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Aeolian Removal of Dust Types from Photovoltaic Surfaces on Mars

Dust elevated in local or global dust storms on the Martian surface could settle on photovoltaic (PV) surfaces and seriously hamper their performance. Using a recently developed technique to apply a uniform dust layer, PV surface materials were subjected to simulated Martian winds in an attempt to determine whether natural Aeolian processes on Mars would sweep off the settled dust. Three different types of dust were used; an optical polishing powder, basaltic "trap rock", and iron (III) oxide crystals. The effects of wind velocity, angle of attack, height above the Martian surface, and surface coating material were investigated. It was found that arrays mounted with an angle of attack approaching 45 degrees show the most efficient clearing. Although the angular dependence is not sharp, horizontally mounted arrays required significantly higher wind velocities to clear off the dust. From this test it appears that the arrays may be erected quite near the ground, but previous studies have suggested that saltation effects can be expected to cause such arrays to be covered by soil if they are set up less than about a meter from the ground. Particle size effects appear to dominate over surface chemistry in these experiments, but additional tests are required to confirm this. Providing that the surface chemistry of Martian dusts is not drastically different from simulated dust and that gravity differences have only minor effects, the materials used for protective coatings for photovoltaic arrays may be optimized for other considerations such as transparency, and chemical or abrasion resistance. The static threshold velocity is low enough that there are regions on Mars which experience winds strong enough to clear off a photovoltaic array if it is properly oriented. Turbulence fences proved to be an ineffective strategy to keep dust cleared from the photovoltaic surfaces.

Gaier, James R.↗

Experimental Constraints on the Partitioning Behavior of F, Cl, and OH Between Apatite and Basaltic Melt

The mineral apatite is present in a wide range of planetary materials. The presence of volatiles (F, Cl, and OH) within its crystal structure (X-site) have motivated numerous studies to investigate the partitioning behavior of F, Cl, and OH between apatite and silicate melt with the end goal of using apatite to constrain the volatile contents of planetary magmas and mantle sources. A number of recent experimental studies have investigated the apatite-melt partitioning behavior of F, Cl, and OH in magmatic systems. Apatite-melt partitioning of volatiles are best described as exchange equilibria similar to Fe-Mg partitioning between olivine and silicate melt. However, the partitioning behavior is likely to change as a function of temperature, pressure, oxygen fugacity, apatite composition, and melt composition. In the present study, we have conducted experiments to assess the partitioning behavior of F, Cl, and OH between apatite and silicate melt over a pressure range of 0-6 gigapascals, a temperature range of 950-1500 degrees Centigrade, and a wide range of apatite ternary compositions. All of the experiments were conducted between iron-wustite oxidation potentials IW minus 1 and IW plus 2 in a basaltic melt composition. The experimental run products were analyzed by a combination of electron probe microanalysis and secondary ion mass spectrometry (NanoSIMS). Temperature, apatite crystal chemistry, and pressure all play important roles in the partitioning behavior of F, Cl, and OH between apatite and silicate melt. In portions of apatite ternary space that undergo ideal mixing of F, Cl, and OH, exchange coefficients remain constant at constant temperature and pressure. However, exchange coefficients vary at constant temperature (T) and pressure (P) in portions of apatite compositional space where F, Cl, and OH do not mix ideally in apatite. The variation in exchange coefficients exhibited by apatite that does not undergo ideal mixing far exceeds the variations induced by changes in temperature (T) or pressure (P) . In regions where apatite undergoes ideal mixing of F, Cl, and OH, temperature has a stronger effect than pressure on the partitioning behavior, but both are important. Furthermore, fluorine becomes less compatible in apatite with increasing pressure and temperature. We are still in the process of analyzing our experimental run products, but we plan to quantify the effects of P and T on apatite-melt partitioning of F, Cl, and OH.

