Fluxes of Cu,Zn, Pb,Cd, Cr,and Ni in temperate forest ecosystems

The literature on the fluxes of six heavy metals in temperate forest ecosystems is reviewed. Special attention is given to wet and dry deposition and internal flux, to metal budgets for ecosystems and soils, to concentrations in aqueous compartments of the ecosystem and to speciation in soil solutions. Metal fluxes are discussed in relation to pollution load, soil type, tree species and land use. The mobility of Cu and Pb is strongly dependent on the solubility of organic matter. These metals are commonly accumulated in forest soils. Zinc, Cd and Ni are greatly influenced by soil acidity and are often lost in considerable amounts from acidified soils. Chromium is often at balance in forest ecosystems. Implications for metal solubility and budgets in forest soils are discussed in connection with an increase in soil acidification.     

Distribution of Cd, Ni, Cr, and Pb in Amended Soils from Alicante Province (SE, Spain)

Heavy metals can be transferred from soils to other ecosystem parts and affect ecosystems and human health through the food chain. Today the use of biosolids to improve the nutrient contents of a soil is a common practice. Contamination of soils by potentially toxic elements (e.g., Cd, Ni, Cr, Pb) from amendments of biosolids is subject to strict controls within the European Community in relation to total permissible metal concentrations, soil properties and intended use. In this context, heavy metal concentrations were studied in agricultural soils devoted to vegetable crops in the province of Alicante (SE Spain), where an intensive agriculture takes place. This study is aimed at ascertaining the chemical partitioning of Cd, Ni, Cr, and Pb in agricultural soils repeatedly amended with sludge. Selected soil properties relevant to control the mobility and bioavaibility of heavy metals were analyzed for the general characterisation of these agricultural soils. The distribution of chemical forms of Cd, Ni, Cr, and Pb in five biosolids-amended soils was studied using a sequential extraction procedure that fractionates the metal into soluble-exchangeable, specifically sorbed-carbonate bound, oxidizable, reducible, and residual forms. The biosolids incorporation has modified the soil composition, leading to the increment of heavy metals. The residual, reducible, and carbonate-sorbed forms were dominant. Detailed knowledge of the soil at the application site, especially pH, CEC, buffering capacity, organic matter, clay minerals, and clay content, is essential.     

Simultaneous Sorption of Cd,Cu, Ni,Zn, Pb,and Cr on Soils Treated with Sewage Sludge Supernatant

Disposal of sewage sludge creates the potential for heavy metal accumulation in theenvironment. This study assessed nine soils currently used as Dedicated Land Disposal units(DLDs) for treatment and disposal of municipal sewage sludge in the vicinity of Sacramento,California. Adsorption characteristics of these soils for Cd, Cu, Ni, Zn, Pb, and Cr were studiedby simultaneously mixing these elements in the range of 0-50 µmol L-1 with sludgesupernatant and reacting with the soil using a soil:supernatant ratio of 1:30, pH = 4.5 or 6.5, andconstant ionic strength (0.01 M Na-acetate). The concentration of metals in the supernatant wasdetermined after a 24 hr equilibration period. Adsorption isotherms showed that metal sorptionwas linearly related to its concentration in the supernatant solution. The distribution coefficientKd (Kd = concentration on solid phase/concentration in solution phase) was computed as theslope of the sorption isotherm. The distribution coefficients were significantly correlated to soilorganic matter content for Ni, Cu, Cd, and Pb at pH 4.5 and for Ni, Cu, Zn, and Cd at pH 6.5.There was also a correlation between Kd and soil specific surface area but no relationship to othersoil properties such as CEC, clay content, and noncrystalline Fe and Al materials. Therefore, soilorganic carbon and surface area appear to be the most important soil properties influencing metaladsorption through formation of organo-metal complexes. The Kd values for all elements werehigher at pH 6.5 than at 4.5. Selectivity between metals resulted in the following metal affinitiesbased on their Kd values: Pb>Cu>Zn>Ni>Cd≈Cr at pH 4.5 andPb>Cu≈Zn>Cd>Ni>Cr at pH 6.5.     

