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Wofsy, S. C.

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

At least 55 records · Page 3

The Amazon Boundary Layer Experiment (ABLE 2A) - Dry season 1985

The Amazon Boundary Layer Experiment (ABLE 2A) used data from aircraft, ground-based, and satellite platforms to characterize the chemistry and dynamics of the lower atmosphere over the Amazon Basin during the early-to-middle dry season, July and August 1985. This paper reports the conceptual framework and experimental approach used in ABLE 2A and serves as an introduction to the detailed papers which follow in this issue. The results of ABLE 2A demonstrate that isoprene, methane, carbon dioxide, nitric oxide, dimethylsulfide, and organic aerosol emissions from soils and vegetation play a major role in determining the chemical composition of the atmospheric mixed layer over undisturbed forest and wetland environments. As the dry season progresses, emissions from both local and distant biomass burning become an important source of carbon monoxide, nitric oxide and ozone in the atmosphere over the central Amazon Basin.

Harriss, R. C.↗

Emission of NO and deposition of O3 in a tropical forest system

Rates for emission of NO and deposition of O3 were measured at a tropical forest site in Reserve Adolfo Ducke, near Manaus, Brazil. Two independent techniques were used to determine the NO flux: (1) a soil enclosure method and (2) a method based on simultaneous observations of NO and O3 vertical profiles at night, when NO is irreversibly removed by reaction with O3. Results obtained using the two techniques agreed well, giving an average NO flux of 5.2 + or - 1.7 x 10 to the 10th molecules/sq cm per sec and an average vertical exchange coefficient of 2.2 x 10 to the 3rd cu cm/sec. Sources of NO from tropical forest soils may be important for global atmospheric chemistry. Rapid removal of O3 was observed in the lowest levels of the forest. The nocturnal deposition rate was estimated to be 5.6 + or - 2.5 x 10 to the 11th molecules/sq cm per sec through the 6-m level. The large deposition rate for O3 is consistent with the strong sink inferred from observations of ozone in the Amazon region.

Kaplan, W. A.↗

Emissions of N2O from tropical forest soils - Response to fertilization with NH4(+), NO3(-), and PO4(3-)

Undisturbed oxisols in a central Amazon tropical forest were fertilized with ammonium, nitrate, or phosphate. Enhanced emissions of N2O were observed for all treatments within one day of fertilization, with the response NO3(-) much greater than NH4(+) much greater than PO4(3-). Approximately, 0.5 percent of applied NO3(-) was converted to N2O within two weeks after application, with less than 0.1 percent of the NH4(+) converted to N2O. These experiments reveal a potentially large source of N2O from microbial reduction of NO3(-) in the clay soils of Amazonia.

Keller, M.↗

Sources of atmospheric nitrous oxide from combustion

Emissions of nitrous oxide (N2O) have been analyzed from industrial boilers and from a large experimental combustor burning natural gas, oil, or coal. Production of N2O and production of NO(x) were observed to be correlated, with an average molar ratio of 0.58:1 (N2O-N:NO). In conventional single-stage combustors, about 14 percent of fuel nitrogen is converted to N2O and 24 percent is converted to NO(x). Conversion of fuel nitrogen to N2O was much less efficient in a two-stage experimental combustor and in wood fires. A model is presented describing emissions of N2O globally, from the beginning of the industrial revolution to the present. It is expected that concentrations of N2O should rise more than 20 percent to about 367 ppb by the year 2050, based on conservative projections of world energy consumption.

Hao, W. M.↗

Reductions of Antarctic ozone due to synergistic interactions of chlorine and bromine

The vertical column density of ozone observed in October over Antarctica has fallen precipitously over the past 10 yr. The concentration at Halley Bay (76 deg S, 27 deg W), expressed conventionally in Dobson units (DU), has dropped from about 300 DU in 1975 to less than 200 DU in 1984. Values in 1985 were even lower, comparable with the lowest values recorded anywhere on earth. It is suggested here that the loss of O3 in Antarctica may be attributed to catalysis of O3 recombination by a scheme in which the rate-limiting step is defined by the reaction of ClO + BrO - Cl + Br + O2. Concentrations of NO2 must be low and heterogeneous reactions involving particles in the polar stratospheric clouds must be an important element of the relevant chemistry. Industrial sources make important contributions to the contemporary budgets of both BrO and ClO and are likely to grow significantly in the future.

