The CU ground MAX-DOAS instrument: Characterization of RMS noise limitations and first measurements near Pensacola, FL of BrO, IO, and CHOCHO

Abstract

We designed and assembled the University of Colorado Ground Multi AXis Differential Optical Absorption Spectroscopy (CU GMAX-DOAS) instrument to retrieve bromine oxide (BrO), iodine oxide (IO), formaldehyde (HCHO), glyoxal (CHOCHO), nitrogen dioxide (NO 2) and the oxygen dimer (O 4) in the coastal atmosphere of the Gulf of Mexico. The detection sensitivity of DOAS measurements is proportional to the root mean square (RMS) of the residual spectrum that remains after all absorbers have been subtracted. Here we describe the CU GMAX-DOAS instrument and demonstrate that the hardware is capable of attaining RMS of ∼6 × 10 -6 from solar stray light noise tests using high photon count spectra (compatible within a factor of two with photon shot noise). Laboratory tests revealed two critical instrument properties that, in practice, can limit the RMS: (1) detector non-linearity noise, RMS NLin, and (2) temperature fluctuations that cause variations in optical resolution (full width at half the maximum, FWHM, of atomic emission lines) and give rise to optical resolution noise, RMS FWHM. The non-linearity of our detector is low (∼10 -2) yet-unless actively controlled-is sufficiently large to create RMS NLin of up to 2 × 10 -4. The optical resolution is sensitive to temperature changes (0.03 detector pixels °C -1 at 334 nm), and temperature variations of 0.1°C can cause RMS FWHM of ∼1 × 10 -4). Both factors were actively addressed in the design of the CU GMAX-DOAS instrument. With an integration time of 60 s the instrument can reach RMS noise of 3 × 10 -5), and typical RMS in field measurements ranged from 6 × 10 -5) to 1.4 × 10 -4). The CU GMAX-DOAS was set up at a coastal site near Pensacola, Florida, where we detected BrO, IO and CHOCHO in the marine boundary layer (MBL), with daytime average tropospheric vertical column densities (average of data above the detection limit), VCDs, of ∼2 × 10 13) molec cm -2), 8 × 10 12) molec cm -2) and 4 × 10 14) molec cm -2), respectively. HCHO and NO 2 were also detected with typical MBL VCDs of 1 × 10 16) and 3 × 10 15) molec cm -2). These are the first measurements of BrO, IO and CHOCHO over the Gulf of Mexico. The atmospheric implications of these observations for elevated mercury wet deposition rates in this area are briefly discussed. The CU GMAX-DOAS has great potential to investigate RMS-limited problems, like the abundance and variability of trace gases in the MBL and possibly the free troposphere (FT). © 2011 Author(s).