Modeling Novel Aqueous Particle and Cloud Chemistry Processes of Biomass Burning Phenols and Their Potential to Form Secondary Organic Aerosols.

Phenols emitted from biomass burning contribute significantly to secondary organic aerosol (SOA) formation through the partitioning of semivolatile products formed from gas-phase chemistry and multiphase chemistry in aerosol liquid water and clouds. The aqueous-phase SOA (aqSOA) formed via hydroxyl radical (•OH), singlet molecular oxygen (1O2*), and triplet excited states of organic compounds (3C*), which oxidize dissolved phenols in the aqueous phase, might play a significant role in the evolution of organic aerosol (OA). However, a quantitative and predictive understanding of aqSOA has been challenging. Here, we develop a stand-alone box model to investigate the formation of SOA from gas-phase •OH chemistry and aqSOA formed by the dissolution of phenols followed by their aqueous-phase reactions with •OH, 1O2*, and 3C* in cloud droplets and aerosol liquid water. We investigate four phenolic compounds, i.e., phenol, guaiacol, syringol, and guaiacyl acetone (GA), which represent some of the key potential sources of aqSOA from biomass burning in clouds. For the same initial precursor organic gas that dissolves in aerosol/cloud liquid water and subsequently reacts with aqueous phase oxidants, we predict that the aqSOA formation potential (defined as aqSOA formed per unit dissolved organic gas concentration) of these phenols is higher than that of isoprene-epoxydiol (IEPOX), a well-known aqSOA precursor. Cloud droplets can dissolve a broader range of soluble phenols compared to aqueous aerosols, since the liquid water contents of aerosols are orders of magnitude smaller than cloud droplets. Our simulations suggest that highly soluble and reactive multifunctional phenols like GA would predominantly undergo cloud chemistry within cloud layers, while gas-phase chemistry is likely to be more important for less soluble phenols. But in the absence of clouds, the condensation of low-volatility products from gas-phase oxidation followed by their reversible partitioning to organic aerosols dominates SOA formation, while the SOA formed through aqueous aerosol chemistry increases with relative humidity (RH), approaching 40% of the sum of gas and aqueous aerosol chemistry at 95% RH for GA. Our model developments of biomass-burning phenols and their aqueous chemistry can be readily implemented in regional and global atmospheric chemistry models to investigate the aqueous aerosol and cloud chemistry of biomass-burning organic gases in the atmosphere.

Direct Determination of Absolute Radical Quantum Yields in Hydroxyl and Sulfate Radical-Based Treatment Processes.

The absolute radical quantum yield (Φ) is a critical parameter to evaluate the efficiency of radical-based processes in engineered water treatment. However, measuring Φ is fraught with challenges, as current quantification methods lack selectivity, specificity, and anti-interference capabilities, resulting in significant error propagation. Herein, we report a direct and reliable time-resolved technique to determine Φ at pH 7.0 for commonly used radical precursors in advanced oxidation processes. For H2O2 and peroxydisulfate (PDS), the values of Φ•OH and ΦSO4•- at 266 nm were measured to be 1.10 ± 0.01 and 1.46 ± 0.05, respectively. For peroxymonosulfate (PMS), we developed a new approach to determine Φ•OHPMS with terephthalic acid as a trap-and-trigger probe in the nonsteady state system. For the first time, the Φ•OHPMS value was measured to be 0.56 by the direct method, which is stoichiometrically equal to ΦSO4•-PMS (0.57 ± 0.02). Additionally, radical formation mechanisms were elucidated by density functional theory (DFT) calculations. The theoretical results showed that the highest occupied molecular orbitals of the radical precursors are O-O antibonding orbitals, facilitating the destabilization of the peroxy bond for radical formation. Electronic structures of these precursors were compared, aiming to rationalize the tendency of the Φ values we observed. Overall, this time-resolved technique with specific probes can be used as a reliable tool to determine Φ, serving as a scientific basis for the accurate performance evaluation of diverse radical-based treatment processes.

Evaluation of Probes to Measure Oxidizing Organic Triplet Excited States in Aerosol Liquid Water.

