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Menzies C.D.,UK National Oceanography Center | Teagle D.A.H.,UK National Oceanography Center | Craw D.,University of Otago | Cox S.C.,Institute of Geological & Nuclear Sciences | And 4 more authors.
Earth and Planetary Science Letters | Year: 2014

Rapid tectonic uplift on the Alpine Fault, New Zealand, elevates topography, regional geothermal gradients, and the depth to the brittle ductile transition, and drives fluid flow that influences deformation and mineralisation within the orogen. Oxygen and hydrogen stable isotopes, fluid inclusion and Fourier Transform Infrared (FT-IR) analyses of quartz from veins which formed at a wide range of depths, temperatures and deformation regimes identify fluid sources and the depth of penetration of meteoric waters. Most veins formed under brittle conditions and with isotope signatures (δ18OH2O = -9.0 to +8.7‰VSMOW and δD = - 73 to - 45‰VSMOW) indicative of progressively rock-equilibrated meteoric waters. Two generations of quartz veins that post-date mylonitic foliation but endured further ductile deformation, and hence formation below the brittle to ductile transition zone (>6-8 km depth), preserve included hydrothermal fluids with δD values between -84 and -52‰, indicating formation from meteoric waters. FT-IR analyses of these veins show no evidence of structural hydrogen release, precluding this as a source of low δD values. In contrast, the oxygen isotopic signal of these fluids has almost completely equilibrated with host rocks (δ18OH2O = +2.3 to +8.7‰). These data show that meteoric waters dominate the fluid phase in the rocks, and there is no stable isotopic requirement for the presence of metamorphic fluids during the precipitation of ductilely deformed quartz veins. This requires the penetration during orogenesis of meteoric waters into and possibly below the brittle to ductile transition zone. © 2014 The Authors.

Petchey F.,University of Waikato | Spriggs M.,Australian National University | Leach F.,Archaeozoology Laboratory | Seed M.,Isoprime Ltd | And 3 more authors.
Journal of Archaeological Science | Year: 2011

Archaeologists have long debated the origins and mode of dispersal of the immediate predecessors of all Polynesians and many populations in Island Melanesia. Such debates are inextricably linked to a chronological framework provided, in part, by radiocarbon dates. Human remains have the greatest potential for providing answers to many questions pertinent to these debates. Unfortunately, bone is one of the most complicated materials to date reliably because of bone degradation, sample pre-treatment and diet. This is of particular concern in the Pacific where humidity contributes to the rapid decay of bone protein, and a combination of marine, reef, C4, C3 and freshwater foods complicate the interpretation of 14C determinations. Independent advances in bone pre-treatment, isotope multivariate modelling and radiocarbon calibration techniques provide us, for the first time, with the tools to obtain reliable calibrated ages for Pacific burials. Here we present research that combines these techniques, enabling us to re-evaluate the age of burials from key archaeological sites in the Pacific. © 2010 Elsevier Ltd.

Gagnevin D.,Number 1 Products and Services | Menuge J.F.,University College Dublin | Kronz A.,University of Gottingen | Barrie C.,Isoprime Ltd | Boyce A.J.,Scottish Universities Environmental Research Center
Economic Geology | Year: 2014

This study tests the utility of the minor to trace element composition of sphalerite to discriminate between possible sources of ore-forming fluids, and to constrain processes involved in ore genesis of the world-class Irish-type Navan Zn-Pb orebody, Ireland. Detailed petrography and electron microprobe microanalyses were performed on layered sphalerite previously analyzed for Zn, Fe, and S isotope compositions. Layered sphalerite displays a wide range of chemical composition at both sample and crystal scales. The color, style, and scale of layering show variations with chemical composition, but none of these correlations are consistent between samples. However, there are strong intersample correlations between chemical and S-Fe-Zn isotope compositions at the millimeter scale. Sphalerite precipitated from deep, hydrothermal fluids with 34S-enriched sulfide is enriched in Cd, Sb, Cu, and Ag, whereas Fe and As are enriched in sphalerite precipitated from shallow, bacteriogenic brines with isotopically light S. Significant chemical variations also occur at the micrometer scale in sphalerite regardless of its genetic affinity. These variations are interpreted as being due to variations in temperature, pH, and sulfur activity following the arrival at the site of deposition of pulses of hydrothermal fluids at specific stages of sphalerite growth. Therefore the chemistry of sphalerite, coupled with its texture, appears to be a powerful tool to elucidate fluid typing and ore genesis. The results support the hypothesis that layered sphalerite forms by rapid crystallization due to mixing of two fluids of contrasting physicochemical properties, a process required for the formation of Irish-type and some other hydrothermal deposits including, most notably, Mississippi Valley-type (MVT) deposits. The existence of layered sphalerite, coupled with its texture and chemical composition, may therefore provide useful insight for the mineral exploration industry in Ireland and elsewhere. © 2014 Society of Economic Geologists, Inc.

