title: Non-linear dynamics of stable carbon and hydrogen isotope signatures based on a biological kinetic model of aerobic enzymatic methane oxidation.
abstract: The non-linear dynamics of stable carbon and hydrogen isotope signatures during methane oxidation by the methanotrophic bacteria Methylosinus sporium strain 5 (NCIMB 11126) and Methylocaldum gracile strain 14 L (NCIMB 11912) under copper-rich (8.9 µM Cu(2+)), copper-limited (0.3 µM Cu(2+)) or copper-regular (1.1 µM Cu(2+)) conditions has been described mathematically. The model was calibrated by experimental data of methane quantities and carbon and hydrogen isotope signatures of methane measured previously in laboratory microcosms reported by Feisthauer et al. [ 1 ] M. gracile initially oxidizes methane by a particulate methane monooxygenase and assimilates formaldehyde via the ribulose monophosphate pathway, whereas M. sporium expresses a soluble methane monooxygenase under copper-limited conditions and uses the serine pathway for carbon assimilation. The model shows that during methane solubilization dominant carbon and hydrogen isotope fractionation occurs. An increase of biomass due to growth of methanotrophs causes an increase of particulate or soluble monooxygenase that, in turn, decreases soluble methane concentration intensifying methane solubilization. The specific maximum rate of methane oxidation υm was proved to be equal to 4.0 and 1.3 mM mM(-1) h(-1) for M. sporium under copper-rich and copper-limited conditions, respectively, and 0.5 mM mM(-1) h(-1) for M. gracile. The model shows that methane oxidation cannot be described by traditional first-order kinetics. The kinetic isotope fractionation ceases when methane concentrations decrease close to the threshold value. Applicability of the non-linear model was confirmed by dynamics of carbon isotope signature for carbon dioxide that was depleted and later enriched in (13)C. Contrasting to the common Rayleigh linear graph, the dynamic curves allow identifying inappropriate isotope data due to inaccurate substrate concentration analyses. The non-linear model pretty adequately described experimental data presented in the two-dimensional plot of hydrogen versus carbon stable isotope signatures.
authors.affiliation: a Russian Academy of Sciences , Ecological Department of Water Problems Institute , Moscow , Russian Federation.
authors.forename: Vasily A
authors.initials: VA
authors.lastname: Vavilin
authors.affiliation: a Russian Academy of Sciences , Ecological Department of Water Problems Institute , Moscow , Russian Federation.
authors.forename: Sergey V
authors.initials: SV
authors.lastname: Rytov
authors.affiliation: a Russian Academy of Sciences , Ecological Department of Water Problems Institute , Moscow , Russian Federation.|b College of Engineering , University of Georgia , Athens , GA , USA.
authors.forename: Natalia
authors.initials: N
authors.lastname: Shim
authors.affiliation: c Department of Isotope Biogeochemistry , Helmholtz Center for Environmental Research - UFZ , Leipzig , Germany.
authors.forename: Carsten
authors.initials: C
authors.lastname: Vogt
mesh_terms: D000332:Aerobiosis; D002247:Carbon Isotopes; D003300:Copper / Q000378:metabolism; D003903:Deuterium; D007700:Kinetics; D008697:Methane / Q000378:metabolism*; D008772:Methylococcaceae / Q000201:enzymology / Q000378:metabolism*; D020581:Methylosinus / Q000201:enzymology / Q000378:metabolism*; D008954:Models, Biological; D017711:Nonlinear Dynamics; D010084:Oxidation-Reduction; D010105:Oxygenases / Q000378:metabolism*
chemical_list: D002247:Carbon Isotopes; D003300:Copper; D003903:Deuterium; D010105:Oxygenases; C021555:methane monooxygenase; D008697:Methane
keywords: carbon-13; copper; hydrogen-2; isotope ecology; isotope effects; isotope fractionation; theory