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At least 19 records

Were kinetics of Archean calcium carbonate precipitation related to oxygen concentration?

Archean carbonates commonly contain decimetre- to metre-thick beds consisting entirely of fibrous calcite and neomorphosed fibrous aragonite that precipitated in situ on the sea floor. The fact that such thick accumulations of precipitated carbonate are rare in younger marine carbonates suggests an important change in the modes of calcium carbonate precipitation through time. Kinetics of carbonate precipitation depend on the concentration of inhibitors to precipitation that reduce crystallization rates and crystal nuclei formation, leading to kinetic maintenance of supersaturated solutions. Inhibitors also affect carbonate textures by limiting micrite precipitation and promoting growth of older carbonate crystals on the sea floor. Fe2+, a strong calcite-precipitation inhibitor, is thought to have been present at relatively high concentrations in Archean seawater because oxygen concentrations were low. The rise in oxygen concentration at 2.2-1.9 Ga led to the removal of Fe2+ from seawater and resulted in a shift from Archean facies, which commonly include precipitated beds, to Proterozoic facies, which contain more micritic sediment and only rare precipitated beds.

Non-NASA Center↗

Evaluation of ERTS data for certain oceanographic uses

The author has identified the following significant results. Upwelling along the eastern shore of Lake Michigan was occurring during the 3 and 21 August 1973 visits by ERTS-1. The NOAA-2 VHRR thermal-IR data are being digitized for comparison. Early indications are that these upwellings induced a calcium carbonate precipitate to form in the surface waters. It is most pronounced in the MSS-4 channel. On the lake bottom this jell-like sediment is known as marl and adds to the eutrophication of the lake. This phenomenon may help to explain the varve-like nature of bottom cores that have been observed in the Great Lakes.

Strong, A. E.↗

Extensive summer upwelling on Lake Michigan during 1973 observed by NOAA-2 and ERTS-1 satellites

Two studies are presented that utilize data from the NOAA-2 and ERTS-1 satellites. The studies are concentrated on two summer upwelling episodes in Lake Michigan when considerable contrast was observed in both surface water temperature as observed by NOAA-2 and surface water color as observed by ERTS-1. Physical, biological and chemical processes support the hypothesis that much of the observed 'whitening' is calcium carbonate precipitating as an immediate result of the upwelling.

Strong, A. E.↗

Soil stabilization by a prokaryotic desert crust - Implications for Precambrian land biota

The ecology of the cyanophyte-dominated stromatolitic mat forming the ground cover over desert areas of Utah and Colorado is investigated and implications for the formation of mature Precambrian soils are discussed. The activation of the growth of the two species of filamentous cyanophyte identified and the mobility of their multiple trichromes upon wetting are observed, accompanied by the production and deposition of a sheath capable of accreting and stabilizing sand and clay particles. The formation of calcium carbonate precipitates upon the repeated wetting and drying of desert crust is noted, and it is suggested that the desert crust community may appear in fossil calcrete deposits as lithified microscopic tubes and cellular remains of algal trichromes. The invasion of dry land by both marine and freshwater algae on the model of the desert crust is proposed to be responsible for the accumulation, stabilization and biogenic modification of mature Precambrian soils.

Campbell, S. E.↗

Effect of salinity on the preservation of biomarkers in hypersaline microbial mat kerogens

