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All sourcesNASA NTRSDOE OSTI
NASA NTRS1990

The photochemical origins of life and photoreaction of ferrous ion in the archaean oceans

A general argument is made for the photochemical origins of life. A constant flux of free energy is required to maintain the organized state of matter called life. Solar photons are the unique source of the large amounts of energy probably required to initiate this organization and certainly required for the evolution of life to occur. The completion of this argument will require the experimental determination of suitable photochemical reactions. It is shown that biogenetic porphyrins readily photooxidize substrates and emit hydrogen in the presence of a catalyst. These results are consistent with the Granick hypothesis, which relates a biosynthetic pathway to its evolutionary origin. It has been shown that photoexcitation of ferrous ion at neutral pH with near ultraviolet light produces hydrogen with high quantum yield. This same simple system may reduce carbon dioxide to formaldehyde and further products. These reactions offer a solution to the dilemma confronting the Oparin-Urey-Miller model of the chemical origin of life. If carbon dioxide is the main form of carbon on the primitive earth, the ferrous photoreaction may provide the reduced carbon necessary for the formation of amino acids and other biogenic molecules. These results suggest that this progenitor of modern photosynthesis may have contributed to the chemical origins of life.

Mauzerall, David C.↗
NASA NTRS1999

Environmental Conditions and Threatened and Endangered Species Populations near the Titain, Atlas, and Delta Launch Complexes, Cape Canaveral Air Station

Launches of Delta, Atlas, and Titan rockets from Cape Canaveral Air Station (CCAS) have potential environmental effects. These could occur from direct impacts of launches or indirectly from habitat alterations. This report summarizes a three-year study (1995-1998) characterizing the environment, with particular attention to threatened and endangered species, near Delta, Atlas, and Titan launch facilities. Cape Canaveral has been modified by Air Force development and by 50 years of fire suppression. The dominant vegetation type around the Delta and Atlas launch complexes is coastal oak hammock forest. Oak scrub is the predominant upland vegetation type near the Titan launch complexes. Compositionally, these are coastal scrub communities that has been unburned for greater than 40 years and have developed into closed canopy, low-stature forests. Herbaceous vegetation around active and inactive facilities, coastal strand and dune vegetation near the Atlantic Ocean, and exotic vegetation in disturbed areas are common. Marsh and estuarine vegetation is most common west of the Titan complexes. Launch effects to vegetation include scorch, acid, and particulate deposition. Discernable, cumulative effects are limited to small areas near the launch complexes. Water quality samples were collected at the Titan, Atlas, and Delta launch complexes in September 1995 (wet season) and January 1996 (dry season). Samples were analyzed for heavy metals, chloride, total organic carbon, calcium, iron, magnesium, sodium, total alkalinity, pH, and conductivity. Differences between fresh, brackish, and saline surface waters were evident. The natural buffering capacity of the environment surrounding the CCAS launch complexes is adequate for neutralizing acid deposition in rainfall and launch deposition. Populations of the Florida Scrub-Jay (Aphelocoma coerulescens), a Federally- listed, threatened species, reside near the launch complexes. Thirty-seven to forty-one scrub-jay territories were located at Titan, Atlas, and Delta launch complexes between 1995 and 1997. No direct impacts to scrub-jays were observed as a result of normal launches. The explosion of the Delta rocket in January 1997 caused direct impacts to the habitat of several scrub-jays families, from fire and debris; however, no scrub-jay mortality was observed. Mortality exceeded reproductive output at all areas over the course of the study. Populations of the southeastern beach mouse (Peromyscus polionotus niveiventris) populations, a Federally listed, threatened species, reside near all the launch complexes. Hurricane Erin and several other tropical storms impacted several areas at the inception of the study in 1995 causing coastal habitat alterations as a result of salt-water intrusion. Both the habitat and the beach mice populations recovered during the course of the study. No direct impacts to southeastern beach mice were observed as a result of normal launch operations. Direct impacts were observed to the habitat as a result of the explosion of the Delta rocket in January 1997. This alteration of the habitant resulted in a shift in use with the mice moving on to the newly burned part of the site. Waterbirds use wetlands and aquatic systems near the launch complexes. Species include the Federally-listed, endangered Wood Stork (Mycteria americana) and several state-listed species of special concern including the Snowy Egret (Egretta thula thula), Reddish Egret (Egretta rufescens rufescens), White Ibis (Eudocimus albus), Roseate Spoonbill (Ajaia ajaja), Tricolored Heron (Egretta tricolor ruficolis), and Little Blue Heron (Egretta caerulea). No impacts to these populations resulting from any launch operations were observed. Gopher tortoises (Gopherus polyphemus) also occur around the launch complexes. Most of those observed appeared to be in good condition; however, upper respiratory tract disease is known to occur in the population. Cape Canaveral Air Station, including areas near active launch complexes, remains important habitat for a variety of native plants and animals including threatened and endangered species. Direct negative effects of current launch systems appear limited. Additional monitoring of these populations and habitats is required to determine if subtle, long-term changes are occurring, to determine if new launch systems and facilities cause other effects, and to determine the effects of habitat restoration and management.

