1960~2013年华南地区霾污染的时空变化及其与关键气候因子的关系

利用线性回归、聚类分析及相关分析等统计方法对华南地区57个地面气象站的观测资料进行分析,探究近54年华南地区霾日数的时空变化特征及其气候成因.结果表明,年平均霾日数大值区主要分布在广东珠江三角洲(珠三角)地区和广西中东部.54年来霾日数呈现显著的上升趋势,而2008年后有所下降.霾日数的季节变化表现为冬季最多,其次是秋季和春季,夏季最少.2008年以后春、夏、秋3季霾日数有所下降,而冬季仍维持在较高水平.不同等级霾日数在近54年来均有不同程度的上升,霾污染不仅在日数上有明显的增加趋势,而且污染强度在加强.不同地区霾日数的快速增长时期不一样,污染严重和正常污染地区发生在20世纪90年代,而相对清洁地区发生在2000年以后.另外近10年污染严重和正常污染地区霾日数有所下降,但相对清洁地区仍维持快速的增长趋势.近54年华南地区年降水日数、年平均风速、大风日数和年小风日数等气候因子变化结果致使气溶胶粒子的湿沉降减弱,污染物扩散能力下降,霾天气生成概率增加.     

天津地区霾天气特征研究

基于2014~2017年天津地区PM_2.5质量浓度，能见度和相对湿度监测数据开展霾天气特征研究.结果表明：天津中度以上霾过程分为五类：高压后部型，北部弱高压型，低压槽型，均压场型和锋前低压型.在现行标准下，中度霾一般对应重度污染天气，重度霾对应重度到严重污染天气；五级重度污染天气一般有中-重度霾发生，六级严重污染天气有重度霾天气发生.2013年“大气污染防治行动计划”开展以后，天津PM_2.5质量浓度和霾日均显著减少，2017年相比2013年霾日减少了55%，中度及其以上霾日由2013年的41d下降到2017年的20d，下降幅度超过50%.基于实况监测的PM_2.5质量浓度，能见度和相对湿度，可以较好的构建区域能见度计算方程.统计数据显示，其估算的能见度和实况值相关系数为0.94，相对误差为18.6%，非霾日辨识准确率为85%，霾日辨识准确率为95.6%，轻微霾辨识准确率为83%，轻度霾辨识准确率为78%，中度霾辨识准确率为93%，重度及以上霾辨识准确率为94%，对于判断霾等级，有较强的适用性.将该方程与空气质量模式结合开展霾等级预报，2015~2017年24h预报产品检验显示：能见度预报值与实况值相关系数为0.75，预报均值13.9km，实况均值14.1km，相对误差为29.6%，FAC2（预报值在实况值两倍范围内百分比）为98.1%，霾日预报准确率81.4%，霾日漏报率18.6%，霾日空报率20.6%，如果容错1级，轻微霾日预报准确率为96%，轻度霾日预报准确率为85%，中度及以上霾日预报准确率为69%，可有效支撑天津霾等级预报的开展.     

近50年华中地区霾污染的特征

基于1962~2011年霾日观测资料,使用线性回归、聚类分析及相关分析等统计方法分析了近50年华中地区霾污染的时空变化特征及其成因.结果表明,华中地区的霾高发中心位于河南中北部、湖北中西部和湖南中部人口集中的气溶胶浓度高值区,其中霾日数最多的站点为河南新乡,年均达到79.1d.霾的季节性变化表现为冬季霾日数最多,夏季最少,霾污染是典型的冬季大气环境事件.但随着近年春夏秋三季霾日的增加,华中地区霾污染的季节性差异减小.城市地区是华中霾污染严重的区域.近50年污染地区霾发生频率增多,而相对清洁地区霾污染发生频率减少.华中地区大气环境呈现出两极分化的变化特征.近50年来华中地区霾日增加受人为污染物排放加强和东亚季风减弱的共同影响.     

福州市春冬季灰霾天气PM10和PM2．5污染水平和气象特征分析

分析和探讨了福州市霾日和非霾日气溶胶PM10和PM2.5污染水平,无论春季或冬季,霾日福州市气溶胶PM10和PM2．5的质量浓度是非霾日的1．6倍;通过对霾日与非霾日的天气形势与及地面气象要素场的分析,揭示了福州市灰霾天气形成原因。为政府用空气扩散能力来对大气污染物排放进行调控,为开展相应的大气污染防治工作提供科学依据。     

1981~2010年深圳市不同等级霾天气特征分析

利用1981~2010年深圳市地面观测及空气质量监测资料,分析深圳不同等级霾天气的长期变化特征以及大气水平能见度、空气质量与霾的关系.结果表明:深圳霾日数总体呈增多趋势,强度增强,中度以上霾增多;各等级霾日数均呈增多态势,但不同等级霾日占年总霾日的比例变化趋势不同,轻微霾所占比例下降,轻度以上霾上升; 霾天气呈现冬季>秋季>春季>夏季的季节特征,但重度霾却是夏季最多; 霾导致大气水平能见度明显下降,霾日平均能见度较非霾日低6~7km,霾等级越高,能见度下降越明显,霾日能见度日变化幅度较非霾日小;霾日SO2、NO2浓度为非霾日的1.4~1.7倍,PM10是非霾日的2.2倍,大气颗粒物污染加剧可能是深圳能见度恶化、霾天气增多的一个重要原因;针对荔香站霾日SO2浓度日变化不明显,PM10 、NO2浓度呈双峰型分布,与上下班时段吻合,说明机动车的增加也是深圳霾天气增多的主因之一;霾等级越高,空气中PM10、SO2、NO2的浓度越高,从轻微到重度霾各级之间SO2、NO2和PM10浓度增幅大都在15%~20%.     

