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

机译:估计大气总有机碳(TOC) - 铺设碳预算闭合的路径

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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 8ppbC 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 2ppmC) as a result of local anthropogenic activity. On weekends and holidays, with a mean (standard error) of 102 (8)ppbC, 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 analyzer, while operating our system alternately with and without a particle filter should enable a better separation of semi-volatile and particulate organics from the VOCs within the TOC budget. Future concurrent measurements of TOC, CO, and a more comprehensive range of speciated VOCs would enable a better characterization and understanding of the atmospheric organic carbon budget.
机译:气氛含有丰富的反应性有机化合物,包括气态挥发性有机碳(VOC),碳质气溶胶和其他有机化合物,在不同的挥发性下。在这里,我们提出了一种基于批量空气催化氧化在二氧化碳中的有机物催化氧化的新颖和简单的方法来测量大气非甲烷总有机碳(TOC)。该方法对所有测试的VOC的湿度和接近100%的氧化效率略微敏感。在二氧化碳,甲烷和一氧化碳(CO)的低环境变异期间,我们估计了8pPBC的最佳情况每小时精度。作为这种方法的概念证明,我们在8月至9月期间显示了TOC + CO的测量?2016来自英国西南部的沿海城市。由于局部人为活动,TOC + CO在白天(偶尔超过2ppmc)的日期基本上升高。在周末和假期,具有102(8)PPBC的平均值(标准误差),TOC + CO较低,呈现较少的昼夜变异性。当我们排除白天白天时,当风脱离大西洋时,托克+ CO明显降低。通过从TOC + CO中减去估计的CO,在此期间,我们将大西洋主导的空气质量中的平均(不确定性)TOC限制为大约23(±≥8)PPBC。同时展开质子转移反应质谱仪(PTR-MS),检测大量的有机化合物(含氧VOC,生物转向VOC,芳烃,二甲基硫醚)。来自PTR-MS的总所指标的VOC,这里表示为SUM(VOC),其在海洋空气中为12(±≤3)PPBC的平均值(不确定度)。在TOC预算的范围内评估来自PTR-MS未检测到的海洋空气中存在的许多已知有机化合物的可能贡献。最后,我们注意到使用短,加热的样品管可以改善有机物传递到分析仪,同时交替使用粒子过滤器操作我们的系统,应该能够从VOC中更好地分离半挥发性和颗粒物有机物在TOC预算中。 TOC,CO和更全面的规格VOC的未来并发测量将能够更好地表征和对大气有机碳预算的理解。

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