High-precision determination of ¹³C-¹⁸O bonds in CO₂ using multicollector peak hopping.

Abstract

Rapid development of the CO2 'clumped-isotope' temperature proxy (Δ47 ) has involved both resource- and labor-intensive analytical methods. We report strategies for measuring Δ47 on a conventional mass spectrometer, with the usual CO2 set of three Faraday collectors while reducing the time devoted to standardization with temperature-equilibrated CO2. We measured Δ47 in CO2 on a mass spectrometer using only three Faraday cups by 'multicollector peak hopping', directing (46)CO2(+) and (47)CO2(+) ion beams into the Faraday cups normally used for m/z 44 and 45. Δ47 was calculated from the previously measured δ(13) C and δ(18) O values and we then measured (47)CO2(+)/(46)CO2(+). We invoke a protocol for correcting ion-beam intensities for secondary electrons to address common problems with compositional non-linearity and both long- and short-term measurement stability. Our method eliminates the need for six Faraday cups for measuring Δ47, a possible advantage for many laboratories. In addition, by using a correction based on removing the effects of secondary electrons, we remove the Δ47 dependence on δ(47)CO2. As a result, our methods are robust against mass spectrometer operating conditions. Δ47 can be precisely measured on mass spectrometers currently employed for measuring δ(13) C and δ(18) O values without significant resource investment. Accounting for ion scatter during measurements of CO2 results in improved external precision and long-term stability, while significantly increasing the machine time available for sample analysis.