唐山夏季大气VOCs污染特征及臭氧生成潜势

在唐山市区对大气环境VOCs进行样品采集,对VOCs污染特征及臭氧生成潜势进行了分析。结果表明:唐山市区VOCs主要以烷烃和芳香烃为主,分别占VOCs总质量浓度的50.3%和30.4%。烷烃和烯烃以丁烷和丙烯等组分为主,芳香烃以苯、甲苯、乙苯和二甲苯为主。由于污染源排放强度、气象条件和光化学反应强弱的影响,VOCs浓度有明显的小时变化特征,8:00—10:00浓度最高,中午较低,且与早上相比,烯烃浓度降低比例中午最大。VOCs臭氧生成潜势敏感性组分以烯烃为主,占总VOCs臭氧生成潜势贡献的49.0%~66.8%,其主要敏感性种类为丙烯。     

典型地方炼化企业VOCs排放特征及其对二次污染生成的贡献

为研究石化行业VOCs的排放特征及其环境影响,选取山东省3家典型地方炼化企业开展样品采集和物种分析,并利用MIR(最大增量反应活性)法和SOAP(二次有机气溶胶生成潜势)法量化其对二次污染生成的贡献.结果表明,不同生产类型企业VOCs排放组成差异较大.从体积浓度来看,企业A各采样点位以芳香烃(30.4%~92.2%)为主要排放化合物;企业B排放以烷烃(15.4%~53.8%)、烯炔烃(11.4%~71.7%)和含氧VOCs(0.1%~53.8%)为主;企业C则主要排放烷烃(6.1%~95.3%)和烯炔烃(1.2%~93.1%).从合成源谱来看,企业A以芳香烃为主要化合物,乙苯、苯、苯乙烯、甲苯为高排放物种;企业B中烷烃、烯炔烃和含氧VOCs均有较高占比,1-丁烯、甲基乙基酮、反-2-丁烯、异丁烷、甲苯为主要物种;企业C则主要排放烷烃类化合物,包括异丁烷、丙烷、环戊烷.OFP(臭氧生成潜势)评估结果表明,芳香烃化合物包括乙苯、苯乙烯、苯和甲苯,其对企业A的贡献最大;企业B中,烯炔烃化合物包括1-丁烯、反-2-丁烯、异戊二烯,其OFP占比最高;企业C则以烯炔烃和烷烃为高贡献化合物,其中丙烯、异丁烷、间/对-二甲苯、顺-2-丁烯为关键活性物种.SOAP评估结果表明,各企业SOA(二次有机气溶胶)的生成均由芳香烃主导,关键活性物种为甲苯、苯乙烯、苯、间/对-二甲苯.研究显示,地方炼化企业所排的VOCs组分复杂且存在显著的工艺差异,应根据筛选出的关键活性组分制定针对性的VOCs减排策略.      

成都市工业挥发性有机物排源成分谱

选取成都市汽车制造和石油化工等典型工业行业,通过瓶采样和SUMMA罐采样及GC-MS分析方法,研究了不同生产工艺环节的挥发性有机物(VOCs)排放特征.结果表明,汽车制造各工艺环节均有各自的优势组分,其中喷漆排放以烷烃(32%)和芳香烃(35%)为主.家具制造排放特征与使用原辅料高度相关,以芳香烃(50%)和OVOCs(38%)为主.石油化工各装置区VOCs浓度范围为49～1 387μg·m~(-3),不同装置区存在较大差异,主要是由于炼油区主要产品为C_5～C_9的汽油和苯系物等,化工区则较多使用了溶剂同时生成烯烃类产品.电子制造均以OVOCs为主,占VOCs总排放的50%以上.制鞋行业排放VOCs主要由烷烃和OVOCs贡献,平均占比分别为52%和36%,与所用溶剂组分高度相关.汽车制造VOCs排放组分差异较大,主要以正十二烷和2-丁酮等为主.家具制造排放组分主要为苯乙烯、乙酸乙酯和间/对-二甲苯等,为涂料和稀释剂的典型组分.石油化工各装置区排放组分有差异,炼油区以苯乙烯等为主,化工区主要为1,3-丁二烯等,仓储区主要为C_3～C_5烷烃等,废水处理则主要为C_6～C_8烷烃等.电子制造主要组分均为乙醇和丙酮等醛酮组分.制鞋企业排放组分以C_5和C_6等烷烃为主.通过臭氧生成潜势计算比较,汽车制造和石油化工行业对臭氧生成潜势贡献较大的VOCs排放组分以烯烃和芳香烃为主,具有较高的污染源反应活性.研究表明各工业行业OVOCs排放比例(17%～96%)和对臭氧生成潜势贡献均较为显著,因此在进行VOCs排放控制时,除重点管控芳香烃和烯烃外,亦应提高对OVOCs组分的关注.     

