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Gold mining not only introduces mercury (Hg) contamination to soils but also facilitates the mobilization of other toxic substances, including arsenic (As). This study assessed the total content, chemical species, and bioavailable fraction of As in surface soils impacted by mining residues during frequent flooding. Analysis of 207 soil samples across the floodplain region of La Mojana, Colombia, screened to 2 mm with polyethylene mesh, revealed significant correlations (p < 0.05) between inorganic As, the residual phase, sulphur (S), iron (Fe), manganese (Mn), and aluminum (Al), indicating associations with sulfides and oxyhydroxides of Fe and Mn. The origin of toxicity was linked to suspended materials transported by rivers during flooding in areas with intense mining activity. Sites with better oxidizing conditions exhibited a higher presence of phases associated with amorphous and crystalline oxides in non-flooded areas. Although the bioavailable fraction was minimal in flooded sites, reducing conditions facilitated As mobility, resulting in higher concentrations in deeper soil layers, particularly as As(III). The contamination factor (CF) ranged from 1.3 to 11.1, and the geochemical index (Igeo) ranged from -0.2 to 2.9, indicating a moderate to high As contamination level in soils. This poses potential health risks, considering the agricultural use of these soils.

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Arsenic (As) and Cadmium (Cd) are toxic to rice plants. However, selenium (Se) has the potential to regulate As and Cd toxicity. The present study aimed to evaluate the co-exposure to As5+ and Se6+ species in two rice cultivars, BRS Pampa and EPAGRI 108. The plants were divided into six groups and cultivated until complete maturation of the grains, under greenhouse conditions. Regarding total As and inorganic As (i-As) accumulation in grains, the highest concentrations were found for BRS Pampa. For Se, EPAGRI 108 presented the highest concentration of inorganic and organic Se (i-Se and o-Se). The exposure assessments showed that Se biofortification can mitigate the As accumulation in rice and, consequently, the risk of As and Cd toxicity in grains for human consumption. The combined effect of As and Se in rice plants could represent an alternative to biofortify this food in a safe way and with a higher percentage of bioavailable Se. Although Se is able to mitigate As toxicity in rice plants, in the present study we showed that co-exposure in different cultivars under the same growing conditions may present different responses to As and Se exposure.

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Mushrooms may incorporate significant levels of Hg making its consumption harmful to human health. Mercury remediation induced by Se competition in edible mushrooms represents a valuable alternative since Se plays effective roles against Hg uptake, accumulation, and toxicity. In this way, Pleurotus ostreatus and Pleurotus djamor were cultivated on Hg-contaminated substrate simultaneously supplemented with Se(IV) or Se(VI) under different dosages in this study. The protective role of Se was assessed taking into account morphological characteristics and Hg and Se total concentrations determined by ICP-MS, as well as proteins and protein-bound Hg and Se distribution by SEC-UV-ICP-MS, and Hg speciation studies (Hg(II) and MeHg) by HPLC-ICP-MS. Both Se(IV) and Se(VI) supplementation were able to recover the morphology mainly of Hg-contaminated Pleurotus ostreatus. The mitigation effects induced by Se(IV) stood out more than Se(VI) in terms of Hg incorporation, decreasing the total Hg concentration up to 96 %. Also, it was found that supplementation mainly with Se(IV) reduced the fraction of Hg bound to medium molecular weight compounds (17-44 kDa) up to 80 %. Finally, it was shown a Se-induced inhibitory effect on Hg methylation, decreasing MeHg species content in mushrooms exposed to Se(IV) (51.2 µg g-1) up to 100 %.

