Scientific References

Peer Reviewed Literature: H2S interference on CO2 isotopic measurements using a Picarro G1101-i cavity ring-down spectrometer

Presented at
Atmospheric Measurement Techniques Discussions, vol. 8, p. 5651-5675, doi:10.5194/amtd-8-5651-2015, 2015

Abstract

Cavity ring-down spectrometers (CRDS) have the capacity to make isotopic measurements of CO2 where concentrations range from atmospheric (~ 400 ppm) to 6000 ppm. Following field trials, it has come to light that the spectrographic lines used for CO2 have an interference with elevated (higher than ambient) amounts of hydrogen sulfide (H2S), which causes significant depletions in the δ13C measurement by the CRDS. In order to deploy this instrument in environments with elevated H2S concentrations (i.e., active volcanoes), we require a robust method for eliminating this interference. Controlled experiments using a Picarro G1101-i optical spectrometer were done to characterize the H2S interference at varying CO2 and H2S concentrations. The addition of H2S to a CO2 standard gas reveals an increase in the 12CO2 concentration and a more significant decrease in the 13CO2 concentration, resulting in a depleted δ13C value. Reacting gas samples containing H2S with copper prior to analysis can eliminate this effect. However, experiments also revealed that the addition of H2S to CO2 results in the formation of carbonyl sulfide (OCS) and carbon disulfide (CS2), causing a decrease in the overall CO2 concentration without affecting the δ13C value. It is important for future work with CRDS, particularly in volcanic regions where H2S is abundant, to be aware of the H2S interference on the CO2 spectroscopic lines and to remove all H2S prior to analysis. We suggest employing a scrub composed of copper to remove H2S from all gas samples that have concentrations in excess of 1 ppb.