沧州市大气降水化学特征分析

为了解沧州大气降水化学特征,于2009年4-11月采集了沧州大气降水样品,测定了pH值、电导率和主要离子(Na+、NH4+、K+、Mg2+、Ca2+、F-、Cl-、NO3-和SO42-)浓度。结果表明,观测期间降水pH值为4.18~7.30,降水量加权平均pH值为5.23,降水酸化频率为34%;电导率值为18.5~245.0μS/cm,降水量加权平均电导率值为39.2μS/cm;降水主要离子加权平均浓度为641.36μeq/L;降水中主要阳离子成分是NH4+和Ca2+,降水量加权平均浓度分别为191.06和96.81μeq/L,分别占到阳离子总量的53%和27%;阴离子主要成分是SO42-和NO3-,降水量加权平均浓度分别为175.05和58.19μeq/L,分别占到阳离子总量的63%和21%。降水中[SO42-]/[NO3-]值为3.01,仍属于硫酸型降水,但酸雨类型逐渐由硫酸型向硫酸-硝酸混合型过渡;[NH4+]/[Ca2+]值为1.97,NH4+对降水酸度的中和作用要大于Ca2+;NH4+、SO42-和NO3-等二次组分占到降水中主要离子总量的66%,表明二次污染比较严重。降水离子相关分析表明,SO42-、NO3-、Ca2+、NH4+的相关性较好,SO42-和NO3-的相关系数为0.732,NH4+与SO42-(R=0.540)、NO3-(R=0.628)的相关系数分别大于Ca2+与SO42-(R=0.532)、NO3-(R=0.410)相关系数。气流轨迹分析表明,研究区降水主要受到5类气团影响,不同气团影响下,降水pH值、电导率和离子组成存在差异。     

泰山降水化学及大气传输的研究

为了解泰山降水的化学组成特征及其来源,于2004年7月至12月间在泰山上采集了23场降水样品,进行了pH值、电导率的测定、主要水溶性阴阳离子的分析以及每场降水的后推气流轨迹分析.结果表明,降水pH的雨量加权均值为4.74,电导率的雨量加权均值为2.26mS·m-1,泰山降水已受到酸性污染;降水中浓度较高的阳离子是NH4 和Ca2 ,雨量加权均值浓度分别为50.62和29.04μeq·L-1,浓度较高的阴离子是SO42-和NO3-,雨量加权均值浓度分别为70.32和23.44μeq·L-1;SO42-/NO3-、NH4 /Ca2 当量浓度比的平均值依次为3.41、2.13.对降水的化学组成作了相关性分析,发现NH4 、Ca2 、SO42-、NO3-浓度之间具有很好的相关性;通过气流轨迹分析发现酸性最强的降水气团来自于我国的南部地区或沿途经过华东地区,离子浓度最高的降水气团来自于我国的北部地区或欧洲大陆,来自东亚地区的降水气团的离子浓度最低.     

浙江宁波天童地区酸性降水化学特征研究

为了解浙江宁波天童地区降水的化学特征、离子来源及酸性降水的成因,于2010年3月—2011年2月在该地区采集了90个降水样品,并运用离子色谱法分析其化学组分.结果显示,天童地区降水的酸化频率和酸化程度非常高,酸雨频率为97%,雨量加权pH平均值为4.37,离子浓度的大小顺序为SO24->NH4+>NO3->Ca2+>Cl->Na+>Mg2+>K+>F-,降水较清洁;降水pH值和各离子含量存在明显的季节变化,总体表现为冬、春季污染程度高于夏、秋季;SO24-/NO3-的浓度比值为1.9,表明该地区酸雨类型为硫酸和硝酸复合型;SO24-、NO3-、NH4+和部分Ca2+主要来自人为污染源,Na+、Cl-和大部分Mg2+主要来自海洋源,K+和大部分Ca2+则主要来自地壳源,海洋对天童地区降水离子组分影响较大,但对降水酸度影响并不显著;NH4+与SO42-(r=0.90)、NO3-(r=0.88)的相关性分别大于Ca2+与SO24-(r=0.67)、NO3-(r=0.73)的相关性,且NH4+/Ca2+的浓度比值为1.47,说明NH4+对降水酸性的中和作用大于Ca2+,与我国其他城市降水相比,天童地区降水中的碱性离子,尤其是Ca2+浓度较低,从而导致降水酸度高于北方地区和西南其他地区.     

