Imperial College London


Faculty of EngineeringDepartment of Earth Science & Engineering

Professor of Geology



j.wilkinson Website




PA418Natural History MuseumNatural History Museum





Publication Type

156 results found

Wilkinson JJ, 2023, Tracing metals from source to sink in Irish-type Zn-Pb(-Ba-Ag) deposits, IAEG 50 - 50 Years of Irish-type Zn-Pb Deposits, Publisher: IAEG, Pages: 147-168

The Irish Midlands Zn-Pb(-Ba-Ag) Orefield represents one of the best studied palaeo-hydrothermalsystems worldwide. Despite this, the detailed origins of ore and trace metals and the controls of their variability indeposits across the Orefield, have not been considered in detail. In this contribution, I have used diverse data sourcesin an attempt to track the metals from their source and assess how they were fractionated at various stages alongthe reconstructed flow path. This includes: (1) circulation of fluids to depths of up to ~7 km in the Lower Palaeozoicwedge of arc-derived detritus that underlies the Orefield and through a primary ‘reaction zone’; (2) fluid transitwithin the wedge and then up through the redox boundary represented by the Old Red Sandstone; and (3) fluidingress into the receptive Lower Carboniferous host rocks in the ore deposits themselves, initially through focusedfeeder pipes and then spreading out upwards and especially laterally into the surrounding carbonate units. Theresults show that the Lower Palaeozoic package was a particularly fertile source from which metals were easilyextracted and that this exerted a primary control on metal tenor in the overlying deposits. However, additionalfractionation steps, including loss to and extraction of metals from, the Old Red Sandstone, and sequential deposition of metals during cooling, neutralisation and fluid mixing were also important. The presence beneath the IrishMidlands Basin of a weakly metamorphosed rock package formed from arc-derived detritus is considered to be acritical component of the mineral system.

Conference paper

Nathwani CL, Large SJE, Brugge ER, Wilkinson JJ, Buret Yet al., 2023, Apatite evidence for a fluid-saturated, crystal-rich magma reservoir forming the Quellaveco porphyry copper deposit (Southern Peru), Contributions to Mineralogy and Petrology, Vol: 178, Pages: 1-21, ISSN: 0010-7999

Large volume, intermediate-felsic magma reservoirs are the source of melt and mineralising fluids which generate porphyry copper deposits. Cooling and crystallisation of hydrous magmas drives the exsolution and expulsion of a magmatic volatile phase—a process which remains challenging to constrain in porphyry Cu systems where the record of magma volatile compositions is rarely preserved. Here, we use the halogen compositions of apatite inclusions shielded as inclusions within zircon to constrain volatile evolution in magma reservoirs which pre-date and are synchronous with porphyry Cu mineralisation at Quellaveco, Southern Peru. Geochemical and textural data confirm that the zircon-included apatites escaped re-equilibration with hydrothermal fluids, unlike apatites found in the groundmass of the same rocks. We, therefore, recommend that future studies attempting to reconcile magmatic volatile budgets using apatite in porphyry Cu systems should focus on apatite inclusions in zircon. By combining the apatite inclusion data with numerical modelling, we find evidence that the magma reservoir sourcing porphyry Cu mineralisation remained fluid-saturated for the entire period recorded by apatite crystallisation. By contrast, the pre-mineralisation batholith shows more variable, potentially fluid-undersaturated behaviour. Our modelling suggests that in order to attain the porphyry melt volatile compositions inferred from apatite, the magma reservoir must have exsolved a large proportion of its volatile budget, consistent with having been held at high crystallinity (40–60% crystals). This crystallisation interval coincides with peak chlorine and copper extraction from intermediate-felsic magmas, and would have permitted efficient fluid migration and accumulation at the roof of the system. We suggest that the storage of large-volume, long-lived, crystal-rich magma reservoirs in magmatic arcs may be a critical step in generating world-class porphyry copper deposits

Journal article

Matthews TJ, Loader MA, Wilkinson JJ, Buret Y, Large SJE, Birt EAet al., 2023, The Strontian Intrusive Complex: petrography, thermobarometry and the influence of titanite on residual melt chemistry, Journal of Petrology, Vol: 64, Pages: 1-23, ISSN: 0022-3530

Although the evolution of residual melts in magmatic systems controls their eruptability and ore-forming potential, their compositions are obscured in plutonic rocks by a protracted near-solidus evolution and the absence of interstitial glass. Here, we trace the evolution of residual melt compositions in rocks from the Strontian Intrusive Complex, Scotland, using the trace element chemistry of amphiboles, and titanites which are intergrown with amphibole rims. Laser ablation mapping reveals an abrupt change in certain trace elements in the amphibole rims, with sharp increases in Eu/Eu* and Sr/Y, and decreases in rare earth elements, Ta, Nb, and Ta/Nb ratios. Core-rim variations in these elements in titanite show the same variations as in amphibole, but are more gradual. By reconstructing the crystallisation sequence of the Strontian magmas using textural observations and thermobarometric estimates, we determine that amphibole cores crystallised prior to titanite saturation, but amphibole rims crystallised simultaneously with titanite. Using the trace element composition of the mineral phases and their modal abundance in the rock, with comparison to the whole-rock chemistry, we determine that titanite hosts the majority of the rare earth and high field strength element budget of the rocks. We therefore propose that the onset of titanite crystallisation had a profound effect on the trace element composition of late-stage residual melts at Strontian, which were inherited by the amphibole rims and subsequent titanites. This is supported by Rayleigh fractional crystallisation modelling, which demonstrates that the composition of amphibole rims cannot be explained without the influence of titanite. We therefore show that the saturation of trace element-rich phases in magmas represents a significant geochemical event in the petrogenesis of intermediate to silicic magmas. This has implications for provenance studies that attempt to reconstruct bulk rock compositions from mi

Journal article

Hicks S, Bie L, Rychert C, Harmon N, Goes S, Rietbrock A, Wei SS, Collier J, Henstock T, Lynch L, Prytulak J, Macpherson C, Schlaphorst D, Wilkinson J, Blundy J, Cooper G, Davy R, Kendall J-M, VoiLA Working Groupet al., 2023, Slab to back-arc to arc: fluid and melt pathways through the mantle wedge beneath the Lesser Antilles, Science Advances, Vol: 9, Pages: 1-14, ISSN: 2375-2548

