>0.047 ± 0.045</td><td>0.15</td><td>0.15 ± 0.20</td><td>nd</td><td>8.0</td><td>2.2</td><td>23.8</td><td>20.0</td><td>nd</td><td>41.3 ± 5.6</td><td>5.1 ± 1.5</td><td>20.4 ± 6.8</td><td>16.4 ± 2.2</td></tr><tr><td>CB153</td><td>nd</td><td>1.12 ± 0.78</td><td>0.11 ± 0.12</td><td>0.69</td><td>0.86 ± 2.27</td><td>nd</td><td>12.9</td><td>2.4</td><td>24.3</td><td>21.3</td><td>nd</td><td>68.7 ± 2.8</td><td>6.9 ± 1.7</td><td>39.4 ± 10.5</td><td>25.6 ± 3.9</td></tr><tr><td>CB180</td><td>nd</td><td>0.71 ± 0.38</td><td>0.032 ± 0.035</td><td>0.26</td><td>0.23 ± 0.43</td><td>nd</td><td>14.4</td><td>1.0</td><td>12.9</td><td>11.1</td><td>nd</td><td>37.4 ± 2.0</td><td>2.4 ± 0.5</td><td>92.9 ± 26.0</td><td>10.9 ± 1.8</td></tr><tr><td>Σ7 PCBs</td><td>nd</td><td>49 ± 2.8</td><td>2.6 ± 2.2</td><td>4.8</td><td>4.8 ± 5.6</td><td>nd</td><td>42.0</td><td>11.8</td><td>134</td><td>82.0</td><td>nd</td><td>188 ± 10.0</td><td>26.9 ± 6.5</td><td>211 ± 55.0</td><td>113 ± 20.9</td></tr><tr><td>ΣDL-PCBs</td><td>nd</td><td>1.5 ± 1.2</td><td>3.0 ± 2.5</td><td>7.0</td><td>5.2 ± 6.0</td><td>nd</td><td>14.7</td><td>3.2</td><td>21.2</td><td>16.5</td><td>nd</td><td>24.3 ± 4.7</td><td>7.4 ± 2.1</td><td>30.0 ± 13.3</td><td>24.3 ± 3.9</td></tr><tr><td>Σ21 PCBs</td><td>nd</td><td>7.2 ± 3.9</td><td>4.3 ± 3.2</td><td>8.7</td><td>7.9 ± 9.7</td><td>nd</td><td>74.3</td><td>15.7</td><td>199</td><td>106</td><td>nd</td><td>234 ± 46</td><td>32.6 ± 8.2</td><td>248 ± 68</td><td>139 ± 31</td></tr><tr><td>BDE 28</td><td>0.002</td><td>0.009 ± 0.008</td><td>0.003 ± 0.001</td><td>0.004</td><td>0.003 ± 0.002</td><td>&lt;LQ</td><td>0.017</td><td>0.007</td><td>0.060</td><td>0.089</td><td>0.026 ± 0.069</td><td>0.57 ± 0.17</td><td>0.03 ± 0.01</td><td>0.20 ± 0.04</td><td>0.34 ± 0.13</td></tr><tr><td>BDE 47</td><td>0.045</td><td>0.14 ± 0.11</td><td>0.050 ± 0.027</td><td>0.080</td><td>0.072 ± 