Metals in subduction related magmatism: Insights from melt inclusions and associated glassy groundmass from the Southern Kermadec Arc, New Zealand

<p>The southern Kermadec Arc – Havre Trough (SKAHT) is an intra-oceanic arc – back-arc system where the Pacific plate is subducting beneath the Australian plate. The Kermadec volcanic arc front consists of 33 volcanic centres, four of which host hydrothermal mineralization (Brothers, Haungaroa, Rumble II West, and Clark) such as volcanogenic massive sulfide (VMS) deposits, which are characterised by high concentrations of base and precious metals (e.g., Au, Cu, Zn, Pb). The sources of these metals are strongly tied to the metal contents within underlying magmatic rocks and associated magmatic systems with which the hydrothermal fluids interact. Understanding the sources, movements, and accumulation of metals associated with porphyry copper and exhalative base metal deposits within a subduction – arc setting remains limited. This study reports major, trace, and volatile element contents in basaltic groundmass glasses and olivine-hosted melt inclusions from lavas from four locations within the arc – back-arc setting of the SKAHT. The focus is on understanding the controls on base metal (Pb, Cu, Zn, Mo, V) contents in the magmas. The sample locations, Rumble III and Rumble II West volcanoes, and back-arc Basins D and I, form an arc-perpendicular transect extending from arc front into the back-arc. The analysed melt inclusion and groundmass glasses are all basalt to basaltic andesite in composition, with back-arc basin samples more mafic than arc front volcano samples. The magmatic evolution of the melts is primarily controlled by crystal fractionation of olivine + pyroxene + plagioclase. All glasses have undergone variable degassing, indicated by an absence of detectable CO₂ and curvilinear decreases in S contents with increasing SiO₂. Of the volatile phases analysed, only Cl appears unaffected by degassing. Distinct compositional differences are apparent between arc front and back-arc melts. The arc front magmas formed from higher degrees of melting of a less fertile mantle source and are more enriched in trace elements then the back-arc magmas due to greater additions of slab-derived aqueous fluids to their source. Magmas from a single arc front volcano (Rumble II West) incorporate melts that have tapped variably enriched sources, indicating heterogeneity of the mantle at small scales. Significant variation in mantle composition, however, is also apparent laterally along strike of the arc. Rumble III volcano and Basin I lie on an arc-perpendicular transect south of Rumble II West volcano and Basin D. Their greater enrichment in trace elements and higher concentrations of base metals than Rumble II West and Basin D lavas can be attributed to higher fluxes of subduction derived components. Base metals (Cu, Zn, Pb, Mo, and V) are variably enriched in the SKAHT melts compared with typical mid-ocean ridge basalts with relative enrichments in the order Pb >> Cu > Mo, V > Zn. All metals appear to be affected by mantle metasomatism related to slab-derived fluids, either directly from slab components introduced to the mantle source (e.g., Pb) or through mobilisation of metals within the ambient mantle wedge. The apparently compatible behaviour of Zn, Cu, and V in the mantle means that these elements may be enriched in arc front magmas relative to back-arc magmas by higher degrees of partial melting and/or melting of more depleted sources. All base metals behave incompatibly in the magma during crystal fractionation between 48 – 56 wt.% SiO₂. Lead and Cu concentrations, however, begin to level out from ~ 52 wt.% SiO₂ suggesting some subsequent loss to fractionating volatile phases as metal sulfide complexes. Rumble III samples show a decrease in metal concentration (Pb, Cu, V), from melt inclusions to groundmass glasses, suggestive of more significant loss associated with sulfur degassing. Although other factors such as heat generation, hydrothermal flow, fault systems, and magma venting are key in the development of VMS deposits, this study shows that variations in subduction parameters can significantly affect metal concentrations in arc magmas that may host hydrothermal systems, and hence the amount of metals available to be scavenged into the deposits.</p>

Metals in subduction related magmatism: Insights from melt inclusions and associated glassy groundmass from the Southern Kermadec Arc, New Zealand

