原位化学氧化法在土壤和地下水修复中的研究进展

综述了原位化学氧化法修复污染土壤及地下水的最新进展，着重介绍了几种氧化剂，如二氧化氯、双氧水及Fenton试剂、高锰酸钾和臭氧在土壤修复中的应用、不足及改进，并对化学氧化修复技术的发展前景进行了展望。     

污染土壤化学修复技术研究与进展

污染土壤修复环境工程近年来发展迅猛,欧美等发达国家在其技术创新和设备改进2个层面都取得了长足进展。本文概述了化学淋洗修复技术(原位化学修复技术和异位化学修复技术)、化学还原与还原脱氯修复技术、化学氧化修复技术、溶剂浸提技术和土壤性能化学改良修复技术等污染土壤的化学修复技术原理、进展与适用性以及有关关键技术参数,并对其发展前景进行了展望。     

污染土壤化学修复技术研究与进展

污染土壤修复环境工程近年来发展迅猛，欧美等发达国家在其技术创新和设备改进2个层面都取得了长足进展。本文概述了化学淋洗修复技术（原位化学修复技术和异位化学修复技术）、化学还原与还原脱氯修复技术、化学氧化修复技术、溶剂浸提技术和土壤性能化学改良修复技术等污染土壤的化学修复技术原理、进展与适用性以及有关关键技术参数，并对其发展前景进行了展望。     

异位类Fenton化学氧化在多环芳烃污染场地修复中的应用

多环芳烃作为土壤的主要污染源之一,其修复技术的研究对土壤可持续利用具有重要的意义;但目前的研究主要基于室内小试实验,对具体修复技术在实际现场中的应用少有报道。基于上海青浦区西虹桥沈海高速东侧17-02污染场地的工程实践,结合室内实验,详细地介绍了原场异位类Fenton化学氧化修复多环芳烃污染土壤施工工艺。处理结果表明:以柠檬酸为催化助剂的类Fenton化学氧化能够有效地处理场地污染土壤中的苯并(a)蒽、苯并(a)芘、苯并(b)荧蒽和茚并(1, 2, 3-cd)芘等超标污染物;修复后场地土壤各项物理指标相比修复前变化较小;同时,类Fenton氧化反应放热,修复过程中土壤微生物能够将有机柠檬酸快速降解,有效降低了化学氧化对土壤p H的影响。     

土壤及地下水有机污染的化学与生物修复

本文综述了土壤及地下水有机污染的化学与生物修复技术研究的最新进展。比较详细地介绍了土壤及地下水有机污染的化学修复、生物修复、化学与生物相结合修复的具体方法、治理效率及其影响因素。     

我国有机物污染场地土壤修复技术的专利计量分析

以我国公开的691项有机物污染场地土壤修复技术专利为依据,分析研究了有机物污染场地土壤修复技术的发展趋势和进展,同时对化学氧化修复技术、生物修复技术、热脱附技术、淋洗技术等的研究进展进行分析,总结了目前国内有机物污染场地修复专利技术发展现状,并提出了今后的发展方向,以期为我国今后开展相关修复技术的研究与应用提供参考。结果显示:我国有机物污染场地土壤修复技术相关专利于2010年后开始快速发展,研究创新点基本集中于高效技术的开发、节能以及二次污染的防治;热脱附技术在该领域应用广泛;氧化修复技术的开发是2017年的技术发展特点,具有一定的研究前景;而联合多种修复技术更能灵活地适用于实际场地修复的需要,其已成为重要的研究趋势。     

化学预氧化-生物强化-生物刺激对土壤中菲降解的联合效应

通过室内实验,探究了低浓度过硫酸盐预氧化耦合生物强化或生物刺激技术处理下土壤中菲的降解率和修复效应。结果表明,浓度为0.1 mmol·g~(-1)、温度为50℃热活化的过硫酸钠对土壤中菲7 d的降解率为22.7%。预氧化后,加入高效降解菌和营养物质,强化微生物对菲的降解,继续培育21 d,最终降解率较第7天可提高8.08%～18.59%。同时添加高效降解菌和营养物质N,对土壤中菲的降解促进作用最强,最终降解率可达41.29%,较仅进行化学氧化的对照组和仅进行微生物降解的对照组分别提高17.44%和22.86%,较预氧化后不进行微生物强化的对照组提高12.9%。降解期间,土壤微生物数量和pH呈先下降,后上升趋势,最终维持在相对稳定水平。相关性分析结果表明,土壤中菲的降解率与氧化剂和营养物质N的添加呈显著正相关,土壤微生物数量与pH呈正相关,与氧化剂呈负相关,土壤pH与氧化剂及营养物质P呈负相关。研究结果证实了化学预氧化耦合生物强化和生物刺激技术能有效促进微生物对菲污染土壤的修复。     

