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.     

胡敏酸改性膨润土钝化污染土壤Pb&Cd及机理

通过盆栽试验,探讨了胡敏酸改性膨润土对重金属铅、镉污染土壤的钝化效果及机理。结果表明,铅、镉污染土壤中施加胡敏酸改性膨润土能显著降低小白菜中Pb、Cd的含量,在添加Cd(3 mg/kg)/Pb(250 mg/kg)污染土壤和Cd(1 0 mg/kg)/Pb(5 00 mg/kg)污染土壤上小白菜地上部分Pb含量分别比对照降低19.08%和47.91%,Cd含量分别比对照降低9.79%和14.89%。土壤本身对添加的重金属Pb/Cd有一定的耐受力和自我净化能力,在添加重金属后,添加的Pb/Cd元素大部分直接转化为较为稳定的碳酸盐结合态和铁锰氧化结合态。相关性分析显示小白菜的鲜重与小白菜Pb/Cd含量极显著负相关,进一步说明胡敏酸改性膨润土是通过提高小白菜的生物量,从而降低Pb/Cd在小白菜中的含量。     

石灰、粉煤灰处理铅镉污染土壤的试验研究

试验模拟了Cd,Pb污染土壤,加入石灰、粉煤灰等浸出毒性,试验结果表明,加入质量分数为5％的石灰后,浸出液中的Cd,Pb浸出浓度最低,比模拟污土样品分别降低85．5％,45．2％,其它处理样品的浸出浓度和浸出率都较高,处理效果不理想。Cd,Pb污染土壤进入生活垃圾填埋场之前,添加少量石灰做预处理,是一种较好的方法。另外,浸提刺pH值对Cd,Pb的浸出影响很大。在浸提剂1#（pH值为4．93±0．05）和浸提刺2#（pH值为2．64±0．05）2种浸提剂下,Cd浸出浓度相差约30～40倍,Pb的浸出浓度相差约10～20倍。     

电镀场地污染土壤稳定化修复药剂的设计优化

以Cu和Ni等重金属含量较高的污染土壤为研究对象,选取Na_2S、铁粉、Fe S、高岭土、nano-HAP、油菜秸秆生物炭和石硫合剂对其进行稳定化研究,以重金属浸出浓度下降率和单位成本的重金属浸出浓度下降率综合评价各材料单独添加时的修复效果,并进一步选取铁粉、Fe S和石硫合剂进行混料设计实验和添加量梯度实验,分析修复药剂的最佳配比和用量。研究结果表明:1)单一材料修复实验中,石硫合剂的修复效果最佳,综合修复效果评价值顺序为石硫合剂>油菜秸秆生物炭>铁粉>FeS>高岭土>nano-HAP>Na_2S; 2)混料实验中,使用高岭土和石硫合剂按照质量比为0. 76∶1. 24配制稳定化修复药剂,药剂添加量为土壤质量的2. 0%时,综合修复效果最优,污染土壤中Cu和Ni的浸出浓度分别可由7. 01,2. 06 mg/L降至0. 94,0. 47 mg/L。     

CGF固化/稳定化重金属污染土强度及浸出特性

通过CGF(由电石渣、粒化高炉矿渣、粉煤灰组成的固废基固化剂)固化/稳定化不同土质种类(由不同黏粒、粉粒、砂粒配比调配)、不同复合重金属(Cu、Ni、Pb、Zn)含量的污染土,借助宏微观试验研究固化/稳定化污染土的强度特性、重金属浸出特性以及固化/稳定化机理.研究结果表明:CGF固化/稳定化重金属污染土强度和重金属浸出浓度主要由养护龄期、重金属含量和土质种类共同决定;随着养护龄期的增加,固化/稳定化污染土强度逐渐增加,但不同重金属含量的强度变化规律不同,存在重金属”临界含量”;随着养护龄期的增加,重金属浸出浓度逐渐减小,其浸出浓度变化规律亦存在重金属"临界含量",该"临界含量"由养护龄期和土质种类控制,固化/稳定化Clay污染土在7,28,90d的"临界含量"分别为200,300,600mg/kg,28d时固化/稳定化Clay、CSSM511、CSSM111污染土"临界含量"分别为300,200,200mg/kg,固化/稳定化CSSM011污染土不存在"临界含量".CGF固化/稳定化重金属污染土作用机理包括固化剂对重金属离子的化学沉淀、包裹、吸附、离子交换等稳定化作用和土中黏土矿物对重...     

