Competitive adsorption between phosphate and carboxylic acids: quantitative effects and molecular mechanisms

The competitive adsorption at the water‐goethite interface between phosphate and a carboxylic acid, either oxalate, citrate, 1,2,3,4‐butanetetracarboxylic acid (BTCA), mellitate or Suwannee River Standard Fulvic Acid 1S101F (FA), was investigated over a wide pH range (3–9) by means of batch experiments and attenuated total reflectance Fourier transform infrared (ATR‐FTIR) spectroscopy. The quantitative results from the competitive adsorption measurements show that the efficiency of the organic acids in competing with phosphate was in the order oxalate < citrate < BTCA ≅ FA < mellitate. Oxalate showed no detectable effect, whereas the effect in the mellitate system was strong, and the aggregative results indicate that an increasing number of carboxylic groups favours competitive ability towards phosphate. The infrared spectroscopic results show conclusively that competition for goethite surface sites between carboxylic acids and phosphate is not a ligand‐exchange reaction between inner‐sphere surface complexes. Instead, ligands capable of multiple H‐bonding interactions are required to out‐compete and desorb surface complexes of phosphate. The fact that partially protonated organic acids are the most efficient emphasizes the importance of both H‐accepting carboxylate groups and H‐donating carboxylic acid groups for the competitive effect.     

Sorption of iron‐cyanide complexes on goethite investigated in long‐term experiments

The iron‐cyanide complexes ferrocyanide, [Fe^II(CN)₆]^4–, and ferricyanide, [Fe^III(CN)₆]^3–, are anthropogenic contaminants in soil. We investigated their sorption on goethite, α‐FeOOH, in batch experiments in a time range from 1 d to 1 yr, their desorption by phosphate and chloride as well as their surface complexes on goethite by Fourier‐transform infrared spectroscopy (FTIR). The sorption of both complexes continued over the whole time range. Percent desorption of ferricyanide by phosphate decreased, whereas that of ferrocyanide increased until it amounted to approximately 87% for both complexes. By FTIR spectroscopy inner‐sphere complexation of both complexes on the goethite surface was indicated. With both complexes, a Berlin‐Blue‐like layer (Fe₄[Fe(CN)₆]₃) was formed initially on the goethite surface which disappeared with increasing reaction time. After at least 30 d reaction time, ferricyanide was the only sorbed iron‐cyanide complex detected even when ferrocyanide was initially added. This resulted from slow oxidation of ferrocyanide, most probably by dissolved oxygen. Based on all results, we propose that ferricyanide forms monodentate inner‐sphere complexes on the goethite surface.     

Presence of bacteria reduced phosphate adsorption on goethite

Despite extensive studies, the information obtained from pure iron and aluminum (hydr)oxides cannot fully explain phosphate fixation in natural soils because of the ubiquitous interactions between (hydr)oxides and bacteria in soil. The effect of bacteria (Bacillus subtilis subsp. and Pseudomonas fluorescens) on phosphate adsorption on goethite (α‐FeOOH) was systematically examined under varying reaction times, phosphate concentrations, pH, ionic strength and bacteria dosage. Batch experiments in all cases showed significantly less adsorption on bacteria–goethite complexes than on pure goethite, demonstrating an inhibitory effect of bacteria. The inhibition of phosphate adsorption increased with bacterial loading, and showed a significant, non‐linear correlation with the decrease in the goethite positive charge induced by the bacteria. Moreover, in both the desorption experiment and in situ, the attenuated total reflectance Fourier‐transform infrared (ATR‐FTIR) spectra suggested a competition of bacteria surface groups (phosphate and carboxyl) with solution phosphate for hydroxyl on goethite. Therefore, the negative influences of bacteria on phosphate adsorption on goethite were probably caused by the surface charge modification and the competitive adsorption induced by the bacteria. Under most conditions, the effects of B. subtilis subsp. were conspicuous, while only slight influences were found for P. fluorescens. This difference between the two bacteria species was explained by differences in their surface charge, group content and chemical interaction with goethite. These findings uncover an important role of bacteria in phosphate phyto‐availability and mobility in natural environments.     

