The environmental photolysis of perfluorooctanesulfonate,perfluorooctanoate, and related fluorochemicals

A field study on the photolysis of perfluoroalkyl substances (PFASs) was conducted at high altitudes in Mt. Mauna Kea (Hawaii, USA; 4200 m) and Mt. Tateyama (Toyama, Japan; 2500 m). Results of photolysis of PFASs in the field were further confirmed in laboratory studies. Perfluorooctanesulfonate (PFOS), which is perceived as a non-degradable chemical in the environment, can undergo photolysis. Long chain PFASs can be successively dealkylated to short chain compounds such as perfluorobutyric acid (PFBA) and perfluorobutane sulfonate (PFBS), but the short chain compounds were relatively more resistant to photodegradation. These results suggest that environmental levels of short chain PFASs would increase both due to their formation from photolysis of long chain PFASs and from direct releases. Earlier studies on photolysis of PFASs were focused on the formation of perfluorocarboxylic acids (PFCAs) and perfluorosulfonic acids (PFSAs) from precursor compounds (such as fluorotelomer alcohols) under laboratory conditions. Our study suggests that PFSAs and PFCAs themselves can undergo photodegradation in the environment.     

Modelling atmospheric bulk deposition of Pb,Zn and Cd near a former Pb–Zn mine in West Greenland using transplanted Flavocetraria nivalis lichens

Atmospheric deposition of lead (Pb), zinc (Zn) and cadmium (Cd) was investigated near the former Black Angel Pb–Zn mine in Maarmorilik, West Greenland during 2010–2011. Thalli of the lichen Flavocetraria nivalis were transplanted from an uncontaminated site into sites near the mine and collected the following year. At 20 of the total 21 sites, concentrations of Pb, Zn and Cd were significantly elevated in lichens after 1 year of transplantation compared to initial concentrations. Elevated concentrations were observed within a distance of approx. 20 km from the mining area. Concentrations decreased with increasing distance from the mine and the relation was well described using a power function with a negative exponent (r² = 0.90; 0.83 and 0.83 for Pb; Zn and Cd). To examine the relation between metal concentrations/uptake in lichen transplants and atmospheric bulk deposition, 10 Bergerhoff dust samplers were placed near lichen transplants and samplers and lichens were collected after a 7-weeks exposure period. A significant linear correlation was observed between metal concentrations in lichen transplants and atmospheric bulk metal deposition (r² = 0.94; 0.88 and 0.89 for Pb; Zn and Cd). Combining the results and including an area distribution within a defined metal deposition area, the “annual” deposition of Pb, Zn and Cd as dust was estimated during the 2010–2011 snow-free period (～5 months). The results reveal that 20 years after mine closure, 770 kg Pb, 3700 kg Zn and 24 kg Cd were still being deposited as dust per year (snow-free period only) within a distance of 20 km from the mine.     

Enhanced metal and metalloid concentrations in the gut system comparing to remaining tissues of Gammarus pulex L

Invertebrate shredders such as Gammarus pulex are key species in contaminated stream ecosystems. Although a number of previous studies examining differences in metal accumulation between the gut system and remaining tissues of invertebrates exist, few focus on wide range of metals and metalloids that are relevant to contaminated systems. This study compared accumulation of the commonest (at study site) 15 metals and metalloids between the gut system including feces and remaining tissues of G. pulex. All metals and metalloids measured were significantly higher (p<0.001, except Cu p<0.005) in the gut system including feces than remaining tissues of G. pulex. Metals and metalloids in body tissues without the gut system including feces were significantly lower (Al, Cr, Fe and Mn (p<0.005), Sr and U (p<0.01), Co (p<0.05)) in content for a number of elements when compared to washed, whole G. pulex specimens. As well, all elements measured were significantly higher (all elements (p<0.005) except Cu and Co (p<0.05)) in gut system including feces than washed, whole G. pulex specimens. These results indicate that in G. pulex the uptake of all 15 metals and metalloids examined across the gut epithelium is minimalized or that sequestration of these elements in gut epithelial cells may occur.     

Assessing the Impacts of Long-Range Sulfur and Nitrogen Deposition on Arctic and Sub-Arctic Ecosystems

