Oxygen isotope composition of xenoliths from the oceanic crust and volcanic edifice beneath Gran Canaria (Canary Islands): consequences for crustal contamination of ascending magmas

Xenolith samples of marine terrigenous sediments and altered Jurassic MORB from Gran Canaria (Canary Islands) represent samples of sub-island oceanic crust. These samples are postulated to define end-members for crustal contamination of basaltic and felsic ocean island magmas. The meta-igneous rocks show great heterogeneity in oxygen isotope compositions (δ¹⁸O 3.3–8.6‰), broadly correlating with their stratigraphic position in the oceanic crust. Gabbros interpreted as fragments of oceanic crust layer 3 have δ¹⁸O values of 3.3–5.1‰, which is lower than MORB (5.7–6.0‰). Layer 2 lavas and dykes show a broader range of δ¹⁸O of 4.1–8.6‰. Therefore, high-temperature metamorphism seems to have been the dominant process in layer 3, while both high- and low-temperature alteration have variably affected layer 2 rocks. Siliciclastic sediments have high δ¹⁸O values (14.1–16.4‰), indicating diagenesis and low-temperature interaction with seawater. The oxygen isotope stratigraphy of the crust beneath Gran Canaria is typical for old oceanic crust and resembles that in ophiolites. The lithologic boundary between older oceanic crust and the igneous core complex at 8–10 km depth—as postulated from geophysical data—probably coincides with a main magma stagnation level. There, the Miocene shield phase magmas interacted with preexisting oceanic crust. We suggest that the range in δ¹⁸O values (5.2–6.8‰) [Chem. Geol. 135 (1997) 233] found for shield basalts on Gran Canaria, and those in some Miocene felsic units (6.0–8.5‰), are best explained by assimilation of various amounts and combinations of oceanic and island crustal rocks and do not necessarily reflect mantle source characteristics.     

Hydration, 18O enrichment and oxidation during ocean floor hydrothermal metamorphism of ophiolitic metabasic rocks from E. Liguria,Italy

During ocean-floor hydrothermal metamorphism of a 225 m thick allochthonous Jurassic sequence of ophiolitic pillow lavas and underlying material in E. Liguria, Italy, the rocks were hydrated, enriched in ¹⁸O and oxidised. H₂O⁺ contents increased from ~0.3 to 3.8 wt.%, δ¹⁸O values increased from ~ +6‰ to values as high as +13.2‰, and ($\text{Fe}{}_2\text{O}{}_3\text{FeO}$1) increased from 0.18 to ratios as high as 1.0. Both δ¹⁸O values and oxidation ratios decrease in the original direction of increasing depth. Pillow margins are consistently more enriched in ¹⁸O and are more oxidised than cores.These observations are qualitatively interpreted in terms of a non-isothermal, heterogeneous reaction model of interaction of basalt with oxygen-bearing sea water during flow through the packed bed of pillows. Fluid flow approximated undirectional downward motion, and occurred in the recharge part of a cycle of single pass convection. Mass transfer through the pile was by flow (infiltration metasomatism), whereas intra-pillow mass transfer was diffusional. Oxygen isotope exchange and oxidation did not occur under conditions of perfect incremental equilibrium. An integrated bulk volumetric water/rock ratio of ~2 × 10³:1 is estimated from the oxidation profile.     

Modelling the geochemical cycle of boron: Implications for the long-term δ11B evolution of seawater and oceanic crust

The boron geochemical cycle has been simulated using a time-dependent geochemical box model that was coupled to a one-dimension model of seawater–oceanic crust interactions. Boron elemental and isotopic compositions of oceanic rocks as a function of depth were calculated by mass balance, using the temperature and porosity profiles of the crust as well as the available experimental and empirical distribution coefficients and fractionation factors between mineral and water. Ranges of boron elemental and isotopic variations of seawater were calculated for crust–seawater interactions that take place from the ridge-axis to the off-axis closure of the hydrothermal system. The present-day δ¹¹B of seawater (40‰) could represent a steady-state value. However, depending on crustal permeability, lifetime of water–rock interactions, and expansion rate of the oceanic ridge, the δ¹¹B of seawater may vary from 30‰ to 50‰ at the 10 million year scale.Some boron isotope compositions of Cretaceous biogenic carbonates and ophiolitic serpentinites from Oman are comparable to modern rock samples, suggesting that the δ¹¹B of Cretaceous seawater was close to the present-day value. Low δ¹¹B values of some biogenic carbonates cannot be attributed to low pH values of past seawater, but more probably to δ¹¹B variations of seawater or diagenetic alteration by crustal aqueous fluids. Boron isotope composition of hydrothermally altered serpentines could be considered as a promising proxy of the seawater composition.     

