民用燃煤排放分级颗粒物中碳组分排放因子

中国是全球碳质气溶胶最重要的贡献者之一,民用燃煤排放占有很大的比重.排放因子的不确定性直接影响碳气溶胶排放清单的准确性.本研究基于室内模拟燃烧实验和稀释通道采样系统,采用FA-3型9级撞击采样器采集了3种蜂窝煤(考虑明烧和闷烧)和包括烟煤与褐煤在内的4种块煤燃烧排放的九级粒径颗粒物,采用热光法分析了不同粒径颗粒物中有机碳(OC)和元素碳(EC)的含量,计算得到排放因子.结果表明:(1)对于蜂窝煤的明烧与闷烧,PM2.1中OC排放因子分别为0.07g·kg~(-1)和0.10 g·kg~(-1),EC的排放因子为0.002 g·kg~(-1)和0.001 g·kg~(-1);闷烧排放的有机碳颗粒物高于明烧;元素碳排放因子低于明烧.块煤排放PM2.1中OC与EC排放因子分别是1.4 g·kg~(-1)和0.02 g·kg~(-1),高出蜂窝煤排放一个数量级.(2)粒径分析结果表明,民用煤燃烧排放的颗粒物及其载带的碳组分集中在细颗粒物上,碳组分的质量中值粒径均小于2.5μm,总碳(OC+EC)的排放因子粒径分布表明蜂窝煤燃烧排放的碳组分富集于≤0.43μm粒径段,块煤富集于0.43~0.65μm粒径段.     

云南宣威地区燃煤排放PM10的微观形貌和粒度特征

宣威地区肺癌发病率居全国首位,并且肺癌与室内燃煤关系密切. 为了解宣威地区室内燃煤排放PM₁₀的微观形貌和粒度特征,使用小流量Minivol采样器,分别于2011年1月、3月和12月对宣威地区6个代表性乡镇的18个农户及对照点——贵州六盘水幸福村2个农户室内、外的PM₁₀进行采样. 采用扫描电子显微镜分析样品的微观形貌,并对颗粒物粒度进行统计分析. 根据微观形貌特征将PM₁₀分为烟尘集合体(链状、蓬松状、密实状)、球形颗粒(燃煤飞灰和焦油球)、矿物颗粒(规则和不规则状)、生物颗粒及超细未知颗粒. 结果表明:宣威地区室内PM₁₀微观形貌差别较大;室、内外PM₁₀的粒度分布在0.1~0.4μm内的颗粒数量所占比例较大,而1μm以上颗粒体积所占比例较大;小粒径颗粒对颗粒物数量贡献较大,而少数大粒径颗粒对体积贡献较大;宣威地区和对照点室内的PM₁₀数量-粒度和体积-粒度分布相似,室外PM₁₀数量-粒度特征相似但体积-粒度分布有所差异. 宣威地区室内的烟尘集合体和球形颗粒分别占颗粒物总数的10.5%和23.6%,高于对照点 (分别为7.7%和11.3%).      

杭州市灰霾与非灰霾日不同粒径大气颗粒物来源解析

在2011年典型灰霾和非灰霾天气下,采集了杭州市不同粒径的大气颗粒物样品,测定并分析各粒径段颗粒物的质量浓度及其化学成分;同时采集并分析了主要污染源排放的颗粒物样品,通过CMB(化学质量平衡)模型进行源解析. 结果表明:灰霾天气下,二次粒子是杭州市各粒径段颗粒物的首要贡献源,其对≤1.1、>1.1~3.3、>3.3~5.8和>5.8~10μm粒径段的颗粒物贡献率分别为60.4%、62.2%、54.8%和46.5%. 在一次排放源中,机动车尾气是≤1.1和>1.1~3.3μm粒径段颗粒物的重要来源,贡献率分别为13.8%和12.2%;城市扬尘是>3.3~5.8μm粒径段颗粒物的重要来源,贡献率达到16.0%;而建筑施工尘是>5.8~10μm粒径段颗粒物的重要来源,贡献率为14.2%. 非灰霾天气下,随着颗粒物粒径的增加,二次粒子的贡献率显著下降,对≤1.1μm粒径段颗粒物的贡献率为42.7%,而对>5.8~10μm粒径段颗粒物的贡献率仅为15.5%;机动车是各粒径段颗粒物的重要贡献源,贡献率均在20%以上;煤烟尘是≤3.3μm细粒径段颗粒物的重要贡献源类,贡献率为22.0%;城市扬尘是>3.3~5.8μm粒径段颗粒物的重要来源,贡献率为18.3%;建筑施工尘依然是>5.8~10μm粒径段颗粒物的重要来源,贡献率为21.4%.      

