Using regression models to evaluate the formation of trihalomethanes and haloacetonitriles via chlorination of source water with low SUVA values in the Yangtze River Delta region,China

The purpose of this study was to develop the multiple regression models to evaluate the formation of trihalomethanes (THMs) and haloacetonitriles (HANs) during chlorination of source water with low specific ultraviolet absorbance (SUVA) in Yangtze River Delta, China. The results showed that the regression models of THMs exhibited good accuracy and precision, and 86–97 % of the calculated values fell within ±25 % of the measured values. While the HANs models showed relatively weak evaluation ability, as only 75–83 % of the calculated values were within ±25 % of the measured values. The organic matter [dissolved organic carbon (DOC) or UV absorbance at 254 nm] and bromide exerted the most important influence on the formation of HANs. While for THMs, besides the organic matter and bromide, reaction time was also a key factor. Comparing the models for total THMs (T-THMs) in this study with others revealed that the regression models from the low SUVA waters may have low DOC coefficients, but high bromide coefficients as compared with those from the high SUVA waters.     

Characteristics of residual organochlorine pesticides in soils under different land-use types on a coastal plain of the Yellow River Delta

The residual levels of organochlorine pesticides (OCPs) were examined in soils covering five types of land use along a salinity gradient on the Yellow River Delta. The most prominent OCPs were dichlorodiphenyltrichloroethane (∑DDT, arithmetic mean = 5.11 μg kg^?1), hexachlorocyclohexane (∑HCH, 1.69 μg kg^?1) and ∑endosulfan (10.4 μg kg^?1). The spatial variability of OCPs composition shifted from γ-HCH and o,p′-DDT dominated pesticides in coastal soils to p,p′-DDE dominated pesticides in inland soils. In different land-use types, the percentages of β-HCH and p,p′-DDE are characterized by more recalcitrant components in decreasing order of vegetable fields, cereal fields, cotton fields, wetlands and tidal flats with increasing soil salinity. However, the less recalcitrant components, γ-HCH and o,p′-DDT, showed an opposite trend. Endosulfan sulfate predominated in all land-use types. Residual levels of β-HCH were affected by soil organic matter. The correlations between γ-HCH and clay content and between p,p′-DDE, o,p′-DDT and salinity might associate with the influence of sediment cotransport by the Yellow River and the density of anthropogenic activities in coastal region. Depth distribution of the OCPs in typical soil profiles also implied that local historical usage and sediment transport by the Yellow River both affected the OCPs residual in this region.     

Photochemical indicators of ozone sensitivity: application in the Pearl River Delta,China

Surface O₃ production has a highly nonlinear relationship with its precursors. The spatial and temporal heterogeneity of O₃-NO _x -VOC-sensitivity regimes complicates the control-decision making. In this paper, the indicator method was used to establish the relationship between O₃ sensitivity and assessment indicators. Six popular ratios indicating ozone-precursor sensitivity, HCHO/NO _y , H₂O₂/ HNO₃, O₃/NO _y , O₃/NO _z , O₃/HNO₃, and H₂O₂/NO _z , were evaluated based on the distribution of NO_x- and VOC-sensitive regimes. WRF-Chem was used to study a serious ozone episode in fall over the Pearl River Delta (PRD). It was found that the south-west of the PRD is characterized by a VOCsensitive regime, while its north-east is NO _x -sensitive, with a sharp transition area between the two regimes. All indicators produced good representations of the elevated ozone hours in the episode on 6 November 2009, with H₂O₂/HNO₃ being the best indicator. The threshold sensitivity levels for HCHO/NO_y, H₂O₂/HNO₃, O₃/NO _y , O₃/NO _z , O₃/HNO₃, and H₂O₂/NO _z were estimated to be 0.41, 0.55, 10.2, 14.0, 19.1, and 0.38, respectively. Threshold intervals for the indicators H₂O₂/HNO₃, O₃/NO _y , O₃/NO _z , O₃/HNO₃, and H₂O₂/NO _z were able to identify more than 95% of VOC- and NO _x -sensitive grids. The ozone episode on 16 November 16 2008 was used to independently verify the results, and it was found that only H₂O₂/HNO₃ and H₂O₂/NO _z were able to differentiate the ozone sensitivity regime well. Hence, these two ratios are suggested as the most appropriate indicators for identifying fall ozone sensitivity in the PRD. Since the species used for indicators have seasonal variation, the utility of those indicators for other seasons should be investigated in the future work.

