Kinetics of phosphate adsorption on iron oxides formed under the influence of citrate

C. Liu and P. M. Huang1

Department of Soil Science, University of Saskatchewan, 51 Campus Drive, Saskatoon, Saskatchewan, Canada S7N 5A8. Received 5 August 1999, accepted 11 April 2000.
Liu, C. and Huang, P. M. 2000. Kinetics of phosphate adsorption on iron oxides formed under the influence of citrate. Can. J. Soil Sci. 80: 445454. The influence of organic acids on the formation of Fe oxyhydroxides and oxides has been intensively studied. However, scant attention has been paid to the subsequent effect on surface chemistry of the Fe oxides formed. The kinetics and mechanisms of phosphate adsorption by the Fe oxides formed in the presence of citrate ligands at initial citrate/Fe(II) molar ratios (MR) of 0, 0.001, 0.01, and 0.1 were investigated using the conventional batch method. The adsorption studies were conducted at the initial phosphate concentration of 0.5 mM and pH 4.0 during the reaction period from 2 min to 56 h at 278, 288, 298, and 313 K. The results show that the phosphate adsorption followed multiple second-order kinetics and had two distinct rates in each reaction system. The amount, rate coefficient, activation energy and pre-exponential factor of phosphate adsorption by the Fe oxides formed greatly varied with their structural and surface properties. These properties, which included crystal structure, specific surface area, surface porosity, surface geometry, and point of zero salt effect (PZSE), differed significantly with the initial citrate/Fe(II) MR at which Fe oxides were formed. The results of this study have cast the light on the role of organic acids such as citric acid in influencing the surface chemistry of naturally occurring Fe oxides through fundamental structural perturbation and the impact on the dynamics of phosphate in terrestrial and aquatic environments. Key words: Kinetics, activation energy, pre-exponential factor, phosphate, iron oxides, citric acid, structural perturbation Liu, C. et Huang, P. M. 2000. Cintique de ladsorption des phosphates sur les oxydes de fer forms sous linfluence des citrates. Can. J. Soil Sci. 80: 445454. Bien que linfluence des acides organiques sur la formation des oxyhydroxydes et des oxydes de fer ait fait lobjet dtudes intensives, on sest peu intress leffet des oxydes ainsi forms sur la chimie du sol de surface. Nous tudions selon la mthode classique par fractionnement la cintique et les mcanismes de ladsorption des phosphates sur les oxydes de Fe forms en prsence de ligands de citrate, pour des rapports molaires (RM) citrates/Fe (II) de 0, 001, 0,01 et 0,1. Les tudes dadsorption taient ralises la concentration initiale de phosphate de 0,5 mM au pH 4,0 durant des priodes allant de 2 min 56 h, 278, 288, 298 et 313 K. Les rsultats obtenus montrent que ladsorption du phosphate suivait une cintique multiple du second degr comportant deux taux distincts, dans chaque systme de raction. La quantit, le coefficient de taux, lnergie dactivation et le facteur pr-exponentiel dadsorption des phosphates sur les oxydes de Fe forms variaient grandement selon les proprits structurales et les proprits de surface des oxydes : structure cristalline, surface spcifique, porosit, gomtrie ainsi que le point effet zro des sels (PZSE). Ces dernires proprits diffraient de faon significative selon le RM citrate/Fe (II) initial auquel les oxydes avaient t forms. Nos observations jettent de la lumire sur linfluence des acides organiques, comme lacide citrique, sur la chimie de surface des oxydes de Fe naturels par voie de perturbations structurales fondamentales et sur limpact de la cintique des phosphates dans les milieux terrestres et les milieux aquatiques. Mots cls: Cintique, nergie dactivation, facteur pr-exponentiel, phosphate, oxyde de fer, acide citrique, perturbation structurale

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The chemical reactions that occur in soils and aquatic environments are dynamic processes (Sparks 1998) and, therefore, a kinetic study is essential to describe and predict the adsorption and desorption reactions occurring in natural environments. Phosphorus is a major nutrient in soils (Tisdale et al. 1993) and a pollutant in aquatic environments (Bagotskii and Vavilin 1989); its fate in soils and associated environments has been of interest to scientists concerned with plant nutrition and environmental protection for a long time. Phosphate adsorption by soils is affected by a number of soil components, including Fe oxides (Borggaard 1983). Thus, close relationships between phosphate adsorption and the total amount (dithionite-citrate-bicarbonate-extractable
1To

whom correspondence should be addressed.

