Carbohydrates in thermophile metabolism: calculation of the standard molal thermodynamic properties of aqueous pentoses and hexoses at elevated temperatures and pressures

Experimental thermodynamic data for aqueous organic compounds can be combined with the revised Helgeson-Kirkham-Flowers (HKF) equations of state to generate parameters that can be used to estimate standard molal properties as functions of temperature and pressure. In this study, we regressed thermodynamic data for aqueous carbohydrates at temperatures up to 393 K reported in the literature to permit the calculation of the apparent standard molal Gibbs free energies and enthalpies of formation (G o and H o , respectively) and the standard molal entropies (S2 ), heat capacities (CP,2 o ), and volumes (V 2 o )t o 423 Ka nd several hundred MPa of aqueous C5 aldoses (ribose, arabinose, xylose, lyxose) and C 5 ketoses (ribulose, xylulose) as well as C6 aldoses (glucose, mannose, galactose) and C6 ketoses (fructose, sorbose). Values of G o for these 11 aqueous carbohydrates are given as a function of temperature at the saturated water vapor pressure (PSAT) and at 50 MPa. Values of G o for aqueous glucose are then combined with those of other aqueous organic and inorganic compounds to calculate values of the standard molal Gibbs free energies of 13 fermentation and respiration reactions (Gr ) known or likely to be carried out by thermophilic microorgan- isms. Finally, values of the overall Gibbs free energies of these reactions (Gr) are calculated at the temperature, pressure, and chemical composition that obtain in the hydrothermal fluids of Vulcano Island, southern Italy, a site that is widely known for its tremendous diversity of organisms able to live at high temperatures. At likely activities of aqueous glucose, it is shown that thermophiles in the hot springs of Vulcano at 373 K and 0.1 MPa can gain between 400 and 3000 kJ per mole of glucose fermented or respired. Copyright © 2001 Elsevier Science Ltd

[1]  A. Hakin,et al.  Group additivity calculations of the thermodynamic properties of unfolded proteins in aqueous solution: a critical comparison of peptide-based and HKF models. , 2001, Biophysical chemistry.

[2]  B. Simoneit,et al.  Hydrocarbons in waters and particulate material from hydrothermal environments at the East Pacific Rise, 13°N , 1988 .

[3]  J. Amend,et al.  Determination of volatile fatty acids in the hot springs of Vulcano, Aeolian Islands, Italy , 1998 .

[4]  D. G. Archer,et al.  The Dielectric Constant of Water and Debye‐Hückel Limiting Law Slopes , 1990 .

[5]  M. B. Pinto,et al.  Optimized δ expansion for relativistic nuclear models , 1997, nucl-th/9709049.

[6]  P. Tremaine,et al.  Amino acids under hydrothermal conditions: Apparent molar heat capacities of aqueous α-Alanine, β-Alanine, glycine, and proline at temperatures from 298 to 500 K and pressures up to 30.0 MPa , 2000 .

[7]  B. Simoneit,et al.  Amino acid abundances and stereochemistry in hydrothermally altered sediments from the Juan de Fuca Ridge, northeastern Pacific Ocean. , 2000, Applied geochemistry : journal of the International Association of Geochemistry and Cosmochemistry.

[8]  J. Deming,et al.  Deep-sea smokers: windows to a subsurface biosphere? , 1993, Geochimica et cosmochimica acta.

[9]  M. Schulte,et al.  Organic synthesis during fluid mixing in hydrothermal systems , 1998 .

[10]  C. M. Criss,et al.  Apparent molar volumes of aqueous solutions of some organic solutes at the pressure 28 MPa and temperatures to 598 K , 1996 .

[11]  G. Goodfriend.  Perspectives in amino acid and protein geochemistry , 2000 .

[12]  J. Amend,et al.  Relative stabilities of biomolecules at high temperatures and pressures , 1994 .

[13]  B. Simoneit,et al.  Survey of hydrothermally-generated petroleums from the Guaymas Basin spreading center , 1987 .

[14]  E. Oelkers,et al.  Calculation of the thermodynamic properties of aqueous species at high pressures and temperatures. Effective electrostatic radii, dissociation constants and standard partial molal properties to 1000 °C and 5 kbar , 1992 .

[15]  J. Amend,et al.  Energetics of amino acid synthesis in hydrothermal ecosystems. , 1998, Science.

[16]  R. Parkes,et al.  Bacterial profiles in hydrothermally active deep sediment layers from Middle Valley (NE Pacific), Sites 857 and 858 , 1994 .

[17]  J. Amend,et al.  Group additivity equations of state for calculating the standard molal thermodynamic properties of aqueous organic species at elevated temperatures and pressures. , 1997 .

[18]  J. C. Ahluwalia,et al.  Partial molar heat capacities and volumes of some mono-, di- and tri-saccharides in water at 298.15, 308.15 and 318.15 K , 1997 .