<p>The southern Kermadec Arc – Havre Trough (SKAHT) is an intra-oceanic arc – back-arc system where the Pacific plate is subducting beneath the Australian plate. The Kermadec volcanic arc front consists of 33 volcanic centres, four of which host hydrothermal mineralization (Brothers, Haungaroa, Rumble II West, and Clark) such as volcanogenic massive sulfide (VMS) deposits, which are characterised by high concentrations of base and precious metals (e.g., Au, Cu, Zn, Pb). The sources of these metals are strongly tied to the metal contents within underlying magmatic rocks and associated magmatic systems with which the hydrothermal fluids interact. Understanding the sources, movements, and accumulation of metals associated with porphyry copper and exhalative base metal deposits within a subduction – arc setting remains limited. This study reports major, trace, and volatile element contents in basaltic groundmass glasses and olivine-hosted melt inclusions from lavas from four locations within the arc – back-arc setting of the SKAHT. The focus is on understanding the controls on base metal (Pb, Cu, Zn, Mo, V) contents in the magmas. The sample locations, Rumble III and Rumble II West volcanoes, and back-arc Basins D and I, form an arc-perpendicular transect extending from arc front into the back-arc. The analysed melt inclusion and groundmass glasses are all basalt to basaltic andesite in composition, with back-arc basin samples more mafic than arc front volcano samples. The magmatic evolution of the melts is primarily controlled by crystal fractionation of olivine + pyroxene + plagioclase. All glasses have undergone variable degassing, indicated by an absence of detectable CO₂ and curvilinear decreases in S contents with increasing SiO₂. Of the volatile phases analysed, only Cl appears unaffected by degassing. Distinct compositional differences are apparent between arc front and back-arc melts. The arc front magmas formed from higher degrees of melting of a less fertile mantle source and are more enriched in trace elements then the back-arc magmas due to greater additions of slab-derived aqueous fluids to their source. Magmas from a single arc front volcano (Rumble II West) incorporate melts that have tapped variably enriched sources, indicating heterogeneity of the mantle at small scales. Significant variation in mantle composition, however, is also apparent laterally along strike of the arc. Rumble III volcano and Basin I lie on an arc-perpendicular transect south of Rumble II West volcano and Basin D. Their greater enrichment in trace elements and higher concentrations of base metals than Rumble II West and Basin D lavas can be attributed to higher fluxes of subduction derived components. Base metals (Cu, Zn, Pb, Mo, and V) are variably enriched in the SKAHT melts compared with typical mid-ocean ridge basalts with relative enrichments in the order Pb >> Cu > Mo, V > Zn. All metals appear to be affected by mantle metasomatism related to slab-derived fluids, either directly from slab components introduced to the mantle source (e.g., Pb) or through mobilisation of metals within the ambient mantle wedge. The apparently compatible behaviour of Zn, Cu, and V in the mantle means that these elements may be enriched in arc front magmas relative to back-arc magmas by higher degrees of partial melting and/or melting of more depleted sources. All base metals behave incompatibly in the magma during crystal fractionation between 48 – 56 wt.% SiO₂. Lead and Cu concentrations, however, begin to level out from ~ 52 wt.% SiO₂ suggesting some subsequent loss to fractionating volatile phases as metal sulfide complexes. Rumble III samples show a decrease in metal concentration (Pb, Cu, V), from melt inclusions to groundmass glasses, suggestive of more significant loss associated with sulfur degassing. Although other factors such as heat generation, hydrothermal flow, fault systems, and magma venting are key in the development of VMS deposits, this study shows that variations in subduction parameters can significantly affect metal concentrations in arc magmas that may host hydrothermal systems, and hence the amount of metals available to be scavenged into the deposits.</p>

The Westwood Deposit, Southern Abitibi Greenstone Belt, Canada: An Archean Au-Rich Polymetallic Magmatic-Hydrothermal System—Part II. Hydrothermal Alteration, Mineralization, and Geologic Model

