土壤重金属环境质量矿物学评价方法

利用环境矿物学理论和方法阐明了土壤矿物控制重金属活动状态,具体分析了重金属在矿物表面、层间域和孔道内可能的赋存位置。实验研究结果表明,矿物吸附重金属的作用受到介质pH值、介质离子强度等因素的影响。采用系统聚类分析方法,能定量地分析稳定的硫化物结合态微量有毒有害重金属元素的数量。利用粉晶X射线衍射分析方法,能定量地测定土壤矿物组成和含量。新提出土壤环境质量矿物学方法评价流程。该方法是在利用生态地球化学方法所完成的元素总量调查成果的基础上,开展单元性与剖面性土壤矿物组成与含量测定,查明表层土壤和深层土壤的矿物组成和分布,评价土壤中重金属的赋存状态及其对食物链的影响。旨在为农业地质环境评价提供新方法,切实提高农业地质环境调查质量与服务水平。     

Contamination and potential mobility assessment of heavy metals in urban soils of Hangzhou,China: relationship with different land uses

Concentration and distribution of heavy metals (Cd, Cu, Pb and Zn) in urban soils of Hangzhou, China, were measured based on different land uses. The contamination degree of heavy metals was assessed on the basis of pollution index (PI), integrated pollution index (IPI) and geoaccumulation index (I _geo). The 0.1 mol l⁻¹ HCl extraction procedure and gastric juice simulation test (GJST) were used to evaluate the potential mobility and environmental risk of heavy metals in urban soils. The average concentration of Cd, Cu, Pb and Zn in urban soils was measured at 1.2 (with a range of 0.7–4.6), 52.0 (7.4–177.3), 88.2 (15.0–492.1) and 206.9 (19.3–1,249.2) mg kg⁻¹, respectively. The degree of contamination increased in the order of industrial area (IA) > roadside (RS) > residential and commercial areas (RC) > public park and green areas (PG). The PIs for heavy metals indicated that there is a considerable Cd, Cu, Pb and Zn pollution, which originate from traffic and industrial activities. The IPI of these four metals ranged from 1.6 to 11.8 with a mean of 3.5, with the highest IPI in the industrial area. The assessment results of I _geo also supported that urban soil were moderately contaminated with Cd and to a lesser extent also with Cu, Pb and Zn. The IP and I _geo values reveal the pollution degree of heavy metal was the order of Cd > Pb > Zn ≈ Cu. It was shown that mobility and bioavailability of the heavy metals in urban soils increased in the order of Cd > Cu > Zn ≈ Pb. Owing to high mobility of Cd and Cu in the urban soils, further investigations are needed to understand their effect on the urban environment and human health. It is concluded that industrial activities and emissions from vehicles may be the major source of heavy metals in urban contamination. Results of this study present a rough guide about the distribution and potential environmental and health risk of heavy metals in the urban soils.     

Relationship between aquatic insects and heavy metals in an urban stream using multivariate techniques

In the study, the relationship between some aquatic insect species (Ephemeroptera, Plecoptera, Trichoptera and Odonata) and some heavy metals (cadmium, lead, copper, zinc, nickel, iron and manganese) and boron were assessed using data obtained from the Ankara Stream, which flows through Ankara, the capital city of Turkey and receives high organic and industrial wastes. Sampling was carried out monthly along the Ankara Stream in 1991. environmental data were used to explain biological variation using multivariate techniques provided by the program canonical correspondence analysis ordination. The ordination method canonical correspondence analysis was applied to evaluate the relationships between environmental variables and distribution of aquatic insect larvae. Data sets were classified by two way indicator species analysis. In this study, aquatic insecta communities have been shown by canonical correspondence analysis ordination as related to total hardness, pH, cadmium, lead, copper, zinc, nickel, iron, manganese and boron. Cadmium, lead, copper and boron exceeded limits of the United States Environmental Protection Agency criteria for aquatic life. Trichopteran, Dinarthrum iranicum was an indicator of two way indicator species analysis and was placed close to the arrow representing copper. Odonate, Aeschna juncea was an indicator of two way indicator species analysis in site 10 and was placed close to the arrows representing manganese, lead, and nickel. Trichopteran, Cheumatopsyche lepida and odonate, Platycnemis pennipes were indicators of two way indicator species analysis for sites 6, 7, 11, 14, 15, 18 and were placed close to the arrows representing cadmium, boron, iron and total hardness.     

