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.     

Sorption and desorption of cobalt by soils and soil components

The sorption of Co by individual soil components was studied at solution Co concentrations that were within the range found in natural soil solutions. Soil-derived oxide materials sorbed by far the greatest amounts of Co although substantial amounts were also sorbed by organic materials (humic and fulvic acids). Clay minerals and non-pedogenic iron and manganese oxides sorbed relatively little Co. It is considered that clay minerals are unlikely to have a significant influence on the sorption of Co by whole soils. Cobalt sorbed by soil oxide material was not readily desorbed back into solution and, in addition, rapidly became non-isotopically exchangeable with solution Co. In contrast, Co was relatively easily desorbed from humic acid and a large proportion of the Co sorbed by humic acid remained isotopically exchangeable. Cobalt sorbed by montmorillonite was more easily desorbed than that sorbed by soil oxide but less easily than that sorbed by humic acid. Cobalt sorption isotherms for whole soils at low site coverage were essentially linear and the gradients of isotherms increased with pH. A comparison of isotherm gradients for whole soils and individual soil components supported the suggestion that Co sorption in whole soils is largely controlled by soil oxide materials.     

THE CONTENTS AND SORPTION OF CADMIUM IN SOME AGRICULTURAL SOILS OF ENGLAND AND WALES

Cadmium sorption was measured in 10 agricultural soils with pH ranging from 4.5 to 7.9, and total Cd content from 0.27 to 1.04 μg g^?1 dry soil. With initial Cd concentrations of 0.5 to 100.0 μM, sorption from 0.002 M CaCl₂ was described by the Freundlich adsorption equation but the gradients of the isotherms increased when the initial concentrations were below 0.5 μm. This indicates that there are specific sites of differing sorption energy; differences between soils in the gradients of the isotherms at low initial concentration could largely be accounted for by their contents of ‘free’ Fe₂O₃. When initial concentrations were below 0.5 μm there was a linear relationship between the quantity of Cd sorbed and the final concentration in solution. This relationship held with all soils except that of lowest pH from which there was a net loss of Cd to the solutions. Desorption was measured from three soils with contrasting pH. With the soil of lowest pH, over 80 per cent of sorbed Cd was desorbed to 0.002 m CaCl₂ and up to 30 per cent to 100 or 500 μm solutions of heavy metal chlorides. In contrast, only very small proportions (<1.25 per cent) were desorbed from the other soils with pH 6.7 and 7.8. The results indicate that Cd is strongly sorbed by soils of pH of above 6.0 when added in amounts comparable to additions in sewage sludges or phosphatic fertilizers, and illustrate the importance of liming as a means of reducing the mobility of this metal in soils.     

Competitive sorption of cadmium and lead in acid soils of Central Spain

The bioavailability and ultimate fate of heavy metals in the environment are controlled by chemical sorption. To assess competitive sorption of Pb and Cd, batch equilibrium experiments (generating sorption isotherms) and kinetics sorption studies were performed using single and binary metal solutions in surface samples of four soils from central Spain. For comparisons between soils, as well as, single and binary metal solutions, soil chemical processes were characterized using the Langmuir equation, ionic strength, and an empirical power function for kinetic sorption. In addition, soil pH and clay mineralogy were used to explain observed sorption processes. Sorption isotherms were well described by the Langmuir equation and the sorption kinetics were well described by an empirical power function within the reaction times in this study. Soils with higher pH and clay content (characterized by having smectite) had the greatest sorption capacity as estimated by the maximum sorption parameter (Q) of the Langmuir equation. All soils exhibited greater sorption capacity for Pb than Cd and the presence of both metals reduced the tendency for either to be sorbed although Cd sorption was affected to a greater extent than that of Pb. The Langmuir binding strength parameter (k) was always greater for Pb than for Cd. However, these k values tended to increase as a result of the simultaneous presence of both metals that may indicate competition for sorption sites promoting the retention of both metals on more specific sorption sites. The kinetic experiments showed that Pb sorption is initially faster than Cd sorption from both single and binary solutions although the simultaneous presence of both metals affected the sorption of Cd at short times while only a minor effect was observed on Pb. The estimated exponents of the kinetic function were in all cases smaller for Pb than for Cd, likely due to diffusion processes into micropores or interlayer space of the clay minerals which occurs more readily for Cd than Pb. Finally, the overall sorption processes of Pb and Cd in the smectitic soil with the highest sorption capacity of the studied soils are slower than in the rest of the soils with a clay mineralogy dominated by kaolinite and illite, exhibiting these soils similar sorption rates. These results demonstrate a significant interaction between Pb and Cd sorption when both metals are present that depends on important soil properties such as the clay mineralogy.     

