E. J. Hintsa

Environmental turbulent mixing controls on air-water gas exchange in marine and aquatic systems

[1] Air-water gas transfer influences CO 2 and other climatically important trace gas fluxes on regional and global scales, yet the magnitude of the transfer is not well known. Widely used models of gas exchange rates are based on empirical relationships linked to wind speed, even though physical processes other than wind are known to play important roles. Here the first field investigations are described supporting a new mechanistic model based on surface water turbulence that predicts gas exchange for a range of aquatic and marine processes. Findings indicate that the gas transfer rate varies linearly with the turbulent dissipation rate to the 1/4 power in a range of systems with different types of forcing - in the coastal ocean, in a macro-tidal river estuary, in a large tidal freshwater river, and in a model (i.e., artificial) ocean. These results have important implications for understanding carbon cycling.

The effect of climate change on ozone depletion through changes in stratospheric water vapour

Several studies have predicted substantial increases in Arctic ozone depletion due to the stratospheric cooling induced by increasing atmospheric CO2 concentrations. But climate change may additionally influence Arctic ozone depletion through changes in the water vapour cycle. Here we investigate this possibility by combining predictions of tropical tropopause temperatures from a general circulation model with results from a one-dimensional radiative convective model, recent progress in understanding the stratospheric water vapour budget, modelling of heterogeneous reaction rates and the results of a general circulation model on the radiative effect of increased water vapour. Whereas most of the stratosphere will cool as greenhouse-gas concentrations increase, the tropical tropopause may become warmer, resulting in an increase of the mean saturation mixing ratio of water vapour and hence an increased transport of water vapour from the troposphere to the stratosphere. Stratospheric water vapour concentration in the polar regions determines both the critical temperature below which heterogeneous reactions on cold aerosols become important (the mechanism driving enhanced ozone depletion) and the temperature of the Arctic vortex itself. Our results indicate that ozone loss in the later winter and spring Arctic vortex depends critically on water vapour variations which are forced by sea surface temperature changes in the tropics. This potentially important effect has not been taken into account in previous scenarios of Arctic ozone loss under climate change conditions.

Observed OH and HO2 in the upper troposphere suggest a major source from convective injection of peroxides

ER-2 aircraft observations of OH and HO_2 concentrations in the upper troposphere during the NASA/STRAT campaign are interpreted using a photochemical model constrained by local observations of O_3, H_2O, NO, CO, hydrocarbons, albedo and overhead ozone column. We find that the reaction Q(^(1)D) + H_2O is minor compared to acetone photolysis as a primary source of HO_x (= OH + peroxy radicals) in the upper troposphere. Calculations using a diel steady state model agree with observed HO_x concentrations in the lower stratosphere and, for some flights, in the upper troposphere. However, for other flights in the upper troposphere, the steady state model underestimates observations by a factor of 2 or more. These model underestimates are found to be related to a recent (< 1 week) convective origin of the air. By conducting time-dependent model calculations along air trajectories determined for the STRAT flights, we show that convective injection of CH_3OOH and H_2O_2 from the boundary layer to the upper troposphere could resolve the discrepancy. These injections of HO_x reservoirs cause large HO_x increases in the tropical upper troposphere for over a week downwind of the convective activity. We propose that this mechanism provides a major source of HO_x in the upper troposphere. Simultaneous measurements of peroxides, formaldehyde and acetone along with OH and HO_2 are needed to test our hypothesis.

