Enrichment In High Field Strength Elements Research Articles

Hydrothermal high field strength element enrichment in the Bükk Mts. (NE Hungary)

This study demonstrates the possibility of high field strength element (HFSE) enrichment in a geological setting which differs from the known models, as no contacted alkaline magmatic rock body, or other potential source is known. Metasomatised rock bodies were discovered recently in fault blocks of two major fault zones of the Bükk Mts. The existence of this rock alteration implies long-range transport of mobilized HFSE in a carbonate-dominated lithological environment. Enriched elements are Zr, Nb, Ta, Th, U, Y, and rare earth elements except Eu which is depleted together with Ti and P. Host rocks are beds or layers of metavolcanics and metasediments dominated by silicate minerals, embedded in non-anomalous carbonate formations. These rocks are also enriched in potassium hosted by phengite or K-feldspars. The most abundant HFSE-carrier minerals are zircon, monazite-(Ce) and niobian Ti-oxides, but these are invisible due to their micrometric or submicrometric grain size. The metasomatic mineral assemblage overprints the texture formed during the Late Cretaceous regional metamorphism.

Mineralogical, geochemical, and isotopic data of a new special agpaitic dyke, enriched in high field strength elements (Eastern Part of Baltic Shield, Russia)

We present the petrography, bulk major and trace elements, and isotopic compositions for the recently identified Mohnatye Roga agpaitic syenite dyke, located 30 km from the Kovdor carbonatite complex, Kola Peninsula, Russia. The dyke was identified below Quaternary deposits as the result of a gravimetric survey and subsequent drilling. A K–Ar age on lamprophyllite of 368 ± 9 Ma, coincides with the age of the Devonian Kola Alkaline Carbonatite Province (KACP). In the total alkalis vs. silica diagram, the Mohnatye Roga dyke exhibits a compositional trend from lamprophyre to peralkaline phonolite as well as mineralogical and geochemical affinities with the nearby Niva intrusion. The dyke is composed of orthoclase, Ti-rich aegirine-augite, aenigmatite, lamprophyllite-group minerals, K-amphibole, and astrophyllite with accessory noonkanbahite, calcite, ilmenite, rutile, barite, apatite, and sulfides. Late stage minerals include natrolite and ferripyrophyllite. A notable feature of this dуke is its extremely high agpaicity and enrichment in HFSEs (high-field strength elements). The concentrations of a number of HFSEs are higher in this dyke than in the Lovozero rare metal deposit. Mohnatye Roga dyke and Niva intrusion are examples of a gradual transition from melt to hydrothermal fluid. Isotopic data indicate a mantle source for the dyke, and seemingly an absence of contamination by continental crust during its formation. The geochemical and isotopic data suggest that the source of the KACP rocks, including the Mohnatye Roga dyke, is FOZO mantle which is believed to be related to plume magmatism. • Origin and age of the recently identified lamprophyllite-bearing agpaitic syenite Mohnatye Roga dyke (Kola peninsula) • Great similarity with the Niva intrusion and the link to Devonian Kola Alkaline Carbonatite province • Agpaitic SiO 2 -undersatured melts preserving the depleted FOZO plume signature • Enrichment in HFSEs of Mohnatye Roga dyke and comparison with gigant Lovozero and Khibiny deposits.

ПРОСТРАНСТВЕННО-ВРЕМЕННАЯ СМЕНА ГЛУБИННЫХ ИСТОЧНИКОВ КАЙНОЗОЙСКИХ ВУЛКАНИЧЕСКИХ ПОРОД ВОСТОКА КОРЯКСКОГО НАГОРЬЯ

A spatiotemporal analysis of the trace element ratios and the isotopic composition of Sr, Nd and Pb in Cenozoic post-accretionary volcanic rocks in the east of the Koryak Highlands (Northeastern Russia) has been carried out. The Early Paleogene volcanic complex is shown to be represented by moderately Ti-rich aluminous tholeiites with elevated contents of high field strength elements (HFSE) (except for Ta and Nb), which makes them similar to E-MORBs. Low (La/Yb)n and high Zr/Nb (25–35) ratios characterize one of the source components as depleted and similar to MORBs. At the same time, low ratios of Nb/Ta, Ce/Pb, Nb/La with a high ratio of K/Nb were determined in basalts, which indicates the presence of a subduction component in the source. Low Zr/Hf and (Dy/Yb)n ratios indicate melting of the garnet-free substratum. The second (Miocene) stage is represented by the subalkaline basalt flows and dacite extrusions and dikes forming a bimodal series. Basalts are characterized by low concentrations of large ion lithophile elements (LILE), enrichment in HFSE, and fractionated distribution of REE, with (La/Yb)n ratios varying from the values characteristic of E-MORBs to the values corresponding to intraplate tholeiites. The Nb/Ta, Ce/Pb, La/Ta, and Hf/Th ratios tend to exhibit compositions of intraplate tholeiites. The (Dy/Yb)n and (La/Yb)pm - Ybpm ratios indicate the formation of Miocene basalts during the selective melting of garnet peridotite with varying garnet contents in the source. Dikes of dacites, in comparison with effusive facies, differ in calc-alkaline differentiation trends and other absolute concentrations of a number of elements. Early Quaternary alkaline olivine basalts and basanites of the Navarin area are high in HFSE, LILE, and REE and are compositionally similar to intraplate volcanics of oceanic islands and continental rifts. Data points of these rocks plotted on discriminant diagrams are confined to the field of the garnet-rich intraplate source with low degrees of partial melting. The initial isotopic ratios of Sr, Nd, and Pb in the Cenozoic basaltoids characterize the deep sources of Cenozoic rocks in the eastern part of the Koryak Highlands as depleted. The similarity of isotope ratios in the basalts of the Miocene and Early Quaternary stages of volcanism suggests that the mantle region was isotopically homogenized as a result of local convection.

