O3 Photolysis Research Articles

Sources and Cycling of Tropospheric Hydroxyl Radicals – An Overview

Abstract The hydroxyl radical is the principal oxidizing agent in the troposphere. It controls and determines the oxidizing power of the atmosphere and thus governs the atmospheric lifetime of many species, and their potential to contribute to climate change, air pollution and ozone formation. Owing to the development of new measurement techniques and the discovery of new reaction mechanisms, the understanding of the OH chemistry has witnessed significant advances during the last decades. This article presents a comprehensive review of the current understanding of OH radical chemistry with an outlook to future work in this active research area of atmospheric chemistry.Among the different OH radical initiation sources, e.g. O3 photolysis, HCHO photolysis, ozonolysis of alkenes and the photolysis of nitrous acid (HONO), the latter has been shown in recent field and model studies to make a major contribution to tropospheric OH levels. New photochemical sources of HONO have been discovered in the laboratory which can explain unexpectedly high concentrations of HONO observed in the atmosphere during daytime. A detailed analysis of HONO sources in the atmosphere is presented. OH radicals react with volatile organic compounds (VOCs) in a complex cycle regenerating OH radicals in the propagation cycle. Recent field and model studies show that the OH radical propagation cycle is balanced for high NOx conditions. Thus, radical losses by reactions with VOCs are balanced by OH formation through the reaction HO2+NO. However, studies at low NO and high VOC levels imply that unknown radical sources of OH exist in rural and forested areas. Possible sources of OH radicals under these conditions are discussed.

Oxidative capacity of the Mexico City atmosphere – Part 1: A radical source perspective

Abstract. A detailed analysis of OH, HO2 and RO2 radical sources is presented for the near field photochemical regime inside the Mexico City Metropolitan Area (MCMA). During spring of 2003 (MCMA-2003 field campaign) an extensive set of measurements was collected to quantify time-resolved ROx (sum of OH, HO2, RO2) radical production rates from day- and nighttime radical sources. The Master Chemical Mechanism (MCMv3.1) was constrained by measurements of (1) concentration time-profiles of photosensitive radical precursors, i.e., nitrous acid (HONO), formaldehyde (HCHO), ozone (O3), glyoxal (CHOCHO), and other oxygenated volatile organic compounds (OVOCs); (2) respective photolysis-frequencies (J-values); (3) concentration time-profiles of alkanes, alkenes, and aromatic VOCs (103 compound are treated) and oxidants, i.e., OH- and NO3 radicals, O3; and (4) NO, NO2, meteorological and other parameters. The ROx production rate was calculated directly from these observations; the MCM was used to estimate further ROx production from unconstrained sources, and express overall ROx production as OH-equivalents (i.e., taking into account the propagation efficiencies of RO2 and HO2 radicals into OH radicals). Daytime radical production is found to be about 10–25 times higher than at night; it does not track the abundance of sunlight. 12-h average daytime contributions of individual sources are: Oxygenated VOC other than HCHO about 33%; HCHO and O3 photolysis each about 20%; O3/alkene reactions and HONO photolysis each about 12%, other sources <3%. Nitryl chloride photolysis could potentially contribute ~15% additional radicals, while NO2* + water makes – if any – a very small contribution (~2%). The peak radical production of ~7.5 107 molec cm−3 s−1 is found already at 10:00 a.m., i.e., more than 2.5 h before solar noon. O3/alkene reactions are indirectly responsible for ~33% of these radicals. Our measurements and analysis comprise a database that enables testing of the representation of radical sources and radical chain reactions in photochemical models. Since the photochemical processing of pollutants in the MCMA is radical limited, our analysis identifies the drivers for ozone and SOA formation. We conclude that reductions in VOC emissions provide an efficient opportunity to reduce peak concentrations of these secondary pollutants, because (1) about 70% of radical production is linked to VOC precursors; (2) lowering the VOC/NOx ratio has the further benefit of reducing the radical re-cycling efficiency from radical chain reactions (chemical amplification of radical sources); (3) a positive feedback is identified: lowering the rate of radical production from organic precursors also reduces that from inorganic precursors, like ozone, as pollution export from the MCMA caps the amount of ozone that accumulates at a lower rate inside the MCMA. Continued VOC reductions will in the future result in decreasing peak concentrations of ozone and SOA in the MCMA.

