Métodos de digestão de solos e fertilizantes para análises de metais pesados

A utilização de métodos analíticos adequados tem grande importância para a avaliação de risco e para o monitoramento de metais potencialmente tóxicos em solos. Neste sentido, o objetivo deste trabalho foi comparar a eficiência de dois métodos de digestão de amostras de solo recomendados pela legislação brasileira para o gerenciamento de áreas contaminadas e que visam à determinação de teores ambientalmente disponíveis de metais (USEPA 3050B, USEPA 3051A), além de um método de digestão total de amostras (USEPA 3052). Foram analisadas amostras de dez classes de solo para os metais Cu, Zn, Cd, Pb, Ni e Hg. Os resultados obtidos demonstram que o método USEPA 3051A é mais eficiente que o USEPA 3050B na extração dos teores consideradas ambientalmente disponíveis dos metais Zn, Cu, Cd, Pb e Ni, pois, além de proporcionar maiores recuperações destes elementos, exige menor tempo de digestão, menor consumo de ácidos e reduzidos riscos de contaminações. O USEPA 3051A apresentou ainda maior eficiência para extração de Hg para solos com maiores teores de argila, devendo ser indicado para situações em que uma ampla gama de solos com diferentes características mineralógicas são analisados ou visando diminuir as perdas por volatilização do elemento em sistemas abertosThe use of appropriate analytical methods is of paramount importance for risk assessment and monitoring of potentially toxic metals in soils. In this sense, the objective of this study was to compare the effectiveness of two sample digestion methods, recommended by the Brazilian legislation for the management of contaminated areas (CONAMA, 2009), aiming at the determination of environmentally available metal concentrations (USEPA 3050B, USEPA 3051A), as well as a total digestion method (USEPA 3052). Samples from 10 classes of soils were analyzed for Cu, Zn, Cd, Pb, Ni and Hg. The results showed that the USEPA method 3051A is more efficient than the USEPA method 3050B in the extraction of levels considered environmentally available of Zn, Cu, Cd, Pb and Ni. Besides providing a higher recovery of these elements, the method requires shorter digestion time, lower consumption of acids and reduced risk of contamination. The USEPA method 3051A showed greater efficiency in Hg extraction in soils with higher clay content. Therefore, it is suitable for situations where a wide range of soils with different mineralogical characteristics are analyzed or in order to decrease the losses due to volatilization of the element in open systems.Conselho Nacional de Pesquisa e Desenvolvimento Científico e Tecnológico - CNP

Ultramafic soils and nickel phytomining opportunities: A review

Ultramafic soils are originated from ultramafic rocks such as peridotite and serpentinite and are highly enriched in metals (e.g., Ni, Cr, and Co) and depleted in plant nutrients (e.g., P, K, and Ca). Such characteristics make these soils unfavorable for agriculture and have raised environmental concerns on metal release to the environment. From another perspective, ultramafic soils host a diverse flora with higher endemism than surrounding non-ultramafic areas, which has provided scientists with an opportunity to investigate the evolutionary genetics of plant adaptation. Some plant species adapted to these stressful edaphic conditions developing the ability to accumulate uncommonly high metal concentrations in the harvestable biomass. Such species, called metal hyperaccumulators, can extract metals from ultramafic soils, especially Ni, in a circular economy approach in which the metal-rich biomass is incinerated to generate valuable bio-ores. Phytomining promises to turn ultramafic soils and low-grade ore bodies into economically viable alternatives to metal extraction. Here, we review the current knowledge on ultramafic soils and the most promising hyperaccumulators used to exploit them in temperate and tropical climates. In the tropics, including Brazil, the search for new hyperaccumulator candidates for phytomining and the knowledge to crop these species is incipient and holds untapped opportunities. Despite the feasibility of the phytomining chain has been proven, large-scale demonstrations of profitability are needed to establish the technology

Geochemistry and Spatial Variability of Rare Earth Elements in Soils under Different Geological and Climate Patterns of the Brazilian Northeast

