Characterization of Heavy Metals in Soil by High Gradient Magnetic Separation

In recent years forecasting soil cleaning efficiencies of polluted soil, especially those contaminated with heavy metals, has become an important issue. Failure of the methods to predict the right efficiency has resulted in financial losses and penalties. This article describes an addition to the traditional characterization methods for soils contaminated by heavy metals, improving the quality of the basic decisions to be made. The method is based on magnetic separation using a Frantz Isodynamic Separator (FIS) for this study. The FIS isolates soil particles containing heavy metals so that these particles, which are relevant for soil cleaning, can be studied in more detail. Four contaminated soils were tested, for example, soils that were a problem for the soil-cleaning industry. The experiments indicate that each soil has its own magnetic properties that should be regarded as a fingerprint. Density measurements of two soils show that densities approach the quartz density separated at moderate and high magnetic fields suggesting that some of the heavy metals cannot be removed by density separation techniques. A pilot plant scale test supports this conclusion. It also shows that a part of the heavy metals are found in particles lighter than quartz. Based on the results, a qualitative model is proposed to account for the presence of the heavy metals in soil.     

A perspective on metals in soils

Soil contaminated with metals from a variety of sources can be toxic to plants and animals, including humans. The extent of contamination is often determined by comparison with the total elemental composition of an uncontaminated soil, although some leaching tests have also been proposed. In any event, knowledge of the natural background concentrations of metals at the site is required. Analysis of a control sample from the site will provide some information, but soils are still inherently variable. This review summarizes the total elemental composition of soils not known to be contaminated from anthropogenic sources. The total concentrations of 50 metals reported for these soils were shown to be log‐normally distributed, making the geometric mean (GM) and geometric standard deviation (GS) appropriate. Thus, 99.7% of the data should fall between GM/GS³ and GM*GS³. Fifteen metals were above the upper 99.7% limit and eight were below the lower limit. Most fell between the 99.9% limits of GIWGS⁴ and GM*GS⁴. The exceptions are nine metals (At. Ca, Fe, Mg, K Na, S, Si, and Ti) present at high concentrations with large GS values of 7500 to 66,400. GSs exceeding 5.0 probably indicate distributions with multiple modes. For K and Si, the arithmetic mean may be more appropriate. Available information on the concentrations of metals in relation to soil taxonomy is included, along with some specific data for soils in the Northeast. Data for the EPA target analytes are tabulated to assist regulators and others in cases where the soil is contaminated and remediation is required.     

Effects of ferric soils on arthropod abundance and herbivory on <Emphasis Type="Italic">Tibouchina heteromalla</Emphasis> (Melastomataceae): is fluctuating asymmetry a good indicator of environmental stress?

High concentration of heavy metals in the soils represents an important factor of physiological stress that influences the normal functioning of plants through oxidation processes, and negatively affects insect performance and leaf consumption by herbivorous insects. One useful indicator to evaluate environmental stress in plants by heavy metals and herbivory is the fluctuating asymmetry, which describes the random differences in size or shape between the two sides of a bilateral character in organisms and it is a widely used measure of developmental instability in plants. We evaluated under natural conditions, the effects of variation of heavy metals in the soils on herbivore patterns, fluctuating asymmetry and arthropod abundance in Tibouchina heteromalla in rupestrian grasslands along the Espinhaço chain in Brazil. We selected two study areas, the first characterized by the presence of soils with low concentration of heavy metals (quartzite soils). In the second area, the soils are characterized by the presence of high concentration of heavy metals such as iron (ferric soils). We found that leaf thickness was higher in ferric soils than in quartzite soils. Conversely, total leaf area was greater in quartzite soils in comparison to ferric soils. Plants in soils with heavy metals had both lower herbivory levels and arthropod abundance than plants in soils with low concentrations of heavy metals. Fluctuating asymmetry levels were significantly greater in individuals from quartzite soils compared to individuals from ferric soils. Herbivory was positively related with individual fluctuating asymmetry in quartzite soils. Our results suggest that T. heteromalla presents tolerance to soils with heavy metals suggesting an acclimatization to these environmental conditions, and therefore, ferric soils may not represent a factor of environmental stress.     

