珊瑚钨锡矿硅质尾矿中Cd、As、Zn、F富集迁移及环境污染

硅质尾矿在释放中性矿山废水(NMD)时所伴生的多元素复合污染问题值得重视。本文以桂东北珊瑚矿尾矿作为研究对象,通过分析该尾矿的组构、元素富集及迁移特性,筛选出主要污染元素,并探讨尾矿胶结层对元素富集迁移的影响。结果表明:(1)该尾矿中Cd、As、Zn及F富集程度较高、可交换态含量(易迁移释放量)较大,是主要的污染元素,而Cu、Pb、Tl产生污染的可能性较小;(2)胶结层对重金属具有再富集作用,但其对可交换态Cd、As(Tl)再富集明显,而对可交换态Cu、Pb、Zn再富集则不明显。胶结层中次生伊利石、石膏等胶结物趋向于吸附富集活性可交换态Cd、As。这表明该尾矿可能迁移释放出含Cd、As浓度较高的NMD。研究表明,硅质尾矿风化释出NMD的同时,可能伴生Cd、As、Zn等重金属以及F的复合污染。     

海南岛西部非农用地土壤中的稀土元素地球化学特征

对海南岛西部发育典型的12个非农业土壤剖面REE的组成特征及其纵向变化规律进行研究发现,区内非农业土壤剖面不同层位之间的稀土元素具有一定的继承性,风化成土的基岩奠定了土壤中稀土元素的初始含量及土壤中呈现的LREE富集与Eu亏损的特点,而成土过程中稀土元素分异作用则进一步加剧土壤中LREE的富集和Eu亏损,土壤剖面浅部的氧化和水解作用致使Ce在浅层土壤中的富集,并导致由剖面深部至浅部,Ce呈现出正异常增大之趋势。区内稀土元素的赋存状态与稀土元素性质及其所处的土壤地球化学环境有密切联系,同一层中不同形态稀土元素含量总体上表现为残渣态>Fe-Mn结合态>有机态>可交换态(含水溶态)>碳酸盐态,而往土壤深部,残渣态所占比例逐步增大,Fe-Mn结合态、有机态与可交换态(含水溶态)所占比例逐步降低。     

苏南典型工农业交错区土壤铅富集特征及源解析——基于PCA-PMF方法

为阐明长江三角洲典型工农业交错区土壤中Pb富集特征以及污染源贡献,以常熟地区典型水稻土为研究对象,分析了该地区表层土壤和土壤剖面中Pb、Cu、Zn、Cd以及主量元素等的含量及Pb形态分布.结果显示,研究区表层土壤发生了显著的Pb富集,土壤Pb平均含量超出了当地水稻土Pb背景值近一倍,地学统计分析反映表层土壤Pb处于轻度污染水平.外源铅在土壤中主要以铁锰氧化态和残渣态存在.相对于表层土壤,深层土壤(20~60cm)具有较高的碳酸盐结合态Pb占比和残渣态Pb占比,以及较低的腐殖酸结合态Pb占比和铁锰氧化态Pb占比.主成分分析法(PCA)和正定矩阵因子分析法(PMF)分析结果均显示表层土壤Pb主要来自4种污染源:约42.8%继承于岩石风化的自然产物、15.5%来自于含Pb汽油等化石燃料燃烧排放(通过大气沉降形式输送到土壤等方式)、21.6%来自于电镀等有色金属冶炼的工业活动和20.1%的可能为地表其它混合源.PCA-PMF源解析方法所得结果能较好地解析土壤中重金属来源.     

贵州从江县大融砖厂新元古界浅变质岩现代风化壳剖面中微量元素分布特征与相关性分析

前人对贵州第四纪碳酸盐岩风化壳红粘土已经进行大量的地球化学研究,但贵州东部大片的新元古界浅变质岩分布区第四纪风化壳地球化学至今尚未被研究。作者以从江大融砖厂新元古界浅变质岩风化壳为研究对象,对该系统的微量元素分布状况进行研究,发现风化壳剖面具有与碳酸盐岩风化红粘土类似的特征,即上部发育褐铁矿层,底部富集Mn、Co、Mo、Cd、Cs、Ba、Tl、Pb等元素,pH值的增加对多种微量元素沉淀富集起至关重要的作用。母岩微量元素含量背景值低及岩石节理发育可能是研究剖面微量元素含量整体表现为亏损特征的主要原因。利用SPSS软件对大融砖厂风化剖面土壤中各种微量元素进行R型聚类分析,根据其相关性大小划分为四类。在聚类过程中,突出地表现出一条原则,即为表生环境中地球化学活动性相似的元素往往归为一类。     

