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NASA NTRS2001

Thiols in Hydrothermal Solution: Standard Partial Molal Properties and Their Role in the Organic Geochemistry of Hydrothermal Environments

Modern seafloor hydrothermal systems are locations where great varieties of geochemistry occur due to the enormous disequilibrium between vent fluids and seawater. The disequilibrium geochemistry has been hypothesized to include reactions to synthesize organic compounds. Despite the incomplete understanding of the carbon budget in hydrothermal systems, the organic geochemistry of these sites has received little attention. Experimental simulations of these environments, however, indicate that organic compounds may have difficulty forming in a purely aqueous environment. On the other hand, thiols, thioesters and disulfides have been implicated as reaction intermediates between CO or CO2 in experiments of carbon reduction in hydrothermal environments, as well as in a variety of biological processes and other abiotic reactions. The reduction of CO2 to thesis, for example, is observed using the FeS-H2S/FeS2 couple to provide the reducing power. We have used recent advances in theoretical geochemistry to estimate the standard partial moral thermodynamic properties and parameters for the revised Helgeson-Kirkham-Flowers equation of state for aqueous straight-chain alkyl thesis. With these data and parameters we have evaluated the role that organic sulfur compounds may play as reaction intermediates during organic compound synthesis. We conclude that organic sulfur compounds may hold the key to the organic chemistry leading to the origin of life in hydrothermal settings. These results may also explain the presence of sulfur in a number of biomolecules present in ancient thermophilic microorganisms.

Schulte, Mitchell D.↗

NASA NTRS2001

The Role of Cyanobacteria in Stromatolite Morphogenesis, Highborn Cay Bahamas: An Integrated Field and Laboratory Simulation Study

Geomicrobiological phenomena are among the most fundamental of interactions between Earth and its biosphere. Actively growing and lithifying stromatolites at Highborne Cay Bahamas, have recently been documented and allow for detailed examination of the roles microbes play in the mineralization process. These stromatolites contain a variety of complex microbial communities with distinct distribution patterns for different microbial groups. Cyanobacteria are the primary producers in this system providing energy, directly or indirectly, for the entire stromatolite microbial community. They also play key roles in the trapping and binding of sediments. Most of these species are highly motile and can adjust their position and orientation within the sediment matrix in order to optimize their access to irradiance and nutrients. As individual species have different physical and metabolic properties, this motility generally results in segregated distributions of species, which in turn contributes to the laminated textures observed in these actively forming stromatolites. Increasingly our studies suggest that the activities and locations of various cyanobacterial species also contribute greatly to the localization of new mineral precipitation through a variety of processes. We are investigating these contributions using an integrated approach combining detailed observations of field samples with manipulative experiments using both field samples and cultures of specific organisms isolated from these stromatolites. Experiments are conducted both in standard laboratory conditions and in outdoor running seawater flumes. A variety of standard techniques; SEM (scanning electron microscopy), petrographic analyses, TEM (transmission electron microscopy), are used to compare mineralization processes in field samples with those generated in laboratory-flume simulations. Using this approach we are able to more thoroughly investigate the effects of irradiance, CaCO3 saturation, and hydrodynamic regime on cyanobacterial distribution, trapping and binding and mineral precipitation. Simulation results will be presented and compared with community and mineralization distribution patterns seen in the field samples from which these communities were isolated.

Prufert-Bebout, Leslie↗

NASA NTRS2002

Biogeochemical Cycles of Carbon and Sulfur

The elements carbon (C) and sulfur (S) interact with each other across a network of elemental reservoirs that are interconnected by an array of physical, chemical and biological processes. These networks are termed the biogeochemical C and S cycles. The compounds of C are highly important, not only as organic matter, but also as atmospheric greenhouse gases, pH buffers in seawater, oxidation-reduction buffers virtually everywhere, and key magmatic constituents affecting plutonism and volcanism. The element S assumes important roles as an oxidation-reduction partner with C and Fe in biological systems, as a key constituent in magmas and volcanic gases, and as a major influence upon pH in certain environments. This presentation describes the modern biogeochemical C and S cycles. Measurements are described whereby stable isotopes can help to infer the nature and quantitative significance of biological and geological processes involved in the C and S cycles. This lecture also summarizes the geological and climatologic aspects of the ancient C and S cycles, as well as the planetary and extraterrestrial processes that influenced their evolution over millions to billions of years.

