土壤-植物系统中磷对重金属生物有效性的影响机制

磷对植物吸收重金属元素的影响作用属于植物营养和重金属污染生态研究的前沿。污染土壤中施入磷是否能够降低重金属离子的生物有效性，除了与重金属离子本身特性有关外，还与含磷化合物的性质及土壤环境条件有关。在分析中，就土壤中磷与重金属离子间交互作用机制、土壤中影响磷降低重金属离子生物有效性的环境因子及磷与重金属交互作用的国内外研究进展作了简要综述，并对今后的研究提出了展望。     

重金属离子Cd^2＋、Pb^2＋污染对土壤酶活性的影响

通过对土壤中比较重要的两种酶（过氧化氢酶、脲酶）活性的测定,研究了重金属离子（Cd^2＋、Pb^2＋）单因素污染、复合污染对两种酶活性的影响,进而找出重金属污染程度与土壤酶活性的关系,为建立土壤中的酶活性可以表征重金属污染程度的生化指标平台提供试验依据。结果表明,在Cd^2＋、Pb^2＋单因素污染影响中,在一定浓度下的重金属离子对土壤酶活性会有激活效应,但大多表现为抑制效应;Cd^2＋、Pb^2＋复合污染对两种土壤酶活性的影响存在着明显差异,其复合污染对脲酶表现出协同抑制负效应的特征;对过氧化氢酶表现出一定的屏蔽作用。通过重金属离子形态对土壤酶有效性影响的研究,脲酶活性可以作为土壤重金属离子（Cd^2＋、Pb^2＋）单因素和复合污染程度的主要生化指标。     

生物炭吸附重金属的研究进展

生物炭是一种废弃物资源化利用的产物。作为新型环境功能材料,生物炭以其优良的环境效应和生态效应成为环境科学等学科研究的前沿热点。因其孔隙结构发达、比表面积巨大和独特的表面化学性质,对环境介质中的重金属离子有很强的吸附作用,进而影响了重金属离子的迁移与归宿。主要从生物炭的材料来源、吸附重金属离子的机制、影响因素以及对土壤中重金属生物有效性的影响等方面进行综述,并提出生物炭吸附重金属离子的未来研究方向。     

微生物矿化修复重金属污染土壤

以选矿厂附近土壤为研究对象,分析了土壤中交换态重金属含量,As、Pb、Cd、Zn和Cu的交换态浓度为14.01、4.95、0.64、33.46和12.95 mg/kg。基于生物矿化原理,利用碳酸盐矿化菌生长代谢过程产生的脲酶来分解底物尿素,产生碳酸根离子,固结重金属离子,使得土壤中活泼的重金属离子转变为碳酸盐矿物态,降低其危险。研究了温度、pH和重金属离子对酶活性的影响,发现环境30℃温度有利于促进酶活性;在弱酸性条件下,底物分解量减少15%;重金属离子在低浓度时对脲酶活性影响不大,浓度提高后对酶活性抑制作用没有加剧。将制备好的微生物矿化修复制剂喷洒于1 000 m2的污染土壤中,实验结果发现,土壤中交换态重金属离子含量在0～20 cm范围内明显减少,As、Pb、Cd、Zn和Cu的交换态浓度分别减少至2.37、1.25、0.31、16.67和3.42 mg/kg。     

土壤重金属的植物污染化学研究进展

针对中国土壤重金属污染加剧的趋势,为改善土壤环境质量和保障农产品安全,提出了土壤重金属的植物污染化学研究领域.结合多年的研究工作,从土壤重金属的植物根际化学行为、土壤重金属的植物吸收与解毒机制和重金属污染土壤的植物-微生物交互作用等方面简要阐述了土壤-植物系统中重金属的分布、存在形态、迁移转化、累积及生物学效应和控制规律的研究进展,并对将来的植物污染化学理论研究提出了展望.     

