Relative Humidity on Mars: New Results From the Phoenix TECP Sensor.

In situ measurements of relative humidity (RH) on Mars have only been performed by the Phoenix (PHX) and Mars Science Laboratory (MSL) missions. Here we present results of our recalibration of the PHX thermal and electrical conductivity probe (TECP) RH sensor. This recalibration was conducted using a TECP engineering model subjected to the full range of environmental conditions at the PHX landing site in the Michigan Mars Environmental Chamber. The experiments focused on the warmest and driest conditions (daytime) because they were not covered in the original calibration (Zent et al., 2010, https://doi.org/10.1029/2009JE003420) and previous recalibration (Zent et al., 2016, https://doi.org/10.1002/2015JE004933). In nighttime conditions, our results are in excellent agreement with the previous 2016 recalibration, while in daytime conditions, our results show larger water vapor pressure values. We obtain vapor pressure values in the range ~0.005-1.4 Pa, while Zent et al. (2016, https://doi.org/10.1002/2015JE004933) obtain values in the range ~0.004-0.4 Pa. Our higher daytime values are in better agreement with independent estimates from the ground by the PHX Surface Stereo Imager instrument and from orbit by Compact Reconnaissance Imaging Spectrometer for Mars. Our results imply larger day-to-night ratios of water vapor pressure at PHX compared to MSL, suggesting a stronger atmosphere-regolith interchange in the Martian arctic than at lower latitudes. Further, they indicate that brine formation at the PHX landing site via deliquescence can be achieved only temporarily between midnight and 6 a.m. on a few sols. The results from our recalibration are important because they shed light on the near-surface humidity environment on Mars.

H2O at the Phoenix landing site.

The Phoenix mission investigated patterned ground and weather in the northern arctic region of Mars for 5 months starting 25 May 2008 (solar longitude between 76.5 degrees and 148 degrees ). A shallow ice table was uncovered by the robotic arm in the center and edge of a nearby polygon at depths of 5 to 18 centimeters. In late summer, snowfall and frost blanketed the surface at night; H(2)O ice and vapor constantly interacted with the soil. The soil was alkaline (pH = 7.7) and contained CaCO(3), aqueous minerals, and salts up to several weight percent in the indurated surface soil. Their formation likely required the presence of water.

Mars water-ice clouds and precipitation.

The light detection and ranging instrument on the Phoenix mission observed water-ice clouds in the atmosphere of Mars that were similar to cirrus clouds on Earth. Fall streaks in the cloud structure traced the precipitation of ice crystals toward the ground. Measurements of atmospheric dust indicated that the planetary boundary layer (PBL) on Mars was well mixed, up to heights of around 4 kilometers, by the summer daytime turbulence and convection. The water-ice clouds were detected at the top of the PBL and near the ground each night in late summer after the air temperature started decreasing. The interpretation is that water vapor mixed upward by daytime turbulence and convection forms ice crystal clouds at night that precipitate back toward the surface.

Peroxide-modified titanium dioxide: a chemical analog of putative Martian soil oxidants.

Hydrogen peroxide chemisorbed on titanium dioxide (peroxide-modified titanium dioxide) is investigated as a chemical analog to the putative soil oxidants responsible for the chemical reactivity seen in the Viking biology experiments. When peroxide-modified titanium dioxide (anatase) was exposed to a solution similar to the Viking labeled release (LR) experiment organic medium, CO2 gas was released into the sample cell headspace. Storage of these samples at 10 degrees C for 48 hr prior to exposure to organics resulted in a positive response while storage for 7 days did not. In the Viking LR experiment, storage of the Martian surface samples for 2 sols (approximately 49 hr) resulted in a positive response while storage for 141 sols essentially eliminated the initial rapid release of CO2. Heating the peroxide-modified titanium dioxide to 50 degrees C prior to exposure to organics resulted in a negative response. This is similar to, but not identical to, the Viking samples where heating to approximately 46 degrees C diminished the response by 54-80% and heating to 51.5 apparently eliminated the response. When exposed to water vapor, the peroxide-modified titanium dioxide samples release O2 in a manner similar to the release seen in the Viking gas exchange experiment (GEx). Reactivity is retained upon heating at 50 degrees C for three hours, distinguishing this active agent from the one responsible for the release of CO2 from aqueous organics. The release of CO2 by the peroxide-modified titanium dioxide is attributed to the decomposition of organics by outer-sphere peroxide complexes associated with surface hydroxyl groups, while the release of O2 upon humidification is attributed to more stable inner-sphere peroxide complexes associated with Ti4+ cations. Heating the peroxide-modified titanium dioxide to 145 degrees C inhibited the release of O2, while in the Viking experiments heating to this temperature diminished but did not eliminated the response. Although the thermal stability of the titanium-peroxide complexes in this work is lower than the stability seen in the Viking experiments, it is expected that similar types of complexes will form in titanium containing minerals other than anatase and the stability of these complexes will vary with surface hydroxylation and mineralogy.