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2种毒性评估方法对PAHs污染场地人体健康风险的比较研究

毒性评估是人体健康风险评价的重要部分,目前主要存在2种方法,一种基于PAHs相对于苯并[a]芘(BaP)的毒性当量因子,采用Ba P致癌斜率因子参数(方法 1),另一种直接采用各PAHs致癌斜率因子和非致癌参考剂量等参数(方法 2)。然而2种毒性评估方法得到的风险及修复量是否存在差异以及引起差异的原因等问题鲜有讨论。针对苏南某焦化厂PAHs污染土壤,采用分层土壤健康风险评价模型,对比了2种毒性评估方法确定的PAHs风险、修复目标污染物及土方量的差异,并对引起差异的关键因素进行探讨。结果表明:对于0.0~1.0 m表层土壤,方法 1和方法 2确定的致癌风险最大值分别1.48E-05和1.32E-05,均超过可接受致癌风险,修复土方量分别为27 846 m~3和28 667 m3,修复目标污染物均为Ba P和二苊烃(Acy)。对于1.0~3.0 m深层土壤,方法 1确定的致癌风险最大值为3.36E-08,低于可接受致癌风险,不需要修复;而方法 2确定的致癌风险最大值为3.73E-04,非致癌危害指数最大值为6.96E+01,分别超过可接受致癌风险和非致癌危害商,需要修复,修复目标污染物为萘(NaP),修复土方量为35 944 m~3。最终,方法 2确定的总修复土方量(64 611 m~3)为方法 1确定土方量(27 846 m~3)的2.45倍,而这种差异主要是由于方法 1低估了深层土壤中高挥发性PAH单体尤其是NaP的风险所致。因此,从保守角度建议采用方法 2进行PAHs风险评价。     

丙烯腈-丁二烯-苯乙烯塑料、四溴双酚A混合物的热解实验:含溴二噁英生成研究

模拟电子垃圾热回收处理过程,将丙烯腈-丁二烯-苯乙烯塑料(ABS)、四溴双酚A(TBBPA)分别与4种金属(Cu、Fe、Zn和Ni)进行混合,在自制的加热装置内开展了不同气氛、不同温度条件下热解实验研究。对产物溴代二噁英(PBDD/Fs)检测显示,2,3,7,8-TBDF、2,3,7,8-TBDD及1,2,3,4,7,8-与1,2,3,6,7,8-Hx BDD为主要产物,其中2,3,7,8-TBDF含量最高,约占总PBDD/Fs的12%~90%。反应生成的8种2,3,7,8-PBDD/Fs浓度范围为0.05~2 082 ng·g-1。在同等实验条件下,温度升高有利于ABS塑料混合物中PBDD/Fs的生成。Cu、Fe、Zn和Ni四种金属都具有催化效应。空气、氮气气氛下热解实验显示,空气气氛下PBDD/Fs的生成量大,2种条件下生成的二噁英总量比值在0.8~99.6之间变化。无金属催化条件下此比值变化范围较小,为0.8~1.5;在金属参与条件下,此比值变化范围加大,为1.2~99.6;其中,在Cu和Fe参与下,此比值较高。各种热解条件下形成的PBDD/Fs都具有PBDFsPBDDs的特征。研究结果说明,虽然无金属参与条件下含TBBPA的ABS热解生成溴代二噁英浓度较低,但金属(如Cu等)存在时,此类污染物的浓度显著增加。     

腐殖酸与典型碳纳米材料协同光致产生活性氧物种的研究

采用电子自旋共振光谱(EPR)技术,分析腐殖酸在光照下对4种典型碳纳米材料诱导产生单线态氧(~1O_2)和羟基自由基(·OH)的影响。基于密度泛函理论计算4种典型碳纳米材料的前线轨道能,比较了它们分别经能量转移诱导产生~1O_2的能力以及经电子传递诱导产生·OH的能力。结果显示,4种不同形状的碳纳米材料(富勒烯、单壁碳纳米管、多壁碳纳米管以及石墨烯)悬浮液在紫外光照下均无~1O_2和·OH产生。与腐殖酸共同存在下,4种碳纳米材料均显著诱导~1O_2的产生,且富勒烯和石墨烯还能光致生成·OH。协同产生~1_O2的能力大小为:单壁碳纳米管富勒烯多壁碳纳米管石墨烯,协同产生·OH的能力大小为:石墨烯富勒烯。~1O_2的产生能力与碳纳米材料的能隙大小和颗粒聚集程度有关,而诱导产生·OH的能力主要取决于化学硬度。总之,我们的研究表明腐殖酸与碳纳米颗粒可协同产生活性氧物种。     