1960~2016年江西省霾日变化特征及气候成因分析

利用江西省1960~2016年82个气象站水平能见度、相对湿度和天气现象等资料,重建了江西省霾日序列,分析了江西省霾日数的年际变化特征,并通过霾日数与降水日数、大风日数和静风日数的相关关系,探讨了不同季节霾日数年际变化的气候成因.结果表明：1960~2016年江西省霾日数表现为在1970s有明显偏高、1980年后显著增加趋势（0.53d/a）,赣北地区霾日多且增加速率快.四季霾日数均有增加,其中秋季贡献最大（0.21d/a,P<0.001）,春季其次（0.12d/a,P<0.001）,冬季霾日数最多,但年际趋势并不显著（0.10d/a,P>0.05）,夏季年均霾日数较低,增加幅度最小（0.09d/a,P<0.001）.过去几十年降水日数减少（-0.26d/a,P>0.05）导致大气湿沉降能力减弱,以及大风日数减少（-0.33d/a,P<0.01）和静风日数增加（1.73d/a,P<0.01）导致大气扩散能力降低,为江西省霾日增加提供了有利气候背景.但主要气候成因因季节不同：春季霾日数增加的主要气候成因是大风日数减少（r=-0.48,P<0.01）,与其他要素的关系不显著;夏季亦与大风日数减少显著相关（r=-0.50,P<0.01）,同时与静风日数增加显著相关（r=0.37,P<0.05）;秋季受大风日数减少、静风日数增加以及降水日数减少共同影响,导致秋季霾日增加速率最快;冬季霾日数仅与降水日数显著相关（r=-0.36,P<0.05）,但由于冬季降水日数变化趋势不明显（-0.26d/a,P>0.05）,冬季霾日数变化不显著.     

江苏省一次重霾污染天气的特征和机理分析

利用PM10, SO2,O3,NH3, NOx,CO等6种大气成分浓度数据、常规气象观测数据和天气图资料,结合HYSPLIT4后向轨迹模式,对2008年10月28~30日发生在江苏省的一次大面积重霾污染天气的特征和成因进行了综合分析.结果表明,此次重霾污染天气过程观测到的PM10, NOx,CO最大地面浓度分别达到0.553, 0.170, 2.738mg/m3,水平能见度达到1km以下.其中城市中CO和NOx浓度较郊区高,而SO2和O3则较低.该污染事件与大范围秋收秸秆集中燃烧,造成大量污染物排放有密切关系.平稳的高空环流形势、暖平流、地面高压场分布为重霾污染天气的发生、发展提供了有利的气象条件,地面表现为稳定的大气层结、静小风和低湿环境,非常不利于污染物的扩散.后向轨迹计算分析表明,造成此次重霾污染天气的气团主要来自河南中东部、苏北和安徽等重要产粮地区,长距离输送对区域霾污染产生重要影响.     

基于人工与自动观测对比分析的霾日重建

以杭州、宁波、衢州、温州气象观测站为代表站,基于浙江省2012~2014年人工与自动能见度、相对湿度观测资料,对比分析并建立拟合方程,对历史能见度及相对湿度进行修正,再利用《霾的观测与预报等级》标准对浙江历史霾日进行重建.研究表明,自动观测能见度与人工能见度线性相关性较好,但自动较人工明显偏低,人工能见度较好的沿海地区偏低更明显,全省自动能见度较人工平均偏低28.6%;自2004年开展相对湿度自动观测以来,相对湿度明显下降,根据人工与自动相对湿度对比观测数据,两种观测数据线性相关性较好,自动观测平均值小于人工平均值3%~6%;在对能见度与相对湿度采取线性回归方法进行均一性修正后,重建了霾日序列,结果表明重建后的霾曰序列消除人工与自动观测资料的误差,比原观测霾日气候序列质量有明显提高,重建的霾日变化趋势稳定,各站判定标准统一,更加合理.通过与各站2013年PM_(2.5)达到轻微污染日数与重建霾日数比较,二者的重合率大部分地区达到50%以上.利用修正重建的霾日对浙江1971年以来的霾日进行评估,20世纪70年代霾日较少,80年代逐步增加,本世纪以来增加明显,中心区域逐步由浙江中北部向浙北区域及沿海发展,尤其是一些中心城市霾日数最多.     

