不同钝化剂对碱性镉污染土壤钝化效果研究

该研究以河南栾川石宝沟典型铅锌矿区镉污染农田土壤作为供试土壤,采用室内培养试验法,分别添加熟石灰、方解石、白云石、沸石、蒙脱石、生物炭等6种钝化材料,采用Tessier修正顺序七步提取法进行镉形态含量分析,研究不同钝化剂在1%、3%、5%添加量条件下对典型北方碱性土壤镉的钝化效果。结果显示,试验选用的6种钝化材料在不同程度上提升了土壤pH值,对p H值提升效果排序为熟石灰蒙脱石沸石白云石生物炭方解石。不同钝化剂对离子交换态Cd的钝化作用具有一定的差异性,钝化效果排序为熟石灰方解石生物炭沸石白云石蒙脱石,其中碱性物质熟石灰对离子交换态Cd的降低效果显著,同为碳酸盐矿物的方解石明显优于白云石,同为黏土矿物的沸石优于蒙脱石,生物炭钝化效果居中。其中5%添加量熟石灰、3%添加量方解石、1%添加量沸石、1%添加量生物炭钝化效果最为明显,对土壤离子交换态Cd含量分别降低了61.11%、25.32%、14.84%、24.76%。6种钝化剂的添加在不同程度上改变了Cd在土壤中的形态含量比例,总体来看,离子交换态镉含量显著降低,碳酸盐结合态、腐殖酸结合态、铁锰氧化物结合态镉含量明显增加,硅酸盐残余态镉含量小幅上升,强有机结合态略微下降。     

凹凸棒石组配硫酸锌对土壤Cd的钝化效果及生态风险评价

为明确凹凸棒石组配硫酸锌作为修复材料在钝化土壤Cd以及促进玉米生长方面的应用潜力,以凹凸棒石为原料,通过液相浸渍制备凹凸棒石组配硫酸锌作为钝化剂开展钝化试验与盆栽试验,研究了凹凸棒石与硫酸锌配比分别为3∶1、5∶1、7∶1、9∶1、11∶1时对土壤Cd有效性、玉米生长状况及其对Cd富集能力的影响,并采用扫描电镜初步探讨钝化剂的表面特征. 结果表明:与对照相比,添加凹凸棒石组配硫酸锌钝化处理使Cd的DTPA(二乙基三胺五乙酸)有效态含量降低了5.22%~32.77%,TCLP(毒性浸出方法)有效态含量降低了12.43%~35.65%,Cd的钝化效率随硫酸锌添加量的增加而显著提高(P<0.05). 钝化处理可显著降低玉米植株中Cd的含量,其茎部Cd含量的最大降幅为60.06%,根部Cd含量的最大降幅为32.69%,Cd主要集中分布在根部;同时,钝化剂的加入缓解了Cd对玉米生长的胁迫,随硫酸锌用量的增加,玉米生物量显著提升. 研究显示,凹凸棒石组配硫酸锌可作为对Cd污染农田修复的钝化剂,在钝化剂同等剂量水平下,凹凸棒石与硫酸锌配比为3:1时,对土壤中Cd的钝化效果最佳.      

药渣生物炭联合麦饭石对铜镉污染土壤修复研究

期望以板蓝根药渣为原材料制备生物炭,用于修复重金属Cu、Cd污染土壤,实现以废治污。该研究探讨以板蓝根中药渣为原材料制备的生物炭联合天然麦饭石对重金属Cu、Cd污染土壤的钝化修复效果及作用机理,采用室内土壤培养试验,研究钝化剂施加量为2%土壤质量时,500℃下制备的药渣生物炭(BC500)、天然麦饭石(MS)和等质量的生物炭与麦饭石组合钝化剂(BC500+MS)共3种钝化剂处理对重金属Cu、Cd污染土壤p H、土壤养分、铜镉形态的影响。土壤培养30 d研究结果表明,3种钝化剂均能提高土壤pH、土壤养分;施加单一药渣生物炭对铜的钝化效果好于天然麦饭石,但天然麦饭石对镉的钝化比药渣生物炭的效果更优;采用修正BCR三步连续提取法提取不同处理的Cu、Cd形态,与对照值(CK)相比,BC500处理的弱酸可提取态Cu、Cd含量分别降低了9.00%和6.82%,残渣态Cu、Cd含量分别增加了16.08%和16.67%;MS处理的弱酸可提取态Cu含量较对照无变化,Cd的酸可提取态降低了17.05%,残渣态Cu、Cd含量分别增加7.75%和59.52%;BC500+MS处理的弱酸可提取态Cu、Cd含量分别降低4.44%和26.14%,残渣态Cu、Cd含量分别增加10.16%和78.57%。通过表征分析表明,生物炭对Cu、Cd污染土壤钝化机制是吸附固定和形成沉淀作用,麦饭石对Cu、Cd污染土壤钝化机制主要是吸附作用。     

