Properties of sub soils in relation to various measures of surface area and water content

Neither the specific surface area values (from N₂ sorption) nor the ethylene glycol monoethyl ether (EGME) retention values of 21 soil samples from New Zealand and Fiji could all be accounted for by the sum of the contributions from their component minerals. Much EGME is probably retained by internal surfaces of inter layered and interstratified clay minerals. EGME retention correlated well with cation exchange capacity (CEC) and a number of measures of water content of these soils. The water contents of air-dried soils (measured as ‘moisture factors’ or the ratios of air-dry and oven-dry weights) showed almost as close a relationship to CEC as EGME retention for this set of 21 subsoils. Moisture factors and CEC were closely related, within groups defined by dominant clay mineralogies, for a much wider selection of 1318 New Zealand soil horizons with low carbon contents. The relationships between surface area and a number of other soil properties including dispersibility of soils were also examined.     

Comparison of various methods for the determination of specific surfaces of sub soils

Retention of ethylene glycol monoethylether (EGME) and ethylene glycol (EG), and sorption of nitrogen and water vapour, were studied on a wide range of soils from New Zealand and Fiji. EGME retention was mainly affected by the amount of EGME liquid present in the desiccator, the interaction with the desiccant (CaCl₂), the amount of residual water in the samples, and the time taken to establish end-points. The extent to which each of these factors influences the weight of EGME retained was different for each sample. Surface areas from nitrogen sorption (BET) were not related to those derived from EGME retention in the same way for all soils; EGME retentions did not vary systematically with clay mineralogy. A constant conversion factor cannot be used to convert retentions of polar liquids (EGME, water and EG) to specific surface values, and retention data by itself cannot be used to measure the absolute surface areas of soils.     

Specific surface area and surface charges of some argentinian soils

The specific surface areas of nine argentinian soils obtained by adsorption followed the order N₂ < ethylene glycol < H₂O, attributed to the presence of smectites (verified by XRD analysis) and some organic coating. The H₂O₂ treatment of these soils modified the former order of surface area determined by different absorbents. This order was modified because the mineral surface was evidenced and an increase of cation adsorption was produced by organic matter removal. This fact was supported by the decrease of PZC values of soils after H₂O₂ treatment. The specific surface area of initial soils obtained by water and ethylene glycol adsorptions showed a good correlation with carbon content and CEC of untreated soils and with the PZC of protonated soils.     

Influence of Increasing Soil Copper Concentration on the Susceptibility of Phosphomonoesterase and Urease to Heat Disturbance

The sorption of chromium (Cr) species to soil has become the focus of research as it dictates the bioavailability and also the magnitude of toxicity of Cr. The sorption of two environmentally important Cr species [Cr(III) and Cr(VI)] was examined using batch sorption, and the data were fitted to Langmuir and Freundlich adsorption isotherms. The effects of soil properties such as pH, CEC, organic matter (OM), clay, water-extractable SO₄ ^2– and PO₄ ^3–, surface charge, and different iron (Fe) fractions of 12 different Australian representative soils on the sorption, and mobility of Cr(III) and Cr(VI) were examined. The amount of sorption as shown by K _f was higher for Cr(III) than Cr(VI) in all tested soils. Further, the amount of Cr(III) sorbed increased with an increase in pH, CEC, clay, and OM of soils. Conversely, the chemical properties of soil such as positive charge and Fe (crystalline) had a noticeable influence on the sorption of Cr(VI). Desorption of Cr(VI) occurred rapidly and was greater than desorption of Cr(III) in soils. The mobility of Cr species as estimated by the retardation factor was higher for Cr(VI) than for Cr(III) in all tested soils. These results concurred with the results from leaching experiments which showed higher leaching of Cr(VI) than Cr(III) in both acidic and alkaline soils indicating the higher mobility of Cr(VI) in a wide range of soils. This study demonstrated that Cr(VI) is more mobile and will be bioavailable in soils regardless of soil properties and if not remediated may eventually pose a severe threat to biota.     

