NO2 Photolysis Research Articles

Nonnegligible Generation of Hydroxyl Radicals from UVC Photolysis of Aqueous Nitrous Oxide.

Nitrous oxide (N2O) is widely used in radiation-chemistry and photochemistry as a scavenger to convert a hydrated electron ( eaq-) into a hydroxyl radical (·OH). However, few investigations pay attention to the photochemistry of dissolved N2O itself. The effects of purged N2O on photochemical processes are unclear and neglected. In the present work, the effects of N2O on the hydroxylation of terephthalic acid (TPA) were investigated with both medium-pressure and low-pressure mercury lamps as the light sources. Under short-wavelength UV (200-300 nm) irradiation, N2O accelerated the decay of TPA and the formation of 2-hydroxylterephthalic acid (hTPA). The effective quantum yield of ·OH from the photolysis of dissolved N2O at 254 nm was determined as 1.15-1.63, which was far larger than those of NO3- (0.09) and NO2- (0.046). On the basis of the kinetic analysis in N2 and N2O purged solutions, isotope fractionation with heavy oxygen water, and ·OH scavenging experiments with tert-butyl alcohol, the contribution of the ·OH radicals generated from the photolysis of N2O to the formation of hTPA (61.7%) was determined to be 1 order of magnitude higher than that from the converted eaq- (6.5%). These results demonstrate that using N2O and ·OH probes to quantify photogenerated eaq- in UVC irradiation might lead to false results. The work here is helpful for the proper design of scavenging and probing experiments by the combination of N2O and ·OH probes.

Impacts of biogenic and anthropogenic emissions on summertime ozone formation in the Guanzhong Basin, China

Abstract. This study is the first attempt to understand the synergistic impact of anthropogenic and biogenic emissions on summertime ozone (O3) formation in the Guanzhong (GZ) Basin where Xi'an, the oldest and the most populous city (with a population of 9 million) in northwestern China, is located. Month-long (August 2011) WRF-Chem simulations with different sensitivity experiments were conducted and compared with near-surface measurements. Biogenic volatile organic compounds (VOCs) concentrations was characterized from six surface sites among the Qinling Mountains, and urban air composition was measured in Xi'an city at a tower 100 ma.s. The WRF-Chem control experiment reasonably reproduced the magnitudes and variations of observed O3, VOCs, NOx, PM2.5, and meteorological parameters, with normalized mean biases for each parameter within ±21 %. Subsequent analysis employed the factor separation approach (FSA) to quantitatively disentangle the pure and synergistic impacts of anthropogenic and/or biogenic sources on summertime O3 formation. The impact of anthropogenic sources alone was found to be dominant for O3 formation. Although anthropogenic particles reduced NO2 photolysis by up to 60 %, the anthropogenic sources contributed 19.1 ppb O3 formation on average for urban Xi'an. The abundant biogenic VOCs from the nearby forests promoted O3 formation in urban areas by interacting with the anthropogenic NOx. The calculated synergistic contribution (from both biogenic and anthropogenic sources) was up to 14.4 ppb in urban Xi'an, peaking in the afternoon. Our study reveals that the synergistic impact of individual source contributions to O3 formation should be considered in the formation of air pollution control strategies, especially for big cities in the vicinity of forests.

Photochemical Formation and Transformation of Birnessite: Effects of Cations on Micromorphology and Crystal Structure.

As important components with excellent oxidation and adsorption activity in soils and sediments, manganese oxides affect the transportation and fate of nutrients and pollutants in natural environments. In this work, birnessite was formed by photocatalytic oxidation of Mn2+aq in the presence of nitrate under solar irradiation. The effects of concentrations and species of interlayer cations (Na+, Mg2+, and K+) on birnessite crystal structure and micromorphology were investigated. The roles of adsorbed Mn2+ and pH in the transformation of the photosynthetic birnessite were further studied. The results indicated that Mn2+aq was oxidized to birnessite by superoxide radicals (O2•-) generated from the photolysis of NO3- under UV irradiation. The particle size and thickness of birnessite decreased with increasing cation concentration. The birnessite showed a plate-like morphology in the presence of K+, while exhibited a rumpled sheet-like morphology when Na+ or Mg2+ was used. The different micromorphologies of birnessites could be ascribed to the position of cations in the interlayer. The adsorbed Mn2+ and high pH facilitated the reduction of birnessite to low-valence manganese oxides including hausmannite, feitknechtite, and manganite. This study suggests that interlayer cations and Mn2+ play essential roles in the photochemical formation and transformation of birnessite in aqueous environments.

