The structure and petrology of the Cnoc nan Cuilean Intrusion, Loch Loyal Syenite Complex, NW Scotland

In NW Scotland, several alkaline intrusive complexes of Silurian age intrude the Caledonian orogenic front. The most northerly is the Loch Loyal Syenite Complex, which is divided into three separate intrusions (Ben Loyal, Beinn Stumanadh and Cnoc nan Cuilean). Mapping of the Cnoc nan Cuilean intrusion shows two main zones: a Mixed Syenite Zone (MZ) and a Massive Leucosyenite Zone (LZ), with a gradational contact. The MZ forms a lopolith, with multiple syenitic lithologies, including early basic melasyenites and later felsic leucosyenites. Leucosyenite melts mixed and mingled with melasyenites, resulting in extreme heterogeneity within the MZ. Continued felsic magmatism resulted in formation of the relatively homogeneous LZ, invading western parts of the MZ and now forming the topographically highest terrane. The identification of pegmatites, microgranitic veins and unusual biotite-magnetite veins demonstrates the intrusion's complex petrogenesis. Cross-sections have been used to create a novel 3D GoCad™ model contributing to our understanding of the intrusion. The Loch Loyal Syenite Complex is known to have relatively high concentrations of rare earth elements (REEs), and thus the area has potential economic and strategic value. At Cnoc nan Cuilean, abundant REE-bearing allanite is present within melasyenites of the MZ. Extensive hydrothermal alteration of melasyenites here formed steeply dipping biotite-magnetite veins, most enriched in allanite and other REE-bearing accessories. This study has thus identified the area of greatest importance for further study of REE enrichment processes in the Cnoc nan Cuilean intrusion

The origin(s) and geodynamic significance of Archaean ultramafic-mafic bodies in the mainland Lewisian Gneiss Complex, North Atlantic Craton

The geodynamic regime(s) that predominated during the Archaean remains controversial, with the plethora of competing models largely informed by felsic lithologies. Ultramafic-mafic rocks displaying distinctive geochemical signatures are formed in a range of Phanerozoic geotectonic environments. These rocks have high melting points, making them potentially useful tools for investigating Archaean geodynamic processes in highly metamorphosed regions. We present field mapping, petrography, traditional bulk-rock geochemistry, and platinum-group element geochemistry for 12 ultramafic-mafic bodies in the Lewisian Gneiss Complex (LGC), which is a highly metamorphosed fragment of the North Atlantic Craton in northwest Scotland. Our data indicate that most of these occurrences are layered intrusions emplaced into the tonalite-trondhjemite-granodiorite (TTG)-dominated crust prior to polyphase metamorphism, representing a significant re-evaluation of the LGC's magmatic evolution. Of the others, two remain ambiguous, but one (Loch an Daimh Mor) has some geochemical affinity with abyssal/orogenic peridotites and may represent a fragment of Archaean mantle, although further investigation is required. The ultramafic-mafic bodies in the LGC thus represent more than one type of event/process. Compared with the TTG host rocks, these lithologies may preserve evidence of protolith origin(s), with potential to illuminate tectonic setting(s) and geodynamic regimes of the early Earth

The geochemistry and petrogenesis of the Paleoproterozoic du Chef dyke swarm, Quebec, Canada

The du Chef dyke swarm in southern Québec, Canada is composed of numerous northeast trending, greenschist-amphibolite facies, gabbronoritic dykes that crop out either side of the Grenville Front. The age of the du Chef swarm (2408 ± 3 Ga) has led previous authors to suggest a genetic link between the du Chef dykes and coeval swarms (including the Ringvassøy, Scourie, Widgemooltha and Sebanga) preserved on other Archean cratons. These now disparate dyke swarms are proposed to have formed in response to mantle plume-induced continental breakup during the early Proterozoic. This work represents the first geochemical study of the du Chef dykes and shows that the swarm evolved through fractional crystallisation of a tholeiitic parent magma that remained largely uncontaminated during its residence in, and ascent through, the crust. We also show that the primary magma for the du Chef swarm was derived through partial melting of an enriched region of the mantle, with a similar trace element composition to the modern-day HIMU reservoir and that the magma produced was significantly hotter than the ambient mantle at the time. We contend that the du Chef dykes are the product of early Proterozoic mantle plume magmatism and may help pinpoint an ancient hotspot centre that initiated continental break up along the margin of the Superior Craton at ∼2.4 Ga. Other dyke swarms proposed to be genetically linked with the du Chef dykes record a distinctly different petrogenetic history to that of the du Chef dykes, as evidenced by their more volcanic arc-like geochemical signature. These contrasting geochemical signatures in supposedly cogenetic continental tholeiitic rocks may be evidence of early Proterozoic mantle heterogeneity sampled by the rising du Chef mantle plum

