Zebra dolomitization as a result of focused fluid flow in the Rocky Mountains Fold and Thrust Belt, Canada

Discordant zebra dolomite bodies occur locally in the Middle Cambrian Cathedral and Eldon Formations of the Main Ranges of the Canadian Rocky Mountains Fold and Thrust Belt. They are characterized by alternating dark grey (a) and white (b) bands, forming an ‘abba’ diagenetic cyclicity. These bands developed parallel to both bedding and cleavage. Dark grey (a) bands consist of fine (< 300 μm) non-planar crystalline impure dolomite. The white (b) bands are composed of coarse (up to several millimetres) milky-white pure saddle dolomites (b1) which are often covered by pore-lining zoned dolomite (b2). The b phases often possess a saddle-shaped morphology. In contrast to the replacement origin of the a dolomite, the zoned b2 dolomite rims are interpreted as a cement formed in open cavities. The b1 dolomite is interpreted as the result of recrystallization with diagenetic leaching of non-carbonate components. All the zebra dolomites studied are (nearly) stoichiometric and are characterized by enriched Na and depleted Sr concentrations. Fe and Mn concentrations in these dolomites differ depending on the sample locality. Fluid inclusion data indicate that the dolomites formed from relatively hot (T_H = 130–200 °C), saline (20–23 wt% CaCl₂ eq.) fluids. A diagenetic high temperature origin is also supported by depleted δ¹⁸O values (−20 to −14‰ VPDB). A contribution of ⁸⁷Sr-enriched fluids is reflected in the ⁸⁷Sr/⁸⁶Sr values (0·7091–0·7123). Zebra dolomite development is explained by focused fluid flow, which exploited areas of structural weaknesses (e.g. basin-platform, rim areas, faults, etc.). Expulsion of hot basinal brines in a tectonically active regime generated overpressures, which explains the development of secondary porosity during zebra dolomitization as well as the intra-zebra fracturing at decimetre to micrometre scale.     

Preferential embrittlement of graphitic schists during extensional unroofing in the Alps: the effect of fluid composition on rheology in low-permeability rocks

Interlayered graphitic and non‐graphitic schists from the Tauern Window, Eastern Alps, record contrasting mechanical behaviour during extensional exhumation. Graphitic schists contain mesoscale extension fractures, pervasive microcracks in garnet, and abundant secondary fluid inclusion planes; all three types of structures are oriented perpendicular to the stretching lineation. Crack spacings in garnet from graphitic samples are tightly clustered around a mean of 180 μm. Non‐graphitic schists have fewer and more randomly oriented microcracks and fluid inclusion planes and maintained strain compatibility via crystal plasticity. The presence or absence of graphite appears to have exerted a fundamental control on rheology during unroofing. Calculations for a model graphitic rock at 500 °C and f_O2 = 10^?24 MPa show that the equilibrium metamorphic fluid evolves from X_CO2 = 0.07 to 0.38 during decompression from 700 to 400 MPa, in agreement with microcrack fluid inclusion data that show a change from X_CO2 < 0.1 to 0.45 in graphitic samples over the same pressure interval. This compositional shift results in >60% expansion of the pore fluid during decompression. H₂O‐rich fluid in non‐graphitic rocks expands <15% over the same pressure interval. The greater pore fluid expansion in low‐permeability graphitic horizons likely promoted tensile failure during unroofing. These results suggest that microcracking should be an inevitable consequence of decompression in many graphitic schists, whereas rocks that lack graphite are less likely to undergo microcracking. Microseismicity is predicted to be more common in graphitic than non‐graphitic rocks during unroofing of mountain belts.     

