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Wofsy, S. C.

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

At least 37 records · Page 2

The Arctic Boundary Layer Expedition (ABLE-3B): July - August 1990

The Arctic Boundary Layer Expedition (ABLE) 3B used data from ground-based, aircraft, and satellite platforms to characterize the chemistry and dynamics of the troposphere in subarctic and Arctic regions of midcontinent and eastern Canada during July - August 1990. This paper reports the experimental design for ABLE 3B and a brief overview of results. The detailed results are presented in a series of papers in this issue. The chemical composition of the atmospheric mixed layer over remote tundra, boreal wetland, and forested environments was influenced by emissions of CH4 and nonmethane hydrocarbons from biogenic sources, emissions of gases and aerosols from local biomass burning, and transport of pollutants into the study areas from urban/industrial sources. Minimum concentrations of both trace gas and aerosol species in boundary layer air were associated with Arctic source areas. In the free troposphere the biospheric influence was undetectable, and major sources of chemical variability were related to long-range transport of pollutants into the study areas from biomass burning and industrial sources in Alaska and the Great Lakes regions, respectively. Minimum concentrations of both trace gas and aerosol species in the free troposphere were associated with a persistent, widespread air mass which both chemistry and air mass trajectory analyses suggested had originated in the tropical Pacific. Subsidence of air from the upper troposphere and lower stratosphere frequently enhanced ozone and influenced other trace gas and aerosol species at midtropospheric altitudes. The North American Arctic is a complex dynamical and chemical environment with considerable spatial and temporal variability in aerosol and trace gas concentrations. The use of atmospheric chemical indicators for climate change detection will require a much more comprehensive Arctic monitoring program than currently exists.

Harriss, R. C.

Balloon-borne measurements of ClO, NO, and O3 in a volcanic cloud: An analysis of heterogeneous chemistry between 20 and 30 km

Balloon profiles of chlorine monoxide (ClO), nitric oxide (NO), and ozone (O3) were measured on March 11, 1992 from 100 to 10 mb over Greenland (67.0 deg N, 50.6 deg W). Measurements from SAGE II indicate that the aerosol surface area in the region was enhanced by sulfur from the eruption of Mt. Pinatubo, reaching 50 times background near 20 km. Concentrations of ClO were enhanced and concentrations of NO were suppressed relative to low aerosol conditions consistent with the effects of hydrolysis of N2O5 on the surface of sulfuric acid aerosols. The data are consistent with a value of 2 x 10(exp -4) for the reaction probability of the heterogeneous hydrolysis of ClONO2, indicating a minor role for this reaction at as temperature of 220 K. At these temperatures, we find no evidence for the catastrophic loss of ozone predicted to occur under conditions of enhanced aerosol surface area.

Dessler, A. E.

Balloon-Borne Measurements of CLO, NO and O3 in a Volcanic Cloud: An Analysis of Heterogeneous Chemistry between 20 and 30 KM

Balloon profiles of chlorine monoxide (ClO), nitric oxide (NO), and ozone (O3) were measured on March 11, 1992 from 100 to 10 mb over Greenland (67.0 deg N, 50.6 deg W). Measurements from SAGE II indicate that the aerosol surface area in the region was enhanced by sulfur from the eruption of Mt. Pinatubo, reaching 50 times background near 20 km. Concentrations of ClO were enhanced and concentrations of NO were suppressed relative to low aerosol conditions consistent with the effects of hydrolysis of N2O5 on the surface of sulfuric acid aerosols. The data are consistent with a value of 2 x 10(exp -4) for the reaction probability of the heterogeneous hydrolysis of ClONO2, indicating a minor role for this reaction at a temperature of 220 K. At these temperatures, we find no evidence for the catastrophic loss of ozone predicted to occur under conditions of enhanced aerosol surface area.

Dessler, A. E.

