固化/稳定化修复后土壤重金属稳定性及再活化研究进展

固化/稳定化技术是一种经济、有效、快捷的重金属污染主流修复技术,随着我国以风险管控为主导策略的土壤污染防治工作的推进,该技术正发挥着极其重要的作用。固化/稳定化技术处置后土壤中的重金属并未移除,存在再活化的风险。本文对固化/稳定化技术特点、修复效果评估方法、评价标准等进行了系统总结,概述了修复后重金属赋存形态、生物有效性、微观形态等特征,着重阐述了冻融、水环境和酸雨淋溶3类环境胁迫下重金属的再活化行为和影响因素。在此基础上,讨论了当前固化/稳定化修复后土壤和场地环境监管体系构建的现状、不足和发展需求,提出需注重修复后重金属环境行为、再活化定量化等研究方向。     

利用粘粒矿物修复重金属污染农业土壤研究进展

Heavy metal contamination of agricultural soils poses risks and hazards to humans.The remediation of heavy metal-polluted soils has become a hot topic in environmental science and engineering.In this review,the application of clay minerals for the remediation of heavy metal-polluted agricultural soils is summarized,in terms of their remediation effects and mechanisms,influencing factors,and future focus.Typical clay minerals,natural sepiolite,palygorskite,and bentonite,have been widely utilized for the in-situ immobilization of heavy metals in soils,especially Cd-polluted paddy soils and wastewater-irrigated farmland soils.Clay minerals are able to increase soil pH,decrease the chemical-extractable fractions and bioavailability of heavy metals in soils,and reduce the heavy metal contents in edible parts of plants.The immobilization effects have been confirmed in field-scale demonstrations and pot trials.Clay minerals can improve the environmental quality of soils and alleviate the hazards of heavy metals to plants.As main factors affecting the immobilization effects,the pH and water condition of soils have drawn academic attention.The remediation mechanisms mainly include liming,precipitation,and sorption effects.However,the molecular mechanisms of microscopic immobilization are unclear.Future studies should focus on the long-term stability and improvement of clay minerals in order to obtain a better remediation effect.     

Cosolvent-enhanced Desorption and Transport of Heavy Metals and Organic Contaminants in Soils during Electrokinetic Remediation

Numerous sites are contaminated with both heavy metals and polycyclic aromatic hydrocarbons (PAHs) and the technologies to treat such mixed contaminants are very limited. Electrokinetic remediation has the potential to remediate mixed contaminants in soils, including low permeability soils; however, the efficiency of this technology depends on the extracting solution employed. Previous studies on electrokinetic remediation have focused on the removal of heavy metals and organic compounds when they exist individually in clayey soils. In the present study, the feasibility of using cosolvents to enhance the electrokinetic removal of PAHs from clayey soils in the presence of heavy metals is investigated. A series of laboratory electrokinetic experiments was conducted using kaolin soil spiked with phenanthrene and nickel at concentrations of 500 mg/kg each to simulate typical field mixed contamination. Experiments were performed using n-butylamine (cosolvent) at concentrations of 10 and 20% and deionized water, each mixed with 0.01 M NaOH solution and circulated at the anode to maintain alkaline conditions. A periodic voltage gradient of 2 VDC/cm in cycles of 5 days on and 2 days off was applied in all the tests. During the initial stages when the soil pH was low, nickel existed as a cation and electromigrated towards the cathode. However, as the soil pH increased due to hydroxyl ions generated at the cathode and also flushing of high pH n-butylamine solution from the anode, nickel precipitated with no further migration. Phenanthrene was found migrating towards the cathode in proportion to the concentration of n-butylamine. The extent of phenanthrene removal was found to depend on both the electroosmotic flow and the concentration of n-butylamine, but the presence of nickel did not influence the transport and removal of phenanthrene.     

