土壤修复过程中重金属形态的研究综述

重金属污染土壤的修复是现阶段污染土壤治理中的难点之一,在土壤修复过程中对重金属的形态研究已在多个领域中开展,并且在重金属形态及其与生物有效性和毒性等研究领域取得了一定的成果。本文综述了现阶段在污染土壤修复过程中对重金属形态研究的主要领域,分析研究重金属形态的必要性,总结出土壤修复过程中重金属形态方面应当从重金属在土壤与植物中的存在形态入手,研究重金属元素在不同界面间的迁移转化规律,通过阻断重金属元素在污染源、土壤、生物之间的传递链条,以阻止重金属对生物体造成危害,从而为土壤重金属污染的治理修复提供理论基础。     

Heavy metal accumulation in soil after application of organic wastes

Municipal solid waste compost and cattle manure are used as organic fertilizers in agriculture and horticulture. These wastes, however, may also have some negative effects on the agricultural environment. This study investigates the effects of municipal solid waste compost of Kerman (MSC) and cattle manure (CM) on availability of the heavy metal in calcareous soil (extractable with EDTA) in greenhouse conditions. The MSC and CM were mixed thoroughly with soil at rates of 0%, 2%, and 4% of dry matter. After 90 days of incubation, the soil samples were analyzed. Addition of levels of each two organic wastes into soil significantly decreased the soil pH and increased the soil EC as compared with control (unamended soil).The available contents (EDTA-extractable) of Cd, Pb, Cu, Zn, and Cu in the soil samples were increased because of each two organic treatments applied. The heavy metal contents in the soil samples amended with MSC were more than CM. The heavy metal contents of organic wastes were well below the maximum allowed by USEPA. It is recommended that in Iran, the legal maximum permissible limit for heavy elements in organic wastes must be determined.     

Heavy metal retention by soil mineral phases during a potential soil contamination by sewage sludge

The immobilization conditions of heavy metals （Ni, Cu, Zn, Pb） potentially released from sewage sludge to soils were examined. Competitive adsorption experiments, sequential extraction and analytical electron microscopic studies were performed on soils with different compositional characteristics to gain information about the interaction and association of metals with soil minerals. The results showed that Cu and Pb can be characterized by a preferred adsorption in contrast to Zn and Ni independent of initial metal concentrations, ratios, and soil composition. Precipitation is the dominating retardation process in the sample containing carbonates, but it is also characteristic of metals with inhibited adsorption in samples free of carbonate. Both Cu and Pb show high affinity towards organic matter. Differences in metal affinities towards different clay minerals show the immobilization of Cu rather by specific adsorption and that of Pb rather by ion exchange. According to the sequential extraction studies the role of ion exchange is the most important process for the retardation of Zn, and in the sample containing montmorillonite. The specific adsorption is significant mostly for Cu and Pb, and primarily in samples rich in organic matter and containing vermiculite. The co-precipitation of metals with Fe-Mn oxides is significant primarily for Cu, but in some cases Pb and Zn can be also found in this fraction. In general, the strength of immobilization for the studied metals is as follows： Cu〉Pb〉Zn〉Ni. Significantly higher metal adsorption was found by the phases in the sample containing carbonates, as well as in samples characterized by the close association of clay minerals and iron oxides. Smectite and vermiculite are the most important adsorbents in soils for all of the metals. Additionally, iron-oxides immboilize significant amounts of Cu and Zn, too.     

通辽地区污灌区土壤中重金属迁移规律

通辽地区污灌区土壤土层剖面不同深度重金属铬、铜、镉、铅元素测试和分析结果表明，重金属在垂直方向上的浓度随着土层加深，含量减少，土壤对重金属具有吸附和过滤作用，污灌区地下水目前没有受到污染。     

Heavy metal pollution in the soil surrounding a thermal power plant in Playas de Rosarito,Mexico