基于多卫星遥感的东北地区霾污染时空特征研究

利用多卫星(MODIS、CALIPSO、VIIRS)观测的气溶胶产品、地面空气质量监测数据和气象资料,获取了东北地区2006—2015年期间气溶胶光学厚度(AOD)的季节和年际变化特征,并对2014年10月14日东北地区一次典型重霾污染过程的特征及其潜在传输路径进行了深入讨论.研究结果显示,自2008年起东北地区灰霾污染范围扩大且污染程度加剧,呈带状空间分布(营口-长春-哈尔滨);区域内AOD值呈春、秋和冬季高,夏季低的时间变化特征.采用CALIPSO星载激光雷达数据与MODIS、VIIRS卫星获取的AOD开展综合分析,可有效弥补MODIS、VIIRS卫星因冬季积雪亮地表干扰所产生的AOD缺省区域,增强对长期积雪覆盖地区霾污染的时空特征分析能力.与反映霾污染空间分布范围更广的VIIRS卫星相比,MODIS卫星AOD值与东北地区地面观测获取的AQI、PM10和PM2.5相关系数更高,分别为0.89、0.73和0.83.进一步研究结果显示,秋末冬初东北地区的霾污染事件与农作物秸秆焚烧有关,同时,华北地区灰霾污染可跨越渤海湾传输至东北地区,进一步形成更大尺度的带状区域污染.     

1960~2013年我国霾污染的时空变化

利用近54年（1960～2013年）我国霾日以及一些相关气象要素的观测资料,采用气候倾向估计、聚类分析、累积距平和突变检验等多种方法,分析了我国霾日数变化特征.结果表明：我国的霾污染主要发生在中东部和南部,尤以北京、山西中部和南部、河南局部地区、长江三角洲和珠江三角洲等地最为严重,我国西部和东北部地区相对较少.霾日发生的频率总体呈增加的趋势,而且与能源消耗总量有很好的正相关关系.我国霾日数的增加除了依赖于污染源排放加剧外,不利的气候条件加剧了霾天气的发生.近54年降水日数、平均风速、日照时数和相对湿度与霾日数的相关系数分别为-0.653、-0.635、-0.462和-0.699,远远超出了99.9%的信度检验标准.聚类分析表明,上升极显著、上升显著和上升明显的站点年平均霾日数近年来均有加速上升的趋势,其累积距平的变化趋势为下降-平缓-上升型.轻微上升站点上升时期为20世纪60年代至70年代末与2000年之后,累积距平为多波动型.轻微下降与下降明显的站点快速上升时期为60年代至70年代末,随后均有不同程度的下降,累积距平呈上升-平缓-下降型,且在1992～1993年间霾日数发生了由多到少的突变.     

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.     

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.     

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.     

Potential of plant polyphenol oxidases in the decolorization and removal of textile and non-textile dyes

In this study an effort has been made to use plant polyphenol oxidases; potato （Solanum tuberosum） and brinjal （Solanum melongena）, for the treatment of various important dyes used in textile and other industries. The ammonium sulphate fractionated enzyme preparations were used to treat a number of dyes under various experimental conditions. Majority of the treated dyes were maximally decolorized at pH 3.0. Some of the dyes were quickly decolorized whereas others were marginally decolorized. The initial first hour was sufficient for the maximum decolorization of dyes. The rate of decolorization was quite slow on long treatment of dyes. Enhancement in the dye decolorization was noticed on increasing the concentration of enzymes. The complex mixtures of dyes were treated with both preparations of polyphenol oxidases in the buffers of varying pH values. Potato polyphenol oxidase was significantly more effective in decolorizing the dyes to higher extent as compared to the enzyme obtained from brinjal polyphenol oxidase. Decolorization of dyes and their mixtures, followed by the formation of an insoluble precipitate, which could be easily removed simply by centrifugation.     

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.     

Effect of sorbed and desorbed Zn(Ⅱ) on the growth of a green alga (Chlorella pyrenoidosa)

Toxic effect of Zn(Ⅱ) on a green alga (Chlorella pyrenoidasa) in the presence of sepiolite and kaolinite was investigated.The Zn-free clays were found to have a negative impact on the growth of C.pyrenoidosa in comparison with control samples (without adding any clay or Zn(Ⅱ)).When Zn(Ⅱ) was added,the algae in the presence of clays could be better survived than the control samples,which was actually caused by a decrease in Zn(Ⅱ) concentration in the solution owing to the adsorption of Zn(Ⅱ) on the clays.When the solution system was diluted,the growth of algae could be further inhibited as compared to that in a system which had the same initial Zn(Ⅱ) concentration as in the diluted system.This in fact resulted from desorption of Zn(Ⅱ) from the zinc-contaminated clays,although the effect varied according to the different desorption capabilities of sepiolite and kaolinite.Therefore the adsorption and desorption processes of Zn(Ⅱ) played an important part in its toxicity,and adsorption and desorption of pollutants on soils/sediments should be well considered in natural eco-environmental systems before their risk of toxicity to aquatic organisms was assessed objectively.