EDTA和柠檬酸淋洗去除污染粉土柱中Pb的研究

以场地重金属污染的修复治理为背景,通过室内压实制备Pb污染土柱以模拟现场污染土,采用乙二胺四乙酸二钠二水合物(EDTA)和柠檬酸对Pb污染粉土柱进行淋洗,考察淋洗剂类型、淋洗剂浓度、淋洗时间和污染土中Pb的负载量等各个因素对污染土中Pb的释放特性的影响。研究表明:相较于柠檬酸,EDTA对Pb的去除效果明显更优。随淋洗时间延长,不同浓度的EDTA对Pb的淋洗效率趋于一致。污染土中Pb负载量越小,EDTA对Pb的去除率越高,64.5%～83.6%的Pb可以从污染土中解吸出来;柠檬酸浓度越高,对Pb的去除效果越好。由于柠檬酸浓度较低时易吸附于土体表面,并且抑制Pb的解吸,低浓度柠檬酸淋洗总体效果偏差,最高去除率仅为11.4%。因此,现场修复Pb污染土若采用EDTA可采用较低浓度(0.005 mol/L)淋洗,而若选择柠檬酸需要提高其浓度。     

黄土体对重金属（Cd、Pb、Zn、Cu）吸附试验研究

本文主要研究了土壤环境ｐＨ值的变化对黄土吸附重金属的影响，得出随着ｐＨ值增大土壤对重金属吸附量增大；随着重金属离子浓度的增大，水溶液的ｐＨ值降低；随着重金属离子浓度的增大，黄土对重金属的吸附量增大；黄土对重金属（Ｃｄ、Ｐｂ、Ｚｎ、Ｃｕ）吸附力亲和顺序为：Ｐｂ２＋＞Ｃｄ２＋＞Ｃｕ２＋＞Ｚｎ２＋。     

生物表面活性剂对河道底泥重金属的淋洗效果比较

为了比较生物表面活性剂性质、活性剂浓度和淋洗时间等对河道底泥中重金属淋洗效果的影响。研究中选取了3种不同的生物活性剂即茶皂素、皂角苷和槐糖脂。研究结果表明:活性剂不同,淋洗效果不同;生物活性剂的胶束形成性质会影响淋洗效果;在3种活性剂中,临界胶束浓度低的槐糖脂淋洗效果最好;此外,活性剂浓度为8%时,淋洗效果已达到最佳。淋洗时间对淋洗效果的研究则证明:茶皂素、皂角苷和槐糖脂对重金属淋洗动力学过程可以用Elovich方程进行描述,淋洗过程为非均相扩散过程。研究中还对淋洗前后重金属形态进行了分析,淋洗可以有效去除底泥中弱结合态(离子交换态和碳酸盐结合态)重金属,使得强结合态的重金属所占比例增加,从而降低重金属的生物有效性。     

河道底泥中重金属的EDTA淋洗研究

以城市河道底泥为研究对象,用EDTA淋洗进行底泥无害化处理研究。分别探讨了EDTA浓度、淋洗时间、液固比等因素对底泥淋洗效果的影响。目的是为了给底泥中重金属的淋洗实际应用提供技术参数。实验结果表明:淋洗条件如EDTA浓度、淋洗时间和液固比都对淋洗效果有显著影响。本实验中所用底泥0.1 mol/L的EDTA在液固比10∶1的条件下,淋洗效果最好,淋洗30 min就能去除掉70%~80%的Cu和Cd。研究中还比较了淋洗前后底泥中重金属形态分布的变化,详细探讨了底泥与重金属的结合方式对淋洗效果的影响。从形态分析可以得出,原底泥中重金属的分布形态可以用来预测淋洗效果。EDTA淋洗主要针对的是离子态和碳酸盐结合态的重金属,对结合力较强的铁锰氧化物、有机物结合态和残渣态重金属效果较差。因此,可预先进行重金属形态分析来确定底泥是否可用EDTA进行淋洗。     

