Mineralization in Layered Mafic-Ultramafic Intrusions

This is the author accepted manuscript. The final version is available from Elsevier via the DOI in this recordLayered mafic-ultramafic intrusions (LMI) host a variety of metal deposits including chromium in chromitites; titanium and vanadium in magnetitites; scandium in clinopyroxene; and precious metals such as the platinum-group elements (PGE) and gold, and some base metals (nickel, cobalt and copper) associated with sulfide minerals. They also contain important resources of magnesium-silicate minerals (olivine, serpentine and talc) that are likely to become particularly important for the decarbonisation of our industries, economy and our daily lives. Many of these resources have real scope to become widely used for carbon capture and greenhouse gas reduction from our atmosphere in the imminent future. A range of geological processes govern how and where these elements and minerals become concentrated, or mineralized, into potentially economic deposits. In LMI, these are largely controlled by magmatic differentiation processes such as partial melting, crystallization, contamination and liquid immiscibility, and may be thought of as the culmination of four key factors: source, pathway, agent and deposition. In this chapter, we outline the current thinking behind the mineralization processes that operate in LMI and provide a synopsis of the grades, tonnages and characteristics of ore deposits in these intrusions

The Skaergaard trough layering: sedimentation in a convecting magma chamber.

The upper parts of the floor cumulates of the Skaergaard Intrusion, East Greenland, contain abundant features known as troughs. The troughs are gently plunging synformal structures comprising stacks of crescentic modally graded layers with a sharply defined mafic base that grades upward into plagioclase-rich material. The origin of the troughs and layering is contentious, attributed variously to deposition of mineral grains by magmatic currents descending from the nearby walls, or to in situ development by localised recrystallisation during gravitationally-driven compaction. They are characterised by outcrop-scale features such as mineral lineations parallel to the trough axis, evidence of erosion and layer truncation associated with migration of the trough axis, and disruption of layering by syn-magmatic slumping. A detailed microstructural study of the modal trough layers, using electron backscatter diffraction together with geochemical mapping, demonstrates that these rocks do not record evidence for deformation by either dislocation creep or dissolution-reprecipitation. Instead, the troughs are characterised by the alignment of euhedral plagioclase crystals with unmodified primary igneous compositional zoning. We argue that the lineations and foliations are, therefore, a consequence of grain alignment during magmatic flow. Post-accumulation amplification of the modal layering occurred as a result of differential migration of an unmixed immiscible interstitial liquid, with upwards migration of the Si-rich conjugate into the plagioclase-rich upper part of the layers, whereas the Fe-rich immiscible conjugate remained in the mafic base. Both field and microstructure evidence support the origin of the troughs as the sites of repeated deposition from crystal-rich currents descending from the nearby chamber walls

Distinct sulfur saturation histories within the Palaeogene Magilligan Sill, Northern Ireland: Implications for Ni-Cu-PGE mineralisation in the North Atlantic Igneous Province

This is the author accepted manuscript. The final version is available from NRC Research Press via the DOI in this record.The ~60 m thick Magilligan Sill is part of the British Palaeogene Igneous Province in the North Atlantic. The sill comprises layers of dolerite and olivine gabbro, and it intrudes a thick sequence of Mesozoic mudstones and marls, which are locally baked at the sill margins. Since 2014, the sill has been an exploration target for orthomagmatic Ni-Cu-PGE sulfide mineralisation analogous to the Noril’sk-Talnakh intrusion in Russia. We present new petrological, geochemical and S-isotope data to assess the prospectivity of the sill and the underlying magmatic plumbing system. Most sulfides in the dolerite portions of the sill are < 50 μm in size and comprise only pyrite with PGE abundances below detection limit. In the olivine gabbros, > 150 μm size pentlandite, chalcopyrite and pyrrhotite grains contain < 4 ppm total PGE, 1 460 ppm Co and 88 ppm Ag. Pyrite from the dolerites have δ34S ranging from -10.0 to +3.4 ‰ and olivine gabbro sulfides range from -2.5 to -1.1 ‰, suggesting widespread crustal contamination. The S/Se ratios of sulfides in the dolerites and olivine gabbros range from 3 500 to 19 500 and from 1 970 to 3 710, respectively, indicating that the latter may have come from upstream in the magma plumbing system. The Magilligan Sill records multiple injections of mafic magma into an inflating sill package, each with distinct mechanisms towards S-saturation. Whilst the sulfide minerals in the sill do not constitute significant mineralisation themselves, detailed in-situ studies highlight a divergence in Ssaturation histories, and suggest that a larger volume of olivine gabbro sulfides at depth may be prospective

Sources of fluids and metals and evolution models of skarn deposits in the Qimantagh metallogenic belt: A case study from the Weibao deposit, East Kunlun Mountains, northern Tibetan Plateau.

