Engineering topics
Publications and source records attributed to Stewart, Richard W..
The 2007 Technical Highlights describes the efforts of all members of the Laboratory for Atmospheres. Their dedication to advancing Earth Science through conducting research, developing and running models, designing instruments, managing projects, running field campaigns, and numerous other activities, is highlighted in this report.
The 2006 Technical Highlights describes the efforts of all members of the Laboratory for Atmospheres. Their dedication to advancing Earth science through conducting research, developing and running models, designing instruments, managing projects, running field campaigns, and numerous other activities, are highlighted in this report.
The troposphere above the West Antarctic Ice Sheet (WAIS) was sampled for hydroperoxides at 21 locations during 2-month-long summer traverses from 2000 to 2002, as part of US ITASE (International Transantarctic Scientific Expedition). First time quantitative measurements using an HPLC method showed that methylhydroperoxide (MHP) is the only important organic hydroperoxide occurring in the Antarctic troposphere, and that it is found at levels ten times those previously predicted by photochemical models. During three field seasons, means and standard deviations for hydrogen peroxide (H2O2) were 321+/-158 pptv, 650+/-176 pptv and 330+/-147 pptv. While MHP was detected, but not quantified in December 2000, levels in summer 2001 and 2002 were 317+128 pptv and 304+/-172.2 pptv. Results from firn air experiments and diurnal variability of the two species showed that atmospheric H2O2 is significantly impacted by a physical snow pack source between 76 and 90degS, whereas MHP is not. We show strong evidence of a positive feedback between stratospheric ozone and H2O2 at the surface. Between November-27 and December-12 in 2001, when ozone column densities dropped below 220 DU (means in 2000 and 2001 were 318 DU and 334 DU, respectively), H2O2 was 1.7 times that observed in the same period in 2000 and 2002, while MHP was only 80% of the levels encountered in 2002. Photochemical box model runs suggest that NO and OH levels on WAIS are closer to coastal values, while Antarctic Plateau levels are higher, confirming that region to be a highly oxidizing environment. The modeled sensitivity of H2O2 and particularly MHP to NO offers the potential to use atmospheric hydroperoxides to constrain the NO background and thus estimate the past oxidation capacity of the remote atmosphere. Index Terms: 0365 Atmospheric Composition and Structure: Troposphere: composition and chemistry; 0322 Atmospheric Composition and Structure: Constituent sources and sinks; 1610 Global Change: Atmosphere (03 15,0325); 0736 Cryosphere: Snow (1827, 1863); 0724 Cryosphere: Ice Cores (4932) Keywords: hydrogen peroxide, methylhydroperoxide, Antarctica, air-snow exchange, stratospheric ozone, atmospheric oxidation capacity
Multiple steady-state solutions are a fairly robust feature of simplified models of tropospheric photochemistry and have been reported for a range of different modeling assumptions. Multiple solutions occur through a bifurcation as changes in a control parameter induce a transition from low to high NO(x) conditions. The usual control parameters are the sources of NO and of CO, CH4 or non-methane hydrocarbons. Typically, with increasing NO source, bifurcations occur at NO(x). concentrations that are higher than would be expected of even heavily polluted conditions. However, there are other ways of inducing a low NO(x) - high NO(x) transition. In this paper the primary control parameter is solar zenith angle. This is varied throughout the year by computing noontime steady states on successive days. Background NO(x), varied by assuming different NO(x) sources values, is used as a secondary control parameter. It is found that bifurcations can occur from high to low NO(x) conditions, for reasonable background NO(x) levels, as the model progresses through spring and then from low to high NO,, during the progression through fall. A time dependent version of this model has been run for the same parameter values as in the steady state runs. This shows rapid spring and fall transitions between high and low NO(x) states. H2O2, for example, rises from sub-ppb levels to about 2 ppb over a five day period in spring and declines quickly, but less precipitously, in fall. This study supports the suggestions that the rapid change in peroxide concentrations between summer and winter conditions may be understood as a manifestation of different underlying steady-state behavior.
