Sergio Ribeiro Guevara

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.

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.

Mercury methylation and reduction potentials in marine water: An improved methodology using 197Hg radiotracer

A highly sensitive laboratory methodology for simultaneous determination of methylation and reduction of spiked inorganic mercury (Hg(2+)) in marine water labelled with high specific activity radiotracer ((197)Hg prepared from enriched (196)Hg stable isotope) was developed. A conventional extraction protocol for methylmercury (CH(3)Hg(+)) was modified in order to significantly reduce the partitioning of interfering labelled Hg(2+) into the final extract, thus allowing the detection of as little as 0.1% of the Hg(2+) spike transformed to labelled CH(3)Hg(+). The efficiency of the modified CH(3)Hg(+) extraction procedure was assessed by radiolabelled CH(3)Hg(+) spikes corresponding to concentrations of methylmercury between 0.05 and 4ngL(-1). The recoveries were 73.0±6.0% and 77.5±3.9% for marine and MilliQ water, respectively. The reduction potential was assessed by purging and trapping the radiolabelled elemental Hg in a permanganate solution. The method allows detection of the reduction of as little as 0.001% of labelled Hg(2+) spiked to natural waters. To our knowledge, the optimised methodology is among the most sensitive available to study the Hg methylation and reduction potential, therefore allowing experiments to be done at spikes close to natural levels (1-10ngL(-1)).

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.

Apple snails and their endosymbionts bioconcentrate heavy metals and uranium from contaminated drinking water

PurposeThe differential ability of apple snail tissues, endosymbionts, and eggs to bioaccumulate several metals (Sb, As, Ba, Br, Zn, Cr, Fe, Hg, Se, and U) was investigated.MethodsMetal concentrations were determined by neutron activation analysis in several tissues, endosymbionts, and eggs from mature apple snails cultured in either drinking water or reconstituted water (prepared with American Society for Testing and Materials type I water).ResultsThe highest bioconcentration factors (BCFs) in the midgut gland were found for Ba, Zn, Se, As, U, Br, and Hg (in decreasing order), while the highest in the kidney were for Ba, Br, and Hg. The foot showed the highest BCFs for Ba, Hg, Br, and Se (in decreasing order). Calcified tissues (uterus, shell) and eggs showed low BCFs, except for Ba. Both C corpuscles and gland tissue showed statistically higher BCFs than K corpuscles for Ba, Fe, U, Br, and Sb. The concentration of most of the studied elements was significantly lower in tissues and endosymbionts obtained from snails cultured in reconstituted water instead of drinking water. Snails cultured in reconstituted water and then exposed or not to Hg, As, and U (at the maximum contaminant level allowed by the US Environmental Protection Agency) also resulted in high levels accumulated in midgut gland, endosymbionts and kidney.ConclusionsOur findings suggest that the midgut gland (and the symbionts contained therein), the kidney, and the foot of Pomacea canaliculata may be useful bioindicators of Hg, As and U pollution in freshwater bodies and that the unrestricted use of ampullariid snails as human and animal food must be considered with caution..

HEAVY METAL CONTAMINATION IN SEDIMENTS OF LAKE NAHUEL HUAPI, NAHUEL HUAPI NATIONAL PARK, NORTHERN PATAGONIA, ARGENTINA

Trace metals (Sb, As, Br, Cs, Co, Cr, Ag and Hg), rare earth elements (Ce, Eu, La, Lu, Sm, Tb and Yb), and Sc. were analysed in suspended load and in two sediment cores from Lake Nahuel Huapi, Nahuel Huapi National Park, Patagonia, Argentina, by using Instrumental Neutron Activation Analysis. The core activity profiles of 210Pb and 137Cs were measured to estimate the age of the sediments. Silver was enriched in the upper layers of both cores, and correlated with the strong growthof the population of Bariloche City in the last 50 yr. Concentrations are higher in the core sampled near Bariloche, andindicate some transport in the water body. Silver concentrationsmeasured in the suspended load were 4.58±0.36 and 3.46±0.40 μg g-1 in the southern margin of the lake, near San Carlos de Bariloche City, whereas in the northern margin the concentrations were 1.68±0.18 and 1.88±0.23 μg g-1. Concentration ratio for silver in suspended load and upper core layers were equal in both sampling points. These facts suggest that Ag contents correspond to inputs associated with human activities. Bromine concentrations show a strong increase abovebase line values, similar to silver. In contrast, caesium, chromium, and cobalt concentrations do not differ from base linevalues. The metalloids antimony and arsenic show little variationwith regard to base line concentration. Noticeable, the mercurycontents found in the suspended load.

Differential mercury transfer in the aquatic food web of a double basined lake associated with selenium and habitat.