The effects of different amendments on the mobility and toxicity of nickel and copper in polluted soils

The efficiency of different amendments for the remediation of acidic sandy soils contaminated with heavy metals was assessed in a model laboratory experiment with podzols from the Kola Peninsula. The addition of SLOVAKITE®, lime, and vermiculite leads to significant reduction of the acidity and mobility of nickel and copper in polluted soils, as well as an increase in the length and phytomass of shoots and roots of Festuca rubra. The application of superphosphate for the remediation of soils that were polluted with nickel and copper was less helpful, while the apatite and zeolite additives were inefficient.     

铁/锰氧化菌诱导土壤重金属生物成矿研究进展

综述了铁锰氧化菌诱导成矿对重金属环境行为的影响,分别从铁/锰氧化菌与生物成矿、铁/锰氧化菌诱导铁锰氧化物沉淀耦合重金属稳定化以及铁锰氧化物对土壤中重金属的作用方面进行阐述;并从铁/锰氧化菌生物成矿方式、铁/锰氧化菌诱导生物成矿过程对土壤重金属的稳定化机制等方面进一步总结了铁/锰氧化菌在不同重金属生物成矿修复中的应用,以及微生物诱导成矿过程的调控因素,分析胞外聚合物、温度与酸碱度、共存离子和其他因素对成矿过程的影响,以期为微生物诱导成矿修复重金属污染提供理论参考。未来工作可进一步关注生成矿物稳定重金属的长效性,不同微生物菌群组合对成矿效果的调控,以及铁/锰氧化菌在重金属复合污染场地土壤修复中的应用等方面。     

Methods for remediation of metal‐contaminated soils: Preliminary results

Abstract

Contamination of soils by heavy metals is one of the environmental problems that the scientific community faces today. Such soils are difficult to treat because the heavy metals cannot be destroyed. Moreover, they are usually bonded with other contaminants, in particular organic ones. The presence of these organic pollutants can make the removal of metals from soils substantially more complicated. One way of coping with the problem which has been studied in recent years is the use of fixing agents which make the heavy metals unavailable to the plants, or prevent their leaching towards the groundwater. Inorganic fixing agents in particular have been tested and found to be suitable, but some organic ones can also be used, at least as temporary fixing materials. This paper gives preliminary results on remediation techniques using compost and Trichoderma viride Pers.: Fr. as heavy metal fixing agents.     

土壤重金属复合污染的化学固定修复研究

本文研究糠醛渣、磷矿粉、风化煤3 种修复剂对重金属复合污染土壤的化学固定修复效果.结果表明:糠醛渣、磷矿粉、风化煤3 种修复剂都可一定程度地降低复合污染土壤中的Cu、Zn、Pb、Cd含量,其中以风化煤降低土壤有效态Zn、Cu的效果较好,在风化煤添加量为80 g/kg时土壤有效态Zn的含量降低了37.22%,土壤有效态Cu的含量降低了31.22%;磷矿粉处理修复Pb的效果比糠醛渣、风化煤好,在磷矿粉添加量为80 g/kg时,土壤有效态Pb的含量降低了23.79%;3 种修复剂都能显著降低土壤有效态Cd,在磷矿粉添加量为40 g/kg时,土壤有效态Cd的含量降低最显著,较对照降低了83.09%.在本试验条件下,3 种修复剂对4 种重金属复合污染土壤的修复效果,以Cd 较好,其次是Zn,对Pb的修复效果较差.     

改性纳米黑碳应用于钝化修复重金属污染土壤中的问题探讨

通过有关文献资料调研,综述纳米黑碳在钝化修复污染土壤中的应用,分析其应用于钝化修复重金属污染土壤时尚待弄清的几个问题。结果表明：（1）由于纳米黑碳是疏水的非极性吸附剂,选择纳米黑碳作为土壤重金属钝化修复剂时,需对其进行氧化改性,以进一步提高其钝化能力。目前常用的氧化剂为氧化性无机酸、酸性高锰酸钾、双氧水、臭氧等,强烈的氧化过程,会破坏纳米黑碳微孔结构,一定程度上降低其吸附量。（2）为了明确其应用的可能性和适用范围,需揭示改性纳米黑碳对土壤中重金属的钝化机理及其影响因素。土壤CEC、pH、重金属离子的性质等可能是影响改性纳米黑碳对土壤中重金属吸附性能的主要因素。（3）充分利用改性纳米黑碳在土壤修复中的有益作用的同时,还需考虑其可能存在的生态环境负面效应,研究其在土壤中的径流迁移、渗漏等,明确其污染地表水和地下水的可能性,研究其生物效应和将吸附钝化后的纳米黑碳从土壤中移除的可能性,明确其潜在的生态环境风险。     

