Adsorption of Phosphate on Variable Charge Soils

The study about the adsorption of phosphate on four variable charge soils and some minerals revealed that two stage adsorption appeared in the adsorption isotherms of phosphate on 4 soils and there was a maximum adsorption on Al-oxide-typed surfaces between pH 3.5 to pH 5.5 as suspension pH changed from 2 to 9, but the adsorption amount of phosphate decreased continually as pH rose on Fe-oxide typed surfaces. The adsorption amount of phosphate and the maximum phosphate adsorption pH decreased in the order of yellow-red soil > lateritic red soil > red soil > paddy soil, which was coincided with the content order of amorphous Al oxide. The removement of organic matter and Fe oxide made the maximum phosphate adsorption pH rise from 4.0 to 5.0 and 4.5, respectively. The desorption curves with pH of four soils showed that phosphate desorbed least at pH 5. Generally the desorption was contrary to the adsorption with pH changing.     

有机酸对污染土壤中镉释放的影响

There is limited information on the release behavior of heavy metals from natural soils by organic acids. Thus, cadmium release, due to two organic acids (tartrate and citrate) that are common in the rhizosphere, from soils polluted by metal smelters or tailings and soils artificially contaminated by adding Cd were analyzed. The presence of tartrate or citrate at a low concentration (≤ 6 mmol L^-1 for tartrate and ≤ 0.5 mmol L^-1 for citrate) inhibited Cd release, whereas the presence of organic acids in high concentrations (≥ 2 mmol L^-1 for citrate and ≥ 15 mmol L^-1 for tartrate) apparently promoted Cd release. Under the same conditions, the Cd release in naturally polluted soils was less than that of artificially contaminated soils. Additionally, as the initial pH rose from 2 to 8 in the presence of citrate, a sequential valley and then peak appeared in the Cd release curve, while in the presence of tartrate the Cd release steadily decreased. In addition, Cd release was clearly enhanced as the electrolyte concentration of KNO₃ or KCl increased in the presence of 2 mmol L^-1 tartrate. Moreover, a higher desorption of Cd was shown with the KCl electrolyte compared to KNO₃ for the same concentration levels. This implied that the bioavailability of heavy metals could be promoted with the addition of suitable types and concentrations of organic acids as well as reasonable field conditions.     

黑土轻组分C与团聚体水稳性的关系

To evaluate the role of kaolinite and variable charge soils on the hydrolytic reaction of Al, the hydrolysis of Al ions in suspensions of a kaolinite and an Oxisol influenced by organic anions was investigated using changes of pH, Al adsorption, and desorption of pre-adsorbed Al. Kaolinite and the Oxisol promoted the hydrolytic reaction of Al above a certain initial Al concentration （0.1 mmol L^-1 for kaolinite and 0.3 mmol L^-1 for the Oxisol）. The Al hydrolysis accelerated by kaolinite and the Oxisol increased with an increase in initial concentration of Al and was observed in the range of pH from 3.7 to 4.7 for kaolinite and 3.9 to 4.9 for the Oxisol. The acceleration of Al hydrolysis also increased with the increase of solution pH, reached a maximum value at pH 4.5, and then decreased sharply. Al hydrolysis was promoted mainly through selective adsorption for hydroxy-Al. Soil free iron oxides compensated a portion of the soil negative charge or masked some soil surface negative sites leading to a decrease in Al adsorption, which retarded acceleration to some extent. For the Oxisol organic anions increased the proportion of adsorbed Al^3＋ in total adsorbed Al with the increase in soil negative surface charge and eliminated or reduced the acceleration of Al hydrolysis. Different organic anions inhibited the hydrolysis of Al in the order： citrate 〉 oxalate 〉 acetate （under initial pH of 4.5）. The formation of Al-organic complexes in solution also inhibited the hydrolysis of Al.     

