K. Kita

Ozone production in transpacific Asian pollution plumes and implications for ozone air quality in California

[1] We examine the ozone production efficiency in transpacific Asian pollution plumes, and the implications for ozone air quality in California, by using aircraft and surface observations in April–May 2002 from the Intercontinental Transport and Chemical Transformation 2002 (ITCT 2K2) campaign off the California coast and the Pacific Exploration of Asian Continental Emission–B (PEACE-B) campaign over the northwest Pacific. The observations are interpreted with a global three-dimensional chemical transport model (GEOS-CHEM). The model reproduces the mean features observed for CO, reactive nitrogen oxides (NOy), and ozone but underestimates the strong (20 ppbv) stratospheric contribution to ozone in the middle troposphere. The ITCT 2K2 aircraft sampled two major transpacific Asian pollution plumes, one on 5 May at 5–8 km altitude with CO up to 275 ppbv but no elevated ozone and one on 17 May at 2.5–4 km altitude with CO up to 225 ppbv and ozone up to 90 ppbv. We show that the elevated ozone in the latter plume is consistent with production from peroxyacetylnitrate (PAN) decomposition during subsidence of the plume over the northeast Pacific. This production is particularly efficient because of the strong radiation and low humidity of the subsiding environment. We argue that such PAN decomposition represents a major and possibly dominant component of the ozone enhancement in transpacific Asian pollution plumes. Strong dilution of Asian pollution plumes takes place during entrainment in the U.S. boundary layer, greatly reducing their impact at U.S. surface sites. California mountain sites are more sensitive to Asian pollution because of their exposure to the free troposphere. Model results indicate a mean Asian pollution enhancement of 7 ppbv ozone at Sequoia National Park in May 2002 on those days when the 8-hour average ozone concentration exceeded 80 ppbv. INDEX TERMS: 0368 Atmospheric Composition and Structure: Troposphere—constituent transport and chemistry; 0365 Atmospheric Composition and Structure: Troposphere—composition and chemistry; 0345 Atmospheric Composition and Structure: Pollution—urban and regional (0305); KEYWORDS: ozone, Asian pollution, ITCT 2K2, PEACE-B, transpacific transport

Impacts of biomass burning in Southeast Asia on ozone and reactive nitrogen over the western Pacific in spring

[1] 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 (NOx, 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 altitudetheincreasesinNOyandO3were810partspertrillionbyvolume(pptv)and26parts 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/NOx 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

Emission estimates of selected volatile organic compounds from tropical savanna burning in northern Australia

[i] Here we present measurements of a range of carbon-based compounds: carbon dioxide (CO 2 ), carbon monoxide (CO), methane (CH 4 ), nonmethane hydrocarbons (NMHCs), methyl halides, and dimethyl sulfide (DMS) emitted by Australian savanna fires studied as part of the Biomass Burning and Lightning Experiment (BIBLE) phase B aircraft campaign, which took place during the local late dry season (28 August to 13 September 1999). Significant enhancements of short-lived NMHCs were observed in the boundary layer (BL) over the region of intensive fires and indicate recent emissions for which the mean transport time was estimated to be about 9 hours. Emission ratios relative to CO were determined for 20 NMHCs, 3 methyl halides, DMS, and CH 4 based on the BL enhancements in the source region. Tight correlations with CO were obtained for most of those compounds, indicating the homogeneity of the local savanna source. The emission ratios were in good agreement with some previous measurements of savanna fires for stable compounds but indicated the decay of emission ratios during transport for several reactive compounds. Based on the observed emission ratios, emission factors were derived and compared to previous studies. While emission factors (g species/kg dry mole) of CO 2 varied little according to the vegetation types, those of CO and NMHCs varied significantly. Higher combustion efficiency and a lower emission factor for methane in this study, compared to forest fires, agreed well with results for savanna fires in other tropical regions. The amount of biomass burned was estimated by modeling methods using available satellite data, and showed that 1999 was an above average year for savanna burning. The gross emissions of the trace gases from Australian savanna fires were estimated.