Volatiles expelled from subducted plates promote melting of the overlying warm mantle, feeding arc volcanism. However, debates continue over the factors controlling melt generation and transport, and how these determine the placement of volcanoes. To broaden our synoptic view of these fundamental mantle wedge processes, we image seismic attenuation beneath the Lesser Antilles arc, an end-member system that slowly subducts old, tectonized lithosphere. Punctuated anomalies with high ratios of bulk-to-shear attenuation (Qκ−1/Qμ−1 > 0.6) and VP/VS (>1.83) lie 40 km above the slab, representing expelled fluids that are retained in a cold boundary layer, transporting fluids toward the back-arc. The strongest attenuation (1000/QS ~ 20), characterizing melt in warm mantle, lies beneath the back-arc, revealing how back-arc mantle feeds arc volcanoes. Melt ponds under the upper plate and percolates toward the arc along structures from earlier back-arc spreading, demonstrating how slab dehydration, upper-plate properties, past tectonics, and resulting melt pathways collectively condition volcanism.

Journal article

Nathwani CL, Wilkinson JJ, Brownscombe W, John CMet al., 2023, Mineral texture classification using deep convolutional neural networks: An application to zircons from porphyry copper deposits, Journal of Geophysical Research: Solid Earth, Vol: 128, Pages: 1-19, ISSN: 2169-9313

The texture and morphology of igneous zircon indicates magmatic conditions during zircon crystallization and can be used to constrain provenance. Zircons from porphyry copper deposits are typically prismatic, euhedral, and strongly oscillatory zoned which may differentiate them from zircons associated with unmineralized igneous systems. Here, cathodoluminescence images of zircons from the Quellaveco porphyry copper district, Southern Peru, were collected to compare zircon textures between the premineralization Yarabamba Batholith and the Quellaveco porphyry copper deposit. Quellaveco porphyry zircons are prismatic, euhedral, and strongly oscillatory zoned, whereas the batholith zircons are subhedral-anhedral with weaker zoning. We adopt a deep convolutional neural network (CNN) approach to demonstrate that a CNN can classify Quellaveco porphyry zircons with high success. We trial several CNN architectures to classify zircon images: LeNet-5, AlexNet and VGG, including a transfer learning approach where we used the weights of a VGG model pretrained on the ImageNet data set. The VGG model with transfer learning is the most effective approach, with accuracy and receiver operating characteristic-area under curve (ROC-AUC) scores of 0.86 and 0.93, indicating that a Quellaveco porphyry zircon CL image can be ranked higher than a batholith zircon with 93% probability. Visualizing model layer outputs demonstrates that the CNN models can recognize crystal edges, zoning, and mineral inclusions. We trial implementing trained CNN models as unsupervised feature extractors, which can empirically quantify crystal textures and morphology. Therefore, deep learning provides a tool for the extraction of information from large, imaged-based petrographic data sets which can facilitate petrologic and provenance studies.

Journal article

Loader M, Nathwani C, Wilkinson J, Armstrong Ret al., 2022, Controls on the magnitude of Ce anomalies in zircon, Geochimica et Cosmochimica Acta, Vol: 328, ISSN: 0016-7037

Increases in the magnitude of positive Ce anomalies in zircons from igneous rocks are often interpreted to be controlled by progressive melt oxidation and have been used to provide evidence for the elevated redox state of magmas associated with porphyry Cu deposits. In this paper, we test this idea by comparing trace element compositions of zircons from the Resolution porphyry Cu-Mo deposit, Arizona, with numerical models of melt Ce systematics and zircon-melt trace element partitioning. We show that although Ce anomalies in Resolution zircons (estimated by the chondrite-normalised ratio of Ce and Nd) may increase by over an order of magnitude throughout the period of zircon crystallisation, oxybarometric estimates in fact indicate a constant melt redox during this time. We employ a Monte Carlo approach to model the evolution of the Ce anomaly in zircon as a function of temperature, fO2, and melt composition, and compare our model against literature zircon data from chemically well-constrained volcanic rocks. We find that large increases in the magnitude of the Ce anomaly can be reproduced by cooling at fixed oxidation state and that this effect is magnified by increasing the melt Ce/Nd ratio, which can be driven by the co-crystallisation of amphibole, apatite and especially titanite. Increases in melt oxidation state are not sufficient to explain high positive Ce anomalies in zircons from some hydrous, oxidised volcanic and hypabyssal rocks, which additionally require a combination of titanite co-crystallisation and low crystallisation temperature. We therefore caution against the interpretation of zircon Ce anomalies solely in the context of melt fO2 variation.

Journal article

Riveros Jensen K, Campos E, Wilkinson J, Wilkinson C, Kearsley A, Miranda-Diaz G, Veliz Wet al., 2022, Hydrothermal fluid evolution in the Escondida porphyry copper deposit, northern Chile: evidence from SEM-CL imaging of quartz veins and LA-ICP-MS of fluid inclusions, Mineralium Deposita: international journal of geology, mineralogy, and geochemistry of mineral deposits, Vol: 57, Pages: 279-300, ISSN: 0026-4598

The origin of hypogene alteration and mineralization features in the Escondida 27porphyry Cu deposit resulted from intense overprinting related to three main hydrothermal 28stages. The beginning of each stage is recorded by deposition of bright quartz crystals on 29vein walls that precipitated from high-temperature fluids. In the deepest zones of the 30deposit, the earliest stage started with exsolution of intermediate-density fluids, which 31transported high concentrations of Cu, whereas Mo was not detected. However, in the 32shallow zones, the early stage began with depressurization and unmixing of intermediate-33density fluids, which generated both a hypersaline and vapour-rich fluid phase, producing 34an important geochemical segregation between both phases. The transitional stage also 35started with circulation of intermediate-density fluids but never experienced unmixing. 36These fluids transported the highest Mo concentrations in the deposit; however, Cu displays 37lower concentrations relative to intermediate-density fluids from the early stage. The 38beginning of the late stage was also associated with intermediate-density fluids; however, 39Cu and Mo were below the detection limits in most of the analysed fluids. During the 40evolution of the three stages, the fluids experienced gradual cooling, which promoted the 41precipitation of euhedral and zoned quartz crystals that overgrew the early high-42luminescence quartz generations. Sometimes, sulfide minerals display euhedral crystal 43boundaries with zoned quartz, suggesting that mineralization started during these phases.44The latest events detected in each main stage are linked to cooler and low-salinity fluids, from which dark quartz and hypogene sulfide sprecipitated along microfractures and 46interstitial spaces developed in the earlier quartz generations.