受污染珠江水源水的生物预处理试验研究

作者利用生物陶粒技术对受污染的珠江水源水进行了生物预处理试验。初步试验结果表明，在水力停留时间为３０ｍｉｎ，气水比为１∶１的工艺运行条件下，生物陶粒预处理对ＮＨ３－Ｎ的去除率为９２．７％，对ＣＯＤＣｒ、ＯＣ和ＢＯＤ５的去除率分别为２９．３％、３６．６％和９０．１％，同时对色度和浊度也有一定的去除作用。     

基于EDTA淋洗离心—硫酸盐还原菌固化法去除污泥中重金属镉的研究

为研究如何分离和去除污泥中重金属镉（Cd）,采取二氨基乙烷四乙酸(ethylene diamine tetraacetic acid, EDTA)淋洗离心与硫酸盐还原菌( sulfate-reducing bacteria, SRB)固化相结合的方法进行了污泥试验并统计分析了污泥中重金属Cd的形态分布和含量变化。结果表明：在离心力100g、淋洗时间12 h、淋洗2次和离心温度30 ℃的条件下采用EDTA对污泥原样进行淋洗离心,污泥中Cd含量由6.793 mg/kg降至5.241 mg/kg,去除率达22.8%。然后采用SRB对淋洗离心后的污泥试样进行固化,不稳定态Cd含量由2.589 mg/kg降至1.103 mg/kg,固化后污泥中的Cd含量低于《绿化种植土壤》（CJ/T 340-2016）中重金属要求的Ⅳ级标准2 mg/kg。与传统单一修复方法相比,该联合方法有效地降低了污泥中活性大、污染程度高形态Cd的含量,减轻了其环境危害性。     

农田土壤重金属Cd的环保淋洗剂筛选研究

土壤淋洗是一种有效修复重金属污染土壤的方法,而淋洗剂的选择是淋洗过程的关键因素,直接影响淋洗效率。研究了4种淋洗剂(乙酸、柠檬酸、CaCl₂、FeCl₃)对Cd轻度污染的农田土壤淋洗性能及影响因素。结果表明:淋洗效果依次为FeCl₃＞柠檬酸＞乙酸＞CaCl₂;FeCl₃的淋洗机理是Fe³⁺与土壤中的Cd²⁺离子交换,其水解出的H⁺可促进碳酸盐结合态Cd溶出,Cl^-还可与Cd²⁺形成稳定的螯合物;经优化后的最佳的淋洗条件是固液比为1∶5,浸提时间为4 h,此时乙酸、柠檬酸、CaCl₂和FeCl₃的最大土壤Cd去除率分别为30.24%,24.62%,24.82%,81.90%;pH值对淋洗效果的影响较大,除CaCl₂外,3种淋洗剂的淋洗效果都随pH值的升高而降低(pH值在2.5～5.0范围内),FeCl₃的淋洗效果降低最为显著。研究成果可为Cd污染农田土壤修复提供技术支撑。     

ＭＳＷＩＢＡ改良海相淤泥质工程渣土性能与机理研究

利用ＭＳＷＩＢＡ与氢氧化钙－矿粉（ＧＧＢＳ）协同固化改良渣土,通过强度及浸出试验探究ＭＳＷＩ-ＢＡ改良渣土的性能,采用ＸＲＤ以及ＳＥＭ－ＥＤＳ对改良土进行微观表征。结果表明:掺入5％～10％的ＭＳＷＩＢＡ能改良渣土水稳性,有效降低渣土的液限;5％ＭＳＷＩＢＡ掺量的改良土具有较佳的应用效益,其水稳系数提高了16％、液限降低了5％,7ｄ无侧限抗压强度为1．95ＭＰａ,符合路基填筑强度要求;改良土重金属浸出浓度均低于0．05ｍｇ／Ｌ,符合Ⅲ类地下水以及Ⅱ类地表水的要求;ＭＳＷＩＢＡ改良土的主要水化产物为（Ｎ,Ｃ）－Ａ－Ｓ－Ｈ以及钙矾石,强度和污染组分的稳定性均有提升,材料低碳经济,具有良好应用前景。     

