Reaction of hydroquinone with hematite; II. Calculated electron-transfer rates and comparison to the reductive dissolution rate

The rate of reaction of hematite with quinones and the quinone moieties of larger molecules may be an important factor in limiting the rate of reductive dissolution of hematite, especially by iron-reducing bacteria. It is possible that the rate of reductive dissolution of hematite in the presence of excess hydroquinone at pH 2.5 may be limited by the electron-transfer rate. Here, a reductive dissolution rate was measured and compared to electron-transfer rates calculated using Marcus theory. An experimental rate constant was measured at 9.5 x 10 (-6) s(-1) and the reaction order with respect to the hematite concentration was found to be 1.1. Both the dissolution rate and the reaction order of hematite concentration compare well with previous measurements. Of the Marcus theory calculations, the inner-sphere part of the reorganization energy and the electronic coupling matrix element for hydroquinone self-exchange electron transfer are calculated using ab initio methods. The second order self-exchange rate constant was calculated to be 1.3 x 10 (7) M(-1)s(-1), which compares well with experimental measurements. Using previously published data calculated for hexaquairon(III)/(II), the calculated electron-transfer rate for the cross reaction with hydroquinone also compares well to experimental measurements. A hypothetical reductive dissolution rate is calculated using the first-order electron-transfer rate constant and the concentration of total adsorbed quinone. Three different models of the hematite surface are used as well as multiple estimates for the reduction potential, the surface charge, and the adsorption density of hydroquinone. No calculated dissolution rate is less than five orders of magnitude faster than the experimentally measured one.     

On the Spreading of Glycerol Trioleate

The benzoquinone/hydroquinone (Q/H(2)Q) redox reaction has been studied by electrochemical-scanning tunneling microscopy (EC-STM) at a Pd(111)-(square3xsquare3)R30 degrees -I electrode surface in a solution that contained 10(-4) M H(2)Q in 0.05 M H(2)SO(4); iodine-pretreatment of the Pd(111) surface was to prevent chemisorption of organic-derived species. The molecule-resolved EC-STM images indicated that: (i) at a potential where only H(2)Q is present in solution, a self-assembled (square21xsquare21)R10.9 degrees -eta(6)-H(2)Q monolayer is produced in which the H(2)Q molecules are oriented parallel to the surface; (ii) at a potential where partial oxidation (to Q) occurs, a self-assembled (square21xsquare21)R10.9 degrees -eta(6)-QH adlayer is generated, where QH represents quinhydrone, an equimolar mixture of Q and H(2)Q; in this structure, the Q and H(2)Q molecules are oriented vertically, face-to-face, and arranged alternately along a given row, reminiscent of the crystal structure of quinhydrone. The partial oxidation-induced molecular reorientation, which is reversible, most likely arises from favorable Q-H(2)Q face-to-face interactions; that is, complete oxidation would yield only flat-oriented Q species. Unfortunately, at potentials where only Q would be present in solution, I-catalyzed corrosion of the Pd starts to occur, which leads to noise-laden EC-STM images. Copyright 2001 Academic Press.     

Surface reactivity of the quinone/hydroquinone redox center tethered to gold: comparison of delocalized and saturated bridges

We found that when a quinone headgroup, present in a mixed self-assembled monolayer on gold, reacts with a nucleophile, dissolved in the bulk phase, the reaction rate widely depends on the chemical nature of the tether, being 7 times faster for quinones attached via a delocalized bridge as compared to a saturated alkane chain. Cyclic voltammetry (CV) of the quinone/hydroquinone redox couple was used to monitor the nucleophilic addition, while simulated CVs compared to experimental runs permitted the determination of rate constants. Analysis of CV data also suggests that the delocalized oligo(phenylene ethynylene) bridge facilitates the addition of two mercaptoethanol molecules as compared to the alkane bridge, where only one molecule is being added. The use of delocalized bridges for tethering quinones to electrodes is of great potential in electrochemically controlled "tuning" of surfaces needed in biosensor applications.     

