电动修复不同形态铬污染土壤的研究

研究了土壤中铬的价态对电动修复效率的影响以及电动修复前后土壤中铬形态的变化.结果表明,电动修复对于土壤中1 000 mg Cr(Ⅵ)/kg的去除效果明显,总铬去除率达59.7%;而对1 000 mg Cr(Ⅲ)/kg的去除效率较低,仅为6.2%;Cr(Ⅲ)和Cr(Ⅵ)(各500 mg/kg)同时污染的土壤,铬的去除率介于中间,为18.7%.电动修复前后,土壤中铬的形态也发生了明显的变化.其中,电动修复对土壤中Cr(Ⅵ)的提取形态影响最大,而对Cr(Ⅲ)提取形态并无太大的影响.总体上,电动修复后对于生物有效的弱酸可提取态铬的浓度都保持在较低水平,预期铬的环境风险(物理流动性和生态风险)将大大降低.     

污染土壤电动修复及供能方式研究进展

污染土壤电动修复是一项新兴的绿色原位修复技术.其原理是在土壤上施加直流电场,利用电迁移和电渗流去除污染物.电动修复的效率主要受到土壤pH、Zeta电位以及土壤化学性质等因素影响.在研究中使用的供能方式有两种控制电位法和控制电流法.这两种供能方式有不同特点和应用范围.控制电压法在理论模型、酸碱增强法以及阳离子膜增强修复方面有着广泛应用;控制电流法在计算目标污染物的迁移数、电渗析修复法以及难溶性重金属污染物的修复中得到应用.     

交换电极法强化电动修复铬污染土壤

pH值是影响污染土壤电动修复的主要因素。为此提出了交换电极法强化电动修复，并对该技术进行了实验研究。实验土壤Cr污染浓度为506.36 mg/kg，工作电压为1 V/cm，结果显示，固定电极方向运行模式下，运行2 d，产生聚焦效应，运行8 d，碱性区Cr(III)残留量和酸性区Cr(VI)残留量较大，分别是97.88 mg/kg和328 mg/kg，总铬去除率为59.04%。采用交换电极法，交换频率为4 d，运行8 d，总铬去除率为70.18%；交换频率为2 d，运行8 d，总铬去除率高达86.10%，土壤中总铬平均含量从506.36 mg/kg降至73.56 mg/kg，达到酸性土壤环境质量一级标准。该技术可控制土壤pH值在中性范围，电流密度高，不添加化学试剂，操作简单。     

高浓度铬污染土壤水浸泡与电动修复联合处理实验

对含铬量为2 142 mg/kg的铬污染土壤首先使用蒸馏水进行6轮浸泡试验,然后再进行电动修试验。土壤经过浸泡、通电24 h和72 h处理后总铬的去除率分别为:47%、61%和70%,表明预浸泡可以显著降低电动修复的负荷从而降低整个土壤修复费用。电动修复过程中对土壤两端的温度进行了测量以间接反映土壤电阻的分布和变化情况。结果显示土壤电阻逐渐上升,从阴极端开始逐渐过渡到阳极端,60 h之后达到最高值并保持稳定。电动修复的电流效率随土壤中铬浓度的降低而下降。此外,浸泡和电动修复均导致整个土壤和各断面铬浓度分布不均匀性增大。     

污染土壤电动修复增强方法研究进展

污染土壤电动修复是一项新兴绿色原位修复技术。其原理是在土壤上施加直流电场 ,利用电迁移和电渗去除污染物 ,土壤pH、Zeta电位以及土壤化学性质等因素影响电动修复效果。为了提高修复效率和扩大电动修复应用范围 ,现在已经发展了针对不同类型土壤和污染物的增强修复技术。本文归纳总结了 1995年以来土壤电动修复中常用增强处理效果的 8种方法 ,即酸碱中和法、阳离子选择膜法、电渗析法、络合剂法、表面活性剂法、氧化 还原法、EK 生物联用和LasagnaTM法 ,且对每种方法的典型实验装置、增强原理、方法特点和适用范围等进行了分析和讨论 ,为以后的实验设计提供了有益的参考     

