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Coccolithophorid blooms in the global ocean

The global distribution pattern of coccolithophrid blooms was mapped in order to ascertain the prevalence of these blooms in the world's oceans and to estimate their worldwide production of CaCO3 and dimethyl sulfide (DMS). Mapping was accomplished by classifying pixels of 5-day global composites of coastal zone color scanner imagery into bloom and nonbloom classes using a supervised, multispectral classification scheme. Surface waters with the spectral signature of coccolithophorid blooms annually covered an average of 1.4 x 10(exp 6) sq km in the world oceans from 1979 to 1985, with the subpolar latitudes accounting for 71% of this surface area. Classified blooms were most extensive in the Subartic North Atlantic. Large expanses of the bloom signal were also detected in the North Pacific, on the Argentine shelf and slope, and in numerous lower latitude marginal seas and shelf regions. The greatest spatial extent of classified blooms in subpolar oceanic regions occurred in the months from summer to early autumn, while those in lower latitude marginal seas occurred in midwinter to early spring. Though the classification scheme was effcient in separating bloom and nonbloom classes during test simulations, and biogeographical literature generally confirms the resulting distribution pattern of blooms in the subpolar regions, the cause of the bloom signal is equivocal in some geographic areas, particularly on shelf regions at lower latitudes. Standing stock estimates suggest that the presumed Emiliania huxleyi blooms act as a significant source of calcite carbon and DMS sulfur on a regional scale. On a global scale, however, the satellite-detected coccolithophorid blooms are estimated to play only a minor role in the annual production of these two compounds and their flux from the surface mixed layer.

Brown, Christopher W.↗

Carbonates and sulfates in the Chassigny meteorite: Further evidence for aqueous chemistry on the SNC parent planet

Scanning electron microscopy and energy-dispersive X-ray spectrometry of untreated interior chips from three different specimens of the Chassigny meteorite confirm the presence of discrete grains of Ca-carbonate, Mg-carbonate, and Ca-sulfate. Morphologies of these salt grains suggest that the Ca-carbonate is calcite (CaCO3) and that the Ca-sulfate is gypsum (CaSO4-2H2O) or bassanite (CaSO4-1/2H2O). The morphologic identification of the Mg-carbonate is equivocal, but rhombohedral and acicular crystal habits suggest magnesite and hydromagnesite, respectively. The salts in Chassigny occur as discontinuous veins in primary igneous minerals and are similar to those previously documented in the nakhlites, Nakhla and Lafayette, and in shergottite EETA79001. Unlike those in nakhlites, however, the Chassigny salts occur alone, without associated ferric oxides or aluminosilicates clays. Traces of Cl and P in Chassigny salts are consistent with precipitation of the salts from short-lived, saline, aqueous solutions that postdated igneous crystallization. In contrast with the clear case for nakhlites, stratigraphic evidence for a preterrestrial origin of the salts in Chassigny is ambiguous; however, a preterrestrial origin of the Chassigny salts best explains all available evidence. The water-precipitated salts provide clear physical evidence for the hypothesis, proposed by other workers, that the igneous amphiboles in Chassigny might have experienced isotope-exchange reactions with near-surface water, thereby compromising the original stable-isotope signature of any magmatic water in melt inclusions.

Wentworth, Susan J.↗

Carbonates in the Kaidun chondrite

Kaidun is a remarkable chondrite breccia fall containing lithic clasts that span a wide range of chondrite groups including C and E chondrites, as well as having clasts with characteristics not yet found in existing chondrite samples. The dominant lithology in Kaidun appears to be CR chondritic, consonant with recent O isotope data. The carbonates in Kaidun are presented as one mineralogical basis for comparing it to the other hydrated chondrites and to better understand its relative alteration history. The four polished thin sections of Kaidun studied contained a variety of lithologies that we classified into four groups -- CR, E, CM-like, and dark inclusions (DIs). DIs contain sulfide and magnetite morphologies that superficially resemble CI chondrites, and some of the previously reported CI lithologies in Kaidun may be what we term DIs. Carbonates were found in all lithologies studied. Carbonates in Kaidun are similar in composition to those in CR chondrites. Some of the DIs in Kaidun, previously characterized as CI, have carbonates similar to those in CR chondrites and are unlike those in CI or CM chondrites. Most carbonates in Kaidun and CR chondrites are calcites, some of which formed at temperatures above 250 C. Dolomite is less common and some may be metastable. Alteration temperatures in the Renazzo CR chondrite were estimated to be approximately 300 C, based on O isotope fractionation between phyllosilicates and magnetite. Temperatures of up to 450 C were proposed for the alteration of a CR-like dark inclusion in Kaidun, based on the presence of hydrothermal pentlandite veins. The alteration temperatures for Kaidun and the other CR chondrites are considerably higher than those suggested for CI or CM parent bodies.

