RATE-CONTROLLING PROCESSES IN THE RELEASE OF SOIL PHOSPHATE

The isotopic exchange of phosphate ions in a deep river gravel soil, maintained at different pHs from 3.5 to 6.7 in a field experiment, established by the N.A.A.S. at Shardlow, was governed initially (<20 h) by simultaneous ‘first-order’ and ‘bulk diffusion’ kinetics, but later by ‘bulk-diffusion’ kinetics only. The ‘bulk-’ or ‘intracrumb-’ diffusion coefficient was independent of phosphate manuring, was least at pH 5.5 and increased on either side of this critical pH. The rate constant for the phosphate component exchanging initially with ‘first-order’ kinetics increased significantly with phosphate manuring at pH 3.5, 4.4, and 5.5, although the constants for unmanured and manured soils did not change with soil pH. But at pH 6.7, the rate constants for the unmanured and phosphate-treated soils were greater than those in the more acid soils, although the constant for the manured soil was just significantly greater than that of the unmanured soil. Residual phosphate (i.e. the difference between manured and unmanured soils) adsorbed on the soil was greatest in the more acid soils but water-soluble residual phosphate increased with soil pH to a maximum at pH 5.5. Residual phosphate, exchanging initially, decreased to nothing above pH 6.5.     

Manganese extracted from different chemical fractions of bulk and rhizosphere soil as affected by method of sample preparation

Abstract

Rhizosphere soils had higher amounts of ‘readily soluble’, ‘weakly adsorbed’, ‘carbonate bound’ and ‘specifically adsorbed’ Mn, but had lower amounts of ‘oxide‐Mn’, than did bulk soils. This observation was true regardless of whether the comparison was based on values within moist or air‐dried treatments. Observed trends in Mn distribution between different soil fractions were qualitatively similar regardless of method of sample preparation. However, there were substantial quantitative differences depending on the method of sample preparation. Air‐dried samples increased significantly in the ‘oxide‐Mn’ fraction and decreased in its soluble and adsorbed fractions relative to moist soil samples. There was a significant effect of method of air‐drying on the distribution of Mn in rhizosphere samples. Samples that were extracted moist at first and then air‐dried accumulated more adsorbed Mn and were depleted in ‘oxide‐Mn’ relative to samples that were air‐dried initially. There was a significant rhizosphere x air‐drying interaction. Air‐drying of some rhizosphere samples resulted in a significant underestimation of the ‘readily soluble’, ‘specifically adsorbed’, and ‘oxide‐Mn’ fractions beyond the overall effect of air‐drying. The results of this study suggested that soil samples used for Mn analyses be extracted immediately in a moist condition rather than air‐dried, particularly for analyses of rhizosphere soil samples.     

氧化铁对磷酸根和氟离子的竞争吸附

吸附在氧化铁表面上的磷酸根包括同位素可交换性的和非交换性的二种类型.当磷酸根的吸附量低时,非交换性磷酸根与磷酸根的吸附量之比大于磷酸根的吸附量,高时二者之比非交换性磷酸根的量不受平衡悬浮液中磷酸根的浓度的影响.当磷酸根先被吸附,或磷酸根和氟离子同时吸附时,磷酸根的吸附不受氟离子的影响.当氟离子先被吸附时,它对磷酸根的吸附有一定的影响.当氟离子的吸附量低时,大部分被吸附的氟不能被磷酸根取代.随着氟的吸附量的增加,可被取代的氟离子的比例增大.     

Forms and extractability of manganese in potting media

Abstract

Sequential extraction of pine bark medium alone and after amendment with either manganese sulfate (MnSO₄), composted rice hulls, or soil showed that at pH 5.5–7.0 most of the manganese (Mn) exists in a form that is extracted by acidic hydroxylamine hydrochloride, and which could therefore be in oxide or strongly‐bound forms. Acidification to pH 4.5–5.0 transferred large amounts of this ‘oxide’ Mn into ‘readily available’ and ‘weakly adsorbed’ fractions. Similar extractions of Sitka spruce bark showed that most of its Mn was extracted by weak cationic reagents ('readily available’ and ‘weakly adsorbed’ fractions). Growth of oats in pine bark, peat, and eucalypt sawdust media, with and without MnSO₄ amendment, lowered the amounts of Mn in ‘readily soluble’ and ‘weakly adsorbed’ fractions and caused some loss of ‘oxide’ Mn. Comparison of data for Mn extracted by 2 mM DTPA (1:1.5 v/v) with Mn in sequential fractions showed that DTPA dissolves some ‘oxide’ Mn. The data further suggest that up to about 36 mg/L DTPA‐extractable Mn would not be toxic to most plants growing in media of pH 6.0, but 60 mg/L DTPA‐extractable Mn may be if the medium pH falls below 5.5.     

