纳米零价铁(NZVI)对厌氧产甲烷活性、污泥特性和微生物群落结构的影响

重点比较了纳米零价铁(NZVI)和微米级铁(ZVI)短期暴露条件下,厌氧产甲烷过程中污泥产甲烷活性、污泥生理生化特征、细胞膜磷脂组成和微生物群落结构的变化.结果表明,NZVI组中累积产甲烷量随着NZVI投加浓度的增加降低.5 000mg·L~(-1)ZVI组累积产甲烷量未受影响.5 d时NZVI(100~5 000 mg·L~(-1))组铁离子浓度是空白组的1.6~7.4倍,5 000mg·L~(-1)ZVI组铁离子浓度略高于空白组.5 000 mg·L~(-1)NZVI组胞外聚合物总量大幅下降为空白组的21.1%,而活菌比仍可保持在空白组的79.7%.辅酶F420和辅酶M含量在5 000 mg·L~(-1)NZVI组中为空白组的40.2%和61.6%,但100 mg·L~(-1)NZVI组和5 000 mg·L~(-1)ZVI组中辅酶F420含量升高为空白组的1.3倍.不同实验组污泥支链脂肪酸和不饱和脂肪酸的总含量为:ZVI-5 000(21.18%)空白组(19.37%)NZVI-1000(16.69%)NZVI-5000(15.94%)NZVI-100(12.08%).NZVI可使环境中铁离子浓度升高和细胞膜流动性下降,降低细胞活性和产甲烷关键辅酶活性,从而对产甲烷过程造成抑制;主成分分析和冗余分析表明,厌氧系统中微生物群落组成可受到NZVI的影响发生较大变化,Nakamurella、Bacillus、Trichococcus和Petrimonas对NZVI耐受性高.     

基于紫外光谱分析的腐殖质混凝控制

腐殖质是水溶性天然有机物(DOM)的主要成分,对水处理过程有重要影响.为探究利用紫外光谱分析实现饮用水处理在线混凝控制的可行性和理论基础,以含腐殖酸和高岭土配水为实验对象,通过烧杯实验考察了不同水质条件对PACl混凝剂最佳投加量的影响,研究了SUVA_(254)和光谱特征斜率与混凝效果的相关性,利用排阻色谱分析了紫外光谱斜率与水体有机物组分之间的关系.结果表明,混凝剂最佳投加量与DOM浓度呈正比关系,两者计量学关系(以Al/DOC计)为0.61mg·mg~(-1).随混凝剂投加量的增加,腐殖酸溶液的SUVA_(254)从8.9 L·(mg·m)~(-1)下降并稳定至2.0 L·(mg·m)~(-1),有机物去除率与SUVA_(254)值呈正相关.光谱斜率与SUVA_(254)的变化趋势一致,且S_(275~295)与SUVA_(254)线性相关最优(R2=0.81).排阻色谱结果表明,混凝优先去除DOM中的腐殖质组分,S275~295与有机物中腐殖质组分对总UVA_(254)的占比存在明显的线性相关,光谱斜率测定对实现饮用水混凝过程的控制有重要意义.     

Molecular characterization of effluent organic matter in secondary effluent and reclaimed water: Comparison to natural organic matter in source water

Municipal wastewater reclamation is becoming of increasing importance in the world to solve the problem of water scarcity. A better understanding of the molecular composition of effluent organic matter(Ef OM) in the treated effluents of municipal wastewater treatment plants(WWTPs) is crucial for ensuring the safety of water reuse. In this study, the molecular composition of Ef OM in the secondary effluent of a WWTP in Beijing and the reclaimed water further treated with a coagulation–sedimentation–ozonation process were characterized using a non-target Fourier transform ion cyclotron resonance mass spectrometry(FT-ICR MS) method and compared to that of natural organic matter(NOM) in the local source water from a reservoir. It was found that the molecular composition of Ef OM in the secondary effluent and reclaimed water was dominated by CHOS formulas, while NOM in the source water was dominated by CHO formulas. The CHO formulas of the three samples had similar origins. Anthropogenic surfactants were responsible for the CHOS formulas in Ef OM of the secondary effluent and were not well removed by the coagulation-sedimentation-ozonation treatment process adopted.     

