Discrimination of the type of air mass along mountain slopes can be a challenge and is not commonly performed, but is critical for identifying factors responsible for influencing montane weather, climate, and air quality. A field campaign to measure air mass type and transitions on the summit of Mount Washington, New Hampshire, USA was performed on 19 August 2016. Meteorological observations were taken at the summit and at several sites along the east and west slopes. Ozone concentrations were measured at the summit and on the valley floor. Additionally, water vapor stable isotopes were measured from a truck that drove up and down the Mount Washington Auto Road concurrent with radiosonde launches that profiled the free atmosphere. This multivariate perspective revealed thermal, moisture, and air mass height differences among the free atmosphere, leeward, and windward mountain slopes. Both thermally and mechanically forced upslope flows helped shape these differences by altering the height of the boundary layer with respect to the mountain surface. Recommendations for measurement strategies hoping to develop accurate observational climatologies of air mass exposure in complex terrain are discussed and will be important for evaluating elevation-dependent warming and improving forecasting for weather and air quality.