阜新市农田土壤重金属含量及其分布特征

通过对辽宁省阜新市城郊区县180处农田土壤的取样调查分析,初步了解了农田土壤重金属As、Cu、Zn、Ni的含量特征及其空间分布,并探讨了当地矿业开采活动对农田土壤重金属积累及空间分布的影响.结果表明,研究区域内农田土壤Cu、Zn和Ni的几何平均含量均高于背景值,且这3种重金属存在普遍累积的现象;不同种植类型土壤中,菜地土壤Cu、Zn、As含量显著高于粮田,且重金属积累更为明显;4种重金属的空间分布均呈城区高于郊县的趋势;重金属含量较高的区域与矿山开采区域基本重叠.研究区域内采矿活动是农田重金属的重要来源,同时畜禽养殖业所产生的畜禽粪便可能对农田土壤中Cu、Zn和As的增加有一定作用.当地农牧业生产和布局应适当考虑土壤污染的风险.     

Source identification and availability of heavy metals in peri-urban vegetable soils: A case study from China

The purpose of this study was to investigate the total and available concentrations of Pb, Cr, Cu, Ni, and Zn in the vegetable soils from the outskirts of a heavy industry city, Northeast China, and to assess the sources of heavy metals and their availability. The average concentrations of Pb, Cu, and Zn were significantly higher than their background values of Changchun topsoil. Principal component analysis, cluster analysis, and geostatistical analysis results suggested that Pb, Cu, and Zn were consistently from anthropogenic sources, while Cr and Ni were from natural sources with low concentrations. Kriging results showed that several hotspots of high metal concentration were identified by the geochemical maps and caused by different environmental factors. Although the available (ethylene-diamine-tetraacetic acid-extractable) fractions showed much lower values than total concentrations of metals, Pb and Cu had relatively high AR^a (average availability ratio of metals) values. Our findings show that most of the studied metals had accumulated to some extent in vegetable soils and several hotspots of high metal concentration appeared at the peri-urban of Changchun. The concentrations of some metals in peri-urban vegetable soils have been largely affected by anthropogenic activities. Appropriate measures should be taken to effectively control heavy metal levels in vegetable soils and thus protect human health.     

根际圈在污染土壤修复中的作用与机理分析

根际圈以植物根系为中心聚集了大量的生命物质及其分泌物,构成了极为独特的“生态修复单元”。本文叙述了根在根际圈污染土壤修复中的生理生态作用,富集、固定重金属,吸收、降解有机污染物等功能;菌根真菌对根际圈内重金属的吸收、屏障及螯合作用,对有机污染物的降解作用;根际圈内细菌对重金属的吸附与固定,对有机污染物的降解作用以及根际圈真菌和细菌的联合修复作用等,同时对可能存在的机理进行了分析,认为根际圈对污染土壤的修复作用是植物修复的重要组成部分和主要理论基础之一,并指出利用重金属超富集植物修复重金属污染土壤具有广阔的应用前景;筛选对水溶性有机污染物高吸收富集及其根 发泌能力强的特异植物,同时接种利于有机污染物降解的专性或非专性真菌和细菌可能会成为有机污染土壤植物修复研究的重要方向之一。     

Hyperaccumulation of nickel by two Alyssum species from the serpentine soils of Iran

Serpentine soils, which contain relatively high concentrations of nickel and some other metals, are the preferred substrate for some plants, especially those that accumulate Ni in their tissues. In temperate regions more Ni-hyperaccumulator plants are found in Alyssum than in any other genus. In this study, serpentine soils of two areas (Marivan and Dizaj) in the west/northwest of Iran and also perennial Alyssum plants growing on these soils were analyzed for Ni and some other metals. The highest concentrations of total metals in the soils of these areas for Ni, Cr, Co and Mn were 1,350, 265, 94 and 1,150 μg g⁻¹, respectively, while concentrations of Fe, Mg and Ca reached 3.55%, 16.8% and 0.585% respectively. The concentration of exchangeable Ni in these soils is up to 4.5 μg g⁻¹. In this study two Alyssum species, A. inflatum and A. longistylum, have been collected from Marivan and Dizaj, respectively. Analysis of leaf dry matter shows that they can contain up to 3,700 and 8,100 μg Ni g⁻¹, respectively. This is the first time that such high Ni concentrations have been found in these species. The concentrations of other metals determined in these species were in the normal range for serpentine plants, except for Ca, which was higher, up to 5.3% and 3.5%, respectively     