Determination of Lithium, Beryllium and Boron at Trace Levels by Laser Ablation-Inductively Coupled Plasma-Sector Field Mass Spectrometry

The analytical capabilities of laser ablation (LA)-ICP-MS in determining Li, Be and B at trace levels in geological samples have been tested on a series of glass reference materials and natural samples. The LA-ICP-MS instrument used consisted of a sector-field ICP-MS coupled with a laser ablation microprobe operating at either 266 or 213 nm wavelength. Reference glasses from NIST (SRM 612, 614 and 616) and MPI-DING (KL2-G, ML3B-G, StHs6/80-G, GOR128-G, GOR132-G, T1-G and ATHO-G) were selected to develop the analytical method and to assess the best instrumental configuration. A series of calcic amphiboles with different Li, Be and B concentrations were also analysed using both LA-ICP-MS and SIMS to test the applicability of the method to natural minerals. Results indicated that with a spot size of 40 μm the agreement between measured and reference values of Li, Be and B is generally better than 10% for NIST SRM 612 and 20% for NIST SRM 614. Average reproducibility at the 2s level was 10% for Li, 20% for Be and 15% for B. Limits of detection were approximately 100 ng g^-1 for Be and B and 200 ng g^-1 for Li. These results were confirmed by analyses carried out on natural amphiboles and compared well in terms of precision and accuracy with those commonly achieved by SIMS.     

Hydrothermal Quartz Vein Formation, Revealed by Coupled SEM-CL Imaging and Fluid Inclusion Microthermometry: Shuteen Complex, South Gobi, Mongolia

Abstract. Scanning electron microscopy-cathodoluminescence (SEM-CL) imaging of vein quartz in the Cu-mineralised, Shuteen Complex (South Gobi, Mongolia) has revealed a complex history of crystal growth, dissolution and microfracture healing, associated with several hydrothermal events that could not be detected using other observational techniques (e.g. transmitted/reflected light microscopy, back-scattered electron imaging, or secondary electron imaging).
The quartz initially grew as CL-bright/grey crystals in a 345±30C liquid reservoir, as inferred by the analysis of primary liquid fluid inclusions (average Th of 343C; 6.6∼7.7 wt% NaCl_eq). Quartz precipitation occurred at the edge of the crystals as reservoir fluids cooled to 260±25C, as indicated by micron-scale CL-dark/CL-bright quartz growth bands containing abundant fluid inclusions (with an average T_h values of 261C). Pressure fluctuations were the likely cause of dissolution, as SEM-CL imaging reveals the quartz have corroded or rounded crystal edges, and precipitation of later quartz into open space. SEM-CL imaging shows the quartz contains healed microfractures that trapped low salinity fluids (3.9 wt% NaC1_eq) with Th values of 173±15C.
SEM-CL imaging provides a means of deciphering the thermal and chemical evolution of the fossil Shuteen hydrothermal system, and the nature of hydrothermal quartz vein-forming processes, by facilitating the correlation of distinct fluid inclusion populations and their relative chronology, with specific hydrothermal events.     

Primary Ore Mineral Assemblage and Fluid Inclusion Study of the Batu Hijau Porphyry Cu-Au Deposit, Sumbawa, Indonesia