Geochemistry of serpentinized and multiphase altered Atlantis Massif peridotites (IODP Expedition 357): Petrogenesis and discrimination of melt-rock vs. fluid-rock processes

International Ocean Discovery Program (IODP) Expedition 357 drilled 17 shallow sites distributed ~10 km in the spreading direction (from west to east) across the Atlantis Massif oceanic core complex (Mid-Atlantic Ridge, 30°N). Mantle exposed in the footwall of the Atlantis Massif oceanic core complex is predominantly nearly wholly serpentinized harzburgite with subordinate dunite. Altered peridotites are subdivided into three types: (I) serpentinites, (II) melt-impregnated serpentinites, and (III) metasomatic serpentinites. Type I serpentinites show no evidence of melt-impregnation or metasomatism apart from serpentinization and local oxidation. Type II serpentinites have been intruded by gabbroic melts and are distinguishable in some cases on the basis of macroscopic and microscopic observations, e.g., mm-cm scale mafic-melt veinlets, rare plagioclase (˂0.5 modal % in one sample) or by the local presence of secondary (replacive) olivine after orthopyroxene; in other cases, ‘cryptic’ melt-impregnation is inferred on the basis of incompatible element enrichments. Type III serpentinites are characterized by silica metasomatism manifest by alteration of orthopyroxene to talc and amphibole, and by anomalously high anhydrous SiO2 concentrations (59–61 wt%) and low MgO/SiO2 values (0.48–0.52). Although many chondrite-normalized rare earth element (REE) and primitive mantle-normalized incompatible trace element anomalies, e.g., negative Ce-anomalies, are attributable to serpentinization, other compositional heterogeneities are due to melt-impregnation. On the basis of whole rock incompatible trace elements, a dominant mechanism of melt-impregnation is distinguished in the central and eastern serpentinites from fluid-rock alteration (mostly serpentinization) in the western serpentinites, with increasing melt-impregnation manifest as a west to east increase in enrichment in high-field strength elements and light REE. High degrees of melt extraction are evident in low whole-rock Al2O3/SiO2 values and low concentrations of Al2O3, CaO and incompatible elements. Estimates of the degree of melt extraction based on whole rock REE patterns suggest a maximum of ~20% non-modal fractional melting, with little variation between sites. As some serpentinite samples are ex situ rubble, the magmatic histories observed at each site are consistent with a local source (from the fault zone) rather than rafted rubble that would be expected to show more heterogeneity and no spatial pattern. In this case, the studied sites may provide a record of enhanced melt-rock interactions with time, consistent with proposed geological models. Alternatively, sites may signify heterogeneities in these processes at spatial scales of a few km.

Early Neoproterozoic Metapicrite–Basalt Association of the Angara Region, Yenisei Ridge: Petrogeochemical Composition, Tectonic Settings, and Pb–Zn Mineralization

In the Angara part of the Yenisei Ridge, a sequential section of the metapicritic–basalt sequence and overlying carbonate rocks of the Gorevskaya Formation is established. This section is considered as a single volcanic–sedimentary complex formed at the Late Mesoproterozoic–Early Neoproterozoic boundary in the riftogenic marginal–continental paleobasin in the southwestern Siberian Craton. It is proposed to introduce the metapicrite–basaltic sequence into the stratigraphic legend of the Shirokaya Group of the western Yenisei Ridge under the name “Nizhnerechinskaya Sequence”. In the studied section, metamorphosed picrobasalts and picrites predominate in the lower part of the Nizhnerechinskaya Sequence, while the middle and upper parts consist mainly of basalts containing Pb–Zn mineralization (Stepanovsky ore occurrence). At the contact with carbonate deposits of the Gorevskaya Formation, an alternation of volcanogenic rocks and terrigenous–carbonate sediments and metabasaltic sills are observed. The petrochemical and trace-element composition of metavolcanic rocks has much in common, which indicates the paragenetic relationship of rocks of this high-Mg rock association. All these rocks are enriched in Fe and Ti, while metabasalts and metagabbros show elevated alkalinity and P2O5 content. In terms of total alkalinity, metabasalt–picrobasalts deviate from the normal petrochemical series towards the subalkaline series, which correlates with their elevated Ti content. Basites enriched in alkalis, especially, in potassium and corresponding to trachybasalts are observed among them. The contents of incompatible trace elements clearly increase from picrites to basalts and reach maximum in trachybasalts, which show 1.5–3 times enrichment in high-field strength elements compared to the basalts. The paragenetic nature of the considered association is supported by the similar REE distribution patterns: (La/Yb)n = 6–7 at Eu/Eu* = 0.9–1. The Late Mesoproterozoic–Early Neoproterozoic rifting of the Earth’s crust in the Angara region led to the opening of the marginal–continental sea basin, where basalt-picrite volcanism occurred simultaneously with accumulation of terrigenous–carbonate sediments, including ore–bearing (Pb–Zn) rocks of the Gorevskaya Formation, which host the Gorevskoye Pb–Zn deposit. The basin under consideration is interpreted as a relict rift-related paleobasin on the western margin of the Siberian craton, while the volcanic–sedimentary Nizhnerechinskaya Sequence is considered as the lower potential stratigraphic level of the base-metal mineralization in the Gorevsky ore field.

