Experimental hydrogen isotope studies—I. Systematics of hydrogen isotope fractionation in the systems epidote-H2O,zoisite-H2O and AlO(OH)-H2O

$\text{H}\text{D}$ Fractionation factors between epidote minerals and water, and between the AlO(OH) dimorphs boehmite and diaspore and water, have been determined between 150 and 650°C. Small water mineral ratios were used to minimise the effect of incongruent dissolution of epidote minerals. Waters were extracted and analysed directly by puncturing capsules under vacuum. Hydrogen diffusion effects were eliminated by using thick-walled capsules.$\text{H}\text{D}$ Exchange rates are very fast between epidote and water (and between boehmite and water), complete exchange taking only minutes above 450°C but several months at 250°C. Exchange between zoisite and water (and between diaspore and water) is very much slower, and an interpolation method was necessary to determine fractionation factors at 450 and below.For the temperature range 300–650°C, the $\text{H}\text{D}$ equilibrium fractionation factor (α^e) between epidote and water is independent of temperature and Fe content of the epidote, and is given by 1000 In α_epidote-H2O^e = ?35.9 ± 2.5, while below 300°C 1000 In , with a ‘cross-over’ estimated to occur at around 185°C. By contrast, zoisite-water fractionations fit the relationship 1000 In .All studied minerals have hydrogen bonding. Fractionations are consistent with the general relationship: the shorter the O-H -- O bridge, the more depleted is the mineral in D.On account of rapid exchange rates, natural epidotes probably acquired their H-isotope compositions at or below 200°C, where fractionations are near or above 0%.; this is in accord with the observation that natural epidotes tend to concentrate D relative to other coexisting hydrous minerals.     

Isotopic geochemistry (O,Sr, Pb) of the Golda Zuelva and Mboutou anorogenic complexes,North Cameroun: mantle origin with evidence for crustal contamination

The annular (6–8 km diameter) Golda Zuelva and Mboutou anorogenic complexes of North Cameroun are composed of a suite of alkaline plutonic rocks ranging from olivine gabbro to amphibole and biotite granite. For the Mboutou complex there are two overlapping centres. In the Golda Zuelva complex the plutonic rocks are associated with a later hawaiite to rhyolite volcanic suite. A Rb/Sr whole rock isochron gives an age of 66±3 Ma for the Golda Zuelva granites, with initial⁸⁷Sr/⁸⁶Sr ratio of 0.7020, and demonstrates that plutonism and volcanism were essentially contemporaneous and probably cogenetic. For Golda Zuelva and the north Mboutou centre¹⁸O/¹⁶O (5.6–6.2),⁸⁷Sr/⁸⁶Sr (0.7030–0.7045) and Pb isotopic ratios (²⁰⁷Pb/²⁰⁴Pb: 15.60–15.64) support a mantle origin for the initial magmas. Unlike Sr isotopes, the O isotopic ratios of the granitic end members at Golda Zuelva (～7.5) indicate crustal contamination. Post-magmatic alteration was not significant.For the younger south Mboutou centre the O-, Sr- and Pb-isotopic data indicate more extensive magma-crust interaction and in a different (higher level?) crustal environment with δ¹⁸O granite=3.3‰,⁸⁷Sr/⁸⁶Sr ratios up to 0.706 and Pb isotopic ratios more markedly displaced from the oceanic volcanic field. The low-¹⁸O granites probably record, at least in part, a magmatic process with subsequent minor post-magmatic alteration effects. The major and trace element systematics between the north and south Mboutou centres are directly comparable. The evolution of the magmas were dominated by fractional crystallisation and progressive crustal contamination processes.     

Relationships between heavy metals and major cations along pollution gradients

Along some pollution gradients, animal tissue concentrations of several major, physiologically important cations vary greatly in a way that corresponds with levels of toxic metals. Changes in concentration from normal of these major cations can be as much as fourfold which may be an underlying cause of much of the stress experienced by these species in polluted environments.     

Fluid flow in cataclastic thrust fault zones in sandstones, Sub-Andean Zone, southern Bolivia

The Bolivian Sub-Andean Zone (SAZ) corresponds to a Neogene thrust system that affects an about 10-km thick Palaeozoic to Neogene siliciclastic succession. The analysis of macro and microstructures and cement distribution in thrust fault zones shows that they are sealed by quartz at depths >3 km, due to local silica transfer by pressure-solution/precipitation activated at temperatures >70–90 °C. At shallower depths, faults have remained open and could be preferential drains for lateral flow of carbonate-bearing fluids, as shown by the occurrence of carbonate cements in fractures and their host-sandstone. Due to decreasing burial, resulting from foothill erosion during fault activity, critically buried fault segments can be affected by non-quartz-sealed structures that post-date initial quartz-sealed structures. The integration of textural, fluid inclusion and isotopic data shows that carbonates precipitated at shallow depth (<3 km), low temperature (<80 °C) and relatively late during the thrusting history. Isotopic data also show that precipitation occurred from the mixing of gravity-driven meteoric water with deeper formation water bearing carbonate carbon derived from the maturation of hydrocarbon source rocks (Silurian and Devonian shales). The combined microstructural and isotopic analyses indicate that: (i) fluid flow in fault zones often occurred with successive pulses derived from different or evolving sources and probably related to episodic fault activity, and (ii) at a large-scale, the faults have a low transverse permeability and they separate thrust sheets with different fluid histories.     

Fluid-Rock Interaction in the Granulites of Madagascar and Lithospheric-Scale Transfer of Fluids

The nature of synmetamorphic fluids and their flow is examined in the granulitic lower crust of Madagascar, part of a Precambrian crustal-scale network of vertical ductile shear zones. Based on three independent data sets - field and satellite mapping, C-, O- and H-isotope geochemistry and gravimetry - this crust is divided into three zones: outside of shear zones, minor shear zones (<140 km long and 7 km wide), and major shear zones (>350 km long and 20–35 km wide). The major shear zones are rooted in and are controlled by the mantle. They tapped mantle-derived CO₂ with carbon fluxes of the same order of magnitude as oceanic ridge degassing. One major shear zone shows abundant phlogopite-diopside-apatite-calcite mineralizations (a well known paragenesis in mantle metasomatism) due to mantle-fluid infiltration and their interaction with the crust. Carbonatitic magmas possibly collected in the major shear zones at the base of the crust and may be the source for CO₂ upwellings as well as other metasomatic agents. Small-scale minor shear zones were controlled by crustal deformation processes and focused crustally-derived H₂O-rich fluids. Pervasive fluid circulation was restricted to the vicinity (< 100 m) of synmetamorphic plutons. Fluid absent conditions dominate everywhere else. Mantle-CO₂ flushing is not required for granulite genesis but is a consequence of the high associated heat flux. Fluid transfer at the mantle/crust interface is controlled by the tectonic setting and the associated geothermal gradient. The C- and O- isotope systematics of metamorphosed carbonates sampled on a regional scale within a known petrological and structural framework are shown to be of great help to identify the distribution of major fluid-rock interaction processes associated with plate tectonics.