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Fishman, J.

Publications and source records attributed to Fishman, J..

28 records · Page 2

A two-dimensional photochemical model of the atmosphere. I Chlorocarbon emissions and their effect on stratospheric ozone

A two-dimensional photochemical model is used to examine changes to the ozone layer caused by emissions of CFCl3, CF2Cl2, CH3CCl3 and CCl4. The influence of a possible secular increase in tropospheric methane up to 2 percent per year was found to be small, although it acts to mask decreases in total ozone caused by the chlorocarbons. Increasing NO(x) emissions caused by industralization also tend to mask decreases in total ozone and may have caused total ozone to increase by about 1 percent. The model-calculated ozone decreases are estimated to be about 3 percent by 1980. This estimate is higher than estimates by similar models, although it is noted that CCl4 and CH3CCl3 emissions are included in the model in addition to CFCl3 and CF2Cl2. This is significant because the model indicates that CCl4 has dominated the ozone depletions so far, and knowledge of the historical emission rate of CCl4 to the atmosphere is incomplete. There remain sufficient significant disagreements between theoretical and observed concentrations and variabilities, particularly for odd nitrogen and ClO, to caution against assigning too much confidence in the calculated ozone depletion.

Gidel, L. T.↗

Correlative nature of ozone and carbon monoxide in the troposphere - Implications for the tropospheric ozone budget

The small-scale vertical variability of troposheric O3 and CO is examined using a set of simultaneous measurements obtained in July and August 1974 between 55 deg S and 67 deg N. From this set of vertical profiles, it is found that many of the fluctuations are coincident in both species, and a method is presented that quantifies the correlation between the observed O3 and CO variability. A two-dimensional depiction of the distribution of these O3-CO correlations reveals that there are regions in the troposphere where these trace gases are positively correlated and that, at the same time, there are preferred locations where these two species are primarily anticorrelated. The regions of anticorrelation are found to be consistent with the traditional picture of the tropospheric ozone cycle, suggesting that this gas is chemically unreactive in the troposphere. On the other hand, the location and magnitude of the region in which these two species are positively correlated indicates that there is considerable in situ production of tropospheric ozone.

Fishman, J.↗

The distribution of carbon monoxide and ozone in the free troposphere

The two-dimensional distributions of CO and O3 in the free troposphere during July and August, 1974, are discussed. The data confirm the previous findings that both of these gases are considerably more abundant in the northern hemisphere, but the degree of the asymmetry is somewhat different from what had been reported previously, especially for CO. When examined with respect to other available data sets, the conclusion is drawn that a pronounced seasonal cycle exists for CO in both hemispheres which may be driven by the likely seasonal cycle of the OH radical. The data also indicate that CO concentrations exhibit significant variability with height in the northern hemisphere, whereas southern hemispheric concentrations are quite constant with altitude except in cases where interhemispheric exchange of air may be occurring. A discussion on the vertical and horizontal transport processes inferred from the CO and O3 measurements is presented. The possible interdependence of the photochemical cycles of these two trace gases is also discussed.

Seiler, G.↗

Simultaneous measurements of NO/x/, NO, and O3 production in a laboratory discharge - Atmospheric implications

Simultaneous measurements of NO(x) (NO + NO2), NO, and O3 production in a laboratory discharge show that within the uncertainties of the experiment, all of the NO(x) produced was NO, and no detectable enhancement of O3 after the discharge was observed. The laboratory experiments described gave an NO production rate of 5 + or - 2 x 10 to the 16th molecules/joule mole for a 100,000-1,000,000 joules/m spark. Assuming that the global dissipation of lightning energy is about 10 to the -8th joules/sq cm per sec (Dawson, 1980; and Hill et al., 1980), the NO production rate results in a global source of NO due to lightning of about 1.8 Mt(N)/yr, which is considerably lower than earlier estimates. This lower value for NO(x) production by lightning suggests that NO(x) emissions from anthropogenic sources, estimated to be at least 20 MT(N)/yr, may be the dominant source of NO(x) to the global troposphere. Furthermore, since most of the anthropogenic sources of NO(x) are located in the Northern Hemisphere, this new interpretation of the relative source strengths of this species favors a highly skewed asymmetric distribution of NO(x).

