Air quality, metal(loid) sources identification and environmental assessment using (bio)monitoring in the former mining district of Salsigne (Orbiel valley, France).

The former mining district of Salsigne is situated in the Orbiel valley. Until the 20th century, it was the first gold mine in Europe and the first arsenic mine in the world. Rehabilitation has been performed during the 20 years that followed closure of the mines and factories, which led to the accumulation of storage of several million tons of waste in this valley. Nevertheless, a detailed description of the air quality of this area is still missing. The goal of the present study is to evaluate atmospheric contamination in the valley and identify the potential sources of this contamination. Active monitors (particulate matter samplers) and passive bioindicators (Tillandsia usneoides) were placed in strategic sites including remote areas. Over the year 2022, we assessed the air quality using microscopic and spectroscopic techniques, as well as environmental risk indicators to report the level of contamination. Results indicate that the overall air quality in the valley is good with PM10 levels in accordance with EU standards. Elemental concentrations in the exposed plants were lower than reported in the literature. Among the different sites studied, Nartau and La Combe du Saut, corresponding to waste storage and former mining industry sites, were the most affected. Chronic exposure over 1 year was highlighted for Fe, Ni, Cu, Pb, Sb and As. Pollution Load Index and Enrichment Factors, which provided valuable information to assess the environmental condition of the valley's air, suggested that dust and resuspension of anthropogenic materials were the principle sources for most of the elements. Finally, this study also highlights that using T. usneoides could be a convenient approach for biomonitoring of metal (loid)-rich particles in the atmosphere within a former mining area, for at least one year. These results in turn allow to better understand the effects of chronic exposure on the ecosystem.

Elemental Composition of Plankton Exometabolites (Mucous Macroaggregates): Control by Biogenic and Lithogenic Components.

Among the various exometabolitic effects of marine microorganisms, massive mucilage events in the coastal zones of temperate and tropical seas are the most spectacular and environmentally important. Abundant mucilage material in the form of aggregates appears in late spring/early summer in the water column of the Adriatic Sea. These macroaggregate biopolymers originate mainly from plankton exometabolites, with both autochthonous and allochthonous components, and strongly impact the tourism, fisheries, and economy of coastal countries. In contrast to extensive studies on the structural and chemical nature of macroaggregates performed over past decades, the full elemental composition of these substances remains poorly known, which does not allow for a complete understanding of their origin, evolution, and necessary remediation measures. Here, we report the results of comprehensive analyses of 55 major and trace elements in the composition of macro aggregates collected at the surface and in the water column during massive mucilage events. Through normalization of the elemental chemical composition of the upper earth crust (UCC), river suspended material (RSM), mean oceanic plankton, and mean oceanic particulate suspended material, we demonstrate that the water column macroaggregates reflect a superposition of the signal from plankton and marine particulate matter. The surface macroaggregates were preferentially enriched in lithogenic component, and carried the signature of planktonic material. The rare earth element (REE) signal was strongly dominated by plankton and, to a lesser degree, by oceanic particulate matter, while at the same time being strongly (>80 times) impoverished compared with UCC and RSM. Taken together, the elemental composition of macroaggregates allows for distinguishing the lithogenic and biogenic impacts on the occurrence of these unique large-scale mucilage events, linked to the exometabolism of marine plankton combined with the input of allochthonous inorganic material.

The use of copper isotopes for understanding metal transfer mechanisms within the continuum mine-river-dam (Huelva Region, Spain).

