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Andreas C Gerecke

Publications and source records attributed to Andreas C Gerecke.

9 recordsLinked to original sources

The historical record of PCB and PCDD/F deposition at Greifensee, a lake of the Swiss plateau, between 1848 and 1999.

Dated sediment cores provide an excellent way to investigate the historical input of persistent organic pollutants into the environment and to identify possible sources of pollution. The vertical distribution of polychlorinated dibenzo-p-dioxins/polychlorinated dibenzofurans (PCDD/F) and polychlorinated biphenyls (PCB) was investigated in a sediment core from Greifensee to elucidate the historical trends of PCDD/F and PCB inputs between 1848 and 1999. Concentrations of PCB and PCDD/F increased by more than one order of magnitude between 1930 and 1960. PCB and PCDD/F concentrations were 5700 ng/kg dry weight (dw) and 160 ng/kg dw, respectively, in sediments originating from the late 1930s and reached a maximum of 130,000 ng/kg dw and 2400 ng/kg dw, respectively, in the early 1960s. From 1960 on, concentrations decreased to the 1930s level by the mid 1980s. A remarkable shift in the PCDD/F pattern was observed after the early 1940s. Before 1940, the PCDD/F pattern was PCDF dominated (ratio of PCDD to PCDF=0.41+/-0.11), while the PCDD started to be the major species after the early 1940s (ratio of PCDD to PCDF=1.46+/-0.38). The temporal trends of PCB and PCDD/F correlate surprisingly well with each other. This might be due to the coincidence of two factors. The introduction of PCB on the market in the 1930s resulted in emissions due to the widespread use of these industrial chemicals. In the same time period, waste incineration became an increasingly popular way to get rid of garbage, boosting the PCDD/F emissions significantly. The rapid decline of PCDD/F and PCB concentrations in the sediment starting in the early 1960s reflects the result of better emission control techniques in thermal processes and the improvement of waste water treatment in the catchment of Greifensee.

Benzofurans↗

Hexabromocyclododecanes (HBCDs) in the environment and humans: a review.

Hexabromocyclododecanes (HBCDs) are brominated aliphatic cyclic hydrocarbons used as flame retardants in thermal insulation building materials, upholstery textiles, and electronics. As a result of their widespread use and their physical and chemical properties, HBCDs are now ubiquitous contaminants in the environment and humans. This review summarizes HBCD concentrations in several environmental compartments and analyzes these data in terms of point sources versus diffuse sources, biomagnification potential, stereoisomer profiles, time trends, and global distribution. Generally, higher concentrations were measured in samples (air, sediment, and fish) collected near point sources (plants producing or processing HBCDs), while lower concentrations were recorded in samples from locations with no obvious sources of HBCDs. High concentrations were measured in top predators, such as marine mammals and birds of prey (up to 9600 and 19 200 ng/g lipid weight, respectively), suggesting a biomagnification potential for HBCDs. Relatively low HBCD concentrations were reported in the few human studies conducted to date (median values varied between 0.35 and 1.1 ng/g lipid weight). HBCD levels in biota are increasing slowly and seem to reflect the local market demand. One important observation is the shiftfrom the high percentage of the gamma-HBCD stereoisomer in the technical products to a dominance of the alpha-HBCD stereoisomer in biological samples. A combination of factors such as variations in solubility, partitioning behavior, uptake, and, possibly, selective metabolism of individual isomers may explain the observed changes in stereoisomer patterns. Recommendations for further work include research on how HBCDs are transferred from products into the environment upon production, use, and disposal. Time trends need to be analyzed more in detail, including HBCD stereoisomers, and more data on terrestrial organisms are needed, especially for humans. Whenever possible, HBCDs should be analyzed as individual stereoisomers in order to address their fate and effects.

Animals↗

Anaerobic degradation of brominated flame retardants in sewage sludge.

