Differential Sorption Behavior of Cadmium,Lead, Zinc,and Copper in Some Tropical Soils and Their Environmental Implications

This study evaluated cadmium (Cd), lead (Pb), zinc (Zn), and copper (Cu) sorption characteristics of three tropical soils. Data obtained conformed to Freundlich sorption model and the S-shaped isotherm curve. Sorption efficiency of Zn and Pb were highest in alkaline soil while slightly acid soil had the highest Cd and Cu sorption efficiency for monometal sorption. In competitive sorption, metals were more sorbed in slightly acid soil while the least efficiency was recorded in acid soil. Distribution coefficient; K_d (average across soil types) in monometal sorption followed the order: Pb > Zn > Cd > Cu. For competitive sorption, the order was Zn > Pb > Cu > Cd. When in competition, Cd was preferentially sorbed in slightly acid and alkaline soils and Zn for acid soil. Conclusively, lead is more in equilibrium solution when in competition with Cd, Zn and Cu making it potential agent of soil and groundwater pollution.     

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.     

Zinc sorption by acid tropical soils as affected by cultivation

The sorption of zinc (Zn) by two acid tropical soils, Mazowe clay loam (kaolinitic, coarse, Rhodic Kandiustalf) and Bulawayo clay loam (coarse, kaolinitic, Lithic Rodustalf), was studied over a wide range of Zn solution concentrations. Samples of the two soils used in the experiments were collected at both uncleared, uncultivated (virgin) sites and cultivated sites. The two virgin soils showed similar abilities to bind Zn. Mazowe soil (40 g organic matter kg^?1) presented the highest affinity for Zn. Yet, Bulawayo soil (23.5 g organic matter kg^?1) sorbed almost the same amount. Bulawayo soil had higher pH and Fe and Mn-oxide content than Mazowe soil. Once cultivated, the two soils behaved quite differently. After 50 years, Mazowe soil had lost 60% of its organic matter and effective cation exchange capacity (ECEC). In this soil, Zn sorption capacity had also been decreased by 60%. Clearing and 10 years under cultivation had affected neither the organic matter content nor the ECEC of Bulawayo soil. For this soil, Zn sorption was even higher in the cultivated soil, presumably due to an increase in the amount of Fe and Mn oxide from subsoiling. Zinc sorption was dependent upon pH, with retention dramatically increasing in the pH range 6–7. Sorption occurred at pH values below the point of zero charge (PZC), indicating that the sorption reaction can proceed even in the presence of electrostatic repulsion between the positively charged soil surface and the cation. In the two soils, the reversibility of the sorption reaction was very low. More than 90% of the sorbed Zn was apparently strongly bonded.     

Heavy metal accumulation by two earthworm species and its relationship to total and DTPA-extractable metals in soils

The concentrations of Zn, Cd, Pb and Cu in earthworm tissues were compared with the total and DTPA-extractable contents of these heavy metals in contaminated soils. Samples were taken from a pasture polluted by waste from a metallurgic industry over 70 y ago. Three individuals of Aporrectodea caliginosa and Lumbricus rubellus and soil samples were collected at six points along a gradient of increasing pollution. Total metal contents of earthworms, soil, and metals extracted by DTPA from the soil were measured. Total heavy metal contents of the soils ranged from 165.7 to 1231.7 mg Zn kg⁻¹, 2.7 to 5.2 mg Cd kg⁻¹, 45.8 to 465.5 mg Pb kg⁻¹ and 30.0 to 107.5 mg Cu kg⁻¹. Their correlations with metals extracted by DTPA were highly significant. Contents of the metals in earthworm tissues were higher in A. caliginosa than in L. rubellus, with values ranging from 556 to 3381 mg Zn kg⁻¹, 11.6 to 102.9 mg Cd kg⁻¹, 1.9 to 182.8 mg Pb kg⁻¹ and 17.9 to 35.9 mg Cu kg⁻¹ in A. caliginosa, and from 667.9 to 2645 mg Zn kg⁻¹, 7.7 to 26.3 mg Cd kg⁻¹, 0.5 to 37.9 mg Pb kg⁻¹ and 16.0 to 37.6 mg Cu kg⁻¹ in L. rubellus, respectively. Correlations between body loads in earthworms with either total or DTPA-extractable contents of soil metals were significant, except for Cd in L. rubellus and Cu in A. caliginosa. Considering its simple analytical procedure, DTPA-extractable fraction may be preferable to total metal content as a predictor of bio-concentrations of heavy metals in earthworms. Biota-to-Soil Accumulation Factor (BSAF) of these four metals are Cd>Zn>Cu>Pb, with range of mean values between: Cd (6.18-17.02), Zn (1.95-7.91), Cu (0.27-0.89) and Pb (0.08-0.38) in A. caliginosa, and Cd (3.64-6.34), Zn (1.5-6.35), Cu (0.29-0.87) and Pb (0.04-0.13) in L. rubellus. The BSAF of Ca, Fe and Mn are Ca>Mn>Fe, with mean values of: Ca (0.46-1.31), Mn (0.041-0.111), Fe (0.017-0.07) in A. caliginosa and Ca (0.98-2.13), Mn (0.14-0.23), Fe (0.019-0.048) in L. rubellus, respectively. Results of principal component analysis showed that the two earthworm species differ in the pattern of metal bioaccumulation which is related to their ecological roles in contaminated soils.     

