Phosphate reactions with natural allophane, ferrihydrite and goethite

The reactions of phosphate with natural samples of allophane, ferrihydrite, hematite and goethite were measured for up to 30 d. The amount of phosphate sorbed on allophane showed the biggest increase with time whereas the amount sorbed on goethite showed the least increase with time. The total amount of phosphate sorbed either at high levels of phosphate addition or after 10 d followed the order hematite < goethite < ferrihydrite < allophane and was probably related to the specific surface. Si was desorbed as phosphate was adsorbed on the minerals.
The reactions of phosphate on allophane involved rapid, strong adsorption, probably at defect sites, followed by weaker adsorption, followed, probably, by disruption of the allophane structure together with precipitation of aluminium phosphates. Previous suggestions either of diffusive penetration of phosphate into surfaces or about the formation of aluminium phosphate coatings, are unlikely to hold for allophane, if all the Al is at the surface and if the structure can be ruptured.
The reactions of phosphate with iron oxides involved a rapid, strong ligand exchange, followed by weaker ligand exchange, and, probably, by a relatively slow penetration at defect sites and pores. Highly crystalline goethite has virtually no slow reaction and therefore solid-state diffusion of phosphate does not readily occur. The extent of phosphate uptake during the slow penetration reactions probably depends on the degree of crystallinity or porosity of iron oxides.
The most reactive adsorbents, such as allophane, ferrihydrite and Al-humus complexes do not have planar surfaces, and this needs to be considered when modelling phosphate reactions.     

Simple modelling of the sorption of iron‐cyanide complexes on ferrihydrite

The sorption of the iron‐cyanide complexes ferricyanide, [Fe(CN)₆]^3—, and ferrocyanide, [Fe(CN)₆]^4—, on ferrihydrite was investigated in batch experiments including the effects of pH (pH 3.5 to 8) and ionic strength (0.001 to 0.1 M). The pH‐dependent sorption data were evaluated with a model approach by Barrow (1999): c = a exp(bS)S/(S_max‐S), where c is the solution concentration; S is the sorbed amount; S_max is maximum sorption; b is a parameter; and a is a parameter at constant pH. Ferricyanide sorption was negatively affected by increasing ionic strength, ferrocyanide sorption not at all. More ferricyanide than ferrocyanide was sorbed in the acidic range. In the neutral range the opposite was true. Fitting the pH‐dependent sorption to the model resulted in a strong correlation for both iron‐cyanide complexes with a common sorption maximum of 1.6 μmol m^—2. Only little negative charge was conveyed to the ferrihydrite surface by sorption of iron‐cyanide complexes. The sorption of iron‐cyanide complexes on ferrihydrite is weaker than that on goethite, as a comparison of the model calculations shows. This may be caused by the lower relative amount of high‐affinity sites present on the ferrihydrite surface.     

石灰性土壤与磷酸盐的反应及吸持态磷的同位素交换性

本文研究了种石灰性土壤（Ｌｏｕ土）与磷酸盐的反应动态过程，短期反应的等温吸附研究表明，在低磷浓度下，以吸附反应机制为主，吸持态磷的同位素交换性随着吸持量的增加而增加；在高磷浓度下，以形成磷酸盐的沉淀反应机制为主，吸持态磷的同位素交换性随着反应时间的延长和吸持量磷数量的增加而了降低。认为在低施磷水平下，土壤中铁，铝氧化物对磷的吸持起重要作用。本文还探讨了在长期（２６０天）恒温恒湿培养过程中，土壤可溶     

Sorption of organic acids in acid soils and its implications in the rhizosphere

Organic acids have been implicated in many soil-forming and rhizosphere processes, but their fate in soil is poorly understood. We examined the sorption of four simple short-chain organic acids (citric, oxalic, malic and acetic) in five acid soils and on synthetic iron hydroxide (ferrihydrite). The results for both soils and ferrihydrite indicated that the sorption depended on concentration in the following order of strength: phosphate >> oxalate > citrate > malate >> acetate. The sorption reactions in soil were shown to be little influenced by pH, whereas for ferrihydrite, sorption of all ligands increased strongly with decreasing pH. The sorption of organic anions onto ferrihydrite was influenced to a lesser extent by the presence of metal cations in solution. From the results we calculated that when organic acids enter solution they rapidly become sorbed onto the soil's exchange complex (> 80% within 10 min), and we believe that this sorption will greatly diminish their effectiveness to mobilize nutrients from the rhizosphere.     

