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Lab-Scale Study of the Calcium Carbonate Dissolution and Deposition by Marine Cyanobacterium Phormidium subcapitatum

Suggestions that calcification in marine organisms changes in response to global variations in seawater chemistry continue to be advanced (Wilkinson, 1979; Degens et al. 1985; Kazmierczak et al. 1986; R. Riding 1992). However, the effect of [Na+] on calcification in marine cyanobacteria has not been discussed in detail although [Na+] fluctuations reflect both temperature and sea-level fluctuations. The goal of these lab-scale studies therefore was to study the effect of environmental pH and [Na+] on CaCO3 deposition and dissolution by marine cyanobacterium Phormidium subcapitatum. Marine cyanobacterium P. subcapitatum has been cultivated in ASN-III medium. [Ca2+] fluctuations were monitored with Ca(2+) probe. Na(+) concentrations were determined by the initial solution chemistry. It was found that the balance between CaCO3 dissolution and precipitation induced by P. subcapitatum grown in neutral ASN III medium is very close to zero. No CaCO3 precipitation induced by cyanobacterial growth occurred. Growth of P. subcapitatum in alkaline ASN III medium, however, was accompanied by significant oscillations in free Ca(2+) concentration within a Na(+) concentration range of 50-400 mM. Calcium carbonate precipitation occurred during the log phase of P. subcapitatum growth while carbonate dissolution was typical for the stationary phase of P. subcapitatum growth. The highest CaCO3 deposition was observed in the range of Na(+) concentrations between 200-400 mM. Alkaline pH also induced the clamping of P. subcapitatum filaments, which appeared to have a strong affinity to envelop particles of chemically deposited CaCO3 followed by enlargement of those particles size. EDS analysis revealed the presence of Mg-rich carbonate (or magnesium calcite) in the solution containing 10-100 mM Na(+); calcite in the solution containing 200 mM Na(+); and aragonite in the solution containing with 400 mM Na(+). Typical present-day seawater contains xxmM Na(+). Early (Archean) seawater was likely less saline. The division of marine cyanobacterium P. subcapitatum is associated with periodic deposition and dissolution of CaCO3, the rhythms and intensity of which are dependent on concentrations of both OH(-) and Na(+). Thus, the role of present-day marine cyanobacteria in the global carbonate cycle might be reduced to aggregation and recrystallization of available CaCO3 particles in marine water rather than long-term precipitation and accumulation of CaCO3 deposits. For lower Na(+) concentrations, precipitation of carbonates by cyanobacteria would be even less significant. These results suggest that the lack of calcified cyanobacteria in stromatalite-bearing Precambrian sequences can be explained not only by high dissolved inorganic carbon concentrations but also by lower salinity, as well as possible lower pH compared to present-day oceans.

