农田重金属污染原位钝化修复研究进展

污染土壤重金属原位钝化修复是通过向土壤中施加一些活性钝化修复材料,通过溶解沉淀、离子交换吸附、氧化还原、有机络合等反应来改变重金属在土壤中的赋存状态,降低土壤中重金属的有效浓度、迁移性和生物有效性。这种方法成本较低、操作简单、见效快且适合大面积推广,在重金属污染土壤修复中有着不可替代的作用。尤其对主要由污水灌溉、大气沉降等造成的农田土壤面源污染,一些具有吸附固定土壤中重金属离子特性的天然物质和工业副产品都可运用在实地的钝化修复中,且不同类型的钝化修复剂对重金属污染土壤的钝化修复效果各不相同。采用实验室评价和实地应用评价,一方面可以评估钝化修复材料对污染土壤中重金属离子的固定效率;另一方面可以评估钝化修复材料对土壤理化性状、养分状况和生物活性的影响。对重金属污染土壤原位钝化修复中不同来源的钝化剂进行了分类,目前广泛使用的钝化修复剂主要包括硅钙物质、含磷材料、有机物料、黏土矿物、金属及金属氧化物、生物碳及新型材料等,概述了它们各自对重金属污染土壤的钝化修复效果。从研究方法、评价指标、环境影响因子、钝化机制以及环境风险评价等方面分析了该领域的研究现状以及存在的主要问题,今后应重点关注钝化修复剂对土壤-作物系统的潜在环境风险以及钝化材料修复效果的田间长期稳定性评价。     

Remediation of soil and groundwater contaminated with organic chemicals using stabilized nanoparticles: Lessons from the past two decades

▪ Overviewed evolution and environmental applications of stabilized nanoparticles. ▪ Reviewed theories on particle stabilization for enhanced reactivity/deliverability. ▪ Examined various in situ remediation technologies based on stabilized nanoparticles. ▪ Summarized knowledge on transport of stabilized nanoparticles in porous media. ▪ Identified key knowledge gaps and future research needs on stabilized nanoparticles. Due to improved soil deliverability and high reactivity, stabilized nanoparticles have been studied for nearly two decades for in situ remediation of soil and groundwater contaminated with organic pollutants. While large amounts of bench- and field-scale experimental data have demonstrated the potential of the innovative technology, extensive research results have also unveiled various merits and constraints associated different soil characteristics, types of nanoparticles and particle stabilization techniques. Overall, this work aims to critically overview the fundamental principles on particle stabilization, and the evolution and some recent developments of stabilized nanoparticles for degradation of organic contaminants in soil and groundwater. The specific objectives are to: 1) overview fundamental mechanisms in nanoparticle stabilization; 2) summarize key applications of stabilized nanoparticles for in situ remediation of soil and groundwater contaminated by legacy and emerging organic chemicals; 3) update the latest knowledge on the transport and fate of stabilized nanoparticles; 4) examine the merits and constraints of stabilized nanoparticles in environmental remediation applications; and 5) identify the knowledge gaps and future research needs pertaining to stabilized nanoparticles for remediation of contaminated soil and groundwater. Per instructions of this invited special issue, this review is focused on contributions from our group (one of the pioneers in the subject field), which, however, is supplemented by important relevant works by others. The knowledge gained is expected to further advance the science and technology in the environmental applications of stabilized nanoparticles.     

