Engineering topics

Brune, W. H.

Publications and source records attributed to Brune, W. H..

At least 19 records

NASA NTRS2011

Emissions of Black Carbon, Organic, and Inorganic Aerosols From Biomass Burning in North America and Asia in 2008

Reliable assessment of the impact of aerosols emitted from boreal forest fires on the Arctic climate necessitates improved understanding of emissions and the microphysical properties of carbonaceous (black carbon (BC) and organic aerosols (OA)) and inorganic aerosols. The size distributions of BC were measured by an SP2 based on the laser-induced incandescence technique on board the DC-8 aircraft during the NASA ARCTAS campaign. Aircraft sampling was made in fresh plumes strongly impacted by wildfires in North America (Canada and California) in summer 2008 and in those transported from Asia (Siberia in Russia and Kazakhstan) in spring 2008. We extracted biomass burning plumes using particle and tracer (CO, CH3CN, and CH2Cl2) data. OA constituted the dominant fraction of aerosols mass in the submicron range. The large majority of the emitted particles did not contain BC. We related the combustion phase of the fire as represented by the modified combustion efficiency (MCE) to the emission ratios between BC and other species. In particular, we derived the average emission ratios of BC/CO = 2.3 +/- 2.2 and 8.5 +/- 5.4 ng/cu m/ppbv for BB in North America and Asia, respectively. The difference in the BC/CO emission ratios is likely due to the difference in MCE. The count median diameters and geometric standard deviations of the lognormal size distribution of BC in the BB plumes were 136-141 nm and 1.32-1.36, respectively, and depended little on MCE. These BC particles were thickly coated, with shell/core ratios of 1.3-1.6. These parameters can be used directly for improving model estimates of the impact of BB in the Arctic.

Kondo, Y.↗

NASA NTRS2007

Surface and Lightning Sources of Nitrogen Oxides over the United States: Magnitudes, Chemical Evolution, and Outflow

We use observations from two aircraft during the International Consortium for Atmospheric Research on Transport and Transformation (ICARTT) campaign over the eastern United States and North Atlantic during summer 2004, interpreted with a global 3-D model of tropospheric chemistry (GEOS-Chem) to test current understanding of the regional sources, chemical evolution, and export of nitrogen oxides. The boundary layer NO(x) data provide top-down verification of a 50% decrease in power plant and industry NO(x) emissions over the eastern United States between 1999 and 2004. Observed 8-12 8 km NO(x) concentrations in ICARTT were 0.55 +/- 36 ppbv, much larger than in previous United States aircraft campaigns (ELCHEM, SUCCESS, SONEX). We show that regional lightning was the dominant source of this NO(x) and increased upper tropospheric ozone by 10 ppbv. Simulating the ICARTT upper tropospheric NO(x) observations with GEOS-Chem require a factor of 4 increase in the model NO(x) yield per flash (to 500 mol/flash). Observed OH concentrations were a factor of 2 lower than can be explained from current photochemical models, and if correct would imply a broader lightning influence in the upper troposphere than presently thought.An NO(y)-CO correlation analysis of the fraction f of North American NO(x) emissions vented to the free troposphere as NO(y) (sum of NO(x) and its oxidation products PAN and HNO3) s shows observed f=16+/-10 percent and modeled f=14 +/- 8 percent, consistent with previous studies. Export to the lower free troposphere is mostly HNO3 but at higher altitudes is mostly PAN. The model successfully simulates NO(y) export efficiency and speciation, supporting previous model estimates of a large U.S. contribution to tropospheric ozone through NO(x) and PAN export.

Hudman, Rynda C.↗

NASA NTRS2007

Summertime Influence of Asian Pollution in the Free Troposphere over North America

We analyze aircraft observations obtained during INTEX-A (1 July 14 - August 2004) to examine the summertime influence of Asian pollution in the free troposphere over North America. By applying correlation analysis and Principal Component Analysis (PCA) to the observations between 6-12 km, we find dominant influences from recent convection and lightning (13 percent of observations), Asia (7 percent), the lower stratosphere (7 percent), and boreal forest fires (2 percent), with the remaining 71 percent assigned to background. Asian airmasses are marked by high levels of CO, O3, HCN, PAN, acetylene, benzene, methanol, and SO4(2-). The partitioning of reactive nitrogen species in the Asian plumes is dominated by peroxyacetyl nitrate (PAN) (approximately 600 pptv), with varying NO(x)/HNO3 ratios in individual plumes consistent with different plumes ages ranging from 3 to 9 days. Export of Asian pollution in warm conveyor belts of mid-latitude cyclones, deep convection, and lifting in typhoons all contributed to the five major Asian pollution plumes. Compared to past measurement campaigns of Asian outflow during spring, INTEX-A observations display unique characteristics: lower levels of anthropogenic pollutants (CO, propane, ethane, benzene) due to their shorter summer lifetimes; higher levels of biogenic tracers (methanol and acetone) because of a more active biosphere; as well as higher levels of PAN, NO(x), HNO3, and O3 (more active photochemistry possibly enhanced by injection of lightning NO(x)). The high delta O3/delta CO ratio (0.76 mol mol(exp -1)) of Asian plumes during INTEX-A is due to a combination of strong photochemical production and mixing with stratospheric air along isentropic surfaces. The GEOS-Chem global chemical transport model captures the timing and location of the Asian plumes remarkably well. However, it significantly underestimates the magnitude of the enhancements.

