An Arsenic-76 radiotracer to study the routes of assimilation, hemolymph distribution, and tissue inventories in the bioindicator organism Pomacea canaliculata.

The aim of this work was to study the absorption, distribution through the hemolymph, and bioaccumulation of arsenic by the freshwater Pomacea canaliculata using a short-lived tracer (76As, t1/2: 1.07 d) with high specific activity. Arsenic travels mainly dissolved in the plasma of the snail's hemolymph. This element is transferred from the hemolymph to the tissues (87%) 4 h after the inoculation of 50 µL of a 0.04 g/L of 76As radiotracer solution, being the digestive gland, kidney, and head-foot the main places of arsenical inventories. Snails exhibited a rapid arsenic accumulation response in a wide range of concentrations (from 1 to 1000 µg/L) of the metalloid dissolved in water and in a concentration-dependent manner. Also, snails incorporated As from the digestive system when they received a single safe dose of ~2 µg of 76As inoculated in a fish food pellet. The (semi) physiologically based toxicokinetic model developed in this study is based on anatomical and physiological parameters (blood flow, irrigation, tissue volume and other). Together, these findings make P. canaliculata an excellent sentinel organism to evaluate freshwater bodies naturally contaminated with As.

High status of mercury and selenium in false killer whales (Pseudorca crassidens, Owen 1846) stranded on Southern South America: A possible toxicological concern?

The study was carried out to determine Hg and Se concentrations in false killer whales stranded on the Estrecho de Magallanes, Chile, South America. Tissue samples of five mature specimens were analyzed (two females and three males). Mean Hg concentration in liver 1068 (234) µg g-1 dry weight (DW) (standard deviation in parenthesis) was markedly higher than those in kidney 272 (152) µg g-1 DW, lung 423 (325) µg g-1 DW, spleen 725 (696) µg g-1 DW, muscle 118 (94) µg g-1 DW and testicle 18.0 (2.8) µg g-1 DW. Mean Se concentration in liver, 398 (75) µg g-1 DW, was higher than those in kidney 162 (69) µg g-1 DW, lung 128 (84) µg g-1 DW, spleen 268 (245) µg g-1 DW, muscle 47 (38) µg g-1 DW and testicle 25.4 (2.1) µg g-1 DW. Positive correlations were found between Hg and Se molar concentrations in muscle, lung, spleen and kidney. Molar ratio of Se/Hg in liver, lung and muscle were <1, but those in kidney and testicle were markedly >1 suggesting a Se protection against Hg toxicity. In all the examined specimens Hg values exceeded the toxic thresholds defined for hepatic damage in marine mammals, with Se/Hg molar ratios below 1 implying limited protective action of Se. Generally, our results showed that individuals are carrying a significant burden, reflecting a high exposure to this toxic metal. This constitutes the first report on Hg and Se levels for a large subantarctic odontocete in South America region, providing insights into their contamination status and with information to the understanding of possible impacts on wild populations.

Bioindication of mercury, arsenic and uranium in the apple snail Pomacea canaliculata (Caenogastropoda, Ampullariidae): Bioconcentration and depuration in tissues and symbiotic corpuscles.

Pomacea canaliculata is a mollusk potentially useful as a biomonitor species of freshwater quality. This work explores the ability of snail tissues and symbiotic corpuscles to bioconcentrate and depurate mercury, arsenic, and uranium. Adult snails cultured in metal-free reconstituted water were exposed for eight weeks (bioaccumulation phase) to water with Hg (2 µgL-1), As (10 µgL-1), and U (30 µgL-1) and then returned to the reconstituted water for other additional eight weeks (depuration phase). Elemental concentrations in digestive gland, kidney, symbiotic corpuscles and particulate excreta were determined by neutron activation analysis. The glandular symbiotic occupancy was measured by morphometric analysis. After exposure, the kidney showed the highest concentration of Hg, while the digestive gland accumulated mainly As and U. The subcellular distribution in symbiotic corpuscles was ∼71%, ∼48%, and ∼11% for U, Hg, and As, respectively. Tissue depuration between weeks 8 and 16 was variable amongst elements. At week 16, the tissue depuration of U was the highest (digestive gland = 92%; kidney = 80%), while it was lower for Hg (digestive gland = 51%; kidney = 53%). At week 16, arsenic showed a differential pattern of tissue depuration (digestive gland = 23%; kidney = 88%). The symbiotic detoxification of the three elements in excreta was fast between weeks 8 and 10 and it was slower after on. At the end of the depuration, each element distributed differentially in digestive gland and symbiotic corpuscles. Our findings show that symbiotic corpuscles, digestive gland and kidney P. canaliculata are sensitive places for biomonitoring of Hg, As and U.

