Evolution Of Trace Gases Research Articles

The Influence of Stratospheric Hydration From the Hunga Eruption on Chemical Processing in the 2023 Antarctic Vortex

AbstractWe use measurements of trace gases from the Microwave Limb Sounder and polar stratospheric clouds (PSCs) from the Cloud‐Aerosol Lidar with Orthogonal Polarization to investigate how the extraordinary stratospheric water vapor enhancement from the 2022 Hunga eruption affected polar processing during the 2023 Antarctic winter. Although the dynamical characteristics of the vortex itself were generally unexceptional, the excess moisture initially raised PSC formation threshold temperatures above typical values. Cold conditions, especially in early July, prompted ice PSC formation and unusually severe irreversible dehydration at higher levels (500–700 K), while atypical hydration occurred at lower levels (380–460 K). Heterogeneous chemical processing was more extensive, both vertically (up to 750–800 K) and temporally (earlier in the season), than in prior Antarctic winters. The resultant HCl depletion and ClO enhancement redefined their previously observed ranges at and above 600 K. Albeit unmatched in the satellite record, the early‐winter upper‐level chlorine activation was insufficient to induce substantial ozone loss. Chlorine activation, denitrification, and dehydration processes ran to completion by July/August, with trace gas evolution mostly following the climatological mean thereafter, but with chlorine deactivation starting slightly later than usual. While cumulative ozone losses at 410–550 K were relatively large, probably because of the delayed chlorine deactivation, they were not unprecedented. Thus, ozone depletion was unremarkable throughout the lower stratosphere. Although Hunga enhanced PSC formation and chemical processing in early winter, saturation of lower stratospheric denitrification, dehydration, and chlorine activation (as is typical in the Antarctic) prevented an exceptionally severe ozone hole in 2023.

Evolution of trace gases and particles emitted by a chaparral fire in California

Abstract. Biomass burning (BB) is a major global source of trace gases and particles. Accurately representing the production and evolution of these emissions is an important goal for atmospheric chemical transport models. We measured a suite of gases and aerosols emitted from an 81 hectare prescribed fire in chaparral fuels on the central coast of California, US on 17 November 2009. We also measured physical and chemical changes that occurred in the isolated downwind plume in the first ~4 h after emission. The measurements were carried out onboard a Twin Otter aircraft outfitted with an airborne Fourier transform infrared spectrometer (AFTIR), aerosol mass spectrometer (AMS), single particle soot photometer (SP2), nephelometer, LiCor CO2 analyzer, a chemiluminescence ozone instrument, and a wing-mounted meteorological probe. Our measurements included: CO2; CO; NOx; NH3; non-methane organic compounds; organic aerosol (OA); inorganic aerosol (nitrate, ammonium, sulfate, and chloride); aerosol light scattering; refractory black carbon (rBC); and ambient temperature, relative humidity, barometric pressure, and three-dimensional wind velocity. The molar ratio of excess O3 to excess CO in the plume (ΔO3/ΔCO) increased from −5.13 (±1.13) × 10−3 to 10.2 (±2.16) × 10−2 in ~4.5 h following smoke emission. Excess acetic and formic acid (normalized to excess CO) increased by factors of 1.73 ± 0.43 and 7.34 ± 3.03 (respectively) over the same time since emission. Based on the rapid decay of C2H4 we infer an in-plume average OH concentration of 5.27 (±0.97) × 106 molec cm−3, consistent with previous studies showing elevated OH concentrations in biomass burning plumes. Ammonium, nitrate, and sulfate all increased over the course of 4 h. The observed ammonium increase was a factor of 3.90 ± 2.93 in about 4 h, but accounted for just ~36% of the gaseous ammonia lost on a molar basis. Some of the gas phase NH3 loss may have been due to condensation on, or formation of, particles below the AMS detection range. NOx was converted to PAN and particle nitrate with PAN production being about two times greater than production of observable nitrate in the first ~4 h following emission. The excess aerosol light scattering in the plume (normalized to excess CO2) increased by a factor of 2.50 ± 0.74 over 4 h. The increase in light scattering was similar to that observed in an earlier study of a biomass burning plume in Mexico where significant secondary formation of OA closely tracked the increase in scattering. In the California plume, however, ΔOA/ΔCO2 decreased sharply for the first hour and then increased slowly with a net decrease of ~20% over 4 h. The fraction of thickly coated rBC particles increased up to ~85% over the 4 h aging period. Decreasing OA accompanied by increased scattering/particle coating in initial aging may be due to a combination of particle coagulation and evaporation processes. Recondensation of species initially evaporated from the particles may have contributed to the subsequent slow rise in OA. We compare our results to observations from other plume aging studies and suggest that differences in environmental factors such as smoke concentration, oxidant concentration, actinic flux, and RH contribute significantly to the variation in plume evolution observations.

