Sorption and Binding Mechanism of Polysaccharide Cleaving Soil Enzymes by Clay Minerals

Analyses of the sorption of five polysaccharide cleaving soil enzymes by Na-homoionic clay minerals revealed a dependency on the cation exchange capacity of the clays: montmorillonite displayed the highest sorbing capacity, followed by palygorskite and kaolinite. Variation of the experimental conditions using cellulase and montmorillonite showed a maximum sorption at pH 4.8 and temperatures between 25°C and 45°C. Urea had no effect on the sorption, whereas humic acids and acetylation of enzymes lead to a decrease. No sorption was observed in the presence of bivalent cations. A discussion of possible binding mechanisms lead to the conclusion that interactions can be ascribed to van der Waals forces rather than to ionic reactions. It is assumed that the enzymes penetrate into the interlayers of montmorillonite, but not of palygorskite and kaolinite.     

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.     

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

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

The adsorption characteristics of soils and removal of cadmium and nickel from wastewaters

The interactions between the adsorption characteristics of 27 experimental soils and the sorption of Cd and Ni from the municipal wastewaters were investigated in this study. The removal of these elements from soil solution was followed for 50 days. All the adsorption characteristics, except cation exchange capacity and organic matter, were significantly correlated to the sorption of Cd after one day shaking. After 7 days of shaking, none of the soil adsorption characteristics except free CaCO₃ was significantly correlated to Cd removal from wastewater. The soil saturated paste pH and suspension pH were strongly correlated to Cd sorption throughout this experiment. The behavior of Ni in soils was different from that of Cd. Surface area, total Fe, and total Al were significantly correlated to Ni sorption. The correlation between Ni removal and pH was the strongest than any other parameter studied. After 7 days shaking, clay content and total Ca were not significantly correlated to Ni sorption. The cation exchange capacity of the soils was not significantly correlated to Cd or Ni sorption in this experiment. It seems that in the experimental soils, concentration of Cd and Ni were probably not controlled by adsorption process. The precipitation process was probably playing a major role in the removal of these elements from the municipal wastewaters. As observed in this experiment, the cation exchange capacity of experimental soils was a poor parameter to define sorption capacity of these soils for Cd and Ni. The guidelines for determining the soil sludge load, which are mainly based on the cation exchange capacity of soils, should be revised.     

Effect of Al hydroxide polymers on cation exchange of montmorillonite

Al hydroxide polymers (AlHO) can significantly influence the cation exchange behaviour of clays. We have determined the effect of synthesized AlHO on Ca–Na, Zn–Na and Pb–Na exchange for a series of exchanger compositions and two Al loadings at pH 6.0 and an ionic strength of 0.01  m . The preference for Ca on the siloxane surface of the clay–AlHO system (CAlHO) was greater than for the pure clay, and the average K _V (Vanselow selectivity coefficient) was determined to be 2.16 and 1.24, respectively. The selectivity coefficients for the exchange reactions Zn–Na and Pb–Na were not directly determined in CAlHO systems, because heavy-metal ions bind as well to the clay surface as to the AlHO over a wide range of pH. We have estimated the effect of the presence of AlHO on the selectivity coefficients of Zn–Na and Pb–Na exchange by extrapolation of the experimental results of Ca–Na, Zn–Na and Pb–Na exchange for pure clay and Ca–Na exchange for CAlHO. The average K _V was increased by the presence of the AlHO from 1.23 to 2.16 for Zn–Na exchange and from 1.59 to 2.77 for Pb–Na exchange. The increase in the preference for the divalent cations is probably caused by parallel alignment of clay platelets by sorption of AlHO. Increasing the amount of AlHO did not change the selectivity for Ca–Na exchange, and probably the structure of the system or the arrangement of the clay platelets and AlHO particles was not substantially changed. This was supported by the linear reduction of the cation exchange capacity with amount of AlHO present at pH 6.6. It seems likely that the selectivity coefficients for Ca–Na, Zn–Na and Pb–Na exchange that we found apply in naturally occurring montmorillonite–AlHO systems.     

The interaction of hydrazine hydrate with humic acid preparations at pH 4

Sorption isotherms were obtained by a continuous-flow method for the interaction of hydrazine hydrate with freeze-dried hydrogen-, aluminium- and calcium-exchanged humic acid preparations in aqueous suspensions at pH 4. The application of the continuous-flow method is outlined and the fit of the isotherms to three sorption equations is examined. Microcalorimetry was used to measure directly the differential enthalpies of reaction as functions of sorptive concentrations. Exchange by hydrazinium ions of the exchangeable cations on the humates, chemisorption by interaction of hydrazine with humate carbonyl groups, and non-specific sorption involving weakly- and strongly-held hydrazinium ions and hydrazine molecules are shown to be the major sorption processes in these systems. The relative importance of each of these processes for the different hydrazine/humate systems is discussed, and the influence of the exchangeable cation on humate reactivity is considered.     