The Petrology of the Tarosero Volcanic Complex: Constraints on the Formation of Extrusive Agpaitic Rocks

Abstract The Quaternary Tarosero volcano is situated in the East African Rift of northern Tanzania and mainly consists of trachyte lavas and some trachytic tuffs. In addition, there are minor occurrences of extrusive basalts, andesites and latites, as well as peralkaline trachytes, olivine trachytes and phonolites. Some of the peralkaline phonolites contain interstitial eudialyte, making Tarosero one of the few known occurrences for extrusive agpaitic rocks. This study investigates the genetic relationships between the various rock types and focuses on the peculiar formation conditions of the extrusive agpaitic rocks using a combination of whole-rock geochemistry, mineral chemistry, petrography, thermodynamic calculations, and major and trace element modelling. The Tarosero rocks formed at redox conditions around or below the fayalite–magnetite–quartz buffer (FMQ). During multi-level magmatic fractionation at depths between ∼40 km and the shallow crust, temperature decreased from >1100 °C at near-liquidus conditions in the basalts to ∼700 °C in the peralkaline residue. Fractional crystallization models and trace element characteristics do not indicate a simple genetic relationship between the trachytes and the other rock types at Tarosero. However, the genetic relationships between the primitive basalts and the intermediate latites can be explained by high-pressure fractional crystallization of olivine + clinopyroxene + magnetite + plagioclase + apatite. Further fractionation of these mineral phases in addition to amphibole and minor ilmenite led to the evolution towards the peralkaline trachytes and phonolites. The eudialyte-bearing varieties of the peralkaline phonolites required additional low-pressure fractionation of alkali feldspar and minor magnetite, amphibole and apatite. In contrast to the peralkaline trachytes and phonolites, the peralkaline olivine trachytes contain olivine instead of amphibole, thus indicating a magma evolution at even lower pressure conditions. They can be modelled as a derivation from the latites by fractional crystallization of plagioclase, clinopyroxene, magnetite and olivine. In general, agpaitic magmas evolve under closed-system conditions, which impede the escape of volatile phases. In the case of the extrusive agpaitic rocks at Tarosero, the early exsolution of fluids and halogens was prevented by a low water activity. This resulted in high concentrations of rare earth elements (REE) and other high field strength elements (HFSE) and the formation of eudialyte in the most evolved peralkaline phonolites. Within the peralkaline rock suite, the peralkaline olivine trachytes contain the lowest HFSE and REE concentrations, consistent with mineralogical evidence for formation at a relatively high water activity. The lack of amphibole fractionation, which can act as a water buffer of the melt, as well as the evolution at relatively low-pressure conditions caused the early exsolution of fluids and loss of water-soluble elements. This prevented a strong enrichment of HFSE and REE before the magma was finally extruded.

Enrichment of REE and HFSE during the magmatic-hydrothermal evolution of the Baerzhe alkaline granite, NE China: Implications for rare metal mineralization

The Baerzhe Cretaceous (123.7 ± 0.9 Ma) peralkaline pluton underwent extensive fractional crystallization and extreme enrichment in incompatible elements including rare earth elements (REE) and the high field strength elements (HFSE). It is one of the largest resources of rare metals in China, containing approximately 100 million tons of ore with an average grade of 1.84 wt% ZrO2, 1.00 wt% REE2O3 (34% heavy rare-earth oxides), and 0.26 wt% Nb2O5. Zr, REE and Nb are mainly hosted by hydrothermal minerals, such as zircon, hingganite-(Y), monazite-(Ce), polycrase, pyrochlore, fergusonite and columbite. An integrated investigation of field geology, mineral textures and compositions of minerals and host granites was carried out to examine the evolution of the Baerzhe pluton and the roles of magmatic and hydrothermal processes in concentrating REE and HFSE. Most minerals in the intensively altered subsolvus granite show secondary textures or replaced pseudomorphs, such as the replacement of arfvedsonite by aegirine, zircon dissolution and reprecipitation, and the replacement of monazite-(Ce) and polycrase-(Y) by hingganite-(Y). Compositions of the key economic minerals and changes with respect to these alteration stages reveal evidence that hydrothermal alteration played a role in the mineralization of the pluton. In-situ analyses and element mappings suggest that large volume of metals were remobilized and redistributed during hydrothermal replacement, such as the replacing of monazite-(Ce) and polycrase by hingganite-(Y). It is suggested that subsolidus re-equilibration and hydrothermal alteration, in addition to magmatic fractionation, is critical for further concentrating REE and HSFE in peralkaline granitic systems.

Partial melting, fractional crystallisation, liquid immiscibility and hydrothermal mobilisation – A ‘recipe’ for the formation of economic A-type granite-hosted HFSE deposits

A number of A-type granites host resources of the high field strength elements (HFSE), including the rare earth elements (REE), that have been considered for economic exploitation. The best known of them is the Strange Lake pluton (Canada) with a resource of 20 Mt grading 1.44 wt% REE2O3, of which ~50% are heavy rare-earth oxides. In this paper, we examine the various processes that are likely to be responsible for the hyper-enrichment of the HFSE, starting with the generation of a parental magma through a very low degree of partial melting of a mantle plume or a metasomatically enriched mantle, in both cases, below a continental crust (continental rift). We trace the evolution of this magma (olivine nephelinite) through fractional crystallisation of olivine and clinopyroxene followed by plagioclase, K-rich alkali feldspar and arfvedsonite to the final residues of hyper-enriched HFSE granitic pegmatites. In so doing, we show that at least two additional steps are essential to the process of HFSE enrichment. The first of these is the abrupt termination of plagioclase crystallisation prior to the final consumption of Ca or assimilation of a Ca source and the resulting exsolution of an immiscible Ca-fluoride melt that sequesters the LREE and Y. The second of these steps is prolonged crystallisation of arfvedsonite, which delays saturation of the magma with an aqueous phase and ensures the development of an agpaitic assemblage of Na-bearing HFSE minerals (e.g., Na-zirconosilicates and Na-titanosilicates). Finally, we show that saturation of the magma with an aqueous‑carbonic fluid, which evolves to a very acidic composition, is an essential ingredient in the ‘recipe’ for the formation of an economic A-type granite-hosted HFSE deposit.

