Oxygen and hydrogen isotope fractionation in serpentine–water and talc–water systems from 250 to 450°C 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 18O–16O 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 18O–16O 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 × 106/T2 − 25.49 × 103/T + 12.48 and 1000 ln = 3.49 × 106/T2 − 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 × 106/T2 − 41.52 × 103/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 × 106/T2 − 34.736 × 103/T + 21.67 where T is temperature in Kelvin. These new data should improve the application of D–H and 18O–16O isotopes to constrain the temperature and origin of hydrothermal fluids responsible for serpentine formation in a variety of geologic settings

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 (1000lnαbr-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 18O/16O fractionation, 1000lnαbr-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 18O 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 18O/16O brucite-water fractionation factors from available calibrations of the salt-effect on 18O/16O fractionation between coexisting phases. The resulting values were fit to the following equation that is valid from 250 to 450°C 1000ln αbr-w = 9.54 × 106T−2 − 3.53 × 104T−1 + 26.58 where T is temperature in Kelvins. These new data have been used to improve the prediction of 18O/16O 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 δ18O 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 18O enrichment: talc \u3e serpentine \u3e brucite

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

Author Posting. © The Author(s), 2009. This is the author's version of the work. It is posted here by permission of Elsevier B.V. for personal use, not for redistribution. The definitive version was published in Geochimica et Cosmochimica Acta 73 (2009): 6789-6804, doi:10.1016/j.gca.2009.07.036.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 18O-16O 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 18O-16O exchange with the coexisting aqueous phase.This work was supported by NSF Grants OCE-9313980 to the Woods Hole Oceanographic Institution and OCE-9820287 to Bridgewater State College (BSC)

Geochemistry of hydrothermal fluids from the PACMANUS, Northeast Pual and Vienna Woods hydrothermal fields, Manus Basin, Papua New Guinea

Processes controlling the composition of seafloor hydrothermal fluids in silicic back-arc or near-arc crustal settings remain poorly constrained despite growing evidence for extensive magmatic–hydrothermal activity in such environments. We conducted a survey of vent fluid compositions from two contrasting sites in the Manus back-arc basin, Papua New Guinea, to examine the influence of variations in host rock composition and magmatic inputs (both a function of arc proximity) on hydrothermal fluid chemistry. Fluid samples were collected from felsic-hosted hydrothermal vent fields located on Pual Ridge (PACMANUS and Northeast (NE) Pual) near the active New Britain Arc and a basalt-hosted vent field (Vienna Woods) located farther from the arc on the Manus Spreading Center. Vienna Woods fluids were characterized by relatively uniform endmember temperatures (273–285 °C) and major element compositions, low dissolved CO2 concentrations (4.4 mmol/kg) and high measured pH (4.2–4.9 at 25 °C). Temperatures and compositions were highly variable at PACMANUS/NE Pual and a large, newly discovered vent area (Fenway) was observed to be vigorously venting boiling (358 °C) fluid. All PACMANUS fluids are characterized by negative δDH2O values, in contrast to positive values at Vienna Woods, suggesting substantial magmatic water input to circulating fluids at Pual Ridge. Low measured pH (25 °C) values (∼2.6–2.7), high endmember CO2 (up to 274 mmol/kg) and negative δ34SH2S values (down to −2.7‰) in some vent fluids are also consistent with degassing of acid-volatile species from evolved magma. Dissolved CO2 at PACMANUS is more enriched in 13C (−4.1‰ to −2.3‰) than Vienna Woods (−5.2‰ to −5.7‰), suggesting a contribution of slab-derived carbon. The mobile elements (e.g. Li, K, Rb, Cs and B) are also greatly enriched in PACMANUS fluids reflecting increased abundances in the crust there relative to the Manus Spreading Center. Variations in alkali and dissolved gas abundances with Cl at PACMANUS and NE Pual suggest that phase separation has affected fluid chemistry despite the low temperatures of many vents. In further contrast to Vienna Woods, substantial modification of PACMANUS/NE Pual fluids has taken place as a result of seawater ingress into the upflow zone. Consistently high measured Mg concentrations as well as trends of increasingly non-conservative SO4 behavior, decreasing endmember Ca/Cl and Sr/Cl ratios with increased Mg indicate extensive subsurface anhydrite deposition is occurring as a result of subsurface seawater entrainment. Decreased pH and endmember Fe/Mn ratios in higher Mg fluids indicate that the associated mixing/cooling gives rise to sulfide deposition and secondary acidity production. Several low temperature (⩽80 °C) fluids at PACMANUS/NE Pual also show evidence for anhydrite dissolution and water–rock interaction (fixation of B) subsequent to seawater entrainment. Hence, the evolution of fluid compositions at Pual Ridge reflects the cumulative effects of water/rock interaction, admixing and reaction of fluids exsolved from silicic magma, phase separation/segregation and seawater ingress into upflow zones

Hydrothermal sediment alteration at a seafloor vent field: Grimsey Graben, Tjörnes Fracture Zone, north of Iceland

