Distribution and diagenesis of organic compounds in JOIDES sediment from Gulf of Mexico and western Atlantic.
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The major carotenoids at three levels (3, 40, and 175 m below the sediment-water interface) in a core from a marine sediment (Cariaco Trench, off Venezuela) have been examined. Mass and electronic spectral data have provided evidence for the onset of a progressive reduction of carotenoids in the geological column. The time scale of the process appears to depend on the particular carotenoid. Reduction of up to two double bonds is observed for the diol, zeaxanthin, in the oldest sediment (about 340,000 years old) but no reduction is observed in the younger samples (about 5000 and 56,000 years old). The diketone, canthaxanthin, shows evidence of reduction of up to two double bonds in the 56,000-yr sample and up to five double bonds in the oldest sample. No reduction of beta-carotene was observed in any of the samples.
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Anomalous isotopic composition has been reported for the carbon in carbonate minerals of banded iron formations. Well studied examples show an enrichment in the light isotope of carbon, C-12. This enrichment presumably reflects unusual circumstances in the deposition of these sedimentary rocks. It is suggested here that the isotopically light carbonate results from early diagenetic oxidation by bacteria of substantial amounts of isotopically light organic carbon. The electron acceptor that permits oxidation in the absence of free oxygen is presumed to be Fe(III), which may have been significantly more abundant in the initial chemical precipitate than in the postdiagenetic sedimentary rock.
A model is proposed which eases the thermal constraints imposed by earlier models of low-temperature aqueous alteration in primitive extraterrestrial materials in which formation of an aqueous medium promoting these alterations required complete melting of the water-ice. It is argued that low-temperature alterations in a protoplanetary body such as the formation of hydrated silicates will occur because of the presence of an interfacial water layer.
Spherules with relict glass cores in the K/T boundary bed of Haiti allow for a comparison of these bodies with hollow goyazite shells in the K/T boundary claystone of Wyoming and with younger microtektites of the Ivory Coast strewn field. Samples of the Haitian beds from undisturbed sections at Beloc, as determined by Jehanno et al., contain both hollow shells and relict glass cores rimmed by palagonite that has been partially converted to smectite. These palagonite rims developed from hydration zones formed when hot, splash-form droplets of andesitic impact glass were deposited into water. Mutual collisions between these droplets in the ejecta curtain may have formed point-source stresses on their surfaces. Initiation of hydration would be facilitated at these surface stress points and propagated radially into the glass. The inner surface of these merged hemispherical fronts appears mammillary, which is reflected as scalloping in Haitian relict glass cores.
A carbon isotope mass balance was determined for the sediments of Cape Lookout Bight, NC to constrain the carbon budgets published previously. The diffusive, ebullitive and burial fluxes of sigma CO2 and CH4, as well as the carbon isotope signatures of these fluxes, were measured. The flux-weighted isotopic signature of the remineralized carbon (-18.9 plus or minus 2.7 per mil) agreed with the isotopic composition of the remineralized organic carbon determined from the particulate organic carbon (POC) delta(C-13) profiles (-19.2 plus or minus 0.2), verifying the flux and isotopic signature estimates. The measured delta(C-13) values of the sigma CO2 and CH4 diffusive fluxes were significantly different from those calculated from porewater gradients. The differences appear to be influenced by methane oxidation at the sediment-water interface, although other potential processes cannot be excluded. The isotope mass balance provides important information concerning the locations of potential diagenetic isotope effects. Specifically, the absence of downcore change in the delta(C-13) value of the POC fraction and the identical isotopic composition of the POC and the products of remineralization indicate that no isotopic fractionation is expressed during the initial breakdown of the POC, despite its isotopically heterogeneous composition.
