污灌区稻田汞污染特征及健康风险评价

选择天津北排污河灌区作为研究区域,调查了土壤和水稻总汞和甲基汞的含量及分布特征,评估污灌区稻米食用汞暴露风险,并对污灌区土壤-稻米甲基汞的影响因素进行了初步分析.结果表明,1.调查的29个污灌区稻田,土壤总汞含量为(367.04 ± 129.36) μg/kg,显著高于区域土壤Hg背景值73 μg/kg,甲基汞含量为(0.87 ± 0.77) μg/kg;水稻各部位总汞含量依次为稻叶 > 稻根 > 稻茎 > 稻米,稻米总汞含量为(12.80 ± 5.14) μg/kg,甲基汞含量依次为稻米 > 稻根 > 稻茎 > 稻叶,稻米对甲基汞具有很强的富集能力,甲基汞含量为(2.09 ± 1.20) μg/kg,甲基化率均值超过10%.污灌区稻米总汞每周摄入量为0.068~1.25μg/(kg·bw),甲基汞每周摄入量为0.0095~0.49μg/(kg·bw),污灌区稻米总汞及甲基汞暴露对居民健康风险总体仍在安全阈值内,但个别汞污染较严重地块甲基汞暴露风险值得高度关注.土壤甲基汞含量仅与土壤总汞含量及黏粒含量的相关性达到显著性水平,稻米甲基汞含量与土壤总汞含量、土壤甲基汞含量、稻米总汞含量及黏粒含量的相关性达到显著性水平.     

贵州草海底栖动物汞分布及其对沉积物汞的响应特征

以国家自然保护区贵州草海湿地为研究对象,系统采集草海湖中深水区和湖边浅水区生长的底栖动物,测定其总汞和甲基汞,探讨底栖动物汞和甲基汞分布特征及其对沉积物汞的响应特征,并评估了其面临的汞污染风险.结果表明,底栖动物总汞含量范围为0.51~46.55 ng·g~(-1)(均值7.82 ng·g~(-1)),甲基汞含量范围为0.04~27.71 ng·g~(-1)(均值4.31 ng·g~(-1)),低于其他自然保护区报道的底栖动物的汞含量.对比发现,夏季底栖动物总汞和甲基汞含量均高于其他季节;湖边点底栖动物总汞和甲基汞含量均高于湖中点同种类底栖动物汞含量,这与沉积物中甲基汞含量的空间分布特征一致,却与沉积物总汞含量空间分布特征相反,且中华圆田螺甲基汞含量与沉积物甲基汞含量呈显著相关(r=0.52,P0.05),表明湖边浅水区沉积物汞的甲基化程度、生物可利用性都明显高于湖中深水区.湖中湖边沉积物有机质的含量差异以及湖边沉积物存在干湿交替可能导致了这种明显的差异.底栖动物对水体或沉积物总汞和甲基汞的富集系数均较高,这些高富集系数足以引起对草海湿地水生食物链中汞污染风险的重视.     

三峡库区消落带沉积物-水界面汞的扩散特征

通过模拟实验研究了三峡库区消落带沉积物-水界面汞及甲基汞的扩散。结果表明,三峡库区消落带浅水沉积物中的甲基汞占总汞的比例为0.41%±0.29%,深水沉积物中的甲基汞占总汞的比例为0.74%±0.52%。深水沉积物比浅水沉积物具有更高的甲基汞产率。随着淹水时间的延长,沉积物中甲基汞的含量呈指数增长。沉积物中的甲基汞生成动力学方程符合零级反应方程。沉积物中无机汞的扩散以Freundlich修正式拟合效果最好,相对好氧的环境更有利于沉积物中无机汞的释放。相应地,甲基汞的扩散以抛物线扩散方程拟合效果最好,黑暗厌氧的环境更有利于沉积物中甲基汞的释放。三峡库区消落带沉积物-水界面无机汞的扩散通量为154.65±47.12~160.23±56.19 ng/(m~2·d),甲基汞扩散通量为7.61±3.39~7.79±4.56 ng/(m~2·d)。随着淹水时间的增加,孔隙水无机汞及甲基汞向上覆水体的释放通量均表现为先增加后减小的趋势。沉积物中的甲基汞对上覆水体甲基汞含量的贡献率为1.5%~14.3%,释放量为0.28~0.85 kg/a。而沉积物中的汞对上覆水体汞含量的贡献率为0.20%~1.70%,释放量为5.64~17.55 kg/a。     

三峡库区消落带甲基汞变化特征的模拟

为探寻三峡水库消落带在干湿交替条件下甲基汞的变化规律,以库区典型消落带土壤为研究对象,采用模拟试验,研究了干湿交替条件下消落带土壤和水体甲基汞含量和动态变化趋势及其影响因素.结果表明:淹水过程会促进土壤无机汞向有机汞转化,土壤甲基汞含量在淹水和落干过程均呈现先增加后减少的趋势;随着干湿交替周期的增加,土壤甲基汞含量增加,第二次淹水后土壤甲基汞平均含量比第一次淹水增加了22.13%,第二次落干后土壤甲基汞平均含量比第一次落干增加了58.17%.第二次淹水过程土壤甲基汞占总汞的比例明显高于第一次淹水,土壤中汞的甲基化主要与干湿交替循环有关.土壤淹水后会迅速向水体释放甲基汞,水体中甲基汞含量明显增加,两次淹水过程增幅分别为119.42%和334.72%,水体甲基汞和土壤甲基汞之间无显著相关.干湿交替环境土壤甲基汞含量主要受pH值、有机质含量、Eh和土壤含水量等因素的影响;水体中甲基汞含量的影响因素则主要有水体pH值、DO、DOM、水温等.     

