Cytochrome c adducts with PCB quinoid metabolites

Polychlorinated biphenyls (PCBs) are a group of 209 individual congeners widely used as industrial chemicals. PCBs are found as by-products in dye and paint manufacture and are legacy, ubiquitous, and persistent as human and environmental contaminants. PCBs with fewer chlorine atoms may be metabolized to hydroxy- and dihydroxy-metabolites and further oxidized to quinoid metabolites both in vitro and in vivo. Specifically, quinoid metabolites may form adducts on nucleophilic sites within cells. We hypothesized that the PCB-quinones covalently bind to cytochrome c and, thereby, cause defects in the function of cytochrome c. In this study, synthetic PCB quinones, 2-(4′-chlorophenyl)-1,4-benzoquinone (PCB3-pQ), 4-4'-chlorophenyl)-1,2-benzoquinone (PCB3-oQ), 2-(3′, 5′-dichlorophenyl)-1,4-benzoquinone, 2-(3′,4′, 5′-trichlorophenyl)-1,4-benzoquinone, and 2-(4′-chlorophenyl)-3,6-dichloro-1,4-benzoquinone, were incubated with cytochrome c, and adducts were detected by liquid chromatography-mass spectrometry (LC-MS) and matrix-assisted laser desorption/ionization time of flight mass spectrometry (MALDI TOF). Sodium dodecyl sulfate polyacrylamide gel electrophoresis (SDS-PAGE) was employed to separate the adducted proteins, while trypsin digestion and liquid chromatography-tandem mass spectrometry (LC-MS/MS) were applied to identify the amino acid binding sites on cytochrome c. Conformation change of cytochrome c after binding with PCB3-pQ was investigated by SYBYL-X simulation and cytochrome c function was examined. We found that more than one molecule of PCB-quinone may bind to one molecule of cytochrome c. Lysine and glutamic acid were identified as the predominant binding sites. Software simulation showed conformation changes of adducted cytochrome c. Additionally, cross-linking of cytochrome c was observed on the SDS-PAGE gel. Cytochrome c was found to lose its function as electron acceptor after incubation with PCB quinones. These data provide evidence that the covalent binding of PCB quinone metabolites to cytochrome c may be included among the toxic effects of PCBs.     

The effects of 3,3′,4,4′-tetrabromobiphenyl on rats fed diets containing a constant level of copper and varying levels of molybdenum

Copper (Cu) metabolism is altered in rats fed diets high in molybdenum (Mo) and low in Cu. This 10-week study was carried out to examine the effects of supplemental Mo (7.5–240 μg/g diet) on male Sprague–Dawley rats fed diets adequate in Cu (5 μg/g diet) and to determine the susceptibility of Mo-treated animals to the environmental pollutant 3,3′,4,4′-tetrabromobiphenyl (TBB). After 7 weeks of dietary treatment, half of the rats in each group received a single IP injection of TBB (150 μM/kg bw), while the other half received the corn oil vehicle. Rats sacrificed at 10 weeks showed no effects of Mo on growth, feed efficiency, or selected organ or tissue weights. Dose-dependent effects on plasma Mo (0–5.1 μg/mL), plasma Cu (0.95–0.20 μg/mL), and bone Cu (3.4–10 μg/g) in control through the high dose were found. Cu sequestration in the bone of Mo-treated rats is a new finding. TBB treatment resulted in dramatic weight loss and loss of absolute organ mass. Relative organ weights were increased, except for the thymus. TBB altered the concentrations of certain amino acids. Compared to control rats, this polybrominated biphenyl congener significantly decreased plasma Cu and ceruloplasmin at higher concentrations of dietary Mo and promoted the process of plasma Cu decrease by Mo, suggesting a combined effect.     

