泉州市大气PM2.5镧系元素组成特征及来源解析

2014年3月、4月和7月分别采集了泉州市5个采样点共49个PM_(2.5)样品,采用电感耦合等离子体质谱(ICP-MS)测定样品镧系元素(Loid)及其他微量金属元素浓度水平.分析了PM_(2.5)镧系元素组成特征和配分模式,利用La-Ce-V三元图和化学质量平衡(CMB)受体模型解析了泉州市大气PM_(2.5)污染来源.结果表明:(1)泉州市大气PM_(2.5)总镧系元素(Σ Loid)浓度为2.490~5.708 ng·m~(-3)(含量65.682~126.529μg·g~(-1)),轻重镧系元素比值(L/H)为12.086~14.319;(2)PM_(2.5)镧系元素配分模式与福建土壤相似,PM_(2.5)中Ce元素表现为正异常,而Eu元素表现为负异常;(3)城市扬尘、燃煤尘、汽车尾气尘和垃圾焚烧飞灰是泉州市大气PM_(2.5)的主要来源,贡献率分别为18.9%、10.9%、30.6%和30.2%.     

Ethanol mediated As(III) adsorption onto Zn-loaded pinecone biochar: Experimental investigation, modeling, and optimization using hybrid artificial neural network-genetic algorithm approach

Organic matters (OMs) and their oxidization products often influence the fate and transport of heavy metals in the subsurface aqueous systems through interaction with the mineral surfaces. This study investigates the ethanol (EtOH)-mediated As(III) adsorption onto Zn-loaded pinecone (PC) biochar through batch experiments conducted under Box–Behnken design. The effect of EtOH on As(III) adsorption mechanism was quantitatively elucidated by fitting the experimental data using artificial neural network and quadratic modeling approaches. The quadratic model could describe the limiting nature of EtOH and pH on As(III) adsorption, whereas neural network revealed the stronger influence of EtOH (64.5%) followed by pH (20.75%) and As(III) concentration (14.75%) on the adsorption phenomena. Besides, the interaction among process variables indicated that EtOH enhances As(III) adsorption over a pH range of 2 to 7, possibly due to facilitation of ligand–metal(Zn) binding complexation mechanism. Eventually, hybrid response surface model–genetic algorithm (RSM–GA) approach predicted a better optimal solution than RSM, i.e., the adsorptive removal of As(III) (10.47 μg/g) is facilitated at 30.22 mg C/L of EtOH with initial As(III) concentration of 196.77 μg/L at pH 5.8. The implication of this investigation might help in understanding the application of biochar for removal of various As(III) species in the presence of OM.     

Shifts in microbial community structure and diversity in a MBR combined with worm reactors treating synthetic wastewater

The chemical oxygen demand (COD) and NH₃-N removal, membrane fouling, sludge characteristics and microbial community structure in a membrane bioreactor (MBR) coupled with worm reactors (SSBWR) were evaluated for 210 days. The obtained results were compared to those from a conventional MBR (C-MBR) operated in parallel. The results indicated that the combined MBR (S-MBR) achieved higher COD and NH₃-N removal efficiency, slower increase in membrane fouling, better sludge settleability and higher activities of the related enzymes in the activated sludge. Denaturing gradient gel electrophoresis was used to analyze the microbial community structures in the C-MBR and the S-MBR. The microbial community structure in the S-MBR was more diverse than that in the C-MBR. Additionally, the slow-growing microbes such as Saprospiraceae, Actinomyces, Frankia, Clostridium, Comamonas, Pseudomonas, Dechloromonas and Flavobacterium were enriched in the S-MBR, further accounting for the sludge reduction, membrane fouling alleviation and wastewater treatment.     

北京市郊区夏季臭氧重污染特征及生成效率

为研究北京郊区夏季O₃(臭氧)重污染过程特征及O₃生成的光化学敏感性,基于2016年夏季在北京郊区开展的针对O₃及其相关污染物的强化观测试验(7月23日—8月31日,共计40 d),分析了观测期间O₃浓度[以φ(O₃)计]变化特征、O₃重污染过程主控因素与O₃敏感性化学特征.结果表明:观测期间φ(O₃)超标时有发生,最大小时φ(O₃)为151.1×10-9,其中有15 d的φ(O₃)最大8 h滑动平均值(O₃-max-8h)超过了GB 3095—2012《环境空气质量标准》二级标准限值,占观测天数的37.5%;不同O₃重污染过程成因有所不同,城市烟羽传输的污染物对郊区O₃重污染过程影响显著(观测期间臭氧重污染过程:过程1,7月27—29日;过程3,8月9—11日;过程4,8月16日;过程5,8月21—24日),区域光化学污染对郊区O₃重污染过程也有贡献(观测期间O₃重污染过程2:8月4—6日);结合后向气流轨迹进一步辅助说明了不同重污染过程中O₃的来源不同.研究还发现,观测区域存在反“周末效应”现象,说明观测区域周末受人为影响较为明显;基于观测数据计算的OPE(O₃生成效率)分析了O₃光化学敏感性表明,在有OPE值的22 d内NO_x控制区和VOCs控制区出现的概率(41%)相等,即观测区域O₃对NO_x和VOCs均敏感;此外还发现,在O₃重污染过程中光化学敏感性会随其反应进程发生改变,由NO_x控制区逐渐转变为VOCs控制区.      

