Modelling trace metal background to evaluate anthropogenic contamination in arable soils of south-western France

The trace metal (TM) content in arable soils has been monitored across a region of France characterised by a large proportion of calcareous soils. Within this particular geological context, the objectives were to first determine the natural levels of trace metals in the soils and secondly, to assess which sites were significantly contaminated. Because no universal contamination assessment method is currently available, four different methods were applied and compared in order to facilitate the best diagnosis of contamination. First, the TM geochemical background was determined by using basic descriptive statistics and linear regression models calculated with semi-conservative major elements as predictors. The natural concentrations of trace metals varied greatly due to the high soil heterogeneity encountered on the regional scale and were more-or-less accurately modelled according to the considered TM. Second, the basic descriptive statistics and the linear regression methods were then compared with the enrichment factor (EF) method and multivariate analysis (PCA), in order to evaluate whether the concentrations measured in soils were abnormally high or not. The advantages and disadvantages of each method were discussed and their results used to identify the most probable contamination cases, the influence of the soils characteristics, as well as the agricultural land cover. The basic descriptive method was good as a first and easy approach to describe the TM ambient concentrations, but may misinterpret the natural anomalies as contaminations. Based on geochemical associations, the linear regression method provided more realistic results even if the relationships between major and trace metals were not significant for the most mobile TM. The EF method was useful to identify high point source contaminations, but it was not suitable when considering a large dataset of low TM concentrations. Finally, the PCA method was a good preliminary tool for the description of the global TM concentrations in a studied area, but it could only give indication on the highest contaminated points. By comparing the results of the different methods in the studied region, we estimated that 24% of the arable soils were contaminated by at least one trace metal, mainly Cu in vineyards/orchards and Cd, Pb and/or Zn in grazing lands. In addition, the calcareous soils exhibited globally higher natural and anthropogenic TM concentrations than non-calcareous soils, probably because of the lower TM mobility at alkaline pH

Measurement of isotopically-exchangeable Zn in Zn-deficient paddy soil

The changes in soil chemistry following submergence of a soil for rice production result in zinc (Zn) being immobilized in very insoluble forms. Consequently, Zn deficiency is widespread in rice crops and in human populations that subsist on rice. We explored the use of stable isotopic dilution assays for assessing Zn dynamics in submerged paddy soil with two types of strongly Zn-deficient soil for rice cultivation in the Philippines. We optimized the isotope enrichment, electrolyte and equilibration time to measure isotopically-exchangeable Zn (E-values) without changing redox conditions. Available Zn was rapidly and strongly immobilized following submergence, which was controlled by CO2 accumulation. Addition of the isotopic tracer before submergence produced unreliable E-values because irreversible immobilization of the tracer progressed faster than isotopic exchange. Addition of the tracer to already reduced soil produced stable E-values for tracer–soil contact of up to 1 week. Longer periods produced unreliable E-values because of continuing irreversible fixation of the tracer. We discuss the implications for applications of isotopic dilution methods to measure trace-element dynamics in submerged soil

Diagnostic de la contamination des eaux par les éléments traces métalliques dans la zone aurifère de Komabangou – Tillabéri, Niger

A Komabangou, dans la région de Tillabéri au Niger, l’or est exploité, durant des décennies, de manière artisanale avec l’utilisation des méthodes inadéquates et des substances peu respectueuses de l’environnement comme le mercure et le cyanure. La présente étude a pour objectif de déterminer les teneurs en éléments traces métalliques (ETM) des eaux de Komabangou afin de prévoir les risques environnementaux et sanitaires liés à leur utilisation. Ainsi, des prélèvements d’eau ont été effectués sur 8 sites d’extraction d’or, 4 forages et 3 mares, et leurs concentrations en métaux tels que As, Cd, Cu, Hg, Ni, Pb et Zn ont été analysées par spectrométrie de masse avec plasma à couplage inductif (ICP-MS). Les résultats obtenus révèlent une contamination importante de ces eaux et soulignent une variabilité significative des concentrations des ETM en fonction du métal analysé et du type d’eau. Dans la plupart des eaux, les valeurs limites réglementaires notamment celles de l’OMS ont été dépassées, cela pourrait poser des problèmes de toxicité pour les plantes, les animaux et la population locale. Par conséquent, la mise en place d’un programme de surveillance et de traitement des eaux contaminées de la zone de Komabangou serait nécessaire pour réduire les risques de contamination humaine.Mots clés : ETM, eaux, risque, site aurifère, Komabangou, Niger

Using isotopic dilution to assess chemical extraction of labile Ni, Cu, Zn, Cd and Pb in soils