Behaviour of Reduction–Sorption of Chromium (Vi) from an Aqueous Solution on a Modified Sorbent from Rice Husk

A carbonaceous sorbent produced from rice husk via sulphuric acid treatment was used to remove Cr(VI) from aqueous solutions varying contact time, pH, Cr(VI) concentration and sorbent status (wet and dry). Cr(VI) was removed from the aqueous solution via reduction to Cr(III) and sorption. Reduction and sorption processes were investigated in terms of kinetics and equilibrium. The rate of reduction removal of Cr(VI) at pH 2 followed a pseudo first-order model while the rate of sorption of total chromium followed pseudo second-order model. Chromium sorption was highly dependent on the initial pH value with reduction taking place in solution with pH up to 7 showing sorption maxima in the pH range 1.8–2.8 for concentration range 100–500 mg/l with an increase in the equilibrium pH. Carbon dioxide evolved from the sorption media was determined. Reduction–sorption mechanism was investigated via physicochemical tests including cation exchange capacity, base neutralization and sorbent acidity in addition to FTIR studies for sorbent samples before and after sorption reaction.     

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

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

Origin of the pH-dependent cation exchange capacities of Irish soil clays

Values of cation exchange capacity determined at pH 4.8 and at pH 8.2 are reported for peroxidized clay separates from a group of Irish soils derived from a variety of parent materials. The correlation between the two measurements was poor. The differences between the values (pH-dependent CEC's) ranged from 0.1 to 58.6 mequiv./100 g, with a mean of 12.9 mequiv./100 g. The highest values were associated with clays from spodic horizons and clays from basalt-derived soils. CEC at pH 8.2 and pH-dependent CEC were highly correlated with citrate-dithionite-bicarbonate (CDB) extractable Al. In contrast, CEC at pH 4.8 was negatively correlated with this parameter, suggesting that hydrous oxides reduced CEC at low pH values.Values of CEC of pH 4.8 and pH 8.2 are also reported for a selection of 16 clays subjected to sequential extraction with CDB and NaOH. CDB treatment reduced mean pH-dependent CEC from 20.4 to 9.0 mequiv./100 g, which was reduced to 3.9 mequiv./100 g by subsequent extraction with NaCH. The material removed by CDB was apparently positively charged at pH 4.8 and negatively charged at pH 8.2. Most of the pH-dependent CEC remaining after CDB treatment was associated with the clays from spodic horizons. The material extracted by NaOH was apparently negatively charged at both pH 4.8 and pH 8.2. No direct evidence of the physical nature of this material was obtained but it was present in sufficient amounts to suggest that it existed in particular forms in some of the clays from the spodic horizons. Following the dissolution treatments, the correlation between CEC values at pH 4.8 and pH 8.2 was very good (r = 0.99).     

Molybdate sorption by oxides of aluminium and iron

The sorption of molybdate by goethite, hematite, bayerite and α-Al₂O₃ was studied as a function of molybdate concentration and pH. The sorption isotherms exhibited double sorption plateaus in which the amount of Mo sorbed in the second plateau was double that in the first. This was attributed to the polymerization of molybdates as the concentration increases. Furthermore Mo sorption was found to be associated with a cosorption of Na cations, probably present to maintain electroneutrality in the surface zone. The sorption showed high sensitivity towards the pH, attaining a maximum at pH 4. For the iron oxides the decrease in sorption was much less pronounced on the acid side of the pH maximum and occured at lower pH values than that of the Al oxides. Molybdate sorption is explained in terms of a ligand exchange reaction between molybdate and surface hydroxyls.     

Influence of some chelates of aluminium on the sorption of phosphate by hydrous Al-oxides

Sorption of phosphate by hydrous oxides of aluminium was studied as a function of pH, presence of chelates of aluminium and of the specific surface areas of the oxides. Aluminon was most effective in reducing P sorption followed by oxalic acid and EDTA. Acetylacetone, 8-hydroxyquinoline, salicylic acid and fluoride affected little P sorption. The sorption was found to be higher the higher the value of the specific surface area of the oxide, but the shape of the sorption curve was the same for all the oxides studied, exhibiting a maximum at about pH 5. This maximum was found to coincide with the point of zero charge as determined in the presence of acetate ions. The sorption data are explained in terms of a ligand exchange mechanism in which phosphate chemisorbs on surface aluminium atoms displacing uncharged surface hydroxyls.     

