Forms of Rare Earth Elements in Soils: Ⅱ. Differentiation of Rare Earth Elements

The present paper deals mainly with the relationships between the distribution of rare earth elements (REE) in different forms in soils and the atomic number and with the odd-even phenomenon in the distribution of ionic lanthanides in soils.The enrichment tendency of light REE relative to heavy REE in soils was pointed out on the experimental results about the proportions of Ce-group and Y-group elements in different REE forms in soils.Meanwhile,the differentiation of Tm in different soil REE forms was compared and the reasons why Tm is enriched in soils were preliminarily discussed.     

Forms of Rare Earth Elements in Soils: Ⅰ. Distribution

The distribution of rare earth element (REE) forms in soils is given in the present paper on the basis of sequential fractionation and determination of 34 representative surface soils collected from all parts of China.Results obtained show that the extraction rate of water soluble and exchangeable REE had the odd-even phenomenon and that of organically bound REE from La to Lu tended to reduce gradually with the increase of atomic number.The stability of Sc and the activity and enrichment of Tm in soils are proposed.Furthermore,the paper makes a preliminary discussion on the differences in the concentration distribution of various forms of individual REE in some soils.     

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.     

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.     

湿地土壤NH4+吸附解吸对冻融循环的响应

Nitrogen (N) cycling in boreal peatland ecosystems may be influenced in important ways by freeze-thaw cycles (FTCs).Adsorption and desorption of ammonium ions (NH + 4) were examined in a controlled laboratory experiment for soils sampled from palustrine wetland,riverine wetland,and farmland reclaimed from natural wetland in response to the number of FTCs.The results indicate that freeze-thaw significantly increased the adsorption capacity of NH + 4 and reduced the desorption potential of NH + 4 in the wetland soils.There were significant differences in the NH + 4 adsorption amount between the soils with and without freeze-thaw treatment.The adsorption amount of NH + 4 increased with increasing FTCs.The palustrine wetland soil had a greater adsorption capacity and a weaker desorption potential of NH + 4 than the riverine wetland soil because of the significantly higher clay content and cation exchange capacity (CEC) of the riverine wetland soil.Because of the altered soil physical and chemical properties and hydroperiods,the adsorption capacity of NH + 4 was smaller in the farmland soil than in the wetland soils,while the desorption potential of the farmland soil was higher than that of the wetland soils.Thus,wetland reclamation would decrease adsorption capacity and increase desorption potential of NH + 4,which could result in N loss from the farmland soil.FTCs might mitigate N loss from soils and reduce the risk of water pollution in downstream ecosystems.     

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.     

草酸对土壤和矿物中钾素的释放规律研究

Oxalic acid plays an important role in improving the bioavailability of soil nutrients. Batch experiments were employed to examine the influences of oxalic acid on extraction and release kinetics of potassium （K） from soils and minerals along with the adsorption and desorption of soil K^＋. The soils and minerals used were three typical Chinese soils, black soil （Mollisol）, red soil （Ultisol）, and calcareous alluvial soil （Entisol）, and four K-bearing minerals, biotite, phlogopite, muscovite, and microcline. The results showed that soil K extracted using 0.2 mol L^-1 oxalic acid was similar to that using 1 mol L^-1 boiling HNO3. The relation between K release （y） and concentrations of oxalic acid （c） could be best described logarithmically as y = a ＋ blogc, while the best-fit kinetic equation of K release was y = a ＋ b√t, where a and b are the constants and t is the elapsed time. The K release for minerals was ranked as biotite 〉 phlogopite 〉〉 muscovite 〉 microcline and for soils it was in the order： black soil 〉 calcareous alluvial soil 〉 red soil. An oxalic acid solution with low pH was able to release more K from weathered minerals and alkaline soils. Oxalic acid decreased the soil K^＋ adsorption and increased the soil K^＋ desorption, the effect of which tended to be greater at lower solution pH, especially in the red soil.     