Aircraft observations of thin cirrus clouds near the tropical tropopause

This work describes aircraft-based lidar observations of thin cirrus clouds at the tropical tropopause in the central Pacific obtained during the Tropical Ozone Transport Experiment/Vortex Ozone Transport Experiment (TOTE/VOTE) in December 1995 and February 1996. Thin cirrus clouds were found at the tropopause on each of the four flights which penetrated within 15° of the equator at 200–210 east longitude. South of 15°N, thin cirrus were detected above the aircraft about 65% of the time that data were available. The altitudes of these clouds exceeded 18 km at times. The cirrus observations could be divided into two basic types: thin quasi-laminar wisps and thicker, more textured structures. On the basis of trajectory analyses and temperature histories, these two types were usually formed respectively by (1) in situ cooling on both a synoptic scale and mesoscale and (2) recent (a few days) outflow from convection. There is evidence from one case that the thicker clouds can also be formed by in situ cooling. The actual presence or absence of thin cirrus clouds was also consistent with the temperature and convective histories derived from back trajectory calculations. Notably, at any given time, only a relatively small portion (at most 25%) of the west central tropical Pacific has been influenced by convection within the previous 10 days. The structures of some of the thin cirrus clouds formed in situ strongly resembled long-wavelength (500–1000 km) gravity waves observed nearly simultaneously by the ER-2 on one of the flights. Comparison with in situ water vapor profiles made by the NASA ER-2 aircraft provide some observational support for the hypothesis that thin cirrus clouds play an important role in dehydrating tropospheric air as it enters the stratosphere.

New fast response photofragment fluorescence hygrometer for use on the NASA ER‐2 and the Perseus remotely piloted aircraft

We have developed an in situ instrument to measure water vapor on the NASA ER‐2 as a prototype for use on the Perseus remotely piloted aircraft. It utilizes photofragment fluorescence throughout the stratosphere and the upper to middle troposphere (mixing ratios from 2 to 300 ppmv) with simultaneous absorption measurements in the middle troposphere (water vapor concentrations ≳5×1014 mol/cc). The instrument flew successfully on the NASA ER‐2 aircraft during the 1993 CEPEX and SPADE campaigns. The 2σ measurement precision for a 10 s integration time, limited by variation in the background from scattered solar radiation, is ±6% and the data were tightly correlated with other long‐lived stratospheric tracers throughout the SPADE mission. Its accuracy is estimated to be ±10%, based on laboratory calibrations using a range of water vapor concentrations independently determined by both standard gas addition techniques and by absorption. This accuracy is confirmed by in‐flight absorption measurements in the trop...

Mechanisms controlling water vapor in the lower stratosphere: “A tale of two stratospheres”

We present an analysis of the mechanisms controlling stratospheric water vapor based on in situ profiles made at 37.4°N and at altitudes up to 20 km. The stratosphere can be conveniently divided into two air masses : the overworld (potential temperature θ>380 K) and the lowermost stratosphere (θ<380). Our data support the canonical theory that air primarily enters the overworld by passing through the tropical tropopause. The low water vapor mixing ratios in the overworld, a few parts per million by volume (ppmv), are determined by the low temperatures encountered at the tropical tropopause, as well as oxidation of methane and molecular hydrogen. Air enters the lowermost stratosphere both by diabatically descending from the overworld across the 380-K potential temperature surface and by passing through the extratropical tropopause. Air parcels crossing the extratropical tropopause experience higher temperatures than air crossing the tropical tropopause, allowing higher water vapor in the lowermost stratosphere (tens of ppmv) than in the overworld. Our data are consistent with the pathway for air crossing the extratropical tropopause being isentropic advection from lower latitudes, although we cannot exclude contributions from other paths.

Empirical age spectra for the lower tropical stratosphere from in situ observations of CO2: Implications for stratospheric transport