Observed NO/NO2 Ratios in the Upper Troposphere Imply Errors in NO‐NO2‐O3 Cycling Kinetics or an Unaccounted NOx Reservoir

AbstractObservations from the SEAC4RS aircraft campaign over the southeast United States in August–September 2013 show NO/NO2 concentration ratios in the upper troposphere that are approximately half of photochemical equilibrium values computed from Jet Propulsion Laboratory (JPL) kinetic data. One possible explanation is the presence of labile NOx reservoir species, presumably organic, decomposing thermally to NO2 in the instrument. The NO2 instrument corrects for this artifact from known labile HNO4 and CH3O2NO2 NOx reservoirs. To bridge the gap between measured and simulated NO2, additional unaccounted labile NOx reservoir species would have to be present at a mean concentration of ~40 ppt for the SEAC4RS conditions (compared with 197 ppt for NOx). An alternative explanation is error in the low‐temperature rate constant for the NO + O3 reaction (30% 1‐σ uncertainty in JPL at 240 K) and/or in the spectroscopic data for NO2 photolysis (20% 1‐σ uncertainty). Resolving this discrepancy is important for understanding global budgets of tropospheric oxidants and for interpreting satellite observations of tropospheric NO2 columns.

Vertical distributions of N<sub>2</sub>O isotopocules in the equatorial stratosphere

Abstract. Vertical profiles of nitrous oxide (N2O) and its isotopocules, isotopically substituted molecules, were obtained over the Equator at altitudes of 16–30 km. Whole air samples were collected using newly developed balloon-borne compact cryogenic samplers over the eastern equatorial Pacific in 2012 and Biak Island, Indonesia, in 2015. They were examined in the laboratory using gas chromatography and mass spectrometry. The mixing ratio and isotopocule ratios of N2O in the equatorial stratosphere showed a weaker vertical gradient than the previously reported profiles in the subtropical and mid-latitude and high-latitude stratosphere. From the relation between the mixing ratio and isotopocule ratios, further distinct characteristics were found over the Equator: (1) observed isotopocule fractionations (ε values) in the middle stratosphere (25–30 km or [N2O] < ca. 260 nmol mol−1) are almost equal to ε values reported from broadband photolysis experiments conducted in the laboratory; (2) ε values in the lower stratosphere (< ca. 25 km or [N2O] > ca. 260 nmol mol−1) are about half of the experimentally obtained values, being slightly larger than those observed in the mid-latitude and high-latitude lower stratosphere ([N2O] > ca. 170 nmol mol−1). These results from the deep tropics suggest the following. (i) The timescale for quasi-horizontal mixing between tropical and mid-latitude air in the tropical middle stratosphere is sufficiently slow relative to the tropical upwelling rate that isotope fractionation approaches the Rayleigh limit for N2O photolysis. (ii) The air in the tropical lower stratosphere is exchanged with extratropical air on a timescale that is shorter than that of photochemical decomposition of N2O. Previously observed ε values, which are invariably smaller than those of photolysis, can be explained qualitatively using a three-dimensional chemical transport model and using a simple model that assumes mixing of “aged” tropical air and extratropical air during residual circulation. Results show that isotopocule ratios are useful to examine the stratospheric transport scheme deduced from tracer–tracer relations.

