Benzenecarboxylate Surface Complexation at the Goethite (α-FeOOH)/Water Interface: III. The Influence of Particle Surface Area and the Significance of Modeling Parameters

doi:10.1006/jcis.2000.6886

Journal of Colloid and Interface Science

Volume 227, Issue 1, 1 July 2000, Pages 132-140

https://doi.org/10.1006/jcis.2000.6886 Get rights and content

Abstract

A surface complexation model describing the adsorption of three benzenecarboxylates (phthalate, trimellitate, and pyromellitate) on goethite (α-FeOOH) was calibrated on data using goethite particles of 37 and 43 m²/g surface area. The models predict potentiometric titration and batch adsorption data with the multisite complexation model coupled with the three-plane model to account for surface electrostatics. The modeling parameters were found to be similar to those calibrated on benzenecarboxylate adsorption data on goethite particles of 90 m²/g (Boily et al. Geochim. Cosmochim. Acta, in press). The significance of the benzenecarboxylate-dependent values of the modeling parameters is also discussed. The values of the capacitances of the inner- and outer-Helmholtz planes were shown to be important modeling parameters to model the benzenecarboxylate-dependent slopes of the adsorption edges. It was shown that the larger the charge of the ligand, the larger the capacitance of the outer-Helmholtz plane.

References (17)

T. Hiemstra et al.
J. Colloid Interface Sci.
(1996)
U. Schwertmann
Thermochim. Acta
(1984)
P. Venema et al.
J. Colloid Interface Sci.
(1998)
N. Nilsson et al.
Geochim. Cosmochim. Acta.
(1996)
P. Venema
Charging and Ion Adsorption Behaviour of Different Iron (Hydr)oxides
(1997)
Boily, J.-F, Lützenkirchen, J, Balmes, O, Beattie, J, and, Sjöberg, S, Colloid Surf. A,...
Boily, J.-F, Persson, P, and, Sjöberg, S, Geochim. Cosmochim. Acta, in...
R.J. Atkinson et al.
J. Phys. Chem.
(1967)

There are more references available in the full text version of this article.

Cited by (31)

