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Using GC Orbitrap mass spectrometry to address analytical challenges with trace level detection of persistent organic pollutants in Antarctica.

In the first multiyear sampling effort for POPs in the eastern Antarctic atmosphere, 32 PCBs and 38 organochlorine pesticides were targeted in air collected with a high-flow-through passive sampler. Agricultural chemicals were found to dominate atmospheric profiles, in particular HCB and endosulfan-I, with average concentrations of 12 600 and 550 fg/m3, respectively. HCB showed higher concentrations in the austral summer, indicative of local, temperature-dependent volatilisation, while endosulfan-I appeared to show fresh, late-austral-summer input followed by temporally decreasing levels throughout the year. The current-use herbicide, trifluralin, and the legacy pesticides mirex and toxaphene, were detected in Antarctic air for the first time. Trifluralin was observed at low but increasing levels over the five-year period. Its detection in the Antarctic atmosphere provides evidence of its persistence and long-range environmental transport capability. While a time frame of five years exceeds the duration of most Antarctic air monitoring efforts, it is projected that continuous monitoring at the decadal scale is required to detect an annual 10% change in atmospheric concentrations of key analytes. This finding emphasizes the importance of continuous, long-term monitoring efforts in polar regions, that serve a special role as sentinel environments of hemispheric chemical usage trends.

This is the first survey to investigate the occurrence and extent of microplastic (MPs) contamination in sub surface waters collected near-shore and off-shore the coastal area of the Ross Sea (Antarctica). Moreover, a non-invasive method to analyze MPs, consisting in filtration after water sampling and analysis of the dried filter through Fourier Transform Infrared Spectroscopy (FTIR) 2D Imaging, using an FPA detector, was proposed. The non-invasiveness of analytical set-up reduces potential bias and allows subsequent analysis of the filter sample for determination of other classes of contaminants. MPs ranged from 0.0032 to 1.18 particle per m3 of seawater, with a mean value of 0.17 ± 0.34 particle m−3, showing concentrations lower than those found in the oceans worldwide. MPs included fragments (mean 71.9 ± 21.6%), fibers (mean 12.7 ± 14.3%), and others (mean 15.4 ± 12.8%). The presence of different types of MPs was confirmed by FTIR spectroscopy, with predominant abundance of polyethylene and polypropylene. The potential environmental impact arising from scientific activities, such as marine activities for scientific purposes, and from the sewage treatment plant, was also evidenced.

Sanchís et al. (2015) recently reported the occurrence of volatile methyl siloxanes (VMS) in soil, vegetation, phytoplankton, and krill samples from Antarctica. As the paper’s title suggests, findings of these chemicals in such a remote region is unexpected and of significant concern. However, our experience with the analysis of these compounds at trace concentrations suggests that the observations reported may have been influenced by artifacts. Here we present our concerns based upon known emissions, physicochemical properties and on apparent quality control measures including treatment of blank samples and detection limits.

This study investigated the role of a permanently manned Australian Antarctic research station (Casey Station) as a source of contemporary persistent organic pollutants (POPs) to the local environment. Polybrominated diphenyl ethers (PBDEs) and poly- and perfluoroalkylated substances (PFASs) were found in indoor dust and treated wastewater effluent of the station. PBDE (e.g., BDE-209 26–820 ng g–1 dry weight (dw)) and PFAS levels (e.g., PFOS 3.8–2400 ng g–1 (dw)) in dust were consistent with those previously reported in homes and offices from Australia, reflecting consumer products and materials of the host nation. The levels of PBDEs and PFASs in wastewater (e.g., BDE-209 71–400 ng L–1) were in the upper range of concentrations reported for secondary treatment plants in other parts of the world. The chemical profiles of some PFAS samples were, however, different from domestic profiles. Dispersal of chemicals into the immediate marine and terrestrial environments was investigated by analysis of abiotic and biotic matrices. Analytes showed decreasing concentrations with increasing distance from the station. This study provides the first evidence of PFAS input to Polar regions via local research stations and demonstrates the introduction of POPs recently listed under the Stockholm Convention into the Antarctic environment through local human activities.