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.     

Sorption of trace cadmium on clay minerals and river sediments: effects of pH and Cd(II) concentrations in a synthetic river water medium

The sorption of Cd(II) on illite was studied at initial Cd concentrations from 1 to 1000 μg 1^?1, with a constant solid phase concentration of 0.5 g 1^?1. Percentage sorbed at equilibrium increased sharply from pH 6.5 to 9.0, with a shift toward increased adsorption at lower initial concentrations, indicating specific, non-equivalent sites. Freundlich log-log plots were linear with a slope of 0.83. Susquehanna River sediments (silt/clay fraction) showed similar behavior, sorbing Cd somewhat more strongly than illite, as did mont-morillonite, while kaolinite sorbed Cd less strongly. Sorption on illite was not altered appreciably by removing the Fe- or Mn-oxide coating with dithionite, by removing organic matter with H₂O₂, or by using a carbonate-free medium. Equilibration time, desorption at lower pH's, and the effect of citrate in shifting the sorption to higher pH's were also studied. The data are discussed in terms of Cd speciation equilibria and possible sorption mechanisms.     

Sorption and desorption of selenium in different soils of the mediterranean area

Abstract

The adsorption of selenium (Se) in the selenate form and its desorption by phosphate in four soils with different physiochemical properties were studied in the laboratory. To determine adsorption isotherms for selenate 25 mL of solutions containing 1 to 100 ppm of Se were added to 2.5 g of soil. Desorption isotherms were determined by resuspending the samples in phosphate solution. The selenate sorption process was adequately described by the Freundlich equation. In pine forest and woodland soils, characterized by the highest organic matter content and cation exchange capacity (CEC) values, the isotherms were classified as L type, since the amount of Se sorbed appeared to move towards saturation. The organic matter content played the most important part in the adsorption of Se, while pH appeared to have a small effect on the ability of the soil to adsorb Se. The high CaCO₃ content of the pine forest soil may have contributed in increasing the Se adsorption notwithstanding the high pH value. The cultivated and arable soils showed a reduced sorption capacity. The sorption could be described by an S type curve. At low concentrations of Se the affinity of the solid phase was less than that of the liquid phase. By increasing the concentration of Se in solution, the affinity of the solid phase increased and the sorption was favored. Selenate desorption by water was negligible, whereas the amount of Se desorbed by phosphate varied among the different soils. The desorption experiments indicated that a significant portion of the sorbed Se was irreversibly retained. This suggests the existence of linkages which allow the release of Se in the soil solution only after physico‐chemical variation such as exchange with phosphate ions.     

The sorption of Cd,Zn and Ni by soil clay fractions: Procedures for partition of bound forms and their interpretation

This work is the first of several projects concerned with the study of higher-affinity reactions of Cd, Zn and Ni ions with soil clay fractions. Procedures for the separation of sorbed metals into fractions of lower and higher affinity for soil surfaces are described and evaluated.Various concentrations of Cd, Zn and Ni were allowed to react in the presence of 0.01 M Ca(NO₃)₂ with soil clays for 1 week after stabilization of suspension pH. The adsorbed metals were partitioned by a brief extraction with 0.01 M Ca(NO₃)₂ and the resultant fractions, called specifically and non-specifically sorbed metals, were measured by radioisotopic procedures.Measured separation factors showed that the fraction of sorbed metals that was desorbed by a rapid Ca(NO₃)₂ extraction still had a preference, sometimes marked, over Ca on the soil clay fraction. Separation of fractions of sorbed metals on the basis of affinity was reproducible, but the boundary conditions defined by separation factors vary appreciably between adsorbents, with values in the range 3–20 for amounts sorbed equivalent to ≦ 0.05% of cation exchange capacity and for pH values < 7.The proportions of Cd, Zn and Ni bound at high-affinity sites were strongly dependent on experimental conditions of pH, equilibrium time and surface saturation in relation to each soil clay. Hence, comparisons of affinities of trace metals for soils by reliance on measures of total sorption only, without assessing the contribution of lower-affinity forms, may prejudice conclusions and predictions arising from studies of the possible retention of metal pollutants in soils and fixation of micronutrients from fertilizers.     

