Engineering topics

Talbot, R.

Publications and source records attributed to Talbot, R..

15 records

NASA NTRS2004

Analysis of the Atmospheric Distribution, Sources, and Sinks of Oxygenated Volatile Organic Chemicals Based on Measurements over the Pacific during TRACE-P

Airborne measurements of a large number of oxygenated volatile organic chemicals (OVOC) were carried out in the Pacific troposphere (0.1-12 km) in winter/spring of 2001 (24 February to 10 April). Specifically, these measurements included acetone (CH3COCH3), methylethyl ketone (CH3COC2H5, MEK), methanol (CH3OH), ethanol (C2H5OH), acetaldehyde (CH3CHO), propionaldehyde (C2H5CHO), peroxyacylnitrates (PANs) (C(sub n)H(sub 2n+1)COO2NO2), and organic nitrates (C(sub n)H(sub 2n+1)ONO2). Complementary measurements of formaldehyde (HCHO), methyl hydroperoxide (CH3OOH), and selected tracers were also available. OVOC were abundant in the clean troposphere and were greatly enhanced in the outflow regions from Asia. Background mixing ratios were typically highest in the lower troposphere and declined toward the upper troposphere and the lowermost stratosphere. Their total abundance (Summation of OVOC) was nearly twice that of nonmethane hydrocarbons (Summation of C2-C8 NMHC). Throughout the troposphere, the OH reactivity of OVOC is comparable to that of methane and far exceeds that of NMHC. A comparison of these data with western Pacific observations collected some 7 years earlier (February-March 1994) did not reveal significant differences. Mixing ratios of OVOC were strongly correlated with each other as well as with tracers of fossil and biomass/biofuel combustion. Analysis of the relative enhancement of selected OVOC with respect to CH3Cl and CO in 12 plumes originating from fires and sampled in the free troposphere (3-11 km) is used to assess their primary and secondary emissions from biomass combustion. The composition of these plumes also indicates a large shift of reactive nitrogen into the PAN reservoir thereby limiting ozone formation. A three-dimensional global model that uses state of the art chemistry and source information is used to compare measured and simulated mixing ratios of selected OVOC. While there is reasonable agreement in many cases, measured aldehyde concentrations are significantly larger than predicted. At their observed levels, acetaldehyde mixing ratios are shown to be an important source of HCHO (and HO x ) and PAN in the troposphere. On the basis of presently known chemistry, measured mixing ratios of aldehydes and PANs are mutually incompatible. We provide rough estimates of the global sources of several OVOC and conclude that collectively these are extremely large (150-500 Tg C / yr) but remain poorly quantified.

Singh, H. B.↗

NASA NTRS2003

Reactive Nitrogen in Asian Continental Outflow over the Western Pacific: Results from the NASA Transport and Chemical Evolution over the Pacific (TRACE-P)Airborne Mission

We present here results for reactive nitrogen species measured aboard the NASA DC-8 aircraft during the Transport and Chemical Evolution over the Pacific TRACE-P) mission. The large-scale distributions total reactive nitrogen (NO(sub y,sum) = NO + NO2 + HNO3 + PAN + C(sub 1)-C(sub 5) alkyl nitrates) and O3 and CO were better defined in the boundary layer with significant degradation of the relationships as altitude increased. Typically, NO(sub y,sum) was enhanced over background levels of approx.260 pptv by 20-to-30-fold. The ratio C2H2/CO had values of 1-4 at altitudes up to 10 km and as far eastward as 150degE, implying significant vertical mixing of air parcels followed by rapid advection across the Pacific. Analysis air parcels originating from five principal Asian source regions showed that HNO3 and PAN dominated NO(sub y,sum). Correlations of NO(sub y,sum) with C2Cl4 (urban tracer) were not well defined in any of the source regions, and they were only slightly better with CH3Cl (biomass tracer). Air parcels over the western Pacific contained a complex mixture of emission sources that are not easily resolvable as shown by analysis of the Shanghai mega-city plume. It contained an intricate mixture of pollution emissions and exhibited the highest mixing ratios of NO(sub y,sum) species observed during TRACE-P. Comparison of tropospheric chemistry between the earlier PEM-West B mission and the recent TRACE-P data showed that in the boundary layer significant increases in the mixing ratios of NO(sub y,sum)species have occurred, but the middle and upper troposphere seems to have been affected minimally by increasing emissions on the Asian continent over the last 7 years.