Cadmium sorption by two acid soils as affected by clearing and cultivation

Abstract

The objective of this study was to determine the effect of clearing and cultivation on the sorption of cadmium (Cd) by two acid soils from Zimbabwe with differing cultivation stories. In their original state, not cleared‐not cultivated (virgin soils), the two soils exhibited noticeable and similar capacities to sorb Cd. The Mazowe soil contains the highest level of organic matter (40 g kg^‐1) and a effective cation exchange capacity (ECEC) of 144 mmol_c kg^‐1. Yet, Bulawayo soil (23.5 g kg^‐1 organic matter and ECEC of 146 mmol_c kg^‐1) has higher pH and Mn and Fe oxide content and these characteristics seemed to counteract the effect of lower organic matter. After 50 years of cultivation, The Mazowe soil has lost 60% of its organic matter and ECEC, and consequently the ability of its soil matrix to bind Cd has proportionally decreased. In Bulawayo (cleared in 1983 and first ploughed in 1984), on the contrary, the organic matter and ECEC of the cultivated soil remains over 95% of the values on its virgin counterpart. In this soil, the retaining ability for Cd has not still been affected. In the two soils Cd sorption was highly pH‐dependent. The extent of sorption was minimal under acidic conditions and increased sharply as the pH was raised. The immediate reversibility of the sorption process proved to be very low. When sorption and desorption data were compared it was clear that soil characteristics like high organic matter and oxide content which showed to enhanced Cd sorption, contributed at the same time to slow down the backward reaction.     

Competitive Effect of Copper,Zinc, Cadmium and Nickel on Ion Adsorption and Desorption by Soil Clays

This study evaluated the effect of competing copper, zinc, cadmium and nickel ions in 0.01 M Ca(NO₃)₂ on heavy metal sorption and desorption by soil clay fractions. Initial Cu addition levels varied from 99 mg kg^-1 to 900 mg kg^-1 and Zn, Cd and Ni levels were 94, 131 and 99 mg kg^-1, respectively. Sorption of Cu conformed to a Freundlich equation. The amounts of metals not displaced by successive 48 h desorption cycles with 0.01 M Ca(NO₃)₂ were considered ‘specifically adsorbed’. Total sorption of Zn and Cd generally decreased in the order: Vertisol > Gleyic Acrisol > Planosol clay. More than 70% of the copper was specifically sorbed. Specific sorption of Zn was depressed by competition with Cu in the three clays investigated. At surface coverages higher than 200 mg Cu per kg of soil clay, zinc sorption in the Planosol and Gleyic Acrisol clays took place at low affinity sites. The exchangeable component of sorbed cadmium accounted for >:60% of the sorption in the Vertisol clay, >70% in the Gleyic Acrisol clay and was almost 100% in the Planosol clay. Nickel was not retained by the Planosol and Gleyic Acrisol clays and was ionexchangeably adsorbed by the Vertisol clay. At the conditions studied, Ni and Cd remain a ready source of pollution hazard.     

