Protomylonite evolution potentially revealed by the 3D depiction and fractal analysis of chemical data from a feldspar

Tourmalinization associated with peraluminous granitic intrusions in metapelitic host-rocks has been widely recorded in the Iberian Peninsula, given the importance of tourmaline as a tracer of granite magma evolution and potential indicator of Sn-W mineralizations. In the Penamacor-Monsanto granite pluton (Central Eastern Portugal, Central Iberian Zone), tourmaline occurs: (1) as accessory phase in two-mica granitic rocks, muscovite-granites and aplites, (2) in quartz (±mica)-tourmaline rocks (tourmalinites) in several exocontact locations, and (3) as a rare detrital phase in contact zone hornfels and metapelitic host-rocks. Electron microprobe and stable isotope (δ¹⁸O, δD, δ¹¹B) data provide clear distinctions between tourmaline populations from these different settings: (a) schorl–oxyschorl tourmalines from granitic rocks have variable foititic component (^X□ = 17–57 %) and Mg/(Mg + Fe) ratios (0.19–0.50 in two-mica granitic rocks, and 0.05–0.19 in the more differentiated muscovite-granite and aplites); granitic tourmalines have constant δ¹⁸O values (12.1 ± 0.1 ‰), with wider-ranging δD (?78.2 ± 4.7 ‰) and δ¹¹B (?10.7 to ?9.0 ‰) values; (b) vein/breccia oxyschorl [Mg/(Mg + Fe) = 0.31–0.44] results from late, B- and Fe-enriched magma-derived fluids and is characterized by δ¹⁸O = 12.4 ‰, δD = ?29.5 ‰, and δ¹¹B = ?9.3 ‰, while replacement tourmalines have more dravitic compositions [Mg/(Mg + Fe) = 0.26–0.64], close to that of detrital tourmaline in the surrounding metapelitic rocks, and yield relatively constant δ¹⁸O values (13.1–13.3 ‰), though wider-ranging δD (?58.5 to ?36.5 ‰) and δ¹¹B (?10.2 to ?8.8 ‰) values; and (c) detrital tourmaline in contact rocks and regional host metasediments is mainly dravite [Mg/(Mg + Fe) = 0.35–0.78] and oxydravite [Mg/(Mg + Fe) = 0.51–0.58], respectively. Boron contents of the granitic rocks are low (<650 ppm) compared to the minimum B contents normally required for tourmaline saturation in granitic melts, implying loss of B and other volatiles to the surrounding host-rocks during the late-magmatic stages. This process was responsible for tourmalinization at the exocontact of the Penamacor-Monsanto pluton, either as direct tourmaline precipitation in cavities and fractures crossing the pluton margin (vein/breccia tourmalinites), or as replacement of mafic minerals (chlorite or biotite) in the host-rocks (replacement tourmalinites) along the exocontact of the granite. Thermometry based on ¹⁸O equilibrium fractionation between tourmaline and fluid indicates that a late, B-enriched magmatic aqueous fluid (av. δ¹⁸O ~12.1 ‰, at ~600 °C) precipitated the vein/breccia tourmaline (δ¹⁸O ~12.4 ‰) at ~500–550 °C, and later interacted with the cooler surrounding host-rocks to produce tourmaline at lower temperatures (400–450 °C), and an average δ¹⁸O ~13.2 ‰, closer to the values for the host-rock. Although B-metasomatism associated with some granitic plutons in the Iberian Peninsula seems to be relatively confined in space, extending integrated studies such as this to a larger number of granitic plutons may afford us a better understanding of Variscan magmatism and related mineralizations.     

Quartz Reference Materials for Oxygen Isotope Analysis by SIMS

Two quartz samples of igneous origin, UNIL‐Q1 (Torres del Paine Intrusion, Chile) and BGI‐Q1 (Shandong province, China), were calibrated for their oxygen isotope composition for SIMS measurements. UNIL‐Q1 and BGI‐Q1 were evaluated for homogeneity using SIMS. Their reference δ¹⁸O values were determined by CO₂ laser fluorination. The average δ¹⁸O value found for UNIL‐Q1 is 9.8 ± 0.06‰ and that for BGI‐Q1 is 7.7 ± 0.11‰ (1s). The intermediate measurement precision of SIMS oxygen isotope measurements was 0.32–0.41‰ (2s; UNIL‐Q1) and 0.40–0.48‰ (2s; BGI‐Q1), respectively. While less homogeneous in its oxygen isotope composition, BGI‐Q1 is also suitable for SIMS trace element measurements.     

Iron isotope fractionation in subduction-related high-pressure metabasites (Ile de Groix,France)

Characterisation of mass transfer during subduction is fundamental to understand the origin of compositional heterogeneities in the upper mantle. Fe isotopes were measured in high-pressure/low-temperature metabasites (blueschists, eclogites and retrograde greenschists) from the Ile de Groix (France), a Variscan high-pressure terrane, to determine if the subducted oceanic crust contributes to mantle Fe isotope heterogeneities. The metabasites have δ⁵⁶Fe values of +0.16 to +0.33‰, which are heavier than typical values of MORB and OIB, indicating that their basaltic protolith derives from a heavy-Fe mantle source. The δ⁵⁶Fe correlates well with Y/Nb and (La/Sm)_PM ratios, which commonly fractionate during magmatic processes, highlighting variations in the magmatic protolith composition. In addition, the shift of δ⁵⁶Fe by +0.06 to 0.10‰ compared to basalts may reflect hydrothermal alteration prior to subduction. The δ⁵⁶Fe decrease from blueschists (+0.19 ± 0.03 to +0.33 ± 0.01‰) to eclogites (+0.16 ± 0.02 to +0.18 ± 0.03‰) reflects small variations in the protolith composition, rather than Fe fractionation during metamorphism: newly-formed Fe-rich minerals allowed preserving bulk rock Fe compositions during metamorphic reactions and hampered any Fe isotope fractionation. Greenschists have δ⁵⁶Fe values (+0.17 ± 0.01 to +0.27 ± 0.02‰) similar to high-pressure rocks. Hence, metasomatism related to fluids derived from the subducted hydrothermally altered metabasites might only have a limited effect on mantle Fe isotope composition under subsolidus conditions, owing to the large stability of Fe-rich minerals and low mobility of Fe. Subsequent melting of the heavy-Fe metabasites at deeper levels is expected to generate mantle Fe isotope heterogeneities.     