This is the author accepted manuscript. The final version is available from Elsevier via the DOI in this record.The Weibao Cu-Pb-Zn deposit is typical of skarn deposits in the Qimantagh metallogenic belt (QMB), EastKunlun Mountains, northern Tibetan Plateau. It comprises three ore blocks from west to east, known as Weixi,Main and Weidong. Mineralization in the Weibao deposit is intimately related to Late Triassic intrusions oc-curring at Weixi and Weidong, and orebodies are predominantly hosted by the Langyashan Formation (marinecarbonate rocks), and to a lesser extent the Devonian volcanic rocks. Skarns from Weixi and Weidong arecharacterized by a high garnet/pyroxene ratio and diopside- and andradite-rich composition of pyroxenes andgarnets, indicating a proximal, oxidized type. In contrast, skarn mineralogy of Main indicates a slightly reducedcondition, typical of Pb-Zn skarn deposits. At least five hydrothermal mineralization stages can be identified andthe microthermometric study indicates a general trend of cooling and dilution of the magmatic-hydrothermalfluids. Significant precipitation of Cu-Fe sulfides commenced from the fluid with the temperature of 340–448 °Cand the salinity of 2.1–15.0 wt% NaCl equiv. Pb-Zn sulfides however mainly precipitated when the temperaturesdeclined to < 370 °C and the salinity declined to < 7.6 wt% NaCl equiv. Carbon, hydrogen and oxygen isotopiccomposition of the fluids suggests a predominantly igneous source for the initial fluids, which were modifiedoutward by fluid-rock interaction and mixing with meteoric waters. Both sulfur and lead isotope composition ofsulfides supports a mixed sulfur and metal reservoir consisting of Triassic intrusive rocks and wall rocks.Compared to early skarn-forming and late quartz-carbonate stages, two ore-forming stages show clear evidenceof fluid boiling and fluid-rock interaction. Combined with microthermometric data of ore-forming stages, it canbe deduced that fluid cooling, boiling and fluid-rock interaction were responsible for the significant metalprecipitation. The Weibao deposit shows many similarities with skarn deposits in the QMB, and its genetic modeltherefore can be extrapolated to other skarn deposits in this region.This study was financially supported by the Geological Survey Program (Grant 1212011085528) of the China Geological Survey; the Program of High-level Geological Talents (201309) and Youth Geological Talents (201112) of the China Geological Survey; and the IGCP–592 project sponsored by IUGS–UNESCO. SZ appreciates the co-operation with the Natural History Museum (RS, AD) and the Camborne School of Mines, University of Exeter (JA) for hosting his skarn re-search. This is a contribution to their research on mineralized skarn systems funded by the EU Horizon 2020 project “FAME” (grant# 641650) and the Chinese Scholarship Council (fellowship to SZ). Dr. Hongying Qu, Jiannan Liu, Hui Wang and Jianhou Zhou from the CAGSare acknowledged for their assistance during the fieldwork

From Continent to Ocean: Investigating the Multi-Element and Precious Metal Geochemistry of the Paraná-Etendeka Large Igneous Province Using Machine Learning Tools

