土壤重金属污染现状与修复技术研究

土壤是农业的基础,也是人类获取食物和其他再生资源的物质基础。随着工业发展和农业生产的现代化,重金属污染已经成为一个危害全球环境质量的主要问题。本文通过土壤重金属污染的来源、现状、不同修复技术的原理、优缺点、前景作了概述,并重点对目前常用改良剂的修复效果、存在的问题、改良剂原位修复土壤重金属污染的作用机制以及国内外研究进展作简要综述及对未来趋势提出一些看法,为实现对重金属污染土壤进行有效的生态整治和安全高效的利用提供技术途径。     

有机改良剂在重金属污染土壤修复治理中的应用

土地利用逐渐成为重要的废物利用和处置方式,因此土壤被视为重金属的主要来源,通过植物吸收和动物转换进入食物链。随着公众逐渐意识到污染土壤对人类和动物健康带来的不良影响,场地污染修复技术的开发也得到了广泛的研究。生物修复是通过土壤微生物和植物改变重金属的生物利用率,添加有机改良剂提高其作用效果。堆肥、污泥和城市固体废物等许多有机改良剂可改善土壤物理性质和肥力,通过吸附、络合、还原、挥发等作用降低土壤中重金属的生物利用率。基于此,综述了有机改良剂在生物修复中的作用机制,并讨论了土壤重金属吸收与生物利用率的现实意义。     

农田土壤重金属污染化学钝化修复研究进展

土壤重金属化学钝化修复是指向污染土壤中添加钝化剂,使重金属由活性向稳定化形态转化,以降低重金属的迁移和生物可利用性,从而修复重金属污染土壤的方法。本文综述了近些年国内外各类钝化材料修复重金属污染土壤的作用效果和机理、实例等方面的研究进展,并讨论了原位修复土壤重金属中亟待解决的问题,旨在为农田土壤重金属污染的化学钝化剂筛选与应用提供参考依据。     

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,旨在为污染土壤修复提供理论支撑。     

壳聚糖修复重金属污染土壤的研究进展

壳聚糖是一种来源广泛、具有良好的生物相容性、生物降解性的高分子材料,其含有大量氨基、羟基等活性基团,能与重金属离子进行螯合,发生吸附作用。壳聚糖还具有改良土壤、促进植物生长,诱导植物抗逆的作用,在重金属污染农田土壤修复中具有独特的应用优势。综述了近年来国内外有关壳聚糖修复重金属污染土壤的研究进展,探讨了壳聚糖对土壤重金属污染修复的潜力,阐述了壳聚糖在重金属原位钝化修复、土壤淋洗修复、强化植物提取修复三个方面的应用,并指出壳聚糖在重金属污染土壤修复中存在的问题以及对其在未来修复重金属污染土壤的发展进行了展望,以期为壳聚糖重金属修复技术的推广和应用提供参考。     

重金属污染农田土壤化学钝化修复的稳定性研究进展

化学钝化修复是一种应用广泛的重金属污染农田土壤修复方法,但钝化修复只是暂时降低了土壤中重金属的移动性和生物有效性,随着时间的推移被固定的重金属有可能重新释放到土壤中,因此钝化修复重金属污染土壤的稳定性是重金属污染土壤原位钝化修复成功的关键。本文探讨了钝化修复剂的种类、修复机制、修复稳定性的影响因素以及修复稳定性的研究方法,深入分析了钝化修复稳定性的研究现状和存在问题,并提出今后应加强钝化修复稳定性机制和修复稳定性预测模型的研究,建立和完善科学的钝化修复稳定性的研究方法。     

土壤有机质对镉污染土壤修复的影响

镉是生物非必需具生物毒性元素,有机质作为修复镉污染土壤的重要改良剂之一而备受关注。土壤有机质通过对土壤理化性质、对镉的吸附-解析、络合作用、生物有效性作用影响镉污染土壤修复效果。主要阐述了土壤有机质对镉污染土壤修复的影响作用机制,探讨了有机质的适用条件、影响因子,分析了工程应用过程存在的问题,以期为重金属污染土壤修复技术研究提供新的思路。     

化学淋洗和深层土壤固定联合技术修复重金属污染土壤

联合技术用于修复重金属污染土壤是土壤修复领域的研究热点,本研究主要是利用化学试剂淋洗污染土壤,在深层土壤添加固定剂,固定从耕作层淋下来的重金属,旨在形成一种原位修复重金属污染土壤的新方法。     

