Evaluating landfill disposal of chromated copper arsenate (CCA) treated wood and potential effects on groundwater: evidence from Florida

Chromated copper arsenate (CCA) treated wood has been used for more than 50 years. Recent attention has been focused on appropriate disposal of CCA-treated wood when its service life ends. Groups in the US and Europe concerned with the possibility of arsenic migration to groundwater from disposed CCA-treated wood have proposed that consumers be required to dispose of the wood as a hazardous waste, in the most protective of landfills. We examined available data for evidence of arsenic migration from unlined construction and demolition (C&D) debris landfills in Florida, where CCA-treated wood is disposed. Florida was chosen because soil, groundwater, landfill design, weather, and levels of CCA-treated wood use make the state a uniquely sensitive indicator for observing arsenic migration from CCA-treated wood disposal sites, should it occur. We developed and quality-checked a CCA-treated wood disposal model to estimate the amount of wood and associated arsenic disposed. By 2000, an estimated 13 million kg of arsenic in CCA-treated wood was disposed in Florida; however, groundwater monitoring data do not indicate that arsenic is migrating from unlined C&D landfills. Our results provide evidence that highly stringent regulation of CCA-treated wood disposal, such as treatment as a hazardous waste, is unnecessary.     

Increased PCDD/F formation in the bottom ash from fires of CCA-treated wood

Bottom ash that was the result of the combustion of chromated copper arsenate (CCA) treated wood under controlled fire conditions showed an increase of several orders of magnitude in the levels of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), compared to that of untreated timber. Wood that has been pressure treated with CCA contains copper (II), which is known to catalyse the so-called de novo formation of PCDD/Fs. Comparable levels of PCDD/Fs would be expected in residual ash from burning CCA-treated wood in backyard fires, stoves and wood heaters, as a consequence of similar combustion conditions.     

Environmental fate and bioavailability of wood preservatives in freshwater sediments near an old sawmill site.

Impacts of an old contaminated sawmill site located in Eastern Finland were studied, with emphasis on transportation and bioaccumulation of wood preservatives in the surrounding water system. To assess the transportation of chlorophenols and chromated copper arsenate (CCA) from the sawmill to the nearby lake, the concentrations of these compounds in selected sediment samples were analyzed. To assess the contribution of a pulp mill further upstream, the concentration of extractable organic halogens (EOX) was analyzed. Bioaccumulation of wood preservatives from sediments was examined using Lumbriculus variegatus as test organism. In sediments collected from the sawmill area, concentrations of chlorophenols, arsenic, chromium and copper were high. In the surrounding area the concentrations of these compounds were slightly elevated at some sampling points but were mostly within the natural range of variation. Thus, it can be concluded that transportation of wood preservatives from the sawmill area to its surroundings is fairly low. However, 60 microg/l of arsenic and 50 microg/l of copper were found in water taken from a brook that runs through a landfill area of the sawmill to the nearby river, and the concentration of arsenic in the surface sediment at one sampling point in the lake was slightly elevated. The total amount of organohalogens in sediment was higher in the river and the lake than in the sawmill area. Of all the wood preservatives studied, only arsenic was found to bioaccumulate in present conditions, reaching a tissue concentration of 362 microg/g dw in organisms exposed for 28 days to sediment from the brook. High concentration of arsenic in oligochaeta tissue was related to high concentration of arsenic in the pore water.     

Fractionation of heavy metals in liquefied chromated copper arsenate 9-treated wood sludge using a modified BCR-sequential extraction procedure

