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At least 55 records · Page 3

Acid Sulfate Alteration in Gusev Crater, Mars

The Mars Exploration Rover (MER) Spirit landed on the Gusev Crater plains west of the Columbia Hills in January, 2004, during the Martian summer (sol 0; sol = 1 Martian day = 24 hr 40 min). Spirit explored the Columbia Hills of Gusev Crater in the vicinity of Home Plate at the onset on its second winter (sol approximately 900) until the onset of its fourth winter (sol approximately 2170). At that time, Spirit became mired in a deposit of fined-grained and sulfate-rich soil with dust-covered solar panels and unfavorable pointing of the solar arrays toward the sun. Spirit has not communicated with the Earth since sol 2210 (January, 2011). Like its twin rover Opportunity, which landed on the opposite side of Mars at Meridiani Planum, Spirit has an Alpha Particle X-Ray Spectrometer (APXS) instrument for chemical analyses and a Moessbauer spectrometer (MB) for measurement of iron redox state, mineralogical speciation, and quantitative distribution among oxidation (Fe(3+)/sigma Fe) and coordination (octahedral versus tetrahedral) states and mineralogical speciation (e.g., olivine, pyroxene, ilmenite, carbonate, and sulfate). The concentration of SO3 in Gusev rocks and soils varies from approximately 1 to approximately 34 wt%. Because the APXS instrument does not detect low atomic number elements (e.g., H and C), major-element oxide concentrations are normalized to sum to 100 wt%, i.e., contributions of H2O, CO2, NO2, etc. to the bulk composition care not considered. The majority of Gusev samples have approximately 6 plus or minus 5 wt% SO3, but there is a group of samples with high SO3 concentrations (approximately 30 wt%) and high total iron concentrations (approximately 20 wt%). There is also a group with low total Fe and SO3 concentrations that is also characterized by high SiO2 concentrations (greater than 70 wt%). The trend labeled "Basaltic Soil" is interpreted as mixtures in variable proportions between unaltered igneous material and oxidized and SO3-rich basaltic dust. The Moessbauer parameters are not definitive for mineralogical speciation (other than octahedrally-coordinated Fe(3+) but are consistent with a schwertmannite-like phase (i.e., a nanophase ferric oxide). The high oxidation state and values of Moessbauer parameters (center shift and quadrupole splitting) for the high-SO3 samples imply ferric sulfate (i.e., oxidized sulfur), although the hydration state cannot be constrained. In no case is there an excess of SO3 over available cations (i.e., no evidence for elemental sulfur), and Fe sulfide (pyrite) has been detected in only one Gusev sample. The presence of both high-SiO2 (and low total iron and SO3) and high SO3 (and high total iron as ferric sulfate) can be accommodated by a two-step geochemical model developed with the Geochemist's Workbench. (1) Step 1 is anoxic acid sulfate leaching of Martian basalt at high water-to rock ratios (greater than 70). The result is a high-SiO2 residue0, and anoxic conditions are required to solubilize Fe as Fe(2+). (2) Step 2 is the oxic precipitation of sulfate salts from the leachate. Oxic conditions are required to produce the high concentrations of ferric sulfate with minor Mg-sulfates and no detectable Fe(2+)-sulfates.

Morris, R. V.↗

Acid-Sulfate Alteration at Gusev Crater and Across Mars: High-SiO2 Residues and Ferric Sulfate Precipitates

The Mars Exploration Rover Spirit ended its mission in Gusev crater on sol 2210 after it had become stuck in a deposit of fined-grained and sulfate rich soil with dust covered solar panels unfavorably pointed toward the sun. Final analysis of remaining data from Spirit's Moessbauer spectrometer (Fe redox and mineralogy) for sols 1529 through 2071 is now complete. We focus here on chemical (APXS) and MB data for targets having high-SiO2 or high-SO3 and process link the targets through mixing and geochemical modelling to an acid-sulfate system centered at Home Plate, which is considered to be a hydrovolcanic complex.

