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Appendix D THE MEASUREMENT OF TRACE REACTIVE SPEC I ES I N THE STRATOSPHERE: A REVIEW OF RACE NT RESULTS J.G. Anderson Harvard University INTRODUCTI ON The central objective of this report is to review critically the data base on trace species observations in the stratosphere for the specific purpose of testing predictions of global ozone depletion resulting from th release of compounds containing chlorine and nitrogen into the lower atmosphere. A corollary objective is to appraise prospects for significant advances in the next five years and to suggest a strategy for that research. Achieving the first objective in a reasonably concise document must confront the often incompatible elements of data quality, quantity, and applicability to theory. For example, a large body of data may exist on a particular radical that is of demonstrably superior quality with respect to the analytical method, but that, if not taken at the proper time of day and referenced to the local tropopause height, may be uninterpretable in terms of a modeled distribution. We will deal with the sheer volume of information by referencing the recent WMO/NASA report document, "The Stratosphere 1981: Theory and Measure- ments," whenever possible while attempting to maintain reasonable continuity in this report (Hudson et al. 1982). The species that are of interest to the stratospheric photochemistry of ozone are divided into groups and listed in Table D.1. The ordering of groups and of the species within each group in the table is rather arbitrary, but the choice seeks to represent the fact that the central objective of this report is an assessment of the effect of fluorocarbon release on stratospheric ozone. Thus, the photochemically active chlorine components are treated first. e 206 on

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207 TABLE D.1 Chemical Species of Interest In the Stratospheric Chemistry of Ozone Species Group 1 2 3 4 6 l 8 5 ~ 1 C10 C1 C100 OC10 HC1 HOC1 C1ONO2 2 OH HO2 H H2 H2O2 H2O 3 0(3P) O(iD) 02(~/\) 02(~) 0*2 O3 (other) 4 NO NO2 N NO3 N2Os HONO2 5 BrO Br BrO2 OBrO HBr HOBr BrONO2 6 FO F FO2 OFO HF A review of the data appears first. Then we examine . ~ ~ ~ _ how well the current data base constrains morel prealc- tions of ozone reduction. ~ uncertainties in the reaction rate constant data by defining a series of six "cases," tracing the impact of rate constant assumptions on the key free radicals and on the altitude dependence of odd oxygen destruction. objective is first to correlate each case with the observed vertical distribution of the key free radicals to determine whether a consistent picture evolves, and, second, to identify the altitude regime in which the maximum impact on ozone occurs, resulting from changes in total chlorine or reactive nitrogen. Finally we abstract from the analysis a series of questions that must be addressed by measurement of trace species in the stratosphere. The answers are essential for significant progress to be realized in the near future. Following each question is an appraisal of the prospects for progress in the next three years. The ~ And 1 vet in f irst summarizes The REVIEW OF DATA BASE ON TRACE SPECIES Group 1: Reactive Trace Constituents Containing Chlorine While the case linking fluorocarbons released at the earth's surface to the global distribution of ozone is made up of innumerable elements, the single most important observable in the stratosphere for a first-order appraisal of ozone destruction rates resulting from the decomposi- tion of fluorocarbons is the concentration of the chlorine monoxide free radical, C10. The reason for this is that C10 is the rate limiting (RL) chlorine constituent in the

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208 major catalytic cycles (see the recent discussion by Weubbles and Chang (1981)): C1 + O3 C1O + 0 C1O + O2 C1 + O2 (RL) O + O3 C1 + O3 2o2 C1O + O2 + HOC1 + O2 (RL) C1O + HO2 OH + O3 ~ HO' + OK HOC1 + he ~ OH + C1 O3 + O3 ~ 3O2 C1 + O3 ~ C1O + O2 NO + O3 ~ NO2 + O2 C1O + NO2 + M ~ ClONO2 + M ClONO2 + he ~ NO3 + C1~ NO3 + he ~ NO + O2 >(RL) O3 + O3 ~ 3O2 C1O has thus been the focus of experimental attention since Molina and Rowland (1974) first linked fluorocarbon release to global ozone reduction. In addition, because C1O dominates the chlorine free radical system with respect to concentration, reaching nearly 1 part per billion (ppb) in the middle to upper stratosphere (its reactive partner, C1, for example, reaches only 1 part per trillion [ppt] in the stratosphere), it is amenable to a broader class of observational techniques. Four other chlorine-containing constituents are of central importance: HC1, C1, HOC1, and C1ONO2 (with possible isomeric forms). Chlorine Monoxide (C1O) Three methods have been successfully applied to the detection of stratospheric C1O (listed here in the chronological order of their application): 1. Balloon-borne in situ resonance fluorescence methods (Anderson et al. 1977, 1980; Weinstock et al. 1981). 2. Ground-based millimeter(mm)-wave emission spectroscopy of the C1O total column at 204 GHz (Parrish et al. 1981). -

