The Potential for Abiotic Organic Synthesis and Biosynthesis at Seafloor Hydrothermal Systems

Shock, Everett L.; Canovas, Peter A.

doi:10.1002/9781444394900.ch12

Cited by 34 publications

(46 citation statements)

References 169 publications

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“…The effect of changing activity of hydrogen on the relative stabilities of proteins from M. jannaschii and M. voltae parallels differences in oxidation state of the natural environments of these two organisms. A likely range of activities of dissolved hydrogen in the mixing zones of submarine hydrothermal vents and ocean water, representative of the environments inhabited by M. jannaschii , is to at °C [30]. In lower-temperature estuarine sediments, typical of the growth setting of M. voltae , lower hydrogen concentrations of to have been observed [32].…”

Section: Methodsmentioning

confidence: 99%

“…In many environments, the synthesis of larger molecules, per mole, demands more energy, so for proteins of otherwise equal chemical composition and thermodynamic properties (such as two proteins of different size but with the same relative frequencies of amino acids), the smaller one would generally be thought of as more stable. In more reduced settings, the overall synthesis of organic molecules can actually release energy [30], so the synthesis of larger molecules would be favored. Taking the polymeric nature of the proteins into account, the relative stabilities of proteins of different size can be assessed by first writing formation reactions that are normalized by numbers of amino acid residues.…”

Section: Methodsmentioning

confidence: 99%

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Calculation of the Relative Chemical Stabilities of Proteins as a Function of Temperature and Redox Chemistry in a Hot Spring

Dick

Shock

2011

PLoS ONE

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Uncovering the chemical and physical links between natural environments and microbial communities is becoming increasingly amenable owing to geochemical observations and metagenomic sequencing. At the hot spring known as Bison Pool in Yellowstone National Park, the cooling of the water in the outflow channel is associated with an increase in oxidation potential estimated from multiple field-based measurements. Representative groups of proteins whose sequences were derived from metagenomic data also exhibit an increase in average oxidation state of carbon in the protein molecules with distance from the hot-spring source. The energetic requirements of reactions to form selected proteins used in the model were computed using amino-acid group additivity for the standard molal thermodynamic properties of the proteins, and the relative chemical stabilities of the proteins were investigated by varying temperature, pH and oxidation state, expressed as activity of dissolved hydrogen. The relative stabilities of the proteins were found to track the locations of the sampling sites when the calculations included a function for hydrogen activity that increases with temperature and is higher, or more reducing, than values consistent with measurements of dissolved oxygen, sulfide and oxidation-reduction potential in the field. These findings imply that spatial patterns in the amino acid compositions of proteins can be linked, through energetics of overall chemical reactions representing the formation of the proteins, to the environmental conditions at this hot spring, even if microbial cells maintain considerably different internal conditions. Further applications of the thermodynamic calculations are possible for other natural microbial ecosystems.

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Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Calculation of the Relative Chemical Stabilities of Proteins as a Function of Temperature and Redox Chemistry in a Hot Spring

Dick

Shock

2011

PLoS ONE

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“…Recently it was shown that many conversions between alkanes and alkenes, alkenes and alcohols, and alcohols and ketones are reversible reactions at temperatures and pressures of upper-crustal hydrothermal systems (Yang et al 2012;Shipp et al in press). Abundances of organic compounds in sedimentary basins suggest that, in some cases, metastable equilibrium states also include CO 2 (Shock 1988(Shock , 1989(Shock , 1994Helgeson et al 1993), leading to the hypothesis that abiotic organic synthesis in hydrothermal systems proceeds from CO 2 to organic compounds (Shock 1990(Shock , 1992Shock and Schulte 1998;McCollom and Seewald 2007;Shock and Canovas 2010;McCollom 2013).…”

Section: Kinetic Inhibition Of Ch 4 Formationmentioning

confidence: 99%

The Chemistry of Carbon in Aqueous Fluids at Crustal and Upper-Mantle Conditions: Experimental and Theoretical Constraints

