María Arribére

Heavy metals in the vicinity of a chlor-alkali factory in the Upper Negro River ecosystem, Northern Patagonia, Argentina.

A study on heavy metal contents was performed in sediments and biota of the Upper Negro River (Alto Valle) aquatic system, Northern Patagonia, Argentina. The irrigation system of the Neuquén and Negro Rivers runs alongside these rivers for 150 km, supporting intensive agricultural and economical activities, mainly related to fruit production. A mercury cell chlor-alkali factory operated between 1951 and 1995. Close attention was given to the surroundings of the plant, located next to the Main Irrigation Channel, and to the PII drainage channel which received the plants effluents between 1951 and 1979. From 1979 until its closure, the effluents were pumped above a ravine to a series of evaporation and decantation pools. Mercury and other heavy metals and metalloids (Ag, As, Ba, Co, Cr, Cs, Ni, Sb, Se, U and Zn) contents were measured for bottom sediments of the river and irrigation and drainage channels, for two widespread species of macrophytes (Potamogeton pectinatus and Myriophyllum brasiliensi), and for liver and muscle of native fish Odontesthes microlepidotus. River bed sediments show no evidence of heavy metal accumulation, however, biota might indicate that contaminants are entering the rivers. Mercury was the only element accumulated in the Main Irrigation channel sediments, the highest contents occurring in the surroundings of the nowadays shut-down chlor-alkali plant, returning to background values approximately 40 km downstream the plant. At the plant site, sediments from the center of the channel showed a decrease in Hg content in the upper 10 cm layer, ranging from 0.8 to 3.4 microg g(-1), and from 2.8 to 13.7 microg g(-1) in the next 10 cm lower layer. Conversely, the PII drainage channel sediments showed accumulation of Hg (2-4 microg g(-1)), distributed uniformly at different depths and along the channel, until its mouth at Negro river. Mercury contents of macrophytes downstream the chlor-alkali plant are higher than the baseline for the area, and macrophytes and fish liver from the PII drainage channel present the highest content in this element. The drainage channel system showed different degrees of impact, those channels flowing through densely populated areas being the most affected.

Elemental composition of lichens at Nahuel Huapi National Park, Patagonia, Argentina

Five species of epiphytic lichens were sampled from urban and periurban areas of Bariloche, a non industrial city located on the East side of the Nahuel Huapi National Park, North-Western Patagonia, Argentina, and from pristine areas of the Park. Each individual lichen was analyzed using Instrumental Neutron Activation Analysis. The results of the analysis showed high concentrations of lithophile elements, with very good correlations among them. The relative concentration of these elements in all lichen species is in good agreement with the elemental composition of sediments collected in the Park. Elemental concentrations which are not related to detritical inputs are also presented.

Rare earth geochemistry in sediments of the Upper Manso River Basin, Rio Negro, Argentina

Abstract The abundance, distribution and fractionation of rare earth elements was studied in solid material transported by the Upper Manso River and in the sediments deposited in Lake Mascardi, Argentina. The pristine condition of the area offers an ideal environment for assessing geochemical processes, and the seasonal cycles to which the basin is subjected permit us to study seasonal variations that are mainly influenced by glacial pulses. The most remarkable characteristics observed in the REE-normalized patterns are a strong HREE enrichment and a positive Eu anomaly. These normalized patterns are atypical as compared to those considered representative of the worlds major rivers and are caused by drainage basin geology. Due to the dissected topography and the small size of the basin, intense mixing phenomena are not favoured and the weathering reactions are inhibited by the fast-flowing river. These physicochemical conditions and near-neutral pH values have an important influence on the REE patterns of the sediments, which mainly originated by glacial erosion, that are transported by the river. The feldspars and their secondary products, which are both enriched in Eu, might be the cause of the Eu anomaly. HREE enrichment, which is mainly associated with high-pH systems or with the presence of accessory phases, shows a clear dependence on source rocks. The calculated(La/Yb) N ratios oscillate between 0.5 and 0.6, contrasting with the values reported in the literature as average values for suspended load material. Nevertheless, these values are consistent with the dependence of(La/Yb) N values on the age of drainage area rocks as was observed by Goldstein and Jacobsen [3]. Seasonal variations are not manifested in REE concentrations, and additional elemental determinations showed coherent behaviour during weathering for all elements except Sr and Ba, which exhibited selective elemental mobilization during periods of minimum discharge.