Oxygen isotope signatures in olivines from São Miguel (Azores) basalts: implications for crustal and mantle processes

Oxygen isotope ratios were measured in olivines from eight São Miguel basalt lavas. With one exception (4.57‰), the olivines are indistinguishable from one another with an average δ¹⁸O of 4.92±0.03‰ (1σ). This value is slightly lower than that characteristic of upper mantle peridotite and MORB olivines (5.2±0.2‰). Assimilation of ≥10–20% of high-temperature altered lower oceanic crust or 4–9% hydrothermally altered volcanic edifice rocks could produce the low δ¹⁸O signatures in the São Miguel olivines; both of these assimilation models are permitted by the trace element and radiogenic isotope variations in the São Miguel basalts. However, the limited variation in δ¹⁸O despite eruption of the basalts through compositionally and tectonically variable lithosphere, and the lack of correlation of δ¹⁸O with olivine forsterite content, are more easily explained if the olivine δ¹⁸O signatures are inherited from their mantle source. If the δ¹⁸O signatures reflect mantle source compositions, then the relatively low and uniform δ¹⁸O signatures allow constraints to be placed on the origin of the mantle sources beneath São Miguel. Extreme variations in radiogenic isotope signatures have previously been attributed to two component source mixing between a predominant Azores plume source with mild HIMU-like characteristics, and an EMII-type mantle with very radiogenic Sr. The low δ¹⁸O signatures in the São Miguel basalt olivines suggest that the predominant Azores plume source contains >10% hydrothermally altered recycled oceanic crust. The limited variation in δ¹⁸O is consistent with a component of recycled sediment in the São Miguel EMII-type source, although, unlike the case for other EMII OIB (e.g. Samoa and Society), the relatively low δ¹⁸O signatures in São Miguel restrict any involvement of recycled sediment to <2% of a relatively low δ¹⁸O and very radiogenic Sr or high Rb/Sr sediment. Involvement of several percent metasomatized subcontinental lithospheric mantle could alternatively produce the EMII-type Sr–Nd–Pb isotope signatures without significantly affecting the plume-related low δ¹⁸O signatures. The São Miguel δ¹⁸O data are thus consistent with mixing between a low δ¹⁸O Azores plume source with a component of subducted, hydrothermally altered lower oceanic crust, and either minor recycled sediment or localized EMII-rich delaminated subcontinental lithospheric mantle. The latter could have been introduced into the lithosphere or shallow asthenosphere during opening of the Atlantic ocean basin.     

Strontium isotopic contamination and oxidation during ocean floor hydrothermal metamorphism of the ophiolitic rocks of the Troodos Massif,Cyprus

Twenty-six new high precision ${}^{87}\text{Sr}{}^{86}\text{Sr}$ratio determinations and existing analyses are used to discuss the strontium isotopic composition of the Upper Cretaceous ophiolitic rocks of the Troodos Massif, Cyprus. Relative to initial magmatic ${}^{87}\text{Sr}{}^{86}\text{Sr}$ ratios (0.70338 ± 0.00010 to 0.70365 ± 0.00005), the hydrothermally metamorphosed pillow lavas and dyke complex have been contaminated by isotopically heavier strontium.This observation confirms the hypothesis that hydrothermal metamorphism was a consequence of sea water-rock interaction, since sea water was the only readily accessible reservoir of isotopically heavier strontium. The fact that metagabbros and altered trondhjemites were also Sr isotopically contaminated shows that sea water penetrated approximately 2 km into the oceanic crust represented by the ophiolitic sequence.The amount of Sr isotopic contamination requires that the bulk sea water: rock ratio was at least ~15:1 and shows that water-rock interaction occurred in a flow system. The degree of oxidation decreases with increasing depth. This shows that the vertical component of fluid flow was downward. The absolute bulk water/rock ratio (for water at S.T.P.), as estimated from the oxidation profile, may have been as large as ~3 × 10³:1 —a large figure which independently confirms that rocks showing strong δ¹⁸O shifts have interacted with large volumes of water.The sites of discharge of the hot fluid, which must have come out of the system, are identified as the cupriferous pyrite ore deposits. This process of mass transfer corresponds to hydrothermal convection in a permeable medium with an open upper boundary surface.     

