Sorption of trace quantities of cadmium by soils with different chemical and mineralogical composition

Cadmium sorption experiments were performed using four soil separates of different chemical and mineralogical composition, adding Cd solutions with initial concentrations ranging from 15 to 150 μg l^?1. At the soils pHs, the sorption isotherms were a mixture of a constant partition isotherm with a high affinity one. Also, more than 90% of the initially added Cd was sorbed by all four soils. These results indicate a high affinity of these soils for trace amounts of Cd. The effect of pH was, in general, to decrease the amount of sorbed Cd as the pH decreased. The sorption isotherms were linear at all pH's. Also, the data fitted the Freundlich's sorption isotherm in all cases, but not Langmuir's. Freundlich's k values were found to be a good index of the relative Cd sorption affinities of the four soils at all the pH's used. It was found that the structural and chemical nature of the soils sorbent complex was a more important parameter than the CEC when studying the sorption of these trace amounts of Cd by soils.     

Retention of cobalt by an oxisol in relation to the content of iron and manganese oxides

Abstract

The study aims at determining the cobalt retention properties of various soil components. Therefore, cobalt (Co) sorptions and extractions were carried out using an Oxisol sample before (untreated) and after successive removal of organic matter and active manganese (Mn) oxides (H₂O₂‐treated) and iron (Fe) oxides (H₂O₂+CBD‐treated). A synthetic goethite was included for comparison. Sorption of the four sorbents was determined over a range of Co concentrations (initially 10^‐8 M to 10^‐4 M), pH values (3 to 8) and reaction times (2 hours to 504 hours). The Co species sorbed was Co(ll), since oxygen exclusion during sorption had no effect on the amount sorbed. The pH‐dependent sorption curve (sorption edge) was shifted to lower pH at decreasing initial Co concentration and increasing reaction time. The displacements, in particular of the sorption edges corresponding to the lowest initial Co concentrations, to successively higher pH following removal of Mn oxides, organic matter and Fe oxides could be attributed to sorption onto sites of decreasing Co affinity [Mn oxides (and organic matter) > Fe oxides > kaolinite]. Extractions of sorbed Co at pH 5.5–7.5 with 2 M HCI showed that the extractability decreased with increasing sorption time and decreasing initial Co concentration. The untreated and H₂O₂‐treated soil samples retained sorbed Co at least as firmly as the synthetic goethite, whereas the H₂O₂+CBD‐treated sample (kaolinite) was clearly less effective. The results emphasized the importance of the soil Mn and Fe oxides for Co retention in soils but also the necessity of taken interior sorption sites into consideration.     

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.     

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.     

印度Chattisgarh州两种新开发土和一种淋溶土中磷酸盐吸附-解析特征研究

Two Inceptisols and an Alfisol of the Indravati Catchment area in Chattisgarh, India, comprising several gradients in physical and chemical properties were studied to relate phosphate sorption and desorption to soil properties. From the P isotherm curve, the standard P requirement （SPR） of the soils was determined. Phosphate sorption data were also fitted both to the Langmuir and Freundlich Equations. The mean sorption maximum values for three different soil series were： Bastar 〉 Geedam 〉 Mosodi. The fraction of added phosphate sorbed for the 3 series followed this same trend as did SPR; the phosphate sorption maximum and the maximum phosphate buffering capacity, which were estimated by the Langmuir isotherm; and the Freundlich constant 1/n. However, phosphate desorption, as well as the maximum recovery percent did not follow this order. The phosphate affinity constant （K） was also different following the same progression for the 3 soil series as the Freundlich constant K＇, which measured sorption strength. Meanwhile, an inverse order existed for K and K＇ versus the percent desorbed relative to the sorbed as well as the maximum recovery percent. In addition, significant correlation coefficients among sorption parameters of P and soil factors were found.     

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.     

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.     

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.     

