土壤和地下水污染的监控自然衰减修复技术研究进展

我国土壤和地下水污染形势严峻,污染场地数量巨大、类型复杂,相应的管理和修复技术体系仍然滞后.监控自然衰减（MNA）作为一种基于污染风险管控的场地修复和长期监测方法,是土壤和地下水污染修复中较为经济和有效的方法之一,可以实现修复的成本效益最大化.近几年来MNA在美国污染场地修复中的应用比例约占30%左右,场地修复的平均成本为数十万美元.本文介绍了MNA方法的来源和发展,总结了MNA的国内外研究应用进展和相关的核心技术手段,与典型修复方法的成本进行了比较,以期为MNA相关的研究和应用提供参考借鉴.     

硫化纳米铁反应带修复硝基苯污染地下水

采用前置硫化合成法制备硫化纳米铁（S-NZVI）并进行表征,采用模拟砂柱创建S-NZVI原位反应带,研究其对硝基苯（NB）污染地下水的修复效能.X射线衍射（XRD）、X射线光电子能谱（XPS）、透射电子显微镜（TEM）表征结果表明,S-NZVI是以Fe（0）为核心,硫铁化合物为外壳的颗粒,可以有效抑制S-NZVI颗粒的团聚,具有较好的分散性.与NZVI相比,S-NZVI对NB的去除效率更高,最高去除率可达99.65%,在砂柱中具有更强的穿透能力.S-NZVI对NB的去除过程符合准一级动力学模式.S-NZVI对NB的去除机理是先将NB快速吸附于表面,然后再进一步通过化学还原降解,因此NB去除较快而苯胺生成较慢.S-NZVI反应带对NB泄露区的削减幅度较大,增加单井S-NZVI注入量和增加注入井均可提高修复效果,7d内NB累计去除率最高达87.43%,但前2d出水NB浓度仍然较高;S-NZVI反应带对NB传输区具有较好的修复效果,增加注入井比增加单井S-NZVI注入量具有更好的持续性和更高的NB去除率,7d内NB累计去除率最高达99.90%.     

热修复过程中重质非水相液体(DNAPL)共沸实验

本研究开展单组分和多组分DNAPL加热实验,旨在建立热处理过程中温度与DNAPL去除之间的联系.结果表明,单组分DNAPL实验中可以观察到明显的共沸温度平台,而多组分DNAPL实验则是一段温度逐渐上升的共沸区域,两组实验中共沸时间均与初始DNAPL饱和度呈正相关.仅根据局部温度数据判断热修复进程可能会导致错误的结论,当温度结果显示共沸结束后,体系内仍残留有饱和度0.94%~1.60%的DNAPL.温度数据会受到DNAPL组成和温度监测点位置影响,它通常仅能反映局部加热情况,修复时可结合气体和土壤样品中污染物组分变化情况辅助判断修复进程.     

污染场地土壤气被动采样技术研究进展

在VOCs（挥发性有机物）污染场地调查中,土壤气采样的重要性日益受到重视.常规的土壤气采样主要依赖吸附管和采样罐等主动采样方法,但主动采样有很多缺点.作为一种新兴的采样技术,被动采样具有成本低、操作简单、更能代表长时间人体暴露、可用于低渗透性地层等优点,已经成为污染场地调查领域的研究热点.对被动采样的理论基础、采样器类型、吸附剂类型、采样误差的来源进行了介绍,对土壤气被动采样中存在的技术难题以及前沿研究方向进行了讨论,并对该技术在我国场地调查领域的应用前景进行了展望和建议.结果表明:在被动采样中准确控制采样器的采样速率（uptake rate）是保证其定量能力的关键,当控制采样速率低于土壤气中VOCs的补给速率时,可以实现良好的定量效果.影响采样速率的主要因素包括待测VOCs的性质、吸附剂种类、采样器结构以及各类环境因素,挥发性强的VOCs较难被捕集且容易发生逃逸.不同被动采样器用于不同种类VOCs采样时的采样速率可以相差6个数量级,从最低的0.005 5 mL/min到最高的125 mL/min.因此,建议在实际采样中应选用结构合理的采样器,控制采样速率不宜过大,以降低饥饿效应的产生;应选用与待测物匹配的吸附剂,对待测物兼具良好的保留能力和脱附能力;应加强环境因素（温度、湿度、土壤性质）对采样速率影响机制及场地校准方法的研究;应该结合研究和实践经验制定符合我国国情的土壤气被动采样技术指南.      