Dietary antioxidants (selenium and N-acetylcysteine) modulate paraoxonase 1 (PON1) in PCB 126-exposed rats

Environmental pollutants polychlorinated biphenyls (PCBs), especially dioxin-like PCBs, cause oxidative stress and associated toxic effects, including cancer and possibly atherosclerosis. We previously reported that PCB 126, the most potent dioxin-like PCB congener, not only decreases antioxidants such as hepatic selenium (Se), Se-dependent glutathione peroxidase, and glutathione (GSH) but also increases levels of the antiatherosclerosis enzyme paraoxonase 1 (PON1) in liver and serum. To probe the interconnection of these three antioxidant systems, Se, GSH, and PON1, we examined the influence of varying levels of dietary Se and N-acetylcysteine (NAC), a scavenger of reactive oxygen species (ROS) and precursor for GSH synthesis, on PON1 in the absence and presence of PCB 126 exposure. Male Sprague–Dawley rats, fed diets with differing Se levels (0.02, 0.2, or 2 ppm) or NAC (1 %), were treated with a single intraperitoneal injection of corn oil or various doses of PCB 126 and euthanized 2 weeks later. PCB 126 significantly increased liver PON1 mRNA, protein level and activity, and serum PON1 activity in all dietary groups but did not consistently increase thiobarbituric acid levels (thiobarbituric acid reactive substances, TBARS), an indicator of lipid oxidation and oxidative stress, in liver or serum. Inadequate (high or low) dietary Se decreased baseline and PCB 126-induced aryl hydrocarbon receptor (AhR) expression but further increased PCB 126-induced cytochrome P450 1A1 (CYP1A1) expression, the enzyme believed to be the cause for PCB 126-induced oxidative stress. In addition, a significant inverse relationship was observed not only between dietary Se levels and PON1 mRNA and PON1 activity but also with TBARS levels in the liver, suggesting significant antioxidant protection from dietary Se. NAC lowered serum baseline TBARS levels in controls and increased serum PON1 activity but lowered liver PON1 activities in animals treated with 1 μmol/kg PCB 126, suggesting antioxidant activity by NAC primarily in serum. These results also show an unexpected predominantly inverse relationship between Se or NAC and PON1 during control and PCB 126 exposure conditions. These interactions should be further explored in the development of dietary protection regimens.     

工业企业集聚区周边土壤环境质量综合评价指标体系与分区管理对策研究

土壤环境质量综合评价指标体系是识别土壤环境污染、指导土壤环境管理及开发利用的有效工具。在土壤环境质量评价方法和国内外标准分析的基础上,提出了建立土壤环境质量综合评价指标体系的基本框架;结合"压力-状态-响应"模型(PSR模型),考虑不同工业区特征污染物,建立了包含通用指标和备选指标的土壤环境质量综合评价指标体系。以此评价指标体系为导向,为指导不同类型工业集聚区科学发展提出了工业区周边土壤环境质量分区管理的对策建议。     

响应面法优化电渗析处理褐藻酸钠废水工艺

采用电渗析器处理过滤的褐藻酸钠废水,褐藻酸钠废水初始水质如下:Ca2+(56 mg/L)、Cl-(1 808 mg/L)、电导率(7.24 mS/cm)。处理目标值如下:Ca2+(60 mg/L)、Cl-(300 mg/L)、电导率(2.50 mS/cm)。运用Design-Expert分析软件,采用Box-Behnken的中心组合设计方法,研究了流量、电压及淡水浓水体积比及其交互作用对直流电耗的影响。建立了电渗析处理褐藻酸钠废水的二次多项数学模型,并以电渗析的直流电耗为响应值做响应面,确定电渗析处理褐藻酸钠废水的最佳工艺条件为:流量200 L/h、电压40 V、淡水浓水体积比1∶1。在此条件下电渗析的直流电耗最小为0.45 kWh/kg,电渗析器处理后的水质如下:Ca2+(56 mg/L)、Cl-(259 mg/L)、电导率(2.00 mS/cm),达到处理目标。     

