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.     

Influence of organic matter on phosphate adsorption by aluminium and iron oxides in sandy soils

The phosphate adsorption capacity (P_max) of samples from various horizons of five Danish podzolized soils were investigated before and after organic matter removal. Removal of organic matter had no direct influence on P_max suggesting that organic matter did not compete with phosphate for adsorption sites. In the soils investigated aluminium and iron oxides were the main phosphate adsorbents. Thus, more than 96% of the variation in P_max could be accounted for by poorly crystalline aluminium and iron oxides (extractable by oxalate) and by well-crystallized iron oxides (taken as the difference between dithionite-citrate-bicarbonate-extractable iron and oxalate-extractable iron). Organic matter affected phosphate adsorption indirectly by inhibiting aluminium oxide crystallization. The resulting poorly crystalline oxides had high P_max. In contrast, the influence of organic matter on the crystallinity of the iron oxides, and therefore on their capacity to adsorb phosphate, seemed limited.     

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.     

Sorption of isotopically exchangeable and non-exchangeable phosphate by some soils of Colombia and Brazil, and comparisons with soils of southern Nigeria

Fourteen soils from Colombia and Brazil provided a wide range of sorption characteristics. Curves of sorbed phosphate that was exchangeable to ³²P were described by Freundlich's equation, and of non-exchangeable phosphate by Temkin's equation. Exchangeable phosphate was associated with aluminium in poorly-crystalline oxides and in organic complexes. Non-exchangeable phosphate was related to aluminium in organic complexes, and especially to the ratio of AI/C in them. In Nigerian soils similar mechanisms controlled sorption of phosphate but oxides and organic complexes of iron were important. The concentration of phosphate in solution when affinities of soil for exchangeable and non-exchangeable phosphate are equal, and the importance of organic matter, are discussed in relation to soil management and to responses of crops to fertilizer phosphate. The results indicate that sorption curves should not be split into sections.     

The influence of iron oxides on phosphate adsorption by soil

Soils from Denmark and Tanzania were extracted with ammonium acetate (controls), EDTA to dissolve amorphous iron oxides, and dithionite-EDTA (DE) to dissolve crystalline iron oxides. The phosphate adsorption capacities of the extracted soils were taken as the maximum quantity of phosphate adsorbed computed from the Langmuir equation. The decreases in the phosphate adsorption capacity following EDTA extraction and DE extraction were attributed to the removal of iron oxides. Close correlations (P<0.001) were found (i) between EDTA-extractable iron (amorphous iron oxides) and the decrease in phosphate adsorption capacity following EDTA extraction, and (ii) between the difference between DE-extractable iron and EDTA-extractable iron (crystalline iron oxides) and the further decrease in phosphate adsorption capacity following DE extraction. The phosphate adsorption capacity, estimated to be approximately 2.5 μmol P m^?2, was in good agreement with the capacity of various synthetic iron oxides. The calculated phosphate adsorption capacity of soil iron oxides, obtained from the contents and specific surfaces of amorphous and crystalline iron oxides together with the phosphate adsorption capacity per m² for synthetic iron oxides, compared favourably with the measured phosphate adsorption capacity.     

ADSORPTION OF PHOSPHATE BY VARIOUS OXIDES: THEORETICAL TREATMENT OF THE ADSORPTION ENVELOPE

An explanation is put forward for the shape of adsorption envelopes found for phosphate adsorption by various metallic oxides. The equation x_m= C₁ (μH₃PO⁴⁺μ∑anions) is proposed, where μH₃pO₄ is the chemical potential of undissociated H₃PO₄; μ∑anions is the chemical potential of all phosphate anions considered as one. component; C₁ is a constant that includes influences of surface charge, chemical affinity of the metal for phosphate, specific surface area, etc., and x_mis the calculated Langmuir maximum adsorption of P at each pH. The dependence of C₁ on the metal present in the oxide is shown.     

