NO2 Mixing Ratios Research Articles

Effects of the solar eclipse on 15 January 2010 on the surface O<sub>3</sub>, NO, NO<sub>2</sub>, NH<sub>3</sub>, CO mixing ratio and the meteorological parameters at Thiruvanathapuram, India

Abstract. In this paper, we present the effect of total solar eclipse on surface O3, NO, NO2, NH3, CO mixing ratio and the meteorological parameters on 15 January 2010 at Thiruvanathapuram, India. On the day of total solar eclipse (i.e., 15 January 2010), the decrease in mixing ratio of surface O3 and NO2 is observed after the beginning of the solar eclipse events (11:15 to 15:30). Decrease in surface O3 may be due to decreased efficiency of the photochemical ozone formation, whereas, mixing ratio of NO and NH3 have been changed following the night time chemistry. Surface O3 reduced to 20.3 ppb after 22 min of full phase of the eclipse. During the solar eclipse period, the ambient temperature and wind speed have decreased, whereas, relative humidity has increased as expected.

Kinetics of Soot Oxidation by NO2

Modern technologies use NO(2) to promote low-temperature soot oxidation for diesel particulate filter regeneration. In this study, the online aerosol technique of high-temperature oxidation tandem differential mobility analysis is used to study kinetics of soot oxidation by NO(2). Soot particles are exposed to varying temperature and NO(2) mixing ratio inside the furnace resulting from thermal decomposition of NO(2) to NO. This causes soot oxidation rates to vary throughout the furnace. Variations in temperatures and NO(2) mixing ratio are thoroughly accounted for the first time. Soot oxidation rates are calculated as a function of frequency factor A(soot), activation energy E(soot), and concentration of NO(2) within the furnace at temperatures ranging from 500 to 950 degrees C. Results suggest A(soot) and E(soot) values for soot oxidation of 2.4 x 10(-14) (nm K(-0.5) s(-1) cm(3) molecule(-1)) and 47.1 kJ mol(-1), respectively, when reaction order to NO(2) is assumed as unity. The activation energy for soot oxidation with NO(2) is significantly lower than oxidation with air. However, parts per million levels of NO(2) cause soot oxidation at low temperatures suggesting NO(2) is a stronger oxidant than O(2).

Uptake of NO<sub>3</sub> and N<sub>2</sub>O<sub>5</sub> to Saharan dust, ambient urban aerosol and soot: a relative rate study

Abstract. The uptake of NO3 and N2O5 to Saharan dust, ambient aerosols and soot was investigated using a novel and simple relative rate method with simultaneous detection of both NO3 and N2O5. The use of cavity ring down spectroscopy to detect both trace gases enabled the measurements to be carried out at low mixing ratios (<500 pptv or 1×1010 molecule cm−3). The uptake coefficient ratio, γ(NO3)/γ(N2O5), was determined to be 0.9±0.4 for Saharan dust, independent of relative humidity, NO3 or N2O5 mixing ratio and exposure time. Ambient (urban) aerosols showed a very limited capacity to take up N2O5 but were reactive towards NO3 with γ(NO3)/γ(N2O5)>15. A value of γ(NO3)/γ(N2O5)~1.5–3 was obtained when using candle generated soot. The relative rate obtained for Saharan dust can be placed on an absolute basis using our recently determined value of γ(N2O5)=1×10−2 to give γ(NO3)=9×10−3, which is significantly smaller than the single previous value. With the present uptake coefficient, reaction of NO3 with mineral dust will generally not contribute significantly to its NO3 loss in the boundary atmosphere or to the nitration of mineral dust.