Two distinct generations of microfossils occur in silicified carbonates from a previously undescribed locality of the Lower Proterozoic Duck Creek Dolomite, Western Australia. The earlier generation occurs in discrete organic-rich clasts and clots characterized by microquartz anhedra; it contains a variety of filamentous and coccoidal fossils in varying states of preservation. Second generation microfossils consist almost exclusively of well-preserved Gunflintia minuta filaments that drape clasts or appear to float in clear chalcedony. These filaments appear to represent an ecologically distinct assemblage that colonized a substrate containing the partially degraded remains of the first generation community. The two assemblages differ significantly in taxonomic frequency distribution from previously described Duck Creek florules. Taken together, Duck Creek microfossils exhibit a range of assemblage variability comparable to that found in other Lower Proterozoic iron formations and ferruginous carbonates. With increasing severity of post-mortem alteration, Duck Creek microfossils appear to converge morphologically on assemblages of simple microstructures described from early Archean cherts. Two new species are described: Oscillatoriopsis majuscula and O. cuboides; the former is among the largest septate filamentous fossils described from any Proterozoic formation.
Polycyclic aromatic hydrocarbons with varying degrees of aromatization were isolated from the Eocene Messel Shale (Rheingraben, Germany). The high abundances of these compounds and their structural resemblances to cyclic triterpenoid lipids are consistent with derivation from microbial rather than thermal processes. Compounds structurally related to oleanane contain from five to nine double bonds; those within a series of aromatized hopanoids contain from three to nine. All are products of diagenetic reactions that remove hydrogen or methyl groups, and, in several cases, break carbon-carbon bonds to open rings. Aromatized products are on average depleted in 13C relative to possible precursors by l.2% (range: l.5% enrichment to 4% depletion, n = 9). The dependence of 13C content on the number of double bonds is not, however, statistically significant and it must be concluded that there is no strong evidence for isotopic fractionation accompanying diagenetic aromatization. Isotopic differences between series (structures related to ursane, des-A-ursane, des-A-lupane, des-A-arborane, and possibly, des-A-gammacerane are present) are much greater, indicating that 13C contents are controlled primarily by source effects. Fractionations due to chromatographic isotope effects during HPLC ranged from 0.1 to 2.8%.
Samples from the Huns Limestone Member, Urusis Formation, Nama Group, at two adjacent localities in southern Namibia contain thin foliose to arched, sheet-like carbonate crusts that are 100-500 micrometers thick and up to 5 cm in lateral dimension. Morphologic, petrographic, and geochemical evidence supports the interpretation of these delicate crusts as biogenic, most likely the remains of calcified encrusting metaphytes. The original sediments of the fossiliferous samples contained aragonitic encrusting algae, botryoidal aragonite cements, and an aragonite mud groundmass. Spherulites within the precursor mud could represent bacterially induced mineral growths or the concretions of marine rivularian cyanobacteria. Original textures were severely disrupted during the diagenetic transition of aragonite to low-magnesian calcite, but some primary structures remain discernible as ghosts in the neomorphic mosaic. Gross morphology, original aragonite mineralogy, and hypobasal calcification indicate that the crusts are similar to late Paleozoic phylloid algae and extant peyssonnelid red algae. Structures interpreted as possible conceptacles also suggest possible affinities with the Corallinaceae. Two species of Cloudina, interpreted as the remains of a shelly metazoan, are also known from limestones in the Nama Group. It is possible, therefore, that skeletalization in metaphytes and animals arose nearly simultaneously near the end of the Proterozoic Eon.
The Athena science payload onboard the Opportunity rover identified hematite-rich spherules (mean diameter of 4.2 +/- 0.8 mm) embedded in outcrops and occurring as lag deposits at Meridiani Planum. They have formed as diagenetic concretions from the rapid breakdown of pre-existing jarosite and other iron sulfates when chemically distinct groundwater passed through the sediments. Diagenetic, Fe-cemented concretions found in the Jurassic Navajo Formation, Utah and hematite-rich spherules found within sulfate-rich volcanic breccia on Mauna Kea volcano, Hawaii are possible terrestrial analogues for Meridiani spherules. The Navajo Formation concretions form in porous quartz arenite from the dissolution of iron oxides by reducing fluids and subsequent Fe precipitation to form spherical Fe- and Si-rich concretions. The Mauna Kea spherules form by hydrothermal, acid-sulfate alteration of basaltic tephra. The formation of hematite-rich spherules with similar chemical, mineralogical, and morphological properties to the Meridiani spherules is rare on Earth, so little is known about their formation conditions. In this study, we have synthesized in the laboratory hematite-rich spherules that are analogous in nearly all respects to the Meridiani spherules.