不同燃烧过程颗粒物粒径排放特征

采用荷电低压颗粒物撞击器(ELPI)和稀释采样系统研究重庆市工业源、交通源、生物质燃烧以及餐饮业油烟等各类燃烧过程的颗粒物排放特征.结果表明:燃煤锅炉以及各类柴油交通源颗粒物数浓度峰值都表现出单峰型的变化特征,峰值主要出现在0.20~0.48μm之间;生物质燃烧和餐饮业油烟颗粒物的数浓度都呈现出双峰型的变化趋势,分别出现在核模态(0.02~0.07μm)和积聚态(0.2μm);水泥窑炉的数浓度也出现双峰型变化特征,分别出现在积聚态(0.12μm)以及接近粗颗粒物态的1.23~1.96μm粒径范围处.各污染源颗粒物质量浓度峰值主要出现在粗粒径态,交通源排放的颗粒物质量浓度相对较高.各类污染源数浓度分布主要集中在积聚模态,粗颗粒态的数浓度累计贡献都不到1%;质量浓度主要分布在粗颗粒态,核模态的质量浓度贡献都小于0.1%.     

霾与非霾期间汞在不同粒径颗粒物上的分布特征

在我国高速经济增长过程中,霾污染日趋突出,同时大气汞污染也十分严重,而颗粒汞对于汞在大气中的循环演化意义重大.为了探讨霾污染期间汞在不同粒径颗粒物中的分布特征,采用Nano-moudi 12级(6.2~9.9μm、3.1~6.2μm,1.8~3.1μm、1.0~1.8μm、0.56~1.0μm、0.32~0.56μm、0.18~0.32μm、0.10~0.18μm,0.056~0.10μm、0.032~0.056μm、0.018~0.032μm、0.010~0.018μm)大气颗粒物采样器,对上海霾与非霾期间不同粒径大气颗粒物中的汞进行分析.结果表明,颗粒态汞含量与颗粒物含量正相关;采样期间霾天颗粒态汞平均浓度0.31 ng·m-3是非霾天颗粒态汞平均浓度0.11 ng·m-3的2~3倍;霾和非霾天颗粒态汞浓度以及颗粒物质量浓度随粒径分布呈双峰型,霾期间峰值分别出现在0.56~1.0μm粒径段和3.1~6.2μm粒径段,而非霾期峰值分别出现在0.32~0.56μm和3.1~6.2μm粒径段;霾天较非霾天颗粒态汞和颗粒物的粒径分布均出现了向大粒径方向偏移;颗粒态汞主要分布在粒径≤1μm粒子上,能够长时间停留和长距离输送;非霾期间颗粒态汞在颗粒物中的平均含量为0.029 ng·μg-1,而霾期间为0.015 ng·μg-1;霾污染过程中其他污染物迅速成长,而汞成长较慢;霾天积聚核模态粒子中颗粒态汞质量浓度为2.06 ng·m-3,而非霾天为0.55 ng·m-3,积聚态颗粒物的大幅增加,是灰霾形成的主要原因.本地源燃煤等的排放以及风沙扬尘的增加和外地源的输送是导致霾天污染严重的重要原因.     

云南宣威地区燃煤排放颗粒物中石英矿物的特征

云南宣威地区是我国人群肺癌死亡率最高的地区之一,过往研究表明,该区的高肺癌死亡率可能与居民室内燃煤排放颗粒物中的多环芳烃(PAHs)有关,而最近研究发现,其中的nm级石英可能是导致肺癌发生的原因, 但鲜见该区燃煤排放颗粒物中细粒石英矿物的研究. 为探究燃煤排放细粒矿物的分布特征,采集了肺癌高发区宣威市来宾镇及周边5个乡镇煤矿中的15个煤样,使用光学显微镜、X射线衍射仪(XRD)、带能谱的扫描电镜(SEM/EDS)分析了煤样的煤岩组分及矿物组成. 结果表明:宣威煤以中挥发分、较高镜质组烟煤为主,煤中主要矿物为石英、鲕绿泥石、高岭石和方解石;不同煤样中,矿物质的结晶程度有所差异;单颗粒统计结果显示,在所统计的775个矿物颗粒中,石英颗粒占37.9%,并且粒径多分布在1~2μm之间; 石英矿物颗粒的形状不规则且以微粒的形式填充在煤缝隙中. 石英与鲕绿泥石共存的现象显示,宣威煤中石英来源于富含Fe和Al的硅质热液流,而非岩石碎屑沉积;此外,在肺癌高发区(来宾镇),其煤中Si+Fe质矿物颗粒含量较Si质矿物高. 今后将重点研究石英颗粒在Fe参与下的生物活性.      

重庆市典型工业源颗粒物排放特征

利用稀释通道系统采集重庆市主城区典型燃煤锅炉和水泥窑炉烟道气中的颗粒物样品,并利用静电低压撞击器将其按粒径分为12级,分析了工业源颗粒物粒径谱(0.02~10μm)特征。结果表明,水泥窑炉排放颗粒物数浓度表现出双峰型的对数分布特征,分别出现在积聚模态(0.12μm)以及接近粗粒子模态(1.23~1.96μm)粒径范围处,燃煤锅炉排放颗粒物数浓度变化特征以及浓度水平都有较大的差异,主要呈积聚模态单峰型变化趋势;火电厂1燃煤锅炉排放颗粒物的数浓度和质量浓度均为最高,其峰值分别为2.2×106cm-3和174.2 mgm3;水泥窑炉PM2.5中OC、Al、Ca所占比例较高,分别为17.96%、17.32%和9.90%,燃煤锅炉PM2.5中Al、SO42-和OC所占比例较高,分别为9.17%、8.92%和6.15%;相对于水溶性组分和碳组分,无机元素所占比例相对较高,其对水泥窑炉和燃煤锅炉PM2.5质量浓度的贡献分别达到了44.28%和18.07%。     

