Randy D. May

Aircraft (ER-2) laser infrared absorption spectrometer (ALIAS) for in-situ stratospheric measurements of HCl, N 2 O, CH 4 , NO 2 , and HNO 3

The Aircraft Laser Infrared Absorption Spectrometer (ALIAS) instrument is a high-resolution (0.0003 cm-(1)) scanning tunable-diode-laser spectrometer designed, tested, and flown more than 30 times on the National Aeronautics and Space Administrations high-altitude ER-2 aircraft in the Airborne Arctic Stratospheric Expedition of 1991-1992. Using long-path infrared laser absorption spectroscopy to detect optical absorptions as small as 10-(5), ALIAS provides fast, continuous in-situ measurements of key atmospheric gases, with gas detection sensitivities of tens of parts in 10(12). With four lasers and detectors in a single liquid-nitrogen Dewar, simultaneous measurements of HCI, NO(2), HNO(3), CH(4), and N(2)O are made using laser sources at 3.4-8 µm, injected into a 1-m-long, 80-pass Herriott cell.

Open-path, near-infrared tunable diode laser spectrometer for atmospheric measurements of H2O

A new instrument for in situ measurements of atmospheric water vapor from aircraft platforms has been developed based upon near-infrared turnable diode laser sources operating near 1.37 μm. The spectrometer features a unique open-path, multipass (Herriott) cell for true in situ monitoring of water vapor concentrations with precision levels exceeding those of existing Lyman α and frost point hygrometers. External sampling outside of the aircraft boundary layer minimizes ambiguities in the measured water vapor abundances. Variable spectrum acquisition rates up to 10 Hz provide fast temporal resolution free from sampling or flow rate limitations. In its current configuration the instrument operates from the right wing pod of the NASA ER-2 research aircraft and is optimized for measurements in the upper troposphere and stratosphere (to 20 km). Measurement precision is ±0.05 ppmv in the stratosphere for a 2-s measurement integration period. The flight-ready instrument weight is 8.2 kg, and power consumption, exclusive of structural heaters, is 7.5 W.

Chlorine chemistry on polar stratospheric cloud particles in the Arctic winter

Simultaneous in situ measurements of hydrochloric acid (HCl) and chlorine monoxide (ClO) in the Arctic winter vortex showed large HCl losses, of up to 1 part per billion by volume (ppbv), which were correlated with high ClO levels of up to 1.4 ppbv. Air parcel trajectory analysis identified that this conversion of inorganic chlorine occurred at air temperatures of less than 196 � 4 kelvin. High ClO was always accompanied by loss of HCI mixing ratios equal to �(ClO + 2Cl2O2). These data indicate that the heterogeneous reaction HCl + ClONO2 → Cl2 + HNO3 on particles of polar stratospheric clouds establishes the chlorine partitioning, which, contrary to earlier notions, begins with an excess of ClONO2, not HCl.

Comparison of MkIV balloon and ER‐2 aircraft measurements of atmospheric trace gases

On May 8, 1997, vertical profiles of over 30 different gases were measured remotely in solar occultation by the Jet Propulsion Laboratory MkIV Interferometer during a balloon flight launched from Fairbanks, Alaska. These gases included H 2 O, N 2 O, CH 4 , CO, NO x , NO y , HCI, ClNO 3 , CCl 2 F 2 , CCl 3 F, CCl 4 , CHClF 2 , CClF 2 CCl 2 F, SF 6 , CH 3 Cl, and C 2 H 6 , all of which were also measured in situ by instruments on board the NASA ER-2 aircraft, which was making flights from Fairbanks during this same early May time period as part of the Photochemistry of Ozone Loss in the Arctic Region in Summer (POLARIS) experiment. A comparison of the gas volume mixing ratios in the upper troposphere and lower stratosphere reveals agreement better than 5% for most gases. The three significant exceptions to this are SF 6 and CCl 4 for which the remote measurements exceed the in situ observations by 15-20% at all altitudes, and H 2 O for which the remote measurements are up to 30% smaller than the in situ observations near the hygropause.