Variability of ozone in the marine boundary layer of the equatorial Pacific Ocean

This study examines the processes controlling the diurnal variability of ozone (O3) in the marine boundary layer of the Kwajalein Atoll, Republic of the Marshall Islands (latitude 8° 43′ N, longitude 167° 44′ E), during July to September 1999. At the study site, situated in the equatorial Pacific Ocean, O3 mixing ratios remained low, with an overall average of 9–10 parts per billion on a volume basis (ppbv) and a standard deviation of 2.5 ppbv. In the absence of convective storms, daily O3 mixing ratios decreased after sunrise and reached minimum during the afternoon in response to photochemical reactions. The peak-to-peak amplitude of O3 diurnal variation was approximately 1–3 ppbv. During the daytime, O3 photolysis, hydroperoxyl radicals, hydroxyl radicals, and bromine atoms contributed to the destruction of O3, which explained the observed minimum O3 levels observed in the afternoon. The entrainment of O3-richer air from the free troposphere to the local marine boundary layer provided a recovery mechanism of surface O3 mixing ratio with a transport rate of 0.04 to 0.2 ppbv per hour during nighttime. In the presence of convection, downward transport of O3-richer tropospheric air increased surface O3 mixing ratios by 3–12 ppbv. The magnitude of O3 increase due to moist convection was lower than that observed over the continent (as high as 20–30 ppbv). Differences were ascribed to the higher O3 levels in the continental troposphere and weaker convection over the ocean. Present results suggest that moist convection plays a role in surface-level O3 dynamics in the tropical marine boundary layer.

Angular momentum polarisation in the O(1D) products of O2 photolysis via the B state

The first fully allowed spectroscopic transition in O2 is the transition comprising the well-known Schumann–Runge bands and continuum. We report a velocity-map imaging study in which the O(1 D) angular momentum polarisation and O(3 P) spin–orbit branching ratios arising from this process have been measured. We show that direct 157 nm excitation into the Schumann–Runge continuum leads to extremely strong angular momentum polarisation in the O(1D) product. Comparison with previous studies indicates that this is a general feature of dissociation via the B state. The fine structure branching ratios in the co-fragment O(3P J=2,1,0) were measured to be 88.5 ± 1.6 : 9.7 ± 1.4 : 1.9 ± 0.4. Based on a consideration of the Massey parameter for the system, the data were modelled using theoretical calculations based on adiabatic and diabatic models of the dissociation. While both models were able to describe some aspects of the dissociation accurately, neither was able to predict both the fine structure branching ratios of the O(3P) products and the O(1D2) alignment. We have also investigated O(1D2) alignment arising from 203.8 and 205.5 nm photodissociation via the state of O2 vibrationally excited to v=6–11. As in the 157 nm photodissciation of vibrationally ground state O2, strong polarisation of the O(1D2) photofragments is observed.

Angular distributions and angular momentum alignment of O(3PJ) atoms formed in the photolysis of O2via the Herzberg continuum

Sliced velocity-map imaging has been used to measure photofragment scattering distributions for the O((3)P(2)) and O((3)P(1)) products of O(2) photolysis following laser excitation into the Herzberg continuum between 205 and 241 nm. The images were analysed to extract the photofragment spatial anisotropy parameter, β, together with the alignment parameters a(∥), a(⊥), a(⊥), and Re[a(∥, ⊥)]. Our alignment measurements bridge the gap between the recent 193 nm measurement of Brouard et al., Phys. Chem. Chem. Phys., 2006, 8, 5549 and those of Alexander et al., J. Chem. Phys., 2003, 118, 10566 at 222 and 237 nm, and extend out to the threshold at 241 nm. Our measured parameters show no strong dependence on photolysis wavelength. Near the threshold we were able to separate the contributions from the O((3)P(2)) + O((3)P(2)) and O((3)P(2)) + O((3)P(1)) channels, and found significantly different photofragment alignments for the two cases.