Oddy, Donna M.↗
NASA NTRS1999

Environmental Conditions and Threatened and Endangered Species Populations near the Titan, Atlas, and Delta Launch Complexes, Cape Canaveral Air Station

Launches of Delta, Atlas, and Titan rockets from Cape Canaveral Air Station (CCAS) have potential environmental effects. These could occur from direct impacts of launches or indirectly from habitat alterations. This report summarizes a three-year study (1 995-1 998) characterizing the environment, with particular attention to threatened and endangered species, near Delta, Atlas, and Titan launch facilities. Cape Canaveral has been modified by Air Force development and by 50 years of fire suppression. The dominant vegetation type around the Delta and Atlas launch complexes is coastal oak hammock forest. Oak scrub is the predominant upland vegetation type near the Titan launch complexes. Compositionally, these are coastal scrub communities that has been unburned for > 40 years and have developed into closed canopy, low-stature forests. Herbaceous vegetation around active and inactive facilities, coastal strand and dune vegetation near the Atlantic Ocean, and exotic vegetation in disturbed areas are common. Marsh and estuarine vegetation is most common west of the Titan complexes. Launch effects to vegetation include scorch, acid, and particulate deposition. Discernable, cumulative effects are limited to small areas near the launch complexes. Water quality samples were collected at the Titan, Atlas, and Delta launch complexes in September 1995 (wet season) and January 1996 (dry season). Samples were analyzed for heavy metals, chloride, total organic carbon, calcium, iron, magnesium, sodium, total alkalinity, pH, and conductivity. Differences between fresh, brackish, and saline surface waters were evident. The natural buffering capacity of the environment surrounding the CCAS launch complexes is adequate for neutralizing acid deposition in rainfall and launch deposition. Populations of the Florida Scrub-Jay (Aphelocoma coerulescens), a Federally-listed, threatened species, reside near the launch complexes. Thirty-seven to forty-one scrub-jay territories were located at Titan, Atlas, and Delta launch complexes between 1995 and 1997. No direct impacts to scrub-jays were observed as a result of normal launches. The explosion of the Delta rocket in January 1997 caused direct impacts to the habitat of several scrub-jays families, from fire and debris; however, no scrub-jay mortality was observed. Mortality exceeded reproductive output at all areas over the course of the study. Populations of the southeastern beach mouse (Peromyscus polionotus niveiventris) populations, a Federally listed, threatened species, reside near all the launch complexes. Hurricane Erin and several other tropical storms impacted several areas at the inception of the study in 1995 causing coastal habitat alterations as a result of salt-water intrusion. Both the habitat and the beach mice populations recovered during the course of the study. No direct impacts to southeastern beach mice were observed as a result of normal launch operations. Direct impacts were observed to the habitat as a result of the explosion of the Delta rocket in January 1997. This alteration of the habitat resulted in a shift in use with the mice moving on to the newly burned part of the site. Waterbirds use wetlands and aquatic systems near the launch complexes. Species include the Federally-listed, endangered Wood Stork (Mycferia americana) and several state-listed species of special concern including the Snowy Egret (Egretfa thula fhula), Reddish Egret (Egreffa rufescens rufescens), White Ibis (Eudocimus albus), Roseate Spoonbill (Ajaia ajaja), Tricolored Heron (Egreffa tricolor ruficolis), and Little Blue Heron (Egreffa caerulea). No impacts to these populations resulting from any launch operations were observed. Gopher tortoises (Gopherus polyphemus) also occur around the launch complexes. Most of those observed appeared to be in good condition; however, upper respiratory tract disease is known to occur in the population. Cape Canaveral Air Station, including areas near active launch colexes, remains important habitat for a variety of native plants and animals including threatened and endangered species. Direct negative effects of current launch systems appear limited. Additional monitoring of these populations and habitats is required to determine if subtle, long-term changes are occurring, to determine if new launch systems and facilities cause other effects, and to determine the effects of habitat restoration and management.