Nocturnal nitrogen oxides at a rural mountain-site in south-western Germany

Abstract. A new, two-channel instrument for simultaneous NO3 and N2O5 monitoring was used to make the first comprehensive set of nocturnal NOx measurements (NO, NO2, NO3 and N2O5) at the Taunus Observatory, a rural mountain site (Kleiner Feldberg) in South-western Germany. In May 2008, NO3 and N2O5 mixing ratios were well above the instrumental detection limit (a few ppt) on all nights of the campaign and were characterised by large variability. The concentrations of NO3, N2O5 and NO2 were consistent with the equilibrium constant, K2, defining the rates of formation and thermal dissociation of N2O5. A steady-state lifetime analysis is consistent with the loss of nocturnal NOx being dominated by the reaction of NO3 with volatile organic compounds in this forested region, with N2O5 uptake to aerosols of secondary importance. Analysis of a limited dataset obtained at high relative humidity indicated that the loss of N2O5 by reaction with water vapour is less efficient (>factor 3) than derived using laboratory kinetic data. The fraction of NOx present as NO3 and N2O5 reached ~20% on some nights, with night-time losses of NOx competing with daytime losses.

Intercomparison of measurements of NO<sub>2</sub> concentrations in the atmosphere simulation chamber SAPHIR during the NO3Comp campaign

Abstract. NO2 concentrations were measured by various instruments during the NO3Comp campaign at the atmosphere simulation chamber SAPHIR at Forschungszentrum Jülich, Germany, in June 2007. Analytical methods included photolytic conversion with chemiluminescence (PC-CLD), broadband cavity ring-down spectroscopy (BBCRDS), pulsed cavity ring-down spectroscopy (CRDS), incoherent broadband cavity-enhanced absorption spectroscopy (IBB\\-CEAS), and laser-induced fluorescence (LIF). All broadband absorption spectrometers were optimized for the detection of the main target species of the campaign, NO3, but were also capable of detecting NO2 simultaneously with reduced sensitivity. NO2 mixing ratios in the chamber were within a range characteristic of polluted, urban conditions, with a maximum mixing ratio of approximately 75 ppbv. The overall agreement between measurements of all instruments was excellent. Linear fits of the combined data sets resulted in slopes that differ from unity only within the stated uncertainty of each instrument. Possible interferences from species such as water vapor and ozone were negligible under the experimental conditions.

Variations in Mixing Ratios of Ambient Ammonia, Nitric Oxide and Nitrogen Dioxide in Different Environments of India

° 38'N, 77 ° 10'E; 220m m.s.l.), India (Figure 1) during July 2009. Delhi, the capital city of India, located in the northern part of India. It is one of the ten most polluted cities of the world and third most polluted city of the country having numerous industries in and around the city. The total number of registered vehicles in the city Abstract Mixing ratios of ambient NH3, NO and NO2 were measured over three different environments viz Delhi, Dibrugarh and Thiruvananthapuram during 2009-10 to study their diurnal variations, concentration and source strength. The average mixing ratio of NH 3 over Delhi, Dibrugarh and Thiruvananthapuram were recorded as 13.24 ± 0.39, 13.46 ± 2.52 and 12.65 ± 1.51 ppb respectively. The average mixing ratio of NO2 was recorded as 12.69 ± 0.39 with maxima of 20.22 ppb and minima of 0.75 ppb over Delhi whereas, the mixing ratio of ambient NO 2 ranges from 0.65 to 3.65 ppb and 0.83 to 3.02 over Dibrugarh and Thiruvananthapuram respectively. The mixing ratio of NO and NO2 varying significantly at all the three locations except NH 3 might be due to source strength and meteorological conditions of the locations. Result reveals that the mixing ratio of ambient NH 3 is positively correlated with ambient temperature (r 2 = 0.872) and NO2 (r 2 = 0.975) over Delhi whereas non-significant at other locations.

NO<sub>x</sub> production by lightning in Hector: first airborne measurements during SCOUT-O3/ACTIVE