高岭石和氧化土悬液中铝的水解行为及有机酸对铝水解反应的影响

To evaluate the role of kaolinite and variable charge soils on the hydrolytic reaction of Al, the hydrolysis of Al ions in suspensions of a kaolinite and an Oxisol influenced by organic anions was investigated using changes of pH, Al adsorption, and desorption of pre-adsorbed Al. Kaolinite and the Oxisol promoted the hydrolytic reaction of Al above a certain initial Al concentration (0.1 mmol L^-1 for kaolinite and 0.3 mmol L^-1 for the Oxisol). The Al hydrolysis accelerated by kaolinite and the Oxisol increased with an increase in initial concentration of Al and was observed in the range of pH from 3.7 to 4.7 for kaolinite and 3.9 to 4.9 for the Oxisol. The acceleration of Al hydrolysis also increased with the increase of solution pH, reached a maximum value at pH 4.5, and then decreased sharply. Al hydrolysis was promoted mainly through selective adsorption for hydroxy-Al. Soil free iron oxides compensated a portion of the soil negative charge or masked some soil surface negative sites leading to a decrease in Al adsorption, which retarded acceleration to some extent. For the Oxisol organic anions increased the proportion of adsorbed Al³⁺ in total adsorbed Al with the increase in soil negative surface charge and eliminated or reduced the acceleration of Al hydrolysis. Different organic anions inhibited the hydrolysis of Al in the order: citrate > oxalate > acetate (under initial pH of 4.5). The formation of Al-organic complexes in solution also inhibited the hydrolysis of Al.     

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.     

有机配体、竞争阳离子和pH对土壤中Zn分解的影响

A series of experiments were conducted to examine the interactive effects of an organic ligand, a competing cation, and pH on the dissolution of zinc （Zn） from three California soils, Maymen sandy loam, Merced clay, and Yolo clay loam. The concentrations of soluble Zn of the three soils were low in a background solution of Ca（NO3）2. Citric acid, a common organic ligand found in the rhizosphere, was effective in mobilizing Zn in these soils; its presence enhanced the concentration of Zn in soil solution by citrate forming a complex with Zn. The ability of Zn to form a complex with citric acid in the soil solution was dependent on the concentration of citric acid, pH, and the concentration of the competing cation Ca^2＋. The pH of the soil solution determined the extent of desorption of Zn in solid phase in the presence of citric acid. The amounts of Zn released from the solid phase were proportional to the concentration of citric acid and inversely proportional to the concentration of Ca（NO3）2 background solution, which supplied the competing cation Ca^2＋ for the formation of a complex with citrate. When the soil suspension was spiked with Zn, the adsorption of Zn by the soils was retarded by citric acid via the formation of the soluble Zn-citrate complex. The dissolution of Zn in the presence of citric acid was pH dependent in both adsorption and desorption processes.     

柠檬酸盐和磷酸盐存在下酸性磷素酶在矿物和土壤胶体上的吸附

The aim of this work was to study the influence of phosphate and citrate, which are common inorganic andorganic anions in soils, on the adsorption of acid phosphatase by kaolin, goethite and the colloids separatedfrom yellow-brown soil (YBS) and latosol (LS) in central-south China. The YBS colloid has the major claymineral composition of 1.4 nm mineral, illite and kaolinite while the LS colloid mainly contains kaolinite andoxides. The adsorption isotherm of acid phosphatase on the examined soil colloids and minerals fitted tothe Langmuir model. The amount of enzyme adsorbed in the absence of ligands was in the order of YBScolloid ＞LS colloid＞kaolin≈goethite. In the presence of phosphate or citrate, the amounts of the enzymeadsorbed followed the sequence YBS colloid＞kaolin＞LS colloid＞goethite. The presence of ligands alsodecreased the binding energy between the enzyme and soil colloids or minerals. With the increase of ligandconcentration from 10 mmol L-1 to 400 m mol L-1, different behaviors for the adsorption of enzyme werefound in the colloid and mineral systems studied. A sharp decrease in enzyme adsorption was observed ongoethite while gradual decreases of enzyme adsorption were recorded in the two soil colloid systems. However,no any decrease was found for the amount of enzyme adsorbed on kaolin at higher ligand concentrations.When phosphate or citrate was introduced to the system before the addition of enzyme, the ligands usuallyenhanced the adsorption of enzyme. The results obtained in this study suggested the important role ofkaolinite mineral in the adsorption of enzyme molecules in acidic soils in the presence of various ligands.     

有机酸对高岭石, 针铁矿和水铝英石吸附镉的影响

Effects of organic acids （oxalic, acetic, and citric） on adsorption characteristics of Cadmium （Cd） on soil clay minerals （kaolinite, goethite, and bayerite） were studied under different concentrations and different pH values. Although the types of organic acids and minerals were different, the effects of the organic acids on the adsorption of Cd on the minerals were similar, i.e., the amount of adsorbed Cd with an initial solution pH of 5.0 and initial Cd concentration of 35 mg L^-1 increased with increasing concentration of the organic acid in solution at lower concentrations, and decreased at higher concentrations. The percentage of Cd adsorbed on the minerals in the presence of the organic acids increased considerably with increasing pH of the solution. Meanwhile, different Cd adsorption in the presence of the organic acids, due to different properties on both organic acids and clay minerals, on kaolinite, goethite, or bayerite for different pHs or organic acid concentrations was found.     

