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All sourcesNASA NTRSDOE OSTI
NASA NTRS2015

Constraining the Texture and Composition of Pore-Filling Cements at Gale Crater, Mars

The Mars Science Laboratory (MSL) rover Curiosity has encountered a wide variety of sedimentary rocks deposited in fluvio-lacuestrine sequences at the base of Gale Crater. The presence of sedimentary rocks requires that initial sediments underwent diagenesis and were lithified. Lithification involves sediment compaction, cementation, and re-crystallization (or authigenic) processes. Analysis of the texture and composition of the cement can reveal the environmental conditions when the cements were deposited, enabling better understanding of early environments present within Gale Crater. The first step in lithification is sediment compaction. The Gale crater sediments do not show evidence for extensive compaction prior to cementation; the Sheepbed mudstone in Yellowknife Bay (YKB) has preserved void spaces ("hollow nodules"), indicating that sediments were cemented around the hollow prior to compaction, and conglomerates show imbrication, indicating minimal grain reorganization prior to lithification. Furthermore, assuming the maximum burial depth of these sediments is equivalent to the depth of Gale Crater, the sediments were never under more than 1 kb of pressure, and assuming a 15 C/km thermal gradient in the late Noachian, the maximum temperature of diagenesis would have been approximately 75 C. This is comparable to shallow burial diagenetic conditions on Earth. The cementation and recrystallization components of lithification are closely intertwined. Cementation describes the precipitation of minerals between grains from pore fluids, and recrystallization (or authigenesis) is when the original sedimentary mineral grains are altered into secondary minerals. The presence of authigenic smectites and magnetite in the YKB formation suggests that some recrystallization has taken place. The relatively high percentage of XRD-amorphous material (25-40%) detected by CheMin suggests that this recrystallization may be limited in scope, and therefore may not contribute significantly to the cementing material. However, relatively persistent amorphous components could exist in the Martian environment (e.g. amorphous MgSO4), so recrystallization, including loss of crystallinity, cannot yet be excluded as a method of cementation. In order to describe the rock cementation, both the rock textures and their composition must be considered. Here, we attempt to summarize the current understanding of the textural and compositional aspects of the cement across the rocks analyzed by Curiosity to this point.

Siebach, K. L.↗
NASA NTRS1985

Role of minerals in the thermal alteration of organic matter. I - Generation of gases and condensates under dry condition

Pyrolysis experiments conducted at 200 and 300 C on kerogen and bitumen from the Monterey formation and on the Green River Formation kerogen with montmorillonite, illite, and calcite added are described. The pyrolysis products are identified and gas and condensate analyses are performed. A catalytic effect is detected in the pyrolysis of kerogen with montmorillonite; however, illite and calcite display no catalytic activity. The increased production of C1-C6 hydrocarbons and the dominance of branched hydrocarbons in the C4-C6 range reveals a catalytic influence. It is observed that the catalysis of montmorillonite is greater during bitumen pyrolysis than for kerogen, and catalysis with minerals affects the production of CO2. It is concluded that a mineral matrix is important in determining the type and amount of gases and condensates forming from organic matter under thermal stress.