Role of root exudates on the sorption of arsenate by ferrihydrite

Iron oxy‐hydroxides in soil are known to have a large affinity for arsenate (As(V)) inorganic species. At the soil–root interface such mineral components are embedded by mucilaginous material that is secreted from continuously growing root cap cells. In order to determine the role of plant mucilages in As(V) sorption by iron oxy‐hydroxides, we layered a calcium (Ca)‐polygalacturonate network (CaPGA) on to amorphous iron (Fe) (III) hydroxide (ferrihydrite, Fh) particles. The scanning electron micrographs of the CaPGA network coating the ferrihydrite (Fh–CaPGA) show a regular structure with a honeycomb‐like pattern where interlacing fibrils form a porous system. The FT‐IR spectra of Fh–CaPGA suggest that CaPGA fibrils are retained by the surface Fe(III) nuclei of Fh through electrostatic interactions. The sorption experiments carried out at pH 4.3 and 5.8 indicated a smaller amount of As(V) sorbed by Fh–CaPGA than by Fh alone, being less after 3 and 24 hours of reaction by about 70 and 30%, respectively. The sorption of As(V) by Fh was also studied in the presence of caffeic acid (CAF), an important root exudate. Simultaneous sorption kinetics show that As(V) sorption by Fh is almost independent of CAF concentration, indicating a greater affinity of arsenate ions towards the Fh surfaces. However, the amount of As(V) sorbed by the Fh coated by CaPGA, in the presence of 0.25, 0.5 and 1.0 mm CAF, is markedly smaller by about 20, 27 and 40%, respectively, than that found in the As(V)–CAF‐Fh ternary systems. This is caused mainly by redox reactions involving CAF and the surface Fe(III) nuclei of Fh leading to the formation of CAF oxidation products which prevent As(V) sorption.     

Die Sorption von Phosphat an carbonatreichen Unterwasserböden

The sorption of phosphate by underwater soils rich in carbonate The phosphate sorption isotherms for carbonate rich under water soils (Unterwasserboden) can frequently be linearized by a modified Freundlich-isotherm when one assumes that, because of previously sorbed phosphate, the concentration of the equilibrium soil solution, P_1,0 is greater than 0. However, in many cases, the character of the phosphate sorption can be adequately determined with only one phosphate addition (P_s,500). Both methods show that for dried samples from under water soils, the samples from reduced horizons have a higher P sorption than for the associated oxidized horizons. This can be explained by the presence of very sorption active ferrihydrite which has precipitated from previously biologically reduced material.     

A mechanistic model for describing the sorption and desorption of phosphate by soil

A model of phosphate reaction is constructed and its output compared with observations for the sorption and desorption of phosphate by soil. The model has three components: first, the reaction between divalent phosphate ions and a variable-charge surface; second, the assumption that there is a range of values of surface properties and that these are normally distributed; third, the assumption that the initial adsorption induces a diffusion gradient towards the interior of the particle which begins a solid-state diffusion process. The model closely describes the effects on sorption of phosphate of: concentration of phosphate, pH, temperature, and time of contact. It also reproduces the effects on desorption of phosphate of: period of prior contact, period and temperature of desorption, and soil: solution ratio. The model is general and should apply to other specifically adsorbed anions and cations. It suggests that phosphate that has reacted with soil for a long period is not ‘fixed’ but has mostly penetrated into the soil particles. The phosphorus can be recovered slowly if a low enough surface activity is induced.     

The effects of phosphate on zinc sorption by a soil

Zinc sorption curves were obtained after treatment of a soil with several rates of phosphate and with two rates of lime. The lime permitted evaluation of the effects of phosphate on Zn sorption via its effects on pH. The phosphate was either incubated with the soil at a high temperature before reaction with Zn or was supplied at the same time as the Zn. This produced treatments with similar concentration of phosphate in solution but different amounts of sorbed phosphate.
Two distinct effects of phosphate addition on Zn sorption were detected. One arose from effects of phosphate on pH. This effect could be large and could either increase or decrease Zn sorption depending on the direction of the pH effect. A second effect was correlated with the amount of sorbed phosphate and was assumed to operate through the effects of phosphate on charge. The effects were small at low levels of Zn but larger at higher levels. This suggested that Zn and phosphate were sorbed at opposite ends of a spectrum of electrostatic potentials and overlap only occurred when the level of application was high. A third possible effect, due to reaction of the soil with zinc phosphate complexes in solution, was not proved.     

