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Artisanal small-scale gold mining (ASGM), an increasingly prevalent activity in South America, generates mercury-contaminated tailings that are often disposed of in the environment, leading to the introduction of mercury into ecosystems and the food web, where it bioaccumulates. Therefore, studying the geochemical processes involved in the desorption and dissolution of mercury in these tailings is essential for critical risk evaluations in the short and long term. For this purpose, sequential extraction procedures (SEPs) can be useful because they help to identify the phases to which Hg is associated, although they also have limitations such as a lack of selectivity and specificity. In this work, we propose a modified four-step SEP: exchangeable mercury (F1), oxidizable mercury (F2), mercury bound to Fe oxides (F3), and strongly bound mercury (F4). To test this adapted sequential extraction method, we evaluated the Hg contamination in mercury-contaminated tailings of the Amazon basin. The results revealed a total mercury concentration of 103 ± 16 mg·kg-1 in the tailings, with a significant portion in F1 (28% of the total), where Hg was bioavailable. The large Hg concentration in F3 (36%) suggested that Fe oxides likely contribute to mercury retention. Together, the SEP results emphasize the urgent need for improved surveillance of gold mining activities and responsible tailings management practices to mitigate environmental contamination and safeguard the health of the Amazon ecosystem.

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Cell wall polysaccharides were isolated by sequential extractions from coffee pulp, the main solid waste from coffee processing. Extractions were conducted with distilled water at room and boiling temperatures, 0.5 % ammonium oxalate and 0.05 M Na2CO3 to obtain pectic fractions. Hemicelluloses were extracted by using 2 M and 4 M NaOH. The composition of the hemicellulose fractions suggested the presence of xyloglucans, galactomannans and arabinogalactan-proteins (AGPs). The main part of the cell wall polysaccharides recovered from coffee pulp were pectins branched with arabinogalactans. Coffee pulp pectic fractions were low-methoxylated with various amounts of protein (0.5-8.4 %) and phenolics (0.7-8.5 %). Detection at 280 nm in the HPSEC analyses and radial gel diffusion assay using Yariv reagent indicated the presence of AGPs in most of these fractions. NMR analyses of chelating agent (CSP) and dialyzed water (WSPD) extracted pectins were carried out. The results demonstrated that CSP contains only AG I. On the other hand, AG I and AG II are present in WSPD, probably covalently linked to the pectic portion. Comparison with the literature indicated similarities between the cell wall polysaccharides from coffee pulp and green coffee beans.

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The Sepetiba Bay (Southeast Brazil) is a known Cd- and Zn-contaminated site that received spills of a large slag pile leachate from a Zn smelter. With important harbors, Sepetiba Bay demands periodic dredging operations which affect the mobility of the metals. The main goal of this work was to assess metal mobility in sediments and its associated toxicity in a fictive dredging area, to evaluate the risks of the operation. To achieve this goal, 18 superficial sediment samples were collected and characterized for pH and Eh. Sediments were analyzed for grain size, organic carbon, and total nitrogen, and metal mobility was evaluated with a sequential extraction procedure, proposed by the European Community Bureau of Reference (BCR). The results demonstrate that Cd and Zn are mainly associated with the exchangeable fraction (mean concentrations 1.4 mg kg-1 and 149.4 mg kg-1, respectively) and reducible fractions (mean concentrations 0.3 mg kg-1 and 65.5 mg kg-1, respectively), while Fe, Cr, Cu, Ni, and Al were associated with the residual fraction. Metals in the residual fraction are probably associated with the mineral lattice of the sediment and should not represent an environmental risk for the biota. The application of the enrichment factor and three risk assessment indexes (Risk Assessment Code, Risky Pollution Index, and Bioavailability Risk Assessment Index) show that the sediments are considerably enriched in metals that constitute a relevant risk for the sediment biota. In the case of dredging operations, Cd and Zn should be released to the overlying waters and be available to organisms, threatening the whole ecosystem. The proposed approach was shown to be much more precise than what is frequently presented in the Environmental Impact Assessments that only consider the threshold limits of the legislation.

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Faced with a potential risk of a colossal amount of sludge released into the Doce River basin in the most shocking Brazilian mining disaster, we proposed to assess the environmental risk from a new perspective: Understanding the mobilization of potentially toxic elements (PTE) with the geochemical fractions. Soil and sediment samples were taken in nine sites throughout the basin and characterized. The environmental risk was assessed from the PTE sequential extraction in three fractions: soluble, reducible, and oxidizable, in addition to the pseudo-total concentration. The potential mobile fraction (PMF) showed a considerable PTE mobilization from the soil and sediment samples. Principal component statistical analysis indicated the sludge as the single source of PTE. The risk assessment depended on the fractional distribution and the PTE enrichment degree in the affected samples. The fractional distribution contributed mainly to Mn, Sb, and Pb mobility, with PMF of 96%, 81%, and 100%, respectively. The mobilization of Cd, Co, Ag, Ni, Pb, Zn, and Cu was predominantly related to the degree of enrichment. The risk assessment from the geochemical fractions pointed to the magnitude of the disaster and the dispersion of PTE with severe effects on the affected populations. Therefore, more strongly enforced regulations in the basin are needed, in addition to the urgent use of more secure containment dams. It is also essential to emphasize the transferability of the design of this study to other environmental units in mining disaster conditions.