Mining areas and in particular those containing massive sulfides have left a heavy environmental legacy with soils and hydrographic networks highly contaminated with metals and metalloids as for example in the Iberian Pyrite Belt (Huelva, Spain). Here, we present new data on copper (Cu) isotopic composition of waters and solids collected along a continuum Mine (Tharsis)-River (Meca)-Lake (Sancho) in the Iberian Pyrite Belt. Our results show that the isotopic signature of pit lakes is spatially variable, but remains stable over the seasons; this signature seems to be controlled by water-rock interaction processes. The data obtained on the Meca River imply a number of attenuation processes such as decrease in the metal concentration by precipitation of secondary minerals. This is accompanied by preferential retention of the heavy isotope (65Cu) with a possibility of living organisms (e.g., algae) participation. The terminal Sancho lake demonstrated constant isotopic signature over the entire depth of the water column despite sizable variations in Cu concentrations, which can be tentatively explained by a superposition of counter-interacting biotic and abiotic processes of Cu fractionation. Overall, the understanding of the isotopic variations along the hydrological continuum is useful for a better understanding of metal element transfer within mining environments and surrounding surface waters.

Chemical status of zinc in plant phytoliths: Impact of burning and (paleo)environmental implications.

Phytoliths are microscopic structures made of amorphous opal (opal-A), an amorphous hydrated silica, dispersed within plant tissues and persisting after the decay of the plant. Silicon is known to alleviate metal toxicity in plants, but the role of phytoliths in metal sequestration and detoxification is unclear. Dry ashing, the most common protocol for phytolith extraction, was previously shown to lead to sequestration of metals by the phytoliths; however, the mechanisms of this process remained elusive. The purpose of this study was to evaluate whether the association between metals and phytoliths results from dry ashing or pre-exists in plant tissues. Thus, we compared phytoliths extracted by dry ashing at 700 °C and plant leaves before and after dry ashing. A combination of ICP-MS, XRD, SEM-EDX and Zn-K-edge EXAFS spectroscopy was used to assess elemental concentrations, morphology and crystallography of silica, and chemical status of Zn. Results demonstrated a phase transition from amorphous opal (opal-A) to opal-CT and α-cristobalite, and the sequestration of metal in phytoliths during dry ashing. For Zn, Mn and Pb, a linear relationship was found between the concentration in phytoliths and in leaves. In the phytoliths, Zn was sequestered in silica in tetrahedral configuration. We hypothesize that this association results form a solid-state reaction during ashing, involving a redistribution of Zn from the organic material to the silica, possibly promoted by the release of structural water from amorphous opal throughout the heating procedure. This study improves our understanding of the impact of high temperature treatments on plant biomass and phytoliths. It suggests that Zn toxicity alleviation in plants by silicon does not rely on its sequestration by phytoliths. In natural settings, wild fire events and biomass burning may lead to metal sequestration in low-soluble form, which should be considered in modeling of biogeochemical cycles and in paleoenvironmental studies.

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.

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.

Elemental and Isotopic Variations of Copper and Zinc Associated with the Diel Activity of Phototrophic Biofilm.

The response in metal concentrations and isotopic composition to variations in photosynthetic activity of aquatic micro-organisms is crucially important for understanding the environmental controls on metal fluxes and isotope excursions. Here we studied the impacts of two successive diel cycles on physicochemical parameters, Cu and Zn concentrations, and isotopic composition in solution in the presence of mature phototrophic biofilm in a rotating annular bioreactor. The diel cycles induced fluctuations in temperature, pH, and dissolved oxygen concentration following the variation in the photosynthesis activity of the biofilm. Diel variations in metal concentrations were primarily related to the pH variation, with an increase in metal concentration in solution related to a pH decrease. For both metals, δ(66Zn) and δ(65Cu) in solution exhibited complex but reproducible diel cycles. Diel variations in photosynthetic activity led to alternatively positive and negative isotope fractionation, producing the sorption of light Zn (Δ(66Znsorbed-solution) = -0.1 ± 0.06‰) and heavy Cu isotopes (Δ(65Cusorbed-solution) = +0.17 ± 0.06‰) during the day at high pH and the excretion of lighter Zn isotopes (-0.4‰ < Δ(66Znexcreted-biofilm) < +0.14‰) and heavy Cu isotopes (Δ(65Cuexcreted-biofilm) = +0.7 ± 0.3‰) during the night at lower pH. We interpreted Zn and Cu diel cycles as a combination of a desorption of exopolymeric substance-metal complexes and a small active efflux during the night with adsorption and incorporation via an active uptake during the day. The hysteresis of metal concentration in solution over the diel cycle suggested the more important role of uptake compared to desorption and efflux from the biofilm. The phototrophic biofilm presents a non-negligible highly labile metal pool with important potential for contrasting isotopic fractionation at the diel scale.