上海市生态系统质量评价及其演变特征分析研究

城市化发展引起的土地利用方式和生态系统质量的变化逐渐引起人们的重视,人类的社会经济活动已经对生态系统的结构和功能造成了很大影响。以上海市为研究对象,从生态系统结构、功能和胁迫3个方面构建生态系统质量评价模型,研究了2000年、2005年、2010年3个时期生态系统质量变化、空间差异及其影响因素。结果表明,崇明县和中心城区生态结构指数最高;崇明县功能指数最高,中心城区最低;崇明县受城市化胁迫最小,中心城区胁迫最大。崇明县是上海市生态系统质量最好的区域,3个时期生态系统质量指数均处于1级水平,中心城区生态系统质量最差。提供了一种生态系统质量评价的方法,研究结果揭示了上海市2000-2010年生态系统质量演变趋势,可以为上海市生态系统管理提供参考依据。     

低声能密度超声波破解污泥的效果研究

以生活污水处理厂污泥为研究对象,采用超声波技术进行污泥破解,研究不同声能密度和超声作用时间对污泥预处理效果的影响。结果表明,低声能密度超声波在120min内可破碎污泥絮体,分解细胞壁,使胞内有机物溶出;延长超声作用时间、增加声能密度均有助于污泥中有机物、氮、磷等物质的释放,当声能密度为0.10 W/mL、超声作用时间为120 min时,溶解性COD(SCOD)、可溶性蛋白质、可溶性多糖、TN、氨氮、TP、正磷酸盐的浓度较破解前分别提高了29.99、44.49、17.31、14.06、3.19、1.35、1.00倍;破解污泥释放出的氮以有机氮为主,磷的释放作用不明显。利用Pearson相关性分析得知,在声能密度变化条件下,除TP外,SCOD、可溶性蛋白质、可溶性多糖、TN、氨氮、正磷酸盐之间均呈极显著相关(p0.01);在超声作用时间变化条件下,各指标间均呈极显著相关(p0.01)。     

论排污许可证制度对点源排放控制政策的整合

中国水污染防治政策很多,包括环境影响评价、"三同时"、排污收费等,但各项政策基本是分散和独立执行的,没有核心和基础的政策,不成体系,缺乏效率。基于排污许可证作为政府的执法文件的角度,论证了将分散的点源排放控制政策围绕排污许可证整合为系统的排放控制政策体系。中国已具备实施排污许可证制度的基础条件,以排污许可证制度为基础的政策整合对现有点源排放控制政策进行了修改、补充和改进,将其整合为一个系统的点源排放控制政策体系,使各级管理部门可以各司其职,协调合作;协调整合不同类型的政策手段,使命令控制、经济激励和劝说鼓励3类手段相互补充,进一步提高政策执行效率,降低政策执行成本,提高排放控制政策效果、效率,降低执法和守法成本。     

一种兼顾水质目标和成本投入的流域减排措施优化方法

综合考虑断面水质及治污成本,构建流域治污减排措施优化模型,分析单位污染物去除成本与断面水质改善间的关系,并以承德市武烈河流域治污减排优化为例,绘制治污减排措施优化曲线,提出优化方案。结果表明,在达到流域水质要求的情况下,优化后,治污减排项目由34项缩减到22项,平均单位COD去除成本由1.44万元/t下降到0.65万元/t,同时实现了流域水质达标和降低投入成本的要求。     

定电位电解法和非分散红外法测定误差分析

随着环保部和中国环境监测总站对标准的更新,非分散红外吸收法测定固定污染源废气中二氧化硫和氮氧化物已列入国家环境监测标准方法,并在各级环境监测站中逐渐普及应用。同时,作为国家标准的定电位电解法依然在用,且测量的可靠性、稳定性能良好。在相同环境下使用两种方法同时测定同一污染源废气中的二氧化硫和氮氧化物,探讨了其结果间产生偏差的原因,并对各种影响因素进行了分析和评价。