A tunable diode laser absorption spectrometer for formaldehyde atmospheric measurements validated by simulation chamber instrumentation

A tunable diode laser absorption spectrometer (TDLAS) for formaldehyde atmospheric measurements has been set up and validated through comparison experiments with a Fourier transform infrared spectrometer (FT-IR) in a simulation chamber. Formaldehyde was generated in situ in the chamber from reaction of ethene with ozone. Three HCHO ro-vibrational line intensities (at 2909.71, 2912.09 and 2914.46 cm(-1)) possibly used by TDLAS were calibrated by FT-IR spectra simultaneously recorded in the 1600-3200 cm(-1) domain during ethene ozonolysis, enabling the on-line deduction of the varying concentration for HCHO in formation. The experimental line intensities values inferred confirmed the calculated ones from the updated HITRAN database. In addition, the feasibility of stratospheric in situ HCHO measurements using the 2912.09 cm(-1) line was demonstrated. The TDLAS performances were also assessed, leading to a 2sigma detection limit of 88 ppt in volume mixing ratio with a response time of 60 sec at 30 Torr and 294 K for 112 m optical path. As part of this work, the room-temperature rate constant of this reaction and the HCHO formation yield were found to be in excellent agreement with the compiled literature data.