This is the fourth semi-annual report for NAS5-97039, covering the time period July through December 1998. The overall objective of this project is to improve the understanding of coupling processes between atmospheric chemistry and climate. Model predictions of the future distributions of trace gases in the atmosphere constitute an important component of the input necessary for quantitative assessments of global change. We will concentrate on the changes in ozone and stratospheric sulfate aerosol, with emphasis on how ozone in the lower stratosphere would respond to natural or anthropogenic changes. The key modeling tools for this work are the Atmospheric and Environmental Research (AER) two-dimensional chemistry-transport model, the AER two-dimensional stratospheric sulfate model, and the AER three-wave interactive model with full chemistry. For this six month period, we report on a modeling study of new rate constant which modify the NOx/NOy ratio in the lower stratosphere; sensitivity to changes in stratospheric water vapor in the future atmosphere; a study of N2O and CH4 observations which has allowed us to adjust diffusion in the 2-D CTM in order to obtain appropriate polar vortex isolation; a study of SF6 and age of air with comparisons of models and measurements; and a report on the Models and Measurements II effort.

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 NOx 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 H2O. 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.

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 × 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 × 1029 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.

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.

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 (<3 km). The ΔO3/ΔCO ratio (linear regression slope of O3‐CO correlation) is found to be 0.12 ppbv/ppbv, which is comparable to the ratio of 0.15 ppbv/ppbv observed at 0–4 km over the Amazon and Africa in previous studies. The net flux of O3 exported from northern Australia during BIBLE‐B is estimated to be 0.3 Gmol O3/day. In the biomass burning region, large enhancements of O3 were coincident with the locations of biomass burning hot spots, suggesting that major O3 production occurred near fires (horizontal scale <50 km).

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.

The Biomass Burning and Lightning Experiment Phase B (BIBLE‐B) aircraft measurement campaign was conducted over the western Pacific and Australia in August and September 1999. In situ aircraft measurements of carbon monoxide (CO), nitric oxide (NO), total reactive nitrogen (NOy), ozone (O3), nonmethane hydrocarbons (NMHCs), and other species were made during BIBLE‐B. Meteorological analysis shows that the trace gases emitted from biomass burning in northern Australia were mostly confined within the planetary boundary layer (below ∼3 km) by strong subsidence in the free troposphere. Removal processes of NOx (equal to measured NO + calculated NO2) and NOy in biomass burning plumes in the boundary layer are examined on the basis of correlation analysis. The photochemical lifetime of NOx in biomass burning plumes during the daytime is estimated to be 0.1 to 0.3 days using the correlations of NOx with short‐lived NMHCs and hydroxyl radical (OH) concentration calculated from a constrained photochemical model. Correlation of NOy with CO shows that ∼60% of the NOy molecules originating from biomass burning were removed in the boundary layer within 2–3 days. This result is consistent with dry deposition of nitric acid (HNO3) in the plumes. It is likely that only a small fraction of NOy emitted from biomass burning was exported from the boundary layer to the free troposphere during the BIBLE‐B period.

The Biomass Burning and Lightning Experiment phase A (BIBLE A) aircraft campaign was carried out over the tropical western Pacific in September and October 1998. During this period, biomass burning activity in Indonesia was quite weak. Mixing ratios of NOx and NOy in air masses that had crossed over the Indonesian islands within 3 days prior to the measurement (Indonesian air masses) were systematically higher than those in air masses originating from the central Pacific (tropical air masses). Sixty percent of the Indonesian air masses at 9–13 km (upper troposphere, UT) originated from the central Pacific. The differences in NOy mixing ratio between these two types of air masses were likely due to processes that occurred while air masses were over the Islands. Evidence presented in this paper suggests convection carries material from the surface, and NO is produced from lightning. At altitudes below 3 km (lower troposphere, LT), typical gradient of NOx and NOy to CO (dNOy/dCO and dNOx/dCO) was smaller than that in the biomass burning plumes and in urban areas, suggesting that neither source has a dominant influence. When the CO‐NOx and CO‐NOy relationships in the UT are compared to the reference relationships chosen for the LT, the NOx and NOy values are higher by 40–60 pptv (80% of NOx) and 70–100 pptv (50% of NOy). This difference is attributed to in situ production of NO by lightning. Analyses using air mass trajectories and geostationary meteorological satellite (GMS) derived cloud height data show that convection over land, which could be accompanied by lightning activity, increases the NOx values, while convection over the ocean generally lowers the NOx level. These processes are found to have a significant impact on the O3 production rate over the tropical western Pacific.

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.