Tetrabromobisphenol A (TBBPA), hexabromocyclododecane (HBCD), and decabromodiphenyl ether (DecaBDE) are high production volume chemicals used as flame retardants in plastics for products such as electronic equipment, insulation panels, and textiles. The environmental safety of brominated flame retardants, especially their persistence, bioaccumulation, and toxicity is a controversial topic. Here, we studied and compared the degradation of TBBPA, HBCD, and DecaBDE under anaerobic conditions in digested sewage sludge. The half-lives of TBBPA and a technical HBCD mixture were 0.59 and 0.66 d, respectively. The fact that (+/-)-alpha-HBCD exhibited an almost doubled half-life compared to (+/-)-beta-HBCD and (+/-)-gamma-HBCD is an important finding with respect to the discussion on the persistence of individual HBCD stereoisomers and the recent reports on strong relative enrichment of alpha-HBCD in biota. We found no statistically significant enantioselective degradation of alpha-, beta-, or gamma-HBCD. Half-lives of TBBPA and a technical HBCD mixture were not dependent on the presence of additional nutrients or primers. Concentrations of TBBPA and a technical HBCD mixture decreased also in sterile control samples, however, at a rate that was more than a factor of 50 smaller than in incubations under non-sterile conditions. Compared to TBBPA and a technical HBCD mixture, DecaBDE exhibited a much longer half-life of 7 x 10(2)d in the same system. Pseudo-first-order degradation rate constants decreased according to the following sequence: TBBPA congruent with(+/-)-gamma-HBCD congruent with(+/-)-beta-HBCD>(+/-)-alpha-HBCD>>DecaBDE. Preliminary investigations suggest that degradation of TBBPA, HBCD, and DecaBDE occurs in full-scale anaerobic digesters, as well.

Anaerobiosis↗

Anaerobic degradation of decabromodiphenyl ether.

The environmental safety of decabromodiphenyl ether (BDE-209), a widely used flame retardant, has been the topic of controversial discussions during the past several years. Degradation of BDE-209 into lower brominated diphenyl ether congeners, exhibiting a higher bioaccumulation potential, has been a critical issue. Here, we report on the degradation of BDE-209 and the formation of octa- and nonabromodiphenyl ether congeners under anaerobic conditions. Sewage sludge collected from a mesophilic digester was used as the inoculum and incubated up to 238 days with and without a set of five primers. Following Soxhlet extraction and a liquid chromatography cleanup procedure, parent compounds and debromination products were analyzed by GC/HRMS. In experiments with primers, concentrations of BDE-209 decreased by 30% within 238 days. This corresponds to a pseudo-first-order degradation rate constant of 1 x 10(-3) d(-1). Without primers, the degradation rate constant was 50% lower. Formation of two nonabromodiphenyl ether and six octabromodiphenyl ether congeners proved that BDE-209 underwent reductive debromination in these experiments. Debromination occurred at the para and the meta positions, whereas debromination at the ortho position was not statistically significant. All three nonabromodiphenyl ether congeners (BDE-206, BDE-207, and BDE-208) were found to undergo reductive debromination as well. No significant change of the BDE-209 concentration and no formation of lower brominated congeners was observed in sterile control experiments. To our knowledge, this is the first report demonstrating microbially mediated reductive debromination of BDE-209 under anaerobic conditions.

Animals↗

Structure elucidation of hexabromocyclododecanes--a class of compounds with a complex stereochemistry.

Hexabromocyclododecanes (HBCDs) are high production volume chemicals (16700 t worldwide in 2001) used as flame-retardants for plastics and textiles. HBCDs exhibit typical properties of persistent organic pollutants (POPs). They are highly lipophilic and accumulate in biota. Increasing environmental concentrations of HBCDs, mostly reported as sum values, have been observed. As such, HBCDs have to be considered as potential emerging POPs, but their occurrence and environmental fate have not yet been addressed at the level of individual HBCD stereoisomers. Considering the six stereogenic centers of HBCDs, 16 stereoisomers, six diastereomeric pairs of enantiomers as well as four meso forms, can be deduced. Herein, we report spectroscopic and chromatographic data for eight out of 16 possible HBCD stereoisomers, which were isolated from a technical product. Six stereoisomers were identified as three pairs of enantiomers ((+/-) alpha-, beta-, and gamma-HBCDs), differing in optical rotation and chromatographic retention on a chiral phase. The crystal structures of these pairs of enantiomers were determined. Another two of these eight HBCD stereoisomers, not yet described in the literature, showed no optical rotation and are tentatively assigned as meso forms (delta- and epsilon-HBCD). The given spectroscopic and chromatographic information allows the unambiguous identification of eight HBCD stereoisomers and the occurrence, fate, and toxicology of these individual stereoisomers can now be studied.