大连市城区夏季环境空气VOCs污染特征及来源分析

利用Synspec GC955-611/811在线气相色谱仪对大连市城区2019年夏季(5～8月)大气中VOCs进行了连续监测,研究了VOCs组分浓度情况和月变化特征。结果表明,烷烃是城区大气中最丰富的VOCs物种,其他依次是芳香烃、炔烃和烯烃。5～7月大连市城区VOCs浓度整体保持稳定,8月份浓度明显升高。利用最大增量反应活性(MIR)计算了各类VOCs的臭氧生成潜势(OFP),各组分对臭氧生成潜势贡献排名分别为烷烃、芳香烃、烯烃和炔烃,分别占比45.8%、29.3%、19.8%和5.1%。关键VOCs活性物种甲苯、异戊烷和正丁烷分别占VOCs总体积浓度的5.6%、10.7%和13.0%。利用PMF受体模型对VOCs的来源进行解析研究,2019年夏季大连市VOCs主要来源来自涂料/溶剂使用(45.1%)、机动车排放(24.0%)、油气挥发(16.1%)、液化石油气(10.7%)、天然源(4.0%)。     

基于包扎法的石化乙烯装置挥发性有机物排放特征

装置泄露是石油炼化生产过程中重要的挥发性有机物(VOCs)无组织排放源.基于动态吹扫包扎法采样和预浓缩­­-GC/MS分析方法,对我国南方某石化企业乙烯生产过程中裂解装置的压缩、分离系统及芳烃抽提装置的泄漏组件进行了VOCs排放特征研究.结果表明:烷烃(49.7%~82.4%)含量最高,其次是烯烃(3.2%~35.7%)和芳香烃(5.5%~14.4%); 2-甲基戊烷、甲基环己烷、3-甲基己烷及2,3-二甲基丁烷在整个乙烯生产中都有重要比重.乙烯和反-2-丁烯是裂解装置的重要标志,而苯和甲苯是芳烃抽提装置的重要标志;臭氧生成潜势主要来自于烯烃,尤其是乙烯的贡献率最大,占总烯烃贡献的47.0%~73.0%.参考美国环保局推荐的Method-21,计算了轻液介质阀门的排放速率,获得其泄露排放速率与泄露浓度之间的定量关系为y=3×10^-7x^0.993(R²=0.788).     

深圳大气VOCs浓度的变化特征与化学反应活性

对深圳2010年4个季节大气中VOCs进行了监测,研究了VOCs组分、季节变化和日变化特征.结果表明,烷烃是大气中含量最丰富的VOCs物种,占总VOCs的50%以上,其他依次是芳香烃和烯烃.总VOCs浓度季节变化表现为冬季最高和夏季最低,日变化特征则表现为夜晚浓度高、白天浓度低,峰值出现在早晨7:00左右,最低值则出现在下午14:00.通过VOCs物种间的比值特征分析了部分物种的来源,结果显示,反式-2-丁烯和顺式-2-丁烯主要来源于机动车尾气,甲苯和正己烷则受到了溶剂挥发的影响.利用最大增量反应活性(MIR)计算了各类VOCs的臭氧生成潜势(OFP),大气各类VOCs的OFP芳香烃最高、其次为烯烃,烷烃最低,甲苯、间,对-二甲苯和乙烯对臭氧生成的贡献在VOCs物种中排名前3.     