445

Fe) and/or the noncrystalline fraction (oxalate-extractable Fe) of Fe oxides in soils and sediments have frequently been demonstrated (Ballard and Fiskell 1974; Schwertmann and Schieck 1980; Le Mare 1981; Borggaard 1983; Schwertmann and Taylor 1989). The kinetics of phosphate adsorption by pure Fe oxides has been intensively studied over the last two decades (Kuo and Lotse 1973; Parfitt and Atkinson 1976; Anderson et al. 1985; Bolan et al. 1985; Hansmann and Anderson 1985; Madrid and de Arambarri 1985; Shang et al. 1993). However, pure Fe oxides seldom occur in natural environments, since other ions present in the environment can influence their formation (Krishnamurti and Huang 1990; Cornell and Schwertmann 1996). The presence of low-molecular-weight organic acids such as citric acid during the formation of Fe oxides can greatly modify the surface prop-

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erties of the Fe oxides formed, such as surface structure, surface geometry, specific surface area, surface porosity, surface charge, and PZSE, through fundamental structural modifications (Liu and Huang 1999). Ainsworth and Sumner (1985) found that Al substitution in goethite affected the pseudo-first-order rate constant of phosphate adsorption by the goethite at all pH levels and lower phosphate concentrations. It is postulated that Al substitution may sterically hinder the sorption of phosphate. The isomorphous substitution of the smaller Al3+ ion (0.051-nm radius) for the larger Fe3+ ion (0.064-nm radius) may cause aberrations in the surface that would affect the adsorption process (Ainsworth and Sumner 1985). Two possible aberrations that could affect the adsorption process are the primary surface structure involving the symmetry and spacing of the surface atoms and the secondary surface structure consisting of steps, edges, and other microtopographical features (Ainsworth and Sumner 1985). These changes in surface geometry appear to affect the activation energies, the strengths of adsorption and desorption, and the rate of phosphate adsorption onto the goethite. However, little is known of the influence of surface properties resulting from fundamental structural modifications of Fe oxides by the presence of organic ligands during their formation on the kinetics of adsorption of phosphate. The kinetics of phosphate adsorption by soils or soil constituents is characteristically a rapid reaction followed by a slow reaction (Barrow et al. 1981; Ainsworth and Sumner 1985). Kinetic models, that have been used to investigate phosphate adsorption by soil and soil materials are firstorder and second-order kinetic equations, the two-constant rate equation, and the Elovich equation (Atkinson et al. 1970; Kuo and Lotse 1972, 1973; Griffin and Jurinak 1974; Vig et al. 1979; Chien and Clayton 1980; Chien et al. 1980; Sharpley 1983; Shang et al. 1993). These equations were used to calculate the rate coefficients of the reactions. Although the activation energies of phosphate adsorption on short-range ordered Fe precipitates were reported (Shang et al. 1993), scant attention has been paid to the investigation of the pre-exponential factor in the Arrhenius equation in phosphate adsorption. The objective of this study was to investigate the kinetics and mechanisms of phosphate adsorption by the Fe oxides formed at citrate concentrations ranging from 10 M to 1000 M. This concentration range of citrate is common in soil environments (Robert and Berthelin 1986). MATERIALS AND METHODS Preparation and Characteristics of Iron Oxides Iron oxides were formed in a 0.01 M ferrous perchlorate solution at pH 6.00 0.05 and 296.5 K at initial citrate/ Fe(II) molar ratios (MRs) of 0, 0.001, 0.01, and 0.1. The citrate concentrations were 0, 10, 100, and 1000 M, respectively. A 0.01 M ferrous iron perchlorate solution was made by dissolving 7.257 g of Fe(ClO4)26H2O (Analar grade, Pflatz and Bauer, Waterbury, CT) in 2 L of deionized distilled water in which N2 gas was constantly bubbled. Suitable amounts of the ligand (C6H8O7H2O, Analar grade,

BDH Inc., Toronto, ON) were added into the solution to result in the different initial citrate/Fe(II) MR values. The pH of the solution was adjusted to 6.00 with 0.1 M NaOH using a Metrohm titroprocessor (683 model, Metrohm Ltd., Herisau, Switzerland) in a set-mode. When the pH of the solution was stabilized at 6.00, the N2 bubbling was replaced by air with a flow rate of 40 mL min1. The flow rate of air was controlled by a regulator. The air was passed through 1 M NaOH solution to remove the CO2. The oxidation of ferrous iron was terminated after 2.5 h. The suspensions were filtered through a membrane (pore size of 0.025 m) and washed with deionized distilled water until the conductivity of the filtrate was about 5 S cm1. Finally, the precipitates were freeze-dried. The Fe oxide minerals were examined by X-ray powder diffraction (XRD) on a Rigaku diffractometer (Rigaku Company, Tokyo, Japan) with Fe-K radiation filtered by a graphite monochromator at 40 kV and 130 mA. The X-ray diffractograms were recorded from 4 to 902 with 0.012 steps at 102 per min and 2 s counting time. The specific surface area of the Fe oxides was measured by using a five-point BET N2 adsorption isotherm (Gregg and Sing 1982) obtained with a Quantachrome Autosorb-1 apparatus (Quantachrome Corp., Syosset, NY). Prior to N2 adsorption, 100-mg samples were outgassed for 24 h at 10 mTorr and room temperature (296.5 0.5 K). During N2 adsorption the solids were thermostated in liquid N2 (7778 K). The pore specific surface area of the Fe oxides was also determined from the 93-point N2 adsorption isotherms using the t-plot method of de Boer and the average pore diameter was estimated using the Kelvin equation (assuming cylindrical pores) (Gregg and Sing 1982). The PZSE of the Fe oxides was determined in 0.01, 0.1 and 1 M NaCl solutions by the potentiometric method of Parks and de Bruyn (1962) as modified by Atkinson et al. (1967). The automatic titration as described by Sakurai et al. (1989) used a Metrohm titroprocessor (682 model, Metrohm Ltd., Herisau, Switzerland). The organic carbon content of the Fe oxides was determined with a Leco CR12 C analyzer (Leco Corp., St, Joseph, MI) (Wang and Anderson 1998). Roughness of a surface is characterized by the fluctuations of the height of the surface relative to an appropriate reference plane (Gouyet et al. 1991). Several parameters are applied in surface science to describe surface roughness of an object. Mean surface roughness, which is the average deviation of nonplanar surface from its center plane, is one of these parameters. When the material surfaces are irregular and rough, the mathematical description of the topography can also be achieved by the fractal dimension. A fractal is an object that appears the same, regardless of the scale of observation (Anderson et al. 1998). The fractal dimension of a material surface lies between 2 and 3. A surface fractal dimension 2 is for a planar surface and a surface fractal dimension 3 is for an extremely rough surface that is so irregular that it takes up the whole of three-dimensional space. The mean surface roughness and surface fractal dimension of the Fe oxides formed at varying citrate/Fe(II) MR values were determined based on a scanning area 100 nm 100 nm using atomic force microscopy (NanoScopeTM