A Nd- and O-isotope study of the REE-rich peralkaline Strange Lake granite: implications for Mesoproterozoic A-type magmatism in the Core Zone (NE-Canada)

It is well established that A-type granites enriched in high field strength elements, such as Zr, Nb and the REE, form in anorogenic tectonic settings. The sources of these elements and the processes controlling their unusual enrichment, however, are still debated. They are addressed here using neodymium and oxygen isotope analyses of samples from the 1.24 Ga Strange Lake pluton in the Paleoproterozoic Core Zone of Québec-Labrador, an A-type granitic body characterized by hyper-enrichment in the REE, Zr, and Nb. Age-corrected εNd values for bulk rock samples and sodic amphiboles (mainly arfvedsonite) from the pluton range from ?0.6 to ?5.7, and ?0.3 to ?5.3, respectively. The εNd values for the Napeu Kainiut quartz monzonite, which hosts the pluton, range from ?4.8 to ?8.1. The ¹⁴⁷Sm/¹⁴⁴Nd ratios of the suite and the host quartz monzonite range from 0.0967 to 0.1659, large variations that can be explained by in situ fractionation of early LREE-minerals (Strange Lake), and late hydrothermal HREE remobilization. Oxygen isotope analyses of quartz of both Strange Lake and the host yielded δ¹⁸O values between +8.2 and +9.1, which are considerably higher than the mantle value of 5.7 ± 0.2‰. Bulk rock oxygen isotope analyses of biotite-gneisses in the vicinity of the Strange Lake pluton yielded δ¹⁸O values of 6.3, 8.6 and 9.6‰. The negative εNd values and positive δ¹⁸O values of the Strange Lake and Napeu Kainiut samples indicate that both magmas experienced considerable crustal contamination. The extent of this contamination was estimated, assuming that the contaminants were sedimentary-derived rocks from the underlying Archean Mistinibi (para-) gneiss complex, which is characterized by low εNd and high δ¹⁸O values. Mixing of 5–15% of a gneiss, having an εNd value of ?15 and a δ¹⁸O value of +11, with a moderately enriched mantle source (εNd = +0.9, δ¹⁸O = +6.3) would produce values similar to those obtained for the Strange Lake granites. Based on analogies between the Nain Plutonic Suite and the Gardar alkaline igneous province (SW-Greenland), we conclude that the Strange Lake pluton and associated REE-mineralized anorogenic bodies formed from a combination of subduction-induced fertilization of the sublithospheric mantle, crustal extension and in situ magma evolution.     

On the iron isotope heterogeneity of lithospheric mantle xenoliths: implications for mantle metasomatism, the origin of basalts and the iron isotope composition of the Earth

With the aim to better understand the cause of the iron isotope heterogeneity of mantle-derived bulk peridotites, we compared the petrological, geochemical and iron isotope composition of four xenolith suites from different geodynamic settings; sub-arc mantle (Patagonia); subcontinental lithospheric mantle (Cameroon), oceanic mantle (Kerguelen) and cratonic mantle (South Africa). Although correlations were not easy to obtain and remain scattered because these rocks record successive geological events, those found between δ⁵⁷Fe, Mg#, some major and trace element contents of rocks and minerals highlight the processes responsible for the Fe isotope heterogeneity. While partial melting processes only account for moderate Fe isotope variations in the mantle (<0.2 ‰, with bulk rock values yielding a range of δ⁵⁷Fe ± 0.1 ‰ relative to IRMM-14), the main cause of Fe isotope heterogeneity is metasomatism (>0.9 ‰). The kinetic nature of rapid metasomatic exchanges between low viscosity melts/fluids and their wall-rocks peridotite in the mantle is the likely explanation for this large range. There are a variety of responses of Fe isotope signatures depending on the nature of the metasomatic processes, allowing for a more detailed study of metasomatism in the mantle with Fe isotopes. The current database on the iron isotope composition of peridotite xenoliths and mafic eruptive rocks highlights that most basalts have their main source deeper than the lithospheric mantle. Finally, it is concluded that due to a complex geological history, Fe isotope compositions of mantle xenoliths are too scattered to define a mean isotopic composition with enough accuracy to assess whether the bulk silicate Earth has a mean δ⁵⁷Fe that is chondritic, or if it is ~0.1 ‰ above chondrites as initially proposed.     

