Iain K. Pitcairn

Detecting hydrothermal graphite deposition during metamorphism and gold mineralization

Fourier Transform IR analyses of carbonaceous material from the Otago and Alpine Schists and the Macraes gold deposit of the South Island, New Zealand, show the progressive effects of graphitization during metamorphism and suggest that the majority of carbonaceous material identified at the Macraes deposit precipitated from hydrothermal fluids. Given that the distinction of sedimentary carbonaceous material from fluid-precipitated graphite is a key to better understanding the redox state of crustal rocks, ore depositional processes and the extent of carbon cycling in the crust, this study highlights the importance of IR spectroscopy in the characterization of reduced carbon-bearing rocks.

Golden plumes: Substantial gold enrichment of oceanic crust during ridge-plume interaction

Mantle plume events are increasingly implicated as the source of gold (Au) in regions of the Earth that show a high Au endowment. However, the process of enriching oceanic crust in Au by plume activity is poorly understood and unconstrained. We present the first systematic study of Au concentrations in oceanic basalts as a function of distance from a plume center. We show that the influence of the Iceland plume on the Mid-Atlantic Ridge progressively enriches the oceanic crust in Au along the Reykjanes Ridge by as much as 13 times normal levels, over a distance of ∼600 km, and that the enrichment can be attributed to specific plume components. This Au enrichment by the Iceland plume implies a genetic relationship between deep mantle upwelling and major gold mineralization.

Regional mapping of pre-metamorphic spilitization and associated chemical mobility in greenschist-facies metabasalts of the SW Scottish Highlands

Abstract: Both spilitic and non-spilitic metabasaltic sills are hosted by greenschist-facies metasediments in the SW Scottish Highlands. Spilitization is mainly characterized by enrichment in Na2O, elevated modal plagioclase and epidote segregations. Mapping of the spatial distribution of spilitic metabasalts reveals an ancient sub-sea-floor fluid cell centred on the extrusive Tayvallich Volcanics. Fluid circulation was most extensive at shallow levels where most sills were spilitized. We attribute this to pervasive flow of saline fluid, which was thermally driven by the cooling suite of lava flows and sills. Spilitization below this lithostratigraphic depth was restricted to only a few sills. Their spilitization is largely unrelated to specific properties of these sills (e.g. width, chemistry or host lithology). We conclude that fluid channelling was an intrinsic property of sub-sea-floor fluid flow either at deeper levels or earlier during fluid circulation. By profiling of the size distributions of relic phenocrysts in a partly spilitized sill, we conclude that spilitization proceeds with the symmetric propagation of a spilitization front from the sill margins towards the sill interior. Based on chemical profiling across the margin of an epidote segregation, we conclude that spilitization is associated with chemical transport on scales ranging from 0.1 to 10 m.

Contrasting geochemistry of orogenic gold deposits in Yukon, Canada and Otago, New Zealand

The Yukon-Tanana Terrane (YTT) of western Yukon Territory in NW Canada and Otago Schist belt (OSB) of South Island, New Zealand share similar geological evolutionary histories as convergent orogenic belts. Both belts host orogenic gold deposits of mainly Jurassic to Early Cretaceous age. Jurassic mineralization in the YTT occurred during convergent orogenesis and stacking of previously-metamorphosed (Palaeozoic) greenschist-amphibolite facies metasediments, metavolcanic rocks, and metagranitoids. Early Cretaceous OSB mineralization occurred in the latter stages of terrane accretion of un-metamorphosed turbidites with minor basaltic rocks. Metamorphism of the OSB turbidites mobilised background levels of Au (0.6–1.3 ppb), As (2–20 ppm), Sb (0.1–1 ppm), and W (< 10 ppm), primarily under greenschist to lower amphibolite facies conditions when diagenetic pyrite (Au c. 0.5–2 ppm; As c. 500–10 000 ppm) transformed to pyrrhotite on a regional scale. In contrast, the previously-metamorphosed YTT rocks had generally low background As contents (1–2 ppm) apart from some As-rich quartzites (up to 100 ppm As). Consequently, there was less As available for orogenic mobilisation, and YTT Au deposits generally have lower concentrations of this pathfinder element compared to the OSB. YTT host rocks, especially metagranitoids, have anomalous levels of Mo (10–300 ppm), and many orogenic deposits contain elevated Mo, locally including molybdenite. OSB turbidites have elevated Mo (2–200 ppm), along with elevated Au and As, in diagenetic pyrite, but this Mo became largely dispersed through the metamorphic pile as metamorphic grade increased and pyrite transformed to pyrrhotite. OSB orogenic deposits have only marginally elevated Mo (c. 1 ppm), no molybdenite, and accessory scheelite in these deposits is distinctly Mo-poor. Only minor mobilisation of base metals occurred in these orogenic belts, and orogenic Au deposits contain sparse base metal sulphides. Orogenic deposits in the YTT and OSB differ in that Au (and other associated elements) in many of the orogenic deposits in the YTT was remobilised from relatively local sources (e.g. pre-existing Cu-Mo-Au porphyry or volcanogenic sulphide mineralization) whereas Au in the OSB was mobilised from larger volumes of homogeneous rock at depth.