Effects of Municipal Sewage Sludge Application on Soil and Purple Moor-grass (Molinia caerulea) Contamination by Metals in a Maritime Pine Forest

Granular bentonite has been assessed regarding its capacity to remove Hg(II), Cd(II) and Pb(II) from aqueous solutions. Sorption capacities, kinetics and the dependence of the sorption process on pH were determined. Fractional power, pseudo-first-order, pseudo-second-order and intra-particle diffusion equations were used to model the kinetics of metal adsorption. The pseudo-second-order model showed the best fit to experimental data. Different two-parameter sorption isotherm models (Langmuir, Freundlich, Temkin and Dubinin?CRadushkevich) were used to fit the equilibrium data. Freundlich's isotherm model gave the best fit to experimental data. The selectivity of granular bentonite towards these metals is Pb(II)?>?Cd(II)?>?Hg(II). The adsorption capacities of granular bentonite towards the metals expressed in milligramme metal per gramme granular bentonite are 19.45, 13.05 and 1.7 for Pb(II), Cd(II) and Hg(II), respectively (for an initial concentration of 100 mg metal/L).     

Tree Response to Experimental Watershed Acidification

In this study, lead (Pb) and antimony (Sb) sorption experiments were conducted to elucidate the mechanisms of Pb and Sb sorption by combined applications using single or combined applications of hydroxyapatite (HAP) and ferrihydrite (FH), to evaluate the contribution of each material in Pb and Sb sorption, and to assess the chemical stability of the sorbed Pb and Sb. In the combined application, isotherms of Pb sorption and Sb sorption were well fitted to Langmuir and Freundlich isotherm models, respectively. The Pb and Sb amounts sorbed in the combined application were the same levels as the summed totals of those sorbed in the single applications, indicating that in the combined application, Pb sorption and Sb sorption were not suppressed. Pb was mainly sorbed on HAP in the combined application, at a 90 % level of the total adsorbed Pb. The HAP and FH contributions to Sb sorption were 32 and 68 % of the total adsorbed Sb, respectively, and Sb was sorbed on each material independently even in the combined application. The percentages of both Pb and Sb dissolved from the sorbed materials in the combined applications at pH 4 and 6 were the same levels as those in the single applications. However, the percentages of Sb dissolved in both combined and single applications were high at an alkaline pH. These results suggest that HAP and FH in a combined application would be useful for simultaneous Pb and Sb immobilization in soil with acidic to neutral pH, but not in soil with an alkaline pH.     

Sorption of isotopically exchangeable and non-exchangeable phosphate by some soils of Colombia and Brazil, and comparisons with soils of southern Nigeria

Fourteen soils from Colombia and Brazil provided a wide range of sorption characteristics. Curves of sorbed phosphate that was exchangeable to ³²P were described by Freundlich's equation, and of non-exchangeable phosphate by Temkin's equation. Exchangeable phosphate was associated with aluminium in poorly-crystalline oxides and in organic complexes. Non-exchangeable phosphate was related to aluminium in organic complexes, and especially to the ratio of AI/C in them. In Nigerian soils similar mechanisms controlled sorption of phosphate but oxides and organic complexes of iron were important. The concentration of phosphate in solution when affinities of soil for exchangeable and non-exchangeable phosphate are equal, and the importance of organic matter, are discussed in relation to soil management and to responses of crops to fertilizer phosphate. The results indicate that sorption curves should not be split into sections.     

