基于危险化学品储存的区域生态环境风险评价

借鉴现有的生态风险评价方法,提出适合危险化学品储存的区域生态风险评价体系,即区域生态风险受体确定,评价终点选择,暴露途径和方式,暴露剂量分析与计算,风险表征以及区域生态风险管理对策等。研究结果表明:在有风模式中,鸟类的不可接受风险范围最远可达下风向7km,蛙类的不可接受风险最远可达下风向27km。大部分敏感点的蛙类急性暴露剂量都超标,处于不可接受风险水平;80%的敏感点的鸟类处于不可接受风险水平。根据风险评价结果,提出从防范措施、应急预案、环境监测和生态补偿4个方面制定区域生态风险管理措施。该区域生态环境风险评价研究为同类型区域生态环境风险评价提供借鉴作用。     

Trace contamination with dioxin-like chemicals: evaluation of bioassay-based TEQ determination for hazard assessment and regulatory responses

Many recent dioxin contamination events have been traced back to poisoned animal feed or feed ingredients. Therefore, enforcement authorities placed limits on the levels of dioxins in food and feed or implemented strict monitoring and control programs. The levels in force are generally expressed as TEQ values, which inherently accepts the underlying hypothesis that the effects of dioxin-like chemicals are additive. TEQ determination involves either chemo-analysis, with high-resolution gas chromatography in combination with high-resolution mass spectroscopy, or bio-analysis. Bio-analytical methods, more particularly the reporter gene expression method CALUX, are advantageous due to their high throughput rate and low cost. Moreover, the CALUX methodology detects the overall dioxin-like toxicity, rather than the limited number of compounds investigated by chemo-analysis. Bioanalytical methods such as CALUX also differ from chemo-analysis in that the contribution of antagonistic as well as synergistic effects, which violate the additivity principle, can be detected. The application of bio-analytical methods can facilitate a broader assessment of public health risks by intensifying the current monitoring programs in terms of both sample numbers and types. Bio-analysis provides information on the total dioxin-like activity of the samples under study (hazard assessment); however, chemo-analysis is still needed to identify the predominant contaminants (congener identification) for risk management.     

Assays of polychlorinated biphenyl congeners and co-contaminated heavy metals in the transgenic Arabidopsis plants carrying the recombinant guinea pig aryl hydrocarbon receptor-mediated β-glucuronidase reporter gene expression system

The transgenic Arabidopsis plant XgD2V11-6 carrying the recombinant guinea pig (g) aryl hydrocarbon receptor (AhR)-mediated β-glucuronidase (GUS) reporter gene expression system was examined for assay of polychlorinated biphenyl (PCB) congeners and co-contaminated heavy metals. When the transgenic Arabidopsis plants were treated with PCB126 (toxic equivalency factor; TEF: 0.1) and PCB169 (TEF: 0.03), the GUS activity of the whole plants was increased significantly. After treatment with PCB80 (TEF: 0), the GUS activity was nearly the same level as that treated with 0.1% dimethylsulfoxide (DMSO) as a vehicle control. After exposure to a 1:1 mixture of PCB126 and PCB169, the GUS activity was increased additively. However, after exposure to a mixture of PCB126 and PCB80, the GUS activity was lower than that of the treatment with PCB126 alone. Thus, PCB80 seemed to be an antagonist towards AhR. When the transgenic plants were treated with each of the heavy metals Fe, Cu, Zn, Cd and Pb together with PCB126, Cd and Pb increased the PCB126-induced GUS activity. On the other hand, Fe, Cu and Zn did not affect the PCB126-induced GUS activity. In the presence of the biosurfactant mannosylerythritol lipid-B (MEL-B) and the carrier protein bovine serum albumin (BSA), the PCB126-induced GUS activity was increased, but the Cd-assisted PCB126-induced GUS activity was not affected. Thus, MEL-B and BSA seemed to increase uptake and transport of PCB126, respectively.     

