Search NASA⌕ Search

SEARCH · Search NASA

Results for “ocean pH”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 91 records · Page 5
All sourcesNASA NTRSDOE OSTI
NASA NTRS2004

Composition of Simulated Martian Brines and Implications for the Origin of Martian Salts

We report on laboratory experiments that have produced dilute brines under controlled conditions meant to simulate past and present Mars. We allowed an SNC-derived mineral mix to react with pure water under a simulated present-Mars atmosphere for seven months. We then subjected the same mineral mix to a similar aqueous environment for one year, but with a simulated Mars atmosphere that contained the added gases SO2, HCl and NO2. The addition of acidic gases was designed to mimic the effects of volcanic gases that may have been present in the martian atmosphere during periods of increased volcanic activity. The experiments were performed at one bar and at two different temperatures in order to simulate subsurface conditions where liquid water and rock are likely to interact on Mars. The dominant cations dissolved in the solutions we produced were Ca(2+), Mg(2+), Al(3+) and Na(+), while the major anions are dissolved C, F(-), SO4(2-) and Cl(-). Typical solution pH was 4.2 to 6.0 for experiments run with a Mars analog atmosphere, and 3.6-5.0 for experiments with acidic gases added. Abundance patterns of elements in the synthetic sulfate-chloride brines produced under acidic conditions were distinctly unlike those of terrestrial ocean water, terrestrial continental waters, and those measured in the martian fines at the Mars Pathfinder and Viking 1 and 2 landing sites. In particular, the S/Cl ratio in these experiments was about 200, compared with an average value of approx. 5 in martian fines. In contrast, abundance patterns of elements in the brines produced under a present day Mars analog atmosphere were quite similar to those measured in the martian fines at the Mars Pathfinder and Viking 1 and 2 landing sites. This suggests that salts present in the martian regolith may have formed over time as a result of the interaction of surface or subsurface liquid water with basalts in the presence of a martian atmosphere similar in composition to that of today, rather than in an atmosphere higher in acidic volatiles.

Bullock, M. A.↗
NASA NTRS2004

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

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

Greenhouse Effect↗
DOE OSTI2024

Pulse Electrodeposition for Carbonate-Rich Deposits from Seawater

Seawater electrodeposition is gaining renewed interest in the context of sustainable development, both to build climate-resilient coastal infrastructure and for ocean-based decarbonization applications. Most of the applications benefit from CaCO 3 -rich deposits, but constant-voltage electrodeposition results in a mixture of CaCO 3 and Mg(OH) 2 , especially at higher voltages where precipitation rates are more desirable. The use of pulse voltages can help control interfacial pH that dictates the precipitation reactions. Here, we explore the use of pulse electrodeposition as a function of pulse frequency and duty cycle to control deposit composition. The most CaCO 3 -rich deposits were obtained under 10 Hz frequency and 10% duty cycle conditions for the voltage window investigated (-0.8 V to -1.2 V vs. SCE). While pulsing the voltage increases the amount of CaCO 3 deposited, the energy required per gram of CaCO 3 is significantly higher (14.5×) when compared to the base case of applying a constant voltage of -0.8 V vs. SCE. Further optimization of pulse conditions, electrode materials, and system configuration could lead to finding parameters that result in exclusively carbonate deposits without compromising precipitation rates, which may prove to be more useful for corrosion protection, coastal infrastructure, and other applications in sustainable development.

54 ENVIRONMENTAL SCIENCES↗
NASA NTRS2023

A Hyperspectral Inversion Framework for Estimating Absorbing Inherent Optical Properties and Biogeochemical Parameters in Inland and Coastal Waters

