Sulfur K-edge XANES analysis of natural and synthetic basaltic glasses: Implications for S speciation and S content as function of oxygen fugacity

XANES analyses at the sulfur K-edge were used to determine the oxidation state of S species in natural and synthetic basaltic glasses and to constrain the fO₂ conditions for the transition from sulfide (S²⁻) to sulfate (S⁶⁺) in silicate melts. XANES spectra of basaltic samples from the Galapagos spreading center, the Juan de Fuca ridge and the Lau Basin showed a dominant broad peak at 2476.8 eV, similar to the spectra obtained from synthetic sulfide-saturated basalts and pyrrhotite. An additional sharp peak at 2469.8 eV, similar to that of crystalline sulfides, was present in synthetic glasses quenched from hydrous melts but absent in anhydrous glasses and may indicate differences in sulfide species with hydration or presence of minute sulfide inclusions exsolved during quenching. The XANES spectra of a basalt from the 1991 eruption of Mount Pinatubo, Philippines, and absarokitic basalts from the Cascades Range, Oregon, USA, showed a sharp peak at 2482.8 eV, characteristic of synthetic sulfate-saturated basaltic glasses and crystalline sulfate-bearing minerals such as hauyne. Basaltic samples from the Lamont Seamount, the early submarine phase of Kilauea volcano and the Loihi Seamount showed unequivocal evidence of the coexistence of S²⁻ and S⁶⁺ species, emphasizing the relevance of S⁶⁺ to these systems. XANES spectra of basaltic glasses synthesized in internally-heated pressure vessels and equilibrated at fO₂ ranging from FMQ − 1.4 to FMQ + 2.7 showed systematic changes in the features related to S²⁻ and S⁶⁺ with changes in fO₂. No significant features related to sulfite (S⁴⁺) species were observed. These results were used to construct a function that allows estimates of S⁶⁺/ΣS from XANES data. Comparison of S⁶⁺/ΣS data obtained by S Kα shifts measured with electron probe microanalysis (EPMA), S⁶⁺/ΣS obtained from XANES spectra, and theoretical considerations show that data obtained from EPMA measurements underestimate S⁶⁺/ΣS in samples that are sulfate-dominated (most likely because of photo-reduction effects during analysis) whereas S⁶⁺/ΣS from XANES provide a close match to the expected theoretical values. The XANES-derived relationship for S⁶⁺/ΣS as a function of fO₂ indicates that the transition from S²⁻ to S⁶⁻ with increasing fO₂ occurs over a narrower interval than what is predicted by the EPMA-derived relationship. The implications for natural systems is that small variation of fO₂ above FMQ + 1 will have a large effect on S behavior in basaltic systems, in particular regarding the amount of S that can be transported by basaltic melts before sulfide saturation can occur.     

The Paleoarchean Northern Mundo Novo Greenstone Belt,São Francisco Craton: Geochemistry,U–Pb–Hf–O in zircon and pyrite δ34S-Δ33S-Δ36S signatures

Greenstone belts contain several clues about the evolutionary history of primitive Earth. Here, we describe the volcano-sedimentary rock association exposed along the eastern margin of the Gavião Block, named the Northern Mundo Novo Greenstone Belt (N-MNGB), and present data collected with different techniques, including U–Pb–Hf–O isotopes of zircon and multiple sulfur isotopes (³²S, ³³S, ³⁴S, and ³⁶S) of pyrite from this supracrustal sequence. A pillowed metabasalt situated in the upper section of the N-MNGB is 3337 ± 25 Ma old and has zircon with ε_Hf(t) =  ?2.47 to ?1.40, Hf model ages between 3.75 Ga and 3.82 Ga, and δ¹⁸O = +3.6‰ to +7.3‰. These isotopic data, together with compiled whole-rock trace element data, suggest that the mafic metavolcanic rocks formed in a subduction-related setting, likely a back-arc basin juxtaposed to a continental arc. In this context, the magma interacted with older Eoarchean crustal components from the Gavião Block. Detrital zircons from the overlying quartzites of the Jacobina Group are sourced from Paleoarchean rocks, in accordance with previous studies, yielding a maximum depositional age of 3353 ± 22 Ma. These detrital zircons have ε_Hf(t) =  ?5.40 to ?0.84, Hf model ages between 3.66 Ga and 4.30 Ga, and δ¹⁸O = +4.8‰ to +6.4‰. The pyrite multiple sulfur isotope investigation of the 3.3 Ga supracrustal rocks from the N-MNGB enabled a further understanding of Paleoarchean sulfur cycling. The samples have diverse isotopic compositions that indicate sulfur sourced from distinct reservoirs. Significantly, they preserve the signal of the anoxic Archean atmosphere, expressed by MIF-S signatures (Δ³³S between ?1.3‰ to +1.4‰) and a Δ³⁶S/Δ³³S slope of ?0.81 that is indistinguishable from the so-called Archean array. A BIF sample has a magmatic origin of sulfur, as indicated by the limited δ³⁴S range (0 to +2‰), Δ³³S ~ 0‰, and Δ³⁶S ~ 0‰. A carbonaceous schist shows positive δ³⁴S (2.1‰–3.5‰) and elevated Δ³³S (1.2‰–1.4‰) values, with corresponding negative Δ³⁶S between ?1.2‰ to ?0.2‰, which resemble the isotopic composition of Archean black shales and suggest a source from the photolytic reduction of elemental sulfur. The pillowed metabasalt displays heterogeneous δ³⁴S, Δ³³S, and Δ³⁶S signatures that reflect assimilation of both magmatic sulfur and photolytic sulfate during hydrothermal seafloor alteration. Lastly, pyrite in a massive sulfide lens is isotopically similar to barite of several Paleoarchean deposits worldwide, which might indicate mass dependent sulfur processing from a global and well-mixed sulfate reservoir at this time.     

