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.

Overview of the Alaskan Layered Pollution and Chemical Analysis (ALPACA) Field Experiment.

The Alaskan Layered Pollution And Chemical Analysis (ALPACA) field experiment was a collaborative study designed to improve understanding of pollution sources and chemical processes during winter (cold climate and low-photochemical activity), to investigate indoor pollution, and to study dispersion of pollution as affected by frequent temperature inversions. A number of the research goals were motivated by questions raised by residents of Fairbanks, Alaska, where the study was held. This paper describes the measurement strategies and the conditions encountered during the January and February 2022 field experiment, and reports early examples of how the measurements addressed research goals, particularly those of interest to the residents. Outdoor air measurements showed high concentrations of particulate matter and pollutant gases including volatile organic carbon species. During pollution events, low winds and extremely stable atmospheric conditions trapped pollution below 73 m, an extremely shallow vertical scale. Tethered-balloon-based measurements intercepted plumes aloft, which were associated with power plant point sources through transport modeling. Because cold climate residents spend much of their time indoors, the study included an indoor air quality component, where measurements were made inside and outside a house to study infiltration and indoor sources. In the absence of indoor activities such as cooking and/or heating with a pellet stove, indoor particulate matter concentrations were lower than outdoors; however, cooking and pellet stove burns often caused higher indoor particulate matter concentrations than outdoors. The mass-normalized particulate matter oxidative potential, a health-relevant property measured here by the reactivity with dithiothreiol, of indoor particles varied by source, with cooking particles having less oxidative potential per mass than pellet stove particles.

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.

Chemical and Light-Absorption Properties of Water-Soluble Organic Aerosols in Northern California and Photooxidant Production by Brown Carbon Components.

Atmospheric brown carbon (BrC) can impact the radiative balance of the earth and form photooxidants. However, the light absorption and photochemical properties of BrC from different sources remain poorly understood. To address this gap, dilute water extracts of particulate matter (PM) samples collected at Davis, CA over one year were analyzed using high resolution aerosol mass spectrometry (HR-AMS) and UV-vis spectroscopy. Positive matrix factorization (PMF) on combined AMS and UV-vis data resolved five water-soluble organic aerosol (WSOA) factors with distinct mass spectra and UV-vis spectra: a fresh and an aged water-soluble biomass burning OA (WSBBOAfresh and WSBBOAaged) and three oxygenated OA (WSOOAs). WSBBOAfresh is the most light-absorbing, with a mass absorption coefficient (MAC365 nm) of 1.1 m2 g-1, while the WSOOAs are the least (MAC365 nm = 0.01-0.1 m2 g-1). These results, together with the high abundance of WSBBOAs (∼52% of the WSOA mass), indicate that biomass burning activities such as residential wood burning and wildfires are an important source of BrC in northern California. The concentrations of aqueous-phase photooxidants, i.e., hydroxyl radical (·OH), singlet molecular oxygen (1O2*), and oxidizing triplet excited states of organic carbon (3C*), were also measured in the PM extracts during illumination. Oxidant production potentials (PPOX) of the five WSOA factors were explored. The photoexcitation of BrC chromophores from BB emissions and in OOAs is a significant source of 1O2* and 3C*. By applying our PPOX values to archived AMS data at dozens of sites, we found that oxygenated organic species play an important role in photooxidant formation in atmospheric waters.

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.

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.

Photodecay of guaiacol is faster in ice, and even more rapid on ice, than in aqueous solution.

Snowpacks contain a wide variety of inorganic and organic compounds, including some that absorb sunlight and undergo direct photoreactions. How the rates of these reactions in, and on, ice compare to rates in water is unclear: some studies report similar rates, while others find faster rates in/on ice. Further complicating our understanding, there is conflicting evidence whether chemicals react more quickly at the air-ice interface compared to in liquid-like regions (LLRs) within the ice. To address these questions, we measured the photodegradation rate of guaiacol (2-methoxyphenol) in various sample types, including in solution, in ice, and at the air-ice interface of nature-identical snow. Compared to aqueous solution, we find modest rate constant enhancements (increases of 3- to 6-fold) in ice LLRs, and much larger enhancements (of 17- to 77-fold) at the air-ice interface of nature-identical snow. Our computational modeling suggests the absorption spectrum for guaiacol red-shifts and increases on ice surfaces, leading to more light absorption, but these changes explain only a small portion (roughly 2 to 9%) of the observed rate constant enhancements in/on ice. This indicates that increases in the quantum yield are primarily responsible for the increased photoreactivity of guaiacol on ice; relative to solution, our results suggest that the quantum yield is larger by a factor of roughly 3-6 in liquid-like regions and 12-40 at the air-ice interface.