the effect of phosphate on the transformation of ferrihydrite into crystalline products in alkaline media

The presence of phosphate retards the transformation of ferrihydrite into crystalline products. Increasing phosphate from 0 to 1 mole % results in an order of magnitude decrease in the rate of transformation of ferrihydrite at pH 12. Levels of phosphate of ～1 mol % suppress the formation of goethite (α-FeO(OH)) and result in the formation of a product consisting ofη-Fe₂O₃. Higher levels of phosphate result in the ferrihydrite remaining amorphous, even after several hundred hours. Phosphate prevents formation of goethite by hindering the dissolution of ferrihydrite rather than by interfering with nucleation and growth of goethite in solution. The transformation rate of pure ferrihydrite is also strongly inhibited in the presence of dissolved phosphate. This is due to surface complexation. The transformation rate was measured at temperatures of 60 °C and 70 °C. The rate of transformation was found to be described by either (i) a solid-state reaction equation for powdered compacts or (ii) a zero-order reaction controlled by desorption. The transformation of the ferrihydrite matrix was accompanied by the loss of the phosphate trace component. X-ray diffraction indicates that no solid solution involving phosphate substitution intoη-Fe₂O₃ is formed. Transmission electron microphotographs of the original precipitates containing phosphate confirm the presence of the phosphate and demonstrate its involvement in linking together extremely small particles of ferrihydrite.     

磷酸根在矿物表面的吸附-解吸特性研究进展

综述了磷酸根在一些常见土壤矿物表面吸附-解吸特性的研究进展.磷酸根在矿物表面的吸附特性受环境pH、离子强度、温度、反应时间、矿物类型等多种因素的共同影响.一般说来,矿物表面的磷吸附量随pH降低而增加,受离子强度的影响较小.磷酸根在矿物表面的吸附动力学过程可分为快速吸附过程和慢速吸附过程,且在弱结晶矿物中存在微孔扩散过程...     

Effect of phosphate status and pH on sulphate sorption and desorption

For soils from tea estates in northern India, sulphate sorption was of a similar magnitude to, and sometimes exceeded, phosphate sorption. Only a small part of this relatively large sulphate sorption was caused by the low pH of these soils. Most was caused by increased negative charge as a result of prior reaction over many decades with phosphate fertilizers. This decreased sorption of both phosphate and sulphate, but the effect on phosphate was larger. This is compatible with a model in which the mean location of the charge on the adsorbed phosphate ions is closer to the surface than for sulphate. On soils of low phosphate status, sulphate desorption curves showed hysteresis; on soils of high phosphate status, they did not. Further, on soils of high phosphate status, displacement of sulphate by phosphate solutions was faster. We interpret these observations as showing that, for low phosphate status soils, sulphate ions penetrated the surface, but for high phosphate status soils it did not because the pathways by which sulphate diffuses into the adsorbing material were blocked. We also show that, with increasing soil phosphate status, phosphate solutions were less effective in displacing sorbed sulphate. We think this also occurred because reaction with phosphate had decreased the affinity for phosphate more than it decreased the affinity for sulphate.     

Testing a mechanistic model. XI. The effects of time and of level of application on isotopically exchangeable phosphate

A model for the reaction of ions with soil was improved to permit time trends to be followed at a given level of phosphate addition. Difference equations were also developed to describe the rate of reaction of ions with both vacant sites and occupied sites, while diffusive penetration of the surface was occurring. The model was applied to data for the effects of time and of level of application on exchangeable phosphate. Many of the observed values for isotopically exchangeable phosphate could be well-described if it was assumed that equilibration of ³²P with surface sites was very rapid and this was followed by a diffusive penetration into the adsorbing particles. However, for short periods of contact between soil and ³²P, it was necessary to also take into account the rate of the reaction between ³²P and surface sites. This reaction was largely with vacant sites. Reaction with occupied sites–that is, true exchange–was unimportant. It is suggested that the electric potential of the surface may determine whether reaction is with occupied or vacant sites. In contrast to reaction of ³²P with occupied sites, reaction with vacant sites involves a net transfer of charge. Reaction with vacant sites would be slow if the potential was large and negative. It is shown that when reaction with vacant sites is slow, the proportion of previously added ³¹P recorded as exchangeable increases with level of addition of ³¹P. This may explain published observations of slow and non-linear exchange in some soils.     