Abstract. During the SCOUT-O3/ACTIVE field phase in November–December 2005, airborne in situ measurements were performed inside and in the vicinity of thunderstorms over northern Australia with several research aircraft (German Falcon, Russian M55 Geophysica, and British Dornier-228. Here a case study from 19 November is presented in detail on the basis of airborne trace gas measurements (NO, NOy, CO, O3) and stroke measurements from the German LIghtning Location NETwork (LINET), set up in the vicinity of Darwin during the field campaign. The anvil outflow from three different types of thunderstorms was probed by the Falcon aircraft: (1) a continental thunderstorm developing in a tropical airmass near Darwin, (2) a mesoscale convective system (MCS), known as Hector, developing within the tropical maritime continent (Tiwi Islands), and (3) a continental thunderstorm developing in a subtropical airmass ~200 km south of Darwin. For the first time detailed measurements of NO were performed in the Hector outflow. The highest NO mixing ratios were observed in Hector with peaks up to 7 nmol mol−1 in the main anvil outflow at ~11.5–12.5 km altitude. The mean NOx (=NO+NO2) mixing ratios during these penetrations (~100 km width) varied between 2.2 and 2.5 nmol mol−1. The NOx contribution from the boundary layer (BL), transported upward with the convection, to total anvil-NOx was found to be minor (<10%). On the basis of Falcon measurements, the mass flux of lightning-produced NOx (LNOx) in the well-developed Hector system was estimated to 0.6–0.7 kg(N) s−1. The highest average stroke rate of the probed thunderstorms was observed in the Hector system with 0.2 strokes s−1 (here only strokes with peak currents ≥10 kA contributing to LNOx were considered). The LNOx mass flux and the stroke rate were combined to estimate the LNOx production rate in the different thunderstorm types. For a better comparison with other studies, LINET strokes were scaled with Lightning Imaging Sensor (LIS) flashes. The LNOx production rate per LIS flash was estimated to 4.1–4.8 kg(N) for the well-developed Hector system, and to 5.4 and 1.7 kg(N) for the continental thunderstorms developing in subtropical and tropical airmasses, respectively. If we assume, that these different types of thunderstorms are typical thunderstorms globally (LIS flash rate ~44 s−1), the annual global LNOx production rate based on Hector would be ~5.7–6.6 Tg(N) a−1 and based on the continental thunderstorms developing in subtropical and tropical airmasses ~7.6 and ~2.4 Tg(N) a−1, respectively. The latter thunderstorm type produced much less LNOx per flash compared to the subtropical and Hector thunderstorms, which may be caused by the shorter mean flash component length observed in this storm. It is suggested that the vertical wind shear influences the horizontal extension of the charged layers, which seems to play an important role for the flash lengths that may originate. In addition, the horizontal dimension of the anvil outflow and the cell organisation within the thunderstorm system are probably important parameters influencing flash length and hence LNOx production per flash.

In-situ measurements of oxygen, carbon monoxide and greenhouse gases from Ochsenkopf tall tower in Germany

Abstract. We present 2.5 years (from June 2006 to December 2008) of in-situ measurements of CO2, O2, CH4, CO, N2O and SF6 mixing ratios sampled from 23, 90 and 163 m above ground on the Ochsenkopf tower in the Fichtelgebirge range, Germany (50°01'49" N, 11°48'30" E, 1022 m a.s.l.). In addition to the in-situ measurements, flask samples are taken at Ochsenkopf at approximately weekly intervals and are subsequently analysed for the mixing ratios of the same species, as well as H2, and the stable isotopes, δ13C, δ18O in CO2. The in-situ measurements of CO2 and O2 from 23 m show substantial diurnal variations that are modulated by biospheric fluxes, combustion of fossil fuels, and by diurnal changes in the planetary boundary layer height. Measurements from 163 m exhibit only very weak diurnal variability, as this height (1185 m a.s.l.) is generally above the nocturnal boundary layer. CH4, CO, N2O and SF6 show little diurnal variation even at 23 m owing to the absence of any significant diurnal change in the fluxes and the absence of any strong local sources or sinks. From the in-situ record, the seasonal cycles of the gas species have been characterized and the multi-annual trends determined. Because the record is short, the calculation of the trend is sensitive to inter-annual variations in the amplitudes of the seasonal cycles. However, for CH4 a significant change in the growth-rate was detected for 2006.5–2008.5 as compared with the global mean from 1999 to 2006 and is consistent with other recent observations of a renewed increasing global growth rate in CH4 since the beginning of 2007.

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.