Baseline Levels of Metals in Volcanic Soils of the Azores (Portugal)

Data on metal concentrations present in the soils of the Azores (Portugal) are scarce. The goal of this study was to measure the current levels of several metals in the top horizon of soils of two areas, distinguishable by their volcanic activity and physical characteristics, in order to establish some baseline concentrations of these elements. Soil samples were taken in similar ways from five sites in a volcanically active area and another five sites in an area without volcanic activity. Particle-size fractions, % organic matter, moisture content, pH, and major and trace elements compositions were measured. In general, the concentrations of trace metals in the soils from Santa Maria (inactive volcanism) were higher than those from Furnas (active volcanism), with the exception of Zn. The soils from Furnas, which have slightly lower pH and less % clay-silt than Santa Maria, will probably make such trace metals as Zn become more readily bioaccessible, and therefore pose a larger threat to living organisms inhabiting these soils.     

磷酸盐修复重金属污染土壤的研究进展

从研究方法、反应机理以及风险评价等方面综述了磷酸盐修复重金属污染土壤的研究进展,分析和讨论了其中存在的问题和不足,提出了今后加强研究的重点。目前磷酸盐修复重金属污染土壤时,使用的主要研究方法有化学形态提取法、化学平衡形态模型法和光谱及显微镜技术,各个方法都有其优缺点,应该结合使用并探索新方法。磷酸盐稳定重金属的作用机理主要有3个:磷酸盐诱导重金属吸附、磷酸盐和重金属生成沉淀或矿物和磷酸盐表面吸附重金属,但磷酸盐与重金属反应的机理十分复杂,人们尚不完全清楚,因此难以有效区分和评价诱导吸附机理和沉淀机理或其它固定机理,相应地对磷酸盐修复重金属的长期稳定性难以预测。磷酸盐修复重金属污染土壤时由于其较高的施用量可能会造成磷的积聚从而引发一些环境风险,如磷淋失造成水体富营养化,营养失衡造成作物必需的中量和微量元素缺乏以及土壤酸化等。所以应该谨慎选择磷肥种类和用量,最好是水溶性磷肥和难溶性磷肥配合、磷肥与石灰物质等配合施用。今后应着重研究磷酸盐与重金属相互作用的机理区分和评价;关注磷酸盐修复重金属污染土壤时存在的潜在风险,特别是加强植物长期不断吸收磷或其它环境条件变化致使土壤磷素持续减少过程中稳定的重金属溶解性和移动性的研究,磷酸盐修复重金属污染土壤的长期田间实践等。     

Metallomics and chemical speciation: towards a better understanding of metal-induced stress in plants

Most metal ions are toxic to plants, even at low concentrations, despite the fact that some are essential for growth and play key roles in metabolism. The majority of metals induce the formation of reactive oxygen species, which require the synthesis of additional antoxidant compounds and enzymes for their removal. New techniques that have greatly improved the identification, localisation and quantification of metals within plant tissues have led to the science of metallomics. This advancement in knowledge should eventually allow the characterisation of plants used in the process of phytoremediation of soils contaminated with toxic metals.     

我国农田生态系统重金属的循环与调控

本文系统分析了我国农田土壤重金属的含量状况,探讨了农田生态系统中重金属的输入、输出及其平衡.农田生态系统中重金属存在一定的累积效应,但整体上超标风险较小,而部分作物、特别是蔬菜可能存在一定的超标风险.在采矿区和冶炼厂周边地区,以及废弃物利用强度较大的农区,土壤和作物中重金属超标的风险较大,是普通农区的十倍甚至数十倍以上.针对我国农田重金属污染现状,提出了调控农田生态系统重金属循环的有效措施,并对相关领域今后的研究进行了展望.     

Metal concentrations in plants and soils from two British serpentine sites

Summary The concentrations of several metals in plants and soils from two British serpentine sites were investigated. Large interspecific differences in plant tissue concentrations of metals were found and are believed to reflect innate differences in plant response to the unusual soil conditions. Particularly noteworthy are the high iron levels in some of the species.     