A springtime comparison of tropospheric ozone and transport pathways on the east and west coasts of the United States

[1] We have conducted a study to determine the influence of Asian pollution plumes on free tropospheric ozone above the west coast of the United States during spring. We also explored the additional impact of North American emissions on east coast free tropospheric ozone. Long-term ozone monitoring sites in the United States are few, but we obtained ozonesonde profiles from Trinidad Head on the west coast, Huntsville, Alabama, in the southeast, and Wallops Island, Virginia, on the east coast. Additional east coast ozone profiles were measured by the MOZAIC commercial aircraft at Boston, New York City, and Philadelphia. Kilometer-averaged ozone was compared between Trinidad Head and the three east coast sites (MOZAIC, Wallops Island, and Huntsville). Only in the 0–1 km layer did the MOZAIC site have a statistically significant greater amount of ozone than Trinidad Head. Likewise only the 0–1 and 1–2 km layers had greater ozone at Wallops Island and Huntsville in comparison to Trinidad Head. While Wallops Island did show greater ozone than Trinidad Head at 6–9 km, this excess ozone was attributed to a dry air mass sampling bias. A particle dispersion model was used to determine the surface source regions for each case, and the amount of anthropogenic NOx tracer that would have been emitted into each air mass. Transport times were limited to 20 days to focus on the impact of direct transport of pollution plumes from the atmospheric boundary layer. As expected, the amount of NOx tracer emitted into the east coast profiles was much greater in the lower and mid troposphere than at the west coast. At various altitudes at both coasts there existed a significant positive correlation between ozone and the NOx tracer, but the explained variance was generally less than 30%. On the east coast, Wallops Island had the weakest relationship between ozone and the NOx tracer, while Huntsville had the strongest. During spring, differences in photochemistry and transport pathways in the lowest 2 km of the troposphere results in an extra 5–14 ppbv of ozone on the east coast in comparison to Trinidad Head. However, despite differing amounts of NOx tracer from Asia and North America in the free troposphere, we found no significant difference in free tropospheric ozone between the east and west coasts of the United States during spring.

Photochemical production of O3 in biomass burning plumes in the boundary layer over northern Australia

Author(s): Takegawa, N; Kondo, Y; Ko, M; Koike, M; Kita, K; Blake, DR; Hu, W; Scott, C; Kawakami, S; Miyazaki, Y; Russell-Smith, J; Ogawa, T | Abstract: 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 (l3 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 l50 km).

Airborne vacuum ultraviolet resonance fluorescence instrument for in situ measurement of CO

An airborne instrument for fast-response, high-precision measurement of tropospheric carbon monoxide (CO) was developed using a vacuum ultraviolet (VUV) resonance fluorescence technique. The excitation radiation is obtained by a DC discharge CO resonance lamp combined with an optical filter for the CO fourth positive band emission around 150 nm. The optical filter consists of a VUV monochromator and a crystalline quartz window (<147-nm cutoff). The crystalline quartz window ensures a sharp discrimination against wavelengths below 135.7 nm that yield a positive interference from water vapor. Laboratory tests showed that the optical system achieved a precision of 1. 1 parts per billion by volume (ppbv) at a CO concentration of 100 ppbv for a 1-s integration period, and the flow system provided a response time (1/e time constant) of ∼2 s. The aircraft measurement campaign Biomass Burning and Lightning Experiment-phase B (BIBLE-B) was conducted between August and September 1999 over the western Pacific and Australia. The flight data obtained during this campaign were used to demonstrate the high precision and fast response of the instrument. An intercomparison of the VUV CO measurement and a gas chromatographic CO measurement was conducted during BIBLE-B. Overall, these two independent measurements showed good agreement, within the experimental uncertainties.