重金属Cd、Pb对褐菖鲉肝脏组织中HSPs基因表达的影响

为了解重金属污染对海洋鱼类热休克蛋白(HSPs)基因表达的影响,将褐菖鲉(Sebastiscus marmoratus)分别暴露于1.6、8、40、200、500μg·L~(-1)Cd、Pb溶液中,用环介导等温扩增技术(loop-mediated isothermal amplification,LAM P)定量检测褐菖鲉肝脏HSP60、HSP70、HSP90、HSC70 mRNA表达量。结果表明:Pb仅在40μg·L-1时显著抑制HSP60、HSP90、HSC70 mRNA表达量,8μg·L~(-1)时即可显著抑制HSP70 m RNA表达量,并在40μg·L~(-1)时达到最小值;Cd对HSP60、HSP90、HSC70的诱导不明显,但能显著诱导HSP70,并在500μg·L~(-1)时达到最大值。相比之下,褐菖鲉肝HSP70基因对重金属Cd、Pb污染较为敏感,有潜力成为监测海洋重金属污染的预警分子。     

浓度效应对卡马西平在生物炭上的吸附动力学影响

为了解人工合成药物在生物炭上的吸附动力学特征及其浓度效应的影响,选择卡马西平(CBZ)为目标污染物。探讨不同初始质量浓度(2、4、25、50 mg·L~(-1))在不同裂解温度(200、300、500℃)下制备的生物炭上的吸附动力学特征。结果表明,双室一级动力学模型可以精确地描述CBZ在生物炭上的吸附动力学特征。CBZ的快室吸附对总体吸附的贡献随初始浓度的增大而减小,而慢室吸附贡献则增大。π-π作用可能对CBZ的吸附贡献较大。孔隙填充可以描述慢室吸附过程,可能是吸附速率的控制环节。     

镉胁迫对苎麻(Boehmeria nivea)根系及叶片抗氧化系统的影响

镉(Cd)是非必需和毒性最强的重金属元素之一,不合理的开发利用可导致土壤受到Cd的严重污染,严重危及土壤环境或水环境。以苎麻为材料,采用模拟镉(Cd)污染盆栽培养法,选择21 d和49 d等2个不同胁迫期,测定不同浓度Cd2+胁迫下苎麻根系与叶片中渗透调节物质含量、超氧化物岐化酶(SOD)活性、过氧化物酶(POD)活性、过氧化氢酶(CAT)活性、丙二醛(MDA)含量及根系活力的变化。结果表明,高浓度胁迫49 d后,苎麻根系中的渗透调节物质含量明显高于叶片含量,且极显著高于对照,并在240 mg·L~(-1)Cd处理下出现最高值;胁迫49 d时,根系与叶片的渗透调节物质含量与Cd2+浓度极显著正相关。在2个不同胁迫周期,苎麻根系的SOD与POD活性均明显高于叶片;在胁迫21 d时,根系的CAT活性低于叶片,而胁迫49 d后,则明显高于叶片;胁迫21 d时,苎麻根系与叶片的抗氧化酶活性均较胁迫49 d要高;胁迫49 d时,根系POD活性与Cd2+浓度呈极显著正相关,表明根系POD酶在抗氧化酶中占主导地位。不同胁迫时长下苎麻根系或叶片的MDA含量变化趋势不明显,但根系或叶片受胁迫21 d后的MDA含量随Cd2+浓度增加的波动相对受胁迫49 d后的更明显,表明植物早期生理功能出现暂时性的修复。2个不同胁迫周期内,不同浓度镉胁迫下苎麻的根系活力均比对照组下降。研究显示,苎麻根系与叶片对镉胁迫的应答机制不同,且在不同胁迫时间下的响应机理差异较大,根系表现出更强的耐受能力。     

纳米二氧化硅对两性生殖和孤雌生殖卤虫无节幼体毒性影响的比较研究

研究了纳米二氧化硅(Nano-SiO_2)悬浮液对美国大盐湖两性生殖型卤虫(Artemia francisana,GSL)和渤海湾孤雌生殖型卤虫(Artemia parthenogenetica,BH)无节幼体的急性毒性和抗氧化酶系统的影响。研究结果表明,Nano-SiO_2对GSL和BH无节幼体24 h-LC50分别为23.02 mg·m L~(-1)和20.96 mg·m L~(-1),属低级毒性。Nano-SiO_2降低了GSL和BH无节幼体还原型谷胱甘肽(GSH)含量,抑制了过氧化氢酶(CAT)和超氧化物歧化酶(SOD)活性,致丙二醛(MDA)含量升高,表明氧化应激反应是导致Nano-SiO_2对卤虫无节幼体致死的作用机制之一。