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LIU AND HUANG KINETICS OF P ABSORPTION BY FE OXIDES 447

Table 1. Basic surface properties of the iron oxides formed at various initial citrate/Fe(II) MR Initial citrate/Fe(II) MR Property 0 0.001 0.01 L, nc. 189.3 22.2 1.94 2.19 6.2 5.6 0.1 nc. 209.6 136.1 3.68 2.24 55.7 3.9 LSD0.05z 1.6 1.8 0.36 0.02 1.9 0.6 0 0.001 0.01 0.1 1.13 1.58 0.90 0.97 Dominant mineraly G, M L Specific surface area 135.2 102.8 (m2 g1) Micropore area NDx ND (m2 g1) Mean surface roughness 1.36 1.01 (nm) Surface fractal dimension 2.17 2.15 Organic C content 0.2 1.1 (g kg1) PZSE 7.0 6.0 Table 2. The amounts of phosphate adsorbed in the Fe oxide systems at different temperatures at the end of a 56-h reaction period Initial citrate/Fe(II) MR 278 0 0.001 0.01 0.1 15.3 16.3 17.0 20.4 Temperature (K) 288 298 313 32.3 22.4 25.6 40.0 2.39 2.18 1.35 1.91 (cmol kg1)z 22.6 28.6 17.9 20.5 19.1 22.8 33.2 36.8 (mol m2)yx 1.67 2.12 1.74 1.99 1.01 1.20 1.58 1.76

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zLeast significant difference at a 95% confident level. yG, goethite; M, maghemite; L, lepidocrocite; and nc, X-ray xNot detectable.

noncrystalline.

zLSD 0.05 = 0.6 and LSD0.01 = 0.9 for phosphate adsorbed per unit weight of Fe oxides. yLSD 0.05 = 0.07 and LSD0.01 = 0.09 for phosphate adsorbed per unit area. xbased on the specific surface area determined by N -BET method. 2

III, Digital Instruments, Santa Barbara, CA) as described by Liu and Huang (1999). After a height image was captured, the computer automatically recorded all the three-dimensional data of the surface. The mean surface roughness and surface fractal dimension of the Fe oxides were respectively obtained by executing roughness and fractal command in off-line of the NanoScopeTM III Software version 3.0 (Digital Instruments, Inc. 1993) at the same fractal Z ratio of 1. Since the scanning area (100 nm 100 nm) is very small, the determination of the mean surface roughness and surface fractal dimension were conducted in 15 replicates. The basic properties of the Fe oxides are listed in Table 1. Kinetics of Phosphate Adsorption The phosphate adsorption by the Fe oxides formed at the initial citrate/Fe(II) MRs of 0, 0.001, 0.01 and 0.1 was investigated by the conventional batch method. The Fe oxides were dispersed as suspensions by ultrasonification (Sonifier, Model 350, Danbury, CT) at 150 W for 2 min. An aliquot of the suspension containing 50 mg of the Fe oxides was transferred to a series of 125-mL flasks which contained 30 mL of deionized distilled water and then shaken overnight at 278, 288, 298, and 313 K. The pH of the suspensions was adjusted to 4.0 with 0.1 M HClO4 or NaOH. The total volume of the Fe oxide suspension after the pH adjustment was 35 mL. An aliquot of 5 mL of phosphate stock solution (pH 4.0) as NaH2PO4 (4 mM) containing NaClO4 (0.08 M) was added to each flask to adjust the concentrations of phosphate and NaClO4 to 0.5 mM and 10 mM, respectively, bringing the final volume of the mixed suspension to 40 mL. The mixed suspension was shaken for 0.033, 0.083, 0.25, 0.5, 1, 2, 4, 8, 12, 15, 24 and 56 h at 278, 288, 298 and 313 K. The suspensions at the end of each adsorption period were filtered through a 0.1 m Millipore membrane within 15 s. The concentration of phosphate remaining in the filtrates was determined by the molybdophosphoric blue colorimetric method (Jackson 1958). The amount of phosphate adsorbed was determined by taking the