Wavelength-Resolved Photon Fluxes of Indoor Light Sources: Implications for HOx Production

Photochemistry is a largely unconsidered potential source of reactive species such as hydroxyl and peroxy radicals (OH and HO2, "HOx") indoors. We present measured wavelength-resolved photon fluxes and distance dependences of indoor light sources including halogen, incandescent, and compact fluorescent lights (CFL) commonly used in residential buildings; fluorescent tubes common in industrial and commercial settings; and sunlight entering buildings through windows. We use these measurements to predict indoor HOx production rates from the photolysis of nitrous acid (HONO), hydrogen peroxide (H2O2), ozone (O3), formaldehyde (HCHO), and acetaldehyde (CH3CHO). Our results suggest that while most lamps can photolyze these molecules, only sunlight and fluorescent tubes will be important to room-averaged indoor HOx levels due to the strong distance dependence of the fluxes from compact bulbs. Under ambient conditions, we predict that sunlight and fluorescent lights will photolyze HONO to form OH at rates of 106-107 molecules cm-3 s-1, and that fluorescent lights will photolyze HCHO to form HO2 at rates of ∼106 molecules cm-3 s-1; rates could be 2 orders of magnitude higher under high precursor concentrations. Ozone and H2O2 will not be important photochemical OH sources under most conditions, and CH3CHO will generally increase HO2 production rates only slightly. We also calculated photolysis rate constants for nitrogen dioxide (NO2) and nitrate radicals (NO3) in the presence of the different light sources. Photolysis is not likely an important fate for NO3 indoors, but NO2 photolysis could be an important source of indoor O3.

Photoconversion of 2-Chloronaphthalene in Water.

The photoconversion of 2-chloronaphthalene (CN-2) in water in a simulated sunlight system was investigated. The photoconversion efficiency, photoproducts and mechanisms were inspected, and the effects of inorganic ions (NO3-, NO2-) and fulvic acid (FA) were discussed. The results showed that CN-2 could be transformed in water under the irradiation. NO3- and NO2- promoted the photoconversion of CN-2 owing to ·OH generated by the photolysis of NO3- and NO2-; FA at a lower concentration promoted the photoconversion, but it had an inhibition effect at a higher concentration. It was demonstrated that the acidic conditions promoted the photoconversion of CN-2 by the active groups such as superoxide radical anion, hydrogen peroxide and hydroxyl radical produced in the system. Eight photoproducts of CN-2 were characterized by the GC-MS method and the possible photoconversion mechanisms were proposed accordingly.

Observed trends in ground-level O<sub>3</sub> in Monterrey, Mexico, during 1993–2014: comparison with Mexico City and Guadalajara

Abstract. Here, we present an assessment of long-term trends in O3 and odd oxygen (O3 + NO2) at the industrial Monterrey metropolitan area (MMA) in NE Mexico. Diurnal amplitudes in Ox (AVd) are used as a proxy for net O3 production, which is influenced by the NO2 photolysis rate. No significant differences in the AVd are observed between weekends and weekdays, although the largest AVd values are observed at sites downwind of industrial areas. The highest O3 mixing ratios are observed in spring, with minimum values in winter. The largest annual variations in O3 are typically observed downwind of the MMA, with the lowest variations generally recorded in highly populated areas and close to industrial areas. A wind sector analysis of mixing ratios of O3 precursors revealed that the dominant sources of emissions are located in the industrial regions within the MMA and surrounding area. Significant increasing trends in O3 in spring, summer, and autumn are observed depending on site location, with trends in annual averages ranging between 0.19 and 0.33 ppb yr−1. Overall, from 1993 to 2014, within the MMA, O3 has increased at an average rate of 0.22 ppb yr−1 (p < 0. 01), which is in marked contrast with the decline of 1.15 ppb yr−1 (p < 0. 001) observed in the Mexico City metropolitan area (MCMA) for the same period. No clear trend is observed from 1996 to 2014 within the Guadalajara metropolitan area (GMA).

Experimental and Theoretical Investigation of the Reaction NO + OH + O2 → HO2 + NO2.

Photolysis of NO2 is the only major pathway for O3 formation as products from the reaction of OH and NO under atmospheric conditions in competition to the formation of HONO has been investigated experimentally and theoretically. Experiments have been carried out by directly measuring the formation of HO2 radicals using laser photolysis coupled to cw-CRDS. OH radicals have been generated from the reaction of F atoms with H2O, and absolute HO2 and OH profiles have been recorded at different NO concentrations. The potential energy surface has been calculated and the rate constant has been obtained from RRKM master equation modeling. Both experiment and theory show that the OH + NO reaction in the presence of O2 bath gas is not a competitive source of HO2 + NO2.