Adsorption of trimethyl phosphate on maghemite, hematite, and goethite nanoparticles

Adsorption of trimethyl phosphate (TMP) on well-characterized hematite, maghemite and goethite nanoparticles was studied by in situ DRIFT spectroscopy as a model system for adsorption of organophosphorous (OP) compounds on iron minerals. The iron minerals were characterized by X-ray diffraction (XRD), Raman spectroscopy, transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), specific surface area, and pore size distribution. The minerals were found to consist of stoichimetrically and morphologically well-defined maghemite, hematite, and goethite nanoparticles. Analysis of in situ diffuse reflectance Fourier transform (DRIFT) spectroscopy shows that TMP bonds mainly to Lewis acid Fe sites through the O phosphoryl atom (-P═O-Fe) on hematite and maghemite. On goethite most TMP molecules bond to Br?nstedt acid surface OH groups and form hydrogen bonded surface complexes. The vibrational mode analysis and uptake kinetics suggest two main reasons for the observed trend of reactivity toward TMP (hematite > maghemite > goethite): (i) larger number of accessible Lewis acid adsorption sites on hematite; (ii) stronger interaction between the Lewis acid Fe sites and the phosphoryl O atom on TMP for hematite and maghemite compared to goethite with concomitant formation of surface coordinated TMP and dimethyl phosphate intermediates. As a result, on the oxides a surface oxidation pathway dominates during the initial adsorption, which results in the formation of surface methoxy and formate. In contrast, on goethite a slower hydrolysis pathway is identified, which eventually yields phosphoric acid. The observed trends of the reactivity and analysis of the corresponding surface structure and particle morphology suggest an intimate relation between the surface chemistry of exposed crystal facets on the iron minerals. These results are important to understand OP surface chemistry on iron minerals.     

Studies on porphyrin-quinhydrone complexes: molecular recognition of quinone and hydroquinone in solution.

Free-base and zinc(II) porphyrins bearing either one, two, or four hydroquinone entities at the meso positions are shown to bind quinones in solutions via a quinhydrone pairing mechanism. Electrochemical studies reveal that the quinhydrone complexes are stabilized by charge-transfer interactions between the donor (hydroquinone) and the acceptor (quinone). The redox potentials of the quinhydrone complexes are governed by the potentials of the quinones utilized to form quinhydrone. The (1)H NMR studies reveal that the quinhydrone complexes are stabilized by H-bonding in addition to the charge-transfer interactions. Singlet emission studies have shown that the fluorescence quenching of the porphyrin increases with an increase in the number of receptors, i.e., hydroquinone entities on the porphyrin macrocycle. Control experiments performed by using zinc porphyrin bearing a dimethoxyphenyl group, i.e., a receptor entity with no H-bonding ability, indicate that the H-bonding plays an important role in quinhydrone formation. Porphyrin-quinhydrone formed by using covalently linked porphyrin-quinone and hydroquinone present in solution shows fluorescence enhancement. The measured fluorescence quantum yields, phi(f), are found to depend on the metal ion in the porphyrin cavity and the oxidation potential of the employed hydroquinones. The present studies also reveal that the measured phi(f) values depend on how the quinhydrone is linked to the porphyrin macrocycle, i.e., either through quinone or hydroquinone. Generally, porphyrin-quinhydrone formed by hydroquinone-appended porphyrins shows decreased phi(f) values as compared to porphyrin-quinhydrone formed by quinone-appended porphyrins.     

Metal ion interaction with phosphorylated tyrosine analogue monolayers on gold

Phosphorylated tyrosine analogue molecules (pTyr-PT) were assembled onto gold substrates, and the resulting monolayers were used for metal ion interaction studies. The monolayers were characterized by X-ray photoelectron spectroscopy (XPS), infrared reflection-absorption spectroscopy (IRAS), cyclic voltammetry (CV), and electrochemical impedance spectroscopy (EIS), both prior to and after exposure to metal ions. XPS verified the elemental composition of the molecular adsorbate and the presence of metal ions coordinated to the phosphate groups. Both the angle-dependent XPS and IRAS results were consistent with the change in the structural orientation of the pTyr-PT monolayer upon exposure to metal ions. The differential capacitance of the monolayers upon coordination of the metal ions was evaluated using EIS. These metal ions were found to significantly change the capacitance of the pTyr-PT monolayers in contrast to the nonphosphorylated tyrosine analogue (TPT). CV results showed reduced electrochemical blocking capabilities of the phosphorylated analogue monolayer when exposed to metal ions, supporting the change in the structure of the monolayer observed by XPS and IRAS. The largest change in the structure and interfacial capacitance was observed for aluminum ions, compared to calcium, magnesium, and chromium ions. This type of monolayer shows an excellent capability to coordinate metal ions and has a high potential for use as sensing layers in biochip applications to monitor the presence of metal ions.     