Tillandsia usneoides as biomonitors of trace elements contents in the atmosphere of the mining district of Cartagena-La Unión (Spain): New insights for element transfer and pollution source tracing.

Nowadays, atmospheric pollution has a major impact on the human health and the environment, encouraging the development of biomonitors of the air quality over a wide zone. In this study, the relevance of the epiphyte plants Tillandsia usneoides is studied to estimate the transfer of metal(loid)s from a former Zn and Pb mining zone in the Southeast of Spain (Cartagena-La Unión) to the local atmosphere. Biomonitoring was performed by installing plants in 5 sites along a transect from the main mining area to the urban and the coastal zones. An aliquot of plants was collected in every site every 2 months over 1 year. The Tillandsia usneoides have been observed with SEM-EDX, and analysed by ICP-MS to determine trace element concentrations, magnetic susceptibility signals and Zn and Pb isotopes ratios. Results show that atmospheric particles are distributed homogeneously at the plant surface. By comparing elemental contents in Tillandsia usneoides with regard to the values of the geochemical background of the region of Murcia, significant enrichments are observed in the epiphyte plants for Sb, As, Cd, Zn and Pb. The statistical analyses (decentred PCA and PLS) also suggest that the kinetics of dust deposition is slower for the urban and coastal sites compared to the mining sites and highlight an influence of agricultural activities in Cu deposition. The similarity of isotopic compositions (Zn and Pb) between Tillandsia usneoides, soils and atmospheric particles also put in evidence that these plants could be a powerful tool to trace the source of matter in the atmosphere. Finally, this experiment provides new insight to better understand the foliar absorption mechanisms.

Accumulation of heavy metals in phytoliths from reeds growing on mining environments in Southern Europe.

In Southern Europe, soil contamination by heavy metals (HM) due to mining and industrial activities is a long-known problem. Yet, despite soils being widely contaminated through decades, some plants are still able to grow. Some of these plants, like giant reed (Arundo donax) or common reed (Phragmites australis) are capable of accumulating substantial amount of HM. These reeds also contain small silica structures in their shoots, called phytoliths. However, the role of phytoliths in reducing stress caused by these HM remains unknown. The aim of this work is then to determine if phytoliths represent a preferential structure for the bioacccumulation of HM in plants. Therefore, plants from mining-contaminated sites in Spain and France were sampled and HM concentrations in total plant shoots were compared to those in phytoliths for eight metal(oid)s: As, Cd, Cu, Mn, Pb, Sb, Sn and Zn. Results show that Arundo donax and Phragmites australis tend to accumulate Cd, Sb and Sn but limit the uptake of As, Cu, Mn, Pb and Zn in plant shoots despite that the concentration of these HM in soil is quite high. Therefore, reeds appear as tolerant to high metal concentrations in soils, and phytoliths are identified as preferential structures for encapsulation of As, Cu, Mn, Pb and Zn, while Cd, Sb and Sn were mainly found to be accumulated in organic tissues rather than in phytoliths.

Atmospheric dust characterisation in the mining district of Cartagena-La Unión, Spain: Air quality and health risks assessment.