Morris, R. V.↗

Sulfur and Metal Fertilization of the Lower Continental Crust

Mantle-derived melts and metasomatic fluids are considered to be important in the transport and distribution of trace elements in the subcontinental lithospheric mantle. However, the mechanisms that facilitate sulfur and metal transfer from the upper mantle into the lower continental crust are poorly constrained. This study addresses this knowledge gap by examining a series of sulfide- and hydrous mineral-rich alkaline mafic-ultramafic pipes that intruded the lower continental crust of the Ivrea-Verbano Zone in the Italian Western Alps. The pipes are relatively small (<300 m diameter) and primarily composed of a matrix of subhedral to anhedral amphibole (pargasite), phlogopite and orthopyroxene that enclose sub-centimeter-sized grains of olivine. The 1 to 5 m wide rim portions of the pipes locally contain significant blebby and disseminated Fe-Ni-Cu-PGE sulfide mineralization.Stratigraphic relationships, mineral chemistry, geochemical modeling and phase equilibria suggest that the pipes represent open-ended conduits within a large magmatic plumbing system. The earliest formed pipe rocks were olivine-rich cumulates that reacted with hydrous melts to produce orthopyroxene, amphibole and phlogopite.Sulfides precipitated as immiscible liquid droplets that were retained within a matrix of silicate crystals and scavenged metals from the percolating hydrous melt. New high-precision chemical abrasion TIMS-UPb dating of zircons from one of the pipes indicates that these pipes were emplaced at 249.1+/-0.2 Ma, following partial melting of lithospheric mantle pods that were metasomatized during the Eo-Variscan oceanic to continental subduction (approx. 420-310 Ma). The thermal energy required to generate partial melting of the metasomatized mantle was most likely derived from crustal extension, lithospheric decompression and subsequent asthenospheric rise during the orogenic collapse of the Variscan belt (<300 Ma). Unlike previous models, outcomes from this study suggest a significant temporal gap between the occurrence of mantle metasomatism, subsequent partial melting and emplacement of the pipes.We argue that this multi-stage process is a very effective mechanism to fertilize the commonly dry and refractory lower continental crust in metals and volatiles. During the four-dimensional evolution of the thermo-tectonic architecture of any given terrain, metals and volatiles stored in the lower continental crust may become available as sources for subsequent ore-forming processes, thus enhancing the prospectivity of continental block margins for a wide range of mineral systems.

Marek Locmelis↗

Organic-rich fluids in Pluto’s interior—A source of cryovolcanic activity

The highly variegated surface of Pluto revealed by the New Horizons spacecraft is composed of both volatile ices (N2, CH4, CO) and H2O ice, all of which are intrinsically colorless. The colors on Pluto reveal a non-ice component generally acknowledged to be a refractory complex organic material (tholins) produced by photolysis in the planet’s atmosphere [1], and by photolysis and radiolysis of the surface ices [2-4]. These processes have produced a range of colors from pale yellow to red to brown, and result in a variation of a factor of 10in albedo across the surface. Tholins are disordered polymer-like materials made of repeating chains of linked subunits and complex combinations of functional groups containing carbon. Nitrogen, oxygen, and other elements can be substituted in both the aliphatic and aromatic subunits. The detection of the spectral absorption of an ammoniated compound associated with surface exposures of red-colored H2O ice (herein, RAW) in the LEISA spectral mapping data from New Horizons suggests that a third source of a colored material is ejected from Pluto’s interior as a water-rich fluid(cryomagma) that rapidly freezes at the low temperature (~40K) of the surface [5,6]. The ammoniated compound is thought to be an ammonia hydrate or an ammoniated salt; the spectral data cover a limited wavelength range, resulting in ambiguity in the identification of the form of the ammonia. The distribution of RAW in the vicinity of tectonically stressed and deformed geological structures, particularly graben (fossae), is seen as the result of both fluid effusion and fountaining ejection of cryoclastic materials in Pluto’s Virgil Fossae region [5,6]. RAW is seen elsewhere on Pluto, both in association with graben complexes and on broad expanses of old surface, but primarily in zones of tectonic stress. The nature of the putative subsurface fluid is unknown, but it must have existed at relatively shallow depths such that the graben faulting could reach it. Geochemical modeling of fluids in the interiors of small planetary bodies in the outer Solar System[7] shows that ammonia-bearing H2O in contact with rock and metal components produce a rich chemical soup, including gases that can, in principle, help propel the fluid from shallow reservoirs through crustal fractures to reach the surface. An organic component of the fluid cryomagma is predicted to originate from thermal processing of the components [ref] and may be an example of one-pot synthesis of such complexes as amino acid precursors [ref].

