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.     

Modelling the effects of pH on phosphate sorption by soils

Samples of six soils were incubated at 60°C for 24 h with several levels of either calcium carbonate or hydrochloric acid. Phosphate sorption was then measured on sub-samples of the treated soils over 24 h at 25°C. In one set of measurements on all soils, 0.01 M calcium chloride was used as the background electrolyte. In another set, on two soils, 0.01 M sodium chloride was used. An interpolation method was used to give points on the three-dimensional surface relating the final pH of the suspensions to sorption of phosphate at specified solution concentrations of phosphate. The effects of pH on phosphate sorption differed between soils. For unfertilized soils, increases in pH up to about pH 5.5 decreased sorption. Further increases in pH decreased sorption further in one soil and increased it in three others. For fertilized soils, measured sorption increased with pH. When sodium chloride was used instead of calcium chloride, there was a more marked trend for sorption to decrease as pH increased. Differences between the soils were ascribed to differences in two soil properties. One was the rate at which the electrostatic potential in the plane of adsorption decreased as pH increased. Only small differences in the rate of change of potential were needed to reproduce the observed differences between soils. The electrostatic potential would decrease more quickly in solutions of a sodium salt than in solutions of a calcium salt and this explains the observed differences between these media. The other soil property that affected observed sorption was the release of phosphate from the soil. The amount released was largest at low pH. Consequently, for fertilized soils, measured sorption increased with pH.     

Biochar-induced soil phosphate sorption and availability depend on soil properties: a microcosm study

Journal of Soils and Sediments - The effects of soil properties on biochar-induced soil phosphate sorption and availability are not well investigated. An alkaline biochar-induced soil phosphate...     

红壤基质组分对磷吸持指数的影响

在红壤旱地肥料长期定位试验(始于1988年)中,选取了无机肥试验区的NPK、NP、NK、PK,有机无机配施试验区的CK、CK+猪厩肥(BM)及CK+花生秸秆(SR)等7个施肥处理土壤,测定了土壤磷吸持指数(Phosphate sorption index,PSI),分析了PSI与红壤最大吸磷量(Xm)的相关关系,讨论了土壤pH、有机质、黏粒、铁铝氧化物及无机磷酸盐等基质组分对PSI的影响。结果表明:长期施磷或配施有机肥均可显著降低红壤PSI值,随着土壤pH的升高、有机质及铁结合态磷酸盐(Fe-P)含量的增加,红壤PSI显著降低;土壤游离铁铝氧化物及黏粒含量越高,PSI也越大。PSI与Xm呈显著线性相关关系(Xm=0.5PSI+412.8,n=15,r=0.967**,p<0.01),因此,可以用PSI替代Xm来表征土壤固磷能力,亦可由PSI的大小来推断土壤磷的供磷能力。     

Effect of soil microorganisms on the sorption of zinc and lead compounds by goethite

The objectives of this study were (1) to determine the effect of microorganisms during in‐vitro incubation on the amount of Zn and Pb from solution retained on goethite precipitated as coatings on a sand matrix and (2) to evaluate accumulation of heavy metals in the biomass of soil microorganisms in the fresh soil samples using an extractive approach. A mixture of colonies of cultivated microorganisms extracted from a Haplic Luvisol (Russia) and an Antropi‐urbic Regosol (Germany) were used to prepare the cell and the microbial‐debris suspensions. The concentrations of Zn and Pb in the studied solutions supplied with microbial suspensions and/or goethite coated sand were 0.1 mM (130.8 and 414 mg kg^–1 of sand, respectively). Exchangeable forms of metals were determined by extraction with 10 mL of 1.0 M KNO₃. Nonexchangeable forms of Zn and Pb were recovered using 40 mL of 0.3 M NH₂OH‐HCl in 1 M HNO₃. Concentrations of Pb increased in the solutions and decreased on the surface of the Fe‐mineral due to living microorganisms. In comparison to incubation of heavy‐metal solutions with goethite only, the absolute concentrations of nonexchangeable forms of metal were reduced by microbial suspension to a greater extent than those of the exchangeable forms, whereas the relative content of both fractions decreased by a factor of almost two. Sorption of Pb by goethite was inversely correlated with the concentration of organic C in the solution. Microorganisms clearly influenced the Zn sorption by goethite at concentrations of C_org > 400 mg L^–1. The amount of Zn retained was decreased primarily due to decreasing Zn portions in the exchangeable fraction. Microbial debris prepared by autoclaving reduced the Pb sorption by goethite similar to the results for living cells. Living microorganisms accumulated more Zn than did microbial debris. The data of this paper show that a direct determination of heavy‐metal accumulation in soil microorganisms by extraction with 2.0 M KCl as well as by extraction with 1 M CH₃COONH₄ at the natural pH of the soils after chloroform fumigation of fresh soils samples with different concentrations of organic C was not possible.     