Emulation and Sensitivity Analysis of the Community Multiscale Air Quality Model for a UK Ozone Pollution Episode.

Gaussian process emulation techniques have been used with the Community Multiscale Air Quality model, simulating the effects of input uncertainties on ozone and NO2 output, to allow robust global sensitivity analysis (SA). A screening process ranked the effect of perturbations in 223 inputs, isolating the 30 most influential from emissions, boundary conditions (BCs), and reaction rates. Community Multiscale Air Quality (CMAQ) simulations of a July 2006 ozone pollution episode in the UK were made with input values for these variables plus ozone dry deposition velocity chosen according to a 576 point Latin hypercube design. Emulators trained on the output of these runs were used in variance-based SA of the model output to input uncertainties. Performing these analyses for every hour of a 21 day period spanning the episode and several days on either side allowed the results to be presented as a time series of sensitivity coefficients, showing how the influence of different input uncertainties changed during the episode. This is one of the most complex models to which these methods have been applied, and here, they reveal detailed spatiotemporal patterns of model sensitivities, with NO and isoprene emissions, NO2 photolysis, ozone BCs, and deposition velocity being among the most influential input uncertainties.

Evaluation of an explicit NOx chemistry method in AERMOD

ABSTRACTAn explicit NOx chemistry method has been implemented in AERMOD version 15181, ADMSM. The scheme has been evaluated by comparison with the methodologies currently recommended by the U.S. EPA for Tier 3 NO2 calculations, that is, OLM and PVMRM2. Four data sets have been used for NO2 chemistry method evaluation. Overall, ADMSM-modeled NO2 concentrations show the most consistency with the AERMOD calculations of NOx and the highest Index of Agreement; they are also on average lower than those of both OLM and PVMRM2. OLM shows little consistency with modeled NOx concentrations and markedly overpredicts NO2. PVMRM2 shows performance closer to that of ADMSM than OLM; however, its behavior is inconsistent with modeled NOx in some cases and it has less good statistics for NO2. The trend in model performance can be explained by examining the features particular to each chemistry method: OLM can be considered as a screening model as it calculates the upper bound of conversion from NO to NO2 possible with the background O3 concentration; PVMRM2 includes a much-improved estimate of in-plume O3 but is otherwise similar to OLM, assuming instantaneous reaction of NO with O3; and ADMSM allows for the rate of this reaction and also the photolysis of NO2. Evaluation with additional data sets is needed to further clarify the relative performance of ADMSM and PVMRM2.Implications: Extensive evaluation of the current AERMOD Tier 3 chemistry methods OLM and PVMRM2, alongside a new scheme that explicitly calculates the oxidation of NO by O3 and the reverse photolytic reaction, shows that OLM consistently overpredicts NO2 concentrations. PVMRM2 performs well in general, but there are some cases where this method overpredicts NO2. The new explicit NOx chemistry scheme, ADMSM, predicts NO2 concentrations that are more consistent with both the modeled NOx concentrations and the observations.

Model inter-comparison and validation of ADMS plume chemistry schemes

Two schemes for the determination of NO2 concentrations in the atmospheric dispersion model ADMS are evaluated using data from two sites in Alaska. Both schemes take account of the rate of oxidation of NO and photolysis of NO2 in the plume using identical chemical formulations. The differences lie in the approaches used for the entrainment and mixing of ambient ozone into the plume. In the standard scheme it is assumed that ozone is mixed instantaneously into the plume at source; in the entrainment limited scheme ozone is entrained into the plume at a rate determined by the rate of dilution of the instantaneous plume. A methodology comprising a scatter plot of the ratio of modelled to observed NO2 vs. modelled to observed NOx is used to distinguish errors in the chemistry schemes from errors in the prediction of NOx. Both schemes show good performance statistics with the standard scheme predicting higher NO2 concentrations.