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209 3. Balloon-borne, mm-wave emission spectroscopy of C10 at 204 GHz (Waters et al. 1981). Aircraft-borne observations by this group had previously established an upper limit on stratosphere C10 (Waters et al. 1979). A fourth method, that of balloon-borne, laser hetero- dyne radiometry (see Menzies 1978, Menzies et al. 1981), has been applied to the problem, but ambiguities in spectral line position prevent an interpretation of the results. While a clear consensus on several aspects of the stratospheric C10 distribution has not emerged, the last two years have witnessed several crucial steps toward a first-order understanding of [C10] (where square brackets indicate concentration) at middle latitudes. We consider first results from the two balloon-borne techniques that provide a direct determination of the altitude dependence of [C10]. Figure D.1 summarizes 10 observations reported by Weinstock et al. (1981) obtained using method 1. All observations contained in Figure D.1 represent midday conditions at 32N latitude; variations in solar zenith angle primarily reflect changes in solar declination. The in situ observations fall into two classes; 8 of the 10 define an envelope with deviations limited to about +50 percent about the observed mean; two of the observations, both obtained in July, fall clearly outside of the envelope and are not representative of the mean distribution of C10 at middle latitudes. Without independent substantiation, the two July observations cannot be included in the data base defining the mean distribution of C10. In Figure D.2, the envelope of in situ observations is superposed with the recent balloon-borne observations of Waters et al. (1981) using mm-wave emission techniques. Included in the in situ array is an observation (June 1, 1978) not included in the Weinstock et al. (1981) publication because it was obtained using an instrument with no previous flight history; the results are not at variance and are included for completeness. The consistency in both absolute magnitude and gradient between the two techniques is one of the most important results to be achieved since the last NRC report (NRC 1979). _ ~ It underscores the importance of using independent techniques to cross-calibrate observational methods for all of the key radicals involved directly in processes that control the rate of odd oxygen destruction.

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210 . . ~ ~ ~''1 ' 41 30 29 _ 27 _ 26 28 2S l _ C 10 M IXING RATIO . 40 - o 39 - O 38 _ 37 V 36 _ 36 _ 34 _ 33 _ ~ 32 - X 7 O 26 SEPTEMBER X'38 W~~Y///~J 28 JULY 1976 8 DECEM BER 1976 14 JULY 1977 20 SEPTEMBER 1977 25 OCTOBER 1977 2 DECEMBER 1977 X~ 50 16 NOVEMBER 1978 X =soo ;N X ~43 5SO 41 41 15 JUNE 1979 ;~: AUGUST 1979 ~! I ~: ~ [r~X 1 . ~.. 10 11 T ~_ . 1 IOK) 0/ h/ _ , , . , , , ., 1 , . . . . [CIO] / [M] . . . . . . 10 9 - - 10'. FIGURE D.1 Summary of the vertical distribution of C10 obtained between July 28, 1976, and September 26, 1979, using in situ resonance fluorescence methods (from Weinstock et al. 1981~. 50 45 40 35 LLI 30 25 C{O N SITU RESULTS 12/8/76 9/20/77 . 10/25/77 12/2/77 o 6/1/78 11/16/78 6/1 5/79 8/7/79 x 9/26/77 ~ __ 15 lo-12 COMPARISON BETWEEN BALLCON-BORNE IN SITU AND mm-WAVE EMISS!ON RESULTS O O OXe ~ _ x~ ~ O eK Oe ~ 0 - O_ _ x. 0. .-{ ~ - . . 0. 0 ~ P. o . 3e "* 0 ~ . ' O ~ ~ ~ ao ~ ~ ~ . . ~0 0 x - 0 0 ~ 0 0 ~0 OD ~ X.O x ~ I t mm WAVE EM I SS ION | | DATA ~ .... 10 9 [C{O]/[M] .d 109 FIGURE D.2 Comparison between balloon-borne in situ and mm-wave emission observations of C10 (from Weinstock et al. 1981, Waters et al. 1981).

