Trace elements in sediments and plankton from two high-altitude lakes in a volcanic area from North Patagonia, Argentina.

This study analyzes the distribution of nine potentially toxic trace elements (arsenic, antimony, bromine, cobalt, chromium, mercury, rubidium, selenium, and zinc) in sediments and plankton from two small mesotrophic lakes in a non-industrialized area impacted by the Caviahue-Copahue volcanic complex (CCVC). The two lakes have different plankton community structures and received different amounts of pyroclastic material after the last CCVC eruption. Trace element concentrations of surface sediments differed between lakes, according to the composition of the volcanic ashes deposited in the lakes. The size of organisms was the principal factor influencing the accumulation of most trace elements in plankton within each lake, being trace element concentrations generally higher in the microplankton than in the mesozooplankton. The planktonic biomass in the shallower lake was dominated by small algae and copepods, while mixotrophic ciliates and different-sized cladocerans dominated the deeper lake. These differences in the community structure and species composition influenced the trace element bioaccumulation, especially in microplankton, while habitat use and feeding strategies seem more relevant in mesozooplankton bioaccumulation. This work contributes to the scarce records of trace elements and their dynamics in plankton from freshwater ecosystems impacted by volcanic activity.

Calibration Approach for Gaseous Oxidized Mercury Based on Nonthermal Plasma Oxidation of Elemental Mercury.

Atmospheric mercury measurements carried out in the recent decades have been a subject of bias largely due to insufficient consideration of metrological traceability and associated measurement uncertainty, which are ultimately needed for the demonstration of comparability of the measurement results. This is particularly challenging for gaseous HgII species, which are reactive and their ambient concentrations are very low, causing difficulties in proper sampling and calibration. Calibration for atmospheric HgII exists, but barriers to reliable calibration are most evident at ambient HgII concentration levels. We present a calibration of HgII species based on nonthermal plasma oxidation of Hg0 to HgII. Hg0 was produced by quantitative reduction of HgII in aqueous solution by SnCl2 and aeration. The generated Hg0 in a stream of He and traces of reaction gas (O2, Cl2, or Br2) was then oxidized to different HgII species by nonthermal plasma. A highly sensitive 197Hg radiotracer was used to evaluate the oxidation efficiency. Nonthermal plasma oxidation efficiencies with corresponding expanded standard uncertainty values were 100.5 ± 4.7% (k = 2) for 100 pg of HgO, 96.8 ± 7.3% (k = 2) for 250 pg of HgCl2, and 77.3 ± 9.4% (k = 2) for 250 pg of HgBr2. The presence of HgO, HgCl2, and HgBr2 was confirmed by temperature-programmed desorption quadrupole mass spectrometry (TPD-QMS). This work demonstrates the potential for nonthermal plasma oxidation to generate reliable and repeatable amounts of HgII compounds for routine calibration of ambient air measurement instrumentation.

Validating an Evaporative Calibrator for Gaseous Oxidized Mercury.

Understanding atmospheric mercury chemistry is the key for explaining the biogeochemical cycle of mercury and for improving the predictive capability of computational models. Increased efforts are being made to ensure comparable Hg speciation measurements in the air through establishing metrological traceability. While traceability for elemental mercury has been recently set, this is by no means the case for gaseous oxidized mercury (GOM). Since a calibration unit suitable for traceable GOM calibrations based on evaporation of HgCl2 solution was recently developed, the purpose of our work was to extensively evaluate its performance. A highly specific and sensitive 197Hg radiotracer was used for validation over a wide range of concentrations. By comparing experimental and calculated values, we obtained recoveries for the calibration unit. The average recoveries ranged from 88.5% for 1178 ng m-3 HgCl2 gas concentration to 39.4% for 5.90 ng m-3 HgCl2 gas concentration. The losses were due to the adsorption of oxidized Hg on the inner walls of the calibrator and tubing. An adsorption isotherm was applied to estimate adsorption enthalpy (ΔHads); a ΔHads value of -12.33 kJ mol-1 was obtained, suggesting exothermal adsorption. The results of the calibrator performance evaluation suggest that a newly developed calibration unit is only suitable for concentrations of HgCl2 higher than 1 µg m-3. The concentration dependence of recoveries prevents the system from being used for calibration of instruments for ambient GOM measurements. Moreover, the previously assessed uncertainty of this unit at µg m-3 level (2.0%, k = 2) was re-evaluated by including uncertainty related to recovery and was found to be 4.1%, k = 2. Calibrator performance was also evaluated for HgBr2 gas calibration; the recoveries were much lower for HgBr2 gas than for HgCl2 gas even at a high HgBr2 gas concentration (>1 µg m-3). As HgBr2 is often used as a proxy for various atmospheric HgBr species, the suitability of the unit for such calibration must be further developed.