Residual effects of tobacco biochar along with different fixing agents on stabilization of trace elements in multi-metal contaminated soils

The residual effect of tobacco biochar(TB ≥ 500°C) mono and co-application with Cahydroxide(CH),Ca-bentonite(CB) and natural zeolite(NZ) on the bio-availability of trace elements TE(s) in alkaline soils has not been deeply studied yet.A pot study that had earlier been investigated TB mono and blended with CH,CB and NZ on the immobilization of Pb,Cu Cd,and Zn by Chinese cabbage.Maize crop in the rotation was selected as test plant to assess the residual impact of amendments on stabilization of Pb,Cu Cd,and Zn in mine polluted(M-P),smelter heavily and low polluted(S-HP and S-LP,respectively) soils.The obtained results showed that stabilization of Pb,Cd,Cu and Zn reached 63.84% with TB + CB,61.19% with TB + CH,83.31% with TB + CH and 35.27% with TB + CH for M-P soil,36.46% with TB + NZ,38.46% with TB + NZ,19.40% with TB + CH and 62.43% with TB + CH for S-LP soil,52.94% TB + NZ,57.65% with TB + NZ,52.94% with TB + NZ,and 28.44% with TB + CH for S-LP soil.Conversely,TB + CH and TB alone had mobilized Pb and Zn up to19.29% and 34.96% in M-P soil.The mobility of Zn reached 8.38% with TB + CB and 66.03%with TB for S-HP and S-LP soils.The uptake and accumulation of Pb,Cd,Cu and Zn in shoot and root were reduced in three polluted soils.Overall,the combination of TB along with CH,CB and NZ has been proven to be effective in Pb,Cd,Cu and Zn polluted mine/smelter soils restoration.     

市政污泥堆肥对矿山废弃地生态恢复影响的研究进展

市政污泥作为城市污水处理过程中的副产物,含有大量的有机质和丰富的氮、磷、钾等营养物质,经堆肥处理后可用作矿山废弃地生态恢复的土壤改良基质.已有实验室模拟和场地规模研究结果表明,污泥堆肥的施用可同步实现矿山废弃地土壤基本理化性质改善、土壤微生物数量和代谢活性提高、植被的快速生长和生态功能的快速重建.污泥堆肥所含的氮、磷、有机质和重金属,在降雨渗流、微生物和植物根系的共同作用下淋溶进入水体或被植物富集,已有淋滤柱试验和短期植物种植研究结果表明,矿山有短期的二次污染风险,但风险可控.国外污泥/污泥堆肥用于矿山生态修复的案例证明,市政污泥经稳定化处理可促进矿山生态恢复,形成有效碳汇,而长期生态影响未来需要开展不同地域的场地跟踪监测并进行系统定量评估,从而进一步探讨该技术路线的可行性和安全性,同步实现市政污泥处理处置和矿山废弃地生态修复的双重目标,这也将成为未来评估市政污泥堆肥用于矿山生态恢复可行性的重要研究方向.      

DISSOLVED HEAVY METALS IN SHALLOW GROUND WATER IN A SOUTHEASTERN MICHIGAN URBAN WATERSHED1

ABSTRACT: The occurrence of dissolved heavy metal concentrations in shallow ground water were measured at 126 sites within an urban watershed in southeastern Michigan. A total of 1,140 samples were collected from the first saturated zone, and the mean concentrations of 11 heavy metals (arsenic, barium, cadmium, chromium, copper, lead, mercury, nickel, selenium, silver, and zinc) were obtained and compared to their corresponding mean concentrations within surface soil. The results suggest that former and current land use processes have resulted in significant adverse impacts on the study region. Levels of Cr 20 to 30 times the maximum contaminant level (MCL) have been detected in the ground water beneath industrial sites. In addition, Cd and Pb have been found at levels exceeding their MCLs where surface soils are clay‐rich, and in sandy soils at more than 10 times their MCLs. The high levels of Cr in ground water strongly suggest that the chromium is in a hexavalent form, and this likelihood is supported by current studies. Given the hydraulic connection between the watershed's surface waters and the Great Lakes, these findings raise significant ecological and public health concerns.     

