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Salawitch, Ross J.

Publications and source records attributed to Salawitch, Ross J..

At least 19 records
All sourcesNASA NTRSDOE OSTI
NASA NTRS2017

BrO and Inferred Bry Profiles over the Western Pacific: Relevance of Inorganic Bromine Sources and a Bry Minimum in the Aged Tropical Tropopause Layer

We report measurements of bromine monoxide (BrO) and use an observationally constrained chemical box model to infer total gas-phase inorganic bromine (Br(sub y)) over the tropical western Pacific Ocean (tWPO) during the CONTRAST field campaign (January-February 2014). The observed BrO and inferred Bry profiles peak in the marine boundary layer (MBL), suggesting the need for a bromine source from sea-salt aerosol (SSA), in addition to organic bromine (CBry ). Both profiles are found to be C-shaped with local maxima in the upper free troposphere (FT). The median tropospheric BrO vertical column density (VCD) was measured as 1.6 x 10(exp 13) molec cm(exp -2), compared to model predictions of 0.9 x 10(exp 13) molec cm(exp -2) in GEOS-Chem (CBr(sub y) but no SSA source), 0.4 x 10(exp 13) molec cm(exp -2) in CAM-Chem (CBr(sub y) and SSA), and 2.1 x 10(exp 13) molec cm(exp -2) in GEOS-Chem (CBry and SSA). Neither global model fully captures the Cshape of the Br(sun y) profile. A local Br(sub y) maximum of 3.6 ppt (2.9-4.4 ppt; 95% confidence interval, CI) is inferred between 9.5 and 13.5 km in air masses influenced by recent convective outflow. Unlike BrO, which increases from the convective tropical tropopause layer (TTL) to the aged TTL, gas-phase Br(sub y) decreases from the convective TTL to the aged TTL. Analysis of gas-phase Br(sub y) against multiple tracers (CFC-11, H2O/O3 ratio, and potential temperature) reveals a Br(sub y) minimum of 2.7 ppt (2.3-3.1 ppt; 95% CI) in the aged TTL, which agrees closely with a stratospheric injection of 2.6 +/- 0.6 ppt of inorganic Br(sub y) (estimated from CFC-11 correlations), and is remarkably insensitive to assumptions about heterogeneous chemistry. Bry increases to 6.3 ppt (5.6-7.0 ppt; 95% CI) in the stratospheric "middleworld" and 6.9 ppt (6.5-7.3 ppt; 95% CI) in the stratospheric "overworld". The local Br(sub y) minimum in the aged TTL is qualitatively (but not quantitatively) captured by CAM-Chem, and suggests a more complex partitioning of gas-phase and aerosol Br(sub y) species than previously recognized. Our data provide corroborating evidence that inorganic bromine sources (e.g., SSA-derived gas-phase Br(sub y) ) are needed to explain the gas-phase Br(sub y) budget in the upper free troposphere and TTL. They are also consistent with observations of significant bromide in Upper Troposphere-Lower Stratosphere aerosols. The total Br(sub y) budget in the TTL is currently not closed, because of the lack of concurrent quantitative measurements of gas-phase Br(sub y) species (i.e., BrO, HOBr, HBr, etc.) and aerosol bromide. Such simultaneous measurements are needed to (1) quantify SSA-derived Br(sub y) in the upper FT, (2) test Br(sub y) partitioning, and possibly explain the gas-phase Br(sub y) minimum in the aged TTL, (3) constrain heterogeneous reaction rates of bromine, and (4) account for all of the sources of Br(sub y) to the lower stratosphere.

Atmospheric Chemistry; bromine; troposphere; CONTR↗
NASA NTRS2017

Impact of Evolving Isoprene Mechanisms on Simulated Formaldehyde: An Inter-comparison Supported by in Situ Observations from SENEX