The generation of electricity has been identified as one of the main pollutant activities, and some studies have established an increment of heavy metals in soil in the areas surrounding these plants. The aim of this study was to evaluate the soil concentrations of heavy metals in the zone surrounding a thermoelectric power in Mexico. Thirty-two top soil samples (0–5 cm) were collected; additionally, four depth profiles (1 m) were investigated. Median concentrations for chromium, vanadium, nickel, mercury, and cadmium were 47, 47, 73, 0.02, and 0.01 mg/kg, respectively. Higher Cr, Ni, and V concentrations were observed in the soil depth profiles located closer to the plant in comparison with the concentrations found in the soil depth profile located further away from the plant; these results may indicate a possible accumulation of these metals. The geoaccumulation index results indicated that most of the sites were in the classifications of unpolluted and unpolluted to moderately polluted (classes 1 and 2). The statistical results showed that downwind of the plant in relation to the prevailing winds, there was a strong correlation between soil concentrations of chromium, copper, nickel, and vanadium. Based on the results of this study, it can be concluded that the use of fuel oil at the thermoelectric plant contributed to the accumulation of vanadium and nickel in the soil of the surrounding areas, as well as chromium and copper.     

Heavy metal pollution and soil magnetic susceptibility in urban soil of Beni Mellal City (Morocco)

The assessment of anthropogenic impact in the urban environment can be evaluated according to heavy metal contents of soils such as Pb, Cu, Zn, Cd and Fe. These elements have more affinity to establish metallic bond with ferrous material leading to enhancement of soil magnetic susceptibility. The objective of this study was to undertake joint magnetic and geochemical investigations of road-side urban soil materials to address the environmental pollution of Beni Mellal city that has been subjected to environmental stress, due to population overpressure and related urbanization. Twenty three soils magnetic susceptibility profiles were made along 5 km peripheral national road (N8) in Beni Mellal. The magnetic survey reported here for the first time on this City’s topsoils tries to establish the link between magnetic properties and the content of heavy metals. High magnetic susceptibility values and high contents of heavy metals were found near the paved edge of the road and within the place reserved as large engine park. Magnetic extracts of highly polluted areas and unpolluted soil (olive plantation) were analyzed by SEM coupled with RDX in order to discriminate anthropogenic magnetic spherules and pedo-lithogenic magnetite-like minerals. Magnetic mineralogy determined by Mössbauer spectroscopy suggests the presence of hematite, magnetite and goethite in highly polluted areas. The iron oxides and especially goethite are efficient in incorporating and/or adsorbing foreign ions.     

Heavy metal distribution in soil and plant in municipal solid waste compost amended plots

A field study was carried out to evaluate long-term heavy metal accumulation in the top 20 cm of a Tunisian clayey loam soil amended for four consecutive years with municipal solid waste compost at three levels (0, 40 and 80 t/ha/y). Heavy metals uptake and translocation within wheat plants grown on these soils were also investigated. Compared to untreated soils, compost-amended soils showed significant increases in the content of all measured metals: cadmium, chromium, copper, nickel, lead and zinc in the last three years, especially for plots amended with municipal solid waste compost at 80 t/ha/y. Wheat plants grown on compost-amended soils showed a general increase in metal uptake and translocation, especially for chromium and nickel. This heavy metal uptake was about three folds greater in plots amended at 80 t/ha/y as compared to plots amended at 40 t/ha/y. At the end of the experimental period, the diluting effect resulting from enhanced growth rates of wheat plants due to successive compost applications resulted in lower concentrations in the plants (grain part) grown on treated plots. On the other hand, chromium and nickel were less mobile in the aerial part of wheat plants and were accumulated essentially in root tissues. Plant/soil transfer coefficients for compost-amended treatments were higher than threshold range reported in the literature, indicating that there was an important load/transfer of metal ions from soils to wheat plants.     