EVALUATION OF HEAVY METAL REMEDIATION USING MINERAL APATITE

The current study investigated the sorption and desorption of dissolved lead (Pb), cadmium (Cd) and zinc (Zn) from aqueous solutions and a contaminated soil by North Carolina mineral apatite. Aqueous solutions of Pb, Cd, and Zn were reacted with the apatite, followed by desorption experiments under a wide variety of pH conditions ranging from 3 to 12, including the extraction fluids used in the Toxicity Characteristic Leaching Procedure (TCLP) of the United States Environmental Protection Agency (US EPA). The sorption results showed that the apatite was very effective in retaining Pb and was moderately effective in attenuating Cd and Zn at pH 4–5. Approximately 100% of the Pb applied was removed from solutions, representing a capacity of 151 mg of Pb/g of apatite, while 49% of Cd and 29% of Zn added were attenuated, with removal capacities of 73 and 41 mg g^-1, respectively. The desorption experiments showed that the sorbed Pb stayed intact where only 14–23% and 7–14% of the sorbed Cd and Zn, respectively, were mobilized by the TCLP solutions. The apatite was also effective in removing dissolved Pb, Cd, and Zn leached from the contaminated soil using pH 3–12 solutions by 62.3–99.9, 20–97.9, and 28.6–98.7%, respectively. In particular, the apatite was able to reduce the metal concentrations in the TCLP-extracted soil leachates to below US EPA maximum allowable levels, suggesting that apatite could be used as a cost-effective option to remediating metal-contaminated soils, wastes, and/or water. The sorption mechanisms are variable in the reactions between the apatite and dissolved Pb, Cd, and Zn. The Pb removals primarily resulted from the dissolution of the apatite followed by the precipitation of hydroxyl fluoropyromorphite. Minor otavite precipitation was observed in the interaction of the apatite with aqueous Cd, but other sorption mechanisms, such as surface complexation, ion exchange, and the formation of amorphous solids, are primarily responsible for the removal of Zn and Cd.     

Flüssebilanzen und aktuelle Änderungsraten der Schwermetall-Vorräte in Wald-Ökosystemen des Soiling

Flux balances and current rates of change of heavy metal stores in forest ecosystems of the Soiling The inventory of the heavy metals Cr, Mn, Fe, Co, Ni, Cu, Zn, Cd, and Pb is calculated for a beech and a spruce forest ecosystem in the Soiling mountains on the basis of measured concentrations in the vegetation and soil compartments and their dry mass per hectare. The inventory is compared with measured heavy metal fluxes coupled with precipitation above and below the canopy, with seepage water fluxes below the rooting zone (50 cm depth), with litterfall, and with the current increment to biomass. The ratios between heavy metal stores in the forest floor layers (table 3) and the annual flux with litterfall (table 4) show decreasing tendency for liberation of the elements by decomposition of organic matter (OM) in the following order: Mn>OM>Ni>Cd>Cu>Cr ≈? Zn>Co ≈? Fe ≈? Pb Manganese is set free faster than total organic matter. The flux balances for the total ecosystems (table 4) show input > output in the case of Cr, Fe, Cu, Cd, and Pb; input ≈? output for Ni and Zn; input < output for Mn and Co. Heavy metal stores in mineral soil are decreasing by percolation losses and increment to biomass (mainly wood) in the case of all elements investigated, except Zn (under beech), Cd and Pb (table 4). The concentrations of Cu and Pb in the forest floor layers have reached levels at which deleterious effects on microorganisms and litter decomposition are to be expected.     

Assaying the effects of chemical ameliorants with earthworms and plants exposed to a heavily polluted metalliferous soil

