Ozone Cross-Section Measurement by Gas Phase Titration.

Elevated values of ground-level ozone damage health, vegetation, and building materials and are the subject of air quality regulations. Levels are monitored by networks using mostly ultraviolet (UV) absorption instruments, with traceability to standard reference photometers, relying on the UV absorption of ozone at the 253.65 nm line of mercury. We have redetermined the ozone cross-section at this wavelength based on gas phase titration (GPT) measurements. This is a well-known chemical method using the reaction of ozone (O) with nitrogen monoxide (NO) resulting in nitrogen dioxide (NO) and oxygen (O). The BIPM GPT facility uses state-of-the-art flow measurement, chemiluminescence for NO concentration measurements, a cavity phase shift analyzer (CAPS) for NO measurements, and a UV ozone analyzer. The titration experiment is performed over the concentration range 100-500 nmol/mol, with NO and NO reactants/calibrants diluted down from standards with nominal mole fractions of 50 μmol/mol. Accurate measurements of NO, NO, and O mole fractions allow the calculation of ozone absorption cross section values at 253.65 nm, and we report a value of 11.24 × 10 cm molecule with a relative expanded uncertainty of 1.8% (coverage factor k = 2) based on nitrogen monoxide titration values and a value of 11.22 × 10 cm molecule with a relative expanded uncertainty of 1.4% (coverage factor k = 2) based on nitrogen dioxide titration values. The excellent agreement between these values and recently published absorption cross-section measurements directly on pure ozone provide strong evidence for revising the conventionally accepted value of ozone cross section at 253.65 nm.