Chemical characteristics of air from different source regions during the second Pacific Exploratory Mission in the Tropics (PEM-Tropics B)

Ten-day backward trajectories are used to determine the origins of air parcels arriving at locations of airborne DC-8 chemical measurements during NASA's second Pacific Exploratory Mission in the Tropics B that was conducted during February-April 1999. Chemical data at sites where the trajectories had a common geographical origin and transport history are grouped together, and statistical measures of chemical characteristics are computed. Temporal changes in potential temperature are used to determine whether trajectories experienced a significant convective influence during the 10-day period. Trajectories describing the aged marine Southern Hemispheric category remain over the South Pacific Ocean during the 10-day period, and their corresponding chemical signature indicates very clean air. The category aged marine air in the Northern Hemisphere is found to be somewhat dirtier. Subdividing its trajectories based on the direction from which the air had traveled is found to be important in explaining the various chemical signatures. Similarly, long-range northern hemispheric trajectories passing over Asia are subdivided depending on whether they had followed a mostly zonal path, had originated near the Indian Ocean, or had originated near Central or South America and subsequently experienced a stratospheric influence. Results show that the chemical signatures of these subcategories are different from each other. The chemical signature of the southern hemispheric long-range transport category apparently exhibits the effects of pollution from Australia, southern Africa, and South America. Parcels originating over Central and northern South America are found to contain the strongest pollution signature of all categories, due to biomass burning and other sources. The convective category exhibits enhanced values of nitrogen species, probably due to emissions from lightning associated with the convection. Values of various species, including peroxides and acids, confirm that parcels were influenced by the removal of soluble gas and particle species due to precipitation. Finally, current results are compared with those from the first PEM-Tropics mission that was conducted in the same region during the southern hemispheric dry season (August-October 1996) when extensive biomass burning occurred. Results show that air samples during PEM-Tropics B are considerably cleaner than those of its dry season counterpart. Copyright 2001 by the American Geophysical Union

Chemical characteristics of Pacific tropospheric air in the region of the Intertropical Convergence Zone and South Pacific Convergence Zone

The Pacific Exploratory Mission (PEM)-Tropics provided extensive aircraft data to study the atmospheric chemistry of tropospheric air in Pacific Ocean regions, extending from Hawaii to New Zealand and from Fiji to east of Easter Island. This region, especially the tropics, includes some of the cleanest tropospheric air of the world and, as such, is important for studying atmospheric chemical budgets and cycles. The region also provides a sensitive indicator of the global-scale impact of human activity on the chemistry of the troposphere, and includes such important features as the Pacific "warm pool," the Intertropical Convergence Zone (ITCZ), the South Pacific Convergence Zone (SPCZ), and Walker Cell circulations. PEM-Tropics was conducted from August to October 1996. The ITCZ and SPCZ are major upwelling regions within the South Pacific and, as such, create boundaries to exchange of tropospheric air between regions to the north and south. Chemical data obtained in the near vicinity of the ITCZ and the SPCZ are examined. Data measured within the convergent zones themselves are not considered. The analyses show that air north and south of the convergent zones have different chemical signatures, and the signatures are reflective of the source regions and transport histories of the air. Air north of the ITCZ shows a modest urban/industrialized signature compared to air south of the ITCZ. The chemical signature of air south of the SPCZ is dominated by combustion emissions from biomass burning, while air north of the SPCZ is relatively clean and of similar composition to ITCZ south air. Chemical signature differences of air north and south of the zones are most pronounced at altitudes below 5 km, and, as such, show that the ITCZ and SPCZ are effective low-altitude barriers to the transport of tropospheric air. At altitudes of 8 to 10 km, chemical signatures are less dissimilar, and air backward trajectories (to 10 days) show cross-convergent-zone flow. At altitudes below about 5 km, little cross-zonal flow is observed. Chemical signatures presented include over 30 trace chemical species including ultrafine, fine, and heated-fine (250°C) aerosol. Copyright 1999 by the American Geophysical Union

A case study of transport of tropical marine boundary layer and lower tropospheric air masses to the northern midlatitude upper troposphere

Low-ozone (<20 ppbv) air masses were observed in the upper troposphere in northern midlatitudes over the eastern United States and the North Atlantic Ocean on several occasions in October 1997 during the NASA Subsonic Assessment, Ozone and Nitrogen Oxide Experiment (SONEX) mission. Three cases of low-ozone air masses were shown to have originated in the tropical Pacific marine boundary layer or lower troposphere and advected poleward along a warm conveyor belt during a synoptic-scale disturbance. The tropopause was elevated in the region with the low-ozone air mass. Stratospheric intrusions accompanied the disturbances. On the basis of storm track and stratospheric intrusion climatologies, such events appear to be more frequent from September through March than the rest of the year. Copyright 2000 by the American Geophysical Union