Oddy, Donna M.↗
NASA NTRS2005

Characterization of a Subsurface Biosphere in a Massive Sulfide Deposits at Rio Tinto, Spain: Implications for Extant Life on Mars

The recent discovery of abundant sulfate minerals, particularly Jarosite by the Opportunity Rover at Sinus Merdiani on Mars has been interpreted as evidence for an acidic lake or sea on ancient Mars [1,2], since the mineral Jarosite is soluble in liquid water at pH above 4. The most likely mechanism to produce sufficient protons to acidify a large body of liquid water is near surface oxidation of pyrite rich deposits [3]. The acidic waters of the Rio Tinto, and the associated deposits of Hematite, Goethite, and Jarosite have been recognized as an important chemical analog to the Sinus Merdiani site on Mars [4]. The Rio Tinto is a river in southern Spain that flows 100 km from its source in the Iberian pyrite belt, one of the Earth s largest Volcanically Hosted Massive Sulfide (VHMS) provinces, into the Atlantic ocean. The river originates in artesian springs emanating from ground water that is acidified by the interaction with subsurface pyrite ore deposits. The Mars Analog Rio Tinto Experiment (MARTE) has been investigating the hypothesis that a subsurface biosphere exists at Rio Tinto living within the VHMS deposit living on chemical energy derived from sulfur and iron minerals. Reduced iron and sulfur might provide electron donors for microbial metabolism while in situ oxidized iron or oxidants entrained in recharge water might provide electron acceptors.

Stoker, C. R.↗
NASA NTRS2005

Characterization of a Subsurface Biosphere in a Massive Sulfide Deposit At Rio Tinto, Spain: Implications For Extant Life On Mars

The recent discovery of abundant sulfate minerals, particularly Jarosite by the Opportunity Rover at Sinus Merdiani on Mars has been interpreted as evidence for an acidic lake or sea on ancient Mars [1,2], since the mineral Jarosite is soluble in liquid water at pH above 4. The most likely mechanism to produce sufficient protons to acidify a large body of liquid water is near surface oxidation of pyrite rich deposits [3]. The acidic waters of the Rio Tinto, and the associated deposits of Hematite, Goethite, and Jarosite have been recognized as an important chemical analog to the Sinus Merdiani site on Mars [4]. The Rio Tinto is a river in southern Spain that flows 100 km from its source in the Iberian pyrite belt, one of the Earth's largest Volcanically Hosted Massive Sulfide (VHMS) provinces, into the Atlantic ocean. The river originates in artesian springs emanating from ground water that is acidified by the interaction with subsurface pyrite ore deposits. The Mars Analog Rio Tinto Experiment (MARTE) has been investigating the hypothesis that a subsurface biosphere exists at Rio Tinto living within the VHMS deposit living on chemical energy derived from sulfur and iron minerals. Reduced iron and sulfur might provide electron donors for microbial metabolism while in situ oxidized iron or oxidants entrained in recharge water might provide electron acceptors.

