Franck Lefèvre

Chemistry of the 1991–1992 stratospheric winter: Three-dimensional model simulations

A three-dimensional chemistry-transport model of the stratosphere is used to simulate the evolution of trace constituents during the 1991–1992 Arctic winter. It is shown that heterogeneous reactions on polar stratospheric clouds led in early January to almost complete activation of atmospheric chlorine inside the polar vortex, in remarkable coincidence with observations by the ER-2 aircraft (Toohey et al., 1993) and the microwave limb sounder on the Upper Atmosphere Research Satellite (Waters et al., 1993). Sulfate aerosols resulting from the eruption of Mount Pinatubo also produced a significant increase in chlorine monoxide (ClO) concentrations at middle and high latitudes. The net chemical destruction of ozone found in the vortex at the end of the simulation (25% at 50 hPa and 25 DU), although substantial, was limited by available sunlight and the short period during which stratospheric clouds occurred.

Observed variations of methane on Mars unexplained by known atmospheric chemistry and physics

The detection of methane on Mars has revived the possibility of past or extant life on this planet, despite the fact that an abiogenic origin is thought to be equally plausible. An intriguing aspect of the recent observations of methane on Mars is that methane concentrations appear to be locally enhanced and change with the seasons. However, methane has a photochemical lifetime of several centuries, and is therefore expected to have a spatially uniform distribution on the planet. Here we use a global climate model of Mars with coupled chemistry to examine the implications of the recently observed variations of Martian methane for our understanding of the chemistry of methane. We find that photochemistry as currently understood does not produce measurable variations in methane concentrations, even in the case of a current, local and episodic methane release. In contrast, we find that the condensation–sublimation cycle of Mars’ carbon dioxide atmosphere can generate large-scale methane variations differing from those observed. In order to reproduce local methane enhancements similar to those recently reported, we show that an atmospheric lifetime of less than 200 days is necessary, even if a local source of methane is only active around the time of the observation itself. This implies an unidentified methane loss process that is 600 times faster than predicted by standard photochemistry. The existence of such a fast loss in the Martian atmosphere is difficult to reconcile with the observed distribution of other trace gas species. In the case of a destruction mechanism only active at the surface of Mars, destruction of methane must occur with an even shorter timescale of the order of ∼1 hour to explain the observations. If recent observations of spatial and temporal variations of methane are confirmed, this would suggest an extraordinarily harsh environment for the survival of organics on the planet.

Three‐dimensional modeling of ozone on Mars

We present the first three-dimensional model simulations of ozone on Mars. The model couples a state-of-the-art gas-phase photochemical package to the general circulation model developed at Laboratoire de Me´te´orologie Dynamique (LMD). The results do not contradict the classical picture of a global anticorrelation between the ozone (O3) and water vapor columns. However, the quantitative approach shows significant departures from this relationship, related to substantial orbital variations in the O3 vertical distribution. Over the period Ls = 180–330, low-latitude to midlatitude O3 is essentially confined below 20 km, has a weak diurnal cycle, and is largely modulated by topography. During the rest of the year (Ls = 330–180) the model predicts the formation of an O3 layer at 25–70 km altitude, characterized by nighttime densities about one order of magnitude larger than during the day. Throughout the year, high-latitude O3 peaks near the surface and reaches maximum integrated amounts (40 mm-atm) in the winter polar vortex, with considerable (30 to 50%) dynamically induced day-to-day variations. The most stringent comparison to date with O3 observational data reveals contrasted results. A good quantitative agreement is found in the postperihelion period (Ls = 290–10), but the model fails to reproduce O3 columns as large as those measured near aphelion (Ls = 61–67). Current uncertainties in absorption cross sections and gas-phase kinetics data do not seem to provide credible explanations to explain this discrepancy, which may suggest the existence of heterogeneous processes.

The 1997 Arctic Ozone depletion quantified from three-dimensional model simulations

Three-dimensional simulations of total ozone are reported for the 1996-97 Arctic winter. The record low ozone values observed by satellite in late March are well reproduced by the chemistry-transport model. The comparison between the chemically integrated ozone and a passive tracer with identical initialization allows us to discrimate chemical changes from variations due to dynamical processes. In addition to a substantial total ozone chemical loss (60 to 120 Dobson Units), the simulation reveals an dynamically-induced reduction of ∼70 DU also responsible for the ozone minimum observed in the Arctic in late March 1997.

