Biologically produced molecular hydrogen (H-2) is characterised by a very strong depletion in deuterium. Although the biological source to the atmosphere is small compared to photochemical or combustion sources, it makes an important contribution to the global isotope budget of H-2. Large uncertainties exist in the quantification of the individual production and degradation processes that contribute to the atmospheric budget, and isotope measurements are a tool to distinguish the contributions from the different sources. Measurements of delta D from the various H-2 sources are scarce and for biologically produced H-2 only very few measurements exist. Here the first systematic study of the isotopic composition of biologically produced H-2 is presented. In a first set of experiments, we investigated delta D of H-2 produced in a biogas plant, covering different treatments of biogas production. In a second set of experiments, we investigated pure cultures of several H-2 producing microorganisms such as bacteria or green algae. A Keeling plot analysis provides a robust overall source signature of delta D = -712 parts per thousand (+/-13 parts per thousand) for the samples from the biogas reactor (at 38 degrees C, delta D-H2O = +73.4 parts per thousand), with a fractionation constant epsilon H-2-H2O of -689 parts per thousand (+/-20 parts per thousand) between H-2 and the water. The five experiments using pure culture samples from different microorganisms give a mean source signature of delta D = -728 parts per thousand (+/-28 parts per thousand), and a fractionation constant epsilon H-2-H2O of -711 parts per thousand (+/-34 parts per thousand) between H-2 and the water. The results confirm the massive deuterium depletion of biologically produced H-2 as was predicted by the calculation of the thermodynamic fractionation factors for hydrogen exchange between H-2 and water vapour. Systematic errors in the isotope scale are difficult to assess in the absence of international standards for delta D of H-2. As expected for a thermodynamic equilibrium, the fractionation factor is temperature dependent, but largely independent of the substrates used and the H-2 production conditions. The equilibrium fractionation coefficient is positively correlated with temperature and we measured a rate of change of 2.3 parts per thousand/degrees C between 45 degrees C and 60 degrees C, which is in general agreement with the theoretical prediction of 1.4%/degrees C. Our best experimental estimate for epsilon H-2-H2O at a temperature of 20 degrees C is -731 parts per thousand (+/-20 parts per thousand) for biologically produced H-2. This value is close to the predicted value of -722 parts per thousand, and we suggest using these values in future global H-2 isotope budget calculations and models with adjusting to regional temperatures for calculating delta D values.
- atmospheric hydrogen
Walter, S., Laukenmann, S., Stams, A. J. M., Vollmer, M. K., Gleixner, G., & Rockmann, T. (2012). The stable isotopic signature of biologically produced molecular hydrogen (H-2). Biogeosciences, 9(10), 4115-4123. https://doi.org/10.5194/bg-9-4115-2012