阳宗海湖泊砷污染来源解析与防治

2008年以来,云南阳宗海湖泊发生了砷污染,导致水体功能下降,对周边社会经济造成了重要影响。通过对阳宗海湖泊水环境、入湖河流、泉眼、周边工业源的砷监测分析以及地质环境状况的研究,弄清了阳宗海深水湖泊砷污染的水平、时空变化规律、污染来源解析,研究结果显示,其砷污染来源于阳宗海南岸地下多个上升出露泉眼。     

珠江流域五大高原湖泊近10年水质状况及变化趋势分析

基于珠江流域五大高原湖泊2007—2016年水质监测数据,分别对其水质进行了单因子评价、污染特征的层次聚类分析、水质变化趋势的spearman秩相关系数分析,结果表明:(1)采用单因子指数法评价,五大高原湖泊的水质类别均不符合其水质目标的要求;(2)根据聚类分析,第一类为以面源为主的抚仙湖、星云湖及杞麓湖,第二类为城镇生活污水及工业废水点源污染突出的异龙湖,第三类为以砷污染为明显特征的阳宗海;(3)根据spearman秩相关分析,除抚仙湖外,其它湖泊水质均呈现变差趋势,高锰酸盐指数、五日生化需氧量呈普遍变差趋势。     

Myrothecium verrucaria NF-08产漆酶条件的响应面法优化及粗酶染料脱色研究

以半知菌属疣孢漆斑菌Myrothecium verrucaria NF-08为供试菌,采用响应面方法优化菌株产漆酶条件,并以其漆酶粗酶进行3种结构类型6种染料的脱色试验,考察了粗酶浓度、温度和p H值对脱色率的影响.两水平析因设计、中心组合设计和验证试验结果表明:葡萄糖浓度为15.4 g·L~(-1)、蛋白胨浓度为43.3 g·L~(-1)和培养基初始p H值为6.68时,漆酶活性达到最大值(25.58±1.60)U·m L~(-1),是单因素试验(16.82 U·m L~(-1))的1.52倍,提高了52.1%.以上述发酵条件获得的M.verrucaria NF-08漆酶粗酶对3种结构类型染料均有脱色效果,排序为偶氮类优于芳甲烷类优于蒽醌类.脱色率随粗酶浓度增大(2~8 U·m L~(-1))、反应温度升高(15~35℃)而上升,随p H值上升(4~10)而下降.粗酶浓度为5 U·m L~(-1),反应温度为25℃,p H值为4时,偶氮类染料铬黑T和芳甲烷类染料碱性品红即可几乎完全脱色,脱色率分别为99.2%和94.6%.     

云南阳宗海砷污染治理后水体和沉积物中砷的赋存特征

通过采集阳宗海表层水样、上覆水水样和表层沉积物,测定水体砷含量和沉积物砷形态的组成,探讨阳宗海砷污染治理后表层水、上覆水和沉积物砷的空间分布特征和季节变化规律。结果表明,阳宗海表层水中高砷区域分布在西部和北部,平均浓度为18.46μg/L;上覆水中高砷区只集中在北部和东南部,上覆水总砷平均浓度为25.39μg/L;除春季表层水总砷浓度高于上覆水,其他三个季节表层水和上覆水总砷浓度差异不大,平均浓度为35μg/L。水体总砷浓度为春季含量最低,沉积物总砷春季含量最高。阳宗海表层沉积物砷平均浓度为24.13mg/kg,主要以残渣态砷为主,离子态砷、碳酸盐结合态砷和铁锰结合态砷含量很低。综上所述,阳宗海经过治理后,目前湖泊水体和沉积物中的砷浓度逐渐下降,生态风险进一步降低。     