酒石酸强化重金属复合污染模拟土壤电动修复过程及机理分析

为提高电动修复重金属复合污染土壤的效率,通过配制重金属复合污染模拟土壤,构建电动修复实验装置,利用2因素完全随机实验设计研究了酒石酸浓度和时间对重金属去除效果的影响;采用BCR法对土壤金属赋存形态进行了分析表征。结果表明:与对照相比,以酒石酸为电解液显著提高了重金属的去除率;重金属去除率受酒石酸浓度和修复时间影响显著;以0.05 mol·L~(-1)酒石酸为电解液修复120 h后,重金属去除效果最好,重金属总去除率为86.15%,Cu~(2+)、Mn~(2+)、Cd~(2+)、Pb~(2+)、Zn~(2+)的去除率分别为75.67%、98.11%、85.1%、70.75%和90.9%。BCR分析表明,酒石酸有助于提高土壤中弱酸提取态重金属含量,提高了重金属的迁移性能,从而有利于电动修复过程。     

均匀电场下多环芳烃在土壤中的迁移

当循环电解液流速为800 mL/h,电解液为无菌水时,电渗流流量、菲和芘在土壤中迁移量在电压梯度为1 V/cm作用下比电压梯度为0.5 V/cm时要多;电动注入表面活性剂Tween80和HPCD均可以提高菲和芘在土壤中的迁移,注入Tween80和HPCD浓度分别为500和1 000 mg/L时,相应地Phe提高5.8倍和11.7倍、芘提高2倍和3.4倍;而BaP在水中的溶解度太小,电场作用和电动注入表面活性剂对BaP在土壤中的迁移量影响很小。为建立电动修复有机污染物污染提供了技术基础。     

铜污染土壤电动修复研究

应用实验方法研究了土壤重金属污染的电动力学修复方法,分析了土壤重金属污染物的迁移和变化特征。实验结果表明,在电场作用下土壤中重金属的浓度分布发生明显变化,使得大部分重金属能在电极附近富集而被去除。当实验的电场强度为0.5 V/cm时,在阳极附近土壤中铜的去除效率达到71.1%。阳极附近的pH值由开始时的6.8逐渐变小到4.4,而阴极附近则相反,由开始时的6.6逐渐增大到9.1,此外电动修复过程中电极附近的温度会发生相应的变化。     

不同预处理对电镀污泥电动过程的影响

以风干电镀污泥为电动处理试验材料，水为阳极电解液，柠檬酸柠檬酸铵缓冲液为阴极电解液，施加25 V直流电压条件下电动运行5 d，研究了水、低浓度木钙和硝酸等预处理对电镀污泥电动过程的影响。结果表明，各处理的阴极电解液pH值变化平稳，都维持在3～3.5较理想的范围。而1％木钙、1％硝酸饱和预处理电镀污泥，明显改变了电动过程中电渗流和电流密度的大小，对电镀污泥Cu、Ni的去除率也有明显增加。其中，木钙、硝酸预处理后对Cu的去除率由对照的13.24％分别提高到19.05％和25.55％，即去除量分别增大3 516.35 mg/kg和7 457.62 mg/kg；木钙、硝酸预处理后对Ni的去除率由对照的14.68％分别提高到16.47％和28.85％，即去除量分别增大800.91 mg/kg和6 359.92 mg/kg。     

铜污染土壤电动修复研究

应用实验方法研究了土壤重金属污染的电动力学修复方法，分析了土壤重金属污染物的迁移和变化特征。实验结果表明，在电场作用下土壤中重金属的浓度分布发生明显变化，使得大部分重金属能在电极附近富集而被去除。当实验的电场强度为0.5 V/cm时，在阳极附近土壤中铜的去除效率达到71.1%。阳极附近的pH值由开始时的6.8逐渐变小到4.4，而阴极附近则相反，由开始时的6.6逐渐增大到9.1，此外电动修复过程中电极附近的温度会发生相应的变化。     

电催化氧化技术处理制革综合废水

选择DSA电极中的钛基掺硼金钢石膜电极(Ti/BDD),用于制革综合废水的电催化氧化处理研究,考察了在不同的电流密度、电压、电解质、pH值和电解时间等因素对COD去除率和电流效率的影响。结果表明,控制电流密度为30mA/cm2,电压为8.0 V,电解质(NaCl)浓度为2.0 g/L,pH为4.0,电催化氧化处理2 h后,废水的COD和NH4+-N的去除率分别达到了83.6%和90.3%,BOD/COD为0.45,比能耗为35.34 kWh/kg COD,电流效率为37%。     