On the reversibility of phosphate sorption by soils

Sorption of phosphate was induced by incubating phosphate with samples of two soils. Both desorption and further sorption of phosphate were then measured on separate subsamples of the incubated soils. The effects of varying the amount of phosphate incubated with the soil and of period of desorption, or of further sorption, were measured on one soil; the effect of period of incubation was measured on the other. Plots of desorbed phosphate versus concentration were continuous with plots of newly sorbed phosphate versus concentration. Neither of these coincided with the plots of the original additions of phosphate. These results were compatible with a model for the reaction between soil and phosphate in which phosphate is initially adsorbed and subsequently diffuses beneath the adsorbing surfaces. Sorption is reversible in the sense that a continuous curve of sorbed and desorbed phosphate is obtained when these are measured in opposite directions by increasing, or decreasing, the solution concentration of phosphate. However, because dynamic processes are involved, an earlier position of a plot of sorbed phosphate against concentration is not retraced when the concentration is changed.     

Assessing the fixation and availability of sorbed phosphate in soil using an isotopic exchange method

An isotopic exchange method was used to characterize quantitatively the fixation and plant availability of phosphate previously sorbed by soils. In general, the exchangeability of the sorbed phosphate was much higher than its desorbability for both soils and clay minerals. Isotopic exchangeability of the sorbed phosphate increased with sorption saturation during the initial stage (15–60% saturation), but the increase was less with increasing saturation from 60–90% for all soils tested. Therefore a sorption saturation of 60% was recommended as the upper limit of P fertilization in terms of economical efficiency. For clay minerals, with increasing sorption saturation, the isotopic exchangeability of the sorbed P increased significantly for kaolinite and sesquioxides, but decreased for montmorillonite. Most of the phosphate sorbed by montmorillonite and kaolinite was found to be isotopically exchangeable, but only a small amount of the P sorbed by goethite could be exchanged. The P sorbed by Al oxide exhibited isotopic exchangeability between that of kaolinite and Fe oxide. The isotopically exchangeable phosphate pool could readily account for the P uptake of plants and the available P determined by some commonly used chemical methods, such as Olsen-P and Bray-P.     

Loss of availability of phosphate in New Zealand soils

Phosphate sorption was measured by the method of Barrow (1980) using a laboratory incubation procedure for up to 60 d on four soils which had different mineralogies but medium to high phosphate retention. All the soils had slow reactions where phosphate sorption continued, but at a decreasing rate, with time. The rate of decrease in the slow reactions was similar on all the soils. Phosphate became less available to plants during the slow reactions, and results of a pot trial with white clover showed that, on all the soils, phosphate incubated with the soils for 218 d was about 65% as effective as phosphate incubated for 10d.
When 700 mg P kg⁻¹ was added to allophanic soils (Andisols), about 100 mg kg⁻¹ was strongly adsorbed, about 200 mg kg⁻¹ became unavailable in about 200 days and the remainder was weakly adsorbed. A similar result was obtained on Waiarikiki soil (Inceptisol), which contained ferrihydrite and Al-humus as the predominant reactive species. On the Kerikeri soil (Oxisol) about 150 mg P kg⁻¹ became unavailable with time as a result of reactions with geothite, hematite and Al-humus.
The phosphate uptake by the microbial biomass was similar to the uptake by the clover, and immobilization of phosphate in the biomass can contribute to the loss of availability of phosphate in soils.     

Sorption of phosphate and oxalate by a synthetic aluminium hydroxysulphate complex

We studied the sorption of phosphate and oxalate on a synthetic aluminium hydroxysulphate complex and the associated release of sulphate from this complex. In the pH range 4.0–9.0 the presence of phosphate or oxalate tended to increase the release of sulphate. Much more phosphate than oxalate was sorbed, but in most cases oxalate caused more removal of sulphate than did phosphate. Only in acid systems may these results be partly attributed to the greater solubilization of the complex in the presence of oxalate than in the presence of phosphate. At pH > 8.0 in the presence of phosphate, and at pH > 6.5 in the presence of oxalate, the quantities of sulphate replaced were greater than the quantities of phosphate or oxalate sorbed, suggesting that hydroxyl ions competed with phosphate and oxalate for sorption sites and sulphate removal. Sulphate was only partly removed from the complex even after repeated washings with phosphate or oxalate solutions or after 120 h in the presence of these ligands at pH 6.0. When phosphate and oxalate were added as a mixture much more phosphate than oxalate was retained. Phosphate strongly inhibited oxalate sorption, whereas oxalate partly prevented phosphate sorption only at pH < 7.0. More sulphate was removed in the presence of both the anions than in the presence of phosphate alone, but less than that desorbed in the presence of oxalate alone.     

