Sulphur-containing metabolites of the fungicides pentachloronitrobenzene (PCNB) and hexachlorobenzene (HCB) II. Mass spectra

Mass spectrometric data of synthesized sulphur-containing derivatives of the fungicides pentachloronitrobenzene (PCNB) and hexachlorobenzene (HCB), such as thiophenols, thioanisoles, disulphides, pentachlorophenylmethylsulphoxide, pentachlorophenylmethylsulphone, and acetylcysteine-conjugates, as well as non sulphur-containing derivatives, such as phenols, pentachloroanisole, and chlorinated benzenes are reported.     

Photochemistry of pesticides, 61). Comparative photochemical studies on methyl 2-benzimidazolecarbamate (Carbendazim) and methyl (1-n-butylcarbamoyl)-2-benzimidazolecarbamate (Benlate) in aqueous hydrochloric acid

The singlet oxygen photolysis of methyl 2-benzimidazolecarbamate (Carbendazim, 1) in aqueous hydrochloric acid has been investigated. 2-Guanidinobenzimidazole 7, benzimidazole 9, 2,4′- (13) and 2,5′-bibenzimidazole 14, were isolated from the reaction products and identified. A comparative study on the singlet oxygen photolysis of Benlate 2 both in MeOH and aqueous hydrochloric acid, was also undertaken.     

Photochemistry of pesticides, 3: Photolysis of methyl 2-benzimidazolecarbamate (Carbendazim) in the presence of singlet oxygen

The photolysis of methyl 2-benzimidazolecarbamate (Carbendazim, $\text{1}$) in methanol and in the presence of singlet oxygen, was studied. Dimethyl oxalate $\text{4}$, 2-aminobenzimidazole $\text{7}$, benzimidazole $\text{9}$, N,N′-dicarbomethoxyguanidine $\text{13}$, monocarbomethoxyguanidine $\text{14}$, monocarbomethoxyurea $\text{15}$, and 2-guanidinobenzimidazole $\text{17}$, were isolated and identified in this reaction.A mechanism that accounts for the formation of the photoreaction products, is presented.     

Identification and significance of phenazone drugs and their metabolites in ground- and drinking water

Residues of three phenazone-type pharmaceuticals have been identified in routine analyses of groundwater samples from selected areas in the north-western districts of Berlin, Germany. Phenazone, propiphenazone, and dimethylaminophenazone have been detected in some wells at concentrations up to the low microg/l-level. Additionally, three phenazone-type metabolites namely 1-acetyl-1-methyl-2-dimethyl-oxamoyl-2-phenylhydrazide (AMDOPH), 1-acetyl-1-methyl-2-phenylhydrazide, and dimethyloxalamide acid-(N'-methyl-N-phenyl)-hydrazide have also been identified in these groundwater samples. The residues are suspected to originate from former production spills of a pharmaceutical plant located in a city north of Berlin. It was observed that with the exception of AMDOPH all other residues were efficiently removed during conventional drinking water treatment. The drug metabolite AMDOPH deriving from dimethylaminophenazone residues was found at concentrations of 0.9 microg/l in finished drinking water. However, a following study on the toxicological relevance of the AMDOPH residues has shown that there is no toxicological harm for humans at the low concentrations of AMDOPH observed in Berlin drinking water.     

Vertical distributions of persistent organic pollutants (POPs) caused from organochlorine pesticides in a sediment core taken from Ariake bay, Japan

