矿物超细颗粒的形成机制、结构特征及其环境行为和效应

矿物超细颗粒在自然环境中普遍存在,具有独特的环境行为和效应,对元素地球化学循环、污染物迁移转化和生态环境演变等有重要影响.矿物超细颗粒的环境行为和效应与其形成过程和结构特征密切相关.综述了物理、化学和生物过程驱动的矿物超细颗粒的形成机制,介绍了用于表征矿物超细颗粒结构特征的显微镜、光谱、质谱和同步辐射技术,分析了矿物超细颗粒在环境中的迁移转化及其与污染物的吸附、氧化还原和催化转化作用,总结了矿物超细颗粒的食物链积累、生物和生态毒性等环境效应,并对颗粒结晶路径、风险管控和微纳界面调控等重要研究方向进行了展望.超细颗粒是连接微观物质与宏观矿物晶体之间的桥梁,全面认识复杂基质中矿物颗粒的环境属性及其与污染物的微观作用机制,有助于指导矿物超细颗粒在环境污染修复中的应用,从而优化功能材料的设计,促进绿色低碳纳米技术的发展.     

济南秋季大气PM_(2.5)中水溶性离子的在线观测

2008年9月29日—10月15日使用大气细颗粒物快速捕集系统实时、在线分析了济南秋季PM2.5中水溶性离子的质量浓度,并结合气象资料和部分前体物(SO2,NOx和O3)浓度进行了相关分析.结果表明:济南秋季燃煤污染严重,SO42-,NO3-和NH4+是大气PM2.5中水溶性离子的主要组分,三者质量浓度之和占总水溶性离子(TW SI)质量浓度的90%以上;SO42-污染物主要受远距离传输的影响,NO3-和NH4+污染物主要受局地源的影响;SO42-和NO3-的昼夜形成机理不同,它们的形成过程主要受相对湿度、温度和O3浓度的影响.周边地区生物质燃烧导致了济南重污染天气的产生,降水对污染物的清除作用较强.对比土壤和海盐中各种离子的质量浓度比可知,济南秋季PM2.5中的K+受生物质燃烧的影响较大,C l-主要来源于海盐和生物质燃烧,Na+主要来源于海盐.     

Transparent exopolymer particles (TEPs)-associated protobiofilm: A neglected contributor to biofouling during membrane filtration

• Bacteria could easily and quickly attached onto TEP to form protobiofilms. • TEP-protobiofilm facilitate the transport of bacteria to membrane surface. • More significant flux decline was observed in the presence of TEP-protobiofilms. • Membrane fouling shows higher sensitivity to protobiofilm not to bacteria level. Transparent exopolymer particles (TEPs) are a class of transparent gel-like polysaccharides, which have been widely detected in almost every kind of feed water to membrane systems, including freshwater, seawater and wastewater. Although TEP have been thought to be related to the membrane fouling, little information is currently available for their influential mechanisms and the pertinence to biofouling development. The present study, thus, aims to explore the impact of TEPs on biofouling development during ultrafiltration. TEP samples were inoculated with bacteria for several hours before filtration and the formation of “protobiofilm” (pre-colonized TEP by bacteria) was examined and its influence on biofouling was determined. It was observed that the bacteria can easily and quickly attach onto TEPs and form protobiofilms. Ultrafiltration experiments further revealed that TEP-protobiofilms served as carriers which facilitated and accelerated transport of bacteria to membrane surface, leading to rapid development of biofouling on the ultrafiltration membrane surfaces. Moreover, compared to the feed water containing independent bacteria and TEPs, more flux decline was observed with TEP-protobiofilms. Consequently, it appeared from this study that TEP-protobiofilms play a vital role in the development of membrane biofouling, but unfortunately, this phenomenon has been often overlooked in the literature. Obviously, these findings in turn may also challenge the current understanding of organic fouling and biofouling as membrane fouling caused by TEP-protobiofilm is a combination of both. It is expected that this study might promote further research in general membrane fouling mechanisms and the development of an effective mitigation strategy.     