The simultaneous remote estimation of biogeochemical parameters (BPs) and inherent optical properties (IOPs) from hyperspectral satellite imagery of globally distributed optically distinct inland and coastal waters is a complex, unsolved, non-unique inverse problem. To tackle this problem, we leverage a machine-learning model termed Mixture Density Networks (MDNs). MDNs outperform operational algorithms by calculating the covariance between the simultaneously estimated products. We train the MDNs on a large ( N = 8237) dataset of co-aligned, in situ measured, hyperspectral remote sensing reflectance (R rs ), BPs, and absorbing IOPs from globally representative optically distinct inland and coastal waters. The estimated IOPs include absorption due to phytoplankton (a ph ), chromophoric dissolved organic matter (a cdom ), and non-algal particles (a nap ). The estimated BPs include chlorophyll-a, total suspended solids, and phycocyanin (PC). MDNs dramatically reduce uncertainty in the retrievals, relative to operational algorithms, when using a 50/50 dataset split, where the MDNs are trained on a randomly selected half of the in situ dataset and validated on the other half. Our model is shown to have higher, or equivalent, generalization performance than the calculated operational algorithms available for all BPs and IOPs (except PC) via a leave-one-out cross-validation assessment. The MDNs are sensitive to uncertainties in the hyperspectral satellite R rs , resulting from instrument noise and atmospheric correction; there is a difference of ~37.4–62.8% (using median symmetric accuracy) between the MDNs’ estimates derived from co-located satellite-derived R rs and in situ R rs . Of the IOPs, a cdom and a nap are less sensitive to uncertainties in hyperspectral satellite imagery relative to a ph , with remote estimates of a ph exhibiting incorrect spectral shape and magnitude relative to in situ measured IOPs. Despite the uncertainties in satellite derived R rs , the spatial distributions of BPs and IOPs in MDN-derived product maps of Lake Erie and the Curonian Lagoon, based on imagery taken with the Hyperspectral Imager for the Coastal Ocean (HICO) and PRecursore Iper-Spettrale della Missione Applicativa (PRISMA), are confirmed via co-aligned in situ measurements and agree with the literature’s understanding of these well-studied regions. The consistency and accuracy of the model on HICO and PRISMA imagery, despite radiometric uncertainties, demonstrate its applicability to future hyperspectral missions, such as the Plankton, Aerosol, Cloud, ocean Ecosystem (PACE) mission, where the simultaneous estimation model will serve as a key part of phytoplankton community composition analysis.

Ryan E. O'Shea↗
NASA NTRS1992

Water Sensors

Mike Morris, former Associate Director of STAC, formed pHish Doctor, Inc. to develop and sell a pH monitor for home aquariums. The monitor, or pHish Doctor, consists of a sensor strip and color chart that continually measures pH levels in an aquarium. This is important because when the level gets too high, ammonia excreted by fish is highly toxic; at low pH, bacteria that normally break down waste products stop functioning. Sales have run into the tens of thousands of dollars. A NASA Tech Brief Technical Support Package later led to a salt water version of the system and a DoE Small Business Innovation Research (SBIR) grant for development of a sensor for sea buoys. The company, now known as Ocean Optics, Inc., is currently studying the effects of carbon dioxide buildup as well as exploring other commercial applications for the fiber optic sensor.

Source record↗
NASA NTRS2003

Two Strategies for Microbial Production of an Industrial Enzyme-Alpha-Amylase

Extremophiles are microorganisms that thrive in, from an anthropocentric view, extreme environments including hot springs, soda lakes and arctic water. This ability of survival at extreme conditions has rendered extremophiles to be of interest in astrobiology, evolutionary biology as well as in industrial applications. Of particular interest to the biotechnology industry are the biological catalysts of the extremophiles, the extremozymes, whose unique stabilities at extreme conditions make them potential sources of novel enzymes in industrial applications. There are two major approaches to microbial enzyme production. This entails enzyme isolation directly from the natural host or creating a recombinant expression system whereby the targeted enzyme can be overexpressed in a mesophilic host. We are employing both methods in the effort to produce alpha-amylases from a hyperthermophilic archaeon (Thermococcus) isolated from a hydrothermal vent in the Atlantic Ocean, as well as from alkaliphilic bacteria (Bacillus) isolated from a soda lake in Tanzania. Alpha-amylases catalyze the hydrolysis of internal alpha-1,4-glycosidic linkages in starch to produce smaller sugars. Thermostable alpha-amylases are used in the liquefaction of starch for production of fructose and glucose syrups, whereas alpha-amylases stable at high pH have potential as detergent additives. The alpha-amylase encoding gene from Thermococcus was PCR amplified using carefully designed primers and analyzed using bioinformatics tools such as BLAST and Multiple Sequence Alignment for cloning and expression in E.coli. Four strains of Bacillus were grown in alkaline starch-enriched medium of which the culture supernatant was used as enzyme source. Amylolytic activity was detected using the starch-iodine method.