钝化剂在烟草植物修复铅镉污染土壤中的作用

重金属钝化剂可以改变土壤中重金属的形态,降低其在土壤中的有效浓度、植物毒性及生物有效性,影响污染土壤中植物的生长及其对重金属的吸收。在温室盆栽条件下研究了施加羟基磷灰石（HA）、纳米羟基磷灰石（nHA）、纳米零价铁（nFe0）和纳米TiO2（nTiO2）对烟草植物修复铅镉污染土壤的作用。结果表明,HA降低土壤中Ph、cd的有效性、促进烟草生长、增加了烟草叶、茎、根中cd的吸收量和根系中Pb的吸收量,有利于Ph、cd的钝化和植物修复。nHA也可以降低土壤中Pb、cd的有效性,增加了烟草叶中cd的吸收量,有利于Pb、cd的钝化和cd的植物提取。nFe0和nTiO2：对于土壤Pb和cd的钝化作用和植物修复均没有显著影响。综合来看,HA最适合应用于烟草植物修复铅镉污染土壤。     

土壤胶体对重金属迁移及生物有效性影响的研究进展

土壤中重金属能够通过土壤孔隙迁移至地下水中,对生态环境造成污染,对人体健康构成威胁。土壤胶体因其巨大的比表面积和特殊的双电层结构能够对土壤中重金属的迁移和生物有效性产生影响。总结归纳了pH、离子强度、水动力作用、胶体粒径和孔隙尺寸等因素对重金属迁移行为的阻滞和促进作用。探讨了土壤胶体对重金属生物有效性的影响机制,并对今后的研究方向进行了展望。     

有机肥料联合东南景天修复重金属污染土壤的研究

将两种有机肥料黄腐酸钾和紫云英(Astragalus sinensis)分别与重金属超积累植物东南景天(Sedum alfredii)联用修复重金属污染土壤,研究有机肥料对污染土壤重金属生物有效性、形态以及东南景天重金属积累量的影响。结果显示,修复0～4个月,施加有机肥料对土壤重金属生物有效性均有一定的促进作用;而修复4～8个月,土壤重金属向可氧化态和残渣态转化,生物有效性受到抑制。从东南景天地上部重金属积累量看,修复0～4个月,施加0.3%(质量分数)黄腐酸钾促进东南景天对锌、镉的吸收积累,锌、镉积累量分别比对照提高了280.37%、265.44%;而修复4～8个月,东南景天地上部重金属积累量相较对照均下降。由此可见,提升重金属污染土壤的植物修复效果,还需考虑修复周期的影响。     

含磷材料对矿区铅镉污染土壤重金属形态转化的影响

以湖南郴州东江湖风景区矿区遗留地重金属污染土壤为研究对象,研究了3种含P材料,及其与蒙脱石的组合材料,对矿区土壤铅镉污染的修复效果.实验设6组处理,分别为P1组、P2组、P3组、P1 +M组、P2+M组、P3 +M组,通过添加5％的稳定剂,稳定2d后,分析土壤中铅镉的形态变化.实验结果表明:添加含P材料,及组合材料后,土壤中铅镉的离子交换态、铁锰结合态、有机结合态大幅度降低,残渣态显著升高.对Pb离子转化效果均在90.00％以上,Cd离子的转化效率相对较差,最优P1处理效果为74.20％.离子交换态的减少,有效地降低了重金属的生物有效性,有效地降低了环境风险.同时,含P材料均增加了土壤有效磷的含量,对矿区土壤的肥力也有一定提升.     

土壤/沉积物中重金属生物有效性和生物可利用性的研究进展

土壤/沉积物中重金属的污染问题越来越引起重视,而重金属在环境中的生态风险与其生物可利用性和生物有效性密切相关。在总结国内外研究的基础上,明确了重金属生物有效性和生物可利用性的定义;概述了用于研究土壤/沉积物中重金属生物有效性的生物模型(小鼠、猪、兔子等);总结了用于研究土壤/沉积物中重金属生物可利用性的几种体外方法,包括模拟人类肠胃消化(PBET、SBRC、UBM等)和底栖生物消化;分析了土壤/沉积物中重金属生物有效性和生物可利用性的关键影响因素(土壤/沉积物理化性质和分析方法)。提出了未来土壤/沉积物中重金属生物有效性和生物可利用性的研究方向,以期为重金属生态风险的评价和控制提供参考。     