中国显示器件行业VOCs排放特征及控制对策

为掌握和了解我国电子行业VOCs的排放特征,以显示器件行业为研究对象,梳理和分析其生产工艺及排污环节;通过典型企业有机废气的实际排放监测,掌握其VOCs排放水平;利用排放因子法,核算了2011-2016年我国显示器件行业VOCs的排放量,分析其排放量的变化趋势及空间分布特征.结果表明:受产量和污染控制效率变化的双重影响,2011-2016年我国显示器件行业VOCs排放量（文中涉及"全国"的各要素范围均未包含港澳台地区）呈先增后降的趋势,2015年达到最大值（15 605 t）,此后在产量增长放缓和污染控制效率提高的作用下,2016年的排放量有所下降;从排放占比来看,显示器件行业无组织VOCs排放占比从2011年的45%升至2016年的53%,车间无组织VOCs逸散,以及废水处理过程、有机原辅料和有机废液储运等环节的VOCs无组织排放是行业污染控制的重点和难点.研究显示,我国显示器件行业VOCs无组织排放量占比逐年上升,为控制未来行业VOCs排放,企业应将无组织排放转化为有组织排放,之后再通过高效的末端处理装置来减少VOCs排放量.      

天津市区夏季碳气溶胶特征及改进的二次有机碳估算方法

为更加准确地估算环境受体PM_2.5中SOC（二次有机碳）的质量浓度,于2015年6-8月利用在线监测仪器同步采集小时分辨率的PM_2.5及OC（有机碳）和EC（元素碳）样品数据,分析碳气溶胶的变化特征,并尝试运用改进的EC示踪法估算ρ（SOC）.结果表明:天津市区夏季ρ（PM_2.5）为（70.9±46.0）μg/m3,ρ（OC）和ρ（EC）分别为（7.6±3.1）（2.2±1.5）μg/m3,占ρ（PM_2.5）的11.8%±4.6%和3.1%±1.4%,OC/EC（质量浓度之比,下同）的平均值为4.0±2.0.ρ（OC）与ρ（EC）之间的Pearson相关系数（R）仅为0.66,说明OC和EC的来源较为复杂,SOC的产生可能是重要影响因素.ρ（NO₂）与OC/EC呈显著负相关（R=-0.47,P < 0.01）,并且OC/EC（4.0）相对较低,说明天津市区机动车可能对碳气溶胶具有重要影响.ρ（SO₂）与ρ（OC）、ρ（EC）的相关性较低（R均为0.33,P均小于0.01）,说明天津市区碳气溶胶可能受燃煤源的影响较低.改进的EC示踪法主要是利用O₃和CO、EC作为光化学反应和一次源排放的指标,并结合ρ（OC）、ρ（EC）和OC/EC的变化特征,逐步筛选一次排放源主导的时间段的ρ（OC）和ρ（EC）数据,然后利用最小二乘法拟合获得ρ（OC）和ρ（EC）的线性方程,最后进行ρ（SOC）和ρ（POC）（POC为一次有机碳）的估算.天津市区夏季ρ（SOC）的平均值为（2.5±2.0）μg/m3,分别占ρ（OC）和ρ（PM_2.5）的28.8%±15.0%和3.7%±3.6%;ρ（POC）的平均值为（5.2±1.7）μg/m3,分别占ρ（OC）和ρ（PM_2.5）的71.2%±15.0%和8.1%±5.2%,说明天津市区夏季有机碳的主要来源是一次排放源.研究显示,相比于EC示踪法,改进的EC示踪法估算的ρ（SOC）明显降低,ρ（POC）明显升高.AT（大气温度）对ρ（SOC）的影响较为显著,而WS（风速）对ρ（POC）的影响较为显著.      

