The internal barriers of rotation for the 209 polychlorinated biphenyls

The internal barrier of rotation (Erot) was calculated for all 209 polychlorinated biphenyls (PCBs) by using a semi-empirical method, viz. the Austin Model 1 (AMI) Hamiltonian. The difference in total energy between a forced planar state and an optimised twisted structure was defined as Erot. The Erot values were in the range of 8.33 to 483 kj/mol, and were significantly influenced by the number of chlorine atoms inortho position. An additional structural characteristic of the PCBs influencing Erot ofortho substituted congeners was substitution by chlorine atoms in vicinalmeta positions, which is assumed to prevent outward bending ofortho substituents. This so-called buttressing effect contributed with 4 to 31 kj/mol per added chlorine atom. In conclusion, the internal barrier of rotation, calculated for all 209 PCBs, provides an important structure dependent physico-chemical parameter for multivariate modelling of future quantitative structure-activity and structure-property relationships (QSARs/QSPRs).     

Applications of polychlorinated biphenyls

Background, aim, and scope  

In the 50 years or so that polychlorinated biphenyls (PCBs) were manufactured in the USA and elsewhere, they were widely used in numerous applications because of their desirable properties. The purpose of this paper is to review and summarize in one place the factual information about the uses of PCBs, as well as to correct some misconceptions that have arisen over the years. The focus is on applications in the USA for which there is ample documentation. However, use patterns were probably similar worldwide.     

Reductive dechlorination for remediation of polychlorinated biphenyls

Technologies such as thermal, oxidative, reductive, and microbial methods for the remediation of polychlorinated biphenyls (PCBs) have previously been reviewed. Based on energy consumption, formation of PCDD/F, and remediation efficiency, reductive methods have emerged as being advantageous for remediation of PCBs. However, many new developments in this field have not been systematically reviewed. Therefore, reductive technologies published in the last decade related to remediation of PCBs will be reviewed here. Three categories, including catalytic hydrodechlorination with H₂, Fe-based reductive dechlorination, and other reductive dechlorination methods (e.g., hydrogen-transfer dechlorination, base-catalyzed dechlorination, and sodium dispersion) are specifically reviewed. In addition, the advantages of each remediation technology are discussed. In this review, 108 articles are referenced.     

Neurotoxicology of ortho-substituted polychlorinated biphenyls

Ortho-substituted, non-planar PCBs reduce dopamine content in both nonhuman primate brain and pheochromocytoma (PC12) cells. Planar, dioxin-like, congeners have no effect on dopamine content in PC12 cells. Additional in-vitro results indicate that dopamine reduction by PCBs is due to inhibition of tyrosine hydroxylase activity.     

Partitioning behavior of polychlorinated biphenyls

Partitioning of polychlorinated biphenyls (PCBs) among several idealized environmental compartments was investigated using equilibrium conditions. Simulations with single equilibrations suggested that PCB mixtures do not weather significantly. However, simulations with multiple equilibrations of a selected phase with renewed phases suggested that PCB mixtures have the potential to weather. These simulations were strongly influenced by temperature; both the compositions and total amount of the PCBs in each phase at equilibrium changed significantly with temperature. These simulations lend support to the hypothesis that lower and higher chlorinated PCBs behave differently in the environment.     

Quantifying the global fractionation of polychlorinated biphenyls

Due to the wide range of their physical-chemical properties, polychlorinated biphenyls (PCBs) have played an important role in the derivation of the global fractionation hypothesis, which predicts changes in the composition of persistent organic pollutant mixtures with latitude. Recent historical emission estimates, the derivation of an internally consistent property data set, in combination with a zonally averaged global fate and transport model, allow a quantitative investigation of the compositional shifts PCBs experience as a function of environmental compartment, latitude and time. Model simulations reproduce the higher relative abundance of lighter PCB congeners with increasing latitude, observed in air and soil, and quantify the relative importance of partitioning, persistence and emissions in establishing PCB patterns. Compositional variations consistent with global fractionation, as well as inverted concentration profiles with higher levels in the Arctic than at lower latitudes, are consistent with only minor fractions of the global PCB inventory being transferred northward.     

