贵州汞矿矿区不同位置土壤中总汞和甲基汞污染特征的研究

为了深入理解汞矿矿区土壤中总汞和甲基汞的污染特征,应用AAS、GC-CVAFS方法,分别对贵州万山、务川和滥木厂汞矿矿区不同位置土壤以及对照区土壤中的总汞(THg)和甲基汞(MeHg)进行了测定.结果表明,万山汞矿区土壤THg和MeHg含量范围分别为1.1～790 mg·kg^-1和0.19～15μg·kg^-1,务川汞矿区土壤THg和MeHg含量范围分别为0.33～317mg·kg^-1和0.41～20μg·kg^-1,滥木厂汞矿区土壤THg和MeHg含量范围分别为0.41～610 mg·kg^-1和0.70～8.8μg·kg^-1.对照区土壤汞含量明显低于矿区土壤,其THg和MeHg含量范围分别为0.14～1.2 mg·kg^-1和0.09～0.23μg·kg^-1;对照区土壤THg含量接近或稍高于全球背景土壤THg含量0.01～0.5 mg·kg^-1.研究表明,汞矿区稻田土壤具有较强的汞甲基化能力,其MeHg含量明显高于菜地和旱田土壤;万山汞矿区土壤汞污染程度明显高于滥木厂和务川汞矿区土壤汞污染.     

古水稻土中多环芳烃的分布特征及其来源判定

测定了马家浜文化(距今约6 000a)遗址2个剖面表层土壤、古代水稻土和古代旱地土壤、以及底层土壤中15种多环芳烃的含量,并对其可能来源进行了判定.结果表明,表层土壤中PAHs的含量分别为202.9μg·kg^-1和207.7μg·kg^-1,主要来源于大气沉降;古水稻土中PAHs含量明显降低,仅为56.0μg·kg^-1,但高于古旱地土壤及底层土壤。古旱地土壤及底层土壤PAHs含量在32.0～36.9μg·kg^-1.古水稻土中,2环和3环所占比例较大,达63%,萘和菲含量最高,而4环以上的多环芳烃含量较低.Phe/Ant和BaA/Chr比值和有机质¹³C-NMR图谱显示,古水稻土中的多环芳烃主要来源于水稻秸秆的焚烧,同时还原条件下的生物合成可能是其另一个重要来源.     

利用KOC*值判别杭州市地面水中多环芳烃污染来源

测定了2002年12月杭州市钱塘江和运河杭州段地面水、底泥和土壤中10种多环芳烃的含量,计算了底泥和土壤中PAHs富集倍数K和有机碳标化表观分配系数K_OC^*.结果表明,地面水中PAHs总浓度范围为1.104～9.663μg·L^-1,底泥中为132.7～7343μg·kg^-1(干重),土壤为59.71～219.5μg·kg^-1(干重),污染较为严重.钱塘江底泥PAHs的K值随水流而降低,而运河杭州段则增大.钱塘江底泥和土壤的K_OC^*比值接近1,PAHs主要来自土壤淋溶输入,污染历史不长.运河在城区(如拱宸桥和卖鱼桥)的KK_OC^*比值远大于1,地面径流输入少,而工业排放输入多,且污染历史较长.     

贵州万山汞矿区汞的环境污染及对生态系统的影响

通过对贵州万山汞矿地区环境样品(水、土壤、植物、农作物和动物)的系统研究,发现该地区的环境汞污染以土壤、大气污染为主,水体基本处于正常范围.土壤汞含量为24.31～347.52mg·kg^-1,比全国土壤平均值高出2～3个数量级;水中汞含量除了冶炼厂荷花池中含量较高外,其它水体为0.10～0.68ng·mL^-1.由于矿山长期的开采和冶炼,整个环境的汞污染严重,当地的植被、农作物、动物中存在明显的汞蓄积,各种植物不同部位的汞含量为0.47～331.4mg·kg^-1;苔藓可以高度富集汞.     

