改性壳聚糖CAD与微生物絮凝剂MBF8复配絮凝研究

采用水溶液自由基聚合反应,将丙烯酰胺(AM)、二甲基二烯丙基氯化铵(DMDAAC)接枝到壳聚糖分子上制成了阳离子改性壳聚糖(CAD).经FT-IR、XRD、zeta(ξ)电位、凝胶色谱等分析确定,CAD为淡黄色透明液体,pH值为3.7,相对分子质量为2.88×10⁶,阳离子度为16.7,等电点(0.1%溶液)约为pH值10.5,有效成分2.6%,主要特征官能团有羟基、氨基、季铵基和酰胺基, 呈不规则晶体结构.将CAD与相对分子质量3.67×10⁵的多糖类电负性微生物絮凝剂MBF8复配,对浊度12~460 NTU、离子强度3.0 mmol·L^-1的高岭土悬浊液进行烧杯实验.结果表明,MBF8与CAD的最佳使用方式为先投加MBF8后投加CAD,复配比5:3时效果最好,适用的pH范围为6.0~10.0.采用PAC(3.0 mg·L^-1)+MBF8+CAD(1.0 mg·L^-1)复配絮凝,pH=8.0下,对浊度为110 NTU的高岭土悬浊液,浊度去除率>97%,残余铝<0.08 mg·L^-1,絮体大、沉降快,絮凝效果优于PAC+分子量800万、1200万的阴离子PAM及分子量1500万的阳离子PAM.     

太湖主要环湖河道沉积物反硝化潜力及其控制因子

河流反硝化作用是水体氮素去除的重要途径,对流域氮负荷削减具有重要意义.为探究河网区河道的反硝化脱氮能力及其主要控制因子,本研究调查了太湖14条主要环湖河道的水质和沉积物特征,通过泥浆培养实验,利用氮氩比的方法和膜接口质谱仪分析技术,测定了14条环湖河道的沉积物反硝化潜力.结果表明,太湖环湖河道的反硝化潜力为-9.93~35.71 μmol·L^-1·d^-1,均值为（20.79±14.79） μmol·L^-1·d^-1,南部河道的反硝化潜力显著低于北部河道,负值代表沉积物的吸附或固氮行为.水柱中的硝态氮浓度、溶解氧、溶解性有机碳（DOC）和沉积物中的碳含量均会对沉积物反硝化潜力产生影响.相关分析结果表明,硝态氮浓度对河道反硝化作用的影响有限,反硝化作用对硝态氮底物的响应遵从米氏动力学模型（R²=0.77）的规律.而在太湖氮负荷严重的西部和北部河道区,水体中的DOC是反硝化潜力的主要限制因素.改善氮的去除环境对促进水体氮去除过程和区域氮管理具有重要意义,在氮负荷严重的流域河道,水体的DOC应该得到更多的关注.     

施氏矿物协同Cu（II）活化过硫酸盐去除水中土霉素的效果

畜禽粪污排放致使水体遭受土霉素（OTC）及重金属污染已成为环境领域的热点问题.本研究考察了施氏矿物协同Cu（II）活化过硫酸盐去除水中OTC的效果及施氏矿物循环利用效果.结果表明,在施氏矿物（Sch）加入量为0.8 g·L^-1,过硫酸钠（PS）浓度为180 μmol·L^-1,Cu（II）浓度为40 mmol·L^-1的条件下作用3 h,水中OTC（60 μmol·L^-1）去除率为74.3%.当用100 W功率紫外灯照射OTC+Cu（II）+PS+Sch处理体系,OTC在3 h时的去除率为98.5%,TOC去除率达到78.2%.施氏矿物循环第4批与首批结果相比较,体系OTC与TOC去除率无明显差异,OTC+ Cu（II）+PS+Sch体系在暗反应条件下首批与循环利用第4批对OTC的去除率分别为74.3%、78.4%,相应TOC的去除率分别为39.1%、39.8%;当用100 W功率紫外灯照射该体系,首批与循环第4批对OTC的去除率分别为98.5%、98.6%,相应TOC的去除率分别为78.2%、80.7%.本研究结果可为含有抗生素及铜离子废水的高级氧化处理提供一定的参数支撑.     