Nascent Vibrational Energy Distributions of O2(X3Σg−, v = 6−13) Generated in the Photolysis of O3 at 266 nm

The vibrational levels of O2(X3Sigma(g)-) generated in the ultraviolet photolysis of O3 at 266 nm were detected via laser-induced fluorescence (LIF) of the B3Sigma(u)- - X3Sigma(g)- system. The nascent vibrational energy distributions of O2(X3Sigma(g)-, nu = 6-13) have been measured by two different methods. One is a kinetic analysis based on the originally developed integrated profiles method (IPM). The time-resolved LIF of a single vibrational level has been recorded in the presence of CF4 or O2 as a relaxation partner. The IPM analysis of the profiles gave the relative detectabilities of adjacent vibrational levels, and the initial relative populations of the vibrational levels have been determined from the intensities of LIF subsequent to the photolysis. The other is the analysis of the area intensities of the LIF of the vibrational levels of interest. The rotational levels with the identical quantum numbers of different vibrational levels in the X3Sigma(g)- state were excited to a common vibrational level nu' = 0 in the B3Sigma(u)- state. Correction for the LIF intensities with the Franck-Condon factors was made, and the initial relative populations have been obtained. The two different methods have given similar nascent vibrational energy distributions, and comparison to the previous reports has been made.

Measurements of OH and HO<sub>2</sub> concentrations during the MCMA-2006 field campaign – Part 2: Model comparison and radical budget

Abstract. Measurements of hydroxyl (OH) and hydroperoxy (HO2) radicals were made during the Mexico City Metropolitan Area (MCMA) field campaign as part of the MILAGRO (Megacity Initiative: Local and Global Research Observations) project during March 2006. These measurements provide a unique opportunity to test current models of atmospheric ROx (OH + HO2 + RO2) photochemistry under polluted conditions. A zero-dimensional box model based on the Regional Atmospheric Chemical Mechanism (RACM) was constrained by 10-min averages of 24 J-values and the concentrations of 97 chemical species. Several issues related to the ROx chemistry under polluted conditions are highlighted in this study: (i) Measured concentrations of both OH and HO2 were underpredicted during morning hours on a median campaign basis, suggesting a significant source of radicals is missing from current atmospheric models under polluted conditions, consistent with previous urban field campaigns. (ii) The model-predicted HO2/OH ratios underestimate the measurements for NO mixing ratios higher than 5 ppb, also consistent with previous urban field campaigns. This suggests that under high NOx conditions, the HO2 to OH propagation rate may be overestimated by the model or a process converting OH into HO2 may be missing from the chemical mechanism. On a daily basis (08:40 a.m.–06:40 p.m.), an analysis of the radical budget indicates that HONO photolysis, HCHO photolysis, O3-alkene reactions and dicarbonyls photolysis are the main radical sources. O3 photolysis contributes to less than 6% of the total radical production.

Seasonal dependence of the oxidation capacity of the city of Santiago de Chile

The oxidation capacity of the highly polluted urban area of Santiago de Chile has been evaluated during a winter measurement campaign from May 25 to June 07, 2005, with the results compared and contrasted with those previously evaluated during a summer campaign from March 8 to 20, 2005. The OH radical budget was evaluated in both campaigns employing a simple quasi-photostationary state model (PSS) constrained with simultaneous measurements of HONO, HCHO, O3, NO, NO2, j(O1D), j(NO2), 13 alkenes and meteorological parameters. In addition, a zero dimensional photochemical box model based on the Master Chemical Mechanism (MCMv3.1) has been used for the analysis of the radical budgets and concentrations of OH, HO2 and RO2. Besides the above parameters, the MCM model has been constrained by the measured CO and other volatile organic compounds (VOCs) including alkanes and aromatics. Total production and destruction rates of OH and HO2 in winter are about two times lower than that during summer. Simulated OH levels by both PSS and MCM models are similar during the daytime for both winter and summer indicating that the primary OH sources and sinks included in the simple PSS model are predominant. On a 24 h basis, HONO photolysis was shown to be the most important primary OH radical source comprising 81% and 52% of the OH initiation rate during winter and summer, respectively followed by alkene ozonolysis (12.5% and 29%), photolysis of HCHO (6.1% and 15%), and photolysis of O3 (<1% and 4%), respectively. During both winter and summer, there was a balance between the OH secondary production (HO2 + NO) and destruction (OH + VOCs) showing that initiation sources of RO2 and HO2 are no net OH initiation sources. This result was found to be fulfilled also for all other studies investigated. Seasonal impacts on the radical budgets are also discussed.

