Potential and limitations of the MAX-DOAS method to retrieve the vertical distribution of tropospheric nitrogen dioxide

Abstract

Muliple Axis Differential Optical Absorption Spectroscopy (MAX-DOAS) instruments can measure from the ground the absorption by nitrogen dioxide (NO 2) of scattered sunlight seen in multiple viewing directions. This paper studies the potential of this technique to derive the vertical distribution of NO 2 in the troposphere. Such profile information is essential in validation studies in which MAX-DOAS retrievals play a role. The retrieval algorithm used is based on a pre-calculated look-up table and assumes homogeneous mixing of aerosols and NO 2 in layers extending from the surface to a variable height. Two retrieval models are compared: one including and one excluding an elevated NO 2 layer at a fixed altitude in the free troposphere. An ensemble technique is applied to derive retrieved model uncertainties. Sensitivity studies demonstrate that MAX-DOAS based retrievals can make a distinction between an NO 2 layer that extends from the surface to a certain height (having a constant mixing ratio, or a mixing ratio that decreases with altitude) and an elevated NO 2 layer. The height of the elevated NO 2 layer can only be retrieved accurately when the aerosol extinction profile is known and the measurement noise is low. The uncertainty in this elevated NO 2 layer height provides the main source of uncertainty in the retrieval of the free tropospheric contribution to the tropospheric NO 2 column. A comparison was performed with independent data, based on observations done at the CINDI campaign, held in the Netherlands in 2009. Comparison with lidar partial tropospheric NO 2 columns showed a correlation of 0.78, and an average difference of 0.1× 10 15 molec cm -2. The diurnal evolution of the NO 2 volume mixing ratio measured by in-situ monitors at the surface and averaged over five days with cloud-free mornings, compares quite well to the MAX-DOAS retrieval: a correlation was found of 0.8, and an average difference of 0.2 ppb.