Liang, Q.↗

NASA NTRS1994

Measurement of tropospheric OH and HO2 by laser-induced fluorescence at low pressure

The hydroxyl radical (OH) is the primary oxidant in the atmosphere, responsible for many photochemical reactions that affect both regional air quality and global climate change. Because of its high reactivity, abundances of OH in the troposphere are less than 1 part per trillion by volume (pptv) and thus difficult to measure accurately. This paper describes an instrument for the sensitive detection of OH in the troposphere using low-pressure laser-induced fluorescence. Ambient air is expanded into a low pressure detection chamber, and OH is both excited and detected using the A(sup 2) Epsilon(+)(v prime = 0) yields X(sup 2)Pi(v double prime = 0) transition near 308 nm. An injector upstream of the detection axis allows for the addition of reagent NO to convert ambient HO2 to OH using the fast reaction HO2 + NO yields OH + NO2. Using recent advances in laser and detector technologies, this prototype instrument is able to detect less than 1 x 10(exp 5) molecules/cu cm (0.004 pptv) of OH with an integration time of 30 s with negligible interferences.

Stevens, P. S.↗

NASA NTRS1993

Balloon-borne in situ measurements of ClO and ozone - Implications for heterogeneous chemistry and mid-latitude ozone loss

In situ measurements of chlorine oxide (ClO) obtained on 31 March 1991 with a new balloon-borne instrument are compared to results from a photochemical model which incorporates hydrolysis of N2O5 on sulfate aerosols. With the addition of this process, there is better agreement between calculation and measurement over most of the profile, except below 20 km where observed ClO is greater by as much as a factor of four. In a model which is constrained to reproduce the observed ClO below 20 km, ozone loss by catalytic cycles involving halogen oxides becomes larger than that from NO(x), which would dominate under gas-phase or standard heterogeneous conditions.

Avallone, L. M.↗

NASA NTRS1991

Measurements of ClO and O3 from 21 deg N to 61 deg N in the lower stratosphere during February 1988 - Implications for heterogeneous chemistry

The decline in stratospheric ozone at northern midlatitudes in wintertime may be caused by chlorine photochemistry that has been enhanced by heterogeneous reactions. The possibility that the heterogeneous reaction of N2O5 on sulfate aerosols is the cause of this decadal ozone decline is examined by comparing ClO and O3 measurements made in the lower stratosphere during February, 1988, with results from a 2D model. At midlatitudes, the abundances, latitudinal, and seasonal gradients of the observed ClO are similar to the results of a model with heterogeneous chemistry, but are in strong disagreement with the results from the model with only gas-phase chemistry. At low latitudes, agreement is best with the results of the model with only gas-phase chemistry. Limited observations indicate that the amount of reactive chlorine is being enhanced, and that heterogeneous chemistry is a likely cause.

King, J. C.↗

NASA NTRS1991

The potential for ozone depletion in the Arctic polar stratosphere

The nature of the Arctic polar stratosphere is observed to be similar in many respects to that of the Antarctic polar stratosphere, where an ozone hole has been identified. Most of the available chlorine (CHl and ClONO2) was converted by reactions on polar stratospheric clouds to reactive ClO and Cl2O2 thoroughout the Arctic polar vortex before midwinter. Reactive nitrogen was converted to HNO3, and some, with spatial inhomogeneity, fell out of the stratosphere. These chemical changes ensured characteristic ozone losses of 10 to 15 percent at altitudes inside the polar vortex where polar stratospheric clouds had occurred. These local losses can translate into 5 to 8 percent losses in the vertical column abundance of ozone. As the amount of stratospheric chlorine inevitably increases by 50 percent over the next two decades, ozone losses recognizable as an ozone hole may well appear.

