Organic pollutants in compost and digestate. Part 1. Polychlorinated biphenyls, polycyclic aromatic hydrocarbons and molecular markers

In Europe, 9.3 x 10(6) t(dry weight (dw)) of compost and digestate are produced per year. Most of this is applied to agricultural land, which can lead to considerable inputs of organic pollutants, such as polychlorinated biphenyls (PCB) and polycyclic aromatic hydrocarbons (PAH) to soil. This paper presents an inventory of the pollutant situation in source-separated composts, digestates and presswater in Switzerland by a detailed analysis of over 70 samples. PCB concentrations ( summation PCB 28, 52, 101, 118, 138, 153, 180) were significantly higher in urban (median: 30 microg kg(-1)dw, n = 52) than in rural samples (median: 14 microg kg(-1)dw, n = 16). Together with low concentrations in general, this points to aerial deposition on compost input material as the major contamination pathway. Enantiomeric fractions of atropisometric PCB were close to racemic. Median PAH concentration was 3010 microg kg(-1)dw( summation 15PAH, n = 69), and one quarter of the samples exhibited concentrations above the relevant Swiss guide value for compost (4000 microg kg(-1)dw). The levels were influenced by the treatment process (digestate > compost), the season of input material collection (spring-summer > winter > autumn), the particle size (coarse-grained > fine-grained), and maturity (mature > less mature). The main source of PAH in compost was pyrogenic, probably influenced mainly by liquid fossil fuel combustion and some asphalt abrasion, as suggested by multiple linear regression. This study, together with a companion paper reporting on other organic contaminates including emerging compound classes, provides a starting point for a better risk-benefit estimation of the application of compost and digestate to agricultural soil in Switzerland.     

Occurrence of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) in Lake Maggiore (Italy and Switzerland)

Samples of air (gas and particulate phases), bulk deposition, aquatic settling material and sediments were collected in Lake Maggiore (LM) in order to determine their content of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs). Air (gas and particulate phases) concentrations were 0.5 pg m(-3), 80 pg m(-3), 13 pg m(-3) and 106 pg m(-3) for SigmaPCDD/Fs, SigmaPCBs, Sigma dioxin-like PCBs (DL-PCBs) and SigmaPBDEs, respectively. Deposition fluxes ranged from 0.7 ng m(-2) d(-1) for SigmaPCDD/Fs to 32 ng m(-2) d(-1) for SigmaPCBs. Aquatic settling material presented concentrations of 0.4 ng g(-1) dry weight (dw) for SigmaPCDD/Fs, 13 ng g(-1) dw for SigmaPCB, 3.4 ng g(-1) dw for SigmaDL-PCBs and 5.7 ng g(-1) dw for SigmaPBDEs. Mean sediment concentrations were 0.4 ng g(-1) dw for SigmaPCDD/Fs, 11 ng g(-1) dw for SigmaPCB, 3 ng g(-1) dw for SigmaDL-PCBs and 5.1 ng g(-1) dw for SigmaPBDEs. Similar PCDD/F and DL-PCB congener patterns in all the environmental compartments of LM point to an important, if not dominant, contribution of atmospheric deposition as source of these pollutants into LM. In contrast, PBDE congener distribution was not similar in the different environmental compartments. BDE 47 dominated air and settling material, while BDE 209 was the predominant congener in the bulk atmospheric deposition. Moreover, sediments showed two distinct PBDE congener profiles. Lower PBDE concentrated sediments were dominated by congeners 47 and 99, while BDE 209 dominated in higher PBDE concentrated samples. This suggests the influence of local sources as well as atmospheric input of PBDEs into LM.     

Persistent organic pollutants in sediment from the southern Baltic: risk assessment

