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34 records · Page 2

A comparison of iron extraction methods for the determination of degree of pyritisation and the recognition of iron-limited pyrite formation

Measurements of degree of pyritisation require an estimate of sediment iron which is capable of reaction with dissolved sulphide to form pyrite, either directly or indirectly via iron monosulphide precursors. Three dissolution techniques (buffered dithionite, cold 1 M HCl, boiling 12 M HCl) were examined for their capacity to extract iron from a variety of iron minerals, and iron-bearing sediments, as a function of different extraction times and different grain sizes. All the iron oxides studied are quantitatively extracted by dithionite and boiling HCl (but not by cold HCl). Both HCl techniques extract more iron from silicates than does dithionite but probably about the same amounts as are potentially capable of sulphidation. Modern sediment studies indicate that most sedimentary pyrite is formed rapidly from iron oxides, with smaller amounts formed more slowly from iron silicates (if sufficient geologic time is available). It is therefore recommended that the degree of pyritisation be defined with respect to the dithionite-extractable (mainly iron oxide) pool and/or the boiling HCl-extractable pool (which includes some silicate iron) for the recognition of iron-limited pyritisation.

NASA Discipline Exobiology↗

Lipophilic pigments from the benthos of a perennially ice-covered Antarctic lake

The benthos of a perennially ice-covered Antarctic lake, Lake Hoare, contained three distinct 'signatures' of lipophilic pigments. Cyanobacterial mats found in the moat at the periphery of the lake were dominated by the carotenoid myxoxanthophyll; carotenoids: chlorophyll a ratios in this high light environment ranged from 3 to 6.8. Chlorophyll c and fucoxanthin, pigments typical of golden-brown algae, were found at 10 to 20 m depths where the benthos is aerobic. Anaerobic benthic sediments at 20 to 30 m depths were characterized by a third pigment signature dominated by a carotenoid, tentatively identified as alloxanthin from planktonic cryptomonads, and by phaeophytin b from senescent green algae. Pigments were not found associated with alternating organic and sediment layers. As microzooplankton grazers are absent from this closed system and transformation rates are reduced at low temperatures, the benthos beneath the lake ice appears to contain a record of past phytoplankton blooms undergoing decay.

NASA Discipline Number 52-30↗

The Flin Flon paleosol and the composition of the atmosphere 1.8 BYBP

Within the 1800 to 1900 my old Flin Flon-Snow Lake greenstone belt, Amisk Group volcanics are overlain by Missi Group fluvial sediments. Several localities along the Missi-Amisk contact, the volcanics show evidence of subaerial weathering. Field relationships, mineralogical evidence, and chemical analyses confirm that this alteration zone is a paleosol. Pedogenic fabrics and mineralogy were somewhat obscured by greenschist-grade metamorphism associated with the Hudsonian orogeny (1750 my). This is especially true in the upper meter of the paleosol, where metamorphic paragonite and sericitic micas developed in a crenulated fabric. This metamorphism did not, however, obliterate the imprint of weathering on the Amisk volcanics. Features characteristic of well-drained modern soils are evident in the paleosol. Corestones of spheroidally weathered pillow lavas occur at depth within the paleosol (Cr horizon). The corestones decrease in size upward and eventually disappear into a hematite-rich horizon at the top of the paleosol. These macroscopic changes are accompanied by a decrease in CaO and MgO and by an increase in Al2O3, TiO2, and total iron toward the paleosol-Missi contact. Ferrous iron decreases upward toward the contact; FeO was apparently oxidized to ferric iron and retained within the paleosol during weathering. The oxidation and retention of iron within the Flin Flon paleosol indicates that PO2 was probably > or = 10(-2) P.A.L. at the time of weathering. The behavior of iron in the Flin Flon paleosol contrasts sharply with its behavior in the 2200 my Hekpoort paleosol, which is strongly depleted in iron. This difference suggests that a significant increase in the ratio of PO2/PCO2 in the atmosphere took place between 2200 and 1800 mybp.

