Inhibition of carbonate synthesis in acidic oceans on early Mars

Several lines of evidence have recently reinforced the hypothesis that an ocean existed on early Mars. Carbonates are accordingly expected to have formed from oceanic sedimentation of carbon dioxide from the ancient martian atmosphere. But spectral imaging of the martian surface has revealed the presence of only a small amount of carbonate, widely distributed in the martian dust. Here we examine the feasibility of carbonate synthesis in ancient martian oceans using aqueous equilibrium calculations. We show that partial pressures of atmospheric carbon dioxide in the range 0.8-4 bar, in the presence of up to 13.5 mM sulphate and 0.8 mM iron in sea water, result in an acidic oceanic environment with a pH of less than 6.2. This precludes the formation of siderite, usually expected to be the first major carbonate mineral to precipitate. We conclude that extensive interaction between an atmosphere dominated by carbon dioxide and a lasting sulphate- and iron-enriched acidic ocean on early Mars is a plausible explanation for the observed absence of carbonates.     

Perennial water ice identified in the south polar cap of Mars

The inventory of water and carbon dioxide reservoirs on Mars are important clues for understanding the geological, climatic and potentially exobiological evolution of the planet. From the early mapping observation of the permanent ice caps on the martian poles, the northern cap was believed to be mainly composed of water ice, whereas the southern cap was thought to be constituted of carbon dioxide ice. However, recent missions (NASA missions Mars Global Surveyor and Odyssey) have revealed surface structures, altimetry profiles, underlying buried hydrogen, and temperatures of the south polar regions that are thermodynamically consistent with a mixture of surface water ice and carbon dioxide. Here we present the first direct identification and mapping of both carbon dioxide and water ice in the martian high southern latitudes, at a resolution of 2 km, during the local summer, when the extent of the polar ice is at its minimum. We observe that this south polar cap contains perennial water ice in extended areas: as a small admixture to carbon dioxide in the bright regions; associated with dust, without carbon dioxide, at the edges of this bright cap; and, unexpectedly, in large areas tens of kilometres away from the bright cap.     

Early geochemical environment of Mars as determined from thermodynamics of phyllosilicates

Images of geomorphological features that seem to have been produced by the action of liquid water have been considered evidence for wet surface conditions on early Mars. Moreover, the recent identification of large deposits of phyllosilicates, associated with the ancient Noachian terrains suggests long-timescale weathering of the primary basaltic crust by liquid water. It has been proposed that a greenhouse effect resulting from a carbon-dioxide-rich atmosphere sustained the temperate climate required to maintain liquid water on the martian surface during the Noachian. The apparent absence of carbonates and the low escape rates of carbon dioxide, however, are indicative of an early martian atmosphere with low levels of carbon dioxide. Here we investigate the geochemical conditions prevailing on the surface of Mars during the Noachian period using calculations of the aqueous equilibria of phyllosilicates. Our results show that Fe3+-rich phyllosilicates probably precipitated under weakly acidic to alkaline pH, an environment different from that of the following period, which was dominated by strongly acid weathering that led to the sulphate deposits identified on Mars. Thermodynamic calculations demonstrate that the oxidation state of the martian surface was already high, supporting early escape of hydrogen. Finally, equilibrium with carbonates implies that phyllosilicate precipitation occurs preferentially at a very low partial pressure of carbon dioxide. We suggest that the possible absence of Noachian carbonates more probably resulted from low levels of atmospheric carbon dioxide, rather than primary acidic conditions. Other greenhouse gases may therefore have played a part in sustaining a warm and wet climate on the early Mars.     

Indirect radiative forcing of climate change through ozone effects on the land-carbon sink