The concentrations of organochlorine pesticides, PCBs, and PCDD/Fs were measured in sediment samples collected from the Gulf of Gdańsk, the Gdańsk Deep, the Vistula Lagoon and the off-shore waters in the southern Baltic Sea. The determinations were conducted in the fraction <63 μm. The highest levels of pollutants were found in sediments from the Gulf of Gdańsk and the Gdańsk Deep. In these sediments, concentrations of pp'-DDT and its metabolites (pp'-DDE and pp'-DDD) ranged from 2 to 11 μg kg(-1) dw. Concentrations of HCB were between 0.1 and 1.0 μg kg(-1) dw. Concentrations of the sum of α-, β-, γ-HCH were between 0.3 and 2.58 μg kg(-1) dw. Concentrations of marker PCBs ranged from about 2 to 11 μg kg(-1) dry weight. Total TEQ PCDD/F/dl-PCB values in the studied samples varied between 1 and 18 ng kg(-1) dw. The data were evaluated in terms of ecotoxicological criteria based on the environmental impact of the pollutant effects. Our research indicated that in the sediment from the southern Baltic Sea, the PCDD/F and PCBs occurred at concentrations which could be dangerous to marine organisms.     

Chlorinated and brominated dibenzo-p-dioxins and dibenzofurans in surface sediment from Taihu Lake, China

Polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and polybrominated dibenzo-p-dioxins and dibenzofurans (PBDD/Fs) in surface sediment samples from Taihu Lake--an important water supply of the Yangtze River Delta, China--were investigated in the present study. Concentrations of PCDD/Fs ranged from 0.91 to 4.8 pg TEQ g(-1) dw (mean: 2.9 pg TEQ g(-1) dw, TEQ: Toxic Equivalent), which were all higher than the threshold effect level established by interim sediment quality guidelines in Canada (0.85 pg TEQ g(-1) dw). The levels of PBDD/Fs ranged from 0.16 to 1.6 pg TEQ g(-1) dw (mean: 0.52 pg TEQ g(-1) dw) and accounted for 5-33% (mean: 14%) of the total PCDD/Fs and PBDD/Fs TEQ. Comparatively, the abundance of sedimentary PCDD/Fs in the three regions (Meiliang Bay, Gonghu Bay, and Xukou Bay) showed a decreasing trend from the inflow region to the outflow region, while no significant difference was observed among their 2,3,7,8-PBDD/Fs levels, which suggested that the sources of PCDD/Fs and PBDD/Fs differed in this area. Principal component analysis suggested that the historical production/usage of pentachlorophenol and sodium pentachlorophenate was the dominant source of PCDD/Fs in the sediment of these regions. Although the specific sources of PBDD/Fs in the sediment of Taihu Lake were unclear, it was suspected to be due to atmospheric deposition; however, an additional study is needed to confirm this.     

Levels and distribution of PCDD/Fs, dl-PCBs, and organochlorine pesticides in sediments from the lower reaches of the Haihe River basin, China

The concentrations of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), dioxin-like polychlorinated biphenyls (dl-PCBs), and organochlorine pesticides (OCPs) in surface sediments from the lower reaches of the Haihe River basin, northern China, were determined by high-resolution gas chromatograph–high-resolution mass spectrometer. The concentrations of 2,3,7,8-substituted PCDD/Fs, dl-PCBs, and total OCPs [sum of hexachlorobenzene, hexachlorocyclohexanes, and dichlorodiphenyltrichloroethane (DDTs)] in 17 sediment samples were in the ranges of 11.6–1,180,924 pg/g dry weight (dw), 18.7–50,017 pg/g dw, and 1.7–35,280 ng/g dw, respectively. The contamination levels in the samples varied significantly between the different sites. Abnormally high concentrations of PCDD/Fs, dl-PCBs, and some OCPs were found in sediments from the lower reaches of the main channel of the Haihe River and the Dagu Drainage River, which were attributed to the historical production of pentachlorophenol and other pesticides near these locations. High levels of DDTs were detected in the Yongding New River sediment, which were likely to have originated from the discharge of wastewater from a dicofol factory upstream. In samples taken from other sites, the concentrations of these pollutants were at levels comparable to those documented in other areas of China. This preliminary investigation suggests that historical pesticide production in the Haihe River basin has contributed significantly to the contamination of this aquatic ecosystem and that further attention to this issue is warranted.     

