Octachlorodibenzo-p-dioxin in wood treatment materials and treated wood

The octachlorodibenzo-p-dioxin (OCDD) concentrations have been determined in aged samples of commercial pentachlorophenol (PCP), in wood protection formulations containing PCP and in wood treated with PCP as a preservative or as an anti-sapstain treatment. The concentrations of OCDD found in the various samples are within the range expected from the amount of commercial PCP initially present in the samples. In view of the known stability of OCDD the results are interpreted as indicating that the formulation, treatment and ageing processes have not led to any substantial conversion of PCP to OCDD; although one result indicates that outdoor exposure of treated samples increased the OCDD concentration by a factor of approximately 2 after $\text{3}\text{1}\text{2}$ years. Analysis of aged samples of treated wood indicate that OCDD is lost much less rapidly from the wood than PCP.     

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.     

Ash from the combustion of wood treated with inorganic wood preservatives: Element composition and leaching

Wood samples impregnated with inorganic wood preservatives containing the elements arsenic, boron, chromium, copper, fluorine, and/or zinc were burned in a furnace. Three different kinds of ash were collected: furnace, boiler, and so-called fly ash. Analyses showed that the ash contained large amounts of elements originating from the inorganic wood preservatives. Further interest was focused on the leachability of the above-mentioned elements. For this purpose a laboratory batch leaching test according to the German Standard DIN 38 414 part 4 was chosen. The results indicate that the leachability is in a range where the release of these elements to the environment from deposited ash can be considered as detrimental.     

Long term changes in polychlorodibenzo-p-dioxin concentrations in wood treated with technical pentachlorophenol

Wood samples treated with technical pentachlorophenol (PCP), technical sodium pentachlorophenoxide (NaPCP) and octachlorodibenzo-p-dioxin have been exposed outdoors for periods up to $\text{2}\text{1}\text{2}$ years. Analysis of extracts from the samples show that photolytic reductive dechlorination of highly chlorinated dibenzo-p-dioxins to less chlorinated isomers occurs. However there is no discernible increase in polychlorodibenzo-p-dioxin concentrations in the technical PCP treated wood presumably because further photolytic reactions and volatilisation compete effectively with the photolytic formation. There is no evidence for formation of octachlorodibenzo-p-dioxin (OCDD) in technical PCP treated wood in this study, probably because photolytic destruction and volatilisation compete effectively with formation reactions when the initial OCDD concentration is relatively high.     

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.     

Rebound of a coal tar creosote plume following partial source zone treatment with permanganate

The long-term management of dissolved plumes originating from a coal tar creosote source is a technical challenge. For some sites stabilization of the source may be the best practical solution to decrease the contaminant mass loading to the plume and associated off-site migration. At the bench-scale, the deposition of manganese oxides, a permanganate reaction byproduct, has been shown to cause pore plugging and the formation of a manganese oxide layer adjacent to the non-aqueous phase liquid creosote which reduces post-treatment mass transfer and hence mass loading from the source. The objective of this study was to investigate the potential of partial permanganate treatment to reduce the ability of a coal tar creosote source zone to generate a multi-component plume at the pilot-scale over both the short-term (weeks to months) and the long-term (years) at a site where there is >10 years of comprehensive synoptic plume baseline data available. A series of preliminary bench-scale experiments were conducted to support this pilot-scale investigation. The results from the bench-scale experiments indicated that if sufficient mass removal of the reactive compounds is achieved then the effective solubility, aqueous concentration and rate of mass removal of the more abundant non-reactive coal tar creosote compounds such as biphenyl and dibenzofuran can be increased. Manganese oxide formation and deposition caused an order-of-magnitude decrease in hydraulic conductivity. Approximately 125 kg of permanganate were delivered into the pilot-scale source zone over 35 days, and based on mass balance estimates <10% of the initial reactive coal tar creosote mass in the source zone was oxidized. Mass discharge estimated at a down-gradient fence line indicated >35% reduction for all monitored compounds except for biphenyl, dibenzofuran and fluoranthene 150 days after treatment, which is consistent with the bench-scale experimental results. Pre- and post-treatment soil core data indicated a highly variable and random spatial distribution of mass within the source zone and provided no insight into the mass removed of any of the monitored species. The down-gradient plume was monitored approximately 1, 2 and 4 years following treatment. The data collected at 1 and 2 years post-treatment showed a decrease in mass discharge (10 to 60%) and/or total plume mass (0 to 55%); however, by 4 years post-treatment there was a rebound in both mass discharge and total plume mass for all monitored compounds to pre-treatment values or higher. The variability of the data collected was too large to resolve subtle changes in plume morphology, particularly near the source zone, that would provide insight into the impact of the formation and deposition of manganese oxides that occurred during treatment on mass transfer and/or flow by-passing. Overall, the results from this pilot-scale investigation indicate that there was a significant but short-term (months) reduction of mass emanating from the source zone as a result of permanganate treatment but there was no long-term (years) impact on the ability of this coal tar creosote source zone to generate a multi-component plume.     