珠江三角洲4种代表性土壤/沉积物中自由态与结合态有机氯农药的含量与分布特征

有机氯农药在土壤/沉积物中主要以自由态和结合态存在.本研究选取珠江三角洲地区4种代表不同沉积环境的典型土壤/沉积物样品,先采用碱萃取、盐酸/氢氟酸去矿物等方法对样品进行了组分分离,再采用有机溶剂萃取法对不同组分中自由态和结合态有机氯农药进行了系统分析.结果显示,4种土壤/沉积物总有机氯农药含量为20.96～134.22 μg·kg^-1,其中HCHs总含量为5.66～22.87　μg·kg^-1,DDTs总含量为1.51～11.70　μg·kg^-1,β-HCH、七氯、艾氏剂、异狄氏剂、硫丹硫酸盐和甲氧滴滴涕等6种农药为主要成分,占总有机氯农药的53.56%～77.26%.自由态有机氯农药含量为8.46～88.45　μg·kg^-1,占总有机氯农药的40.37%～65.90%.结合态有机氯农药含量为11.46～45.77　μg·kg^-1,占总有机氯农药的34.10%～59.63%,主要存在于土壤/沉积物的腐殖酸和胡敏素组分,反映了环境中结合态有机氯农药的大量存在.自由态DDT和HCH类有机氯农药的分布情况表明,4种样品均没有新鲜HCH类农药输入而部分样品仍有新鲜DDT类农药输入.结合态有机氯农药在腐殖酸和胡敏素间的分布与有机质碳含量相关,占总有机碳57.71%～80.55%的胡敏素结合了94.78%～97.48%的结合态有机氯农药.风险评价结果表明,部分游离态有机氯农药如γ-HCH、艾氏剂、异狄氏剂、DDT类农药可能存在一定的生态风险.由于单个化合物的总量要比自由态高出约1～30倍,同时结合态农药在一定条件下有释放到环境的可能,因此有机氯农药的环境风险评价和环境标准建立均需考虑结合态有机氯农药.     

三元土壤调理剂对田间水稻镉砷累积转运的影响

通过镉砷复合污染稻田的土壤调理剂原位治理,研究了三元土壤调理剂QFJ（羟基磷灰石+沸石+改性秸秆炭）对稻田土壤基本理化性质和水稻各部位镉砷累积转运的影响.结果表明,在土壤Cd总量3.58 mg·kg^-1,As总量124.79 mg·kg^-1污染程度下,施用QFJ后,水稻根际土壤pH值、阳离子交换量及有机质含量有增大的趋势;土壤交换态Cd和As含量可分别从0.37 mg·kg^-1、0.07 mg·kg^-1下降到0.12 mg·kg^-1、0.04 mg·kg^-1.QFJ的施用,可有效降低水稻各部位中Cd和As含量,在9.00 t·hm^-2施用量水平,可将糙米中Cd含量从0.46 mg·kg^-1下降到0.18 mg·kg^-1,无机As含量从0.25 mg·kg^-1降低到0.16 mg·kg^-1,同时低于国家食品污染物限量标准0.2 mg·kg^-1的要求,实现水稻安全生产.施用QFJ减少了水稻根系对Cd和As的富集,降低了水稻植株将Cd从地下部转运到地上部的能力,降低了根系转运Cd的能力以及茎叶、谷壳转运As的能力.     

来利山锡尾矿区优势植物调查与生态修复潜力分析

为了筛选用于锡矿区生态恢复的优势植物,对云南来利山锡尾矿废弃地进行实地调查,记录并采集了15种优势植物样本及相应根际土壤.测定其铜（Cu）、镉（Cd）、砷（As）、镍（Ni）、铅（Pb）和锡（Sn）含量,计算这15种植物对6种重金属的转移和富集系数,同时测定分析了植物根系菌根侵染率及根际土壤的化学性质,综合评估本土植物的应用潜力.结果表明,废弃地土壤pH均值为3.13,呈强酸性;有机质、全氮、全磷、全钾、碱解氮和有效磷均值分别为6.07 g·kg^-1、5.74 g·kg^-1、0.62 g·kg^-1、8.66 g·kg^-1、30.84 mg·kg^-1和2.08 mg·kg^-1,养分较贫瘠;土壤Cu、Cd、Ni、Pb、As和Sn含量均值分别为347.40、1.02、1.34、168.47、25.81和2299.02 mg·kg^-1,其中Cd的含量已达到三级污染警戒值,Cu和Pb含量大且空间分布差异大,呈现Cu、Pb和Cd复合污染的风险.此外,木犀榄（Olea europaea L.）和柃木（Eurya japonica Thunb.）根系的菌根侵染率相对较高,桤木（Alnus cremastogyne Burk.）、小丝琴竹［Bambusa multiplex （Lour.） Raeusch.ex Schult.‘Alphonse-Kar’ R.A.Young］、灯心草（Juncus effusus L.）和莎草（Cyperus rotundus L.）等对重金属有较强的吸收和转运能力,其余植物也适应锡尾矿废弃地的生长环境,具有修复该矿区的潜在价值.     