涂料制造行业挥发性有机物排放成分谱及影响

采用不锈钢采样罐对华东地区8家涂料制造企业生产车间排口进行采集,运用气相色谱-质谱联用技术（GC-MS）测定了106种VOCs组分,识别了VOCs排放特征,建立了溶剂型涂料和水性涂料VOCs排放成分谱,分析了VOCs对臭氧生成的贡献.结果表明,涂料制造行业VOCs特征组分主要为芳香烃和含氧烃,两者浓度范围在65.5%~99.9%,溶剂型涂料VOCs排放主要以芳香烃为主,占总VOCs的63.0%~94.0%;水性涂料VOCs排放主要以含氧烃为主,占总VOCs的54.5%~99.9%.间/对-二甲苯（32.4%）、乙苯（19.0%）和乙酸乙酯（12.1%）为溶剂型涂料源排放特征,乙酸乙酯（83.7%）与2-丁酮（8.0%）为水性涂料源排放特征.芳香烃和含氧烃是涂料制造行业的主要活性组分,对臭氧生成潜势（OFP）的总贡献率在92.9%~99.9%之间.源反应活性分析（SR）表明,水性涂料单位质量VOCs对臭氧的生成贡献低于溶剂型涂料,因此可显著降低臭氧的生成潜势.研究显示,针对涂料制造行业VOCs污染治理,应重点关注芳香烃和含氧烃中对臭氧生成潜势贡献较大的VOCs组分,进行源头和精细化控制.     

上海市城区春节和“五一”节期间大气挥发性有机物的组成特征

挥发性有机物(VOCs)是对流层臭氧和二次有机气溶胶等二次污染生成过程的关键前体物.研究VOCs的浓度水平、组成特征和反应活性对揭示复合型大气污染的形成机制具有重要意义.本研究利用在线气相-氢离子火焰法测量了2009年春节和"五一"节期间上海市城区大气中56种VOCs.结果表明,上海市城区大气受机动车尾气排放源影响明显,VOCs浓度日变化特征呈双峰状,与上下班交通高峰基本吻合.大气中VOCs平均体积分数为(28.39±18.35)×10-9;各组分百分含量依次为:烷烃46.6%,芳香烃27.0%,烯烃15.1%,乙炔11.2%.用OH消耗速率和臭氧生成潜势(OFP)评估了VOCs大气化学反应活性,结果表明,上海市城区大气VOCs化学反应活性与VOCs体积浓度相关性良好;VOCs活性与乙烯相当,平均化学反应活性较强;OH消耗速率贡献最大的物种是烯烃51.2%和芳香烃31.8%;OFP贡献最大的物种是芳香烃53.4%和烯烃30.2%;对臭氧生成贡献最大的关键活性物种为丙烯、乙烯、甲苯、二甲苯以及丁烯类物质.     

天津市夏季不同臭氧浓度级别VOCs特征及来源

为深入了解挥发性有机物（VOCs）对臭氧（O₃）污染的影响,基于2019年夏季天津市O₃和VOCs高时间分辨率在线监测数据,对不同O₃浓度级别VOCs污染特征及来源进行分析.结果表明,2019年夏季天津市O₃浓度为优、良、轻度污染和中度污染时,VOCs浓度分别为32.94、38.10、42.41和47.12μg·m^-3.VOCs组分中烷烃、烯烃、炔烃和芳香烃浓度占比分别为61.72%~63.36%、14.96%~15.51%、2.73%~4.13%和18.53%~19.10%,其中烷烃在O₃浓度为良和轻度污染时占比略高,烯烃和炔烃在O₃浓度为优时占比最高,芳香烃在O₃浓度为中度污染时占比最高.浓度较高的VOCs物种主要为丙烷、乙烷、乙烯、甲苯、正丁烷、异戊烷、间/对-二甲苯、丙烯、乙炔、正己烷、异丁烷、苯、正戊烷、异戊二烯和1,2,3-三甲苯,其中异戊烷、正戊烷、苯、乙烯、丙烯、正丁烷和异丁烷浓度贡献随O₃浓度级别上升逐步增加,异戊二烯和1,2,3-三甲苯浓度贡献在轻中度污染时明显升高.烯烃和芳香烃对臭氧生成潜势（OFP）贡献较高,随着O₃浓度级别上升,烯烃对OFP贡献下降,芳香烃贡献上升.乙烯、丙烯、间/对-二甲苯、1,2,3-三甲苯、甲苯、异戊二烯、反-2-丁烯和顺-2-戊烯是影响臭氧生成的关键物种,其中1,2,3-三甲苯、异戊二烯、丙烯和乙烯对OFP的贡献比例在O₃为轻中度污染时明显增加.源解析结果显示,机动车排放源、溶剂使用源、LPG/汽油挥发源、燃烧源、石化工业排放源、天然源和其他工艺过程源是天津市夏季VOCs主要来源,随着O₃浓度级别上升,机动车排放源、LPG/汽油挥发源、石化工业排放源和天然源贡献逐渐增加,燃烧源和其他工艺过程源贡献总体下降,溶剂使用源贡献在轻中度污染时有所下降.     