RATIONALIZATION OF IONIC STRENGTH AND CATION EFFECTS ON PHOSPHATE SORPTION BY SOILS

The amounts of inorganic phosphate (P) sorbed by four contrasting unfertilized soils during 40 h were influenced by the ionic strength and cation species of the contacting solution (support medium) used, as indicated by isotherms over the final P concentration range of 0 to 1 μg P/ml and 0 to 10 μg P/ml. An increase in ionic strength enhanced P sorption during 40 h but the species of cation also influenced the amount of P sorbed, as shown by the isotherms obtained in 10^?2M Ca and 3 × 10^?2M Na systems. Although pH affected the amounts of P sorbed, pH effects alone could not adequately explain the differences in P sorption. Kinetic studies indicated that within the range of P addition used for each soil, the equilibrium P concentration, at infinite time, was independent of ionic strength and cation species. Consequently, the composition of the solution affected only the rate at which equilibrium was attained. The results are attributed to the effects of ionic strength on the surface charge of retaining components and the thickness of the diffuse double layer, and the effects of specilic sorption of a divalent cation on surface charge, as they relate to the rate of P sorption.     

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.     

Cadmium Sorption and Desorption Characteristics of Tropical Alfisols from Different Land Uses

Cadmium (Cd) sorption and desorption characteristics by Alfisols from different land uses were examined, and the relationships between soil and sorption/desorption characteristics were investigated. Adsorption studies were done using Cd concentrations (0–100 mg Cd kg^?1) in 0.01 M CaCl₂. The Cd sorbed by the soils was then subjected to two desorption runs. The soils' adsorption conformed to Freundlich and Langmuir equations. The amount of Cd sorbed by the soils varied. Two desorption runs detached more than 95% of sorbed Cd, but the first accounted for more than 80% of the total. Desorption of Cd in degraded soils was more than in soils from other land uses. The amount of Cd desorbed correlated with amount applied (r = 0.90??), solution concentration (r = 0.83??), and amount sorbed (r = 0.70??). A positive relationship exists between the adsorption maxima of the soils and soil organic matter (r = 0.13, p = 0.87). The relationship between amount of Cd desorbed and sorbed is quadratic for all the soil.     

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.     

DESORPTION AND ISOTOPIC EXCHANGE RELATIONSHIPS OF PHOSPHATE SORBED BY SOILS AND HYDROUS FERRIC OXIDE GEL

Sorption of added inorganic phosphate (P) was irreversible in four contrasting soils and hydrous ferric oxide gel during 16 h desorption after 40 h sorption at the same (iso)pH. Irreversibility increased with increasing time of desorption above 30 h. When the amount of P which was chemisorbed during the sorption step was subtracted from the amount desorbed, the latter fell on the isotherm describing the more-physical, potential-determining sorption. No pH change occurred during desorption and net negative charge decreased by 1 equivalent per mole P desorbed. These results suggested that only more-physically sorbed P was desorbed at the iso-pH. The more-physically sorbed P was also reversible with respect to changes in the ionic strength and cation species of the desorbing solution. The isotopic exchangeability of the more-physically sorbed P was at least ten times greater than that of chemisorbed P. With increasing sorption time, both the ease of desorption and exchangeability of sorbed P decreased. Subsequent to desorption, the exchangeability of the remaining sorbed P also decreased. These observations are interpreted in terms of the concurrent changes in the amounts of chemisorbed and more-physically sorbed P.     

Zinc sorption–desorption by two Andepts: effect of pH and support medium

Laboratory experiments were carried out to evaluate the effect of pH, ionic strength and electrolyte composition on zinc sorption–desorption by two Andepts from the Canary Islands (Spain). At the natural soil pH, the soils exhibited little net negative surface charge and small Zn sorption capacities. More than 75% of the sorbed Zn was apparently strongly bonded. The pH greatly influenced the sorption–desorption reactions. Sorption increased with increasing pH, and retention increased abruptly at pH > 6.0. Sorption also occurred at pH values below the point of zero charge (PZC) of the soils, when most of the surface sites are positively charged. Desorption decreased continuously with rising pH and became a trace at pH > 6.0. An increase in the ionic strength of the background electrolyte decreased Zn sorption and enhanced the amount of sorbed metal that could be subsequently released. In the two soils, Zn sorption diminished somewhat in the K and Ca electrolytes as compared with the Na electrolyte. However, this did not happen at small Zn loadings. Desorption was not affected by the type of electrolyte and cation used. The results are consistent with chemisorption being responsible for most of the sorption. The results also suggested a strong affinity sorption or even precipitation at high pHs.     

