碳纳米管对水中多氯联苯的吸附动力学

通过静态吸附实验研究了碳纳米管（CNTs）对水中多氯联苯（PCBs）的吸附动力学特性,包括1种单壁碳纳米管（SWCNTs）和3种多壁碳纳米管（MWCNTs）,并对4种CNTs的物理特征及孔径分布进行了分析。结果表明,SWCNTs的比表面积和总孔容最大,分别为228.210 m2·g-1和1.515 4 cm3·g-1。CNTs对PCBs的吸附速率很快,40 min吸附量可达到平衡时的90%以上,80 min左右达到吸附平衡,且SWCNTs的吸附能力远大于MWCNTs。运用拟一级和拟二级动力学模型对实验数据进行拟合,表明拟二级模型更适合描述CNTs对PCBs的吸附过程。     

Reaction of polychlorinated biphenyls with mercaptans in non-polar media: Formation of polychlorobiphenyl sulfides

Polychlorinated biphenyls (PCB's) react readily with alkyl mercaptans in non-polar solvents such as toluene or transformer oil. Reactions occur readily with KOH as the base in the presence of a variety of phase transfer catalysts, including phosphonium salts, crown ethers, and poly (ethylene glycols).     

Generator column determination of aqueous solubilities for non-ortho and mono-ortho substituted polychlorinated biphenyls

Aqueous solubilities of four non-ortho and eight mono-ortho substituted PCBs were determined using a generator-column technique followed by subsequent off-line GC/ECD analysis of the aqueous solutions. The method is based on pumping water through a column containing glass beads coated with the congener being studied and has been used to measure solubilities at room temperature. The method circumvents many of the experimental difficulties encountered with the traditional shake-flask system. Aqueous solubility of 3,3′,4,4′-tetrachlorobiphenyl determined by this procedure is compared with data obtained from the shake-flask method and the computational method. The precision of replicate measurements is better than ±6.5%. Aqueous solubilities determined for 12 congeners ranged from 6.07 × 10⁻¹¹ to 4.47 × ⁻⁹ mol/L and generally decreased with molecular weight and increased with degree of ortho-chlorine substitution within a molecular-weight class.     

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.     

Improved extraction procedures for polychlorinated biphenyls in solid samples with aqueous sodium hydroxide under autoclave conditions

The efficacy of the extraction of polychlorinated biphenyls (PCBs) from varnish-infiltrated insulating papers as a model of solid materials with an aqueous sodium hydroxide (NaOH) by autoclaving at 121 degrees C for 30 min was compared with those for the conventional procedures, i.e., saponification with 1 N ethanolic NaOH in a boiling water bath for 60 min and extraction with benzene in a Soxhlet apparatus. The newly invented autoclaving method was found to be superior to the conventional ones, yielding approximately 5- to 6-fold cumulative PCB congeners without being accompanied by extended decomposition. Therefore, the autoclave-based sample treatment is recommended for more accurate determination of PCBs in the case of PCB-impregnated solid materials such as hardened oils and resin-coated or -infiltrated papers instead of being treated conventionally.     

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.     

Background levels of polychlorinated biphenyls in British soils

The concentrations of PCBs in soil samples collected at rural and urban locations in Britain are reported. PCBs were detected in all samples analysed, within the range 2.3 to 444 μg kg⁻¹ (ppb), with a mean concentration of 22.8 μg kg⁻¹ and a median value of 7.2 μg kg⁻¹. A distinct sub-group of samples has a range of 2.3 to 19.2 μg kg⁻¹, with a mean of 7.5 μg kg⁻¹ and a median value of 6.8 μg kg⁻¹. These values are consistent with published data from other industrialised countries. Measurement was carried out using a two stage clean-up of soil extracts, with concentrated sulphuric acid and florisil, followed by gas chromatography and electron capture detection.     

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%.     