Solubilization of zinc phosphate by a strain of Pseudomonas fluorescens isolated from a forest soil

 A strain of Pseudomonas fluorescens, able to solubilize zinc phosphate, was isolated from a forest soil. Colonies of the microorganism produced clear haloes on solid medium incorporating zinc phosphate, but only when glucose was provided as the carbon source. Solubilization of zinc phosphate occurred by both an increase in the H⁺ concentration of the medium, probably a consequence of ammonia assimilation, and the production of gluconic acid. High concentrations of gluconic acid were produced when P. fluorescens 3a was cultured in the presence of zinc phosphate. Although under some conditions gluconic acid is purportedly able to solubilize metals by the formation of chelates, no evidence of zinc chelation was obtained in our experiments. Furthermore, the increased Zn²⁺ concentration caused by the solubilization process resulted in the manifestation of toxic effects on the culture. A sample of the culture, sonicated to disrupt cells, still possessed the ability to produce gluconic acid from glucose, in the presence and absence of zinc phosphate. The lack of gluconic acid overproduction in cultures of P. fluorescens 3a which were not amended with zinc phosphate suggests that at least some of the glucose oxidation required for the zinc solubilization occurred as a result of the toxic stress caused by the high Zn²⁺ concentration. Received: 16 December 1997     

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.     

复垦沉积池土壤中镍、铅、锌的吸附

The wastes used to amend soils sometimes have high concentrations of metals such as nickel (Ni), lead (Pb) and zinc (Zn). To determine the capacity of soils to retain these metals, the sorption capacities of different mine soils with and without reclamation treatments (tree vegetation and waste amendment) for Ni, Pb and Zn in individual and competitive situations were evaluated using the batch sorption technique. The untreated settling pond soil had low capacity for Ni, Pb and Zn retention. The site amended with wastes (sewage sludges and paper mill residues) increased the sorption capacity most, probably because of the higher concentrations of soil components with high retention capacity such as carbon and clay fraction. No significant competition was observed between metals in the competitive sorption experiment, indicating that the maximum of sorption was not achieved by adding 0.5 mmol L^-1 of metal. We can conclude that, despite the possible additions of Ni, Pb and Zn from wastes to degraded soils, sewage sludges and paper mill residues have a high sorption capacity that would prevent the metals from being in a mobile form.     

A statistical study of seven curves for describing the sorption of phosphate by soil

Seven mathematical models, which have been advanced for describing phosphate sorption by soils, are studied here with respect to their statistical behaviour in estimation. These seven non-linear regression models include the Langmuir equation and two extensions of it, the Freundlich equation and two extensions of it, and Gunary's equation. Measures of non-linear behaviour, such as the Bates & Watts (1980) curvature measure of intrinsic non-linearity and the Lowry & Morton (1983) asymmetry measure of non-linearity, were calculated for each model in combination with each of six data sets. It was found that the Freundlich equation and the extension of it proposed by Sibbesen behaved best, with Gunary's equation also having acceptable statistical properties, whereas the Langmuir equation and its extensions behaved worse, exhibiting properties which indicate that the estimators of their parameters would be severely biased and non-normal in distribution. It is believed that similar conclusions may apply to other processes involving surface adsorption.     