Silver bioaccumulation in chironomid larvae as a potential source for upper trophic levels: a study case from northern Patagonia.

Silver (Ag) is a pollutant of high concern in aquatic ecosystems, considered among the most toxic metallic ions. In lacustrine environments, contaminated sediments are a source of Ag for the food web. Chironomidae (Insecta: Diptera) are the most abundant, diverse, and representative insect groups in aquatic ecosystems. Chironomid larvae are closely associated to benthic substrates and link primary producers and secondary consumers. Given their trophic position and their life habits, these larvae can be considered the entry point for the transference of Ag, from the benthic deposit to the higher trophic levels of the food web. Previous studies in lakes from Nahuel Huapi National Park (Northern Patagonia) showed Ag enrichment over background levels (0.04-0.1 µg g-1 dry weight) both in biota (bivalves and fish liver) and sediments from sites near human settlements. The aim of this study was to analyze the role of chironomids in the transference of Ag from the benthic reservoir of Lake Moreno Oeste to the food web. The concentration of Ag in chironomid larvae tissue ranged from 0.1 to 1.5 µg g-1 dry weight, reaching a bioaccumulation factor up to 17 over substrates and depending on the associated substrate type, feeding habitats, larval stage, and season. The main Ag transfer to higher trophic levels by chironomids occurs in the littoral zone, mostly from larvae inhabiting submerged vegetation (Myriophyllum quitense) and sediment from vegetated zones. This study presents novel evidence of the doorway role played by chironomid larvae in Ag pathways from the sediments into food webs of freshwater ecosystems.

Natural origin arsenic in aquatic organisms from a deep oligotrophic lake under the influence of volcanic eruptions.

Volcanic eruptions are recognized sources of toxic elements to freshwater, including arsenic (As). In order to study the short term changes in the bioaccumulation of naturally occurring As by aquatic organisms in Lake Nahuel Huapi (Argentina), located close to the Puyehue-Cordón Caulle volcanic complex (PCCVC), we described As concentrations at different trophic levels and food web transfer patterns in three sites of the lake prior to the last PCCVC eruption (June 2011), and compared As concentrations in biota before and after the eruption. The highest As concentrations and greater variations both between sites and position in the water column, were observed in phytoplankton (3.9-64.8 µg g(-1) dry weight, DW) and small zooplankton (4.3-22.3 µg g(-1) DW). The pattern of As accumulation in aquatic organisms (whole body or muscle) was: primary producers (phytoplankton) > scrapper mollusks (9.3-15.3 µg g(-1) DW) > filter feeding mollusks (5.4-15.6 µg g(-1) DW) > omnivorous invertebrates (0.4-9.2 µg g(-1) DW) > zooplankton (1.2-3.5 µg g(-1) DW) > fish (0.2-1.9 µg g(-1) DW). We observed As biodilution in the whole food web, and in salmonids food chains, feeding on fish prey; but biomagnification in the food chain of creole perch, feeding on benthic crayfish. The impact of the 2011 PCCVC eruption on the As levels of biota was more evident in pelagic-associated organisms (zooplankton and planktivorous fish), but only in the short term, suggesting a brief high bioavailability of As in water after ash deposition. In benthic organisms As variations likely responded to shift in diet due to coverage of the littoral zone with ashes.

Source and trophic transfer of mercury in plankton from an ultraoligotrophic lacustrine system (Lake Nahuel Huapi, North Patagonia).