水力压裂结合化学氧化法修复多环芳烃污染的低渗土壤

渗透性较低的污染土壤,由于氧化剂在土壤中传质受阻,导致修复效果较差。采用水力压裂结合化学氧化法探究了不同水力压裂工艺参数对土柱渗透系数和压裂效果的影响,并比较了H₂O₂、KMnO₄和活化过硫酸钠3种氧化剂对菲和芘两种多环芳烃(PAHs)的去除效果。结果表明：当压裂液注入流量为347.3 L/h、压裂液黏度为294 mPa·s、土柱含水率为20.0%、注入方式为间歇注入时,土柱渗透系数和压裂效果最佳。添加2.5 mmol/g的活化过硫酸钠对菲和芘的去除最经济高效。在最佳水力压裂条件下进行化学氧化,与无水力压裂时相比,菲和芘的去除率分别提高19.2、21.2百分点,说明水力压裂可有效增强化学氧化法对PAHs污染的低渗土壤的修复效果。     

磷矿粉修复重金属污染土壤的研究进展

重金属污染土壤的化学钝化修复技术可以有效控制重金属对植物及环境的危害。不同的改良剂对重金属污染土壤的改良效果不同,已有的研究表明难溶性磷矿粉是较好的选择。磷矿粉是一种性价比很高的改良剂,而且不会对环境造成破坏。总结了磷矿粉修复重金属污染土壤的化学机制和影响因素,重点综述了近年来不同粒径磷矿粉、改性磷矿粉修复重金属污染土壤的研究进展,旨在为重金属污染土壤的修复研究提供参考。     

上海市某污染场地土壤异位化学氧化修复方案设计

上海市某钢材剪切厂生产过程中机油泄漏等原因导致遗留场地被石油烃(C10～C40)和苯并(a)芘污染.在对场地开展污染状况调查和风险评估的基础上,确定了场地修复工程量和修复方案.采用过硫酸盐氧化+生石灰活化的异位化学氧化技术对污染场地土壤进行修复,确定过硫酸钠和生石灰的添加量都为1.5％(质量分数),根据实际情况控制在1...     

A rapid spectrophotometric determination of persulfate anion in ISCO

Due to a gradual increase in the use of persulfate as an in situ chemical oxidation (ISCO) oxidant, a simple measurement of persulfate concentration is desirable to analyze persulfate distribution at designated time intervals on/off a site. Such a distribution helps evaluate efficacy of ISCO treatment at a site. This work proposes a spectrophotometric determination of persulfate based on modification of the iodometric titration method. The analysis of absorption spectra of a yellow color solution resulting from the reaction of persulfate and iodide in the presence of sodium bicarbonate reveals an absorbance at 352 nm, without significant interferences from the reagent matrix. The calibration graph was linear in the range of persulfate solution concentration of 0-70 mM at 352 nm. The proposed method is validated by the iodometric titration method. The solution pH was at near neutral and the presence of iron activator does not interfere with the absorption measurement. Also, analysis of persulfate in a groundwater sample using the proposed method indicates a good agreement with measurements by the titration method. This proposed spectrophotometric quantification of persulfate provides a simple and rapid method for evaluation of ISCO effectiveness at a remediation site.     

Impact of injection system design on ISCO performance with permanganate--mathematical modeling results

In situ chemical oxidation (ISCO) using permanganate (MnO(4)(-)) can be a very effective technique for remediation of soil and groundwater contaminated with chlorinated solvents. However, many ISCO projects are less effective than desired because of poor delivery of the chemical reagents to the treatment zone. In this work, the numerical model RT3D was modified and applied to evaluate the effect of aquifer characteristics and injection system design on contact and treatment efficiency. MnO(4)(-) consumption was simulated assuming the natural oxidant demand (NOD) is composed of a fraction that reacts instantaneously and a fraction that slowly reacts following a 2nd order relationship where NOD consumption rate increases with increasing MnO(4)(-) concentration. MnO(4)(-) consumption by the contaminant was simulated as an instantaneous reaction. Simulation results indicate that the mass of permanganate and volume of water injected has the greatest impact on aquifer contact efficiency and contaminant treatment efficiency. Several small injection events are not expected to increase contact efficiency compared to a single large injection event, and can increase the amount of un-reacted MnO(4)(-) released down-gradient. High groundwater flow velocities can increase the fraction of aquifer contacted. Initial contaminant concentration and contaminant retardation factor have only a minor impact on volume contact efficiency. Aquifer heterogeneity can have both positive and negative impacts on remediation system performance, depending on the injection system design.     