McCubbin, Francis M.↗

Commercialization and Human Settlement of the Moon and Cislunar Space – A Look Ahead at the Possibilities over the Next 50 Years

Over 50 years have passed since the movie 2001: A Space Odyssey debuted in April 1968. In the film, Dr. Heywood Floyd flies to a large artificial gravity space station orbiting Earth aboard a commercial space plane. He then embarks on a commuter flight to the Moon arriving there 25hours later. Today, on the 50th anniversary of the Apollo 11 lunar landing, the images portrayed in 2001 still remain well beyond our capabilities. This paper examines key technologies and systems (in-situ resource utilization, fission power, advanced chemical and nuclear propulsion),and orbiting infrastructure elements (providing a propellant depot and cargo transfer function),that could be developed by NASA and the private sector in future decades allowing the operational capabilities presented in 2001 to be achieved, albeit on a more spartan scale. Lunar derived propellants (LDPs) will be essential to reducing the launch mass requirements from Earth and developing a reusable lunar transportation system (LTS) that can allow initial outposts to evolve into settlements supporting a variety of commercial activities like in-situ propellant production. Deposits of icy regolith found within permanently shadowed craters at the lunar pole scan supply the feedstock material to produce liquid oxygen (LO2) and hydrogen (LH2) propellan tneeded by surface-based lunar landing vehicles (LLVs) using chemical rocket engines. Along the Moon's nearside equatorial corridor, iron oxide-rich volcanic glass beads from vast pyroclasticdeposits, together with mare regolith, can provide the materials to produce lunar-derived LO2plus other important solar wind implanted (SWI) volatiles, including H2 and helium-3. Mega watt classfission power systems will be essential for providing continuous "24/7" power to LLVs will provide cargo and passenger "orbit-to-surface" access and willalso be used to transport LDP to Space Transportation Nodes (STNs) located in lunar polar(LPO) and equatorial orbits (LLO). Spaced-based, reusable lunar transfer vehicles (LTVs),operating between STNs in low Earth orbit (LEO), LLO, and LPO, and able to refuel with LDPs,can offer unique mission capabilities including short transit time crewed cargo transports. Even acommuter shuttle service similar to that portrayed in 2001 appears possible, allowing 1-way trip times to and from the Moon as short as 24 hours. The performance of LTVs using both RL10B-2chemical rockets, and a variant of the nuclear thermal rocket (NTR), the LO2-Augmented NTR(LANTR), are examined and compared. The bipropellant LANTR engine utilizes its divergent nozzle section as an afterburner into which oxygen is injected and supersonically combusted with reactor-heated hydrogen emerging from the engine's sonic throat. If only 1% of the LDP obtained from icy regolith, volcanic glass, and SWI volatile deposits were available for use in lunar orbit,such a supply could support routine commuter flights to the Moon for many thousands of years!This paper provides a look ahead at what might be possible in the not too distant future,quantifies the operational characteristics of key in-space and surface technologies and systems,and provides conceptual designs for the various architectural elements discussed.

Borowski, Stanley K.↗

Commercial and Human Settlement of the Moon and Cislunar Space – A Look Ahead at the Possibilities over the Next 50 Years