Oxidizing triplet excited states of organic matter (3C*) drive numerous reactions in fog/cloud drops and aerosol liquid water (ALW). Quantifying oxidizing triplet concentrations in ALW is difficult because 3C* probe loss can be inhibited by the high levels of dissolved organic matter (DOM) and copper in particle water, leading to an underestimate of triplet concentrations. In addition, illuminated ALW contains high concentrations of singlet molecular oxygen (1O2*), which can interfere with 3C* probes. Our overarching goal is to find a triplet probe that has low inhibition by DOM and Cu(II) and low sensitivity to 1O2*. To this end, we tested 12 potential probes from a variety of compound classes. Some probes are strongly inhibited by DOM, while others react rapidly with 1O2*. One of the probe candidates, (phenylthiol)acetic acid (PTA), seems well suited for ALW conditions, with mild inhibition and fast rate constants with triplets, but it also has weaknesses, including a pH-dependent reactivity. We evaluated the performance of both PTA and syringol (SYR) as triplet probes in aqueous extracts of particulate matter. While PTA is less sensitive to inhibition than SYR, it results in lower triplet concentrations, possibly because it is less reactive with weakly oxidizing triplets.

Aqueous ·OH Oxidation of Highly Substituted Phenols as a Source of Secondary Organic Aerosol.

Biomass burning (BB) releases large quantities of phenols (ArOH), which can partition into cloud/fog drops and aerosol liquid water (ALW), react, and form aqueous secondary organic aerosol (aqSOA). While simple phenols are too volatile to significantly partition into particle water, highly substituted ArOH partition more strongly and might be important sources of aqSOA in ALW. To investigate this, we measured the ·OH oxidation kinetics and aqSOA yields for six highly substituted ArOH from BB. Second-order rate constants are high, in the range (1.9-14) × 109 M-1 s-1 at pH 2 and (14-25) × 109 M-1 s-1 at pH 5 and 6. Mass yields of aqSOA are also high, with an average (±1σ) value of 82 (±12)%. ALW solutes have a range of impacts on phenol oxidation by ·OH: a BB sugar and some inorganic salts suppress oxidation, while a nitrate salt and transition metals enhance oxidation. Finally, we estimated rates of aqueous- and gas-phase formation of SOA from a single highly substituted phenol as a function of liquid water content (LWC), from conditions of cloud/fog (0.1 g-H2O m-3) to ALW (10 µg-H2O m-3). Formation of aqSOA is significant across the LWC range, although gas-phase ·OH becomes dominant under ALW conditions. We also see a generally large discrepancy between measured and modeled aqueous ·OH concentrations across the LWC range.

Kinetics and Mass Yields of Aqueous Secondary Organic Aerosol from Highly Substituted Phenols Reacting with a Triplet Excited State.

Biomass burning emits large amounts of phenols, which can partition into cloud/fog drops and aerosol liquid water (ALW) and react to form aqueous secondary organic aerosol (aqSOA). Triplet excited states of organic compounds (3C*) are likely oxidants, but there are no rate constants with highly substituted phenols that have high Henry's law constants (KH) and are likely important in ALW. To address this gap, we investigated the kinetics of six highly substituted phenols with the triplet excited state of 3,4-dimethoxybenzaldehyde. Second-order rate constants at pH 2 are all fast, (2.6-4.6) × 109 M-1 s-1, while values at pH 5 are 2-5 times smaller. Rate constants are reasonably described by a quantitative structure-activity relationship with phenol oxidation potentials, allowing rate constants of other phenols to be predicted. Triplet-phenol kinetics are unaffected by ammonium sulfate, sodium chloride, galactose (a biomass-burning sugar), or Fe(III). In contrast, ammonium nitrate increases the rate of phenol loss by making hydroxyl radicals, while Cu(II) inhibits phenol decay. Mass yields of aqueous SOA from triplet reactions are large and range from 59 to 99%. Calculations using our data along with previous oxidant measurements indicate that phenols with high KH can be an important source of aqSOA in ALW, with 3C* typically the dominant oxidant.