Persistent organic pollutants (POPs) of organochlorine pesticides such as dichlorodiphenyl trichloroethane (DDTs) and its metabolites, hexachlorobenzene (HCB), heptachlor, chlordane compounds (CHLs), aldrin, dieldrin, endrin, mirex and isomers of hexachlorocyclohexane (HCHs), were analyzed in sediment cores collected from Ariake Bay, Japan. Although Chikugo River has the largest flow in Ariake Bay, the total concentration of POPs in surface sediment was found in St.3, mouth of the Yabe River, where that level was two times higher than St.1, mouth of the Chikugo River. It could be assumed that the potential source of POPs contamination is relatively close to this study area. Relatively high residue levels of HCB, HCHs and DDTs in sediment core were found during the period from 1967 to 1970. In this layer, the HCB concentration investigated in sediment cores of Ariake Bay was maximum, 2.6 ng g(-1) dry weight and higher than that of Tokyo Bay and subsequently detected in deeper sediment cores. The ratio of (DDD+DDE)/SigmaDDTs was high in top sediments (0-2 cm). Although there was a concentration of DDTs in the top sediment, it was noticed that DDT emission did not cause direct input of DDT recently. The HCHs determined in upper sediment cores might be originated from long-range accumulation in environment after dispersing of technical-grade HCH. Moreover, the CHLs, dieldrin and heptachlor concentrations were detected and recently increased in sediment core. POPs in sediment cores of Ariake Bay based on the possibility of PCP contamination during the early 1960s were reflected.     

Chemical, biological, and ecotoxicological assessment of pesticides and persistent organic pollutants in the Bahlui River, Romania

Background, aim, and scope  

Current knowledge on environmental impacts of industrial activities in Romania, particularly persistent organic pollutants (POPs), indicates that environmental standards of the European Union are not systematically met. In our study area, additional sources of POPs are agriculture and domestic wastes. Very scarce information is available upon environmental contaminations and effects. In the present study, we investigated the chemical pollution and their eventual impact on the ecosystem by measuring POPs and by using biological indicators of pollution.     

Multiresidue determination of carbamate,organochlorine, organophosphorus,and dicarboximide pesticides in lettuce by GC/MS

An extraction method based on matrix solid-phase dispersion was developed to determine pirimicarb, methyl parathion, malathion, procymidone, α -endosulfan and β -endosulfan in lettuce using gas chromatography-mass spectrometry. The best results were obtained using 4.0 g of lettuce, 2.0 g of silica as dispersant sorbent, 0.1 g of activated carbon as clean up sorbent and acetonitrile as eluting solvent. The method was validated using lettuce samples fortified with pesticides at six different concentration levels (0.1 to 2.0 mg/kg). Average recoveries (7 replicates) ranged from 50 to 120 %, with relative standard deviations between 0.6 and 8.0 %. Detection and quantification limits for lettuce ranged from 0.01 to 0.02 mg/kg and 0.04 to 0.10 mg/kg, respectively.     

Chemical,biological, and ecotoxicological assessment of pesticides and persistent organic pollutants in the Bahlui River,Romania

Background, aim, and scope

Current knowledge on environmental impacts of industrial activities in Romania, particularly persistent organic pollutants (POPs), indicates that environmental standards of the European Union are not systematically met. In our study area, additional sources of POPs are agriculture and domestic wastes. Very scarce information is available upon environmental contaminations and effects. In the present study, we investigated the chemical pollution and their eventual impact on the ecosystem by measuring POPs and by using biological indicators of pollution.

Materials and methods

The survey was carried out at six main sample sites along the Bahlui River. Sediments were chemically analysed for their content in polychlorinated biphenyls (PCBs), polycyclic aromatic hydrocarbons (PAHs) and organochlorine pesticides (OCPs)—hexachlorocyclohexanes (HCHs) isomers and the dichlorodiphenyl trichloroethane (DDT) family. River water was biologically monitored at the level of phytoplankton and benthic invertebrates’ communities. Water samples from six locations have been analyzed for algal species composition and correspondence to various water quality indices. Biological samples have been taken from the same locations so as to calculate the macroinvertebrate indices. In the most polluted areas, as revealed by previous methods, toxicity was tested by exposing the green alga Pseudokirchneriella subcapitata and the cladoceran Daphnia magna to various dilutions of water sample.