Quantum Yield for the Aqueous Photochemical Degradation of Chlorantraniliprole and Simulation of Its Environmental Fate in a Model California Rice Field.

The photochemical degradation of chlorantraniliprole (3-bromo-N-[4-chloro-2-methyl-6-(methylcarbamoyl)phenyl]-1-(3-chloro-2-pyridine-2-yl)-1H-pyrazole-5-carboxamide; CAP) was characterized under simulated solar light with 2-nitrobenzaldehyde (2NB) actinometry. Overall, aqueous CAP degraded quickly via direct photodegradation with no significant difference observed between high-purity water and filtered rice field water. The 24-h average half-life normalized to summer sunlight using 2NB was 34.5 ± 4.0 h (jCAP,env = 0.020 ± 0.0023 h-1 , n = 3), and the calculated apparent quantum yield in simulated sunlight was 0.0099 ± 0.00060. These new values were used-alongside previously characterized data for air/and soil/water partitioning, degradation in soil, and hydrolysis-in the Pesticides in Flooded Applications Model to simulate CAP dissipation in a model California (USA) rice field. The model estimates an environmental half-life of 26 d in the aqueous phase, but the bulk of applied CAP remains in the benthic zone and degrades, with estimated half-lives of 29 and 92 d in flooded and drained fields, respectively. Environ Toxicol Chem 2020;39:1929-1935. © 2020 SETAC.

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.

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.

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.

Aqueous Photolysis of Benzobicyclon Hydrolysate.

Benzobicyclon [3-(2-chloro-4-(methylsulfonyl)benzoyl)-2-phenylthiobicyclo[3.2.1]oct-2-en-4-one] is a pro-herbicide used against resistant weeds in California rice fields. Persistence of its active product, benzobicyclon hydrolysate, is of concern. As an acidic herbicide, the neutral species photolyzed faster than the more predominant anionic species ( t1/2 = 1 and 320 h, respectively; natural sunlight), from a >10-fold difference in the quantum yield. Dissolved organic matter in natural waters reduced direct photolysis and increased indirect photolysis compared to high-purity water. Light attenuation appears significant in rice field water and can slow photolysis. These results, used in the pesticides in flooded applications model with other experimental properties, indicate that a floodwater hold time of 20 days could be sufficient for dissipation of the majority of initial aqueous benzobicyclon hydrolysate prior to release. However, soil recalcitrance of both compounds will keep aqueous benzobicyclon hydrolysate levels constant months after benzobicyclon application.

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.

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.

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.

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%.

Concentrations of a triplet excited state are enhanced in illuminated ice.

Photochemical reactions influence the fates and lifetimes of organic compounds in snow and ice, both through direct photoreactions and via photoproduced transient species such as hydroxyl radical (˙OH) and, perhaps, triplet excited states of organic compounds (i.e., triplets). While triplets can be important oxidants in atmospheric drops and surface waters, little is known of this class of oxidants in frozen samples. To investigate this, we examined the photoreaction of phenol with the triplet state of 3,4-dimethoxybenzaldehyde (3DMB*), a product from biomass combustion, in illuminated laboratory ices. Our results show that the rate of phenol loss due to 3DMB* is, on average, increased by a factor of 95 ± 50 in ice compared to the equivalent liquid sample. We find that this experimentally measured freeze concentration factor, FEXP, is independent of total solute concentration and temperature, in contrast to what is expected from a liquid-like region whose composition follows freezing point depression. We also find that FEXP for triplets is independent of pH, although the rates of phenol loss increase with decreasing pH in both solution and ice. The enhancement in the rate of phenol loss in/on ice indicates that concentrations of triplet excited states are enhanced in ice relative to solution and suggests that this class of oxidants might be a significant sink for organics in snow and ice.