Over 50 years have passed since the movie 2001: A Space Odyssey debuted in April 1968. In the film, Dr. Heywood Floyd flies to a large artificial gravity space station orbiting Earth aboard a commercial space plane. He then embarks on a commuter flight to the Moon arriving there 25 hours later. Today, on the 50th anniversary of the Apollo 11 lunar landing, the images portrayed in 2001 still remain well beyond our capabilities. This paper examines key technologies and systems (in-situ resource utilization, fission power, advanced chemical and nuclear propulsion), and orbiting infrastructure elements (providing a propellant depot and cargo transfer function), that could be developed by NASA and the private sector in future decades allowing the operational capabilities presented in 2001 to be achieved, albeit on a more spartan scale. Lunar-derived propellants (LDPs) will be essential to reducing the launch mass requirements from Earth and developing a reusable lunar transportation system (LTS) that can allow initial outposts to evolve into settlements supporting a variety of commercial activities like in-situ propellant production. Deposits of icy regolith found within permanently shadowed craters at the lunar poles can supply the feedstock material to produce liquid oxygen (LO2) and hydrogen (LH2) propellant needed by surface-based lunar landing vehicles (LLVs) using chemical rocket engines. Along the Moon’s nearside equatorial corridor, iron oxide-rich volcanic glass beads from vast pyroclastic deposits, together with mare regolith, can provide the materials to produce lunar-derived LO2 plus other important solar wind implanted (SWI) volatiles, including H2 and helium-3. Megawatt-class fission power systems will be essential for providing continuous “24/7” power to processing plants, evolving human settlements, and other commercial activities that develop on the Moon and in orbit. Reusable LLVs will provide cargo and passenger “orbit-to-surface” access and will also be used to transport LDP to Space Transportation Nodes (STNs) located in lunar polar (LPO) and equatorial orbits (LLO). Spaced-based, reusable lunar transfer vehicles (LTVs), operating between STNs in low Earth orbit (LEO), LLO, and LPO, and able to refuel with LDPs, can offer unique mission capabilities including short transit time crewed cargo transports. Even a commuter shuttle service similar to that portrayed in 2001 appears possible, allowing 1-way trip times to and from the Moon as short as 24 hours. The performance of LTVs using both RL10B-2 chemical rockets, and a variant of the nuclear thermal rocket (NTR), the LO2-Augmented NTR (LANTR), are examined and compared. The bipropellant LANTR engine utilizes its divergent nozzle section as an afterburner into which oxygen is injected and supersonically combusted with reactor-heated hydrogen emerging from the engine’s sonic throat. If only 1% of the LDP obtained from icy regolith, volcanic glass, and SWI volatile deposits were available for use in lunar orbit, such a supply could support routine commuter flights to the Moon for many thousands of years! This paper provides a look ahead at what might be possible in the not too distant future, quantifies the operational characteristics of key in-space and surface technologies and systems, and provides conceptual designs for the various architectural elements discussed.

Borowski, Stanley K.↗

The Chemistry and Mineralogy of Mars Soils: A Tour of Landed Mission Results from the Last 45 years

Eight landed missions demonstrated that martian soils (defined as loose, unconsolidated surface material) consist of basaltic mineralogy, iron (hydr)oxides, amorphous material, sulfate, chloride, (per)chlorate, nitrate, carbonate, and possible organic C. The Viking Lander 1 and 2 (1976), Mars Pathfinder (1997), and Mars Exploration Rover (MER-A,B) (2004) missions determined that martian soil was similar at all landing sites by having mafic chemistry, high S (~ 7 wt.% SO3) and Cl (0.7 wt.%), and spectral detections of poorly crystalline and crystalline Fe-(hydr)oxide phases. The MER Mössbauer spectrometers detected Fe-bearing olivine and pyroxene along with magnetite, nano-phase Fe-oxides (npOx), hematite, and ferric sulfate. The 2008 Phoenix Lander instrumentation measured a soil pH of 7.7 and detected ~0.6 wt.% perchlorate, 3-5 wt.% Ca-rich carbonate and carbon (500 gC/g) consistent with oxidized organics and Fe-rich carbonate. The 2012 Mars Science Laboratory (MSL) rover (Gale Crater) through X-ray diffraction detected plagioclase feldspar, pyroxene, magnetite, hematite, anhydrite, and quartz, with the balance being composed of Si/Fe-containing amorphous (30 to 40 wt.%) material. MSL evolved gas analysis detected (per)chlorate (0.4 wt.% ClO4), nitrate (0.23 wt.%), along with minor Fe/Mg sulfate and oxidized organic C (~2000 gC/g). Limited pedogenesis may have occurred at the 2018 InSight landing site and in one Gusev Crater soil (MER-B) which have 3 to 10 cm-thick duricrust horizons consistent with atmospheric water vapor interactions with soil salts. Martian soil primary mineralogy was derived mostly from local rock (volcanic, sedimentary) that is largely basaltic planet wide. Secondary minerals [e.g., sulfate, chloride, perchlorate, nitrate, carbonate, Fe-(hydr)oxides] in martian soils formed from oxidative aqueous alteration processes and were likely derived from a combination of local sedimentary rock sources and the global bright dust. The Mars 2020 mission will collect soil for Earth return to enable a thorough assessment of the nature and origin of martian soil.