Effect of zeolite application and soil pH on cadmium sorption in soils

Abstract

In this study the influence of zeolite application and soil liming on cadmium (Cd) sorption by soils in Greece was investigated. The zeolite was natural and consisted mainly of clinoptilolite. The soil samples were strongly acid surface horizons of an Alfisol limed from a pH of 4.0 to 8.5, and a neutral Bt horizon. The result showed that liming and zeolite application substantially increased sorption of Cd in the soils. Cadmium sorption was described adequately by the Freundlich equation whereas the Langmuir model failed to describe Cd sorption in the soils. The Freundlich constant K increased in value by zeolite application as well as by soil liming. A strong relationship was observed between this parameter and soil pH. A high percentage of cadmium sorbed was released in the desorption procedure. The amount of Cd released was reduced by zeolite application as well as by soil liming. It is concluded that zeolite application as well as soil liming increased Cd sorption by the soils.     

Predicting phosphorus sorption isotherm parameters in soil using data of routine laboratory tests

Knowledge of phosphorus(P) sorption dynamics across different soil types could direct agronomic and environmental management of P. The objective of this study was to predict P isotherm parameters for a national soil population using data of routine laboratory tests. Langmuir and Freundlich sorption parameters were calculated from two different ranges(0–25 and 0–50 mg P L~(-1)) using an archive of representative agricultural soil types from Ireland.Multiple linear regression(MLR) identified labile forms of aluminium(Al) and iron(Fe), organic matter(OM), cation exchange capacity(CEC), and clay as significant drivers. Langmuir and Freundlich sorption capacities, Freundlich affinity constant, and Langmuir buffer capacity were predicted reliably, with R~2 of independent validation 0.9. Sorption isotherm parameters were predicted from P sorbed at a single concentration of 50 mg P L~(-1)(S_(50)). An MLR prediction of P sorption maximum in the 0–50 mg P L~(-1) range was achieved, to an accurate standard, using S_(50), OM, and Mehlich-3 Fe(R~2 of independent calibration and validation being 0.91 and 0.95, respectively). Using Giles' four shapes of isotherms(C, L, H, and S), L non-strict-and C-shaped isotherm curves accounted for 64% and 27% of the soils, respectively. Hierarchical clustering identified a separation of isotherm curves influenced by two ranges of Mehlich-3 Al. Soils with a low range of Mehlich-3 Al(2.5–698 mg kg~(-1)) had no incidence of rapid sorption(C shape). Single point indices, Al, or available soil data make the regression approach a feasible way of predicting Langmuir parameters that could be included with standard agronomic soil P testing.     

The specific sorption of trace amounts of Cu,Pb, and Cd by inorganic particulates

Thin film A.S.V. was used to study the specific sorption of Cd, Pb and Cu by hydrous oxides (Mn, Fe, and Al) or clay mineral suspensions from acetate buffer solutions containing 10 to 100 μg L^?1 of each metal ion. The amount sorbed varied with system pH (range 3 to 9), substrate crystal form, the ratio of adsorbent to absorbate present, and the metal ion involved. Uptake by hydrous Mn(IV) oxide was near total over the whole pH range. With other particulates the pH required for onset of sorption varied with solid phase composition, with uptake subsequently increasing steadily with increasing pH. In general, affinity and relative uptake values followed the sequences Pb > Cu > Cd and Mn(IV) oxides > Fe(III) oxides > A1(OH)₃ > clays > iron ores. The solid phases loaded with sorbed metal were equilibrated with a range of extractant solutions used in soil/sediment studies, and the results confirmed that chemi-sorption was the main retention process. Significant release was achieved using extractants that attacked the substrate or formed stable complexes with the metal ion.     

Retention of dissolved organic matter by illitic soils and clay fractions: Influence of mineral phase properties

The dependency of the retention of dissolved organic carbon (DOC) on mineral phase properties in soils remains uncertain especially at neutral pH. To specifically elucidate the role of mineral surfaces and pedogenic oxides for DOC retention at pH 7, we sorbed DOC to bulk soil (illitic surface soils of a toposequence) and corresponding clay fraction (< 2 μm) samples after the removal of organic matter and after removal of organic matter and pedogenic oxides. The DOC retention was related to the content of dithionite‐extractable iron, specific surface area (SSA, BET‐N₂ method) and cation exchange capacity (pH 7). The reversibility of DOC sorption was determined by a desorption experiment. All samples sorbed 20–40 % of the DOC added. The DOC sorption of the clay fractions explained the total sorption of the bulk soils. None of the mineral phase properties investigated was able to solely explain the DOC retention. A sorption of 9 to 24 μg DOC m^–2 indicated that DOC interacted only with a fraction of the mineral surface, since loadings above 500 μg m^–2 would be expected for a carbon monolayer. Under the experimental conditions used, the surface of the silicate clay minerals seemed to be more important for the DOC sorption than the surface of the iron oxides. The desorption experiment removed 11 to 31 % of the DOC sorbed. Most of the DOC was strongly sorbed.     

