A Novel Tandem of Thermal Desorption Carbon Analyzer and Off-Axis Integrated Cavity Output Spectroscopy for Aerosol Stable Carbon Isotope Ratio Measurement

A novel approach for measurement of stable carbon isotopic ratio of atmospheric aerosols was developed by tandem operation of two instruments: a Sunset Organic Carbon-Elemental Carbon (OC-EC) analyzer and an online Carbon Dioxide Stable Isotope Analyzer (LGR, CCIA-36d). Sensitivity, accuracy and measurement uncertainty of the CCIA was comprehensively investigated using the standard reference CO_2 gas with known concentration and isotopic ratio. Drift in CCIA measurement due to varying CO_2 and water vapor concentration was evaluated and a humidity stabilizer was designed and developed to control the water vapor concentration of exhaust gas flow from OC-EC prior to entering the CCIA. A Keeling approach was applied to separate the ratio in the samples from the mixture of PM sample-produced CO_2 and reference gas and we developed a protocol to derive the isotopic composition of the particle samples. A lithium carbonate standard (in powder form) from National Institute of Standards and Technology (NIST) was used to validate measurement of δ^(13)C ratios by CCIA. Offline measurement on ambient aerosol and diesel exhaust aerosols produced comparable results of isotopic ratio with literature values. This study demonstrates the utility of this tandem operation for carbon isotopic measurement of atmospheric particles with better than 1.0 per mille precision as a cost-effective alternative of conventional Isotopic Ratio Mass Spectrometer (IR-MS).