水溶性有机碳在各种粘土底土中的吸附：土壤性质的影响

Clay-rich subsoils are added to sandy soils to improve crop yield and increase organic carbon (C) sequestration; however, little is known about the influence of clay subsoil properties on organic C sorption and desorption. Batch sorption experiments were conducted with nine clay subsoils with a range of properties. The clay subsoils were shaken for 16 h at 4 ^oC with water-extractable organic C (WEOC, 1 224 g C L^-1) from mature wheat residue at a soil to extract ratio of 1:10. After removal of the supernatant, the residual pellet was shaken with deionised water to determine organic C desorption. The WEOC sorption was positively correlated with smectite and illite contents, cation exchange capacity (CEC) and total organic C, but negatively correlated with kaolinite content. Desorption of WEOC expressed as a percentage of WEOC sorbed was negatively correlated with smectite and illite contents, CEC, total and exchangeable calcium (Ca) concentrations and clay content, but positively correlated with kaolinite content. The relative importance of these properties varied among soil types. The soils with a high WEOC sorption capacity had medium CEC and their dominant clay minerals were smectite and illite. In contrast, kaolinite was the dominant clay mineral in the soils with a low WEOC sorption capacity and low-to-medium CEC. However, most soils had properties which could increase WEOC sorption as well as those that could decrease WEOC sorption. The relative importance of properties increasing or decreasing WEOC sorption varied with soils. The soils with high desorption had a low total Ca concentration, low-to-medium CEC and low clay content, whereas the soils with low desorption were characterised by medium-to-high CEC and smectite and illite were the dominant clay minerals. We conclude that WEOC sorption and desorption depend not on a single property but rather a combination of several properties of the subsoils in this study.     

Zinc sorption–desorption by sand,silt and clay fractions in calcareous soils of Iran

Zinc sorption–desorption by sand, silt and clay fractions of six representative calcareous soils of Iran were measured. Sand, silt and clay particles were fractionated after dispersion of soils with an ultrasonic probe. Zinc sorption analysis was performed by adding eight rates of Zn from 6 to 120 μmol g^?1. For the desorption experiment, samples retained after the measurement of Zn sorption were resuspended sequentially in 0.01 M NaNO₃ solution and shaken for 24 h. Results indicated that Zn sorption by soil fractions increased in the order clay > silt > sand, and correlated negatively with CaCO₃ content and positively with cation exchange capacity (CEC) and smectite content. Results indicated that for all fractions, the Langmuir equation described the sorption rates fairly well. In contrast to sorption, Zn desorption from soil fractions increased in the order sand > silt > clay, and correlated positively with CaCO₃ content, CEC and smectite content. Results showed that parabolic diffusion and two constant equations adequately described the reaction rates of Zn desorption. In general, for all soils studied, the coarser the particle size, the less Zn sorption and more Zn desorption, and this reflects much higher risk of Zn leaching into groundwater or plant uptake in contaminated soils.     

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.     

Formation of hydrate films on the surface of calcium silicate and aluminate in the presence of polyelectrolytes

To elucidate the mechanism of moistening and overmoistening of soils and mineral soil components capable of chemical hydration, the sorption of water vapor has been studied in combination with synchronous conductometric measurements. Effect of organic polyelectrolyte molecules on the hydration kinetics and the formation of hydrate films on their surface has been revealed for dehydrated calcium silicate and aluminate simulating minor soil components. The plotting of sorption–desorption curves has shown that hydrate–polymer films formed by aliphatic or aromatic polyelectrolytes with different functional groups (–COOH,–OH,–NH₂,–CONH, etc.) significantly vary in dispersion and structure. The changes in dispersion during hydration are frequently not correlated with the amount of resulting hydrates, the content of which is controlled by the crystallochemical features of sorbents, the structure and activity of the polymer functional groups, and the conditions of sorption kinetic studies. It has been shown that the formation of low-permeable surface organomineral layers is typical for aliphatic polyelectrolytes, while more permeable layers determining the water-physical and structure-forming properties of soils are typical for aromatic polyelectrolytes.     