Modeling ferricyanide adsorption on goethite: Basics and applications

Ferricyanide, [Fe^III(CN)₆]^3–, is an anthropogenic and potentially toxic contaminant in soil. Its adsorption on goethite has been previously studied, but not evaluated with a surface complexation model (SCM) considering the effects of pH and ionic strength. Therefore, we carried out batch experiments with ferricyanide and goethite suspensions with different ferricyanide concentrations (0.075 mM and 0.15 mM), ionic strengths (0.01 and 0.1 M), and pH (ranging from 4 to 7.4). Adsorption data were then interpreted with the 1‐pK Stern and the charge distribution model assuming monodentate inner‐sphere ferricyanide surface complexes on goethite (lg K = 10.6), which are known from infrared spectroscopy. Furthermore, we applied the SCM to ferricyanide adsorption in previous studies on ferricyanide adsorption in the presence of sulfate and on the solubility of Fe‐cyanide complexes in a suspension of a loess loam. The SCM correctly reflected ferricyanide adsorption in the batch experiments as well as the effects of pH and ionic strength. The SCM also described ferricyanide adsorption in the presence of sulfate, because the ferricyanide adsorption measured and that modeled were significantly correlated (R² = 0.80). Furthermore, we applied the SCM to a study on the solubility of Fe‐cyanide complexes in soil under varying redox conditions so that ferricyanide adsorption on goethite and precipitation of Fe‐cyanide complexes were considered. The actual ferricyanide concentrations were rather reflected when applying the SCM compared to those modeled in an approach in which exclusively precipitation was taken into account. We conclude that ferricyanide adsorption on goethite should be included into geochemical modeling approaches on the mobility of Fe‐cyanide complexes in subsoils.     

Sorption of iron-cyanide complexes on goethite

Iron‐cyanide complexes are present in soils on sites of former gas plants and coke ovens. We have studied the sorption of the complexes ferricyanide, [Fe(CN)₆]^3–, and ferrocyanide, [Fe(CN)₆]^4–, on goethite in batch experiments, including the effects of concentration, time, ionic strength, pH, and the extent of reversibility. The sorption of ferricyanide showed features of both outer‐sphere and inner‐sphere complexation: its extent decreased with increasing pH; it depended on ionic strength; it was quickly and completely reversible; and it induced a change in surface electric potential. In contrast, sorption of ferrocyanide depended on pH to a lesser extent and was not affected by ionic strength at different pHs. The desorption was slower and incomplete. For ferrocyanide we conclude that sorption involves inner‐sphere complexation and precipitation of a Berlin‐Blue‐like phase on the goethite surface.     

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.     

Beta-thujaplicin: new quantitative CZE method and adsorption to goethite

Beta-thujaplicin (beta-TH) is a toxic tropolone derivative present in the heartwood of western red cedar (Thuja plicata) and is used as a preservative and antimicrobial additive in a number of commercial goods. beta-TH released from western red cedar timber used outdoor and from other products containing beta-TH may transfer to soil and leach to groundwater and surface waters. The objective of this study was to quantify the adsorption of beta-TH to goethite as a typical model for geosorbents. Adsorption was studied using pH-adjusted goethite suspensions with solid:solution ratios of 1:500, 0.01 M NaNO(3) electrolyte, and 20 degrees C. beta-TH was determined using a new capillary zone electrophoresis (CZE) method providing a detection limit of 0.21 microM. Near-sorption equilibrium was attained within 48 h. beta-TH showed maximum adsorption at low pH (3.8) and a 70% drop in adsorption from pH 6.2 to 8.8. The Langmuir type adsorption isotherm at pH 5.5 approached a maximum adsorption of 220 micromol/g (= 6.2 micromol/m(2)), which is more than twice the amount of phosphate adsorbed under similar conditions. The affinity of beta-TH for goethite is low as compared with organic ligands such as citrate, oxalate, and 2,4-dihydroxybenzoate. The adsorption data and FTIR analyses indicate that beta-TH is most likely adsorbed as monodentate mononuclear surface complexes at the surface of goethite. Hydrophobic adsorption is thought to contribute to the adsorption, in particular at low pH. The strong adsorption of beta-TH to goethite suggests low mobility in most soil environments, the risk of contamination increasing in soils with high pH (calcareous material), low contents of iron and aluminum oxides, phyllosilicates, and organic matter.     

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.

