Measurements of 13C/12C methane from anaerobic digesters: comparison of optical spectrometry with continuous-flow isotope ratio mass spectrometry.

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.