Bernhardsdotter, Eva C. M. J.↗
NASA NTRS2024

Effect of the Liquid-Vacuum Transition on the Relative Abundances of Amino and Fatty Acids Sought as Biosignatures on Icy Ocean Worlds

Interpreting measurements by robotic missions searching for signs of life in material erupted by cryovolcanic ocean worlds (e.g., Enceladus, Europa, Ceres) requires linking the composition of this material to that of its subsurface liquid source. Irrespective of the properties of –and processes along– the path of ejection, material erupted on airless worlds undergoes a transition from liquid to vacuum. Here, we investigate experimentally the effect of a direct transition from liquid to vacuum environments on the relative abundances of amino and carboxylic (fatty) acids, a metric used to distinguish between biological and abiotic sources for these compounds. Amino acids were dissolved in parent solutions prepared with 1 wt.% NaCl and pH 9–10 to match properties inferred from Enceladus plume grains. Compositional analysis of the dry solids resulting from the injection of this solution into vacuum indicates a < 50% change in amino acid abundances relative to glycine. Injection of two fatty acids, phenylacetic acid (soluble and undersaturated in the parent solution) and palmitic acid (insoluble and supersaturated) resulted in a change of less than a factor of 7 in their relative abundances. At this bulk scale (all grains aggregated together), proportions of amino and fatty acids were sufficiently conserved to allow distinction between end-member example biological and abiotic sources. We did not find strong correlations between the relative enrichment or depletion of amino or fatty acids with molecular properties such as molecular mass, hydrophobicity, functionality, or charge, other than high under-or supersaturation. Most of the organic residue was deposited along the experimental injection path, which suggests that cryovolcanic conduit walls on icy ocean worlds may be enriched in organic material relative to material having undergone the liquid-vacuum transition.

Amino acids↗
DOE OSTI2022

Ocean Deacidification Technologies for Marine Aquaculture

The increase in partial pressure of CO 2 in the oceans directly affects the productivity and survival of coastal industries and ecosystems. For marine aquaculture, the decreased alkalinity of seawater results in reduced availability of carbonates for marine organisms to build their shells, leading to decreased aquaculture quality and productivity. The industry has been implementing recirculating aquaculture systems (RASs) to reduce CO 2 in feedwaters, but recent interest in ocean-based CO 2 capture has led to additional strategies that may be relevant. The new methods in addition to CO 2 removal offer capture options for enhanced aquaculture sustainability. Here, we review and compare early-stage and commercially available technologies for deacidification of seawater and their suitability for aquaculture. Most methods considered rely on a voltage-induced pH swing to shift the carbonate/bicarbonate equilibrium toward the release of CO 2 , with subsequent capture of the released CO 2 as a gas or as solid mineral carbonates. The modular design and distributed deployment potential of these systems offers promise, but current demonstrations are limited to bench scale, highlighting the need for sustained research and development before they can be implemented for marine aquaculture.

42 ENGINEERING↗
NASA NTRS1983

Atmospheric composition - Influence of biology

The variability of atmospheric constituents influenced by biological organisms over various time scales is examined, together with the human contribution to atmospheric sulfur. The biogeochemistry of nitrogen is discussed, with an emphasis on N2O, NO, and microbially mediated reactions in soil and water. Carbon species are bound up mainly in sediments and the deep ocean, but human activities involving combustion may cause a doubling of the atmospheric levels of CO2 in the near future, which could produce a general low-level atmospheric warming. Longer term measurements are required to assess the effects of CH4 augmentation in the atmosphere through fuel combustion. Coal burning effectively doubles the amount of SO2 produced by natural sources, and reduces the pH of rainwater, thus posing hazards to fish, plankton, and mollusc life.