Karakis, S. G.↗

Panel Discussion: Life in the Cosmos

Water appears to be essential to all life on Earth. For this reason, "Follow the Water" has been adopted as a mantra for the search for Life in the Cosmos. Expeditions have helped to establish the limits and biodiversity of life in the most extreme environments on Earth. Microbial extremophiles inhabit acidic streams; hypersaline and hyperalkaline lakes and pools; the cold deep sea floor, permafrost, rocks, glaciers, and perennially ice-covered lakes of the polar environments; geysers, volcanic fumaroles, hydrothermal vents and hot rocks deep within the Earth's crust. The ESA Venus Express Spacecraft entered Venusian Orbit in 2006 and continues to produce exciting results. The Visible and Infrared Thermal Imaging Spectrometer (VIRTIS) instrument made the first detection of hydroxyl in the atmosphere of Venus, indicating it is much more similar to Earth and Mars than previously thought. Huge hurricane-like vortices have been found above the poles of the planet and as yet unidentified UV absorbers that form mysterious dark bands in the upper atmosphere. At 70 km and below, water vapor and sulfur dioxide combine to form sulfuric acid droplets that create a haze above the cloud tops. Thermophilic acidophiles, such as have recently been discovered on Earth, could possibly survive in the hot sulfuric acid droplets that exist in the upper atmosphere of Venus. In order to understand how to search for life elsewhere in the Solar System, over 40 VIRTIS images of Earth from Venus have been obtained to search for evidence of life on Earth. The signatures of water and molecular Oxygen were detected in the Earth s atmosphere, but the atmosphere of Venus also exhibits these signatures. The water and water ice are far more abundant on comet, the polar caps and permafrost of Mars and the icy moons of Jupiter and Saturn. These "frozen worlds" of our Solar System, are much more promising regimes where extant or extinct microbial life may exist. The ESA Mars Advanced Radar for Subsurface and Ionospheric Sounding (MARSIS) probe has found that both the North and South Polar Caps of Mars are approximately 3.5 km thick and are composed almost entirely of water ice. In winter, a thin dry ice layer covers the caps, but it sublimates directly to CO2 in the spring. The ESA Mars Express Orbiter images reveal Rupes Tenuis to be a vast snow-laden region on the southern edge of the Martian North Polar Cap. The Mars Exploration Rover Spirit found alkaline volcanic rocks in the Gusev Crater and the Phoenix Mars Lander has shown that the soil of Mars is much more alkaline than previously expected. The Phoenix Mars Lander has also made direct observations of frozen and liquid water on Mars. It is known that microorganisms from Alaska, Siberia and Antarctica can remain alive frozen in permafrost or ice for long periods of time. These discoveries increase the possibility that the Labeled Release Experiment may have discovered life on Mars during the Viking Mission and provide strong impetus for the return of life detection experiments to Mars. Changes in the spin rate of Saturn's moon Titan indicate that it may also harbor a 300 km thick liquid water ocean beneath its icy crust. The NASA/ESA/Italian Space Agency Cassini Spacecraft has imaged geysers containing water vapor, methane, carbon dioxide and organics erupting from the "tiger stripe" regions near the South Pole of Saturn's moon Enceladus. The high temperatures observed, the water vapor and large number of ice particles expelled suggest that a liquid water lake may exist beneath the "tiger stripe" ice cracks of Enceladus. The NASA Deep Impact probe found the surface temperature of comet 9P/Temple 1 at 1.5 AY was slightly above the ice/water phase change temperature (273 K). This suggests melting of water ice near the comet surface. A spectrometer the spacecraft detected a mixture of clay and carbonate minerals (that form in the presence of liquid water) streaming off the comet after the collision with the pactor. The study of chemical and mineral biomarkers, chiral amino acids and possible indigenous microfossils in SNC and carbonaceous meteorites continues. These results suggest that comets should be considered prime targets in the search for Life in the Cosmos. The ESA Rosetta mission is on track to rendezvous with comet 67P/Churyumov-Gerasimenko. The recent space observations combined with new information about the ability of microbial extremophiles to thrive in polar environments suggest that life may be far more widely distributed in the Cosmos than previously thought possible. The Panelists will review recent discoveries and provide their own insights about Life in the Cosmos -- followed by a question and answer session with the audience.

Hoover, Richard B.↗

The Formation of Fe/Mg Smectite Under Mildly Acidic Conditions on Early Mars

The detection of Fe/Mg smectites and carbonate in Noachian and early Hesperian terrain of Mars suggests that neutral to mildly alkaline conditions prevailed during the early history of Mars. If early Mars surface geochemical conditions were neutral to moderately alkaline with a denser CO2 atmosphere than today, then large carbonates deposits should be more widely detected in Noachian terrain. Why have so few carbonate deposits been detected compared to Fe/Mg smectites? Fe/Mg smectites on early Mars formed under mildly acidic conditions, which would preclude the extensive formation of carbonate deposits. The goal of the proposed work is to evaluate the formation of Fe/Mg smectites under mildly acidic conditions.

Sutter, B.↗

Friction modifier using adherent metallic multilayered or mixed element layer conversion coatings

A process for creating conversion coatings and spin, drawing, and extrusion finishes for surfaces, wherein the conversion coatings and spin, drawing, and extrusion finishes contain potassium, phosphorus, nitrogen, silicon, and one or more non-alkaline metals. The process comprises forming a first aqueous solution of silicate, potassium hydroxide, and ammonium hydroxide; forming a second aqueous solution of water, phosphoric acid, ammonium hydroxide, an alkali metal hydroxide, and one or more non-alkaline metals, and then combining the first solution with the second solution to form a final solution. This final solution forms an anti-friction multi-layer conversion coating or a spin, drawing, and extrusion finish on a surface when applied to the surface, either directly or as an additive in lubricating fluids.