Mars↗

Mesoporous nickel-iron-manganese-alloy based metal/metal oxide composite thick film catalysts

Selective alloy corrosion is used to synthesize a robust and ultrafine mesoporous NiFeMn-based metal/metal oxide oxygen evolving catalyst with ligament and pore sizes in the range of 10 nm and a BET surface area of 43 m2/g. As an oxygen evolving catalyst, the mesoporous catalyst exhibits high stability (>264 hours) at a high current density (500 mA/cm2) with a low overpotential (360 mV) using a moderate electrolyte concentration (1 M KOH). The catalyst is made from non-precious metals and its fabrication is straight forward and directly applicable to large-scale synthesis.

36 MATERIALS SCIENCE↗

The Stability of SiO{sub 2} Fe{sub 3}O{sub 4} Nanoparticles for Uranium Extraction in Acidic Media - 20189

This comprehensive study has shown that the proposed strategy of SiO{sub 2} coating of Fe{sub 3}O{sub 4} nanoparticles (NPs) for the use of uranium (U) extraction in acidic media was successful. The breakdown of Fe{sub 3}O{sub 4} in acidic media has proven to be a challenge when applying to a nuclear waste removal scenario, leading to the dissolution of Fe{sub 3}O{sub 4} and preventing uptake of U ions in the waste. To overcome this a SiO{sub 2} passivating layer was grafted to the Fe{sub 3}O{sub 4} NPs, to which an acid stability test was conducted between pH 3 and pH 4. It has been shown via Transmission Electron Microscopy (TEM) and zeta potential measurements that the uncoated Fe{sub 3}O{sub 4} NPs exhibit rapid coagulation when exposed to acidic conditions, moving from a stable zeta potential of -44 mV to an unstable zeta potential of +6 mV. SiO{sub 2} coated Fe{sub 3}O{sub 4} on the other hand can remain stable for several hours and continue to be stable beyond that. Throughout acid exposure the zeta potential of these NPs remained at ∼ -38 mV, showing great stability. As a functionality is needed on the surface of the NPs for separation and extraction, the phosphate complex used was also tested for its acid stability. It was determined that with a constant zeta potential of ∼ -20 mV, the phosphate functionality was able to remain stable in the acidic conditions simulating the environment of certain nuclear wastes. Overall SiO{sub 2} coated (PO)x-Fe{sub 3}O{sub 4} NPs show great promise for application in separation and removal of U in acid media. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