Chromated copper arsenate (CCA)-treated wood was liquefied with polyethylene glycol/glycerin and sulfuric acid. After liquefaction, most CCA metals (98% As, 92% Cr, and 83% Cu) were removed from liquefied CCA-treated wood by precipitation with calcium hydroxide. The original CCA-treated wood and liquefied CCA-treated wood sludge were fractionated by a modified Community Bureau of Reference (BCR) sequential extraction procedure. The purpose of the BCR-sequential extraction used in this study was to examine the availability of CCA metals in treated wood for reuse. Both As and Cr had a slightly higher concentration in the sludge sample than in original CCA-treated wood. The sequential extraction showed that As and Cr were principally existed in an oxidizable fraction (As, 67%; Cr, 88%) in original CCA-treated wood. Only 1% of both As and Cr were extracted by hot nitric acid with the last extraction step. The distribution of As and Cr changed markedly in liquefied CCA-treated wood sludge.The amount of As in the exchangeable/acid extractable fraction increased from 16% to 85% while the amount of Cr increased from 3% to 54%. Only about 3% of As was present in the oxidizable fraction. However, there was still about 34% of Cr in the same fraction. Based on these results from sequential extraction procedures, it can be concluded that the accessibilities of CCA metals increase markedly by the liquefaction–precipitation process.     

Fungal biodegradation of CCA-treated wood and removal of its metal components

In the present study, 5 isolates of brown-rot fungi were used for fungal bioprocessing (FB) of chromated copper arsenate (CCA)-treated wood wastes: Antrodia vaillantii SEL8501, Fomitopsis palustris TYP0507 and TYP6137, and Crustoderma sp. KUC8065 and KUC8611. The isolates showed notable capacity for the degradation of treated wood and removal of CCA components via the American Wood Protection Association soil block test. Among them, Crustoderma sp. KUC8611 effectively decayed the treated wood, causing a mass loss of up to 60%. F. palustris caused extensive leaching of CrO₃ of up to 79% and As₂O₅ of up to 87%, but only moderate leaching of CuO of up to 50%. This high capacity for removal of CrO₃ and As₂O₅ showed a strong logarithmic relationship with the amount of oxalic acid produced in the decayed wood. The majority of metals removed from treated wood during the decay process were deposited in the soil and feeder strip. Further investigation will be required to establish the capability of selected fungi for FB of full-sized lumber treated with CCA.     

Chemical Stabilization of Mixed Organic and Metal Compounds: EPA SITE Program Demonstration of the Silicate Technology Corporation Process

In November 1990, the Silicate Technology Corporation's (STC) proprietary process for treating soil contaminated with toxic semivolatile organic and inorganic contaminants was evaluated in a Superfund Innovative Technology Evaluation (SITE) field demonstration at the Selma Pressure Treating (SPT) wood preserving site in Selma, California. The SPT site was contaminated principally with pentachlorophenol (PCP) and arsenic, as well as lesser amounts of chromium and copper. Because of their importance when selecting a remedy for the site, PCP and arsenic were identified as critical analytes to evaluate the effectiveness of treatment.

Evaluation of STC's treatment process was based on contaminant mobility, measured by numerous leaching tests, and structural integrity of the solidified material, measured by physical, engineering, and morphological tests. An economic analysis was also performed, using cost information supplied by STC and supplemented by information generated during the demonstration.

Conclusions drawn from this SITE demonstration evaluation are: (1) the STC process can chemically stabilize contaminated soils similar to those at the Selma site that contain both semivolatile organic and inorganic contaminants; (2) PCP was successfully treated as demonstrated by total waste analysis; (3) heavy metals such as arsenic can be immobilized successfully based on various leach-test criteria; (4) the short-term physical stability of the treated waste was good, with unconfined compressive strengths (UCS) well above landfill solidification standards; (5) treatment resulted in a volume increase of 59 to 75 percent (68 percent average) and a slight increase in bulk density; and (6) the process is expected to cost approximately $190 to $360 per cubic yard when it is used to treat 15,000 cubic yards of waste similar to that found at the STC demonstration site, assuming that on-site, in-place disposal is performed.     

Arsenic species and leachability in the fronds of the hyperaccumulator Chinese brake (Pteris vittata L.)