Schramm, Harry F.↗

Air-Independent Solid Oxide Fuel Cells for NASA's LOX-CH4 Landers

Gemini, Apollo, and Space Shuttle used fuel cells as main power source for vehicle and water source for life support and thermal PEM (Gemini) and Alkaline (Apollo, Shuttle) fuel cells were used Ideal for short (less than 3 weeks) missions when the required O2 and H2 can be launched with the vehicle. New missions that might require long‐duration stays in orbit or at a habitat, cannot rely on the availability of pure reactants but should also aim to be sun‐independent - a problem for which Solid Oxide Fuel Cells might be the answer. Recently, NASA has investigated & developed LOX/CH4‐propelled landers (Altair, MORPHEUS). In order to preserve mission flexibility, fuel cells are being studied as a potential power source. Much of NASA's fuel cell development has been focused on creating a dead‐headed, non‐flow through PEM fuel cells which would weigh less and be more reliable than the existing Alkaline and PEM technology; however, LOX/CH4 as a propellant introduces SOFCs as a power option due to their ability to accept those reactants without much reforming.

Ryan, Abigail C.↗

Effects of Resistive Vibration Exercise Combined with Whey Protein and KHCO3 on Bone Tturnover Markers in Head-down Tilt Bed Rest (MTBR-MNX Study)

High protein intake further increases bone resorption markers in head-down tilt bed rest (HDBR), most likely induced by low-grade metabolic acidosis. Adding an alkaline salt to a diet with high protein content prevents this additional rise of bone resorption markers in HDBR. In addition, high protein intake, specifically whey protein, increases muscle protein synthesis and improves glucose tolerance, which both are affected by HDBR. Resistive vibration exercise (RVE) training counteracts the inactivity-induced bone resorption during HDBR. To test the hypothesis that WP plus alkaline salt (KHCO3) together with RVE during HDBR will improve bone turnover markers, we conducted a randomized, three-campaign crossover design study with 12 healthy, moderately fit male subjects (age 34+/-8 y, body mass [BM] 70 +/- 8 kg). All study campaigns consisted of a 7-d ambulatory period, 21days of -6 deg. head-down tilt bed rest (HDBR), and a 6-d recovery period. Diet was standardized and identical across phases. In the control (CON) campaign, subjects received no supplement or RVE. In the intervention campaigns, subjects received either RVE alone or combined with WP and KHCO3 (NEX). WP was applied in 3 doses per day of 0.6 g WP/kg BM together with 6 doses of 15 mmol KHCO3 per day. Eleven subjects completed the RVE and CON campaign, 8 subjects completed all three campaigns. On day 21 of HDBR excretion of the bone resorption marker C-telopeptide (CTX) was 80+/-28% (p<0.001) higher than baseline, serum calcium concentrations increased by 12 +/- 29% (p<0.001) and serum osteocalcin concentrations decreased by 6+/-12% (p=0.001). Urinary CTX excretion was 11+/- 25% (p=0.02) lower on day 21 of HDBR in the RVE- and tended to decrease by 3+/- 22% (p=0.06) in the NEX campaign compared to CON. Urinary calcium excretion was higher on day 21 in HDBR in the RVE and NEX (24+/- 43% p=0.01; 25+/- 37% p=0.03) compared to the CON campaign. We conclude that combination of RVE with WP/KHCO3 was not superior to RVE alone in any of these results.

Graf, Sonja↗

Friction Modifier Using Adherent Metallic Multilayered or Mixed Element Layer Conversion Coatings

A process for creating conversion coatings and spin, drawing, and extrusion finishes for surfaces, wherein the conversion coatings and spin, drawing, and extrusion finishes contain potassium, phosphorus, nitrogen, and one or more non-alkaline metals and/or one or more metalloids. The process comprises forming an aqueous solution of water, phosphoric acid or sulfuric acid, ammonium hydroxide, an alkali metal hydroxide, and one or more non-alkaline metals and/or one or more metalloids. The aqueous solution forms an anti-friction multilayer conversion and/or mixed element coating or a spin, drawing, and extrusion finish on a surface when applied to the surface, either directly without the use of applied external electromotive force, or as an additive in lubricating fluids.

Schramm, Harry F.↗

Rapid Solid-State Metathesis Routes to Nanostructured Silicon-Germainum

Methods for producing nanostructured silicon and silicon-germanium via solid state metathesis (SSM). The method of forming nanostructured silicon comprises the steps of combining a stoichiometric mixture of silicon tetraiodide (SiI4) and an alkaline earth metal silicide into a homogeneous powder, and initating the reaction between the silicon tetraiodide (SiI4) with the alkaline earth metal silicide. The method of forming nanostructured silicon-germanium comprises the steps of combining a stoichiometric mixture of silicon tetraiodide (SiI4) and a germanium based precursor into a homogeneous powder, and initiating the reaction between the silicon tetraiodide (SiI4) with the germanium based precursors.

