Analysis of occurrence, bioaccumulation and molecular targets of arsenic and other selected volcanic elements in Argentinean Patagonia and Antarctic ecosystems.

In Latin America, the high proportion of arsenic (As) in many groundwaters and phreatic aquifers is related to the volcanism of the Andean Range. Nevertheless, there is still very little published research on As and other elements occurrence, and/or transference to biota in Southern regions such as Argentinean Patagonia and the South Shetland Islands in Antarctica, where there are active volcanoes and geothermal processes. Therefore, this study was aimed to describe water quality from the main rivers of Argentinean Northern Patagonia through physicochemical analysis. The Patagonian and Antarctic biota (including samples of animal, plants, algae and bacteria) was characterized through the analysis of their As and other elemental concentrations (P, S, Cl, K, Ca, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, Se, Br, Rb and Sr), by synchrotron radiation x-ray fluorescence spectroscopy (SRXRF). Finally, the analysis of metal and As-proteins associations in As-accumulating organisms was performed by SRXRF after sodium dodecyl sulphate-polyacrylamide gel electrophoresis (SDS-PAGE). A wide range of metal concentration including As (up to 950 µg/L As) was found in water samples from Patagonian rivers. A hierarchical cluster analysis revealed that the elemental concentration of analysed biological samples was related to volcanic environments and their place in the trophic chain. Moreover, the results suggest that Se, Co, Cu, Br, and Cl are strong predictors of As in biota. On the other hand, As was not detected in proteins from the studied samples, suggesting biotransformation into soluble As-organic compounds. This is the first study to describe environmental pollution as a consequence of active volcanism, and its influence on water quality and elemental composition of biota in Argentinean Northern Patagonia and Antarctica.

Bacterial communities and chemical parameters in soils and coastal sediments in response to diesel spills at Carlini Station, Antarctica.

A diesel spill occurring at Carlini Station (King George Island (Isla 25 de Mayo), South Shetland Islands) in 2009 started the study of the fate of the hydrocarbons and their effect on the bacterial communities of the Potter Cove ecosystem. Soils and sediments were sampled across the 200-meter long diesel plume towards Potter Cove four and 15months after the spill. The sampling revealed a second fuel leakage from an underground pipeline at the spill site. The hydrocarbon fraction spilt over frozen and snow-covered ground reached the sea and dispersed with the currents. Contrary, diesel that infiltrated unfrozen soil remained detectable for years, and was seeping with ground water towards coastal marine sediments. Structural changes of the bacterial communities as well as hydrocarbon, carbon and nitrogen contents were investigated in sediments in front of the station, two affected terrestrial sites, and a terrestrial non-contaminated reference site. Bacterial communities (16S rRNA gene clone libraries) changed over time in contaminated soils and sediments. At the underground seepage site of highest contamination (5812 to 366µgg-1dw hydrocarbons from surface to 90-cm depth), communities were dominated by Actinobacteria (18%) and a betaproteobacterium closely related to Polaromonas naphthalenivorans (40%). At one of the spill sites, affected exclusively at the surface, contamination disappeared within one year. The same bacterial groups were enriched at both contaminated sites. This response at community level suggests that the cold-adapted indigenous microbiota in soils of the West Antarctic Peninsula have a high potential for bioremediation and can support soil cleaning actions in the ecosystem. Intensive monitoring of pollution and site assessment after episodic fuel spills is required for decision-making towards remediation strategies.

Heavy metals in sediments and soft tissues of the Antarctic clam Laternula elliptica: more evidence as a possible biomonitor of coastal marine pollution at high latitudes?

Studies on metal contamination in 25 de Mayo Island, Antarctica, yielded controversial results. In this work, we analyzed Antarctic marine sediments and Antarctic clam (Laternula elliptica) tissues to investigate the possible use of this mollusk as a biomonitor of metals and to identify the sources of metal pollution. Different types of paint from several buildings from Carlini Station were examined to assess their contribution to the local and random metal pollution. Five sediment samples, 105 L. elliptica specimens (40.2-78.0mm length) and four types of paint were analyzed to quantify Cd, Cr, Cu, Fe, Mn, Pb and Zn using inductively coupled plasma-optical emission spectrometry. Metal concentrations in sediments were lower than the global averages of the earth's crust, with the exception of Cd and Cu. These results were related to the contribution of the local fresh-water runoff. The different varieties of paint showed low levels of Cu, Mn, Fe and Zn, whereas a broad range of values were found in the case of Cr and Pb (20-15,100 µg·g(-1) and 153-115,500 µg·g(-1) respectively). The remains of the paint would be responsible for the significant increases in Cr and Pb which are randomly detected by us and by other authors. High levels of Fe and Cd, in comparison to other Antarctic areas, appear to be related to the terrigenous materials transported by the local streams. Accumulation indexes suggested that kidney tissue from L. elliptica could be an adequate material for biomonitoring pollution with Cd, Zn and probably also Pb. In general, relationships between size and metal contents reported by other authors were not verified, suggesting that this issue should be revised.

