The use of NO₂ absorption cross section temperature sensitivity to derive NO₂ profile temperature and stratospheric–tropospheric column partitioning from visible direct-sun DOAS measurements

Abstract

This paper presents a temperature sensitivity method (TESEM) to accurately calculate total vertical NO₂ column, atmospheric slant NO₂ profile-weighted temperature (T ), and to separate stratospheric and tropospheric columns from direct-sun (DS), ground-based measurements using the retrieved T . TESEM is based on differential optical absorption spectroscopy (DOAS) fitting of the linear temperature-dependent NO₂ absorption cross section, σ (T ), regression model (Vandaele et al., 2003). Separation between stratospheric and tropospheric columns is based on the primarily bimodal vertical distribution of NO₂ and an assumption that stratospheric effective temperature can be represented by temperature at 27 km ± 3 K, and tropospheric effective temperature is equal to surface temperature within 3–5 K. These assumptions were derived from the Global Modeling Initiative (GMI) chemistry-transport model (CTM) simulations over two northern midlatitude sites in 2011. TESEM was applied to the Washington State University Multi-Function DOAS instrument (MFDOAS) measurements at four midlatitude locations with low and moderate NO₂ anthropogenic emissions: (1) the Jet Propulsion Laboratory’s Table Mountain Facility (JPLTMF), CA, USA (34.38◦ N/117.68◦ W); (2) Pullman, WA, USA (46.73◦ N/117.17◦ W); (3) Greenbelt, MD, USA (38.99◦ N/76.84◦ W); and (4) Cabauw, the Netherlands (51.97◦ N/4.93◦ E) during July 2007, June–July 2009, July– August and October 2011, November 2012–May 2013, respectively. NO₂ T and total, stratospheric, and tropospheric NO₂ vertical columns were determined over each site