A Backscatter Moessbauer Spectrometer (BaMS) for use on Mars

The use of Moessbauer spectroscopy for in situ analysis on the surface of Mars was proposed and the design and implementation of a backscatter Moessbauer spectrometer (BaMS) instrument suitable for planetary missions to the surfaces of Mars (MESUR), the Moon (Artemis and lunar outpost), asteroids, or other solid solar system objects is discussed. The BaMS instrument is designed to be capable of analysis of a sample for the mineralogy of its iron-bearing phases without any sample preparation. A requirement of lander missions to Mars is instrumentation for in situ mineralogical analyses. Such analyses provide data needed for primary characterization as to the type of surface materials present and by inference the processes that formed and subsequently modified them. For purposes of providing diagnostic information about naturally occurring materials, the element iron is particularly important because it is abundant and multivalent (primarily 0, +2, and +3 oxidation states). Knowledge of the oxidation state of iron and its distribution among iron-bearing mineralogies tightly constrains the types of materials present. The pivotal role of iron was already recognized in 1978 by COMPLEX, who recommended development of flight instruments that would identify mineralogy and the oxidation state of iron in planetary surface materials. The near-term U.S. strategy for the exploration of Mars is the MESUR (Mars Environmental SURvey) program, which entails emplacement of a network of small, long-lived surface landers. For the Moon, BaMS was recommended as part of a three-instrument landed payload for the Artemis missions, targeted for 1997. BaMS would prospect for ilmenite, an oxygen resource material, and provide data to assess the maturity of lunar soil. Because instrumental characteristics are low mass, low volume, and low power consumption, BaMS is suitable for implementation on even small landers and rovers, as are being envisioned in MESUR and Artemis concepts. In addition to providing highly diagnostic data, a BaMS analyzer is inherently simple and, as is highly desirable for remote operation, no sample preparation is required.

Agresti, D. G.↗

Label-Free In Situ Chemical Characterization of Amyloid Plaques in Human Brain Tissues

The accumulation of amyloid plaques and increased brain redox burdens are neuropathological hallmarks of Alzheimer’s disease. Altered metabolism of essential biometals is another feature of Alzheimer’s, with amyloid plaques representing sites of disturbed metal homeostasis. Despite these observations, metal-targeting disease treatments have not been therapeutically effective to date. A better understanding of amyloid plaque composition and the role of the metals associated with them is critical. To establish this knowledge, the ability to resolve chemical variations at nanometer length scales relevant to biology is essential. Here, we present a methodology for the label-free, nanoscale chemical characterization of amyloid plaques within human Alzheimer’s disease tissue using synchrotron X-ray spectromicroscopy. Our approach exploits a C–H carbon absorption feature, consistent with the presence of lipids, to visualize amyloid plaques selectively against the tissue background, allowing chemical analysis to be performed without the addition of amyloid dyes that alter the native sample chemistry. Using this approach, we show that amyloid plaques contain elevated levels of calcium, carbonates, and iron compared to the surrounding brain tissue. Chemical analysis of iron within plaques revealed the presence of chemically reduced, low-oxidation-state phases, including ferromagnetic metallic iron. The zero-oxidation state of ferromagnetic iron determines its high chemical reactivity and so may contribute to the redox burden in the Alzheimer’s brain and thus drive neurodegeneration. Ferromagnetic metallic iron has no established physiological function in the brain and may represent a target for therapies designed to lower redox burdens in Alzheimer’s disease. Additionally, ferromagnetic metallic iron has magnetic properties that are distinct from the iron oxide forms predominant in tissue, which might be exploitable for the in vivo detection of amyloid pathologies using magnetically sensitive imaging. We anticipate that this label-free X-ray imaging approach will provide further insights into the chemical composition of amyloid plaques, facilitating better understanding of how plaques influence the course of Alzheimer’s disease.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Impact of Acid–Base Stimulation Sequence on Mineral Stability for Tight/Impermeable Unconventional Carbonate-Rich Rocks: A Delaware Basin Case Study

