In this study, we adopt a unique approach by utilizing the responses of human autonomic systems to gauge the abundance of pollutants in inhaled air. Air pollution has numerous impacts on human health on a variety of time scales. This study uses biometric observations of the human autonomic response on the second timescale to investigate how the human body autonomically responds to inhaled pollutants in microenvironments, including particulate matter. PM1 and PM2.5, carbon dioxide (CO2), nitrogen dioxide (NO2), and nitric oxide (NO) on small temporal and spatial scales. These pollutants are exemplars of the wider human exposome. We compare two experimental approaches that use a similar methodology, employing a biometric suite to capture the physiological responses of cyclists and sensors to monitor the pollutants in the air surrounding them. We employ machine learning algorithms to estimate the levels of these pollutants and decipher the body’s automatic reactions to them. We observed high precision in predicting PM1, PM2.5 and CO2 using a limited set of biometrics from participants. Although the predictions for NO2 and NO were reliable at lower concentrations, the precision varied throughout the data range. This discrepancy suggests the potential to improve our models with more comprehensive data collection or advanced machine learning techniques.