Adsorption of trichlorphon on phyllosilicate minerals: Effect of low-molecular-weight organic acids
2024, Pedosphere
The use of trichlorphon in large quantities causes a large number of organic pollutants to enter water, sediments, and soils. Phyllosilicate minerals are considered effective adsorbents for organic pollutants. However, the adsorption behavior of organic pollutants on soil minerals affected by low-molecular-weight organic acids (LMWOAs) is not fully understood. In this study, the effect of LMWOAs on the adsorption behavior of trichlorphon on phyllosilicate minerals was investigated using a combination of adsorption measurements and molecular spectroscopic techniques (attenuated total reflection-Fourier transform infrared spectroscopy (ATR-FTIR) and X-ray photoelectron spectroscopy (XPS)). The adsorption of trichlorphon onto kaolinite (KAO) and montmorillonite (MON) was suppressed by increasing pH, indicating that electrostatic interaction played a key role in adsorption, especially at low pH. In the presence of citric acid (CA), there was an obvious promotion of trichlorphon adsorption on KAO and MON. In the presence of oxalic acid (OA), the adsorption of trichlorphon on KAO was promoted, whereas the adsorption on MON was inhibited, especially at pH 4.0. The presence of CA and OA increased the adsorption by increasing the exposure of hydrophobic sites of KAO and MON. The results from ATR-FTIR and XPS also indicated that the hydrophobic Si–O sites of phyllosilicate minerals were the preferred adsorption sites for trichlorphon in the presence of CA and OA, probably driven by the hydrophobic effect. However, the weak effect of OA on MON caused an increase in the electrostatic repulsion between MON and trichlorphon molecules, thus inhibiting adsorption. This study is significant for a deeper understanding of self-purification of soil and sediment systems in the presence of organic pollutants.
Using chromatographic and spectroscopic parameters to characterize preference and kinetics in the adsorption of humic and fulvic acid to goethite
2019, Science of the Total Environment
Citation Excerpt :
The adsorption envelopes of HA and FA measured with the batch adsorption experiments were depicted in Fig. 2. The amount of adsorbed HA and FA decreased with increasing pH, in line with other findings in the literatures (e.g. Boily et al., 2000; Ramos-Tejada et al., 2003; Martias et al., 2015). When expressed in mass (in the unit of mg C/m2), HA adsorbed much stronger than FA.
Humic substances (HS) are very heterogeneous, and preferential adsorption of certain components takes place during their interaction with minerals. Our results indicated that for fulvic acid (FA) the relatively large (3.6–18.2 kDa) particles were preferred in the adsorption to goethite, whereas for humic acid (HA) the intermediate sized (3.6–12.0 kDa) fractions were preferred. Correlations between molar mass (M_w) and specific UV absorption values (SUVA) with ratios of UV light absorbance (E₂/E₃, E₄/E₆) were observed. The adsorption did not change the relation between E₂/E₃ and M_w, E₄/E₆ and SUVA. The E₂/E₃ and E₄/E₆ can probably be used as indicators of molar mass and aromaticity of HS in studying the preferential adsorption. The adsorption of HA and FA to goethite was fast and reached a steady state in about 6 h. The intermediate sized HA particles (3.6–12.0 kDa) were adsorbed quickly, and part of them was subsequently replaced by somewhat larger particles (>50 kDa). For FA, preferential adsorption of relative large particles (3.6–18.2 kDa) took place quickly, and there was a limited substitution by particles with higher aromaticity. Without specifying the property especially the molar mass range of HS under study, confusion can arise from researches using different HS materials.
Dynamic adsorption process of phthalate at goethite/aqueous interface: An ATR-FTIR study
2014, Colloids and Surfaces A: Physicochemical and Engineering Aspects
Insights into the molecular-level behaviors of phthalate at the goethite/aqueous interface can further our understanding of the fate and transport of natural organic matter analogs in the environment. The motivation of this work is to explore the interfacial configuration and dynamic adsorption process of phthalate on goethite at the molecular scale. The flow-cell ATR-FTIR measurement, curve-fitting analysis, and pseudo-second-order kinetic simulation were used to investigate the adsorption mechanisms. The results showed that phthalate formed one electrostatic outer-sphere complex and two inner-sphere configurations in mononuclear bidentate and binuclear bidentate structures. The contribution of outer-sphere complex to the overall phthalate adsorption was suppressed with increasing ionic strength and decreasing pH values. The ratio of adsorption capacity between these two inner-sphere configurations was slightly affected under different experimental conditions. Furthermore, the dynamic adsorption process of these three interfacial configurations followed the pseudo-second-order kinetics model, and reached equilibrium rapidly within 60 min.
An overview of the role of goethite surfaces in the environment
2014, Chemosphere
Goethite, one of the most thermodynamically stable iron oxides, has been extensively researched especially the structure (including surface structure), the adsorption capacity to anions, organic/organic acid (especially for the soil organic carbon) and cations in the natural environment and its potential application in environmental protection. For example, the adsorption of heavy metals by goethite can decrease the concentration of heavy metals in aqueous solution and immobilize; the adsorption to soil organic carbon can decrease the release of carbon and fix carbon. In this present overview, the possible physicochemical properties of the goethite surface contributing to the strong affinity of goethite to nutrients and contaminants in natural environment are reported. Moreover, these chemicals adsorbed by goethite were also summarized and the suggested adsorption mechanism for these adsorbates was elucidated, which will help us understand the role of goethite in natural environment and provide some information about goethite as an absorbent. In addition, the feasibility of goethite used as catalyst carrier and the precursor of NZVI was proposed for removal of environmental pollution.
Effect of aging time and Al substitution on the morphology of aluminous goethite
2012, Journal of Colloid and Interface Science
Citation Excerpt :
Obviously, the decrease in BET is attributed to the re-crystalline and growth of Al-substituted goethite, which is good agreement with the results of XRD. As well-known, goethite has been proved to be a good absorbent to adsorb many potential contaminants in natural such as arsenic, antimony, copper, zinc, cadmium, lead, and others [29–33]. Specific surface area plays an important role in the adsorption/desorption process of goethite [34], the larger the specific surface area, the greater the adsorption at a given condition.
Goethite and Al-substituted goethite were synthesized from the reaction between ferric nitrate and/or aluminum nitrate and potassium hydroxide. XRF, XRD, TEM with EDS were used to characterize the chemical composition, phase and lattice parameters, and morphology of the synthesized products. The results show that d(020) decreases from 4.953 to 4.949 Å and the b dimension decreases from 9.951 Å to 9.906 Å when the aging time increases from 6 days to 42 days for 9.09 mol% Al-substituted goethite. A sample with 9.09 mol% Al substitution in Al-substituted goethite was prepared by a rapid co-precipitation method. In the sample, 13.45 mol%, 12.31 mol% and 5.85 mol% Al substitution with a crystal size of 163, 131, and 45 nm are observed as shown in the TEM images and EDS. The crystal size of goethite is positively related to the degree of Al substitution according to the TEM images and EDS results. Thus, this methodology is proved to be effective to distinguish the morphology of goethite and Al substituted goethite.
Development of a ceramic adsorbent for the removal of 2-methylisoborneol from aqueous solution
2011, Desalination
Removal of 2-methylisoborneol (2-MIB), a common musty odor compound, by a novel ceramic adsorbent (CA), developed with a mixture of akadama mud, wheat starch, and Fe₂O₃ is presented. The physicochemical characteristics of the CA are examined with scanning electron microscope (SEM), Energy Dispersive X-ray (EDX) and gas adsorption porosimetry analyses. The effects of initial 2-MIB concentration, contact time and initial solution pH are investigated. It is observed that the adsorption of 2-MIB by CA occurs by a pseudo-first-order mechanism. CA exhibits high removal efficiency for 2-MIB in both high (600 ng/L) and low (200 ng/L) initial 2-MIB concentrations at room temperature (25 °C) and can adapt to a wide range of pH (2–12) for 2-MIB adsorption. Over 80% of 2-MIB is removed by the CA within 600 min at an initial concentration of 200 ng/L with 20 g/L of CA dose. High regeneration performance shows that CA has great potential for reuse. These results suggest that the developed CA could be a promising material for effective and rapid removal of musty odor compounds in drinking water. Data on the adsorption kinetics and mechanism of adsorption are also presented.

View all citing articles on Scopus

¹: To whom correspondence should be addressed. Fax: +41 01/632 1088. E-mail: [email protected].

²: New address: Institut für Mineralogie und Petrographie, Eidgenössiche Technische Hochschule, ETH-Zentrum, CH-8092 Zürich, Switzerland.

View full text

Regular ArticleBenzenecarboxylate Surface Complexation at the Goethite (α-FeOOH)/Water Interface: III. The Influence of Particle Surface Area and the Significance of Modeling Parameters

Abstract

J. Colloid Interface Sci.

Thermochim. Acta

J. Colloid Interface Sci.

Geochim. Cosmochim. Acta.

Charging and Ion Adsorption Behaviour of Different Iron (Hydr)oxides

J. Phys. Chem.

Regular Article
Benzenecarboxylate Surface Complexation at the Goethite (α-FeOOH)/Water Interface: III. The Influence of Particle Surface Area and the Significance of Modeling Parameters