Mobile Metal Ion® analysis of European agricultural soils: bioavailability, weathering, geogenic patterns and anthropogenic anomalies

Two thousand one hundred and eight agricultural soils (0–20 cm depth) collected at a density of one sample per 2500 km2 under the auspices of the Geochemical Mapping of Agricultural Soils (GEMAS) project over most of the European continent have been analysed using the Mobile Metal Ion (MMI®) partial extraction technique with ICP-MS finish. For a number of elements, notably Ce, Ni, and Ca, coherent geogenic patterns have been observed which relate to underlying lithology. For Fe and Al, coherent patterns are also observed but the effects of weathering are evident, and provide a mechanism to explain the acidity of soils in high rainfall areas. Individual anomalies, many related to anthropogenic activity (mining, metallurgy, agriculture) have been observed for Ag, Au, Cu, Pb, Cd and Zn. Comparison of the results with aqua regia digestion and the equivalent National Geochemistry Survey of Australia (NGSA) provides insights into weathering processes and the concept of bioavailability

GEMAS: Prediction of solid-solution partitioning coefficients (Kd) for cationic metals in soils using mid-infrared diffuse reflectance spectroscopy

Partial least squares regression (PLSR) models, using mid-infrared (MIR) diffuse reflectance Fourier-transformed (DRIFT) spectra,wereusedtopredictdistributioncoefficient(Kd)valuesforselectedaddedsolublemetalcations(Agþ,Co 2þ,Cu 2þ,Mn 2þ,Ni 2þ, Pb2þ, Sn 4þ, and Zn2þ) in 4813 soils of the Geochemical Mapping of Agricultural Soils (GEMAS) program. For the development of the PLSR models, approximately 500 representative soils were selected based on the spectra, and Kd values were determined using a singlepointsolublemetal orradioactiveisotopespike.Theoptimummodels, usingacombinationofMIR–DRIFTspectra andsoilpH,resulted ingoodpredictionsforlogKdþ1forCo,Mn,Ni,Pb,andZn(R20.83)butpoorpredictionsforAg,Cu,andSn(R2<0.50).Thesemodels wereappliedtothepredictionoflogKdþ1valuesintheremaining4313unknownsoils.ThePLSRmodelsprovidearapidandinexpensive tool to assess the mobility and potential availability of selected metallic cations in European soils. Further model development and validationwillbeneededtoenablethepredictionoflogKdþ1valuesinsoilsworldwidewithdifferentsoiltypesandpropertiesnotcovered in the existing mode