Isoprene oxidation schemes vary greatly among gas-phase chemical mechanisms, with potentially significant ramifications for air quality modeling and interpretation of satellite observations in biogenic-rich regions. In this study, in situ observations from the 2013 SENEX mission are combined with a constrained O-D photochemical box model to evaluate isoprene chemistry among five commonly used gas-phase chemical mechanisms: CBO5, CB6r2, MCMv3.2, MCMv3.3.1, and a recent version of GEOS-Chem. Mechanisms are evaluated and inter-compared with respect to formaldehyde (HCHO), a high-yield product of isoprene oxidation. Though underestimated by all considered mechanisms, observed HCHO mixing ratios are best reproduced by MCMv3.3.1 (normalized mean bias = -15%), followed by GEOS-Chem (-17%), MCMv3.2 (-25%), CB6r2 (-32%) and CB05 (-33%). Inter-comparison of HCHO production rates reveals that major restructuring of the isoprene oxidation scheme in the Carbon Bond mechanism increases HCHO production by only approx. 5% in CB6r2 relative to CBO5, while further refinement of the complex isoprene scheme in the Master Chemical Mechanism increases HCHO production by approx. 16% in MCMv3.3.1 relative to MCMv3.2. The GEOS-Chem mechanism provides a good approximation of the explicit isoprene chemistry in MCMv3.3.1 and generally reproduces the magnitude and source distribution of HCHO production rates. We analytically derive improvements to the isoprene scheme in CB6r2 and incorporate these changes into a new mechanism called CB6r2-UMD, which is designed to preserve computational efficiency. The CB6r2-UMD mechanism mimics production of HCHO in MCMv3.3.1 and demonstrates good agreement with observed mixing ratios from SENEX (-14%). Improved simulation of HCHO also impacts modeled ozone: at approx. 0.3 ppb NO, the ozone production rate increases approx. 3% between CB6r2 and CB6r2-UMD, and rises another approx. 4% when HCHO is constrained to match observations.

isoprene↗
NASA NTRS2017

Quantifying the Causes of Differences in Tropospheric OH Within Global Models

The hydroxyl radical (OH) is the primary daytime oxidant in the troposphere and provides the main loss mechanism for many pollutants and greenhouse gases, including methane (CH4). Global mean tropospheric OH differs by as much as 80% among various global models, for reasons that are not well understood. We use neural networks (NNs), trained using archived output from eight chemical transport models (CTMs) that participated in the Polar Study using Aircraft, Remote Sensing, Surface Measurements and Models, of Climate, Chemistry, Aerosols and Transport Model Intercomparison Project (POLMIP), to quantify the factors responsible for differences in tropospheric OH and resulting CH4 lifetime (Tau CH4) between these models. Annual average Tau CH4, for loss by OH only, ranges from 8.0 to 11.6 years for the eight POLMIP CTMs. The factors driving these differences were quantified by inputting 3-D chemical fields from one CTM into the trained NN of another CTM. Across all CTMs, the largest mean differences in Tau CH4 (Delta Tau CH4) result from variations in chemical mechanisms (Delta Tau CH4 = 0.46 years), the photolysis frequency (J) of O3 yields O(D-1) (0.31 years), local O3 (0.30 years), and CO (0.23 years). The Delta Tau CH4 due to CTM differences in NO(x) (NO + NO2) is relatively low (0.17 years), although large regional variation in OH between the CTMs is attributed to NO(x). Differences in isoprene and J(NO2) have negligible overall effect on globally averaged tropospheric OH, although the extent of OH variations due to each factor depends on the model being examined. This study demonstrates that NNs can serve as a useful tool for quantifying why tropospheric OH varies between global models, provided that essential chemical fields are archived.

Surface Measurements and Models↗
NASA NTRS2016

Airborne Measurements of BrO and the Sum of HOBr and Br2 over the Tropical West Pacific from 1 to 15 Km During the CONvective TRansport of Active Species in the Tropics (CONTRAST) Experiment

A chemical ionization mass spectrometer was used to measure BrO and HOBr + Br2 over the Tropical West Pacific Ocean within the altitude range of 1 to 15 km, during the CONvective TRansport of Active Species in the Tropics (CONTRAST) campaign in 2014. Isolated episodes of elevated BrO (up to 6.6 pptv) and/or HOBr + Br2 (up to 7.3 pptv) were observed in the tropical free troposphere (TFT) and were associated with biomass burning. However, most of the time we did not observe significant BrO or HOBr + Br2 in the TFT and the tropical tropopause layer (TTL) above our limits of detection (LOD). The 1 min average LOD for BrO ranged from 0.6 to 1.6 pptv and for HOBr + Br2 ranged from 1.3 to 3.5 pptv. During one flight, BrO observations from the TTL to the extratropical lowermost stratosphere were used to infer a profile of inorganic bromine (Br(sub y)). Based on this profile, we estimated the product gas injection of bromine species into the stratosphere to be 2 pptv. Analysis of Br(sub y) partitioning further indicates that BrO levels are likely very low in the TFT environment and that future studies should target the measurement of HBr or atomic Br.