Trace elements in subantarctic false killer whale (Pseudorca crassidens) tissues, including the skin as an offshore bioindicator.

On a global scale, cetaceans are recognized well indicators of marine ecosystem health. Trace elements accumulate in their bodies and potentially constitute a toxicological threat. Here, the concentrations of essential Se; unknown physiological elements Br, Rb, Cs, Ni, and Sr; and pollutants arsenic, Cd, Hg, and Ag were assessed in the skin of false killer whales (Pseudorca crassidens) stranded at Estrecho de Magallanes, South America, and next, tissue comparisons and relationships between elemental concentrations in the skin and internal tissues (liver, kidney, spleen, lung, skeletal muscle, and testis) were assessed. Results showed elemental concentration variations among tissues. Selenium concentration was found to be higher in the liver 398 (75) µg g-1 dry weight (DW) (standard deviation in parenthesis), followed by skin. Rubidium and Br concentrations were higher in testis 7.92 (0.42) and 99.1 (5.4) µg g-1 DW, respectively, and Cs in muscle 0.36 (0.12) µg g-1 DW, while Ni concentrations range (<0.05-0.91 µg g-1 DW) did not show differences among tissues. Cadmium and arsenic were found to be higher in kidneys, 71.2 (17.6) and 2.54 (1.77) µg g-1 DW, respectively, while Hg was highest in the liver 1068 (234) µg g-1 DW. Concerning inter-tissue relationships, a positive skin-to-kidney and skin-to-muscle correlations were observed for Cs concentrations, and also Hg showed positive skin-to-spleen, skin-to-kidney, and skin-to-testis correlations, which support its use as potential offshore marine biomonitor.

Stranded false killer whales, Pseudorca crassidens, in Southern South America reveal potentially dangerous silver concentrations.

Silver (Ag) is a non-essential metal known to bioaccumulate in aquatic organisms. We determined Ag concentrations in five false killer whales stranded in South America. Silver concentrations (in dry weight basis) range as 6.62-10.78 µg g-1 in liver, 0.008-7.41 µg g-1 in spleen, 0.004-5.71 µg g-1 in testis, 0.757-1.69 µg g-1 in kidney, 0.011-0.078 µg g-1 in lung and < 0.01-0.038 µg g-1 in muscle, whereas in the single samples of uterus and ovary were 0.051 and 0.023 µg g-1; respectively. Overall, Ag concentration in liver and kidney exceeded the cetacean toxic thresholds, proposed as "unhealthy concentrations" and "critically dangerous" in liver and kidney. These results warrant further eco-toxicological studies, to examine biological effects of elevated silver levels for individuals and to assess the species' conservation status with respect to marine pollution.

The microbial mercury link in oligotrophic lakes: Bioaccumulation by picocyanobacteria in natural gradients of dissolved organic matter.