Photochemical Removal of N2O in N2 or Air Using 172 nm Excimer Lamps

N2O removal was investigated in N2 or air using 172 nm Xe2 excimer lamps (50 or 300 mW/cm2) without using any expensive catalysts. The residual amount of N2O and the formation ratios of products were measured as functions of photoirradiation time, N2O concentration, and O2 concentration. N2O (100 ppm) was completely converted to N2 and O2 without NOx emission in N2 at atmospheric pressure after 30 min photoirradiation using a high-power Xe2 excimer lamp (300 mW/cm2). 76% of N2O (100 ppm) was also converted to N2, O2, and HNO3 in air (20% O2) after 30 min photoirradiation using the high-power lamp. We concluded that N2O is dominantly decomposed by 172 nm photolysis in N2 and by the O(1D) + N2O reaction in air, where O(1D) atoms dominantly arise from the 172 nm photolysis of O2. The conversion of N2O in air increased more than twofold by decreasing the total pressure from atmospheric pressure to 20 kPa by suppressing the collisional quenching of O(1D) by N2 and O2 buffer gases. In a flow experiment, the conversion of N2O in N2 was only 6–18% in the total flow rate range of 0.1–1 L/min owing to the short residence time of N2O in the photolysis chamber.

Oxidation capacity of the city air of Santiago, Chile

Abstract. The oxidation capacity of the highly polluted urban area of Santiago, Chile has been evaluated during a summer measurement campaign carried out from 8–20 March 2005. The hydroxyl (OH) radical budget was evaluated employing a simple quasi-photostationary-state model (PSS) constrained with simultaneous measurements of HONO, HCHO, O3, NO, NO2, j(O1D), j(NO2), 13 alkenes and meteorological parameters. In addition, a zero dimensional photochemical box model based on the Master Chemical Mechanism (MCMv3.1) has been used to estimate production rates and total free radical budgets, including OH, HO2 and RO2. Besides the above parameters, the MCM model has been constrained by the measured CO and volatile organic compounds (VOCs) including alkanes and aromatics. Both models simulate the same OH concentration during daytime indicating that the primary OH sources and sinks included in the simple PSS model predominate. Mixing ratios of the main OH radical precursors were found to be in the range 0.8–7 ppbv (HONO), 0.9–11 ppbv (HCHO) and 0–125 ppbv (O3). The alkenes average mixing ratio was ~58 ppbC accounting for ~12% of the total identified non-methane hydrocarbons (NMHCs). During the daytime (08:00 h–19:00 h), HONO photolysis was shown to be the most important primary OH radical source comprising alone ~55% of the total initial production rate, followed by alkene ozonolysis (~24%) and photolysis of HCHO (~16%) and O3 (~5%). The calculated average and maximum daytime OH production rates from HONO photolysis was 1.7 ppbv h−1 and 3.1 ppbv h−1, respectively. Based on the experimental results a strong photochemical daytime source of HONO is proposed. A detailed analysis of the sources of OH radical precursors has also been carried out.

Tropospheric O3 from photolysis of O2

Photolytic dissociation of molecular oxygen (O2) at wavelengths about 205 nm produces ozone (O3) in the upper tropical troposphere. In tropospheric chemistry models that ignore this process, the O3 abundance above 14 km in the tropics (a.k.a. Tropopause Transition Layer) is underestimated by 5 to 20 ppb. Even for models including O2 photolysis, uncertainty in the O2 cross sections yields similar uncertainty in TTL O3. The related impact on global atmospheric chemistry is small, i.e., ±0.2% in CO and CH4 budgets, but the change in the O3 column, ±1.6 DU in the tropics, may be important in calculating heating rates and climate forcing.

Accommodation of Two Diatomic Molecules in Cytochrome bo3: Insights into NO Reductase Activity in Terminal Oxidases

