G. J. Flesch

Volatile, Isotope, and Organic Analysis of Martian Fines with the Mars Curiosity Rover

Samples from the Rocknest aeolian deposit were heated to ~835°C under helium flow and evolved gases analyzed by Curiosity’s Sample Analysis at Mars instrument suite. H2O, SO2, CO2, and O2 were the major gases released. Water abundance (1.5 to 3 weight percent) and release temperature suggest that H2O is bound within an amorphous component of the sample. Decomposition of fine-grained Fe or Mg carbonate is the likely source of much of the evolved CO2. Evolved O2 is coincident with the release of Cl, suggesting that oxygen is produced from thermal decomposition of an oxychloride compound. Elevated δD values are consistent with recent atmospheric exchange. Carbon isotopes indicate multiple carbon sources in the fines. Several simple organic compounds were detected, but they are not definitively martian in origin.

Mars methane detection and variability at Gale crater

Of water and methane on Mars The Curiosity rover has been collecting data for the past 2 years, since its delivery to Mars (see the Perspective by Zahnle). Many studies now suggest that many millions of years ago, Mars was warmer and wetter than it is today. But those conditions required an atmosphere that seems to have vanished. Using the Curiosity rover, Mahaffy et al. measured the ratio of deuterium to hydrogen in clays that were formed 3.0 to 3.7 billion years ago. Hydrogen escapes more readily than deuterium, so this ratio offers a snapshot measure of the ancient atmosphere that can help constrain when and how it disappeared. Most methane on Earth has a biological origin, so planetary scientists have keenly pursued its detection in the martian atmosphere as well. Now, Webster et al. have precisely confirmed the presence of methane in the martian atmosphere with the instruments aboard the Curiosity rover at Gale crater. Science, this issue p. 412, p. 415; see also p. 370 Curiosity confirms the presence and variability of atmospheric methane, implying episodic production from an unknown source. [Also see Perspective by Zahnle] Reports of plumes or patches of methane in the martian atmosphere that vary over monthly time scales have defied explanation to date. From in situ measurements made over a 20-month period by the tunable laser spectrometer of the Sample Analysis at Mars instrument suite on Curiosity at Gale crater, we report detection of background levels of atmospheric methane of mean value 0.69 ± 0.25 parts per billion by volume (ppbv) at the 95% confidence interval (CI). This abundance is lower than model estimates of ultraviolet degradation of accreted interplanetary dust particles or carbonaceous chondrite material. Additionally, in four sequential measurements spanning a 60-sol period (where 1 sol is a martian day), we observed elevated levels of methane of 7.2 ± 2.1 ppbv (95% CI), implying that Mars is episodically producing methane from an additional unknown source.

Chemical depletion of Arctic ozone in winter 1999/2000

During Arctic winters with a cold, stable stratospheric circulation, reactions on the surface of polar stratospheric clouds (PSCs) lead to elevated abundances of chlorine monoxide (ClO) that, in the presence of sunlight, destroy ozone. Here we show that PSCs were more widespread during the 1999/2000 Arctic winter than for any other Arctic winter in the past two decades. We have used three fundamentally different approaches to derive the degree of chemical ozone loss from ozonesonde, balloon, aircraft, and satellite instruments. We show that the ozone losses derived from these different instruments and approaches agree very well, resulting in a high level of confidence in the results. Chemical processes led to a 70% reduction of ozone for a region ∼1 km thick of the lower stratosphere, the largest degree of local loss ever reported for the Arctic. The Match analysis of ozonesonde data shows that the accumulated chemical loss of ozone inside the Arctic vortex totaled 117 ± 14 Dobson units (DU) by the end of winter. This loss, combined with dynamical redistribution of air parcels, resulted in a 88 ± 13 DU reduction in total column ozone compared to the amount that would have been present in the absence of any chemical loss. The chemical loss of ozone throughout the winter was nearly balanced by dynamical resupply of ozone to the vortex, resulting in a relatively constant value of total ozone of 340 ± 50 DU between early January and late March. This observation of nearly constant total ozone in the Arctic vortex is in contrast to the increase of total column ozone between January and March that is observed during most years.

Low upper limit to methane abundance on Mars

No Methane to Be Found On Earth, atmospheric methane is mostly produced biologically. Atmospheric methane has also been detected on Mars, but these reports have been controversial. Based on data from the Sample Analysis at Mars instrument suite on the Curiosity rover, which arrived at the surface of Mars in August 2012, Webster et al. (p. 355, published online 19 September) report no methane, with an upper limit of only 1.3 parts per billion by volume, about 6 times lower than previous measurements. Data from the Curiosity rover reveal an upper limit on Mars of only 1.3 parts per billion by volume for atmospheric methane. By analogy with Earth, methane in the Martian atmosphere is a potential signature of ongoing or past biological activity. During the past decade, Earth-based telescopic observations reported “plumes” of methane of tens of parts per billion by volume (ppbv), and those from Mars orbit showed localized patches, prompting speculation of sources from subsurface bacteria or nonbiological sources. From in situ measurements made with the Tunable Laser Spectrometer (TLS) on Curiosity using a distinctive spectral pattern specific to methane, we report no detection of atmospheric methane with a measured value of 0.18 ± 0.67 ppbv corresponding to an upper limit of only 1.3 ppbv (95% confidence level), which reduces the probability of current methanogenic microbial activity on Mars and limits the recent contribution from extraplanetary and geologic sources.