The evolution of the Earth's climate over the twenty-first century depends on the rate at which anthropogenic carbon dioxide emissions are removed from the atmosphere by the ocean and land carbon cycles. Coupled climate-carbon cycle models suggest that global warming will act to limit the land-carbon sink, but these first generation models neglected the impacts of changing atmospheric chemistry. Emissions associated with fossil fuel and biomass burning have acted to approximately double the global mean tropospheric ozone concentration, and further increases are expected over the twenty-first century. Tropospheric ozone is known to damage plants, reducing plant primary productivity and crop yields, yet increasing atmospheric carbon dioxide concentrations are thought to stimulate plant primary productivity. Increased carbon dioxide and ozone levels can both lead to stomatal closure, which reduces the uptake of either gas, and in turn limits the damaging effect of ozone and the carbon dioxide fertilization of photosynthesis. Here we estimate the impact of projected changes in ozone levels on the land-carbon sink, using a global land carbon cycle model modified to include the effect of ozone deposition on photosynthesis and to account for interactions between ozone and carbon dioxide through stomatal closure. For a range of sensitivity parameters based on manipulative field experiments, we find a significant suppression of the global land-carbon sink as increases in ozone concentrations affect plant productivity. In consequence, more carbon dioxide accumulates in the atmosphere. We suggest that the resulting indirect radiative forcing by ozone effects on plants could contribute more to global warming than the direct radiative forcing due to tropospheric ozone increases.     

The formation of cubic ice under conditions relevant to Earth's atmosphere

An important mechanism for ice cloud formation in the Earth's atmosphere is homogeneous nucleation of ice in aqueous droplets, and this process is generally assumed to produce hexagonal ice. However, there are some reports that the metastable crystalline phase of ice, cubic ice, may form in the Earth's atmosphere. Here we present laboratory experiments demonstrating that cubic ice forms when micrometre-sized droplets of pure water and aqueous solutions freeze homogeneously at cooling rates approaching those found in the atmosphere. We find that the formation of cubic ice is dominant when droplets freeze at temperatures below 190 K, which is in the temperature range relevant for polar stratospheric clouds and clouds in the tropical tropopause region. These results, together with heat transfer calculations, suggest that cubic ice will form in the Earth's atmosphere. If there were a significant fraction of cubic ice in some cold clouds this could increase their water vapour pressure, and modify their microphysics and ice particle size distributions. Under specific conditions this may lead to enhanced dehydration of the tropopause region.     

Global warming and climate forcing by recent albedo changes on Mars

For hundreds of years, scientists have tracked the changing appearance of Mars, first by hand drawings and later by photographs. Because of this historical record, many classical albedo patterns have long been known to shift in appearance over time. Decadal variations of the martian surface albedo are generally attributed to removal and deposition of small amounts of relatively bright dust on the surface. Large swaths of the surface (up to 56 million km2) have been observed to darken or brighten by 10 per cent or more. It is unknown, however, how these albedo changes affect wind circulation, dust transport and the feedback between these processes and the martian climate. Here we present predictions from a Mars general circulation model, indicating that the observed interannual albedo alterations strongly influence the martian environment. Results indicate enhanced wind stress in recently darkened areas and decreased wind stress in brightened areas, producing a positive feedback system in which the albedo changes strengthen the winds that generate the changes. The simulations also predict a net annual global warming of surface air temperatures by approximately 0.65 K, enhancing dust lifting by increasing the likelihood of dust devil generation. The increase in global dust lifting by both wind stress and dust devils may affect the mechanisms that trigger large dust storm initiation, a poorly understood phenomenon, unique to Mars. In addition, predicted increases in summertime air temperatures at high southern latitudes would contribute to the rapid and steady scarp retreat that has been observed in the south polar residual ice for the past four Mars years. Our results suggest that documented albedo changes affect recent climate change and large-scale weather patterns on Mars, and thus albedo variations are a necessary component of future atmospheric and climate studies.     

Albedo of the south pole on Mars determined by topographic forcing of atmosphere dynamics

The nature of the martian south polar cap has remained enigmatic since the first spacecraft observations. In particular, the presence of a perennial carbon dioxide ice cap, the formation of a vast area of black 'slab ice' known as the Cryptic region and the asymmetric springtime retreat of the cap have eluded explanation. Here we present observations and climate modelling that indicate the south pole of Mars is characterized by two distinct regional climates that are the result of dynamical forcing by the largest southern impact basins, Argyre and Hellas. The style of surface frost deposition is controlled by these regional climates. In the cold and stormy conditions that exist poleward of 60 degrees S and extend 180 degrees in longitude west from the Mountains of Mitchel (approximately 30 degrees W), surface frost accumulation is dominated by precipitation. In the opposite hemisphere, the polar atmosphere is relatively warm and clear and frost accumulation is dominated by direct vapour deposition. It is the differences in these deposition styles that determine the cap albedo.     

