Acetate and other Volatile Fatty Acids – Key Intermediates in marine sediment metabolism - Thermodynamic and kinetic implications

Abstract:

Volatile fatty acids (VFAs) play important roles as key intermediates in the anaerobic metabolism of subsurface microbial communities. Usually they are present in marine sediment pore water in low concentrations as a result of balanced production and consumption, both occurring in the same sediment zone. Thus their low concentrations represent a steady state condition regulated by either thermodynamics or kinetics. We have developed a novel analytical approach for the parallel measurement of several VFAs directly from marine pore water without any sample pretreatment by the use of a 2-dimensional ion chromatography coupled to mass spectrometry. In a first study we analyzed acetate, formate, and propionate in pore water from sediment cores retrieved from 5 different stations within and offshore of the Godhåbsfjord (Greenland). The sediment cores represent different sedimentological conditions, ranging from a typical marine sedimentation site to a glacier/freshwater dominated site. In addition to VFA concentrations, we measured sulfate concentrations, sulfate reduction rates, and cell abundances. We calculated the Gibbs free energy (ΔG) available for sulfate reduction (SR), as well as the VFA turnover times by the in-situ SR rates. The turnover time for acetate by SR ranged from several hours to days in the top cm of sediment and increased to several hundred years at the bottom of the SR zone. From the associated cell abundances we calculated that the VFA turnover times were significantly longer than the diffusion times of the VFA between individual cells. This shows that VFA consumption in the SR zone, and concomitantly the observed pore water concentrations, are not constrained by diffusion. DG values for SR using acetate were >36 kJ/mol which is significantly above the lower limit for anaerobic microbial energy metabolism. It thus remains unclear what controls the VFA concentrations in the sediment.