粘土原位除藻技术研究

对利用当地粘土治理水华蓝藻的原位除藻技术进行了研究.实验表明,经壳聚糖改性的当地不同类型粘土都能有效地絮凝除藻,改性粘土的矿物组成和有机质成分对絮凝除藻没有明显的影响.溶液中有机质(TOC≤40 mg/L) 的存在对壳聚糖改性粘土絮凝除藻有一定的负面影响.在太湖梅梁湾水域围隔中进行的原位除藻试验表明,采用经壳聚糖改性的当地粘土除藻效果明显,在用量仅为0.025 g/L (53 g/m²)时,除藻后SD透明度由15　cm提高至90　cm,叶绿素a的去除率达到98.6%.     

高藻原水预臭氧强化混凝除藻特性研究

采用有机物表观分子量分级、树脂分级等手段表征了原水有机物特征,通过实验室试验和中试运行对预臭氧强化混凝藻类去除效果、溶解性有机物（dissolved organic carbon,DOC）的变化和去除、消毒副产物的控制等进行了研究,并利用藻类活性测试研究了预臭氧强化混凝除藻机制.结果表明,采用适当浓度的臭氧（如1.0 mg·L^-1）进行预氧化,可有效提高藻类去除率,从常规混凝沉后水的55%～85%上升到95%左右,最高去除率达到99.3%（预臭氧1.0 mg·L^-1,PACl 3.0 mg·L^-1）;THMFP(trihalomethanes formation potential)总体去除效果从常规处理的117 μg·L^-1降至46 μg·L^-1;高投量（≥2.0 mg·L^-1）预臭氧,促进了藻类灭活,但影响了有机物的去除.藻类活性评价臭氧氧化和常规水处理过程对藻类作用存在显著差别.常规混凝对藻类活性影响不明显,不同剂量混凝剂对藻类活性影响差异不大;而臭氧对水体中的藻类有灭活作用,在0.5～2.0 mg·L^-1臭氧条件下,藻类活性降低至12以下,且该指标随着臭氧剂量的加大显著降低.紧随其后的混凝过程中,混凝剂或者其水解过程的某些成分对臭氧灭活藻类有增效/催化作用.与传统的显微计数法相比,藻类活性试验更明确地表征水处理过程对藻类生存状态的影响,为水处理除藻机制研究和工艺设计提供更清晰的信息.     

三峡小江回水区叶绿素a季节变化及其同主要藻类的相互关系

通过分析三峡小江回水区2007年5月～2008年4月115个样品叶绿素a的季节特点,提出了适用于表征小江回水区叶绿素a与不同藻类细胞密度和生物量的3种状态：Chla≤5 μg·L^-1、5 μg·L^-1-1和Chla>19 μg·L^-1,目的是探讨小江回水区不同水平下Chla与同期各主要藻类细胞密度和生物量的相互关系,为进一步了解三峡水库特定水域藻类季节演替特征提供参考. 全年数据下,小江回水区藻类总细胞密度、生物量和叶绿素a间均呈极显著的正相关关系（R>>0.70,Sig.≤0.01）. 研究期间小江回水区叶绿素a、绿藻、硅藻、蓝藻、甲藻生物量均值分别为(9.58±10.77)、(1605±647)、(707±124)、(511±266)和(4019±1345) μg·L^-1. Chla≤5 μg·L^-1的水平下,绿藻、硅藻与Chla浓度呈显著正相关;5 μg·L^-1-1水平下,仅有蓝藻与Chla含量呈显著正相关关系;Chla>19 μg·L^-1时,甲藻与Chla含量呈显著的正相关关系,但其它藻门与Chla含量无显著相关关系.     

崇明东滩沉积物再悬浮对沉积物-水界面氮、磷交换行为的影响

2002年7月采集崇明东滩低潮滩沉积物样和水样,运用模拟实验研究沉积物再悬浮作用对沉积物-水界面三态氮和可溶磷交换行为的影响实验发现,在沉积物不断发生再悬浮的过程中,水体中三态氮的含量明显增加,其中NO₃^--N变化最为显著,升高浓度值达11.869μmol·L^-1,NH₄⁺-N增长2.1713μmol·L^-1,NO₂^--N的释放约为0.2μmol·L^-1,可溶磷的含量也有少量的增加.同时,再悬浮作用对沉积物-水界面三态氮和可溶磷的环境地球化学行为也有一定的影响,与静置状态相比,NH₄⁺-N和NO₃^--N表现出与静置状态截然相反的变化规律,NO₂^--N受多种因素的影响,变化比较复杂,初期与静置状态相反而后表现一致.再悬浮颗粒物浓度也是制约沉积物-水界面三态氮和可溶磷变化的主要因子之一.实验结果显示,NH₄⁺-N在前7h以内的变化和悬浮颗粒物浓度表现出较好的相关关系,后5h呈负相关关系;NO₂^--N和可溶磷在整个过程中与悬浮颗粒物浓度的变化都有着很好的相关性,只有NO₃^--N的变化与其关系比较薄弱.     