0.033</td><td>0.18</td><td>0.77</td><td>0.20</td><td>1.8</td><td>3.6</td><td>3.2 ± 0.8</td><td>15.6 ± 2.93</td><td>0.86 ± 0.37</td><td>11.4 ± 2.73</td><td>10.4 ± 4.6</td></tr><tr><td>BDE 99</td><td>0.021</td><td>0.11 ± 0.06</td><td>0.032 ± 0.013</td><td>0.064</td><td>0.044 ± 0.008</td><td>&lt;LQ</td><td>0.86</td><td>0.15</td><td>6.7</td><td>5.1</td><td>&lt;LQ</td><td>0.013 ± 0.004</td><td>0.003 ± 0.004</td><td>0.27 ± 0.47</td><td>0.13 ± 0.43</td></tr><tr><td>BDE 100</td><td>0.000</td><td>0.04 ± 0.04</td><td>0.012 ± 0.032</td><td>0.015</td><td>0.015 ± 0.021</td><td>&lt;LQ</td><td>0.22</td><td>0.045</td><td>0.44</td><td>0.84</td><td>0.39 ± 0.27</td><td>1.51 ± 0.31</td><td>0.16 ± 0.06</td><td>3.1 ± 3.5</td><td>1.5 ± 0.7</td></tr><tr><td>BDE 153</td><td>0.003</td><td>0.035 ± 0.048</td><td>0.014 ± 0.002</td><td>0.017</td><td>0.012 ± 0.002</td><td>&lt;LQ</td><td>0.13</td><td>0.022</td><td>0.42</td><td>0.66</td><td>&lt;LQ</td><td>0.30 ± 0.36</td><td>0.02 ± 0.02</td><td>0.16 ± 0.10</td><td>0.10 ± 0.04</td></tr><tr><td>BDE 154</td><td>0.000</td><td>0.007 ± 0.005</td><td>0.004 ± 0.027</td><td>0.011</td><td>0.007 ± 0.011</td><td>&lt;LQ</td><td>0.10</td><td>0.018</td><td>0.23</td><td>0.45</td><td>0.210 ± 0.116</td><td>0.748 ± 0.344</td><td>0.063 ± 0.023</td><td>0.646 ± 0.077</td><td>0.662 ± 0.362</td></tr><tr><td>BDE 209</td><td>0.42</td><td>2.0 ± 2.2</td><td>1.23 ± 1.09</td><td>2.9</td><td>1.3 ± 0.6</td><td>&lt;LQ</td><td>41.3</td><td>4.3</td><td>104</td><td>297</td><td>0.71 ± 0.63</td><td>1.7 ± 3.2</td><td>0.08 ± 0.08</td><td>0.19 ± 0.001</td><td>0.25 ± 0.21</td></tr><tr><td>Σtri hexa</td><td>0.071</td><td>0.35 ± 0.27</td><td>0.11 ± 0.10</td><td>0.19</td><td>0.15 ± 0.08</td><td>0.18</td><td>2.1</td><td>0.44</td><td>9.68</td><td>10.8</td><td>3.8 ± 1.2</td><td>20.7 ± 3.9</td><td>1.1 ± 0.5</td><td>15.8 ± 6.9</td><td>13.1 ± 5.8</td></tr></tbody></table>