Kerogen is the residue that remains after the minerals and organic compounds have been extracted from a rock using acid and organic solvents, respectively [1]. It is not only the largest organic carbon sink in the geological record but the best-preserved fraction due to its recalcitrance and ability to retain syngenetic source information during deposition [2]. Due to the complex, macromolecular, cross-linked polymeric structure of kerogen, it is difficult to analyse intact, often requiring breakdown into smaller subunits through thermal (pyrolysis) or chemical treatment (chemolysis) [3]. Saline and hypersaline environments host diverse microbial communities, which can trap and bind organic matrices such as cellular components (e.g., extracellular polymeric substances, cell wall, peptidoglycan, sheath material, etc.) with sediments, forming layered, laminated structures called microbial mats. Here we present depth profiles of two hypersaline cores through a microbial mat with differing total salinities. We looked at the composition of organic compounds released from kerogen during high temperature, hydrogen-assisted, pyrolysis to understand the effect of salinity on the composition and timing of their incorporation [4]. Field Site: The Exportadora del Sal S. A. (ESSA) saltern of Guerrero Negro (Baja California Sur, Mexico) lies within a typical sabhka environment adjacent to Laguna Ojo de Liebre. Note the spatial extent of the 13 major ponds of the ESSA system. The GN ponds thrive under well-monitored and stable conditions with steady state accretion and degradation of mat layers (around 0.5–1.4 cm per year). Organic mats typically attain up to 10 cm in thickness, depending on the location, which represents about 60 years of growth since these ponds were established. Sedimentation rate is rapid in these non-lithifying and non-mineralising mats, 1–1.5 cm per year. This environment is ideal for investigating in situ lipid preservation and diagenesis without the influence of constantly changing physical parameters. Methods: P4n5 and P5AB cores were collected as ~9 cm and 6.5 cm fresh cores, respectively, in June 2001 and September 2010, respectively from the ESSA saltern. The P4n5 core (9-9.1% salinity) was taken from Pond 4 near 5 and sub-divided into 10 layers. The P5AB core (11.2% salinity) was taken from Pond 5A near 5B and sub-divided into 8 layers. Lyophilised microbial mat powders were solvent-extracted using a modified Bligh-Dyer method and analysed by gas chromatography-mass spectrometry (GC-MS). Additionally, a subset of layers—layer 4 and layer 7—which represented active biomass and sediment-processed, respectively, were subjected to mild-acid methanolysis. The respective residues from conventional solvent extraction and acid methanolysis were loaded with a molybdenum sulfide catalyst and placed into a stainless-steel reactor. Samples were run on the hydropyrolysis set up (heated to 500 °C with 13-15 MPa of H2 pressure), extracted, and analysed by GC-MS. Results: Molecular profiles from the two ponds were significantly different and reflect the contributions of different photosynthetic and respiratory microbial communities to preserved organic matter. For example, the higher salinity P5AB core showed evidence of greater archaeal inputs (similarly observed in lab culture experiments [5]) as well as potential kerogen-bound carotenoids/carotenoid rearranged products or fragments. A hydrophobic emulsion formed during the acid methanolysis processing of layer 4 from both P4n5 and P5AB and layer 7 of P5AB. Hydropyrolysis of this hydrophobic residues released a greater abundance of polycyclic lipids relative to the pre-extracted control. Implications and Future Work: Catalytic hydropyrolysis of kerogen can rapidly generate abundant saturated pyrolysate products from the bound biomarker pool without altering the structures or stereochemistries of the products [6]. Chemical processing of solvent-extractable residues indicated that cellular matrices such as extracellular polymeric substances (EPS) may play a role in the sequestration of polycyclic lipid biomarkers such as steranes and hopanes. Their higher relative abundance compared to the pre-extracted control in the higher salinity layers and cores preliminarily aligns with this hypothesis, although further experiments are required to confirm this. It has been well-documented that EPS plays an important role in mineralisation, specifically carbonate formation, in microbial ecosystems. EPS can enhance calcium carbonate precipitation by providing diffusion-limited sites that create alkalinity gradients in response to microbial processes [7]. It has been experimentally demonstrated that salinity influences the total amount of EPS (both loosely- and tightly-bound) which increases with increasing salinity [8]. The higher salinity at Guerrero Negro switches the microbial population from filamentous Microcoleus to being dominated by Phormidium, Oscillatoria, and unicellular cyanobacteria. We demonstrated that lipid binding into kerogen via strong covalent linkages occurs at the very earliest stages of sedimentary diagenesis. We are currently investigating the influence of salinity on organic preservation through experimental and modelling approaches. Understanding how key biomarkers transform into preserved organic matter (i.e., from precursor biolipids to bound geolipids) in brine ecosystems will aid the search for organic biosignatures on other planetary bodies, especially Icy Moons and modern Mars.