Isolated episodes of elevated BrO↗
NASA NTRS2016

An Observationally Constrained Evaluation of the Oxidative Capacity in the Tropical Western Pacific Troposphere

Hydroxyl radical (OH) is the main daytime oxidant in the troposphere and determines the atmospheric lifetimes of many compounds. We use aircraft measurements of O3, H2O, NO, and other species from the Convective Transport of Active Species in the Tropics (CONTRAST) field campaign, which occurred in the tropical western Pacific (TWP) during January-February 2014, to constrain a photochemical box model and estimate concentrations of OH throughout the troposphere. We find that tropospheric column OH (OHCOL) inferred from CONTRAST observations is 12 to 40% higher than found in chemical transport models (CTMs), including CAM-chem-SD run with 2014 meteorology as well as eight models that participated in POLMIP (2008 meteorology). Part of this discrepancy is due to a clear-sky sampling bias that affects CONTRAST observations; accounting for this bias and also for a small difference in chemical mechanism results in our empirically based value of OHCOL being 0 to 20% larger than found within global models. While these global models simulate observed O3 reasonably well, they underestimate NOx (NO +NO2) by a factor of 2, resulting in OHCOL approx.30% lower than box model simulations constrained by observed NO. Underestimations by CTMs of observed CH3CHO throughout the troposphere and of HCHO in the upper troposphere further contribute to differences between our constrained estimates of OH and those calculated by CTMs. Finally, our calculations do not support the prior suggestion of the existence of a tropospheric OH minimum in the TWP, because during January-February 2014 observed levels of O3 and NO were considerably larger than previously reported values in the TWP.

Hydroxyl radical↗
NASA NTRS2016

A Pervasive Role for Biomass Burning in Tropical High Ozonelow Water Structures

Air parcels with mixing ratios of high O3 and low H2O (HOLW) are common features in the tropical western Pacific (TWP) mid-troposphere (300-700 hPa). Here, using data collected during aircraft sampling of the TWP in winter 2014, we find strong, positive correlations of O3 with multiple biomass burning tracers in these HOLW structures. Ozone levels in these structures are about a factor of three larger than background. Models, satellite data and aircraft observations are used to show fires in tropical Africa and Southeast Asia are the dominant source of high O3 and that low H2O results from large-scale descent within the tropical troposphere. Previous explanations that attribute HOLW structures to transport from the stratosphere or mid-latitude troposphere are inconsistent with our observations. This study suggest a larger role for biomass burning in the radiative forcing of climate in the remote TWP than is commonly appreciated.

Satellite data↗
NASA NTRS2014

The Efficacy of Air Pollution Control Efforts: Evidence from AURA

Observations of NO2, SO2, and H2CO from OMI on AURA provide an excellent record of pollutant concentrations for the past decade. Abatement strategies to control criteria pollutants including ozone and fine particulate matter (PM2.5) have met with varying degrees of success. Sulfur controls had a profound impact on local SO2 concentrations and a measurable impact on PM2.5. Although substantial effort has gone into VOC control, ozone in the eastern US has responded dramatically to NOx emissions controls.

efficacy of air pollution↗
NASA NTRS2014

Changes in Global Tropospheric OH Expected as a Result of Climate Change Over the Last Several Decades

The oxidizing capacity of the troposphere is controlled primarily by the abundance of hydroxyl radical (OH). The global mean concentration of OH, [OH]_GLOBAL, inferred from measurements of methyl chloroform, has remained relatively constant during the past several decades, despite rising levels of CH4 that should have led to a steady decline. Here we examine other factors that may have affected [OH]_GLOBAL, such as the changing overhead burden of stratospheric O3 using observations from OMI, TOMS and SBUV; rising tropospheric H2O using observations from AIRS and reanalysis fields from MERRA; and widening of the climatological tropics using widening rate estimates from the literature and global OH fields from the GEOS Chemistry-Climate Model. Our analysis suggests these factors may have contributed a positive trend to [OH]_GLOBAL large enough to counter the decrease due to CH4.