硝基苯类化合物在黄河小浪底至高村河段水体中的分布特征

研究了黄河中下游小浪底-花园口-高村河段表层水、悬浮颗粒物和沉积物中10种硝基苯类有机污染物的含量.结果表明,水样中检测到8种硝基苯类有机污染物,其中孟州一干渠中硝基苯浓度最高,为8.426 8μg·L^-1,但都没有超过国家标准(GB3838—2002).伊洛河的悬浮颗粒物中硝基苯类有机物的总浓度达164.382μg·kg^-1.洛阳石化沉积物中硝基苯类有机物的总浓度最高,为14.718μg·kg^-1.在三相(表层水、悬浮颗粒物和沉积物)中,硝基苯的含量最高.硝基苯类有机物在水、沉积物和悬浮颗粒物中的大体分布趋势为悬浮颗粒物>沉积物>表层水,沉积物中的污染物有再次释放到水体中的趋势.     

海河干流及河口地区土壤中有机氯农药的分布特征

以海河干流沿岸及海河河口周边地区为研究区域,采集了31个表层土壤样品,利用加速溶剂萃取（ASE）技术,使用气相色谱-电子捕获检测器（GC-ECD）分析方法测定了样品中的六六六（HCHs）和滴滴涕（DDTs）的含量.结果显示,海河河口地区土壤中HCHs和DDTs的含量范围分别为n.d.～1 728 μg·kg^-1（平均含量为93.9 μg·kg^-1）和n.d.～288 μg·kg^-1（平均含量为34.4 μg·kg^-1）.其中HCHs占优势,约占有机氯农药（OCPs）总残留量的72%.从海河干流到河口地区,OCPs的含量分布呈非均一性,受污染点源的分布影响较大,农药化工企业分布的区域土壤中的有机氯农药含量明显高于其它区域,海河干流区域相对高于河口地区.土壤中有机氯农药的成分分析结果表明,该地区土壤中除个别采样点OCPs仍有新的污染源输入外,大部分点位土壤中的OCPs主要来自于工业点源的历史输入和农业面源即有机氯农药的历史施用.与国内外其他地区土壤相比,该地区土壤中OCPs污染处于较高水平.     

亚热带典型景观单元土壤有机碳含量和密度特征

以我国亚热带四类典型景观单元表层土壤为对象,对比分析了土壤有机碳（SOC）含量和密度特征.结果表明,四类景观单元SOC含量加权平均值差异明显,以平原湖区加权平均值最高（25.10 g·kg^-1）,其次为喀斯特低山（20.84 g·kg^-1）和红壤低山（17.75 g·kg^-1）,红壤丘陵平均值最低（12.07 g·kg^-1）.四类景观单元SOC含量变异系数在24.06%～43.76%之间,均属于中等程度变异.平原湖区景观SOC含量主要分布区高于20 g·kg^-1,其它三类景观单元主要分布区则相反.四类景观单元SOC密度加权平均值大小顺序与SOC含量高低极为一致,其顺序为平原湖区（6.12 kg·m^-2）> 喀斯特低山（4.30 kg·m^-2）> 红壤低山（4.25 kg·m^-2）> 红壤丘陵（3.04 kg·m^-2）.研究结果揭示成土母质、耕作强度、地形差异和土地利用方式比例是SOC含量景观变异的主要原因,亚热带地区典型景观单元土壤可能是我国重要的碳库.     

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.     

基于综合水质标识指数和对应分析法的校园河道水质评价

以三峡大学的校园河道求索溪为研究对象,利用综合水质标识指数法确定求索溪水质类别,分析其水质时空变化规律,并利用对应分析法得出求索溪中不同监测点的主要污染因子.研究结果表明:求索溪整体的综合水质标识指数为7.423,整体水质为劣V类(地表水环境质量标准GB 3838-2002)且黑臭.从时间变化来看,求索溪4月份的水质最差,5月份次之,4、5月份所有监测点的水质都劣于V类且黑臭;8月份水质最好,水质为Ⅳ类;从空间分布来看,8个监测点综合水质标识指数均超过6.0,水质为劣V类,其中6号监测点的水质相对最好,监测点3号的水质相对最差;对应分析法得出求索溪的整体水体污染程度受总氮因子的影响最大,其次为总磷.该研究拟为求索溪及类似校园河道的水环境治理研究提供基础依据和参考.     

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.