Trace gas evolution in the lowermost stratosphere from Aura Microwave Limb Sounder measurements

[1] Daily global measurements from NASA's Aura Microwave Limb Sounder (MLS) allow comprehensive investigation of interhemispheric and interannual variations in chemical and transport processes throughout the lowermost stratosphere (LMS). We analyze nearly seven years of MLS O3, HNO3, HCl and ClO measurements along with meteorological analyses to place chemical processing in and dispersal of processed air from the winter polar lowermost vortex and subvortex in a global context. The MLS data, the first simultaneous observations of HCl and ClO covering much of the LMS, reveal that chlorine activation is widespread in the Antarctic subvortex and can occur to a significant degree in the Arctic subvortex. Unusually low temperatures and strong, prolonged chlorine activation in the lowermost vortex and subvortex promoted large ozone losses there in the 2006 (and 2008) Antarctic and 2004/2005 Arctic winters, consistent with reported record low column ozone. Processed air dispersing from the decaying vortex in spring induces rapid changes in extravortex trace gas abundances. After vortex breakdown, the subtropical jet/tropopause becomes the major transport barrier in the LMS. Quasi-isentropic transport of tropical tropospheric air into the LMS, associated with the summer monsoon circulations, leads to decreases in extratropical O3, HNO3, and HCl in both hemispheres. Strong mixing in the summertime LMS homogenizes extratropical trace gas fields. MLS measurements in the tropics show signatures of monsoon-related cross-equatorial stratosphere-to-troposphere transport. Observed seasonal and interannual variations in trace gas abundances in the LMS are consistent with variations in the strength of transport barriers diagnosed from meteorological analyses.

Jet characterization in the upper troposphere/lower stratosphere (UTLS): applications to climatology and transport studies

Abstract. A method of classifying the upper tropospheric/lower stratospheric (UTLS) jets has been developed that allows satellite and aircraft trace gas data and meteorological fields to be efficiently mapped in a jet coordinate view. A detailed characterization of multiple tropopauses accompanies the jet characterization. Jet climatologies show the well-known high altitude subtropical and lower altitude polar jets in the upper troposphere, as well as a pattern of concentric polar and subtropical jets in the Southern Hemisphere, and shifts of the primary jet to high latitudes associated with blocking ridges in Northern Hemisphere winter. The jet-coordinate view segregates air masses differently than the commonly-used equivalent latitude (EqL) coordinate throughout the lowermost stratosphere and in the upper troposphere. Mapping O3 data from the Aura Microwave Limb Sounder (MLS) satellite and the Winter Storms aircraft datasets in jet coordinates thus emphasizes different aspects of the circulation compared to an EqL-coordinate framework: the jet coordinate reorders the data geometrically, thus highlighting the strong PV, tropopause height and trace gas gradients across the subtropical jet, whereas EqL is a dynamical coordinate that may blur these spatial relationships but provides information on irreversible transport. The jet coordinate view identifies the concentration of stratospheric ozone well below the tropopause in the region poleward of and below the jet core, as well as other transport features associated with the upper tropospheric jets. Using the jet information in EqL coordinates allows us to study trace gas distributions in regions of weak versus strong jets, and demonstrates weaker transport barriers in regions with less jet influence. MLS and Atmospheric Chemistry Experiment-Fourier Transform Spectrometer trace gas fields for spring 2008 in jet coordinates show very strong, closely correlated, PV, tropopause height and trace gas gradients across the jet, and evidence of intrusions of stratospheric air below the tropopause below and poleward of the subtropical jet; these features are consistent between instruments and among multiple trace gases. Our characterization of the jets is facilitating studies that will improve our understanding of upper tropospheric trace gas evolution.