海河干流水产品汞污染特征及摄入风险评估

通过现场实地采样和实验测定分析了天津市海河干流水产品中汞含量水平及食用人群的暴露风险.结果表明,海河淡水水产品中甲基汞和总汞的含量(以湿重计)分别为42.51 ng·g~(-1)和77.31 ng·g~(-1),甲基汞是水生生物中汞的最主要存在形式,且与鱼体中总汞含量水平显著相关.鱼体在不同器官中和不同养殖方式下的汞含量水平差异显著.海河淡水鱼类和底栖动物的甲基汞富集系数(BCF)分别为1.00×105m L·g~(-1)和4.23×104m L·g~(-1),与总汞相比,甲基汞具有更强的生物富集特性.海河淡水生物生物链中的甲基汞和总汞营养级放大系数分别为1.38和1.36.水产品中的甲基汞和总汞含量最大允许含量均低于我国国家标准限定值,但同时应该注意,以海河淡水野生鱼类为食的儿童,汞摄入风险相对较高,其总汞和甲基汞摄入量分别达到154.07 ng·(kg·d)~(-1)和81.11 ng·(kg·d)~(-1).     

典型钢铁行业汞排放特征及质量平衡

以重庆市某钢铁企业各工艺单元的进出物料为研究对象,分析样品总汞及各物料中汞的输入输出量,初步探讨钢铁生产各工序汞的排放特性及其质量平衡.结果发现,各工艺输入物料汞含量为2.93~159.11μg·kg~(-1),其中,高炉所用块矿汞含量最高,其次为烧结以及高炉用煤.输出物料中汞含量为3.09~18.13μg·kg~(-1),除尘灰汞含量最高,其次为转炉渣.该钢铁企业自备焦化厂汞输入量和输出量分别为1 346.74 g·d~(-1)±36.95 g·d~(-1)和177.42 g·d~(-1)±13.73 g·d~(-1),焦化工序中的汞主要来源于焦煤的燃烧.钢铁生产过程中烧结工序汞输入量最高,为1 075.27 g·d~(-1)±60.89 g·d~(~(-1)),占钢铁生产总汞带入量的68.06%,其来源主要是铁矿粉.固体输出物料中,烧结工序输出汞量为14.15 g·d~(-1)±0.38 g·d~(-1),占总固体输出量22.61%.经估算,该钢铁企业2013年汞排放量约为553.83 kg,汞排放因子为0.092 g·t~(-1)钢产量.为控制汞排放,钢铁企业应结合生产实际,进一步降低焦化以及烧结工序能耗水平,或提高原料质量,减少汞的输入.     

汞在小浪底水库的赋存形态及其时空变化

为了解小浪底水库汞的赋存状况,采用冷原子荧光光谱法测定了小浪底水库水体、表层沉积物、沉积物间隙水以及鱼类肌肉样品中的总汞,采用乙基化衍生-气相色谱-原子荧光法测定了上述样品中的甲基汞,进而分析了小浪底水库鱼体中汞的富集状况.结果表明,小浪底水库水体中丰、枯水期总汞浓度分别为0.71~1.42 ng·L-1和0.90~2.49 ng·L-1,均符合国家地表水环境质量标准(GB 3838-2002)一类水汞浓度标准限值,水样中未检出甲基汞.丰、枯水期沉积物中总汞浓度分别为51.74~90.42 ng·g-1和95.66~172.52 ng·g-1,甲基汞浓度分别为0.09~0.26 ng·g-1和0.18~0.39 ng·g-1,甲基汞浓度较低,这可能与水体底层溶解氧浓度较高以及沉积物中有机碳浓度较低有关.丰、枯水期沉积物间隙水总汞浓度分别为4.27~9.49 ng·L-1和5.46~41.04 ng·L-1,甲基汞浓度分别为0.09~0.99 ng·L-1和0.07~1.01 ng·L-1,间隙水中总汞和甲基汞浓度明显高于上覆水体,与水体间存在汞浓度梯度,可能存在从沉积物间隙水向水体中的扩散.鱼体肌肉总汞浓度在43.47~304.98 ng·g-1之间,甲基汞浓度为10.77~265.23 ng·g-1,甲基汞低于食品安全国家标准规定的污染物限量(GB 2762-2012)(非肉食性鱼500 ng·g-1和肉食性鱼1 000 ng·g-1).水库鱼体总汞的生物富集系数分别为鳙鱼1.3×105,梭鱼9.3×104,鲫鱼4.7×104,白条5.0×104,黄颡鱼1.7×105,弓鱼3.9×104.     