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211 It also should be pointed out that while the envelope of C10 data appears to be rather well defined, the dispersion about the mean exceeds +50 percent; the cited experimental uncertainty is +30 percent. As we will see, when the results are applied to the problem of constraining model-predicted ozone reduction, this dispersion constitutes a serious impediment. In anticipation of that fact, we represent the nine in situ ~_..~l ;~r`e Atom =;~rllr" n ~ in ~ ~m~wh~t different V~JO=L VCI ~=v11= ~ ~ Call ~ _~ ~ ~ ~ way. Figure D.3 displays a composite ot the data converted to absolute concentration to eliminate the steep gradient, and in each frame a single profile is highlighted against the background array. The variety in profile shape is significant, with clear evidence of vertical structure on the order of 2 km in some cases, but nearly absent in others. In addition, the top-side shape of [C10] exhibits significant variation. We summarize next the results recently reported by Parrish et al. (1981) using the ground-based, mm-wave emission technique noted earlier (method 2), which were obtained between 10 a.m. and 4 p.m. on 17 separate days (between January 10, 1980, and February 18, 1980) at 43N latitude from the Five College Radio Astronomy Observatory, Amherst, Massachusetts. Such ground-based observations, which employ purely rotational transitions, are affected by collisional (pressure) broadening by approximately 4 MHz/mb at stratospheric pressures. This is both a blessing, in that low-resolution altitude information can be extracted from the emission line shape, and a curse, in that one must have a first-order estimate of the shape of the emitting layer in order to obtain the absolute column concentration for the observed brightness temperature as a function of frequency. In practice, however, the balloon-borne observations have provided the information on the layer shape, and thus absolute column measurements can be extracted. It should be noted, however, that even without knowledge of the shape of the emitting layer, some information on absolute concentration can be extracted. Parrish et al. (1981) have taken the mean of seven in situ profiles, specifically those appearing in the enve- lope of Figure D.2, excluding the last profile obtained on September 26, 1979, and the June 1, 1978, data (which do not alter the conclusions to be drawn), scaled those results by 0.8, integrated the signal that would have resulted, and then overlayed that profile with the observed brightness as a function of frequency. The

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212 50r 451 r ~ 40 . . 35 3C 2C 50r 45 . . ~ 40 . . ILI 35 30 25 20 JVI 451 . . ~ 40 . . ~ 35 J ~ 30 . T __ . i , ~, . ~ , . ; CtO IN ' ilTU DATA 1 i --12/8/76 _: ~ ~ ~ X 2 . . ~ : : I . _ ~. ' -i ,I ~, .. .... __ _ . __ i 1 . ~ . . .. CtO IN SITU DATA , I ~ i, 9/20/77 --i ~ I ~ 1 ' ~ I ' ~ . :. . . . ... ... .... :. .~ .. , _ . .. CtO IN SITU DATA 10/25/77 . . . . . . . . ! _' : ; ; o ~ : :~: ... . - , - .. ~ . - , to !X _ ' ~ +*O O : X ., I :oj~' o to. eX, x lo8 FIGURE D.3a Composite of the C10 profiles 12/8/76, 9/20/77, and 10/25/77.