Results

Important concentrations of POPs were identified only in sediments at river mouths (sites S5 and S6). Along the year, the sum of PCB concentrations ranged between 3 and 10 ng/g dw (S5), and between 4 and 26 ng/g dw (S6). Concentration of HCHs ranged between 0.4 and 3 ng/g dw (both S5 and S6) with a higher contribution of the gamma-HCH (30–70%), followed by beta-HCH (20–50%). The beta-HCH isomer was found at lower concentrations or even not detected in outer city sites. DDTs were found at higher concentrations than HCHs and ranged between 0.18 and 4 ng/g dw (S5) and between 0.56 and 18 ng/g dw (S6). The parent compound, p,p′-DDT, could be detected only in low concentrations (up to 5 ng/g dw) and contributed with less than 30% to the sum of DDTs in sediment. The principal contributors of the ΣDDTs in sediment were p,p′-DDE, and p,p′-DDD. The o,p′-DDD and DDT isomers were minor contributors to the sum of DDT. PAHs were found at higher concentrations than DDTs and ranged between 6 and 36 ng/g dw (S5) and between 36 and 155 ng/g dw (S6). Fluoranthene was predominant (up to 40%), followed by phenantrene (up to 30%), naphthalene (up to 35%), and benzo-(g,h,i)-perylene (up to 23%). The saprobity index and the diatom index increased from springs to river mouth, indicating a decrease in the water quality, but within the limits of moderate pollution. The saprobity index varied between 1.99 at spring to 2.70 at mouth. The diatom index varied from 3.48 to 3.14. The species’ richness in phytoplankton has a less clear pattern along the river, but in general, it appears to be negatively influenced by pollution. At the level of biological consumer species, the analyses of the macroinvertebrates confirm the situation and the tendency shown with algae. In addition, the Shannon–Wiener index, the Pielou evenness index, and the McNaughton dominance index indicate a peculiar pattern: invertebrate communities appear to a have a more stable structure along the river, with visible shifts at springs and at river mouths. Water toxicity testing indicates low toxicity of river waters around the city of Iasi, with two notable exceptions: the point pollution at the domestic wastewater treatment discharge and at the old open-air deposit of domestic solid wastes. Another important result was that tested algae appeared to be more readily affected than tested cladoceran: EC₅₀ (percent effluent) was 16 in algae and 28 in cladocerans. The slope of toxic effect was also much steeper in cladocerans (6) than in algae (1.8), which means that the toxic effect is more sudden on the tested invertebrates than on the tested algae.

Discussion

Pollutant concentrations reported herein are lower or similar than those reported for the sediments by earlier studies (RIZA 2000; Dragan et al., Int J Environ Anal Chem 86:833–842, 2006). Ratios of individual PAH compounds indicate important pyrolytic inputs and suggest that PAHs in the area are derived from the combustion of fossil fuels. Biologically, the waters appear to be beta-mesosaprobic towards alpha-mesosaprobic according to the saprobic index classification and undergo moderate pollution according to the diatom index classification. Water quality decreases from springs to river mouths. Algal species richness index has a less clear pattern along the river. Water toxicity is low, but certain sources of point pollution require increased attention.

Conclusions

The water quality is better than expected, probably because of the drop in pollution intensity following the collapse of local agricultural and industrial activity following the fall of communism in 1989. Nevertheless, further studies will be needed to confirm and refine our results. While this study draws no strident alarm, it appeals for high attention, particularly because the economic activity in the area is expected to increase.

Recommendations and perspectives

Future close monitoring will be necessary for insuring compliance with the Water Framework Directive, and for refining standards and understanding of the local situation, but with relevance for the wider international community. On the basis of the situation described in the present study, we recommend that future studies dedicate specific efforts to point pollution and effluent toxicity, particularly around the city of Iasi. For a better understanding of pollution and its effects, we recommend pursuing the type of multidisciplinary investigations proposed by the present study: chemical, ecotoxicological, and ecological. We also recommend that new methods should be developed and/or refined, like the empirical determination of partitioning coefficients in water and soils, process-based toxicity methods in ecotoxicological assessments, searching for interactions between pollution, producers, and consumers in aquatic ecosystems. We also recommend preference for cheaper survey methods, as these will be more applicable locally.