Factors affecting phosphate sorption along a Mediterranean, dolomitic soil and vegetation chronosequence

Phosphate sorption by calcareous soils has been studied mainly on heavily fertilized agricultural soils and soils with calcite as the main carbonate mineral. We examined factors affecting phosphate adsorption in the soils of a semi-arid, mediterranean, dolomitic, soil and vegetation chrono-sequence in southeastern Spain. The youngest soils are highly eroded, Sandy Regosols (Typic Xerorthents) under gorse-scrubland vegetation. These have small P sorption capacities, large Mg-Ca carbonate contents but small amounts of Fe and Al oxides. Small total P (HNO₃/HClO₄ digestion) concentrations (30–130 μg P g^?1), of which up to 90% is Ca-bound (HCl-extractable), are typical of these young soils. P sorption markedly increased when Ca²⁺ was added to the solution. The fractionation of previously sorbed P indicates that the fate of most of this extra-sorbed P is the labile-P fraction sorbed on to (carbonate) surfaces and the apatite-like fraction (NaHCO₃-extractable and HCl-extractable fractions). At the other extreme, older more-intensively weathered, sandy-clay-loam rendzinas (Entic Haploxerolls), supporting dense mature garrigue, have a much greater P adsorption capacity and larger clay and Fe and Al oxide concentrations. They have more total P (ca 400 μg P g^?1), much of it in occluded form (residual fraction). These soils show no significant differences in P sorption whether or not CaCl₂ was used as a background electrolyte. Considering the overall variations within the chronosequence, dithionite extractable Fe and Al are the properties best correlated with P sorption. This support the general finding that crystalline Fe-oxides (e.g. goethite and haematite) appear to be the most important P-sorbing component for soils in the Mediterranean region, rather than amorphous Fe-oxides (e.g. ferrihydrite) as is reported for more mesic areas. Stepwise multiple regression and fractionation data, however, suggest that, provided the soil solution is rich in Ca²⁺, carbonate may also be a significant contributing factor to P sorption, especially in the youngest of these dolomitic soils.     

Influence of phosphate on cadmium sorption by calcium carbonate

Laboratory investigation was conducted to investigate the mechanism of cadmium sorption by pure calcium carbonate and to examine whether, reaction products of phosphate with calcium carbonate serve as a sink for sorption of toxic heavy metal cations like cadmium. The phosphatization of calcium carbonate (G.R) was carried out by treating it with orthophosphoric acid in Ca:P ratio of 5:3, 3:2, 4:3 and 1:1, representing the Ca–P ratios of carbonate apatite, tricalcium phosphate, octacalcium phosphate and dicalcium phosphate and then equilibrated for two months. The X-ray diffraction of the phosphate reaction products revealed that calcite along with monetite, brushite and carbonate apatite were present in each case. The cadmium was effectively retained on CaCO₃ by the mechanism of chemisorption at lower Cd²⁺ concentrations as the pH of the equilibrium system remained constant (8.6) up to initial Cd²⁺ concentrations of 10⁻⁴ mol, coinciding to 100% sorption of Cd²⁺ from the solution. At higher concentrations, precipitation of CdCO₃ on CaCO₃ surface or as a separate phase predominated. Enrichment of CaCO₃ with P reduced the Cd-sorption. The chemisorption of Cd probably involved the exchange of Ca²⁺ by Cd²⁺ from CaCO₃ surface. The Cd²⁺ concentration in equilibrium solution followed the solubility diagram of CdCO₃ at pH ≤ 8.6, whereas the concentration of Ca²⁺ started deviating from the solubility line at pH ≤ 8.2.     

Effect of liming on phosphate sorption by acid soils

The sorption of phosphate (P) by four strongly acid Fijian soils from 0.01 M CaCl₂ decreased with increasing pH up to pH 5.5–6.0 and then increased again. The initial decrease in P sorption with increasing pH appears to result from an interaction between added P, negative charge, and the electrostatic potential in the plane of sorption. The results of a sorption study, involving KCl or CaCl₂ of varying concentrations as the background electrolyte and using Nadroloulou soil incubated with KOH or Ca(OH)₂, suggested that the increase in P sorption at pH values > 6.0 was caused by the formation of insoluble Ca-P compounds. For some soils this is consistent with the results of an isotopic-exchange study in which incubation with lime caused marked reductions in the amounts of exchangeable P at high pH.     

The effects of pH and chloride concentration on mercury sorption. II. By a soil

The pH of a soil was altered by incubation with either acid or lime, and the sorption of mercury was measured in the absence of chloride and at three chloride concentrations. In the absence of chloride there were only small effects of pH on sorption between pH 4 and 6; sorption decreased at higher pH. Addition of chloride decreased sorption at low pH but had little effect on sorption at high pH. Consequently, in the presence of chloride, sorption increased with increasing pH between pH 4 and 6 and then decreased. Many of the mercury sorption curves were sigmoid. This was explained by assuming that a small amount of complexing material was present in the solution after mixing with the soil. Calculation of the mercury species present in solution was made difficult by uncertainties about the postulated complexing material. Nevertheless, between pH 4 and pH 5.8, it was possible to explain the effects of pH and of chloride concentration on sorption as entirely due to changes in the HgOH⁺ concentration.     