Correlations between heavy metals and organic carbon extracted by dry oxidation procedure in urban roadside soils

The organic fraction in soils has a significant influence on heavy metal transport. In this study, the organic carbon content was measured by dry oxidation procedure from 21 Xuzhou urban roadside soils to assess the relationships between the concentrations of heavy metals (Pb, Cu, Zn, and Cr) and the amount of organic carbon. The anthropogenic heavy metals (e.g. Pb, Cu, Zn) were strongly correlated with organic carbon (denoted by C_org−c) extracted by dry oxidation while natural heavy metal (e.g. Cr) showed no correlation to the C_org−c. The anthropogenic heavy metals were also strongly correlated with the amount of the total carbon. These results show that the anthropogenic heavy metals are mainly enriched in the organic matter in the Xuzhou urban roadside soils.     

Distribution of heavy metals in Gaborone urban soils (Botswana) and its relationship to soil pollution and bedrock composition

The capital city of Botswana, Gaborone, has seen unprecedented population, economic, and industrial growth in recent years. In order to assess how this rapid urbanisation process impacts the environment, 106 silt and clay (particle size <0.053 mm) samples, separated from Gaborone surface soil samples representing urban, agricultural and rural sites, were investigated. The concentrations of nine heavy metals (Sc, Cr, Co, Ni, Cu, Zn, Nb, Cd, and Pb) were measured using ICP–MS and GFAAS, and the resulting patterns were correlated to the bedrock composition and anthropogenic activities. As expected, we found that samples from soils on top of dolerites show higher levels of Cr, Ni, and Cu than those on top of granites and rhyolites. However, our studies also show that Gaborone city centre soils are moderately polluted by Pb (up to 222 mg/kg, i.e. 5.7-fold the concentration in comparable rural soils), as a result of heavy traffic. Furthermore, Cr and Ni pollution originating from agrochemicals were shown to be accumulating in Gaborone crop soils. Our studies also showed moderate levels of Zn pollution and low level, dot-shaped pollution of Cr, Co, Ni, Cu detected in Gaborone residential and industrial soils that are correlated to waste disposal. Interestingly, the highest levels of Sc, Cr, Co, Ni and Zn pollution are found near two abandoned sewage works. The results of sequential extraction indicate that the polluting Co and Ni exist in all speciations; the polluting Cu mainly exists in the residue of the sequential extraction, whereas the polluting Pb is mostly bound to organic matters and Fe- and Mn-oxides. These results highlight the need for instituting a systematic and continuous monitoring of heavy metals and other forms of pollutants in Gaborone to ensure that pollution does not become a serious problem in the future.     

Relationships between heavy metals and iron oxides,fulvic acids,particle size fractions in urban roadside soils

Urban roadside soils are the “recipients” of large amounts of heavy metals from a variety of sources including vehicle emissions, coal burning waste and other activities. The behavior of heavy metals in urban roadside soils depends on the occurrence as well as the total amount. Accordingly, knowledge of the interactions between heavy metals and other constituents in the soil is required to judge their environmental impact. In this study, correlations of heavy metal concentrations (Pb, Zn, Cu, Ag, Se, Ni, Cr and Ba) to iron extracted using dithionite–citrate–bicarbonate (DCB) buffer (Fe_DCB), fulvic acids and particle size fractions were examined from the Xuzhou urban roadside soils. Heavy metals except for Cr and fulvic acids had a positive significant correlation with Fe_DCB, indicating these metals and fulvic acids are principally associated with the surfaces of iron oxides of the soils. Significant positive correlations were also found between the contents of fulvic acids and heavy metals, showing these heavy metals (especially for Cu, Ni and Cr) form stable complexes with fulvic acids. Such finding is of importance with regard to the increased mobilization of heavy metals, e.g., into freshwater ecosystems. Ag, Se and Cr are independent of particle size fractions because of their low concentrations of Ag and Se in the studied soils. Pb, Zn, Cu, Ba and Ag are mainly enriched in the finer soil particles (especially <16 μm).     