     

Atmospheric chemistry of HFE-7000 (CF(3)CF (2)CF (2)OCH (3)) and 2,2,3,3,4,4,4-heptafluoro-1-butanol (CF (3)CF (2)CF (2)CH (2)OH): kinetic rate coefficients and temperature dependence of reactions with chlorine atoms

Background, aim, and scope  The adverse environmental impacts of chlorinated hydrocarbons on the Earth’s ozone layer have focused attention on the effort to replace these compounds by nonchlorinated substitutes with environmental acceptability. Hydrofluoroethers (HFEs) and fluorinated alcohols are currently being introduced in many applications for this purpose. Nevertheless, the presence of a great number of C–F bonds drives to atmospheric long-lived compounds with infrared absorption features. Thus, it is necessary to improve our knowledge about lifetimes and global warming potentials (GWP) for these compounds in order to get a complete evaluation of their environmental impact. Tropospheric degradation is expected to be initiated mainly by OH reactions in the gas phase. Nevertheless, Cl atoms reaction may also be important since rate constants are generally larger than those of OH. In the present work, we report the results obtained in the study of the reactions of Cl radicals with HFE-7000 (CF₃CF₂CF₂OCH₃) (1) and its isomer CF₃CF₂CF₂CH₂OH (2). Materials and methods  Kinetic rate coefficients with Cl atoms have been measured using the discharge flow tube–mass spectrometric technique at 1 Torr of total pressure. The reactions of these chlorofluorocarbons (CFCs) substitutes have been studied under pseudo-first-order kinetic conditions in excess of the fluorinated compounds over Cl atoms. The temperature ranges were 266–333 and 298–353 K for reactions of HFE-7000 and CF₃CF₂CF₂CH₂OH, respectively. Results  The measured room temperature rate constants were k(Cl+CF₃CF₂CF₂OCH₃) = (1.24 ± 0.28) × 10⁻¹³ cm³ molecule⁻¹ s⁻¹and k(Cl+CF₃CF₂CF₂CH₂OH) = (8.35 ± 1.63) × 10⁻¹³ cm³ molecule⁻¹ s⁻¹ (errors are 2σ + 10% to cover systematic errors). The Arrhenius expression for reaction 1 was k ₁(266–333 K) = (6.1 ± 3.8) × 10⁻¹³exp[−(445 ± 186)/T] cm³ molecule⁻¹ s⁻¹ and k ₂(298–353 K) = (1.9 ± 0.7) × 10⁻¹²exp[−(244 ± 125)/T] cm³ molecule⁻¹ s⁻¹ (errors are 2σ). The reactions are reported to proceed through the abstraction of an H atom to form HCl and the corresponding halo-alkyl radical. At 298 K and 1 Torr, yields on HCl of 0.95 ± 0.38 and 0.97 ± 0.16 (errors are 2σ) were obtained for CF₃CF₂CF₂OCH₃ and CF₃CF₂CF₂CH₂OH, respectively. Discussion  The obtained kinetic rate constants are related to the previous data in the literature, showing a good agreement taking into account the error limits. Comparing the obtained results at room temperature, k ₁ and k ₂, HFE-7000 is significantly less reactive than its isomer C₃F₇CH₂OH. A similar behavior has been reported for the reactions of other fluorinated alcohols and their isomeric fluorinated ethers with Cl atoms. Literature data, together with the results reported in this work, show that, for both fluorinated ethers and alcohols, the kinetic rate constant may be considered as not dependent on the number of –CF₂– in the perfluorinated chain. This result may be useful since it is possible to obtain the required physicochemical properties for a given application by changing the number of –CF₂– without changes in the atmospheric reactivity. Furthermore, lifetimes estimations for these CFCs substitutes are calculated and discussed. The average estimated Cl lifetimes are 256 and 38 years for HFE-7000 and C₃H₇CH₂OH, respectively. Conclusions  The studied CFCs’ substitutes are relatively short-lived and OH reaction constitutes their main reactive sink. The average contribution of Cl reactions to global lifetime is about 2% in both cases. Nevertheless, under local conditions as in the marine boundary layer, τ _Cl values as low as 2.5 and 0.4 years for HFE-7000 and C₃H₇CH₂OH, respectively, are expected, showing that the contribution of Cl to the atmospheric degradation of these CFCs substitutes under such conditions may constitute a relevant sink. In the case of CF₃CF₂CF₂OCH₃, significant activation energy has been measured, thus the use of kinetic rate coefficient only at room temperature would result in underestimations of lifetimes and GWPs. Recommendations and perspectives  The results obtained in this work may be helpful within the database used in the modeling studies of coastal areas. The knowledge of the atmospheric behavior and the structure–reactivity relationship discussed in this work may also contribute to the development of new environmentally acceptable chemicals. New volatile materials susceptible of emission to the troposphere should be subject to the study of their reactions with OH and Cl in the range of temperature of the troposphere. The knowledge of the temperature dependence of the kinetic rate constants, as it is now reported for the case of reactions 1 and 2, will allow more accurate lifetimes and related magnitudes like GWPs. Nevertheless, a better knowledge of the vertical Cl tropospheric distribution is still required.     