Kaner, Richard B.↗

Elemental Gains/Losses Associated with Alteration Fractures in an Eolian Sandstone, Gale Crater, Mars

The Mars Science Laboratory rover Curiosity has traversed up section through approximately 100 m of sedimentary rocks deposited in fluvial, deltaic, lacustrine, and eolian environments (Bradbury group and overlying Mount Sharp group). The Stimson formation unconformably overlies a lacustrine mudstone at the base of the Mount Sharp group and has been interpreted to be a cross-bedded sandstone of lithified eolian dunes. Unaltered Stimson sandstone has a basaltic composition similar to the average Mars crustal composition, but is more variable and ranges to lower K and higher Al. Fluids passing through alteration "halos" adjacent to fractures have altered the chemistry and mineralogy of the sandstone. Elemental mass gains and losses in the alteration halos were quantified using immobile element concentrations, i.e., Ti (taus). Alteration halos have elemental gains in Si, Ca, S, and P and large losses in Al, Fe, Mn, Mg, Na, K, Ni, and Zn. Mineralogy of the altered Stimson is dominated by Ca-sulfates, Si-rich X-ray amorphous materials along with plagioclase feldspar, magnetite, and pyroxenes. The igneous phases were less abundant in the altered sandstone with a lower pyroxene/plagioclase feldspar. Large elemental losses suggest acidic fluids initially removed these elements (Al mobile under acid conditions). Enrichments in Si, Ca, and S suggest secondary fluids (possibly alkaline) passed through these fractures leaving behind X-ray amorphous Si and Ca-sulfates. The mechanism for the large elemental gains in P is unclear. The geochemistry and mineralogy of the altered sandstone suggests a complicated diagenetic history with multiple episodes of aqueous alteration under a variety of environmental conditions (e.g., acidic, alkaline).

Ming, D. W.↗

Biological Potential in Serpentinizing Systems

Generation of the microbial substrate hydrogen during serpentinization, the aqueous alteration of ultramafic rocks, has focused interest on the potential of serpentinizing systems to support biological communities or even the origin of life. However the process also generates considerable alkalinity, a challenge to life, and both pH and hydrogen concentrations vary widely across natural systems as a result of different host rock and fluid composition and differing physical and hydrogeologic conditions. Biological potential is expected to vary in concert. We examined the impact of such variability on the bioenergetics of an example metabolism, methanogenesis, using a cell-scale reactive transport model to compare rates of metabolic energy generation as a function of physicochemical environment. Potential rates vary over more than 5 orders of magnitude, including bioenergetically non-viable conditions, across the range of naturally occurring conditions. In parallel, we assayed rates of hydrogen metabolism in wells associated with the actively serpentinizing Coast Range Ophiolite, which includes conditions more alkaline and considerably less reducing than is typical of serpentinizing systems. Hydrogen metabolism is observed at pH approaching 12 but, consistent with the model predictions, biological methanogenesis is not observed.

the potential of serpentinizing systems to support↗

Smectite Formation in the Presence of Sulfuric Acid: Implications for Acidic Smectite Formation on Early Mars

The excess of orbital detection of smectite deposits compared to carbonate deposits on the martian surface presents an enigma because smectite and carbonate formations are both favored alteration products of basalt under neutral to alkaline conditions. We propose that Mars experienced acidic events caused by sulfuric acid (H2SO4) that permitted phyllosilicate, but inhibited carbonate, formation. To experimentally verify this hypothesis, we report the first synthesis of smectite from Mars-analogue glass-rich basalt simulant (66 wt% glass, 32 wt% olivine, 2 wt% chromite) in the presence of H2SO4 under hydrothermal conditions (approximately 200 degC). Smectites were analyzed by X-ray diffraction, Mossbauer spectroscopy, visible and near-infrared reflectance spectroscopy and electron microprobe to characterize mineralogy and chemical composition. Solution chemistry was determined by Inductively Coupled Plasma Mass Spectrometry. Basalt simulant suspensions in 11-42 mM H2SO4 were acidic with pH less than or equal to 2 at the beginning of incubation and varied from acidic (pH 1.8) to mildly alkaline (pH 8.4) at the end of incubation. Alteration of glass phase during reaction of the basalt simulant with H2SO4 led to formation of the dioctahedral smectite at final pH approximately 3 and trioctahedral smectite saponite at final pH approximately 4 and higher. Anhydrite and hematite formed in the final pH range from 1.8 to 8.4 while natroalunite was detected at pH 1.8. Hematite was precipitated as a result of oxidative dissolution of olivine present in Adirondack basalt simulant. Formation of secondary phases, including smectite, resulted in release of variable amounts of Si, Mg, Na and Ca while solubilization of Al and Fe was low. Comparison of mineralogical and solution chemistry data indicated that the type of smectite (i.e., dioctahedral vs trioctahedral) was likely controlled by Mg leaching from altering basalt and substantial Mg loss created favorable conditions for formation of dioctahedral smectite. We present a model for global-scale smectite formation on Mars via acid-sulfate conditions created by the volcanic outgassing of SO2 in the Noachian and early Hesperian.