Journal article

Nathwani C, Wilkinson J, Fry G, Armstrong R, Smith D, Ihlenfeld Cet al., 2022, Machine learning for geochemical exploration: classifying metallogenic fertility in arc magmas and insights into porphyry copper deposit formation, Mineralium Deposita: international journal of geology, mineralogy, and geochemistry of mineral deposits, Vol: 57, Pages: 1143-1166, ISSN: 0026-4598

A current mineral exploration focus is the development of tools to identify magmatic districts predisposed to host porphyry copper deposits. In this paper, we train and test four, common, supervised machine learning algorithms: logistic regression, support vector machines, artificial neural networks and Random Forest to classify metallogenic “fertility” in arc magmas based on whole-rock geochemistry. We outline pre-processing steps that can be used to mitigate against the undesirable characteristics of geochemical data (high multicollinearity, sparsity, missing values, class imbalance and compositional data effects) and therefore produce more meaningful results. We evaluate the classification accuracy of each supervised machine learning technique using a 10-fold cross validation technique and by testing the models on deposits unseen during the training process. This yields 81-83% accuracy for all classifiers, and receiver operating characteristic (ROC) curves have mean area under curve (AUC) scores of 87-89% indicating the probability of ranking a “fertile” rock higher than an “unfertile” rock. By contrast, bivariate classification schemes show much lower performance, demonstrating the value of classifying geochemical data in high dimension space. Principal component analysis suggests that porphyry-fertile magmas fractionate deep in the arc crust, and that calc-alkaline magmas associated with Cu-rich porphyries evolve deeper in the crust than more alkaline magmas linked with Au-rich porphyries. Feature analysis of the machine learning classifiers suggests that the most important parameters associated with fertile magmas are low Mn, high Al, high Sr, high K and 1 listric REE patterns. These signatures further highlight the association of porphyry Cu deposits with hydrous arc magmas that undergo amphibole fractionation in the deep arc crust.

Journal article

McFall K, McDonald I, Wilkinson J, 2021, Assessing the role of tectono-magmatic setting in the precious metal (Au, Ag, PGE) and critical metal (Te, Se, Bi) endowment of Porphyry Cu deposits, Tectonomagmatic Influences on Metallogeny and Hydrothermal Ore Deposits: A Tribute to Jeremy P. Richards (Volume II), Editors: Sholeh, Wang, Publisher: Society of Economic Geologists, Inc., Pages: 277-295, ISBN: 978-1-629496-44-3

Porphyry Cu deposits commonly contain critical and precious metal by-products, including the chalcophile and siderophile elements, Au, Pd, Pt, Ag, Te, Se, and Bi. These elements partition into residual sulfides duringthe partial melting of mantle wedge peridotite during subduction, potentially depleting the source magma for subduction-related porphyry Cu deposits. The chalcophile-rich residual sulfides in subduction-modified sub-continental lithosphere are thought to be the source of metals in postsubduction porphyry Cu deposits, and as such these deposits may be more enriched in chalcophile and siderophile elements than subduction-related porphyry deposits, although many postsubduction deposits have low Au grades. We test this by presenting whole-rock assay and PGE data with in situ LA-ICP-MS trace element data from sulfide minerals from three porphyry Cu deposits. The Skouries Cu-Au-(PGE) porphyry deposit, Greece, and the Muratdere Cu-Au-Mo porphyry deposit, Turkey are both postsubduction; these are contrasted with the El Teniente Cu-Mo porphyry deposit, Chile, which is a classic subduction-related system. By comparing these results with a newly compiled global dataset of trace element concentrations in sulfides from 18 other porphyry Cu deposits we show that postsubduction porphyry Cu deposit sulfides are relatively enriched in Bi, Sb, Te, and Se compared to sulfide minerals from subduction-related deposits. However, although some critical and precious metals (Ag, Bi, and Se) mainly reside in primary sulfide ore minerals, others (Au, Te, Pd, and Pt) are predominantly hosted in minoraccessory minerals. Whole-rock data from mineralized samples show that although the Skouries and Muratdere deposits are enriched in Au compared with El Teniente, globally both subduction-related and postsubductiondeposits can be precious and critical metal enriched, with metal endowment independent of tectonic setting. PGE-enriched porphyry Cu deposits are also enriched in Bi, Te, and

Book chapter

Braszus B, Goes S, Allen R, Rietbrock A, Collier J, Harmon N, Henstock T, Hicks S, Rychert CA, Maunder B, van Hunen J, Bie L, Blundy J, Cooper G, Davy R, Kendall JM, Macpherson C, Wilkinson J, Wilson Met al., 2021, Subduction history of the Caribbean from upper-mantle seismic imaging and plate reconstruction, Nature Communications, Vol: 12, Pages: 1-14, ISSN: 2041-1723

The margins of the Caribbean and associated hazards and resources have been shaped by a poorly understood history of subduction. Using new data, we improve teleseismic P-wave imaging of the eastern Caribbean upper mantle and compare identified subducted-plate fragments with trench locations predicted from plate reconstruction. This shows that material at 700–1200 km depth below South America derives from 90–115 Myr old westward subduction, initiated prior to Caribbean Large-Igneous-Province volcanism. At shallower depths, an accumulation of subducted material is attributed to Great Arc of the Caribbean subduction as it evolved over the past 70 Ma. We interpret gaps in these subducted-plate anomalies as: a plate window and tear along the subducted Proto-Caribbean ridge; tearing along subducted fracture zones, and subduction of a volatile-rich boundary between Proto-Caribbean and Atlantic domains. Phases of back-arc spreading and arc jumps correlate with changes in age, and hence buoyancy, of the subducting plate.