DesMarais, David J.↗

NASA NTRS1976

Space Paint

Developed at Goddard, this improved inorganic paint may help protect coastal bridges subject to extreme corrosion from seawater spray. Potassium silicate formulated into a thin waterbase binder that sprays easily, adheres readily, and can be heavily loaded with zinc particles to provide uniform coverage in a single coat. Stanford Research Institute has measured an annual market in excess of $2 billion in painting highway bridges, utility pipelines, nuclear reactors, and railcar hoppers. Other suitable markets include offshore drilling facilities, railroad bridges, and ships.

Source record↗

NASA NTRS2003

The Use of Ion Vapor Deposited Aluminum (IVD) for the Space Shuttle Solid Rocket Booster (SRB)

This viewgraph representation provides an overview of the use of ion vapor deposited aluminum (IVD) for use in the Space Shuttle Solid Rocket Booster (SRB). Topics considered include: schematics of ion vapor deposition system, production of ion vapor deposition system, IVD vs. cadmium coated drogue ratchets, corrosion exposure facilities and tests, seawater immersion facilities and tests and continued research and development issues.

Novak, Howard L.↗

NASA NTRS2003

Ejecta from Ocean Impacts

Numerical simulations of deep-ocean impact provide some limits on the size of a projectile that will not mix with the ocean floor during a deep-ocean impact. For a vertical impact at asteroidal velocities (approx. 20 km/s), mixing is only likely when the projectile diameter is greater than 112 of the water depth. For oblique impacts, even larger projectiles will not mix with ocean floor silicates. Given the typical water depths of 4 to 5 km in deep-ocean basins, asteroidal projectiles with diameters as large as 2 or 3 km may commonly produce silicate ejecta that is composed only of meteoritic materials and seawater salts. However, the compressed water column beneath the projectile can still disrupt and shock metamorphose the ocean floor. Therefore, production of a separate, terrestrial ejecta component is not ruled out in the most extreme case. With increasing projectile size (or energy) relative to water depths, there must be a gradation between oceanic impacts and more conventional continental impacts. Given that 60% of the Earth's surface is covered by oceanic lithosphere and 500 m projectiles impact the Earth on 10(exp 5) y timescales, there must be hundreds of oceanic impact deposits in the sediment record awaiting discovery.

Kyte, Frank T.↗

NASA NTRS2004

Brine Pockets in the Icy Shell on Europa: Distribution, Chemistry, and Habitability

On Earth, sea ice is rich in brine, salt, and gas inclusions that form through capturing of seawater during ice formation. Cooling of the ice over time leads to sequential freezing of captured sea-water, precipitation of salts, exsolution of gases, and formation of brine channels and pockets. Distribution and composition of brines in sea ice depend on the rate of ice formation, vertical temperature gradient, and the age of the ice. With aging, the abundance of brine pockets decreases through downward migration. De- spite low temperatures and elevated salinities, brines in sea ice provide a habitat for photosynthetic and chemosynthetic organisms. On Europa, brine pockets and channels could exist in the icy shell that may be from a few km to a few tens of km thick and is probably underlain by a water ocean. If the icy shell is relatively thick, convection could develop, affecting the temperature pattern in the ice. To predict the distribution and chemistry of brine pockets in the icy shell we have combined numerical models of the temperature distribution within a convecting shell, a model for oceanic chemistry, and a model for freezing of Europan oceanic water. Possible effects of brine and gas inclusions on ice rheology and tectonics are discussed.

Zolotov, M. Yu↗

NASA NTRS2004

Gas Hydrate Stability at Low Temperatures and High Pressures with Applications to Mars and Europa

Gas hydrates are implicated in the geochemical evolution of both Mars and Europa [1- 3]. Most models developed for gas hydrate chemistry are based on the statistical thermodynamic model of van der Waals and Platteeuw [4] with subsequent modifications [5-8]. None of these models are, however, state-of-the-art with respect to gas hydrate/electrolyte interactions, which is particularly important for planetary applications where solution chemistry may be very different from terrestrial seawater. The objectives of this work were to add gas (carbon dioxide and methane) hydrate chemistries into an electrolyte model parameterized for low temperatures and high pressures (the FREZCHEM model) and use the model to examine controls on gas hydrate chemistries for Mars and Europa.