S-rich apatite-hosted glass inclusions in xenoliths from La Palma: constraints on the volatile partitioning in evolved alkaline magmas

The composition of S-rich apatite, of volatile-rich glass inclusions in apatite, and of interstitial glasses in alkaline xenoliths from the 1949 basanite eruption in La Palma has been investigated to constrain the partitioning of volatiles between apatite and alkali-rich melts. The xenoliths are interpreted as cumulates from alkaline La Palma magmas. Apatite contains up to 0.89 wt% SO₃ (3560 ppm S), 0.31 wt% Cl, and 0.66 wt% Ce₂O₃. Sulfur is incorporated in apatite via several independent exchange reactions involving (P⁵⁺, Ca²⁺) vs. (S⁶⁺, Si⁴⁺, Na⁺, and Ce³⁺). The concentration of halogens in phonolitic to trachytic glasses ranges from 0.15 to 0.44 wt% for Cl and from <0.07 to 0.65 wt% for F. The sulfur concentration in the glasses ranges from 0.06 to 0.23 wt% SO₃ (sulfate-saturated systems). The chlorine partition coefficients (D_Cl^{apatite/glass}) range from 0.4 to 1.3 (average D_Cl^{apatite/glass} = 0.8), in good agreement with the results of experimental data in mafic and rhyolitic system with low Cl concentrations. With increasing F in glass inclusions D_F^{apatite/glass} decreases from 35 to 3. However, most of our data display a high partition coefficient (~30) close to D_F^{apatite/glass} determined experimentally in felsic rock. D_S^{apatite/glass} decreases from 9.1 to 2.9 with increasing SO₃ in glass inclusions. The combination of natural and experimental data reveals that the S partition coefficient tends toward a value of 2 for high S content in the glass (>0.2 wt% SO₃). D_S^{apatite/glass} is only slightly dependent on the melt composition and can be expressed as: SO_{3 apatite} (wt%) = 0.157 * ln SO_{3 glass} (wt%) + 0.9834. The phonolitic compositions of glass inclusions in amphibole and haüyne are very similar to evolved melts erupted on La Palma. The lower sulfur content and the higher Cl content in the phonolitic melt compared to basaltic magmas erupted in La Palma suggest that during magma evolution the crystallization of haüyne and pyrrhotite probably buffered the sulfur content of the melt, whereas the evolution of Cl concentration reflects an incompatible behavior. Trachytic compositions similar to those of the (water-rich) glass inclusions analyzed in apatite and clinopyroxene are not found as erupted products. These compositions are interpreted to be formed by the reaction between water-rich phonolitic melt and peridotite wall-rock.     

Oxidized sulfur-rich mafic magma at Mount Pinatubo,Philippines

Basaltic fragments enclosed in andesitic dome lavas and pyroclastic flows erupted during the early stages of the 1991 eruption of Mount Pinatubo, Philippines, contain amphiboles that crystallized during the injection of mafic magma into a dacitic magma body. The amphiboles contain abundant melt inclusions, which recorded the mixing of andesitic melt in the mafic magma and rhyolitic melt in the dacitic magma. The least evolved melt inclusions have high sulfur contents (up to 1,700 ppm) mostly as SO₄ ^2–, which suggests an oxidized state of the magma (NNO+1.4). The intrinsically oxidized nature of the mafic magma is confirmed by spinel–olivine oxygen barometry. The value is comparable to that of the dacitic magma (NNO+1.6). Hence, models invoking mixing as a means of releasing sulfur from the melt are not applicable to Pinatubo. Instead, the oxidized state of the dacitic magma likely reflects that of parental mafic magma and the source region in the sub-arc mantle. Our results fit a model in which long-lived SO₂ discharge from underplated mafic magma accumulated in the overlying dacitic magma and immiscible aqueous fluids. The fluids were the most likely source of sulfur that was released into the atmosphere during the cataclysmic eruption. The concurrence of highly oxidized basaltic magma and disproportionate sulfur output during the 1991 Mt. Pinatubo eruption suggests that oxidized mafic melt is an efficient medium for transferring sulfur from the mantle to shallow crustal levels and the atmosphere. As it can carry large amounts of sulfur, effectively scavenge sulfides from the source mantle and discharge SO₂ during ascent, oxidized mafic magma forms arc volcanoes with high sulfur fluxes, and potentially contributes to the formation of metallic sulfide deposits.Editorial responsibility: J. Hoefs

---

The latest Jurassic protoliths of the Sangsang mafic schists in southern Tibet: Implications for the spatial extent of Greater India

Field observations, petrology, zircon geochronology, whole-rock geochemistry, and Sr-Nd isotopes were used to reveal the lithology, age, and tectonic setting of the protoliths of the Sangsang mafic schists in the Yarlung Zangbo Suture Zone (YZSZ), central southern Tibet. The mafic schists occur as exotic blocks within the accretionary complex of the YZSZ. Relic amygdaloidal features indicate the schist protoliths were volcanic rocks. The mineral assemblage mainly comprises riebeckite + magnesioriebeckite + chlorite + sericite + albite + relic clinopyroxene. The youngest group of zircon ages constrains the formation time of the protoliths to 149.2 ± 2.2 Ma (i.e., latest Jurassic). Abundant Paleozoic and older zircons suggest the protolith volcanic rocks were erupted onto a continental terrane. Whole-rock geochemical and Sr-Nd isotopic data indicate the protoliths were of ocean island basalt affinity. The mafic schists mostly have high-Ti, alkaline, basaltic compositions with 43.57–46.93 wt% SiO₂, 3.27–7.24 wt% Na₂O + K₂O, and 4.04–4.69 wt% TiO₂. The schists are enriched in light rare earth elements relative to heavy rare earth elements, and have (La/Yb)_N = 5.85–8.53 and small positive Ta and negative Zr-Hf anomalies. (⁸⁷Sr/⁸⁶Sr)_i values vary from 0.7044 to 0.7055, while (¹⁴³Nd/¹⁴⁴Nd)_i ranges from 0.512670 to 0.512727, with εNd(t) values of +4.4 to +5.5. The protoliths of the mafic schists were probably formed in a within-plate extension setting associated with mantle plume upwelling and melting of continental lithosphere. This setting was related to the Late Jurassic continental breakup of Argoland off the northern margin of east Gondwana, and thus marked the paleoposition of the northern edge of Greater India before the breakup of India from east Gondwana during Early Cretaceous. The N-S extent of Greater India at that time was ~2400 km. This further indicates how the India–Eurasia continental convergence has been accommodated.     

