Interactions between Cd,Cu, Pb,and Zn and four different mine soils

The chemical associations of Cd, Cu, Pb, and Zn in four mine soil samples from the Amizour-Bejaia Pb/Zn mine (Algeria) have been investigated by a five-step sequential extraction procedure. Although Cd preferentially binds to carbonates, Cu, Pb, and Zn are mainly associated with the organic and reducible fractions. Batch adsorption experiments with either mono- or multi-metallic solutions are described with the Freundlich isotherm model. Whatever the nature of the soil sample, the sorption behavior for each given metal except Pb is very similar, indicating that the binding sites at the soil surface are progressively occupied by the metal from the solution. On each soil sample, the decreasing order of sorption can be established as Pb >> Cu > Cd > Zn. When the four metals are simultaneously applied to each soil sample, their specific behavior is strongly affected by their interactions and/or competition for the available surface sites: we generally observed isotherm curves with a slight maximum before the plateau at higher solution concentration. Although Cu is only slightly affected by the other metals, in the case of Pb, Cd, and Zn, the sorbed amounts strongly decreased.     

Distribution and sorption of potentially toxic metals in four forest soils from Hungary

Metals of natural and anthropogenic origin behave differently in soils mostly due to their different mobility. In this study, sequential extractions and batch sorption experiments were performed to relate the fractionation of native Ni, Cu, Zn and Pb to the sorption properties of added metals in four soils with contrasting physiochemical characteristics. A significant effect due to sample composition on both the mobility and sorption characteristics of these metals was found. The efficiency of soil components in metal immobilization was in the order of carbonate > organic matter > swelling clay minerals. The partitioning of native metals together with the information gained through the sorption isotherms allows a deeper insight on the fate and behavior of metals in soils with various compositions.     

The concentration of Cu(II), Pb(II) and Zn(II) from aqueous solutions by particulate algal matter

Experimental studies of the reactions of Cu(II), Pb(II), and Zn(II) in aqueous solutions with organic matter derived from fresh samples of the green filamentous algae Ulothrix spp. and the green unicellular algae Chlamydomonas spp. and Chlorella vulgaris show that, under suitable conditions, a significant proportion of the metals is removed from solution by sorption onto the particulate organic matter of the algal suspension.The metal sorption is strongly suppressed by H⁺ but is only marginally influenced by the proportion of whole cells in the suspension and by complexing of metals in solution by the soluble organic matter. The presence of relatively small amounts of the cations Na⁺ and Mg²⁺ in solution reduces the sorption of Zn(II) to near zero, but Pb(II) and Cu(II) sorption occurs to an appreciable extent even in strong brines. This may be a means for the selective precipitation of Pb(II) from brines rich in Pb(II) and Zn(II).Metal “saturation” values indicate that particulate algal matter of the type used in these experiments could sorb sufficient quantities of metal to form an ore deposit if a weight of organic matter of similar order of magnitude to that of the inorganic sediments in the deposits was available. However, the metal sorption is an equilibrium reaction, and the experimentally determined “enrichment factors” suggest that the “saturation” values could be approached only in solutions whose metal contents were initially at least two orders of magnitude above those of normal seawater.     

Exploring Cd,Cu, Pb,and Zn dynamic speciation in mining and smelting-contaminated soils with stable isotopic exchange kinetics