Nowadays, air pollution has a major impact on the environment and human health. Owen gauges allow the sampling of atmospheric depositions in polluted sites for further characterisation. This paper shows the study of the air particles of an old mining zone in Cartagena-La Unión (South-east of Spain) in order to quantify their potential risk on human health. There were 4 strategic sites monitored: the main mining tailing (Avenque), the urban area (La Unión), an agricultural zone (formerly mining) and a site in the Mediterranean coast. Physico-chemical and mineralogical characterisation was applied to atmospheric fallouts. The granulometry revealed a dust particle size around 15 µm, with the coarsest particles in the urban area and the thinnest at the tailing site. XRD analyses showed the presence of quartz, carbonates, sulphides and sulphates. Observations with SEM-EDX confirmed chemical spectra and allowed us to classify the particles into well-crystallised minerals and heterogeneous dusts. Total metal content determination was carried out by ICP-MS analyses and results showed Zn, Pb, As and Cd fluxes (respectively 2549, 1275, 68 and 7 µg·m-2·d-1) exceeding the limit values set by European legislations in the mining area. The fluxes of Zn, Pb and As also exceed these standards in the urban area whereas the coastal zone only exceeds the thresholds in the case of As. Inhalation health risk (defined by US EPA, 2009) was quantified in the sites using total and bioaccessible metal contents of the dusts. Risk calculations using total metal content considering a residential scenario showed acceptable risk for all sites except for the mining tailing which presented non-acceptable cancer and hazard risk mainly due to the total As and Pb contents. When considering the bioaccessible fraction of As and Pb, the risk diminished to acceptable values, demonstrating the overestimation produced when using total metal contents.

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.

Body size determines soil community assembly in a tropical forest.

Tropical forests shelter an unparalleled biological diversity. The relative influence of environmental selection (i.e., abiotic conditions, biotic interactions) and stochastic-distance-dependent neutral processes (i.e., demography, dispersal) in shaping communities has been extensively studied for various organisms, but has rarely been explored across a large range of body sizes, in particular in soil environments. We built a detailed census of the whole soil biota in a 12-ha tropical forest plot using soil DNA metabarcoding. We show that the distribution of 19 taxonomic groups (ranging from microbes to mesofauna) is primarily stochastic, suggesting that neutral processes are prominent drivers of the assembly of these communities at this scale. We also identify aluminium, topography and plant species identity as weak, yet significant drivers of soil richness and community composition of bacteria, protists and to a lesser extent fungi. Finally, we show that body size, which determines the scale at which an organism perceives its environment, predicted the community assembly across taxonomic groups, with soil mesofauna assemblages being more stochastic than microbial ones. These results suggest that the relative contribution of neutral processes and environmental selection to community assembly directly depends on body size. Body size is hence an important determinant of community assembly rules at the scale of the ecological community in tropical soils and should be accounted for in spatial models of tropical soil food webs.

Are Cu isotopes a useful tool to trace metal sources and processes in acid mine drainage (AMD) context?

In the South-West Europe (Iberian Pyrite Belt), acid mine drainage (AMD) processes are especially problematic because they affect the environmental quality of watersheds, restricting the use of surface water. Recent studies have shown that Cu isotopes are fractionated during the oxidative dissolution of primary sulfide minerals and could be used to trace metal cycling. However the chemistry of Cu in such environment is complex because Cu is redistributed within numerous secondary minerals and strongly dependent on the hydroclimatic conditions that control key parameters (pH, redox conditions). Finally, it remains difficult to compare the various field studies and deliver some strong general tendencies because of these changing conditions. For these reasons, concerted studies on Cu isotopes fractionation in waters impacted by AMD may help to reveal the sources and transport pathways of this important pollutant. To address this issue, we used a representative scenario of strong contamination by AMD in the Iberian Pyrite Belt (SW Spain), the Cobica River. The aim of our study is to measure the Cu isotopes signature in the waters (river, mine lake, water draining waste) of the small Cobica River system (Huelva, Spain), sampled during a short period (8 h) to avoid any change in the hydro-climatic conditions. This provided an instantaneous image of the isotopic Cu signature in a small mining systems and helped us to constrain both the processes affecting Cu isotopes and their use a potential tracer of metals in contaminated environments.

A critical examination of the possible application of zinc stable isotope ratios in bivalve mollusks and suspended particulate matter to trace zinc pollution in a tropical estuary.