Characteristics and mixing state of S-rich particles in haze episodes in Beijing

Direct individual analysis using Scanning Electron Microscopy combined with online observation was conducted to examine the S-rich particles in PM_2.5 of two typical polluted haze episodes in summer and winter from 2014 to 2015 in Beijing. Four major types of S-rich particles, including secondary CaSO₄ particles (mainly observed in summer), S-rich mineral particles (SRM), S-rich water droplets (SRW) and (C, O, S)-rich particles (COS) were identified.We found the different typical morphologies and element distributions of S-rich particles and considered that (C, O, S)-rich particles had two major mixing states in different seasons. On the basis of the S-rich particles’ relative abundances, S concentrations and their relationships with PM_2.5 as well as the seasonal comparison, we revealed that the S-participated formation degrees of SRM and SRW would enhance with increasing PM_2.5 concentration. Moreover, C-rich matter and sulfate had seasonally different but significant impacts on the formation of COS.

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基于PMF模式的南京市大气细颗粒物源解析

为研究南京市大气细颗粒物(PM2.5)污染来源,分别在3个点位、4个季节开展了PM2.5环境样品的采集,共获得170个有效样本.对样本进行了化学成分分析,包括Al、Fe、Na、Mg、K、Ba、Li、Tl、Mn、Co、Ni、Cu、Zn、Sb、Pb、Cr、Ce、Na+、NH4+、Mg2+、Ca2+、SO42-、NO3-、Cl-、以及OC、EC,共计26种.首先采用OC/EC最小比值法估算出二次有机气溶胶(SOA)的含量;然后利用正矩阵因子分解法(PMF)对PM2.5的非SOA部分进行来源解析,共解析出6类因子:二次无机气溶胶(SIA)、燃煤、机动车排放、地面扬尘、冶金和其它源,贡献率分别25.0%、23.5%、20.4%、17.1%、3.0%和11.0%;最后基于南京市SO2、NOx、VOCs三种主要前体污染物的排放量,分别对SIA和SOA在一次来源中进行再分配.最终结果表明,南京市PM2.5主要来源为燃煤、机动车、扬尘、工业和其它源,其贡献率分别为29.6%、22.4%、14.6%、18.7%和14.7%.     

细微泥沙对活性污泥系统的影响及其恢复特征

不同地区、排水体制和季节下,我国城市污水厂进水中细微泥沙含量〔以ρ(ISS)/ρ(COD_Cr)表征,ISS为无机悬浮固体〕差异较大,细微泥沙进入生化处理单元将会对活性污泥系统的正常运行产生一定影响. 考察在不同进水细微泥沙浓度下,活性污泥系统各运行参数的变化及系统恢复情况,结果表明:①随着进水中细微泥沙浓度的增大,活性污泥系统ρ(MLVSS)/ρ(MLSS)、SOUR′(单位质量污泥活性)、CST(污泥毛细吸水时间)和SVI(污泥容积指数)降低;在影响期,ρ(MLVSS)/ρ(MLSS)最小值、SOUR′平均值、CST平均值与细微泥沙浓度均呈良好的线性关系,R2(相关系数)分别为0.963 7、0.979 9和0.786 5;系统恢复所需时间与进水细微泥沙浓度呈正相关. ②污泥中细微泥沙浓度的增加导致SOUR′下降,使得ρ(MLSS)和剩余污泥量增加,不利于污水厂的节能减排. 可见进水中细微泥沙浓度的增大不利于污水厂的稳定高效运行.      