[19]  H. Helgeson.  Calculation of the thermodynamic properties and relative stabilities of aqueous acetic and chloroacetic acids, acetate and chloroacetates, and acetyl and chloroacetyl chlorides at high and low temperatures and pressures , 1992 .

[20]  K. Miyajima,et al.  Studies on Aqueous Solutions of Saccharides. II. Viscosity B-Coefficients, Apparent Molar Volumes, and Activity Coefficients of D-Glucose, Maltose, and Maltotriose in Aqueous Solutions , 1983 .

[21]  R. Colwell,et al.  Particulate DNA in Smoker Fluids: Evidence for Existence of Microbial Populations in Hot Hydrothermal Systems , 1990, Applied and environmental microbiology.

[22]  W. Zillig,et al.  The Archaebacterium Thermococcus celer Represents, a Novel Genus within the Thermophilic Branch of the Archaebacteria. , 1983, Systematic and applied microbiology.

[23]  Carla M. Koretsky,et al.  Metal-organic complexes in geochemical processes: Estimation of standard partial molal thermodynamic properties of aqueous complexes between metal cations and monovalent organic acid ligands at high pressures and temperatures , 1995 .

[24]  F. Kawaizumi,et al.  Heat-capacity measurements of aqueous solutions of mono-, di-, and tri-saccharides using an isoperibol twin calorimeter , 1981 .

[25]  Everett L. Shock,et al.  Calculation of the thermodynamic and transport properties of aqueous species at high pressures and temperatures: Standard partial molal properties of organic species , 1990 .

[26]  P. Tremaine,et al.  Amino Acids under Hydrothermal Conditions: Apparent Molar Volumes of Aqueous α-Alanine, β-Alanine, and Proline at Temperatures from 298 to 523 K and Pressures up to 20.0 MPa , 1999 .

[27]  Jody W. Deming,et al.  Growth of ‘black smoker’ bacteria at temperatures of at least 250 °C , 1983, Nature.

[28]  Everett L. Shock,et al.  Correlation strategy for determining the parameters of the revised Helgeson-Kirkham-Flowers model for aqueous nonelectrolytes , 2001 .

[29]  T. Yamanaka,et al.  Organic geochemistry of hydrothermal petroleum generated in the submarine Wakamiko caldera, southern Kyushu, Japan , 2000 .

[30]  W. Zillig,et al.  Chemolithoautotrophic metabolism of anaerobic extremely thermophilic archaebacteria , 1983, Nature.

[31]  B. Simoneit,et al.  Hydrothermal pyrolysis of organic matter in Guaymas Basin. I: Comparison of hydrocarbon distributions in subsurface sediments and seabed petroleums , 1994 .

[32]  F. Kawaizumi,et al.  Determination of the Specific Heat Capacities of Aqueous Solutions of Pentose , 1981 .

[33]  B. Simoneit,et al.  Phenols in hydrothermal petroleums and sediment bitumen from Guaymas Basin, Gulf of California. , 1996, Organic geochemistry.

[34]  R. Jasra,et al.  Enthalpies and heat capacities of dissolution, apparent molar heat capacities, and apparent molar volumes of some mono-, di-, tri-, and tetra-saccharides in water , 1984 .

[35]  K. Stetter.  Ultrathin mycelia-forming organisms from submarine volcanic areas having an optimum growth temperature of 105 °C , 1982, Nature.

[36]  Holger W. Jannasch,et al.  Staphylothermus marinus sp. nov. Represents a Novel Genus of Extremely Thermophilic Submarine Heterotrophic Archaebacteria Growing up to 98 °C , 1986 .

[37]  B. Simoneit.  PETROLEUM GENERATION IN SUBMARINE HYDROTHERMAL SYSTEMS: AN UPDATE , 1988 .

[38]  P. Debenedetti.  Supercritical fluids : fundamentals and applications , 1994 .

[39]  K. Kiyosawa.  The Volumes of Hydrated Glucose, Sucrose and Raffinose Molecules, and the Osmotic Pressures of These Aqueous Saccharide Solutions as Measured by the Freezing-Point-Depression Method , 1988 .

[40]  R. Daniel.  Modern Life at High Temperatures , 1992 .

[41]  J. O’Connell.  Thermodynamics and Fluctuation Solution Theory with Some Applications to Systems at Near- or Supercritical Conditions , 1994 .

[42]  P. G. Hill.  A UNIFIED FUNDAMENTAL EQUATION FOR THE THERMODYNAMIC PROPERTIES OF H2O , 1990 .

[43]  R. Jasra,et al.  Enthalpies of solution, partial molal heat capacities and apparent molal volumes of sugars and polyols in water , 1982, Journal of Solution Chemistry.