Investigating missing sources of glyoxal over China using a regional air quality model (RAMS-CMAQ)

Currently, modeling studies tend to significantly underestimate observed space-based glyoxal(CHOCHO) vertical column densities(VCDs), implying the existence of missing sources of glyoxal. Several recent studies suggest that the emissions of aromatic compounds and molar yields of glyoxal in the chemical mechanisms may both be underestimated, which can affect the simulated glyoxal concentrations. In this study, the influences of these two factors on glyoxal amounts over China were investigated using the RAMS-CMAQ modeling system for January and July 2014. Four sensitivity simulations were performed, and the results were compared to satellite observations. These results demonstrated significant impacts on glyoxal concentrations from these two factors.In case 1, where the emissions of aromatic compounds were increased three-fold,improvements to glyoxal VCDs were seen in high anthropogenic emissions regions. In case 2, where molar yields of glyoxal from isoprene were increased five-fold, the resulted concentrations in July were 3–5-fold higher, achieving closer agreement between the modeled and measured glyoxal VCDs. The combined changes from both cases 1 and 2 were applied in case 3, and the model succeeded in further reducing the underestimations of glyoxal VCDs. However, the results over most of the regions with pronounced anthropogenic emissions were still underestimated. So the molar yields of glyoxal from anthropogenic precursors were considered in case 4. With these additional mole yield changes(a two-fold increase), the improved concentrations agreed better with the measurements in regions of the lower reaches of the Yangtze River and Yellow River in January but not in July.     

Insights into the formation of secondary organic carbon in the summertime in urban Shanghai

To investigate formation mechanisms of secondary organic carbon(SOC) in Eastern China,measurements were conducted in an urban site in Shanghai in the summer of 2015. A period of high O_3 concentrations(daily peak 120 ppb) was observed, during which daily maximum SOC concentrations exceeding 9.0 μg/(C·m~3). Diurnal variations of SOC concentration and SOC/organic carbon(OC) ratio exhibited both daytime and nighttime peaks. The SOC concentrations correlated well with O_x(= O_3+ NO_2) and relative humidity in the daytime and nighttime, respectively, suggesting that secondary organic aerosol formation in Shanghai is driven by both photochemical production and aqueous phase reactions. Single particle mass spectrometry was used to examine the formation pathways of SOC. Along with the daytime increase of SOC, the number fraction of elemental carbon(EC) particles coated with OC quickly increased from 38.1% to 61.9% in the size range of 250–2000 nm, which was likely due to gas-to-particle partitioning of photochemically generated semi-volatile organic compounds onto EC particles. In the nighttime, particles rich in OC components were highly hygroscopic, and number fraction of these particles correlated well with relative humidity and SOC/OC nocturnal peaks. Meanwhile, as an aqueous-phase SOC tracer, particles that contained oxalate-Fe(III) complex also peaked at night. These observations suggested that aqueous-phase processes had an important contribution to the SOC nighttime formation. The influence of aerosol acidity on SOC formation was studied by both bulk and single particle level measurements, suggesting that the aqueous-phase formation of SOC was enhanced by particle acidity.     

FeCl3改性MOFs在低温下对Hg0的吸附性能

为提高吸附剂对Hg0（零价汞）的吸附效率,利用MOFs（金属有机框架）材料发达的孔隙结构和高比表面积（1 997.010 0 m2/g）,采用FeCl₃溶液浸渍改性,制备了吸附剂FeCl₃@MIL-101（Cr）用于脱除Hg0.在小型固定床反应器上考察了浸渍浓度、反应温度、氧含量等对Hg0去除的影响.结果表明:FeCl₃@MIL-101（Cr）在进口ρ（Hg0）为2×10-3 mg/L,c（FeCl₃）为0.2 mol/L,反应温度60℃,气体流速400 mL/min,φ（O₂）为1%的条件下,吸附穿透时间长达62 h,相应的吸附容量为14.27 mg/g.在此基础上,进一步利用BET（比表面积测试）、SEM（扫描电镜）-EDX（能量色散X射线光谱）、XRD（X射线衍射）、XPS（X射线光电子能谱）等常用表征手段研究了改性前后吸附剂的物理化学特性,证明了吸附剂FeCl₃@MIL-101（Cr）吸附零价汞是物理吸附与化学吸附共同作用的结果,含氯官能团在吸附Hg0过程中也发挥了相当大的作用,并且氧气可促进其吸附效果.最后,分析了其吸附机理.研究显示,该种吸附剂在低温条件下具有较为优良的脱汞性能,应用前景良好.      

