LEAD POLLUTION IN AGRICULTURAL SOILS

High concentrations of lead, copper, zinc and cadmium, are reported in agricultural soils of the southern Peak District in association with mining and smelting sites. A reliable background range of lead concentrations in non-contaminated soil was established and the relative topsoil enhancement (RTE) ratio was found to be a useful index of pollution. A wide range of amounts of lead was extracted from soils by dilute nitric acid; the higher end of the range may result from free lead oxides being present in some polluted soils. The amount of lead extracted also depended on the composition of the soil, a soil containing vermiculitic clay minerals maintained a very low lead concentration in solution. The effects of site history, weathering and redistributive processes are discussed.     

Kinetics of Iron and Manganese Release from Contaminated Calcareous Soils

Knowledge of the release of heavy metals (HM) and their chemical speciation is necessary for characterizing HM behavior in soils. The kinetics and characteristics of iron (Fe) and manganese (Mn) release were studied in 10 contaminated calcareous soils using 0.01 M calcium chloride (CaCl₂), 0.01 M ethylenediamine tetraacetic acid (EDTA), and 0.01 M malic acid (malic acid) extractions. Iron and Mn in soil samples were fractionated before and after 2084 h kinetic release using a sequential extraction procedure. The proportion of Fe and Mn released by EDTA was greater than that with CaCl₂ and malic acid. A power model satisfactorily described Fe and Mn release from soils. In general, the mean release rate of Fe was greater than that of Mn, indicating a greater rate of Fe release from contaminated soils. It was shown that Fe and Mn distributions were similar in native soils and they were mainly found in Fe-Mn oxides and organic-matter (OM) fractions. There were changes in the proportional distribution of Fe and Mn in all soils during the 2084 h kinetic study with different extraction solutions. In general, the proportions of Fe and Mn associated with carbonate (CARB) and OM fractions tended to decrease, with corresponding increases in the Fe-Mn oxides for Mn and residual (RES) fractions for Fe during the kinetic study with all extraction solutions. The Fe and Mn solubility at the initial and final stages of release was controlled by siderite (FeCO₃), vivianite [(Fe)₃(PO₄)₂·8H₂O], MnCO₃(am), MnHPO₄, and rhodochrosite (MnCO₃) minerals in all extraction solutions. Based on a risk assessment and percentage of release of metals, there is a high potential for Mn release into the food chain from contaminated soils.     

The role of iron compounds in fixing heavy metals and arsenic in alluvial and soddy-podzolic soils in the Perm area

In Perm, alluvial soils are strongly contaminated with heavy metals (Zn, Cu, and Ni, in particular) due to the ingress of liquid sewage. The concentration of a number of chemical elements is far higher in Fe-rohrensteins (tubular concretions around plant roots) of alluvial soils as compared to the fine earth. Ni and Cu are associated with Fe in rohrensteins of alluvial soils. The soddy-podzolic soils are in general less contaminated at a distance of 30 km to the northwest of Perm. Their contamination results from aerosols emitted by Perm industrial enterprises. Fe-Mn nodules that concentrate Ni and As are formed in hydromorphic podzolic soils. Mn oxides represent a separate phase carrying heavy metals and metalloids (manganophiles). Oxianions (As, Cr, and P) are closely bound to Fe in nodules, which are formed because of the alternating redox regime in soddy-podzolic soils. However, oxianions are not associated with Fe in rohrensteins of alluvial soils.     

