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Multilayer diffraction gratings are designed to improve the detection limit and sensitivity of soft x-ray flat-field spectrographs in the region of 300–1000 eV, placing emphasis on Fe-L (705 eV), Cu-L (930 eV), and Zn-L (1012 eV) emissions. For this purpose, spectral flux was used as the performance index, which is proportional to the amount of optical flux incident into a detector and correlated with detection sensitivity. A super-mirror-type W/B4C multilayer coating [Koike et al., Rev.Sci. Instrum. 94, 045109 (2023)] was employed to improve diffraction efficiency in a wide energy region. The unique feature of the multilayer structure is that the average refractive index and the period length of W/B4C layer pairs are increased from the bottom to top layers. In addition, the incidence angle was reduced to 86.03° from 88.65° and the nominal groove density was increased to 3200 lines/mm from 2400 lines/mm of our previous design, to improve spectral flux while maintaining dispersion and spectral resolution. A holographic varied-line-spacing spherical grating and a soft x-ray flat-field spectrograph were designed, using the aspherical-wavefront-recording method, assuming the nominal grating constant and incident angle described above. The numerical simulation results showed that the spectrograph employing the newly designed grating with the W/B4C multilayer indicated 3.2–8.2 times higher spectral flux compared with those using the previously designed grating while keeping the same spectral resolution. [ABSTRACT FROM AUTHOR]

Extensive measurements of black carbon (BC) aerosol were conducted in and near the North American Arctic during the Arctic Research of the Composition of the Troposphere from Aircraft and Satellites (ARCTAS) aircraft campaign in April and June-July 2008. We identify the pathways and mechanisms of transport of BC to the Arctic from the Asian continent using these data. The concentration, transport efficiency, and measured altitude of BC over the North American Arctic were highly dependent on season and origin of air parcels, e.g., biomass burning (BB) in Russia (Russian BB) and anthropogenic (AN) in East Asia (Asian AN). Russian BB air was mainly measured in the middle troposphere and caused maximum BC concentrations at this altitude in spring. The median BC concentration and transport efficiency of the Russian BB air were 270 ng m -3 (at STP) and 80% in spring and 20 ng m-3 and 4% in summer, respectively. Asian AN air was measured most frequently in the upper troposphere, with median values of 20 ng m-3 and 13% in spring and 5 ng m-3 and 0.8% in summer. These distinct differences are explained by differences in the transport mechanisms and accumulated precipitation along trajectories (APT), which is a measure of wet removal processes during transport. The transport of Russian BB air to the Arctic was nearly isentropic with slow ascent (low APT), while Asian AN air underwent strong uplift associated with warm conveyor belts (high APT). The APT values in summer were much larger than those in spring due to the increase in humidity in summer. These results show that the impact of BC emitted from AN sources in East Asia on the Arctic was very limited in both spring and summer. The BB emissions in Russia in spring are demonstrated to be the most important sources of BC transported to the North American Arctic. Copyright 2011 by the American Geophysical Union.

We evaluate the impact of transport from midlatitudes on aerosol number concentrations in the accumulation mode (light-scattering particles (LSP) with diameters >180 nm) in the Arctic during the Arctic Research of the Composition of the Troposphere from Aircraft and Satellites (ARCTAS) campaign. We focus on transport from the Asian continent. We find marked contrasts in the number concentration (NLSP), transport efficiency (TE N-LSP, the fraction transported from sources to the Arctic), size distribution, and the chemical composition of aerosols between air parcels from anthropogenic sources in East Asia (Asian AN) and biomass burning sources in Russia and Kazakhstan (Russian BB). Asian AN air had lower NLSP and TEN-LSP (25 cm-3 and 18% in spring and 6.2 cm-3 and 3.0% in summer) than Russian BB air (280 cm-3 and 97% in spring and 36 cm-3 and 7.6% in summer) due to more efficient wet scavenging during transport from East Asia. Russian BB in this spring is the most important source of accumulation-mode aerosols over the Arctic, and BB emissions are found to be the primary source of aerosols within all the data in spring during ARCTAS. On the other hand, the contribution of Asian AN transport had a negligible effect on the accumulation-mode aerosol number concentration in the Arctic during ARCTAS. Compared with background air, NLSP was 2.3-4.7 times greater for Russian BB air but 2.4-2.6 times less for Asian AN air in both spring and summer. This result shows that the transport of Asian AN air decreases aerosol number concentrations in the Arctic, despite the large emissions of aerosols in East Asia. The very low aerosol number concentrations in Asian AN air were caused by wet removal during vertical transport in association with warm conveyor belts (WCBs). Therefore, this cleansing effect will be prominent for air transported via WCBs from other midlatitude regions and seasons. The inflow of clean midlatitude air can potentially have an important impact on accumulation-mode aerosol number concentrations in the Arctic. Copyright 2011 by the American Geophysical Union.

