Bioaccessibility is a measurement of a substance's 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).
Chromated copper arsenate (CCA) has been used to treat lumber for over 60 years to increase the expected lifetime of CCA-treated wood. Because of the toxicity of the arsenic and chromium used in CCA treatment, regulatory and public attention has become focused on the potential risks from this exposure source. In particular, exposure of children to arsenic from CCA-treated wood used in decks and play sets has received considerable attention. X-ray Absorption Spectroscopy (XAS) was used to evaluate the chemical structure of As and Cr in three samples of CCA-treated materials: newly treated wood, aged wood (5 years as decking), and dislodgeable residue from aged (1-4 years as decking) CCA-treated wood. The form of the Cr and As in CCA-treated material is the same in fresh and aged samples, and between treated wood and dislodged residue. In all cases, the dominant oxidation state of the two elements is As(V) and Cr(III), and the local chemical environment of the two elements is best represented as a Cr/As cluster consisting of a Cr dimer bridged by an As(V) oxyanion. Long-term stability of the As/Cr cluster is suggested by its persistence from the new wood through the aged wood and the dislodgeable residue.
This report summarizes the results of a study to develop an in vitro bioaccessibility (IVBA) extraction technique for estimating the relative bioavailability (RBA) of arsenic (As) in soil. The study was implemented in several steps. In step 1, key variables in the extraction protocol were identified. In step 2, 21 different extraction conditions were tested on 12 different soils with reliable RBA values measured in swine or monkeys to identify which yielded useful in vivo-in vitro correlations (IVIVC). In step 3, three extraction conditions were evaluated using 39 different test soils to make a final selection of the best IVIVC. In step 4, the within- and between-lab reproducibility of the extraction method was examined. The optimum IVIVC model for swine utilized a pH 1.5 IVBA extraction fluid, with an R (2) value of .723. For monkeys, the optimum IVIVC model was obtained using a pH 7 IVBA extraction fluid that contained phosphate, with an R (2) value of .755. Within-lab precision of IVBA results was typically less than 3%, with an average of 0.8% for all 4 labs. Between-lab variation in mean IVBA values was generally less than 7%, with an overall average of 3%. The principal advantages of this IVBA method compared to other in vitro methods described in the literature are that (1) the fluids and extraction conditions are simple, (2) the results have been calibrated against a larger data set than any other method, and (3) the method has been demonstrated to be reproducible both within and between labs.
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