ND no determination; <LQ less than the LQ
total PCBs were 2 µg g⁻¹ dw at Marnay-sur-Seine and approximately 7.5 µg g⁻¹ dw downstream of Paris area, which corroborates their prohibition (Blanchard et al. 1997). In the same way, Wiener and Sandheinrich (2010) reported substantial decrease of PCB contents in fillets of common carp (*Cyprinus carpio*) from the Upper Mississippi River since the 1970s. However, a persistence roach contamination hot spot has been observed at Epinay-sur-Seine since the 1990s and 8 µg g⁻¹ dw in 1996 (Blanchard et al. 1999).

Comparison PCB contamination of roach muscle (n = 37) with that of water and sediment at the four sites (Viry-Châtillon on the Orge River and the three sites on the Seine River) showed a significant correlation for water (p < 0.05) and for sediment (p < 0.01). That is consistent with Morgan and Lohmann (2010) who stated that contaminated sediment could be a major source of PCBs to fish. Thus, roach seems to be a reliable bioindicator for the evaluation of both water and sediment contamination.

The TEQ values of roach from Viry-Châtillon (Orge), Marnay-sur-Seine, Epinay-sur-Seine, and Triel-sur-Seine were 4.4, 0.9, 5.8, and 5.3 pg TEQ(OMS/98)/g dw, respectively. Eljarrat et al. (2008), for the Ebro River (Spain), reported similar TEQ values (8 pg g⁻¹ dw) in *R. arcasii*. Greater contamination level in the roach from another French river, the Rhône, which is characterized by densely industrialized areas, was reported at Σ7PCBi from 24 to 732 ng g⁻¹ dw and TEQ from 2.7 to 36 pg g⁻¹ dw (Babut et al. 2009). PCB contents found by Phua et al. (2008) in a marine species, the Southern blue Tuna, in South Australia were similar to our results (4.7 pg g⁻¹ dw of TEQ), thus underscoring PCB worldwide contamination.

PBDE fish contents did not vary significantly between two sites, Epinay-sur-Seine and Triel-sur-Seine, downstream of the Paris area (Fig. 2c). The highest values were encountered in the Orge River, whereas water contamination was similar between Viry-Châtillon and Epinay-sur-Seine. This observation could be explained by differences in metabolic activities, particularly debromination processes, which varied with the environmental conditions. Thus, roach seems to be a less reliable bioindicator for the evaluation of PBDE contamination of both water and sediment.

Fish contents are in accordance with those from the European environment (Law et al. 2006). BDE roach contents by decreasing importance order were BDE47 > BDE100 > BDE154 > BDE28 > BDE153 > BDE209 > BDE99, which is contrary to findings in water and sediment where BDE209 then BDE99 were predominant, thus corroborating biodegradation processes in the roach for the later two compounds. Fish from other European rivers, the Rhône River (France), and the Po River (Italy) presented the same PBDE pattern (Miège et al. 2012; Viganò et al. 2008). However, De Boer et al. (2010) observed a decrease of

BDE47 in eel from the Rhine and Meuse rivers of 4–10 times since 1984, which was related to the agreement between Dutch authorities and the bromine industry regarding the restricted use of a technical penta-mix (BDE47 prevailing) in the Netherlands.

Moreover, the BDE209 domination observed in the sediment BDE pattern was not detected in both benthic and pelagic fish species from the Po River (Viganò et al. 2008). Indeed, Munschy et al. (2011) investigated the turnover of BDE28, 47, 99, 100, 153, and 209 in juvenile common sole (*Solea solea*) exposed to spiked food. All of the investigated PBDEs, as well as BDE49 and BDE202, were found in fish tissue, thus yielding evidence of PBDE biotransformation by way of debromination, which appears to be a major degradation route.

A significant correlation was observed between PCB and PBDE concentrations (r = 0.956 and p < 0.05), although they represent two distinct classes with different uses and although PCB were banned in all of their applications, suggesting similar sources, bioavailability, or absorption processes. In the same way, a good correlation was found between PCBs and PBDEs in whitefish from Lake Thun, Switzerland (Bogdal et al. 2009). The investigators hypothesized similar input pathways to ecosystems for both chemicals and major part played by atmospheric deposition. Generally, PBDEs were widely distributed in fish, including those from European high mountain lakes, as a consequence of impacts from long-range atmospheric transport and deposition (Law et al. 2006). However, Wu et al. (2008) reported bioaccumulation of PCBs and PBDEs in wild aquatic species at 1.2–8.4 ng g⁻¹ dw for PCBs and of 2.9–5.3 ng g⁻¹ dw for PBDEs as a consequence of electronic waste recycling activity in south China.

Roach from the Seine River displayed a spatial distribution of phthalates different from the other two classes of chemicals with the highest levels found at Triel-sur-Seine, far downstream of the Paris area as shown for water and sediment (Fig. 2C). A large part of industrial discharge is carried through the sewer network, and DEHP was quantified in 53 % of industrial discharges with an average flux of 12.2 kg d⁻¹ for 2003–2005. Moreover, DEHP flux in the “Seine Aval” treatment plant downstream of Epinay-sur-Seine, which treats most wastewaters from the Paris area, was 80 kg d⁻¹ as inputs and 3.7 kg d⁻¹ as outputs (Dargnat 2008).