The imprint of atmospheric evolution in the D/H of hesperian clay minerals on Mars

Of water and methane on Mars The Curiosity rover has been collecting data for the past 2 years, since its delivery to Mars (see the Perspective by Zahnle). Many studies now suggest that many millions of years ago, Mars was warmer and wetter than it is today. But those conditions required an atmosphere that seems to have vanished. Using the Curiosity rover, Mahaffy et al. measured the ratio of deuterium to hydrogen in clays that were formed 3.0 to 3.7 billion years ago. Hydrogen escapes more readily than deuterium, so this ratio offers a snapshot measure of the ancient atmosphere that can help constrain when and how it disappeared. Most methane on Earth has a biological origin, so planetary scientists have keenly pursued its detection in the martian atmosphere as well. Now, Webster et al. have precisely confirmed the presence of methane in the martian atmosphere with the instruments aboard the Curiosity rover at Gale crater. Science, this issue p. 412, p. 415; see also p. 370 A measurement with the Curiosity rover probes the Hesperian era and constrains the timing of hydrogen loss. [Also see Perspective by Zahnle] The deuterium-to-hydrogen (D/H) ratio in strongly bound water or hydroxyl groups in ancient martian clays retains the imprint of the water of formation of these minerals. Curiosity’s Sample Analysis at Mars (SAM) experiment measured thermally evolved water and hydrogen gas released between 550° and 950°C from samples of Hesperian-era Gale crater smectite to determine this isotope ratio. The D/H value is 3.0 (±0.2) times the ratio in standard mean ocean water. The D/H ratio in this ~3-billion-year-old mudstone, which is half that of the present martian atmosphere but substantially higher than that expected in very early Mars, indicates an extended history of hydrogen escape and desiccation of the planet.

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.

Evolution of HCL concentrations in the lower stratosphere from 1991 to 1996 following the eruption of Mt. Pinatubo

In situ measurements of hydrochloric acid in the lower stratosphere reveal that its mean abundance relative to that of total inorganic chlorine (Cly) has evolved upwards from HCl/Cly = 40% in late 1991 to 70% in 1996. This fraction is generally anticorrelated with aerosol surface area concentration, which has been diminishing since the 1991 volcanic eruption of Mt. Pinatubo. Calculations incorporating new laboratory results of faster heterogeneous chemistry show that air parcels with high aerosol loading exposed to temperatures below 205 K can experience enough chlorine activation to drive the HCl/Cly below 50%, but overestimate observed ClO/Cly.

Mars laser hygrometer

We have designed and built a miniature near-IR tunable diode laser (TDL) spectrometer for measuring in situ the water vapor mixing ratio either in the Martian atmosphere or thermally evolved from Martian soil or ice samples. The laser hygrometer uses a thermoelectrically cooled single-mode distributed-feedback TDL at 1.87 microm to scan over a selected vibration-rotation line of both H2O and CO2 near 5327.3 cm(-1). A working prototype that weighs only 230 g has been built and used to generate spectra whose analysis demonstrates precision sensitivities as fine as 1 part in 10(6) by volume in 1 s or 0.1 part in 10(6) in 10 s at Martian pressures and temperatures. Absolute uncertainties of approximately 5% are calculated.

Background levels of methane in Mars’ atmosphere show strong seasonal variations

Measuring martian organics and methane The Curiosity rover has been sampling on Mars for the past 5 years (see the Perspective by ten Kate). Eigenbrode et al. used two instruments in the SAM (Sample Analysis at Mars) suite to catch traces of complex organics preserved in 3-billion-year-old sediments. Heating the sediments released an array of organics and volatiles reminiscent of organic-rich sedimentary rock found on Earth. Most methane on Earth is produced by biological sources, but numerous abiotic processes have been proposed to explain martian methane. Webster et al. report atmospheric measurements of methane covering 3 martian years and found that the background level varies with the local seasons. The seasonal variation provides an important clue for determining the origin of martian methane. Science, this issue p. 1096, p. 1093; see also p. 1068 The background level of methane in Mars’ atmosphere varies with season, providing a clue to its origin. Variable levels of methane in the martian atmosphere have eluded explanation partly because the measurements are not repeatable in time or location. We report in situ measurements at Gale crater made over a 5-year period by the Tunable Laser Spectrometer on the Curiosity rover. The background levels of methane have a mean value 0.41 ± 0.16 parts per billion by volume (ppbv) (95% confidence interval) and exhibit a strong, repeatable seasonal variation (0.24 to 0.65 ppbv). This variation is greater than that predicted from either ultraviolet degradation of impact-delivered organics on the surface or from the annual surface pressure cycle. The large seasonal variation in the background and occurrences of higher temporary spikes (~7 ppbv) are consistent with small localized sources of methane released from martian surface or subsurface reservoirs.

Adaptive control of tunable laser spectrometers for space flight applications

An architecture and process for the rapid prototyping and subsequent development of an adaptive tunable laser absorption spectrometer (TLS) are described.12 Adaptive in this context refers to the real-time autonomous response of software and electronics to the harsh and hard-to-predict conditions that can be encountered in space flight missions. This approach takes advantage of both software tools as well as highly integrated RTOS/FPGA hardware modules now commercially available. The current state of space-qualified tunable laser spectrometers is described, along with motivations for adaptability.