We report mineral precipitation due to reactions with injected fluids during unconventional fracture stimulation is a well-recognized problem. The goal of this study is to evaluate secondary mineral precipitation and permeability attenuation under chemical injection scenarios specific to the Delaware basin. Whole cylindrical cores (2.54 cm diameter and 2.54 cm height) and ground shale (150–250 μm) from the carbonate-rich Bone Spring Formation, Delaware Basin TX (Leonardian), were reacted at 80 °C and 85 bar using a hydraulic fracturing fluid (HFF) recipe and an injection sequence typical of the Delaware Basin. The reacted shales and solutions were analyzed using a variety of laboratory- and synchrotron-based techniques to characterize both the chemical and spatial distributions of secondary mineral precipitation and identify changes in permeability and mineralogy. This carbonate-rich shale (>84% calcite) rapidly neutralized the acidic HFF. Synchrotron-based X-ray fluorescence mapping coupled with X-ray absorption spectroscopy (both bulk and micro) showed that most of the iron was in an oxidized form prior to exposure to HFF and that almost all iron(II) became fully oxidized after the reaction. Scanning electron microscopy images of the ground shale samples primarily identified iron(oxyhydr)oxide microcrystals on grain surfaces. A few small isolated iron-rich areas also contained sulfur, suggesting that some pyrite was preserved when isolated within a calcite crystal but that most was oxidized. The rapid neutralization of the acid spearhead in these carbonate-rich samples demonstrates that the acid spearhead is useful for initiating fractures in extremely calcite-rich rocks but does little to enhance rock permeability. This suggests that the impact of the acid spearhead is significantly smaller for carbonate-rich shales compared to clay-rich shales, which has broad implications for acidizing in carbonate-rich shale formations and iron transformations within these shales.

58 GEOSCIENCES↗

Theoretical constraints on oxygen and carbon dioxide concentrations in the Precambrian atmosphere

Simple (one-dimensional) climate models suggest that carbon dioxide concentrations during the Archean must have been at least 100-1000 times the present level to keep the Earth's surface temperature above freezing in the face of decreased solar luminosity. Such models provide only lower bounds on CO2, so it is possible that CO2 levels were substantially higher than this and that the Archean climate was much warmer than today. Periods of extensive glaciation during the early and late Proterozoic, on the other hand, indicate that the climate at these times was relatively cool. To be consistent with climate models CO2 partial pressures must have declined from approximately 0.03 to 0.3 bar around 2.5 Ga ago to between 10(-3) and 10(-2) bar at 0.8 Ga ago. This steep decrease in carbon dioxide concentrations may be inconsistent with paleosol data, which implies that pCO2 did not change appreciably during that time. Oxygen was essentially absent from the Earth's atmosphere and oceans prior to the emergence of a photosynthetic source, probably during the late Archean. During the early Proterozoic the atmosphere and surface ocean were apparently oxidizing, while the deep ocean remained reducing. An upper limit of 6 x 10(-3) bar for pO2 at this time can be derived by balancing the burial rate of organic carbon with the rate of oxidation of ferrous iron in the deep ocean. The establishment of oxidizing conditions in the deep ocean, marked by the disappearance of banded iron formations approximately 1.7 Ga ago, permitted atmospheric oxygen to climb to its present level. O2 concentrations may have remained substantially lower than today, however, until well into the Phanerozoic.

Review, Tutorial↗

The role of catalytic iron in enhancing volumetric sugar productivity during autothermal pyrolysis of woody biomass

Passivation of naturally occurring AAEM in biomass enhances sugar yields from the fast pyrolysis of biomass by preventing these metals from catalyzing the fragmentation of pyranose rings in cellulose and hemicellulose. However, because AAEM also catalyzes lignin depolymerization, its passivation can be accompanied by undesirable char agglomeration. Pretreatment of biomass with ferrous sulfate both passivates AAEM and substitutes ferrous ions as lignin depolymerization catalysts. This pretreatment has been particularly successful for high ash biomass like corn stover, but of limited value for low ash biomass like wood. This study explores the reasons for this discrepancy and offers a combined pretreatment of ferrous sulfate and ferrous acetate pretreatment to overcome char agglomeration in wood. Furthermore, this new pretreatment increased sugar yields from 4.4 wt% to 15.5 wt% and 5.4 wt% to 19.0 wt% for hardwood and softwood biomasses, respectively. This pretreatment produces an iron-rich biochar that catalyzes oxidation of the biochar under the oxygen-rich conditions of autothermal pyrolysis, which is preferentially consumed to provide the enthalpy for pyrolysis, preserving bio-oil as a more desirable energy product. Instead of producing carbon monoxide, which dominates oxidation of biochar from untreated biomass, the iron catalyzes oxidation to carbon dioxide, producing more energy per mole of oxygen consumed. In fact, oxygen demand to support autothermal pyrolysis of red oak and southern yellow pine was reduced 15% by the presence of iron in the biochar.