Remediation efficacy of Sedum plumbizincicola as affected by intercropping of landscape plants and oxalic acid in urban cadmium contaminated soil

Journal of Soils and Sediments - Intercropping is a promising technique for remediation of soils contaminated with heavy metals. Organic acids can increase the availability of heavy metals in soil....     

污染农田土壤的重金属钝化技术研究 ——基于Web of Science数据库的计量分析

为全面直观了解全球农田土壤重金属污染钝化修复研究进展和发展趋势,本文基于Web of Science(简称WoS)核心合集数据库利用WoS数据库自带分析工具、HistCite引文图谱分析软件和VOSviewer可视化分析软件,从发文量或被引频次TOP10的国家、研究机构、作者、期刊、研究热点等方面对1990―2019年...     

重金属污染土壤的螯合剂诱导植物修复研究进展

植物修复作为一种生态友好型原位绿色修复技术成为重金属污染土壤修复研究的热点。然而,目前最具有推广价值的超积累植物因生物量低、生长缓慢、对重金属的积累具有专一性等缺点,大大限制了植物修复技术在重金属污染尤其是复合重金属污染土壤治理方面的推广应用。利用生长速度快、生物量大的普通植物借助其它技术辅助的联合植物修复便成了有效可行的替代途径和研究焦点。近年来,金属螯合剂诱导的化学-植物联合修复技术备受关注。本文综述了螯合剂诱导植物修复技术的研究进展、修复机理和目前存在的问题,并对该项技术的未来研究方向给予了展望。     

Accumulation of heavy metals in oil-contaminated peat soils

X-ray fluorescence and X-ray radiometry represent easy and simple methods to determine concentrations of heavy metals in the ash of peat soils contaminated with oil and can be applied for soil monitoring purposes. Oil spills on peat bogs produce two contamination zones differing in the composition of heavy metals. In the zone of primary contamination, the peat surface is covered by a bitumen crust with V, Ni, Sr, Ba, Ce, and La accumulating there. This zone adjoins the zone of secondary peat contamination, where heavy alkaline-earth metals (Sr, Ba) and lanthanides (Ce and La) are accumulated to a lesser extent. Biological preparations recommended for remediation of oil-contaminated peat soils should be tolerant to high concentrations of heavy metals, particularly, V, Ni, and Ba that are present in the oil contaminated soils in relatively high amounts.     

3种有机酸对伴矿景天修复效率及土壤微生物数量的影响

伴矿景天(Sedumplumbizincicola)是一种Cd和Zn的超积累植物,常用于Cd污染土壤的植物修复。有机酸能够提高土壤重金属的有效性,促进植物对重金属的积累,对重金属污染土壤的植物修复效率具有强化作用,并对土壤微生物数量有重要影响。以河潮土和红黄泥为供试土壤,探讨了乙二胺四乙酸(EDTA)、柠檬酸、草酸对伴矿景天修复效率和土壤微生物数量的影响。结果表明,有机酸能显著提高土壤有效态Cd含量,柠檬酸处理的效果最好,河潮土和红黄泥中有效态Cd含量较单种伴矿景天分别增加72.73%,12.99%(P<0.05);伴矿景天地上部Cd含量在河潮土和红黄泥中以EDTA处理最高,在河潮土和红黄泥中分别比单种伴矿景天增加99.24%和33.32%;与单种伴矿景天相比,添加有机酸处理河潮土和红黄泥中伴矿景天修复效率显著提高。添加有机酸比单种伴矿景天显著增加土壤中微生物数量,其中柠檬酸处理河潮土中细菌和真菌数量分别增加34.38%和68.42%(P<0.05),草酸处理红黄泥中放线菌数量增加150.00%。研究结果可为重金属污染土壤的植物强化修复提供理论支撑。     

