Robert B. Chatfield

Measurements and model simulations of the photostationary state during the Mauna Loa Observatory Photochemistry Experiment: Implications for radical concentrations and ozone production and loss rates

Simultaneous measurements of [NO2], [NO], [O3], and the NO2 photo-dissociation rate coefficient, J2, were made during a one-month field study in the spring of 1988 at Mauna Loa, Hawaii, and were used to evaluate the photostationary state ratio, ϕ = J2[NO2]/k1[NO][O3]. Over 5600 measurements were made for clear sky conditions, allowing a detailed comparison with photochemical theory. Values of ϕ determined from the observations were consistently higher than unity, approaching 2.0 for high sun, and indicated peroxy radical mixing ratios near 60 pptv. High sun values of ϕ were independent of NOx (NO + NO2), but correlated well with ozone and water vapor through the expression ϕ−1 = (0.11 ± 0.21) + (1.59 ± 0.64) × 10−3 × ([H2O]/[O3])½. A photochemical box model is shown to give good agreement with the values of ϕ, the peroxy radical concentrations, and the correlations with physical and chemical environmental variables determined from the observations. The rate of photochemical production of ozone was estimated from measurements of ϕ, and the rate of photochemical ozone destruction was estimated from the box model. For free tropospheric air samples characteristic of altitudes near 3.4 km, the 24-hour average net ozone production rate is shown to be −0.5 ppbv/d (net ozone destruction), and is determined primarily by photolytic destruction.

Biomass burning and deep convection in southeastern Asia: Results from ASHOE/MAESA

There was extensive biomass burning in Indonesia, northern Australia, and New Guinea during September and October 1994. This paper discusses two accidental encounters of biomass plumes from the 1994 Airborne Southern Hemisphere Ozone Experiment and Measurements for Assessing the Effects of Stratospheric Aircraft campaign (ASHOE/MAESA). During the October 23 descent into Fiji, and an ascent from Fiji on October 24, the NASA ER-2 passed through layers highly enhanced in NO, NO y , CO, and O 3 . These layers occurred near an altitude of 15 km. Back trajectories and satellite images indicate that the layers probably originated as outflow from a convective disturbance near New Guinea. The measurements indicate that deep convection can inject emissions from southeast Asian biomass burning to near tropical tropopause altitudes. Deep convection magnifies the impact of biomass burning on tropospheric chemistry because of the much longer residence times and chemical lifetimes of species in the upper tropical troposphere. Transport of the products of southeast Asian biomass burning into the upper tropical troposphere, followed by southward high-level outflow and advection by the subtropical jet, may play a significant role in dispersing these emissions on a global scale. Anthropogenic emissions from countries in southeast Asia are likely to increase in the future as these countries become more highly industrialized. This transport mechanism may play a role in increasing the impact of these types of emissions as well.

Nitric acid scavenging by mineral and biomass burning aerosols

The abundance of gas phase nitric acid in the upper troposphere is overestimated by global chemistry-transport models, especially during the spring and summer seasons. Recent aircraft data obtained over the central US show that mineral aerosols were abundant in the upper troposphere during spring. Chemical reactions on mineral dust may provide an important sink for nitric acid. In regions where the mineral dust abundance is low in the upper troposphere similar HNO3 removal processes may occur on biomass burning aerosols. We propose that mineral and biomass burning aerosols may provide an important global sink for gas phase nitric acid, particularly during spring and summer when aerosol composition in the upper troposphere may be greatly affected by dust storms from east Asia or tropical biomass burning plumes.

Intercontinental Chemical Transport Experiment Ozonesonde Network Study (IONS) 2004: 1. Summertime upper troposphere/lower stratosphere ozone over northeastern North America

Coordinated ozonesonde launches from the Intercontinental Transport Experiment (INTEX) Ozonesonde Network Study (IONS) (http://croc.gsfc.nasa.gov/intex/ions.html) in July-August 2004 provided nearly 300 O3 profiles from eleven North American sites and the R/V Ronald H. Brown in the Gulf of Maine. With the IONS period dominated by low-pressure conditions over northeastern North America (NENA), the free troposphere in that region was frequently enriched by stratospheric O3. Stratospheric O3 contributions to the NENA tropospheric O3 budget are computed through analyses of O3 laminae (Pierce and Grant, 1998; Teitelbaum et al., 1996), tracers (potential vorticity, water vapor), and trajectories. The lasting influence of stratospheric incursions into the troposphere is demonstrated, and the computed stratospheric contribution to tropospheric column O3 over the R/V Ronald H. Brown and six sites in Michigan, Virginia, Maryland, Rhode Island, and Nova Scotia, 23% ± 3%, is similar to summertime budgets derived from European O3 profiles (Collette and Ancellet, 2005). Analysis of potential vorticity, Wallops ozonesondes (37.9°N, 75.5°W), and Measurements of Ozone by Airbus In-service Aircraft (MOZAIC) O3 profiles for NENA airports in June-July-August 1996–2004 shows that the stratospheric fraction in 2004 may be typical. Boundary layer O3 at Wallops and northeast U.S. sites during IONS also resembled O3 climatology (June-July-August 1996–2003). However, statistical classification of Wallops O3 profiles shows the frequency of profiles with background, nonpolluted boundary layer O3 was greater than normal during IONS.