微生物与重金属间的相互作用及其应用研究

从多方面阐述了微生物与重金属二者间相互作用,指出微生物在生长代谢过程中能淋滤、吸收和转化重金属,对重金属有一定的抗性和解毒作用;但是,一定浓度的重金属对微生物过程及其种群具有较大的毒性。影响微生物在环境介质中的活动,矿业工程生产工艺已充分利用微生物能淋滤,吸收和转化重金属等特性来处理低品位难浸矿石,环境保护领域也积极利用微生物对重金属的抗性和解毒作用来实现工业废弃物的处理以及被重金属污染土壤的修复。利用微生物的生物量及其活性可以评价环境中不同介质的重金属污染水平。     

Ecology of nematophagous fungi: Effect of the soil nutrients N,P and K,and seven major metals on distribution

The effects of the major soil nutrients and seven common metals on the distribution of nematophagous fungi were evaluated by comparing the concentration of the elements in soils with and without nematophagous fungi. Mineral nutrients, which were all positively correlated with nematode density, were the most important elements determining the presence of such fungi. Endoparasites producing adhesive conidia were independent of all the elements tested, while those species forming ingested conidia were isolated from soils high in nutrients, indicating a strong dependence on nematode density. Knob forming predators which rely on their ability to spontaneously produce traps to obtain nutrients were isolated from soils with low concentrations of mineral nutrients, while species with constricting rings were isolated from richer soils containing a greater density of nematodes. Net-forming species were largely independent of soil fertility, although generally they were isolated from soils with limited nutrientsd, especially K. Like other fungi, nematophagous fungi are generally not found in soils containing elevated concentrations of heavy metals. The results indicate that even concentrations of heavy metals which naturally occur in Irish soils can restrict the distribution of this fungal group. However the endoparasiteMeria coniospora is tolerant to all metals and to Cu in particular.     

Hyperaccumulators, arbuscular mycorrhizal fungi and stress of heavy metals

Use of plants, with hyperaccumulating ability or in association with soil microbes including the symbiotic fungi, arbuscular mycorrhiza (AM), are among the most common biological methods of treating heavy metals in soil. Both hyperaccumulating plants and AM fungi have some unique abilities, which make them suitable to treat heavy metals. Hyperaccumulator plants have some genes, being expressed at the time of heavy metal pollution, and can accordingly localize high concentration of heavy metals to their tissues, without showing the toxicity symptoms. A key solution to the issue of heavy metal pollution may be the proper integration of hyperaccumulator plants and AM fungi. The interactions between the soil microbes and the host plant can also be important for the treatment of soils polluted with heavy metals.     

Recent developments in the application of proteomics to the analysis of plant responses to heavy metals

Pollution of soils by heavy metals is an ever‐growing problem throughout the world, and is the result of human activities as well as geochemical weathering of rocks and other environmental causes such as volcanic eruptions, acid rain and continental dusts. Plants everywhere are continuously exposed to metal‐contaminated soils. The uptake of heavy metals not only constrains crop yields, but can also be a major hazard to the health of humans and to the entire ecosystem. Although analysis of gene expression at the mRNA level has enhanced our understanding of the response of plants to heavy metals, many questions regarding the functional translated portions of plant genomes under metal stress remain unanswered. Proteomics offers a new platform for studying complex biological functions involving large numbers and networks of proteins, and can serve as a key tool for revealing the molecular mechanisms that are involved in interactions between toxic metals and plant species. This review focuses on recent developments in the applications of proteomics to the analysis of the responses of plants to heavy metals; such studies provide a deeper understanding of protein responses and the interactions among the possible pathways that are involved in detoxification of toxic metals in plant cells. In addition, the challenges faced by proteomics in understanding the responses of plants to toxic metal are discussed, and some possible future strategies for meeting these challenges are proposed.     

The Effect of Electrolyte Type and Concentration on the Release of Cd,Cu, Ni,and Zn in Some Contaminated Calcareous Soils

This paper reports the results of desorption experiments of cadmium (Cd), copper (Cu), nickel (Ni), and zinc (Zn) from some contaminated calcareous soils under four electrolyte types (CaCl₂, MgCl₂, NaCl and Na₂SO₄) with different electrolyte concentrations (0.5, 4 and 10 mM). Among electrolytes, CaCl₂ significantly released more metals from soils. There was a negative relationship between total Cu and Zn content and percentage of Cu and Zn released (average of electrolyte concentrations) using CaCl₂ solution, indicating a higher Cu and Zn released when their total content was low. Generally, Cd, Cu, and Zn speciation was affected by both type of electrolytes and their concentrations, whereas Ni speciation stayed mostly stable and was almost unaffected by applied solutions. It can be suggested that beside competition with cations, chloro-complexation is important parameter in Cd release, while CuOH⁺, and to some extent ZnOH⁺ are important species affecting release of Cu and Zn. The distribution coefficient (K_d) values for each metals greatly varied with the types of electrolytes and electrolyte concentration. On the basis of average percentage of metal released under different electrolytes and concentrations the following sequences was found: Cd > Cu > Ni > Zn. The results are important in understanding the mobility of metals under different solutions and indicating that, Cd and Zn soils may pose a higher and lower mobility and ecological risk in contaminated calcareous soils, respectively.     

