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.     

Contamination of River Kymijoki sediments with polychlorinated dibenzo-p-dioxins, dibenzofurans and mercury and their transport to the Gulf of Finland in the Baltic Sea

Kymijoki, the fourth largest river in Finland, has been heavily polluted by pulp mill effluents as well as the chemical industry. Up to 24,000 ton of wood preservative, chlorophenol known as Ky-5, was manufactured in the upper reaches of the river, an unknown amount of which was discharged into the river between 1940 and 1984. Polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) occurred as impurities in the final Ky-5 product. The PCDD/F concentrations and burden in the river sediments were studied and the transport of PCDD/Fs from contaminated sites downstream and into the Gulf of Finland in the Baltic Sea was estimated. More than 190 sediment cores were sampled to estimate the volume of contaminated sediments and the total PCDD/F burden. The transport of PCDD/Fs was estimated using sediment traps placed at several sites. The survey revealed that sediments in the river were heavily polluted by PCDD/Fs, the main toxic congener being 1,2,3,4,6,7,8-heptachlorodibenzofuran, a major contaminant in the Ky-5 product. The mean total concentration at the most polluted river site downstream from the main source was 42000 microg kg(-1) d.w. (106 microg I-TEQ kg(-1)). The elevated concentrations in the coastal region and the present estimated transport from the River Kymijoki confirm earlier assessments that the river is a major source of PCDD/F for the Gulf of Finland.     

Dioxin exposure in contaminated sawmill area: the use of molar teeth and bone of bank vole (Clethrionomys glareolus) and field vole (Microtus agrestis) as biomarkers

Developmental disorders of teeth are among the most sensitive targets of polychlorinated dibenzo-p-dioxin and -furan (PCDD/F) exposure. In rats, 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) reduces dose-dependently the size of molars, most severely the third lower molars. Dioxins also have effects on developing bone, including altered bone mineral density as well as reduced bending breaking force and stiffness. The aim of this study was to evaluate the use of the third lower molar and long bones as biomarkers of PCDD/F exposure in two wild vole species, the bank vole (Clethrionomys glareolus) and the field vole (Microtus agrestis) collected from a PCDD/F contaminated former sawmill area. Survey of soil and biota of the sawmill area indicated a PCDD/F contamination with a congener profile characteristic for the chlorophenol wood preservative Ky-5. The PCDD/F concentration in the bank vole was notably higher than in the field vole. The third molar of the bank vole was significantly smaller in dioxin-exposed animals compared to control group, while there was no difference between these two groups in the field vole. No significant alterations were observed in bone density and strength in either species except for reduced bending strength of the femur neck in bank vole males exposed to dioxins. Even though the bone changes are among the sensitive endpoints of dioxin-exposure, high variability due to age, size and gender limits their use as biomarkers of wildlife exposure. In conclusion, the size of molar teeth seems to be a sensitive and robust biomarker for PCDD/F exposure in wild bank vole populations and thus worth of further studies.     

Bioaccumulation, bioavailability and environmental fate of chlorophenol impurities, polychlorinated hydroxydiphenylethers and their methoxy analogues

The bioaccumulation potential and environmental fate of polychlorinated hydroxydiphenyl ethers (HO-PCDEs; polychlorinated phenoxyphenols, PCPP), the major impurities of chlorophenol formulations and their methoxy analogues (MeO-PCDEs; polychlorinated methoxyanisoles, PCPAs) were investigated. Oligochaete worms (Lumbriculus variegatus) exposed to sediment spiked with a model substance of one HO-hexaCDE (4'-HO-PCDE 161) or its methoxy analogue (4'-MeO-PCDE 161) clearly accumulated the test compounds revealing the potential for environmental risk of HO-PCDEs and MeO-PCDEs. The HO-PCDE tested has earlier been reported as an abundant component in a Finnish chlorophenol formulation (Ky-5) and its methoxy analogue is recognized as an abundant MeO-PCDE in sawmill soil contaminated by the formulation. The occurrence of 4'-HO-PCDE 161 and its methoxy analogue among other HO-PCDEs and MeO-PCDEs in lake mussels (Anodonta piscinalis) incubated in a river contaminated via the manufacture of Ky-5 showed that these compounds are bioavailable and transported in the aquatic environment. Mussel comparison with sediment data pointed to a higher accumulation potential for MeO-PCDEs than for HO-PCDEs. The finding of HO-PCDEs in groundwater samples collected from a groundwater reservoir, which had been contaminated by chlorophenols, points to potential of HO-PCDEs for transport with water in soil.     