三峡水库消落带植物汞的分布特征

以三峡库区重庆段忠县石宝寨、涪陵珍溪和开县汉丰湖消落带为主要研究地点,调查并采集了植物样品,分析样品总汞和甲基汞,探讨三峡水库消落带植物汞的分布特征及植物汞库存量.结果表明,调查区域消落带植物总汞含量在(1.62±0.57)~(49.42±3.93)μg·kg-1范围,植物各部位总汞的含量呈根叶茎的趋势分布;植物甲基汞含量在(15.27±7.09)~(1 974.67±946.10)ng·kg-1范围,植物根部甲基汞含量高于茎和叶.同类植物中,开县汉丰湖消落带植物总汞和甲基汞含量均较忠县石宝寨、涪陵珍溪镇消落带植物略高;不同高程植物总汞及甲基汞储存量存在差异,145~150、150~160、160~170和170~175 m高程的植物总汞储存量分别为145.3、166.4、124.3和88.2 mg·hm-2,甲基汞储存量分别为1.9、2.7、3.6和3.2 mg·hm-2.消落带优势种植物对总汞的富集能力相对较弱(BAF1),而对甲基汞的富集能力相对较强(BAF1).     

三峡库区消落带甲基汞变化特征的模拟

为探寻三峡水库消落带在干湿交替条件下甲基汞的变化规律,以库区典型消落带土壤为研究对象,采用模拟试验,研究了干湿交替条件下消落带土壤和水体甲基汞含量和动态变化趋势及其影响因素.结果表明:淹水过程会促进土壤无机汞向有机汞转化,土壤甲基汞含量在淹水和落干过程均呈现先增加后减少的趋势;随着干湿交替周期的增加,土壤甲基汞含量增加,第二次淹水后土壤甲基汞平均含量比第一次淹水增加了22.13%,第二次落干后土壤甲基汞平均含量比第一次落干增加了58.17%.第二次淹水过程土壤甲基汞占总汞的比例明显高于第一次淹水,土壤中汞的甲基化主要与干湿交替循环有关.土壤淹水后会迅速向水体释放甲基汞,水体中甲基汞含量明显增加,两次淹水过程增幅分别为119.42%和334.72%,水体甲基汞和土壤甲基汞之间无显著相关.干湿交替环境土壤甲基汞含量主要受pH值、有机质含量、Eh和土壤含水量等因素的影响;水体中甲基汞含量的影响因素则主要有水体pH值、DO、DOM、水温等.     

纳米TiO2对底泥中汞释放及活化的影响

为了研究纳米TiO2对底泥汞的释放及活化的影响,采用模拟淹水实验,分析纳米TiO2对底泥和上覆水中总汞和甲基汞浓度的影响,并结合底泥中各形态汞的变化情况探讨纳米TiO2对汞的迁移转化的影响.结果表明,纳米TiO2可促进底泥中汞的释放,导致更多的汞释放到水中,与对照相比,4g·kg-1纳米TiO2导致上覆水中总汞浓度最高时上升91.32%,最终土壤汞的释放量增加约10%,主要原因是纳米TiO2可促进氧化态汞的溶解,这可能会提高水体汞污染的风险.此外,在本实验条件下,短期内纳米TiO2可能降低了底泥甲基汞的形成和释放,但长期淹水后没有明显的影响.总体来看,纳米TiO2对底泥汞释放和转化的影响随浓度升高而增大.因此,随着底泥或土壤中纳米TiO2含量的升高,其对汞的地球化学循环过程的影响可能加剧.     

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.     

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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Organochlorine pesticides in soils under different land usage in the Taihu Lake region, China

A field study was conducted in the Taihu Lake region, China in 2004 to reveal the organochlorine pesticide concentrations in soils after the ban of these substances in the year 1983. Thirteen organochlorine pesticides (OCPs) were analyzed in soils from paddy field, tree land and fallow land. Total organochlorine pesticide residues were higher in agricultural soils than in uncultivated fallow land soils. Among all the pesticides, ΣDDX (DDD, DDE and DDT) had the highest concentration for all the soil samples, ranging from 3.10 ng/g to 166.55 ng/g with a mean value of 57.04 ng/g and followed by ΣHCH, ranging from 0.73 ng/g to 60.97 ng/g with a mean value of 24.06 ng/g. Dieldrin, endrin, HCB and α-endosulfan were also found in soils with less than 15 ng/g. Ratios of p,p'-(DDD DDE)/DDT in soils under three land usages were: paddy field ＞ tree land ＞ fallow land, indicating that land usage inlfuenced the degradation of DDT in soils. Ratios of p,p'-(DDD DDE)/DDT ＞1, showing aged residues of DDTs in soils of the Taihu Lake region. The results were discussed with data from a former study that showed very low actual concentrations of HCH and DDT in soils in the Taihu Lake region, but according to the chemical half-lives and their concentrations in soils in 1980s, the concentration of DDT in soils seemed to be underestimated. In any case our data show that the ban on the use of HCH and DDT resulted in a tremendous reduction of these pesticide residues in soils, but there are still high amounts of pesticide residues in soils, which need more remediation processes.     

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.