Tannenbaum, E.↗
NASA NTRS2017

Surveying Clay Mineral Diversity in the Murray Formation, Gale Crater, Mars

The CheMin XRD instrument aboard Mars Science Laboratory (MSL) has documented clay minerals in various drill samples during its traverse of Gale Crater's floor and ascent of Mt. Sharp. The most recent samples, named Marimba, Quela and Sebina were acquired from the Murray Formation in the Murray Buttes region of lower Mt. Sharp. Marimba and Quela come from a approx. 30 m package of finely laminated lacustrine mudstones. Sebina comes from an overlying package of heterolithic mudstone-sandstones. Clay minerals make up approx.15-25 wt.% of the bulk rock with similar contributions to XRD patterns in all three samples. Broad basal reflections at approx. 10deg 2(theta) CoK(alpha) indicate the presence of 2:1 group clay minerals. The 02(lambda) clay mineral band lies at approx. 22.9deg 2(theta), a region typically occupied by Fe-bearing dioctahedral 2:1 clay minerals like nontronite or Fe-illite. The low humidity within the CheMin instrument, which is open to the martian atmosphere, promotes loss of interlayer H2O and collapse of smectite interlayers making them difficult to distinguish from illites. However, based on the low K content of the bulk samples, it appears that smectitic clay minerals are dominant. Peak dehydroxylation of the Marimba sample measured by the SAM instrument on MSL occurred at 610C and 780C. Fe-bearing smectites are not consistent with these dehydroxylation temperatures. Thus, we suggest that a mixture of dioctahedral and trioctahedral smectite phases are present giving the appearance of intermediate octahedral occupancy in XRD. Dioctahedral smectites have not previously been reported in Gale Crater by MSL. Earlier in the mission, relatively clay mineral rich samples (approx. 20 wt.%) from lacustrine mudstones in Yellowknife Bay (YKB) were found to contain ferrian saponites. It is proposed that YKB saponites formed via isochemical aqueous alteration of detrital olivine close to the time of sediment deposition, under anoxic to poorly oxidizing conditions. In terrestrial settings where alteration sequences of basaltic rocks or sediments are observed, first-stage alteration clay minerals are typically trioctahedral smectite species, as reported from YKB. In later alteration stages trioctahedral clay minerals are replaced by dioctahedral clays as a result of removal and/or oxidation of Fe2+ and Mg. Observed changes in clay mineralogy between YKB and Murray Buttes samples correspond with differences in bulk mineralogy, including: 1) a transition from magnetite to hematite as the main Fe-oxide, 2) increasing abundances of Ca-sulfates and 3) a reduction in the quantity of reactive mafic minerals. This mineralogical change indicates an increasing degree of aqueous alteration and oxidation of mafic detritus in the upper part of the Murray Formation. These results broaden the spectrum of mineralogical facies documented by MSL. Together sedimentology and mineralogy indicate a long-lasting, dynamic fluvial-lacustrine system encompassing a range aqueous geochemical processes under varying redox conditions. Future work is needed to unravel the influence of global and local controls on the range of ancient conditions observed at Gale Crater.

MSL↗
NASA NTRS2020

Isotopic and Microstructural Analyses of Opaque Mineral Assemblages and Their Alteration Products Hosted in a Refractory Inclusion

Calcium-aluminum-rich inclusions (CAIs) hosted in primitive meteorites are the oldest solids formed in the Solar System. Some CAIs contain metal nuggets that are complex assemblages of Fe-Ni alloys, along with rare ultra-refractory metals such as platinum group elements (PGEs), and their alteration products such as magnetite, sulfides, and phosphates. Three possible mechanisms proposed to explain the origin of these metal nuggets include condensation in circumstellar settings, condensation in the solar nebula within the CAI-forming region, or crystallization from immiscible metal-silicate melt. However, secondary alteration processes may have also affected some of these assemblages. Additionally, similar metal assemblages observed in chondrules and chondritic matrix indicate that all of these metal nuggets could share common high-temperature origins. These metal assemblages record early Solar System conditions that are reflected in their distinctive chemical composition, mineralogy and microstructures. Here we report a detailed mineralogical, microstructural and oxygen isotopic study of one such metal assemblage hosted in a CAI to understand the physical and chemical settings in which it formed.

Mane, P.↗
DOE OSTI2026

Desorption of Phosphate from Iron-Bearing Soil Minerals by a Plant Secondary Metabolite

In soils, phosphorus readily adsorbs to the surfaces of ubiquitous iron (oxyhydr)oxide minerals, rendering it less accessible to plants and microorganisms. Plants have a number of strategies to access iron, among them the secretion of redox-active metabolites from their roots. Although these strategies likely increase the bioavailability of surface-adsorbed phosphorus through reductive dissolution, their effect on phosphorus cycling has not yet been investigated. We tested the ability of fraxetin, a coumarin-type redox-active metabolite produced by the model plant Arabidopsis thaliana and other dicotyledon plant species, to reductively solubilize phosphate from the surface of ferrihydrite. Our findings show that, at low and neutral pH, fraxetin increased aqueous phosphate concentrations under both oxic and anoxic conditions; at high pH, it was only effective in anoxic experiments. Additionally, a combination of liquid chromatography–mass spectrometry and spectroscopic methods demonstrated substantial fraxetin adsorption to the mineral surface but showed that iron reduction did not alter the mineral structure or change the nature of the chemical environment of the phosphorus atom over short time scales. These results provide evidence that the secretion of redox-active metabolites from roots is likely to be an effective phosphorus acquisition tactic in iron-rich soils.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Metasomatic alteration of coarse‐grained igneous calcium‐aluminum‐rich inclusions from CK3 carbonaceous chondrites