Crust-derived felsic magmatism in the Emeishan large igneous Province: New evidence from zircon U-Pb-Hf-O isotope from the Yangtze Block,China

Numerous intrusive bodies of mafic–ultramafic to felsic compositions are exposed in association with volcanic rocks in the Late Permian Emeishan large igneous province (ELIP), southwestern China. Most of the granitic rocks in the ELIP were derived by differentiation of basaltic magmas with a mantle connection, and crustal magmas have rarely been studied. Here we investigate a suite of mafic dykes and I-type granites that yield zircon U-Pb emplacement ages of 259.9 ± 1.2 Ma and 259.3 ± 1.3 Ma, respectively. The ε_Hf(t) values of zircon from the DZ mafic dyke are –0.3 to 9.4, and their corresponding T_DM1 values are in the range of 919–523 Ma. The ε_Hf(t) values of zircon from the DSC I-type granite are between –1 and 3, with T_DM1 values showing a range of 938–782 Ma. We also present zircon O isotope data on crust-derived felsic intrusions from the ELIP for the first time. The δ¹⁸O values of zircon from the DSC I-type granite ranges from 4.87‰ to 7.5‰. The field, petrologic, geochemical and isotopic data from our study lead to the following salient findings. (i) The geochronological study of mafic and felsic intrusive rocks in the ELIP shows that the ages of mafic and felsic magmatism are similar. (ii) The DZ mafic dyke and high-Ti basalts have the same source, i.e., the Emeishan mantle plume. The mafic dyke formed from magmas sourced at the transitional depth between from garnet-lherzolite and spinel-lherzolite, with low degree partial melting (<10%). (iii) The Hf-O isotope data suggest that the DSC I-type granite was formed by partial melting of Neoproterozoic juvenile crust and was contaminated by minor volumes of chemically weathered ancient crustal material. (iv) The heat source leading to the formation of the crust-derived felsic rocks in of the ELIP is considered to be mafic–ultramafic magmas generated by a mantle plume, which partially melted the overlying crust, generating the felsic magma.     

Petrogenesis of Middle-Eocene granitoids and their Mafic microgranular enclaves in central Urmia-Dokhtar Magmatic Arc (Iran): Evidence for interaction between felsic and mafic magmas

Whole rock major and trace element geochemistry together with zircon U-Pb ages and Sr-Nd isotope compositions for the Middle Eocene intrusive rocks in the Haji Abad region are presented. The granitoid hosts, including granodiorite and diorite, yielded zircon U-Pb ages with a weighted mean value of 40.0 ± 0.7 Ma for the granodiorite phase. Mafic microgranular enclaves(MMEs) are common in these plutons, and have relatively low SiO_2 contents(53.04-57.08 wt.%) and high Mg#(42.6-60.1), probably reflecting a mantle-derived origin. The host rocks are metaluminous(A/CNK = 0.69-1.03), arc-related calc-alkaline, and I-type in composition, possessing higher SiO_2 contents(59.7-66.77 wt.%) and lower Mg#(38.6-52.2); they are considered a product of partial melting of the mafic lower crust. Chondritenormalized REE patterns of the MMEs and granitoid hosts are characterized by LREE enrichment and show slight negative Eu anomalies(Eu/Eu* = 0.60-0.93). The host granodiorite samples yield(⁸⁷Sr/⁸⁶Sr);ratios ranging from 0.70498 to 0.70591,positive eNd(t) values varying from +0.21 to +2.3, and TDM2 ranging from 760 to 909 Ma, which is consistent with that of associated mafic microgranular enclaves(⁸⁷Sr/⁸⁶Sr)i = 0.705111-0.705113, ε_Nd(t)= +2.14 to +2.16, T_DM2 = 697-785 Ma). Petrographic and geochemical characterization together with bulk rock Nd-Sr isotopic data suggest that host rocks and associated enclaves originated by interaction between basaltic lower crust-derived felsic and mantlederived mafic magmas in an active continental margin arc environment.     

Chromitites from the Luanga Complex,Carajás,Brazil: Stratigraphic distribution and clues to processes leading to post-magmatic alteration