Distribution of polychlorinated dibenzo-p-dioxins, polychlorinated dibenzofurans and non-ortho coplanar polychlorinated biphenyls in river and offshore sediments

Polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and non-ortho chlorine substituted coplanar polychlorinated biphenyl (Co-PCBs, non-ortho Cl CBs) in river and offshore sediment samples were analyzed isomer-specifically using (13)C-labeled their respective internal standards and a selected ion monitoring method of high resolution gas chromatograph-mass spectrometry (GC-MS). These compounds were found in all samples analyzed. The average concentrations of the total PCDDs, PCDFs and Co-PCBs in the 23 sediment samples taken from rivers were 11 000, 1300 and 160 pgg(-1) of dry wt, respectively, those in six offshore sediments were 7600, 980 and 52 pgg(-1), respectively. The concentrations of Co-PCBs were much lower than those of PCDDs and PCDFs in all sediment samples. The magnitude of these concentrations was in the order of lower reach of river > offshore area > upper reach of river. The concentrations of PCDDs and PCDFs in the rural river were higher than those in the urban river, whereas the Co-PCB concentration in an urban river was six times higher than that in a rural river. The Co-PCB concentrations in the urban area and industrial area were higher than that in any other area. These findings suggest that the pollution by PCDDs and PCDFs was derived from some kinds of incinerations and herbicides applied in the past and that Co-PCB pollution was caused by PCB preparation used in the past in urban and industrial areas and by municipal waste incineration in urban areas.     

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.     

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.     

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).     

Concentrations of polychlorinated dibenzo-p-dioxins, polychlorinated dibenzofurans, and non-ortho and mono-ortho polychlorinated biphenyls in blood of Yusho patients

We measured the concentrations of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), non-ortho polychlorinated biphenyls (non-ortho PCBs) and mono-ortho polychlorinated biphenyls (mono-ortho PCBs) in blood collected from 279 Yusho patients living in Japan, 92 Yusho-suspected persons living in Japan and 127 normal controls living in Fukuoka Prefecture, and compared among the groups in terms the concentrations of these compounds. The total toxic equivalents (TEQ) concentrations of PCDDs, PCDFs, non-ortho PCBs, and mono-ortho PCBs in the bloods of Yusho patients and Yusho-suspected persons were 161.4 and 51.2 pg TEQ/g lipid, respectively and were about 3.5 and 1.1 times higher than those of normal controls, respectively. Although the TEQ concentrations of PCDDs, non-ortho PCBs, and mono-ortho PCBs among Yusho patients, Yusho-suspected persons and normal controls were nearly the same, the PCDFs levels of Yusho patients were significantly higher than those of Yusho-suspected persons and about 10.3 times higher than those of normal controls. In Yusho patients, PCDFs contributed about 65% to the total TEQ concentration. Among the PCDFs congeners for Yusho patients, the concentration of 2,3,4,7,8-pentachlorodibenzofuran (PeCDF) was about 11.3 times higher than that of normal controls. These findings indicated that Yusho patients even now, more than 34 years after the outbreak of Yusho, have much higher blood levels of 2,3,4,7,8-PeCDF in general than do unaffected persons.     

Monitoring of polychlorinated biphenyls in Belgian human adipose tissue samples

Polychlorinated biphenyls (PCBs) were monitored in Belgian human adipose tissue samples from deceased individuals (n=100). Their mean age was 52, ranging from 2 to 91 years. There were 57 men and 43 women. Other known variables were date of autopsy and place of residence. No information about diet or occupation was available. The seven marker congeners PCB 28, 52, 101, 118, 138, 153 and 180 were analysed in the samples with a GC-MS/MS method validated according to Commission Decision 2002/657/EC. Extracted fat was cleaned-up over a glass column filled with n-hexane, acid silica, deactivated alumina and anhydrous sodium sulfate. The whole procedure was subjected to a rigorous quality control programme with retention times, ion chromatograms and intensity ratios of the monitored product ions as identification criteria. The total PCB concentration ranged between 10 and 1640 ng g-1 fat, with a mean value of 658 ng g-1 fat. In the age groups of 0-9 (n=1), 10-19 (n=4), 20-29 (n=11), 30-39 (n=13), 40-49 (n=15), 50-59 (n=14), 60-69 (n=14), 70-79 (n=20), 80-89 (n=6) and 90-99 (n=2), the mean total PCB concentrations were 10, 134, 253, 445, 557, 687, 807, 962, 959, and 1191 ng g-1 fat, respectively. So, there was an increase of PCB body burden with age. For the male subjects (n=57; mean age of 53) the mean total PCB concentration was 633 ng g-1 fat. For the female subjects (n=43; mean age of 52) it was 690 ng g-1 fat. There was no significant sex-related difference in the concentrations of marker PCBs.     