农业土壤重金属污染原位修复技术

农业土壤重金属污染是土壤环境安全研究的热点问题之一,它影响食品安全,威胁人类健康。农业重金属土壤污染以中低浓度污染为主,对其修复的要求不同于一般重金属修复,需满足农用条件的要求。本文从农业土壤重金属污染特点入手,综述了国内外农业土壤重金属防治技术上已有的一些方法与实践,对以土壤原位修复为主的各类农业土壤原位修复技术的优势和局限性进行了比较,分析了物理修复、化学修复、生物修复和联合修复等几类农业土壤原位修复方法的优缺点,对农业土壤原位修复技术发展进行了展望。     

应用灰色关联度法评价砷污染土壤修复效果

采用盆栽试验进行砷污染土壤修复研究,根据4种不同改良剂对土壤修复的效果来评价改良剂的优劣,确定土壤修复最优模式.并采用灰色关联分析和聚类分析评价方法,以生菜生物量、农艺性状和生菜砷吸收量等为指标,对污染土壤修复贡献值进行定量分析和聚类评价.结果表明,磷石膏(20 g/kg)处理关联度值r=0.824最大,聚类分析为最优,是修复砷污染土壤的最优改良剂处理.     

不同钝化剂和培养时间对Cd污染土壤中可交换态Cd的影响

原位化学钝化技术是修复重金属污染土壤的重要途径之一,通过施入一些钝化剂以降低土壤中重金属有效态含量,从而减少其迁移及对植物的毒害。选取羟基磷灰石（HA）、磷矿粉（PRX和PRH）、沸石、赤泥、新鲜植物残体、玉米秸秆粉末以及相应的处理共21种钝化剂,在同一培养条件和添加浓度下,比较其对人工Cd污染土壤中可交换态Cd含量的影响,并分析了其在不同培养时间对钝化效果的时间效应,试验的结果对于筛选Cd污染土壤钝化剂有着重要的意义。结果表明,纳米化赤泥、羟基磷灰石和纳米化酸洗赤泥可显著降低土壤中可交换态Cd含量,钝化比例高达35%-55%;赤泥、酸洗赤泥、沸石达15%-25%;富含巯基植物蒜苗、油菜、大葱植物残体也可达20%-25%。磷矿粉、大葱粉末、玉米秸秆和巯基化玉米秸秆的钝化效果相对较差;HA、铵型沸石、纳米赤泥、酸洗纳米赤泥、干油菜粉末、酸洗赤泥对可交换态Cd的钝化效果的时间效应不明显;赤泥、大葱残体、特别是玉米秸秆和巯基玉米秸秆随时间增长钝化效果增加显著,在8周和16周时段钝化效果较好。     

Soil Immobilization of Heavy Metal Using Soil Amendments in a Greenhouse Study

ABSTRACT

The application of soil amendments to immobilize heavy metals is a promising technology to meet the requirements for environmentally sound and cost-effective remediation. The present work was carried out to evaluate the effect of phosphogypsum (PG) used alone and in combination with compost (CP) at a mix ratio of 1:1 wet weight ratio (PG+CP) at 10 and 20 g dry weight kg^?1 dry soil, on heavy metal immobilization in contaminated soil, and on canola growth (Brassica napus). The results were then compared with untreated soil (control). The results revealed that the Pb, Cd, and Zn uptake of canola plants was reduced by the application of PG alone and when it was mixed with CP. At an application rate of 10 g dry weight kg^?1 dry soil of (PG+CP), the dry weight of canola plants increased by 66.8%, which was increased in comparison on its weight in the untreated soil (control). The addition of PG alone resulted in more pronounced immobilization of heavy metals as compared to PG mixed with CP. Plant growth was improved with CP addition but heavy metals immobilization was greatest in PG alone treatments. Results suggest that PG may be useful for the immobilization of heavy metals in contaminated soils.     

Heavy Metal Immobilization in Contaminated Soils using Phosphogypsum and Rice Straw Compost

The application of soil amendments to immobilize heavy metals is a promising technology to meet the requirements for environmentally sound and cost‐effective remediation. The present study was carried out to evaluate the result of phosphogypsum (PG) used alone and in combination with compost (CP) at a mix ratio of 1:1 wet weight ratio (PG + CP) at 10 and 20 g dry weight kg⁻¹ dry soil, on heavy metal immobilization in contaminated soil and on canola growth. The results revealed that the Pb, Cd and Zn uptake of canola plants was reduced by the application of PG alone and when it was mixed with CP as compared with untreated soil. At an application rate of 10 g dry weight kg⁻¹ dry soil of (PG + CP) the dry weight of canola plants increased by 66·8% was increased in comparison with its weight in the untreated soil. The addition of PG alone resulted in more pronounced immobilization of heavy metal as compared with PG mixed with CP. Plant growth was improved with CP addition, but heavy metals immobilization was the greatest in PG alone treatments. Results suggest that PG may be useful for the immobilization of heavy metals in contaminated soils. Copyright © 2014 John Wiley & Sons, Ltd.     