铁铝氧化物和高岭石对转化酶的吸附及活性的影响

Experiments were conducted to study the influences of synthetic bayerite, non-crystalline aluminum oxide (N-AlOH), goethite, non-crystalline iron oxide (N-FeOH) and kaolinite on the adsorption, activity, kinetics and thermal stability of invertase. Adsorption of invertase on iron, aluminum oxides fitted Langmuir equation. The amount of invertase held on the minerals followed the sequence kaolinite > goethite > N-AlOH > bayerite > N-FeOH. No correlation was found between enzyme adsorption and the specific surface area of minerals examined. The differences in the surface structure of minerals and the arrangement of enzymatic molecules on mineral surfaces led to the different capacities of minerals for enzyme adsorption. The adsorption of invertase on bayerite, N-AlOH, goethite, N-FeOH and kaolinite was differently affected by pH. The order for the activity of invertase adsorbed on minerals was N-FeOH > N-AlOH > bayerite > reak goethite > kaolinite. The inhibition effect of minerals on enzyme activity was kaolinite > crystalline oxides > non-crystalline oxides. The pH optimum of iron oxide- and aluminum oxide-invertase complexes was similar to that of free enzyme (pH 4.0), whereas the pH optimum of kaolinite-invertase complex was one pH unit higher than that of free enzyme. The affinity to substrate and the maximum reaction velocity as well as the thermal stability of combined invertase were lower than those of the free enzyme.     

PHOSPHATE ADSORPTION BY SYNTHETIC AMORPHOUS ALUMINOSILICATES

Phosphate adsorption isotherms were determined for four synthetic amorphous aluminosilicate gels with A1: A1 + Si molar ratios of 0.29 to 0.88. The concomitant silicate release and acid consumed to maintain the pH of the suspensions constant were also measured. The adsorption isotherms were analysed applying a two-term Langmuir equation–assuming two types of sites. The experimental points fitted the predicted adsorption curves only up to a certain amount of phosphate adsorbed. The deviation at high phosphate adsorption values suggested the presence of more than two types of adsorption site. A comparison of phosphate adsorbed with the silicate released and acid consumed to maintain the pH constant indicated that, for a 3 h reaction time at concentrations below about 10 μmol cm^?3, phosphate exchanges mainly with aquo and hydroxo ligands and with adsorbed silicate. At higher concentrations phosphate is adsorbed (i) on sites arising from the disruption of hydroxy aluminium polymers in the gels and (ii) by the displacement of structural silicate.     

STUDIES ON SOIL COPPER

Adsorption isotherms were determined for the specific adsorption of copper by soils and soil constituents. Adsorption was found to conform to the Langmuir equation. The Langmuir constants, a (adsorption maximum) and b (bonding term), were calculated. Soils were found to have specific adsorption maxima at pH 5.5 of between 340 and 5780 μg g^?1, and a multiple regression analysis revealed that organic matter and free manganese oxides were the dominant constituents contributing towards specific adsorption. Adsorption maxima for soil constituents followed the order manganese oxides > organic matter > iron oxides > clay minerals, which supported the findings for whole soils. The cation exchange capacities (non-specific adsorption) of the test soils were found to be far greater than the specific adsorption maxima. However, evidence suggests that, for the relatively small amounts of copper normally present in soils, specific adsorption is the more important process in controlling the concentration of copper in the soil solution.     

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.     

Adsorption of DNA on clay minerals and various colloidal particles from an Alfisol

Adsorption and desorption of salmon sperm DNA on four different colloidal fractions from Brown Soil and clay minerals were studied. The adsorption isotherms of DNA on the examined soil colloids and minerals conformed to the Langmuir equation. The amount of DNA adsorbed followed the order: montmorillonite?fine inorganic clay>fine organic clay>kaolinite>coarse inorganic clay>coarse organic clay. A marked decrease in the adsorption of DNA on organic clays and montmorillonite was observed with the increase of pH from 2.0 to 5.0. Negligible DNA was adsorbed by organic clays above pH 5.0. As for inorganic clays and kaolinite, a slow decrease in DNA adsorption was found with increasing pH from 2.0 to 9.0. The results implied that electrostatic interactions played a more important role in DNA adsorption on organic clays and montmorillonite. Magnesium ion was more efficient than sodium ion in promoting DNA adsorption on soil colloids and minerals. DNA molecules on soil colloids and minerals were desorbed by sequential washing with 10 mM Tris, 100 mM NaCl and 100 mM phosphate at pH 7.0. A percentage of 53.7-64.4% of adsorbed DNA on organic clays and montmorillonite was released, while only 10.7-15.2% of DNA on inorganic clays and kaolinite was desorbed by Tris and NaCl. The percent desorption of DNA from inorganic clays, organic clays, montmorillonite and kaolinite by phosphate was 39.7-42.2, 23.6-28.8, 29.7 and 11.4%, respectively. Data from this work indicated that fine clays dominate the amount of DNA adsorption and coarse clays play a more important role in the binding affinity of DNA in soil. Organic matter may not favor DNA adsorption in permanent-charge soil. The information obtained is of fundamental significance for the understanding of the ultimate fate of extracellular DNA in soil.     