Microbial dechlorination of polychlorinated biphenyls in anaerobic sewage sludge.

The potential of a chlorophenol (CP)-adapted consortium to dechlorinate polychlorinated biphenyls (PCBs) in sewage sludge was investigated. Results show that dechlorination rates differed significantly depending on sludge source and PCB congener. Higher total solid concentrations in sewage sludge and higher concentrations of chlorine in PCB resulted in slower dechlorination rates. No significant difference was found for 2,3,4,5-CB dechlorination from pH 6.0 to pH 8.0; however, dechlorination did not occur at pH 9.0 during a 41-day incubation period. Results show that at concentrations of 1 to 10 mg/L, the higher the PCB concentration, the faster the dechlorination rate. In addition, dechlorination rates were in the following order: methanogenic conditions > sulfate-reducing conditions > denitrifying conditions. The addition of acetate, lactate, pyruvate, and ferric chloride decreased lag times and enhanced dechlorination; however, the addition of manganese dioxide had an inhibitory effect. Dechlorination rates were also enhanced by the addition of PCB congeners, including 2,3,4-CB, 2,3,4,5-CB and 2,3,4,5,6-CB in mixture. Overall results show that the CP-adapted consortium has the potential to enhance PCB dechlorination. The optimal dechlorination conditions presented in this paper may be used as a reference for feasibility studies of PCB removal from sludge.     

Lactational transfer of mercury and polychlorinated biphenyls in polar bears

We examined concentrations of total mercury (tHg, inorganic and methylated forms) and polychlorinated biphenyls (PCBs) in blood and milk from free-ranging Southern Beaufort-Chukchi Sea polar bears (Ursus maritimus) to assess maternal transfer of contaminants during lactation and the potential health risk to nursing young. Concentrations of contaminants in the blood of dependent and juvenile animals (ages 1-5 years) ranged from 35.9 to 52.2 μg kg(-1) ww for tHg and 13.9 to 52.2 μg kg(-1) ww (3255.81-11067.79 μg kg(-1) lw) for ΣPCB(7)s, similar to those of adult females, but greater than adult males. Contaminant concentrations in milk ranged from 5.7 to 71.8 μg tHg kg(-1)ww and 160 to 690 μg ΣPCB(11)s kg(-1) ww (547-5190 μg kg(-1) lw). The daily intake levels for tHg by milk consumption estimated for dependent young were below the tolerable daily intake level (TDIL) of tHg established for adult humans. Although the daily intake levels of PCBs through milk consumption for cubs of the year exceeded the TDIL thresholds, calculated dioxin equivalents for PCBs in milk were below adverse physiological thresholds for aquatic mammals. Relatively high concentrations of non-dioxin like PCBs in polar bear milk and blood could impact endocrine function of Southern Beaufort-Chukchi Sea polar bears, but this is uncertain. Transfer of contaminants during mid to late lactation likely limits bioaccumulation of dietary contaminants in female polar bears during spring. As polar bears respond to changes in their arctic sea ice habitat, the adverse health impacts associated with nutritional stress may be exacerbated by tHg and PCBs exposure, especially in ecologically and toxicologically sensitive polar bear cohorts such as reproductive females and young.     

Spatial distribution of polychlorinated biphenyls in High Tatras lake sediments

The objective of the present study was to gain insight on the spatial distribution of seven polychlorinated biphenyl (PCB) congeners in the High Tatras mountain range in Eastern Europe. Twenty high mountain lakes were sampled on their top-core sediment. Despite the relative uniform composition of PCB congeners among the lakes, there are important differences in the observed concentrations. Moderate top-core sediment concentrations of PCB congeners were observed (1.9 to 38 ng/g dw for ∑PCB) in comparison to other high mountain or Arctic areas. The variation in PCB concentrations can partly be explained by a possible altitudinal effect, resulting in higher PCB concentrations at higher (colder) altitudes. Part of this enhanced accumulation of PCBs could be caused by external factors (topography and meteorology) and internal lake factors (sediment dynamics). Many of these factors were not quantified for all individual lakes and their influence could, therefore, only be studied for some.