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213 50 : 45 ,_ ~ 40 ~_ LIJ 35 30 2C 40 ~U 45 40 ~_ 35 30 ~ I I I i ~'~ ~ CtO IN SITU DATA - 12/2/77--- I I ~ 'I I, I I ~ ' ~x I 1 ~:.1 i 1 1 ........ __ _ :_ ' , ! . 1 CtO IN SITU DATA . 6/1i78 . 1, 1 1' i ... .... . . . CtO IN SITU DATA 11/16/7E 25 2C 107 : : . .* o ;ao X, .. . . . . . -,- e. ~ ~ ~ ~ : ~ i 0 ' ~ o ' ~ ~x ; ~0 ~ ~ O' - ox . ~. . . , . ~ . . ., . ~. : ~ : ~ ~ V Xi f ! o o. ~ ,.0 ~ ~' ~' ~ ~ 4 ~ , t4~., V ,6 q o , X ~ , .0,; ~: ., ,' .o o- K ~ : ; : : 0 a ~x c. ~ , ; O K e~ ~ ~; [ClO] _ _ lo8 FIGURE D.3b Composite of the C10 profiles, 12/2/77, 6/1/78, and 11/16/78.

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214 50r ~ , ~ , ~ 45t 2C- 45t ._ ~ 4C ~_ llJ Z) 3~ 3C 25 . . . .. ... _ . . . . . . . . . CtO IN SITU DATA 6/15/79 _ , V~ ~ ~ ~ , ~ . 40 .... _ ~ ~x . ~ -- I~0 ~X ex 35 ~__ - '_'3- ~ ~ -- 30 ~. .o. 1, _. . .:. .-..\ D i !X ~ , .e ,, 25 cF :~ ~_ee . ~ , ~ ', , ''''',' , ' ~ ' ', ' ~'j '' ', , 50 ~j j 1 . ;; , : .. 1 . __ _ ___,. . . . . . . : CtO IN SITU DATA 8/7/79 - - - - - - _ ~. , o . ,x ,. , I , ~io~a O eX . . . . . . . . ! 1 1 ~ 0 o, ex, ___ ~ e* :~ x ,' .: I ~o ~ i '1ai, ~, : l _ __ ,! , ~g ... _ ~D ~ ~ O ---- - - -# ~- - ,~ 1 ~, l, I '' '1 ' ~ 20 ~! ! . : : : 50 j ~, : .. . . . _ ,, .: .. . .. : , .CtO IN SITU DATA 9/26/79 1 ~ , : . . . . . . . . I ,- ; j 45 _.. 1 . -4 I ~ 3C . , oi d . _ _ ~ 1 ~ I O ' ., I t. ~X, I . . - _~- ''' ' ' '' ' . v i c' ~ ,~, &,o Do.~ ,~;;~ ,e, 25 _ . ~_ *~ ~ , ._ _ . .. . , . , . , . ~. , , ., I : ~ 20 107 [CdO] FIGURE D.3c Composite of the C10 profiles, 6/15/79, 8/7/79, and 9/26/79.

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215 results are shown in Figure D.4. The first conclusion to be drawn is that substantial agreement exists with respect to absolute magnitude, since both techniques quote uncertainties of greater than or equal to 25 percent. However, it must be noted that the ground-based observa- tions were done at a latitude 10 northward of the balloon m-~,rements , and are confined to a relatively short I l e ~ ~ ~ ~ ~ a ~ ~ ~ period of time in midwinter. A broader data base and observations done in the same latitude band are clearly needed. Parrish et al. (1981) report that no single day of observation exceeded the average by more than a factor of 2.5, and tentative evidence for variations on the order of a factor of 2 in total C1O column density occurred on a time scale of a few days. An inspection of Figure D.4 indicates a point of major importance: The mm-wave, emission line shape is consistent with the distribution determined by both balloon-borne techniques. The ability of the ground-based observations to discriminate among the available model calculations is demonstrated in the three panels of Figure D.5. These figures compare the line shape that would be observed for three modeled cases: Case (a) with a mixing ratio of 2.7 ppb for total chlorine, a chemical reaction scheme comparable to that used for the previous NRC report, and an elevated stratospheric water vapor mixing ratio of 8 ppm (uniform from troposphere to stratosphere, as discussed in Logan et al. (1978)); Case (b) with 2.6 ppb for total chlorine and a "normal" mixing ratio for H2O of ~ ppm (see Sze and Ko 1981); and, finally, Case (c) with 1.3 ppb for total chlorine and 5 ppm H2O (see Crutzen et al. 1978). The point is not that those ground-based observations cast new light on the selection of a preferred combination of total chlorine and water; the determination of total chlorine (Berg et al. 1980) and H2O (see Kley et al. 1980) had established that point. Rather, the line shape resulting from the calculated distribution of C1O using chemistry consistent with the previous NRC report (Case a) is distinctly broader than that observed by the mm-wave method. This reflects the larger concentration of C1O calculated by the model at lower altitudes in the stratosphere. A reasonably thorough discussion of the experimental uncertainties associated with each of the methods discussed above appears in Chapter 1 of Hudson et al. (1982).