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In this study, the concentration of six metal(loid)s was examined in the fish Oreochromis aureus collected from El Comedero dam during a massive mortality event induced by a mine tailing spill. A major spill (~ 300,000 m3) of waste was released into the San Lorenzo River System following a rupture in the tailing dam of a mining plant in NW Mexico; consequently, the discharged material flowed into El Comedero dam. The accumulation of metal(oid)s in the tissues of O. aureus showed higher levels in the liver than in the guts and muscle. Concentrations in the liver were high (As, 1.1-1063; Cd, 8.9-392; Cu, 372-59,129; Hg, 0.46-19.79; Se, 8.7-748; and Zn, 116-820 µg g-1), revealing that these fish were exposed to high concentrations of these elements. The mortality of fish could have resulted from the combined effect of the six analyzed metal(loid)s, as well as other residues present in mine tailings.

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Inorganic forms of As (arsenite - As(III) and arsenate - As(V)) are prevalent in soil and recognized for their high toxicity. Once in the soil, these forms of As can compromise key organisms for ecological processes, such as earthworms. The aim of the study was to evaluate the toxicity of arsenite and arsenate in the Californian earthworm Eisenia andrei exposed in natural soil and tropical artificial soil (TAS). Adverse effects were evaluated using avoidance test, acute toxicity test, and a sublethal concentration test to assess biochemical parameters. LC50 values for arsenite were 21.27 mg/kg in natural soil and 19.0 mg/kg in TAS and for arsenate were 76.18 mg/kg in natural soil and above 120 mg/kg in TAS. In the avoidance test, this behavior was shown to be significantly higher in the natural soil and for earthworms exposed to arsenite, while total antioxidant capacity, glutathione levels, lipid damage, and DNA damage were significantly higher in animals exposed to arsenite, but without differences in relation to the two types of soil tested. Animals exposed to As(V) showed increased activity of enzymes related to glutathione metabolism. The results obtained in the present study show the impact of As exposure on the health of the Californian earthworm E. andrei, especially in the form of arsenite, and alert the public authorities that legal limits should, whenever possible, consider the soil properties and also the different chemical species of the contaminants.

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The protection of wetlands is essential for sustainable development. The particular hydrology of wetlands creates conditions for the formation of hydric soils. Hydric soils are formed in oxide-reducing environments and perform important removal and re-oxidation of Fe and Mn oxides and hydroxides. They are also characterized by the formation of a superficial horizon enriched by the accumulation of organic matter. The objective of this study was to determine the concentration of essential (Co, Cu, Fe, Mn, Ni, Zn) and toxic (Al, Cd, Pb) elements in the soil solution in a wetland, surrounded by an intense agricultural activity area. The concentrations of the elements were evaluated according to the level of hydromorphy (border to the center) and the depth of the soil. The physical fractionation of these elements was also assessed (total and < 30 kDa), and the results were compared with the chemical speciation of these elements. Despite the high total concentrations of Al and Fe, the concentration of these elements was very low in the < 30 kDa fraction, which suggests that these elements are complexed with organic matter, in the form of hydroxides. Evidence of removal of Fe and Mn from the surface horizon was observed at the center of the wetland, where the highest level of hydromorphy is found. The results showed that the concentration of metals in the fraction < 30 kDa is insignificant, suggesting that the mechanisms of precipitation and/or adsorption to soil colloids play an important role in the regulation of this ecosystem.

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The artisanal and small-scale gold mining (ASGM) sector uses the most mercury (Hg) worldwide. Despite health concerns associated with high Hg exposures in these communities, ASGM sites are often situated in resource limited and remote regions which challenge traditional human biomonitoring approaches. To help overcome such challenges, here we report on the development of a high-quality method to characterize chemical speciation of Hg in dried blood spots (DBS), and then apply this method to assess Hg exposures in people sampled from an ASGM community (Pueblito Mejia) and a nearby town (Barranco de Loba) in Colombia. We collected DBS and urine samples from 35 individuals in 2018, and used these to assess occupational (DBS inorganic Hg (InHg) and urine total Hg (THg) measures) and environmental (DBS methylmercury (MeHg) measures) exposure of participants to different forms of Hg. The accuracy and precision of the DBS-based measures generally met assay performance guideline. In study participants, the mean concentrations of DBS MeHg, InHg, and THg, and urine THg were 1.9, 4.1, 6.0, and 3.1 µg/L, respectively. For 37% of the participants, DBS THg values exceeded the 5 µg/L 'alert level' proposed by the German HBM Commission. About 60% of the blood Hg was in the InHg form thus exemplifying a need to speciate Hg in blood sampled from ASGM sites to better understand the contributions of environmental and occupational exposure sources. This study demonstrates the feasibility of using DBS for Hg speciation exposure assessments in remote and resource-limited areas such as ASGM communities.