     

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.     

pH变化条件下针铁矿表面吸附的磷酸盐联合态的转化

X-ray photoelectron spectroscopy(XPS) and automatic titrimeter were used to study the relation bewteen pH and the transformation of the coordinate forms of P on goethite surfaces.The results showed that for a given P concentration,increasing the pH of suspension could cause a fast transformation of monodentate complexes of phosphate ions on goethite surfaces to binuclear ones,When lowering the pH,additional adsorption of P occurred and the binuclear complexes reverted slowly to the monodentate ones,The dissociation and association of protons of the sorbed P caused by pH changes was considered to be a major reason leading to the transformation of the coordinate forms of P on the surfaces.The stability of binuclear surface complex of P was greater than that of monodentate omplex.The possible reactions on the interface of goethite and solutions with pH changes,and the reasons causing the different stabilities of the two coordinate P complexes are discussed in the paper.     

铁氧化物-胡敏酸复合物对磷的吸附吸附

本试验通过设置不同磷酸根浓度、 pH和不同电解质及电解质强度梯度,研究磷酸根在针铁矿-胡敏酸（HA）复合物和赤铁矿-胡敏酸（HA）复合物表面的吸附特性。X射线衍射（XRD）、 扫描电镜（SEM）和红外光谱（FTIR）图谱显示: 铁氧化物包覆胡敏酸后其内部结构特性保持不变; 氧化铁与胡敏酸通过氢键形成粒径大、 表面光滑的铁氧化物-HA复合微粒,且复合物比表面减小; 形成的氧化铁-胡敏酸复合物对磷的吸附能力增强,且针铁矿复合物的吸附能力大于赤铁矿复合物,均为多层吸附过程; pH增高抑制铁氧化物复合物对磷的吸附,同时电解质浓度增加促进复合体对磷的吸附,且反应后体系pH随之降低。     

On the mechanism of specific phosphate adsorption by hydroxylated mineral surfaces: A review

Abstract

The mechanism of specific phosphate adsorption by hydroxy‐lated mineral surfaces comprises two aspects: the phosphate‐hydroxyl surface reaction and the configuration of the adsorbed phosphate ion. Evidence pointing to ligand exchange as the mechanism of the phosphate‐surface hydroxyl reaction include kinetics of adsorption and desorption; hydroxyl ion release; infrared spectroscopy, and stereochemical calculations. Data pertaining to the coordination of adsorbed phosphate on hydroxy‐lated mineral surfaces have not been conclusive overall. Isotopic exchange experiments and studies of desorption kinetics do not provide definitive information on surface coordination. Measurements of hydroxyl ion release and crystallographic calculations provide support for the existence of both monodentate and bidentate surface complexes of phosphate ions. Infrared spectroscopic investigations suggest a binuclear complex on dried, phosphated goethite. However, these studies cannot be extrapolated automatically to soil minerals, since the addition of water favors formation of a monodentate surface complex. Further research is needed to establish the configuration of adsorbed phosphate ions.     

Comparison of phosphate adsorption on clay minerals for soilless root media

Abstract

The greenhouse industry aims to decrease phosphate discharge to help reduce eutrophication of surface waters, to reduce fertilizer consumption, and to maintain a more constant level of plant‐available phosphate. Iron and aluminum oxides and some aluminosilicate minerals are efficient sorbents for phosphate. The phosphate adsorption characteristics of synthetic hematite (α‐Fe₂O₃), goethite (α‐FeOOH), and allophane (Si₃Al₄O₁₂ nH₂O), and a commercial alumina (A1₂O₃) were evaluated to determine their potential for reducing phosphate leaching from soilless root media. The pH dependence of phosphate adsorption and maximum adsorption capacities were determined by reacting each mineral with various levels of phosphate between pH 4.0 and 9.0 in a 10 mM potassium chloride (KCl) background solution. Adsorbed phosphate was determined by loss from solution. Adsorption envelopes (adsorbed phosphate versus pH) showed a decrease in phosphate adsorption with increasing pH, particularly for alumina and allophane, and at greater added phosphate concentrations. The maximum adsorption capacities per unit mass of the minerals at pH 5.4 decreased in the order allophane > alumina ? goethite > hematite. When expressed on a surface area basis, the order of maximum adsorption capacity remains the same except that alumina exceeded that of goethite. The allophane, goethite, and alumina sorbed enough phosphate that 3 to 9 g of these minerals would retain the amount of phosphate required for a high nutrient element requiring plant such as chrysanthemum.     