Evaluation of CLaMS, KASIMA and ECHAM5/MESSy1 simulations in the lower stratosphere using observations of Odin/SMR and ILAS/ILAS-II

Abstract. 1-year data sets of monthly averaged nitrous oxide (N2O) and ozone (O3) derived from satellite measurements were used as a tool for the evaluation of atmospheric photochemical models. Two 1-year data sets, one solar occultation data set derived from the Improved Limb Atmospheric Spectrometer (ILAS and ILAS-II) and one limb sounding data set derived from the Odin Sub-Millimetre Radiometer (Odin/SMR) were employed. Here, these data sets are used for the evaluation of two Chemical Transport Models (CTMs), the Karlsruhe Simulation Model of the Middle Atmosphere (KASIMA) and the Chemical Lagrangian Model of the Stratosphere (CLaMS) as well as for one Chemistry-Climate Model (CCM), the atmospheric chemistry general circulation model ECHAM5/MESSy1 (E5M1) in the lower stratosphere with focus on the Northern Hemisphere. Since the Odin/SMR measurements cover the entire hemisphere, the evaluation is performed for the entire hemisphere as well as for the low latitudes, midlatitudes and high latitudes using the Odin/SMR 1-year data set as reference. To assess the impact of using different data sets for such an evaluation study we repeat the evaluation for the polar lower stratosphere using the ILAS/ILAS-II data set. Only small differences were found using ILAS/ILAS-II instead of Odin/SMR as a reference, thus, showing that the results are not influenced by the particular satellite data set used for the evaluation. The evaluation of CLaMS, KASIMA and E5M1 shows that all models are in agreement with Odin/SMR and ILAS/ILAS-II. Differences are generally in the range of ±20%. Larger differences (up to −40%) are found in all models at 500±25 K for N2O mixing ratios greater than 200 ppbv, thus in air masses of tropical character. Generally, the largest differences were found for the tropics and the lowest for the polar regions. However, an underestimation of polar winter ozone loss was found both in KASIMA and E5M1 both in the Northern and Southern Hemisphere.

Additional stratospheric NOx production by relativistic electron precipitation during the 2004 spring NOx descent event

We analyze in detail the February 2004 Global Ozone Monitoring by Occultation of Stars (GOMOS) NO2 observations in the northern polar latitudes during the springtime descent of NOx from the mesosphere into the stratosphere. We combine GOMOS observations with SABER‐observed NO 5.3 μm radiated power and an AARDDVARK‐derived radio wave index (RWI) to describe the impact of the 11 February geomagnetic storm. Energetic electron precipitation generated some additional NOx, supplementing the original amounts that were already descending. At altitudes of 50–70 km, GOMOS observations of NO2 showed a delayed response to the geomagnetic storm, with NO2 being generated 3 days after the start of the storm. The delayed response and duration of NO2 production was found to be consistent with the increase in the flux of relativistic electrons measured by GOES at geostationary orbit and by POES through relativistic electron contamination of the >16 MeV proton channel. Using the Sodankylä Ion and Neutral Chemistry model (SIC), we found that a good fit to the observed NO2 mixing ratios at the peak of the geomagnetic storm effect was produced by a monoenergetic 1.25 MeV electron beam with a flux of ∼0.3 × 106 el cm−2 sr−1 s−1 keV−1 or with a “hard” electron spectra taken from Gaines et al. (1995) but with fluxes enhanced by a factor of 15, i.e., 8 × 104 el cm−2 sr−1 s−1 for 2–6 MeV. Prior to the storm the descending NO2 had average mixing ratio values of ∼150 ppbv. The geomagnetic storm–induced relativistic electron precipitation event doubled the amount of NOx descending into the stratosphere to ∼300 ppbv after the storm.