Satellite observations and modeling of transport in the upper troposphere through the lower mesosphere during the 2006 major stratospheric sudden warming

Abstract. An unusually strong and prolonged stratospheric sudden warming (SSW) in January 2006 was the first major SSW for which globally distributed long-lived trace gas data are available covering the upper troposphere through the lower mesosphere. We use Aura Microwave Limb Sounder (MLS), Atmospheric Chemistry Experiment-Fourier Transform Spectrometer (ACE-FTS) data, the SLIMCAT Chemistry Transport Model (CTM), and assimilated meteorological analyses to provide a comprehensive picture of transport during this event. The upper tropospheric ridge that triggered the SSW was associated with an elevated tropopause and layering in trace gas profiles in conjunction with stratospheric and tropospheric intrusions. Anomalous poleward transport (with corresponding quasi-isentropic troposphere-to-stratosphere exchange at the lowest levels studied) in the region over the ridge extended well into the lower stratosphere. In the middle and upper stratosphere, the breakdown of the polar vortex transport barrier was seen in a signature of rapid, widespread mixing in trace gases, including CO, H2O, CH4 and N2O. The vortex broke down slightly later and more slowly in the lower than in the middle stratosphere. In the middle and lower stratosphere, small remnants with trace gas values characteristic of the pre-SSW vortex lingered through the weak and slow recovery of the vortex. The upper stratospheric vortex quickly reformed, and, as enhanced diabatic descent set in, CO descended into this strong vortex, echoing the fall vortex development. Trace gas evolution in the SLIMCAT CTM agrees well with that in the satellite trace gas data from the upper troposphere through the middle stratosphere. In the upper stratosphere and lower mesosphere, the SLIMCAT simulation does not capture the strong descent of mesospheric CO and H2O values into the reformed vortex; this poor CTM performance in the upper stratosphere and lower mesosphere results primarily from biases in the diabatic descent in assimilated analyses.

The high Arctic in extreme winters: vortex, temperature, and MLS and ACE-FTS trace gas evolution

Abstract. The first three Arctic winters of the ACE mission represented two extremes of winter variability: Stratospheric sudden warmings (SSWs) in 2004 and 2006 were among the strongest, most prolonged on record; 2005 was a record cold winter. Canadian Arctic Atmospheric Chemistry Experiment (ACE) Validation Campaigns were conducted at Eureka (80° N, 86° W) during each of these winters. New satellite measurements from ACE-Fourier Transform Spectrometer (ACE-FTS), Sounding of the Atmosphere using Broadband Emission Radiometry (SABER), and Aura Microwave Limb Sounder (MLS), along with meteorological analyses and Eureka lidar temperatures, are used to detail the meteorology in these winters, to demonstrate its influence on transport, and to provide a context for interpretation of ACE-FTS and validation campaign observations. During the 2004 and 2006 SSWs, the vortex broke down throughout the stratosphere, reformed quickly in the upper stratosphere, and remained weak in the middle and lower stratosphere. The stratopause reformed at very high altitude, near 75 km. ACE measurements covered both vortex and extra-vortex conditions in each winter, except in late-February through mid-March 2004 and 2006, when the strong, pole-centered vortex that reformed after the SSWs resulted in ACE sampling only inside the vortex in the middle through upper stratosphere. The 2004 and 2006 Eureka campaigns were during the recovery from the SSWs, with the redeveloping vortex over Eureka. 2005 was the coldest winter on record in the lower stratosphere, but with an early final warming in mid-March. The vortex was over Eureka at the start of the 2005 campaign, but moved away as it broke up. Disparate temperature profile structure and vortex evolution resulted in much lower (higher) temperatures in the upper (lower) stratosphere in 2004 and 2006 than in 2005. Satellite temperatures agree well with lidar data up to 50–60 km, and ACE-FTS, MLS and SABER show good agreement in high-latitude temperatures throughout the winters. Consistent with a strong, cold upper stratospheric vortex and enhanced radiative cooling after the SSWs, MLS and ACE-FTS trace gas measurements show strongly enhanced descent in the upper stratospheric vortex in late January through March 2006 compared to that in 2005.

Behaviour of tracer diffusion in simple atmospheric boundary layer models

Abstract. 1-D profiles and time series from an idealised atmospheric boundary layer model are presented, which show agreement with boundary layer measurements of polar NOx. Diffusion models are increasingly being used as the framework for studying tropospheric air chemistry dynamics. Models based on standard boundary layer diffusivity profiles have an intrinsic behaviour that is not necessarily intuitive, due to the variation of turbulent diffusivity with height. The simple model presented captures the essence of the evolution of a trace gas released at the surface, and thereby provides both a programming and a conceptual tool in the analysis of observed trace gas evolution. A time scale inherent in the model can be tuned by fitting model time series to observations. This scale is then applicable to the more physically simple but chemically complex zeroth order or box models of chemical interactions.