The exchange kinetics of Cd, Cu, Pb, and Zn in seven mining and smelting-contaminated soils and the other two anthropogenically contaminated soils was investigated by using multi-elementary stable isotopic exchange kinetic (SIEK) method, and the experimental results were successfully interpreted by modelling using a sum of pseudo first order kinetics equations. SIEK results show that in the studied soils the isotopic exchange of Cd is a relatively fast process, and the exchange almost reaches an apparent plateau after 3-d equilibration; whereas for Cu, Pb, and Zn, the exchange is more sluggish, suggesting that it is important to understand the time-dependent metal mobility for risk assessment and management of contaminated soils. In most of the soils, the total isotopically exchangeable pool is divided, for all the metals, into two distinct pools: a fast exchangeable pool (E₁) with a kinetic rate constant k₁ having values around 1 min⁻¹ and a much slower exchangeable pool (E₂) with k₂ ranging from 0.0001 min⁻¹ to 0.001 min⁻¹. The distribution of the two exchangeable pools varies significantly among metals. The amount of isotopically exchangeable Cd related to the fast pool is dominant, accounting for on average 60% of total isotopically exchangeable pool in the soils; whereas this pool is smaller for Cu, Zn, and Pb. The sequence of average k₁ values is Cd > Pb ≈ Zn > Cu, consistent with the reported sequence of stability constants of metal-humic substances (HS) complexes while the average k₂ values follow the order: Cd > Pb > Cu > Zn, probably controlled by the slow desorption of metal ions associated with soil organic matter (SOM) fraction. Our results imply that further study on the exchange kinetics of metals on each individual sorption surface in soils, especially SOM, is critical to help understanding the overall exchange kinetics of heavy metals in whole soils.     

Monitoring and modelling of the solid-solution partitioning of metals and As in a river floodplain redox sequence

For a period of 2 a, pore water composition in a heavily contaminated river floodplain soil was monitored in situ. Pore water samples were collected 12 times over all seasons in a profile ranging from aerobic to sulphidic redox conditions, and As, Cd, Cr, Cu, Pb, Zn, Mn, Fe, Ca, Cl, SO₄, DOC, IOC and pH were determined. The variability of pH, IOC, DOC and Ca was found to be rather small during the year and within the profile (rsd < 0.04, 0.16, 0.24 and 0.22, respectively). The temporal variability of the metal and As concentrations was small, too, whereas changes with depth were distinct. Under sulphidic conditions, concentrations were below 1 μg L⁻¹ (Cd, Cu, Pb) or 10 μg L⁻¹ (Zn, As). The data set was compared with results from a geochemical model that was fully parameterised from literature data and included equilibrium speciation, sorption and mineral dissolution. The general pattern of the solid–solution partitioning of Cd, Cu, Zn and As in the profile was predicted well by mechanistic geochemical modelling on the basis of solid phase composition. Metals strongly bound to organic matter such as Cd and Cu were predicted better than metals mainly present within a mineral. Detailed information regarding the presence of colloidal Fe and Mn in pore water might improve the prediction of the solid–solution partitioning of a number of metals. The study also indicates that the chemical behaviour of Pb is still not understood sufficiently.     

Contamination assessment and health risk of heavy metals in dust from Changqing industrial park of Baoji,NW China

The contents of Co, Cr, Cu, Mn, Ni, Pb and Zn in the dust samples collected from Changqing industrial park of Baoji city, NW China, were measured by XRF, while As and Hg in the dust samples were analyzed by AFS. Geo-accumulation index (I _geo), pollution index (PI) and integrated pollution index (IPI) were calculated to evaluate the heavy metal contamination level of dust. The health risk due to exposure to heavy metals in dust was analyzed by the Health Risk Assessment Model of US EPA. The results show that the arithmetic means of As, Co, Cr, Cu, Hg, Mn, Ni, Pb and Zn are 23.3, 16.4, 1591.8, 178.2, 0.243, 346.5, 40.2, 1,586.2 and 1,918.8 mg kg^?1, respectively, which are higher than the background values of Shaanxi soil, especially for Cr, Cu, Hg, Pb, and Zn. The mean values of I _geo reveal the order of Pb > Zn > Cr > Hg > Cu > As > Co > Ni > Mn. The high I _geo of Cr, Cu, Hg, Pb and Zn in dust indicates that there is considerable pollution from Cr, Cu, Hg, Pb and Zn, while the low I _geo of As, Co, Mn and Ni presents no pollution in dust. The assessment results of PI support the results of I _geo, and IPI indicates heavy metals in dust polluted seriously. The health risk assessment shows that ingestion of dust particles is the route for exposure to heavy metals from dust, followed by dermal adsorption. Exposure to As, Cr and Pb from dust may pose a potential health threat to children and adults. The risk of cancer from As, Co, Cr and Ni due to dust exposure is low.     

