Cadmium soil sorption at low concentrations: V. Evidence of competition by other heavy metals

Sorption of Cd at low concentrations onto 12 Danish soils (coarse sands to sandy loams) was studied with respect to competitive effects of other heavy metals by means of laboratory batch experiments. Both a mixture of Ni, Co, and Zn and of Cr, Cu, and Pb effectively reduced the sorption of Cd onto the soils. The employed mixtures of competing heavy metals were considered to resemble moderately polluted conditions. Cadmium distribution coefficients were reduced 2 to 14 times due to competition, but at constant concentrations of competing heavy metals the shape of Cd isotherms was not affected. The effect of Ni, Co, and Zn, which like Cd is primarily governed in soil environments by sorption, was also studied individually. Apparently Zn, which is present in relatively higher concentrations than Ni and Co, accounts for most of the observed competition with Cd.     

Surface loading effect on Cd and Zn sorption by kaolinite and montmorillonite from low concentration solutions

Studies of Cd and Zn sorption using Na-saturated kaolinite and montmorillonite, and low metal solution concentrations similar to those found in the environment, showed that metal sorption affinity (measured by K _d values) decreased markedly with increasing surface metal loading for both layer silicates. For equilibrium solution concentrations <0.1 μmol L^?1 for Cd, and < 1 μmol L^?1 for Zn, both metals were sorbed with greater affinity by kaolinite than montmorillonite. These results were probably due to the higher proportion of weakly acidic edge sites present on kaolinite surfaces. In the case of Zn there was an affinity reversal for equilibrium solution concentrations > 1 μmol L^?1, which was attributed to the permanent charge sites of montmorillonite. Cadmium ions were sorbed, by kaolinite, with greater affinity than Zn for equilibrium solution concentrations between 0.3 to 1.5 μmol L^?1. This result was attributed to retention of these metal ions through electrostatic attraction by permanent charge sites present on the kaolinite used in this work. According of these results it seems that metal sorption by these layer silicates involves predominantly edge weak acid sites at lower surface coverages (higher affinity sites), and permanent charge sites at higher metal coverages (lower affinity sites). It was concluded that Cd and Zn sorption by those two layer silicates is greatly influenced by surface metal coverage, and results cannot be extrapolated from low to high surface coverages, and viceversa.     

Cadmium soil sorption at low concentrations: I. Effect of time,cadmium load,pH, and calcium

Sorption of Cd at low concentrations onto two Danish soils (loamy sand, sandy loam) was examined in terms of kinetics and governing factors. From an environmental point of view soil sorption of Cd is a fast process: More than 95% of the sorption takes place within 10 min, equilibrium is reached in 1 hr, and exposures up to 67 wk did not reveal any long term changes in Cd sorption capacities. The soils have very high affinity for Cd at pH = 6.00 (10^?3 M CaCl₂) exhibiting distribution coefficients in the order of 200 to 250 (soil Cd concentration/solute Cd concentration). However, the sorption isotherms describing the distribution of Cd between soil and solute are slightly curvelinear. In the pH-interval 4 to 7.7, the sorption capacity of the soil approximately increases 3 times for a pH increase of one unit. Increasing the Ca concentration from 10^?3 to 10^?2 M reduces the sorption capacity of the sandy loam to one third.     

Concentration Changes of Cd, Ni and Zn in Sugarcane Cultivated Soils

In the southwest of Iran over 130,000 ha of land are under sugarcane (Saccarum officinarum). In these sugarcane fields, about 400 kg ha^?1 diamonium phosphate (DAP) and 400 kg ha^?1 urea are applied annually. Four sugarcane growing sites were selected for this study: Haft-tapeh, Karoon, Shoeibieh and Ghazali with cultivation histories of 36, 20, 2 and 1 years, respectively. For each area, soil samples (0–30 cm) were taken from a transect of uncultivated, and both furrows and ridges of cultivated land. Electrical conductivity (EC), pH, clay, and calcium carbonate and organic carbon (OC) contents, Cl, Cd, Ni and Zn of 101 soil samples were measured. Cadmium profile distribution to a soil depth of 300 cm was determined, and the heavy metal concentrations in sugarcane and the associated soil samples of the three sugarcane sites were measured. The Cd and Ni contents among the sugarcane sites differed where Cd was related to clay content and Ni was related to OC content of soils. Cadmium content in sugarcane cultivated soil was lower compared to uncultivated soil even after years of application of P fertilizers. Nickel and Cd contents of sugarcane were much higher than levels in top soils but there was no significant relationship between Cd or Ni contents of sugarcane and soil chemical properties. The Zn content of soils decreased as either EC or Cl concentration of soils increased. There were no significant differences in Zn contents between different sugarcane sites and also between cultivated and uncultivated soils. Results also indicated that Cd was accumulated in bagasse and Ni was primarily accumulated in bagasse and molasses, but these heavy metals of white sugar were lower than the detectable values.     

