Aerobic biodegradation of selected polybrominated diphenyl ethers (PBDEs) in wastewater sewage sludge.

Due to widespread accumulation of polybrominated diphenyl ethers (PBDEs) in our surroundings, it is important to clarify their fate in the environment and the options of their elimination. The aim of this study was to monitor the biodegradation of the most frequent congeners (BDE 28, 47, 49, 66, 85, 99, 100, 153, 154, 183 and 209) under aerobic condition by indigenous microflora in 2 industrially contaminated sewage sludge samples. BDE 209 was detected as the predominating congener in concentrations 685 ng/g and 1403 ng/g dry weight in sewage sludge from WWTPs (waste water treatment plants) Hradec Kralove and Brno, respectively. The total amount of 10 lower PBDEs was 605 and 205 ng/g dry weight, respectively. The aerobic degradation was significantly enhanced by the addition of yeast extract and 4-bromobiphenyl. The total concentrations of all 11 PBDE congeners were lowered and their elimination was detected reaching 62­78% of their initial amounts after 11 months of cultivation. The degradation of most abundant congener BDE 209 followed the first-order kinetics with constant detected between 2.77 × 10(−3) d(−1) and 3.79 × 10−(3)d(−1) and the half-lives of BDE 209 degradation ranged between 6.0 and 8.2 months. This work clearly demonstrates that both lower brominated PBDEs as well as the major representative BDE 209 could be successfully removed from municipally contaminated sludge under aerobic conditions.

Brominated flame retardants and perfluoroalkyl substances in sediments from the Czech aquatic ecosystem.

This study reports results of analysis of various groups of halogenated chemicals, including brominated flame retardants (BFRs), such as polybrominated diphenyl ethers (PBDEs), hexabromocyclododecanes (HBCDs), tetrabromobisphenol A (TBBPA) and perfluoroalkyl substances (PFASs) in 31 sediment samples collected in different localities of the Czech Republic. In this survey, identification of potential sources of these compounds was also performed; therefore several sampling sites located in highly industrialized areas were involved. Concentrations of target groups of analytes determined in sediments from several Czech rivers examined within this study decreased in the following order: decabromodiphenyl ether (BDE 209) >>> TBBPA~HBCDs~linear perfluorooctane sulfonate (L-PFOS)>other PBDEs~perfluorinated carboxylic acids (PFCAs)~perfluorooctane sulfonamide (FOSA). When compared the contamination by two monitored groups of halogenated compounds, the total content of ∑BFRs was significantly higher, i.e. in the range from the method quantification limit (MQL) to 528 µg/kg dry weight (dw) (median value 5.68 µg/kg dw), than the total concentration of ∑PFASs, that was in the range from MQL to 25.5 µg/kg dw (median value 1.48 µg/kg dw). The extremely highest content of BFR group (265-528 µg/kg dw) was found in sediments collected in sampling sites on the Labe and Luzická Nisa Rivers, which are located in highly chemical industrialized areas and also in the sample from the locality Lampertice obtained from the sedimentation tank close to the factory processing and storing waste. These concentrations were a little bit higher or comparable to those found in similar highly industrialized areas worldwide.

Occurrence of perfluoroalkyl substances (PFASs) in various food items of animal origin collected in four European countries.

This study summarises the results of the levels of 21 perfluoroalkyl substances (PFASs) in 50 selected pooled samples representing 15 food commodities with the special focus on those of animal origin, as meat, seafood, fish, milk, dairy products and hen eggs, which are commonly consumed in various European markets, e.g. Czech, Italian, Belgian and Norwegian. A new, rapid sample preparation approach based on the QuEChERS extraction procedure was applied. Ultra-performance liquid chromatography (UHPLC) coupled to tandem mass spectrometry (MS/MS) employing electrospray ionisation (ESI) in negative mode was used for the quantification of target analytes. Method quantification limits (MQLs) were in the range of 1-10 ng kg(-1) (ng l(-1)) for fish, meat, hen eggs, cheese and milk, and in the range of 2.5-125 ng kg(-1) for butter. Only 16 of the group of 21 PFASs were found in at least one analysed sample. From 16 PFASs, perfluorooctane sulfonate (PFOS) was the most frequently detected analyte present in approximately 50% of samples (in the range of 0.98-2600 ng kg(-1)). PFCAs with C8-C14 carbon chain were presented in approximately 20% of samples. The concentration ranges of individual compounds in the respective groups of PFASs were: 2.33-76.3 ng kg(-1) for PFSAs (without PFOS), 4.99-961 ng kg(-1) for PFCAs, 10.6-95.4 ng kg(-1) for PFPAs, and 1.61-519 ng kg(-1) for FOSA. The contamination level in the analysed food commodities decreased in the following order: seafood > pig/bovine liver >> freshwater/marine fish > hen egg > meat >> butter. When comparing the total contamination and profiles of PFASs in food commodities that originated from various sampling countries, differences were identified, and the contents decreased as follows: Belgium >> Norway, Italy > Czech Republic.