Food web trophodynamics of total mercury (THg) and selenium (Se) were assessed for the double-basined ultraoligotrophic system of Lake Moreno, Patagonia. Each basin has differing proportions of littoral and pelagic habitats, thereby providing an opportunity to assess the importance of habitat (e.g. food web structure or benthic MeHg production) in the transfer of Hg and Se to top trophic fish species. Pelagic plankton, analyzed in three size classes (10-53, 53-200, and >200 μm), had very high [THg], exceeding 200 μg g(-1) dry weight (DW) in the smallest, and a low ratio of MeHg to THg (0.1 to 3%). In contrast, [THg] in littoral macroinvertebrates showed lower values (0.3 to 1.8 μg g(-1) DW). Juvenile and small fish species feeding upon plankton had higher [THg] (0.2 to 8 μg g(-1) muscle DW) compared to large piscivore fish species (0.1 to 1.6 μg g(-1) muscle DW). Selenium concentrations exhibited a much narrower variation range than THg in the food web, varying from 0.5 to 2.7 μg g(-1) DW. Molar Se:Hg ratios exceeded 1 for the majority of organisms in both basins, with most ratios exceeding 10. Using stable nitrogen isotopes as indicator of trophic level, no significant correlations were found with [THg], [Se] or Se:Hg. The apparent lack of biomagnification trends was attributed to elevated [THg] in plankton in the inorganic form mostly, as well as the possibility of consistent Se supply reducing the biomagnification in the food web of the organic portion of THg.

Influence of precipitation, landscape and hydrogeomorphic lake features on pelagic allochthonous indicators in two connected ultraoligotrophic lakes of North Patagonia

We investigated the terrestrial influence on two chained deep ultraoligotrophic lakes of North Patagonia (Argentina) through the seasonal analysis of two pelagic allochthonous indicators: i) water color, as a proxy of allochthonous dissolved organic matter in lakes; and ii) the color to chlorophyll a ratio (Color:Chla), as an indicator of the relationship between allochthonous and autochthonous carbon pools. We also evaluated the potential transfer pathways of the allochthonous dissolved organic matter into the pelagic food webs of these deep lakes, including the natural zooplankton δ(13)C in the analysis. The dynamics of the allochthonous indicators were related to the precipitation regime, water level fluctuations, and hydrogeomorphic and catchment features of lakes Moreno East and Moreno West. The water color (absorbance at 440 nm) was extremely low (<0.28 m(-1)) in both lakes regardless of the season. However, precipitation and snowmelt regimes drove the increase and decrease of water color, respectively. A significant positive relationship between the zooplankton bulk δ(13)C with the water color would suggest an input of allochthonous organic carbon into the pelagic consumers. The incorporation of the dissolved allochthonous material into higher trophic levels is likely favored by the bacterivorous behavior of planktonic organisms, mixotrophic flagellates and ciliates, which dominate the pelagic food webs of these Patagonian lakes. Morphometric aspects, mainly the higher water residence time, led to lower values of allochthony in Moreno East compared to Moreno West, probably accentuated by its upper position in the lake chain. Overall, our results suggest that these allochthonous signals can bring insight into the magnitude of the interaction between terrestrial environments and lake ecosystems, even in extremely clear and ultraoligotrophic systems, such as the Andean Patagonian lakes.

Mercury in an ultraoligotrophic North Patagonian Andean lake (Argentina): concentration patterns in different components of the water column.

The deep, ultraoligotrophic piedmont lakes of Northern Patagonia (Argentina) are located in pristine and barely impacted areas, along a wide latitudinal range. Several studies have reported moderate to high total mercury (Hg) concentrations and contrasting methylmercury (CH3Hg+) production in different lake compartments. Sources of Hg for western Patagonian terrestrial and aquatic ecosystems are still not clear; while point sources can be ruled out and atmospheric deposition is a plausible source, along with contribution from active volcanic areas of the Andes. In this investigation, we reported a noticeably seasonal, spatial (between lake branches), and vertical (between water column strata) heterogeneity in the total Hg concentrations found in the pelagic zone of Lake Moreno. Sterile water samples taken in a depth profile of the lake showed moderate to high concentrations of CH3Hg+ in autumn with a decreasing trend with depth. Our results indicated that Hg is largely allocated in the plankton fraction between 10-53 microm; which dominated within the euphotic (epilimnetic) zone of the lake due to the high densities attained by two species of the dinoflagellate Gymnodinium. The 53-200 microm planktonic size fraction (comprising rotifers, ciliates and immature stages of crustaceans) and the > 200 microm fraction (calanoid copepods and cladocerans) were found to bear strikingly lower total Hg concentrations, suggesting that the magnification of Hg at the planktonic consumer level is negligible.

Mercury and selenium in the food web of Lake Nahuel Huapi, Patagonia, Argentina

Despite located far from point sources of Hg pollution, high concentrations were recorded in plankton from the deep oligotrophic Lake Nahuel Huapi, located in North Patagonia. Native and introduced top predator fish with differing feeding habits are a valuable economic resource to the region. Hence, Hg and Se trophic interactions and pathways to these fish were assessed in the food web of this lake at three sites, using stable nitrogen and carbon isotopes. As expected based on the high THg in plankton, mercury did not biomagnify in the food web of Lake Nahuel Huapi, as most of the THg in plankton is in the inorganic form. As was observed in other aquatic systems, Se did not biomagnify either. When trophic pathways to top predator fish were analyzed, they showed that THg biomagnified in the food chains of native fish but biodiluted in the food chains of introduced salmonids. A more benthic diet, typical of native fish, resulted in higher [THg] bioaccumulation than a more pelagic or mixed diet, as in the case of introduced fish. Se:THg molar ratios were higher than 1 in all the fish species, indicating that Se might be offering a natural protection against Hg toxicity.