This is the final report for NAS5-97039 for work performed between December 1996 and November 1999. The overall objective of this project is to improve the understanding of coupling processes among atmospheric chemistry, aerosol and climate, all important for quantitative assessments of global change. Among our priority are changes in ozone and stratospheric sulfate aerosol, with emphasis on how ozone in the lower stratosphere would respond to natural or anthropogenic changes. The work emphasizes two important aspects: (1) AER's continued participation in preparation of, and providing scientific input for, various scientific reports connected with assessment of stratospheric ozone and climate. These include participation in various model intercomparison exercises as well as preparation of national and international reports. (2) Continued development of the AER three-wave interactive model to address how the transport circulation will change as ozone and the thermal properties of the atmosphere change, and assess how these new findings will affect our confidence in the ozone assessment results.
Understanding the photochemistry of the Antarctic region is important for several reasons. Analysis of ice cores provides historical information on several species such as hydrogen peroxide and sulfur-bearing compounds. The former can potentially provide information on the history of oxidants in the troposphere and the latter may shed light on DMS-climate relationships. Extracting such information requires that we be able to model the photochemistry of the Antarctic troposphere and relate atmospheric concentrations to deposition rates and sequestration in the polar ice. This paper deals with one aspect of the uncertainty inherent in photochemical models of the high latitude troposphere: that arising from imprecision in the kinetic data used in the calculations. Such uncertainties in Antarctic models tend to be larger than those in models of mid to low latitude clean air. One reason is the lower temperatures which result in increased imprecision in kinetic data, assumed to be best characterized at 298K. Another is the inclusion of a DMS oxidation scheme in the present model. Many of the rates in this scheme are less precisely known than are rates in the standard chemistry used in many stratospheric and tropospheric models.
Analysis of meteorological, chemical and microphysical data from the airborne SUCCESS (SUbsonic aircraft Contrail and Cloud Effects Special Study) mission is reported. Careful analysis of the complex DC-8 flight pattern of May 2, 1996 reveals 19 linear flight segments within six main geographical areas, which we have analyzed. Significant mountain wave activity is revealed in the data from the MMS (Meteorology Measurement System) and MTP (Microwave Temperature Profiler) instruments on the DC-8, which resembles previous observations of mountain wave structures near Boulder, Colorado. Strong mountain-wave-induced upwelling downwind of the Rockies is noted. Turbulence is also noted in regions of the mountain wave consistent with overturning near the tropopause. Zonal winds recorded on the ER-2 are shown to be consistent with mountain wave breaking at or near critical levels in the stratosphere, consistent with the strong turbulence reported by the pilot during the ER-2 flight. These observations have been supported with spectral analyses and modeling studies. 'Postcasts' of mountain wave activity on May 2, 1996 using the Naval Research Laboratory Mountain Wave Forecast Model predicts both strong mountain wave activity near the tropopause and strong mountain-wave-induced turbulence in the stratosphere.
Monte Carlo methods are frequently applied to the evaluation of uncertainties in models with multiple inputs that themselves have associated imprecisions. In the case of photochemical models used to evaluate changes in O3 or OH, inputs analyzed include rate coefficients measured in the laboratory, and chemical and physical constituents measured in the atmosphere. The Monte Carlo method was used with the 1-dimensional GSFC tropospheric photochemical model to examine uncertainty propagation to calculation of NO(x) and the major oxidants (O3, OH) in the upper troposphere. In all cases chemical kinetics inputs are varied and the NO(x) perturbation of a subsonic fleet is simulated. A series of model runs is used to explore sensitivities of model-computed parameters to other parameters: heterogeneous processes, the uncertainty in upper tropospheric H2O vapor measurements, aircraft emissions at different latitudes.