Water stability of aggregates in subtropical and tropical soils (Georgia and China) and its relationships with the mineralogy and chemical properties

Water-stable aggregates isolated from three subtropical and one tropical soil (Western Georgia and China) were studied for their organic carbon, cation exchange capacity (CEC), specific surface area, magnetic susceptibility, and total chemical elements. The soils were also studied for their particle-size distribution, mineralogy, and nonsilicate Fe and Al oxides. Describe the water stability, three indices have been used: the content of water-stable macroaggregates (>0.25 mm), the mean weighted diameter of the aggregates, and the numerical aggregation index. The yellow-cinnamonic soil (China) was neutral, and the three other soils were acid. The soils were degraded with a low content of organic matter. The yellow-cinnamonic soil was characterized by the lowest water stability due to the predominantly vermiculite composition of the clay. The high water stability of the Oxisol structure was determined by the kaolinites and high content of oxides. In three out of the four soils studied, the hierarchical levels of the soil structure organization were defined; they were identified by the content of organic matter and the Ca + Mg (in Oxisols). Iron oxides mainly participated in the formation of micro-aggregates; Al and Mn contributed to the formation of macroaggregates. The water-stable aggregates acted as sorption geochemical barriers and accumulated Pb, Zn, Cd, Cs, and other trace elements up to concentrations exceeding their levels in the soil by 5 times and more. The highest correlations were obtained with CEC, Mn, and P rather than with organic carbon and Fe.     

Die Sorption von Phosphat an carbonatreichen Unterwasserböden

The sorption of phosphate by underwater soils rich in carbonate The phosphate sorption isotherms for carbonate rich under water soils (Unterwasserboden) can frequently be linearized by a modified Freundlich-isotherm when one assumes that, because of previously sorbed phosphate, the concentration of the equilibrium soil solution, P_1,0 is greater than 0. However, in many cases, the character of the phosphate sorption can be adequately determined with only one phosphate addition (P_s,500). Both methods show that for dried samples from under water soils, the samples from reduced horizons have a higher P sorption than for the associated oxidized horizons. This can be explained by the presence of very sorption active ferrihydrite which has precipitated from previously biologically reduced material.     

Evaluation of the sorption process for imidacloprid and diuron in eight agricultural soils from southern Europe using various kinetic models

Kinetic studies are of great concern for understanding the processes and parameters involved in the sorption of pollutants by soils. Sorption kinetics of imidacloprid and diuron in eight soils of different characteristics, with very low organic carbon content were investigated. Pseudosecond-order kinetic reactions closely correlate with the experimental kinetic (R(2) > 0.98) in all soils. The sorbed amount of diuron was higher than that for imidacloprid. The low OC content of these soils correlated neither with the sorbed amount nor with the kinetic parameters for both pesticides. Imidacloprid sorption was correlated with silt and sand content and cation exchange capacity (CEC); meanwhile for diuron, no correlation was found. Thus, sorption kinetics take place throughout different mechanisms related mainly to the chemical character of the pesticides. Sorption kinetic parameters determined using three of the four models selected (pseudosecond-order kinetic reactions, Elovich equation, and Weber-Morris models) have been shown to be worthy to distinguish the process controlling the sorption kinetic of both pesticides.     