Hg, Cu, Pb, Cd, and Zn Accumulation in Macrophytes Growing in Tropical Wetlands

The concentrations of Hg, Cu, Pb, Cd, and Zn accumulated by regional macrophytes were investigated in three tropical wetlands in Colombia. The studied wetlands presented different degrees of metal contamination. Cu and Zn presented the highest concentrations in sediment. Metal accumulation by plants differed among species, sites, and tissues. Metals accumulated in macrophytes were mostly accumulated in root tissues, suggesting an exclusion strategy for metal tolerance. An exception was Hg, which was accumulated mainly in leaves. The ranges of mean metal concentrations were 0.035?C0.953 mg g^?1 Hg, 6.5?C250.3 mg g^?1 Cu, 0.059?C0.245 mg g^?1 Pb, 0.004?C0.066 mg g^?1 Cd, and 31.8?363.1 mg g^?1 Zn in roots and 0.033?C0.888 mg g^?1 Hg, 2.2?C70.7 mg g^?1 Cu, 0.005?C0.086 mg g^?1 Pb, 0.001?C0.03 mg g^?1 Cd, and 12.6?C140.4 mg g^?1 Zn in leaves. The scarce correlations registered between metal concentration in sediment and plant tissues indicate that metal concentrations in plants depend on several factors rather than on sediment concentration only. However, when Cu and Zn sediment concentrations increased, these metal concentrations in tissues also increased in Eichhornia crassipes, Ludwigia helminthorriza, and Polygonum punctatum. These species could be proposed as Cu and Zn phytoremediators. Even though macrophytes are important metal accumulators in wetlands, sediment is the main metal compartment due to the fact that its total mass is greater than the corresponding plant biomass in a given area.     

Fractionation of Cu, Pb, Cr, and Zn in a Soil Column Amended with an Anaerobic Municipal Sewage Sludge

The objective of this study was to investigate the changes in the chemical partitioning of Cu, Pb, Cr and Zn within a column of soil incubated with an anaerobic sewage sludge (ANSS) for 2.5 months. The soil was irrigated during the incubation period. A sequential extraction method was used to fractionate these metals into exchangeable, weakly adsorbed, organic, Al oxide, Fe–Mn oxide, and residual, respectively. ANSS was applied at a loading rate of 69 Mg ha^?1. The soil is a Dystric Cambisol with low pH (<3.8), low CEC [<10 cmol(+) kg^?1 below the first 4 cm depth], and low base saturation (<7%). The addition of the ANSS caused a decrease in concentrations of Cu, Pb, and Cr in the A1 horizon, and an increase in the concentrations with depth. Below the A1 horizon, concentrations of Cu increased uniformly (~1 mg cm^?1), and the greatest increases were observed in the residual, Fe–Mn oxides, and weakly adsorbed fractions. Maximum increases in Pb occurred at 4–9 cm of depth (1.6 mg cm^?1), and mainly affected the weakly adsorbed fraction. Chromium essentially accumulated at the limit between the A2 and the Bw horizons (1.1–1.5 mg cm^?1) as residual and organic bound forms, probably through particulate transport. Zinc mainly accumulated in the A1 horizon (2.9 mg cm^?1) as exchangeable Zn. At depth, Zn increments were predominantly observed in the residual fraction. The results of this study thus demonstrate the redistribution of contaminants into different chemical pools and soil layers after sludge amendment.     

THE SPECIFIC ADSORPTION OF DIVALENT Cd, Co, Cu, Pb, AND Zn ON GOETHITE

The specific adsorption of divalent Cd, Co, Cu, Pb, and Zn on goethite is measured as a function of pH. For each mole of heavy metal adsorbed approximately two moles of H+ ions are displaced from the interface. Using these results the heavy metal adsorption data are expressed as functions of the solution concentrations of both H+ and metal ions, and the interfacial reaction is described by the equation, ₂SH+M²⁺= S₂M+₂H⁺. The adsorption data are consistent with an electrochemical model of the simultaneous adsorption of H⁺ ions and divalent metal ions on to the oxide. The intrinsic affinities of the metal ions for the oxide surface increase in the order, Cd < Co < Zn < Pb < Cu. However, besides the affinity of the metal ion for the surface, the adsorption curves are considered to be influenced by surface charge, the adsorption density of the metal ions and their size. The analysis of the data in terms of H⁺ and M²⁺ ion adsorption is considered to be complementary to the hydrolysis model for heavy metal adsorption.     