Modelling of the oxygen isotope evolution of seawater: implications for the climate interpretation of the δ18O of marine sediments

It is often argued that the δ¹⁸O value of oceanic water was maintained close to 0‰ for hundreds of millions of years, as a consequence of oxygen isotope exchange between oceanic crust and seawater. However, for several decades, the interpretation of the biosedimentary oxygen isotope record has conflicted with the igneous record because, with increasing age, a general trend of decreasing δ¹⁸O values (about 6‰) is observed in most carbonates, cherts and phosphates, especially for the Paleozoic and early Mesozoic. We developed a dynamical model of seawater-crust interaction that computes the δ¹⁸O value in these two reservoirs as function of time. This model takes into account the continuous production of crust at oceanic ridges, its expansion rate, the permeability profile with space and time, the mineralogical mode of the crust, and the kinetics of oxygen isotope exchange between rock-forming minerals and seawater. The model indicates that the δ¹⁸O value of seawater may vary by ±2‰ with a time response ranging from 5 to 50 Ma for expansion rates of 1 to 10 cm.a⁻¹. The variation of ±2‰ is fixed by both integrated water-rock ratio and closure time of the seawater-crust system by sediments. Variations in the oxygen isotope ratio of seawater through time have important implications for the interpretation of the systematically low δ¹⁸O values of pre-Jurassic marine sediments. According to our model, marine paleotemperatures could be up to 10°C lower than those expected when applying the classical hypothesis of an ice-free ocean with a δ¹⁸O value of −1‰.     

Nature of serpentinization and carbonation of ophiolitic peridotites (Eastern Desert,Egypt): constrains from stable isotopes and whole-rock geochemistry

Serpentinites are widespread in the Arabian-Nubian Shield (ANS) of the Eastern Desert of Egypt and usually enclose a tremendous carbonate alteration. Combined investigation of the stable isotope compositions of both O-H in serpentines and O-C in the whole-rock and the chemistry of the fluid-mobile elements (FMEs) in whole-rock serpentinites from Wadi (W.) Alam, Gabal (G.) El-Maiyit, and W. Atalla (Eastern Desert of Egypt) allowed to better understand the subsequent fluid sources of serpentinization and carbonation, as well as impact of these processes on the geochemistry of protolith ultramafic rocks. δ ¹⁸O values of W. Alam and W. Atalla serpentine minerals are close to the unaltered mantle and propose a lower temperature serpentinization if compared with those of G. El-Maiyit rocks. Moreover, δD values of W. Alam and W. Atalla serpentines (? 94 to ? 65‰) correspond to an igneous source that might be hydrothermal solutions mixed with the seawater in the mid-ocean ridge-arc transition setting. On the other hand, G. El-Maiyit serpentine is more depleted in ¹⁸O (with lower δ ¹⁸O values = 4.08–4.85‰), and its δD values (? 73 to 56 ‰) are most probably caused by an interaction with metamorphic fluids, acquired during on-land emplacement of oceanic peridotites or during burial in fore-arc setting. In addition, the oceanic oxygen isotope composition of most studied ophiolitic serpentinites points to the preservation of the pre-obduction δ ¹⁸O signatures and thus local-scale fluid flow at low water/rock ratios. Serpentinization fluids were CO₂-poor and the carbonation of the serpentinites resulted from infiltration of externally derived fluids. δ ¹⁸O_VSMOW values of carbonates in the studied serpentinites vary between heavier oxygen isotope composition in G. El-Maiyit samples (av. = 25.32‰) to lighter composition in W. Alam samples (av. = 19.43‰). However, δ ¹³C values of all serpentinites point mantle source of carbon. This source might have been evolved in mid-ocean ridge (W. Atalla) and subduction zone (W. Alam and G. El-Maiyit) settings. The studied serpentinites are usually enriched in FMEs, particularly Pb, Sr, Cs, and U. These enrichments were most probably the result of serpentinization and/or carbonation.     

Low-O18 basalts from Iceland

The volcanic rocks of Iceland are anomalous in their oxygen isotope content. Recent tholeiitic and transitional alkali basalts from Iceland range in (δO¹⁸ from 1·8 to 5δ7%. Most of the tholeiitic basalts and their phenocrysts are at least 1% lower in δO¹⁸ than unaltered basalts from other oceanic islands or oceanic ridges. The Icelandic basalts that resemble ridge basalts in δO¹⁸ also resemble them in major element chemistry. δO¹⁸ values of alkali olivine basalts are closest to those of other oceanic islands. Secondary alteration processes have lowered as well as raised the δO¹⁸ values of some Icelandic rocks, but such surface mechanisms cannot account for the distribution of oxygen isotopes in the Recent basalts of Iceland. Three mechanisms that could give rise to the low-O¹⁸ magmas are (1) exchange of oxygen between magma and low-O¹⁸ hydrothermally altered rock, (2) exchange with low-O¹⁸ meteoric water, or (3) an exceptional mantle under Iceland. None of the above models can satisfactorily account for all the observations.     