Heavy metal retention in secondary precipitates from a mine rock dump and underlying soil, Dalarna, Sweden

This study investigates the retention of heavy metals in secondary precipitates from a sulfidic mine rock dump and underlying podzolic soils by means of mineralogical and chemical extraction methods. The rock dump, which is at least 50 years old, consists of a 5–10-cm-thick leached zone and an underlying 110–115-cm-thick accumulation zone. Optical microscopy and electron microprobe analyses confirm that pyrrhotite weathering has proceeded much further in the leached horizon relative to the accumulation horizon. The weathering of sulfides in the leached zone has resulted in the migration of most heavy metals to the accumulation zone or underlying soils, where they are retained in more stable phases such as secondary ferric minerals, including goethite and jarosite. Some metals are temporarily retained in hydrated ferrous sulfates (e.g., melanterite, rozenite). Received: 28 October 1996 · Accepted: 24 February 1997     

Heavy metal geochemistry and mineral magnetic characterization of urban soil in Xuzhou,China

In the present study, the enrichment, availability, speciation of heavy metals including Pb, Zn, Cu, Cd, Ni and Sb and magnetic properties of urban soils of Xuzhou (China) were investigated. All analyzed metals showed elevated concentrations compared to local background concentrations. Cadmium and Sb are the metals most enriched in the analyzed area, presenting enrichment factor, on average, of 16.5 and 8.3, respectively. By self-organizing map in combination with diagnostic ratios, the source of Sb, Cd, Cu and Pb in soils might be mainly from traffic emissions. Sequential extractions indicate that metals were primarily associated with the reducible fraction with the exception of Ni. The order of extraction efficiency of various metals was SBET (simplified physiologically based extraction test) > DTPA (diethylenetriaminepentaacetic acid) > CaCl₂. The magnetic results show that soil samples were dominated by a strong ferrimagnetic mineral component with multi- and single-domain magnetic grains. Only CaCl₂ extractable Sb was found to show significant correlations with χlf and SIRM. For both DTPA and SBET extractions, all metals investigated showed significant associations with both χlf and SIRM (saturation isothermal remanent magnetization).     

Heavy metal contents in soil of major towns in the east coast of Peninsular Malaysia

A total of 63 soil samples from 3 different soil profiles （urban, suburban and industrial areas） in major towns in the east coast of Peninsular Malaysia were analyzed for the total concentrations of Cu, Zn, Pb, Ni and Cr. The soil samples were subjected to acid digestion and the concentrations of total metals extracted were measured or flame atomic absorption spectrometry and inductively coupled plasma - atomic emission spectrometry. According to the result of this study, Pb and Zn concentrations in urban soils are much higher than those of industrial and suburban soils. Total concentrations of Cu and Cr in industrial soil samples are high compared to other two soil profiles and Ni concentrations in the suburban area are slightly higher those of urban and industrial soils. Since Malaysia has not yet to come up with her own soil maximum allowable limit, the heavy metal concentrations were compared with the Dutch maximum allowable limit. The results indicated that the median of heavy metals values in the three different soil profiles is still below the Dutch system limit. From the maximum allowable value obtained from the Dutch system, a contamination/pollution （C/p） index for each site was calculated for the set of these five heavy metals. An advantage of using this method is to make a differentiation between pollution （C/p〉1） and contamination （C/p〈1） status in soils as well as being able to characterize each status into 5 different categories （slight, moderate, severe, very severe and excessive）.     

Heavy metal contamination of soil around Pali Industrial Area,Rajasthan, India

Due to rapid industrialization, urbanization and intensive agriculture in India increasing contamination of heavy metals in soil has become a major concern. An environmental geochemical investigation was carried out in and around the Pali industrial development area of Rajasthan to determine the effect of contamination in the study area. Soil samples collected near the Pali industrial area were analyzed for Pb, Cr, Cu, Zn, Sr and V contents by using Philips PW 2440 X-ray fluorescence spectrometer. Samples were collected from the industrial area of Pali from the top 10 cm layer of the soil. Most of the samples were collected near small streams adjacent to industrial areas, and near Bandi River. Levels of the metals in soils around the industrial area were found to be significantly higher than their normal distribution in soil such as Pb – 293 mg/kg, Cr – 240 mg/kg, Cu – 298 mg/kg, Zn – 1,364 mg/kg, Sr – 2,694 mg/kg and V – 377 mg/kg. High concentration of these toxic elements in soil is responsible for the development of toxicity in agriculture products, which in turn affects human life. Distribution of metals, their contents at different locations, correlation of heavy metals in soil and their effect on human health are discussed in the paper.     