Mcelroy, M. B.↗

The chemical control of soluble phosphorus in the Amazon estuary

The role of sediments in controlling concentrations of soluble phosphorous in the Amazon estuary is examined. The efflux of phosphorous through the estuary is calculated using data collected on field excursions in December 1982 and May 1983, and laboratory mixing experiments. It is observed that soluble phosphorus was released from bottom sediments at a rate of 0.2 micro-M/day, when in seawater and deionizd water mixtures. The relation between release rates and salinity and sediment concentrations is studied. A one-dimensional dispersion model was developed to estimate phosphate inputs to the estuary. The model predicted total fluxes of soluble inorganic phosphorous of 15 x 10 to the 6th mole/day for December 1982 and 27 x 10 to the 6th mole/day for May 1983; the predictions correlate with field observations. It is noted that phosphorous removal is between 0 and 4 ppt at a rate of 0.044 + or - 0.01 micron-M/ppt per day and the annual mean input of phophorous from Amazon to outer-estuary is 23 x 10 to the 6th moles/day.

Fox, L. E.↗

Tropospheric trace gases

Trace gas concentrations in the atmosphere reflect in part the overall metabolism of the biosphere, and in part the broad range of human activities such as agriculture, production of industrial chemicals, and combustion of fossil fuels and biomass. There is compelling evidence that the composition of the atmosphere is now changing. Observed trends in trace gas levels are reviewed and implications for the chemistry of the atmosphere are discussed. Throughout the discussion, particular emphasis is given to those species which are now increasing in the atmosphere.

Gammon, R.↗

Reductions in ozone at high concentrations of stratospheric halogens

An increase in the concentration of inorganic chlorine to levels comparable to that of oxidized reactive nitrogen could cause a significant change in the chemistry of the lower stratosphere leading to a reduction potentially larger than 15 percent in the column density of ozone. This could occur, for example by the middle of the next century, if emissions of man-made chlorocarbons were to grow at a rate of 3 percent per year. Ozone could be further depressed by release of industrial bromocarbon.

Prather, M. J.↗

Production of nitrous oxide and consumption of methane by forest soils

Soils in an Amazonian rainforest are observed to release N2O at a rate larger than the global mean by about a factor of 20. Emissions from a New England hardwood forest are approximately 30 times smaller then Brazilian values. Atmospheric methane is consumed by soils in both systems. Tropical forests would provide a major source of atmospheric N2O if the Brazilian results are representative.

Keller, M.↗

A stratospheric chemical instability

The equations which determine partitioning of Cl(x) in steady state have multiple (three) solutions under conditions which might arise in the high-latitude winter stratosphere. Two of these solutions are stable, one is unstable, to infinitesimal perturbations. The relative stability of solutions is examined by subjecting the system to finite perturbations. The more stable solution is found to eliminate the less stable when semi-infinite volumes of the two solutions are placed in contact. The high-ClO, low NO2 solution is more stable under most conditions. Transitions from less to more stable states are slow in winter but may occur more rapidly when the seasonal variation of insolation is taken into account.

Fox, J. L.↗

Production of NO and N2O by soil nitrifying bacteria

The composition of the atmosphere is influenced both directly and indirectly by biological activity. Evidence is presented here to suggest that nitrification in soil is a potentially significant source of both NO and N2O. Between 0.3 and 10% of the ammonium oxidized by cultures of the soil bacterium Nitrosomonas europaea is converted to these gases. The global source for NO associated with nitrification could be as large as 15,000,000 tonnes N/yr, with a source for N2O of 5,000,000-10,000,000 tonnes N/yr. Nitric oxide has a key role in tropospheric chemistry, participating in a complex set of reactions regulating OH and O3. Nitrous oxide is a dominant source of stratospheric NO and has a significant influence on climate.

