Epigenetic gold occurrence in a Paleoproterozoic meta-evaporitic sequence in the Rompas-Rajapalot Au system, Peräpohja belt, northern Finland

Abstract The Rompas-Rajapalot gold prospect is located in the northern part of the Paleoproterozoic Peräpohja belt. It covers an area of at least 10 × 10 km and comprises various styles of gold mineralization ranging from localized high-grade Au pockets in uraninite- and pyrobitumen-bearing calcsilicate-carbonate-quartz veins in mafic metavolcanic rocks (Rompas area) to disseminated gold grains in Fe-Mg-rich metasediments and quartz-tourmaline-sulfide-native gold veins (Palokas area). This study deals with the petrography and mineral chemistry of the gold mineralization at Palokas, which occurs in the eastern part of the Rompas-Rajapalot prospect. Major and trace element data and fluid inclusion characteristics of tourmaline are used to evaluate the origin and the pressure-temperature-fluid composition parameters of hydrothermal fluids. Whole-rock geochemical analyses are utilized to evaluate the nature of the protolith of the host rocks. Gold occurs in a native form in at least two different textural settings: 1) single, relatively coarse grains disseminated among the rock-forming silicates in cordierite-orthoamphibole rocks and 2) smaller grains occurring in fractures of tourmaline in quartz-sulfide-tourmaline breccias and in fractures of chloritized cordierite-orthoamphibole rocks adjacent to the tourmaline-rich breccias. Fracture-related gold is associated with Bi-Se-S-bearing tellurides, native Bi, molybdenite, chalcopyrite, and pyrrhotite. Coarser-grained disseminated gold were not found to be clearly associated with sulfides nor any fractures. Statistical correlations show that the Au concentration correlates strongly with Te, Cu, Co, Se, Bi, Mo, and Ag (ρ = 0.730–0.619) whereas Au correlates moderately with As, Fe, W (ρ = 0.523–0.511) and to a lesser extent with U, Pb, and Ni (ρ = 0.492–0.407). Gold has the strongest negative correlations with Sr and Ca. The chondrite-normalized REE patterns of tourmaline from the Au-mineralized rocks (both vein type and host-rock tourmaline) and the late- to post-orogenic granite partly overlap and show similar LREE-enriched trends, with the enrichment being lower in tourmaline from the granite. Fluid inclusion studies from tourmaline in gold-bearing quartz-tourmaline-sulfide veins indicate that the veins were formed from H₂O-Na₂O-CO₂-CH₄-(H₂S) fluids in a boiling system under pressure conditions ranging from lithostatic to hydrostatic, with the depth being ~5 km and the temperature ~300°C. The properties of the ore-forming fluids support the genetic link between the late- to post-orogenic granitoid magmatism at ~1.78 Ga and the formation of the fracture-hosted gold mineralization, suggested based on earlier studies (including Re-Os-molybdenite age and boron isotope data from tourmaline). Based on the whole-rock geochemistry, it is highly plausible that the cordierite-orthoamphibole rocks and interlayered calcsilicatealbite rocks are part of a basin-wide lacustrine, at least partly evaporitic, sequence. The protolith of the cordierite-orthoamphibole rock was most probably a lake-margin sedimentary pile with abundant Mg-rich clays

A machine learning based-approach to predict the water content of mid-ocean ridge basalts

Abstract Water is critical in the evolution of the mantle due to its strong influence on the physicochemical properties of mantle rocks. Mid-ocean ridge basalts (MORBs) are commonly used to study the compositional characteristics of the convecting upper mantle. However, there remains abundant samples in the global MORB data sets without direct measurements of water contents. The commonly observed good correlation between H₂O and other incompatible trace components, such as Ce, has been applied to quantify water contents of MORBs. However, this approach assumes constant H₂O/Ce in the target samples, which is not always true as the H₂O/Ce ratios of MORBs could be rather heterogeneous even in some short ridge segments. Utilizing the present compositional data of global MORB glasses with measured water contents (n = 1,467), we construct a Random Forest Regression model based on machine learning, which can predict water concentrations of samples based on selected major and trace element data, without assuming a ratio between H₂O and other trace elements. This model allows us to precisely recover water contents for MORBs with comparable accuracy with traditional analytical methods. The predicted results of MORB glasses from this model (n = 1,931) expand the water content database of global MORBs and indicate a broad existence of high-H₂O MORBs. This new approach allows us to investigate the water content of MORBs from some ridges lacking previous water content measurements (e.g., the Chile Ridge and the Pacific-Antarctic Ridge) and infer changes in the water content of MORB sources through applying the model to transform fault samples

