Release of arsenic to the environment from CCA-treated wood. 1. Leaching and speciation during service

Insufficient information exists about the speciation of arsenic leaching from in-service chromated copper arsenate (CCA)-treated products and the overall impact to soils and groundwater. To address this issue, two decks were constructed, one from CCA-treated wood and the other from untreated wood. Both decks were placed in the open environment where they were impacted by rainfall. Over a one-year period, rainwater runoff from the decks and rainwater infiltrating through 0.7 m of sand below the decks was collected and analyzed for arsenic species by HPLC-ICP-MS. The average arsenic concentration in the runoff of the untreated deck was 2-3 microg/L, whereas from the CCA-treated deck it was 600 microg/L. Both inorganic As(III) and As(V) were detected in the runoff from both decks, with inorganic As(V) predominating. No detectable levels of organoarsenic species were observed. The total arsenic concentration in the infiltrated water of the treated deck had risen from a background concentration of 3 microg/L to a concentration of 18 microg/L at the end of the study. Data from the deck study were combined with annual CCA-treated wood production statistics to develop a mass balance model to estimate the extent of arsenic leaching from in-service CCA-treated wood structures to Florida soils. Results showed that during the year 2000, of the 28 000 t of arsenic imported into the state and utilized for in-service CCA-treated wood products, approximately 4600 t had already leached. Future projections suggest that an additional 11,000 t of arsenic will leach during in-service use within the next 40 years.     

Arsenic speciation of solvent-extracted leachate from new and weathered CCA-treated wood

For the past 60 yr, chromate-copper-arsenate (CCA) has been used to pressure-treat millions of cubic meters of wood in the United States for the construction of many outdoor structures. Leaching of arsenic from these structures is a possible health concern as there exists the potential for soil and groundwater contamination. While previous studies have focused on total arsenic concentrations leaching from CCA-treated wood, information pertaining to the speciation of arsenic leached is limited. Since arsenic toxicity is dependent upon speciation, the objective of this study was to identify and quantify arsenic species leaching from new and weathered CCA-treated wood and CCA-treated wood ash. Solvent-extraction experiments were carried out by subjecting the treated wood and the ash to solvents of varying pH values, solvents defined in the EPA's Synthetic Precipitation Leaching Procedure (SPLP) and Toxicity Characteristic Leaching Procedure (TCLP), rainwater, deionized water, and seawater. The generated leachates were analyzed for inorganic As(III) and As(V) and the organoarsenic species, monomethylarsonic acid (MMAA) and dimethylarsinic acid (DMAA), using high-performance liquid chromatography followed by hydride generation and atomic fluorescence spectrometry (HPLC-HG-AFS). Only the inorganic species were detected in any of the wood leachates; no organoarsenic species were found. Inorganic As(V) was the major detectable species leaching from both new and weathered wood. The weathered wood leached relatively more overall arsenic and was attributed to increased inorganic As(III) leaching. The greater presence of As(III) in the weathered wood samples as compared to the new wood samples may be due to natural chemical and biological transformations during the weathering process. CCA-treated wood ash leached more arsenic than unburned wood using the SPLP and TCLP, and ash samples leached more inorganic As(III) than the unburned counterparts. Increased leaching was due to higher concentrations of arsenic within the ash and to the conversion of some As(V) to As(III) during combustion.     

Landfill disposal of CCA-treated wood with construction and demolition (C&D) debris: arsenic, chromium, and copper concentrations in leachate

Although phased out of many residential uses in the United States, the disposal of CCA-treated wood remains a concern because significant quantities have yet to be taken out of service, and it is commonly disposed in landfills. Catastrophic events have also led to the concentrated disposal of CCA-treated wood, often in unlined landfills. The goal of this research was to simulate the complex chemical and biological activity of a construction and demolition (C&D) debris landfill containing a realistic quantity of CCA-treated wood (10% by mass), produce leachate, and then evaluate the arsenic, copper, and chromium concentrations in the leachate as an indication of what may occur in a landfill setting. Copper concentrations were not significantly elevated in the control or experimental simulated landfill setting (alpha = 0.05). However, the concentrations of arsenic and chromium were significantly higher in the experimental simulated landfill leachate compared to the control simulated landfill leachate (alpha = 0.05, p < 0.001). This indicates that disposal of CCA-treated wood with C&D debris can impact leachate quality which, in turn could affect leachate management practices or aquifers below unlined landfills.     

Chemical structure of arsenic and chromium in CCA-treated wood: implications of environmental weathering

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.     