南阳市冬春交替期大气VOCs污染特征及来源解析

近年来我国中部地区臭氧污染问题日益凸显,而挥发性有机物(VOCs)作为近地面臭氧生成的关键前体物,有关其来源研究相较于我国东部地区相对欠缺.为了解我国中部地区VOCs污染特征及其来源,本研究于2017年2—3月在豫鄂陕三省交界处的河南省南阳市南阳理工学院站点开展了为期1个月的VOCs在线监测.测量结果显示,观测期间总VOCs平均浓度为(37.4±18.5)×10~(-9).与国内外已有研究的VOCs测量结果相比,本研究中烷烃、烯烃和炔烃的浓度处于中等偏上水平,而芳香烃浓度则较低.烯烃对臭氧潜势的贡献最高(37%),其次是芳香烃(28%).乙烯、二甲苯、甲苯、丙烯和C4~C5烷烃是最重要的活性组分.利用正交矩阵因子分析(PMF)解析出4个因子,分别是天然气/液化石油气使用+背景、交通排放、溶剂涂料使用和燃煤+生物质燃烧.观测期间南阳理工学院站点对VOCs浓度贡献最高的是燃煤+生物质燃烧因子,平均贡献率为35%,其次是交通排放因子(25%)、天然气/LPG使用+背景(23%)和溶剂涂料使用(17%).研究结果对于认识我国中部地区VOCs来源结构,进而开展VOCs和臭氧防治具有重要意义.     

Distribution and ecological effect of mercury in Laogang landfill, Shanghai, China

Laogang landfill near Shanghai is the largest landfill in China, and receives about 10000 t of daily garbage per day, Samples of topsoil and plants were analyzed to evaluate mercury pollution from the landfill. For topsoil samples, there were significant correlations among total mercury （HgT）, combinative mercury （Hgc） and gaseous mercury （HgG）, and content of total organic carbon （TOC）, but, no significantly relationship was found between Hg content and filling time. Hg content changes in vertical profiles with time showed that the average Hgv of profiles 1992, 1996, and 2000 was similar, but their average HgG was quite different. HgT was significantly correlated with Hgc in profile 1992 and 2000, and Hgv was significantly correlated with Hg6 in profile 1996. HgG/Hgv ratio in profile samples decreased in the order of （HgG,/HgT）1992〉（HgG/HgT）1996〉〉（HgG/HgT）2000. A simple outline of Hg release in landfill could be drawn： with increasing of filling time, degradation undergoes different biodegradation, accordingly, gaseous mercury goes through small, more, and small proportion to total mercury. Distribution of Hg in plants was inhomogeneous, following the order of leaf〉root〉stem. The highest value of leaf may be associated with higher atmospheric Hg from landfill. Ligneous plants （e.g. Phyllostachys glanca, Prunus salicina and Ligustrum lucidum） are capable of enriching more Hg than herbaceous plants.     