Bacterial heme-copper terminal oxidases react quickly with NO to form a heme-nitrosyl complex, which, in some of these enzymes, can further react with a second NO molecule to produce N(2)O. Previously, we characterized the heme a(3)-NO complex formed in cytochrome ba(3) from Thermus thermophilus and the product of its low-temperature illumination. We showed that the photolyzed NO group binds to Cu(B)(I) to form an end-on NO-Cu(B) or a side-on copper-nitrosyl complex, which is likely to represent the binding characteristics of the second NO molecule at the heme-copper active site. Here we present a comparative study with cytochrome bo(3) from Escherichia coli. Both terminal oxidases are shown to catalyze the same two-electron reduction of NO to N(2)O. The EPR and resonance Raman signatures of the heme o(3)-NO complex are comparable to those of the a(3)-NO complex. However, low-temperature FTIR experiments reveal that photolysis of the heme o(3)-NO complex does not produce a Cu(B)-nitrosyl complex, but that instead, the NO remains unbound in the active-site cavity. Additional FTIR photolysis experiments on the heme-nitrosyl complexes of these terminal oxidases, in the presence of CO, demonstrate that an [o(3)-NO.OC-Cu(B)] tertiary complex can form in bo(3) but not in ba(3). We assign these differences to a greater iron-copper distance in the reduced form of bo(3) compared to that of ba(3). Because this difference in metal-metal distance does not appear to affect the NO reductase activity, our results suggest that the coordination of the second NO to Cu(B) is not an essential step of the reaction mechanism.

Long-term observation of mass-independent oxygen isotope anomaly in stratospheric CO&amp;lt;sub&amp;gt;2&amp;lt;/sub&amp;gt;

Abstract. Stratospheric and upper tropospheric air samples were collected during 1994–2004 over Sanriku, Japan and in 1997 over Kiruna, Sweden. Using these archived air samples, we determined the triple oxygen-isotope composition of stratospheric CO2 and the N2O mixing ratio. The maximum Δ17OCO2 value of +12.2‰, resembling that observed previously in the mesosphere at 60 km height, was found in the middle stratosphere over Kiruna at 25.6 km height, suggesting that upper stratospheric and mesospheric air descended to the middle stratosphere through strong downward advection. A least-squares regression analysis of our observations on a δ18OCO2−δ17OCO2 plot (r2&gt;0.95) shows a slope of 1.63±pm0.10, which is similar to the reported value of 1.71±0.06, thereby confirming the linearity of three isotope correlation with the slope of 1.6–1.7 in the mid-latitude lower and middle stratosphere. The slope decrease with increasing altitude and a curvy trend in three-isotope correlation reported from previous studies were not statistically significant. Using negative linear correlations of Δ17OCO2 and δ18OCO2 with the N2O mixing ratio, we quantified triple oxygen-isotope fluxes of CO2 to the troposphere as +48‰ GtC/yr (Δ17OCO2) and +38‰ GtC/yr (δ18OCO2) with ~30% uncertainty. Comparing recent model results and observations, underestimation of the three isotope slope and the maximum Δ17OCO2 value in the model were clarified, suggesting a smaller O2 photolysis contribution than that of the model. Simultaneous observations of δ18OCO2, δ17OCO2, and N2O mixing ratios can elucidate triple oxygen isotopes in CO2 and clarify complex interactions among physical, chemical, and photochemical processes occurring in the middle atmosphere.

Atmospheric production of nitrous oxide from excited ozone and its potentially important implications for global change studies

Nitrous oxide (N2O) is a greenhouse gas included in the Kyoto Protocol. Its production from excited ozone (O3) may potentially influence inverse modeling, future growth projection, and the use of mass‐independent Δ17O anomaly of N2O for probing paleoatmospheric O3. On the basis of the three‐component model of N2O quantum yield in photolysis of O3 in air, the globally averaged atmospheric production of N2O from O3 electronically excited by the Hartley‐Huggins band and from highly vibrationally excited ground‐state O3 are 1.01 and 0.26 Tg N a−1, respectively. The sum of the two productions is 9.4 and 7.7%, respectively, of the N2O from microbial and anthropogenic activities estimated by Global Emissions Inventory Activity and by the Intergovernmental Panel on Climate Change (2001). Uncertainties in these results are discussed. Subject to those uncertainties, inverse modeling of N2O that neglects productions from O3 could yield artificially magnified (by about 7%) globally averaged emission of N2O from microbial and anthropogenic activity and introduce distortion in the regional and seasonal pattern in that emission. Experiments that could narrow the uncertainties are discussed. Production from highly vibrationally excited O3 reduces the steepness in the decrease of N2O volume‐mixing ratios (VMR) above 35 km. Modeled and observed VMR comparisons show latitude‐ and season‐dependent overestimation and underestimation of the N2O VMR by models. Globally averaged comparison suggests possible N2O source deficit in the stratosphere. Limitations, uncertainties, and need for experiments associated with this possibility are also discussed. If proven real, the possible missing N2O source could influence the atmospheric affects of solar UV variability, subject to conditions that are discussed.