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The present study performed geochemical fractioning of major and minor elements in a cross-shelf gradient of the Abrolhos Bank, where the largest and most diverse coral reefs in the South Atlantic are concentrated. The fractioning was performed using sequential extractions to determine the degree of availability and toxicity of the elements. The mobility pattern of the elements investigated were in the following order: Ca > Mn > Pb > Cr > Zn > Fe > V > Cu > Ba>Al > Ni > Ti. For elements, such as (Ti, Ni, Al, Ba, Cu, V, Fe, Zn, Cr, Pb), the highest concentrations were in the residual phase at some sampling sites. As established by Environment Canada (Threshold Effect Level - TEL and Probable Effect Level - PEL), Ba, Cr, and Ni produced values higher than the limits, associated with higher concentrations of other elements. In addition, significant proportions of these elements were found in mobile phases in the same sites. Thus, more rigorous measures are critical to avoid alarming levels of chronic environmental pollution inside and outside protected areas of the region. To enhance the sustainability of the region, more effective enforcement is crucial to prevent anthropic contamination that may threaten its biodiversity. The results provide the baseline for future studies regarding the potential impacts of the breach of the tailings dam in the region of Mariana, Minas Gerais.

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Naturally elevated contents of copper (Cu) and nickel (Ni) are found in soils worldwide, and their potential toxicity is better understood when geochemical reactive fractions are identified and monitored. Thus, this study aimed to assess the bioavailability of Cu and Ni and estimate environmental risks in naturally metal-enriched soils of Carajás Mining Province, Eastern Amazon, Brazil. For that, 58 surficial soil samples were analyzed for their extractable contents of Cu and Ni by Mehlich 1. Next, 13 soil samples were selected for additional single and sequential extractions, for the determination of metal content in the shoots of grasses naturally growing in these soils and for calculating the risk assessment code. Despite the naturally high total concentrations, the contents of easily available Cu and Ni are a minor fraction of total concentrations (up to 10.15%), and the reducible oxide and residual pools hold the major proportion of total content of metals. This contributed to low bioavailability, low environmental risk, and also to low concentrations of these metals on grasses collected in the field. Soil organic matter, Fe2O3, Al2O3 and clay content have a dominant role in metals retention on studied soils. Our findings on the bioavailability of Cu and Ni in a region of great economic relevance for Brazil are important not only for predicting the elements' behavior in the soil-plant system but also for refining risk assessments and to provide useful data for environmental quality monitoring.

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Studies regarding the role of geochemical processes in urban environmental matrices (UEM) and their influence on respiratory bioaccessibility in humans are scarce in humid tropical regions, especially in Brazil. Contaminated UEM are potentially hazardous to humans if particles <10 µm in diameter are inhaled and reach the tracheobronchial region. In this study, we evaluated samples collected in Brazilian UEMs with a large environmental liability left by former mining industries and in a city with strong industrial expansion. UEM samples were classified into soil, sediment and mine tailings according to the characteristics of the collection sites. The respiratory bioaccessibility of potentially harmful elements (PHE) was evaluated using artificial lysosomal fluid (ALF, pH 4.5), and the BCR-sequential extraction was performed to evaluate how the respiratory bioaccessibility of the PHE was related to the solid phase partitioning. The bioaccessible fraction (BAF) ranged from 54 to 98% for Cd; 21-89% for Cu; 46-140% for Pb, 35-88% for Mn and; 41-84% for Zn. The average BAF of the elements decreased in the following order: Soil: Cd > Pb > Mn > Zn > Cu; Tailing: Pb > Cd > Zn > Mn > Cu; and Sediments: Pb > Mn > Cd > Zn > Cu. BCR-fractions were useful to predict the PHE bioaccessibility (R2 = 0.79-0.98), thus suggesting that particle geochemistry and mineralogy can influence PHE behaviour in the pulmonary fluid. Therefore, this approach provides a combination of quantitative and qualitative data, which allows us to carry out a more realistic assessment of the current situation of the potentially contaminated site and possible alternatives for decision making by the stakeholders.

