腐殖质及其模型化合物的H2O2光化学生成研究

在模拟太阳光下研究了多种腐殖质及其模型化合物的过氧化氢（H₂O₂）生成动力学,并对其生成机制进行了探讨.结果表明不同来源或不同形式的腐殖质在模拟太阳光照射下均能产生H₂O₂.不同腐殖质生成H₂O₂速率差异不大,范围为6.379~15.784nmol/（L·min）,腐殖酸生成H₂O₂速率略快于富里酸.对于腐殖质模型化合物,邻苯二酚、间苯二酚、对苯二酚、苯醌、邻茴香胺、对茴香胺、水杨酸和2,6-二甲氧基-1,4-苯醌等8种模型化合物没有产生明显的H₂O₂,而藜芦醇、对氨基苯甲酸、3,5-二羟基苯甲酸（DHBA）、2,5-二羟基-1,4-苯醌、苯酚、苯甲酸和苯胺等7种化合物均可检测到H₂O₂产生.但其产生H₂O₂的速率差异较大,相差1~2个数量级,生成H₂O₂速率最快的化合物为2,5-二羟基-1,4-苯醌和DHBA,较慢的为苯酚、苯甲酸和对氨基苯甲酸.基于腐殖质生成H₂O₂机制,推测典型模型化合物DHBA的H₂O₂生成机制可能为光照条件下该化合物跃迁为单重激发态,该激发态发生分子内电子转移,生成还原性自由基中间体,该中间体和O₂反应,生成了超氧负离子（O₂·^-）,随后与水中H⁺反应生成了H₂O₂.     

以污水流行病学监测广西某市12个污水处理厂服务区域精神活性物质的消耗量

精神活性物质滥用和使用量逐年递增正成为社会稳定、环境健康新的关注点。准确地估算某一地区这类化合物的消耗总量是管理这类物质的关键。本研究对中国广西某市12个污水处理厂(wastewater treatment plants,WWTPs)服务区域中的8种精神活性物质消耗量进行了调查。首先,采用固相萃取-液相色谱-串联质谱法测定了广西某市12个WWTPs进水中8种精神活性物质的浓度,检测到在<方法检测(method detection limit,MDL)至170.9 ng·L^-1范围内的5种精神活性物质。然后,依据污水流行病学(wastewater-based epidemiology,WBE)进行消耗量反算。结果表明,氯胺酮(ketamine,KET)、吗啡(morphine,MOR)、冰毒(methamphetamine,METH)、摇头丸(3,4-methylenedioxymethamphetamine,MDMA)是主要检出的精神活性物质,平均消耗量分别为682.4、167.8、44.6、11.3 mg·d^-1·1000inh^-1;而可卡因(cocaine,COC)、苯甲酰爱康宁(benzoylecgonine,BE)、甲卡西酮(methcathinone,MC)没有被检出。对WWTPs进水中精神活性物质的残留进行分析,估算这些物质在特定区域的消耗量,为防控风险提供支持。     

Biotoxicity evaluation of zinc oxide nanoparticles on bacterial performance of activated sludge at COD,nitrogen, and phosphorus reduction