Depositional age and tectonic environment of the Gouap banded iron formations from the Nyong group,SW Cameroon:Insights from isotopic,geochemical and geochronological studies of drillcore samples

The discovery of the Gouap banded iron formations(BIFs)-hosted iron mineralization in the northwestern of the Nyong Group(Ntem Complex)in southwestern Cameroon provides unique insights into the geology of this region.In this contribution,we firstly report detailed study of geochemistry,isotopic and geochronology of well preserved samples of the Gouap BIFs collected from diamond drillcores.The Gouap BIFs consist mainly of amphibole BIFs and amphibole-pyrite BIFs characterized by dominant Fe₂O₃+SiO₂contents and variable contents of CaO,MgO and SO₃,consistent with the presence of amphibole,chlorite,epidote and pyrite,formed during amphibolite facies metamorphism and overprinted hydrothermal event.The amphibole–pyrite BIFs are typically enriched in trace and rare earth elements(REE)compared to the amphibole BIFs,suggesting the influence of detrital materials as well as secondary hydrothermal alteration.The Post Archean Australian Shale(PAAS)-normalized REE–Y profiles of the Gouap BIFs display positive La,Eu anomalies,weak negative Ce anomalies,indicating a mixture of low-temperature hydrothermal fluids and relatively oxic conditions probably under relative shallow seawater.We present here the first isotopic data of BIFs within the Ntem Complex.Theδ³⁰Si_NBS28values of the quartz from the Gouap BIFs vary from-1.5‰to-0.3‰and from-0.8‰to-0.9‰for the amphibole BIFs and amphibole–pyrite BIFs,respectively.The quartz hasδ¹⁸OV-SMOW values of 6.8‰–9.5‰(amphibole BIFs)and 9.2‰–10.6‰(amphibole–pyrite BIFs).The magnetite from the Gouap BIFs showsδ¹⁸O values ranging from-3.5‰to-1.8‰and from-3‰to-1.7‰for the amphibole BIFs and amphibole–pyrite BIFs,respectively.Moreover,the pyrite grains in the amphibole–pyrite BIFs displayδ34S values of 1.1‰–1.8‰.All isotopic data of the Gouap BIFs confirm that they might have precipitated from low-temperature hydrothermal fluids with detrital input distant from the volcanic activity.According to their geochemical and isotopic characteristics,we propose that the Gouap BIFs belong to the Superior type.In situ U–Pb zircon dating of BIFs was conducted to assess the BIF depositional age based on strong evidence of zircon in thin section.The Gouap BIFs were probably deposited at 2422±50 Ma in a region where sediments extended from continental shelf to deep-water environments along craton margins like the Caue Formation of the Minas Supergroup,Brazil.The studied BIFs have experienced regional hydrothermal activity and metamorphism at 2089±8.3 Ma during the Eburnean–Transamazonian orogeny.These findings suggest a physical continuity between the protocratonic masses of both Sao Francisco and Congo continents in the Rhyacian Period.     

Stable isotope characteristics of precipitation of Pamba River basin,Kerala, India

Stable isotope composition of precipitation from Pamba River basin, Kerala, India, is evaluated to understand the role of spatial and temporal variations on rainwater isotope characteristics. Physiographically different locations in the basin showed strong spatial and temporal variations. δ ¹⁸O varied from ?7.63 to ?1.75 ‰ in the lowlands; from ?9.32 to ?1.94 ‰ in the midlands and from ?11.6 to ?4.00 ‰ in the highlands. Local Meteoric Water Lines (LMWL) for the three regions were determined separately and an overall LMWL for the whole of the basin was found to be δ ²H = 6.6 (±0.4) δ ¹⁸ O+10.4 (±2.0). Altitude effect was evident for the basin (0.1 ‰ for δ ¹⁸O and 0.8 ‰ for δ ²H per 100 m elevation), while the amount effect was weak. The precipitation formed from the marine moisture supplied at a steady rate, without much isotopic evolution in this period may have masked the possible depletion of heavier isotopes with increasing rainfall. Consistently high d-excess values showed the influence of recycled vapour, despite the prevailing high relative humidity. The oceanic and continental vapour source origins for the south-west and north-east monsoons were clearly noted in the precipitation in the basin. Rayleigh distillation model showed about 30% rainout of the monsoon vapour mass in the basin.     

Oxygen isotopes in mammal bone phosphate: A new tool for paleohydrological and paleoclimatological research?

Oxygen isotope analyses of water in blood of humans and domestic pigs indicate that the oxygen isotope fractionation effects between ingested water and body water are the same in all specimens of the same species. The δ¹⁸O of body water has been shown to vary linearly with the mean δ¹⁸O of local meteoric water. This conclusion also holds for the bone phosphate. Thus, δ¹⁸O(PO^3?₄) values of unaltered fossil bones from humans and domestic pigs can be used to reconstruct the δ¹⁸O values of local meteoric waters during the life-times of the mammals. Such data can be used for paleohydrological and paleoclimatological studies both on land and at sea.     