工业废渣-过硫酸钠协同固化/稳定化石油污染土配比优选研究

采用过硫酸钠、石灰、粉煤灰、电石渣为固化剂材料,设置4因素4水平正交试验,研究不同配比下石油污染土的无侧限抗压强度、毒性浸出浓度、酸中和容量的变化规律,并通过模糊优选理论筛选出固化剂最优配比,利用pH值、温度、S₂O₈^2–含量、总石油烃含量、X射线衍射(XRD)和扫描电镜(SEM)试验分析固化机理.试验结果表明:从极差分析得到过硫酸钠对石油污染土的无侧限抗压强度和毒性浸出浓度影响最大,石灰对酸中和容量影响最大;以无侧限抗压强度、毒性浸出浓度、酸中和容量和处理成本作为模糊优选指标,过硫酸钠、石灰、粉煤灰、电石渣掺量分别为0.6%、8.0%、10.0%、6.0%时为最优配比,此时处理后的污染土7d无侧限抗压强度为630.40kPa,毒性浸出浓度为4.44mg/L,酸中和容量为385.71cmol/kg,处理成本为136.46元/t,处理后的污染土达到了废物再利用的强度和环境安全要求;过硫酸钠氧化去除土中部分石油,石灰、粉煤灰和电石渣水化反应生成胶凝物质包裹吸附石油,并胶结土壤颗粒,使处理后的污染土毒性浸出浓度降低,强度及酸中...     

镁基膨润土和水泥对砷铅复合污染土壤的钝化效能与机理研究

利用镁基膨润土（MB）和水泥（SN）作为钝化剂修复化工厂砷（As）、铅（Pb）复合污染土壤,探索了两种钝化剂对土壤pH值、有机碳含量（OC）、阳离子交换量（CEC）、浸出毒性及重金属形态分布的影响,结合钝化前后土壤形貌的变化,初步揭示了钝化机理.结果表明,两种钝化剂均可使土壤pH值显著升高,有机碳含量增加,阳离子交换能力增强.钝化30 d后,MB-5对As、Pb的钝化率分别达到67.09%和65.93%;SN-5对As、Pb的钝化率分别达到65.76%和65.04%.经两种钝化剂处理后,Pb的弱酸提取态和可还原态向更加稳定的可氧化态和残渣态转化.MB处理使土壤As由可交换态、可氧化态向无定形铁结合态、结晶性铁结合态转化,SN处理使土壤As向残渣态转化.两种钝化剂均可使土壤的微观形态从片状转变为碎屑状、增加团聚颗粒.与SN相比,MB更能促使土壤As（Ⅲ）向As（V）转化,从而显著降低土壤毒性.     

赤泥基纳米零价铁对多金属污染土壤修复效果

为实现重金属复合污染（Pb、Zn、Cu和Cd）土壤同步修复,构建土壤-小白菜体系,探究赤泥（RM）、纳米赤泥（RMn）以及纳米赤泥负载纳米零价铁（RMn-nZVI）这3种不同赤泥基钝化剂对Pb、Zn、Cu和Cd复合污染土壤的修复效果与机制,并考察土壤中Pb、Zn、Cu和Cd形态分布对小白菜积累Pb、Zn、Cu和Cd的控制作用.结果显示,3种钝化剂施用可显著提高土壤pH,降低土壤酸可提取态（F1）Pb、Zn、Cu和Cd含量,增加残渣态（F4）含量,最终钝化效果表现为：RMn-nZVI>RMn>RM.此外,3种钝化剂显著降低了小白菜可食用部分Pb、Zn、Cu和Cd的积累,其中RMn-nZVI处理下降低程度最高,Pb、Zn、Cu和Cd含量分别下降35.11%、45.05%、69.52%和59.63%.结果表明,纳米赤泥负载纳米零价铁新型钝化材料在重金属复合污染土壤修复领域具有一定的应用潜力.     