Arsenic speciation is important not only for understanding the mechanisms of arsenic accumulation and detoxification by hyperaccumulators, but also for designing disposal options of arsenic-rich biomass. The primary objective of this research was to understand the speciation and leachability of arsenic in the fronds of Chinese brake (Pteris vittata L.), an arsenic hyperaccumulator, with an emphasis on the implications for arsenic-rich biomass disposal. Chinese brake was grown for 18 weeks in a soil spiked with 50 mg As kg(-1) as arsenate (AsO4(3-)), arsenite (AsO3(3-)), dimethylarsinic acid (DMA), or methylarsonic acid (MMA). Plant samples were extracted with methanol/water (1:1) and arsenic speciation was performed using high performance liquid chromatography coupled with atomic fluorescence spectrometry. The impacts of air-drying on arsenic species and leachability in the fronds were examined in the laboratory. After 18 weeks, water-soluble arsenic in soil was mainly present as arsenate with little detectable organic species or arsenite regardless of arsenic species added to the soil. However, arsenic in the fronds was primarily present as inorganic arsenite with an average of 94%. Arsenite re-oxidation occurred in the old fronds and the excised dried tissues. Arsenic species in the fronds were slightly influenced by arsenic forms added to the soil. Air-drying of the fronds resulted in leaching of substantial amounts of arsenic. These findings can be of significance when looking at disposal options of arsenic-rich biomass from the point of view of secondary contamination.     

Field-scale leaching of arsenic, chromium and copper from weathered treated wood

Earlier studies documented the loss of wood preservatives from new wood. The objective of this study was to evaluate losses from weathered treated wood under field conditions by collecting rainfall leachate from 5 different wood types, all with a surface area of 0.21 m². Wood samples included weathered chromate copper arsenate (CCA) treated wood at low (2.7 kg/m³), medium (4.8 kg/m³) and high (35.4 kg/m³) retention levels, new alkaline copper quat (ACQ) treated wood (1.1 kg/m³ as CuO) and new untreated wood. Arsenic was found to leach at a higher rate (100 mg in 1 year for low retention) than chromium and copper (<40 mg) in all CCA-treated wood samples. Copper leached at the highest rate from the ACQ sample (670 mg). Overall results suggest that metals' leaching is a continuous process driven by rainfall, and that the mechanism of release from the wood matrix changes as wood weathers.     

Leaching of chromated copper arsenate wood preservatives: a review

Recent studies have generated conflicting data regarding the bioaccumulation and toxicity of leachates from preservative-treated wood. Due to the scale of the wood preserving industry, timber treated with the most common preservative, chromated copper arsenate (CCA), may form a significant source of metals in the aquatic environment. The existing literature on leaching of CCA is reviewed, and the numerous factors affecting leaching rates, including pH, salinity, treatment and leaching test protocols are discussed. It is concluded from the literature that insufficient data exists regarding these effects to allow accurate quantification of leaching rates, and also highlights the need for standardised leaching protocols.     

An uptake and elimination kinetics approach to assess the bioavailability of chromium,copper, and arsenic to earthworms (Eisenia andrei) in contaminated field soils

The aim of this study was to determine the bioavailability of metals in field soils contaminated with chromated copper arsenate (CCA) mixtures. The uptake and elimination kinetics of chromium, copper, and arsenic were assessed in the earthworm Eisenia andrei exposed to soils from a gradient of CCA wood preservative contamination near Hartola, Finland. In soils contaminated with 1480–1590 mg Cr/kg dry soil, 642–791 mg Cu/kg dry soil, and 850–2810 mg Ag/kg dry soil, uptake and elimination kinetics patterns were similar for Cr and Cu. Both metals were rapidly taken up and rapidly excreted by Eisenia andrei with equilibrium reached within 1 day. The metalloid As, however, showed very slow uptake and elimination in the earthworms and body concentrations did not reach equilibrium within 21 days. Bioaccumulation factors (BAF) were low for Cu and Cr (< 0.1), but high for As at 0.54–1.8. The potential risk of CCA exposure for the terrestrial ecosystem therefore is mainly due to As.