Abstract. The Batu Hijau porphyry Cu‐Au deposit, Sumbawa Island, Indonesia, is associated with a tonalitic intrusive complex. The temperature‐pressure condition of mineralization at the Batu Hijau deposit is discussed on the basis of fluid inclusion microthermometry. Then, the initial Cu‐Fe sulfide mineral assemblage is discussed. Bornite and chalcopyrite are major copper ore minerals associated with quartz veinlets. The quartz veinlets have been classified into ‘A’ veinlets associated with bornite, digenite, chalcocite and chalcopyrite, ‘B’ veinlets having chalcopyrite bornite along vuggy center‐line, rare ‘C’ chalcopyrite‐quartz veinlets, and late ‘D’ veinlets consisting of massive pyrite and quartz (Clode et al., 1999). Copper and gold mineralization is associated with abundant ‘A’ quartz veinlets. Abundant fluid inclusions are found in veinlet quartz consisting mainly of gas‐rich inclusions and polyphase inclusions throughout the veinlet types. The hydrothermal activity occurred in temperature‐pressure conditions of aqueous fluid immiscibility into hypersaline brine and dilute vapor. The halite dissolution (Tm[halite]) and liquid‐vapor homogenization (Th) temperatures of the polyphase inclusions in veinlet quartz range from 270 to 472d?C and from 280 to 454d?C, respectively. The estimated salinity ranges from 36 to 47 wt% (NaCl equiv.). The apparent pressures lower than 300 bars are estimated to have been along the liquid‐vapor‐halite curve for the fluid inclusions having the Th lower than the Tm that trapped the brine saturated with halite, or at slightly higher pressure relative to liquid‐vapor‐halite curve for the fluid inclusions having the Th higher than the Tm that trapped the brine unsaturated with halite. The actual temperature and pressure during the hydrothermal activity at the Batu Hijau deposit are estimated to have been around 300d?C and 50 bars. At such temperature‐pressure conditions, the principal and initial Cu‐Fe sulfide mineral assemblages are thought to be chalcopyrite + bornite solid solution (bnss) for the chalcopyrite‐bearing assemblage, and chalcocite‐digenite solid solution and bnss for the chalcopyrite‐free assemblage.     

Evolution of Hydrothermal System at the Dizon Porphyry Cu-Au Deposit, Zambales, Philippines

Abstract. Evolution of hydrothermal system from initial porphyry Cu mineralization to overlapping epithermal system at the Dizon porphyry Cu‐Au deposit in western central Luzon, Zambales, Philippines, is documented in terms of mineral paragen‐esis, fluid inclusion petrography and microthermometry, and sulfur isotope systematics. The paragenetic stages throughout the deposit are summarized as follows; 1) stockwork amethystic quartz veinlets associated with chalcopyrite, bornite, magnetite and Au enveloped by chlorite alteration overprinting biotite alteration, 2) stockwork quartz veinlets with chalcopyrite and pyrite associated with Au and chalcopyrite and pyrite stringers in sericite alteration, 3) stringer quartz veinlets associated with molybdenite in sericite alteration, and 4) WNW‐trending quartz veins associated with sphalerite and galena at deeper part, while enargite and stibnite at shallower levels associated with advanced argillic alteration. Chalcopyrite and bornite associated with magnetite in quartz veinlet stockwork (stage 1) have precipitated initially as intermediate solid solution (iss) and bornite solid solution (bnss), respectively. Fluid inclusions in the stockwork veinlet quartz consist of gas‐rich inclusions and polyphase inclusions. Halite in polyphase inclusions dissolves at temperatures ranging from 360d?C to >500d?C but liquid (brine) and gas (vapor) do not homogenize at <500d?C. The maximum pressure and minimum temperature during the deposition of iss and bnss with stockwork quartz veinlets are estimated to be 460 bars and 500d?C. Fluid inclusions in veinlet stockwork quartz enveloped in sericite alteration (stage 2) consist mainly of gas‐rich inclusions and polyphase inclusions. In addition to the possible presence of saturated NaCl crystals at the time of entrapment of fluid inclusions that exhibit the liquid‐vapor homogenization temperatures lower than the halite dissolution temperatures in some samples, wide range of temperatures of halite dissolution and liquid‐vapor homogenization of polyphase inclusions from 230d?C to >500d?C and from 270d?C to >500d?C, respectively, suggests heterogeneous entrapment of gaseous vapor and hypersaline brine. The minimum pressure and temperature are estimated to be about 25 bars and 245d?C. Fluid inclusions in veinlet quartz associated with molybdenite (stage 3) are dominated by gas‐rich inclusions accompanied with minor liquid‐rich inclusions that homogenize at temperatures between 350d?C and 490d?C. Fluid inclusions in vuggy veinlet quartz associated with stibnite (stage 4) consist mainly of gas‐rich inclusions with subordinate polyphase inclusions that do not homogenize below 500d?C. Fluid inclusions in veinlet quartz associated with galena and sphalerite (stage 4) are composed of liquid‐rich two‐phase inclusions, and they homogenize into liquid phase at temperatures ranging widely from 190d?C to 300d?C (suggesting boiling) and the salinity ranges from 1.0 wt% to 3.4 wt% NaCl equivalent. A pressure of about 15 bars is estimated for the dilute aqueous solution of 190d?C from which veinlet quartz associated with galena and sphalerite precipitated. In addition to a change in temperature‐pressure regime from lithostatic pressure during the deposition of iss and bnss with stockwork quartz veinlets to hydrostatic pressure during fracture‐controlled quartz veinlet associated with galena and sphalerite, a decrease in pressure is supposed to have occurred due to unroofing or removal of the overlying piles during the temperature decrease in the evolution of hydrothermal system. The majority of the sulfur isotopic composition of sulfides ranges from ±0 % to +5 %. Sulfur originated from an iso‐topically uniform and homogeneous source, and the mineralization occurred in a single hydrothermal system.     