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.     

Phosphate sorption by synthetic amorphous aluminium hydroxides: a 27Al and 31P solid-state MAS NMR spectroscopy study

The sorption of phosphate on amorphous aluminium hydroxides was investigated using ²⁷Al and ⁷¹P solid-state magic-angle spinning nuclear magnetic resonance (MAS NMR) spectroscopy, following the effect of different exposures to soluble phosphate. The spectra obtained were compared with the spectrum of amorphous aluminium phosphate. Aluminium in the unreacted hydroxide had a 100% octahedral co-ordination. When dried at 200°C and exposed to soluble phosphate, very little (maximum 0.1%) amorphous aluminium hydroxide transformed to a tetrahedral co-ordination (A1 bound by oxygen bridges to four P atoms), even after 120d. The tetrahedral co-ordination exists in aluminium phosphate gel, although most of its A1 atoms exhibit an octahedral co-ordination. For the aluminium hydroxide dried at 200°C, no formation of aluminium phosphate in which aluminium is in octahedral co-ordination could be detected, not even when the aluminium hydroxide was exposed to a phosphate solution for 120 d. We concluded that the formation of aluminium phosphate is restricted to the surface of the hydroxide. Most of the phosphate which is bound to the aluminium oxide however may not have formed a ‘bulk solid’ aluminium phosphate, but is adsorbed on the internal and external surface of the oxide. The same amorphous aluminium hydroxide, dried at 70°C instead of 200°C, is converted much more rapidly to aluminium phosphate when exposed to soluble phosphate. We propose a P-induced weathering mechanism to describe P sorption on amorphous aluminium hydroxides at high P concentrations. In addition to NMR, phosphate adsorption experiments conducted on aluminium hydroxides dried at different temperatures produced evidence that the porosity of the aluminium hydroxide aggregated particles can also be a factor controlling the rate of phosphate uptake from solution, if the aggregate is stable (is not resuspended) in solution.     

PHOSPHATE ADSORPTION IN ALLOPHANIC SOILS

The kinetics and heats of phosphate adsorption were measured on the <2 μm Na-saturated fractions of three allophanc-rich soils from Japan. Between 50 and 2250 μmol P g^?1 as sodium phosphate were added to the soil fractions at pH 5 and pH 7, and at initial concentrations of 5 and 25 × 10^?4m to avoid aluminium phosphate precipitation. An initial ‘instantaneous’ adsorption associated with exposed sites and, simultaneously, two inverse exponential rates of adsorption on internal and freshly forming external sites were observed. These rates are attributed to changes in the microstructure of allophane and to the desorption of organic matter held on allophanic surfaces. This interpretation is strongly supported by corresponding changes in the heats of adsorption with time. Calorimetry clearly indicates that when very large amounts of phosphate are added, new and very reactive surfaces are progressively exposed. More phosphate was adsorbed when the soil was acid and when the soil contained less organic matter.     

表面吸附层对磷矿石磷素释放的影响

次生磷矿石表面的Ｃａ－Ｐ吸附层对磷矿石磷的释放有重要影响,以ＮａＣｌ,ＫＣｌ或ＮＨ４Ｃｌ浸提除去磷矿石表面的吸附态Ｃａ,导致了随后的水提取磷的大量增加。认为磷矿石表面的吸附层给磷灰石的加速溶解提供了Ｃａ的接收率。     

Anion Adsorption and Desorption Characteristics of a Piedmont Ultisol: Some Implications for the Fate of Sulfate Deposition