The Neoarchean (ca. 2.75 Ga) Luanga Complex, located in the Carajás Mineral Province in Brazil, is a medium-size layered intrusion consisting, from base to top, of ultramafic cumulates (Ultramafic Zone), interlayered ultramafic and mafic cumulates (Transition Zone) and mafic cumulates (Mafic Zone). Chromitite layers in the Luanga Complex occur in the upper portion of interlayered harzburgite and orthopyroxenite of the Transition Zone and associated with the lowermost norites of the Mafic Zone. The stratigraphic interval that hosts chromitites (∼150 meters thick) consists of several cyclic units interpreted as the result of successive influxes of primitive parental magma. The compositions of chromite in chromitites from the Transition Zone (Lower Group Chromitites) have distinctively higher Cr# (100Cr/(Cr + Al + Fe³⁺)) compared with chromite in chromitites from the Mafic Zone (Upper Group Chromitites). Chromitites hosted by noritic rocks are preceded by a thin layer of harzburgite located 15–20 cm below each chromitite layer. Lower Cr# in chromitites hosted by noritic rocks are interpreted as the result of increased Al₂O₃ activity caused by new magma influxes. Electron microprobe analyses on line transverses through 35 chromite crystals indicate that they are rimmed and/or extensively zoned. The composition of chromite in chromitites changes abruptly in the outer rim, becoming enriched in Fe³⁺ and Fe²⁺ at the expense of Mg, Cr, Al, thus moving toward the magnetite apex on the spinel prism. This outer rim, characterized by higher reflectance, is probably related to the metamorphic replacement of the primary mineralogy of the Luanga Complex. Zoned chromite crystals indicate an extensive exchange between divalent (Mg, Fe²⁺) cations and minor to none exchange between trivalent cations (Cr³⁺, Al³⁺ and Fe³⁺). This Mg-Fe zoning is interpreted as the result of subsolidus exchange of Fe²⁺ and Mg between chromite and coexisting silicates during slow cooling of the intrusion. A remarkable feature of chromitites from Luanga Complex is the occurrence of abundant silicate inclusions within chromite crystals. These inclusions show an adjacent inner rim with higher Cr# and lower Mg# (100 Mg/(Mg + Fe²⁺)) and Al# (100Al/(Cr + Al + Fe³⁺)). This compositional shift is possibly due to crystallization from a progressively more fractionated liquid trapped in the chromite crystal. Significant modification of primary cumulus composition of chromite, as indicated in our study for the Luanga Complex, is likely to be common in non-massive chromitites and the rule for disseminated chromites in mafic intrusions.     

A greenstone belt in southeast Tibet: An accreted middle–late Permian oceanic plateau

Studies of accreted oceanic plateau sections provide crucial information on their structures, compositions, and origins. We investigate the petrogenesis of ultramafic–mafic rocks in the Tangjia–Sumdo greenstone belt of southeast Tibet using petrography, whole-rock geochemistry, and U-Pb zircon geochronology. These rocks are divided into four groups based on geochemical characteristics that include depleted and tholeiitic mafic rocks, transitional mafic rocks, enriched and alkaline mafic rocks, and picritic ultramafic rocks. Depleted and tholeiitic mafic rocks have the oldest crystallization ages (～272 Ma), followed by picritic ultramafic rocks (～270 Ma), transitional mafic rocks (267–254 Ma), and enriched and alkaline mafic rocks (252–250 Ma). Hafnium and neodymium isotope ratios of depleted and tholeiitic mafic rocks (ε_Hf(t) = +13.1–+16.9; ε_Nd(t) = +6.9–+7.1), transitional mafic rocks (ε_Hf(t) = +1.8–+16.9; ε_Nd(t) = +0.8–+5.5), enriched and alkaline mafic rocks (ε_Hf(t) = +0.5–+5.4; ε_Nd(t) = ?1.5 to +1.9) and picritic ultramafic rocks (ε_Hf(t) = +14.9–+17.2; ε_Nd(t) = +7.8–+9.0) are similar to those of N-MORB, E-MORB, OIB and depleted-type picritic mafic rocks in other oceanic plateaus, respectively. The geochemical characteristics of the depleted and tholeiitic mafic rocks suggest that they formed by partial melting of depleted spinel lherzolite in a mid-ocean ridge setting, whereas the picritic ultramafic rocks suggest a high degree of partial melting of depleted lherzolite in a hot mantle plume head. The transitional mafic rocks formed by partial melting of moderately enriched garnet lherzolite. The youngest rocks (enriched and alkaline mafic rocks) formed by partial melting of a more enriched garnet lherzolite (compared to transitional mafic rocks) at relatively low temperatures. We propose that the depleted and tholeiitic mafic rocks represent normal oceanic crust of the Sumdo Paleo-Tethys Ocean and the transitional mafic rocks, enriched and alkaline mafic rocks and picritic ultramafic rocks are the fragments of the oceanic plateau, which were related to middle–late Permian mantle plume activity in the Sumdo Paleo-Tethys Ocean. We further suggest that the majority of the Tangjia–Sumdo greenstone belt represents a middle–late Permian oceanic plateau that reflects a previously unrecognized middle–late Permian mantle plume.     

U–Pb (zircon) and geochemical constraints on the age,origin, and evolution of Paleozoic arc magmas in the Oyu Tolgoi porphyry Cu–Au district,southern Mongolia

Uranium–Pb (zircon) ages are linked with geochemical data for porphyry intrusions associated with giant porphyry Cu–Au systems at Oyu Tolgoi to place those rocks within the petrochemical framework of Devonian and Carboniferous rocks of southern Mongolia. In this part of the Gurvansayhan terrane within the Central Asian Orogenic Belt, the transition from Devonian tholeiitic marine rocks to unconformably overlying Carboniferous calc-alkaline subaerial to shallow marine volcanic rocks reflects volcanic arc thickening and maturation. Radiogenic Nd and Pb isotopic compositions (ε_Nd(t) range from + 3.1 to + 7.5 and ²⁰⁶Pb/²⁰⁴Pb values for feldspars range from 17.97 to 18.72), as well as low high-field strength element (HFSE) contents of most rocks (mafic rocks typically have < 1.5% TiO₂) are consistent with magma derivation from depleted mantle in an intra-oceanic volcanic arc. The Late Devonian and Carboniferous felsic rocks are dominantly medium- to high-K calc-alkaline and characterized by a decrease in Sr/Y ratios through time, with the Carboniferous rocks being more felsic than those of Devonian age. Porphyry Cu–Au related intrusions were emplaced in the Late Devonian during the transition from tholeiitic to calc-alkaline arc magmatism. Uranium–Pb (zircon) geochronology indicates that the Late Devonian pre- to syn-mineral quartz monzodiorite intrusions associated with the porphyry Cu–Au deposits are ~ 372 Ma, whereas granodiorite intrusions that post-date major shortening and are associated with less well-developed porphyry Cu–Au mineralization are ~ 366 Ma. Trace element geochemistry of zircons in the Late Devonian intrusions associated with the porphyry Cu–Au systems contain distinct Th/U and Yb/Gd ratios, as well as Hf and Y concentrations that reflect mixing of magma of distinct compositions. These characteristics are missing in the unmineralized Carboniferous intrusions. High Sr/Y and evidence for magma mixing in syn- to late-mineral intrusions distinguish the Late Devonian rocks associated with giant Cu–Au deposits from younger magmatic suites in the district.     

