广州城区秋季大气PM_(2.5)中主要水溶性无机离子分析

分别在广州市中心城区高楼顶(距地50m)和交通干线路边(距地1.2m),于2006年秋季连续一周采集了大气PM2.5样品,对比分析了SO42-、NO3-、Cl-、F-、Na+、NH4+、Ca2+、K+、Mg2+等9种水溶性无机离子含量。结果表明,楼顶相对充分混合大气中PM2.5的质量浓度范围59.5～129.5μg/m3,均值为83.7μg/m3;交通干线路边大气PM2.5的质量浓度范围为108.4～132.2μg/m3,均值为121.1μg/m3。9种离子总浓度平均达到50.9(楼顶)和44.1(路边)μg/m3,占PM2.5质量浓度的60.8%(楼顶)和36.4%(路边)。SO42-和NO3-为水溶性无机离子主要组成,其占PM2.5质量浓度的比例均是楼顶高于路边,显示二次气溶胶对楼顶充分混合大气中PM2.5有较大贡献,而路边样品中一次来源贡献相对较大。计算表明采样期间海盐对广州大气PM2.5中的水溶性组分贡献较小。NH4+当量浓度远小于SO42-和NO3-的当量浓度,中和度远1,反映PM2.5酸性较强,且楼项PM2.5粒子酸性高于路边样品。     

青岛采暖期不同天气状况下大气颗粒态无机氮分布研究

于2007-10～2008-04采集了青岛近海采暖前及采暖期内大气气溶胶样品,并运用离子色谱法(IC)分析了颗粒物中的无机氮组分.结果表明,采暖期内青岛颗粒物和无机氮的浓度都有明显增加,采暖期颗粒物质量浓度为137.41μg/m3,比采暖前增加了82.2%;NO3--N和NH4+-N浓度分别由采暖前的2.48μg/m3和6.95μg/m3增加到采暖期的4.43μg/m3和10.28μg/m3.天气过程对于青岛颗粒物浓度和无机氮离子浓度均有较大影响.采暖期晴天颗粒物浓度均值为181.34μg/m3,较采暖前增加32.0%,主要源于二次气溶胶的NH4+-N和NO3--N浓度分别为5.56μg/m3和1.86μg/m3,低于采暖前.雾天因为低温高湿和污染物的循环积累,样品中颗粒物、NH4+-N和NO3--N平均浓度比采暖前浓度增加了1～2倍.大风降温天气下颗粒物浓度及无机氮组分浓度均有所降低.采暖期烟尘和飞灰的排放明显影响青岛大气颗粒物和无机氮的粒径分布,特别是细粒子部分.青岛近海颗粒物及NO3--N质量浓度呈现双峰分布,采暖前峰值出现在0.43～0.65μm与3.3～4.7μm的范围内,采暖期积聚模态峰值移至0.65～1.1μm范围内.NH4+-N粒径分布均呈现明显的单峰分布,峰值出现在积聚模态.     

云南宣威燃煤室内可吸入颗粒物质量浓度变化特征

应用中流量采样器TSP-PM10-PM2.5对我国肺癌高发区宣威地区6个乡村19家农户进行采样,运用滤膜称重法来分析不同燃料类型室内及相应室外的大气颗粒物质量浓度特征.结果显示,各村庄室内、室外PM10质量浓度比值(I/O)变化范围为1.74~2.87,说明室内PM10污染主要由室内污染源引起;做饭时段室内PM10污染比其他时段严重,尽管烟囱可以将大量的污染物排出室外,但室内颗粒物的质量浓度依然较高.室内PM10质量浓度依燃料类型从高到低依次为块煤用户>型煤用户>燃柴用户>用电用户,室内PM2.5质量浓度依燃料类型从高到低表现为块煤用户>燃柴用户>用电用户;块煤、型煤用户的室内PM10的质量浓度平均值(442.49μg/m3、399.14μg/m3)超过国家室内空气质量标准日均值150μg/m3,污染严重;燃柴和用电用户室内PM10的质量浓度平均值(145.50μg/m3、119.91μg/m3)低于国家室内空气质量标准日均值150μg/m3,污染较轻.块煤用户PM2.5质量浓度日均值(132.58μg/m3)超过2012年2月29日环境保护部发布的环境空气质量标准二级标准75μg/m3,而燃柴和用电户PM2.5的质量浓度(55.24μg/m3、65.02μg/m3)均低于环境空气质量标准二级标准75μg/m3,说明块煤用户室内细颗粒污染较重,用电和燃柴用户室内细颗粒物污染相对较轻.     