农田土壤重金属污染状况及修复技术研究

重金属污染因具有毒性、易通过食物链在植物,动物和人体内累积,对生态环境和人体健康构成严重威胁。随着工业快速发展、农药及化肥的广泛使用,农田土壤重金属污染越来越严重,研究农田土壤重金属污染现状及修复技术对农产品安全具有重要意义。综合国内外农田土壤重金属污染状况,农田土壤重金属污染主要来源于固体废弃物堆放及处置、工业废物大气沉降、污水农灌和农用物质的不合理施用。该文综述了国内外有关农田重金属污染土壤修复技术（物理修复、化学修复、生物修复、农业生态和联合修复）的研究进展,并针对各种修复方法,阐述了其原理、修复条件、应用实例及其优缺点,重点论述了植物修复的机理和应用,提出了草本与木本联合修复可有效提高农田土壤重金属复合污染的修复效率,为农田土壤土壤重金属复合污染修复提出了新的途径。最后在对已有研究分析的基础上,提出了联合修复技术（如生物联合技术、物理化学联合技术和物理化学-生物联合技术）可以在一定程度上克服使用单一修复手段存在的缺点,可提高复合污染的修复效率、降低修复成本,未来应深入探索联合修复技术间的相互作用机理,以期为农田土壤重金属综合治理与污染修复提供科学依据。     

Stabilization treatment of contaminated soil: a field-scale application in Shanghai,China

Stabilization is one of the best demonstrated available technologies for treating toxic pollutants in soils and has been used worldwide but is rarely used for treatment of contaminated sites in China despite many bench-scale studies. Here, a field-scale application of stabilization treatment in Shanghai, China was summarized to demonstrate the whole engineering process and the key technical issues regarding stabilization of contaminated soil. A site contaminated with arsenic (As) and polycyclic aromatic hydrocarbons (PAHs), formerly used as a lighting plant in Shanghai, was chosen as the demonstration site. Stabilizing measures were taken to treat the contaminated soil to reuse the site for residential purposes. The whole engineering remediation process consisted of phase I environmental site assessment (ESA) and phase II ESA, quantitative human health risk assessment, remediation alternatives evaluation, bench-scale testing, remedial design, engineering implementation, and post-remediation assessment. A third party conducted evaluation monitoring indicated desirable results were achieved via the stabilization treatment. In addition, some technical obstacles related to soil stabilization treatment were discussed, including soil quality evaluation, stabilization effectiveness validation, and soil reuse assessment.     

污染土壤的修复技术研究进展

分析了当前我国严峻的土壤环境状况，并从重金属和有机污染物两个方面，全面介绍了当前污染土壤的各种修复技术，包括物理化学修复方法、植物修复方法和微生物修复方法等；对各种方法的修复原理、已取得的研究进展、存在的优缺点及其将来的发展趋势进行了较全面的综述和展望。文章认为，污染土壤修复将是一项非常具有挑战性同时又是一项非常有前途的修复技术，将会对人类健康和经济可持续发展发挥重要作用。     

草灌混播在边坡绿化防护中的应用

边坡绿化防护是对人工开挖建设形成的各种坡面进行生态修复以及防止水土流失的一项重要措施。草、灌木混播应用于边坡防护与修复,较之于单一的草被措施,更有利于形成立体的、多样的植被结构,对边坡的稳定和美化有更好的效果。     

土壤原位修复技术研究与应用进展

土壤原位修复技术是指不经挖掘,直接在污染场地就地修复污染土壤的土壤修复技术,具有投资低,对周边环境影响小的特点,是土壤修复的研究热点。土壤原位修复技术主要有淋洗,气相抽提（SVE）,多相抽提（MPVE）,气相喷射（IAS）,生物降解,原位化学氧化（ISCO）,原位化学还原,污染物固定,植物修复等。淋洗法主要用于治理高渗透性土壤中的重金属和难挥发降解的有机物。土壤气相抽提和喷射技术适用于处理土壤中的易挥发污染物,并有常与加热技术,生物处理技术等联用,可以起到促进污染物挥发,增氧促分解的作用。多相抽提法主要用于治理存在大量非水相流体的污染场地,可将土壤中有机相污染物直接抽出。生物降解有生物好氧降解、生物厌氧降解、生物还原降解多种,降解方式由污染物种类和地质条件决定。化学方法可将污染物氧化或还原为低毒无毒物质,周期一般较短。固定污染物可以直接加入药剂反应生成沉淀,也可制造合适条件使微生物生成可沉淀重金属的离子。植物修复主要用于富集重金属,成本低廉,但富集了重金属的植物体的有效利用尚待进一步研究。土壤原位修复需要因地制宜,灵活结合工期、污染情况、地质条件、地面设施等,得出最经济实用的修复方法,并在辅助提高技术上展开更多研究,使原位修复技术更经济有效。     

