The distribution of low molecular weight carboxylic acids (LMWCA) was investigated in pore water profiles from two porphyry copper tailings impoundments in Chile (Piuquenes at La Andina and Cauquenes at El Teniente mine). The objectives of this study were (1) to determine the distribution of LMWCA, which are interpreted to be the metabolic byproducts of the autotroph microbial community in this low organic carbon system, and (2) to infer the potential role of these acids in cycling of Fe and other elements in the tailings impoundments. The speciation and mobility of iron, and potential for the release of H+ via hydrolysis of the ferric iron, are key factors in the formation of acid mine drainage in sulfidic mine wastes. In the low-pH oxidation zone of the Piuquenes tailings, Fe(III) is the dominant iron species and shows high mobility. LMWCA, which occur mainly between the oxidation front down to 300 cm below the tailings surface at both locations (e.g., max concentrations of 0.12 mmol/L formate, 0.17 mmol/L acetate, and 0.01 mmol/L pyruvate at Piuquenes and 0.14 mmol/L formate, 0.14 mmol/L acetate, and 0.006 mmol/L pyruvate at Cauquenes), are observed at the same location as high Fe concentrations (up to 71.2 mmol/L Fe(II) and 16.1 mmol/L Fe(III), respectively). In this zone, secondary Fe(III) hydroxides are depleted. Our data suggest that LMWCA may influence the mobility of iron in two ways. First, complexation of Fe(III), through formation of bidentate Fe(III)-LMWCA complexes (e.g., pyruvate, oxalate), may enhance the dissolution of Fe(III) (oxy)hydroxides or may prevent precipitation of Fe(III) (oxy)hydroxides. Soluble Fe(III) chelate complexes which may be mobilized downward and convert to Fe(II) by Fe(III) reducing bacteria. Second, monodentate LMWCA (e.g., acetate and formate) can be used by iron-reducing bacteria as electron donors (e.g., Acidophilum spp.), with ferric iron as the electron acceptor. These processes may, in part, explain the low abundances of secondary Fe(III) hydroxide precipitates below the oxidation front and the high concentrations of Fe(II) observed in the pore waters of some low-sulfide systems. The reduction of Fe(III) and the subsequent increase of iron mobility and potential acidity transfer (Fe(II) oxidation can result in the release of H+ in an oxic environment) should be taken in account in mine waste management strategies.

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Loss of volatile organics during sampling is a well‐recognized source of bias in ground water monitoring; sampling protocols attempt to minimize such loss. Such bias could be enhanced for ground water highly charged with dissolved gases such as methane. Such ground water was the object of this study. A positive‐displacement bladder pump, a momentum‐lift pump and a suction‐lift, peristaltic pump were employed in sampling both methane‐charged ground water for volatile aromatic hydrocarbons and a CO2‐charged reservoir water for volatile chlorinated hydrocarbons. In both cases, the suction‐lift pump produced samples with a significant negative bias (9 to 33 percent) relative to the other methods. Little difference between samples produced by the other pump Systems was noted at the field site, but in sampling the reservoir, the bladder pump produced samples that were 13 to 19 percent lower in halocarbon concentration than were samples from the momentum‐lift pump. These negative biases are tentatively interpreted as losses due to volatilization during sampling. Slightly greater negative biases occur for compounds of higher volatility as estimated from their Henry's law constants. Additional studies appear to be warranted in order to adequately establish the scientific basis for recommending protocols for sampling ground water in which degassing could enhance the loss of volatile organics during sampling.

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