北京市一次沙尘过程中降水化学组分的监测分析

2010-4-5北京市出现了罕见的沙尘过程中降水,在市中心采集了雨水样品,用离子色谱方法分析了样品中9种离子组分浓度,结果表明:该次降水pH值较高(7.33)、电导率偏高(24.50mS/m)、可溶性离子浓度普遍高,9种离子浓度总和为3080meq/L;降水中离子当量浓度之比SO42-/NO3-为1.27, Ca2+/NH4+为1.25.为了进一步研究沙尘对降水化学组成的影响,统计了2005年至2010年全市3个监测点每年4月(沙尘高发期)监测的39次降水,得到其平均pH值为6.84、电导率为9.20 mS/m;降水中当量浓度之比SO42-/NO3-和Ca2+/NH4+分别为2.37和1.87.比较2组数据可见,发生在沙尘过程中的这次降水NO3-离子浓度的增加较为突出.而与历年年平均水平相比,4月降水均凸显了Ca2+和NO3-大幅增加的特征.进一步分析该次过程中同一监测点酸根离子前体物SO2、NO2的浓度变化特征发现:在沙尘和降水持续期间NO2浓度较低,在降水持续的时段SO2浓度显著降低,表明大气湿度对于SO2气粒转化起到了制约作用.     

上海金山区酸雨分布特征及降水酸度主控因子探讨

依据上海金山区2006-2010年降水监测数据,分析了该地区降水pH年均值、酸度及酸雨频率的分布特征,并对降水化学组成及各离子间的相关性进行了分析。结果表明,2006-2010年金山区降水的酸化及酸化频率较高,pH均值为4.24,酸雨频率为86.4%。降水主要离子为SO42-、NO3-、NH4+、Ca2+和Na+,上述5种离子占降水离子总浓度的87.8%,主要酸性离子SO42-、NO3-与阳离子NH4+、Ca2+和Mg2+均具有较高相关性。通过对降水酸度主控因子的探讨发现,主要致酸物质为SO42-,但NO3-对降水酸度的影响越来越大,碱性物质中和作用中起主导地位的是NH4+,雨水酸化的最主要来源为人为污染源。     

崇明东滩湿地降水化学特征及来源解析

2009年5月~2010年4月收集了崇明东滩湿地降水,测定了样品的pH值、电导率和主要水溶性离子的浓度,并利用富集因子法和后向轨迹分析对降水中无机离子成分进行源解析.结果表明,崇明东滩整体空气质量良好,大气污染物浓度较低.降水的pH值和电导率的加权均值分别为5.24,17.49μS/cm,为轻度污染的弱酸性水平;SO42?和NO3?是主要的致酸离子,加权浓度分别为52.27,21.39μeq/L;NH4+和Ca2+是主要的碱性离子,加权浓度分别为33.36,27.13μeq/L;离子来源分析表明,Na+和Cl?主要来自于海洋,NH4+的中和作用大于Ca2+和Mg2+,大气颗粒物主要以(NH4)2SO4、NH4HSO4、NH4NO3的形式存在;后向轨迹分析表明降水主要受海洋风向影响,西北、西南方向和长江三角洲地区的人为污染物的中长尺度传输是造成崇明东滩酸雨的重要原因.     

丽江-玉龙雪山不同区域大气降水化学特征

2008─2009年在丽江-玉龙雪山地区的丽江市区、玉龙雪山冰川公园索道下部站(索道地区)和白水1号冰川区(冰川区)3个采样点采集了113个降水样品,对其pH、电导率和主要离子(Cl-、SO42-、NO3-、Ca2+、Mg2+、Na+、K+和NH4+)质量浓度进行了分析.结果表明,所有样品实测pH均高于5.6.3个采样点ρ(总离子)平均值为丽江市区>索道地区>冰川区,其中ρ(SO4 2-)和ρ(Ca2+)均最高.丽江市区季风前后各离子质量浓度变化显著,其中海盐离子质量浓度〔ρ(Na+)和ρ(Cl-)〕从季风前期到季风期变化不大,在季风后期增加;ρ(NO3-)、ρ(SO42-)、ρ(NH4+)、ρ(Ca2+)、ρ(K+)和ρ(Mg2+)在季风前期显著高于季风期和季风后期.采用相关分析和主因子分析法对降水中离子来源进行研究,表明SO42-、NO3-和NH4+主要来自局地人类活动的贡献,Na+、K+和Cl-是海洋源贡献,Ca2+和Mg2+主要来源于地表粉尘.      