Heavy Metal and Other Trace Elements in Native Mussel Diplodon chilensis from Northern Patagonia Lakes, Argentina

Native mussels, Diplodon chilensis, were sampled from four lakes in Nahuel Huapi National Park, Northern Patagonia, Argentina in order to evaluate heavy-metal distribution in the region and to assess the contribution of this compartment of the trophic web to their circulation in the food chain. The concentration of potential pollutants Ag, As, Cr, Hg, Sb, and Se, and other nine elements of interest (Ba, Br, Ca, Co, Cs, Fe, Na, Sr, and Zn) were determined in Diplodon chilensis pooled samples. Digestive glands were analyzed separately from soft tissues. Geological tracers Sc, Ta, Th, and rare earth elements were also determined in order to discriminate lithophile contributions. Elemental concentrations of Ba, Br, Fe, Sr, Se, and Zn in total soft tissues samples do not show significant differences among sampling sites. Arsenic and Cr contents in total soft tissues and digestive gland pooled samples are higher in sampling points close to zones with human settlements. Silver contents in samples collected in Lake Nahuel Huapi were higher than in the other lakes studied, and up to 50-fold higher than the sample collected in Lake Traful, considered as the reference. Mercury highest concentration values measured in total soft tissues pooled samples from lakes Nahuel Huapi and Moreno were found to be similar to those observed in other reported Hg contamination situations, and they are three to five times higher than those of the reference samples collected in Lake Traful.

137Cs dating of lake cores from the Nahuel Huapi National Park, Patagonia, Argentina: Historical records and profile measurements

Historical records of short lived (140Ba, 131I, 103Ru and 95Zr+95Nb) and long-lived (137Cs and 90Sr) fission products by fallout measurements performed in Argentina since 1959 were analyzed in order to define the main characteristics of 137Cs fallout time evolution in the Nahuel Huapi National Park, Patagonia, Argentina. Sedimentary cores were sampled from Lake Nahuel Huapi and Lake Morenito, which are located within Nahuel Huapi National Park. 137Cs specific activity profiles were measured and 210Pb dating was performed in each core. The time evolution of 137Cs fallout shows different characteristics than records taken in the Northern Hemisphere.137Cs specific activity profiles of the cores studied reproduce the fallout time sequence observed in the historical records, and the chronology obtained shows excellent agreement with 210Pb dating.

Mercury in the biotic compartments of Northwest Patagonia lakes, Argentina.

We report on total mercury (THg) concentrations in the principal components of food webs of selected Northern Patagonia Andean Range ultraoligotrophic lakes, Argentina. The THg contents were determined using Instrumental Neutron Activation Analysis in muscle and liver of four fish species occupying the higher trophic positions (the introduced Salmo trutta, Oncorhynchus mykiss and Salvelinus fontinalis, and the native Percichthys trucha) accounted for eight lakes belonging to Nahuel Huapi and Los Alerces National Parks. We studied the food web components of both the West and East branches of Lake Moreno, including benthic primary producers such as biofilm, mosses, and macrophytes, three plankton fractions, fish, riparian tree leaves, and benthic invertebrates, namely decapods, molluscs, insect larvae, leeches, oligochaetes, and amphipods. Mercury concentrations in fish muscle varied in a wide range, from less than 0.05 to 4 μg g(-1) dry weight (DW), without a distribution pattern among species but showing higher values for P. trucha and S. fontinalis, particularly in Lake Moreno. The THg contents of the food web components of Lake Moreno varied within 4 orders of magnitude, with the lower values ranging from 0.01 to 0.5 μg g(-1) DW in tree leaves, some macrophytes, juvenile salmonids or benthic macroinvertebrates, and reaching concentrations over 200 μg g(-1) DW in the plankton. Juvenile Galaxias maculatus caught in the pelagic area presented the highest THg contents of all fish sampled, reaching 10 μg g(-1) DW, contents that could be associated with the high THg concentrations in plankton since it is their main food source. Although Lake Moreno is a system without local point sources of contamination, situated in a protected area, some benthic organisms presented high THg contents when compared with those from polluted ecosystems.

Source identification of volcanic ashes by geochemical analysis of well preserved lacustrine tephras in Nahuel Huapi National Park.

Well preserved volcanic ashes produced in recent events, recovered from sedimentary sequences extracted from three lakes belonging to Nahuel Huapi National Park, Northern Patagonia, were geochemically characterized in order to reveal patterns that allow the identification of the source. Two water bodies are situated in the direct impact area of volcanoes Calbuco and Puyehue-Cordón Caulle, while the third, lake Moreno, is situated in-between. The sedimentary sequences were dated by (210)Pb and (137)Cs techniques; the elemental composition was determined by Instrumental Neutron Activation Analysis. Distinctive patterns were found out when comparing glass shards, and also white pumice but in a lesser degree, of tephra layers extracted from lake Ilón, related mostly to volcano Calbuco events, and lake Nahuel Huapi (Brazo Rincón site), associated to Puyehue-Cordón Caulle eruptions. The geochemical parameters that showed decisive differences were SiO(2) and Na(2)O+K(2)O contents, the Eu anomaly, Rare Earth element ratios; the concentration of incompatible elements Cs, Rb, Th, Hf, Ta and Zr, and the compatible elements Cr and V. The six upper tephra layers extracted from lake Moreno showed geochemical patterns that allowed clear association with Calbuco and Puyehue-Cordón Caulle sources. These results set up the base for tephrochronological applications in historical periods in Nahuel Huapi National Park area.