Prevalence of ice-supersaturated regions in the upper troposphere: Implications for optically thin ice cloud formation

In situ measurements of water vapor and temperature from recent aircraft campaigns have provided evidence that the upper troposphere is frequently supersaturated with respect to ice. The peak relative humidities with respect to ice (RHI) occasionally approached water saturation at temperatures ranging from −40°C to −70°C in each of the campaigns. The occurrence frequency of ice supersaturation ranged from about 20% to 45%. Even on flight segments when no ice crystals were detected, ice supersaturation was measured about 5–20% of the time. A numerical cloud model is used to simulate the formation of optically thin, low ice number density cirrus clouds in these supersaturated regions. The potential for scavenging of ice nuclei (IN) by these clouds is evaluated. The simulations suggest that if less than about 5 × 10-3 to 2 × 10-2 cm-3 ice nuclei are present when these supersaturations are generated, then the cirrus formed should be subvisible. These low ice number density clouds scavenge the IN from the supersaturated layer, but the crystals sediment out too rapidly to prevent buildup of high supersaturations. If higher numbers of ice nuclei are present, then the clouds that form are visible and deposition growth of the ice crystals reduces the RHI down to near 100%. Even if no ice clouds form, increasing the RHI from 100% to 150% between 10 and 10.5 km results in a decrease in outgoing longwave radiative flux at the top of the atmosphere of about 8 W m-2. If 0.02–0.1 cm-3 IN are present, the resulting cloud radiative forcing reduces the net radiative flux several watts per square meter further. Given the high frequency of supersaturated regions without optically thick clouds in the upper troposphere, there is a potential for a climatically important class of optically thin cirrus with relatively low ice crystal number densities. The optical properties of these clouds will depend very strongly on the abundance of ice nuclei in the upper troposphere.

On the accuracy of in situ water vapor measurements in the troposphere and lower stratosphere with the Harvard Lyman-α hygrometer

In an effort to better constrain atmospheric water vapor mixing ratios and to understand the discrepancies between different measurements of water vapor in the stratosphere and troposphere, we have carefully examined data from the Harvard Lyman-α photofragment fluorescence hygrometer, which has flown on the NASA ER-2 aircraft from 1992 through 1998. The instrument is calibrated in the laboratory before and after each deployment, and the calibration is checked by direct absorption measurements in the troposphere. On certain flights, the ER-2 flew level tracks during which water vapor varied by up to 80 ppmv, under nearly constant atmospheric conditions; These flights provide a stringent test of our calibration via direct absorption and indicate agreement to within 3%. During the 1997 Photochemistry of Ozone Loss in the Arctic Region In Summer (POLARIS) mission, our Lyman-α instrument was compared with a new diode laser hygrometer from the Jet Propulsion Laboratory. Overall agreement was 5% during the June/July deployment and 1% for potential temperatures of 490 to 540 K. The accuracy of our instrument is shown to be ±5%, with an additional offset of at most 0.1 ppmv. Data from this instrument, combined with simultaneous measurements of CH4 and H2, are therefore ideal for studies of the hydrogen budget of the lower stratosphere.

An examination of chemistry and transport processes in the tropical lower stratosphere using observations of long‐lived and short‐lived compounds obtained during STRAT and POLARIS

A suite of compounds with a wide range of photochemical lifetimes (3 months to several decades) was measured in the tropical and midlatitude upper troposphere and lower stratosphere during the Stratospheric Tracers of Atmospheric Transport (STRAT) experiment (fall 1995 and winter, summer, and fall 1996) and the Photochemistry of Ozone Loss in the Arctic Region in Summer (POLARIS) deployment in late summer 1997. These species include various chlorofluorocarbons, hydrocarbons, halocarbons, and halons measured in whole air samples and CO measured in situ by tunable diode laser spectroscopy. Mixing ratio profiles of long-lived species in the tropical lower stratosphere are examined using a one-dimensional (1-D) photochemical model that includes entrainment from the extratropical stratosphere and is constrained by measured concentrations of OH. Profiles of tracers found using the 1-D model agree well with all the observed tropical profiles for an entrainment time scale of 8.5 -4 +6 months, independent of altitude between potential temperatures of 370 and 500 K. The tropical profile of CO is used to show that the annually averaged ascent rate profile, on the basis of a set of radiative heating calculations, is accurate to approximately ±44%, a smaller uncertainty than found by considering the uncertainties in the radiative model and its inputs. Tropical profiles of ethane and C 2 Cl 4 reveal that the concentration of Cl is higher than expected on the basis of photochemical model simulations using standard gas phase kinetics and established relationships between total inorganic chlorine and CFC-11. Our observations suggest that short-lived organic chlorinated compounds and HCI carried across the tropical tropopause may provide an important source of inorganic chlorine to the tropical lower stratosphere that has been largely unappreciated in previous studies. The entrainment timescale found here is considerably less than the value found by a similar study that focused on observations obtained in the lower stratosphere during 1994. Several possible explanations for this difference are discussed.