Neoproterozoic magmatism in the northern margin of the Yangtze Block, China: Implications for slab rollback in a subduction-related setting

The South Qinling Belt was located in the northern part of the Yangtze Block during the Neoproterozoic. Here we investigate two major magmatic intrusions in the northern and southern part of the belt, the Douling plutons (DLP) and the Fenghuangshan plutons (FHSP), to gain insights into the Neoproterozoic tectonic processes along the northern segment of the Yangtze Block. Zircon grains in the DLP yield weighted mean 206Pb/238U ages of 750–709 Ma, whereas those from the FHSP show ages of 749–728 Ma. The new results, together with the published data, reveal that these plutons were emplaced at ca. 759–685 Ma and ca. 802–704 Ma, respectively. Geochemically, the intermediate-felsic rocks from the DLP and FHSP show enrichment of light rare earth elements (LREE) and large-ion lithophile elements (LILE) (Rb, Ba and K), depletion of high field strength elements (HFSE) (Nb, Ta, P and Ti), and low Sr/Y and (La/Yb)N values, which are typical features of arc magmatic rocks. The gabbros from the FHSP have high Mg#, and display LREE and LILE (Rb, Ba, K, and Sr) enrichment and depletion of HFSE (Th, U, Nb, Ta, and Ti), suggesting that they were probably formed in a mantle wedge setting. Both DLP and FHSP show arc-related geochemistry modified by slab-derived fluids, and were formed at relatively high-temperature and low-pressure conditions. However, they display distinct Sr-Nd-Hf isotopic compositions. Zircon grains of two samples from the DLP respectively show mean εHf(t) values of −2.6 ± 0.3 and 0.9 ± 0.3, whereas zircon grains of four samples from the FHSP show mean εHf(t) values ranging from 7.5 ± 0.5 to 8.7 ± 0.4. The DLP shows dominantly negative εNd(t) values and inconsistent initial 87Sr/86Sr ratios, whereas FHSP shows relatively constant and positive εNd(t) values (3.69–3.74) but variable initial 87Sr/86Sr ratios. The Sr-Nd-Hf isotopic and geochemical features suggest that the enriched mantle and crustal materials were involved in the magma evolution of the DLP, whereas the FHSP is characterized by significant juvenile components with a rising asthenospheric mantle source playing a key role. We propose a subduction-related setting for these intrusions, and envisage slab rollback during the Neoproterozoic.

Petrology and geochemistry of high niobium eclogite in the North Qaidam orogen, Western China: Implications for an eclogite facies metamorphosed island arc slice

To better understand the evolution of the North Qaidam orogen, eclogite that forms lens-like bodies in granitic gneiss was studied in the Lüliangshan terrane, North Qaidam ultrahigh-pressure (UHP) metamorphic belt. Petrographic and mineralogical studies as well as pressure-temperature calculations showed that the eclogite underwent at least three metamorphic stages. Peak eclogite-facies metamorphism at 647–768 °C and ≥3.0 GPa was followed by high-pressure (HP) granulite-facies metamorphism at 815–929 °C/1.61–1.75 GPa and cooling to amphibolite-facies metamorphism at 606–720 °C/0.41–0.56 GPa. Three age groups can be identified via LA-ICP-MS zircon U–Pb eclogite dating: (1) an eclogite-facies metamorphic age of ca. 432–428 Ma, (2) an HP granulite-facies retrograde age of ca. 424–420 Ma, and (3) ages of 415–382 Ma, which constrained the timing of amphibolite-facies metamorphism. The studied eclogite is characterized by high field strength element enrichment, particularly in Nb content (57.8–124 ppm) and flat rare earth element patterns similar to high Nb island arc basalts described in many modern arcs that feature subduction of oceanic slabs. The samples have positive εNd (t) values (+2.1 to +5.1) and positive εHf (t) values (+4.9 to +10.0), indicating that the protolith of the high Nb eclogite was directly derived from the depleted mantle with little crustal contamination. These island arc basalts have been interpreted to have arisen from the partial melting of mantle wedge garnet-amphibole or garnet peridotite metasomatized by slab-dehydrated melts of a subducted oceanic slab. They were emplaced onto the continental block by arc magmatism prior to the main collision event. Then, the island arc materials were dragged into the subduction channel with eclogite-facies metamorphism via subduction of the Qaidam Block.

