Hydrochemistry of carbonate terrains in alpine glacial settings

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Abstract
Nearly 200 analyses of meltwaters, ice and snow from three alpine glacial sites in carbonate terrain are summarized and discussed in terms of sources of solutes and kinetic controls on the progress of weathering reactions. Most data derive from the Swiss Glacier de Tsanfleuron which is based on Cretaceous and Tertiary pure and impure limestones. Two other sites (Marmolada, Italian Dolomites and the Saskatchewan Glacier, Alberta) are based on a mixed calcitic‐dolomitic substrate.Most solutes originate from carbonate dissolution; moreover, where pyrite is present its oxidation supplies significant sulphate and forces more dissolution of carbonate. The ratios Sr2+/Ca2+ and Mg2+/Ca2+ are much higher in Tsanfleuron melt‐waters than local bedrock, a phenomenon that can be reproduced in the laboratory at small percentages of dissolution. These anomalous ratios are attributed to incongruent dissolution of traces of the metastable carbonates Mg‐calcite and aragonite. These phases also provide Na+ to solution. K+ is argued to originate mainly by ion‐exchange on clays with solute Ca2+. Quartz and very minor feldspar dissolution are also inferred. Locally enhanced input from atmospheric sources is recognized by high Cl− and associated Na+.The progress of weathering reactions has been evaluated by the trends in the data, computer modelling and some simple laboratory experiments. The most dilute samples show a trend towards removal of CO2 to low partial pressures (c. 10−5.5 atmospheres), reflecting initially rapid carbonate dissolution and relatively slow dissolution of gaseous CO2. Later addition of atmospheric CO2 or acid from pyrite oxidation allows further carbonate dissolution, but solutions show a wide range of saturations, and CO2 pressures as high as 10−2.2 where pyrite oxidation is important.In a carbonate terrain, measurement of electroconductivity (corrected to 25°C) and alkalinity in the field allows the following preliminary deductions (where meq stands for milliequivalents): magnified image where S is the minimum meq(Ca2+ + Mg2+) produced by simple dissolution of carbonate unconnected with pyrite oxidation. As with any proxy method, these deductions do not remove the need for chemical analysis of waters in a given study area.