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[1] Meteorological conditions are described during the Intercontinental Chemical Transport Experiment–North America (INTEX-NA) that was conducted over the United States during July and August 2004. Relatively zonal flow dominated the contiguous United States during the first 2 weeks of the mission, while a series of large amplitude troughs traversed the eastern half of the country during the final 4 weeks. These troughs were accompanied by cold fronts reaching the Gulf of Mexico, an uncommon occurrence during August. Frontal passages over the northeast were somewhat above average, but the short time interval between passages precluded the formation of stagnant high-pressure centers containing abundant pollution. Atmospheric chemistry during INTEX-NA was heavily influenced by record-breaking fires over Alaska and western Canada. Persistent high pressure over Alaska provided ideal conditions for the wildfires and for transporting their burning by-products southeastward toward the INTEX domain where they were sampled frequently by INTEX aircraft. Forward trajectories and satellite imagery showed that the plumes later were carried to parts of Europe, Africa, and even the Arctic. Deep convection and lightning were important factors during INTEX-NA. Cloud-to-ground (CG) lightning data show that horizontal patterns and numbers of lightning flashes during INTEX-NA are similar to those of 2003 and 2005. Statistics derived from 10 day backward trajectories indicate that the DC-8 often sampled lightning influenced air.

[1] Warm conveyor belts (WCBs) are important mechanisms for transporting pollution during the cool season. These airstreams distribute surface emissions throughout the troposphere, playing a major role in the long-range transport of chemical species. Previous efforts to understand the lofting of WCBs have not investigated the relative importance of vertical forcing. In this study, we use fine resolution model-derived meteorological data, air parcel trajectories, flux calculations, and a diagnostic package for weather systems to perform a focused investigation of WCBs during the warm season INTEX-A period. Lifting and transport mechanisms during INTEX-A are compared to a well-documented cool season WCB case in the literature. Results show that weak, midlatitude cyclones are capable of producing vertical transport as great or greater than much stronger cyclones. An analysis of forcing terms contributing to vertical motion reveals that the Laplacian of latent heat release is the primary contributor to vertical motion during some cases of INTEX-A. The latent heating term is found to be greatest in areas of deep convection. This convection allows weak cyclones to produce WCB-like transport. WCB pathways are similar for the cases studied. In each example, air which originates far south of the low in the warm sector ascends to the north and joins the upper level westerly flow northeast of the low center. Although the transport pathways are similar, the forcing mechanism and location of maximum vertical transport are found to exhibit strong case-to-case variability. When cyclone-scale dynamics are relatively weak, widespread deep convection, especially south of the cyclone's center, is necessary to produce transport resembling a WCB.

Four global scale and three regional scale chemical transport models are intercompared and evaluated during NASA's TRACE-P experiment. Model simulated and measured CO are statistically analyzed along aircraft flight tracks. Results for the combination of eleven flights show an overall negative bias in simulated CO. Biases are most pronounced during large CO events. Statistical agreements vary greatly among the individual flights. Those flights with the greatest range of CO values tend to be the worst simulated. However, for each given flight, the models generally provide similar relative results. The models exhibit difficulties simulating intense CO plumes. CO error is found to be greatest in the lower troposphere. Convective mass flux is shown to be very important, particularly near emissions source regions. Occasionally meteorological lift associated with excessive model-calculated mass fluxes leads to an overestimation of mid- and upper- tropospheric mixing ratios. Planetary Boundary Layer (PBL) depth is found to play an important role in simulating intense CO plumes. PBL depth is shown to cap plumes, confining heavy pollution to the very lowest levels.