高含盐量石油发酵工业废水处理研究

石油发酵工业废水中高含盐量对于生物处理有强抑制作用，本研究利用ＳＢＲ活性污泥法对该类废水进行有机物降解试验，在废水中溶解性总固体浓度（ＴＤＳ）５００００ｍｇ／Ｌ～６５０００ｍｇ／Ｌ和ＣＯＤＣｒ浓度３０００ｍｇ／Ｌ～６０００ｍｇ／Ｌ范围内高含盐量对驯化后的耐盐活性污泥并无明显抑制作用，ＣＯＤＣｒ去除率稳定在９０％以上，ＢＯＤ５去除率稳定在９５％以上，半速度常数Ｋｓ＝３４０ｍｇ／Ｌ，最大比降解速度Ｋ＝１９６ｄ－１。驯化活性污泥以菌胶团和少量原生动物（裂口虫和漫游虫）为主，菌落形态相对较少。     

生物活性剂淋洗对河道底泥重金属毒性和生态风险影响评价

以河道底泥为研究对象,采用Tessier五步连续提取法比较了淋洗前后底泥中重金属的形态分布变化,并采用生物活性评价法,浸出毒性法,地累积指数法和潜在生态风险指数法比较及评价了生物活性剂槐糖脂淋洗前后底泥重金属的生物活性、浸出毒性和生态风险系数的变化。研究同时还采用三维荧光对底泥中溶解性有机质进行了分析。结果表明:淋洗后底泥重金属形态分布发生变化,重金属的迁移能力降低,生物活性和危害性降低,浸出毒性减小,单一和综合潜在生态风险降低,说明淋洗是一种有效的降低底泥重金属环境危害的方法。经淋洗后的底泥中重金属稳定性提高,对生态风险小,可以进一步进行资源化利用。     

Use of citric acid for heavy metals extraction from contaminated sewage sludge for land application.

Recent studies revealed that organic acids such as citric and oxalic acids seemed to be more promising as chemical extracting agents for removal of heavy metals from contaminated sludge, since they are biodegradable and can attain a higher metal extraction efficiency at mildly acidic pH compared to other extracting agents. Results of a lab-scale study on the efficiency of citric acid in the extraction of chromium (Cr), copper (Cu), lead (Pb), nickel (Ni) and zinc (Zn) from anaerobically digested sludge, revealed that citric acid seemed to be highly effective in extracting Cr (at 100%), Cu (at 88%), Ni (at 98%) and Zn (at 100%) at pH 2.33, mostly at 5 days leaching time except for Cu and Zn, which are at 1 day and 2 h contact times respectively. Lead removal at the same pH was also high at 95% but at a longer leaching time of 11 days. At pH 3, citric acid seemed to be highly effective in extracting Pb (at 100%) at 1 day leaching time, although higher removals were also attained for Ni (70%) and Zn (80%) at only 2 h leaching time. Chemical speciation studies showed that Cr, Cu and Ni in the sludge sample seem to predominate in residual fractions, while Pb and Zn were found mostly bound to organic and inorganic matter forms, hence the potential of the sludge for land application.     

Heavy metal displacement in EDTA-assisted phytoremediation of biosolids soil.

Chelating agents are added to soil to solubilise the metals for enhanced phytoextraction. Yet no studies follow the displacement and leaching of heavy metals in soil with biosolids following solubilisation with chelates. The objective of this work was to determine the mobility of heavy metals in biosolids in a soil from a sludge farm that had received biosolids for 25 years. The soil was placed in columns in a greenhouse. Columns either had a plant (poplar) or no plant. After the poplar seedlings had grown for 144 d, the tetrasodium salt of the chelating agent EDTA was irrigated onto the surface of the soil at a rate of 1 g per kg of soil. Drainage water was analysed for three toxic heavy metals and four essential heavy metals. Without EDTA, concentrations of the seven heavy metals in the leachate from columns with or without plants were low or below detection limits. With or without plants, the EDTA mobilised all heavy metals and increased their concentration in drainage water. Without plants, the concentrations of Cd, Cu, Fe, and Zn in the leachate from columns with EDTA were above drinking-water standards. The presence of poplar plants in the soil reduced the concentrations of Cu, Fe, and Zn in the leachate so it fell within drinking-water standards. Concentrations of Cd and Pb in the leachate remained above drinking-water standards with or without plants.     

