On the mechanism of specific phosphate adsorption by hydroxylated mineral surfaces: A review

Abstract

The mechanism of specific phosphate adsorption by hydroxy‐lated mineral surfaces comprises two aspects: the phosphate‐hydroxyl surface reaction and the configuration of the adsorbed phosphate ion. Evidence pointing to ligand exchange as the mechanism of the phosphate‐surface hydroxyl reaction include kinetics of adsorption and desorption; hydroxyl ion release; infrared spectroscopy, and stereochemical calculations. Data pertaining to the coordination of adsorbed phosphate on hydroxy‐lated mineral surfaces have not been conclusive overall. Isotopic exchange experiments and studies of desorption kinetics do not provide definitive information on surface coordination. Measurements of hydroxyl ion release and crystallographic calculations provide support for the existence of both monodentate and bidentate surface complexes of phosphate ions. Infrared spectroscopic investigations suggest a binuclear complex on dried, phosphated goethite. However, these studies cannot be extrapolated automatically to soil minerals, since the addition of water favors formation of a monodentate surface complex. Further research is needed to establish the configuration of adsorbed phosphate ions.     

Competitive and noncompetitive adsorption of silicate and phosphate by two acid Si-deficient soils and their effects on P and Si extractability

The effects of pH on the adsorption of silicate and phosphate, either singly or in competition, by two acid soils were investigated. Both soils adsorbed two to three times more P than Si and adsorption isotherms at pH 5.0, 5.5, 6.0 and 6.5 showed that increasing pH greatly increased Si adsorption but decreased that of P. Silicate adsorption was very low below pH 5.0, increased rapidly up to pH 9–10 before decreasing again. Adsorption of P was at a maximum at pH 2.0, decreased slowly up to pH 7.0 and then more rapidly above pH 7.0. When Si and P were added at equimolar concentrations, the presence of P decreased Si adsorption between pH 6.0 and 8.0 while the presence of Si decreased P adsorption in the pH region 6.0 and 11. Addition of calcium silicate at rates equivalent to 300, 600 and 1200 kg Si ha^?1 resulted in a progressive increase in soil pH. Separate samples of soil were treated with Ca(OH)₂ to give the same pH values so that the effect of Si could be identified. The highest rate of Si (1200 kg ha^?1 which gave a pH of 6.5) caused a significant decrease in P adsorption (as determined by adsorption isotherms) and an increase in resin-extractable P but the lower rates had little effect. Addition of P to the soil as calcium phosphate at rates equivalent to 30, 60 and 100 kg P ha^?1 all caused a decrease in Si adsorption capacity and an increase in CaCl₂-extractable Si. It was concluded that the strategy of adding Si to lower P requirements in acid soils is not likely to be effective while addition of fertilizer P may well lower Si adsorption and promote Si desorption and its increased mobility.     

Extraction methods for aluminium and iron in relation to phosphate adsorption

Abstract

Three extraction methods for aluminium and two for iron were compared with phosphate sorptivity (Bache and Williams index) for 40 tropical and 40 British soil samples. Extractable aluminium was well correlated with phosphate sorptivity in both groups, but extractable iron was well correlated only in British soils. In general methods which extracted more sesquioxides gave higher correlation coefficients. With aluminium, N ammonium acetate (pH 4.8) or 0.1N HCl gave better correlation than N KCl, while with iron dithionitecitrate was better than 0.1N HCl.     

Effects of soil organic matter on pH-dependent phosphate sorption by soils

Effects of soil organic matter (80M) on P sorption of soils still remain to be clarified because contradictory results have been reported in the literature. In the present study, pH-dependent P sorption on an allophanic Andisol and an alluvial soil was compared with that on hydrogen peroxide (H₂0₂)-treated, acid-oxalate (OX)-treated, and dithionite-citrate- bicarbonate (DCB)-treated soils. Removal of 80M increased or decreased P sorption depending on the equilibrium pH values and soil types. In the H₂O₂ OX-, and DCB-treated soils, P sorption was pH-dependent, but this trend was not conspicuous in the untreated soils. It is likely that 80M affects P sorption of soils through three factors, competitive sorption, inhibition of polymerization and crystallization of metals such as AI and Fe, and flexible structure of metal-80M complexes. As a result, the number of available sites for P sorption would remain relatively constant in the wide range of equilibrium pH values in the presence of 80M. The P sorption characteristics were analyzed at constant equilibrium pH values (4.0 to 7.0) using the Langmuir equation as a local isotherm. The maximum number of available sites for P sorption (Q _max) was pH-dependent in the H₂0₂-, OX-, and DCBtreated soils, while this trend was not conspicuous in the untreated soils. Affinity constants related to binding strength (K) were less affected by the equilibrium pH values, soil types, and soil treatments, and were almost constant (log K ≈ 4.5). These findings support the hypothesis that 80M plays a role in keeping the number of available sites for P sorption relatively constant but does not affect the P sorption affinity. By estimating the Q _max and K values as a function of equilibrium pH values, pH-dependent P sorption was well simulated with four or two adjustable parameters. This empirical model could be useful and convenient for a rough estimation of the pH-dependent P sorption of soils.     

