Prediction of the Response of a Photoionization Detector to a Complex Gaseous Mixture of Volatile Organic Compounds Produced by -Pinene Oxidation

Photoionization detectors (PIDs) are lightweight and respond in real time to the concentrations of volatile organic compounds (VOCs), making them suitable for environmental measurements on many platforms. However, the nonselective sensing mechanism of PIDs challenges data interpretation, particularly when exposed to the complex VOC mixtures prevalent in the Earth's atmosphere. Herein, two approaches to this challenge are investigated. In the first, quantum-chemistry calculations are used to estimate photoionization cross sections and ionization potentials of individual species. In the second, machine learning models are trained on these calculated values, as well as empirical PID response factors, and then used for prediction. For both approaches, the resulting information for individual species is used to model the overall PID response to a complex VOC mixture. In complement, laboratory experiments in the Harvard Environmental Chamber are carried out to measure the PID response to the complex molecular mixture produced by alpha-pinene oxidation under various conditions. The observations show that the measured PID response is 15% to 30% smaller than the PID response modeled by quantum-chemistry calculations of the photoionization cross section for the photo-oxidation experiments and 15% to 20% for the ozonolysis experiments. By comparison, the measured PID response is captured within a 95% confidence interval by the use of machine learning to model the PID response based on the empirical response factor in all experiments. Taken together, the results of this study demonstrate the application of machine learning to augment the performance of a nonselective chemical sensor. The approach can be generalized to other reactive species, oxidants, and reaction mechanisms, thus enhancing the utility and interpretability of PID measurements for studying atmospheric VOCs.