Regional aerosol model calculations were made using the Weather Research and Forecasting (WRF)-Community Multiscale Air Quality (CMAQ) and WRF-chem models to study spatial and temporal variations of aerosols around Beijing, China, in the summer of 2006, when the Campaigns of Air Quality Research in Beijing and Surrounding Region 2006 (CAREBeijing) intensive campaign was conducted. Model calculations captured temporal variations of primary (such as elemental carbon. (EC)) and secondary (such as sulfate) aerosols observed in and around Beijing. The spatial distributions of aerosol optical depth observed by the MODTS satellite sensors were also reproduced over northeast China. Model calculations showed distinct differences in spatial distributions between primary and secondary aerosols in association with synoptic-scale meteorology. Secondary aerosols increased in air around Beijing on a scale of about 1000 × 1000 km2 under an anticyclonic pressure system. This air mass was transported northward from the high anthropogenic emission area extending south of Beijing with continuous photochemical production. Subsequent cold front passage brought clean air from the north, and polluted air around Beijing was swept to the south of Beijing. This cycle was repeated about once a week and was found to be responsible for observed enhancements/reductions of aerosols at the intensive measurement sites. In contrast to secondary aerosols, the spatial distributions of primary aerosols (EC) reflected those of emissions, resulting in only slight variability despite the changes in synopticscale meteorology. In accordance with these results, source apportionment simulations revealed that primary aerosols around Beijing were controlled by emissions within 100 km around Beijing within the preceding 24 h, while emissions as far as 500 km and within the preceding 3 days were found to affect secondary aerosols. Copyright 2009 by the American Geophysical Union.

Measurements of the major reactive nitrogen species (NOy)i (NOx, peroxyacyl nitrates, HNO3, and particulate nitrate (NO3-), total reactive nitrogen (NOy), volatile organic compounds, OH and HO2, and organic aerosol were made near the urban center of Tokyo in different seasons of 2003-2004 to study the processes involving oxidized forms of reactive nitrogen and O3. Generally, NOx constituted the dominant fraction of NOy throughout the seasons. The NOx/NOy and HNO3/NOy ratios were lowest and highest, respectively, in summer, owing to the seasonally high OH concentration. The fraction of NOy that remained in the atmosphere after emission (RNOy) decreased with the decrease in the NOx/NOy ratio in summer and fall. It is likely that the median seasonal-diurnal variations Of Ox = O3 + NO2 were controlled by those of the background O3 levels, photochemical O3 formation, and vertical transport. Ox showed large increases during midday under stagnant conditions in mid-August 2004. Their in situ production rates calculated by a box model were too slow to explain the observed increases. The high Ox was likely due to the accumulation of Ox from previous days in the upper part of the boundary layer (BL) followed by transport down to near the surface by mixing after sunrise. Considering the tight correlation between Ox and secondary organic aerosol (SOA), it is likely that SOA also accumulated during the course of sea-land breeze circulation in the BL. Copyright 2008 by the American Geophysical Union.

The seasonal variation of ozone (O3) in the boundary layer (BL) over the western Pacific is investigated using a chemistry-transport model. The model results for January and April-May 2002 were evaluated by comparison with PEACE aircraft observations. In January, strong northwesterlies efficiently transported NOx from the continent, leading to an O3 increase of approximately 5-10 ppbv over a distance of about 3000 km. In April, southwesterlies dominated due to anticyclone development over the western Pacific. Along this flow, O3 continued to be produced by NO x emitted from East Asia. This resulted in the formation of a high-O3 (> 50 ppbv) region extending along the coastal areas of East Asia. This seasonal change in O3 was driven in part by a change in the net O3 production rate due to increases in solar UV and H 2O. Its exact response depended on the NOx values in the BL. The net O3 production rate increased between winter and spring over the Asian continent and decreased over the remote western Pacific. Model simulations show that about 25% of the total O3 (of 10-20 ppbv) increase over the coastal region of Northeast Asia was due to local production from NOx emissions from China, and the rest was due to changes in background levels as well as emissions from Korea, Japan, and east Siberia. Uplift of BL air over Asia, horizontal transport in the free troposphere, and subsidence were the principal mechanisms of transporting Asian O3 to the central and eastern North Pacific Copyright 2008 by the American Geophysical Union.

