The fate of chlorobenzenes and permethrins during anaerobic sewage sludge digestion

Mixed primary sewage sludge was incubated anaerobically with and without azide addition to prevent biological activity. The behaviour of 1,3-, 1,4- and 1,2-dichlorobenzene, 1,3,5-, 1,2,4- and 1,2,3-trichlorobenzene, 1,2,3,4- and 1,2,4,5-tetrachlorobenzene, hexachlorobenzene, and cis- and trans-permethrin was examined to determine their potential removal during anaerobic digestion. All the chlorobenzenes were removed to varying extents over 32 days of incubation, ranging from 25% removal for 1,3,5-trichlorobenzene to 80% removal for 1,4-dichlorobenzene. Biodegradation may have been responsible for the reductions in 1,3- and 1,4-dichlorobenzene and 1,2,4- and 1,2,3-trichlorobenzene as there was no significant removal of these compounds in azide treated sludge. The removal over 32 days of cis- and transpermethrin was 87% and 96% respectively. These removals were attributed to a chemical or physical process.     

The acute toxicity of chlorobenzenes for earthworms (Eisenia andrei) in different exposure systems

Earthworms (Eisenia andrei) were exposed to different concentrations of two chlorobenzenes (1,2,3-trichloro- and pentachlorobenzene) using different routes of administration: in water, in soil, via food and on filter paper. Except for the contact paper toxicity test, lethal body burdens (LBBs) measured in these different exposure systems were similar for the same test chemical. LBBs for 1,2,3-trichlorobenzene varied between 0.44 and 2.1 μmol/g and for pentachlorobenzene between 1.29 and 2.34 μmol/g. These values correspond with literature data for fish. For 1,4-dichloro- and 1,2,3,4-tetrachlorobenzene LBBs measured with the contact paper toxicity test were 0.33 and 3.2 μmol/g, respectively. Exposure to hexachlorobenzene and hexabromobenzene using the contact toxicity test did not result in death within 48 hours.     

Incidence of chlorinated benzenes and chlorinated ethylenes in Lake Ontario Herring Gulls

Great Lakes Herring Gulls (Larus argentatus) and their eggs have proven to be useful integrators on a lakewide basis of high molecular weight, relatively involatile organochlorine pollutants such as PCRs. A search for relatively volatile organochlorine compounds by GC/MS also revealed the presence of tri- and tetrachloroethylene, and isomers of di-, tri-, tetra-, penta- and hexachlorobenzene in the body lipid of adult Herring Gulls from Lake Ontario. Analysis of pooled eggs from colonies throughout the Great Lakes in 1978 showed that pentachlorobenzene and hexachlorobenzene were ubiquitous contaminants at levels from 14–50 ng/kg and 90–350 ng/kg, respectively. Hexachlorobenzene levels were 2–3 times higher in Lake Ontario than the other lakes, whereas pentachlorobenzene was more evenly distributed geographically. Levels of 1,2,3,4-tetra-, 1,2,4,5-tetra- and 1,2,4-trichlorobenzene near the detection limit of 10–20 ng/kg were found in a few samples.     

The metabolization of lindane in a culture of mould and the degradation scheme of lindane

The metabolism of Lindane, gamma-Pentachlorcyclohexene and isomeric Tetrachlorobenzenes in a culture of Mould was investigated in this work. 1,2-, 1,4-Dichlorobenzene, 1,2,3-, 1,2,4-, 1,3,5-Trichlorobenzene, 1,2,3,4-, 1,2,4,5- and/or 1,2,3,5-Tetrachlorobenzene, Pentachlorobenzene, gamma-Pentachlorocyclohexene, Hexachlorobenzene, Tetrachlorocyclohexenol, 2,3,4-, 2,4,6-Trichlorophenol, 2,3,4,5-, 2,3,4,6- and/or 2,3,5,6-Tetrachlorophenol and Pentachlorophenol could be identified as metabolites of Lindane. A degradation scheme is proposed. It includes gamma-Pentachlorocyclohexene, Hexachlorocyclohexene, Pentachlorocyclohexenol, Tetrachlorocyclohexenol and Polychlorophenols as main metabolites. The pathway based on many earlier published experimental results of these and other authors so far as possible.In former papers we have already reported about the known literature concerning the metabolism of Lindane (1 – 4).Comprehensive studies about the metabolism of Lindane in cultures of mould (1, 5, 6), in rats (7 – 9), and in men (2, 3) are to contribute in explaining away any uncertainties about the degradation of Lindane. Many investigations contributed to work out degradation schemes of Lindane (10 – 21).     

