北部湾文蛤对石油烃和多氯联苯的氧化应激响应

为探讨海域现场双壳类动物对有机污染物积累的抗氧化响应,在北部湾潮间带11个采样点采集文蛤(Meretrix meretrix)样品,测定其软组织中w(TPHs)(TPHs为石油烃)、w(PCBs)(PCBs为多氯联苯)以及鳃、内脏中GSH(还原型谷胱甘肽),GSSG(氧化型谷胱甘肽)、SOD(超氧化物歧化酶)、CAT(过氧化氢酶)、GPx(谷胱甘肽过氧化物酶)、GST(谷胱甘肽转硫酶)、TBARS(硫代巴比妥酸反应物)7种氧化应激物的水平,分析其空间分布特征,并进行有机污染物含量与氧化应激物响应值之间的相关性分析. 结果表明:文蛤软组织中w(TPHs)和w(PCBs)分别为78.22~300.71μg/g和4.23~26.68ng/g,最大值均出现在S10采样点(防城港西湾);内脏中CAT活性较高,其他氧化应激物均在鳃中有较高水平. 与对照采样点S1(湛江流沙湾)相比,S2、S3、S6、S10、S11等5个采样点文蛤组织内SOD、CAT、GST、GPx、GSH水平较低;大多数采样点文蛤鳃中w(GSSG)较低,而S3、S4、S6、S7、S9、S11等6个采样点文蛤内脏中w(GSSG)较高;大多数采样点文蛤组织中TBARS含量较低,表明其抗氧化防御机能尚未丧失. TPHs显著抑制文蛤鳃中的w(GSSG) (R=-0.64,P<0.05),PCBs显著抑制文蛤鳃中的GPx(R=-0.72,P<0.05)和GST(R=-0.72,P<0.05)的活性,表明w(GSSG)及GPx和GST的活性可作为指示北部湾有机污染的生物标志物.      

西安城区大气中多氯联苯的气粒分配研究

为了解西安城区大气中多氯联苯(PCBs)的气粒分配规律,于2012年春季对西安城区大气中气态和颗粒态样品进行每周一次的主动采样.结果表明,西安城区大气中PCBs的总浓度(气态和颗粒态)为62.05~454.18pg/m3,主要以气态为主.由Clausius-Clapeyron方程得到的斜率较陡(-5193.24),表明春季大气中的PCBs主要受西安城区附近地面挥发释放的影响.PCBs的气粒分配系数(KP)与过冷饱和蒸汽压(PoL)高度相关,由logKP和logPoL线性回归得到的斜率mr(-0.46~-0.37)均高于平衡状态理论值-1,说明西安城区大气中的PCBs气粒分配尚未达到平衡状态.采用Junge-Pankow吸附模型和Harner-Bidleman吸收模型对PCBs颗粒态百分比(φ)及KP进行了模拟,结果显示两种模型均较好地预测了PCBs的气粒分配行为,但与实验测得的值相比,两种模型均高估了φ值及KP值.     

硫化纳米零价铁对PCB153的降解研究

硫化纳米零价铁(S-nZVI)是近年来兴起的一种纳米零价铁改性材料,已有研究发现其在重金属污染物去除方面具有较好的效果,而有关其对多氯联苯(PCBs)的反应活性目前尚未见报道.因此,本研究对比了采用前置硫化合成法制备的S-nZVI(S/Fe=0.103)、纳米零价铁(nZVI)和羧甲基纤维素稳定纳米零价铁(CMC-nZVI)3种纳米零价铁材料降解六氯联苯PCB153的反应动力学,研究了pH值、阴离子、腐殖酸(HA)等因素对该反应的影响,分析了反应前后材料表面性质的变化,探讨了脱氯路径和反应机理.结果表明,3种纳米零价铁材料对PCB153的降解反应符合准一级动力学,降解机理相似,降解效果依次为CMC-nZVInZVIS-nZVI.硫化改性降低了nZVI去除PCB153的反应活性,S-nZVI表面的硫铁化物并未直接参与PCB153降解反应,S-nZVI反应活性低的原因可能是硫铁化物的形成损耗了一部分Fe~0的还原能力.此外,与CMC-nZVI、nZVI不同,高pH更有利于S-nZVI对PCB153的降解,阴离子和HA对3种纳米零价铁活性的影响规律相似.研究结果可为S-nZVI在持久性有机污染物降解中的应用提供理论依据和技术支持.     