Assessment of a heavy metals‐contaminated site using sequential extraction,TCLP, and risk assessment techniques

The mobility of selected heavy metals in contaminated soil at a previous industrial site in Brisbane, Australia, was assessed using a sequential extraction technique. Copper, Pb, Zn, Cr, Fe, and Mn were extracted from the soil solution/exchangeable, carbonate, Fe and Mn oxides, and organic matter fractions. The amounts of metals adsorbed by these fractions were used as an indicator of each metal's mobility in the soil. Copper and Pb were largely adsorbed by the organic and oxide fractions, while a significant amount of Zn was extracted from the carbonate fraction. The potential mobility and biological availability of the metals in these soils is Zn > Cr = Cu ≈ Pb. Soils were also analyzed using the toxicity characteristic leaching procedure (TCLP) to determine whether the contaminated soil could be disposed of by landfilling. The leachability of all metals from the soils was very low, with metal concentrations below the allowable limits. The TCLP also showed that Zn was the most mobile metal in these soils. An environmental and health risk assessment was undertaken, and it was concluded that the site did not represent a risk despite the “total”; concentrations of some metals being up to 40 times the investigation threshold value adopted in Australia.     

Arbuscular mycorrhiza can depress translocation of zinc to shoots of host plants in soils moderately polluted with zinc

There is increasing and widespread interest in the maintenance of soil quality and remediation strategies for management of soils contaminated with organic pollutants and trace metals or metalloids. There is also a growing body of evidence that arbuscular mycorrhizal (AM) fungi can exert protective effects on host plants under conditions of soil metal contamination. Research has focused on the mechanisms involved and has raised the prospect of utilizing the mutualistic association in soil re-vegetation programmes. In this short paper we briefly review this research, summarize some recent work and highlight some new data which indicate that the alleviation of metal phytotoxicity, particularly Zn toxicity, by arbuscular mycorrhiza may occur by both direct and indirect mechanisms. Binding of metals in mycorrhizal structures and immobilization of metals in the mycorrhizosphere may contribute to the direct effects. Indirect effects may include the mycorrhizal contribution to balanced plant mineral nutrition, especially P nutrition, leading to increased plant growth and enhanced metal tolerance. Further research on the potential application of arbuscular mycorrhiza in the bioremediation or management of metal-contaminated soils is also discussed.     

Diversity of Arbuscular Mycorrhizal Fungus Populations in Heavy-Metal-Contaminated Soils

High concentrations of heavy metals have been shown to adversely affect the size, diversity, and activity of microbial populations in soil. The aim of this work was to determine how the diversity of arbuscular mycorrhizal (AM) fungi is affected by the addition of sewage-amended sludge containing heavy metals in a long-term experiment. Due to the reduced number of indigenous AM fungal (AMF) propagules in the experimental soils, several host plants with different life cycles were used to multiply indigenous fungi. Six AMF ecotypes were found in the experimental soils, showing consistent differences with regard to their tolerance to the presence of heavy metals. AMF ecotypes ranged from very sensitive to the presence of metals to relatively tolerant to high rates of heavy metals in soil. Total AMF spore numbers decreased with increasing amounts of heavy metals in the soil. However, species richness and diversity as measured by the Shannon-Wiener index increased in soils receiving intermediate rates of sludge contamination but decreased in soils receiving the highest rate of heavy-metal-contaminated sludge. Relative densities of most AMF species were also significantly influenced by soil treatments. Host plant species exerted a selective influence on AMF population size and diversity. We conclude based on the results of this study that size and diversity of AMF populations were modified in metal-polluted soils, even in those with metal concentrations that were below the upper limits accepted by the European Union for agricultural soils.