The Cl-initiated oxidation of CH3C(O)OCH=CH2, CH3C(O)OCH2CH=CH2, and CH2=CHC(O)O(CH2)3CH3 in the troposphere

Background, aim, and scope  

Unsaturated esters are emitted to the atmosphere from biogenic and anthropogenic sources, including those from the polymer industry. Little information exists concerning the atmospheric degradation of unsaturated esters, which are mainly initiated by OH radicals. Limited information is available on the degradation of alkenes by Cl atoms and almost no data exists for the reactions of unsaturated esters with Cl atoms. This data is necessary to assess the impact of such reactions in maritime environments where, under circumstances, OH radical- and Cl atom-initiated oxidation of the compounds can be important. Rate coefficients for the reactions of chlorine atoms with vinyl acetate, allyl acetate, and n-butyl acrylate have been determined at 298 ± 3 K and atmospheric pressure. The kinetic data have been used in combination with that for structurally similar compounds to infer the kinetic contributions from the possible reaction channels to the overall reaction rate.     

Rat urinary metabolites from O,O-diethyl-O-(3,5,6-trichloro-2-pyridyl) phosphorothioate.

Rats metabolized single oral doses of O,O-diethyl-O(3,5,6-trichloro-2-pyridyl-2,6-14C) phosphorothioate to at least six radiolabeled urinary metabolites. The urine contained about 90 percent of the dose. Three of these metabolites were identified as the glucuronide of 3,5,6-trichloro-2-pyridinol (80% the urinary 14C), a glycoside of 3,5,6-trichloro-2-pyridinol (4%), and 3,5,6-trichloro-2-pyridinol (12%).     

Simultaneous conversion of CHClF(2) and CH(3)Br to CH(2)CF(2)

Gas phase reaction of CHClF(2) with CH(3)Br in an alumina tube reactor at 773-1123 K as a function of various input ratios of CH(3)Br to CHClF(2) is presented. The major products detected include C(2)F(4), CH(2)CF(2), and CH(4). Minor products include CH(3)Cl, CHF(3), C(2)H(4), C(2)H(2), CH(2)CF-CF(3), and C(2)H(3)F. The reaction produces a high yield of CH(2)CF(2) (53% based on CHClF(2) feed) at 1123 K and an input molar ratio of CH(3)Br to CHClF(2) of 1.8, suggesting that the reaction potentially can be developed as a process to convert two ozone depleting substances (CHClF(2) and CH(3)Br) to a highly valuable chemical, CH(2)CF(2). The reaction of CHClF(2) with CH(3)Cl and CH(3)I was also investigated under similar reaction conditions, to assist in understanding the reaction chemistry involved in the reaction of CHClF(2) with CH(3)Br.     