Anatomy of a large Ag–Pb–Zn deposit in the Great Xing'an Range,northeast China: metallogeny associated with Early Cretaceous magmatism

The Bairendaba vein-type Ag–Pb–Zn deposit, hosted in a Carboniferous quartz diorite, is one of the largest polymetallic deposits in the southern Great Xing'an Range. Reserves exceeding 8000 tonnes of Ag and 3 million tonnes of Pb?+?Zn with grades of 30 g/t and 4.5% have been estimated. We identify three distinct mineralization stages in this deposit: a barren pre-ore stage (stage 1), a main-ore stage with economic Ag–Pb–Zn mineralization (stage 2), and a post-ore stage with barren mineralization (stage 3). Stage 1 is characterized by abundant arsenopyrite?+?quartz and minor pyrite. Stage 2 is represented by abundant Fe–Zn–Pb–Ag sulphides and is further subdivided into three substages comprising the calcite–polymetallic sulphide stage (substage 1), the fluorite–polymetallic sulphide stage (substage 2), and the quartz–polymetallic sulphide stage (substage 3). Stage 3 involves an assemblage dominated by calcite with variable pyrite, galena, quartz, fluorite, illite, and chlorite. Fluid inclusion analysis and mineral thermometry indicate that the three stages of mineralization were formed at temperatures of 320–350°C, 200–340°C, and 180–240°C, respectively. Stage 1 early mineralization is characterized by low-salinity fluids (5.86–8.81 wt.% NaCl equiv.) with an isotopic signature of magmatic origin (δ¹⁸O_fluid = 10.45–10.65‰). The main ore minerals of stage 2 precipitated from aqueous–carbonic fluids (4.34–8.81 wt.% NaCl equiv.). The calculated and measured oxygen and hydrogen isotopic compositions of the ore-forming aqueous fluids (δ¹⁸O_fluid = 3.31–8.59‰, δD_fluid?=??132.00‰ to??104.00‰) indicate that they were derived from a magmatic source and mixed with meteoric water. Measured and calculated sulphur isotope compositions of hydrothermal fluids (δ³⁴S_∑S?=??1.2–3.8‰) indicate that the ore sulphur was derived mainly from a magmatic source. The calculated carbon isotope compositions of hydrothermal fluids (δ¹³C_fluid?=??26.52‰ to??25.82‰) suggest a possible contribution of carbon sourced from the basement gneisses. The stage 3 late mineralization is dominated (1.40–8.81 wt.% NaCl equiv.) by aqueous fluids. The fluids show lower δ¹⁸O_fluid (?16.06‰ to??0.70‰) and higher δD_fluid (?90.10‰ to??74.50‰) values, indicating a heated meteoric water signature. The calculated carbon isotope compositions (δ¹³C_fluid?=??12.82‰ to??6.62‰) of the hydrothermal fluids in stage 3 also suggest a possible contribution of gneiss-sourced carbon. The isotopic compositions and fluid chemistry indicate that the ore mineralization in the Bairendaba deposit was related to Early Cretaceous magmatism.     

A-type granites induced by a breaking-off and delamination of the subducted Junggar oceanic plate,West Junggar,Northwest China

The A-type granites with highly positive ε_Nd(t) values in the West Junggar, Central Asian Orogenic Belt (CAOB), have long been perceived as a group formed under the same tectonic and geodynamic setting, magmatic sourceq and petrogenetic model. Geological evidence shows that these granites occurred at two different tectonic units related to the southeastern subduction of Junggar oceanic plate: the Hongshan and Karamay granites emplaced in the southeast of West Junggar in the Baogutu continental arc; whereas the Akebasitao and Miaoergou granites formed in the accretionary prism. Here the authors present new bulk-rock geochemistry and Sr-Nd isotopes, zircon U-Pb ages and Hf-O isotopes data on these granites. The granites in the Baogutu continental arc and accretionary prism contain similar zircon ε_Hf(t) values (+10.9 to +16.2) and bulk-rock geochemical characteristics (high SiO₂ and K₂O contents, enriched LILEs (except Sr), depleted Sr, Ta and Ti, and negative anomalies in Ce and Eu). The Hongshan and Karamay granites in the Baogutu continental arc have older zircon U-Pb ages (315–305 Ma) and moderate ¹⁸O enrichments (δ¹⁸O_zircon=+6.41‰–+7.96‰); whereas the Akebasitao and Miaoergou granites in the accretionary prism have younger zircon U-Pb ages (305–301 Ma) with higher ¹⁸O enrichments (δ¹⁸O_zircon=+8.72‰–+9.89‰). The authors deduce that the elevated ¹⁸O enrichments of the Akebasitao and Miaoergou granites were probably inherited from low-temperature altered oceanic crusts. The Akebasitao and Miaoergou granites were originated from partial melting of low-temperature altered oceanic crusts with juvenile oceanic sediments below the accretionary prism. The Hongshan and Karamay granites were mainly derived from partial melting of basaltic juvenile lower crust with mixtures of potentially chemical weathered ancient crustal residues and mantle basaltic melt (induced by hot intruding mantle basaltic magma at the bottom of the Baogutu continental arc). On the other hand, the Miaoergou charnockite might be sourced from a deeper partial melting reservoir under the accretionary prism, consisting of the low-temperature altered oceanic crust, juvenile oceanic sediments, and mantle basaltic melt. These granites could be related to the asthenosphere’s counterflow and upwelling, caused by the break-off and delamination of the subducted oceanic plate beneath the accretionary prism Baogutu continental arc in a post-collisional tectonic setting.©2022 China Geology Editorial Office.     

