An examination of the relation between runoff rate, R, and concentration, C, of twelve major constituents in four small watersheds in eastern Puerto Rico demonstrates a consistent pattern of responses. For solutes that are not substantially bioactive (alkalinity, silica, calcium, magnesium, sodium, and chloride), the log(R)–log(C) relation is almost linear and can be described as a weighted average of two sources, bedrock weathering and atmospheric deposition. The slope of the relation for each solute depends on the respective source contributions to the total river load. If a solute were strictly derived from bedrock weathering, the slope would be −0.3 to −0.4, whereas if strictly derived from atmospheric deposition, the slope would be approximately −0.1. The bioactive constituents (dissolved organic carbon, nitrate, sulfate, and potassium), which are recycled by plants and concentrated in shallow soil, demonstrate nearly flat or downward-arched log(R)–log(C) relations. The peak of the arch represents a transition from dominantly soil-matrix flow to near-surface macropore flow, and finally to overland flow. At highest observed R (80 to >90 mm/h), essentially all reactive surfaces have become wetted, and the input rate of C becomes independent of R (log(R)–log(C) slope of –1). The highest R are tenfold greater than any previous study. Slight clockwise hysteresis for many solutes in the rivers with riparian zones or substantial hyporheic flows indicates that these settings may act as mixing end-members. Particulate constituents (suspended sediment and particulate organic carbon) show slight clockwise hysteresis, indicating mobilization of stored sediment during rising stage.