土壤重金属迁移模拟研究的现状与展望

随着工业发展和废弃物的排放不断增加,土壤重金属污染已经成为一个世界性环境问题。土壤重金属的分布转化以及污染修复的研究受到广泛关注,数学模型及计算机模拟研究成为重要的研究手段。该文对土壤重金属迁移的模拟研究的进展进行了回顾与归纳,集中阐述了对流弥散和经验随机两大类模型的特点和应用,并指出了研究中存在的问题及今后研究的发展方向。将数学模拟与土壤重金属信息系统及地理信息系统GIS的有机结合,将有可能为环境保护和农业决策提供新的重要依据。     

铁氧化物固定土壤重金属的研究进展

铁氧化物及其前体在重金属污染土壤的原位修复方面已得到广泛应用,它既可单独使用亦可与其他钝化剂联用.尽管应用铁氧化物修复重金属污染土壤取得了部分成功,但对长期、大规模应用的效果及其稳定性等,目前尚缺乏统一的认识.在对铁氧化物修复重金属污染土壤研究结果进行归纳总结的基础上,探讨了植物和微生物对铁氧化物稳定砷效果的影响,旨在...     

滇西某油用牡丹种植区镉铅污染及钝化修复效果评估

油用牡丹是一种新型的木本食用油料植物，其在重金属污染耕地上的生产安全性鲜有报导。本文对云南西部某矿区周边油用牡丹种植区的土壤和植物镉（Cd）、铅（Pb）污染状况进行调查，并结合田间小区试验探讨中重度污染耕地化学钝化修复的可行性。结果表明，油用牡丹种植区的土壤和植物可食部分存在严重的Cd、Pb污染，土壤全量Cd、Pb较风险筛选值（GB 15618-2018）的超标率分别为100%和82.8%；油用牡丹籽粒中Cd和Pb浓度超标率高达100%和82.1%（GB 2762-2017），中药材牡丹皮中Cd超标率也高达77.1%以上。钝化修复显著提高了中重度污染耕地上油用牡丹根系生物量和根长，但对其成活率和株高无显著影响。生石灰和海泡石复合钝化剂施用显著降低了土壤CaCl2提取态Cd、Pb浓度，降幅在56%和59%以上，且随着钝化剂用量的增加钝化效果显著增强。虽然钝化修复显著降低了重度污染土壤上牡丹皮Cd浓度，但牡丹皮Cd浓度仍存在较高的超标风险。为保证中重度污染耕地的油用牡丹生产安全性，应提高钝化剂施用量以持续降低污染土壤中重金属有效性，并加强土壤和农产品Cd、Pb的协同监测。     

大宝山矿区农田土壤重金属污染及其植物累积特征

对金属矿山选冶活动影响的农田土壤,不同灌溉水源会影响重金属的分布累积特征。根据实际情况将大宝山矿区农田土壤分为污水灌溉区、清水灌溉区、自然修复区和对照区,并进行土壤和植物样品采集,调查研究了土壤的基本理化性质,Cd、Pb、Cu、Zn、Mn 5种重金属的含量和化学形态分布,以及不同区域植物中重金属的含量。结果表明:污灌区Cd、Pb、Cu、Zn的含量最高,是自然修复区和清水灌溉区的1.75倍~10.51倍,对照区最低;Mn在各采样点的含量无显著差别。土壤Cd、Cu、Zn、Pb含量两两之间显著正相关,Mn与Cu、Zn、Cd、Pb呈负相关关系;土壤pH与重金属环境有效态关系密切。残渣态是5种重金属的主要存在形态,有机态含量也较高;Cd的环境有效态含量占总量的比例是其他4种重金属的2倍左右。稻米中5种重金属在清水灌溉区的含量均比污水灌溉区低,其中Cu和Zn的含量在两区域均未超标(NY861-2004),而Pb和Cd的含量严重超标。重金属在自然修复区和清水灌溉区呈现较低的土壤污染和人体健康风险,该研究数据可为金属矿区土壤污染控制提供科学的依据。     

