ABSTRACT Identifying sediment sources is fundamental for protecting and improving soil and water quality. Conventional fingerprinting studies have often collected sediments at the overall watershed outlet only, resulting in an important spatial scale dependency. This study aimed to identify and to assess the delivery patterns of sediment sources within three priority sub-catchments (Sapocaji, Piedade and Minas) located in the downstream portion of the Ipojuca River watershed in Brazil. This research would build on understanding sediment sources in the studied watershed by elucidating source type contributions on a sub-catchment basis. Both bed and suspended sediment samples were collected in these sub-catchments, and two types of sources were sampled: surface and subsurface sources. A total of 21 geochemical tracers were measured. The tracers were evaluated for their conservation and discriminatory ability (Kruskal-Wallis test and linear discriminant analysis), and the best set of tracers was selected for source apportionment modeling using MixSIAR. Surface (i.e., sugarcane croplands) sources contributed the highest to suspended sediments in the Piedade and Minas sub-catchments. There was a difference in the quality of riverbank management, which helped explain contrasts in the importance of this source. Overall, sub-catchment-specific sediment control management measures, such as the revegetation of riparian forests, need to be implemented, mainly in the Sapocaji sub-catchment. These results underscore the importance of connectivity for surface source contributions. only dependency subcatchments sub catchments Sapocaji, (Sapocaji Brazil subcatchment catchment basis subcatchments, catchments, sampled 2 measured KruskalWallis Kruskal Wallis analysis, analysis , analysis) MixSIAR i.e., ie i e (i.e. croplands subcatchments. catchments. Overall subcatchmentspecific specific measures forests implemented subcatchment. catchment. i.e. (i.e i.e

ABSTRACT 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.

ABSTRACT: Environmental impacts caused by the addition of rare earth elements (REEs) to agricultural soils are a growing concern. The sedimentary basin of the Gurguéia River is located in one of the last agricultural frontiers in Brazil; nevertheless, data regarding quality reference values (QRVs) for REEs in soils are still scarce. The objective of this study was therefore to determine the natural concentration and establish the QRVs of REEs in soils of Gurguéia watershed, Brazil. Fifty-five composite soil samples were collected at sites under no or minimal anthropic interference. The average REE natural concentrations in soils from the Gurguéia watershed were lower than those found in other regions of Brazil and worldwide, following the order (mg kg−1): Ce (14.01) > Nd (6.19) > La (5.52) > Pr (2.51) > Sm (1.45) > Gd (0.93) > Dy (0.63) > Er (0.42) > Yb (0.39) > Tb (0.28) > Eu (0.26) > Lu (0.20). The parent material was the main factor that controlled the distribution of REEs in soils. The QRVs in soils followed the order (mg kg−1): Ce (18.8) > Nd (7.92) > La (6.32) > Pr (3.3) > Sm (1.97) > Gd (1.35) > Dy (0.85) > Er (0.55) > Yb (0.47) > Tb (0.37) > Lu (0.25). These values serve as a basis to assist the development of legislation, including REE thresholds for Brazilian soils.

ABSTRACT. We studied the mineralogical properties and chemical composition of different granites using energy dispersive X-ray spectroscopy coupled with scanning electron microscopy to understand the relationship between granite signatures and soil characteristics, including weathering patterns and soil fertility status. The discriminant analysis (DA) was based on soil physical and chemical properties and was used to differentiate soils developed from I- and S-type granites across contrasting climatic conditions in northeast Brazil. The DA identified the highest values of organic carbon, clay and plant nutrients as key variables to recognize soil profiles derived from I-type granites. In contrast, the greater sand contents and Al saturation distinguished soils developed from S-type granites. These results were related to the mineralogical characteristics of each granite type, such as a high percentage of silica-bearing minerals in the S-type granites. The highest concentrations of K, Ca, Mg, and P in I-type granites were found in feldspars, amphiboles, and apatite. These elements account for the majority of nutrients derived in their soil profiles. However, it seems that the harsh conditions of the humid tropical environment equalized the effect of the rocks on weathering rates-the difference in chemical index of alteration is more extreme in the dry region.

ABSTRACT. Metal concentrations in suspended sediments of one of the most polluted rivers in Brazil were measured. Concentrations of Cd, Cr, Cu, Fe, Mn, Ni, Pb, and Zn were determined by inductively coupled plasma while Hg and As were analyzed with hydride generation flow injection atomic absorption spectroscopy. Contamination of As, Cd, Cr, Cu, Fe, Hg, Mn, Ni, Pb, and Zn was assessed using pollution indices, ecological risk assessment, statistical multivariate techniques and comparison with sediment quality guidelines. Suspended sediments of the upstream portion of the Ipojuca River are moderately contaminated, especially with Mn and As. On the other hand, sediments of the downstream section are highly contaminated, mainly with Zn, Pb, and As. Furthermore, the mean Ei (potential ecological risk) values of Pb and As showed considerable ecological risk in the downstream cross section. The comparison of our data with sediment guideline values indicated that the concentrations of Mn and Pb in the upstream section of the Ipojuca River pose a risk to sediment-dwelling organisms, while Pb and Zn are the metals of concern in the downstream section.

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.

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.

A ausência de normatização de um método-padrão para determinar os metais pesados em fertilizantes no Brasil e a consequente utilização de diversos métodos de digestão têm provocado variações nos resultados, dificultando a sua interpretação. Nesse contexto, o objetivo deste trabalho foi comparar a eficiência de três métodos de digestão de fertilizantes para delimitar os metais Cd, Ni, Pb e Cr. Foram utilizadas 45 amostras de fertilizantes comercializados no nordeste do Brasil, além de uma amostra de fertilizante com teores de metais certificados pelo National Institute of Standards and Technology (NIST), incluindo fosfato natural, fertilizante organomineral com fosfato natural, superfosfato simples, superfosfato triplo, fertilizante misto e fertilizante com micronutrientes, que foram digeridos pelos métodos do Ministério da Agricultura, Pecuária e Abastecimento (MAPA) e da Agência Americana de Proteção Ambiental (USEPA): 3051A e 3052. Os resultados demonstraram que o método USEPA 3052 apresentou maiores recuperações para metais menos solúveis, como Ni e Pb, evidenciando que os teores totais desses elementos são subestimados pelos métodos convencionais de digestão para fertilizantes. O método USEPA 3051A evidenciou resultados muito semelhantes ao método atualmente em uso no Brasil (Brasil, 2006), sendo preferido seu uso em razão da diminuição dos custos com ácidos, do menor tempo de digestão e da maior reprodutibilidade.

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.