Dale P Cruikshank↗

A Quantitative Geochemical Target for Modeling the Formation of the Earth and Moon

The past decade has been one of geochemical, isotopic, and computational advances that are bringing the laboratory measurements and computational modeling neighborhoods of the Earth-Moon community to ever closer proximity. We are now however in the position to become even better neighbors: modelers can generate testable hypthotheses for geochemists; and geochemists can provide quantitive targets for modelers. Here we present a robust example of the latter based on Cl isotope measurements of mare basalts.

Boyce, Jeremy W.↗

A hybrid model of the CO2 geochemical cycle and its application to large impact events

The effects of a large asteriod or comet impact on modern and ancient marine biospheres are analyzed. A hybrid model of the carbonate-silicate geochemical cycle, which is capable of calculating the concentrations of carbon dioxide in the atmosphere, ocean, and sedimentary rocks, is described. The differences between the Keir and Berger (1983) model and the hybrid model are discussed. Equilibrium solutions are derived for the preindustrial atmosphere/ocean system and for a system similar to that of the late Cretaceous Period. The model data reveal that globl darkening caused by a stratospheric dust veil could destroy the existing phytoplankton within a period of several weeks or months, nd the dissolution of atmospheric NO(x) compounds would lower the pH of ocean surface waters and release CO2 into the atmosphere. It is noted that the surface temperatures could be increased by several degrees and surface oceans would be uninhabitable for calcaerous organisms for approximately 20 years.

Kasting, J. F.↗

Chemical mixing model studies of lunar orbital geochemical data - Apollo 16 and 17 highlands compositions

Chemical mixing model studies of lunar geochemical data for the central and Taurus-Littrow lunar highlands were performed utilizing pristine highland rock types as end member compositions. The central highlands show considerable diversity in composition; anorthosite is the principal rock type in the Apollo 16/Descartes region, while norite predominates in the highlands west of the landing site. This change in crustal composition is coincident with a major color boundary seen in earth-based multispectral data and probably represents the presence of distinct geochemical provinces within the central highlands. The Taurus-Littrow highlands are dominated by norite; anorthosite is far less abundant than in the central highlands. This suggests that the impact target for the Serenitatis basin was different than that of the Nectaris basin and further strengthens the hypothesis that the lunar highlands are petrologically heterogeneous on a regional basis. It is suggested that the lunar highlands should be viewed in terms of geochemical provinces that have undergone distinct and complex igneous and impact histories.

Spudis, P. D.↗

Chemical modeling constraints on Martian surface mineralogies formed in an early, warm, wet climate, and speculations on the occurrence of phosphate minerals in the Martian regolith

This is one in a series of reports summarizing our chemical modeling studies of water-rock-gas interactions at the martian surface through time. The purpose of these studies is to place constraints on possible mineralogies formed at the martian surface and to model the geochemical implications of martian surficial processes proposed by previous researchers. Plumlee and Ridley summarize geochemical processes that may have occurred as a result of inferred volcano- and impact-driven hydrothermal activity on Mars. DeBraal et al. model the geochemical aspects of water-rock interactions and water evaporation near 0 C, as a prelude to future calculations that will model sub-0 C brine-rock-clathrate interactions under the current martian climate. In this report, we discuss reaction path calculations that model chemical processes that may have occurred at the martian surface in a postulated early, warm, wet climate. We assume a temperature of 25 C in all our calculations. Processes we model here include (1) the reaction of rainwater under various ambient CO2 and O2 pressures with basaltic rocks at the martian surface, (2) the formation of acid rain by volcanic gases such as HCl and SO2, (3) the reactions of acid rain with basaltic surficial materials, and (4) evaporation of waters resulting from rainwater-basalt interactions.

