Adsorption of DNA on clay minerals and various colloidal particles from an Alfisol

Adsorption and desorption of salmon sperm DNA on four different colloidal fractions from Brown Soil and clay minerals were studied. The adsorption isotherms of DNA on the examined soil colloids and minerals conformed to the Langmuir equation. The amount of DNA adsorbed followed the order: montmorillonite?fine inorganic clay>fine organic clay>kaolinite>coarse inorganic clay>coarse organic clay. A marked decrease in the adsorption of DNA on organic clays and montmorillonite was observed with the increase of pH from 2.0 to 5.0. Negligible DNA was adsorbed by organic clays above pH 5.0. As for inorganic clays and kaolinite, a slow decrease in DNA adsorption was found with increasing pH from 2.0 to 9.0. The results implied that electrostatic interactions played a more important role in DNA adsorption on organic clays and montmorillonite. Magnesium ion was more efficient than sodium ion in promoting DNA adsorption on soil colloids and minerals. DNA molecules on soil colloids and minerals were desorbed by sequential washing with 10 mM Tris, 100 mM NaCl and 100 mM phosphate at pH 7.0. A percentage of 53.7-64.4% of adsorbed DNA on organic clays and montmorillonite was released, while only 10.7-15.2% of DNA on inorganic clays and kaolinite was desorbed by Tris and NaCl. The percent desorption of DNA from inorganic clays, organic clays, montmorillonite and kaolinite by phosphate was 39.7-42.2, 23.6-28.8, 29.7 and 11.4%, respectively. Data from this work indicated that fine clays dominate the amount of DNA adsorption and coarse clays play a more important role in the binding affinity of DNA in soil. Organic matter may not favor DNA adsorption in permanent-charge soil. The information obtained is of fundamental significance for the understanding of the ultimate fate of extracellular DNA in soil.     

Reactions of nucleic acid bases with inorganic soil constituents

The adsorption at pH's 4, 6 and 8 of adenine, guanine, cytosine, thymine and uracil on clays (montmorillonite, illite and kaolinite), Fe- and Al-oxides (goethite, hematite and gibbsite), a soil, and on a laboratory-prepared fulvic acid-montmorillonite complex was investigated. Portions of the clays and soil were saturated with H⁺, Fe³⁺ and Ca²⁺.Quantitatively, the extent of adsorption of nucleic acid bases by the clays was proportional to their exchange capacities, but the nature of the dominant cation had only minor effects. By contrast, the adsorption was strongly affected by pH, tending to decrease with increase in pH. Adsorption on goethite and gibbsite was lower than that on clays, while adsorption of nucleic acid bases on soils was slightly lower than that on oxides. The fulvic acid-montmorillonite complex adsorbed substantial, although smaller amounts of purines and pyrimidines, than did montmorillonite alone. The main adsorption mechanism at pH 4 appeared to be cation exchange whereas at pH 8 complex formation between the nucleic acid bases and cations on inorganic surfaces seemed to occur.The results of this and earlier work show that both inorganic and organic soil constituents adsorb nucleic acid bases. Which adsorption reaction predominates will depend on the clay and organic matter content and on the pH.     

Adsorption of pure and dirty bacterial DNA on clay minerals and their transformation frequency

Several studies have investigated the adsorption of pure DNA on soil particles and its transformation ability. However, the presence of not purified (dirty) rather than pure DNA is more common in the extracellular soil environment. For this reason, we have investigated the adsorption and binding of dirty DNA on montmorillonite (M) and kaolinite (K) and their transforming ability in comparison to pure DNA. After lysis of Bacillus subtilis cells, induced by KCl, dirty DNA was characterized by the presence of cellular wall debris (cwd) and other constitutional organic components (coc). The dirty DNA was then divided into two fractions, one with cellular wall debris (DNA +cwd) and the other without cellular wall debris (DNA −cwd). B. subtilis BD 1512 (Cm^r) and BD 170 (Cm^s) were selected as donor and recipient bacteria, respectively, for adsorption and transformation studies. Both cwd and coc seem to facilitate the adsorption of DNA to clay minerals, whereas only cwd promote the DNA binding on clays, protecting also the DNA fragments below 400 bp against nucleases. Both dirty DNA fractions adsorbed and bound on clay minerals were able to transform competent cells.     

