Redox conditions and biochar pyrolysis temperature affecting As and Pb biogeochemical cycles and bacterial community of sediment from mining tailings.

Despite the widespread use of biochar for soil and sediment remediation, little is known about the impact of pyrolysis temperature on the biogeochemistry of arsenic (As) and lead (Pb) and microorganisms in sediment under reducing conditions. In this study, we investigated the effects of pyrolysis temperature and the addition of glucose on the release and transformation of As and Pb, as well as their potential effects on the bacterial community in contaminated sediments. The addition of biochar altered the geochemical cycle of As, as it favors specific bacterial groups capable of changing species from As(V) to As(III) through fermentation, sulfate respiration and nitrate reduction. The carbon quality and content of N and S in solution shaped the pH and redox potential in a way that changed the microbial community, favoring Firmicutes and reducing Proteobacteria. This change played a fundamental role in the reductive dissolution of As and Pb minerals. The addition of biochar was the only efficient way to remove Pb, possibly as a function of its sorption and precipitation mechanisms. Such insights could contribute to the production or choice of high-efficiency biochar for the remediation of sediments subjected to redox conditions.

Desorption kinetic and sequential extraction of Pb and Zn in a contaminated soil amended with phosphate, lime, biochar, and biosolids.

The mining and metallurgical industry sector activities often release potential toxic elements (PTE) surrounding exploitation area. We evaluated the addition of phosphate and lime using the dosage of 0.5:1, 1:1, and 2:1 molar ratio of PO43- and CO32- to the sum of PTE, respectively, and also, biochar and biosolids using the dosage of 2.5, 5, and 10% (m:m) to immobilize PTE in contaminated forest soil (Pb (270 mg kg-1) and Zn (858 mg kg-1)) near an abandoned mine site in Brazil. The desorption by stirred flow kinetics revealed that 15% of the total Zn and 12% Pb contents are mobile before any amendment application. Phosphate amendment decreased Pb desorption but increased Zn desorption. Biochar and biosolids immobilize high amounts of Zn and Pb because of their high cation exchange capacities and alkaline properties; however, 20% biosolid dose increased Pb desorption. X-ray absorption spectroscopy suggested Zn-kerolite as the major species in the contaminated soil, likely from mine dust. The change in Zn speciation after soil amendment addition indicated that biochar and lime kept a high proportion of Zn-Al species, whereas phosphate and biosolids led to more Zn-Fe species. Our results pointed out that lime might reduce both Pb and Zn mobilities; however, field trials are crucial to confirm the immobilization efficiency of lime and other amendments over long term.

Intentional creation of carbon-rich dark earth soils in the Amazon.

Fertile soil known as Amazonian dark earth is central to the debate over the size and ecological impact of ancient human populations in the Amazon. Dark earth is typically associated with human occupation, but it is uncertain whether it was created intentionally. Dark earth may also be a substantial carbon sink, but its spatial extent and carbon inventory are unknown. We demonstrate spatial and compositional similarities between ancient and modern dark earth and document modern Indigenous practices that enrich soil, which we use to propose a model for the formation of ancient dark earth. This comparison suggests that ancient Amazonians managed soil to improve fertility and increase crop productivity. These practices also sequestered and stored carbon in the soil for centuries, and we show that some ancient sites contain as much carbon as the above-ground rainforest biomass. Our results demonstrate the intentional creation of dark earth and highlight the value of Indigenous knowledge for sustainable rainforest management.

Effect of selenium and soil pH on cadmium phytoextraction by Urochloa decumbens grown in Oxisol.

