Carbonate chemistry of surface waters in a temperate karst region: the southern Yorkshire Dales, UK

Abstract

A detailed study of surface water chemistry is described from an important limestone region in northern England. Major ions and pH were determined for 485 sites (springs, seeps, streams, rivers and lakes) during summertime. The saturation state of the waters with respect to calcite was determined as the calcite saturation ratio (Ω). An unexpectedly large number of samples were found to be supersaturated (65.5% of the 268 km of watercourses surveyed). As a consequence, several streams entering major cave systems were incapable of further limestone solution, at least during periods of low flow. Many waters were supersaturated from their source and some deposited travertine. A significant negative correlation was found between spring discharge and both (Ω) and pH. Supersaturation was caused primarily by atmospheric degassing, with some contribution from aquatic plant photosynthesis. The median total dissolved inorganic carbon and Ca concentrations were 2.49 and 1.35 millimoles 1 −1 respectively. Calcium originated exclusively from limestone, and carbon dioxide mainly from the soil and dissolved limestone. South facing catchments provided springwaters with significantly higher levels of TDIC and Ca when compared with north facing catchments. The study suggests that acid rain made a measurable contribution to limestone dissolution. Carboniferous limestone denudation rates were estimated as 54 to 63 m 3 km −2 a −1 (54 to 63 mm 1000 years −1). About 50% of the Mg came from limestone and the remainder, together with most K, Na, SO 4 and Cl from precipitation. Concentrations of dissolved nutrients were low, medians for NO 3, NH 4, total PO 4 and SiO 3 were 24 μmol, 1.4 μmol, 0.64 μmol and 15.5 μmol 1 −1 respectively. The concentration of a further 23 trace elements was determined.