Environmental contaminants in male river otters from Oregon and Washington, USA, 1994–1999

This study reports hepatic concentrations and distribution patterns of select metals, organochlorine pesticides (OCs), polychlorinated biphenyls (PCBs), polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) in 180 male river otters (Lontra canadensis) collected from Oregon and Washington, 1994-1999. Seven regional locations of western Oregon and Washington were delineated based on associations with major population centers, industry or agriculture. Cadmium (Cd) was not found above 0.5 microg g(-1), dry weight (dw) in juveniles, but increased with age in adults though concentrations were generally low (nd-1.18 microg g(-1), dw). Regional geometric means for total mercury (THg) ranged from 3.63 to 8.05 microg g(-1), dw in juveniles and 3.46-12.6 microg g(-1) (dw) in adults. The highest THg concentration was 148 microg g(-1), dw from an apparently healthy adult male from the Olympic Peninsula of Washington. Although THg increased with age in adult otters, the occurrence of the more toxic form methylmercury (MeHg) was not evaluated. Mean OC and PCB concentrations reported in this study declined dramatically from those reported in 1978-1979 from the lower Columbia River. Organochlorine pesticide and metabolite means for both juvenile and adult river otter males were all below 100 microg kg(-1), wet weight (ww), with only DDE, DDD and HCB having individual concentrations exceeding 500 microg kg(-1), ww. Mean SigmaPCB concentrations in both juvenile and adult male otters were below 1 microg g(-1) for all regional locations. Mean juvenile and adult concentrations of non-ortho substituted PCBs, PCDDs and PCDFs were in the low ng kg(-1) for all locations studied.     

PBDEs in marine and freshwater sediments from Belgium: levels, profiles and relations with biota

Sediments from the Belgian North Sea (BNS), the Western Scheldt Estuary (SE) and freshwater watercourses from the Scheldt basin were analysed for eight PBDE congeners, namely BDEs 28, 47, 99, 100, 153, 154, 183 and 209. Previously analysed biological samples from the same locations in the BNS and the SE have been shown to contain large amounts of PBDEs. Surprisingly, PBDE concentrations in the sediments were below the LOQ for samples from the BNS (except BDE 209), while in those from the SE the sum of PBDEs (not including BDE 209) were higher and ranged from 0.20 to 0.41 ng g(-1) dw. BDE 209 could be detected in 83% of the samples from the BNS and in all the samples from the SE. Concentrations up to 1200 ng g(-1) were hereby measured in the SE. Compared to the marine and estuarine locations, the sediments from the freshwater watercourses were relatively more polluted with the lower brominated PBDEs (<0.20-19 ng g(-1) dw). BDE 209 concentrations up to 320 ng g(-1) dw were measured in those sediments. However, the contribution of BDE 209 to the total amount of PBDEs varied much more at the freshwater locations than in the SE, which suggests a different input of pollutants. PBDE profiles observed in biological samples do not match the profiles of the sediments. BDE 183 and 209 could not be quantified in biota, although these congeners were undoubtedly present in the sediments. This raises questions about the bioavailability of these congeners in the environment.     

Monitoring dioxins and furans in the vicinity of an old municipal waste incinerator after pronounced reductions of the atmospheric emissions

In order to get an overall picture of the environmental impact of an old municipal solid waste incinerator (MSWI) from S. Adrià del Besòs (Barcelona, Catalonia, Spain), a monitoring program addressed at determining the levels of a number of pollutants in the vicinity of the facility was initiated in 1998. In March 1999, an adaptation was carried out due to EU legislation on pollutant emissions from the stack. As a result, emissions of polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) were notably reduced, and a significant (30%) decrease was found in the levels of PCDD/F in herbage samples collected in the vicinity of the MSWI. In March 2001, herbage samples were collected at the same sampling points and the PCDD/F levels measured again. The current PCDD/F concentrations range from 0.23 to 1.43 ng I-TEQ kg(-1) (dry matter), with median and mean values of 0.58 and 0.66 ng I-TEQ kg(-1) (dry matter), respectively, while in the 2000 survey the PCDD/F concentrations ranged from 0.22 to 1.20 ng I-TEQ kg(-1) (dry matter), with median and mean values of 0.57 and 0.61 ng I-TEQ kg(-1) (dry matter), respectively. Although the current PCDD/F concentrations in herbage samples are comparable to those found in recent surveys carried out in various places of Catalonia, an exhaustive evaluation of the data, including principal component analysis, indicates that other emission sources of PCDD/Fs also have a notable environmental impact on the area under direct influence of the MSWI.     

