Accurate sampling of PCDD/F in high temperature flue-gas using cooled sampling probes

In a laboratory-scale combustion reactor, flue-gas samples were collected at two temperatures in the post-combustion zone, 700 °C and 400 °C, using two different water-cooled sampling probes. The probes were the cooled probe described in the European Standard method EN-1948:1, referred to as the original probe, and a modified probe that contained a salt/ice mixture to assist the cooling, referred to as the sub-zero probe. To determine the efficiency of the cooling probes, internal temperature measurements were recorded at 5 cm intervals inside the probes. Flue-gas samples were analyzed for polychlorinated dibenzo-p-dioxin and dibenzofurans (PCDD/Fs). Samples collected at 700 °C using the original cooling probe showed higher concentrations of PCDD/Fs compared to samples collected using the sub-zero probe. No significant differences were observed between samples collected at 400 °C. The results indicated that artifact formation of PCDD/Fs readily occurs during flue-gas sampling at high temperatures if the cooling within the probe is insufficient, as found for the original probe at 700 °C. It was also shown that this problem could be alleviated by using probes with an enhanced cooling capacity, such as the sub-zero probe.Although this may not affect samples collected for regulatory purposes in exit gases, it is of great importance for research conducted in the high-temperature region of the post-combustion zone.     

河流沉积物中有机污染物的分析研究进展

总结了近年来河流沉积物中有机污染物的研究进展 ,集中评述了国内有关沉积物中多环芳烃、有机氯农药和多氯联苯的分析研究现状 ,包括样品采集、样品前处理和样品分析 ,并对今后河流、湖泊及水库沉积物中污染物的分析工作作了展望     

Principal component analysis for soil contamination with organochlorine compounds

In order to investigate the distribution pattern of individual organochlorine compounds in soil samples collected from the sites (Canary Island – Spain, China, Germany, India, Romania, Russia, Serbia, Swiss, UK) affected by industrial activities to the more remote areas, principal component analysis was performed on the data taken from literature. Loading plots pointed out the strong correlation among the variables. Score plots revealed similar PCB- and OCP-soil patterns for majority of the investigated sites. Nevertheless, the temporal differences of PCB-soil loads have been identified: the late 1990s and early 2000s concentrations are similar to those of the early 1940s, and they are below the levels existed in 1980. The most pronounced PCB concentrations characterized the soil from 1966. For OCPs the influence of sites location on the detected concentration has been revealed: China and India were characterized by comparably higher loads of DDX (DDT and its metabolites) and of HCH-isomers, respectively.     

广州地区孕妇羊水中PCBs暴露水平初步研究

随机采集广州地区非职业PCBs(polychlorinated biphenyls,多氯联苯)暴露单胎孕妇分娩时羊水,分析羊水中PCBs浓度水平;结合孕妇临床资料(年龄、孕周、身体质量指数(body mass index,BMI))以及孕妇居住环境信息等,阐明了广州地区非职业暴露孕妇羊水PCBs蓄积的影响因素。结果表明,∑33PCBs浓度为15.91-324.38 ng·g-1,平均值为114.34±83.52 ng·g-1,中值为84.8 5ng·g-1;其中十氯含量最低,平均浓度为2.66±3.46 ng·g-1,中值为1.47 ng·g-1;六氯PCBs含量最高,平均浓度为28.79±33.84 ng·g-1,中值为17.48 ng·g-1。样本中有31种PCBs同分异构体在孕妇羊水中检出,分别为PCB 8、28、30、49、52、70、74、77、82、87、99、101、105、114、118、126、128、138、153、156、158、166、169、170、179、180、183、187、189、198和209;羊水主要的PCBs暴露以五氯PCBs、六氯PCBs和七氯PCBs为主,主要的同分异构体为PCB 138(4.73%)、179(4.15%)、153(3.92%)、183(3.89%)、166(3.77%)、187(3.74%)以及180(3.67%);暴露水平与美国、西班牙、加拿大等地区相比属于严重水平。统计结果显示,年龄、身体质量指数和孕周与PCBs蓄积有显著性正相关关系;工业区居住的孕妇相与非工业区居住孕妇相比,上述统计结果更为显著。     