Contribution of particulate nitrate to airborne measurements of total reactive nitrogen

[1] Simultaneous measurements of speciated, total reactive nitrogen (NOy) and particulate NO3 (particle diameter <1.3 mm) were made on board the NASA P-3B aircraft over the western Pacific in February–April 2001 during the Transport and Chemical Evolution over the Pacific (TRACE-P) experiment. Gas-phase and particulate NOy was measured using a gold tube catalytic converter. For the interpretation of particulate NOy, conversion efficiencies of particulate NH4NO3, KNO3, NaNO3, and Ca(NO3)2 were measured in the laboratory. Only NH4NO3 showed quantitative conversion, and its conversion efficiency was as high as that for HNO3 .N Oy measured on board the aircraft was found to be systematically higher by 10–30% than the sum of the individual NOy gas components ( P (NOy)i) at 0–4 km. Particulate NO3 concentrations measured by a particle-into-liquid

Effects of wet deposition on the abundance and size distribution of black carbon in East Asia

An improved understanding of the variations in the mass concentration and size distribution of black carbon (BC) in the free troposphere (FT) over East Asia, where BC emissions are very high, is needed to reliably estimate the radiative forcing of BC in climate models. We measured these parameters and the carbon monoxide (CO) concentration by conducting the Aerosol Radiative Forcing in East Asia (A-FORCE) 2013W aircraft campaign in East Asia in winter 2013 and compared these data with measurements made in the same region in spring 2009. The median BC concentrations in the FT originating from North China (NC) and South China (SC) showed different seasonal variations, which were primarily caused by variations in meteorological conditions. CO concentrations above the background were much higher in SC than in NC in both seasons, suggesting a more active upward transport of CO. In SC, precipitation greatly increased from winter to spring, leading to an increased wet deposition of BC. As a result, the median BC concentration in the FT was highest in SC air in winter. This season and region were optimal for the effective transport of BC from the planetary boundary layer to the FT. The count median diameters of the BC size distributions generally decreased with altitude via wet removal during upward transport. The altitude dependence of the BC size distributions was similar in winter and spring, in accord with the similarity in the BC mixing state. The observed BC concentrations and microphysical properties will be useful for evaluating the performance of climate models.

Variability of aerosol particle number concentrations observed over the western Pacific in the spring of 2009

Airborne measurements of aerosols were conducted over the western Pacific in the spring of 2009 during the Aerosol Radiative Forcing in East Asia (A-FORCE) aircraft campaign. The A-FORCE flights intensively covered an important vertical-latitudinal range in the outflow region of East Asia (0–9 km altitude; 27°N–38°N). This paper presents the variability of aerosol particle number concentrations obtained by condensation particle counters and a Single-Particle Soot Photometer (SP2), with the focus on those in the free troposphere. The number concentration data include total condensation nuclei with particle diameters (dp) larger than 10 nm (total CN10), PM0.17-CN10 (dp ~10–130 nm), and SP2 black carbon (NBC; dp ~75–850 nm). Large increases in total CN10 that were not associated with NBC were observed in the free troposphere, suggesting influences from new particle formation (NPF). Statistical characteristics of total CN10, PM0.17-CN10, and NBC in the lower troposphere (LT; 0–3 km), middle troposphere (MT; 3–6 km), and upper troposphere (UT; 6–9 km) are investigated. The correlation between total CN10 and NBC, along with the ratio of PM0.17 to total CN10 and carbon monoxide mixing ratio (CO), is used to interpret the observed variability. The median concentrations of total CN10 and PM0.17-CN10 in the UT were higher than those in the MT by a factor of ~1.4 and ~1.6, respectively. We attribute the enhancements of CN10 in the UT to NPF. Possible mechanisms affecting NPF in the free troposphere are discussed.

A study of BRDF over Tokyo for the spaceborne measurements of atmospheric trace gases

In the present study, we aim at developing an empirical model of BRDF over Tokyo, Japan, which is one of the most polluted areas in Asia, to evaluate the effect of the surface albedo on air-pollution monitoring from space. We used the RossThick-LiSparseReciprocal model with MODIS data to retrieve BRDF information. The BRDF had a strong dependence on season and local time, and the magnitude of the seasonal and local time change was up to 50%.