Model inter-comparison and validation of ADMS plume chemistry schemes

Two schemes for the determination of NO2 concentrations in the atmospheric dispersion model ADMS are evaluated using data from two sites in Alaska. Both schemes take account of the rate of oxidation of NO and photolysis of NO2 in the plume using identical chemical formulations. The differences lie in the approaches used for the entrainment and mixing of ambient ozone into the plume. In the standard scheme it is assumed that ozone is mixed instantaneously into the plume at source; in the entrainment limited scheme ozone is entrained into the plume at a rate determined by the rate of dilution of the instantaneous plume. A methodology comprising a scatter plot of the ratio of modelled to observed NO2 vs. modelled to observed NOx is used to distinguish errors in the chemistry schemes from errors in the prediction of NOx. Both schemes show good performance statistics with the standard scheme predicting higher NO2 concentrations.

Kinetics of the Reaction of CH3O2 Radicals with OH Studied over the 292-526 K Temperature Range.

Reaction of methyl peroxy radicals with hydroxyl radicals, CH3O2 + OH → CH3O + HO2 (1a) and CH3O2 + OH → CH2OO + H2O (1b) was studied using pulsed laser photolysis coupled to transient UV-vis absorption spectroscopy over the 292-526 K temperature range and pressure 1 bar (bath gas He). Hydroxyl radicals were generated in the reaction of electronically excited oxygen atoms O((1)D), produced in the photolysis of N2O at 193.3 nm, with H2O. Methyl peroxy radicals were generated in the reaction of methyl radicals, CH3, produced in the photolysis of acetone at 193.3 nm, and subsequent reaction of CH3 with O2. Temporal profiles of OH were monitored via transient absorption of light from a DC discharge H2O/Ar low-pressure resonance lamp at ca. 308 nm. The absolute intensity of the photolysis light was determined by accurate in situ actinometry based on the ozone formation in the presence of molecular oxygen. The overall rate constant of the reaction is k1a+1b = (8.4 ± 1.7) × 10(-11)(T/298 K)(-0.81) cm(3) molecule(-1) s(-1) (292-526 K). The branching ratio of channel 1b at 298 K is less than 5%.

A global simulation of brown carbon: implications for photochemistry and direct radiative effect

Abstract. Recent observations suggest that a certain fraction of organic carbon (OC) aerosol effectively absorbs solar radiation, which is also known as brown carbon (BrC) aerosol. Despite much observational evidence of its presence, very few global modelling studies have been conducted because of poor understanding of global BrC emissions. Here we present an explicit global simulation of BrC in a global 3-D chemical transport model (GEOS-Chem), including global BrC emission estimates from primary (3.9 ± 1.7 and 3.0 ± 1.3 TgC yr−1 from biomass burning and biofuel) and secondary (5.7 TgC yr−1 from aromatic oxidation) sources. We evaluate the model by comparing the results with observed absorption by water-soluble OC in surface air in the United States, and with single scattering albedo observations at Aerosol Robotic Network (AERONET) sites all over the globe. The model successfully reproduces the seasonal variations of observed light absorption by water-soluble OC, but underestimates the magnitudes, especially in regions with high secondary source contributions. Our global simulations show that BrC accounts for 21 % of the global mean surface OC concentration, which is typically assumed to be scattering. We find that the global direct radiative effect of BrC is nearly zero at the top of the atmosphere, and consequently decreases the direct radiative cooling effect of OC by 16 %. In addition, the BrC absorption leads to a general reduction of NO2 photolysis rates, whose maximum decreases occur in Asia up to −8 % (−17 %) on an annual (spring) mean basis. The resulting decreases of annual (spring) mean surface ozone concentrations are up to −6 % (−13 %) in Asia, indicating a non-negligible effect of BrC on photochemistry in this region.

