Engineering topics

Atlas, Elliot L.

Publications and source records attributed to Atlas, Elliot L..

8 records

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 NTRS2016

Model Sensitivity Studies of the Decrease in Atmospheric Carbon Tetrachloride

Carbon tetrachloride (CCl4) is an ozone-depleting substance, which is controlled by the Montreal Protocol and for which the atmospheric abundance is decreasing. However, the current observed rate of this decrease is known to be slower than expected based on reported CCl4 emissions and its estimated overall atmospheric lifetime. Here we use a three-dimensional (3-D) chemical transport model to investigate the impact on its predicted decay of uncertainties in the rates at which CCl4 is removed from the atmosphere by photolysis, by ocean uptake and by degradation in soils. The largest sink is atmospheric photolysis (74% of total), but a reported 10% uncertainty in its combined photolysis cross section and quantum yield has only a modest impact on the modelled rate of CCl4 decay. This is partly due to the limiting effect of the rate of transport of CCl4 from the main tropospheric reservoir to the stratosphere, where photolytic loss occurs. The model suggests large interannual variability in the magnitude of this stratospheric photolysis sink caused by variations in transport. The impact of uncertainty in the minor soil sink (9%of total) is also relatively small. In contrast, the model shows that uncertainty in ocean loss (17%of total) has the largest impact on modelled CCl4 decay due to its sizeable contribution to CCl4 loss and large lifetime uncertainty range (147 to 241 years). With an assumed CCl4 emission rate of 39 Gg year(exp -1), the reference simulation with the best estimate of loss processes still underestimates the observed CCl4 (overestimates the decay) over the past 2 decades but to a smaller extent than previous studies. Changes to the rate of CCl4 loss processes, in line with known uncertainties, could bring the model into agreement with in situ surface and remote-sensing measurements, as could an increase in emissions to around 47 Gg year(exp -1). Further progress in constraining the CCl4 budget is partly limited by systematic biases between observational datasets. For example, surface observations from the National Oceanic and Atmospheric Administration (NOAA) network are larger than from the Advanced Global Atmospheric Gases Experiment (AGAGE) network but have shown a steeper decreasing trend over the past 2 decades. These differences imply a difference in emissions which is significant relative to uncertainties in the magnitudes of the CCl4 sinks.

Carbon Trechloride↗

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

Isotopic Ordering in Atmospheric O2 as a Tracer of Ozone Photochemistry and the Tropical Atmosphere

The distribution of isotopes within O2 molecules can be rapidly altered when they react with atomic oxygen. This mechanism is globally important: while other contributions to the global budget of O2 impart isotopic signatures, the O(3P) + O2 reaction resets all such signatures in the atmosphere on subdecadal timescales. Consequently, the isotopic distribution within O2 is determined by O3 photochemistry and the circulation patterns that control where that photochemistry occurs. The variability of isotopic ordering in O2 has not been established, however. We present new measurements of 18O18O in air (reported as delta36 values) from the surface to 33 km altitude. They confirm the basic features of the clumped-isotope budget of O2: Stratospheric air has higher delta36 values than tropospheric air (i.e., more 18O18O), reflecting colder temperatures and fast photochemical cycling of O3. Lower delta36 values in the troposphere arise from photochemistry at warmer temperatures balanced by the influx of high-delta36 air from the stratosphere. These observations agree with predictions derived from the GEOS-Chem chemical transport model, which provides additional insight. We find a link between tropical circulation patterns and regions where delta36 values are reset in the troposphere. The dynamics of these regions influences lapse rates, vertical and horizontal patterns of O2 reordering, and thus the isotopic distribution toward which O2 is driven in the troposphere. Temporal variations in delta36 values at the surface should therefore reflect changes in tropospheric temperatures, photochemistry, and circulation. Our results suggest that the tropospheric O3 burden has remained within a +/-10 percent range since 1978.

oxygen↗

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 NTRS2012

On the Sources of Methane to the Los Angeles Atmosphere

We use historical and new atmospheric trace gas observations to refine the estimated source of methane (CH4) emitted into California's South Coast Air Basin (the larger Los Angeles metropolitan region). Referenced to the California Air Resources Board (CARB) CO emissions inventory, total CH4 emissions are 0.44 +/- 0.15 Tg each year. To investigate the possible contribution of fossil fuel emissions, we use ambient air observations of methane (CH4), ethane (C2H6), and carbon monoxide (CO), together with measured C2H6 to CH4 enhancement ratios in the Los Angeles natural gas supply. The observed atmospheric C2H6 to CH4 ratio during the ARCTAS (2008) and CalNex (2010) aircraft campaigns is similar to the ratio of these gases in the natural gas supplied to the basin during both these campaigns. Thus, at the upper limit (assuming that the only major source of atmospheric C2H6 is fugitive emissions from the natural gas infrastructure) these data are consistent with the attribution of most (0.39 +/- 0.15 Tg yr-1) of the excess CH4 in the basin to uncombusted losses from the natural gas system (approximately 2.5-6% of natural gas delivered to basin customers). However, there are other sources of C2H6 in the region. In particular, emissions of C2H6 (and CH4) from natural gas seeps as well as those associated with petroleum production, both of which are poorly known, will reduce the inferred contribution of the natural gas infrastructure to the total CH4 emissions, potentially significantly. This study highlights both the value and challenges associated with the use of ethane as a tracer for fugitive emissions from the natural gas production and distribution system.

