Influence of rice straw burning on the levels of polycyclic aromatic hydrocarbons in agricultural county of Taiwan

Atmospheric particulate and polycyclic aromatic hydrocarbons (PAHs) size distribution were measured at Jhu-Shan (a rural site) and Sin-Gang (a town site) in central Taiwan during the rice straw burning and non-burning periods. The concentrations of total PAHs accounting for a roughly 58% (34%) increment in the concentrations of total PAHs due to rice-straw burning. Combustion-related PAHs during burning periods were 1.54–2.57 times higher than those during non-burning periods. The mass median diameter (MMD) of 0.88–1.21 m in the particulate phase suggested that rice-straw burning generated the increase in coarse particle number. Chemical mass balance (CMB) receptor model analyses showed that the primary pollution sources at the two sites were similar. However, ricestraw burning emission was specifically identified as a significant source of PAH during burning periods at the two sites. Open burning of rice straws was estimated to contribute approximately 6.3%–24.6% to total atmospheric PAHs at the two sites.     

深圳主要河流中雌激素污染调查

调查了深圳市10条主要河流雌激素污染现状,结果表明,双酚A在深圳市河流中28个监测点中27个点有检出,检出率96.4％,质量浓度为未检出～6.042 μg/L;17β雌二醇(E2)在深圳市河流中28个监测点中8个点有检出,检出率28.6％,质量浓度为未检出～0.011 6μg/L,能检出的17β雌二醇(E2)值大都在0.001 5μg/L～0.003 9 μg/L之间;雌三醇(E3)仅在1个监测点(新洲河河口)有检出,对壬基酚均未检出.     

多溴联苯醚与雌激素受体作用的CoMFA／CoMSIA研究

以多溴联苯醚类化合物的ER亲合力为生物活性指标，运用基于配体结构信息的CoMFA／CoMSIA方法，模拟该类化合物与雌激素受体的结合作用机制，结果表明，这些结构类似化合物中存在的不同受体作用模式，需要结合基于受体功能区结构的QSAR方法进一步探讨。     

氨基脲诱导的大鼠神经行为毒性及其生化机制

为探究氨基脲（SEM）染毒对SD大鼠的神经行为毒性及其作用机制,将44只SPF级SD雄性大鼠随机分为4组：对照组,SEM低、中、高剂量组,每组11只,分别以0,7.5,15,30mg/（kg·bw）SEM的剂量连续灌胃染毒28d.染毒前后分别通过旷场实验和高架十字迷宫实验测试神经行为.采用液相色谱法测定γ-氨基丁酸（GABA）和谷氨酸（GLU）,ELISA法测定5-羟色胺（5-HT）、去甲肾上腺素（NE）、多巴胺（DA）、单胺氧化酶（MAO）以及N-甲基-D-天氡氨酸受体（NMDAR）含量.结果显示,高剂量染毒组大鼠在旷场实验中运动总距离和中央区域距离显著低于对照组（P<0.05）,各剂量组大鼠在高架十字迷宫实验中进入开臂时间百分比和进入开臂次数百分比均显著低于对照组（P<0.05或P<0.01）.与对照组相比,各染毒组大鼠脑组织中GABA含量和MAO活性均有不同程度降低,而GLU,NMDAR,5-HT,NE和DA水平均有不同程度上升.SEM诱导大鼠神经行为毒性的机制与破坏GABA和GLU的相互转化、增加NMDAR含量以及抑制MAO活性导致单胺类神经递质水平上升3个途径有关.     

基于动态综合评价的区域环境风险差异化管理

借鉴灾害风险管理理论,运用“纵横向拉开档次法”和“时序加权平均算子法”构建了区域环境风险动态综合评价模型,提出了“风险评价-等级分区-差异化管理”的区域环境风险管理方法,并以河南省为案例研究对象,开展河南省18个市级单元环境风险的动态综合评价和“差异化”管理研究.结果显示：（1）郑州、许昌、漯河等市综合环境风险指数最高,分别为13.79、13.46和13.28,信阳、南阳和三门峡等市综合环境风险指数最低,分别为4.15、4.16和5.01;（2）采用系统分层聚类法将河南省18个市级单元聚为5类环境风险等级区,其中,郑州、许昌、漯河等属于高风险区;焦作、濮阳、鹤壁等属于较高风险区;安阳、开封属于中风险区;平顶山、商丘、周口等市属于较低风险区;洛阳、三门峡、南阳等市属于低风险区;（3）根据河南省各市环境风险等级及主导因素的差异,遵循高、较高风险区“重点控制、优先管理”、中低风险区“逐步控制、加强防范”的原则,提出了“差异化”的风险管理方案.研究结果表明,该方法不仅可实现区域环境风险动态综合评价,识别区域环境风险主要贡献因子,而且“差异化”的风险管理方案更符合地方经济社会环境协调发展的实际需求.     

