Gérald J. Zagury

Partitioning and speciation of chromium, copper, and arsenic in CCA-contaminated soils: influence of soil composition

This study focused on the influence of soil composition and physicochemical characteristics on the retention and partitioning of Cu, Cr and As in nine chromated copper arsenate (CCA) artificially contaminated soils. A statistical mixture design was used to set up the number of soils and their respective composition. Sequential extraction and modified solvent extraction were used to assess Cu and Cr partitioning and As speciation [As(III) or As(V)]. It was found that peat had a strong influence on CEC (232 meq/100 g), on buffer capacity and on Cu and Cr retention, whereas kaolinites contribution to the CEC was minor (38 meq/100 g). Average metal retention in mineral soils was low (58% for Cu and 23% for Cr) but increased dramatically in highly organic soils (96% for Cu and 78% for Cr). However, both organic and mineral soils demonstrated a very high sorption of added As (71-81%). Levels of Cu and Cr in a soluble or exchangeable form (F1) in highly organic soils were very low, whereas the levels strongly bound to organic matter were much higher. Conversely, in mineral soils, 47% of Cu and 18% of Cr were found in F1. As a result, Cr and Cu in moderately and highly organic contaminated soils were present in less mobile and less bioavailable forms, whereas in mineral soils, the labile fraction was higher. The modified method used for selective determination of mineral As species in CCA-contaminated soils was found to be quantitative and reliable. Results revealed that arsenic was principally in the pentavalent state. Nevertheless, in organic soils, arsenite was found in significant proportions (average value of 29% in highly organic soils). This indicates that some reduction of arsenate to arsenite occurred since the original species in CCA is As(V).

Multiple factor design for reactive mixture selection for use in reactive walls in mine drainage treatment

Sulfate-reducing reactive walls installed in situ in the path of acid mine drainage contaminated groundwater, present a promising passive treatment technology. However, a rigorous and methodical selection of the most appropriate reactive mixture composition still needs to be investigated. The aim of this study was the selection of the most reactive medium using a multiple factor design and the modeling of the sulfate-reduction rate. Reactivity of 17 mixtures was assessed in batch reactors (in duplicates) using a synthetic AMD. Results indicate that within 41 days, sulfate concentrations decreased from initial concentrations of 2,000-3,200 mg/l to final concentrations of <90 mg/l. Metal removal efficiencies ranged between 51-84% for Ni and 73-93% for Zn. Generated sulfate-reduction rate predictive models which had very satisfactory parameters (R2 = 0.86, F = 62.38 (p-level < 10(-13)) and R2 = 0.90. F = 62.30 (p-level < 10(-13))) identified poultry manure and two other carbon sources as the critical variables for sulfate-reduction rate.

Exposure assessment and risk characterization from trace elements following soil ingestion by children exposed to playgrounds, parks and picnic areas.

Soil ingestion is an important pathway for exposure to metals for children. The objectives of this study were to: (1) Assess urban soil contamination by selected metals (As, Cr, Cu, Ni, Pb, and Zn) in 24 sites (127 soil samples) in Istanbul, Turkey, (2) Investigate relationships between soil contamination and site properties (type of site, equipment type, soil properties), (3) Characterize the risk for critically contaminated sites by taking oral metal bioaccessibility and two soil ingestion scenarios into account. Average metal concentrations were similar in the 17 playgrounds, 4 parks and 3 picnic areas sampled. Five out of 24 sites (all equipped with treated wood structures) had systematically higher contamination than background for As, Cu, Cr or Zn, and measured concentrations generally exceeded Turkish regulatory values. High Cu concentrations in these sites were attributed to the leaching from wood treated with Cu-containing preservatives other than chromated copper arsenate (CCA). Risk characterization for these sites showed that hazard index was below one in both involuntary soil ingestion and soil pica behaviour scenarios for all metals. However, probabilistic carcinogenic risk for As uptake exceeded 1x10(-6) in both scenarios. A sensitivity analysis showed that soil ingestion rate was the most important parameter affecting risk estimation. Risk from As uptake for children from soils of parks, playgrounds and picnic areas may be serious, especially if soil pica behaviour is present.

Biological treatment of highly contaminated acid mine drainage in batch reactors: Long-term treatment and reactive mixture characterization.

Passive bioreactors involving sulphate-reducing bacteria (SRB) are a practical alternative technology to treat acid mine drainage (AMD). Careful selection of the organic carbon source is important to ensure performance and long-term efficiency of the treatment. However, a rigorous and methodical characterization to predict the biodegradability of organic substrates by SRB still needs to be investigated. In the present study, four natural organic materials were thoroughly characterized to assess their ability to serve as substrates and to find a parameter that links organic carbon sources with their biodegradability. Three reactive mixtures were then comparatively evaluated for their performance to treat a highly contaminated AMD in long-term (152 days) batch experiments. All three mixtures were successful for sulphate reduction and metal (Fe, Ni, Cd, Zn, and Mn) removal (91.8-99.8%). Higher efficiencies were observed in the reactors with 30% (w/w) cellulosic wastes (maple wood chips and sawdust) which decreased sulphate concentrations from 5500 mg/L to <1mg/L, than in reactors with 2-3% cellulosic wastes, where final sulphate concentrations were in the range 2000-2750 mg/L. Organic material characterization indicated that higher C/N ratios, chemical oxygen demand (COD)/SO(4)(2-) ratios and dissolved organic carbon (DOC)/SO(4)(2-) ratios were associated with better sulphate-reducing conditions and metal removal. This work suggests that C/N and DOC/SO(4)(2-) ratios considered together are key parameters to assess the biodegradability of natural organic wastes under sulphate-reducing conditions.