Petrogenesis of Late Triassic mafic enclaves and host granodiorite in the Eastern Kunlun Orogenic Belt,China: Implications for the reworking of juvenile crust by delamination-induced asthenosphere upwelling

Late Triassic granitoids containing abundant mafic microgranular enclaves (MMEs) occur widely in the Eastern Kunlun Orogenic Belt (EKOB). In this work, we present mineral chemistry, zircon U-Pb ages and L-Hf isotopes, whole-rock chemistry and S-Nd isotope compositions of the MMEs and host granodiorite from the Huda pluton in the Elashan area within the easternmost domain of the EKOB. These rocks contain inherited (Meso- to Neoproterozoic) and xenocrystic (ca. 240 Ma) zircon grains that yield apparent older ages, whereas the magmatic zircons from MMEs and granodiorite yield similar weighted mean ages around 224 Ma, which are interpreted as their crystallization ages. The MMEs have low SiO₂ but high TiO₂, TFe₂O₃, CaO, MgO and MnO concentrations with relatively high Mg^# values (48–54) and 100MnO/(MnO + MgO + TFe₂O₃) ratios (1.2–1.6). They display identical Sr-Nd-Hf isotope compositions to the host granite. Combined with petrological evidence, we suggest that the MMEs are cognate cumulates that formed by pressure quenching during the late stage of magma evolution from the same parental magma of the host granodiorite, rather than a magma mixing origin. The granodiorite is calc-alkaline to high-K calc-alkaline, metaluminous I-type granite. They show relatively low SiO₂ and MnO, but high MgO, Al₂O₃, CaO and TFe₂O₃ contents with Mg^# values of 45–50. They are enriched in light rare earth elements (LREEs) and large ion lithophile elements (LILEs), such as Rb, Th, K and Pb, and are depleted in P and high field strength elements (HFSE) including Nb, Ta and Ti. These rocks display slightly negative Eu anomalies and low Sr/Y and La/Yb ratios. Together with the rim-ward chemically evolved nature of some phenocrysts, the comparatively high initial Sr isotope (0.70888–0.70912), low whole-rock ε_Nd(t) (−5.6 to −6.0) and zircon ε_Hf(t) (−3.3 to −0.1) values, and low Nb/Th (0.11–0.26) and Ta/U (0.53–0.68) ratios, we suggest that the granodiorite magma was sourced from the lower crust. Considering their comparatively young two-stage Nd and Hf model ages (1.42–1.49 Ga and 1.13–1.42 Ga, respectively) and same trace element character with the juvenile crust beneath the EKOB, we interpret the juvenile lower crust as the dominant source rocks for the granodiorite. Based on our data and regional geological evidence, we suggest that the partial melting of juvenile crust resulted from delamination-related asthenosphere mantle upwelling. The latter process resulted in extensive melting of the lower crust, producing a major Late Triassic magmatic flare-up event in the EKOB.     

Petrology of mafic and ultramafic layered rocks from the Jaboncillo Valley,Sierra de Valle Fértil,Argentina: Implications for the evolution of magmas in the lower crust of the Famatinian arc

This work presents the field setting, petrography, mineralogy and geochemistry of a gabbroic and peridotitic layered body that is lens-shaped and surrounded by gabbronorites, diorites, and metasedimentary migmatites. This body exposed at Jaboncillo Valley is one among several examples of mafic and ultramafic layered sequences in the Sierras Valle Fértil and La Huerta, which formed as part of the lower crust of the Ordovician Famatinian magmatic arc in central-western Argentina. The layered sequence grew at deep crustal levels (20–25 km) within a mafic lower crust. The base of the layered body was detached during the tectonic uplift of the Famatinian lower crust, whereas the roof of the layered body is exposed in the eastern zone. In the inferred roof, olivine-bearing rocks vanish, cumulate textures are less frequent, and the igneous sequence becomes dominated by massive or thinly banded gabbronorites. Mainly based on the petrographic relationships, the inferred order of crystallization in the gabbroic and peridotitic layered sequence is: (1) Cr–Al-spinel + olivine, (2) Cr–Al-spinel + olivine + clinopyroxene + magnetite, (3) Cr–Al-spinel + olivine + plagioclase + magnetite ± orthopyroxene, and (4) Al-spinel + orthopyroxene + amphibole. A strong linear negative correlation between olivine and plagioclase modal proportions combined with field, petrographic and geochemical observations are used to demonstrate that the physical separation of olivine and plagioclase results in rock diversity at scales of a few centimeters to tens of meters. However, the composition of olivine (Fo ～ 0.81) and plagioclase (An > 94%) remains similar throughout the layered sequence. Spinels are restricted to olivine-bearing assemblages, and display chemical trends characteristic of spinels found in arc-related cumulates. Gabbroic and peridotitic layered rocks have trace element concentrations reflecting cumulates of early crystallizing minerals. The trace element patterns still retain the typical features of subduction-related arc magmatism, showing that the process of cumulate formation did not obscure the trace element signature of the parental magma. Using the composition of cumulus minerals and whole-rock chemical trends, we show that the parental magma was mafic (SiO₂ ～ 48 wt.%) with Mg-number around 0.6, and hydrous. The oxygen fugacity (fO₂) of the parental magma estimated between +0.8 and ?0.6 log fO₂ units around the fayalite–magnetite–quartz (FMQ) buffer is also characteristic of primitive hydrous arc magmas. The initially high water content of the parental magma allowed amphibole to crystallize as an interstitial phase all over the crystallization evolution of the layered sequence. Amphibole crystallization in the inter-cumulus assemblage gives rise to the retention of many trace elements which would otherwise be incompatible with the mineral assemblage of mafic–ultramafic cumulates. This study shows that there exist strongly mafic and primitive magmas that are both generated and emplaced within the lower crustal levels of subduction-related magmatic arc. Our findings together with previous studies suggest that the Early Ordovician magmatic paleo-arc from central-northwestern Argentina cannot be regarded as a typical Andean-type tectono-magmatic setting.     