铝(氢)氧化物对有机酸和磷酸根的竞争吸附研究

研究了磷 /草酸浓度比 (Cp/Cox)、草酸 (OX)与磷 (P)加入顺序、多种有机酸共存等条件下铝 (氢 )氧化物 (Al(OH)x)对有机酸和磷的吸附量变化。结果表明 :磷浓度一定时 ,随Cp/Cox减小 ,Al(OH)x吸附磷量降低 ,吸附OX量增高 ,吸附阴离子总量一般随浓度升高而增加 ;Cp/Cox相同时 ,5种加入方式吸P顺序为P/OX P -OX OX +P OX -P OX/P ;Cp/Cox不同时 ,Al (OH)x吸附配位体的总量也相应变化 ;几种有机酸共存时 ,Al(OH)x对体系中的各种阴离子均有吸附 ,且相互影响和制约 ,总吸附量取决于离子种类和浓度 ,3种有机酸影响P吸附量的顺序为柠檬酸 (CA) 草酸 (OX) 酒石酸 (Tar) ;Al (OH)x加磷后随平衡时间延长 ,先吸附的OX和CA对吸附P量的影响逐渐减弱 ,它们的相对亲合力越来越成为主导因素。     

Studies on the maturing process of newly reclaimed soils under cultivation (Part 5) Change of the methoxyl content and the heat of combustion of soil humus under cultivation

It has been considered by investigators, no matter whether they stand by the lignin-protein complex theory or not, that lignin plays an important role in the humus formation of plant residues. When plant residues are added to the soil, though almost all the plant constituents are decomposed, only lignin accumulates in the soil as a component of humus, as it is resistant to the microbial decomposition. However, lignin does not remain unchanged in this case and is thought to be modified, either through chemical agencies or as a result of specific microbial action. Though it is not yet fully clarified what changes it undergoes in the humification process, at least it is indicated that the methoxyl, as a characteristic radical of lignin, is attacked during the process.     

Effect of drying soil on the measurement of phosphate adsorption

Abstract

Drying a soil increased the measured adsorption of phosphate; the drier the soil the larger was the effect. After drying at moderate temperatures, the effects were greatly reduced by re‐moistening the soil for a day before measuring adsorption.     

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.     

Phosphate release from synthetic glasses and inhibition of phosphate fixation on ferric hydroxide

Release of phosphate from glasses in the systems basalt-K₃PO₄ granite-K₂SiO₃ Na₂SiO₃-apatite has been studied. Equilibrium leachate concentrations in water are attained in 3-5 hr (K⁺, 5-60 μg cm^-3; PO₄ ³-, 2-15 μg cm^-3). Glass composition, pH, and grain size influence solubility.

Phosphate fixation on freshly precipitated Fe(OH)₃ and on iron-rich laterites appear to be inhibited when glasses are rich in Na-K silicates. This may be due to surface modification of Fe(OH)₃ by the formation of sodium ferric silicates which are known to be stable at low temperatures.     

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.     

pH对针铁矿表面磷酸盐吸附的化学形态的影响

Chemical forms of the phosphate adsorbed on goethite surfaces and characteristics of the coordinate groups which exchange with P on goethite surfaces in solutions with different pll values were investigated.Results showed that the chemical forms of P on goethite surfaces changed from the dominance of monodentate corrdination to that of bidentate one with increasing pH of the solution.By influencing types of phosphate ions in solutions,pH affected the chemical forms of P on goethite surfaces,The amount of OH^- displaced by phosphae on goethite surfaces was the most at pH 7.0,the second at pH 9.0,and the least at pH 4.5.     