A stable isotope study of serpentinization and metamorphism in the Highland Border Suite,Scotland, U.K.

$\text{D}\text{H}$ and ${}^{18}\text{O}{}^{16}\text{O}$ ratios have been measured for whole-rock samples and mineral separates from the mafic and ultramatic rocks of the Cambro-Ordovician Highland Border Suite. The H- and O- isotopic compositions of these rocks record individual stages in a relatively complex 500 Myr old hydrothermal/metamorphic history. Lizardite serpentinites (δD ～ ? 105‰; δ¹⁸O ～ + 6.2‰) record a premetamorphic history and indicate that parent harzburgites, dunites, and pyroxenites were serpentinized through low-temperature interaction with meteoric waters during cooling. The other rocks of the Highland Border Suite record subsequent interaction with metamorphic fluids. Amphibolite facies hornblende schists were produced through thrust-related (dynamothermal) metamorphism of spilitic pillow lavas. During dehydration, D-enriched fluids were driven off from the spilites thus leaving the hornblende schists to equilibrate with a relatively D-depleted internal fluid reservoir (δD ～ ? 45‰). The expelled D-enriched fluids may have mixed with more typical Dalradian metamorphic waters which then exchanged with the remaining mafic rocks and lizardite serpentinites during greenschist facies regional metamorphism to produce antigorite serpentinites (δD ～ ? 62‰; δ¹⁸O ～ + 8‰) and greenschist metaspilites (δD ～ ? 57‰; δ¹⁸O ～ + 7.3‰) with similar H- and O-isotopic compositions. Serpentinites which have been only partially metamorphosed show intermediate H-isotopic compositions between that of metamorphic antigorite (δD ～ ? 62‰) and non-metamorphic lizardite δD ～ ? 105‰) end members.     

Correlation of δ<Superscript>18</Superscript>O and initial<Superscript>87</Superscript>Sr/<Superscript>86</Superscript>Sr ratios in Kirkpatrick basalt on Mt. Falla,transantarctic mountains

Theδ¹⁸O (SMOW) values of the Kirkpatrick Basalt (Jurassic) on Mt. Falla, Queen Alexandra Range, vary between +6.3‰ and +8.6‰ The apparent enrichment of these rocks in¹⁸O excludes the possibility that they were altered by interaction with aqueous solutions of meteoric origin. Theδ¹⁸O values of the flows correlate significantly with the initial⁸⁷Sr/⁸⁶Sr ratios and all major elements. These correlations confirm the hypothesis that the basalt magma was contaminated by rocks of the continental crust through which it was extruded. Estimates of the chemical composition of the basalt magma and the contaminant, based on extrapolations of the new oxygen data, generally confirm earlier estimates based on extrapolations of initial⁸⁷Sr/⁸⁶Sr ratios. The⁸⁷Sr/⁸⁶Sr ratio of the uncontaminated basalt was 0.7093 which indicates that magma may have originated by melting either in old Rb-enriched lithospheric mantle under Antarctica or in the overlying crust, or both.     

Laboratory chalcopyrite oxidation by Acidithiobacillus ferrooxidans: Oxygen and sulfur isotope fractionation