Non-NASA Center↗

Natural abundances of carbon isotopes in acetate from a coastal marine sediment

Measurements of the natural abundances of carbon isotopes were made in acetate samples isolated from the anoxic marine sediment of Cape Lookout Bight, North Carolina. The typical value of the total acetate carbon isotope ratio (delta 13C) was -16.1 +/- 0.2 per mil. The methyl and carboxyl groups were determined to be -26.4 +/- 0.3 and -6.0 +/- 0.3 per mil, respectively, for one sample. The isotopic composition of the acetate is thought to have resulted from isotopic discriminations that occurred during the cycling of that molecule. Measurements of this type, which have not been made previously in the natural environment, may provide information about the dominant microbial pathways in anoxic sediments as well as the processes that influence the carbon isotopic composition of biogenic methane from many sources.

NASA Discipline Exobiology↗

Carbon-isotopic analysis of dissolved acetate

Heating of dried, acetate-containing solids together with oxalic acid dihydrate conveniently releases acetic acid for purification by gas chromatography. For determination of the carbon-isotopic composition of total acetate, the acetate-containing zone of the chromatographic effluent can be routed directly to a combustion furnace coupled to a vacuum system allowing recovery, purification, and packaging of CO2 for mass-spectrometric analysis. For analysis of methyl carbon, acetic acid can be cryogenically trapped from the chromatographic effluent, then transferred to a tube containing excess NaOH. The tube is evacuated, sealed, and heated to 500 degrees C to produce methane by pyrolysis of sodium acetate. Subsequent combustion of the methane allows determination of the 13C content at the methyl position in the parent acetate. With typical blanks, the standard deviation of single analyses is less than 0.4% for acetate samples larger than 5 micromoles. A full treatment of uncertainties is outlined.

Non-NASA Center↗

Does sedimentary organic delta 13C record variations in quaternary ocean [CO2(aq)]?

Ocean surface water [CO2(aq)] variations based on glacial/interglacial changes in sediment delta 13Corg are shown to compare favorably with reconstructions based on ice core [CO2]. In particular, an approximate 80 microatmospheres increase in atmospheric pCO2 during the last glacial-interglacial transition is calculated to correspond to a 3-4 micromolar increase in ocean surface water [CO2(aq)] at atmospheric equilibrium. A widespread marine delta 13Corg decrease of 1-2% accompanied this event and was not preceded by an equivalent isotopic change in surface water total dissolved inorganic carbon. These observations support the hypothesis that [CO2(aq)] influences photosynthetic isotope fractionation between marine inorganic and organic carbon pools, and therefore that plankton/sediment delta 13Corg may serve as a proxy for surface water [CO2(aq)].

NASA Program Exobiology↗

Origin of petroporphyrins. 2. Evidence from stable carbon isotopes

Compared with the carbon-13 isotopic composition of the ubiquitous C32DPEP (DPEP, deoxophylloerythroetioporphyrin) the heavy but equivalent carbon-13 isotopic composition for the porphyrin structures 15(2)-methyl-15,17-ethano-17-nor-H-C30DPEP and 15,17-butano-, 13,15-ethano-13(2),17-propano-, and 13(1)-methyl-13,15-ethano-13(2),17-propanoporphyrin suggests a common precursor, presumably chlorophyll c, for these petroporphyrins isolated from the marine Julia Creek oil shale and the lacustrine Condor oil shale. Similarly, the heavy but variable carbon-13 isotopic composition of 7-nor-H-C31DPEP compared with C32DPEP is consistent with an origin from both chlorophyll b and chlorophyll c3. The equivalent carbon-13 isotopic composition for 13(2)-methyl-C33DPEP compared with C32DPEP suggests a common origin resulting from a weighted average of chlorophyll inputs.

