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.     

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.     

无机水合盐中水的状态与相变潜热的关系

选择3种典型的样品CuSO₄·5H₂O (胆矾)、Na₂HPO₄·12H₂O和Na₂SO₄·10H₂O (芒硝)进行测试, 利用热重?差式扫描量热(TG-DSC)同步测试仪检测样品的热效应, 并通过拉曼光谱进行结构分析。结果表明, 对于在相变点以脱结晶水为主的相变材料, 水在晶体中的状态不同, 会使相变材料在脱水过程中产生不同的热效应, 直接影响相变潜热的大小, 但并非所有无机水合盐的相变潜热都随着结晶水数目增多而增大。大部分无机水合盐所带结晶水数目越少, 每摩尔水的平均潜热越高。通过对在相变点脱去部分结晶水的Na₂HPO₄·12H₂O与在相变点脱去全部结晶水的Na₂SO₄·10H₂O的对比研究认为, 对于前人关于无机水合盐的潜热大小与结晶水数目之间普遍存在定量关系这一结论是否具有普适性还有待进一步研究。     

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.     

Geochemical evidence for magmatic water within Mars from pyroxenes in the Shergotty meteorite

Observations of martian surface morphology have been used to argue that an ancient ocean once existed on Mars. It has been thought that significant quantities of such water could have been supplied to the martian surface through volcanic outgassing, but this suggestion is contradicted by the low magmatic water content that is generally inferred from chemical analyses of igneous martian meteorites. Here, however, we report the distributions of trace elements within pyroxenes of the Shergotty meteorite--a basalt body ejected 175 million years ago from Mars--as well as hydrous and anhydrous crystallization experiments that, together, imply that water contents of pre-eruptive magma on Mars could have been up to 1.8%. We found that in the Shergotty meteorite, the inner cores of pyroxene minerals (which formed at depth in the martian crust) are enriched in soluble trace elements when compared to the outer rims (which crystallized on or near to the martian surface). This implies that water was present in pyroxenes at depth but was largely lost as pyroxenes were carried to the surface during magma ascent. We conclude that ascending magmas possibly delivered significant quantities of water to the martian surface in recent times, reconciling geologic and petrologic constraints on the outgassing history of Mars.     

Evidence for magmatic evolution and diversity on Mars from infrared observations

Compositional mapping of Mars at the 100-metre scale with the Mars Odyssey Thermal Emission Imaging System (THEMIS) has revealed a wide diversity of igneous materials. Volcanic evolution produced compositions from low-silica basalts to high-silica dacite in the Syrtis Major caldera. The existence of dacite demonstrates that highly evolved lavas have been produced, at least locally, by magma evolution through fractional crystallization. Olivine basalts are observed on crater floors and in layers exposed in canyon walls up to 4.5 km beneath the surface. This vertical distribution suggests that olivine-rich lavas were emplaced at various times throughout the formation of the upper crust, with their growing inventory suggesting that such ultramafic (picritic) basalts may be relatively common. Quartz-bearing granitoid rocks have also been discovered, demonstrating that extreme differentiation has occurred. These observations show that the martian crust, while dominated by basalt, contains a diversity of igneous materials whose range in composition from picritic basalts to granitoids rivals that found on the Earth.     

Jarosite as an indicator of water-limited chemical weathering on Mars

The Mars Exploration Rover Opportunity identified the ferric sulphate mineral jarosite and possible relicts of gypsum at the Meridiani Planum landing site. On Earth, jarosite has been found to form in acid mine drainage environments, during the oxidation of sulphide minerals, and during alteration of volcanic rocks by acidic, sulphur-rich fluids near volcanic vents. Jarosite formation is thus thought to require a wet, oxidizing and acidic environment. But jarosite on Earth only persists over geologically relevant time periods in arid environments because it rapidly decomposes to produce ferric oxyhydroxides in more humid climates. Here we present equilibrium thermodynamic reaction-path simulations that constrain the range of possible conditions under which such aqueous alteration phases are likely to have formed on Mars. These calculations simulate the chemical weathering of basalt at relevant martian conditions. We conclude that the presence of jarosite combined with residual basalt at Meridiani Planum indicates that the alteration process did not proceed to completion, and that following jarosite formation, arid conditions must have prevailed.     

Recent and episodic volcanic and glacial activity on Mars revealed by the High Resolution Stereo Camera

The large-area coverage at a resolution of 10-20 metres per pixel in colour and three dimensions with the High Resolution Stereo Camera Experiment on the European Space Agency Mars Express Mission has made it possible to study the time-stratigraphic relationships of volcanic and glacial structures in unprecedented detail and give insight into the geological evolution of Mars. Here we show that calderas on five major volcanoes on Mars have undergone repeated activation and resurfacing during the last 20 per cent of martian history, with phases of activity as young as two million years, suggesting that the volcanoes are potentially still active today. Glacial deposits at the base of the Olympus Mons escarpment show evidence for repeated phases of activity as recently as about four million years ago. Morphological evidence is found that snow and ice deposition on the Olympus construct at elevations of more than 7,000 metres led to episodes of glacial activity at this height. Even now, water ice protected by an insulating layer of dust may be present at high altitudes on Olympus Mons.     