Journal article

Schlaphorst D, Harmon N, Kendall JM, Rychert CA, Collier J, Rietbrock A, Goes Set al., 2021, Variation in upper plate crustal and lithospheric mantle structure in the Greater and Lesser Antilles from ambient noise tomography, G3: Geochemistry, Geophysics, Geosystems: an electronic journal of the earth sciences, Vol: 22, Pages: 1-17, ISSN: 1525-2027

The crust and upper mantle structure of the Greater and Lesser Antilles Arc provides insights into key subduction zone processes in a unique region of slow convergence of old slow-spreading oceanic lithosphere. We use ambient noise tomography gathered from island broadband seismic stations and the temporary ocean bottom seismometer network installed as part of the Volatile Recycling in the Lesser Antilles experiment to map crustal and upper mantle shear-wave velocity of the eastern Greater Antilles and the Lesser Antilles Arc. Taking the depth to the 2.0 km/s contour as a proxy, we find sediment thickness up to 15 km in the south in the Grenada and Tobago basins and thinner sediments near the arc and to the north. We observe thicker crust, based on the depth to the 4.0 km/s velocity contour, beneath the arc platforms with the greatest crustal thickness of around 30 km, likely related to crustal addition from arc volcanism through time. There are distinct low velocity zones (4.2–4.4 km/s) in the mantle wedge (30–50 km depth), beneath the Mona Passage, Guadeloupe-Martinique, and the Grenadines. The Mona passage mantle anomaly may be related to ongoing extension there, while the Guadeloupe-Martinique and Grenadine anomalies are likely related to fluid flux, upwelling, and/or partial melt related to nearby slab features. The location of the Guadeloupe-Martinique anomaly is slightly to the south of the obliquely subducted fracture zones. This feature could be explained by either three-dimensional mantle flow, a gap in the slab, variable slab hydration, and/or melt dynamics including ponding and interactions with the upper plate.

Journal article

Davey J, Roberts S, Wilkinson J, 2021, Copper- and cobalt-rich, ultrapotassic bittern brines responsible for the formation of the Nkana-Mindola deposits, Zambian Copperbelt, Geology (Boulder), Vol: 49, Pages: 341-345, ISSN: 0091-7613

The Central African Copperbelt (CACB) is Earth’s largest repository of sediment-hosted copper and cobalt. The criticality of these elements in battery technology and electricity transmission establishes them as fundamental components of the carbon-free energy revolution, yet the nature and origin of the hydrothermal fluids responsible for ore formation in the CACB remain controversial. Here, we present microthermometric, scanning electron microscopy and laser ablation–inductively coupled plasma–mass spectrometry analyses of fluid inclusions from the Nkana-Mindola deposits in Zambia. We find that base metal concentrations vary by one to two orders of magnitude between “barren” and “ore” fluids, with concomitant distinctions in major salt chemistry. Primary fluid inclusions, hosted by pre- to synkinematic mineralized quartz veins, are characterized by high homogenization temperatures (~200–300 °C) and salinities, with K/Na >0.8 and elevated metal concentrations (102 to 103 ppm Cu and Co). Conversely, barren, post-kinematic vein quartz contains lower homogenization temperature (~110–210 °C) and lower-salinity primary inclusions, characterized by K/Na <0.8 with low metal contents (<102 ppm Cu and Co). We propose a model in which high-temperature, sulfate-deficient, metalliferous, potassic residual brines, formed during advanced evaporation of CaCl2-rich, mid-Neoproterozoic seawater, were responsible for ore formation. During basin closure, lower-temperature, halite-undersaturated fluids interacted with evaporites and formed structurally controlled, sodic metasomatism. Reconciliation of these fluid chemistries and base metal concentrations with reported alteration assemblages from a majority of Zambian Copperbelt deposits suggests highly evolved, residual brines were critical to the formation of this unique metallogenic province.

Journal article

Nathwani CL, Simmons AT, Large SJE, Wilkinson JJ, Buret Y, Ihlenfeld Cet al., 2021, From long-lived batholith construction to giant porphyry copper deposit formation: petrological and zircon chemical evolution of the Quellaveco District, Southern Peru, Contributions to Mineralogy and Petrology, Vol: 176, ISSN: 0010-7999

Porphyry Cu ore deposits are a rare product of arc magmatism that often form spatiotemporal clusters in magmatic arcs. The petrogenetic evolution of igneous rocks that cover the temporal window prior to and during porphyry Cu deposit formation may provide critical insights into magmatic processes that are key in generating these systems. This study documents the magmatic evolution of the Palaeocene–Eocene Yarabamba Batholith, Southern Peru, that was incrementally assembled between ~ 67 and ~ 59 Ma and hosts three, nearly contemporaneous, giant porphyry Cu–Mo deposits that formed at 57–54 Ma (Quellaveco, Toquepala and Cuajone). Whole-rock geochemistry, U–Pb geochronology and zircon trace element chemistry are reported from Yarabamba rocks that span the duration of plutonic activity, and from six porphyry intrusions at Quellaveco that bracket mineralisation. A change in whole-rock chemistry in Yarabamba intrusive rocks to high Sr/Y, high La/Yb and high Eu/Eu* is observed at ~ 60 Ma which is broadly coincident with a change in vector of the converging Nazca plate and the onset of regional compression and crustal thickening during the first stage of the Incaic orogeny. The geochemical changes are interpreted to reflect a deepening of the locus of lower crustal magma evolution in which amphibole ± garnet are stabilised as early and abundant fractionating phases and plagioclase is suppressed. Zircons in these rocks show a marked change towards higher Eu/Eu* (> 0.3) and lower Ti (< 9 ppm) compositions after ~ 60 Ma. Numerical modelling of melt Eu systematics and zircon-melt partitioning indicates that the time series of zircon Eu/Eu* in these rocks can be explained by a transition from shallower, plagioclase-dominated fractionation to high-pressure amphibole-dominated fractionation at deep crustal levels from ~ 60 Ma. Our modelling suggests

Journal article


Journal article

Cooper GF, Macpherson CG, Blundy JD, Maunder B, Allen RW, Goes S, Collier JS, Bie L, Harmon N, Hicks SP, Iveson AA, Prytulak J, Rietbrock A, Rychert CA, Davidson JP, Kendall MJ, Schlaphorst Det al., 2020, Variable water input controls evolution of the Lesser Antilles volcanic arc (vol 87, pg 931, 2020), Nature, Vol: 584, Pages: E36-E36, ISSN: 0028-0836

Journal article

Loader MA, Wilkinson JJ, Armstrong RN, 2020, The effect of titanite crystallisation on Eu and Ce anomalies in zircon and its implications for the assessment of porphyry Cu deposit fertility, 14th SGA Biennial Meeting on Mineral Resources to Discover, Publisher: SGA, Pages: 1091-1094

The redox sensitivity of Ce and Eu anomalies in zircon has been well demonstrated by experimental studies and these parameters may represent important tools in the exploration of porphyry Cu systems which are thought to be derived from oxidised magmas. However, Ce and Eu anomalies in zircon are also affected by the co-crystallisation of REE-bearing phases such as titanite. Here, we report the trace element chemistry of zircons from titanite-bearing intrusions associated with mineralisation at the world class Oyu Tolgoi porphyry Cu-Au deposit (Mongolia). Based on these data, we suggest that neither Eu/Eu*, nor Ce4+/Ce3+ are robust proxies for melt redox conditions, because they are both too strongly dependent on melt REE concentrations, which are usually poorly constrained and controlled by the crystallisation of titanite and other REE-bearing phases. In spite of this, Eu/Eu* can broadly distinguish between fertile and barren systems, so may still be a useful indicator of porphyry magma fertility.