Heavy metal distribution between parent soil and pepper in an unpolluted area,Hainan Island,China

Consuming edible plants contaminated by heavy metals transferred from soil is an important pathway for human exposure to environmental contaminants. In the past several decades, heavy metal accumulation in contaminated soil has been widely studied; however, few researches investigated the background levels of metals in plants and evaluated the difference in plants grown in soils produced from different parent rocks. In this study, a systemic survey of heavy metal distribution and accumulation in the soil–pepper system was investigated in an unpolluted area, Hainan Island, China. Levels of Cu, Pb, Zn and Cd were measured in soils and pepper fruits from five representative pepper-growing areas with different soil parent rocks (i.e. basalt, granite, sedimentary rock, metamorphic rock and alluvial deposits). Average concentrations of Cu, Pb, Zn and Cd in pepper fruits were 11.52, 0.84, 8.77 and 0.05 mg/kg, respectively. The concentrations of heavy metals in soils are controlled by the parent materials and varied greatly from in different areas. Heavy metal contents in all pepper samples were lower than the Chinese maximum contaminant levels. The relationship between heavy metals in soils and biological absorption coefficient (BAC) of pepper fruits suggests that the uptake ability of pepper for soil metals depends mainly on the physiological mechanism, while in some cases, the soil types and supergene environment are also important.     

Heavy metal exchange processes in sediment-water systems

Experimental data for sorption of Hg, Cd, Cu, and Pb by sand, silt, and organic-rich sediments from the Ottawa River, Canada show significant conformity to Langmuir's equation. Values of the bonding energy constant and the sorption maximum correlate directly with organic content and mean grain size (φ). Desorption experiments indicate that the heavy metals form stable complexes in nitrilotriacetate (NTA) and NaCl Solutions, with the following desorption ratios: Hg, 1:1 (Cl⁻:NTA); Pb, 1:10; Cd, 1:2. Serial and batch desorption studies under various conditions show that the cation-exchange order in the sediments is Hg>Pb>Cu>Cd. For a given heavy metal the partition coefficient between sediment and solution is not greatly changed by the presence of another cation, provided the latter has the same order of concentration. If, the concentration of one cation exceeds another by more than 10, however, significant desorption of the less concentrated ion takes place on a mass action basis.     

Heavy metal pollution and human health risk assessment for exposure to surface soil of mining area: a comprehensive study

Climate change projections indicate an increase in intense rainfall events with consequent river flooding, which could lead to devastating natural disaster     

Heavy metal content in the stream sediments adjacent to a sanitary landfill

Samples of stream sediments were collected along two streams adjacent to a sanitary landfill. One of the streams drained the landfill directly. In addition, control of background samples were also analyzed from a stream not affected by the landfill. All samples were analyzed for Ag, Zn, Cu, Cd, and Pb content using atomic adsorption techniques. The pH of the three streams were monitored since pH differences in the streams may affect the quantities of metals adsorbed or precipitated on the sediments. The comparison between the content of Ag, Zn, and Cu in the sediments of the two study streams and the same metals in the control sediments indicated the landfill emitted these metals into the two adjacent streams. However, since the Cd and Pb contents in the sediments of both streams were similar to that of the control stream sediments, these metals may not be emitted into the two study streams from the landfill and they represent only background quantities. The comparisons of each metal in the sediments of each stream were made by the use of a metal trend chart, the individual calculated mean metal content values, and by the statistical two sample t-test. No decreasing trends of the quantities of Ag, Zn, or Cu as a function of increasing distance from the landfill was present in the sediments along the stream that drained the landfill directly. These sediments might have been affected by stream action and became mixed with other sediments downstream.     

