Cadmium soil sorption at low concentrations. VII: Effect of stable solid waste leachate complexes

Soil sorption of Cd in solid waste leachates of landfill, sewage sludge, and incinerator residue was studied in the laboratory with emphasis on the behavior of Cd present as stable complexes. A previously developed speciation method was employed to determine free divalent Cd and complexed Cd of various stability. The experiments involved 13 soils covering a wide range of clay contents. Speciation of Cd present in solution after exposure to increasing amounts of soil showed that stable Cd complexes did not sorb onto the soil. This was supported by equilibrium isotherms exhibiting similar solute concentration intercepts and by a leaching study of soil columns which resulted in the same concentration of stable Cd complexes. The stable complexes were of the order of 1 to 10 μg Cd L^?1, the higher values found in landfill and sewage sludge leachate. Very little Cd present in the leachates was free divalent Cd (a few percent), which may explain the low Cd distribution coefficients (3 to 70 L kg^?1).     

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.     

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.     

A model for sorption,flux and plant uptake of cadmium in a soil profile: Model structure and sensitivity analysis

Fluxes of cadmium in a soil profile are simulated by coupling a model for linear and nonlinear equilibrium sorption to an existing hydrological model. The aim is to develop a model for Cd transport in soil systems. A separate flow model is used to calculate the water fluxes, which are then used in an equilibrium sorption model, allowing different Freundlich isotherms to be chosen. The model is tested and a sensitivity analysis is made. The variation of soil compartment sizes gave small changes in the results, which is interpreted as a measure of the solution stability. The factor influencing Cd transport most, according to these simulations, is the sorption isotherm. The degree to which Cd sorbs to soil decides how much will be available in the soil water for plant uptake or transport through the soil to the ground water. Other studied factors such as root distribution and hydrological properties influence the result only to a limited degree. With an application of 10 mg Cd/m² in the given range of Freundlich isotherms, the simulations gave a plant uptake of between 0 and 30% of the applied Cd in two years. At the concentration mainly used in this study (with 10 mg Cd/m² applied), the nonlinear isotherms found in the literature gave Cd lower mobility than the linear isotherms used for comparison. For high Cd concentrations the situation would be the reverse.     

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.     

Solubility,sorption and desorption of native and added cadmium in relation to properties of soils in New Zealand

Solution cadmium (Cd) concentrations and sorption and desorption of native and added Cd were studied in a range of New Zealand soils. The concentration of Cd in solution and the concentrations and patterns of native soil Cd desorbed and added Cd sorbed and desorbed varied greatly between the 29 soils studied. Correlation analysis revealed that pH was the most dominant soil variable affecting solution Cd concentration and sorption and desorption of native and added Cd in these soils. However, organic matter, cation exchange capacity (CEC) and total soil Cd were also found to be important. Multiple regression analysis showed that the log concentration of Cd in solution was strongly related to soil pH, organic matter and total Cd, which in combination explained 76% of the variation between soils. When data from the present study were combined into a single multiple regression with soil data from a previously published study, the equation generated could explain 81% of the variation in log Cd solution concentration. This reinforces the importance of pH, organic matter and total Cd in controlling solution Cd concentrations. Simple linear regression analysis could at best explain 53% of the total variation in Cd sorption or desorption for the soils studied. Multiple regression analysis showed that native Cd desorption was related to pH, organic matter and total Cd, which in combination explained 85% of the variation between soils. For sorption of Cd (from 2 μg Cd g^–1 soil added), pH and organic matter in combination explained 75% of the variation between soils. However, for added Cd desorption (%), pH and CEC explained 77%. It is clear that the combined effects of a range of soil properties control the concentration of Cd in solution, and of sorption and desorption of Cd in soils. The fraction of potentially desorbable added Cd in soils could also be predicted from a soil’s K_d value. This could have value for assessing both the mobility of Cd in soil and its likely availability to plants.     