Batch-type experiments were used to determine the anion (fluoride, nitrate, sulfate, and phosphate) adsorption and desorption characteristics of an Ultisol from the Piedmont Province of Georgia. The results were best described using ‘initial mass’ isotherms when the initial anion concentration was less than two meq l^-1. The Langmuir adsorption maximum for sulfate (initial concentration range of 0.2–20 meq l^-1) was 24.4 meq kg^-1. Oxalate, acetate, nitrate, fluoride, and phosphate were used as exchangeable ‘counter’ anions to investigate the sulfate retention characteristics of this soil. High concentrations (> one meq l^-1) of oxalate, phosphate and fluoride were shown to release sulfate from this soil. However, little sulfate desorption resulted when lower and more environmentally realistic concentrations of competing anions were applied. Application of oxalate revealed that a minimum of 19 meq kg^-1 of sulfate has been adsorbed on this soil through natural processes. The Langmuir adsorption maximum suggests that this Ultisol, typical of many B horizons within this region, has a large capacity to adsorb additional inputs of atmospheric sulfate.     

THE COVARIANCE OF PHOSPHATE SORPTION WITH OTHER SOIL PROPERTIES IN SOME BRITISH AND TROPICAL SOILS

Phosphate sorption capacity estimated by Piper's (1942) ‘anion exchange capacity’ and Bache and Williams's (1971) phosphate sorption index were correlated with soil pH, clay, organic matter, ‘free iron oxides’ and ‘extractable aluminium’ (McLean et al., 1958) for topsoil and subsoil samples from twenty tropical and twenty British acidic soil profiles. These two groups of soils did not differ significantly in phosphate sorption. Extractable aluminium and free iron oxide were well correlated with phosphate sorption, free iron oxide being superior to aluminium in freely drained British soils but not in poorly drained ones. Organic matter content correlated well with phosphate sorption for the poorly drained British soils, and for the tropical soils when sorption capacitywas measured using a high phosphate concentration.     

发育程度对海南玄武岩发育土壤吸附铬酸根和磷酸根的影响

选择海南岛北部3个不同年代喷发的玄武岩发育的土壤研究了其对铬酸根(CrO42-)和磷酸根(PO43-)的吸附特征,结果表明随着母岩年龄的增加,土壤发育程度提高,土壤游离氧化铁和表面正电荷数量增加,对2种阴离子的吸附量增加。土壤CrO42-的解吸率在19.8%~39.6%之间,表明土壤对CrO42-的吸附涉及静电吸附和专性吸附2种机制,且随着土壤发育程度增加,CrO42-静电吸附所占比例增加。土壤对PO43-的吸附以非静电吸附为主,吸附的PO43-的解吸量非常低,其解吸率不超过6%。吸附PO43-在去离子水中的解吸量高于在0.1 mol/L NaNO3和KNO3中的解析量,KNO3体系中的解吸量低于NaNO3体系中的,电解质主要通过改变胶体表面离子吸附面上的静电电位影响PO43-的解吸。     

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.     

Modelling the effect of adsorption of phosphate and other anions on the surface charge of variable charge oxides

Adsorption of anions by iron and aluminium oxides decreases the charge on the surface. However, the negative charge conveyed to the surface by an adsorbed anion varies with the amount of anion adsorbed. This has been explained qualitatively by postulating a mixture of reactions at different surface coverage (Rajan, 1976) or by postulating different reaction mechanisms at different concentrations of phosphate (Ryden & Syers, 1975). We show that these effects may also be reproduced by the adsorption model of Bowden et al. (1974, 1977, 1980). This model does not require a mixture of equations to describe the variations in charge conveyed to the surface. Instead it describes the electrostatic consequences of adsorption. The charge conveyed to the surface by each increment of phosphate differs from that of the previous increment because each successive increment reacts with a surface with a different net charge. The model also reproduces the observed effects of ionic strength and pH on the charge conveyed to the surface by adsorption. Further, it suggests that differences between anions on the charge conveyed to the surface are explicable in differences in the mean distance of the adsorbed anion from the original surface.     