It has been speculated that selenium (Se) supply can affect cadmium (Cd) 'availability' and increase the Cd tolerance of plants used for phytoextraction, in a pH-dependent process. Thus, we evaluated the interaction Cd-Se and the effects of soil pH in this interaction on plant availability of Cd and phytoextraction efficiency of Urochloa decumbens cv. Basilisk grown in Oxisol. Two soil concentrations of Cd (0.93 and 3.6 mg kg-1) and Se (<0.2 and 1 mg kg-1) and two soil pH (0.01 mol L-1 CaCl2) conditions (4.1 and 5.7) were considered. At both pH, Se supply increased the exchangeable fraction of Cd and decreased the residual Cd fraction. At pH 4.1, the growth of U. decumbens was impaired by Se addition, regardless of Cd exposure. The lower root growth and tillering of U. decumbens exposed to Cd disappeared at pH 5.7 due to uptake of low Se concentrations. Thus, the toxic or beneficial effects of Se on growth of U. decumbens used for Cd phytoextraction depend on the amount of Se assimilated. The Cd phytoextraction efficiency of U. decumbens was not improved by Se supply, regardless of soil pH. Therefore, we cannot recommend the application of Se to increase Cd phytoextraction by this grass.

Zinc speciation and desorption kinetics in a mining waste impacted tropical soil amended with phosphate.

Mining is an important component of the Brazilian economy. However, it may also contribute to environmental problems such as the pollution of soils with zinc and other potentially toxic metals. Our objective was to evaluate changes in the chemical speciation and mobility of Zn in a soil amended with phosphate. Soil samples were collected from a deactivated mining area in the state of Minas Gerais, Brazil, and amended with NH4H2PO4 saturated with deionized water to 70 % of maximum water retention and incubated at 25 ± 2 °C in open containers for 60 days. The soil was chemically and mineralogically characterized, and sequential extraction, desorption kinetics, and speciation were carried out using synchrotron bulk-sample and micro-X-ray Absorption Near-Edge Structure (XANES/µ-XANES) spectroscopy at the Zn K-edge, and X-ray fluorescence microprobe analysis (µ-XRF). The combination of µ-XRF and µ-XANES techniques made it possible to identify Zn hotspots in the main species formed after phosphate remediation. The best fit combination for bulk XANES and µ-XANES was observed in Zn-montmorillonite, Zn-kerolite, Zn-ferrihydrite, and gahnite. In the course of phosphate treatment, gahnite, Zn layered double hydroxides (Zn-LDH), Zn3(PO4), and ZnO were identified by bulk XANES, while Zn-ferrihydrite, Zn-montmorillonite, and scholzite were identified by µ-XANES. Zinc in the phosphate-amended soil had the strongest partial correlations (r' > 0.05) with Ni, Co, Fe, Cr, Mn, Si, P, Cd, Pb, and Cd, while the unamended soil showed the strongest correlation with Cu, Pb, Fe, and Si. The application of NH4H2PO4 altered Zn speciation and favored an increase in Zn desorption. The most available Zn contents after phosphate amendment were correlated with the release of exchangeable Zn fractions, associated with carbonate and organic matter.

Pristine and biochar-supported nano zero-valent iron to immobilize As, Zn and Pb in soil contaminated by smelting activities.

Nano zero-valent iron (nZVI) is one of the most studied nanomaterials for environmental remediation during the past 20 years. However, few studies have focused on nZVI combination with other materials (e.g., biochar) for enhancement of soil remediation. In this study, pristine nZVI and a composite of wood sawdust biochar (BC) and nZVI (nZVI-BC) were added to a highly contaminated soil to compare their efficacy in immobilizing available arsenic (As = 28.6 mg kg-1), zinc (Zn = 1707 mg kg-1), and lead (Pb = 6759 mg kg-1). Sediment quality guidelines were used to evaluate the extent of soil contamination and ascertain its source. The mineralogy of soil and slags were assessed by X-ray Diffractometry Spectroscopy (XRD), and the geochemical fractions of Pb, Zn, and As were obtained by chemical sequential extractions. The average Pollution Load Index (PLI) was 10.66, indicating elevated multi-elemental contamination. Contamination Factor (CF) values for As, Zn, Pb, cadmium (Cd), and copper (Cu) were all higher than 6 which implies extreme contamination. Secondary minerals frequently found in Pb/Zn smelter sites, such as cerussite and anglesite, were detected in the slags through XRD. Pb and Zn were mainly bound to carbonates and residual fractions in soil and presented a high risk considering the sediment quality guidelines, sequential extraction results, and XRD analysis. The treatment with nZVI-BC was more effective than pristine nZVI on concurrently decreasing 97% of available As, 84% of Pb and 81% of Zn compared to control. The application of nZVI-BC is a promising green and sustainable remediation technique for soils contaminated with potentially toxic elements of distinct chemical behavior.

