Abstract:Stream water was analysed to determine how induced watershed acidification changed the chemistry of peakflow and baseflow and to compare the relative timing of these changes. Two watersheds in north-central West Virginia, WS3 and WS9, were subjected to three applications of ammonium sulphate fertilizer per year to induce acidification. A third watershed, WS4, was the control. Samples were collected for 8 years from WS9 and for 9 years from WS3. Prior to analyses, concentration data were flow adjusted, and the influence of natural background changes was removed by accounting for the chemical responses measured from WS4. This yielded residual values that were evaluated using robust locally weighted regression and Mann-Kendall tests. On WS3, analyte responses during baseflow and peakflow were similar, although peakflow responses occurred soon after the first treatment whereas baseflow responses lagged 1-2 years. This lag in baseflow responses corresponded well with the mean transit time of baseflow on WS3. Anion adsorption on WS3 apparently delayed increases in SO 4 leaching, but resulted in enhanced early leaching losses of Cl and NO 3 . Leaching of Ca and Mg was strongly tied, both by timing and stoichiometrically, to NO 3 and SO 4 leaching. F-factors for WS3 baseflow and peakflow indicated that the catchment was insensitive to acid neutralizing capacity reductions both before and during treatment, although NO 3 played a large role in reducing the treatment period F-factor. By contrast, the addition of fertilizer to WS9 created an acid sensitive system in both baseflow and peakflow. On WS9, baseflow and peakflow responses also were similar to each other, but there was no time lag after treatment for baseflow. Changes in concentrations generally were not as great on WS9 as on WS3, and several ions showed no significant changes, particularly for peakflow. The lesser response to treatment on WS9 is attributed to the past abusive farming and site preparation before larch planting that resulted in poor soil fertility, erosion, and consequently, physical and chemical similarities between upper and lower soil layers. Even with fertilizer-induced NO 3 and SO 4 leaching increases, base cations were in low supplies and, therefore, unavailable to leach via charge pairing. The absence of a time lag in treatment responses for WS9 baseflow indicates that it has substantially different flow paths than WS3. The different hydrologies on these nearby watersheds illustrates the importance of understanding watershed hydrology when establishing a monitoring programme to detect ecosystem change. Published in