Photosensitized Reactions of a Phenolic Carbonyl from Wood Combustion in the Aqueous Phase-Chemical Evolution and Light Absorption Properties of AqSOA.

Guaiacyl acetone (GA) is a phenolic carbonyl emitted in significant quantities by wood combustion that undergoes rapid aqueous-phase oxidation to produce aqueous secondary organic aerosol (aqSOA). We investigate the photosensitized oxidation of GA by an organic triplet excited state (3C*) and the formation and aging of the resulting aqSOA in wood smoke-influenced fog/cloud water. The chemical transformations of the aqSOA were characterized in situ using a high-resolution time-of-flight aerosol mass spectrometer. Additionally, aqSOA samples collected over different time periods were analyzed using high-performance liquid chromatography coupled with a photodiode array detector and a high-resolution Orbitrap mass spectrometer (HPLC-PDA-HRMS) to provide details on the molecular composition and optical properties of brown carbon (BrC) chromophores. Our results show efficient formation of aqSOA from GA, with an average mass yield around 80%. The composition and BrC properties of the aqSOA changed significantly over the course of reaction. Three generations of aqSOA products were identified via positive matrix factorization analysis of the aerosol mass spectrometry data. Oligomerization and functionalization dominated the production of the first-generation aqSOA, whereas fragmentation and ring-opening reactions controlled the formation of more oxidized second- and third-generation products. Significant formation of BrC was observed in the early stages of the photoreaction, while organic acids were produced throughout the experiment. High-molecular weight molecules (m/z > 180) with high aromaticity were identified via HPLC-PDA-HRMS and were found to account for a majority of the UV-vis absorption of the aqSOA.

Air-Water Partitioning of Biomass-Burning Phenols and the Effects of Temperature and Salinity.

Biomass burning (BB) emits organic gases that, with chemical aging, can form secondary organic aerosol (SOA) in both the gas and aqueous phases. One class of biomass-burning emissions, phenols, are of interest because they react rapidly in the aqueous phase to efficiently form SOA, which might affect climate and human health. However, while measurements exist for the air-water partitioning constants of some simple phenols, Henry's law constants (KH) are unknown for more complex BB phenols. In this work, we use a custom-built apparatus to measure KH for a suite of biomass-burning phenols that span a wide range of air-water partitioning coefficients. Comparing our measurements to predicted values from EPI Suite shows that this model consistently overestimates KH unless a suitable measured phenol KH value is included to adjust the calculations. In addition, we determine the effect of five salts on phenol partitioning by measuring the Setschenow coefficients (KS). Across the eight phenols we examined, values of KS depend primarily on salt identity and descend in the order (NH4)2SO4 > NaCl > NH4Cl ≥ KNO3 > NH4NO3. Lastly, we use our KH and KS results to discuss the aqueous processing of biomass-burning phenols in cloud/fog water versus aerosol liquid water.

Bathochromic Shift in the UV-Visible Absorption Spectra of Phenols at Ice Surfaces: Insights from First-Principles Calculations.

Some organic pollutants in snowpacks undergo faster photodegradation than in solution. One possible explanation for such effect is that their UV-visible absorption spectra are shifted toward lower energy when the molecules are adsorbed at the air-ice interface. However, such bathochromic shift is difficult to measure experimentally. Here, we employ a multiscale/multimodel approach that combines classical and first-principles molecular dynamics, quantum chemical methods, and statistical learning to compute the light absorption spectra of two phenolic molecules in different solvation environments at the relevant thermodynamic conditions. Our calculations provide an accurate estimate of the bathochromic shift of the lowest-energy UV-visible absorption band when these molecules are adsorbed at the air-ice interface, and they shed light into its molecular origin.

First Measurements of Organic Triplet Excited States in Atmospheric Waters.