Brune, W. H.↗

NASA NTRS1991

In situ measurements of midlatitude ClO in winter

In situ measurements of ClO in the winter lower stratosphere are presented for six flights of the NASA ER-2 aircraft from 38 deg N to 61 deg N. Enhanced abundances, increasing in severity with date, were observed below 20 km, where HCl and ClONO2 dominate the inorganic chlorine budget. The greatest mixing ratios, over 150 pptv, were encountered on February 20 and 21, 1989, as the vortex experienced a major warming. Although the timing of these ClO enhancements and the evidence that vortex air can reach midlatitudes suggest that heterogeneous conversion of chlorine compounds within the vortex influences chemistry at midlatitudes, the enhacements observed early in the winter could have been caused by unknown chemistry occurring outside the vortex. In either case, photochemical loss of ozone due to catalytic reactions involving ClO at these mixing ratios may be responsible in part for the ozone decreases observed at high latitudes in the Northern Hemisphere.

Toohey, D. W.↗

NASA NTRS1990

Interpretation of aircraft measurements of NO, ClO, and O3 in the lower stratosphere

Results are presented from an October 17, 1988, flight of the NASA ER-2 stratospheric research aircraft. The flight sampled a nearly constant air mass at 20 km altitude, near 39 deg N latitude, from before sunrise until near noon. The instrumentation on board simultaneously measured NO, ClO, O3, temperature, and pressure. The measurements are combined with modeled photodissociation coefficients and known reaction kinetics to infer abundances of other important species, and the results are compared to previous estimates as a test for consistency in the understanding of the photochemical processes governing the species distributions.

Kawa, S. R.↗

NASA NTRS1990

Heterogeneous chemistry on liquid sulfate aerosols - A comparison of in situ measurements with zero-dimensional model calculations

The possibility that stratospheric chlorine is converted from reservoir to reactive forms by heterogeneous reactions on background sulfate aerosols is examined. Tightly constrained photochemical models have been used to calculate ClO abundances for the morning and the afternoon conditions observed on January 24, 1989 outside the Arctic polar vortex by instruments on the NASA ER-2 aircraft. Calculations involving gas-phase chemistry only and calculations with heterogeneous chemistry including HCl evaporation from the aerosol both produce ClO abundances that agree with observations; calculations in which HCl removal from the aerosol is controlled by heterogeneous reactions produce ClO abundances that are 3 to 3.5 times larger than observations. These results suggest that HCl evaporation must be included in a model of the chemistry of background aerosols.

Mather, J. H.↗

NASA NTRS1990

In situ observations of ClO in the Arctic Stratosphere - ER-2 aircraft results from 59 deg N to 80 deg N latitude

Large abundances of ClO were observed inside the Arctic polar vortex during 14 flights of the NASA ER-2 aircraft from Stavanger, Norway (59 deg N, 6 deg E) to 80 deg N latitude. Flights were conducted at altitudes between 14 and 20 km when the solar zenith angle was between 79 and 101 deg. Data are reported for three flights that represent the main features observed during the mission. These data, comparable to those obtained in the Antarctic ozone hole, indicate that the springtime Arctic polar vortex was extensively perturbed by heterogeneous chemistry and contained enough ClO to catalytically destroy ozone rapidly.

Brune, W. H.↗

NASA NTRS1990

The sunrise and sunset variation of ClO in the lower stratosphere

The abundances of ClO have been measured, in situ, in the lower stratosphere during sunrise and sunset. Measurements were made with an instrument mounted on the NASA ER-2 aircraft, which was flown at an altitude of 20 km and latitudes between 35 and 47 deg N during a morning and an evening flight. The abundances of ClO were observed over a dynamic range of 20 from a detection threshold of 1 part per trillion volume (pptv). These data confirm the sunrise variation of the photolysis of chlorine nitrate that is predicted by a zero-dimensional photochemical model. They also suggest that the absolute photolysis and termolecular formation of chlorine nitrate occur at rates consistent with nominal ClONO2 and NO2 concentrations.

Brune, W. H.↗

NASA NTRS1990

In situ measurements of BrO in the Arctic stratosphere

Mixing ratios of BrO have been measured in the Arctic lower statosphere with an instrument mounted on the NASA ER-2 aircraft. Observations from fourteen flights above the Arctic Circle in January and February of 1989 defined mixing ratios within the vortex of 4 + or - 2 parts per trillion by volume (pptv) at a potential temperature of 400 K, rising to 8 + or - 2 pptv at 470 K. These values are twice as large as values found at equivalent potential temperatures at lower latitudes, and are comparable to the mixing ratios found inside the antarctic polar vortex. Within the statistical uncertainty of the measurements, no BrO was observed in darkness at any time either inside or outside of the vortex, indicating that active bromine was sequestered in long-lived reservoirs, probably BrONO2 and BrCl. These measurements, in conjuction with measurements of ClO, demonstrate that the interaction of bromine and chlorine could represent a major sink for ozone in the presence of sunlight.