Stoker, C. R.↗
NASA NTRS2013

Algorithm Development for Predicting Biodiversity Based on Phytoplankton Absorption

Ocean color remote sensing has provided the scientific community with unprecedented global coverage of chlorophyll a, an indicator of phytoplankton biomass. Together, satellite-derived chlorophyll a and knowledge of Phytoplankton Functional Types (PFTs) will improve our limited understanding of marine ecosystem responses to physiochemical climate drivers involved in carbon cycle dynamics and linkages. Using cruise data from the Gulf of Maine and the Middle Atlantic Bight (N 269 pairs of HPLC and phytoplankton absorption samples), two modeling approaches were utilized to predict phytoplankton absorption and pigments. Algorithm I predicts the chlorophyll-specific absorption coefficient (a*(sub ph) (m(exp 2) mg chl a(exp - 1)) using inputs of temperature, light, and chlorophyll a. Modeled r(exp 2) values (400700 nm) ranged from 0.79 to 0.99 when compared to in situ observations with approximately 25 percent lower r(exp 2) values in the UV region. Algorithm II-a utilizes matrix inversion analysis to predict a(sub ph)(m(exp -1), 400700 nm) and r(exp 2) values ranged from 0.89 to 0.99. The prediction of phytoplankton pigments with Algorithm II-b produced r(exp 2) values that ranged from 0.40 to 0.93. When used in combination, Algorithm I, and Algorithm II-a are able to use satellite products of SST, PAR, and chlorophyll a (Algorithm I) to predict pigment concentrations and ratios to describe the phytoplankton community. The results of this study demonstrate that the spatial variation in modeled pigment ratios differ significantly from the 10-year SeaWiFS average chlorophyll a data set. Contiguous observations of chlorophyll a and phytoplankton biodiversity will elucidate ecosystem responses with unprecedented complexity.

phytoplankton↗
NASA NTRS2003

Alpha-amylase from the Hyperthermophilic Archaeon Thermococcus thioreducens

Extremophiles are microorganisms that thrive in, from an anthropocentric view, extreme environments such as hot springs. The ability of survival at extreme conditions has rendered enzymes from extremophiles to be of interest in industrial applications. One approach to producing these extremozymes entails the expression of the enzyme-encoding gene in a mesophilic host such as E.coli. This method has been employed in the effort to produce an alpha-amylase from a hyperthermophile (an organism that displays optimal growth above 80 C) isolated from a hydrothermal vent at the Rainbow vent site in the Atlantic Ocean. alpha-amylases catalyze the hydrolysis of starch to produce smaller sugars and constitute a class of industrial enzymes having approximately 25% of the enzyme market. One application for thermostable alpha-amylases is the starch liquefaction process in which starch is converted into fructose and glucose syrups. The a-amylase encoding gene from the hyperthermophile Thermococcus thioreducens was cloned and sequenced, revealing high similarity with other archaeal hyperthermophilic a-amylases. The gene encoding the mature protein was expressed in E.coli. Initial characterization of this enzyme has revealed an optimal amylolytic activity between 85-90 C and around pH 5.3-6.0.

Bernhardsdotter, E. C. M. J.↗
NASA NTRS2019

Sensitivity of Inherent Optical Properties from Ocean Reflectance Inversion Models to Satellite Instrument Wavelength Suites

