Investigation of the β-pinene photooxidation by OH in the atmosphere simulation chamber SAPHIR

Beside isoprene, monoterpenes are the non-methane volatile organic compounds (VOC) with the highest global emission rates. Due to their high reactivity towards OH, monoterpenes can dominate the radical chemistry of the atmosphere in forested areas. In the present study the photochemical degradation mechanism of β-pinene was investigated in the Jülich atmosphere simulation chamber SAPHIR. The focus of this study is on the OH budget in the degradation process. Therefore the SAPHIR chamber was equipped with instrumentation to measure radicals (OH, HO2, RO2), the total OH reactivity, important OH precursors (O3, HONO, HCHO), the parent VOC beta-pinene, its main oxidation products, acetone and nopinone, and photolysis frequencies. All experiments were carried out under low NOx conditions (≤ 2 ppb) and at atmospheric beta-pinene concentrations (≤ 5 ppb) with and without addition of ozone. For the investigation of the OH budget, the OH production and destruction rates were calculated from measured quantities. Within the limits of accuracy of the instruments, the OH budget was balanced in all β-pinene oxidation experiments. However, even though the OH budget was closed, simulation results from the Master Chemical Mechanism 3.2 showed that the OH production and destruction rates were underestimated by the model. The measured OH and HO2 concentrations were underestimated by up to a factor of two whereas the total OH reactivity was slightly overestimated because of the poor reproduction of the measured nopinone by the model by up to a factor of three. A new, theory-derived first-generation product distribution by Vereecken and Peeters was able to reproduce the measured nopinone time series and the total OH reactivity. Nevertheless the measured OH and HO2 concentrations remained underestimated by the numerical simulations. These observations together with the fact that the measured OH budget was closed suggest the existence of unaccounted sources of HO2

Detection of nitrous acid in the atmospheric simulation chamber SAPHIR using open-path incoherent broadband cavity-enhanced absorption spectroscopy and extractive long-path absorption photometry

An instrument based on 20 m open-path incoherent broadband cavity-enhanced absorption spectroscopy (IBBCEAS) was established at the Jülich SAPHIR chamber in spring 2011. The setup was optimized for the detection of HONO and NO2 in the near-UV region 352–386 nm, utilizing a bright hot-spot Xe-arc lamp and a UV-enhanced charge-coupled device (CCD) detector. A 2σ detection limit of 26 pptv for HONO and 76 pptv for NO2 was achieved for an integration time of 1 min. Methacrolein (MACR) was also detected at mixing ratios below 5 ppbv with an estimated 2σ detection limit of 340 pptv for the same integration time. The IBBCEAS instrument's performance for HONO and NO2 detection was compared to that of extractive wet techniques, long-path absorption photometry (LOPAP), and chemiluminescence spectrometry (CLS) NOx detection, respectively. For the combined data sets an overall good agreement for both trend and absolute mixing ratios was observed between IBBCEAS and these established instruments at SAPHIR. Correlation coefficients r for HONO range from 0.930 to 0.994 and for NO2 from 0.937 to 0.992. For the single measurement of MACR r=0.981 is found in comparison to proton-transfer-reaction mass spectrometry (PTRMS)