Sorption of phosphate by aluminium and iron(iii)-hydroxy species on mica surfaces

Freshly cleaved mica sheets with aluminium- or iron(III)-hydroxy species on the cationexchange surface were prepared by suitable treatment with AlCl₃ or FeCl₃. These surfaces were considered as model soilk mineral surfaces and their interaction with phosphate studied using techniques previously developed for the study of single planar surfaces.Adsorption isotherms for both the iron(III) and aluminium systems were very similar and could be interpreted as two Freundlich isotherms indicating two different adsorption processes, one operating below a solution concentration of 10^?5 M and thee other above. Results obtained from the continuous monitoring of adsorption indicate that a rearrangement of adsorbed phosphate occurs with time on both the aluminium- and iron(III)hydroxy surfaces. This rearrangement reduces the rate of desorption and could be a cause of phosphate fixation in soils.     

玉米秸秆对Cr(VI)表观吸附过程的研究

玉米秸秆是一种重要的有机物料,它能通过表观吸附过程(包括物理吸附和化学反应过程)降低Cr(VI)污染。本试验采用间歇振荡法,初步研究了玉米秸秆对Cr(VI)的表观吸附动力学和等温线,并用吸附方程进行拟合。结果表明:玉米秸秆对Cr(VI)的表观吸附动力学以一级动力学方程为最优方程;表观吸附等温线可用Freundlich、Langmuir和Temkin方程描述,而以Freundlich方程的拟合效果最好;土壤或水体中的Cr(VI)含量越高,玉米秸秆的修复效果越差。     

Pectin adsorption on amorphous Fe/Al hydroxides and its effect on surface charge properties and Cu(II) adsorption

Purpose

The purpose of this study was to elucidate the mechanisms for pectin-enhanced adsorption of heavy metal cations on variable charge minerals.

Materials and methods

Batch experiments were conducted to investigate the adsorption of pectin and copper(II) by amorphous Fe/Al hydroxides. The morphology, mineralogy, and functional groups of pectin–Fe/Al hydroxides were examined using X-ray diffraction, scanning electron microscopy, and Fourier transform infrared spectroscopy analysis.

Results and discussion

The amount of pectin adsorbed by amorphous Al(OH)₃ was much greater than that by amorphous Fe(OH)₃ at pH values between 3.5 and 6.5 due to the higher positive charge density on Al(OH)₃ and greater electrostatic attraction between the hydroxide and pectin compared with Fe(OH)₃. The addition of pectin decreased the positive surface charge on amorphous Fe and Al hydroxides. The presence of pectin enhanced the adsorption of Cu(II) by the Fe and Al hydroxides. The increase in Cu(II) adsorption on amorphous Fe hydroxide was more obvious at low pH values than at higher pH values, while an opposite changing trend was observed for amorphous Al hydroxide. At pH 3.9, 4.3, and 4.9, pectin increased Cu(II) adsorption by Fe hydroxide from 24.4, 76.6, and 177.0 mmol/kg to 61.6, 98.8, and 192.0 mmol/kg, i.e., Cu(II) adsorption was increased by 37.2, 22.2, and 15.0 mmol/kg, respectively. At pH 4.3 and 4.9, pectin increased Cu(II) adsorption by Al hydroxide from 3.7 and 27.0 mmol/kg to 17.3 and 69.4 mmol/kg, i.e., Cu(II) adsorption was increased by 13.6 and 42.4 mmol/kg, respectively. The greater adsorption of pectin by Al hydroxide was mainly responsible for the larger enhancement of pectin on Cu(II) adsorption on Al hydroxide at higher pH values compared with Fe hydroxide.

Conclusions

The adsorption of pectin on Fe and Al hydroxides decreased the positive charge on the hydroxides and thus enhanced the adsorption of Cu(II) by the hydroxides.

     

Effect of phosphate and sulfate fertilizers on selenium uptake by wheat (Triticum aestivum)

The objective of this study was to investigate whether oxyanionic phosphate (P) and sulfate (S) fertilizer management could influence selenium (Se) uptake by wheat (Triticum aestivum) in medium and high Se areas. Field studies were established at two locations for two growing seasons in central South Dakota, USA. Phosphate fertilizer was applied using three different methods (banded with seed, surface-broadcasted in the fall, or surface-broadcasted in the spring) using six different P rates. Sulfate fertilizers were broadcasted at four rates in the fall. Selenium concentration in wheat grain was significantly influenced by the interaction of P application methods and rates, but it was dependent on location. Grain Se concentration decreased in high Se availability soil when P fertilizer was applied, due to the dilution effect. Grain Se concentration and uptake was significantly decreased as S applications increased due to the competition effect, but the depression was apparent in high Se availability soil. The results from this study showed that P and S fertilizer management can influence Se level in wheat grain grown in naturally high Se areas, even though overall grain Se level was strongly associated with location variation.     