In situ iron activated persulfate oxidative fluid sparging treatment of TCE contamination--a proof of concept study

In situ chemical oxidation (ISCO) is considered a reliable technology to treat groundwater contaminated with high concentrations of organic contaminants. An ISCO oxidant, persulfate anion (S(2)O(8)(2-)) can be activated by ferrous ion (Fe(2+)) to generate sulfate radicals (E(o)=2.6 V), which are capable of destroying trichloroethylene (TCE). The property of polarity inhibits S(2)O(8)(2-) or sulfate radical (SO(4)(-)) from effectively oxidizing separate phase TCE, a dense non-aqueous phase liquid (DNAPL). Thus the oxidation primarily takes place in the aqueous phase where TCE is dissolved. A bench column study was conducted to demonstrate a conceptual remediation method by flushing either S(2)O(8)(2-) or Fe(2+) through a soil column, where the TCE DNAPL was present, and passing the dissolved mixture through either a Fe(2+) or S(2)O(8)(2-) fluid sparging curtain. Also, the effect of a solubility enhancing chemical, hydroxypropyl-beta-cyclodextrin (HPCD), was tested to evaluate its ability to increase the aqueous TCE concentration. Both flushing arrangements may result in similar TCE degradation efficiencies of 35% to 42% estimated by the ratio of TCE degraded/(TCE degraded+TCE remained in effluent) and degradation byproduct chloride generation rates of 4.9 to 7.6 mg Cl(-) per soil column pore volume. The addition of HPCD did greatly increase the aqueous TCE concentration. However, the TCE degradation efficiency decreased because the TCE degradation was a lower percentage of the relatively greater amount of dissolved TCE by HPCD. This conceptual treatment may serve as a reference for potential on-site application.     

Characteristics and applications of controlled-release KMnO4 for groundwater remediation

In situ chemical oxidation (ISCO) using potassium permanganate (KMnO4) has been widely used as a practical approach for remediation of groundwater contaminated by chlorinated solvents like trichloroethylene. The most common applications are active flushing schemes, which target the destruction of some contaminant source by injecting concentrated permanganate (MnO4(-)) solution into the subsurface over a short period of time. Despite many promising results, KMnO4 flushing is often frustrated by inefficiency associated with pore plugging by MnO2 and bypassing. Opportunities exist for the development of new ISCO systems based on KMnO4. The new scheme described in this paper uses controlled-release KMnO4 (CRP) as an active component in the well-based reactive barrier system. This scheme operates to control spreading of a dissolved contaminant plume. Prototype CRP was manufactured by dispersing fine KMnO4 granules in liquid crystal polymer resin matrix. Scanning electron microscope data verified the formation of micro-scale (ID=20-200 microm) secondary capillary permeability through which MnO4(-) is released by a reaction-diffusion process. Column and numerical simulation data indicated that the CRP could deliver MnO4(-) in a controlled manner for several years without replenishment. A proof-of-concept flow-tank experiment and model simulations suggested that the CRP scheme could potentially be developed as a practical approach for in situ remediation of contaminated aquifers. This scheme may be suitable for remediation of sites where accessibility is limited or some low-concentration contaminant plume is extensive. Development of delivery systems that can facilitate lateral spreading and mixing of MnO4(-) with the contaminant plume is warranted.     

Coupling permanganate oxidation with microbial dechlorination of tetrachloroethene.

For sites contaminated with chloroethene non-aqueous-phase liquids, designing a remediation system that couples in situ chemical oxidation (ISCO) with potassium permanganate (KMnO4) and microbial dechlorination may be complicated because of the potentially adverse effects of ISCO on anaerobic bioremediation processes. Therefore, one-dimensional column studies were conducted to understand the effect of permanganate oxidation on tetrachloroethene (PCE) dechlorination by the anaerobic mixed culture KB-1. Following the confirmation of PCE dechlorination, KMnO4 was applied to all columns at a range of concentrations and application velocities to simulate varied distances from oxidant injection. Immediately following oxidation, reductive dechlorination was inhibited; however, after passing several pore volumes of sterile growth medium through the columns after oxidation, a rebound of PCE dechlorination activity was observed in every inoculated column without the need to reinoculate. The volume of medium required for a rebound of dechlorination activity differed from 1.1 to 8.1 pore volumes (at a groundwater velocity of 4 cm/d), depending on the specific condition of oxidant application.     