硫酸盐对聚羧酸减水剂吸附-分散性能的影响

系统研究了硫酸盐对掺聚羧酸减水剂水泥浆体流变性及水化性能的影响.结果表明:硫酸盐降低了聚羧酸减水剂在水泥颗粒表面的吸附量,削弱了聚羧酸减水剂对水泥浆体的分散作用.随着硫酸盐掺量的增加,聚羧酸减水剂分散性能下降.少量硫酸盐延缓了水化加速期最大水化放热速率峰的出现,并且提高了最大水化放热速率.而大量硫酸盐则使得水泥水化诱导期缩短,最大水化速率峰显著提前.大量硫酸盐的加入促进了水泥浆体中钙矾石(AFt)的生成,削弱了水化铝酸钙(CAH)的生成.MgSO4对于水泥浆体中水化产物生成的促进作用最明显.掺加MgSO4的水泥水化产物中含有大量细丝状水化硫铝酸盐产物.MgSO4对水泥水化具有显著延缓作用,水化产物结晶成核作用较缓慢,从而使得水化产物生成及分布更加均匀,形状更加细小.     

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.     

The crust and mantle of Mars.

Clues to the history of Mars are recorded in the chemistry and structure of the planet's crust and mantle. The mantle is the rocky, interior region of the planet that transports heat generated during accretion and subsequent core formation. The crust formed by melting of the upper mantle, and has been shaped and re-distributed by impact, volcanism, mantle flow and erosion. Observations point to a dynamically active interior in the early phases of martian history, followed by a rapid fall-off in heat transport that significantly influenced the geological, geophysical and geochemical evolution of the planet, including the history of water and climate.     

Indication of drier periods on Mars from the chemistry and mineralogy of atmospheric dust

The ubiquitous atmospheric dust on Mars is well mixed by periodic global dust storms, and such dust carries information about the environment in which it once formed and hence about the history of water on Mars. The Mars Exploration Rovers have permanent magnets to collect atmospheric dust for investigation by instruments on the rovers. Here we report results from M?ssbauer spectroscopy and X-ray fluorescence of dust particles captured from the martian atmosphere by the magnets. The dust on the magnets contains magnetite and olivine; this indicates a basaltic origin of the dust and shows that magnetite, not maghemite, is the mineral mainly responsible for the magnetic properties of the dust. Furthermore, the dust on the magnets contains some ferric oxides, probably including nanocrystalline phases, so some alteration or oxidation of the basaltic dust seems to have occurred. The presence of olivine indicates that liquid water did not play a dominant role in the processes that formed the atmospheric dust.     

Keggin型有机膦钨杂多酸的制备、结构表征和酸量的电位滴定法测定

首次以2-氨乙基膦酸及其N-取代物为配位中心,制得一系列有机膦钨杂多酸.由IR光谱、重量分析、扫描电镜能谱分析和C,H,N元素分析相结合确定该系列杂多酸一级结构均为Keggin结构,通式为R     

C3S和β-C2S单矿物在水蒸气中的水化

研究了水泥熟料单矿物C     

螺旋藻_S_platensis_S_maxima_培养液的筛选

通过用粗海盐取代Ｚａｒｒｏｕｋ培养液中部分微量元素，得到钝顶螺旋藻（Ｓ．ｐｌａｔｅｎｓｉｓ）和巨大螺旋藻（Ｓ．ｍａｘｉｍａ）的简化培养基：用１．０ｇ／Ｌ粗海盐代替Ｚａｒｒｏｕｋ培养液中Ａ＿５和Ｂ＿６液成分，ＭｇＳＯ３·７Ｈ２Ｏ剂量为０．２５ｇ／Ｌ，其它成分同Ｚａｒｒｏｕｋ培养液．     

Martian stepped-delta formation by rapid water release

Deltas and alluvial fans preserved on the surface of Mars provide an important record of surface water flow. Understanding how surface water flow could have produced the observed morphology is fundamental to understanding the history of water on Mars. To date, morphological studies have provided only minimum time estimates for the longevity of martian hydrologic events, which range from decades to millions of years. Here we use sand flume studies to show that the distinct morphology of martian stepped (terraced) deltas could only have originated from a single basin-filling event on a timescale of tens of years. Stepped deltas therefore provide a minimum and maximum constraint on the duration and magnitude of some surface flows on Mars. We estimate that the amount of water required to fill the basin and deposit the delta is comparable to the amount of water discharged by large terrestrial rivers, such as the Mississippi. The massive discharge, short timescale, and the associated short canyon lengths favour the hypothesis that stepped fans are terraced delta deposits draped over an alluvial fan and formed by water released suddenly from subsurface storage.     

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.     

两种长链共轭体系非线性光学性质的计算及基组研究

本文以aug-cc-pVTZ基组作为标准,用不同大小的基组分别对两种长链共轭化合物:聚炔类化合物H(C≡C)nH、聚乙炔化合物(PA) H(CH＝CH)nH（n=2～10）的非线性光学性质进行计算,并对基组进行逐一的比较、筛选,最后得到了较小的且计算结果较好的6-31 G*基组。在计算中还发现在计算不同的长链聚合物时,在HF和MP2水平下计算得到的二阶超极化率有显著的不同。     

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.