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Agricultural soils were collected from Mocorito river basin, to determine potentially toxic elements (PTEs) subtotal concentrations and geochemical fractionation, and evaluate their environmental and health risks. All sites showed low As and Cr concentrations. Subtotal concentrations (mg/kg) ranged between 6.8 and 25.6 for As, 1.9 and 2.5 for Cd and 22.5 and 55.1 for Cr. These values were classified as moderately contaminated for As, while a considerable contamination was presented for Cd and Cr. Geochemical partitioning revealed that PTEs are strongly linked with residual phase. Arsenic was associated with amorphous Fe-oxyhydroxides. Ecotoxicological indices showed from low (As and Cr) to considerable (Cd) potential ecological risk factors; potential non-carcinogenic risks by As, Cd and Cr, and potential carcinogenic risks by As and Cr. Lithogenic and anthropogenic sources were identified. Arsenic and Cr showed lithogenic influence, while Cd increased, caused by nearby activities, representing an environmental and health risk.

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The Paraiba do Sul (PSR) and Guandu Rivers (GR) water diversion system (120 km long) is located in the main industrial pole of Brazil and supplies drinking water for 9.4 million people in the metropolitan region of Rio de Janeiro. This study aims to discern the trace metals dynamics in this complex aquatic system. We used a combined approach of geochemical tools such as geochemical partitioning, Zn isotopes signatures, and multivariate statistics. Zinc and Pb concentrations in Suspended Particulate Matter (SPM) and sediments were considerably higher in some sites. The sediment partition of As, Cr, and Cu revealed the residual fraction (F4) as the main fraction for these elements, indicating low mobility. Zinc and Pb were mostly associated with the exchangeable/carbonate (F1) and the reducible (F2) fractions, respectively, implying a higher susceptibility of these elements to being released from sediments. Zinc isotopic compositions of sediments and SPM fell in a binary mixing source process between lithogenic (δ66/64ZnJMC ≈ + 0.30‰) and anthropogenic (δ66/64ZnJMC ≈ + 0.15‰) end members. The lighter δ66/64ZnJMC values accompanied by high Zn concentrations in exchangeable/carbonate fraction (ZnF1) enable the tracking of Zn anthropogenic sources in the studied rivers. Overall, the results indicated that Hg, Pb, and Zn had a dominant anthropogenic origin linked to the industrial activities, while As, Cr, and Cu were mainly associated with lithogenic sources. This work demonstrates how integrating geochemical tools is valuable for assessing geochemical processes and mixing source effects in anthropized river watersheds.

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Cationic micronutrients bioavailability depends on the chemical characteristics of soil fractions. Fourteen soils received individual doses of five micronutrients (Cu, Fe, Mn, Zn, B) arranged in seven treatments set according a Baconian Matrix. The soils incubated with treatments during 15 days had corn cultivated in greenhouse for 30 days, in three consecutive growth cycles. The cationic micronutrients were determined in the corn shoots after each growth cycle. Soil samples collected before the first and after each growth cycle had the available concentrations of Cu, Fe, Mn and Zn determined by single extractions (Mehlich-1 and DTPA-pH 7.3) and by sequential extraction. Correlation analysis was performed for the Cu, Fe, Mn and Zn concentrations determined in the corn shoots, the available concentrations of Cu, Fe, Mn and Zn in the soils (Mehlich-1 and DTPA) and the concentrations of Cu, Fe, Mn and Zn in the soil fractions (sequential extraction). The distribution of available metals forms in fractions reflected their affinity with soil components. Soil available Cu correlated with Cu bound to organic matter. The exchangeable fraction was the main source of soil available Mn and Zn. The Fe availability related mainly to the Mn oxides, Fe oxides, and exchangeable fractions. The plants absorbed Cu mainly from the Mn-oxides and organic matter fractions.

A biodisponibilidade dos micronutrientes catiônicos depende das características químicas das frações do solo. Quatorze solos receberam doses individuais de cinco micronutrientes (Cu, Fe, Mn, Zn, B) em sete tratamentos, estabelecidos conforme uma Matriz Baconiana. Os solos, com os tratamentos, foram incubados em vasos plásticos durante 15 dias, cultivando-se milho durante 30 dias, em três ciclos consecutivos. Amostras de solo e planta foram coletadas após cada ciclo de crescimento. Os metais foram determinados na parte aérea das plantas e correlacionados com sua disponibilidade no solo (DTPA/Mehlich-1) e concentrações nas frações do solo (extração sequencial). A distribuição dos metais disponíveis nas frações refletiu sua afinidade com os componentes do solo. O Cu disponível correlacionou-se com o ligado à matéria orgânica. Enquanto a fração trocável foi a principal fonte de Mn e Zn disponíveis, a disponibilidade de Fe esteve ligada às frações óxidos de Mn, óxidos de Fe, e fração trocável. As plantas absorveram o Cu, principalmente, das frações óxidos de Mn e matéria orgânica; o Mn das frações trocável e óxidos de Mn; e o Zn da fração trocável. As extrações com DTPA e Mehlich-1 se correlacionaram positivamente com Cu, Mn e Zn absorvidos pelas plantas

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