A new approximation is proposed to estimate O 3 and NO 2 mixing ratios in the northern subtropical free tro-posphere (FT). The proposed method uses O 4 slant column densities (SCDs) at horizontal and near-zenith geometries to estimate a station-level differential path. The modified geo-metrical approach (MGA) is a simple method that takes ad-vantage of a very long horizontal path to retrieve mixing ra-tios in the range of a few pptv. The methodology is presented, and the possible limitations are discussed. Multi-axis differ-ential optical absorption spectroscopy (MAX-DOAS) high-mountain measurements recorded at the Izaña observatory (28 • 18 N, 16 • 29 W) are used in this study. The results show that under low aerosol loading, O 3 and NO 2 mixing ratios can be retrieved even at very low concentrations. The ob-tained mixing ratios are compared with those provided by in situ instrumentation at the observatory. The MGA reproduces the O 3 mixing ratio measured by the in situ instrumentation with a difference of 28 %. The different air masses scanned by each instrument are identified as a cause of the discrep-ancy between the O 3 observed by MAX-DOAS and the in situ measurements. The NO 2 is in the range of 20–40 ppt, which is below the detection limit of the in situ instrumenta-tion, but it is in agreement with measurements from previous studies for similar conditions.