In situ aircraft measurements of O3, CO, total reactive nitrogen (NOy), NO, and non‐methane hydrocarbons (NMHCs) were made over the western Pacific Ocean and Australia during the Biomass Burning and Lightning Experiment (BIBLE) A and B conducted in August–October 1998 and 1999. Generally, similar features were seen in the BIBLE A and B data in the latitudinal variations of these species in the troposphere from 35°N to 28°S at longitudes of 120°–150°E. The focus of this paper is to describe the characteristics of air masses sampled at 15°N–10°S (tropical Pacific) and 10°S–28°S (over Australia). With the exception of occasional enhancements in reactive nitrogen seen over New Guinea associated with lightning activities, the tropical Pacific region is distinguished from the rest of the region by smaller concentrations of these trace species. This can be explained in terms of the absence of surface sources over the ocean, lack of stratospheric intrusion, and the preclusion of midlatitude air and air from the west due to active convection throughout the troposphere. The median O3, CO, NOy, and NO mixing ratios in tropical air above 4 km were about 15–20 parts per billion by volume (ppbv), 60–75 ppbv, 20–100 parts per trillion by volume (pptv), and 5–40 pptv, respectively. Data obtained from PEM‐West A and B conducted in 1991 and 1994 showed similar latitudinal features, although the PEM‐West A values were somewhat elevated due to dominating westerly winds in the lower troposphere associated with El Niño. Over Australia, the levels of O3, CO, NOy, NO, and NMHCs were elevated throughout the troposphere over those observed in the tropical Pacific both in 1998 and 1999. The effect from biomass burning that occurred in northern Australia was limited to within the boundary layer because of strong subsidence in the period. Analyses based on 14‐day back trajectories identified free tropospheric air over Australia that originated from Indonesia, the Indian Ocean, Africa, and southern midlatitudes. The levels of O3, CO, NOy, and NMHCs in these air masses were much higher than those from the tropical Pacific due to their stronger sources from biomass burning and lightning. These values are compared with those obtained in the South Pacific during PEM‐Tropics A. Effects of biomass burning and lightning are discussed as possible sources of O3 and its precursors in these air masses.

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.

Using the measured concentrations of NO, O3, H2O, CO, CH4, and NMHCs along the flight tracks, a photochemical box model is used to calculate the concentrations of the Ox radicals, the HOx radicals, and the nitrogen species at the sampling points. The calculations make use of the measurements from radiometers to scale clear sky photolysis rates to account for cloud cover and ground albedo at the sampling time/point. The concentrations of the nitrogen species in each of the sampled air parcels are computed assuming they are in instantaneous equilibrium with the measured NO and O3. The diurnally varying species concentrations are next calculated using the box model and used to estimate the diurnally averaged production and removal rates of ozone for the sampled air parcels. Clear sky photolysis rates are used in the diurnal calculations. The campaign also provided measured concentration of NOy. The observed NO/NOy ratio is usually larger than the model calculated equilibrium value. There are several possible explanations. It could be a result of recent injection of NO into the air parcel, recent removal of HNO3 from the parcel, recent rapid transport of an air parcel from another location, or a combination of all processes. Our analyses suggest that the local production rate of O3 can be used as another indicator of recent NO injection. However, more direct studies using air trajectory analyses and other collaborative evidences are needed to ascertain the roles played by individual process.

Results from a numerical model of the global emissions, transport, chemistry, and deposition of mercury (Hg) in the atmosphere are presented. Hg (in the form of Hg(0) and Hg(II)) is emitted into the atmosphere from natural and anthropogenic sources (estimated to be 4000 and 2100 Mg yr−1, respectively). It is distributed between gaseous, aqueous and particulate phases. Removal of Hg from the atmosphere occurs via dry deposition and wet deposition, which are calculated by the model to be 3300 and 2800 Mg yr−1, respectively. Deposition on land surfaces accounts for 47% of total global deposition. The simulated Hg ambient surface concentrations and deposition fluxes to the Earth's surface are consistent with available observations. Observed spatial and seasonal trends are reproduced by the model, although larger spatial variations are observed in Hg(0) surface concentrations than are predicted by the model. The calculated atmospheric residence time of Hg is ∼1.7 years. Chemical transformations between Hg(0) and Hg(II) have a strong influence on Hg deposition patterns because Hg(II) is removed faster than Hg(0). Oxidation of Hg(0) to Hg(II) occurs primarily in the gas phase, whereas Hg(II) reduction to Hg(0) occurs solely in the aqueous phase. Our model results indicated that in the absence of the aqueous reactions the atmospheric residence time of Hg is reduced to 1.2 from 1.7 years and the Hg surface concentration is ∼25% lower because of the absence of the Hg(II) reduction pathway. This result suggests that aqueous chemistry is an essential component of the atmospheric cycling of Hg.