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Peter J. Saccocia

Publications and source records attributed to Peter J. Saccocia.

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Oxygen and hydrogen isotope fractionation in serpentine-water and talc-water systems from 250 to 450 °C, 50 MPa

Oxygen and hydrogen isotope fractionation factors in the talc–water and serpentine–water systems have been determined by laboratory experiment from 250 to 450 °C at 50 MPa using the partial exchange technique. Talc was synthesized from brucite + quartz, resulting in nearly 100% exchange during reaction at 350 and 450 °C. For serpentine, D–H exchange was much more rapid than 18 O– 16 O exchange when natural chrysotile fibers were employed in the initial charge. In experiments with lizardite as the starting charge, recrystallization to chrysotile enhanced the rate of 18 O– 16 O exchange with the coexisting aqueous phase. Oxygen isotope fractionation factors in both the talc–water and serpentine–water systems decrease with increasing temperature and can be described from 250 to 450 °C by the relationships: 1000 ln = 11.70 × 10 6 /T 2 − 25.49 × 10 3 /T + 12.48 and 1000 ln = 3.49 × 10 6 /T 2 − 9.48 where T is temperature in Kelvin. Over the same temperature interval at 50 MPa, talc–water D–H fractionation is only weakly dependent on temperature, similar to brucite and chlorite, and can be described by the equation: 1000 ln = 10.88 × 10 6 /T 2 − 41.52 × 10 3 /T + 5.61 where T is temperature in Kelvin. Our D–H serpentine–water fractionation factors calibrated by experiment decrease with temperature and form a consistent trend with fractionation factors derived from lower temperature field calibrations. By regression of these data, we have refined and extended the D–H fractionation curve from 25 to 450 °C, 50 MPa as follows: 1000 ln = 3.436 × 10 6 /T 2 − 34.736 × 10 3 /T + 21.67 where T is temperature in Kelvin. These new data should improve the application of D–H and 18 O– 16 O isotopes to constrain the temperature and origin of hydrothermal fluids responsible for serpentine formation in a variety of geologic settings.

Geochimica et Cosmochimica Acta

Hydrogen and oxygen isotope fractionation between brucite and aqueous NaCl solutions from 250 to 450°C

Hydrogen and oxygen isotope fractionation factors between brucite and aqueous NaCl solutions (1000lnα br-sw ) have been calibrated by experiment from 250 to 450°C at 0.5 Kb. For D/H fractionation, 1000lnα br-sw values are as follows: −32 ± 6‰ (250°C, 3.2 wt% NaCl), −21 ± 2‰ (350°C, 10.0 wt% NaCl), and −22 ± 2‰ (450°C, 3.2 wt% NaCl), indicating that brucite is depleted in D relative to coexisting aqueous NaCl solutions. These results are in good agreement with previous D/H fractionation factors determined in the brucite-water system, indicating that any effects of dissolved salt on D/H fractionation are relatively small, particularly in solutions with near seawater salinity. The maximum salt effect (+4‰) was observed in 10.0 wt% NaCl solutions at 350°C, suggesting that the addition of dissolved NaCl increases the amount of deuterium fractionated into mineral structures. For 18 O/ 16 O fractionation, 1000lnα br-sw values in 3.0 wt% NaCl solutions are −6.0 ± 1.3‰, −5.6 ± 0.7‰ and −4.1 ± 0.2‰, at 250, 350, and 450°C, respectively, and −5.8 ± 0.6‰ in 10.0 wt % NaCl at 350°C. These data indicate that brucite is depleted in 18 O relative to coexisting aqueous NaCl solutions and that the degree of depletion decreases slightly with increasing temperature and is not strongly dependent on salinity. We calculated 18 O/ 16 O brucite-water fractionation factors from available calibrations of the salt-effect on 18 O/ 16 O fractionation between coexisting phases. The resulting values were fit to the following equation that is valid from 250 to 450°C 1000ln α br-w = 9.54 × 10 6 T −2 − 3.53 × 10 4 T −1 + 26.58 where T is temperature in Kelvins. These new data have been used to improve the prediction of 18 O/ 16 O fractionation factors in the talc-water and serpentine-water systems by modifying existing empirical bond-water models. The results of this analysis indicate that the δ 18 O composition of talc-brucite and serpentine-brucite pairs could be used as a geothermometer and that these coexisting phases should display the following order of 18 O enrichment: talc > serpentine > brucite.

Geochimica et Cosmochimica Acta