Potentiometric investigation of the oxidation of ferrous chloride by oxygen
Effect of various catalyzers, hydrochloric acid, and iron chloride concentrations on oxidation rate of bivalent iron ions at room temperature
OXIDATION↗
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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.↗
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↗
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.↗
Mineralogy at Gusev Crater and Meridiani Planum from the Moessbauer Spectrometers on the Mars Exploration Rovers
The Moessbauer spectrometers on the twin MER rovers Spirit and Opportunity have provided significant new information on the distribution of iron among its oxidation states, the identification of the mineralogical composition of iron-bearing phases, and the distribution of iron among those phases for rock and soil at Gusev Crater and Meridiani Planum. The plains of Gusev Crater are dominated by olivine-bearing basalt (approximately Fo(60)) and Fe(3+)/Fe(total)=0.1 - 0.5. The oxide mineral generally present is magnetite. In contrast, initial results for the Columbia Hills are consistent with the presence of hematite and a ferrous iron phase, possibly pyroxene. Gusev spectra also have a ferric doublet (not jarosite) that is tentatively associated with nano-phase ferric oxide. A wider diversity of material is present at Meridiani Planum. Significantly, jarosite-bearing outcrop is present throughout the region, with good exposures in impact craters such as Eagle and Endurance (Fe(3+)/Fe (total) approx. 0.9). The Moessbauer identification of jarosite (a hydroxyl-bearing sulfate mineral) is evidence for aqueous, acid-sulfate processes on Mars. Hematite is observed within the outcrop matrix and in the spheroidal particles (Blueberries) found within the outcrop and as a surface lag. An isolated rock (Bounce Rock) was the only sample at either landing site whose iron-bearing phase was dominated by pyroxene. The basaltic sand in the central portion of Eagle crater, in the intercrater plains, and between slabs of outcrop at both Eagle and Endurance craters is olivine-bearing basalt. The widespread occurrence of olivine-bearing basalt at both MER landing sites implies that physical, rather than chemical, weathering processes dominate at the surface of contemporary Mars.
Morris, Richard V.↗
An empirical approach to predicting long term behavior of metal particle based recording media
Alpha iron particles used for magnetic recording are prepared through a series of dehydration and reduction steps of alpha-Fe2O3-H2O resulting in acicular, polycrystalline, body centered cubic (bcc) alpha-Fe particles that are single magnetic domains. Since fine iron particles are pyrophoric by nature, stabilization processes had to be developed in order for iron particles to be considered as a viable recording medium for long term archival (i.e., 25+ years) information storage. The primary means of establishing stability is through passivation or controlled oxidation of the iron particle's surface. Since iron particles used for magnetic recording are small, additional oxidation has a direct impact on performance especially where archival storage of recorded information for long periods of time is important. Further stabilization chemistry/processes had to be developed to guarantee that iron particles could be considered as a viable long term recording medium. In an effort to retard the diffusion of iron ions through the oxide layer, other elements such as silicon, aluminum, and chromium have been added to the base iron to promote more dense scale formation or to alleviate some of the non-stoichiometric behavior of the oxide or both. The presence of water vapor has been shown to disrupt the passive layer, subsequently increasing the oxidation rate of the iron. A study was undertaken to examine the degradation in magnetic properties as a function of both temperature and humidity on silicon-containing iron particles between 50-120 deg C and 3-89 percent relative humidity. The methodology to which experimental data was collected and analyzed leading to predictive capability is discussed.
Hadad, Allan S.↗
Moessbauer Mineralogical Evidence for Aqueous Processes at Gusev Crater and Meridiani Planum
The Moessbauer spectrometers on the MER rovers have measured the relative abundances of iron with respect to both oxidation state and iron-bearing phase at Gusev Crater (Spirit rover) and Meridiani Planum (Opportunity rover). The assemblage of phases indicates aqueous alteration processes at both landing sites. Although the rock and soil of the Gusev Crater plains are dominated by Fe(2+) in olivine-bearing basalt (approx.Fo60), a Fe(3+)-rich component (nanophase ferric oxide, np-Ox) has significant abundance in surface soils (13-28% of total Fe) and in the surface coatings (rinds) of certain rocks (39%) but not in rock interiors exposed by grinding (5-6%). The mode of occurrence of np-Ox implies that it is the product of oxidative alteration of Fe(2+) silicate and oxide phases in the presence of H2O. The ubiquitous presence of sulfur in soil and in rock coatings, as determined by the MER-A APXS instrument, suggests that the alteration occurred under acid-sulfate conditions, so that both hydrolytic and sulfatic reactions are viable. A possible source for the weathering agents is volcanic emanations rich in H2O and SO2. Generally, rocks in the Columbia Hills are significantly more altered than those in the Gusev plains, with a higher proportion of Fe(3+) oxide phases compared to Fe(2+) silicate phases. This mineralogical dichotomy implies a difference in the timing, rate, duration, and/or mechanism of alteration for basaltic material in the Gusev plains compared to basaltic material in the Columbia Hills. It is possible, for example, that the basaltic material in the Columbia Hills underwent aqueous alteration in a paleoclimate that favored nearly complete alteration and that the basaltic material of the Gusev plains will not achieve the degree of alteration exhibited by the Columbia Hills under current martian surface conditions.