Selective chemical extraction of heavy metals in tailings and soils contaminated by mining activity: Environmental implications

Total concentrations of chemical elements in soils may not be enough to understand the mobility and bioavailability of the elements. It is important to characterise the degree of association of chemical elements in different physical and chemical phases of soil. Another geochemical characterisation methodology is to apply sequential selective chemical extraction techniques. A seven-step sequential extraction procedure was used to investigate the mobility and retention behaviour of Al, Fe, Mn, Cu, Zn, Pb, Cr, Co, Ni, Mo, Cd, Bi, Sn, W, Ag, As and U in specific physical–chemical and mineral phases in mine tailings and soils in the surroundings of the abandoned Ervedosa mine. The soil geochemical data show anomalies associated with mineralised veins or influenced by mining. Beyond the tailings, the highest recorded concentrations for most elements are in soils situated in mineralised areas or under the influence of tailings. The application of principal components analysis allowed recognition of (a) element associations according to their geochemical behaviour and (b) distinction between samples representing local geochemical background and samples representing contamination. Some metal cations (Mn, Cd, Cu, Zn, Co, Cr, Ni) showed important enrichment in the most mobilisable and bioavailable (i.e., water-soluble and exchangeable) fractions due likely to the acidic conditions in the area. In contrast, oxy-anions such as Mo and As showed lower mobility because of adsorption to Fe oxy-hydroxides. The residual fraction comprised largest proportions of Sn and Al and to a lesser extent Zn, Pb, Ni, Cr, Bi, W, and Ag, which are also present at low concentrations in the bioavailable fractions. The elements in secondary mineral phases (mainly Fe, Mn, Cu, Zn, Cd, Pb, W, Bi, Mo, Cr, Ni, Co, As and U) as well as in organic matter and sulphides are temporarily withheld, suggesting that they may be released to the environment by changes in physico-chemical conditions.     

Correlation between magnetic susceptibility and heavy metals in urban topsoil: a case study from the city of Xuzhou, China

Anthropogenic influence, mainly due to urban and industrial activities and traffic exhaust, may affect urban topsoil via atmospheric contamination and solid waste. Magnetic susceptibility measurements were conducted on 21 urban topsoil samples from the city of Xuzhou, China. High intensities of magnetic susceptibility were detected in the majority of the samples. SEM analysis shows that magnetic minerals are in the form of spherules and mainly due to anthropogenic inputs. The heavy metals Pb, Cu, Zn, Se, Sc, Mo, Fe, and Bi show strong correlations with magnetic susceptibility, and Ag, Ba, Cd, Ni, Cr, Sb, and Sn, on the other hand, show a weak correlation with magnetic susceptibility. Whereas, of these metals studied, only Hg has no significant correlation with the susceptibility. The Tomlinson pollution load index (PLI) also shows significant correlation with the susceptibility (χ). The present study shows that magnetic susceptibility is a fast, inexpensive, and non-destructive method for the detection and mapping of contaminated soils.     

Distribution and sequential extraction of some heavy metals in urban soils of Guiyang City,China

Sixty-two soil samples collected from different functional zones of Guiyang were analyzed for total concentrations and sequential extraction of Cr, Cu, Pb, Zn and Cd by ICP spectrometry. The average total concentrations ofCr, Cu, Pb, Zn and Cd in the soils of Guiyang were 92.9, 51.6, 44.1,139.3 and 0.28 mg/kg, respectively. The soils have been polluted by Cr, Cu, Pb, Zn and Cd to some extent in comparison with the background values of Guiyang. Significant differences were recognized in the concentrations of Cr, Cu, Pb, Zn and Cd in different functional zones. As for the sequential extraction, Cr, Cu and Zn were present mainly in the residual fraction, and Pb was present mainly in the oxidizable fraction. The reducible fraction of Cd accounts for 47.5%, and the residual fraction is lowest. The mobility and bioavailability of heavy metals follow the order of Cd〉Pb〉Cu〉Cr〉Zn.     

Spatial distribution of metals in urban topsoils of Xuzhou (China): controlling factors and environmental implications

The contamination of soils by metals from various sources is a subject of increasing concern in recent times. Twenty-eight elements (Fe, Ti, Cr, Al, Ga, Pb, Sc, Ba, Li, Cd, Be, Co, Cu, Mn, Ni, V, Zn, Mo, Pt, Pd, Au, As, Sb, Se, Hg, Bi, Ag and Sn) have been analyzed from urban topsoil from the city of Xuzhou. The concentrations of these analyzed elements have been correlated to some soil parameters such as organic matter, pH, cation exchange capacity, carbonate content, and granulometric fractions (clay, silt and sand). Results of the statistical analysis show a large variety and complexity in these relationships. The spatial distributions of these metal concentrations were also constructed using geographical information system. The spatial distribution patterns of the elements analyzed show that traffic and industrial activities are the principal anthropogenic pollutant sources.     