Impact erosion of the primordial atmosphere of Mars

Abundant geomorphic evidence for fluvial processes on the surface of Mars suggests that during the era of heavy bombardment, Mars's atmospheric pressure was high enough for liquid water to flow on the surface. Many authors have proposed mechanisms by which Mars could have lost (or sequestered) an earlier, thicker atmosphere but none of these proposals has gained general acceptance. Here we examine the process of atmospheric erosion by impacts and show that it may account for an early episode of atmosphere loss from Mars. On the basis of this model, the primordial atmospheric pressure on Mars must have been in the vicinity of 1 bar, barring other sources or sinks of CO2. Current impact fluxes are too small to erode significantly the present martian atmosphere.     

Recent ice-rich deposits formed at high latitudes on Mars by sublimation of unstable equatorial ice during low obliquity

Observations from the gamma-ray spectrometer instrument suite on the Mars Odyssey spacecraft have been interpreted as indicating the presence of vast reservoirs of near-surface ice in high latitudes of both martian hemispheres. Ice concentrations are estimated to range from 70 per cent at 60 degrees latitude to 100 per cent near the poles, possibly overlain by a few centimetres of ice-free material in most places. This result is supported by morphological evidence of metres-thick layered deposits that are rich in water-ice and periglacial-like features found only at high latitudes. Diffusive exchange of water between the pore space of the regolith and the atmosphere has been proposed to explain this distribution, but such a degree of concentration is difficult to accommodate with such processes. Alternatively, there are suggestions that ice-rich deposits form by transport of ice from polar reservoirs and direct redeposition in high latitudes during periods of higher obliquity, but these results have been difficult to reproduce with other models. Here we propose instead that, during periods of low obliquity (less than 25 degrees), high-latitude ice deposits form in both hemispheres by direct deposition of ice, as a result of sublimation from an equatorial ice reservoir that formed earlier, during a prolonged high-obliquity excursion. Using the ice accumulation rates estimated from global climate model simulations we show that, over the past ten million years, large variations of Mars' obliquity have allowed the formation of such metres-thick, sedimentary layered deposits in high latitude and polar regions.     

Biosignatures as revealed by spectropolarimetry of Earthshine

Low-resolution intensity spectra of Earth's atmosphere obtained from space reveal strong signatures of life ('biosignatures'), such as molecular oxygen and methane with abundances far from chemical equilibrium, as well as the presence of a 'red edge' (a sharp increase of albedo for wavelengths longer than 700?nm) caused by surface vegetation. Light passing through the atmosphere is strongly linearly polarized by scattering (from air molecules, aerosols and cloud particles) and by reflection (from oceans and land). Spectropolarimetric observations of local patches of Earth's sky light from the ground contain signatures of oxygen, ozone and water, and are used to characterize the properties of clouds and aerosols. When applied to exoplanets, ground-based spectropolarimetry can better constrain properties of atmospheres and surfaces than can standard intensity spectroscopy. Here we report disk-integrated linear polarization spectra of Earthshine, which is sunlight that has been first reflected by Earth and then reflected back to Earth by the Moon. The observations allow us to determine the fractional contribution of clouds and ocean surface, and are sensitive to visible areas of vegetation as small as 10 per cent. They represent a benchmark for the diagnostics of the atmospheric composition, mean cloud height and surfaces of exoplanets.     

The interstellar N2 abundance towards HD 124314 from far-ultraviolet observations

The abundance of interstellar molecular nitrogen (N2) is of considerable importance: models of steady-state gas-phase interstellar chemistry, together with millimetre-wavelength observations of interstellar N2H+ in dense molecular clouds predict that N2 should be the most abundant nitrogen-bearing molecule in the interstellar medium. Previous attempts to detect N2 absorption in the far-ultraviolet or infrared (ice features) have hitherto been unsuccessful. Here we report the detection of interstellar N2 at far-ultraviolet wavelengths towards the moderately reddened star HD 124314 in the constellation of Centaurus. The N2 column density is larger than expected from models of diffuse clouds and significantly smaller than expected for dense molecular clouds. Moreover, the N2 abundance does not explain the observed variations in the abundance of atomic nitrogen (N I) towards high-column-density sightlines, implying that the models of nitrogen chemistry in the interstellar medium are incomplete.     