Chemical extractants used to measure labile soil metal must ideally select for and solubilise the labile fraction, with minimal solubilisation of non-labile metal. We assessed four extractants (0.43 M HNO3, 0.43 M CH3COOH, 0.05 M Na2H2EDTA and 1 M CaCl2) against these requirements. For soils contaminated by contrasting sources, we compared isotopically exchangeable Ni, Cu, Zn, Cd and Pb (EValue, mg kg-1), with the concentrations of metal solubilised by the chemical extractants (MExt, mg kg-1). Crucially, we also determined isotopically exchangeable metal in the soil–extractant systems (EExt, mg kg-1). Thus ‘EExt - EValue’ quantifies the concentration of mobilised non-labile metal, while ‘EExt - MExt’ represents adsorbed labile metal in the presence of the extractant. Extraction with CaCl2 consistently underestimated EValue for Ni, Cu, Zn and Pb, while providing a reasonable estimate of EValue for Cd. In contrast, extraction with HNO3 both consistently mobilised non-labile metal and overestimated the EValue. Extraction with CH3COOH appeared to provide a good estimate of EValue for Cd; however, this was the net outcome of incomplete solubilisation of labile metal, and concurrent mobilisation of non-labile metal by the extractant (MExt EValue). The Na2H2EDTA extractant mobilised some non-labile metal in three of the four soils, but consistently solubilised the entire labile fraction for all soil-metal combinations (MExt ≈ EExt). Comparison of EValue, MExt and EExt provides a rigorous means of assessing the underlying action of soil chemical extraction methods and could be used to refine long-standing soil extraction methodologies

Bioavailability in soils

The consumption of locally-produced vegetables by humans may be an important exposure pathway for soil contaminants in many urban settings and for agricultural land use. Hence, prediction of metal and metalloid uptake by vegetables from contaminated soils is an important part of the Human Health Risk Assessment procedure. The behaviour of metals (cadmium, chromium, cobalt, copper, mercury, molybdenum, nickel, lead and zinc) and metalloids (arsenic, boron and selenium) in contaminated soils depends to a large extent on the intrinsic charge, valence and speciation of the contaminant ion, and soil properties such as pH, redox status and contents of clay and/or organic matter. However, chemistry and behaviour of the contaminant in soil alone cannot predict soil-to-plant transfer. Root uptake, root selectivity, ion interactions, rhizosphere processes, leaf uptake from the atmosphere, and plant partitioning are important processes that ultimately govern the accumulation ofmetals and metalloids in edible vegetable tissues. Mechanistic models to accurately describe all these processes have not yet been developed, let alone validated under field conditions. Hence, to estimate risks by vegetable consumption, empirical models have been used to correlate concentrations of metals and metalloids in contaminated soils, soil physico-chemical characteristics, and concentrations of elements in vegetable tissues. These models should only be used within the bounds of their calibration, and often need to be re-calibrated or validated using local soil and environmental conditions on a regional or site-specific basis.Mike J. McLaughlin, Erik Smolders, Fien Degryse, and Rene Rietr

Using isotope dilution assays to understand speciation changes in Cd, Zn, Pb and Fe in a soil model system under simulated flooding conditions

Flooded soils are systems with complex chemistry and understanding the mechanisms that control the mobility and bioavailability of metals in these soils is important for their management. This work uses stable metal multi-element isotopic dilution combined with sequential extraction assays to help understand the changes in solid and solution speciation of Cd, Fe, Pb and Zn in a contaminated soil following submergence. However, it is necessary to ensure that the isotopic dilution principles, originally developed for aerobic soils, are not compromised; in particular due to the presence of non-labile colloids in the solution phase. In particular, no studies examining the validity of these assays in systems where rapid pH and Eh changes are occurring due to fermentation reactions have been published. Thus sucrose (0.42% and 1.26% added C) was used as a carbon source to stimulate bacterial mediated fermentation reactions allowing changes in Cd, Zn, Fe and Pb isotopic exchangeability, speciation and solution chemistry to be examined after 10, 20 and 42 days of submergence. Without the addition of added C, submergence for 42 days only produced minor changes in the speciation of the metals in solid or solution phases. However, the presence of easily labile carbon produced significant responses depending on the quantity of C added. Assessments of whether fermentation products caused over-estimation of the isotopically exchangeable pool of metals (E-values) were made by measuring concentrations with and without a resin purification step. Results showed generally good agreement over a pH range of 4–7 for Pb, Cd, Zn and Fe and demonstrate that fermentation by-products do not induce the formation of non-exchangeable metal colloids. E-value concentrations were compared with fractions extracted using a modified Tessier sequential extraction. With no carbonate phases present in the soils, the E-values for Cd, Zn, Fe and Pb compared favourably with the concentrations of metal present in the combined solution, exchangeable and specifically adsorbed fractions. This provided additional evidence that the conditions for the isotopic dilution assays were not violated as these fractions should be isotopically exchangeable. Combining results from the different treatments and stages of the reduction process, strong pH dependence was found for the isotopically exchangeable and the solution pools of Cd, Zn and Pb

Ecological changes in historically polluted soils: Metal(loid) bioaccumulation in microarthropods and their impact on community structure