Responses of three grass species to creosote during phytoremediation

Phytoremediation of creosote-contaminated soil was monitored in the presence of Tall fescue, Kentucky blue grass, or Wild rye. For all three grass species, plant growth promoting rhizobacteria (PGPR) were evaluated for plant growth promotion and protection of plants from contaminant toxicity. A number of parameters were monitored including plant tissue water content, root growth, plant chlorophyll content and the chlorophyll a/b ratio. The observed physiological data indicate that some plants mitigated the toxic effects of contaminants. In addition, in agreement with our previous experiments reported in the accompanying paper (Huang, X.-D., El-Alawi, Y., Penrose, D.M., Glick, B.R., Greenberg, B.M., 2004. A multi-process phytoremediation system for removal of polycyclic aromatic hydrocarbons from contaminated soil. Environ. Poll. doi: 10.1016/j.envpol.2003.09.031), PGPR were able to greatly enhance phytoremediation. PGPR accelerated plant growth, especially roots, in heavily contaminated soils, diminishing the toxic effects of contaminants to plants. Thus, the increased root biomass in PGPR-treated plants led to more effective remediation.     

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.     

Leaching behaviour of Cd, Cu, Pb and Zn in surface soils derived from dredged sediments

Leaching of heavy metals from land-disposed dredged sediment spoils is a potential environmental hazard. The leaching behavior of Cd, Cu, Pb and Zn in surface soils sampled from abandoned dredged sediment disposal sites was assessed. Using simple mass-balance calculations, the significance of the leaching test results with respect to metal migration into underlying clean soil was appraised. The potential leachability, defined as the amounts released at constant pH 4, decreased in the order (% of total contents): Zn (58%) approximately equal to Cd (49%)>Cu (5%) approximately equal to Pb (2%). The kinetics of metal release were determined in a cascade shaking test using de-mineralized water acidified to pH 4 (HNO(3)). Metal concentrations in the leachates were low and metal migration was, assuming uniform convective flow, predicted to be of no environmental concern. It is emphasized that any long-term prediction of metal migration is uncertain.     

Differential sorption behaviour of aromatic hydrocarbons on charcoals prepared at different temperatures from grass and wood

Naturally occurring charcoals are increasingly being recognized as effective sorbents for organic compounds. In this study we investigated the sorption of benzene and toluene in single-sorbate and bi-sorbate systems on different types of charcoals produced in laboratory, employing the batch sorption technique. Air dried plant materials from Phalaris grass (Phalaris tuberosa) and Red Gum wood (Eucalyptus camadulensis) were combusted under limited oxygen supply at 250 degrees C, 450 degrees C, and 850 degrees C. The resulting charcoals were characterized for their specific surface areas, total cation content, and pore size distributions (pore size distribution only for wood combusted at 450 degrees C and 850 degrees C). For the materials treated at 850 degrees C not only the surface area, microporosity, and total amount of sorbed sorbate increased markedly, but also the non-linearity of the sorption isotherm. The pore size distributions and surface areas as well as an indifferent sorption behaviour and competition effects for both sorbates indicated that pore filling mechanisms were the dominating processes governing the sorption on these microporous, high temperature treated materials. For the materials treated at lower temperatures the affinity of toluene was higher compared to that of benzene. In the bi-sorbate system the overall uptake of benzene increased. These phenomena might be due to the stronger hydrophobicity of toluene, and to a varying potential for swelling of the matrix and pore deformation by the two sorbates. The significantly lower sorption capacity of the Phalaris-derived material compared to the Red Gum charcoal correlated with its smaller surface area and higher cation content.     