Smectite↗

Constraining the Climate and Ocean PH of the Early Earth with a Geological Carbon Cycle Model

The early Earth's environment is controversial. Climatic estimates range from hot to glacial, and inferred marine pH spans strongly alkaline to acidic. Better understanding of early climate and ocean chemistry would improve our knowledge of the origin of life and its coevolution with the environment. Here, we use a geological carbon cycle model with ocean chemistry to calculate self-consistent histories of climate and ocean pH. Our carbon cycle model includes an empirically justified temperature and pH dependence of seafloor weathering, allowing the relative importance of continental and seafloor weathering to be evaluated. We find that the Archean climate was likely temperate (0-50deg C) due to the combined negative feedbacks of continental and seafloor weathering. Ocean pH evolves monotonically from 6.6(sup + 0.6) (sub -0.4) (2 sigma) at 4.0 Ga to 7.0(sup +0.7) (sub-0.5) (2 sigma) at the Archean-Proterozoic boundary, and to 7.9(sup +0.1) (sub -0.2) (2 sigma) at the Proterozoic-Phanerozoic boundary. This evolution is driven by the secular decline of pCO2, which in turn is a consequence of increasing solar luminosity, but is moderated by carbonate alkalinity delivered from continental and seafloor weathering. Archean seafloor weathering may have been a comparable carbon sink to continental weathering, but is less dominant than previously assumed, and would not have induced global glaciation. We show how these conclusions are robust to a wide range of scenarios for continental growth, internal heat flow evolution and outgassing history, greenhouse gas abundances, and changes in the biotic enhancement of weathering.

Krissansen-Totton, Joshua↗

Pre-Demonstration Development of Controlled-Release Corrosion Inhibitors and Healing Agents as Alternatives to Hexavalent Chromium

This Limited Scope Study was directed to achieve the following objectives: (1) Scale-up of materials that can meet MIL-PRF-23377 (solvent-based primer). (2) Provide evidence of resistance to aircraft alkaline cleaners and de-icing fluids. (3) Provide formulation for initial ecological and toxicity screening. (4) Submit an interim report that will provide the basis for a future ESTCP (the Dept. of Defense's (DoD's) Environmental Security Technology Certification Program) demonstration effort.The encapsulation procedure for two corrosion inhibitors was scaled up from lab scale to 2.0 kilograms. This scale will accommodate high volume production of coatings with encapsulated corrosion inhibitors for large surface areas during a follow-on ESTCP demonstration effort. Test results provided evidence of resistance to alkaline cleaners and aircraft de-icing fluids and compliance with MIL-PRF-23377. All the MIL-PRF-23377 requirements were met with the exception of the adhesion requirement, in top coated panels, and the flexibility requirement. Work on solving these two problems will be done prior to validation and demonstration of the technology. An initial ecological and toxicity screening identified several factors that were not critical to the acceptance of the encapsulated corrosion inhibitor. This new technology will lead to environmentally friendly alternatives to hexavalent chromium that will enable DoD to protect its assets. Field demonstration, licensing, qualification, and commercialization will allow its real world utilization. Abstract for Appendix A. Toxicology Report: Corrosion controls a significant problem for military equipment. Many surface treatment materials currently in use on items of military or aerospace materiel contain chromium (VI) as a component, a source of significant human health and environmental hazard. The formulation under evaluation contains no chromium. Most of the proposed components are low to moderate toxicity and are not a significant concern. Two of the formulation components are associated with some cancer hazard - 2-mercaptobenzothiazole and formaldehyde, but both find widespread use in industry and additional investigation is not required for this project.