Soil chemical properties affecting NH4+ sorption in forest soils

Fourteen European forest soils from the boreal to the mediterranean climate on different parent materials were investigated with respect to their ability to store NH₄⁺ in exchangeable form, using sorption isotherms. Distribution coefficients for NH₄⁺ sorption per unit weight of soil were in the range of 0.02 to 0.77. NH₄⁺ sorption coefficients were usually highest in the forest floor of a given soil. NH₄⁺ sorption behaviour of mineral soil horizons was correlated to soil parameters that are determined during routine soil analysis. A combination of CEC and base saturation explained up to 95% of the variability Of NH₄⁺ sorption. In the forest floors, variability in NH₄⁺ sorption could not be explained quantitatively from independent soil parameters. The affinity of the sorption sites for NH₄⁺ was the most important factor for explanation of the variability in NH₄⁺ sorption in the forest floors but was of low importance in mineral soil horizons. As NH₄⁺ exchanges predominantly base cations, susceptibility of NH₄⁺ to transport through the soil profile increases with Iowbase saturation of a soil as well as with low CEC values.     

A rapid method to determine cation exchange capacity and exchangeable bases in calcareous,gypsiferous, saline and sodic soils

Summary

A simple, single‐step extraction with LiEDTA for the estimation of CEC and exchangeable bases in soils has been developed. Multivalent cations are stripped from the soil adsorption sites by the strongly chelating agent EDTA, and are replaced by Li. In soils without CaCO₃ or water soluble salts, exchangeable divalent cations (Ca, Mg) are chelated by EDTA and exchangeable monovalent cations (Na, K) are replaced in a single extraction step using 0.25–2.5 g of soil and 10.0 ml of extractant.

In calcareous soils the CEC can be determined in the same way, but for the extraction of exchangeable Ca and Mg, another separate extraction is needed because dissolution of calcite by EDTA is unavoidable. This extraction is done with as much NaEDTA as needed to extract only exchangeable Ca and Mg in a 1:2 (m/V) soil/alkaline‐50% (V/V) aethanolic solution to minimize dissolution of calcite.

In gypsiferous soils gypsum is transformed into insoluble BaSO₄ and soluble CaEDTA by LiBaEDTA thus avoiding interference of Ca from dissolution of gypsum, which renders the traditional methods for determining CEC unsuitable for such soils. To determine exchangeable Ca and Mg, Na₄EDTA is used as for calcareous soils.

In saline/sodic soils replacement of Na by Li is incomplete but the Na/Li‐ratio at the complex after extraction is proportional to the molar Na/Li‐ratio in the extracts, so that the CEC and original exchangeable sodium (ESP) content can be calculated. Additional analysis of Cl and, if necessary, SO₄ in the extracts of saline soils can be used to correct for the effect of dissolution of the salts on the sum of exchangeable cations.

This new method is as convenient as the recently developed AgTU (silverthiourea), but is better suitable for calcareous and gypsiferous soils.     

Effects of equilibrating salt solutions on phosphate sorption by soils

Abstract

Several equilibrating salt solutions have been used in the studies of P sorption by soils and sediments. This study was conducted to evaluate the effects of 10 salt solutions on estimation of P sorption by soils. Results obtained showed that, when the equilibrating solution was made to contain 0.01M with respect to CaCl₂, Ca(NO₃)₂, CaSO₄, MgCl₂, KCl, LiCl, Nacl, or KHCO₃, the amount of P sorbed by soil always exceeded the amount sorbed from the soil‐water system. In comparison with the amount of P sorbed from water, 0.01M NaHCO₃ reduced P sorption by soils. Use of THAM buffer (0.05M pH 7.0) to control the pH increased P sorption by some soils and decreased P sorption by others, relative to that sorbed from the soil‐water system. The results indicated that inclusion of salts in the equilibrating solution for P‐sorption studies should be avoided, especially in studies related to water quality.     