The incorporation and trophic transfer of total and methyl mercury (THg, MeHg) were examined in three size classes of plankton (10-53, 53-200, and >200 µm size range) and a small planktivorous fish, Galaxias maculatus, from the large multi-branched Lake Nahuel Huapi (North Patagonia, Argentina). Three sites representing a large range of lake benthic-pelagic structures (based on depth and shoreline characteristics) and precipitation regimes were sampled. Nitrogen and carbon stable isotopes (δ(15)N, δ(13)C) were analyzed to assess Hg trophodynamics. Selenium concentrations were determined together with THg in order to consider its potential effect on Hg trophodynamics. High THg concentrations (0.1-255 µg g(-1) dry weight (DW)) were measured in plankton, largely in inorganic form (MeHg: 3-29 ng g(-1) DW, 0.02-7% of THg, in the two larger size classes). A trend of increasing THg concentrations, varying in two to three orders of magnitude, with decreasing plankton size was associated with precipitation measured prior to each sampling event. Passive adsorption of dissolved Hg(2+) from wet deposition and runoff is considered to be the principal Hg uptake mechanism at the base of the pelagic food web. Despite the initially high THg uptake in the smaller plankton classes, the transfer to G. maculatus, and consequently to the entire food web, is likely limited due to low proportion of MeHg to THg in plankton. Furthermore, evidence of G. maculatus with benthic feeding habits having higher impact on MeHg trophic transfer compared to the same species with more pelagic (e.g., zooplankton) feeding habits, was observed. Although there is a high THg uptake in plankton, limited amounts are incorporated in the entire food web from the pelagic compartment.

Mercury and selenium in subantarctic Commerson's dolphins (Cephalorhynchus c. commersonii).

Total mercury (THg) and selenium (Se) concentrations were determined in hepatic, renal, and muscle tissues of seven specimens of Commerson's dolphins incidentally captured in artisanal fisheries of Tierra del Fuego, Argentina, by instrumental neutron activation analysis. Liver yielded the mean highest concentration of THg 9.40 (9.92) µg g(-1) dry weight (DW) (standard deviation of the average in parenthesis); kidney and muscle showed similar values, ranging from 2.34 to 3.63 µg g(-1) DW. Selenium concentrations were similar in hepatic and renal tissues, with values from 13.62 to 14.56 µg g(-1) DW; the lowest concentration was observed in muscle, 4.13 (2.05) µg g(-1) DW. Among the specimens analyzed, the maximum concentrations of THg and Se were observed in the single adult female studied. An increasing age trend is observed for THg concentrations in tissues analyzed. The molar ratio of Se/Hg in the hepatic, renal, and muscle tissues were 8.7 (9.6), 13.2 (9.5), and 9.0 (11.4), respectively, suggesting Se protection against Hg toxicity. Silver concentrations in the three tissues were included, and the Se/(Hg + 0.5×Ag) molar ratio showed values closer to 1. Both Hg and Se concentrations in liver and kidney were comparable to those found in other small odontocetes from Argentine and Brazilian waters. This study constitutes the first joint description reported of Hg and Se concentrations in liver, kidney, and muscle of the Commerson's dolphin species.

Influence of dissolved organic matter character on mercury incorporation by planktonic organisms: an experimental study using oligotrophic water from Patagonian lakes.

Ligands present in dissolved organic matter (DOM) form complexes with inorganic divalent mercury (Hg2+) affecting its bioavailability in pelagic food webs. This investigation addresses the influence of a natural gradient of DOM present in Patagonian lakes on the bioaccumulation of Hg2+ (the prevailing mercury species in the water column of these lakes) by the algae Cryptomonas erosa and the zooplankters Brachionus calyciflorus and Boeckella antiqua. Hg2+ accumulation was studied through laboratory experiments using natural water of four oligotrophic Patagonian lakes amended witht'97Hg2+. The bioavailability of Hg2+ was affected by the concentration and character of DOM. The entrance of Hg2+ into pelagic food webs occurs mostly through passive and active accumulation. The incorporation of Hg2+ by Cryptomonas, up to 27% of the Hg2+ amended, was found to be rapid and dominated by passive adsorption, and was greatest when low molecular weight compounds with protein-like or small phenolic signatures prevailed in the DOM. Conversely, high molecular weight compounds with a humic or fulvic signature kept Hg2+ in the dissolved phase, resulting in the lowest Hg2+ accumulation in this algae. In Brachionus and Boeckella the direct incorporation of Hg from the aqueous phase was up to 3% of the Hg2+ amended. The dietary incorporation of Hg2+ by Boeckella exceeded the direct absorption of this metal in natural water, and was remarkably similar to the Hg2+ adsorbed in their prey. Overall, DOM concentration and character affected the adsorption of Hg2+ by algae through competitive binding, while the incorporation of Hg2+ into the zooplankton was dominated by trophic or dietary transfer.