Calle, Luz Marina↗

Pre-demonstration Development of Controlled-Release Corrosion Inhibitors and Healing Agents as Alternatives to Hexavalent Chromium

This Limited Scope Study was directed to achieve the following objectives:(1) Scale-up of materials that can meet MIL-PRF-23377 (solvent-based primer).(2) Provide evidence of resistance to aircraft alkaline cleaners and deicing fluids.(3) Provide formulation for initial ecological and toxicity screening.(4) Submit an interim report that will provide the basis for a future ESTCP demonstration effort.The encapsulation procedure for two corrosion inhibitors was scaled up from lab scale to 2.0 kg. This scale will accommodate high volume production of coatings with encapsulated corrosion inhibitors for large surface areas during a follow on ESTCP demonstration effort.Test results provided evidence of resistance to alkaline cleaners and aircraft deicing fluids and compliance with MIL-PRF-23377. All the MIL-PRF-23377 requirements were met with the exception of the adhesion requirement, in top coated panels, and the flexibility requirement. Work on solving these two problems will be done prior to validation and demonstration of the technology. An initial ecological and toxicity screening identified several factors that were not critical to the acceptance of the encapsulated corrosion inhibitor. This new technology will lead to environmentally friendly alternatives to hexavalent chromium that will enable DoD to protect its assets. Field demonstration, licensing, qualification, and commercialization will allow its real world utilization.

Calle, L. M.↗

Investigation of Magmatic Activities on Early Mars Using Igneous Mineral Chemistry in Gale Crater, Mars