     

Immobilization of antimony waste slag by applying geopolymerization and stabilization/solidification technologies

During the processing of antimony ore by pyrometallurgical methods, a considerable amount of slag is formed. This antimony waste slag is listed by the European Union as absolutely hazardous waste with a European Waste Catalogue code of 10 08 08. Since the levels of antimony and arsenic in the leachate of the antimony waste slag are generally higher than the landfilling limits, it is necessary to treat the slag before landfilling. In this study, stabilization/solidification and geopolymerization technologies were both applied in order to limit the leaching potential of antimony and arsenic. Different combinations of pastes by using Portland cement, fly ash, clay, gypsum, and blast furnace slag were prepared as stabilization/solidification or geopolymer matrixes. Sodium silicate–sodium hydroxide solution and sodium hydroxide solution at 8 M were used as activators for geopolymer samples. Efficiencies of the combinations were evaluated in terms of leaching and unconfined compressive strength. None of the geopolymer samples prepared with the activators yielded arsenic and antimony leaching below the regulatory limit at the same time, although they yielded high unconfined compressive strength levels. On the other hand, the stabilization/solidification samples prepared by using water showed low leaching results meeting the landfilling criteria. Use of gypsum as an additive was found to be successful in immobilizing the arsenic and antimony.

ImplicationsDespite the wide use of antimony for industrial purposes, disposal options for an antimony waste such as slag from thermal processing of antimony ore were not reported in the existing literature. This study aimed to develop a disposal strategy for the hazardous antimony waste slag. The findings of this study would contribute to understand the immobilization mechanisms of antimony and arsenic and will also be of interest to the owners of the antimony ore processing plants and to researchers investigating the efficiency of stabilization/solidification and geopolymerization technologies.     

Cu,Cr and As distribution in soils adjacent to pressure-treated decks,fences and poles

Chromated copper arsenate (CCA)-treated wood has been widely used in the Southeastern United States to protect wood products from microbial and fungal decay. The aims of this study were to (1). determine the distribution of arsenic (As), chromium (Cr), and copper (Cu), in soils surrounding CCA-treated wood structures such as decks, fences and poles; and (2). evaluate the impacts of these structures on As, Cr and Cu loading of the soils. Profile and lateral soil samples were collected under CCA-treated decks and adjacent to poles and fences. The results showed elevation of As, Cr and Cu concentrations close to and under the structures, with mean As concentrations as high as 23 mg x kg(-1) close to utility poles compared with less than 3 mg x kg (-1) at distances of about 1.5 m away. Concentrations of As, Cr, and Cu decreased with depth in areas close to CCA-treated poles. However, these results were only apparent in relatively new structures. A combination of weathering and leaching with time may have reduced the impact in older poles. Increased concentrations of As, Cu and Cr were also observed close to CCA-treated decks and fences, with age showing a similar impact. These results are helpful for CCA-treated wood product users to determine the safe use of these structures.     

Use of handheld X-ray fluorescence spectrometry units for identification of arsenic in treated wood

The objective of this study was to evaluate the performance of handheld XRF analyzers on wood that has been treated with a preservative containing arsenic. Experiments were designed to evaluate precision, detection limit, effective depth of analysis, and accuracy of the XRF arsenic readings. Results showed that the precision of the XRF improved with increased sample concentration and longer analysis times. Reported detection limits decreased with longer analysis times to values of less than 1mg/kg or 18 mg/kg, depending on the model used. The effective depth of analysis was within the top 1.2 cm and 2.0 cm of sample for wood containing natural gradients of chemical preservative and concentration extremes, respectively. XRF results were found to be 1.5-2.3 times higher than measurements from traditional laboratory analysis. Equations can be developed to convert XRF values to results which are consistent with traditional laboratory testing.     

