A spectroscopic study of atmospherically relevant concentrated aqueous nitrate solutions

Concentrated aqueous nitrate aerosols are present in the Earth's atmosphere as a result of heterogeneous reactions of sea salt and mineral dust aerosol with nitrogen oxides (e.g., NO2, NO3, HNO3 and N2O5). Because the water content of these aerosols depends on relative humidity (RH), the composition and nitrate ion concentration will also depend on RH. Unlike the original aerosols, aqueous nitrate aerosols are photochemically active at solar wavelengths. To gain a better understanding of the nitrate ion chromophore in concentrated aqueous nitrate aerosols, we have measured the ATR-FTIR and UV/vis spectra of concentrated nitrate solutions over a large concentration range. Both ATR-FTIR and UV/vis spectroscopy show changes in the nitrate ion spectra with increasing concentration. Ab initio calculations are used to aid in the assignment and interpretation of these spectra. From these data, we predict that the photoreactivity of aqueous nitrate aerosols will strongly depend on relative humidity as the molecular and electronic structure of the nitrate ion becomes increasingly perturbed from that of the isolated ion in highly concentrated atmospherically relevant solutions.     

Surface-catalyzed chlorine and nitrogen activation: mechanisms for the heterogeneous formation of ClNO, NO, NO2, HONO, and N2O from HNO3 and HCl on aluminum oxide particle surfaces

It is well-known that chlorine active species (e.g., Cl(2), ClONO(2), ClONO) can form from heterogeneous reactions between nitrogen oxides and hydrogen chloride on aerosol particle surfaces in the stratosphere. However, less is known about these reactions in the troposphere. In this study, a potential new heterogeneous pathway involving reaction of gaseous HCl and HNO(3) on aluminum oxide particle surfaces, a proxy for mineral dust in the troposphere, is proposed. We combine transmission Fourier transform infrared spectroscopy with X-ray photoelectron spectroscopy to investigate changes in the composition of both gas-phase and surface-bound species during the reaction under different environmental conditions of relative humidity and simulated solar radiation. Exposure of surface nitrate-coated aluminum oxide particles, from prereaction with nitric acid, to gaseous HCl yields several gas-phase products, including ClNO, NO(2), and HNO(3), under dry (RH < 1%) conditions. Under humid more conditions (RH > 20%), NO and N(2)O are the only gas products observed. The experimental data suggest that, in the presence of adsorbed water, ClNO is hydrolyzed on the particle surface to yield NO and NO(2), potentially via a HONO intermediate. NO(2) undergoes further hydrolysis via a surface-mediated process, resulting in N(2)O as an additional nitrogen-containing product. In the presence of broad-band irradiation (λ > 300 nm) gas-phase products can undergo photochemistry, e.g., ClNO photodissociates to NO and chlorine atoms. The gas-phase product distribution also depends on particle mineralogy (Al(2)O(3) vs CaCO(3)) and the presence of other coadsorbed gases (e.g., NH(3)). These newly identified reaction pathways discussed here involve continuous production of active ozone-depleting chlorine and nitrogen species from stable sinks such as gas-phase HCl and HNO(3) as a result of heterogeneous surface reactions. Given that aluminosilicates represent a major fraction of mineral dust aerosol, aluminum oxide can be used as a model system to begin to understand various aspects of possible reactions on mineral dust aerosol surfaces.     

Heterogeneous photochemistry of trace atmospheric gases with components of mineral dust aerosol