hypersaline↗

Evaluation of ERTS data for certain oceanographic uses

The author has identified the following significant results. According to Lake Michigan records, the pH levels have been steadily increasing as the lake becomes more eutrophic. Numerous upwellings during the summer of 1973, beginning with the late July event, appear to be triggering a chemical precipitation of calcium carbonate. The upwelling provides abundant carbon dioxide into the surface water and results in massive blooms of phytoplankton. As the CO2 is utilized by these microscopic plants the pH is increased (acidity decreases) and CaCO3 no longer is able to remain in solution. The precipitation takes place where the phytoplankton are living, near depths of 10 meters. Therefore, the whiting observed by ERTS-1 is only seen in the green band, as red cannot penetrate but a few meters. With these whitings, secci disc readings lower in July from 10-15 meters to 3-5 meters and green, milky water is observed by research vessels. It appears that whitings have been becoming more frequent since the middle 60's but until ERTS-1 the extent had never been realized. Calcium levels are too low, presently, for a similar precipitate in Lakes Huron or Superior. However, whitings have been seen by ERTS-1 in Lakes Erie and Ontario where the calcium ion and pH levels are more like those found in Lake Michigan.

Strong, A. E.↗

Chemical evolution of the early Martian hydrosphere

The chemical evolution of the early Martian hydrosphere is discussed. The early Martian ocean can be modeled as a body of relatively pure water in equilibrium with a dense carbon dioxide atmosphere. The chemical weathering of lavas, pyroclastic deposits, and impact melt sheets would have the effect of neutralizing the acidity of the juvenile water. As calcium and other cations are added to the water by chemical weathering, they are quickly removed by the precipitation of calcium carbonate and other minerals, forming a deposit of limestone beneath the surface of the ocean. As the atmospheric carbon dioxide pressure and the temperature decrease, the Martian ocean would be completely frozen. Given the scenario for the chemical evolution of the northern lowland plains of Mars, it should be possible to draw a few conclusions about the expected mineralogy and geomorphology of this regions.

Schaefer, M. W.↗

Chemical whitings and chlorophyll distributions in the Great Lakes as viewed by Landsat

A chemical precipitation of calcium carbonate, or whiting, was first observed by satellite in Lake Michigan during August 1973. Since that initial observation similar events have been noted in Lakes Michigan, Erie, and Ontario with imagery from Landsat, Skylab, and NOAA satellites. By the use of Landsat multispectral data together with NOAA thermal infrared data, it has been observed that whitings occur several meters below the lake surface in relatively warm water. They are most vividly displayed during and after periods of upwelling. As the epilimnetic waters become supersaturated with Ca(+2) ions during summer, a triggering mechanism (presumably biological or physical) initiates the whiting, which may continue for several months. The effects on the biota of the euphotic zone when this milky cloud is present in the upper layers are poorly understood. However, Great Lakes circulation studies are taking advantage of these natural dye tracers.

Strong, A. E.↗

Hydrogeological Interpretation of Candidate Origin Sites for Martian Meteorite ALH84001