Environmental contaminants in Canadian shorebirds

Canadian shorebirds are exposed to environmental contaminants throughout their annual cycle. Contaminant exposure among species varies with diet, foraging behaviour and migration patterns. We sampled twelve species of shorebirds from four locations across Canada to assess their exposure to PCBs, organochlorine pesticides, as well as four trace elements (Hg, Se, Cd, As). SigmaPCB and SigmaDDT followed by SigmaCHL were most frequently found above trace level in the shorebird carcasses. In general, the plover species (American golden, semipalmated, black-bellied) appear to be the most contaminated with organochlorines, whereas Hudsonian and marbled godwits appear to be the least contaminated. Among adult birds, the greater and lesser yellowlegs had the highest hepatic Hg concentrations (2.4-2.7 microg g(-1) dw), whereas American golden plovers as well as Hudsonian and marbled godwits contained relatively low levels of Hg (<1 microg g(-1) dw). Renal Se concentrations varied from 3.2 to 16.7 microg g(-1) dw and exhibited little interspecific or seasonal variation. Renal Cd levels in adult birds were highest in Hudsonian godwits from Quill Lakes (43 microg g(-1) dw) and Cape Churchill (12 microg g(-1) dw), and lowest (0.8-1.5 microg g(-1) dw) in greater and lesser yellowlegs from Cape Churchill and Bay of Fundy. Renal As concentrations varied from 0.06 microg g(-1) dw in golden plovers from Cape Churchill to 4.6 and 5.1 microg g(-1) dw in dunlin samples from the Pacific coast. There is no evidence that contaminants were adversely affecting the shorebirds sampled from the Canadian locations in this study.     

Quantification and source identification of polycyclic aromatic hydrocarbons in sediment, soil, and water spinach from Hanoi, Vietnam

Polycyclic aromatic hydrocarbons (PAHs) were quantified in sediment, soil, and plant material from Hanoi, Vietnam, and an aquatic production system in peri-urban Hanoi. The sum of the concentration of 16 US-EPA priority PAHs ( summation PAH16) ranged between 0.44 and 6.21 mg kg(-1) dw in sediment and between 0.26 and 1.35 mg kg(-1) dw in soil, with decreasing concentrations from the urban area to the peri-urban area, indicating contributions from urban and industrial sources. Double plots of diagnostic source ratios indicate that PAHs originate from mixed petrogenic and pyrogenic sources, the latter being predominant. The predominance of low molecular weight (LMW) PAHs in the sediment samples suggests that petrogenic sources are more prevalent in the water environment than in the soil. In contrast, high molecular weight (HMW) PAHs dominated in water spinach which probably reflects the plant's uptake of particle-bound PAHs that originate from pyrogenic sources.     

Polybrominated diphenyl ethers (PBDEs) in the riverine and marine sediments of the Laizhou Bay area, North China

62 riverine and marine sediments were collected from the Laizhou Bay area, where the largest manufacturing base of brominated flame retardants (BFRs) in Asia is located. Eight polybrominated diphenyl ethers (PBDEs) were analyzed to investigate the impact of rapidly-developed bromine industries on the regional aquatic system. PBDE concentrations varied largely in riverine sediments. Σ(7)PBDEs (including BDE 28, 47, 99, 100, 153, 154 and 183) and BDE 209 ranged from 0.01 to 53 ng g(-1) dw and from 0.74 to 285 ng g(-1) dw with a mean value of 4.5 ng g(-1) dw and 54 ng g(-1) dw, respectively, indicating a strong influence of direct pollution discharges from local factories. In marine sediments, Σ(7)PBDEs and BDE 209 ranged from not detected (nd) to 0.66 ng g(-1) dw and from 0.66 to 12 ng g(-1) dw with a mean value of 0.32 ng g(-1) dw and 5.1 ng g(-1) dw, respectively. PBDE concentrations were mostly <10 ng g(-1) dw for Σ(7)PBDEs and <50 ng g(-1) dw for BDE 209, which are at a relatively low level for monitored riverine and coastal sediments around the world. Even at the most contaminated sites in Laizhou Bay area, PBDE concentrations were not among the highest concentrations reported in the literature. Congener compositions were dominated by BDE 209 (57.2-99.9% of the sum of BDE congeners), with minor contributions from penta- and octa-BDE products. Tri- to octa-BDE congeners were well correlated among each other (r > 0.75) and thus sources from similar mixing of penta- and octa-BDE products were suggested in this area. Compared with riverine sediments, a much better correlation between PBDE concentrations with TOC was observed in marine environment. The congener pattern changed and their correlation coefficients among each other were remarkably reduced. Contributions of BDE 28, 47 and 99 to Σ(7)PBDEs were generally the same in almost all the marine sites, while it was distinctively higher for BDE 153. These are probably attributable to several reasons, such as contributions by atmospheric deposition and/or redistribution between particles of various sizes during and/or after fluvial transportation combined with the difference of physiochemical properties of BDE congeners.     