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.     

Reconstitution des apports en éléments traces métalliques et bilan de leur migration dans un Luvisol sableux soumis à 100 ans d'irrigation massive par des eaux usées brutes

Raw wastewaters were massively spread on sandy luvisols near Paris from 1899 to 2002, leading to high trace metals (TM) pollution of soils. Mass balance calculations were performed on a soil profile to assess vertical migration of TM. The contamination was estimated by subtracting the natural pedo-geochemical background of the horizons. TM inputs were estimated using Cr as an invariant. It is shown that Pb and Cr remained in the surface horizon, while Ni, Cd, Cu and Zn migrated downward, being more or less trapped depending on the physicochemical properties of the horizons. To cite this article: C. Dère et al., C. R. Geoscience 338 (2006).     

Impact of historical metalworks on the concentrations of major and trace elements in sediments: a case study in Finland

The concentrations of major and trace elements were determined (aqua regia leach and ICP-AES analyses) in stream, lake and dredged sediments downstream of the historical Antskog iron- and copperworks, S.Finland. The levels of Ag, Cd, Cu, Pb and Zn are highly elevated in all studied sediment types: roughly half of the studied lake-sediment samples contain >5 ppm Ag, >15 ppm Cd, >0.1% Cu, >0.1% Pb and >0.3% Zn. In the dredged sediment material located onshore, the concentrations of Ag, Cu and Pb are comparable to those in the polluted lake-sediment samples, while in stream sediments elevated metal concentrations are found especially in samples characterised by high concentrations of organic material. The source of the elevated metal concentrations is the historical metalworks at Antskog, mainly the copperworks of the 19th century. Compared to the limit values for contaminated soils in Finland, the concentrations of Cu, Pb and Zn are on average elevated by factors >10 in the polluted horizons of lake sediments, >5 in the dredged sediment located onshore and >2 at the most heavily contaminated site in the stream. Since the surface waters in the area are used for agricultural purposes and for various leisure activities, it is necessary to make further detailed investigations into the extent of the metal pollution and to determine species, mobility and bioavailability of the metals.     

Nitric-acid soluble fractions of 21 elements in Norwegian podzols: Factors affecting regional differences in vertical distribution

Distributions of 21 major and trace elements in HNO₃ extracts of different horizons were studied in 13 podzol profiles from the boreal forest in different parts of Norway using ICP–MS. On the basis of ratios between the HNO₃-extractable fractions in the various horizons some general trends were elucidated. Two different groups of elements concentrated in the humus layer relative to the mineral horizons were identified, one mainly associated with contributions from air pollution (As, Cd, Sb, Pb), another one with plant nutrient circulation (K, Ca, Mn and to a lesser extent Mg, Co, Ni, Rb) and some with both mechanisms (Cu, Zn, Tl). The elements most clearly enriched along with Fe in the B horizon were V, Pb, Al, and Cr in that order, Pb partly because of leaching from the polluted organic surface soil. Four soils in the far south showed a behaviour distinctly different from the rest and were treated as a separate group. Relative to the more northerly sites the surface horizons of these soils were strongly depleted in lithogenic elements (Mg, Al, K, Ca, Sc, V, Cr, Mn, Fe, Co, La) and enriched in elements typical of long-range transport of pollutants (As, Cd, Sb, Tl, Pb). Also the B horizon in the southern soils was strongly depleted in the lithogenic group elements, including Fe and the associated metals. The main reason for this difference is assumed to be the greater influence of transboundary air pollution and associated metals and stronger soil acidification in the far south of the country.     