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.     

Improved cadmium sorption isotherms by the determination of initial contents using the radioisotope 109Cd

Cadmium (Cd) sorption isotherms were estimated by two different analytical approaches to assess the influence of initial Cd concentrations of soil matrix on the sorption of added Cd. For the laboratory experiments a heterogeneous set of samples was collected to include a wide range of different initial Cd concentrations. Comparison of both analytical methods (conventional analysis, radioanalysis) resulted in a strong conformity of Cd contents in solution at equilibrium. The calculated Cd concentrations in the soil solid phase differ according to the analytical approach for considering the initial contents. The determination of the initial contents by the proposed radioanalytical method with ¹⁰⁹Cd resulted in long linear Freundlich‐isotherms, even in the low concentration range. Thus, radioanalysis seems to be the most suitable method to recognise the initial contents of Cd in soil. EDTA extractable Cd represent the initial concentrations, which are averaged over solid and liquid phase. However, depending on the sorption characteristics of the soil these rates vary. In the investigated set of soil samples 52.3 to 99.3% of Cd must be added to the solid phase.     

General purpose Freundlich isotherms for cadmium,copper and zinc in soils

Assessing the accumulation and transport of trace metals in soils and the associated toxicological risks on a national scale requires generally applicable sorption equations. Therefore Freundlich equations were derived for Cd, Zn and Cu using multiple linear regression on batch sorption data from the literature with a wide variety of soil and experimental characteristics, and metal concentrations ranging over five orders of magnitude. Equations were derived based on both total dissolved metal concentrations and free metal activities in solution. Free metal activities were calculated from total metal concentrations taking into account ionic activity, and inorganic (all metals) and organic complexation (Cu only). Cadmium and Zn were present in solution predominantly as free ions, while Cu was present as organic complexes. Since actual dissolved organic carbon (DOC) concentrations were not available they were estimated using an empirical field relation between DOC and organic matter content. The logarithmic transformation of the Freundlich constant for Cd was regressed on the logarithmic transformations of cation exchange capacity (CEC) (H⁺) and dissolved Ca, and for Zn with CEC and (H⁺). For Cu the log–log regression model of the Freundlich constant included the solid:solution ratio of the batch to account for dilution of DOC in the batch as compared with the field. The explained variance for the fitted Freundlich equations was 79% for Cd, 65% for Cu and 83% for Zn, using log-transformed adsorbed concentrations and soil solution activities. The Freundlich adsorption models underestimated metal contents determined from 1 m HNO₃ digestion on field samples, up to a factor of 6 (Cd and Cu) or 10 (Zn).     

共存阳离子（Ca、Zn、K）对土壤镉有效性的影响

采用盆栽与吸附试验,研究了镉污染赤红壤上,施用相同摩尔浓度的钙、钾与锌对小油菜生物量、镉吸收量及土壤镉吸附的影响。结果表明,低和高镉污染赤红壤上,施用锌明显增加小油菜地上部生物量,较对照分别增产21.1%和7.82%。不同阳离子（钠、钙、钾和锌离子）共存改变土壤吸附镉能力的程度不同,与钠体系相比,钙、钾和锌体系中土壤镉吸附量分别降低65.6%、72.0%和96.9%,共存离子降低土壤镉吸附量的次序为锌离子〉钾离子和钙离子,锌离子的影响最为明显。高镉污染赤红壤上,钙和钾使小油菜吸镉量分别增加5.5%和14.4%,低于低镉污染赤红壤上钙和钾使小油菜吸镉的增加量（分别为16.6%和19.6%）;锌明显降低小油菜吸镉量,高和低镉污染赤红壤上,较对照分别减少45.8%和35.0%。3种阳离子与镉共存时,对土壤镉生物有效性的影响差异取决于竞争吸附与竞争吸收的大小,其机制有待进一步探讨。     

Cadmium Uptake by Winter Wheat Seedlings in Response to Interactions Between Phosphorus and Zinc Supply in Soils