Adsorption of glycerophosphate on goethite (α‐FeOOH): A macroscopic and infrared spectroscopic study

Adsorption, desorption, and precipitation reactions at environmental interfaces govern the bioavailability, mobility, and fate of organic phosphates in terrestrial and aquatic environments. Glycerophosphate (GP) is a common environmental organic phosphate, however, surface adsorption reactions of GP on soil minerals have not been well understood. The adsorption characteristics of GP on goethite were studied using batch adsorption experiments, zeta (ζ) potential measurements, and in situ attenuated total reflectance‐Fourier transform infrared spectroscopy (ATR‐FTIR). GP exhibited fast initial adsorption kinetics on goethite, followed by a slow adsorption. The maximum adsorption densities of GP on goethite were 2.00, 1.95, and 1.44 μmol m^?2 at pH 3, 5, and 7, respectively. Batch experiments showed decreased adsorption of GP with increasing pH from 3 to 10. Zeta potential measurements showed a remarkable decrease in the goethite isoelectric point upon GP adsorption (from 9.2 to 5.5), suggesting the formation of inner‐sphere surface complexes. In addition, the ATR‐FTIR spectra of GP sorbed on goethite were different from those of free GP at various pH values. These results suggested that GP was bound to goethite through the phosphate group by forming inner‐sphere surface complexes.     

Effects of phthalic and salicylic acids on Cu(II) adsorption by variable charge soils

In the present study, the effect of two substituted benzoic acids on Cu(II) adsorption onto two variable charge soils was investigated, with the emphasis on the adsorption and desorption equilibrium of Cu(II). Results showed that the presence of organic acids induced an increase in Cu(II) adsorption onto the two soils. The extent of the effect was related to the initial concentrations of Cu(II) and organic acid, the system pH, and the nature of the soils. The effect of organic acids was greater for Oxisol than for Ultisol. Phthalic acid affected Cu(II) adsorption to a greater extent than salicylic acid did. The effect of organic acids varied with pH. The adsorption of Cu(II) induced by organic acids increased with increasing pH and reached a maximum value at approximately pH 4.5, and then decreased. It can be assumed that the main reason for the enhanced adsorption of Cu(II) is an increase in the negative surface charge caused by the specific adsorption of organic anions on soils because the desorption of Cu(II) adsorbed in organic acid systems was greater than that for the control. The desorption of Cu(II) absorbed in both control and organic acid systems also increased with increasing pH; it reached a maximum value at pH ∼5.25 for control and salicylic acid systems and at pH ∼5.1 for a phthalic acid system, then decreased. This interesting phenomenon was caused by the characteristics of the surface charge of variable charge soils.     

莱州湾海涂海水灌溉菊芋的磷肥效应的研究

在连续3年莱州湾海涂海水灌溉试验的基础上,2003年就不同浓度海水灌溉菊芋的磷肥效应进行了田间试验研究。结果表明,在海水灌溉下,磷肥对菊芋的增加产量与增产幅度均高于淡水灌溉,在50%海水浓度范围内,随着灌溉海水浓度增加磷肥的增产效应也逐渐提高,以50%浓度海水灌溉磷肥增产效应最大;海水灌溉下,施磷肥能显著促进菊芋对K+、Ca2+和Mg2+等有益离子的吸收与运输,尤其是明显提高菊芋在海水灌溉下的SK,Na,而抑制菊芋对Na+及Cl-等有害离子的吸收;在75%的海水浓度范围内,灌溉的海水浓度越高,磷肥对上述离子的影响强度越大;海水灌溉下,施用磷肥明显促进菊芋根部氮的含量,P3(P2O560kg/hm2)与P1(P2O50kg/hm2)处理相比较,在淡水、25%海水、50%海水、75%海水灌溉处理下,菊芋根部含氮量增加0.43、0.64、0.64、0.51个百分点。     

Mutual influence of copper and paraquat on their adsorption in soil

Paraquat and copper (Cu) are commonly used and detected in soil.Therefore,it is important to understand their mobility in the environment.In this study,the competitive effects of paraquat and Cu on their adsorption in five representative Chinese soils were investigated using batch adsorption equilibrium experiments and spectroscopic analysis.The results showed that the adsorption of paraquat in soil varied with soil type and was positively correlated with both soil cation exchange capacity and o...