Tree Response to Experimental Watershed Acidification

In this study, lead (Pb) and antimony (Sb) sorption experiments were conducted to elucidate the mechanisms of Pb and Sb sorption by combined applications using single or combined applications of hydroxyapatite (HAP) and ferrihydrite (FH), to evaluate the contribution of each material in Pb and Sb sorption, and to assess the chemical stability of the sorbed Pb and Sb. In the combined application, isotherms of Pb sorption and Sb sorption were well fitted to Langmuir and Freundlich isotherm models, respectively. The Pb and Sb amounts sorbed in the combined application were the same levels as the summed totals of those sorbed in the single applications, indicating that in the combined application, Pb sorption and Sb sorption were not suppressed. Pb was mainly sorbed on HAP in the combined application, at a 90 % level of the total adsorbed Pb. The HAP and FH contributions to Sb sorption were 32 and 68 % of the total adsorbed Sb, respectively, and Sb was sorbed on each material independently even in the combined application. The percentages of both Pb and Sb dissolved from the sorbed materials in the combined applications at pH 4 and 6 were the same levels as those in the single applications. However, the percentages of Sb dissolved in both combined and single applications were high at an alkaline pH. These results suggest that HAP and FH in a combined application would be useful for simultaneous Pb and Sb immobilization in soil with acidic to neutral pH, but not in soil with an alkaline pH.     

Sorption of iron‐cyanide complexes on goethite investigated in long‐term experiments

The iron‐cyanide complexes ferrocyanide, [Fe^II(CN)₆]^4–, and ferricyanide, [Fe^III(CN)₆]^3–, are anthropogenic contaminants in soil. We investigated their sorption on goethite, α‐FeOOH, in batch experiments in a time range from 1 d to 1 yr, their desorption by phosphate and chloride as well as their surface complexes on goethite by Fourier‐transform infrared spectroscopy (FTIR). The sorption of both complexes continued over the whole time range. Percent desorption of ferricyanide by phosphate decreased, whereas that of ferrocyanide increased until it amounted to approximately 87% for both complexes. By FTIR spectroscopy inner‐sphere complexation of both complexes on the goethite surface was indicated. With both complexes, a Berlin‐Blue‐like layer (Fe₄[Fe(CN)₆]₃) was formed initially on the goethite surface which disappeared with increasing reaction time. After at least 30 d reaction time, ferricyanide was the only sorbed iron‐cyanide complex detected even when ferrocyanide was initially added. This resulted from slow oxidation of ferrocyanide, most probably by dissolved oxygen. Based on all results, we propose that ferricyanide forms monodentate inner‐sphere complexes on the goethite surface.     

The self diffusion of sodium in a naturally aggregated soil

The self diffusion coefficient, in a naturally aggregated soil, of a solute which exists in both liquid and sorbed phases, was measured using a pulse labelling technique. This technique could have given evidence of slow equilibration between the two phases, but none was found. The magnitude of the self diffusion coefficient indicated that the solute is mobile in the sorbed phase. The mobility in the sorbed phase is described by a ‘virtual mobile fraction’. Within the limits set by the heterogeneity of natural aggregates, this was independent of both the volumetric moisture content and the bulk density.     

Retention of Ni,Zn and Cd by Si-associated goethite

Synthetic goethite used to study the effects of reaction time and temperature on the pH-dependent sorption of Ni, Zn and Cd was associated with amorphous silica. Ni interacted with dissolved Si and formed a Ni/Si precipitate on the goethite surface. Individual metals added at a concentration of 0.5 μmol g^?1 and sorbed during a reaction period of 504 hours (21 days) at 35°C were extracted by 0.7 M HNO₃ for 14 days. At the end of this period 11,28 and 40 percent of Ni, Cd and Zn, respectively, were not extracted whereas 20 percent of the total Fe content of the goethite and 39 percent of the associated Si were dissolved. During the sorption process metals became immobilized in the goethite particles. This effect can be related to a diffusion of metal ions into micropores. A total mobilization of sorbed metals can only be achieved by a complete dissolution of the goethite. The strong fixation of Ni, Zn and Cd by goethite suggests that additions of this Fe oxide could be used to ameliorate highly contaminated sludges or soils.