Plumlee, Geoffrey S.↗

Petrogenetic modeling of Hawaiian tholeiitic basalts - A geochemical approach

The abundances of 29 elements in 33 samples of tholeiitic basalts from five volcanoes in Hawaii are determined by neutron-activation analysis; the results are presented in tables and graphs with the data of Murali et al. (1977) for a sixth volcano and characterized in detail; and geochemical partial-melting models are constructed to explain the origin of these basalts. The models proposed are based on olivine crystallization from three distinct source compositions (determined from the REE and Sc partitioning) and correspond to the volcano groups Mauna Kea, Kohala, and Kilauea; Mauna Loa and Lanai; and Koolau.

Budahn, J. R.↗

The Little Ice Age and Human-Environmental Interactions in the Central Balkans: Insights from a New Serbian Paleorecord

This paper presents a 600-year well-dated, high-resolution Central Balkan paleo-record including the Little Ice Age (LIA; 1450-850 CE). Utilizing pollen-based REVEALS modelling estimates, geochemical indicators, rarefaction analyses and the AMS 14C-based Bacon age model, this first-hand record from the Sava Basin reveals the transformation of the Central Balkan landscape involving linkages between changing climatic and socio-political regimes. The pre-LIA interval (1370-1418 CE) in the Sava Region reveals a wooded steppe and increased cultivation under warmer/stable climatic and socio-political conditions. In contrast, the LIA interval in the region is expressed through continuous transitions between forest and grassland, extensive land erosion and stressed agriculture, potentially as a collective artifact of the climatic variability and human impact associated with socio- political stressors of the time. The post-LIA/Industrial Era interval (1850-2012 CE) in the Sava Region shows an overall increase in woodland as well as agriculture following the exit of the Ottomans. However, increased population pressures and the subsequent onset of the Industrial Revolution as well as increased trade led to intense deforestation throughout the 20th Century, which continued during the Socialist period.

Societal impacts of climate change↗

Comments on the BLAG model - The carbonate-silicate geochemical cycle and its effect on atmospheric carbon dioxide over the past 100 million years

A self-consistent method of determining initial conditions for the model presented by Berner, Lasaga, and Garrels (1983) (henceforth, the BLAG model) is derived, based on the assumption that the CO2 geochemical cycle was in steady state at t = -100 m.y. (million years). This initialization procedure leads to a dissolved magnesium concentration higher than that calculated by Berner, Lasaga, and Garrels and to a low ratio of dissolved calcium to bicarbonate prior to 60 m.y. ago. The latter prediction conflicts with the geologic record of evaporite deposits, which requires that this ratio remain greater than 0.5. The contradiction is probably caused by oversimplifications in the BLAG model, such as the neglect of the cycles of organic carbon and sulfur.

Kasting, J. F.↗

Comments on the BLAG model: the carbonate-silicate geochemical cycle and its effect on atmospheric carbon dioxide over the past 100 million years

A self-consistent method of determining initial conditions for the model presented by Berner, Lasaga, and Garrels (1983) (henceforth, the BLAG model) is derived, based on the assumption that the CO2 geochemical cycle was in steady state at t = -100 my (million years). This initialization procedure leads to a dissolved magnesium concentration higher than that calculated by Berner, Lasaga, and Garrels and to a low ratio of dissolved calcium to bicarbonate prior to 60 my ago. The latter prediction conflicts with the geologic record of evaporite deposits, which requires that this ratio remain greater than 0.5. The contradiction is probably caused by oversimplifications in the BLAG model, such as the neglect of the cycles of organic carbon and sulfur.

