SEQUENTIAL EXTRACTION OF PHOSPHORUS BY MEHLICH-1 AND ION EXCHANGE RESIN FROM B HORIZONS OF FERRIC AND PERFERRIC LATOSOLS (OXISOLS)

In general, Latosols have low levels of available P, however, the influence of the parent material seems to be decisive in defining the pool and predominant form of P in these soils. This study evaluated P availability by extraction with Mehlich-1 (M-1) and Ion Exchange Resin (IER), from samples of B horizons of Ferric and Perferric Latosols developed from different parent materials. To this end, in addition to the physical and chemical characterization of soils, 10 sequential extractions were performed with M-1 and IER from samples of B horizons (depth between 0.8 and 1.0 m). Total contents of Ca, P, Fe, Al, and Ti were determined after digestion with nitric, hydrofluoric and perchloric acids. The effects of sequential P extractions on Fe oxides were also evaluated from the analyses of dithionite-citrate-bicarbonate and ammonium acid oxalate. The high similarity between contents of P accumulated after sequential extractions with M-1 and IER in soils developed on tuffite indicated a predominance of P-Ca. Higher contents of P after a single IER extraction show greater efficiency in P removal from highly weathered soils, as from the Latosols studied here. The P contents also show the high sensitivity of extractant M-1 in highly buffered soils. Furthermore, a single extraction with extractant M-1 or IER is not sufficient to estimate the amount of labile P in these soils.

Lead and zinc in the structure of organic and mineral soil components

In addition to the more reactive forms, metals can occur in the structure of minerals, and the sum of all these forms defines their total contents in different soil fractions. The isomorphic substitution of heavy metals for example alters the dimensions of the unit cell and mineral size. This study proposed a method of chemical fractionation of heavy metals, using more powerful extraction methods, to remove the organic and different mineral phases completely. Soil samples were taken from eight soil profiles (0-10, 10-20 and 20-40 cm) in a Pb mining and metallurgy area in Adrianópolis, Paraná, Brazil. The Pb and Zn concentrations were determined in the following fractions (complete phase removal in each sequential extraction): exchangeable; carbonates; organic matter; amorphous and crystalline Fe oxides; Al oxide, amorphous aluminosilicates and kaolinite; and residual fractions. The complete removal of organic matter and mineral phases in sequential extractions resulted in low participation of residual forms of Pb and Zn in the total concentrations of these metals in the soils: there was lower association of metals with primary and 2:1 minerals and refractory oxides. The powerful methods used here allow an identification of the complete metal-mineral associations, such as the occurrence of Pb and Zn in the structure of the minerals. The higher incidence of Zn than Pb in the structure of Fe oxides, due to isomorphic substitution, was attributed to a smaller difference between the ionic radius of Zn2+ and Fe3+.

MERCURY QUANTIFICATION IN SOILS USING THERMAL DESORPTION AND ATOMIC ABSORPTION SPECTROMETRY: PROPOSAL FOR AN ALTERNATIVE METHOD OF ANALYSIS

Despite the considerable environmental importance of mercury (Hg), given its high toxicity and ability to contaminate large areas via atmospheric deposition, little is known about its activity in soils, especially tropical soils, in comparison with other heavy metals. This lack of information about Hg arises because analytical methods for determination of Hg are more laborious and expensive compared to methods for other heavy metals. The situation is even more precarious regarding speciation of Hg in soils since sequential extraction methods are also inefficient for this metal. The aim of this paper is to present a technique of thermal desorption associated with atomic absorption spectrometry, TDAAS, as an efficient tool for quantitative determination of Hg in soils. The method consists of the release of Hg by heating, followed by its quantification by atomic absorption spectrometry. It was developed by constructing calibration curves in different soil samples based on increasing volumes of standard Hg2+ solutions. Performance, accuracy, precision, and quantification and detection limit parameters were evaluated. No matrix interference was detected. Certified reference samples and comparison with a Direct Mercury Analyzer, DMA (another highly recognized technique), were used in validation of the method, which proved to be accurate and precise.

