Zn isotope fractionation in a pristine larch forest on permafrost-dominated soils in Central Siberia.

Stable Zn isotopes fractionation was studied in main biogeochemical compartments of a pristine larch forest of Central Siberia developed over continuous permafrost basalt rocks. Two north- and south-oriented watershed slopes having distinctly different vegetation biomass and active layer depth were used as natural proxy for predicting possible future climate changes occurring in this region. In addition, peat bog zone exhibiting totally different vegetation, hydrology and soil temperature regime has been studied. The isotopic composition of soil profile from Central Siberia is rather constant with a δ(66)Zn value around 0.2‰ close to the value of various basalts. Zn isotopic composition in mosses (Sphagnum fuscum and Pleurozium schreberi) exhibits differences between surface layers presenting values from 0.14 to 0.2‰ and bottom layers presenting significantly higher values (0.5 - 0.7‰) than the underlain mineral surface. The humification of both dead moss and larch needles leads to retain the fraction where Zn bound most strongly thus releasing the lighter isotopes in solution and preserving the heavy isotopes in the humification products, in general accord with previous experimental and modeling works [GCA 75:7632-7643, 2011]. The larch (Larix gmelinii) from North and South-facing slopes is enriched in heavy isotopes compared to soil reservoir while larch from Sphagnum peatbog is enriched in light isotopes. This difference may result from stronger complexation of Zn by organic ligands and humification products in the peat bog compared to mineral surfaces in North- and South-facing slope. During the course of the growing period, Zn followed the behavior of macronutrients with a decrease of concentration from June to September. During this period, an enrichment of larch needles by heavier Zn isotopes is observed in the various habitats. We suggest that the increase of the depth of rooting zone, and the decrease of DOC and Zn concentration in soil solution from the root uptake zone with progressively thawing soil could provoke heavy isotopes to become more available for the larch roots at the end of the vegetative season compared to the beginning of the season, because the decrease of DOC will facilitate the uptake of heavy isotope as it will be less retained in strong organic complexes.

Pedo-geochemical background and sediment contamination of metal(loid)s in the old mining-district of Salsigne (Orbiel valley, France).

The mining district of Salsigne in the Orbiel valley (Aude, France) was at one time the first gold mine in Europe and the first arsenic mine in the world. However, no scientific studies have evaluated the magnitude of its environmental impact. In this study, the pedo-geochemical background (PGB) was determined for 14 metal (loid) elements, including As. It appears that the PGB values for As and Sb are relatively high with 44±12 and 0.9±1.2 mg kg-1, respectively, because of the geological particularities of this area. In a second step, these PGB values (normalized with Ti concentrations) were used as local references to determine enrichment factors (EFs) of bed river sediments for the Orbiel River and two of its major tributaries (Gresillou and Russec rivers) collected between November 2018 and July 2020. Results showed that riverine sediments are contaminated by past mining activity and/or current storage areas. If we except the major elements (Fe, Ti and at a lesser extent Mn), we observed that As, Cu, Sb, Pb present the highest concentrations relative to the remaining elements (Cd, Co, V, Ni and Cr). In the case of As, EFs can reach 74 in the Orbiel River, 1000 in the Gresillou River and 27 in the Russec River. These calculations were also performed for sediments transported by the extreme flood of October 14, 2018, that killed 15 people and potentially remobilized contamination in the valley. We observed that the As concentrations of suspended samples from Grésillou and Russec rivers have reached 870 mg kg-1. Finally, the As concentrations measured in the river sediments of this valley are of the same order of magnitude than those published in the literature for environments strongly impacted by mining or mineral processing activities.

Distribution of Burkholderia pseudomallei within a 300-cm deep soil profile: implications for environmental sampling.