Photodegradation of polychlorinated dibenzo-p-dioxins and dibenzofurans in soil with vegetable oil

GOAL, SCOPE AND BACKGROUND: This study was carried out to investigate the effect of olive oil on the photodegradation of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in contaminated sawmill soil. Previous studies had shown that the solubility of PCDD/Fs in olive oil is high and a rapid photodegradation of PCDD/Fs takes place in olive oil when irradiated with ultraviolet (blacklight) lamps. The efficiency of this treatment method was evaluated under more practical conditions. These included the use of sunlight irradiation and a lower-grade olive oil, without a preliminary extraction of soil with olive oil. METHODS: A 1-cm layer of contaminated sawmill soil was blended with 20 weight-% of olive oil and exposed to sunlight for four weeks. In another experiment, a new dose of olive oil was added at the middle of the exposure period. The PCDD/F concentrations of the soils were monitored periodically. RESULTS AND DISCUSSION: A reduction in the concentration of 2,3,7,8-chlorinated PCDD/Fs by 59% and in WHO-TEQ in contaminated sawmill soil by 48% was attained after blending the soil with two doses (20 + 20%) of olive oil and exposing the mixture to sunlight for four weeks. Photodegradation with only one dose of olive oil was less efficient. This suggests that periodical additions of olive oil would be needed to maintain a proper degradation rate. After the oil additions, the WHO-TEQ content of the soil declined with first order reaction half-lives of 19.2 to 19.7 d. The overall half-life during the four-week treatment, however, was 30 d. CONCLUSION: A significant reduction in the PCDD/F concentration of aged sawmill soil can be achieved with a relatively simple olive oil-sunlight treatment. RECOMMENDATIONS AND OUTLOOK: Some theoretical and technological questions need to be solved before using the investigated soil decontamination method in larger-scale applications. The functions of vegetable oils in photodegradation processes should be studied in more detail. The amount of oil that is needed for a proper solubilisation and photodegradation of PCDD/Fs should be minimised. Moreover, special care should be taken to prevent mobilisation of PCDD/Fs to the surrounding environment and to avoid leaving bioavailable residuals of PCDD/Fs in soil.     

Mobility of chloroaromatic compounds in soil: case studies of Swedish chlorophenol-contaminated sawmill sites

This paper summarizes recent studies on the environmental fate of chloroaromatic compounds in chlorophenol (CP)-contaminated soil and groundwater at Swedish sawmill sites. Relative proportions of CPs, polychlorinated phenoxy phenols (PCPPs), polychlorinated diphenyl ethers (PCDEs), polychlorinated dibenzo-p-dioxins (PCDDs), and polychlorinated dibenzofurans (PCDFs) were determined in preservatives, particulate organic matter (POM), dissolved organic matter (DOM), groundwater, and particles filtered from groundwater. All compound classes were found in the different compartments. The fraction of PCPPs, PCDEs, PCDDs, and PCDFs had increased in the soil samples relative to the proportions in the preservatives. This increase showed correlation with the hydrophobicity, that is, PCDDs had the largest increase. Similar correlation was found between hydrophobicity and the importance of partitioning to POM over DOM. The more water soluble compound group, CP, was found equally distributed between POM and DOM. For PCPPs, PCDEs, PCDDs, and PCDFs, the relative partitioning to POM increased with increased hydrophobicity. Despite the relative partitioning towards POM, compared with DOM, cotransport with DOM and suspended colloidal fractions was found to substantially increase the transport of these compounds in the groundwater samples.     

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.     

Residual congener pattern of dioxins in human breast milk in southern Vietnam

This study evaluated residual congener patterns of dioxin/furan (=PCDD/DF) related to tactical herbicides aerially sprayed over the regions of southern Vietnam through Operation Ranch Hand. The study focused on Cam Chinh (CC) commune, Quang Tri province (an area sprayed with tactical herbicides), and the Cam Phuc (CP) commune, Ha Tinh province (a non-sprayed area). Breast milk samples for analysis were collected in September 2002 and July 2003 from lactating primiparous and multiparous mothers born after the war (<31 years old). We found the levels of each congener in the CC commune were higher than in the CP commune, and determined specificity in the PCDD/DF congener pattern in CC commune samples by cluster analysis. The congener pattern is characterized by higher (the hexa-, the hepta-, and the octa-) chlorinated PCDD/DFs; this appears to be the same profile as that presented by pentachlorophenol (PCP), rather than 2,4,5-trichlorophenoxy acid (2,4,5-T) contaminated with 2,3,7,8-TCDD. A GC/MS study in the 1970s detected the chlorophenols 2,4-di and 2,4,6-trichlorophenol in some Agent Orange samples, which contained, like PCP, a wide variety of PCDD/DF congeners. In this context, it may be expected that certain tactical herbicides contaminated with various chlorophenol impurities, have a unique congener pattern when compared with pure 2,4,5-T formulations.     

