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.     

Describing the effect of time on sorption of phosphate by iron and aluminium hydroxides

Iron and aluminium hydroxides were precipitated both in the presence and absence of kaolinite. The reaction between phosphate and these hydroxides was measured for periods which ranged from 5 min to 72 h. The effect of time on phosphate sorption was examined by plotting the sorption data according to different, simple, kinetic equations such as the first order, second order, the parabolic diffusion equation, the Elovich equation and the modified Freundlich equation. The effect of time on sorption was also examined by the mechanistic model recently developed by Barrow (1983b) for the sorption and desorption of phosphate by soils. The sorption of phosphate by iron and aluminium hydroxides increased with time and the reaction continued through the period of observation without reaching a true equilibrium. Curvilinear relationships were obtained when the data were plotted according to the simple kinetic equations. These simple kinetic equations fail to describe the effect of time on sorption partly because the mechanism is different from that postulated and partly because they do not consider electrostatic effects when phosphate ions react with a charged surface. The mechanistic model of Barrow (1983b), which takes this effect into account, described effect of both concentration and time on phosphate sorption. According to this model, the increase in phosphate sorption with time was caused by a redistribution of adsorbed phosphate into the interior of the particles of iron and aluminium hydroxides by solid-state diffusion.     

Formation and properties of hydroxy iron(iii) oligomer-citrate complex

Instantaneous neutralization of Fe (III) chloride dissolved in N a citrate by powdery NaHC03 gave stable clear brown sols. The sol particles separated by dialysis and freeze-drying showed a single diffraction peak at 2 nm and a citrate/Fe molar ratio of about 0.2 irrespective of the composition of the starting solutions. This indicates that the product may be a novel phase of Fe (III) citrate.     

Proton consumption with phosphate adsorption on amorphous fe(iii) hydroxide

Proton consumption with phosphate adsorption on amorphous Fe (III) hydroxide (am-Fe(OH)₃) was compared between two different pH-controlled conditions in a 0.1 mol dm^-3 NaClO₄ solution at initial pH values of 5.50 and 4.50, at 298±0.005 K.

The number of protons caused by phosphate dissociation was subtracted from the total number of protons consumed, then the amount of surface OH groups released by the ligand exchange reaction were determined. When a sequential acid titration by a pH-stat maintained pH values of the systems at initial pH values, the percentage of OH groups released during the ligand exchange reaction was almost constant, 29–37%. When the pH values of the systems increased with phosphate adsorption, the percentage of OH groups released by the ligand exchange reaction varied from -4.3 to 33%. The difference in the proton migration between the two pH-controlled conditions not only depended on the phosphate dissociation, but on the difference in the adsorption mechanism, i.e. the ratio of ligand exchange with OH groups to total phosphate adsorption.     

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.     

Sorption of phosphate by bayerite

The chemisorption of phosphate on aluminium hydroxide (bayerite) and its kinetics were studied. A rate equation was derived on the basis that each phosphate molecule replaces a surface hydroxyl group and binds directly to an aluminium atom. The rate constants were evaluated and the free energy change of the sorption reaction was calculated as 20.4 KJ/mol.     

Sorption and degradation of azimsulfuron on iron(III)-rich soil colloids

The sorption of N-[[(4,6-dimethoxypyrimidin-2-yl)amino]carbonyl]-1-methyl-4-(2-methyl-2H-tetrazole-5-yl)1H-pyrazole-5-sulfonamide (AZS) on an iron oxide, iron(III)-humate, and an Fe3+-saturated clay was studied using a batch equilibrium method. Generally, 20 mg of each colloid was equilibrated with 20 mL of AZS solution (1.5-12.7 microM). The sorption on iron-montmorillonite and iron oxide was rapid, and the equilibrium was attained within 1.5 and 5 h, respectively. In the case of Fe-saturated humic acid the equilibrium time was 20 h. After equilibration, the phases were centrifuged (19000g, 15 min) and the supernatant was sampled and analyzed by HPLC. The values of Freundlich constants indicate that iron oxide (Kads = 199.5) shows the highest sorptive capacity toward AZS, followed by iron(III)-clay (Kads = 146.6) and iron(III)-humate (Kads = 108.2). With elapsing time, AZS degradation was observed in all colloidal suspensions. Iron-humate (t(1/2) = 136 h) is most effective in promoting AZS degradation, followed by iron oxide (t(1/2) = 204 h) and iron-clay (t(1/2) = 385 h). The metabolites 2-amino-4,6-dimethoxypyrimidine and 1-methyl-4-(2-methyl-2H-tetrazole-5-yl)-1H-pyrazole-5-sulfonamide, arising from a hydrolytic cleavage of the sulfonylurea bridge, were the only byproducts observed. A Fourier transform infrared study suggests that the sorption of AZS on iron-clay involves the protonation of one of the two basic pyrimidine nitrogens induced by the acidic water surrounding the saturating Fe3+ ions. Instead, the formation of a six-membered chelated complex favors the sorption of AZS on iron oxide.     

