PCBs fires: Correlation of chlorobenzene isomer and PCB homolog contents of PCB fluids with PCDD and PCDF contents of soot

PCBs, PCDDs, and PCDFs are subject to new regulations promulgated under the Toxic Substances Control Act and the Resource Conservation and Recovery Act. The finding of PCDDs and PCDFs in PCBs could restrict disposal options for PCBs. A review of major fire incidents in the U.S., indicates that PCDDs have been found only in the Binghamton, N.Y., transformer fire incident. Laboratory combustion studies further support PCDFs formation from PCBs and PCDDs from chlorobenzenes. No PCDDs were found in analyses of fluids from transformers involved in transformer fire incidents. PCDFs do not appear to increase in PCBs askarel fluids from normal usage in electrical equipment.     

PCDD/PCDF contamination following a plastics fire in a university lecture hall building

Polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) were detected in soot from a building fire involving synthetic materials not containing polychlorinated biphenyls (PCBs) or chlorobenzenes.     

Formation of polychlorinated diphenyl ethers from condensation of chlorophenols with chlorobenzenes

BACKGROUND AND AIMS: Polychlorinated diphenyl ethers (PCDEs), which are among the members of persistent organic pollutants, and PCDEs have been determined in a number of environmental samples. The main possible sources are the technical production of chlorinated phenols and all processes of incomplete combustion. PCDEs were observed in the fly ash from a municipal waste incinerator (MWI). It was speculated that the condensation of chlorophenols with chlorobenzenes occurred via PCDEs to form polychlorinated dibenzofurans (PCDFs). Nevertheless, PCDEs formation from condensation of chlorophenols with chlorobenzenes has not been confirmed by experimental observation. The objective of this paper is to investigate the formation mechanism of PCDEs from the condensation of chlorophenols with chlorobenzenes. The results are expected to be helpful in understanding the formation of PCDEs and in controlling and abating PCDEs emissions from MWI. METHODS: The pyrolysis of pentachlorophenol (PCP) and/or polychlorobenzenes (PCBz) was carried out in a sealed glass tube. The reaction products were extracted and purified with K2CO3 solution. The samples were concentrated and then cleaned up on an alumina column. GC/MS was used for identification and quantification of reaction products. RESULTS AND DISCUSSION: The results showed that the pyrolysis of hexachlorobenzene (HCB) at 340 degrees C for 6 h led to the formation of decachlorodiphenyl ether (DCDE) (2.41 microg/mg) and octachlorodibenzo-p-dioxins (OCDD) (0.24 micropg/mg), while the pyrolysis of PCP yielded DCDE (13.08 microg/mg) and OCDD (180.13 microg/mg). In addition, the amount of DCDE formation from the pyrolysis of the mixture of PCP and HCB was 4.65 times higher than the total amount of DCDE formation from the pyrolysis of HCB and PCP, respectively. This indicated that PCP and HCB were prone to condensation and formation of DCDE. DCDE was the main congener of PCDEs from condensation of PCP with HCB at 340, 400 and 450 degrees C. A small amount of nonachlorodiphenyl ether (NCDE) was formed by dechlorination reaction at 450 degrees C. The condensation of PCP with 1,2,4,5-tetrachlorobenzene (Cl4Bz) formed 2,2',3,4,4',5,5',6-octachlorodiphenyl ether (OCDE). Small amounts of heptachlorodiphenyl ether (HpCDE) and hexachlorodiphenyl ether (HxCDE) were detected at 450 degrees C. Meanwhile, polychlorinated dibenzo-p-dioxins (PCDDs) and PCDFs were detected from the condensation of PCP and PCBz. CONCLUSIONS: Experimental studies clarified the behavior of the formation of PCDEs from condensation of polychlorophenols and PCBz. The condensation of polychlorophenols with PCBz formed PCDEs through elimination of HCl between polychlorophenols and PCBz molecules. Another pathway of PCDEs formation was elimination of H2O between two polychlorophenol molecules. In addition, dechlorination processes had caused the specific homologous pattern of PCDEs under higher temperatures.     