Phthalate contents in roach from the Orge River were low at the upstream part of the basin and remained less than those in roach from the Seine River at the basin output. Our values were consistent with those reported in the Netherlands, for phthalates commonly found in bream (*A. brama*): DEHP from 280 to 6,012 ng g⁻¹ dw and DEP from 88 to 1,280 ng g⁻¹ dw (Vethaak et al. 2005).

Relationships between compound distributions in roach muscle at sites upstream and downstream of urbanized
<table><caption>**Table 5** Mann Whitney test results for comparisons of surface water and roach contamination in the Seine and the Orge rivers</caption><thead><tr><th></th><th></th><th></th><th>Viry Châtillon</th><th>Marnay</th><th></th><th></th></tr></thead><tbody><tr><td rowspan="10">Surface water (ng L<sup>-1</sup>)</td><td>Viry Châtillon (Orge)</td><td>∑ 8 BDEs</td><td>1</td><td></td><td></td><td></td></tr><tr><td>(n 8)</td><td>∑ 6 Phthalates</td><td>1</td><td></td><td></td><td></td></tr><tr><td rowspan="3">Marnay (Seine)</td><td>∑ 8 BDEs</td><td>p &lt; 0.05</td><td>1</td><td></td><td></td></tr><tr><td>∑ 6 Phthalates</td><td>p &lt; 0.05</td><td>1</td><td></td><td></td></tr><tr><td>∑ 21 PCBs</td><td>p &lt; 0.05</td><td>1</td><td></td><td></td></tr><tr><td rowspan="3">Triel (Seine)</td><td>∑ 8 BDEs</td><td>NS</td><td>p &lt; 0.05</td><td></td><td></td></tr><tr><td>∑ 6 Phthalates</td><td>NS</td><td>p &lt; 0.05</td><td></td><td></td></tr><tr><td>∑ 21 PCBs</td><td>NS</td><td>p &lt; 0.05</td><td></td><td></td></tr><tr><td rowspan="10">Roach (ng g<sup>-1</sup> dw)</td><td>Roinville (Orge)</td><td>∑ 8 BDEs</td><td>1</td><td></td><td></td><td></td></tr><tr><td>(n 7)</td><td>∑ 6 Phthalates</td><td>1</td><td></td><td></td><td></td></tr><tr><td rowspan="3">Viry Châtillon (Orge)</td><td>∑ 8 BDEs</td><td>p &lt; 0.05</td><td>1</td><td></td><td></td></tr><tr><td>∑ 6 Phthalates</td><td>p &lt; 0.01</td><td>1</td><td></td><td></td></tr><tr><td>∑ 8 BDEs</td><td>p &lt; 0.05</td><td>p &lt; 0.001</td><td>1</td><td></td></tr><tr><td rowspan="3">Marnay (Seine)</td><td>∑ 6 Phthalates</td><td>NS</td><td>NS</td><td>1</td><td></td></tr><tr><td>∑ 21 PCBs</td><td>ND</td><td>p &lt; 0.001</td><td>1</td><td></td></tr><tr><td>∑ 8 BDEs</td><td>p &lt; 0.05</td><td>NS</td><td>p &lt; 0.05</td><td>1</td></tr><tr><td rowspan="3">Epinay (Seine)</td><td>∑ 6 Phthalates</td><td>p &lt; 0.05</td><td>NS</td><td>NS</td><td>1</td></tr><tr><td>∑ 21 PCBs</td><td>ND</td><td>p &lt; 0.001</td><td>1</td><td></td></tr><tr><td>∑ 8 BDEs</td><td>p &lt; 0.05</td><td>NS</td><td>p &lt; 0.001</td><td>NS</td></tr><tr><td rowspan="3">Triel (Seine)</td><td>∑ 6 Phthalates</td><td>p &lt; 0.001</td><td>p &lt; 0.05</td><td>p &lt; 0.01</td><td>NS</td></tr><tr><td>∑ 21 PCBs</td><td>ND</td><td>p &lt; 0.05</td><td>p &lt; 0.001</td><td>p &lt; 0.05</td></tr></tbody></table>

ND no determination, NS not significant

areas were explored. Correlations were found, particularly between low molecular-weight PCB congeners (CB28, CB52, CB101) (*p* < 0.05) and PBDE congeners (BDE28, BDE47, BDE100) (*p* < 0.05). Moreover, BDE99 and BDE209 displayed a particular behaviour and showed no correlation with other PBDEs or with PCBs or phthalates (Table 6).

