Levels of chlorinated compounds (CPs, PCPPs, PCDEs, PCDFs and PCDDs) in soils at contaminated sawmill sites in Sweden

Soil samples from five contaminated sawmill sites in Sweden were characterized with respect to chlorophenols (CP), chlorinated phenoxy phenols (PCPP, hydroxylated chlorinated diphenyl ethers), chlorinated diphenyl ethers (PCDE), chlorinated dibenzofurans (PCDF) and chlorinated dibenzo-p-dioxins (PCDD). The composition of chlorinated compounds in the soil samples was compared to the composition of two preservatives commonly used in the Scandinavian wood impregnation industry: the 2,3,4,6-tetrachlorophenol preservative called Ky-5 and the pentachlorophenol preservative Dowicide G. The levels of CPs in the soil samples ranged from 0.1 to 4500 mgkg-1 d.w., PCPPs from <0.15 to 940 mgkg-1 d.w., PCDEs from <38 to 6800 microgkg-1 d.w., PCDFs from 7.4 to 18000 microgkg-1 d.w. and PCDDs from 9.9 to 35000 microgkg-1 d.w. The resulting WHO-TEQ of PCDD/Fs in the soil samples ranged from 0.14 to 3000 microgkg-1 d.w. Despite a wide range of concentrations the congener compositions were similar within tetrachlorophenate and pentachlorophenate contaminated soils respectively. The contamination at each sawmill site may be linked to the use of either a tetrachlorphenol preservative, e.g. Ky-5, or a pentachlorophenol preservative, e.g. Dowicide G. Best-fit calculations were used to compare the chlorinated phenol contents of the preservatives to those of the soil samples. This revealed a positive correlation between the hydrophobicity (logKow) of contaminants and the ratio of their levels in soil to preservatives. The relative abundance of the chlorinated compounds varied greatly between the five sites studied, suggesting that their transport parameters differ substantially.     

Chlorinated phenols as contaminants of soil and water in the vicinity of two Finnish sawmills

Contamination of soil and water in the vicinity of two sawmills using preservative against blue staining fungi that contained chlorophenols was studied. The soil around the treatment basins was found to contain up to 70 mg chlorophenols per kg and that in the storage area for treated lumber up to 6 mg per kg. Contamination extended to a depth of at least 2 meters near the treatment basins. Surface water inside the sawmill area was found to contain the same chlorophenols as those used in wood preservation, plus some additional isomers. The ground water and lake water around the sawmill areas was found to be contaminated by wood preservative.     

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.     

Contents and origin of polychlorinated diphenyl ethers (PCDE) in salmon from the Baltic Sea, Lake Saimaa and the Tenojoki river in Finland

The presence of 26 congeners of polychlorinated diphenyl ethers (PCDEs) was investigated in salmon from three locations in Finland. In addition to salmon, one chlorophenol wood preservative (Ky-5) and one fly ash sample were analyzed for PCDEs. Concentrations of PCDE congeners in salmon muscle measured by high resolution gas chromatography/low resolution mass spectrometry ranged from < 0.02 to 2.4 ng/g fresh weight. The major components of tetra- to octachlorinated PCDEs in salmon were one TeCDE (22′44′-), two PeCDEs (22′44′5- and 23′44′5-) and three HxCDEs (22′44′56′-, 22′44′55′- and 22′344′5-). The Baltic salmon caught from the Simojoki River had higher levels of PCDEs than the Atlantic salmon from the Tenojoki River or salmon from Lake Saimaa in South-Finland. Same PCDE congeners which were abundant in the wood preservative were also detected in salmon, whereas PCDE congeners in the fly ash were different from those in salmon or in Ky-5.     

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.     

Photodegradation of PCDD/Fs adsorbed on spruce (Picea abies (L.) Karst.) needles under sunlight irradiation

Spruce (Picea abies (L.) Karst.) needles were exposed to exhaust gas containing polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) generated by combustion of polyvinyl chloride, wood, high-density polyethylene, and styrene. Photodegradation of PCDD/Fs adsorbed on spruce needles under sunlight irradiation was studied. The photodegradation of PCDD/Fs follows pseudo-first-order reaction kinetics, with photolysis half-lives ranging between 40 and 100 h. The photolysis rates of PCDF congeners are higher than PCDD congeners with the same chlorinated substitutions. Higher chlorinated PCDD/Fs tend to photolyze slowly. The wax components in spruce needles may act as proton donors and accelerate the photolysis rate. C-Cl cleavage through the addition of protons to PCDD/F molecules may be an important route for PCDD/Fs photodegradation.     

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.     