[44]  Everett L. Shock,et al.  Prediction of the thermodynamic properties of aqueous metal complexes to 1000°C and 5 kb , 1997 .

[45]  Everett L. Shock,et al.  Stability of peptides in high-temperature aqueous solutions , 1992 .

[46]  Everett L. Shock,et al.  Metal-organic complexes in geochemical processes: temperature dependence of the standard thermodynamic properties of aqueous complexes between metal cations and dicarboxylate ligands , 1999 .

[47]  V. Majer,et al.  Volumes and heat capacities of H3BO3(aq) at temperatures from 298.15 K to 705 K and at pressures to 35 MPa , 1995 .

[48]  Eric M. Suuberg,et al.  Vapor Pressures and Enthalpies of Sublimation of d-Glucose, d-Xylose, Cellobiose, and Levoglucosan , 1999 .

[49]  D. Hafenbradl,et al.  Ferroglobus placidus gen. nov., sp. nov., a novel hyperthermophilic archaeum that oxidizes Fe2+ at neutral pH under anoxic conditions , 1996, Archives of Microbiology.

[50]  V. Majer,et al.  Volumes of aqueous solutions of CH4, CO2, H2S and NH3at temperatures from 298.15 K to 705 K and pressures to 35 MPa , 1996 .

[51]  J. Engberts,et al.  INFORMATIVE THERMODYNAMIC PROPERTIES OF THE EFFECT OF STEREOCHEMISTRY ON CARBOHYDRATE HYDRATION , 1993 .

[52]  E. Shock,et al.  Petroleum, oil field waters, and authigenic mineral assemblages Are they in metastable equilibrium in hydrocarbon reservoirs☆ , 1993 .

[53]  E. Shock,et al.  Geochemical constraints on chemolithoautotrophic metabolism by microorganisms in seafloor hydrothermal systems. , 1997, Geochimica et cosmochimica acta.

[54]  F. Millero,et al.  The Apparent Molal Volume and Adiabatic Compressibility of Some Organic Solutes in Water at 25 C , 1978 .

[55]  Everett L. Shock,et al.  Metal-organic complexes in geochemical processes: Calculation of standard partial molal thermodynamic properties of aqueous acetate complexes at high pressures and temperatures , 1993 .

[56]  P. Debenedetti,et al.  Attractive, weakly attractive, and repulsive near‐critical systems , 1989 .

[57]  D. Karl,et al.  Dissolved free amino acids in hydrothermal vent habitats of the Guaymas Basin , 1989 .

[58]  E. Shock,et al.  Organic acids in hydrothermal solutions: standard molal thermodynamic properties of carboxylic acids and estimates of dissociation constants at high temperatures and pressures. , 1995, American journal of science.

[59]  Everett L. Shock,et al.  Halocarbons in the environment: Estimates of thermodynamic properties for aqueous chloroethylene species and their stabilities in natural settings , 1999 .

[60]  B. Simoneit.  Petroleum generation, an easy and widespread process in hydrothermal systems: an overview , 1990 .

[61]  J. Bada,et al.  Submarine hot springs and the origin of life , 1988, Nature.

[62]  E. Oelkers,et al.  SUPCRT92: a software package for calculating the standard molal thermodynamic properties of minerals, gases, aqueous species, and reactions from 1 to 5000 bar and 0 to 1000 ° C , 1992 .

[63]  P. Tremaine,et al.  Excess molar volumes and densities of (methanol+water) at temperatures between 323 K and 573 K and pressures of 7.0 MPa and 13.5 MPa , 1997 .

[64]  J. Morel,et al.  Interactions between cations and sugars. II. Enthalpies, heat capacities, and volumes of aqueous solutions of Ca2+–D-ribose and Ca2+–D-arabinose at 25 °C , 1986 .

[65]  E. M. Woolley,et al.  Apparent molar volumes and apparent molar heat capacities of aqueous D-glucose and D-galactose at temperatures from 278.15 K to 393.15 K and at the pressure 0.35 MPa , 2000 .

[66]  H. Helgeson,et al.  Theoretical prediction of the thermodynamic behavior of aqueous electrolytes at high pressures and temperatures , 1974 .

[67]  H. Helgeson,et al.  Theoretical prediction of the thermodynamic behavior of aqueous electrolytes by high pressures and temperatures; IV, Calculation of activity coefficients, osmotic coefficients, and apparent molal and standard and relative partial molal properties to 600 degrees C and 5kb , 1981 .

[68]  M. Schulte,et al.  Aldehydes in hydrothermal solution: standard partial molal thermodynamic properties and relative stabilities at high temperatures and pressures. , 1993, Geochimica et cosmochimica acta.

[69]  A. Teja,et al.  Krichevskii Parameters and the Solubility of Heavy n-Alkanes in Supercritical Carbon Dioxide , 2000 .

