Method to assess component contribution to toxicity of complex mixtures: Assessment of puberty acquisition in rats exposed to disinfection byproducts

A method based on regression modeling was developed to discern the contribution of component chemicals to the toxicity of highly complex, environmentally realistic mixtures of disinfection byproducts(DBPs). Chemical disinfection of drinking water forms DBP mixtures.Because of concerns about possible reproductive and developmental toxicity, a whole mixture(WM) of DBPs produced by chlorination of a water concentrate was administered as drinking water to Sprague–Dawley(S–D) rats in a multigenerational study. Age of puberty acquisition,i.e., preputial separation(PPS) and vaginal opening(VO), was examined in male and female offspring, respectively. When compared to controls, a slight, but statistically significant delay in puberty acquisition was observed in females but not in males. WM-induced differences in the age at puberty acquisition were compared to those reported in S–D rats administered either a defined mixture(DM) of nine regulated DBPs or individual DBPs. Regression models were developed using individual animal data on age at PPS or VO from the DM study. Puberty acquisition data reported in the WM and individual DBP studies were then compared with the DM models. The delay in puberty acquisition observed in the WM-treated female rats could not be distinguished from delays predicted by the DM regression model, suggesting that the nine regulated DBPs in the DM might account for much of the delay observed in the WM. This method is applicable to mixtures of other types of chemicals and other endpoints.     

Control of aliphatic halogenated DBP precursors with multiple drinking water treatment processes: Formation potential and integrated toxicity

The comprehensive control efficiency for the formation potentials(FPs) of a range of regulated and unregulated halogenated disinfection by-products(DBPs)(including carbonaceous DBPs(C-DBPs), nitrogenous DBPs(N-DBPs), and iodinated DBPs(I-DBPs)) with the multiple drinking water treatment processes, including pre-ozonation, conventional treatment(coagulation–sedimentation, pre-sand filtration), ozone-biological activated carbon(O_3-BAC) advanced treatment, and post-sand filtration, was investigated. The potential toxic risks of DBPs by combing their FPs and toxicity values were also evaluated.The results showed that the multiple drinking water treatment processes had superior performance in removing organic/inorganic precursors and reducing the formation of a range of halogenated DBPs. Therein, ozonation significantly removed bromide and iodide,and thus reduced the formation of brominated and iodinated DBPs. The removal of organic carbon and nitrogen precursors by the conventional treatment processes was substantially improved by O_3-BAC advanced treatment, and thus prevented the formation of chlorinated C-DBPs and N-DBPs. However, BAC filtration leads to the increased formation of brominated C-DBPs and N-DBPs due to the increase of bromide/DOC and bromide/DON.After the whole multiple treatment processes, the rank order for integrated toxic risk values caused by these halogenated DBPs was haloacetonitriles(HANs)》haloacetamides(HAMs) haloacetic acids(HAAs) trihalomethanes(THMs) halonitromethanes(HNMs) 》I-DBPs(I-HAMs and I-THMs). I-DBPs failed to cause high integrated toxic risk because of their very low FPs. The significant higher integrated toxic risk value caused by HANs than other halogenated DBPs cannot be ignored.     

Capability of cation exchange technology to remove proven N-nitrosodimethylamine precursors

N-nitrosodimethylamine(NDMA) precursors consist of a positively charged dimethylamine group and a non-polar moiety, which inspired us to develop a targeted cation exchange technology to remove NDMA precursors. In this study, we tested the removal of two representative NDMA precursors, dimethylamine(DMA) and ranitidine(RNTD), by strong acidic cation exchange resin. The results showed that pH greatly affected the exchange efficiency, with high removal(DMA 78% and RNTD 94%) observed at pH pk_a-1 when the molar ratio of exchange capacity to precursor was 4. The exchange order was obtained as follows: Ca~(2+) Mg~(2+) RNTD~+ K~+ DMA~+ NH_4~+ Na~+. The partition coefficient of DMA~+to Na~+was 1.41 ± 0.26, while that of RNTD~+to Na~+was 12.1 ± 1.9. The pseudo second-order equation fitted the cation exchange kinetics well. Bivalent inorganic cations such as Ca~(2+)were found to have a notable effect on NA precursor removal in softening column test. Besides DMA and RNTD, cation exchange process also worked well for removing other 7 model NDMA precursors. Overall, NDMA precursor removal can be an added benefit of making use of cation exchange water softening processes.     