CO oxidation reaction on Pt(111) studied by the dynamic Monte Carlo method including lateral interactions of adsorbates

The dynamics of adsorbate structures during CO oxidation on Pt(111) surfaces and its effects on the reaction were studied by the dynamic Monte Carlo method including lateral interactions of adsorbates. The lateral interaction energies between adsorbed species were calculated by the density functional theory method. Dynamic Monte Carlo simulations were performed for the oxidation reaction over a mesoscopic scale, where the experimentally determined activation energies of elementary paths were altered by the calculated lateral interaction energies. The simulated results reproduced the characteristics of the microscopic and mesoscopic scale adsorbate structures formed during the reaction, and revealed that the complicated reaction kinetics is comprehensively explained by a single reaction path affected by the surrounding adsorbates. We also propose from the simulations that weakly adsorbed CO molecules at domain boundaries promote the island-periphery specific reaction.     

Dimer pinning and the assignment of semiconductor-adsorbate surface structures

It has been observed in scanning tunneling microscopy (STM) that the adsorption of molecules on the (001) surface of a Group IV semiconductor can lead to an asymmetric ordering of the dimers immediately adjacent to the adsorbate. This so-called pinning may occur along the dimer row on only one, or both sides of the adsorbate. Here we present a straightforward methodology for predicting such pinning and illustrate this approach for several different adsorbate structures on the Si(001) surface. This approach extends earlier work by including the effects of coupling across the adsorbate as well as the nearest-neighbor interactions between the chemisorbed dimer and its adjacent dimers. The results are shown to be in excellent agreement with the room temperature experimental STM data. The examples also show how this approach can serve as a powerful tool for discriminating between alternative possible adsorbate structures on a dimerized semiconductor (001) surface, especially in cases of molecular adsorption where the STM measurements provide insufficient details of the underlying atomic structure.     

STM studies of fusion of cholesterol suspensions and mixed 1,2-dimyristoyl-sn-glycero-3-phosphocholine (DMPC)/cholesterol vesicles onto a Au(111) electrode surface

Electrochemical scanning tunneling microscopy (EC-STM) has been applied to study the structure of the film formed by fusion of cholesterol suspensions and mixed dimyristoylphosphatidylcholine (DMPC)/cholesterol vesicles on a Au(111) electrode surface. It has been demonstrated that cholesterol molecules assemble at the gold support into several structures templated by the crystallography of the metal surface and involving flat or edge-on adsorbed molecules. Studies of the film formed by fusion of mixed DMPC/cholesterol vesicles revealed that ordered domains of either pure DMPC or pure cholesterol were formed. These results indicate that, at the metal surface, the molecules released by the rupture of a vesicle initially self-assemble into a well-ordered monolayer. The self-assembly is controlled by the hydrocarbon skeleton-metal surface interaction. In the case of mixed DMPC/cholesterol vesicles, the molecule-metal interactions induce segregation of the two components into single component domains. However, the molecule-metal interaction induced monolayer is a transient phenomenon. When more molecules accumulate at the surface, the molecule-molecule interactions dominate the assembly, and the monolayer is transformed into a bilayer.     

Size control for two-dimensional iron oxide nanodots derived from biological molecules

We demonstrated the fabrication of size-controlled two-dimensional iron oxide nanodots derived from the heat treatment of ferritin molecules self-immobilized on modified silicon surfaces. Ferritin molecules were immobilized onto 3-aminopropyltrimethoxysilane (3-APMS)-modified silicon surfaces by electrostatic interactions between negatively charged amino acids of ferritin molecules and amino terminal functional groups of 3-APMS. Heat treatments were performed at 400 degrees C for 60 min to fabricate two-dimensional nanodots based on ferritin cores. XPS and FT-IR results clearly indicate that ferritin shells were composed of amino acids and 3-APMS modifiers on silicon surfaces were eliminated by heat treatment. Nanodots on substrate surfaces corresponded to iron oxides. The size of nanodots was tunable in the range of 0-5 (+/-0.75) nm by in situ reactions of iron ion chelators with ferritin molecules immobilized on substrates before heat treatment.     