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In this work, fast sequential determination and chemical speciation analysis of inorganic arsenic and antimony in airborne particulate matter collected in outdoor and indoor environments using slurry sampling and detection by hydride generation atomic absorption spectrometry (HG-AAS) is proposed. A Doehlert design was applied to optimise the hydride generation conditions of As and Sb for fast sequential determination in the same aliquot of particulate matter samples after preparation of the slurry. The limits of quantification (LoQ) obtained for As and Sb were 0.3 and 0.9 ng m-3, respectively. The accuracy of the analytical method was confirmed by analysis of the certified reference material of urban particulate matter (SRM NIST 1648a), presenting concordance with certified values of 92.7±7.7% for As and 91.2±9.5% for Sb. Precision was expressed as relative standard deviation (% RSD, n=3), with our results presenting values better than 3.4% and 4.2% for total inorganic As and Sb, respectively. For all analysed samples, total As concentrations and its inorganic species were below the LoQ of the analytical method (<0.3 ng m-3). However, the averages of total inorganic Sb concentrations in airborne particulate matter, collected as total suspended outdoor particles (TSPoutdoor), inhalable particulate matter (PM10), and total suspended indoor particles (TSPindoor), were 3.1±0.5, 2.4±0.6, and 2.6±0.4 ng m-3, respectively. Trivalent Sb (Sb3+) was the predominant inorganic species in all samples investigated, with mean percentages of 76%, 72%, and 73% in TSPoutdoor, PM10, and TSPindoor, respectively. The presence of Sb and its predominant inorganic form (Sb3+) can be attributed to vehicular traffic close to the sampled urban areas. Therefore, fast sequential determination of As and Sb and their inorganic species in particulate matter samples prepared as slurry by FS-HG-AAS is an efficient, accurate, and precise method and can be successfully applied to routine analysis.

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Copper based pesticides are used to protect vineyards from fungal infections. Plants like black oats (Avena strigosa Schreb) can promote chemical changes in the rhizosphere, reducing copper (Cu) bioavailability in contaminated soils. The objective of this study was to evaluate how copper additions would affect growth, morphology and nutrient uptake by black oats and how the plants affect the chemical composition in rhizosphere and bulk soil. The soil was collected in grassland of southern Brazil. The soil was air-dried, adjusted pH and added phosphorus and potassium amendments, and then it was incubated. Three Cu levels were established in the soil with the addition of 0, 40 and 80 mg Cu kg-1. The experimental design consisted of pots containing 8 plants with 10 kg of soil. Rhizosphere (2 kg of soil) and bulk (8 kg of soil) separated by a 30 µm nylon membrane. Black oat plants were grown for 54 days. The soil and solution were chemically characterized throughout cultivation for Cu speciation. At 54 days after emergence, the soil was sampled and proceeded chemical analysis and plants were collected to determine yield dry matter, morphological parameters and nutrient concentration. Black oat plants induce increase of pH and dissolved organic carbon in the rhizosphere. These root-induced processes increase the percentage of complexed chemical species and decrease free Cu+2 in soil solution, decreasing Cu toxicity. However, soil contamination with Cu induces morphological changes and nutritional imbalances. Black oats could thus be planted along with vineyards, for such increasing protect the soil and promote nutrient cycling, as well as reduce the free Cu available fraction due to the root-induced modifications in the rhizosphere.

