Lead acetate ecotoxicity in tropical soils.

Lead acetate (AcPb) is an important raw material used in chemical industries worldwide. The potential toxicity of AcPb is generally attributed to the presence of Pb. However, the effect of AcPb on the environment as a whole is still poorly known. This study aimed to evaluate AcPb toxicity on three standard species of soil invertebrates and two plant species using ecotoxicology tests. Three tropical soils (Oxisol, Inceptisol, and Tropical Artificial Soil (TAS)) were contaminated with different concentrations of AcPb and one dose of K-acetate (positive control). These soils were used in tests with Eisenia andrei (earthworm), Folsomia candida (springtail), Enchytraeus crypticus (enchytraeid), Zea mays (maize), and Phaseolus vulgaris (common bean). Dose-response curves obtained in the laboratory tests were used to estimate the EC50 values for each species. Among invertebrates, the highest sensitivity to AcPb was observed for E. crypticus in the TAS (EC50 = 29.8 mg AcPb kg-1), whereas for E. andrei and F. candida the highest sensitivity was observed in the Oxisol (EC50 = 141.9 and 1835 mg AcPb kg-1, respectively). Folsomia candida was the least sensitive invertebrate species to AcPb in all soils. Among plant species, Z. mays was less sensitive (EC50 = 1527.5 mg AcPb kg-1) than P. vulgaris (EC50 = 560.5 mg AcPb kg-1) in the Oxisol. The present study evidenced that the toxicity of AcPb should not be attributed uniquely to the presence of Pb, as the treatment containing uniquely Ac provoked the same toxicity as the highest dose of AcPb.

Critical mercury concentration in tropical soils: Impact on plants and soil biological attributes.

Mercury is a toxic element that becomes a problem when present at high concentrations in soils. Mercury toxicity in soils varies depending on chemical species, concentration, exposure routes, and organism vulnerability. There is little information regarding the toxicity of Hg in tropical soils, especially for establishing safe levels of this pollutant. The purpose of this study was to investigate Hg concentrations in two tropical soils and their effect on oats and common beans, as well as on soil biological attributes. The experiment was carried out in a greenhouse, following ISO 11.269-2 and OECD-208 guidelines. Oat and common bean were cultivated in a Typic Hapludox (TyHpx) and Rhodic Acrudox (RhAcx) contaminated with HgCl2 at the following concentrations: 0, 2.5, 5.0, 10.0, 20.0, 40.0, and 80.0 mg of Hg kg-1 of dry soil. The biological variables analyzed were seedling emergence, vegetative growth, chlorophyll content (SPAD index), gas exchange (photosynthetic rate, internal CO2 concentration, transpiration rate, and stomatal conductance), and Hg concentration and accumulation in shoot dry matter. Microbial biomass carbon, soil basal respiration, and metabolic quotient (qCO2) were also analyzed. Due to the sorptive characteristics of TyHpx, it had higher Hg concentrations than RhAcx. Mercury showed toxic effects on both oat and common bean species. However, common bean was affected only at concentrations higher than 20 mg kg-1. The microbial community showed high sensitivity to soil Hg concentrations, but external factors, such as the plant species cultivated, influenced the sensitivity of the community. The microbiota was most sensitive in pots with common bean, and this effect was more pronounced at low clay and low organic matter contents (TyHpx). In this study, the concentration of 0.36 mg kg-1 was critical for Hg in these soils, based on its deleterious effects on oat and common bean and on biological soil attributes.

Natural variation of selenium in Brazil nuts and soils from the Amazon region.

Brazil nut tree (Bertholletia excelsa) is native of the Amazon rainforest. Brazil nuts are consumed worldwide and are known as the richest food source of selenium (Se). Yet, the reasoning for such Se contents is not well stablished. We evaluated the variation in Se concentration of Brazil nuts from Brazilian Amazon basin, as well as soil properties, including total Se concentration, of the soils sampled directly underneath the trees crown, aiming to investigate which soil properties influence Se accumulation in the nuts. The median Se concentration in Brazil nuts varied from 2.07 mg kg-1 (in Mato Grosso state) to 68.15 mg kg-1 (in Amazonas state). Therefore, depending on its origin, a single Brazil nut could provide from 11% (in the Mato Grosso state) up to 288% (in the Amazonas state) of the daily Se requirement for an adult man (70 µg). The total Se concentration in the soil also varied considerably, ranging from <65.76 to 625.91 µg kg-1, with highest Se concentrations being observed in soil samples from the state of Amazonas. Se accumulation in Brazil nuts generally increased in soils with higher total Se content, but decreased under acidic conditions in the soil. This indicates that, besides total soil Se concentration, soil acidity plays a major role in Se uptake by Brazil nut trees, possibly due to the importance of this soil property to Se retention in the soil.

