超声波协同柠檬酸淋洗去除土壤中的重金属

利用超声波协同柠檬酸淋洗技术处理重金属污染土壤,研究淋洗剂浓度、固液比、超声波处理时间、功率密度对重金属淋洗修复效果的影响,采用Tessier连续提取法分析了只施用柠檬酸和超声波协同施用柠檬酸两种处理方式下,淋洗前后重金属的形态变化,并提出采用内梅罗污染综合指数法来评价淋洗试验对污染土壤的修复效果。结果表明,在淋洗过程中,柠檬酸的作用是主要的,超声波起到良好的强化协同作用,不仅能促进去除可交换态、碳酸盐结合态和铁锰氧化物结合态存在的包括Pb、Cd、Cu在内的重金属,而且有助于去除以这些重金属中以有机结合态和残渣态存在组分。经超声处理后,对土壤中重金属Pb、Cd、Cu的有机结合态和残渣态最优去除率可达89. 1%、94. 5%、69. 3%和49. 4%、86. 5%、49. 7%。     

不同淋洗剂对重金属镉污染土壤有效镉的去除

为解决土壤重金属镉污染问题，在实验室条件下研究了EDTA、柠檬酸、乙醇酸、氯化镁、十二烷基硫酸钠(SDS)对某地镉超标土壤的解吸作用，探究以上几种淋洗剂最佳去除浓度及液固比，并探究几种淋洗剂复配对土壤淋洗效果的影响。结果表明，有效镉的去除效果为EDTA(84%)>乙醇酸(71.02%)>氯化镁(59.45%)>柠檬酸(56.69%)>SDS(11.02%)。在液固比3时淋洗剂达到最佳淋洗效果。复配方案中EDTA与乙醇酸混合体积比为1︰2时达到最大值87.48%，与柠檬酸混合体积比为1︰1时达到85.91%，增强了EDTA的效果，与SDS混合则无明显影响。氯化镁与柠檬酸、乙醇酸复配效率分别可以达到81.5%、82.6%，与SDS混合则呈现轻微拮抗的效果。两种酸与SDS的混合淋洗剂虽未提高重金属去除率，但在调节土壤pH、节省酸用量上起到一定作用。综合淋洗效率及对土壤pH、有机质、阳离子交换量的影响，0.13 mol/L EDTA与1 mol/L柠檬酸在液固比3、混合体积比1︰1时达到最佳淋洗效率85.91%。试验结果可为利用柠檬酸与EDTA复配和氯化镁与两种小分子酸复配提高重金属在土壤介质中的解吸率提供参考，为污染土壤的治理提供思路。     

超声强化柠檬酸淋洗修复锑污染土壤的研究

采用超声波强化柠檬酸淋洗修复锑污染土壤,研究了超声波功率、超声时间和初始pH值对超声波强化柠檬酸淋洗修复锑污染土壤效果的影响,同时采用Wenzel连续提取法对处理前后土壤中锑的形态变化进行了分析。结果表明,超声波功率、超声时间以及初始pH值对柠檬酸淋洗效果具有显著影响。当超声波功率为550 W、超声时间为60 min、初始pH值=3时,土壤中锑的淋出率达到最大。与单独柠檬酸淋洗相比,超声波强化柠檬酸淋洗效果提高了16.18%。通过形态分析可知,超声波强化能显著提高土壤中各种形态锑的淋出,非特异性结合态锑、特异性结合态锑、无定型铁铝氧化物结合态锑、晶型铁铝氧化物结合态锑以及残渣态锑的淋出分别提高了19.29%、33.5%、29.9%、15.8%和6.4%。     

螯合剂调控下短毛蓼对锰污染土壤的修复潜力

采用盆栽试验,通过对锰尾矿区、恢复区和模拟锰污染土壤中加入不同质量摩尔浓度的抗坏血酸、酒石酸和EDTA,研究加入螯合剂对超富集植物短毛蓼累积土壤中锰的影响.结果表明:短毛蓼对不同土壤中锰的累积效果有很大不同,添加螯合剂能显著提高短毛蓼对尾矿区和恢复区锰的累积,却抑制了其对模拟区锰的吸收;EDTA对提高短毛蓼富集、转运土壤中锰的影响明显大于抗坏血酸和酒石酸,其中,10 mmol/kg EDTA对尾矿区短毛蓼地上部富集能力的影响达到了最大;植物对重金属的迁移总量与地上部生物量有密切关系,而螯合剂对植物有一定毒害作用,如果浓度过高会严重影响植物的产量,如10 mmol/kg EDTA使地上部的生物量减产过半.总的来说,不同浓度的不同螯合剂对短毛蓼累积锰的调控效应各不相同,从修复潜力和潜在的环境风险来看,5 mmol/kg EDTA是提高锰尾矿区短毛蓼对锰的转运能力和修复效率的最佳调控螯合剂.     