Effects of Heavy metals on plants and resistance mechanisms

GOAL, SCOPE AND BACKGROUND: As one of the consequences of heavy metal pollution in soil, water and air, plants are contaminated by heavy metals in some parts of China. To understand the effects of heavy metals upon plants and the resistance mechanisms, would make it possible to use plants for cleaning and remediating heavy metal-polluted sites. METHODS: The research results on the effects of heavy metals on plants and resistant mechanisms are compiled from Chinese publications from scientific journals and university journals, mostly published during the last decade. RESULTS AND DISCUSSION: Effects of heavy metals on plants result in growth inhibition, structure damage, a decline of physiological and biochemical activities as well as of the function of plants. The effects and bioavailability of heavy metals depend on many factors, such as environmental conditions, pH, species of element, organic substances of the media and fertilization, plant species. But, there are also studies on plant resistance mechanisms to protect plants against the toxic effects of heavy metals such as combining heavy metals by proteins and expressing of detoxifying enzyme and nucleic acid, these mechanisms are integrated to protect the plants against injury by heavy metals. CONCLUSIONS: There are two aspects on the interaction of plants and heavy metals. On one hand, heavy metals show negative effects on plants. On the other hand, plants have their own resistance mechanisms against toxic effects and for detoxifying heavy metal pollution. RECOMMENDATIONS AND OUTLOOK: To study the effects of heavy metals on plants and mechanisms of resistance, one must select crop cultivars and/or plants for removing heavy metals from soil and water. More highly resistant plants can be selected especially for a remediation of the pollution site. The molecular mechanisms of resistance of plants to heavy metals should be studied further to develop the actual resistance of these plants to heavy metals. Understanding the bioavailability of heavy metals is advantageous for plant cultivation and phytoremediation. Decrease in the bioavailability to farmlands would reduce the accumulation of heavy metals in food. Alternatively, one could increase the bioavailability of plants to extract more heavy metals.     

水体沉积物重金属生物有效性及评价方法

在研究以重金属为主要污染物的水体中,通常把沉积物视为探索环境重金属污染的工具。由于沉积物中重金属化学行为和生态效应的复杂性,对沉积物中重金属生物有效性的研究是当前学术界的热点研究课题。本文就沉积物中重金属的生物有效性及沉积物质量评价方法作了简要评述。包括沉积物对水生生物的作用机理,孔隙水重金属浓度的估算,沉积物质量评价方法,沉积物质量基准。     

Mobility of heavy metals associated with the natural weathering of coal mine spoils

Knowledge of chemical mobility of heavy metals is fundamental to understanding their toxicity, bioavailability, and geochemical behavior. In this paper, two different methods, i.e. mineralogical means and sequential extractions, were employed to analyze the total contents, existing states, and chemical forms of heavy metals in coal mine spoils. The results demonstrate that the mobility of heavy metals in coal mine spoils depends not only on their existing states and the stability of their host minerals but also on the properties of the coal mine spoils. In the process of coal mine spoils-water interaction, sulfides that contain heavy metals first break down and release metals, which are then adsorbed and complexed by the iron oxyhydroxide colloid resulting from pyrite oxidization and organic matter. During the natural weathering of coal mine spoils, only a small fraction of these metals are released to the environment, and most of them still remains in the residual material.     

Assessment of heavy metal bioavailability in contaminated sediments and soils using green fluorescent protein-based bacterial biosensors

A green fluorescent protein (GFP)-based bacterial biosensor Escherichia coli DH5alpha (pVLCD1) was developed based on the expression of gfp under the control of the cad promoter and the cadC gene of Staphylococcus aureus plasmid pI258. DH5alpha (pVLCD1) mainly responded to Cd(II), Pb(II), and Sb(III), the lowest detectable concentrations being 0.1 nmol L(-1), 10 nmol L(-1), and 0.1 nmol L(-1), respectively, with 2h exposure. The biosensor was field-tested to measure the relative bioavailability of the heavy metals in contaminated sediments and soil samples. The results showed that the majority of heavy metals remained adsorbed to soil particles: Cd(II)/Pb(II) was only partially available to the biosensor in soil-water extracts. Our results demonstrate that the GFP-based bacterial biosensor is useful and applicable in determining the bioavailability of heavy metals with high sensitivity in contaminated sediment and soil samples and suggests a potential for its inexpensive application in environmentally relevant sample tests.     