Talbot, R.↗

NASA NTRS2003

Oxygenated Organic Chemicals in the Pacific Troposphere: Distribution, Sources and Chemistry

Airborne measurements of a large number of oxygenated organic chemicals (Oxorgs) were carried out in the Pacific troposphere (0.1-12 km) in the Spring of 2001 (Feb. 24-April 10). Specifically these measuremen ts included acetone, methylethyl ketone (MEK), methanol, ethanol, ace taldehyde, propionaldehyde, PANS, and organic nitrates. Complementary measurements of formaldehyde, organic peroxides, and tracers were al so available. Ox-orgs were abundant in the clean troposphere and were greatly enhanced in the outflow regions from Asia. Their mixing ratios were typically highest in the lower troposphere and declined toward s the upper troposphere and the lowermost stratosphere. Their total a bundance (Ox-orgs) significantly exceeded that of NMHC (C2-C8 NMHC). A comparison of these data with observations collected some seven yea rs earlier (Feb.-March, 1994), did not reveal any significant changes . Throughout the troposphere mixing ratios of Ox-orgs were strongly c orrelated with each other as well as with tracers of fossil and bioma sshiof'uel combustion. Analysis of the relative enhancement of selected Oxorgs with respect to CH3Cl and CO in twelve sampled plumes, origi nating from fires, is used to assess their primary and secondary sour ces from biomass combustion. The composition of these plumes also ind icates a large shift of reactive nitrogen into the PAN reservoir ther eby limiting ozone formation. The Harvard 3-D photochemical model, th at uses state of the art chemistry and source information, is used to compare simulated and observed mixing ratios of selected species. A 1 -D model is used to explore the chemistry of aldehydes. These results will be presented.

Singh, Hanwant B.↗

NASA NTRS2002

Measurements of Oxygenated Organic Chemicals In the Pacific Troposphere During TRACE-P: Higher Aldehydes (less than C(sub 1)), Their Sources, and Potential Role In Atmospheric Oxidation

Airborne measurements of a large number of oxygenated organics were carried out in the Pacific troposphere (to 12 km) in the Spring of 2001 (Feb. 24-April 10). Specifically these measurements included acetaldehyde, propanaldehyde, acetone, methylethyl ketone, methanol, ethanol, PAM and organic nitrates. Independent measurements of formaldehyde, peroxides, and tracers were also available. Highly polluted as well as pristine air masses were sampled. Oxygenated organics were abundant in the clean In troposphere and were greatly enhanced in the outflow regions from Asia. Extremely high concentrations of aldehydes could be measured in the troposphere. It is not possible to explain the large abundances of aldehydes in the background troposphere without invoking significant oceanic sources. A strong correlation between the observed mixing ratios of formaldehyde and acetaldehyde is present. We infer that higher aldehydes (such as acetaldehyde and propanaldehyde) may provide a large source of formaldehyde and sequester Cox throughout the troposphere. The atmospheric behavior of acetone, methylethyl ketone, and methanol is generally indicative of their common terrestrial sources with a Image contribution from biomass/biofuel burning. A vast body of data has been collected and it is being analyzed both statistically and with the help of models to better understand the role that oxygenated organics play in the atmosphere and to unravel their sources and sinks. These results will be presented.