Marion, G. M.↗

NASA NTRS2004

Winds, Water Budgets and Stable Isotopes in Tropical Cyclones using TRMM and QUICKSCAT

Water vapor is the most abundant greenhouse gas in the atmosphere. Changes in its concentration and distribution are controlled by the hydrologic cycle. Because of its capacity to absorb and emit long wave radiation, release latent heat during condensation in storms and reflect short wave radiation when clouds form it has a major impact on Global climate change. The stable isotope ratios of water are H20 H2l6O and H0 H2l6O. These ratios change whenever water undergoes a phase change. They also change in both rain and water vapor whenever an air parcel is exposed to rain. In addition the relative changes in the two ratios differ as a &nction of the relative humidity. In short, the stable isotope ratios in water vapor in the atmosphere contain an integrated history of the processes affecting the concentration and distribution of water vapor in the atmosphere. Therefore the measurement and interpretation of changes in these stable isotope ratios are a powerful tool matched by no other method in tracing the transport history of water in the atmosphere. Our initial studies under this grant focused on the changes of the stable isotope ratios of precipitation and water vapor in tropical cyclones. The changes in time and space were found to be very large and to trace the transport of water in the storms reflecting changes in basic structural features. Because the stable isotope ratios of rains from tropical cyclones are so low flooding associated with land falling tropical cyclones introduces a negative isotopic spike into the coastal surface waters. In addition the stable isotope ratios of water vapor in the vicinity of tropical cyclones is anomalously low. This suggests that carbonate shelled organisms such as ostracoda living in coastal waters have the potential to record the isotopic spike and thereby provide a long term record of tropical storm activity in sediment cores containing fossil shells. Likewise, tree rings in coastal environments offer a similar potential. We have analyzed the oxygen isotopic composition of ostrcoda shells formed in the floodwaters of Tropical Storm Allison (2001) and discovered the negative isotopic 1 16 spike. Because we had learned that storm activity has a major impact on the stable isotope ratios of water vapor in the tropics and sub-tropics we decided to analyze the isotopic compositions of water vapor in different locations in the tropics. We did this in Puerto Escondido, Mexico in July 1998, near Kwajalein Island in the Pacific in 1999 as part of a TRMM summer field program and in 2001 in Key West, Florida as part of the CAMEX 4 summer field program. Our isotopic studies along with our earlier tropical cyclone studies showed that the low isotopic ratios in water vapor induced by exposure to rains the storms persisted for 48 hours often far away from the original storm site. We also noted that positive isotopic spikes were introduced into atmospheric water vapor if winds were high and extensive sea spray was present. These findings have a significant impact on the interpretation of the stable isotope studies of tropical ice cores found in the high mountain regions of the tropics. The assumption made in interpreting the ice core record is that the source water vapor evaporated from the sea surface is in near isotopic equilibrium with the seawater and undergoes a decrease during its transport that reflects the change in temperature from the sea surface to the site of the ice core. Because an additional isotopic depletion occurs at the sea surface source area that depends on the intensity, duration and size of the tropical rain system the isotopic variations found in the ice cores must take into account changes in past storm activity in the tropics. These systems must be an important source of water vapor to the ice cores because they charge the troposphere with water vapor to a far greater vertical height than evaporation in quiescent regions. Finally, an interest in increased heat transfer in thnterior of tropical cyclones resulting from greater amounts of sea spray is a topic of considerable interest to the research community. Increases in sea spray may be related to rapid changes in the intensity of hurricanes, a feature of hurricanes that currently is very poorly forecast. Project CBLAST of the Hurricane Research Division of NOAA is an active program that uses P3 research aircraft to evaluate this problem. An instrument has been designed and built at the University of Houston that will be placed on the P3 research aircraft during the 2004 hurricane season. It continuously measures the salt content of rain in hurricanes. Changes in the salt content of the rains should reflect the abundance of sea spray at the sea surface. In this way maps of sea spray intensity in hurricanes may be forthcoming. This should help computer modelers who simulate hurricanes to better understand the potential of changes in sea spray to change the intensity of hurricanes. The cost of designing, building and installing this instrument was borne largely by funding from this NASA grant. A list of presentations at national meetings and publications that were as the result of funding from this NASA grant are found in the report.