Evaluation of Electrokinetic Remediation of Arsenic-contaminated Soils

The potential of electrokinetic (EK) remediation technology has been successfully demonstrated for the remediation of heavy metal-contaminated fine-grained soils through laboratory scale and field application studies. Arsenic contamination in soil is a serious problem affecting both site use and groundwater quality. The EK technology was evaluated for the removal of arsenic from two soil samples; a kaolinite soil artificially contaminated with arsenic and an arsenic-bearing tailing-soil taken from the Myungbong (MB) gold mine area. The effectiveness of enhancing agents was investigated using three different types of cathodic electrolytes; deionized water (DIW), potassium phosphate (KH₂PO₄) and sodium hydroxide (NaOH). The results of the experiments on the kaolinite show that the potassium phosphate was the most effective in extracting arsenic, probably due to anion exchange of arsenic species by phosphate. On the other hand, the sodium hydroxide seemed to be the most efficient in removing arsenic from the tailing-soil. This result may be explained by the fact that the sodium hydroxide increased the soil pH and accelerated ionic migration of arsenic species through the desorption of arsenic species as well as the dissolution of arsenic-bearing minerals.     

Enhanced electrokinetic remediation of chromium-contaminated soil using approaching anodes

As a new technology used for the cleaning of chromium-contaminated soil, worldwide interest in eletrokinetic (EK) remediation has grown considerably in recent times. However, owing to the fact that chromium exists as both cationic and anionic species in the soil, it is not an efficient method. This paper reports upon a study in which a process using approaching anodes (AAs) was used to enhance the removal efficiency of chromium by eletrokinetics. Two bench-scale experiments to remove chromium from contaminated soil were performed, one using a fixed anode (FA) and the other using AAs. In the AAs experiment, the anode moved toward the cathode by 7 cm every three days. After remediation, soil pH, total chromium, and fractionation of chromium in the soil were determined. The average removal efficiency of total chromium was 11.32% and 18.96% in the FA and AAs experiments, respectively. After remediation, acidic soil conditions throughout the soil were generated through the use of AAs, while 80% of the soil remained neutral or alkalic when using the FA approach. The acidic soil environment and high field intensity in the AAs experiment might have favored chromium desorption, dissolution and dissociation from the soil, plus the mobility of chromium in the soil was also enhanced. The results demonstrate that AAs used in the process of EK remediation can enhance the efficiency of chromium removal from soil.     

水土环境介质中阿特拉津修复过程研究进展

除草剂阿特拉津农用后的残留物会随地表径流或地下渗漏作用进入江河湖泊等自然水体,由于阿特拉津的环境内分泌干扰作用,其会造成水资源污染和水生态失衡。根据阿特拉津的生产和使用状况,将阿特拉津的污染对象分为土壤、市政污水、河流湖泊等地表水和地下水系统模块,分别阐述了这几种环境介质中阿特拉津的物理、化学和生物修复技术以及阿特拉津在修复过程中的变化特点,介绍了土壤在淋溶过程中阿特拉津的固定手段和今后污染水体中阿特拉津修复的研究重点。     