Supramolecular pattern of fullerene on 2D bimolecular "chessboard" consisting of bottom-up assembly of porphyrin and phthalocyanine molecules

Two-component adlayers consisting of zinc(II) phthalocyanine (ZnPc) and a metalloporphyrin, such as zinc(II) octaethylporphyrin (ZnOEP) or zinc(II) tetraphenylporphyrin (ZnTPP), were prepared by immersing either an Au(111) or Au(100) substrate in a benzene solution containing those molecules. The bimolecular adlayers thus prepared were investigated in 0.1 M HClO4 by cyclic voltammetry (CV) and electrochemical scanning tunneling microscopy (EC-STM). A supramolecularly organized "chessboard" structure was formed for the ZnPc and ZnOEP bimolecular array on Au(111), while characteristic nanohexagons were found in the ZnTPP and ZnOEP bimolecular adlayer. EC-STM revealed that the surface mobility and the molecular re-organization of ZnPc and ZnOEP on Au(111) were tunable by manipulating the electrode potential, whereas the ZnTPP and ZnOEP bimolecular array was independent of the electrode potential. A "bottom-up" hybrid assembly of fullerene molecules was formed successfully on an alternate array of bimolecular ZnPc and ZnOEP molecules. The bimolecular "chessboard" served as a template to form the supramolecular assembly of C60 by selective trapping in the open spaces. A supramolecular organization of ZnPc and ZnOEP was also found on the reconstructed Au(100)-(hex) surface. A highly ordered, compositionally disordered but alternate array of ZnPc and ZnOEP was formed on the reconstructed Au(100)-(hex) surface, indicating that the bimolecular adlayer structure is dependent on the atomic arrangement of underlying Au in the formation of supramolecular nanostructures composed of those molecules. On the bimolecular array consisting of ZnPc and ZnOEP on the Au(100)-(hex), no highly ordered supramolecular assembly of C60 was found, suggesting that the supramolecular assembly of C60 molecules is strongly dependent upon the bimolecular packing arrangement of ZnPc and ZnOEP.     

FT-IR、XPS和DFT研究水杨酸钠在针铁矿或赤铁矿上的吸附机理

采用傅里叶变换红外(FT-IR)光谱、X射线光电子能谱(XPS)以及基于周期平面波的密度泛函理论(DFT)分别研究了水杨酸钠在针铁矿或赤铁矿表面上的吸附结构,并将计算得到的光电子能谱移动(CLS)和电荷转移与实验得到的XPS结果进行对比。FT-IR结果表明,水杨酸钠可能以双齿双核(V)和双齿单核(IV)的形式分别吸附于针铁矿或赤铁矿表面。由DFT计算结果可知,水杨酸钠在针铁矿(101)晶面上形成双齿双核化合物(V)的吸附能为-5.46 eV。而水杨酸钠在针铁矿(101)晶面上形成双齿单核化合物(IV)的吸附能为3.80 eV,因此水杨酸钠在针铁矿上基本不以双齿单核化合物(IV)构型存在。水杨酸钠在赤铁矿(001)晶面上形成双齿单核化合物(IV)时吸附能为-4.07 eV,说明水杨酸钠在赤铁矿(001)晶面上形成了双齿单核化合物(IV)。另外,理论计算的针铁矿(101)晶面上吸附位点铁原子的Fe 2p的CLS值(-0.68 eV)与实验观察到的Fe 2p的CLS值(-0.5 eV)吻合。理论计算的赤铁矿(001)晶面上吸附位点铁原子的Fe 2p的CLS值(-0.80 eV)与实验观察到的Fe 2p的CLS值(-0.8 eV)吻合。因此,水杨酸钠吸附在针铁矿表面时能够通过羧酸基团上一个氧原子和酚羟基上的氧原子与针铁矿(101)表面上的两个铁原子形成双齿双核(V)结构,而在赤铁矿(001)表面上,水杨酸钠中羧酸基团上一个氧原子和酚羟基上的氧原子与赤铁矿(001)表面上的一个铁原子形成了双齿单核(IV)结构。     

Molecular adsorption at well-defined electrode surfaces: hydroquinone on Pd(111) studied by EC-STM

The interaction of hydroquinone (H2Q) with well-defined Pd(111) surfaces at preselected potentials in dilute H2SO4 has been studied by molecule-resolved electrochemical scanning tunneling microscopy (EC-STM). H2Q spontaneously undergoes oxidative chemisorption to benzoquinone (Q), which adopts a slightly tilted parallel orientation. Evidently, the surface coordination is through the quinone pi-electron system. At potentials within the double-layer region, a close-packed well-ordered Pd(111)-(3 x 3)-Q adlattice was formed. A potential excursion to 0.7 V, a potential at which the solution-phase Q/H2Q redox reaction takes place, introduced disorder into the organic adlayer; this positive-potential-induced order-to-disorder phase transition is reversible because the ordered (3 x 3)-Q adlattice was regenerated when the potential reverted to 0.4 V. When the potential was poised at 0.2 V, a potential at which hydrogen evolution was initiated, an appreciable fraction of Q was (hydrogenatively) desorbed; the remnant Q molecules were agglomerated in small islands that retained the (3 x 3) symmetry of the full adlayer. Two possible structural models of the Pd(111)-(3 x 3)-Q adlattice are described.     

