Methane Clumped Isotopes: Progress and Potential for a New Isotopic Tracer

The isotopic composition of methane is of longstanding geochemical interest, with important implications for understanding petroleum systems, atmospheric greenhouse gas concentrations, the global carbon cycle, and life in extreme environments. Recent analytical developments focusing on multiply substituted isotopologues (‘clumped isotopes’) are opening a valuable new window into methane geochemistry. When methane forms in internal isotopic equilibrium, clumped isotopes can provide a direct record of formation temperature, making this property particularly valuable for identifying different methane origins. However, it has also become clear that in certain settings methane clumped isotope measurements record kinetic rather than equilibrium isotope effects. Here we present a substantially expanded dataset of methane clumped isotope analyses, and provide a synthesis of the current interpretive framework for this parameter. In general, clumped isotope measurements indicate plausible formation temperatures for abiotic, thermogenic, and microbial methane in many geological environments, which is encouraging for the further development of this measurement as a geothermometer, and as a tracer for the source of natural gas reservoirs and emissions. We also highlight, however, instances where clumped isotope derived temperatures are higher than expected, and discuss possible factors that could distort equilibrium formation temperature signals. In microbial methane from freshwater ecosystems, in particular, clumped isotope values appear to be controlled by kinetic effects, and may ultimately be useful to study methanogen metabolism

Recovery of Odorants from an Olfactometer Measured by Proton-Transfer-Reaction Mass Spectrometry

The aim of the present study was to examine the recovery of odorants during the dilution in an olfactometer designed according to the European standard for dynamic olfactometry. Nine odorants in the ppmv-range were examined including hydrogen sulfide, methanethiol, dimethyl sulfide, acetic acid, propanoic acid, butanoic acid, trimethylamine, 3-methylphenol and n-butanol. Each odorant was diluted in six dilution steps in descending order from 4,096 to 128 times dilutions. The final recovery of dimethyl sulfide and n-butanol after a 60-second pulse was only slightly affected by the dilution, whereas the recoveries of the other odorants were significantly affected by the dilution. The final recoveries of carboxylic acids, trimethylamine and 3-methylphenol were affected by the pulse duration and the signals did not reach stable levels within the 60-second pulse, while sulfur compounds and n-butanol reach a stable signal within a few seconds. In conclusion, the dilution of odorants in an olfactometer has a high impact on the recovery of odorants and when olfactometry is used to estimate the odor concentration, the recoveries have to be taken into consideration for correct measurements

Key Odorants from Pig Production Based on Improved Measurements of Odor Threshold Values Combining Olfactometry and Proton-Transfer-Reaction Mass Spectrometry (PTR-MS)

Analytical measurements of odorants in combination with odor threshold values is an alternative to sensory measurements that can be used to evaluate abatement technologies for pig production facilities. The purpose of the present study was to estimate odor threshold values for key odorants found in pig house air. A new method was applied where an olfactometer was used to dilute the sample air and the concentrations of odorants presented to the panelists at the dilutions steps were measured by proton-transfer-reaction mass spectrometry (PTR-MS). The results demonstrate that the odor threshold values of acetic acid, butanoic acid, and 4-methylphenol are considerably lower than reported previously, whereas the values of hydrogen sulfide, methanethiol and dimethylsulfide were comparable. Consequently, acetic acid, butanoic acid, and 4-methyl-phenol will have a larger influence on odor from pig production facilities than previously assumed. The results highlight the necessity for directly measuring exposure concentrations when determining odor threshold values

Recovery of Odorants from an Olfactometer Measured by Proton-Transfer-Reaction Mass Spectrometry

The aim of the present study was to examine the recovery of odorants during the dilution in an olfactometer designed according to the European standard for dynamic olfactometry. Nine odorants in the ppmv-range were examined including hydrogen sulfide, methanethiol, dimethyl sulfide, acetic acid, propanoic acid, butanoic acid, trimethylamine, 3-methylphenol and n-butanol. Each odorant was diluted in six dilution steps in descending order from 4,096 to 128 times dilutions. The final recovery of dimethyl sulfide and n-butanol after a 60-second pulse was only slightly affected by the dilution, whereas the recoveries of the other odorants were significantly affected by the dilution. The final recoveries of carboxylic acids, trimethylamine and 3-methylphenol were affected by the pulse duration and the signals did not reach stable levels within the 60-second pulse, while sulfur compounds and n-butanol reach a stable signal within a few seconds. In conclusion, the dilution of odorants in an olfactometer has a high impact on the recovery of odorants and when olfactometry is used to estimate the odor concentration, the recoveries have to be taken into consideration for correct measurements

Key Odorants from Pig Production Based on Improved Measurements of Odor Threshold Values Combining Olfactometry and Proton-Transfer-Reaction Mass Spectrometry (PTR-MS)

Analytical measurements of odorants in combination with odor threshold values is an alternative to sensory measurements that can be used to evaluate abatement technologies for pig production facilities. The purpose of the present study was to estimate odor threshold values for key odorants found in pig house air. A new method was applied where an olfactometer was used to dilute the sample air and the concentrations of odorants presented to the panelists at the dilutions steps were measured by proton-transfer-reaction mass spectrometry (PTR-MS). The results demonstrate that the odor threshold values of acetic acid, butanoic acid, and 4-methylphenol are considerably lower than reported previously, whereas the values of hydrogen sulfide, methanethiol and dimethylsulfide were comparable. Consequently, acetic acid, butanoic acid, and 4-methyl-phenol will have a larger influence on odor from pig production facilities than previously assumed. The results highlight the necessity for directly measuring exposure concentrations when determining odor threshold values