One objective of rover missions is exploring the geological context of the surroundings. Over the years, igneous petrology and sedimentology have been disconnected, the first investigating magmatic processes and volcanic activities, and the second seeking environmental conditions in the past and assessing the habitability of the planet. Although different, one is related to the other: igneous rocks are altered and broken down, leading to the formation of sedimentary rocks, which can in turn be used to back out the nature of their magmatic source. The Curiosity rover that landed in the 3.7 Gyr old impact crater Gale is traveling through sedimentary rocks. About fifty float rocks have been observed, and several of them with ambiguous texture and composition have been classified as igneous or sedimentary depending on studies such as Jake_M. The composition of several unambiguous igneous rocks has been analyzed [4- 6] but their heterogeneity at a larger instrumental (measurement size < 2 cm) scale prevents the measurement of a bulk composition as performed on Earth. An original approach avoiding these two last issues is to consider igneous mineral chemistry analyzed within igneous and sedimentary rocks to assess magmatic processes that could have formed them. Most Curiosity data are used to explore ancient environmental conditions, and a significant number of compositional analyses are under-explored for constraining magmatic activities. We will present how we can make use of sedimentary data for investigating igneous processes in the vicinity of Gale crater. Geological Context: We focus on the first 750 martian days, corresponding to measurements in a coherent lacustrine sedimentary unit called Bradbury, because all sedimentary rocks were sourced from the same watershed and appear to have a consistent source with minimal alteration [2-3]. Igneous detrital minerals including feldspar and pyroxene, are observed in sedimentary rocks. Monte Carlo models showed that minimal cation loss is observed based on the composition of all Bradbury rocks, implying negligible weathering [3]. Although clay minerals are detected in few rocks [7], chemical compositions of rocks can be explained by a mixture of primary igneous minerals [3]. Variation of composition within Bradbury rocks can be explained by mineral sorting and one distinct source component. While a common magmatic source is suggested, Bradbury sediments likely come from several volcanic eruptions from a single magmatic chamber [9- 10]. The occurrence of alkali minerals like sanidine and K-rich rocks throughout Bradbury supports the presence of a potassic component, likely trachytic, while plagioclase and a mafic composition suggest a basaltic component [8-9]. Instruments: Mineral chemistry can be estimated by three instruments onboard Curiosity. The CheMin instrument enables detection of mineral assemblages using X-ray diffraction (XRD). Using Rietveld refinement, each mineral is identified according to their 1D XRD pattern [11]. Note that distinction between pyroxene minerals is challenging with the CheMin instrument due to overlapping peaks on XRD patterns and low angular resolution of the instrument [12]. Then, using least square regression and optimization algorithms based on unit-cell parameters, mineral chemistry has been estimated by [11]. Plagioclase composition has been estimated using the NaAlSi3O8- CaAl2Si2O8 system and alkali feldspar is based on the NaAlSi3O8-KAlSi3O8 system (stars in Fig.1). Two mudstone samples (John Klein and Cumberland) and one sandstone sample (Windjana) were analyzed by CheMin at Yellowknife Bay and Kimberley, respectively. Figure 1. Ternary diagrams of feldspars (top) and pyroxene (bottom) quadrilateral. Stars correspond to CheMin composition and the gray patches to ChemCam composition. The colored dots are the composition of feldspar and pyroxene that crystallized during fractional crystallization at FMQ+1 of a melt extracted at distinct melting degree during the adiabatic ascent of a primitive mantle composition, without any water (left panels) and with 0.5 wt.% of water (right panels) at distinct pressure. The ChemCam instrument enables the analysis of the chemical compositions of rocks at hundreds of micrometer scale (350-550 μm) using laser induced breakdown spectroscopy (LIBS), which may provide the composition of minerals when they are larger than the beam spot (>550 μm) [13]. Within >5000 LIBS points, we performed a typical stoichiometric filtering allowing us to distinguish 56 feldspar and 10 pyroxene mineral compositions (grey patches in Fig. 1). Finally, the Alpha Particle X-ray Spectrometer (APXS) analyzes the composition of rocks with a 1.6 cm diameter spot size. Monte Carlo mass balance modeling allowed [3] to decipher a feldspar range varying between An30 and An40 (Fig. 1). Discussion: Although there could be a more complex history and other ways to form the whole compositional range of igneous minerals analyzed within the Bradbury formation, we are presenting here simple magmatic pathways commonly occurring on Earth using the thermodynamical softwares pMELTS and rhyoliteMELTS [14]. The objective is to find reasonable igneous processes that produce minerals that parallel the compositions of feldspar and pyroxene analyzed by the Curiosity rover. As commonly observed for mid-ocean ridge basalts, the adiabatic ascent of a primitive mantle composition [15] partially melting at 2 GPa has been modeled, followed by the extraction of a liquid at distinct degrees of partial melting, which undergoes fractional crystallization at an oxygen fugacity +1 log unit above the fayalite-magnetite-quartz (FMQ) buffer within the crust (0.02-0.4 GPa) with H2O = 0- 0.5 wt. %. These latter conditions correspond to those recorded within igneous clasts from the Noachian martian breccia NWA 7034 and paired and within Gale igneous rocks (colored dots in Fig. 1) [16-17]. To check the reliability of these 2-step models, we also tested fractional crystallization at similar conditions (FMQ+1; P=0.02-0.4 GPa; H2O = 0-0.5 wt. %) of starting compositions corresponding to that of magmas with distinct melting degrees obtained from isobaric experiments at 2 GPa [18]. Mineral compositions obtained from both models are similar. As shown on Fig. 1, the whole range of observed feldspar compositions cannot be reproduced by fractionation of one magma only. Indeed, while alkali feldspar and Na-plagioclase likely crystallized from fractional crystallization of a low-degree melt (here <15%), plagioclase and pyroxene can only be formed by fractional crystallization of a higher degree melt (here >19%). The corresponding liquid descent lines are broadly in agreement with compositions estimated by ChemCam corresponding to float igneous rocks (Fig. 2) [4-6]. Figure 2. Silica versus alkali content. Lines show the liquid lines of descent from magmas with distinct degrees of melting. Gray patches represents the composition of Gale igneous rocks [4-6]. Trachytic to rhyolitic magmas crystallize alkali feldspar, and andesite to dacite magmas likely form plagioclase. Therefore, at least two starting magmas at distinct melting degrees, which could easily come from a single mantle source, are necessary to explain the whole compositional range of feldspar and pyroxene analyzed within Bradbury rocks. Conclusion: Because rocks from the Bradbury formation are likely originating from the same magmatic source with minimal weathering as supported by several studies using different approaches, igneous mineral chemistry analyzed by CheMin and ChemCam allows us to back out reasonable magmatic pathways that could have crystallized them. Fractional crystallization of at least two starting magmas originating from distinct melting degrees of a single mantle source can explain the whole range of feldspar and pyroxene composition. Both alkaline and sub-alkaline liquids can be produced, with compositions corresponding to those of the igneous rocks analyzed by ChemCam within the Bradbury formation, highlighting the complexity of Mars magmatism.

Payre, V.↗

Pre-Demonstration Development of Controlled-Release Corrosion Inhibitors and Healing Agents as Alternatives to Hexavalent Chromium