Photooxidants chemically transform organic compounds in atmospheric drops and particles. Photooxidants such as hydroxyl radical (•OH) and singlet molecular oxygen (1O2*) have been characterized in cloud and fog drops, but there are no measurements of the triplet excited states of organic matter (3C*). These "triplets", which are formed from excitation of chromophoric dissolved organic matter (CDOM), i.e., brown carbon, are difficult to measure because they are a mixture of species instead of a single entity. Here, we use a two-probe technique to measure the steady-state concentrations, rates of photoformation, and quantum yields of oxidizing triplet states during simulated-sunlight illumination of bulk fog waters. Concentrations of 3C* are (0.70-15) × 10-14 M with an average (±σ) value of 5.0 (±5.1) × 10-14 M. The average 3C* photoformation rate is 130 (±130) µM h-1, while the average quantum yield is 3.7 (±4.5)%. Based on our previous measurements of •OH and 1O2* in the same fog samples, the ratio of the steady-state concentrations for 1O2*:3C*:•OH is approximately 3:1:0.04, respectively. At our measured concentrations, triplet excited states can be the dominant aqueous oxidants for organic compounds such as phenols from biomass combustion.

Photodegradation Rate Constants for Anthracene and Pyrene Are Similar in/on Ice and in Aqueous Solution.

Snowpacks contain a variety of chemicals, including organic pollutants such as toxic polycyclic aromatic hydrocarbons (PAHs). While PAHs undergo photodegradation in snow and ice, the rates of these reactions remain in debate. Some studies report that photochemical reactions in snow proceed at rates similar to those expected in a supercooled aqueous solution, but other studies report faster reaction rates, particularly at the air-ice interface (i.e., the quasi-liquid layer, or QLL). In addition, one study reported a surprising nonlinear dependence on photon flux. Here we examine the photodegradation of two common PAHs, anthracene and pyrene, in/on ice and in solution. For a given PAH, rate constants are similar in aqueous solution, in internal liquid-like regions of ice, and at the air-ice interface. In addition, we find the expected linear relationship between reaction rate constant and photon flux. Our results indicate that rate constants for the photochemical loss of PAHs in, and on, snow and ice are very similar to those in aqueous solution, with no enhancement at the air-ice interface.

Nitrate Photochemistry at the Air-Ice Interface and in Other Ice Reservoirs.

The photolysis of snowpack nitrate (NO3-) is an important source of gaseous reactive nitrogen species that affect atmospheric oxidants, particularly in remote regions. However, it is unclear whether nitrate photochemistry differs between the three solute reservoirs in/on ice: in liquid-like regions (LLRs) in the ice; within the solid ice matrix; and in a quasi-liquid layer (QLL) at the air-ice interface, where past work indicates photolysis is enhanced. In this work, we explore the photoformation of nitrite in these reservoirs using laboratory ices. Nitrite quantum yields, Φ(NO2-), at 313 nm for aqueous and LLR ice samples agree with previous values, e.g., 0.65 ± 0.07% at -10 °C. For ice samples made via flash-freezing solution in liquid nitrogen, where nitrate is possibly present as a solid solution, the nitrite quantum yield is 0.57 ± 0.05% at -10 °C, similar to the LLR results. In contrast, the quantum yield at the air-ice interface is enhanced by a factor of 3.7 relative to LLRs, with a value of 2.39 ± 0.24%. These results indicate nitrate photolysis is enhanced at the air-ice interface, although the importance of this enhancement in the environment depends on the amount of nitrate present at the interface.

Formation and Evolution of aqSOA from Aqueous-Phase Reactions of Phenolic Carbonyls: Comparison between Ammonium Sulfate and Ammonium Nitrate Solutions.