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.     

有机磷与土壤矿物相互作用及其环境效应研究进展

土壤有机磷是土壤环境中重要的磷组分,其在环境中的界面反应影响着磷素的迁移、转化、生物有效性以及环境行为。本文主要总结了土壤中典型有机磷在矿物表面的吸附-解吸、溶解-沉淀等反应特性和微观机制,以及有机磷-矿物相互作用对有机磷形态、金属离子界面反应行为,以及矿物胶体化学稳定性与溶解转化的影响等环境效应。土壤有机磷可含多个磷酸基团,相对分子质量大,电荷密度高,通过界面反应与环境矿物发生强烈的相互作用,并影响矿物的电荷性质、共存金属离子的吸附特性、以及胶体化学稳定性。有机磷界面反应特性和机制受矿物类型和结晶度、有机磷相对分子质量、pH、温度和共存离子等因素的影响。有机磷在矿物表面的吸附密度一般随着体系pH、矿物结晶度和有机磷相对分子质量的升高而降低。有机磷一般可在矿物表面形成内圈络合物,某些情况下还存在氢键作用,甚至转化形成表面沉淀。有机磷和金属离子在矿物表面的吸附一般存在协同效应(尤其是在低pH条件下),即金属离子促进了有机磷的吸附,有机磷也促进金属离子的固定;吸附机制因反应体系而异,主要包括形成三元表面络合物和表面沉淀等,多数时候存在多种机制的共同作用。最后讨论了环境中有机磷与矿物相互作用的主要研究热点和方向。     

Competitive adsorption of humus acids and phosphate on goethite, gibbsite and two tropical soils

Competition in adsorption between humic acid (HA) or fulvic acid (FA) and phosphate on synthetic goethite, gibbsite and two tropical soils was studied. The results for both goethite and gibbsite showed that HA and FA competed strongly with phosphate for adsorption sites at low pH values. The soils showed a similar result with a reduction in phosphate adsorption resulting from the addition of HA at the pH of the soils. The competition between HA and phosphate at different pH levels is illustrated by comparing the adsorption envelopes for phosphate on goethite, gibbsite and the two soils in the presence and absence of HA. The trends observed may be explained by the relative positions of the maximum buffer-power (buffer capacity) of the organic acids and of phosphoric acid which are shown to lie in different pH ranges.     

Desorption of myo‐inositol hexakisphosphate and phosphate from goethite by different reagents

Inositol phosphates are abundant organic phosphates found widely in the environment. The sorption and desorption of organic phosphate (P_o) are important processes in controlling the mobility, bioavailability and fate of phosphorus (P) in soil and sediment. The desorption characteristics of myo‐inositol hexakisphosphate (IHP) and inorganic phosphate (P_i) from goethite were studied by pre‐sorption of IHP or P_i followed by desorption by KCl, H₂O, and citrate. Batch experiments and in situ attenuated total reflectance Fourier transform infrared (ATR‐FTIR) spectroscopy were used to investigate the desorption of IHP/P_i. The desorption percentage of IHP/P_i by citrate was much higher than that by H₂O/KCl. The desorption of P by citrate was mainly achieved through ligand exchange, and the desorption increased with decreasing pH. Desorption by H₂O was slightly greater than that by 0.02 M KCl because the electrostatic repulsion between the P molecules is larger in H₂O. Due to the higher affinity of IHP for goethite than that of P_i, the maximum desorption of IHP was lower than that of P_i. Desorption curves (desorption concentration in solution vs. sorption density) of IHP or P_i on goethite by KCl or H₂O was well fitted by an exponential equation, while those by citrate were well fitted by a linear equation. The desorption amounts of P in the first cycle account for more than 58% of the total desorption followed by substantial decreases in the second and third cycles. There was a re‐sorption of P_i from solution in the late stage of desorption by KCl and H₂O, resulting in a sharp decrease in desorption. Re‐sorption of IHP did not occur, which is probably due to its poor diffusion into goethite. The initial desorption rate of P_i with KCl and H₂O decreased with increasing pre‐sorption time, whereas that of IHP was opposite. This study indicates that strong sorption on and weak desorption of IHP from iron (hydr)oxides may explain the accumulation of IHP in soils.     