Validation of water sorption‐based clay prediction models for calcareous soils

Soil particle size distribution (PSD), particularly the active clay fraction, mediates soil engineering, agronomic and environmental functions. The tedious and costly nature of traditional methods of determining PSD prompted the development of water sorption‐based models for determining the clay fraction. The applicability of such models to semi‐arid soils with significant amounts of calcium carbonate and/or gypsum is unknown. The objective of this study was to validate three water sorption‐based clay prediction models for 30 calcareous soils from Iran and identify the effect of CaCO₃ on prediction accuracy. The soils had clay content ranging from 9 to 61% and CaCO₃ from 24 to 97%. The three water sorption models considered showed a reasonably fair prediction of the clay content from water sorption at 28% relative humidity (RMSE and ME values ranging from 10.6 to 12.1 and −8.1 to −4.2, respectively). The model that considers hysteresis had better prediction accuracy than the other two that do not. Moreover, the prediction errors of all three models arose from under‐prediction of the clay content. The amount of hygroscopic water scaled by clay content decreased with increasing CaCO₃ content. The low organic carbon content of the soils and the low fraction of low‐activity clay minerals like kaolinite suggested that the clay content under‐predictions were due to large CaCO₃ contents. Thus, for such water‐sorption based models to work accurately for calcareous soils, a correction factor that considers the reduction of water content due to large CaCO₃ content should be included.     

苏南水稻土对铜离子专性吸附的初步研究

六十年代以来,土壤对多价离子特别是重金属离子的专性吸附,已日益成为土壤化学领域中一个受人注意的问题。土壤胶体中铁、锰、铝、硅等氧化物及其水合物和土壤有机质是专性吸附的主要载体^{[12,16,17,19,20,21]},它们对许多重金属元素的专性吸附所引起的富集过程,起着控制这些金属元素在土壤溶液和海水中浓度的作用^[9,15,18];一些微盒营养元素在土壤中的移动及其对植物的有效性,也深受土壤中氧化物胶体的专性吸附的影响^[11,14,21]。因此,铁、锰等水合氧化物对重金属离子的专性吸附的研究,不仅是土壤化学领域,而且也是土壤环境保护和地球化学等领域中的重要研究课题。     

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.     

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.     

Zinc Sorption in Sandy Soils from Central Vietnam as a Function of Soil Characteristics

Zinc (Zn) sorption curves were established for 11 cultivated sandy soils from central Vietnam. Soil samples (10 g) were equilibrated with 5 mM calcium chloride (CaCl₂) solutions (50 mL) at five zinc chloride (ZnCl₂) concentrations (0 to 80 mg Zn L^–1). The experimental sorption data were fitted with the Freundlich equation. The amounts of Zn sorbed by soil (Q_Zn) at different Zn concentrations in the equilibrium solution (C_Zn) were closely related to cation exchange capacity (CEC) and pH, that is, to the available exchange sites at given pH values. More specifically, an excellent correlation was found between Zn sorption and exchangeable calcium (Ca_ex), which evidently also depends on CEC and pH. A unique equation was proposed to predict Q_Zn from C_Zn and Ca_ex in the range of Zn loading covered in our research, that is, from traces to Q_Zn ≈ 60 mg Zn kg^–1.     

Addition of phosphorus to soils with low to medium phosphorus retention capacities. I. effect on soil phosphorus sorption properties

Abstract

Twelve soils with low‐medium phosphorus (P) retention capacities were equilibrated for 3 months with soluble phosphate at a rate of 100 mg P kg^‐1 soil. The P sorption properties of these soils both with and without added P were studied, including equilibrium P concentration (EPCo), standard P requirement (SPR), soil P sorption capacity (b), maximum buffer capacity (MBC), and P sorption index (P‐SI). In general, the soils with no added P showed low values of all the above parameters. Oxalate extractable aluminum appeared to be the major responsible element for the control of P sorption in these soils. The addition of P to these soils had a considerable effect on their P sorption properties. The changes in EPCo were well correlated with P sorption index (r=0.80; p≤0.01 ). The EPCo values of the soils with and without added P were closely correlated to bicarbonate extractable P (P_0lsen) and calcium chloride extractable P (P_CaC12), with r=0.80, and r=0.99 (p≤0.001), respectively. Ninety percent of the variability in EPCo was explained by the corresponding variability in P_Olsen when a curvilinear relationship was adopted. The P sorption properties examined appear to be useful parameters to assess the environmental impact of soil P on the quality of surface waters.