被动加标在水生生态风险评价中的应用——以多氯联苯分配系数的测定为例

准确的水生生态风险评价需要可靠的毒性数据,而其获取要求在一定时间范围内,水体中污染物的浓度保持恒定。对疏水性有机污染物进行水体生物毒性测试时,通常采用有机溶剂加标,然而该方式可能因为污染物的挥发和降解、容器壁吸附、生物摄取等问题,水体中污染物浓度持续下降,导致污染物的浓度-效应关系难以明确。近期为了克服这些问题,被动加标用于替代溶剂加标,通过污染物在加标体系中平衡分配来维持精确和恒定的水体浓度,同时还可通过测定加标聚合物中污染物的浓度来监测水体浓度。首先介绍了被动加标方法及其材料选择,讨论了该方法在生态风险评价中的主要应用,包括分配系数的测定、体外细胞测试、体内生物积累及毒性测试,以及沉积物毒性评价等。然后,以测定代表污染物多氯联苯在聚二甲基硅氧烷与水间的分配系数为例,详细说明被动加标的操作流程。最后,讨论了被动加标方法的优缺点,并对其在水生生态风险中的应用前景进行了展望。     

北江中上游地表水和沉积物中PAHs和PCBs污染特征和风险评估

采用气相色谱-质谱法（GC-MS）测定了北江中上游流域地表水和沉积物样品中多环芳烃（PAHs）和多氯联苯（PCBs）类污染物的含量,分析了PAHs和PCBs的污染水平和空间分布,并评估了污染物的健康风险和生态风险.结果表明,16种PAHs单体在所有水样和沉积物样品中均被检出,检出范围分别为41.82~443.04 ng·L^-1和59.58~635.73 ng·g^-1,北江中上游PAHs的污染水平为中、轻度.水中PAHs以二环芳烃和三环芳烃为主,沉积物中以三环芳烃和四环芳烃为主.在水样中检出了17种PCBs,浓度范围0.81~287.50 ng·L^-1,以六氯联苯和七氯联苯为主;沉积物中检出了8种PCBs,含量范围0.13~3.96 ng·g^-1,以五氯联苯和七氯联苯为主.整个调查区域内地表水中PAHs和PCBs的终生致癌风险指数小于10^-4,处于中、低水平;非致癌风险指数均小于1,不存在非致癌风险.采用风险商值（RQ）法对地表水中污染物进行生态风险评价,研究区域内地表水中PAHs和PCBs生态风险总体处于中低风险水平,个别点位存在重度风险的污染物单体,值得引起重视.采用沉积物质量基准法（SQGs）对沉积物中污染物进行生态风险评估,沉积物中PAHs和PCBs均处于较低的生态风险水平.     

Sexual difference in PCB congener distributions of burbot (Lota lota) from Lake Erie

Concentrations of 86 congeners of polychlorinated biphenyls (PCBs) were determined for 25 adult female and 25 adult male burbot (Lota lota) from Lake Erie. Significant differences in mean proportions of total PCB concentration between males and females ages 14–17 were found for 26 congeners. Males generally had higher mean proportions of hexachloro congeners, whereas females had higher mean proportions of more highly chlorinated congeners. In contrast, only four congeners exhibited differences between males and females ages 6–13 in mean proportions of total PCB. Therefore, the sexual difference in PCB congener distribution widened for older burbot. Males ages 14–17 also had higher proportions of certain hexachloro congeners than the other three demographic groups (males ages 6–13, females ages 6–13, and females ages 14–17) we examined. The reverse was true for more highly chlorinated congeners. The results supported a previous hypothesis that older male burbot spent a substantial amount of time feeding in the vicinity of mouths of rivers with sediment contaminated with PCBs. However, additional studies are needed to clarify and corroborate this apparent “hot spot” effect, such as seasonal movements, spatial distributions, and diet of burbot; and PCB congener distributions of various species of prey fishes captured at various locations throughout the eastern basin of Lake Erie and at different locations in the contaminated rivers.     