Lipschultz, F.↗

Tropospheric chemistry - A global perspective

Processes that affect the concentration of tropospheric OH are considered, taking into account linkages between the chemistry of OH and the chemistry of H, HO2, and H2O2. A review is presented of observational data of special relevance to OH, notably the distributions of CO, CH4, O3, H2O, HNO3, NO, and NO2. Most of the results presented in connection with the description of the model were obtained by solving time-dependent continuity equations. Rates for photolytic processes were allowed to vary diurnally with insolation. It is found that a well-calibrated and reliable model for OH places important constraints on global budgets for a variety of gases including CH4, H2, and CH3Cl in addition to CO. Accurate measurements of species such as CH3CCl3 can provide valuable checks on global models that must integrate over a variety of atmospheric conditions. However, emission rates for the relevant gases must be adequately quantified.

Logan, J. A.↗

Production of NO2/-/ and N2O by nitrifying bacteria at reduced concentrations of oxygen

The influence of oxygen concentration on the production of NO2(-) and N2O by nitrifying marine bacteria of the genus Nitrosomonas is investigated. Pure cultures of the ammonium-oxiding bacteria isolated from the Western Tropical Atlantic Ocean were grown at oxygen partial pressures from 0.005 to 0.2 atm, and concentrations of N2O in the air above the growth medium and dissolved NO2(-) were determined. Decreasing oxygen concentrations are observed to induce a marked decrease in NO2(-) production rates and increase in N2O evolution, leading to an increase of the relative yield of N2O with respect to NO2(-) from 0.3% to nearly 10%. Similar yields of N2O at atmospheric oxygen levels are found for nitrifying bacteria of the genera Nitrosomonas, Nitrosolobus, Nitrosospira and Nitrosococcus, while nitrite-oxydizing bacteria and a dinoflagellate did not produce detectable quantities of N2O. Results support the view that nitrification is a major source of N2O in the environment.

Goreau, T. J.↗

Oxidation of CS2 and COS - sources for atmospheric SO2

The oxidation of COS and CS2 by reaction with hydroxyl radicals is investigated as a possible source of atmospheric SO2 in remote marine regions. Calculations of the vertical profiles of SO2 were performed based on a one-dimensional photochemical model of the formation and destruction of SO2 by various processes for observed O3, CO, CH4 and H2O profiles at 15 deg S. Variations in the rate of SO2 destruction, the chosen deposition velocity and the loss due to aerosols are shown to lead to similar SO2 profiles, which indicate higher mixing ratios at high altitude, while the oxidation of dimethyl sulfide or hydrogen sulfide can not account for the profiles observed. Possible diffuse sources of CS2 and COS are indicated, and it is concluded that the oxidation of COS and possibly CS2 may provide an explanation for the existence of a uniform background level of SO2.

Logan, J. A.↗

Aquatic sources and sinks for nitrous oxide

Data are presented which suggest the complexity of the aquatic nitrogen cycle as it affects N2O. The data are from studies made in the central and south-east tropical regions of the Pacific Ocean and in Chesapeake Bay. The data indicate that oxidation of ammonium and amino nitrogen and nitrification form the principle source for marine N2O. It is estimated that the yearly global yield for oceanic N2O is less than about 10 to the 7th power tons. The consumption of atmospheric N2O by the open ocean has not been evidenced, although data from the south-east tropical Pacific and Chesapeake Bay show the consumption of dissolved N2O in low-oxygen conditions. Preliminary observations have also indicated the consumption of atmospheric N2O by aquatic systems such as freshwater pond and a tidal saltmarsh.

Elkins, J. W.↗

Temporal and latitudinal variations of stratospheric trace gases - A critical comparison between theory and experiment

Global calculations of stratospheric HOx, Clx, and NOx are presented which include the effects of planetary albedo and diurnal and seasonal variations of the insolation. Comparisons are made with a wide range of atmospheric measurements at different latitudes and altitudes. Agreement between theory and observations is generally within a factor of 2. The theory appears to explain adequately the major features of latitude and seasonal distributions of NO2 and HNO3. The results indicate that mesospheric OH makes an appreciable contribution to the total OH column abundance and strongly suggest that nitrogen oxides exist principally in the form of HNO3 at high latitudes in winter. There are difficulties in reconciling OH, ClO, and O3 observations in the upper stratosphere.

Wofsy, S. C.↗