Mineral dust aerosol is known to provide a reactive surface in the troposphere for heterogeneous chemistry to occur. Certain components of mineral dust aerosol, such as semiconductor metal oxides, can act as chromophores that initiate chemical reactions, while adsorbed organic and inorganic species may also be photoactive. However, relatively little is known about the impact of heterogeneous photochemistry of mineral dust aerosol in the atmosphere. In this study, we investigate the heterogeneous photochemistry of trace atmospheric gases including HNO(3) and O(3) with components of mineral dust aerosol using an environmental aerosol chamber that incorporates a solar simulator. For reaction of HNO(3) with aluminum oxide, broadband irradiation initiates photoreactions to form gaseous NO and NO(2). A complex dynamic balance between surface adsorbed nitrate and gaseous nitrogen oxide products including NO and NO(2) is observed. For heterogeneous photoreactions of O(3), iron oxide shows catalytic decompositions toward O(3) while aluminum oxide is deactivated by ozone exposure. Furthermore, the role of relative humidity, and, thus, adsorbed water, on heterogeneous photochemistry has been explored. The atmospheric implications of these results are discussed.     

Photochemistry of adsorbed nitrate

In the atmosphere, gas-phase nitrogen oxides including nitric acid react with particle surfaces (e.g., mineral dust and sea salt aerosol) to yield adsorbed nitrate, yet little is known about the photochemistry of nitrate on the surface of these particles. In this study, nitrate adsorbed on alumina surfaces, a surrogate for mineral dust aerosol, is irradiated with broadband light (lambda > 300 nm) in the absence and presence of coadsorbed water, at <1% and 45 +/- 2% relative humidity (%RH), respectively, and molecular oxygen. Upon irradiation, the nitrate ion readily undergoes photolysis to yield nitrogen-containing gas-phase products, NO2, NO, and N2O. Although NO2, NO, and N2O form under the different conditions investigated, both coadsorbed water and molecular oxygen change the gas-phase product distribution, with NO being the major product under dry and humid conditions in the absence of molecular oxygen and NO2 the major product in the presence of molecular oxygen. To the best of our knowledge, this is the first study to investigate the role of solvation by coadsorbed water in the photochemistry of adsorbates at solid interfaces and the roles that molecular oxygen, adsorbed water, and relative humidity may have in photochemical processes on aerosol surfaces that have the potential to alter the chemical balance of the atmosphere.     

Synergistic reaction between SO2 and NO2 on mineral oxides: a potential formation pathway of sulfate aerosol

Sulfate is one of the most important aerosols in the atmosphere. A new sulfate formation pathway via synergistic reactions between SO(2) and NO(2) on mineral oxides was proposed. The heterogeneous reactions of SO(2) and NO(2) on CaO, α-Fe(2)O(3), ZnO, MgO, α-Al(2)O(3), TiO(2), and SiO(2) were investigated by in situ Diffuse Reflectance Infrared Fourier Transform Spectroscopy (in situ DRIFTS) at ambient temperature. Formation of sulfate from adsorbed SO(2) was promoted by the coexisting NO(2), while surface N(2)O(4) was observed as the crucial oxidant for the oxidation of surface sulfite. This process was significantly promoted by the presence of O(2). The synergistic effect between SO(2) and NO(2) was not observed on other mineral particles (such as CaCO(3) and CaSO(4)) probably due to the lack of the surface reactive oxygen sites. The synergistic reaction between SO(2) and NO(2) on mineral oxides resulted in the formation of internal mixtures of sulfate, nitrate, and mineral oxides. The change of mixture state will affect the physicochemical properties of atmospheric particles and therefore further influence their environmental and climate effects.     

Reactive uptake of acetic acid on calcite and nitric acid reacted calcite aerosol in an environmental reaction chamber

The heterogeneous chemistry of gas-phase acetic acid with CaCO(3)(calcite) aerosol was studied under varying conditions of relative humidity (RH) in an environmental reaction chamber. Infrared spectroscopy showed the loss of gas-phase reactant and the appearance of a gaseous product species, CO(2). The acetic acid is observed to adsorb onto the calcite aerosol through both a fast and a slow uptake channel. While the fast channel is relatively independent of RH, the slow channel exhibits enhanced uptake and reaction as the RH is increased. In additional experiments, the calcite aerosol was exposed to both nitric and acetic acids in the presence of water vapor. The rapid conversion of the particulate carbonate to nitrate and subsequent deliquescence significantly enhances the uptake and reaction of acetic acid. These results suggest a possible mechanism for observed correlations between particulate nitrate and organic acids in the atmosphere. Calcium rich mineral dust may be an important sink for simple organic acids.     