Characterization of a Smog Chamber for Studying Formation and Physicochemical Properties of Secondary Organic Aerosol

An indoor smog chamber facility has been built for carrying out secondary organic aerosol (SOA) formation and for studying physicochemical properties of SOA. This facility comprises of ~7 m3 FEP Teflon reactor placed in temperature controlled room coupled with instruments for gas and particle phase data. Detailed characterization experiments have been presented describing control of reactor temperature, relative humidity (RH), effective mixing time, wall loss rates of gases and particles, light source, and air purification. This chamber showed a wide range of temperature control with acceptable precision (i.e., 18–33 ± 0.5°C). The gas wall loss rates for NO, NO2, and O3 were found to be 3.78 × 10–4 min–1, 4.48 × 10–5 min–1, and 6.47 × 10–5 min–1, respectively. NO2 photolysis rate constant was 0.17 min–1. Particle wall loss constant was found to be 3.96 × 10–3 min–1 at Dp = 100 nm. SOA yields of dark α-pinene ozonolysis ranged from 0.025 to 0.378 for α-pinene concentrations from 10 ppb to 100 ppb.

Preparation, characterization and photocatalytic performance of TiO2 prepared by using pressurized fluids in CO2 reduction and N2O decomposition

TiO2 photocatalyst was prepared unconventionally, using the sol–gel process controlled within the reverse micelles and the processing by pressurized hot fluids as an alternative to standard calcination. Conventional calcined TiO2 was prepared as well. Textural, microstructural and optical properties of prepared photocatalysts were characterized by using nitrogen physisorption, powder X-ray diffraction and DR UV–Vis spectroscopy. The photocatalytic properties of developed TiO2 catalysts were investigated in the photocatalytic reduction of CO2 and photocatalytic decomposition of N2O. It was revealed that TiO2 processed by pressurized hot fluids shows significantly improved textural properties and different crystallinity compared to its calcined analog. Yields of both reaction products (H2 and CH4) of CO2 photoreduction were higher for the extracted TiO2 photocatalyst. The same result was achieved in N2O photodecomposition. The maximum N2O conversion (83 % after 20 h of illumination) in inert gas was reached also over the TiO2 extracted photocatalyst, and it can be attributed to simultaneous N2O photocatalytic decomposition and N2O photolysis. Reaction kinetics of N2O-photoinduced decomposition was described well by the pseudo-first-rate law. The surface heterojunction of bicrystalline anatase–brookite phase corresponded to better catalytic activity of TiO2 processed by pressurized hot fluids in both reactions, in a consequence of reduced electron–hole pair recombination.

The impact of parameterising light penetration into snow on the photochemical production of NO<sub><i>x</i></sub> and OH radicals in snow

Abstract. Snow photochemical processes drive production of chemical trace gases in snowpacks, including nitrogen oxides (NOx = NO + NO2) and hydrogen oxide radical (HOx = OH + HO2), which are then released to the lower atmosphere. Coupled atmosphere–snow modelling of theses processes on global scales requires simple parameterisations of actinic flux in snow to reduce computational cost. The disagreement between a physical radiative-transfer (RT) method and a parameterisation based upon the e-folding depth of actinic flux in snow is evaluated. In particular, the photolysis of the nitrate anion (NO3-), the nitrite anion (NO2-) and hydrogen peroxide (H2O2) in snow and nitrogen dioxide (NO2) in the snowpack interstitial air are considered. The emission flux from the snowpack is estimated as the product of the depth-integrated photolysis rate coefficient, v, and the concentration of photolysis precursors in the snow. The depth-integrated photolysis rate coefficient is calculated (a) explicitly with an RT model (TUV), vTUV, and (b) with a simple parameterisation based on e-folding depth, vze. The metric for the evaluation is based upon the deviation of the ratio of the depth-integrated photolysis rate coefficient determined by the two methods, vTUV/vze, from unity. The ratio depends primarily on the position of the peak in the photolysis action spectrum of chemical species, solar zenith angle and physical properties of the snowpack, i.e. strong dependence on the light-scattering cross section and the mass ratio of light-absorbing impurity (i.e. black carbon and HULIS) with a weak dependence on density. For the photolysis of NO2, the NO2- anion, the NO3- anion and H2O2 the ratio vTUV/vze varies within the range of 0.82–1.35, 0.88–1.28, 0.93–1.27 and 0.91–1.28 respectively. The e-folding depth parameterisation underestimates for small solar zenith angles and overestimates at solar zenith angles around 60° compared to the RT method. A simple algorithm has been developed to improve the parameterisation which reduces the ratio vTUV/vze to 0.97–1.02, 0.99–1.02, 0.99–1.03 and 0.98–1.06 for photolysis of NO2, the NO2- anion, the NO3- anion and H2O2 respectively. The e-folding depth parameterisation may give acceptable results for the photolysis of the NO3- anion and H2O2 in cold polar snow with large solar zenith angles, but it can be improved by a correction based on solar zenith angle and for cloudy skies.