磷酸盐在水铁矿及水铁矿-胡敏酸复合体表面的吸附

The adsorption of phosphate onto ferrihydrite (FH) and two FH-humic acid (HA) complexes, obtained by co-precipitating FH with low (FH-HA1) and relatively high amounts of humic acid (FH-HA2), was studied through kinetics and isotherm experiments to determine the differences in phosphate adsorption between FH-HA complexes and FH and to reveal the mechanism of phosphate adsorption onto two soil compositions. The isoelectric point (IEP) and the specific surface area (SSA) of the mineral decreased as the particle porosity of the mineral increased, which corresponded to an increase in the amount of organic carbon. The adsorption capacity of phosphate was higher on FH than on FH-HA1 and FH-HA2 at the scale of micromoles per kilogram. The initial adsorption rate and adsorption affinity of phosphate decreased with an increase in the amount of HA in the mineral. The sensitivity of phosphate adsorption to the change in the pH was greater for FH than for FH-HA complexes. Ionic strength did not affect the adsorption of phosphate onto FH and FH-HA1 at a lower pH, and the increase in the ionic strength promoted phosphate adsorption at a higher pH. However, for the FH-HA2 complex, the increase in the ionic strength inhibited the adsorption of phosphate onto FH-HA2 at a lower pH and increased the adsorption at a higher pH.     

Study of Interaction Between Glyphosate and Goethite Using Several Methodologies: an Environmental Perspective

Glyphosate (N-(phosphonomethyl) glycine) is one of the most widely used herbicides in the world. Experiments using distilled water or CaCl₂ extractor resulted in as much as 60% of glyphosate being desorbed from goethite. When Mehlich 1 extractor was used, desorption could reach up to 73%. At pHs 2.0, 4.0, 6.0, and 8.0, an increase in salt content decreased the adsorption of glyphosate onto goethite. This indicates that most of the glyphosate is bound weakly to goethite through an outer-sphere complex. Thus, in soils with a high goethite content, glyphosate will contaminate groundwaters or rivers easily. FT-IR spectra showed that glyphosate interacts with goethite through the phosphate group and, at high pH, the amine group could be involved. Evidences of the interaction of the amine group of glyphosate with goethite were also obtained from the EPR spectra that showed, at high pH, a distortion in the octahedral symmetry of iron. In addition to the adsorption decrease with an increase in pH, a decrease of desorption at high pH occurs. This probably occurs because, at high pH, glyphosate interacts with goethite as a monodentate complex and through the amine group. The adsorption results fit best to a Freundlich isotherm model. This is in good agreement with the desorption results, indicating the presence of at least two adsorption sites—one for outer-sphere complexes and the other of inner-sphere complexes. The experimental results fit well with both pseudo-second-order and diffusion-limited models. The experimental results also fit well with a diffusion-limited model; however, the C value was different from zero. Therefore, the adsorption process was not controlled by diffusion only. Adsorption of glyphosate onto goethite is a complex process that could involve intra-particle diffusion. After adsorption of glyphosate onto goethite, a large decrease of pH_pzc was observed. The surface area and pore volume of goethite did not change with the adsorption of glyphosate.     

ADSORPTION ON HYDROUS OXIDES I. OXALATE AND BENZOATE ON GOETHITE

The adsorption of oxalic acid on synthetic goethite (α-FeOOH) was studied using adsorption isotherms. Infrared spectra were obtained for goethite-oxalate complexes at several points on the isotherms. On a goethite preparation with a phosphate sorption capacity of 200|μmolg^?1 the amounts of oxalate strongly adsorbed varied from near zero at pH 8 to about l00μmolg^?1 at pH 4 and below. At pH 3.4, the first l00μmolg^?1 of oxalic acid added was strongly adsorbed as a binuclear complex (FeOOC–COOFe), replacing two singly-coordinated OH groups by ligand exchange. At higher concentrations a further 200 μrnol g^?1 of oxalic acid formed a monodentate complex (FeOOC–COOH) so that more oxalate could be accommodated. Benzoic acid was weakly adsorbed on goethite with one benzoate oxygen replacing one singly-coordinated OH. The other oxygen of the COO group fitted into the goethite surface so that the benzene ring was at a high angle to the (100) face.