Distribution of hydrogen peroxide and methylhydroperoxide over the Pacific and South Atlantic Oceans

The gas phase hydrogen peroxide and methylhydroperoxide concentrations were measured in the troposphere over the tropical Pacific Ocean as a component of NASA's Global Tropospheric Experiment/Pacific Exploratory Mission-Tropics A field campaign. Flights on two aircraft covered the Pacific from 70°S to 60°N and 110°E to 80°W and South Atlantic from 40°S to 15°N and 45°W to 70°E, and extending from 76 to 13,000 m altitude. H2O2 and CH3OOH have the highest concentrations at a given altitude at the equator and decrease with increasing latitude in both the northern and southern hemispheres. Above 4 km the gradient is substantially reduced for both H2O2 and CH3OOH with latitude, and at altitudes in excess of 8 km there is no latitudinal dependence. H2O2 and CH3OOH exhibit maximum mixing ratios between 1 and 2 km at all latitudes. The mean mixing ratio of H2O2 at the equator was 1600 ± 600 parts per trillion by volume (pptv) decreasing to 500 ± 250 pptv at latitudes greater than 55° north and south between 1 and 2 km altitude. CH3OOH at the equator was 1400 ± 250 pptv, decreasing to 330 ± 200 pptv at high latitudes at altitudes between 1 and 2 km. The concentration of peroxides at high latitudes in the northern hemisphere was generally a factor of 2 higher than at corresponding latitudes in the southern hemisphere. The ratio of H2O2 to CH3OOH was between 1 and 2 from 45°S to 35°N at altitudes below 4 km. Between 5° to 15°N the ratio is less than 1, due to preferential removal of H2O2 in the Intertropical Convergence Zone. Copyright 1999 by the American Geophysical Union

Chemical signatures of aged Pacific marine air: Mixed layer and free troposphere as measured during PEM-West A

The Pacific Ocean is one of the few remaining regions of the northern hemisphere that is relatively free of direct anthropogenic emissions. However, long-range transport of air pollutants is beginning to have a significant impact on the atmosphere over the Pacific. In September and October 1991, NASA conducted the Pacific Exploratory Mission-West A expedition to study the atmospheric chemistry and background budgets of key atmospheric trace species. Aircraft sampling centered on the northern Pacific, 0° to 40°N and 115° to 180°E. The paper summarizes the chemical signature of relatively well-aged Pacific marine air (residence time ≥10 days over the ocean). The chemical signatures show that marine air is not always devoid of continental influences. Aged marine air which circulates around the semipermanent subtropical anticyclone located off the Asian continent is influenced by infusion of continental air with anthropogenic emissions. The infusion occurs as the result of Asian outflow swept off the continent behind eastward moving cold fronts. When compared to aged marine air with a more southerly pathway, this infusion results in enhancements in the mixing ratio of many anthropogenic/continental species and typically those with lifetimes of weeks in the free troposphere. Less enhancement is seen for the short-lived species with lifetimes of a few days as infused continental emissions are depleted during transport (about a week) around the semipermanent subtropical high. Copyright 1996 by the American Geophysical Union