Distribution of trace elements in soils surrounding the El Teniente porphyry copper deposit,Chile: the influence of smelter emissions and a tailings deposit

In the area surrounding the El Teniente giant porphyry copper deposit, eight soil sites were sampled at three depth levels in the summer 2004. The sites were selected for their theoretical potential of being influenced by past SO₂ emissions from the smelter and/or seepage from a now idle tailings impoundment. The soil mineralogy, grain size distribution, total organic matter contents, major element composition, cation exchange capacity, and Cu, Mo, Pb, Zn, As and SO₄ ²⁻ concentrations were determined for all samples after nitric acid extraction and separate leaches by ammonium acetate (pH 7) and sodium acetate (pH 5). For water rinses, only Cu could be determined with the analytical set-up used. Cu and SO₄ ²⁻ enrichment in topsoils was found at six sites either downwind from the smelter or within the combined influence of the smelter and the tailings impoundment. Both elements were released partially by ammonium and sodium acetate extractions. Due to the scarce background trace element concentrations of soil and rock outside the immediate mine area, assessment of trace element mobility for Mo, Zn, Pb and As was difficult. Arsenic was found to be concentrated in soil horizons with high smectite and/or organic matter contents. Mo appears to be linked to the presence of windblown tailings sediment in the soils. Mobilization of Mo, Zn, and As for the acetate extractions was minimal or below the detection limits for the AAS technique used. The presence of windblown tailings is considered to be an additional impact on the soils in the foothills of the El Teniente compound, together with the potential of acidity surges and Cu mobilization in topsoils after rainfalls. Two sites located at the western limit of the former SO₂ saturated zone with strongly zeolitized soils and underlying rock did not show any Cu or SO₄ ²⁻ enrichment in the topsoils, and remaining total trace element concentrations were below the known regional background levels.     

Similar Adsorption Parameters for Trace Metals with Different Aquatic Particles

Conditional surface binding constants and complexation capacities for Zn, Pb, Cd, and Cu were determined from surface titration experiments of heterogeneous natural aquatic particulate matter of different origin and composition. Metals and particles were evaluated in naturally occurring concentration ranges in river water.The adsorption of trace metals can be adequately described with a single conditional binding constant over a wide range of metal : particle ratios. Binding constants for aquatic particles at pH 8.0 are remarkably independent from particle composition and are specific for each metal: log K^ads _Zn = 8.39, log K^ads _Pb = 9.67, log K^ads _Cd = 8.61, log ^ads _Cu = 9.84. From competition experiments with Ca and Pb we extracted a sorption coefficient for Ca of log K^ads _Ca = 2.5 (pH 8.0). Maximum surface binding capacities for all metal ions were found for particles containing high fractions of Mn-oxides which are associated with large specific surface areas. Generally, we found sorption capacities to decrease in the sequence Cu Pb, Zn > Cd.The experiments suggest that the conditional surface binding constants and complexation capacities are applicable to model trace metal adsorption in the concentration ranges of natural waters under conditions similar to the experiments. Results also imply that the chemical nature of particle surface sites is rather uniform in the intermediate concentration range or that the array of binding sites averages out differences in sorption strength over the prevailing concentration range of metal ions, respectively.     

Uptake of metals by plants in urban areas

In the present study, bulk contents of Ni, Zn, Cu, Pb and Mn in urban area of Tehran city are determined. Subsequently, the chemical bonds of metals with various soil fractions are brought out. Chemical partitioning studies revealed that various percentile of Ni, Zn, Cu, Pb and Mn is found in anthropogenic portion of soils. Zinc, Ni, Cu, Pb and Mn fall within “low pollution” class in accordance with index of pollution (I _POLL). The trend of anthropogenic share of studied metals in soils of Tehran is Zn (55 %) > Cu (31 %) > Ni and Pb (30 %) > Mn (12 %). The overall potential of studied plants in metal removal from soil is Salvia > Viola > Portulaca. It should be pointed out that roots have higher potential in metal removal from soil when compared with leaf and stem. Lithogenic portion of metals remains intact before and after pot analysis. Thus, phytoremediation is highly dependent on the chemical bonds of metals. Present study showed that metal contents of loosely bonded ions, sulfide bonds and organometallic bonds are reduced after 90 days of plant cultivation. The overall removal trend of studied metals is Zn (16 %) > Cu (14 %) > Ni (11 %) > Pb (7 %) > Mn (6 %). The obtained results show that the anthropogenic portion of metals is reduced after the phytoremediation practice. For instance, the initial anthropogenic portion of Zn (55 %) is changed to 39 % showing an overall reduction of about 16 %. The anthropogenic portions of Cu, Ni, Pb and Mn are also reduced by 14, 11, 7 and 6 %, respectively.     