Presence and distribution of persistent toxic substances in sediments and marine organisms of Potter Cove, Antarctica.

Levels of butyltin compounds, polychlorinated biphenyls, and heavy metals were analyzed in marine sediments and organisms (Notothenia coriiceps, Laternula elliptica, and Nacella concinna), each of which has a different feeding strategy, in Potter Cove, Antarctica. PCBs were lower than detection limits in all samples. Only butyltin compounds were detected in a restricted area near the scientific station. Chromium, copper, magnesium, lead (Pb), and zinc had similar behavior in the cove, probably because they are regulated by similar process and conditions. However, Pb levels in some sites of the cove seem to be related to human activities in the area. Cadmium levels were relatively low, with the highest values found close to the shoreline, which is probably influenced by seasonal streams draining waters from Potter Peninsula. Results showed that despite the fact that Jubany Station has been operating for > 50 years, surface sediment and biota from Potter Cove do not exhibit levels of pollutants representing environmental concern.

Polycyclic aromatic hydrocarbons in soil and surface marine sediment near Jubany Station (Antarctica). Role of permafrost as a low-permeability barrier.

Although Antarctica is still considered as one of the most pristine areas of the world, the growing tourist and fisheries activities as well as scientific operations and their related logistic support are responsible for an increasing level of pollutants in this fragile environment. Soils and coastal sediments are significantly affected near scientific stations particularly by polycyclic aromatic hydrocarbons (PAHs). In this work sediment and soil were sampled in two consecutive summer Antarctic expeditions at Potter Cove and peninsula, in the vicinity of Jubany Station (South Shetland Islands). Two- and 3-ring PAHs (methylnaphthalene, fluorene, phenanthrene and anthracene) were the main compounds found in most sites, although total PAH concentrations showed relatively low levels compared with other human-impacted areas in Antarctica. Pattern distribution of PAHs observed in samples suggested that low-temperature combustion processes such as diesel motor combustion and open-field garbage burning are the main sources of these compounds. An increase in PAH concentrations was observed from surface to depth into the active soil layer except for a unique sampling site where a fuel spill had been recently reported and where an inverted PAH concentration gradient was observed. The highest level was detected in the upper layer of permafrost followed by a sharp decrease in depth, showing this layer is acting as a barrier for downward PAH migration. When PAH levels in soil from both sampling programs were compared a significant decrease (p<0.01) was observed in summer 2005 (range at 75-cm depth: 12+/-1-153+/-22 ng/g) compared to summer 2004 (range at 75-cm depth: 162+/-15-1182+/-113 ng/g) whereas concentrations in surface sediment collected nearby the station PAHs increased drastically in 2005 (range: 36+/-3-1908+/-114 ng/g) compared to 2004 (range: 28+/-3-312+/-24 ng/g). Precipitation regime and water run off suggest that an important wash out of soil-PAHs occurred during the interval time between samplings. Results showed that the present PAH contamination level of Jubany Station is relatively low compared to other reported cases in Antarctica but also suggests that an increase in rain and in thawing processes caused by the global warming could result in an important soil-associated PAH mobilization with unpredictable consequences for the biota of Potter Cove.

Total and inorganic arsenic in Antarctic macroalgae.

The Antarctic region offers unparalleled possibilities of investigating the natural distribution of metals and metalloids, such as arsenic. Total and inorganic As were analysed in nine species of Antarctic macroalgae collected during the 2002 summer season in the Potter Cove area at Jubany-Dallmann Station (South Shetland Islands, Argentinian Base). Total As was determined by inductively coupled plasma-optical emission spectrometry after microwave-assisted acid digestion. Inorganic As was determined by acid digestion, solvent extraction, flow injection-hydride generation-atomic absorption spectrometry. Total As ranged from 5.8 microg g(-1) dry weight (dw) (Myriogramme sp.) to 152 microg g(-1)dw (Himantothallus grandifolius). Total As concentrations were higher in Phaeophytes (mean+/-SD: 71+/-44 microg g(-1)dw) than in Rhodophytes (mean+/-SD: 15+/-11 microg g(-1)dw). Inorganic As ranged from 0.12 microg g(-1) (Myriogramme sp.) to 0.84 microg g(-1)dw (Phaeurus antarcticus). The percentage of inorganic As with respect to total As was 0.7 for Phaeophytes, but almost 4 times higher for Rhodophytes (2.6). The work discusses possible causes for the presence of As in marine organisms in that pristine environment.