Chromatography↗

A N-Nitrosodimethylamine (NDMA) precursor analysis for chlorination of water and wastewater.

N-nitrosodimethylamine (NDMA) is a potent carcinogen formed during chloramination of water and wastewater treatment plant effluents. A procedure is described for quantifying the concentration of the organic precursors of NDMA that could be formed during chlorination of wastewaters and natural waters. The method involves applying a high dose of monochloramine to a pH-buffered sample followed by a 10-day contact period, during which the monochloramine decays at a rate unrelated to the composition of the sample. Analyses of samples of municipal wastewater effluents and surface waters indicate that the method provides a robust and reproducible measurement of NDMA precursors over a wide range of conditions. A sensitive GC/CI/MS/MS analytical procedure for dimethylamine also is described and used to demonstrate that NDMA formation during chlorination of wastewater and natural waters cannot be explained by dimethylamine concentrations alone.

Carcinogens↗

Polybrominated diphenyl ethers in whitefish from Swiss lakes and farmed rainbow trout.

A method for trace analysis of polybrominated diphenyl ethers (PBDE) in fish based on gas chromatography/electron ionization high resolution mass spectrometry (GC/EI-HRMS) was developed, and levels of PBDE were determined in whitefish (Coregonus sp.) from eight Swiss lakes and in rainbow trout (Oncorhynchus mykiss) from four Swiss fish farms. PBDE concentrations (sum of PBDE congeners BDE-28, BDE-47, BDE-99, BDE-100, BDE-153, BDE-154, and BDE-183) in filet from whitefish between 36 and 165 ng/g lipid weight (lw) were found, corresponding to wet weight (ww) concentrations of 1.6-7.4 ng/gww. PBDE contents in filet from farmed rainbow trout were significantly lower than in wild whitefish (12-24 ng/glw, 0.74-1.3 ng/gww), and the PBDE congener patterns were different for both species (a higher BDE-47 to BDE-99 ratio for farmed rainbow trout compared to wild whitefish was found). Whitefish PBDE levels [ng/glw] correlate better with the surface/volume ratio of the respective lakes (r(2)=0.70) than with other lake properties such as catchment area (size or number of inhabitants) or residence time, suggesting atmospheric deposition as an input pathway for PBDE. Based on an average daily consumption of 20 g whitefish (Switzerland) with a PBDE content of 7.4 ng/gww (highest PBDE concentration detected in this study), a maximum daily intake of 0.15 microg PBDE was estimated (0.026 microg/day for farmed trout). This number corresponds to the lower end of the estimate for the total PBDE intake of the Nordic consumer of 0.2-0.7 microg/day.

Animals↗

Sources of pesticides in surface waters in Switzerland: pesticide load through waste water treatment plants--current situation and reduction potential.

Concentrations of pesticides in Swiss rivers and lakes frequently exceed the Swiss quality goal of 0.1 microg/l for surface waters. In this study, concentrations of various pesticides (e.g., atrazine, diuron, mecoprop) were continuously measured in the effluents of waste water treatment plants and in two rivers during a period of four months. These measurements revealed that in the catchment of Lake Greifensee, farmers who did not perfectly comply with 'good agricultural practice' caused at least 14% of the measured agricultural herbicide load into surface waters. Pesticides, used for additional purposes in urban areas (i.e. protection of materials, conservation, etc.), entered surface waters up to 75% through waste water treatment plants.

Agriculture↗