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Hintsa, Eric J.

Publications and source records attributed to Hintsa, Eric J..

Constraining Remote Oxidation Capacity with ATom Observations

The global oxidation capacity, defined as the tropospheric mean concentration of the hydroxyl radical (OH), controls the lifetime of reactive trace gases in the atmosphere such as methane and carbon monoxide (CO). Models tend to underestimate the methane lifetime and CO concentrations throughout the troposphere, which is consistent with excessive OH. Approximately half the oxidation of methane and non-methane volatile organic compounds (VOCs) is thought to occur over the oceans where oxidant chemistry has received little validation due to a lack of observational constraints. We use observations from the first two deployments of the NASA ATom aircraft campaign during July–August 2016 and January–February 2017 to evaluate the oxidation capacity over the remote oceans and its representation in the GEOS-Chem chemical transport model. The model successfully simulates the magnitude and vertical profile of remote OH within the measurement uncertainties. Comparisons against the drivers of OH production (water vapor, ozone, and NOy concentrations, ozone photolysis frequencies) also show minimal bias with the exception of wintertime NOy, for which a model overestimate may indicate insufficient wet scavenging and/or missing loss on seasalt aerosol but large uncertainties remain that require further studies of NOy partitioning and removal in the troposphere. During the ATom-1 deployment, OH reactivity (OHR) below 3 km is significantly enhanced, and this is not captured by the sum of its measured components (cOHRobs) or by the model (cOHRmod). This enhancement could suggest missing reactive VOCs but cannot be explained by new estimates of ocean VOC sources and additional modeled reactivity in this region would be difficult to reconcile with the full suite of ATom measurement constraints. The model generally reproduces the magnitude and seasonality of cOHRobs but underestimates the contribution of oxygenated VOC, mainly acetaldehyde, which is severely underestimated throughout the troposphere despite its calculated lifetime of less than a day. Missing model acetaldehyde in previous studies was attributed to measurement uncertainties that have been largely resolved. Observations of peroxyacetic acid (PAA) provide new support for remote levels of acetaldehyde. The underestimate in modeled acetaldehyde and PAA is present throughout the year in both hemispheres and peaks during Northern Hemisphere summer. The addition of ocean VOC sources in the model increases annual surface cOHRmod by 10 % and improves model-measurement agreement for acetaldehyde particularly in winter but cannot resolve the model summertime bias. Doing so would require a 100 Tg yr−1 source of a long-lived unknown precursor throughout the year with significant additional emissions in the Northern Hemisphere summer. Improving the model bias for remote acetaldehyde and PAA is unlikely to fully resolve previously reported model global biases in OH and methane lifetime, suggesting that future work should examine the sources and sinks of OH over land.

Travis, Katherine R.↗

The Viability of Trajectory Analysis for Diagnosing Dynamical and Chemical Influences on Ozone Concentrations in the UTLS

The viability of trajectory analysis for diagnosing the interplay between chemistry and dynamics is investigated by comparing ozone mixing ratios modelled using air-parcel pathways to values observed along flight tracks during ATTREX (Airborne Tropical TRopopause EXperiment). Trajectories are initiated at the locations of ozone observations and tracked backward in time to their sources at termini of backward trajectories. The modelled values of ozone utilize 3-dimensional analysis fields from WACCM (Whole Atmosphere Community Climate Model) (a chemical-climate model with dynamical fields nudged towards MERRA (Modern-Era Retrospective Analysis and Research Applications) reanalysis) and ERA-interim (product of ECMWF - the European Centre for Medium-Range Weather Forecasts) to determine source mixing ratios with chemical production and loss terms derived from the ozone chemistry used in WACCM. A statistical base of modelled ozone is constructed with 6 trajectory platforms (adiabatic, diabatic, and kinematic forced by ERA-interim and MERRA), two chemical models (WACCM chemistry and no chemistry), and 4 trajectory lengths (5, 10, 20, and 30 days). Linear regression is employed to separate systematic errors from random errors and to characterize the impact of source mixing ratios, path length, vertical motion, and chemistry on modelled ozone errors. Errors in the analysis ozone fields are large, if not dominant, contributors to model error. Random errors are particularly large for point-by-point comparisons, however averaging over 800 km (75 minutes) flight segments substantially reduces random error and exposes systematic errors. Of the two analysis ozone data sets, WACCM, which incorporates detailed chemistry, provides the smaller systematic errors while ERA-interim, which has crude chemistry but assimilates observational data, has the smaller random errors. Of the different trajectory platforms, adiabatic calculations produce the smaller random errors (irrespective of the use of chemistry) but both vertical motion and chemistry are required to optimally reduce systematic errors. These results suggest that meaningful analysis of dynamical and chemical interactions that control ozone mixing ratios are viable on spatial scales larger than a few reanalysis grid spaces, that errors in the analyzed ozone data sets are large but not prohibitively so, and that vertical velocities and heating rates from reanalysis data, while problematic, contain useful information [on the ozone concentrations in the UTLS (Upper Troposphere/Lower Stratosphere)].