[1] Chemical and physical aerosol data collected on the DC-8 during TRACE-P were grouped into four sectors based on back trajectories. The four sectors represent long-range transport from the west (WSW), regional circulation over the western Pacific and Southeast Asia (SE Asia), polluted transport from northern Asia with substantial sea salt at low altitudes (NNW) and a substantial amount of dust (Channel). WSW has generally low mixing ratios at both middle and high altitudes, with the bulk of the aerosol mass due to non-sea-salt water-soluble inorganic species. Low altitude SE Asia also has low mean mixing ratios in general, with the majority of the aerosol mass comprised of non-sea-salts, however, soot is also relatively important in this region. NNW had the highest mean sea salt mixing ratios, with the aerosol mass at low altitudes (

We investigate the sources, prevalence, and fine-particle inorganic composition of biosmoke over the western Pacific Ocean between 24 February and 10 April 2001. The analysis is based on highly time-resolved airborne measurements of gaseous and fine- particle inorganic chemical composition made during the NASA Transport and Chemical Evolution over the Pacific (TRACE-P) experiment. At latitudes below approximately 25 deg. N, relatively pure biomass burning plumes of enhanced fine-particle potassium, nitrate, ammonium, light-absorbing aerosols, and CO concentrations were observed in plumes that back trajectories and satellite fire map data suggest originated from biomass burning in southeast Asia. Fine-particle water-soluble potassium (K+) is confirmed to be a unique biosmoke tracer, and its prevalence throughout the experiment indicates that approximately 20% of the TRACE-P Asian outflow plumes were influenced, to some extent, by biomass or biofuel burning emissions. At latitudes above 25 deg. N, highly mixed urban/industrial and biosmoke plumes, indicated by SO(sup 2, sub 4) and K+, were observed in 5 out of 53 plumes. Most plumes were found in the Yellow Sea and generally were associated with much higher fine-particle loadings than plumes lacking a biosmoke influence. The air mass back trajectories of these mixed plumes generally pass through the latitude range of between 34 deg. and 40 deg. N on the eastern China coast, a region that includes the large urban centers of Beijing and Tianjin. A lack of biomass burning emissions based on fire maps and high correlations between K+ and pollution tracers (e.g., S(sup 2, sub 4) suggest biofuel sources. Ratios of fine-particle potassium to sulfate are used to provide an estimate of relative contributions of biosmoke emissions to the mixed Asian plumes. The ratio is highly correlated with fine-particle volume (r(sup 2) = 0.85) and predicts that for the most polluted plume encounter in TRACE-P, approximately 60% of the plume is associated with biosmoke emissions. On average, biosmoke contributes approximately 35-40% to the measured fine inorganic aerosol mass in the mixed TRACE-P plumes intercepted north of 25% latitude.

[1] Airborne whole air samples collected over the western Pacific in spring, 2001 showed depletion of tetrachloroethene (C2Cl4) in every upper tropospheric (UT) air parcel that had interacted with large areas of cirrus less than three days upwind. The amount of C2Cl4 depletion showed a negative correlation with time since the interaction, consistent with the C2Cl4-depleted air parcels mixing with the ambient air as they moved downwind of the cirrus. Ethane and C2Cl4 both react relatively quickly with atomic chlorine (Cl) but ethane was not significantly depleted in these same air parcels, indicating that the C2Cl4 depletion cannot be attributed to Cl chemistry alone. Based on the minimum ethane depletion that can be detected by our measurements, a daytime upper limit of roughly 3 10 4 atom Cl cm 3 is indirectly estimated for heterogeneous chlorine activation by cirrus clouds in the UT in tropical- and mid-latitudes during spring. INDEX TERMS: 0317 Atmospheric Composition and Structure: Chemical kinetic and photochemical properties; 0320 Atmospheric Composition and Structure: Cloud physics and chemistry; 0365 Atmospheric Composition and Structure: Troposphere— composition and chemistry; 0368 Atmospheric Composition and Structure: Troposphere—constituent transport and chemistry