Simulations of Dynamics and Transport during the September 2002 Antarctic Major Warming

Abstract A mechanistic model simulation initialized on 14 September 2002, forced by 100-hPa geopotential heights from Met Office analyses, reproduced the dynamical features of the 2002 Antarctic major warming. The vortex split on ∼25 September; recovery after the warming, westward and equatorward tilting vortices, and strong baroclinic zones in temperature associated with a dipole pattern of upward and downward vertical velocities were all captured in the simulation. Model results and analyses show a pattern of strong upward wave propagation throughout the warming, with zonal wind deceleration throughout the stratosphere at high latitudes before the vortex split, continuing in the middle and upper stratosphere and spreading to lower latitudes after the split. Three-dimensional Eliassen–Palm fluxes show the largest upward and poleward wave propagation in the 0°–90°E sector prior to the vortex split (coincident with the location of strongest cyclogenesis at the model’s lower boundary), with an additional region of strong upward propagation developing near 180°–270°E. These characteristics are similar to those of Arctic wave-2 major warmings, except that during this warming, the vortex did not split below ∼600 K. The effects of poleward transport and mixing dominate modeled trace gas evolution through most of the mid- to high-latitude stratosphere, with a core region in the lower-stratospheric vortex where enhanced descent dominates and the vortex remains isolated. Strongly tilted vortices led to low-latitude air overlying vortex air, resulting in highly unusual trace gas profiles. Simulations driven with several meteorological datasets reproduced the major warming, but in others, stronger latitudinal gradients at high latitudes at the model boundary resulted in simulations without a complete vortex split in the midstratosphere. Numerous tests indicate very high sensitivity to the boundary fields, especially the wave-2 amplitude. Major warmings occurred for initial fields with stronger winds and larger vortices, but not smaller vortices, consistent with the initiation of wind deceleration by upward-propagating waves near the poleward edge of the region where wave 2 can propagate above the jet core. Thus, given the observed 100-hPa boundary forcing, stratospheric preconditioning is not needed to reproduce a major warming similar to that observed. The anomalously strong forcing in the lower stratosphere can be viewed as the primary direct cause of the major warming.

The Tropospheric Ozone Production about the Spring Equinox (TOPSE) Experiment: Introduction

The Tropospheric Ozone Production about the Spring Equinox (TOPSE) experiment was conducted during February–March, 2000 to study the evolution of tropospheric chemistry at mid to high latitudes over North America. The experiment used airborne in situ and remote sensing measurements of trace gases, radiation, and aerosols, combined with model simulations, to describe the major processes that control evolution of ozone and oxidants during the winter‐spring transition. This paper introduces the major scientific questions of the TOPSE experiment, describes the conduct of the mission, and introduces the scientific results discussed in a series of companion papers in this special section. Among the significant findings of the experiment was that tropospheric ozone increases from winter to spring were dominated by in situ photochemical production in the troposphere, rather than by transport from the stratosphere. Also unique observations of widespread surface ozone depletion events, and of seasonal evolution of trace gases and aerosols as a function of latitude and altitude, were obtained over the course of the mission.

The seasonal evolution of NMHCs and light alkyl nitrates at middle to high northern latitudes during TOPSE

The Tropospheric Ozone Production about the Spring Equinox (TOPSE) experiment was designed to follow the role of photochemistry in the evolution of the springtime maximum of tropospheric ozone (O3) in the Northern Hemisphere (NH) at high latitudes. Determination of the composition and seasonal evolution of volatile organic carbon (VOC) species, which take part in and are good indicators for photochemical processes in the troposphere, was an important part of this study. We report measurements of a large number of C2–C10 nonmethane hydrocarbons (NMHCs), selected C1–C2 halocarbons, and C1–C4 alkyl nitrates. These gases were quantified in whole air samples collected aboard the National Center for Atmospheric Research (NCAR) C‐130 aircraft at altitudes between 30 m and 8 km. Seven TOPSE sampling trips were flown between early February and mid‐May 2000 covering the region from Colorado (40°N) to Churchill (in Manitoba, Canada), Thule (in northern Greenland), and as far north as 85°N. These measurements represent the most comprehensive spatial characterization of the North American Arctic to date and revealed strong latitudinal, vertical, and temporal NMHC gradients. In the midtroposphere north of Churchill (58°N), ΣNMHCs decreased by ∼6.2 ppbC between February and May (1.6 ppbC month−1) and the magnitude of this change diminished with altitude. Over the same period, midtropospheric O3 levels increased by ∼16 ppbv (4.2 ppbv month−1). Free tropospheric NMHC decreases were consistent with removal by hydroxyl (OH) radicals at an average mixing ratio for mid‐March to mid‐May of 4.1 × 105 mol cm−3. The alkyl nitrates, which are a reservoir species for tropospheric reactive odd nitrogen (NOY), revealed similar latitudinal, vertical, and temporal gradients to their parent NMHCs. Their total decreased by ∼4 pptv month−1, representing 10% or less of NOY. In conjunction with meteorological trajectory analysis, different trace gas signatures provided significant clues to the origins of individual polluted air masses. Several of these air masses were rapidly advected over the Pole from source regions in northeastern and western Europe as well as an air mass that originated over the southwestern United States/Baja California that contained unusually high levels of alkanes. In addition, episodes of low boundary layer (BL) O3 associated with low NMHC mixing ratios and trajectories from over the Arctic Ocean were frequently sampled toward the latter part of the experiment. The TOPSE data described here provide a unique picture of NH trace gas evolution from winter to summer that will be invaluable to models investigating the role that anthropogenic emissions play in high latitude O3 chemistry.