Levels of Persistent Organochlorine Residues in Eggs of Greater Flamingos from the Guadalquivir Marshes (Doñana), Spain

Organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs) residue levels were determined in 53 unhatched eggs from greater roseus flamingos (Phoenicopterus ruber). Eggs were collected in 1996 from the National Park of Doñana (Guadalquivir marshes, Southwest Spain), immediately after one breeding colony abandoned the nesting site due to predator attacks. The main metabolite of p,p′-DDT, p,p′-DDE, was the OCP residue found at higher concentrations, with a geometric mean of 721 ng/g wet weight. Residues of other pesticides, including some hexachlorocyclohexane isomers, hexachlorobenzene, aldrin, heptachlor, and heptachlor-epoxide, were detected at much lower concentrations. The sum of PCBs was 528 ng/g, with PCB congeners #187 and #153 being the most prominent in eggs. The pattern observed in these compounds of industrial origin corresponded more to Aroclor 1260 than to any other commercial mixture. Levels of organochlorine residues indicate a medium degree of exposure, and they are not considered of any concern for the flamingo population. In particular, neither p,p′-DDE nor PCB levels were found to be correlated with the eggshell thickness.     

Confirmation of polychlorinated biphenyl (PCB) distribution in the blood and verification of simple quantitative method for PCBs based on specific congeners

We measured the concentration of each polychlorinated biphenyl (PCB) congener in whole blood, plasma and blood cells, and investigated the distribution of PCBs in human blood using high-resolution gas chromatography/high-resolution mass spectrometry (HRGC/HRMS). The PCB concentrations in plasma and whole blood in terms of lipid concentrations were almost equal, with a correlation coefficient of r = 0.972. In the blood, the ratio of PCBs in blood cells to those in plasma was generally about 1:9 and the congener distribution patterns in blood cells and plasma were similar.We performed verification of a simple mass screening method by obtaining information on the main PCB congeners for investigations on human accumulation and exposure. The total concentration of the seven PCB congeners (UNEP-7) proposed to the United Nations Environment Programme (UNEP) by Muir and Morita was about 50% of the total concentration of all PCB congeners, and UNEP-30 was about 80%. The seven main congeners in the blood (MCB-7) showed a value that was about 60%, and MCB-30 showed a value that was about 90%. Determinations with the main congeners in the blood showed a correlation of r = 0.990 or more between the main eight congeners (MCB-7 plus #74) and the total PCB concentration for all congeners. The results suggest that, although total PCB concentration can be effectively estimated from the main seven congeners, the main eight congeners would be preferable, and that the use of these congeners in the simple mass screening method would be effective for populations in areas uncontaminated by PCBs.     

Spatial character of polychlorinated biphenyls from soil and respirable particulate matter in Taiyuan, China

As one of China’s great metropolises, Taiyuan is affected by heavy chemical industry and manufacture of chemical products, and faces pollution from polychlorinated biphenyls (PCBs). Therefore, this study was conducted to determine the PCB concentrations in various environmental media in Taiyuan. We collected 15 soil samples, 34 respirable particulate matter (PM) samples (17 of PM_2.5 and 17 of PM₁₀) from urban areas of Taiyuan, and measured a total of 144 PCB congeners (including some coeluting PCB congeners). The total PCB concentrations were 51–4.7 × 10³ pg g⁻¹ in soil, 27–1.4 × 10² pg m⁻³ in PM_2.5 and 16–1.9 × 10² pg m⁻³ in PM₁₀. Of the PCB homologues, the dominant PCBs detected in the various media were all tri-CBs. Soil was relatively the most polluted media. Furthermore, principal-component analysis revealed that the major PCB source in Taiyuan may be associated with the main commercial PCB through long-range transmission. Toxic equivalency (TEQ) concentrations (based on ten dioxin-like PCBs) ranged from N.D. to 5.9 × 10⁻³ pg-WHO TEQ g⁻¹ in soil, 2.0 × 10⁻⁴–3.4 × 10⁻³ pg-WHO TEQ m⁻³ and 1.0 × 10⁻⁴–1.2 × 10⁻³ pg-WHO TEQ m⁻³ in PM_2.5 and PM₁₀, respectively. In previous studies, PCBs were not a severe component of contaminant in Taiyuan; however, this study suggested there is a potential threat of human exposure to PCBs for residents of Taiyuan.