The application of zinc (Zn) isotopes in bivalve tissues to identify zinc sources in estuaries was critically assessed. We determined the zinc isotope composition of mollusks (Crassostrea brasiliana and Perna perna) and suspended particulate matter (SPM) in a tropical estuary (Sepetiba Bay, Brazil) historically impacted by metallurgical activities. The zinc isotope systematics of the SPM was in line with mixing of zinc derived from fluvial material and from metallurgical activities. In contrast, source mixing alone cannot account for the isotope ratios observed in the bivalves, which are significantly lighter in the contaminated metallurgical zone (δ66ZnJMC = +0.49 ± 0.06‰, 2σ, n = 3) compared to sampling locations outside (δ66ZnJMC = +0.83 ± 0.10‰, 2σ, n = 22). This observation suggests that additional factors such as speciation, bioavailability and bioaccumulation pathways (via solution or particulate matter) influence the zinc isotope composition of bivalves.

Amazon River dissolved load: temporal dynamics and annual budget from the Andes to the ocean.

The aim of the present study is to estimate the export fluxes of major dissolved species at the scale of the Amazon basin, to identify the main parameters controlling their spatial distribution and to identify the role of discharge variability in the variability of the total dissolved solid (TDS) flux through the hydrological cycle. Data are compiled from the monthly hydrochemistry and daily discharge database of the "Programa Climatologico y Hidrologico de la Cuenca Amazonica de Bolivia" (PHICAB) and the HYBAM observatories from 34 stations distributed over the Amazon basin (for the 1983-1992 and 2000-2012 periods, respectively). This paper consists of a first global observation of the fluxes and temporal dynamics of each geomorphological domain of the Amazon basin. Based on mean interannual monthly flux calculations, we estimated that the Amazon basin delivered approximately 272 × 10(6) t year(-1) (263-278) of TDS during the 2003-2012 period, which represents approximately 7 % of the continental inputs to the oceans. This flux is mainly made up by HCO3, Ca and SiO2, reflecting the preferential contributions of carbonate and silicate chemical weathering to the Amazon River Basin. The main tributaries contributing to the TDS flux are the Marañon and Ucayali Rivers (approximately 50 % of the TDS production over 14 % of the Amazon basin area) due to the weathering of carbonates and evaporites drained by their Andean tributaries. An Andes-sedimentary area-shield TDS flux (and specific flux) gradient is observed throughout the basin and is first explained by the TDS concentration contrast between these domains, rather than variability in runoff. This observation highlights that, under tropical context, the weathering flux repartition is primarily controlled by the geomorphological/geological setting and confirms that sedimentary areas are currently active in terms of the production of dissolved load. The log relationships of concentration vs discharge have been characterized over all the studied stations and for all elements. The analysis of the slope of the relationship within the selected contexts reveals that the variability in TDS flux is mainly controlled by the discharge variability throughout the hydrological year. At the outlet of the basin, a clockwise hysteresis is observed for TDS concentration and is mainly controlled by Ca and HCO3 hysteresis, highlighting the need for a sampling strategy with a monthly frequency to accurately determine the TDS fluxes of the basin. The evaporite dissolution flux tends to be constant, whereas dissolved load fluxes released from other sources (silicate weathering, carbonate weathering, biological and/or atmospheric inputs) are mainly driven by variability in discharge. These results suggest that past and further climate variability had or will have a direct impact on the variability of dissolved fluxes in the Amazon. Further studies need to be performed to better understand the processes controlling the dynamics of weathering fluxes and their applicability to present-day concentration-discharge relationships at longer timescales.

Antimony isotopic composition in river waters affected by ancient mining activity.