超声辅助柠檬酸化学淋洗复合污染土壤的研究

以某尾矿库周边重金属污染土壤作为研究对象,采用超声辅助淋洗方式,使用柠檬酸作为淋洗剂对Th、Fe、Mn进行去除。通过改变淋洗剂浓度、液固比、温度等条件,比较并分析其对去除量的影响并确定最优条件,结合淋洗动力学模型和热力学参数探究淋洗动力学表征与反应特性。结果表明,柠檬酸超声辅助化学淋洗90 min,适当提高淋洗剂浓度与温度、扩大液固比可提高重金属去除量,最优条件为：浓度0.1 mol/L、液固比为10 mL/g、温度45 ℃。重金属的去除量由大到小依次为Mn>Fe>Th,分别为5 055.09、1 750.98、61.48 mg/kg。三种重金属的淋洗动力学均符合双常数模型,Mn的淋洗动力学同时符合抛物扩散模型。Th和Fe为非均相扩散,Mn为抛物扩散、非均相扩散的混合扩散。Mn平均反应速率最大,为0.82,Th的表观活化能最小,为12.90 kJ/mol,表明Mn与柠檬酸反应更快,Th更易与柠檬酸反应。     

砂土中铵氮的吸附形态研究

[目的]利用浸提试验研究不同粒径组成的砂土中吸附的铵氮存在形态,为了解铵在包气带中的迁移转化提供参考.[方法]首先用不同初始浓度的NH4Cl溶液浸泡采集于某垃圾填埋场背景区的砂土以及从此砂土中筛分出的粗砂和细砂,再用3种不同浸提能力的浸提剂--水.KCl、CaCl2浸提吸附于土样上的不同形态的铵.[结果]不同浸提剂的浸提能力为:水相似文献   

三聚磷酸钠——碘量法测定铜精矿和原、尾矿石中铜

碘量法测定铜,常以氟化物、酒石酸、柠檬酸、六偏磷酸钠、磷酸钠、焦磷酸钠或Zn—EDTA对铁等干扰离子进行掩蔽。其中氟化物对铁的掩蔽效果较好,但对环境和玻璃器皿有污染和腐蚀作用,遇高钙、铝易形成氟化物沉淀吸附铜,使测定结果偏低。酒石酸、柠檬酸和Zn—EDTA对铁也有较     

菊花中重金属、砷盐的化学形态分析

[目的]了解菊花中的重金属和砷盐存在的化学形态及其分布.[方法]采用Tessier的连续提取法制备样品,采用原子吸收分光光度法测定铅、镉、铬、铜、砷,采用原子荧光光度法测定汞.[结果]菊花样品中铜以有机态和残渣态为主,碳酸盐结合态和铁锰结合态未检出;铅以有机结合态为主;镉以离子交换态为主;样品中汞以有机态和残渣态为主;砷盐各形态中,水溶态和离子交换态占总量与有机态和残渣态占总量相当.[结论]以有害元素总量做指标评价药材的安全性有失偏颇.     

矿区污染土壤的土柱模拟淋洗修复研究

以某矿区的污染样品为研究对象,采集表层土壤、中层土壤以及深层土壤,对各深度的土壤进行基本理化性质分析,并进行土柱模拟试验.结果表明:清水对土壤中铅、锌的淋洗效果不明显,淋洗率在10％以下;EDTA对污染土壤中铅、锌的最佳淋洗时间分别为8h和7h,去除率分别为32.21％和28.01％.达到最佳淋洗时间后,EDTA对土壤...     