Nitrous acid (HONO) and its daytime sources at a rural site during the 2004 PRIDE‐PRD experiment in China

High HONO level during daytime was observed at a rural site Xinken in southeastern China during the 2004 Program of Regional Integrated Experiments of Air Quality over Pear River Delta (PRIDE‐PRD). The high HONO concentration led to a daytime (9:00–15:00) OH formation up to three times faster than that from O3 photolysis. An unexplained daytime HONO source, approximately four times faster than the reaction of OH with NO, has been derived from the HONO budget estimation. According to current understanding, this unknown source was attributed to heterogeneous reactions of NO2 on ground and aerosol surfaces. The good correlation between the unknown source and J values is consistent with the photolytic HONO source observed in laboratory studies.

Kinetic Study of Vibrational Energy Transfer from a Wide Range of Vibrational Levels of O2(X3Σg−, v = 6−12) to CF4

A wide range of vibrational levels of O2(X(3)Sigma(g)(-), v = 6-13) generated in the ultraviolet photolysis of O3 was selectively detected by the laser-induced fluorescence (LIF) technique. The time-resolved LIF-excited B(3)Sigma(u)(-)-X(3)Sigma(g)(-) system in the presence of CF4 has been recorded and analyzed by the integrated profiles method (IPM). The IPM permitted us to determine the rate coefficients k(v)(CF4) for vibrational relaxation of O2(X(3)Sigma(g)(-), v = 6-12) by collisions with CF4. Energy transfer from O2 (v = 6-12) to CF4 is surprisingly efficient compared to that of other polyatomic relaxation partners studied so far. The k(v)(CF4) increases with vibrational quantum number v from [1.5 +/- 0.2(2sigma)] x 10(-12) for v = 6 to [7.3 +/- 1.5(2sigma)] x 10(-11) for v = 12, indicating that the infrared-active nu3 vibrational mode of CF4 mainly governs the energy transfer with O2(X(3)Sigma(g)(-), v = 6-12). The correlation between the rate coefficients and fundamental infrared intensities has been discussed based on a comparison of the efficiency of energy transfer by several collision partners.

Seasonal cycle of C16O16O, C16O17O, and C16O18O in the middle atmosphere: Implications for mesospheric dynamics and biogeochemical sources and sinks of CO2

The isotopic anomaly of oxygen in atmospheric CO2 is caused by exchange reactions with isotopically anomalous O(1D) in the middle atmosphere. In the stratosphere, the major source of O(1D) is O3 photolysis; O3 is known to possess mass‐independent isotopic composition, with δ49O3 ≈ δ50O3 ≈ 100‰ relative to atmospheric O2. Higher in the mesosphere, Lyman α‐driven photodissociation of O2 provides a more important source of heavy O(1D) than O3 photolysis. Here we present a two‐dimensional simulation of the isotopic composition of CO2 from the surface to an altitude of ∼130 km that adequately reproduce the observed seasonal cycle of CO2 in the upper troposphere and the age of air in the stratosphere. Our model results suggest that stratospheric‐tropospheric exchange not only modifies the level of heavy CO2 in the troposphere, but also influences its seasonal cycle. Thus the isotopic composition of CO2 in the troposphere/biosphere could be affected by the downwelling air from the stratosphere. The predicted size of the effect is detectable by current instrumentation. Implications for the use of the isotopic composition of CO2 to constrain the gross carbon flux between the atmosphere and terrestrial biosphere and the dynamics in the remote mesosphere are discussed.

Photolysis of surface O3 and production potential of OH radicals in the atmosphere over the Tibetan Plateau

