Spatial distribution of Pb and Zn in soils under native vegetation in Southeast Brazil.

Heavy metals can play an important biological role as micronutrients but also as potentially toxic elements (PTEs). Understanding the natural concentrations of PTEs-Pb and Zn included-in soils allows for the identification and monitoring of contaminated areas and their role in environmental risk assessment. In this study, we aim to determine semi-total or natural and available concentrations of Pb and Zn in topsoils (0-20 cm depth) from 337 samples under native vegetation in the State of Minas Gerais, Brazil. Additionally, we sought to interpret the spatial geochemical variability using geostatistical techniques and quality reference values for these elements in soils were established. The semi-total concentrations were determined by flame and graphite furnace atomic absorption after microwave-assisted nitric acid digestion method. The available concentrations were extracted using the Mehlich-I extractor and determined by atomic absorption spectrometer. Spatial variability was modeled using semivariance estimators: Matheron's classic, Cressie and Hawkins' robust, and Cressie median estimators, the last two being less sensitive to extreme values. This allowed the construction of digital maps through kriging of semi-total Pb and Zn contents using the median estimator, as well as other soil properties by the robust estimator. The dominance of acidic pH and low CEC values reflects highly weathered low-fertility soils. Semi-total Pb contents ranged from 2.1 to 278 mg kg-1 (median: 9.35 mg kg-1) whereas semi-total Zn contents ranged from 2.7 to 495 mg kg-1 (median: 7.7 mg kg-1). The available Pb contents ranged from 0.1 to 6.92 mg kg-1 (median: 0.54 mg kg-1) whereas available Zn contents ranged from 0.1 to 78.2 mg kg-1 (median: 0.32 mg kg-1). The highest Pb and Zn concentrations were observed near Januária, in the northern part of the territory, probably on limestone rocks from the Bambuí group. Finally, the QRVs for Pb and Zn in natural soils were lower than their background values from other Brazilian region and below the prevention values suggested by Brazilian environmental regulations.

Geochemistry signatures of mercury in soils of the Amazon rainforest biome.

Mercury (Hg) toxicity in soils depends on Hg species and other physical and chemical attributes, as selenium (Se) hotspots in soils, particularly relevant in Amazonian soils. The study of Hg species and their relations in representative locations of the Amazon rainforest biome is critical for assessing the potential risks of Hg in this environment. This work aimed to determine the concentration of total Hg and its species (Hg0, Hg22+ and Hg2+), and to correlate Hgtotal concentration with total elemental composition, magnetic susceptibility, and physicochemical attributes of Amazon soils. Nine sites in the Amazon rainforest biome, Brazil, were selected and analyzed for their chemical, physical, and mineralogical attributes. The clay fraction of the studied Amazon soils is dominated by kaolinite, goethite, hematite, gibbsite, and quartz. Mica was also found in soils from the States of Acre and Amazonas. Hgtotal ranged from 21.5 to 208 µg kg-1 (median = 104 µg kg-1), and the concentrations did not exceed the threshold value established for Brazilian soils (500 µg kg-1). The Hg2+ was notably the predominant species. Its occurrence and concentration were correlated with the landscape position and soil attributes. Hgtotal was moderately and positively correlated with TiO2, clay, and Se. The findings showed that geographic location, geological formation, and pedological differences influence the heterogeneity and distribution of Hgtotal in the studied soil classes. Thus, a detailed characterization and knowledgment of the soil classes is very important to clarify the complex behavior of this metal in the Amazon rainforest biome.

Steel mill waste application in soil: dynamics of potentially toxic elements in rice and health risk perspectives.

Potentially toxic elements (PTEs) are of great concern in steel mill wastes. Therefore, in order to use them as potential fertilizers in soil, risk assessments are needed. Three steel mill wastes were tested as possible amendments for soils at seven different doses (0, 0.5, 1, 2, 4, 8, 16 t ha-1): phosphate mud (PM), metallurgical press residue (MPR), and filter press mud (FPM) during rice cultivation in a pot experiment in a Haplic Gleisol. Analysis on rice tissues, including roots, shoots, husk, and grains, were conducted and contents of Cu, Cd, Ni, Zn, Mn, and Pb were assessed. Translocation and bioaccumulation factors were calculated for each element. In general, PTEs are more accumulated in roots and greater contents of Zn and Mn were found, while the lowest ones were found for Pb, probably due to its lack of functional roles during plants development. Higher translocation was observed for Mn, which is associated to the redox conditions of rice cultivation and the high mobility of this element under this condition. Application of steel mill wastes can increase PTE bioavailability and translocation factors, especially PM, but all of the wastes reveal a high hazard index.

Steel mill waste effects on rice growth: comparison of chemical extractants on lead and zinc availability.