三峡库区降水化学组成及时空变化特征

对2000-2009年三峡库区巴南、涪陵和万州3个观测点降水的pH、电导率及其主要化学成分的时空变化进行了分析研究.结果表明,巴南、涪陵、万州降水pH平均值分别为5.76、6.03和5.52,平均电导率分别为117.3、72.3和63.1 μS·cm-1,降水酸化趋势在逐渐增强,污染程度高于北京、成都、深圳、湖南等地.降水中SO42-占阴离子总量的77％,NH4+和Ca2为主要的阳离子.巴南、涪陵、万州3个监测点的[NO3-]/[SO42-]比值较低,分别为0.125、0.164和0.169,表明降水酸化类型为硫酸型.由于排放与气象条件(包括降雨量等)的季节性变化,各离子组分呈现明显的时空变化特征,总体表现为冬春季降水中离子浓度高于夏秋季,污染程度为巴南＞涪陵＞万州.     

兴隆大气气溶胶中水溶性无机离子分析

2009年9月～2010年8月在兴隆大气背景站,利用Andersen分级采样器进行大气气溶胶样品的采集,并利用离子色谱分析了其中的水溶性无机离子的成分含量.结果表明,TSP、PM2.1和PM1.1中总水溶性无机盐的年平均浓度分别为(89.66±47.66)、(54.44±34.08)和(44.39±29.95)μg·m-3,其中SO42-、NO3-、Ca2+和NH4+为兴隆大气气溶胶中最主要的水溶性无机离子.PM2.1中总水溶性无机离子的年平均浓度占TSP的61%.PM1.1总水溶性无机离子的年平均浓度占TSP的50%,占PM2.1的82%.PM1.1、PM2.1和TSP中水溶性无机离子总浓度季节性变化趋势一致,夏季>秋季>春季>冬季.NH4+与SO42-的摩尔比>2,表明NH4+未被SO42-完全中和.在细粒子中NH4+和SO42-、NO3-均有较好的相关性,相关系数分别为0.96和0.87,表明NH4+可能以(NH4)2SO4和NH4NO3的形式存在.     

北京东北部城区大气细粒子与相关气体污染特征研究

于2008年7月~2009年4月的4个季节,在北京市朝阳区北部,利用VAPS通用型大气污染物采样仪(URG3000K)对大气细粒子(PM2.5)和环境空气中相关气体进行了同时采集,并利用IC离子色谱仪(DX-600型)分析了PM2.5中水溶性无机离子成分和环境空气中相关气体的含量.结果表明,PM2.5质量浓度春季>夏季>冬季>秋季;SO42-、NO3-和NH4+是PM2.5中最主要的3种水溶性无机离子,年均质量浓度分别为14.82μg/m3、11.57μg/m3和8.35μg/m3,三者浓度之和占PM2.5中总水溶性无机离子浓度的86.28%.SO42-、NH4+浓度占PM2.5浓度百分比均为夏、秋季高于冬、春季; NO3-浓度占PM2.5浓度的百分比为秋季>春季>夏季>冬季.空气中的SO2、NO2和NH3等气态污染物的含量直接影响PM2.5中二次离子SO42-、NO3-和NH4+的浓度, SO2、NO2浓度的季节特征为冬、春季高于夏、秋季,与SO42-、NO3-的季节变化规律相反; NH3浓度在夏季最高,冬季最低. PM2.5酸度在夏、秋季高于冬、春季,且夏、秋季PM2.5样品全部呈酸性,冬、春季PM2.5样品一部分呈酸性,一部分呈碱性.夏季SOR值和NOR值分别为冬季的4.8倍和3倍,表明夏季SO2和NO2更易转化生成SO42-和NO3-.PM2.5中SO42-、NO3-和NH4+主要以(NH4)2SO4、NH4NO3的形式共存于气溶胶体系中.     

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.