Heavy metal relationships in a Pennsylvania soil

Soils of loamy sand on weathered, sandy dolomite were cored from six holes up to 70 ft beneath a municipal waste landfill in central Pennsylvania. Mn, Fe, Ni, Co, Cu, Zn, Cd, Pb, and Ag were determined in exchangeable and non-exchangeable forms in total and < 15 μm soil samples. Most of these metals were bound in Mn oxides, non-exchangeable with 0.5 M CaCl₂. The Mn oxides (often X-ray amorphous) identified when crystalline as todorokite occurred chiefly as coatings on quartz grains.Somewhat higher amounts of acid leachable trace metals were found in the < 15 μm size fraction than in the total soil samples; however, trace metal/Mn ratios were similar in both. In general, the initial mild soil leaching, which dissolved chiefly Mn oxides, gave MnFeX>Co>Ni>Pb>Zn> Cu>Cd>Ag. The final leaching, which dissolved chiefly ferric oxides, gave Fe>Mn>Ni>Zn>Co> Cu>Pb>Cd>Ag. Samples taken from an unpolluted site and from the same soils affected for seven years by leachate from the refuse had similar metal contents.Soil extractable Co, Ni, Cu, and Zn could be predicted from the Mn extracted. Based in part on factor analysis of the data, Mn-rich oxides had at least tenfold higher heavy metal percentages than Fe-rich oxides (crystalline component goethite), reflecting their greater coprecipitation potential. Because of this potential and because of the generally higher solubility of Mn than Fe oxides, more heavy metals may be released from Mn-rich than from Fe-rich soils by disposal of organic-bearing wastes. However, leaching of the moisture-unsaturated soils in situ is rarely severe enough to completely dissolve both Mn and Fe oxides. Based on the Mn content, Cd, Cu, and Pb were depleted in soil moisture beneath the landfill relative to their amounts in the soil. This depletion may reflect factors including heterogeneity in metal content of the soil oxides; preferential resorption of these metals; and removal of the Cd, Cu, and Pb as organic precipitates or as inorganic precipitates such as carbonates.     

Competitive sorption and desorption of cadmium and lead in paddy soils of eastern China

To assess the competitive sorption and desorption of cadmium (Cd) and lead (Pb), batch equilibrium experiments were performed using single- and binary-metal solutions in surface samples of three paddy soils from eastern China. Sorption isotherms were well fitted with one-metal and competitive Langmuir equation for single- and binary-metal system, respectively. The distribution coefficient (K _d) values were K _{d single} (Pb) > K _{d binary} (Pb) > K _{d single} (Cd) > K _{d binary} (Cd), indicating that Pb was stronger sorbed by these soils than Cd in binary metal system. Soils with high pH and clay content had the greatest sorption capacity as estimated by the maximum sorption parameter (Q). The co-existence of both metals reduces their tendency of sorption, whereas Cd sorption was affected to a greater extent than that of Pb. The Langmuir binding strength parameter (b) in binary sorption system was greater than that in single sorption system for all soils (b < b ₁), indicating that competition for sorption sites promote the retention of both metals into more specific sorption sites. Sorption of Cd and Pb decreased soil pH by 1.61 U for YRS, 1.39 U for PCS, and 0.91 U for SLS. The decreases of pH in binary metal system were greater than in single-metal system for three soils. Cadmium and Pb desorption increased with increasing Cd and Pb sorption saturation for all soils; however, Cd desorption ratio in binary metal system (d _Cd*) was much greater than Pb (d _Pb*), indicating that under the competitive sorption conditions, the sorbed Cd was more readily desorbed from the soils than the sorbed Pb.     