We investigate the effects of sulfate and nitrate on the formation and evolution of secondary organic aerosol formed in the aqueous phase (aqSOA) from photooxidation of two phenolic carbonyls emitted from wood burning. AqSOA was formed efficiently from the photooxidation of both syringaldehyde (C9H10O4) and acetosyringone (C10H12O4) in ammonium sulfate and ammonium nitrate solutions, with mass yields ranging from 30% to 120%. Positive matrix factorization on the organic mass spectra acquired by an Aerosol Mass Spectrometer revealed a combination of functionalization, oligomerization, and fragmentation processes in the chemical evolution of aqSOA. Functionalization and oligomerization dominated in the first 4 h of reaction, with phenolic oligomers and their derivatives significantly contributing to aqSOA formation; and oxidation of the first-generation products led to an abundance of oxygenated ring-opening products. Degradation rates of syringaldehyde and acetosyringone in nitrate solutions were 1.5 and 3.5 times faster than rates in sulfate solutions, and aqSOA yields in nitrate experiments are twice as high as in sulfate experiments. Nitrate likely promoted the reactions because it is a photolytic source of OH radicals, while sulfate is not, highlighting the importance of aerosol-phase nitrate in the formation of aqSOA by facilitating the photooxidation of organic precursors.

Quantum Yield of Nitrite from the Photolysis of Aqueous Nitrate above 300 nm.

Photolysis of nitrate (NO3-) produces reactive nitrogen and oxygen species via three different channels, forming: (1) nitrogen dioxide (NO2) and hydroxyl radical (•OH), (2) nitrite (NO2-) and oxygen atom (O(3P)), and (3) peroxynitrite (ONOO-). These photoproducts are important oxidants and reactants in surface waters, atmospheric drops, and snowpacks. While the efficiency of the first channel, to form NO2, is well documented, a large range of values have been reported for the second channel, nitrite, above 300 nm. In part, this disagreement reflects secondary chemistry that can produce or destroy nitrite. In this study, we examine factors that influence nitrite production and find that pH, nitrate concentration, and the presence of an •OH scavenger can be important. We measure an average nitrite quantum yield (Φ(NO2-)) of (1.1 ± 0.2)% (313 nm, 50 µM nitrate, pH ≥ 5), which is at the upper end of past measurements and an order of magnitude above the smallest-and most commonly cited-value reported for this channel. Nitrite production is often considered a very minor channel in nitrate photolysis, but our results indicate it is as important as the NO2 channel. In contrast, at 313 nm we observe no formation of peroxynitrite, corresponding to Φ(ONOO-) < 0.26%.

Quantum Yields of Nitrite (NO2-) from the Photolysis of Nitrate (NO3-) in Ice at 313 nm.

Photochemical reactions of nitrate in snow release reactive nitrogen species via two channels, which produce (1) nitrogen dioxide (NO2) and hydroxyl radical (•OH) and (2) nitrite (NO2-) and oxygen atom (O(3P)). Quantum yields (Φ) for these channels are generally well characterized, except for channel 2 in ice. In this study, we quantify Φ(NO2-) in water ices and examine the impacts of pH and organic scavengers of •OH. Compared to solution results, we find that nitrite quantum yields in ice are more sensitive to pH and that •OH scavengers are less effective, although 2-propanol appears to work well. The temperature dependence (-30 to 25 °C) of Φ(NO2-) in samples containing 2-propanol is well described by a single regression line, ln(Φ(NO2-)) = -(1330 ± 100)(1/T(K)) + (0.09 ± 0.39). At -10 °C, the resulting quantum yield is 4.6 times larger than the previously reported (and recommended) value without an •OH scavenger. Although some reports suggest nitrite is a minor product from nitrate photolysis, based on our current and past results, rates of photoproduction of NO2- and NO2 are similar at room temperature, while NO2- production dominates at lower temperatures in solution and ice.

A bias in the "mass-normalized" DTT response - an effect of non-linear concentration-response curves for copper and manganese.

