Chemiluminometric Measurement of Atmospheric Ozone with Photoactivated Chromotropic Acid

A highly sensitive, robust, fast, affordable measurement system based on interfacial gas-liquid chemiluminescence (CL) on a wetted transparent screen directly on top of a miniature photomultiplier tube provides the basis of an attractive method for ozone (O₃). Alkaline chromotropic acid (CA, 4,5-dihydroxynaphthalene-2,7-disulfonic acid) chemiluminesces upon exposure to ozone. No light emission is observed from exposure of alkaline CA to NO ₂ or H₂O₂. However, response to ozone is highly dependent on the age and storage condition of the CA solution. As such, quantitative analysis will require frequent calibration, and the method will not be attractive. We have discovered that photoactivation plays the key role in producing (a) compound(s) from chromotropic acid that appear(s) to be the primary agent(s) responsible for the CL reaction with O₃. We thus devised a method wherein a flowing solution of CA (that is stable in neutral/acidic solutions) is rendered alkaline and then exposed for a few seconds on-line to UV radiation. The solution then reacts with ozone on a screen consisting of an "invisible" nylon stocking that provides for low liquid residence time and high light throughput and results in an LOD of 40 pptv, a determination range at least up to 230 ppbv, and 10-90% and 90-10% response times of 130 and 80 ms, respectively. Intra- and interday repeatabilities at the same concentration were 0.32 and 3.8% in relative standard deviation. On the basis of aging, CL, chromatography, and chromatography-mass spectrometry studies, we suggest that the primary CL-active species are likely dimeric semiquinone species derived from CA by a series of radical reactions.