Characterization of submicron particles during autumn in Beijing, China

In this study, we performed a highly time-resolved chemical characterization of nonrefractory submicron particles(NR-PM_1) in Beijing by using an Aerodyne high-resolution time-of-flight aerosol mass spectrometer(HR-ToF-AMS). The results showed the average NR-PM_1 mass concentration to be 56.4 ± 58.0 μg/m~3, with a peak at 307.4 μg/m~3. Due to the high frequency of biomass burning in autumn, submicron particles significantly increased in organic content, which accounted for 51% of NR-PM_1 on average. Secondary inorganic aerosols(sulfate + nitrate + ammonium) accounted for 46% of NR-PM_1, of which sulfate,nitrate, and ammonium contributed 15%, 20%, and 11%, respectively. To determine the intrinsic relationships between the organic and inorganic species, we used the positive matrix factorization(PMF) model to merge the high-resolution mass spectra of the organic species and NO+and NO_2~+ions. The PMF analysis separated the mixed organic and nitrate(NO+and NO_2~+) spectra into four organic factors, including hydrocarbon-like organic aerosol(HOA), oxygenated organic aerosol(OOA), cooking organic aerosol(COA), and biomass burning organic aerosol(BBOA), as well as one nitrate inorganic aerosol(NIA) factor. COA(33%) and OOA(30%) contributed the most to the total organic aerosol(OA) mass, followed by BBOA(20%) and HOA(17%). We successfully quantified the mass concentrations of the organic and inorganic nitrates by the NO+and NO2+ions signal in the organic and NIA factors. The organic nitrate mass varied from 0.01-6.8 μg/m~3, with an average of 1.0 ±1.1 μg/m~3, and organic nitrate components accounted for 10% of the total nitrate mass in this observation.     

Simultaneous removal of ammonia and N-nitrosamine precursors from high ammonia water by zeolite and powdered activated carbon

When adding sufficient chlorine to achieve breakpoint chlorination to source water containing high concentration of ammonia during drinking water treatment, high concentrations of disinfection by-products(DBPs) may form. If N-nitrosamine precursors are present, highly toxic N-nitrosamines, primarily N-nitrosodimethylamine(NDMA), may also form. Removing their precursors before disinfection should be a more effective way to minimize these DBPs formation. In this study, zeolites and activated carbon were examined for ammonia and N-nitrosamine precursor removal when incorporated into drinking water treatment processes.The test results indicate that Mordenite zeolite can remove ammonia and five of seven N-nitrosamine precursors efficiently by single step adsorption test. The practical applicability was evaluated by simulation of typical drinking water treatment processes using six-gang stirring system. The Mordenite zeolite was applied at the steps of lime softening, alum coagulation, and alum coagulation with powdered activated carbon(PAC) sorption. While the lime softening process resulted in poor zeolite performance, alum coagulation did not impact ammonia and N-nitrosamine precursor removal. During alum coagulation, more than67% ammonia and 70%–100% N-nitrosamine precursors were removed by Mordenite zeolite(except 3-(dimethylaminomethyl)indole(DMAI) and 4-dimethylaminoantipyrine(DMAP)). PAC effectively removed DMAI and DMAP when added during alum coagulation. A combination of the zeolite and PAC selected efficiently removed ammonia and all tested seven N-nitrosamine precursors(dimethylamine(DMA), ethylmethylamine(EMA), diethylamine(DEA), dipropylamine(DPA), trimethylamine(TMA), DMAP, and DMAI) during the alum coagulation process.     

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.     