Adsorption-desorption reactions of selenium (VI) in tropical cultivated and uncultivated soils under Cerrado biome.

Soil management may affect selenium (Se) adsorption capacity. This study investigated adsorption and desorption of Se (VI) in selected Brazilian soils from the Cerrado biome, an area of ever increasing importance for agriculture expansion in Brazil. Soil samples were collected from cultivated and uncultivated soils, comprising clayed and sandy soils. Following chemical and mineralogical characterization, soil samples were subjected to Se adsorption and desorption tests. Adsorption was evaluated after a 72-h reaction with increasing concentrations of Se (0-2000 µg L-1) added as Na2SeO4 in a NaCl electrolyte solution (pH 5.5; ionic strength 15 mmol L-1). Desorption, as well as distribution coefficients (Kd) for selenate were also assessed. Soil management affected Se adsorption capacity, i.e., Se adsorbed amounts were higher for uncultivated soils, when compared to cultivated ones. Such results were also supported by data of Kd and maximum adsorption capacity of Se. This fact was attributed mainly to the presence of greater amounts of competing anions, especially phosphate, in cultivated soils, due to fertilizer application. Phosphate may compete with selenate for adsorption sites, decreasing Se retention. For the same group of soils (cultivated and uncultivated), Se adsorption was greater in the clayed soils compared to sandy ones. Our results support the idea that adding Se (VI) to the soil is a good strategy to increase Se levels in food crops (agronomic biofortification), especially when crops are grown in soils that have been cultivated over the time due to their low Se adsorption capacity (high Se availability).

Investigation of arsenic species in tailings and windblown dust from a gold mining area.

Research has shown the presence of high levels of arsenic (up to 2666 mg As kg(-1)) in tailings from a gold mining area of Brazil. This is an important point of attention, generating concerns about impacts on human health. Yet, a recent study showed that As bioaccessibility in the same area was very low (<4.4%). Thus, determination of the direct solid-phase speciation of As in the mine tailings and windblown dust is needed to explain this low bioaccessibility. Mine samples were collected from four subareas and windblown dust from eight sites. Synchrotron-based bulk-X-ray absorption near-edge structure (bulk-XANES) spectroscopy, micro-X-ray absorption near-edge structure (µ-XANES), and µ-X-ray fluorescence (µ-SXRF) spectroscopy were applied to determine As speciation. Bulk-XANES spectra indicated that As occurs as the As(V) oxidation state. Micro-XANES and µ-SXRF analyses revealed that As was also present as arsenopyrite (FeAsS) and its weathering products, but mostly it was As(V) as poorly crystalline ferric arsenate. This supports the findings of low bioaccessible As and highlights the importance of Fe oxides in immobilizing As in the terrestrial environment. All air particulate samples exhibited As-rich particles (up to 313 mg As kg(-1)). The air particulates exhibited solid-phase As species very similar to those found in the mine samples, which indicates that As in the windblown dust is not easily available.

Beneficial use of industrial by-products for phytoremediation of an arsenic-rich soil from a gold mining area.

This study investigated two industrial by-products - red mud (RM) and its mixture with phosphogypsum (RMG), as amendments in an As((5+))-contaminated soil from a gold mining area in Brazil in order to grow three plant species: Brachiaria decumbens, Crotalaria spectabilis, and Stylosanthes cv. Campo Grande. These amendments were applied to reach a soil pH of 6.0. Using RM and RMG increased shoot dry matter (SDM) and root dry matter (RDM) of most plants, with RMG being more effective. Adding RMG increased the SDM of Brachiaria and Crotalaria by 18 and 25% and the RDM by 25 and 12%, respectively. Stylosanthes was sensitive to As toxicity and grew poorly in all treatments. Arsenic concentration in shoots of Brachiaria and Crotalaria decreased by 26% with the use of RMG while As in roots reduced by 11 and 30%, respectively. Also, the activities of the plant oxidative stress enzymes varied following treatments with the by-products. The plants grew in the As-contaminated soil from the gold mining area. Thus, they might be employed for phytoremediation purposes, especially with the use of RMG due to its potential advantage in terms of nutrient supply (Ca(2+) and SO4(2-) from phosphogypsum).

Bioaccessibility of Cd and Pb in tailings from a zinc smelting in Brazil: implications for human health.