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.     

清淤底泥处置中添加粉煤灰/炉渣对重金属生物有效性及毒性的影响

在清淤底泥中添加碱性粉煤灰、燃煤炉渣进行钝化处理后,通过浸出毒性实验、重金属形态分级实验及植物生长实验对底泥基质中重金属的活性及生物有效性进行了研究.结果表明:清淤底泥中添加粉煤灰、燃煤炉渣等碱性物质后显著降低了底泥基质中可溶态重金属含量,其中,交换态、有机结合态Pb、Zn所占比例显著降低;碱性物质的加入缓解了重金属的浸出危害,钝化底泥基质中粉煤灰、炉渣对Cu的稳定率可达90.34%~96.88%;与此同时也抑制了底泥中重金属在植物体内的富集与迁移,降低了重金属的生物有效性.相关性分析表明,底泥基质中交换态重金属含量、浸出浓度、植物茎叶中重金属含量及植物根伸长抑制率之间存在显著正相关关系(p0.01).     

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.     

Degradation of metabolites accumulated of benzo[a]pyrene by coupling Penicillium Chrysogenum with KMnO4

Several main metabolites of benzo[a]pyrene （BaP） formed by Penicillium chrysogenum, Benzo[a]pyrene-1,6-quinone （BP 1,6- quinone）, trans-7,8-dihydroxy-7,8-dihydrobenzo[a]pyrene （BP 7,8-diol）, 3-hydroxybenzo[a]pyrene （3-OHBP）, were identified by high-performance liquid chromatography （HPLC）. The three metabolites were liable to be accumulated and were hardly further metabolized because of their toxicity to microorganisms. However, their further degradation was essential for the complete degradation of BaP. To enhance their degradation, two methods, degradation by coupling Penicillium chrysogenum with KMnO4 and degradation only by Penicillium chrysogenum, were compared; Meanwhile, the parameters of degradation in the superior method were optimized. The results showed that （1） the method of coupling Penicillium chrysogenum with KMnO4 was better and was the first method to be used in the degradation of BaP and its metabolites; （2） the metabolite, BP 1,6-quinone was the most liable to be accumulated in pure cultures; （3） the effect of degradation was the best when the concentration of KMnO4 in the cultures was 0.01% （w/v）, concentration of the three compounds was 5 mg/L and pH was 6.2. Based on the experimental results, a novel concept with regard to the bioremediation of BaP-contaminated environment was discussed, considering the influence on environmental toxicity of the accumulated metabolites.     

Impact of atrazine and nitrogen fertilizers on the sorption of chlorotoluron in soil and model sorbents

Sorption of chlorotoluron in ammonium sulfate, urea and atrazine multi-solutes system was investigated by batch experiments. The results showed application of nitrogen fertilizers to the soil could affect the behavior of chlorotoluron. At the same concentration of N, sorption of chlorotoluron decreased as the concentration of atrazine increased on the day 0 and 6 in soil, respectively. The sorption of chlorotoluron increased from 0 to 6 d when soils were preincubated with deionized water, ammonium sulfate and urea solution for 6 d. That indicated incubation time was one of the most important factors for the sorption of chlorotoluron in nitrogen fertilizers treatments. The individual sorption isotherms of chlorotoluron in rubbery polymer and silica were strictly linear in single solute system, but there were competition sorption between pesticides or between pesticides and nitrogen fertilizers. That indicated the sorption taken place by concurrent solid-phase dissolution mechanism and sorption on the interface of water-organic matter or water-mineral matter.     

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.     

Removal of heavy metals from sewage sludge by low costing chemical method and recycling in agriculture

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