Type of probability distribution reflects how close mixing dynamics in river chemistry are to thermodynamic equilibrium

Abstract

The distribution of geochemical species are typically either (log)normally distributed or follow power laws. Here we link these types of distributions to the dynamics of the system that generates these distributions, showing that power laws can emerge in dissipative systems far from equilibrium while (log)normal distributions are found for species for which the concentrations are close to equilibrium. We use observations of the chemical composition of river water from the sampling space in central Italy as well as discharge data to test this interpretation. We estimate the dissipation rate that results when groundwater drains into the river and the dissolved chemical species mix with the river water. We show that calcium (Ca2+) and bicarbonate (HCO3−) concentrations are close to saturation along most of the downstream length of the Arno river, with decreasing dissipation rates and a lognormal distribution, while sodium (Na+) and chloride (Cl−) concentrations increase substantially downstream, show increased dissipation rates, and are power-law distributed. This supports our hypothesis that power law distributions appear to be indicative of dissipative systems far from thermodynamic equilibrium, while (log)normal distributions indicate weakly dissipative systems close to equilibrium. What this implies is that probability distributions are likely to be indicative of the thermodynamics of the system and the magnitude of disequilibrium constrains the range over which power-law scaling may be observed. This should help us to better identify the generalities and mechanisms that result in these common types of distributions and to better classify variability in systems according to how dissipative these are.