The Thermal Emission Spectrometer (TES) onboard the Mars Global Surveyor (MGS) orbiter discovered a large area at Meridiani Planum (MP) covered with the Fe-oxide hematite (alpha-Fe2O3) [1,2]. This discovery and favorable landing site characteristics led to selection of MP as the landing site for the Opportunity Mars Exploration Rover (MER) [3]. The Athena science payload onboard the Opportunity rover identified hematite-rich spherules (mean spherule diameter approx.4.2+/-0.8 mm) embedded in S-rich outcrop rock and also as lag deposits of whole and broken spherules [4,5,6,7,8,9]. Although the chemical and mineralogical compositions of spherules are not fully constrained, Moessbauer spectrometer (MB) Miniature Thermal Emission Spectrometer (Mini-TES) and chemical analyses from the Alpha Particle X-Ray Spectrometer (APXS) are consistent with a hematite mineralogical composition and an oxide bulk chemical composition consisting of Fe2O3. MGS-TES, also provides an important constraint that emission from the hematite-rich spherules is dominated by emission along the crystallographic c-axis [1,2,10,11]. The formation of hematite-rich spherules with similar chemical, mineralogical, morphological, and crystallographic properties to the MP spherules is rare on Earth, to date, only two natural analogs have been proposed; one from Utah (Navaho Concretions) and the other from Mauna Kea, Hawaii [12,13]. In this study, we synthesized in the laboratory hematite-rich spherules using conditions that may have existed on Early Mars [14] and compared their properties to those for MP hematite spherules of Mars and the analog spherules from Utah and Mauna Kea in order to assess their relative merit as MP hematite spherule analogs. Such comparisons yield clues to the formation pathway for MP spherules.
Mars landed missions returned im-ages at increasingly higher spatial resolution (Table 1). These images help to constrain the microstructure of Martian soils, i.e. the grain-by-grain association of chemistry and mineralogy with secondary properties, such as albedo, color, magnetic properties, and mor-phology (size, shape, texture). The secondary charac-teristics are controlled by mineralogical composition as well as the geo-setting (transport and weathering modes, e.g. water supply, pH, atmospheric properties, exposure to radiation, etc.). As of today this association is poorly constrained. However, it is important to un-derstand soil-forming processes on the surface of Mars. Here we analyze high-resolution images of soils re-turned by different landed missions. Eventually these images must be combined with other types of data (chemistry and mineralogy at small spatial scale) to nail down the microstructure of Martian soils.
The Mars Science Laboratory (MSL) Curiosity rover began investigating the rocks of Mt. Sharp in September 2014. The Murray formation is the lowermost unit, which is mostly comprised of finely laminated mudstones, suggesting these sediments were deposited in a lacustrine environment. It is important to characterize the geochemical and mineralogical trends throughout the Murray Fm to interpret the aqueous conditions of the ancient lake, the sources of the lake sediments, and post-depositional alteration processes. Four samples have been drilled from the Murray Fm so far: Confidence Hills, Mojave 2, and Telegraph Peak were collected from the Pahrump Hills member - the basal portion of the Murray Fm, and Buckskin was collected in the Marias Pass region (Fig. 1). The drill fines were delivered to the instruments inside the rover, including the CheMin instrument, a combination X-ray diffractometer and X-ray fluorescence spectrometer. Rietveld refinements and FULLPAT analyses of 1D CheMin XRD patterns were performed to determine quantitative abundances of minerals and amor-phous phases and the unit cell parameters of minerals present in abundances greater than 4-5 wt.%.