深圳大运会前后大气含碳气溶胶污染特征

2011年8月12~24日,深圳市成功举办了第26届世界大学生运动会.为保证空气质量,两个观测点的PM2.5(空气动力学直径?2.5μm的大气颗粒物)质量浓度均值分别为(12.99±3.73)μg/m3和(25.24±5.20)μg/m3.然而,8月24日(含)大运会结束、主要污染控制措施取消之后,PM2.5的质量浓度呈现台阶式突增,测得观测点所处位置PM2.5分别为(48.01±8.73)μg/m3和(54.05±6.53)μg/m3.为探讨大气颗粒物污染水平变化的原因,对大运会结束前后深圳市大气含碳气溶胶的变化特征进行了分析,利用元素碳示踪法对大运会结束前后的一次和二次含碳气溶胶污染水平进行估算,结果显示大运会结束后的2个观测点的一次有机碳估算浓度较大运会期间增长了55%和22%,二次有机碳分别增长了442%和169%.结合气象因素及后向轨迹聚类模型的分析结果,认为在大运会结束后的大气颗粒物浓度阶梯状增加的原因除本地污染累积外,污染气团远距离传输以及气象条件都对阶梯型污染有一定的贡献.     

2013年夏季嘉兴市一次光化学事件的观测分析

为研究2013年8月5~11日嘉兴地区一次光化学事件形成的高浓度O3污染的变化特征及成因,对8月2~14日的主要污染气体(O3、NO2、NO、CO、SO2)、颗粒物(PM10、PM2.5)以及气象要素进行了观测分析.结果表明,嘉兴污染日的O3平均浓度是正常日的2.4倍,超标率多在29.0%以上,9日超标率高达45.8%,此次污染事件是高温下剧烈的光化学反应以及低湿低风速的稳定天气形势共同作用造成的.污染日和正常日的O3日变化均呈单峰分布,峰值出现在14:00左右,O3在污染日和正常日生成期的增长速率分别为50.3μg·(m3·h)-1和21.6μg·(m3·h)-1,在消耗期的下降速率分别为16.8μg·(m3·h)-1和23.4μg·(m3·h)-1,NO、NO2和CO在污染日的浓度分别是正常日的1.1、1.5和1.5倍,为光化学反应提供了有利的反应条件.污染日PM2.5浓度、PM10浓度、PM2.5/PM10的比值分别是正常日的2.5、2.3、1.1倍,污染日大气光化学反应异常活跃,更有利于细颗粒物的生成.     

北京市2009年8月大气颗粒物污染特征

为研究2008年8月北京奥运会1a之后北京市大气颗粒物的污染特征,于2009年8月对北京市大气颗粒物PM10、PM2.5样品进行采集,测量其质量浓度并对其中的水溶性离子组分进行分析.研究发现2009年8月北京市大气颗粒物PM10、PM2.5质量浓度日均值分别为176.9μg/m3和102.5μg/m3.PM10质量浓度比2008年观测值上升了180%,比2007年降低了10%; PM2.5质量浓度比2008年观测值上升了126%,比2007年上升了31%.水溶性离子是大气颗粒物的重要组分,分别占PM10和PM2.5质量浓度的43%和61%.对比发现,污染天气条件下PM2.5/PM10和NO3-/SO42-比值升高,移动源是北京地区主要的污染物来源.风向风速和降水等天气条件对颗粒物质量浓度有很大影响,其中0.5~1.0m/s的东南风条件下大气颗粒物污染最为严重.     

北京大气气溶胶中有机碳及可萃取有机卤素污染物

研究了2002年5月～2003年4月北京城区大气中PM2.5和PM10中有机碳(OC)及可萃取有机卤素污染物(EOX)的浓度.结果表明,PM10和PM2.5的年均值分别为172.8μg/m3和110.9μg/m3,分别是美国年均值标准(PM10, 50μg/m3; PM2.5, 15μg/m3)的3.5倍和7.4倍,说明污染相当严重;PM2.5与PM10中OC的月均浓度分别为9.1～33.9μg/m3和13.1～46.2μg/m3,冬季大气中OC的浓度最高,夏季最低; PM2.5中OC和EOX的百分含量高于PM10,细粒子更易于富集有机污染物; PM2.5和PM10中EOX的含量顺序为EOCl>> EOBr(EOI),约有73%～88%和69%～91%的EOX为EOCl,大气中的有机卤素污染物主要为有机氯污染物;PM2.5中OC与EOX的含量变化趋势一致,细颗粒物中OC对EOX的含量起到了控制作用,PM10中OC对EOX的含量影响有限.     

上海市中心城区低空大气臭氧污染特征和变化状况

对2005年1月～12月上海闸北地区地面空气臭氧污染浓度连续监测结果分析,表明臭氧小时浓度均值超过GB3095-1996<环境空气质量标准>二级标准160μg/m3的频率为2.88%,其中6月份超标率居全年之首,1月、2月和12月超标率为零.臭氧浓度日变化规律表明,日最大值出现在12时～14时之间,具有受污染地区光化学过程臭氧生成的典型日变化特征.臭氧浓度日振幅6月最大,2月最小.5月份臭氧月均浓度91μg/m3全年最高,最高小时均值浓度350μg/m3出现在5月19日,说明上海中心城区空气中臭氧生成可能受到前体污染物的浓度影响更大.太阳紫外辐射、气温、风速、风向、相对湿度、降水等气象因素的变化对O3变化的影响分析,在高温晴朗的天气中观察到NO2/NO比值与O3成显著线性关系.     