Geochemical signatures of mesothermal Au-mineralized late-metamorphic deformation zones, Otago Schist, New Zealand

Hydrothermal processes along two regional-scale shear zones in the Otago Schist were dominated by structurally controlled fluid flow and mineralization in the host schist, with relatively minor quartz vein formation, and mineralized rocks are only subtly different from unmineralized rocks. Most Au in the shear zones is associated with sulphide minerals (pyrite and arsenopyrite) disseminated through the host schist or along microshears. Minor enrichment of Sb, Mo and Bi (ppm level) is detectable in the Hyde-Macraes Shear Zone (HMSZ). Hydrothermal muscovite is slightly more aluminous (1–2 wt%) than metamorphic muscovite in both shear zones. HMSZ muscovite averages >900 ppm N, in contrast to metamorphic muscovite that averages c. 200 ppm N. In both shear zones, rutile has replaced metamorphic titanite and epidote has altered to carbonate and phyllosilicates, but these reactions were nearly isochemical. Structurally controlled hydrothermal graphite in the HMSZ occurs in microshears (up to 3 wt%, above background <0.2 wt%). Alteration in the Rise & Shine Shear Zone (RSSZ) was accompanied by addition of abundant ankerite. The two shear zones have subtly different geochemical signatures and are not directly genetically related. However, As enrichment is a key exploration target for both shear zones.

Carbonate alteration of ophiolitic rocks in the Arabian–Nubian Shield of Egypt: sources and compositions of the carbonating fluid and implications for the formation of Au deposits

ABSTRACT Ultramafic portions of ophiolitic fragments in the Arabian–Nubian Shield (ANS) show pervasive carbonate alteration forming various degrees of carbonated serpentinites and listvenitic rocks. Notwithstanding the extent of the alteration, little is known about the processes that caused it, the source of the CO2 or the conditions of alteration. This study investigates the mineralogy, stable (O, C) and radiogenic (Sr) isotope composition, and geochemistry of suites of variably carbonate altered ultramafics from the Meatiq area of the Central Eastern Desert (CED) of Egypt. The samples investigated include least-altered lizardite (Lz) serpentinites, antigorite (Atg) serpentinites and listvenitic rocks with associated carbonate and quartz veins. The C, O and Sr isotopes of the vein samples cluster between −8.1‰ and −6.8‰ for δ13C, +6.4‰ and +10.5‰ for δ18O, and 87Sr/86Sr of 0.7028–0.70344, and plot within the depleted mantle compositional field. The serpentinites isotopic compositions plot on a mixing trend between the depleted-mantle and sedimentary carbonate fields. The carbonate veins contain abundant carbonic (CO2±CH4±N2) and aqueous-carbonic (H2O-NaCl-CO2±CH4±N2) low salinity fluid, with trapping conditions of 270–300°C and 0.7–1.1 kbar. The serpentinites are enriched in Au, As, S and other fluid-mobile elements relative to primitive and depleted mantle. The extensively carbonated Atg-serpentinites contain significantly lower concentrations of these elements than the Lz-serpentinites suggesting that they were depleted during carbonate alteration. Fluid inclusion and stable isotope compositions of Au deposits in the CED are similar to those from the carbonate veins investigated in the study and we suggest that carbonation of ANS ophiolitic rocks due to influx of mantle-derived CO2-bearing fluids caused break down of Au-bearing minerals such as pentlandite, releasing Au and S to the hydrothermal fluids that later formed the Au-deposits. This is the first time that gold has been observed to be remobilized from rocks during the lizardite–antigorite transition.

The mechanism of infiltration of metamorphic fluids recorded by hydration and carbonation of epidote-amphibolite facies metabasaltic sills in the SW Scottish Highlands

Abstract In this study we investigate a group of metabasaltic sills from the SW Scottish Highlands metamorphosed at epidote-amphibolite facies conditions that provide useful insight into the mechanisms and characteristics of fluid infiltration during metamorphism. The sills are amphibole and garnet bearing and exhibit a strong foliation in the sill margins that developed pre- to syn-peak metamorphism. Fluid infiltration caused hydration and carbonation in the sills, expressed as (1) replacement of garnet and amphibole by chlorite and calcite and (2) replacement of amphibole and epidote to form chlorite and calcite. Using garnet-amphibole and garnet-chlorite geothermometers we show that these reactions occurred after peak metamorphism at T = 290 to 400 °C. Reaction textures show that the fluid infiltration into the sill that caused hydration and carbonation occurred in the absence of deformation. The fluid infiltration was mineralogically controlled with greater fluid access in areas of abundant fine-grained elongate minerals such as amphibole and chlorite. The replacement of garnet by chlorite most likely occurred by an interface-coupled dissolution-precipitation mechanism as evidenced by perfect pseudomorphic textures of garnet, porosity generation behind the reactive interface and fracturing ahead of this interface. Porosity generated in the product chlorite enhanced fluid access to the replacement front. The study shows that deformation was not required for extensive fluid infiltration and alteration during metamorphism. Fluid flow uses a pre-existing foliation to gain access to the rock, taking advantage of the anisotropic shape of the aligned minerals.

