We present an analysis of multifrequency measurements of atmospheric emission in the Rayleigh-Jeans portion of the cosmic microwave background spectrum (1-90 GHz) taken since 1986 from White Mountain, CA, and from the South Pole. Correlations of simultaneous data at 10 and 90 GHz and accurate low-frequency measurements show good agreement with model predictions for both sites. Our data from the South Pole 1989 campaign combined with real-time measurements of the local atmospheric profiles provide accurate verification of the expected independent contributions of H2O and O2 emission. We show that variations on the order of 10% of the oxygen emission (both resonant and nonresonant components) are present on timescales of hours to days, mainly due to the evolution of the atmospheric pressure profile. Oxygen emission fluctuations appear larger than previously expected and may have significant consequences for ground-based cosmic microwave background experiments.