NASA Program Exobiology↗

Evidence from massive siderite beds for a CO2-rich atmosphere before approximately 1.8 billion years ago

It is generally thought that, in order to compensate for lower solar flux and maintain liquid oceans on the early Earth, methane must have been an important greenhouse gas before approximately 2.2 billion years (Gyr) ago. This is based upon a simple thermodynamic calculation that relates the absence of siderite (FeCO3) in some pre-2.2-Gyr palaeosols to atmospheric CO2 concentrations that would have been too low to have provided the necessary greenhouse effect. Using multi-dimensional thermodynamic analyses and geological evidence, we show here that the absence of siderite in palaeosols does not constrain atmospheric CO2 concentrations. Siderite is absent in many palaeosols (both pre- and post-2.2-Gyr in age) because the O2 concentrations and pH conditions in well-aerated soils have favoured the formation of ferric (Fe3+)-rich minerals, such as goethite, rather than siderite. Siderite, however, has formed throughout geological history in subsurface environments, such as euxinic seas, where anaerobic organisms created H2-rich conditions. The abundance of large, massive siderite-rich beds in pre-1.8-Gyr sedimentary sequences and their carbon isotope ratios indicate that the atmospheric CO2 concentration was more than 100 times greater than today, causing the rain and ocean waters to be more acidic than today. We therefore conclude that CO2 alone (without a significant contribution from methane) could have provided the necessary greenhouse effect to maintain liquid oceans on the early Earth.

Greenhouse Effect↗

Terminal Proterozoic reorganization of biogeochemical cycles

The Proterozoic aeon (2,500-540 million years ago) saw episodic increases in atmospheric oxygen content, the evolution of multicellular life and, at its close, an enormous radiation of animal diversity. These profound biological and environmental changes must have been linked, but the underlying mechanisms have been obscure. Here we show that hydrocarbons extracted from Proterozoic sediments in several locations worldwide are derived mainly from bacteria or other heterotrophs rather than from photosynthetic organisms. Biodegradation of algal products in sedimenting matter was therefore unusually complete, indicating that organic material was extensively reworked as it sank slowly through the water column. We propose that a significant proportion of this reworking will have been mediated by sulphate-reducing bacteria, forming sulphide. The production of sulphide and consumption of oxygen near the ocean surface will have inhibited transport of O2 to the deep ocean. We find that preservation of algal-lipid skeletons improves at the beginning of the Cambrian, reflecting the increase in transport by rapidly sinking faecal pellets. We suggest that this rapid removal of organic matter will have increased oxygenation of surface waters, leading to a descent of the O2-sulphide interface to the sea floor and to marked changes in the marine environment, ultimately contributing to the Cambrian radiation.

Non-NASA Center↗

Evidence from carbon isotope measurements for diverse origins of sedimentary hydrocarbons

The organic matter found in sedimentary rocks must derive from many sources; not only from ancient primary producers but also from consumers and secondary producers. In all of these organisms, isotope effects can affect the abundance and distribution of 13C in metabolites. Here, by using an improved form of a previously described technique in which the effluent of a gas chromatograph is continuously analysed isotopically, we report evidence of the diverse origins of sedimentary organic matter. The record of 13C abundances in sedimentary carbonate and total organic carbon can be interpreted in terms of variations in the global carbon cycle. Our results demonstrate, however, that isotope variations within sedimentary organic mixtures substantially exceed those observed between samples of total organic carbon. Resolution of isotope variations at the molecular level offers a new and convenient means of refining views both of localized palaeoenvironments and of control mechanisms within the global carbon cycle.

Non-NASA Center↗

Iron and sulfur in the pre-biologic ocean

Tentative geochemical cycles for the pre-biologic Earth are developed by comparing the relative fluxes of oxygen, dissolved iron, and sulfide to the atmosphere and ocean. The flux of iron is found to exceed both the oxygen and the sulfide fluxes. Because of the insolubility of iron oxides and sulfides the implication is that dissolved iron was fairly abundant and that oxygen and sulfide were rare in the atmosphere and ocean. Sulfate, produced by the oxidation of volcanogenic sulfur gases, was the most abundant sulfur species in the ocean, but its concentration was low by modern standards because of the absence of the river-borne flux of dissolved sulfate produced by oxidative weathering of the continents. These findings are consistent with the geologic record of the isotopic composition of sedimentary sulfates and sulfides. Except in restricted environments, the sulfur metabolism of the earliest organisms probably involved oxidized sulfur species not sulfide.