碳酸盐岩风化形成的土壤剖面上氟的分布及影响因素

选择贵州省新蒲、平坝和罗吏地区的3个碳酸盐岩原地就位风化成土剖面为研究对象,通过对剖面土壤中氟形态、矿物组成、主量地球化学元素和理化性质等的测定实验,讨论了土壤剖面中氟的赋存形态、分布特征及与影响机制。结果表明:罗吏、平坝和新蒲3个剖面残渣态氟含量分别介于896~1 667 mg/kg、897~2 827 mg/kg和1 386~2 852 mg/kg之间,均占各剖面总氟含量的98%以上,3个碳酸盐岩风化形成的土壤剖面中氟主要为残渣结合态;除罗吏剖面外,其它几个剖面吸附性强的无定形铁铝氧化物、结晶态铁铝氧化物与氟含量皆无显著中度以上正相关,有机碳甚至在三个剖面中和氟显著负相关,表明吸附作用对氟富集的贡献有限;次生粘土矿物是氟的主要载体,且主要以残渣态的形式存在于粘土矿物的晶格中,但氟含量与粘粒含量相关性并不显著;采用SPSS软件对氟与各种理化性质进行多元逐步回归分析,回归方程表明镁对氟富集具有重要作用。     

海南土壤中稀土元素含量及分布特征

对海南四种不同母质来源的土壤样品中的稀土元素含量及分布特征进行了研究,结果表明:除砂岩母质外,海南省其它母质的土壤中稀土元素总量都高于全国土壤、世界土壤和地壳中稀土元素的平均含量;各母质类型土壤中Eu亏损明显。花岗岩上发育的土壤中稀土元素含量最高,总量达419.42mg/kg。砂岩和花岗岩上发育的土壤中LREE相对富集。LREE和HREE在不同母质来源的土壤剖面中的富集、迁移等地球化学行为不完全相同,这说明:土壤发育过程中,稀土元素的含量和分布不仅仅和成土过程、气候及其它地球化学因素有关,而且与母质也有重要的关系,母质往往制约着风化成土过程中稀土元素的地球化学行为。     

某硫铁矿区废水池沉积物剖面中重金属化学形态分布和环境污染评价

矿山开采是造成环境重金属污染的重要途径,揭示重金属在污染区的富集特征及潜在生态效应对重金属污染防治有重要意义。以粤西某硫铁矿区废水池沉积物剖面为研究对象,采用电感耦合等离子质谱仪和分级提取法分析底泥中Tl、Cr、Ni、Co与Cd总量和各化学形态的分布特征及生态风险,并结合矿物组成分析阐明富集及迁移机制。结果表明：底泥中Cd含量远超我国土壤背景值,且Cd主要以弱酸可交换态的形式存在;Tl含量同样远超我国土壤背景值,以残余态的形式为主;Cr和Ni含量均略高于我国土壤背景值,也主要以残余态的形式存在;Co含量小于我国土壤环境背景值,具有较大的弱酸可交换态比例。综合富集因子法和风险评价指数分析,底泥中Cd具有很强的环境潜在危害性;Tl具有强的环境潜在危害性;Cr和Ni具有中等程度的环境潜在危害性;Co没有环境潜在的危害。硫铁矿区废水池底泥是重金属（Cd、Tl、Ni和Cr）重要的汇和潜在二次污染源。硫铁矿区废水池底泥中Cd和Tl高度富集,Ni和Cr具有低—中等程度的富集,废水池底泥的污染防治与资源回收同样值得思考关注。     