Residential and biological exposure assessment of chemicals from a wood treatment plant

This paper evaluates the results of contamination of residents and residential homes located in close proximity to a Wood Treatment Plant. The plant has produced treated wood products continuously since 1904. The principle chemicals used to treat the wood, which is primarily used for railroad ties (oblong objects laid perpendicular to the rails to act as a base for the tracks), are creosote and pentachlorophenol. For a number of years, the plant burned treated waste wood products containing creosote and pentachlorophenol. First the plant pressure impregnates the wood with creosote and pentachlorophenol, and then the wood is stacked on open ground to allow it to air dry. Chemicals from recently treated wood ties are allowed to evaporate into the air or drip onto the ground surrounding the stacked wood. Small drainage ditches carry the liquid wastes into larger water channels where eventually the waste streams are discharged into a river adjacent to the plant. The river serves as a source of drinking water for the nearby community. Prevailing wind patterns favor a drift of air emissions from the plant's boiler stack over the nearby community and its residents. Over the past few years, the town's residents have become increasingly concerned about their health status and have voiced concerns regarding multiple health problems (including cancer), possibly associated with plant discharges. The intention of this study is to examine a representative sample of the potentially affected residents and to evaluate their residential environment for the presence of dioxin and/or its congeners. Data obtained from EPA's Toxic Release Information (TRI) database revealed the plant routinely discharged creosote, pentachlorophenol, dioxin and dioxin-like compounds into the ambient air via fugitive air emissions and surface waste waters. Sampling of household dust and water sediment within and outside of residences within a 2-mile radius of the plant revealed the presence of significantly elevated levels of dioxins, principally octachlorodibenzo-p-dioxin (OCDD) and 1,2,3,4,6,7,8-hepta-CDD. Biomonitoring of 29 subjects identified the presence of significantly elevated chlorinated dioxins and furan levels (OCDD=1049 ppt for exposed and 374 ppt for controls and 1,2,3,4,6,7,8-hepta CDD=132 ppt for exposed and 45.1 ppt for controls). These levels are consistent with exposures to pentachlorophenol in this group of subjects. And they confirm the presence of unsafe levels of chlorinated dioxins in these persons.     

Monitoring losses of copper based wood preservatives in the Thames estuary

Field trials were conducted at two sites in the Thames estuary to monitor losses of copper, chromium and arsenic from wood preservative treated timbers of varying sizes and treatment regimes. Results indicated that leaching tests conducted under standard laboratory conditions might overestimate losses compared to losses resulting from real environmental exposures. Amine copper treated wood was noted to leach higher levels of copper compared to chromated copper arsenate treated wood, and was therefore considered an inappropriate replacement biocide for fresh and marine construction purposes on this basis. Increases in copper concentrations in the outer sections of amine copper treated posts may have represented re-distribution of this component in this timber. No accumulation of metals was found in sediments surrounding field trial posts.     

Dioxins,chlorophenols and other chlorinated organic pollutants in colloidal and water fractions of groundwater from a contaminated sawmill site

BACKGROUND, AIM, AND SCOPE: The distribution of chlorinated organic contaminants in groundwater and the importance of colloids were studied in groundwater from a sawmill site contaminated by chlorophenol preservatives. MATERIALS AND METHODS: The groundwater was fractionated into three different size ranges: (1) >0.7 mum, (2) 0.4-0.7 mum and (3) 0.2-0.4 mum and the filtered water phase. The concentrations of chlorophenols (CP), chlorinated phenoxy phenols (PCPP), chlorinated diphenyl ethers (PCDE), chlorinated dibenzofurans (PCDF) and chlorinated dibenzo-p-dioxins (PCDD) were determined in each fraction. The colloids were characterised regarding the chemical composition using X-ray photoelectron spectroscopy (XPS). RESULTS: Chlorophenols were mostly found in the water fraction and PCDD/Fs were found almost exclusively in the particulate fractions. For example, the filtered water phase contained 2,100 mug l(-1) and 0.72 ng l(-1) for CPs and PCDD/Fs, respectively, and the particulate fractions contained 27 mug l(-1) and 32 ng l(-1) for CPs and PCDD/Fs, respectively. XPS evaluation of the particulate phases showed no correlation between the surface chemistry of the particle properties and the distribution of chlorinated compounds. DISCUSSION: The results suggest that groundwater transport of CPs, PCPPs, PCDEs and PCDD/Fs may occur from contaminated sawmill sites and that the colloid-facilitated transport, especially of PCDD/Fs, is substantial. The results correlated well with previous studies of compounds sorbed to dissolved organic carbon, which indicate that dissolved and colloidal organic carbon facilitated the transport of PCDEs, PCDFs and PCDDs particularly. CONCLUSIONS: Several classes of chlorinated compounds were readily detected in the groundwater samples. Due to the differences in their physicochemical properties, CPs, PCPPs, PCDEs and PCDD/Fs vary in their partitioning between colloidal fractions and the filtered groundwater. The proportion of the bound fraction increased with an increasing hydrophobicity of the chlorinated compounds. The groundwater transport of colloid-associated pollutants from the site may be significant. RECOMMENDATIONS AND PERSPECTIVES: The results imply that colloidal particles <0.7 mum are freely mobile in groundwater from this site. The groundwater transport of colloid-associated pollutants may be significant. However, the extent of the problem is not yet known and, thus, further research is needed to evaluate the impact of colloidal transport of hydrophobic organic contaminants. In Sweden alone, 400 to 500 sawmill sites are estimated to be contaminated with PCDD/Fs as a result of the former use of CP-based wood preservatives. The widespread use of CP mixtures for a variety of applications, including wood preservation, indicates that potential colloidal transport will be an issue of concern in many countries.     