The equations describing the distributions and concentrations of trace species are nonlinear and may thus possess more than one solution. This paper develops methods for searching for multiple physical solutions to chemical continuity equations and applies these to subsets of equations describing tropospheric chemistry. The calculations are carried out with a box model and use two basic strategies. The first strategy is a 'search' method. This involves fixing model parameters at specified values, choosing a wide range of initial guesses at a solution, and using a Newton-Raphson technique to determine if different initial points converge to different solutions. The second strategy involves a set of techniques known as homotopy methods. These do not require an initial guess, are globally convergent, and are guaranteed, in principle, to find all solutions of the continuity equations. The first method is efficient but essentially 'hit or miss' in the sense that it cannot guarantee that all solutions which may exist will be found. The second method is computationally burdensome but can, in principle, determine all the solutions of a photochemical system. Multiple solutions have been found for models that contain a basic complement of photochemical reactions involving O(x), HO(x), NO(x), and CH4. In the present calculations, transitions occur between stable branches of a multiple solution set as a control parameter is varied. These transitions are manifestations of hysteresis phenomena in the photochemical system and may be triggered by increasing the NO flux or decreasing the CH4 flux from current mean tropospheric levels.
Random photochemical reaction rates are employed in a 1D photochemical model to examine uncertainties in tropospheric concentrations and thereby determine critical kinetic processes and significant correlations. Monte Carlo computations are used to simulate different chemical environments and their related imprecisions. The most critical processes are the primary photodissociation of O3 (which initiates ozone destruction) and NO2 (which initiates ozone formation), and the OH/methane reaction is significant. Several correlations and anticorrelations between species are discussed, and the ozone/transient OH correlation is examined in detail. One important result of the modeling is that estimates of global OH are generally about 25 percent uncertain, limiting the precision of photochemical models. Techniques for reducing the imprecision are discussed which emphasize the use of species and radical species measurements.
A one-dimensional model based on the sensitivity coefficients of Thompson (1990) is used to calculate regional changes in tropospheric O3 and OH due to specified global or regional changes in CH4 and CO emissions over the period 1985-2035. The methods applied are explained, and the results are presented in extensive tables and graphs and characterized in detail. A 10-15-percent increase in global tropospheric O3 and a 10-15-percent decrease in OH are predicted for both (1) global scenarios with continuing increases in CH4 and CO and (2) regional scenarios where emissions are limited in some regions but not in others; significant regional variation in O3 is predicted for (2). If depletion of O3 in the stratosphere and global warming are introduced into (1) or (2), however, they nearly cancel out the tropospheric O3 increases and OH decreases.
A major tropospheric loss of soluble species such as nitric acid results from scavenging by water droplets. Several theoretical formulations have been advanced which relate an effective time-independent loss rate for soluble species to statistical properties of precipitation such as the wet fraction and length of a precipitation cycle. In this paper, various 'effective' loss rates that have been proposed are compared with the results of detailed time-dependent model calculations carried out over a seasonal time scale. The model is a stochastic precipitation model coupled to a tropospheric photochemical model. The results of numerous time-dependent seasonal model runs are used to derive numerical values for the nitric acid residence time for several assumed sets of preciptation statistics. These values are then compared with the results obtained by utilizing theoretical 'effective' loss rates in time-independent models.
The sensitivities of tropospheric HO2 and hydrogen peroxide (H2O2) levels to increases in CH4, CO, and NO emissions and to changes in stratospheric O3 and tropospheric O3 and H2O have been evaluated with a one-dimensional photochemical model. Specific scenarios of CH4-CO-NO(x) emissions and global climate changes are used to predict HO2 and H2O2 changes between 1980 and 2030. Calculations are made for urban and nonurban continental conditions and for low latitudes. Generally, CO and CH4 emissions will enhance H2O2; NO emissions will suppress H2O2 except in very low NO(x) regions. A global warming or stratospheric O3 depletion will add to H2O2. Hydrogen peroxide increases from 1980 to 2030 could be 100 percent or more in the urban boundary layer.
A model for the effective scavenging rate of a soluble species has been developed. The model takes into account the possibility of positive as well as negative correlations between departures from the mean of the scavenging rate and species concentration. The model is demonstrated for the case of late afternoon rainout of nitric acid occurring just prior to the nighttime cessation of its chemical production. The calculations give effective scavenging rates which are about a factor of 2 to 3 greater than those calculated using the models of Rodhe and Grandell (1972) and Giorgi and Chameides (1985).