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.     

Chlorinated components in lime used in production contaminated citrus pulp pellets from Brazil

In order to further understand the contamination of the citrus pulp pellets (CPP) that were exported to Europe in 1997 we examined both contaminated lime and CPP samples for the distribution of polychlorinated biphenyls (PCBs) and chlorinated benzenes (tri–hexa). Standard isotope dilution techniques were applied for all samples, which were analysed by selected ion monitoring high resolution GC–MS. Lime that is used in the production of CPP product is highly contaminated with PCBs and chlorobenzenes.     

Correlation of gas chromatographic properties of chlorobenzenes and polychlorinated biphenyls with the occurrence of reductive dechlorination by untamed microorganisms

To understand the dechlorination ability of chlorobenzenes (CBs) and polychlorinated biphenyls (PCBs) by untamed microorganisms under anaerobic condition and to correlate gas chromatographic properties with the occurrence of reductive dechlorination, introduction of CBs and PCBs in the culture medium inoculated with microorganisms from sludge and sediment, respectively, were performed. Three kinds of culture media preparing from sludge, river water and a synthetic medium were used in the experiments. HCB was degraded to 1,3,5-trichlorobenzene (1,3,5-TCB) and 1,3-dichlorobenzene (1,3-DCB) in both sludge medium and synthetic medium with inoculated microorganisms. Three PCB congeners including 2,3,4-, 3,4,5- and 2,3,4,5-CBp (chlorinated biphenyl) were not found to be dechlorinated in the river water medium with inoculation culture but to be dechlorinated in the synthetic medium. MNDO methodology was used to compute theoretical dechlorination reaction heats and GC-ECD techniques were used to estimate chromatographic data of CB and PCB congeners. Both CB and PCB congeners showed that dechlorination by untamed microorganisms under anaerobic mixed cultures were more likely to occur when larger amounts of energy were released and greater deltaln RRT value between the parent congener and the daughter product was observed. Deltaln RRT provided a more precise information on the singularity of PCBs ortho-dechlorination in an aspect of thermodynamic favorable rule.     

Thermally induced formation of PCDD and PCDF from tri- and tetrachlorobenzene in dielectric fluids

The thermal behavior of dilute (5000-50 ppm) solutions of tri- and tetrachlorobenzene in mineral oil, silicone oil, and tetrachloroethylene (TCE) has been investigated. Although pyrolyses or combustion of neat chlorobenzenes readily forms significant yields of PCDDs/PCDFs, corresponding treatment of dilute solutions was generally non-productive. This result is consistent with the proposition that, under the conditions studied, the rate-limiting step for PCDD/PCDF formation is bimolecular in chlorobenzene. In contrast, earlier studies of PCBs implied a rate-limiting step that was unimolecular in chloroaromatics. Combustion of dilute solutions of chlorobenzenes in tetrachloroethylene did produce detectable concentrations of PCDF; this result reflects combination of chlorobenzene and TCE- or TCE-derived species.     

Thermal degradation of 2-chlorophenol promoted by CuCl2 or CuCl: formation and destruction of PCDD/Fs

The oxidative degradation of 2-chlorophenol in air (equivalence ratio phi=0.8) was investigated at 350 degrees C by using the sealed tube technique under different conditions: in the gas phase and in the presence of copper chlorides (CuCl2 and CuCl in different proportions). Not only PCDD/Fs but carbon oxides and other organic products such as chlorophenols, chlorobenzenes, tetrachloroethylene and tetrachlorocyclopentenedione were quantified in order to evaluate the relative importance of reaction pathways. Additional experiments were performed to analyse the degradation products of octachlorodibenzodioxin and 2-monochlorodibenzodioxin. Although it was stated that chlorobenzenes could be formation precursors for PCDD/Fs, experimental data obtained in this work show that chlorobenzenes can also be degradation products of PCDD/Fs.     