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 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.

Comment on the article 'Radionuclide dating (Pb-210, Cs-137, Am-241) of recent lake sediments in a highly active geodynamic setting (Lakes Puyehue and Icalma-Chilean Lake District)'.

The correlation of Cs-137 specific activity profiles with the historical fallout sequence in the study region is essential in sediment cores dating using this technique. The authors of the referenced article considered 1965 the end of Cs-137 fallout in the study region, omitting the South Pacific nuclear test from 1966 to 1974, proved that generated the most intense Cs-137 fallout.

Methodological considerations regarding the use of inorganic 197Hg(II) radiotracer to assess mercury methylation potential rates in lake sediment.

Methodological considerations on the determination of benthic methyl-mercury (CH(3)Hg) production potentials were investigated on lake sediment, using (197)Hg radiotracer. Three methods to arrest bacterial activity were compared: flash freezing, thermal sterilization, and gamma-irradiation. Flash freezing showed similar CH(3)Hg recoveries as thermal sterilization, which was both 50% higher than the recoveries obtained with gamma-ray irradiation. No additional radiolabel was recovered in kill-control samples after an additional 24 or 65 h of incubation, suggesting that all treatments were effective at arresting Hg(II)-methylating bacterial activity, and that the initial recoveries are likely due to non-methylated (197)Hg(II) carry-over in the organic extraction and/or [(197)Hg]CH(3)Hg produced via abiotic reactions. Two CH(3)Hg extraction methods from sediment were compared: (a) direct extraction into toluene after sediment leaching with CuSO(4) and HCl and (b) the same extraction with an additional back-extraction step to thiosulphate. Similar information was obtained with both methods, but the low efficiency observed and the extra work associated with the back-extraction procedure represent significant disadvantages, even tough the direct extraction involves higher Hg(II) carry over.

Silver contamination on abiotic and biotic compartments of Nahuel Huapi National Park lakes, Patagonia, Argentina.

The Ag contents of abiotic and biotic compartments of different lakes of Nahuel Huapi National Park, Patagonia, Argentina were analyzed. The water bodies studied were lakes Nahuel Huapi, Moreno, Escondido, Espejo Chico and Traful, the latter chosen as a reference lake. The Ag concentration profiles of short sediment cores, dated by (210)Pb and (137)Cs techniques, were analyzed, as well as suspended load collected from three sites of lake Nahuel Huapi. The biota studied were the native mussel Diplodon chilensis (digestive gland and total soft tissues pooled samples) and five species of fish, two native and three introduced (liver and muscle pooled samples). Ag contents were determined by Instrumental Neutron Activation Analysis (INAA). The upper layers of the sediment cores sampled in lake Nahuel Huapi were enriched in Ag contents compared to deep layers in accumulation periods corresponding to the second half of the 20th century, but this enrichment was neither observed in the reference lake Traful, nor in lakes Espejo Chico and Escondido. Ag was enriched over background level (0.1 microg g(-1)) also in suspended load collected in lake Nahuel Huapi. Ag fluxes to sediments were computed for suspended load and enriched sediment core layers. Highest Ag fluxes, from 350 to 470 microg m(-2) year(-1), were measured in Nahuel Huapi near the site where the liquid effluents of the Bariloche city sewage treatment plant are released to the lake. The spatial distribution of the other Ag fluxes suggests that this is the main source of Ag to lake Nahuel Huapi and lateral transport occurs within the water body. Ag concentrations on biota samples were consistent with these conclusions. Mussels collected in lake Nahuel Huapi showed higher Ag concentrations than in the other lakes, especially when compared to lake Traful. Ag contents in mussels were strongly associated with sediment intake, but enriched probably due to sediment grain size sorting during the intake processes. Evidence of food chain biomagnification of Ag in fish liver was observed. Ag contents in fish liver were higher at lake Nahuel Huapi even considering the high intra-specific variability, with highest values ranging from 10 to 29 microg g(-1) dry weight for brown trout and rainbow trout.