Mcelroy, M. B.↗
NASA NTRS1995

Dissolution and reduction of magnetite by bacteria

Magnetite (Fe3O4) is an iron oxide of mixed oxidation state [Fe(II), Fe(III)] that contributes largely to geomagnetism and plays a significant role in diagenesis in marine and freshwater sediments. Magnetic data are the primary evidence for ocean floor spreading and accurate interpretation of the sedimentary magnetic record depends on an understanding of the conditions under which magnetite is stable. Though chemical reduction of magnetite by dissolved sulfide is well known, biological reduction has not been considered likely based upon thermodynamic considerations. This study shows that marine and freshwater strains of the bacterium Shewanella putrefaciens are capable of the rapid dissolution and reduction of magnetite, converting millimolar amounts to soluble Fe(II)in a few days at room temperature. Conditions under which magnetite reduction is optimal (pH 5-6, 22-37 degrees C) are consistent with an enzymatic process and not with simple chemical reduction. Magnetite reduction requires viable cells and cell contact, and it appears to be coupled to electron transport and growth. In a minimal medium with formate or lactate as the electron donor, more than 10 times the amount of magnetite was reduced over no carbon controls. These data suggest that magnetite reduction is coupled to carbon metabolism in S. putrefaciens. Bacterial reduction rates of magnetite are of the same order of magnitude as those estimated for reduction by sulfide. If such remobilization of magnetite occurs in nature, it could have a major impact on sediment magnetism and diagenesis.

Non-NASA Center↗
NASA NTRS2011

A Multifunctional Coating for Autonomous Corrosion Control

This slide presentation reviews the effects of corrosion on various structures at the Kennedy Space Center, and the work to discover a corrosion control coating that will be autonomous and will indicate corrosion at an early point in the process. Kennedy Space Center has many environmental conditions that are corrosive: ocean salt spray, heat, humidity, sunlight and acidic exhaust from the Solid Rocket Boosters (SRBs). Presented is a chart which shows the corrosion rates of carbon steel at various locations. KSC has the highest corrosion rates with 42.0 mils/yr, leading the next highest Galeta Point Beach, in the Panama Canal Zone with 27 mils/yr corrosion. A chart shows the changes in corrosion rate with the distance from the ocean. The three types of corrosion protective coatings are described: barrier (passive), Barrier plus active corrosion inhibiting components, and smart. A smart coating will detect and respond actively to changes in its environment in a functional and predictable manner and is capable of adapting its properties dynamically. The smart coating uses microcapsules, particles or liquid drops coated in polymers, that can detect and control the corrosion caused by the environment. The mechanism for a pH sensitive microcapsule and the hydrophobic core microcapsule are demonstrated and the chemistry is reviewed. When corrosion begins, the microcapsule will release the contents of the core (indicator, inhibitor, and self healing agent) in close proximity to the corrosion. The response to a pH increase is demonstrated by a series of pictures that show the breakdown of the microcapsule and the contents release. An example of bolt corrosion is used, as an example of corrosion in places that are difficult to ascertain. A comparison of various coating systems is shown.

Calle, L. M.↗
NASA NTRSDate not supplied

Identifying Sources of Sulfate Preserved in High Elevation Lava Tubes From Mauna Loa, Hawaii

Volcanic sulfates record a history of their formation pathways in their triple oxygen isotope compositions, making them a powerful target for understanding atmospheric chemistry. To understand how these isotopic signals may be preserved in sulfate minerals, we investigate multiple O and S isotopes of thenardite, mirabilite, and gypsum from in a Mars analog environment: a pair of lava tubes near the summit of Mauna Loa, Hawaii. Based on 16 O-, 17 O- 18 O compositions, the primary oxygen sources for sulfates in the lava tube are atmospheric oxygen (O 2 ), peroxide (H 2 O 2 ), and ozone (O 3 ). We suggest the isotopic signature of O 2 originates from combustion of reduced sulfur gases and/or elemental sulfur at the eruptive source or within the lava tube soon after skylight collapse. Sulfate with isotopic signatures of peroxide and ozone are typically expected from aqueous reactions in cloud droplets. Chemical modeling indicates the observed proportion of ozone sourced sulfate requires pH greater than ~5.4, higher than measured cloud water pH, instead suggesting the observed O 3 signature could not have formed in cloud water droplets. We interpret that sulfate possessing an ozone signature in the lava tube sulfates formed on wetted surfaces of the lava tubes with alkalinity from alteration of basaltic glass. Furthermore, the oxygen and sulfur isotopes of the sulfate are uncorrelated. Multiple sulfur isotopes ( 32 S- 33 S- 34 S- 36 S) from the Mauna Loa sulfates are consistent with ocean island basalt from Pitcairn, suggesting the sulfate-sulfur has not been modified compared to its volcanic source. The findings of this study indicate that oxidation by ozone plays a key role in the formation of sulfate within lava tubes. We also find that combustion is a significant pathway toward sulfuric acid formation in volcanic environments. Similar signatures should be expected on other planets if volcanism is a significant sulfate source, as has been suggested for Mars. If true, sulfates in returned samples from Mars may hold key information on pO 2 , pCO 2 and planetary scale oxygen fluxes at the time of sulfate formation.