This Limited Scope Study was directed to achieve the following objectives: (1) Scale-up of materials that can meet MIL-PRF-23377 (solvent-based primer). (2) Provide evidence of resistance to aircraft alkaline cleaners and deicing fluids. (3) Provide formulation for initial ecological and toxicity screening. (4) Submit an interim report that will provide the basis for a future ESTCP demonstration effort. The encapsulation procedure for two corrosion inhibitors was scaled up from lab scale to 2.0 kg. This scale will accommodate high volume production of coatings with encapsulated corrosion inhibitors for large surface areas during a follow on ESTCP demonstration effort. Test results provided evidence of resistance to alkaline cleaners and aircraft deicing fluids and compliance with MIL-PRF-23377. All the MIL-PRF-23377 requirements were met with the exception of the adhesion requirement, in top coated panels, and the flexibility requirement. Work on solving these two problems will be done prior to validation and demonstration of the technology. An initial ecological and toxicity screening identified several factors that were not critical to the acceptance of the encapsulated corrosion inhibitor. This new technology will lead to environmentally friendly alternatives to hexavalent chromium that will enable DoD to protect its assets. Field demonstration, licensing, qualification, and commercialization will allow its real world utilization.

Alternatives to Hexavalent Chromium↗

Pre-Demonstration Development of Controlled-Release Corrosion Inhibitors and Healing Agents as Alternatives to Hexavalent Chromium

This Limited Scope Study was directed to achieve the following objectives: (1) Scale-up of materials that can meet MIL-PRF-23377 (solvent-based primer). (2) Provide evidence of resistance to aircraft alkaline cleaners and deicing fluids. (3) Provide formulation for initial ecological and toxicity screening. (4) Submit an interim report that will provide the basis for a future ESTCP demonstration effort. The encapsulation procedure for two corrosion inhibitors was scaled up from lab scale to 2.0 kg. This scale will accommodate high volume production of coatings with encapsulated corrosion inhibitors for large surface areas during a follow on ESTCP demonstration effort. Test results provided evidence of resistance to alkaline cleaners and aircraft deicing fluids and compliance with MIL-PRF-23377. All the MIL-PRF-23377 requirements were met with the exception of the adhesion requirement, in top coated panels, and the flexibility requirement. Work on solving these two problems will be done prior to validation and demonstration of the technology. An initial ecological and toxicity screening identified several factors that were not critical to the acceptance of the encapsulated corrosion inhibitor. This new technology will lead to environmentally friendly alternatives to hexavalent chromium that will enable DoD to protect its assets. Field demonstration, licensing, qualification, and commercialization will allow its real world utilization.

Alternatives to Hexavalent Chromium, Controlled Re↗

The Effect of Europa and Enceladus Analog Seawater Composition on Isotopic Measurements of Volatile CO2

Science goals for icy ocean worlds missions include characterizing the chemical compositionof the surface and interior using remote sensing and in situ techniques. The next class of flightmass spectrometers for these missions will obtain compositional identifications and isotope ratiomeasurements of volatiles evolved from the ice surface (exosphere) and plumes. These massspectra will be combined with data from other flight instruments to infer the composition of theinterior from volatiles. To ensure accurate interpretation of these measurements, it is critical toverify whether the fundamental assumption that volatiles observed in icy ocean world exospheresor plumes will be a direct reflection of the sub-ice ocean. The present study evaluates whether isotopologues from an initial CO2 gas fractionate by interacting with seawater (brine) of varyingsalt composition and concentration. δ13CCO2 are affected by the pH of the brine and subsequentspeciation of {CO2}, where {CO2} represents the combination of CO2, H2CO3, HCO3-, and CO32-.{CO2} for low pH brines hypothesized for Europa will preferentially speciate as CO2. Analyzedδ13CCO2 for low pH brines are within error of the original δ13CCO2, demonstrating that volatile CO2in a low pH system will be a direct reflection of the original CO2. However, Europa’s radiativeenvironment and rapid depressurization due to plume ejection may impose fractionation effects.In contrast, high pH systems relevant to Enceladus or a more alkaline Europa are expected toform all carbonate species, while favoring speciation as HCO3-. High pH brines in theseexperiments include both an original CO2 gas and an isotopically distinct HCO3- (from NaHCO3salt). These alkaline experiments demonstrate that δ13CCO2 values are highly variable, and dependon the concentration of the dominant carbonate species, (Na)HCO3-. Mass balance estimatesindicate that measured δ13CCO2 is a thermodynamically predictable mixture of both carbonsources, suggesting that measurements of δ13C at Enceladus would directly reflect of the sourcesof CO2 and carbonate buffering in the ocean. δ18O measurements for CO2 interacting with KCland MgCl2 follow established models for δ18O-ionic strength. CO2 interacting with MgSO4,Na2SO4, and NaCl demonstrate an offset from established δ18O-ionic strength models dependingon the concentration of initial CO2. These results suggest that current predictive models for δ18Oin brines need to be resolved for changing concentrations of CO2

Ocean Worlds↗