鱼中氯化二苯并二噁(PCDD)和氯化二苯并呋喃(PCDF)的分析

本工作建立了鱼中从四氯到八氯的二苯并二(口恶)(口英)和二苯并呋喃的分析方法。鱼样品经消化后以己烷提取,提取液经两套层析柱净化后,用反相HPLC进一步净化并分为两个级份。采用GC/SIM-MS测定各PCDD和PCDF。     

Organochlorines in the surface sediments of the Bahiret el Bibane lagoon (Tunisia,Southwestern Mediterranean Sea)

Organochlorines (including organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs)) were analysed in 10 surface sediment samples collected from the Bahiret el Bibane lagoon, which is one of the most productive lagoons and one of the most important active commercial fish traps in the southern Tunisia. The aim was to obtain information concerning the recent deposition of these compounds in this area, together with the levels, the distribution and any potential biological risk. Total concentrations of OCPs and PCBs in the sediments ranged from below the limit of detection (?1 and from 29.5 to 88.2?ng?g^?1?dw, respectively. The spatial distribution of PCBs suggested that the sources of these contaminants are probably located outside the lagoon and are transported by water currents and atmospheric deposition. Compared with some other regions of the world, the Bahiret el Bibane lagoon exhibited low to moderate levels of PCBs and OCPs. According to established sediment quality guidelines, PCBs and Lindane at most of the study sites would be more concerned for the ecotoxicological risk in the Bahiret el Bibane lagoon. The results of this study could provide a useful aid for the sustainable marine management of the region.     

Hydroxypropyl-β-cyclodextrin as non-exhaustive extractant for organochlorine pesticides and polychlorinated biphenyls in muck soil

Hydroxypropyl-β-cyclodextrin (HPCD) was used as a non-exhaustive extractant for organochlorine pesticides (OCs) and polychlorinated biphenyls (PCBs) in muck soil. An optimized extraction method was developed which involved using a HPCD to soil mass ratio of 5.8 with a single extraction period of 20 h. An aging experiment was performed by spiking a muck soil with ¹³C-labeled OCs and non-labeled PCBs. The soil was extracted with the optimized HPCD method and Soxhlet apparatus with dichloromethane over 550 d periodically. The HPCD extractability of the spiked OCs was greater than of the native OCs. A decreased in HPCD extractability was observed for the spiked OCs after 550 d of aging and their extractability approached those of the natives. The partition coefficient between HPCD and soil (log K_CD-Soil) was negatively correlated with the octanol-water partition coefficient (log K_OW) with r² = 0.67 and p < 0.05.     

生物与化学表面活性剂协同洗脱土壤中PCBs的研究

通过序批实验和土柱淋洗实验研究了由生物表面活性剂鼠李糖脂(RL)与非离子化学表面活性剂十二烷基醇聚氧乙烯(6)醚(POE(6))混合得到的复配试剂洗脱污染土壤中多氯联苯(PCBs)的作用效果及其作用机理。结果表明,同一土样中,从批实验得到的PCBs洗脱率略高于土柱淋洗实验。RL与POE(6)两种单一试剂对人工污染土样中的PCBs洗脱率均大于60%,而对陈化土样中的洗脱率均不到20%,且土壤中的TOC含量越高,PCBs的洗脱率越低。在质量浓度为301 mg/L(10 CMC)及1 505 mg/L(50 CMC)的RL-POE(6)复配试剂中,RL与POE(6)对人工污染土壤中PCBs的洗脱具有一定的协同作用。当复配试剂的浓度为301 mg/L时,RL与POE(6)对陈化土样中PCBs的洗脱没有协同作用;但当RL-POE(6)的浓度增加到1 505 mg/L时,RL与POE(6)对陈化土样中PCBs的洗脱具有明显的协同作用。     