The Westwood deposit, located in the Archean Doyon-Bousquet-LaRonde mining camp in the southern Archean Abitibi greenstone belt, contains 4.5 Moz (140 metric t) of gold. The deposit is hosted in the 2699–2695 Ma submarine, tholeiitic to calc-alkaline volcanic, volcaniclastic, and intrusive rocks of the Bousquet Formation. The deposit is located near the synvolcanic (ca. 2699–2696 Ma) Mooshla Intrusive Complex that hosts the Doyon epizonal intrusion-related Au ± Cu deposit, whereas several Au-rich volcanogenic massive sulfide (VMS) deposits are present east of the Westwood deposit. The Westwood deposit consists of stratigraphically stacked, contrasting, and overprinting mineralization styles that share analogies with both the intrusion-related and VMS deposits of the camp. The ore zones form three distinct, slightly discordant to stratabound corridors that are, from north (base) to south (top), the Zone 2 Extension, the North Corridor, and the Westwood Corridor. Syn- to late-main regional deformation and upper greenschist to lower amphibolite facies regional metamorphism affect the ore zones, alteration assemblages, and host rocks. The Zone 2 Extension consists of Au ± Cu sulfide (pyrite-chalcopyrite)-quartz veins and zones of disseminated to semimassive sulfides. The ore zones are spatially associated with a series of calc-alkaline felsic sills and dikes that crosscut the mafic to intermediate, tholeiitic to transitional, lower Bousquet Formation volcanic rocks. The metamorphosed proximal alteration consists of muscovite-quartz-pyrite ± gypsum-andalusite-kyanite-pyrophyllite argillic to advanced argillic-style tabular envelope that is up to a few tens of meters thick. The North Corridor consists of auriferous semimassive to massive sulfide veins, zones of sulfide stringers, and disseminated sulfides that are hosted in intermediate volcaniclastic rocks at the base of the upper Bousquet Formation. The Westwood Corridor consists of semimassive to massive sulfide lenses, veins, zones of sulfide stringers, and disseminated sulfides that are located higher in the stratigraphic sequence, at or near the contact between calc-alkaline dacite domes and overlying calc-alkaline rhyodacite of the upper Bousquet Formation. A large, semiconformable distal alteration zone that encompasses the North Corridor is present in the footwall and vicinity of the Westwood Corridor. This metamorphosed alteration zone consists of an assemblage of biotite-Mn garnet-chlorite-carbonate ± muscovite-albite. A proximal muscovite-quartz-chlorite-pyrite argillic-style alteration assemblage is associated with both corridors. The Zone 2 Extension ore zones and associated alteration are considered synvolcanic based on crosscutting relationships and U-Pb geochronology and are interpreted as being the distal expression of an epizonal magmatic-hydrothermal system that is centered on the upper part of the synvolcanic Mooshla Intrusive Complex. The North and Westwood corridors consist of bimodal-felsic Au-rich VMS-type mineralization and alteration produced by the convective circulation of modified seawater that included a magmatic contribution from the coeval epizonal Zone 2 Extension magmatic-hydrothermal system. The Westwood Au deposit represents one of the very few documented examples of an Archean magmatic-hydrothermal system—or at least of such systems formed in a subaqueous environment. The study of the Westwood deposit resulted in a better understanding of the critical role of magmatic fluid input toward the formation of Archean epizonal intrusion-related Au ± Cu and seafloor/subseafloor Au-rich VMS-type mineralization.

Vectors to ore in replacive volcanogenic massive sulfide (VMS) deposits of the northern Iberian Pyrite Belt: mineral zoning, whole rock geochemistry, and application of portable X-ray fluorescence

In this work we have performed a detailed study of vectors to ore to a representative volcanic-rock-hosted replacive volcanogenic massive sulfide (VMS) deposit located in the northern Iberian Pyrite Belt (Spain), the Aguas Teñidas deposit. The investigated vectors include the following: (1) mineralogical zoning, (2) host sequence characterization and mineralized unit identification based on whole rock geochemistry discrimination diagrams, (3) study of the characteristics and behaviour of whole rock geochemical anomalies around the ore (e.g. alteration-related compositional changes, characteristics and extent of geochemical halos of indicative elements such as Cu, Zn, Pb, Sb, Tl, and Ba around the deposit), and (4) application of portable X-ray fluorescence (p-XRF) analysis to the detection of the previous vectors. In the footwall, a concentric cone-shaped hydrothermal alteration zone bearing the stockwork passes laterally, from core to edge, from quartz (only local) to chlorite–quartz, sericite–chlorite–quartz, and sericite–quartz alteration zones. The hydrothermal alteration is also found in the hanging wall despite being tectonically allochthonous to the orebody: a proximal sericite alteration zone is followed by a more distal albite-rich one. Whole rock major elements show an increase in alteration indexes (e.g. AI, CCPI) towards the mineralization, a general SiO2 enrichment, and FeO enrichment as well as K2O and Na2O depletion towards the centre of the hydrothermal system, with MgO showing a less systematic behaviour. K2O and Na2O leached from the centre of the system are transported and deposited in more external areas. Copper, Pb, and Zn produce proximal anomalies around mineralized areas, with the more mobile Sb, Tl, and Ba generating wider halos. Whereas Sb and Tl halos form around all mineralized areas, Ba anomalies are restricted to areas around the massive sulfide body. Our results show that proposed vectors, or adaptations designed to overcome p-XRF limitations, can be confidently used by analysing unprepared hand specimens, including the external rough curved surface of drill cores. The data presented in this work are not only applicable to VMS exploration in the Iberian Pyrite Belt, but on a broader scale they will also contribute to improving our general understanding of vectors to ore in replacive-type VMS deposits.