Chemical loss of ozone in the Arctic polar vortex in the winter of 1991- 1992

In situ measurements of chlorine monoxide, bromine monoxide, and ozone are extrapolated globally, with the use of meteorological tracers, to infer the loss rates for ozone in the Arctic lower stratosphere during the Airborne Arctic Stratospheric Expedition II (AASE II) in the winter of 1991-1992. The analysis indicates removal of 15 to 20 percent of ambient ozone because of elevated concentrations of chlorine monoxide and bromine monoxide. Observations during AASE II define rates of removal of chlorine monoxide attributable to reaction with nitrogen dioxide (produced by photolysis of nitric acid) and to production of hydrochloric acid. Ozone loss ceased in March as concentrations of chlorine monoxide declined. Ozone losses could approach 50 percent if regeneration of nitrogen dioxide were inhibited by irreversible removal of nitrogen oxides (denitrification), as presently observed in the Antarctic, or without denitrification if inorganic chlorine concentrations were to double.

Salawitch, R. J.

Chemical Loss of Ozone in the Arctic Polar Vortex in the Winter of 1991-1992

In situ measurements of chlorine monoxide, bromine monoxide, and ozone are extrapolated globally, with the use of meteorological tracers, to infer the loss rates for ozone in the Arctic lower stratosphere during the Airborne Arctic Stratospheric Expedition II (AASE II) in the winter of 1991-1992. The analysis indicates removal of 15 to 20 percent of ambient ozone because of elevated concentrations of chlorine monoxide and bromine monoxide. Observations during AASE II define rates of removal of chlorine monoxide attributable to reaction with nitrogen dioxide (produced by photolysis of nitric acid) and to production of hydrochloric acid. Ozone loss ceased in March as concentrations of chlorine monoxide declined. Ozone losses could approach 50 percent if regeneration of nitrogen dioxide were inhibited by irreversible removal of nitrogen oxides (denitrification), as presently observed in the Antarctic, or without denitrification if inorganic chlorine concentrations were to double.

Salawitch, R. J.

Net exchange of CO2 in a mid-latitude forest

The eddy correlation method was used to measure the net ecosystem exchange of carbon dioxide continuously from April 1990 to December 1991 in a deciduous forest in central Massachusetts. The annual net uptake was 3.7 +/- 0.7 metric tons of carbon per hectare per year. Ecosystem respiration calculated from the relation between nighttime exchange and soil temperature, was 7.4 metric tons of carbon per hectare per year, implying gross ecosystem production of 11.1 metric tons of carbon per hectare per year. The observed rate of accumulation of carbon reflects recovery from agricultural development in the 1800s. Carbon uptake rates were notably larger than those assumed for temperate forests in global carbon studies. Carbon storage in temperate forests can play an important role in determining future concentrations of atmospheric carbon dioxide.

Wofsy, S. C.

The Arctic Boundary Layer Expedition (ABLE 3A) - July-August 1988

The Arctic Boundary Layer Expedition (ABLE 3A), conducted in Arctic and sub-Arctic regions of North America and Greenland during July and August 1988, was the first comprehensive investigation of the sources, sinks, and distribution of trace gas and aerosol chemical species in a northern high-latitude region during summer months. The experimental design emphasized the role of biosphere-atmosphere interactions in determining the chemical composition of the troposphere and in processes which influence the tropospheric O3 budget. This paper reports the overall experimental design of ABLE 3A and includes a brief overview of results.

Harriss, R. C.

Summertime photochemistry of the troposphere at high northern latitudes

Budgets of O3, NO(x), and NO(y), and acetic acid in the Arctic Boundary Layer Expedition (ABLE 3A) flight region are constructed using photochemical model statistics based on aircraft observations. A Lagrangian model is used to reconstruct the photochemical history of two aged biomass fire plumes sampled by the ABLE 3A aircraft. It is shown that anthropogenic influence on O3 levels in the Arctic may manifest itself not by long-range transport of pollution-derived O3, but rather by a decrease of the regional photochemical sink due to the presence of small amounts of NO(x). The low concentrations of NO(x) measured in ABLE 3A were sufficient to reduce the rate of photochemical loss appreciably relative to a NO(x)-free atmosphere, thus increasing the O3 lifetime. It is shown that decomposition of PAN can account for most of the NO(x) measured below 4-km altitude, but for only 20 percent at 6-km altitude. A lifetime of 29 days is estimated for NO(y) in the ABLE 23A flight region.