ABSTRACT Growth in the agricultural and industrial sectors has increased the demand for rare earth elements (REEs) in the production of technological devices and fertilizers. Thus, the accumulation of these elements in the soil has become an environmental concern. Here, we aim to determine the natural contents of REEs in soils derived from different parent materials and under climatic conditions ranging from humid to semi-arid. We then evaluate the influence of major elements and soil properties on the geochemistry of REEs. The contents of REEs were determined using inductively coupled plasma optical emission spectroscopy. Major elements were determined by X-ray fluorescence spectrometry. The mean content of REEs in soils from Rio Grande do Norte (RN), Brazil, were in the followed order (mg kg-1): Ce (40.4) > La (18.9) > Nd (15.8) > Pr (7.3) > Sm (3.0) > Gd (2.6) > Dy (1.0) > Er (0.7) > Yb (0.6) > Eu (0.5) = Tb (0.5) > Ho (0.3) > Lu (0.2). The parent material was the main factor that governed the geochemistry of the REEs in soils of RN. Higher levels of REEs were observed in soils derived from igneous and metamorphic rocks. In contrast, sedimentary rocks - except for the region formed from limestone - generated soils with lower contents of REEs in the state. In addition, soils developed from the same parent material and under different climatic conditions showed the same geochemical signatures for REEs in soils. These results confirm the small effect of climate on REE geochemistry in soils of RN and lead to the conclusion that the geochemical signature of REEs in these soils reflects the composition of the underlying parent material. The lack of significant correlation between (La/Yb)N ratio and the Chemical Alteration Index also confirms the low influence of climate on soil REE geochemistry. Among the major elements, Fe and Si had a greater influence on soil REE geochemistry. Higher REEs were seen in areas with more Fe and less Si. These REE levels were clearly controlled by the type of parent material. The Nd, Sm, Tb, Dy, Ho, Yb, and Er levels showed strong spatial dependence; this dependence was moderate for the Pr, La, Ce, Eu, Gd, and Lu levels. Spatial variability maps of REEs are particularly important to identify areas under environmental impact. Our results represent the most detailed study of the surface geochemistry of REEs in Brazilian soils and contribute to the scarce data available on these elements in Brazil

Rare Earth Element Concentrations in Brazilian Benchmark Soils

ABSTRACT: Studies regarding background concentrations of rare earth elements (REEs) are scarce and have mainly focused on a limited number of soil types from the northern hemisphere. The aim of this study was to determine REE concentrations in thirty-five benchmark soils of Brazil. Composite soil samples were taken from areas under native vegetation or with minimal anthropogenic influence. Concentrations of La, Ce, Pr, Nd, Sm, Eu, Gd, Yb, Lu, Dy, Er, Ho, Tb, Tm, Y, Sc, and Fe were determined by ICP-OES using a cyclonic spray chamber/nebulizer system after microwave acid digestion. Results were assessed by descriptive statistics, Pearson correlation, and principal component analysis (PCA). Regression analyses among Fe, organic carbon, and REEs were performed to provide a tool for estimating REE concentrations in soils. The REE concentrations in the Brazilian benchmark soils were in the following order: Ce > La > Nd > Pr > Y > Sm > Gd > Sc > Dy > Yb > Eu > Er > Tb > Ho > Lu > Tm. The clear decoupling between light and heavy rare earth elements in soils, indicated by multivariate analysis, is mainly related to differences in parent material. The lowest REE concentrations were found in sandy sediments, whereas the highest REE concentrations were observed in basalt, biotite gneiss, and clayey sediments. The organic carbon and Fe concentrations can properly predict REE concentrations in soils; such a finding can assist in estimating REE concentrations in soils not only in Brazil but also in similar soils developed under tropical conditions

Comparison of digestion methods to determine heavy metals in fertilizers

The lack of a standard method to regulate heavy metal determination in Brazilian fertilizers and the subsequent use of several digestion methods have produced variations in the results, hampering interpretation. Thus, the aim of this study was to compare the effectiveness of three digestion methods for determination of metals such as Cd, Ni, Pb, and Cr in fertilizers. Samples of 45 fertilizers marketed in northeastern Brazil were used. A fertilizer sample with heavy metal contents certified by the US National Institute of Standards and Technology (NIST) was used as control. The following fertilizers were tested: rock phosphate; organo-mineral fertilizer with rock phosphate; single superphosphate; triple superphosphate; mixed N-P-K fertilizer; and fertilizer with micronutrients. The substances were digested according to the method recommended by the Ministry for Agriculture, Livestock and Supply of Brazil (MAPA) and by the two methods 3051A and 3052 of the United States Environmental Protection Agency (USEPA). By the USEPA method 3052, higher portions of the less soluble metals such as Ni and Pb were recovered, indicating that the conventional digestion methods for fertilizers underestimate the total amount of these elements. The results of the USEPA method 3051A were very similar to those of the method currently used in Brazil (Brasil, 2006). The latter is preferable, in view of the lower cost requirement for acids, a shorter digestion period and greater reproducibility