Weisberg, M. K.↗

Hydrous carbonates on Mars? Evidence from Mariner 6/7 infrared spectrometer and ground-based telescopic spectra

Absorption features at 2.28 and 5.4 micrometers identified in Mariner 6/7 infrared spectrometer and terrestrial telescopic spectra are consistent with the spectra of hydrous magnesium carbonates such as hydromagnesite and artinite. Spectral characteristics of these hydrous carbonates are different from those of the anhydrous carbonates, as the former do not have the strong spectral features typically associated with anhydrous carbonates such as calcite and siderite. Theoretical mixing indicates that, depending on the type of hydrous carbonate, 10-20 wt % can be incorporated into the regolith without contradicting the spectral observations or the Viking x ray fluorescence chemical analysis. Hydrous carbonates form as weathering products of mafic minerals in the presence of H2O and CO2, even in the Antarctic. Their formation as evaporite minerals from either original magmas or hydrothermally altered rocks is consistent with the Martian environment, provided liquid water is or has been at least transiently present. On Earth, formation of hydrous Mg carbonates is associated with the production of amorphous iron oxides, which is consistent with both the environment and the inferred surface mineralogy of Mars. These minerals are about 60 wt % H2O, CO3, and OH; if they are abundant everywhere at the 10% level, then about 6% of the surface weight could be volatiles bound in this type of mineral. Although the spectroscopic evidence for anhydrous carbonates is scant, the possible presence of hydrous carbonates provides an appealing mechanism for the existence of carbonates on Mars.

Calvin, Wendy M.↗

Development of the gravity-sensing organs in the Japanese red-bellied newt, Cynops pyrrhogaster

Pre-mated adult female newts and fertilized eggs will be flown on the International Microgravity Laboratory-2 flight, schedule for 1994. One objective of the flight will be to observe the influence of microgravity on the development of the gravity-sensing organs in the inner ear. These organs contain sensory hair cells covered by a layer of dense stones (otoliths). Gravity and linear acceleration exert forces on these masses, leading to excitation of the nerve fibers innervating the hair cells. If the production of the otoliths is regulated to reach an optimal weight, their development would be abnormal in microgravity. Ground-based control experiments are reported describing the developmental sequence in which the otoliths and their associated sensory epithelium appear and increase in size. Three-dimensional reconstruction of serial sections through the otic vesicle of newt embryos at stages 31 through 40 demonstrate the first appearance, relative position and growth of the otoliths. In adult newts, the otoconia in the utricle appear similar to mammalian otoconia, which are composed of calcite. The newt saccular otoconia are at least 99% aragonite, as is found in most aquatic species. Reports of experiments in which fertilized frog eggs were flown on a Russian Cosmos mission conclude that the utricular otolith is increased in volume, whereas the saccular otolith maintains normal size, suggesting that at least the utricular weight might be regulated.

