基于TEM-EDS对四川盆地大气单颗粒气溶胶的研究

为了解四川盆地大气中单颗粒气溶胶理化特征,分别在该区域典型城市（成都市）和背景地区（峨眉山）进行了大气单颗粒样品采集.基于带能谱的透射电子显微镜（TEM-EDS）对两地累计3923个单颗粒的化学组成、形貌特征及混合状态等进行了全面观测和分析,并对两地颗粒物差异性进行了对比分析.结果发现：两地气溶胶颗粒主要包括有机物、富硫、矿物、烟尘和飞灰/金属颗粒,除了以单独的外混形式存在外,大多数颗粒以两种及两种以上颗粒类型混合（即内混）形式存在.通过对成都市不同污染状况下单颗粒特征对比发现,"污染天"的内混颗粒占比高于"清洁天",分别为74.2%和68.6%;相比"清洁天","污染天"颗粒物粒径分布范围更广且峰值区间更大,表明污染过程中颗粒物的大气混合趋于更强.对比成都市与峨眉山分析结果得知,成都市以内混的有机物-硫颗粒为主导（占比为50.2%）,而峨眉山以外混的有机物颗粒为主导（占比为50.5%）;成都市含硫类颗粒物（如有机物-硫颗粒）贡献高于峨眉山,而峨眉山两种含碳类颗粒（如烟尘和有机物-烟尘颗粒）占比高于成都市;此外,成都市与峨眉山两地大气颗粒物粒径分布范围及峰值区间均存在一定差异,进一步体现了两地颗粒物来源和老化混合的差异.在峨眉山,与非降雨天相比,一些易溶于水的颗粒物（如含硫类颗粒）在降雨天占比明显降低,而源自当地燃烧过程、粒径较小且疏水性强的颗粒物（如烟尘和有机物-烟尘颗粒）占比相应升高.     

厦门春季气溶胶特征初探

1993年春季对厦门市大气气溶胶进行了研究,其中包括对3种不同粒径的气溶胶质量浓度?气溶胶元素浓度?气溶胶离子浓度?气溶胶酸度和酸化缓冲能力的研究?结果表明:厦门大气气溶胶质量浓度接近于国家一级标准,细粒子的气溶胶的贡献较高;气溶胶中元素含量较高的为Ca,Al,Fe和S等;在厦门地区气溶胶中NH+₄和SO2-₄主要分布在细粒子中,Ca2+和Mg2+则多分布在粗粒子中,并且其值远小于华南地区;气溶胶中细粒子的酸性大于粗粒子,且酸化缓冲能力远低于粗粒子。      

上海不同污染等级下气溶胶光学特性垂直分布特征

气溶胶光学特性是可吸入颗粒物的重要表征指标之一,而针对不同空气污染等级的气溶胶光学特性的垂直分布特征当前研究较少.本文利用上海地区(30°E,120°N~33°E,123°N)2006年6月至2011年12月的星载云-气溶胶激光雷达(Cloud-Aerosol Lidar and Infrared Pathfinder Satellite Observations,CALIOPSO)资料分析不同季节气溶胶光学特性垂直分布的基础上,深入探讨了不同空气污染等级下的气溶胶垂直(0~6km)分布特征.结果表明:上海地区气溶胶粒子多聚集在0~2 km的高度上且具有明显的季节特征,冬春季节气溶胶粒子后向散射系数集中于0.005以上,颗粒物散射能力较大,其中冬季偏振比范围为0.15~0.25,色比范围为0.57~0.77,主要为不规则的小颗粒;夏季气溶胶粒子的偏振比(0.03~0.09)较小,气溶胶颗粒物较为规则;秋季各种形态的颗粒混合程度较高,其偏振比的范围为0.12~0.23,色比范围为0.58~0.90;不同污染等级下的气溶胶光学特性在垂直分布上具有明显的差异,在重污染时期散射能力大不规则颗粒物增多,垂直差异不明显,污染高度较高;轻度污染以规则颗粒物为主,颗粒物散射能力较小,表现出低层以粗颗粒为主,高层以细颗粒物为主的特征;轻微污染和无污染的气溶胶垂直分布类似,颗粒物散射能力较小.     