Contamination and distribution of heavy metals in urban and suburban soils in Zhangzhou City,Fujian, China

The urban environment is of growing concern as its continued population increase in China. Due to the urbanization and industrialization, heavy metals have been continuously discharged into the soil recently, and creating the anthropogenic contamination. This study investigated heavy metals contamination in urban and suburban soils in Zhangzhou City, Fujian, China. Multivariate analysis and geographical information system technology were employed in source identification and contamination assessment of heavy metals in the city soils. The survey results indicated that the urban soils were contaminated by heavy metals, especially by Hg, Cd and Pb. The multivariate analysis demonstrated that the distribution of Cu, Zn, Cr and Ni was controlled by pedogenesis, Cd and Pb had been disturbed by industrialization in some urban locations, and Hg was mainly influenced by the hot-spring in some urban park sites. The distribution of heavy metals and soil pollution index suggested the soils of Zhangzhou City have been affected by human activities.     

Contamination and distribution of heavy metals in urban soil in Zhangzhou City, Fujian, China

The urban environment quality is of vital importance as the majority of people now live in cities. Due to the continuous urbanization and industrialization with rapidly increasing economy in China, metals are continuously emitted into soils, imposing a great threat on human health. Urban soils might be affected by industrial activities, transport, agricultural practice, and waste disposal. An extensive survey was conducted in the highly urbanized Zhangzhou City （Fujian Province, China） using a systematic sampling strategy. Concentrations of Hg, Cd, Pb, Zn, Cu, As, Cr and Ni were measured on 108 topsoil samples collected from parks （0-15 cm）, residential areas and suburban agricultural soils. Statistic approach （cluster analysis） was adopted for identification of natural and anthropogenic influence on heavy metal contents. The maps of metal concentrations in surface soils were made based on geographical information system （GIS） data. All of these aim at assessing the distribution of these heavy metals in the urban environment.     

Quantitative spatial characteristics and environmental risk of toxic heavy metals in urban dusts of Shanghai,China

Associated with the rapid urbanization and industrialization, most of the urban parks and recreational areas in Shanghai are built close to major roads or industrial areas, where they are subject to many potential pollution source, including automobile exhaust and factory emissions. Urban dusts, containing many toxic heavy metals such as Pb, Cr, Cd, Hg and As, are one of main contributors for environmental pollution. In this study, 261 dust samples were collected from two different localities (streets and parks) in the urban area of Shanghai, China. Pb and Cr concentrations of all samples were determined by atomic adsorption spectrophotometer analyzer, and Cd, As and Hg concentrations in 74 samples by atomic fluorescence spectroscopy. The mean concentrations of Pb, Cr, Cd, As and Hg are 287, 157, 1.24, 8.73 and 0.16 mg kg⁻¹, respectively. Each heavy metal shows a wide range of concentration values. In comparison with heavy metal background values of soil in Shanghai, urban dusts have elevated metal concentrations as a whole, except those of As. The concentrations of Pb, Cr, Cd, As and Hg are 11.3, 2.1, 10.3, 0.997, 1.7 times of the soil background values, respectively. Compared with the global mean concentrations, Cr concentration in urban dusts is slightly higher. Pb, Cr and Hg show normal distribution after logarithmic transformation. Pb, Cr, Cd, As and Hg have second-order variation trends of the spatial distribution. The spatial distribution features of five toxic heavy metals, in general, illustrate relatively high levels within the regions of the inner-city ring highway and southwestern Shanghai. Cr and Cd are higher in Baoshan industrial park and the shipbuilding industries regions. The order of environmental risk is Pb > Cd > Cr > Hg > As. Pb and Cd have the highest risk for environment pollution and human health among the five metals. The pollutant sources of toxic heavy metals in Shanghai urban dusts are preliminarily concluded as follows: As may have mainly a natural source. Burning of coal has become the main source of Hg pollution. Pb, Cr and Cd have three sources, traffic, building construction, and weathering corrosion of building materials.     