Wiederhold, Michael L.↗

Near-Surface Geologic Units Exposed Along Ares Vallis and in Adjacent Areas: A Potential Source of Sediment at the Mars Pathfinder Landing Site

A sequence of layers, bright and dark, is exposed on the walls of canyons, impact craters and mesas throughout the Ares Vallis region, Chryse Planitia, and Xanthe Terra, Mars. Four layers can be seen: two pairs of alternating dark and bright albedo. The upper dark layer forms the top surface of many walls and mesas. The upper dark-bright pair was stripped as a unit from many streamlined mesas and from the walls of Ares Valles, leaving a bench at the top of the lower dark layer, approximately 250 m below the highland surface on streamlined islands and on the walls of Ares Vallis itself. Along Ares Vallis, the scarp between the highlands surface and this bench is commonly angular in plan view (not smoothly curving), suggesting that erosion of the upper dark-bright pair of layers controlled by planes of weakness, like fractures or joints. These near-surface layers in the Ares Vallis area have similar thicknesses, colors, and resistances to erosion to layers exposed near the tops of walls in Valles Marineris (Treiman et al.) and may represent the same pedogenic hardpan units. From this correlation, and from analogies with hardpans on Earth, the light-color layers may be cemented by calcite or gypsum. The dark layers are likely cemented by an iron-bearing mineral. Mars Pathfinder instruments should permit recognition and useful analyses of hardpan fragments, provided that clean uncoated surfaces are accessible. Even in hardpan-cemented materials, it should be possible to determine the broad types of lithologies in the Martian highlands. However, detailed geochemical modeling of highland rocks and soils may be compromised by the presence of hardpan cement minerals.

Treiman, Allan H.↗

Development of a Technique for Separating Raman Scattering Signals from Background Emission with Single-Shot Measurement Potential

A novel technique for extracting Q-branch Raman signals scattered by a diatomic species from the emission spectrum resulting from the irradiation of combustion products using a broadband excimer laser has been developed. This technique is based on the polarization characteristics of vibrational Raman scattering and can be used for both single-shot Raman extraction and time-averaged data collection. The Q-branch Raman signal has a unique set of polarization characteristics which depend on the direction of the scattering while fluorescence signals are unpolarized. For the present work, a calcite crystal is used to separate the horizonal component of a collected signal from the vertical component. The two components are then sent through a UV spectrometer and imaged onto an intensified CCD camera separately. The vertical component contains both the Raman signal and the interfering fluorescence signal. The horizontal component contains the fluorescence signal and a very weak component of the Raman signal; hence, the Raman scatter can be extracted by taking the difference between the two signals. The separation of the Raman scatter from interfering fluorescence signals is critically important to the interpretation of the Raman for cases in which a broadband ultraviolet (UV) laser is used as an excitation source in a hydrogen-oxygen flame and in all hydrocarbon flames. The present work provides a demonstration of the separation of the Raman scatter from the fluorescence background in real time.

Hartfield, Roy J., Jr.↗

Calcium Solubility and Cation Exchange Properties in Zeoponic Soil

An important aspect of a regenerative life support system at a Lunar or Martian outpost is the ability to produce food. Essential plant nutrients, as well as a solid support substrate, can be provided by: (1) treated Lunar or Martian regolith; (2) a synthetic soil or (3) some combination of both. A synthetic soil composed of ammonium- and potassium-saturated chinoptlolite (a zeolite mineral) and apatite, can provide slow-release fertilization of plants via dissolution and ion-exchange reactions. Previous equilibrium studies (Beiersdorfer, 1997) on mixtures of synthetic hydroxyapatite and saturated-clinoptilolite indicate that the concentrations of macro-nutrients such as ammonium, phosphorous, potassium, magnesium, and calcium are a function of the ratio of chinoptilolite to apatite in the sample and to the ratio of potassium to ammonium on the exchange sites in the clinoptilolite. Potassium, ammonium, phosphorous, and magnesium are available to plants at sufficient levels. However, calcium is deficient, due to the high degree of calcium adsorption by the clinoptilolite. Based on a series of batch-equilibration experiments, this calcium deficiency can be reduced by (1) treating the clinoptilolite with CaNO3 or (2) adding a second Ca-bearing mineral (calcite, dolomite or wollastonite) to the soil. Treating the Cp with CaNO3 results in increased Ca in solution, decreased P in solution and decreased NH4 in solution. Concentrations of K were not effected by the CaNO3 treatment. Additions of Cal, Dol and Wol changed the concentrations of Ca and P in solution in a systematic fashion. Cal has the greatest effect, Dol the least and Wol is intermediate. The changes are consistent with changes expected for a common ion effect with Ca. Higher concentrations of Ca in solution with added Cal, Dol or Wol do not result in changes in K or NH4 concentrations.