PARTITIONING OF HEAVY METALS IN PODZOL SOILS CONTAMINATED BY MINE DRAINAGE WATERS,DALARNA, SWEDEN

The discharge of acidic mine drainage waters onto a hillslope in Dalarna, central Sweden, has lead to the contamination of the podzol soils with Cu, Fe, Ni, Pb, Zn and sulfate. Samples from contaminated and reference soils have been collected for chemical and mineralogical analyses. Jarosite is identified by x-ray diffraction analysis as a precipitate in the upper horizons (A, E, B) of the contaminated soils, where the soil acidity (pH_KCl～2.6) promotes jarosite stability. The sequential chemical extraction of soil samples indicates that, in the reference A horizon, Cu, Pb, Ni and Zn are bound primarily to cation exchange sites and organic matter. In the A horizon of the contaminated soils closest to the rock dump, metal partitioning is dominated by the Fe oxide fractions, despite the high organic matter content; Pb is almost completely bound to crystalline Fe oxides, possibly adsorbed to Fe oxides or occuring in a jarosite solid solution. In the reference B and C horizons, Cu, Ni and Zn are primarily adsorbed/coprecipitated in the Fe oxide fractions, while Pb remains with a large fraction bound to organic matter. In the Fe-rich B horizon of the contaminated soils, the partitioning of the metals in cation exchange sites and to organic matter has greatly increased relative to the reference soils, resulting from the mobilization of organo-metal complexes down the profile.     

Zinc forms in soils (Review of publications)

Zinc has no particular bearing phases in soils, and it forms very diverse compounds; this complicates zinc’s identification by chemical fractionation. However, Zn-containing particles may be identified using synchrotron X-ray analysis. Franklinite, willemite, hemimorphite, and Zn-containing magnetite are found to be the main technogenic Zn-containing pollutants in the heavy fraction of the contaminated surface soil horizon. Among the secondary zinc compounds, Zn-containing trioctahedral structures and clay minerals (unidentifiable by chemical extraction), as well as zinc fixed by manganese oxides and iron hydroxides, predominate in the soil clay fraction. Being a chalcophile element, zinc precipitates in the form of sulfides and forms complexes with organic substances in organic soils and peats. The degree of affinity to chalcophile metals increases in the following sequence: O-, P-, N-, and S-containing functional groups of organic substances.     

Factors affecting the three-dimensional distribution of exogenous zinc in a sandy Luvisol subjected to intensive irrigation with raw wastewaters

Massive volumes of raw wastewater have been spread on sandy Luvisols in the Paris region since 1899, causing major soil contamination with metallic trace elements (MTE). To identify the factors influencing the vertical and horizontal redistribution of MTE at the plot scale, a study was carried out of the three‐dimensional distribution of zinc. The background and exogenous fractions of zinc in the contaminated soil were discriminated using correlations between zinc and iron defined from unpolluted soils of the area. At the surface, the spatial distribution of zinc is determined by the geometry of the irrigation system and the terrain topography. The highest concentrations are observed near the irrigation outlets and in areas of very slight slope. The exogenous zinc has migrated down to the base of the studied solums (1 m depth), and its subsurface distribution depends upon the physico‐chemical properties of the horizons. In the E horizon, the trapping of exogenous zinc is governed by the number of available reactive sites, whereas in the Bt horizon it is a function of the vertical and lateral behaviour of the drainage. Moreover, lateral transfer of exogenous zinc occurs in the C horizon. In the case of soil contaminated with raw wastewater, the organization of water flow on the surface and in the subsurface is a determining factor in the redistribution of zinc within a plot.     

Mercury content of soils in Western Britain with special reference to contamination from base metal mining

Mercury was determined in 51 soil samples from historic base metal mining areas of England and Wales, together with cadmium, copper, lead, zinc, pH and organic content. Background mercury was calculated as 0.093 ppm whence 51% of the samples were judged to be contaminated. A very strong statistical correlation between mercury and lead and weaker but significant correlations between mercury and copper and zinc were found. Highest levels of mercury (maximum, 1.78 ppm Hg) and other metals occurred in soils derived from the floodplain of a river which was at one time badly polluted by mine waste. In a profile pit near a lead mine in the west of England both mercury and lead were enriched in surface horizons. It is concluded that land contaminated by heavy metals, especially lead, in the historic metal mining areas of England and Wales is also likely to be contaminated by mercury.     