Origin and evolution of Pliocene–Pleistocene granites from the Larderello geothermal field (Tuscan Magmatic Province, Italy)

Extensive, mainly acidic peraluminous magmatism affected the Tuscan Archipelago and the Tuscan mainland since late Miocene, building up the Tuscan Magmatic Province (TMP) as the Northern Apennine fold belt was progressively thinned, heated and intruded by mafic magmas. Between 3.8 and 1.3 Ma an intrusive complex was built on Larderello area (Tuscan mainland) by emplacement of multiple intrusions of isotopically and geochemically distinct granite magmas. Geochemical and isotopic investigations were carried out on granites cored during drilling exploration activity on the Larderello geothermal field. With respect to the other TMP granites the Larderello intrusives can be classified as two-mica granites due to the ubiquitous presence of small to moderate amounts of F-rich magmatic muscovite. They closely resemble the almost pure crustal TMP acidic rocks and do not show any of the typical petrographic features commonly observed in the TMP hybrid granites (enclaves, patchy zoning of plagioclase, amphibole clots). On the basis of major and trace elements, as well as REE patterns, two groups of granites were proposed: LAR-1 granites (3.8–2.3 Ma) originated by biotite-muscovite breakdown, and LAR-2 granites (2.3–1.3 Ma) generated by muscovite breakdown. At least three main crustal sources (at 14–23 km depth), characterized by distinct ε_Nd(t) and ⁸⁷Sr/⁸⁶Sr values, were involved at different times, and the magmas produced were randomly emplaced at shallow levels (3–6 km depth) throughout the entire field. The partial melting of a biotite-muscovite-rich source with low ε_Nd(t) value (about −10.5) produced the oldest intrusions (about 3.8–2.5 Ma). Afterwards (2.5–2.3 Ma), new magmas were generated by another biotite-rich source having a distinctly higher ε_Nd(t) value (−7.9). Finally, a muscovite-rich source with high ε_Nd(t) (about −8.9) gave origin to the younger group of granites (2.3–1.0 Ma). The significant Sr isotope disequilibrium recorded by granites belonging to the same intrusion is interpreted, as due to the short residence time of magmas in the source region followed by their rapid transfer to the emplacement level. Partial melting was probably triggered by multiple, small-sized mafic intrusions, distributed over the last 3.8 Ma that allowed temporary overstepping of biotite- and muscovite-dehydration melting reactions into an already pre-heated crust. Dilution in time of the magmatic activity probably prevented melt mingling and homogenization at depth, as well as the formation of a single, homogeneous, hybrid pluton at the emplacement level. Moreover the high concentrations of fluxing elements (B, F, Li) estimated for the LAR granites modified melt properties by reducing solidus temperatures, decreasing viscosity and increasing H₂O solubility in granite melts. The consequences were a more efficient, fast, magma extraction and transfer from the source, and a prolonged time of crystallization at the emplacement level. These key factors explain the long-lived hydrothermal activity recorded in this area by both fossil (Plio-Quaternary ore deposits) and active (Larderello geothermal field) systems.     

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