Recombinant human AhR-mediated GUS reporter gene assays for PCB congeners in transgenic tobacco plants in comparison with recombinant mouse and guinea pig AhRs

Four expression plasmids for recombinant human aryl hydrocarbon receptor (hAhR) consisting of a ligand binding domain of hAhR, a DNA-binding domain of LexA and a transactivation domain of VP16 as well as β-glucuronidase (GUS) reporter genes were constructed. All the expression plasmids were transformed into tobacco plants. The selected transgenic tobacco plants were used to assay. PCB congeners showed GUS activity in a TEF-dependent manner. The selected transgenic tobacco plant XhD4V17 was compared with the transgenic tobacco plants XmD4V26 and XgD2V23 containing recombinant mouse (m) AhR-mediated GUS reporter gene expression cassette and recombinant guinea pig (g) AhR-mediated GUS reporter gene expression cassette for PCB congener-inducible GUS activity. The data revealed that the tobacco plant XgD2V23 was the most active in PCB congener-inducible GUS activity. In a 1:1 mixture of PCB126 and PCB80 a reduced PCB126-induced GUS activity was observed in plant XgD2V23, which could possibly be due to interaction between PCB126 and PCB80.     

精确三维光谱数据活性关系方法应用于ToxCast数据库中雌激素受体数据分类、验证和特征提取的建模策略

本文利用三维光谱数据活性关系方法(3D-SDAR)对ToxCast数据库中1 528种化合物的雌激素潜能(表示为18分复合高通量筛选生物测定)进行建模。由于缺少170核磁共振(NMR)仿真软件,信息量最大的碳-碳3D-SDAR指纹随着一些指标变量增强,这些指标变量包括来自羰基和酰胺的氧原子、酯基、磺酰、硝基、脂肪族羟基和酚羟基官能团。为了评价本文作者所开发模型的预测性能的真实性,美国环境保护署为研究人员提供了2 008种化合物组成一套盲测。其中,543种化合物有文献可查数据—他们的结合力有助于评估开发模型的外部分类精度：得到预测精度0.62,敏感度0.71,和特异度0.53的结果。与其他建模技术相比,本文作者开发的模型几乎没有简化建模集和预测集之间的性能。3D-SDAR映射技术可以识别拟雌激素活性所必需的结构特征：1) 存在一个酚的OH官能团或环己烯酮,2)与第一苯酚环上的氧距离6 ?到8 ?的第二芳香或酚环,3) 存在一个与苯酚环的几何中心距离大约6 ?的甲基官能团,4)一个靠近(距离几何中心～4?)某个苯酚环的羰基官能团。
精选自Svetoslav H. Slavov, Richard D. Beger. Rigorous 3-dimensional spectral data activity relationship approach modeling strategy for toxcast estrogen receptor data classification, validation, and feature extraction. Environmental Toxicology and Chemistry: Volume 36, Issue 3, pages 823–830, July 2017. DOI: 10.1002/etc.3578
详情请见http://onlinelibrary.wiley.com/wol1/doi/10.1002/etc.3578/full
     

重庆市煤矸山周边农用地土壤重金属污染评价和定量溯源解析

以重庆市南川区某煤矸山周边农用地土壤为研究对象,运用内梅罗指数法、地累积指数法和GIS地统计分析土壤重金属污染水平和分布特征,并采用相关性分析、主成分分析（PCA）和绝对因子得分-多元线性回归分析（APCS-MLR）,探析研究区土壤重金属来源及其贡献率.结果表明,煤矸山周边旱地土壤中8项重金属含量均显著高于水田（P<0.05）,Cd、Hg、As、Pb和Cr含量显著高于园地（P<0.05）;园地土壤中Cu、Ni和Zn含量显著高于水田（P<0.05）.内梅罗综合污染指数表现为旱地（2.77）>园地（1.04）>水田（0.59）,重金属污染程度由大到小表现为：Cd>Cu>Ni>Zn>Hg、As、Cr和Pb.污染累积程度由大到小表现为：Cd>Hg>Cu>Ni>Zn>As>Cr>Pb.污染源解析表明,Cd和Hg存在显著正相关关系（r=0.756,P<0.01）,主要受到煤矸山长期堆存等矿业活动影响,贡献率分别为51.6%和52.9%.Cu、Ni和Zn之间存在显著正相关关系（r为0.755~0.955,P<0.01）,主要受到施肥等农业活动影响,贡献率分别为72.3%、63.3%和59.2%.As和Pb主要受到土壤母质等自然因素影响,贡献率分别为60.8%和86.9%.Cr主要受到施肥等农业活动和土壤母质等自然因素共同影响,贡献率分别为38.9%和40.9%.应重点加强对Cd的来源管控和污染防治.     