Extraction methods for aluminium and iron in relation to phosphate adsorption

Abstract

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

Sorption and desorption characteristics of organic phosphates of different structures on aluminium (oxyhydr)oxides

Sorption and desorption characteristics of four organic phosphates (OPs) with different molecular sizes and structures (glycerophosphate, GP; glucose‐6‐phosphate, G6P; adenosine triphosphate, ATP; myo‐inositol hexakisphosphate, IHP) and inorganic phosphate (P_i) on three aluminium (Al) (oxyhydr)oxides (amorphous Al(OH)₃, boehmite and α‐Al₂O₃) were investigated. The maximum sorption amounts of OPs and P_i increased with decreasing crystallinity of the minerals on a per mass basis: α‐Al₂O₃ < boehmite < amorphous Al(OH)₃. With an exception of IHP sorption on amorphous Al(OH)₃, the maximum surface area‐based sorption densities increased with decreasing molecular weight (MW) of OPs and P_i: IHP < ATP < G6P < GP < P_i. Despite having the largest MW, IHP had greater sorption amounts on amorphous Al(OH)₃ than the other OPs because of the transformation of surface complexes to surface precipitates. Sorption kinetics of OPs was first a rapid sorption followed by a long and slow sorption process. Of the three Al (oxyhydr)oxides, amorphous Al(OH)₃ had the greatest first rapid sorption density and initial sorption rate of OPs within 5 minutes, both factors decreasing with increasing MW of OPs. The initial desorption percentages of OPs by KCl generally increased with decreasing MW of OPs, whereas the maximum desorption percentages of OPs by citrate were four to five times those achieved with KCl. Overall, strong specific sorption of OPs occurs on the surface of Al (oxyhydr)oxides, and molecular structure and size of OPs, as well as crystallinity and crystal structure of the minerals, are the key factors affecting the interfacial reactions and environmental behaviour of OPs.     

Molybdate sorption by oxides of aluminium and iron

The sorption of molybdate by goethite, hematite, bayerite and α-Al₂O₃ was studied as a function of molybdate concentration and pH. The sorption isotherms exhibited double sorption plateaus in which the amount of Mo sorbed in the second plateau was double that in the first. This was attributed to the polymerization of molybdates as the concentration increases. Furthermore Mo sorption was found to be associated with a cosorption of Na cations, probably present to maintain electroneutrality in the surface zone. The sorption showed high sensitivity towards the pH, attaining a maximum at pH 4. For the iron oxides the decrease in sorption was much less pronounced on the acid side of the pH maximum and occured at lower pH values than that of the Al oxides. Molybdate sorption is explained in terms of a ligand exchange reaction between molybdate and surface hydroxyls.     

Sorption of antimony species by humic acid

The retention of antimony (a potential toxin) in polluted soils or waterway sediments can involve interaction with several component phases. One of these, humic acid, has been found to adsorb antimony (III) from solutions of Sb(OH)₃ or potassium antimonyl tartrate (C₈H₄K₂Sb₂O₁₂) in accordance with Langmuir type isotherms. Using Sb(OH)₃ solutions (initial Sb levels < 10 μM) the bonding constant value (at pH 4) was 6 × 10⁵, with a calculated saturation capacity of 23 μmol g^?1. In the antimonyl tartrate systems (initial Sb levels 0.5 to 75 μM) the bonding constant value for the sorbed species was 1.6 × 10⁵ and the saturation capacity 53 μmol g^?1. Addition of small amounts of HCl or NaOH (to vary the pH between 3.1 and 5.4) had little effect on the amount sorbed from KSbT solutions but with Sb(OH)₃ solutions uptake was reduced (by about 15%). In the presence of NaCl (0.5 or 0.05M) Sb uptake increased (by about 15%). Antimony (V) (introduced as KSb (OH)₆) was not sorbed from solutions < 10 μM in this salt. Using more concentrated solutions, uptake gradually increased, reaching a plateau value of around 8 μmol g^?1 with solutions initially 50 or 75 μM.     