Behavior of sartans (antihypertensive drugs) in wastewater treatment plants,their occurrence and risk for the aquatic environment

Pharmaceuticals and other anthropogenic trace contaminants reach wastewaters and are often not satisfactorily eliminated in sewage treatment plants. These contaminants and/or their degradation products may reach surface waters, thus influencing aquatic life. In this study, the behavior of five different antihypertonic pharmaceuticals from the sartan group (candesartan, eprosartan, irbesartan, olmesartan and valsartan) is investigated in lab-scale sewage plants. The elimination of the substances with related structures varied broadly from 17 % for olmesartan up to 96 % for valsartan. Monitoring data for these drugs in wastewater effluents of six different sewage treatment plants (STPs) in Bavaria, and at eight rivers, showed median concentrations for, e.g. valsartan of 1.1 and 0.13 μg L^?1, respectively. Predicted environmental concentrations (PEC) were calculated and are mostly consistent with the measured environmental concentrations (MEC). The selected sartans and the mixture of the five sartans showed no ecotoxic effects on aquatic organisms in relevant concentrations. Nevertheless, the occurrence of pharmaceuticals in the environment should be reduced to minimize the risk of their distribution in surface waters, ground waters and bank filtrates used for drinking water.     

Qualitative and quantitative cancer risk assessment of 2, 3, 7, 8-tetrachloro-dibenzo-p-dioxin (2, 3, 7, 8-TCDD)

The carcinogenicity of 2,3,7,8-TCDD at multiple organ sites in animals has been well established by several cancer bioassays. Results of two of the most notable of these, the Kociba et al. (1978) rat feeding study and the National Toxicology Program (1980) gavage study in rats and mice showed hepatocellular carcinomas in two strains of female rats and male and female mice. Other tumor sites included carcinomas of the lung, tongue, hard palate and nasal turbinates, thyroid, and subcutaneous tissue. The evidence for carcinogenicity of 2,3,7,8-TCDD in animals is regarded as “sufficient” using the classification system of the International Agency for Research on Cancer (IARC).

Two Swedish epidemiologic case-control studies (Hardell and Sandstrom, 1979; Eriksson et al. 1979, 1981) reported a significant five- to sevenfold excess risk of soft-tissue sarcomas (STS) from occupational exposure to chlorinated phenoxyacetic acid herbicides and/or chlorophenols. Additionally, several small cohort studies collectively exhibited an unusual cluster of STS, significantly increased over combined expected incidence. Problems with these studies do not appear to be sufficient to discount this excess risk. The human evidence alone for the carcinogenicity of 2,3,7,8-TCDD is “inadequate” using the IARC classification. However, for 2,3,7,8-TCDD in combination with chlorinated phenoxyacetic acid herbicides and/or chlorophenols, the human evidence is considered to be “limited.” The overall evidence for carcinogenicity considering both animal and human studies would place 2,3,7,8-TCDD alone in the IARC category 2B, meaning that the substance is probably carcinogenic in humans. The overall weight of evidence for 2,3,7,8-TCDD in combination with chlorinated phenoxyacetic acid herbicides and/or chlorophenols is regarded as IARC category 2A, also meaning that they are probably carcinogenic for humans.