Zinc deficiency is widespread in cultivated soils, limiting the grain crop production and the adequate human nutrition. Several wastes from metallurgical activity can be used as Zn source, but these materials generally also have other potentially toxic elements, such as Pb, that can be highly toxic for plants and humans. This study aimed to evaluate the efficiency of five chemical extractors (water, citric acid, DTPA, Mehlich 1, and USEPA 3051A) in better correlating with the bioavailable contents of Zn and Pb in soils treated with steel mill wastes (metallurgic press residue (MPR), filter press mud (FPM), and phosphate mud (PM)). Rice plants were cultivated in pots with 4 kg of a Haplic Eutrophic Gleisol and steel mill wastes were applied in soil at increasing doses (0, 0.5, 1, 2, 4, 8, and 16 t ha-1). The availability of the potentially toxic elements Zn and Pb was assessed as total contents in rice shoots, grains, husks, and roots. The results showed that the USEPA 3051A method extracted greater contents of Zn and Pb from soil compared with other extractants. Due to their greater natural Pb and Zn contents, MPR and PM promoted higher contents of these elements in soils, respectively. Doses of PM influenced Zn contents in grains. After adding 16 t ha-1 of PM, Zn content in rice grains was 0.1 mg kg-1. However, at doses 0.5, 1, 2, and 4 t ha-1, the average concentration of Zn in the grains was 40 mg kg-1. The wastes MPR and FPM at 16 t ha-1 promoted Zn concentration in grains of 42 and 45 mg kg-1, respectively. The greatest contents of Pb in grains were found after addition of FPM at doses 0.5, 1, and 2 t ha-1: 6.67, 4.96, and 0.45 mg kg-1, respectively, and above 4 t ha-1 (4, 8, and 16 t ha-1); Pb content in grains was less than 0.3 mg kg-1. The content of Pb in roots at 16 t ha-1 of PM, MPR, and FPM was 18, 25, and 155 mg kg-1, respectively, and for Zn, under the same conditions, 100, 255, and 813 mg kg-1 for MPR, FPM, and PM, respectively. USEPA 3051A can be used to assess Pb and Zn available contents, and positive correlations with bioavailable contents of these elements in roots prove its feasibility. Further studies are necessary to state the safety of using steel mill application, including the use of other crop species, but PM is a promising waste for soil Zn fertilization.

Comparison of bioaccessibility methods in spiked and field Hg-contaminated soils.

Estimating bioaccessible content of mercury in soils is essential in evaluating risks that contaminated soils pose. In this study, soil samples spiked with HgCl2 through adsorption were used to test the effects of liming, soil organic matter, soil depth, and Hg concentration on the following bioaccessibility tests: dilute nitric acid at room temperature, dilute nitric acid at body temperature, Simplified Bioaccessibility Extraction Test (SBET) method, and gastric phase of the In vitro Gastrointestinal (IVG) protocol. Soil and sediment samples from Descoberto, Minas Gerais (Brazil), a city with a well-known record of Hg contamination from artisanal mining, were subjected to these bioaccessibility tests for the first time, and the different methods of estimating bioaccessible content were compared. Bioaccessible fractions in spiked samples ranged from 10% to 60%, and this high bioaccessibility was due to the highly soluble species of Hg and the short time under adsorption. In general, clay and organic matter decreased bioaccessible content. Although the soil in Descoberto is undoubtedly polluted, mercury bioaccessibility in that area is low. In general, dilute nitric acid estimated higher bioaccessible content in soil samples, whereas the SBET method estimated higher bioaccessible content in sediment samples. In multivariate analysis, two groups of bioaccessibility tests arise: one with the two nitric acid tests, and the other with SBET and the gastric phase of the IVG protocol. The addition of pepsin and glycine in the last two tests suggests a more reliable test for assessing mercury bioaccessibility.

Mercury fractionation in tropical soils: A critical point of view.

Problems related to specificity and re-precipitation of metals in sequential chemical extractions can impair their routine use. In order to test the efficiency of a sequential chemical procedure, model compounds composed by soil components commonly found in tropical soils such as goethite, Al-goethite, ferrihydrite, hematite, bauxite, and humic acid were incubated with either Hg(NO3)2 or HgSO4 and submitted to chemical extraction. The procedure aims to assess: (i) water soluble Hg; (ii) bioaccessible Hg at pH near human stomach; (iii) Hg associated with organic matter; (iv) reduced Hg; (v) Hg associated with Fe, Al, and Mn oxides; and, (vi) residual Hg. This procedure was also tested via single and sequential extractions using the surface and subsurface samples of two tropical soils, i.e., a Rhodic Acrudox and a Typic Hapludox, with and without lime application. Soil samples were submitted to an adsorption experiment with HgCl2 and a high adsorption percentage was observed. The majority of Hg at both single and sequential procedure was extracted by an acetic acid solution (pH = 2). Liming, soil depth, and soil type were not determinative on Hg extractability. The sequential extraction applied showed a lack specificity of Hg fractions, confirmed by the model components.