Textures and high field strength elements in hydrothermal magnetite from a skarn system: Implications for coupled dissolution-reprecipitation reactions

There is increasing evidence to suggest that high field strength elements (HFSE) could be mobile to some extent in hydrothermal fluid due to the influence of halogens (e.g., fluorine and chlorine). However, in natural hydrothermal (fluid) systems, “coupled dissolution reprecipitation” (CDR) reactions at fluid-mineral interfaces that have been emphasized in the past decade may play a key role in controlling the final textures and mineral assemblages. The influences of the CDR reactions in hydrothermal systems on HFSE enrichment or depletion at the mineral scale are enigmatic. In this study, we show that enrichment of Nb and Zr can occur in magnetite on the mineral scale formed by hydrothermal fluids at medium-to-lower temperature in a skarn system. Four stages of mineralization and alteration of magnetite have been identified in the Baishiya iron skarn deposit of the East Kunlun Mountains of China. Magnetite formed in stage 1 (S1) developed obvious oscillatory zonation, whereas that formed in stages 2 (S2) and 3 (S3) shows hydrothermal alteration and metasomatic textures, and that in stage 4 (S4) developed euhedral crystals with simple zoning. Systematic variations in the trace element compositions of different magnetite grains analyzed by EMPA and LA-ICP-MS suggest that the magnetite from S1 to S3 may have formed in a metasomatic process at relatively constant temperature, whereas the magnetite from S4 formed by re-equilibrium processes at lower temperature. The magnetite from each stage can be divided into light and dark domains based on backscattered electron images. The dark domains in the magnetite from S1 and S2 have higher Nb/Ta (8.52–27.00) and Zr/Hf (18.22–52.64) ratios and silicon contents than the light domains (0.55–5.66 and 2.54–16.43, respectively). Compared with other magnetite ores, the ores from S1 and S2 are depleted of V and Ni. This depletion may be induced by increased oxygen and co-crystallized sulfide. However, these variations are unlikely to be responsible for the enrichment of Nb and Zr in magnetite at equilibrium conditions. Conversely, the dark domains of the magnetite from S1 and S2 are porous, irregular, and/or oscillatory with quartz inclusions, indicating nonequilibrium conditions. These textural features could be attributed to the CDR reactions that are ubiquitous in skarn systems. The increased silicon concentrations in magnetite due to the CDR reactions could affect the lattice parameters of the magnetite structure, leading to an overall change in the volume of magnetite ores. The reduplicative processes of volume change, dissolution, and porosity formation within magnetite are further imporved due to an incresed oxygen fugacity and co-crystallized sulfide (e.g., decreased temperature or increased sulfur fugacity) at far-from-equilibrium or local equilibrium conditions, resulting in oscillatory magnetite dark domains of S1. Ripening of the transient porosity can trap nanoscale precipitates of columbite and zircon within pores of Si-magnetite, and this precipitation could be attributed to the co-crystallized phlogopite that would incorporate fluorine from the hydrothermal fluid, and subsequently decrease the solubility of Nb and Zr in the skarn system. This scenario highlights that Nb and Zr could be scavenged and enriched into in the reaction fronts (porosity) by controlling the reaction pathway at a local scale that does not reflect the overall fluid-rock interaction history of the mineral assemblage.

Fluid evolution in the Strange Lake granitic pluton, Canada: Implications for HFSE mobilisation

Strange Lake is a mid-Proterozoic peralkaline granite pluton (Québec-Labrador, Canada) that underwent extreme enrichment in high field strength elements (HFSE), including the rare earth elements (REE). The HFSE mineralisation is confined to highly altered pegmatites and the most altered parts of the granites, implying a genetic association between hydrothermal fluids and HFSE enrichment. This study uses analyses of fluid inclusions to investigate the hydrothermal evolution of the Strange Lake pluton and the role of hydrothermal processes in concentrating the HFSE to potentially exploitable levels.Five groups of inclusions were distinguished. From earliest to latest, these groups are: primary aqueous inclusions (~25wt% NaCl eq.) associated with melt inclusions (Group 1); primary aqueous inclusions (13–23wt% NaCl eq.) associated with CH4 inclusions (Groups 2a and b); primary aqueous inclusions (~9wt% NaCl eq.) associated with CO2 inclusions (Group 3); primary aqueous inclusions (~9wt% NaCl eq.), which contain no carbonic component (Group 4); and finally, secondary aqueous inclusions (19wt% NaCl eq.), including inclusions that outline mineral pseudomorphs, also with no detectable carbonic component (Group 5). Most of the inclusions (except those in Group 5) have conspicuous ‘implosion’ haloes, evident as numerous tiny voids. This indicates that the inclusions re-equilibrated, most likely during isobaric cooling.Fluid evolution commenced with the exsolution of a saline aqueous liquid (~25wt% NaCl eq.) and an immiscible CH4+H2 gas from the pegmatitic melt at temperatures of ~450–500°C and a pressure of ~1100bars. During isobaric cooling, the gas component of the fluid was gradually oxidised, evolving from being CH4-dominant to a CH4 fluid with a significant proportion of higher order hydrocarbons (due to oxidative coupling of methane induced by the consumption of O2 through the alteration of arfvedsonite to aegirine; ~325–360°C), and finally to a CO2-dominated fluid at ~300°C. The apparent salinity of the aqueous fluid decreased from ~25 to ~4.5wt% NaCl eq. due to fluid-rock interaction. The latter also caused precipitation of nahcolite (as a result of the reaction of newly formed CO2 with sodium from decomposing minerals), formation of pseudomorphs after primary Na-zirconosilicates and Na-titanosilicates and replacement of primary REE-silicates by bastnäsite-(Ce). Owing to this interaction, the carbonic component of the fluid was consumed which, together with the consumption of H2O to form Al-, K- and Fe-phyllosilicates, contributed to an increase in the fluid salinity (up to ~19wt% NaCl eq.).Light rare earth elements (LREE) were remobilised over 10s to 100s of metres by the high temperature high salinity fluid (preserved as Group 1 and 2a inclusions), whereas heavy rare earth elements (HREE) were remobilised on a much smaller scale by a late, low temperature high salinity fluid (trapped as inclusion Group 5). Fluid preserved as inclusion Group 3 may have been responsible for remobilisation of Zr and Ti.

