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Wofsy, Steven C.

Publications and source records attributed to Wofsy, Steven C..

At least 37 records · Page 2

Simulation of summertime ozone over North America

The concentrations of O3 and its precursors over North America are simulated for three summer months with a 3D, continental-scale photochemical model using meteorological input from the Goddard Institute for Space Studies (GISS) GCM. The model has 4 x 5 deg grid resolution and represents nonlinear chemistry in urban and industrial plumes with a subgrid nested scheme. Simulated median afternoon O3 concentrations at rural U.S. sites are within 5 ppb of observations in most cases, except in the south central U.S., where concentrations are overpredicted by 15-20 ppb. The model captures successfully the development of regional high-O3 episodes over the northeastern United States on the back side of weak, warm, stagnant anticyclones. Simulated concentrations of CO and nonmethane hydrocarbons are generally in good agreement with observations, concentrations of NO(x) are underpredicted by 10-30 percent, and concentrations of PANs are overpredicted by a factor of 2 to 3. The overprediction of PANs is attributed to flaws in the photochemical mechanism, including excessive production from oxidation of isoprene, and may also reflect an underestimate of PANs deposition. Subgrid nonlinear chemistry as captured by the nested plumes scheme decreases the net O3 production computed in the U.S. boundary layer by 8 percent on average.

Jacob, Daniel J.↗

Factors regulating ozone over the United States and its export to the global atmosphere

Attention is given to the factors regulating summertime O3 over the U.S. and its export to the global atmosphere, which are examined via a 3-mo simulation involving a continental-scale 3D photochemical model. It is found that reducing NO(x) emissions by 50 percent from 1985 levels would decrease rural O3 concentrations over the eastern U.S. by about 15 percent under almost all meteorological conditions, while reducing anthropogenic hydrocarbon emissions by 50 percent would have less than a 4 percent effect except in the largest urban plumes. The correlation between O3 concentrations and temperature observed at eastern U.S. sites is attributed in part to the association of high temperatures with regional stagnation, and in part to an actual dependence of O3 production on temperature driven primarily by conversion of NO(x) to PAN.

Jacob, Daniel J.↗

Measurement of HO2 and other trace gases in the stratosphere using a high resolution far-infrared spectrometer at 28 km

This report covers the time period 1 January 1993 to 30 June 1993. During this reporting period we had our third Upper Atmosphere Research Satellite (UARS) correlative balloon flight and submitted the results from this flight to the Central Data Handling Facility (CDHF). We made a number of improvements in our data processing software in preparation for a new analysis of our old balloon data sets. Finally, we continue to analyze the data obtained during the second Airborne Arctic Stratospheric Expedition (AASE 2).

Traub, Wesley A.↗

Vapor pressures of solid hydrates of nitric acid - Implications for polar stratospheric clouds

Thermodynamic data are presented for hydrates of nitric acid: HNO3.H2O, HNO3.2H2O, HNO3.3H2O, and a higher hydrate. Laboratory data indicate that nucleation and persistence of metastable HNO3.2H2O may be favored in polar stratospheric clouds over the slightly more stable HNO3.3H2O. Atmospheric observations indicate that some polar stratospheric clouds may be composed of HNO3.2H2O and HNO3.3H2O. Vapor transfer from HNO3.2H2O to HNO3.3H2O could be a key step in the sedimentation of HNO3, which plays an important role in the depletion of polar ozone.

Worsnop, Douglas R.↗

Measurements of NO(x) and NO(y) concentrations and fluxes over Arctic tundra

Measurements of the atmospheric concentrations of NO, NO2, total NO(y), and O3 were made during the NASA Arctic Boundary Layer Expedition (ABLE 3A) at a remote location in a tundra bog ecosystem in southeastern Alaska during the growing season (July-August 1988). Concentrations of NO(x) and NO(y) were found to be very low compared to other remote continental sites, indicating that anthropogenic influences were small at this site during this time of year. The NO(y) emission rate from the soil were 0.13 +/- 0.05 x 10 exp 9 molecules/sq cm/s. Direct measurements of the flux of total NO(y) were made for the first time, indicating downward flux of NO(y) at all times of day, with maximum deposition of 2.5 +/- 0.9 x 10 exp 9 molecules/sq cm/s in the afternoon. Deposition of HNO3 appears to dominate the atmosphere/surface exchange of NO(y). The mean dry deposition rate of NO(y) to the tundra was 1.8 +/- 1.0 x 10 exp 9 molecules/sq cm/s.