Enhanced surface photochemistry in chloride-nitrate ion mixtures

Heterogeneous reactions of sea salt aerosol with various oxides of nitrogen lead to replacement of chloride ion by nitrate ion. Studies of the photochemistry of a model system were carried out using deliquesced mixtures of NaCl and NaNO3 on a Teflon substrate. Varying molar ratios of NaCl to NaNO3 (1 : 9 Cl- : NO3-, 1 : 1 Cl- : NO3-, 3 : 1 Cl- : NO3-, 9 : 1 Cl- : NO3-) and NaNO3 at the same total concentration were irradiated in air at 299 +/- 3 K and at a relative humidity of 75 +/- 8% using broadband UVB light (270-380 nm). Gaseous NO2 production was measured as a function of time using a chemiluminescence NO(y) detector. Surprisingly, an enhanced yield of NO2 was observed as the chloride to nitrate ratio increased. Molecular dynamics (MD) simulations show that as the Cl- : NO3- ratio increases, the nitrate ions are drawn closer to the interface due to the existence of a double layer of interfacial Cl- and subsurface Na+. This leads to a decreased solvent cage effect when the nitrate ion photodissociates to NO2+O*-, increasing the effective quantum yield and hence the production of gaseous NO2. The implications of enhanced NO2 and likely OH production as sea salt aerosols become processed in the atmosphere are discussed.     

Heterogeneous reaction of acetic acid on MgO, α-Al2O3, and CaCO3 and the effect on the hygroscopic behaviour of these particles

Mixtures of organic compounds with mineral dust are ubiquitous in the atmosphere, whereas the formation pathways and hygroscopic behavior of these mixtures are not well understood. In this study, in situ DRIFTS, XRD, and a vapor sorption analyzer were used to investigate the heterogeneous reaction of acetic acid on α-Al(2)O(3), MgO, and CaCO(3) particles under both dry and humid conditions while the effect of reactions on the hygroscopic behavior of these particles was also measured. In all cases, formation of acetate is significantly enhanced in the presence of surface water. However, the reaction extent varied with the mineral phase of these particles. For α-Al(2)O(3), the reaction is limited to the surface with the formation of surface coordinated acetate under both dry and humid conditions. For MgO, the bulk of the particle is involved in the reaction and Mg(CH(3)COO)(2) is formed under both dry and humid conditions, although it exhibits a saturation effect under dry conditions. In the case of CaCO(3), acetic acid uptake is limited to the surface under dry conditions while it leads to the decomposition of the bulk of CaCO(3) under humid conditions. While coordinated surface acetate species increased the water adsorption capacity slightly, the formation of bulk acetate promoted the water absorption capacity greatly. This study demonstrated that heterogeneous reaction between CH(3)COOH and mineral dust is not only an important sink for CH(3)COOH, but also has a significant effect on the hygroscopic behavior of mineral dust.     

Heterogeneous uptake of ozone on reactive components of mineral dust aerosol: an environmental aerosol reaction chamber study

We have undertaken a kinetic study of heterogeneous ozone decomposition on alpha-Fe2O3 (hematite) and alpha-Al2O3 (corundum) aerosols under ambient conditions of temperature, pressure, and relative humidity in order to better understand the role of mineral dust aerosol in ozone loss mechanisms in the atmosphere. The kinetic measurements are made in an environmental aerosol reaction chamber by use of infrared and ultraviolet spectroscopic probes. The apparent heterogeneous uptake coefficient, gamma, for ozone reaction with alpha-Fe2O3 and alpha-Al2O3 surfaces is determined as a function of relative humidity (RH). The uptake of ozone by the iron oxide surface is approximately an order of magnitude larger than that by the aluminum oxide sample, under dry conditions. At the pressures used, alpha-Fe2O3 shows clear evidence for catalytic decomposition of ozone while alpha-Al2O3 appears to saturate at a finite ozone coverage. The measured uptake for both minerals decreases markedly as the RH is increased. Comparison with other literature reports and the atmospheric implications of these results are discussed.     