Eighteen C2-C7 NMHCs (nonmethane hydrocarbons) were measured hourly during the Integrated Measurement Program for Aerosol and Oxidant Chemistry in Tokyo (IMPACT) measurement campaigns conducted in central Tokyo during four different periods (summer/autumn of 2003 and winter/summer of 2004). The ambient atmospheric concentrations of NMHCs showed an inverse correlation with wind speed and mixing height and were significantly affected by mesoscale weather conditions. The mixing ratio of isoprene tightly correlated with solar flux and temperature in summer, as it was dominantly emitted by the local vegetation. All the observed NMHCs except isoprene showed high correlation with each other in winter (r2 > 0.5), suggesting concurrent accumulation under stagnant condition and common sources. Emission ratios were calculated on the basis of the correlation with carbon monoxide and ethyne. Compared to the typical winter NMEC composition, during summer there was a significant increase (up to 7 times higher than wintertime) of C4-C5 alkanes from ftiel evaporation; of C2-C3 alkenes, n-hexane and benzene from chemical industry; and of toluene from local manufacturers, reflecting the temperature dependence of these evaporative emissions. In addition to the online measurements in Tokyo, canister sampling at a suburban site (Kisai) followed by multidimensional GC analyses was conducted during the summer campaign in 2004. The atmospheric concentrations of longer-lived compounds (≥ several days) at Kisai showed the buildup under sea breeze circulation. The average ambient, concentration of toluene was 2 times higher than that in central Tokyo, likely because of substantial emissions from local industries as reported in the prefectural statistics. Copyright 2007 by the American Geophysical Union.

The Biomass Burning and Lightning Experiment phase C (BIBLE-C) aircraft mission was carried out near Darwin, Australia (12°S, 131°E) in December 2000. This was the first aircraft experiment designed to estimate lightning NO production rates in the tropics, where production is considered to be most intense. During the two flights (flights 10 and 13 made on December 9 and 11-12, respectively) enhancements of NOx (NO + NO2) up to 1000 and 1600 parts per trillion by volume (pptv, 10-s data) were observed at altitudes between 11.5 and 14 km. The Geostationary Meteorological Satellite (GMS) cloud (brightness temperature) data and ground-based lightning measurements by the Global Positioning and Tracking System (GPATS) indicate that there were intensive lightning events over the coast of the Gulf of Carpentaria, which took place upstream from our measurement area 10 to 14 h prior to the measurements. For these two flights, air in which NOx exceeded 100 pptv extended over 620 × 140 and 400 × 170 km2 (wind direction x perpendicular direction), respectively, suggesting a significant impact of lightning NO production on NOx levels in the tropics. We estimate the amount of NOx observed between 11.5 and 14 km produced by the thunderstorms to be 3.3 and 1.8 × 1025 NO molecules for flights 10 and 13, respectively. By using the GPATS lightning flash count data, column NO production rates are estimated to be 1.9-4.4 and 21-49 × 1025 NO molecules per single flash for these two flight data sets. In these estimations, it is assumed that the column NO production between 0 and 16 km is greater than the observed values between 11.5 and 14 km by a factor of 3.2, which is derived using results reported by Pickering et al. (1998). There are however large uncertainties in the GPATS lightning data in this study and care must be made when the production rates are referred. Uncertainties in these estimates are discussed. The impact on the ozone production rate is also described. Copyright 2007 by the American Geophysical Union.

We report the evolution of the mixing state of black carbon (BC) particles in urban plumes measured by an airborne single particle soot photometer. The aircraft observations were conducted over the ocean near the coast of Japan in March 2004. The number fiaction of coated BC particles with a core diameter of 180 mn increased from 0.35 to 0.63 within 12 hours (h), namely 2.3% h-1, after being emitted from the Nagoya urban area in Japan. BC particles with a core diameter of 250 nm increased at the slower rate of 1.0% h-1. The increase in coated BC particles was associated with increases in non-sea salt sulfate and water-soluble organic carbon by a factor of approximately two, indicating that these compounds contributed to the coating on the BC particles. These results give direct evidence that BC particles become internally mixed on a time scale of 12 h in urban plumes. Copyright 2007 by the American Geophysical Union.