Sulfur multilayer formation on Au(111): new insights from the study of hexamethyldisilathiane

Hexamethyldisilathiane was successfully used as a new precursor for the formation of S layers on Au and to study their interaction. Characterization of the S modified gold surface was done by X-ray photoelectron spectroscopy (XPS), cyclic voltammetry (CV), and scanning tunneling microscopy (STM). Key findings include the direct observation by STM of (i) coexistence of different phases, (ii) multiple sulfur layers formation, (ii) formation of rectangular structures not only on the adlayer but also on the top layer, and (iv) rectangular structure mobility on different layers. These results provide clear evidence regarding the adsorbate nature of the rectangular structures, solving a highly debated question.     

Ionic hydrogen bonds controlling two-dimensional supramolecular systems at a metal surface

Hydrogen-bond formation between ionic adsorbates on an Ag(111) surface under ultrahigh vacuum was studied by scanning tunneling microscopy/spectroscopy (STM/STS), X-ray photoelectron spectroscopy (XPS), near-edge X-ray absorption fine structure (NEXAFS), and molecular dynamics calculations. The adsorbate, 1,3,5-benzenetricarboxylic acid (trimesic acid, TMA), self-assembles at low temperatures (250-300 K) into the known open honeycomb motif through neutral hydrogen bonds formed between carboxyl groups, whereas annealing at 420 K leads to a densely packed quartet structure consisting of flat-lying molecules with one deprotonated carboxyl group per molecule. The resulting charged carboxylate groups form intermolecular ionic hydrogen bonds with enhanced strength compared to the neutral hydrogen bonds; this represents an alternative supramolecular bonding motif in 2D supramolecular organization.     

Hemin interaction with bare and 4,4'-thio-bis-benzene-thiolate covered n-GaAs (110) electrodes

Cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) investigations on the redox behavior of hemin at bare and 4,4'-thio-bis-benzene-thiolate (TBBT) covered n-GaAs (110) electrodes in dimethylsulfoxide (DMSO) revealed the high irreversibility of the electroreduction process, which appeared to be closely related to the stable adsorbed species strongly interfering with the electronic properties of the semiconducting substrate. The subsequent exploration of the hemin-modified electrodes by second harmonic generation (SHG), X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM) measurements pointed to significant differences between the iron protoporphyrin species adsorbed on the bare- and TBBT-GaAs (110) electrodes. Only Fe(2+) species having a flat configuration with the porphyrin plane oriented parallel to the surface were detected on GaAs, unlike the TBBT-GaAs, where Fe(2+) and Fe(3+) species having both flat and vertical adsorption positions could be observed. These differences originate from the mutual interactions between the solvent, hemin and dithiolate molecules as well as their competition for the surface sites found to play a key role in the electrochemical process under discussion.     

Spectroscopic study on sorption of hydrogen sulfide by means of red soil

This paper reports the results of the characterization of red soils in relation to the sorption of H2S from coal gas at 500 degrees C by spectroscopic techniques in order to provide more information on red soils' structural change both before and after reaction. In addition, by-products analysis has also been studied using Fourier transform infrared (FTIR) spectroscopy. Before and after the experiments the red soils were characterized with X-ray powder diffraction (XRPD), energy dispersion spectrum (EDS), X-ray photoelectron spectroscopy (XPS) and FTIR spectroscopy. XRPD results indicate that iron oxide species disappear from the original to reacted red soil. EDS analysis shows that a significant amount of sulfur is present in the reacted red soil, which is in agreement with the results of the elemental analysis and the calculated value based on breakthrough curve. XPS regression fitting results further indicate that sulfur retention may be associated with the iron oxides. S 2p XPS fittings point out that the major sulfur species present in the reacted red soil are composed of S(-2), elemental sulfur, polysulfide, sulfite and sulfate. Additionally, the binding energy of iron shifts to a lower position for the reacted red soil, which indicates that iron oxides in the original red soil have been converted into iron sulfide. Appreciable amounts of the by-products CO2, SO2 and COS are detected by on-line FTIR spectroscopy during the initial and later stages of the sorption process. The formation of CO2 is related to the water-shift reaction, and SO2 is probably attributable to the reaction of organic matters and H2S. The concentration of COS is quantified by GC/FPD and found it to be about 350 ppm, which is close to the equilibrium concentration of the reaction of inlet CO and H2S at a temperature of 500 degrees C.     