Photodegradation of pentachlorophenol and its degradation pathways predicted using density functional theory

The objectives of the present research were (i) to report the mass balance of chlorine during pentachlorophenol (PCP) photodegradation and (ii) to reveal the photodegradation pathway experimentally with a theoretical proof based on the density functional theory (DFT). The chlorine of PCP was completely mineralized to produce chloride ions after 24h of UV irradiation. As intermediates, 2,3,5,6-tetrachlorophenol, 2,3,4,6-tetrachlorophenol and 2,5-dichlorophenol were identified. At least 80% of the chlorine balance during PCP photodegradation was accounted by PCP, these intermediates, and chloride ions. A DFT calculation showed differences in the C-Cl bond dissociation energy level and the positions of respective PCP molecular and the PCP intermediates. The dechlorination intermediates predicted using the calculated C-Cl bond dissociation energy were consistent with those experimentally confirmed, indicating the feasibility of this theoretical method in predicting the dechlorination pathway.     

The in vitro metabolism of lindane by an enzyme preparation from chicken liver.

The soluble fraction (105,000 x g, 30 min) of chicken liver homogenates contained an enzyme(s), probably a dehydrochlorinase(s), which metabolized lindane in vitro. The reaction was glutathione dependent and took place anaerobically. The enzyme(s) also metabolized the alpha- and delta-isomers but not the beta-isomer. About 66% of the in vitro metabolites were soluble in petroleum ether. From the ether-soluble fraction, o-, p- amd m-dichlorobenzene, 1,2,3- and 1,2,4-trichlorobenzene, gamma-2,3,4,5,6-pentachlorocyclohex-1-ene (gamma-PCCH), 2,3- and 2,4-dichlorophenol and 2,4,6-trichlorophenol were identified by comparison of mass spectra and gas chromatographic data with those of reference compounds. Seven additional metabolites were tentatively identified from their mass spectra data. These metabolites were: chlorobenzene, 2 isomers of trichlorocyclohexene, dichlorocyclohexadienetriol, chlorophenol, trichlorocyclohexenol and trichlorocyclohexanediol. The petroleum ether-extracted aqueous phase contained a number of unidentified conjugated metabolites. It was concluded that the metabolic pathway for lindane in the chicken is quite similar to that in the pheasant.     

Bioconcentration and uptake kinetics of chlorobenzenes in soy-bean roots

Excised soy-beanroots were exposed to an aqueous solution of five homologous chlorobenzenes in constant concentration. The results were in general agreement with water-lipid partitioning. The relationship between the bioconcentration factor and the octanol-water partition coëfficiënt (K_OW) can be used to estimate bioconcentration. Effective equilibrium was reached within 2.5 hours for 1,2-di-, 1,3,5-tri- and 1,2,3,4-hexachlorobenzene and after a mean of 10.1 and 17.9 hours for penta- and hexachlorobenzene respectively. For 1,2-dichlorobenzene, 1,3,5-trichlorobenzene and 1,2,3,4-tetrachlorobenzene the elimination rate constant was > 4.1, and 0.46 and 0.30 hr⁻¹ for penta- respectively hexachlorobenzene. In the range log K_ow 4.56–5.77, k₂ was negatively correlated with log K_OW but k₁ was not correlated with log K_OW..     