Soils and wastes enriched with heavy metals may present ecological and human health risks. A considerable number of mining areas exist in Brazil, where high levels of metals have been found. However, studies of bioaccessibility of metals in soils/tailings from these areas are scarce, despite their potential informational contribution concerning exposure risks of residents near these areas. This study evaluated tailings collected from four sites of a zinc smelting area located in Brazil with aims to: (1) evaluate the presence of metals of potential concern; (2) investigate Cd and Pb bioaccessibility; and (3) determine the desorption kinetics of Cd and Pb. High concentrations of total Cd and Pb (up to 1743 mg Cd kg(-1) and 8675 mg Pb kg(-1)) and great variability were found in the tailings, indicating the importance of adequate planning for their final disposal, in order to avoid contamination in the surrounding environment. Cadmium and Pb bioaccessibility percentages in the intestinal phase were less than 47 and 4 %, respectively, which represents significant fractions not available for absorption in the intestinal tract. However, this material has to be monitored since its bioaccessibility may increase with eventual physicochemical changes, releasing Cd and Pb. Desorption kinetics experiments revealed that Pb in the samples remained in less labile fractions, whereas Cd was found in more labile fractions, which is in accordance with the bioaccessibility results.

Binding intensity and metal partitioning in soils affected by mining and smelting activities in Minas Gerais, Brazil.

Mining and smelting activities are potential sources of heavy metal contamination, which pose a threat to human health and ecological systems. This study investigated single and sequential extractions of Zn, Pb, and Cd in Brazilian soils affected by mining and smelting activities. Soils from a Zn mining area (soils A, B, C, D, E, and the control soil) and a tailing from a smelting area were collected in Minas Gerais state, Brazil. The samples were subjected to single (using Mehlich I solution) and sequential extractions. The risk assessment code (RAC), the redistribution index (U ts ), and the reduced partition index (I R ) have been applied to the sequential extraction data. Zinc and Cd, in soil samples from the mining area, were found mainly associated with carbonate forms. This same pattern did not occur for Pb. Moreover, the Fe-Mn oxides and residual fractions had important contributions for Zn and Pb in those soils. For the tailing, more than 70 % of Zn and Cd were released in the exchangeable fraction, showing a much higher mobility and availability of these metals at this site, which was also supported by results of RAC and I R . These differences in terms of mobility might be due to different chemical forms of the metals in the two sites, which are attributable to natural occurrence as well as ore processing.

Phosphorus improves arsenic phytoremediation by Anadenanthera peregrina by alleviating induced oxidative stress.

Due to similarities in their chemical behaviors, studies examining interactions between arsenic (As)--in special arsenate--and phosphorus (P) are important for better understanding arsenate uptake, toxicity, and accumulation in plants. We evaluated the effects of phosphate addition on plant biomass and on arsenate and phosphate uptake by Anadenanthera peregrina, an important Brazilian savanna legume. Plants were grown for 35 days in substrates that received combinations of 0, 10, 50, and 100 mg kg(-1) arsenate and 0, 200, and 400 mg kg(-1) phosphate. The addition of P increased the arsenic-phytoremediation capacity of A. peregrina by increasing As accumulation, while also alleviating As-induced oxidative stress. Arsenate phytotoxicity in A. peregrina is due to lipid peroxidation, but not hydrogen peroxide accumulation. Added P also increased the activity of important reactive oxygen species-scavenging enzymes (catalase and ascorbate peroxidase) that help prevent lipid peroxidation in leaves. Our findings suggest that applying P represents a feasible strategy for more efficient As phytoremediation using A. peregrina.

Zinc tolerance modulation in Myracrodruon urundeuva plants.

We investigated Zn tolerance and related tolerance mechanisms of Myracrodruon urundeuva by evaluating the growth (biomass production, pigment content, and photosynthetic activity) and antioxidant systems (redox potential and antioxidant enzyme activities) of seedlings exposed to increasing Zn doses. Plants were grown for 120 days in substrates with 0, 50, 80, 120 and 200 mg Zn kg(-1) and demonstrated Zn-tolerance. Zn doses greater than 80 mg Zn kg(-1) were phytotoxic but not lethal, and Zn toxicity under these conditions was imposed by oxidative stress caused by hydrogen peroxide (H2O2) accumulation and related lipid peroxidation. Zn tolerance in M. urundeuva is linked to the activity of antioxidant systems in their leaves that are modulated by that metal: both superoxide dismutase (SOD) and catalase (CAT) were always higher in the presence of Zn; lower Zn doses stimulated ascorbate peroxidase (APX) and glutathione reductase (GR) activities, but enzyme activity was inhibited at high doses; APX appeared to be the main peroxidase in H2O2 scavenging as stimulated guaiacol peroxidase (GPX) activity was not sufficient to avoid H2O2 accumulation at higher Zn doses; the modulation of APX and GR activities was linked to changes in the redox status of leaves.

Arsenic bioaccessibility in gold mine tailings of Delita, Cuba.