螯合剂对沉积物中铬的去向的影响

A laboratory investigation on reaction between chelating agents and chromium was conducted to evaluate the effect of chelating agents on the adsorption and desorption of chromium in sediment. The amount of adsorbed chromium(Ⅵ) in sediment decreased slightly by 5%-10% because of addition of chelating agents. Chelating agents inhibited the removal of Cr(Ⅲ) by sediment from solutions and the inhibiting effect was in the order: citric acid > tartaric acid > EDTA, salicylic acid. No effect of chelating agents on desorption of chromium in sediment was observed.     

阴离子对加入到土壤中的铅吸附与提取的影响

The effect of accompanying anions on the adsorbability and extractability of Pb added in soils was studied by using bach equilibria and incubation-extraction mothods.Pb concentration ranged between 0.48-2.41 mM in the adsorption experiment,and Pb added to soil from 2.14 to 19.31mM Pb/kg with an incubation time of 2-16 weeks in the incubation-extraction test in which 1M NH4OAc(pH 7) was taken as an extraction agent,and the Pb compounds used are PbCl2,Pb(NO3)2 and Pb(OAc)2.The values of pH50 for Pb retention and the parameters,b and k values,of Langmuir equation were used to distinguish the difference of adsorbability and extractability of Pb affected by anions,respectively.Judging from the results of either pH50 value or b value,the influences of Cl^- and NO3^- on the adsorbability and extractability of Pb in soils were similar but quite different from those of OAc^-.The relative loading capacities of soils to Pb calculated according to the extraction rate showed that the values of Pb(OAc)2 were higher than those of PbCl2 and Pb(NO3)2.     

苏云金芽胞杆菌毒素在累托石上的吸附与杀虫活性研究

The adsorption and desorption of the toxin from Bacillus thuringiensis strain WG-001 on rectorite were studied at different toxin and/or rectorite concentrations, pH values and temperatures. The insecticidal activity of the adsorbed toxin was evaluated by determining the lethal concentration to kill 50% of the larvae of Heliothis armigera （LC50）. The adsorption of the toxin on rectorite in sodium carbonate buffer （pH 9） reached equilibrium within 0.5-1.0 h and the adsorption isotherm of the toxin followed the Langmuir equation （R^2 〉 0.99）. In the pH range from 9 to 11 （carbonate buffer）, the adsorbed toxin decreased with increasing pH. The adsorption amounts decreased with increasing rectorite：toxin ratio. The adsorption was not significantly affected by the temperature between 10 and 50 ℃. The X- ray diffraction analysis indicated occurrence of the intercalation of the rectorite by the toxin. The infrared absorption spectrum showed that the binding of the toxin did not alter its structure. The LC50 wlues of the adsorbed toxin were smaller than those of the free toxin. The rectorite protected the toxin from ultraviolet irradiation damage. The desorption of the adsorbed toxin in water ranged from 37.5% to 56.4% and from 27.4% to 41.8% in a carbonate buffer. The desorption percentage also decreased with increasing rectorite：toxin ratio.     

Adsorption of Acrylonitrile on Some Soils and Minerals from Aqueous Solutions

Equilibrium and kinetic studies have been made on the adsorption of acrylonitrile(CH2=CHCN) on three soils and four minerals from aqueous solutions.It was shown that the organic matter was the major factor affecting the adsorption process in the soils.The conformity of the equilibrium data to linear type(one soil) and Langmuir type(two soils) isotherms indicated that different mechanisms were involved in the adsorption.This behavior appears bo be related to the hydrophobicity of soil organic matter due to their composition and E4/E6 ratio of humic acids.The adsorption kinetics were also different among the soils,indicating the difference in porosity of organic matter among the soils,and the kinetics strongly affected the adsorption capacity of soils for acrylonitrile.Acrylonitrile was slightly adsorbed from aqueous solutions on pyrophyllite with electrically neutral and hydrophobic nature,and practically not on montmorillonite and kaolinite saturated with Ca.However,much higher adsorption occurred on the zeolitized coal ash,probably caused by high organic carbon content(107g/kg).     