Conference paper

Cooper GF, Macpherson CG, Blundy JD, Maunder B, Allen RW, Goes S, Collier JS, Bie L, Harmon N, Hicks SP, Iveson AA, Prytulak J, Rietbrock A, Rychert CA, Davidson JPet al., 2020, Variable water input controls evolution of the Lesser Antilles volcanic arc, Nature, Vol: 582, Pages: 525-529, ISSN: 0028-0836

Oceanic lithosphere carries volatiles, notably water, into the mantle through subduction at convergent plate boundaries. This subducted water exercises control on the production of magma, earthquakes, formation of continental crust and mineral resources. Identifying different potential fluid sources (sediments, crust and mantle lithosphere) and tracing fluids from their release to the surface has proved challenging1. Atlantic subduction zones are a valuable endmember when studying this deep water cycle because hydration in Atlantic lithosphere, produced by slow spreading, is expected to be highly non-uniform2. Here, as part of a multi-disciplinary project in the Lesser Antilles volcanic arc3, we studied boron trace element and isotopic fingerprints of melt inclusions. These reveal that serpentine—that is, hydrated mantle rather than crust or sediments—is a dominant supplier of subducted water to the central arc. This serpentine is most likely to reside in a set of major fracture zones subducted beneath the central arc over approximately the past ten million years. The current dehydration of these fracture zones coincides with the current locations of the highest rates of earthquakes and prominent low shear velocities, whereas the preceding history of dehydration is consistent with the locations of higher volcanic productivity and thicker arc crust. These combined geochemical and geophysical data indicate that the structure and hydration of the subducted plate are directly connected to the evolution of the arc and its associated seismic and volcanic hazards.

Journal article

Davy R, Collier JS, Henstock TJ, the VoiLA consortiumet al., 2020, Wide‐angle seismic imaging of two modes of crustal accretion in mature Atlantic Ocean crust, Journal of Geophysical Research: Solid Earth, Vol: 125, Pages: 1-21, ISSN: 2169-9313

We present a high‐resolution 2‐D P‐wave velocity model from a 225 km long active seismic profile, collected over ~60‐75 Ma central Atlantic crust. The profile crosses five ridge segments separated by a transform and three non‐transform offsets. All ridge discontinuities share similar primary characteristics, independent of the offset. We identify two types of crustal segment. The first displays a classic two‐layer velocity structure with a high gradient layer 2 (~0.9 s‐1) above a lower gradient layer 3 (0.2 s‐1). Here PmP coincides with the 7.5 km s‐1 contour and velocity increases to >7.8 km s‐1 within 1 km below. We interpret these segments as magmatically‐robust, with PmP representing a petrological boundary between crust and mantle. The second has a reduced contrast in velocity gradient between upper and lower crust, and PmP shallower than the 7.5 km s‐1 contour. We interpret these segments as tectonically dominated, with PmP representing a serpentinized (alteration) front. Whilst velocity depth profiles fit within previous envelopes for slow‐spreading crust, our results suggest that such generalizations give a misleading impression of uniformity. We estimate that the two crustal styles are present in equal proportions on the floor of the Atlantic. Within two tectonically dominated segments we make the first wide‐angle seismic identifications of buried oceanic core complexes in mature (> 20 Ma) Atlantic Ocean crust. They have a ~20 km wide “domal” morphology with shallow basement and increased upper‐crustal velocities. We interpret their mid‐crustal seismic velocity inversions as alteration and rock‐type assemblage contrasts across crustal‐scale detachment faults.

Journal article

Cooke DR, Wilkinson JJ, Baker M, Agnew P, Phillips J, Chang Z, Chen H, Wilkinson CC, Inglis S, Hollings P, Zhang L-J, Gemmell BJ, White NC, Danyushevsky L, Martin Het al., 2020, Using mineral chemistry to aid exploration: a case study from the resolution porphyry Cu-Mo deposit, Arizona, Economic Geology, Vol: 115, Pages: 813-840, ISSN: 0013-0109

The giant, high-grade Resolution porphyry Cu-Mo deposit in the Superior district of Arizona is hosted in Proterozoic and Paleozoic basement and in an overlying Cretaceous volcaniclastic breccia and sandstone package. Resolution has a central domain of potassic alteration that extends more than 1 km outboard of the ore zone, overlapping with a propylitic halo characterized by epidote, chlorite, and pyrite that is particularly well developed in the Laramide volcaniclastic rocks and Proterozoic dolerite sills. The potassic and propylitic assemblages were overprinted in the upper parts of the deposit by intense phyllic and advanced argillic alteration. The district was disrupted by Tertiary Basin and Range extension, and the fault block containing Resolution and its Cretaceous host succession was buried under thick mid-Miocene dacitic volcanic cover, obscuring the geologic, geophysical, and geochemical footprint of the deposit.To test the potential of propylitic mineral chemistry analyses to aid in the detection of concealed porphyry deposits, a blind test was conducted using a suite of epidote-chlorite ± pyrite-altered Laramide volcaniclastic rocks and Proterozoic dolerites collected from the propylitic halo, with samples taken from two domains located to the north and south and above the Resolution ore zone. Laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) data of epidote provided indications of deposit fertility and proximity. Competition for chalcophile elements (As, Sb, Pb) between coexisting pyrite and epidote grains led to a subdued As-Sb fertility response in epidote, consistent with epidote collected between 0.7 and 1.5 km from the center of a large porphyry deposit. Temperature-sensitive trace elements in chlorite provided coherent spatial zonation patterns, implying a heat source centered at depth between the two sample clusters, and application of chlorite proximitor calculations based on LA-ICP-MS analyses provided a precisely