Heavy metals concentration in soils under rainfed agro-ecosystems and their relationship with soil properties and management practices

Heavy metals are governed by parent material of soils and influenced by the soil physicochemical properties and soil and crop management practices. This paper evaluates total heavy metal concentrations in rainfed soils under diverse management practices of tropical India. Vertisols (clayey soils with high shrink/swell capacity) had the highest concentrations of heavy metals. However, chromium (Cr) content was above the threshold value in Aridisol [calcium carbonate (CaCO₃)]-containing soils of the arid environments with subsurface horizon development. Concentration increased at lower depths (>30 cm). Basaltic soils showed higher concentrations of nickel (Ni), copper (Cu) and manganese (Mn). Cadmium (Cd), cobalt (Co), Cu and Mn concentrations were higher in soils cultivated to cotton, whereas Cr concentration was above the threshold level of 110 mg kg^?1 in food crop cultivated soils. As the specific soil surface is closely related to clay content and clay type, soil’s ability to retain heavy metals is more closely tied to the specific surface than to the soil cation exchange capacity. Higher positive correlations were found between heavy metal concentrations and clay content [Cd(r = 0.85; p ≤ 0.01); Co (r = 0.88; p ≤ 0.05); Ni (r = 0.87; p ≤ 0.01); Co (r = 0.81; p ≤ 0.05); Zn (r = 0.49; p ≤ 0.01); Cr (r = 0.80; p ≤ 0.05); Mn (r = 0.79; p ≤ 0.01)]. The amounts of nitrogen–phosphorus–potassium applied showed a positive correlation with Co and Ni (r = 0.62; p ≤ 0.05). As several soils used for growing food crops are high in Ni, Cr and Mn, the flow of these metals in soil–plant–livestock/human chain needs further attention.     

青藏高原东部表土磁化率特征与环境意义

现代表土磁化率与气候因子关系的研究是黄土古气候重建的重要内容,在黄土高原地区取得了重要进展,但在青藏高原地区相对不足。在青藏高原东部系统采集了106个表土样品,分析了其磁化率的变化特征;并通过表土磁化率与气候因子的相关分析,讨论了气候因子对高原东部现代表土低频磁化率和频率磁化率的影响。结果表明：研究区表土磁化率特征主要受到温度和降水量的影响,水热组合差异影响表土磁化率值的高低。低频磁化率与气候因子的相关性较弱,总体上与温度的相关性优于降水量,可能表明其与气候因子的关系比较复杂;频率磁化率百分比与降水呈较好的正相关关系,表明该指标对降水量的变化更为敏感,可以用于青藏高原东部的古降水定量重建。     

Heavy meals in urban roadside soils, part 1: effect of particle size fractions on heavy metals partitioning

Urban roadside soils are important environmental media for assessing heavy metal concentrations in urban environment. However, among other things, heavy metal concentrations are controlled by soil particle grain size fractions. In this study, two roadside sites were chosen within the city of Xuzhou (China) to reflect differences in land use. Bulk soil samples were collected and then divided by particle diameter into five physical size fractions, 500–250, 250–125, 125–74, 74–45, < 45 μm. Concentrations of metals (Ti, Cr, Al, Ga, Pb, Ba, Cd, Co, Cu, Mn, Ni, V, Zn, Mo, As, Sb, Se, Hg, Bi, Ag) were determined for each individual fraction. These metals could be roughly classified into two groups: anthropogenic element (Pb, Ba, Cd, Cu, Zn, Mo, As, Sb, Se, Hg, Bi, Ag) and lithophile element (Ti, Cr, Al, Ga, Co, Mn, Ni, V) in terms of values of enrichment factor. As expected, higher concentrations of anthropogenic heavy metals (Cu, Zn, Mo, As, Hg, Bi, Ag) are observed in the finest particle grain size fraction (i.e. < 45 μm). However, heavy metals Se, Sb and Ba behave independently of selected grain size fractions. From the viewpoint of mass loading, more than 30% of the concentrations for all anthropogenic heavy metals are contributed by the particle grain size fractions of 45–74 μm at site 1 and more than 70% of the concentrations for all heavy metals are contributed by the particle grain size fractions of 45–74 and 74–125 μm at site 2. These results are important for transport of soil-bound heavy metals and pollution control by various remedial options.     