Dehalogenation Potential of Municipal Waste Incineration Fly Ash

BACKGROUND, AIMS AND SCOPE: In the first part of this paper the main principles which control the dehalogenation of polychlorinated aromatic compounds on municipal waste incineration fly ash (MWI-FA) have been discussed and the model fly ash of similar dehalogenation activity has been proposed. Even if both systems show comparable dehalogenation properties, the main question concerning the postulated identical reaction mechanism in both cases is left unanswered. The other very important point is to what extent is this dechlorination mechanism thermodynamically controlled. The same problem is often discussed in the literature also for the de novo synthetic reactions. From the data it is clear that metallic copper plays a decisive role in the mechanism of the dehalogenation reaction. Although the results reported in the first part strongly support the idea that copper acts in this dechlorination as the reaction component, in contrast to its generally accepted catalytic behaviour, we believed that additional support for this conclusion can be obtained with the help of a thermodynamic interpretation of the mechanism of the reaction. RESULTS AND DISCUSSION: The pathways of hexachlorobenzene dechlorination on MWI-FA and model fly ash were studied in a closed system at 260-300 degrees C under nitrogen atmosphere. These pathways were the same for both systems, with the following prevailing sequences: hexachlorobenzene --> pentachlorobenzene --> 1,2,3,5-tetrachlorobenzene --> 1,3,5-trichlorobenzene --> 1,3-dichlorobenzene. Thermodynamic calculations were carried out by using the method of minimization total Gibbs energy of the whole system. In the calculations, the following reaction components were taken into account: all gaseous chlorinated benzenes, benzene, hydrogen chloride, a gaseous trimer Cu3Cl3, and also Cu2O and CuCl2 as solid components. The effect of the reaction temperature and the amount of copper and water vapour were considered as well. The effect of reaction temperature was determined from the data calculated for the 500 to 750 K temperature region. The effect of the initial composition was determined for the molar amounts of copper = 0.01-3 moles and water vapour = 0.2 to 3 moles per mole of chlorobenzene isomer CONCLUSIONS: The results of hexachlorobenzene dechlorination by MWI-FA and model fly ash under comparable reaction conditions allow us to conclude that both dechlorinations proceed via the same dechlorination pathways, which can be taken as an evidence of the identical dehalogenation mechanism for both systems. The relative percentual distribution of the dehalogenated products depends on the temperature, but not on the initial amount of water vapour or copper metal. On the other hand, the initial amount of copper substantially affects the conversion of the dehalogenation as well as the molar ratio of Cu3Cl3 to HCl in the equilibrium mixture. Comparison of the experimental with thermodynamic results supports the idea that dehalogenation reactions are thermodynamically controlled. RECOMMENDATIONS AND OUTLOOK: Thermodynamic analysis of the dehalogenation reactions may prove useful for a wide range of pollutants. The calculations concerning polychlorinated biphenyls and phenols are under study.     

Dioxin and dioxin-like PCB impurities in some Japanese agrochemical formulations

The profile and amount of dioxin impurity in agrochemicals were studied through detailed analysis of historic Japanese formulations. The chemicals analyzed include pentachlorophenol (PCP), 2,4,6-trichlorophenyl-4'-nitrophenyl ether (chloronitrofen, CNP), 2,4-dichlorophenyl-4'-nitrophenyl ether (nitrofen, NIP), tetrachloro-iso-phthalonitrile (chlorothalonil, TPN), 2-methyl-4-chloro-phenoxyacetic acid (MCP) and 2,4-dichlorophenoxyacetic acid (2,4-D). Among the six, two herbicides, PCP and CNP, produced during the 1960s and 1970s, contained very high concentrations of PCDD/DFs and TEQ. Others contained relatively low concentrations of PCDD/DFs. Dioxin-like PCB concentrations in all chemicals studied were low and their contributions to TEQ were negligible. The total dioxin emissions from the use of agrochemicals in Japan during the past 40 years (1955-1995) were estimated to be about a few hundred thousand kg of PCDD/DFs and 250 kg of WHO-TEQ from PCP and 190 x 10(3) kg of PCDD/DFs and 440 kg of WHO-TEQ from CNP. The major dioxin congeners present in PCP formulations were highly chlorinated PCDD/DFs that can be formed by the coupling of PCP and/or 2,3,4,6-tetrachlorophenol, and those in the CNP formulations were tetra- to hexa-chlorinated PCDD/DFs that can be formed from 2,4,6-trichlorophenol and/or 2,3,4,6-tetrachlorophenol.     