Manning

Shock

Sverjensky

2013

Reviews in Mineralogy and Geochemistry

135

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Carbon in aqueous fluids of crust and mantle Numerous lines of evidence indicate that carbon may be an important component of crustal and mantle fluids. Fluid inclusions provide direct samples of carbon-bearing fluids from a range of environments. Carbon species in fluid inclusions include molecular gas species (CO 2 , CH 4), carbonate ions, and complex organic compounds, including petroleum (Roedder 1984). Carbon-bearing fluid inclusions occur in all crustal metamorphic settings, but they have also been reported in samples derived from mantle depths, including nearly pure CO 2 inclusions in olivine in mantle xenoliths (Roedder 1965; Deines 2002), inclusions in ultrahigh-pressure metamorphic minerals exhumed from mantle depths (Fu et al. 2003b; Frezzotti et al. 2011), and carbon-bearing fluid inclusions in diamonds from depths corresponding to more than 5 GPa (Navon et al. 1988; Schrauder and Navon 1993). The formation of carbon-bearing minerals in fluid-flow features such as veins and segregations are prima facie indications of carbon transport by deep fluids. Environments in which carbonate veins have been observed range from shallow crustal settings to rocks exhumed from subduction zones (Gao et al. 2007) and, rarely, mantle xenoliths (Demeny et al. 2010). Graphite is also widely observed as a vein mineral, most famously perhaps in the Borrowdale graphite deposit of the Lake District in the United Kingdom (e.g., Barrenechea et al. 2009). The occurrence of C-bearing minerals in metamorphic veins is consistent with the observation that the C content of metamorphic rocks decreases with increasing metamorphic grade. For example, pelagic clay lithologies ("pelites") progressively decarbonate during metamorphism: whereas the global average oceanic sediment has 3.01 wt% CO 2 , low-grade metapelites have an average of 2.31 wt% CO 2 , and high-grade metapelites average 0.22 wt% CO 2 (Shaw 1956; Plank and Langmuir 1998). The decarbonation correlates with dehydration, clearly demonstrating that prograde metamorphic reactions liberate a fluid phase containing both H 2 O and carbon as components. Similarly, the development of calc-silicate skarns in carbonate lithologies (Einaudi et al. 1981), in which fluid flow induces replacement of carbonate minerals (chiefly calcite) by silicates and oxides, requires liberation of carbon to water-rich fluids. Finally, spring waters discharging from active metamorphic terranes commonly contain carbon derived from depth (

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“…Hydrothermal vent systems have been discussed as plausible environments for the origin of life by providing templates for macromolecular assembly (Baross and Hoffman, 1985;Shock and Canovas, 2010;Sleep et al, 2011). The disequilibria established by mixing hot, hydrothermal fluids (<350 ºC) with the overlying cold seawater (2 ºC) may drive the formation of some prebiotic molecules (Shock and Schulte, 1998;Shock and Canovas, 2010). A different type of hydrothermal system known as the Lost City hydrothermal field was discovered off the Mid-Ocean Ridge Axis (Kelley et al, 2001).…”

Section: Introductionmentioning

confidence: 99%

Interaction between l-aspartate and the brucite [Mg(OH)2]–water interface

Estrada

Sverjensky

Pelletier

et al. 2015

Geochimica et Cosmochimica Acta

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The interaction of biomolecules at the mineral-water interface could have played a prominent role in the emergence of more complex organic species in life's origins. Serpentinite-hosted hydrothermal vents may have acted as a suitable environment for this process to occur, although little is known about biomolecule-mineral interactions in this system. We used batch adsorption experiments and surface complexation modeling to study the interaction of L-aspartate onto a thermodynamically stable product of serpentinization, brucite [Mg(OH) 2 ], over a wide range of initial aspartate concentrations at four ionic strengths governed by [Mg 2+ ] and [Ca 2+ ]. We observed that up to 1.0 µmol of aspartate adsorbed per m 2 of brucite at pH~10.2 and low Mg 2+ concentrations (0.7x10-3 M), but surface adsorption decreased at high Mg 2+ concentrations (5.8x10-3 M). At high Ca 2+ concentrations (4.0x10-3 M), aspartate surface adsorption doubled (to 2.0 µmol•m-2), with Ca 2+ adsorption at 29.6 µmol•m-2. We used the extended triple-layer model (ETLM) to construct a quantitative thermodynamic model of the adsorption data. We proposed three surface reactions involving the adsorption of aspartate (HAsp-) and/or Ca 2+ onto brucite: 2>SOH + H + + HAsp-= >SOH 2 + >SAsp-+ H 2 O, >SOH + HAsp-+ Ca 2+ = >SO-_Ca(HAsp) + + H + , and >SOH + Ca 2+ + 2H 2 O = >SOH 2 + _ Ca(OH) 2 + H +. We used the ETLM to predict that brucite particle surface charge becomes more negative with increasing [Mg 2+ ], creating an unfavorable electrostatic environment for a negativelycharged aspartate molecule to adsorb. In contrast, our addition of Ca 2+ to the system resulted in Ca 2+ adsorption and development of positive surface charge. Our prediction of surface speciation of aspartate on brucite with Ca 2+ revealed that the calcium-aspartate complex is the predominant surface aspartate species, which suggests that the increase in aspartate adsorption with Ca 2+ is primarily driven by calcium adsorption. The cooperative effect of Ca 2+ and the inhibitive effect of Mg 2+ on aspartate adsorption onto brucite indicate that serpentinite-hosted hydrothermal fluids provide an ideal environment for these interactions to take place.

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The Potential for Abiotic Organic Synthesis and Biosynthesis at Seafloor Hydrothermal Systems

Cited by 34 publications

References 169 publications

Calculation of the Relative Chemical Stabilities of Proteins as a Function of Temperature and Redox Chemistry in a Hot Spring

Calculation of the Relative Chemical Stabilities of Proteins as a Function of Temperature and Redox Chemistry in a Hot Spring

The Chemistry of Carbon in Aqueous Fluids at Crustal and Upper-Mantle Conditions: Experimental and Theoretical Constraints

Interaction between l-aspartate and the brucite [Mg(OH)2]–water interface

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