Barlow (this meeting) has identified two potential source craters for the martian meteorite ALH84001. The craters are at 11.7 deg S, 243.3 deg W (Mare Tyrrhenum site) and 14.0 deg S, 343.5 deg W (Sinus Sabaeus site). As noted by Barlow, both craters lie in the heavily cratered terrain (HCT) and are adjacent to fluvial valleys, Here I explore the fluvial history of these areas based upon the surrounding valley morphology. The most prominent valley network at the Sabaeus site is Evros Vallis. This wide, flat-floored valley is approximately 600 km long with an average width of 2.5 km and a depth of 220 m. The eroded volume of the entire Evros network is approximately 6 x 10(exp 11) cc. This is typical for networks located in the heavily cratered terrain (e.g. Warrego and Parana Valles). Evros is also an isolated valley system. No similar networks are found in the surrounding terrain. Thus it is unlikely that Evros formed as a result of widespread rainfall. A localized water source, such as discharge of a hydrothermal system or localized melting of snowfall, seems more consistent Previous modeling has demonstrated that only hydrothermal systems associated with high permeability subsurfaces can discharge sufficient water to form a valley network. The bulk of the discharge from such systems is consequently low temperature, slightly heated water Precipitation of calcium carbonate by low temperature fluids is consistent with most interpretations of the geochemistry of ALH84001. Available imagery at the Tyrrhenum site is of lesser quality. While eroded units of the HCT are nearby, there are no comparable well developed valley networks at this site. Erosion is instead manifested predominantly as gullies on slopes. This style of erosion suggests that water was not present at this site for the length of time as at the more integrated Sabaeus site. The superposition of fluidized ejecta blankets suggests however that ground water or ground ice was still present at this locality fairly recently, if the chosen crater is indeed correct.

Gulick, Virginia C.↗

Sulfur Cycling Mediates Calcium Carbonate Geochemistry in Modern Marine Stromatolites

Modem marine stromatolites forming in Highborne Cay, Exumas (Bahamas), contain microbial mats dominated by Schizothrix. Although saturating concentrations of Ca2+ and CO32- exist, microbes mediate CaCO3 precipitation. Cyanobacterial photosynthesis in these stromatolites aids calcium carbonate precipitation by removal of HS+ through CO2 use. Photorespiration and exopolymer production predominantly by oxygenic phototrophs fuel heterotrophic activity: aerobic respiration (approximately 60 umol/sq cm.h) and sulfate reduction (SR; 1.2 umol SO42-/sq cm.h) are the dominant C- consuming processes. Aerobic microbial respiration and the combination of SR and H2S oxidation both facilitate CaCO3 dissolution through H+ production. Aerobic respiration consumes much more C on an hourly basis, but duel fluctuating O2 and H2 depth profiles indicate that overall, SR consumes only slightly less (0.2-0.5) of the primary production. Moreover, due to low O2 concentrations when SR rates are peaking, reoxidation of the H2S formed is incomplete: both thiosulfate and polythionates are formed. The process of complete H2S oxidation yields H+. However, due to a low O2 concentration late in the day and relatively high O2 concentrations early in the following morning, a two-stage oxidation takes place: first, polythionates are formed from H2S, creating alkalinity which coincides with CaCO3 precipitation; secondly, oxidation of polythionates to sulfate yields acidity, resulting in dissolution, etc. Vertical profiles confirmed that the pH peaked late in the afternoon (greater than 8.8) and had the lowest values (less than 7.4) early in the morning. Thus, the effect of this S-cycling through alkalinity production, followed by acidification during H2S oxidation, results in a six times stronger fluctuation in acidity than photosynthesis plus aerobic respiration accomplish. This implies that anaerobic processes play a pivotal role in stromatolite formation.

Visscher, P. T.↗

Possible limits on the composition of the Archaean Ocean

The potential impact of high carbon dioxide partial pressure on ocean chemistry is examined in order to investigate what constraints are imposed by the known record of chemical sedimentation through time. The evidence consists of the persistence of calcium carbonate and sulfate precipitation throughout almost the entire sedimentary rock record. A uniformitarian point of view that assumes no very great change in the conditions for the deposition of these chemical sediments. The methods of Holland (1972) are used to set limits on the composition of the water from which precipitation occurred. No inconsistencies between the sedimentary rock record and presumed higher partial pressure of carbon dioxide early in earth history, provided that high partial pressure was accompanied by a generally lower pH for seawater, higher concentrations of calcium and biocarbonate ions, and lower concentrations of carbonate and sulfate ions.

