From Volume to Mass: Transforming Volatile Organic Compound Detection with Photoionization Detectors and Machine Learning.

(1) Objective: Volatile organic compounds (VOCs) monitoring in industrial parks is crucial for environmental regulation and public health protection. However, current techniques face challenges related to cost and real-time performance. This study aims to develop a dynamic calibration framework for accurate real-time conversion of VOCs volume fractions (nmol mol) to mass concentrations (μg m) in industrial environments, addressing the limitations of conventional monitoring methods such as high costs and delayed response times. (2) Methods: By innovatively integrating photoionization detector (PID) with machine learning, we developed a robust conversion model utilizing PID signals, meteorological data, and a random forest's (RF) algorithm. The system's performance was rigorously evaluated against standard gas chromatography-flame ionization detectors (GC-FID) measurements. (3) Results: The proposed framework demonstrated superior performance, achieving a coefficient of determination (R) of 0.81, root mean squared error (RMSE) of 48.23 μg m, symmetric mean absolute percentage error (SMAPE) of 62.47%, and a normalized RMSE (RMSE) of 2.07%, outperforming conventional methods. This framework not only achieved minute-level response times but also reduced costs to just 10% of those associated with GC-FID methods. Additionally, the model exhibited strong cross-site robustness with R values ranging from 0.68 to 0.69, although its accuracy was somewhat reduced for high-concentration samples (>1500 μg m), where the mean absolute percentage error (MAPE) was 17.8%. The inclusion of SMAPE and RMSE provides a more nuanced understanding of the model's performance, particularly in the context of skewed or heteroscedastic data distributions, thereby offering a more comprehensive assessment of the framework's effectiveness. (4) Conclusions: The framework's innovative combination of PID's real-time capability and RF's nonlinear modeling achieves accurate mass concentration conversion (R = 0.81) while maintaining a 95% faster response and 90% cost reduction compared to GC-FID systems. Compared with traditional single-coefficient PID calibration, this framework significantly improves accuracy and adaptability under dynamic industrial conditions. Future work will apply transfer learning to improve high-concentration detection for pollution tracing and environmental governance in industrial parks.