覆盖金属氧化物对湖泊沉积物溶解性有机质特征的影响

为揭示不同金属氧化物对湖泊沉积物DOM（溶解性有机质）影响机制,通过室内模拟试验,在沉积物表层分别覆盖Fe、Al、Mn氧化物及湖沙后培养1 a,并利用三维荧光和紫外光谱方法进行表征.结果表明:① 覆盖Al、Fe、Mn氧化物和湖沙主要降低了0~3 cm沉积物的w（DOC）,降幅分别为8.61%、6.27%、22.38%和0.44%. ② 沉积物中DOM的类络氨酸峰（peak B₁）和类色氨酸峰（peak T₂）均产生较大变化.其中三种氧化物均显著降低了上层沉积物中DOM的peak T₂,使底层DOM的peakT₂显著增加. Mn氧化物使DOM的peak B₁降低,Fe和Al氧化物使DOM的peak B₁增加,湖沙则使两类峰均降低. ③ 覆盖金属氧化物改变了沉积物DOM结构特征,其中覆盖Fe氧化物增强了其芳香性,而覆盖Mn氧化物和Al氧化却降低其芳香性,但三者均使DOM腐质化程度及官能团数量增加,并使FI（Fluorescence Index,荧光指数）增大,表明DOM向生物源转化.研究显示,沉积物表层覆盖金属氧化物影响了沉积物中DOM迁移和转化,并促进了其降解,导致其分子量和腐殖化程度增加.      

2001-2010年三江源区草地净生态系统生产力估算

三江源区位于青藏高原腹地,是我国长江、黄河、澜沧江三大河流的发源地.为了准确估算该地区草地生态系统的净生态系统生产力,收集整理了2001—2010年青藏高原10个通量观测站点的观测数据,构建了三江源区草地生态系统NEP（net ecosystem production,净生态系统生产力）估算模型,并在站点尺度进行了模型参数化和精度验证;结合区域尺度气象和遥感数据,估算了三江源区草地生态系统NEP.结果表明:① 2001—2010年三江源区草地生态系统多年平均NEP空间分布具有明显的空间异质性,大部分地区表现为碳汇,NEP（以C计）平均值为41.8 g/（m2·a）.② 三江源区草地生态系统NEP呈波动增加趋势,从2001年的20.0 g/（m2·a）增至2010年的82.5 g/（m2·a）;除2002年表现为弱碳源外,其余年份均表现为碳汇,并以2010年碳汇能力为最强.③ 2001—2010年三江源区草地生态系统NEP平均年增长率为5.4 g/m2;NEP年际变化率空间分布显示,大部分地区NEP呈增加趋势,仅有东南部和中部部分区域NEP呈下降趋势.研究显示,2001—2010年三江源区草地生态系统表现为碳汇,并且由于气候的暖湿化趋势,碳汇强度总体表现为增强.      

大冶湖表层水和沉积物中重金属污染特征与风险评价

于2014年4月采集大冶湖表层水和表层沉积物,用原子吸收分光光度法测定其重金属含量,并基于健康风险评价模型和潜在生态风险指数法开展表层水和沉积物重金属污染的潜在健康风险和生态风险评价.结果表明,表层水和沉积物重金属(Ni、Cd、Cu和Pb)含量平均值分别为49.27、2.19、12.18、12.13μg·L~(-1)和78.46、77.13、650.13、134.22 mg·kg~(-1).富集系数显示,Cd、Cu和Pb均为重度富集,尤其是Cd累积最为明显.与国内典型湖泊重金属污染相比,表层水和沉积物中重金属元素含量均相对较高.表层水和沉积物重金属元素均表现为湖湾处含量较高,中部含量较均匀的分布规律,其来源主要受多种人为活动污染.环境风险评价显示,重金属类化学物质通过饮水途径产生健康风险范围为9.77E-08~1.63E-05 a-1,Ni和Cd是水环境健康风险的优先管理对象.沉积物重金属的潜在生态风险高低为CdCuPbNi,其中Cd是生态风险的贡献元素.     

基于污泥掺烧的某生活垃圾焚烧厂烟道气、飞灰及炉渣中的二(口恶)英特征

以我国南方某生活垃圾焚烧厂掺烧10%市政污泥的生活垃圾为研究对象,对前/后口废气、飞灰、炉渣及用于掺烧的污泥中17种二(口恶)英的含量进行了测定,并分析了其指纹分布特征.结合焚烧工况及处理设施,从生成机理角度探讨了二(口恶)英的排放特征、毒性当量浓度主成分特征及主要单体的排放因子线性关系.结果表明：掺烧10%的市政污泥后,废气中二(口恶)英的去除率为99.4%,低于国家排放标准;固体废物中二(口恶)英含量为飞灰 > 炉渣 > 污泥.这说明采用高温焚烧和"活性炭喷射+布袋除尘"装置不会影响掺烧10%污泥的达标排放.指纹分布特征表明,前口废气以1,2,3,4,6,7,8-HpCDF和OCDD为主,后口废气以OCDD和OCDF为主;飞灰、炉渣及污泥中的主要单体为OCDD、1,2,3,4,6,7,8-HpCDD、OCDF、1,2,3,4,6,7,8-HpCDF.主成分分析显示,前口废气和飞灰中的二(口恶)英毒性分布特征相似;炉渣和污泥的毒性分布特征相似;后口废气有自身的特征.这说明在相同工况条件下,经同一设施处理的废物中二(口恶)英排放特征相似.排放因子分析表明,2,3,4,7,8-PeCDF和1,2,3,6,7,8-HxCDF、1,2,3,6,7,8-HxCDD和1,2,3,7,8,9-HxCDD与总毒性排放因子具有较强的线性关系,且呋喃类（PCDFs）强于二(口恶)英类（PCDDs）.     