The Earth science community seeks to develop climate data records (CDRs) from satellite measurements of ocean color, a continuous data record that now exceeds 20 years. Space agencies will launch additional instruments in the coming decade that will continue this data record, including the NASA PACE spectrometer. Inherent optical properties (IOPs) quantitatively describe the absorbing and scattering constituents of seawater and can be estimated from satellite-observed spectroradiometric data using semi-analytical algorithms (SAAs). SAAs exploit the contrasting optical signatures of constituent matter at spectral bands observed by satellite sensors. SAA performance, therefore, depends on the spectral resolution of the satellite spectroradiometer. A CDR spanning SeaWiFS, MODIS, OLCI, and PACE, for example, would include IOPs derived using varied wavelength suites if all available wavelengths were considered. Here, we explored differences in derived IOPs that stem simply from the use of (eight) different wavelength suites of input radiometric measurements. Using synthesized data and SeaWiFS Level-3 mission-long composites, we demonstrated equivalent SAA performance for all wavelength suites, but that IOP retrievals vary by several percent across wavelength suites and as a function of water type. The differences equate to roughly ≤ 6, 12, and 7% for a(sub dg)(443), a(sub ph)(443), and b(sub bp)(443), respectively, for waters with C(sub a) ≤ 1 mg -cu m. These values shrink for sensors with similar wavelength suites (e.g., SeaWiFS, MODIS, and MERIS) and rise to substantially larger values for higher C(sub a) waters. Our results also indicate that including 400 nm (in the case of OLCI) influences the derived IOPs, using longer wavelengths (>600 nm) influences the derived IOPs when there is a red signal, and, including additional spectral information shows potential for improved IOP estimation, but not without revisiting SAA parameterizations and execution. While modest in scope, we believe this study contributes to the knowledge base for CDR development. The implication of ignoring such an analysis as CDRs continue to be developed is a prolonged inability to distinguish between algorithmic and environmental contributions to trends and anomalies in the IOP time-series.

ocean color satellites↗
NASA NTRSDate not supplied

Autonomous Measurement of Electrochemical Redox Couples for In-Situ Characterization of Enceladus Plume Samples

A 3D-printed microfluidic electrochemical cell with integrated electrodes was developed to demonstrate autonomous in-situ electrochemical characterization of terrestrial seawater samples. The system is designed to extend the capabilities of the 2008 Phoenix Lander’s Wet Chemistry Laboratory (WCL) that analyzed the soluble chemistry of the Martian soil, by miniaturizing its fluidic architecture for analysis of µL-volume samples as expected from an Enceladus fly-by mission. The microfluidic device has a total fluid volume of 48 µL and includes dual channels each populated with 7 electrodes. Measurement of pH was measured using an iridium oxide electrode. Cyclic voltammetry with Au, Pt, and glassy carbon working electrodes was used to measure redox couples in synthetic seawater that contained inorganic and bio-organic molecules. Glassy carbon was found to have minimal risk of interference from constituents of synthetic seawater when measuring molecular organic redox species; however, care must be used to prevent interference due to potential oxidation or dissolution in the case of Au working electrodes. A completely autonomous end-to-end run including sample delivery was performed, to demonstrate the feasibility of microfluidic-based cyclic voltammetry measurements for in-situ characterization of redox couples in Ocean World samples.

Planetary Instruments↗
NASA NTRS1983

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.↗
NASA NTRS1995

Geochemical constraints on chemolithoautotrophic reactions in hydrothermal systems

Thermodynamic calculations provide the means to quantify the chemical disequilibrium inherent in the mixing of reduced hydrothermal fluids with seawater. The chemical energy available for metabolic processes in these environments can be evaluated by taking into account the pressure and temperature dependence of the apparent standard Gibbs free energies of reactions in the S-H2-H2O system together with geochemical constraints on pH, activities of aqueous sulfur species and fugacities of H2 and/or O2. Using present-day mixing of hydrothermal fluids and seawater as a starting point, it is shown that each mole of H2S entering seawater from hydrothermal fluids represents about 200,000 calories of chemical energy for metabolic systems able to catalyze H2S oxidation. Extrapolating to the early Earth, which was likely to have had an atmosphere more reduced than at present, shows that this chemical energy may have been a factor of two or so less. Nevertheless, mixing of hydrothermal fluids with seawater would have been an abundant source of chemical energy, and an inevitable consequence of the presence of an ocean on an initially hot Earth. The amount of energy available was more than enough for organic synthesis from CO2 or CO, and/or polymer formation, indicating that the vicinity of hydrothermal systems at the sea floor was an ideal location for the emergence of the first chemolithoautotrophic metabolic systems.