Empirical age spectra for the lower tropical stratosphere (from the tropopause to ∼19.5 km) have been derived from in situ measurements of CO 2 , using information provided by the vertical propagation of the tropospheric seasonal cycle and long-term positive trend. Our method provides accurate and unambiguous mean ages for this region which are difficult to obtain by simple analysis of lag times from tracer measurements. We find that the air is 30-40% younger in northern spring than in autumn. For example, at 460 K the mean age (relative to the tropical tropopause) was 0.4 years in March and 0.6 years in September. The phase lag times and attenuation of CO 2 seasonal extrema in the stratosphere are shown to depend on seasonal variations in transport rates and on the presence of harmonics in the CO 2 boundary condition with frequencies higher than 2π/yr. Profiles of stratospheric water vapor, generated from the derived age spectra with a stratospheric boundary condition based on observed tropical tropopause temperatures, are consistent with in situ observations of H 2 O. Comparison of the predicted water vapor seasonal cycle with satellite observations suggests that satellite-borne instruments underestimate the amplitude near the tropical tropopause. We relate the empirical age spectra to the analytic solution for the 1-D advection-diffusion tracer continuity equation to obtain seasonally resolved estimates of the ascent rate and the vertical diffusion coefficient. The derived age spectra provide a unique observation-based diagnostic for evaluating the simulation of tracer transport in models.

In situ observations in aircraft exhaust plumes in the lower stratosphere at midlatitudes

Instrumentation on the NASA ER-2 high-altitude aircraft has been used to observe engine exhaust from the same aircraft while operating in the lower stratosphere. Encounters with the exhaust plume occurred approximately 10 min after emission with spatial scales near 2 km and durations of up to 10 s. Measurements include total reactive nitrogen, NO(y), the component species NO and NO2, CO2, H2O, CO, N2O, condensation nuclei, and meteorological parameters. The integrated amounts of CO2 and H2O during the encounters are consistent with the stoichiometry of fuel combustion (1:1 molar). Emission indices (EI) for NO(x) (= NO + NO2), CO, and N2O are calculated using simultaneous measurements of CO2. EI values for NO(x) near 4 g/(kg fuel) are in good agreement with values scaled from limited ground-based tests of the ER-2 engine. Non-NO(x) species comprise less than about 20% of emitted reactive nitrogen, consistent with model evaluations. In addition to demonstrating the feasibility of aircraft plume detection, these results increase confidence in the projection of emissions from current and proposed supersonic aircraft fleets and hence in the assessment of potential long-term changes in the atmosphere.

Troposphere‐to‐stratosphere transport in the lowermost stratosphere from measurements of H2O, CO2, N2O and O3

The origin of air in the lowermost stratosphere is investigated with measurements from the NASA ER-2 aircraft. Air with high water vapor mixing ratios was observed in the stratosphere at θ∼330–380 K near 40 N in May 1995, indicating the influence of intrusions of tropospheric air. Assuming that observed tracer-tracer relationships reflect mixing lines between tropospheric and stratospheric air masses, we calculate mixing ratios of H2O (12–24 ppmv) and CO2 for the admixed tropospheric air at θ=352–364 K. Temperatures on the 355 K surface at 20–40 N were low enough to dehydrate air to these values. While most ER-2 CO2 data in both hemispheres are consistent with tropical or subtropical air entering the lowermost stratosphere, measurements from May 1995 for θ<362 K suggest that entry of air from the midlatitude upper troposphere can occur in conjunction with mixing processes near the tropopause.

An examination of the total hydrogen budget of the lower stratosphere

We analyze the hydrogen budget of the lower stratosphere using simultaneous in situ measurements of northern hemispheric water vapor (H2O) and methane (CH4) obtained during the spring Stratospheric Photochemistry, Aerosols, and Dynamics Expedition (SPADE), as well as previously published in situ H2 data. Based on this data, we conclude that approximately two H2O molecules are produced for each CH4 molecule destroyed. This implies that H2 production from CH4 oxidation is balanced by H2 oxidation. The uncertainty in this analysis is greatly reduced by the use of multiple data sets. Additionally, we infer that, on an annual and global average, H2O enters the stratosphere with a mixing ratio of 4.2±0.5 ppmv, and that the quasi-conserved quantity 2×[CH4] + [H2O] has a value of 7.6±0.6 ppmv in these northern hemisphere air parcels (where [ξ] denotes the mixing ratio of the constituent ξ).