Temporal changes in arsenic and lead pools in a contaminated sediment amended with biochar pyrolyzed at different temperatures.

Globally, tons of soils and sediments are experiencing degradation due to the presence of high concentrations of potentially toxic elements (PTEs), such as arsenic (As) and lead (Pb), in areas in the vicinity of metal mining activities. The addition of biochar to contaminated sediments is a promising in situ remediation approach, and the effects of pyrolysis temperature and biochar aging are important factors for the immobilization and fate of PTEs. In this study, we evaluated the temporal changes in pools of As and Pb in sediment amended with biochars produced from sugarcane (Saccharum officinarum) pyrolyzed at 350 (BC350), 550 (BC550), and 750 °C (BC750). Biochars were aged by natural process (without additional acid or heat), and changes in As and Pb pools were evaluated every 45 days until completing 180 days of incubation. Changes in the As and Pb pools were extracted with water (bioavailable), magnesium chloride (exchangeable), nitric acid (active geochemical fraction), and exchangeable Mehlich-3 (associated with organic matter). As and Pb available contents have increased over time. BC750 was more effective in reducing the bioavailable and exchangeable As contents, while BC550 and BC350 were more effective in reducing the contents of bioavailable and exchangeable Pb.

Immobilization of lead by amendments in a mine-waste impacted soil: Assessing Pb retention with desorption kinetic, sequential extraction and XANES spectroscopy.

Chemical stabilization is an in-situ remediation that uses amendments to reduce contaminant availability in polluted soils. Rates of phosphate, lime, biochar, and biosolids were evaluated as affecting Pb speciation and mobility in soil samples of a mining area located in Vazante, state of Minas Gerais, Brazil. Chemical and mineralogical characterization, desorption kinetics, sequential extraction, leaching evaluation in columns and speciation using X-ray absorption near edge structure were performed. Pb adsorbed on bentonite and on anglesite were the predominant species in the unamended soil. The treatments with phosphate and lime transformed part of the Pb species to pyromorphite. Conversely, part of Pb species was transformed to Pb adsorbed on citrate in the soil amended with biochar, while PbCl2 was formed in soil samples amended with biosolids. Phosphate and lime increased the Pb extracted in the residual fraction, thus showing that more recalcitrant species, such as pyromorphite, were formed. Biosolids and biochar treatments decreased the Pb in the residual fraction, and the fraction associated to organic matter increased after the addition of biosolids. Phosphate and lime were effective to immobilize Pb and to decrease Pb desorption kinetics, but the organic amendments increased the desorption kinetics of Pb in all rates applied. The soil amended with phosphate decreased the Pb leached in the experiment with leaching columns.

Are Grasses Really Useful for the Phytoremediation of Potentially Toxic Trace Elements? A Review.

The pollution of soil, water, and air by potentially toxic trace elements poses risks to environmental and human health. For this reason, many chemical, physical, and biological processes of remediation have been developed to reduce the (available) trace element concentrations in the environment. Among those technologies, phytoremediation is an environmentally friendly in situ and cost-effective approach to remediate sites with low-to-moderate pollution with trace elements. However, not all species have the potential to be used for phytoremediation of trace element-polluted sites due to their morpho-physiological characteristics and low tolerance to toxicity induced by the trace elements. Grasses are prospective candidates due to their high biomass yields, fast growth, adaptations to infertile soils, and successive shoot regrowth after harvest. A large number of studies evaluating the processes related to the uptake, transport, accumulation, and toxicity of trace elements in grasses assessed for phytoremediation have been conducted. The aim of this review is (i) to synthesize the available information on the mechanisms involved in uptake, transport, accumulation, toxicity, and tolerance to trace elements in grasses; (ii) to identify suitable grasses for trace element phytoextraction, phytostabilization, and phytofiltration; (iii) to describe the main strategies used to improve trace element phytoremediation efficiency by grasses; and (iv) to point out the advantages, disadvantages, and perspectives for the use of grasses for phytoremediation of trace element-polluted soils.