A general model of how fire emissions and chemistry produce African/oceanic plumes (O3, CO, PAN, smoke) in TRACE A

A full-chemistry simulation of the Great African Plume gives one example of a broad conceptual model of the intercontinental pollution of the tropical middle troposphere by lofted biomass burning plumes. This two-dimensional idealization “calibrated” by carbon monoxide distributions links conventional estimates of burning emissions to oceanic concentrations of pollutants. This paper makes use of GRACES, a modular photochemical simulation system, in two forms. The results of the chemically intensive two-dimensional form, using idealized winds, mixing, deposition, and rainout, match the general concentration patterns of a three-dimensional GRACES model study of CO during the TRACE A/SAFARI period of October 1992 (reported separately). The study highlights the importance of simulating the vertical and diurnal variation of the planetary boundary layer and cloud activity. These correlate temporally with the intensity of tropical agricultural burning. We emphasize one situation, the drift northward and eastward of pollution into the interocean convergence region, where it rises by small-scale motions and rides out westward in the lower midtroposphere (<5 km). These effects help set in place large strata of enhanced CO, ozone, and other pollution over the equatorial Atlantic Ocean. Overall, our comparisons of simulations with the TRACE A data on the cycling of CO, NOx, and O3 in the tropical atmosphere suggest substantial agreement of current emission estimates and atmospheric concentrations. In certain regions, ozone is simulated slightly below observed levels. The striking major disagreements are in NOy, (total reactive nitrogen) and HNO3, which are intimately related to CO and O3; this suggests that current theory omits at least one fundamental process.

Passive tracer transport relevant to the TRACE A experiment

This paper explores some of the mechanisms governing the accumulation of passive tracers over the tropical southern Atlantic Ocean during the northern hemisphere fall season. There has been a pioneering observation regarding ozone maxima over the South Atlantic during austral spring. The understanding of the formation of this maxima has been the prime motivation for this study. Using a global model as a frame of reference, we have carried out three kinds of experiments during the period of the Transport and Atmospheric Chemistry Near the Equator-Atlantic (TRACE A) project of 1992. The first of these is a simple advection of total ozone (a passive tracer) in time using the Florida State University global spectral model. Integration over the period of roughly 1 week showed that the model quite closely replicates the behavior of the observed total ozone from the total ozone mapping spectrometer (TOMS). This includes many of the changes in the features of total ozone over the tropical and subtropical region of the southern Atlantic Ocean. These studies suggest a correlation of 0.8 between the observed ozone over this region and ozone modeled from “dynamics alone,” i.e., without recourse to any photochemistry. The second series of experiments invoke sustained sources of a tracer over the biomass burn region of Africa and Brazil. Furthermore, sustained sources were also introduced in the active frontal “descending air” region of the southern hemisphere and over the Asian monsoons east-west circulation. These experiments strongly suggest that air motions help to accumulate tracer elements over the tropical southern Atlantic Ocean. A third series of experiments address what may be required to improve the deficiencies of the vertical stratification of ozone predicted by the model over the flight region of the tropical southern Atlantic during TRACE A. Here we use the global model to optimally derive plausible accumulation of burn elements over the fire count regions of Brazil and Africa to provide passive tracer advections to closely match what was observed from reconnaissance aircraft-based measurements of ozone over the tropical southern Atlantic Ocean.

Impact of acetone on ozone production and OH in the upper troposphere at high NOx

The impact of acetone (or any HOx source) on tropospheric photochemistry is largest in the high NOx regime. The fractional increases in OH and ozone production associated with acetone increase rapidly with NOx when NOx mixing ratios become larger than 300 parts per trillion by volume (pptv). This occurs in part because the HOx yield of acetone is larger at higher NOx mixing ratios, going from about 1 HOx at NOx ∼ 10 pptv to 3 HOx at NOx ∼ 1000 pptv. We also investigate the effect of acetone on the partitioning of the NOy family. Acetone increases the conversion of NO to NO2, HNO4, HNO3, and peroxyacetylnitrate (PAN). Conversion of NO to PAN dominates at low NOx, while conversion of NO to HNO3 dominates at high NOx. These NO decreases significantly diminish the increases in OH and ozone production one would otherwise anticipate from the increases in HO2. In particular, acetone can be expected to reduce ozone production for NOx<25 pptv. We also show that most of the changes in species concentrations arising from the introduction of a HOx source can be accurately predicted using simple expressions derived from linear perturbation theory.