Distribution patterns of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans in sediments of the Xiangjiang River, China

We investigated the occurrence and distribution patterns of 2,3,7,8-substituted polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in six sediment samples from the Xiangjiang River, Hunan Province, People’s Republic of China. Total concentrations of PCDD/Fs ranged from 876 to 497,759 (mean 160,766) ng/kg dw, the highest of which exceeded that have ever been reported for sediment samples. World Health Organization total toxicity equivalent (WHO-TEQ) concentrations in three out of six samples were significantly higher than the guidance level (21.5?ng WHO-TEQ/kg dw) suggested by Canadian Sediment Quality Guideline. A predominance of octachlorodibenzo-p-dioxin (OCDD) was observed with an average contribution of 90.8% to the total PCDD/F concentrations, while 1,2,3,4,6,7,8-heptachlorodibenzo-p-dioxin (HpCDD) was the major contributor to the PCDD/F WHO-TEQ concentrations in most of the sites. Such high levels of OCDD and HpCDD may be attributed to the presence of PCP/PCP-Na pollution, although MB-WW, agricultural straw open burning, and boilers–hazardous wastes were also the potential sources of PCDD/Fs. This is the first report for the concentrations and congener profiles of PCDD/Fs in sediment samples from the Xiangtan, Zhuzhou, and Changsha sections of the Xiangjiang River, providing scientific evidence for establishing priorities to reduce ecological risks posed by PCDD/Fs in the rapidly developing areas of Hunan Province and elsewhere.     

Heavy metals and PCDD/Fs in solid waste incinerator fly ash in Zhejiang province,China: chemical and bio-analytical characterization

Fly ash samples were taken from solid waste incinerators with different feeding waste, furnace type, and air pollution control device in six cities of Zhejiang province. The solid waste incinerators there constitute one fifth of incinerators in China. Heavy metals and polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) were analyzed in the fly ash. Moreover, the fly ash samples were extracted by toxicity characteristic leaching procedure (TCLP). The biotoxicity of the leachate was evaluated by Chlorella pyrenoidosa. High variation and contents were found for both the heavy metals and PCDD/Fs. The contents of Zn, Cu, As, Pb, Cd, Cr, Ni, and Hg in the fly ash samples varied from 300 to 32,100, 62.1–1175, 1.1–57, 61.6–620, 0.4–223, 16.6–4380, 1.2–94.7, and 0.03–1.4 μg g⁻¹ dw, respectively. The total contents of 17 PCDD/Fs varied from 0.1128 to 127.7939 μg g⁻¹ dw, and the 2,3,7,8-TeCDD toxic equivalents (TEQ) of PCDD/Fs ranged from 0.009 to 6.177 μg g⁻¹ dw. PCDF congeners were the main contributor to the TEQ. The leachate of the fly ash showed biotoxicity to C. pyrenoidosa. A significant correlation was found between the Cd and EC₅₀ values. Further research is required to investigate the environmental impact of the various pollutants in the fly ash.     