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216 30 An ~20 LL on 1 0 LLJ an I Y O O a: ~ -10 - 1\ 1 1 1 1 1 1 1 1 1 -80 0 1 1 1 80 FREQUENCY AROUND 204.352 MHz FIGURE D.4 An overlay of the ground-based mm-wave emission data of Parrish et al. (1981) and the signal that would result from an integral of the mean of the balloon- borne in situ observations multiplied by 0.8. The mean was taken excluding the July 28, 1976, and July 14, 1977, in situ C1O profiles. C"* a 40 30 hi ~20 a: C3 > ye 10 m O O _O 40 . an :10 1 1 1 1 1 1 1 1 1 1 1 1 o Case b ~ ~ O 1 1 1 1 1 1 1 1 1 1 1 1 lo Case c 30 20 0 _ 1 1 1 1 1 1 1 1 1 1 1 1 -80 0 80 -80 0 80 -80 0 80 FREQUENCY AROUND 204.352 MHz FIGURE D.S A comparison between the ground-based mm-wave emission data of Parrish et al. (1981) and three modeled predictions: Case a from Logan et al. (1978) with 8 ppm H2 O throughout the stratosphere; Case b with 5 ppm H2 O and 2.3 ppb total chlorine from Sze and Ko (1981~; and Case c for 5 ppm H2O and 1.3 ppb total chlorine from Crutzen et al. (1978~. .,

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295 The absence of published high-resolution data of the solar flux as a function of altitude, solar zenith angle, and wavelength is a shortcoming of major importance. Without those direct measurements, the loss rate of the critical "source" terms (e.g., CFC13, CF2C12, and CH3C1) cannot be checked. PROSPECTS: Within the next year, publication of the first high-resolution data on the penetration or solar flux in the 180- to 240-nm spectral interval should begin to eliminate a serious shortcoming on the question. If this does not clear up discrepancies in the loss rates of, for example, CFC13, then it may be necessary to consider the difficult observations of dissociation rates directly measured in situ. A discussion of the discrepancies between observed and calculated source molecules (CH4, N2O, CH3C1, CFC13, ethane) appears in Appendix C. QUESTION 7: What is the vertical distribution of C1O, NO, NOD, OH, and HO' between 15 and 45 km in the equatorial latitudes? Far too much emphasis has been placed on the analysis of mid-latitude data as a result of the concentration of experimental results on this region. However, the domi- nant region of global ozone production exists at latitudes below 30N, and it is of first-order importance to discover whether [C1O], for example, exhibits the behavior characterized by a rapid decrease below 30 km as it does at 32N. There are comparably important examples in the HOk and NC2 systems. PROSPECTS: Within two years, the new generation of tech- niques previously discussed should have provided the first high-quality soundings of these key radicals, hopefully with simultaneous observation of H2O and O3 with the OH and HO2 experiments. It will require, perhaps, another two years to establish with considerable confi- dence the mean distribution of those radicals, but the large observed fluctuations in H2O above the tropopause may yield valuable insight into the chemical linking between the NOk, HOk, and ClOk families by studying the covariance between these radicals. Simultaneous in situ observations of ozone may yield exceedingly impor- tant insight into the odd oxygen budget from the same series of observations.