Shock, Everett L.↗
NASA NTRS2002

Ultramafic Terranes and Associated Springs as Analogs for Mars and Early Earth

Putative extinct or extant Martian organisms, like their terrestrial counterparts, must adopt metabolic strategies based on the environments in which they live. In order for organisms to derive metabolic energy from the natural environment (Martian or terrestrial), a state of thermodynamic disequilibrium must exist. The most widespread environment of chemical disequilibrium on present-day Earth results from the interaction of mafic rocks of the ocean crust with liquid water. Such environments were even more pervasive and important on the Archean Earth due to increased geothermal heat flow and the absence of widespread continental crust formation. The composition of the lower crust and upper mantle of the Earth is essentially the-same as that of Mars, and the early histories of these two planets are similar. It follows that a knowledge of the mineralogy, water-rock chemistry and microbial ecology of Earth's oceanic crust could be of great value in devising a search strategy for evidence of past or present life on Mars. In some tectonic regimes, cross-sections of lower oceanic crust and upper mantle are exposed on land as so-called "ophiolite suites." Such is the case in the state of California (USA) as a result of its location adjacent to active plate margins. These mafic and ultramafic rocks contain numerous springs that offer an easily accessible field laboratory for studying water/rock interactions and the microbial communities that are supported by the resulting geochemical energy. A preliminary screen of Archaean biodiversity was conducted in a cold spring located in a presently serpentinizing ultramafic terrane. PCR and phylogenetic analysis of partial 16s rRNA, sequences were performed on water and sediment samples. Archaea of recent phylogenetic origin were detected with sequences nearly identical to those of organisms living in ultra-high pH lakes of Africa.

Blake, David↗
NASA NTRS1991

Attempted nonenzymatic template-directed oligomerizations on a polyadenylic acid template: implications for the nature of the first genetic material

Previous attempts to produce nonenzymatic template-directed oligomerizations of activated pyrimidines on polypurine templates have been unsuccessful. The only efficient reactions are those where the template is composed primarily of pyrimidines, especially cytosine. Because molecular evolution requires that a synthesized daughter polynucleotide be capable of acting as a template for the synthesis of the original polynucleotide, the one-way replication achieved thus far is inadequate to initiate an evolving system. Several uracil analogs were used in this investigation in order to search for possible replacements for uracil. The monomers used in this investigation were the imidazolides of UMP, xanthosine 5'-monophosphate, the bis-monophosphates of the acyclic nucleosides of uracil, and 2,4-quinazolinedione. The concentrations of various salts, buffers, pH, and temperature were among the different variables investigated in attempts to find conditions that would permit template-directed oligomerizations. Although the different monomers in this study demonstrated varying abilities to form very short oligomers, we were unable to detect any enhancement of this oligomerization that could be attributed to the poly(A) template. Although special conditions might be found that would allow purine-rich templates to work, these reactions cannot be considered robust. The results of our experiments suggest that pyrimidines were not part of the original replicating system on the primitive Earth. It has already been shown that ribose is an unlikely component of the first replicating systems, and we now suggest that phosphate was absent as well. This is due to the low solubility of phosphate in the present ocean (3 x 10(-6) M), as well as the difficulty of prebiotic activation of phosphates.