Journal article

Wilkinson JJ, Baker MJ, Cooke DR, Wilkinson CCet al., 2020, Exploration targeting in porphyry Cu systems using propylitic mineral chemistry: a case study of the El Teniente deposit, Chile, Economic Geology, Vol: 115, Pages: 771-791, ISSN: 0013-0109

The mineral chemistry of epidote and chlorite from the propylitic halo at El Teniente, in samples collected at distances up to 6.6 km from the deposit center, was determined by microprobe and laser ablation-inductively coupled plasma-mass spectrometry. Results show that both minerals systematically incorporated a range of trace elements that define a much larger footprint to the system than is easily recognized using conventional means such as whole-rock geochemistry. Apart from Fe and Mg in chlorite, there is no significant control of mineral chemistry by bulk-rock composition. For chlorite, geothermometry temperatures and Ti and V concentrations are high proximal, whereas Li, As, Co, Sr, Ca, and Y are low proximal and elevated in distal positions. Ratios of these elements define gradients toward ore varying over three to five orders of magnitude. The proximal-high Ti content is thought to reflect crystallization temperature, whereas proximal-low signatures are believed to characterize elements that are relatively fluid mobile in the inner parts of the propylitic halo in the presence of mildly alkaline to mildly acidic and oxidized fluids so that they are not incorporated into crystallizing chlorite, despite being generally compatible within the mineral structure. These elements begin to substitute into chlorite in the distal parts of the propylitic halo where fluids are largely rock buffered in terms of major element chemistry. In epidote, As defines a broad proximal low and is generally elevated at distances of at least 3 km from the edge of the ore shell. Zinc, La, Yb, Y, and Zr in epidote, among others, appear to define a geochemical shoulder that surrounds the deposit. These patterns are broadly similar to those observed in previous work at Batu Hijau and in the Baguio district, suggesting that these minerals behave consistently in porphyry systems and can therefore provide useful exploration tools within propylitic green rocks.

Journal article

Baker MJ, Wilkinson JJ, Wilkinson CC, Cooke DR, Ireland Tet al., 2020, Epidote trace element chemistry as an exploration tool in the collahuasi district, Northern Chile, Economic Geology, Vol: 115, Pages: 749-770, ISSN: 0013-0109

The Collahuasi district of northern Chile hosts several late Eocene-early Oligocene world-class porphyry Cu-Mo deposits, including Rosario, Ujina, and Quebrada Blanca deposits, and associated high-sulfidation epithermal mineralization at La Grande. Mineralization is hosted by intermediate to felsic intrusive and volcanic rocks of the upper Paleozoic to Lower Triassic Collahuasi Group, which experienced lower greenschist facies regional metamorphism prior to mineralization. Extensive hydrothermal alteration zones surround the porphyry and epithermal deposits, associated with hypogene ore-forming processes. However, outside of the observed sulfide halo the limits of geochemical anomalism associated with mineralization are difficult to define due to mineralogical similarities between weak, distal propylitic alteration and regional metamorphism affecting the host rocks.Recent advancements in laser ablation-inductively coupled plasma-mass spectrometry analysis of epidote from hydrothermal alteration zones around porphyry and skarn deposits have shown that low-level hypogene geochemical anomalies can be detected at distances farther from the center of mineralization than by conventional rock chip sampling. Selective analysis of propylitic epidote from the Collahuasi district indicates that anomalous concentrations of distal pathfinder elements in epidote, including As (>50 ppm), Sb (>25 ppm), Pb (>100 ppm), and Mn (>5,000 ppm), were detectable 1.5 to 4.0 km from deposit centers. Significantly, the concentrations of these trace elements in epidote were obtained from samples that contained whole-rock concentrations of <25 ppm As, <2 ppm Sb, <100 ppm Pb, and <5,000 ppm Mn. Systematic increases in Cu, Mo, and Sn concentrations in epidote near deposit centers, and corresponding decreasing As, Sb and Pb concentrations, also provide effective tools for assessing the fertility and locating the centers of porphyry mineralization. In addition, anomalous conc

Journal article

Pacey A, Wilkinson JJ, Cooke DR, 2020, Chlorite and epidote mineral chemistry in porphyry ore systems: a case study of the Northparkes district, NSW, Australia, Economic Geology, Vol: 115, Pages: 701-727, ISSN: 0361-0128

Propylitic alteration, characterized by the occurrence of chlorite and epidote, is typically the most extensive and peripheral alteration facies developed around porphyry ore deposits. However, exploration within this alteration domain is particularly challenging, commonly owing to weak or nonexistent whole-rock geochemical gradients and the fact that similar assemblages can be developed in other geologic settings, particularly during low-grade metamorphism. We document and interpret systematic spatial trends in the chemistry of chlorite and epidote from propylitic alteration around the E48 and E26 porphyry Cu-Au deposits of the Northparkes district, New South Wales, Australia. These trends vary as a function of both distance from hydrothermal centers and alteration paragenesis.The spatial trends identified in porphyry-related chlorite and epidote at Northparkes include (1) a deposit-proximal increase in Ti, As, Sb, and V in epidote and Ti in chlorite, (2) a deposit-distal increase in Co and Li in chlorite and Ba in epidote, and (3) a pronounced halo around deposits in which Mn and Zn in chlorite, as well as Mn, Zn, Pb, and Mg in epidote, are elevated. Chlorite Al/Si ratios and epidote Al/Fe ratios may show behavior similar to that of Mn-Zn or may simply decrease outward, and V and Ni concentrations in chlorite are lowest in the peak Mn-Zn zone. In comparison to porphyry-related samples, chlorite from the regional metamorphic assemblage in the district contains far higher concentrations of Li, Ca, Ba, Pb, and Cu but much less Ti. Similarly, metamorphic epidote contains higher concentrations of Sr, Pb, As, and Sb but less Bi and Ti.These chlorite and epidote compositional trends are the net result of fluid-mineral partitioning under variable physicochemical conditions within a porphyry magmatic-hydrothermal system. They are most easily explained by the contribution of spent magmatic-derived ore fluid(s) into the propylitic domain. It is envisaged that such fluids exp

Journal article

Pacey, Adam, Wilkinson J, Boyce A, Millar Iet al., 2020, Magmatic fluids implicated in the formation of propylitic alteration: oxygen, hydrogen and strontium isotopic constraints from the Northparkes Porphyry Cu-Au District, NSW, Australia, Economic Geology and the Bulletin of the Society of Economic Geologists, Vol: 115, Pages: 729-748, ISSN: 0361-0128

In porphyry ore deposit models, the propylitic facies is widely interpreted to be caused by convective 16circulation ofmeteoric waters. However, recent field-­‐based and geochemical data suggest that magmatic-­‐derived fluids are likely to contribute to development of the propylitic assemblage. In order to test this hypothesis, we etermined the oxygenand hydrogen isotope compositions of propylitic mineral separates 19(epidote, chlorite and quartz), selected potassic mineral separates (quartz and magnetite) and quartz-­‐hosted fluid inclusionsfrom around the E48 and E26 deposits in the Northparkes porphyry Cu-­‐Au district, NSW,Australia. In addition, the strontiumisotope composition of epidote was determined to test for the potential contribution of seawater in the Northparkes system given the postulated island arc setting and submarine character of some country rocks.

