外源添加磷和有机酸模拟铅污染土壤钝化效果及产物的稳定性研究

有机酸可提高土壤磷有效性,且能影响对重金属的固定,其在磷活化和重金属钝化方面具有非常复杂的功能.本研究以模拟铅污染土壤为对象,外源添加磷和柠檬酸,采用BCR三步连续提取法、0.01 mol·L-1CaCl2提取和毒性淋溶提取法(TCLP)评价有机酸存在下磷对模拟铅污染土壤的钝化效果;以苹果酸、NaNO3溶液为解吸剂探讨磷-柠檬酸-铅体系的稳定性.结果表明,无柠檬酸时,酸提取态Pb含量随磷浓度的增加而降低;加磷100 mg·kg-1、400 mg·kg-1时,酸提取态Pb含量随柠檬酸浓度增加而显著增加.残渣态Pb与酸提取态Pb的变化趋势相反,说明磷能降低土壤铅的生物有效性,柠檬酸则作用相反.有机酸浓度一定时,随磷浓度增加,0.01 mol·L-1CaCl2提取和TCLP提取的铅含量均呈降低趋势,表明磷具有钝化铅污染土壤的效果;但磷浓度一定时,它们提取铅含量随柠檬酸浓度增加表现出相反的变化趋势.土壤铅的解吸率随苹果酸浓度增加、pH值减小、离子强度增加而提高,且只添加磷处理的土壤铅解吸量较添加磷和柠檬酸共同处理的土壤少,前者钝化的铅稳定性更高.     

不同磷处理对污染土壤中有效态铅及磷迁移的影响

为了研究不同含磷化合物对污染土壤中铅有效性的影响及其在土壤剖面中的迁移状况,对3种不同性质的含磷化合物按含量为2500、5000 mg·kg-1进行了土柱试验.结果表明,对铅污染土壤施入磷酸氢钙(SSP)、磷矿粉(PR)及羟基磷灰石(HA)能显著降低土壤表层CaCl2(0.01 mol·L-1)提取态铅的含量,且有效铅的含量随磷施入含量的增加而显著降低.在施磷270 d后,施入含量为5000 mg·kg-1的磷酸氢钙(SSP5)、磷矿粉(PR5)及羟基磷灰石(HA5)处理土壤有效铅的含量分别比对照降低了86.6%、81.1%和89.7%.对不同深度土壤有效磷和全磷含量分析表明,土壤中施入不同溶解性质的磷显著增加了土壤表层(0～10 cm)的有效磷(Olsen-p)及全磷的含量,土壤中有效磷及全磷的含量随着土柱深度的增加而显著降低.除了SSP5处理外,上述不同磷处理对于大于50 cm深度的土壤中的有效磷和全磷变化没有显著影响,而所有处理对于大于70 cm深度的土壤中有效磷和全磷含量没有显著影响.这表明在铅污染土壤中施入不同性质的磷能显著降低土壤中CaCl2(0.01 mol·L-1)提取态铅的含量,而土壤中施入的磷在土壤垂直剖面的迁移却很少,即使是易溶性的磷酸氢钙(SSP)也不会造成大于70cm深度的土壤剖面中磷含量的显著性差异,其原因可能与土壤胶体对磷的强力吸附有关.     

杀菌剂对湖泊水体温室气体浓度分析的影响

通过往湖泊水样中添加杀菌剂(CuSO4和HgCl2),利用平衡法,用气相色谱仪测定CO2、CH4、N2O浓度,研究杀菌剂(CuSO4和HgCl2)添加对湖泊水体CO2、CH4、N2O浓度分析的影响.实验设计:对照组(CK)不加任何试剂;处理组T1加1mL CuSO4溶液,T2加5 mL CuSO4溶液,T3加0.5 mL HgCl2溶液;每组的水样分两批分析:(Ⅰ)预处理完成后立即分析和(Ⅱ)预处理完成后静置两天再分析.结果表明,CuSO4和HgCl2的添加均能明显增加水体中CO2的浓度,CK(Ⅰ)和CK(Ⅱ)的CO2平均浓度分别为(11.5±1.47)μmol·L-1和(14.38±1.59)μmol·L-1,T1(Ⅰ)和T1(Ⅱ)的CO2平均浓度分别为(376±70)μmol·L-1和(448±246.83)μmol·L-1;T2(Ⅰ)和T2(Ⅱ)的CO2平均浓度分别为(885±51.53)μmol·L-1和(988.83±101.96)μmol·L-1;T3(Ⅰ)和T3(Ⅱ)的CO2平均浓度分别为(287.19±30.01)μmol·L-1和(331.33±22.06)μmol·L-1.但CuSO4和HgCl2添加对水体中CH4和N2O的浓度没有影响.对比Ⅰ和Ⅱ的实验结果可知,在水样预处理完成后需当天分析其温室气体(CO2、CH4、N2O)浓度.本研究表明,杀菌剂的添加能显著增加水体CO2的浓度.     