Chloroacetic acids in European soils and vegetation

Trichloroacetic acid (TCA) and dichloroacetic acid (DCA) are possible minor atmospheric degradation products of perchloroethylene and trichloroethylene, respectively. These acids may be wet- or dry-deposited from the atmosphere to land surfaces and hence possibly affect plant growth. However, the existing database on TCA levels in soil is limited to a few studies carried out in the late 1980's and the early to mid-1990's and it was concluded that there is a need for further measurements of concentrations of TCA and DCA in soils. In this study soil samples from 10 locations in 5 European countries, as well as vegetation samples, and a limited number of rainwater and air samples were collected and analysed for DCA and TCA to determine the concentrations of these compounds. An isotope dilution method using GC-MS was used for the determination of these acids in the samples. The method was briefly validated and the performance characteristics are presented. The results of the analysis of the soil samples show that the DCA and TCA concentrations in soil from different sites in Europe are more or less comparable, with the exception of Germany, especially Freudenstadt, where significantly higher TCA concentrations (up to 12 microg kg(-1) dw) were found. The average DCA and TCA concentrations in soil in this study were 0.25 +/- 0.12 and 0.64 +/- 1.40 microg kg(-1) dw, respectively. Generally, the concentration in soils from forest areas are about twice those from open-land areas. The DCA and TCA concentrations in vegetation samples ranged from 2.1 to 73 microg kg(-1) dw for DCA and from 4.7 to 17 microg kg(-1) dw for TCA. Thus, the concentrations in vegetation samples are 10-20 times higher than the soil concentrations. DCA and TCA concentrations in wet deposition samples and air samples collected in The Netherlands were 0.14 and 0.15 microg l(-1) for wet deposition samples and <0.5 and 0.7 ng m(-3) for air samples respectively. For these samples taken in The Netherlands, the estimated values for soil and air concentrations calculated from the wet deposition concentrations are in agreement with the concentrations measured in this study.     

One-year monitoring survey of organic compounds (PAHs, PCBs, TBT), heavy metals and biomarkers in blue mussels from the Arcachon Bay, France

Marine mussels Mytilus sp. were transplanted on a monthly basis in cages over one year to oyster farms and harbours in the Arcachon Bay (France) in order to assess the water quality of the bay. Contaminant levels (organotin compounds, trace metals, PCBs and PAHs) were measured in tissues of transplanted mussels and mussels from a reference station, along with physiological parameters of the mussels (condition indexes, lipid content and dry weight). Four biomarkers (AChE: acetylcholinesterase activity, GST: gluthathione S-transferase activity, CAT: catalase activity and TBARS: thiobarbituric acid-reactive substance content) were also monitored. The remote stations monitored (oyster parks) exhibited no accumulation pattern of pollutants. Their respective concentrations therefore constitute a background level of the contamination in the bay ([TBT]= 30 ng Sn g(-1) dw, [SigmaHAPs]= 100 ng g(-1) dw, [SigmaPCBs]= 35 ng g(-1) dw). The elevated chemical contamination of the largest harbour of the bay, the Arcachon harbour, can be interpreted in terms of persistence of organotin compounds ([SigmaOTs]= 1500-2000 ng Sn g(-1) dw) and PAHs ([SigmaHAPs]= 4500-5000 ng g(-1) dw) in sediments and, to a lesser extent, of direct inputs of copper ([Cu]= 20 microg g(-1) dw in harbours versus 7 in oyster parks) and petrogenic PAHs ([methylphenanthrenes]= 1600 ng g(-1) dw in the dockyard versus 170 at the gas stations), related to the use of copper-based antifouling paints and to dockyard activity, respectively. However, the Arcachon Bay presents a low contamination level by PCBs and metals, including harbour stations. Furthermore, higher levels of other PAHs (particularly alkyl PAHs such as methylphenanthrenes/1600 ng g(-1) dw) not included in the 16 PAHs from the EPA priority list (usually studied in biomonitoring programmes/1500 ng g(-1) dw) in the Arcachon harbour underline the need to integrate these compounds in biomonitoring of highly PAH-polluted areas such as harbours in order to avoid misinterpretation of the biological responses observed. Biomarker responses were not able to discriminate the different chemical contamination levels recorded in the Arcachon Bay and rather reflected changes in environmental factors. Furthermore, the strong intraspecies variability of biological responses could be due to genetic differences of mussels from the Arcachon Bay. It is the first time that such an integrated monitoring is performed in the Arcachon Bay, also taking into account seasonal variations of chemical contents and biomarkers levels in mussel tissues.     