Tropical entrainment time scales inferred from stratospheric N2O and CH4 observations

Simultaneous in situ measurements of N_2O and CH_4 were made with a tunable diode laser spectrometer (ALIAS II) aboard the Observations from the Middle Stratosphere (OMS) balloon platform from New Mexico, Alaska, and Brazil during 1996 and 1997. We find different compact relationships of CH_4 with N_2O in the tropics and extra-tropics because mixing is slow between these regions. Transport into the extra-tropics from the tropics or the polar vortex leads to deviations from the normal compact relationship. We use measured N_2O and CH_4 and a simple model to quantify entrainment of mid-latitude stratospheric air into the tropics. The entrainment time scale is estimated to be 16 (+17, −8) months for altitudes between 20 and 28 km. The fraction of tropical air entrained from the extra-tropical stratosphere is 50% (+18%, −30%) at 20 km, increasing to 78% (+11%, −19%) at 28 km.

AIRBORNE LASER INFRARED ABSORPTION SPECTROMETER (ALIAS-II) FOR IN SITU ATMOSPHERIC MEASUREMENTS OF N2O, CH4, CO, HCL, AND NO2 FROM BALLOON OR REMOTELY PILOTED AIRCRAFT PLATFORMS

The Airborne Laser Infrared Absorption Spectrometer II (ALIAS-II) is a lightweight, high-resolution (0.0003-cm(-1)), scanning, mid-infrared absorption spectrometer based on cooled (80 K) lead-salt tunable diode laser sources. It is designed to make in situ measurements in the lower and middle stratosphere on either a balloon platform or high-altitude remotely piloted aircraft. Chemical species that can be measured precisely include long-lived tracers N(2)O and CH(4), the shorter-lived tracer CO, and chemically active species HCl and NO(2). Advances in electronic instrumentation developed for ALIAS-I, with the experience of more than 250 flights on board NASAs ER-2 aircraft, have been implemented in ALIAS-II. The two-channel spectrometer features an open cradle, multipass absorption cell to ensure minimal contamination from inlet and surfaces. Time resolution of the instrument is <or=3 s, allowing rapid in situ measurements with excellent spatial resolution. ALIAS-II has completed successful balloon flights from New Mexico, Alaska, and Brazil providing CH(4) and N(2)O vertical profiles in the tropics, mid-latitudes, and high northern latitudes up to altitudes of 32 km.

Data processing and calibration for tunable diode laser harmonic absorption spectrometers

Data processing and calibration methods are described for tunable diode laser absorption spectrometers which produce harmonic absorption spectra as raw data for measuring gas mixing ratios down to parts-per-trillion levels at a variety of pressures. The methods, which take advantage of modern computer speed, memory, and data storage capabilities, are applicable to the detection of weakly absorbing gases in quantitative industrial monitoring, in addition to aircraft and balloon atmospheric measurements for which they were designed. Algorithms for calibration and data analysis, including rejection of erroneous spectra, variation of effective integration time, spectral alignment prior to averaging, and plotting and archiving of results, have been tested on actual stratospheric laser spectra recorded by the Aircraft Laser Infrared Absorption Spectrometer (ALIAS) spectrometer in numerous flights of NASAs ER-2 aircraft.