ABSTRACT

Effects of application of zinc (Zn) (0, 1, 5, 10 mg kg^?1 soil) and phosphorus (P) (0, 10, 50, 100 mg kg^?1 soil) on growth and cadmium (Cd) accumulations in shoots and roots of winter wheat (Triticum aestivum L.) seedlings were investigated in a pot experiment. All soils were supplied with a constant concentration of Cd (6 mg kg^?1 soil). Phosphorus application resulted in a pronounced increase in shoot and root biomass. Effects of Zn on plant growth were not as marked as those of P. High Zn (10 mg kg^?1) decreased the biomass of both shoots and roots; this result may be ascribed to Zn toxicity. Phosphorus and Zn showed complicated interactions in uptake by plants within the ranges of P and Zn levels used. Cadmium in shoots decreased significantly with increasing Zn (P < 0.001) except at P addition of 10 mg kg^?1. In contrast, root Cd concentrations increased significantly except at Zn addition of 5 mg kg^?1 (P < 0.001). These results indicated that Zn might inhibit Cd translocation from roots to shoots. Cadmium concentrations increased in shoots (P < 0.001) but decreased in roots (P < 0.001) with increasing P supply. The interactions between Zn and P had a significant effect on Cd accumulation in both shoots (p = 0.002) and roots (P < 0.001).     

Specific sorption of trace amounts of cadmium by soils

Abstract

Sorption of trace quantities of Cd in four soils of different chemical and mineralogical properties, was studied. Initial Cd concentrations were between 15 to 150 μg. 1^?1. The sorption isotherms were linear and had a positive intercept in three of the soils, indicating a constant partition‐high affinity sorption isotherm (Giles et. al⁶). The data also followed the Freundlich sorption isotherm, and the Freundlich K parameter was taken as a measure of the relative affinity of the different soils for the Cd metal sorbed. Cadmium sorbed was extracted by IN‐NH₄C1 followed by 0.1N HC1, and the fraction remaining in the soils was considered specifically sorbed Cd. This fraction also followed a linear sorption isotherm, and was around 30% for the four soils studied. The sorption order for the amount of specifically sorbed Cd showed that the Boomer soil (kaolinite‐iron oxides) had the lowest affinity for specific sorption of this metal. This was taken as evidence that kaolinite and iron oxides have a lower capacity for retaining cadmium through specific sorption mechanism(s) than the materials present on the other soils (2:1 layer silicates and humic substances). The existence of specific mecha‐nism(s) responsible by the sorption of trace quantities of Cd in soil solutions has important implications on soil‐plant relationships, Cd mobility in soil profiles and control of Cd activity in soil solutions.     

Effect of elevated concentrations of Cd and Zn in soil on spring wheat yield and the metal contents of the plants

The effect of increasing concentrations of Cd and Zn in a sandy soil on spring wheat (Triticum vulgare L.) yields and the metal contents of the plants was examined in a pot experiment to establish critical levels of these metals in soil. The metals were added (individually and jointly) to the soil as sulfates in the following doses (in μg g^?1, dry wt.): Cd — 2, 3, 5,10, 15, 25, and 50; Zn ?200, 300, 500, 1000, 1500, 2500, and 5000. Cadmium added to soil did not affect yields of wheat. The Zn dose of 1000 μg g^?1 strongly reduced crop yields; at 1500 μg g^? Zn dose wheat did not produce grain. The metal contents of wheat increased with increasing concentrations of Cd and Zn in soil up to 10.3 and 1587 μ g^? of Cd and Zn in straw, respectively. The concentrations of both metals were higher in straw than in grain by factors of 3–7 and 1.5–2 for Zn and Cd, respectively. The relationships between Cd and Zn contents of the plants and soils were best expressed by exponential equations. High concentrations of Zn in soils (1042 and 1542 μg g^?1) enhanced uptake of Cd by plants. The tested threshold concentrations of the metals in soils (3 μg g^?1 for Cd and 200–300 μg g^?1 for Zn) are safe for Zn but are too high for Cd in terms of protecting plants from excessive metal uptake. The critical Cd content of sandy soil should not exceed 1.5 μg g^?.     

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.     