A preliminary investigation of BDE-209, OCPs, and PAHs in urban road dust from Yangtze River Delta, China

Urban road dust samples were collected from different land use areas in Suzhou, Wuxi, and Nantong, Yangtze River Delta, China. The dust samples were analyzed for the levels and compositional profiles of deca-polybrominated diphenyl ethers (Deca-BDE), 22 organochlorine pesticides (OCPs), and 16 polycyclic aromatic hydrocarbons (PAHs). The levels of BDE-209, ∑OCPs, and ∑PAHs in samples ranged from 4.01–1,439 μg/kg, 3.15–615 μg/kg, and 2.24–58.2 mg/kg, respectively. PAHs were the predominant target compounds in road dust samples, comprising on average 97.7 % of total compounds. The spatial gradient of the pollutants (commercial/residential area> industrial area > urban park concentrations) was observed in the present study. The results indicated that the levels of BDE-209, OCPs, and PAHs observed in road dust were usually linked to anthropogenic activities in the urban environment. In addition, there might be a reflection of current usage or emissions of OCPs in urban environment.     

Analysis and occurrence of emerging chlorinated and brominated flame retardants in surficial sediment of the Dalian coastal area in China

The concentrations and distributions of some typical chlorinated flame retardants (Dechlorane or Mirex, Dechlorane 602 (Dec 602), Dechlorane 603 (Dec 603), Dechlorane 604 (Dec 604) and Dechlorane Plus (DP)) and brominated FRs (polybrominated diphenyl ethers (PBDEs), pentabromoethylbenzene (PBEB) and 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE)) were analyzed in surficial sediment collected from the Dalian coastal area in northeast China. Dec 603, Dec 604, and BTBPE were below their respective limits of detection (LOD) in all sediment samples, while Dechlorane, Dec 602, DP, Σ13BDE (tri- to hepta-BDEs), BDE 209, and PBEB were identified in the ranges <0.015-39.9 ng g(-1) dry weight (dw), <0.011-0.156 ng g(-1) dw, 0.69-7.00 ng g(-1) dw, 0.017-1.33 ng g(-1) dw, 3.94-103 ng g(-1) dw, and <0.073-1.9 ng g(-1) dw, respectively. Relationships between these chlorinated and brominated FRs were analyzed using Pearson's correlation and principal component analysis (PCA). DP, Dechlorane, Σ13BDE, and BDE 209 showed significantly positive correlation (p<0.05), and these relationships showed excellent agreement with PCA results. The spatial trends for Dechlorane, DP, BDE 209, and Σ13BDE showed that high concentrations were found in the industrial zone and lower concentrations in residential and garden zones. The results imply that these FRs are originating from a common source, and support the view that direct input from the effluent of sewage outlets is a major source of these compounds in Dalian sediment.     

Analysis of per- and polyfluorinated alkyl substances in air samples from Northwest Europe

Air samples were collected from 4 field sites in Europe: 2 sites from the UK, Hazelrigg (semi-rural) and Manchester (urban); 1 site from Ireland: Mace Head (rural); and 1 site from Norway: Kjeller (rural). Additionally, air samples were taken from indoor locations in Troms?, Norway. Air samples were collected using high-volume air samplers employing sampling modules containing glass-fibre filters (GFFs, particle phase), and glass columns with a polyurethane foam (PUF)-XAD-2-PUF sandwich (gaseous phase). Typical outdoor air volumes required for the determination of per- and polyfluorinated alkyl substances (PFAS) ranged from 500-1800 m3. GFFs and PUF-XAD columns were analysed separately to obtain information on phase partitioning. All air samples were analysed for volatile, neutral PFAS, with selected GFF samples halved for analysis of both neutral and airborne particle-bound ionic PFAS. Volatile PFAS were extracted from air samples by cold-column immersion with ethyl acetate, and were analysed by gas chromatography-mass spectrometry in the positive chemical ionisation mode (GC-PCI-MS). Ionic PFAS were extracted from GFFs by sonication in methanol, and were analysed by liquid chromatography-time-of-flight-mass spectrometry (LC-TOF-MS) using electrospray ionisation in the negative ion mode (ESI-). Perfluorooctanoate (PFOA) was often the predominant analyte found in the particulate phase at concentrations ranging from 1-818 pg m(-3), and 8:2 fluorotelomer alcohol (FTOH) and 6:2 FTOH were the prevailing analytes found in the gas phase, at 5-243 pg m(-3) and 5-189 pg m(-3), respectively. These three PFAS were ubiquitous in air samples. Many other PFAS, both neutral and ionic, were also present, and levels of individual analytes were in the 1-125 pg m(-3) range. Levels of some PFAS exceeded those of traditional persistent organic pollutants (POPs). In this study, the presence of 12:2 FTOH and fluorotelomer olefins (FTolefins), and ionic PFAS other than perfluorooctane sulfonate (PFOS) and PFOA, are reported in air samples for the first time. Concentrations of neutral PFAS were several orders of magnitude higher in indoor air than outdoor air, making homes a likely important diffuse source of PFAS to the atmosphere. Our repeated findings of non-volatile ionic PFAS in air samples raises the possibility that they might directly undergo significant atmospheric transport on particles away from source regions, and more atmospheric measurements of ionic PFAS are strongly recommended.     