Climate Change↗
NASA NTRS2013

Emissions Estimation from Satellite Retrievals: a Review of Current Capability

Since the mid-1990s a new generation of Earth-observing satellites has been able to detect tropospheric air pollution at increasingly high spatial and temporal resolution. Most primary emitted species can be measured by one or more of the instruments. This review article addresses the question of how well we can relate the satellite measurements to quantification of primary emissions and what advances are needed to improve the usability of the measurements by U.S. air quality managers. Built on a comprehensive literature review and comprising input by both satellite experts and emission inventory specialists, the review identifies several targets that seem promising: large point sources of NOx and SO2, species that are difficult to measure by other means (NH3 and CH4, for example), area sources that cannot easily be quantified by traditional bottom-up methods (such as unconventional oil and gas extraction, shipping, biomass burning, and biogenic sources), and the temporal variation of emissions (seasonal, diurnal, episodic). Techniques that enhance the usefulness of current retrievals (data assimilation, oversampling, multi-species retrievals, improved vertical profiles, etc.) are discussed. Finally, we point out the value of having new geostationary satellites like GEO-CAPE and TEMPO over North America that could provide measurements at high spatial (few km) and temporal (hourly) resolution.

air quality↗
NASA NTRS2006

Attribution of Recovery in Lower-stratospheric Ozone

Multiple satellite and ground-based observations provide consistent evidence that the thickness of Earth's protective ozone layer has stopped declining since 1997, close to the time of peak stratospheric halogen loading. Regression analyses with Effective Equivalent Stratospheric Chlorine (EESC) in conjunction with further analyses using more sophisticated photochemical model calculations constrained by satellite data demonstrate that the cessation of ozone depletion between 18-25 km altitude is consistent with a leveling off of stratospheric abundances of chlorine and bromine, due to the Montreal Protocol and its amendments. However, ozone increases in the lowest part of the stratosphere, from the tropopause to 18 km, account for about half of the improvement in total column ozone during the past 9 years at northern hemisphere mid-latitudes. The increase in ozone for altitudes below 18 km is most likely driven by changes in transport, rather than driven by declining chlorine and bromine. Even with this evidence that the Montreal Protocol and its amendments are having the desired, positive effect on ozone above 18 km, total column ozone is recovering faster than expected due to the apparent transport driven changes at lower altitudes. Accurate prediction of future levels of stratospheric ozone will require comprehensive understanding of the factors that drive temporal changes at various altitudes, and partitioning of the recent transport-driven increases between natural variability and changes in atmospheric structure perhaps related to anthropogenic climate change.

Yang, Eun-Su↗
NASA NTRS2005

Denitrification in the Arctic mid-winter 2004/2005 observed by airborne submillimeter radiometry

We present measurements of unusually low mixing ratios of HNO3 in the exceptionally cold Arctic vortex of late-January and early-February 2005. The measurements were obtained by the airborne submillimeter radiometer ASUR during the polar aura validation experiment (PAVE). The distribution of HNO3 inside the vortex reaches minima below 4 ppbv around 22 km altitude and maxima above 13 ppbv around 16 km altitude, with a considerable spatial variability.

measurements↗
NASA NTRS2005

Attribution of Recovery in Lower-Stratospheric Ozone

Multiple satellite and ground-based observations provide consistent evidence that the thickness of Earth's protective ozone layer has stopped declining since 1997, close to the time of peak stratospheric halogen loading. Regression analyses with Effective Equivalent Stratospheric Chlorine (EESC) in conjunction with further analyses using more sophisticated photochemical model calculations constrained by satellite data demonstrate that the cessation of ozone depletion between 18-25 km altitude is consistent with a leveling off of stratospheric abundances of chlorine and bromine, due to the Montreal Protocol and its amendments. However, ozone increases in the lowest part of the stratosphere, from the tropopause to 18 km, account for about half of the improvement in total column ozone during the past 9 years at northern hemisphere mid-latitudes. The increase in ozone for altitudes below 18 km is most likely driven by changes in transport, rather than driven by declining chlorine and bromine. Even with this evidence that the Montreal Protocol and its amendments are having the desired, positive effect on ozone above 18 km, total column ozone is recovering faster than expected due to the apparent transport driven changes at lower altitudes. Accurate prediction of future levels of stratospheric ozone will require comprehensive understanding of the factors that drive temporal changes at various altitudes, and partitioning of the recent transport-driven increases between natural variability and changes in atmospheric structure perhaps related to anthropogenic climate change.