人为干扰对小兴安岭森林湿地土壤碳组分和酶活性的影响

以小兴安岭落叶林沼泽湿地为研究对象,对比研究皆伐地、火烧地和落叶松湿地土壤碳组分和酶活性.结果表明:(1)3种湿地类型土壤SOC含量表现为对照地显著高于皆伐地和火烧地(p0.05),在0~10 cm土层中皆伐地与对照地相比降低了58.38%,火烧地与对照地相比降低了61.96%.皆伐地与火烧地在不同土层的土壤中SOC含量差异不显著(p0.05);DOC含量对照地显著高于皆伐地和火烧地(p0.05).在0~10cm土层中火烧地DOC含量是皆伐地的1.99倍,两者差异不显著(p0.05);不同干扰方式对土壤MBC含量影响的差异主要表现在0~10 cm的土层土壤,对照地分别比皆伐地和火烧地高23.13%和95.79%(p0.05).在不同的土层中皆伐地MBC含量均大于火烧地,与SOC含量的变化趋势一致.(2)与对照地相比,皆伐地与火烧地0~10 cm土层的土壤蔗糖酶活性分别降低了45.59%和36.76%,脲酶活性显著降低了18.22%和55.69%(p0.05),蛋白酶活性降低了19.65%和17.34%,淀粉酶活性降低了6.29%和10.69%.土壤碳组分和酶活性在垂直方向上均表现为随着土层深度增加而减小.皆伐和火烧造成森林湿地土壤碳组分和酶活性降低.     

新型重金属絮凝剂巯基乙酰化羟甲基聚丙烯酰胺的优化制备

为提高含铜废水的处理效果及简化处理流程,以聚丙烯酰胺(PAM)、甲醛、氢氧化钠、巯基乙酸(TGA)为原料,先经羟甲基化反应制备中间产物羟甲基聚丙烯酰胺(MPAM),再通过酰胺化反应将巯基接枝到MPAM分子链上,制备出新型重金属絮凝剂巯基乙酰化羟甲基聚丙烯酰胺(MAMPAM).以水样中Cu(Ⅱ)的去除率为考察目标,采用Plackett-Burman实验、最陡爬坡实验和响应面法中CCD实验优化MAMPAM的制备条件.结果表明,MAMPAM最优制备条件为:MPAM浓度0.31%、MPAM与TGA物质的量比为1∶3.2、反应介质p H值为4.76、反应温度为25℃、反应时间为2 h,在此条件下制备的MAMPAM对Cu(Ⅱ)的去除率为95.30%,与模型的理论预测值94.47%接近,相对偏差仅为0.83%,模型合理可靠.红外分析表明MPAM分子链上成功接上了巯基.MAMPAM对不同初始浓度的含Cu(Ⅱ)水样具有很好的去除效果,Cu(Ⅱ)去除率均能达到90%以上.MAMPAM有望成为一种有效的含铜废水处理剂,具有一定的应用前景.     

亚硝氮停供及恢复供给对Anammox反应器中氮去除的影响

在Anammox-UASB反应器中研究了亚硝氮停供及恢复供给后不同进水亚硝氮/氨氮比(R_I)对Anammox系统脱氮的影响,对Anammox系统停供亚硝氮培养后的污泥微生物群落进行了分析.结果表明,Anammox反应器在长期停供亚硝氮培养后,微生物多样性增加,氨氧化菌(Nitrosomonas)和Anammox菌都大量增殖,这两种微生物通过协同作用使得部分氨氮得以去除,NH_4~+-N最大去除速率可达68.77 mg·L~(-1)·d~(-1),出水p H低于进水.反应器恢复亚硝氮供给后,脱氮效果快速恢复.Anammox反应器中存在的氨氮"超量去除"现象是由氨氧化菌作用引起的,氨氧化菌活性易受亚硝氮浓度抑制.氨氮"超量去除"量占氨氮总去除量的百分比与R_I呈负相关关系.当R_I为0.17时,氨氮"超量去除"量占氨氮总去除量的百分比高达68.83%;当R_I增加到1.30∶1后,氨氮"超量去除"现象基本消失.