Iron isotope compositions of carbonatites record melt generation, crystallization, and late-stage volatile-transport processes

Carbonatites define the largest range in Fe isotope compositions yet measured for igneous rocks, recording significant isotopic fractionations between carbonate, oxide, and silicate minerals during generation in the mantle and subsequent differentiation. In contrast to the relatively restricted range in δ⁵⁶Fe values for mantle-derived basaltic magmas (δ⁵⁶Fe?=?0.0?±?0.1‰), calcite from carbonatites have δ⁵⁶Fe values between ?1.0 and +0.8‰, similar to the range defined by whole-rock samples of carbonatites. Based on expected carbonate-silicate fractionation factors at igneous or mantle temperatures, carbonatite magmas that have modestly negative δ⁵⁶Fe values of ~ ?0.3‰ or lower can be explained by equilibrium with a silicate mantle. More negative δ⁵⁶Fe values were probably produced by differentiation processes, including crystal fractionation and liquid immiscibility. Positive δ⁵⁶Fe values for carbonatites are, however, unexpected, and such values seem to likely reflect interaction between low-Fe carbonates and Fe³⁺-rich fluids at igneous or near-igneous temperatures; the expected δ⁵⁶Fe values for Fe²⁺-bearing fluids are too low to produced the observed positive δ⁵⁶Fe values of some carbonatites, indicating that Fe isotopes may be a valuable tracer of redox conditions in carbonatite complexes. Further evidence for fluid-rock or fluid-magma interactions comes from the common occurrence of Fe isotope disequilibrium among carbonate, oxide, silicate, and sulfide minerals in the majority of the carbonatites studied. The common occurrence of Fe isotope disequilibrium among minerals in carbonatites may also indicate mixing of phenocyrsts from distinct magmas. Expulsion of Fe³⁺-rich brines into metasomatic aureols that surround carbonatite complexes are expected to produce high-δ⁵⁶Fe fenites, but this has yet to be tested.     

Iron isotopic systematics of UHP eclogites respond to oxidizing fluid during exhumation

The iron stable isotope compositions (δ⁵⁶Fe) and iron valence states of ultrahigh‐pressure eclogites from Bixiling in the Dabie orogen belt, China, were measured to trace the changes of geochemical conditions during vertical transportation of earth materials, for example, oxygen fugacity. The bulk Fe³⁺/ΣFe ratios of retrograde eclogites, determined by Mössbauer spectroscopy, are consistently higher than those of fresh eclogites, suggesting oxidation during retrograde metamorphism and fluid infiltration. The studied eclogites (five samples) display limited mid‐ocean ridge basalts (MORB)‐like (~0.10‰) δ⁵⁶Fe values, which are indistinguishable from their protoliths, that is, gabbro cumulates formed through differentiation of mantle‐derived basaltic magma. This suggests that Fe isotope fractionation during continental subduction is limited. Garnet separates display limited δ⁵⁶Fe variation ranging from ?0.08 ± 0.07 ‰ to 0.02 ± 0.07‰, whereas coexisting omphacite displays a large variation of δ⁵⁶Fe values from 0.15 ± 0.07‰ to 0.47 ± 0.07‰. Omphacite also has highly variable Fe³⁺/ΣFe ratios from 0.367 ± 0.025 to 0.598 ± 0.024, indicating modification after peak metamorphism. Omphacite from retrograde eclogites has elevated Fe³⁺/ΣFe ratios (0.54–0.60) compared to that from fresh eclogites (~0.37), whereas garnet displays a narrow range of ferric iron content with Fe³⁺/ΣFe ratios from 0.039 ± 0.013 to 0.065 ± 0.022. The homogenous δ⁵⁶Fe values and Fe³⁺/ΣFe ratios of garnet suggest that it survived the retrograde metamorphism and preserved its Fe‐isotopic features and ferric contents of peak metamorphism. Because of similar diffusion rates of Fe and Mg in garnet and omphacite, and constant Δ²⁶Mg_{omphacite‐garnet} values (1.14 ± 0.04‰), equilibrium iron isotope fractionation between garnet and omphacite was probably achieved during peak metamorphism. Elevated Fe³⁺/ΣFe ratios of omphacite from retrograde eclogites and variant Δ⁵⁶Fe_{omphacite‐garnet} values of the studied eclogites (0.13 ± 0.10‰ to 0.48 ± 0.10‰) indicate that oxidized geofluid infiltration resulted in the elevation of δ⁵⁶Fe values of omphacite during retrograde metamorphism.     

Oxygen isotopic study of Late Mesozoic cooling of the Mount Barcroft area,central White Mountains,eastern California