Abstract We report on the primary and secondary mineralogies of three coarse‐grained igneous calcium‐aluminum‐rich inclusions (CAIs) (Compact Type A [CTA], Type B [B], and forsterite‐bearing type B [FoB]) from the Northwest Africa (NWA) 5343 (CK3.7) and NWA 4964 (CK3.8) carbonaceous chondrites, compare them with the mineralogy of igneous CAIs from the Allende (CV3.6) chondrite, and discuss the nature of the alteration processes that affected the CK and CV CAIs. The primary mineralogy and mineral chemistry of the CK3 CAIs studied are similar to those from Allende; however, primary melilite and anorthite are nearly completely absent. Although the secondary minerals identified in CK CAIs (Al‐diopside, andradite, Cl‐apatite, clintonite, forsterite, ferroan olivine, Fe,Ni‐sulfides, grossular, ilmenite, magnetite, plagioclase, spinel, titanite, and wadalite) occur also in the Allende CAIs, there are several important differences: (i) In addition to melilite and anorthite, which are nearly completely replaced by secondary minerals, the alteration of CK CAIs also affected high‐Ti pyroxenes (fassaite and grossmanite) characterized by high Ti 3+ /Ti 4+ ratio and spinel. These pyroxenes are corroded and crosscut by veins of Fe‐ and Ti‐bearing grossular, Fe‐bearing Al,Ti‐diopside, titanite, and ilmenite. Spinel is corroded by Fe‐bearing Al‐diopside and grossular. (ii) The secondary mineral assemblages of grossular + monticellite and grossular + wollastonite, commonly observed in the Allende CAIs, are absent; the Fe‐bearing grossular + Fe‐bearing Al‐diopside ± Fe,Mg‐spinel, Fe‐bearing grossular + Fe,Mg‐olivine ± Fe,Mg‐spinel, and Ca,Na‐plagioclase + Fe‐bearing Al‐diopside + Fe‐bearing grossular assemblages are present instead. These mineral assemblages are often crosscut by veins of Fe‐bearing Al‐diopside, Fe,Mg‐olivine, Fe,Mg‐spinel, and Ca,Na‐plagioclase. The coarse‐grained secondary grossular and Al‐diopside often show multilayered chemical zoning with distinct compositional boundaries between the layers; the abundances of Fe and Ti typically increase toward the grain edges. (iv) Sodium‐rich secondary minerals, nepheline and sodalite, commonly observed in the peripheral portions of the Allende CAIs, are absent; Ca,Na‐plagioclase is present instead. We conclude that coarse‐grained igneous CAIs from CK3.7–3.8 s and Allende experienced an open‐system multistage metasomatic alteration in the presence of an aqueous solution–infiltration metasomatism. This process resulted in localized mobilization of all major rock‐forming elements: Si, Ca, Al, Ti, Mg, Fe, Mn, Na, K, and Cl. The metasomatic alteration of CK CAIs is more advanced and occurred under higher temperature and higher oxygen fugacity than that of the Allende CAIs.

Geochemistry & Geophysics↗
NASA NTRS2005

Stability of Magnesium Sulfate Minerals in Martian Environments

Viking Lander, Pathfinder, and Mars Exploration Rover missions to Mars have found abundant sulfur in surface soils and rocks, and the best indications are that magnesium sulfates are among the key hosts. At Meridiani Planum, MgSO4 salts constitute 15 to 40 wt.% of sedimentary rocks. Additional S is hosted by gypsum and jarosite. Reflectance and thermal emission spectroscopy is consistent with the presence of kieserite (MgSO4 H2O) and epsomite (MgSO4*7H2O). Theoretically, the dodecahydrate (MgSO4*12H2O) should also have precipitated. We first examine theoretically which MgSO4 minerals should have precipitated on Mars, and then how dehydration might have altered these minerals.

