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Pollock, W. H.

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

In situ measurements of BrO during AASE II

BrO measured from the NASA ER-2 during Airborne Arctic Stratospheric Expedition (AASE) II exhibited a mean value (for 20-minute averages) of 5.4 +/- 0.3 pptv, with a standard deviation of 3.1 pptv. Ratios of BrO to available inorganic bromine (Br(sub y)) show only slight increases in polar regions relative to midlatitudes. A comparison between observed latitudinal and diurnal variations of this same ratio and that calculated by photochemical models shows reasonable agreement in behavior, but significant discrepancies in magnitude. It is unclear whether this difference is due to errors in measurements, models or both.

Avallone, L. M.↗

Measurements of halogenated organic compounds near the tropical tropopause

The amount of organic chlorine and bromine entering the stratosphere have a direct influence on the magnitude of chlorine and bromine catalyzed ozone losses. Twelve organic chlorine species and five organic bromine species were measured from 12 samples collected near the tropopause between 23.8 deg N and 25.3 deg N during AASE 2. The average mixing ratios of total organic chlorine and total organic bromine were 3.50 +/- 0.06 ppbv and 21.1 +/- 0.8 pptv, respectively. CH3Cl represented 15.1% of the total organic chlorine, with CFC 11 (CCl3F) and CFC 12 (CCl2F2) accounting for 22.6% and 28.2%, respectively, with the remaining 34.1% primarily from CCl4, CH3CCl3, and CFC 113 (CCl2FCClF2). CH3Br represented 54% of the total organic bromine. The 95% confidence intervals of the mixing ratios of all but four of the individual compounds were within the range observed in low and mid-latitude mid-troposphere samples. The four compounds with significantly lower mixing ratios at the tropopause were CHCl3, CH2Cl2, CH2Br2, and CH3CCl3. The lower mixing ratios may be due to entrainment of southern hemisphere air during vertical transport in the tropical region and/or to exchange of air across the tropopause between the lower stratosphere and upper troposphere.

Schauffler, S. M.↗

Measurements of Halogenated Organic Compounds near the Tropical Tropopause

The amount of organic chlorine and bromine entering the stratosphere have a direct influence on the magnitude of chlorine and bromine catalyzed ozone losses. Twelve organic chlorine species and five organic bromine species were measured from 12 samples collected near the tropopause between 23.8 deg N and 25.3 deg N during AASE 2. The average mixing ratios of total organic chlorine and total organic bromine were 3.50 +/- 0.06 ppbv and 21.1 +/- 0.8 pptv, respectively. CH3Cl represented 15.1% of the total organic chlorine, with CFC 11 (CCl3F) and CFC 12 (CCl2F2) accounting for 22.6% and 28.2%, respectively, with the remaining 34.1% primarily from CCl4, CH3CCl3, and CFC 113 (CCl2FCClF2). CH3Br represented 54% of the total organic bromine. The 95% confidence intervals of the mixing ratios of all but four of the individual compounds were within the range observed in low and mid-latitude midtroposphere samples. The four compounds with significantly lower mixing ratios at the tropopause were CHCl3, CH2Cl2, CH2Br2, and CH3CCl3. The lower mixing ratios may be due to entrainment of southern hemisphere air during vertical transport in the tropical region and/or to exchange of air across the tropopause between the lower stratosphere and upper troposphere.

Schauffler, S. M.↗

Bromoalkane production by Antarctic ice algae

Ice microalgae, collected from the underside of annual sea ice in McMurdo Sound, Antarctica, were found to contain and release to seawater a number of brominated hydrocarbons. These included bromoform, dibromomethane, mixed bromochloromethanes, and methyl bromide. Atmospheric measurements in the McMurdo Sound vicinity revealed the presence of bromoform and methyl bromide in the lower atmosphere, with lowest concentrations inland, further indicating that biogenic activity in the Sound is a source of organic bromine gases to the Antarctic atmosphere. This may have important implications for boundary layer chemistry in Antarctica. In the Arctic, the presence of bromoform has been linked to loss of surface ozone in the spring. We report here preliminary evidence for similar surface ozone loss at McMurdo Station.

Sturges, W. T.↗

On the age of stratospheric air and ozone depletion potentials in polar regions

Observations of the nearly inert, man-made chlorofluorocarbon CFC-115 obtained during January 1989 are used to infer the age of air in the lower stratosphere. These observations together with estimated release rates suggest an average age of high-latitude air at pressure altitudes near 17-21 km of about 3 to 5 yr. This information is used together with direct measurements of HCFC-22, HCFC-142b, CH3Br, H-1301, H-1211, and H-2402 to examine the fractional dissociation of these species within the Arctic polar lower stratosphere compared to that of CFC-11 and hence to estimate their local ozone depletion potentials in this region. It is shown that these HCFCs are much less efficiently dissociated within the stratosphere than CFC-11, lowering their ozone depletion potentials to only about 30-40 percent of their chlorine loading potentials. In contrast, the observations of CH3Br and the Halons considered confirm that they are rapidly dissociated within the stratosphere, with important implications for their ozone depletion potentials.

Pollock, W. H.↗

Photochemical partitioning of the reactive nitrogen and chlorine reservoirs in the high-latitude stratosphere

The correlated set of measurements in the lower stratosphere from polar missions of the NASA ER-2 is used to derive partitioning of the major components of the reactive nitrogen and inorganic chlorine reservoirs. The results provide a consistent method for comparing distributions, and hence the controlling processes, between different areas of the near-polar regions. Clear evidence of the effects of heterogeneous processes in the atmosphere is found. Values for NO2, ClONO2, N2O5, and Cl2O2 are derived in a simplified steady-state model based on in situ NO, ClO, O3, temperature, and pressure measurements, laboratory-measured reaction rates; and modeled photodissociation rates. Values for the reservoir totals are independently derived from measurements of N2O, organic chlorine, and total reactive nitrogen. The relative abundances of the measured and derived species within the reservoirs are calculated, and the longer-lived species HCl and HNO3 are estimated as the residuals of their respective reservoirs.

Kawa, S. R.↗

Redistribution of reactive odd nitrogen in the lower arctic stratosphere

In-situ measurements of total reactive odd nitrogen NO(y), were made from the NASA DC-8 aircraft in the lower arctic stratosphere during the 1989 Airborne Arctic Stratospheric Expedition. Throughout January and February, NO(y) mixing ratios were typically between 0.5 and 3 parts per billion by volume (ppbv) at altitudes between 10 and 12.5 km. During several flights late in the mission, events of unusually light NO(y) occurred with mixing ratios up to 12 ppbv at these altitudes. Simultaneous measurements of N2O, O3, and H2O during these events suggest that large changes in NO(y) are not expected. The elevated NO(y) values are interpreted as a vertical redistribution of NO(y) in the lower stratosphere resulting from gravitational sedimentation of aerosol particles containing HNO3. No evidence of the redistribution of H2O is noted, consistent with observations of denitrification without dehydration higher in the stratosphere.

Huebler, G.↗

Trace gases in the Antarctic Atmosphere

Whole-air samples collected aboard the NASA ER-2 and DC-8 aircraft as part of the Airborne Antarctic Ozone Experiment were analyzed in a field laboratory set up at Punta Arenas, Chile. Mixing ratios obtained from gas chromatographic analyses of these samples are presented for CH4, CO, N2O, CFCl3, CF2Cl2, C2F3Cl3, CH3CCl3, and CCl4. A comparison of CFCl3/N2O mixing ratios from the flights of September 16-29, 1987 provides evidence of sustained subsidence.

Heidt, L. E.↗