Formation of hydroxylated and dimeric intermediates during oxidation of chlorinated phenols in aqueous solution

The oxidation of selected chlorophenols (2-chlorophenol, 4-chlorophenol, 2,4-dichlorophenol, 2,4,6-trichlorophenol, 2,3,4,6-tetrachlorophenol and pentachlorophenol) was studied in aqueous solutions using UV/H2O2 and O3 methods. The formation of oxidation intermediates was measured to elucidate their importance in the treatment of chlorophenols. Results indicated that chlorophenols can be treated efficiently by the methods studied, but the dechlorination of the compounds was insufficient. Analysis of intermediates in the acetylated extraction fractions showed that hydroxylation of chlorophenols and formation of dimeric products were involved in the oxidation of chlorophenols in both treatment processes. The majority of the intermediates detected were transient, and thus were not detectable after an extended treatment time. The presence of a complicated mixture of intermediates suggests the need for toxicity testing to confirm the detoxifying effect of the chemical oxidation of chlorophenols.     

Detoxification of hexachlorobenzene by dechlorination with potassium-sodium alloy

Dechlorination of hexachlorobenzene (HCB) was achieved by a liquid potassium–sodium (K–Na)-alloy. HCB in a cyclohexane/benzene solution (22 mmol/l, 4.67 g/l as chlorine) was dechlorinated by almost 100% after a 30-min reaction, indicating high reactivity of K–Na alloy and high proton donating power of cyclohexane. Decreasing orders of chlorobenzenes identified after a 15-min reaction, by amount were 1,2,3,4- > 1,2,3,5- > 1,2,4,5- for tetrachlorobenzenes, 1,2,4- > 1,2,3- > 1,3,5- for trichlorobenzenes, and 1,4- > 1,3- > 1,2- for dichlorobenzenes. It was hypothesized that once one chlorine atom in HCB was replaced with a proton, the adjacent chlorine atom to the proton tended to be replaced with another hydrogen atom. A total of 63 PCBs formed via the Wurtz–Fittig reaction were identified as by-products in the sample after a 15-min reaction. Among PCBs found, 2,3^′,4^′,5-tetrachlorobiphenyl, which was a product from 1,2,4-trichlorobenzene formed via the Wurtz–Fittig reaction, was detected in relatively high concentration (48.9 nmol/ml). The sample obtained from a reaction mixture after 30 min contained only 14 PCBs in trace amounts, indicating that the PCBs formed were also further dechlorinated by K–Na alloy. Non-chlorinated compounds––such as methylbenzene, dimethylbenzene, dimer of tetrahydrofuran, and dicyclohexyl (dimer of cyclohexane)––were also identified in the samples. A method using K–Na alloy developed in the present study dechlorinated satisfactorily HCB at room temperature.     

Metabolism of beta-hexachlorocyclohexane-14C in rats following low dosing in the daily diet

beta-Hexachlorocyclohexane-14C (1.5 ppm) was administered in the diet to rats for one week. During the elimination phase three therapeutic agents were fed to enhance the clearance. Renal and fecal excreted radioactive products were collected for 8 weeks and extracted. Although significant differences in the total excreted amount of radioactivity were registered between controls and treated rats, there were no quantitative differences in the extractability of the excreta and no differences in the chemical nature of metabolites found. Radioactivity in urine consisted to 100% of conversion products, about 30% of which were unextractable residues. In the organic soluble fraction the 2,4,6-trichlorophenol was the major metabolite in urine and the only metabolite detected in feces. Minor conversion products of beta-HCH in urine were a trichlorohydroxyme-thoxybenzene, a dichlorophenol and a trace of a tetrachlorocyclohexane-isomer.     