溶解性有机质在岩溶水系统中的迁移转化及影响因素分析

溶解性有机质(DOM)的荧光物质是一种较好的示踪剂,用于鉴别DOM的来源及其在水文系统中的地球化学行为.该物质在岩溶水系统中的研究较少,并且要作为潜在示踪剂,系统中有很多因素影响其光谱信息.实验选取一典型岩溶流域,通过三维荧光光谱技术(EEMs)和平行因子分析(PARAFAC),结合水化学数据分析,揭示DOM荧光物质在不同岩溶含水空间的组成和转化关系,刻画流域尺度DOM的来源,探讨水化学因素对DOM荧光物质转移的影响机制.结果表明,流域外源地表水和岩溶地表水中的DOM以类蛋白色氨酸为主,浅层岩溶水和深层岩溶水以类蛋白色氨酸和酪氨酸为主.荧光指数(FI)、生物指数(BIX)和腐殖化指数(HIX)的综合分析认为,浅层岩溶水和深层岩溶水的DOM主要来自于内源微生物分解,岩溶地表水和外源地表水的DOM既有陆源输入又有内源微生物分解,且内源贡献占有较大比例.受岩溶水化学参数的影响,3种荧光物质具有明显的分异特征:类酪氨酸物质对Ca~(2+)和HCO_3~-具有较强的适应性,在岩溶水中存在的比例比较大.类色氨酸物质则相反,类富里酸物质则与TDS、浊度、Cl~-、SO_4~(2-)等呈现极显著正相关关系.流域上游浅层岩溶水中的DOM主要来自内源.出露地表以后,其有机质同时来自内源和外源输入.在流域下游渗入深层岩溶地下水以后,DOM逐渐向低芳香烃有机质化合物转化,大分子DOM逐渐减少,荧光强度减弱.主成分分析(PCA)提取出3个主成分,分别为反映岩溶水渗滤、转化、水流条件的水体矿化指标,反映土壤淋滤和自然渗滤关系的TOC、NO_3~-及类蛋白质指标,以及反映岩溶水系统水化学、生物化学过程的Ca~(2+)、HCO_3~-、荧光指数和类富里酸指标.此外研究还认为,总荧光强度,类富里酸物质和类蛋白物质可以分别作为岩溶水快速渗流、转化及岩溶含水层脆弱性的示踪剂.研究结果有助于认识岩溶地下水DOM的生物地球化学循环,进行岩溶系统有机污染控制,为岩溶水系统中物质的地球化学过程表征提供一种新的工具.     

厌氧条件下可溶性有机质对汞的还原与氧化作用

在沉积物、湿地和淹水的水稻土中天然可溶性有机质(DOM),如胡敏酸(HA)和富里酸(FA)处于还原状态,其介导Hg(Ⅱ)的还原,影响汞的转化及地球化学循环.本文通过模拟黑暗厌氧环境,研究还原态HA与FA对Hg(Ⅱ)的还原.结果表明,还原态HA与FA的还原容量高于对照氧化态HA与FA.还原态HA与FA对Hg(Ⅱ)的还原最佳浓度分别是0. 2mg·L~(-1)和1. 5 mg·L~(-1).而高于最佳浓度时,由于发生巯基竞争性络合作用,抑制Hg(Ⅱ)的还原;特别是还原态HA大于5mg·L~(-1)时,不能还原Hg(Ⅱ)为Hg(0).还原态HA与FA对Hg(Ⅱ)的还原反应动力学表明:有机碳(DOC)与Hg(Ⅱ)摩尔比DOC∶Hg(Ⅱ)=400∶1时,还原反应速率IHSS-HA FRC-HA FRC-FA;高摩尔比[DOC∶Hg(Ⅱ)=10 000∶1]时,还原态HA对Hg(Ⅱ)的还原反应停止,甚至向相反方向进行.还原态HA与FA对Hg(0)氧化结果表明,当还原态HA与FA浓度分别增加至5 mg·L~(-1)和10 mg·L~(-1)时,样品中检测不到Hg(0),还原态HA与FA对Hg(0)发生诱导性氧化络合作用.在汞的氧化还原与络合作用中,还原态DOM扮演双重角色,影响活性汞的可利用性,进而影响微生物汞的甲基化.