Hydrogen peroxide stabilization in one-dimensional flow columns

Rapid hydrogen peroxide decomposition is the primary limitation of catalyzed H(2)O(2) propagations in situ chemical oxidation (CHP ISCO) remediation of the subsurface. Two stabilizers of hydrogen peroxide, citrate and phytate, were investigated for their effectiveness in one-dimensional columns of iron oxide-coated and manganese oxide-coated sand. Hydrogen peroxide (5%) with and without 25 mM citrate or phytate was applied to the columns and samples were collected at 8 ports spaced 13 cm apart. Citrate was not an effective stabilizer for hydrogen peroxide in iron-coated sand; however, phytate was highly effective, increasing hydrogen peroxide residuals two orders of magnitude over unstabilized hydrogen peroxide. Both citrate and phytate were effective stabilizers for manganese-coated sand, increasing hydrogen peroxide residuals by four-fold over unstabilized hydrogen peroxide. Phytate and citrate did not degrade and were not retarded in the sand columns; furthermore, the addition of the stabilizers increased column flow rates relative to unstabilized columns. These results demonstrate that citrate and phytate are effective stabilizers of hydrogen peroxide under the dynamic conditions of one-dimensional columns, and suggest that citrate and phytate can be added to hydrogen peroxide before injection to the subsurface as an effective means for increasing the radius of influence of CHP ISCO.     

中国土壤环境污染态势及预防、控制和修复策略

在综述中国土壤环境污染态势及成因的基础上,提出了土壤环境污染的预防、控制和修复策略.指出了当前中国土壤环境污染态势严峻,表现出土壤污染范围在扩大,污染物种类在增多,出现了复合型、混合型的高风险污染区,呈现出从污灌型向与大气沉降型并重转变、城郊向农村延伸、局部向区域蔓延的趋势;体现出土壤污染与土壤酸化的叠加、多种传统污染物与新兴污染物相互混合的态势,危及粮食生产、食物质量、生态安全、人体健康以及区域可持续发展.认为以预防为主,预防、控制和修复相结合是中国在相当长时期内的土壤环境保护策略;土壤污染预防需要法律法规、评价标准、管理政策和公众参与,土壤污染控制需要发展物化控制、生物学控制及其协同控制技术,土壤污染修复需要研发工程修复技术、材料、产品与设备,建立技术规范、评价标准和管理体系,推动市场化和产业化发展.     

污染土壤修复效果评定方法的研究

在实施污染土壤修复的环境工程后，需要通过灵敏和有效的评定方法对污染土壤修复的效果进行评定。然而，单纯依靠化学方法进行污染土壤修复效果的评定，不能揭示土壤的整体质量特征，因此需要生态毒理方法作为相互补充的手段。本文概述了植物毒性评定法、陆生无脊椎动物评定法和土壤微生物评定法及其在污染土壤修复效果评定中的应用，并对污染土壤修复效果评定方法的发展前景进行展望。     

Soil remediation techniques at uncontrolled hazardous waste sites. A critical review

The objective of this critical review is to address soil remediation techniques at uncontrolled hazardous waste sites with regard to the following areas: 1) important regulatory and technical issues and information needs concerning soil remediation at uncontrolled hazardous waste sites; 2) approaches for selection of remediation techniques; and 3) the current state of knowledge regarding soil remediation techniques, including applications and limitations. The areas identified above are addressed with regard to current information, selected milestone publications, and specific applications of technologies to provide a synthesis of the topic. The information concerning current issues, approaches, and soil remediation techniques presented was critically reviewed in order to: 1) identify deficiencies in current approaches; 2) develop a conceptual framework for remediation; and 3) recommend improved approaches for selection of remediation technologies.     

污染土壤修复效果评定方法的研究

在实施污染土壤修复的环境工程后,需要通过灵敏和有效的评定方法对污染土壤修复的效果进行评定.然而,单纯依靠化学方法进行污染土壤修复效果的评定,不能揭示土壤的整体质量特征,因此需要生态毒理方法作为相互补充的手段.本文概述了植物毒性评定法、陆生无脊椎动物评定法和土壤微生物评定法及其在污染土壤修复效果评定中的应用,并对污染土壤修复效果评定方法的发展前景进行展望.