Andean Patagonian lakes are oligotrophic systems characterized by low dissolved organic carbon (DOC) levels and moderate to high Hg concentration that determine naturally high Hg/DOC ratios and bioavailability. In these lakes, microbial food webs are extremely important in Hg trophodynamics, being that the picophytoplankton fraction is a major entrance path of Hg2+ into pelagic food webs. This study analyzed the bioaccumulation of Hg2+ by the picocyanobacteria Synechococcus sp. using the radiotracer 197Hg2+ and water from four Andean Patagonian lakes presenting a natural gradient of DOM concentration and quality. Hg2+ bioaccumulation by Synechococcus was calculated as the uptake of Hg2+ per biovolume unit (volume concentration factor VCF; pL µm-3). Hg uptake showed a wide variation (13 < VCF< 300 pL µm-3) in the natural DOC gradient tested (0.7-4 mg L-1; Hg2+/DOC ratio: 1.8-14 ng mg-1). The bioaccumulation of Hg2+ in Synechococcus decreased exponentially with DOC concentration. Differences in the quality of dissolved organic matter (DOM) among lake water influenced also Hg2+ bioaccumulation. Naturally degraded DOM, with low molecular weight/size, promoted higher Hg uptakes in Synechococcus compared to humic DOM, rich in high molecular weight/size aromatic compounds, that retained Hg in the dissolved phase. In Andean Patagonian lakes picocyanobacteria are pivotal organisms in the Hg cycling, taking dissolved Hg2+ and transferring it to pelagic food webs, as well as fueling the benthic Hg pathway through sedimentation.

Zinc in an ultraoligotrophic lake food web.

Zinc (Zn) bioaccumulation and trophic transfer were analyzed in the food web of Lake Nahuel Huapi, a deep, unpolluted ultraoligotrophic system in North Patagonia. Benthic macroinvertebrates, plankton, and native and introduced fish were collected at three sites. The effect of pyroclastic inputs on Zn levels in lacustrine food webs was assessed by studying the impact of the eruption of Puyehue-Cordón Caulle volcanic complex (PCCVC) in 2011, by performing three sampling campaigns immediately before and after the PCCVC eruption, and after 2 years of recovery of the ecosystem. Zinc trophodynamics in L. Nahuel Huapi food web was assessed using nitrogen stable isotopes (δ15N). There was no significant increase of Zn concentrations ([Zn]) in L. Nahuel Huapi biota after the PCCVC eruption, despite the evidence of [Zn] increase in lake water that could be associated with volcanic ash leaching. The organisms studied exhibited [Zn] above the threshold level considered for dietary deficiency, regulating Zn adequately even under a catastrophic situations like PCCVC 2011 eruption. Zinc concentrations exhibited a biodilution pattern in the lake's food web. To the best of our knowledge, present research is the first report of Zn biodilution in lacustrine systems, and the first to study Zn transfer in a freshwater food web including both pelagic and benthic compartments.

Inorganic mercury (Hg2+) accumulation in autotrophic and mixotrophic planktonic protists: Implications for Hg trophodynamics in ultraoligotrophic Andean Patagonian lakes.

Microbial assemblages are typical of deep ultraoligotrophic Andean Patagonian lakes and comprise picoplankton and protists (phytoflagellates and mixotrophic ciliates), having a central role in the C cycle, primary production and in the incorporation of dissolved inorganic mercury (Hg2+) into lake food webs. In this study we evaluated the mechanisms of Hg2+ incorporation in hetero- and autotrophic bacteria, in the autotrophic dinoflagellate (Gymnodinium paradoxum) and in two mixotrophic ciliates (Stentor araucanus and Ophrydium naumanni) dominating the planktonic microbial assemblage. The radioisotope 197Hg was used to trace the Hg2+ incorporation in microbiota. Hg uptake was analyzed as a function of cell abundance (BCF: bioconcentration factor), cell surface (SCF: surface concentration factor) and cell volume (VCF: volume concentration factor). Overall, the results obtained showed that these organisms incorporate substantial amounts of dissolved Hg2+ passively (adsorption) and actively (bacteria consumption or attachment), displaying different Hg internalization and therefore, varying potential for Hg transfer. Surface area and quality, and surface:volume ratio (S:V) control the passive uptake in all the organisms. Active incorporation depends on bacteria consumption in the mixotrophic ciliates, or on bacteria association to surface in the autotrophic dinoflagellate. Hg bioaccumulated by pelagic protists can be transferred to higher trophic levels through plankton and fish feeding, regenerated to the dissolved phase by excretion, and/or transferred to the sediments by particle sinking. In ultraoligotrophic Andean Patagonian lakes, picoplankton and planktonic protists are key components of lake food webs, linking the pelagic and benthic Hg pathways, and thereby playing a central role in Hg trophodynamics.