The environmental distribution of Burkholderia pseudomallei, the causative agent of melioidosis, remains poorly understood. B. pseudomallei is known to have the ability to occupy a variety of environmental niches, particularly in soil. This paper provides novel information about a putative association of soil biogeochemical heterogeneity and the vertical distribution of B. pseudomallei. We investigated (1) the distribution of B. pseudomallei along a 300-cm deep soil profile together with the variation of a range of soil physico-chemical properties; (2) whether correlations between the distribution of B. pseudomallei and soil physico-chemical properties exist and (3) when they exist, what such correlations indicate with regards to the environmental conditions conducive to the occurrence of B. pseudomallei in soils. Unexpectedly, the highest concentrations of B. pseudomallei were observed between 100 and 200 cm below the soil surface. Our results indicate that unravelling the environmental conditions favorable to B. pseudomallei entails considering many aspects of the actual complexity of soil. Important recommendations regarding environmental sampling for B. pseudomallei can be drawn from this work, in particular that collecting samples down to the water table is of foremost importance, as groundwater persistence appears to be a controlling factor of the occurrence of B. pseudomallei in soil.

Stable Cu Isotope Ratios Show Changes in Cu Uptake and Transport Mechanisms in Vitis vinifera Due to High Cu Exposure.

Even though copper (Cu) is an essential plant nutrient, it can become toxic under certain conditions. Toxic effects do not only depend on soil Cu content, but also on environmental and physiological factors, that are not well understood. In this study, the mechanisms of Cu bioavailability and the homeostasis of Vitis vinifera L. cv. Tannat were investigated under controlled conditions, using stable Cu isotope analysis. We measured Cu concentrations and δ65Cu isotope ratios in soils, soil solutions, roots, and leaves of grapevine plants grown on six different vineyard soils, in a 16-week greenhouse experiment. The mobility of Cu in the soil solutions was controlled by the solubility of soil organic matter. No direct relationship between Cu contents in soils or soil solutions and Cu contents in roots could be established, indicating a partly homeostatic control of Cu uptake. Isotope fractionation between soil solutions and roots shifted from light to heavy with increasing Cu exposure, in line with a shift from active to passive uptake. Passive uptake appears to exceed active uptake for soil solution concentrations higher than 270 µg L-1. Isotope fractionation between roots and leaves was increasingly negative with increasing root Cu contents, even though the leaf Cu contents did not differ significantly. Our results suggest that Cu isotope analysis is a sensitive tool to monitor differences in Cu uptake and translocation pathways even before differences in tissue contents can be observed.

Soil chemistry and meteorological conditions influence the elemental profiles of West European wines.

Elemental profiles of wines have been used successfully to distinguish their geographical provenience around the world; however, underlying mechanisms are poorly understood. In this study, Ba, Ca, Mg, Mn and Sr contents were determined in 215 wines from several West European wine-growing areas using an easy-to-perform analysis based on ICP-OES. Major environmental and wine-making parameters (soil type as "calcareous" or not, rainfall, temperature and wine color) were used to explain variations within the dataset. The combined effects of wine-making processes (expressed by wine color) and soil type explained 28.5% of total variance. The effect of climatic conditions explained 24.1% of variance and could be interpreted as intensity of drought stress. Finally, carbonate occurrence in soils and climatic conditions systematically influenced the elemental composition of the wines. These findings provide insights into the mechanisms underlying elemental fingerprinting and allow prediction of which wine-growing regions can easily be distinguished based on elemental profiles as a marker of the terroir in viticulture.

Metal concentration and bioaccessibility in different particle sizes of dust and aerosols to refine metal exposure assessment.

Refined exposure assessments were realized for children, 7-9yrs, in the mining/smelting city of Oruro, Bolivia. Aerosols (PM>2.5, PM1-2.5, PM0.4-1 and PM0.5) and dust (separated in different particle size fractions: 2000-200µm, 200-50µm, 50-20µm, 20-2µm and <2µm) were sampled on football fields highly frequented by children in both the mining and smelting areas. Trace element concentrations (Ag, As, Cd, Cu, Pb, Sb, Sn and Zn) in each size fraction of dust and aerosols, lung bioaccessibility of metals in aerosols, and gastric bioaccessibility of metals in dust were measured. Exposure was assessed considering actual external exposure (i.e. exposure pathways: metals inhaled and ingested) and simulated internal exposure (i.e., complex estimation using gastric and lung bioaccessibility, deposition and clearance of particles in lungs). Significant differences between external and simulated internal exposure were attributed to dissemblances in gastric and lung bioaccessibilities, as well as metal distribution within particle size range, revealing the importance of both parameters in exposure assessment.