EDTA-enhanced phytoremediation of lead contaminated soil by Bidens maximowicziana

Phytoremediation is a potential cleanup technology for the removal of heavy metals from contaminated soils.Bidens maximowicziana is a new Pb hyperaccumulator,which not only has remarkable tolerance to Pb but also extraordinary accumulation capacity for Pb.The maximum Pb concentration was 1509.3 mg/kg in roots and 2164.7 mg/kg in overground tissues.The Pb distribution order in the B. maximowicziana was:leaf>stem>root.The effect of amendments on phytoremediation was also studied.The mobility of soil Pb and the Pb concentrations in plants were both increased by EDTA application.Compared with CK(control check),EDTA application promoted translocation of Pb to overground parts of the plant.The Pb concentrations in overground parts of plants was increased from 24.23-680.56 mg/kg to 29.07-1905.57 mg/kg.This research demonstrated that B.maximowicziana appeared to be suitable for phytoremediation of Pb contaminated soil,especially,combination with EDTA.     

Decomposition of alachlor by ozonation and its mechanism

Decomposition and corresponding mechanism of alachlor, an endocrine disruptor in water by ozonation were investigated. Results showed that alachlor could not be completely mineralized by ozone alone. Many intermediates and final products were formed during the process, including aromatic compounds, aliphatic carboxylic acids, and inorganic ions. In evoluting these products, some of them with weak polarity were qualitatively identified by GC-MS. The information of inorganic ions suggested that the dechlorination was the first and the fastest step in the ozonation of alachlor.     

Enzymatic oxidation of aqueous pentachlorophenol

The influence of the nonionic surfactant Tween 80 on pentachlorophenol （PCP） oxidation catalyzed by horseradish peroxidase was studied. The surfactant was tested at concentrations below and above its critical micelle concentration （CMC）. Enhancement of PCP removal was observed at sub-CMCs. The presence of Tween 80 in the reaction mixture reduced enzyme inactivation which occurred through a combination of free radical attack and sorption by precipitated products. A simple first-order model was able to simulate time profiles for enzyme inactivation in the presence or absence of Tween 80. At supra-CMCs, the surfactant caused noticeable reductions in PCP removal, presumably through micelle partitioning of PCP which precluded the hydrophobic PCP molecule from interacting with the enzyme.     

基于综合水质标识指数和对应分析法的校园河道水质评价

以三峡大学的校园河道求索溪为研究对象,利用综合水质标识指数法确定求索溪水质类别,分析其水质时空变化规律,并利用对应分析法得出求索溪中不同监测点的主要污染因子.研究结果表明:求索溪整体的综合水质标识指数为7.423,整体水质为劣V类(地表水环境质量标准GB 3838-2002)且黑臭.从时间变化来看,求索溪4月份的水质最差,5月份次之,4、5月份所有监测点的水质都劣于V类且黑臭;8月份水质最好,水质为Ⅳ类;从空间分布来看,8个监测点综合水质标识指数均超过6.0,水质为劣V类,其中6号监测点的水质相对最好,监测点3号的水质相对最差;对应分析法得出求索溪的整体水体污染程度受总氮因子的影响最大,其次为总磷.该研究拟为求索溪及类似校园河道的水环境治理研究提供基础依据和参考.     

Effects of chitosan on growth of an aquatic plant (Hydrilla verticillata) in polluted waters with different chemical oxygen demands

Effects of chitosan on a submersed plant, Hydrilla verticillata, were investigated. Results indicated that H. venicillata could prevent ultrastructure phytotoxicities and oxidativereaction from polluted water with high chemical oxygen demand (COD). Superoxide dismutase (SOD) activity and malondialdehyde (MDA) contents in H. verticillata treated with 0.1% chitosan in wastewater increased with high COD (980 mg/L) and decreased with low COD (63 mg/L), respectively. Ultrastructural analysis showed that the stroma and grana of chloroplast basically remained normal. However, plant cells from the control experiment (untreated with chitosan) were vacuolated and the cell interval increased. The relict of protoplast moved to the center, with cells tending to disjoint. Our findings indicate that wastewater with high COD concentration can cause a substantial damage to submersed plant, nevertheless, chitosan probably could alleviate the membrane lipid peroxidization and ultrastructure phytotoxicities, and protect plant cells from stress of high COD concentration polluted water.     