Lawrence, James R.↗

NASA NTRS2004

A New Method for Estimating Bacterial Abundances in Natural Samples using Sublimation

We have developed a new method based on the sublimation of adenine from Escherichia coli to estimate bacterial cell counts in natural samples. To demonstrate this technique, several types of natural samples including beach sand, seawater, deep-sea sediment, and two soil samples from the Atacama Desert were heated to a temperature of 500 C for several seconds under reduced pressure. The sublimate was collected on a cold finger and the amount of adenine released from the samples then determined by high performance liquid chromatography (HPLC) with UV absorbance detection. Based on the total amount of adenine recovered from DNA and RNA in these samples, we estimated bacterial cell counts ranging from approx. l0(exp 5) to l0(exp 9) E. coli cell equivalents per gram. For most of these samples, the sublimation based cell counts were in agreement with total bacterial counts obtained by traditional DAPI staining. The simplicity and robustness of the sublimation technique compared to the DAPI staining method makes this approach particularly attractive for use by spacecraft instrumentation. NASA is currently planning to send a lander to Mars in 2009 in order to assess whether or not organic compounds, especially those that might be associated with life, are present in Martian surface samples. Based on our analyses of the Atacama Desert soil samples, several million bacterial cells per gam of Martian soil should be detectable using this sublimation technique.

Glavin, Daniel P.↗

NASA NTRS2003

Mars Surveyor Program '01 Mars Environmental Compatibility Assessment wet chemistry lab: a sensor array for chemical analysis of the Martian soil

The Mars Environmental Compatibility Assessment (MECA) instrument was designed, built, and flight qualified for the now canceled MSP (Mars Surveyor Program) '01 Lander. The MECA package consisted of a microscope, electrometer, material patch plates, and a wet chemistry laboratory (WCL). The primary goal of MECA was to analyze the Martian soil (regolith) for possible hazards to future astronauts and to provide a better understanding of Martian regolith geochemistry. The purpose of the WCL was to analyze for a range of soluble ionic chemical species and electrochemical parameters. The heart of the WCL was a sensor array of electrochemically based ion-selective electrodes (ISE). After 20 months storage at -23 degrees C and subsequent extended freeze/thawing cycles, WCL sensors were evaluated to determine both their physical durability and analytical responses. A fractional factorial calibration of the sensors was used to obtain slope, intercept, and all necessary selectivity coefficients simultaneously for selected ISEs. This calibration was used to model five cation and three anion sensors. These data were subsequently used to determine concentrations of several ions in two soil leachate simulants (based on terrestrial seawater and hypothesized Mars brine) and four actual soil samples. The WCL results were compared to simulant and soil samples using ion chromatography and inductively coupled plasma optical emission spectroscopy. The results showed that flight qualification and prolonged low-temperature storage conditions had minimal effects on the sensors. In addition, the analytical optimization method provided quantitative and qualitative data that could be used to accurately identify the chemical composition of the simulants and soils. The WCL has the ability to provide data that can be used to "read" the chemical, geological, and climatic history of Mars, as well as the potential habitability of its regolith.

