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Merrill, J. T.

Publications and source records attributed to Merrill, J. T..

Insights into Tropospheric Ozone from the INTEX Ozonesonde Network Study (IONS)

Ozone profile data from soundings integrate models, aircraft and other ground-based measurements for better interpretation of atmospheric chemistry and dynamics. A well-designed network of ozonesonde stations, with consistent sampling, can answer questions not possible with short campaigns or current satellite technology. The SHADOZ (Southern Hemisphere Additional Ozonesondes) project, for example, has led to these findings about tropical ozone: definition of the zonal tropospheric wave-one pattern in equatorial ozone, characterization of the "Atlantic ozone paradox" and establishment of a link between tropical Atlantic and Indian Ocean pollution. Building on the SHADOZ concept, a short-term ozone network was formed in July-August 2004 to coordinate ozonesonde launches during the ICARTT/INTEX/NEAQS (International Consortium on Atmospheric Research on Transport and Transformation)/Intercontinental Transport Experiment/New England Air Quality Study. In IONS (INTEX Ozonesonde Network Study), more than 250 soundings, with daily frequency at half the sites, were launched from eleven North American stations and an oceanographic ship in the Gulf of Maine. Although the goal was to examine pollution influences under stable high-pressure systems and transport associated with "warm conveyor belt" flows, the INTEX study region was dominated by a series of weak frontal system that mixed aged pollution with stratospheric ozone in the middle troposphere. Deconvoluting ozone sources provides new insights into ozone in the transition between mid-latitude and polar air.

Thompson, Anne M.

Chemical Characteristics of Continental Outflow from Asia to the Troposphere Over the Western Pacific Ocean during February - March 1994: Results from PEM-West B

We present here the chemical composition of outflow from the Asian continent to the atmosphere over the western Pacific basin during the Pacific Exploratory Mission-West (PEM-West B) in February-March 1994. Comprehensive measurements of important tropospheric trace gases and aerosol particulate matter were performed from the NASA DC-8 airborne laboratory. Backward 5 day isentropic trajectories were used to partition the outflow from two major source regions- continental north (greater than 20 deg N) and continental south (less than 20 deg N). Air parcels that had not passed over continental areas for the previous 5 days were classified as originating from an aged marine source. The trajectories and the chemistry together indicated that there was extensive rapid outflow of air parcels at altitudes below 5 km, while aged marine air was rarely encountered and only at less than 20 deg N latitude. The outflow at low altitudes had enhancements in common industrial solvent vapors such as C2Cl4, CH3CCl3, and C6H6, intermixed with the combustion emission products C2H2, C2H6, CO, and NO. The mixing ratios of all species were up to tenfold greater in outflow from the continental north compared to the continental south source region, with Pb-210 concentrations reaching 38 fCi (10(exp -15) curies) per standard cubic meter. In the upper troposphere we again observed significant enhancements in combustion-derived species in the 8-10 km altitude range, but water-soluble trace gases and aerosol species were depleted. These observations suggest that ground level emissions were lofted to the upper troposphere by wet convective systems which stripped water-soluble components from these air parcels. There were good correlations between C2H2 and CO and C2H6 (r(sup 2) = 0.70 - 0.97) in these air parcels and much weaker ones between C2H2 and H2O2 or CH3OOH (r(sup 2) = 0.50). These correlations were the strongest in the continental north outflow where combustion inputs appeared to be recent (1 - 2 days old). Ozone and PAN showed general correlation in these same air parcels but not with the combustion products. It thus appears that several source inputs were intermixed in these upper tropospheric air masses, with possible contributions from European or Middle Eastern source regions. In aged marine air mixing ratios of 03 (approximately equals 20 parts per billion by volume) and PAN (less than or equal to 10 parts per trillion by volume) were nearly identical at less than 2 km and 10 - 12 km altitudes due to extensive convective uplifting of marine boundary layer air over the equatorial Pacific even in wintertime. Comparison of the Pacific Exploratory Mission-West A and PEM-West B data sets shows significantly larger mixing ratios of SO2 and H2O2 during PEM-West A. Emissions from eruption of Mount Pinatubo are a likely cause for the former, while suppressed photochemical activity in winter was probably responsible for the latter. This comparison also highlighted the twofold enhancement in C2H2, C2H6, and C3H8 in the continental north outflow during /PEM-West B. Although this could be due to reduced OH oxidation rates of these species in wintertime, we argue that increased source emissions are primarily responsible.

Talbot, R. W.