Fruit Mineral Contents of Six Wild Species of the North Andean Patagonia, Argentina

The fruit mineral contents (K, Ca, Ba, Br, Zn, Co, Cr, Fe, Na, Rb, Cs, and Sr) of four native and two exotic naturalized shrubs growing in different areas of the Andean Patagonian region of Argentina were investigated. Native species Berberis darwinii, Berberis microphylla (Berberidaceae), Aristotelia chilensis (Elaeocarpaceae) and Ribes magellanicum (Saxifragaceae) produce small berries while the fruits of the exotic species Rosa rubiginosa and Rosa canina (Rosaceae) are aggregates of aquenes. They are used to prepare jams, tea, liquors, and ice creams. Native shrub fruits had higher content of Br, Zn, Co, Cr, Fe, Mo, and Na than those of the exotic naturalized species. Rosa species showed the highest contents of Ca and Ba in their fruits (the mean content doubled those of the native plant fruits). The fruit nutrient content found in the studied species was similar or higher than other values reported for fruits of temperate and tropical species in the world.

Bioindication of volatile elements emission by the Puyehue-Cordón Caulle (North Patagonia) volcanic event in 2011

The emission of volatile pollutants from the volcanic eruption of the Puyehue-Cordón Caulle complex (North Patagonia Andean Range) that started in June 4th, 2011, was investigated by bioindication means with the epyphytic fruticose lichen Usnea sp. The elemental composition of pooled samples made up with 10 lichen thalli were analysed by Instrumental Neutron Activation Analysis. Eleven sampling sites were selected within the impacted region at different distance from the volcanic source. Five sites were selected as they were already sampled in a previous study prior to the eruption. Two other new sampling sites were selected from outside the impacted zone to provide non-impacted baseline sites. The elements associated with the lichen incorporation of particulate matter (PM) of geological origin were identified by linear correlation with a geochemical tracer (Sm concentrations). The elements associated with PM uptake were Ce, Eu, Fe, Hf, La, Lu, Na, Nd, Sb, Sc, Se, Ta, Tb, Th, U, and Yb. Arsenic and Cs concentrations showed contributions exceeding the PM fraction in sites near the volcanic centre, also higher than the baseline concentrations, which could be associated with permanent emissions from the geothermal system of the Puyehue-Cordón Caulle complex. The lichen concentrations of Ba, Ca, Co, Hg, K, Rb, Sr, and Zn were not associated with the PM, not showing higher concentrations in the sites nearby the volcanic source or respect to the baseline values either. Therefore, there is no indication of the emission of volatile forms of these elements in the lichen records. The lichen records only identified Br volatile emissions associated with the Puyehue-Cordón Caulle complex eruption in 2011.

Methylmercury production in the water column of an ultraoligotrophic lake of Northern Patagonia, Argentina.

Methyl-mercury (CH3Hg+) production was studied in freshwaters from lake Moreno, an ultraoligotrophic system belonging to Northern Patagonia. Hg2+ labelled with high specific activity 197Hg was spiked to water samples in concentrations of 10 ng l(-1), and incubated in laboratory for 3d time trends under different conditions. Experimental water was sampled daily to evaluate CH3(197)Hg+ production. Lake water used in the experiments was sampled just below the upper limit of the metalimnion ( approximately 30 m depth), where maximum values of chlorophyll a have been measured previously. Sampling was performed in late autumn, when the plankton fraction <50 microm exhibited mercury concentrations up to 260 microg g(-1) dry weight. The experiments analysed lake water filtered through 50, 20, and 0.2 microm (filter-sterilized) mesh nets. ASTM grade 1 water was also incubated for control. All the experiments were run in an environmental chamber under controlled temperature and light regime. High Hg2+ conversion to CH3Hg+, up to 50%, was measured in lake water, in a process stimulated by light. CH3Hg+ production was two-fold higher after 3d of incubation with illumination compared to total darkness. Sterile lake water showed conversions up to 30%, while the planktonic components seem to enhance the CH3Hg+ production. Overall, our results provide evidence that lake Moreno waters favour CH3Hg+ production in processes stimulated by light. Although biotic components certainly contribute to enhance mercury methylation, water chemistry plays a key role in this process. We hypothesize that dissolved organic matter, particularly its quality, could be decisive.