Marion, G. M.↗
NASA NTRS2017

Effects of Martian Surface Materials on the Thermal Decomposition of Hydrogen Peroxide

While hydrogen peroxide (H2O2) has been detected in the martian atmosphere, it has not been detected in surface materials. Since the Viking lander mission, we have sent instruments to Mars with the capability to detect H2O2. The Sample Analysis at Mars (SAM) instrument onboard the Curiosity Rover and Thermal and Evolved Gas Analyzer (TEGA) instrument on the Phoenix lander both detected water and oxygen releases from analyzed sediments but whether or not peroxide could be the source of these gases has not been investigated. We are investigating the possible presence of H2O2 in martian materials by analyzing Mars-relevant minerals that have been mixed with hydrogen peroxide using lab instruments configured as analogs to Mars mission instruments. The object of this research is to use lab instruments to find the effects of Mars analog minerals on hydrogen peroxide gas release temperatures, specifically gas releases of water and oxygen and also determine the effect of the peroxide on the minerals. Data that we get from the lab can then be compared to the data collected from Mars. The minerals hematite, siderite, San Carlos olivine, magnetite and nontronite were chosen as our Mars analog minerals. ~20 mg of analog Mars minerals with 5μl of 50% H2O2, and were either run immediately or placed in a sealed tube for 2, 4, or 9 days to look for changes over time with two reps being done at each time step to determine repeatability. Each sample was heated from -60 degC to 500 degC at 20 degC/min and the evolved gases were monitored with a mass spectrometer. Each sample was also analyzed with an X-ray diffraction instrument to look for changes in mineralogy. Preliminary results show three potential outcomes: 1) peroxide has no effect on the sample (e.g., hematite), 2) the mineral is unaffected but catalyzes peroxide decomposition (magnetite, siderite), or 3) peroxide alters the mineral (pyrrhotite, San Carlos olivine).

Archer, P. D., Jr.↗
NASA NTRS2018

Adrianite, Ca12(Al4Mg3Si7)O32Cl6, a New Cl-rich Silicate Mineral from the Allende Meteorite: An Alteration Phase in a Ca-Al-rich Inclusion

Adrianite (IMA 2014-028), Ca12 (Al4Mg3Si7)O32Cl6, is a new Cl-rich silicate mineral and the Si, Mg analog of wadalite. It occurs with monticellite, grossular, wadalite, and hutcheonite in altered areas along some veins between primary melilite, spinel, and Ti, Al-diopside in a Type B1 FUN (Fractionation and Unidentified Nuclear effects) Ca-Al-rich inclusion (CAI), Egg-3, from the Allende CV3 carbonaceous chondrite. The mean chemical composition of type adrianite by electron probe microanalysis is (wt%) CaO 41.5, SiO2 27.5, Al2O3 12.4, MgO 7.3, Na2O 0.41, Cl 13.0, O=Cl –2.94, total 99.2, giving rise to an empirical formula of (Ca11.69Na0.21) (Al3.85Mg2.88Si7.23) O32Cl5.80. The end-member formula is Ca12 (Mg5Si9) O32Cl6. Adrianite has the I43d wadalite structure with a = 11.981 Å, V = 1719.8 Å3, and Z = 2, as revealed by electron backscatter diffraction. The calculated density using the measured composition is 3.03 g/cm3. Adrianite is a new secondary mineral in Allende, apparently formed by alkali-halogen metasomatic alteration of primary CAI minerals such as melilite, anorthite, perovskite, and Ti,Al-diopside on the CV chondrite parent asteroid. Formation of secondary Cl-rich minerals sodalite, adrianite, and wadalite during metasomatic alteration of the Allende CAIs suggests that the metasomatic fluids had Cl-rich compositions. The mineral name is in honor of Adrian J. Brearley, mineralogist at the University of New Mexico, U.S.A., in recognition of his many contributions to the understanding of secondary mineralization in chondritic meteorites.