Mercury in a stream-lake network of Andean Patagonia (Southern Volcanic Zone): Partitioning and interaction with dissolved organic matter.

Lake Nahuel Huapi (NH) is a large, ultraoligotrophic deep system located in Nahuel Huapi National Park (NHNP) and collecting a major headwater network of Northwestern Patagonia (Argentina). Brazo Rincón (BR), the westernmost branch of NH, is close to the active volcanic formation Puyehue-Cordón Caulle. In BR, aquatic biota and sediments display high levels of total Hg (THg), ranging in contamination levels although it is an unpolluted region. In this survey, Hg species and fractionation were assessed in association with dissolved organic matter (DOM) in several aquatic systems draining to BR. THg varied between 16.8 and 363 ng L-1, with inorganic Hg (Hg2+) contributing up to 99.8% and methyl mercury (MeHg) up to 2.10%. DOC levels were low (0.31-1.02 mg L-1) resulting in high THg:DOC and reflecting in high Hg2+ availability for binding particles (partitioning coefficient log Kd up to 6.03). In streams, Hg fractionation and speciation related directly with DOM terrestrial prints, indicating coupled Hg-DOM inputs from the catchment. In the lake, DOM quality and photochemical and biological processing drive Hg fractionation, speciation and vertical levels. Dissolved gaseous Hg (Hg0) reached higher values in BR (up to 3.8%), particularly in upper lake layers where solar radiation enhances the photoreduction of Hg2+ and Hg-DOM complexes. The environmental conditions in BR catchment promote Hg2+ binding to abiotic particles and bioaccumulation and the production of Hg0, features enhancing Hg mobilization among ecosystem compartments. Overall, the aquatic network studied can be considered a "natural Hg hotspot" within NHNP.

Species- and habitat-specific bioaccumulation of total mercury and methylmercury in the food web of a deep oligotrophic lake.

Niche segregation between introduced and native fish in Lake Nahuel Huapi, a deep oligotrophic lake in Northwest Patagonia (Argentina), occurs through the consumption of different prey. Therefore, in this work we analyzed total mercury [THg] and methylmercury [MeHg] concentrations in top predator fish and in their main prey to test whether their feeding habits influence [Hg]. Results indicate that [THg] and [MeHg] varied by foraging habitat and they increased with greater percentage of benthic diet and decreased with pelagic diet in Lake Nahuel Huapi. This is consistent with the fact that the native creole perch, a mostly benthivorous feeder, which shares the highest trophic level of the food web with introduced salmonids, had higher [THg] and [MeHg] than the more pelagic feeder rainbow trout and bentho-pelagic feeder brown trout. This differential THg and MeHg bioaccumulation observed in native and introduced fish provides evidence to the hypothesis that there are two main Hg transfer pathways from the base of the food web to top predators: a pelagic pathway where Hg is transferred from water, through plankton (with Hg in inorganic species mostly), forage fish to salmonids, and a benthic pathway, as Hg is transferred from the sediments (where Hg methylation occurs mostly), through crayfish (with higher [MeHg] than plankton), to native fish, leading to one fold higher [Hg].

Variations in anthropogenic silver in a large Patagonian lake correlate with global shifts in photographic processing technology.