Effects of physical and chemical properties of soils on adsorption of the insecticidal protein (Cry1Ab) from Bacillus thuringiensis at Cry1Ab protein concentrations relevant for experimental field sites

The adsorption of the insecticidal Cry1Ab protein of Bacillus thuringiensis (Bt) on Na-montmorillonite (M-Na) and soil clay fractions was studied. The aim of this study was not to find the adsorption capacity of the soils from the experimental field site, where Bt corn (MON810) was cultivated, but rather to characterize the adsorption behavior of the Cry1Ab protein at concentrations typically found at experimental field sites. In kinetic experiments, the Cry1Ab protein adsorbed rapidly (<60 min) on M-Na. As the concentration of M-Na was varied and the added Cry1Ab protein concentration was kept constant (20 and 45 ng ml⁻¹), the adsorption per unit weight of Cry1Ab protein decreased with increasing concentrations of M-Na. Adsorption of Cry1Ab protein on M-Na decreased as the pH value of the suspension increased. All adsorption isotherms could be described mathematically by a linear regression with the parameter k, the distribution coefficient, being the slope of the regression line. Although their mineralogical composition was nearly identical, the soil clay fractions showed different k values. The different k values were correlated with the physical and chemical properties of the soil clay fractions, such as the organic carbon content, the specific external surface area, and the electrokinetic charge of the external surfaces of the clays, as well as with the external surface charge density. An increase in the amount of soil organic matter, as well as an increase in the electrokinetic external surface charge of the soil clays, decreased the distribution coefficient k. An increase of the specific external surface areas of the soil clays resulted in a higher distribution coefficient k.Less than 10% of adsorbed Cry1Ab protein was reversibly adsorbed on the soil clays and, thus, desorbed. The desorption efficiency of distilled water was higher than that of a solution of CaCl₂ (2.25 mmol) and of dissolved organic carbon (50 mg C l⁻¹).     

Base cation,aluminum, and phosphorus release potential in Danish forest soils

Long‐term nutrient supply in forest ecosystems is due to the dissolution of primary and secondary minerals in soils. The potential of nutrient release in 19 forest soils in a cool humid climate was examined. The soil profiles are classified as Alfisols (10), Spodosols (2), Entisols (4), Ultisols (1), and Mollisols (2), thus covering a gradient in soil fertility. Short‐term and long‐term release of calcium, magnesium, potassium, phosphorus, and aluminum was evaluated by a batch extraction using dilute nitric acid (0.1 M) for 2 hours, followed by 2 days (48 h), and 7 days (168 h). The solution was renewed after 2 and 50 hours extraction time. Nutrient pools expressed as g m^–2 to soil depth 100 cm, and a base index (Ca²⁺+ Mg²⁺+ K⁺ (mol_c m^–2) : Ca²⁺ + Mg²⁺ + K⁺ + Al³⁺ (mol_c m^–2)) were interpreted in relation to soil texture classes. Subsoil texture classes: Coarse: < 5 % clay; medium 5–10 % clay or (> 5 % silt or > 50 % fine sand), or fine > 10 % clay were evaluated as an indicator of forest soil quality. Base cation and phosphorus release decreased in the order fine > medium > coarse. Texture classes explained base cation release by about 80 % of total variation, and phosphorus release by 40–50 %. The base index generally increased by extraction time for sandy soils and decreased for loamy soils. This indicated that sandy soils released accumulated reactive aluminum in the 0–2 hour extraction. Subsoil texture class is suggested as a pedotransfer function for long‐term nutrient release potential in Danish forest soils.     

Microbial utilisation of two proteins adsorbed to a vertisol clay fraction: toxin from Bacillus thuringiensis subsp. tenebrionis and bovine serum albumin

Clay minerals have been shown to reduce the extent and rate of biodegradation of several compounds. Here, we investigated the ability of soil clays to protect proteins from biodegradation: the insecticidal protein from Bacillus thuringiensis subsp. tenebrionis (Btt toxin) and Bovine Serum Albumin (BSA). The two proteins adsorbed in large amounts (up to 0.24 g BSA g⁻¹ clay and 0.74 g Btt toxin g⁻¹ clay) and irreversibly to smectite clay particles from a vertisol. We measured the growth of a soil inoculum in the presence of each of proteins as the sole source of carbon. When clay was present in the medium, microbial growth was directly proportional to the amount of free protein (i.e. nonadsorbed). Hence, the two proteins were unavailable when adsorbed to clay. The clay had little influence on the ability of microorganisms to hydrolyse a soluble substrate. The inhibitory effect of clays on utilisation of BSA and Btt toxin was interpreted as being the result of the adsorption of the proteins to clay, which rendered the proteins unavailable for microbial utilisation.     