建筑垃圾骨料浸出重金属对环境影响研究

为了探究建筑垃圾骨料作为渗透性路面底基层替代材料的适用性,必须考虑建筑垃圾对地下水的污染问题。选取2种常见的建筑垃圾再生骨料:再生砖骨料(CB)和再生混凝土骨料(RCA),探究其浸出重金属浓度含量及其污染物的释放特征及规律,分析建筑垃圾试样配比、液固比、pH 值等因素对重金属浓度的影响。结果表明:在纯砖块条件下时,重金属Cd、Cu、Ni和Zn含量最小;在纯混凝土条件下时,重金属Cr和Pb含量最小。Cd和Zn的含量随着液固比的变化上下起伏不大,浸出浓度基本保持不变,可见Cd和Zn达到了溶解平衡;Cr和Pb的浸出率随着液固比的增加而增加,浸出量也在不断增加;Cu和Ni的浸出率随着液固比的增加而减小。Cd、Ni和Pb在不同pH值时的浸出浓度随时间变化趋势也基本相似,随着pH值的升高,Cd、Ni和Pb的平衡浓度降低;Cr的浸出浓度与pH值的增高呈正相关;Cu和Zn具有两性浸出,形成U形曲线,在极端的酸性和碱性pH值时浓度升高。建筑垃圾再生骨料浸出后的重金属浓度低于我国相关标准,可作为路面填料。     

重金属在消落带土壤-水体系中的迁移研究

以三峡库区消落带土壤和江水构成的有机体系为对象,通过动态模拟实验,研究了Pb、Zn、Cu、Cr在土壤江水体系中的迁移情况。研究表明,长江水体一旦受Pb、Zn、Cu、Cr的污染,消落带土壤中的Pb、Zn、Cu质量比将显著升高,Zn会迁移至各层(0~10 cm,10~20 cm,20~30 cm)土壤中,Pb和Cu主要滞留在土壤表层,而土壤中的Cr的质量比降低;并且土样中Pb、Cr、Cu和Zn的质量比均会随江水中的重金属浓度的升高而增加。     

Bioleaching of heavy metals from contaminated aquatic sediments using indigenous sulfur-oxidizing bacteria: A feasibility study

The removal of heavy metals from contaminated river sediments was studied using suspension leaching under laboratory conditions and percolation leaching in a pilot plant. The leaching potential of indigenous sulfur-oxidizing bacteria was compared with acid treatment. Bioleaching with elemental sulfur as substrate was found to be better than treatment with sulfuric acid for the solubilization of all metals tested. The physical and chemical properties of the sediments used in this study did not affect leaching capacity under optimum conditions in the laboratory.Under the practical conditions in the pilot plant, the redox state of sludge had a considerable influence on leaching efficiency. In a deposited oxic sediment with good permeability, about 62% of the metals tested were removed by percolation leaching after 120 days. Zn, Cd, Ni, Co and Mn were sufficiently leached to enable treated sediments to be reused as soil. In a freshly dredged anoxic sediment, only a total of 9 % of metals were removed. The results indicate that freshly dredged sediments need to undergo pretreatment before percolation leaching to improve mass transfer and to activate the leaching active bacteria.     

Effect of irrigation water quality on organic matter, Cd and Cu mobility in soils of Central Mexico.

Untreated wastewater has been used for irrigation since 1912 at the Irrigation District 03, Central Mexico. Accumulated heavy metals are dominantly bound to the organic soil fraction. In a field study we evaluated the effect of wastewater irrigation on the quality of soil organic matter and the amount of water extractable Cu and Cd. In a column experiment we tested if water treatment affects the leaching of both metals and dissolved organic carbon (DOC) out of soils that have been irrigated for more than 90 years with untreated wastewater. The field study shows that long term irrigation increases the mineralizable carbon fraction and the DOC concentrations. The water extractable Cu and Cd concentrations also increase and correlate with DOC. In the column leachates the Cu concentrations also correlate with DOC, the Cd concentrations correlate with the sum of cations, chloride and DOC concentrations. Water treatment reduced Cd leaching, but it did have no substantial effect on Cu leaching.     