High spatial resolution measurements of NO<sub>2</sub> applying Topographic Target Light scattering-Differential Optical Absorption Spectroscopy (ToTaL-DOAS)

Abstract. Topographic Target Light scattering – Differential Optical Absorption Spectroscopy (ToTaL-DOAS), also called Target-DOAS, is a novel experimental procedure to retrieve trace gas concentrations present in the low atmosphere. Scattered sunlight (diffuse or specular) reflected from natural or artificial targets located at different distances are analyzed to retrieve the spatial distribution of the concentration of different trace gases like NO2, SO2 and others. We report high spatial resolution measurements of NO2 mixing ratios in the city of Montevideo (Uruguay) observing three buildings as targets with a Mini-DOAS instrument. Our instrument was 146 m, 196 m, and 280 m apart from three different buildings located along a main Avenue. We obtain temporal variation of NO2 mixing ratios between 30 ppb and 65 ppb from measurements of November 2007 and mixing ratios up to 50 ppb from measurements of August and September 2008. Our measurements demonstrate that ToTaL-DOAS observations can be made over relative short distances. In polluted air masses, the retrieved absorption signal was found to be sufficiently strong to allow measurements over distances in the range of several tens of meters.

Measurements of HNO<sub>3</sub> and N<sub>2</sub>O<sub>5</sub> using ion drift-chemical ionization mass spectrometry during the MILAGRO/MCMA-2006 campaign

Abstract. An ion drift-chemical ionization mass spectrometer (ID-CIMS) was deployed in Mexico City between 7 and 31 March to measure gas-phase nitric acid (HNO3) and dinitrogen pentoxide (N2O5 during the Mexico City Metropolitan Area (MCMA)-2006 field campaign. The observation site was located at the Instituto Mexicano del Petróleo in the northern part of Mexico City urban area with major emissions of pollutants from residential, vehicular and industrial sources. Diurnally, HNO3 was less than 200 parts per trillion (ppt) during the night and early morning. The concentration of HNO3 increased steadily from around 09:00 a.m. central standard time (CST), reached a peak value of 0.5 to 3 parts per billion (ppb) in the early afternoon, and then declined sharply to less than half of the peak value near 05:00 p.m. CST. An inter-comparison between the ID-CIMS and an ion chromatograph/mass spectrometer (ICMS) showed a good agreement between the two HNO3 measurements (R2=0.75). The HNO3 mixing ratio was found to anti-correlate with submicron-sized aerosol nitrate, suggesting that the gas-particle partitioning process was a major factor in determining the gaseous HNO3 concentration. Losses by irreversible reactions with mineral dust and via dry deposition also could be important at this site. Most of the times during the MCMA 2006 field campaign, N2O5 was found to be below the detection limit (about 30 ppt for a 10 s integration time) of the ID-CIMS, because of high NO mixing ratio at the surface (>100 ppb) during the night. An exception occurred on 26 March 2006, when about 40 ppt N2O5 was observed during the late afternoon and early evening hours under cloudy conditions before the build-up of NO at the surface site. The results revealed that during the MCMA-2006 field campaign HNO3 was primarily produced from the reaction of OH with NO2 and regulated by gas/particle transfer and dry deposition. The production of HNO3 from N2O5 hydrolysis during the nighttime was small because of high NO and low O3 concentrations near the surface.

Formation of Nitro Products from the Gas-Phase OH Radical-Initiated Reactions of Toluene, Naphthalene, and Biphenyl: Effect of NO2Concentration

Aromatic hydrocarbons, including polycyclic aromatic hydrocarbons (PAHs), are released into the atmosphere principally during incomplete combustion and account for approximately 20% of nonmethane organic compounds in urban air. Reaction with OH radicals is the dominant atmospheric chemical loss process for aromatic hydrocarbons, leading mainly to the formation of an OH-aromatic or OH-PAH adduct which then reacts with O2 and/or NO2. For OH-monocyclic aromatic adducts, reaction with O2 dominates under atmospheric conditions; however, no data are available concerning the relative importance of reactions of OH-PAH adducts with O2 and NO2. We have measured formation yields of 3-nitrotoluene, 1- and 2-nitronaphthalene, and 3-nitrobiphenyl from the OH radical-initiated reactions of toluene, naphthalene, and biphenyl as a function of NO2 concentration. Our data showthatthe OH-aromatic adduct reactions with O2 and NO2 are of equal importance in the atmosphere at NO2 mixing ratios of approximately 3.3 ppmV for toluene, approximately 0.06 ppmV for naphthalene, and approximately 0.6 ppmV for biphenyl. Ambient concentrations of toluene, naphthalene, and biphenyl and their nitrated products measured at a site in the Los Angeles air basin are consistent with our laboratory measurements.

