We demonstrate that the relationship between the abundance of particulate surface area observed at sea-level and measurements of backscattered light by a ceilometer can be used to classify the mixing state of the atmospheric layer beneath the lowest observed cloud, where the relationship is defined by the Spearman Rank correlation. The accuracy of this correlation-based method was compared to two methods of detecting boundary layer decoupling based on radiosonde measurements. An optimized version of the new methodology correctly determined the mixing state of the below-cloud layer for 76 ± 4% of the radiosondes available for comparison. Further, it was more accurate than an alternative ground-based metric used to determine the below-cloud mixing state. For the majority of the time series in which the correlation analysis could be applied, the below-cloud boundary layer was well-mixed (54%), or else fog was present (27%), which indicated that aerosol particles observed at sea-level often have a direct pathway into low-cloud (81%). In the remaining analysis period, the near-surface atmospheric layer was stable and the atmospheric layer near the ocean surface was decoupled from the overlying cloud (19%). Forecasts from the Antarctic Mesoscale Prediction System also support our findings, showing that conditions that mix aerosol particles from the ocean surface to the lowest observed cloud occur 84% of the time over the open Southern Ocean. As a result, aerosol particles measured near sea-level are often tightly coupled to low-cloud formation over the Southern Ocean, highlighting the utility of shipborne aerosol observations in the region.