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%.      

“组合火焰型”焦炉大气主要污染物排放特征分析

为了研究"组合火焰型"焦炉对大气环境的实际影响,通过实测主要污染物排放浓度,对其排放规律及达标情况进行分析。结果表明:颗粒物有组织排放浓度特征规律为,筛焦处>备煤处>焦炉烟囱>装煤处>推焦处;SO2、NOx有组织排放浓度特征规律为,焦炉烟囱>推焦处>装煤处;BaP有组织排放浓度特征规律为,装煤处>推焦处>焦炉烟囱;装煤处、推焦处以BaP污染为主,焦炉顶以NOx污染为主。受装煤、出焦的双重影响,颗粒物无组织排放由塔南向塔北浓度逐渐降低,BaP、BSM在装煤塔两侧浓度水平相当。在生产负荷大于90%的情况下,所测污染物排放浓度均能达标且优于传统型焦炉,在BaP、BSM控制方面具有明显优势。     

杭州市大气颗粒物消光组分的粒径分布特征研究

2010年8月在杭州市朝晖、云栖、杭钢和下沙4个点位采集了不同粒径大气颗粒物样品,并对其主要消光组分的粒径分布特征进行了分析,包括SO42-、NO3-、NH4+、OC和EC等.同时在朝晖点位对多种气态污染物和多个气象要素进行了同步观测,以评估杭州市能见度下降的影响因素.结果表明:PM2.5、RH、SO2和NO2均与能见度呈一定负相关关系.4个监测点位颗粒物浓度变化均呈双峰型,峰值出现在0.4~0.7μm和9.0~10μm粒径段.以3.3μm为粗细颗粒的分界线,不同监测点位PM10中粗、细颗粒所占比例均等.水溶性离子消光组分的浓度大小顺序为:SO42->NH4+>NO3-. SO42-、NO3-和NH4+均显单峰结构,SO42-和NH4+的峰值出现在0.4~1.1μm的粒径段,NO3-峰值出现在5.8~10μm粒径段.OC显单峰结构,峰值出现在0.4~0.7μm粒径段;EC显双峰结构,峰值出现在0.4~0.7μm和2.1~3.3μm范围内.因而,要解决杭州的能见度问题,应减少细颗粒物,尤其是粒径<1.1μm的颗粒物的污染. NO3-、SO42-、OC和EC对杭州市颗粒物消光能力相对贡献率之比为2.2%:13.7%:29.8%:43.8%.因此要有效控制杭州市大气能见度的降低趋势, 首要的就是控制EC的主要排放源,即机动车尾气的排放.     

典型焦化厂大气挥发性有机物排放表征分析

焦化行业是我国重要工业类别,但因其工艺过程复杂,所以VOCs（挥发性有机物）排放特征尚不明确.以典型机械焦化厂为研究对象,对焦炉烟囱、推焦、装煤和焦炉顶等不同排放环节进行采样,并利用GC/MS（气相色谱质谱联用仪）进行多物种分析,并对焦化厂排放VOCs的OFP（生成O₃的潜势）进行探索性研究.结果表明:①焦化厂排放的VOCs包括烷烃、烯烃、炔烃、芳香烃、卤代烃和含氧VOCs等六大类,共90多个物种.②不同环节排放的ρ（VOCs）差异显著,其中,焦炉烟囱ρ（VOCs）排放量（87.1 mg/m3）最大,其次为推焦（4.0 mg/m3）、装煤（3.3 mg/m3）和焦炉顶（1.1 mg/m3）.③不同环节排放的VOCs种类不同,但均以烷烃和烯烃为主,其中,焦炉烟囱排放的烯烃最多（占比达66%）,装煤和推焦排放的则以烷烃为主（占比分别为42%和36%）,焦炉顶排放的烷烃和烯烃相近（占比分别为31%和29%）.④基于排放特征和最大增量反应活性法研究发现,焦炉烟囱是焦化厂VOCs减排的重点环节,烯烃是重点减排的物种,特别是乙烯、丙烯、丁烯和1,3-丁二烯等,但乙醛、苯、甲苯等也不容忽视.研究显示,以乙烷/丙烷/乙烯（三者质量浓度之比）为指标,可明显区分焦炉烟囱、推焦、装煤和焦炉顶等不同环节的VOCs排放.      