Phosphate adsorption on uncoated and humic acid-coated iron oxides

Purpose

The phosphate adsorption on natural adsorbents is of particular importance in regulating the transport and bioavailability of phosphates in environmental system. In soils, oxides are often associated with organic matter and form mineral-organic complexes. The aim of the present paper was to investigate the mechanisms of phosphate adsorption on these complexes.

Materials and methods

Phosphate adsorption on uncoated and humic acid (HA)-coated iron oxide complexes was investigated at different ionic strengths and pH by isotherm experiments and attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy.

Results and discussion

Results showed that HA-coated iron oxide complexes caused a decrease in the specific surface area (SSA) and the isoelectric point (IEP) of oxides. Phosphate adsorption on iron oxides was insensitive to changes of ionic strength, while it increased on the complexes with increasing ionic strength. The presence of HA decreased the maximum adsorption and the affinity of phosphate on the complexes. The zeta potential of phosphate-bound iron oxides linearly reduced with the increment of phosphate surface coverage, while the zeta potential of complexes with adsorbed phosphate kept at the same level. ATR-FTIR analysis suggested the formation of phosphate-metal complexation. The presence of HA promotes the formation of the monodentate phosphate complexes at pH 4.5 and significantly influenced phosphate species at pH 8.5.

Conclusions

The amount of phosphate adsorbed was reduced, and the phosphate speciation was also influenced when phosphate was adsorbed on HA-coated iron oxide complexes compared with phosphate adsorption on pure goethite and hematite.

     

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.     

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.     

THE HIGH- AND LOW-ENERGY PHOSPHATE ADSORBING SURFACES IN CALCAREOUS SOILS

The two-surface Langmuir equation was used to study P adsorption by 24 calcareous soils (pH 7.2-7.6; 0.8-24.2 per cent CaCO₃) from the Sherborne soil series, which are derived from Jurassic limestone. High-energy P adsorption capacities (x″_m) ranged from 140–345 μg P/g and were most closely correlated with dithionite-soluble Fe. Hydrous oxides therefore appear to provide the principal sites, even in calcareous soils, on which P is strongly adsorbed (x″_m 6–51 ml/μg P). The low-energy adsorption capacities (x″_m) ranged from 400–663 μg P/g and were correlated with organic matter contents and the total surface areas of CaCO₃ but not with per cent CaCO₃, pH, or dithionite-soluble Fe. Total surface areas of CaCO₃ in the soils ranged from 4.0 to 8.5 m²/g soil. Low-energy P adsorption capacities agree reasonably with values (100 pg P/m²) for the sorption of phosphate on Jurassic limestones but phosphate was bonded much less strongly by soil carbonates (k″= 0.08–0.45 ml/μg P) than by limestones (k～10.0 ml/μg P). Low-energy P adsorption in these soils is tentatively ascribed to adsorption on sites already occupied by organic anions (and probably also by bicarbonate and silicate ions) which lessen the bonding energy of co-adsorbed P.     

Isolating the influence of pH on the amounts and forms of soil organic phosphorus

