Identification of Anthropogenic CO₂ Using Triple Oxygen and Clumped Isotopes

Quantification of contributions from various sources of CO₂ is important for understanding the atmospheric CO₂ budget. Considering the number and diversity of sources and sinks, the widely used proxies such as concentration and conventional isotopic compositions (δ¹³C and δ¹⁸O) are not always sufficient to fully constrain the CO₂ budget. Additional constraints may help in understanding the mechanisms of CO₂ production and consumption. The anomaly in triple oxygen isotopes or ¹⁷O excess (denoted by Δ¹⁷O) and molecules containing two rare isotopes, called clumped isotopes, are two recently developed tracers with potentials to independently constrain some important processes that regulate CO₂ in the atmosphere. The clumped isotope for CO₂, denoted by Δ₄₇, is the excess of ¹³C¹⁶O¹⁸O over a random distribution of isotopes in a CO₂ molecule. We measured the concentrations of δ¹³C, δ¹⁸O, Δ¹⁷O, and Δ₄₇ in air CO₂ samples collected from the Hsuehshan tunnel (length: 12.9 km), and applied linear and polynomial regressions to obtain the fossil fuel end-members for all these isotope proxies. The other end-members, the values of all these proxies for background air CO₂, are either assumed or taken as the values obtained over the tunnel and ocean. The fossil fuel (anthropogenic) CO₂ end-member values for δ¹³C, δ¹⁸O, Δ¹⁷O, and Δ₄₇ are estimated using the two component mixing approach: the derived values are -26.76 ± 0.25‰, 24.57 ± 0.33‰, -0.219 ± 0.021‰, and 0.267 ± 0.036‰, respectively. These four major CO₂ isotope tracers along with the concentration were used to estimate the anthropogenic contribution in the atmospheric CO₂ in urban and suburban locations. We demonstrate that Δ¹⁷O and Δ₄₇ have the potential to independently estimate anthropogenic contribution, and the advantages of these two over the conventional isotope proxies are discussed.