Adrianite↗
NASA NTRSDate not supplied

Mineralogy of the Greenheugh Pediment and Underlying Murray Formation from the Mars Science Laboratory CheMin Instrument

The Mars Science Laboratory Curiosity rover has been investigating a sequence of ancient fluvio-lacustrine and eolian units in Gale crater. For much of the mission, Curiosity has studied the fluvio-lacustrine deposits of the Murray formation. Curiosity has also studied the ancient eolian Stimson formation in a few locations, which unconformably overlies the Murray fm. The Stimson formation was previously studied at the Naukluft and Emerson Plateaus and recently studied at the Greenheugh pediment capping unit. The Curiosity science team also investigated the Murray formation directly underlying the pediment. Curiosity drilled the “Edinburgh” target within the pediment capping unit and the “Hutton” target in the Murray formation near the contact with the pediment and delivered these materials to the CheMin X-ray diffractometer to characterize bulk mineralogy. Edinburgh contains abundant plagioclase, pyroxene, magnetite, olivine, and X-ray amorphous materials, with 10 wt.% smectite and minor sanidine. The mineralogy of the Stimson at Greenheugh is distinct from the mineralogy of the Stimson at Naukluft and Emerson because previous Stimson targets did not contain olivine or clay minerals. This suggests sediments in the pediment may have a different source and/or different aqueous alteration history than those from Naukluft and Emerson. Hutton contains abundant plagioclase, pyroxene, magnetite, and X-ray amorphous materials, 6 wt.% smectite, and minor cristobalite, opal-CT, sanidine, hematite, fluorapatite, and anhydrite. Other Murray targets in the surrounding Glen Torridon region that are farther from the pediment contact contain ~30 wt.% smectite and lack cristobalite and opal-CT. Cristobalite and/or opal-CT are present in a few other targets elsewhere along the traverse, including the top of the nearby Vera Rubin ridge and the top of the Pahrump Hills outcrop. Stimson overlies the Pahrump Hills, and, based on projections of the pediment slope, the Stimson may have overlain Vera Rubin ridge. The proximity of the low-smectite and cristobalite- and/or opal-CT-bearing outcrops to the contact between the Murray and Stimson suggests the contact provided a conduit for diagenetic fluids that altered clay minerals and formed crystalline and paracrystalline silica.

E. B. Rampe↗
NASA NTRS1992

Mineralization on the moon? Theoretical considerations of Apollo 16 'rusty rocks', sulfide replacement in 67016, and surface-correlated volatiles on lunar volcanic glass

Theoretical considerations of vapor-rock interactions in the lunar environment are a useful supplement to petrologic studies of mineralization or alteration in rocks from the moon. They also provide insights into the potential for the existence of more extensive mineralization on the moon than is found in the limited sample set. Discussed in this paper are the coexistence and textural association in 66095 of the phases lawrencite, troilite, schreibersite, iron metal, and sphalerite; the replacement of olivine in certain clasts of 67016 by troilite and enstatite; and the existence of Zn + S deposits on the surfaces of volcanic glass beads. Particular attention is given in each case to whether the observed mineralization implies that metals, as well as S, P, or Cl, have been mobilized in the vapor. Vapor species that might mobilize metals in the absence of H2O are considered. Most importantly, the suggestion is made that in the dry lunar environment carbonyl species may be important carriers of S and metals. The implications of this possibility are discussed.

Colson, Russell O.↗
NASA NTRS2018

Adrianite, Ca12(Al4Mg3Si7)O32Cl6, a New Cl-rich Silicate Mineral From the Allende Meteorite: An Alteration Phase in a Ca-Al-rich Inclusion

Adrianite (IMA 2014-028), Ca12(Al4Mg3Si7)O32Cl6, is a new Cl-rich silicate mineral and the Si,Mg analog of wadalite. It occurs with monticellite, grossular, wadalite, and hutcheonite in altered areas along some veins between primary melilite, spinel, and Ti,Al-diopside in a Type B1 FUN (Fractionation and Unidentified Nuclear effects) Ca-Al-rich inclusion (CAI), Egg-3, from the Allende CV3 carbona-ceous chondrite. The mean chemical composition of type adrianite by electron probe microanalysis is (wt%) CaO 41.5, SiO2 27.5, Al2O3 12.4, MgO 7.3, Na2O 0.41, Cl 13.0, O=Cl –2.94, total 99.2, giving rise to an empirical formula of (Ca11.69Na0.21)(Al3.85Mg2.88Si7.23)O32Cl5.80. The end-member formula is Ca12(Mg5Si9)O32Cl6. Adrianite has the I43d wadalite structure with a = 11.981 Å, V = 1719.8 Å3, and Z = 2, as revealed by electron backscatter diffraction. The calculated density using the measured composition is 3.03 g/cm3. Adrianite is a new secondary mineral in Allende, apparently formed by alkali-halogen metasomatic alteration of primary CAI minerals such as melilite, anorthite, perovskite, and Ti,Al-diopside on the CV chondrite parent asteroid. Formation of secondary Cl-rich minerals sodalite, adrianite, and wadalite during metasomatic alteration of the Allende CAIs suggests that the metasomatic fluids had Cl-rich compositions. The mineral name is in honor of Adrian J. Brearley, mineralogist at the University of New Mexico, U.S.A., in recognition of his many contributions to the understanding of secondary mineralization in chondritic meteorites.