Re-evaluating ambiguous age relationships in Archean cratons: Implications for the origin of ultramafic-mafic complexes in the Lewisian Gneiss Complex

Archean ultramafic-mafic complexes have been the focus of important and often contentious geological and geodynamic interpretations. However, their age relative to the other components of Archean cratons are often poorly-constrained, introducing significant ambiguity when interpreting their origin and geodynamic significance. The Lewisian Gneiss Complex (LGC) of the northwest Scottish mainland – a high-grade, tonalite-trondhjemite-granodiorite (TTG) terrane that forms part of the North Atlantic Craton (NAC) – contains a number of ultramafic-mafic complexes whose origin and geodynamic significance have remained enigmatic since they were first described. Previous studies have interpreted these complexes as representing a wide-range of geological environments, from oceanic crust, to the sagducted remnants of Archean greenstone belts. These interpretations, which are often critically dependent upon the ages of the complexes relative to the surrounding rocks, have disparate implications for Archean geodynamic regimes (in the NAC and globally). Most previous authors have inferred that the ultramafic-mafic complexes of the LGC pre-date the TTG magmas. This fundamental age relationship is re-evaluated in this investigation through re-mapping of the Geodh’ nan Sgadan Complex (where tonalitic gneiss reportedly cross-cuts mafic rocks) and new mapping of the 7 km2 Ben Strome Complex (the largest ultramafic-mafic complex in the LGC), alongside detailed petrography and spinel mineral chemistry. This new study reveals that, despite their close proximity in the LGC (12 km), the Ben Strome and Geodh’ nan Sgadan Complexes are petrogenetically unrelated, indicating that the LGC (and thus NAC) records multiple temporally and/or petrogenetically distinct phases of ultramafic-mafic Archean magmatism that has been masked by subsequent high-grade metamorphism. Moreover, field observations and spinel mineral chemistry demonstrate that the Ben Strome Complex represents a layered intrusion that was emplaced into a TTG-dominated crust. Further to representing a significant re-evaluation of the LGC’s magmatic evolution, these findings have important implications for the methodologies utilised in deciphering the origin of Archean ultramafic-mafic complexes globally, where material suitable for dating is often unavailable and field relationships are commonly ambiguous

Paradoxical co-existing base metal sulphides in the mantle: The multi-event record preserved in Loch Roag peridotite xenoliths, North Atlantic Craton

