Estimation of atmospheric total organic carbon (TOC) - paving the path towards carbon budget closure

摘要

The atmosphere contains a rich variety of reactive organic compounds, including gaseous volatile organic carbon (VOCs), carbonaceous aerosols, and other organic compounds at varying volatility. Here we present a novel and simple approach to measure atmospheric non-methane total organic carbon (TOC) based on catalytic oxidation of organics in bulk air to carbon dioxide. This method shows little sensitivity towards humidity and near 100% oxidation efficiencies for all VOCs tested. We estimate a best-case hourly precision of 8 ppbC during times of low ambient variability in carbon dioxide, methane, and carbon monoxide (CO). As proof of concept of this approach, we show measurements of TOC + CO during August-September 2016 from a coastal city in the southwest United Kingdom. TOC + CO was substantially elevated during the day on weekdays (occasionally over 2 ppm C) as a result of local anthropogenic activity. On weekends and holidays, with a mean (standard error) of 102 (8) ppb C, TOC + CO was lower and showed much less diurnal variability. TOC + CO was significantly lower when winds were coming off the Atlantic Ocean than when winds were coming off land if we exclude the weekday daytime. By subtracting the estimated CO from TOC + CO, we constrain the mean (uncertainty) TOC in Atlantic-dominated air masses to be around 23 (+/- = 8) ppbC during this period. A proton-transfer-reaction mass spectrometer (PTR-MS) was deployed at the same time, detecting a large range of organic compounds (oxygenated VOCs, biogenic VOCs, aromatics, dimethyl sulfide). The total speciated VOCs from the PTR-MS, denoted here as Sum(VOC), amounted to a mean (uncertainty) of 12 (+/- = 3) ppbC in marine air. Possible contributions from a number of known organic compounds present in marine air that were not detected by the PTR-MS are assessed within the context of the TOC budget. Finally, we note that the use of a short, heated sample tube can improve the transmission of organics to the analy