At the beginning of the 21st century, digital imaging technology replaced the traditional silver-halide film photography which had implications in Ag contamination. Lake Nahuel Huapi is a popular Patagonia tourist destination impacted by municipal silver (Ag) contamination from photographic processing facilities since 1990's. Silver concentrations in a dated sediment core from the lake bottom showed a 10-fold increase above background levels in the second half of the 20th century, then a decrease. This trend corresponds well with published annual global photography industry demand for Ag, which clearly shows the evolution and replacement of the traditional silver-halide film photography by digital imaging technology. There were significant decreases in Ag concentrations in sediments, mussels and fish across the lake between 1998 and 2011. Lower trophic organisms had variable whole-body Ag concentrations, from 0.2-2.6 µg g-1 dry weight (DW) in plankton to 0.02-3.1 µg g-1 DW in benthic macroinvertebrates. Hepatic Ag concentrations in crayfish, mussels and predatory fish were significantly elevated relative to muscle which often have Ag concentrations below the detection limit (0.01-0.05 µg g-1 DW). Trophodynamic analyses using δ15N and whole-body invertebrate and muscle Ag concentrations indicated food web biodilution trends. High sedimentation rates in conjunction with the reduction of silver waste products discharged to the lake, as a result of the change to digital image processing technologies, are resulting in unplanned but welcome remediation of the Ag contamination in Lake Nahuel Huapi.

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.

Heavy metal and trace elements in riparian vegetation and macrophytes associated with lacustrine systems in Northern Patagonia Andean Range.

Vegetation associated with lacustrine systems in Northern Patagonia was studied for heavy metal and trace element contents, regarding their elemental contribution to these aquatic ecosystems. The research focused on native species and exotic vascular plant Salix spp. potential for absorbing heavy metals and trace elements. The native species studied were riparian Amomyrtus luma, Austrocedrus chilensis, Chusquea culeou, Desfontainia fulgens, Escallonia rubra, Gaultheria mucronata, Lomatia hirsuta, Luma apiculata, Maytenus boaria, Myrceugenia exsucca, Nothofagus antarctica, Nothofagus dombeyi, Schinus patagonicus, and Weinmannia trichosperma, and macrophytes Hydrocotyle chamaemorus, Isöetes chubutiana, Galium sp., Myriophyllum quitense, Nitella sp. (algae), Potamogeton linguatus, Ranunculus sp., and Schoenoplectus californicus. Fresh leaves were analyzed as well as leaves decomposing within the aquatic bodies, collected from lakes Futalaufquen and Rivadavia (Los Alerces National Park), and lakes Moreno and Nahuel Huapi (Nahuel Huapi National Park). The elements studied were heavy metals Ag, As, Cd, Hg, and U, major elements Ca, K, and Fe, and trace elements Ba, Br, Co, Cr, Cs, Hf, Na, Rb, Se, Sr, and Zn. Geochemical tracers La and Sm were also determined to evaluate contamination of the biological tissues by geological particulate (sediment, soil, dust) and to implement concentration corrections.

Hepatic and renal metallothionein concentrations in Commerson's dolphins (Cephalorhynchus commersonii) from Tierra del Fuego, South Atlantic Ocean.

The Commerson's dolphin is the most common endemic odontocete of subantarctic waters of Tierra del Fuego, Argentina incidentally caught in fishing nets. The species is classified as "Data Deficient" by the IUCN. Metallothioneins (MTs) are considered as suitable biomarkers for health and environmental monitoring. The aims of the study were to assess MT concentrations in the liver and kidney of bycaught specimens. Moreover, correlations with Zn, Se, Cd, Ag and Hg, and the molar ratios of MT:metals were estimated to evaluate if there is an indication of their respective protective role against metal toxicity in tissues. Hepatic and renal MT concentrations were similar, ranging from 11.6 to 29.1nmol·g(-1) WW, and Kidney/Liver ratios ranging from 0.73 to 1.93 corresponded to normal ranges. Results suggest that MTs are related to physiological ranges for the species. This information constitutes the first MT report on Commerson's dolphins and possibly considered as baseline for species' conservation.

Historical records of mercury in southern latitudes over 1600 years: Lake Futalaufquen, Northern Patagonia.