[70]  K. Stetter,et al.  Isolation of Extremely Thermophilic Sulfate Reducers: Evidence for a Novel Branch of Archaebacteria , 1987, Science.

[71]  R. Goldberg,et al.  Apparent molar heat capacities and apparent molar volumes of aqueous glucose at temperatures from 298.15 K to 327.01 K , 1993 .

[72]  Robert N. Goldberg,et al.  Thermodynamic and Transport Properties of Carbohydrates and their Monophosphates: The Pentoses and Hexoses , 1989 .

[73]  H. Uedaira,et al.  Sugar-water interaction from diffusion measurements , 1985 .

[74]  W. Hook,et al.  Apparent molar volumes, isobaric expansion coefficients, and isentropic compressibilities, and their HD isotope effects for some aqueous carbohydrate solutions☆☆☆ , 1986 .

[75]  L. Hnedkovsky,et al.  Apparent molar heat capacitites of aqueous solutions of CH4, CO2, H2S, and NH3at temperatures from 304 K to 704 K at a pressure of 28 MPa , 1997 .

[76]  D. Hafenbradl,et al.  Pyrolobus fumarii, gen. and sp. nov., represents a novel group of archaea, extending the upper temperature limit for life to 113°C , 1997, Extremophiles.

[77]  W. Goodfellow,et al.  Hydrothermal petroleum at the seafloor and organic matter alteration in sediments of Middle Valley, Northern Juan de Fuca Ridge , 1992 .

[78]  Robert H. White.  Hydrolytic stability of biomolecules at high temperatures and its implication for life at 250 °C , 1984, Nature.

[79]  H. Høiland,et al.  Partial molal volumes and compressibilities of carbohydrates in water , 1978 .

[80]  K. Stetter.  Archaeoglobus fulgidus gen. nov., sp. nov.: a new taxon of extremely thermophilic archaebacteria , 1988 .

[81]  J. Amend,et al.  Calculation of the standard molal thermodynamic properties ofaqueous biomolecules at elevated temperatures and pressures Part1L-α-Amino acids , 1997 .

[82]  M. Born.  Volumen und Hydratationswärme der Ionen , 1920 .

[83]  B. Simoneit.  Hydrothermal petroleum: genesis, migration, and deposition in Guaymas Basin, Gulf of California , 1985 .

[84]  J. Amend,et al.  Energetics of overall metabolic reactions of thermophilic and hyperthermophilic Archaea and bacteria. , 2001, FEMS microbiology reviews.

[85]  B. Simoneit,et al.  Polycyclic aromatic hydrocarbons in hydrothermal petroleums from the Guaymas Basin spreading center , 1990 .

[86]  E. Shock,et al.  Estimation of the Krichevskii parameter for aqueous nonelectrolytes , 2001 .

[87]  F. Shahidi,et al.  Partial molar volumes of organic compounds in water. III. Carbohydrates , 1976 .

[88]  Everett L. Shock,et al.  Standard partial molal properties of aqueous alkylphenols at high pressures and temperatures , 1997 .

[89]  Everett L. Shock,et al.  Calculation of the thermodynamic and transport properties of aqueous species at high pressures and temperatures: Correlation algorithms for ionic species and equation of state predictions to 5 kb and 1000°C , 1988 .

[90]  J. Amend,et al.  Calculation of the standard molal thermodynamic properties of aqueous biomolecules at elevated temperatures and pressures II. Unfolded proteins. , 2000, Biophysical chemistry.

[91]  J. Trent,et al.  Possible artefactual basis for apparent bacterial growth at 250 °C , 1984, Nature.

[92]  R. Huber,et al.  The complete genome of the hyperthermophilic bacterium Aquifex aeolicus , 1998, Nature.

[93]  B. Simoneit.  Aqueous high-temperature and high-pressure organic geochemistry of hydrothermal vent systems. , 1993, Geochimica et cosmochimica acta.

[94]  H. Helgeson,et al.  Calculation of the Thermodynamic and Transport Properties of Aqueous Species at High Pressures and Temperatures; Revised Equations of State for the Standard Partial Molal Properties of Ions and Electrolytes , 1988, American Journal of Science.

[95]  B. Simoneit,et al.  High molecular weight polycyclic aromatic hydrocarbons in hydrothermal petroleums from the Gulf of California and Northeast Pacific Ocean. , 1996, Organic geochemistry.

[96]  Derek R. Lovley,et al.  Microbiological evidence for Fe(III) reduction on early Earth , 1998, Nature.

[97]  R. Gagosian,et al.  Suspended particulate organic material from hydrothermal vent waters at 21° N , 1984, Nature.

[98]  D. Reid,et al.  Thermodynamic studies of dilute aqueous solutions of cyclic ethers and simple carbohydrates , 1972 .