Jacob, D. J.

Deposition of ozone to tundra

Eddy correlation measurements of O3 deposition fluxes to tundra during the Arctic Boundary Layer Expedition (ABLE 3A) are reported. The mean O3 deposition velocity was 0.24 cm/s in the daytime and 0.12 cm/s at night. The day-to-day difference in deposition velocity was driven by both atmospheric stability and surface reactivity. The mean surface resistance to O3 deposition was 2.6 s/cm in the daytime and 3.4 s/cm at night. The relatively low surface resistance at night is attributed to light-insensitive uptake of O3 at dry upland tundra surfaces. The small day-tonight difference in surface resistance is attributed to additional stomatal uptake by wet meadow tundra plants in the daytime. The mean O3 deposition flux to the world north of 60 deg N in July-August is estimated at 8.2 x 10 exp 10 molecules/sq cm/s. Suppression of photochemical loss by small anthropogenic inputs of nitrogen oxides could have a major effect on O3 concentrations in the summertime Arctic troposphere.

Jacob, D. J.

Micrometeorological measurements of CH4 and CO2 exchange between the atmosphere and subarctic tundra

Eddy correlation flux measurements and concentration profiles of total hydrocarbons (THC) and CO2 were combined to provide a comprehensive record of atmosphere-biosphere exchange for these gases over a 30-day period in July-August 1988 in the Yukon-Kuskokwin River Delta of Alaska. Over 90 percent of net ecosystem exchanges of THC were due to methane. Lakes and wet meadow tundra provided the major sources of methane. The average fluxes from lake, dry tundra, and wet tundra were 11 +/- 3, 29 +/- 3, and 57 +/- 6 mg CH4/sq m/d, respectively. The mean remission rate for the site was 25 mg/sq m/d. Maximum uptake of CO2 by the tundra was 1.4 gC/sq m/d between 1000 and 1500 hrs, and nocturnal respiration averaged 0.73 gC/sq m/d. Net uptake of CO2 was 0.30 gC/sq m/d for the 30 days of measurement; methane flux accounted for 6 percent of CO2 net uptake.

Fan, S. M.

Atmospheric chemistry in the Arctic and subarctic - Influence of natural fires, industrial emissions, and stratospheric inputs

Layers with enhanced concentrations of trace gases intercepted by the NASA Electra aircraft over Alaska during the Arctic Boundary Layer Expedition (ABLE 3A) in July-August 1988 are discussed. Haze layers apparently associated with boreal fires were enriched in hydrocarbons and NO(y), with emission factors corresponding closely to laboratory data for smoldering combustion. It is argued that atmospheric composition was strongly modified by wildfires during several periods of the ABLE 3A mission. The associated enhancement of NO(y) was smaller than observed for most other combustion processes but was nonetheless significant in the context of very low background concentrations. Ozone production in fire plumes was negligible. Ambient O3 was supplied by the stratosphere, with little direct input from midlatitude source during summer. It is argued that NO(y) was supplied about equally by the stratosphere and by wildfires. Hydrocarbons and CO appear to derive from biomass fires and from human activities.

Wofsy, S. C.

A numerical method for parameterization of atmospheric chemistry - Computation of tropospheric OH

An efficient and stable computational scheme for parameterization of atmospheric chemistry is described. The 24-hour-average concentration of OH is represented as a set of high-order polynomials in variables such as temperature, densities of H2O, CO, O3, and NO(t) (defined as NO + NO2 + NO3 + 2N2O5 + HNO2 + HNO4) as well as variables determining solar irradiance: cloud cover, density of the overhead ozone column, surface albedo, latitude, and solar declination. This parameterization of OH chemistry was used in the three-dimensional study of global distribution of CH3CCl3. The proposed computational scheme can be used for parameterization of rates of chemical production and loss or of any other output of a full chemical model.

Spivakovsky, C. M.