Fate of 14C‐allylalcohol herbicide in soils and crop residues

Abstract

Residue disappearance and leaching of ¹⁴C‐allyl‐alcohol from different soils were studied in laboratory experiments. Additionally, the uptake of residues by lettuce and carrots was investigated in the greenhouse. In laboratory experiments, residue disappearance and leaching from soils was correlated negatively to the organic matter content. In greenhouse experiments with a sandy loam soil at an application rate normally used in practice, an average of 12.5 % of the applied radioactivity was recovered after an eight day interval between application and sowing. Furthermore, an average of 8 % (sum in soil and plants) of the applied radioactivity was recovered after lettuce or carrot growing. Uptake of residues was higher by carrots than by lettuce, and higher by lettuce roots than by lettuce tops. No bioaccumulation was observed. The residues in soils and plants were, to a high percentage, unextractable and, to a smaller extent, fully water‐soluble products. Unchanged allylalcohol could not be detected by the analytical methods used.     

Investigation of organic xenobiotic transfers,partitioning and processing in air-soil-plant systems using a microcosm apparatus. Part II: comparing the fate of chlorobenzenes in grass planted soil

A microcosm system was used to investigate and compare transfers of 14C labeled-1,2-dichlorobenzene (DCB), 1,2,4-trichlorobenzene (TCB) and hexachlorobenzene (HCB) in an air-soil-plant system using single grass tillers planted into spiked soil. This study was the second phase of a development investigation for eventual study of a range of xenobiotic pollutants. Recoveries from the system were excellent at >90%. The predominant loss pathway for 14C labeled-1,2-DCB and 1,2,4-TCB was volatilisation with 85% and 76% volatilisation of parent compound and volatile metabolites over 5 weeks respectively. Most of the added label in the hexachlorobenzene spiked system remained in soil. Mineralisation was <1% for all compounds. 14C plant burdens expressed as microg parent compound/g plant fresh weight were significant and suggest that plant uptake of chlorobenzenes from soil may be an important exposure pathway for grazing herbivores. Both shoot and root uptake of 14C was detected, with foliar uptake of volatilised compounds dominating shoot uptake, and being greatest in TCB spiked systems. The microcosm is shown as potentially an ideal system with which to investigate organic xenobiotic partitioning in air-soil-plant systems to improve understanding of the equilibria and kinetics of exchanges. However, limitations imposed by the lab based conditions must be recognized and data should be compared with field based data sets as a consequence.     

Chlorophenols in lake bottom sediments: A retrospective study of drinking water contamination

Lake and brook bottom sediments were analyzed for chlorophenols to provide historical data of exposure assessment, after the water intake plant of a Finnish village had been found to be contaminated in 1987, and subsequently elevated non-Hodgkin lymphoma risk was detected. Highly elevated 2,3,4,6-tetrachlorophenol and pentachlorophenol levels were found in all four lake sediment cores investigated. The distribution was uneven with much higher concentrations in the estuary, in contrast to PCB compounds which were more evenly distributed within the basin. The inlet origin of the chlorophenols in the sediments was further supported by the regional distribution pattern of these compounds in the sediment and water along transects of the inlet and its tributaries. The composition of chlorophenol congeners in the sediments was similar to that in a commercial fungicide used by a local sawmill, but different from other sediment analyses reported in Finland, also implying a local source. Dating of three cores by Pb-210 and soot ball chronology indicated that the contamination of the watercourse started in the early 1970s at the latest but possibly earlier. This would provide the latency time required for tumour appearance in the 1970s and 1980s.     