Beiersdorfer, Raymond E.↗

Raman Gas Species Measurements in Hydrocarbon-Fueled Rocket Engine Injector Flows

Propellent injector development at MSFC (Marshall Space Flight Center) includes experimental analysis using optical techniques, such as Raman, fluorescence, or Mie scattering. For the application of spontaneous Raman scattering to hydrocarbon-fueled flows a technique needs to be developed to remove the interfering polycyclic aromatic hydrocarbon fluorescence from the relatively weak Raman signals. A current application of such a technique is to the analysis of the mixing and combustion performance of multijet, impinging-jet candidate fuel injectors for the baseline Mars ascent engine, which will burn methane and liquid oxygen produced in-situ on Mars to reduce the propellent mass transported to Mars for future manned Mars missions. The present technique takes advantage of the strongly polarized nature of Raman scattering. It is shown to be discernable from unpolarized fluorescence interference by subtracting one polarized image from another. Both of these polarized images are obtained from a single laser pulse by using a polarization-separating calcite rhomb mounted in the imaging spectrograph. A demonstration in a propane-air flame is presented.

Wehrmeyer, Joseph A.↗

Raman Gas Species Measurements in Hydrocarbon-Fueled Rocket Engine Injector Flows

Rocket engine propellent injector development at NASA-Marshall includes experimental analysis using optical techniques, such as Raman, fluorescence, or Mie scattering. For the application of spontaneous Raman scattering to hydrocarbon-fueled flows a technique needs to be developed to remove the interfering polycyclic aromatic hydrocarbon fluorescence from the relatively weak Raman signals. A current application of such a technique is to the analysis of the mixing and combustion performance of multijet, impinging-jet candidate fuel injectors for the baseline Mars ascent engine, which will burn methane and liquid oxygen produced in-situ on Mars to reduce the propellent mass transported to Mars for future manned Mars missions. The Raman technique takes advantage of the strongly polarized nature of Raman scattering. It is shown to be discernable from unpolarized fluorescence interference by subtracting one polarized image from another. Both of these polarized images are obtained from a single laser pulse by using a polarization-separating calcite rhomb mounted in the imaging spectrograph. A demonstration in a propane-air flame is presented, as well as a high pressure demonstration in the NASA-Marshall Modular Combustion Test Artice, using the liquid methane-liquid oxygen propellant system

Wehrmeyer, Joseph↗

Calcium Solubility In Zeolite Synthetic-Apatite Mixtures

Life support systems at a lunar or martian outpost will require the ability to produce food growing in 1) treated lunar or martian regolith; 2) a synthetic soil, or 3) some combination of both. Zeoponic soil, composed of NH4 (-) and K-exchanged clinoptilolite (Cp) and synthetic apatite (Ap), can provide slow-release fertilization via dissolution and ion-exchange. Equilibrium studies indicate that KNH4, P, and Mg are available to plants at sufficient levels, however, Ca is deficient. Ca availability can be increased by adding a second Ca-bearing mineral: calcite (Cal); dolomite (Dol); or wollastonite (Wol). Additions of Cal, Dol, and Wol systematically change the concentrations of Ca and P in solution. Cal has the greatest effect, Dol the least, and Wol is intermediate.

Beiersdorfer, R.↗

Mineralogical and Geochemical Analyses of Antarctic Lake Sediments: A Reflectance and Moessbauer Spectroscopy Study with Applications for Remote Sensing on Mars