Tropospheric OH in a three-dimensional chemical tracer model - An assessment based on observations of CH3CCl3

The paper introduces the representation of tropospheric chemistry allowing for calculation of chemical reaction rates within a chemical tracer model (CTM) simulation with the accuracy comparable to that of a detailed chemical model. The global distribution of tropospheric OH is calculated as a function of time, atmospheric composition, temperature, and solar irradiance. The globally integrated OH concentration weighted by frequency of reaction with CH3CCl3 is evaluated, along with the feasibility of using the observed latitudinal distribution of CH3CCl3 as a test for computed concentrations of OH. Seasonal variations of CH3CCl3 are also considered as a potential test for computed concentrations of OH. It is demonstrated that annual cycles of CH3CCl3 are controlled, or strongly influenced, by dynamical processes at latitudes northward of 25 deg South.

Spivakovsky, C. M.

Measurements of soil and canopy exchange rates in the Amazon rain forest using Rn-222

Measurements were taken of the emission of Rn-222 from Amazon forest rocks and soils and used as a tracer of ventilation of the forest canopy layer at night. It was determined that the greatest resistance to transfer of trace gases from the soil to the atmosphere lies in the soil air space. Profiles of Rn-222 and CO2 showed steepest concentration gradients in the layer between 0 and 3 m above soil surface. Aerodynamic resistances calculated for this layer from Rn-222 and CO2 varied from 1.6 to 18 s/cm, with greater resistance during the afternoon than at night. The resistance to exchange with air from the entire 41 m layer below the canopy averaged 4.8 s/cm during 13 nights of CO2 profiles. The calculated average time to flush the layer below 41 m is 5.5 hr, and it is concluded that this indicates that significant exchange occurs despite nocturnal stratification.

Trumbore, S. E.

Condensation of HNO3 on falling ice particles - Mechanism for denitrification of the polar stratosphere

Ice particles created in polar stratospheric cooling events are predicted to descend into Type I PSCs and accrete a coating of nitric acid trihydrate (NAT) that inhibits evaporation. Coated particles efficiently strip HNO3 from the atmosphere, providing a mechanism for denitrification without significant dehydration. Coatings that disintegrate may release large particles of NAT that influence subsequent particle growth.

Wofsy, S. C.

Denitrification in the Antarctic stratosphere

Rapid loss of ozone over Antarctica in spring requires that the abundance of gaseous nitric acid be very low. Precipitation of particulate nitric acid has been assumed to occur in association with large ice crystals, requiring significant removal of H2O and temperatures well below the frost point. However, stratospheric clouds exhibit a bimodal size distribution in the Antarctic atmosphere, with most of the nitrate concentrated in particles with radii of 1 micron or greater. It is argued here that the bimodal size distribution sets the stage for efficient denitrification, with nitrate particles either falling on their own or serving as nuclei for the condensation of ice. Denitrification can therefore occur without significant dehydration, and it is unnecessary for temperatures to drop significantly below the frost point.

Salawitch, R. J.

The chemistry of Antarctic ozone 1960-1987

The factors that influence Antarctic ozone are examined with a view to understanding the observed historical trend. Researchers show that reduced ambient temperatures can dramatically enhance the efficiency of chemical removal processes. Attention is focused on positive feedback between levels of ozone, temperature, and rates of heterogeneous chemical reactions. ClO and its dimer, and high levels of these gases are maintained until the clouds evaporate, on 15 September for the simulation shown here.

Salawitch, R. J.

Interactions between HCl, NO(x), and H2O ice in the Antarctic stratosphere - Implications for ozone

The role of PSC particles in determining the distributions of HCl and chlorine radicals is studied. The thermodynamics of HCl in ice is discussed, showing that significant quantities of HCl may be dissolved in ice when PSCs form. It is argued that HCl and HNO3 will be removed from the gas phase early in the condensation process, when only small quantities of H2O have been condensed, reflecting the thermodynamic properties of the solid phases of HCl, HNO3, and H2O. Rapid heterogeneous chemical reactions then volatilize reactive chlorine gases and convert NO(x) to solid-phase nitrates, which can be removed by gravitational settling. Analysis of the suite of heterogeneous chemical processes in the polar stratosphere implies a threshold for HCl concentrations, above which chemical loss rates for ozone increase dramatically.

Wofsy, S. C.