曝气加氢氧化钙复合技术抑制底泥磷释放及对底泥微生物多样性的影响

底泥磷释放是导致水体富营养化的主要原因之一,本文通过在样泥中分别投加0、0.01和0.02 mol·L-1Ca(OH)2溶液,同时进行微臭氧曝气(0.6 g·min-1),研究了曝气加氢氧化钙复合技术抑制底泥磷释放的效果及对底泥微生物多样性的影响.结果显示,投加0.02 mol·L-1Ca(OH)2组上覆水中总磷(TP)浓度的最终值与对照组相比,抑制率达到34%;从各形态磷的角度进一步分析发现,与对照组相比,该组底泥中可溶性磷和铁磷含量分别降低了92%和60%,其最终转化为钙磷是该技术的关键.通过聚合酶链式反应-变性梯度凝胶电泳技术(PCRDGGE)研究发现,各试验组微生物相似性在65%~85%之间;Berger-Parker优势度指数、Margalef丰富度指数、Shannon多样性指数变化不明显,表明该技术不会影响底泥微生物多样性.     

NTA和DTPA对小麦幼苗对金属吸收的诱导效应

通过盆栽试验和化学提取实验研究了有机配体NTA和DTPA对小麦对沙土中外源重金属Cd,Cu,Pb和Zn的吸收的影响.研究表明,在所试验的土壤金属浓度下,有机配体NTA和DTPA的添加均明显导致小麦幼苗中金属Cu,Zn,Cd和Pb富集量的增加,且DTPA的作用效果高于NTA.10mmol·kg-1DTPA作用效果高于5mmol·kg-1DTPA,但提高程度有限.NTA处理组各金属14 d茎叶富集系数高于7 d茎叶富集系数.对于不同金属,DTPA的作用导致小麦幼苗茎叶富集系数随时间变化的规律不同.5mmol·kg-1NTA,5mmol·kg-1DTPA和10mmol·kg-1DTPA的添加明显导致土壤中4种外源金属的0.01 mol·L-1CaCl2提取态含量的增加.小麦茎叶重金属富集量与0.01mol·L-1CaCl2提取态金属含量具有较好的相关性,说明配体NTA和DTPA的添加导致小麦幼苗对4种金属的富集量的增加是与其导致0.01 mol·L-1CaCl2提取态含量的增加是密切相关的.     

氨水混合吸收剂脱除CO2实验研究

氨水作为一种很有应用前景的CO2化学吸收剂,存在吸收速率慢的问题.使用湿壁塔实验台,考察了不同种类的添加剂(MEA、PZ、1-MPZ、2-MPZ)对氨水吸收CO2速率的影响.结果表明,4种添加剂均能明显提高氨水吸收CO2的速率,其中PZ具有最好的促进效果.0、0.1、0.3和0.5 mol·mol-1负荷下,3 mol·L-1NH3+0.3 mol·L-1PZ溶液的总传质系数(KG)分别是3 mol·L-1NH3溶液在相应负荷下的3、3.2、3.2和2.9倍.改变反应温度、添加剂量、PZ浓度等条件对基于NH3/PZ混合吸收剂吸收CO2的反应过程进行实验,得到了其在不同条件下的KG,初步探讨CO2吸收的反应机制,并计算出准一级反应速率常数为42.7 m3·(mol·s)-1.     

