Tropospheric reactive odd nitrogen over the South Pacific in austral springtime

The distribution of reactive nitrogen species over the South Pacific during austral springtime appears to be dominated by biomass burning emissions and possibly lightning and stratospheric inputs. The absence of robust correlations of reactive nitrogen species with source-specific tracers (e.g., C2H2 [combustion], CH3Cl [biomass burning], C2Cl4 [industrial],210Pb [continental], and 7Be [stratospheric]) suggests significant aging and processing of the sampled air parcels due to losses by surface deposition, OH attack, and dilution processes. Classification of the air parcels based on CO enhancements indicates that the greatest influence was found in plumes at 3–8 km altitude in the distributions of HNO3 and peroxyacetyl nitrate (PAN). Here mixing ratios of these species reached 600 parts per trillion by volume (pptv), values surprisingly large for a location several thousand kilometers removed from the nearest continental areas. The mixing ratio of total reactive nitrogen (the NOy sum), operationally defined in this paper as measured (NO + HNO3 + PAN + CH3ONO2 + C2H5ONO2) + modeled (NO2), had a median value of 285 pptv within these plumes compared with 120 pptv in nonplume air parcels. Particle NO−3 was not included in this analysis of the NOy sum due to its 10- to 15-min sampling time resolution, but, in general, it was \u3c10% of the NOy sum. Comparison of the two air parcel classifications for NOy and alkyl nitrate distributions showed no perceivable plume influence, but recycling of reactive nitrogen may have masked this direct effect. In the marine boundary layer, the NOy sum averaged 50 pptv in both air parcel classifications, being somewhat isolated from the polluted conditions above it by the trade wind inversion. In this region, however, alkyl nitrates appear to have an important marine source where they comprise 20–80% of the NOy sum in equatorial and high-latitude regions over the South Pacific

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