Singh, Hanwant B.↗

NASA NTRS1999

Biomass Burning Influences on the Composition of the Remote South Pacific Troposphere: Analysis Based on Observations from PEM Tropics-A

Airborne, in-situ measurements from PEM-Tropics-A (September/October 1996) are analyzed to show the presence of distinct pollution plumes in the middle-tropical troposphere of the remote South Pacific (10-30degS). These elevated plumes cause a relative maximum at about 5-7km attitude in the vertical distribution of primary and secondary species characteristic of fuel combustion and biomass burning (CO, C2H2, C2H6, CH3Cl, PAN, O3). Similar plumes were also observed at mid-latitudes in the middle troposphere during three flights east of New Zealand (40-45degS). In all, pollution plumes with CO larger than 100 ppb were observed 24 times on 7 separate flight days south of the equator. The observed plumes were generally embedded in very dry air. Ten-day back trajectory analysis supports the view that these originated from the biomass burning regions of South Africa (and South America) and were transported to the South Pacific along long-distance subsiding trajectories. The chemical composition of the southern Pacific troposphere analyzed from the PEM-Tropics-A data is compared with data from the tropical regions of the northern Pacific (PEM-West-A) and southern Atlantic (TRACE-A) during the same Sept/Oct time period. Sizable perturbations in the abundance of ozone and its key precursors, resulting from the transport of pollution originating from biomass burning sources, are observed in much of the Southern Hemispheric troposphere.

Singh, H. B.↗

NASA NTRS1997

An Assessment of Ozone Photochemistry in the Extratropical Western North Pacific: Impact of Continental Outflow During the Late Winter/Early Spring

This study examines the influence of photochemical processes on tropospheric ozone distributions over the extratropical western North Pacific. The analysis presented here is based on data collected during the Pacific Exploratory Mission-West Phase B (PEM-West B) field study conducted in February-March 1994. Sampling in the study region involved altitudes of 0-12 km and latitudes of 10deg S to 50deg N. The extratropical component of the data set (i.e., 20-50deg N) was defined by markedly different photochemical environments north and south of 30deg N. This separation was clearly defined by an abrupt decrease in the tropopause height near 30deg N and a concomitant increase in total O3 column density. This shift in overhead O3 led to highly reduced rates of O3 formation and destruction for the 30-50deg N latitude regime. Both latitude ranges, however, still exhibited net O3 production at all altitudes. Of special significance was the finding that net O3 production prevailed even at boundary layer and lower free tropospheric altitudes (e.g., less than 4 km), a condition uncommon to Pacific marine environments. These results reflect the strong impact of continental Outflow of O3 precursors (e.g., NO and NMHCS) into the northwestern Pacific Basin. Comparisons with PEM-West A, which sampled the same region in a different season (September-October), revealed major differences at altitudes below 4 km, the altitude range most influenced by continental outflow. The resulting net rate of increase in the tropospheric O3 column for PEM-West B was 1-3 % per day, while for PEM-West A it was approximately zero. Unique to the PEM-West B study is the finding that even under wintertime conditions substantial column production of tropospheric O3 can occur at subtropical and mid-latitudes. While such impacts may not be totally unexpected at near coast locations, the present study suggests that the impact from continental outflow on the marine BL could extend out to distances of more than 2000 km from the Asian Pacific Rim.

Crawford, J.↗

NASA NTRS1997

Implications of Large Scale Shifts in Tropospheric NO(x) Levels in the Remote Tropical Pacific

A major observation recorded during NASA's western Pacific Exploratory Mission (PEM-West B) was the large shift in tropical NO levels as a function of geographical location. High-altitude NO levels exceeding 100 pptv were observed during portions of tropical flights 5-8, while values almost never exceeded 20 pptv during tropical flights 9 and 10. The geographical regions encompassing these two flight groupings are here labeled "high" and "low" NOx regimes. A comparison of these two regimes, based on back trajectories and chemical tracers, suggests that air parcels in both were strongly influenced by deep convection. The low NO(x) regime appears to have been predominantly impacted by marine convection, whereas the high NO(x) regime shows evidence of having been more influenced by deep convection over a continental land mass. DMSP satellite observations point strongly toward lightning as the major source of NOx in the latter regime. Photochemical ozone formation in the high NOx regime exceeded that for low NO(x) by factors of 2 to 6, whereas O3 destruction in the low NO(x)regime exceeded that for high NOx by factors of up to 3. Taking the tropopause height to be 17 km, estimates of the net photochemical effect on the O3 column revealed that the high NO(x) regime led to a small net production. By contrast, the low NOx regime was shown to destroy O3 at the rate of 3.4 % per day. One proposed mechanism for off-setting this projected large deficit would involve the transport of 03 rich midlatitude air into the tropics. Alternatively, it is suggested that O3 within the tropics may be overall near self-sustaining with respect to photochemical activity. This scenario would require that some tropical regions, unsampled at the time of PEM-B, display significant net column O3 production, leading to an overall balanced budget for the "greater" tropical Pacific basin. Details concerning the chemical nature of such regimes are discussed.

