Isotope Fractionation of Gaseous-, Supercritical-, and Dual-Phase Carbon Dioxide in Pressurized Cylinders Exposed to Variable Temperatures.

Abstract

This work examines the stable isotope fractionation of carbon and oxygen in gaseous, supercritical, and liquid carbon dioxide systems at temperatures from −27.1 to +43.5 °C. For pressurized single-, supercritical-, and dual-phase carbon dioxide, both carbon and oxygen isotope fractionations can be measured and are significant when subjected to variations within this temperature range. The δ13C and δ18O values ranged from −41.55 to −41.38 ‰ (VPDB) and −27.74 to −24.9 ‰ (VPDB), respectively, for gas-phase carbon dioxide from 9.3 to 39 °C. A pressure variation of 27.58 barg to 34.48 barg was measured throughout this temperature range. In order to evaluate the effect of supercritical formation and liquefaction on the stable isotope values, cylinders were filled to varying pressures. When stored at cold temperatures, the δ13C value as measured in the headspace of the liquid phase varied from −41.23 to −41.13 ‰ (VPDB) and −41.50 to −41.44 ‰ (VPDB) in the supercritical phase. The δ18O value was between −25.51 and −25.36 ‰ (VPDB) in the liquid phase and between −24.79 and −24.77 ‰ (VPDB) in the supercritical phase. Temperatures in these experiments were selected to mimic outdoor conditions (winter and summer) that stable isotope laboratory practitioners may encounter when storing compressed carbon dioxide cylinders containing stable isotope working reference gases. The carbon and oxygen isotope composition of carbon dioxide gas within these pressurized cylinders return to their precooled isotope values within ∼24 h when warmed to laboratory temperatures (∼24 °C). A headspace analysis performed immediately after the carbon dioxide cylinder was removed from the cold environment yielded δ13C values that were relatively enriched, while δ18O values were relatively depleted. This is likely an effect of 12C and 18O being preferentially partitioned in the liquid phase within the cylinder. As the cylinder warmed, both liquid and gas equilibrated, and carbon and oxygen homogenized isotopically. As the cylinder was heated into the supercritical phase, a slight opposite isotope effect at higher pressure and temperatures was noted. That is, a slight 13C depletion and 18O enrichment were observed in the gas phase. However, these isotope variations were just slightly outside of the analytical error. Additionally, a separate gas-phase carbon dioxide cylinder was kept at a constant laboratory temperature as a control. This carbon dioxide showed no measurable carbon or oxygen isotope variation throughout the duration of the experimental work. The measured isotope fractionation was significantly higher comparing the phase transition from the gaseous to liquid phase versus the gaseous phase to supercritical phase. The proper handling of pressurized carbon dioxide cylinders used as reference gases for an isotope ratio mass spectrometer includes using carbon dioxide at pressures of less than ∼34.88 barg to ensure that the gas is present as a single phase, storing the gas in a temperature-controlled environment, and allowing the gaseous carbon dioxide to equilibrate to ambient conditions for 24–48 h if storage in a controlled ambient environment is not feasible.