Sequential treatment via Trametes versicolor and UV/TiO2/Ru(x)Se(y) to reduce contaminants in waste water resulting from the bleaching process during paper production

An efficient sequential, biological and photocatalytic treatment to reduce the pollutant levels in wastewater due to the bleaching process during paper production is reported. For a biological pre-treatment, 800 ml of non-sterilized effluent was inoculated with Trametes versicolor immobilized in polyurethane foam, with 25 g l(-1) glucose, 6.75 mM CuSO(4), and 0.22 mM MnSO(4) added, and cultured at 25 degrees C with an air flow of 800 ml min(-1) for 8d. The fungus did not inhibit growth of the heterotropic populations of the effluent. After 4d of culture, the chemical oxygen demand (COD) reduction and colour removal (CR) were 82% and 80%, respectively, with laccase (LAC) and manganese peroxidase (MnP) activities of 345 U l(-1) and 78 U l(-1), respectively. The COD reduction and CR correlated positively (p<0.0001) with LAC and MnP activities. Chlorophenol removal was 99% of pentachlorophenol, 99% of 2,3,4,6-tetrachlorophenol (2,3,4,6-TCP), 98% of 3,4-dichlorophenol (3,4-DCP) and 77% of 4-chlorophenol (4-CP), while 2,4,5-trichlorophenol (2,4,5-TCP) increased to 0.2 mg l(-1). The pre-treated effluent was then exposed to a photocatalytic treatment. The treatment with photolysis resulted in 9% CR and 46% COD reduction, 42% CR and 60% COD reduction by photocatalysis, and 62% CR and 85% COD reduction by heterogeneous photocatalysis with the system TiO(2)/Ru(x)Se(y) (Fig. 4). With this treatment the bacterial and fungal populations also decreased by 5 logarithmic units with respect to the biological treatment alone (Fig. 5). The total sequential treatment resulted in a 92% CR (from 5800 UC), 97% COD reduction (from 59 g l(-1)) and 99% chlorophenol removal at 96 h and 20 min.     

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.     

Chlorobenzenes and hexachlorocyclohexanes (HCHs) in the atmosphere of Bitterfeld and Leipzig (Germany)

Concentrations of tetrachlorobenzenes, pentachlorobenzene, hexachlorobenzene and alpha-, beta-, gamma- and delta-HCH in air and deposition were measured at three different contaminated sites in Greppin, Roitzsch (both near Bitterfeld) and Leipzig during five time intervals of 14 days in the summer months of 1998. The mean values of the chlorobenzene concentrations (gas phase and particle bound portions) over the whole sampling time were 0.11 ng/Nm3 (Leipzig), 0.17 ng/Nm3 (Roitzsch) and 0.37 ng/Nm3 (Greppin), the mean values of the HCH concentrations were 0.22 ng/Nm3 (Leipzig), 0.31 ng/Nm3 (Roitzsch) and 0.69 ng/Nm3 (Greppin). This increase of the concentration values from Leipzig over Roitzsch to Greppin indicates the influences of industrial waste sites in the Bitterfeld region on the atmospheric environment. The significantly higher values of hexachlorobenzene, alpha- and beta-HCH in Greppin are probably caused by emissions from the former chemical plant Bitterfeld-Wolfen and the landfill 'Antonie' near Greppin. Compared with literature data from other industrial impacted areas the measured air concentration and deposition values are relatively low.     

Reactions of 2,4,6-trichlorophenol on model fly ash: oxidation to CO and CO2, condensation to PCDD/F and conversion into related compounds

Thermal treatment of 2,4,6-trichlorophenol on a magnesium silicate-based model fly ash in the temperature range between 250 degrees C and 400 degrees C leads predominantly to carbon monoxide and carbon dioxide. The fraction of 2,4,6-trichlorophenol which is oxidized to CO and CO2 increases from 3% at 250 degrees C to 75% at 400 degrees C. Further products are polychlorinated benzenes, dibenzo-p-dioxins, dibenzofurans and phenols. The homologue and isomer patterns of the chlorobenzenes suggest chlorination in the ipso-position of the trichlorophenol. The formation of PCDD from 2,4,6-trichlorophenol and 2,3,4,6-tetrachlorophenol on municipal solid waste incinerator fly ashes and model fly ash were compared and the reaction order calculated.