[1] Pathways of synoptic-scale uplifted transport of pollutants from East Asia and their effects on chemical distributions of NOy species are investigated based on a subset of the aircraft data obtained during the NASA Transport and Chemical Evolution over the Pacific (TRACE-P) experiment, conducted in February–April 2001. Meteorological and chemical analyses indicate that 73% of the uplifted transport was associated with warm conveyor belts (WCBs) and convective outflow (COF), which transported air masses strongly impacted by biomass burning over Southeast Asia. The rest (27%) of the uplifted air masses originated over coastal regions of northeast China, where fossil fuel combustion was a dominant source of pollutants. Both WCB associated with a midlatitude cyclone and COF associated with a stationary front over southeast China are examined in detail for the April 4 case. During the TRACE-P period, low NOx(= NO + NO2)/NOy ratios in the WCB and COF indicate that a significant part of the NOx was oxidized to nitric acid (HNO3) and peroxyacetyl nitrate (PAN) during transport. Low HNO3/NOy ratios in the WCB and COF airstreams indicate that a large amount of HNO3 was removed during transport on timescales within 1–3 days. PAN was found to be the dominant form of NOy in air masses transported by the WCB and COF, likely due to the production of PAN in regions of biomass burning and industrial emissions, as well as due to the rapid removal of HNO3 during transport. For emissions that were transported to the free troposphere by WCBs and COF, about 10–20% of the NOy remained after transport to the free troposphere, and 30% of the NOy surviving in the boundary layer in limited cases. The results indicate that the WCB and COF provide both an efficient sink for HNO3 and an efficient mechanism for the transport of PAN from the boundary layer to the free troposphere over the western Pacific.

[1] We report here airborne measurements of atmospheric CO2 over the western North Pacific during the March–April 2001 Transport and Chemical Evolution over the Pacific (TRACE-P) mission. The CO2 spatial distributions were notably influenced by cyclogenesis-triggered transport of regionally polluted continental air masses. Examination of the CO2 to C2H2/CO ratio indicated rapid outflow of combustion-related emissions in the free troposphere below 8 km. Although the highest CO2 mixing ratios were measured within the Pacific Rim region, enhancements were also observed further east over the open ocean at locations far removed from surface sources. Near the Asian continent, discrete plumes encountered within the planetary boundary layer contained up to 393 ppmv of CO2. Coincident enhancements in the mixing ratios of C2Cl4, C2H2, and C2H4 measured concurrently revealed combustion and industrial sources. To elucidate the source distributions of CO2, an emissions database for Asia was examined in conjunction with the chemistry and 5-day backward trajectories that revealed the WNW/W sector of northeast Asia was a major contributor to these pollution events. Comparisons of NOAA/CMDL and JMA surface data with measurements obtained aloft showed a strong latitudinal gradient that peaked between 35° and 40°N. We estimated a net CO2 flux from the Asian continent of approximately 13.93 Tg C day−1 for late winter/early spring with the majority of the export (79%) occurring in the lower free troposphere (2–8 km). The apportionment of the flux between anthropogenic and biospheric sources was estimated at 6.37 Tg C day−1 and 7.56 Tg C day−1, respectively.

[1] Airborne measurements of CH2O were acquired employing tunable diode laser absorption spectroscopy during the 2001 Transport and Chemical Evolution Over the Pacific (TRACE-P) study onboard NASA's DC-8 aircraft. Above ∼2.5 km, away from the most extreme pollution influences and heavy aerosol loadings, comprehensive comparisons with a steady state box model revealed agreement to within ±37 pptv in the measurement and model medians binned according to altitude and longitude. Likewise, a near unity slope (0.98 ± 0.03) was obtained from a bivariate fit of the measurements, averaged into 25 pptv model bins, versus the modeled concentrations for values up to ∼450 pptv. Both observations suggest that there are no systematic biases on average between CH2O measurements and box model results out to model values ∼450 pptv. However, the model results progressively underpredict the observations at higher concentrations, possibly due to transport effects unaccounted for in the steady state model approach. The assumption of steady state also appears to contribute to the scatter observed in the point-by-point comparisons. The measurement-model variance was further studied employing horizontal flight legs. For background legs screened using a variety of nonmethane hydrocarbon (NMHC) tracers, measurement and model variance agreed to within 15%. By contrast, measurement variance was ∼60% to 80% higher than the model variance, even with small to modest elevations in the NMHC tracers. Measurement-model comparisons of CH2O in clouds and in the lower marine troposphere in the presence of marine aerosols suggest rather significant CH2O uptake by as much as 85% in one extreme case compared to expectations based on modeled gas phase processes.