The study examined the effects of chemical ameliorant additions (1% montmorillonite, 1% hydroxylapatite, or 1% ferrous oxide) on the availability of cadmium (Cd), copper (Cu), lead (Pb) and zinc (Zn) to the earthworm, Lumbricus rubellus, exposed for 4 weeks to a circumneutral heavily polluted soil (Cd = 220 μg g^–1; Cu = 35 μg g^–1; Pb = 6070 μg g^–1; Zn = 124500 μg g^–1) in 1:0–1:3 dilutions with a clean soil, under laboratory conditions. Soil type (i.e. the dilution series) had a strong influence on the 1 M ammonium acetate extractable metal fractions in soil and on worm-tissue concentrations of Cd, Pb and Zn. Soil treatments (i.e. amelioration) significantly reduced only the soil Zn extractable fraction; Zn concentrations in worms tended to be lower in amended soils. A second experiment, involving curly cress (Lepidium sativum), grown either directly in the serial soil dilutions with 5% ameliorant additions or in the water-extractable fractions of the soils, indicated that root growth is a more sensitive endpoint of metal availability than chlorophyll assays. It was concluded that: (i) chemical immobilization of metals is probably most effective in soils with low to moderate degrees of metal pollution; (ii) an integrated suite of bioassays incorporating different, ecologically relevant, taxa is to be recommended for monitoring metal bioavailabilities and biological effects.     

Selective removal of heavy metals from contaminated kaolin by chelators

The competitive desorption/dissolution of kaolin-adsorbed heavy metal mixtures and mixtures of adsorbed Cd with Mg and/or Ca by four chelators (NTA, EDTA, EGTA, and DCyTA) was investigated. Metals were adsorbed on kaolin at pH 7 and the effects of chelator type and concentration on the extent of metal dissolution was studied at a solution pH of 10. EGTA addition. EGTA was the most effective chelator in selectively removing Cd from kaolin in the presence of adsorbed alkaline-earth metals. Approximately 90% of the adsorbed Ca and Mg were retained on the kaolin until almost all (> 80%) of the cadmium was dissolved by EGTA chelator. NTA was the least effective chelator in selectively dissolving Cd from kaolin contaminated with both Cd and Ca (≈ 45% of the adsorbed Cd could not be removed). All four chelators exhibited some desorption/dissolution selectivity for Cd, Cu, and Pb adsorbed on kaolin. When the concentration of chelator in solution was insufficient to dissolve all adsorbed metals, the observed metal ordering for chelation and dissolution was Cd > Cu > Pb (for EGTA), Cd > Pb > Cu (for EDTA and DCyTA), and Cu > Cd > Pb (for NTA).     

Competitivity,selectivity, and heavy metals-induced alkaline cation displacement in soils

Abstract

The simultaneous incorporation of heavy metals into the soil is still a matter of great concern. Interaction (competitive sorption) between these metals and the soil solid phase may result in a deterioration of soil quality which relies basically on amounts of alkaline cations saturating soils sorptive complex. Results of this study indicate that Pb, Cu, C d, and Zn have induced solution pH decreases which were more intensive at highest metal loading rates. Partition parameters (Kd)-based sequences showed that Pb and Cu were more competitive than Cd and Zn and the overall selectivity sequence followed: Pb > Cu > Cd > Zn. Metal loadings and their competitive sorption have led to a strengthened displacement of alkaline cations (i.e. Ca²⁺, Mg²⁺, K⁺, Na⁺), especially of Ca²⁺ as a factor “stabilizing” soil sorptive complex. Such metals impact jointly with soils acidification are of great environmental concern since tremendous amounts of alkaline cations (especially Ca²⁺) may be potentially leached out, irrespective of the degree of soil contamination, as evidenced in the current study. High and positive ΔG values implied that the studied soils were characterized by generally low concentrations of exchangeable potassium which required high energy to get displaced (desorbed). Further studies on heavy metal uncontaminated or contaminated areas should be undertaken to provide with data which should be used for predictions on changes related to soil buffering capacity as impacted by heavy metal inputs.     

Trace metal concentrations in the pink shrimp Penaeus notialis from the coast of Ghana

Studies were conducted on the concentrations of Cu, Pb, Zn, Hg, Cd, and Fe in 48 samples of the pink shrimp Penaeus notialis caught off the mouth of the Korle Lagoon, the most polluted coastal lagoon in Ghana. The pattern of occurence in order of decreasing concentration was Zn> Fe> Cu> Pb> Hg> Cd. A positive correlation was found between Hg and body weight suggesting its accumulation by shrimp. Comparatively, the concentrations obtained in the present study were similar to corresponding values for shrimp caught off the coast of West and Central Africa. However, they, except Hg, were higher than values for fin fishes from the Ghanaian coast. Results indicate that the shrimp are safe for human consumption.     