The Mars oxidant experiment (MOx) for Mars '96.

The MOx instrument was developed to characterize the reactive nature of the martian soil. The objectives of MOx were: (1) to measure the rate of degradation of organics in the martian environment; (2) to determine if the reactions seen by the Viking biology experiments were caused by a soil oxidant and measure the reactivity of the soil and atmosphere: (3) to monitor the degradation, when exposed to the martian environment, of materials of potential use in future missions; and, finally, (4) to develop technologies and approaches that can be part of future soil analysis instrumentation. The basic approach taken in the MOx instrument was to place a variety of materials composed as thin films in contact with the soil and monitor the physical and chemical changes that result. The optical reflectance of the thin films was the primary sensing-mode. Thin films of organic materials, metals, and semiconductors were prepared. Laboratory simulations demonstrated the response of thin films to active oxidants.

On the thickness of the oxidized layer of the Martian regolith.

A revised model of the diffusion of H2O2 through the Martian regolith is presented, which argues that oxidant diffusion may be more efficient than previously thought. Recent models of the adsorption of H2O at Mars-like conditions indicate that it adsorbs more poorly than previously believed. H2O adsorption is a necessary proxy for peroxide adsorption; hence the adsorptive slowing of peroxide diffusion is modeled as less efficient. Because the peroxide has a finite lifetime, it has a finite extinction depth as well. The effects of regolith gardening by impacts are quantitatively estimated and combined with the effects of oxidation by atmospheric gases to produce estimates of the degree of oxidation of the Martian surface with depth. We explore the effects of different crater production populations along with variations in H2O2 extinction depths, and hydrothermal oxidation of ejecta. In very select circumstances involving very early onset of oxidizing conditions during heavy bombardment, 150-200 m of regolith could be fully oxidized. More likely scenarios for the crater production population, onset of oxidizing conditions, and oxidant extinction depth yield estimates of no more than a few meters to putative reducing material. In addition, uncertainties remain regarding the degree to which hydrothermal or other high-temperature chemistry might oxidize materials in ejecta blankets. The trade-off between accessing unlithified sediments or rock interiors must be considered.

Evolution of the Martian water cycle.

The current Martian water cycle is extremely asymmetric, with large amounts of vapor subliming off a permanent north polar water ice cap in northern summer, but with no apparent major source of water vapor in the southern hemisphere. Detailed simulations of this process with a three-dimensional circulation model indicate that the summertime interhemispheric exchange (Hadley cell) is very much stronger than transport by eddies in other seasons. As a result, water ice would be distributed globally were it not for the buffering action of regolith soil adsorption which limits the net flux of water vapor off the north polar cap to amounts that are insignificant even on the scale of thousands of years. It has been suggested that the polar layered deposits are the result of exchange on these long time scales, driven by changes in Martian orbital parameters. We therefore are conducting simulations to test the effect of varied orbital parameters on the Martian water cycle. We find that when the perihelion summer pole is charged with a polar water ice cap, large quantities of water are quickly transfered to the aphelion summer pole, setting up an annual cycle that resembles the present one. Thus, the adsorptivity of the Martian regolith may be in the narrow range where it can limit net transport from the aphelion but not the perihelion pole.

The circum-Chryse region as a possible example of a hydrologic cycle on Mars: geologic observations and theoretical evaluation.