我国几种主要土壤胶体的NH4+吸附特征

本文讨论我国几种主要土壤胶体的NH₄⁺吸附特征。土壤胶体对NH₄⁺的吸附符合两种表面Langmuir方程。土壤胶体对NH₄⁺的结合能力强弱顺序是:黄棕壤>黑土、(土娄)土>红壤>砖红壤,而NH₄⁺的解吸率大小顺序与此相反。Langmuir吸附方程参数K₁与土壤胶体的粘粒矿物组成有关,并与土壤胶体对NH₄⁺的相对偏好性(A值)呈正相关。Langmuir参数(M₁+M₂)与土壤胶体的CEC呈正相关,去有机质(OM.)前后△K₁与△OM.呈反相关。去有机质可增加土壤胶体对NH₄⁺的偏好性。土壤胶体的NH₄⁺吸附和解吸特征决定于其组成和表面性质,并受有机无机复合作用的影响。永久电荷吸附位对NH₄⁺的偏好性较强,而可变电荷吸附位则较弱。     

CLAY DISPERSION IN TYPICAL SOILS OF NORTH CAMEROON AS A FUNCTION OF PH AND ELECTROLYTE CONCENTRATION

Knowledge of clay dispersion behaviour [which is highly influenced by ion concentration in the aqueous phase and by related surface charge (SC) of colloids] is important for rating soil erosion risk (by water). It can also be useful for improving soil management systems. Clay fractions separated from samples of the A‐horizon of a Vertisol, Ultisol and Oxisol were collected, representing typical soils of North Cameroon. These soils were very different in physicochemical and mineral parameters. The effect of pH and the multivalent ions Ca²⁺, SO₄²⁻ and PO₄³⁻ on SC and dispersion characteristics were determined. The water dispersible clay was found to be higher in the Vertisol and Ultisol than in the Oxisol, indicating that the <2 µm fractions from the Vertisol and Ultisol are more dispersible than that from the Oxisol. The clay dispersion ratio together with the dispersion ratio were found to be in good agreement with water dispersible clay and are negatively correlated with the amount of organic matter and dithionite citrate bicarbonate soluble Fe and Al. Generally, SC of the <2 µm fraction was found to be negative when the pH was in the region of 3 to 9; thus the absolute value is highly pH‐dependent. At pH 6 and 8, CaCl₂, Na₂SO₄ and Na₂HPO₄ additions had antagonistic effects on SC: Ca²⁺ increased SC, whereas SO₄²⁻ and PO₄³⁻decreased SC indicating the adsorption of positively as well as negatively charged multivalent ions by soil colloids. Along with the increase of SC, there was a fall in repulsive forces and formation of Ca‐bridges, the addition of Ca²⁺ induced flocculation more rapidly than SO₄²⁻ and PO₄³⁻ amendments. Copyright © 2011 John Wiley & Sons, Ltd.     

Mineralogy of soil kaolinites from Cameroon

Different particle-size fractions of soil clays from the semi arid north and the humid tropical south of Cameroon have been characterized with reference to their chemical composition, clay mineralogy and kaolinite crystallinity (Hinckley indices). Selected samples were also examined by Mössbauer spectroscopy. Hinckley indices of kaolinites, which were a major component of the coarse clays, varied considerably (< 0.1 - 0.69) and differed significantly as a function of the geographic and landscape positions of the soil profiles. The Hinckley indices averaged 0.31 in soils from southern Cameroon and 0.30 and 0.07 in soils from high and low landscape positions in northern Cameroon, respectively. Kaolinite crystallinity is therefore considered to vary as a function of transport and/or depositional environment of the kaolinite-containing material. Mössbauer spectra showed that kaolinite-dominated Vertisol coarse clays contained higher relative amounts of Fe²⁺ than the corresponding fine clay, which is dominated by smectite. It is conceivable that the Fe²⁺ content of the kaolinite reflects the redox environment of the samples.     