Review↗

The limits of palaeontological knowledge: finding the gold among the dross

Palaeontological interpretation rests on two interwoven sets of comparisons with the modern world. Palaeobiological interpretation relies on the placement of fossils within a phylogenetic and functional framework based primarily on the comparative biology of living organisms. Analogy to currently observable chemical, physical and taphonomic processes enables palaeoenvironmental inferences to be drawn from geological data. In older rocks, comparisons with the modern Earth can become tenuous, limiting palaeontological interpretation. The problem reaches its apogee in Archaean successions, yet pursuit of multiple lines of evidence establishes that complex microbial communities, fuelled by autotrophy and, likely, photoautotrophy, existed 3500 million years ago. Although Archaean palaeontology has to date focused on silicified coastal sediments, improved understanding of Earth's earliest biosphere may depend on the development of alternative environmental and taphonomic analogies. Spring precipitates and hydrothermal metal deposits are promising candidates. Terrestrial organisms may be of limited value in interpreting such fossils as may be found on Mars, although some points of comparison could prove general. Given limited opportunities for exploration, proper choice of environmental analogy is critical. Spring precipitates constitute excellent deposits for addressing questions of biology on another planet.

NASA Discipline Exobiology↗

Stable light isotope biogeochemistry of hydrothermal systems

The stable isotopic composition of the elements O, H, S and C in minerals and other chemical species can indicate the existence, extent, conditions and the processes (including biological activity) of hydrothermal systems. Hydrothermal alteration of the 18O/16O and D/H values of minerals can be used to detect fossil systems and delineate their areal extent. Water-rock interactions create isotopic signatures which indicate fluid composition, temperature, water-rock ratios, etc. The 18O/16O values of silica and carbonate deposits tend to increase with declining temperature and thus help to map thermal gradients. Measurements of D/H values can help to decipher the origin(s) of hydrothermal fluids. The 34S/32S and 13C/12C values of fluids and minerals reflect the origin of the S and C as well as oxygen fugacities and key redox processes. For example, a wide range of 34S/32S values which are consistent with equilibration below 100 degrees C between sulfide and sulfate can be attributed to sulfur metabolizing bacteria. Depending on its magnitude, the difference in the 13C/12C value of CO2 and carbonates versus organic carbon might be attributed either to equilibrium at hydrothermal temperatures or, if the difference exceeds 1% (10/1000), to organic biosynthesis. Along the thermal gradients of thermal spring outflows, the 13C/12C value of carbonates and 13C-depleted microbial organic carbon increases, principally due to the outgassing of relatively 13C-depleted CO2.

Review, Tutorial↗

An integrated view of the chemistry and mineralogy of martian soils

The mineralogical and elemental compositions of the martian soil are indicators of chemical and physical weathering processes. Using data from the Mars Exploration Rovers, we show that bright dust deposits on opposite sides of the planet are part of a global unit and not dominated by the composition of local rocks. Dark soil deposits at both sites have similar basaltic mineralogies, and could reflect either a global component or the general similarity in the compositions of the rocks from which they were derived. Increased levels of bromine are consistent with mobilization of soluble salts by thin films of liquid water, but the presence of olivine in analysed soil samples indicates that the extent of aqueous alteration of soils has been limited. Nickel abundances are enhanced at the immediate surface and indicate that the upper few millimetres of soil could contain up to one per cent meteoritic material.

Geologic Sediments/chemistry↗

Elemental Geochemistry of Sedimentary Rocks at Yellowknife Bay, Gale Crater, Mars

Sedimentary rocks examined by the Curiosity rover at Yellowknife Bay, Mars, were derived from sources that evolved from an approximately average martian crustal composition to one influenced by alkaline basalts. No evidence of chemical weathering is preserved, indicating arid, possibly cold, paleoclimates and rapid erosion and deposition. The absence of predicted geochemical variations indicates that magnetite and phyllosilicates formed by diagenesis under low-temperature, circumneutral pH, rock-dominated aqueous conditions. Analyses of diagenetic features (including concretions, raised ridges, and fractures) at high spatial resolution indicate that they are composed of iron- and halogen-rich components, magnesium-iron-chlorine-rich components, and hydrated calcium sulfates, respectively. Composition of a cross-cutting dike-like feature is consistent with sedimentary intrusion. The geochemistry of these sedimentary rocks provides further evidence for diverse depositional and diagenetic sedimentary environments during the early history of Mars.

Research Support, U.S. Gov't, Non-P.H.S.↗