长江干流沿江地区土壤重金属的分布、来源及潜在生态风险

为掌握长江干流沿江地区土壤重金属状况,开展土壤表层样品采集和重金属空间分布研究,使用PMF（positive matrix factorization）模型解析土壤重金属来源,并选取地累积和潜在生态风险等方法,评估重金属的污染状况和生态风险。结果表明：1）土壤重金属的积累程度不同,As、Cd和Cu的超标率高,污染明显。Cd和Cu的变异系数高于1.0,分布不匀,受某些污染源的影响显著。2）各重金属含量呈现条带状的空间格局,在多个地区出现高值,土壤环境质量受到人类活动的负面影响。3）土壤重金属积累主要来源于自然、工业排放、交通运输和农业生产,贡献率分别为36.65%、28.48%、20.07%和14.80%。其中Cd与工业活动有关,Pb和Zn来自交通排放,Cr和Ni与自然源密切相关,As和Cu来源于农业生产。4）Cd的污染程度最高,81.88%的点位达到轻度污染。40%以上的点位受到As、Cu、Ni和Pb污染。75%以上点位的Cr和Zn含量较低,污染程度不高。单项生态风险指数的均值从大到小依次为：Cd、As、Ni、Cu、Pb、Zn、Cr。综合生态风险指数均值为63.17,处于轻微风险水平。该研究作为土壤生态调查的核心,可为土壤环境管理和重金属污染修复提供科学依据。     

Response of the sorption behavior of Cu,Cd, and Zn to different soil management

This study investigated the effect of different farming practices over long time periods on the sorption‐desorption behavior of Cu, Cd, and Zn in soils. Various amendments in a long‐term field experiment over 44 y altered the chemical and physical properties of the soil. Adsorption isotherms obtained from batch sorption experiments with Cu, Cd, and Zn were well described by Freundlich equations for adsorption and desorption. The data showed that Cu was adsorbed in high amounts, followed by Zn and Cd. In most treatments, Cd ions were more weakly sorbed than Cu or Zn. Generally, adsorption coefficients K_F increased among the investigated farming practices in the following order: sewage sludge ≤ fallow < inorganic fertilizer without N ≈ green manure < peat < Ca(NO₃)₂ < animal manure ≤ grassland/extensive pasture. The impact of different soil management on the sorption properties of agricultural soils for trace metals was quantified. Results demonstrated that the soil pH was the main factor controlling the behavior of heavy metals in soil altered through management. Furthermore, the constants K_F and n of isotherms obtained from the experiments significantly correlated with the amount of solid and water‐soluble organic carbon (WSOC) in the soils. Higher soil pH and higher contents of soil organic carbon led to higher adsorption. Carboxyl and carbonyl groups as well as WSOC significantly influenced the sorption behavior of heavy metals in soils with similar mineral soil constituents.     

Pollution and Ecological Risk Assessment of Heavy Metals in Farmland Soils in Yanqi County,Xinjiang, Northwest China

A total of 50 farmland soil samples were collected from the Yanqi County, Xinjiang, China, and the concentrations of eight heavy metal elements (As, Cd, Cr, Cu, Mn, Ni, Pb and Zn) were determined by standard methods. The spatial distribution, pollution level and ecological risk status of heavy metals were analyzed based on GIS technology, the Geo-accumulation Index (Igeo), the Pollution Load Index (PLI) and the Potential Ecological Risk Index (RI). Results indicated that: (1) The average contents of Cd, Cr, Ni, Pb, and Zn of farmland soils exceeded the background values of irrigation soils in Xinjiang by 1.5, 1.40, 1.33, 2.63, and 4.92 times, respectively. Cd showed a no-pollution level, Zn showed a partially moderate pollution level, Pb showed a slight pollution level, and Cr, Cu, As, Mn, and Ni showed no-pollution level, compared to the classification standard. The PLI values of heavy metal elements of farmland soils varied from 0.83 to 1.89, with an average value of 1.29, at the moderate pollution level. (2) The Individual Potential Ecological Risk Index for heavy metals in the study area was ranked in the order of: As > Ni > Cu > Cd > Pb > Cr> Zn. The RI values of heavy metals of farmland soils varied from 3.45 to 11.34, with an average value of 6.13, at the low ecological risk level. (3) Cu and Mn of farmland soils were mainly originated from the soil parent material and topography of the study area. As, Cd, Ni and Pb were mainly originated from human activities, and Cr and Zn may originated from both natural and anthropogenic factors in the study area.     