Crawford, J. H.↗

NASA NTRS1997

Upper Tropospheric/Lower Stratospheric Distribution of Reactive Nitrogen and Ozone

In-situ measurements of a large number of trace chemicals from upper troposphere/lower stratosphere (UT/LS) were performed with the NASA DC-8 aircraft during February/March 1994 over the Pacific Ocean (10 S to 60 N). Mixing ratios in the UT were relatively low in the warm tropical and subtropical air south of the polar jetstream (approx. =28 N) but increased sharply with latitude in the cold polar air north of the jetstream. At about 45 N, high concentrations of PAN (300 ppt) coexisted with extremely low (approx. = 20 ppt) concentrations of NOx. Elevated NOx levels in the UT did not always correspond to continental outflow conditions. Deepest penetrations into the stratosphere (550 ppb O3, 279 ppb NOx, and 350 K potential temperature) corresponded to a region that has been defined as the 'lowermost stratosphere' (LS) by Holton et al. Analysis of data shows that the mixing ratios of long-lived tracer species (e.g., CH4, HNO3, NOy, CFCs, HCFCs) are linearly correlated with those of O3 and N2O. A delta-NOY/delta-O3 of 0.0054 ppb/ppb and delta-NOy/delta-N2O of -0.081 ppb/ppb is in good agreement with other reported measurements from the DC-8. These slopes are however, somewhat steeper than those reported from the ER-2 studies. We find that the reactive nitrogen budget in the UT/LS is largely balanced with shortfalls that are no greater than 15%. A number of oxygenated species (e.g., acetone, H2O2) are present and may provide an important in-situ source of HOx in the UT/LS region.

Singh, H. S.↗

NASA NTRS1994

Global Ozone and Reactive Nitrogen : Composition, Chemistry and Sources

Ozone plays a central role in the chemistry of the atmosphere both as an ultraviolet shield and as a source of hydroxyl radicals (OH), a potent initiator of atmospheric chemistry. There is evidence to suggest that the ozone abundance in the troposphere (0-10 km) has doubled since the industrial revolution and continues to increase to date. The principle reason for this increase is thought to be the increasing emissions of nitrogen oxides (NO(x)) from anthropogenic activities. Although NO(x) is highly reactive and its products such as HN03 are easily removed by deposition, it now appears that its chemistry is quite complex and it can be transported over long distances via its conversion to a variety of nitrates and penetrates. The sources of atmospheric NO(x) include free tropospheric sources such as lightning and subsonic aircraft, as well as surface emissions which are transported to the free troposphere via convective processes. Recent experimental and theoretical studies have tried to unravel the chemistry of reactive nitrogen species, its sources, and their role in ozone formation. In this presentation we shall describe the results from these studies.

Sing, Hanwant B.↗

NASA NTRS1994

Summertime distribution of PAN and other reactive nitrogen species in the northern high-latitude atmosphere of eastern Canada