In this study, antimony (Sb) isotopic composition was determined in natural water samples collected along two hydrosystems impacted by historical mining activities: the upper Orb River and the Gardon River watershed (SE, France). Antimony isotope ratio was measured by HG-MC-ICP-MS (Hydride Generation Multi-Collector Inductively Coupled Plasma Mass Spectrometer) after a preconcentration and purification step using a new thiol-cellulose powder (TCP) procedure. The external reproducibility obtained for δ(123)Sb measurements of our in-house Sb isotopic standard solution and a certified reference freshwater was 0.06‰ (2σ). Significant isotopic variations were evident in surface waters from the upper Orb River (-0.06‰≤δ(123)Sb≤+0.11‰) and from the Gardon River watershed (+0.27‰≤δ(123)Sb≤+0.83‰). In particular, streams that drained different former mining sites exploited for Sb or Pb-Zn exhibited contrasted Sb isotopic signature, that may be related to various biogeochemical processes occurring during Sb transfer from rocks, mine wastes and sediments to the water compartment. Nevertheless, Sb isotopic composition appeared to be stable along the Gardon River, which might be attributed to the conservative transport of Sb at distance from mine-impacted streams, due to the relative mobile behavior of Sb(V) in natural oxic waters. This study suggests that Sb isotopic composition could be a useful tool to track pollution sources and/or biogeochemical processes in hydrologic systems.

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.

Persisting impact of historical mining activity to metal (Pb, Zn, Cd, Tl, Hg) and metalloid (As, Sb) enrichment in sediments of the Gardon River, Southern France.

In this study, we assessed past and present influence of ancient mining activity on metal(loid) enrichment in sediments of a former mining watershed (Gardon River, SE France), that is now industrialized and urbanized. A sedimentary archive and current sediments were characterized combining geochemical analyses, zinc isotopic analyses and sequential extractions. The archive was used to establish local geochemical background and recorded (i) increasing enrichment factors (EFs) for Pb, Zn, Cd, Tl, Hg, As and Sb throughout the industrial era, (ii) a contamination peak in 1976 attributed to a tailings dam failure, and (iii) current levels in 2002 and 2011 similar to those of 1969, except for Sb and Hg, reflecting a persisting contamination pattern. Inter-element relationships and spatial distribution of EF values of current sediments throughout the watershed suggested that both ancient and current contamination had a common origin for Pb, Zn, Cd, Tl and As related to the exploitation of Pb/Zn mineralization while old Sb mines and coal extraction area were the main sources for Sb and Hg respectively. This prevailing mining origin was reflected for Zn by a relatively uniform isotopic composition at δ(66)Zn=0.23 ± 0.03‰, although slight decrease from 0.23‰ to 0.18‰ was recorded from upstream to downstream sites along the river course in relation with the contribution of the lighter δ(66)Zn signature (~0.08‰) of acid mine drainage impacted tributaries. Results from sequential extractions revealed that the potential mobility of the studied metal(loid)s varied in the order Sb

Chemical composition of suspended sediments in World Rivers: New insights from a new database.

The aim of this paper is to present a new database on the chemical composition of suspended matter in World Rivers, together with the associated elemental fluxes. There is a lack of any recent attempt in the literature to update the pioneering work of Martin and Meybeck [Martin, J.-M., Meybeck, M., 1979. Elemental mass balance of material carried by major world rivers. Mar. Chem. 7, 173-206.] and Martin and Whitfield [Martin, J.-M., Whitfield, M., 1983. The significance of the river input of chemical elements to the ocean. Trace metals in sea water Wong, Boyle, Bruland, Burton, Goldberg (Eds) Plenum Publishing Corporation.] regarding the worldwide average major and trace element chemistry of riverine particulate matter. Apart from compiling a new database on particulate matter, this paper also aims to give a "snap-shot" of elemental fluxes for each continent. This approach should allow us to obtain new insights on weathering conditions in different environments and assess the influence of human activities on natural geochemical cycles. Finally, this study demonstrates the large uncertainties currently associated with estimating the flux of sediments transported by rivers. By comparing the riverine suspended sediment fluxes of some metals (Cd, Zn, Ni, Cu, Cr and Pb) given in this study with estimates of the anthropogenic fluxes of these metals to the atmosphere, soils and waters (natural ecosystems) [Nriagu, J.O., 1988. A silent epidemic of environmental poisoning. Environ. Pollut. 50, 139-161.], we can see that riverine fluxes are similar to anthropogenic fluxes. This casts light on the effect of human activities on the cycles of trace elements at the Earth's surface.