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.     

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。     

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。     

大气降水中离子化学特征及来源分析

通过研究2006-2010年上海市闸北区大气降水中离子的组成特征和变化,分析了离子可能的来源和酸雨的成因。结果表明,近年来酸雨污染有所改善,酸雨成因也有所改变。阴阳离子当量浓度之比小于1,可能缺少对某些低分子弱有机酸离子的监测。降水化学组份中浓度最高的四种离子分别是SO42-、NH4+、Ca2+和NO3-,SO42-浓度是NO3-的3.14倍,NH4+是Ca2+的2.76倍,降水的主要致酸物质是硫酸盐,主要中和物质是铵盐。大多数离子间有较好的相关性,NO3-和SO42-绝大部分来自人为源的贡献。降水中SO42-的致酸作用和Ca2+的中和作用逐渐下降,Cl-的致酸作用在逐渐增大。     

近2年上海市夏季降水地球化学特征研究

在连续监测采样分析基础上运用相关性分析、主成分分析、海盐示踪法和HYSPLIT模型,分析了上海市2008年和2009年夏季降水主要成分的化学特征、来源及酸性降水的成因.近2年夏季降水中,pH平均值分别为4.72和4.68,酸雨频率分别为53.30%和63.30%;离子浓度的大小顺序为SO24-NH 4+NO 3-Cl-Ca2+Na+Mg2+K+,其中SO42-、NH 4+、NO 3-等二次组分在降水中占有较高比例,三者之和分别占降水中离子总量的55.01%和65.97%,表明上海市大气环境中二次污染比较突出;SO42-/NO 3-的当量比分别为3.19和2.13,表明该市夏季酸性降水类型为硫酸和硝酸复合型;可溶性有机碳(DOC)含量变化范围为1.36～10.69 mg/L,平均含量为2.44 mg/L;NH 4+同SO24-(r=0.81)、NO 3-(r=0.58)的相关性分别大于Ca2+同SO24-(r=0.72)、NO 3-(r=0.57)的相关性,且NH 4+/Ca2+的当量比分别为1.31和2.49,说明NH 4+对夏季降水酸性的中和作用大于Ca2+;夏季降水中,SO42-、NH 4+、NO 3-、K+、Ca2+主要是陆源物质输入,Mg2+、Cl-两者海、陆源物质都有贡献且陆源贡献大于海源.后向轨迹分析表明上海市夏季酸性降水不仅与局地污染源有关,还与来自其西南方向的远距离污染物质输入有关.     

酸雨作用下中亚带森林冠层淋溶规律研究

2001年1月～2002年6月对韶山亚热带常绿阔叶林4个采样区进行了酸雨的监测,以监测数据为依据,分析研究了林内穿透水中主要离子的淋溶规律。结果表明:大气降水经过森林冠层后pH值明显升高,韶山亚热带常绿阔叶林对SO42-、NO3-、Mg2+、NH4+离子具有吸收作用,特别是NH4+和NO3-离子。SO42-、Ca2+和Mg2+离子的冠层淋溶百分率随降雨量的增加有明显减少的趋势。Ca2+、K+和Cl-随着pH的增加,其冠层淋溶百分率呈增加趋势。韶山地区在常年酸沉降作用下,森林冠层对酸性离子SO42-、NO3-的吸收作用最强。根据18个月离子浓度平均值来计算,韶山地区森林冠层离子的淋溶序列为:K+>Ca2+>Cl->Mg2+>SO42->NO3->NH4+>Na+。     

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.     

2007年北京夏季降水分段采样酸度和化学成分分析

为掌握降水酸度和污染性化学成分随降水持续时间的变化规律,对北京2007年夏季5次典型降水过程分时段采样,分别测定了pH值、电导率,并分析了其中水溶性大气污染成分SO42-、NO3-、NH4+等随时间的变化特征.结果表明,pH加权平均值在降水初期为5.70±0.73,为非酸雨;平缓期为4.35±0.56,呈酸雨特征.pH、电导率和各离子浓度随降水时间的持续而迅速下降,10~45 min后进入平缓期,各污染离子随之下降率为50%~90%.来自北京西北方向云团的降水(8月1日)pH值较高、污染物浓度较低,SO42-、NO3-和NH4+分别为65.4、23.9和117.3μeq/L;而来自偏南云团降水(8月6日)pH值较低、污染物浓度较高,SO42-、NO3-和NH4+浓度分别为310.8、95.7和249.8μeq/L.北京夏季二次粒子浓度升高,将使降水酸化加剧.     

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.     

徐州市大气降水现状分析

利用1990年－1993年大气降水监测数据，分析了徐州市大气降水污染现状及其化学成分。徐州市大气降水pH值范围为4．47－8．12，酸雨多出现在春、冬季。大气降水中主要离子为SO、NH、Ca2+。pH值和离子浓度随季节不同变化明显，冬季pH值较低，各离子浓度偏高；夏季pH值较高，各离子浓度偏低。大气降水体现了煤烟型污染的特点。     

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.     

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.     

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.     

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

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