热解吸对土壤中POPs农药的去除及土壤理化性质的影响

为探索土壤热解吸修复技术对POPs污染土壤的修复效果及修复后土壤可耕作性,选择北京某农药厂旧址的POPs农药污染土壤,研究了不同温度下热解吸处理后土壤中滴滴涕(DDTs)和六六六(HCHs)各组分的去除率以及土壤理化性质的变化。结果表明,热解吸修复技术可有效去除土壤中POPs农药,其中,p,p’-DDE与α-HCH组分去除率受热解吸温度的影响比其他组分更为明显。∑HCH与∑DDT在310℃、340℃时分别达到97%、99%的去除率,且此时土壤中的污染物含量低于我国《展览会用地土壤环境质量评价标准》,此后去除率受温度的影响不明显。热解吸温度对修复后土壤的理化性质有一定的影响,不同温度影响的程度各不相同,其中,有机质含量与全氮含量分别由0.78%、0.0352%降至0.14%、0.0107%;pH波动幅度较小,由7.80变至8.25;阳离子交换量变化存在波动,但呈整体下降趋势,由7.87 mg/kg降至5.00mg/kg;土壤中速效磷显著增加,由7.59 mg/kg升至21.8 mg/kg。而在最优温度条件下,土壤理化性质受热解吸温度的影响较小。由此可以说明,热解吸技术可以用于POPs污染土壤的修复,选择适当的热解吸温度对土壤的可耕作性影响有限,因而是一种潜在的绿色修复技术。     

EDTA-enhanced extraction of heavy metals from a coarse grained simulated soil by the CEHIXM process

The effect of ethylenediaminetetraacetic acid (EDTA) in extracting heavy metal contaminants, namely Pb, Cd, Zn, and Mn, from soils with organometallic complexes, was explored using the coupled electric-hydraulic gradient assisted by ion exchange medium (CEHIXM) decontamination process. The experiments were conducted with a constant electric voltage of 50 DC V and a constant hydraulic flow rate of 4 cm3/min. The results obtained from the experiments demonstrated that EDTA was effective in extracting Pb, Cd, Zn, and Mn from soils in which acidic pH did not produce significant dissolution. Metal removal as high as 99% was achieved with 0.05 M EDTA solution within 200 hr.     

Removal of PCBs from a Contaminated Soil Using CF-Systems® Solvent Extraction Process

ABSTRACT

The U.S. Environmental Protection Agency’s (EPA) Superfund Technical Assistance Response Team (START) in cooperation with EPA’s Superfund Innovative Technology Evaluation (SITE) program evaluated a pilot scale solvent extraction process developed by CF-Systems. This process uses liquefied propane to extract organic contaminants from soils, sludges, and sediments. A pilot-scale evaluation was conducted in Golden, CO at Hazen Research, Inc., using CF-Systems’ trailer-mounted organics extraction unit. Approximately 1,000 pounds of soil, with an average poly-chlorinated biphenyl (PCB) concentration of 260 mg/kg, was obtained from a remote Superfund site. Six 100-pound batches of the contaminated soil were extracted using multiple extraction sequences. Three of the six batch runs were subjected to three extraction sequences each, so that process variability could be evaluated. Results showed that PCB removal efficiencies varied between 91.4 and 99.4%, with the propane-extracted soils retaining low concentrations of PCBs (19.0–1.8 mg/kg). Removal efficiencies of oil and grease (O&G) were found to be 96.0 to 99.6% with propane-extracted soils retaining O&G concentrations from 279 to <20 mg/kg. Overall extraction efficiency was found to be dependant upon the numberof extraction cycles used.     

Removal of polycyclic aromatic hydrocarbons from manufactured gas plant-contaminated soils using sunflower oil: laboratory column experiments

Laboratory column experiments were performed to remove PAHs (polycyclic aromatic hydrocarbons) from two contaminated soils using sunflower oil. Two liters of sunflower oil was added to the top of the columns (33 cm x 21 cm) packed with 1 kg of PAH-contaminated soil. The sunflower oil was applied sequentially in two different ways, i.e. five additions of 400 ml or two additions of 1l. The influence of PAH concentration and the volume of sunflower oil on PAH removal were examined. A soil respiration experiment was carried out and organic carbon contents of the soils were measured to determine degradability of remaining sunflower oil in the soils. Results showed that the sunflower oil was effective in removing PAHs from the two soils, more PAHs were removed by adding sunflower oil in two steps than in five steps, probably because of the slower flow rate in the former method. More than 90% of total PAHs was removed from a heavily contaminated soil (with a total 13 PAH concentration of 4721 mg kg(-1)) using 4 l of sunflower oil. A similar removal efficiency was obtained for another contaminated soil (with a total 13 PAH concentration of 724 mg kg(-1)), while only 2l was needed to give a similar efficiency. Approximately 4-5% of the sunflower oil remained in the soils. Soil respiration curves showed that remaining sunflower oil was degraded by allowing air exchange and supplying with nutrients. Organic carbon content of the soil was restored to original level after 180 d incubation. These results indicated that the sunflower oil had a great capacity to remove PAHs from contaminated soils, and sunflower oil solubilization can be an alternative technique for remediation of PAH contaminated soils.     