Reduction of bioavailability and leachability of heavy metals during vermicomposting of water hyacinth

Vermicomposting of water hyacinth is a good alternative for the treatment of water hyacinth (Eichhornia crassipes) and subsequentially, beneficial for agriculture purposes. The bioavailability and leachability of heavy metals (Zn, Cu, Mn, Fe, Ni, Pb, Cd, and Cr) were evaluated during vermicomposting of E. crassipes employing Eisenia fetida earthworm. Five different proportions (trials 1, 2, 3, 4, and 5) of cattle manure, water hyacinth, and sawdust were prepared for the vermicomposting process. Results show that very poor biomass growth of earthworms was observed in the highest proportion of water hyacinth (trial 1). The water soluble, diethylenetriaminepentaacetic acid (DTPA) extractable, and leachable heavy metals concentration (percentage of total heavy metals) were reduced significantly in all trials except trial 1. The total concentration of some metals was low but its water soluble and DTPA extractable fractions were similar or more than other metals which were present in higher concentration. This study revealed that the toxicity of metals depends on bioavailable fraction rather than total metal concentration. Bioavailable fraction of metals may be toxic for plants and soil microorganisms. The vermicomposting of water hyacinth by E. fetida was very effective for reduction of bioavailability and leachability of selected heavy metals. Leachability test confirmed that prepared vermicompost is not hazardous for soil, plants, and human health. The feasibility of earthworms to mitigate the metal toxicity and to enhance the nutrient profile in water hyacinth vermicompost might be useful in sustainable land renovation practices at low-input basis.     

Using biochar for remediation of soils contaminated with heavy metals and organic pollutants

Soil contamination with heavy metals and organic pollutants has increasingly become a serious global environmental issue in recent years. Considerable efforts have been made to remediate contaminated soils. Biochar has a large surface area, and high capacity to adsorb heavy metals and organic pollutants. Biochar can potentially be used to reduce the bioavailability and leachability of heavy metals and organic pollutants in soils through adsorption and other physicochemical reactions. Biochar is typically an alkaline material which can increase soil pH and contribute to stabilization of heavy metals. Application of biochar for remediation of contaminated soils may provide a new solution to the soil pollution problem. This paper provides an overview on the impact of biochar on the environmental fate and mobility of heavy metals and organic pollutants in contaminated soils and its implication for remediation of contaminated soils. Further research directions are identified to ensure a safe and sustainable use of biochar as a soil amendment for remediation of contaminated soils.     

Speciation of heavy metals in marine sediments vs their bioaccumulation by mussels.

Total contents and speciation of selected heavy metals, including Al, Fe, Co, Ni, Pb, Zn, Cu, Cr, were measured in sediment samples and mussels Mya arenaria and Astarte borealis collected in the Horsund Fjord off Spitsbergen (Norwegian Sea) and the Bay of Gdansk (Baltic Sea). The investigation aimed at revealing differences in the accumulation pattern of heavy metals in mussels inhabiting sediments characterized by varying metal bioavailability. The contents of metals adsorbed to sediments and associated with iron and manganese hydroxides, which were obtained by sequential extraction, were utilized as a measure of metal bioavailability. The contents of Cd, Pb, Zn, Cu and Cr in mussels collected off Spitsbergen were generally lower than those in mussels from the Baltic Sea. In sediments collected off Spitsbergen the bioavailable fraction represented a small proportion (0-3.7% adsorbed metals and 0-11% associated with metals hydroxides) of total heavy metal contents. In sediments from the Baltic Sea the percentages of metals adsorbed and bound to hydroxides were 1-46% and 1-13%, respectively. The differences in bioavailable metal contents measured in sediments were utilized to explain the different contents of metals in mussels collected in the corresponding sites.     