ozone↗

Physical Processes Controlling the Distribution of Relative Humidity in the Tropical Tropopause Layer over the Pacific

The distribution of relative humidity with respect to ice (RHI) in the Boreal wintertime Tropical Tropopause Layer (TTL - about 14-19 km) over the Pacific is examined with the extensive dataset of measurements from the NASA Airborne Tropical TRopopause EXperiment (ATTREX). Multiple deployments of the Global Hawk during ATTREX provided hundreds of vertical profiles spanning the Pacific with accurate measurements of temperature, pressure, water vapor concentration, ozone concentration, and cloud properties. We also compare the measured RHI distributions with results from a transport and microphysical model driven by meteorological analysis fields. Notable features in the distribution of RHI versus temperature and longitude include (1) the common occurrence of RHI values near ice saturation over the western Pacific in the lower TTL (temperatures greater than 200 K) and in airmasses with low ozone concentrations indicating recent detrainment from deep convection; (2) low RHI values in the lower TTL over the eastern Pacific where deep convection is infrequent; (3) RHI values following a constant H2O mixing ratio in the upper TTL (temperatures below about 195 degrees Kelvin), particularly for samples with ozone mixing ratios greater than about 50-100 parts-per-billion-volume indicating mixtures of tropospheric and stratospheric air, and (4) RHI values typically near ice saturation in the coldest airmasses sampled (temperatures less than about 190 degrees Kelvin). We find that the typically saturated air in the lower TTL over the western Pacific is largely driven by the frequent occurrence of deep convection in this region. The nearly-constant water vapor mixing ratios in the upper TTL result from the combination of slow ascent (resulting in long residence times) and wave-driven temperature variability on a range of time scales (resulting in most air parcels having experienced low temperature and dehydration).

ozone↗

Mechanisms for Midlatitude Ozone Loss: Heterogeneous Chemistry in the Lowermost Stratosphere?

The question of midlatitude ozone erosion by chlorine free radical catalysis is examined. We present and analyze simultaneous, high-resolution observations of ClO, H2O, tropopause height, particle reactive surface area, and ice saturation occurrence frequency obtained from the NASA ER-2 aircraft. The objective is to test the hypothesis that the existence of cirrus clouds or cold aerosols in the first few kilometers above the tropopause at midlatitudes is responsible for increasing the ratio of chlorine free radicals to total inorganic chlorine, thus amplifying the rate of catalytic ozone destruction. The observations reveal a sharp decrease in ice saturation frequency at the tropopause, a marked degree of undersaturation just above the tropopause, a corresponding sharp gradient in the product of cold aerosol reactive surface area and reaction probability, gamma-S(sub a), and, finally, the consistent absence of enhanced concentrations of ClO immediately above the tropopause. These results suggest that midlatitude ozone loss is not controlled in situ by the mechanism of cirrus cloud and/or cold aerosol enhancement of chlorine radicals in the vicinity of the tropopause.

Smith, Jessica B.↗

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 vapor 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 vapor budget, modelling of heterogeneous reaction rates and the results of a general circulation model on the radiative effect of increased water vapor. 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 vapor and hence an increased transport of water vapor from the troposphere to the stratosphere. Stratospheric water vapor 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 vapor 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.

Kirk-Davidoff, Daniel B.↗

On the Accuracy of In Situ Water Vapor Measurements in the Troposphere and Lower Stratosphere with the Harvard Lyman-Alpha 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-alpha 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-alpha 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.

Hintsa, Eric J.↗

SPADE H2O measurements and the seasonal cycle of statospheric water vapor

We present measurements of lower statospheric water vapor obtained during the Stratospheric Phototchemistry, Aerosols and Dynamics Expedition (SPADE) mission with a new high precision, fast response, Lyman-alpha hygrometer. The H2O data show a distinct seasonal cycle. For air that recently entered the statosphere, data collected during the fall show much more water vapor than data from the spring. Fast quasi-horizontal mixing causes compact relationships between water and N2O to be established on relatively short time scales. The measurements are consistent with horizontal mixing times of a few months or less. Vertical mixing appears to cause the seasonal variations in water vapor to propagate up to levels corresponding to air that has been in the stratosphere approximately one year.

Hintsa, Eric J.↗