Non-NASA Center↗

NASA NTRS2002

Renal effects of fresh water-induced hypo-osmolality in a marine adapted seal

With few exceptions, marine mammals are not exposed to fresh water; however quantifying the endocrine and renal responses of a marine-adapted mammal to the infusion of fresh water could provide insight on the evolutionary adaptation of kidney function and on the renal capabilities of these mammals. Therefore, renal function and hormonal changes associated with fresh water-induced diuresis were examined in four, fasting northern elephant seal ( Mirounga angustirostris) (NES) pups. A series of plasma samples and 24-h urine voids were collected prior to (control) and after the infusion of water. Water infusion resulted in an osmotic diuresis associated with an increase in glomerular filtration rate (GFR), but not an increase in free water clearance. The increase in excreted urea accounted for 96% of the increase in osmotic excretion. Following infusion of fresh water, plasma osmolality and renin activity decreased, while plasma aldosterone increased. Although primary regulators of aldosterone release (Na(+), K(+) and angiotensin II) were not significantly altered in the appropriate directions to individually stimulate aldosterone secretion, increased aldosterone may have resulted from multiple, non-significant changes acting in concert. Aldosterone release may also be hypersensitive to slight reductions in plasma Na(+), which may be an adaptive mechanism in a species not known to drink seawater. Excreted aldosterone and urea were correlated suggesting aldosterone may regulate urea excretion during hypo-osmotic conditions in NES pups. Urea excretion appears to be a significant mechanism by which NES pups sustain electrolyte resorption during conditions that can negatively affect ionic homeostasis such as prolonged fasting.

NASA Center ARC↗

NASA NTRS1995

Anomalous carbonate precipitates: is the Precambrian the key to the Permian?

Late Permian reefs of the Capitan complex, west Texas; the Magnesian Limestone, England; Chuenmuping reef, south China; and elsewhere contain anomalously large volumes of aragonite and calcite marine cements and sea-floor crusts, as well as abundant microbial precipitates. These components strongly influenced reef growth and may have been responsible for the construction of rigid, open reefal frames in which bryozoans and sponges became encrusted and structurally reinforced. In some cases, such as the upper biostrome of the Magnesian Limestone, precipitated microbialites and inorganic crusts were the primary constituents of the reef core. These microbial and inorganic reefs do not have modern marine counterparts; on the contrary, their textures and genesis are best understood through comparison with the older rock record, particularly that of the early Precambrian. Early Precambrian reefal facies are interpreted to have formed in a stratified ocean with anoxic deep waters enriched in carbonate alkalinity. Upwelling mixed deep and surface waters, resulting in massive seafloor precipitation of aragonite and calcite. During Mesoproterozoic and early Neoproterozoic time, the ocean became more fully oxidized, and seafloor carbonate precipitation was significantly reduced. However, during the late Neoproterozoic, sizeable volumes of deep ocean water once again became anoxic for protracted intervals; the distinctive "cap carbonates" found above Neoproterozoic tillites attest to renewed upwelling of anoxic bottom water enriched in carbonate alkalinity and 12C. Anomalous late Permian seafloor precipitates are interpreted as the product, at least in part, of similar processes. Massive carbonate precipitation was favored by: 1) reduced shelf space for carbonate precipitation, 2) increased flux of Ca to the oceans during increased continental erosion, 3) deep basinal anoxia that generated upwelling waters with elevated alkalinities, and 4) further evolution of ocean water in the restricted Delaware, Zechstein, and other basins. Temporal coincidence of these processes resulted in surface seawater that was greatly supersaturated by Phanerozoic standards and whose only precedents occurred in Precambrian oceans.

Non-NASA Center↗

NASA NTRS1997

High-temperature life without photosynthesis as a model for Mars

Discoveries in biology and developments in geochemistry over the past two decades have lead to a radical revision of concepts relating to the upper temperature at which life thrives, the genetic relationships among all life on Earth, links between organic and inorganic compounds in geologic processes, and the geochemical supply of metabolic energy. It is now apparent that given a source of geochemical energy, in the form of a mixture of compounds that is far from thermodynamic equilibrium, microorganisms can take advantage of the energy and thrive without the need for photosynthesis as a means of primary productivity. This means that life can exist in the subsurface of a planet such as Mars without necessarily exhibiting a surface expression. Theoretical calculations quantify the geochemically provided metabolic energy available to hyperthermophilic organisms in submarine hydrothermal systems on the Earth, and help to explain the enormous biological productivity of these systems. Efforts to place these models in the context of the early Earth reveal that substantial geochemical energy would have been available and that organic synthesis would have been thermodynamically favored as hydrothermal fluids mix with seawater.