A review of combinations of electrokinetic applications

Anthropogenic activities contaminate many lands and underground waters with dangerous materials. Although polluted soils occupy small parts of the land, the risk they pose to plants, animals, humans, and groundwater is too high. Remediation technologies have been used for many years in order to mitigate pollution or remove pollutants from soils. However, there are some deficiencies in the remediation in complex site conditions such as low permeability and complex composition of some clays or heterogeneous subsurface conditions. Electrokinetic is an effective method in which electrodes are embedded in polluted soil, usually vertically but in some cases horizontally, and a low direct current voltage gradient is applied between the electrodes. The electric gradient initiates movement of contaminants by electromigration (charged chemical movement), electro-osmosis (movement of fluid), electrolysis (chemical reactions due to the electric field), and diffusion. However, sites that are contaminated with heavy metals or mixed contaminants (e.g. a combination of organic compounds with heavy metals and/or radionuclides) are difficult to remediate. There is no technology that can achieve the best results, but combining electrokinetic with other remediation methods, such as bioremediation and geosynthetics, promises to be the most effective method so far. This review focuses on the factors that affect electrokinetic remediation and the state-of-the-art methods that can be combined with electrokinetic.     

模拟镉污染土壤的电动力学修复研究

采用阳离子交换膜调控电解过程中pH值的变化和电解富集土壤中的元素,在pH=5.0的缓冲溶液中进行土壤的电动强化处理.通过对镉形态的分析,找到镉在电场中迁移转换的规律.在处理时间内,阳极附近镉的去除率达99%以上,阴极镉的富积系数达2.026,表明电场对土壤中重金属的迁移溶出有强化去除作用.     

Engineering practice of mechanical soil aeration for the remediation of volatile organic compound-contaminated sites in China: Advantages and challenges

In recent years, many industrial enterprises located in the urban centers of China have been relocated owing to the rapid increase in urban development. At the sites abandoned by these enterprises, volatile organic compounds have frequently been detected, sometimes at high concentrations, particularly at sites abandoned by chemical manufacturing enterprises. With the redevelopment of sites and changes in land-use type associated with these sites, substantial amounts of contaminated soils now require remediation. Since China is a developing country, soil remediation warrants the usage of techniques that are suitable for addressing the unique challenges faced in this country. Land shortage is a common problem in China; the large numbers of contaminated sites, tight development schedules, and limited financial resources necessitate the development of cost-effective methods for land reclamation. Mechanical soil aeration is a simple, effective, and low-cost soil remediation technique that is particularly suitable for the remediation of large volatile organic compound-contaminated sites. Its effectiveness has been confirmed by conducting laboratory studies, pilot tests, and full-scale projects. This study reviews current engineering practice and developmental trends of mechanical soil aeration and analyzes the advantages and disadvantages of this technology for application in China as an emerging soil remediation market. The findings of this study might aid technology development in China, as well as assist other developing countries in the assessment and implementation of costeffective hazardous waste site soil remediation programs.

Open image in new window

     

微生物修复土壤多环芳烃污染的研究进展

多环芳烃是一类具有致癌、致畸、致突变性质的持久性有机污染物,主要来源于煤、石油等燃料的不完全燃烧,易吸附于固体颗粒表面和有机腐殖质,化学结构稳定,能长期存在于自然环境,给人类健康和生态环境带来很大的危害。中国土壤多环芳烃污染严重,因此急需寻求有效的修复方法进行治理。在众多的多环芳烃污染修复方法中,微生物修复因其低成本、高效、污染少等优点成为研究热点。科学家们从自然界中分离出了多种细菌、真菌等具有降解多环芳烃能力的微生物,并对多环芳烃的降解机理进行了探索,结果表明,微生物在代谢活动过程中能够产生酶来实现对土壤中多环芳烃的降解。细菌主要通过产生双加氧酶来催化多环芳烃的加氧反应,而真菌可以通过分泌木质素降解酶系或单加氧酶来氧化多环芳烃。两种途径均是首先通过降低多环芳烃的稳定性,使之容易被进一步降解。目前,微生物修复技术正逐步应用于PAHs污染土壤的实地修复,且已取得一定成效。文章简要介绍了降解多环芳烃的微生物,对多环芳烃的微生物降解机制进行了综述,讨论了影响微生物修复过程的因素,列举了常见的微生物修复相关技术,展望了今后的研究趋势。     