Fluoride sorption and desorption on soils located in the surroundings of an aluminium smelter in Galicia (NW Spain)

Aluminium smelters are major sources of F emission to the environment. We studied, in laboratory experiments, the sorption and desorption of fluoride on organic and mineral horizons of soils located within 2 km from one of these factories, situated in the northern coast of Galicia (NW Spain). The soils, developed from granite, are acid (pH H₂O 3.9–5.5), rich in organic matter (4–16 % C in the A horizon) and most A horizons have high Al saturation in the exchange complex. All samples showed a notable F sorption, between 1,066 and 1,589 mg kg^?1, after adding 200 mg F L^?1, which accounts for 53–80 % of F added. The sorption was slightly higher in the A horizons than in the respective organic horizons (differences of up to 194 mg kg^?1). The fluoride sorption upon addition of 200 mg F L^?1 correlated significantly (p < 0.05) with soil pH in water (r = ?0.77), iron extracted by acid ammonium oxalate (r = 0.68), aluminium plus iron extracted by acid ammonium oxalate (r = 0.63), exchange aluminium (r = 0.52) and clay percentage in soil (r = 0.76). The F sorption fitted to both Langmuir and Freundlich models. Desorbed F accounted for only 12–22 % of sorbed fluoride and correlated (p < 0.05) negatively with non-crystalline (extracted by acid ammonium oxalate) Fe (r = ?0.51) and clay content (r = ?0.74) and positively with organic matter (r = 0.69) and with the effective cation exchange capacity of the soil (r = 0.50).     

Using atmospheric fallout to date organic horizon layers and quantify metal dynamics during decomposition

High concentrations of metals in organic matter can inhibit decomposition and limit nutrient availability in ecosystems, but the long-term fate of metals bound to forest litter is poorly understood. Controlled experiments indicate that during the first few years of litter decay, Al, Fe, Pb, and other metals that form stable complexes with organic matter are naturally enriched by several hundred percent as carbon is oxidized. The transformation of fresh litter to humus takes decades, however, such that current datasets describing the accumulation and release of metals in decomposing organic matter are timescale limited. Here we use atmospheric ²¹⁰Pb to quantify the fate of metals in canopy-derived litter during burial and decay in coniferous forests in New England and Norway where decomposition rates are slow and physical soil mixing is minimal. We measure ²¹⁰Pb inventories in the O horizon and mineral soil and calculate a 60-630 year timescale for the production of mobile organo-metallic colloids from the decomposition of fresh forest detritus. This production rate is slowest at our highest elevation (∼1000 m) and highest latitude sites (>63°N) where decomposition rates are expected to be low.We calculate soil layer ages by assuming a constant supply of atmospheric ²¹⁰Pb and find that they are consistent with the distribution of geochemical tracers from weapons fallout, air pollution, and a direct ²⁰⁷Pb application at one site. By quantifying a gradient of organic matter ages with depth in the O horizon, we describe the accumulation and loss of metals in the soil profile as organic matter transforms from fresh litter to humus. While decomposition experiments predict that Al and Fe concentrations increase during the initial few years of decay, we show here that these metals continue to accumulate in humus for decades, and that enrichment occurs at a rate higher than can be explained by quantitative retention during decomposition alone. Acid extractable Al and Fe concentrations are higher in the humus layer of the O horizon than in the mineral soil immediately beneath this layer: it is therefore unlikely that physical soil mixing introduces significant Al and Fe to humus. This continuous enrichment of Al and Fe over time may best be explained by the recent suggestion that metals are mined from deeper horizons and brought into the O horizon via mycorrhizal plants. In sharp contrast to Al and Fe, we find that Mn concentrations in decomposing litter layers decrease exponentially with age, presumably because of leaching or rapid uptake, which may explain the low levels of acid extractable Mn in the mineral soil. This study quantifies how metals are enriched and lost in decomposing organic matter over a longer timescale than previous studies have been able to characterize. We also put new limits on the rate at which metals in litter become mobile organo-metallic complexes that can migrate to deeper soil horizons or surface waters.     