Bakwin, Peter S.↗

Biosphere/atmosphere CO2 exchange in tundra ecosystems - Community characteristics and relationships with multispectral surface reflectance

CO2 exchange rates were measured at selected tundra sites near Bethel, Alaska using portable, climate-controlled, instrumented enclosures. The empirically modeled exchange rate for a representative area of vegetated tundra was 1.2 +/- 1.2 g/sq m/d, compared to a tower-measured exchange over the same time period of 1.1 +.0- 1.2 g/sq m/d. Net exchange in response to varying light levels was compared to wet meadow and dry upland tundra, and to the net exchange measured by the micrometeoroidal tower technique. The multispectral reflectance properties of the sites were measured and related to exchange rates in order to provide a quantitative foundation for the use of satellite remote sensing to monitor biosphere/atmosphere CO2 exchange in the tundra biome.

Whiting, Gary J.↗

Budgets of reactive nitrogen, hydrocarbons, and ozone over the Amazon forest during the wet season

The atmospheric composition over the Amazon forest during the wet season is simulated with a one-dimensional photochemical model for the planetary boundary layer (PBL) extending from the ground to 2000-m altitude. The model is constrained and evaluated using observations from the Amazon Boundary Layer Experiment 2B field expedition. Results indicate that only about 20 percent of NO(x) emitted by soils is exported to the atmosphere above the forest canopy. The balance is deposited to vegetation before leaving the canopy layer. The small NO(x) flux that escapes from the canopy is nevertheless sufficient to account for the low NO concentrations observed in the PBL. Soil emission can account for only a portion of NO(y) observed over the forest. Organic nitrates of nonbiogenic origin likely account for the balance of NO(y). Enhancements of CO observed in the PBL appear to reflect direct emission of CO by the forest ecosystem. Concentrations of O3 in the PBL are regulated largely by transport from aloft and deposition to the canopy, with little net influence from photochemistry. Ozone is photochemically produced immediately above the forest where NO concentrations are relatively high, but is photochemically consumed in the upper portion of the PBL.

Jacob, Daniel J.↗

Emission of nitric oxide (NO) from tropical forest soils and exchange of NO between the forest canopy and atmospheric boundary layers

Emissions of NO from soils in the Amazon rain forest were measured at 66 locations using an enclosure technique, and continuous vertical profiles of NO and O3 were measured between the ground and 41-m altitude. Fluxes of NO averaged 8.9 (+ or - 1.5) x 10 to the 9th molecules/sq cm per sec from the dominant (yellow clay) soils of the region, with larger fluxes observed from adjacent white sand soils. Fluxes from clay soils were lower by more than a factor of 5 than fluxes observed during the dry season at a nearby site. Low soil emission rates were reflected in lower concentrations of NO at the top of the forest canopy in the wet season, only 30-50 parts per trillion by volume during the daytime. The measured fluxes are consistent with chemical mass balances for NO within the forest canopy, calculated from the NO and O3 profiles taken at night, and with observations of NO between 150 and 5000 m altitude. Measurements of NO emission rates from soil plots fertilized using NaNO3, NH4Cl, or sucrose indicated that a reductive pathway (denitrification) may have been primarily responsible for production of the NO released by both clay and sand soils.