赤泥颗粒对韭菜吸收污染土壤中铅锌的抑制效应研究

采用盆栽试验方法,通过添加赤泥颗粒修复铅锌污染土壤,按照火焰原子吸收分光光度法测定不同时期种植韭菜的土壤中重金属的含量,分析赤泥颗粒对土壤中重金属的钝化行为与机理,确定赤泥颗粒对土壤修复和对韭菜生长促进最佳的添加量。结果表明,赤泥颗粒能缓释OH-,促进重金属铅、锌化学形态转化和抑制生物吸收。铅、锌污染土壤修复的最佳赤泥颗粒添加量为5%,此时,土壤中铅、锌的生物有效态含量在修复期内分别降低了41.03%、26.55%;结合铅锌污染土壤修复与韭菜生长影响,初步确定赤泥颗粒的最佳施用量为1%,此时,土壤中铅、锌的生物有效态含量在修复期内分别降低了24.81%、15.9%;赤泥颗粒对铅锌污染土壤的修复能力大小为铅〉锌。     

Kinetics of speciation of copper,lead, and zinc loaded to soils that differ in cation exchanger composition at low moisture content

Abstract

A better understanding of the fates of heavy metals in wide range of soils is important in improving efficiency of remediation technologies of heavy metals polluted soils. To contribute to this field we studied the kinetics of speciation of copper (Cu), leaf (Pb), and zinc (Zn) in six soils differed in major cation exchanger composition. Soluble salts of Cu, Pb, and Zn were loaded to the soils, incubated at field moisture contents, and the change in chemical forms of the metals was traced by sequential extraction. In Inceptisols predominated by 2:1 layer silicates and poorly crystalline iron oxides, the added Cu and Pb were found mostly in exchangeable and oxide bound fractions, with decreasing and increasing proportion of the former and the latter during 50 days after addition, respectively. In allophanic and humic Andisols, about 50 to 70% of the total Cu and Pb was found in oxide bound fraction with a significant amount in organically complexed fraction in the latter. The amounts of Cu and Pb in each fraction varied only slightly with time in these soils. The proportion of oxide bound Cu arid Pb was relatively low in a kaolinitic Ultisol irrespective of its higher iron oxide content. Zinc was found mostly in exchangeable and soluble fractions except in Andisols. Low crystallinity of oxide minerals as well as their amount is important factors determining heavy metal retaining capacity of soils. The exchangeable and oxide bound heavy metals should be treated separately in models simulating removal of heavy metal cations by washing and electrokinetic methods.     

不同钝化剂对Cu、Cr和Ni复合污染土壤的修复研究

利用盆栽试验研究了不同钝化剂(沸石、牡蛎壳、鸡蛋壳、硅藻土和聚丙烯酰胺(PAM))对生长在重金属污染土壤上的青菜(Brassica chinensis L.)生物量、重金属吸收以及超氧化物歧化酶的活性(SOD)和丙二醛(MDA)含量的影响,同时,通过对土壤p H和土壤重金属提取态的分析,探讨了钝化剂影响青菜生物量和重金属吸收的可能原因。结果表明:钝化剂加入可显著降低青菜地上部分Cu、Zn、Ni和Cd的含量及其氧化性损伤和脂膜损伤(SOD和MDA指标显著降低)。施入钝化剂后,土壤p H显著提高,重金属提取态Cu、Zn、Pb、Ni和Cd普遍降低(硅藻土处理除外)。相关性分析表明,土壤p H与提取态重金属Pb、Zn、Ni和Cd呈显著的负相关,而青菜中的重金属Zn、Ni和Cd的含量与土壤提取态含量呈显著正相关。综合考虑,单一钝化剂牡蛎壳和沸石+牡蛎壳+鸡蛋壳(FMJ)组合对降低青菜重金属吸收的效果尤为显著,可推荐作为重金属复合污染土壤的改良剂。本研究为重金属中轻度污染菜地的土壤修复提供了一种新方法。