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.     

中国民用煤燃烧排放细颗粒物中重金属的清单

基于稀释通道采样系统和室内模拟燃烧实测,并搜集全国各省区煤中11种重金属的含量,推算出两种常用民用煤(蜂窝煤和块煤)燃烧排放的细颗粒物(PM_(2.5))中V、Cr、Mn、Co、Ni、Cu、Zn、As、Cd、Sb和Pb等11种重金属排放因子.计算了2012年全国(除港、澳、台地区)民用燃煤排放PM_(2.5)中重金属的排放量,并建立了全国30 km×30 km的网格化清单.结果表明,蜂窝煤燃烧排放PM2.5中,Pb、Zn、As和Cu的排放因子较高,分别为27.1、16.8、0.99和0.97 mg·kg-1,分别是块煤的56、6、10和2倍.2012年我国民用燃煤燃烧排放PM_(2.5)中V、Cr、Mn、Co、Ni、Cu、Zn、As、Cd、Sb和Pb的排放总量分别为0.5、30.1、59.5、1.1、29.3、20.0、188.9、64.9、1.6、3.4和176.7 t.湖南、河北、内蒙古、河南和山东等省区民用煤燃烧排放的各种重金属总排放量较高,分别占全国排放总量的12.4%、12.3%、10.4%、9.9%和9.3%.不同重金属的单位面积排放强度与人均排放量显示,北京、河南、山东、湖南、江西、贵州以及内蒙古等地区存在较高的重金属健康风险.空间分布信息显示,Zn和Pb年排放量较大的地区分布较广,主要分布在内蒙古、河北、北京、天津、山东、河南、甘肃、湖南以及江西等省(市)区.本研究所得细粒子中重金属清单可为区域空气质量模拟、人体健康风险评估等提供基础数据.     

民用燃煤排放细颗粒中金属元素排放特征及单颗粒分析

通过模拟民用煤炭燃烧,采集了5种不同成熟度的典型块煤燃烧排放的单颗粒和PM_2.5样品.利用带能谱仪的透射电镜研究了金属颗粒的单颗粒特征,运用电感耦合等离子体质谱仪和发射光谱仪获得了PM_2.5样品中14种金属元素（包括8种重金属）的浓度特征.结果显示,民用燃煤排放的含金属元素的颗粒物主要有矿物颗粒、部分碳质颗粒、富K颗粒、富S[K]颗粒、富Fe颗粒、富Zn颗粒和富Pb颗粒共7种.5种民用燃煤排放的14种金属元素占PM_2.5的1.29%~15.54%,其中Al、Ca和Na占金属元素总量的57%~80%,是民用燃煤排放的主要的金属元素;V、Cr、Mn、Co、Ni、Cu、Zn和Pb这8种重金属元素占PM_2.5的0.09%~2.53%,其中Zn和Pb占重金属总量的54%~91%,在民用燃煤排放的重金属中占主导.单颗粒分析结果显示Zn和Pb元素主要富集在粒径小于1μm的富Zn和富Pb颗粒中,这些细颗粒能够直接进入人体,对人体健康造成威胁.因此,建议居民应通过使用精煤或天然气等清洁能源来减少重金属的排放.     

垃圾焚烧厂排放颗粒物组分粒径分布特征

本研究采用静电低压撞击器(ELPI)采集垃圾焚烧厂排放颗粒物,分析颗粒物中元素和碳组分,对其中OC、EC和重金属元素在14个粒径段的粒径特征进行分析,并建立了垃圾焚烧厂源PM_1、PM_(2.5)和PM_(10)的元素和碳组分成分谱,以期为精细化来源解析提供参考.结果表明,垃圾焚烧厂排放颗粒物的主要组分有Al、Si、S、Ca、Cr、Fe、OC和EC等(质量分数≥1%),其中OC和Ca的含量较高,在PM_(2.5)中的质量分数分别为10. 15%和12. 37%;重金属含量Cr Pb Zn Mn Cu Cd Ni,其中Cr和Pb在PM_(2.5)中的质量分数分别为1. 83%和0. 74%,Cr在PM_1中的质量分数达到3. 53%; OC在2. 39～3. 99μm和6. 68～9. 91μm这2个粒径段的含量达到峰值,分别占OC总含量的15. 02%和20. 45%,但在细颗粒物中的含量高于在粗颗粒物中的含量,EC在细颗粒物中的含量远高于在粗颗粒物中的含量,在0. 382～0. 613μm粒径段占14. 8%; Cr、Mn、Ni、Cu、Zn、Cd和Pb等重金属元素主要富集于细颗粒中.     