几种有机酸对可变电荷和恒电荷土壤吸附镉的影响

The objectives of this study were to illustrate the reaction processes, to identify and quantify the precipitates formed, and to estimate the porosity losses in order to eliminate drawbacks during remediating monochlorobenzene （MCB） and trichloroethylene （TCE）-contaminated aquifers using the ORC-GAC-Fe^0-CaCO3 system. The system consisted of four columns （112 cm long and 10 cm in diameter） with oxygen-releasing compound （ORC）, granular activated carbon （GAC）, zero-valent iron （Fe^0）, and calcite used sequentially as the reactive media. The concentrations of MCB in the GAC column effluent and TCE in the Fe^0 column effluent were below the detection limit. However, the concentrations of MCB and TCE in the final calcite column exceeded the maximum contaminant level （MCL） under the Safe Drinking Water Act of the US Environmental Protection Agency （US EPA） that protects human health and environment. These results suggested that partitioning of MCB and TCE into the gas phase could occur, and also that transportation of volatile organic pollutants in the gas phase was important. Three main precipitates formed in the ORC-GAC-Fe^0-CaCO3 system： CaCO3 in the ORC column along with Fe（OH）2 and FeCO3 in the Fe^0 column. The total porosity losses caused by mineral precipitation corresponded to about 0.24% porosity in the ORC column, and 1% in the Fe^0 column. The most important cause of porosity losses was anaerobic corrosion of iron. The porosity losses caused by gas because of the production and entrapment of oxygen in the ORC column and hydrogen in the Fe^0 column should not be ignored. Volatilization, precipitation and porosity losses were considered to be the main drawbacks of the ORC-GAC-Fe^0-CaCO3 system in remediating the MCB and TCE-contaminated aquifers. Thus, measurements such as using a suitable oxygen-releasing compound, weakening the increase in pH using a buffer material such as soil, stimulating biodegradation rates and minimizing the plugging caused by the relatively high dissolved oxygen levels should be taken to eliminate the drawbacks and to improve the efficiency of the ORC-GAC-Fe^0-CaCO3 system.     

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.     

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.     

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).     

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.     

Soil Organic Matter Impacts upon Fluxes of Cadmium in Soils Measured using Diffusive Gradients in Thin Films

Abstract

Classical analytical methods limit understanding of the dynamics of geochemical processes in soils. The technique of diffusive gradients in thin films (DGT) allows the quantification of the mobilization fluxes of traces metals in soils and more specifically the metal supply from the soil's solid phase. Diffusive gradients in thin films, measuring fluxes from soil solids to solutions, were reported in three different cadmium (Cd)–contaminated soils with different levels of soil organic matter (SOM). The soil solution concentration ratio between the labile Cd, determined using differential pulse anodic stripping voltammetry, and the total Cd obtained by inductively coupled plasma–atomic emission spectrometry was compared. The data suggest that SOM affected the complexation of Cd in the soil solution, and the values obtained by DGT also demonstrated that the sorption of the Cd to the solid phase was also affected. The fluxes of Cd into the DGT were decreased when organic matter was added to the soils but were also decreased when SOM was reduced using hydrogen peroxide (H₂O₂).     

Immobilization of heavy metals in soils amended by nanoparticulate zeolitic tuff: Sorption‐desorption of cadmium

Immobilization of Cd in contaminated soil is a technique to improve soil quality. Zeolites are potentially useful additives to bind heavy metals. This study examines the influence of decreasing the grain size of raw zeolitic tuff to the nano‐range on Cd sorption‐desorption isotherms in a sandy soil. The aim was to evaluate the feasibility of using nanoparticulate zeolitic tuff as a sequestering agent for Cd in soil. Sorption and desorption of Cd on zeolitic nanotuff was investigated in batch experiments. The sandy soil was amended with zeolitic nanotuff, synthetic Al oxide nanoparticles, or raw zeolitic tuff. After a 48 h sorption step, three desorption steps were induced using the sequential dilution method. The measured sorption‐desorption data were adequately described by the Freundlich equation. A nonlinear two‐stage one‐rate model matched well with measured Cd sorption‐desorption isotherms of zeolitic nanotuff, raw zeolitic tuff, Al oxide nanoparticle, and control soil. The batch experiments demonstrated the strong influence of pH on Cd sorption. Zeta‐potential measurements of zeolitic nanotuff indicated that electrostatic interaction was important for sorption. Soil amended with zeolitic nanotuff showed the lowest hysteresis index based on the differences obtained from sorption‐desorption isotherms regarding the amount of Cd sorbed. The index decreased with increasing metal concentration. For soil amended with nanoparticulate zeolitic tuff, the estimated Freundlich coefficient was 4 orders of magnitude higher than in the control soil and 2 orders of magnitude higher than the soil amended with raw zeolitic tuff. In addition, this sorbent decreased the amount of Cd released after three desorption steps by up to 12 and 7 times compared to the control soil and the soil amended with raw zeolitic tuff, respectively. The effect on Cd sorption of grinding the raw zeolitic tuff to the nanorange was considerably more pronounced than the effect of raw zeolitic tuff.     