Screening of dioxin-like compounds in bio-composts and their materials: chemical analysis and fractionation-directed evaluation of AhR ligand activities using an in vitro bioassay

Application of the dioxin responsive-chemical activated luciferase gene expression (DR-CALUX) bioassay to three compost products (kitchen garbage compost, treated sludge compost, and poultry manure compost) and their organic waste materials was performed for the screening of dioxin-like compounds. Phased sample preparation was conducted for the bioassay to yield separate crude, acid-stable, and carbon column fractions. Chemical analyses were also conducted for polychlorinated dibenzo-p-dioxin and dibenzofurans (PCDD/Fs), polychlorinated biphenyls (PCBs), and polyaromatic hydrocarbons (PAHs). Their determined WHO-PCDD/PCDF/dl-PCB-TEQ values were compared to the DR-CALUX results expressed as CALUX-TEQ to ascertain their contributions to overall activity. Overall all three compost products were polluted to a low level by persistent PCDD/PCDF/dl-PCBs in a few pg/g WHO-TEQ concentration range. The organic crude fraction showed non-persistent CALUX-TEQ values 2-4 orders of magnitude higher than those of WHO-TEQ. For the acid-resistant fractions of all samples, persistent CALUX-TEQ values were 1-8-fold higher than WHO-PCDD/PCDF/dl-PCB-TEQ values. Both TEQs correlated well for this fraction, which confirms the availability of CALUX for estimation of the actual WHO-TEQ level of the samples using reflux method with 44% sulfuric acid/silica gel, although the compost and material samples examined in this study contained much lower levels of WHO-TEQ: less than 1 pg/g in almost all cases. Additional carbon column treatment enhanced the potency and efficacy of CALUX activity in the three compost samples, which showed 1.6-4.4 times higher values of CALUX-TEQ than those obtained for the acid-resistant fraction. Although further DR-CALUX data collection for compost samples will be necessary, DR-CALUX is useful as a rapid screening method for monitoring dioxin-like compounds in compost.     

PAH and PCB in soils of Switzerland--status and critical review

The surface soil concentrations (0-20 cm) of the Swiss soil monitoring network (NABO) with 105 observation sites representing all major land use types ranged for the sum of 16 EPA PAH (PAH(16)) from 32 to 8465 microg kg(-1) (median 163 microg kg(-1)), for benzo[a]pyrene (BaP) from 0.5 to 1129 microg kg(-1) (median 13 microg kg(-1)) and for the sum of seven IRMM PCB (PCB(7)) from 0.5 to 12 microg kg(-1) (median 1.6 microg kg(-1)). The legal guide values of Switzerland were exceeded for PAH(16) at only three and for BaP at two sites. The PCB(7) concentrations were clearly below any assessment value. The concentration ranges were overlapping between all land use types. Tendencies for higher concentrations were observed at urban and viticulture sites. The overall measurement precision at repeatability conditions ranged from 1 to 37% RSD for PAH(16), BaP and PCB(7). The median bias for the chemical analysis was around zero for PAH(16), +5% for BaP and -5% for PCB(7) with spreads ranging from less than -20% up to more than +30%. The PAH profiles were clearly dominated by phenanthrene. Stratification by land use revealed a prevalence of benzo[a]pyrene at urban and naphthalene at conservation sites. For PCB, the general congener rank order was PCB no. 153 > 138 > 101 > 180. From a broad correlation screening only PAH(16)/BaP (r = 0.88**) were relevant for practical soil protection. The extensive comparison with other studies was severely biased by the lack of harmonisation, especially concerning sampling depth, sampling support, analytical method and the sum calculation procedure.