Aircraft measurements of key reactive nitrogen species (NO, NO2, HNO3, PAN, PPN, NO3(-), NO(y)), C1 to C6 hydrocarbons, acetone, O3, chemical tracers (C2Cl4, CO), and important meteorological parameters were performed over eastern Canada during July to August 1990 at altitudes between 0 and 6 km as part of an Arctic Boundary Layer Expedition (ABLE3B). In the free troposphere, PAN was found to be the single most abundant reactive nitrogen species constituting a major fraction of NO(y) and was significantly more abundant than NO(x) and HNO3. PAN and O3 were well correlated both in their fine and gross structures. Compared to data previously collected in the Arctic/subarctic atmosphere over Alaska (ABLE3A), the lower troposphere (0-4 km) over eastern Canada was found to contain larger reactive nitrogen and anthropogenic tracer concentrations. At higher altitudes (4-6 km) the atmospheric composition was in many ways similar to what was seen over Alaska and supports the view that a large-scale reservoir of PAN (and NO(y)) is present in the upper troposphere over the entire Arctic/subarctic region. The reactive nitrogen budget based on missions conducted from the North Bay site (missions 2-10) showed a small shortfall, whereas the budget for data collected from the Goose Bay operation (missions 11-19) showed essential balance. It is calculated that 15-20 ppt of the observed NO(x) may find its source from the available PAN reservoir. Meteorological considerations as well as relationships between reactive nitrogen and tracer species suggest that the atmosphere over eastern Canada during summer is greatly influenced by forest fires and transported industrial pollution.

Singh, H. B.↗

NASA NTRS1994

Summertime partitioning and budget of NO(y) compounds in the troposphere over Alaska and Canada: ABLE 3B

As part of NASA's Arctic Boundary Layer Expedition 3A and 3B field measurement programs, measurements of NO(x), HNO3, PAN, PPN, and NO(y) were made in the middle to lower troposphere over Alaska and Canada during the summers of 1988 and 1990. These measurements are used to assess the degree of closure within the reactive odd nitrogen (N(x)O(y)) budget through the comparison of the values of NO(y) measured with a catalytic convertor to the sum of individually measured NO(y) (i) compounds (i.e., sigmaNO(y)(i) = NO(x) + HNO3 + PAN + PPN). Significant differences were observed between the various study regions. In the lower 6 km of the troposphere over Alaska and the Hudson Bay lowlands of Canada a significant fraction of the NO(y) budget (30 to 60%) could not be accounted for by the measured sigmaNO(y)i. This deficit in the NO(y) budget is about 100 to 200 parts per trillion by volume (pptv) in the lower troposphere (0.15 to 3 km) and about 200 to 400 pptv in the middle free troposphere (3 to 6.2 km). Conversely, the NO(y) budget in the northern Labrador and Quebec regions of Canada is almost totally accounted for within the combined measurement uncertainties of NO(y) and the various NO(y)(i) compounds. A substantial portion of the NO(y) budget's 'missing compounds' appears to be coupled to the photochemical and/or dynamical parameters influencing the tropospheric oxidative potential over these regions. A combination of factors are suggested as the causes for the variability observed in the NO(y) budget. In addition, the apparent stability of compounds represented by the NO(y) budget deficit in the lower-altitude range questions the ability of these compounds to participate as reversible reservoirs for 'active' odd nitrogen and suggest that some portion of the NO(y) budget may consist of relatively unreactive nitrogen-containing compounds.

Sandholm, S.↗

NASA NTRS1994

Low Ozone in the Marine Boundary Layer of the Tropical Pacific Ocean

Aircraft measurements of ozone, its key precursors, and a variety of chemical tracers were made in the troposphere of the western and central Pacific in October 1991. These data are presented and analyzed to examine the occurrence of low ozone concentrations in the remote marine boundary layer of the tropical and equatorial Pacific Ocean. The data from these flights out of Guam, covering an area extending from the equator to 20 N and from south of the Philippines to Hawaii, show average O3 concentrations as low as 8-9 ppb (ppb=10(exp-9)v/v) at altitudes of 0.3-0.5 km in the boundary layer. Individual measurements as low as 2-5 ppb were recorded. Low O3 concentrations do not always persist in space and time. High O3, generally associated with the transport of upper tropospheric air, was also encountered in the boundary layer. In practically all cases, O3 increased to values as large as 25-30 ppb within 2 km above the boundary layer top. Steady state model computations are used to suggest that these low O3 concentrations are a result of net photochemical O3 destruction in a low NO environment, sea-surface deposition, and extremely low net entrainment rates (1-2 mm per second) from the free troposphere. Day/night measurements of ethane, propane, gaseous and aerosol Cl suggest that daytime (morning) Cl atom concentrations in the vicinity of 10(exp 5) molecules per cubic centimeter may be present in the marine boundary layer. This Cl atom abundance can be rationalized only if sea salt aerosols can release free chlorine (Cl2) to the gas phase in the presence of sun light (and possibly O3). These Cl atom concentrations, however, are still insufficient and Cl (or Br) chemistry is not likely to be an important cause of the observed low O3.