Behaviors and kinetics of toluene adsorption‐desorption on activated carbons with varying pore structure

This work was undertaken to investigate the behaviors and kinetics of toluene adsorption and desorption on activated carbons with varying pore structure. Five kinds of activated carbon from different raw materials were selected. Adsorption isotherms and breakthrough curves for toluene were measured. Langmuir and Freundlich equations were fitted to the equilibrium data, and the Freundlich equation was more suitable for simulating toluene adsorption. The process consisted of monolayer, multilayer and partial active site adsorption types. The effect of the pore structure of the activated carbons on toluene adsorption capacity was investigated. The quasi-first-order model was more suitable for describing the process than the quasi-second-order model. The adsorption data was also modeled by the internal particle diffusion model and it was found that the adsorption process could be divided into three stages. In the external surface adsorption process, the rate depended on the specific surface area. During the particle diffusion stage, pore structure and volume were the main factors affecting adsorption rate. In the final equilibrium stage, the rate was determined by the ratio of meso-and macro-pores to total pore volume. The rate over the whole adsorption process was dominated by the toluene concentration. The desorption behavior of toluene on activated carbons was investigated,and the process was divided into heat and mass transfer parts corresponding to emission and diffusion mechanisms, respectively. Physical adsorption played the main role during the adsorption process.     

东海浅陆架区溶解有机氮的时空分布特征及生物可利用性

通过2014年5~6月(春末夏初季)和9~10月(秋季)在东海浅陆架区的现场调查,分析该海域DON来源和时空分布特征,结合同步进行的船基受控生物降解培养实验,评价了该海域两个季节DON的生物可利用性。春末夏初季和秋季东海浅陆架区DON为总溶解态氮(TDN)的主要存在形式,在TDN中占比均值分别为57.88%±21.42%和66.09%±19.74%。受陆源输入和黑潮水涌升及浮游生物分泌和微生物降解作用共同影响,表层海水DON春末夏初季呈现近岸高、远岸低的变化特征,高值区与长江冲淡水影响范围基本一致;秋季高值区则位于该海域的东北部和东南部;而受长江冲淡水影响显著的调查海域北部DON浓度高于南部;从水体表层到底层DON浓度及其在TDN中的占比都呈现逐步降低的变化趋势。该海域DON的生物可利用性具有较大时空差异性,具有高生物可利用性的DON(L-DON)含量基本呈现近岸高、远岸低的分布特征,春末夏初季和秋季受陆源输入影响显著的海域中L-DON在DON中占比分别达到28.3%和23.6%,高于受陆源输入影响小的海域的1.3%和18.9%。     

基于IVE模型和大数据分析的杭州市道路移动源主要温室气体排放清单研究

利用IVE模型和对杭州市机动车排放管理数据库大数据的分析,得到杭州市2015年各类机动车主要温室气体高分辨率排放清单,分析了排放分担情况及时间变化特征,并利用Arc GIS及杭州市路网信息建立了1 km×1 km网格化空间分布.结果表明,杭州市道路移动源温室气体排放中CO_2、CH_4和N_2O的年排放量分别为818.11×10~4、0.85×10~4和0.07×10~4t,合计856.79×10~4t(以CO2当量计).从温室气体种类来看,CO_2占道路移动源温室气体排放总量的绝大部分,为95.5%;从机动车类型来看,小微型客车对道路移动源温室气体排放的贡献率最大,占72.8%;从道路类型的排放情况来看,杭州市市中心、城区、城郊和郊区中温室气体合计CO_2当量贡献率最高的均为主干路,分别为43.4%、61.8%、58.0%和42.4%.杭州市道路移动源温室气体排放强度均呈现由城市中心向城市边缘递减的趋势,同时温室气体排放量日变化特征明显,均出现弱双峰现象.     

