Abstract

Limestone drains are an integral component of some of the most efficacious passive systems for the treatment of acid rock drainage (ARD). A critical design parameter for a limestone drain is the mass of limestone that will be required for effective treatment. This in turn depends on the flow rate, limestone dissolution rate, and associated hydraulic detention time necessary to achieve a certain effluent alkalinity for a given design life. Rates of alkalinity generation and limestone dissolution, and the quality of the limestone in terms of weight fraction of CaCO3 and percentage CaCO3 available must be known to determine the required mass of limestone. These parameters were experimentally determined for a natural and synthetic suite of ARD waters. The experimental results show that the empirical change in the alkalinity over time cannot simply be modeled as a first-order process. During the initial stage, the concentration increase is extremely fast, giving a linear and steep rise in the alkalinity. Alkalinity concentrations peaked at elapsed times of 90 to 180 minutes and then declined to a nearly constant value. The decline in alkalinity corresponds with a decline in concentrations of dissolved iron and aluminum, implying that the consumption of alkalinity by the hydrolysis of these metals is faster than the rate of alkalinity production by the dissolution of limestone, so that the reaction appears zero order in the early stage and pseudo-first order later. Because the changes in concentration were complex, considerable uncertainty exists in the rate constants for estimating alkalinity concentration. This causes problems in design equations based solely on a limestone dissolution rate that is estimated from alkalinity generation rates. A more applicable design procedure, combining the kinetics of alkalinity production and consumption with the hydraulics and chemical equilibrium of the system, is illustrated.

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