Emissions of chromium, copper, arsenic, and PCDDs/Fs from open burning of CCA-treated wood

Aged and weathered chromated copper arsenate (CCA) treated wood was burned in an open burn research facility to characterize the air emissions and residual ash. The objectives were to simulate, to the extent possible, the combustion of such waste wood as might occur in an open field or someone's backyard; to characterize the composition and particle size distribution (PSD) of the emitted fly ash; to determine the partitioning of arsenic, chromium, and copper between the fly ash and residual ash; and to examine the speciation of the CCA elements. This work reports preliminary air emission concentrations and estimated emission factors for total particulate matter, arsenic (As), chromium (Cr), copper (Cu), and polychlorinated dibenzodioxins/dibenzofurans (PCDD/F) totals and toxic equivalents (TEQs). The partitioning of As, Cr, and Cu between the emitted fly ash and residual ash is examined and thermochemical predictions from the literature are used to explain the observed behavior. Results indicate a unimodal fly ash PSD between 0.1 and 1.0 microm diameter. In addition to a large carbonaceous component, between 11 and 14% of the As present in the burned CCA treated wood was emitted with the air emissions, with the remainder present in the residual ash. In contrast, less than 1% of both the Cr and Cu present in the wood was emitted with the air emissions. PCDD/F levels were unremarkable, averaging 1.7 ng TEQ/kg of treated wood burned, a value typical for wood combustion. Scanning electron microscopy (SEM) was unable to resolve inorganic particles consisting of Cu, Cr, or As in the wood samples, but X-ray absorption fine structure (XAFS) spectroscopy confirmed that the oxidation states of the CCA elements in the wood were Cu2+, Cr3+, and As5+. SEM examination of the fly ash samples revealed some inorganic microcrystals within the mostly carbonaceous fly ash, while XAFS spectroscopy of the same samples showed that the oxidation states after combustion were mixed Cu+ and Cu2+, Cr3+, and mixed As3+ and As5+. Estimates of the ratios of the mixed oxidation states based on the XAFS spectra were As3+/(total As) = 0.8-0.9 and Cu+/(total Cu) = 0.65-0.7. The Cu and Cr present in the fly ash were determined to coexist predominantly in the two oxide phases CuCrO2 and CuCr2O4. These results indicate that the open burning of CCA-treated wood can lead to significant air emissions of the more toxic trivalent form of As in particle sizes that are most respirable.     

Coupling speciation and isotope dilution techniques to study arsenic mobilization in the environment

We have developed an approach to isolate mechanisms controlling mobility and speciation of As in soil-water systems. The approach uses a combination of isotopic exchange and chromatographic/mass spectrometric As speciation techniques. We used this approach to identify mechanisms responsible for changes in the concentration of soluble As in two contaminated soils (Eaglehawk and Tavistock) subjected to different redox conditions and microbial activity. A high proportion of the total As in both soils was present in a nonlabile form. Incubation of the soils under anaerobic conditions led to changes in the concentration of soluble As in each soil but did not change the As speciation or the proportion of total As in labile forms in the soils. Hence, a decrease in soluble As in the Eaglehawk soil was the result of an Eh-induced pH decrease, enhancing the solid-phase sorption of As(V). An increase in soluble As in the Tavistock soil was due to an Eh-induced pH increase, decreasing solid-phase sorption of As(V). Incubation of the soils under aerobic conditions with microbial activity stimulated by addition of glucose resulted in no change in the solution concentration or speciation of As in the Eaglehawk soil, but led to a large increase in the concentration of soluble As in the Tavistock soil. This increase was due to conversion of exchangeable forms of As(V) into less strongly sorbed As(III) species. Incubation under anaerobic conditions in the presence of glucose resulted in a large increase in the concentration of soluble As in both soils; however, different mechanisms were found to be responsible for the increase in each soil. In the Eaglehawk soil higher concentrations of As were again due to conversion of exchangeable forms of As(V) into less strongly sorbed As(III) species. In contrast in the Tavistock soil, the increased As in solution was the result of release of As(V) from the large reservoir of nonlabile soil As.     

Chemical speciation and bioaccessibility of arsenic and chromium in chromated copper arsenate-treated wood and soils

This research compares the As and Cr chemistry of dislodgeable residues from chromated copper arsenate (CCA)-treated wood collected by two different techniques (directly from the board surface either by rubbing with a soft bristle brush or by rinsing from human hands after contact with CCA-treated wood) and demonstrates that these materials are equivalent in terms of both the chemical form and bonding of As and Cr and in terms of the As leaching behavior. This finding links the extensive chemical characterization and bioavailability testing that has been done previously on the brush-removed residue to a material that is derived from human skin contact with CCA-treated wood. Additionally, this research characterizes the arsenic present in biological fluids (sweat and simulated gastric fluid) following contact with these residues. The data demonstrate that in biological fluids the arsenic is present primarily as free arsenate ions. Arsenic-containing soils were also extracted into human sweat to evaluate the potential for arsenic dissolution from soils at the skin surface. For soils from field sites, only a small fraction of the total arsenic is soluble in sweat. Based on comparisons to reference materials that have been used for in vivo dermal absorption studies, these findings suggest that the actual relative bioavailability via dermal absorption of As from CCA residues and soil may be well below the current default value of 3% used by U.S. EPA.     