Wennberg, Paul O.↗

NASA NTRS2002

Tracer-based Determination of Vortex Descent in the 1999/2000 Arctic Winter

A detailed analysis of available in situ and remotely sensed N2O and CH4 data measured in the 1999/2000 winter Arctic vortex has been performed in order to quantify the temporal evolution of vortex descent. Differences in potential temperature (theta) among balloon and aircraft vertical profiles (an average of 19-23 K on a given N2O or CH4 isopleth) indicated significant vortex inhomogeneity in late fall as compared with late winter profiles. A composite fall vortex profile was constructed for 26 November 1999, whose error bars encompassed the observed variability. High-latitude extravortex profiles measured in different years and seasons revealed substantial variability in N2O and CH4 on theta surfaces, but all were clearly distinguishable from the first vortex profiles measured in late fall 1999. From these extravortex-vortex differences we inferred descent prior to 26 November: as much as 397 plus or minus 15 K (lsigma) at 30 ppbv N2O and 640 ppbv CH4, and falling to 28 plus or minus 13 K above 200 ppbv N2O and 1280 ppbv CH4. Changes in theta were determined on five N2O and CH4 isopleths from 26 November through 12 March, and descent rates were calculated on each N2O isopleth for several time intervals. The maximum descent rates were seen between 26 November and 27 January: 0.82 plus or minus 0.20 K/day averaged over 50- 250 ppbv N2O. By late winter (26 February to 12 March), the average rate had decreased to 0.10 plus or minus 0.25 K/day. Descent rates also decreased with increasing N2O; the winter average (26 November to 5 March) descent rate varied from 0.75 plus or minus 0.10 K/day at 50 ppbv to 0.40 plus or minus 0.11 K/day at 250 ppbv. Comparison of these results with observations and models of descent in prior years showed very good overall agreement. Two models of the 1999/2000 vortex descent, SLIMCAT and REPROBUS, despite theta offsets with respect to observed profiles of up to 20 K on most tracer isopleths, produced descent rates that agreed very favorably with the inferred rates from observation.

Greenblatt, Jeffrey B.↗

NASA NTRS2001

Tracer-Based Determination of Vortex Descent in the 1999-2000 Arctic Winter

A detailed analysis of available in situ and remotely sensed N2O and CH4 data measured in the 1999-2000 winter Arctic vortex has been performed in order to quantify the temporal evolution of vortex descent. Differences in potential temperature (theta) among balloon and aircraft vertical profiles (an average of 19-23 K on a given N2O or CH4 isopleth) indicated significant vortex inhomogeneity in late fall as compared with late winter profiles. A composite fall vortex profile was constructed for November 26, 1999, whose error bars encompassed the observed variability. High-latitude, extravortex profiles measured in different years and seasons revealed substantial variability in N2O and CH4 on theta surfaces, but all were clearly distinguishable from the first vortex profiles measured in late fall 1999. From these extravortex-vortex differences, we inferred descent prior to November 26: 397+/-15 K (1sigma) at 30 ppbv N2O and 640 ppbv CH4, and 28+/-13 K above 200 ppbv N2O and 1280 ppbv CH4. Changes in theta were determined on five N2O and CH4 isopleths from November 26 through March 12, and descent rates were calculated on each N2O isopleth for several time intervals. The maximum descent rates were seen between November 26 and January 27: 0.82+/-0.20 K/day averaged over 50-250 ppbv N2O. By late winter (February 26-March 12), the average rate had decreased to 0.10+/-0.25 K/day. Descent rates also decreased with increasing N2O; the winter average (November 26-March 5) descent rate varied from 0.75+/-0.10 K/day at 50 ppbv to 0.40+/-0.11 K/day at 250 ppbv. Comparison of these results with observations and models of descent in prior years showed very good overall agreement. Two models of the 1999-2000 vortex descent, SLIMCAT and REPROBUS, despite theta offsets with respect to observed profiles of up to 20 K on most tracer isopleths, produced descent rates that agreed very favorably with the inferred rates from observation.

Greenblatt, Jeffery B.↗