Local and non-local sources of airborne particulate pollution at Beijing--The ratio of Mg/Al as an element tracer for estimating the contributions of mineral aerosols from outside Beijing

A new element tracer technique has firstly been established to estimate the contributions of mineral aerosols from both inside and outside Beijing. The ratio of Mg/Al in aerosol is a feasible element tracer to distinguish between the sources of inside and outside Beijing. Mineral aerosol, inorganic pollution aerosol mainly as sulfate and nitrate, and organic aerosol are the major components of airborne particulates in Beijing, of which mineral aerosol accounted for 32%―67% of total suspended particles (TSP), 10%―70% of fine particles (PM2.5), and as high as 74% and 90% of TSP and PM2.5, respectively, in dust storm. The sources from outside Beijing contributed 62% (38%―86%) of the total mineral aerosols in TSP, 69% (52%―90%) in PM10, and 76% (59%―93%) in PM2.5 in spring, and 69% (52%―83%), 79% (52%―93%), and 45% (7%―79%) in TSP, PM10, and PM2.5, respectively, in winter, while only ～20% in summer and autumn. The sources from outside Beijing contributed as high as 97% during dust storm and were the dominant source of airborne particulates in Beijing. The contributions from outside Beijing in spring and winter are higher than those in summer, indicating clearly that it was related to the various meteorological factors.     

The heterogeneous chemical kinetics of NO3 on atmospheric mineral dust surrogates

Uptake experiments of NO3 on mineral dust powder were carried out under continuous molecular flow conditions at 298 +/- 2 K using the thermal decomposition of N2O5 as NO3 source. In situ laser detection using resonance enhanced multiphoton ionization (REMPI) to specifically detect NO2 and NO in the presence of N2O5, NO3 and HNO3 was employed in addition to beam-sampling mass spectrometry. At [NO3] = (7.0 +/- 1.0) x 10(11) cm(-3) we found a steady state uptake coefficient gamma(ss) ranging from (3.4 +/- 1.6) x 10(-2) for natural limestone to (0.12 +/- 0.08) for Saharan Dust with gamma(ss) decreasing as [NO3] increased. NO3 adsorbed on mineral dust leads to uptake of NO2 in an Eley-Rideal mechanism that usually is not taken up in the absence of NO3. The disappearance of NO3 was in part accompanied by the formation of N2O5 and HNO3 in the presence of NO2. NO3 uptake performed on small amounts of Kaolinite and CaCO3 leads to formation of some N2O5 according to NO((3ads)) + NO(2(g)) --> N2O(5(ads)) --> N2O(5(g)). Slow formation of gas phase HNO3 on Kaolinite, CaCO3, Arizona Test Dust and natural limestone has also been observed and is clearly related to the presence of adsorbed water involved in the heterogeneous hydrolysis of N2O(5(ads)).     

Magnesium sulfate aerosols studied by FTIR spectroscopy: hygroscopic properties, supersaturated structures, and implications for seawater aerosols