PCA was performed for $\alpha$ = 0.05 on 18 active variables consisting of compound concentrations in roach muscle (Fig. 3). From a great number of data and factors, the PCA allowed comparisons by way of a diagram underlining the main trends. In addition, investigations of the links between variables lead to the creation of a few synthetic variables (F1 and F2) called “principal components.” The same importance is attributed, a priori, to each variable and the same weight to each subject. Thus, the similarity between two subjects is represented by the Euclidean distance between two points. The cosinus values, which are geometrical basis, are interpreted as the visual support of the correlation coefficients listed in Table 6.

For $\alpha$ = 0.05, the nil hypothesis could be rejected, and correlations between variables were investigated. The first and second axis, corresponding to F1 and F2 factors represented, respectively, 41.49 and 19.39 % of the explained variance level. Relationships between subjects and variables are well represented in the two-dimensional plot, and the explained variance was 60.88 % of the total variance.

Thirty-six fish subjects were distributed according to the sampling sites with three distinct groups being clearly identified: Marnay-sur-Seine, Viry-Châtillon, and Epinay-sur-Seine/Triel-sur-Seine, all of which receive contamination downstream of the Paris area. The fish cluster of Viry-Châtillon was strongly linked to high-brominated PBDEs (BDE153 and BDE209). At this site, fish might integrate pollution released from sediments and from wastewater-treatment plant (WWTP) discharges. Indeed, concentrations of 0.5 ng L<sup>-1</sup> for $\sum$tri-hexa and 7.5 ng L<sup>-1</sup> for <BDE209 were reported in WWTP outputs in the same area (Labadie et al. 2010b). For the Seine River, Gasperi et al. (2012) reported that PBDEs were efficiently removed
<table><caption>Table 6 Spearman's r coefficient values for PCA (18 variables, significant r values for $\alpha = 0.05$)</caption><thead><tr><th></th><th>DEHP</th><th>CB28</th><th>CB52</th><th>CB101</th><th>CB118</th><th>CB153</th><th>CB138</th><th>CB180</th><th>ΣPCBi</th><th>BDE28</th><th>BDE47</th><th>BDE100</th><th>BDE99</th><th>BDE154</th><th>BDE153</th><th>BDE209</th></tr></thead><tbody><tr><td>DEHP</td><td>1</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>Σ6-phthalates</td><td>0.410</td><td>1</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>CB28</td><td>0.537</td><td>0.459</td><td>1</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>CB52</td><td>0.486</td><td>0.527</td><td>0.922</td><td>1</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>CB101</td><td>0.435</td><td>0.449</td><td>0.606</td><td>0.759</td><td>1</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>CB118</td><td>0.530</td><td></td><td>0.686</td><td>0.772</td><td>0.783</td><td>1</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>CB153</td><td></td><td></td><td></td><td></td><td>0.555</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>CB138</td><td></td><td></td><td></td><td></td><td>0.439</td><td>0.392</td><td>0.503</td><td>1</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>CB180</td><td></td><td></td><td></td><td></td><td>0.441</td><td></td><td>0.974</td><td>0.498</td><td>1</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>ΣPCBi</td><td></td><td></td><td></td><td></td><td>&gt;0.730</td><td>0.585</td><td>0.821</td><td>0.780</td><td>0.781</td><td>1</td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>BDE28</td><td>0.384</td><td></td><td></td><td></td><td>0.426</td><td></td><td>0.627</td><td></td><td>0.562</td><td>0.468</td><td>1</td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>BDE47</td><td>0.346</td><td></td><td></td><td></td><td>0.558</td><td>0.430</td><td>0.674</td><td>0.461</td><td>0.595</td><td>0.656</td><td>0.861</td><td>1</td><td></td><td></td><td></td><td></td></tr><tr><td>BDE100</td><td>0.480</td><td></td><td>0.390</td><td>0.440</td><td>0.619</td><td>0.608</td><td>0.529</td><td>0.520</td><td>0.443</td><td>0.639</td><td>0.659</td><td>0.893</td><td>1</td><td></td><td></td><td></td></tr><tr><td>BDE99</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>BDE154</td><td>0.416</td><td></td><td></td><td>0.416</td><td></td><td></td><td>0.496</td><td></td><td>0.420</td><td>0.350</td><td>0.763</td><td>0.774</td><td>0.661</td><td>1</td><td></td><td></td></tr><tr><td>BDE153</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>0.598</td><td>0.369</td><td></td><td></td><td></td><td></td></tr><tr><td>BDE209</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>1</td></tr><tr><td>ΣTri-hexa BDE</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>0.761</td><td>0.347</td><td>0.433</td></tr></tbody></table>
<figure><img src="image_5.png" /><figcaption>**Fig. 3** PCA projections of muscle concentrations as ng g⁻¹ dw for 36 objects (fish subgroups (*circles* Marnay; stars Epinay, diamonds Triel; and triangles Viry Châtillon) and 18 variables (*solid lines* represent compound concentrations)</figcaption></figure>