Factors controlling tropospheric O3, OH, NOx, and SO2 over the tropical Pacific during PEM-Tropics B

Observations over the tropical Pacific during the Pacific Exploratory Mission (PEM)-Tropics B experiment (March-April 1999) are analyzed. Concentrations of CO and long-lived nonmethane hydrocarbons in the region are significantly enhanced due to transport of pollutants from northern industrial continents. This pollutant import also enhances moderately O3 concentrations but not NOx concentrations. It therefore tends to depress OH concentrations over the tropical Pacific. These effects contrast to the large enhancements of O3 and NOx concentrations and the moderate increase of OH concentrations due to biomass burning outflow during the PEM-Tropics A experiment (September-October 1996). Observed CH3I concentrations, as in PEM-Tropics A, indicate that convective mass outflux in the middle and upper troposphere is largely independent of altitude over the tropical Pacific. Constraining a one-dimensiohal model with CH3I observations yields a 10-day timescale for convective turnover of the free troposphere, a factor of 2 faster than during PEM-Tropics A. Model simulated HO2, CH2O, H2O2, and CH3OOH concentrations are generally in agreement with observations. However, simulated OH concentrations are lower (∼25%) than observations above 6 km. Whereas models tend to overestimate previous field measurements, simulated HNO3 concentrations during PEM-Tropics B are too low (a factor of 2-4 below 6 km) compared to observations. Budget analyses indicate that chemical production of O3 accounts for only 50% of chemical loss; significant transport of O3 into the region appears to take place within the tropics. Convective transport of CH3OOH enhances the production of HOx and O3 in the upper troposphere, but this effect is offset by HOx loss due to the scavenging of H2O2. Convective transport and scavenging of reactive nitrogen species imply a necessary source of 0.4-1 Tg yr-1 of NOx in the free troposphere (above 4 km) over the tropics. A large fraction of the source could be from marine lightning. Oxidation of DMS transported by convection from the boundary layer could explain the observed free tropospheric SO2 concentrations over the tropical Pacific. This source of DMS due to convection, however, would imply in the model free tropospheric concentrations much higher than observed. The model overestimate cannot be reconciled using recent kinetics measurements of the DMS-OH adduct reaction at low pressures and temperatures and may reflect enhanced OH oxidation of DMS during convection. Copyright 2001 by the American Geophysical Union

On the origin of tropospheric ozone and NOx over the tropical South Pacific

The budgets of ozone and nitrogen oxides (NOx = NO + NO2) in the tropical South Pacific troposphere are analyzed by photochemical point modeling of aircraft observations at 0-12 km altitude from the Pacific Exploratory Mission-Tropics A campaign flown in September-October 1996. The model reproduces the observed NO2/NO concentration ratio to within 30% and has similar success in simulating observed concentrations of peroxides (H2O2, CH3OOH), lending confidence in its use to investigate ozone chemistry. It is found that chemical production of ozone balances only half of chemical loss in the tropospheric column over the tropical South Pacific. The net loss is 1.8 x 1011 molecules cm-2 s-1. The missing source of ozone is matched by westerly transport of continental pollution into the region. Independent analysis of the regional ozone budget with a global three-dimensional model corroborates the results from the point model and reveals the importance of biomass burning emissions in South America and Africa for the ozone budget over the tropical South Pacific. In this model, biomass burning increases average ozone concentrations by 7-8 ppbv throughout the troposphere. The NOx responsible for ozone production within the South Pacific troposphere below 4 km can be largely explained by decomposition of peroxyacetylnitrate (PAN) transported into the region with biomass burning pollution at higher altitudes. Copyright 1999 by the American Geophysical Union

Seasonal differences in the photochemistry of the South Pacific: A comparison of observations and model results from PEM-Tropics A and B

A time-dependent photochemical box model is used to examine the photochemistry of the equatorial and southern subtropical Pacific troposphere with aircraft data obtained during two distinct seasons: the Pacific Exploratory Mission-Tropics A (PEM-Tropics A) field campaign in September and October of 1996 and the Pacific Exploratory Mission-Tropics B (PEM-Tropics B) campaign in March and April of 1999. Model-predicted values were compared to observations for selected species (e.g., NO2, OH, HO2) with generally good agreement. Predicted values of HO2 were larger than those observed in the upper troposphere, in contrast to previous studies which show a general underprediction of HO2 at upper altitudes. Some characteristics of the budgets of HOx, NOx, and peroxides are discussed. The integrated net tendency for O3 is negative over the remote Pacific during both seasons, with gross formation equal to no more than half of the gross destruction. This suggests that a continual supply of O3 into the Pacific region throughout the year must exist in order to maintain O3 levels. Integrated net tendencies for equatorial O3 showed a seasonality, with a net loss of 1.06×1011 molecules cm-2 s-1 during PEM-Tropics B (March) increasing by 50% to 1.60×1011 molecules cm-2 s-1 during PEM-Tropics A (September). The seasonality over the southern subtropical Pacific was somewhat lower, with losses of 1.21×1011 molecules cm-2 s-1 during PEM-Tropics B (March) increasing by 25% to 1.51×1011 molecules cm-2 s-1 during PEM-Tropics A (September). While the larger net losses during PEM-Tropics A were primarily driven by higher concentrations of O3, the ability of the subtropical atmosphere to destroy O3 was ∼30% less effective during the PEM-Tropics A (September) campaign due to a drier atmosphere and higher overhead O3 column amounts. Copyright 2001 by the American Geophysical Union