铝(氢)氧化物对有机酸和磷酸根的竞争吸附研究

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

Sorption of trace metals by suction cups of aluminium oxide,ceramic and plastics

The sorption properties of ceramic, aluminium oxide and plastic suction cups in respect to trace metals (Be, Cd, Co, Cu, Mn, Ni, Pb, Zn) were compared in laboratory and field experiments. The sorption effect is determined by the level of the cation exchange capacity of the cup material, the pH-value of the soil solution, the content of dissolved organic carbon, the sampling rate and the sampled volume. Sorption was generally negligible only in case of cobalt, manganese and nickel. At low pH-values no retention of trace metals occurred with the exception of lead in the aluminium oxide and the ceramic cups. At pH-values of about 8 cadmium and zinc were strongly sorbed only by aluminium oxide and ceramic cups whereas beryllium, copper and lead were markedly sorbed at this pH-range by all cup types. These results are only valid for the boundary conditions used. Whenever a suction cup's suitability is in doubt it should be tested after a conditioning procedure using realistic boundary conditions.     

Dissolution of aluminum and iron phosphate by humic acids

Abstract

An investigation was conducted to study the effect of humic (HA) and fulvic acid (FA) on the dissolution of aluminum phosphate (AlPO₄) and iron phosphate (FePO₄), to analyze the dissolution products, and assess their availability to plants. The rate of dissolution was determined by shaking 10 mg of Al‐ or FePO₄ with 0 to 800 mg L^‐1 of HA or FA solutions at pH 7.0 for 0 to 192 hours. The phosphorus (P) concentration was measured in the extracts by spectrophotometry, whereas the nature of P‐humic acid complexes was determined by ³¹P NMR analysis. Availability of dissolution products was studied by growing corn plants in aerated hydroponic solutions receiving treatments of 50 mg Al‐ or FePO₄ and 0 to 800 mg L^‐1 of HA or FA at pH 5.0. The results indicated that the amount of P released by HA or FA increased with time. Humic acid was more effective than FA in dissolving the metal phosphates. The ³¹P NMR analysis showed that the dissolution products contained free orthophosphates and minor amounts of P‐humic acid complexes. This confirms the role of HA as a powerful chelator of Al and Fe, liberating in this way the orthophosphate anions. Corn plants grown in hydroponics, with AlPO₄ or FePO₄ as the source of P, exhibited better growth performance when HA or FA are present.     

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.     

Comparison of different models for phosphate sorption as a function of the iron and aluminium oxides of soils

Phosphate sorption on topsoil and subsoil samples from different soils located in the eastern part of Germany was studied. Two models were fitted to sorption data obtained after 4 and 40 d of gentle shaking. The models differ with respect to the fractions of iron and aluminium (hydr)oxides that are considered and whether the phosphate initially sorbed in the soil is taken into zccount. Oxalate-extractable P, (P_ox), appears to be a major part of the total soil P. The total P sorption measured, F, was predominantly related to the amounts of amorphous iron (Fe_ox) and aluminium (Al_ox). A significant relation between crystalline iron (Fe_d– Fe_ox) and total P sorption was not found. Reversibly adsorbed phosphate (P_i), measured after 40 d reaction time, was a function of clay content and content of amorphous iron and aluminium (hydr)oxides.     