Justin Hayles↗
DOE OSTI2021

Propagation of the 2014–2016 Northeast Pacific Marine Heatwave Through the Salish Sea

Effects and impacts of the Northeast Pacific marine heatwave of 2014–2016 on the inner coastal estuarine waters of the Salish Sea were examined using a combination of monitoring data and an established three-dimensional hydrodynamic and biogeochemical model of the region. The anomalous high temperatures reached the U.S. Pacific Northwest continental shelf toward the end of 2014 and primarily entered the Salish Sea waters through an existing strong estuarine exchange. Elevated temperatures up to + 2.3°C were observed at the monitoring stations throughout 2015 and 2016 relative to 2013 before dissipating in 2017. The hydrodynamic and biogeochemical responses to this circulating high-temperature event were examined using the Salish Sea Model over a 5-year window from 2013 to 2017. Responses of conventional water-quality indicator variables, such as temperature and salinity, nutrients and phytoplankton, zooplankton, dissolved oxygen, and pH, were evaluated relative to a baseline without the marine heatwave forcing. The simulation results relative to 2014 show an increase in biological activity (+14%, and 6% Δ phytoplankton biomass, respectively) during the peak heatwave year 2015 and 2016 propagating toward higher zooplankton biomass (+14%, +18% Δ mesozooplankton biomass). However, sensitivity tests show that this increase was a direct result of higher freshwater and associated nutrient loads accompanied by stronger estuarine exchange with the Pacific Ocean rather than warming due to the heatwave. Strong vertical circulation and mixing provided mitigation with only ≈+0.6°C domain-wide annual average temperature increase within Salish Sea, and served as a physical buffer to keep waters cooler relative to the continental shelf during the marine heatwave.

54 ENVIRONMENTAL SCIENCES↗
NASA NTRS2012

Concentration Effects and Ion Properties Controlling the Fractionation of Halides during Aerosol Formation

During the aerosolization process at the sea surface, halides are incorporated into aerosol droplets, where they may play an important role in tropospheric ozone chemistry. Although this process may significantly contribute to the formation of reactive gas phase molecular halogens, little is known about the environmental factors that control how halides selectively accumulate at the air−water interface. In this study, the production of sea spray aerosol is simulated using electrospray ionization (ESI) of 100 nM equimolar solutions of NaCl, NaBr, NaI, NaNO2, NaNO3, NaClO4, and NaIO4. The microdroplets generated are analyzed by mass spectrometry to study the comparative enrichment of anions (f (Isub x-)) and their correlation with ion properties. Although no correlation exists between f (sub x-) and the limiting equivalent ionic conductivity, the correlation coefficient of the linear fit with the size of the anions R(sub x-), dehydration free-energy ΔGdehyd, and polarizability alpha, follows the order: (R(sub x-)(exp −2)) > (R(sub x-)(exp −1)) >(R(sub x-) > delta G(sub dehyd) > alpha. The same pure physical process is observed in H2O and D2O. The factor f (sub x-) does not change with pH (6.8−8.6), counterion (Li+, Na+, K+, and Cs+) substitution effects, or solvent polarity changes in methanol − and ethanol−water mixtures (0 <= xH2O <= 1). Sodium polysorbate 20 surfactant is used to modify the structure of the interface. Despite the observed enrichment of I− on the air−water interface of equimolar solutions, our results of seawater mimic samples agree with a model in which the interfacial composition is increasingly enriched in I− < Br− < Cl− over the oceanic boundary layer due to concentration effects in sea spray aerosol formation.