Evaluation of pressure treated wood impact on landfill waste decomposition using a methane yield assay

Research was conducted to investigate the potential impact of CCA-treated wood and other arsenic-free Cu-based preservative-treated wood on microorganisms, involved in the anaerobic decomposition of waste in landfills. Wood preservatives used included alkaline copper quat (ACQ), copper citrate (CC), copper boron azole (CBA), copper dimethyldithiocarbamate (CDDC), and chromated copper arsenate (CCA). The biochemical methane potential (BMP) assay was used to estimate the possible impacts. The methane yields of mixtures of preservative-treated wood or untreated wood with cellulose (group 1) and these wood samples only (group 2) were determined. An analysis of variance (ANOVA) test found that there were no significant differences among methane yields results in either group 1 or group 2, at the 0.05 level of significance. The results indicate that under the conditions tested, none of the treated wood products evaluated were toxic to the methane-producing organisms. At the end of the assays, test bottle contents were analyzed for Cu, Cr, and As. When the fraction of each metal in the solution (relative to original metal in the wood, leachability %) was examined, As was present at the great extent. The leachability of As was in the range from 15.1% to 21.7% while relatively low leachability (1.7-7.6%) of Cu was observed.     

Using polymer solutions to enhance recovery of mobile coal tar and creosote DNAPLs

Direct pumping and enhanced recovery of coal tar and creosote dense, non-aqueous phase liquids (DNAPLs) from the subsurface have had mixed results because these DNAPLs are viscous fluids that can potentially alter aquifer wettability. To improve the inefficiencies associated with waterflooding, the research presented here considered the use of a polymer solution that can be added to the injected flood solution to increase the viscosity and decrease the velocity of the flooding solution. Results from one-dimensional, vertically oriented laboratory column experiments that evaluate the recovery of coal-derived DNAPL with both water and polymer flooding solutions are presented. The final DNAPL saturation remaining in the column was assessed in water and oil-wet systems for three viscous DNAPLs. Adding polymer to increase the aqueous solution viscosity did not have a significant impact in water-wet systems. A final DNAPL saturation of approximately 19% was achieved for both water and polymer floods. In contrast, the addition of polymer significantly improved recovery in oil-wet systems. The final saturation was over 40% in oil-wet systems after waterflooding, but approximately 19% with a polymer flushing solution. Although the final saturation produced with polymer flooding was similar between the oil- and water-wet systems, differences in the relative permeability and distribution of DNAPL in the porous matrix caused the DNAPL recovery to be much slower in the oil-wet system.     

Review of disposal technologies for chromated copper arsenate (CCA) treated wood waste, with detailed analyses of thermochemical conversion processes

Several alternative methods for the disposal of chromated copper arsenate (CCA) treated wood waste have been studied in the literature, and these methods are reviewed and compared in this paper. Alternative disposal methods include: recycling and recovery, chemical extraction, bioremediation, electrodialytic remediation and thermal destruction. Thermochemical conversion processes are evaluated in detail based on experiments with model compounds as well as experimental and modelling work with CCA treated wood. The latter category includes: determination of the percentage of arsenic volatilised during thermal conversion of CCA treated wood, identification of the mechanisms responsible for arsenic release, modelling of high temperature equilibrium chemistry involved when CCA treated wood is burned, overview of options available for arsenic capture, characterisation of ash resulting from (co-)combustion of CCA treated wood, concerns about polychlorinated dibenzo-p-dioxins/furans (PCDD/F) formation. Finally, the most appropriate thermochemical disposal technology is identified on short term (co-incineration) and on long term (low-temperature pyrolysis or high-temperature gasification).     

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.     

Transport of creosote compounds in a large, intact, macroporous clayey till column

