GEMAS: establishing geochemical background and threshold for 53 chemical elements in European agricultural soil

The GEMAS (geochemical mapping of agricultural soil) project collected 2108 Ap horizon soil samples from regularly ploughed fields in 33 European countries, covering 5.6 million km2. The <2 mm fraction of these samples was analysed for 53 elements by ICP-MS and ICP-AES, following a HNO3/HCl/H2O (modified aqua regia) digestion. Results are used here to establish the geochemical background variation and threshold values, derived statistically from the data set, in order to identify unusually high element concentrations for these elements in the Ap samples. Potentially toxic elements (PTEs), namely Ag, B, As, Ba, Bi, Cd, Co, Cr, Cu, Hg, Mn, Mo, Ni, Pb, Sb, Se, Sn, U, V and Zn, and emerging ‘high-tech’ critical elements (HTCEs), i.e., lanthanides (e.g., Ce, La), Be, Ga, Ge, In, Li and Tl, are of particular interest. For the latter, neither geochemical background nor threshold at the European scale has been established before. Large differences in the spatial distribution of many elements are observed between northern and southern Europe. It was thus necessary to establish three different sets of geochemical threshold values, one for the whole of Europe, a second for northern and a third for southern Europe. These values were then compared to existing soil guideline values for (eco)toxicological effects of these elements, as defined by various European authorities. The regional sample distribution with concentrations above the threshold values is studied, based on the GEMAS data set, following different methods of determination. Occasionally local contamination sources (e.g., cities, metal smelters, power plants, agriculture) can be identified. No indications could be detected at the continental scale for a significant impact of diffuse contamination on the regional distribution of element concentrations in the European agricultural soil samples. At this European scale, the variation in the natural background concentration of all investigated elements in the agricultural soil samples is much larger than any anthropogenic impact

Near-zero-waste processing of low-grade, complex primary ores and secondary raw materials in Europe: technology development trends

With an increasing number of low-grade primary ores starting to be cog-effectively mined, we are at the verge of mining a myriad of low-grade primary and secondary mineral materials. At the same time, mining practices and mineral waste recycling are both evolving towards sustainable near-zero-waste processing of low-grade resources within a circular economy that requires a shift in business models, policies and improvements in process technologies. This review discusses the evolution towards low-grade primary ore and secondary raw material mining that will allow for sufficient supply of critical raw materials as well as base metals. Seven low-grade ores, including primary (Greek and Polish laterites) and secondary (fayalitic slags, jarosite and goethite sludges, zincrich waste treatment sludge and chromium-rich neutralisation sludge) raw materials are discussed as typical examples for Europe. In order to treat diverse and complex low-grade ores efficiently, the use of a new metallurgical systems toolbox is proposed, which is populated with existing and innovative unit operations: (i) mineral processing, (ii) metal extraction, (iii) metal recovery and (iv) matrix valorisation. Several promising novel techniques are under development for these four unit-operations. From an economical and environmental point of view, such processes must be fitted into new (circular) business models, whereby impacts and costs are divided over the entire value chain. Currently, low-grade secondary raw material processing is only economic and environmentally beneficial when the mineral residues can be valorised and landfill costs are avoided and/or incentives for waste processing can be taken into account

Use of GEMAS data for risk assessment of cadmium in European agricultural and grazing land soil under the REACH Regulation

Over 4000 soil samples were collected for the “Geochemical Mapping of Agricultural and Grazing Land Soil of Europe” (GEMAS) project carried out by the EuroGeoSurveys Geochemistry Expert Group. Cadmium concentrations are reported for the <2 mm fraction of soil samples from regularly ploughed fields (agricultural soil, Ap, 0 - 20 cm, N - 2218) and grazing land soil (Gr, 0 - 10 cm, N - 2127)

Copper toxicity in soils amended with copper containing fungicides

The long-term application of copper containing pesticides can cause a significant accumulation of Cu in soils. In order to assess the potential toxic effects of these increased Cu concentrations, a comprehensive comparison of Cu toxicity in a set of soils with high Cu concentrations due to the application of Cu pesticides and corresponding reference soils was performed. Soils with a long history of application of Cu containing fungicides were sampled at 11 vineyards across Europe including an uncontaminated control soil outside each vineyard. Standard ecotoxicity tests for plant yield, root length, nitrification and invertebrates (Enchythraeus albidus) reproduction were performed on each soil of both the vineyard gradient and the corresponding control soil spiked with CuCl2. For all vineyard gradients, the increased Cu concentration (maximum 349 - 689 mg Cu/kg) did not decrease the response of any test compared to the corresponding control soils. Spiking these control soils with CuCl2 however resulted in clear dose-response curves and toxicity data for these freshly spiked control soils are in the range of toxicity data for these endpoints reported in the European Voluntary Risk Assessment Report (VRAR) on Cu and its compounds. Soil limits (Predicted No Effect Concentration, PNEC) calculated according to this VRAR are a factor 2.2 to 5.7 below the Cu concentrations observed in the sampled vineyard soils and therefore seem to be over-protective for soils contaminated with Cu due to the long term use of Cu containing pesticides. It is assumed that long-term accumulation of Cu in soils due to the annual application of small amounts of Cu, as is the case for Cu plant protection products, may result in stronger attenuation of Cu availability with time and hence a lower toxicity of Cu in soils compared to the default assumptions in the VRAR on the effect of ageing on toxicity (as reflected in the so-called leaching-ageing factor). Therefore, a larger scenario-specific leaching/ageing factor is proposed for the effects assessment of Cu in soils affected by long-term application of Cu containing pesticides.status: accepte

