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.

Phytoliths as indicators of pedogenesis and paleoenvironmental changes in Spodosols of the state of Rio de Janeiro, Brazil.

This study aims to contribute toward a better understanding of the current biodiversity patterns existing in the Atlantic Forest of the state of Rio de Janeiro from a paleo-ecological approach. Three soil profiles, each formed from distinct source materials under varied climate and vegetation conditions were selected from the coastal regions of Rio de Janeiro, Brazil. Soil horizon samples for chemical and physical characterization were collected from 10 cm-interval depths, and the total organic carbon was determined in addition to performing isotype and phytolithic analyses. The phytolithic analysis associated with the isotopic techniques (δ13C) permitted the characterization of three stages of paleo-environmental evolution for the studied soils, presenting valid trends that indicate small variations within the phytosociological structure of the vegetation along a Spodosols line in the studied areas. These stages indicated that the phytolithic assemblage was formed from a vegetation profile containing more trees, adapted to conditions colder than the existing vegetation, although no environmental changes were detected using the isotopic data. The milder temperature conditions may have favored the pedogenetic processes of the spodic B horizon formation as well as the maintenance of the organic matter contained in the soil. This study serves as the first draft for the paleo-environmental association among the regions where the analyzed profiles are found.