Geochemical and Volcanological Criteria in Assessing the Links between Volcanism and VMS Deposits: A Case on the Iberian Pyrite Belt, Spain

VMS deposits in the Iberian Pyrite Belt (IPB), Spain and Portugal, constitute the largest accumulation of these deposits on Earth. Although several factors account for their genetic interpretation, a link between volcanism and mineralization is generally accepted. In many VMS districts, research is focused on the geochemical discrimination between barren and fertile volcanic rocks, these latter being a proxy of VMS mineralization. Additionally, the volcanological study of igneous successions sheds light on the environment at which volcanic rocks were emplaced, showing an emplacement depth consistent with that required for VMS formation. We describe a case on the El Almendro–Villanueva de los Castillejos (EAVC) succession, Spanish IPB, where abundant felsic volcanic rocks occur. According to the available evidence, their geochemical features, εNd signature and U–Pb dates suggest a possible link to VMS deposits. However, (paleo)volcanological evidence here indicates pyroclastic emplacement in a shallow water environment. We infer that such a shallow environment precluded VMS generation, a conclusion that is consistent with the absence of massive deposits all along this area. We also show that this interpretation lends additional support to previous models of the whole IPB, suggesting that compartmentalization of the belt had a major role in determining the sites of VMS deposition.

Vectors to ore in replacive VMS deposits of the northern Iberian Pyrite Belt: mineral zoning, whole rock geochemistry, and use of portable XRF

Volcanogenic Massive Sulphide (VMS) deposits represent a major source of base, precious and other metals of economic and industrial importance. As in other mineral systems, progressive exhaustion of the shallowest and most easily accessible deposits is leading to increasingly complex exploration. In this context vectors to ore play a vital role. The Iberian Pyrite Belt (IPB) is an outstanding VMS district located in the SW Iberian Peninsula, which represents the main mining area in Spain and one of the main zones of base metal production in Europe. But the work on vectors to ore in the IPB is far from systematic or complete. In this work we have performed a detailed study of the main vectors to ore related to mineral zoning and whole rock geochemistry that are currently used in the exploration of VMS systems to a representative volcanic rock hosted replacive VMS deposit located in the northern IPB, the Aguas Teñidas deposit. Results have been compared to other deposits in the IPB and in other VMS districts. The investigated vectors include: mineralogical zoning, host sequence characterization and mineralized unit identification based on whole rock geochemistry, the study of the characteristics and behaviour of whole rock geochemical anomalies around the ore (e.g. alteration-related compositional changes, characteristics and extent of geochemical halos around the deposit), with definition of threshold values for the mineralization-related indicative elements, and application of portable XRF analysis to the detection of the previous vectors. In the footwall, a concentric cone-shaped hydrothermal alteration bearing the stockwork passes laterally, from core to edge, from quartz (only locally), to chlorite, sericite–chlorite, and sericite alteration zones. The hydrothermal alteration is also found in the hanging wall despite its thrusted character: a proximal sericite alteration zone is followed by a more distal albite one, which is described here for the first time in the IPB. Whole rock major elements show an increase in alteration indexes (e.g. AI, CCPI) towards the mineralization, with a general SiO2 enrichment, FeO enrichment in the central portion of the system, K2O and Na2O leaching towards the outside areas, and a less systematic MgO behaviour. Copper, Pb and Zn produce proximal anomalies around mineralized areas, with the more mobile Sb, Tl and Ba generating wider halos. Whereas Sb and Tl halos form around all mineralized areas, Ba anomalies are restricted to areas around the massive sulphide body. Our results show that proposed vectors, or adaptations designed to overcome p-XRF limitations, can be confidently used by analysing unprepared hand specimens, including the external rough curved surface of drill cores. The data presented in this work are not only applicable to VMS exploration in the IPB, but on a broader scale they will also contribute to improve our general understating of vectors to ore in replacive-type VMS deposits.

Subseafloor sulphide deposit formed by pumice replacement mineralisation

Seafloor massive sulphide (SMS) deposits, modern analogues of volcanogenic massive sulphide (VMS) deposits on land, represent future resources of base and precious metals. Studies of VMS deposits have proposed two emplacement mechanisms for SMS deposits: exhalative deposition on the seafloor and mineral and void space replacement beneath the seafloor. The details of the latter mechanism are poorly characterised in detail, despite its potentially significant role in global metal cycling throughout Earth’s history, because in-situ studies require costly drilling campaigns to sample SMS deposits. Here, we interpret petrographic, geochemical and geophysical data from drill holes in a modern SMS deposit and demonstrate that it formed via subseafloor replacement of pumice. Samples from the sulphide body and overlying sediment at the Hakurei Site, Izena Hole, middle Okinawa Trough indicate that sulphides initially formed as aggregates of framboidal pyrite and matured into colloform and euhedral pyrite, which were replaced by chalcopyrite, sphalerite and galena. The initial framboidal pyrite is closely associated with altered material derived from pumice, and alternating layers of pumiceous and hemipelagic sediments functioned as a factory of sulphide mineralisation. We infer that anhydrite-rich layers within the hemipelagic sediment forced hydrothermal fluids to flow laterally, controlling precipitation of a sulphide body extending hundreds of meters.