Contribution of residential wood combustion to PM10 levels in Portugal

Wood is commonly used in residential combustion for heating purposes; however, it can be a major source of air pollutants, namely fine particles, volatile organic compounds and carbon monoxide. Since 2004, the PM10 daily limit value has been surpassed in Portugal, and the European Commission has stated that plans and programs must be designed in order to reduce these levels. In Portugal, 18% of PM10 emissions are due to residential wood combustion, which may deeply impact the PM10 levels in the atmosphere. The main aim of this study is to investigate the impact of residential wood combustion on the air quality in Portugal. The air quality modelling system MM5/CHIMERE was applied over Portugal for a winter month, for the following three scenarios: the reference scenario, considering the actual emissions of PM10; scenario 1, where residential wood combustion emissions are not considered; and scenario 2, which takes into account a complete conversion from traditional fireplaces to certified appliances (with a 90% reduction in PM emissions). The residential wood combustion contribution to PM10 air quality concentration values during January 2007 ranges from 0 to 14 μg m^?3, with a mean contribution of 10 μg m^?3 in the Lisboa area and 6 μg m^?3 in the Porto region. Concerning the legislated values, the area where the daily average limit value (50 μg m^?3) is exceeded decreases by 46% in the simulation when residential combustion is not considered. The modelling results for scenario 2 are not significantly different from those for scenario 1. In summary, the regulation of the residential wood combustion sector is as an effective way to reduce the PM10 levels in the atmosphere as regards air quality plans and programs.     

Elemental analysis of ash residue from combustion of CCA treated wood waste before and after electrodialytic extraction

Element distribution in a combined fly ash and bottom ash from combustion of copper chromate arsenate (CCA) treated wood waste was investigated by scanning electron microscopy (SEM/EDX) before and after electrodialytic extraction. The untreated ash contained various particles, including pieces of incompletely combusted wood rich in Cr and Ca, and irregular particles rich in Si, Al and K. Cr was also found incorporated in silica-based matrix particles. As was associated with Ca in porous (char) particles, indicating that Ca-arsenates had been formed during combustion. Cu was associated with Cr in the incompletely combusted wood pieces and was also found in almost pure form in a surface layer of some matrix particles - indicating surface condensation of volatile Cu species. In treated ash, Ca and As were no longer found together, indicating that Ca-arsenates had been dissolved due to the electrodialytic treatment. Instead particles rich in Ca and S were now found, indicating precipitation of Ca-sulphates due to addition of sulphuric acid in connection with the electrodialytic treatment. Cu and Cr were still found associated with incompletely combusted wood particles and incorporated in matrix particles. Chemical analyses of untreated and treated ash confirmed that most As, but only smaller amounts of Cu and Cr was removed due to the electrodialytic extraction. Overall metal contents in the original ash residue were: 1.4 g As, 2.76 g Cu and 2.48 g Cr, after electrodialytic extraction these amounts were reduced by 86% for As, 15% for Cu and 33% for Cr.     

A Comparison of In situ Vitrification and Rotary Kiln Incineration for Soils Treatment

In the hazardous waste community, the term “thermal destruction” is a catchallphrase that broadly refers to high temperature destruction of hazardous contaminants. Included in the thermal destruction category are treatment technologies such as rotary kiln incineration, fiuidized bed incineration, infrared thermal treatment, wet air oxidation, pyrolytic incineration, and vitrification. Among them, conventional rotary kiln incineration, a disposal method for many years, is the most well established, and often serves as a barometer to gauge the relative success of similar technologies. Public sentiment on environmental issues and increasingly stringent environmental regulations has, over time, spurred design and development of innovative thermal treatment processes directed toward reducing harmful emissions and residuals that may require further treatment or disposal. In situ vitrification (ISV), a technology that combines heat and immobiliztion, is one such innovative and relatively new technology.

This paper presents a comparison of ISV and rotary kiln incineration for soils treatment in the areas of process performance, process residuals, process limitations, applicable or relevant and appropriate (ARAJRs) regulations, criteria and limitations, and costs.     

A comparison of in situ vitrification and rotary kiln incineration for soils treatment.