Non-NASA Center↗
NASA NTRS2003

Autotrophic Ecosystems on the Early Earth

Ophiolite sequences, sections of lower oceanic crust and upper mantle that have been thrust onto continental craton, are located in northern and central California and provide easily accessible areas that serve as good analogs for similar, more extensive areas of the early Earth. We have begun investigating and characterizing these sites in order to understand better the processes that may be responsible for the water chemistry, mineralogy and biology of similar environments on the early Earth. The geophysical and geochemical processes in these terranes provide niches for unique communities of extremeophiles and likely provide a good analog to the location that first gave rise to life on Earth. The ophiolites found in northern and central California include the Trinity, Josephine, Coast Range and Point Sal, all of which are approximately 160 million years old. Fluids from serpentinizing springs are generally alkaline with high pH and H2 contents, indicating that the mafic rock compositions control the fluid composition through water-rock reactions during relatively low-grade hydrothermal processes. There are significant amounts of primary mineralogy remaining in the rocks, meaning that substantial alteration processes are still occurring in these terranes. The general reaction for serpentinization of olivine is given by one of the authors. olivine + H2O = serpentine + brucite + magnetite + H2. We have analyzed the mineralogical composition of several rock samples collected from the Coast Range Ophiolite near Clear Lake, CA by electron microprobe. The remnant primary mineralogy is fairly urnform in composition, with an olivine composition of Fo(sub 90), and with pyroxene compositions of En(sub 90) for orthopyroxene and En(sub 49)Wo(sub 48)Fs(sub 03) for the clinopyroxene. Other primary phases observed include chromites and other spinels. Examination of petrographic thin sections reveals that serpentinization reactions have occurred in these locations. The serpentine resulting from aqueous alteration of olivine resides in veins that are see to cross cut the primary mineral grains. There are several generations of alteration products, comprised mostly of serpentines that are magnesium rich, with magnetite, brucite and carbonates observed as accessory minerals. The formation of carbonates can be taken to indicate the presence of CO2 in the altering fluids. We collected samples from a spring in the Coast Range Ophiolite in order to determine whether the geochemical environment serves as a habitat for chemotrophic microorganisms. DNA was extracted from the sediment samples and the 16s rRNA gene was PCR amplified using universal Archaeal primers. Denaturing gradient gel electrophoresis (DGGE) was used to determine the community of Archaea thriving in these samples. Our results indicate that there were 8 different genera of Archaea from a single sample. A sequence was obtained from one of these eight. The sequence is of an organism similar to Halorubrum tibetense, and alkalophilic Archaeon. This result suggests that these environments are likely hosts for communities of organisms that are adapted for the unique chemistry provided by the alkaline spring.

Schulte, M.↗
NASA NTRS2017

Sample Processor for Life on Icy Worlds (SPLIce): Design and Test Results

We report the design, development, and testing of the Sample Processor for Life on Icy Worlds (SPLIce) system, a microfluidic sample processor to enable autonomous detection of signatures of life and measurements of habitability parameters in Ocean Worlds. This monolithic fluid processing-and-handling system (Figure 1; mass 0.5 kg) retrieves a 50-L-volume sample and prepares it to supply a suite of detection instruments, each with unique preparation needs. SPLIce has potential applications in orbiter missions that sample ocean plumes, such as found in Saturns icy moon Enceladus, or landed missions on the surface of icy satellites, such as Jupiters moon Europa. Answering the question Are we alone in the universe? is captivating and exceptionally challenging. Even general criteria that define life very broadly include a significant role for water [1,2]. Searches for extinct or extant life therefore prioritize locations of abundant water whether in ancient (Mars), or present (Europa and Enceladus) times. Only two previous planetary missions had onboard fluid processing: the Viking Biology Experiments [3] and Phoenixs Wet Chemistry Laboratory (WCL) [4]. SPLIce differs crucially from those systems, including its capability to process and distribute L-volume samples and the integration autonomous control of a wide range of fluidic functions, including: 1) retrieval of fluid samples from an evacuated sample chamber; 2) onboard multi-year storage of dehydrated reagents; 3) integrated pressure, pH, and conductivity measurement; 4) filtration and retention of insoluble particles for microscopy; 5) dilution or vacuum-driven concentration of samples to accommodate instrument working ranges; 6) removal of gas bubbles from sample aliquots; 7) unidirectional flow (check valves); 8) active flow-path selection (solenoid-actuated valves); 9) metered pumping in 100 nL volume increments. The SPLIce manifold, made of three thermally fused layers of precision-machined cyclo-olefin polymer, supports all fluidic components (Figure 1) and integrated microchannels (125 x 250 m). Fluid is pumped by a stepper-motor-driven pump (Lee Co.). The functionality of the integrated MEMS pressure sensor (Honeywell) and passive check valves (Figure 2) were tested in conjunction with our newly designed integral bubble traps (Figure 3) and hydrophobic membrane-based concentrator (Figure 4). The concentrator (initially tested as a standalone component) demonstrated 5-fold vacuum-evaporative concentration. Polyethylene fused bead beds (PEFBBs; 50 porosity) store drylyophilized buffers, calibrants, and fluorescent dyes, and also promote mixing of sample with calibrant, dye, or H2O. Software-controlled automated tests demonstrated successful 1) fluid delivery to each component 2) valve and pump synchronization 3) sample aliquot delivery to instrument interface ports, and 4) rehydration of vacuum-dried fluorescent dye. In Figure 5, fluorescein on PEFBBs was rehydrated for 15 min using a pump-delivered water aliquot; it is displaced as H2O enters the bottom of the channel and pushes the dye into a check valve. Ultimately, SPLIce will fluorescently label amino acids in the sample for microchip-based electrophoretic (MCE) chiral separation and detection to seek and quantify key organic bio-signatures [5]; it will also deliver sample to a microfluidic version of WCL (mWCL) to measure soluble ions and redox-active species.