天然矿物负载Fe/Co催化H2O2氧化降解阳离子红3R

类Fenton反应关键是催化剂的活性,利用浸渍法负载铁、钴双金属对天然矿物材料进行改性,提高其催化活性,并运用扫描式电子显微镜(SEM)、X射线能谱仪(EDS)、X射线衍射(XRD)等表征手段对负载前后的材料进行表征分析.结果表明负载后材料中生成Fe2O3和Co Fe2O4两种新物质.将合成的催化剂用于催化H2O2氧化阳离子红3R染料废水,在催化剂投加量3 g·L-1,H2O2投加量0.3 m L·L-1,反应时间1 h条件下,100 mg·L-1阳离子红3R废水脱色率可达99.8%,TOC去除率可达58.4%,催化剂中活性组分主要为表面负载的Fe2O3和Co Fe2O4,电子自旋共振(ESR)分析表明催化氧化过程中产生羟基自由基,阳离子红3R发色基团在1 min已被完全破坏,光谱分析表明反应过程中有小分子物质生成.催化氧化效果受染料废水初始p H值影响小,适应p H范围广,解决了传统Fenton反应p H条件苛刻的问题.研究结果为印染废水处理提供了具有工程应用潜力的技术方法.     

水稻不同生育期根际及非根际土壤砷形态迁移转化规律

选取湖南某矿区污染稻田土,以盆栽试验的方式,采用美国TCLP(toxicity characteristic leaching procedure)和砷形态分析分级测定法,研究了水稻(Oryza sativa L.)各生育期(分蘖期、拔节期、孕穗期、灌浆期、成熟期)根际和非根际土壤中砷的赋存形态及转化规律.结果表明:1随着水稻生育期的延长,根际及非根际土壤p H值和砷TCLP提取态含量均逐渐上升,且非根际土壤p H值和砷TCLP提取态含量均高于同时期根际土壤.2水稻各生育期根际和非根际土壤中交换态砷(AE-As)含量均低于水稻种植前,并随着水稻生育期的延长逐渐上升.与水稻种植前相比,铝型砷(Al-As)、铁型砷(Fe-As)和钙型砷(Ca-As)含量在水稻种植后逐渐上升,但并不显著.残渣态砷(O-As)和总砷(T-As)含量在水稻种植后逐渐下降,在根际土壤中下降了37.30%和14.69%,在非根际土壤中分别下降了31.38%、8.67%.3在水稻不同生育期,土壤中各形态砷含量均表现为:残渣态铁型砷铝型砷钙型砷交换态砷.在p H值为5.0~5.8的范围内,各砷形态和砷TCLP提取态含量与p H值之间大都呈极显著或显著正相关,但根际土壤中钙型砷与p H值的相关关系较差.     

砷污染治理后阳宗海沉积物砷的分布与稳定性

阳宗海砷污染治理后,大量的砷随絮凝剂沉积到沉积物中。通过测定阳宗海沉积物及其上覆水中的总砷,用Tessier连续提取法分析了不同深度沉积物中砷的形态和稳定性,并用潜在生态风险指数法、地累积指数法评价了沉积物中砷的污染状况,旨在评估用絮凝剂治理湖泊砷污染是否存在二次污染的风险。研究表明,表层沉积物砷含量在湖底的水平分布不均匀,且随沉积物深度的增加而略有降低。沉积物中砷含量随着时间的推移而增加。地累积污染级别大部分为0级,潜在生态危害为Ⅰ级,沉积物砷污染程度相对较低,潜在生态危害风险小。各层沉积物中稳定性高的残渣态砷含量(14.12~18.38 mg/kg)及比例(93.47%~97.30%)均较高,因此,目前沉积物中砷稳定,不易溶出形成二次污染。     

