Rare earth elements (REEs): geochemical patterns and contamination aspects in Brazilian benchmark soils

Rare earth elements have been increasingly used in modern societies and soils are likely to be the final destination of several REE-containing (by)products. This study reports REE contents for topsoils (0-20 cm) of 175 locations in reference (n = 68) and cultivated (n = 107) areas in Brazil. Benchmark soil samples were selected accomplishing a variety of environmental conditions, aiming to: i) establishing natural background and anthropogenic concentrations for REE in soils; ii) assessing potential contamination of soils - via application of phosphate fertilizers - with REE; and, iii) predicting soil-REE contents using biomes, soil type, parent material, land use, sand content, and biomes-land use interaction as forecaster variables through generalized least squares multiple regression. Our hypotheses were that the variability of soil-REE contents is influenced by parent material, pedogenic processes, land use, and biomes, as well as that cultivated soils may have been potentially contaminated with REE via input of phosphate fertilizers. The semi-total concentrations of REE were assessed by inductively coupled plasma mass spectrometry (ICP-MS) succeeding a microwave-assisted aqua regia digestion. Analytical procedures followed a rigorous QA/QC protocol. Soil physicochemical composition and total oxides were also determined. Natural background and anthropogenic concentrations for REE were established statistically from the dataset by the median plus two median absolute deviations method. Contamination aspects were assessed by REE-normalized patterns, REE fractionation indices, and Ce and Eu anomalies ratios, as well as enrichment factors. The results indicate that differences in the amounts of REE in cultivated soils can be attributed to land use and agricultural sources (e.g., phosphate-fertilizer inputs), while those in reference soils can be attributed to parent materials, biomes, and pedogenic processes. The biomes, land use, and sand content helped to predict concentrations of light REE in Brazilian soils, with parent material being also of special relevance to predict heavy REE contents in particular.