Heijlen, Wouter7; Appel, P. W. U.8; Frezzotti, M. L.9; Horsewell, Andy5; Touret, J. L. R.6
1 Department of Management Engineering, Technical University of Denmark2 University of Leeds3 Geological Survey of Denmark and Greenland4 University of Siena5 Department of Mechanical Engineering, Technical University of Denmark6 Ecole de Mines7 University of Leeds8 Geological Survey of Denmark and Greenland9 University of Siena
Fluid inclusions in quartz globules and quartz veins of a 3.8-3.7 Ga old, well-preserved pillow lava breccia in the northeastern Isua Greenstone Belt (IGB) were studied using microthermometry, Raman spectrometry and SEM Cathodoluminescence Imaging. Petrographic study of the different quartz segregations showed that they were affected by variable recrystallization which controlled their fluid inclusion content. The oldest unaltered fluid inclusions found are present in vein crystals that survived dynamic and static recrystallization. These crystals contain a cogenetic, immiscible assemblage of CO2-rich (+H2O, +graphite) and brine-rich (+CO2, +halite, +carbonate) inclusions. The gas-rich inclusions have molar volumes between 44.8 and 47.5 cm(3)/Mol, while the brine inclusions have a salinity of similar to 33 eq. wt% NaCl. Modeling equilibrium immiscibility using volumetric and compositional properties of the endmember fluids indicates that fluid unmixing occurred at or near peak-metamorphic conditions of similar to 460 degrees C and similar to 4 kbar. Carbonate and graphite were precipitated cogenetically from the physically separated endmember fluids and were trapped in fluid inclusions. In most quartz crystals, however, recrystallization obliterated such early fluid inclusion assemblages and left graphite and carbonate as solid inclusions in recrystallized grains. Intragranular fluid inclusion trails in the recrystallized grains of breccia cementing and crosscutting quartz veins have CO2-rich assemblages, with distinctly different molar volumes (either between 43.7 and 47.5 cm(3)/mol or between 53.5 and 74.1 cm(3)/Mol), and immiscible, halite-saturated H2O-CO2-NaCl(-other salt) inclusions. Later intergranular trails have CH4-H-2 (X-H2 up to similar to 0.3) inclusions of variable density (ranging from 48.0 to > 105.3 cm(3)/Mol) and metastable H2O NaCl(-other salt?) brines (similar to 28 eq. wt% NaCl). Finally, the youngest fluid inclusion assemblages are found in non-luminescent secondary quartz and contain low-density CH4 (molar volume > 105.33 cm(3)/Mol) and low-salinity H2O-NaCl (0.2-3.7 eq. wt% NaCl.) These successive fluid inclusion assemblages record a retrograde P-T evolution close to a geothermal gradient of similar to 30 degrees C/km, but also indicate fluid pressure variations and the introduction of highly reducing fluids at similar to 200-300 degrees C and 0.5-2 kbar. The quartz globules in the pillow fragments only contain sporadic CH4(+H-2) and brine inclusions, corresponding with the late generations present in the cementing and crosscutting veins. We argue that due to the large extent of static recrystallization in quartz globules in the pillow breccia fragments, only these relatively late fluid inclusions have been preserved, and that they do not represent remnants of an early, seafloor-hydrothermal system as was previously proposed. Modeling the oxidation state of the fluids indicates a rock buffered system at peak-metamorphic conditions, but suggests a change towards fluid-graphite disequilibrium and a log fH(2)/f(H2O) above the Quartz-Fayalite-Magnetite buffer during retrograde evolution. Most likely, this indicates a control on redox conditions and on fluid speciation by ultramafic rocks in the IGB.
Geochimica Et Cosmochimica Acta, 2006, Vol 70, Issue 12, p. 3075-3095