Constraints on the mobilization of Zr in magmatic-hydrothermal processes in subduction zones from in situ fluid-melt partitioning experiments

The partitioning of Zr between high P-T aqueous fluids and melts has been investigated in situ in the haplogranite-H2O and haplogranite-(F)-H2O systems to assess the mobilization of high field strength elements (HFSE) in magmatic-hydrothermal processes in subduction zones. The partition coefficients Df/Zmr were determined from Zr concentrations measured in situ by synchrotron X-ray fluorescence (SXRF) in both aqueous fluids and F-free or F-bearing hydrous haplogranite melts equilibrated in diamond-anvil cells at 575 to 800 °C and 0.3 to 2.4 GPa. This experimental approach eliminates the need for internal or external calibrations of the SXRF signal and/or post-mortem analysis of the melt phase, hence decreasing the total uncertainties on Df/Zmr below 16%. Above 0.6 GPa, Zr partitions favorably into the hydrous silicate melt in both F-free and F-bearing systems, with Df/Zmr that range between 0.19 ± 0.02 and 0.38 ± 0.03. However, the relatively high Df/Zmr values indicate that alkali-silica rich aqueous fluids generated by metamorphic devolatilization may contribute significantly to the recycling of HFSE in subduction zones. The efficient uptake of Zr (and likely other HFSE) by subduction zone fluids, regardless of their nature (aqueous fluid, hydrous melt, or supercritical fluid), supports the idea that the typical HFSE depletion recorded in arc magmas does not result from their incompatibility in water-rich slab-derived fluids but most probably originates from complex fluid-melt-rock interactions occurring at the slab interface and within the mantle wedge. At shallow crustal pressure conditions (800 °C and 0.3 GPa), Zr partitions reversely into the aqueous fluid in the presence of fluorine (Df/Zmr = 1.40 ± 0.10) as observed for Nb at similar conditions by Webster et al. (1989). The enrichment of the aqueous phase in HFSE (Zr, Nb) at shallow crustal conditions is likely related to the enhanced peralkalinity of low pressure, F-bearing aqueous fluid with temperature, that provides the favorable conditions for their mobilization via the formation of HFSE-O-Si/Na clusters. This mechanism may control the enrichment in HFSE (and plausibly other rare metals such as REE) in early magmatic fluids exsolved from granitic melts, leading to the formation of HFSE-enriched aggregates in shallow magmatic-hydrothermal environments (e.g., Strange Lake and Thor Lake Nechalacho deposit, Canada; Galineiro complex, Spain).

Source character, mixing, fractionation and alkali metasomatism in Palaeoproterozoic greenstone dykes, Dannemora area, NE Bergslagen region, Sweden

AbstractThe geochemical and isotopic characteristics of metamorphosed Svecofennian mafic dykes from the Dannemora area in the NE part of the Bergslagen region in central Sweden were investigated and compared to mafic intrusive rocks in their vicinity. The dykes, with an inferred age of c. 1860–1870 Ma, are calc-alkaline, sub-alkaline and basaltic in composition and have a mixed subduction and within-plate geochemical affinity. They are the result of mixing of at least three mantle source components with similar basaltic major element composition, but different concentrations of incompatible trace elements. Magma M1 is strongly enriched both in Rare Earth Elements (REE) and High-Field-Strength Elements (HFSE); magma M2 is highly enriched in Large-Ion Lithophile Elements (LILE, except Sr) with only moderate enrichment in HFSE and REE (particularly low in Heavy Rare Earth Elements); and magma M3 is enriched in Sr and has a flat REE profile. Magma M3 also has a somewhat more positive (depleted) initial εNd value of +1.8, compared to +0.4 to +0.5 for magmas M1 and M2. The magma evolution was controlled by a mixture of fractionation (mainly affecting the compatible elements) and mixing, best seen in the incompatible element concentrations and the Nd isotope data. The basaltic overall composition indicates little or no wholesale contamination by upper continental crust, but the dykes have undergone later metasomatic changes mainly affecting the alkali elements.

Na-Metasomatism and Uranium Mineralization during a Two-Stage Albitization at Kitongo, Northern Cameroon: Structural and Geochemical Evidence