Cadmium leaching from some New Zealand pasture soils

Cadmium (Cd) inputs and losses from agricultural soils are of great importance because of the potential adverse effects Cd can pose to food quality, soil health and the environment in general. One important pathway for Cd losses from soil systems is by leaching. We investigated loss of Cd from a range of contrasting New Zealand pasture soils that had received Cd predominantly from repeated applications of phosphate fertilizer. Annual leaching losses of Cd ranged between 0.27 and 0.86 g ha^–l, which are less than most losses recorded elsewhere. These losses equate to between 5 and 15% of the Cd added to soil through a typical annual application of single superphosphate, which in New Zealand contains on average 280 mg Cd kg^?1 P. It appears that Cd added to soil from phosphate fertilizer is fairly immobile and Cd tends to accumulate in the topsoil. The pH of the leachate and the total volume of drainage to some extent control the amount of Cd leached. Additional factors, such as the soil sorption capacity, are also important in controlling Cd movement in these pasture soils. The prediction of the amount of Cd leached using the measured concentrations of Cd in the soil solution and rainfall data resulted in an overestimation of Cd losses. Cadmium concentrations in drainage water are substantially less than the current maximum acceptable value of 3 µg l^?1 for drinking water in New Zealand set by the Ministry of Health.     

Cadmium and zinc additions to wisconsin soils by commercial fertilizers and wastewater sludge application

Cadmium and Zn concentrations were determined on 21 commercial fertilizer samples by atomic absorption. The Cd concentration ranged from 1.5 to 9.7 mg kg^?1, the median being 4.3 mg kg^?1. Zinc showed a much wider range. The Cd added to soil by commercial fertilizers may be as much as 2150 kg annually in Wisconsin, compared to a potential of 1700 kg if wastewater sludges from all municipal sewage treatment plants in the state were disposed of on land. However, because of the higher application rates, sludge Cd on a soil concentration basis is a much more concentrated source of Cd than that from phosphate fertilizers.     

Availability of Cadmium and Zinc as Affected by the Use of Reactive Phosphate Rock,Lime, and Chicken Manure on an Indonesian Acidic Upland Soil under Field Conditions

We assessed cadmium (Cd) and zinc (Zn) availability when applying reactive phosphate rock (RPR) in combination with lime and chicken manure on Indonesian acidic upland soils. Maize plants were grown on unamended soil and soils treated with several combinations of 2 tons dolomite ha^–1, 2 tons of chicken manure ha^–1, 1 ton ha^–1 of RPRL (reactive phosphate rock containing 4 mg Cd kg^–1 and 224 mg Zn kg^–1), and 1 ton ha^–1 of RPRH (RPR containing 69 mg Cd kg^–1 and 745 mg Zn kg^–1). In addition to its positive effect on plant yield, application of RPR in combination with chicken manure did not result in toxic Cd concentrations. Although liming is effective to reduce plant Cd concentrations, it results in more soil Cd accumulation and more plant Zn deficiency. Cadmium and Zn concentrations in shoots and grains can be predicted well from amounts extracted from the soil by 0.5 M ammonium (NH₄) acetate + 0.02 M ethylenediaminetetraacetic acid (EDTA) at pH 4.65.     

Affinity constants and behavior of Cd sorption in some acid soils

Cadmium sorption was studied in several acidic soils in a pH range from 4.5 to 6.5. The soils had two classes of surfaces with acidity constants (pKa₁ = 4.09 and pKa₂ = 6.39) similar to those for weakly and very weakly cidic carboxyls, and N-containing groups in fulvic acid. Titratable H and acidity constants were used to estimate the number of exchange sites at each pH level. Sorption of Cd was closely related to Cd concentration, pH, and soil type. Although the inclusion of pH and organic C contents in a regression accounted for some variations in the Cd distribution coefficient defined as the ratio of the quantity of Cd sorbed to the solution Cd concentration, the number of sorption sites was a more appropriate factor to explain the variability. Because of a negligible contribution to the number of exchange sites from Fe oxides, the sorption of Cd at pH = 4.5 was considered to be of a one-surface Langmuir type. A two-surface Langmuir equation was considered to model sorption at higher pH values. The average affinity constants (log K) were 3.61 and 4.89 for Cd sorption by the two classes of surfaces.     

The relative affinities of Cd,Ni and Zn for different soil clay fractions and goethite

