Silver origins and spatial distribution in soils of southwestern France: A first assessment with cokriging

Ag is a rare, non-essential metal with many applications in different forms, including nanoparticles (Ag-NPs). Its release into the soil environment can represent a risk, due to the toxicity of silver. This study is based on the analysis of samples from the two sampling campaigns of the Soil Quality Measurement Network, RMQS1 and RMQS2, to establish the spatial distribution and origin of Ag in the soils of southwestern France (area of 90,293 km2). Given the progress of the second campaign (completion in 2027), we chose to do a cokriging to estimate the spatial distribution, with Pb, Cd or Cu as potential secondary variables. The results of the analyzes of the 35 samples of the RMQS2 indicate a range of Ag concentration in the soils going from 0.015 to 0.222 mg kg-1 and a median of 0.081 mg kg -1. Correlations were found between the concentrations of Ag Cd, Cu and Pb, and also between Ag concentrations and distance to Pb mines and deposits (r = 0.62). This suggests a common origin for Ag and Pb linked to historical exploitations of argentiferous galena. No link could be demonstrated between the concentration of Ag and the high density of anti-hail ground generators in the region. The analysis of the (auto-) variograms showed that Pb is the most relevant variable compared to Cd and Cu to achieve a cokriging. Thus, based on Ag concentrations from RMQS2 and Pb concentrations from RMQS1 (356 samples), a linear co -regionalization model was established and the co-kriging of Ag concentrations in soils calculated. Compared to ordinary kriging, cokriging improved the quality of the interpolation (decrease in the root mean square error).