Photosynthetic Parameters and Growth of Rice, Lettuce, Sunflower and Tomato in an Entisol as Affected by Soil Acidity and Bioaccumulation of Ba, Cd, Cu, Ni, and Zn.

The bioaccumulation of trace elements (TEs) in crops consumed by humans can reduce food production as a consequence of photosynthetic damage in plants and cause several diseases in humans. Liming is a soil management strategy designed to alleviate soil acidity and mitigating these problems by reducing the TE bioavailability. In this study, we evaluated the effect of liming on photosynthesis, growth, and bioaccumulation of barium (Ba), cadmium (Cd), copper (Cu), nickel (Ni), or zinc (Zn) in lettuce (Lactuca sativa L.), rice (Oryza sativa L.), sunflower (Helianthus annuus L.), and tomato (Solanum lycopersicum L.) grown in a sandy Entisol. The crops were grown in either uncontaminated or contaminated Entisol, at two base saturation (BS%) ratios: 30% for all crops or 50% for rice and 70% for lettuce, sunflower, and tomato. The photosynthesis-related parameters varied depending on the metal and the crop, but in general, increasing BS% did not attenuate photosynthetic damage induced by Ba, Cd, Cu, Ni, and Zn in the crops. There was no strong correlation between the photosynthetic parameters and biomass production, which indicates that the suppression of biomass induced by Ba, Cd, Cu, Ni, or Zn is related to other metabolic disorders in addition to the impairment of CO2 assimilation or chlorophyll synthesis in the crops assayed, with the exception of Ni and Zn in lettuce. In conclusion, increasing BS% was not consistent in reducing Ba, Cd, Cu, Ni, and Zn accumulation in the edible parts of lettuce, rice, sunflower, and tomato grown in the sandy soil, which is probably related to the low capacity of this soil to control TE bioavailability.

Proposal of new distribution coefficients (Kd) of potentially toxic elements in soils for improving environmental risk assessment in the State of São Paulo, southeastern Brazil.

Soil solid-solution distribution coefficients (Kd) are used in predictive environmental models to assess public health risks. This study was undertaken to determine Kd for potentially toxic elements (PTE) Cd, Co, Cr, Cu, Ni, Pb, and Zn in topsoil samples (0-20 cm) from 30 soils in the State of São Paulo, southeastern Brazil. Batch sorption experiments were carried out, and PTE concentrations in the equilibrium solution were determined by High Resolution Inductively Coupled Plasma Mass Spectrometry (HR-ICPMS). Sorption data was fitted to the Freundlich model. The Kd values were either obtained directly from the slope coefficients of C-type isotherms or derived from the slope of the straight line tangent to the non-linear L-type and H-type isotherms. Stepwise multiple regression models were used to estimate the Kd values through the combined effect of a number of soil attributes [pHH2O, effective cation exchange capacity (ECEC) and contents of clay, organic carbon, and Fe (oxy)hydroxides]. The smallest variation in Kd values was recorded for Cu (105-4598 L kg-1), Pb (121-7020 L kg-1), Ni (6-998 L kg-1), as variation across four orders of magnitude was observed for Cd (7-14,339 L kg-1), Co (2-34,473 L kg-1), and Cr (1-21,267 L kg-1). The Kd values for Zn were between 5 and 123,849 L kg-1. According to median values of Kd, PTE were sorbed in the following preferential order: Pb > Cu > Cd > Ni > Zn > Cr > Co. The Kd values were best predicted using metal-specific and highly significant (p < 0.001) linear regressions that included pHH2O, ECEC, and clay contents. The Kd values reported in this study are a novel result that can help minimize erroneous estimates and improve both environmental and public health risk assessments under humid tropical edaphoclimatic conditions.