夏季太湖CDOM光学特性空间差异及其来源解析

为进一步探究夏季太湖CDOM（有色溶解性有机质）光学特性在空间分布上的差异性与其来源的关系,对其紫外-可见吸收及三维荧光光谱特性进行了分析研究,在此基础上进一步分析了CDOM吸尘系数及其荧光组分（C1、C2、C3、C4）强度和各水质参数间的相关性.结合主成分分析法探讨了CDOM的来源以及与各参数指标[ρ（DOC）除外]之间的来源关系.结果表明:CDOM吸收系数α（355）、S值（光谱斜率）变化范围分别为3.27~8.27 m-1和0.011~0.021 nm-1;太湖西部、北部及南部湖区CDOM丰度较大,S值较低,受陆源输入的影响较为明显.CDOM的三维荧光光谱揭示其中含有两种类蛋白质组分C1和C2以及类腐殖质组分C3和C4,并且以类蛋白质组分为主.此外,大部分采样点的荧光指数（FI）为1.70~2.01,自生源指数（BIX）大于1,腐殖化指数（HIX）小于0.6,r_（T/C）（荧光峰T与荧光峰C荧光强度比值）小于2,表明夏季太湖CDOM内源特性相对强烈.研究显示,除ρ（DOC）外,CDOM与其他水质参数在第一主成分上（贡献率为90.8%）均存在显著相关关系,说明各水质参数的来源存在相似性,并且受生物自生源影响更为显著.      

重庆市夏秋季VOCs对臭氧和二次有机气溶胶生成潜势的估算

为估算重庆市夏秋季VOCs（挥发性有机物）对O₃和SOA（二次有机气溶胶）的生成潜势,利用在线GC-MS/FID在2015年8月22日-9月23日对重庆市区点和郊区点VOCs开展了为期一个月的实时观测,获得市区点和郊区点$ \varphi $（TVOCs）（总挥发性有机物）分别为41.35×10-9和22.72×10-9,其中市区点以烷烃（35.2%）和烯炔烃（25.2%）为主,郊区点以含氧挥发性有机物（oxygenated volatile organic compounds,OVOCs）（30.6%）和烷烃（26.0%）为主.结合最大增量反应活性量化市区点和郊区点VOCs的OFPs（臭氧生成潜势）分别为149.11×10-9和71.09×10-9,市区点OFPs最大的是乙烯、丙烯、甲苯、C8和C9的芳香烃等,郊区点OFPs最大的VOCs是丙烯醛、异戊二烯和甲基乙烯基酮.结合气溶胶生成系数量化郊区点和市区点VOCs对SOA的生成贡献分别为0.36和1.26 μg/m3,相比国内其余城市VOCs的SOAP（二次有机气溶胶生成潜势）较小,主要以甲基环己烷、正壬烷、正葵烷和十一烷等高碳烷烃,以及甲苯、苯、二甲苯和乙苯等芳香烃的SOAP为主.研究显示,控制烯炔烃和芳香烃的浓度有助于控制重庆市O₃的生成,控制高碳烷烃和芳香烃则有助于控制重庆市SOA的生成.      

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.     

Nano-sized Fe2O3/Fe3O4 facilitate anaerobic transformation of hexavalent chromium in soil–water systems

The purpose of this study is to investigate the effects of nano-sized or submicro Fe_2O_3/Fe_3O_4 on the bioreduction of hexavalent chromium(Cr(VI)) and to evaluate the effects of nano-sized Fe_2O_3/Fe_3O_4 on the microbial communities from the anaerobic flooding soil.The results indicated that the net decreases upon Cr(VI) concentration from biotic soil samples amended with nano-sized Fe_2O_3(317.1 ± 2.1 mg/L) and Fe_3O_4(324.0 ± 22.2 mg/L) within21 days,which were approximately 2-fold of Cr(VI) concentration released from blank control assays(117.1 ± 5.6 mg/L).Furthermore,the results of denaturing gradient gel electrophoresis(DGGE) and high-throughput sequencing indicated a greater variety of microbes within the microbial community in amendments with nano-sized Fe_2O_3/Fe_3O_4 than the control assays.Especially,Proteobacteria occupied a predominant status on the phylum level within the indigenous microbial communities from chromium-contaminated soils.Besides,some partial decrease of soluble Cr(VI) in abiotic nano-sized Fe_2O_3/Fe_3O_4 amendments was responsible for the adsorption of nano-sized Fe_2O_3/Fe_3O_4 to soluble Cr(VI).Hence,the presence of nano-sized Fe_2O_3/Fe_3O_4 could largely facilitate the mobilization and biotransformation of Cr(VI) from flooding soils by adsorption and bio-mediated 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.      

结合WRF/Chem和PMF方法的邯郸市PM_(2.5)源解析

<正>向源模型法和反向受体模型法是进行城市PM_(2.5)源解析的2种方法,两者各有所长。该研究应用三维空气质量模型Weather Research and Forecasting Model with Chemistry(WRF-Chem)模型和受体模型Positive Matrix Factorization(PMF),以2014年10月为研究时段,分别对邯郸市的细微颗粒物(PM_(2.5))进行源解析。PMF模型的解析结果表明,邯郸市PM_(2.5)来源为二次源30.2%,燃煤源25.4%、金属冶炼源15.1%、机动车源14.4%、扬尘源9.8%,生物质燃烧源5.2%。应用WRF-Chem模型,Brute-Force方法解析出的结果为,在本地源贡献中,工业源贡献了49.0%,民用源11.9%、农业源9.6%、交通源3.8%和电厂源-1.5%(负值由于PM_(2.5)前体物之间的非线性反应所致)。应用源模型对二次成分(SO_4~(2-)、NO_3~-和NH_4~+)进行再解析,结果显示,燃煤源源贡献率最大,达到25.7%,其次分别为农业源(24.0%)、工业源(6.5%)、生物质源(1.8%)和机动车(0.03%)。结合2种方法得出,邯郸市的PM_(2.5)中,本地燃煤源贡献了37.1%,其次分别为金属冶炼源(18.4%)、机动车源(15.1%)、扬尘源(13.3%)、生物质燃烧源(6.2%)。