Laminar-type spherical diffraction gratings overcoated with carbon-based materials were designed, fabricated, and evaluated for the purpose of enhancing the analytical sensitivity of the flat-field spectrograph in a vacuum ultraviolet region of 35–110 eV. As the design benchmark for numerical calculations, diffraction efficiency (DE) and spectral flux, which are defined by the product of the DE and numerical aperture and correlate with the analytical sensitivity of the spectrograph, were used. To simplify the feasibility study on the overcoating effects, we assumed a laminar-type grating having a grating constant of 1/1000 mm and coated with a Au layer of 30.0 nm thickness and an incidence angle of 84.0°. The optimized groove depth and duty ratio were 30.0 nm and 0.3, respectively. In addition, the optimum thicknesses of the overcoating layer were 44, 46, 24, and 30 nm for B4C, C, diamond-like-carbon, and SiC, respectively. Based on these results, we have fabricated a varied-line-spacing holographic grating overcoated with B4C with a thickness of 47 nm. For the experimental evaluation, we used the light source of Mg-L and Al-L emissions excited by the electron beam generated from an electron microscope, an objective flat-field spectrograph, and a CCD imaging detector. The experimental results showed that the spectrograph employing a new grating overcoated with the B4C layer indicated almost the same spectral resolution and 2.9–4.2 times higher analytical sensitivity compared with those obtained with a previously designed Au-coated grating having a grating constant of 1/1200 mm and used at an incidence of 86.0°. [ABSTRACT FROM AUTHOR]

[ 1] Tropospheric carbon monoxide ( CO) was measured throughout 2001 using groundbased Fourier transform IR ( FTIR) spectrometers at Moshiri (44.4 degrees N) and Rikubetsu (43.5 degrees N) observatories in northern Japan, which are separated by 150 km. Seasonal and day-to-day variations of CO are studied using these data, and contributions from various CO sources are evaluated using three-dimensional global chemistry transport model (GEOS-CHEM) calculations. Seasonal maximum and minimum FTIR-derived tropospheric CO amounts occurred in April and September, respectively. The ratio of partial column amounts between the 0 - 4 and 0 - 12 km altitude ranges is found to be slightly greater in early spring. The GEOS-CHEM model calculations generally reproduce these observed features. Source-labeled CO model calculations suggest that the observed seasonal variation is caused by seasonal contributions from various sources, in addition to a seasonal change in chemical CO loss by OH. Changes in meteorological fields largely control the relative importance of various source contributions. The contributions from fossil fuel (FF) combustion in Asia and photochemical CO production have the greatest yearly averaged contribution at 1 km among the CO sources (31% each). The Asian FF contribution increases from winter to summer, because weak southwesterly wind in summer brings more Asian pollutants to the observation sites. The seasonal variation from photochemical CO production is small ( +/- 17% at 1 km), likely because of concurrent increases ( decreases) of photochemical production and loss rates in summer ( winter), with the largest contribution between August and December. The contribution from intercontinental transport of European FF combustion CO is found to be comparable to that of Asian FF sources in winter. Northwesterly wind around the Siberian high in this season brings pollutants from Europe directly to Japan, in addition to southward transport of accumulated pollution from higher latitudes. The influences are generally greater at lower altitudes, resulting in a vertical gradient in the CO profile during winter. The model underestimates total CO by 12 - 14% between March and June. Satellite-derived fire-count data and the relationship between FTIR-derived HCN and CO amounts are generally consistent with biomass burning influences, which could have been underestimated by the model calculations.

Ground-based measurements of aerosols and trace gases were conducted at an urban site in Tokyo (Komaba) and a site 50 km to the north (Kisai) during July-August 2004. An Aerodyne aerosol mass spectrometer (AMS) was deployed at each measurement site to investigate the chemical evolution of submicron organic aerosol (OA) in polluted air. The mass concentrations of OA at the Kisai site were systematically higher than those at the Komaba site and were correlated with ozone under southerly conditions. The rate of increase of OA at the Kisai site is investigated using the photochemical age derived from the ratio of alkyl nitrates to their parent hydrocarbons. The OA concentrations in processed air (age of 8-16 h) were 4-5 times larger than those in fresh emissions (age ∼ 0), suggesting that the OA concentrations can be significantly enhanced within ∼0.5 days under conditions of high photochemical activity. Copyright 2006 by the American Geophysical Union.