Ultrasonically-assisted electrocatalytic dechlorination of polychlorinated biphenyls

Commercial mixtures of PCB's (Aroclors) were dechlorinated to biphenyl by ultrasonically-assisted electroreduction with and without soluble catalysts. Ultrasound increased the rate of electrolysis at stirred-mercury-pool electrodes by 2- to 3-fold.     

利用紫外光降解多氯联苯(PCBs)的研究进展

本文综述了PCBs在各种溶剂中的紫外光化学反应特性和降解途径 :PCB的光化学反应以氢取代氯的脱氯反应为主 ,除此之外 ,在水或醇等极性溶液中 ,还存在羟基化反应 ;PCB的光化学反应活性与其氯原子的数量和取代位置有关。文章最后还简述了光降解在治理受PCB污染土壤方面的应用     

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.     

Fungal laccase-catalyzed degradation of hydroxy polychlorinated biphenyls

Hydroxy polychlorinated biphenyls (hydroxy PCBs) are toxic metabolites of PCBs. Their toxicity such as strong endocrine disruption demands effective remediation methods. Laccases from Trametes versicolor and Pleurotus ostreatus were tested to degrade hydroxy PCBs. Optimum pHs for both enzymes were around 4.0. Laccase from T. versicolor degrades hydroxy PCBs more rapidly than that from P. ostreatus. The enzymatic activities remained little changes in up to 10% organic solvents, but decreased rapidly in more than 10% acetone, acetonitrile or DMSO. Degradation rate constants decreased with increase of chlorination and no degradation was observed with tetra-, penta- and hexa-chloro hydroxy PCBs in non-mediated reactions. However, the tetra- to hexa-chloro hydroxy PCBs were degraded by laccase from T. versicolor in the presence of the mediator 2,2,6,6-tetramethylpiperidine-N-oxy radical. The other mediators, 4-ethyl-2-methoxyphenol, 2,2'-azino-bis(3-ethylbenzthiazoline sulfonic acid) diammonium salt and 1-hydroxybenzotriazole and humic acid, also enhanced degradation of all the hydroxy PCBs except 4-hydroxy-2',3,3',4',5,5'-hexachlorobiphenyl. The results showed that 3-hydroxy biphenyl was more resistant to laccase degradation than 2- or 4-hydroxy analogues. Significant linear-correlations (coefficient of determination, r2 = 0.9097 and 0.8186 for laccases from P. ostreatus and T. versicolor, respectively) were found between the ionization potentials and the removal rate constants of hydroxy PCBs.     

Detailed study on the levels of polychlorinated dibenzo-p-dioxins,polychlorinated dibenzofurans and polychlorinated biphenyls in Yusho rice oil

One bottle of Yusho rice oil was obtained from a Yusho family in 1998. The levels of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and polychlorinated biphenyls (PCBs) in the causal oil were investigated with two different approaches and the individual concentrations of all the 17 2,3,7,8-substituted PCDD/F and 14 coplanar PCB (Co-PCB) congeners were elucidated for the first time. The concentrations of PCDDs and PCDFs were found to be 0.60 and 8.8 ppm, respectively. For PCBs, more than 130 PCB peaks were observed and a total concentration of 850 ppm including 170 ppm of Co-PCBs was obtained. The toxic equivalents (TEQs) of PCDDs, PCDFs, and Co-PCBs were calculated to be 17, 470, and 120 ppb, respectively. The relative contribution of these classes to the total TEQ in Yusho oil is 3%, 77%, and 20%, respectively, indicating that PCDFs play a major role in the toxicity of Yusho oil. Furthermore, it was confirmed that 2,3,4,7,8-penta-CDF contributes 58% to the total TEQ, supporting the view that this compound is the principal causal agent in Yusho poisoning. It is noteworthy that the most toxic 2,3,7,8-tetra-CDD was newly discovered, although it contributes only 0.1% to the total TEQ. Based on our data, the smallest TEQ intake during the latent period was estimated to be 0.067 mg for Yusho patients. This value is about 60% of that previously reported, suggesting a lower minimum threshold level for the development of the toxic symptoms of Yusho.     