上海市郊区大气细颗粒和超细颗粒物中元素粒径分布研究

用同步辐射X荧光光谱分析了上海市郊区大气细颗粒和超细颗粒物（0.028 7～2.40 μm）中元素粒径分布、质量中值粒径、元素相关性和不同粒径颗粒物中的富集因子.Ca、Ti主要分布于粒径>2 μm的颗粒物中,它们之间的相关系数达0.933,富集因子在0.1～3.2之间,且与粒径无明显关联,主要来自土壤扬尘等自然来源.V、Cr、Mn、Ni、Zn、Cu、Pb、Cl、S等元素主要分布在0.1～1.0 μm颗粒物中,质量中值粒径在0.56～0.94 μm之间.V、Cr、Ni、Cu、Zn、Pb显著富集,且富集程度随粒径减小而增大.其中Pb在超细颗粒物（<0.1 μm）中的富集因子达2 023.7～2 244.2,远大于在细颗粒和 PM_2.5中的富集程度.这些元素主要来自燃油、燃煤、冶金和机动车尾气等人为污染.Fe在>0.2 μm颗粒物中分布较均匀,质量中值粒径1.3 μm.除了局部污染源,远距离传输对该地区大气颗粒物污染有不可忽略的影响.     

废电路板热拆解过程中颗粒污染物的排放特征

文章对废旧电路板(WPCBs)加热拆解过程产生的颗粒物、颗粒物所富集的重金属(Sb、Zn、Cr、Pb、Cd、Cu)与多溴联苯醚(PBDEs)进行研究。结果表明,加热拆解过程中排放的PM_(10)颗粒物总浓度、颗粒态重金属总含量、颗粒态∑_(39)PBDEs含量分别为2 243μg/m~3、33.53μg/m~3、9 535 ng/m~3。PM_(2.5)细颗粒占释放颗粒物的63%,其中0.4～0.7μm粒径段的颗粒物浓度最大。PM_(10)中各重金属含量由高到低依次为:SbPbZnCuCrCd,其中Sb和Pb的排放浓度分别为21.86μg/m~3和6.74μg/m~3。Pb、Cd、Cu的质量中值直径(MMAD)2.5μm,主要分布于细颗粒,而Sb、Zn、Cr集中于粗颗粒。PBDEs的排放以四溴联苯醚为主,占78.68%。∑_(39)PBDEs的MMAD值1,低溴代PBDEs主要集中于细颗粒,而高溴代PBDEs主要吸附于粗颗粒。对WPCBs加热拆解过程产生不同粒径颗粒中重金属和PBDEs的分布特征研究,为颗粒物的污染控制和风险评价提供科学依据。     

民用燃料燃烧排放PM2.5和PM10中碳组分排放因子对比

在实验室中模拟民用燃料在家庭炉灶中的燃烧,应用稀释通道系统采集颗粒物,获得玉米秸秆、薪柴、蜂窝煤和块煤四种常用民用燃料燃烧排放PM10,PM2.5及载带碳组分的排放因子.结果表明,民用燃料燃烧排放的颗粒物以细颗粒为主, PM2.5占PM10的70%~90%.颗粒物排放因子最大的为块煤,其PM2.5和PM10的排放因子分别为9.837和11.929g/kg,分别是蜂窝煤的12.6和13.7倍;玉米秸秆和薪柴PM2.5和PM10的排放因子稍低于块煤,为7.359~10.444g/kg.4种燃料燃烧OC排放因子块煤最高,其在PM2.5和PM10中分别为5.29和5.19g/kg.薪柴燃烧EC的排放因子最高,其在PM2.5和PM10 中的排放因子分别为1.065和1.126g/kg.块煤两种粒径上EC的排放因子略低于薪柴.蜂窝煤EC的排放因子最低,比薪柴低300倍左右,玉米秸秆EC的排放因子也要比薪柴低10倍左右.碳组分是块煤,秸秆,薪柴排放颗粒物的主要成分,其含量在40%~60%之间,该值比蜂窝煤高3倍.四种燃料对应的OC/EC比值差异很大,薪柴和块煤燃烧排放颗粒该值为3~6,秸秆和蜂窝煤燃烧排放颗粒其值高达30~50.     