Unraveling the mechanisms controlling Cd accumulation and Cd-tolerance in Brachiaria decumbens and Panicum maximum under summer and winter weather conditions.

We evaluated the mechanisms that control Cd accumulation and distribution, and the mechanisms that protect the photosynthetic apparatus of Brachiaria decumbens Stapf. cv. Basilisk and Panicum maximum Jacq. cv. Massai from Cd-induced oxidative stress, as well as the effects of simulated summer or winter conditions on these mechanisms. Both grasses were grown in unpolluted and Cd-polluted Oxisol (0.63 and 3.6 mg Cd kg-1 soil, respectively) at summer and winter conditions. Grasses grown in the Cd-polluted Oxisol presented higher Cd concentration in their tissues in the winter conditions, but the shoot biomass production of both grasses was not affected by the experimental conditions. Cadmium was more accumulated in the root apoplast than the root symplast, contributing to increase the diameter and cell layers of the cambial region of both grasses. Roots of B. decumbens were more susceptible to disturbed nutrients uptake and nitrogen metabolism than roots of P. maximum. Both grasses translocated high amounts of Cd to their shoots resulting in oxidative stress. Oxidative stress in the leaves of both grasses was higher in summer than winter, but only in P. maximum superoxide dismutase (SOD) and ascorbate peroxidase (APX) activities were increased. However, CO2 assimilation was not affected due to the protection provided by reduced glutathione (GSH) and phytochelatins (PCs) that were more synthesized in shoots than roots. In summary, the root apoplast was not sufficiently effective to prevent Cd translocation from roots to shoot, but GSH and PCs provided good protection for the photosynthetic apparatus of both grasses.

Respiratory bioaccessibility and solid phase partitioning of potentially harmful elements in urban environmental matrices.

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.

Effects of winter and summer conditions on Cd fractionation and bioavailability, bacterial communities and Cd phytoextraction potential of Brachiaria decumbens and Panicum maximum grown in a tropical soil.

The interactions between soil properties, microorganisms, plant species and climate affect cadmium (Cd) availability in tropical soils. In this study, we investigated the effects of simulated summer and winter conditions on Cd fractionation and bacterial communities in Oxisols and on growth of two high biomass production-grasses (Brachiaria decumbens and Panicum maximum) that were evaluated for their Cd phytoextraction potential. We also assessed how these interactions could influence the availability of Cd and its possible phytoextraction by these grasses. The Cd fraction bound to carbonates was higher in the winter conditions, while Cd bound to Fe- and Mn oxides was higher in the summer conditions, which resulted in a higher Cd availability in winter compared to summer conditions. B. decumbens and P. maximum took up more Cd when grown in the winter conditions, but their biomasses were not affected by the higher Cd uptake. The occurrence and relative abundance of bacterial taxa in the bare soil differed from the soils cultivated with grasses, where the Gammaproteobacteria predominated. However, no positive correlations were observed between the rhizosphere bacterial community in the cultivated soils and Cd availability, irrespective of the season conditions.

Human intestinal Caco-2 cell line in vitro assay to evaluate the absorption of Cd, Cu, Mn and Zn from urban environmental matrices.