Simultaneous measurements of speciated, total reactive nitrogen (NOy) and particulate NO3 (particle diameter

Aircraft measurements of ozone (O3) and its precursors, including NO, CO, H2O, and nonmethane hydrocarbons (NMHCs), were made over the western Pacific in the 20° - 45°N latitude range in January and April-May 2002 during the Pacific Exploration of Asian Continental Emission (PEACE)-A and B campaigns. These measurements have provided data sets that, in combination with Transport and Chemical Evolution over the Pacific (TRACE-P) data taken in March 2001, enable studies of O3 photochemistry from winter to late spring. A photochemical box model is used to calculate ozone formation (F(O3)) and destruction (D(O3)) rates constrained by the observed species concentrations. The values of F(O3) and D(O3) are controlled directly by NO, J(O1D) (O3 photolysis frequency), H2O, OH, and HO2. Changes in HO2 concentration cause corresponding changes in both F(O3) and D(O3) leading to their coupling. Concentrations of these species, which are strongly influenced by photochemistry and transport from the Asian continent, underwent large seasonal variations. In the boundary layer (0-3 km), NO was much higher in January than in April-May, because of stronger winds, lower convective activities, and lower oxidation rates by OH in winter. The net O3 formation rate, given by P(O3) = F(O3) - D(O3), was largely positive in the boundary layer at 30°-45°N (1.5-4 ppbv d-1) in January, mainly because of high NO and low H2O values. Net O3 formation continued from January to the end of March, demonstrating that the western Pacific is an important O3 source region during this season. Net O3 formation nearly ceased by late April/May because of the decrease in NO and the increase in H2O. In the latitude range of 20°-30°N, P(O3) in the boundary layer was positive in January and turned negative by March. The earlier transition was mainly due to lower NO and higher H2O concentrations, combined with weaker transport and higher temperatures than those at 30°-45°N. The upper troposphere (6-12 km) has been shown to be a region of net O3 formation throughout most of the year because of high NO and low H2O. The present study illustrates that a decrease in the net O3 formation rate at 20°-45°N latitude from winter to late spring is explained systematically by the increases in J(O1D), H2O, OH, and HO2 (primarily due to increases in temperature and solar radiation) and the decrease in NO (primarily due to decrease in transport from the Asian continent). Differences in the seasonal variation of O3 photochemistry observed over the North American continent are interpreted in terms of the differences in factors controlling O3 formation and destruction. Copyright 2004 by the American Geophysical Union.

The Pacific Exploration of Asian Continental Emission Phase A (PEACE-A) aircraft measurement campaign was conducted over the western Pacific in January 2002. Correlations of carbon monoxide (CO) with carbon dioxide (CO2) and back trajectories are used to identify plumes strongly affected by Asian continental emissions. ΔCO/ΔCO2 ratios (i.e., linear regression slopes of CO-CO2) in the plumes generally fall within the variability range of the CO/CO2 emission ratios estimated from an emission inventory for east Asia, demonstrating the consistency between the aircraft measurements and the emission characterization. Removal rates of reactive nitrogen (NOx and NOy) for the study region (altitude

The Pacific Exploration of Asian Continental Emission phase B (PEACE-B) aircraft mission was conducted over the western Pacific during April-May 2002. During several flights large enhancements of CO greater than 200 parts per billion by volume (ppbv) were served at altitudes between 5 and 10 km. In this paper, we describe vertical transport mechanisms over east Asia that were responsible for these enhancements, using the European Centre for Medium-Range Weather Forecasts (ECMWF) meteorological data and infrared cloud data obtained by the Geostationary Meteorological Satellite (GMS)-5. A case study for the highest CO event shows that it was likely due to vertical transport of pollutants caused by deep cumulus convection along a quasi-stationary frontal zone, which was formed over central China (around the Yangtze River at 30°N). In the mean meteorological field during the PEACE-B period, the warm, moist low-level southerlies converged into the frontal zone, sustaining cross-frontal temperature and moisture contrasts. Along the frontal zone, the mean vertical motion was distinctively upward, and a subtropical jet aloft was found to transport uplifted air parcels efficiently into the western Pacific. In this study, criteria to identify deep convection are defined using both the ECMWF and GMS data. The results show that convective activity, which was generally high below the subtropical jet, played an important role in producing updrafts over central China. The convective transport resulted mainly from a limited number of episodes, each of which followed the development of a weak cyclonic disturbance. Back trajectories of air parcels sampled at altitudes between 4 and 13 km on board the aircraft during PEACE-B show that among the air parcels originating from the 800-hPa level or below, 69% were likely to have undergone convective uplifting. In addition to convection, sloping isentropes often observed along the quasi-stationary jet axis yielded persistent slow quasi-adiabatic uplifting of air over the Far East, which was occasionally intensified with a classical warm conveyor belt (WCB) airstream on the passage of migratory cyclonic disturbances. Meteorological conditions during PEACE-B were thus favorable for the upliffing of boundary layer air influenced by anthropogenic emissions over central China. These results are consistent with the relatively high levels of Halon 1211 (CF2ClBr), a good tracer of Chinese anthropogenic emissions, observed in the air parcels that were likely uplifted in the frontal zone. Coyright 2004 by the American Geophysical Union.