Effects of Organic Anions on Phosphate Adsorption and Desorption from Variable—Charge Clay Minerals and Soil

Effects of citrate and tartrate on phosphate adsorption and desorption from kaolinite,goethite,amorphous Al-oxide and Ultisol were studied.P adsorption was significantly decreased as the concentration of the organic anions increased from 10^-5 to 10^-1 M.At 0.1 M and pH 7.0,tartrate decreased P adsorption by 27.6%-50.6% and citrate by 37.9-80.4%,depending on the kinds of adsorbent.Little Al and/or Fe were detected in the equilibrium solutions,even at the highest concentration of the organic anions.Effects of the organic anions on phosphate adsorption follow essentially the competitive adsorption mechanism.The selectivity coefficients for competitive adsorption can be used to compare the effectiveness of different organic anions in reducing P adsorption under given gonditions. Phosphate desorption was increased by 3 to 100 times in the presence of 0.001 M citrate or tartrate compared to that in 0.02 M KCl solution alone.However,for all the soil and clay minerals studied the amount of P desorbed by citrate or tartrate was generally lower than or close to that of isotopically exchangeable P.The effect of organic anions on phosphate desorption arises primarily from ligand exchange.     

根瘤菌存在下土壤胶体和矿物对镉的吸附

Experiments were conducted to study the adsorption of Cd on two soil collids(red soil and yellowbrown soil) and three variable-charge minerals (goethite,noncrystalline Fe oxide and kaolin) in the absence and presence of rhizobia.The tested strain Rhizobium fredii C6,tolerant to 0.8 mmol L^-1 Cd,was selected from 30 rhizobial strains.Results showed that the isotherms for the adsorption of Cd by examined soil colloids and minerals in the presence of rhizobia could be described by Langmuir equation.Within the range of the numbers of rhizobial cells studied,the amount of Cd adsorbed by each system increased with increasing rhizobial cells,Greater increases for the adsorption of Cd were found in red soil and kaolin systems.Rhizobia influence on the adsorption of Cd by examined soil colloids and minerals was different from that on the adsorption of Cu.The presence of rhizobia increased the adsorption affinity of soil colloids and minerals for Cd,particularly for the goethite and kaolin systems.The discrepancies in the influence of rhizobia on the adsorbability and affinity of selected soil colloids and minerals for Cd suggesed the different interactions of rhizobia with various soil components.It is assumed that bacterial biomass plays an important role in controlling the mobility and bioavailability of Cd in soils with kaolinite and goethite as the major colloidal compnents,such as in variable-charge soil.     

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.     

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).     

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.     

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.     

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 Potassium and Calcium Ions by Variable Charge Soils

Interactions of potassium and calcium ions with four typical variable charge soils in South China were examined by measuring pK-0.5pCa value with a potassium ion-selective electrode and a calcium ion-selective electrode,and pK value with a potassium ion-selective electrode.The results showed that adsorption of potassium and calcium ions increased with soil suspension pH,and the tendency of the pK-0.5pCa value changing with pH differed with respect to pH range and potassium to calcium ratio.Adsorption of equal amount of calcium and potassium ions led to release of an identical number of protons,suggesting similar adsorption characteristics of these two ions when adsorbed by variable charge soils.Compared with red soil,latosol and lateritic red soil had higher adsorption selectivities for calcium ion.The red soil had a greater affinity for potassium ion than that for calcium ion at low concentration,which seems to result from its possession of 2:1 type minerals,such as vermiculite and mica with a high affinity for potassium ion.The results indicated that adsorption of potassium and calcium ions by the variable charge soils was chiefly caused by the electrostatic attraction between the cations and the soil surfaces.Moreover,it was found that sulfate could affect the adsorption by changing soil surface properties and by forming ion-pair.     

Effect of Continuous Vegetable Cultivation on PhosphorusLevels of Fluvo-Aquic Soils

oil P status, inorganic P fractions, and P sorption properties were studied using sandy fluvo-aquic horticultural soils,which are high in organic matter content for vegetable production in comparison with a soil used for grain crop productionin Zhengzhou, Henan Province, China. P fractions, Olsen-P, and OM were determined at different depths in the soilprofile and sorption isotherm experiments were performed. Most P in excess of plant requirements accumulated in thetopsoil and decreased with soil depth. Total P, inorganic P, and OM concentrations increased with continued horticulturaluse.Olsen-P concentrations in the 0-20 cm depth of horticultural soils were 9 to 25 times higher than those of the graincrop soil. A linear transformation of the Langmuir equation showed that the P adsorption maximum (491.3 mg P kg^-1)and the maximum phosphate buffering capacity (162.1 L kg^-1) for 80-100 cm were greater in the grain crop soil than thehorticultural soils. Thus, the most immediate concern with excess P were in areas where heavy P fertilizer was used forvegetable crops and where soil P sorption capacities were low due to sandy soils and high organic matter content.     