Levine, J. S.↗

Simultaneous presence of O3 and CO bands in the troposphere

Vertical profiles of CO and O3 in the troposphere and lower stratosphere have been constructed during a series of flights conducted in July and August 1974 over the American continents between 53 deg S and 67 deg N. The mixing ratios of both gases show large fluctuations with altitude in the Northern Hemisphere. Most of the observed bands of O3 in the free troposphere are coexistent with elevated CO concentrations indicating that this O3 is probably not of stratospheric origin, but most likely produced in the troposphere. From the observations, it is not clear whether these high concentrations of ozone were produced in situ in the remote troposphere or had been transported out of a polluted boundary layer. Isentropic trajectory calculations likewise indicate that the air containing these elevated ozone and carbon monoxide concentrations had been situated in the troposphere for at least 72 h prior to being sampled.

Fishman, J.↗

Actinometric measurements and theoretical calculations of j/O3/, the rate of photolysis of ozone to O/1D/

The paper presents an experimental technique which measures j/O3-O(1-D)/, the rate of solar photolysis of ozone to singlet oxygen atoms. It is shown that a flow actinometer carries dilute O3 in N2O into direct sunlight where the O(1D) formed reacts with N2O to form NO which chemiluminescence detects, with a time resolution of about one minute. Measurements indicate a photolysis rate of 1.2 (+ or - .2) x 10 to the -5/s for a cloudless sky, 45 deg zenith angle, 0.345 cm ozone column and zero albedo. Finally, ground level results compare with theoretical calculations based on the UV actinic flux as a function of ozone column and solar zenith angle.

Dickerson, R. R.↗

Observational and theoretical evidence in support of a significant in-situ photochemical source of tropospheric ozone

The latitudinal and seasonal variation of ozone in the troposphere is discussed. Of particular interest is the asymmetrical behavior of this gas with respect to the two hemispheres. These asymmetries, when coupled with a diagnostic photochemical model of the troposphere, lends support to the view that ozone cannot be viewed as an inert tracer of stratospheric origin. In the calculations it is noted that it is likely that the budgets of carbon monoxide and tropospheric ozone may be quite dependent on each other and the calculations are discussed in light of the uncertainty which currently exists about representative global tropospheric background concentrations of the nitrogen oxides. In addition, the seasonal variation of excess (C-14)O2 (a stratospheric tracer) is examined and compared with the seasonal ozone variation during the same period of observations at the same location and altitudes. The distinct maxima for ozone found during the summer in the lower troposphere are not present for the (C-14)O2 data. This finding likewise suggests that photochemical processes taking place in the troposphere are an important source term for tropospheric ozone.

Fishman, J.↗

The origin of ozone in the troposphere

Examination of the distribution of tropospheric ozone indicates that surface destruction in the Northern Hemisphere (NH) should be about three times larger than in the Southern Hemisphere (SH). If, according to the traditional understanding of ozone, this species were a passive tracer in the troposphere, a threefold larger flux out of the stratosphere should exist in the NH than in the SH. However, meteorological analyses fail to support such pronounced hemispheric differences in stratosphere-troposphere exchange. Alternatively, therefore, it is hypothesized that photochemical synthesis of ozone in the troposphere may be particularly important in the NH because of asymmetries in the sources and distribution of carbon monoxide, hydrocarbons and nitric oxide.

Fishman, J.↗

Estimates on the production of CO and H2 from the oxidation of hydrocarbon emissions from vegetation

Extrapolating from extensive field measurements on foliar emissions in the U.S. approximate global inputs of isoprene and terpenes of 3.5 times 10 to the 14th power and 4.8 times 10 to the 14th power g(C)/yr, respectively, are obtained. The oxidation of these hydrocarbons could contribute in an important way to the atmospheric sources of CO (4.2-13.3 times 10 to the 14th power g/yr) and H2 (10-35 times 10 to the 12th power g/yr), and to organic species soluble in rainwater

Zimmerman, P. R.↗