MAVEN observations of the response of Mars to an interplanetary coronal mass ejection

Coupling between the lower and upper atmosphere, combined with loss of gas from the upper atmosphere to space, likely contributed to the thin, cold, dry atmosphere of modern Mars. To help understand ongoing ion loss to space, the Mars Atmosphere and Volatile Evolution (MAVEN) spacecraft made comprehensive measurements of the Mars upper atmosphere, ionosphere, and interactions with the Sun and solar wind during an interplanetary coronal mass ejection impact in March 2015. Responses include changes in the bow shock and magnetosheath, formation of widespread diffuse aurora, and enhancement of pick-up ions. Observations and models both show an enhancement in escape rate of ions to space during the event. Ion loss during solar events early in Mars history may have been a major contributor to the long-term evolution of the Mars atmosphere.

Heterogeneous chemistry in the atmosphere of Mars

Hydrogen radicals are produced in the martian atmosphere by the photolysis of water vapour and subsequently initiate catalytic cycles that recycle carbon dioxide from its photolysis product carbon monoxide. These processes provide a qualitative explanation for the stability of the atmosphere of Mars, which contains 95 per cent carbon dioxide. Balancing carbon dioxide production and loss based on our current understanding of the gas-phase chemistry in the martian atmosphere has, however, proven to be difficult. Interactions between gaseous chemical species and ice cloud particles have been shown to be key factors in the loss of polar ozone observed in the Earth’s stratosphere, and may significantly perturb the chemistry of the Earth’s upper troposphere. Water-ice clouds are also commonly observed in the atmosphere of Mars and it has been suggested previously that heterogeneous chemistry could have an important impact on the composition of the martian atmosphere. Here we use a state-of-the-art general circulation model together with new observations of the martian ozone layer to show that model simulations that include chemical reactions occurring on ice clouds lead to much improved quantitative agreement with observed martian ozone levels in comparison with model simulations based on gas-phase chemistry alone. Ozone is readily destroyed by hydrogen radicals and is therefore a sensitive tracer of the chemistry that regulates the atmosphere of Mars. Our results suggest that heterogeneous chemistry on ice clouds plays an important role in controlling the stability and composition of the martian atmosphere.

Polar vortex evolution during the 2002 Antarctic major warming as observed by the Odin satellite

In September 2002 the Antarctic polar vortex split in two under the influence of a sudden warming. During this event, the Odin satellite was able to measure both ozone (O3) and chlorine monoxide (ClO), a key constituent responsible for the so-called “ozone hole”, together with nitrous oxide (N2O), a dynamical tracer, and nitric acid (HNO3) and nitrogen dioxide (NO2), tracers of denitrification. The submillimeter radiometer (SMR) microwave instrument and the Optical Spectrograph and Infrared Imager System (OSIRIS) UV-visible light spectrometer (VIS) and IR instrument on board Odin have sounded the polar vortex during three different periods: before (19–20 September), during (24–25 September), and after (1–2 and 4–5 October) the vortex split. Odin observations coupled with the Reactive Processes Ruling the Ozone Budget in the Stratosphere (REPROBUS) chemical transport model at and above 500 K isentropic surfaces (heights above 18 km) reveal that on 19–20 September the Antarctic vortex was dynamically stable and chemically nominal: denitrified, with a nearly complete chlorine activation, and a 70% O3 loss at 500 K. On 25–26 September the unusual morphology of the vortex is monitored by the N2O observations. The measured ClO decay is consistent with other observations performed in 2002 and in the past. The vortex split episode is followed by a nearly complete deactivation of the ClO radicals on 1–2 October, leading to the end of the chemical O3 loss, while HNO3 and NO2 fields start increasing. This acceleration of the chlorine deactivation results from the warming of the Antarctic vortex in 2002, putting an early end to the polar stratospheric cloud season. The model simulation suggests that the vortex elongation toward regions of strong solar irradiance also favored the rapid reformation of ClONO2. The observed dynamical and chemical evolution of the 2002 polar vortex is qualitatively well reproduced by REPROBUS. Quantitative differences are mainly attributable to the too weak amounts of HNO3 in the model, which do not produce enough NO2 in presence of sunlight to deactivate chlorine as fast as observed by Odin.