Torremans K.,Catholic University of Leuven | Gauquie J.,Catholic University of Leuven | Boyce A.J.,Scottish Enterprise | Barrie C.D.,Scottish Enterprise | And 4 more authors.
Journal of African Earth Sciences | Year: 2013

The Konkola deposit is a high grade stratiform Cu-Co ore deposit in the Central African Copperbelt in Zambia. Economic mineralisation is confined to the Ore Shale formation, part of the Neoproterozoic metasedimentary rocks of the Katanga Supergroup. Petrographic study reveals that the copper-cobalt ore minerals are disseminated within the host rock, sometimes concentrated along bedding planes, often associated with dolomitic bands or clustered in cemented lenses and in layer-parallel and irregular veins. The hypogene sulphide mineralogy consists predominantly of chalcopyrite, bornite and chalcocite. Based upon relationships with metamorphic biotite, vein sulphides and most of the sulphides in cemented lenses were precipitated during or after biotite zone greenschist facies metamorphism. New δ34S values of sulphides from the Konkola deposit are presented. The sulphur isotope values range from -8.7‰ to +1.4‰ V-CDT for chalcopyrite from all mineralising phases and from -4.4‰ to +2.0‰ V-CDT for secondary chalcocite. Similarities in δ34S for sulphides from different vein generations, earlier sulphides and secondary chalcocite can be explained by (re)mobilisation of S from earlier formed sulphide phases, an interpretation strongly supported by the petrographic evidence. Deep supergene enrichment and leaching occurs up to a km in depth, predominantly in the form of secondary chalcocite, goethite and malachite and is often associated with zones of high permeability. Detailed distribution maps of total copper and total cobalt contents of the Ore Shale formation show a close relationship between structural features and higher copper and lower cobalt contents, relative to other areas of the mine. Structural features include the Kirilabombwe anticline and fault zones along the axial plane and two fault zones in the southern limb of the anticline. Cobalt and copper behave differently in relation to these structural features. These structures are interpreted to have played a significant role in (re)mobilisation and concentration of the metals, in agreement with observations made elsewhere in the Zambian Copperbelt. © 2012 Elsevier Ltd.

Gagnevin D.,University College Dublin | Boyce A.J.,Scottish Universities Environmental Research Center | Barrie C.D.,Scottish Universities Environmental Research Center | Barrie C.D.,Isoprime Ltd | And 2 more authors.
Geochimica et Cosmochimica Acta | Year: 2012

The genesis of hydrothermal ore deposits is of crucial economic importance. This study investigates the extent, causes and consequences of zinc and iron isotope fractionation in a large hydrothermal system at the world-class Navan Zn-Pb orebody, Ireland. Large variations in Zn, Fe and S isotope compositions have been measured in microdrilled sphalerite (ZnS) at the millimetre scale. δ 66Zn and δ 56Fe display a well-defined positive correlation and both also correlate with δ 34S. These relationships represent the combined effects of kinetic Zn and Fe isotope fractionation during sphalerite precipitation, and S isotope variation through mixing of hot, metal-rich hydrothermal fluids and cool, bacteriogenic sulfide-bearing brines. Combined with S isotope data, δ 56Fe and δ 66Zn data on mine concentrates confirm that hydrothermal sulfide is a minor component of the overall deposit signature. Our data suggest that incoming pulses of metal-rich hydrothermal fluid triggered sulfide mineralisation, and that rapid precipitation of sphalerite from hydrothermal fluids will lead to strong kinetic fractionation of Zn and Fe isotopes at very short time and length scales, thereby limiting the use of Fe and Zn isotopes as exploration tools within deposits, but revealing the possibility of detecting new deposits from isotopically heavy Zn-Fe geochemical halos. © 2012 Elsevier Ltd.

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