Aircraft measurements of ozone (O3) and its precursors (reactive nitrogen, CO, nonmethane hydrocarbons) were made over the western Pacific during the Transport and Chemical Evolution Over the Pacific (TRACE-P) campaign, which was conducted during February-April 2001. Biomass burning activity was high over Southeast Asia (SEA) during this period (dry season), and convective activity over SEA frequently transported air from the boundary layer to the free troposphere, followed by eastward transport to the sampling region over the western Pacific south of 30°N. This data set allows for systematic investigations of the chemical and physical processes in the outflow from SEA. Methyl chloride (CH3Cl) and CO are chosen as primary and secondary tracers, respectively, to gauge the degree of the impact of emissions of trace species from biomass burning. Biomass burning is found to be a major source of reactive nitrogen (NO x, PAN, HNO3, and nitrate) and O3 in this region from correlations of these species with the tracers. Changes in the abundance of reactive nitrogen during upward transport are quantified from the altitude change of the slopes of the correlations of these species with CO. NOx decreased with altitude due to its oxidation to HNO3. On the other hand, PAN was conserved during transport from the lower to the middle troposphere, consistent with its low water solubility and chemical stability at low temperatures. Large losses of HNO3 and nitrate, which are highly water soluble, occurred in the free troposphere, most likely due to wet removal by precipitation. This has been shown to be the major pathway of NOy loss in the middle troposphere. Increases in the mixing ratios of O3 and its precursors due to biomass burning in SEA are estimated using the tracers. Enhancements of CO and total reactive nitrogen (NOy), which are directly emitted from biomass burning, were largest at 2-4 km. At this altitude the increases in NOy and O3 were 810 parts per trillion by volume (pptv) and 26 parts per billion by volume (ppbv) above their background values of 240 pptv and 31 ppbv, respectively. The slope of the O3-CO correlation in biomass burning plumes was similar to those observed in fire plumes in northern Australia, Africa, and Canada. The O3 production efficiency (OPE) derived from the O3-CO slope and NOx/CO emission ratio (ER) is shown to be positively correlated with the C2H4 /NOx ER, indicating that the C2H4/NO x ER is a critical parameter in determining the OPE. Comparison of the net O3 flux across the western Pacific region and total O3 production due to biomass burning in SEA suggests that about 70% of O3 produced was transported to the western Pacific. Copyright 2004 by the American Geophysical Union.

In situ aircraft measurements of ozone (O3) and its precursors were made over northern Australia in August-September 1999 during the Biomass Burning and Lightning Experiment Phase B (BIBLE-B). A clear positive correlation of O3 with carbon monoxide (CO) was found in biomass burning plumes in the boundary layer (