A bioaccessibility test was carried out in four tailings collected at a former mining area in Delita, Cuba. A previous risk assessment study identified arsenic (As) as the main critical contaminant in this area and showed that the tailings had high As concentrations (up to 3.5%). This study aimed at: (i) evaluating As bioaccessibility in four tailings (R1, R2, R3 and R4) from a gold mining area to obtain a better health risk estimate; and, (ii) identifying the mineral phases responsible for most of the bioaccessible As using XRD, SEM-EDS, and XAS. The results showed that bioaccessible As in the tailings ranged from 0.65 to 40.5%. The main factors influencing As bioaccessibility were a high occurrence of amorphous iron arsenate; occurrence, even at low content, of iron oxyhydroxides and stability of mineral phases in the environment of the gastrointestinal tract. Although arsenopyrite, arsenates and goethite were confirmed by mineralogical methods such as optical microscopy, XRD, and SEM-EDS, XAS showed that scorodite-oxidation state As(+V)-was dominant in most of the tailings. This confirms that the low bioaccessibility of As in most of the tailings is due to the slow kinetics of As release from scorodite.

Increasing arsenic sorption on red mud by phosphogypsum addition.

Mining by-products have been tested as adsorbents for arsenic in order to reduce As bioavailability. This study evaluated a red mud (RM) treated with or without phosphogypsum (G) in order to improve its As retention. Red mud and G samples and their mixtures were chemically and mineralogically characterized to gather information concerning their composition, which is key for a better understanding of the adsorbent properties. Phosphogypsum was added to RM in the following proportions: 0, 1, 2, 5, 10, and 25% by weight. These mixtures were subjected to As adsorption and desorption and tested for their maximum adsorption capacity of As (AsMAC). Arsenic adsorption increased upon increasing the proportion of G added to RM. The AsMAC at pure RM reached 909 mg kg(-1), whereas the 75%-RM+25%-G mixture sorbed up to 3333 mg kg(-1) of As, i.e., a 3.5-fold increase in AsMAC. Using G in mixtures with RM increases the efficiency of As adsorption due to the presence of Ca(2+), which alters the charge balance of the adsorbent, leading to the formation of ternary complexes. Addition of G to RM is thus a promising technique to improve As retention, while providing additional value to both by-products, G and RM.

Accumulation of arsenic and nutrients by castor bean plants grown on an As-enriched nutrient solution.

Phytoextraction is a remediation technique that consists in using plants to remove contaminants from soils and water. This study evaluated arsenic (As) accumulation in Castor bean (Ricinus communis cv. Guarany) grown in nutrient solution in order to assess its phytoextraction ability. Castor bean plants were grown under greenhouse conditions in pots containing a nutrient solution amended with increasing doses of As (0, 10, 50, 100, 250, 500 and 5000 microg L(-1)) in a completely randomized design with four replications. Shoot and roots dry matter production as well as arsenic and nutrient tissue concentrations were measured at the end of the experiment. The results showed that increasing As concentration in nutrient solution caused a decrease in shoot and root biomass but did not result in severe toxicity symptoms in castor bean growing under a range of As concentration from 0 to 5000 microg L(-1). The As doses tested did not affect the accumulation of nutrients by castor bean. Although castor bean did not pose characteristics of a plant suitable for commercial phytoextraction, it could be useful for revegetation of As-contaminated areas while providing an additional income by oil production.

Atrazine sorption and fate in a Ultisol from humid tropical Brazil.

This study combined laboratory based microcosm systems as well as field experiments to evaluate the mobility of atrazine on a Ultisol under humid tropical conditions in Brazil. Results from sorption experiments fit to the Freundlich isotherm model [K(f) 0.99 mg kg(-1)/(mg l(-1))(1/n)], and indicate a low sorption capacity for atrazine in this soil and consequently large potential for movement by leaching and runoff. Microcosm systems using (14)C-atrazine to trace the fate of the applied herbicide, showed that 0.33% of the atrazine was volatilized, 0.25% mineralized and 6.89% was recorded in the leachate. After 60 d in the microcosms, 75% of the (14)C remained in the upper 5 cm soil layer indicating atrazine or its metabolites remained close to the soil surface. In field experiments, after 60 d, only 5% of the atrazine applied was recovered in the upper soil layers. In the field experiments atrazine was detected at a depth of 50 cm indicating leaching. Simulating tropical rain in field experiments resulted in 2.1% loss of atrazine in runoff of which 0.5% was adsorbed onto transported soil particles and 1.6% was in solution. Atrazine runoff was greatest two days after herbicide application and decreased 10 fold after 15 d. The use of atrazine on Ultisols, in the humid tropics, constitutes a threat to water quality, causing surface water and ground water pollution.