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Biologically produced molecular hydrogen (H2) 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 H2. 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 δD from the various H2 sources are scarce and for biologically produced H2 only very few measurements exist. Here the first systematic study of the isotopic composition of biologically produced H2 is presented. In a first set of experiments, we investigated δD of H2 produced in a biogas plant, covering different treatments of biogas production. In a second set of experiments, we investigated pure cultures of several H2 producing microorganisms such as bacteria or green algae. A Keeling plot analysis provides a robust overall source signature of δD = -712‰ (±13 ‰) for the samples from the biogas reactor (at 38 δC, δDH2O = +73.4 ‰), with a fractionation constant εH2-H2O of -689‰ (±20 ‰) between H2 and the water. The five experiments using pure culture samples from different microorganisms give a mean source signature of δD = -728‰ (±28 ‰), and a fractionation constant εH2-H2O of -711‰(±34 ‰) between H2 and the water. The results confirm the massive deuterium depletion of biologically produced H2 as was predicted by the calculation of the thermodynamic fractionation factors for hydrogen exchange between H2 and water vapour. Systematic errors in the isotope scale are difficult to assess in the absence of international standards for δD of H2. As expected for a thermodynamic equilibrium, the fractionation factor is temperature dependent, but largely independent of the substrates used and the H2 production conditions. The equilibrium fractionation coefficient is positively correlated with temperature and we measured a rate of change of 2.3‰/ δC between 45 δC and 60 δC, which is in general agreement with the theoretical prediction of 1.4‰/ δC. Our best experimental estimate for εH2-H2O at a temperature of 20 δC is -731‰ (±20 ‰) for biologically produced H2. This value is close to the predicted value of -722 ‰, and we suggest using these values in future global H2 isotope budget calculations and models with adjusting to regional temperatures for calculating δD values. [ABSTRACT FROM AUTHOR]

Biologically produced molecular hydrogen (H2) is characterized 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 molecular hydrogen (H2). 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 δD from the various H2 sources are scarce and for biologically produced H2 only very few measurements exist. Here the first systematic study of the isotopic composition of biologically produced H2 is presented. We investigated δD of H2 produced in a biogas plant, covering different treatments of biogas production, and from several H2 producing microorganisms such as bacteria or green algae. A Keeling plot analysis provides a robust overall source sig15 nature of δD = -712‰ (±13 ‰) for the samples from the biogas reactor (at 38 °C, Due to image rights restrictions, multiple line equation(s) cannot be graphically displayed = 73.4 ‰), with a fractionation constant Due to image rights restrictions, multiple line equation(s) cannot be graphically displayed of -689‰ (±20 ‰). The pure culture samples from different microorganisms give a mean source signature of δD =-728‰ (± 39 ‰), and a fractionation constant Due to image rights restrictions, multiple line equation(s) cannot be graphically displayed -711‰ (± 45 ‰) between H2 and the water, respectively. The results confirm the massive deuterium depletion of biologically produced H2 as was predicted by calculation of the thermodynamic fractionation factors for hydrogen exchange between H2 and water vapor. As expected for a thermodynamic equilibrium, the fractionation factor is largely independent of the substrates used and the H2 production conditions. The predicted equilibrium fractionation coefficient is positively correlated with temperature and we measured a change of 2.2 ‰/°C between 45 °C and 60 °C. This is in general agreement with the theoretical predictions. [ABSTRACT FROM AUTHOR]

Between 2008 and 2010 various batch experiments were carried out to study the stable carbon isotopic composition of biogas (CH4 and CO2) produced from (i) pure sludge and (ii) sludge including maize. From the evolution of the natural isotopic signature, a temporal change of methanogenic pathways could be detected for the treatment with maize showing that a dominance in acetotrophic methanogenesis was replaced by a mixture of hydrogenotrophic and acetotrophic methanogenesis. For pure sludge, hydrogenotrophic methanogenesis was the dominant or probably exclusive pathway. Experiments with isotopically labelled acetate (99% (13)CH3COONa and 99% CH3(13)COONa) indicated a significant contribution of syntrophic acetate oxidation (SAO) for all the investigated treatments. In the case of pure sludge, experiments from 2008 showed that acetate was almost entirely oxidised to CO2, i.e. acetotrophic methanogenesis was negligible. However, in 2010, the sludge showed a clear dominance in acetotrophic methanogenesis with a minor contribution by SAO indicating a significant change in the metabolic character. Our results indicate that SAO during anaerobic degradation of maize might be a significant process that needs to be considered in biogas research.

Methane production by anaerobic digestion of biomass has recently become more attractive because of its potential for renewable energy production. Analytical tools are needed to study and optimize the ongoing processes in biogas reactors. It is considered that optical methods providing continuous measurements at high temporal resolution of carbon isotope ratios of methane (delta(13)C(CH4)) might be of great help for this purpose. In this study we have tested near-infrared laser optical spectrometry and compared it with conventional continuous-flow isotope ratio mass spectrometry (CF-IRMS) using several methane carbon isotope standards and a large number of biogas samples from batch anaerobic reactors. Results from measurements on these samples were used to determine and compare the precision of the two techniques and to quantify for systematic offsets. With pure standards analytical precision of measurements for delta(13)C(CH4) was found to be in the range of 0.33 and 0.48 per thousand, and 0.09 and 0.27 per thousand for the optical method and CF-IRMS, respectively. Biogas samples showed an average mean deviation of delta(13)C(CH4) of 0.38 per thousand and 0.08 per thousand for the optical method and CF-IRMS, respectively. Although the tested laser optical spectrometer showed a dependence of delta(13)C(CH4) on CH(4) mixing ratio in the range of 500 to 8000 ppm this could be easily corrected. After correction, the delta(13)C(CH4) values usually varied within 0.7 per thousand from those measured by conventional CF-IRMS and thus results from both methods agreed within the given analytical uncertainties. Although the precision of the conventional CF-IRMS is higher than the tested optical system, both instruments were well within the acceptable delta(13)C(CH4) precision required for biogas methane measurements. The advantages of the optical system are its simplicity of operation, speed of analysis, good precision, reduced costs in comparison to IRMS, and the potential for field applications.