化学氧化强化化学淋洗修复汞污染土壤的试验研究

分别采用KI、Na_2S_2O_3、EDTA溶液对汞污染土壤进行淋洗修复,筛选出修复效果最好的淋洗剂,确定了最佳淋洗工艺条件,并研究了化学氧化对化学淋洗修复汞污染土壤的强化作用。结果表明,Na_2S_2O_3溶液对汞的淋洗效果最好,最佳淋洗工艺条件为Na_2S_2O_3浓度0.05 mol/L、固液比1∶6(g/mL)、淋洗时间5 h,在此条件下,土壤中汞的淋洗效率达到62.54%。化学氧化能大大提高土壤汞的淋洗效率,经化学氧化强化化学淋洗处理后,土样汞含量降低到1.65 mg/kg,且淋洗效率达到78.85%。     

Enhanced Electrokinetic Remediation of Heavy Metals in Glacial Till Soils Using Different Electrolyte Solutions

Previous electrokinetic remediation studies involving the geochemical characterization of heavy metals in high acid buffering soils, such as glacial till soil, revealed significant hexavalent chromium migration towards the anode. The migration of cationic contaminants, such as nickel and cadmium, towards the cathode was insignificant due to their precipitation under the high pH conditions that result when the soil has a high acid buffering capacity. Therefore the present laboratory study was undertaken to investigate the performance of different electrolyte (or purging) solutions, which were introduced to either dissolve the metal precipitates and/or form soluble metal complexes. Tests were conducted on a glacial till soil that was spiked with Cr(VI), Ni(II), and Cd(II) in concentrations of 1,000, 500, and 250 mg/kg, respectively, under the application of a 1.0 VDC/cm voltage gradient. The electrolyte solutions tested were 0.1M EDTA (ethylenediaminetetraacetic acid), 1.0M acetic acid, 1.0M citric acid, 0.1M NaCl/0.1M EDTA, and 0.05M sulfuric acid/0.5M sulfuric acid. The results showed that 46–82% of the Cr(VI) was removed from the soil, depending on the purging solution used. The highest removal of Ni(II) and Cd(II) was 48 and 26%, respectively, and this removal was achieved using 1.0M acetic acid. Although cationic contaminant removal was low, the use of 0.1M NaCl as an anode purging solution and 0.1M EDTA as a cathode purging solution resulted in significant contaminant migration towards the soil regions adjacent to the electrodes. Compared to low buffering capacity soils, such as kaolin, the removal of heavy metals from the glacial till soil was low, and this was attributed to the more complex composition of glacial till. Overall, this study showed that the selection of the purging solutions for the enhanced removal of heavy metals from soils should be primarily based upon the contaminant characteristics and the soil composition.     

A study of different analytical extraction methods for nondetrital heavy metals in aquatic sediments

4.0 N HNO3-0.7 N HCl, 0.5 N HCl, 1 N hydroxylamine hydrochloride-25% acetic acid and 0.05 N EDTA were investiagted as extractants of nondetrital heavy metals from the sediments of the Rideau River. A comparison of these partial extraction methods with a total extraction method, showed that the 4.0 N HNO3-0.7 N HCl attacks the silicate crystal lattice considerably. 1 N hydroxylamine hydrochloride-25% acetic acid was found to be unsuitable for copper extraction. Both of the other two methods were suitable for the simultaneous extraction of Cd, Cu, Pb, Zn, Ni, Cr, Co, Mn, Fe, and Al from the organic adsorbed and precipitated phases of sediments. They both gave a measure of nondetrital heavy metals in sediments and are thus useful to environmental contamination studies.     

Reaction Kinetics of magnesite ore in dilute ethanoic acid

The leaching of naturally occurring magnesite in dilute ethanoic acid is achieved to optimize the reaction conditions affecting the reaction kinetics. In the current study effect of various reaction parameters (The particle size of ore, concentration of leaching agent, the reaction temperature and rate of stirring) on the dissolution of magnesium carbonate ore with aqueous solutions of acetic acid is probed. It is inferred that the rate of leaching reaction of magnesium carbonate ore in the aqueous solutions of acetic acid rises with a rise in temperature of reaction medium, acetic acid solution strength and decreases with the increase in particle size of the magnesite ore samples. The analysis of kinetic data done by the application of graphical and statistical approaches reveals that the leaching kinetics of magnesite ore in dilute solutions of acetic acid follows a surface chemically controlled mechanism. The calculated value of energy of activation for the dissolution reaction of magnesium carbonate in acetic acid is 46.39 kJ mol^–1.     