In the hazardous waste community, the term "thermal destruction" is a catchall phrase that broadly refers to high temperature destruction of hazardous contaminants. Included in the thermal destruction category are treatment technologies such as rotary kiln incineration, fluidized bed incineration, infrared thermal treatment, wet air oxidation, pyrolytic incineration, and vitrification. Among them, conventional rotary kiln incineration, a disposal method for many years, is the most well established, and often serves as a barometer to gauge the relative success of similar technologies. Public sentiment on environmental issues and increasingly stringent environmental regulations has, over time, spurred design and development of innovative thermal treatment processes directed toward reducing harmful emissions and residuals that may require further treatment or disposal. In situ vitrification (ISV), a technology that combines heat and immobilization, is one such innovative and relatively new technology. This paper presents a comparison of ISV and rotary kiln incineration for soils treatment in the areas of process performance, process residuals, process limitations, applicable or relevant and appropriate (ARARs) regulations, criteria and limitations, and costs.     

Effects of compost and phosphate on plant arsenic accumulation from soils near pressure-treated wood

Leaching of arsenic (As) from chromated copper arsenate (CCA)-treated wood may elevate soil arsenic levels. Thus, an environmental concern arises regarding accumulation of As in vegetables grown in these soils. In this study, a greenhouse experiment was conducted to evaluate As accumulation by vegetables from the soils adjacent to the CCA-treated utility poles and fences and examine the effects of soil amendments on plant As accumulation. Carrot (Daucus carota L.) and lettuce (Lactuca sativa L.) were grown for ten weeks in the soil with or without compost and phosphate amendments. As expected, elevated As concentrations were observed in the pole soil (43 mg kg(-1)) and in the fence soil (27 mg kg(-1)), resulting in enhanced As accumulation of 44 mg kg(-1) in carrot and 32 mg kg(-1) in lettuce. Addition of phosphate to soils increased As accumulation by 4.56-9.3 times for carrot and 2.45-10.1 for lettuce due to increased soil water-soluble As via replacement of arsenate by phosphate in soil. However, biosolid compost application significantly reduced plant As uptake by 79-86%, relative to the untreated soils. This suppression is possibly because of As adsorbed by biosolid organic mater, which reduced As phytoavailability. Fractionation analysis showed that biosolid decreased As in soil water-soluble, exchangeable, and carbonate fraction by 45%, whereas phosphate increased it up to 2.61 times, compared to the untreated soils. Our results indicate that growing vegetables in soils near CCA-treated wood may pose a risk of As exposure for humans. Compost amendment can reduce such a risk by reducing As accumulation by vegetables and can be an important strategy for remediating CCA-contaminated soils. Caution should be taken for phosphate application since it enhances As accumulation.     

Arsenic contamination in wood mice (Apodemus sylvaticus) and bank voles (Clethrionomys glareolus) on abandoned mine sites in southwest Britain

Arsenic can be highly toxic to mammals but there is relatively little information on its transfer to and uptake by free-living small mammals. The aim of this study was to determine whether intake and accumulation of arsenic by wild rodents living in arsenic-contaminated habitats reflected environmental levels of contamination and varied between species, sexes and age classes. Arsenic concentrations were measured in soil, litter, wood mice (Apodemus sylvaticus) and bank voles (Clethrionomys glareolus) from six sites which varied in the extent to which they were contaminated. Arsenic residues on the most contaminated sites were three and two orders of magnitude above background in soil and litter, respectively. Arsenic concentrations in the stomach contents, liver, kidney and whole body of small mammals reflected inter-site differences in environmental contamination. Wood mice and bank voles on the same sites had similar concentrations of arsenic in their stomach contents and accumulated comparable residues in the liver, kidney and whole body. Female bank voles, but not wood mice, had significantly higher stomach content and liver arsenic concentrations than males. Arsenic concentration in the stomach contents and body tissues did not vary with age class. The bioaccumulation factor (ratio of arsenic concentration in whole body to that in the diet) in wood mice was not significantly different to that in bank voles and was 0.69 for the two species combined, indicating that arsenic was not bioconcentrated in these rodents. Overall, this study has demonstrated that adult and juvenile wood mice and bank voles are exposed to and accumulate similar amounts of arsenic on arsenic-contaminated mine sites and that the extent of accumulation depends upon the level of habitat contamination.