• ZnO-NP disrupted metabolic/catabolic balance of bacteria by affecting DHA activity. • ZnO-NPs toxicity was related to Zn²⁺ ion, interaction with cell and ROS generation. • Exposure to ZnO-NPs resulted in changed bacterial community structure at sludge. • The change in the EPS content was observed during exposure to ZnO-NPs. The unique properties and growing usage of zinc oxide nanoparticles increase their release in municipal wastewater treatment plants. Therefore, these nanoparticles, by interacting with microorganisms, can fail the suitable functioning of biological systems in treatment plants. For this reason, research into the toxicity of ZnO is urgent. In the present study, the toxicity mechanism of ZnO-NPs towards microbial communities central to granular activated sludge (GAS) performance was assessed over 120-day exposure. The results demonstrate that the biotoxicity of ZnO-NPs is dependent upon its dosage, exposure time, and the extent of reactive oxygen species (ROS) production. Furthermore, GAS performance and the extracellular polymeric substances (EPS) content were significantly reduced at 50 mg/L ZnO-NPs. This exposure led to decreases in the activity of ammonia monooxygenase (25.2%) and nitrate reductase (11.9%) activity. The Field emission scanning electron microscopy images confirmed that ZnO-NPs were able to disrupt the cell membrane integrity and lead to cell/bacterial death via intracellular ROS generation which was confirmed by the Confocal Laser Scanning Microscopy analysis. After exposure to the NPs, the bacterial community composition shifted to one dominated by Gram-positive bacteria. The results of this study could help to develop environmental standards and regulations for NPs applications and emissions.     

Influence of extracellular polymeric substances from activated sludge on the aggregation kinetics of silver and silver sulfide nanoparticles

• The NPs aggregation in the electrolyte solution is consistent with the DLVO theory. • In NaNO₃ and low Ca(NO₃)₂, EPS alleviates the NPs aggregation by steric repulsion. • In high Ca(NO₃)₂, EPS accelerates the NPs aggregation by exopolysaccharide bridging. • Ag₂S NPs have stronger stability compared with Cit-Ag NPs in aqueous systems. Extracellular polymeric substances (EPS) in activated sludge from wastewater treatment plants (WWTPs) could affect interactions between nanoparticles and alter their migration behavior. The influence mechanisms of silver nanoparticles (Ag NPs) and silver sulfide nanoparticles (Ag₂S NPs) aggregated by active EPS sludge were studied in monovalent or divalent cation solutions. The aggregation behaviors of the NPs without EPS followed the Derjaguin-Landau-Verwey-Overbeek (DLVO) theory. The counterions aggravated the aggregation of both NPs, and the divalent cation had a strong neutralizing effect due to the decrease in electrostatic repulsive force. Through extended DLVO (EDLVO) model analysis, in NaNO₃ and low-concentration Ca(NO₃)₂ (<10 mmol/L) solutions, EPS could alleviate the aggregation behaviors of Cit-Ag NPs and Ag₂S NPs due to the enhancement of steric repulsive forces. At high concentrations of Ca(NO₃)₂ (10‒100 mmol/L), exopolysaccharide macromolecules could promote the aggregation of Cit-Ag NPs and Ag₂S NPs by interparticle bridging. As the final transformation form of Ag NPs in water environments, Ag₂S NPs had better stability, possibly due to their small van der Waals forces and their strong steric repulsive forces. It is essential to elucidate the surface mechanisms between EPS and NPs to understand the different fates of metal-based and metal-sulfide NPs in WWTP systems.     

预浓缩-GC/MS测定空气中的27种ODS和HFCs

优化预浓缩仪二级冷阱温度和柱温箱初始温度,建立了预浓缩-气相色谱 /质谱联用(GC/MS)技术测定空气中27种消耗臭氧层物(ODS)和氢氟烃(HFCs)的分析方法。结果表明,27种ODS和HFCs峰形良好,分离度较好,校准曲线相对响应因子标准偏差为1.7%~15.9%,方法检出限为0.016~0.172 μg/m³。空白加标样品连续测定6次的相对标准偏差为0.9%~13.4%,回收率为70.4%~116%。基体加标样品连续测定6次的相对标准偏差为1.0%~7.8%,回收率为94.3%~108%。实验楼周边的环境空气以及实验室内部工作环境空气均检出不同浓度的ODS和HFCs,该方法适用于空气中ODS和HFCs的测定。     

Role of competition in phytoplankton population for the occurrence and control of plankton bloom in the presence of environmental fluctuations