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.     

Transport of chlorinated dioxins and furans in soil columns: modeling pentachlorophenol pole-treating oil influence

Column experiments were conducted to validate a screening model predicting the influence of pentachlorophenol (PCP) pole-treating oil on the vertical migration of its impurities, chlorinated dioxins and furans (PCDD/Fs). PCP pole-treating oil (15 mL d⁻¹) and water (20 mL d⁻¹) were added daily to the top of sand and organic soil columns during 35 d. Column soil samples were analyzed to determine concentrations of hydrocarbons and PCDD/Fs at several depths in the columns (0-30 cm) and their evolution in time (7, 14, 21 and 35 d).The model predicted a significant vertical migration of PCDD/Fs due to the presence of oil as a free phase and PCDD/Fs were found in the different column layers at concentrations consistent with model predictions (same order of magnitude). Measured PCDD/Fs concentrations are in total disagreement with literature data and with model prediction in the absence of oil free phase, which implies PCDD/F properties alone cannot be used to predict their fate in the current context: the influence of PCP pole-treating oil must be accounted for to properly explain their migration.     

PCDD/F and PCB history in dated sediments of a rural lake

Concentrations of polychlorinated dibenzo-p-dioxins (PCDD), dibenzofurans (PCDF) and biphenyls (PCB) were analysed from a sediment core, which had been sampled from a remote lake in Finland. The deepest subsamples were analysed from a depth of 4.0 m, and were more than 8000 years old. At the surface of the sediment core, low levels of industrial background contamination were detected. The sum of 2,3,7,8-substituted PCDD/Fs was 35 ng/kg d.w. (dry weight), or 1.2 ng/kg d.w. in WHO's toxicity equivalent, WHO-TEQ. The annual accumulation rate of 2,3,7,8-substituted PCDD/Fs was 1.26 ng m(-2) a(-1). Deeper in the core, PCDD/F concentrations ranged between 2.11 and 11.1 ng/kg d.w. (0.24 and 1.70 ng/kg d.w. WHO-TEQ) and the accumulation rate was 0.11 ng m(-2) a(-1). A characteristic PCDD/F congener profile was found in all pre-industrial sediment layers. The order of concentrations was OCDD > 1,2,3,4,6,7,8-HpCDD > 1,2,3,7,8,9-HxCDD > 1,2,3,4,7,8-HxCDD > 2,3,7,8-TCDD, and concentrations of 2,3,7,8-chlorinated dibenzofurans were below the detection limit. Similar congener profiles have previously been described in samples for which natural PCDD/F formation has been proposed. PCBs were present at low levels in all of the sediment samples. The sum of the PCB concentrations of the sediment subsamples ranged between 50 and 2540 ng/kg d.w., and the three predominant congeners in the core were PCBs 18, 52, and 110.     

Polychlorinated dibenzo-p-dioxins,dibenzofurans, biphenyls,paraffins and polybrominated diphenyl ethers in marine fish species from Ebro River Delta (Spain)

The results of a surveillance programme on the determination of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs) and short chain chlorinated paraffins (SCCPs) in marine fish and shellfish species which are fished, commercialised and consumed in the Ebro River Delta area (NE, Spain) are presented. The study included the analysis of five marine fish species (sardine, gilthead sea bream, conger, eel and flounder) and three shellfish species (murex, carpet shell and mussel) collected in 2012 in five fishing harbours near to this area. WHO-TEQ concentrations for PCDD/Fs and dioxin like PCBs (dl-PCBs) ranged from 0.03 to 0.31 pg WHO-TEQ_2005PCDD/F g⁻¹ wet weight (ww) and from 0.02 to 3.15 pg WHO-TEQ_2005PCB g⁻¹ ww, respectively. All levels were below the maximum concentrations established by the EU Regulation. The PCBs and PCDD/Fs accumulation pattern found in the samples analysed showed a distribution typically reported for marine samples. For marker PCBs and PBDEs, concentration levels ranging from 929 to 57 494 pg g⁻¹ ww and from 36.2 to 827 pg g⁻¹ ww were obtained, respectively, meanwhile for SCCPs levels were between 3.1 and 141 ng g⁻¹ ww. Finally, the trends in the levels of PCDD/F and dl-PCBs found from 2006 to 2012 in fish and shellfish species were studied. A slight decrease of PCDD/F and dl-PCB concentrations was found since 2006.     