Using current EPA methodology for quantitatively estimating cancer risks, several animal data sets have been analyzed. Comparing the results, the upper-limit incremental unit risk estimate is 1.6 × 10⁻² for a lifetime exposure of 1 ng/kg/day. This estimate is derived from a lifetime feeding study (Kociba et al., 1978) in which 2,3,7,8-TCDD induced tumors of the liver, lungs, hard palate, and nasal turbinates in female rats. Incremental unit cancer risks are also extrapolated for lifetime 2,3,7,8-TCDD exposures in water and air. Based on continuous lifetime exposure to 1 ng/L 2,3,7,8-TCDD in drinking water, the upper-limit estimate of extra cancer risk per individual is 4.5 × 10⁻³. For lifetime exposure to 1 pg 2,3,7,8-TCDD/m³ in the ambient air, the upper-limit individual risk is 3.3 × 10⁻⁵.     

Expression alterations of cytochromes P4501A1, 2E1, and 3A,and their receptors AhR and PXR caused by 1-octyl-3-methylimidazolium chloride in mouse mammary carcinoma cells

Cytochrome P450s (CYPs) play a key role in the metabolism of a wide range of environmental xenobiotics and endogenous compounds. The expression and activity levels of CYPs can be elevated by a process of induction involving the activation of nuclear receptors. The effects of the ionic liquid 1-octyl-3-methylimidazolium chloride ([C₈mim][Cl]) on the expression of cytochrome P450 members, including CYP1A1, CYP2E1, and CYP3A, as well as on aryl hydrocarbon receptor (AhR) and pregnane X receptor (PXR) in mouse mammary carcinoma cells (EMT6) were investigated by using quantitative real-time PCR in the present study. The results reveal that [C₈mim][Cl]-exposure up-regulates the expressions of CYP1A1, CYP2E1, and CYP3A at mRNA level, suggesting that imidazolium-based ionic liquids can activate CYPs. Our results also suggest that [C₈mim][Cl]-mediated CYP3A induction be PXR-dependent. This result may be beneficial to evaluating the environmental toxicity of imidazolium-based ionic liquids and investigating the metabolism of imidazolium-derivative drugs.     

Emerging pollutants in sewage, surface and drinking water in Galicia (NW Spain)

A monitoring programme was carried out on wastewater, surface and drinking water on the NW area of Spain during the four seasons of a year period (November 2007-September 2008). This study covered a series of emerging pollutants of different classes, including pharmaceuticals, neutral and acidic organophosphorus flame retardant/plasticizers (OPs), triclosan, phenoxy-herbicides, insect repellents and UV filters. From the total set of 53 compounds, 19 were found in raw wastewater with median concentrations higher than 0.1 μg L⁻¹. Among them, salicylic acid, ibuprofen and the UV filter benzophenone-4 (BP-4) were the most concentrated, exceeding the 1 μg L⁻¹ median value. Subsequently, 11 of these contaminants are not efficiently enough removed in the small WWTPs tested and their median concentrations in effluents still surpassed the 0.1 μg L⁻¹, so that they can spread through surface water. These chemicals are the pharmaceuticals naproxen, diclofenac and atenolol; the OPs tri(2-chloroethyl) phosphate (TCEP), tri(chloropropyl) phosphate (TCPP), tri-n-butyl phosphate (TnBP), diphenyl phosphate (DPhP) and diethylhexyl phosphate (DEHP); and the sulphonate UV filters BP-4 and 2-phenylbenzimidazole-5-sulphonic acid (PBSA). These OPs were then the dominant emerging pollutants occurring in surface and drinking water, where they are detected in the 20-200 ng L⁻¹ range. Pharmaceuticals and UV filters are typically below the 10 ng L⁻¹ level. Finally, herbicides were only detected in the last sampling campaign under the 100 ng L⁻¹ drinking water European Union limit.     