Long-term observation of mass-independent oxygen isotope anomaly in stratospheric CO<sub>2</sub>

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>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.

Measurement-based modeling of bromine chemistry in the Dead Sea boundary layer – Part 2: The influence of NO<sub>2</sub> on bromine chemistry at mid-latitude areas

Abstract. Understanding the interaction between anthropogenic air pollution and Reactive Halogen Species (RHS) activity has had only limited support from direct field measurements, due to the fact that past field measurements of RHS have been mainly performed in Polar Regions. The present paper investigates the interaction between NO2 and Reactive Bromine Species (RBS) activity by model simulations based on extensive field measurements performed in the Dead Sea area, as described in a companion paper (Tas et al., 2006). The Dead Sea is an excellent natural laboratory for this investigation since elevated mixing ratios of BrO (up to more than 150 pptv) are frequently observed, while the average levels of NO2 are around several ppb. The results of the present study show that under the chemical mechanisms that occur at the Dead Sea, higher levels of NO2 lead to higher daily average mixing ratios of BrOx. This is the result of an increase in the rate of the heterogeneous decomposition of BrONO2, which in turn causes an increase in the rate of the "Bromine Explosion" mechanism. However, above a certain threshold level of NO2 (daily average mixing ratios of 0.2 ppbv during RBS activity), the daily average mixing ratios of BrOx decrease for a further increase in the NO2 mixing ratios. This investigation shows that the influence of NO2 on BrOx production clearly reflects an enhancement of RBS activity caused by anthropogenic activity.

Evaluation of a new lightning-produced NO<sub>x</sub> parameterization for cloud resolving models and its associated uncertainties

Abstract. A new parameterization of the lightning-produced NOx has been developed for cloud-resolving models. This parameterization is based on the unique characteristics of identifying which convective cells are capable of producing lightning based on a vertical velocity threshold and estimating the lightning flash rate in each convective cell from the non-precipitation and precipitation ice mass flux product. Further, the source location is filamentary instead of volumetric as in most previous parameterizations. This parameterization has been tested on the 10 July 1996 Stratospheric-Tropospheric Experiment: Radiation, Aerosols and Ozone (STERAO) storm. Comparisons of the simulated flash rate and NO mixing ratio (control experiment) with observations at different locations and stages of the storm show good agreement. An individual flash produces on average 121±41 moles of NO (7.3±2.5×1025 molecules NO) for the simulated high cloud base, high shear storm that is dominated by intra-cloud flash activity. Sensitivity tests have been performed to study the impact of the flash rate, the cloud-to-ground flash ratio, the flash length, the spatial distribution of the NO molecules, and the production rate per flash on the NO concentration and distribution. Results show a strong impact from the flash rate, the spatial placement of the lightning-NOx source and the number of moles produced per flash. On the other hand, the simulations show almost no impact from the different cloud-to-ground (CG) ratios and the lightning-NOx production rates per CG flash used as input to the model.

Urban photochemistry in central Tokyo: 2. Rates and regimes of oxidant (O3 + NO2) production

Net photochemical production rates of oxidant (Ox = O3 + NO2), F‐D(Ox), were determined in Tokyo during the winter and summer of 2004 using observed and calculated HO2 radical concentrations. In both cases, calculated RO2 (organic peroxy) radical concentrations were used. The rates calculated using the two HO2 data sets are similar. In summer, morning F‐D(Ox) values on smog days (those with midday O3 concentrations exceeding 100 ppbv) were higher than those on smog‐free days (with typical midday O3 concentrations of 30 ppbv); however, the amount of ozone produced in a single day, as estimated by integrating F‐D(Ox) over the daytime, was not significantly different for the two periods. This analysis suggests that the occurrence of smog events in the city center cannot readily be explained by day‐to‐day variations in the strength of in situ photochemistry. On smog days, the coupling of photochemistry and meteorology appears to be important, as air masses in which oxidants accumulated over successive days arrive at the city center at approximately midday, transported by land‐sea breeze circulation. The average maximum daytime F‐D(Ox) values in summer, 11 and 13 ppbv h−1 using observed and calculated HO2 levels, respectively, were only 1.5 and 2.2 times higher than those in winter (8 and 6 ppbv h−1). In winter, an underestimation of HO2 levels at high NO concentrations resulted in an underestimation of F‐D(Ox) when calculated using modeled HO2. While the model predicted a volatile organic compounds (VOC)‐limited regime for Ox production in winter, F‐D(Ox) based on observed HO2 did not show features of the VOC‐limited regime and only steadily increased with increasing NO mixing ratio, even when it exceeded 20 ppbv. In summer, the dependence of F‐D(Ox) on nonmethane hydrocarbons (NMHCs) and NOx concentrations was similar in the two cases, in which observed and calculated HO2 levels were used. A VOC‐limited regime, predicted on smog‐free days, changed to a NOx‐limited regime on smog days. The F‐D(Ox) values determined for Tokyo are also compared with values for other cities.