Laboratory experiments were conducted to simulate chalcopyrite oxidation under anaerobic and aerobic conditions in the absence or presence of the bacterium Acidithiobacillus ferrooxidans. Experiments were carried out with 3 different oxygen isotope values of water (δ¹⁸O_H2O) so that approach to equilibrium or steady-state isotope fractionation for different starting conditions could be evaluated. The contribution of dissolved O₂ and water-derived oxygen to dissolved sulfate formed by chalcopyrite oxidation was unambiguously resolved during the aerobic experiments. Aerobic oxidation of chalcopyrite showed 93 ± 1% incorporation of water oxygen into the resulting sulfate during the biological experiments. Anaerobic experiments showed similar percentages of water oxygen incorporation into sulfate, but were more variable. The experiments also allowed determination of sulfate–water oxygen isotope fractionation, ε¹⁸O_SO4–H2O, of ~ 3.8‰ for the anaerobic experiments. Aerobic oxidation produced apparent ε_SO4–H2O values (6.4‰) higher than the anaerobic experiments, possibly due to additional incorporation of dissolved O₂ into sulfate. δ³⁴S_SO4 values are ~ 4‰ lower than the parent sulfide mineral during anaerobic oxidation of chalcopyrite, with no significant difference between abiotic and biological processes. For the aerobic experiments, a small depletion in δ³⁴S_SO4 of ~? 1.5 ± 0.2‰ was observed for the biological experiments. Fewer solids precipitated during oxidation under aerobic conditions than under anaerobic conditions, which may account for the observed differences in sulfur isotope fractionation under these contrasting conditions.     

Stable isotope(δ~(13)C_(ker),δ~(13)C_(carb),δ~(18)O_(carb)) distribution along a Cambrian outcrop section in the eastern Tarim Basin,NW China and its geochemical significance

This study investigated the geochemical features of the lower Paleozoic strata of Yaerdang Mountain outcrop along with the core samples from well TD2∈ in the eastern Tarim Basin,NW China.The total organic carbon abundance,hydrocarbon-generating precursor biospecies,and stable isotope ratios of organics and carbonate(δ~(13)C_(ker),δ~(13)C_(carb) and δ~(18)O_(carb)) were comprehensively studied for their possible correlative constraints during sedimentary evolution.The results revealed that the δ~(13)C_(ker)(VPDB) of Cambrian kerogens along the outcrop section varied from-34.6‰ to-28.4‰,indicating an increasing tendency from the lower Cambrian to the upper Cambrian.This was on the whole accompanied by the variation in the δ~(13)C_(carb) and δ~(18)O_(carb) along the profile,which might be associated with the changes in the sea level and also in the compositional variation of benthic and planktonic biomass.The large variation in the stable carbon isotope ratios up to 6‰ along the outcrop section reflected the heterogeneity of the Cambrian source rocks from the eastern Tarim Basin.Hence,the ~(13)C-enriched crude oils from well TD2∈might have been derived from a localized stratum of Cambrian source rocks.The results from this study showed the possibility of multiple source kitchens in the Cambrian-lower Ordovician portion of Tarim Basin.     

Fingerprinting a multistage metamorphic fluid–rock history: Evidence from grain scale Sr,O and C isotopic and trace element variations in high-grade marbles from East Antarctica

Granulite grade marble layers interlayered with metapelitic granulites from Lützow Holm Bay, East Antarctica, provide insight into fluid–rock interactions during burial to and exhumation from lower crustal levels. Sub-millimeter scale strontium, oxygen and carbon isotope variations along with LA-ICPMS trace element geochemistry and mineral chemistry of texturally characterized carbonates and associated minerals helped to reconstruct the multistage metamorphic fluid history.Fluid–rock interaction dating back to prograde metamorphism are still preserved in consistently low oxygen and high strontium isotope compositions (δ¹⁸O = 12‰; ⁸⁷Sr/⁸⁶Sr_(550Ma) = 0.7248) within a massif dolomitic marble layer that escaped significant later metasomatism. In most marbles, total re-crystallization and isotopic resetting occurred in the presence of “externally derived” hyper-saline fluids that circulated along the carbonate layers during the early stages of prograde metamorphism. This leads to a trend of increased radiogenic Sr in marbles towards the value of associated metapelitic rocks that have ⁸⁷Sr/⁸⁶Sr_(550Ma) of 0.764.LA-ICPMS studies on trace elements in carbonate and associated silicate minerals at different textural settings, distinguished using cathodoluminescence microscopy, revealed multiple metasomatic events during retrograde metamorphism. Trace element contents of Ba, Sr, Pb and U gave compelling evidence for metasomatic alteration that postdate the exsolution of carbonate at ~ 600 ºC, which can be correlated with the fluids released from the crystallization of anatectic melts and pegmatites. Subsequently, meteoric fluid infiltration occurred at a shallower level of the crust and caused extreme oxygen isotopic heterogeneity (δ¹⁸O = 14.7 ~ ? 4.9‰) and imprinted high concentration of fluid mobile elements. Taken together our results emphasize the importance of integrating textural and chemical heterogeneities to reveal the multiple episodes of fluid–rock interaction processes in a dynamic continental crust, which has major implications on migration of fluids and material and help in formulating models on the geodynamic evolution of crust.     