Occurrence of brominated flame retardants and perfluoroalkyl substances in fish from the Czech aquatic ecosystem.

This study reports results of analysis of various groups of halogenated compounds, including brominated flame retardants (BFRs), such as polybrominated diphenylethers (PBDEs), hexabromocyclododecane (HBCD), tetrabromobisphenol A (TBBPA) and perfluoroalkyl substances (PFASs) in 48 fish samples collected in eight localities from the Czech Republic. In this survey, identification of potential sources of these chemicals was also performed; therefore several sampling sites located in highly industrialized areas were also selected. Perfluorooctanesulfonate (PFOS) was dominating in all tested fish samples. Generally, the content of ∑BFRs was significantly lower, i.e. in the range of 0.21-19.9 µg/kg wet weight, ww (median value 2.37 µg/kg ww) compared to the concentration of ∑PFASs that was in the range of 0.15-877 µg/kg ww (median value 8.5 µg/kg ww). The extremely high content of PFOS (842 µg/kg ww) was found in fish muscle tissue from the locality situated on the Bílina River, where chemical industry is located. This concentration was comparable to those found in similar highly industrialized areas worldwide.

Occurrence of halogenated contaminants in fish from selected river localities and ponds in the Czech Republic.

The occurrence of organohalogenated compounds including major persistent chlorinated pollutants, such as polychlorinated biphenyls (PCBs) and DDT and its metabolites, brominated flame retardants (BFRs), represented by polybrominated diphenylethers (PBDEs) and hexabromocyclododecane (HBCD), together with currently widely discussed perfluorinated compounds (PFCs), mainly perfluorooctane sulfonic acid was monitored in several fish species collected from Czech rivers. Eleven sampling locations in highly industrialized areas were chosen. In addition, wild species of 14 farmed fish (grown in dedicated ponds) were also analysed. With respect to the contamination in different areas, chlorinated chemicals were dominant. PCBs and DDTs ranged from 4.8 to 211 and 2 to 791 µg/kg wet weight, respectively. Concentrations of BFRs and PFCs were significantly lower and ranged from 0.6 to 10.2 and 0.9 to 62 µg/kg wet weight, respectively. The highest levels of target analyte groups were found in fish muscle tissue in localities situated on the lower part of the Elbe River: Levels of DDT, HCB, PBDEs, and perfluorooctane sulfonic acid (PFOS) were as high as 791, 77.6, 14.4 and 193 µg/kg wet weight, respectively, in Usti nad Labem and in the sample originated from the confluence of Elbe with Bilina River; a sum of PCBs at a level of 211 µg/kg was detected.

Simple, high throughput ultra-high performance liquid chromatography/tandem mass spectrometry trace analysis of perfluorinated alkylated substances in food of animal origin: milk and fish.

The present study documents development and validation of a novel approach for determination of 23 perfluorinated alkylated substances (PFASs) in food of animal origin represented by milk and fish. The list of target analytes comprises four classes of PFASs, both ionic and non-ionic: 11 perfluorocarboxylic acids (PFCAs), 4 perfluorosulphonic acids (PFSAs), 5 perfluorosulphonamides (FOSAs) and 3 perfluorophosphonic acids (PFPAs). Fast sample preparation procedure is based on an extraction of target analytes with acetonitrile (MeCN) and their transfer (supported by inorganic salts and acidification) into the organic phase. Removing of matrix co-extracts by a simple dispersive solid phase extraction (SPE) employing ENVI-Carb and C18 sorbents is followed by an efficient sample pre-concentration performed by acetonitrile evaporation and subsequent dilution of residue in a small volume of methanol (matrix equivalent in the final extracts was 16 and 8 g mL(-1), for milk and fish respectively). Using modern instrumentation consisting of ultra-high performance liquid chromatography (UHPLC) hyphenated with a tandem mass spectrometer (MS/MS), limits of quantification (LOQs) as low as 0.001-0.006 µg kg(-1) for milk and 0.002-0.013 µg kg(-1) for fish can be achieved. Under these conditions, a wide spectrum of PFASs, including minor representatives, can be determined which enables collecting data required for human exposure studies. The pilot study employing the new method for examination of milk and canned fish samples was realized. Whereas in majority of canned fish products a wide spectrum of PFCAs, perfluorooctanesulphonic acid (PFOS) and perfluoro-1-octanesulphonamide (PFOSA) was detected, only in a few milk samples very low concentrations (LOQ levels) of PFOS and perfluorooctansulphonic acid (PFDS) were found.