Arsenic bioaccessibility in CCA-contaminated soils: Influence of soil properties, arsenic fractionation, and particle-size fraction

Arsenic bioaccessibility in soils near chromated copper arsenate (CCA)-treated structures has recently been reported, and results have shown that soil properties and arsenic fractionation can influence bioaccessibility. Because of the limited data set of published results, additional soil samples and a wider range of soil properties are tested in the present work. The objectives are: (1) to confirm previous results regarding the influence of soil properties on arsenic bioaccessibility in CCA-contaminated soils, (2) to investigate additional soil properties influencing arsenic bioaccessibility, and to identify chemical extractants which can estimate in vitro gastrointestinal (IVG) bioaccessibility, (3) to determine arsenic speciation in the intestinal phase of the IVG method and, (4) to assess the influence of two particle-size fractions on arsenic bioaccessibility. Bioaccessible arsenic in eight soils collected near CCA-treated utility poles was assessed using the IVG method. Five out of the eight soils were selected for a detailed characterization. Moreover, these five soils and two certified reference materials were tested by three different metal oxide extraction methods (citrate dithionite (CD), ammonium oxalate (OX), and hydroxylamine hydrochloride (HH)). Additionally, VMINTEQ was used to determine arsenic speciation in the intestinal phase. Finally, two particle-size fractions (<250 microm, <90 microm) were tested to determine their influence on arsenic bioaccessibility. First, arsenic bioaccessibility in the eight study-soils ranged between 17.0+/-0.4% and 46.9+/-1.1% (mean value 30.5+/-3.6%). Using data from 20 CCA-contaminated soil samples, total organic carbon (r=0.50, p<0.05), clay content (r=-0.57, p<0.01), sand content (r=0.48, p<0.05), and water-soluble arsenic (r=0.66, p<0.01) were correlated with arsenic bioaccessibility. The mean percentage of total arsenic extracted from five selected soils was: HH (71.9+/-4.1%)>OX (58.0+/-3.1%)>water-soluble arsenic (2.2+/-0.5%), while the mean value for arsenic bioaccessibility was 27.3+/-2.8% (n=5). Arsenic extracted by HH (r=0.85, p<0.01, n=8) and OX (r=0.93, p<0.05, n=5), showed a strong correlation with arsenic bioaccessibility. Moreover, dissolved arsenic in the intestinal phase was exclusively under the form of arsenate As(V). Finally, arsenic bioaccessibility (in mg/kg) increased when soil particles <90 mum were used.

Mercury fractionation, bioavailability, and ecotoxicity in highly contaminated soils from chlor-alkali plants

Mercury (Hg) fractionation, speciation, bioavailability, and ecotoxicity were investigated in three highly contaminated soils from chlor-alkali plants. Single extractions and a validated four-step sequential extraction scheme were used. Total, volatile, and methyl-Hg concentrations were determined. Mercury was then separated in fractions defined as water-soluble (F1), exchangeable (F2), organic (F3), and residual (F4). Germination and growth inhibition of barley (Hordeum vulgare) and mortality of earthworms (Eisenia andrei) were assessed, and tissue-Hg concentrations of exposed organisms were determined. Results revealed highly (295 +/- 18-11,500 +/- 500 microg Hg/g) contaminated soils, but extracted fractions indicated relatively low mobility of Hg. Nevertheless, the water-soluble and the CaCl2-extractable fractions represented significant Hg concentrations (299 +/- 18 microg/g in soil 3, 67.4 +/- 2.3 microg/g in soil 1, and 9.5 +/- 0.3 microg/g in soil 2), and volatile Hg ranged between 14 and 98% of total Hg. Overall, Hg concentrations reached 6,560 +/- 240 microg/g in roots, 4,200 +/- 1,070 microg/g in aerial plants, and 1,410 +/- 120 microg/g in E. andrei. Earthworm mortality was 100% after exposure to the soil with the highest concentration of mobile Hg. In the latter soil, earthworm fragmentation and chlorotic plants were observed. Bioconcentration factors (BCFs) were higher in barley compared to earthworms, but BCFs yielded misleading values after exposure to the extremely contaminated soil. This study shows that Hg accumulated primarily in the roots, but results also indicate uptake of gaseous Hg by the aerial plants of barley. Tissue-Hg concentrations of both exposed organisms were correlated with water-soluble and CaCl2-extractable Hg, and growth inhibition was in agreement with Hg fractionation.