iodine↗
NASA NTRS1988

REE in the Great Whale River estuary, northwest Quebec

A report on REE concentrations within the estuary of the Great Whale River in northwest Quebec and in Hudson Bay is given, showing concentrations which are less than those predicted by conservative mixing of seawater and river water, indicating removal of REE from solution. REE removal is rapid, occurring primarily at salinities less than 2 percent and ranges from about 70 percent for light REE to no more than 40 percent for heavy REE. At low salinity, Fe removal is essentially complete. The shape of Fe and REE vs. salinity profiles is not consistent with a simple model of destabilization and coagulation of Fe and REE-bearing colloidal material. A linear relationship between the activity of free ion REE(3+) and pH is consistent with a simple ion-exchange model for REE removal. Surface and subsurface samples of Hudson Bay seawater show high REE and La/Yb concentrations relative to average seawater, with the subsurface sample having a Nd concentration of 100 pmol/kg and an epsilon(Nd) of -29.3; characteristics consistent with river inputs of Hudson Bay. This indicates that rivers draining the Canadian Shield are a major source of nonradiogenic Nd and REE to the Atlantic Ocean.

Goldstein, Steven J.↗
NASA NTRS1999

Prebiotic Nitrogen Fixation by FeS Reduction of Nitrite Under Acidic Conditions

Theories for the origin of life require the availability of reduced nitrogen for the formation of such species as amino acid and nucleic acids. In a strongly reducing atmosphere, compounds essential to the chemical evolution of life, such as amino acids, can form by reactions between HCN, NH3, and carbonyl compounds produced in spark discharges. However, under non-reducing atmospheres, electric discharges produced NO rather than HCN or NH3. This raises the questions of; how ammonia can be formed under a neutral atmosphere, and what conditions are needed such formation to occur? On possibility is the conversion of NO into nitric and nitrous acids (through HNO) and rained into the oceans. The reduction of nitrite by aqueous Fe(II) (6 Fe(+2) + 7 H(+) + NO2(-) yields 6 Fe(III) + 2 H2O + NH3) such as was present on the early Earth could then have produced ammonia. However, this reaction does not proceed at pHs less than 7.3. An alternative is reduction by other forms of Fe(II), such as FeS. We will present results that show that FeS can reduce nitrite to ammonia at pHs as low as pH 5 under a variety of conditions.

Summers, David P.↗
DOE OSTI2026

Optimizing a chemical cleaning protocol to determine the nickel isotopic composition of ancient seawater from carbonates

Reconstructing the ancient marine cycle of Ni, a trace metal in the oceans essential to enzymes regulating the C, N, and O cycles, would inform how Ni bioavailability shaped early life. The Ni isotopic composition of seawater (δ 60 Ni SW ) through time could provide insight, but this approach requires sedimentary archives that faithfully record δ 60 Ni SW . Carbonates are an often-used record of seawater chemistry, but contaminants could bias the measured δ 60 Ni of bulk sediment. To isolate the true carbonate-bound δ 60 Ni signal, we optimized a chemical cleaning protocol designed to minimize non‑carbonate Ni contributions and maximize carbonate recovery. We analyzed ODP Site 1007 sediments and evaluated oxidative and reductive pre-cleaning steps and carbonate dissolution protocols. Our results show that only reductive cleaning significantly altered the subsequent carbonate leachate composition, lowering Ni/Ca ratios by up to 60% and δ 60 Ni values by as much as 0.4 ‰. In contrast, δ 60 Ni values were largely insensitive to premature carbonate dissolution during pre-cleaning or to partial leaching of silicates during carbonate dissolution, even at higher acid molarities or longer reaction times. We recommend an evidence-based protocol that removes hydro-soluble salts and clays, applies reductive cleaning and oxidative cleaning for certain sample compositions, and dissolves carbonate using 0.5 M acetic acid, adjusted to pH 5. Using these results, we infer a ∼ 0.9 ‰ Ni isotopic fractionation between chemically cleaned deep-water carbonates (+0.4 ± 0.1 ‰) and deep seawater. This method development is a key step toward accurately reconstructing ancient marine Ni cycles.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
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.↗