Supersaturated MgSO4 aerosols and dilute MgSO4 solutions were studied by FTIR spectroscopic techniques (i.e., aerosol flow tube (AFT) and attenuated total reflection (ATR)). The hygroscopic properties of MgSO4 aerosols were investigated with results in good agreement with previous measurements by a scanning electrodynamic balance (SEDB). Well-defined spectral evolutions with changing relative humidity (RH) for the v3 band of SO4(2-) and the water O-H stretching envelope could be directly related to the observed hygroscopic properties of MgSO4 aerosols. When the RH decreased from approximately 55 to approximately 40%, the v1 band of SO4(2-) in supersaturated MgSO4 aerosols was observed to transform from a sharp peak at approximately 983 cm(-1) into a wide band at approximately 1005 cm(-1). The sharp peak at approximately 983 cm(-1) was mainly assigned to such associated complexes of Mg2+ and SO4(2-) as double solvent-separated ion pairs (2SIPs), solvent-shared ion pairs (SIPs), and simple contact ion pairs (CIPs) in supersaturated MgSO4 aerosols, while the wide band at approximately 1005 cm(-1) was due to polymeric CIPs chains, probably the main component of gels formed in MgSO4 aerosols at low RHs. Relating to this v1 band transformation, the peak position of the v(3) band was first shown to be a sensitive indicator of CIPs formation, spanning across approximately 40 cm(-1) on the formation of polymeric CIPs chains, which could also be supported by aerosol composition analysis in the form of water-to-solute molar ratios (WSR). In the water O-H stretching envelope, the absorbance intensities at 3371 and 3251 cm(-1) were selected to represent contributions from weak and strong hydrogen bonds, respectively. The absorbance intensity ratio changing with RH of 3371 to 3251 cm(-1) could be related to the previous observations with the v1 and v3 bands of SO4(2-). As a result, the formation of CIPs with various structures in large amounts was supposed to significantly weaken hydrogen bonds in supersaturated MgSO4 aerosols, while 2SIPs and SIPs were not expected to have similar effects even when occurring in abundance. In comparison with MgSO4 aerosols, the peak positions of the v3 band of SO4(2-) in artificial seawater aerosols implied that the MgSO4 component should be contained as gels or concentrated solutions in the fissures of microcrystals of sea salts for freshly formed seawater aerosols at low RHs.     

Interaction between biopolyelectrolytes and sparingly soluble mineral particles

We investigate the complex physicochemical behavior of dispersions containing calcium carbonate (CaCO(3)) particles, a sparingly soluble mineral salt; and carrageenans, negatively charged biopolyelectrolytes containing sulfate groups. We reveal that the carrageenans suspend and stabilize CaCO(3) particles in neutral systems by absorbing on the particle surface which provides electrosteric stabilization. In addition, carrageenans provide a weak apparent yield stress which keeps the particles suspended for several months. The absorption measurements of carrageenan on the CaCO(3) particle indicate that more carrageenan is removed from the solution than expected from the case of a simple monolayer adsorption. Confocal laser scanning microscopy observations confirm that polyelectrolyte-containing precipitate is formed in both CaCO(3)-carrageenan and CaCl(2)-carrageenan mixtures. On the basis of these results, we confirm that in the presence of carrageenan some CaCO(3) dissolves and the Ca(2+) ions interact with the sulfate groups leading to aggregation and formation of particle-like structures. These new insights are important for fundamental understanding of other mineral-polyelectrolyte systems and have important implications for various industrial applications where calcium carbonate is used.     

N(2)O(5) reaction on submicron sea salt aerosol: kinetics, products, and the effect of surface active organics

The reaction of N(2)O(5) on sea salt aerosol is a sink for atmospheric nitrogen oxides and a source of the Cl radical. We present room-temperature measurements of the N(2)O(5) loss rate on submicron artificial seawater (ASW) aerosol, performed with an entrained aerosol flow tube coupled to a chemical ionization mass spectrometer, as a function of aerosol phase (aqueous or partially crystalline), liquid water content, and size. We also present an analysis of the product growth kinetics showing that ClNO(2) is produced at a rate equal to N(2)O(5) loss, with an estimated lower limit yield of 50% at 50% relative humidity (RH). The reaction probability for N(2)O(5), gamma(N(2)(O)(5)), depends strongly on the particle phase, being 0.005 +/- 0.004 on partially crystalline ASW aerosol at 30% RH and 0.03 +/- 0.008 on aqueous ASW aerosol at 65% RH. At 50% RH, N(2)O(5) loss is relatively insensitive to particle size for radii greater than 100 nm, and gamma(N(2)(O)(5)) displays a statistically insignificant increase from 0.022 to approximately 0.03 for aqueous ASW aerosol over the RH range of 43-70%. We find that the presence of millimolar levels of hexanoic acid in the aerosol bulk decreases the gamma(N(2)(O)(5)) at 70% RH by a factor of 3-4 from approximately 0.025 to 0.008 +/- 0.004. This reduction is likely due to the partitioning of hexanoic acid to the gas-aerosol interface at a surface coverage that we estimate to be equivalent to a monolayer. This result is the first evidence that a monolayer coating of aqueous organic surfactant can slow the reactive uptake of atmospheric trace gases to aerosol.     