Dynamics of ozone and nitrogen oxides at Summit, Greenland. II. Simulating snowpack chemistry during a spring high ozone event with a 1-D process-scale model

Observed depth profiles of nitric oxide (NO), nitrogen dioxide (NO2), and ozone (O3) in snowpack interstitial air at Summit, Greenland were best replicated by a 1-D process-scale model, which included (1) geometrical representation of snow grains as spheres, (2) aqueous-phase chemistry confined to a quasi-liquid layer (QLL) on the surface of snow grains, and (3) initialization of the species concentrations in the QLL through equilibrium partitioning with mixing ratios in snowpack interstitial air. A comprehensive suite of measurements in and above snowpack during a high O3 event facilitated analysis of the relationship between the chemistry of snowpack and the overlying atmosphere. The model successfully reproduced 2 maxima (i.e., a peak near the surface of the snowpack at solar noon and a larger peak occurring in the evening that extended down from 0.5 to 2 m) in the diurnal profile of NO2 within snowpack interstitial air. The maximum production rate of NO2 by photolysis of nitrate (NO3−) was approximately 108 molec cm−3 s−1, which explained daily observations of maxima in NO2 mixing ratios near solar noon. Mixing ratios of NO2 in snowpack interstitial air were greatest in the deepest layers of the snowpack at night and were attributed to thermal decomposition of peroxynitric acid, which produced up to 106 molec NO2 cm−3 s−1. Highest levels of NO in snowpack interstitial air were confined to upper layers of the snowpack and observed profiles were consistent with photolysis of NO2. Production of nitrogen oxides (NOx) from NO3− photolysis was estimated to be two orders of magnitude larger than NO production and supports the hypothesis that NO3− photolysis is the primary source of NOx within sunlit snowpack in the Arctic. Aqueous-phase oxidation of formic acid by O3 resulted in a maximum consumption rate of ∼106–107 molec cm−3 s−1 and was the primary removal mechanism for O3.

Characterization and testing of a new environmental chamber

Abstract. A 29 m3 Teflon chamber, designed for studies on the aging of combustion aerosols, at the University of Eastern Finland is described and characterized. The chamber is part of a research facility, called Ilmari, where small-scale combustion devices, a dynamometer for vehicle exhaust studies, dilution systems, the chamber, and cell and animal exposure devices are located side by side under the same roof. The small surface-to-volume ratio of the chamber enables reasonably long experiment times, with particle wall loss rate constants of 0.088, 0.080, 0.045, and 0.040 h−1 for polydisperse, 50, 100, and 200 nm monodisperse aerosols, respectively. The NO2 photolysis rate can be adjusted from 0 to 0.62 min−1. The irradiance spectrum is centered at either 350 or 365 nm, and the maximum irradiance, produced by up to 160 blacklight lamps, is 29.7 W m−2, which corresponds to the ultraviolet (UV) irradiance in Central Finland at noon on a sunny day in the midsummer. The temperature inside the chamber is uniform and can be kept at 25±1 °C. The chamber is kept in an overpressure with a moving top frame, which reduces sample dilution and entrance of contamination during an experiment. The functionality of the chamber was tested with oxidation experiments of toluene, resulting in secondary organic aerosol (SOA) yields of 12–42%, depending on the initial conditions, such as NOx concentration and UV irradiation. The highest gaseous oxidation product yields of 12.4–19.5% and 5.8–19.5% were detected with ions corresponding to methyl glyoxal (m/z 73.029) and 4-oxo-2-pentenal (m/z 99.044), respectively. Overall, reasonable yields of SOA and gaseous reaction products, comparable to those obtained in other laboratories, were obtained.