Singh, Hanwant B.↗

NASA NTRS1992

Relationship of peroxyacetyl nitrate to active and total odd nitrogen at northern high latitudes - Influence of reservoir species on NO(x) and O3

The partitioning of relative nitrogen in the Arctic and the sub-Arctic troposphere based on measurements conducted during the 1988 Arctic Boundary Layer Expedition (ABLE 3A) is described. The first set of comprehensive odd nitrogen and O3 measurements from the Arctic/sub-Arctic free troposphere shows that a highly aged air mass that has persisted under very cold conditions is present. A large fraction of the odd nitrogen appears to be present in the form of reservoir species such as PAN. Significant quantities of as yet unknown reactive nitrogen species, such as complex alkyl nitrates and pernitrates, are expected to be present. Together with PAN, these nitrate and pernitrate reservoir species could control the entire NO(x) availability of the high-latitude troposphere and in turn influence the O3 photochemistry of the region. The role of PAN in influencing the O3 reservoir is shown to be important and may be responsible for the increasing O3 temporal trend observed at high latitudes.

Singh, H. B.↗

NASA NTRS1992

Relationship of peroxyacetyl nitrate to active and total odd nitrogen at northern high latitudes: influence of reservoir species on NOx and O3

Measurements of peroxyacetyl nitrate (PAN), NO, NO2, HNO3, NOy (total odd nitrogen), and O3 were made in the high-latitude troposphere over North America and Greenland (35 degrees to 82 degrees N) during the Arctic Boundary Layer Expedition (ABLE 3A) (July-August 1988) throughout 0-to 6-km altitudes. These data are analyzed to quantitatively describe the relationships between various odd nitrogen species and assess their significance to global tropospheric chemistry. In the free troposphere, PAN was as much as 25 times more abundant than NOx. PAN to NOx ratio increased with increasing altitude and latitude. PAN was found to be the single most abundant reactive nitrogen species in the free troposphere and constituted a major fraction of NOy, PAN to NOy ratios were about 0.1 in the boundary layer and increased to 0.4 in the free troposphere. A 2-D global photochemical model with C1-C3 hydrocarbon chemistry is used to compare model predictions with measured results. A sizable portion (approximately 50%) of the gaseous reactive nitrogen budget is unaccounted for, and unknown organic nitrates and pernitrates are expected to be present. Model calculations (August 1, 70 degrees N) show that a major fraction of the observed NOx (50 to 70% of median) may find its source in the available PAN reservoir. PAN and the unknown reservoir species may have the potential to control virtually the entire NOx availability of the high latitude troposphere. It is predicted that the summer NOx and O3 mixing ratios in the Arctic/sub-Arctic troposphere would be considerably lower in the absence of the ubiquitous PAN reservoir. Conversely, this PAN reservoir may be responsible for the observed temporal increase in tropospheric O3 at high latitudes.

NASA Center ARC↗

NASA NTRS1992

Saharan dust in the Amazon Basin

It is shown that Saharan dust enters the Central Amazon Basin in bursts that accompany major wet season rain systems. Low-level horizontal convergence feeding these rain systems draws dust from plumes that have crossed the tropical Atlantic under the large-scale circulation fields. Mass exchange of air between the surface and four kilometers over the eastern Amazon basin is calculated utilizing rawinsonde data collected during storm events. Mean concentrations of dust observed by aircraft over the western tropical Atlantic are employed to calculate the amount of dust injected into the basin.

Swap, R.↗