Abiotic uptake of gases by organic soils

Methodological and experimental studies of the abiotic uptake of gaseous substances by organic soils were performed. The static adsorption method of closed vessels for assessing the interaction of gases with the solid and liquid soil phases and the dynamic method of determining the sorption isotherms of gases by soils were analyzed. The theoretical substantiation of the methods and their practical implementations on the basis of a PGA-7 portable gas analyzer (Russia) were considered. Good agreement between the equilibrium sorption isotherms of the gases and the Langmuir model was revealed; for the real ranges of natural gas concentrations, this model can be reduced to the linear Henry equation. The limit values of the gas sorption (Langmuir monolayer capacity) are typical for dry samples; they vary from 670–4000 g/m³ for methane and oxygen to 20 000–25 000 g/m³ for carbon dioxide. The linear distribution coefficients of gases between the solid and gas phases of organic soils (Henry constants) are 8–18 units for poorly sorbed gases (O₂, CH₄) and 40–60 units for CO₂. The kinetics of the chemicophysical uptake of gases by the soil studied is linear in character and obeys the relaxation kinetic model of the first order with the corresponding relaxation constants, which vary from 1 h ^?1 in wet samples to 10 h ^?1 in dry samples.     

Effect of pH on Zinc Sorption–Desorption by Soils

The objective of this study was to examine the effect of soil pH on zinc (Zn) sorption and desorption for four surface soils from the Canterbury Plains region of New Zealand. Zinc sorption by the soils, adjusted to different pH values, was measured from various initial solution Zn concentrations in the presence of 0.01 M calcium nitrate [Ca(NO₃)₂]. Zinc desorption isotherms were derived from the cumulative Zn desorbed (µg g^?1 soil) after each of 10 desorption periods by sequentially suspending the same soil samples in fresh Zn‐free 0.01 M Ca(NO₃)₂. Zinc sorption and desorption varied widely with soil pH. Desorption of both native and added Zn decreased continuously with rising pH and became very low at pH values greater than 6.5. The proportion of sorbed Zn that could be desorbed back into solution decreased substantially as pH increased to more than 5.5. However, there were differences between soils regarding the extent of the hysteresis effect.     

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.     

天然土壤中典型多溴联苯醚解吸过程的初步研究

选择5种有机质含量不同的天然土壤,采用批量实验方法考察典型多溴联苯醚8DE47的解吸行为,并尝试利用非线性Freundlich模型和线性模型模拟不同初试浓度条件下BDE47的土壤解吸过程。针对较为显著的器壁吸附影像,所有检测数据均进行器壁吸附定量修正。结果表明,BDE47土壤解吸过程总体分为初始的快解吸和后续的慢解吸两个阶段。在初始阶段,BDE47解吸过程表现为线性行为,但非线性特征随解吸时间延长呈现增强趋势。土壤有机质（用TOC表征）释放的溶解有机质是影响土壤中BDE47解吸行为差异的主要因素之一。     

七种钾释放动力学方程的比较和动力学参数的应用

Batch equilibrium experiments were conducted to investigate cadmium （Cd） sorption by two permanent-charge soils, a yellow-cinnamon soil and a yellow-brown soil, and two variable-charge soils, a red soil and a latosol, with addition of selected organic acids （acetate, tartrate, and citrate）. Results showed that with an increase in acetate concentrations from 0 to 3.0 mmol L^-1, Cd sorption percentage by the yellow-cinnamon soil, the yellow-brown soil, and the latosol decreased. The sorption percentage of Cd by the yellow-clnnamon soil and generally the yellow-brown soil （permanent-charge soils） decreased with an increase in tartrate concentration, but increased at low tartrate concentrations for the red soil and the latosol. Curves of percentage of Cd sorption for citrate were similar to those for tartrate. For the variable-charge soils with tartrate and citrate, there were obvious peaks in Cd sorption percentage. These peaks, where organic acids had maximum influence, changed with soil type, and were at a higher organic acid concentration for the variable-charge soils than for the permanent charge soils. Addition of cadmium after tartrate adsorption resulted in higher sorption increase for the varlable-charge soils than permanent-charge soils. When tartrate and Cd solution were added together, sorption of Cd decreased with tartrate concentration for the yellow-brown soil, but increased at low tartrate concentrations and then decreased with tartrate concentration for the red soil and the latosol.