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296 QUESTION 8: What is the altitude distribution of the important intermediates, HOC1, ClONOo, HO2N22, Nit, Nigh, and MONO' in the stratosphere? The reasons that these products of radical-radical recombination reactions are important are discussed throughout this report and need not be repeated. They present a particularly difficult analytical problem, however, because they are in general large polyatomic molecules that do not possess strong electronic transi- tions, yet their predicted concentrations fall below the detection threshold of long-path IR absorption techniques. PROSPECTS: The first three molecules in this group constitute an exceedingly difficult triplet from the point of view of analytical techniques that can be applied to the stratosphere. Initial detection of ClONO2 has been reported, but the detection is marginally possible with the best IR methods available, and no method has reported observation of HOC1 and HO2NO2. Significant difficulties are predicted for progress on these molecules, but the options have not been exhausted. Double photon ionization methods and fragment fluorescence may be applicable, although the ubiquitous nature of the hydrogen, nitrogen, and oxygen fragments in pernitric acid will make such measurements difficult to interpret. Initial measurements of NC3 at night are encouraging. Attempts to detect N2O5 by thermal dissociation followed by detection of the NOk products formed have been made in the laboratory, but have not shown sufficient promise to warrant stratospheric application. It would, in addition, be exceedingly important if an unambiguous technique for detecting HONC2 in situ could be developed. This would contribute significantly to the question of the NO2, HONO2, OH chemistry of the lower stratosphere. QUESTION 9: What is the concentration of NC', NO, C10, OH and OF simultaneously determined in an air mass characterized by the very low NC: concentration observed by Noxon northward of the high-latitude ledge features, described in Figure D.34? The apparent intrusion of polar air to northern mid-latitudes in the spring represents the opportunity to test in an interesting way the nitrogen, hydrogen, and chlorine chemistry of the stratosphere.

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297 PROSPECTS: The analytical techniques will be available within two years to explore in situ and simultaneously the concentration of NO, NO2, C10, OH, HO2, and O3 in the vicinity of the NO2 "ledge" reported by Noxon, based on ground-based observations of nitrogen dioxide. A detailed understanding of the free radical concentra- tion in such an event would be an exceedingly interesting perturbation experiment. QUESTION 10: Is water vapor the constituent responsible for inducing the variability in free radical concentra- tions evident in virtually all the results reported in this paper? Given the extreme sensitivity of [H2O] to the tropopause temperature and the large observed fluctua- tions of water above the tropical tropopause, it seems plausible that fluctuations in H2O, which in turn cause fluctuations in OH and HO2, constitute a starting point for observed local changes in NO, NO2, and C10. The mechanistic links are discussed both here and in Appendix C. PROSPECTS: As the signal-to-noise ratio, absolute call bration, altitude resolution, and capability to make a large number of simultaneous observations improve in the next three to four years, a wealth of information about how fluctuations in local water vapor concentrations affect the HOx, NOx, and C10x chemistry of the stratosphere will evolve. Thus correlation experiments may best be carried out in the equatorial region, where fluctuations in H2O may be the most dramatic. If local variability reported from aircraft observations well above the tropopause hold at higher altitudes, an entirely new class of correlation experiments will evolve. Such measurements hold great promise for establishing cause-and-effect links within the complex net of reactions linking the various families through radical-radical reactions. QUESTION 11: Does the odd oxygen production/destruction budget balance, based on observed concentrations of the rate limiting free radicals? Although transport times in the odd oxygen continuity equation obviate the possibility of applying a purely chemical test to the balance of local odd oxygen produc