Magma mixing origin for the Aolunhua porphyry related to Mo–Cu mineralization,eastern Central Asian Orogenic Belt

Many Cu–Mo–Au deposits are considered to be related to adakitic porphyries formed in non-arc settings, e.g., in collisional orogenic zones and intra-plate environments, but their genesis is still under discussion. The Aolunhua porphyry complex and its related Mo–Cu deposit from the eastern Central Asian Orogenic Belt (CAOB) provide important insights into this issue. The porphyries are characterized by high Sr (496–705 ppm) and Sr/Y and La/Yb ratios similar to those of typical adakitic rocks, and low I_Sr ratios (0.7049–0.7052) and positive ε_Nd(t) (+ 0.5 to + 1.4) and ε_Hf(t) (+ 3.5 to + 9.8) values. These features, along with the occurrence of mafic microgranular enclaves (MMEs), compositional and textural disequilibrium of plagioclase phenocrysts and relatively high Mg# values (45–52), indicate that they were derived from mixing of felsic magma from partial melting of a juvenile arc-type lower crust and mafic magma from a lithospheric mantle previously metasomatized by subduction zone fluids/melts. High Sr/Y and La/Yb ratios are indicative of contribution from enriched mantle-derived materials (with high LILEs; e.g., Sr, La), which were strengthened by subsequent fractionation of ferromagnesian phases such as pyroxene and hornblende. MMEs hosted by the ore-bearing porphyry have zircon U–Pb ages of ca. 132 Ma, similar to those of the host rocks. The enclaves have elevated Mg^# (56–63), LILEs (e.g., Sr = 660–891 ppm), LREE (La_N = 68–150, (La/Sm)_N = 3.0–4.0, (La/Yb)_N = 12.0–19.6) and ratios of radiogenic isotopes of Nd- and Hf (ε_Nd = + 0.7 to + 1.6; ε_Hf = + 3.3 to + 10.9), suggesting that their parental magmas were derived from the metasomatized mantle source. The Mo–Cu mineralization was probably related to the high water content, high oxygen and sulfur fugacity of hybrid magma. Formation of the adakitic porphyries and related Mo–Cu deposits of the eastern CAOB could be related to the Early Cretaceous lithospheric extension, caused by the subduction of the Paleo-Pacific plate and its induced reactivation of juvenile arc-type lower crust.     

Evidence for hybridisation in the Tynong Province granitoids,Lachlan Fold Belt,eastern Australia

The role of mafic–felsic magma mixing in the formation of granites is controversial. Field evidence in many granite plutons undoubtedly implies interaction of mafic (basaltic–intermediate) magma with (usually) much more abundant granitic magma, but the extent of such mixing and its effect on overall chemical features of the host intrusion are unclear. Late Devonian I-type granitoids of the Tynong Province in the western Lachlan Fold Belt, southeast Australia, show typical evidence for magma mingling and mixing, such as small dioritic stocks, hybrid zones with local host granite and ubiquitous microgranitoid enclaves. The latter commonly have irregular boundaries and show textural features characteristic of hybridisation, e.g. xenocrysts of granitic quartz and K-feldspars, rapakivi and antirapakivi textures, quartz and feldspar ocelli, and acicular apatite. Linear (well defined to diffuse) compositional trends for granites, hybrid zones and enclaves have been attributed to magma mixing but could also be explained by other mechanisms. Magmatic zircons of the Tynong and Toorongo granodiorites yield U–Pb zircon ages consistent with the known ca 370 Ma age of the province and preserve relatively unevolved ?_Hf (averages for three samples are +6.9, +4.3 and +3.9). The range in zircon ?_Hf in two of the three analysed samples (8.8 and 10.1 ?_Hf units) exceeds that expected from a single homogeneous population (～4 units) and suggests considerable Hf isotopic heterogeneity in the melt from which the zircon formed, consistent with syn-intrusion magma mixing. Correlated whole-rock Sr–Nd isotope data for the Tynong Province granitoids show a considerable range (0.7049–0.7074, ?_Nd +1.2 to –4.7), which may map the hybridisation between a mafic magma and possibly multiple crustal magmas. Major-element variations for host granite, hybrid zones and enclaves in the large Tynong granodiorite show correlations with major-element compositions of the type expected from mixing of contrasting mafic and felsic magmas. However, chemical–isotopic correlations are poorly developed for the province as a whole, especially for ⁸⁷Sr/⁸⁶Sr. In a magma mixing model, such complexities could be explained in terms of a dynamic mixing/mingling environment, with multiple mixing events and subsequent interactions between hybrids and superimposed fractional crystallisation. The results indicate that features plausibly attributed to mafic–felsic magma mixing exist at all scales within this granite province and suggest a major role for magma mixing/mingling in the formation of I-type granites.     