The role of the subcontinental lithospheric mantle as a source of precious metals for mafic magmas is contentious and, given the chalcophile (and siderophile) character of metals such as the platinum-group elements (PGE), Se, Te, Re, Cu and Au, the mobility of these metals is intimately linked with that of sulphur. Hence the nature of the host phase(s), and their age and stability in the subcontinental lithospheric mantle may be of critical importance. We investigate the sulphide mineralogy and sulphide in situ trace element compositions in base metal sulphides (BMS) in a suite of spinel lherzolite mantle xenoliths from northwest Scotland (Loch Roag, Isle of Lewis). This area is situated on the margin of the North Atlantic Craton which has been overprinted by a Palaeoproterozoic orogenic belt, and occurs in a region which has undergone magmatic events from the Palaeoproterozoic to the Eocene. We identify two populations of co-existing BMS within a single spinel lherzolite xenolith (LR80) and which can also be recognised in the peridotite xenolith suite as a whole. Both populations consist of a mixture of Fe-Ni-Cu sulphide minerals, and we distinguished between these according to BMS texture, petrographic setting (i.e., location within the xenolith in terms of ‘interstitial’ or within feldspar-spinel symplectites, as demonstrated by X-ray Computed Microtomography) and in situ trace element composition. Group A BMS are coarse, metasomatic, have low concentrations of total PGE (< 40 ppm) and high (Re/Os)N (ranging 1 to 400). Group B BMS strictly occur within symplectites of spinel and feldspar, are finer-grained rounded droplets, with micron-scale PtS (cooperite), high overall total PGE concentrations (15–800 ppm) and low (Re/Os)N ranging 0.04 to 2. Group B BMS sometimes coexist with apatite, and both the Group B BMS and apatite can preserve rounded micron-scale Ca-carbonate inclusions indicative of sulphide-carbonate-phosphate immiscibility. This carbonate-phosphate metasomatic association appears to be important in forming PGE-rich sulphide liquids, although the precise mechanism for this remains obscure. As a consequence of their position within the symplectites, Group B BMS are particularly vulnerable to being incorporated in ascending mantle-derived magmas (either by melting or physical entrainment). Based on the cross-cutting relationships of the symplectites, it is possible to infer the relative ages of each metasomatic BMS population. We tally these with major tectono-magmatic events for the North Atlantic region by making comparisons to carbonatite events recorded in crustal and mantle rocks, and we suggest that the Pt-enrichment was associated with a pre-Carboniferous carbonatite episode. This method of mantle xenolith base metal sulphide documentation may ultimately permit the temporal and spatial mapping of the chalcophile metallogenic budget of the lithospheric mantle, providing a blueprint for assessing regional metallogenic potential. Abbreviations: NAC, North Atlantic Craton; GGF, Great Glen Fault; NAIP, North Atlantic Igneous Province; BPIP, British Palaeogene Igneous Province; SCLM, subcontinental lithospheric mantle; PGE, platinum-group elements; HSE, highly siderophile elements; BMS, base metal sulphid

Homogenisation of sulphide inclusions within diamonds: A new approach to diamond inclusion geochemistry

Base metal sulphide (BMS) inclusions in diamonds provide a unique insight into the chalcophile and highly siderophile element composition of the mantle. Entombed within their diamond hosts, these provide a more robust (closed system) sample, from which to determine the trace element, Re-Os and S-isotopic compositions of the mantle than mantle xenoliths or orogenic peridotites, as they are shielded from alteration during ascent to the Earth’s crust and subsequent surface weathering. However, at temperatures below 1100 °C some BMS inclusions undergo subsolidus re-equilibration from an original monosulphide solid solution (Mss) and this causes fractionation of the major and trace elements within the inclusions. Thus to study the subjects noted above, current techniques require the entire BMS inclusion to be extracted for analyses. Unfortunately, ‘flaking’ of inclusions during break-out is a frequent occurrence and hence the risk of accidentally under-sampling a portion of the BMS inclusion is inherent in current practices. This loss may have significant implications for Re-Os isotope analyses where incomplete sampling of a Re-rich phase, such as chalcopyrite that typically occurs at the outer margins of BMS inclusions, may induce significant bias in the Re-Os and 187Os/188Os measurements and resulting model and isochron ages. We have developed a method for the homogenisation of BMS inclusions in diamond prior to their break-out from the host stone. Diamonds are heated to 1100 °C and then quenched to chemically homogenise any sulphide inclusions for both major and trace elements. Using X-ray Computed Microtomography (µCT) we determine the shape and spatial setting of multiple inclusions within a host stone and crucially show that the volume of a BMS inclusion is the same both before and after homogenisation. We show that the homogenisation process significantly reduces the inherent variability of in situ analysis when compared with unhomogenised BMS, thereby widening the scope for multiple methods for quantitative analysis, even on ‘flakes’ of single BMS inclusions. Finally we show that the trace elements present in peridotite (P-type) and eclogitic (E-type) BMS are distinct, with P-type diamonds having systematically higher total platinum-group element (particularly Os, Ir, Ru) and Te and As concentrations. These distinctions suggest that the PGE and semi-metal budgets of mantle-derived partial melts will be significantly dependent upon the type(s) and proportions of sulphides present in the mantle source

Cobalt and precious metals in sulphides of peridotite xenoliths and inferences concerning their distribution according to geodynamic environment: A case study from the Scottish lithospheric mantle