Formation of chlorinated phenols, dibenzo-p-dioxins, dibenzofurans, benzenes, benzoquinnones and perchloroethylenes from phenols in oxidative and copper (II) chloride-catalyzed thermal process

Formation of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), and chlorinated phenols on CuCl(2) from unsubstituted phenol and three monochlorophenols was studied in a flow reactor over a temperature range of 100-425 degrees C. Heated nitrogen gas streams containing 8.0% oxygen were used as carrier gas. The 0.00024mol of unsubstituted phenol and 0.00039mol of each monochlorophenol were passed through a 1g and 1cm SiO(2) particle containing 0.5% (Cu by mass) CuCl(2). Chlorination preferentially occurred on ortho-(2, 6) and para-(4) positions. Chlorination increased up to 200 degrees C, and thereafter decreased as temperature increased. Chlorination of phenols plays an important role in the formation of the more chlorinated PCDD/Fs. Chlorinated benzenes are formed possibly from both chlorination of benzene and chlorodehydroxylation of phenols. Chlorinated phenols with ortho chlorine formed PCDD products, and major PCDD products were produced via loss of one chlorine. For PCDF formation, at least one unchlorinated ortho carbon was required.     

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.     

碱法麦草浆漂白废水脱色白腐菌的筛选及脱色研究

从腐木上采集,经多次分离纯化筛选出2株具有较高漂白废水脱色能力的菌株F7、F9,与Phanerochaete Chrysosporium在相同的条件下处理碱法麦草浆CE段混合漂白废水,培养4d脱色率分别为74．44％,46．67％和62．22％。延长培养时间至第8d,F7菌脱色效果不明显,而F9菌脱色可增至67．58％。     

Evaluation of the antifungal effects of bio-oil prepared with lignocellulosic biomass using fast pyrolysis technology

This study was performed to investigate the utility of bio-oil, produced via a fast pyrolysis process, as an antifungal agent against wood-rot fungi. Bio-oil solutions (25-100 wt.%) were prepared by diluting the bio-oil with EtOH. Wood block samples (yellow poplar and pitch pine) were treated with diluted bio-oil solutions and then subjected to a leaching process under hot water (70 °C) for 72 h. After the wood block samples were thoroughly dried, they were subjected to a soil block test using Tyromyces palustris and Trametes versicolor. The antifungal effect of the 75% and 100% bio-oil solutions was the highest for both wood blocks. Scanning electron microscopy analysis indicated that some chemical components in the bio-oil solution could agglomerate together to form clusters in the inner part of the wood during the drying process, which could act as a wood preservative against fungal growth. According to GC/MS analysis, the components of the agglomerate were mainly phenolic compounds derived from lignin polymers.     

Octachlorinated dioxin in pulps and effluents: Where does it come from?

Studies on the formation/destruction of dioxins associated with the pulping of wood artificially impregnated with an industrial grade of pentachlorophenol lend support to an earlier observation that ambient dioxins deposition may not necessarily be a unique source of the higher chlorinated dioxins occasionally found in pulps and final effluent discharges. These dioxins, which seemingly occur in products from a wide range of pulping technologies including recycle operations, may also originate from pentachlorophenol-based fungicides.     

