Severe biomass burning (BB) events have become increasingly common in South America in the last few years, mainly due to the high number of wildfires observed recently. Such incidents can negatively influence the air quality index associated with PM2.5 (particulate matter, which is harmful to human health). A study performed in the Metropolitan Area of São Paulo (MASP) took place on selected days of July 2019, evaluated the influence of a BB event on air quality. Use of combined remote sensing, a surface monitoring system and data modeling and enabled detection of the BB plume arrival (light detection and ranging (lidar) ratio of (50 ± 34) sr at 532 nm, and (72 ± 45) sr at 355 nm) and how it affected the Ångström exponent (>1.3), atmospheric optical depth (>0.7), PM2.5 concentrations (>25 µg.m−3), and air quality classification. The utilization of high-order statistical moments, obtained from elastic lidar, provided a new way to observe the entrainment process, allowing understanding of how a decoupled aerosol layer influences the local urban area. This new novel approach enables a lidar system to obtain the same results as a more complex set of instruments and verify how BB events contribute from air masses aloft towards near ground ones.