基于地基太阳光度计观测的长安区气溶胶光学特性变化及其与颗粒物浓度的关系

气溶胶地基观测数据和颗粒物浓度数据的同步定量评估可为了解长安区大气污染的垂直分布特征,制定合理的大气污染控制提供更有效的依据.基于CE-318太阳光度计观测数据,分析了2018年10月～2021年4月西安市长安区月均和季均气溶胶光学特性分布和变化特征,结合近地面颗粒物浓度数据,分析了不同季节、不同污染程度下气溶胶光学厚度（AOD）对颗粒物浓度的响应.结果表明：（1）观测期间长安区AOD季节变化分明：秋季（1.02）>冬季（1.00）>夏季（0.63）>春季（0.47）; AOD月度、年际差异大,2019年AOD（0.51）略高于2020年（0.48）.（2）整个观测期间长安区气溶胶主控模态存在明显的季节、月度差异,从春季到冬季气溶胶主控模态逐渐从粗模态向细模态转变;2019年气溶胶主控模态的季节变化与整个观测时段类似,2020年各季节气溶胶Angstrom波长指数（Angstrom）分布稳定,气溶胶粒子均以粗模态的形式存在;整个观测时段来看长安区气溶胶类型以混合型气溶胶为主.（3）AOD和Angstrom的关系存在明显的季节差异,春季大气污染以粗模态的气溶胶粒子为主导...     

基于多源探测的南京市大气污染状况分析

南京市作为长三角地区的核心城市之一,工业发达,大气污染状况较为严重.为深入研究南京市污染状况,利用MODIS以及CALIPSO的气溶胶产品对南京市2011-2019年气溶胶特性进行分析,并基于地基反应性气体分析仪数据分析了冬季南京市大气中4种常见反应性气体（SO₂、NO、NO₂、O₃）的体积分数时序状况.结果表明:①南京市2011-2019年气溶胶光学厚度（AOD）整体呈下降趋势,冬季AOD值可达0.7,污染程度为四季中最高,且气溶胶以粗粒子和吸收性粒子为主.②南京市近地层大气（2 km以内）以大粒子和不规则颗粒物为主,2~6 km高度层内细粒子与规则颗粒物的占比逐渐增多,且2~6 km高度层内粒子的体积大小变化不大.③冬季4种常见的反应性气体中,φ（NO）在大气中的变化最为显著,且最高值可达160×10-9,φ（NO₂）与φ（O₃）在大气中的变化趋势相反.由于排放限制措施、工厂脱硫措施的推广以及光化学反应的影响,导致φ（SO₂）较低,仅在3×10-9左右.结合OMI卫星观测数据发现,受新冠肺炎疫情下工厂停工的影响,2020年初南京市φ（NO_x）维持在较低水平.研究显示,近年来南京市颗粒物污染状况有所改善,但仍需注意粗颗粒物的排放,需严格控制工厂气态污染物,尤其是NO_x的排放.      

2021年一次春季北方沙尘过程对广州空气质量的影响

2021年3月,中国北方地区发生了大范围的沙尘天气,广州出现了连续3 d都以PM10为首要污染物的罕见现象.为进一步加深关于北方粗粒子气溶胶传输对广州市空气质量影响的理解,本文利用广东省广州生态环境监测中心站的污染物与气象监测数据,结合富集因子法、特征雷达图和后向轨迹法分析了沙尘影响前后广州市大气污染特征的转变.结果表明：沙尘影响期间,(1)粗细粒子浓度比(PM_2.5/PM₁₀)呈明显下降趋势,从沙尘影响前的0.59降低至0.27,广州市的污染特征由标准型、偏钢铁型转变为偏扬尘型;(2)大气颗粒物中Si、Fe、Ca、Pb、Al、Cu、K浓度显著升高,增幅超过50%,这7种元素的富集因子也显著升高,说明其污染源主要来自于粗颗粒气溶胶的长距离输送;(3)大气颗粒物中Zn和Mn浓度增长不明显,增幅均低于50%,V、Cr、Ni、As的浓度有所降低,这6种元素的富集因子也有所降低,说明其污染源主要来自于广州本地;(4)广州本次污染特征的转变受到源于蒙古国、中国内蒙古西部及南疆盆地的粗离子气溶胶远距离输送和本地生成的共同影响,反映了在大气颗粒物污染不断改...     