Contributions to ecological chemistry CXL: Isolation and identification of a metabolite of pentachlorophenol- 14C in rice plants

Pentachlorophenol (PCP) is a fungicide used in wood protection and a herbicide used against weeds in various crops^2–4, especially in rice. Up to 1971, it contributed more than 50% to the herbicides used in Japan. However, because it has a high fish- and shellfish-toxicity, its application to paddy fields has been restricted since 1971. Today, PCP is still in use to a fair extent in paddy fields and upland crops either as a single herbicide or in combination with others⁴. Numerous publications are concerned with its abiotic decomposition^5–8 including photomineralization⁹ and microbial degradation^4,10–16 leading to the formation of carbon dioxide^17–18. Furthermore, studies with bacteria using PCP as a sole carbon source have been done^13,19. At least ten metabolites have been isolated from soil and identified^{4,10–11,14, 20–21}, the main metabolic steps being methylation of the hydroxyl group, dechlorination resulting in tetrachloro- and trichlorophenols, and hydroxylation to chlorinated hydroquinones or catechols.According to our knowledge, no reports are available on identification of metabolites in the protected organisms, the higher plants. In one study it has been suggested that cotton plants accumulate and metabolize PCP, but no metabolites were reported²². This first paper on our respective experiments deals with the isolation and identification of a metabolite found in rice plants.     

Determination of pentachlorophenol (PCP) in waste wood--method comparison by a collaborative trial

Two independently developed and validated procedures for the determination of pentachlorophenol (PCP) in waste wood were compared by means of a collaborative trial. Both methods foresee quantification of PCP by gas chromatography (GC-ECD) after acetylation and differ with regard to the use of methanol or toluene/sulphuric acid, respectively, as solvent in the sonication extraction step. Test samples with established analyte homogeneity were prepared from a ground "real life" starting material. A total of 23 participating laboratories with experience in wood preservative analysis were instructed to apply both methods to three levels of content in the range of 0.5-20 mg PCP/kg. In case of the toluene/sulphuric acid extraction, lower recoveries and higher interlaboratory dispersion of results at the higher PCP contents were observed. Seen against the background of the Horwitz equation a reproducibility standard deviation of approximately 19% for the methanol extraction at the 4.5 mg/kg level meets the requirement for a sound analytical method. Thus, the sonication extraction procedure with methanol has been annexed as a reference method to the German waste wood regulation.     

Polychlorinated organic compounds in the Arctic cod liver: trends and profiles

Polychlorinated organic compounds (POCs) have been measured in Arctic cod liver from Vestertana Fjord for a period of 1987-1998. Significant decrease was observed for DDD (p = 0.043), alpha-HCH (p = 0.001), and gamma-HCH (lindane; p = 0.001). Contents of DDE, 2,3,7,8-tetrachlorodibenzofuran, PCBs, chlordanes, chloronaphthalenes, hexachlorobenzene and polychlorodiphenyl ethers had no significant trend. Contents of three hexa- and two heptachlorodibenzofurans and octachlorodibenzofuran increased slightly from 1987 to 1994, but then at very high rate from 1994 to 1998. Trends of HCHs, profiles of PCBs and levels of chlordanes are in accordance with atmospheric long range transport. The hexa-, hepta- and octachlorodibenzofurans observed are major impurities in chlorophenol formulation Ky-5, which has been used as wood preservative and as fungicide/slimicide in industrial processes. Their profile in Vestertana cod was similar to that observed in Ky-5 contaminated fish.     

难降解氯代有机物污染环境的生物修复技术研究进展

氯代有机物是一类在生产和生活中广泛应用并被大量排放到环境中的难降解有机污染物质,一旦进入生态环境,就会在水体、土壤和底质中长期残留,并在食物链中不断积累、富集,从而对生物体产生危害。因此,对受这类难降解有机物污染的环境修复是目前所迫切需要解决的环境问题之一。基于物理和化学修复方法成本较高易造成二次污染,文中探讨了国内外生物修复技术的研究进展,并对难降解氯代有机物污染环境修复的研究方向进行了展望,由于环境中的污染物质复杂多变,联合生物修复技术将成为未来的研究热点。     

Microbial transformation and degradation of polychlorinated biphenyls

This paper reviews the potential of microorganisms to transform polychlorinated biphenyls (PCBs). In anaerobic environments, higher chlorinated biphenyls can undergo reductive dehalogenation. Meta- and para-chlorines in PCB congeners are more susceptible to dechlorination than ortho-chlorines. Anaerobes catalyzing PCB dechlorination have not been isolated in pure culture but there is strong evidence from enrichment cultures that some Dehalococcoides spp. and other microorganisms within the Chloroflexi phylum can grow by linking the oxidation of H(2) to the reductive dechlorination of PCBs. Lower chlorinated biphenyls can be co-metabolized aerobically. Some aerobes can also grow by utilizing PCB congeners containing only one or two chlorines as sole carbon/energy source. An example is the growth of Burkholderia cepacia by transformation of 4-chlorobiphenyl to chlorobenzoates. The latter compounds are susceptible to aerobic mineralization. Higher chlorinated biphenyls therefore are potentially fully biodegradable in a sequence of reductive dechlorination followed by aerobic mineralization of the lower chlorinated products.