difference between the initial and final concentrations of phosphate in solutions. Statistical Analysis The whole experiment was carried out in duplicate. Two Fe oxide samples formed at each citrate/Fe(II) molar ratio were used for phosphate adsorption experiment and for the determination of the surface properties. The statistical analysis in the present study was carried out by calculating least significant difference (LSD) values based on the standard error of the experimental data and the t values at 95% and 99% confident levels. The LSD value of the rate coefficient and that of the activation energy were calculated based on the standard error of the slope of the rate equation and that of the Arrhenius equation, respectively. The LSD value of the preexponential factor was computed on the basis of the standard error of the intercept of the Arrhenius equation. The LSD values of the mean surface roughness and the surface fractal dimension were calculated based on 15 replicates. RESULTS AND DISCUSSION Amount of P Adsorbed by the Fe Oxides The amounts of phosphate adsorbed by the Fe oxides, which had been formed at the various initial citrate/Fe(II) MRs, at the end of the 56-h reaction period at different temperatures are presented in Table 2. The amounts of phosphate adsorbed by the different Fe oxides increased with increasing temperature, since there is higher energy for the bond breaking and bond formation at a higher temperature. Except for the data obtained at 278 K, the amount of phosphate adsorbed per unit weight of the Fe oxides initially decreased with an increase in the initial citrate/Fe(II) MR from 0 to 0.001 and then steadily increased with the increase in the MR to 0.01 and 0.1. The Fe oxides formed at the initial citrate/Fe(II) MRs of 0.1 and 0.001 adsorbed the largest and smallest amounts of phosphate, respectively, at 288, 298 and 313 K; the former had the largest specific surface and the latter had the smallest specific surface (Table 1). The Fe

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oxides formed at the MR of 0 adsorbed the lowest amount of phosphate at 278 K. The Fe oxides formed at the initial citrate/Fe(II) MR of 0 were predominantly goethite and maghemite, whereas the Fe oxides formed at the MRs of 0.001, 0.01 and 0.1 were lepidocrocite and/or X-ray noncrystalline oxides. Goethite is a more stable phase of Fe oxide than lepidocrocite (Krishnamurti and Huang 1993; Cornell and Schwertmann 1996). The surface OH and/or OH2 of goethite may be bonded to Fe more strongly than those of lepidocrocite (Benjamin and Leckie 1981; Hiemstra et al. 1989a,b). Goethite may need higher energy compared with lepidocrocite to adsorb phosphate by replacing the OH and OH2 groups. At the low temperature, there is not enough energy to break the same number of FeOH bonds on the goethite surfaces as the number of FeOH bonds on the lepidocrocite. Although the Fe oxides formed at the initial citrate/Fe(II) MR of 0.01 had a larger specific surface area compared with those formed in the absence of citrate, more phosphate was adsorbed per unit weight of the latter oxides at 288, 298 and 313 K, indicating that the citrate anion coprecipitated with the Fe oxides may block some of the phosphate adsorption sites. In the present study, citrate ligand was introduced to the system when the Fe oxides were synthesized. After the Fe oxides were formed, the phosphate adsorption experiment was carried out. Therefore, citrate ligands had already occupied some reactive sites on the Fe oxide surface before phosphate was added into the Fe oxide systems. This phenomena is referred to as blocking effect. Further, citrate has a relatively large molecular structure. The presence of citrate on the Fe oxide surface would block some reactive sites on the Fe oxide surface through steric effect and thus reduced the adsorption of phosphate. In addition, the coprecipitation of citrate with Fe oxides during the formation of Fe oxides also changed the porosity of the Fe oxides. Especially when the micropore was formed at citrate/Fe(II) MRs of 0.01 and 0.1 (Table 1), the pore with the diameter less than that of phosphate ions would block the entry of phosphate ions into these micropore surface. This interpretation is substantiated by the amount of citrate coprecipitated with Fe (Table 1) and the amount of phosphate adsorbed per m2 of Fe oxides (Table 2). The amount of citrate coprecipitated with the Fe oxides increased with increasing initial citrate/Fe(II) MR. The phosphate adsorbed per unit surface area of the Fe oxides decreased when the initial citrate/Fe(II) MR increased, except for the initial citrate/Fe(II) MR of 0.1. At this MR, the Fe oxides formed adsorbed more phosphate than that formed at the initial citrate/Fe(II) MR of 0.01. Citrate at the initial citrate/Fe(II) MR of 0.1 inhibited the crystallization of Fe oxides through its incorporation into the structural network of the Fe oxide, resulting in the formation of X-ray noncrystalline Fe oxides. The higher values of mean surface roughness and surface fractal dimension of the noncrystalline oxides formed at the initial citrate/Fe(II) MR of 0.1 (Table 1) indicate that their surface was much rougher compared with the Fe oxides formed at the MRs of 0, 0.001, and 0.01. More edges and corners exist on the rougher surface. Therefore, compared