(>80 %) by the Seine-Aval treatment plant. Concentrations in clarified effluents were 0.2 ng L⁻¹ for BDE100, 2 ng L⁻¹ for BDE47 and BDE99, and 4 ng L⁻¹ for BDE209.

Epinay and Triel fish clusters seem to be linked to low-chlorinated PCBs (CB28, CB52, CB101, and CB118). These congeners, characterized by a high volatility, might originate from atmospheric deposits. Indeed, several inputs occurring during rainy periods from storm overflows located downstream of Paris might bring contamination from atmospheric washout and runoff on surfaces impervious to the river. Σ7PCBi concentrations, as an annual mean in total air of the Paris area, were estimated at 0.254 ng m⁻³ and their fluxes in bulk deposition at 9.9 ng m² d⁻¹ with the highest values for CB28 (2.27 ng m² d⁻¹) and CB52 (2.78 ng m² d⁻¹) (Blanchard et al. 2006).

## Evaluation of BAFs for PCBs, PBDEs, and Phthalates

High bioaccumulations with BAF > E+04 were found for PCBs from CB101 to CB180 with a maximal value for CB138 (Fig. 4). Moreover, BAF showed a strong parabolic correlation with log Kow (*r* = 0.631, *p* < 0.001, *n* = 27) for PCB congeners in muscle tissue with a decrease in bioaccumulation for CB153 and CB180 (Fig. 5). The most hydrophobic PCBs seem to migrate poorly from water toward organisms. Our observations are consistent

with the parabolic correlation profile between fish bio-concentration and log Kow described for catfish (*Ictalurus punctatus*) from the Potomac River (USA) by Crimmins et al. (2002). CB77 was not taken into account in this relationship processes because of its very low BAF of 3.1E+02 related to active biodegradation by way of cytochrome P450 and subsequent low bioaccumulation (Bucheli and Fent 1995). In the REACH program, the bioaccumulation criteria for predicting accumulation in fish is BAF > 2000 and for a highly bioaccumulative compound is BAF > 5000 (Inoue et al. 2012). Modelling of PCB bioaccumulation in a Baltic trophic web showed that log Kow emerged as the single most important parameter for PCB uptake and bioaccumulation (Nfon and Cousins 2007).

Inversely, for PBDEs, the highest BAFs were obtained for the slightly brominated tri- and tetra- congeners as a consequence of their occurrence from debromination of heavier BDEs, particularly BDE209 and BDE99, which display lower BAF values (Fig. 4). Moreover, a negative correlation (*p* < 0.05) was found between BAFs and log Kow (Fig. 5).