42 ENGINEERING↗

Iron precipitation under controlled oxygen flow: Mineralogical implications for BIF precursors in the Archean ocean

Banded iron formation (BIF) deposition in the Archean ocean is thought to have been initiated by the oxidation of dissolved iron into ferric primary precursor phases that descended through the water column and were deposited on the seafloor. Effective interpretation of the trace element and isotopic composition of BIFs in the geologic record requires an understanding of the identity and longevity of those precursor phases. Temporal and spatial variation in oxidant concentration and ocean chemistry may have driven precursor mineralogy. Furthermore, precursor phases may undergo transitions during descent and burial. This experimental study follows the evolution of iron mineralogy, speciation, and redox state during the precipitation of iron under variable oxygen fluxes and in fluids containing different iron-complexing anions (chloride, sulfate, and phosphate). Additionally, suspensions collected after incomplete oxidation were anoxically aged to simulate changes to precursor mineralogy during descent below the seawater redoxcline. Results from X-ray diffraction, sequential dissolution, colorimetric determination of Fe redox state, and Fe K-edge X-ray absorption fine structure spectroscopy showed that under all experimental conditions, intermediate precipitates collected before complete iron uptake contained mineralized ferrous iron. Purely ferric mineral assemblages were not observed until iron was removed from solution. In low-oxygen experiments, intermediate precipitates contained phases with stoichiometric Fe 2+ , including magnetite, vivianite, and green rust (GR). Chloride green rust (GR1) had more ferric iron than sulfate green rust (GR2) and more readily transitioned to magnetite via disproportionation. GR2 was stable over a broader range of iron uptake; magnetite appeared mainly as an additional oxidation product in sulfate solution. In high oxygen experiments, mineralized ferrous iron occurred in amorphous phases or as a non-stoichiometric component in ferric oxides; final ferric assemblages were less crystalline than in low-oxygen equivalents. Low concentrations of phosphate increased the total iron oxidation rate, but also increased the ferrous content of intermediate precipitates. The incorporation of phosphate stabilized GR2 and facilitated GR2 precipitation over a larger range of iron uptake. In higher concentrations of phosphate, vivianite and poorly crystalline ferric hydroxides formed in place of GR. Here, these findings suggest that over a range of possible ocean chemistries, mixed-valence phases may have been short lived but relevant precursors to BIF. Additionally, anionic chemistry and oxidant concentration are shown to influence the crystallinity and chemical resistivity of final ferric assemblages, affecting their reactivity during later anoxic burial.

58 GEOSCIENCES↗

Early diagenetic processes in an iron-dominated marine depositional system

The early diagenetic interplay between reactive iron, sulfur, and organic matter in the bathymetrically isolated Santa Monica Basin (SMB) sediments are investigated in this study. Here, we explore solid-phase and porewater profiles from the basin, supplemented with a transect from 71 to 907 m water depth that includes oxygenated (>60 μM O 2 ) bottom waters near the coast and oxygen-deficient waters (~4 µM O 2 ) in the basin. The geochemical data of the basin sediments are further scrutinized by means of reactive transport modeling. The results show that the basin sediments do not follow the traditional geochemical signatures of oxygen-deficient settings. A lack of dissolved sulfide accumulation and sulfurized iron persists despite the sediments being deposited under reducing conditions (without bioturbation/bioirrigation), strong organic carbon input (TOC up to 5.0 wt%), and active dissimilatory sulfate reduction. Not only did we find an exceptional enrichment in highly reactive Fe in the surface sediments (~45 % of total Fe), but the enrichment of reactive Fe, including ferrihydrite, persists downcore and coexists with high levels of dissolved Fe. The enhanced preservation of Fe oxides and lack of iron-sulfide precipitation is in part explained by detection via Mössbauer spectra of iron oxides bounded to organic matter (Fe[III]-OM coprecipitates). The modeled Fe budget shows that most of the Fe oxides in the surface sediments are internally recycled by upward diffusion and subsequent oxidation of Fe 2+ . Sulfide oxidation coupled to Fe reduction effectively precludes sulfide accumulation while enhancing build-up of dissolved Fe, fueling the Fe cycle within the first 5 cm depth. Continuous reoxidation of Fe 2+ enhances the formation of Fe(III)-OM coprecipitates, limiting the amount of reactive organic matter. In the unavailability of labile organic matter, other than within the uppermost layers, the organic-rich sediment profiles are dominated by Fe cycling that limits the production and preservation of sulfides and enhances the preservation of Fe oxides and organic carbon. Finally, this study highlights key local controls on Fe availability in marginal basins and describes an intricate biogeochemical C-Fe-S cycling in modern and possibly ancient marine systems with important implications for Fe availability in the marine realm.