Heterogeneous interactions of calcite aerosol with sulfur dioxide and sulfur dioxide-nitric acid mixtures

The heterogeneous chemistry of sulfur dioxide with CaCO(3) (calcite) aerosol as a function of relative humidity (RH) has been studied under isolated particle conditions in an atmospheric reaction chamber using infrared absorption spectroscopy. The reaction of SO(2) with calcite produced gas phase CO(2) as a product in addition to the conversion of the particulate carbonate to sulfite. The reaction extent was found to increase with elevated RH, as has been observed for the similar reaction with HNO(3), but much higher relative humidities were needed to significantly enhance the reaction. Mixed experiments in which calcite aerosol was exposed to both HNO(3) and SO(2) were also performed. The overall reaction extent at a given relative humidity did not appear to be increased by having both reactant gases present. The role of carbonate aerosol as an atmospheric sink for sulfur dioxide and particulate nitrogen and sulfur correlations are discussed.     

Local and non-local sources of airborne particulate pollution at Beijing

A new element tracer technique has firstly been established to estimate the contributions of mineral aerosols from both inside and outside Beijing. The ratio of Mg/Al in aerosol is a feasible element tracer to distinguish between the sources of inside and outside Beijing. Mineral aerosol, inorganic pollution aerosol mainly as sulfate and nitrate, and organic aerosol are the major components of airborne particulates in Beijing, of which mineral aerosol accounted for 32%–-67% of total suspended particles (TSP), 10% –70% of fine particles (PM2.5), and as high as 74% and 90% of TSP and PM_2.5, respectively, in dust storm. The sources from outside Beijing contributed 62% (38%–-86%) of the total mineral aerosols in TSP, 69% (52%–-90%) in PM₁₀, and 76% (59%–-93%) in PM_2.5 in spring, and 69% (52%–-83%), 79% (52%–-93%), and 45% (7% – 79%) in TSP, PM₁₀, and PM_2.5, respectively, in winter, while only ≈20% in summer and autumn. The sources from outside Beijing contributed as high as 97% during dust storm and were the dominant source of airborne particulates in Beijing. The contributions from outside Beijing in spring and winter are higher than those in summer, indicating clearly that it was related to the various meteorological factors.     

Heterogeneous conversion of calcite aerosol by nitric acid

The reaction of nitric acid with calcite aerosol at varying relative humidities has been studied under suspended particle conditions in an atmospheric reaction chamber using infrared absorption spectroscopy. The reactant concentration in the chamber, as well as the appearance of gas phase products and surface adsorbed species, was spectroscopically monitored before and after mixing with CaCO(3) (calcite) particles. The interaction with HNO(3) was found to lead to gas phase CO(2) evolution and increased water uptake due to heterogeneous conversion of the carbonate to particulate nitrate. The reaction was enhanced as the relative humidity of the system was increased, especially at relative humidities above the reported deliquescence point of particulate Ca(NO(3))(2). The measured reaction extent demonstrates that the total calcite particulate mass is available for reaction with HNO(3) and the conversion process is not limited to the particle surface. The spectroscopy of the surface formed nitrate suggests a highly concentrated solution environment with a significant degree of ion pairing. The implications of the HNO(3) loss and the formation of the particulate nitrate product for atmospheric chemistry are discussed.     