紫色水稻土的有机金属-矿物胶体复合物对磷的吸附、解吸特征

The kinetic characteristics of P adsorption and desorption by organo-mineral colloidal complexes (OMC) were studied using acid, calcareous and neutral purple paddy soils taken from Chongqing and Sichuan, China. The results showed that the P adsorption capacity of the organo-mineral colloidal complexes differed with the soil tyes, being higher for the acid and calcareous purple soils than for the neutral purple soils. Partial removal of the organic matter increased the adsorption capacity of the colloidal complexes. A very significant positive correlation was found between the amounts of P desorbed from OMC and the P saturation degrees. The P adsorption reaction was quick at the early stage and slowed later. The raise of temperature increased P adsorption capacity and P adsorption rate of the colloidal complexes. The adsorption processes could be described by the Elovich equation.     

Adsorption of emerging sodium p-perfluorous nonenoxybenzene sulfonate (OBS) onto soils: Kinetics, isotherms and mechanisms

The widespread use of sodium p-perfluorous nonenoxybenzene sulfonate(OBS), a typical alternative to perfluorooctane sulfonate, has resulted in potential threats to the environment, but the adsorption behavior of OBS in soils has not yet been reported. In this study, the adsorption behaviors of OBS on five soils with different physicochemical properties were investigated. The rate of OBS adsorption was fast, and most of the OBS uptake was completed within 12 h. The good model fit of OBS adsorption to the pseudo-second-order and Elovich models indicated the occurrence of chemical adsorption. The adsorption isotherms of OBS on the soils were better described by the Freundlich model than by the Langmuir model, suggesting that the OBS adsorption sites on the soils were heterogeneous. This is possibly associated with various adsorption mechanisms including hydrophobic, π-π, hydrogen bonding, and electrostatic interactions,further confirmed by the good model fit to the D-R isotherm. Adsorption of OBS occurred on the soils, and the adsorption process was spontaneous and endothermic. In addition, the soils were more suitable for OBS adsorption at lower pH values due to the stronger electrostatic adsorption. The OBS adsorption on the soils decreased with the increase of soil depth from 0 to 30 cm. Moreover, the presence of organic matter and ammonia nitrogen in the soils was favorable for OBS adsorption, and these parameters decreased with increasing soil depth, making OBS adsorption less prominent in the deeper soil. This study indicates that OBS is easily enriched in surface soils, and that soil organic matter and ammonia nitrogen significantly affect OBS migration in soil.     

Effect of Zn Adsorption on Charge of Variable Charge Soils

The variation in appa rent carge of two typical variable charge soils resulting from Zn adsorption were studied by KCl saturation and NH4NO3 replacement methods.Results showed that zinc were adsorbed specifically to those sites with negative charge.As in different pH ranges,the percantages of specific and electrostatic adsorptions of zine and the mechanisms of specific adsorption were different,the effects of Zn adsorption on apparent charge were varied and could be characterized as:when 1 mmol Zn^2 was adsorbed,a change about 1 mmol in the apparent charge was observed in the low pH range(1),1.4 to 1.5mmol in the moderate pH range(II) and 0.55 to 0.6mmol in the high pH range (III).These experimental data,in terms of soil charge,proved once more author‘s conclusion in the preceding paper(Sun,1993) that in accordance with the behaviors of Zn adsorption by the variable charge soils in relation to pH,three pH ranges with different adsorption mechanisms were delineated;that is,in Range I,specific adsorption was the predominant mechanism,in Ranges II and III,specific and electrostatic adsorptions co-existed,but their specific adsorption mechanisms were not identical.     

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.