Application of ionic liquids for the removal of heavy metals from wastewater and activated sludge

This paper presents the results of adsorption studies on the removal of heavy metals (Cr, Cu, Cd, Ni, Pb and Zn) from standard solutions, real wastewater samples and activated sewage sludge using a new technique of liquid-liquid extraction using quaternary ammonium and phosphonium ionic liquids (ILs). Batch sorption experiments were conducted using the ILs [PR4][TS], [PR4][MTBA], [A336][TS] and [A336][MTBA]. Removal of these heavy metals from standard solutions were not effective, however removal of heavy metals from the industrial effluents/wastewater treatment plants were satisfactory, indicating that the removal depends mainly on the composition of the wastewater and cannot be predicted with standard solutions. Removal of heavy metals from activated sludge proved to be more successful than conventional methods such as incineration, acid extraction, thermal treatment, etc. For the heavy metals Cu, Ni and Zn, ≥90% removal was achieved.     

Heavy metals removal from contaminated sewage sludge by naturally fermented raw liquid from pineapple wastes.

The large amount of unutilised pineapple wastes produced every year in tropical countries, particularly in Thailand, adds to the existing environmental pollution problems of the country. This study investigated the utilisation of pineapple wastes to treat another form of waste (sludge) from wastewater treatment facilities in Thailand. Laboratory scale studies were carried out to determine the potential of using naturally fermented raw liquid from pineapple wastes as a source of citric acid in the extraction of Cr, Cu, Pb, Ni and Zn from anaerobically digested sewage sludge. Results of the leaching study revealed its effectiveness in extracting Zn (at 92%) at pH 3.67 and a short leaching time of only 2 h, and Ni at almost 60% removal at the same leaching time. Chromium removal was also high at almost 75% at a longer leaching time of 11 days. Variation in metal removal efficiencies may also be attributed to the forms of metals in sludge, with metals predominantly in the exchangeable and oxidisable phases showing ease of leachability (such as Zn). Compared to citric acid, at pH approaching 4.0, naturally fermented raw liquid seemed to be more effective in the removal of Zn and Cu at the same leaching time of 2 h, and Cr at a longer leaching time of 11 days. The pineapple pulp, which is a by-product of the process, can still be used as animal feed because of its high protein content.     

大燕河沉积物重金属污染特征及生态风险分析

为了解大燕河表层沉积物重金属污染特征及潜在生态风险,对大燕河干流和支流沉积物重金属污染物进行了分析,并采用Hakanson生态危害指数法进行评价。结果表明,大燕河干流沉积物重金属含量明显高于支流,重金属含量高于广东省土壤背景值,Cu、Cd、Zn、Pb、Hg超出了土壤环境质量Ⅰ级标准。沉积物中重金属Cu、Cd的富集系数明显高于其他重金属,不同采样点重金属超出背景值的程度具有明显的差异性,呈现干流高于支流,下游高于上游的特征。沉积物中重金属具有极强的生态危害,各种重金属造成的平均生态危害程度由大到小依次为:CdHgCuAsPbZnNiCr,其潜在生态风险应引起足够的重视。     

Landfill leachate treatment by an experimental subsurface flow constructed wetland in tropical climate countries.

Municipal leachate was treated in an experimental unit of constructed wetlands of subsurface flow type. The parameters studied were organics (BOD and COD), solids and heavy metals (Zn, Ni, Cu, Cr and Pb). Using two types of emergent plants of Scirpus globulosus and Eriocaulon sexangulare, more than 80% removal was achieved for all the parameters. E. sexangulare removed organics and heavy metals better than Scirpus globulosus. A higher concentration of heavy metals in the influent did not change the removal efficiency.