Evidence of atmospheric sulphur in the martian regolith from sulphur isotopes in meteorites

Sulphur is abundant at the martian surface, yet its origin and evolution over time remain poorly constrained. This sulphur is likely to have originated in atmospheric chemical reactions, and so should provide records of the evolution of the martian atmosphere, the cycling of sulphur between the atmosphere and crust, and the mobility of sulphur in the martian regolith. Moreover, the atmospheric deposition of oxidized sulphur species could establish chemical potential gradients in the martian near-surface environment, and so provide a potential energy source for chemolithoautotrophic organisms. Here we present measurements of sulphur isotopes in oxidized and reduced phases from the SNC meteorites--the group of related achondrite meteorites believed to have originated on Mars--together with the results of laboratory photolysis studies of two important martian atmospheric sulphur species (SO2 and H2S). The photolysis experiments can account for the observed sulphur-isotope compositions in the SNC meteorites, and so identify a mechanism for producing large abiogenic 34S fractionations in the surface sulphur reservoirs. We conclude that the sulphur data from the SNC meteorites reflects deposition of oxidized sulphur species produced by atmospheric chemical reactions, followed by incorporation, reaction and mobilization of the sulphur within the regolith.     

CO2 jets formed by sublimation beneath translucent slab ice in Mars' seasonal south polar ice cap

The martian polar caps are among the most dynamic regions on Mars, growing substantially in winter as a significant fraction of the atmosphere freezes out in the form of CO2 ice. Unusual dark spots, fans and blotches form as the south-polar seasonal CO2 ice cap retreats during spring and summer. Small radial channel networks are often associated with the location of spots once the ice disappears. The spots have been proposed to be simply bare, defrosted ground; the formation of the channels has remained uncertain. Here we report infrared and visible observations that show that the spots and fans remain at CO2 ice temperatures well into summer, and must be granular materials that have been brought up to the surface of the ice, requiring a complex suite of processes to get them there. We propose that the seasonal ice cap forms an impermeable, translucent slab of CO2 ice that sublimates from the base, building up high-pressure gas beneath the slab. This gas levitates the ice, which eventually ruptures, producing high-velocity CO2 vents that erupt sand-sized grains in jets to form the spots and erode the channels. These processes are unlike any observed on Earth.     

Effect of CH_3OOH on the atmospheric concentration of OH radicals

Peroxides play an i mportant role in atmosphericchemistry,because they are not only amongthe prin-ciple oxidants in the chemical conversion of O3andSO2,but also act as an atmospheric sink and tempo-rary reservoir for i mportant oxidizing radicals such asOH, HO2and RO2[1 ,2]. With the development ofmeasurement techniques , several organic peroxideswere identified in the atmosphere in addition to hy-drogen peroxide (H2O2)[3—5]. And among these or-ganic peroxides , methyl hydroperoxide ( MH…     

Partitioning of oxygen during core formation on the Earth and Mars

Core formation on the Earth and Mars involved the physical separation of metal and silicate, most probably in deep magma oceans. Although core-formation models explain many aspects of mantle geochemistry, they have not accounted for the large differences observed between the compositions of the mantles of the Earth (approximately 8 wt% FeO) and Mars (approximately 18 wt% FeO) or the smaller mass fraction of the martian core. Here we explain these differences as a consequence of the solubility of oxygen in liquid iron-alloy increasing with increasing temperature. We assume that the Earth and Mars both accreted from oxidized chondritic material. In a terrestrial magma ocean, 1,200-2,000 km deep, high temperatures resulted in the extraction of FeO from the silicate magma ocean owing to high solubility of oxygen in the metal. Lower temperatures of a martian magma ocean resulted in little or no extraction of FeO from the mantle, which thus remains FeO-rich. The FeO extracted from the Earth's magma ocean may have contributed to chemical heterogeneities in the lowermost mantle, a FeO-rich D" layer and the light element budget of the core.     