不同小分子物质与传统抗菌剂对混合菌生物膜形成的抑制效应

针对污水处理系统混合菌形成的生物膜,比较了两种传统抗菌剂(银离子和氯)及3种小分子物质,包括双(3-氨基丙基)胺、(Z-)-4-溴-5-(溴乙烯)-2(5H)-呋喃酮(BBF)和香兰素对生物膜形成的抑制效应.结果表明,本研究所选用的传统抗菌剂中,0.05~10 mg·L-1Ag+对生物膜形成的抑制率为23%~70%,0.01~20 mg·L-1氯对生物膜形成的抑制率为23%~53%.而在3种小分子物质中,500~2000μmol·L-1双(3-氨基丙基)胺对生物膜形成的抑制率为16%~68%,0.1~200 mg·L-1香兰素对生物膜形成的抑制率为20%~37%,1~20 mg·L-1BBF对生物膜形成的抑制率为11%~18%.高浓度的Ag+(0.1~10 mg·L-1)会显著抑制混合菌的生长,且浓度越高,抑制效果越显著.1000μmol·L-1以下的双(3-氨基丙基)胺基本不会抑制混合菌的生长,但高浓度(2000μmol·L-1)的双(3-氨基丙基)胺会显著抑制混合菌的生长.     

热活化和酸活化给水处理厂废弃铁铝泥的吸磷效果

探讨了酸活化和热活化方式对给水厂废弃铁铝泥(ferric and alum water treatment residuals,FARs)吸附磷能力的影响.结果表明,酸活化和热活化均能提高FARs的磷吸附能力,其中经2mol·L-1HCl酸活化的FARs(AH2.0-FARs)和300℃热活化的FARs(H300-FARs)取得最好的磷吸附效果.结合SEM和XRD表征技术对活化机制分析得知,两种活化方式均会使FARs变得疏松、多孔,从而提高FARs对磷的吸附能力.Langmuir和Freundlich两种模型均可很好地反映活化前后FARs的等温吸附过程,FARs对磷的理论饱和吸附量由活化前的20.48mg·g-1分别增加到22.86mg·g-1(AH2.0-FARs)和29.66mg·g-1(H300-FARs).低pH值有利于FARs对磷的吸附.此外,解吸附实验结果表明活化后的FARs能够更好地固定磷.因此,活化后的FARs是一种相对更好的磷的吸附材料.     

底泥扰动对上覆水中磷形态分布的影响

通过室内试验模拟底泥受持续和间歇扰动的过程.探讨了扰动作用对上覆水中不同形态磷分布的影响.结果表明,持续扰动和间歇扰动显著促进了上覆水中的溶解态磷向底泥迁移.持续扰动与间歇扰动作用下,上覆水中溶解性无机磷(DIP)分别在第6h和第24h达到平衡状态,为0.014mg.L-1和0.015mg.L-1.显著低于对照试验(0.04mg.L-1);而溶解性总磷(DTP)则在第6h和第48h达到平衡状态,为0.047mg·L-1和0.045mg.L-1,显著低于对照试验(0.065mg.L-1).持续扰动促进了颗粒态磷(PC)的释放,扰动6h后,PP达到最大值(9.18mg·L-1).随后下降.第24h后,PP稳定在2.18mg·L-1左右;而间歇扰动作用下,第2h,PP达到最大值(2mg·L-1),随后下降,第96h后,PP稳定在0.093mg·L-1左右.扰动作用下,TP的变化规律与PP一致.与初始状态相比,持续扰动和间歇扰动作用下,DIP/DTP、DIP/TP、DTP/TP显著下降,而上述该值在对照试验中则基本保持不变,说明扰动导致的底泥再悬浮有利于降低上覆水中溶解态磷的含量.     

基于中性盐提取的土壤重金属固液分配与自由态金属离子浓度测定

采用0.01mol·L-1CaCl2、0.002mol·L-1Ca(NO3)2和纯水(UPW)3种常用提取剂对我国南方两种典型农田重金属污染土壤进行提取试验.同时,应用土壤重金属固液分配多表面模型来预测提取液中重金属含量,结合道南膜技术(DMT)测定Ca(NO3)2提取液中自由态金属离子浓度,并与ECOSAT模型计算值进行比较.结果表明,提取剂中Ca2+浓度增加能显著提高土壤重金属溶出率,而提取液pH、溶解态有机碳(DOC)浓度却随溶液Ca2+浓度增加而降低.多表面模型(Multi-Surface Model)对大部分提取液金属浓度有较好的预测效果,部分土样提取液Cu、Pb、Zn浓度的预测效果较差.DMT测定的Ca(NO3)2提取液自由态重金属浓度与模型计算值较为一致,能够较准确地测定土壤溶液自由态重金属离子浓度.     

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.