SORPTION OF INORGANIC PHOSPHATE BY IRON- AND ALUMINIUM- CONTAINING COMPONENTS

The amounts of inorganic P sorbed by a range of Fe- and Al- containing components varied appreciably and decreased in the order allophane > fresh Al gel > Fe gel pseudoboehmite > aged Al gel > dried Fe gel > Fe-coated kaolinite > haematite > goethite > akaganeite > gibbsite = ground kaolinite > dispersed kaolinite. Al gel sorbed 30 to 70 times more P than gibbsite, and Fe gel sorbed approximately 10 times more P than its crystalline analogues (haematite, goethite. and akaganeite). Despite large differences in the extent of P sorption, the form of the isotherm was essentially the same for each sorbent. The ability of freshly-prepared Al gel suspensions to sorb P decreased with ageing, a property not shown by Fe gel. Drying of Fe gel at 80°C, however, caused an approximately 4-fold decrease in P sorption. Precipitation of Fe gel (2% Fe) on the surface of kaolinite increased P sorption by a factor of 10. The occurrence of Fe gel as a coating apparently presents more sorption sites to solution per unit weight of Fe gel than Fe gel alone. A linear relationship (r= 0.98) was obtained between the amount OH^? sorbed per unit increase in pH value (‘hydroxyl buffering’) and the overall P sorption maximum for each sorbent. Hydroxyl buffering provided a better index of P sorption potential than specific surface area. Except for the crystalline Fe sorbents, isotherms obtained by plotting fractional sorption saturation against final solution P concentration for the sorbents were essentially coincident with those for several contrasting soils. For crystalline Fe components a lower relative amount of weaker sorption, as opposed to chemisorption, of the overall sorption maximum was obtained. Differences in the extent of P sorption. however, appear to be primarily related to the number of functional M-OH groups presented at the solid-solution interface.     

EFFECTS OF IONIC STRENGTH ON CHEMISORPTION AND POTENTIAL-DETERMINING SORPTION OF PHOSPHATE BY SOILS

Amounts of inorganic phosphate (P) sorbed by two unfertilized soils, during times less than required to reach equilibrium, were affected by the ionic strength and cation species of the matrix solution. For non-equilibrium conditions the amounts of P sorbed increased with increasing ionic strength and were greater with Ca²⁺ than Na⁺. For higher P additions, resulting in equilibrium solution P concentrations greater than 30 to 40μrnole 1^?1, the effects of the matrix solution on P sorption were maintained at equilibrium, whereas at lower P additions the dependence of sorption on matrix solution composition was eliminated at equilibrium. Equilibrium sorption isotherms for each soil and matrix solution were described by three Langmuir equations, which corresponded to distinct concentration ranges or regions (I, II, and III) on the overall isotherm. The free energies of sorption (ΔG) for each region, were essentially independent of the soil matrix solution. The sorption maxima for regions I and II of the isotherm for a particular soil were also virtually independent of the matrix solution used. The sorption maximum for region III, however, was markedly dependent on the matrix solution, implying a potential-determining (p.d.) sorption mechanism.     

Metabolism of glucose,fructose, and sucrose in tobacco leaves during maturity

Phosphorus sorption and desorption processes in selected soils were investigated to evaluate the usefulness of phosphorus sorption isotherms in the estimation of the phosphorus supplying capacity of soils. There was a distinct hysteresis in the phosphorus sorption and desorption isotherms, resulting in an overestimation of the replenishing ability of soils to supply phosphorus to the soil solution, when phosphorus sorption isotherms were used for the estimations.

To attain a value of 0.2 ppm P in the soil solution, 115 µmol P/g soil are required in the Kuromatsunai Ando soil (Ochric Andosols) based on the estimation by the P desorption isotherms; this value is 29% higher than that indicated by the P sorption isotherm. Also 42 µmol P/g soil are required in the Mikatagahara Yellow soil (Helvic Acrisols)—which corresponds to a value 23% higher than that indicated by the P sorption isotherm.

Two types of hysteresis subloops were observed: A reversible type and an irreversible type. The former was found typically in the highly weathered Mikatahagara Yellow soil while the latter was observed in the Kuromatsunai Ando soil.