A. Halliday | USGS Science

USGS2002

Thallium isotope variations in seawater and hydrogenetic, diagenetic, and hydrothermal ferromanganese deposits

Results are presented for the first in-depth investigation of TI isotope variations in marine materials. The TI isotopic measurements were conducted by multiple collector-inductively coupled plasma mass spectrometry for a comprehensive suite of hydrogenetic ferromanganese crusts, diagenetic Fe-Mn nodules, hydrothermal manganese deposits and seawater samples. The natural variability of TI isotope compositions in these samples exceeds the analytical reproducibility (?? 0.05???) by more than a factor of 40. Hydrogenetic Fe-Mn crusts have ??205TI of + 10 to + 14, whereas seawater is characterized by values as low as -8 (??205TI represents the deviation of the 205TI/203TI ratio of a sample from the NIST SRM 997 TI isotope standard in parts per 104). This ~ 2??? difference in isotope composition is thought to result from the isotope fractionation that accompanies the adsorption of TI onto ferromanganese particles. An equilibrium fractionation factor of ?? ~ 1.0021 is calculated for this process. Ferromanganese nodules and hydrothermal manganese deposits have variable TI isotope compositions that range between the values obtained for seawater and hydrogenetic Fe-Mn crusts. The variability in ??205TI in diagenetic nodules appears to be caused by the adsorption of TI from pore fluids, which act as a closed-system reservoir with a TI isotope composition that is inferred to be similar to seawater. Nodules with ??205TI values similar to seawater are found if the scavenging of TI is nearly quantitative. Hydrothermal manganese deposits display a positive correlation between ??205TI and Mn/Fe. This trend is thought to be due to the derivation of TI from distinct hydrothermal sources. Deposits with low Mn/Fe ratios and low ??205TI are produced by the adsorption of TI from fluids that are sampled close to hydrothermal sources. Such fluids have low Mn/Fe ratios and relatively high temperatures, such that only minor isotope fractionation occurs during adsorption. Hydrothermal manganese deposits with high Mn/Fe and high ??205Ti are generated by scavenging of TI from colder, more distal hydrothermal fluids. Under such conditions, adsorption is associated with significant isotope fractionation, and this produces deposits with higher ??205TI values coupled with high Mn/Fe. ?? 2002 Elsevier Science B.V. All rights reserved.

Earth and Planetary Science Letters↗

USGS1998

Alteration and mineralization of an oceanic forearc and the ophiolite-ocean crust analogy

Mineralogical, chemical, and isotopic (O, C, S, and Sr) analyses were performed on minerals and bulk rocks from a forearc basement section to understand alteration processes and compare with mid-ocean ridges (MOR) and ophiolites. Ocean Drilling Program Hole 786B in the Izu-Bonin forearc penetrates 103 m of sediment and 725 m into volcanic flows, breccias, and basal dikes. The rocks comprise boninites and andesites to rhyolites. Most of the section was affected by low-temperature (<100°C) seawater alteration, with temperatures increasing downward. The rocks are partly (5–25%) altered to smectite, Fe-oxyhydroxide, calcite, and phillipsite, and exhibit gains of K, Rb, and P, loss of Ca, variable changes in Si, Na, Mg, Fe, Sr, and Y, and elevated δ 18 O and 87 Sr/ 86 Sr. Higher temperatures (∼150°C) in the basal dikes below 750 m led to more intense alteration and formation of chlorite-smectite, corrensite, albite, K-feldspar, and quartz (±chlorite). A 5 m thick hydrothermally altered and pyritized zone at 815 m in the basal dikes reacted with mixtures of seawater and hydrothermal fluids to Mg-chlorite, albite, and pyrite, and gained Mg and S and lost Si and Ca. Focused flow of hydrothermal fluids produced serialization halos (Na-K sericite, quartz, pyrophyllite, K-feldspar, and pyrite) along quartz veins at temperatures of 200°–250°C. High 87 Sr/ 86 Sr ratios of chloritized (∼0.7055) and sericitized (∼0.7065) rocks indicate involvement of seawater via mixing with hydrothermal fluids. Low δ 34 S of sulfide (−2 to −5.5‰) and sulfate (12.5‰) are consistent with input of magmatic SO 2 into hydrothermal fluids and disproportionation to sulfide and sulfate. Alteration processes were generally similar to those at MORs, but the arc section is more intensively altered, in part because of the presence of abundant glassy rocks and mafic phases. The increase in alteration grade below 750 m and the mineralization in the basal dikes are analogous to changes that occur near the base of the volcanic section in MOR and the Troodos ophiolite.

Journal of Geophysical Research B: Solid Earth↗