The Middle Jurassic Barcroft mafic granodiorite and Late Cretaceous, ternary-minimum McAfee Creek Granite are important components of the igneous arc sited along the SW North American margin. Bulk-rock analyses of 11 samples of the metaluminous, I-type Barcroft comagmatic suite have an average δ¹⁸O value of 7.4±0.6‰ (all values±1σ). Four Barcroft specimens average ε_Nd=?3.6±1.8, ⁸⁷Sr/⁸⁶Sr=0.707±0.001. The pluton consists of petrochemically gradational, Ca-amphibole-rich gabbro/diorite, granodiorite, metadiorite, and rare alaskite–aplite; for most of the pluton, oxygen isotope exchange of quartz, feldspar(s), biotite, and Ca-amphibole accompanied local deuteric alteration. Eight specimens of slightly peraluminous granitic rocks of the muscovite-bearing McAfee Creek series have an average δ¹⁸O of 8.6±0.5‰. Four McAfee-type samples average ε_Nd=?7.8±1.7, ⁸⁷Sr/⁸⁶Sr=0.711±0.004. For both plutons, bulk-rock evidence of exchange with near-surface water is lacking, suggesting ~5–10 km cooling depths. Barcroft minerals exhibit regular oxygen isotopic partitioning from high to low δ¹⁸O in the sequence quartz>plagioclase>K-feldspar>>amphibole≥biotite. Along the SE margin of the pluton, quartz and biotite in Lower Cambrian quartzites are higher in δ¹⁸O, and show slightly larger fractionations than igneous analogues. Exchange with fluids derived from these heated, contact-metamorphosed country rocks increased bulk ¹⁸O/¹⁶O ratios of Barcroft border rocks (and constituent plagioclase+subsolidus tremolite–actinolite), especially of granitic dikes transecting the wall rocks. Oxygen isotope thermometry for seven Barcroft pluton quartz–amphibole and six quartz–biotite pairs indicate apparent subsolidus temperatures averaging 519±49 °C. Quartz–plagioclase pairs from two Barcroft granodiorites yield values of 519 and 515 °C. A quartz–biotite pair from a quartzite adjacent to the Barcroft pluton yields an apparent temperature of 511 °C, in agreement with estimates based on contact metamorphic parageneses. Except for its SE margin, Barcroft pluton silicates evidently exchanged oxygen isotopes under local deuteric conditions. Compatible with Ca-amphibole thermobarometric analyses, areal distributions for quartz–plagioclase, quartz–amphibole, and quartz–biotite pairs reveal that putative annealing temperatures are lowest in NE-trending axial portions of the Barcroft body, so it simply cooled inwards. Intrusion ~70 million years later by the McAfee Creek Granite had no discernable effect on δ¹⁸O values of Barcroft minerals and bulk rocks.     

A novel model for silicon recycling in the lithosphere: Evidence from the Central Asian Orogenic Belt

Global-scale cycling of silicon through the biosphere, atmosphere, and hydrosphere has received much attention although, silicon cycling in the Earth’s lithosphere remains poorly understood. As the products of internal heat and material exchange, igneous rocks preserve significant information of silicon migration through the lithosphere. Here we report silicon isotopic compositions of nine peraluminous granites from the Chinese Altai, which forms part of the Central Asian Orogenic Belt. These rocks are characterized by the heaviest δ³⁰Si values (−0.13 ± 0.03‰ to +0.78 ± 0.05‰) compared to global granites, with a linear variation in the silicon isotopic values against silica content, with high silica-rich granites displaying more depleted isotopic compositions. In conjunction with the whole rock weakly negative ɛ_Nd(t) and uniform δ²⁶Mg values, as well as high δ¹⁸O values, we suggest that the δ³⁰Si values of these granites were mainly inherited from the magma source, rather than produced by magmatic fractionation. In addition, the wide range of initial ⁸⁷Sr/⁸⁶Sr ratios and high Ba content of the samples suggest the role of aqueous fluids. The Chinese Altai is considered to have formed through accretion of volcanic arcs associated with subduction of the Paleo-Asian oceanic lithosphere. The magma derived through partial melting of metasomatic mantle scavenges the heavy ³⁰Si isotopes derived through fluids released from oceanic sediments and transfers to the upper crust where partial melting of crustal sedimentary rocks occur. Mixing of these two melts generated the peraluminous granites. Our study offers a novel insight into a potentially important mechanism of silicon cycling in the lithosphere.     

Late Triassic granites from the northwestern margin of the Tibetan Plateau,the Dahongliutan example: petrogenesis and tectonic implications for the evolution of the Kangxiwa Palaeo-Tethys

The Dahongliutan granitic pluton consists of two-mica granites and is located in the eastern part of the Western Kunlun Orogen, northwestern Tibetan Plateau. Zircon separates from the pluton yield a SIMS U–Pb age of 217.5 ± 2.8 Ma. Rocks from the pluton contain relatively high and uniform SiO₂ (72.32–73.48 wt%) and total alkalis (Na₂O + K₂O = 8.07–8.67 wt%) and are peraluminous and high-K calc-alkaline to shoshonitic in composition. The Dahongliutan granites are relatively depleted in the high-field-strength elements and the heavy rare earth elements (HREEs) and have relatively high Rb, and low Ba and Sr concentrations. They contain low total rare earth element (REE) concentrations. The light REEs are strongly enriched relative to the HREEs, with (La/Yb)_N values of 28.56–37.01. The ε_Nd(t) values range from ?10.6 to ?8.8, and (⁸⁷Sr/⁸⁶Sr)_i = 0.7142–0.7210. Zircons from the pluton yield ε_Hf(t) values of ?13.8 to ?1.6, and δ¹⁸O = 10.5–11.6‰. Petrographic and geochemical features of the pluton indicate that the granites are S-type and were derived from parting melting of a mixture of metasedimentary and minor metaigneous sources in the middle–lower crust. Magmatic differentiation was dominated by the fractional crystallization of plagioclase, K-feldspar, muscovite, biotite, and accessory monazite, allanite, and Fe–Ti oxides. Regional granitoids were emplaced in the Early-to-Middle Triassic. Other younger granitoids, with ages of 240–200 Ma, are mostly I-type in character and were likely derived from multiple types of source rock, suggesting the source was heterogeneous Triassic crust. Such a scenario is consistent with their formation in a post-collisional setting. Our new data, combined with other geological evidence, suggest that the collision between the Tianshuihai and southern Kunlun terranes occurred between ca. 250 and 240 Ma, resulting in the closure of the Palaeo-Tethys. Post-collisional tectono-magmatic events may have occurred between 240 and 200 Ma.     