Prediction of Contaminants Migration at Unlined Landfill Sites in an Arid Climate – a Case Study

Landfilling of municipal solid waste (MSW) is associated with the generation of leachate that is highly contaminated. Contaminant migration from disposal areas to groundwater poses a threat to the environment and the human health. This study examined the contaminant migration at a landfill site in Kuwait. The migration characteristics of contaminants were analyzed using advanced computing systems to predict the long-term plume concentration in underlying soils and aquifers located directly below the final waste layer. Mathematical models of contaminant migration were applied to existing landfill sites using MIGRATEv9 computer program to illustrate the scope and extent of soil and water contamination. Two main cases were modeled as follows: (1) water table is deep below landfill and (2) water table is rising into the landfill. The models included advective-dispersion, and buried landfills systems. The comparison between models results suggested that vertical Darcy velocity had a significant impact on migration behavior of contaminants. The concentration was increased by 24.5% by increasing the vertical Darcy velocity from 0.005 to 0.009 m/year. Advection–dispersion models and water rising models with fixed top boundary and aquifer bottom boundary at 2 and 3.5 m showed almost the same migration behavior. In addition, models of buried landfill system where water table was 5 m from ground surface produced a maximum contaminant concentration of 17 630 mg/L after 25 years at 5 m depth.     

Einflußgrößen der Schwermetallöslichkeit und -bindung in Böden

Solubility and retention of heavy metals in soils Model experiments were carried out under oxidizing conditions with soil samples from surface and subsurface horizons of different composition in order to investigate the solubility and retention of Cu, Zn, Cd, and Pb in soils. The solubility of heavy metals is mainly determined by ad- and desorption processes and complexation reactions of organic and inorganic ligands. Precipitation and dissolution of definite heavy metal compounds do not seem to govern the solution concentration in soils. An exception may probably be the formation of lead phosphate and zinc silicate under specific reaction conditions. The main factors which determine solubility and retention of heavy metals are total amount (except the proportion incorporated in the silicate structure) of the different metals, soil reaction, content of mobilizing and immobilizing organic substances, content of pedogenic oxides and clay minerals, and kind and concentration of salts and inorganic ligands. The results of the model experiments are used together with the results of other authors and general physico-chemical data to give an interpretation of the solubility behaviour of heavy metals in soils. The relations between heavy metal solubility, availability and mobility and possible procedures for melioration of soils contaminated with heavy metals are discussed.     

Aggregation of soil particles by iron oxides in various size fractions of soil B horizons

Quantitative relationships between aggregation of soil particles and the content of haematite and goethite were studied by removing iron oxides, with dithionitetrate-bicarbonate (DCB) and oxalate reagents, from various sizes of soil separates which were stable to sodium hexametaphosphate, and then determining the particle-size distribution. Significant quantitative relationships were found between DCB-extractable oxides and particles obtained from the separates up to 20 pm, whereas oxalate-extractable oxides were correlated only with < 0.2-μm particles. Oxalate-extractable oxides were observed to aggregate a greater quantity of fine clay and a larger surface area of particles per gram of oxide than DCB-extractable oxides, A more efficient mechanism of aggregation was postulated for the oxalate-extractable oxides than for the DCB-extractable oxides. There were fewer aggregated particles in soils containing haematite and goethite than in soils containing only goethite. This was attributed to differences in pedoenvironment, rather than to a difference in the behaviour of the oxides. Although various clay minerals were identified in the soils studied, no preferential aggregation of any mineral was observed.     

Heavy Metals in Soil, Crops and Grass as a Source of Human Exposure in the Former Mining Areas (6 pp)