Mercury is released to the environment from natural and anthropogenic sources, and through atmospheric transport is distributed globally. Lake Futalaufquen (42.8°S) is an oligotrophic lake located in Los Alerces National Park (Northern Patagonia), providing a remote and unpolluted study system. A lacustrine sedimentary sequence revealed 1600 years of Hg deposition, identifying natural baselines and marked peaks not correlated with long-range atmospheric transport. Organic matter and catchment erosion were discarded as Hg drivers. Natural background, pre-1300 CE Hg concentrations, ranged between 27 and 47 ng g(-1) (accumulation rates from 8 to 15µg m(-2) y(-1)). From 1300 CE on, the Hg background profile did not follow the generally increasing Hg pattern observed in both Southern and Northern Hemisphere since pre-industrial times. It was not until the last century that a 1.6-fold increase is observed in the Hg accumulation rate, considered among the lowest increments in southern South America. Noteworthy local/regional sources of Hg for this area, along with global transport, are forest fires and volcanic activity. Between approx. 1340 and 1510 CE, sharp increase in Hg concentration and accumulation rate (up to 204 ng g(-1) and 51 µg m(-2) y(-1), respectively) were clearly associated with extended fire episodes. Furthermore, high Hg peaks during the last 300 years were associated with volcanic eruptions in northernmost Patagonia together with fairly irregular fire episodes, caused by anthropogenic burning by settling population in the Andes.

The skin of Commerson's dolphins (Cephalorhynchus commersonii) as a biomonitor of mercury and selenium in Subantarctic waters.

The skin of bycaught Commerson's dolphins was tested for mercury (Hg) and selenium (Se) biomonitoring in Subantarctic environments. The correlation of levels detected in the skin with those found in internal tissues - lung, liver, kidney and muscle - was assessed to evaluate how skin represents internal Hg and Se distribution for monitoring purposes. Mercury in skin had a concentration range of 0.68-3.11 µg g(-1) dry weight (DW), while Se had a higher concentration range of 74.3-124.5 µg g(-1) DW. There was no significant correlation between selenium levels in any of the analyzed tissues. Thus, the skin selenium concentration did not reflect the tissular Se levels and did not provide information for biomonitoring. The lack of correlation is explained by the biological role of Se, provided that each tissue regulates Se levels according to physiological needs. However, the skin Hg level had significant positive correlation with the levels in internal tissues (ANOVA p<0.05), particularly with that of muscle (R(2)=0.79; ANOVA p=0.0008). Thus, this correlation permits the estimation of Hg content in muscle based on the multiplication of skin biopsy levels by a factor of 1.85. Mercury bioindication using skin biopsies is a non-lethal approach that allows screening of a large number of specimens with little disturbance and makes possible an adequate sampling strategy that produces statistically valid results in populations and study areas. The correlation between Hg levels in the skin and internal tissues supports the use of the epidermis of Commerson's dolphins for Hg biomonitoring in the waters of the Subantarctic, which is a poorly studied region regarding Hg levels, sources and processes.

Incorporation of inorganic mercury (Hg²âº) in pelagic food webs of ultraoligotrophic and oligotrophic lakes: the role of different plankton size fractions and species assemblages.

In lake food webs, pelagic basal organisms such as bacteria and phytoplankton incorporate mercury (Hg(2+)) from the dissolved phase and pass the adsorbed and internalized Hg to higher trophic levels. This experimental investigation addresses the incorporation of dissolved Hg(2+) by four plankton fractions (picoplankton: 0.2-2.7 µm; pico+nanoplankton: 0.2-20 µm; microplankton: 20-50 µm; and mesoplankton: 50-200 µm) obtained from four Andean Patagonian lakes, using the radioisotope (197)Hg(2+). Species composition and abundance were determined in each plankton fraction. In addition, morphometric parameters such as surface and biovolume were calculated using standard geometric models. The incorporation of Hg(2+) in each plankton fraction was analyzed through three concentration factors: BCF (bioconcentration factor) as a function of cell or individual abundance, SCF (surface concentration factor) and VCF (volume concentration factor) as functions of individual exposed surface and biovolume, respectively. Overall, this investigation showed that through adsorption and internalization, pico+nanoplankton play a central role leading the incorporation of Hg(2+) in pelagic food webs of Andean lakes. Larger planktonic organisms included in the micro- and mesoplankton fractions incorporate Hg(2+) by surface adsorption, although at a lesser extent. Mixotrophic bacterivorous organisms dominate the different plankton fractions of the lakes connecting trophic levels through microbial loops (e.g., bacteria-nanoflagellates-crustaceans; bacteria-ciliates-crustaceans; endosymbiotic algae-ciliates). These bacterivorous organisms, which incorporate Hg from the dissolved phase and through their prey, appear to explain the high incorporation of Hg(2+) observed in all the plankton fractions.