Review on remediation technologies for arsenic-contaminated soil

• Recent progress of As-contaminated soil remediation technologies is presented. • Phytoextraction and chemical immobilization are the most widely used methods. • Novel remediation technologies for As-contaminated soil are still urgently needed. • Methods for evaluating soil remediation efficiency are lacking. • Future research directions for As-contaminated soil remediation are proposed. Arsenic (As) is a top human carcinogen widely distributed in the environment. As-contaminated soil exists worldwide and poses a threat on human health through water/food consumption, inhalation, or skin contact. More than 200 million people are exposed to excessive As concentration through direct or indirect exposure to contaminated soil. Therefore, affordable and efficient technologies that control risks caused by excess As in soil must be developed. The presently available methods can be classified as chemical, physical, and biological. Combined utilization of multiple technologies is also common to improve remediation efficiency. This review presents the research progress on different remediation technologies for As-contaminated soil. For chemical methods, common soil washing or immobilization agents were summarized. Physical technologies were mainly discussed from the field scale. Phytoextraction, the most widely used technology for As-contaminated soil in China, was the main focus for bioremediation. Method development for evaluating soil remediation efficiency was also summarized. Further research directions were proposed based on literature analysis.     

超临界流体萃取在研究土壤和沉积物结合态残留中的应用

许多有机污染物在土壤和沉积物中形成持久稳定的结合态残留；结合态残留对土壤和沉积物的解毒过程、污染物长期分配行为、生物可用性和生物毒性都具有重要影响。为了揭示结合态残留的形成机制及其对污染物环境行为和毒理学参数的影响，从土壤或沉积物中提取出不同结合状态的有机污染物就显得非常重要。超临界流体萃取(SFE)可以实现选择性萃取，从而得到有关污染物一基体间相互作用的信息。文章介绍了SFE应用类型、超临界流体种类以及影响SFE萃取率的因素，对SFE模拟有机污染物长期吸附／解吸行为和生物可用性研究进行了论述，并认为SFE势必发展成为土壤或沉积物中结合态残留形成机理研究、土壤修复和生态风险评价的一种强有力的技术。     

土著微生物原位修复石油污染土壤试验研究

利用当地土著微生物优势菌群,辅以物理和化学的方法,结合当地地质微环境特点,开展了陕北某油井旁的石油污染黄土土壤修复研究。设置两个试验区、一个空白区和一个对照区,在两个试验区中分别加入3%的土著优势菌群制剂,选择优化出的土著菌群经鉴定,主要有：假单胞菌属（Pseudomonas）、微球菌属（Micrococcus）、放线菌属（Actinomayces）、真菌类的青霉属（Penicillium）、曲霉属（Aspergillus）等。试验结果显示：土著优势菌剂一般需要3-7d的延滞期（lag phase）,然后进入对数期（logarithmic phase）;两个试验区土壤中人为添加石油含量分别为1542、1886mg·kg^-1时,经过11-32d原位土著优势微生物菌剂的修复,土壤中的石油污染物降解率可达69.52%-88.11%,而对照区土壤中人为添加的石油含量变化不大,降解率基本在10%以内,说明在自然条件下土壤中石油降解是缓慢的。谷糠黍糠、麦麸两种添加剂对优化菌液的修复效果的作用基本相同。试验过程中对土壤温度、水分、氧和营养物质等影响因素进行了调控,起到了良好的作用。     

Changes in chromium distribution during the electrodialytic remediation of a Cr (VI)-contaminated soil