Background, Aim and Scope   In the former mining area of Northern France, the number of diseases (cancers, malformations, backwardness...) is about ten times above the national average. Environmental surveys conducted by the Ministry of Health have showed that more than 10% of children living around a lead smelter located in this area had lead levels higher than 100 μg L-1 of blood (25% in the closest city). Two main factors contribute to the population exposure: the ingestion of plants produced in the contaminated area, and also the ingestion or the inhalation of contaminated dust or soil. It is usually known that these particles are key routes of exposure to lead for younger children, in particular via hand-to-mouth transfer. For a better understanding of this problem, researchers investigated different exposure sources like soil and vegetable contamination. Materials and Methods: All these parameters that contribute to the assessment of environmental and health risks of metal contamination have been measured. About 170 composite samples of soils around the smelter or from reference areas have been analysed, mainly from fields (70), kitchen gardens (60) and lawns (38). Total contents of Cd and Pd were measured in the organo-mineral layer (0-25cm) of soils. Composite grass samples were also taken on the lawns. Crops and vegetables were sampled from fields and kitchen gardens and then, parts of the plant intended only for consumption were washed and analysed. Results: For the organo-mineral horizon of the studied sites and located in various environmental contexts (contaminated or reference), we found a very broad range of metal concentrations. Generally, the data showed a strong variability of the physicochemical parameters of the urban soils (kitchen gardens, lawns), in particular with regard to lead. This work showed that cultivated plants (agricultural or kitchen garden) or lawn grass are also significantly contaminated by heavy metals, especially lawn grasses, cereal grains (wheat, barley) and lettuces sampled around the smelter. Moreover, the proportion of lead present on lawn grasses could reach 50% of the total contamination of the plants because of the deposition of contaminated dust. Discussion: The values of pollution in agricultural field and kitchen garden soils located near the smelter were respectively about 20 and 30 times above the agricultural regional reference values, probably due to the atmospheric emissions from a smelter that significantly increases the concentrations of metals in the upper horizons of the neighbouring soils. This pollution results in a high level of contamination of plants grown of these soils. Conclusions: The results showed that heavy metals in soils, particles (dust and soil) or plants of kitchen gardens, lawns or playgrounds could be potentially transferable to the users, and in particular to young children, and could then contribute, to a considerable share, to the exposure of the population living in a contaminated area around a smelter brought about through inhalation, direct ingestion of particles or consumption of plants. Recommendations and Perspectives: These results highlight that the consumption of home-grown vegetables can constitute a risk of exposure, in particular for cadmium, and especially in children. This work also underlined the role of the contaminated soil particles in the Pb contamination of the human food chains and their environment. Because of the complexity of the various methods of population exposure, it will be necessary to complete the data base, in partucular in urban areas. The main objective of this future work will be to relate the degree of environmental contamination with the lead level in child bood, and to integrate other environmental compartments like outdoor and indoor dust of the dwellings into the model of pathway exposure.     

澳大利亚东部地区酸性硫酸盐表土的一些重金属的特征

Forty-five acid sulfate topsoil samples (depth < 0.5 m) from 15 soil cores at 11 locations along the New South Wales coast, Australia, were selected to investigate the chemical behavior of Zn, Mn, Cr, Co and Pb in these soils. The amount of HCl-extractable Mn was much smaller than the mean value of the total Mn documented for other soils. This may be attributed to enhanced mobilization of Mn from the soils under the extremely acidic and seasonally flooded conditions encountered in the investigated soils. The pH-dependency of soluble Zn and Mn was strongly affected by the availability of acid reactive Zn and Mn compounds. There were fairly good relationships between soluble Zn and acid reactive Zn compounds, and between soluble Mn and acid reactive Mn compounds. Soluble Zn and soluble Mn concentrations were important controls on exchangeable Zn and Mn concentrations, respectively. In contrast to the suggestion by other authors that adsorption of Co was closely associated with Mn oxides present in soils, the exchangeable Co in the investigated acid sulfate soils was not clearly related to the abundance of Mn minerals. In addition to the fact that there are few Mn minerals present in the soils, this might also be because the availability of cation exchange sites on the crystal surfaces of Mn oxides was reduced under extremely acidic conditions.     

Myriapod and isopod communities in soils contaminated by heavy metals in northern France

Soil invertebrates suffer from contamination of the soil by heavy metals. We have studied the effects of contamination by cadmium, zinc and lead on their communities in soils in northern France by comparing polluted land with non‐contaminated sites. We have followed the seasonal variations and effects of soil properties. Saprophagous invertebrates (Diplopoda, Isopoda) and Chilopoda were sampled by pitfall‐trapping from February to November in fairly contaminated areas. In addition, a Berlese extraction of the litter in two very highly contaminated sites was conducted during autumn; animals were also trapped during June in the same locations. The most active period for myriapods was spring (April and May), whereas isopods were abundant from April to the end of summer. No clear relation was found relating dominant species or number of myriapods or isopods to concentration of heavy metal in the little‐contaminated soils. The dominant species seemed not to be related to pollution but to vegetation or soil characteristics. In the most contaminated sites, with metalliferous grassland and a thick undecomposed litter layer, a threshold in contamination values seemed to be reached: no isopods or millipedes were found, but only Chilopoda and Symphyla.     