五种水生植物对水中铀的去除作用

采用水培实验,研究了浮叶植物野生水葫芦(Eichhornia crassipes)、漂浮植物浮萍(Lemna minor L)、满江红(Azolla imbircata)、沉水植物菹草(Potamogeton crispus)、挺水植物空心莲子草(Alligator Alternanthera Herb)在初始铀浓度分别为0.15、1.50和15.00 mg·L^-1水中的生长状况及它们对水中铀的去除能力.结果表明,在21 d的水培试验期内,满江红对铀表现出了最强的抗性,0.15、1.50和15.00 mg·L^-1的铀对满江红的生长抑制率分别只有4.56%、2.48%和6.79%,而满江红对水中铀的去除率分别达到了94%、97%和92%.进一步的试验表明,每1 L水中种植7.5 g满江红,可以获得最大的铀去除率,将初始铀浓度为1.25、2.50、5.00和10.00 mg·L^-1的水体降至国家排放标准(GB 23727—2009)规定值(0.05 mg·L^-1)以下分别需要17、19、23和25 d.研究结果为进一步开展铀污染水体植物修复的研究打下了基础.     

近海潮间带水体及沉积物中重金属的含量及分布特征

利用ICP-MS分析技术,系统测定了天津沿海潮间带表层海水、悬浮物、沉积物及沉积物间隙水中13种重金属元素的含量.结果表明,不同介质中重金属总含量和个体含量差别较大,最大相差4～7个数量级(水和悬浮物中).在相同介质中,各采样点重金属总含量差别不大,变异系数小于30%,个体重金属浓度除间隙水中差别较大外,变异系数均小于50%.潮间带海水中溶解态重金属含量均值为41.2μg·L^-1,原水、沉积物间隙水、悬浮物和沉积物中重金属含量均值分别为62.7μg·L^-1、112.7μg·L^-1、345.0mg·kg^-1和262.3 mg·kg^-1.潮间带各介质中重金属构成有显著差别,典型重金属元素Zn、Cu、Pb和Cr在原水和过滤水中约占40%～50%,而在悬浮物、沉积物及其间隙水中约占到50%～80%.潮间带水体、悬浮物、沉积物与滨岸土壤中重金属元素组成和分布模式的相似性表明其污染来源为陆源污染物.对悬浮物和沉积物中重金属含量与有机质含量的相关分析结果显示二者间相关性较弱,但各重金属含量之间有显著的相关关系,说明它们有相似的地球化学行为.     

贵阳城市污水及南明河中氯霉素和四环素类抗生素的特征

采用固相萃取-高效液相色谱（UV检测）分析了贵阳城市污水、南明河水和沉积物中氯霉素和四环素类抗生素的特征.结果显示,南北两岸污水中氯霉素、土霉素、四环素和金霉素的平均含量分别为27.0、 2.3、 11.0、 1.1 μg·L^-1和21.2、 2.1、 9.5、 0.5 μg·L^-1,其中以氯霉素的污染为主;污水中抗生素的含量呈现明显的季节变化,这与用水量和疾病特点有关.南明河已广泛受到包括农业、养鱼塘、城市污水等来源的抗生素污染,其中城市污水是最重要的来源,受其影响,污水口下游的抗生素污染尤为严重.河水中氯霉素、土霉素和四环素在冬季的含量范围分别在2.1～19.0、ND～3.0、 0.8～6.8 μg·L^-1之间,夏季分别在0.2～1.3、ND～0.03、 0.2～0.3 μg·L^-1之间,金霉素只在冬季检出,含量范围在0.09～0.14 μg·L^-1之间;沉积物中4种抗生素在冬季的平均含量分别为147.6、 76.6、 99.2和1.6 μg·kg^-1;在夏季分别为195.8、 89.1、 34.4和9.0 μg·kg^-1.数据表明,河水中抗生素的含量受河水流量及来源特点的影响很大,冬季河水中抗生素的含量明显高于夏季;沉积物中抗生素的季节变化不明显.     

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.