[1] We report the first in situ measurements of hydrogen cyanide (HCN) and methyl cyanide (CH 3 CN, 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 CH 3 CN 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 Â 10 15 molecules cm À2 and a CH 3 CN column of 2.5 Â 10 15 molecules cm À2 . This is in good agreement with the 0-12 km HCN column of 4.4 (±0.6) Â 10 15 molecules cm À2 derived from infrared solar spectroscopic observations over Japan. Mixing ratios of HCN and CH 3 CN 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., CH 3 Cl, 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 CH 3 CN. ERs with respect to CH 3 Cl 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 À1 for HCN and 0.4 ± 0.1 Tg (N) yr À1 for CH 3 CN. In comparison, emissions from industry and fossil fuel combustion are quite small (<0.05 Tg (N) yr À1 ). The vertical structure of HCN and CH 3 CN indicated reduced mixing ratios in the marine boundary layer (MBL). Using a simple box model, the observed gradients across the top of the MBL are used to derive an oceanic loss rate of 8.8 Â 10 À15 g (N) cm À2 s À1 for HCN and 3.4 Â 10 À15 g (N) cm À2 s À1 for CH 3 CN. An air-sea exchange model is used to conclude that this flux can be maintained if the oceans are undersaturated in HCN and CH 3 CN by 27% and 6%, respectively. These observations also correspond to an open ocean mean deposition velocity (v d ) of 0.12 cm s À1 for HCN and 0.06 cm s À1 for CH 3 CN. It is inferred that oceanic loss is a dominant sink for these cyanides and that they deposit some 1.4 Tg (N) of nitrogen annually to the oceans. Assuming loss to the oceans and reaction with OH radicals as the major removal processes, a mean atmospheric residence time of 5.0 months for HCN and 6.6 months for CH 3 CN is calculated. A global budget analysis shows that the sources and sinks of HCN and CH 3 CN are roughly in balance but large uncertainties remain in part due to a lack of observational data from the atmosphere and the oceans. Pathways leading to the oceanic (and soil) degradation of these cyanides are poorly known but are expected to be biological in nature.

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.

[1] Airborne measurements of CH 2 O 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 CH 2 O 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 CH 2 O in clouds and in the lower marine troposphere in the presence of marine aerosols suggest rather significant CH 2 O uptake by as much as 85% in one extreme case compared to expectations based on modeled gas phase processes.

[1] Pathways of synoptic-scale uplifted transport of pollutants from East Asia and their effects on chemical distributions of NO y 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 NO x (= NO + NO 2 )/NO y ratios in the WCB and COF indicate that a significant part of the NO x was oxidized to nitric acid (HNO 3 ) and peroxyacetyl nitrate (PAN) during transport. Low HNO 3 /NO y ratios in the WCB and COF airstreams indicate that a large amount of HNO 3 was removed during transport on timescales within 1-3 days. PAN was found to be the dominant form of NO y 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 HNO 3 during transport. For emissions that were transported to the free troposphere by WCBs and COF, about 10-20% of the NO y remained after transport to the free troposphere, and 30% of the NO y surviving in the boundary layer in limited cases. The results indicate that the WCB and COF provide both an efficient sink for HNO 3 and an efficient mechanism for the transport of PAN from the boundary layer to the free troposphere over the western Pacific.

[1] 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 fineparticle inorganic chemical composition made during the NASA Transport and Chemical Evolution over the Pacific (TRACE-P) experiment. At latitudes below approximately 25°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°N, highly mixed urban/industrial and biosmoke plumes, indicated by SO 4 2À 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°and 40°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., SO 4 2À ) 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 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°N latitude.