Abstracts of Nippon Dojo-Hiryogaku Zasshi (Japanese Journal of Soil Science and Plant Nutrition)

The electrokinetic behavior of colloidal particles in three waterlogged soils at 38°C was investigated with reference to the stability changes of soil colloidal suspensions under reductive conditions. The dispersed clay particles of the three soils exhibited a negative zeta (ζ) potential. The absolute value of the ζ-potential, |-ζ|, of these soils in the earlier period of waterlogging decreased, which caused the flocculation of clay particles. The concentrations of divalent cations, i.e., Fe²⁺ and Ca²⁺ in the soil solutions were estimated to be higher than their critical flocculation concentrations (CFCs) on the basis of the observed CFCs of Fe²⁺ and Ca²⁺ for the clay suspension of halloysite as a reference. With the progression of the reduction process, clay particles of one soil still exhibited a low |- ζ| and flocculated. The concentrations of Fe²⁺ and Ca²⁺ in the soil solutions were estimated to be higher than their CFCs, respectively. The clay particles of two sandy soils, however, showed an increase in |- ζ| due to the increase in pH and dispersed. The concentrations of Fe²⁺ and Ca²⁺ in the soil solutions were estimated to be lower than their CFCs, respectively. The stability changes of the soil colloidal suspensions by these divalent cations under sequential soil-reduction can be explained by the alteration of the Stern potential (- ψ _s ), which determines the repulsion energy related to the potential energy of interaction between two particles. The apparent decrease in the Ca²⁺ concentration of the soil solutions in the later period of waterlogging was explained largely by the re-adsorption of water-soluble Ca²⁺ on the exchange sites of soil clays with the decrease in the Fe²⁺ concentration in the soil solution.     

Verhalten von Dünger-NH4 in Böden unterschiedlicher tonmineralischer Zusammensetzung im Inkubationsversuch

Fate of fertilizer ammonium in soils with different composition of clay minerals in an incubation experiment In an incubation experiment with three different soils (gray brown podsolic soil from loess, alluvial gley, and brown earth, derived from basalt) the specific adsorption (fixation) and release of fertilizer NH₄⁺ was investigated. In one treatment 120 mg NH₄–N/kg soil was added, while the other treatment (control) received no nitrogen. Soils samples were taken every ten days and analyzed for nonexchangeable and exchangeable NH₄⁺ and NO₃^?. The experimental results are showing that the specific adsorption of applied NH₄⁺ was related to the type of clay minerals. While the loess soil, rich in illite, and the alluvial soil, rich in expansible clay minerals, bound about 40% of the added NH₄⁺ specifically, the soil derived from basalt with mainly kaolinite bound only about 10 %. From the recently “fixed” fertilizer NH₄⁺ about a half was nitrified during the incubation period of about 9 weeks. In the control there was no significant release of specifically bound NH₄⁺. Obviously this NH₄⁺ is located more deeply in the interlayers of the clay minerals and not available to microorganisms.     

Effect of organic matter on the parameters of the selective sorption of cobalt and zinc by soils and their clay fractions

The sorption and ion-exchange behavior of Co(II) and Zn in the soil-equilibrium solution system was studied for different types and varieties of native soils and their clay fractions before and after mild oxidation with H₂O₂ to remove the organic carbon. The parameters of the ion-exchange adsorption and the selectivity coefficients of the (Co(II), Zn)/Ca ion exchange were determined using different models for describing the relationship between the dissolved and sorbed forms of the metals. These were the empirical Langmuir and Freundlich adsorption isotherms and the model of the ion-exchange adsorption based on the acting mass law. It was found that the soil organic matter played an important role in the selectivity of the ion-exchange adsorption of Co(II) and Zn by the soils and their clay fractions. This was confirmed by an abrupt decrease (to almost 1) of the selectivity coefficients of the Co²⁺/Ca²⁺ and Zn²⁺/Ca²⁺ exchange after the treatment of the clay fraction with hydrogen peroxide.     

Adsorption and desorption of cadmium by synthetic and natural organo-clay complexes

Tracer levels of ¹⁰⁹Cd were used to study the adsorption and desorption of Cd by synthetic and natural organo—clay complexes. Synthetic organo—clay complexes were made by adsorbing humic acid extracted from soil to various forms of < 2 μm diameter montmorillonite (Na, Ca, Al, and Fe saturated and Ca-montmorillonite coated with Al or Fe hydroxide). Natural organo—clay complexes were fractionated from the clay fraction of a Captina silt loam by density-gradient centrifugation in a large-scale zonal rotor.To evaluate the influence of humic acid on adsorption of Cd, Cd was adsorbed to the various forms of montmorillonite before and after humic acid adsorption. No appreciable difference in Cd adsorption was noted except in the case where montmorillonite was coated with Al or Fe hydroxides. Cadmium was found to be strongly bonded to clays coated with Al or Fe hydroxides; however, Cd adsorption to these clays after humic acid adsorption was considerably less. Data indicated Cd and humic acid adsorption sites on Al or Fe coated clays were either identical or prior adsorption of humic acid simply covered available Cd sites.Cadmium adsorption to clay density fractions showed that greatest adsorption was to fractions containing high quantities of organic matter or sesquioxides. Desorption of Cd with 0.01 M Ca (NO₃)₂ showed that Cd was adsorbed more tenaciously to the sesquioxides than organo—clay fractions.     

