Application of a differential fuel-cell analyzer for measuring atmospheric oxygen variations

A commercially available differential fuel-cell analyzer has been adapted to make field-based ppm-level measurements of atmospheric O₂ variations. With the implementation of rapid calibrations and active pressure and flow control, the analysis system described here has a 1σ precision of ±2.5 per meg (≈0.5 ppm) for a 2-min measurement. Allowing for system stabilization after switching inlet lines, a 6-min measurement with a precision of ±1.4 per meg (≈0.3 ppm) every 20 min is obtained. The elimination of biases in any atmospheric O₂ measurement depends critically on careful gas-handling procedures, and after screening for known sources of bias a comparability of ±10 per meg (≈2 ppm) with the present setup is estimated. In comparison to existing techniques, the relatively small size, low cost, fast response, motion insensitivity, and ease of implementation of the fuel-cell analyzer make it particularly useful for a wide range of unattended field applications. This system has been used to measure atmospheric O₂ concentrations at the WLEF tall-tower research site in northern Wisconsin semicontinuously from June 2000 to December 2003. These measurements represent the first extended O₂ record in and above a forest ecosystem, and are being used to investigate global carbon budgeting, plant physiology, continental boundary layer mixing and synoptic transport, and potential means of industrial emission verification. In this paper, the measurement technique is described in detail and several weeks of data are presented to illustrate its performance.