不同钝化剂对土壤有效态铅和镉含量的影响

通过向土壤中添加蚕沙、熟石灰和磷酸二氢钾,研究不同钝化处理对土壤有效态重金属含量、pH值及有机质含量的影响.结果表明:添加蚕沙和熟石灰都能使土壤中高植物有效挂的有效态Pb和有效态Cd大幅下降;其中以单施蚕沙处理效果最优,其对Pb和Cd的钝化效率分别达到36.5％和39.2％,而蚕沙+熟石灰处理钝化效果次之,分别为24.3％和26.9％.磷酸二氢钾的钝化作用不明显.添加熟石灰对土壤pH值影响最大,而蚕沙大幅增加了土壤中有机质含量.经统计分析,土壤pH值、有机质含量都与土壤有效态Pb、Cd含量之间呈负相关,说明通过提高土壤pH值及有机质含量,降低土壤重金属活性是土壤重金属钝化的主要机理.     

不同钝化剂对土壤有效态铅和镉含量的影响

通过向土壤中添加蚕沙、熟石灰和磷酸二氢钾,研究不同钝化处理对土壤有效态重金属含量、pH值及有机质含量的影响。结果表明:添加蚕沙和熟石灰都能使土壤中高植物有效性的有效态Pb和有效态Cd大幅下降;其中以单施蚕沙处理效果最优,其对Pb和Cd的钝化效率分别达到36.5%和39.2%,而蚕沙+熟石灰处理钝化效果次之,分别为24.3%和26.9%。磷酸二氢钾的钝化作用不明显。添加熟石灰对土壤pH值影响最大,而蚕沙大幅增加了土壤中有机质含量。经统计分析,土壤pH值、有机质含量都与土壤有效态Pb、Cd含量之间呈负相关,说明通过提高土壤pH值及有机质含量,降低土壤重金属活性是土壤重金属钝化的主要机理。     

磷酸盐、腐殖酸与粉煤灰联合钝化处理模拟铅镉污染土壤

本研究利用过磷酸钙、腐殖酸、粉煤灰及其复配组合钝化处理人工模拟Pb、Cd污染土壤,并采用CaCl_2浸取法、三乙三胺五乙酸(DTPA)浸取法以及BCR形态分级实验评价钝化效果,利用X射线衍射仪(XRD)和扫描电子显微镜能谱(SEMEDS)分析土壤表面微观形态与结构,进一步探究其钝化机制.结果表明,除了腐殖酸单一处理,其他不同钝化处理均能降低土壤CaCl_2和DTPA提取态Pb、Cd含量,其中先添加过磷酸钙和腐殖酸,然后再添加粉煤灰的联合处理实验组效果最佳.土壤pH值与CaCl_2、DTPA提取态Pb含量存在微弱的正相关关系,与CaCl_2、DTPA提取态Cd含量存在负相关关系,速效磷含量与二者都存在显著的负相关关系,说明速效磷含量是控制土壤Pb、Cd活性的主要因素.施用磷酸盐、腐殖酸和粉煤灰可以促进Pb、Cd由活性较高的弱酸提取态向活性低的残渣态转化,从而有效降低Pb、Cd的迁移能力.XRD和SEM-EDS分析表明,过磷酸钙钝化重金属的机制主要是通过离子交换作用将重金属转化为难溶的Ca-重金属混合磷酸盐,3种钝化剂联合作用机制主要通过溶解/沉淀以及表面吸附作用将重金属转化为稳定的磷酸铅沉淀[Pb_3(PO_4)_2]或者混合重金属矿物[PbFe_3(SO_4)(PO_4)(OH)_6],从而有效钝化重金属.     