Abundances of precious metals and cobalt in the lithospheric mantle are typically obtained by bulk geochemical analyses of mantle xenoliths. These elements are strongly chalcophile and the mineralogy, texture and trace element composition of sulphide phases in such samples must be considered. In this study we assess the mineralogy, textures and trace element compositions of sulphides in spinel lherzolites from four Scottish lithospheric terranes, which provide an ideal testing ground to examine the variability of sulphides and their precious metal endowments according to terrane age and geodynamic environment. Specifically we test differences in sulphide composition from Archaean-Palaeoproterozoic cratonic sub-continental lithospheric mantle (SCLM) in northern terranes vs. Palaeozoic lithospheric mantle in southern terranes, as divided by the Great Glen Fault (GGF). Cobalt is consistently elevated in sulphides from Palaeozoic terranes (south of the GGF) with Co concentrations > 2.9 wt.% and Co/Ni ratios > 0.048 (chondrite). In contrast, sulphides from Archaean cratonic terranes (north of the GGF) have low abundances of Co (< 3600 ppm) and low Co/Ni ratios (< 0.030). The causes for Co enrichment remain unclear, but we highlight that globally significant Co mineralisation is associated with ophiolites (e.g., Bou Azzer, Morocco and Outokumpu, Finland) or in oceanic peridotite-floored settings at slow-spreading ridges. Thus we suggest an oceanic affinity for the Co enrichment in the southern terranes of Scotland, likely directly related to the subduction of Co-enriched oceanic crust during the Caledonian Orogeny. Further, we identify a distinction between Pt/Pd ratio across the GGF, such that sulphides in the cratonic SCLM have Pt/Pd ≥ chondrite whilst Palaeozoic sulphides have Pt/Pd < chondrite. We observe that Pt-rich sulphides with discrete Pt-minerals (e.g., PtS) are associated with carbonate and phosphates in two xenolith suites north of the GGF. This three-way immiscibility (carbonate-sulphide-phosphate) indicates carbonatitic metasomatism is responsible for Pt-enrichment in this (marginal) cratonic setting. These Co and Pt-enrichments may fundamentally reflect the geodynamic setting of cratonic vs. non-cratonic lithospheric terranes and offer potential tools to facilitate geochemical mapping of the lithospheric mantle

Para-infectious brain injury in COVID-19 persists at follow-up despite attenuated cytokine and autoantibody responses

To understand neurological complications of COVID-19 better both acutely and for recovery, we measured markers of brain injury, inflammatory mediators, and autoantibodies in 203 hospitalised participants; 111 with acute sera (1–11 days post-admission) and 92 convalescent sera (56 with COVID-19-associated neurological diagnoses). Here we show that compared to 60 uninfected controls, tTau, GFAP, NfL, and UCH-L1 are increased with COVID-19 infection at acute timepoints and NfL and GFAP are significantly higher in participants with neurological complications. Inflammatory mediators (IL-6, IL-12p40, HGF, M-CSF, CCL2, and IL-1RA) are associated with both altered consciousness and markers of brain injury. Autoantibodies are more common in COVID-19 than controls and some (including against MYL7, UCH-L1, and GRIN3B) are more frequent with altered consciousness. Additionally, convalescent participants with neurological complications show elevated GFAP and NfL, unrelated to attenuated systemic inflammatory mediators and to autoantibody responses. Overall, neurological complications of COVID-19 are associated with evidence of neuroglial injury in both acute and late disease and these correlate with dysregulated innate and adaptive immune responses acutely

A Record Of Assimilation Preserved By Exotic Minerals In The Lowermost Platinum-Group Element Deposit Of The Bushveld Complex: The Volspruit Sulphide Zone

Low-grade platinum-group element mineralisation in the Volspruit Sulphide Zone is sulphide-poor (%), distributed over a ~60 m-thick horizon in the lowermost cumulates of the northern limb of the Bushveld Complex. Unlike any other platinum-group element (PGE) deposit of the Bushveld Complex, the Volspruit Sulphide Zone is hosted exclusively within harzburgitic and dunitic cumulates in the Lower Zone of the Rustenburg Layered Suite. Here, we present a petrological investigation on the distribution of PGEs and chalcophile metals in mineralised pyroxenite cumulates from the Volspruit Sulphide Zone, to determine the origin of the PGE mineralisation in ultramafic cumulates and evaluate whether Volspruit-style mineralisation could occur in the stratigraphically lowest, ultramafic portions of other layered intrusions