The transection and superposition relationships among channels, chaos, surface materials units, and other features in the circum-Chryse region of Mars were used to evaluate relative age relationships and evolution of flood events. Channels and chaos in contact (with one another) were treated as single discrete flood-carved systems. Some outflow channel systems form networks and are inferred to have been created by multiple flood events. Within some outflow channel networks, several separate individual channel systems can be traced to a specific chaos which acted as flood-source area to that specific flood channel. Individual flood-carved systems were related to widespread materials units or other surface features that served as stratigraphic horizons. Chryse outflow channels are inferred to have formed over most of the perceivable history of Mars. Outflow channels are inferred to become younger with increasing proximity to the Chryse basin. In addition, outflow channels closer to the basin show a greater diversity in age. The relationship of subsequent outflow channel sources to the sources of earlier floods is inferred to disfavor episodic flooding due to the progressive tapping of a juvenile near-surface water supply. Instead, we propose the circum-Chryse region as a candidate site of past hydrological recycling. The discharge rates necessary to carve the circum-Chryse outflow channels would have inevitably formed temporary standing bodies of H2O on the Martian surface where the flood-waters stagnated and pooled (the Chryse basin is topographically enclosed). These observations and inferences have led us to formulate and evaluate two hypotheses: (1) large amounts of the sublimated H2O off the Chryse basin flood lakes precipitated (snowed) onto the flood-source highlands and this H2O was incorporated into the near surface, recharging the H2O sources, making possible subsequent deluges; and (2) ponded flood-water in Chryse basin drained back down an anti basinward dipping subsurface layer accessed long the southern edge of the lake, recharging the flood-source aquifers. H2O not redeposited in the flood-source region was largely lost to the hydrologic cycle. This loss progressively lowered the vitality of the cycle, probably by now killing it. Our numerical evaluations indicate that of the two hypotheses we formulated, the groundwater seep cycle seems by far the more viable. Optimally, approximately 3/4 of the original mass of an ice-covered cylindrical lake (albedo 0.5, 1 km deep, 100-km radius, draining along its rim for one quarter of its circumference into substrata with a permeability of 3000 darcies) can be modeled to have moved underground (on timescales of the order of 10(3) years) before the competing mechanisms of sublimation and freeze down choked off further water removal. Once underground, this water can travel distances equal to the separation between Chryse basin and flood-source sites in geologically short (approximately 10(6) year-scale) times. Conversely, we calculate that optimally only approximately 40% of the H2O carried from Chryse can condense at the highlands, and most of the precipitate would either collect at the base of the highlands/lowlands scarp or sublimate at rates greater than it would accumulate over the flood-source sites. Further observations from forthcoming missions may permit the determination of which mechanisms may have operated to recycle the Chryse flood-waters.

A coupled soil-atmosphere model of H2O2 on Mars.

The Viking Gas Chromatograph Mass Spectrometer failed to detect organic compounds on Mars, and both the Viking Labeled Release and the Viking Gas Exchange experiments indicated a reactive soil surface. These results have led to the widespread belief that there are oxidants in the martian soil. Since H2O2 is produced by photochemical processes in the atmosphere of Mars, and has been shown in the laboratory to reproduce closely the Viking LR results, it is a likely candidate for a martian soil oxidant. Here, we report on the results of a coupled soil/atmosphere transport model for H2O2 on Mars. Upon diffusing into the soil, its concentration is determined by the extent to which it is adsorbed and by the rate at which it is catalytically destroyed. An analytical model for calculating the distribution of H2O2 in the martian atmosphere and soil is developed. The concentration of H2O2 in the soil is shown to go to zero at a finite depth, a consequence of the nonlinear soil diffusion equation. The model is parameterized in terms of an unknown quantity, the lifetime of H2O2 against heterogeneous catalytic destruction in the soil. Calculated concentrations are compared with a H2O2 concentration of 30 nmoles/cm3, inferred from the Viking Labeled Release experiment. A significant result of this model is that for a wide range of H2O2 lifetimes (up to 10(5) years), the extinction depth was found to be less than 3 m. The maximum possible concentration in the top 4 cm is calculated to be approximately 240 nmoles/cm3, achieved with lifetimes of greater than 1000 years. Concentrations higher than 30 nmoles/cm3 require lifetimes of greater than 4.3 terrestrial years. For a wide range of H2O2 lifetimes, it was found that the atmospheric concentration is only weakly coupled with soil loss processes. Losses to the soil become significant only when lifetimes are less than a few hours. If there are depths below which H2O2 is not transported, it is plausible that organic compounds, protected from an oxidizing environment, may still exist. They would have been deposited by meteors, or be the organic remains of past life.