Mapping and documentation of lithological varieties and their corresponding geochemistry at the Kitongo uranium mineralization were concerned. The Kitongo U occurrence is hosted by granitic rocks that include interleaved sequences of metasedimentary and metavolcanic rocks of the collectively termed Poli Group. U-mineralization and Na-metasomatism are related and structurally controlled. The most promising uraniferous bodies are intimately related to intersections between the ductile ENE-trending faults and the brittle conjugate R' faults postdating the shearing event. The con- centration of uranium at fault intersections rather than along individual faults suggests that these zones that are dilatational in nature were also highly permeable and therefore the hydrothermal fluids ponded there could readily precipitate U therein. A two-stage albitization has altered the foliated granitic host rock and the second albitization that has over-printed the first one is more effective at fault intersections. Whole rock geochemistry was performed by using ICP-MS and ICP-AES respectively for major oxides, trace and REE. The U-bearing rock suite exhibits restricted range in SiO2 concentration (62.89% - 70.91%) and Al2O3 (13.16% - 18.59%) and it is poor in MgO (0.02% - 1.03%), CaO (0.24% - 1.88%) and K2O (0.08% - 5.32%). The mineralized rocks are however comparatively richer in Na2O (4.33% - 10.92%) compared to their barren counterparts. The host granite and associated granodioritic rocks in the area are weakly metaluminous, peralkaline, and are calc-alkaline. They are moderately to strongly fractionated and have tholeiitic and shoshonitic affinities with moderate to high HFSE (high field strength elements) and LILE (large ion lithophile elements) enrichment. The Rb/Sr, Rb/Ba and Sr/Ba ratios are 0.31, 0.14 and 1.48, respectively. U content in the mineralized granite is up to 651 ppm while the non-mineralized rock has only 2.4 ppm U. The REE patterns of the granite show LREE enrichment and strong Eu negative anomalies (Eu/Eu* = 0.03 to 0.48). The main mineralization stage characterized by local U, Na, Pb, Zn, Ga, Hf, Sr, Fe, Al, P and Zr enrichments is related to the second albitization event and could probably be associated in time with the calcite-uranium stage. The identification of fault segments favorable for uranium mineralization in northern Cameroon (Poli area) is important for understanding the genesis of hydrothermal ore deposits within continental strike-slip faults and therefore has great implications for exploration strategies.

Geoquímica e petrogênese de metabasitos do grupo Votuverava (Terreno Apiaí, Cinturão Ribeira Meridional): evidências de uma bacia retroarco calimiana

The Votuverava Group (ca. 1500 - 1400 Ma), which is part of the Apiai Terrane, a segment of the Southern Ribeira Belt, is composed of distal turbidites with significant basic magmatism represented by concordant lenses of metabasite. Twenty metabasite samples were investigated using geochemical analyses (major and trace elements). Three groups (G1, G2, G3) were identified based on Ti/V ratios, rare earth element patterns and MORB-normalized multi-element diagrams. All samples have tholeiitic signatures. The G1 group has a volcanic arc signature, with Ti/V ratios of 15 - 20, enrichment of large ion lithophile elements (LILE) and depletion in high field strength elements (HFSE) relative to the MORB. The trace element pattern indicates an important contribution of the subduction component. The G2 group has a MORB-type composition, with Ti/V ratios of 22 - 28. Nevertheless, the trace element behavior indicates a small contribution of the subduction component. The G3 group has an enriched MORB signature, with Ti/V ratio of approximately 40 and enrichment of LILE and HFSE. The variability of the TiO2/Yb and Nb/Yb ratios suggests that the G1 and G2 rocks were generated by shallow melting (N-MORB and E-MORB mantle sources, respectively). The G3 rocks are enriched in Ti and Nb, suggesting interaction between MORB and plume mantle sources. The coexistence of volcanic arc basalt and mid-ocean ridge basalt compositions, the overall geochemical patterns, and the sedimentary environment of the Votuverava Group are consistent with a back-arc basin environment.

Magmatic influence on reaction paths and element transport during serpentinization

Small-scale shear zones are present in drillcore samples of abyssal peridotites from the Mid-Atlantic ridge at 15°20′N (Ocean Drilling Program Leg 209). The shear zones act as pathways for both evolved melts and hydrothermal fluids. We examined serpentinites directly adjacent to such zones to evaluate chemical changes resulting from melt–rock and fluid–rock interaction and their influence on the mineralogy. Compared to fresh harzburgite and melt-unaffected serpentinites, serpentinites adjacent to melt-bearing veins show a marked enrichment in rare earth elements (REE), strontium and high field strength elements (HFSE) zirconium and niobium. From comparison with published chemical data of variably serpentinized and melt-unaffected harzburgites, one possible interpretation is that interaction with the adjacent melt veins caused the enrichment in HFSE, whereas the REE contents might also be enriched due to hydrothermal processes. Enrichment in alumina during serpentinization is corroborated by reaction path models for interaction of seawater with harzburgite–plagiogranite mixtures. These models explain both increased amounts of alumina in the serpentinizing fluid for increasing amounts of plagiogranitic material mixed with harzburgite, and the absence of brucite from the secondary mineralogy due to elevated silica activity. By destabilizing brucite, nearby melt veins might fundamentally influence the low-temperature alteration behaviour of serpentinites. Although observations and model results are in general agreement, due to absence of any unaltered protolith a quantification of element transport during serpentinization is not straightforward.

Origin of high field strength element enrichment in volcanic arcs: Geochemical evidence from the Sulu Arc, southern Philippines

Lavas from the Sulu Arc, southern Philippines, exhibit an enrichment in high field strength elements (HFSE) that represents a departure from the typical volcanic arc geochemical signature. It has been postulated that this relative enrichment arises from metasomatism of mantle wedge peridotites by melts derived from the subducting oceanic lithosphere, through formation of amphibole which subsequently breaks down and enriches the mantle source of parental arc magmas in HFSE. Divergent chemical and isotopic characteristics between Sulu Arc HFSE-enriched lavas and the Sulu Sea crust being subducted—the presumed source of slab-derived melts—render it unlikely, however, that HFSE enrichment arises from the influence of such melts. New geochemical data suggest that the varying degrees of HFSE enrichment in Sulu Arc lavas are instead the result of variable amounts of mixing between enriched and depleted mantle end-components—the sources of South China Sea intraplate lavas and Sulu seafloor basalts, respectively—within a compositionally heterogeneous mantle wedge.