Adsorption of Potassium and Sodium Ions by Variable Charge Soils

Adsorption of potassium and sodium ions by four typical variable charge soils of South China was studied.The results indicated that the variable charge soils saturated with H and Al showed a much higher preference for potassium ions relative to sodium ions,and this tendence could not be changed by such factors as the pH,the concentration of the cations,the dielectric constant of solvent,the accompanying anions and the iron oxide content etc.,suggesting that this difference in affinity is caused by the difference in the nature of the two cations.It was observed that a negative adsorption of sodium ions by latosol and lateritic red soil in a mixed system containing equal amount of potassium and sodium ions at low pH,which is caused by a competitive adsorption of potassium and sodium ions and repulsion of positive charge on the surfaces of soil particles for cations.The adsorption of potassium and sodium ions increased with the decreases in the dielectric constant of solvent and the iron oxide content.Sulfate affected the adsorption of potassium and sodium ions through changing the surface properties of the soils.     

甲硫嘧磺隆在土壤中的吸附和解吸特性研究

Methiopyrsulfuron is a new low-rate sulfonylurea herbicide for weed control in wheat; however, there is a lack of published information on its behavior in soils. In this study, methiopyrsulfuron adsorption and desorption were measured in seven soils sampled from Heilongjiang, Shandong, Jiangxi, Sichuan, Anhui, and Chongqing provinces of China using a batch equilibrium method. The Freundlich equation was used to described its adsorption and desorption. Adsorption isotherms were nonlinear with the values of Kf-ads, the Freundlich empirical constant indicative of the adsorption capacity, ranging from 0.75 to 2.46, suggesting that little of this herbicide was adsorbed by any of the seven soils. Soil pH and organic matter content (OM) were the main factors influencing adsorption; adsorption was negatively correlated with pH and positively correlated with OM. Methiopyrsulfuron desorption was hysteretic on the soils with high OM content and low pH.     

沙粒中添加Ca2+、粘土以及富粘土对水溶性有机碳呼吸作用及其吸附的影响研究

Clay addition to light-textured soils is used to ameliorate water repellency and to increase nutrient retention. However, clay addition may also increase the potential to bind organic matter and thus C sequestration. Divalent calcium ions （Ca2＋） play an important role in binding of organic matter to clay because they provide the bridge between the clay particles and organic matter which are both negatively charged. In the first experiment, quartz sand was mixed with clay isolated from a Vertosol at rates of 0, 50 and 300 g kg-1, finely ground mature wheat residues （20 g kg-1） and powdered CaSO4 at 0, 5 and 10 g kg-1. Soil respiration was measured over 28 d. Compared to the sand alone, addition of isolated clay at 300 g kg-1 increased cumulative respiration with a stronger increase than that at 50 g kg-1. Addition of CaSO4 increased electrical conductivity, decreased sodium adsorption ratio and reduced cumulative respiration. The latter can be explained by enhanced sorption of organic matter to clay via Ca2＋ bridges. In a second experiment, isolated clay or subsoil of the Vertosol without or with powdered CaSO4 at 10 g kg-1 were used for a batch sorption with water-extractable organic C （WEOC） from wheat straw followed by desorption with water. Addition of 10 g kg-1 CaSO4 increased sorption and decreased desorption of WEOC in both subsoil and isolated clay. In the third experiment, subsoil of the Vertosol was used for a batch sorption in which WEOC was added repeatedly. Repeated addition of WEOC increased the concentration of sorbed C but decreased the sorbed proportion of the added WEOC. This indicates that sorption of WEOC may be underestimated if it is added only once in batch sorption experaments.     

Types of Crystalline Iron Oxides and Phosphate Adsorption in Variable Charge Soils