Heavy metal distribution in the Godavari River basin

Suspended and bed sediments collected from the entire region of the Godavari River basin were analyzed for Fe, Mn, Cr, Cu, Ni, and Zn. There are pronounced temporal and spatial variations in the heavy metal distributions. The concentrations of heavy metals in the suspended sediments are significantly higher than the bed sediments.Throughout the basin heavy metals are enriched in the finer fractions (<2 µm) of the bed sediments. The average heavymetal composition of the sediments is higher when compared to the average Indian river sediments. Heavy-metal concentration in the two shallow cores collected shows, to some extent, the influence of urbanization. When compared to the other tropical Indian rivers such as the Krishna, the Godavari appears to be a significant contributor of heavy metals to the Bay of Bengal. Considering the enormous sediment load of the Godavari River—170 million tons/yr, the heavy metal fluxes to the Bay of Bengal is very significant. Except for the Pranhita, other tributaries of the Godavari do not contribute significant loads of heavy metals. All the metals show high correlation among themselves and the correlation is more pronounced in suspended sediments than in the bed sediments. The heavy-metal distribution, fractionation, and its relationship with total suspended sediments and depth in various parts of the basin are discussed in detail.     

Heavy metal concentrations in roadside-deposited sediments in Kuwait city

In the present study, roadside-deposited sediment samples collected from Kuwait city district, in Kuwait, were analyzed for specific heavy metals (As, Cr, Cu, Mn, Ni, Pb, and Zn). Contamination assessment status of heavy metals in roadside sediments was made using mathematical models in terms of enrichment factor (EF), geoaccumulation index (I _geo), and contamination factor (CF). The sediments showed remarkably high levels of all the metals, except Ni, above background concentrations in the following order (As, Cu, Pb, Zn, Mn, and Cr). CF and I _geo revealed overall moderately uncontaminated and moderate contamination, respectively, but the EFs for all metals ranged between moderate and significant enrichment.     

Heavy metal contamination of a Greenland fjord system by mine wastes

Since 1973, about 500,000 tons/yr of metal-rich particulate tailings from a lead/zinc flotation mill have been discharged through a submarine outfall into a two fjord system on the west coast of Greenland. Differential solubilization of particulate metals by seawater, seasonal water mixing, and sill exchange tailings dispersal processes have resulted in high, but seasonally variable Zn, Cd, and Pb contamination of the water, and suspended particulate matter (SPM).Chemical partition of the SPM shows that most (85-99 percent) of the Pb, but relatively low proportions of Zn (14-26 percent) and Cd (10–20 percent) are weakly bound to the SPM. Such particulate metal characteristics allow the real time effects of tailings discharges and dispersal on the system to be traced even in the sediments where tailings accumulation is very slow (0.1 cm/yr).Fjord seaweeds and blue mussels also contain varying amounts of Zn, Pb, and Cd depending on the metal and their location relative to the tailings outfall and apparently responded almost instantly to the metal contamination, as did the water and SPM. High Pb concentrations in the fjord mussels most likely derive from the preferential uptake of available particulate Pb, whereas the seaweeds appear to derive most of their heavy metal concentrations from the dissolved phase. The evidence from this and other sites as well as from experimental work, indicates that any discharge of Pb-bearing particles into the marine environment either directly as mine wastes or indirectly as from natural runoff from current and former lead mining sites results in immediate lead contamination of the in situ mussel population.     

Heavy metal trends in the Calabar River, Nigeria

. Heavy metal concentrations in sediments of the Calabar River: Pb (0.6–30 ppm); Ni (1.2–22.5 ppm); Cr (0.6–3.3 ppm); Cu (0.3–48 ppm); Zn (0.8–27 ppm); Fe (0.2–2,880 ppm) and V (0 ppm) are generally below levels that are known to be harmful to aquatic biota. Metal levels displayed marked seasonal, spatial and tidal variations, which are attributed to both anthropogenic influences and natural processes in the environment. Iron and Cr increased during the dry season (January), while Cu, Zn, Pb and Ni had their peak values in the wet season (September). High values of metals during the wet season indicate inputs through human activities mediated by rainfall. Relatively higher concentrations of metals are obtained during high tide compared to low tide regime. This is attributed to redox processes in the sediment and subsequent displacement of sediment pore water rich in metals by seawater intrusion during high tide. Higher values of Fe observed in the dry compared to the wet season may be attributed to oxidation and precipitation of soluble forms brought into the river during the wet season.