Removal of cadmium using MnO2 loaded D301 resin

MnO2 loaded weak basic anion exchange resin D301 （Anion exchange resin, macroreticular weak basic styrene） as adsorbent has been prepared and applied to the removal of cadmium. The adsorption characteristics have been investigated with respect to effect of pH, equilibrium isotherms, removal kinetic data, and interference of the coexisting ions. The results indicated that the Cd^2＋ could be efficiently removed using MnO2 loaded D301 resin in the pH range of 3-8 from aqueous solutions with the co-existence of high concentration of alkali and alkaline-earth metals ions. The saturate adsorption capacity of the Cd^2＋ was 77.88 mg/g. The adsorption process followed the pseudo first-order kinetics. The equilibrium data obtained in this study accorded excellently with the Langmuir adsorption isotherm.     

Effect of coagulation pretreatment on the fouling of ultrafiltration membrane

The purpose of this study is to understand the effect and mechanism of preventing membrane fouling, by coagulation pretreatment, in terms of fractional component and molecular weight of natural organic matter （NOM）. A relatively higher molecular weight （MW） of hydrophobic compounds was responsible for a rapid decline in the ultrafiltration flux. Coagulation could effectively remove the hydrophobic organics, resulting in the increase of flux. It was found that a lower MW of neutral hydrophilic compounds, which could remove inadequately by coagulation, was responsible for the slow declining flux. The fluxes in the filtration of coagulated water and supernatant water were compared and the results showed that a lower MW of neutral hydrophilic compounds remained in the supernatant water after coagulation could be rejected by a membrane, resulting in fouling. It was also found that the coagulated flocs could absorb neutral hydrophilic compounds effectively. Therefore, with the coagulated flocs formed on the membrane surface, the flux decline could be improved.     

Penetration analysis of elements and bioleaching treatment of spent refractory for recycling

Acidithiobacillus ferrooxidans ATCC23270 and Acidithiobacillus thiooxidans TM-32 were used for bioleaching of spent refractories of aluminium and copper melting furnaces for their recycling.Firstly,penetration of elements into aluminium melting furnace refractory was investigated and it was found that up to 7 cm from surface was contaminated.Comparison on leaching efficiency by the strains ATCC23270 and TM-32 found that the strain ATCC23270 could treat larger amount of the refractories than the strain TM-32 could do.In the experiment of bioleaching of spent refractory aluminium melting furnace by the strain ATCC23270,high leaching efficiency were obtained on Al,Si,and Ca,and extremely low leaching performance was,however,shown on the rest of elements i.e.,Na,Mn,and Zn.Under the strain TM-32 use,relatively high leaching performance was recognized on Al,Si,Ca,Na,Mn,and Zn.In the experiment of bioleaching for spent refractory copper melting furnace,almost the same leaching trends were shown on Cu,Zn,Al,and Si under the strains ACTT23270 and TM-32 uses.     

Simultaneous removal of ammonium and phosphate by zeolite synthesized from coal fly ash as influenced by acid treatment

Zeolite synthesized from fly ash （ZFA） without modification is not efficient for the purification of NH4＋ and phosphate at low concentrations that occur in real effluents, despite the high potential removal capacity. To develop an effective technique to enhance the removal efficiency of ammonium and phosphate at low concentrations, ZFA was modified with acid treatment and the simultaneous removal of ammonium and phosphate in a wide range of concentration was investigated. It was seen that when compared with untreated ZFA, only the treatment by 0.01 mol/L of H2SO4 significantly improved the removal efficiency of ammonium at low initial concentrations. The behavior was well explained by the pH effect. Treatment by more concentrated H2SO4 led to the deterioration of the ZFA structure and a decrease in the cation exchange capacity. Treatment by 0.01 mol/L H2SO4 improved the removal efficiency of phosphate by ZFA at all initial P concentrations, while the treatment by concentrated H2SO4 （≥0.9 mol/L） resulted in a limited maximum phosphate immobilization capacity （PIC）. It was concluded that through a previous mild acid treatment （e.g. 0.01 mol/L of H2SO4）, ZFA can be used in the simultaneous removal of NH4＋ and P at low concentrations simulating real effluent.