With an area of 2.5 million km2 and an average altitude of about 4000 m above sea level, the Tibetan Plateau is the largest and highest plateau in the mid‐latitudes of the Northern Hemisphere. The high altitude, low latitude, and large snow coverage create strong surface solar radiation on the plateau. It is therefore likely that the atmosphere over the plateau is very photochemically active, with a high production potential for OH radicals by ozone photolysis. We used the Tropospheric Ultraviolet‐Visible Radiation (TUV) model to calculate the photolysis rate of ozone in the Mt. Qomolangma (Everest) region under clear sky conditions. Field measurement data were used to calculate the production rate and concentration of OH radicals in the atmosphere. In the summer noon, over non‐snow‐covered area, surface ozone photolysis rates J(O1D) were 4–5 × 10−5 s−1, the OH radical production rate range was 1–4 × 106 s−1, and the OH concentrations range was 106 to 107 cm−3. Over areas covered with ice and snow, the J(O1D) and OH production rates could be as high as 1.3 × 10−4 s−1 and 5.5 × 106 cm−3 s−1, respectively, because of strong snow albedo. We also calculated the spatial distributions of J(O1D) and OH production over the whole Tibetan Plateau. Because of the large area covered with snow, the O3 photolysis rates in winter could be equal to or even higher than the rates in summer and might create as photochemically active an atmosphere as in summer.

Diffusion and reactions of interstitial oxygen species in amorphous SiO2: A review

This article briefly summarizes the diffusion and reactions of interstitial oxygen species in amorphous SiO2 (a-SiO2). The most common form of interstitial oxygen species is oxygen molecule (O2), which is sensitively detectable via its characteristic infrared photoluminescence (PL) at 1272nm. The PL observation of interstitial O2 provides key data to verify various processes related to interstitial oxygen species: the dominant role of interstitial O2 in long-range oxygen transport in a-SiO2; formation of the Frenkel defect pair (Si–Si bond and interstitial oxygen atom, O0) by dense electronic excitation; efficient photolysis of interstitial O2 into O0 with F2 laser light (λ=157nm, hν=7.9eV); and creation of interstitial ozone molecule via reaction of interstitial O2 with photogenerated O0. The efficient formation of interstitial O0 by F2 laser photolysis makes it possible to investigate the mobility, optical absorption, and chemical reactions of interstitial O0. The observed properties of O0 are consistent with the model that O0 takes the configuration of Si–O–O–Si bond. Interstitial O2 and O0 react with dangling bonds, oxygen vacancies, and chloride groups in a-SiO2. Reactions of interstitial O2 and O0 with mobile interstitial hydrogen species produce interstitial water molecules and hydroperoxy radicals. Interstitial hydroxyl radicals are formed by F2 laser photolysis of interstitial water molecules.

Diurnal peroxy radical chemistry at a remote coastal site over the sea of Japan

The Rishiri Fall Experiment (RISFEX) was performed in September 2003 at a remote coastal site (45.07°N, 141.12°E, and 35 m asl) on Rishiri Island in the Sea of Japan. Peroxy radicals were measured from 15–21 September using a peroxy radical chemical amplifier (PERCA) instrument. Simultaneously measured were O3, NO, NO2, CO, nonmethane hydrocarbons (NMHCs), biogenic volatile organic compounds (BVOCs), carbonyl compounds, aromatics, volatile organoiodines, organobromines, black carbon, aerosols and photolysis frequencies of j(O1D) and j(NO2) as well as meteorological parameters. The data set covers the measurements under relative background conditions and polluted episodes over the period. The midday 30‐min averages of peroxy radicals ranged from 10 to 40 pptv with the highest observed on the event when the air masses were transported over the polluted continent in northern China before reaching the site. The significant radical signals were observed repeatedly in the early morning and late afternoon when j(O1D) was greatly reduced, resulting in the diurnal cycles of peroxy radicals much broader than those expected from the photolysis of O3 alone. A box model based on RACM (Regional Atmospheric Chemistry Mechanism) was used to calculate OH, HO2 and RO2 concentrations from measured stable species and parameters. The calculated peroxy radical concentrations agree well with measured ones during 0900–1530 Japan Standard Time (JST) (JST = UT + 9 hours) from 19 to 21 September. However, in the early morning and later afternoon when monoterpenes were the dominant VOC, the model overpredicts peroxy radicals by up to 85%. The including of uptake of radicals to aerosols into the model cannot account for the discrepancy. An underprediction by the model up to 45% was observed during noon hours on 18 September when isoprene concentration was high. It appears that unknown terpenes are present, which might produce extra radicals beyond the predicted by the model. The measured‐to‐modeled ratio of peroxy radical concentrations is near unity for [NO] &lt; 120 pptv, but rises up to 15 for [NO] &gt; 120 pptv, suggesting the presence of an unknown radical production process which is related with high NO concentration.