Chi Ma↗
NASA NTRS2024

Revision 1: Characterizing Basalt-Atmosphere Interactions on Venus: A Review of Thermodynamic and Experimental Results

The surface of Venus is in contact with a hot (~470° C), high pressure (92 bars), and caustic (CO 2 with S, but little H 2 O) atmosphere, which should cause progressive alteration of the crust in the form of sulfate and iron-oxide coatings; however, the exact rate of alteration and mineral species are not well constrained. Different experimental approaches, each with its own limitations, are currently being used to constrain mineralogy and alteration rate. One note is that no experimental approach has been able to fully replicate the necessary conditions and sustain them for a significant length of time. Further, geochemical modeling studies can also constrain surface alteration mineralogy, again with different assumptions and limitations. Here we review recent geochemical modeling and experimental studies to constrain the state of the art for alteration mineralogy, rate of alteration, open questions about the surface mineralogy of Venus, and what can be constrained before the fleet of missions arrive later this decade. Combining the new results confirm that basalt on the surface of Venus should react quickly and form coatings of sulfates and iron-oxides; however, the mineralogy and rate of alteration is dependent on physical properties of the protolith (including bulk composition, mineralogy, and crystallinity), as well as atmospheric composition, and surface temperature. Importantly, the geochemically modelling results show that the mineralogy is largely controlled by atmospheric oxygen fugacity, which is not well constrained for the near surface environment on Venus. Therefore, alteration experiments run over a range of oxygen and sulfur fugacities are needed across a wide range of Venus analog materials with varying mineralogy and crystallinity.

Justin Filiberto↗
NASA NTRS1984

Alterations in gut transport of minerals and in binding proteins during simulated weightlessness

The structural components of the skeleton develop and are maintained in a 1 g environment, shaped by the mechanical load to which they are constantly exposed. Altering such a mechanical load by reducing the gravitational force imposed on the system, as in space flight, has profound effects on the skeleton and permits an exploration of the molecular events which regulate normal skeletal homeostasis. The objective was to determine whether simulated weightlessness reduced intestinal calcium transport, and if so, to determine the molecular mechanisms for such an effect. A nonstressful tail suspension in which the rats gained weight normally while suspended was used to simulate weightlessness. A significant change in intestinal calcium transport was not demonstrated. However, a cyclic change in bone formation with suspension was shown. Based on these observations, the objective changed to determination of the hormonal regulation of bone formation during simulated weightlessness.

Bikle, D. D.↗
NASA NTRS1980

The effect of hypodynamia on mineral and protein metabolism in calcified tissues of the maxillodental system (experimental radioisotope study)

Mineral and protein metabolism was studied in experiments on 60 white rats, using P-32 and Ca-45 uptake in the mineral fractions, 2C-14-glycine in the protein fractions, and P-32 in both fractions of calcified tissues as indices over a 100 day period of experimental hypodynamia. Combined alterations in mineral and protein metabolism occurred in the calcified tissues of the experimental animals. The most pronounced changes were found in P-32 and 2C-14-glycine metabolism. In the incisors and femoral bones, these alterations occurred in two phases: P-32 and 2C-14-glycine uptake first increased, then decreased. Changes in Ca-45 metabolism were less pronounced, particularly in the initial period of the experiment. A marked reduction in P-32, Ca-45, and 2C-14-glycine uptake was found in various fractions of the calcified tissues on the 100th day of experimental hypodynamia.

