The effect of temperature on the rate, affinity, and 15N fractionation of NO3 − during biological denitrification in soils

Verfasser / Beitragende:
[Federico Maggi, William Riley]
Ort, Verlag, Jahr:
2015
Enthalten in:
Biogeochemistry, 124/1-3(2015-05-01), 235-253
Format:
Artikel (online)
ID: 605516715
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024 7 0 |a 10.1007/s10533-015-0095-2  |2 doi 
035 |a (NATIONALLICENCE)springer-10.1007/s10533-015-0095-2 
245 0 4 |a The effect of temperature on the rate, affinity, and 15N fractionation of NO3 − during biological denitrification in soils  |h [Elektronische Daten]  |c [Federico Maggi, William Riley] 
520 3 |a Nine independent experiments of NO3 − denitrification were analysed using the Arrhenius law and the Eyring's transition-state theory to highlight how temperature affects reaction rate constants, affinities, and kinetic isotopic effects. For temperatures between 20 and 35°C, the Arrhenius law and the transition-state theory described equally well observed temperature increases in 14NO3 − and 15NO3 −denitrification rates (R>0.99 and residuals NRMSE<3.39%, p<0.01). These increases were partly caused by an increase in frequency factor and a slight decrease in activation energy (enthalpy and entropy). Parametric analysis also showed that the affinity of 14NO3 − and 15NO3 − toward a microbial enzyme increased exponentially with temperature and a strong correlation with the rate constants was found (R=0.93, p<0.01). Experimental time- and temperature-averaged fractionation factor α P/S showed only a slight increase with increasing temperature (i.e. lower isotopic effects); however, a comprehensive sensitivity analysis in the concentration-temperature domain using average thermodynamic quantities estimated here showed a more complex response; α P/S was relatively constant for initial bulk concentrations [NO3 −]0≤0.01molkg−1, while substantial nonlinearities developed for [NO3 −]0≥0.01molkg−1 and appeared to be strongly correlated with microbial biomass, whose concentration and activity varied primarily as a function of temperature and available substrate. Values of α P/S ranging between 0.9 and 0.98 for the tested temperatures suggested that interpretations of environmental isotopic signatures should include a sensitivity analysis to the temperature as this affects directly the rate constants and affinities in biochemical reactions and may hide process- and source-related isotopic effects. 
540 |a Springer International Publishing Switzerland, 2015 
690 7 |a Denitrification  |2 nationallicence 
690 7 |a 14N and 15N  |2 nationallicence 
690 7 |a Kinetic isotopic effects  |2 nationallicence 
690 7 |a Affinity  |2 nationallicence 
690 7 |a Temperature  |2 nationallicence 
690 7 |a Arrhenius  |2 nationallicence 
690 7 |a Transition-state theory  |2 nationallicence 
690 7 |a α : Fractionation factor (-)  |2 nationallicence 
690 7 |a δ : Isotopic composition (-)  |2 nationallicence 
690 7 |a x, y : Stoichiometric coefficients (-)  |2 nationallicence 
690 7 |a G : Gibbs free energy (Jmol−1)  |2 nationallicence 
690 7 |a h : Planck constant (Js)  |2 nationallicence 
690 7 |a H : Heat content (Jmol−1)  |2 nationallicence 
690 7 |a k : Reaction rate constant (Τ−1)  |2 nationallicence 
690 7 |a K b : Boltzmann constant (JK−1 mol−1)  |2 nationallicence 
690 7 |a K : Affinity (half-saturation concentration) (M)  |2 nationallicence 
690 7 |a S : Entropy content (JK−1 mol−1)  |2 nationallicence 
690 7 |a t : Time (T)  |2 nationallicence 
690 7 |a T : Absolute temperature (K)  |2 nationallicence 
690 7 |a NRMSE : Normalized root mean square error (-)  |2 nationallicence 
690 7 |a R : Correlation coefficient (-)  |2 nationallicence 
700 1 |a Maggi  |D Federico  |u Laboratory for Advanced Environmental Engineering Research, School of Civil Engineering, The University of Sydney, 2006, Sydney, NSW, Australia  |4 aut 
700 1 |a Riley  |D William  |u Earth Systems Division, Climate and Carbon Department, Lawrence Berkeley National Laboratory, 94720, Berkeley, CA, USA  |4 aut 
773 0 |t Biogeochemistry  |d Springer International Publishing  |g 124/1-3(2015-05-01), 235-253  |x 0168-2563  |q 124:1-3<235  |1 2015  |2 124  |o 10533 
856 4 0 |u https://doi.org/10.1007/s10533-015-0095-2  |q text/html  |z Onlinezugriff via DOI 
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900 7 |a Metadata rights reserved  |b Springer special CC-BY-NC licence  |2 nationallicence 
908 |D 1  |a research-article  |2 jats 
949 |B NATIONALLICENCE  |F NATIONALLICENCE  |b NL-springer 
950 |B NATIONALLICENCE  |P 856  |E 40  |u https://doi.org/10.1007/s10533-015-0095-2  |q text/html  |z Onlinezugriff via DOI 
950 |B NATIONALLICENCE  |P 700  |E 1-  |a Maggi  |D Federico  |u Laboratory for Advanced Environmental Engineering Research, School of Civil Engineering, The University of Sydney, 2006, Sydney, NSW, Australia  |4 aut 
950 |B NATIONALLICENCE  |P 700  |E 1-  |a Riley  |D William  |u Earth Systems Division, Climate and Carbon Department, Lawrence Berkeley National Laboratory, 94720, Berkeley, CA, USA  |4 aut 
950 |B NATIONALLICENCE  |P 773  |E 0-  |t Biogeochemistry  |d Springer International Publishing  |g 124/1-3(2015-05-01), 235-253  |x 0168-2563  |q 124:1-3<235  |1 2015  |2 124  |o 10533