An active seafloor hydrothermal system subjects the background sediments of the Grimsey Graben (Tjörnes Fracture Zone) to alteration that produces dissolution of the primary volcaniclastic matrix and replacement/precipitation of sulfides, sulfates, oxides, oxyhydroxides, carbonates and phyllosilicates. Three types of hydrothermal alteration of the sediment are defined on the basis of the dominant hydrothermal phyllosilicate formed: smectite, kaolinite, chlorite. The most common alteration is near‐total conversion of the volcaniclastic material to smectite (95–116°C). The dominant smectite in the deepest sediments sampled is beidellite, which is replaced by montmorillonite and an intimate mixture of di‐ and tri‐octahedral smectite up core. This gradual vertical change in smectite composition suggests an increase in the Mg supply upward, the result of sediment alteration by the ascending hydrothermal fluids mixing with descending seawater. The vertical sequence kaolinite → kaolinite‐smectite mixed‐layer → smectite from bottom to top of a core, as well as the distinct zonation across the veins (kaolinite in the central zone → kaolinite‐smectite in the rim), suggests hydrothermal transformation of the initially formed smectite to kaolinite through kaolinite‐smectite mixed‐layer (150–160°C). The cause of this transformation might have been an evolution of the fluids toward a slightly acidic pH or a relative increase in the Al concentration. Minor amounts of chamosite fill thin veins in the deepest sections of some cores. The gradual change from background clinochlore to chamosite across the veins suggests that chamosite replaces clinochlore as Fe is made available from hydrothermal dissolution of detrital Fe‐containing minerals. The internal textures, REE distribution patterns and the mode of occurrence of another magnesian phyllosilicate, kerolite, suggest that this mineral is the primary precipitate in the hydrothermal chimneys rather than an alteration product in the sediment. Kerolite precipitated after and grew on anhydrite in the chimneys. Oxygen isotope ratios are interpreted to reflect precipitation of kerolite at temperatures of 302° to 336°C. It accumulated in the hydrothermal mounds following the collapse of the chimneys and subsequent dissolution of anhydrite, thereby forming highly permeable aquifer layers underlying the vent field. Some kerolite was redeposited in the near vent field sediments by turbidity flows. The altered sediments are depleted in Mn, Rb and Sr, and enriched in U, Mo, Pb, Ba, As, Bi, Sb, Ag, Tl and Ga, as a result of leaching and precipitation, respectively. Conservative elements (Ti, Zr, Hf, Sc, Cr, Nb and Sn) are depleted or enriched in the altered sediments because of passive (precipitation or leaching of other phases) rather than active (because of their mobility) processes

Poster: Exploring the Seafloor-Hot Springs in Back Arc Basins

This is an oral presentation that will describe my research results from work I performed last summer as part of a major oceanographic expedition to the Manus Basin in the western Pacific Ocean. The research was sponsored and supported by both the Woods Hole Oceanographic Institution and CART

Hydrothermal Fluid Chemistry in Back Arc Basins

Hot springs emanate from the seafloor along the global mid-ocean ridge system and in an environment called the back-arc basin. The chemistry of these fluids in the back-arc environment is virtually unknown. In general, hot springs on the seafloor cause a massive amount of chemical exchange between seawater and rocks below the seafloor. Thus, they exert a critical control on the chemistry of seawater and perhaps the development of major metal deposits such as copper and gold on the seafloor. To assess the role that hot springs in the back-arc environment play in these global processes requires that the chemistry of these fluids be known. Thus, the objective of this project is to measure the chemistry of hot spring fluids from a back-arc basin in the western Pacific Ocean. From these measurements, the origin and global significance of these hot springs will be determined

Aqueous volatiles in hydrothermal fluids from the Main Endeavour Field, northern Juan de Fuca Ridge: temporal variability following earthquake activity

The Main Endeavour Field, northern Juan de Fuca Ridge, experienced intense seismic activity in June 1999. Hydrothermal vent fluids were collected from sulfide structures in September 1999 and July 2000 and analyzed for the abundance of H2, H2S, CH4, CO2, NH3, Mg and Cl to document temporal and spatial changes following the earthquakes. Dissolved concentrations of CO2, H2, and H2S increased dramatically in the September 1999 samples relative to pre-earthquake abundances, and subsequently decreased during the following year. In contrast, dissolved NH3 and CH4 concentrations in 1999 and 2000 were similar to or less than pre-earthquake values. Aqueous Cl abundances showed large decreases immediately following the earthquakes followed by increases to near pre-earthquake values. The abundances of volatile species at the Main Endeavour Field were characterized by strong inverse correlations with chlorinity. Phase separation can account for 20–50% enrichments of CO2, CH4, and NH3 in low-chlorinity fluids, while temperature- and pressure-dependent fluid–mineral equilibria at near-critical conditions are responsible for order of magnitude greater enrichments in dissolved H2S and H2. The systematic variation of dissolved gas concentrations with chlorinity likely reflects mixing of a low-chlorinity volatile-enriched vapor generated by supercritical phase separation with a cooler gas-poor hydrothermal fluid of seawater chlorinity. Decreased abundances of sediment-derived NH3 and CH4 in 1999 indicate an earthquake-induced change in subsurface hydrology. Elevated CO2 abundances in vent fluids collected in September 1999 provide evidence that supports a magmatic origin for the earthquakes. Temperature–salinity relationships are consistent with intrusion of a shallow dike and suggest that the earthquakes were associated with movement of magma beneath the ridge crest. These data demonstrate the large and rapid response of chemical fluxes at mid-ocean ridges to magmatic activity and associated changes in subsurface temperature and pressure

Integrating Writing into the Science Classroom

Often the math and science classroom is not a place where undergraduate students expect to write, but the writing across the curriculum (WAC) program is working to change student expectations. As part of the WAC Network initiative, faculty in math, science, and other disciplines completed a full-day WAC workshop to bring more writing activities to the classroom. In this workshop, faculty from physics, earth sciences, and biomechanics share their recent experiences integrating more writing assignments into their courses. Professor Kling will report on the results of a CART summer 2007 grant that was used to develop “Writing to Learn” labs in physics where the lab experience is structured around writing assignments. Bring a pen and paper: writing is required