Copper toxicity in soils under established vineyards in Europe: a survey

Copper (Cu) containing fungicides have been used for more than one century in Europe on agricultural soils, such as vineyard soils. Total Cu concentrations in such soils can exceed toxicological limits that are commonly derived using artificially spiked soils. This study surveyed Cu toxicity in vineyard soils with reference to soils spiked with CuCl2. Soil was collected in six established European vineyards. At each site, samples representing a Cu concentration gradient were collected. A control (uncontaminated) soil sampled nearby the vineyard was spiked with CuCl2. Toxicity was tested using standard ecotoxicity tests: two plant assays (Lycopersicon esculentum Miller (tomato) and Hordeum vulgare L. (barley) growth), one microbial assay (nitrification) and one invertebrate assay (Enchytraeus albidus reproduction). Maximal total Cu concentrations in the vineyard sites ranged 435-690 mg Cu kg-1, well above the local background (23-105 mg Cu kg-1). Toxicity in spiked soils (50% inhibition) was observed at added soil Cu concentrations from 190 to 1039 mg Cu kg-1 (mean 540 mg Cu kg-1) depending on the assay and the site. In contrast, significant adverse effects were only found for three bioassays in vineyard samples of one site and for two bioassays in another site. Biological responses in these cases were more importantly explained by other soil properties than soil Cu. Overall, no Cu toxicity to plants, microbial processes and invertebrates was observed in vineyard soil samples at Cu concentrations well above European Union limits protecting the soil ecosystem.status: publishe

Influence of soil properties on copper toxicity for two soil invertebrates

Although a large body of evidence indicates that metal toxicity to soil organisms is affected by physicochemical soil properties, use of this knowledge in ecological risk assessments is limited because of the lack of a model applicable to a wide range of soils. To study the effect of soil characteristics on the toxicity of copper to terrestrial invertebrates, chronic toxicity tests with Eisenia fetida and Folsomia candida were performed in 19 European field soils. These soils were carefully selected to cover the range of toxicity-influencing parameters encountered in the European Union. Toxicity values varied greatly among soils, with 28-d median effect concentrations ranging from 72.0 to 781 mg Cu/kg dry weight for E.fietida and from 45.4 to 2,270 mg Cu/kg dry weight for F. candida. For both species, variation in copper toxicity values was best explained by differences in the actual cation-exchange capacity (CEC) at soil pH. Using the obtained regression algorithms, the observed toxicity could, in most cases, be predicted within a factor of two for E. fetida and within a factor of three for F. candida. The developed models were validated in three additional European field soils, a standard artificial soil and a standard field soil. The presented regression equations, based on the actual CEC, offer an easy-to-apply method for taking the influence of soil properties on metal toxicity into account

Toxicity in lead salt spiked soils to plants, invertebrates and microbial processes: Unraveling effects of acidification, salt stress and ageing reactions

The fate and effects of toxic trace metals in soil freshly spiked soluble metal salts do not mimic those of metals in the field. This study was set up to test the magnitude of effects of salinity, acidification, and ageing on toxicity of lead (Pb) to plants, invertebrates and soil microbial processes. Three soils were spiked with Pb2+ salts up to a concentration of 8000 mg Pb/kg and were tested either after spiking, after soil leaching followed by pH correction, or after a 5-year outdoor ageing period with free drainage followed by pH correction. Soil solution ionic strength exceeded 150 mmol/L in soils tested directly after spiking and this decreased partially after leaching and returned back to background values after 5-year outdoor equilibration. Chronic toxicity to two plants, two invertebrates, and three microbial endpoints was consistently found in all spiked soils that were not leached. This toxicity significantly decreased or became absent after 5 years of ageing in 19 of the 20 toxicity tests by a factor 8 (median factor; range: 1.4->50), measured by the factor increase of total soil Pb dose required to induce 10% inhibition. The toxicity of Pb in leached soils was intermediate between the other two treatments. The lowest detectable chronic thresholds (EC10) in aged soils ranged 350-5300 mg Pb/kg. Correlation analysis, including data of Pb2+ speciation in soil solution, suggests that reduced ionic strength rather than acidification or true ageing is the main factor explaining the soil treatment effects after spiking. It is suggested that future toxicity studies should test fine PbO powder as a relevant source for Pb in soils to exclude the confounding salt effects.publisher: Elsevier articletitle: Toxicity in lead salt spiked soils to plants, invertebrates and microbial processes: Unraveling effects of acidification, salt stress and ageing reactions journaltitle: Science of The Total Environment articlelink: http://dx.doi.org/10.1016/j.scitotenv.2015.07.067 content_type: article copyright: Copyright © 2015 Elsevier B.V. All rights reserved.status: publishe