Inherent calibration of a blue LED-CE-DOAS instrument to measure iodine oxide, glyoxal, methyl glyoxal, nitrogen dioxide, water vapour and aerosol extinction in open cavity mode

The combination of Cavity Enhanced Absorption Spectroscopy (CEAS) with broad-band light sources (e.g. Light-Emitting Diodes, LEDs) lends itself to the application of cavity enhanced Differential Optical Absorption Spectroscopy (CE-DOAS) to perform sensitive and selective point measurements of multiple trace gases and aerosol extinction with a single instrument. In contrast to other broad-band CEAS techniques, CE-DOAS relies only on the measurement of relative intensity changes, i.e. does not require knowledge of the light intensity in the absence of trace gases and aerosols (I-0). We have built a prototype LED-CE-DOAS instrument in the blue spectral range (420-490 nm) to measure nitrogen dioxide (NO2), glyoxal (CHOCHO), methyl glyoxal (CH3COCHO), iodine oxide (IO), water vapour (H2O) and oxygen dimers (O-4). We demonstrate the first direct detection of methyl glyoxal, and the first CE-DOAS detection of CHOCHO and IO. The instrument is further inherently calibrated for light extinction from the cavity by observing O-4 or H2O (at 477 nm and 443 nm) and measuring the pressure, relative humidity and temperature independently. This approach is demonstrated by experiments where laboratory aerosols of known size and refractive index were generated and their extinction measured. The measured extinctions were then compared to the theoretical extinctions calculated using Mie theory (3-7 x 10(-7) cm(-1)). Excellent agreement is found from both the O-4 and H2O retrievals. This enables the first inherently calibrated CEAS measurement at blue wavelengths in open cavity mode, and eliminates the need for sampling lines to supply air to the cavity, i.e., keep the cavity enclosed and/or aerosol free. Measurements in open cavity mode are demonstrated for CHOCHO, CH3COCHO, NO2, H2O and aerosol extinction. Our prototype LED-CE-DOAS provides a low cost, yet research grade innovative instrument for applications in simulation chambers and in the open atmosphere.