EDTA-Enhanced Washing for Remediation of Pb- and/or Zn-Contaminated Soils

The effects of the operating conditions, the initial concentrations of heavy metals in soils, and the competition among heavy metals during ethylenediaminetetraacetic acid (EDTA)-enhanced soil washing were extensively investigated using batch experiments with Pb- and/or Zn-contaminated soils aiming to determine the heavy-metal removal for different types of contaminations and to optimize the process parameters. Pb or Zn removal efficiency was found to be dependent on contact time, pH, concentrations of EDTA, and their initial concentrations in contaminated soils. The experimental results showed that the heavy-metal removal efficiency increased with a higher initial concentration of heavy metals in soils, and the concentrations of heavy metals in the solutions after washing were linearly correlated with their initial concentrations in soils. The study of the competition among heavy metals indicated that when EDTA was present in solution with the concentration less than the stoichiometric requirements, Pb removal efficiency was higher than that of Zn; on the other hand, when EDTA concentration was greater, Pb and Zn removal efficiencies were almost the same.     

新型缓释EDTA对土壤铅镉释放的影响

利用羧甲基壳聚糖的环境友好性和成模性将其作为缓释载体,将EDTA和羧甲基壳聚糖按照1︰1的配比通过喷雾干燥器制备了的缓释EDTA。以缓释EDTA为研究对象,进行了表征分析、缓释动力学研究、土壤重金属静态活化特性和动态淋溶特性研究。结果表明：缓释EDTA包封率可达87.51%,在水中释放过程符合Higuchi模型,具有明显的缓释效果。缓释EDTA相比EDTA可以在提高土壤溶液中Pb、Cd离子浓度的同时有效控制Pb、Cd离子的突增,促使土壤溶液中的Pb、Cd离子保持适量浓度持续提升。动态淋溶结果表明,添加两种不同形式的EDTA会显著提升Pb、Cd的淋失量,但缓释EDTA处理能显著降低Pb、Cd的初始淋失量和淋失总量,其中Pb和Cd的淋失总量分别降低了19.5%和20.9%。     

EDTA滴定法测定复杂铜阳极泥中铋

铜阳极泥成分受电解工艺参数、阳极板质量、现场控制等多种因素的影响,元素种类和含量复杂多变。采用EDTA滴定法检测含高铅、高钡的复杂铜阳极泥中铋时,样品溶解过程常出现不溶结块,从而易对铋形成包裹,导致测定结果误差大、稳定性差。实验采用王水-硫酸溶解样品,在硝酸介质中用EDTA滴定法检测铋含量。通过试验确定称样量为0.2~1.0g并满足溶液中铋质量浓度不小于140mg/L,以硝酸-酒石酸混合酸作为浸取酸,调节溶液pH值至1.5~1.7,用1.060×10^-2 mol/L EDTA标准溶液测定铋,终点敏锐。按照实验方法测定铜阳极泥实际样品中铋,测定结果的相对标准偏差(RSD,n=9)为0.86%~1.5%,回收率为98%~101%。方法有效解决了复杂铜阳极泥中的铋量不易准确测定的问题,适用于铋含量为1%~12%(质量分数)的复杂铜阳极泥样品的检测。     

EDTA滴定法测定复杂铜阳极泥中铋

铜阳极泥成分受电解工艺参数、阳极板质量、现场控制等多种因素的影响,元素种类和含量复杂多变。采用EDTA滴定法检测含高铅、高钡的复杂铜阳极泥中铋时,样品溶解过程常出现不溶结块,从而易对铋形成包裹,导致测定结果误差大、稳定性差。实验采用王水-硫酸溶解样品,在硝酸介质中用EDTA滴定法检测铋含量。通过试验确定称样量为0.2~1.0g并满足溶液中铋质量浓度不小于140mg/L,以硝酸-酒石酸混合酸作为浸取酸,调节溶液pH值至1.5~1.7,用1.060×10^-2 mol/L EDTA标准溶液测定铋,终点敏锐。按照实验方法测定铜阳极泥实际样品中铋,测定结果的相对标准偏差(RSD,n=9)为0.86%~1.5%,回收率为98%~101%。方法有效解决了复杂铜阳极泥中的铋量不易准确测定的问题,适用于铋含量为1%~12%(质量分数)的复杂铜阳极泥样品的检测。     

