Legacy and Emerging Persistent Organic Pollutants in Antarctic Benthic Invertebrates near Rothera Point, Western Antarctic Peninsula.

Pollutant levels in polar regions are gaining progressively more attention from the scientific community. This is especially so for pollutants that persist in the environment and can reach polar latitudes via a wide range of routes, such as some persistent organic pollutants (POPs). In this study, samples of Antarctic marine benthic organisms were analyzed for legacy and emerging POPs (polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs), and organochlorine pesticides) to comprehensively assess their current POP concentrations and infer the potential sources of the pollutants. Specimens of five benthic invertebrate species were collected at two distinct locations near Rothera research station on the Antarctic Peninsula (67°35'8 ̋ S and 68°7'59 ̋ W). Any impact of the nearby Rothera station as a local source of pollution appeared to be negligible. The most abundant chemicals detected were hexachlorobenzene (HCB) and BDE-209. The highest concentrations detected were in limpets and sea urchins, followed by sea stars, ascidians, and sea cucumbers. The relative congener patterns of PCBs and PBDEs were similar in all of the species. Some chemicals (e.g., heptachlor, oxychlordane, and mirex) were detected in the Antarctic invertebrates for the first time. Statistical analyses revealed that the distribution of the POPs was not only driven by the feeding traits of the species but also by the physicochemical properties of the specific compounds.

The performance of atmospheric pressure gas chromatography-tandem mass spectrometry compared to gas chromatography-high resolution mass spectrometry for the analysis of polychlorinated dioxins and polychlorinated biphenyls in food and feed samples.

Recently, gas chromatography tandem mass spectrometry (GC-MS/MS) has been added in European Union (EU) legislation as an alternative to magnetic sector high resolution mass spectrometry (HRMS) for the analysis of dioxins and dioxin like polychlorinated biphenyls (dl-PCB) in food and feed. In this study the performance of APGC-MS/MS compared to GC-HRMS is investigated and compared with EU legislation. The study includes the legislative parameters, relative intermediate precision standard deviation (SRw,rel), trueness, sensitivity, linear range and ion ratio tolerance. In addition, over 200 real samples of large variety and spanning several orders of magnitude in concentration were analyzed by both techniques and the selectivity was evaluated by comparing chromatograms. The SRw,rel and trueness were evaluated using (in-house) reference samples and fulfill to EU legislation, though the SRw,rel was better with GC-HRMS. The sensitivity was considerably better than of GC-HRMS while the linear range was similar. Ion ratios were mostly within the tolerable range of ±15%. A (temporary unresolved) systematic deviation in ion ratio was observed for several congeners, yet this did not lead to exceeding of the maximum ion ratio limits. The APGC-MS/MS results for the non-dioxin-like-PCBs (ndl-PCBs) were negatively biased, particularly for PCB138 and 153 in contaminated samples. The selectivity of APGC-MS/MS was lower for several matrices. Particularly for contaminated samples, interfering peaks were observed in the APGC chromatograms of the native compounds (dioxins) and labeled internal standards (PCBs). These can lead to biased results and ultimately to false positive samples. It was concluded that the determination of dioxins and PCBs using APGC-MS/MS meets the requirements set by the European Commission. However, due to generally better selectivity and SRw,rel, GC-HRMS is the preferred method for monitoring purposes.

Polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and biphenyls (PCBs) in home-produced eggs.

Home produced eggs from 62 addresses in the Netherlands were investigated for the levels of polychlorinated dibenzo-p-dioxins, dibenzofurans (PCDD/Fs) and biphenyls (PCBs), both dioxin-like (dl) and non-dioxin-like (ndl). Compared to commercial eggs, levels were relatively high with a median of 4.6 pg TEQ g(-1) fat for the sum of PCDD/Fs and dl-PCBs, and a highest level of 18.9 pg TEQ g(-1) fat. A number of samples showed clearly elevated ndl-PCB levels with a median of 13 ng g(-1) fat and a highest level of 80 ng g(-1) fat. There were no clear regional differences, even though part of the samples were derived from the rather industrial Rotterdam/Rijnmond area. Based on the congener patterns, former backyard burning of waste seems the most likely source for most eggs, with two exceptions where other sources contributed to the contamination. Similar is true for the ndl-PCBs. The study shows that average levels are about ten-fold higher than commercial eggs and may substantially contribute to the intake of PCDD/Fs and dl-PCBs by consumers. Intervention measures to reduce the intake of these contaminants by laying hens are advised.

Accumulation of polychlorinated dibenzo-p-dioxins, dibenzofurans, and biphenyls in livers of young sheep.

A major part of sheep livers contains levels of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and polychlorinated biphenyls (PCBs) above the former but to some extent also the new maximum levels (MLs) in the EU. In order to investigate the relationship between the intake of these contaminants and their accumulation in livers, kidney fat and meat, young blackhead sheep were fed with grass pellets containing PCDD/Fs at 2.5 times the maximum level. Levels of PCDD/Fs in livers were already quite high at the start of the exposure but increased 3-fold within 56d, exceeding the new product based MLs. Levels in meat and fat also increased but did not exceed the MLs. Although less elevated in the grass, both dl- and ndl-PCB levels also increased in liver and fat. Their kinetics in the tissues was less clear, potentially caused by increased levels in the straw given to the sheep during the whole experimental period. There was a clear difference in the behavior of the various congeners, the PCDFs and especially the higher chlorinated PCDFs and PCDDs showing a higher accumulation in the liver. In the case of the PCBs, this was particularly true for PCB 126. When switched to clean grass after 56d, the levels in livers and other tissues decreased to about the levels in the control sheep within 56d. This offers a potential solution for decreasing the intake of consumers.

Simultaneous extraction and determination of HBCD isomers and TBBPA by ASE and LC-MSMS in fish.

Since the EFSA enquired a call for data for TBBPA and HBCD in 2009, the analytical determination of these compounds in food became of regulatory interest. Therefore, a method for the simultaneous determination of TBBPA and the three major HBCD stereoisomers was developed. Conventional techniques like soxhlet, ASE, GPC, sulphuric acid digestion, and acidified silica SPE are generally used in sample pre-treatment while detection is mostly performed by LC-MSMS. A combined analysis of HBCD and TBBPA is problematic due to the hydroxyl groups in the TBBPA molecule. However, using a specific mesh-size sodium sulphate in ASE extraction and an acid silica column combined with a Sep-pack Plus silica cartridge for purification resulted in recoveries between 80% and 110% for all compounds. The accuracy and reproducibility determined using proficiency test samples were 104% and 4% for the sum of the HBCD isomers. Typical limits of detection were 0.01 ng/g product or 0.004 ng on column, while the linear dynamic range is between 0.01 ng and 10 ng on column. Levels of TBBPA and HBCD isomers were determined in eel samples. TBBPA was occasionally detected and only marginally above the quantification limit of 0.05 ng/g, whereas total amounts of HBCD were between 0.2 and 150 ng/g with α-HBCD being the dominant HBCD isomer.