Surface water enhances the uptake and photoreactivity of gaseous catechol on solid iron(III) chloride.

Uptake and photoreactivity of catechol-Fe complexes are investigated at the gas/solid interface under humid and dry conditions, along with the nature of the hydrogen-bonding network of adsorbed water. Catechol was chosen as a simple model for organics in aerosols. Iron chloride was used to distinguish ionic mobility from binding to coordinated iron(III) in hematite. Studies were conducted using diffuse reflectance infrared Fourier transform spectroscopy as a function of irradiation time. Results show that adsorbed water at 30% relative humidity (RH), not light, increases the concentration of adsorbed catechol by a factor of 3 over 60 min relative to dry conditions. Also, our data show that, at 30% RH and under light and dark conditions, growth factors describing the concentration of adsorbed catechol are very similar suggesting that light does not significantly enhance the uptake of catechol vapor on FeCl3. Surface water also enhances the initial photodecay kinetics of catechol-Fe complexes at 30% RH by a factor of 10 relative to control experiments (RH < 1%, or no FeCl3 under humid conditions). Absorptions assigned to carbonyl groups were not observed with irradiation time, which was explained by the dominance of FeCl(2+) species relative to FeOH(2+) in the highly acidic "quasi-liquid" phase at 30% RH. Clear differences in the hydrogen-bonding network upon gaseous catechol uptake are observed in the dark and light and during the photodecay of adsorbed catechol. The implications of these results on our understanding of interfacial processes in aged iron-containing surfaces are discussed.

DRIFTS studies on the role of surface water in stabilizing catechol-iron(III) complexes at the gas/solid interface.

Surface water plays a crucial role in facilitating or inhibiting surface reactions in atmospheric aerosols. However, little is known about the role of surface water in the complexation of organic acid molecules to transition metals in multicomponent aerosol systems. We report herein results from real time DRIFTS experiments that show in situ complexation of catechol to Fe(III) under humid conditions. Catechol was schosen as a simple model for humic-like substances (HULIS) in aerosols and aged polyaromatic hydrocarbons (PAH). It was also detected in secondary organic aerosols (SOA) formed from the reaction of hydroxyl radicals with benzene. Given the importance of the iron content in aerosols and its biogeochemistry, our studies were conducted using FeCl3. For comparison, these surface-sensitive studies were complemented with bulk aqueous ATR-FTIR, UV-vis, and HPLC measurements for structural, quantitative, and qualitative information about complexes in the bulk, and potential degradation products in the dark. Under dry conditions, DRIFTS spectra show that gas phase catechol adsorbs molecularly and is fully protonated on samples containing FeCl3 with no evidence of complexation to Fe(III). Upon increasing the relative humidity to a value below the deliquescence of FeCl3, surface water facilitates ionic mobility resulting in the formation of monodentate catechol-Fe complexes. These complexes are stable at the gas/solid interface and do not undergo any further degradation in the dark as shown from bulk UV-vis and HPLC experiments. The implications of our studies on understanding interfacial and condensed phase chemistry relevant to multicomponent aerosols, water thin films on buildings, and ocean surfaces containing transition metals are discussed.

Kinetic ATR-FTIR studies on phosphate adsorption on iron (oxyhydr)oxides in the absence and presence of surface arsenic: molecular-level insights into the ligand exchange mechanism.

The surface chemistry of phosphorus and arsenic compounds in their organic and inorganic forms is of great interest to the scientific and industrial communities due to its role in controlling their transport, bioaccessibility and speciation. We report herein in situ and surface-sensitive rapid kinetic studies on the adsorption of phosphate to Fe (oxyhydr)oxides in the presence and absence of dimethylarsinic acid (DMA) and arsenate. These studies were conducted at pH 7 using ATR-FTIR in the flow mode, which were complemented with detailed kinetic analysis of the desorption behavior of DMA and arsenate over the same range of aqueous [phosphate]. Values for apparent rates of adsorption and desorption were extracted from the time dependence of given spectral components characteristic of surface phosphate, DMA, or arsenate. Results show that pseudo adsorption rate constants of phosphate on Fe (oxyhydr)oxide films increase in this order: arsenate-covered < DMA-covered ≤ freshly prepared. Also, pseudo desorption rate constants of DMA complexes are 7-12 times higher than arsenate using phosphate as a desorbing agent. When these results are combined with earlier work on the thermodynamics, kinetics, and structure of surface complexes, they suggest that, during initial times of surface interactions, increasing organic substitution on arsenate increases the proportion of relatively weakly bonded complexes (monodentate and outer-sphere).

ATR-FTIR studies on the adsorption/desorption kinetics of dimethylarsinic acid on iron-(oxyhydr)oxides.

Dimethylarsinic acid (DMA) is an organoarsenical compound that, along with monomethylarsonic acid, poses a health and an environmental risk, and a challenge to the energy industry. Little is known about the surface chemistry of DMA at the molecular level with materials relevant to geochemical environments and industrial sectors. We report herein the first in situ and surface-sensitive rapid kinetic studies on the adsorption and desorption of DMA to/from hematite and goethite at pH 7 and I = 0.01 M KCl using ATR-FTIR. Values for the apparent rates of adsorption and desorption were extracted from experimental data as a function of spectral components, flow rate of the aqueous phase, film thickness of hematite, and using chloride and hydrogen phosphate as desorbing agents. The adsorption kinetic data show fast and slow rates, consistent with the formation of more than one type of adsorbed DMA. Apparent adsorption and desorption rate constants were extracted from the dependency of the initial adsorption rates on [DMA(aq)]. Desorption rate constants were also extracted from desorption experiments using hydrogen phosphate and chloride solutions, and were found to be higher by 1-2 orders of magnitude than those using chloride. In light of the complex ligand exchange reaction mechanism of DMA desorption by phosphate species at pH 7, apparent desorption rate constants were found to depend on [hydrogen phosphate] with an order of 0.3. The impact of our studies on the environmental fate of DMA in geochemical environments, and the design of technologies to reduce arsenic content in fuels is discussed.