砷及砷的形态检测方法的研究现状

砷是一种广泛分布于自然界的微量元素,摄入过量砷元素容易引起砷的急性中毒而致死,应引起人们足够的重视。砷的毒性主要取决于它的化学形态,形态不同毒性差异很大,所以选择适当、简便、快速的测定方法是现代分析技术取得发展的必要条件。本文综述了近年来砷及其形态常用的测定方法,并且分析了各检测方法的优缺点,展望了砷及其形态检测技术的发展前景。      

Assessing influence of experimental parameters on formation of PCDD/F from ash derived from fires of CCA-treated wood

Ash residues from fires of radiata pine timber, both untreated and treated with chromated copper arsenate (CCA), were analyzed for the presence of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/F). Fire conditions were simulated using a cone calorimeter. The sensitivity of the magnitude and profile of PCDD/F in the ash under controlled experimental conditions were examined to gain an insight into the formation of PCDD/F in a system containing CCA. The total amount of PCDD/F increased from 2.0 ng/kg of ash (0.05 ng of TE/kg of ash, using WHO-TEF) for untreated radiata pine to a maximum of 2700 ng/kg of ash (78 ng of TE/kg of ash) for 0.94% CCA. Ash containing CCA showed a distinct preference for formation of PCDFs, particularly the tetrachloro homologue. It is concluded that PCDD/F formation predominantly occurred via de novo synthesis during smoldering of the char rather than during the initial flaming and pyrolysis. Furthermore, the composition of the CCA constituents present in the timber was controlled to assess whether the physical presence of Cu, a known catalyst in PCDD/F production, was sufficient to account for the formation of PCDD/F in fires of timber impregnated with CCA.     

Release of CFC-11 from disposal of polyurethane foam waste

The halocarbon CFC-11 has extensively been used as a blowing agent for polyurethane (PUR) insulation foams in home appliances and for residential and industrial construction. Release of CFCs is an important factor in the depletion of the ozone layer. For CFC-11 the future atmospheric concentrations will mainly depend on the continued release from PUR foams. Little is known about rates and time frames of the CFC release from foams especially after treatment and disposal of foam containing waste products. The CFC release is mainly controlled by slow diffusion out through the PUR. From the literature and by reevaluation of an old reported experiment, diffusion coefficients in the range of 0.05-1.7 x 10(-14) m2 s-1 were found reflecting differences in foam properties and experimental designs. Laboratory experiments studying the distribution of CFC in the foam and the short-term releases after shredding showed that about 40% of the CFC is solubilized in the PUR phase, and that up to 10% of the total content will be released within a few weeks if the foam is shredded down to 2-cm sized pieces. For smaller pieces the quick release will be larger. Fifty percent of residual CFC content will be released within 9-300 years from 2-cm pieces based on the range in diffusion coefficients reported. For larger pieces the initial release is insignificant, and the release time frames are much longer than for the shredded foam.     

Selenium and arsenic speciation in fly ash from full-scale coal-burning utility plants

X-ray absorption fine structure spectroscopy has been used to determine directly the oxidation states and speciation of selenium and arsenic in 10 fly ash samples collected from full-scale utility plants. Such information is needed to assess the health risk posed by these elements in fly ash and to understand their behavior during combustion and in fly ash disposal options, such as sequestration in tailings ponds. Selenium is found predominantly as Se(IV) in selenite (SeO3(2-)) species, whereas arsenic is found predominantly as As(V) in arsenate (AsO4(3-)) species. Two distinct types of selenite and arsenate spectra were observed depending upon whether the fly ash was derived from eastern U.S. bituminous (Fe-rich) coals or from western subbituminous or lignite (Ca-rich) coals. Similar spectral details were observed for both arsenic and selenium in the two different types of fly ash, suggesting that the postcombustion behavior and capture of both of these elements are likely controlled by the same dominant element or phase in each type of fly ash.     

Determination of total arsenic content and arsenic speciation in different types of rice

Food Science and Biotechnology - The objectives of this study was to examine the amount of total arsenic and arsenic speciation in different types of rice from two areas in Korea using inductively...     