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with the faces, more Fe-OH and Fe-OH2 groups should be exposed per unit area of edges and corners. Consequently, the noncrystalline Fe oxides formed at the initial citrate/Fe(II) MR of 0.1 would have more exposed Fe-OH and Fe-OH2 functional groups per unit area, which are accessible to phosphate. Another exception was that the phosphate adsorbed per unit surface area of the Fe oxides formed at the initial citrate/Fe(II) MR of 0.001 at 278 and 288 K was higher than that at the initial citrate/Fe(II) MR of 0 at 278 and 288 K. This is also attributed to the fact that more energy is required for the replacement of the OH and OH2 groups on goethite by phosphate compared with those on lepidocrocite. Although the phosphate adsorbed per unit area of the Fe oxides formed at the initial citrate/Fe(II) MR of 0.1 was higher than that at the initial citrate/Fe(II) MR of 0.01, it was still lower than those adsorbed at the initial citrate/Fe(II) MRs of 0 and 0.001 (Table 2), indicating that the citrate coprecipitated with Fe had a blocking effect. However, the amount of phosphate adsorbed per unit weight of the Fe oxides formed at the initial citrate/Fe(II) MR of 0.1 was the highest (Table 2), since these noncrystalline Fe oxides had the highest specific surface area (Table 1). The mechanism responsible for increasing phosphate adsorption is the citrate-induced formation of surface area and reaction sites on the Fe oxides. This mechanism is different from the simple competition of citrate with phosphate proposed by Earl et al. (1979) and Bowden et al. (1980) for the reaction sites. The increase in specific surface and reaction sites for phosphate adsorption evidently more than compensated for the blocking of the phosphate adsorption sites by citric acid. In the studies of Earl et al. (1979) and Bowden et al. (1980), both citrate and phosphate were added into the Fe oxide suspension at the begining of the adsorption reaction. Citrate simply competed with phosphate for the adsorption sites and, thus, consistently decreased the phosphate adsorption. In the present systems, citrate, which was present during the formation of Fe oxides, significantly modified the surface properties of the Fe oxides through fundamental structural changes and the blocking of the reaction sites, and, thus, influenced phosphate adsorption. Kwong and Huang (1978) reported that citric acid also increases the ability of aluminum hydroxides to adsorb phosphate through fundamental structural modification. Rates of Phosphate Adsorption After 56-h reaction period, 51.292% of the phosphate initially added at the beginning of the reaction was adsorbed at 298 K (Fig. 1). The percent fraction of phosphate adsorbed at the end of a 24-h reaction period was very close to that of phosphate adsorbed at the end of a 56-h reaction period. Furthermore, the processes of phosphate adsorption by the Fe oxides were very fast. The 41.874.5% and 68.287.4% of phosphate adsorbed by the Fe oxides after 56-h reaction period had already been adsorbed in the first 2-min and 1-h reaction periods, respectively (Fig. 1). Generally, the concentration of phosphate in solution decreased rapidly in the 0.0331 h reaction period and more slowly in the 124 h reaction period, indicating that phosphate adsorption con-

LIU AND HUANG KINETICS OF P ABSORPTION BY FE OXIDES 449

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Fig. 1. The concentration of phosphate remaining in solution vs. time in the system of Fe oxides formed at the initial citrate/Fe(II) molar ratios (MRs) of (a) 0, (b) 0.001, (c) 0.01, and (d) 0.1. The standard errors of all the experimental data were less than 5%.

sisted of a multiple rate process. The multiple-rate characteristic of phosphate adsorption is possibly related to the heterogeneity of adsorption sites. The different accessibility of surface pores and multiple sorption sites with different binding strengths result in an apparent heterogeneity of the surface (Benjamin and Leckie 1981; Madrid and de Arambarri 1985; Hiemstra et al. 1989a,b) and would cause differences in the adsorption rate. The phosphate adsorption may replace the positively charged OH2 groups through ligand exchange and, thus, tends to lower the positive surface potential and increase negative charge (Parfitt and Atkinson 1976). Therefore, the electrostatic repulsion becomes stronger as the adsorption proceeds (Hansmann and Anderson 1985; Shang et al. 1993). The kinetic and empirical equations, including the zeroorder, first-order, and second-order rate equations, the Elovich equation, the modified Freundlich equation, and the overall diffusion equation, were used to fit the phosphate adsorption data. The degree of fit of the rate equations to the

data was examined by using the determination coefficient (r2) and probability (P) of the linear regression analysis as well as the standard error (SE). As an example, the statistical results for the degree of fit of the rate equations to the phosphate adsorption by the Fe oxides formed at the initial citrate/Fe(II) MR of 0.1 at 298 K are presented in Table 3. The multiple second-order kinetic equation better describes the phosphate adsorption by the Fe oxides than the zero-order and 1st-order models. The first reaction occurred between 0.033 and 1 h and the second reaction between 1 and 24 h. Although the phosphate adsorption also can be satisfactorily described by the Elovich, modified Freundlich and overall diffusion equations, the parameters derived by the Elovich and modified Freundlich equations are not well defined physicochemically and the equations may not provide the rate coefficients (Kuo and Lotse 1973; Bolan et al. 1985). The overall diffusion equation is often used to indicate that diffusion-controlled phenomena are rate-limiting and only apparent diffusion coefficients can be obtained (Sparks 1999).