This is the final version. Available on open access from the Geological Society of London via the DOI in this recordData Availability Statement: The original contributions presented in the study are included in the article/Supplementary Material; further inquiries can be directed to the corresponding author.Large Igneous Provinces, and by extension the mantle plumes that generate them, are frequently associated with platinum-group element (PGE) ore deposits, yet the processes controlling the metal budget in plume-derived magmas remains debated. In this paper, we present a new whole-rock geochemical data set from the 135 Ma Paraná-Etendeka Large Igneous Province (PELIP) in the South Atlantic, which includes major and trace elements, PGE, and Au concentrations for onshore and offshore lavas from different developmental stages in the province, which underwent significant syn-magmatic continental rifting from 134 Ma onwards. The PELIP presents an opportunity to observe magma geochemistry as the continent and sub-continental lithospheric mantle (SCLM) are progressively removed from a melting environment. Here, we use an unsupervised machine learning approach (featuring the PCA, t-SNE and k-means clustering algorithms) to investigate the geochemistry of a set of (primarily basaltic) onshore and offshore PELIP lavas. We test the hypothesis that plume-derived magmas can scavenge precious metals including PGE from the SCLM and explore how metal concentrations might change the metal content in intraplate magmas throughout rifting. Onshore lavas on the Etendeka side of the PELIP are classified as the products of deep partial melts of the mantle below the African craton but without significant PGE enrichment. Offshore lavas on both continents exhibit similarities through the multi-element space to their onshore equivalents, but they again lack PGE enrichment. Of the four onshore lava types on the Paraná side of the PELIP, the Type 1 (Southern) and Type 1 (Central-Northern) localities exhibit separate PGE-enriched assemblages (Ir-Ru-Rh and Pd-Au-Cu, respectively). It follows that there is a significant asymmetry to the metallogenic character of the PELIP, with enrichment focused specifically on lavas from the South American continent edge in Paraná. This asymmetry contrasts with the North Atlantic Igneous Province (NAIP), a similar geodynamic environment in which continent-edge lavas are also PGE-enriched, albeit on both sides of the plume-rift system. We conclude that, given the similarities in PGE studies of plume-rift environments, SCLM incorporation under progressively shallowing (i.e., rifting) asthenospheric conditions promotes the acquisition of metasomatic and residual PGE-bearing minerals, boosting the magma metal budget.University of Exete

A machine learning approach for regional geochemical data: Platinum-group element geochemistry vs geodynamic settings of the North Atlantic Igneous Province

This is the author accepted manuscript. The final version is available on open access from Elsevier via the DOI in this recordWhilst traditional approaches to geochemistry provide valuable insights into magmatic processes such as melting and element fractionation, by considering entire regional data sets on an objective basis using machine learning algorithms (MLA), we can highlight new facets within the broader data structure and significantly enhance previous geochemical interpretations. The platinum-group element (PGE) budget of lavas in the North Atlantic Igneous Province (NAIP) have been shown to vary systematically according to age, geographic location and geodynamic environment. Given the large multi-element geochemical data set available for the region, MLA was employed to explore the magmatic controls on these shifting concentrations. The key advantage of using machine learning in analysis is its ability to cluster samples across multi-dimensional (i.e., multi-element) space. The NAIP data set is manipulated using Principal Component Analysis (PCA) and t-Distributed Stochastic Neighbour Embedding (t-SNE) techniques to increase separability in the data alongside clustering using the k-means MLA. The new multi-element classification is compared to the original geographic classification to assess the performance of both approaches. The workflow provides a means for creating an objective high-dimensional investigation on a geochemical data set and particularly enhances the identification of metallogenic anomalies across the region. The techniques used highlight three distinct multi-element end-members which successfully capture the variability of the majority of elements included as input variables. These end-members are seen to fluctuate in prominence throughout the NAIP, which we propose reflects the changing geodynamic environment and melting source. Crucially, the variability of Pt and Pd are not reflected in MLA-based clustering trends, suggesting that they vary independently through controls not readily demonstrated by the NAIP major or trace element data structure (i.e., other proxies for magmatic differentiation). This data science approach thus highlights that PGE (here signalled by Pt/Pd ratio) may be used to identify otherwise localised or cryptic geochemical inputs from the subcontinental lithospheric mantle (SCLM) during the ascent of plume-derived magma, and thereby impact upon the resulting metallogenic basket.University of Exete

Elemental distributions and mineral parageneses of the Skaergaard PGE-Au mineralisation: consequences of accumulation, redistribution, and equilibration in an upward-migrating mush zone