Heavy metals in toys and low-cost jewelry: Critical review of U.S. and Canadian legislations and recommendations for testing

High metal contamination in toys and low-cost jewelry is a widespread problem, and metals can become bioavailable, especially via oral pathway due to common child-specific behaviors of mouthing and pica. In this review, the U.S., Canadian, and European Union (EU) legislations on metals in toys and jewelry are evaluated. A literature review on content, bioavailability, childrens exposure, and testing of metals in toys and low-cost jewelry is provided. A list of priority metals is presented, and research needs and legislative recommendations are addressed. While the U.S. and Canadian legislations put emphasis on lead exposure prevention, other toxic elements like arsenic and cadmium in toy materials are not regulated except in paint and coatings. The EU legislation is more comprehensive in terms of contaminants and scientific approach. Current toy testing procedures do not fully consider metal bioavailability. In vitro bioaccessibility tests developed and validated for toys and corresponding metal bioaccessibility data in different toy matrices are lacking. The U.S. and Canadian legislations should put more emphasis on metal bioavailability and on other metals in addition to lead. A two-step management approach with mandatory testing of toys for total metal concentrations followed by voluntary bioaccessibility testing could be implemented.

Variability of bioaccessibility results using seventeen different methods on a standard reference material, NIST 2710

Bioaccessibility is a measurement of a substances solubility in the human gastro-intestinal system, and is often used in the risk assessment of soils. The present study was designed to determine the variability among laboratories using different methods to measure the bioaccessibility of 24 inorganic contaminants in one standardized soil sample, the standard reference material NIST 2710. Fourteen laboratories used a total of 17 bioaccessibility extraction methods. The variability between methods was assessed by calculating the reproducibility relative standard deviations (RSDs), where reproducibility is the sum of within-laboratory and between-laboratory variability. Whereas within-laboratory repeatability was usually better than (<) 15% for most elements, reproducibility RSDs were much higher, indicating more variability, although for many elements they were comparable to typical uncertainties (e.g., 30% in commercial laboratories). For five trace elements of interest, reproducibility RSDs were: arsenic (As), 22–44%; cadmium (Cd), 11–41%; Cu, 15–30%; lead (Pb), 45–83%; and Zn, 18–56%. Only one method variable, pH, was found to correlate significantly with bioaccessibility for aluminum (Al), Cd, copper (Cu), manganese (Mn), Pb and zinc (Zn) but other method variables could not be examined systematically because of the study design. When bioaccessibility results were directly compared with bioavailability results for As (swine and mouse) and Pb (swine), four methods returned results within uncertainty ranges for both elements: two that were defined as simpler (gastric phase only, limited chemicals) and two were more complex (gastric + intestinal phases, with a mixture of chemicals).

Contamination by ten harmful elements in toys and children's jewelry bought on the North American market.

Toys and childrens jewelry may contain metals to which children can be orally exposed. The objectives of this research were (1) to determine total concentrations (TCs) of As, Ba, Cd, Cr, Cu, Mn, Ni, Pb, Sb, and Se in toys and jewelry (n = 72) bought on the North American market and compare TCs to regulatory limits, and (2) to estimate oral metal bioavailability in selected items (n = 4) via bioaccessibility testing. For metallic toys and childrens jewelry (n = 24) 20 items had TCs exceeding migratable concentration limits (European Union). Seven of seventeen jewelry items did not comply with TC limits in U.S. and Canadian regulations. Samples included articles with very high Cd (37% [w/w]), Pb (65%), and Cu (71%) concentrations. For plastic toys (n = 18), toys with paint or coating (n = 12), and brittle or pliable toys (n = 18), TCs were below the EU migration limits (except in one toy for each category). Bioaccessibility tests showed that a tested jewelry item strongly leached Pb (gastric: 698 μg, intestinal: 705 μg) and some Cd (1.38 and 1.42 μg). Especially in metallic toys and jewelry, contamination by Pb and Cd, and to a lesser extent by Cu, Ni, As, and Sb, still poses an acute problem in North America.

Comparison of four extraction procedures to assess arsenate and arsenite species in contaminated soils

Inorganic arsenic in soils poses an important environmental concern. Several studies reported an oxidation of arsenite to arsenate during its extraction from soils. The objectives of this study were to (1) identify, among published procedures, an extraction method which preserves the oxidation state of arsenic and (2) to assess the influence of soil physicochemical properties on the performance of these methods. Four extraction strategies were compared: 1) 10 M HCl, 2) 15% (v/v) H(3)PO(4), 3) 10 mM phosphate + 0.5% (w/v) NaDDC, and, 4) 1 M H(3)PO(4) + 0.5 M ascorbic acid (C(6)H(8)O(6)). Separation and analysis of As species was performed by HPLC-ICP/MS. Oxidation of As(III) into As(V) during extraction was more important in soils with high content of Mn oxides. Extraction of arsenic from soils with 1 M H(3)PO(4) + 0.5 M C(6)H(8)O(6) under microwaves was the best strategy to extract the majority of As while minimizing conversion of As(III) into As(V).