A compilation of field surveys on gaseous elemental mercury (GEM) from contrasting environmental settings in Europe, South America, South Africa and China: separating fads from facts.

Mercury is transported globally in the atmosphere mostly in gaseous elemental form (GEM, [Formula: see text]), but still few worldwide studies taking into account different and contrasted environmental settings are available in a single publication. This work presents and discusses data from Argentina, Bolivia, Bosnia and Herzegovina, Brazil, Chile, China, Croatia, Finland, Italy, Russia, South Africa, Spain, Slovenia and Venezuela. We classified the information in four groups: (1) mining districts where this contaminant poses or has posed a risk for human populations and/or ecosystems; (2) cities, where the concentration of atmospheric mercury could be higher than normal due to the burning of fossil fuels and industrial activities; (3) areas with natural emissions from volcanoes; and (4) pristine areas where no anthropogenic influence was apparent. All the surveys were performed using portable LUMEX RA-915 series atomic absorption spectrometers. The results for cities fall within a low GEM concentration range that rarely exceeds 30 ng m(-3), that is, 6.6 times lower than the restrictive ATSDR threshold (200 ng m(-3)) for chronic exposure to this pollutant. We also observed this behavior in the former mercury mining districts, where few data were above 200 ng m(-3). We noted that high concentrations of GEM are localized phenomena that fade away in short distances. However, this does not imply that they do not pose a risk for those working in close proximity to the source. This is the case of the artisanal gold miners that heat the Au-Hg amalgam to vaporize mercury. In this respect, while GEM can be truly regarded as a hazard, because of possible physical-chemical transformations into other species, it is only under these localized conditions, implying exposure to high GEM concentrations, which it becomes a direct risk for humans.

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.

Heavy metals and essential elements in Commerson's dolphins (Cephalorhynchus c. commersonii) from the southwestern South Atlantic Ocean.

A survey of the elemental contents of K, Mg, Mn, Na, Cl, Br, Cs, Co, Rb, Fe, Zn, Al, Ti, V, As, Ag, Au and Cd in liver, kidney and muscle was performed in specimens of Commerson's dolphins (Cephalorhynchus c. commersonii) from subantarctic waters. The concentrations were determined by Instrumental Neutron Activation Analysis and the specimens derives from animals incidentally caught in artisanal fishing nets. Liver had the highest concentrations of Fe, 897(79) µg g(-1) DW (dry weight) (average; standard deviation in parenthesis), kidney had the highest Cd, 35 (24) µg g(-1) DW; Cl, 9,200 (1,700) µg g(-1) DW; Na, 6,800 (1,100) µg g(-1) DW and Br, 73(12) µg g(-1) DW; and muscle the highest Mg 954 (71) µg g(-1) DW. Potassium and Cs concentrations in muscle and kidney ranged in 12,510-13,020 and 0.230-0.252 µg g(-1) DW, respectively; Zn and Mn concentrations were similar in liver and kidney (117-122.1 and 3.66-16.5 µg g(-1) DW, respectively). Silver was high in liver 5.4(5.0) µg g(-1) DW and kidney 1.2(2.7) µg g(-1) DW. Gold, Rb, Co and As had no differences among tissues. Likewise, as in other odontocete species, the concentrations of essential elements showed little variation between the specimens analyzed, since they are regulated biochemically; however, heavy metals showed high variability. This study constitutes the first large description of the elemental composition in Commerson's dolphins from subantarctic waters of the South Atlantic Ocean.