Evaluating environmental impact of STPs situated on streams in the Czech Republic: an integrated approach to biomonitoring the aquatic environment.

Sewage water treatment plants (STPs) are frequently associated with the release of xenobiotics and, consequently, with biological responses of fish to these substances. The impact of three STPs situated on small streams was assessed in 2009. Brown trout (Salmo trutta fario L.), captured upstream and downstream of these STPs, were used as biomonitors. The concentrations of 39 organic pollutants (PCBs, OCPs, PBDEs, HBCDs, and MCs), and the biological responses related to oxidative stress (lipid peroxidation and carbonyl protein), and antioxidant responses (superoxide dismutase, glutathione peroxidase and glutathione reductase) were measured. Through chemometrics of these parameters, three groups with 97.62% of the total accumulated variance were distinguished. Integration of the assessed biomarkers using the IBR index, ranked environment impact on sites as: DS Pacov > DS Prachatice > DS Brloh > US Pacov > US Prachatice > US Brloh (most to least affected). STPs are a major source of xenobiotic pollution in streams of the Czech Republic. The combined use of chemical analysis and biological responses is necessary to validate the efficacy of a battery of biomarkers chosen to detect environmental stress due to pollution.

Absorption and translocation of polybrominated diphenyl ethers (PBDEs) by plants from contaminated sewage sludge.

Polybrominated diphenyl ethers (PBDEs) are used as additive flame retardants. PBDEs are persistent, bioaccumulative and toxic compounds. They are often detected in sewage sludge which is applied on agricultural soils as fertilizer. The objective of this study was to find out whether plants are able to accumulate and translocate PBDEs. Tobacco (Nicotiana tabacum) and nightshade (Solanum nigrum) were planted in pots containing contaminated sewage sludge and uncontaminated substrate. After 6 months of plant cultivation in sewage sludge up to 15.4 ng g(-1) dw and 76.6 ng g(-1) dw of PBDE congeners--BDE 47, BDE 99 and BDE 100---were accumulated in the nightshade and tobacco tissue, respectively. Corresponding values in plants vegetated in the control garden substrate were 10 times lower. The bioconcentration factors (BCFs) of accumulated congeners were calculated. Tobacco exhibited higher BCFs values and for both plants BCFs values of BDE 47, BDE 99, BDE 100 and BDE 209 negatively correlated with their octanol-water partition coefficients (logK(ow)). The exception was decaBDE (BDE 209) which was accumulated only in tobacco tissue in the concentration of 116.8 ng g(-1) dw. The majority of PBDEs was detected in above-ground plant biomass indicating that both plants have the ability to translocate PBDEs. To our knowledge this is one of the first studies reporting the accumulation of both lower PBDEs and BDE 209 in plants. Our results suggest that absorption, accumulation and translocation of PBDEs by plants and their transfer to the food chain could represent another possible risk for human exposure.

Brominated flame retardants and other organochlorine pollutants in human adipose tissue samples from the Czech Republic.

Brominated flame retardants (BFRs) represented by polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecane (HBCD) together with major persistent organochlorine pollutants, polychlorinated biphenyls (PCBs) and selected organochlorine pesticides (OCPs), were determined in adipose tissue samples (n=98) obtained by liposuction of Czech subjects. Compared to other organochlorine pollutants (mostly PCBs and DDTs), levels of PBDE were lower by 2 orders of magnitude ranging from 0.2 to 54.3 ng/g lipid weight. PBDE congeners No. 47, 99, 153 and 183 were the most abundant constituting up to 90% of these pollutants in adipose tissue. The PBDEs content measured in this study was comparable with data reported in similar samples collected in Spain, Sweden, Belgium and Japan, whilst slightly lower than in the United States. Regarding PCBs, the dominating congeners were No. 138, 153 and 180 representing up to 90% of indicator congeners. The levels of PCBs were similar to those found in other European countries. While no age dependency was found for PBDEs, an increase of PCB and OCP levels with age was observed. Different exposure routes of donors were documented by the absence of the relationship between PCBs and OCPs.