Oxygen isotope compositions and magmatic epidote from two contrasting metaluminous granitoids,NE Brazil

Oxygen isotope compositions of mineral separates were determined from two metaluminous granitoids (Emas and São Rafael plutons) from northeastern Brazil. The I-type Emas pluton has high δ¹⁸O (WR) values (11.5–11.8‰), whereas the São Rafael pluton has low δ¹⁸O (WR) values (7.5–8.1‰), but Sr and Nd are characteristics of S-type granitoids. Measured mineral–mineral fractionations suggest continuous sub-solidus inter-mineral isotope exchange among all minerals except zircon. There is a large and consistent quartz–epidote fractionation that gives apparent temperatures that are much lower than anticipated closure temperatures for epidote. Oxygen isotope fractionation between natural zircon and magmatic epidote is opposite to that predicted from theoretical determinations, as δ¹⁸O (epidote) <δ¹⁸O (zircon). An empirical calibration based on these results would suggests a closure T for oxygen in epidote of ~500 °C and Δ(qtz–epi) ~5.19 at 500 °C.     

Iron Isotope Compositions of Natural River and Lake Samples in the Karst Area, Guizhou Province, Southwest China

To better understand the Fe isotope characteristics of natural samples in the Karst area, the Fe isotope compositions of riverine suspended particulates, lake suspended particulates, lake sediments, porewaters, phytoplanktons, and aerosols in the watersheds of Lake Aha (a mineralized water system) and Lake Hongfeng (a mesotrophic water system), which are located in the Karst area, southwest China, were investigated. The studied samples displayed a variable range between δ56Fe=?2.03‰ and 0.36‰. Aerosols and phytoplanktons have similar or slightly heavier Fe isotope compositions relative to the average of igneous rocks. Fe isotope compositions of riverine Suspended Particulate Matter (SPM) were mainly affected by the types of tributaries. Suspended particulates collected from tributaries seriously contaminated with coal mine drainages displayed negative δ56Fe values (?0.89‰ to ?0.31‰) during summer, and there were significant increases of δ56Fe values in winter, except AR2, which was polluted with both coal mine drainage and sewage effluent. Characteristics of lakes have important influences on Fe isotope compositions of suspended particulates, lake sediments, and porewaters. The epilimnetic particulate Fe of Lake Hongfeng had δ56Fe=?0.04‰ to 0.13‰, while lighter Fe isotope compositions were measured for particulate Fe from Lake Aha, ranging from ?0.42‰ to ?0.09‰. Sediments collected from Hou Wu (HW) station of Lake Hongfeng have an average δ56Fe value of 0.09‰ and their corresponding porewaters have lighter Fe isotope compositions, ranging from ?0.57‰ to ?0.31‰; no significant variations have been observed. For the Liang Jiang Kou (LJK) station of Lake Aha, the content of reactive Fe and the concentration of sulfate were all high. Due to the reactive Fe recycling, including dissimilatory Fe reduction, adsorption, and Fe–sulfide formation, porewaters sampled near the sediment surface have been found to have a δ56Fe value as low as ?2.03‰ and an increase up to 0.12‰, with a burial depth of 10?cm. In contrast, an opposite variation trend was found for LJK sediments. Sediments sampled at 1-cm depth had a value of δ56Fe=?0.59‰ and decrease as low as ?1.75‰ with burial depth. This investigation demonstrated that significant Fe isotope fractionations occur in surface environments. Fe isotope compositions of particulate Fe were seriously affected by Fe sources, and Fe biogeochemical recycling has an important influence on Fe isotope fractionations in lake sediments, especially when there are significant amounts of reactive Fe and sulfate.     

Combined iron and magnesium isotope geochemistry of pyroxenite xenoliths from Hannuoba,North China Craton: implications for mantle metasomatism

We present high-precision iron and magnesium isotopic data for diverse mantle pyroxenite xenoliths collected from Hannuoba, North China Craton and provide the first combined iron and magnesium isotopic study of such rocks. Compositionally, these xenoliths range from Cr-diopside pyroxenites and Al-augite pyroxenites to garnet-bearing pyroxenites and are taken as physical evidence for different episodes of melt injection. Our results show that both Cr-diopside pyroxenites and Al-augite pyroxenites of cumulate origin display narrow ranges in iron and magnesium isotopic compositions (δ⁵⁷Fe = ?0.01 to 0.09 with an average of 0.03 ± 0.08 (2SD, n = 6); δ²⁶Mg = ? 0.28 to ?0.25 with an average of ?0.26 ± 0.03 (2SD, n = 3), respectively). These values are identical to those in the normal upper mantle and show equilibrium inter-mineral iron and magnesium isotope fractionation between coexisting mantle minerals. In contrast, the garnet-bearing pyroxenites, which are products of reactions between peridotites and silicate melts from an ancient subducted oceanic slab, exhibit larger iron isotopic variations, with δ⁵⁷Fe ranging from 0.12 to 0.30. The δ⁵⁷Fe values of minerals in these garnet-bearing pyroxenites also vary widely (?0.25 to 0.08 in olivines, ?0.04 to 0.25 in orthopyroxenes, ?0.07 to 0.31 in clinopyroxenes, 0.07 to 0.48 in spinels and 0.31–0.42 in garnets). In addition, the garnet-bearing pyroxenite shows light δ²⁶Mg (?0.43) relative to the mantle. The δ²⁶Mg of minerals in the garnet-bearing pyroxenite range from ?0.35 for olivine and orthopyroxene, to ?0.34 for clinopyroxene, 0.04 for spinel and ?0.68 for garnet. These measured values stand in marked contrast to calculated equilibrium iron and magnesium isotope fractionation between coexisting mantle minerals at mantle temperatures derived from theory, indicating disequilibrium isotope fractionation. Notably, one phlogopite clinopyroxenite with an apparent later metasomatic overprint has the heaviest δ⁵⁷Fe (as high as 1.00) but the lightest δ²⁶Mg (as low as ?1.50) values of all investigated samples. Overall, there appears to be a negative co-variation between δ⁵⁷Fe and δ²⁶Mg in the Hannuoba garnet-bearing pyroxenite and in the phlogopite clinopyroxenite xenoliths and minerals therein. These features may reflect kinetic isotopic fractionation due to iron and magnesium inter-diffusion during melt–rock interaction. Such processes play an important role in producing inter-mineral iron and magnesium isotopic disequilibrium and local iron and magnesium isotopic heterogeneity in the subcontinental mantle.     