ASSESSMENT OF BIOAVAILABILITY OF HEAVY METALS AFTER VERMICOMPOSTING IN THE PRESENCE OF ELECTRONIC WASTE

ABSTRACT Heavy metals contained in electronic waste, if discarded improperly, can become bioavailable after vermicomposting, posing a risk to the environment. Small-scale vermicomposting experiments were carried out with printed circuit boards (PCBs) to investigate the migration of heavy metals (Cu, Pb, Zn, Ni, and Sn) to the final compost, as well as the mobility and bioavailability of these metals. High total levels of Pb, Sn and Cu in samples of manure with electronic waste (MEW) and vegetables with electronic waste (VEW) were detected. Based on the initial metal levels in the PCBs and their concentration in the resulting compost, the order of migration of these metals to the MEW and VEW samples was Sn (23.1 %)>Pb (18.4 %)>Ni (4.63 %)>Zn (0.46 %)>Cu (0.14 %) and Sn (24.3 %)>Pb (23.6 %)>Ni (11.33 %)>Zn (1.76 %)>Cu (0.60 %), respectively. Mobility and bioavailability of these metals in the compost were evaluated by three-stage sequential extraction, where F1 was the exchangeable fraction, F2 the organic fraction and F3 the residual fraction. The bioavailability factor (BF) was calculated by the ratio of the sum of fractions F1 and F2 divided by the total sum of the fractions (F1 + F2 + F3). The highest bioavailability factor (BF = 0.92) was found for Pb, the heavy metal considered the greatest environmental concern in this study, indicating the high mobility and the possibility of becoming bioavailable of this metal.

Especiação de cobre e chumbo em sedimento do Rio Tubarão (SC) pelo método Tessier

The sequential extraction procedure proposed by Tessier and total digestion were applied for the analysis of sediment samples from Tubarão River. The recoveries were between 93.5 and 102.5% for Cu and 99.2 and 111% for Pb. The precision was tipically better than 6% for Cu and 3% for Pb. Comparison of the values obtained for the total digest with the sum of the extracted fractions showed that there were no significant losses in the extraction steps so that the method can be used for the monitoring availability and mobility of these analytes. According to ten points of sampling, was possible to determined the average of labiles phases (fractions 1 and 4) for Pb and Cu: 33.70% and 18.18%, respectively; and the inert phases (fraction 5- residual): 66.30% for Pb and 81.82% for Cu.

Avaliação dos métodos de extração sequencial de Tessier, Keller e Miller na determinação de ferro nativo em três tipos de solos: orgânico, brunizem e latossolo

Sequential extraction is not totally effective to dissolve distinct forms of trace elements. The extractive solution, for example, can dissolve less of the target fraction and more than another not wished fraction. The goal of this work is to compare the extraction of native iron with three sequential extraction methods of the heavy metals, using three soils with different physical chemistry characteristics: a histosol, an oxisol, and a mollisol. The results obtained in this work demonstrate that a smaller relation soil/extractor results in a larger extraction in almost all phases. The use of many stages of the sequential extraction, with the purpose of more association of the metal with different components of the soil, can result, among other things, in modification of the substratum by the action of the reagents used, besides reducing the selectivity of the more specific extractors. Readsorption and redistribution of the heavy metals could have happened with larger intensity in the fraction where hidroxilamine was used with higher temperature. Sequential extraction of iron, without enrichment of soil samples, in the respective fractions in each method, it was important to better understand the behavior of the reagents considered specific to each form of the metal in soil.

Adsorção de As, Cu, Pb e Cr na avaliação da capacidade de fixação de metais por resíduo de mineradoras de ferro

Two samples of residues from iron mining plants have been investigated for their retention capacity of As, Cu, Cr, and Pb. The sample with the higher content of iron oxides showed the highest capacity to retain metals. The adsorption affinity series changes from Pb>Cu>Cr~As to As>Pb>Cu>Cr or As>Cu>Cr>Pb, depending on the material and the concentration of the initial solution. In the competitive environment, the Pb adsorption decreases and the As, Cu and Cr adsorption increases. Sequential extraction procedures, carried out after adsorption batch experiments, showed that the most important adsorption process occurs in the oxide fraction and that the major part of the absorbed metal is remobilized from exchangeable and oxide fractions.

Distribuição, fracionamento e mobilidade de elementos traço em sedimentos superficiais

The gold and iron mining activities in the Velhas River yield considerable amounts of suspended solids as well as metals to the hydrological system of the region. The risks were assessed by sequential extraction procedures. They were carried out in sediment samples, aiming to evaluate the presence of Co, Cr, Cu, Ni, Zn and As. Although being at high levels in some parts of the river (e.g. As 527 mg g-1 and Cr 475 mg g-1) they are associated with the residual fraction. Mobility factors were also calculated and show that these species are enriched along the river, e.g. for As 0.02 at the spring and 0.33 at the high course of the river.

Estudo do comportamento do chumbo em latossolos brasileiros tratados com fosfatos: contribuições para a remediação de sítios contaminados

Phosphates have been used for lead immobilization in soils but the influence of soil type is not fully understood. In this work, lead chemical behaviour in two Brazilian latosoils (LA and LV) was studied via treatment with phosphates. The Pb concentration in Toxicity Characteristic Leaching Procedure (TCLP) solutions was decreased in all treatments. After treatment with H3PO4 the Pb concentration in the LA remained within the regulatory limit established by EPA. The ecotoxicological results with Daphnia pulex showed that this treatment reduced the lead bioavailability. Sequential extraction analyses showed that the lead was transferred from the most available to the residual fraction. Relevant decrease of soluble lead was observed in all phosphate treatments.