International audienceSoil pollution by persistent metal(loid)s present environmental and sanitary risks. While the effects of metal(loid)s on vegetation and macrofauna have been widely studied, their impact on microarthropods (millimetre scale) and their bioaccumulation capacity have been less investigated. However, microarthropods provide important ecosystem services, contributing in particular to soil organic matter dynamics. This study focussed on the impact of metal(loid) pollution on the structure and distribution of microarthropod communities and their potential to bioaccumulate lead (Pb). Soil samples were collected from a contaminated historical site with a strong horizontal and vertical gradient of Pb concentrations. Microarthropods were extracted using the Berlese method. The field experiments showed that microarthropods were present even in extremely polluted soils (30,000 mg Pb kg− 1). However, while microarthropod abundance increased with increasing soil C/N content (R2 = 0.79), richness decreased with increasing pollution. A shift in the community structure from an oribatid-to a springtail-dominated community was observed in less polluted soils (R2 = 0.68). In addition, Pb bioamplification occurred in microarthropods, with higher Pb concentrations in predators than in detritivorous microarthropods. Finally, the importance of feeding and reproductive ecological traits as potentially relevant descriptors of springtail community structures was highlighted. This study demonstrates the interest of microarthropod communities with different trophic levels and ecological features for evaluating the global environmental impact of metal(loid) pollution on soil biological quality

Spatially Explicit Analysis of Metal Transfer to Biota: Influence of Soil Contamination and Landscape

Concepts and developments for a new field in ecotoxicology, referred to as “landscape ecotoxicology,” were proposed in the 1990s; however, to date, few studies have been developed in this emergent field. In fact, there is a strong interest in developing this area, both for renewing the concepts and tools used in ecotoxicology as well as for responding to practical issues, such as risk assessment. The aim of this study was to investigate the spatial heterogeneity of metal bioaccumulation in animals in order to identify the role of spatially explicit factors, such as landscape as well as total and extractable metal concentrations in soils. Over a smelter-impacted area, we studied the accumulation of trace metals (TMs: Cd, Pb and Zn) in invertebrates (the grove snail Cepaea sp and the glass snail Oxychilus draparnaudi) and vertebrates (the bank vole Myodes glareolus and the greater white-toothed shrew Crocidura russula). Total and CaCl2-extractable concentrations of TMs were measured in soils from woody patches where the animals were captured. TM concentrations in animals exhibited a high spatial heterogeneity. They increased with soil pollution and were better explained by total rather than CaCl2-extractable TM concentrations, except in Cepaea sp. TM levels in animals and their variations along the pollution gradient were modulated by the landscape, and this influence was species and metal specific. Median soil metal concentrations (predicted by universal kriging) were calculated in buffers of increasing size and were related to bioaccumulation. The spatial scale at which TM concentrations in animals and soils showed the strongest correlations varied between metals, species and landscapes. The potential underlying mechanisms of landscape influence (community functioning, behaviour, etc.) are discussed. Present results highlight the need for the further development of landscape ecotoxicology and multi-scale approaches, which would enhance our understanding of pollutant transfer and effects in ecosystems

Contamination, risk, and source apportionment of potentially toxic microelements in river sediments and soil after extreme flooding in the Kolubara River catchment in Western Serbia

Climate change is contributing to an increase in extreme weather events. This results in a higher river flooding risk, causing a series of environmental disturbances, including potential contamination of agricultural soil. In Serbia, the catastrophic floods of 2014 affected six river basins, including the Kolubara River Basin, as one of the larger sub-catchments of the large regional Sava River Basin, which is characterized by large areas under agricultural cultures, various geological substrates, and different types of industrial pollution. The main aim of this study was to establish the sources of potentially toxic elements in soil and flood sediments and the effect of the flood on their concentrations. Field sampling was performed immediately after water had receded from the flooded area in May 2014. In total, 36 soil samples and 28 flood sediment samples were collected. After acid digestion (HNO3), concentrations of the most frequent potentially toxic elements (PTE) in agricultural production (As, Cd, Cr, Cu, Ni, Pb, Zn) and Co which are closely related to the geological characteristics of river catchments, were analyzed. The origin, source, and interrelations of microelements, as well as BACKGROUND: values of the PTE of the river catchment, the pollution index (Pi), enrichment factor (Ef), and geological index (Igeo), were determined, using statistical methods such as Pearson correlations, principal component analysis (PCA), and multiple linear regression (MLRA). The content of the hot acid-extractable forms of the elements, PCA, and MLRA revealed a heavy geological influence on microelement content, especially on Ni, Cr, and Co, while an anthropogenic influence was observed for Cu, Zn, and Cd content. This mixed impact was primarily related to mines and their impact on As and Pb content. The pseudo-total concentrations of all the analyzed elements did not prove to be a danger in the catchment area, except for Cu in some samples, indicating point-source pollution, and Ni, whose pseudo-total content could be a limiting factor in agricultural production. For the Ef, the Ni content in 59% soil and 68% flood sediment samples is classified into influence classes. The similar pseudo-total contents of the elements studied in soil samples and flood sediment and their origin indicate that the long-term soil formation process is subject to periodic flooding in the Kolubara River Basin without any significant changes taking place. This implies that floods are not an endangering factor in terms of the contamination of soil by potentially toxic elements in the explored area