黄山大气气溶胶新粒子生长特性观测分析

利用2012年9月22日~10月28日黄山地区大气气溶胶、二氧化硫和臭氧观测数据,结合气象数据,分析气溶胶新粒子的生成-增长特征.分析发现,在33个有效观测日中,有新粒子生成-增长的观测日占总数的18.2%,其中晴天的发生频率为37.5%,新粒子生成-增长都开始于晴天上午,与无新粒子观测日相比,太阳辐射量、风速、SO2及O3浓度较高,环境温度和相对湿度较低.气溶胶新粒子的增长具有由小及大的特点,核模态气溶胶粒子(10~20nm)数浓度最先增加,爱根核模态粒子(20~50nm)数浓度随着时间推移逐渐增大,但浓度峰值依次下降,平均增长率为3.58nm/h. SO2浓度先于核模态气溶胶数浓度到达峰值,其氧化后的产物H2SO4为新粒子的核化提供前体物,并且参与新粒子的增长过程,当SO2浓度较低时,不会发生新粒子生长事件.     

Optimizing synthesis conditions of nanoscale zero-valent iron (nZVI) through aqueous reactivity assessment

Nanoscale iron particles (nZVI) is one of the most important engineered nanomaterials applied to environmental pollution control and abatement. Although a multitude of synthesis approaches have been proposed, a facile method to screen the reactivity of candidate nZVI materials produced using different methods or under varying synthesis conditions has yet been established. In this study, four reaction parameters were adjusted in the preparation of borohydride-reduced nZVI. The reductive properties of the resultant nanoparticles were assayed independently using two model aqueous contaminants, Cu(II) and nitrate. The results confirm that the reductive reactivity of nZVI is most sensitive to the initial concentration of iron precursor, borohydride feed rate, and the loading ratio of borohydride to ferric ion during particle synthesis. Solution mixing speed, in contrast, carries a relative small weight on the reactivity of nZVI. The two probing reactions (i.e., Cu(II) and nitrate reduction) are able to generate consistent and quantitative inference about the mass-normalized surface activity of nZVI. However, the nitrate assay is valid in dilute aqueous solutions only (50 mg·L⁻¹ or lower) due to accelerated deactivation of iron surface at elevated nitrate concentrations. Additional insights including the structural and chemical makeup of nZVI can be garnered from Cu(II) reduction assessments. The reactivity assays investigated in this study can facilitate screening of candidate materials or optimization of nZVI production parameters, which complement some of the more sophisticated but less chemically specific material characterization methods used in the nZVI research.     

蒸汽相变促进可溶PM2.5凝结增长的数值分析

为利用蒸汽相变原理促进氨法脱硫系统排放细颗粒物(PM2.5)的脱除,建立多分散颗粒的凝结增长动力学模型,利用数值模拟方法研究了可溶硫酸铵颗粒的凝结增长规律,并将典型粒径可溶与不可溶颗粒的凝结增长过程进行对比分析.结果表明:不同粒径硫酸铵颗粒的增长速率相近,等温系统的凝结增长效果优于绝热系统;对于同一初始粒径分布下的可溶和不可溶颗粒,微米尺度可溶颗粒的增长速率始终大于不可溶颗粒,亚微米尺度可溶颗粒的增长速率先大于而后小于不可溶颗粒,使得二者的增长曲线存在一个交叉点;蒸汽饱和度增大能显著促进硫酸铵颗粒的增长;等温系统中温度对硫酸铵颗粒的增长影响显著,绝热系统中温度的影响较弱.     

北京地区大气细颗粒物的个体暴露水平

于2012年12月至2013年4月采用LD6S型微电脑激光粉尘仪在北京地区采取单人逐日跟踪的方式记录了多名个体对大气细颗粒物(PM2.5)的暴露水平,同时收集研究对象的时间-活动日志,计算日平均暴露水平,再进行多人多日合并处理.并于研究时段内同步记录北京市环境保护监测中心发布的空气质量监测数据.结果表明,研究期间北京地区冬季与春季PM2.5的平均浓度分别为127,69μg/m3.个体日均暴露水平中值为54μg/m3,与大气质量浓度的平均比值为0.60.个体室内暴露分量均值达到总暴露量的80%,室外与交通各占约10%.不同人群及季节的暴露水平之间未表现出显著差异.当大气环境质量浓度高于国家空气质量二级标准浓度限值时,室内住宅、办公室和餐厅,室外公交车、街道微环境中的PM2.5质量浓度与大气环境质量浓度存在显著的相关关系.