Hydrothermal footprint of the Birthday Reef, Reefton goldfield, New Zealand

ABSTRACT The Birthday Reef was the most productive gold producer during historic mining of the Reefton goldfield on the west coast of the South Island of New Zealand. Deep exploration drill holes (up to 1.6 km long) intersected the mineralised quartz vein zone and adjacent hydrothermal alteration halo beneath the historic mine workings. The Paleozoic metasedimentary host rocks contain between 0.5 and 8 ppb Au and between 4 and 30 ppm As, and metamorphic pyrite typically contains 0.1 to 1 ppm Au in solid solution. The Au and As halo, above these background values, extends <20 m from the Birthday Reef, and other petrographic indicators of alteration are also confined to this narrow envelope. Porphyroblasts of pyrite and arsenopyrite, with minor Au enrichment, grew across the metamorphic cleavage in the alteration halo before emplacement of the Birthday Reef and associated shearing, and reflect an earlier, late metamorphic precursor to the main gold mineralisation phase.

Evaluation of phosphate-uptake mechanisms by Fe(III) (oxyhydr)oxides in Early Proterozoic oceanic conditions

Environmental context Reconstructing the Precambrian oceanic P cycle, in conjunction with the As cycle, is critical for understanding the rise of atmospheric O2 in Earth’s history. Bioavailable phosphorus (P) has been found to regulate photosynthetic activity, whereas dissolved arsenic (As) maxima correlate with photosynthetic minima. New data on empirical adsorption and coprecipitation models with Fe(III) (oxyhydr)oxides suggest coprecipitation is a more efficient method of P sorption than is adsorption in Precambrian surface ocean conditions. Abstract Banded iron formations (BIF) are proxies of global dissolved inorganic phosphate (DIP) content in Precambrian marine waters. Estimates of Precambrian DIP rely on constraining the mechanisms by which Fe(III) (oxyhydr)oxides scavenge DIP in NaCl solutions mimicking elevated Precambrian marine Si and Fe(II) concentrations. The two DIP binding modes suggested for Early Proterozoic marine waters are (1) surface attachment on pre-formed Fe(III) (oxyhydr)oxides (adsorption), and (2) incorporation of P into actively growing Fe(III) (oxyhydr)oxides (coprecipitation) during the oxidation of Fe(II) to Fe(III) (oxyhydr)oxides in the presence of DIP. It has been suggested that elevated Si concentrations, such as those suggested for Precambrian seawater, strongly inhibit adsorption of DIP in Fe(III) (oxyhydr)oxides; however, recent coprecipitation experiments show that DIP is scavenged by Fe(III) (oxyhydr)oxides in the presence of Si, seawater cations and hydrothermal As. In the present study, we show that the DIP uptake onto Fe(III) (oxyhydr)oxides by adsorption is less than 5 % of DIP uptake by coprecipitation. Differences in surface attachment and the possibility of structural capture within the Fe(III) (oxyhydr)oxides are inferred from the robust influence Si has on DIP binding during adsorption, meanwhile the influence of Si on DIP binding is inhibited during coprecipitation when As(III) and As(V) are present. In the Early Proterozoic open oceans, Fe(III) (oxyhydr)oxides precipitated when deep anoxic Fe(II)-rich waters rose and mixed with the first permanently oxygenated ocean surface waters. Our data imply that, DIP was removed from surface waters through coprecipitation with those Fe(III) (oxyhydr)oxides, rather than adsorption. Local variations in DIP and perhaps even stratification of DIP in the oceans were likely created from the continuous removal of DIP from surface waters by Fe(III) (oxyhydr)oxides, and by the partial release of DIP into the anoxic bottom waters and buried sediments. In addition to a DIP famine, the selectivity for DIP over As(V) may have led to As enrichment in surface waters, both of which would have most likely decreased the productivity of cyanobacteria and O2 production.

Shock brecciation around the Kidd Creek deposit, Abitibi belt, Canada

The Kidd-Munro assemblage, Abitibi belt, Canada, is an ultramafic-mafic-felsic volcanic sequence that contains the giant Kidd Creek volcanic-hosted massive sulfide (VMS) deposit. The Kidd basin, 1. ...