北京市西三环地区大气颗粒物中多环芳烃的分布特性

于2012年3—12月在北京市西三环地区按粒径分6级采集大气颗粒物样品,采用气相色谱-质谱(GC-MS)对颗粒物样品中16种优控PAHs(多环芳烃)进行分析. 结果表明:颗粒物中ρ(∑₁₆PAHs)(PAHs的总质量浓度)季节变化显著,表现为冬季>春季>秋季>夏季,并且与ρ(PM)(PM为颗粒物)呈良好线性相关;不同粒径颗粒物中ρ(PAHs)呈向小粒子富集的趋势,PM_2.1中ρ(PAHs)约占ρ_sum(∑₁₆PAHs)〔6级颗粒物中ρ(∑₁₆PAHs)总和〕的64%~87%;除夏季3环PAHs占优势外,其他季节均以4~ 5环PAHs占优势;同时,随着粒径的减小,PAHs有向高环数富集的趋势. 运用主成分分析和多元线性回归法进行源解析发现,机动车尾气排放和燃煤是本地区大气颗粒物中PAHs的主要来源;不同粒径颗粒物中的PAHs来源有差异,2.1~10.2μm粒径段颗粒物中PAHs主要来源于机动车尾气排放,贡献率为63.0%;而1.3~2.1μm和<1.3μm的颗粒物中PAHs均主要来源于燃煤,贡献率分别为56.8%和58.7%.      

重庆市北碚城区气溶胶中有机碳和元素碳的污染特征

为了研究重庆市北碚城区大气碳质气溶胶组分的污染特征,于2014年3月~2015年2月采用安德森采样器采集大气颗粒物样品,用DRI Model 2001 A热光碳分析仪测定其中有机碳(OC)和元素碳(EC)的质量浓度.结果表明,北碚城区PM_(2.1)和PM_(9.0)中OC和EC的年平均浓度分别为(16.3±7.6)、(1.8±0.7)和(25.0±9.7)、(3.2±1.3)μg·m-3.在PM_(2.1)中,OC和EC均呈现出冬春季大于夏秋季的季节变化特征,而PM_(9.0)中OC呈现出夏春季大于冬秋季,EC呈现出冬春季大于夏秋季的季节变化特征.对全年OC和EC的粒径进行分析,发现OC在整个粒径上呈现"双峰型"分布,其中细粒子段峰值位于0.43~0.65μm粒径段,粗粒子段峰值位于4.7~5.8μm粒径段;EC呈现出"三峰型"分布,其中细粒子段峰值位于0.43~0.65μm粒径段,粗粒子段峰值位于4.7~5.8μm粒径段,同时2.1~3.3μm粒径段也出现一个明显峰值.对OC和EC进行相关性分析并对PM_(2.1)中的SOC进行估算,发现北碚城区全年SOC浓度为(6.3±5.9)μg·m-3,占全年OC的33.5%±22.6%,且OC和EC显著相关.最后对北碚城区大气气溶胶的污染来源进行分析,发现污染主要来源于汽油车尾气、生物质燃烧和燃煤排放.     

沙尘天气对生物气溶胶中总微生物浓度及粒径分布的影响

为了解沙尘对生物气溶胶中微生物的影响,于2015年3~4月间分别在兰州和青岛沙尘期间运用分级生物气溶胶采样器连续采集了生物气溶胶样品,并利用DAPI染色-荧光显微镜计数方法测定了总微生物浓度.结果表明,沙尘发生时生物气溶胶中总微生物浓度显著增加(P0.05).兰州和青岛总微生物浓度晴天背景均值分别为5.61×10~5cells·m~(-3)和2.08×10~5cells·m~(-3),沙尘时平均浓度分别是晴天的14.8倍和6.42倍.晴天时兰州和青岛两地样品微生物粒径分布均呈双峰分布,最高峰值均出现在7.0μm的粒径上,最低值均出现在4.7~7.0μm的粒径上,浓度次高峰值分别出现在3.3~4.7μm的粒径上和1.1~2.1μm的粒径上.沙尘时粒径分布均发生明显变化,兰州仍呈现双峰分布,但其中一个峰值从7.0μm移动到1.1~2.1μm;而青岛粒径由双峰分布变为粗粒径偏态分布.兰州和青岛沙尘前微生物负荷的背景值分别是2 224 cells·μg~(-1)和1 550 cells·μg~(-1),而沙尘发生时,颗粒物的微生物负荷均大幅增加,最高值分别达26 442 cells·μg~(-1)和10 250 cells·μg~(-1),这说明沙尘天气发生时,微生物浓度的增加不仅仅是因为空气中颗粒物的增加,而是因为长距离传输的沙尘颗粒携带有大量外源微生物.     

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.