Trace element contents of mantle-derived magmas through time

Abstract A large compilation of quality-curated major and trace element data has been assembled to investigate how trace element patterns of mafic and ultramafic magmas have varied with time through particular settings from the Archean to the Phanerozoic, the primary objective being to recognise at what times particular patterns of variation emerge, and how similar these are to baseline data sets representing tectonic settings in the modern Earth. The most informative element combinations involve Nb, Th and the REE, where REE are represented by ‘lambda’ parameters describing slope and shape of patterns. Combinations of the ratios of Th, Nb, La and lambda values from Archean and early Proterozoic basalts and komatiites reveal a distinctive pattern that is common in most well-sampled terranes, defining a roughly linear trend in multi-dimensional space from compositions intermediate between modern n-MORB and primitive mantle at one end, towards compositions approximating middle-to-upper continental crust at the other. We ascribe this ‘Variable Th/Nb’ trend in most instances to varying degrees of crustal contamination of magmas with similar compositions to modern oceanic plateau basalts. Komatiites had slightly more depleted sources than basalts, consistent with the hypothesis of derivation from plume tails and heads, respectively. The most significant difference between Precambrian and Phanerozoic plume-derived basalts is that the distinctive OIB-like enriched source component appears to be largely missing from the Archean and Proterozoic geologic record, although isolated examples of OIB-like trace element characteristics are evident in datasets from even the oldest preserved greenstones. Phanerozoic intra-cratonic LIPs, such as the 260 Ma Emeishan LIP in China, have fundamentally different geochemical characteristics to Archean and Paleoproterozoic assemblages; the oldest Proterozoic LIP we have identified that has this type of ‘modern’ signal is the Midcontinent Rift at 1100 Ma. The data are consistent with plume tail sources having changed from being dominantly depleted in the Archean Earth to dominantly enriched in the Phanerozoic Earth, while plume head sources have hardly changed at all. Trace element patterns considered to be diagnostic of subduction are locally present but rare in Archean terranes and become more prevalent through the Proterozoic, although this conclusion is tempered by the large degree of overlap in compositional space between continental arc magmas and continental flood basalts. This overlap reflects the difficulty of distinguishing the effects of supra-subduction metasomatizm and flux melting from those of crustal contamination. Additional factors must also be borne in mind, particularly that trace element partitioning systematics may have been different in all environments in a hotter planet, and large-scale asthenospheric overturns might have been predominant over modern-style plumes in the Archean Earth. Some basaltic suites in particular Archean terranes, notably the western parts of both the Yilgarn and Pilbara cratons in Western Australia and parts of the Superior Craton, have restricted, but locally predominant, suites of basalts with characteristics akin to modern oceanic arcs, suggesting that some process similar to modern subduction was preserved in these particular belts. Ferropicrite magmas with distinctive characteristics typical of modern OIBs and some continental LIPs (notably Emeishan) are rare but locally predominant in some Archean and early Proterozoic terranes, implying that plume sources were beginning to be fertilised by enriched, probably subducted, components as far back as the Mesoarchean. We see no evidence for discontinuous secular changes in mantle-derived magmatism with time that could be ascribed to major mantle reorganisation events. The Archean–Proterozoic transition appears to be entirely gradational from this standpoint. The transition from Archean-style to Phanerozoic-style plume magmatism took place somewhere between 1900 Ma (age of the Circum-Superior komatiitic basalt suites) and 1100 Ma (the age of the Midcontinent Rift LIP)

The petrology and genesis of the Paleoproterozoic mafic intrusion-hosted Co-Cu-Ni deposit at Hietakero, NW Finnish Lapland