Morris, R. V.↗
New evidence for a dramatic rise in atmosphere oxygen ca. 1,900 m.y. ago
Several lines of geologic evidence have pointed to a significant increase in P sub O2 about 2,000 m.y. ago, but the magnitude of P sub O2 before and after that time has been quite uncertain. The data that we have recently accumulated suggest that P sub O2 was approximately less than 2 x 10 (exp -3) atm more than 2,000 m.y. ago, and approximately greater than 0.03 atm more recently than ca. 1,900 m.y. ago. These estimates are based on the behavior of iron in Precambrian weathering horizons. More than ca. 2,000 m.y. ago, Fe(+2), released during the weathering of basalts was not oxidized to Fe(+3), and was removed in ground water from the upper layers of soil horizons. More recently than ca. 1,850 m.y. ago, Fe(+2) was oxidized to Fe(+3) and precipitated as iron oxides and hydroxides in such soil horizons and in the weathering products of a carbonate facies banded iron formation in Griqualand West, South Africa. The O2 content of the atmosphere must have increased dramatically about 1,900 m.y. ago to explain these observations. The reasons for the increase are still obscure, but are probably related to changes in the biologic productivity of the oceans. Eukaryotes appear to have developed shortly after the increase in P sub O2, perhaps in response to the subsequent increase in the supply of nitrate from the atmosphere to the oceans.
Holland, H. D.↗
Signatures of aging silicate dust
A self-consistent explanation for the width, strength, and position of spectral features which may be diagnostic of the structure and composition of circumstellar and interstellar silicate grains is presented based on a long series of laboratory experiments using simple oxide analogs. The ratio of the integrated absorption strength of the grains near 10 mu to that near 20 mu is shown to decrease monotonically with increased processing. This ratio may be diagnostic of the relative age of the silicate. The oxidation state of iron in the grains is directly related to both the near-IR grain opacity and enhanced absorption in the UV. The oxidation state of both iron and silicon is directly related to the rate of nucleation, growth, and processing in a circumstellar outflow, as well as to the processing history of the grain after it reaches the interstellar medium. Other diagnostic indicators of the average silicon oxidation state, degree of structural polymerization, and dispersion in the average degree of structural polymerization are discussed.
Nuth, Joseph A., III↗
Studies of Lubricating Materials in Vacuum
Lubricating materials for use in a vacuum environment have been the subject of a series of experimental investigations. Evaporation properties were evaluated for solid polymeric compositions. Friction and wear studies explored the behavior during sliding contact for series of polymeric compositions, binary alloys containing soft film-forming phases, complex alloys with film-forming materials, and a burnished MoS2 film. Friction and wear experiments were conducted at 10(exp-9)mm Hg with a 3/16-inch-radius-hemisphere rider specimen sliding on the flat surface of a rotating 2-1/2-inch-diameter disk specimen with materials that had low rates of evaporation. The influence of fillers in polytetrafluoroethylene (PTFE) on decomposition during vacuum friction studies was determined with a mass spectrometer. A real advantage in reducing decomposition and improving friction wear properties is gained by adding fillers (e.g., copper) that improve thermal conductivity through the composite materials. A polyimide and an epoxy-MoS2 composition material were found to have better friction and wear properties than PTFE compositions. A series of alloys (cast binary as well as more complex alloys) that contained microinclusions of potential film-forming material was studied. These materials replaced the normal surface oxides as they were worn away on sliding contact. Iron sulfide, nickel oxide, and tin are typical film-forming materials employed and were demonstrated to be effective in inhibiting surface welding and reducing friction. A burnished MoS2 film applied to type 440-C stainless steel in argon with a rotating soft wire brush had good endurance properties but somewhat higher friction than commercially available bonded films. An oil film applied to the burnished MoS2 markedly reduced its endurance life.