桂林市细颗粒物典型排放源单颗粒质谱特征研究

利用单颗粒气溶胶飞行时间质谱仪(SPAMS)对桂林市四类PM2.5典型污染源排放颗粒物的粒径和化学成分进行分析,结果表明:除扬尘颗粒外,其他几类源排放颗粒物的粒径集中在0.2~1.25μm之间.几类污染源排放颗粒物的化学成分有明显区别,柴油车以EC颗粒为主,占总电离颗粒的74.7%,汽油车以富钙颗粒为主,占总电离颗粒的86.7%,燃煤排放以富铁、富铬颗粒为主,二者合计占了总电离颗粒的59.9%,生物质燃烧以含左旋葡聚糖颗粒为主,占总电离颗粒的44.4%,扬尘颗粒以富铝颗粒为主,占总电离颗粒的69.4%.这些特征为大气颗粒物的源解析提供了可能.     

钢铁企业烟粉尘重点排放源分析

调研并核算了我国典型钢铁企业烧结、球团、炼焦、高炉炼铁、转炉炼钢、热轧、冷轧、自备电站和石灰窑等工序的烟粉尘年排放量及其占全厂的比例。分析了钢铁厂内烟粉尘排放的重点工序,以及各工序中的主要排放源。筛选出了钢铁企业的十大烟粉尘重点排放源,总计占全厂烟粉尘排放量的80.44%。并为钢铁企业的烟粉尘治理及排放监测提出了建议。     

天津市典型城区大气碳质颗粒物的粒径分布特征和来源

为分析天津市典型城区大气碳质颗粒物的粒径分布及其来源,于2009年12月—2010年11月采用9级惯性撞击式分级采样器对大气颗粒物进行采样,采用热光碳分析仪分析了颗粒物中的EC(元素碳)和OC(有机碳)的质量浓度. 结果表明:天津市典型城区大气颗粒物中EC和OC主要存在于细颗粒物中,在≤2.1μm的4个细粒径段中,ρ(EC)的加和年均值为(2.6±0.9)μg/m3,占PM₉(空气动力学直径≤9.0μm)ρ(TEC)的72%;ρ(OC)为(21.5±7.7)μg/m3,占PM₉中ρ(TOC)的60%. ρ(EC)和ρ(OC)季节变化显著,在≤2.1μm粒径段中,春、夏、秋、冬季的ρ(EC)分别为(1.7±0.3)、(2.1±0.4)、(3.1±0.5)和(3.7±0.5)μg/m3;ρ(OC)分别为(17.6±0.4)、(14.4±1.1)、(21.9±1.8)和(32.1±2.5)μg/m3. ρ(EC)峰值分别出现在≤0.43、>0.65~1.1和>4.7~5.8μm 3个粒径段,其中最高值出现在≤0.43μm粒径段;ρ(OC)峰值分别出现在>0.65~1.1和>4.7~5.8μm 2个粒径段,最高值出现在>0.65~1.1μm粒径段. 天津市典型城区细颗粒物中的OC、EC主要来自燃煤、机动车和烹饪排放,粗颗粒物中的OC、EC则更多来自于路面和建筑扬尘.      

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%.     

青岛大气气溶胶水溶性无机离子的粒径分布特征

为了解大气颗粒物中水溶性离子的来源及环境效应,利用安德森采样器连续采集青岛近海2008年1~12月大气颗粒物分级样品,用离子色谱法分析其中主要的水溶性离子,并讨论其粒径分布特征.结果表明, NH4+、K+、Cl-、NO3-、PO43-、SO42-主要存在于粒径小于2.1μm的细粒子中,Na+、Mg2+、Ca2+、F-则主要存在于粒径大于2.1μm的粗粒子中.各离子的粒径分布存在明显的季节变化.NH4+、K+和SO42-四季均主要分布于细粒子中,而Mg2+和Ca2+则主要分布在粗粒子中,两者均在3.3~4.7μm出现峰值;Na+在春、夏、秋3个季节主要存在于粗粒子中,集中分布在3.3~7.0μm粒径范围内,而在冬季则集中分布于0.43~1.1μm且细粒子含量高于粗粒子;春季Cl-在粗粒子中分布较多,尤以2.1~3.3μm范围内的最为突出,而其他3个季节均是细粒子比例明显偏高;NO3-春、夏两季在粗、细粒子中的含量各占50%,秋、冬季节均为细粒子占多数;PO43-夏季只出现在0.65~1.1μm以及>11μm的粒径范围内,粗粒子占95%,其他3个季节则是细粒子含量较高;春季F-在3.3~4.7μm出现峰值,夏季各粒径均未检出,而秋、冬两季粗、细粒子各占50%.K+、NH4+、F-、Cl-、NO3-、SO42-和PO43-受供暖期燃煤取暖的影响较大.K+和NH4+在供暖期和非供暖期峰值均出现在0.43~0.65μm粒径范围;F-供暖期在0.43~0.65μm和3.3~4.7μm粒径段出现峰值;供暖期Cl-的峰值出现在0.43~0.65μm粒径段,而在非供暖期,则出现在2.1~3.3μm的粗粒径段;SO42-和NO3-在供暖期和非供暖期的峰值均出现在0.43~0.65μm和3.3~4.7μm粒径段;供暖期PO43-的最大峰值出现在0.43~0.65μm粒径段,而在非供暖期其最大峰值出现在3.3~4.7μm粒径段.     