Influence of bacteria on Pb and Zn speciation, mobility and bioavailability in soil: A laboratory study

A soil column experiment was carried out to investigate the effects of inoculation of bacteria on metal bioavailability, mobility and potential leachability through single chemical extraction, consequential extraction and in situ soil solution extraction technologies. Results showed that bacteria inoculated, including Azotobacter chroococcum, Bacillus megaterium and Bacillus mucilaginosus, may pose both positive and negative impacts on bioavailability and mobility of heavy metals in soil, depending on the chemical nature of the metals. The activities of bacteria led to an increase of water dissolved organic carbon (DOC) concentration and a decrease of pH value, which enhanced metal mobility and bioavailability (e.g. an increase of water-soluble and HOAc-soluble Zn). On the other hand, bacteria could immobilize metals (e.g. a great reduction of water-soluble Pb) due to the adsorption by bacterial cell walls and possible sedimentation reactions with phosphate or other anions produced through bacterial metabolism.     

Sequential extraction of heavy metals during composting of sewage sludge

The major limitation of soil application of sewage sludge compost is the total heavy metal contents and their bioavailability to the soil-plant system. This study was conducted to determine the heavy metal speciation and the influence of changing the physico-chemical properties of the medium in the course of composting on the concentrations, bioavailability or chemical forms of Cu, Zn, Pb and Ni in sewage sludge. Principal physical and chemical properties and FTIR spectroscopical characterization of sludge compost during treatment show the stability and maturity of end product. The total metal contents in the final compost were much lower than the limit values of composts to be used as good soil fertilizer. Furthermore, it was observed by using a sequential extraction procedure in sludge compost at different steps of treatment, that a large proportion of the heavy metals were associated to the residual fraction (70-80%) and more resistant fractions to extraction X-NaOH, X-EDTA, X-HNO3 (12-29%). Less than 2% of metals bound to bioavailable fractions X-(KNO3+H2O). Heavy metal distribution and bioavailability show some changes during composting depending on the metal itself and the physico-chemical properties of the medium. Bioavailable fractions of all elements tend to decrease except Ni-H2O. Zn and mainly Cu present more affinity to organic and carbonate fractions. In contrast, Pb is usually preferentially bound to sulfide forms X-HNO3. Nickel shows a significant decrease of organic form. Significant degrees of correlation were found between heavy metal fractions and changes of some selected variables (e.g. pH, ash, organic matter, humic substance) during the course of composting. Mobile fractions of metals are poorly predictable from the total content. The R2 value was significantly increased by the inclusion of other variables such as the amount of organic matter (OM) and pH.     

Comparison of a rhizosphere-based method with other one-step extraction methods for assessing the bioavailability of soil metals to wheat

There is no method recognized as a universal approach for evaluation of bioavailability of heavy metals in soil. Based on the simulation of the rhizosphere soil conditions and integration of the combined effects of root-soil interactions as a whole, a rhizosphere-based method has been proposed. Wet fresh rhizosphere soil was extracted by low-molecular-weight organic acids (LMWOAs) to fractionate metal fractions of soil pools, which were then correlated with the metal contents of wheat roots and shoots. The rhizosphere-based method was compared with other one-step extraction methods using DTPA, EDTA, CaCl2, and NaNO3 as extractants and the first step of the Community Bureau of Reference (BCR) method. Simple correlation and stepwise multiple regression analysis were used for the comparison. Simple correlation indicated that the extractable Cu, Zn, Cr, and Cd of soils by the rhizosphere-based method were significantly correlated with the metal contents of wheat roots. For DTPA, BCR1 and EDTA methods there was a relatively poor correlation between the extractable Cu, Zn and Cd of soil and metal contents of wheat roots. Stepwise multiple regression analysis revealed that the equation of the rhizosphere-based method was the simplest one, and no soil properties variables needed to be added. In contrast, the equations of other one-step extraction methods were more complicated, and soil properties variables needed to be entered. The most distinct feature of the rhizosphere-based method was that the recommended method was suitable for acidic, neutral and near alkaline soils. However, the DTPA and EDTA extraction methods were suitable for calcareous soils only-or-only for acidic soils. The CaCl2, and NaNO3 extraction methods were only suitable for exchangeable metals. In short, the rhizosphere-based method was the most robust approach for evaluation of bioavailability of heavy metals in soils to wheat.