New in situ and minimally invasive methods are needed to quantify the presence of liquid water and ice within operating proton exchange membrane fuel cells. A volume sensitive residence time distribution technique was developed based on CO2 tracer and infrared detection. The method, components and operation are detailed (tracer injection and detection, data scaling, calibration, and pressure correction). The measurement system was characterized by an electronic signal processing response time of 43 ms, accuracy and repeatability better than 0.5-5% error in transit time measurement and sufficient sensitivity to detect less than 10% changes in flow field channel and gas diffusion electrode void volumes. Results obtained with a simplified model fuel cell (single flow field channel, absence and presence of a gas diffusion layer) revealed the presence of two time resolved mechanistic steps for negative tracer step cases (convective tracer removal from flow field channel, diffusive tracer removal from gas diffusion layer). A one-dimensional model was derived using convective diffusion in flow field channels and cross-flow tracer exchange proportional to the concentration difference between flow field channel and gas diffusion electrode. Numerical computations showed good agreement with the model fuel cell experimental results. (c) 2006 Elsevier Ltd. All rights reserved.