Mechanism of sulphate adsorption by two tropical SoilS

The mechanism of sulphate (SO₄) adsorption was investigated using two highly-weathered soils with contrasting surface-charge characteristics (one with a net negative charge and the other with a net positive charge). The addition of SO₄ caused a release of OH and increased the adsorption of cations, in keeping with the widely-held view that SO₄ is chemisorbed by replacing -OH and -OH₂ ligands. On the other hand, adsorbed SO₄ was completely recovered by washing with an indifferent electrolyte solution (1 M KC1), an extractant which is usually taken to be specific for ‘exchangeable’ ions. The amounts of SO, adsorbed were several times higher than those of non-specifically adsorbed Cl. It is suggested that the experimental observations can be interpreted in terms of a model in which SO₄ adsorbs in a plane closer to the surface than monovalent anions (e.g. in the Stern layer). The consequence of higher counter-ion valence and proximity to the surface is that additional positive charge is induced onto the surface by OH release. Charge reversal in the diffuse layer allows more cations to be adsorbed. This type of adsorption may involve forces other than the purely electrostatic but, in contrast to chemisorption, the adsorbed anion does not become chemically coordinated to the surface metal atoms.     

RATE PROCESSES IN THE DESORPTION OF PHOSPHATE FROM SOILS BY ION-EXCHANGE RESINS

Phosphate extracted by ion-exchange resins in the chloride and sodium forms from a deep river-gravel soil under widely varying conditions is always from the isotopically exchangeable or‘labile’ pool. At any reaction time, a constant fraction of this pool is desorbed by the chloride form of the anion-exchange resin alone, irrespective of the pH and phosphate manuring of the soil. If, however, a sodium: cation exchange resin is included, increasing fractions of the‘labile pool’ are desorbed with decreasing soil acidity. Phosphate desorption by the anion-exchange resin alone and with the cation exchange resin is shown to be‘particle-diffusion’ controlled in the anion exchange resin and neither a‘chemical reaction’ nor a‘film-diffusion’ mechanism. Over the pH range 4·5–8·5, values between 4·8 and 0·9 × 10^-9 cm² sec^-1 were calculated for the interdiffusion coefficient of the phosphate: chloride exchange process in the resin. The isotopically exchangeable phosphate in the soils seems to behave like sparingly soluble or weakly dissociating compounds towards ion-exchange resins and its rate of desorption depends on the nature and composition of the resins.     

Modifications to the Freundlich equation to describe anion sorption over a large range and to describe competition between pairs of ions

We measured sorption of selenite and phosphate, both separately and in competition, in a Chilean Andisol. We also used previously published data for competitive sorption of arsenate and phosphate by a clay subsoil. We wrote computer programs that allowed us to compare the fits of differing versions of equations to describe individual sorption and competitive sorption. For the selenite–phosphate data, the index term of the Freundlich equation decreased as concentration increased. This was described using the Sibbesen modification of the Freundlich equation. This modification was then included in competition equations. For both the selenite–phosphate and the arsenate–phosphate data, competition was not ‘symmetrical’, that is, the competition terms were not reciprocals of each other. We think this occurred because competition between ions is not only competition for adsorption sites but also involves electrical effects that follow penetration of the surface.     

Influence of soil composition on adsorption of glyphosate and phosphate by contrasting Danish surface soils

The herbicide glyphosate and inorganic phosphate are strongly adsorbed by inorganic soil components, especially aluminium and iron oxides, where they seem to compete for the same adsorption sites. Consequently, heavy phosphate application may exhaust soil's capacity to bind glyphosate, which may lead to pollution of drain‐ and groundwater. Adsorption of phosphate and glyphosate to five contrasting Danish surface soils was investigated by batch adsorption experiments. The different soils adsorbed different amounts of glyphosate and phosphate, and there was some competition between glyphosate and phosphate for adsorption sites, but the adsorption of glyphosate and phosphate seemed to be both competitive and additive. The competition was, however, less pronounced than found for goethite and gibbsite in an earlier study. The soil's pH seemed to be the only important factor in determining the amount of glyphosate and phosphate that could be adsorbed by the soils; consequently, glyphosate and phosphate adsorption by the soils was well predicted by pH, though predictions were somewhat improved by incorporation of oxalate‐extractable iron. Other soil factors such as organic carbon, the clay content and the mineralogy of the clay fraction had no effect on glyphosate and phosphate adsorption. The effect of pH on the adsorption of glyphosate and phosphate in one of the soils was further investigated by batch experiments with pH adjusted to 6, 7 and 8. These experiments showed that pH strongly influenced the adsorption of glyphosate. A decrease in pH resulted in increasing glyphosate adsorption, while pH had only a small effect on phosphate adsorption.     