Fish oil dietary supplements and complementary medicines are pitched to play a role of increasing strategic importance in meeting daily requirements of essential nutrients, such as long-chain (≥C20, LC) omega-3 polyunsaturated fatty acids and vitamin D. Recently a new product category, derived from Antarctic krill, has been launched on the omega-3 nutriceutical market. Antarctic krill oil is marketed as demonstrating a greater ease of absorption due to higher phospholipid content, as being sourced through sustainable fisheries and being free of toxins and pollutants; however, limited data is available on the latter component. Persistent Organic Pollutants (POP) encompass a range of toxic, man-made contaminants that accumulate preferentially in marine ecosystems and in the lipid reserves of organisms. Extraction and concentration of fish oils therefore represents an inherent nutritional-toxicological conflict. This study aimed to provide the first quantitative comparison of the nutritional (EPA and DHA) versus the toxicological profiles of Antarctic krill oil products, relative to various fish oil categories available on the Australian market. Krill oil products were found to adhere closely to EPA and DHA manufacturer specifications and overall were ranked as containing intermediate levels of POP contaminants when compared to the other products analysed. Monitoring of the pollutant content of fish and krill oil products will become increasingly important with expanding regulatory specifications for chemical thresholds.

This article investigates the annual cycle observed in the Antarctic baseline aerosol scattering coefficient, total particle number concentration, and particle number size distribution (PNSD), as measured at Troll Atmospheric Observatory. Mie theory shows that the annual cycles in microphysical and optical aerosol properties have a common cause. By comparison with observations at other Antarctic stations, it is shown that the annual cycle is not a local phenomenon, but common to central Antarctic baseline air masses. Observations of ground-level ozone at Troll as well as backward plume calculations for the air masses arriving at Troll demonstrate that the baseline air masses originate from the free troposphere and lower stratosphere region, and descend over the central Antarctic continent. The Antarctic summer PNSD is dominated by particles with diameters <100 nm recently formed from the gas-phase despite the absence of external sources of condensible gases. The total particle volume in Antarctic baseline aerosol is linearly correlated with the integral insolation the aerosol received on its transport pathway, and the photooxidative production of particle volume is mostly limited by photooxidative capacity, not availability of aerosol precursor gases. The photooxidative particle volume formation rate in central Antarctic baseline air is quantified to 207 ±4 μm3/(MJ m). Further research is proposed to investigate the applicability of this number to other atmospheric reservoirs, and to use the observed annual cycle in Antarctic baseline aerosol properties as a benchmark for the representation of natural atmospheric aerosol processes in climate models.

The concentrations of polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) in 35 soil samples collected from Fildes Peninsula in the Antarctic, Ny-Ålesund in the Arctic, and Zhangmu-Nyalam in the Tibetan Plateau were reported in this study. A comparison of the total concentration and TEQ of PCDD/Fs at the Three Poles was conducted. Both the total concentration and TEQ of PCDD/Fs demonstrates a decreasing trend in the order of Zhangmu-Nyalam (mean: 26.22 pg/g, 0.37 pg I-TEQ/g)>Ny-Ålesund (mean: 9.97 pg/g, 0.33 pg I-TEQ/g)>Fildes Peninsula (mean: 2.18 pg/g, 0.015 pg I-TEQ/g) (p<0.05). In all samples, the congener and homologue profiles dominated with higher (seven and eight) chlorinated PCDD/Fs (more than 85% of the total mass percentage of PCDD/Fs) at the Three Poles. Finally, a FLEXPART backward simulation was used to preliminarily identify the potential local and regional anthropogenic sources of PCDD/Fs. The results imply that the air masses passing over surrounding regions with significant PCDD/F emissions might contribute to the occurrence of PCDD/Fs in both the Arctic and Tibetan Plateau.

A first long-term monitoring of selected persistent organic pollutants (POPs) in Antarctic air has been conducted at the Norwegian research station Troll (Dronning Maud Land). As target contaminants 32 PCB congeners, α- and γ-hexachlorocyclohexane (HCH), trans- and cis-chlordane, trans- and cis-nonachlor, p,p'- and o,p-DDT, DDD, DDE as well as hexachlorobenzene (HCB) were selected. The monitoring program with weekly samples taken during the period 2007–2010 was coordinated with the parallel program at the Norwegian Arctic monitoring site (Zeppelin mountain, Ny-Ålesund, Svalbard) in terms of priority compounds, sampling schedule as well as analytical methods. The POP concentration levels found in Antarctica were considerably lower than Arctic atmospheric background concentrations. Similar to observations for Arctic samples, HCB is the predominant POP compound, with levels of around 22 pg m−3 throughout the entire monitoring period. In general, the following concentration distribution was found for the Troll samples analyzed: HCB > Sum HCH > Sum PCB > Sum DDT > Sum chlordanes. Atmospheric long-range transport was identified as a major contamination source for POPs in Antarctic environments. Several long-range transport events with elevated levels of pesticides and/or compounds with industrial sources were identified based on retroplume calculations with a Lagrangian particle dispersion model (FLEXPART).