Model study of tropospheric trace species distributions during PEM-West A

A three-dimensional mesoscale transport/photochemical model is used to study the transport and photochemical transformation of trace species over eastern Asia and western Pacific for the period from September 20 to October 6, 1991, of the Pacific Exploratory Mission-West A experiment. The influence of emissions from the continental boundary layer that was evident in the observed trace species distributions in the lower troposphere over the ocean is well simulated by the model. In the upper troposphere, species such as O3, NOy (total reactive nitrogen species), and SO2 which have a significant source in the stratosphere are also simulated well in the model, suggesting that the upper tropospheric abundances of these species are strongly influenced by stratospheric fluxes and upper tropospheric sources. In the case of SO2 the stratospheric flux is identified to be mostly from the Mount Pinatubo eruption. Concentrations in the upper troposphere for species such as CO and hydrocarbons, which are emitted in the continental boundary layer and have a sink in the troposphere, are significantly underestimated by the model. Two factors have been identified to contribute significantly to the underestimate: one is emissions upwind of the model domain (eastern Asia and western Pacific); the other is that vertical transport is underestimated in the model. Model results are also grouped by back trajectories to study the contrast between compositions of marine and continental air masses. The model-calculated altitude profiles of trace species in continental and marine air masses are found to be qualitatively consistent with observations. However, the difference in the median values of trace species between continental air and marine air is about twice as large for the observed values as for model results. This suggests that the model underestimates the outflow fluxes of trace species from the Asian continent and the Pacific rim countries to the ocean. Observed altitude profiles for species like CO and hydrocarbons show a negative gradient in continental air and a positive gradient in marine air. A mechanism which may be responsible for the altitude gradients is proposed

Large-scale air mass characteristics observed over the remote tropical Pacific Ocean during March-April 1999: Results from PEM-Tropics B field experiment

Eighteen long-range flights over the Pacific Ocean between 38° S to 20° N and 166° E to 90° W were made by the NASA DC-8 aircraft during the NASA Pacific Exploratory Mission (PEM) Tropics B conducted from March 6 to April 18, 1999. Two lidar systems were flown on the DC-8 to remotely measure vertical profiles of ozone (O3), water vapor (H2O), aerosols, and clouds from near the surface to the upper troposphere along their flight track. In situ measurements of a wide range of gases and aerosols were made on the DC-8 for comprehensive characterization of the air and for correlation with the lidar remote measurements. The transition from northeasterly flow of Northern Hemispheric (NH) air on the northern side of the Intertropical Convergence Zone (ITCZ) to generally easterly flow of Southern Hemispheric (SH) air south of the ITCZ was accompanied by a significant decrease in O3, carbon monoxide, hydrocarbons, and aerosols and an increase in H2O. Trajectory analyses indicate that air north of the ITCZ came from Asia and/or the United States, while the air south of the ITCZ had a long residence time over the Pacific, perhaps originating over South America several weeks earlier. Air south of the South Pacific Convergence Zone (SPCZ) came rapidly from the west originating over Australia or Africa. This air had enhanced O3 and aerosols and an associated decrease in H2O. Average latitudinal and longitudinal distributions of O3 and H2O were constructed from the remote and in situ O3 and H2O data, and these distributions are compared with results from PEM-Tropics A conducted in August-October 1996. During PEM-Tropics B, low O3 air was found in the SH across the entire Pacific Basin at low latitudes. This was in strong contrast to the photochemically enhanced O3 levels found across the central and eastern Pacific low latitudes during PEM-Tropics A. Nine air mass types were identified for PEM-Tropics B based on their O3, aerosols, clouds, and potential vorticity characteristics. The data from each flight were binned by altitude according to air mass type, and these results showed the relative observational frequency of the different air masses as a function of altitude in seven regions over the Pacific. The average chemical composition of the major air mass types was determined from in situ measurements in the NH and SH, and these results provided insight into the origin, lifetime, and chemistry of the air in these regions. Copyright 2001 by the American Geophysical Union