[1] We report the first in situ measurements of hydrogen cyanide (HCN) and methyl cyanide (CH3CN, acetonitrile) from the Pacific troposphere (0–12 km) obtained during the NASA Transport and Chemical Evolution over the Pacific (TRACE-P) airborne mission (February–April 2001). Mean HCN and CH3CN mixing ratios of 243 ± 118 (median 218) ppt and 149 ± 56 (median 138) ppt, respectively, were measured. These in situ observations correspond to a mean tropospheric HCN column of 4.2 × 1015 molecules cm−2 and a CH3CN column of 2.5 × 1015 molecules cm−2. This is in good agreement with the 0–12 km HCN column of 4.4 (±0.6) × 1015 molecules cm−2 derived from infrared solar spectroscopic observations over Japan. Mixing ratios of HCN and CH3CN were greatly enhanced in pollution outflow from Asia and were well correlated with each other as well as with known tracers of biomass combustion (e.g., CH3Cl, CO). Volumetric enhancement (or emission) ratios (ERs) relative to CO in free tropospheric plumes, likely originating from fires, were 0.34% for HCN and 0.17% for CH3CN. ERs with respect to CH3Cl and CO in selected biomass burning (BB) plumes in the free troposphere and in boundary layer pollution episodes are used to estimate a global BB source of 0.8 ± 0.4 Tg (N) yr−1 for HCN and 0.4 ± 0.1 Tg (N) yr−1 for CH3CN. In comparison, emissions from industry and fossil fuel combustion are quite small (

Author(s): Simpson, IJ; Blake, NJ; Blake, DR; Atlas, E; Flocke, F; Crawford, JH; Fuelberg, HE; Kiley, CM; Meinardi, S; Rowland, FS | Abstract: The photochemical production and evolution of six C2-C5 alkyl nitrates (ethyl-, 1-propyl-, 2-propyl-, 2-butyl-, 2-pentyl-, and 3-pentyl nitrate) was investigated using selected data from 5500 whole air samples collected downwind of Asia during the airborne Transport and Chemical Evolution over the Pacific (TRACE-P) field campaign (February-April 2001). Air mass age was important for selecting appropriate field data to compare with laboratory predictions of C5 alkyl nitrate production rates. In young, highly polluted air masses, the ratio between the production rates of 3-pentyl nitrate and 2-pentyl nitrate from n-pentane was 0.60-0.65. These measured ratios show excellent agreement with results from a field study in Germany (0.63 ± 0.06), and they agree better with predicted ratios from older laboratory kinetic studies (0.63-0.66) than with newer laboratory results (0.73 ± 0.08). TRACE-P samples that did not show influence from marine alkyl nitrate sources were used to investigate photochemical alkyl nitrate evolution. Relative to 2-butyl nitrate/n-butane, the measured ratios of ethyl nitrate/ethane and 2-propyl nitrate/propane showed notable deviations from modeled values based on laboratory kinetic data, suggesting additional Asian sources of their alkyl peroxy radical precursors. By contrast, the measured ratios of 1-propyl-, 2-pentyl-, and 3-pentyl nitrate to their respective parent hydrocarbons were fairly close to modeled values. The 1-propyl nitrate findings contrast with field studies in North America, and suggest that air downwind of Asia was not significantly impacted by additional 1-propyl nitrate precursors. The sensitivity of modeled photochemical processing times to hydroxyl radical concentration, altitude, city ventilation times, and dilution is discussed.