Depletion of Column Ozone in the Arctic During the Winters of 1993-94 and 1994-95

The total ozone reduction in the Arctic during the winters of 1993/94 and 1994/95 has been evaluated using the ground-based total ozone measurements of five SAOZ spectrometers distributed in the Arctic and from number density profiles of a balloon-borne version of the instrument. The ozone change resulting from transport has been removed using a 3D Chemistry Transport Model (CTM) run without chemistry. A cumulative total ozone depletion at the end of winter in March of 18% ± 4% in 1994 and of 32% ± 4% in 1995 was observed within the polar vortex, and of 15% ± 4% in both years outside the vortex. This evaluation is not sensitive to the vertical transport in the model. The periods, locations and altitudes at which ozone loss occurred were tightly connected to temperatures lower than NAT condensation temperature. The maximum loss was observed at 50 hPa in 1994 and lower, 60-80 hPa, in 1995. Half of the depletion in 1994 and three quarters in 1995 occurred during the early winter, showing that a late final warming is not a prerequisite for large ozone destruction in the northern hemisphere. The timing, the geographical location and the altitude of the ozone losses are well captured by the 3D CTM photochemical model using current chemistry, but its amplitude at low sun during the early winter, is underestimated. The model simulations also capture the early season reductions observed outside the vortex. This suggests that the losses occurred in situ in the early winter, when low temperatures are frequent, and not later in March, when ozone is most reduced inside the vortex, which would be the case if leakage from the vortex was the cause of the depletion.

Early MAVEN Deep Dip campaign reveals thermosphere and ionosphere variability

The Mars Atmosphere and Volatile Evolution (MAVEN) mission, during the second of its Deep Dip campaigns, made comprehensive measurements of martian thermosphere and ionosphere composition, structure, and variability at altitudes down to ~130 kilometers in the subsolar region. This altitude range contains the diffusively separated upper atmosphere just above the well-mixed atmosphere, the layer of peak extreme ultraviolet heating and primary reservoir for atmospheric escape. In situ measurements of the upper atmosphere reveal previously unmeasured populations of neutral and charged particles, the homopause altitude at approximately 130 kilometers, and an unexpected level of variability both on an orbit-to-orbit basis and within individual orbits. These observations help constrain volatile escape processes controlled by thermosphere and ionosphere structure and variability.

Vertical distribution of ozone on Mars as measured by SPICAM/Mars Express using stellar occultations

[i] The ultraviolet spectrometer of the SPICAM instrument on board the European Mars Express mission has performed stellar occultations to probe the atmosphere. Vertical profiles of ozone are retrieved from inversion of transmission spectra in the altitude range 20-30 to 70 km. They are analyzed here as functions of latitude and season of the observations. These occultations have been monitored on the night side, from northern spring equinox (L s = 8°) to northern winter solstice (L s = 270°). The profiles show the presence of two ozone layers: (1) one located near the surface, the top of which is visible below 30 km altitude, and (2) one layer located in the altitude range 30 to 60 km, a feature that is highly variable with latitude and season. This layer is first seen after L s = 11°, and the ozone abundance at the peak tends to increase until L s ∼ 40°, when it stabilizes around 6-8 x 10 9 cm -3 . After southern winter solstice (L s ∼ 100°), the peak abundance starts decreasing again, and this ozone layer is no longer detected after L s ∼ 130°. A recent model (Lefevre et al., 2004) predicted the presence of these ozone layers, the altitude one being only present at night. Though the agreement between model and observations is quite good, this nocturnal altitude layer is present in SPICAM data over a less extended period than predicted. Though a possible role of heterogeneous chemistry is not excluded, this difference is probably linked to the seasonal evolution of the vertical distribution of water vapor.