Emissions from simulated deep-seated fires in domestic waste

The emissions from deep-seated fires in domestic waste have been investigated. The gas phase yields of PAH, PCDD/F, PCB, HCB, particles, and metals associated to the particulate matter were analysed during a series of simulated deep-seated fires. The method of extinguishment was varied and in cases where water was used for extinguishment, the runoff water was analysed for PAH, PCDD/F, PCB, hexachlorobenzene, and metals. In total six tests were performed. In four of the tests, samples of the fire residue were analysed for PCDD/F, PCBs, and chlorobenzenes.     

Heterogeneous reductive dehalogenation of PCB contaminated transformer oil and brominated diphenyl ethers with zero valent iron

Reductive dechlorination and debromination of halogenated biphenyls (PCBs) and diphenyl ethers (PBDEs) occurs efficiently at moderately elevated temperatures (350-600 °C) with zero valent iron (iron powder) in a nitrogen atmosphere. The proton donors tested were waste transformer oil, iso-octane, and n-decane. Observation of production of biphenyl and diphenyl ether and their condensation products indicates that the reaction is not simple pyrolysis, but a reduction. No halogenated organic products are observed.     

Geographical variation of persistent organochlorine concentrations in blubber of ringed seal (Phoca hispida) from the Canadian Arctic: univariate and multivariate approaches

Geographical variation of organochlorine (OC) concentrations in ringed seal (Phoca hispida) in the Canadian Arctic was studied using univariate and multivariate statistical techniques. The dataset consisted of 80 individual OC components (58 PCB congeners plus DDT- and chlordane (CHL)-related compounds, toxaphene, hexachlorocyclohexanes (HCH), chlorobenzenes (CBz), and dieldrin) determined in 221 ringed seal blubber samples from 13 locations throughout the Canadian Arctic from the period 1983 to 1989. Mean concentrations of the major OC groups in ringed seal blubber (SigmaPCBs, SigmaDDT, SigmaCHL and toxaphene), adjusted for the age and sex of the seals, showed few significant geographical differences. Principal components analysis was used to examine geographical trends. Significant differences in mean factor scores for three of four principal components were found between sampling locations. Locations in the western and high Arctic could be distinguished from those in Hudson Bay by highest scores along principal component two which was associated principally with CBz. PCB congeners with six or more chlorine substitutions declined with increasing north latitude, whereas more volatile OCs (CBz, HCH, less chlorinated PCBs) increased in the proportion of total OCs with latitude. Proportions of less chlorinated PCBs also decreased with increasing longitude, whereas slopes of regressions for more highly chlorinated PCBs increased significantly. The results were generally consistent with the 'cold condensation' hypothesis of increasing proportions of more volatile OCs with increasing latitude and distance from sources.     

Emissions of Chlorinated Organics from Two Municipal Incinerators in Ontario

In this paper the results of sampling for trace chlorinated organics at two municipal refuse incinerators in Ontario are presented. The information may be of Interest to individuals concerned with the assessment of PCDD/PCDF (polychlorinated dibenzo-p-dioxin/polychlorinated dibenzofuran) emissions from incineration of refuse and their impact on the energyfrom- waste program. PCDDs, PCDFs, PCBs (polychlorinated biphenyls), CBs (chlorobenzenes) and CPs (chlorophenols) were quantified in all process streams including refuse, ash and stack emissions. Manual sorting of refuse and collection of ash samples were carried out simultaneously with three 24-hour continuous stack sampling tests at each plant. The results suggested that the total output of PCDDs and PCDFs varied proportionately with their input at both incinerators. However, the input of PCDDs/PCDFs could not account for their total output. The chemistry of PCDDs/PCDFs in the input and output streams were different in that only heptachlorinated and octachlorinated species were present in significant quantities in the refuse while lower chlorinated species were predominant in stack emissions and ash streams. There was no correspondence between the Input of PCBs/CBs/CPs and the output of PCDDs/PCDFs. The output of PCDDs/PCDFs, however, varied Inversely with the total output of PCBs/CBs/CPs, suggesting that the latter compounds could have been partially responsible for the formation of PCDDs and PCDFs. The PCDF emissions were also affected by combustion conditions; they were higher in magnitude and consisted of predominantly tetrachlorinated and pentachlorinated species at the plant where the combustion temperatures were lower.     