东北辽中南基地城市群PM_(2.5)污染特征研究

基于中国环境监测总站"全国城市空气质量实时发布平台"2014年和2015年的PM_(2.5)数据,探讨分析东北辽中南基地城市群PM_(2.5)污染特征。结果表明:研究期间鞍山和沈阳两市的PM_(2.5)污染最为严重,2014年和2015年的超标率分别为31.8%、35.6%和26%、34.5%;城市群PM_(2.5)浓度呈现出显著的冬高夏低、春秋平稳的基本特征,冬季均值高达70.4μg/m3,是一级浓度限值的2倍,而夏季均值低为31.6μg/m3;因人类活动对PM_(2.5)的影响,周末浓度高于工作日;2015年较2014年相比,PM_(2.5)在可吸入颗粒物中比重增加,对大气污染物的贡献显著,但从整体来看辽中南基地城市群的空气质量出现了明显好转。     

南、黄海及青岛地区大气气溶胶中无机氮组分的研究

于2004年冬季在青岛地区采集了大气气溶胶TSP(总悬浮颗粒物)样品,并于2005年3月和5月航次采集了黄、南海TSP和安德森分级样品,分析了气溶胶中无机氮组分(NO2-、NH4 、NO3-)的浓度,探讨了相应区域大气颗粒物中各种无机氮离子的区域分布、粒级分布.青岛地区冬季TSP的月平均值为102.00～227.00 μg·m-3;黄海TSP浓度为80.00～130.00 μg·m-3,低于青岛地区;南海TSP浓度最低,在30.167μg·m-3以下.NH4 -N是南、黄海及青岛地区大气气溶胶中主要的无机氮组分,占到总无机氮含量的53.14%～94.72%;其次是NO3--N,占到总无机氮含量的4.75%～46.64%;NO2--N对无机氮的干沉降贡献很小,仅占不到0.54%.NO3--N的粒径范围较宽,多数呈现双峰分布,峰值出现在4.7～7.0 μm和2.1～3.3 μm范围内;NH4 -N的粒径分布范围较窄,主要集中于1.1μm以下的细粒子范围内;NO2--N性质不稳定,其分布比较复杂.近年来,汽车尾气排放量的增大增加了青岛地区大气气溶胶中NO3--N的含量.     

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.     

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.     

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.     

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.     

Removal of heavy metals from sewage sludge by low costing chemical method and recycling in agriculture

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Isolation and preliminary characterization of a 3-chlorobenzoate degrading bacteria

A study was conducted to compare the diversity of 2-, 3-, and 4-chlorobenzoate degraders in two pristine soils and one contaminated sewage sludge. These samples contained strikingly different populations of mono-chlorobenzoate degraders. Although fewer cultures were isolated in the uncontaminated soils than contaminated one, the ability of microbial populations to mineralize chlorobenzoate was widespread. The 3- and 4-chlorobenzoate degraders were more diverse than the 2-chlorobenzoate degraders. One of the strains isolated from the sewage sludge was obtained. Based on its phenotype, chemotaxonomic properties and 16S rRNA gene, the organism S-7 was classified as Rhodococcus erythropolis. The strain can grow at temperature from 4 to 37℃. It can utilize several （halo）aromatic compounds. Moreover, strain S-7 can grow and use 3-chlorobenzoate as sole carbon source in a temperatures range of 10-30℃ with stoichiometric release of chloride ions. The psychrotolerant ability was significant for bioremediation in low temperature regions. Catechol and chlorocatechol 1,2-dioxygenase activities were present in cell free extracts of the strain, but no （chloro）catechol 2,3- dioxygenase activities was detected. Spectral conversion assays with extracts from R. erythropolis S-7 showed accumulation of a compound with a similar UV spectrum as chloro-cis,cis-muconate from 3-chlorobenzoate. On the basis of these results, we proposed that S-7 degraded 3-chlorobenzoate through the modified ortho-cleave pathway.     

Single and joint effects of pesticides and mercury on soil urease

The influence of two pesticides including chlorimuron-ethyl and furadan and mercury （Hg） on urease activity in 4 soils （meadow burozem and phaeozem） was investigated. The soils were exposed to various concentrations of the two pesticides and Hg individually and simultaneously. Results showed that there was a close relationship between urease activity and organic matter content in soil. Chlorimuron-ethyl and furadan could both activate urease in the 4 soils. The maximum increment of urease activity by chlorimuronethyl was up to 14%-18%. There was almost an equal increase （up to 13%-21%） in the urease activity by furadan. On the contrary, Hg markedly inhibited soil urease activity. A logarithmic equation was used to describe the relationship （P〈0.05） between the concentration of Hg and the activity of soil urease in the 4 tested soils. Semi-effect dose （ED50） values by the stress of Hg based on the inhibition of soil urease in the 4 soils were 88, 5.5, 24 and 20 mg/kg, respectively, according to the calculation of the corresponding equations. The interactive effect of chlorimuron-ethyl or furadan with metal Hg on soil urease was mainly synergic at the highest tested concentrations.