A new approach for measuring the carbon and oxygen content of atmospherically relevant compounds and mixtures

• Main Authors: J. F. Hurley, N. M. Kreisberg, B. Stump, C. Bi, P. Kumar, S. V. Hering, P. Keady, G. Isaacman-VanWertz
• Format: Article
• Language: English
• Published: Copernicus Publications 2020-09-01
• Series: Atmospheric Measurement Techniques
• Online Access: https://amt.copernicus.org/articles/13/4911/2020/amt-13-4911-2020.pdf

<p>Due to its complexity, gas- and particle-phase organic carbon in the atmosphere is often classified by its bulk physicochemical properties. However, there is a dearth of robust, moderate-cost approaches to measure the bulk chemical composition of organic carbon in the atmosphere. This is particularly true for the degree of oxygenation, which critically affects the properties and impacts of organic carbon but for which routine measurement approaches are lacking. This gap has limited the understanding of a wide range of atmospheric components, including particulate matter, the mass of which is monitored worldwide due to its health and environmental effects but the chemical characterization of which requires relatively high capital costs and complex operation by highly trained technical personnel. In this work, we demonstrate a new approach to estimate the mass of carbon and oxygen in analytes and mixtures that relies only on robust, moderate-cost detectors designed for use with gas chromatography. Organic compounds entering a flame ionization detector were found to be converted with approximately complete efficiency to <span class="inline-formula">CO₂</span>, which was analyzed downstream using an infrared detector to measure the mass of carbon analyzed. The ratio of the flame ionization detector (FID) signal generated to <span class="inline-formula">CO₂</span> formed (<span class="inline-formula">FID∕CO₂</span>) was shown to be strongly correlated (<span class="inline-formula"><i>R</i>²=0.89</span>) to the oxygen-to-carbon ratio (<span class="inline-formula">O∕C</span>) of the analyte. Furthermore, simple mixtures of analytes behaved as the weighted average of their components, indicating that this correlation extends to mixtures. These properties were also observed to correlate well with the sensitivity of the FID estimated by structure activity relationships (quantified as the relative effective carbon number). The relationships between measured <span class="inline-formula">FID∕CO₂</span>, analyte <span class="inline-formula">O∕C</span>, and FID sensitivity allow the estimation of one property from another with <span class="inline-formula">&lt;15</span>&thinsp;% error for mixtures and <span class="inline-formula">&lt;20</span>&thinsp;% error for most individual analytes. The approach opens the possibility of field-deployable, autonomous measurement of the carbon and oxygen content of particulate matter using time-tested, low-maintenance detectors, though such an application would require some additional testing on complex mixtures. With some instrumental modifications, similar measurements on gas-phase species may be feasible. Moreover, the potential expansion to additional gas chromatography detectors may provide concurrent measurement of other elements (e.g., sulfur, nitrogen).</p>