华北平原灰霾天气下大气气溶胶的单颗粒分析

为分析灰霾期间单颗粒气溶胶化学组成和混合状态,于2014年12月9日—2015年1月10日,使用单颗粒气溶胶质谱仪（SPAMS）表征华北平原郑州市中牟县的气溶胶颗粒.结果表明:灰霾期（H1:20141213T19:00—20141215T10:00;H2:20150102T10:00—20150106T03:00）和清洁期（C1:20141215T18:00—20141217T18:00;C2:20141231T16:00—20150101T20:00）大气颗粒物种类相同,主要分为有机碳（OC）、元素碳（EC）、生物质燃烧颗粒（BB）、元素碳有机碳（ECOC）、钾二次颗粒（K-Secondary）、矿尘（Dust）以及重金属颗粒（HM）7类.C1时间段,ECOC颗粒占比最高,占总颗粒数的49.8%;其次是OC和EC颗粒物,二者分别占总颗粒数的16.5%和10.8%.H1时间段,K-Secondary颗粒的占比（31.3%）最高;其次是OC和EC颗粒,二者分别占总颗粒数的23.1%和20.2%.清洁期与灰霾期质谱差分结果表明,清洁期颗粒物中含有C₃H+、C₄H₃+、C₅H₃+等有机碳碎片峰,而灰霾期颗粒物中NO₃-、HSO₄-、NO₂-等组分的信号强度显著大于清洁期.混合状态分析表明,从清洁期到灰霾期的过程中,主要颗粒物与NO₃-和HSO₄-的混合程度显著增强.清洁期与灰霾期单颗粒化学组成与混合状态的对比分析表明,清洁期新鲜排放的含碳气溶胶在灰霾期不断老化,单颗粒中二次无机组分增加,气溶胶整体老化严重.此外,灰霾期（H2）EC颗粒占总颗粒数的比例增至18.1%,并且与NO₃-、HSO₄-二次组分的混合状态增强,使平均能见度降低为4.0 km.研究显示,郑州大气能见度主要受化学组分、颗粒物混合状态和污染物质量浓度的影响.      

2004年春季北京一次沙尘暴的理化特性分析

2004-03-27～2004-03-29北京发生沙尘暴天气期间,监测了气溶胶TSP、PM10和PM2.5的浓度,利用撞击式采样器采集了8级膜样品,并用ICP-MS分析了气溶胶中元素的含量,同时监测了地面辐射和风速的变化.结果显示,此次沙尘暴导致TSP浓度比平时增加3～4倍,PM10浓度增加2～3倍,PM2.5浓度有所降低.研究还表明:地壳元素Na、Mg、Al、Mn和Fe主要分布在粗粒子上.而污染元素Zn、Pb主要分布在细粒子上,污染元素主要是本地源.沙尘暴对总辐射有明显的影响,导致地面总辐射衰减了37.8%.受大风影响粗粒子浓度增加显著,细粒子浓度明显减少.     

沈阳冬季大气颗粒物化学成分及其来源的分析

为了解沈阳城区大气颗粒物的元素特征及来源,2009年1月14日至2月2日,用安德森分级撞击式采样器在沈阳市城区进行了大气气溶胶分级采样,并用电感耦合等离子体质谱仪(ICP-MS)对细颗粒物样品中35种元素进行分析。结果表明:大气颗粒物中粗粒子占总元素浓度比重为54.9%,与2008年北京同时期所占比重相似。元素Fe、La、K和Mn分别代表不同来源的四种谱分布类型,富集因子分析表明,沈阳冬季的燃煤,城市交通、建筑扬尘、春节期间烟花爆竹的释放及工业释放是其主要来源。     

用质子X荧光法对广州市气溶胶中无机元素的分析

用8级撞击式采样器在广州市五个代表点采集了大气气溶胶样品,用质子激发X荧光分析(PIXE)法进行了分析。取得了近20种元素的质量浓度及其粒径分布。分别计算了元素中粗粒子和细粒子的富集因子,对元素的产生源及广州市大气气溶胶的特征进行了讨论。文章最后,将广州市中心大气气溶胶中15种元素含量的分析测试结果与我国其它城市大气气溶胶中的元素含量进行了比较和讨论。      