Isotopic constraints on ice age fluids in active geothermal systems: Reykjanes, Iceland

The Reykjanes geothermal system is located on the landward extension of the Mid-Atlantic Ridge in southwest Iceland, and provides an on-land proxy to high-temperature hydrothermal systems of oceanic spreading centers. Previous studies of elemental composition and salinity have shown that Reykjanes geothermal fluids are likely hydrothermally modified seawater. However, δD values of these fluids are as low as −23‰, which is indicative of a meteoric water component. Here we constrain the origin of Reykjanes hydrothermal solutions by analysis of hydrogen and oxygen isotope compositions of hydrothermal epidote from geothermal drillholes at depths between 1 and 3 km. δD_EPIDOTE values from wells RN-8, -9, -10 and -17 collectively range from −60 to −78‰, and δ¹⁸O_EPIDOTE in these wells are between −3.0 and 2.3‰. The δD values of epidote generally increase along a NE trend through the geothermal field, whereas δ¹⁸O values generally decrease, suggesting a southwest to northeast migration of the geothermal upflow zone with time that is consistent with present-day temperatures and observed hydrothermal mineral zones. For comparative analysis, the meteoric-water dominated Nesjavellir and Krafla geothermal systems, which have a δD_FLUID of ∼ −79‰ and −89‰, respectively, show δD_EPIDOTE values of −115‰ and −125‰. In contrast, δD_EPIDOTE from the mixed meteoric-seawater Svartsengi geothermal system is −68‰; comparable to δD_EPIDOTE from well RN-10 at Reykjanes.Stable isotope compositions of geothermal fluids in isotopic equilibrium with the epidotes at Reykjanes are computed using published temperature dependent hydrogen and oxygen isotope fractionation curves for epidote-water, measured isotope composition of the epidotes and temperatures approximated from the boiling point curve with depth. Calculated δD and δ¹⁸O of geothermal fluids are less than 0‰, suggesting that fluids of meteoric or glacial origin are a significant component of the geothermal solutions. Additionally, δD_FLUID values in equilibrium with geothermal epidote are lower than those of modern-day fluids, whereas calculated δ¹⁸O_FLUID values are within range of the observed fluid isotope composition. We propose that modern δD_EPIDOTE and δD_FLUID values are the result of diffusional exchange between hydrous alteration minerals that precipitated from glacially-derived fluids early in the evolution of the Reykjanes system and modern seawater-derived geothermal fluids. A simplified model of isotope exchange in the Reykjanes geothermal system, in which the average starting δD_ROCK value is −125‰ and the water to rock mass ratio is 0.25, predicts a δD_FLUID composition within 1‰ of average measured values. This model resolves the discrepancy between fluid salinity and isotope composition of Reykjanes geothermal fluids, explains the observed disequilibrium between modern fluids and hydrothermal epidote, and suggests that rock-fluid interaction is the dominant control over the evolution of fluid isotope composition in the hydrothermal system.     

Origin of natural sulfur-metal chimney in the Tangyin hydrothermal field,Okinawa Trough: constraints from rare earth element and sulfur isotopic compositions

For the first time, we present the rare earth element (REE) and sulfur isotopic composition of hydrothermal precipitates recovered from the Tangyin hydrothermal field (THF), Okinawa Trough at a water depth of 1206 m. The natural sulfur samples exhibit the lowest ΣREE concentrations (ΣREE= 0.65×10^–6–4.580×10^–6) followed by metal sulfides (ΣREE=1.71×10^–6–11.63×10^–6). By contrast, the natural sulfur-sediment samples have maximum ΣREE concentrations (ΣREE=11.54×10^–6–33.06×10^–6), significantly lower than those of the volcanic and sediment samples. Nevertheless, the δEu, δCe, (La/Yb)_N, La/Sm, (Gd/Yb)_N and normalized patterns of the natural sulfur and metal sulfide show the most similarity to the sediment. Most hydrothermal precipitate samples are characterized by enrichments of LREE (LREE/HREE=10.09–24.53) and slightly negative Eu anomalies or no anomaly (δEu=0.48–0.99), which are different from the hydrothermal fluid from sediment-free mid-oceanic ridges and back-arc basins, but identical to the sulfides from the Jade hydrothermal field. The lower temperature and more oxidizing conditions produced by the mixing between seawater and hydrothermal fluids further attenuate the leaching ability of hydrothermal fluid, inducing lower REE concentrations for natural sulfur compared with metal sulfide; meanwhile, the negative Eu anomaly is also weakened or almost absent. The sulfur isotopic compositions of the natural sulfur (δ³⁴S=3.20‰–5.01‰, mean 4.23‰) and metal sulfide samples (δ³⁴S=0.82‰–0.89‰, mean 0.85‰) reveal that the sulfur of the chimney is sourced from magmatic degassing.