颗粒活性炭改性同步去除水中铅、铬的研究

为提高颗粒活性炭同步去除水中铅、铬污染物的能力,分别使用氧化铁、氧化锰、十六烷基三甲基溴化铵(HTMAB)和氯化十六烷基吡啶(CPC)制作改性活性炭(Fe Cl3-AC,Mn O2-AC,HTMAB-AC,CPC-AC)。通过测定4种改性活性炭表面的等电点p H、酸碱官能团和扫描电子显微镜图像,研究4种改性活性炭吸附效果优异并分析其中原因。结果表明:Fe Cl3-AC同步去除铅、铬效果最佳,HTMAB-AC、CPC-AC与原炭效果持平,Mn O2-AC效果还不及原炭。从等电点p H来看,Fe Cl3-AC拥有较低的等电点p H,有利于静电吸附铬酸根阴离子团;从酸性基团数目来看,Fe Cl3-AC表面拥有较多酸性官能团,有利于离子交换作用,保证了对铅离子较高的吸附效率;从SEM来看,Fe Cl3-AC上Fe Cl3负载均匀,有效改善了活性炭表面特性,有利于吸附。     

氯化铁絮凝-直接过滤工艺对地下水中As(Ⅴ)的去除机制研究

为探明氯化铁(Fe Cl3)絮凝-直接过滤工艺对地下水中砷(As)的去除过程及机制,分别进行了批吸附实验、现场絮凝-直接过滤实验、扩展X射线精细结构光谱(EXAFS)及电荷分布多位络合(CD-MUSIC)模拟.采集的地下水样品As主要为五价[As(Ⅴ)],浓度为40μg·L-1.现场柱实验直接过滤工艺中Fe投加量为1.5 mg·L-1,出水As(Ⅴ)浓度均低于10μg·L-1,92 h内可提供64 984 L安全饮用水.固体废物毒性浸出实验表明泥饼浸出液中As浓度为3.4μg·L-1,远低于美国环保署限定值(5 mg·L-1).EXAFS和CD-MUSIC模拟表明Fe Cl3絮凝去除地下水中As(Ⅴ)存在两种机制:在p H 3~9.5范围内,As(Ⅴ)主要以双齿双核吸附在氢氧化铁上;p H9.5时,As(Ⅴ)主要与Ca2+和Mg2+形成沉淀而去除.     

纳米Fe3C/炭纤维非均相电芬顿降解二甲基砷的研究

针对结构稳定且难以靠常规方法去除的二甲基砷,制备新型负载Fe_3C纳米粒子的炭纤维催化剂,并对其非均相电芬顿降解二甲基砷进行了研究.结果表明,纳米Fe_3C/CF与阴极产生的H2O2发生电芬顿催化反应产生羟基自由基将二甲基砷降解为一甲基砷和As(V),As(V)可被同步吸附在Fe_3C/CF催化剂表面.通过考察电催化过程中初始p H、反应物初始浓度、电流强度和催化剂投加量等因素对催化氧化DMA效果的影响,表明在初始p H为3,二甲基砷初始浓度为5 mg·L~(-1),Fe_3C/CF投量为500 mg·L~(-1)的最佳条件下,经非均相电芬顿反应360 min后,二甲基砷去除率高达96%.     

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.     

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.     

Effects of chitosan on growth of an aquatic plant (Hydrilla verticillata) in polluted waters with different chemical oxygen demands

Effects of chitosan on a submersed plant, Hydrilla verticillata, were investigated. Results indicated that H. venicillata could prevent ultrastructure phytotoxicities and oxidativereaction from polluted water with high chemical oxygen demand (COD). Superoxide dismutase (SOD) activity and malondialdehyde (MDA) contents in H. verticillata treated with 0.1% chitosan in wastewater increased with high COD (980 mg/L) and decreased with low COD (63 mg/L), respectively. Ultrastructural analysis showed that the stroma and grana of chloroplast basically remained normal. However, plant cells from the control experiment (untreated with chitosan) were vacuolated and the cell interval increased. The relict of protoplast moved to the center, with cells tending to disjoint. Our findings indicate that wastewater with high COD concentration can cause a substantial damage to submersed plant, nevertheless, chitosan probably could alleviate the membrane lipid peroxidization and ultrastructure phytotoxicities, and protect plant cells from stress of high COD concentration polluted water.     