Prokhonchukov, A. A.↗
NASA NTRS1982

Infrared airborne spectroradiometer survey results in the western Nevada area

The Mark II airborne spectroradiometer system was flown over several geologic test sites in western Nevada. The infrared mineral absorption bands were observed and recorded for the first time using an airborne system with high spectral resolution in the 2.0 to 2.5 micron region. The data show that the hydrothermal alteration zone minerals, carbonates, and other minerals are clearly visible in the airborne survey mode. The finer spectral features that distinguish the various minerals with infrared bands are also clearly visible in the airborne survey data. Using specialized computer pattern recognition methods, it is possible to identify mineralogy and map alteration zones and lithologies by airborne spectroradiometer survey techniques.

Collins, W.↗
DOE OSTI2020

A general mechanism for gel layer formation on borosilicate glass under aqueous corrosion

Mineral and glass dissolution is a scientific topic deeply investigated but incompletely understood and of a great interest for the geochemical and materials science communities. If the interfacial dissolution/reprecipitation mechanism seems to be applicable to most of silicate minerals, the debate remains open concerning glass. Here we studied two model glasses, a ternary borosilicate (CJ1) and the same glass doped with 4.1 mol% of Al2O3 (CJ2). The two glasses were altered at 90°C, pH 9, and in conditions far and close to saturation with respect to amorphous silica, to determine the initial and residual rates. Moreover, a specific experiment was conducted for a short duration with a solution highly enriched with 18O and 29Si isotopes to understand how passivating gels form. SEM, TEM and ToF-SIMS characterization, along with Monte Carlo simulations were used to understand the rate limiting reactions at play and infer the role of Al. We show that Al yields a slower matrix dissolution in dilute conditions. However, it slows down he formation and the maturation of the passivating gel and favors alteration by partial hydrolysis of Si and Al entities followed by in-situ reorganization/relaxation into a porous network. Unexpectedly, CJ1 experienced both interfacial dissolution/reprecipitation and partial hydrolysis followed by in situ reorganization of the silicate network during the course of a single experiment. This study offers a unified concept that can pave the way for the future development of a predictive kinetic model based on a detailed description of bond breaking and bond forming as a function of glass composition and alteration conditions.

Gin, Stephane↗
DOE OSTI2023

Wettability Alteration with Weak Acid-Assisted Surfactant Flood

Oil-wetness and heterogeneity are two key reasons for low oil recovery by waterflooding in carbonate reservoirs. Surfactants have been effective in altering the oil-wet matrix to a more water-wet condition and initiating spontaneous imbibition. Because it takes time for the surfactant to alter wettability, oil recovery from the tight matrix is slow and sometimes not economically feasible. Acids have the potential of dissolving minerals, which may alter wettability. In this study, the enhanced oil recovery (EOR) performance of an acid-assisted surfactant solution, a novel technique, was evaluated for low-temperature applications. A set of acids and their acetates were tested. Bulk rock-acid reaction, wettability alteration (WA) tests, and spontaneous imbibition measurements were conducted at reservoir temperature (35°C) to identify effective candidates. Coreflood tests were then performed to evaluate the selected acid-surfactant formulations. Before and after a coreflood test, the core was scanned using micro-computed tomography (CT) to investigate pore structure alteration. Bulk reaction measurements showed that weak acids, especially acetic acid (AA), have the desired low reaction rates at 35°C. WA tests showed that AA can remove the crude oil off the rock surface and alter wettability through mineral dissolution. The surfactant can reduce contact angles from 160° to 58°; adding acid into the surfactant can further reduce it to 52°. Spontaneous imbibition experiments showed the synergy between the acid and the surfactant; the AA-surfactant solution had the highest oil recovery (62.6%) among acid-surfactant formulations. The acid improves the WA efficiency by the surfactant through surface mineral dissolution and lower ζ-potential. The imbibition transports the acid-surfactant solutions into the matrix, which minimizes face dissolution. Coreflood tests show that the AA-surfactant flood can increase the oil recovery rate and recover about 8% more oil compared to the surfactant flood. Micro-CT showed that a few mineral particles were transported along the core and partially plugged pore throats, which reduced permeability and diverted flow leading to improved oil recovery. Here, the transport of the acid in reservoirs and the potential plugging issues have to be carefully evaluated in future studies.

58 GEOSCIENCES↗