Spatial distribution of health risks for residents located close to solvent-consuming industrial VOC emission sources

Emissions derived from the consumption of organic solvents have been proven to be the primary industrial source of volatile organic compounds (VOCs). In conjunction with epidemiologic studies, water-based paints (WBPs) and solvent-based paints (SBPs) were selected as representatives of newly developed solvents and traditional solvents, respectively, to simulate the effects of consuming solvents emitted during industrial production. And non-carcinogenic and carcinogenic risks to residents near emission sources were studied in detail. The results showed that the spatial distribution of health risks varied with meteorological conditions and type of emission source, and the prevailing wind direction strongly affected the distribution range and shape of the influenced area. The areas of influence maximized on heavy-polluting days for both WBP and SBP emission sources with the total span reaching 804 m and 16 km, respectively; meanwhile, the areas of influence for carcinogenic risk resulting from WBP emission sources were 1.2 and 2.3 times greater than those measured on fine and rainy days, respectively, and 1.8 and 2.9 times greater for SBP emission sources. Compared with WBPs, the total spans of negatively influenced regions resulting from SBP emission sources were 10.4, 12.5 and 19.9 times greater on fine, rainy and heavy-polluting days, respectively. Therefore, carcinogenic risk was the dominant health threat for populations residing close to solvent-consuming industrial emission sources. The findings suggest that newly developed solvents are capable of significantly reducing consequent health threats, nevertheless, they could still pose occasional threats to nearby residents under specific meteorological conditions.     

西安城区路面细颗粒灰尘重金属污染水平及来源分析

为揭示高强度人类活动对城市环境质量的影响,在西安市采集文教区、居民区、公园景区和交通区这4个主要功能区道路灰尘样品,利用X-Ray荧光光谱仪测定粒径63μm的道路细颗粒灰尘中Cu、Pb、Zn、Cr、Co、V、Mn和Ni的含量,采用地积累指数法和污染载荷指数法评价细颗粒灰尘中重金属的污染水平,运用主成分分析、聚类分析等多元统计学方法识别重金属的可能来源,利用主成分分析-多元线性回归受体模型解析不同来源对道路细颗粒灰尘中重金属的贡献.结果表明,西安市道路细颗粒灰尘中Cu、Pb、Zn和Cr的含量高于陕西土壤背景值,而V、Mn、Ni和Co的含量接近或低于它们的土壤背景值.道路细颗粒灰尘中Co、Mn、Ni、V呈现未污染,Cr、Cu和Zn呈现轻度污染,而Pb为偏中度污染.综合污染评价结果显示,西安市道路细颗粒灰尘中重金属呈现轻度污染.多元统计分析结果表明,Cr、Cu、Pb和Zn显著正相关,属于同一主成分,且在聚类分析中为同一类;V、Mn、Ni和Co为同一类、同一主成分,且显著正相关.结合样品中各重金属元素的含量特征,推断出西安市道路细颗粒灰尘中的重金属主要有两种来源:Cu、Pb、Zn和Cr主要来源于交通源,而V、Co、Mn和Ni主要为自然源.交通源和自然源对西安市道路细颗粒灰尘中重金属的贡献分别为56.7%和43.3%.     

Ah Receptor Agonists in UV-exposed Toluene Solutions of Decabromodiphenyl Ether (decaBDE) and in Soils Contaminated with Polybrominated Diphenyl Ethers (PBDEs) (9 pp)

