Portable ozone calibration source independent of changes in temperature, pressure and humidity for research and regulatory applications

A highly portable ozone (inline-formulaO₃) calibration source that can serve as a U.S. EPA level 4 transfer standard for the calibration of ozone analyzers is described and evaluated with respect to analytical figures of merit and effects of ambient pressure and humidity. Reproducible mixing ratios of ozone are produced by the photolysis of oxygen in inline-formulaO₃-scrubbed ambient air by UV light at 184.9 nm light from a low-pressure mercury lamp. By maintaining a constant volumetric flow rate (thus constant residence time within the photolysis chamber), the mixing ratio produced is independent of both pressure and temperature and can be varied by varying the lamp intensity. Pulse width modulation of the lamp with feedback from a photodiode monitoring the 253.7 nm emission line is used to maintain target ozone mixing ratios in the range 30–1000 ppb. In order to provide a constant ratio of intensities at 253.7 and 184.9 nm, the photolysis chamber containing the lamp is regulated at a temperature of 40 inline-formula^∘C. The resulting inline-formulaO₃ calibrator has a response time for step changes in output ozone mixing ratio of < 30 s and precision (inline-formulaσ_p) of 0.4 % of the output mixing ratio for 10 s measurements (e.g., inline-formula $M6inlinescrollmathml{\mathrm{italic\; \sigma }}_{\mathrm{normal\; p}}=\pm \mathrm{normal\; 0.4}$ 49pt14ptsvg-formulamathimg1f7abf2285cbedf04e738786255de7ec amt-11-4797-2018-ie00001.svg49pt14ptamt-11-4797-2018-ie00001.png  ppb for 100 ppb of inline-formulaO₃). Ambient humidity was found to affect the output mixing ratio of ozone primarily by dilution of the oxygen precursor. This potential humidity interference could be up to a few percent in extreme cases but is effectively removed by varying the lamp intensity to compensate for the reduced oxygen concentration based on feedback from a humidity sensor.