Cadmium, Ni and Zn ions in aqueous solution were allowed to react with clay fractions (< 2 μm) separated from soils with a wide range of mineralogical composition and properties. Sorbed metals were separated into two components, termed specifically and non-specifically bound, by a controlled washing procedure using 10^?2M Ca(NO₃)₂.Sorption reactions were characterized by Δ pH₅₀ values, by shapes of adsorption curves, and by measuring separation factors and distribution coefficients under prescribed conditions. Three reaction types were identified, viz., (i) those associated with soil adsorbing surfaces dominated by iron oxides; these appear to be controlled by mechanisms which involve metal-ion hydrolysis and result accordingly in relative sorption affinities of Zn > Ni > Cd; (ii) those associated with organic surfaces for which metal-ion hydrolysis was of little significance and little difference in metal-ion affinity was evident; at lower pH-values, Cd and Ni were somewhat preferred over Zn, with the converse at higher pH-values; (iii) those associated with 2:1 layer lattice silicates which exhibit greater preference for Zn, i.e., Zn >> Ni, Cd and higher affinities for each metal at lower pH-values (< 5) than is shown by clays dominated by iron oxides. There was also evidence of greater relative affinity for Ni shown by clay fractions dominated by fine kaolinites when compared with other clays.This investigation has shown that a range of sorption processes are involved in reactions of heavy metals with soils. We caution against undue emphasis on any particular sorption process in developing theoretical sorption models as a basis of understanding and solving problems connected with pollution and plant nutrition; we also stress the need for studies with colloids separated from soils in conjunction with those using synthetic adsorbents as models for soil constituents.     

Availability and speciation of cadmium added to a calcareous soil under various managements

Potential risks for human health and adverse effects on soil quality caused by accumulation of cadmium (Cd) in soil at concentrations around or exceeding current European Union (EU) permitted limits have long been recognized. We have assessed availability and partitioning of Cd in a Mediterranean calcareous soil under four management regimes. Cadmium was added as a single pulse of CdSO₄ at the maximum Cd concentration established by the EU for sludge‐amended agricultural soils and concentrations exceeding the mandatory limits. Soils were treated with 0, 3, 10 and 50 mg Cd kg^?1 soil, incubated moist and analysed at selected times up to 600 days. Cadmium availability and distribution in soil were studied by neutral electrolyte and sequential extractions. During the incubation, the availability of Cd was not strictly dependent on the amount of metal added as the exchangeable fractions were similar shortly after the additions of Cd regardless of its initial concentration. Sequential extractions showed that for concentrations of 3 and 10 mg Cd kg^?1 soil Cd was evenly distributed among the soil phases, and its mobility was reduced mainly by adsorption on carbonates. At Cd concentrations exceeding 10 mg Cd kg^?1 soil a residual fraction appeared, perhaps from precipitation of Cd. Most of the Cd was associated with carbonates; land management and organic matter content had no major effects on the Cd distribution among different soil phases. The extraction protocols were effective for studying the fate of Cd in this calcareous soil as almost all of the Cd added was recovered. However, the introduction of a preliminary step with buffered NH₄NO₃ improved the determination of the most labile pools. Availability of Cd in calcareous soils estimated with reference methods appeared to be very small even when its total concentration far exceeded the current EU limits.     

Spatial distribution of soil heavy metal concentrations as indicator of pollution sources at Mount Križna (Great Fatra,central Slovakia)

The objective of this study was to test the suitability of a simple approach to identify the direction from where airborne heavy metals reach the study area as indication of their sources. We examined the distribution of heavy metals in soil profiles and along differently exposed transects. Samples were taken from 10 soils derived from the same parent material along N-, S-, and SE-exposed transects at 0—10, 10—20, and 20—40 cm depth and analyzed for total Al, Cd, Cr, Cu, Fe, Mn, Ni, Pb, and Zn concentrations. The heavy metal concentrations at 0—10 cm were larger than background concentrations in German arable soils except for Cr (Cd: 0.6—1.8 mg kg^—1; Cr: 39—67; Cu: 40—77; Ni: 87—156; Pb: 48—94; Zn: 71—129; Fe: 26—34 g kg^—1; Mn: 1.1—2.4). Decreasing Cd, Cu, Mn, and Pb concentrations with increasing soil depth pointed at atmospheric inputs. Aluminum and Ni concentrations increased with soil depth. Those of Fe, Cr, and Zn did not change with depth indicating that inputs at most equalled leaching losses. The Pb accumulation in the surface layer (i.e. the ratio between the Pb concentrations at 0—10 to those at 20—40 cm depth) was most pronounced at N-exposed sites; Pb obviously reached Mount Križna mainly by long-range transport from N where several industrial agglomerations are located. Substantial Cd, Cu, and Mn accumulations at the S- and SE-exposed sites indicated local sources such as mining near to the study area which probably are also the reason for slight Cr and Zn accumulations in the SE-exposed soils. Based on a principal component analysis of the total concentrations in the topsoils four metal groups may be distinguished: 1. Cr, Ni, Zn; 2. Mn, Cd; 3. Pb (positive loading), Cu (negative loading); 4. Al, Fe, indicating common sources and distribution patterns. The results demonstrate that the spatial distribution of soil heavy metal concentrations can be used as indication of the location of pollution sources.