Evolution, Planetary↗

The Martian ocean: First acid, then alkaline

In Mars' distant past, carbon dioxide and water may have been plentiful. Values of total outgassed CO2 from several to about 10 bar are consistent with present knowledge, and this amount of CO2 implies an amount of water outgassed equal to an equivalent depth of 500 to 1000 m. It is quite reasonable, therefore, to envision an early Mars in which there was a body or bodies of liquid water, perhaps in the northern plains, and a dense carbon dioxide atmosphere. Under such conditions, the pH of the water will be low, due to the dissolution of carbon dioxide in the water to form carbonic acid. This acidic water is capable of weathering the available rock quite intensely, particularly because this rock is likely to be heavily fractured (from meteorite bombardment) or even consist of fine particles (such as pyroclastic deposits). As time goes on, however, the carbon dioxide atmosphere will rapidly pass through the ocean to form carbonate deposits. As the density of the atmosphere decreases, so will the flux of carbonic acid into the ocean. Without this input of carbonic acid, the effect of the dissolved weathering products will be to increase the pH of the water. The ocean will then become alkaline. To study this process, I have developed a geochemical cycle model for the atmosphere-hydrosphere-regolith system of Mars. The treatment of geochemical cycles as complex kinetic chemical reactions has been undertaken for terrestrial systems in recent years with much success. This method is capable of elegantly handling the interactions between the simultaneous chemical reactions needed to understand such a system.

Schaefer, M. W.↗

The relation between the age of the subconducting slab and the recycling of sediments into the mantle

The recycling of sediments into the mantle has become an important issue because recent papers have suggested that the geochemical inverse models of the evolution of radiogenic isotope abundances over the history of the Earth have nonunique solutions. Both the recycling of continent-derived sediments into the mantle and mixing in the mantle could produce similar geochemical effects in the mean isotopic ratios of new igneous material emplaced in continents. Recent models of Archaean heat flow and of plate tectonics during early Earth history have demonstrated that higher internal heat production of the early Earth was mainly dissipated through a higher creation rate of oceanic lithosphere. If the seafloor creation rate was higher on the early Earth, then the residence time of any one piece of oceanic lithosphere on the surface would have been shorter. It is possible that a higher rate of recycling of oceanic lithosphere into the mantle could have resulted in some transport of sediment into the mantle.

Abbott, D.↗

Hydrothermal systems as environments for the emergence of life

Analysis of the chemical disequilibrium provided by the mixing of hydrothermal fluids and seawater in present-day systems indicates that organic synthesis from CO2 or carbonic acid is thermodynamically favoured in the conditions in which hyperthermophilic microorganisms are known to live. These organisms lower the Gibbs free energy of the chemical mixture by synthesizing many of the components of their cells. Primary productivity is enormous in hydrothermal systems because it depends only on catalysis of thermodynamically favourable, exergonic reactions. It follows that hydrothermal systems may be the most favourable environments for life on Earth. This fact makes hydrothermal systems logical candidates for the location of the emergence of life, a speculation that is supported by genetic evidence that modern hyperthermophilic organisms are closer to a common ancestor than any other forms of life. The presence of hydrothermal systems on the early Earth would correspond to the presence of liquid water. Evidence that hydrothermal systems existed early in the history of Mars raises the possibility that life may have emerged on Mars as well. Redox reactions between water and rock establish the potential for organic synthesis in and around hydrothermal systems. Therefore, the single most important parameter for modelling the geochemical emergence of life on the early Earth or Mars is the composition of the rock which hosts the hydrothermal system.

Non-NASA Center↗

An integrated dynamical and geochemical approach to lunar origin modelling

The three major categories of models of lunar origin which explain the Moon's properties are complete and a more general scenario is presented. The model presented is as the Earth grew by planetesimal bombardment, a circumterrestrial cloud of particles was created from a combination of impact ejected mantle material and planetismals captured directly into orbit around the Earth. The compositional properties are explained two ways: (1) a few big late planetismals of diverse composition are captured in orbit and/or hit the Earth; and (2) the circumterrestrial swarm acts as a filter, preferentially capturing small weak silicate bodies, while passing large iron planetismals.

Greenberg, R.↗