Cd、Pb、Cu、Zn、As复合污染对龙须草生长的影响

本文研究了不同处理水平下Cd、Pb、Cu、Zn、As复合污染对龙须草生长的影响。结果表明,龙须草地下部对重金属的抗性大于地上部。在接近土壤环境质量二级标准上限值时,龙须草生长正常,减产幅度<10%;在含Cd5mgkg-1、Pb600mgkg-1、Cu125mgkg-1、Zn300mgkg-1、As50mgkg-1的复合污染土壤上,龙须草地下部干重与对照相比较差异性不显著(α=0.01);在含矿毒水河水污染土壤和尾矿砂污染水稻土壤上,龙须草地下部干重与对照相当,且地上部干重分别为对照的61.58%和40.64%。这些说明龙须草在土壤重金属复合污染修复中具有良好的应用前景。     

Cu、Cd、Pb、Zn、As复合污染对灯心草的生理毒性效应

通过盆栽试验,以现行土壤环境质量标准为浓度设置依据并结合实际污染土壤研究了不同处理水平的Cu、Cd、Pb、Zn、As5种重金属复合污染对灯心草生长、叶绿素含量及保护酶系统的影响。实验结果表明:5种重金属复合污染对灯心草地上部生长有一定程度的抑制作用,在土壤环境质量二级标准上限值处灯心草地上部生物量减产9.15%,<10%,但地下部生物量减产趋势不明显。复合重金属污染抑制灯心草的光合作用使叶绿素含量减少、叶绿素a/b值降低。在接近土壤环境质量标准低浓度设计范围内,灯心草3种保护酶有逐渐被激活的趋势,表现出一定的协调性共同抵制重金属的毒害。但在高浓度处理水平下,酶活性遭到抑制。生长在矿毒水和铅锌尾矿污染土壤中的灯心草地上部生物量分别下降28.23%和37.1%,但POD、SOD和CAT3种酶活性均高于对照。通过应用综合生态环境效益法,以灯心草为指示植物可以将土壤环境质量二级标准上限值设定为土壤中5种重金属的临界毒性效应值。     

Leachability of Arsenic from Field Containers Filled With Plant Growth Medium Amended With Biosolids Compost

The leaching of arsenic (As) from plant growth medium, admixed with different proportions of composted biosolids in field containers, was determined over a four-month period. Eight-week-old perennial flowers, Coreopsis grandiflora L, were transplanted in the field in 2-L containers filled with plant growth media. The treatments were replicated three times and rainfall was supplemented to supply 2 cm of water per day. Water percolating through potted plant containers was collected biweekly and analyzed for As using graphite furnace atomic spectrometry. The concentrations of As in the leachates increased with increasing proportions of compost in the medium and decreased with time of leaching, generally remaining below the drinking water standard of 50 μg/L after two months. Leaching of As occurred at a rapid rate initially but then continued at a slow rate. Compared to other metals of concern, as Cd, Cr, Ni and Pb, As in the compost appeared more mobile.     

Distribution coefficients of Cd, Co, Ni, and Zn in soils

Batch adsorption experiments were conducted with a mixture of solutes at low equilibrium concentrations of Cd (0.7-12.6 μg1⁻¹), Co (18-118μg1⁻¹, Ni (22-330 μg 1⁻¹), and Zn (40-1480 μg1⁻¹) in 38 different soils. Statistical correlations indicated that metal sorption onto the soils was influenced by the presence of clays and hydrous oxides of Fe and Mn. Based on calculated distribution coefficients for these metals, Co will generally exhibit the highest mobility in soils, but the mobility of Zn will increase faster with decreasing pH. Two types of empirical relationships are developed from these data to estimate values for the distribution coefficients.     

长春市城区土壤中Pb、Cu、Zn、Cd及Cr化学形态特征

为弄清长春市城市土壤中Pb、Cu、Zn、Cr及Cd的化学形态分布特征,系统采集了26件城市表层(0~20 cm)土壤样品,采用连续提取法对重金属各化学形态含量进行了测定。结果表明:Pb、Zn、Cu及Cr主要以残渣态存在,其次是铁锰氧化物结合态、腐殖酸结合态和强有机结合态占有次要地位,离子交换态和水溶态所占比例均较低;Cd则主要以碳酸盐结合态存在,同时,水溶态和离子交换态所占比例较高。残渣态Pb和Zn在城区表层土壤中所占比例较近郊土壤中略有下降,但幅度不大,除Cu外,其余各元素易迁移、高生物有效性的水溶态在城区表层土壤中所占比例略有上升。Pearson相关分析结果表明,各元素残渣态与全量均呈极显著正相关,其它各活性态与全量间的相关程度与重金属种类有关。土壤pH值和Fe、Mn含量对重金属的化学形态的影响也与重金属种类有关,而且,同一重金属的不同存在形态受土壤pH值和Fe、Mn含量的影响程度也不同。     

Analytische Bestimmung und Fraktionierung von Cu,Zn, Pb,Cd, Ni und Co in Böden und Unterwasserböden

Analytical methods for determination and fractionation of Cu, Zn, Pb, Cd, Ni, and Co in soils and underwater soils Using a wet oxidation procedure with mixtures of strong acids, even samples rich in both organic carbon and carbonate could be dissolved quantitatively in platinum crucibles. Fractionation of trace elements was performed by extraction with oxalate (boiling and at room temperature), and with EDTA. Analytical problems (mainly by contamination) could be eliminated by simple preventive arrangements.     