WEAR↗
Backscatter Mossbauer Spectrometer (BaMS) for extraterrestrial applications
Mossbauer spectroscopy is a nuclear gamma resonance technique particularly well suited to the study of materials that contain iron (Fe-57). It can provide information on the oxidation state of iron as well as the type and proportion of iron-containing mineral species in a sample of interest. Iron Mossbauer spectroscopy (FeMS) has been applied to samples believed to have come from Mars (SNC meteorites) and has been helpful in refining the choice among putative Martian surface materials by suggesting a likely nanophase component of the Martian regolity. FeMS spectrum of a Martial analogue material (Hawaiian palagonite) is shown; it is dominated by ferric-bearing phases and shows evidence of a nanophase component. FeMS has also been applied to lunar materials. It can be used to measure the maturity of lunar surface material and has been proposed as a prospector for lunar ilmenite, an oxygen resource mineral. Several years ago we suggested a backscatter Mossbauer spectrometer (BaMS) for a Mars rover mission. Backscatter design was selected as most appropriate for in-situ application because no sample preparation is required. Since that time, we have continued to develop the BaMS instrument in anticipation that it would eventually find a home on a NASA planetary mission. Gooding proposed BaMS as a geochemistry instrument on MESUR. More recently, an LPI workshop has recommended that BaMS be included in a three-instrument payload on the next (1996?) lunar lander.
Agresti, D. G.↗
Ordovician paleosols at Arisaig, Nova Scotia, and the evolution of the atmosphere
A series of Late Ordovician andesite flows are exposed along the coastline near Arisaig, Nova Scotia. Field relationships, textural and mineralogical evidence, and chemical analyses of three interflow units confirm that they are paleosols. The chemical variations observed in these paleosols are quite similar to those of modern soils developed on mafic volcanic rocks. Virtually all of the iron in the paleosols was oxidized and retained during weathering; however, in two of the three paleosols a small fraction of the ferrous iron escaped oxidation and was precipitated near the base of the paleosols. This redistribution of ferrous iron may reflect the presence of nonvascular land plants. The variations in the concentration of the major oxides produced by weathering of the andesites at Arisaig are consistent with the probable lower limit of 0.04 atm for the partial pressure of O2 in the atmosphere during the Late Ordovician. The current data base for Paleozoic and Precambrian paleosols indicates that a significant increase in the PO2/PCO2 ratio in the atmosphere took place about 2.0 x 10(9) years ago; since then the ratio of PO2/PCO2 in the atmosphere has been high enough to oxidize all of the iron in soils developed on igneous rocks.
Non-NASA Center↗
The Miniaturized Moessbauer Spectrometer MIMOS II of the Athena Payload for the 2003 MER Missions
A first-order requirement of spacecraft missions that land on Mars is instrumentation for in situ mineralogical analysis. Moessbauer Spectroscopy is a powerful tool for quantitative analysis of Fe-bearing materials. The Athena Moessbauer spectrometer MIMOS II on the martian surface will provide: (1) identification of iron-bearing phases (e.g., oxides, silicates, sulfides, sulfates, and carbonates), (2) quantitative measurement of the distribution of iron among its oxidation states (e.g., Fe(2+)/Fe(3+) ratio), and (3) quantitative measurement of the distribution of iron among iron-bearing phases (e.g., the relative proportions of iron in olivine, pyroxene, and magnetite in a basalt) in rocks and soils. Moessbauer data will also be highly complementary with chemical analyses from the APXS and the Mini-TES compositional data. Mars is a particularly good place to do Moessbauer mineralogy because its surface is iron rich (approx. 20% Fe as Fe2O3). Moessbauer spectrometers that are built with backscatter measurement geometry require no sample preparation, a factor important for in situ planetary measurements.