Lakebottom sediments from the Dry Valleys region of Antarctica have been analyzed here in order to study the influence of water chemistry on the mineralogy and geochemistry of these sediments, as well as to evaluate techniques for remote spectral identification of potential biomarker minerals on Mars. Lakes from the Dry Valleys region of Antarctica have been investigated as possible analogs for extinct lake environments on early Mars. Sediment cores were collected in the present study from perennially ice-covered Lake Hoare in the Taylor Valley. These sediments were taken from a core in an oxic region of the lake and another core in an anoxic zone. Differences between the two cores were observed in the sediment color, Fe(II)/Fe(III) ratio, the presence of pyrite, the abundance of Fe, S and some trace elements, and the C, N and S isotope fractionation patterns. The results of visible-infrared reflectance spectroscopy (0.3-25 microns) Mossbauer spectroscopy (77 and 4 K) and X-ray diffraction are combined to determine the mineralogy and composition of these samples. The sediments are dominated by plagioclase, K-feldspar, quartz and pyroxene. Algal mats grow on the bottom of the lake and organic material has been found throughout the cores. Calcite is abundant in some layers of the aerobic core (shallow region) and pyrite is abundant in some layers of the anaerobic core (deep region). Analysis of the spectroscopic features due to organics and carbonates with respect to the abundance of organic C and carbonate contents was performed in order to select optimal spectral bands for remote identification of these components in planetary regoliths. Carbonate bands near 4 and 6.8 microns (approx.2500 and 1500/cm) were detected for carbonate abundances as low as 0.1 wt.% CO2. Organic features at 3.38, 3.42 and 3.51 microns (2960, 2925 and 2850/cm) were detected for organic C abundances as low as 0.06 wt.% C. The d13C trends show a more complex organic history for the anaerobic sediments than for the aerobic sediments. The biogenic pyrite found in the anaerobic core is associated with lighter d34S values and high organic C levels and could be used as a biomarker mineral for paleolakes on Mars.

Froeschl, Heinz↗

Validation of Surface Bio-Optical Properties in the Gulf of Maine as a Means for Improving Satellite Primary Production Estimates

One of the greatest challenges in providing sea-truth data for various ocean color sensors is climatology. This is particularly true in the Gulf of Maine since it is cloudy and foggy more than it is clear; the climatology shows on average, about one in four to five days has clear skies with clear days slightly more frequent in the late summer and early fall. Our strategy has been to use a ship of opportunity where one has choice of the sampling days. This provides much better flexibility to sample during clear periods with good satellite coverage. Our Sensor Intercomparison and Merger for Biological and Interdisciplinary Oceanic Studies (SIMBIOS) contract has been to use the M/S Scotia Prince ferry as a ship of opportunity, running between Portland, Maine and Yarmouth, NS. Measurements include continuous, surface, along-track fluorescence, two independent measures of backscattering, total light scattering, absorption, beam attenuation, above-water remote sensing reflectance, calcite-dependent light scattering, temperature, and salinity. Expendable bathythermography (XBT) drops allow acquisition of vertical temperature information, useful for defining isopycnal slope, which affects primary production. These data are comparable to a previous program from early 1982, where a ship of opportunity program (SOOP) was run on the truck ferry, M/V Marine Evangeline, which ran along the same transect. These surface data were combined with satellite-derived sea surface temperature fields to examine the Maine coastal current. Unfortunately, this program stopped in 1982. The ongoing SIMBIOS results will dovetail nicely with the previous work (which also had Coastal Zone Color Scanner (CZCS) coverage) for looking at any long-term changes in the Gulf of Maine hydrography, bio-optics, and biogeochemistry.

Balch, William M.↗

Raman Spectroscopy for Instantaneous Multipoint, Multispecies Gas Concentration and Temperature Measurements in Rocket Engine Propellant Injector Flows

Propellent injector development at MSFC includes experimental analysis using optical techniques, such as Raman, fluorescence, or Mie scattering. For the application of spontaneous Raman scattering to hydrocarbon-fueled flows a technique needs to be developed to remove the interfering polycyclic aromatic hydrocarbon fluorescence from the relatively weak Raman signals. A current application of such a technique is to the analysis of the mixing and combustion performance of multijet, impinging-jet candidate fuel injectors for the baseline Mars ascent engine, which will bum methane and liquid oxygen produced in-situ on Mars to reduce the propellent mass transported to Mars for future manned Mars missions. The present technique takes advantage of the strongly polarized nature of Raman scattering. It is shown to be discernable from unpolarized fluorescence interference by subtracting one polarized image from another. Both of these polarized images are obtained from a single laser pulse by using a polarization-separating calcite rhomb mounted in the imaging spectrograph. A demonstration in a propane-air flame is presented.