The influence of the Amazonian floodplain ecosystems on the trace element dynamics of the Amazon River mainstem (Brazil).

The purpose of this paper is to forecast the role of riverine wetlands in the transfer of trace elements. One of the largest riverine wetlands in the world is the floodplain (várzea) of the Amazon River and its tributaries (Junk and Piedade, 1997). The central Amazon wetlands are constituted by a complex network of lakes and floodplains, named várzeas, that extend over more than 300,000 km2 (Junk, W.J., The Amazon floodplain--a sink or source for organic carbon? In Transport of Carbon and Minerals in Major World Rivers, edited by E.T. Degens, S. Kempe, R. Herrera, SCOPE/UNEP; 267-283, 1985.) and are among the most productive ecosystems in the world due to the regular enrichment in nutrients by river waters In order to understand if the adjacent floodplain of Amazon River have a significant influence on the trace element concentrations and fluxes of the mainstem, the concentrations of selected elements (i.e., Al, Mn, Fe, Co, Cu, Mo, Rb, Sr, Ba, and U) have been measured in the Amazon River water (Manacapuru Station, Amazonas State, Brazil) and in lake waters and plants (leaves) from a várzea(Ilha de Marchantaria, Amazonas State, Brazil) during different periods of the hydrological cycle. Four plant species (two perennial species: Pseudobombax munguba and Salix humboldtiana, and two annual herbaceous plants: Echinochloa polystachya and Eichhornia crassipes) were selected to represent the ecological functioning of the site. Time series obtained for dissolved Mn and Cu (<0.20 microm) in Amazon River water could not be explained by tributary mixing or instream processes only. Therefore, the contribution of the waters transiting the floodplains should be considered. These results suggest that the chemical composition of the waters draining these floodplains is controlled by reactions occurring at sediment-water and plant-water interfaces. Trace elements concentrations in the plants (leaves) vary strongly with hydrological seasonality. Based on the concentration data and the biological productivity of floodplain ecosystems, a first order approximation of trace element storage (permanent or temporary) in the vegetation of these floodplains was made. It was found that floodplain-mainstem elemental fluxes make a significant contribution to the dissolved flux of the Amazon River. This study is part of the Brazilian_French joint research program Hybam (Hydrology and Geochemistry of the Amazonian Basin).

Influence of source distribution and geochemical composition of aerosols on children exposure in the large polymetallic mining region of the Bolivian Altiplano.

The Bolivian Altiplano (Highlands) region is subject to intense mining, tailing and smelting activities since centuries because of the presence of large and unique polymetallic ore deposits (Ag, Au, Cu, Pb, Sn, Sb, Zn). A large scale PM(10), PM(2.5) aerosol monitoring survey was conducted during the dry season in one of the largest mining cities of this region (Oruro, 200,000 inhabitants). Aerosol fractions, source distribution and transport were investigated for 23 elements at approximately 1 km(2) scale resolution, and compared to children exposure data obtained within the same geographical space. As, Cd, Pb, Sb, W and Zn in aerosols are present at relatively high concentrations when compared to studies from other mining regions. Arsenic exceeds the European council PM(10) guide value (6 ng/m(3)) for 90% of the samples, topping 200 ng/m(3). Ag, As, Cd, Cu, Pb and Sb are present at significantly higher levels in the district located in the vicinity of the smelter zone. At the city level, principal component analysis combined with the mapping of factor scores allowed the identification and deconvolution of four individual sources: i) a natural magmatic source (Co, Cs, Fe, K, Mn, Na, Rb and U) originating from soil dust, resuspended by the traffic activity; ii) a natural sedimentary source (Mg, Ca, Sr, Ba and Th) resulting from the suspension of evaporative salt deposits located South; iii) an anthropogenic source specifically enriched in mined elements (As, Cd, Cu, Pb, Sb and Zn) mainly in the smelting district of the city; and iv) a Ni-Cr source homogenously distributed between the different city districts. Enrichment factors for As, Cd and Sb clearly show the impact of smelting activities, particularly in the finest PM(2.5) fraction. Comparison to children's hair metal contents collected in five schools from different districts shows a direct exposure to smelting activity fingerprinted by a unique trace elements pattern (Ag, As, Cu, Pb, Sb).