Organochlorinated pesticides, PCBs, dioxins, and PBDEs in grey mullets (Liza ramada) and allis shads (Alosa alosa) from the Vilaine estuary (France)

This study aimed to compare the contamination levels of various organohalogenated compounds in two migratory fish species in the Vilaine River in western France. Organochlorinated pesticides, polychlorinated biphenyls (PCBs), dioxins (polychlorinated dibenzo-p-dioxins/dibenzofurans (PCDDs/Fs)), and polybrominated diphenyl ethers (PBDEs) were analyzed in two diadromous species from the Vilaine estuary, the grey mullet (Liza ramada)—an amphihaline species, and the allis shad (Alosa alosa)—an anadromous species. Fish were collected in spring 2004 and spring 2005, upstream and downstream of the Arzal Dam. PCB contamination varied from 27 to 200 ng?g^?1 dry weight (d.w.). PCDDs/Fs, expressed in toxicity equivalent quantity (TEQ) varied from 0.4 to 2.8 pg?g^?1 d.w. Dioxins and dioxin-like PCBs expressed in total TEQ varied from 1.4 to 18.8 pg?g^?1 d.w. PBDE47 was present at around 2–10 ng?g^?1 d.w. and concentrations of the insecticide dichlorodiphenyltrichloroethane breakdown product p,p′-dichlorodiphenylchloroethylene varied from 1 to 14 ng?g^?1 d.w. For both species, specimens collected upstream were more contaminated. The grey mullet specimens were less contaminated than the allis shad when taken downstream of the dam but were more contaminated upstream. The allis shads presented intermediate contaminant concentrations with a less pronounced difference between upstream and downstream specimens. However, it is thought that shads do not feed when they spawn in the upstream parts of rivers, which should modify the contaminant concentrations. However, measurements in upstream shad samples show an unexpected increase of the contamination, which remains unexplained.     

Concentrations,patterns and metabolites of organochlorine pesticides in relation to xenobiotic phase I and II enzyme activities in ringed seals (Phoca hispida) from Svalbard and the Baltic Sea

The present study investigates the concentrations and patterns of organochlorine pesticides (OCPs) and their metabolites in liver and plasma of two ringed seal populations (Phoca hispida): lower contaminated Svalbard population and more contaminated Baltic Sea population. Among OCPs, p,p′-DDE and sum-chlordanes were the highest in concentration. With increasing hepatic contaminant concentrations and activities of xenobiotic-metabolizing enzymes, the concentrations of 3-methylsulfonyl-p,p′-DDE and the concentration ratios of pentachlorophenol/hexachlorobenzene increased, and the toxaphene pattern shifted more towards persistent Parlar-26 and -50 and less towards more biodegradable Parlar-44. Relative concentrations of the chlordane metabolites, oxychlordane and -heptachlorepoxide, to sum-chlordanes were higher in the seals from Svalbard compared to the seals from the Baltic, while the trend was opposite for cis- and trans-nonachlor. The observed differences in the OCP patterns in the seals from the two populations are probably related to the catalytic activity of xenobiotic-metabolizing enzymes, and also to differences in dietary exposure.     

Organochlorine pesticides (DDTs and HCHs) in soils from the outskirts of Beijing, China

Concentrations of HCH (hexachlorocyclohexane) and DDT (Dichlorodiphenyltrichloroethane) were determined in shallow subsurface (5-30 cm depth) and deep soil layers (150-180 cm depth) from the outskirts of Beijing, China. Concentrations of total HCHs (including alpha, beta, gamma, delta-isomers) and total DDTs (including p,p'-DDT, p,p'-DDE, p,p'-DDD, o,p'-DDT) in shallow subsurface soils ranged from 1.36 to 56.61 ng/g dw (median 5.25 ng/g), and from 0.77 to 2178 ng/g (median 38.66 ng/g), respectively, and those in the deeper layers were approximately an order of magnitude less. The spatial distribution of HCHs and DDTs reflected the known historical usage of these pesticides. No correlation between the concentrations of pesticides and soil organic matter content or clay content can be found. The factors affecting residue levels and compositions of DDT and HCH were discussed. The contour maps of beta/gamma ratios and DDT/DDE ratios for both the shallow subsurface and deep layer soils were drawn.