Effect of magnesium/calcium ratios in solutions treated by electrodialysis: morphological characterization and identification of anion-exchange membrane fouling

The present study aimed the characterization of the fouling formed on anion-exchange membrane during electrodialysis treatment of model salt solutions at different Mg/Ca ratio (0, 1/20, 1/10, 1/5 and 2/5). The membrane fouling was characterized by membrane parameters (membrane thickness and electrical conductivity) and identified by membrane surface analysis (elemental analysis and X-ray diffraction). The mineral deposit was identified as Ca(OH)2 when no magnesium was present in the model salt. As soon as magnesium was present in the model salt solution for neutral pH((concentrate)) conditions a mix between CaCO3 and Ca(OH)2 was formed. This study is the first one to report the influence of magnesium in solution on the formation of CaCO3 fouling at the interface of anion-exchange membrane during electrodialysis.     

An electrostatic micro-collection interface for aerosol collection. Automated ion Chromatographic analysis of aerosols

A miniature aerosol collector based on electrostatic precipitation is described. The sampled aerosol is charged in the device by positive corona discharge and electrostatically collected. The device is operated as a collection interface for aerosol analysis, the collection surfaces can be washed in situ and the effluent subjected to Chromatographic analysis on-line, all in a fully automated manner. At a sampling rate of 0.5 1 min(-1), near unity collection efficiencies are obtained for aerosols of 1 microm and lower size, the size class of greatest environmental interest. Atmospheric aerosol constituents such as sulfate can be measured at the ng m(-3) level. The disadvantage of the present system is that some artifact nitrate is generated (due to NO(x) production in the corona) and reliable values of ambient nitrate aerosol cannot therefore be obtained.     

Heterogeneous reactions of gaseous HNO3 and NO2 on the clay minerals kaolinite and pyrophyllite

Airborne clay mineral particles have long atmospheric lifetimes due to their relatively small size. To assess their impact on trace atmospheric gases, we investigated heterogeneous reactions on prototype clay minerals. Diffuse reflectance infrared spectroscopy identified surface-adsorbed products formed from the uptake of gaseous nitric acid and nitrogen dioxide on kaolinite and pyrophyllite. For kaolinite, a 1:1 phyllosilicate, HNO3 molecularly adsorbed onto the octahedral aluminum hydroxide and tetrahedral silicon oxide surfaces. Also detected on the aluminum hydroxide surface were irreversibly adsorbed monodentate, bidentate, bridged, and water-coordinated nitrate species as well as surface-adsorbed water. Similar adsorbed products formed during the uptake of NO2 on kaolinite at relative humidity (RH) of 0%, and the reaction was second order with respect to reactive surface sites and 1.5 +/- 0.1 for NO2. Reactive uptake coefficients, calculated using Brunauer, Emmett, and Teller surface areas, increased from (8.0 +/- 0.2) x 10(-8) to (2.3 +/- 0.4) x 10(-7) for NO2 concentrations ranging from 0.56 x 10(13) to 8.8 x 10(13) molecules cm(-3). UV-visible spectroscopy detected gaseous HONO as a product for the reaction of NO2 on wet kaolinite. The uptake of HNO3 on pyrophyllite, a 2:1 phyllosilicate, resulted in stronger signal for nitric acid molecularly adsorbed on the silicon oxide surface compared to kaolinite. Monodentate, bridged, and water-coordinated nitrate species bound to aluminum sites also formed during this reaction indicating that reactive sites on edge facets are important for this system. The uptake of NO2 on pyrophyllite, gammaBET = (7 +/- 1) x 10(-9), was significantly lower than kaolinite because NO2 did not react with the dominant tetrahedral silicon oxide surface. These results highlight general trends regarding the reactivity of tetrahedral silicon oxide and octahedral aluminum hydroxide clay surfaces and indicate that the heterogeneous chemistry of clay aerosols varies with mineralogy and cannot be predicted by elemental analysis.