Optimum Dose Of Lime And Fly Ash For Treatment Of Hexavalent Chromium–Contaminated Soil

The presence of hexavalent chromium, Cr(VI), in soil is an environmental concern due to its effect on human health. The concern arises from the leaching and the seepage of Cr(VI) from soil to groundwater. In this paper, a stabilization technology to prevent this problem was simulated on an artificial soil contaminated with hexavalent chromium. The process is a physico-chemical treatment in which the toxic pollutant is physically entrapped within a solid matrix formed by the pozzolanic reactions of lime and fly ash to reduce its leachability and, therefore, its toxicity. This paper presents the optimum ratio of fly ash and lime in order to stabilize artificial soils contaminated with 0.4 wt.% of Cr (VI) in a brief term process. The degree of chromium released from the soil was evaluated using a modified Toxicity Characteristic Leaching Procedure (TCLP) by US Environmental Protection Agency (EPA). Overall, experimental results showed reduced leachability of total and hexavalent chromium from soils treated with both fly ash and quicklime, and that leachability reduction was more effective with increasing amount of fly ash and quicklime. Stabilization percentages between 97.3% and 99.7% of the initial chromium content were achieved, with Cr(VI) concentration in the TCLP leachates below the US EPA limit for chromium of 5 mg/l. Adequate treatment was obtained after 1 day of curing with just 25% fly ash and 10% quicklime.     

内酯型槐糖脂修复石油污染土壤的影响因素

采用内酯型槐糖脂(SL50)修复石油污染土壤。通过单因子实验与正交实验,考察了槐糖脂溶液质量浓度、振荡时间、反应体系初始pH、NaCl加入量以及固液比(土壤质量与表面活性剂溶液体积之比)对污染土壤石油烃洗脱率的影响。单因子模型回归分析结果表明,参数变量均符合二次拟合模型,槐糖脂溶液质量浓度、反应体系初始pH以及NaCl加入量的二次模型拟合效果较好。正交实验结果表明,槐糖脂溶液质量浓度和反应体系初始pH是该实验的敏感性因子,最优洗脱条件为槐糖脂溶液质量浓度40 mg/L、反应体系初始pH 9、NaCl加入量6%(w)。     

Bioremediation of Chlorobenzene-Contaminated Groundwater on Granular Activated Carbon Barriers

During the past decade, various promising technologies have been developed for the decontamination of groundwater insitu which do not require long-term pumping or high energy consumption. One approach is to use funnel and gate technology. In the case described here, the combination of adsorption of contaminants on granular activated carbon (GAC) and its biodegradation is applied to considerably extend the operating time of the filling material in the barrier system. Monochlorobenzene (MCB), a recalcitrant groundwater contaminant under anaerobic conditions, undergoes high-capacity adsorption on GAC up to about 450 mg per gram. Aerobic enrichment cultures, obtained from a contaminated aquifer, were able to mineralize initially adsorbed MCB. In respirometer experiments the rate of carbon dioxide formation was dependent on the equilibrium concentration of MCB. The oxygen consumption of activated carbon by means of autoxidative reactions may delay aerobic biodegradation in GAC filters. The oxygen uptake of pristine activated carbon amounted to 5.6 mg per gram GAC in laboratory column experiments. When GAC was pre-loaded with MCB, autoxidation rates were considerably reduced. Hence, it is advisable not to stimulate the biodegradation of MCB by oxygen supply in GAC biobarriers until after an initial period of solely sorptive MCB removal from the groundwater flow.