Effects of two sludge application on fractionation and phytotoxicity of zinc and copper in the soil

The potential harm of heavy metals is a primary concern in application of sludge to the agricultural land. A pot experiment was conducted to evaluate the effect of two sludges on fractionation of Zn and Cu in soil and their phytotoxicity to pakchoi. The loamy soil was mixed with 0%, 20%, 40%, 60% and 80% (by weight) of digested sewage sludge (SS) and composted sludge (SC). The additions of both sludges caused a significant raise in all fractions, resulting in that exchangeable (EXCH) and organic bound (OM) became predominance of Zn and organic bound Cu occupied the largest portion. There was more available amount of Zn and Cu in SS treatments than SC treatments. During the pot experiment, the concentration of Zn in EXCH, carbonate (CAR) and OM and Cu in EXCH and OM fractions decreased in all treatments, so their bioavailability reduced. Germination rate and plant biomass decreased when the addition rate was high and the best yield appeared in 20% mixtures at the harvest of pakchoi. The two sludges increased tissue contents of Zn and Cu especially in the SS treatments. Zn in pakchoi was not only in relationship to ΔEXCH and ΔCAR forms but also in ΔOM forms in the sludge-soil mixtures. Tissue content of Cu in pakchoi grown on SC-soils could not be predicted by ΔEXCH. These correlation rates between Zn and Cu accumulation in pakchoi and variation of different fractions increased with time, which might indicate that sludges represented stronger impacts on the plant in long-term land application.     

Intraspecific differences in effects of co-contamination of cadmium and

A hydroponic experiment was carried out to study intraspecific differences in the effects of different concentrations of cadmium (Cd)(0-10 mg/L) and arsenate (As(V)) (0-8 mg/L) on the growth parameters and accumulation of Cd and As in six wheat varieties Jing-9428, Duokang-1, Jingdong-11, Jing-411, Jingdong-8 and Zhongmai-8. The endpoints of wheat seedlings, including seed germination,biomass, root length and shoot height, decreased with increasing the Cd and As concentrations. Significant differences in seed germination, biomass, root length, shoot height and the accumulation of Cd and As were observed between the treatments and among the varieties (p ＜ 0.05). The lethal dosage 50% were about 20, 80, 60, 60, 80 and 20 mg As/L for Jing-9428, Duokang-1, Jingdong-11,Jing-411, Jingdong-8 and Zhongmai-8, respectively, and the corresponding values for Cd were about 30, 80, 20, 40, 60 and 10 mg Cd/L, respectively. Among the six varieties, Duokang-1 was found to be the most resistant to Cd and As toxicity, and Zhongmai-8 was the most sensitive to Cd and As co-contamination. The resistance of the six varieties was found dependant on the seedling uptake of Cd and As. Duokang-1 was the most suitable for cultivation in Cd and As co-contaminated soils.     

Toxic effects of acetochlor, methamidophos and their combination on nifH gene in soil

Toxic effects of two agrochemicals on nifH gene in agricultural black soil were investigated using denaturing gradient gel electrophoresis （DGGE） and sequencing approaches in a microcosm experiment. Changes of soil nifH gene diversity and composition were examined following the application of acetochlor, methamidophos and their combination. Acetochlor reduced the nifH gene diversity （both in gene richness and diversity index values） and caused changes in the nifH gene composition. The effects of acetochlor on nifH gene were strengthened as the concentration of acetochlor increased. Cluster analysis of DGGE banding patterns showed that nifH gene composition which had been affected by low concentration of acetochlor （50 mg/kg） recovered firstly. Methamidophos reduced nifH gene richness that except at 4 weeks. The medium concentration of methamidophos （150 mg/kg） caused the most apparent changes in nifH gene diversity at the first week while the high concentration of methamidophos （250 mg/kg） produced prominent effects on nifH gene diversity in the following weeks. Cluster analysis showed that minimal changes of nifH gene composition were found at 1 week and maximal changes at 4 weeks. Toxic effects of acetochlor and methamidophos combination on nifH gene were also apparent. Different nifH genes （bands） responded differently to the impact of agrochemicals： four individual bands were eliminated by the application of the agrochemicals, five bands became predominant by the stimulation of the agrochemicals, and four bands showed strong resistance to the influence of the agrochemicals. Fifteen prominent bands were partially sequenced, yielding 15 different nifH sequences, which were used for phylogenetic reconstructions. All sequences were affiliated with the alpha- and beta-proteobacteria, showing higher similarity to eight different diazotrophic genera.     