The Caco-2 cell line is derived from a human colon adenocarcinoma and is generally used in toxicity assays. The ingestion of soil or dust is a significant route of human exposure to potential harmful elements (PHE), and assays of bioaccessibility or bioavailability can be used to measure the potential hazard posed by exposure to toxic substances. The in vitro digestion (UBM method) and Caco-2 cell model were used to investigate the bioaccessibility and absorption by intestinal cells of the PHE in four matrices (two urban soils and two soils with lead (Pb)-mining tailings) along with the guidance material for bioaccessibility measurements, BGS 102. The gastrointestinal (GI) compartment was simulated, and the resulting material added to Caco-2 cells. In the GI, the average bioaccessibility was 24% for cadmium (Cd), 17% for copper (Cu), 0.2% for Pb, 44% for manganese (Mn) and 6% for zinc (Zn). The poor reproducibility was attributed to the pH (6.3) and the highly complex GI fluid that formed PHE precipitates and complexes. In 2 h, Caco-2 cells absorbed 0.2 ng mg-1 of cellular protein for Cd, 13.4 ng mg-1 for Cu, 5 ng mg-1 for Mn and 31.7 µg mg-1 for Zn. Lead absorption was lower than the limit of quantification (< 2 µg L-1). Cd was presented in the cell monolayer and could interfere in the intracellular accumulation of Cu, Mn and Zn. The use of in vitro assays allowed for an estimation of the absorption of Cd, Cu, Mn and Zn from environmental matrices to be made, and except for Mn, it had a positive correlation with bioaccessible concentration, suggesting a common association of these elements in the cellular environment.

Cadmium sorption and extractability in tropical soils with variable charge.

The availability of cadmium (Cd) for plants and its impact in the environment depends on Cd sorption in soil colloids. The study of Cd sorption in soil and its fractionation is an interesting tool for the evaluation of Cd affinity with soil pools. The objective with this study was to evaluate Cd sorption and desorption in tropical soils with variable charge (three Oxisols), in a Mollisol and in two Entisols with diverse physical, chemical, and mineralogical attributes. We used a thermodynamic approach to evaluate Cd sorption and performed a chemical fractionation of Cd in the six soils. Data from Cd sorption fit the Langmuir model (r > 0.94), and the sorption capacity ranged from 0.33 to 11.5 mmol kg-1. The Gibbs standard free energy was positively correlated to Cd sorption capacity (r = 0.74, except for the Quartzipsamments), and it was more favorable in soils with great sorption capacity. Distribution of Cd among fractions was not affected (t test, α = 0.05) by initial concentration, and there was a predominance of Cd extractable in 0.1 mol L-1 CaCl2.

Background concentrations and quality reference values for some potentially toxic elements in soils of São Paulo State, Brazil.

Quality reference values (QRV) for potentially toxic elements (PTE) in soils are established as a tool for prevention and monitoring of soil pollution. These values should be periodically revised in order to ensure soil safety for agricultural purposes. Brazil is market leader for several commodities; therefore, the safety of Brazilian soils is of worldwide strategic importance. The objective of this study was to determine the natural background concentrations and the QRV for As, Ba, Cd, Cr, Ni, Pb, Se, and Zn by investigating 30 representative pedotypes in the São Paulo State, one of the most important agro-industry economy at worldwide level. Multivariate statistical analysis was applied to determine the sources of PTE and their variability. The mean natural background concentrations of PTE in the soils were generally lower to those reported in literature. QRV, calculated for each element as the 75th and 90th percentiles, were lower (75th for As, Cd, Pb, and Zn), similar (75th for Ba, Cr, and Se) or above (90th for Ba, Cr, and Se and 75-90th for Ni) those previously proposed by the Brazilian environmental protection agencies. The results indicate that 75th percentile may be too restrictive. The PTE in the investigated soils appear to have comes mainly from two primary natural sources: a prevalent one of geogenic and a secondary of pedogenic origin. These results confirm the predominant natural source of selected PTE in the investigated soils, thus sustaining the possibility of using the data set to develop QRV for the State of São Paulo.

Methods and extractants to evaluate silicon availability for sugarcane.

