A nitrate ion chemical-ionization atmospheric-pressure-interface time-of-flight mass spectrometer (NO<sub>3</sub><sup>−</sup> ToFCIMS) sensitivity study

oleh: S. Alage, V. Michoud, S. Harb, B. Picquet-Varrault, M. Cirtog, A. Kumar, M. Rissanen, M. Rissanen, C. Cantrell

Format: Article
Diterbitkan: Copernicus Publications 2024-08-01

Deskripsi

<p>​​​​​​​Volatile organic compounds (VOCs) play a key role in tropospheric chemistry, giving rise to secondary products such as highly oxygenated organic molecules (HOMs) and secondary organic aerosols (SOAs). HOMs, a group of low-volatility gas-phase products, are formed through the autoxidation process of peroxy radicals (RO<span class="inline-formula"><sub>2</sub></span>) originating from the oxidation of VOCs. The measurement of HOMs is made by a NO<span class="inline-formula"><math xmlns="http://www.w3.org/1998/Math/MathML" id="M4" display="inline" overflow="scroll" dspmath="mathml"><mrow><msubsup><mi/><mn mathvariant="normal">3</mn><mo>-</mo></msubsup></mrow></math><span><svg:svg xmlns:svg="http://www.w3.org/2000/svg" width="9pt" height="16pt" class="svg-formula" dspmath="mathimg" md5hash="0723f17b5be9fc41c36a5585631feb47"><svg:image xmlns:xlink="http://www.w3.org/1999/xlink" xlink:href="amt-17-4709-2024-ie00004.svg" width="9pt" height="16pt" src="amt-17-4709-2024-ie00004.png"/></svg:svg></span></span> ToFCIMS instrument, which also detects other species like small highly oxygenated VOCs (e.g., dicarboxylic acids) and sulfuric acid (H<span class="inline-formula"><sub>2</sub></span>SO<span class="inline-formula"><sub>4</sub></span>). The instrument response to HOMs is typically estimated using H<span class="inline-formula"><sub>2</sub></span>SO<span class="inline-formula"><sub>4</sub></span>, as HOMs are neither commercially available nor easily synthesized in the laboratory. The resulting calibration factor is then applied to quantify all species detected using this technique. In this study, we explore the sensitivity of the instrument to commercially available small organic compounds, primarily dicarboxylic acids, given the limitations associated with producing known amounts of HOMs for calibration. We compare these single-compound calibration factors to the one obtained for H<span class="inline-formula"><sub>2</sub></span>SO<span class="inline-formula"><sub>4</sub></span> under identical operational conditions. The study found that the sensitivity of the NO<span class="inline-formula"><math xmlns="http://www.w3.org/1998/Math/MathML" id="M11" display="inline" overflow="scroll" dspmath="mathml"><mrow><msubsup><mi/><mn mathvariant="normal">3</mn><mo>-</mo></msubsup></mrow></math><span><svg:svg xmlns:svg="http://www.w3.org/2000/svg" width="9pt" height="16pt" class="svg-formula" dspmath="mathimg" md5hash="fa1148a5a7ab62133104fb46bf612014"><svg:image xmlns:xlink="http://www.w3.org/1999/xlink" xlink:href="amt-17-4709-2024-ie00005.svg" width="9pt" height="16pt" src="amt-17-4709-2024-ie00005.png"/></svg:svg></span></span> ToFCIMS varies depending on the specific type of organic compound, illustrating how a single calibration factor derived from sulfuric acid is clearly inadequate for quantifying all detected species using this technique. The results highlighted substantial variability in the calibration factors for the tested organic compounds, with 4-nitrocatechol exhibiting the highest sensitivity and pyruvic acid the lowest. The obtained sulfuric acid calibration factor agreed well with the previous values from the literature. In summary, this research emphasized the need to develop reliable and precise calibration methods for progressively oxygenated reaction products measured with a NO<span class="inline-formula"><math xmlns="http://www.w3.org/1998/Math/MathML" id="M12" display="inline" overflow="scroll" dspmath="mathml"><mrow><msubsup><mi/><mn mathvariant="normal">3</mn><mo>-</mo></msubsup></mrow></math><span><svg:svg xmlns:svg="http://www.w3.org/2000/svg" width="9pt" height="16pt" class="svg-formula" dspmath="mathimg" md5hash="ee54bb0fff66afdafaf51bed1fde360d"><svg:image xmlns:xlink="http://www.w3.org/1999/xlink" xlink:href="amt-17-4709-2024-ie00006.svg" width="9pt" height="16pt" src="amt-17-4709-2024-ie00006.png"/></svg:svg></span></span> chemical-ionization mass spectrometer (CIMS), for example, HOMs.</p>