Non-NASA Center↗

NASA NTRS1989

Secular change in chert distribution: a reflection of evolving biological participation in the silica cycle

In the modern oceans, the removal of dissolved silica from sea water is principally a biological process carried out by diatoms, with lesser contributions from radiolaria, silicoflagellates, and sponges. Because such silica in sediments is often redistributed locally during diagenesis to from nodular or bedded chert, stratigraphic changes in the facies distribution of early diagenetic chert provide important insights into the development of biological participation in the silica cycle. The abundance of chert in upper Proterozoic peritidal carbonates suggests that at this time silica was removed from seawater principally by abiological processes operating in part of the margins of the oceans. With the evolution of demosponges near the beginning of the Cambrian Period, subtidal biogenetic cherts became increasingly common, and with the Ordovician rise of radiolaria to ecological and biogeochemical prominence, sedimented skeletons became a principal sink for oceanic silica. Cherts of Silurian to Cretaceous age share many features of facies distribution and petrography but they differ from Cenozoic siliceous deposits. These differences are interpreted to reflect the mid-Cretaceous radiation of diatoms and their subsequent rise to domination of the silica cycle. Biogeochemical cycles provide an important framework for the paleobiological interpretation of the organisms that participate in them.

Non-NASA Center↗

NASA NTRS1995

The carbon-isotopic composition of Proterozoic carbonates: Riphean successions from northwestern Siberia (Anabar Massif, Turukhansk Uplift)

Thick carbonate-dominated successions in northwestern Siberia document secular variations in the C-isotopic composition of seawater through Mesoproterozoic and early Neoproterozoic (Early to early Late Riphean) time. Mesoproterozoic dolomites of the Billyakh Group, Anabar Massif, have delta 13C values that fall between 0 and -1.9 permil versus PDB, with values in the upper part of the succession (Yusmastakh Formation) consistently higher than those of the lower (Ust'-Il'ya and Kotuikan formations). Consistent with available biostratigraphic and radiometric data, delta 13C values for Billyakh carbonates compare closely with those characterizing early Mesoproterozoic carbonates (about 1600-1200 Ma) worldwide. In contrast, late Mesoproterozoic to early Neoproterozoic limestones and dolomites in the Turukhansk Uplift exhibit moderate levels of secular variation. Only the lowermost carbonates in the Turukhansk succession (Linok Formation) have delta 13C values that approximate Billyakh values. Higher in the Turukhansk succession, delta 13C values vary from -2.7 to +4.6 permil (with outliers as low as -5.0 permil interpreted as diagentically altered). Again, consistent with paleontological and radiometric data, these values compare well with isotopic values from 1200 to 850 Ma successions elsewhere. Five sections measured in different parts of the Turukhansk basin show nearly identical patterns of variation, confirming that carbonate delta 13C correlates primarily with time and not facies. The Siberian sections illustrate the potential of integrated biostratigraphic and chemostratigraphic data in the intra- and interbasinal correlation of Mesoproterozoic and early Neoproterozoic rocks.

NASA Discipline Exobiology↗

NASA NTRS1993

3.4-Billion-year-old biogenic pyrites from Barberton, South Africa: sulfur isotope evidence

Laser ablation mass spectroscopy analyses of sulfur isotopic compositions of microscopic-sized grains of pyrite that formed about 3.4 billion years ago in the Barberton Greenstone Belt, South Africa, show that the pyrite formed by bacterial reduction of seawater sulfate. These data imply that by about 3.4 billion years ago sulfate-reducing bacteria had become active, the oceans were rich in sulfate, and the atmosphere contained appreciable amounts (>>10(-13) of the present atmospheric level) of free oxygen.

NASA Discipline Exobiology↗

NASA NTRS1988

Sulfur isotope effects associated with oxidation of sulfide by O2 in aqueous solution

Normal sulfur isotope effects averaging epsilon = -5.2 +/- 1.4% (s.d.) were consistently observed for the oxidation of sulfide in aqueous solution. Reaction products were sulfate, thiosulfate and sulfite at pH 10.8-11 in distilled water; S0 was formed in two experiments with synthetic seawater at pH 8-9.5. Because the -5.2% normal isotope effect differs significantly from the previously measured +2% inverse effect associated with anaerobic oxidation of sulfide by photosynthetic bacteria, stable sulfur isotopic measurements are potentially useful for distinguishing aerobic vs. anaerobic sulfide oxidation in marine and freshwater sulfureta.

NASA Program Exobiology↗