ABSTRACT: Programs of monthly or annual stream water sampling will rarely observe the episodic extremes of acidification chemistry that occur during brief, unpredictable runoff events. When viewed in the context of data from several streams, however, baseflow measurements of variables such as acid neutralizing capacity, pH and NO3· are likely to be highly correlated with the episodic extremes of those variables from the same stream and runoff season. We illustrate these correlations for a water chemistry record, nearly two years in length, obtained from intensive sampling of 13 small Northeastern U.S. streams studied during USEPA's Episodic Response Project. For these streams, simple regression models estimate episodic extremes of acid neutralizing capacity, pH, NO3·, Ca2+, SO42−, and total dissolved Al with good relative accuracy from statistics of monthly or annual index samples. Model performances remain generally stable when episodic extremes in the second year of sampling are predicted from first-year models. Monthly or annual sampling designs, in conjunction with simple empirical models calibrated and maintained through intensive sampling every few years, may estimate episodic extremes of acidification chemistry with economy and reasonable accuracy. Such designs would facilitate sampling a large number of streams, thereby yielding estimates of the prevalence of episodic acidification at regional scales.