Leaching of arsenic from granular ferric hydroxide residuals under mature landfill conditions

Most arsenic bearing solid residuals (ABSR) from water treatment will be disposed in nonhazardous landfills. The lack of an appropriate leaching test to predict arsenic mobilization from ABSR creates a need to evaluate the magnitude and mechanisms of arsenic release under landfill conditions. This work studies the leaching of arsenic and iron from a common ABSR, granular ferric hydroxide, in a laboratory-scale column that simulates the biological and physicochemical conditions of a mature, mixed solid waste landfill. The column operated for approximately 900 days and the mode of transport as well as chemical speciation of iron and arsenic changed with column age. Both iron and arsenic were readily mobilized under the anaerobic, reducing conditions. During the early stages of operation, most arsenic and iron leaching (80% and 65%, respectively) was associated with suspended particulate matter, and iron was lost proportionately faster than arsenic. In later stages, while the rate of iron leaching declined, the arsenic leaching rate increased greater than 7-fold. The final phase was characterized by dissolved species leaching. Future work on the development of standard batch leaching tests should take into account the dominant mobilization mechanisms identified in this work: solid associated transport, reductive sorbent dissolution, and microbially mediated arsenic reduction.     

Variation in arsenic speciation and concentration in paddy rice related to dietary exposure

Ingestion of drinking water is not the only elevated source of arsenic to the diet in the Bengal Delta. Even at background levels, the arsenic in rice contributes considerably to arsenic ingestion in subsistence rice diets. We set out to survey As speciation in different rice varieties from different parts of the globe to understand the contribution of rice to arsenic exposure. Pot experiments were utilized to ascertain whether growing rice on As contaminated soil affected speciation and whether genetic variation accounted for uptake and speciation. USA long grain rice had the highest mean arsenic level in the grain at 0.26 microg As g(-1) (n = 7), and the highest grain arsenic value of the survey at 0.40 microg As g(-1). The mean arsenic level of Bangladeshi rice was 0.13 microg As g(-1) (n = 15). The main As species detected in the rice extract were AsIII, DMAV, and AsV. In European, Bangladeshi, and Indian rice 64 +/- 1% (n = 7), 80 +/- 3% (n = 11), and 81 +/- 4% (n = 15), respectively, of the recovered arsenic was found to be inorganic. In contrast, DMAV was the predominant species in rice from the USA, with only 42 +/- 5% (n = 12) of the arsenic being inorganic. Pot experiments show that the proportions of DMAV in the grain are significantly dependent on rice cultivar (p = 0.026) and that plant nutrient status is effected by arsenic exposure.     

Modeling the effect of algal dynamics on arsenic speciation in Lake Biwa

Algae reduce and methylate arsenate and the end product of the reaction is correlated to their growth rate. At slow growth rates, dimethylarsinate (DMA) is produced, and at fast growth rates arsenite (As(III)) is produced. Previous work has linked this phenomenon to the phosphorus luxury uptake mechanism of algae, and a model was developed for the process (Hellweger et al. Limnol. Oceanogr. 2003, 48, 2275). This paper presents the integration of that process model for arsenic transformation by algae into a full ecological model and application to Lake Biwa, Japan. The model application allows for a quantitative analysis of the field data, consistent with the process model and the ecological dynamics of the lake. The newly developed ecological model includes a variable phytoplankton composition, which is needed to simulate luxury uptake. This is in contrast to most existing ecological models, which typically assume a fixed "Redfield" composition. The model adequately reproduces the observed ecology of Lake Biwa, including the rapid uptake of phosphate by phytoplankton without immediate growth (luxury uptake) following lake overturn. The model also reproduces the observed arsenic speciation, including the gradual appearance of DMA during the summer and peaks in As(III) concentration at the onset of spring and fall algal blooms.     

XAS study of iron and arsenic speciation during Fe(II) oxidation in the presence of As(III)

The speciation of As and Fe was studied during the oxidation of Fe(II)-As(III) solutions by combining XAS analysis at both the Fe and As K-edges. Fe(II) and As(III) were first hydrolyzed to pH 7 under anoxic conditions; the precipitate was then allowed to oxidize in ambient air for 33 h under vigorous stirring. EXAFS analysis at the As K-edge shows clear evidence of formation of inner-sphere complexes between As(III) and Fe(II), i.e., before any oxidation. Inner-sphere complexes were also observed when Fe became sufficiently oxidized, in the form of edge-sharing and double-corner linkages between AsIIIO3 pyramids and FeIIIO6 octahedra. XAS analyses at the Fe K-edge reveal that the presence of As(III) in the solution limits the polymerization of Fe(II) and the formation of green rust and inhibits the formation of goethite and lepidocrocite. Indeed, As(III) accelerates the Fe(II) oxidation kinetics and leads to the formation of nanosized Fe-As subunits of amorphous aggregates. These observations, rather than a presumed weaker affinity of As(III) for iron oxyhydroxides, might explain why As(III) is more difficult to remove than As(V) by aerating reducing groundwater.