Abstract Cobalt is a highly sought-after metal due to its economic importance in many hightech applications. It is mainly obtained from sedimentary-hosted Cu-Co deposits and magmatic Ni-Cu deposits as a by-product. We describe a recently discovered Co-enriched Cu-Ni deposit hosted by the Hietakero mafic intrusion in north-western Finnish Lapland. The intrusion contains gabbroic to pyroxenitic cumulates and was emplaced into a supracrustal strata composed mainly of mafic volcanic rocks, sulfur-bearing graphite schists and felsic volcanic interlayers. Hybrid rocks provide clear evidence for interaction of mafic magma with its country rocks. All these rocks have undergone intensive post-magmatic hydrothermal alteration by influx of H2O-, CO2- and Cl-bearing saline fluids, forming strongly scapolitized (±albitized) rocks and resulting in re-mobilization of sulfides and their metals. The Hietakero deposit is associated with pyroxenitic cumulates and hybrid rocks, with the sulfides (pyrrhotite, cobaltian pentlandite, chalcopyrite and pyrite) occurring as patches, brecciated to net-textured and vein to veinlet forms. Sulfur content is 6.1 wt.% on average, reaching 20 wt.% in some cases. Nickel and Cu tenors are low, but Co is elevated, resulting in very low Ni/Co of 2.6 compared to ‘classic’ Ni-Cu sulfide deposit globally. The average metal tenors are: 0.55 wt.% Ni, 1.07 wt.% Cu, and 0.23 wt.% Co. In-situ sulfur isotope analyses of sulfides from mineralized rocks yielded δ34S values from -2.0 to +4.5‰. In spite of strong post-magmatic alteration, we can conclude that the Hietakero cumulates were formed from a low-MgO and PGE-depleted basaltic magma, which developed in a staging chamber at a deeper crustal level. The magma produced compositionally different gabbroic to pyroxenitic rocks (i.e., high-Ti and low-Ti groups). Model calculations indicate that the relatively high Co tenor and low Ni/Co cannot be explained by an earlier phase of fractional crystallization or sulfide segregation. Instead, an external source of cobalt is needed, which is also consistent with the high Zn, Pb and Mo contents of the mineralized rocks. Based on sulfur isotope compositions, the associated black shales were not the primary source of sulfur, but sulfur was rather derived from a so far unrecognized, potentially Co-bearing contaminant with close to mantle-like δ34S. Our study reveals a new Co-Cu-Ni deposit type related to the widespread Paleoproterozoic mafic magmatism in Lapland

Empirical constraints on partitioning of platinum group elements between Cr-spinel and primitive terrestrial magmas

Abstract Recent experimental studies and in situ LA-ICP-MS analysis on natural Cr-spinel have shown that Rh and IPGEs (Ir-group platinum group elements: Ru, Ir, Os) are enriched in the lattice of Cr-spinel. However, the factors controlling the partitioning behaviour of these elements are not well constrained. In this study, we report the Rh, IPGE, and trace element contents in primitive Cr-spinel, measured by LA-ICP-MS, from nine volcanic suites covering various tectonic settings including island arc picrites, boninites, large igneous province picrites and mid-ocean ridge basalts. The aim is to understand the factors controlling the enrichment of Rh and IPGEs in Cr-spinels, to estimate empirical partition coefficients between Cr-spinel and silicate melts, and to investigate the role of Cr-spinel fractional crystallization on the PGE geochemistry of primitive magmas during the early stages of fractional crystallization. There are systematic differences in trace elements, Rh and IPGEs in Cr-spinels from arc-related magmas (Arc Group Cr-spinel), intraplate magmas (Intraplate Group Cr-spinel), and mid-ocean ridge magmas (MORB Group Cr-spinel). Arc Group Cr-spinels are systematically enriched in Sc, Co and Mn and depleted in Ni compared to the MORB Group Cr-spinels. Intraplate Group Cr-spinels are distinguished from the Arc Group Cr-spinels by their high Ni contents. Both the Arc and Intraplate Group Cr-spinels have total Rh and IPGE contents of 22–689 ppb whereas the MORB Group Cr-spinels are depleted in Rh and IPGE (total < 20 ppb). Palladium and Pt contents are below detection limit for all of the studied Cr-spinels (<1–5 ppb). The time-resolved spectra of LA-ICP-MS data for Cr-spinels mostly show constant count rates for trace element and Rh and IPGEs, suggesting homogeneous distribution of these elements in Cr-spinels. The PGE spikes observed in several Cr-spinels were interpreted to be PGE-bearing mineral inclusions and excluded from calculating the PGE contents of the Cr-spinels. On primitive mantle normalized diagrams the Arc Group Cr-spinels are characterized by a fractionated pattern with high Rh and low Os. The Intraplate Group Cr-spinels show flat patterns with positive Ru anomalies. Our results, together with the experimental and empirical data from previous studies, show that PGE patterns of Cr-spinel largely mimic that of the rock in which they are found, and that Rh, Ir and Os contents increase with increasing Fe3+ contents (i.e. magnetite component) in Cr-spinel, although Ru does not. These observations suggest that the enrichment of Rh and IPGEs in Cr-spinel is controlled by a combination of the Rh and IPGE contents in parental melts and the magnetite component of the spinel. Empirical partition coefficients (D) for Rh and IPGEs between Cr-spinels and silicate melts were calculated using the Rh and IPGE contents of the Cr-spinel and their host volcanic rocks after subtracting the accumulation effect of Cr-spinel. The D values for the Intraplate and MORB Group Cr-spinels increase with increasing magnetite component in Cr-spinel and range from 6 to 512, which is consistent with previously reported experimental and empirical values. In contrast, the Arc Group Cr-spinels have significantly higher D values (e.g. up to ∼3700 for Ru) than those of the Intraplate and MORB Group at the same magnetite concentration in the Cr-spinel, suggesting Rh and IPGEs dissolved in silicate melt have stronger affinity for Cr spinel under arc magma conditions than in intraplate magmas. This may be partly attributed to the low temperature of arc magmas relative to intraplate magmas, which leads to the Arc Group Cr-spinels having more octahedral sites at the same magnetite components than the Intraplate Group Cr-spinels. Because of significantly higher D values for the Arc Group Cr-spinels, compared with the Intraplate Group and MORB Group spinels, fractional crystallization of Cr-spinel will more efficiently fractionate Rh and IPGE from Pd and Pt in arc systems than in intraplate and MORB systems, which accounts for the highly fractionated PGE patterns in arc basalts