Impact of Lightning and Convection on Reactive Nitrogen in the Tropical Free Troposphere

Latitudinal distributions of NO, NO(y), O3, CO, CH3I, and H2O mixing ratios at 8.9-12 km were obtained between 30deg N and 1deg S by DC-8 aircraft measurements made in February 1994 during Pacific Exploratory Mission-West B (PEM-West B). Very low NO(y), mixing ratios with a median value of 51 parts per trillion by volume (pptv) were observed at 9.5-12 km at 1deg N-14deg N during two flights made within 3 days. A very low median O3 mixing ratio of 19 parts per billion by volume (ppbv) and high mixing ratios of H2O and CH3I were simultaneously observed, suggesting that the low NO(y), values were probably due to the convective transport of air from the tropical marine boundary layer to this altitude. The median NO(y)/O3 ratio being a factor of 2 smaller than in the air masses in the tropical marine boundary layer might suggest the possibility that the heterogeneous removal of HNO3 during convective transport further reduced NO(y) levels. In addition to the measurements between 9.5 and 12 km, low values of NO(y) and O3 were observed between 4 and 12 km at 1deg N. Divergent wind fields at 200 and 1000 hPa and infrared (IR) cloud images show that there was large scale convection (greater than 1000 km x 1000 km) in the northeast of New Guinea Island centered around Odeg S and 150deg E as part of systematic convective activity of the Intertropical Convergence Zone (ITCZ) and the South Pacific Convergence Zone (SPCZ). This type of large scale convection could have transported air with low levels of NO(y) and O3 to the middle and upper troposphere over a wide area in the tropics. On the other hand, NO mixing ratios of 50-200 pptv and high NQ,/NOY ratios of 0.4-0.6 were observed at 9.5 km between 4deg S and 10deg S. High H2O Mixing ratios of 600-1200 parts per million by volume (ppmv) and low CO mixing ratios of 65 ppbv observed in the air mass indicated that the high NO values were probably due to NO production by lightning. Satellite observations showed relatively frequent lightning flashes over the New Guinea Island for 3 days prior to the aircraft measurements. These results are considered to be consistent with the idea that, in general, marine convection is not accompanied by lightning activity, whereas convection over land is. Because of the large areal extent of the influences from these processes, the convective transport of low NO(y) air and NO production by lightning should play critical roles in controlling the abundance of reactive nitrogen in the equatorial region.

Kawakami, S.

Reactive Nitrogen and its Correlation with O3 and CO Over the Pacific in Winter and Early Spring

Measurements of NO, NO(y), O3, and CO were made during NASA's Global Tropospheric Experiment/Pacific Exploratory Mission-West B (GTE/PEM-West B) carried out over the western Pacific in February and March 1994. NO(x) was calculated from NO using a photostationary state model ((NO(x)(sub mc)). Correlations between these species are presented, and some insights into the sources of NO(x) and NO(y) are described. The boundaries between the lower, middle, and upper troposphere have been defined at potential temperatures of 311 K and 328 K, which correspond to the geometric altitudes of about 5 and 9 km at 30degN. Enhancements in the mixing ratios of NO(y) and CO were observed in the lower and middle troposphere. A positive correlation was found between these two species suggesting that the high NO(y) values were due to anthropogenic emissions over the continental surface. On the other hand, O3 increased little with increase in CO. As a result, NO(y)/O3 ratios were higher in air more influenced by pollution. NO(y), values in 55 and 28% of the air masses sampled in the lower and middle troposphere, respectively, were higher than the clean free tropospheric NO(y)-O3 range when O3 values simultaneously observed were used. High (NOx)mc/NOy ratios between 0.15 and 0.3 were found in the boundary layer with relatively low mixing ratios of CO and NOy during the three flights. These air masses were transported from a higher altitude (approximately 5 km) and a higher latitude (approximately 50degN) within a few days. The peroxyacetyl nitrate (PAN)/NO(y) ratios were generally high (approximately 0.4) in these air masses, and the thermal decomposition of PAN was a probable source of NO(x). In the middle troposphere the (NO(x))mc mixing ratio did not generally increase with NO(y) or CO, suggesting that the transport of air masses affected by anthropogenic emissions did not increase the NO(x) level significantly. In the upper troposphere, very minor effects from the continental surface sources were seen in the CO mixing ratio. By contrast, NO(y) values in 33% of the air masses were higher than those expected when stratospheric air intrusion is assumed to be a single source of NO(y) based on NO(y)-O3 correlation analyses. This result suggests significant free tropospheric NO(y) sources, namely exhaust from the aircraft and NO production by lightning activity. In fact, spikes in the (NO(x))(sub m)c mixing ratios were observed near the aircraft corridor south of Tokyo at an altitude of 10 km. These two free tropospheric NO(x) sources were considered to be important in determining the levels of the upper tropospheric NO(x) and NO(y) during PEM-West B.

Koike, M.