58 GEOSCIENCES↗

Characterization of a Subsurface Biosphere in a Massive Sulfide Deposits at Rio Tinto, Spain: Implications for Extant Life on Mars

The recent discovery of abundant sulfate minerals, particularly Jarosite by the Opportunity Rover at Sinus Merdiani on Mars has been interpreted as evidence for an acidic lake or sea on ancient Mars [1,2], since the mineral Jarosite is soluble in liquid water at pH above 4. The most likely mechanism to produce sufficient protons to acidify a large body of liquid water is near surface oxidation of pyrite rich deposits [3]. The acidic waters of the Rio Tinto, and the associated deposits of Hematite, Goethite, and Jarosite have been recognized as an important chemical analog to the Sinus Merdiani site on Mars [4]. The Rio Tinto is a river in southern Spain that flows 100 km from its source in the Iberian pyrite belt, one of the Earth s largest Volcanically Hosted Massive Sulfide (VHMS) provinces, into the Atlantic ocean. The river originates in artesian springs emanating from ground water that is acidified by the interaction with subsurface pyrite ore deposits. The Mars Analog Rio Tinto Experiment (MARTE) has been investigating the hypothesis that a subsurface biosphere exists at Rio Tinto living within the VHMS deposit living on chemical energy derived from sulfur and iron minerals. Reduced iron and sulfur might provide electron donors for microbial metabolism while in situ oxidized iron or oxidants entrained in recharge water might provide electron acceptors.

Stoker, C. R.↗

Characterization of a Subsurface Biosphere in a Massive Sulfide Deposit At Rio Tinto, Spain: Implications For Extant Life On Mars

The recent discovery of abundant sulfate minerals, particularly Jarosite by the Opportunity Rover at Sinus Merdiani on Mars has been interpreted as evidence for an acidic lake or sea on ancient Mars [1,2], since the mineral Jarosite is soluble in liquid water at pH above 4. The most likely mechanism to produce sufficient protons to acidify a large body of liquid water is near surface oxidation of pyrite rich deposits [3]. The acidic waters of the Rio Tinto, and the associated deposits of Hematite, Goethite, and Jarosite have been recognized as an important chemical analog to the Sinus Merdiani site on Mars [4]. The Rio Tinto is a river in southern Spain that flows 100 km from its source in the Iberian pyrite belt, one of the Earth's largest Volcanically Hosted Massive Sulfide (VHMS) provinces, into the Atlantic ocean. The river originates in artesian springs emanating from ground water that is acidified by the interaction with subsurface pyrite ore deposits. The Mars Analog Rio Tinto Experiment (MARTE) has been investigating the hypothesis that a subsurface biosphere exists at Rio Tinto living within the VHMS deposit living on chemical energy derived from sulfur and iron minerals. Reduced iron and sulfur might provide electron donors for microbial metabolism while in situ oxidized iron or oxidants entrained in recharge water might provide electron acceptors.

Stoker, C. R.↗