Effect of iron oxide on phosphate sorption by calcite and calcareous soils

Pure calcite (AR grade CaCO₃) was treated with ferrous perchlorate solution to give a surface coating of iron (Fe) oxide. Maximum sorption (x_m) of phosphate (P) by the calcite increased from 18.2 to 160 mg P kg^?1 as the amount of coating increased from 0.00 to 16.0 g Fe₂O₃, kg^?1 CaCO₃. Evidence for Fe oxide coatings on carbonate minerals in two Sudanese soils was obtained by optical microscopy and electron-probe microanalysis. The relative contributions of carbonate and Fe oxide minerals, and Fe oxide coatings to P sorption in these soils were calculated, based on an assumed model of oxide distribution. Separate-phase Fe oxide was the major contributor (30–40%) to P sorption in the soils; the Fe oxide coatings on carbonate minerals were only minor contributors (< 6%), and the contribution of uncoated carbonate minerals was found to be negligible (<1 %). These results suggest a very minor role for carbonate minerals, even when coated with Fe oxide, in the sorption of P by these calcareous, Sudanese soils.     

An investigation of phosphate adsorbed on aluminium oxyhydroxide and oxide phases by nuclear magnetic resonance

The adsorption of phosphate by soil minerals controls availability of P to plants, but the chemical environments of adsorbed phosphate are poorly known. We used ³¹P MAS NMR to study the adsorption of phosphate on to boehmite (γ‐AlOOH) and γ‐Al₂O₃ with large surface areas. The solid phases were reacted in 0.1 m phosphate solutions at pH from 3 to 11 and in solutions with pH 5 at concentrations from 10^?1 m to 10^?4 m . The spectra suggested three different phosphate environments: (i) orthophosphate precipitated from the residual solution after vacuum filtering, (ii) surface‐adsorbed phosphate in inner‐sphere complexes, and (iii) Al‐phosphate precipitates on the surfaces of the minerals. The chemical shifts of both the inner‐sphere complexes and surface precipitates became progressively less shielded with increasing pH and decreasing concentration of phosphate solution. For the inner‐sphere complexes, we interpret these changes to be the result of decreasing phosphate protonation combined with rapid proton exchange among phosphate tetrahedra with different numbers of protons, which causes peak averaging. The chemical shifts of ³¹P of the Al‐phosphate precipitates were more negative than those of the surface phosphates at a given pH and solution concentration, probably because of a larger number of P–O–Al linkages per tetrahedron. The observed trend of decreasing shielding is probably due to the decreasing average number of P–O–Al linkages per tetrahedron combined with decreasing protonation and an increasing number of K⁺ next‐nearest neighbours. Even at small concentrations of phosphate solution, a significant amount of Al‐phosphate precipitate was present.     

Influence of some chelates of aluminium on the sorption of phosphate by hydrous Al-oxides

Sorption of phosphate by hydrous oxides of aluminium was studied as a function of pH, presence of chelates of aluminium and of the specific surface areas of the oxides. Aluminon was most effective in reducing P sorption followed by oxalic acid and EDTA. Acetylacetone, 8-hydroxyquinoline, salicylic acid and fluoride affected little P sorption. The sorption was found to be higher the higher the value of the specific surface area of the oxide, but the shape of the sorption curve was the same for all the oxides studied, exhibiting a maximum at about pH 5. This maximum was found to coincide with the point of zero charge as determined in the presence of acetate ions. The sorption data are explained in terms of a ligand exchange mechanism in which phosphate chemisorbs on surface aluminium atoms displacing uncharged surface hydroxyls.     

A Study on Al(III) and Fe(II) Ions Sorption by Cattle Manure Vermicompost

Cattle manure vermicompost has been used for the adsorption of Al(III) and Fe(II) from both synthetic solution and kaolin industry wastewater. The optimum conditions for Al(III) and Fe(II) adsorption at pH?2 (natural pH of the wastewater) were particle size of ≤250?µm, 1 g/10 mL adsorbent dose, contact time of 4 h, and temperature of 25°C. Langmuir and Freundlich adsorption isotherms fitted reasonably well in the experimental data, and their constants were evaluated, with R ² values from 0.90 to 0.98. In synthetic solution, the maximum adsorption capacity of the vermicompost for Al(III) was 8.35 mg g^?1 and for Fe(II) was 16.98 mg g^?1 at 25°C when the vermicompost dose was 1 g 10 mL^?1, and the initial adjusted pH was 2. The batch adsorption studies of Al(III) and Fe(II) on vermicompost using kaolin wastewater have shown that the maximum adsorption capacities were 1.10 and 4.30 mg g^?1, respectively, at pH?2. The thermodynamic parameter, the Gibbs free energy, was calculated for each system, and the negative values obtained confirm that the adsorption processes were spontaneous.