The transport in macroporous clayey till of bromide and 25 organic compounds typical of creosote was studied using a large intact soil column. The organic compounds represented the following groups: polycyclic aromatic hydrocarbons (PAHs), phenolic compounds, monoaromatic hydrocarbons (BTEXs), and heterocyclic compounds containing oxygen, nitrogen or sulphur in the aromatic ring structure (NSO-compounds). The clayey till column (0.5 m in height and 0.5 m in diameter) was obtained from a depth of 1–1.5 m at an experimental site located on the island of Funen, Denmark. Sodium azide was added to the influent water of the column to prevent biodegradation of the studied organic compounds. For the first 24 days of the experiment, the flow rate was 219 ml day⁻¹ corresponding to an infiltration rate of 0.0011 m day⁻¹. At this flow rate, the effluent concentrations of bromide and the organic compounds increased very slowly. The transport of bromide and the organic compounds were successfully increased by increasing the flow rate to 1353 ml day⁻¹ corresponding to 0.0069 m day⁻¹. The experiment showed that the transport of low-molecular-weight organic compounds was not retarded relative to bromide. The high-molecular-weight organic compounds were retarded significantly. The influence of sorption on the transport of the organic compounds through the column was evaluated based on the observed breakthrough curves. The observed order in the column experiment was, with increasing retardation, the following: benzene=pyrrole=toluene=o-xylene=p-xylene=ethylbenzene=phenol=benzothiophene=benzofuran<naphthalene<1-methylpyrrole<1-methylnaphthalene=indole=o-cresol=quinoline<3,5-dimethylphenol=2,4-dimethylphenol<acridine<carbazole<2-methylquinoline<fluorene<dibenzofuran<phenanthrene=dibenzothiophene. This order could not be predicted from regularly characteristics as octanol/water-distribution coefficients of the organic compounds but only from experimentally determined data. The results indicate that a thin clayey till cover of the type described in this paper does not protect groundwater against contamination by low-molecular-weight organic compounds.     

Transport and biodegradation of creosote compounds in clayey till, a field experiment

The transport and biodegradation of 12 organic compounds (toluene, phenol, o-cresol, 2,6-, 3,5-dimethylphenol, naphthalene, 1-methylnaphthalene, benzothiophene, dibenzofuran, indole, acridine, and quinoline) were studied at a field site located on the island of Funen, Denmark, where a clayey till 10–15 m deep overlies a sandy aquifer. The upper 4.8 m of till is highly fractured and the upper 2.5 m contains numerous root and worm holes. A 1.5–2 m thick sand lens is encountered within the till at a depth of 4.8 m. Sampling points were installed at depths of 2.5 m, 4 m, and in the sand lens (5.5 m) to monitor the downward migration of a chloride tracer and the organic compounds. Water containing organic compounds and chloride was infiltrated into a 4 m×4.8 m basin at a rate of 8.8 m³ day⁻¹ for 7 days. The mass of naphthalene relative to chloride was 0.39–0.98 for the sampling points located at a depth of 2.5 m, 0.11–0.61 for the sampling points located at a depth of 4 m, and 0–0.02 for the sampling points located in the sand lens. A similar pattern was observed for eight organic compounds for which reliable results were obtained (toluene, phenol, o-cresol, 2,6-, 3,5-dimethylphenol, 1-methylnaphthalene, benzothiophene, and quinoline). This shows that the organic compounds were attenuated during the downward migration through the till despite the high infiltration rate. The attenuation process may be attributed to biodegradation.     

乙酸铵浸出高炉瓦斯灰中的锌

采用NH3-CH3COONH4-H2O体系进行了高炉瓦斯灰提锌工艺研究。结果表明：控制浸出温度45 °C,总氨浓度5 mol·L-1,液固比5:1,[NH3]/[NH4]+摩尔比1:1,搅拌速度300 r·min-1,浸出时间60 min,锌浸出率达77.79%。FT-IR及ESI-MS分析显示羧酸阴离子能结合Zn离子形成复杂的羧酸盐配合物,添加CH3COONH4能促进锌的溶出,XRD、SEM-EDS表征分析显示浸出渣中残留ZnFe2O4是导致锌浸出率低的限制性因素。     

鹤壁矿区煤矸石淋滤实验研究

对鹤壁煤矿区第10矿煤矸石进行连续淋溶试验,模拟煤矸石矿井填充后对地下水环境的影响.测定pH值、电导率、F^-、总硬度、Zn、Mn、Cr^6＋、Cd、Cu和Pb等项目,实验结果表明,煤矸石淋出液中F^-和Cr^6＋超标,Mn接近标准,pH值偏高,对地下水环境存在一定影响.其他各元素含量甚微,多未检出.     

鹤壁矿区煤矸石淋滤实验研究

对鹤壁煤矿区第10矿煤矸石进行连续淋溶试验,模拟煤矸石矿井填充后对地下水环境的影响.测定pH值、电导率、F-、总硬度、Zn、Mn、Cr6 、Cd、Cu和Pb等项目,实验结果表明,煤矸石淋出液中F-和Cr6 超标,Mn接近标准,pH值偏高,对地下水环境存在一定影响.其他各元素含量甚微,多未检出.