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 (<0.05 Tg (N) yr-1). The vertical structure of HCN and CH3CN 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 × 10-15 g (N) cm-2 s-1 for HCN and 3.4 × 10-15 g (N) cm-2 s-1 for CH3CN. An air-sea exchange model is used to conclude that this flux can be maintained if the oceans are undersaturated in HCN and CH3CN by 27% and 6%, respectively. These observations also correspond to an open ocean mean deposition velocity (vd) of 0.12 cm s-1 for HCN and 0.06 cm s-1 for CH3CN. 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 CH3CN is calculated. A global budget analysis shows that the sources and sinks of HCN and CH3CN 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.

A comprehensive group of reactive nitrogen species (NO, NO2, HNO3, HO2NO2, PANs, alkyl nitrates, and aerosol-NO3^-) were measured over North America during July/August 2004 from the NASA DC-8 platform (0.1-12 km). Nitrogen containing tracers of biomass combustion (HCN and CH3CN) were also measured along with a host of other gaseous (CO, VOC, OVOC, halocarbon) and aerosol tracers. Clean background air as well as air with influences from biogenic emissions, anthropogenic pollution, biomass combustion, convection, lightning, and the stratosphere was sampled over the continental United States, the Atlantic, and the Pacific. The North American upper troposphere (UT) was found to be greatly influenced by both lightning NOx and surface pollution lofted via convection and contained elevated concentrations of PAN, ozone, hydrocarbons, and NOx. Observational data suggest that lightning was a far greater contributor to NOx in the UT than previously believed. PAN provided a dominant reservoir of reactive nitrogen in the UT while nitric acid dominated in the lower troposphere (LT). Peroxynitric acid (HO2NO2) was present in sizable concentrations peaking at around 8 km. Aerosol nitrate appeared to be mostly contained in large soil based particles in the LT. Plumes from Alaskan fires contained large amounts of PAN and aerosol nitrate but little enhancement in ozone. A comparison of observed data with simulations from four 3-D models shows significant differences between observations and models as well as among models. We investigate the partitioning and interplay of the reactive nitrogen species within characteristic air masses and further examine their role in ozone formation. Copyright 2007 by the American Geophysical Union.

Measurements of important reactive nitrogen species (NO, NO2, HNO3, PAN, PPN, NO3-, NOy), C1 to C6 hydrocarbons, O3, chemical tracers (C2Cl4, CO), and meteorological parameters were made in the troposphere (0 to 12 km) over the western Pacific (0°-50°N) during the Pacific Exploratory Mission-West A campaign (September-October 1991). Under clean conditions, mixing ratios of NO, NO2, NOy, and O3 increased with altitude and showed a distinct latitudinal gradient. PAN showed a midtropospheric maximum, while nitric acid mixing ratios were generally highest near the surface. Measured NOy concentrations were significantly greater than the sum of individually measured nitrogen species (mainly NOx., PAN, and HNO3), suggesting that a large fraction of reactive nitrogen present in the atmosphere is made up of hitherto unknown species. This shortfall was larger in the tropics (≈65%) compared to midlatitudes (≈40%) and was minimal in air masses with high HNO3 mixing ratios (>100 ppt). A global threedimensional photochemical model has been used to compare observations with predictions and to assess the significance of major sources. It is possible that the tropical lightning source is much greater than commonly assumed, and both lightning source and its distribution remain a major area of uncertainty in the budgets of NOy and NOx. A large disagreement between measurement and theory exists in the atmospheric distribution of HNO3. It appears that surface-based anthropogenic emissions provide nearly 65% of the global atmospheric NOy reservoir. Relatively constant NOx/NOy ratios imply that NOy and NOx are in chemical equilibrium and the NOy reservoir may be an important in situ source of atmospheric NOx. Data are interpreted to suggest that only about 20% of the upper tropospheric (7-12 km) NOx is directly attributable to its surface NOx source, and free tropospheric sources are dominant. In situ release of NOx from the NOy reservoir, lightning, direct transport of surface NOx, aircraft emissions, and small stratospheric input collectively maintain the NOx balance in the atmosphere. It is shown that atmospheric ratios of reactive nitrogen and sulfur species, along with trajectory analysis, can be used to pinpoint the source of Asian continental outflow. Compared to rural atmospheres over North America, air masses over the Pacific are highly efficient in net O3 production. Sources of tropospheric NOx cannot yet be accurately defined due to shortcomings in measurements and theory. Copyright 1996 by the American Geophysical Union.