[1] We present an overview of the spatial distributions of nonmethane hydrocarbons (NMHCs) and halocarbons observed over the western north Pacific as part of the NASA GTE Transport and Chemical Evolution over the Pacific (TRACE-P) airborne field campaign (February–April 2001). The TRACE-P data are compared with earlier measurements from the Pacific Rim during the Pacific Exploratory Mission-West B (PEM-West B), which took place in February–March 1994, and with emission inventory data for 2000. Despite the limited spatial and temporal data coverage inherent to airborne sampling, mean levels of the longer-lived NMHCs (including ethane, ethyne, and benzene) were remarkably similar to our results during the PEM-West B campaign. By comparison, mixing ratios of the fire extinguisher Halon-1211 (CF2ClBr) increased by about 50% in the period between 1994 and 2001. Southern China (south of 35°N), and particularly the Shanghai region, appears to have been a substantial source of Halon-1211 during TRACE-P. Our previous analysis of the PEM-West B data employed methyl chloroform (CH3CCl3) as a useful industrial tracer. However, regulations have reduced its emissions to the extent that its mixing ratio during TRACE-P was only one-third of that measured in 1994. Methyl chloroform mixing ratio “hot spots,” indicating regions downwind of continuing emissions, included outflow from the vicinity of Shanghai, China, but particularly high emission ratios relative to CO were observed close to Japan and Korea. Tetrachloroethene (C2Cl4) levels have also decreased significantly, especially north of 25°N, but this gas still remains a useful indicator of northern industrial emissions. Methyl bromide (CH3Br) levels were systematically 1–2 pptv lower from 1994 to 2001, in accord with recent reports. However, air masses that had been advected over Japan and/or South Korean port cities typically exhibited elevated levels of CH3Br. As a consequence, emissions of CH3Br from Japan and Korea calculated employing CH3Br/CO ratios and scaled to CO emission inventory estimates, were almost as large as for all of south China (south of 35°N). Total east Asian emissions of CH3Br and CH3Cl were estimated to be roughly 4.7 Gg/yr and 167 Gg/yr, respectively, in 2001.

[1] The Transport and Chemical Evolution over the Pacific (TRACE-P) experiment was conducted between February and April 2001. It included extensive chemical sampling by two aircraft based primarily in Hong Kong and Yokota Air Base, Japan. TRACE-P examined pathways for the outflow of chemically and radiatively important gases and aerosols and their precursors from eastern Asia to the western Pacific and explored the chemical evolution of Asian outflow. This paper describes meteorological conditions and transport pathways over the Pacific Basin during TRACE-P. Meteorological conditions changed rapidly during the period due to the seasonal winter to spring transition and the decay of prolonged ENSO cold phase (La Nina) conditions. To document these changes, TRACE-P was divided into two halves, and mean flow patterns during each half are presented and discussed. Important circulation features are the semipermanent Siberian anticyclone and transient middle latitude cyclones that form near eastern Asia and then move eastward over the northern Pacific. Five-day backward trajectories from the various flight tracks show that air sampled by the aircraft had been transported from a variety of locations. Some parcels remained over the tropical western North Pacific during the entire period, while other important origins were Southeast Asia, Africa, and central Asia. Specifically, lower tropospheric flight segments out of Hong Kong sampled both prefrontal maritime air as well as postfrontal air from the Asian continent. Conversely, low-level flight segments out of Yokota, Japan mostly sampled postfrontal Asian air. Southern portions of middle and upper tropospheric flight segments from Hong Kong sampled air previously in the deep tropics, while the more northerly flight segments sampled air that originated from the west (e.g., passing over central Africa and India). Most upper level flight segments from Yokota sampled air arriving from the west. Patterns of satellite-derived precipitation and lightning are described. TRACE-P occurs during a neutral to weak La Nina period of relatively cold sea surface temperatures in the tropical Pacific. Compared with climatology, the TRACE-P period exhibits deep convection located west of its typical position; however, tropospheric flow patterns do not exhibit a strong La Nina signal. Circulation patterns during TRACE-P are found to be generally similar to those during NASA's PEM WEST-B mission that occurred in the same region during February–March 1994.