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298 . . . tion and destruction in the lower stratosphere, it is essential that we continue to press the issue of improved analytical techniques for NO2, HO2, C1O, O(3P), and Or to Quantify, as a function of altitude and latitude, the balance between production and destruction of odd oxygen. Although this approach cannot directly test cause-and-effect relationships with the odd oxygen budget and the approach is currently seriously diluted by large experimental uncertainties, it must be carefully pursued. PROSPECTS: The next two years will bring considerably . more accurate detection techniques for the major rate limiting radicals, NO2, C1O, HO2, OH, O(3P), and O3 with cross-calibration against remote techniques and limited latitude coverage. Although such techniques can never prove completeness in our definition of ozone production and loss processes, the detailed accounting will provide important evidence suggesting the altitude dependence of proposed mechanisms. REFERENCES Ackerman, M. and C. Muller (1973) Stratospheric methane and nitrogen dioxide from infrared spectra. Pure and Applied Geophysics 106-108:1325-1335. Ackerman, M., J.C. Fontanella, Do Frimout, A. Girard, N. Louisnard, and C. Muller (197S) Simultaneous measurements of NO and NO2 in the stratosphere. Planetary and Space Science 23:651-660. Aiken, A.C. and E.J.R. Mater (1978) Balloon-borne photo- ionization mass spectrometer for measurement of strato- spheric gases. Review of Scientific Instruments 49:1034-1040. Anderson, J.G. (1971) Rocket measurement of OH in the mesosphere. Journal of Geophysical Research 76:7820. Anderson, J.G. (1975) Measurement of atomic oxygen and hydroxyl in the stratosphere. Pages 458-464, Proceedings, Fourth Conference on CIAP. Symposium No. 17S. Washington, D.C.: U.S. Department of Transportation. Anderson, J.G. (1980) Free radicals in the earth's stratosphere: A review of recent results. Pages 233-251, Proceedings of the NATO Advanced Study Institute on Atmospheric Ozone: Its Variation and Human Influences, edited by A.C. 1979. U.S. Department of Transportation, Aiken. October 1-13, ~ Renort No.

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299 FAA-EE-80-20. Washington, D.C.: Federal Aviation Administration. Anderson, J.G., J.J. Margitan, and D.H. Steoman (1977) Atomic chlorine and the chlorine monoxide free radical in the stratosphere: Three in situ observations. Science 198:501. Anderson, J.G., R.E. Shetter, H.J. Grassel, and J.J. Margitan (1980) Stratospheric free chlorine measured by balloon-borne in situ resonance fluorescence. Journal of Geophysical Research 85:2869. Arnold, F., R. Fabian, G. Henschen, and W. Joos (1980) Stratospheric trace gas analysis from ions: H2O and HNO3. Planetary and Space Science 28:581-585. Bangham, M.J., A. Bonetti, R.H. Bradsell, B. Carli, J.G. Harries, F. Mencaraglia, D.G. Moss, J. Pollitt, E. Rossi, and N.R. Swann (1980) New measurements of stratospheric composition using submillimeter and infrared emission spectroscopy. (Unpublished manuscript available from A. Bonetti, University of Florence, Florence, Italy.) Berg, W.W., P.J. Crutzen, F.E. Grabek, and S.N. Gitlin (1980) First measurements of total chlorine and bromine in the lower stratosphere. Geophysical Research Letters 7:937-940. Blatherwick, R.D., A. Goldman, D.G. Murcray, F.J. Murcray, G.R. Cook, and J.W. Van Allen (1980) Simultaneous mixing ratio profiles of stratospheric NO and NO2 a s derived from balloon-borne infrared solar spectra. Geophysical Research Letters 7:471-473. Buijs, H.L., G.L. Vail, G. Tremblay, and D.J.W. Kendall (1980) Simultaneous measurements of the volume mixing ratio of HF and HC1 in the stratosphere. Geophysical Research Letters 7:205. Burnett, C.R. (1976) Terrestrial OH abundance measurement by spectroscopic observation of resonance absorption by sunlight. Geophysical Research Letters 3:319. Burnett, C.R. (1977) Spectroscopic measurements of atmo spheric OH abundance. Bulletin of the Amer~can Physical Society 22:539. Burnett, C.R. and E.B. Burnett (1981) Spectroscopic measurements of the vertical column abundance of hydroxyl [OH] in the earth's atmosphere. Journal of Geophysical Research 86:5185. Campbell, M.J., J.C. Sheppard, and B.J. An (1979) Measurement of hydroxyl concentration in boundary layer air by monitoring CO oxidation. Geophysical Research Letters 6:175.

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