The dithiothreitol (DTT) assay is widely used to measure the oxidative potential of particulate matter. Results are typically presented in mass-normalized units (e.g., pmols DTT lost per minute per microgram PM) to allow for comparison among samples. Use of this unit assumes that the mass-normalized DTT response is constant and independent of the mass concentration of PM added to the DTT assay. However, based on previous work that identified non-linear DTT responses for copper and manganese, this basic assumption (that the mass-normalized DTT response is independent of the concentration of PM added to the assay) should not be true for samples where Cu and Mn contribute significantly to the DTT signal. To test this we measured the DTT response at multiple PM concentrations for eight ambient particulate samples collected at two locations in California. The results confirm that for samples with significant contributions from Cu and Mn, the mass-normalized DTT response can strongly depend on the concentration of PM added to the assay, varying by up to an order of magnitude for PM concentrations between 2 and 34 µg mL-1. This mass dependence confounds useful interpretation of DTT assay data in samples with significant contributions from Cu and Mn, requiring additional quality control steps to check for this bias. To minimize this problem, we discuss two methods to correct the mass-normalized DTT result and we apply those methods to our samples. We find that it is possible to correct the mass-normalized DTT result, although the correction methods have some drawbacks and add uncertainty to DTT analyses. More broadly, other DTT-active species might also have non-linear concentration-responses in the assay and cause a bias. In addition, the same problem of Cu- and Mn-mediated bias in mass-normalized DTT results might affect other measures of acellular redox activity in PM and needs to be addressed.

Rates of Hydroxyl Radical Production from Transition Metals and Quinones in a Surrogate Lung Fluid.

Hydroxyl radical ((•)OH) is the most reactive, and perhaps most detrimental to health, of the reactive oxygen species. (•)OH production in lungs following inhalation of particulate matter (PM) can result from redox-active chemicals, including iron and copper, but the relative importance of these species is unknown. This work investigates (•)OH production from iron, copper, and quinones, both individually and in mixtures at atmospherically relevant concentrations. Iron, copper, and three of the four quinones (1,2-naphthoquinone, phenanthrenequinone and 1,4-naphthoquinone) produce (•)OH. Mixtures of copper or quinones with iron synergistically produce (•)OH at a rate 20-130% higher than the sum of the rates of the individual redox-active species. We developed a regression equation from 20 mixtures to predict the rate of (•)OH production from the particle composition. For typical PM compositions, iron and copper account for most (•)OH production, whereas quinones are a minor source, although they can contribute if present at very high concentrations. This work shows that Cu contributes significantly to (•)OH production in ambient PM; other work has shown that Cu appears to be the primary driver of HOOH production and dithiothreitol (DTT) loss in ambient PM extracts. Taken together, these results indicate that copper appears to be the most important individual contributor to direct oxidant production from inhaled PM.

Secondary organic aerosol from aqueous reactions of green leaf volatiles with organic triplet excited states and singlet molecular oxygen.

Vegetation emits a class of oxygenated hydrocarbons--the green leaf volatiles (GLVs)--under stress or damage. Under foggy conditions GLVs might be a source of secondary organic aerosol (SOA) via aqueous reactions with hydroxyl radical (OH), singlet oxygen ((1)O2*), and excited triplet states ((3)C*). To examine this, we determined the aqueous kinetics and SOA mass yields for reactions of (3)C* and (1)O2* with five GLVs: methyl jasmonate (MeJa), methyl salicylate (MeSa), cis-3-hexenyl acetate (HxAc), cis-3-hexen-1-ol (HxO), and 2-methyl-3-butene-2-ol (MBO). Second-order rate constants with (3)C* and (1)O2* range from (0.13-22) × 10(8) M(-1) s(-1) and (8.2-60) × 10(5) M(-1) s(-1) at 298 K, respectively. Rate constants with (3)C* are independent of temperature, while values with (1)O2* show significant temperature dependence (Ea = 20-96 kJ mol(-1)). Aqueous SOA mass yields for oxidation by (3)C* are (84 ± 7)%, (80 ± 9)%, and (38 ± 18)%, for MeJa, MeSa, and HxAc, respectively; we did not measure yields for other conditions because of slow kinetics. The aqueous production of SOA from GLVs is dominated by (3)C* and OH reactions, which form low volatility products at a rate that is approximately half that from the parallel gas-phase reactions of GLVs.

Aqueous benzene-diols react with an organic triplet excited state and hydroxyl radical to form secondary organic aerosol.