Solubility control of Cu, Zn, Cd and Pb in contaminated soils

We developed a semiempirical equation from metal complextion theory which relates the metal activity of soil solutions to the soil's pH, organic matter content (OM) and total metal content (MT). The equation has the general form: where pM is the negative logarithm (to base 10) of the metal activity, and a, b and c are constants. The equation successfully predicted free Cu²⁺ activity in soils with a wide range of properties, including soils previously treated with sewage sludge. The significant correlation of pCu to these measured soil properties in long-contaminated soils suggests that copper activity is controlled by adsorption on organic matter under steady state conditions. An attempt was made from separate published data to correlate total soluble Cu, Zn, Cd and Pb in soils to soil pH, organic matter content and total metal content. For Cu, the total Cu content of the soil was most highly correlated with total soluble Cu. Similarly, total soluble Zn and Cd were correlated with total metal content, but were more strongly related to soil pH than was soluble Cu. Smaller metal solubility in response to higher soil pH was most marked for Zn and Cd, metals that tend not to complex strongly with soluble organics. The organic matter content was often, but not always, a statistically significant variable in predicting metal solubility from soil properties. The solubility of Pb was less satisfactorily predicted from measured soil properties than solubility of the other metals. It seems that for Cu at least, solid organic matter limits free metal activity, whilst dissolved organic matter promotes metal solubility, in soils well-aged with respect to the metal pollutant. Although total metal content alone is not generally a good predictor of metal solubility or activity, it assumes great importance when comparing metal solubility in soils having similar pH and organic matter content.     

Effects of Cu, Ni and Zn on Lettuce Grown in Metal-Enriched Vermicompost Amended Soil

A study has been conducted in a salt marsh, located in the coast of the Mar Menor lagoon (SE Spain), in which three watercourses overflow. Water samples were regularly collected over a one-year period from two transects established through the salt marsh towards the lagoon. All the samples were analysed for electrical conductivity, pH, sulphides, chlorides, nitrate, ammonium and dissolved phosphorus. The quality of the water flowing from the watercourses to the salt marsh showed a seasonal pattern, with higher contents of nitrates (> 200 mg NO^? ₃ L^?1) in periods of maximum agricultural activities in the nearby areas, as well as a higher content of ammonium (> 30 mg NH⁺ ₄ L^?1) and phosphorus (> 10 mg PO^3? ₄?P L^?1) when the human population increased in the zone as a result of tourism. The general spatial pattern of nutrient retention in the salt marsh, indicated by a reduction in the nutrient concentrations in the water closer to the lagoon, was modulated depending on the season. In the driest months, the marsh was 100% effective in reducing nutrient concentrations, but in the rainy periods the effectiveness was reduced. This reduction was more evident for phosphorus in autumn, whose concentration increased in the lower part of the salt marsh closer to the lagoon until it reached that of the inflow. This could mainly be explained by the accumulation of water in some sites near the lagoon, which can act as sinks of pollutants. Our data support the existence of polluted water in the surface watercourses of the area, and the associated risk can include soil salinization and the eutrophication of aquatic systems. Based on our data, the Mar Menor coastal marshes have an important role as filters to reduce pollution in this lagoon.     

Modelling of Cd, Cu, Ni, Pb and Zn uptake, by winter wheat and forage maize, from a sewage disposal farm

Abstract. A predictive model of metal concentrations in crops was developed to optimize soil liming and sludge application strategies at a dedicated sewage sludge disposal site. Predictions of metal concentrations in plant tissue were derived from measured values of soil metal concentration, humus content and soil pH. The plant and soil data used to parameterize the model were collected on site using quadrat sampling of mature crop and underlying topsoil. The uptake model was used to map predicted metal concentrations in wheat grain and forage maize based upon a database of soil characteristics (metal content, % humus and pH) measured as part of a routine geochemical survey of the site. The effect of a management strategy to modify uptake of Cd by wheat by changing soil pH was investigated. The effect of soil dust adhering to maize plants at harvest was also simulated to investigate the importance of this pathway for Cd transfer to animal feed such as silage.
The model gave satisfactory predictions for uptake of Cd and Zn but less useful simulations for Pb, Cu and Ni. The results for Cd uptake showed a greater dependence on soil pH in the case of wheat in comparison to maize. It is suggested that, for the study site, liming to pH 7.0 will reduce Cd concentrations in wheat grain to within EC legal standards. However the Cd content of maize may still exceed these guidelines, with a relatively minor contribution from contamination with soil dust.     