Yang, Eun-Su↗
NASA NTRS2000

Measurement of HO2 And Other Trace Gases in The Stratosphere Using a High Resolution Far-Infrared Spectrometer

This report covers the time period 1 April 1999 to 31 March 2000. During this period we continued analyzing data from past flights, exploring issues such as radical partitioning, stratospheric transport, and stratosphere-troposphere exchange. With funding from Smithsonian we have also completed a preliminarY design for a compact, lightweight, next-generation Fourier-transform spectrometer.

Traub, Wesley A.↗
NASA NTRS2000

Modeling Stratospheric Constituents: Reactive Species That Regulate Ozone

Photochemical loss of stratospheric ozone occurs primarily by catalytic cycles whose rates are limited by the concentration of OH, HO2, NO2, ClO, and/or BrO as well as the concentration of either atomic oxygen or of ozone itself. Once the concentrations of these gases are established, the photochemical loss rate of O3 depends on the rate coefficient of only a handful of key reactions. We have developed a method for testing our understanding of stratospheric ozone photochemistry by comparing measured and modeled concentrations of reactive hydrogen, nitrogen, chlorine and bromine radicals using a photochemical steady state model constrained by observed concentrations of long-lived precursors (e.g., NO(y), Cl(y), Br(y), O3, H2O, CH4) and environmental parameters such as ozone column, reflectivity, and aerosol surface area. We will show based on analyses of observations obtained by aircraft, balloon, and satellite platforms during the POLARIS campaign that our overall understanding of the processes that regulate these radical species is very good. The most notable current discrepancies are the tendency to underestimate observed NO2 by 15 to 30% for air masses that experience near continuous solar illumination over a 24 hour period and the tendency to underestimate observed OH and H02 by about 10 to 20% during midday and by much larger amounts at high solar zenith angle (SZA > 85). Possible resolutions to these discrepancies will be discussed. This study was carried out in close collaboration with many members of the POLARIS science team.

Salawitch, Ross J.↗
NASA NTRS1999

Special Diagnostics

This section contains a number of special diagnostics that are designed to examine certain mechanisms. Section 1 reports on the method used to test the photochemical partitioning in the models. Sections 2 and 3 represent efforts to examine the model calculated production and removal rates for ozone and how the values are combined with transport rates in the models to produce the simulated ozone distributions. Sections 4 and 5 concentrate on polar processes including the dynamics aspect of vortex confinement and the chemical aspects of chlorine activation.

Ko, Malcolm K. W.↗
NASA NTRS1995

Measurement of HO2 and other trace gases in the stratosphere using a high resolution far-infrared spectrometer

This report covers the time period 1 January 1994 to 31 December 1994. During this reporting period we had our fourth Upper Atmosphere Research Satellite (UARS) correlative balloon flight; the data from this flight have been reduced and submitted to the UARS CDHF. We have spent most of the past year analyzing data from this and past flights. For example, using data from our September 1989 balloon flight we have demonstrated for the first time ever that the rates of production and loss of ozone are in balance in the upper stratosphere. As part of this analysis, we have completed the most detailed study to date of radical partitioning throughout the stratosphere. We have also produced the first measurement of HBr and HOBr mixing ratio profiles over a full diurnal cycle.

Traub, Wesley A.↗
NASA NTRS1992

The changing stratosphere

The current status of stratospheric research on stratospheric ozone is reviewed. Special attention is given to ozone chemistries in the upper and the lower stratosphere at the Antarctic, Arctic, and tropical latitudes, as well as at midlatitudes. The consequences these changes have on global climate are discussed in the framework of a one-dimensional radiative-convective model.

Mcelroy, Michael B.↗