苏南经济快速发展区土壤Ni的形态分布影响因素——以昆山市为例

以江苏省昆山市为典型区,通过现场采样及室内分析测定,定量研究了几种因素对农田土壤Ni形态分布的影响。结果表明：（1）土壤有效态Ni含量为1.31 mg.kg-1,土壤全Ni含量为40.95 mg.kg-1,土壤Ni的活化率为3.38%。（2）土壤重金属Ni各形态含量相对大小为残渣态（36.20 mg.kg-1）〉有机质结合态（2.80 mg.kg-1）〉铁锰氧化物结合态（1.31 mg.kg-1）〉可交换态（0.54 mg.kg-1）、碳酸盐结合态（0.10 mg.kg-1）,残渣态含量明显高于其他形态,达88.16%。（3）pH值是影响可交换态Ni含量的最主要因素,达极显著负相关水平;全Ni含量是影响碳酸盐结合态Ni含量、铁锰氧化物结合态Ni含量和残渣态Ni含量的最主要因素,达极显著正相关水平;有机质含量是影响有机质结合态Ni含量的最主要因素,呈显著正相关水平。（4）〈0.01 mm粘粒含量是影响可交换态Ni含量的重要因素,有机质含量是碳酸盐结合态Ni含量的重要影响因素,pH值和有机质含量都是影响铁锰氧化物结合态Ni含量的重要因素,〈0.01 mm粘粒含量、pH值都是影响有机质结合态Ni含量的重要因素,pH值是影响残渣态Ni含量的重要因素。     

磁性土壤中Cu和Zn污染的指示作用

Concentrations of copper （Cu） and zinc （Zn） and various magnetic parameters in contaminated urban roadside soils were investigated using chemical analysis and magnetic measurements. The results revealed highly elevated Cu and Zn concentrations as well as magnetic susceptibility in the roadside soils. The mean concentrations of Cu and Zn in these roadside soils were almost twice those in average Chinese soils, with the mean magnetic susceptibility of the roadside soils reaching about 179 ×10^-8 m^3 kg^-1. This enhanced magnetic susceptibility was attributed to the presence of anthropogenic soft ferrimagnetic particles. A low frequency-dependent susceptibility （2.5%± 1.0%） observed in the roadside soils indicated the coarse multidomain （MD） ferrimagnetic grains to be the dominant contributor to magnetic susceptibility. The Cu and Zn concentration of the soils had highly significant linear correlations with magnetic susceptibility （P 〈 0.01）, anhysteretic remanent magnetization （P 〈 0.01）, and saturation isothermal remanent magnetization （P 〈 0.01）. This suggested that heavy metals were associated with ferrimagnetic particles in soils, which were attributed to input of traffic emissions and industrial activities. Scanning electron microscopy and energy dispersive X-ray spectra of magnetic extracts of the roadside soils further suggested the llnk between the magnetic signal and concentrations of heavy metals. Thus, the magnetic parameters could provide a proxy measure for the level of heavy metal contamination and could be a potential tool for the detection and mapping of contaminated soils.     

Effect of steel-making slag as a soil amendment on arsenic uptake by radish (Raphanus sativa L.) in an upland soil

The steel-making slag (SMS), a by-product of steel manufacturing process with an alkaline pH (11–12) and high amount of iron (Fe) and calcium (Ca) oxides, was used to reduce arsenic (As) phytoextractability. The by-product was selected as an alternative to commercial Fe oxides, which can decrease plant uptake, but they are expensive if used as amendments of contaminated arable soils. SMS was applied at rates 0, 2, 4, and 8 Mg ha⁻¹ to an As (1 N HCl-extractable As 25 mg kg⁻¹) contaminated soil prepared by mixing non-contaminated soil and mine tailings and cropped to radish (Raphanus sativa L.) seeding. Calcium hydroxide (Ca(OH)₂), a common liming material in Korea, was applied at the same rates for comparison. Steel-making slag more effectively suppressed radish As uptake and increased yield than Ca(OH)₂ due to stronger As immobilization because it significantly increased extractable Fe concentration and decreased extractable As. The SMS-treated soil showed an apparent increase in As chemisorbed by Fe and Al oxides and hydroxides of surface soil, As associated at the Fe and Al oxides and hydroxides of internal surfaces of soil aggregates, and Ca-associated As. The steel-making slag can be a good soil amendment to suppress As phytoextractability and improve nutrient balance in As-contaminated soil.     