Emission characteristics of PCDD/Fs, PCBs, chlorobenzenes, chlorophenols, and PAHs from polyvinylchloride combustion at various temperatures

The effect of temperature on polyvinylchloride (PVC) combustion using a downstream tubular furnace was investigated for the formation of polycylcic aromatic hydrocarbons (PAHs) and chlorinated compounds. As the temperature increased, higher levels of PAHs were generated. Chlorinated compounds reached a peak at 600 degrees C, with low emissions recorded at 300 and 900 degrees C. There was a close correlation (R2 = 0.97) among polychlorinated biphenyls (PCBs), hexachlorobenzene, pentachlorobenzene, and polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs). PAHs at all temperatures were analyzed in the gas phase. PCDD/Fs and PCBs were emitted as a solid phase at 300 and 600 degrees C and as a gas phase at 900 degrees C. For some PAHs, chlorobenzenes, and PCDD/Fs, a mathematical equation between the gas and solid phase and the reciprocal temperature in semilog proportion was derived. The proposed equation, which is log (amount in gas phase/amount in solid phase) = -A/T + B, where T is the temperature of the furnace and A and B are constants, for these species relating their gas/solid distributions showed a good relationship.     

Reaktionsverhalten von Benzol — In PPM Konzentrationen — Bei der chlorierung mit NaOCl in wässriger Lösung

The reaction behaviour of benzene in aqueous solution (ppm-concentrations) during chlorination with NaOC1 was studied. The dependence of chlorination upon the pH-value was determined quantitatively. All isomeric chlorobenzenes were formed including hexachlorobenzene. Thus, water chlorination can be regarded as another source of environmental hexachlorobenzene contamination.     

Using solar and ultraviolet light to degrade PCBs in sand and transformer oils

The present study describes the effect of the operating variables in the sensitized solar photolysis of sandy sediments contaminated by polychlorinated biphenyls (PCBs) in alkaline isopropanol. PCBs were almost completely removed in two weeks with stoichiometric release of chloride and biphenyl (BP) by a mechanism of reductive dechlorination. The concentration of the sensitizer (acetone) was the variable found to have most influence on the process. Under the same conditions, only partial dechlorination of the PCBs (34%) was observed in dielectric fluids without generating biphenyl to any appreciable extent. Direct photolysis (ultraviolet light at 254nm) of dielectric oils dissolved in alkaline isopropanol lead to 92% removal of PCBs in 60min. The observed mechanism was again that of reductive dechlorination, with stoichiometric release of chloride, and the accumulation of biphenyl, quaterphenyl and condensation products of biphenyl with isopropanol.     

Simultaneous removal of chlorinated aromatic hydrocarbons, nitrate, and chromate using micellar-enhanced ultrafiltration

Feasibility of micellar-enhanced ultrafiltration for the mixed waste that is consisted of chlorinated aromatic hydrocarbons, nitrate, and chromate was investigated using a cationic surfactant. The co-presence of nitrate and chromate did not significantly affect the removal of chlorobenzenes, and the co-presence of chlorobenzenes did not affect the removal of nitrate and chromate because chlorobenzenes were solubilized at the hydrophobic interior of the micelles by hydrophobic interaction, but nitrate and chromate were bound to the outer shell by electrostatic interaction. Micellar-enhanced ultrafiltration can be applied to treat the mixed wastes.     

Persistent organochlorines in beluga whales (Delphinapterus leucas) from the St Lawrence River estuary--II. Temporal trends, 1982-1994