Investigation of saponification for determination of polychlorinated biphenyls in marine sediments

The effects of saponification conditions (temperature and water content of saponifying solution) on the determination of chlorinated biphenyls (CBs) in marine sediments were investigated. Although highly chlorinated biphenyls (nona- to deca-CBs) decomposed during high-temperature saponification, the degree of degradation was reduced by adding water to the ethanolic potassium hydroxide saponifying solution. Room-temperature saponification yielded quantitative recovery of highly chlorinated biphenyl surrogates but low extraction efficiencies of lightly chlorinated biphenyls (mono- to di-CBs). The same samples were analyzed by other extraction techniques, for example, pressurized liquid extraction, and analytical results were compared. The mono- and di-CB concentrations were correlated with the extraction temperatures of various extraction techniques. In particular, the concentrations of some CB congeners (CB11, CB14) were higher with saponification. The low degree of degradation of highly chlorinated biphenyls and the high recovery of lightly chlorinated biphenyls were compatible when room-temperature and high-temperature saponification were combined. Except for the anomalies of CB11 and CB14, the combined method gave satisfactory results for analysis of PCBs.     

Effect of photosensitizer diethylamine on the photodegradation of polychlorinated biphenyls

The objective of this study was to investigate the effect of diethylamine and xenon simulated sunlight on the photodegradation of two forms of PCBs including PCBs in transformer oil and PCB congener 138. The result of GC chromatograms illustrated the shifting pattern of higher chlorinated biphenyls in transformer oil degraded to lower chlorinated biphenyls with the extension of exposure time. The effect of diethylamine and xenon simulated sunlight was significant on the photodegradation of both PCBs in transformer oil and congener 138. The initial degradation rates of congener 138 (1.14 x 10(-9) to 4.47 x 10(-9) mol l(-1) h(-1)) were in direct proportion to the initial concentrations of congener 138 which confirmed the pseudo-first-order reaction of PCB photodegradation. The apparent quantum yields (phi) of congener 138 using diethylamine in xenon photoreactor were ranged between 2.08 x 10(-2) and 9.8 x 10(-4). PCB congeners 123, 97, 70, 67, 33, 29, 17, 12, and 9 were detected as the descendants of the photodegradation of congener 138 through dechlorination. The major pathway of congener 138 photodegradation in this study was via para-dechlorination.     

多氯联苯污染沉积物质量评价研究进展

介绍了多氯联苯污染沉积物质量评价的研究进展 ,其中 ,简单介绍了多氯联苯的有关概况及环境行为、沉积物质量评价方法及基准研究进展 ;最后 ,重点介绍了包括多氯联苯在内的憎水性有机物污染沉积物质量评价的研究现状及存在问题。     

Atmospheric deposition of polychlorinated dibenzo-p-dioxins, polychlorinated dibenzofurans, and dioxin-like polychlorinated biphenyls in the Kanto Region, Japan