Retention of copper, cadmium and zinc in soil and its textural fractions influenced by long-term field management

The present study investigated the impact of long‐term soil management on the metal retention capacity of soil. We examined the sorption behaviour of Cu, Cd and Zn in soils and in the various particle‐size fractions of these soils, which had been amended with farmyard manure, mineral fertilizers or were fallow for 38 years in a long‐term field experiment. The soils investigated contained different amounts and origins of organic matter and differed in soil pH, but the mineral phase showed less response to the different soil managements. Batch adsorption and desorption experiments as well as a sequential fractionation schema, which defines seven geochemical fractions, were used to investigate the retention properties of soil. Sequential extraction was conducted with original as well as with metal‐spiked soils. Results showed that amounts of Cu, Cd and Zn retained differed by a factor of more than 3 among the treatments in the long‐term field experiment, when a massive concentration of metal was added to soil. An increased sorption on smaller particle size fractions occurred (clay ≫ silt > fine sand ≥ coarse sand) due to the larger surface area as well as the greater carbon content in the smaller fractions. Soil sorption behaviour in another long‐term field experiment was estimated based on the present particle‐sorption data. Differences in the sorption behaviour were related to differences in soil mineralogy and amounts of Fe‐ and Mn‐oxides. Fractionation of the original and the metal‐spiked soil underlined the contribution of organic matter to sorption capacity (sequence: Cu ≫ Cd > Zn). Different organic matter contents and a different soil pH considerably changed the amounts of metals in the defined geochemical fractions. Freshly added Cu, Cd and Zn ions were found mainly in more mobile fractions. In contrast, metals in non‐spiked soils appeared in less‐mobile fractions reflecting their long‐term sorption behaviour.     

Modelling trace metal extractability and solubility in French forest soils by using soil properties

Soil/solution partitioning of trace metals (TM: Cd, Co, Cr, Cu, Ni, Sb, Pb and Zn) has been investigated in six French forest sites that have been subjected to TM atmospheric inputs. Soil profiles have been sampled and analysed for major soil properties, and CaCl₂‐extractable and total metal content. Metal concentrations (expressed on a molar basis) in soil (total), in CaCl₂ extracts and soil solution collected monthly from fresh soil by centrifugation, were in the order: Cr > Zn > Ni > Cu > Pb > Co > Sb > Cd , Zn > Cu > Pb = Ni > Co > Cd > Cr and Zn > Ni > Cu > Pb > Co > Cr > Cd > Sb , respectively. Metal extractability and solubility were predicted by using soil properties. Soil pH was the most significant property in predicting metal partitioning, but TM behaviour differed between acid and non‐acid soils. TM extractability was predicted significantly by soil pH for pH < 6, and by soil pH and Fe content for all soil conditions. Total metal concentration in soil solution was predicted well by soil pH and organic carbon content for Cd, Co, Cr, Ni and Zn, by Fe content for Cu, Cr, Ni, Pb and Sb and total soil metal content for Cu, Cr, Ni, Pb and Sb, with a better prediction for acidic conditions (pH < 6). At more alkaline pH conditions, solute concentrations of Cu, Cr, Sb and Pb were larger than predicted by the pH relationship, as a consequence of association with Fe colloids and complexing with dissolved organic carbon. Metal speciation in soil solutions determined by WHAM‐VI indicated that free metal ion (FMI) concentration was significantly related to soil pH for all pH conditions. The FMI concentrations of Cu and Zn were well predicted by pH alone, Pb by pH and Fe content and Cd, Co and Ni by soil pH and organic carbon content. Differences between soluble total metal and FMI concentrations were particularly large for pH < 6. This should be taken into account for risk and critical load assessment in the case of terrestrial ecosystems.     