Copper and iron isotope fractionation in mine tailings at the Laver and Kristineberg mines,northern Sweden

Previous research has shown that Cu and Fe isotopes are fractionated by dissolution and precipitation reactions driven by changing redox conditions. In this study, Cu isotope composition (⁶⁵Cu/⁶³Cu ratios) was studied in profiles through sulphide-bearing tailings at the former Cu mine at Laver and in a pilot-scale test cell at the Kristineberg mine, both in northern Sweden. The profile at Kristineberg was also analysed for Fe isotope composition (⁵⁶Fe/⁵⁴Fe ratios). At both sites sulphide oxidation resulted in an enrichment of the lighter Cu isotope in the oxidised zone of the tailings compared to the original isotope ratio, probably due to preferential losses of the heavier Cu isotope into the liquid phase during oxidation of sulphides. In a zone with secondary enrichment of Cu, located just below the oxidation front at Laver, δ⁶⁵Cu (compared to ERM-AE633) was as low as −4.35 ± 0.02‰, which can be compared to the original value of 1.31 ± 0.03‰ in the unoxidised tailings. Precipitation of covellite in the secondary Cu enrichment zone explains this fractionation. The Fe isotopic composition in the Kristineberg profile is similar in the oxidised zone and in the unoxidised zone, with average δ⁵⁶Fe values (relative to the IRMM-014) of −0.58 ± 0.06‰ and −0.49 ± 0.05‰, respectively. At the well-defined oxidation front, δ⁵⁶Fe was less negative, −0.24 ± 0.01‰. Processes such as Fe(II)–Fe(III) equilibrium and precipitation of Fe-(oxy)hydroxides at the oxidation front are assumed to cause this Fe isotope fractionation. This field study provides additional support for the importance of redox processes for the isotopic composition of Cu and Fe in natural systems.     

Correlated δ18O and [Ti] in lunar zircons: a terrestrial perspective for magma temperatures and water content on the Moon

Zircon grains were separated from lunar regolith and rocks returned from four Apollo landing sites, and analyzed in situ by secondary ion mass spectrometry. Many regolith zircons preserve magmatic δ¹⁸O and trace element compositions and, although out of petrologic context, represent a relatively unexplored resource for study of the Moon and possibly other bodies in the solar system. The combination of oxygen isotope ratios and [Ti] provides a unique geochemical signature that identifies zircons from the Moon. The oxygen isotope ratios of lunar zircons are remarkably constant and unexpectedly higher in δ¹⁸O (5.61 ± 0.07 ‰ VSMOW) than zircons from Earth’s oceanic crust (5.20 ± 0.03 ‰) even though mare basalt whole-rock samples are nearly the same in δ¹⁸O as oceanic basalts on Earth (~5.6 ‰). Thus, the average fractionation of oxygen isotopes between primitive basalt and zircon is smaller on the Moon [Δ¹⁸O(WR-Zrc) = 0.08 ± 0.09 ‰] than on Earth (0.37 ± 0.04 ‰). The smaller fractionations on the Moon suggest higher temperatures of zircon crystallization in lunar magmas and are consistent with higher [Ti] in lunar zircons. Phase equilibria estimates also indicate high temperatures for lunar magmas, but not specifically for evolved zircon-forming melts. If the solidus temperature of a given magma is a function of its water content, then so is the crystallization temperature of any zircon forming in that melt. The systematic nature of O and Ti data for lunar zircons suggests a model based on the following observations. Many of the analyzed lunar zircons are likely from K, rare earth elements, P (KREEP)-Zr-rich magmas. Zircon does not saturate in normal mafic magmas; igneous zircons in mafic rocks are typically late and formed in the last most evolved portion of melts. Even if initial bulk water content is moderately low, the late zircon-forming melt can concentrate water locally. In general, water lowers crystallization temperatures, in which case late igneous zircon can form at significantly lower temperatures than the solidus inferred for a bulk-rock composition. Although lunar basalts could readily lose H₂ to space during eruption, lowering water fugacity; the morphology, large size, and presence in plutonic rocks suggest that many zircons crystallized at depths that retarded degassing. In this case, the crystallization temperatures of zircons are a sensitive monitor of the water content of the parental magma as well as the evolved zircon-forming melt. If the smaller Δ¹⁸O(zircon–mare basalt) values reported here are characteristic of the Moon, then that would suggest that even highly evolved zircon-forming magmas on the Moon crystallized at higher temperature than similar magmas on Earth and that magmas, though not necessarily water-free, were generally drier on the Moon.     