典型酚类污染物内分泌干扰效应研究——对斑马鱼发育及核受体介导基因调控的分子影响

以斑马鱼为研究对象,观察2,4,6-三氯酚（2,4,6-trichlorophenol）、4-氯-3-甲酚（4-chloro-3-methylphenol）和4-硝基苯酚（4-nitrophenol）3种酚类污染物对斑马鱼胚胎发育早期阶段形态学指标的影响,借助q-RT-PCR方法对斑马鱼胚胎分别暴露于0.1,0.5和2.5mg/L至120hpf幼鱼8个重要受体（雄激素受体（AR）、甲状腺激素受体（TR）、芳香烃受体（AhR）、雌激素受体（ER）、糖皮质激素受体（GR）、孕烷X受体（PXR）、盐皮质激素受体（MR）、过氧化物酶体增殖物激活受体（PPAR））相关基因的转录水平进行了研究;进一步采用分子对接和分子动力学模拟的方法研究污染物与筛选出的影响受体（ER、AhR、PXR、GR以及MR）之间的相互作用过程.结果表明,在5和10mg/L的浓度下3种酚类污染物都显著影响斑马鱼的发育,造成脊柱弯曲、心包水肿等不良影响;基因结果显示2,4,6-三氯酚暴露导致ER的基因下调,雌激素受体α（er1）基因在2.5mg/L浓度下下调2.1倍.4-氯-3-甲酚显著影响ER、AhR以及PXR的相关基因,表现为在0.5和2.5mg/L暴露er1基因显著下调1.8和2.2倍,ahr2和pxr基因在0.1和2.5mg/L的浓度下分别下调1.7和1.8倍和上调3.5和3.2倍.4-硝基苯酚暴露使GR、MR核心受体基因发生调控变化,糖皮质激素受体基因（gr）在低中浓度下分别显著上调2.0和2.1倍,最高浓度下下调1.9倍.盐皮质激素受体基因（mr）在中高浓度下分别下调1.9和2.1倍,在最低浓度下显著上调1.7倍;分子计算结果显示它们与相关受体通过疏水和氢键等相互作用而稳定结合,且均方根偏差（RMSD）在5ns后稳定.这3个典型酚类污染物主要通过斑马鱼ER、AhR、PXR、GR、MR受体介导产生内分泌干扰效应并影响其早期生长发育.     

基于多通道分布式VOCs在线监测质谱系统精准识别企业污染源

建立一套适用于工业园区VOCs无组织排放的监管溯源系统,该系统通过多通道分布式质谱在企业内部和厂界进行多个在线监测点位连续监测,实现对VOCs的无组织排放污染源的初步识别.监测数据结合正交矩阵因子分解(PMF)模型和二元条件概率函数(CBPF)方法精准识别园区内不同范围尺度的污染源.该系统成功应用于台州市化工园区内某医...     

应用受体学说模型研究硝基苯类化合物的致毒机理

应用受体学说推出的定量结构活性相关(QSAR)模型研究了硝基苯类化合物的致毒机理,结果表明,硝基苯类化合物的主要致毒机理是化合物亲电中心与受体分子亲核活性中心发生反应．并引入硝基数目和位置指示变量I,分析表明,苯环上硝基的数目和位置的差别引起化合物的最低未占轨道能ELUMO的变化,即化合物亲电结合能的变化,从而影响了化合物的生物活性．     

Dissolved organic carbon from sewage sludge and manure can affect estrogen sorption and mineralization in soils

In this study, effects of sewage sludge and manure borne dissolved organic carbon (DOC) on 17β-estradiol (E2) and 17α-ethinylestradiol (EE2) sorption and mineralization processes were investigated in three agricultural soils. Batch equilibrium techniques and equilibrium dialysis methods were used to determine sorption mechanisms between DOC, estrogens and the soil solid phase. It was found that that the presence of organic waste borne DOC decreased estrogen sorption in soils which seems to be controlled by DOC/estrogen complexes in solution and by exchange processes between organic waste derived and soil borne DOC. Incubation studies performed with ¹⁴C-estrogens showed that DOC addition decreased estrogen mineralization, probably due to reduced bioavailability of estrogens associated with DOC. This increased persistence combined with higher mobility could increase the risk of estrogen transport to ground and surface waters.