Spectroscopic analyses to study the effect of biochar and compost on dry mass of canola and heavy metal immobilization in soil

This research was conducted to use spectroscopic analysis to evaluate the effect of biochar and compost application on heavy metal immobilization during the canola plants grown in the contaminated soil using X-Ray Diffraction (XRD), Energy Dispersive spectroscopy by X-rays (EDX) and Fourier Transmission Infrared Spectroscopy (FTIR). The results showed that the cadmium (Cd) and lead (Pb) concentrations in the root and shoot of canola plants significantly decreased with the addition of rice straw compost (RC) and biochar (RB) to contaminated soil. The use of spectroscopic analysis observed the precipitation, inner-sphere complex reaction, and electrostatic attraction are the dominating mechanisms for heavy metals immobilization with organic amendments. Our results indicate that the rice straw biochar and compost can immobilize heavy metals and improve dry weight of canola plants. Moreover, the spectroscopic analysis is a simple method and can be effective to understand the mechanism of heavy metals immobilization.     

不同改良剂降低矿区土壤水溶态重金属的效果及其长效性

为了解施用不同种类改良剂对降低矿区土壤重金属移动性的长期效果,进行为期6年的模拟试验,用化学提取方法评价磷灰石、农用石灰、坡缕石、钙镁磷肥、沸石、猪粪和水稻秸秆7种常用改良剂对降低土壤重金属溶解性的影响。结果表明,农用石灰、钙镁磷肥、磷灰石、坡缕石和沸石对降低矿区土壤水溶态重金属均有良好的效果,但猪粪和水稻秸秆有机物改良剂的效果较差。降低土壤水溶态Cd的效果以钙镁磷肥为最佳(平均可降至29%),降低土壤水溶态Cu的效果以坡缕石为最佳(平均可降至65%),降低土壤水溶态Pb的效果以磷灰石、石灰和钙镁磷肥3种改良剂为佳(平均可降至27%左右);降低土壤水溶态Zn的效果以钙镁磷肥为最佳(平均可降至48%)。磷灰石和沸石对土壤重金属的稳定性有较长的作用效果,坡缕石、石灰和钙镁磷肥对土壤重金属稳定性随试验时间增加有明显的下降;有机物类改良剂对土壤重金属的稳定效果较差,且随有机物质的降解,其稳定效果显著下降。     

含磷材料及生物炭对复合重金属污染土壤修复效果与修复机理

选取含磷材料（胛）、牛粪生物炭（DM）和水稻秸秆生物炭（Rs）实施Pb、Zn、Cd复合污染土壤化学稳定修复,进而评价修复效果,并分析影响因素;借助BCR连续提取法和x射线衍射光谱（XRD）探讨可能存在的修复机理。经过56d的化学稳定修复,修复材料均能显著降低TCLP提取态Pb、zn、cd,修复效果均为：Pb〉Zn〉Cd。三种修复材料对Pb、cd的修复效果为Er〉DM〉RS,对zn的修复效果基本相同。胛处理使土壤TCLP提取态的Pb、zn、cd分别降低了77．6％、31．5％、27．9％;DM处理使TCLP提取态的Pb、zn、cd分别降低了56．0％、26．1％、10．O％;RS处理使TCLP提取态的Pb、zn、cd分别降低了35．8％,25．0％和4．4％。三种修复材料均可促进Pb、cd从不稳定态向稳定状态转化。胛对Ph的固定机理主要是溶解一沉淀,XRD证明有Ca2Pb8（PO4）6（OH）2和Pb10（PO4）6（OH）2沉淀生成;DM固定Pb包括沉淀、吸附、离子交换等,XRD证明有Ca2Pb8（PO4）6（OH）2生成;Rs固定Pb主要为吸附、离子交换。研究结果表明,含磷材料和牛粪生物炭可作为理想的土壤Pb、zn、cd的修复材料。     