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.     

Phosphate sorption by red mediterranean soils from Greece

Abstract

In nineteen surface horizons of red Mediterranean soils from various locations of Greece, phosphorus (P) sorption experiments were conducted and the sorption characteristics were studied in relation to soil properties. Phosphate sorption data were fitted both to the Langmuir and Freundlich equations. From these equations, the following P sorption parameters were determined from the Freundlich equation, X = ACⁿ, the parameters A (the phosphate sorbed at C = 1 mg P/L), n (the P sorption intensity), the P sorption index (PS = X/log C) and maximum P sorption (Xmfr). From the Langmuir equation, C/X = 1/KXm + C/Xm, the parameters K (showing the bonding energy), maximum P sorption (Xmla), the quantity of P adsorbed at a standard concentration of 0.2 mg P/L (P0.2), and P maximum buffering capacity (PMBC). The Freundlich parameter A was strongly correlated to the clay and sesquioxides ("free”; iron and aluminum oxides and amorphous iron oxides) content. Seventy‐four percent of the variance of this parameter was explained by clay and “free”; iron (Fe) content. The Freundlich parameter n was significantly correlated with pH and amorphous iron oxides content, while 52% of its variance was explained by amorphous Fe and dithionite extrac‐table aluminum (Al). The P sorption maxima calculated from the Freundlich equation were in general lower than those calculated by the Langmuir equation. Both these parameters were strongly correlated with clay and more slightly with sesquioxides content. About 50% of their variance was explained by clay content of the soils. The P sorption index was strongly correlated with the clay content and less strongly with dithionite‐extractable Fe and Al. The P‐buffering capacity calculated from the data of Langmuir equation was also strongly correlated with these two parameters. In addition, clay content and dithionite‐extractable Fe and Al were well correlated to the amounts of P required to obtain an equilibrium concentration of 0.2 mg P/L while 61% of the variation of this parameter was explained by the clay and the dithionite‐extractable Fe content. From these findings, it seems that for the red Mediterranean soils from Greece, P sorption is affected by clay content and iron and aluminum oxide contents.     

Sorption of lead,copper, zinc,and cadmium by soils: effect of nitriloacetic acid on metal retention

Abstract

Laboratory experiments were carried out to evaluate lead (Pb), copper (Cu), zinc (Zn), and cadmium (Cd) sorption‐desorption by three soils of contrasting characteristics. Talamanca (silt loam, montmorillonite, Calcic Haploxeralfs), Mazowe (clay, kaolinite, Rhodic Kandiustalf), and Realejos (sandy silt loam, allophane, Typic Hapludands). A second objective was to study the effect of nitriloacetic acid (NTA) on the sorption process. The Talamanca soil, which had a native pH of 6.4 and presented the highest effective cation exchange capacity (ECEC), sorbed more of each of the metal tested than did the other two soils. When the other two soils were compared metal sorption was also related to pH and ECEC. The very low sorption capacity showed by Realejos may be attributed to the low net surface negative charge density of this soil, arising from its allophanic nature. A common feature of the three soils was the relative strong sorption of both Pb and Cu relative to Cd and Zn with Pb showing the highest sorption levels. The selectivity sequences of metals retention were Pb>Cu>Zn>Cd for Talamanca soil, Pb>Cu>Zn≈Cd for Mazowe, and Pb>Cu>Cd>Zn for Realejos. Metal desorption values were low. The order of metal desorption (Cd≈Zn>Cu>Pb) was the same for the three soils studied. Quantitative differences observed in the extractability of the sorbed metals between the soils (Realejos>Mazowe>Talamanca) indicated that soil properties which enhanced metal sorption contributed at the same time to slow down the backward reaction. The addition of NTA to the soil suspension significantly depressed metal sorption by the three soils investigated. Compared with the free ligand system Pb, Cu, Zn, and Cd sorption in the presence of NTA decreased roughly 50%.     