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.     

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.     

Arsenic uptake by arbuscular mycorrhizal maize （Zea mays L.） grown in an arsenic-contaminated soil with added phosphorus

The effects of arbuscular mycorrhizal (AM) fungus (Glomus mosseae) and phosphorus (P) addition (100 mg/kg soil) on arsenic (As) uptake by maize plants (Zea mays L.) from an As-contaminated soil were examined in a glasshouse experiment.Non-mycorrhizal and zero-P addition controls were included.Plant biomass and concentrations and uptake of As,P,and other nutrients,AM colonization,root lengths,and hyphal length densities were determined.The results indicated that addition of P significantly inhibited root colonization and development of extraradical mycelium.Root length and dry weight both increased markedly with mycorrhizal colonization under the zero-P treatments,but shoot and root biomass of AM plants was depressed by P application.AM fungal inoculation decreased shoot As concentrations when no P was added,and shoot and root As concentrations of AM plants increased 2.6 and 1.4 times with P addition,respectively.Shoot and root uptake of P,Mn,Cu,and Zn increased,but shoot Fe uptake decreased by 44.6%,with inoculation, when P was added.P addition reduced shoot P,Fe,Mn,Cu,and Zn uptake of AM plants,but increased root Fe and Mn uptake of the nonmycorrhizal ones.AM colonization therefore appeared to enhance plant tolerance to As in low P soil,and have some potential for the phytostabilization of As-contaminated soil,however,P application may introduce additional environmental risk by increasing soil As mobility.     

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.     

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.     

Degradation of metabolites accumulated of benzo[a]pyrene by coupling Penicillium Chrysogenum with KMnO4

Several main metabolites of benzo[a]pyrene （BaP） formed by Penicillium chrysogenum, Benzo[a]pyrene-1,6-quinone （BP 1,6- quinone）, trans-7,8-dihydroxy-7,8-dihydrobenzo[a]pyrene （BP 7,8-diol）, 3-hydroxybenzo[a]pyrene （3-OHBP）, were identified by high-performance liquid chromatography （HPLC）. The three metabolites were liable to be accumulated and were hardly further metabolized because of their toxicity to microorganisms. However, their further degradation was essential for the complete degradation of BaP. To enhance their degradation, two methods, degradation by coupling Penicillium chrysogenum with KMnO4 and degradation only by Penicillium chrysogenum, were compared; Meanwhile, the parameters of degradation in the superior method were optimized. The results showed that （1） the method of coupling Penicillium chrysogenum with KMnO4 was better and was the first method to be used in the degradation of BaP and its metabolites; （2） the metabolite, BP 1,6-quinone was the most liable to be accumulated in pure cultures; （3） the effect of degradation was the best when the concentration of KMnO4 in the cultures was 0.01% （w/v）, concentration of the three compounds was 5 mg/L and pH was 6.2. Based on the experimental results, a novel concept with regard to the bioremediation of BaP-contaminated environment was discussed, considering the influence on environmental toxicity of the accumulated metabolites.     

Impact of atrazine and nitrogen fertilizers on the sorption of chlorotoluron in soil and model sorbents

Sorption of chlorotoluron in ammonium sulfate, urea and atrazine multi-solutes system was investigated by batch experiments. The results showed application of nitrogen fertilizers to the soil could affect the behavior of chlorotoluron. At the same concentration of N, sorption of chlorotoluron decreased as the concentration of atrazine increased on the day 0 and 6 in soil, respectively. The sorption of chlorotoluron increased from 0 to 6 d when soils were preincubated with deionized water, ammonium sulfate and urea solution for 6 d. That indicated incubation time was one of the most important factors for the sorption of chlorotoluron in nitrogen fertilizers treatments. The individual sorption isotherms of chlorotoluron in rubbery polymer and silica were strictly linear in single solute system, but there were competition sorption between pesticides or between pesticides and nitrogen fertilizers. That indicated the sorption taken place by concurrent solid-phase dissolution mechanism and sorption on the interface of water-organic matter or water-mineral matter.