Comparative effectiveness of selected adsorbant materials as potential amendments for the remediation of lead-, copper- and zinc-contaminated soil

Bonemeal, coir, compost, green waste compost, peat and wood bark all potentially could be used as amendments to remediate heavy metal contamination in soils. Their ability to sorb Pb, Cu and Zn was evaluated in the laboratory, using metal solutions ranging from 0 to 5 mmol/L as contaminants. The effects on sorption of metal concentration, background salt concentration and metal competition were evaluated. Single metal sorption by the six amendments was significantly different at metal concentrations of 1.5–5 mmol/L, with green waste compost, coir, compost and wood bark having the highest capacities to adsorb Pb, Cu and Zn. Langmuir sorption maxima were approximately 87 mg Pb/g (coir and green waste compost), 30 mg Cu/g (compost and green waste compost) and 13 mg Zn/g (compost and green waste compost) (equivalent to approx. 0.5 mmol/g of Pb and Cu, and 0.2 mmol/g Zn), all in a background solution of 0.001 M Ca(NO₃)₂. A higher background salt concentration and a combination of all three metals led to significant reduction in the amounts of Pb, Cu and Zn sorbed by all the amendments tested. Competing heavy metal cations in solution decreased Pb sorption to about 50–60% of that from a solution containing Pb alone; Cu sorption was reduced to about 30–40%; the effect of competition on Zn sorption was variable. Overall, in both single metal and competitive sorption, the order of strength of binding was Pb>Cu>>Zn.     

Heavy Metal Concentrations,Partitioning, and Storage in Slovak Forest and Arable Soils Along a Deposition Gradient

Along a heavy metal deposition gradient, caused by a Cu smelter, heavy metal concentrations, partitioning, and storage in forest and arable soils were examined. We sampled organic and mineral soil horizons (0—50 cm) at ten pairs of forest and arable sites derived from the same parent material. A-horizons were extracted with a seven-step sequence; O- and subsoil horizons were digested with strong acids (HNO₃/HClO₄). We found high concentrations of Cd (up to 17.38 mg kg^—1 in the O horizons/up to 2.44 mg kg^—1 in the A horizons), Cu (8437/415), Pb (3343/126), and Zn (1482/637) which decreased exponentially with distance from the smelter and with soil depth. The metal concentrations in the organic layers indicate that the average transport distance decreases in the order Cd > Zn > Pb > Cu. With regard to metal partitioning, NH₄NO₃- + NH₄OAc-extractable forms in the A horizons were most affected by the deposition being more pronounced under forest. In the uppermost 50 cm of the four soils nearest to the smelter two to four times higher Cd, Cu, Pb, and Zn storages were found in forest than in arable soils. At greater distance, the higher deposition onto forest soils due to the scavenging effect of the canopy obviously was compensated by stronger leaching.     

Trace metals and metalloids in forest soils and exotic earthworms in northern New England,USA

Trace metals and metalloids (TMM) in forest soils and invasive earthworms were studied at 9 sites in northern New England, USA. Essential (Cu, Mo, Ni, Zn, Se) and toxic (As, Cd, Pb, Hg, U) TMM concentrations (mg kg⁻¹) and pools (mg m⁻²) were quantified for organic horizons (forest floor), mineral soils and earthworm tissues. Essential TMM tissue concentrations were greatest for mineral soil-feeding earthworm Octolasion cyaneum. Toxic TMM tissue concentrations were highest for organic horizon-feeding earthworms Dendobaena octaedra, Aporrectodea rosea and Amynthas agrestis. Most earthworm species had attained tissue concentrations of Pb, Hg and Se potentially hazardous to predators. Bioaccumulation factors were Cd > Se > Hg > Zn > Pb > U > 1.0 > Cu > As > Mo > Ni. Only Cd, Se, Hg and Zn were considered strongly bioaccumulated by earthworms because their average bioaccumulation factors were significantly greater than 1.0. Differences in bioaccumulation did not appear to be caused by soil concentrations as earthworm TMM tissue concentrations were poorly correlated with TMM soil concentrations. Instead, TMM bioaccumulation appears to be species and site dependent. The invasive A. agrestis had the greatest tissue TMM pools, due to its large body mass and high abundance at our stands. We observed that TMM tissue pools in earthworms were comparable or exceeded organic horizon TMM pools; earthworm tissue pools of Cd were up 12 times greater than in the organic horizon. Thus, exotic earthworms may represent an unaccounted portion and flux of TMM in forests of the northeastern US. Our results highlight the importance of earthworms in TMM cycling in northern forests and warrant more research into their impact across the region.