H.P. Taylor | USGS Science

USGS1996

Oxygen isotopic and geochemical evidence for a short-lived, high-temperature hydrothermal event in the Chegem caldera, Caucasus Mountains, Russia

Within the 2.8 Ma Chegem ash-flow caldera (11 ?? 15 km), a single cooling unit of rhyolitic to dacitic welded tuff more than 2 km thick is exposed in deep valleys incised during recent rapid uplift of the Caucasus Mountains. The intracaldera tuff is mineralogically fresh and unaltered, and is overlain by andesite lavas and cut by a resurgent granodiorite intrusion. Major- and trace-element compositions for a 1405-m stratigraphic section of intracaldera tuff display trends of upwardly increasing Na2O, CaO, Al2O3, total Fe, MgO, TiO2, Sr and Zr and decreasing SiO2, K2O and Rb. This mafic-upward zoning (from 76.1 to 69.9% SiO2) reflects an inverted view of the upper part of the source magma chamber. Oxygen isotope studies of 35 samples from this 1405-m section define a striking profile with "normal" igneous ??18O values (+7.0 to +8.5) in the lower 600 m of tuff, much lower ??18O values (-4.0 to +4.3) in a 700-m zone above that and a shift to high ??18O values (+4.4 to -10.9) in the upper 100 m of caldera-fill exposure. Data from two other partial stratigraphic sections indicate that these oxygen isotope systematics are probably a caldera-wide phenomenon. Quartz and feldspar phenocrysts everywhere have "normal" igneous ??18O values of about +8.5 and +7.5, respectively, whereas groundmass and glass ??18O values range from -7.7 to +12.3. Consequently, the ??18O values of coexisting feldspar, groundmass and glass form a steep array in a plot of ??feldspar vs. ??groundmass/glass. Such pronounced disequilibrium between coexisting feldspar and groundmass or glass has never before been observed on this scale. It requires a hydrothermal event involving large amounts of low-18O H2O at sufficiently high temperatures and short enough time (tens of years or less) that glass exchanges thoroughly but feldspar does not. The most likely process responsible for the O depletions at Chegem is a very high temperature (500-600??C), short-lived, vigorous meteoric-hydrothermal event that was focused within the upper 750 m of intracaldera tuff. Mass balance calculations indicate fluid fluxes of = 6 ?? 10-6 mol cm-2 s-1. We believe that the closest historical analogue to this Chegem hydrothermal event is the situation observed in the Valley of Ten Thousand Smokes (Alaska, USA), where hundreds of steam fumaroles with measured temperatures as high as 645??C persisted for 10 to 15 years in the much smaller welded ash-flow tuff sheet (??? 200 m thick) produced by the 1912 Katmai eruption.

Journal of Volcanology and Geothermal Research↗

USGS1989

Oxygen isotope exchange kinetics of mineral pairs in closed and open systems: Applications to problems of hydrothermal alteration of igneous rocks and Precambrian iron formations

The systematics of stable-isotope exchange between minerals and fluids are examined in the context of modal mineralogical variations and mass-balance considerations, both in closed and in open systems. On mineral-pair ??18O plots, samples from terranes that have exchanged with large amounts of fluid typically map out steep positively-sloped non-equilibrium arrays. Analytical models are derived to explain these effects; these models allow for different exchange rates between the various minerals and the external fluids, as well as different fluid fluxes. The steep arrays are adequately modelled by calculated isochron lines that involve the whole family of possible exchange trajectories. These isochrons have initially-steep near-vertical positive slopes that rotate toward a 45?? equilibrium slope as the exchange process proceeds to completion. The actual data-point array is thus analogous to the hand of an "isotopic clock" that measures the duration of the hydrothermal episode. The dimensionless ratio of the volumetric fluid flux to the kinetic rate parameter ( u k) determines the shape of each individual exchange trajectory. In a fluid-buffered system ( u k ??? 1), the solutions to the equations: (1) are independent of the mole fractions of the solid phases; (2) correspond to Taylor's open-system water/rock equation; and (3) yield straight-line isochrons that have slopes that approach 1 f, where f is the fraction reacted of the more sluggishly exchanging mineral. The isochrons for this simple exchange model are closely congruent with the isochrons calculated for all of the more complex models, thereby simplifying the application of theory to actual hydrothermal systems in nature. In all of the models an order of magnitude of time (in units of kt) separates steep non-equilibrium arrays (e.g., slope ??? 10) from arrays approaching an equilibrium slope of unity on a ??-?? diagram. Because we know the approximate lifetimes of many hydrothermal systems from geologic and heat-balance constraints, we can utilize the 18O 16O data on natural mineral assemblages to calculate the kinetic rate constants (k's) and the effective diffusion constants (D's) for mineral-H2O exchange: these calculated values (kqtz ??? 10-14, kfeld ??? 10-13-10-12) agree with experimental determinations of such constants. In nature, once the driving force or energy source for the external infiltrating fluid phase is removed, the disequilibrium mineral-pair arrays will either: (1) remain "frozen" in their existing state, if the temperatures are low enough, or (2) re-equilibrate along specific closed-system exchange vectors determined solely by the temperature path and the mineral modal proportions. Thus, modal mineralogical information is a particularly important parameter in both the open- and closed-system scenarios, and should in general always be reported in stable-isotopic studies of mineral assemblages. These concepts are applied to an analysis of 18O 16O systematics of gabbros (Plagioclase-clinopyroxene and plagioclase-amphibole pairs), granitic plutons (quartz-feldspar pairs), and Precambrian siliceous iron formations (quartz-magnetite pairs). In all these examples, striking regularities are observed on ??-?? and ??-?? plots, but we point out that ??-?? plots have many advantages over their equivalent ??-?? diagrams, as the latter are more susceptible to misinterpretation. Using the equations developed in this study, these regularities can be interpreted to give semiquantitative information on the exchange histories of these rocks subsequent to their formation. In particular, we present a new interpretation indicating that Precambrian cherty iron formations have in general undergone a complex fluid exchange history in which the iron oxide (magnetite precursor?) has exchanged much faster with low-temperature (< 400??C) fluids than has the relatively inert quartz. ?? 1989.

Chemical Geology↗

USGS1987

Kinetic theory of oxygen isotopic exchange between minerals and water

Kinetic and mass conservation equations are used to describe oxygen isotopic exchange between minerals and water in "closed" and open hydrothermal systems. In cases where n coexisting mineral phases having different reaction rates are present, the exchange process is described by a system of n + 1 simultaneous differential equations consisting of n pseudo first-order rate equations and a conservation of mass equation. The simultaneous solutions to these equations generate curved exchange trajectories on ??-?? plots. Families of such trajectories generated under conditions allowing for different fluid mole fractions, different fluid isotopic compositions, or different fluid flow rates are connected by positive-sloped isochronous lines. These isochrons reproduce the effects observed in hydrothermally exchanged mineral pairs including 1) steep positive slopes, 2) common reversals in the measured fractionation factors (??), and 3) measured fractionations that are highly variable over short distances where no thermal gradient can be geologically demonstrated. ?? 1987.

Geochimica et Cosmochimica Acta↗