Toohey, D. W.↗

NASA NTRS1990

The polar stratospheric cloud event of January 24. II - Photochemistry

During the 1988/89 Airborne Arctic Stratospheric Expedition (AASE), observations of the chemical composition, aerosol characteristics and atmospheric state were obtained from two aircraft, a NASA ER-2 and a DC-8. This paper presents a diagnosis of observations obtained using the ER-2 on January 24, 1989, using a Lagrangian coupled microphysical-photochemical model. The high chlorine monoxide mixing ratios observed from the ER-2 on the afternoon of January 24, 1989 are interpreted as a result of in situ heterogeneous release of reactive chlorine from the reservoirs HCl and CIONO2 on type-1 polar stratospheric cloud particles observed to be present at that time. This essential element in theories of polar ozone depletion has never before been observed directly in the stratosphere.

Jones, R. L.↗

NASA NTRS1990

Calculations of ozone destruction during the 1988/89 Arctic winter

Calculations of ozone depletion during the 1988/89 Arctic winter using a Lagrangian coupled photochemical-microphysical model are presented. Abundances of ClO in excess of 1 ppbv were observed at the end of the Airborne Arctic Stratospheric Expedition on February 10, 1989. These are shown to be consistent with the removal of more than 90 percent of the reactive nitrogen and the conversion of more than 80 percent of reservoir chlorine to active forms. This chemical state implies that ozone losses of more than 20 ppbv/day can be sustained in heavily denitrified air throughout much of February according to current photochemistry. As much as 74 percent of the loss is calculated to be due to ClO dimer photolysis. Following the warming of the vortex in mid-February 1989, ozone loss through ClO dimer photolysis becomes less effective as the rate of thermal decomposition of the ClO dimer increases. Thus, model results suggest that thermal decomposition of the dimer plays an important role in limiting ozone loss in the Arctic spring.

Mckenna, D. S.↗

NASA NTRS1989

In situ observations of BrO over Antarctica - ER-2 aircraft results from 54 deg S to 72 deg S latitude

Bromine monoxide was observed in situ during nine flights of the NASA ER-2 aircraft from Punta Arenas, Chile (54 deg S latitude), to 72 deg S latitude over the Palmer Peninsula, Antarctica. The first flight for the BrO detection system was on August 28. The distribution of BrO inside the chemically perturbed region defined by greatly elevated ClO abundances was different from that found just outside. Inside, the BrO mixing ratio was 6.1 + or - 1.1 pptv above the 440 K potential temperature surface, 4.7 + or - 2.0 pptv between the 400 and 440 K surfaces, and less than 4 pptv below the 400 K surface. At high latitudes outside the chemically perturbed region, the BrO mixing ratio was 5.4 + or - 1.4 pptv near the 450 K surface, but decreased to 2.9 + or - 1.2 pptv at the 420 K surface. The abundance of BrO showed no discernible temporal trend during the course of the nine flights. Away from the south polar region, at latitudes between 47 deg S and 37 deg N and potential temperatures between 435 and 500 K (18.5- to 20.7-km altitude), the BrO mixing ratio was 0.5-3.0 pptv.

Brune, W. H.↗

NASA NTRS1989

In situ observations of ClO in the Antarctic - ER-2 aircraft results from 54 deg S to 72 deg S latitude

The spatial and temporal distributions of ClO in the latitude belt from 54 to 72 deg S during the later stages of austral winter were obtained from measurements aboard the ER-2 aircraft flying at the altitude of about 18 km into the Antarctic polar vortex. Mixing ratios of about 10 parts per trillion by volume (pptv) were found in the vicinity of 55 deg S, increasing to 50 pptv at 60 deg S. A steep gradient of the ClO mixing ratio occurred in the vicinity of 65 deg S, where, at a fixed potential temperature, the value of the ClO mixing ratio increased by an order of magnitude within a very few degrees of latitude, defining the edge of the 'chemically perturbed region' (CPR). At the southern extension of the flight track, peak mixing ratios increased sharply from 800 pptv on August 23 to 1100 pptv in early September, and then increased more slowly to 1200 pptv on September 22. This corresponds to enhancements 500 times the typical mid-latitude values.

Brune, W. H.↗

NASA NTRS1989

Ozone destruction by chlorine radicals within the Antarctic vortex - The spatial and temporal evolution of ClO-O3 anticorrelation based on in situ ER-2 data

The chemical evolution of the Antarctic vortex region was studied during August 23-September 22, 1987 on the basis of in situ O3 and ClO data collected by the ER-2 aircraft. Particular attention is given to the evolution of the ClO-O3 anticorrelation from the first flight on August 23, 1987, which penetrated well into the vortex, through the course of 10 flights culminating on September 22, 1987. It is concluded that the disappearance of ozone within the Antarctic vortex results from halogen-catalyzed recombination of O3 to molecular oxygen.

Anderson, J. G.↗