Modelling retention of heavy metals in the Oostriku peat bog,Estonia: Comparison of predicted and observed results

In this study, the retention of Ca and other metals (Pb, Cu, Fe, Zn and Mn) in the Oostriku peat bog (central Estonia) was modelled. Equilibrium sorption of metals on amorphous ferric oxyhydroxide and solid organic matter was simulated at steady-state. Ferric oxyhydroxide formation and possible precipitation of other metals (Mn, Pb and Cu) in the peat was also assessed. Evolution of metal sorption fronts along a peat profile over time was simulated with a dynamic model to test if metal–metal competition effects could cause Pb and Cu to sorb at higher amounts in the uppermost peat than in the lower peat, as observed in the field. The predicted sorbed amounts of metals were compared with those previously observed in the peat. In general, good agreement between both batch and dynamic model results and the independent observations at the Oostriku peat site was obtained. This suggests that the relatively simple model approach employed here might be generally useful for assessing other peat sites and similar applications.     

Metal retention in a thin karstic soil, Christian County, Missouri

 The response of a Wilderness cherty loam series soil to repeated dosages of metals (as sewage sludge) using a two-step sequential extraction procedure was investigated. Variations in metal content between amended and control soils were related to organic matter, clay content, and clay mineralogy. Of the four metals investigated, Cu was found to accumulate in the top 20 cm of amended soils; Pb and Zn were present in even smaller amounts with respect to the control soils, and Cr concentrations were unaffected with respect to both depth and amendment. None of the metals indicated accumulation in deeper (>20 cm) parts of the soil profile. Overall, results suggest that the metals remobilize in the top 20 cm, being readily uptaken by the fescue grass growing in this lot. Precipitation of insoluble forms of metal into deeper parts of the soil profile was proven unlikely based on the distribution of metal concentrations throughout the profile. Received: 15 December 1997 · Accepted: 23 March 1998     

Competitive adsorption of Cd,Cu, Pb and Zn by different soils of Eastern China

Simultaneous competitive adsorption behavior of Cd, Cu, Pb and Zn onto nine soils with a wide physical–chemical characteristics from Eastern China was measured in batch experiments to assess the mobility and retention of these metals in soils. In the competitive adsorption system, adsorption isotherms for these metals on the soils exhibited significant differences in shape and in the amount adsorbed. As the applied concentration increased, Cu and Pb adsorption increased, while Cd and Zn adsorption decreased. Competition among heavy metals is very strong in acid soils with lower capacity to adsorb metal cations. Distribution coefficients (K _dmedium) for each metal and soil were calculated. The highest K _dmedium value was found for Pb and followed by Cu. However, low K _dmedium values were shown for Zn and Cd. On the basis of the K _dmedium values, the selectivity sequence of the metal adsorption is Pb > Cu > Zn > Cd and Pb > Cu > Cd > Zn. The adsorption sequence of nine soils was deduced from the joint distribution coefficients (K _dΣmedium). This indicated that acid soils with low pH value had lower adsorption capacity for heavy metals, resulting in much higher risk of heavy metal pollution. The sum of adsorbed heavy metals on the soils could well described using the Langmuir equation. The maximum adsorption capacity (Q _m) of soils ranged from 32.57 to 90.09 mmol kg⁻¹. Highly significant positive correlations were found between the K _dΣmedium and Q _m of the metals and pH value and cation exchange capacity (CEC) of soil, suggesting that soil pH and CEC were key factors controlling the solubility and mobility of the metals in soils.