Sulfur cycling at the Mid-Atlantic Ridge: A multiple sulfur isotope approach

The role of sulfur in two hydrothermal vent systems, the Logatchev hydrothermal field at 14°45′N/44°58′W and several different vent sites along the southern Mid-Atlantic Ridge (SMAR) between 4°48′S and 9°33′S and between 12°22′W and 13°12′W, is examined by utilizing multiple sulfur isotope and sulfur concentration data. Isotope compositions for sulfide minerals and vent H₂S from different SMAR sites range from + 1.5 to + 8.9‰ in δ³⁴S and from + 0.001 to + 0.051‰ in Δ³³S. These data indicate mixing of mantle sulfur with sulfur from seawater sulfate. Combined δ³⁴S and Δ³³S systematics reveal that vent sulfide from SMAR is characterized by a sulfur contribution from seawater sulfate between 25 and 33%. This higher contribution, compared with EPR sulfide, indicates increased seawater sulfate reduction at MAR, because of a deeper seated magma chamber and longer fluid upflow path length, and points to fundamental differences with respect to subsurface structures and fluid evolution at slow and fast spreading mid-ocean ridges.Additionally, isotope data uncover non-equilibrium isotopic exchange between dissolved sulfide and sulfate in an anhydrite bearing zone below the vent systems at fluid temperatures between 335 and 400 °C. δ³⁴S values between + 0.2 to + 8.8‰ for dissolved and precipitated sulfide from Logatchev point to the same mixing process between mantle sulfur and sulfur from seawater sulfate as at SMAR. δ³⁴S values between ? 24.5 and + 6.5‰ and Δ³³S values between + 0.001 and + 0.125‰ for sulfide-bearing sediments and mafic/ultramafic host rocks from drill cores taken in the region of Logatchev indicate a clear contribution of biogenic sulfides formed via bacterial sulfate reduction. Basalts and basaltic glass from SMAR sites with Δ³³S = ? 0.008‰ reveal lower Δ³³S lower values than suggested on the basis of previously published isotopic measurements of terrestrial materials.We conclude that the combined use of both δ³⁴S and Δ³³S provides a more detailed picture of the sulfur cycling in hydrothermal systems at the Mid-Atlantic Ridge and uncovers systematic differences to hydrothermal sites at different mid-ocean ridge sites. Multiple sulfur isotope measurements allow identification of incomplete isotope exchange in addition to isotope mixing as a second important factor influencing the isotopic composition of dissolved sulfide during fluid upflow. Furthermore, based on Δ³³S we are able to clearly distinguish biogenic from hydrothermal sulfides in sediments even when δ³⁴S were identical.     

Origin and timing of the post-Variscan gabbro–granite complex of Porto (Western Corsica)

The post-Variscan complex of Porto consists of metaluminous to slightly peraluminous A-type biotite granites mingled with gabbro-dioritic rocks, and late dykes with basaltic to trachyandesitic composition. U-Pb zircon dating by LA-ICP-MS on two mafic intrusive samples constrains the time of the gabbro–granite crystallisation at 281 ± 3 Ma and 283 ± 2 Ma. Hornblende ⁴⁰Ar-³⁹Ar ages from a late trachyandesite dyke date the dyking event at 280 ± 2 Ma, which is within error the U-Pb zircon ages of the intrusives. Biotite granites show variable major and trace element compositions and similar initial ε_Nd (−0.3 to +0.9). Whole rock chemistry variations and trace element compositions of plagioclase and allanite indicate that the granites are genetically linked, essentially through fractional crystallisation of feldspars and minor allanite. On the basis of whole-rock chemistry e.g. initial ε_Nd +4.9 to +1.7 and trace element clinopyroxene compositions, we have ascertained that the mafic intrusives and basic dykes formed from isotopically depleted mantle source-derived melts with similar trace element signature. These basic melts experienced slightly different evolutionary histories, controlled by fractional crystallisation and crustal contamination, mainly by the acid magma that gave rise to the associated biotite granites, but also by the enclosing older Variscan granitoids. U-Pb zircon data suggest that the Porto complex was affected by hydrothermal fluid circulation at 259 ± 9 Ma.     

A Potential (U‐Th)/He Zircon Reference Material from Penglai Zircon Megacrysts

In this study (U‐Th)/He dating of the Penglai zircons, which occur as abundant megacrysts in Neogene alkaline basalts in northern Hainan Province, south‐eastern China, was undertaken. A weighted mean age of 4.06 ± 0.35 Ma (2s) with a mean square weighted deviation (MSWD) of 1.79 was obtained from eighteen fragments of four zircon megacrysts using single‐crystal laser fusion He determinations and the U‐Th isotope dilution (ID) method. The (U‐Th)/He ages are consistent, homogeneous and systematically slightly younger than the preferred ²⁰⁶Pb/²³⁸U age of 4.4 ± 0.1 Ma (95% confidence interval) determined by ID‐TIMS and subsequently published U‐Pb results. The U‐Pb isotopic system in zircon has a high closure temperature of ~ 900 °C, and the preferred U‐Pb age may record both the time since eruption and the zircon residence time in the magma chamber. In contrast, the closure temperature of the zircon (U‐Th)/He system is ~ 190 °C and the zircon megacrysts were brought quickly to the surface by the host basaltic magma. Thus, the (U‐Th)/He age represents the timing of the eruption. Based on the unlimited quantity, large grain size, mostly weak broad zoning, rapid cooling and homogenous (U‐Th)/He ages, we consider the Penglai zircons suitable for use as a reference material in (U‐Th)/He isotope geochronology.     