Walker, J. C. G.↗

The evaporation path of seawater and the coprecipitation of Br- and K+ with halite

Brines and salt were sampled at the Morton Bahamas solar salt production facility on Great Inagua Island in the Bahamas. The brines were analyzed by ion chromatography to define more precisely than heretofore the evaporation path of seawater to the end of the halite facies. At Inagua, calcium carbonate begins to precipitate at a brine concentration factor of 1.8 times that of seawater. Gypsum begins to precipitate at a brine concentration of 3.8 times seawater, and halite at a concentration factor of 10.6. Three of the most concentrated brines from Inagua (40 times seawater) were evaporated further in the laboratory. Magnesium sulfate first precipitated at brine concentrations about 70 times those of seawater, and potassium-bearing phases began to precipitate for these brines at concentrations greater than 90 times those of seawater. The distribution of coefficients of Br- and K+ between brines and halite were determined by combining analytical data for the Inagua brines with measurements of the Br- and K+ content of halites from Inagua and of halite which had precipitated from Inagua brines during storage. The observed average value of DBr- is 0.032, in good agreement with some of the previous measurements. The measured values of DK+ are highly variable (0.001 to 0.021); DK+ for halite precipitated early in the halite facies is in the vicinity of 0.015.

NASA Discipline Exobiology↗

Lab-Scale Study of the Calcium Carbonate Dissolution and Deposition by Marine Cyanobacterium Phormidium subcapitatum

Suggestions that calcification in marine organisms changes in response to global variations in seawater chemistry continue to be advanced (Wilkinson, 1979; Degens et al. 1985; Kazmierczak et al. 1986; R. Riding 1992). However, the effect of [Na+] on calcification in marine cyanobacteria has not been discussed in detail although [Na+] fluctuations reflect both temperature and sea-level fluctuations. The goal of these lab-scale studies therefore was to study the effect of environmental pH and [Na+] on CaCO3 deposition and dissolution by marine cyanobacterium Phormidium subcapitatum. Marine cyanobacterium P. subcapitatum has been cultivated in ASN-III medium. [Ca2+] fluctuations were monitored with Ca(2+) probe. Na(+) concentrations were determined by the initial solution chemistry. It was found that the balance between CaCO3 dissolution and precipitation induced by P. subcapitatum grown in neutral ASN III medium is very close to zero. No CaCO3 precipitation induced by cyanobacterial growth occurred. Growth of P. subcapitatum in alkaline ASN III medium, however, was accompanied by significant oscillations in free Ca(2+) concentration within a Na(+) concentration range of 50-400 mM. Calcium carbonate precipitation occurred during the log phase of P. subcapitatum growth while carbonate dissolution was typical for the stationary phase of P. subcapitatum growth. The highest CaCO3 deposition was observed in the range of Na(+) concentrations between 200-400 mM. Alkaline pH also induced the clamping of P. subcapitatum filaments, which appeared to have a strong affinity to envelop particles of chemically deposited CaCO3 followed by enlargement of those particles size. EDS analysis revealed the presence of Mg-rich carbonate (or magnesium calcite) in the solution containing 10-100 mM Na(+); calcite in the solution containing 200 mM Na(+); and aragonite in the solution containing with 400 mM Na(+). Typical present-day seawater contains xxmM Na(+). Early (Archean) seawater was likely less saline. The division of marine cyanobacterium P. subcapitatum is associated with periodic deposition and dissolution of CaCO3, the rhythms and intensity of which are dependent on concentrations of both OH(-) and Na(+). Thus, the role of present-day marine cyanobacteria in the global carbonate cycle might be reduced to aggregation and recrystallization of available CaCO3 particles in marine water rather than long-term precipitation and accumulation of CaCO3 deposits. For lower Na(+) concentrations, precipitation of carbonates by cyanobacteria would be even less significant. These results suggest that the lack of calcified cyanobacteria in stromatalite-bearing Precambrian sequences can be explained not only by high dissolved inorganic carbon concentrations but also by lower salinity, as well as possible lower pH compared to present-day oceans.