Electrochemical and surface characterization of 4-aminothiophenol adsorption at polycrystalline platinum electrodes

The formation of a self-assembled monolayer (SAM) of 4-aminothiophenol (4-ATP) on polycrystalline platinum electrodes has been characterized by surface analysis and electrochemistry techniques. The 4-ATP monolayer was characterized by cyclic voltammetry (CV), linear sweep voltammetry, Raman spectroscopy, reflection-absorption infrared (RAIR) spectroscopy, and X-ray photoelectron spectroscopy (XPS). CV was used to study the dependence of the adsorption time and 4-ATP solution concentration on the relative degree of coverage of 4-ATP monolayers on polycrystalline Pt electrodes. The adsorption time range probed was 24-72 h. The optimal concentration of 4-ATP needed to obtain the highest surface at the lowest adsorption time was 10 mM. RAIR and Raman spectroscopy for 4-ATP-modified platinum electrodes showed the characteristic adsorption bands for 4-ATP, such as nuNH, nuCH(arom), and nuCS(arom), indicating the adsorption on the platinum surface. The XPS spectra for the modified Pt surface presented the binding energy peaks of sulfur and nitrogen. High energy resolution XPS studies, RAIR, and Raman spectrum for platinum electrodes modified with 4-ATP indicate that the molecules are sulfur-bonded to the platinum surface. The formation of a S-Pt bond suggests that ATP adsorption leads to an amino-terminated electrode surface. The thickness of the monolayer was evaluated via angle-resolved XPS (AR-XPS) analyses, giving a value of 8 A. As evidence of the terminal amino group on the electrode surface, the chemical derivatization of the 4-ATP SAM was done with 16-Br hexadecanoic acid. This surface reaction was followed by RAIR spectroscopy.     

Adsorption of sulfur dioxide on hematite and goethite particle surfaces

The adsorption of sulfur dioxide (SO(2)) on iron oxide particle surfaces at 296 K has been investigated using X-ray photoelectron spectroscopy (XPS). A custom-designed XPS ultra-high vacuum chamber was coupled to an environmental reaction chamber so that the effects of adsorbed water and molecular oxygen on the reaction of SO(2) with iron oxide surfaces could be followed at atmospherically relevant pressures. In the absence of H(2)O and O(2), exposure of hematite (alpha-Fe(2)O(3)) and goethite (alpha-FeOOH) to SO(2) resulted predominantly in the formation of adsorbed sulfite (SO(3)(2-)), although evidence for adsorbed sulfate (SO(4)(2-)) was also found. At saturation, the coverage of adsorbed sulfur species was the same on both alpha-Fe(2)O(3) and alpha-FeOOH as determined from the S2p : Fe2p ratio. Equivalent saturation coverages and product ratios of sulfite to sulfate were observed on these oxide surfaces in the presence of water vapor at pressures between 6 and 18 Torr, corresponding to 28 to 85% relative humidity (RH), suggesting that water had no effect on the adsorption of SO(2). In contrast, molecular oxygen substantially influenced the interactions of SO(2) with iron oxide surfaces, albeit to a much larger extent on alpha-Fe(2)O(3) relative to alpha-FeOOH. For alpha-Fe(2)O(3), adsorption of SO(2) in the presence of molecular oxygen resulted in the quantitative formation of SO(4)(2-) with no detectable SO(3)(2-). Furthermore, molecular oxygen significantly enhanced the extent of SO(2) uptake on alpha-Fe(2)O(3), as indicated by the greater than two-fold increase in the S2p : Fe2p ratio. Although SO(2) uptake is still enhanced on alpha-Fe(2)O(3) in the presence of molecular oxygen and water, the enhancement factor decreases with increasing RH. In the case of alpha-FeOOH, there is an increase in the amount of SO(4)(2-) in the presence of molecular oxygen, however, the predominant surface species remained SO(3)(2-) and there is no enhancement in SO(2) uptake as measured by the S2p : Fe2p ratio. A mechanism involving molecular oxygen activation on oxygen vacancy sites is proposed as a possible explanation for the non-photochemical oxidation of sulfur dioxide on iron oxide surfaces. The concentration of these sites depends on the exact environmental conditions of RH.