The flux of Cd,Cu, Pb and Zn in mining polluted soils

The monitoring of heavy metal deposition onto soils surrounding old Pb-Zn mines in two locations in the UK has shown that relatively large amounts of Cd, Pb, Zn and, in one case, Cu are entering the soil annually. Small particles of ore minerals in windblown mine tailings were found to be contributing up to 1.46 g m^?2 yr^?1 of Pb, 1.41 g m^?2 yr^?1 of Zn and 0.027 g m^?2 yr^?1 of Cd. However, when these inputs from bulk deposition are compared with the concentrations of the same metals within the soil profiles it is apparent that relatively little long-term accumulation is occurring. Metals are being lost from the soil profiles, probably through leaching. A calculated relative retention parameter gave values that ranged from 0.01 to 0.17 for Cd, 0.11 to 0.19 for Zn, 0.32 to 0.63 for Cu and over 1 for Pb. These relative retention values were found to follow the order of electronegativity of the elements concerned: Pb>Cu>Zn>Cd. Distribution coefficient (Kd) values quantifying the adsorptive capacity of the mine soils for Cd and Pb showed marked differences for the two metals (12 to 69 cm³ g^?1 for Cd and 14 to 126 cm³ g^?1 for Pb) and may, in part, account for the two to one hundred-fold variation in the relative retention parameter for the different metals within these soils.     

重金属单一污染对龙须草叶绿素含量和抗氧化酶系统的影响

盆栽试验的结果表明:Cd、Pb、Cu、Zn和As单一污染处理时龙须草叶绿素含量随着重金属处理浓度的增加呈现先升后降的趋势,但其总叶绿素含量和叶绿素a/b比值均低于对照;龙须草SOD的活性随着Zn、As单一污染处理浓度增加呈现先升后降的趋势,而随着其它三种重金属处理浓度的增加呈现下降趋势;龙须草CAT和POD的活性随着As处理浓度的增加呈现出上升趋势,而随着其它四种重金属处理浓度的增加呈现先升后降趋势。     

Partitioning of metals (Cd, Co, Cu, Ni, Pb, Zn) in soils: concepts, methodologies, prediction and applications – a review

Prediction of the fate of metals in soil requires knowledge of their solid–liquid partitioning. This paper reviews analytical methods and models for measuring or predicting the solid–liquid partitioning of metals in aerobic soils, and collates experimental data. The partitioning is often expressed with an empirical distribution coefficient or K_d, which gives the ratio of the concentration in the solid phase to that in the solution phase. The K_d value of a metal reflects the net effect of various reactions in the solid and liquid phases and varies by orders of magnitude among soils. The K_d value can be derived from the solid–liquid distribution of added metal or that of the soil‐borne metal. Only part of the solid‐phase metal is rapidly exchangeable with the solution phase. Various methods have been developed to quantify this ‘labile’ phase, and K_d values based on this phase often correlate better with soil properties than K_d values based on total concentration, and are more appropriate to express metal ion buffering in solute transport models. The in situ soil solution is the preferred solution phase for K_d determinations. Alternatively, water or dilute‐salt extracts can be used, but these may underestimate in situ concentrations of dissolved metals because of dilution of metal‐complexing ligands such as dissolved organic matter. Multi‐surface models and empirical models have been proposed to predict metal partitioning from soil properties. Though soil pH is the most important soil property determining the retention of the free metal ion, K_d values based on total dissolved metal in solution may show little pH dependence for metal ions that have strong affinity for dissolved organic matter. The K_d coefficient is used as an equilibrium constant in risk assessment models. However, slow dissociation of metal complexes in solution and slow exchange of metals between labile and non‐labile pools in the solid phase may invalidate this equilibrium assumption.     

Relation Between pH and Desorption of Cu,Cr, Zn,and Pb from Industrially Polluted Soils

Water, Air, & Soil Pollution - Desorption of Cu, Cr, Pb, and Zn from industrially polluted soils as a result of acidification is in focus. The eight soils of the investigation vary greatly in...