生物炭、蒙脱石及其混合添加对复合污染土壤中重金属形态的影响

本文以采自湖南临湘某重金属复合污染的土壤为研究材料,采用室内培养方法,将生物炭(BC)和蒙脱石(MM)按1%、2%、5%单独添加,以及将二者混合添加(1%+1%),通过BCR连续提取法,研究不同钝化剂对复合污染土壤重金属形态变化的影响.结果表明,生物炭处理显著降低了Cu、Pb和Cd的有效态含量.蒙脱石处理中,MM5%处理使Cu、Pb、Zn、Cd的弱酸提取态含量分别降低了27.6%、19.2%、25.6%、19.2%.混合钝化剂处理使Cu、Pb、Zn、Cd的弱酸提取态含量分别降低了15.8%、15.9%、13.1%、12.0%,残渣态含量分别增加了39.0%、110.1%、9.6%、62.5%,显著降低了4种元素的移动性.蒙脱石钝化效果整体优于生物炭,两者结合使用效果更佳.     

生物炭和磷肥复合修复有色矿区重金属污染土壤的效果

以有色矿区污染土壤为研究对象,考察了生物炭和磷肥单施及复合施用对土壤重金属的钝化修复效果。单施生物炭或与磷肥复合处理土壤pH显著升高。单施磷肥及与生物炭复合处理显著提高了土壤TCLP提取态磷。生物炭和磷肥是较好的钝化土壤中Pb、Zn和Cd的修复材料,尤以P+HB处理的效果最好,使土壤TCLP提取态Pb、Zn和Cd分别降低39.4%、18.3%和41.8%,降低了重金属的迁移性和生物有效性。Pb的酸可提取态和可还原态主要向残渣态转化,而Zn和Cd主要向可氧化态转化。生物炭和磷肥复合对污染土壤中Pb、Zn和Cd的钝化有协同作用。     

几种有机、无机钝化剂对铜污染土壤的钝化效果研究

利用石灰、棉花秆生物炭、玉米秆生物炭和阴离子聚丙烯酰胺作为钝化剂,对3种浓度梯度的铜污染土壤进行处理。采用Tessier形态分级试验对钝化能力和效果进行评价,并以此研究土壤中铜的形态变化。结果发现,石灰(0.2%)、棉花秆生物炭(1%)和玉米秆生物炭(1%)和阴离子聚丙烯酰胺2‰对Cu污染土壤治理均具有较为良好的效果。在铜浓度为50 mg/kg的试验组中,石灰、棉花秆生物炭、玉米杆生物炭和阴离子聚丙烯酰胺可分别将有效态铜含量降低为6.73%、7.92%、8.16%、8.83%。Tessier形态分级试验结果表明:1)随着时间延长,水溶态+交换态铜含量自然降低;2)加入钝化剂的试验组,有效态Cu含量明显降低,缓和态和无毒态的Cu含量有不同程度地增加。说明施用钝化剂促进Cu由有效态向缓和态和无毒态转化是土壤原位修复的重要机制。     

2种组配改良剂对稻田土壤重金属有效性的效果

为研究2种组配改良剂LS(碳酸钙+海泡石)和HZ(羟基磷灰石+沸石)对土壤重金属的生物有效性以及水稻吸收累积重金属的影响,在湘南某矿区附近污染稻田中施用了不同添加量(0,2,4,8g/kg)的两种组配改良剂,并进行了水稻种植的田间试验.结果表明,施用2~8g/kg组配改良剂LS和HZ均能使土壤pH值和CEC含量显著增加,有机质含量变化不明显,LS比HZ更能提高土壤pH值和CEC含量.施用2~8g/kg组配改良剂LS能使土壤中Pb、Cd、Cu和Zn的TCLP提取态含量分别降低25.7%~52.2%、12.7%~25.7%、6.4%~17.2%和8.6%~23.4%,施用2~8g/kg HZ使土壤中Pb、Cd、Cu和Zn的TCLP提取态含量分别降低57.6%~80.1%、7.0%~40.9%、2.3%~22.7%和4.5%~33.2%.两种组配改良剂能显著降低土壤中Pb、Cd、Cu和Zn的生物有效性,抑制水稻植株对Pb和Cd的吸收,土壤Pb、Cd和Cu的TCLP提取态含量与水稻根系和糙米中Pb、Cd和Cu的含量之间存在显著或极显著的正相关关系,TCLP提取态含量能较好的表示重金属在土壤中的生物有效性.     

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.