Termination of harmful algal blooms (HABs) and coexistence of phytoplankton–zooplankton populations are of great importance to human health, ecosystem, environment, tourism and fisheries. In this paper, we propose a three component model consisting of non-toxic phytoplankton (NTP), toxin producing phytoplankton (TPP) and zooplankton (Z). The growth of zooplankton species is assume to reduce due to toxic chemicals released by TPP population. We have extended the model proposed by Chattopadhyay et al. [Chattopadhyay, J., Sarkar, R.R., Pal, S., 2004. Mathematical modelling of harmful algal blooms supported by experimental findings. Ecol. Comp. 1, 225–235] by including competition terms between TPP and NTP. We observe the effect of competition factors both in the presence and absence of the environmental fluctuation. From our field as well as model analysis we observe that competition helps in the coexistence of the species, but if the effect of competition is very high on the TPP population, it results in planktonic bloom. It is shown that the coexistence equilibrium loses its stability when the competition coefficient crosses a critical value and resulting Hopf-bifurcation around the positive equilibrium depicting oscillations phenomena of the populations.     

液相色谱-串联质谱法同时测定污水中10种精神活性物质

建立了采用液相色谱-串联质谱法(LC-MS/MS)同时测定污水中10种精神活性物质的分析方法。污水样品经甲酸与甲酸铵调节pH后,加入氘代内标混匀,离心并过滤膜后可直接上样分析。研究表明,在1~250 ng/L的线性范围内,10种精神活性物质的线性相关系数均大于0.992,定量限均低于0.5 ng/L。在3个加标水平下,10种精神活性物质的加标回收率为87.2%~114%,相对标准偏差为0.53%~3.60%(n=3)。将该方法应用于某区域10份生活污水样品的检测,在3份水样中检出吗啡、甲基苯丙胺、氯胺酮等精神活性物质,对应的质量浓度范围分别为3.41~9.55、0.90~1.63、1.06~1.78 ng/L。与经固相萃取前处理后的分析方法相比,该方法可在10 min内完成分离和检测的全过程,具有简单、快速、节约的优点,可用于污水样品中10种痕量水平精神活性物质的定量分析。     

生物反应器填埋场初期的重金属释放行为

以库容10万m³的生物反应器填埋单元1.5年的渗滤液水质监测结果为依据,研究了该填埋单元初期的重金属释放行为.结果表明,渗滤液低pH值和高溶解性有机物(DOM)含量使渗滤液中的重金属浓度超过标准限值;但随着填埋层进入稳定产甲烷化阶段,重金属浓度显著下降,渗滤液中的腐殖质是影响此阶段重金属迁移的重要媒介.渗滤液中悬浮性固体、DOM分子量分级测试和VisualMinteq模型模拟计算结果表明,渗滤液中的重金属主要以与有机物,特别是以与腐殖质结合的形态存在.预测填埋单元内重金属的溶出过程可持续数百年.     

全球地表水中全氟和多氟烷基化合物污染特征演替

综述了全氟和多氟烷基化合物（PFASs）在国内外地表水环境中的空间分布及污染特征,总结归纳了PFASs的来源和特征变化趋势。针对地表水中PFASs的监测种类、监测技术及风险评估等方面存在的问题,提出未来需加强日常监测,重点加强对水环境中新型PFASs的关注;针对流域中不同种类PFASs建立高特异性、高灵敏度监测新技术;筛选适合的水生生物作为环境污染指示物以应用于新污染物的评估等建议。为今后我国地表水环境 PFASs污染的现状调查及治理工作提供确实可行的科学参考。     

原子力显微镜在环境样品研究与表征中的应用与展望

简要阐述了原子力显微镜仪器操作原理及最新成像技术发展情况;结合作者近期的研究工作,从环境微生物界面观察与表征、腐殖酸在微界面上的聚集行为观测、无机高分子絮凝剂的界面形貌及行为观察以及膜材料表面结构观测与表征等4个方面对原子力显微镜在环境领域内的应用情况作了概括介绍．最后,对原子力显微镜在环境微界面研究与表征中的应用前景进行了展望。