Our results underline the trend of highly brominated BDEs (1) to be adsorbed onto particles, which impedes their bioavailability; and (2) to undergo debromination. A small detection frequency for BDE209 and a rapid decrease
<figure><img src="image_6.png" /><figcaption>**Fig. 4** BAF distribution for 6 phthalates, 10 PCBs, and 7 PBDEs in roach muscle</figcaption></figure>

in fish tissue were reported by Voorspoels et al. (2003). Stapleton et al. (2004a, 2004b) showed the occurrence of BDE99 debromination in the common carp (*C. carpio*) as well as the formation of hexa-BDE in juvenile carp exposed to BDE209-spiked food. Bhavsar et al. (2008) proposed a biotransformation pathway for the 13 major PBDEs assuming that bromines in the ortho- and meta-positions are more easily debrominated than those in the para-positions. Moreover, Munschy et al. (2011) found that metabolism by way of debromination appears to be a major degradation route of PBDEs in juvenile sole (*S. solea*) compared with biotransformation into hydroxylated metabolites. In this way, elimination of highly brominated BDEs occurs rapidly with a half-life of 43 days for BDE209 compared with 86 days for BDE28.

Other BAFs were observed for phthalates and did not correlate with log Kow (Fig. 4). They were consistent with BAF < 5000 reported for these compounds by Gobas et al. 2003). Indeed, for high molecular-weight compounds, BAFs were lower than expected from their physicochemical properties. Metabolic transformation and low bioavailability were proposed by Mackintosh et al. (2004) to explain these observations. In addition, Samandar et al. (2009) reported rapid biodegradation leading to hydrolytic and oxidative monoesters. Peijnenburg and Struijs (2006) described fast biotransformation in fish with fugacity lower by several magnitudes compared with water.

## Conclusion

By this work, we contribute the documentation of freshwater fish contamination by three classes of chemicals known as EDs, documentation that was poorly investigated until now in the Seine River basin (France). Distributions of the three endocrine-disruptor classes in roach muscle were evaluated jointly for the first time. This study clearly shows the impact of urbanized areas on the contamination of water and sediment from the Seine and the Orge rivers and, subsequently, on fish. Bioaccumulation of all of the three classes of chemicals was proven in roach from the Ile-de-France rivers, except BDE209, which is poorly bioavailable, and PCB77, which is easily biodegraded. Despite their ban, PCBs still remain in fish. A strong correlation between PCB and PBDE muscle concentrations highlights their common sources and similar environmental fate.

Our findings indicate that biotransformation of heavy PBDEs, namely BDE209, occurs in roach, thus leading to fewer brominated compounds. Considering both the high

<figure><img src="image_7.png" /><figcaption>**Fig. 5** Relationships between BAF and log Kow for PCBs (*p* < 0.001, *n* the Seine River)</figcaption></figure>

<figure><img src="image_8.png" /><figcaption>27) and PBDEs (*p* < 0.05, *n*</figcaption></figure>

<caption>21) in muscle tissue of roach from</caption>
contamination levels of BDE209 in the aquatic environment and the continued use of deca-BDE mixtures, the occurrence of slightly brominated BDEs in surface water by way of debromination processes remains of major concern.

This study provides the distribution of BAF coefficients in roach for a wide range of EDs. From a global viewpoint, our study of BAF for the three chemicals confirms the reliability of these parameters for building predictive models of bioaccumulation assessment that might be helpful for the biomonitoring of aquatic ecosystem quality. The three classes of pollutants encountered in fish muscle might play a part in the involvement of fish endocrine disturbances observed in rivers flowing through highly urbanized basins. The investigation of hydrophobic xenobiotic accumulation by roach from the Seine and the Orge rivers show that (1) this ubiquitous species is a relevant indicator of the contamination level of its habitat; and (2) roach can used as sentinel species for the assessment of surface water quality in the Seine River basin.

**Acknowledgments** This work was supported by the PIREN SEINE Research Programme. ONEMA provided assistance for electric fishing. We thank Catherine Bourges and Annie Desportes for technical assistance.

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