Distribución de Paratión y Mercurio y Biomarcadores de efecto en la exposicióon de Cyprinus Carpio a concentraciones subletales / Distribution of parathion and mercury and biomarkers of effect in Cyprinus carpio exposed to sublethal concentrations

Se avaluó la distribución de mercurio y paration en carpa (Cyprinus carpio), y su efectos sobre biomarcadores en el hígado y el cerebro en la exposición a niveles subletales; constituye este trabajo una primera aproximación al estudio de la exposición a múltilples contaminantes en los cursos de agua de la región Comahue (Agentina). El insecticida paratión marcado co C se distribuyó en forma órgano-rspecífica en el hígado, con con concerntraciones 6 veces más altas que en otros órganos, mientras que la cumulación de mercurio se produjo más lentamente, principalmente en el hígado y el riñón. El paratión no afectó el índice hepatosomático, los niveles de glutatión, ni la producción de peróxidos lipidsicos; sin embargo, provocó una caída significativa del contenido de proteínas totales en el hígado. La aceticolinesterasa cerebral registró una inhibición pronunciada y significativa a las 24 horas de exposición (86 por ciento). Luego de 96 horas de exposición a mercurio solo se registró un 25 por ciento de inhibición de acetilcolisterasa cerebral. Estos resultados sugiere que si bien la exposición a niveles subletales de ambos tóxicos conduce a una concentración preferencial rn órganops críticos, los parámetros biomarcadores se ven afectados en los órganos diana. Esta situación se manisfesto en la acción neurotóxica de ambos compuestos y corrobora la evidencia de que la inhibición de la aceticolinesterasa no es prpducida solamente por insecticidas anticolinesterásicos, sino que metales tóxicos, como el mercurio, tambien pueden hacerlo.

Distribución de Paratión y Mercurio y Biomarcadores de efecto en la exposicióon de Cyprinus Carpio a concentraciones subletales / Distribution of parathion and mercury and biomarkers of effect in Cyprinus carpio exposed to sublethal concentrations

Se avaluó la distribución de mercurio y paration en carpa (Cyprinus carpio), y su efectos sobre biomarcadores en el hígado y el cerebro en la exposición a niveles subletales; constituye este trabajo una primera aproximación al estudio de la exposición a múltilples contaminantes en los cursos de agua de la región Comahue (Agentina). El insecticida paratión marcado co C se distribuyó en forma órgano-rspecífica en el hígado, con con concerntraciones 6 veces más altas que en otros órganos, mientras que la cumulación de mercurio se produjo más lentamente, principalmente en el hígado y el riñón. El paratión no afectó el índice hepatosomático, los niveles de glutatión, ni la producción de peróxidos lipidsicos; sin embargo, provocó una caída significativa del contenido de proteínas totales en el hígado. La aceticolinesterasa cerebral registró una inhibición pronunciada y significativa a las 24 horas de exposición (86 por ciento). Luego de 96 horas de exposición a mercurio solo se registró un 25 por ciento de inhibición de acetilcolisterasa cerebral. Estos resultados sugiere que si bien la exposición a niveles subletales de ambos tóxicos conduce a una concentración preferencial rn órganops críticos, los parámetros biomarcadores se ven afectados en los órganos diana. Esta situación se manisfesto en la acción neurotóxica de ambos compuestos y corrobora la evidencia de que la inhibición de la aceticolinesterasa no es prpducida solamente por insecticidas anticolinesterásicos, sino que metales tóxicos, como el mercurio, tambien pueden hacerlo.(AU)