Fracionamento de metais pesados em solo contaminado antes e após cultivo de arroz

The objective of the present work was to evaluate the distribution of Cd, Cu, Mn, Pb and Zn among the different fractions of contaminated soil, before and after rice cultivation. Seven soil samples with different degrees of contamination were studied using a randomized experimental design, with four replicates. Using an ICP-OES we analyzed the contents of heavy metals in fractions of soil, the organic matter therein, the oxides and the residual content before and after rice cultivation. The largest concentrations of Cd, Cu, Mn and Zn in the soil are found in the fractions with stable chemical bonds.

Estudio de la contaminación por metales en sedimentos acuáticos de la Bahía de Matanzas

Surface sediments of the Bay of Matanzas (Cuba) were studied to assess its environmental quality by using several criteria (metal content index, pollution load index and sediment quality guidelines). Two partial digestion sediment procedures and a modified BCR sequential extraction were used. The concentrations of metals were measured by atomic spectroscopy methods. The founded contents of Cu (2,4-27,9 mg kg-1), Zn (2,5-55,5 mg kg-1) and Ni (8,8-99,2 mg kg-1) were below those reported by other authors. The results obtained suggested that the most polluted sites were 3, 5, and 6. The sequential extraction procedure showed that most of the studied metals were associated to the more stable fractions.

Determinação de Cu, Fe, Mn, Zn e do teor de proteína total em amostras de trigo e soja após procedimento de extração sequencial

A sequential extraction procedure was applied to wheat and soybean seed samples. The total protein content (determined by two distinct methods: Bradford and bicinchoninic acid-BCA) and distribution of Cu, Fe, Mn and Zn in each fraction was determined. The sequential extraction employed four different solutions: water, 0.5 mol L-1 NaCl, ethanol/water (70:30 v v-1) and 0.5 mol L-1 NaOH. For both samples, the highest concentration of metals was observed in those extracts associated with globulin-type proteins using NaCl solution. Regarding protein content, higher levels were obtained using the BCA method.

Distribuição de Zn, Pb, Ni, Cu, Mn e Fe nas frações do sedimento superficial do Rio Cachoeira na região sul da Bahia, Brasil

The metal distribution in the surface sediment fractions of the Cachoeira River was evaluated based on the fractionation method using a five-step sequential extraction. The determination of metals was made by flame atomic absorption spectrophotometry (F AAS). Zn, Pb and Cu exhibit higher concentrations in the residual fraction of the sediment from sites that receive discharges from urban and industrial zones. High levels of Ni (60 ± 1 to 447 ± 9 µg L-1) were found in the river water, which may be detrimental to the "health" of rural communities that utilize the river water for domestic purposes without treatment.

Evaluation of antioxidant activity of agro-industrial waste of acerola (Malpighia emarginata D.C.) fruit extracts

This study was carried out to evaluate the antioxidant capacity of the agro-industrial waste from acerola. Hydroacetone, hydroethanolic, and hydromethanolic extracts were obtained using the sequential extraction process, and they were screened for their free radical DPPH• (1,1-diphenyl-2-picrilhidrazil) and ABTS•+ (2,2'-azino-bis-(3-etilbenzotiazolin 6-sulfonic acid) scavenging activity and their effect on the linoleic acid peroxidation by the ferric thiocyanate method. Soybean oil with the addition of the extracts (200 ppm) was submitted to Schaal oven test (60 °C, 28 days), in which the samples were analyzed for peroxide value and conjugated dienes. Hydroethanolic and hydromethanolic extracts exhibited good DPPH scavenging activity (low value of EC50 and TEC50 and high value of AE), good ABTS scavenging capacity (1445.1 and 1145.5 µMol TEAC.g-1, respectively), and high percentage inhibition of peroxidation of linoleic acid (96.12 and 91.84%, respectively) and showed the ability to retard the formation of peroxides and conjugated dienes.

Antioxidant and fatty acid profile of gabiroba seed (Campomanesisa Xanthocarpa Berg)

This study aimed to evaluate the antioxidant potential and fatty acid profile of gabiroba (Campomanesia xanthocarpa Berg) seeds. In order to obtain the extract, the seeds were dried, crushed, and subjected to sequential extraction by maceration and percolation in a modified soxhlet extractor using solvent polarity gradient composed of hexane, chloroform, ethyl acetate, and alcohol, respectively. The extraction time was six hours. The ethanol extract showed the highest antioxidant potential, given by the EC50 value and the amount of total phenolic compounds. High amounts of unsaturated fatty acids were found in the oil studied, especially the oleic acid.