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.     

Human PCDD/PCDF levels near a pentachlorophenol contamination site in Tainan, Taiwan

A pentachlorophenol (PCP) manufacturing plant in southern Taiwan discontinued production in 1989. The site of the abandoned plant was heavily contaminated by PCDD/PCDFs, impurities formed in the PCP production process. Serum samples collected from 27 residents living near the deserted plant were evaluated to determine whether this contamination had associated serum levels of PCDD/PCDFs in local residents. The average level of 17 tested congeners ranged from 556 to 5240 pg/g lipid (mean, 1670 pg/g lipid). The corresponding 2,3,7,8-TCDD toxicity equivalent quotient values calculated by international toxicity equivalent factors (I-TEFs) and those recommended by WHO (WHO-TEFs) were 47.2 pg I-TEQ/g lipid and 53.4 pg WHO-TEQ/g lipid, respectively. Levels in other parts of Taiwan typically range from 15 to 20 pg WHO-TEQ/g lipid; therefore, it is likely that the heavily contaminated plant site caused these unusually high serum levels. The average PCDD/PCDF levels of 29 fish-tissue and nine soil samples collected from the sea reservoir surrounding the abandoned PCP plant were also abnormally high: 8630 pg/g lipid (985 pg WHO-TEQ/g lipid) and 606000 pg/g-sample (922 pg WHO-TEQ/g-sample), respectively. Factor analysis indicated that the congener pattern of human serum samples collected from residents living near the abandoned PCP plant different from samples collected from other areas in Taiwan without known PCDD/PCDF pollution. Similar results were observed for the fish tissue and soil samples. The current study may have discovered a "hot spot" for elevated dioxin human exposure in Taiwan. The preliminary finding has raised a public health concern in the inspected area and requires further investigations to clarify the nature of the contamination and potential impact on the local environment and human health.     

Comparison of organohalogen compounds in a white-tailed sea eagle egg laid in 1941 with five eggs from 1996 to 2001

Eggs laid by white-tailed sea eagles (Haliaeetus albicilla), one in 1941 and five eggs between 1996 and 2001, all from the same geographical region of the Baltic Sea, were screened for organohalogen substances. The 1941 egg contained hexachlorobenzene (HCB), but did not contain either of the pesticides hexachlorocyclohexane (HCH) or p,p′-DDT, nor any metabolites of the latter. In contrast, the more recent eggs (REs) contained all of these compounds. Of the seven polychlorinated biphenyls (PCBs) analyzed (CB28, −52, −101, −118, −138/−163, −153 and 180), only the more highly chlorinated congeners were detected in the 1941 sample, with CB153 followed by CB180 showing the highest concentrations. All eggs demonstrated the same congener pattern with respect to the more highly chlorinated PCBs, but concentrations were approximately 70-230 times higher in the REs. All of the polychlorinated-p-dioxin and dibenzofuran (PCDD/Fs) congeners analyzed were detected in the eggs, with the dominant congener being 2,3,4,7,8-PeCDF (1250 pg/g l.w. in 1941 and 1540 pg/g l.w. (GM) for the REs, respectively). None of the other congeners exceeded 400 pg/g l.w., and the concentrations of 2,3,7,8-TCDD, 2,3,7,8-TCDF and 1,2,3,7,8-PeCDF were all lower in the REs. None of five congeners of polybrominated diphenyl ethers (PBDEs) found in the REs was detected in the egg from 1941. The three methoxylated brominated diphenyl ethers (MeO-BDEs) analyzed were found at similar levels and with a similar congener pattern in REs as in the egg from 1941.In conclusion, this study has shown the absence of DDE and PBDE and the presence of HCB and PCBs in a white-tailed sea eagle egg laid in 1941, and a strong increase of PCBs, DDE and PBDE in white-tailed sea eagle eggs from the same area in 1996-2001. The MeO-BDEs were found in similar concentrations in the analyzed eggs. The 1941 sample shows substantial concentrations of PCDD/Fs, noteworthy in the same magnitude as in the recent samples, illustrating the historical and recent exposure of these compounds.     