Chemical processing in atmospheric aqueous phases, such as cloud and fog drops, can play a significant role in the production and evolution of secondary organic aerosol (SOA). In this work we examine aqueous SOA production via the oxidation of benzene-diols (dihydroxy-benzenes) by the triplet excited state of 3,4-dimethoxybenzaldehyde, (3)DMB*, and by hydroxyl radical, ˙OH. Reactions of the three benzene-diols (catechol (CAT), resorcinol (RES) and hydroquinone (HQ)) with (3)DMB* or ˙OH proceed rapidly, with rate constants near diffusion-controlled values. The two oxidants exhibit different behaviors with pH, with rate constants for (3)DMB* increasing as pH decreases from pH 5 to 2, while rate constants with ˙OH decrease in more acidic solutions. Mass yields of SOA were near 100% for all three benzene-diols with both oxidants. We also examined the reactivity of atmospherically relevant mixtures of phenols and benzene-diols in the presence of (3)DMB*. We find that the kinetics of phenol and benzene-diol loss, and the production of SOA mass, in mixtures are generally consistent with rate constants determined in experiments containing a single phenol or benzene-diol. Combining our aqueous kinetic and SOA mass yield data with previously published gas-phase data, we estimate a total SOA production rate from benzene-diol oxidation in a foggy area with significant wood combustion to be nearly 0.6 µg mair(-3) h(-1), with approximately half from the aqueous oxidation of resorcinol and hydroquinone, and half from the gas-phase oxidation of catechol.

The effect of cations on NO2 production from the photolysis of aqueous thin water films of nitrate salts.

The photochemistry of nitrate ions in bulk aqueous solution is well known, yet recent evidence suggests that the photolysis of nitrate may be more efficient at the air-water interface. Whether and how this surface enhancement is altered by the presence of different cations is not known. In the present studies, thin aqueous films of nitrate salts with different cations were deposited on the walls of a Teflon chamber and irradiated with 311 nm light at 298 K. The films were generated by nebulizing aqueous 0.5 M solutions of the nitrate salts and the generation of gas-phase NO2 was monitored with time. The nitrate salts fall into three groups based on their observed rate of NO2 formation (R(NO2)): (1) RbNO3 and KNO3, which readily produce NO2 (R(NO2) > 3 ppb min(-1)), (2) Ca(NO3)2, which produces NO2 more slowly (R(NO2) < 1 ppb min(-1)), and (3) Mg(NO3)2 and NaNO3, which lie between the other two groups. Neither differences in the UV-visible spectra of the nitrate salt solutions nor the results of bulk-phase photolysis studies could explain the differences in the rates of NO2 production between these three groups. These experimental results, combined with some insights from previous molecular dynamic simulations and vibrational sum frequency generation studies, show that cations may impact the concentration of nitrate ions in the interface region, thereby directly impacting the effective quantum yields for nitrate ions.

Hydrogen peroxide formation in a surrogate lung fluid by transition metals and quinones present in particulate matter.

Inhaled ambient particulate matter (PM) causes adverse health effects, possibly by generating reactive oxygen species (ROS), including hydrogen peroxide (HOOH), in the lung lining fluid. There are conflicting reports in the literature as to which chemical components of PM can chemically generate HOOH in lung fluid mimics. It is also unclear which redox-active species are most important for HOOH formation at concentrations relevant to ambient PM. To address this, we use a cell-free, surrogate lung fluid (SLF) to quantify the initial rate of HOOH formation from 10 transition metals and 4 quinones commonly identified in PM. Copper, 1,2-naphthoquinone, 1,4-naphthoquinone, and phenanthrenequinone all form HOOH in a SLF, but only copper and 1,2-naphthoquinone are likely important at ambient concentrations. Iron suppresses HOOH formation in laboratory solutions, but has a smaller effect in ambient PM extracts, possibly because organic ligands in the particles reduce the reactivity of iron. Overall, copper produces the majority of HOOH chemically generated from typical ambient PM while 1,2-naphthoquinone generally makes a small contribution. However, measured rates of HOOH formation in ambient particle extracts are lower than rates calculated from soluble copper by an average (±1σ) of 44 ± 22%; this underestimate is likely due to either HOOH destruction by Fe or a reduction in Cu reactivity due to organic ligands from the PM.