This is the author accepted manuscript. The final version is available from Oxford University Press via the DOI in this recordThe Skaergaard PGE-Au mineralisation, aka the Platinova Reef, is a syn-magmatic Platinum Group Element (PGE) and gold (Au) mineralisation that formed after crystallisation of ∼74% of the bulk melt of the intrusion. It is hosted in a more than 600 m deep and bowl-shaped succession of gabbroic macro-rhythmic layers in the upper 100 m of the Middle Zone. The precious metal mineralisation comprises a series of concordant, but compositionally zoned, mineralisation levels identified by distinct PGE, Au and Cu peaks. They formed due to local sulphide saturation in stratiform concentrations of interstitial and evolved mush melts in six MLs over > 2000 years. The PGE-Au mineralisation is compared to a stack of gold-rimmed saucers of PGE-rich gabbro of upward decreasing size. Fundamentally different crystallisation and mineralisation scenarios have been proposed for the mineralisation, including offset reef type models based on sulphide saturation in the melt from which the silicate host crystallised, and the here argued model which restricts the same processes to the melt of the inward migrating mush zone of the magma chamber. The latter is supported by: i) a 3D summary of the parageneses of precious metal minerals and phases (> 4000 grains) from 32 samples across the mineralisation; ii) a 3D compilation of all bulk rock assay data; and iii) a principal component analysis (PCA) of PGE, Au, Cu, and selected major and trace elements. In the main PGE-mineralisation level (Pd5 alias Pd-Zone) the precious metal mineral paragenesis varies across the intrusion with precious metal sulphides and Au-alloys at the W-margin to Precambrian basement, precious metal plumbide and Au- and Ag alloys at the E-margin to flood basalts, and skaergaardite (PdCu) and intermetallic compounds and alloys of PGE-Au and Cu in the central parts of the mineralisation. Precious metal parageneses are distinct for a given sector of the intrusion, i.e., drill core (local control), rather than for a given stratigraphic or temporal interval in the accumulated gabbros. The precious metal “grade times width” number (average g/t x metres) for the mineralisation at an upper and a lower cut off of 100 ppb PGE or Au increases from ∼20 to ∼45 g toward the centre of the mineralisation due to ponding of precious metal bearing melt. A strong increase in (Pd+Pt+Au)/Cu and dominance of (PdCu) alloys in the lower and central parts of the mineralisation demonstrate the partial dissolution of droplets of Cu-rich sulphide melt and fractionation of precious metal ratios. The precious metal parageneses, the distribution of precious metals in the mineralisation, and the PCA support initial accumulation of precious metals in the melt of the mush in the floor, followed by equilibration, sulphide saturation, and reactions with residual and immiscible Fe-rich silicate melt in a series of macro-rhythmic layers in the stratified and upward migrating mush zone in the floor of the magma chamber. Syn-magmatic and upward redistribution of precious metals sets the Skaergaard PGE-Au Mineralisation apart from conventional reef type and offset-reef type precious metal mineralisations, and characterize “Skaergaard type” precious metal deposits.Geological Survey of Denmark and Greenlan

Accessory phase perspectives for ore-forming processes and magmatic sulphide exploration in the Labrador Trough, northern Quebec, Canada

This is the author accepted manuscript. The final version is available from Canadian Science Publishing via the DOI in this recordThe compositions of resistant indicator minerals are diagnostic of their original host environment. They may be used to fingerprint different types of mineral deposit as well as vector towards them. We have characterised the composition of apatite and Fe–Ti oxides in variably mineralised mafic–ultramafic rock units of the Montagnais Sill Complex in the Labrador Trough to assess their suitability for vectoring towards magmatic sulphide occurrences. Two broad types of apatite were identified: (i) flu-oro-to hydroxy-apatite (Cl/(Cl+F) 0.5). The former reflects variable degrees of degassing and Cl loss during Rayleigh fractionation and is not indicative of Ni–Cu mineralisation or host rock. The latter exists only in sulphidic olivine cumulate units and thus may be used to vector towards similar rock types in the Labrador Trough. Ilmenite is the dominant oxide, except for the upper parts of differentiated gabbroic sills in which titanomagnetite is dominant. Magnetite occurs only as a secondary phase in serpentinised olivine cumulates and is not discriminative for magmatic sulphides. Ilmenite and titanomagnetite in the sulphidic olivine-bearing units have characteristically high Mg (~1000–10 000 ppm), Cr (~100–1000 ppm), and Ni (~10–1000 ppm) concentrations relative to those from other rock units. Their composition is consistent with Fe–Ti oxides derived from evolved sulphide melts in ultramafic-hosted Ni–Cu–(PGE) sulphide deposits and thus may be used to vector towards similar magmatic sulphide occurrences in the Labrador Trough.Natural Environment Research Council (NERC

Platinum-group element geochemistry of the Paraná flood basalts – modelling metallogenesis in rifting continental plume environments