Blubber samples from 16 dead beluga whales (Delphinapterus leucas) collected during 1993-1994 in the St Lawrence River estuary were analysed for PCB congeners and other persistent organochlorines (DDT-group, chlorinated bornanes (toxaphene, CHB), chlordane SigmaCHL), hexachloro-cyclohexanes (SigmaHCH), chlorobenzenes (SigmaCBz), tris(p-chlorophenyl methane (TPMe) and mirex). Concentrations and relative proportions of major individual organochlorine components were within the same range as previous results for this population. Temporal trends were studied by combining the results with data from the analysis of 44 samples (1986-1990) and (for DDT and Aroclor PCBs only) with 20 samples (1982-1985) reported by Martineau et al., 1987. Results were lipid normalized and then age-adjusted by an ANCOVA model. Significant relationships between age and concentrations of most organochlorine groups were found for females but not for males. Significant declines were observed in SigmaDDT, and Aroclor PCBs (1.5- and 1.9-fold, respectively) in males between the 1982-1985 and 1993-1994 collection periods. Significant declines were also observed for SigmaHCH and SigmaCBz in males between 1986-1988 and 1993-1994. Mean concentrations of CHBs were significantly higher in 1993-1994 than in earlier years while dieldrin, SigmaCHL, mirex, and TPMe showed no trend. Declines in concentrations of major organochlorine groups were not observed in females possibly because of higher year to year, and within year, variation. The temporal trend in DDT and PCB concentrations in male beluga blubber paralleled trends in seals, eels, and seabirds in the St Lawrence estuary observed during the 1980s.     

Destruction/removal of polychlorinated biphenyls from non-polar media. Reaction of PCB with poly (ethylene glycol)/KOH

We have found that polychlorinated biphenyls (PCB's) and other unactivated chlorobenzenes react with poly (ethylene glycols) and potassium hydroxide under mild conditions. Complete reaction with PEG occurs at 75–120°C in under two hours, to produce aryl polyglycols, the products of nucleophilic aromatic substitution. This reaction has been applied to the destruction and removal of PCB's from non-polar media, including transformer oil.     

Dechlorination of hexachlorobiphenyl by using potassium-sodium alloy

2,2',4,4',5,5'-Hexachlorobiphenyl (HCB) was dechlorinated with potassium-sodium (K-Na) alloy under an inert gas atmosphere. Solvent effect was observed in the reaction. Dechlorination yields in benzene and cyclohexane were 99.9998%, and 99.99996%, respectively. The reaction was exothermic and proceeded at room temperature. In benzene, trace amounts of polychlorinated biphenyls (PCBs) as products by stepwise dechlorination and polychlorinated quarterphenyls as product of Wurtz-Fittig reaction were detected as reaction intermediate. Reaction products were biphenyl, cyclohexylbenzene, and dicyclohexyl. In cyclohexane, there were no products of Wurtz-Fittig reaction. Dechlorination at para-position preferred to that at ortho-position, judging from analysis of PCBs as intermediates of stepwise dechlorination.     

The global re-cycling of persistent organic pollutants is strongly retarded by soils

'Persistent organic pollutants' (POPs) are semi-volatile, mobile in the environment and bioaccumulate. Their toxicity and propensity for long-range atmospheric transport (LRAT) has led to international bans/restrictions on their use/release. LRAT of POPs may occur by a 'single hop' or repeated temperature-driven air-surface exchange. It has been hypothesised that this will result in global fractionation and distillation-with condensation and accumulation in polar regions. Polychlorinated biphenyls (PCBs)--industrial chemicals banned/restricted in the 1970s--provide a classic illustration of POP behaviour. A latitudinally-segmented global PCB inventory has been produced, which shows that approximately 86% of the 1.3 x 10(6) tonnes produced was used in the temperate industrial zone of the northern hemisphere. A global survey of background surface soils gives evidence for 'fractionation' of PCBs. More significantly, however, very little of the total inventory has 'made the journey' via primary emission and/or air-surface exchange and LRAT out of the heavily populated source regions, in the 70 years since PCBs were first produced. Soils generally occlude PCBs, especially soils with dynamic turnover of C/bioturbation/burial mechanisms. This limits the fraction of PCBs available for repeated air-soil exchange. The forested soils of the northern hemisphere, and other C-rich soils, appear to be playing an important role in 'protecting' the Arctic from the advective supply of POPs. Whilst investigations on POPs in remote environments are important, it is imperative that researchers also seek to better understand their release from sources, persistence in source regions, and the significant loss mechanisms/global sinks of these compounds, if they wish to predict future trends.