Genesis of the Au–Bi–Cu–As, Cu–Mo ± W, and base–metal Au–Ag mineralization at the Mountain Freegold (Yukon, Canada): constraints from Ar–Ar and Re–Os geochronology and Pb and stable isotope compositions

The genesis of mineralized systems across the Mountain Freegold area, in the Dawson Range Cu–Au?±?Mo Belt of the Tintina Au province was constrained using Pb and stable isotope compositions and Ar–Ar and Re–Os geochronology. Pb isotope compositions of sulfides span a wide compositional range (²⁰⁶Pb/²⁰⁴Pb, 18.669–19.861; ²⁰⁸Pb/²⁰⁴Pb, 38.400–39.238) that overlaps the compositions of the spatially associated igneous rocks, thus indicating a magmatic origin for Pb and probably the other metals. Sulfur isotopic compositions of sulfide minerals are broadly similar and their δ³⁴S (Vienna-Canyon Diablo Troilite (V-CDT)) values range from ?1.4 to 3.6 ‰ consistent with the magmatic range, with the exception of stibnite from a Au–Sb–quartz vein, which has δ³⁴S values between ?8.1 and ?3.1 ‰. The δ³⁴S values of sulfates coexisting with sulfide are between 11.2 and 14.2 ‰; whereas, those from the weathering zone range from 3.7 to 4.3 ‰, indicating supergene sulfates derived from oxidation of hypogene sulfides. The δ¹³C (Vienna Peedee Belemnite (VPDB)) values of carbonate range from ?4.9 to 1.1 ‰ and are higher than magmatic values. The δ¹⁸O (V-SMOW) values of magmatic quartz phenocrysts and magmatic least-altered rocks vary between 6.2 and 10.1 ‰ and between 5.0 and 10.1 ‰, respectively, whereas altered magmatic rocks and hydrothermal minerals (quartz and magnetite) are relatively ¹⁸O-depleted (4.2 to 7.9 ‰ and ?6.3 to 1.5 ‰, respectively). Hydrogen isotope compositions of both least-altered and altered igneous rock samples are D-depleted (from ?133 to ?161 ‰ Vienna-Standard Mean Ocean Water (V-SMOW)), consistent with differential magma degassing and/or post-crystallization exchange between the rocks and meteoric ground water. Zircon from a chlorite-altered dike has a U–Pb crystallization age of 108.7?±?0.4 Ma; whereas, the same sample yielded a whole-rock Ar–Ar plateau age of 76.25?±?0.53 Ma. Likewise, molybdenite Re–Os model ages range from 75.8 to 78.2 Ma, indicating the mineralizing events are genetically related to Late Cretaceous volcano-plutonic intrusions in the area. The molybdenite Re–Os ages difference between the nearby Nucleus (75.9?±?0.3 to 76.2?±?0.3 Ma) and Revenue (77.9?±?0.3 to 78.2?±?0.3 Ma) mineral occurrences suggests an episodic mineralized system with two pulses of hydrothermal fluids separated by at least 2 Ma. This, in combination with geological features suggest the Nucleus deposit represents the apical and younger portion of the Revenue–Nucleus magmatic-hydrothermal system and may suggest an evolution from the porphyry to the epithermal environments.     

Fluid-induced breakdown of white mica controls nitrogen transfer during fluid–rock interaction in subduction zones

ABSTRACT

In order to determine the effects of fluid–rock interaction on nitrogen elemental and isotopic systematics in high-pressure metamorphic rocks, we investigated three different profiles representing three distinct scenarios of metasomatic overprinting. A profile from the Chinese Tianshan (ultra)high-pressure–low-temperature metamorphic belt represents a prograde, fluid-induced blueschist–eclogite transformation. This profile shows a systematic decrease in N concentrations from the host blueschist (~26 μg/g) via a blueschist–eclogite transition zone (19–23 μg/g) and an eclogitic selvage (12–16 μg/g) towards the former fluid pathway. Eclogites and blueschists show only a small variation in δ¹⁵N_air (+2.1 ± 0.3‰), but the systematic trend with distance is consistent with a batch devolatilization process. A second profile from the Tianshan represents a retrograde eclogite–blueschist transition. It shows increasing, but more scattered, N concentrations from the eclogite towards the blueschist and an unsystematic variation in δ¹⁵N values (δ¹⁵N = + 1.0 to +5.4‰). A third profile from the high-P/T metamorphic basement complex of the Southern Armorican Massif (Vendée, France) comprises a sequence from an eclogite lens via retrogressed eclogite and amphibolite into metasedimentary country rock gneisses. Metasedimentary gneisses have high N contents (14–52 μg/g) and positive δ¹⁵N values (+2.9 to +5.8‰), and N concentrations become lower away from the contact with 11–24 μg/g for the amphibolites, 10–14 μg/g for the retrogressed eclogite, and 2.1–3.6 μg/g for the pristine eclogite, which also has the lightest N isotopic compositions (δ¹⁵N = + 2.1 to +3.6‰).

Overall, geochemical correlations demonstrate that phengitic white mica is the major host of N in metamorphosed mafic rocks. During fluid-induced metamorphic overprint, both abundances and isotopic composition of N are controlled by the stability and presence of white mica. Phengite breakdown in high-P/T metamorphic rocks can liberate significant amounts of N into the fluid. Due to the sensitivity of the N isotope system to a sedimentary signature, it can be used to trace the extent of N transport during metasomatic processes. The Vendée profile demonstrates that this process occurs over several tens of metres and affects both N concentrations and N isotopic compositions.     