电解质种类和浓度影响磷酸根解吸的机理研究

本文研究了吸附性阳离子、电解质浓度和组成影响几种矿物和土壤吸附态磷的解吸的机理。结果表明,吸附性阳离子影响磷酸根解吸与离子桥有关。桥接静电场愈强,被束缚磷的释放就愈困难。电解质阳离子对磷酸根解吸的影响则取决于其对表面负电荷的屏蔽效应。阳离子电价高,屏蔽作用大,磷解吸就少。电解质浓度影响吸附态磷的解吸主要与表面电位的变化有关。当pH>PZC值时,提高电解质浓度降低表面负电位,从而减少磷的吸附;当pH<PZC时,提高电解质浓度则降低表面正电位,促进磷的解吸。磷酸根解吸盐效应零点(P_PZSE)值一般都介于土壤或矿物样品吸附磷酸根前后测得的两个PZC值之间。不同浓度电解质溶液中磷解吸量之差与吸附层电位变化量(△ψ_x)呈正相关。     

Chemisch-mineralogische und mikromorphologische untersuchung einer eutrophen (Ramann-) braunerde des Budapester Hügellandes

In spite of the fact that Ramann's concept of Braunerde was extensively used throughout the world, some pedogenic processes and soil properties which are important for the formation and existence of Brown Forest Soils (eutrophic brown earths) are still not well known. Hence, a soil was investigated which was classified as a “Braunerde” by Ramann in 1909. The main question was, whether there might be soil constituents such as inorganic amorphous substances (allophanes) which are able to stabilize the brown-earth fabric, or to inhibit clay migration. From chemical data as well as from the magnitude of the pH-dependent CEC, it was deduced that there are no appreciable amounts of allophanes within the soil. The fabric, however, seems to be stabilized by colloid-chemical flocculation of the clay particles caused by large amounts of carbonates and silicates deposited with the parent material (loess). The decalcified solum is still rich in silicates, especially sand and coarse-silt-sized micas and feldspars (60–200 and 20–60 μm fractions, respectively). Since - in comparison - loesses and loess-derived soils of the Central German mountain region contain less silicates, mainly in fine and medium silt fractions (2–6 and 6–20 μm diameter, respectively), the coarser-grained silicates were assumed to be important for maintaining the Ca²⁺ and Mg²⁺ saturation of the soil by continuous weathering and thus stabilizing the brown-earth fabric.Although the soil is saturated predominantly with Ca²⁺ and Mg²⁺ ions, clay migration proceeds within the upper horizons. This was shown by calculation of the amounts of clay formed by breakdown of micas originally present in the parent material (“clay formation balance”), as well as by micromorphological studies. Furthermore, micromorphological studies and x-ray diffraction data gave some evidence for the migration of preferably finest grained montmorillonitic clays (smectites) penetrated by organic substances (humus). This kind of “selective clay migration” was assumed to be caused by high Ca²⁺ (or Mg²⁺) concentrations in soil solution required for flocculation of humus-penetrated (humus-coated) smectites. From the occurrence of these “humus-smectites” the possibility was assumed that the soil studied has been developed from a former Chernozem type.Quantitatively, clay migration does not reach the amounts of clay formation (breakdown of micas) accompanied by precipitation of iron oxides on mineral surfaces (“Verbraunung”). Thus, the soil profile visually and macromorphologically clearly exhibits the features of brown earths. On the other hand, however, some clay migration was observed. Hence, the soil was classified as a “brown earth with some clay migration” (“schwach durchschlämmte Braunerde”).Judging from the results of the “clay formation balance” an appreciable pedogenic (autigenic) clay formation from weathering products of feldspars was excluded for the soil studied.     

