Sampling frequency, load estimation and the disproportionate effect of storms on solute mass flux in rivers

Riverine discharge (Q) and dissolved concentrations (C) dictate solute mass export from watersheds. Commonly Q is tracked at a much higher frequency than C for most major solutes, leading to the necessity of load estimation algorithms which are often based on sparse data. The result is that the disproportionate effects of short-duration events (e.g., storms) on solute mass fluxes are poorly known. Here we use novel lab-in-the-field instrumentation to compare high temporal-resolution (∼30 min to 7 h) datasets of major ion chemistry collected over a year of continuous monitoring in three watersheds ranging over four orders of magnitude in drainage area. In these diverse settings, we quantify the errors associated with common load estimation algorithms and reduced sampling frequencies. When sample frequencies are coarsened, the mass flux of solutes which are diluted by storm events (i.e., Ca²⁺, Mg²⁺, Na⁺, Cl^- and SO₄^2-) are systematically overestimated, while nutrients which become mobilized by these events (K⁺ and NO₃^-) are underestimated. This is most pronounced in the largest river, and strongly tied to the increasing likelihood that storm events are missed as sampling frequencies decrease. Coarsening our high-resolution data to monthly sampling frequency yields an average overestimate of 8 % for Na⁺ and an average underestimate of 32.5 % for K⁺ across the three watersheds, illustrating clear implications for estuary and coastal water eutrophication, chemical weathering budgets, and agricultural land management practices. SYNOPSIS: A new 'lab-in-the-field' technology produces continuous high-frequency records of the full suite of major ions in rivers. These data highlight the disproportionate effect of large storms on catchment solute exports and the error associated with temporally coarse monitoring.