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Table 3. The comparison of the degree of fit of the kinetic models to the data of phosphate adsorption by the Fe oxidesz r2 Model Zero-order First-order Second-order Overall diffusion Elovich Freundlich (Modified)
zThe

P sx 0.74 0.88 0.97 0.87 0.97 0.92 f 5.39 102 4.22 102 3.15 102 1.45 102 4.15 103 4.59 103 s 2.70 102 1.71 103 6.71 105 2.07 103 6.41 105 2.04 104

SE (cmol kg1) f 2.78 2.27 1.08 1.66 1.10 1.15 s 2.11 3.90 1.40 1.48 0.74 0.91

fy 0.76 0.80 0.83 0.90 0.96 0.95

Fe oxide was formed at the initial citrate/Fe(II) MR of 0.1; the kinetic experiment was conducted at 298 K; r2 is the determination coefficient; P is the probability; SE is the standard error, which was calculated by the difference between measured amount of P adsorbed A and calculated amount of P adsorbed A* based on the equation SE = [ (A A*)2 / (n 2)]1/2. yThe first reaction. xThe second reaction.

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The 2nd-order kinetic equation was chosen in this study to estimate the rate coefficients of phosphate adsorption and the temperature effect on the phosphate adsorption based on the Arrhenius equation. The 2nd-order kinetic plots for the phosphate adsorption on the Fe oxides, which were formed at the initial citrate/Fe(II) MR of 0.1, at different temperatures are used as an example and illustrated in Fig. 2. The rate coefficients of phosphate adsorption by the Fe oxides generally increased with increasing temperature (Table 4). The rate coefficients of the first reaction were about 419 times those of the second reaction, except that the rate coefficient for the second reaction of phosphate adsorption by the Fe oxides, which were formed at the initial citrate/Fe(II) MR of 0.1, at 313 K was 1.5 times that of the first reaction. The second reaction of phosphate adsorption by the Fe oxides formed at the citrate/Fe(II) MR of 0.1 probably occurred predominantly on the micropore surface area and, thus, was more temperature dependent and required a longer induction period. This phenomenon occurring in the system of the Fe oxides formed at the citrate/Fe(II) MR of 0.1 differs from that in the systems of Fe oxides formed at other citrate/Fe(II) MRs. This is attributed to the differences in the surface properties between the Fe oxide formed at the citrate/Fe(II) MR of 0.1 and those formed at the citrate/Fe(II) MRs of 0, 0.001, and 0.01. Especially, 65% of the surface area of the Fe oxides formed at the citrate/Fe(II) MR of 0.1 was composed of micropore area (Table 1). The greater temperature-dependent and longer induction period were apparently the nature of adsorption reaction occurring on the micropore surface. The movement of phosphate ions into the micropore would be facilitated at higher temperatures. Transport of phosphate ions to the micropore surface of the Fe oxide would require more time compared with transport to the mesopore surface. This would account for the longer induction for the phosphate adsorption on the Fe oxide formed at the MR of 0.1 compared with the adsorption in other Fe oxide systems. Therefore, compared with other Fe oxide systems, the higher micropore surface area of the Fe oxides formed at the citrate/Fe(II) MR of 0.1 would account for the greater rate coefficient. Generally, the rate coefficient of phosphate adsorption by the Fe oxides formed at

various initial citrate/Fe(II) MRs followed the order of the initial citrate/Fe(II) MR: 0.1 > 0 > 0.01 > 0.001. The phosphate adsorption by the Fe oxides formed at the initial citrate/Fe(II) MR of 0.1 had the highest rate coefficients in the two reactions, which may be attributed to its highest specific surface area among the oxides studied, their X-ray noncrystalline nature (Table 1), and the greater number of reaction sites per unit surface area as indicated by their highest mean surface roughness and surface fractal dimension. The rate coefficients of the first and second reactions of phosphate adsorption at 298 and 313 K on the Fe oxides formed at the initial citrate/Fe(II) MR of 0 were higher than those by the Fe oxides formed at the MR of 0.01. First, this is attributed to the blocking of some of the reaction sites by citrate and steric effects of citrate coprecipitated with Fe in the Fe oxides formed at the MR of 0.01. Second, it is attributed to the higher PZSE of the Fe oxides formed at the citrate/Fe(II) MR of 0 than at the MR of 0.01 (Table 1). Therefore, the Fe oxides formed at the initial citrate/Fe(II) MR of 0 would have more net positive charges than those formed at the initial citrate/Fe(II) MR of 0.01 at the same pH value. Compared with the Fe oxides formed at the MR of 0.01, the Fe oxides formed at the MR of 0 should more strongly attract the phosphate anions and account for the increased rate coefficients at higher temperatures. However, the increased rate coefficient of phosphate adsorption by the Fe oxides formed at the citrate/Fe(II) MR of 0 caused by the electrostatic attraction was not significantly pronounced at lower temperatures. As discussed above, goethite and maghemite were predominantly formed at the initial citrate/Fe(II) MR of 0, whereas poorly crystalline lepidocrocite with some X-ray noncrystalline Fe oxides were formed at the initial citrate/Fe(II) MR of 0.01. Since goethite is more stable than lepidocrocite (Krishnamurti and Huang 1993; Cornell and Schwertmann 1996), the rate coefficient of phosphate adsorption by the Fe oxides formed at the initial citrate/Fe(II) MR of 0 (mainly goethite and maghemite) would be more temperature dependent than that of phosphate adsorption by the Fe oxides formed at the citrate/Fe(II) MR of 0.01. Thus, at low temperatures, the elec-

LIU AND HUANG KINETICS OF P ABSORPTION BY FE OXIDES 451

Fig. 2. The second order kinetic plottings of phosphate adsorption on the Fe oxide formed at the initial citrate/Fe(II) molar ratio (MR) of 0.1 at (a) 278, (b) 288, (c) 298, and (d) 313K.