Adsorption and solubility of ten metals in soil samples of different composition

We conducted batch experiments for ten metals [Mg, Cr(III), Fe(III), Co, Ni, Cu, Zn, Sr, Cd, Pb] and four soil samples of different composition to determine the relation of the soluble fraction (’intensity’︁) to an adsorbed or precipitated metal pool (’quantity’︁) and, thus, to investigate the buffer function of soils. The soil samples were spiked with 6 to 12 exponentially increasing metal doses added as metal nitrates. The native metal pool involved in sorption processes was characterized by an extraction with 0.025 M (NH₄)₂EDTA (pH 4.6). The quantity-intensity (Q/I) relations of eight metals [except Cr(III) and Fe(III)] were governed by sorption and complexation processes and can be fitted by Freundlich isotherms. Q/I relations for Cr(III) and two soils indicate a sorption maximum, which can be approximated with the Langmuir isotherm. In a calcareous soil high Cr doses induced the precipitation of a Cr oxide. The solution concentrations of Fe are primarily a function of the pH-dependent solubility of ferrihydrite. For all metals pH was the predominant factor controlling the partitioning between the solid and the liquid phase. Drastic losses in the buffer function of soils primarily occurred in the slightly acidic range. Furthermore, adsorption was also metal specific. On the basis of median Freundlich K values, adsorption increased in the order [median K_F values and K_F range (mg kg^—1) in brackets]: Mg (2.9: 0.9—19) < Sr (4.7: 0.6—21) << Co (17.7: 1.1—143) < Zn (26.7: 1.8—301) = Ni (27.6: 2.4—120) < Cd (71: 2.5—405) << Cr(III) (329: 45—746) < Cu (352: 30—1200) < Pb (1730: 76—4110).     

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.     

Estimation of nitrate retention in a Ferralsol by a transient-flow method

Anion retention is important in highly weathered soils that contain large amounts of iron and aluminium oxides with surfaces of variable charge. Sorption mechanisms retard anionic solute transfer through these soils. We determined the retardation factor for nitrate in highly weathered Ferralsols from New Caledonia from dynamic experiments using a transient‐flow method, and we evaluated the effect of soil solution concentration and organic matter content. A simple method with sectionable tubes was used to determine the nitrate isotherm during non‐steady‐state water flow under unsaturated conditions. The topsoil retarded the movement of nitrate, and the sorption followed a linear isotherm. In subsoils, retardation factors were larger and increased from 1.15 to 2.05 at soil pH as the NO₃^–‐N concentration of the input solution decreased from 71.43 to 0.35 mm , indicative of a non‐linear isotherm. Positive surface charge sites were considered to be of two types: one with strong affinity for nitrate at small concentrations and one with weak affinity for adsorption of nitrate at larger concentrations. This type of isotherm with high‐ and low‐energy sites is similar to those found for oxyanions and heavy metals. The related anion exchange capacity was larger than that usually observed in soils of variable charge. Not all exchange sites were detected with our method, and some sites were obviously not available for nitrate retention.     

Sorption of dimethylselenide by soils

Air-dry and moist soils were shown to possess the capacity to sorb substantial amounts of (⁷⁵Se)dimethylselenide produced by the yeast Candida humicola in culture, or by soil supplied with (⁷⁵Se)selenite, depending largely upon the organic matter content and selenium concentration of the soils. The sorption capacities of individual soil constituents followed the order; organic matter > clay minerals > manganese oxides > iron oxides > acid-washed sand.A chemical fractionation procedure applied to soils fumigated with (⁷⁵Se)dimethylselenide revealed that the majority of the selenium sorbed was converted after 1 month to other forms, extractable mainly with strong acid solutions. Experiments with sterilized (autoclaved and γ-irradiated) soils indicated that soil microorganisms played little, if any, part in the sorption process.The work reported here indicates that soil is an important natural “sink” for atmospheric dimethylselenide.