Wehrmeyer, Joseph A.↗

Raman Spectroscopy for Instantaneous Multipoint, Multispecies Gas Concentration and Temperature Measurements in Rocket Engine Propellant Injector Flows

Propellant injector development at MSFC includes experimental analysis using optical techniques, such as Raman, fluorescence, or Mie scattering. For the application of spontaneous Raman scattering to hydrocarbon-fueled flows a technique needs to be developed to remove the interfering polycyclic aromatic hydrocarbon fluorescence from the relatively weak Raman signals. A current application of such a technique is to the analysis of the mixing and combustion performance of multijet, impinging-jet candidate fuel injectors for the baseline Mars ascent engine, which will burn methane and liquid oxygen produced in-situ on Mars to reduce the propellant mass transported to Mars for future manned Mars missions. The present technique takes advantage of the strongly polarized nature of Raman scattering. It is shown to be discernable from unpolarized fluorescence interference by subtracting one polarized image from another. Both of these polarized images are obtained from a single laser pulse by using a polarization-separating calcite rhomb mounted in the imaging spectrograph. A demonstration in a propane-air flame is presented.

Wehrmeyer, Joseph A.↗

Effects of Microsecond Pulse Laser Irradiation on Vis-NIR Reflectance Spectrum of Carbonaceous Chondrite Simulant: Implications for Martian Moons and Primitive Asteroids

Goal of this study is to make a progress in understanding the optical effects of space weathering on small bodies believed to be similar in composition to carbonaceous chondrites: C, G, B, F, T, D, and P asteroids and possibly Martian satellites Phobos and Deimos. The companion work focuses on petrological and mineralogical aspects of this process. One of the main factors of space weathering is meteorite and micrometeorite bombardment leading, in particular, to impact melting of components of the regolith. Studies of lunar regolith and laboratory experiments simulating impact melting show that the melting products differ from the unmelted material in mineralogy and distribution of chemical components among different phases that results in spectral changes. We simulate impact melting of CM chondrite by pulse laser irradiation of an artificial analog of such a meteorite. The analog is a mixture of 46 wt.% non-magnetic fraction of L5 ordinary chondrite Tsarev, 47 wt.% serpentine, 5 wt.% kerite, and 2 wt.% calcite. It simulates rather well bulk chemistry, including volatiles such as H2O and CO2, and only approximately the CM chondrite mineralogy. Thus, we do not expect the mixture to be spectrally similar to CM chondrites, but expect the laser melting products to be similar to those formed by impact melting of natural CM chondrites.

Hiroi, T.↗

Osmium Isotope Constraints on the Proportion of Bolide Component in Chicxulub Impact Melts

Recent drilling has produced the samples of impact melt breccias examined here. All samples examined here are from the YAX-1 borehole [7]. Two main types of impact breccias have been studied. The first type is a green altered impact meltrock found in the lower portion of the impact sequence. The texture of the rock is microcrystalline and is composed of pyroxene, plagioclase, and alkali feldspars. Its composition is consistent with continental margin rocks. It is generally massive with some flow structure. The rock was brecciated and altered after solidfication and contains small amounts of both shocked and unshocked clasts of the impacted lithologies. These lithologies include lithic quartzite, and isolated feldspar crystals. The compositions of these rocks are similar to those seen in meltrocks sampled by the Yucatan-6 borehole [8-9]. Our study includes samples YAX-1_861.4, YAX-1_863.51, and YAX- 1_876.46, which represent both the top and lower portion of the green impact meltrock. The middle sample in the sequence has the least amount of (mineralogical) alteration [10]. The second type of melt breccia under study is a brown altered impact meltrock. It also has a microcrystalline texture and both shocked and unshocked clasts of the target material. Even though this rock type has been altered, remnant schleiren, metaquartzite, and micritic calcite have been identified. Sample YAX-1_841.32 is representative of this type of rock. It was recovered from a polymict breccia in the middle of the impact sequence.

Gelinas, A.↗