钢铁行业典型烧结机污染物排放特征对比研究

钢铁工业排放是引起空气污染的重要原因之一,烧结工序又是钢铁行业中的排放大户.鉴于此,选取了一台工艺相对落后但仍在我国中西部地区大量存在的90 m2小型步进式烧结机和一台工艺较为先进的450 m2大型带式烧结机,对两台烧结机不同点位的SO₂、NO_x、颗粒物以及烟气Hg等进行实测,并对颗粒物中的元素、水溶性离子、OC和EC进行分析,从而获取不同技术水平、不同污控措施下烧结机污染物排放特征以及与2019年生态环境部办公厅印发的《关于推进实施钢铁行业超低排放的意见》中的超低排放限值之间的差距.结果表明:①烧结机头SO₂、NO_x、CO、颗粒物和烟气Hg排放浓度分别为54.69~123.04 mg/m3、187.28~312.58 mg/m3、6 746.04~7 790.83 mg/m3、11.04~19.93 mg/m3和78.97~2 537.07 ng/m3,烧结机尾颗粒物排放浓度为0.76~16.22 mg/m3,机头颗粒物以PM_2.5为主,占比为81.02%~91.49%,机尾颗粒物主要为PM₁₀,占比为71.17%~73.01%.烧结机头SO₂、NO_x、颗粒物以及烧结机尾颗粒物还需分别减排36.00%~71.55%、73.30%~84.00%、9.40%~49.82%和0~38.35%才能满足超低排放限值.②烧结颗粒物主要成分为K、Ca、Na、Mg、Fe、Cl-、SO₄2-、NH₄+、OC和EC等,其占比与烧结机类型、烧结原辅料以及污染物控制措施等因素有关,石灰石-石膏法脱硫后SO₄2-占比增加28.12%,活性炭移动床脱硫后EC占比增加2.15%.③布袋除尘器对烧结机不同粒径颗粒物和烟气Hg的脱除能力比双室五电场静电除尘器分别高出1.25%~5.06%和9.51%,活性炭移动床系统对烧结不同粒径颗粒物以及烟气Hg的去除效果分别比石灰石-石膏法脱硫系统高出9.40%~11.38%和4.31%.研究显示,不同工艺、不同污控措施烧结机大气污染物排放特征存在一定差异,SO₂、NO_x排放浓度与超低排放限值差距较大,烟尘排放浓度与超低排放限值差距较小.      

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.     

Evaluation of phytoextracting cadmium and lead by sunflower, ricinus, alfalfa and mustard in hydroponic culture

Soil contaminated with heavy metals cadmium(Cd)and lead(Pb)is hard to be remediated.Phytoremediation may be a feasible method to remove toxic metals from soil,but there are few suitable plants which can hyperaccumulate metals.In this study,Cd and Pb accumulation by four plants including sunflower(Helianthus annuus L.),mustard(Brassica juncea L.),alfalfa(Medicago sativa L.), ricinus(Ricinus communis L.)in hydroponic cultures was compared.Results showed that these plants could phytocxtract heavy metals, the ability of accumulation differed with species,concentrations and categories of heavy metals.Values of BCF(bioconcentration factor)and TF(translocation factor)indicated that four species had dissimilar abilities of phytoextraction and transportation of heavy metals.Changes on the biomass of plants,pH and Eh at different treatments revealed that these four plants had distinct responses to Cd and Pb in cultures.Measurements should be taken to improve the phytoremediation of sites contaminated with heavy metals,such as pH and Eh regulations,and so forth.     

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.