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In the last 30 years, since the discovery that vanadium is a cofactor found in certain enzymes of tunicates and possibly in mammals, different vanadium-based drugs have been developed targeting to treat different pathologies. So far, the in vitro studies of the insulin mimetic, antitumor and antiparasitic activity of certain compounds of vanadium have resulted in a great boom of its inorganic and bioinorganic chemistry. Chemical speciation studies of vanadium with amino acids under controlled conditions or, even in blood plasma, are essential for the understanding of the biotransformation of e.g. vanadium antidiabetic complexes at the physiological level, providing clues of their mechanism of action. The present article carries out a bibliographical research emphaticizing the chemical speciation of the vanadium with different amino acids and reviewing also some other important aspects such as its chemistry and therapeutical applications of several vanadium complexes.

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myo-Inositol phosphates are an important group of biomolecules that are present in all eukaryotic cells. The most abundant member of this family in nature is InsP6 (phytate, L12- in its fully deprotonated form). Phytate interacts strongly with inorganic and organic cations, and this interaction is essential for determining the possible functions of this biomolecule. Herein, the chemical, thermodynamic, and structural characterization of phytate-MnII species is presented in a study aimed at understanding how the interaction of the two components modulates their biological roles and their bioavailability. Polynuclear complexes Mn5 (H2 L)⋅16 H2 O (1) and (H2 terpy)2 [Mn(H6 L)(terpy)(H2 O)]⋅17 H2 O (terpy=terpyridine) (2) were prepared and characterized by different techniques. The isolation of 1 and the determination of its solubility, together with potentiometric titrations of the MnII -phytate system, allow the full description of this binary system. The preparation and crystal structure of 2 show a novel coordination mode of phytate, that is, the formation of infinite polymeric chains through equatorial phosphate groups.

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Chemical speciation allows knowing the the different chemical forms of metals in a sample. Sequential extraction procedures are used to evaluate the fractionation of the metals in solid matrices. Few studies are described in the literature related to chemical speciation in food. Residues from fruits and vegetables generated in industry processes results in significant nutritional losses. The nutritional value of a food containing a given mineral depends not only on its content, but also on its bioavailability. The present paper emphasizes the importance of chemical speciation in food, considering the amount of loss of fruits and vegetables, since they are great sources of minerals.

A especiação química permite conhecer as diferentes formas químicas de minerais em uma matriz. A extração sequencial identifica as diferentes frações químicas que um metal está na amostra. Há pouco relato na literatura da aplicação da extração sequencial em alimentos. Muitos resíduos de frutas e hortaliças são gerados em processos industriais caracterizando perda nutricional significativa. O valor nutricional dos minerais em um alimento está relacionado à quantidade deste e à sua biodisponibilidade. O presente estudo enfatiza a aplicação da extração sequencial em alimentos para melhor aproveitamento de resíduos de frutas e hortaliças, que são fontes de minerais.

RESUMO

Chemical speciation allows knowing the the different chemical forms of metals in a sample. Sequential extraction procedures are used to evaluate the fractionation of the metals in solid matrices. Few studies are described in the literature related to chemical speciation in food. Residues from fruits and vegetables generated in industry processes results in significant nutritional losses. The nutritional value of a food containing a given mineral depends not only on its content, but also on its bioavailability. The present paper emphasizes the importance of chemical speciation in food, considering the amount of loss of fruits and vegetables, since they are great sources of minerals.(AU)

A especiação química permite conhecer as diferentes formas químicas de minerais em uma matriz. A extração sequencial identifica as diferentes frações químicas que um metal está na amostra. Há pouco relato na literatura da aplicação da extração sequencial em alimentos. Muitos resíduos de frutas e hortaliças são gerados em processos industriais caracterizando perda nutricional significativa. O valor nutricional dos minerais em um alimento está relacionado à quantidade deste e à sua biodisponibilidade. O presente estudo enfatiza a aplicação da extração sequencial em alimentos para melhor aproveitamento de resíduos de frutas e hortaliças, que são fontes de minerais.(AU)