For more than a decade, anthropogenic sulfur (S) and nitrogen (N) deposition has been identified as a key pollutant in the Arctic. In this study new critical loads of acidity (S and N) were estimated for terrestrial ecosystems north of 60° latitude by applying the Simple Mass Balance (SMB) model using two critical chemical criteria (Al/Bc = 1 and ANC_le = 0). Critical loads were exceeded in large areas of northern Europe and the Norilsk region in western Siberia during the 1990s, with the more stringent criterion (ANC_le = 0) showing the larger area of exceedance. However, modeled deposition estimates indicate that mean concentrations of sulfur oxides and total S deposition within the Arctic almost halved between 1990 and 2000. The modeled exceeded area is much reduced when currently agreed emission reductions are applied, and almost disappears under the implementation of maximum technically feasible reductions by 2020. In northern North America there was no exceedance under any of the deposition scenarios applied. Modeled N deposition was less than 5 kg ha⁻¹ y⁻¹ almost across the entire study area for all scenarios; and therefore empirical critical loads for the eutrophying impact of nitrogen are unlikely to be exceeded. The reduction in critical load exceedances is supported by observed improvements in surface water quality, whereas the observed extensive damage of terrestrial vegetation around the mining and smelter complexes in the area is mainly caused by direct impacts of air pollution and metals.     

Pb isotopes as tracers of mining-related Pb in lichens, seaweed and mussels near a former Pb-Zn mine in West Greenland

Identification of mining-related contaminants is important in order to assess the spreading of contaminants from mining as well as for site remediation purposes. This study focuses on lead (Pb) contamination in biota near the abandoned ‘Black Angel Mine’ in West Greenland in the period 1988-2008. Stable Pb isotope ratios and total Pb concentrations were determined in lichens, seaweed and mussels as well as in marine sediments. The results show that natural background Pb (²⁰⁷Pb/²⁰⁶Pb: 0.704-0.767) and Pb originating from the mine ore (²⁰⁷Pb/²⁰⁶Pb: 0.955) have distinct isotopic fingerprints. Total Pb in lichens, seaweed, and mussels was measured at values up to 633, 19 and 1536 mg kg⁻¹ dry weight, respectively, and is shown to be a mixture of natural Pb and ore-Pb. This enables quantification of mining-related Pb and shows that application of Pb isotope data is a valuable tool for monitoring mining pollution.     

Perfluorinated acids as novel chemical tracers of global circulation of ocean waters

Perfluorinated acids (PFAs) such as perfluorooctanesulfonate (PFOS) and perfluorooctanoate (PFOA) are global environmental contaminants. The physicochemical properties of PFAs are unique in that they have high water solubilities despite the low reactivity of carbon-fluorine bond, which also imparts high stability in the environment. Because of the high water solubilities, the open-ocean water column is suggested to be the final sink for PFOS and PFOA. However, little is known on the distribution of PFAs in the oceans around the world. Here we describe the horizontal (spatial) and vertical distribution of PFAs in ocean waters worldwide. PFOS and PFOA concentrations in the North Atlantic Ocean ranged from 8.6 to 36pg l(-1) and from 52 to 338pg l(-1), respectively, whereas the corresponding concentrations in the Mid Atlantic Ocean were 13-73pg l(-1) and 67-439pg l(-1). These were completely different from the surface waters of the South Pacific Ocean and the Indian Ocean (overall range of <5-11pg l(-1) for PFOS and PFOA). Vertical profiles of PFAs in the marine water column were associated with the global ocean circulation theory. Vertical profiles of PFAs in water columns from the Labrador Sea reflected the influx of the North Atlantic Current in surface waters, the Labrador Current in subsurface waters, and the Denmark Strait Overflow Water in deep layers below 2000m. Striking differences in the vertical and spatial distribution of PFAs, depending on the oceans, suggest that these persistent acids can serve as useful chemical tracers to allow us to study oceanic transportation by major water currents. The results provide evidence that PFA concentrations and profiles in the oceans adhere to a pattern consistent with the global "Broecker's Conveyor Belt" theory of open ocean water circulation.     

Historical trends in persistent organic pollutants and metals recorded in sediment from Lake Ellasjøen, Bjørnøya, Norwegian Arctic

Ellasj?en receives contaminants from both atmospheric and biological transport (seabird guano). Historical trends of selected persistent organic pollutants and metals were determined by interpretation of down-core contaminant profiles in conjunction with sediment layer ages, determined by the (210)Pb method. Polychlorinated biphenyls (PCBs) and dichloro-diphenyl-trichloroethane and metabolites (DDTs) increased from about 1930 until 1970 (max. sum PCBs 71.8 ng/g dry weight (dw), max sum DDTs 4.0 ng/g dw), declining afterwards to 46.4 ng/g dw and 1.6 ng/g dw, respectively. Polybrominated diphenylethers (PBDEs) concentrations are increasing in Ellasj?en, reaching 0.73 ng/g dw in 2001. Hexabromocyclododekane (HBCD) was measured only in sediment from 1-2 cm depth (0.43 and 3.88 ng/g dw of alpha- and gamma-HBCD, respectively). Most metals (As, Cd, Co, Ni and Zn) showed a similar pattern as PCBs. No clear trends were observed for Cr, Pb or V. Mercury (Hg) has increased gradually since the beginning of the industrial era.