CATEGORIZATION OF BRASSICA CULTIVARS FOR PHOSPHORUS ACQUISITION FROM PHOSPHATE ROCK ON BASIS OF GROWTH AND IONIC PARAMETERS

We categorized sixteen Brassica cultivars for their differential growth response and phosphorus (P) acquisition from phosphate rock (PR) and monoammonium phosphate (MAP). Plants were grown with both P sources in a nutrient solution experiment for 40 days. Cultivars differed significantly (P < 0.01) both for absolute as well as relative values of growth and physiological parameters at both P sources. Phosphorus deficiency in PR treatment significantly depressed biomass production (more than 2.5 times than control) and P concentration (about 1.5 times) in all of the cultivars. ‘Rainbow’ and ‘Poorbi Raya’ produced significantly more relative biomass than other cultivars grown with PR. Cultivars were classified into three classes on the basis of mean values of different parameters and their standard deviation viz low, medium and high. Cultivars were also classified into different classes while regressing biomass and P contents. Cultivars ‘Rainbow’ and ‘Poorbi Raya’ accumulated maximum shoot dry matter (1.21 and 1.27 g dry matter/plant, respectively) grown with phosphate rock, hence were categorized as high biomass producers. Cultivars ‘Rainbow’, ‘KS-74’, and ‘Poorbi Raya’ accumulated maximum P (5.58, 5.24, and 4.81 mg P plant^?1, respectively) from PR and were categorized as high P accumulators. Cultivars with high biomass and high P contents such as ‘Rainbow’ and ‘Poorbi Raya’ at low available P (Rock P) would be used in further screening experiments to improve P efficiency in Brassica.     

SOME NEW EQUATIONS TO DESCRIBE PHOSPHATE SORPTION BY SOILS

Phosphate sorption was studied on surface and subsurface soils sampled from the old field experiments at Askov, Denmark. Two empirical three-parameter equations, an extended Freundlich and an extended Langmuir equation are proposed and compared with the Langmuir, the Freundlich, the ‘double’ Langmuir, the Gunary, and the Fitter-Sutton equations. In the proposed equations the affinity parameter of the Langmuir equation and the exponent of the Freundlich equation are replaced by the term Bc ^?D the value of which decreases with increasing phosphate concentration, c. On average the Freundlich equation thus modified yielded the closest fit to the sorption data. This was followed by the Fitter-Sutton, the modified Langmuir, the ‘double’ Langmuir, the Gunary, the Freundlich, and finally the Langmuir equation. Out of the three equations that yielded the closest fit to the sorption data the correlation between the parameters within the equations, furthermore, was least for the proposed extended Freundlich equation. Therefore, this equation may be generally suitable for describing phosphate sorption by soils.     

Composition,Use and Legislation of Spent Mushroom Substrate in the Netherlands

? In The Netherlands, 760,000 metric tons of Spent Mushroom Substrate (sold under the name Champost) were produced in 1993. The annual production is still rising. Analytical data concerning fertilizer elements like N, P, K, Ca and Mg, show that the composition of SMS has been fairly constant since the mid sixties. However, the last few years, dry matter, ash and phosphate content are decreasing due to reduced composting time and cropping cycle. Heavy metals and arsenic were not analyzed until 1983. In connection with manure surpluses in The Netherlands, a ‘Decree Use of Animal Manure’ was laid down as part of the Soil Protection Act, which dates from 1986. The Decree regulates the maximum quantity of manure that may be used, based on its phosphate content. The rules will be accentuated in the next few years. Since 1993, SMS falls under another item of the Soil Protection Act, the ‘Decree Use and Quality of Other Organic Fertilizers,’ controlling sewage sludge and all kinds of composts. The quantity that may be used depends on phosphate and heavy metal content. The total load of heavy metals, supplied per hectare, is controlled by limiting the amount of dry matter. Each year, 6 metric tons of dry matter may be used per hectare, provided that the compost is ‘clean’. To check phosphate and heavy metals, samples have to be analyzed regularly. In 1993, 620 samples have been analyzed. All compost fell within the category ‘clean’ and 17% was even characterized as ‘very clean.’ Production of vegetable, fruit and garden waste, a type of compost very competitive to SMS, is strongly increasing. Alternative ways of disposal of SMS will be discussed briefly.