The correct evaluation of silicon (Si) availability in different soil types is critical in defining the amount of Si to be supplied to crops. This study was carried out to evaluate two methods and five chemical Si extractants in clayey, sandy-loam, and sandy soils cultivated with sugarcane (Saccharum spp. hybrids). Soluble Si was extracted using two extraction methods (conventional and microwave oven) and five Si extractants (CaCl2, deionized water, KCl, Na-acetate buffer (pH 4.0), and acetic acid). No single method and/or extractant adequately estimated the Si availability in the soils. Conventional extraction with KCl was no more effective than other methods in evaluating Si availability; however, it had less variation in estimating soluble Si between soils with different textural classes. In the clayey and sandy soils, the Na-acetate buffer (pH 4.0) and acetic acid were effective in evaluating the Si availability in the soil regardless of the extraction methods. The extraction with acetic acid using the microwave oven, however, overestimated the Si availability. In the sandy-loam soil, extraction with deionized water using the microwave oven method was more effective in estimating the Si availability in the soil than the other extraction methods.

Ecotoxicological impact of arsenic on earthworms and collembolans as affected by attributes of a highly weathered tropical soil.

High levels of heavy metals in soils may impose serious impacts on terrestrial organisms. In Brazil, the prevention values for evaluating the ecological risk of these elements are based only on soil chemical analyses and/or on data from ecotoxicological assays performed in soils of temperate regions. However, the attributes of the Brazilian highly-weathered tropical soils can influence the availability of heavy metals for soil fauna, resulting in different toxic values. To provide more accurate ecotoxicological risk values for arsenic (As) in tropical soils, we assessed the impacts of sodium arsenate (Na2HAsO4·7H2O) on the reproduction of earthworms (Eisenia andrei) and collembolans (Folsomia candida), as well as on As bioaccumulation and growth (weight loss) of E. andrei in a tropical artificial soil (TAS) and in an Oxisol. In TAS, As doses reduced the reproduction of the species and promoted weight loss of earthworms. On the other hand, the reproductions of the species as well as the earthworm growth were not altered by As in the Oxisol. The effective concentrations that reduce the reproduction of E. andrei and F. candida by 50 % (EC50) obtained in TAS (22.7 and 26.1 mg of As kg-1 of dry soil, respectively) were lower than those in the Oxisol (>135 mg kg-1, for both species). Although there was As bioaccumulation in earthworms in both soils, the internal concentrations in the earthworms were much higher in the oligochaetes exposed to arsenic in TAS. All these differences were attributed to the higher availability of As in the TAS, compared to the Oxisol, which increased the exposure of the species to the metal. The lower availability in the Oxisol was related to higher contents of type 1:1 silicate minerals and Fe and Al oxides and hydroxides, which strongly bind to As. These results highlight the importance of using tropical soils of humid regions to derive the Brazilian ecological risk prevention values for heavy metals, since the toxicity values are specific for these soils.

Concentration of Cu, Zn, Cr, Ni, Cd, and Pb in soil, sugarcane leaf and juice: residual effect of sewage sludge and organic compost application.

Many researchers have evaluated the effects of successive applications of sewage sludge (SS) on soil plant-systems, but most have not taken into account the residual effect of organic matter remaining from prior applications. Furthermore, few studies have been carried out to compare the effects of the agricultural use of SS and sewage sludge compost (SSC). Therefore, we evaluated the residual effect of SS and SSC on the heavy metal concentrations in soil and in sugarcane (Saccharum spp.) leaves and juice. The field experiment was established after the second harvesting of unburned sugarcane, when the organic materials were applied. The SS and SSC rates were (t ha(-1), dry base): 0, 12.5, 25, and 50; and 0, 21, 42, and 84, respectively. All element concentrations in the soil were below the standards established by São Paulo State environmental legislation. SS promoted small increases in Zn concentrations in soil and Cu concentrations in leaves. However, all heavy metals concentrations in the leaves were lower than the limits established for toxic elements and were in accordance with the limits established for micronutrients. There were reductions in the concentrations of Ni and Cu in soil and the concentration of Pb in juice, with increasing rates of SSC. The heavy metal concentrations were very low in the juice. Under humid tropical conditions and with short-term use, SS and SSC containing low heavy metal concentrations did not have negative effects on plants and soil.