Thermal history of Mars inferred from orbital geochemistry of volcanic provinces

Reconstruction of the geological history of Mars has been the focus of considerable attention over the past four decades, with important discoveries being made about variations in surface conditions. However, despite a significant increase in the amount of data related to the morphology, mineralogy and chemistry of the martian surface, there is no clear global picture of how magmatism has evolved over time and how these changes relate to the internal workings and thermal evolution of the planet. Here we present geochemical data derived from the Gamma Ray Spectrometer on board NASA's Mars Odyssey spacecraft, focusing on twelve major volcanic provinces of variable age. Our analysis reveals clear trends in composition that are found to be consistent with varying degrees of melting of the martian mantle. There is evidence for thickening of the lithosphere (17-25?km?Gyr(-1)) associated with a decrease in mantle potential temperature over time (30-40?K?Gyr(-1)). Our inferred thermal history of Mars, unlike that of the Earth, is consistent with simple models of mantle convection.     

Mars' core and magnetism.

The detection of strongly magnetized ancient crust on Mars is one of the most surprising outcomes of recent Mars exploration, and provides important insight about the history and nature of the martian core. The iron-rich core probably formed during the hot accretion of Mars approximately 4.5 billion years ago and subsequently cooled at a rate dictated by the overlying mantle. A core dynamo operated much like Earth's current dynamo, but was probably limited in duration to several hundred million years. The early demise of the dynamo could have arisen through a change in the cooling rate of the mantle, or even a switch in convective style that led to mantle heating. Presently, Mars probably has a liquid, conductive outer core and might have a solid inner core like Earth.     

Vapour undersaturation in primitive mid-ocean-ridge basalt and the volatile content of Earth's upper mantle

The analysis of volatiles in magmatic systems can be used to constrain the volatile content of the Earth's mantle and the influence that magmatic degassing has on the chemistry of the oceans and the atmosphere. But most volatile elements have very low solubilities in magmas at atmospheric pressure, and therefore virtually all erupted lavas are degassed and do not retain their primary volatile signatures. Here we report the undersaturated pre-eruptive volatile content for a suite of mid-ocean-ridge basalts from the Siqueiros intra-transform spreading centre. The undersaturation leads to correlations between volatiles and refractory trace elements that provide new constraints on volatile abundances and their behaviour in the upper mantle. Our data generate improved limits on the abundances of carbon dioxide, water, fluorine, sulphur and chlorine in the source of normal mid-ocean-ridge basalt. The incompatible behaviour of carbon dioxide, together with the CO(2)/Nb and CO(2)/Cl ratios, permit estimates of primitive carbon dioxide and chlorine to be made for degassed and chlorine-contaminated mid-ocean-ridge basalt magmas, and hence constrain degassing and contamination histories of mid-ocean ridges.     

High-resolution subsurface water-ice distributions on Mars

Theoretical models indicate that water ice is stable in the shallow subsurface (depths of <1-2 m) of Mars at high latitudes. These models have been mainly supported by the observed presence of large concentrations of hydrogen detected by the Gamma Ray Spectrometer suite of instruments on the Mars Odyssey spacecraft. The models and measurements are consistent with a water-ice table that steadily increases in depth with decreasing latitude. More detailed modelling has predicted that the depth at which water ice is stable can be highly variable, owing to local surface heterogeneities such as rocks and slopes, and the thermal inertia of the ground cover. Measurements have, however, been limited to the footprint (several hundred kilometres) of the Gamma Ray Spectrometer suite, preventing the observations from documenting more detailed water-ice distributions. Here I show that by observing the seasonal temperature response of the martian surface with the Thermal Emission Imaging System on the Mars Odyssey spacecraft, it is possible to observe such heterogeneities at subkilometre scale. These observations show significant regional and local water-ice depth variability, and, in some cases, support distributions in the subsurface predicted by atmospheric exchange and vapour diffusion models. The presence of water ice where it follows the depth of stability under current climatic conditions implies an active martian water cycle that responds to orbit-driven climate cycles. Several regions also have apparent deviations from the theoretical stability level, indicating that additional factors influence the ice-table depth. The high-resolution measurements show that the depth to the water-ice table is highly variable within the potential Phoenix spacecraft landing ellipses, and is likely to be variable at scales that may be sampled by the spacecraft.     

Weather and climate on Mars.

Imagine a planet very much like the Earth, with similar size, rotation rate and inclination of rotation axis, possessing an atmosphere and a solid surface, but lacking oceans and dense clouds of liquid water. We might expect such a desert planet to be dominated by large variations in day-night and winter-summer weather. Dust storms would be common. Observations and simulations of martian climate confirm these expectations and provide a wealth of detail that can help resolve problems of climate evolution.