CALCIUM: ALUMINIUM EXCHANGE EQUILIBRIA IN CLAY MINERALS AND ACID SOILS1

Exchange reactions between 0.0in AlCl₃ solutions of different pH and Ca-saturated montmorillonite, vermiculite, illite, and soils from the Park Grass Experiment at Rothamsted and the Deerpark Experiment, Wexford, Ireland, showed that Al³⁺ and Al(OH)₂⁺ were adsorbed from solutions of pH > 4.0 and Al³⁺ and H⁺ from solutions of pH < 3.0. When Al was adsorbed, the cation exchange capacity of Ca-saturated soils and clays increased. Conventional Ca: Al exchange isotherms showed that Al³⁺ was strongly preferred to Ca²⁺ on all soils and clays. The equilibrium constant for Ca: Al exchange, K, was identical for soils before and after oxidizing their organic matter and did not vary, for any exchanger, with Al-saturation or the initial pH of the AlCl₃ solution. This proved the validity of the procedure used for calculating exchangeable Al³⁺. K values for Ca:Al exchange favoured Al³⁺ in the order: vermiculite > Park Grass soil > Deerpark soil > illite > montmorillonite. The influence of surface-charge densities of the clay minerals on this order is discussed and a method proposed and tested for calculating the K value of a soil from its mineralogical composition.     

恒电荷土壤胶体对Cu2+ 、Pb2+ 的静电吸附与专性吸附特征

供试土壤胶体对Cu2 、Pb2 的吸附强度用pH50 值表示 ,其大小次序为 :土 >黄绵土、黑垆土 >黄褐土。离子强度实验和表面络合反应机制证明恒电荷土壤胶体对Cu2 、Pb2 的吸附含有专性吸附 ,n值可作为判断专性吸附与静电吸附比例的特征值 ,低pH值时 ,以水解 -络合吸附为主 ;高pH值时 ,以水解 -络合与沉淀吸附为主。静电吸附和专性吸附的比例与pH有关 ,各土壤胶体专性吸附百分数大小为 :黄褐土 >土 >黑垆土 >黄绵土。不同土壤胶体在同一介质中对Cu2 、Pb2 的固有络合常数logKintM 值及固有络合ΔG m 负值大小次序与吸附强度大小一致。在定pH定浓条件下 ,考虑离子之间的相互作用时 ,土壤胶体对重金属离子的吸附过程可用BDM等温式描述。供试土壤胶体对Cu2 、Pb2 专性吸附ΔG m 的大小与固有络合ΔG m 接近且大小次序也一致。     

Adsorption sur les argiles de deux lipopolysaccharides rhizosphériques

The adsorption with time has been measured of two well characterized lipopolysaccharides onto aqueous suspensions of a montmorillonite, a kaolinite and an illite at one fixed polymer-clay ratio. The clays were prepared in the Fe⁺⁺⁺ or Ca⁺⁺ forms by washing with FeCl₃ or CaCl₂ followed with water. The competitive sorption of the two polymers was measured also in the presence of an equal concentration of a protein or a basic amino-acid. Sorption of the polymers by themselves was approximately proportional to the external areas of the three clays and independent of the exchangeable cation. The presence of the protein inhibited completely the adsorption of both polymers onto the Ca⁺⁺ clays, but usually enhanced sorption onto the Fe⁺⁺⁺ clays. Sorption in the presence of the amino-acid differed both for each polymer and according to the form of the clay. Possible reasons for the various sorption patterns are discussed.     

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

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

Cation exchange capacities of organo-mineral particle-size fractions in soils from long-term experiments

Soils with and without organic manuring from 10 long-term manurial experiments in East Germany were fractionated into organo-mineral particle-size separates by ultrasonic disaggregation and sedimentation/decantation. The cation exchange capacities (CECs) buffered at pH 8.1 were determined for the size fractions fine+medium clay, coarse clay, fine, medium and coarse silt, sand, and for the total soil samples. In the samples from nine field experiments the CECs decreased with increased equivalent diameters (fine+medium clay: 489–8 13 mmol_c kg^?1, coarse clay: 367–749 mmol_c kg^?1, fine silt: 202–587 mmol_c kg^?1. medium silt: 63–345 mmol_c kg^?1, coarse silt: 12–128 mmol_c kg^?1 and sand: 10–156 mmol_c kg^?1. The CECs varied with genetic soil type, mineralogical composition of the <6.3-μm particles, and the C and N contents of the size fractions. In a pot experiment examining the role of various organic materials in the early stages of soil formation, the clay-size fractions had the largest CECs (85–392 mmol_c kg^?1), followed by the medium-silt (1 9-222 mmol_c kg^?1) and fine-silt fractions (23–192 mmol_c kg^?1). The effect of organic amendments on CEC was in general: compost>fresh farmyard manure = straw + mineral fertilizer = mineral fertilizer.