This is the author accepted manuscript. The final version is available on open access from Elsevier via the DOI in this recordThe 135 Ma Paraná-Etendeka Large Igneous Province (PELIP) is one of the largest areas of continental flood basalt (CFB) volcanism in the world and is widely agreed to be a product of intracontinental melts related to thermal anomalies from the Tristan mantle plume. The province rifted during the break-up of Gondwana, as the plume transitioned into an oceanic geodynamic environment. This study reports analyses of plume-derived basalts from the Brazilian side of the PELIP (the Serra Geral Group) to investigate major, trace and platinum-group element (PGE) abundances in an evolving plume-rift metallogenic setting, with the aim of contextualising metallogenic controls alongside existing magmatic interpretations of the region. The chalcophile geochemistry of these basalts defines three distinct metallogenic groupings that fit with three modern multi-element magma classifications for Serra Geral lavas. In this scheme, Type 4 lavas have a distinctive PGE-poor signature, Type 1 (Central-Northern) lavas are enriched in Pd, Au and Cu, and Type 1 (Southern) lavas are enriched in Ru and Rh. Our trace element melt modelling indicates that the compositional variations result from changes in the melting regime between the garnet and spinel stability fields, in response to the thinning and ‘unlidding’ of the rifting continent above. This process imposes progressively shallower melting depths and higher degrees of partial melting. Accordingly, Type 4 magmas formed from small degree melts, reducing the likelihood of sulfide exhaustion/chalcophile acquisition at source. Type 1 (Central-Northern) magmas incorporated components of the sub-continental lithospheric mantle (SCLM)-derived in higher-degree partial melts; the SCLM was heterogeneously enriched via metasomatism prior to plume melting, and this produced enrichment in volatile metals (Pd, Cu, and Au) in these magmas. In contrast, the Ru-Rh enrichment in Type 1 (Southern) lavas is attributed to increased spinel-group mineral and sulphide incorporation from the mantle into higher degree partial melts close to the continental rift zone. Our models confirm the importance of contributions from SCLM melts in precious metal mineral systems within CFB provinces, and reinforce the role of heterogeneous metasomatic enrichment underneath cratons in boosting intracontinental prospectivity with respect to ore deposits.University of Exete

Extreme enrichment of Se, Te, PGE and Au in Cu sulfide microdroplets: evidence from LA-ICP-MS analysis of sulfides in the Skaergaard Intrusion, east Greenland

The Platinova Reef, in the Skaergaard Intrusion, east Greenland, is an example of a magmatic Cu–PGE–Au sulfide deposit formed in the latter stages of magmatic differentiation. As is characteristic with such deposits, it contains a low volume of sulfide, displays peak metal offsets and is Cu rich but Ni poor. However, even for such deposits, the Platinova Reef contains extremely low volumes of sulfide and the highest Pd and Au tenor sulfides of any magmatic ore deposit. Here, we present the first LA-ICP-MS analyses of sulfide microdroplets from the Platinova Reef, which show that they have the highest Se concentrations (up to 1200 ppm) and lowest S/Se ratios (190–700) of any known magmatic sulfide deposit and have significant Te enrichment. In addition, where sulfide volume increases, there is a change from high Pd-tenor microdroplets trapped in situ to larger, low tenor sulfides. The transition between these two sulfide regimes is marked by sharp peaks in Au, and then Te concentration, followed by a wider peak in Se, which gradually decreases with height. Mineralogical evidence implies that there is no significant post-magmatic hydrothermal S loss and that the metal profiles are essentially a function of magmatic processes. We propose that to generate these extreme precious and semimetal contents, the sulfides must have formed from an anomalously metal-rich package of magma, possibly formed via the dissolution of a previously PGE-enriched sulfide. Other processes such as kinetic diffusion may have also occurred alongside this to produce the ultra-high tenors. The characteristic metal offset pattern observed is largely controlled by partitioning effects, producing offset peaks in the order Pt+Pd>Au>Te>Se>Cu that are entirely consistent with published D values. This study confirms that extreme enrichment in sulfide droplets can occur in closed-system layered intrusions in situ, but this will characteristically form ore deposits that are so low in sulfide that they do not conform to conventional deposit models for Cu–Ni–PGE sulfides which require very high R factors, and settling of sulfide liquids