Goal, Scope and Background The use of polybrominated diphenyl ethers (PBDEs) as flame retardants increases the risk for emissions of other brominated compounds, such as polybrominated dibenzodioxins (PBDDs) and dibenzofurans (PBDFs). The large homology in structure of PBDD/Fs and mechanism of toxic action, i.e. the capacity to activate the Ah receptor (AhR) pathway, compared to their well-studied chlorinated analogues, justifies a raised concern to study the environmental levels and fate of these compounds. Decabromodiphenyl ether (decaBDE) is the most widely used PBDE today. Studies on photolytic debromination of decaBDE in organic solvents have shown debromination of decaBDE, as well as formation of PBDFs. However, little is known about the transformation mechanisms and there are only scarce data on photoproducts and PBDE transformation in environmentally relevant matrices. In this study, mechanism-specific dioxin bioassays were used to study photolytic formation of AhR agonists in toluene solutions of decaBDE. In addition, the influence of irradiation time and UV-light wavelength on the formation was studied. PBDE congener patterns and presence of PBDD/Fs were analysed. Further, AhR agonists were analysed in agricultural soils contaminated with PBDEs. Soils were also exposed to UV-light to study changes in AhR agonist levels. Methods Toluene solutions of decaBDE were irradiated using three different spectra of UV-light, simulating UV-A (320-400 nm), UV-AB (280-400 nm), and UV-ABC (250-400 nm). Additionally, decaBDE solutions were exposed to narrow wavelength intervals (10 nm bandwidth) with the central wavelengths 280, 290, 300, 310, 320, 330, 340, 350, 360 nm. AhR agonists in decaBDE solutions were analysed with two different bioassays, the chick embryo liver-cell assay for dioxins (Celcad) and the dioxin responsive, chemically activated luciferase expression assay (DR-Calux). Also, the decaBDE solutions were analysed with LRGC-LRMS to obtain PBDE congener patterns for breakdown of decaBDE, and with HRGC-HRMS, for presence of PBDD/Fs. Four soils were exposed to UV-AB light, under both dry and moist conditions. Levels of AhR agonists in soil extract fractions, before and after UV-exposure, were analysed with the DR-Calux. Results and Discussion Significant levels of photoproducts able to activate the AhR pathway, up to 31 ng bio-TEQ/ml, were formed in UV-exposed decaBDE solutions. The transformation yield of decaBDE into AhR agonists was estimated to be at the 0.1%-level, on a molar basis. The net formation was highly dependent on wavelength, with the sample irradiated at 330 nm showing the highest level of dioxin-like activity. No activity was detected in controls. PBDE analysis confirmed decaBDE degradation and a clear time-dependent pattern for debromination of PBDE congeners. AhR agonist effect in the recalcitrant fractions of the soils corresponded to the levels of chemically derived TEQs, based only on chlorinated dioxin-like compounds in an earlier study. It was concluded that no significant levels of other AhR agonists, e.g. PBDFs, were accumulated in the soil. UV-light caused changes in AhR-mediated activity in the more polar and less persistent fractions of the soils, but it is not known which compounds are responsible for this. Recommendations and Perspective . The laboratory experiments in this study show that high levels of AhR agonists can be formed as photoproducts of decaBDE and it is important to elucidate if and under which conditions this might occur in nature. However, soil analysis indicates that photoproducts of PBDE do not contribute to the accumulated levels of persistent dioxin-like compounds in agricultural soil. Still, more data is needed to fully estimate the environmental importance of PBDE photolysis and occurrence of its photoproducts in other environmental compartments. Analysis with dioxin bioassays enabled us to gather information about photoproducts formed from decaBDE even though the exact identities of these compounds were not known. Conclusion Bioassays are valuable for studying environmental transformation processes like this, where chemical analysis and subsequent toxicological evaluation requires available standard compounds and information on toxicological potency. The use of bioassays allows a rapid evaluation of toxicological relevance.     

类酶联免疫分析法可行性的研究

多环芳烃作为持久性高毒性的有机污染物,一直受到广泛关注。酶联免疫分析技术因特异性强、快速、便捷等优点而广泛使用。建立了芳香烃受体介导的类酶联免疫竞争方法(类ELISA),用于检测环境中多环芳烃类物质的含量。在实验室条件下,分别检测了5种多环芳烃萘、苊、菲、荧蒽和芘,同时比较与高效液相色谱法(HPLC)和气相色谱-质谱联用法(GC/MS)在灵敏度、准确性和重现性等标的差异。HPLC检出限为2.70~10.71 ng/mL;GC/MS的检出限为2.60~24.40 ng/mL;类ELISA的检出限在1.24~3.10ng/mL。HPLC的加标回收率为58.03%~106.69%;GC/MS的加标回收率为88.16%~154.83%;类ELISA的加标回收率为74.67%~121.84%。HPLC的变异系数为4.26~9.03;GC/MS的变异系数为1.44~5.82;类ELISA的变异系数为2.56~8.16。结果表明,类ELISA方法灵敏度较好,准确性较高;而GC/MS方法重现性较好,检测更为稳定。     

BDE-28对斑马鱼核受体介导的内分泌干扰效应研究

2,4,4’-三溴联苯醚(BDE-28)在环境中普遍存在,且在长江流域多种水生生物中检出。目前,国内外对高溴代PBDEs(如BDE-47、BDE-99等)的水生脊椎动物内分泌干扰效应报道较多,而BDE-28的有关研究则相对较少。将斑马鱼胚胎暴露于2、20和200μg·L~(-1)的BDE-28后,借助q-RT-PCR方法对幼鱼8个重要受体包括雄激素受体(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)和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。结果表明,BDE-28暴露可导致AR、TR和Ah R的基因下调,其中核心受体AR和TR在低中高3种浓度下的下调倍数分别为3.03、2.64、10.10和2.21、2.18、2.31,芳香烃受体基因2(ahr2)在暴露于2和20μg·L~(-1)的BDE-28后,下调倍数分别为12.65和9.23,而雌激素受体(er1)基因在低中高浓度显著上调,上调倍数分别为12.29、12.67和15.87,雌激素受体(er2a)基因在2和20μg·L~(-1)BDE-28下的上调倍数分别为10.83和17.19。进一步采用分子对接和分子动力学模拟的方法研究BDE-28与AR、TR、Ah R和ER之间的相互作用。结果显示,BDE-28与这些受体通过疏水和氢键等相互作用稳定结合,动力学模拟后骨架原子的均方根偏差(RMSD)在5 ns后较稳定。由此可知,BDE-28通过AR、TR、Ah R和ER受体介导产生内分泌干扰效应。