Bakwin, Peter S.↗

Measurements of reactive nitrogen oxides (NO/y/) within and above a tropical forest canopy in the wet season

Measurements of ambient concentrations of reactive nitrogen oxides were made in the Amazon rain forest, near Manaus, Brazil, continuously at 39 m (above the canopy), and on several days and nights at 19 m (within the canopy). Concentrations were very low, typically 100-700 pptv, except for brief periods when up to 5000 pptv of NO(y) was observed, indicating polluted air from the urban area of Manaus. The forest was a net sink for NO(y) with the NO(y) flux = -7.6 + or - 5.0) x 10 to the 9th molecules/sq cm per sec in unpolluted periods, even though soils emitted NO at a significant rate (8.9 + or - 1.5 x 10 to the 9th molecules/sq cm per sec). The deposition rate for NO(y) appeared to be much larger during the daytime than at night, suggesting that uptake was controlled either by plant processes (stomatal opening) or by supply of reactive components of NO(y) (e.g., HNO3) during the daytime. Implications for regional and global atmospheric chemistry are discussed.

Bakwin, Peter S.↗

Atmosphere-biosphere exchange of CO2 and O3 in the Central Amazon Forest

An eddy correlation measurement of O3 deposition and CO2 exchange at a level 10 m above the canopy of the Amazon forest, conducted as part of the NASA/INPE ABLE2b mission during the wet season of 1987, is presented. It was found that the ecosystem exchange of CO2 undergoes a well-defined diurnal variation driven by the input of solar radiation. A curvilinear relationship was found between solar irradiance and uptake of CO2, with net CO2 uptake at a given solar irradiance equal to rates observed over forests in other climate zones. The carbon balance of the system appeared sensitive to cloud cover on the time scale of the experiment, suggesting that global carbon storage might be affected by changes in insolation associated with tropical climate fluctuations. The forest was found to be an efficient sink for O3 during the day, and evidence indicates that the Amazon forests could be a significant sink for global ozone during the nine-month wet period and that deforestation could dramatically alter O3 budgets.

Fan, Song-Miao↗

Nucleation and growth of HNO3-3H2O particles in the polar stratosphere

Growth of nitric acid trihydrate (NAT) particles on background stratospheric aerosols is examined for an isolated air parcel cooled at a uniform rate. During the process of nucleation, the saturation ratio of HNO3 vapor reaches a maximum value between 2 and 15, corresponding to supercooling by 1-4 K. If cooling rates exceed 0.5-1 K/day, small particles of NAT are produced. A major fraction of the available condensation nuclei is activated and removal of HNO3 by gravitational settling is slow. If cooling rates are less than 0.5-1 K/day, the number of aerosols that nucleate is reduced, leading to differential growth of large NAT particles. Observations of 5 micron radius particles in clouds at temperatures above the water frost point may reflect condensation of NAT on ice particles that fall through a column of air as it is cooled. Rapid condensation of HNO3 on ice particles is promoted by the high supersaturation attained during nucleation and maintained during subsequent cooling. This process provides a mechanism for irreversible removal of HNO3.

Wofsy, Steven C.↗

Heterogeneous conversion of COF2 to HF in polar stratospheric clouds

It is argued that the reaction COF2 + H2O - 2HF + CO2 should proceed on surfaces of polar stratospheric clouds, based on laboratory evidence for this reaction in condensed phase and on analysis of column observations of HF during the Airborne Arctic Stratospheric Expedition. If the hypothesis is confirmed, observations of COF2 and HF could provide unambiguous indication of heterogeneous processing of polar air, and could help elucidate the influence of heterogeneous chemistry on concentrations of HCl, ClNO3, and chlorine oxide radicals.

Wofsy, Steven C.↗

Influence of polar stratospheric clouds on the depletion of Antarctic ozone

Precipitation of nitrate in polar stratospheric clouds (PSCs) can provide a significant sink for Antarctic stratospheric odd nitrogen. It is argued that the depth of the Ozone Hole is sensitive to the occurrence of temperatures below about 196 K. An increase in the prevalence of temperatures below 196 K would enhance ozone loss by increasing the spatial extent and persistence of PSCs, and by decreasing the level of HNO3 that remains following PSC evaporation. Concentrations of halogen gases in the 1960s and earlier were insufficient to support major ozone loss, even if thermal conditions were favorable.