Journal article

Sievwright RH, O'Neill HSC, Tolley J, Wilkinson JJ, Berry AJet al., 2020, Diffusion and partition coefficients of minor and trace elements in magnetite as a function of oxygen fugacity at 1150 oC, Contributions to Mineralogy and Petrology, Vol: 175, Pages: 1-21, ISSN: 0010-7999

Lattice diffusion coefficients and partition coefficients have been determined for Li, Mg, Al, Sc, Ti, Cr, V, Mn, Co, Ni, Cu, Zn, Ga, Y, Zr, Nb, Mo, In, Lu, Hf, Ta and U in single crystals of natural magnetite as a function of oxygen fugacity (fO2) at 1150 °C and 1 bar by equilibration with a synthetic silicate melt reservoir. Most experiments were run for twelve hours, which was sufficient to generate diffusion profiles from 25 to > 1000 µm in length. The results were checked at one condition with two additional experiments at 66.9 and 161 h. The profiles were analysed using scanning laser-ablation inductively-coupled-plasma mass-spectrometry. Diffusion coefficients (D) were calculated by fitting data from individual element diffusion profiles to the conventional diffusion equation for one-dimensional diffusion into a semi−infinite slab with constant composition maintained in the melt at the interface. Equilibrium magnetite/melt partition coefficients are given by the ratio of the interface concentrations to those in the melt. Plots of log D as a function of log fO2 produce V-shaped trends for all the investigated elements, representing two different mechanisms of diffusion that depend on (fO2)−2/3 and (fO2)2/3. Diffusion coefficients at a given fO2 generally increase in the order: Cr < Mo ≈ Ta < V < Ti < Al < Hf ≈ Nb < Sc ≈ Zr ≈ Ga < In < Lu ≈ Y < Ni < U ≈ Zn < Mn ≈ Mg < Co < Li < Cu. Thus, Cu contents of magnetites are most susceptible to diffusive reequilibration, whereas the original content of Cr should be best preserved.

Journal article

Cooke DR, Agnew P, Hollings P, Baker M, Chang Z, Wilkinson J, Ahmed A, White NC, Zhang L, Thompson J, Gemmell JB, Chen Het al., 2020, Recent advances in the application of mineral chemistry to exploration for porphyry copper–gold–molybdenum deposits: detecting the geochemical fingerprints and footprints of hypogene mineralization and alteration, Geochemistry: Exploration, Environment, Analysis, Vol: 20, Pages: 176-188, ISSN: 1467-7873

In the past decade, significant research efforts have been devoted to mineral chemistrystudies to assist porphyry exploration. These activities can be divided into two majorfields of research: (1) porphyry indicator minerals (PIMs), which are used to identify thepresence of, or potential for, porphyry-style mineralization based on the chemistry ofmagmatic minerals such as zircon, plagioclase and apatite, or resistate hydrothermalminerals such as magnetite; and (2) porphyry vectoring and fertility tools (PVFTs),which use the chemical compositions of hydrothermal minerals such as epidote,chlorite and alunite to predict the likely direction and distance to mineralized centers,and the potential metal endowment of a mineral district. This new generation ofexploration tools has been enabled by advances in and increased access to laserablation-inductively coupled plasma mass spectrometry (LA-ICP-MS), short wavelength infrared (SWIR), visible near-infrared (VNIR) and hyperspectral technologies.PIMs and PVFTs show considerable promise for exploration and are starting to beapplied to the diversity of environments that host porphyry and epithermal depositsglobally. Industry has consistently supported development of these tools, in the case ofPVFTs encouraged by several successful blind tests where deposit centers havesuccessfully been predicted from distal propylitic settings. Industry adoption is steadilyincreasing but is restrained by a lack of the necessary analytical equipment andexpertise in commercial laboratories, and also by the on-going reliance on well-established geochemical exploration techniques (e.g., sediment, soil and rock-chipsampling) that have aided the discovery of near-surface resources over many decades, are now proving less effective in the search for deeply buried mineral resources, and for those concealed under cover.

Journal article

Hnatyshin D, Creaser RA, Meffre S, Stern RA, Wilkinson JJ, Turner ECet al., 2020, Understanding the microscale spatial distribution and mineralogical residency of Re in pyrite: Examples from carbonate-hosted Zn-Pb ores and implications for pyrite Re-Os geochronology, Chemical Geology, Vol: 533, Pages: 1-21, ISSN: 0009-2541

Accurate and precise geochronology using the Re-Os isotopic system in pyrite is an invaluable tool for developing and confirming genetic models of ore systems. However, as a bulk method, the results produced by pyrite Re-Os geochronology are commonly complex, and many imprecise isochrons exist in the literature. Using LA-ICPMS methods it is now possible to map and quantify Re distribution at the ppb level, allowing an unprecedented look into the Re-Os systematics of pyrite-bearing ore.Two samples from the Lisheen Zn-Pb ore deposit in Ireland showing disparate Re-Os isotopic behavior were investigated. In-situ sulfur isotope measurements using SIMS, an analytical technique not previously attempted on the Irish deposits, was used to supplement the Re-Os dataset. A massive pyrite sample from the Main Zone produced a precise, low-scatter isochron (346.6 ± 3.0 Ma, MSWD = 1.6). The Re distribution in this sample is relatively homogeneous, with the Re budget dominated by pyrite containing 1–5 ppb Re, but the δ34S varies significantly from −45.2‰ to 8.2‰. A second, more paragenetically complex, sample from the Derryville Zone produced a younger age with high scatter (322 ± 11 Ma, MSWD = 206) and this also displays a large variation in δ34S (−53‰ to +4‰). The cores of grains of main-stage iron sulfide are depleted in trace elements and show low Re abundances (<10 ppb) but have been altered in an irregular fashion leading to Re-enriched domains that exceed 100 ppb. Additionally, micron-scale molybdenite crystals, found in close association with altered sulfides, contain Re at levels that locally exceed 10 ppm. The highly scattered (MSWD = 206) and younger age (322 Ma), produced by the Derryville Zone sample are interpreted to result from mixing of different generations of sulfide, potentially involving fluids associated with Variscan deformation (<310 Ma). Therefore, the Re-Os data produced from the