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.     

PCDD/F, PAH and heavy metals in the sewage sludge from six wastewater treatment plants in Beijing, China

In order to better understand land application of sewage sludge, the characterization of heavy metals, PCDD/F and PAHs in sewage sludge was investigated from six different wastewater treatment plants (WWTP) in Beijing City, China. It was found that the total concentrations of Zn in Wujiacun (WJC) sewage sludge, and Cd and Hg in sewage sludge generated from all of the six different places are higher than Chinese regulation limit of pollutants for sludge to be used for agriculture (GB18918-2002). The levels of 16 PAHs that have been categorized as priority pollutants by US EPA in the sewage sludge samples varied from 2467 to 25923 microg/kg (dry weight), the highest values of 25923 microg/kg being found in WJC WWTP. The concentrations of Benzo[a]pyrene were as high as 6.1mg/kg dry weight in WJC sewage sludge, exceeding the maximum permitted content by GB18918-2002. Individual PAH content varies considerably with sewage samples. The ratios of anthracene to anthracene plus phenanthrene (An/178), benz[a]anthracene to benz[a]anthracene plus chrysene (BaA/228), indene[1,2,3-cd]pyrene to indene[1,2,3-cd]pyrene plus benzo[g,h,i]perylene (In/In+BP), and fluoranthene to fluoranthene plus pyrene (Fl/Fl+Py) suggest that petroleum and combustion of fossil fuel were the dominant contributions for the PAHs in sewage sludge. The concentrations of total PCDD/F in the sewage sludge ranged from 330 to 4245 pg/g d.w. The toxicity equivalent concentrations is between 3.47-88.24 pg I-TEQ according to NATO/CCMS, which is below Chinese legislation limit value proposed for land application. The PCDD/F congener/homologue profiles found in the Beijing samples indicated that the high chlorinated PCDD/F contamination might originate mainly from PCP-related source and depositional sources while the low chlorinated PCDD/F homologues could be originating from incineration or coal combustion. The major source of PCDD/Fs in Beijing sludge is still unclear.     

Thermal remediation of PCDD/Fs contaminated soil by zone combustion process

A new thermal process has been proposed for remediating soils contaminated by chlorinated organic compounds, e.g., PCDD/Fs and PCBs. This is to apply the "zone combustion process" which utilizes stable combustion of coke particles in the packed bed to soils with air flow across the bed. The usefulness and validity were obtained the results showing that more than 98.9% of PCDD/Fs in the soil was successfully removed in a laboratory-scale experiment. Some pretreatment of the soil sample, such as drying, pre-granulation and addition of limestone was found to make the removal efficiency better. Although, some fundamentals on the behavior of PCDD/Fs, e.g., decomposition/vaporization ratios and formation of other compounds cannot be certainly identified yet, the present results clearly show a way to remediate the contaminated soils and solid wastes.     

Polychlorinated dibenzo-p-dioxins, dibenzofurans, biphenyls, naphthalenes and polybrominated diphenyl ethers in the edible fish caught from the Baltic Sea and lakes in Finland

A total of 156 fish composite samples were collected from five areas of the Baltic Sea and from three lakes and analysed for polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), polychlorinated biphenyls (PCBs), polychlorinated naphthalenes (PCNs) and polybrominated diphenyl ethers (PBDEs). The European Union's maximum permissible level for PCDD/Fs, 4 pg WHO-TEQ/g fresh weight (fw), was exceeded in salmon, river lamprey and Baltic herring. In other species from the Baltic Sea, the 90th percentile was 3.42 pg WHO(PCDD/F)-TEQ/g fw. In the lake fish, the concentrations of PCDD/Fs, PCBs and PCNs were only 29-46% of those in the same species caught from the Baltic Sea, whereas the concentrations of PBDEs in the lake fish were as high as in the Baltic Sea fish. Dioxin-like PCBs contributed to the total dioxin-like toxicity of PCBs and PCDD/Fs by 49+/-12% in all the analysed samples.     

Synthesis of chlorinated dibenzofurans and chlorinated amino-dibenzofurans from the corresponding diphenyl ethers and nitro-diphenylethers

The synthesis of five chlorinated dibenzofurans and three chlorinated animodibenzofurans from easily available diphenyl ethers is described. Also reported is the preparation of the diphenyl ethers. The ¹H-NMR and mass spectra data for the compounds are also reported.