Mantle hydration and the role of water in the generation of large igneous provinces

Abstract The genesis of large igneous provinces (LIP) is controlled by multiple factors including anomalous mantle temperatures, the presence of fusible fertile components and volatiles in the mantle source, and the extent of decompression. The lack of a comprehensive examination of all these factors in one specific LIP makes the mantle plume model debatable. Here, we report estimates of the water content in picrites from the Emeishan LIP in southwestern China. Although these picrites display an island arc-like H2O content (up to 3.4 by weight percent), the trace element characteristics do not support a subduction zone setting but point to a hydrous reservoir in the deep mantle. Combining with previous studies, we propose that hydrous and hot plumes occasionally appeared in the Phanerozoic era to produce continental LIPs (e.g., Tarim, Siberian Trap, Karoo). The wide sampling of hydrous reservoirs in the deep mantle by mantle plumes thus indicates that the Earth’s interior is largely hydrated

Kivilompolo Mo mineralization in the Peräpohja belt revisited:trace element geochemistry and Re-Os dating of molybdenite

Abstract The Kivilompolo molybdenite occurrence is located in the northern part of the Peräpoh jabelt, within the lithodemic Ylitornio nappe complex. It is hosted within a deformed porphyritic granite belonging to the pre-orogenic 1.99 Ga Kierovaara suite. The mineralization occurs mostly as coarse-grained molybdenite flakes in boudinaged quartz veins, with minor chalcopyrite, pyrite, magnetite, and ilmenite. In this study, we report new geochemical data from the host-rock granite and Re-Os dating results of molybdenite from the mineralization. For the whole-rock geochemistry, the mineralized granite is similar to the Kierovaara suite granites analyzed in previous studies. Also, the ca. 2.0 Ga Re-Os age for molybdenite is equal, within error, to the U-Pb zircon age of the Kierovaara suite granite. In addition, similar molybdenite and uraninite ages have been reported from the Rompas-Rajapalot Au-Co occurrence located 30 km NE of Kivilompolo. We propose that the magmatism at around 2.0 Ga ago initiated the hydrothermal circulation that was responsible for the formation of the molybdenite mineralization at Kivilompolo and the primary uranium mineralization associated with the Rompas-Rajapalot Au-Co occurrence or at least, the magmas provided heating, and in addition potentially saline magmatic fluids and metals from a large, cooling magmatic-hydrothermal system