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trostatic attraction to increase the rate of phosphate adsorption by the Fe oxides formed at the initial citrate/Fe(II) MR of 0 would be masked by the greater temperature dependence of the rate coefficient of phosphate adsorption. The phosphate adsorption by the Fe oxides formed at the MR of 0.001 had the lowest rate coefficients (Table 4), which is attributed to their lowest specific surface among the Fe oxides studied (Table 1). Therefore, the specific surface area, surface porosity, surface geometry described by the mean surface roughness and surface fractal dimension, surface charge and the coprecipitated citrate ligands together influenced the rate coefficient of phosphate adsorption. The coprecipitation of citrate ligands affected the rate coefficient of phosphate adsorption by distorting the structure of Fe oxides formed and modifying their surface geometry and surface charge. Activation Energy and Pre-exponential Factor To further understand the effect of temperature on phosphate adsorption on the Fe oxides, the Arrhenius equation was used to calculate the activation energy (Ea) as well as the pre-exponential factor: k = A eEa/RT

Table 4. The rate coefficient of the 2nd-order kinetic model of phosphate adsorption by the Fe oxides at different temperatures Initial citrate/ Fe(II) MR Temperature (K) 278 288 (mol1 h1) 0 0.001 0.01 0.1 0 0.001 0.01 0.1
zThe

298

313

245ab 142a 190a 634d 13a 11a 15ab 42de

First reactionz 484cd 1052e 242ab 290bc 323bc 515d 1185ef 2216g Second reactiony 25bc 62e 18ab 19abc 20abc 38cde 176f 600g

1613f 495d 599d 3215h 131f 31bcd 59e 4706h

values followed by the same letter are not significantly different at 95% confidence level for the first reaction for both columns and rows. yThe values followed by the same letter are not significantly different at 95% confidence level for the second reaction for both columns and rows.

where k is the rate coefficient, A is the pre-exponential factor (frequency factor), Ea is the Arrhenius activation energy, R is the universal molal gas constant (8.314 J K1 mol1), and T is the absolute temperature. When ln k is plotted versus

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Table 5. The activation energy and pre-exponential factor of phosphate adsorption by the Fe oxides formed at various initial citrate/Fe(II) MR Initial citrate/Fe(II) molar ratio 0 0.001 0.01 0.1
zLSD 0.05 yLSD 0.05

Activation energyz (kJ mol1) First reaction 40 25 24 34 Second reaction 49 19 30 97

Pre-exponential factory (mol1 h1) First reaction 8.2 109 6.5 106 6.9 106 1.7 109 Second reaction 2.4 1010 5.5 105 6.4 106 6.1 1019

= 18 and LSD0.01 = 26 for activation energy. = 5.2 104 and LSD0.01 = 7.5 104 for pre-exponential factor.

1/T, the activation energy and the pre-exponential factor can be obtained based on the slope and intercept, respectively. The activation energy for phosphate adsorption by the Fe oxides ranged from 19 to 97 kJ mol1 phosphate adsorbed (Table 5). The activation energy of a diffusion-controlled process in solution is about 25 kJ mol1 (Sparks 1986). However, in heterogeneous systems such as mineral-water interfaces, diffusion occurs not only in the bulk solution but also in micropores and macropores, in the films around solid particles, on the solid surface, and inside solid particles (Sparks 1989). Therefore, the activation energy for the diffusion processes in heterogeneous systems is higher than that in solutions. Film diffusion typically has an energy of activation of 1721 kJ mol1 and intraparticle diffusion has Ea values of 2142 kJ mol1 (Sparks 1986). Thus, low Ea values (< 42 kJ mol1) indicate diffusion-controlled processes whereas higher Ea values (> 42 kJ mol1) indicate chemically controlled processes (Sparks 1989). The data show that the rate-limiting step of most of the phosphate adsorption reactions by the Fe oxides was a diffusion process, except for the second reaction of phosphate adsorption by the Fe oxides formed at the initial MR of 0.1 as indicated by the activation energy of 97 kJ mol1, where the rate-limiting process was evidently a chemical process, which may involve ligand exchange of citrate by phosphate. Further, the Fe oxides formed at the initial citrate/Fe(II) MR of 0.1 had the lowest PZSE values and, thus, the least net positive charges at pH of 4.0 (Liu and Huang 1999), and the largest micropore surface areas (Table 1). The negative charges on the Fe oxides would result in an electrostatic repulsion of phosphate anions and make it difficult for phosphate to approach the Fe oxide surface. Due to steric effects, micropores would slow down the diffusion of phosphate ions to the Fe oxide surface compared with mesopores. However, the activation energy for the first reaction of phosphate adsorption on the Fe oxides formed at the MR of 0.1 was not significantly different from those for the first reaction of phosphate adsorption on the Fe oxides formed at the MRs of 0, 0.001 and 0.01. The first reaction of phosphate adsorption by the Fe oxides formed at the citrate/Fe(II) MR of 0.1 could predominantly occur through ligand exchange reactions with OH2/OH groups rather than with citrate ligands. The second reaction of phosphate adsorption by the Fe oxides formed at the initial MR of 0 had a higher activation energy than those formed at the initial MRs of 0.001 and 0.01 (Table 5). The Fe oxides formed at the MR of 0 were composed of goethite and maghemite whereas the Fe