The types,contents and morphologies of crystalline Fe oxides and their relations to phosphate adsorption on the clay fractions in soils with varable charge in southern China were investigated by means of XRD,TEM,EMA and chemical analysis methods.Results indicated that the types and contents of crystalline Fe oxides varied with the soils examined.The dominant crystaline Fe oxide was hematite in the latosols and goethites in the red soils.In yellow-brown soils,the only crystalline Fe oxide was goethite.The difference between Ald and Alo came mainly from the Al Substituting for Fe in the Fe oxides.The crystal morphology of goethite appeared mainly as subrounded flat or iso-dimensional rather than acicular particles,Hematities occurred in plates of various thickness,Their MCDa/MCDc ratios in the latosols and red soils were generally above 1.5 and below 1.5,respectively.The MCD values of goethites and hematites were 15-25nm and 20-35nm,and their specific surface areas were 80-120m^2/g and 35-75m^2/g,respectively.The goethite crystals were generally smaller,Variations of the total amounts of crystalline Fe oxides in clay fractions were not related to plhophats adsorption.The types,contents and morphologies of crystalline Fe oxides in the soils remarkably affected phosphate adsorption characteristics of the soils.The phosphate adsorption of goethite was much greater than that of hematite,The higher th MCDa/MCDc ratio of hematite,the lower the phosphate adsorption.     

土壤磷酸盐的吸收对Cu2+二次吸附动力学的影响

The effects of sorbed phosphate on the kinetics of Cu^2 secondary adsorption on three major types of soils in southern and Central China were studied using the batch method and flow (or miscible displacement) techniques.Both of the methods showed that diffusions were the ratedetermining steps in the Cu^2 adsorption by the soils.By the flow method,the course of Cu^2 adsorption kinetics consisted of two steps-sn initial rapid process and a later slow process of Cu^2 adsorption;while by the batch method,the 90% of Cu^2 adsorption reaction was found to finish within first 1 minute.The results obtained using the flow method also indicated that for red soil and yellow-brown soil ,Cu^2 adsorptions during the initial reaction periods were restrained when the soils sorbed phosphate,whereas the adsorption reactions were stimulated at the final time,For grey Chao soil,sorbed phosphate retarded the Cu^2 adsorption in the whole reaction period.The results obtained using the batch method and low techniques all implied that the different effects of sorbed phosphate would be attributed to its effects on Cu^2 ion diffusion in soil solution.     

Adsorption of Chloride, Nitrate and Perchlorate by Variable Charge Soils

Two cells consisting of a chloride-selective electrode and a nitrate-selective electrode or of a chloride-selective electrode and a perchlorate-selective electrode were directly put in the soil suspension to determine the concentration ratios Cl-/ NO3- or Cl-/ ClO4- for studying the adsorption of the three anions by variable charge soils. It was found that all the concentration ratios CCl- / CNO3- and CCl- / CClO4- in suspension were smaller than unity when soil samples were in equilibrium with mixed KCl and KNO3 or KCl and KClO4 solutions of equal concentration. The order of the amount of chloride, nitrate and perchlorate adsorbed by variable charge soils was Cl-> NO3-> ClO4- when the soils adsorbed these anions from the solution containing equal concentrations of Cl-, NO3- and ClO4-. Such factors as the pH of the suspension, the iron oxide content of the soil etc. could affect the amounts and the ratios of anions adsorbed.     

电渗析可变电荷土壤中氢氧根离子的释放与氯离子吸附的关系

The release of hydroxyl ions from two variable charge soils associaed with the adsorption of chloride in NaClO4 solutions was examined.The complete release required about 10 minutes The release decreased with the increase in the NaClO4 concentration at first and eventually was little affected by the latter.The adsorption of Cl^-1 was almost linearly related with the quantity of NaCl added to the system,while the OH^- release-NaCl curve varied with the soil type and the concentration of NaClO4.The logarithm of the quantity of released OH^- was linearly related with the pH ,The ratio of release OH^- to adsorbed Cl^- was larger in dilute NaClO4 solutions than in concentrated solutions and decreased with increasing NaCl.     

磷的吸附对老成土和淋溶土中Cu、Zn离子吸附-解吸及其有效性的影响

Surface charge,secondary adsorption-desorption and form distribution of Cu^2 and Zn^2 in Ultisols and Alfisols having adsorbed phosphate were studied by potentiometric titration,adsorption equilibrium and sequential extraction method,respectively,The soil surface negative charges increased whereas the amount sequential extraction method,respectively.The soil surface ngative charges increased whereas the amount of positive charges decreased with increase of P adsorbed,The soil secondary adsorption capacity for Cu^2 and Zn^2 was positively significantly correlated with the amount of P adsorbed by the soils,which could be described by the Langmuir equation.The amounts of Cu^2 and Zn^2 desorption from soils were decreased after P adsorption by the soils and the relationship between them was linear,After the soils adsorbed P,form distribution of Cu^2 and Zn^2 in soils changed remarkably.