Brominated diphenyl ethers (BDE47, 99, 100, and 209) were measured in air, snow and sea ice throughout western Antarctica between 2001 and 2007. BDEs in Antarctic air were predominantly associated with aerosols and were low compared to those in remote regions of the northern hemisphere, except in Marguerite Bay following the fire at Rothera research station in Sept 2001, indicating that this event was a local source of BDE209 to the Antarctic environment. Aerosol BDE47/100 reflects a mixture of commercial pentaBDE products; however, BDE99/100 is suggestive of photodegradation of BDE99 during long-range atmospheric transport (LRAT) in the austral summer. BDEs in snow were lower than predicted based on snow scavenging of aerosols indicating that atmospheric deposition events may be episodic. BDE47, -99, and -100 significantly declined in Antarctic sea ice between 2001 and 2007; however, BDE209 did not decline in Antarctic sea ice over the same time period. Significant losses of BDE99 and -100 from sea ice were recorded over a 19 day period in spring 2001 demonstrating that seasonal ice processes result in the preferential loss of some BDEs. BDE47/100 and BDE99/100 in sea ice samples reflect commercial pentaBDE products, suggesting that photodegradation of BDE99 is minimal during LRAT in the austral winter.

Long term atmospheric mercury measurements in the Southern Hemisphere are scarce and in Antarctica completely absent. Recent studies have shown that the Antarctic continent plays an important role in the global mercury cycle. Therefore, long term measurements of gaseous elemental mercury (GEM) were initiated at the Norwegian Antarctic Research Station, Troll (TRS) in order to improve our understanding of atmospheric transport, transformation and removal processes of GEM. GEM measurements started in February 2007 and are still ongoing, and this paper presents results from the first four years. The mean annual GEM concentration of 0.93 ± 0.19 ng m−3 is in good agreement with other recent southern-hemispheric measurements. Measurements of GEM were combined with the output of the Lagrangian particle dispersion model FLEXPART, for a statistical analysis of GEM source and sink regions. It was found that the ocean is a source of GEM to TRS year round, especially in summer and fall. On time scales of up to 20 days, there is little direct transport of GEM to TRS from Southern Hemisphere continents, but sources there are important for determining the overall GEM load in the Southern Hemisphere and for the mean GEM concentration at TRS. Further, the sea ice and marginal ice zones are GEM sinks in spring as also seen in the Arctic, but the Antarctic oceanic sink seems weaker. Contrary to the Arctic, a strong summer time GEM sink was found, when air originates from the Antarctic plateau, which shows that the summertime removal mechanism of GEM is completely different and is caused by other chemical processes than the springtime atmospheric mercury depletion events. The results were corroborated by an analysis of ozone source and sink regions.

The primary input of Persistent Organic Pollutant (POP) contamination to the Antarctic is expected to be via Long Range Atmospheric Transport (LRAT) from emissions in neighboring Southern hemisphere nations In addition to LRAT, system input of POPs must increasingly consider alternate pathways Human activity in the Antarctic represents a potential direct source of both legacy and current-use chemicals It has been two decades since the organic chemical composition of air masses arriving in the Australian Antarctic Territory (AAT), which spans the majority of the eastern Antarctic sector, was last investigated Here we present the first atmospheric measurements made as part of a new continuous monitoring effort at Casey station (66°17’ S 110°31’ E), one of Australia’s all-year research stations The results are evaluated alongside POP contamination data of soil samples collected around the Casey station perimeter and the respective sample profiles are assessed for clues as to local and distant contamination sources Results suggest a potential local source of the currently produced, involatile, deca-brominated PBDE congener 209 which contributed substantially to PBDE profiles of all samples Profiles of polychlorinated biphenyls (PCBs) and rganochlorine pesticides on the other hand primarilly support LRAT as the primary input pathway of these contaminants, whilst a dominance of endosulfan in air samples evidences its ongoing application in the southern hemisphere.