批实验中土壤对地乐酚吸附的差异

吸附是决定除草剂地乐酚在土壤中迁移的重要机制之一。通常用简单快捷的批实验来衡量土壤对除草剂的吸附。由大量的批实验确定地乐酚在不同土壤样本中的吸附参数,并对各土壤特性与吸附参数的相关性作统计分析。结果表明土壤有机C含量,粘粒含量及阳离子代换量与吸附参数显著正相关,土壤pH值与吸附参数显著负相关。方差分析表明地乐酚在土壤中的吸附表现出很强的空间差异,在不同地点的地乐酚吸附参数无显著区别,而在不同的深度区别显著。超过85%的地乐酚吸附参数的空间差异可由土壤有机C含量的空间差异来解释。     

伊朗西部地区碱性土壤中共离子对Zn吸附的影响

Zinc(Zn) is essential to plant growth and relatively mobile in soils.This study was conducted to assess the effect of common ions(Ca 2+,K +,Na +,NH + 4,Cl,NO 3,and H 2 PO 4) on sorption of Zn in surface samples of ten calcareous soils from western Iran using 10 mmol L 1 KCl,KNO 3,KH 2 PO 4,Ca(NO 3) 2,NaNO 3,and NH 4 NO 3 solutions as background electrolytes.The results indicated that both NH + 4,K +,and Ca 2+ equally decreased Zn sorption as compared to Na +.Zinc sorption was decreased by H 2 PO 4 as compared to NO 3 and Cl.The Langmuir and Freundlich equations fitted closely to the sorption data of all ions.The Langmuir maximum,bonding energy constant,and Freundlich distribution coefficient for Zn sorption differed among the various ionic background electrolytes.Langmuir sorption parameters showed that the presence of H 2 PO 4 decreased the maximum Zn adsorbed,but increased the bonding energy.Although K + and NH + 4 equally influenced maximum Zn adsorbed,they differed in their effect on the distribution coefficient of Zn in soils.Values of saturation index calculated using Visual MINTEQ indicated that at the low Zn concentration,Zn solubility was controlled by sorption reactions and at the high Zn concentration,it was mainly controlled by sorption and mineral precipitation reactions,such as precipitation of Zn 3(PO 4) 2.4H 2 O,Zn 5(OH) 6(CO 3) 2,and ZnCO 3.For most ionic background electrolytes,soil pH,CaCO 3,and cation exchange capacity(CEC) were significantly correlated with sorption parameters.     

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.     

Modification Effects of Hematite with Aluminum Hydroxide on the Removal of Fluoride Ions from Water

The modification effects of hematite with aluminum hydroxide were investigated on the removal of fluoride ions from water using batch experiments. The effects of pH, contact time, fluoride concentration, and the dose of sorbent on the sorption of fluoride ions by a modified hematite were studied. Characterization of hematite before and after the modification with aluminum hydroxide was studied by X-ray diffraction, scanning electron microscope, and Brunauer–Emmett–Teller. Equilibrium was reached in 48 h of contact time and the maximum sorption of fluoride was found in the pH_eq range between 2.34 and 6.26. The Elovich model described the kinetic sorption processes and the Langmuir–Freundlich model, the sorption isotherm process. These results indicated that the sorption mechanism was chemisorption on a heterogeneous material.     

Modelling cations in three acid soils with differing acid input in Germany

Prediction of concentration changes of cations in soil solutions is complex, and chemical models are necessary for the purpose. The objective of this study was to determine whether the reactions considered in a coupled equilibrium model were appropriate to predict cation concentrations when the initial equilibrium was disturbed by adding small amounts of electrolytes. Multi-ion sorption in three acid soils (two Cambisols and a Podzol) was studied by sequentially adding small amounts of electrolytes to samples of the soils in batch experiments. A chemical equilibrium model that included inorganic complexation and multiple cation exchange was used to interpret the results. For the subsoils, the solubility of jurbanite was also included in the model. Model results for the two Cambisol surface soils agreed well or satisfactorily with the measured pH and sorption values of Na, K, Mg, Ca, Mn, Al and Fe, with a few exceptions. Linear correlation coefficients were generally between 0.97 and 1, and the regressin coefficients for cations (modelled against measured) lay between 0.6 and 1.3. For the subsoils sorption of sulphate was described satisfactorily for the spodic dystric Cambisol and to some extent for the spodic Cambisol. Correlation coefficients for subsoils lay between 0.63 and 1, and the regression coefficients (modelled against measured) were between 0.9 and 1.6 for the Cambisols. The model did not predict pH and sorption data in surface and subsurface soils with very small amounts of exchange capacities, pointing to the significance of cation buffering resulting from exchange sites. This study showed the usefulness and limitations of equilibrium models to predict the composition of the soil solution.     