动电修复不同形态重金属污染土壤效果研究

以钢铁厂附近废地的重金属土壤为对象,研究了动电修复技术去除重金属效果与其各化学形态的关系,讨论了电能消耗。结果表明,同一种重金属,其动电去除效率顺序为交换态碳酸盐结合态Fe-Mn氧化结合态有机结合态残留态,即吸附性越弱的形态,其去除率越高,如交换态去除率95%;吸附性越强的形态,其去除率越低,如有机态和残留态去除率低于29%;对于不同重金属,高移动性和弱吸附性的重金属较弱移动性和强吸附性的重金属去除效果好,即各形态的Cd、Cu和Zn的去除率明显高于相应形态Pb的去除率;能耗分析表明,实验时间超过96 h后,在电能有较大消耗的同时,重金属去除率却提高不明显。     

平板炭气凝胶电极电吸附除氟

采用自制的炭气凝胶平板电极进行模拟水样中氟的电吸附去除研究,通过单因子实验优化了该电吸附技术的操作参数和适用的溶液条件,并研究了反接电极法的再生效果。研究结果表明,自制的炭气凝胶平板由纳米颗粒组成三维网络结构,比表面积为670.90 m2/g,具有良好的充放电可逆性和迅速形成表面双电层的特点。静态电吸附除氟效果最佳的条件为:水样氟离子浓度6 mg/L,pH 7.0,极板间距4 cm,电压1.6 V;共存物质硝酸根、腐殖酸、碳酸根和碳酸氢根等对氟离子的电吸附具有一定的促进作用。吸附氟离子后的炭气凝胶材料的比表面、孔体积、电容值有所减小。对于吸附氟离子后的炭气凝胶平板电极,采用反接电极法取得较好再生效果的条件为:流动状态、电压1.6 V、极板间距4 cm。再生后的炭气凝胶电极与原始炭气凝胶相比,依然具有良好的充放电可逆性。     

脉冲电絮凝法处理黄连素废水

以Fe为电极,采用脉冲电絮凝法对实际黄连素制药废水进行处理。为了确定脉冲电絮凝法处理黄连素废水最优工艺条件,选择占空比、电流密度、脉冲频率、电极间距和pH等5个因素,开展了正交实验研究。对正交实验结果进行极差与方差分析,确定了各因素的显著性及优选条件。结果表明,各因素对废水COD去除率影响程度依次为:占空比>pH>电极间距>脉冲频率>电流密度;对黄连素去除率影响程度依次为:占空比>pH>电流密度>脉冲频率>电极间距。最优工艺条件为电极间距为1.5 cm,电流密度为16.7 mA/cm2(电流3.5 A,电压11.2 V),占空比为0.4,脉冲频率为0.1 kHz,pH为10,此时废水的COD与黄连素的去除率分别为61%与74%。     

Distribution and availability of arsenic in soils from the industrialized urban area of Beijing, China

Concentrations of arsenic (As) were determined in soils of 5 industrial sites in an urban area of Beijing, China. Fifty seven typical surface soils were sampled to determine total concentrations of metals, pH and dissolved organic carbon (DOC). One hundred and eight deep soils were submitted to a four-step, sequential extraction to assess the relative mobility and bioavailability of As in the soil profiles. Total concentrations of As in surface soils ranged from 5.7 to 2.3 x 10(1) mg kg(-1), dw with greater concentrations inside the perimeter of the chemical plant which had greater concentrations than did other plants. 75.4% of surface soil samples in the industrial area contained concentrations of As that were greater than was considered to be the background concentration of 7.8 mg kg(-1), dw for the region. The mean concentration (9.9 mg kg(-1), dw) in the industrial soils was greater than that soils from other type of land use. Concentrations of As were significantly and negatively correlated with soil pH and DOC in industrial soils. Although mean concentration of total As in the soils from all sites were less at greater depths, the entire range from 0 to 180 cm (especially 0-80 cm) contained concentrations of As that were greater than background. Sequential extractions of soil indicated that only some surface soils had relatively great amount of extractable fraction of As. Most soils had relatively great amount of residual As. This result suggests that most arsenic in Beijing industrial soils should be immobile and of limited bioavailability.