Salawitch, Ross J.↗

Carbon dioxide in the atmosphere over the Amazon Basin

As a part of the NASA's Amazon Boundary Layer Experiment 2A mission, the cycle of atmospheric CO2 over the Amazon Basin was examined using measured vertical profiles of CO2 concentrations in the canopy and aloft, and direct measurements of CO2 emissions from soils. The results provide a detailed picture of daily exchanges of air between the tropical forest (0-30) and the atmospheric boundary layer (30-2000 m). A comparison of atmospheric CO2 distributions over forests, wetlands, and rivers shows that the lower atmosphere over forests functions separately from that over rivers or wetlands during the night and to some extent during the day; the basic diurnal cycle of CO2 over wetlands is much weaker than over forests, and the cycle is almost absent over rivers. This result is consistent with expectations based on the biogeochemistry of organic carbon in these systems.

Wofsy, Steven C.↗

Photochemistry of biogenic emissions over the Amazon forest

The boundary layer chemistry over the Amazon forest during the dry season is simulated with a photochemical model. Results are in good agreement with measurements of isoprene, NO, ozone, and organic acids. Photochemical reactions of biogenic isoprene and NOx can supply most of the ozone observed in the boundary layer. Production of ozone is very sensitive to the availability of NOx, but is insensitive to the isoprene source strength. High concentrations of total odd nitrogen (NOy) are predicted for the planetary boundary layer, about 1 ppb in the mixed layer and 0.75 ppb in the convective cloud layer. Most of the odd nitrogen is present as PAN-type species, which are removed by dry deposition to the forest. The observed daytime variations of isoprene are explained by a strong dependence of the isoprene emission flux on sun angle. Nighttime losses of isoprene exceed rates of reaction with NO3 and O3 and appear to reflect dry-deposition processes. The 24-hour averaged isoprene emission flux is calculated to be 38 mg/sq m per day. Photooxidation of isoprene could account for a large fraction of the CO enrichment observed in the boundary layer under unpolluted conditions and could constitute an important atmospheric source of formic acid, methacrylic acid, and pyruvic acid.

Jacob, Daniel J.↗

Chemistry of OClO in the Antarctic stratosphere - Implications for bromine

Previous observations of OClO over the Antarctic obtained in 1986 are used to constrain the stratospheric abundance of bromine. The observed diurnal variation is consistent with the production of OClO via the reaction of ClO with BrO if the branching ratio to the BrCl channel is between 3.5 and 14 percent. Otherwise, an additional source in twilight is indicated. The present results suggest a stratospheric bromine concentration of 16 + or - 4 pptv, a value which is consistent with independent measurements.

Salawitch, Ross J.↗

Chemistry of the Antarctic stratosphere

Interferometric measurements of HCl, ClNO3, HNO3, NO2, and NO obtained over the Antarctic in 1986 are used to model the chemistry of the atmosphere in the region of the Ozone Hole. The low abundance noted in stratospheric HCl is attributed to incorporation of HCl in polar stratospheric clouds and subsequent reaction of HCl with ClNO3. The results point to a net loss of HNO3 from the stratosphere and to the suppression of the abundance of odd nitrogen at high altitudes in the vortex. O3 loss is suggested to be due to the catalytic influence of halogen radicals.

Mcelroy, Michael B.↗

Atmospheric distribution of Kr-85 simulated with a general circulation model

A three-dimensional chemical tracer model for the troposphere is used to simulate the global distribution of Kr-85, a long-lived radioisotope released at northern midlatitudes by nuclear industry. Simulated distributions for the period 1980-1983 are in excellent agreement with data from six latitudinal profiles measured over the Atlantic. High concentrations of Kr-85 are predicted over the Arctic in winter, advected from European sources, and somewhat smaller enhancements arising from the same sources are predicted over the tropical Atlantic in summer. Latitudinal gradients are steepest in the northern tropics, with distinctly different seasonal variations over the Pacific, as compared to the Atlantic. The global inventory of Kr-85 is reconstructed for the period 1980-1983 by combining the concentrations measured over the Atlantic with the global distributions predicted by the model. The magnitude of the Soviet source is derived. The interhemispheric exchange time is calculated as 1.1 years, with little seasonal dependence.

Jacob, Daniel J.↗