Soil pH influences the chemistry, dynamics and biological availability of phosphorus (P), but few studies have isolated the effect of pH from other soil properties. We studied phosphorus chemistry in soils along the Hoosfield acid strip (Rothamsted, UK), where a pH gradient from 3.7 to 7.8 occurs in a single soil with little variation in total phosphorus (mean ± standard deviation 399 ± 27 mg P kg^?1). Soil organic phosphorus represented a consistent proportion of the total soil phosphorus (36 ± 2%) irrespective of soil pH. However, organic phosphorus concentrations increased by about 20% in the most acidic soils (pH < 4.0), through an accumulation of inositol hexakisphosphate, DNA and phosphonates. The increase in organic phosphorus in the most acidic soils was not related to organic carbon, because organic carbon concentrations declined at pH < 4.0. Thus, the organic carbon to organic phosphorus ratio declined from about 70 in neutral soils to about 50 in strongly acidic soils. In contrast to organic phosphorus, inorganic phosphorus was affected strongly by soil pH, because readily‐exchangeable phosphate extracted with anion‐exchange membranes and a more stable inorganic phosphorus pool extracted in NaOH–EDTA both increased markedly as soil pH declined. Inorganic orthophosphate concentrations were correlated negatively with amorphous manganese and positively with amorphous aluminium oxides, suggesting that soil pH influences orthophosphate stabilization via metal oxides. We conclude that pH has a relatively minor influence on the amount of organic phosphorus in soil, although some forms of organic phosphorus accumulate preferentially under strongly acidic conditions.     

Pb adsorption by soils

Pb adsorption for 12 soils from Tuscany was studied. The data fitted the Langmuir and the Freundlich isotherms over a large range of concentrations. Results showed that organic matter and clay content were responsible for adsorption maxima. The effect of Mn oxides, explained independently of organic matter and clay, was negligible. The adsorption maxima were generally found to be greater than CEC; the possible mechanisms are discussed.     

Tillage, mineralization and leaching: phosphate

Phosphate is usually the limiting nutrient for the formation of algal blooms in freshwater bodies, so tillage practices must minimize phosphate losses by leaching and surface run-off from cultivated land. Mineral soils usually contain 30–70% of their phosphate in organic forms, and both organic and inorganic phosphate are found in the soil solution. Some organic phosphates, notably the inositol phosphates, are as strongly sorbed by soil as inorganic phosphates, and this decreases their susceptibility to mineralization. The strength with which both categories are sorbed lessens the risk of their being leached as solutes but makes it more likely that they will be carried from the soil on colloidal or particulate matter, and the greatest losses of phosphate from the soil usually occur by surface run-off and erosion. Recent studies at Rothamsted have, however, shown substantial concentrations of phosphate in drainage from plots that have long received more phosphate as fertilizer than is removed in crops. These losses probably occurred because preferential water flow carried the phosphate rapidly from the surface soil to the field drains. For lessening losses of phosphate by leaching and run-off, the prime requirement of tillage is that it should encourage flows of water through the soil that help it to retain phosphate. Primary and secondary tillage should ensure that the surface roughness and porosity of the top-soil encourage the flow of water into the soil matrix where it will move relatively slowly and allow phosphate to be sorbed, thereby avoiding problems from run-off and preferential flow. Inversion tillage can be useful for lessening the loss of phosphate by run-off and erosion. Secondary tillage could be used to decrease the size of the aggregates and increase the surface area for sorption. Although tillage will increase the mineralization of organic phosphate, pulses of mineralization are unlikely to be so rapid or to lead to such large losses as with nitrate. The strength with which phosphate is sorbed also lessens the problem. As with nitrate, the key to managing phosphate is basically good husbandry.     

Relative Agronomic Effectiveness of phosphate rocks and P adsorption characteristics of an Oxic Rhodustalf in Eastern India

The Relative Agronomic Effectiveness (RAE) of rock phosphates as compared to water soluble Triple Super Phosphate was measured on direct, residual, and cumulative application of the P fertilizers in a field experiment with rice on an Oxic‐Rhodustalf in the eastern plateau region of India. The fertilizers were Morocco Rock Phosphate (MORP), Mussoorie Rock Phosphate (MRP), Partially Acidulated Rock Phosphate (PARP), and Triple Super Phosphate (TSP). The RAE of the rock phosphates were lower for direct application (54–80 %) and cumulative application (70–93 %) of P but roughly equal or larger for the residual effect (92–142 %) as compared to TSP. The P adsorption characteristic of the experimental soil conformed to the linear relationship of both Freundlich and Langmuir isotherm equation. The adsorption data when plotted according to Langmuir equation deviated from a single linear relationship at higher concentration (10 μg ml^–1), thereby giving two adsorption maximum values ( 68.49 μg g^–1 and 256.41 μg g^–1) and binding energies ( 2.86 ml μg^–1 and 0.089 ml μg^–1) for the soil. Two populations of P adsorption site with widely different affinity for P probably existed in the soil.