Karakis, S. G.↗

MN Carbonates in the Martian Meteorite Nakhla: Possible Evidence of Brine Evaporation

The importance of secondary phases in martian meteorites lies in their potential to provide clues about the martian environments responsible for their formation. During this study, we analyzed a number of carbonate-bearing fracture surfaces from the Nakhla meteorite. Here we describe the physical and chemical properties of several manganese-calcium-rich siderites. Additionally, we describe a potential model for the formation and alteration of these carbonates, and we suggest constraints on the conditions responsible for their precipitation. Nakhla is an olivine-bearing clinopyroxenite with minor amounts of feldspar, FeS, and Fe oxides. Secondary mineral assemblages include vein filling clay with embedded iron oxides, a calcium sulfate, amorphous silica, chlorapatite, halite and carbonates. Bridges and Grady suggested that the carbonates in Nakhla formed from brine evaporation. Isotope studies of the Mn rich siderite are also consistent with formation from hydrothermal fluids with an upper T constraint of ~170 C.

Bailey, J. V.↗

Mineral precipitation in north slope aufeis

The Canning and Shaviovik river aufeis fields were studied on the ground and with aircraft data. Powdered calcium carbonate (CaCO3) patches, a few cm in thickness, were found in discrete locations on both aufeis fields. This is indicative of chemical weathering of limestone bedrock which is known to underlie much of the eastern arctic coastal plain of Alaska. Spring or river water which remains unfrozen throughout much of the winter carries CaCO3 in solution; as the river ice freezes more deeply the CaCO3 in solution is forced upwards through cracks in the river ice. Upon exposure to the cold air CaCO3 is excluded as the water freezes, forming successive layers during aufeis growth. In the melt season CaCO3, slush/powder accumulates in patches on top of the ice as the aufeis melts downward.

Hall, D. K.↗

Analytical electron microscopy of biogenic and inorganic carbonates

In the terrestrial sedimentary environment, the mineralogically predominant carbonates are calcite-type minerals (rhombohedral carbonates) and aragonite-type minerals (orthorhombic carbonates). Most common minerals precipitating either inorganically or biogenically are high magnesium calcite and aragonite. High magnesium calcite (with magnesium carbonate substituting for more than 7 mole percent of the calcium carbonate) is stable only at temperatures greater than 700 C or thereabouts, and aragonite is stable only at pressures exceeding several kilobars of confining pressure. Therefore, these carbonates are expected to undergo chemical stabilization in the diagenetic environment to ultimately form stable calcite and dolomite. Because of the strong organic control of carbonate deposition in organisms during biomineralization, the microchemistry and microstructure of invertebrate skeletal material is much different than that present in inorganic carbonate cements. The style of preservation of microstructural features in skeletal material is therefore often quite distinctive when compared to that of inorganic carbonate even though wholesale recrystallization of the sediment has taken place. Microstructural and microchemical comparisons are made between high magnesium calcite echinoderm skeletal material and modern inorganic high magnesium calcite inorganic cements, using analytical electron microscopy and related techniques. Similar comparisons are made between analogous materials which have undergone stabilization in the diagenetic environment. Similar analysis schemes may prove useful in distinguishing between biogenic and inorganic carbonates in returned Martian carbonate samples.

Blake, David F.↗

Early solar system aqueous activity - Sr isotope evidence from the Orgueil CI meteorite

The Sr isotopic composition and Rb-87/Sr-86 ratio have been measured in carbonates and sulfate separated from the Orgueil meteorite in order to determine the time when liquid water may have acted on the parent body. Both of the studied phases probably precipitated from aqueous solution. The results show that carbonate deposition occurred contemporaneously with parent body formation or shortly after it, probably within 100 Myr. On the other hand, at least some of the calcium sulfate seems to have been formed recently.

Macdougall, J. D.↗