The Mars Science Laboratory rover Curiosity has been exploring sedimentary deposits in Gale crater since August 2012. The rover has traversed up section through approx.100 m of sedimentary rocks deposited in fluvial, deltaic, lacustrine, and eolian environments (Bradbury group and overlying Mount Sharp group). The Stimson formation lies unconformable over 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. Mineralogy of the unaltered Stimson sandstone consists of plagioclase feldspar, pyroxenes, and magnetite with minor abundances of hematite, and Ca-sulfates (anhydrite, bassanite). Unaltered sandstone has a composition similar to the average Mars crustal composition. Alteration "halos" occur adjacent to fractures in the Stimson. Fluids passing through these fractures have altered the chemistry and mineralogy of the sandstone. Silicon and S enrichments and depletions in Al, Fe, Mg, Na, K, Ni and Mn suggest aqueous alteration in an open hydrologic system. Mineralogy of the altered Stimson is dominated by Ca-sulfates, Si-rich X-ray amorphous materials along with plagioclase feldspar, magnetite, and pyroxenes, but less abundant in the altered compared to the unaltered Stimson sandstone and lower pyroxene/plagioclase feldspar. The mineralogy and geochemistry of the altered sandstone suggest a complicated history with several (many?) episodes of aqueous alteration under a variety of environmental conditions (e.g., acidic, alkaline).
We model the fluids involved in the alteration processes recorded in the Sheep bed Member mudstones of Yellowknife Bay (YKB), Gale crater, Mars, as revealed by the Mars Science Laboratory Curiosity rover investigations. We compare the Gale crater waters with fluids modeled for shergottites, nakhlites, and the ancient meteorite ALH 84001, as well as rocks analyzed by the Mars Exploration rovers, and with terrestrial ground and surface waters. The aqueous solution present during sediment alteration associated with phyllosilicate formation at Gale was high in Na, K, and Si; had low Mg, Fe, and Al concentrations relative to terrestrial ground waters such as the Deccan Traps and other modeled Mars fluids; and had near neutral to alkaline pH. Ca and S species were present in the 10(exp -3) to 10(exp -2) concentration range. A fluid local to Gale crater strata produced the alteration products observed by Curiosity and subsequent evaporation of this ground water- type fluid formed impure sulfate- and silica-rich deposits veins or horizons. In a second, separate stage of alteration, partial dissolution of this sulfate-rich layer in Yellowknife Bay,or beyond, led to the pure sulfate veins observed in YKB. This scenario is analogous to similar processes identified at a terrestrial site in Triassic sediments with gypsum veins of the Mercia Mudstone Group in Watchet Bay, UK.
The Windjana drill sample, a sandstone of the Dillinger member (Kimberley formation, Gale Crater, Mars), was analyzed by CheMin X-ray diffraction (XRD) in the MSL Curiosity rover. From Rietveld refinements of its XRD pattern, Windjana contains the following: sanidine (21% weight, approximately Or(sub 95)); augite (20%); magnetite (12%); pigeonite; olivine; plagioclase; amorphous and smectitic material (approximately 25%); and percent levels of others including ilmenite, fluorapatite, and bassanite. From mass balance on the Alpha Proton X-ray Spectrometer (APXS) chemical analysis, the amorphous material is Fe rich with nearly no other cations-like ferrihydrite. The Windjana sample shows little alteration and was likely cemented by its magnetite and ferrihydrite. From ChemCam Laser-Induced Breakdown Spectrometer (LIBS) chemical analyses, Windjana is representative of the Dillinger and Mount Remarkable members of the Kimberley formation. LIBS data suggest that the Kimberley sediments include at least three chemical components. The most K-rich targets have 5.6% K2O, approximately 1.8 times that of Windjana, implying a sediment component with greater than 40% sanidine, e.g., a trachyte. A second component is rich in mafic minerals, with little feldspar (like a shergottite). A third component is richer in plagioclase and in Na2O, and is likely to be basaltic. The K-rich sediment component is consistent with APXS and ChemCam observations of K-rich rocks elsewhere in Gale Crater. The source of this sediment component was likely volcanic. The presence of sediment from many igneous sources, in concert with Curiosity's identifications of other igneous materials (e.g.,mugearite), implies that the northern rim of Gale Crater exposes a diverse igneous complex, at least as diverse as that found in similar-age terranes on Earth.