Pre- and post-monsoon variations in the magnetic susceptibilities of soils of Mumbai metropolitan region: implications to surface redistribution of urban soils loaded with anthropogenic particulates

Mumbai metropolitan region (MMR) in India represents one of the most industrialized and thickly populated areas of the monsoon dominated Asian region. We present here pre- and post-monsoon magnetic susceptibility variations in the top-soils representing sampling domains of industrial, heavy traffic and forested areas within MMR. The rock magnetic studies (including isothermal and anhysteric remanent magnetization and hysteresis loop analysis) infer predominant pseudo single domain to multi domain grains in an overall ferrimagnetic dominant mineralogy of the soils. The susceptibility-temperature variations (from ?190 to 700°C) infer maghemite (??-Fe₂O₃) as the chief mineral component of pedogenic origin, and the pure magnetite (Fe₃O₄) is of anthropogenic nature. Spatial distribution of ferrimagnetic concentration is in agreement with polluting sources. The post-monsoon redistribution pattern is greatly controlled by the surface runoff and topographic conditions. The study demonstrates that in a ferrimagnetically reach substrate like MMR, the spatial distribution patterns derived from routine concentration- and grain-size-dependent rock magnetic parameters integrated with topographic and seasonal attributes yield significant information on the style and surface re-distribution of anthropogenically loaded soils and sediments to identify its seasonal dumping. Alternatively, knowing the source of signal, the magnetic susceptibility can be further used as a robust parameter to produce detailed maps to monitor the pollutions in urban areas.     

Magnetic properties of urban topsoils and correlation with heavy metals: a case study from the city of Xuzhou, China

Heavy metals in urban topsoils have been shown to be very useful tracers of environmental pollution. Thus, their detailed studies are of great importance. Apart from expensive and time-consuming chemical methods, several simple, rapid and cheap proxy methods have been developed recently, one of them being based on rock-magnetic parameters. This examines the use of rock-magnetic methods designed to assess the degree of heavy-metal pollution of urban topsoils from the city of Xuzhou (China). The aim was to identify the magnetic properties and to link the “magnetic pollution” to the concentrations of the heavy metals. Since a strong correlation has been found between saturation isothermal remanent magnetization (SIRM) and the heavy metals, namely, Fe, Se, Ti, Sc, Ba, Bi, Pb, Cu, Zn, Cr and Mo, an anthropogenic contamination origin is thought to be the cause. The present study shows that SIRM is a fast, inexpensive and non-destructive method for the detection and mapping of heavy-metal-contaminated urban topsoils.     

Competitive adsorption behavior of selected heavy metals in three soil types of India amended with fly ash and sewage sludge

Laboratory batch experiments were carried out to study the competitive sorption behavior of metals in three types of Indian soils, differing in their physicochemical properties: acid laterite (SL1), red alfisol (SL2) and black vertisol (SL3) treated with different proportions of fly ash and sewage sludge mixture. Representative samples were equilibrated with 10 to 200 µM L ^-1 concentrations of metals simultaneously containing Cd, Cu, Ni, Pb and Zn in 5 mM of Ca(NO ₃) ₂ solution. In most of the cases the affinity sequence of metals was Pb>Cu>Zn>Ni>Cd based on their amount of sorption, which varied little with either metal equilibrating concentrations or the soil/mixture type. The observed metal affinity sequences in different soils amended with mixtures were compared to the predicted affinity sequences based on metal properties and a good match was found with those predicted by metal hydrolysis constants. This indicated that formation and subsequent sorption of metal hydrolysis products on soil surface is the predominant mechanism for sorption. In all the cases, Pb and Cu showed higher affinity followed by Zn, Ni or Cd. The increase in the metal additions further enhanced the competition among metals for exchange sites. Adsorption isotherms showed that metal sorption was linearly related to its concentration in the equilibrium solution. The distribution coefficients (K _D) computed from the slopes of linear regression for different metals were higher in SL3 than in both SL2 and SL1. All the mixture amended soils produced higher K _D values than their respective controls. Selectivity between metals resulted in the following affinities based on their K _D values—Pb>Cu>Zn>Ni or Cd—which was in line with the value of the hydrolysis constant of the metals under study.