A three‐dimensional modeling study of trace species in the Arctic lower stratosphere during winter 1989–1990

A three‐dimensional (3D) radiative‐dynamical‐chemical model has been developed and used to study the evolution of trace gases in the Arctic lower stratosphere during winter 1989–1990. A series of 10‐day model integrations were performed throughout this period. The model includes a comprehensive scheme of gas phase chemical reactions as well as a parameterization of heterogeneous reactions occurring on polar stratospheric cloud (PSC) surfaces. An important element of a 3D chemical model is the transport scheme. In this study the transport of chemical species is achieved by a non diffusive method well suited to the preservation of sharp gradients. During the winter studied temperatures were cold enough for the formation of both type I and type II polar stratospheric clouds from early December to early February. Model simulations in late December show that inside the polar vortex air is rapidly processed by polar stratospheric clouds converting HCl and ClONO2 to active chlorine. The possibility of ozone destruction depends strongly on the amount of sunlight. In early February an average ozone loss of 15 ppbv (parts per billion by volume) /day is predicted in PSC‐processed air at 50 hPa, giving a column loss of just under 1 DU/day. This loss increases to 25 ppbv/day if PSCs persist until March with a column loss of around 1.5 DU/day. The relatively small magnitude of the ozone loss predicted in the model, compared to the variability of ozone induced by dynamics, highlights the problems in identifying the signature of chemical ozone loss in the Arctic. In future years significant ozone depletion could occur if PSCs persist until late March. The efficiency of the catalytic cycles responsible for the ozone loss has been analyzed as a function of latitude, altitude and time. In general, the cycle involving ClO + ClO is the dominant loss mechanism in the polar lower stratosphere. Cycles involving BrO can make a relatively large contribution early in the season and when the levels of ClO are low. The cycle initiated by ClO + O destroys ozone at altitudes above 30 hPa but the loss is compensated, to some extent, by in situ ozone production. The results for trace species are validated, where possible, by comparison with the available measurements, although the sparse nature of the observations does not effectively constrain the model.

Simulation of chemical processes occurring in an atmospheric boundary layer. Influence of light and biogenic hydrocarbons on the formation of oxidants

A photochemical model has been developed to determine the impact of the emission of light and terpenic hydrocarbons (HCs) on the evolution of ozone, HNO 3 and PAN concentrations in the troposphere. The present model, of Lagrangian type, describes the evolution of trace gases in an air mass moving over a large and homogeneous source area. The respective cycles of O 3, NO x , methane and CO are considered. The vertical exchange is treated by introduction of a vertical diffusivity tensor K z varying as a function of time and altitude. The results of this study indicate that both the intensity of vertical exchanges of airborne elements and the ground deposition play an important role on the evolution of vertical concentration profiles. The influence of diffusivity on the integrated concentrations in the boundary layer remains low. The introduction of light HCs (alkanes, alkenes) results in an increase in the O 3 concentration, correlated with the intensity of NO x and HC emissions. For a given level of NO x , both a decrease of the concentration in HNO 3 and an increase in the PAN concentration are observable when the production of light HCs increases. The sensitivity increases with the NO x source. The introduction of terpenic HCs causes a depletion of O 3 in the air masses characterized by low NO x emission rates, and an enrichment in those with higher emission rates. In both cases, the amplitude of the variation increases with the importance of the source of terpenic HCs, and is found higher for α-pinene than for isoprene. For a given NO x emission rate, the HNO 3 concentrations are seen to decrease when the source of natural HCs increase, whereas the concentration in PAN increases. As observed for light HCs, the sensitivity shows a dependence on the magnitude of the NO x source.