Influence of phosphate sorption on dispersion of a Ferralsol

Abstract

Soil dispersion induces soil erosion and colloidal leaching. Nutrients are lost at the same time and this causes water contamination. Phosphate is an essential element for living organisms. Because phosphate influences soil dispersion and it is an important limited resource, this influence must be evaluated well in order to diminish negative effects on soil structure. In this paper, we firstly evaluated the influence of phosphate sorption on soil dispersion by calculating repulsive potential energy between soil particles. Ferralsol, which is a typical soil in rainy tropical regions, was used as the material. The dispersion-flocculation phenomena were investigated with absorbance of soil suspension under different pH, phosphate adsorption and electrolyte concentration in an Na-NO₃-PO₄ system. The repulsive potential energy was calculated based on the diffuse double layer theory and the measured zeta potential. We indicated that the measured absorbance increased with the increase of the repulsive potential energy. The repulsive potential energy increased with increasing phosphate sorption up to about 5 to 20 mmol kg^?1 at all pH, and it induced the soil dispersion, because phosphate sorption increased the negative charge of the soil. After its peak, it decreased with increasing phosphate sorption because the electrolyte concentration increased and the electrolyte screened the electric field near the soil surface. The repulsive potential energy also increased with increasing pH because of the increase of the negative charge of the soil. Even at low pH, after a certain amount of phosphate sorption, the soil dispersed due to the increase of repulsive potential energy, although the soil flocculated before phosphate application. Because the soil dispersion causes soil and phosphorus loss, the influence of soil pH and phosphate sorption on the soil dispersion should be considered for good soil management.     

Effects of equilibrating salt solutions on phosphate sorption by soils

Abstract

Several equilibrating salt solutions have been used in the studies of P sorption by soils and sediments. This study was conducted to evaluate the effects of 10 salt solutions on estimation of P sorption by soils. Results obtained showed that, when the equilibrating solution was made to contain 0.01M with respect to CaCl₂, Ca(NO₃)₂, CaSO₄, MgCl₂, KCl, LiCl, Nacl, or KHCO₃, the amount of P sorbed by soil always exceeded the amount sorbed from the soil‐water system. In comparison with the amount of P sorbed from water, 0.01M NaHCO₃ reduced P sorption by soils. Use of THAM buffer (0.05M pH 7.0) to control the pH increased P sorption by some soils and decreased P sorption by others, relative to that sorbed from the soil‐water system. The results indicated that inclusion of salts in the equilibrating solution for P‐sorption studies should be avoided, especially in studies related to water quality.     

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.     

Speciation and calcium competition effects on cadmium sorption by sandy soil at various pHs

The effects of Ca competition, ionic strength, inorganic complexation and pH on cadmium adsorption by a sandy soil were studied. Sorption of Cd was measured using four different electrolytes CaCl₂, Ca(NO₃)₂, NaNO₃ and NaCl at a constant ionic strength (I) of 0.003 M at three different pHs, at variable Ca/Na ratio with a constant ionic strength of 0.03 and at variable ionic strengths between 0.003 and 0.3 M for two different pHs for Ca(NO₃)₂ and NaNO₃. The measured Cd sorption isotherms were non-linear. In the case of Cl as electrolyte anion, 13% of the Cd in solution is complexed at I= 0.003 (0.002 M Cl) and 91% of Cd is complexed at I= 0.3 (0.2 M Cl). If NO₃ is the anion, none of Cd is complexed at I= 0.003 and 11% at I= 0.3. The Cd complexes do not adsorb significantly. Calcium competition, at an ionic strength of 0.03, reduced the Cd adsorption by 60–80% compared with the case that Na is the cation. Increasing the ionic strength from 0.003 to 0.3 decreased Cd sorption by 60% for Ca(NO₃)₂ and 25% for NaNO₃ due to a decrease of the activity coefficient, increase of inorganic complexation and increase of Ca competition. A decrease of one pH unit reduces Cd sorption of about 75%. Sorption of Cd by soil could be described adequately with the three-species Freundlich (3SF) equation in which pH, complexation, Ca competition and ionic strength effects were taken into account.