Life detection↗
NASA NTRS1991

Catalysis of hydrolysis and nucleophilic substitution at the P-N bond of phosphoimidazolide-activated nucleotides in phosphate buffers

Phosphoimidazolide-activated derivatives of guanosine and cytidine 5'-monophosphates, henceforth called ImpN's, exhibit enhanced rates of degradation in the presence of aqueous inorganic phosphate in the range 4.0 < or = pH < or = 8.6. This degradation is been attributed to (i) nucleophilic substitution of the imidazolide and (ii) catalysis of the P-N bond hydrolysis by phosphate. The first reaction results in the formation of nucleoside 5'-diphosphate and the second in nucleoside 5'-monophosphate. Analysis of the observed rates as well as the product ratios as a function of pH and phosphate concentration allow distinction between various mechanistic possibilities. The results show that both H2PO4- and HPO4(2-) participate in both hydrolysis and nucleophilic substitution. Statistically corrected biomolecular rate constants indicate that the dianion is 4 times more effective as a general base than the monoanion, and 8 times more effective as nucleophile. The low Bronsted value beta = 0.15 calculated for these phosphate species, presumed to act as general bases in facilitating water attack, is consistent with the fact that catalysis of the hydrolysis of the P-N bond in ImpN's has not been detected before. The beta nuc = 0.35 calculated for water, H2PO4-, HPO4(2-), and hydroxide acting as nucleophiles indicates a more associative transition state for nucleotidyl (O2POR- with R = nucleoside) transfers than that observed for phosphoryl (PO3(2-)) transfers (beta nuc = 0.25). With respect to the stability/reactivity of ImpN's under prebiotic conditions, our study shows that these materials would not suffer additional degradation due to inorganic phosphate, assuming the concentrations of phosphate, Pi, on prebiotic Earth were similar to those in the present oceans ([Pi] approximately 2.25 micromoles).

NASA Discipline Number 52-20↗
NASA NTRS1986

Competition for sulfide among colorless and purple sulfur bacteria in cyanobacterial mats

The vertical zonation of light, O2, H2S, pH, and sulfur bacteria was studied in two benthic cyanobacterial mats from hypersaline ponds at Guerrero Negro, Baja California, Mexico. The physical-chemical gradients were analyzed in the upper few mm at < or = 100 micrometers spatial resolution by microelectrodes and by a fiber optic microprobe. In mats, where oxygen produced by photosynthesis diffused far below the depth of the photic zone, colorless sulfur bacteria (Beggiatoa sp.) were the dominant sulfide oxidizing organisms. In a mat, where the O2-H2S interface was close to the photic zone, but yet received no significant visible light, purple sulfur bacteria (Chromatium sp.) were the dominant sulfide oxidizers. Analysis of the spectral light distribution here showed that the penetration of only 1% of the incident near-IR light (800-900 nm) into the sulfide zone was sufficient for the mass development of Chromatium in a narrow band of 300 micromoles thickness. The balance between O2 and light penetration down into the sulfide zone thus determined in micro-scale which type of sulfur bacteria became dominant.

NASA Center ARC↗