Contribution of arbuscular mycorrhizal fungi and soil amendments to remediation of a heavy metal-contaminated soil using sweet sorghum

Owing to their potential advantages such as waste reduction, recycling, and economic attributes, fast-growing bioenergy crops have the capacity to effectively phytoremediate heavy metal-contaminated soils. However, little is known about the role of microbial and chemical amendments in phytoremediation using bioenergy crops. Here, we studied the contributions of inoculation with the arbuscular mycorrhizal fungus (AMF) Acaulospora mellea ZZ and three soil amendments, i.e., hydroxyapatite (HAP), manure, and biochar, at doses of 0.1% and 1% (weight:weight) to heavy metal phytoremediation using sweet sorghum grown on an abandoned agricultural soil, with environmentally realistic contamination (2.6 mg kg^-1 Cd, 1 796 mg kg^-1 Pb, and 1 603 mg kg^-1 Zn), in a plant growth chamber. Mycorrhizal colonization, plant biomass and metal accumulation, metal availability, and soil pH were determined in harvested seedlings 12 weeks after sowing. The results showed that root colonization by indigenous AMF decreased by 28%-46% with HAP, but increased after manure and biochar applications as compared to the no amendment control (CK). The AMF inoculation increased root colonization rates by 16%-128% and in particular, alleviated the inhibition of HAP. The remediation effects were highly dependent on the amendment type and dose. Among the three soil amendments, HAP was the most effective in promoting plant growth and phytostabilization of Cd, Pb, and Zn and phytoextraction of Cd, particularly at a dose of 1%. Compared to CK, 1% HAP decreased DTPA-extractable Cd, Pb, and Zn concentrations in soil by 31%-43%, 30%-38%, and 22%-23%, respectively. Manure and biochar also exerted positive effects on heavy metal immobilization, as indicated by lower DTPA extractability, but only the 1% manure treatment showed plant growth-promoting effect. The AMF inoculation did not affect plant growth, but increased soil pH and induced synergistic interactions with amendments on the immobilization of Cd and Pb. In conclusion, soil amendments, particularly HAP, produced positive impacts and synergistic interactions with AMF on the phytostabilization of heavy metals using sweet sorghum. Accordingly, sweet sorghum combined with soil amendments and AMF may be an effective strategy for heavy metal phytoremediation.     

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。     

Immobilization of Cu and Cd in a contaminated soil: one- and four-year field effects

Purpose

Many amendments have been applied to immobilize heavy metals in soil. However, little information is available on the changes of immobilization efficiencies of heavy metals in contaminated soils over time. This work investigated the immobilization efficiencies of copper (Cu) and cadmium (Cd) in contaminated soils in situ remediated with one-time application of three amendments for 1 year and 4 years.

Materials and methods

Apatite, lime, and charcoal were mixed with the topsoil of each plot with the amounts of 22.3, 4.45, and 66.8 t/ha, respectively. Soil chemical properties and fractions of Cu and Cd were examined after in situ remediation for 1 year and 4 years. Soil sorption and retention capacities and desorption proportions for Cu and Cd were investigated by batch experiments.

Results and discussion

The addition of amendments significantly increased soil pH, but decreased exchange acid and aluminum (Al). The amendments significantly decreased the CaCl₂ extractable Cu and Cd and transformed them from active to inactive fractions. After the application of amendments for 1 year, the maximum sorption capacities ranged from 35.6 to 38.8 mmol/kg for Cu and from 14.4 to 17.0 mmol/kg for Cd, which were markedly higher than those of the application of amendments for 4 years (Cu, 29.6–34.7 mmol/kg; Cd, 10.9–16.4 mmol/kg). Desorption proportions (D) of Cu and Cd using three extractants followed the order of \( {D}_{{\mathrm{NaNO}}_3}<{D}_{{\mathrm{CaCI}}_2}<{D}_{{\mathrm{MgCI}}_2} \) . Moreover, the retention capacities (R) of Cu and Cd both increased and followed the order of R _apatite?>?R _lime?>?R _charcoal, resulting in higher Cu and Cd in the amended soils than the untreated soil.

Conclusions

Apatite, lime, and charcoal increased the soil sorption and retention capacities of Cu and Cd and resulted in higher immobilization efficiencies in the amended soils than the untreated soil. However, the immobilization efficiencies of Cu and Cd decreased with the decrease of sorption capacities after 4 years. It was concluded that apatite had the best effect on the long-term stability of immobilized Cu and Cd and can be applied to immobilize heavy metals in contaminated soils.