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Groundwaters were collected around the Spence porphyry copper deposit, Atacama Desert, northern Chile, to study water-porphyry copper ore bodies interaction and test hypotheses regarding transport of metals through thick overburden leading to the formation of soil geochemical anomalies. The deposit contains 400 Mt of 1% Cu and is completely buried by piedmont gravels of Miocene age. Groundwaters were recovered from the eastern up hydraulic gradient (upflow) margin of the Spence deposit, from within the deposit, and for two kilometers down flow from the deposit. Water table depths decrease from 90 m at the upflow margin to 30 m 1.5 km down flow. Groundwaters at the Spence deposit are compositionally variable with those upflow of the deposit characterized by relatively low salinities (900-7000 mg/L) and Na+-SO42--type compositions. These waters have compositions and stable isotope values similar to regional groundwaters recovered elsewhere in the Atacama Desert of Northern Chile. In contrast, groundwaters recovered within and down flow of the deposit range in salinity from 10,000 to 55,000 mg/L (one groundwater at 145,000 mg/L) and are dominantly Na+-Cl--type waters. Dissolved sulfate values are, however, elevated compared to upflow waters, and delta S-34(CDT) decreases into the deposit (from > 4 parts per thousand to 2 parts per thousand), consistent with increasing influence of sulfur derived from oxidation of sulfide minerals within the deposit. The increase in salinity and conservative tracers (Cl-, Br-, Li+, and Na+) and the relationship between oxygen and hydrogen isotopes suggests that in addition to water-rock reactions within the deposit, most of the compositional variation can be explained by groundwater mixing (with perhaps a minor role for evaporation). A groundwater-mixing scenario implies a deeper, more saline groundwater source mixing with the less saline regional groundwater-flow system. Flow of deeper, more saline groundwater along pre-existing structures has important implications for geochemical exploration and metal-transport models. (c) 2005 Elsevier Inc. All rights reserved.