Removal of cadmium using MnO2 loaded D301 resin

MnO2 loaded weak basic anion exchange resin D301 （Anion exchange resin, macroreticular weak basic styrene） as adsorbent has been prepared and applied to the removal of cadmium. The adsorption characteristics have been investigated with respect to effect of pH, equilibrium isotherms, removal kinetic data, and interference of the coexisting ions. The results indicated that the Cd^2＋ could be efficiently removed using MnO2 loaded D301 resin in the pH range of 3-8 from aqueous solutions with the co-existence of high concentration of alkali and alkaline-earth metals ions. The saturate adsorption capacity of the Cd^2＋ was 77.88 mg/g. The adsorption process followed the pseudo first-order kinetics. The equilibrium data obtained in this study accorded excellently with the Langmuir adsorption isotherm.     

Effect of coagulation pretreatment on the fouling of ultrafiltration membrane

The purpose of this study is to understand the effect and mechanism of preventing membrane fouling, by coagulation pretreatment, in terms of fractional component and molecular weight of natural organic matter （NOM）. A relatively higher molecular weight （MW） of hydrophobic compounds was responsible for a rapid decline in the ultrafiltration flux. Coagulation could effectively remove the hydrophobic organics, resulting in the increase of flux. It was found that a lower MW of neutral hydrophilic compounds, which could remove inadequately by coagulation, was responsible for the slow declining flux. The fluxes in the filtration of coagulated water and supernatant water were compared and the results showed that a lower MW of neutral hydrophilic compounds remained in the supernatant water after coagulation could be rejected by a membrane, resulting in fouling. It was also found that the coagulated flocs could absorb neutral hydrophilic compounds effectively. Therefore, with the coagulated flocs formed on the membrane surface, the flux decline could be improved.     

Penetration analysis of elements and bioleaching treatment of spent refractory for recycling

Acidithiobacillus ferrooxidans ATCC23270 and Acidithiobacillus thiooxidans TM-32 were used for bioleaching of spent refractories of aluminium and copper melting furnaces for their recycling.Firstly,penetration of elements into aluminium melting furnace refractory was investigated and it was found that up to 7 cm from surface was contaminated.Comparison on leaching efficiency by the strains ATCC23270 and TM-32 found that the strain ATCC23270 could treat larger amount of the refractories than the strain TM-32 could do.In the experiment of bioleaching of spent refractory aluminium melting furnace by the strain ATCC23270,high leaching efficiency were obtained on Al,Si,and Ca,and extremely low leaching performance was,however,shown on the rest of elements i.e.,Na,Mn,and Zn.Under the strain TM-32 use,relatively high leaching performance was recognized on Al,Si,Ca,Na,Mn,and Zn.In the experiment of bioleaching for spent refractory copper melting furnace,almost the same leaching trends were shown on Cu,Zn,Al,and Si under the strains ACTT23270 and TM-32 uses.     

Simultaneous removal of ammonium and phosphate by zeolite synthesized from coal fly ash as influenced by acid treatment

Zeolite synthesized from fly ash （ZFA） without modification is not efficient for the purification of NH4＋ and phosphate at low concentrations that occur in real effluents, despite the high potential removal capacity. To develop an effective technique to enhance the removal efficiency of ammonium and phosphate at low concentrations, ZFA was modified with acid treatment and the simultaneous removal of ammonium and phosphate in a wide range of concentration was investigated. It was seen that when compared with untreated ZFA, only the treatment by 0.01 mol/L of H2SO4 significantly improved the removal efficiency of ammonium at low initial concentrations. The behavior was well explained by the pH effect. Treatment by more concentrated H2SO4 led to the deterioration of the ZFA structure and a decrease in the cation exchange capacity. Treatment by 0.01 mol/L H2SO4 improved the removal efficiency of phosphate by ZFA at all initial P concentrations, while the treatment by concentrated H2SO4 （≥0.9 mol/L） resulted in a limited maximum phosphate immobilization capacity （PIC）. It was concluded that through a previous mild acid treatment （e.g. 0.01 mol/L of H2SO4）, ZFA can be used in the simultaneous removal of NH4＋ and P at low concentrations simulating real effluent.