Assessment of the Contamination of Cultivated Soils by Eighteen Trace Elements Around Smelters in the North of France

Ag, As, Bi, Cd, Co, Cr, Cu, Hg, In, Ni, Pb, Sb, Se, Sn,Tl, Th, U and Zn contamination of cultivated surfacehorizons has been assessed around two lead and zincsmelters in the North of France. The verticaldistribution of Ag, As, Bi, Cu, Hg, Se, Sb and Tl inthe soils has also been examined. The soils around thelead and zinc smelter at Noyelles-Godault arecontaminated by Ag, As, Bi, Cd, Cu, Hg, In, Ni, Pb, Sb,Se, Sn, Tl and Zn. The original concentration in themost contaminated soils may be multiplied by a factorof around 2 to 100, according to the element. Cadmium,Pb and Zn are the most abundant contaminants. The Pband Zn concentrations are correlated to those of theother contaminants, with the exception of Se. Aroundthe Auby zinc smelter, there is a contamination by thesame elements, but in different proportions, inaddition to Cr contamination. Contamination by Se canreach a depth of around 1 m, whereas contamination byAg, As, Bi, Cu, Hg, Sb and Tl is confined to the top 30cm. Although the contaminant content in most soilsdepends on the distance from the plant, Secontamination would appear to vary to a greater extentaccording to the physico-chemical soil conditions.     

Immobilization of cadmium in simulated contaminated soils using thermal-activated serpentine

ABSTRACT

The thermal-activated serpentine prepared by heating natural serpentine at different temperatures was used to immobilize cadmium (Cd) in simulated contaminated soils. The results showed that the increasing soil pH induced by adding serpentine was primarily responsible for reducing the content of TCLP-Cd (toxicity characteristic leaching procedure-Cd) in soil. Furthermore, adding thermal-activated serpentine could promote the transformation from exchangeable form of Cd in soil to low bioavailable Cd (Fe-Mn oxides, carbonate, and residual form) by surface adsorption and surface precipitation, and then reduced the bioavailability of Cd in soil. Under the same treatment condition, adding S700 (serpentine activated at 700°C) exhibited better performance to immobilization of Cd, and it could reduce exchangeable Cd by 23.76~36.49%, and increase carbonate, Fe-Mn oxide, and residual form of Cd by 6.03~8.03%, 6.05~8.35%, and 11.17~19.58%, respectively. These results indicated that thermal-activated serpentine would be the great potential for immobilization of Cd in soil.     

ACCUMULATION OF CADMIUM AND ZINC FROM DIFFUSE IMMISSION ON ACID SANDY SOILS,AS A FUNCTION OF SOIL COMPOSITION

Sandy soils, in the border area of Belgium and the Netherlands (the Kempen region), are heavily contaminated by atmospheric deposition of cadmium and zinc from nearby smelters. Groundwater contamination by leaching from these low retention soils is subject of study. There are reports of high cadmium and zinc concentrations in groundwater in the area, but in most cases the direct sources are unknown. In an attempt to predict present or future risk of groundwater contamination by soil leaching, metal binding processes (retardation) were studied that are specific for these soil types under the existing acidifying conditions. From four fields nine contaminated profiles were sampled and analyzed for cadmium and zinc. Average concentrations of 131 μg g^-1 zinc and 1.6 μg g^-1 cadmium with maximum values of 2989 μg g^-1 respectively 16.3 μg g^-1 were found. In addition pH and contents of organic matter, aluminium, iron, and manganese were determined. The relative importance of these soil parameters for metal retardation is derived from the profiles. The data show that organic matter is the most important soil component for binding cadmium and zinc. Adsorption of cadmium and zinc on aluminium, iron and manganese (hydr) oxides appears to be of minor importance at low pH (<5.5).