Hydrocarbon ratios during PEM-WEST A: A model perspective

A useful application of the hydrocarbon measurements collected during the Pacific Exploratory Mission (PEM-West A) is as markers or indices of atmospheric processing. Traditionally, ratios of particular hydrocarbons have been interpreted as photochemical indices, since much of the effect due to atmospheric transport is assumed to cancel by using ratios. However, an ever increasing body of observatonial and theoretical evidence suggests that turbulent mixing associated with atmospheric transport influences certain hydrocarbon ratios significantly. In this study a three-dimensional mesoscale photochemical model is used to study the interaction of photochemistry and atmospheric mixing on select hydrocarbons. In terms of correlations and functional relationships between various alkanes the model results and PEM-West A hydrocarbon observations share many similar characteristics as well as explainable differences. When the three-dimensional model is applied to inert tracers, hydrocarbon ratios and other relationships exactly follow those expected by simple dilution with model-imposed "background air," and the three-dimensional results for reactive hydrocarbons are quite consistent with a combined influence of photochemistry and simple dilution. Analogous to these model results, relationships between various hydrocarbons collected during the PEM-West A experiment appear to be consistent with this simplified picture of photochemistry and dilution affecting individual air masses. When hydrocarbons are chosen that have negligeble contributions to clean background air, unambiguous determinations of the relative contributions to photochemistry and dilution can be estimated from the hydrocarbon samples. Both the three-dimensional model results and the observations imply an average characteristic lifetime for dilution with background air roughly equivalent to the photochemical lifetime of butane for the western Pacific lower troposphere. Moreover, the dominance of OH as the primary photochemical oxidant downwind of anthropogenic source regions can be inferred from correlations between the highly reactive alkane ratios. By incorporating back-trajectory information within the three-dimensional model analysis, a correspondence between time and a particular hydrocarbon or hydrocarbon ratio can be determined, and the influence of atmospheric mixing or photochemistry can be quantified. Results of the three-dimensional model study are compared and applied to the PEM-West A hydrocarbon dataset, yielding a practical methodology for determining average OH concentrations and atmospheric mixing rates from the hydrocarbon measurements. Aircraft data taken below 2 km during wall flights east of Japan imply a diurnal average OH concentration of ∼3 × 106 cm-3. The characteristic time for dilution with background air is estimated to be ∼2.5 days for the two study areas examined in this work. Copyright 1996 by the American Geophysical Union

A meteorological overview of the Pacific Exploratory Mission (PEM) Tropics period

NASA's Pacific Exploratory Mission-Tropics (PEM-T) experiment investigated the atmospheric chemistry of a large portion of the tropical and subtropical Pacific Basin during August to October 1996. This paper summarizes meteorological conditions over the PEM-T domain. Mean flow patterns during PEM-T are described. Important circulation systems near the surface include subtropical anticyclones, the South Pacific Convergence Zone (SPCZ), the Intertropical Convergence Zone (ITCZ), and middle latitude transient cyclones. The SPCZ and ITCZ are areas of widespread ascent and deep convection; however, there is relatively little lightning in these oceanic regions. A large area of subsidence is associated with the subtropical anticyclone centered near Easter Island. PEM-T occurred during a period of near normal sea surface temperatures. When compared to an 11 year climatology (1986-1996), relatively minor circulation anomalies are observed during PEM-T. Some of these circulation anomalies are consistent with much stronger anomalies observed during previous La Nina events. In general, however, the 1996 PEM-T period appears to be climatologically representative. Meteorological conditions for specific flights from each major operations area are summarized. The vertical distribution of ozone along selected DC-8 flights is described using the DIAL remote sensing system. These ozone distributions are related to thermodynamic soundings obtained during aircraft maneuvers and to backward trajectories that arrived at locations along the flight tracks. Most locations in the deep tropics are found to have relatively small values of tropospheric ozone. Backward trajectories calculated from global gridded analyses show that much of this air originates from the east and has not passed over land within 10 days. The deep convection associated with the ITCZ and SPCZ also influences the atmospheric chemistry of these regions. Flights over portions of the subtropics and middle latitudes document layers of greatly enhanced tropospheric ozone, sometimes exceeding 80 ppbv. In situ carbon monoxide in these layers often exceeds 90 ppbv. These regions are located near, and especially south of Tahiti, Easter Island, and Fiji. The layers of enhanced ozone usually correspond to layers of dry air, associated with widespread subsiding air. The backward trajectories show that air parcels arriving in these regions originate from the west, passing over Australia and even extending back to southern Africa. These are regions of biomass burning. The in situ chemical measurements support the trajectory-derived origins of these ozone plumes. Thus the enhanced tropospheric ozone over the central Pacific Basin may be due to biomass burning many thousands of kilometers away. Middle-latitude portions of the PEM-T area are influenced by transient cyclones, and the DC-8 traversed tropopause folds during several flights. The flight area just west of Ecuador experiences outflow from South America. Thus the biomass burning that is prevalent over portions of Brazil influences this area. Copyright 1999 by the American Geophysical Union