Leaching kinetics of copper from natural chalcocite in alkaline Na4EDTA solutions

The leaching behavior of copper from natural chalcocite (Cu₂S) particles in alkaline Na₄EDTA solutions containing oxygen was examined at atmospheric pressure. The EDTA leaching process took place with consecutive reactions, where the solid product of the first reaction, covellite (CuS), became the reactant for the second. The copper leached into the alkaline solutions was immediately consumed by the chelation of copper (II) with EDTA, and the mineral sulfur was completely oxidized to sulfate ion. The experimental data for the leaching rate of copper were analyzed with a familiar shrinking-particle model for reaction control. The conversion rate of chalcocite to covellite was found to be about 10 times as high as the dissolution rate of covellite. The time required for complete dissolution of covellite was directly proportional to the initial particle size and was inversely proportional to the square root of the product of the hydroxide ion concentration and the oxygen partial pressure, but it was independent of the Na4EDTA concentration in the presence of excess Na₄EDTA. The observed effects of the relevant operating variables on the dissolution rate were consistent with a kinetic model for electrochemical reaction control. The kinetic model was developed by applying the Butler-Volmer equation to the electrochemical process, in which the anodic reaction involves the oxidation of covellite to copper (II) ion and sulfate ion and the cathodic reaction involves the reduction of oxygen in alkaline solution. The rate equation allowed us to predict the time required for the complete leaching of copper from chalcocite in the alkaline Na4EDTA solutions.     

Microbial leaching in environmental clean-up programmes

Microbial leaching is a simple and effective technology for extracting valuable metals from low-grade ores and mineral concentrates. Besides the industrial application for raw materials supply, microbial leaching has some potential for remediation of mining sites, treatment of mineral industrial waste products, detoxification of sewage sludge and for remediation of soils and sediments contaminated with heavy metals. There is no routine treatment for toxic metals dispersed in solid materials, and autotrophic and heterotrophic leaching processes may be considered for environmental clean-up programmes. The problems of bioremediation for heavy metal-contaminated sites are very different from those of bioremediation for organic pollution, but intensive interdisciplinary collaboration in basic and applied research in this economically important field is expected to be very beneficial in the near future. It would be ideal if the bioremediation system maximised the extent and rate of degradation of waste materials, simultaneously minimising the level of toxic substances during the operation.     

Sequential Electrokinetic Remediation of Mixed Contaminants in Low Permeability Soils

The coexistence of heavy metals and polycyclic aromatic hydrocarbons (PAHs) at many of the contaminated sites poses a severe threat to public health and the environment. Very few technologies, such as soil washing/flushing and stabilization/solidification, are available to remediate such sites; however, these technologies are ineffective and expensive to treat contaminants in low permeability clayey soils. Previous studies have shown that electrokinetic remediation has potential to remove heavy metals and organic compounds when they exist individually in clayey soils. In the present study, the feasibility of using surfactants and organic acids sequentially and vice versa during electrokinetic remediation was evaluated for the removal of both heavy metals and PAHs from clayey soils. Kaolin was selected as a model clayey soil and it was spiked with phenanthrene and nickel at concentrations of 500 mg/kg dry each to simulate typical field mixed contamination. Bench-scale electrokinetic experiments were performed with the sequential anode conditioning with: (1) 1 M citric acid followed by 5% Igepal CA-720; (2) 1 M citric acid followed by 5% Tween 80; and (3) 5% Igepal CA-720 followed by 1 M citric acid. A periodic voltage gradient of 2 V/cm (with 5 days on and 2 days off cycles) was applied in all the tests. A removal of about 96% of phenanthrene was observed in the test with 5% Igepal CA-720 followed by 1 M citric acid sequence. Most of the nickel (>90%) migrated from anode to cathode in this test; however, it precipitated in the section very close to the cathode due to the high pH conditions. Conversely, the removal efficiency of nickel was about 96 and 88% in the tests with 1 M citric acid followed by 5% Igepal CA-720 sequence and 1?M citric acid followed by 5% Tween 80 sequence, respectively. However, the migration and removal efficiency of phenanthrene in both of these tests were very low. Overall, it can be concluded that the sequential use of 5% Igepal CA-720 followed by 1 M citric acid may be an effective remedial strategy to remove coexisting heavy metals and PAHs from clayey soils.