Thermodynamic driving force of hydrogen on rumen microbial metabolism

Hydrogen is a key product of rumen fermentation and has been suggested to thermodynamically control the production of the various volatile fatty acids (VFA). Previous studies, however, have not accounted for the fact that only thermodynamic near-equilibrium conditions control the magnitude of reaction rate. Furthermore, the role of NAD, which is affected by hydrogen partial pressure (P H 2 ), has often not been considered. The aim of this study was to quantify the control of P H 2 on reaction rates of specific fermentation pathways, methanogenesis and NADH oxidation in rumen microbes. The control of P H 2 was quantified using the thermodynamic potential factor (FT), which is a dimensionless factor that corrects a predicted kinetic reaction rate for the thermodynamic control exerted. Unity FT was calculated for all glucose fermentation pathways considered, indicating no inhibition of P H 2 on the production of a specific type of VFA (e.g., acetate, propionate and butyrate) in the rumen. For NADH oxidation without ferredoxin oxidation, increasing P H 2 within the rumen physiological range decreased FT from unity to zero for different NAD + to NADH ratios and pH of 6.2 and 7.0, which indicates thermodynamic control of P H 2 . For NADH oxidation with ferredoxin oxidation, increasing P H 2 within the rumen physiological range decreased FT from unity at pH of 7.0 only. For the acetate to propionate conversion, FT increased from 0.65 to unity with increasing P H 2 , which indicates thermodynamic control. For propionate to acetate and butyrate to acetate conversions, FT decreased to zero below the rumen range of P H 2 , indicating full thermodynamic suppression. For methanogenesis by archaea without cytochromes, FT differed from unity only below the rumen range of P H 2 , indicating no thermodynamic control. This theoretical investigation shows that thermodynamic control of P H 2 on individual VFA produced and associated yield of hydrogen and methane cannot be explained without considering NADH oxidation.