A laboratory study has been carried out to determine the feasibility of in situ remediation of chromium (VI)-contaminated soil using electrodialysis in relation to its speciation in soil. This technique is best suited for low-permeability soils or sediments, which may be difficult to remediate by other means and implies the application of a low-intensity direct current to the soil, which is separated from the electrode compartments by ion-exchange membranes. A clayey soil was prepared for use in the experiments and was characterized before being mixed with a solution of potassium dichromate for several days to produce a final Cr content of 4,056 mg/kg of soil dry wt. Remediation tests were carried out under constant-voltage conditions for periods of 7–14 days and the evolution of applied current to the cell, pH, and conductivity of the electrolytes were recorded periodically. Fractionation of chromium was determined for soil samples before and after remediation using a standardized four-step sequential extraction procedure (SEP) with acetic acid, hydroxylamine, hydrogen peroxide, and aqua regia solutions. Results show that chromium is mobilized from the most labile phases (soluble/exchangeable/carbonate). In a 15 V test, SEP results show that the amount of chromium extracted in the first step drops from 80% to 9%, but also that changes in the total chromium distribution occur during the treatment with some transferred to other soil phases that are more difficult to mobilize.     

施用城市污泥对土壤生态系统影响的研究进展

城市污泥的合理处置已成为目前环境科学研究领域中的重要课题。因污泥富含有机质和有效营养成分,对土壤改良有积极的促进作用,所以污泥的土地利用普遍被认为是一种积极、有效的处置方式。鉴于此,本文就国内外施用城市污泥对土壤生态系统的．影响及相关的过程和机理进行了综述。结果显示,施用污泥可改善土壤理化性质,提高土壤有机质和氮、磷等养分元素的含量,其改良作用因污泥类型而异。污泥对土壤重金属的积累有所影响,特别是在酸雨频发地区或者长期施用污泥,可能会带来重金属Gu污染的环境风险。污泥普遍有利于提高土壤酶活性,譬如土壤淀粉酶、脲酶和蔗糖酶活性,但污泥施用过量或时间延长,则会抑制多酚氧化酶和磷酸酶的活性,而污泥对过氧化氢酶的影响则不大。污泥对土壤微生物特性短期内有积极的影响,但长期则有负面作用。施用污泥可导致土壤动物活性的增加,但也会对一些土壤动物产生毒性,譬如异壳介虫属和弹尾目昆虫,而且污泥毒性不仅取决于污泥用量,土壤类型也起着重要作用。基于上述分析和评述,提出了未来研究展望如下：（1）针对污泥施用后土壤生态系统生物、物理和化学过程和机理进行系统、综合的基础研究;（2）对污泥土地利用进行长期的系统定位试验和环境监测,并对之进行环境风险评价;（3）对污泥稳定化处理技术的创新及其应用研究。     

Lead particle size and its association with firing conditions and range maintenance: implications for treatment

Six firing range soils were analyzed, representing different environments, firing conditions, and maintenance practices. The particle size distribution and lead (Pb) concentration in each soil fraction were determined for samples obtained from the backstop berms. The main factors that were found to influence Pb fragment size were the type of soil used to construct the berms and the type of weapon fired. The firing of high velocity weapons, i.e., rifles, onto highly angular soils induced significant fragmentation of the bullets and/or pulverization of the soil itself. This resulted in the accumulation of Pb in the finer soil fractions and the spread of Pb contamination beyond the vicinity of the backstop berm. Conversely, the use of clay as backstop and the use of low velocity pistols proved to be favorable for soil clean-up and range maintenance, since Pb was mainly present as large metallic fragments that can be recovered by a simple screening process. Other factors that played important roles in Pb particle size distribution were soil chemistry, firing distance, and maintenance practices, such as the use of water spray for dust suppression and deflectors prior to impact. Overall, coarse Pb particles provide much easier and more cost-effective maintenance, soil clean-up, and remediation via physical separation. Fine Pb particles release Pb more easily, pose an airborne Pb hazard, and require the application of stabilization/solidification treatment methods. Thus, to ensure sustainable firing range operations by means of cost-effective design, maintenance, and clean-up, especially when high velocity weapons are used, the above mentioned factors should be carefully considered.