The atmospheric bulk (dry and wet) deposition of dioxins was investigated at four locations (Tokyo, Yokohama, Tsukuba, and Tanzawa) in the Kanto region (in Japan) over one year using a stainless-steel pot. Annual average polychlorinated dibenzo-p-dioxins/polychlorinated dibenzofurans (PCDD/PCDF) deposition fluxes were estimated to be from 450 to 1300 ng/m2/yr, and the annual average TEQ fluxes from 5.7 to 17 ng-TEQ/m2/yr at the four locations. The PCDD/PCDF deposition flux was higher in winter than in summer. The deposition flux could be related to ambient temperature, particularly for less chlorinated PCDDs/PCDFs, while the deposition flux is not necessarily related to the amount of precipitation. The PCDD/PCDF deposition flux increased as the particle deposition flux increased, for the winter samples. Based on the ratio of the PCDD/PCDF deposition fluxes to the particle deposition fluxes, the contribution of the reentrainment of soil particles to the TEQ of PCDD/PCDF deposition was considered to be negligible in this region. Based on the air concentrations monitored near our deposition sampling points by the municipalities, the ratio of the annual deposition flux to the annual average air concentration was roughly estimated to be 0.082 cm/s. The range of deposition flux in the Kanto region was estimated to be from 1.5 to 31 (median: 9.8) ng-TEQ/m2/yr based on the range of air concentration data measured by the municipalities. The total annual deposition flux in the entire Kanto region was estimated to range from 50 to 900 g-TEQ/yr (median 320 g-TEQ/yr). This estimated flux was of the same order as the sum of estimated emissions from municipal solid waste incinerators and industrial waste incinerators in the Kanto region. The contributions of dioxin-like PCBs in Yokohama, Tsukuba, and Tanzawa depositions were less than 10% of the total TEQ; however, in Tokyo it was almost equal to or more than 50%.     

Synthesis of polychlorinated biphenyls (PCBs) using the Suzuki-coupling

An improved synthesis of polychlorinated biphenyls (PCBs) utilizing a palladium-catalyzed cross-coupling reaction (Suzuki-coupling) is described. The coupling of (chlorinated) aryl boronic acids 1-3 with bromochlorobenzenes 4 using the standard conditions of the Suzuki-coupling gave the desired PCB congeners 5-7 in good to excellent yields. The self-coupling product of the aryl boronic acids is the major impurity of this reaction. 3,4,5-trichlorophenyl derivatives such as 10 can be synthesized by coupling of an aryl boronic acid with the corresponding bromochloroaniline 8. The approach offers the advantage of high selectivity and good yields compared to conventional methods such as the Cadogan reaction and allows the use of less toxic starting materials.     

Performance of a semi-industrial scale gasification process for the destruction of polychlorinated biphenyls

A semi-industrial scale test was conducted to thermally treat mixtures of spent oil and askarels at a concentration of 50,000 ppm and 100,000 ppm of polychlorinated biphenyls (PCBs) under a reductive atmosphere. In average, the dry-basis composition of the synthesis gas (syngas) obtained from the gasification process was: hydrogen 46%, CO 34%, CO2 18%, and CH4 0.8%. PCBs, polychlorinated dibenzo-p-dioxins, and polychlorinated dibenzofurans (PCDDs/PCDFs) in the gas stream were analyzed by high-resolution gas chromatography (GC)-mass spectrometry. The coplanar PCBs congeners 77, 105, 118, 156/ 157, and 167 were detected in the syngas at concentrations < 2 x 10(-7) mg/m3 (at 298 K, 1 atm, dry basis, 7% O2). The chlorine released in the destruction of the PCBs was transformed to hydrogen chloride and separated from the gas by an alkaline wet scrubber. The concentration of PCBs in the water leaving the scrubber was below the detection limit of 0.002 mg/L, whereas the destruction and removal efficiency was > 99.9999% for both tests conducted. The concentration of PCDDs/PCDFs in the syngas were 8.1 x 10(-6) ng-toxic equivalent (TEQ)/m3 and 7.1 x 10(-6) ng-TEQ/m3 (at 298 K, 1 atm, dry basis, 7% O2) for the tests at 50,000 ppm and 100,000 ppm PCBs, respectively. The only PCDD/F congener detected in the gas was the octachloro-dibenzo-p-dioxin, which has a toxic equivalent factor of 0.001. The results obtained for other pollutants (e.g., metals and particulate matter) meet the maximum allowed emission limits according to Mexican, U.S., and European regulations for the thermal treatment of hazardous waste (excluding CO, which is a major component of the syngas, and total hydrocarbons, which mainly represent the presence of CH4).