Comparison of the concentrations of polychlorinated biphenyls and dioxins in mothers affected by the Yusho incident and their children

Accumulated maternal dioxins are passed onto the fetus and neonate via the placenta and maternal milk. In Japan in 1968, an accidental human exposure to rice oil contaminated with polychlorinated biphenyls (PCBs) and other dioxin-related compounds, such as polychlorinated dibenzofurans (PCDFs), led to development of Yusho oil disease. We investigated differences in blood dioxin concentrations in mother-children pairs affected by the Yusho incident. From 2002 to 2008, blood samples were collected from 26 pairs of Yusho mothers and their children (19 mothers, 26 children). Specific congeners of seven polychlorinated dibenzo-p-dioxins (PCDDs), ten PCDFs, and four non-ortho PCBs were analyzed. The children had significantly lower TEQ concentrations of PCDDs, PCDFs, and coplanar PCBs compared to their mothers. The mother-child difference in blood concentrations varied with the congeners; the largest for 2,3,4,7,8-pentaCDF and the smallest for 1,2,3,4,6,7,8-heptaCDD. The level for 2,3,4,7,8-pentaCDF, which characterizes Yusho oil disease, was approximately 17-30 times higher in the mothers than in the general population, whereas there were no significant differences between children in the formula-fed group and the general population. In contrast, the mean level for 2,3,4,7,8-pentaCDF in the breast-fed group was approximately 1.5 times, (range 0.5-6.5 times) higher than that in the general population. Over 30 years after the Yusho incident, the mean blood dioxin levels in the offspring were only a fraction of the levels in their mothers. This is more consistent with exposure via breast milk than via transplacental transfer in the Yusho incident.     

Persistent organochlorine pollutants and menstrual cycle characteristics

An evolving body of evidence suggests an adverse relation between persistent organochlorine pollutants (POPs) and menstruation, though prospective longitudinal measurement of menses is limited and served as the impetus for study. We prospectively assessed the relation between a mixture of persistent organochlorine compounds and menstrual cycle length and duration of bleeding in a cohort of women attempting to become pregnant. Eighty-three (83%) women contributing 447 cycles for analysis provided a blood specimen for the quantification of 76 polychlorinated biphenyls and seven organochlorine pesticides, and completed daily diaries on menstruation until a human chorionic gonadotropin confirmed pregnancy or 12 menstrual cycles without conception. Gas chromatography with electron capture detection was used to quantify concentrations (ng g⁻¹ serum); enzymatic methods were used to quantify serum lipids (mg dL⁻¹). A linear regression model with a mixture distribution was used to identify chemicals grouped by purported biologic activity that significantly affected menstrual cycle length and duration of bleeding adjusting for age at menarche and enrollment, body mass index, and cigarette smoking.A significant 3-d increase in cycle length was observed for women in the highest tertile of estrogenic PCB congeners relative to the lowest tertile (β = 3.20; 95% CI 0.36, 6.04). A significant reduction in bleeding (<1 d) was observed among women in the highest versus lowest tertile of aromatic fungicide exposure (γ = −0.15; 95% CI −0.29, −0.00). Select POPs were associated with changes in menstruation underscoring the importance of assessing chemical mixtures for female fecundity.     

Influence of activated carbon amendment on the accumulation and elimination of PCBs in the earthworm Eisenia fetida

In this study we investigated the use of activated carbon (AC) as a soil amendment for reducing bioavailability of polychlorinated biphenyls (PCBs) to the earthworm Eisenia fetida. Artificial soil was contaminated with PCBs and used in bioaccumulation experiments fresh or after aging for 19 months. PCB bioaccumulation in earthworms was reduced by 68% when AC was placed as a layer without mixing and by 94% when AC was manually mixed into the soil. Aging of the same AC mixed soil for 19 months resulted in an overall reduction of 99% in PCB biouptake. AC-treated aged soil also showed two orders of magnitude lower equilibrium aqueous concentrations of PCBs compared to untreated aged soils. The findings from this study indicate that application of engineered sorbents like AC to PCB impacted soils may greatly reduce PCB uptake at the base of the terrestrial food chain.