Journal article

Nathwani C, Loader M, Wilkinson J, Buret Y, Sievwright R, Hollings Pet al., 2020, Multi-stage arc magma evolution recorded by apatite in volcanic rocks, Geology (Boulder), Vol: 48, Pages: 323-327, ISSN: 0091-7613

Protracted magma storage in the deep crust is a key stage in the formation of evolved, hydrous arc magmas that can result in explosive volcanism and the formation of economically valuable magmatic13 hydrothermal ore deposits. High magmatic water content in the deep crust results in extensive amphibole ± garnet fractionation and the suppression of plagioclase crystallization as recorded by elevated Sr/Y ratios and high Eu (high Eu/Eu*) in the melt. Here, we use a novel approach to track the petrogenesis of arc magmas using apatite trace element chemistry in volcanic formations from the Cenozoic arc of Central Chile. These rocks formed in a magmatic cycle that culminated in high Sr/Y magmatism and porphyry ore deposit formation in the Miocene. We use Sr/Y, Eu/Eu* and Mg in apatite to track discrete stages of arc magma evolution. We apply fractional crystallization modeling to show that early crystallizing apatite inherits a high Sr/Y and Eu/Eu* melt chemistry signature that is predetermined by amphibole-dominated fractional crystallization in the lower crust. Our modeling shows that crystallization of the in-situ host rock mineral assemblage in the shallow crust causes competition for trace elements in the melt that leads to apatite compositions diverging from bulk magma chemistry. Understanding this decoupling behavior is important for the use of apatite as an indicator of metallogenic fertility in arcs and for interpretation of provenance in detrital studies.

Journal article

Bie L, Rietbrock A, Hicks S, Allen R, Blundy J, Clouard V, Collier J, Davidson J, Garth T, Goes S, Harmon N, Henstock T, van Hunen J, Kendall M, Kruger F, Lynch L, Macpherson C, Robertson R, Rychert K, Tait S, Wilkinson J, Wilson Met al., 2020, Along‐arc heterogeneity in local seismicity across the lesser antilles subduction zone from a dense ocean‐bottom seismometer network, Seismological Research Letters, Vol: 91, Pages: 237-247, ISSN: 0895-0695

The Lesser Antilles arc is only one of two subduction zones where slow‐spreading Atlantic lithosphere is consumed. Slow‐spreading may result in the Atlantic lithosphere being more pervasively and heterogeneously hydrated than fast‐spreading Pacific lithosphere, thus affecting the flux of fluids into the deep mantle. Understanding the distribution of seismicity can help unravel the effect of fluids on geodynamic and seismogenic processes. However, a detailed view of local seismicity across the whole Lesser Antilles subduction zone is lacking. Using a temporary ocean‐bottom seismic network we invert for hypocenters and 1D velocity model. A systematic search yields a 27 km thick crust, reflecting average arc and back‐arc structures. We find abundant intraslab seismicity beneath Martinique and Dominica, which may relate to the subducted Marathon and/or Mercurius Fracture Zones. Pervasive seismicity in the cold mantle wedge corner and thrust seismicity deep on the subducting plate interface suggest an unusually wide megathrust seismogenic zone reaching ∼65km∼65  km depth. Our results provide an excellent framework for future understanding of regional seismic hazard in eastern Caribbean and the volatile cycling beneath the Lesser Antilles arc.

Journal article

Harmon N, Rychert C, Collier J, Henstock T, van Hunen J, Wilkinson JJet al., 2019, Mapping geologic features onto subducted slabs, Geophysical Journal International, Vol: 219, Pages: 725-733, ISSN: 0956-540X

Estimating the location of geologic and tectonic features on a subducting plate is important for interpreting their spatial relationships with other observables including seismicity, seismic velocity and attenuation anomalies, and the location of ore deposits and arc volcanism in the over-riding plate. Here we present two methods for estimating the location of predictable features such as seamounts, ridges and fracture zones on the slab. One uses kinematic reconstructions of plate motions, and the other uses multidimensional scaling to flatten the slab onto the surface of the Earth. We demonstrate the methods using synthetic examples and also using the test case of fracture zones entering the Lesser Antilles subduction zone. The two methods produce results that are in good agreement with each other in both the synthetic and real examples. In the Lesser Antilles, the subducted fracture zones trend northwards of the surface projections. The two methods begin to diverge in regions where the multidimensional scaling method has its greatest likely error. Wider application of these methods may help to establish spatial correlations globally.

Journal article

Allen R, Collier J, Stewart A, Henstock T, Goes S, Rietbrock Aet al., 2019, The role of arc migration in the development of the Lesser Antilles: a new tectonic model for the Cenozoic evolution of the eastern Caribbean, Geology, Vol: 47, Pages: 891-895, ISSN: 0091-7613

Continental arc systems often show evidence of large-scale migration both towards and away from the incoming plate. In oceanic arc systems however, whilst slab roll-back and the associated processes of back-arc spreading and arc migration towards the incoming plate are commonplace, arc migration away from the incoming plate is rarely observed. We present a new compilation of marine magnetic anomaly and seismic data in order to propose a new tectonic model for the eastern Caribbean region that includes arc migration in both directions. We synthesise new evidence to show two phases of back-arc spreading and eastward arc migration towards the incoming Atlantic. A third and final phase of arc migration to the west subdivided the earlier back-arc basin on either side of the present-day Lesser Antilles Arc. This is the first example of regional multi-directional arc migration in an intra-oceanic setting and has implications for along-arc structural and geochemical variations. The back and forth arc migrations are probably due to the constraints the neighbouring American plates impose on this isolated subduction system rather than variations in subducting slab buoyancy.

Journal article

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