Description and validation of a limb scatter retrieval method for Odin/OSIRIS

In this paper we present the Modified Onion Peeling (MOP) inversion method, which is for the first time used to retrieve vertical profiles of stratospheric trace gases from Odin/OSIRIS limb scatter measurements. Since the original publication of the method in 2002, the method has undergone major modifications discussed here. The MOP method now uses a spectral microwindow for the NO2 retrieval, instead of the wide UV‐visible band used for the ozone, air, and aerosol retrievals. We give a brief description of the algorithm itself and show its performance with both simulated and real data. Retrieved ozone and NO2 profiles from the OSIRIS measurements were compared with data from the GOMOS and HALOE instruments. No more than 5% difference was found between OSIRIS daytime and GOMOS nighttime ozone profiles between 21 and 45 km. The difference between OSIRIS and HALOE sunset NO2 mixing ratio profiles was at most 25% between 20 and 40 km. The neutral air density was compared with the ECMWF analyzed data and around 5% difference was found at altitudes from 20 to 55 km. However, OSIRIS observations yield as much as 80% greater aerosols number density than GOMOS observations between 15 and 35 km. These validation results indicate that the quality of MOP ozone, NO2, and neutral air is good. The new version of the method introduced here is also easily expanded to retrieve additional species of interest.

Urban photochemistry in central Tokyo: 1. Observed and modeled OH and HO2 radical concentrations during the winter and summer of 2004

We used laser‐induced fluorescence to measure the concentrations of OH and HO2 radicals in central Tokyo during two intensive campaigns (IMPACT IV and IMPACT L) in January–February and July–August 2004. The estimated detection limit for the 10‐min data was 1.3 × 105 cm−3 for the nighttime and 5.2 × 105 cm−3 for the daytime. The median values of the daytime peak concentrations of HO2 were 1.1 and 5.7 pptv for the winter and summer periods, respectively, while the values for OH were 1.5 × 106 and 6.3 × 106 cm−3. High HO2 mixing ratios (>50 pptv) were observed on a day in summer when O3 mixing ratios exceeded 100 ppbv. The average nighttime concentrations of HO2 were 0.7 and 2.6 pptv for the winter and summer periods, respectively, while the values for OH were 1.8 × 105 and 3.7 × 105 cm−3. A photochemical box model constrained by ancillary observations was able to reproduce daytime OH concentrations reasonably well for both periods, although daytime HO2 concentrations were underestimated in winter and overestimated in summer. Increasing the wintertime hydrocarbon concentrations in the model led to an increase in daytime HO2 concentrations, thereby showing better agreement with observations; however, the model continued to underestimate HO2 concentrations at high NO mixing ratios. This underestimate was most pronounced in the mornings of both periods and during the daytime in winter. We studied processes that are capable of explaining this discrepancy, including unknown reactions of HNO4 or an unidentified HOx source that is linearly scalable to the NO mixing ratio. The important processes in terms of producing radicals were the olefin + O3 reactions in the nighttime of both periods and during the daytime in winter, the photolysis of carbonyls in the daytime for both periods, and the photolysis of HONO during the daytime in winter (using measured HONO concentrations) and during mornings in summer (using estimated HONO concentrations).