Observations of HO x and its relationship with NO x in the upper troposphere during SONEX

Simultaneous measurements of the oxides of hydrogen and nitrogen made during the NASA Subsonic Assessment, Ozone and Nitrogen Oxide Experiment (SONEX) afforded an opportunity to study the coupling between these two important families throughout the free troposphere and lowermost stratosphere. Moreover, the suite of measurements made during the campaign was unprecedented in its completeness, thus providing a uniquely detailed picture of the radical photochemistry that drives oxidation and ozone production in this part of the atmosphere. On average, observed hydrogen oxides (HOx = OH + HO2) agree well with both instantaneous and diel steady-state models; however, there is a persistent deviation of the observations that correlates with the abundance of nitrogen oxides (NOx = NO + NO2) in the sampled air mass. Specifically, the observed HOx tends to exceed the model predictions in the presence of high NOx concentrations, by as much as a factor of 5 (> 500 pptv NOx), and is sometimes as little as half that expected by steady state at lower NOx levels. While many possibilities for these discrepancies are discussed, it is argued that an instrumental artifact is not probable and that the discrepancy may bespeak a shortcoming of our understanding of HOx chemistry. The consistently elevated HOx in the presence of elevated NOx leads directly to greater ozone production than expected, thereby extending the NOx-limited regime of the upper troposphere. These results could thus have bearing on the predicted impacts of increasing NOx emissions into this region of the atmosphere from, for example, the growth of global air traffic.

The Great African Plume from biomass burning: Generalizations from a three‐dimensional study of TRACE A carbon monoxide

The “Great African Plume” flows westward from a wind divergence line over Central Africa to pollute the Equatorial Atlantic Ocean. The plume arises from agricultural burning fumes which mix in a 3–4 km deep boundary layer over Africa, then override cooler rainforest air, and finally swerve westward, where their progress into the Atlantic is “gated” by southern storm systems. Another prominent elevated “Global Burning Plume” from Tropical South America flows past South Africa above 8 km altitude. Joining elevated African plumes, it influences the South Indian and Southern Oceans. These are results from our GRACES (Global Regional Atmospheric Chemistry Event Simulator), which was used to study carbon monoxide during an intensive experimental period, September-October 1992. Traces of the plumes are also evident in observations of CO in the Measurement of Air Pollution from Satellites (MAPS) samples of October, 1994, suggesting a general phenomena. To arrive at these conclusions, we used the detailed weather reconstructions afforded by MM5 meteorological model dynamics to drive GRACES. Both statistical and detailed (event) comparisons of CO and observed aboard the NASA DC-8 are good, especially <6 km altitude. The following model adaptations that we required may inform global analysis and global models: (1) Parameterized vertical transport like planetary boundary layer convection and deep cumulonimbus convection strongly control CO, allowing far more precision than trajectory studies and models using only large-scale motions. (2) CO sources during this period were consistent with the Hao and Liu [1994] report-based carbon-burn rates; (3) deep convection is even more active than as parameterized by MM5s Grell-scheme: on the large scale: mass fluxes effective for CO redistribution may be over twice core-updraft values diagnosed strengths.

Improved retrieval of PM2.5 from satellite data products using non-linear methods

Satellite observations may improve the areal coverage of particulate matter (PM) air quality data that nowadays is based on surface measurements. Three statistical methods for retrieving daily PM2.5 concentrations from satellite products (MODIS-AOD, OMI-AAI) over the San Joaquin Valley (CA) are compared--Linear Regression (LR), Generalized Additive Models (GAM), and Multivariate Adaptive Regression Splines (MARS). Simple LRs show poor correlations in the western USA (R(2) ~/= 0.2). Both GAM and MARS were found to perform better than the simple LRs, with a slight advantage to the MARS over the GAM (R(2) = 0.71 and R(2) = 0.61, respectively). Since MARS is also characterized by a better computational efficiency than GAM, it can be used for improving PM2.5 retrievals from satellite aerosol products. Reliable PM2.5 retrievals can fill in missing surface measurements in areas with sparse ground monitoring coverage and be used for evaluating air quality models and as exposure metrics in epidemiological studies.