不同培养方式下絮状污泥颗粒化特性和灰色关联度分析

为探索好氧颗粒污泥形成机理,开展了不同培养方式下絮状污泥颗粒化特性研究.选取3种培养方式:人工配水培养、海藻酸钠强化培养和农村模拟污水培养,利用灰色关联分析法,对比3种不同培养方式下,污泥颗粒化过程中各影响因素灰色关联度系数,筛选好氧颗粒污泥培养的关键因素.研究发现,人工配水培养方式下经过40 d成功出现好氧颗粒污泥,投加海藻酸钠强化培养方式下经过20 d出现好氧颗粒污泥,农村模拟污水经过55 d培养出好氧颗粒污泥.3种培养方式下出现的好氧颗粒污泥均具有密实的结构和较好的沉降性能,同时可实现对污染物的高效去除.利用数据处理系统(Data Processing System,DPS)对各影响因素的灰色关联度进行分析,发现不同培养方式下污泥颗粒化过程中起主导作用的影响因素并非唯一,水力停留时间和胞外聚合物在各培养方式中均具有较高的关联度系数,对好氧颗粒污泥的形成具有关键作用.     

粉煤灰提铝中间产物合成4A分子筛对氨氮的吸附行为研究

采用粉煤灰提铝中间产物合成4A分子筛,利用XRD、SEM、热重分析、化学成分分析、阳离子交换容量对4A分子筛进行表征.考察吸附时间、pH、分子筛投加量、氨氮初始浓度、共存阳离子对其吸附性能的影响,研究其对模拟废水中氨氮的吸附效果,并结合准二级动力学方程、吸附等温线研究吸附性能和机理.结果表明,初始浓度为50 mg·L~(-1)、4A分子筛投加量为5 g·L~(-1)、pH值为6~9、吸附时间为80 min时氨氮去除率可达71.34%;随着氨氮初始浓度升高,其去除率降低,吸附容量增加;共存阳离子Na~+、K~+、Ca~(2+)对NH_4~+有强烈的竞争吸附,Mg~(2+)无明显竞争作用.吸附过程符合准二级动力学方程和Freundlich模型.Langmuir吸附等温线显示最大吸附容量为20 mg·g~(-1).     

腈纶废水溶解性有机物的分级解析及可生化性

采用超滤膜法将腈纶废水中溶解性有机物分离为6个不同相对分子质量组分,分析不同组分的溶解性有机碳、UV₂₅₄、SUVA含量和分布情况,应用紫外吸收光谱、傅里叶变换红外光谱等光谱学分析方法对各组分物质结构进行定性分析,评价各组分的可生化性.结果表明废水中以相对分子质量< 3kDa的有机物为主,占比为（56.75±1.38）%;相对分子质量为3k~10kDa的有机物占比为（25.76±1.40）%;相对分子质量> 10kDa的有机物占比为（17.49±0.98）%,且该组分有机物的芳香度高.不同相对分子质量组分的紫外光谱和红外光谱均呈现相似吸收峰,均存在酰基、羧基、羰基及芳香族化合物和不饱和双键类有机物.各组分可生化性结果表明,废水中相对分子质量> 10kDa有机物是腈纶废水低可生化性的主要原因,可能是造成腈纶废水难以达标排放的根源.研究结果可为该废水处理工艺的开发与优化提供重要的指导.     

粒径和温度对玉米秸秆生物碳吸附锶的耦合影响

以玉米秸秆为原材料,在350℃下采用限氧裂解法制备了4种粒径的生物碳(BC-9.31、BC-20.26、BC-71.07、BC-101.90,数字代表样品的中值径,单位μm),对比研究了15℃、25℃、35℃、45℃下生物碳对锶的吸附行为,旨在阐明生物碳粒径和溶液温度对生物碳吸附锶的耦合影响。结果表明:生物碳粒径和溶液温度对等温吸附曲线的基本特征影响较小,Freundlich模型能较好地拟合吸附过程(R2=0.915~0.997,N=0.513~0.745);生物碳吸附锶是以熵驱动为主的物理吸附过程,熵变ΔS为75.66~99.43 J/(mol·K),焓变ΔH为18.18~25.84 k J/mol;生物碳对锶的吸附性能大体与溶液温度呈正相关,与颗粒粒径呈负相关,同时颗粒粒径与溶液温度存在耦合影响;生物碳粒径越小,锶吸附过程受温度影响越小;温度越高,锶吸附受粒径影响越小。