北京城区公园及其邻近道路国槐叶面尘分布与重金属污染特征

叶面尘可以反映一段时间、一定区域内空气颗粒物的污染状况.为了探究城市公园环境和道路环境的空气颗粒物污染差异,同时采集了北京市12座公园及邻近道路的国槐(Sophora japonica)叶面尘,对比分析其滞尘量、粒径分布、重金属含量的差异,并探讨了重金属的可能来源,结果表明:行道树国槐滞尘量显著高于公园国槐(p =0.041),但后者富集了更多粒径范围在2～ 20 μm之间的颗粒物.叶面尘中的重金属污染程度表现为Cu ＞Pb ＞Zn ＞Cr＞ Ni＞ Mn,其中,Cu、Pb和Zn达到中度污染水平,公园国槐叶面尘重金属元素的含量一般高于行道树国槐.公园国槐叶面尘重金属主要来源于交通排放,其次来自土壤母质,小部分来自工业排放和化石燃料燃烧排放等;行道树国槐叶面尘重金属最重要的来源是交通排放,其次是非特定源(工业排放、化石燃料燃烧排放、地面灰尘的二次扬尘及土壤母质等).本文的研究结果表明,严格控制交通排放是缓解北京城市灰尘污染的重要途径.     

不同粒径垃圾焚烧飞灰重金属分布和浸出性质

对烟气净化系统飞灰(以下简称飞灰)按粒径进行分级,研究了飞灰重金属含量、形态分布和浸出毒性随粒径的变化,讨论了不同粒径的飞灰对重金属总量和浸出总量的贡献率.结果表明:飞灰中粒径>154 μm和<30 μm的颗粒较少,粒径为38.5～74 μm的颗粒约占总量的50%.除Ni和Cr外,重金属含量随飞灰粒径的减小呈增加趋势,且主要表现在酸溶态Cd,Zn,Pb,Cu和有机结合态Pb以及晶形氧化铁态Pb,Zn含量的增加.随着飞灰粒径的减小,Cr,Ni,Zn,Hg和Pb的浸出量也呈逐渐增加趋势,其中Zn,Hg和Pb的表现尤为突出.尽管细颗粒上的重金属对飞灰的重金属总量贡献不大,但高浸出率使细颗粒飞灰对重金属浸出总量仍具有较大贡献,尤其是Pb,Zn和Hg,在占飞灰质量8%的粒径<30 μm的飞灰中,富集了约40%的水溶性Pb,Zn和Hg.      

上海城市地表灰尘重金属污染粒级效应与生物有效性

以上海中心城区为例,在分析地表灰尘重金属污染粒级效应基础上,研究重金属赋存形态及其生物有效性.结果表明,地表灰尘平均中值粒径为132 μm,低于75 μm粒径级别颗粒物占有最大的体积含量.重金属污染显示出明显的粒级效应,随着粒径降低,重金属含量呈现明显的增加趋势,150 μm和75 μm是主要级别,其中<75 μm颗粒物污染物含量依次为Cr>Pb>Cd>Zn>Ni>Cu.对地表灰尘重金属赋存形态研究表明,Zn以碳酸盐态为主;Ni以残渣态为主;Pb主要为铁锰结合态存在,Cu和Cd则以有机态为主;Cr主要以残渣态存在.重金属活性形态比例依次为Zn>Pb>Ni>Cd>Cu>Cr.与国外城市相比,上海城市地表灰尘Zn、Pb和Ni生物活性比例较大,而Cu和Cd活性比例相对较低,Cr活性水平与其它城市相当,环境危害相对最小.     

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.