Response to salinity of three grain legumes for potential cultivation in arid areas

Abstract

The material balance of all the chemical species associated with the phosphate sorption reaction by two amorphous clays, silica-alumina gel and synthetic goethite was investigated adjusting the initial pH to 4.0, 5.0, 6.0, and 7.0. Phosphate sorption was found to decrease with increasing initial pH. During phosphate sorption, the equilibrium pH rose, adsorption of Cl^- decreased to a state of negative adsorption, adsorption of Na⁺ increased markedly, silicate was released, and Al in the solution was precipitated. With increasing initial pH, the amount of apparent released OH^- increased, the amount of Na⁺ adsorption increased, and the amount of released silicate decreased. The overall relationship of the material balance is explained in terms of the charge balance associated with phosphate sorption.     

Sorption Behavior of Ofloxacin to Kaolinite: Effects of pH,Ionic Strength,and Cu(II)

Sorption of antibiotics to clay minerals is a key process controlling their transport and fate in environment. In this study, the effects of pH, ionic strength, and Cu(II) on ofloxacin (OFL) sorption to kaolinite were investigated by batch sorption experiments. The results of sorption edge experiments suggested that OFL sorption to kaolinite was pH and ionic strength dependent. Cation exchange was a major contributor to the sorption of OFL⁺ to kaolinite. The decreased OFL sorption with increasing ionic strength indicated the formation of outer-sphere complexation. When solution pH was lower than 7.0, Cu-OFL complexes facilitated OFL sorption through electrostatic attraction or formation of kaolinite-Cu-OFL and kaolinite-OFL-Cu ternary surface complexes. However, existence of free Cu(II) cation in solution competed for sorption sites, and thus suppressed OFL sorption. When solution pH was higher than 7.0, Cu(II) existed as Cu(OH)₂, and the Cu-OFL complexes in aqueous phase and solid phase (precipitation) enhanced OFL removal efficiency from solution. The results imply that Cu(II) effects should be taken into account in the evaluation of OFL mobility in environment.     

Metsulfuron methyl sorption-desorption in field-moist soils

Pesticide sorption coefficients (K(d)) are generally obtained using batch slurry methods. As a consequence, the results may not adequately reflect sorption processes in field-moist or unsaturated soil. The objective of this study was to determine sorption of metsulfuron methyl, a weak acid, in field-moist soils. Experiments were performed using low density (i.e., 0.3 g mL(-)(1)) supercritical fluid carbon dioxide (SF-CO(2)) to convert anionic metsulfuron methyl to the molecular species and remove it from the soil water phase only, thus allowing calculation of sorption coefficients (K(d)) at low water contents. K(d) values for sorption of the metsulfuron methyl molecular species on sandy loam, silt loam, and clay loam soil at 11% water content were 120, 180, and 320 mL g(-)(1), respectively. Using neutral species K(d) values, the pK(a) of metsulfuron methyl, and the pH of the soil, we could successfully predict the K(d) values obtained using the batch slurry technique, which typically has a predominance of anionic species in solution during the sorption characterization. This application of supercritical fluid extraction to determine sorption coefficients, combined with sulfonylureas' pK(a) values and the soil pH, will provide an easy method to predict sorption in soil at different pH levels.     

Chemical factors affecting selenite sorption by allophanic soils

The sorption of selenite by two allophanic soils containing high amounts of variable charge materials was studied. Selenite sorption exhibited a maximum near pH 4 and decreased, although not proportionally, with increasing pH. Only negligible amounts of selenite were sorbed above pH 7.In the two soils, the addition of selenite caused a release of sulphate (SO²⁻₄), silicate (Si) and hydroxyl ion (OH⁻) and an increase in cation (Na⁺) adsorption. No measurable amount of phosphate (P) was released. Increase in negative charge as measured by Na⁺ adsorption accounted for 48 and 18% of selenite sorbed (soils 1 and 2, respectively), the rest being accounted for by release of anions. The results presented here are consistent with the widely held view that selenite and phosphate are sorbed onto variable charge surfaces by a similar mechanism (ligand exchange).