水源地周边土壤重金属分布特征及潜在风险-以深圳市为例

以深圳市水源地周边三种不同类型土壤(赤红壤､红壤､水稻田土)为研究对象,选择具有较高环境含量且毒性较强的Zn､Pb､As为目标,探究其在三种土壤剖面淋溶层､淀积层和母质层(A、B和C层)中的分布特征及赋存形态,同时分析重金属含量､赋存形态与土壤理化性质的相关性,并利用潜在生态危害指数法和潜在迁移指数法从重金属全量和赋存形态两个角度对土壤重金属的生态风险水平进行评估.结果表明:土壤重金属Zn､Pb､As在三类土壤各层中含量较高,但均低于当地土壤环境质量背景值,重金属含量受当地土壤成岩母质影响较大.形态分析表明三种重金属在三类土壤中均以残渣态为主,但红壤中可还原态Pb含量较高,在低pH时易转化为弱酸可溶态,而后释放并迁移.相关性分析表明Zn､Pb的全量与有机质含量呈极显著正相关,可还原态Zn与pH呈显著正相关,Pb和As的弱酸可溶态与可还原态显著正相关,黏粒和粉粒含量对Pb和As的形态分布造成不同程度的影响.三种重金属潜在生态危害级别均为轻微,对水源地安全潜在生态风险影响较小;重金属迁移能力大小在不同土类中依次为红壤土>赤红壤>水稻田土,元素本身迁移能力强弱依次为Zn>As>Pb;赤红壤和水稻田土A层Zn迁移能力最强,B层As最强,C层Zn､Pb､As均较弱;红壤中A层迁移能力Zn最强,B层Zn､Pb､As均较强,C层Zn､Pb､As均较弱.     

海南东寨港红树林湿地表层沉积物中汞的分布特征及富集因素分析

以海南东寨港红树林湿地为研究区,采集了36个表层沉积物样品,综合分析了沉积物中主微量元素含量、碳氮比(C/N)等地球化学指标,探讨了研究区表层沉积物中汞(Hg)含量的分布特征、来源以及环境因子对表层沉积物中汞富集的影响。结果表明:(1)研究区表层沉积物中Hg含量的平均值为0.33μg/g,表现出潟湖口门和东寨港东岸周围表层沉积物中Hg含量高、东寨港南岸表层沉积物中Hg含量低的特征;(2)表层沉积物的物源为火成岩,表层沉积物中Hg含量与物源的化学风化程度呈负相关关系,且随着Na、Ca的风化流失,Hg也从表层沉积物中迁移释放;(3)表层沉积物中Hg含量与C/N比值具有相关关系,说明内源有机质增强了微生物活性,不利于表层沉积物中Hg的富集;(4)表层沉积物中可迁移释放的Hg,部分以吸附态赋存于沉积物中,影响吸附态Hg迁移行为的主要因素为pH值。     

典型黑色岩系地质高背景区土壤和农产品重金属富集特征与污染风险

土壤重金属污染是我国的重要环境问题,而区域地质高背景是土壤重金属富集的重要影响因素.黑色岩系风化土壤普遍存在重金属富集的现象,潜在生态环境风险较高,但目前农产品重金属富集的基础数据较缺乏,限制了黑色岩系地质高背景区的土地安全利用与农产品安全生产.对重庆典型黑色岩系地质高背景区313件土壤和289件主要农产品重金属的富集特征、污染风险和土壤重金属赋存形态进行研究.结果表明,相对于我国土壤环境背景值和重庆市表层土壤,研究区土壤Cd、 Cr、 Cu、 Zn和Se富集,Pb不富集;其中98.7%的土壤Cd含量超过风险筛选值,47.3%的土壤Cd含量超过风险管制值,Cd的污染水平和潜在生态风险最高,是研究区土壤的特征污染物.土壤Cd主要以离子交换态存在(40.6%),其次为残渣态(19.1%)和弱有机结合态(16.6%); Cr、 Cu、 Pb、 Se和Zn主要以残渣态存在,Se和Cu的有机结合态、 Pb的铁锰结合态也占较高比例;说明Cd的迁移能力和活性高于其它重金属.研究区主要农产品富集重金属的能力较弱,约18.7%的农产品Cd超标,超标倍数相对较低,重金属污染风险较低.研究可为黑色岩系地质高...     

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.