Petrogenesis of mafic and associated silicic end-member magmas for calc-alkaline mixed rocks in the Shirataka volcano,NE Japan

Eruptive products of the Shirataka volcano (0.9–0.7 Ma) in NE Japan are calc-alkaline andesite–dacite, and are divisible into six petrologic groups (G1–G6). Shirataka rocks possess mafic inclusions—basalt–basaltic andesite, except for G3 and G4. All rocks show mixing and mingling of the mafic and silicic end-members, with trends defined by hosts and inclusions divided into high-Cr and low-Cr types; both types coexist in G1, G2, and G5. Estimated mafic end-members are high-Cr (1120–1170°C, 48–51% SiO₂, olv ± cpx ± plg) and low-Cr type magmas (49–52% SiO₂, cpx ± plg) except for the Sr isotopic composition. In contrast, the silicic end-members of both types have similar petrologic features (790–840°C, 64–70% SiO₂, hbl ± qtz ± px + plg). High-Cr type mafic and corresponding silicic end-members have lower ⁸⁷Sr/⁸⁶Sr ratios than the low-Cr ones in each group. The trace element model calculations suggest that the low-Cr type mafic end-member magma is produced through ca. 20% fractional crystallization (olv ± cpx ± plg) from the high-Cr type one with assimilation of granitoids (r = 0.02–0.05). The silicic magmas are producible through <30% partial remelting of previously emplaced basaltic magma with assimilation of crustal components. The compositional difference between the low-K and medium-K basalts in the Shirataka volcano is mainly attributed to the different degrees of the effect of subduction derived fluid by dehydration of phlogopite. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Temperature and Hf-O isotope correlations of young erupted zircons from Tengchong (SE Tibet): Assimilation fractional crystallization during monotonic cooling

Young zircons from crystal-poor volcanic rocks provide the best samples for the investigations of pre-eruption magmatic processes and for testing a possible relationship between zircon Eu anomalies and crustal thickness. We report trace element chemistry and Hf-O isotope compositions of young zircons from 3 Holocene volcanoes in the Tengchong volcanic field, SE Tibet, in order to provide insights into magma evolution processes and conditions for high-K calc-alkaline volcanic rocks in a post-collisional setting. As decreasing zircon Ti content and falling temperature, zircon Hf content and Yb/Sm increase whereas zircon Eu anomaly and Th/U decrease, indicating fractional crystallization of plagioclase and zircon during magma cooling. More importantly, zircon Hf isotope ratio (ε_Hf values) increases with decreasing zircon Ti content and falling temperature (T), suggesting gradually increasing incorporation of relatively high ε_Hf juvenile materials in the crystallizing zircons during magma evolution. Negative correlations between zircon ε_Hf and zircon δ¹⁸O also support open-system magma evolution. Our data suggest fractional crystallization of a magma with simultaneous contamination by high ε_Hf and low δ ¹⁸O juvenile (immature) crustal materials during monotonic cooling after zircon saturation. The low-T, high-ε_Hf and low- δ ¹⁸O zircons may indicate the involvement of the early Cretaceous juvenile granitic country rocks during shallow magma evolution. Average Eu anomalies in zircons from young Tengchong lavas yield crustal thickness of 40.7 ± 6.8 km, consistent with present crustal thickness (42.5 km) determined by geophysical methods.     

Combining trace-element compositions, U–Pb geochronology and Hf isotopes in zircons to unravel complex calcalkaline magma chambers in the Upper Cretaceous Srednogorie zone (Bulgaria)

Precise U–Pb geochronology and Hf isotope tracing of zircon is combined with whole-rock geochemical and Sr and Nd isotope data in order to unravel processes affecting mafic to felsic calcalkaline magmas prior to and during their crystallization in crustal magma chambers along the southern border of Central Srednogorie tectonic zone in Bulgaria (SE Europe). ID-TIMS U–Pb dating of single zircons from felsic and mixed/mingled dioritic to gabbroic horizons of single plutons define crystallization ages of around 86.5–86.0, 85.0–84.5 and 82 Ma. Concordia age uncertainties are generally less than 0.3 Ma (0.35%–2σ), and as good as 0.08 Ma (0.1%), when the weighted mean ²⁰⁶Pb/²³⁸U value is used. Such precision allows the distinction of magma replenishment processes if separated by more than 0.6–1.0 Ma and when they are marked by newly saturated zircons. We interpret zircon dates from a single sample that do not overlap to reflect new zircon growth during magma recharge in a long-lived crustal chamber. Mingling/mixing of the basaltic magma with colder granitoid mush at mid- to upper-crustal levels is proposed to explain zircon saturation and fast crystallization of U- and REE-rich zircons in the hybrid gabbro.Major and trace-element distribution and Sr and Nd whole-rock isotope chemistry define island arc affinities for the studied plutons. Slab derived fluids and a sediment component are constrained as enrichment sources for the mantle wedge-derived magma, though Hf isotopes in zircon suggest crustal assimilation was also important. Inherited zircons, and their corresponding ε-Hf, from the hybrid gabbroic rocks trace the lower crust as possible source for enrichment of the mantle magma. These inherited zircons are about 440 Ma old with ε-Hf of − 7 at 82 Ma, whereas newly saturated concordant Upper Cretaceous zircons reveal mantle ε-Hf values of + 7.2 to + 10.1. The upper and middle crusts contribute in the generation of the granitoid rocks. Their zircon inheritance is Lower Palaeozoic or significantly older and crustal dominated with 82–85 Ma corrected ε-Hf values of − 28. The Cretaceous concordant zircons in the granitoids are mantle dominated with a ε-Hf values spreading from + 3.9 to + 7.