Iron isotope fractionation during biogeochemical cycle: Information from suspended particulate matter (SPM) in Aha Lake and its tributaries,Guizhou, China

Iron isotope compositions of suspended particulate matters (SPM) collected from the Aha Lake, an artificial lake in the karst area of Yun-Gui Plateau, and its tributaries in summer and winter were investigated for our understanding of the behavior of Fe isotopes during iron biogeochemical cycling in lake. δ⁵⁶Fe values of SPM display statistically negative shift relative to IRMM-014. Samples from the lake display a range from ?1.36‰ to ?0.10‰ in summer and from ?0.30‰ to ?0.07‰ in winter, while river samples vary from ?0.88‰ to 0.07‰ in summer and from ?0.35‰ to ?0.03‰ in winter. The average iron isotope composition of aerosol samples is + 0.10‰, which is very similar to that of igneous rocks (0.09‰). The SPM in most rivers and water column showed seasonal variation in δ⁵⁶Fe value: the δ⁵⁶Fe values of SPM in summer were lower than in winter. The seasonal variation in δ⁵⁶Fe value of the riverine SPM should be ascribed to the change in source of particulate Fe and geochemical process in the watershed: More particulate Fe was leached from soil and produced by weathering of pyrite widely distributed in coal-containing strata. It is suggested that both allochthonous inputs and the redox iron cycling control the variations of δ⁵⁶Fe values for SPM in lake.During summer stratification, an Fe cycle named “ferrous wheel” is established near the redox boundary where the upwardly diffusing Fe(II) is oxidized and the reactive Fe oxides formed will continuously sink back into the reduction zone to complete the cycle. The δ⁵⁶Fe values for SPM reach the minima, ?0.88‰ for DB station and ?1.36‰ for LJK station, just near the redox boundary as a result of the Fe cycling, where a rough 45% to 76% of Fe in these particles was produced by the repetitive cycle. Due to random transportation and diffusion, δ⁵⁶Fe values of the particles near the redox zone distributed into approximately a Gaussian shape. The good negative correlation existed between δ⁵⁶Fe values and Fe/Al ratios for DB station, suggesting that they together can be used as good indicators of the redox-driven Fe transformations.     

Nickel isotope fractionation during laterite Ni ore smelting and refining: Implications for tracing the sources of Ni in smelter-affected soils

Nickel isotope ratios were measured in ores, fly ash, slags and FeNi samples from two metallurgical plants located in the Goiás State, Brazil (Barro Alto, Niquelândia). This allowed investigating the mass-dependent fractionation of Ni isotopes during the Ni-laterite ore smelting and refining. Feeding material exhibits a large range of δ⁶⁰Ni values (from 0.02 ± 0.10‰ to 0.20 ± 0.05‰, n = 7), explained by the diversity of Ni-bearing phases, and the average of δ⁶⁰Ni_{feeding materials} was found equal to 0.08 ± 0.08‰ (2SD, n = 7). Both δ⁶⁰Ni values of fly ash (δ⁶⁰Ni = 0.07 ± 0.07‰, n = 10) and final FeNi produced (0.05 ± 0.02‰, n = 2) were not significantly different from the feeding materials ones. These values are consistent with the very high production yield of the factories. However, smelting slags present the heaviest δ⁶⁰Ni values of all the smelter samples, with δ⁶⁰Ni ranging from 0.11 ± 0.05‰ to 0.27 ± 0.05‰ (n = 8). Soils were also collected near and far from the Niquelândia metallurgical plant, to evaluate the potential of Ni isotopes for tracing the natural vs anthropogenic Ni in soils. The Ni isotopic composition of the non-impacted topsoils developed on ultramafic rocks ranges from −0.26 ± 0.09‰ to −0.04 ± 0.05‰ (n = 20). On the contrary, the Ni isotopic composition of the non-ultramafic topsoils, collected close to the plant, exhibit a large variation of δ⁶⁰Ni, ranging from −0.19 ± 0.13‰ up to 0.10 ± 0.05‰ (n = 4). This slight but significant enrichment in heavy isotopes highlights the potential impact of smelting activity in the surrounding area, as well as the potential of Ni isotopes for discerning anthropogenic samples (heavier δ⁶⁰Ni values) from natural ones (lighter δ⁶⁰Ni values). However, given the global range of published δ⁶⁰Ni values (from −1.03 to 2.5‰) and more particularly those associated to natural weathering of ultramafic rocks (from −0.61 to 0.32‰), the use of Ni isotopes for tracing environmental contamination from smelters will remain challenging.     

Assessment of bacterial biomass in the highly contaminated urban Nanming River,Guiyang, SW China

High anthropogenic N loads and abundant bacteria are characteristic of highly contaminated urban rivers. To better understand the dispersal and accumulation of bacteria, we determined contents and isotopic compositions of suspended particulate organic matter (SPOM) and bacteria in a highly contaminated urban river (the Nanming) and effluents in winter and summer of 2013. Relative to SPOM, bacterial biomass in the river was depleted in ¹³C and ¹⁵N and its C/N ratio was lower (δ¹³C: ? 33.2‰ ± 3.1‰; δ¹⁵N: ? 1.5‰ ± 1.2‰; C/N: 4.8 ± 0.6), while effluents showed higher ¹³C and ¹⁵N contents and C/N ratios (δ¹³C: ? 25‰ ± 2.1‰; δ¹⁵N: + 8.5‰ ± 1.1‰; C/N: 8.1 ± 1.2). Source recognition of SPOM was based on carbon isotopes because they are conservative and distinct between end-members (effluent detritus and bacterial biomass). Using a mixing model, bacterial biomass in the river was calculated to account for < 20% and < 56% of bulk suspended particulate organic nitrogen in winter and summer, respectively. An N budget showed that bacterial N was a small proportion of total nitrogen (< 7.4%) in the riverwater.