Product ion distributions using H₃O⁺ proton-transfer-reaction time-of-flight mass spectrometry (PTR-ToF-MS): mechanisms, transmission effects, and instrument-to-instrument variability

<p>Proton-transfer-reaction mass spectrometry (PTR-MS) using hydronium ion (H<span class="inline-formula">₃</span>O<span class="inline-formula">⁺</span>) ionization is widely used for the measurement of volatile organic compounds (VOCs) both indoors and outdoors. H<span class="inline-formula">₃</span>O<span class="inline-formula">⁺</span> ionization, as well as the associated chemistry in an ion–molecule reactor, is known to generate product ion distributions (PIDs) that include other product ions besides the proton-transfer product. We present a method, using gas-chromatography pre-separation, for quantifying PIDs from PTR-MS measurements of nearly 100 VOCs of different functional types including alcohols, ketones, aldehydes, acids, aromatics, organohalides, and alkenes. We characterize instrument configuration effects on PIDs and find that reactor reduced electric field strength (<span class="inline-formula"><math xmlns="http://www.w3.org/1998/Math/MathML" id="M9" display="inline" overflow="scroll" dspmath="mathml"><mrow><mi>E</mi><mo>/</mo><mi>N</mi></mrow></math><span><svg:svg xmlns:svg="http://www.w3.org/2000/svg" width="23pt" height="14pt" class="svg-formula" dspmath="mathimg" md5hash="fd48fd78e758fa1e4257114ffd913757"><svg:image xmlns:xlink="http://www.w3.org/1999/xlink" xlink:href="amt-18-1013-2025-ie00001.svg" width="23pt" height="14pt" src="amt-18-1013-2025-ie00001.png"/></svg:svg></span></span>), ion optic voltage gradients, and quadrupole settings have the strongest impact on measured PIDs. Through an interlaboratory comparison of PIDs measured from calibration cylinders, we characterized the variability of PID production from the same model of PTR-MS across seven participating laboratories. Product ion variability was generally smaller (e.g., <span class="inline-formula">&lt;</span> 20 %) for ions with larger contributions to the PIDs (e.g., <span class="inline-formula">&gt;</span> 0.30) but less predictable for product ions formed through O<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">2</mn><mo>+</mo></msubsup></mrow></math><span><svg:svg xmlns:svg="http://www.w3.org/2000/svg" width="8pt" height="15pt" class="svg-formula" dspmath="mathimg" md5hash="8d99a85f4aef609af9b35ac615cb59a1"><svg:image xmlns:xlink="http://www.w3.org/1999/xlink" xlink:href="amt-18-1013-2025-ie00002.svg" width="8pt" height="15pt" src="amt-18-1013-2025-ie00002.png"/></svg:svg></span></span> and NO<span class="inline-formula">⁺</span> reactions. We present a publicly available library of H<span class="inline-formula">₃</span>O<span class="inline-formula">⁺</span> PTR-MS PIDs that will be updated periodically with user-provided data for the continued investigation into instrument-to-instrument variability of PIDs.</p>