The Biomass Burning and Lightning Experiment phase A (BIBLE-A) aircraft observation campaign was conducted from 24 September to 10 October 1998, during a La Niña period. During this campaign, distributions of ozone and its precursors (NO, CO, and nonmethane hydrocarbons (NMHCs)) were observed over the tropical Pacific Ocean, Indonesia, and northern Australia. Mixing ratios of ozone and its precursors were very low at altitudes between 0 and 13.5 km over the tropical Pacific Ocean. The mixing ratios of ozone precursors above 8 km over Indonesia were often significantly higher than those over the tropical Pacific Ocean, even though the prevailing easterlies carried the air from the tropical Pacific Ocean to over Indonesia within several days. For example, median NO and CO mixing ratios in the upper troposphere were 12 parts per trillion (pptv) and 72 parts per billion (ppbv) over the tropical Pacific Ocean and were 83 pptv and 85 ppbv over western Indonesia, respectively. Meteorological analyses and high ethene (C2H4) mixing ratios indicate that the increase of the ozone precursors was caused by active convection over Indonesia through upward transport of polluted air, mixing, and lightning all within the few days prior to observation. Sources of ozone precursors are discussed by comparing correlations of some NMHCs and CH3Cl concentrations with CO between the lower and upper troposphere. Biomass burning in Indonesia was nearly inactive during BIBLE-A and was not a dominant source of the ozone precursors, but urban pollution and lightning contributed importantly to their increases. The increase in ozone precursors raised net ozone production rates over western Indonesia in the upper troposphere, as shown by a photochemical model calculation. However, the ozone mixing ratio (∼20 ppbv) did not increase significantly over Indonesia because photochemical production of ozone did not have sufficient time since the augmentation of ozone precursors. Backward trajectories show that many air masses sampled over the ocean south of Indonesia and over northern Australia passed over western Indonesia 4-9 days prior to being measured. In these air masses the mixing ratios of ozone precursors, except for short-lived species, were similar to those over western Indonesia. In contrast, the ozone mixing ratio was higher by about 10 ppbv than that over Indonesia, indicating that photochemical production of ozone occurred during transport from Indonesia. The average rate of ozone increase (1.8 ppbv/d during this transport is similar to the net ozone formation rate calculated by the photochemical model. This study shows that active convection over Indonesia carried polluted air upward from the surface and had a discernable influence on the distribution of ozone in the upper troposphere over the Indian Ocean, northern Australia, and the south subtropical Pacific Ocean, combined with NO production by lightning.

Aircraft observations of ozone and its precursors (NO, NOy, CO, and nonmethane hydrocarbons) were made near Japan (26°-44°N) between 21 and 24 April 1998 to investigate the effect of transport and chemistry on the tropospheric ozone over east Asia in spring. The average mixing ratios of ozone and its precursors in the upper troposphere were higher than those observed during February-March 1994. Significantly higher values of CO indicate that the influence of surface sources mediated by convection was large throughout the troposphere during the period. Highly polluted air masses were observed in the upper troposphere at 8-11 km over the Japan Sea on 24 April. These air masses were influenced by cumulus convection associated with a cold front over northeast China about 1 day prior to the observation. However, the majority of observed air masses in the upper troposphere were not directly affected by the recent emissions of the ozone precursors from east Asia. Instead, convection over other regions in the northern midlatitude, followed by long-range transport, affected the abundances of ozone precursors in the upper troposphere. In these air masses, ozone was positively correlated with NOx and C3H8, indicating the effect of photochemical ozone production. The diurnal-average column-integrated rate of ozone production, estimated by a photochemical box model, was larger than the NH average and local stratospheric flux at NH midlatitudes in spring by a factor of 3-20. The net production rates in the majority of the air masses were estimated to be 0.5-4.4 ppbv d-1 in the upper troposphere. These results indicate the important role photochemistry plays in controlling the upper tropospheric ozone abundance in spring.

In situ aircraft measurements of trace gases and aerosols were made in the boundary layer (BL) and free troposphere (FT) over Indonesia and Australia during the Biomass Burning and Lightning Experiment (BIBLE)-A and B conducted in August-October 1998 and 1999. Concentrations of ozone (O3) and its precursors [CO, reactive nitrogen (NOx), non-methane hydrocarbons (NMHCs)] were measured in these campaigns to identify the sources of NOx and to estimate the effects of biomass burning and lightning on photochemical production of O3. Over Indonesia, in-situ production of NOx by lightning was found to be a major source of reactive nitrogen in the upper troposphere during BIBLE-A. In some circumstances, increases in reactive nitrogen were often associated with enhancements in CO and NMHCs, suggesting that the sources were biomass burning and fossil fuel combustion, followed by upward transport by cumulus convection. Over Australia the levels of O3, CO, reactive nitrogen, and NMHCs were elevated throughout the troposphere compared to those observed in the tropical Pacific. However, the mechanisms responsible for the enhanced concentrations in the BL and FT are distinctly different. The emissions from biomass burning that occurred in northern Australia were restricted to the BL because of strong subsidence in the period. In the FT over Australia, elevated concentrations of O3 and its precursors result from injections of emissions as the air masses travel over Africa, South America, the Indian Ocean, and Indonesia en route to Australia. In all cases, O3 levels in the biomass burning plumes were enhanced due to photochemical production.