oxides formed at the MRs of 0.001 and 0.01 were predominantly composed of lepidocrocite (Table 1). As discussed before, goethite may require more energy to adsorb phosphate by replacing the OH and OH2 groups compared with lepidocrocite. Although the second reaction of phosphate adsorption by the Fe oxides formed at an initial MR of 0.1 had the highest activation energy (Table 5), it had the highest rate coefficient for phosphate adsorption (Table 4). This is evidently due to its highest pre-exponential factor for phosphate adsorption among the Fe oxides (Table 5). The pre-exponential factor values for phosphate adsorption differed by 14 orders of magnitude for the different Fe oxide systems studied. Compared with the Fe oxides formed at the initial citrate/Fe(II) MRs of 0.001 and 0.01, the higher pre-exponential factor values for the second reaction of phosphate adsorption by the Fe oxides formed at the initial citrate/Fe(II) MRs of 0 and 0.1 accounted for their higher rate coefficients despite their higher activation energy values. Therefore, both the activation energy and pre-exponential factor must be considered in interpreting the rates of phosphate adsorption on the Fe oxides. The pre-exponential factor is a measurement of the frequency at which reactant molecules collide with each other. In the phosphate adsorption by the Fe oxides formed at various citrate/Fe(II) MRs, the pre-exponential factor is, thus, a measurement of the accessibility of phosphate ions to the surface of the Fe oxides. The specific surface area and the surface site density govern the total number of reaction sites. Micropores with a diameter less than the hydrated diameter of phosphate ions (0.8 nm) and the blocking of surface sites by citrate ligands would reduce the number of effective reaction sites. The surface geometry, surface porosity and citrate coprecipitated with Fe may have a steric effect on the collision between reactant molecules. Therefore, the preexponential factor should be related to the surface area, surface site density, surface geometry, surface porosity, and the blocking of surface sites caused by the coprecipitated citrate ions. In the present study, only four Fe oxide samples were used to investigate phosphate adsorption and it is difficult to establish the mathematical relationships between the preexponential factor and the above-mentioned surface properties. This relationship is worth studying in the future. Although the Fe oxides formed at the citrate/Fe(II) MR of 0.1 had a high micropore volume and a significant amount of coprecipitated citrate (Table 1), they had the highest preexponential factor (Table 5). This is attributed to their high-

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LIU AND HUANG KINETICS OF P ABSORPTION BY FE OXIDES 453

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est specific surface area (Table 1) that was accessible to phosphate. Further, these Fe oxides were X-ray noncrystalline (Table 1) and thus should have a higher surface site density compared with crystalline Fe oxides. The Fe oxides formed at the citrate/Fe(II) MR of 0.001 had the lowest specific surface (Table 1), which accounted for the lowest preexponential factor (Table 5). Although the specific surface area of Fe oxides formed at the citrate/Fe(II) MR of 0.01 was higher than that of Fe oxides formed at the MR of 0 (Table 1), the latter had the higher pre-exponential factor (Table 5). This is attributed to the development of micropores and the coprecipitation of a significant amount of citrate ligands in the former (Table 1). Therefore, some reaction sites on the Fe oxide surface were blocked by the citrate ligands and the effective reaction sites, thus, decreased. CONCLUSIONS The data for phosphate adsorption by the Fe oxides, which were formed at the initial citrate/Fe(II) MRs of 0, 0.001, 0.01, and 0.1, show that the phosphate adsorption followed multiple second-order kinetics. The amount, rate coefficient, activation energy and pre-exponential factor for phosphate adsorption by the Fe oxides were influenced by the surface properties of the Fe oxides such as specific surface area, surface charge, surface porosity and surface geometry, which varied significantly with the initial citrate/Fe(II) MR values during the formation of the Fe oxides. The presence of citrate at a low concentration in the solution in which the Fe oxides formed (initial citrate/Fe(II) MR of 0.001) decreased the amount and rate of phosphate adsorption due to the improvement of lepidocrocite crystallization and the resultant low specific surface area. The presence of citrate at a high concentration (initial citrate/Fe(II) MR of 0.1) increased the amount and rate of phosphate adsorption, although the coprecipitated citrate blocked some of the reaction sites and increased the activation energy for phosphate adsorption. This is apparently due to the citrate-induced formation of reaction sites on the Fe oxides, i.e., the high specific surface area and reaction site density of noncrystalline Fe oxides, and the resultant high pre-exponential factor. The data of this study indicate that the surface properties of Fe oxides formed under the influence of organic acids through fundamental structural perturbation should greatly modify the dynamics of phosphate in terrestrial and aquatic environments. ACKNOWLEDGMENTS This study was supported by the Natural Sciences and Engineering Research Council of Canada Research Grant GP2383-Huang and the University of Saskatchewan Graduate Scholarship.
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