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Aluminum toxicity in soils is considered one of the major limitations to crop production. However, some plants are able to tolerate high aluminum concentrations due to its complexation with root organic acids exudates. The simultaneous effect of pH ranges and aluminum concentration in soil solution on soybean seedlings root development was studied in a Rhodic Paleudult soil solution under natural grasses vegetation. Soybean seedlings were grown in growth chamber for three days in aerated test tubes containing 40ml soil solution (4.2µmol Al L-1), submmited to four aluminum concentrations (0.0, 0.3, 0.6 and 1.2mmol L-1) and three pH levels (4.0, 5.0 and 6.0). Root and aerial growth decreased under more acidic conditions (pH 4.0). Root growth was less affected by rhyzotoxic aluminum species at pH 5.0, even when submitted to high concentration of aluminum to the soil solution.

A toxicidade do alumínio em solos é considerada uma das maiores limitações para a produção das culturas. No entanto, algumas plantas são capazes de tolerar altas concentrações de alumínio por sua complexação com ácidos orgânicos exsudados pelas raízes. No intuito de estudar os efeitos concomitantes de faixas pH e de alumínio no desenvolvimento radicular de plântulas de soja, desenvolveu-se um trabalho na solução de um Argissolo Vermelho distrófico típico de campo natural. Cultivou-se, em câmara de crescimento, plântulas pré-germinadas de soja durante três dias dentro de tubos de ensaio aerados contendo 40ml da solução do solo (4,2µmol de Al L-1), submetidos a quatro concentrações de alumínio (0,0; 0,3; 0,6 e 1,2µmol L-1) e três níveis de pH (4,0; 5,0 e 6,0). O crescimento radicular e da parte aérea da soja foi menor em condições mais ácidas (pH 4,0). Em condições de acidez intermediária (pH H2O 5,0), o crescimento radicular foi menos afetado pelas espécies rizotóxicas de alumínio, mesmo quando submetidas a elevadas concentrações de alumínio na solução do solo.

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Aluminum toxicity in soils is considered one of the major limitations to crop production. However, some plants are able to tolerate high aluminum concentrations due to its complexation with root organic acids exudates. The simultaneous effect of pH ranges and aluminum concentration in soil solution on soybean seedlings root development was studied in a Rhodic Paleudult soil solution under natural grasses vegetation. Soybean seedlings were grown in growth chamber for three days in aerated test tubes containing 40ml soil solution (4.2µmol Al L-1), submmited to four aluminum concentrations (0.0, 0.3, 0.6 and 1.2mmol L-1) and three pH levels (4.0, 5.0 and 6.0). Root and aerial growth decreased under more acidic conditions (pH 4.0). Root growth was less affected by rhyzotoxic aluminum species at pH 5.0, even when submitted to high concentration of aluminum to the soil solution.

A toxicidade do alumínio em solos é considerada uma das maiores limitações para a produção das culturas. No entanto, algumas plantas são capazes de tolerar altas concentrações de alumínio por sua complexação com ácidos orgânicos exsudados pelas raízes. No intuito de estudar os efeitos concomitantes de faixas pH e de alumínio no desenvolvimento radicular de plântulas de soja, desenvolveu-se um trabalho na solução de um Argissolo Vermelho distrófico típico de campo natural. Cultivou-se, em câmara de crescimento, plântulas pré-germinadas de soja durante três dias dentro de tubos de ensaio aerados contendo 40ml da solução do solo (4,2µmol de Al L-1), submetidos a quatro concentrações de alumínio (0,0; 0,3; 0,6 e 1,2µmol L-1) e três níveis de pH (4,0; 5,0 e 6,0). O crescimento radicular e da parte aérea da soja foi menor em condições mais ácidas (pH 4,0). Em condições de acidez intermediária (pH H2O 5,0), o crescimento radicular foi menos afetado pelas espécies rizotóxicas de alumínio, mesmo quando submetidas a elevadas concentrações de alumínio na solução do solo.