G Klingelhoefer↗
Chemical and Microstructural Changes in Metallic and Ceramic Materials Exposed to Venusian Surface Conditions
The chemical and microstructural behavior of steels (304, 310, 316, and 1018), nickel-based alloys (beta-NiAl, G30, and 625), gold, coatings (4YSZ, SilcoNert(TradeMark) 1040 (SilcoTek Co.), Dursan(TradeMark) (SilcoTek Co.), and porcelain), and bulk ceramics (alpha-Al2O3, fused quartz, beta-SiC, and alpha-Si3N4) were probed after exposure to supercritical fluid with temperature, pressure, and composition mimicking the Venus lower atmosphere. Exposures were carried out in the Glenn Extreme Environments Rig (GEER) chamber with the Venusian gas mixture (96.5% CO2, 3.5% N2, 30 ppm H2O, 150 ppm SO2, 28 ppm CO, 15 ppm OCS, 3 ppm H2S, 0.5 ppm HCl, and 5 ppb HF) at 92 bar (1330 psi) and 467 C (873 F) for durations of 10 and 42 days. An additional 21-day exposure was done to stainless steel uncoated and coated with SilcoNert(TradeMark) and Dursan(TradeMark). Samples were characterized before and after the experiment by gravimetric analysis, X-ray diffraction, X-ray photoelectron and Auger electron spectroscopies, and cross section electron microscopy analysis. All steels exposed for 10 and 42 days formed double-layered scales consisting mainly of metal (Cr, Fe, Ni) oxides and sulfides showing different chemistry, microstructure, and crystalline phases. The alloys G30 and 625 formed double-layered scales consisting mainly of nickel sulfides. After 10 days, the beta-NiAl exhibited no detectable scale, suggesting only a very thin film was formed. The 304 and 316 stainless steels coated with 4YSZ that were exposed for 10 and 42 days exhibited no significant oxidation. Steel 1018 coated with 4YSZ exhibited a corrosion scale of iron and/or chromium oxide formed at the base of the alloy. The 304 steel coated with porcelain did not exhibit corrosion, although the coating exhibited recession. SilcoNert(TradeMark) exposed for 10 and 42 days exhibited recession, although no oxidation was found to occur at the base of the alloy. Stainless steel 316 coated with Dursan(TradeMark) exhibited corrosion at the base of the alloy. All ceramics tested showed no clear evidence of reaction. The weight-gain-per-area performance of the materials exposed in the GEER for 10 and 42 days are reported from the lowest to the highest weight gain per area as follows: gold did not exhibit any weight change; nickel-based alloys: beta- NiAl < G30 < 625; steels: 304 < 310 < 316 < 1018; ceramics: considering the experimental uncertainties, no weight change was observed for all ceramics of this work (alpha-Al2O3, Si3N4, SiC, and amorphous SiO2).
Costa, Gustavo C. C.↗
Cutting in-line with iron: ribosomal function and non-oxidative RNA cleavage
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Rebecca Guth-Metzler↗
Deposition Of Cubic BN On Diamond Interlayers
Thin films of polycrystalline, pure, cubic boron nitride (c-BN) formed on various substrates, according to proposal, by chemical vapor deposition onto interlayers of polycrystalline diamond. Substrate materials include metals, semiconductors, and insulators. Typical substrates include metal-cutting tools: polycrystalline c-BN coats advantageous for cutting ferrous materials and for use in highly oxidizing environments-applications in which diamond coats tend to dissolve in iron or be oxidized, respectively.
Ong, Tiong P.↗
Preliminary Characterization of a Microbial Community of Rock Varnish from Death Valley, California
Rock varnish (also referred to as desert varnish in the literature because it is particularly noticeable in desert environments) is a dark, thin (typically 50-500 m thick), layered veneer composed of clay minerals cemented together by oxides and hydroxides of manganese and iron. Some scientists suggest that varnish may provide a historical record of environmental processes such as global warming and long-term climate change. However, despite more than 30 years of study using modern microanalytical and microbial culturing techniques, the nucleation and growth mechanisms of rock varnish remain a mystery. Rock varnish is of interest to the Mars science community because a varnish-like sheen has been reported on the rocks at the Viking Lander sites. It therefore important for us to understand the formation mechanisms of terrestrial varnish abiotic, biotic, or a combination of the two -- as this understanding may give us clues concerning the chemical and physical processes occurring on the surface of Mars. It is strongly believed by some in the biogeochemistry community that microbes have a role in forming rock varnish, and iron- and manganese-oxidation by microbes isolated from varnish has been extensively investigated. Only two of these studies have investigated the microbial genetics of varnish. These studies examined the morphological, physiological and molecular characteristics of microbes that had previously been cultured from various rock varnishes and identified the cultivars using 16S rDNA sequencing techniques. However, it is well known that most of organisms existing in nature are refractory to cultivation, so many important organisms would have been missed. The currently described work investigates the genetics of rock varnish microbial community from a site in the Whipple Mtns., south of Death Valley, CA, near Parker, Arizona. We employed both cultural and molecular techniques to characterize the microorganisms found within the varnish and surrounding soil with the objectives of (a) identifying microorganisms potentially involved in varnish formation, and (b) discovering microorganisms that simply use the varnish as an extreme habitat.
Kuhlman, K. R.↗