Multi-Stage Modification of the Northern Slave Mantle Lithosphere: Evidence from Zircon- and Diamond-Bearing Eclogite Xenoliths Entrained in Jericho Kimberlite, Canada

The Jericho kimberlites are part of a small Jurassic kimberlite cluster in the northern Slave craton, Canada. A variety of dating techniques were applied to constrain the nature and age of two Jericho kimberlites, JD-1 (170·2 ± 4·3 Ma Rb–Sr phlogopite megacrysts, 172·8 ± 0·7 Ma U–Pb eclogite rutile, 178 ± 5 Ma U–Pb eclogite zircon lower intercept) and JD-3 (173 ± 2 Ma Rb–Sr phlogopite megacryst; 176·6 ± 3·2 Ma U–Pb perovskite), and all yielded identical results within analytical uncertainty. As there is no discernible difference in the radiometric ages obtained for these two pipes, the composite Rb–Sr phlogopite megacryst date of 173·1 ± 1·3 Ma is interpreted as the best estimate for the emplacement age of both Jericho pipes. The initial Sr isotope composition of 0·7053 ± 0·0003 derived from phlogopite megacrysts overlaps the range (0·7043–0·7084) previously reported for Jericho whole-rocks. These strontium isotope data, combined with the radiogenic initial 206Pb/204Pb ratio of 18·99 ± 0·33 obtained in this study, indicate that the Jericho kimberlites are isotopically similar to Group 1 kimberlites as defined in southern Africa. The Jericho kimberlites are an important new source of mantle xenoliths that hold clues to the nature of the Slave craton subcontinental mantle. A high proportion (30%) of the Jericho mantle xenolith population consists of various eclogite types including a small number (2–3%) of apatite-, diamond-, kyanite- and zircon-bearing eclogites. The most striking aspect of the Jericho zircon-bearing eclogite xenoliths is their peculiar geochemistry. Reconstructed whole-rock compositions indicate that they were derived from protoliths with high FeO, Al2O3 and Na2O contents, reflected in the high-FeO (22·6–27·5 wt %) nature of garnet and the high-Na2O (8·47–9·44 wt %) and high-Al2O3 (13·12–14·33 wt %) character of the clinopyroxene. These eclogite whole-rock compositions are highly enriched in high field strength elements (HFSE) such as Nb (133–1134 ppm), Ta (5–28 ppm), Zr (1779–4934 ppm) and Hf (23–64 ppm). This HFSE enrichment is linked to growth of large (up to 2 mm) zircon and niobian rutile crystals (up to 3 modal %) near the time of eclogite metamorphism. The diamond-bearing eclogites on the other hand are characterized by high-MgO (19·6–21·3 wt %) garnet and ultralow-Na2O (0·44–1·50 wt %) clinopyroxene. Paleotemperature estimates indicate that both the zircon- and diamond-bearing eclogites have similar equilibration temperatures of 950–1020°C and 990–1030°C, respectively, corresponding to mantle depths of 150–180 km. Integration of petrographic, whole-rock and mineral geochemistry, geochronology and isotope tracer techniques indicates that the Jericho zircon-bearing eclogite xenoliths have had a complex history involving Paleoproterozoic metamorphism, thermal perturbations, and two or more episodes of Precambrian mantle metasomatism. The oldest metasomatic event (Type 1) occurred near the time of Paleoproterozoic metamorphism (∼1·8 Ga) and is responsible for the extreme HFSE enrichment and growth of zircon and high-niobian rutile. A second thermal perturbation and concomitant carbonatite metasomatism (Type 2) is responsible for significant apatite growth in some xenoliths and profound light rare earth element enrichment. Type 2 metasomatism occurred in the period 1·0–1·3 Ga and is recorded by relatively consistent whole-rock eclogite model Nd ages and secondary U–Pb zircon upper intercept dates. These eclogite xenoliths were derived from a variety of protoliths, some of which could represent metasomatized pieces of oceanic crust, possibly linked to east-dipping subduction beneath the Slave craton during construction of the 1·88–1·84 Ga Great Bear continental arc. Others, including the diamond-bearing eclogites, could be cumulates from mafic or ultramafic sill complexes that intruded the Slave lithospheric mantle at depths of about 150–180 km.

Provenance and tectonic setting of Late Proterozoic Buem sandstones of southeastern Ghana: Evidence from geochemistry and detrital modes

The petrography, as well as major and trace element (including rare earth element) compositions of 10 sandstone samples from the Late Proterozoic Buem Structural Unit, southeast Ghana, have been investigated to determine their provenance and tectonic setting. The petrographic analysis has revealed that the sandstones are quartz-rich and were primarily derived from granitic and metamorphic basement rocks typical of a craton interior. The major and trace element compositions are comparable to average Proterozoic cratonic sandstones but with slight enrichment in high-field strength elements (i.e., Zr, Hf, Ta, Nb) and slight depletion in ferromagnesian elements (e.g., Cr, Ni, V) with exception of Co which is unusually enriched in the sandstones. The geochemical data suggest that the Buem sandstones are dominated by mature, cratonic detritus deposited on a passive margin. Elemental ratios critical of provenance (La/Sc, Th/Sc, Cr/Th, Eu/Eu*, La/Lu) are similar to sediments derived from weathering of mostly felsic and not mafic rocks. The rather high Eu/Eu* ratios (0.69–1.09) suggest weathering from mostly a granodiorite source rather than a granite source, consistent with a source from old upper continental crust. The granitoids of the Birimian Supergroup and/or the felsic gneisses of Birimian age exposed to the east and southeast of the Buem Formation appear the most likely source rocks. These results, therefore, support earlier studies that infer passive margin setting for the eastern margin of the West African Craton prior to the Pan-African orogeny.