Constraining input and output fluxes of the southern-central Chile subduction zone: water,chlorine and sulfur

In this paper, we constrain the input and output fluxes of H₂O, Cl and S into the southern-central Chilean subduction zone (31°S–46°S). We determine the input flux by calculating the amounts of water, chlorine and sulfur that are carried into the subduction zone in subducted sediments, igneous crust and hydrated lithospheric mantle. The applied models take into account that latitudinal variations in the subducting Nazca plate impact the crustal porosity and the degree of upper mantle serpentinization and thus water storage in the crust and mantle. In another step, we constrain the output fluxes of the subduction zone both to the subcontinental lithospheric mantle and to the atmosphere–geosphere–ocean by the combined use of gas flux determinations at the volcanic arc, volume calculations of volcanic rocks and the combination of mineralogical and geothermal models of the subduction zone. The calculations indicate that about 68 Tg/m/Ma of water enters the subduction zone, as averaged over its total length of 1,480 km. The volcanic output on the other hand accounts for 2 Tg/m/Ma or 3 % of that input. We presume that a large fraction of the volatiles that are captured within the subducting sediments (which accounts for roughly one-third of the input) are cycled back into the ocean through the forearc. This assumption is however questioned by the present lack of evidence for major venting systems of the submarine forearc. The largest part of the water that is carried into the subduction zone in the crust and hydrated mantle (accounting for two-thirds of the input) appears to be transported beyond the volcanic arc.     

The Alaska Wrangell Arc: ~30 Ma of subduction‐related magmatism along a still active arc‐transform junction

The Oligocene to Present Wrangell Volcanic Belt (WVB) extends for ~500 km across south‐central Alaska (USA) into Canada at a volcanic arc‐transform junction. Previously, geochemistry documented mantle wedge and slab‐edge melting in <12 Ma WVB volcanic rocks; new geochemistry shows that the same processes characterized ~18–30 Ma WVB magmatism in Alaska. New ⁴⁰Ar/³⁹Ar ages demonstrate that WVB magmatism in Alaska initiated at ~30 Ma due to flat‐slab subduction of the Yakutat microplate and that the dextral Totschunda fault was active at this time. Our results, together with prior studies, show that Alaskan WVB magmatism occurred chiefly due to subduction and should be considered a volcanic arc (e.g. the Wrangell Arc). The WVB provides a long‐term geological record of subduction, strike‐slip and magmatism. Slab‐edge upwelling, flat‐slab defocused fluid‐flux and faults acting as magma conduits are likely responsible for the exceptionally large volcanoes and high eruption rates of the Wrangell Arc.     

Flares of the H<Subscript>2</Subscript>O Maser Emission in the Young Stellar Object GH<Subscript>2</Subscript>O 092.67+03.07 (IRAS 21078+5211)

The results of monitoring the H₂O maser observed toward the region GH₂O 092.67+03.07 (IRAS 21078+5211) located in the Giant Molecular Cloud Cygnus OB7 are presented. The observations were carried out with the 22-m radio telescope of the Pushchino Radio Astronomy Observatory in 2006–2017. Strong flares of the H₂O maser emission with flux densities up to 19 800 Jy were detected. The flares exhibited both global (over the source) and local characters. All the flares were accompanied by strong variations in the H₂O spectra within the corresponding radial-velocity ranges. Individual H₂O components form both compact clusters and chains 1–2-AU long. Analysis of the variations of the fluxes, radial velocities, and line shapes of features during the flares showed that the medium may be strongly fragmented, with small-scale turbulent motions taking place in the H₂Omaser region.     

Numerical modeling of thermal structure, circulation of H2O, and magmatism–metamorphism in subduction zones: Implications for evolution of arcs

Numerical models on thermal structure, convective flow of solid, generation and transportation of H₂O-rich fluid in subduction zones are consolidated to have a comprehensive view of the subduction zone processes: heat balance, circulation of H₂O magmatism–metamorphism, growth of arcs and continental margins. A large scale convection model with steady subduction of a cold old slab (130 Myr old) predicts rapid ( 100 Myr) cooling of subduction zones, resulting in cessation of magmatism. The model also predicts that the mantle temperature beneath arcs and continental margins is greatly affected by the effective temperature of the subducting slab, i.e., the age of the subducting slab. If subduction of a young hot slab, including ridge subduction, occurs every 60 to 120 Myr as is suggested for eastern Asia, the average temperature beneath arcs is increased by about 300 °C, which may explain the long-lasting magmatism in eastern Asia. Associated with subduction of young slabs and ridges, thermal structure and circulation of H₂O are greatly modified to cause a transition from (1) normal arc magmatism, (2) forearc mantle melting, to (3) slab melting to produce a significant amount (100 km³) of granitic melts, associated with both high-P/T and low-P/T type metamorphism. The last stage of (3) can result in formation of a granitic batholith belt and a paired metamorphic belts. Synthesis of the numerical models and observations suggest that episodic subduction of young slabs and ridges can explain heat source for generating a large amount of granitic magmas of batholiths, synchronous formation of batholith and regional metamorphic belts, and P–T conditions of the paired metamorphism. Even the high-P/T metamorphism requires an elevated geothermal structure in the forearc region, associated with ridge subduction. Although the emplacement of the batholiths and the regional metamorphic belts, and the mass balance in subduction zones are not well constrained at present, the episodic event associated with ridge subduction is thought to be essential for net growth of arcs and continental margins, as well as for the long-term heat balance in subduction zones.     

Zircon U-Pb Geochronology and Geochemical Characteristics of the Volcanic Host Rocks from the Tongyu VHMS Copper Deposit in the Western North Qinling Orogen and Their Geological Significance

Precise in situ zircon U-Pb dating and Lu–Hf isotopic measurement using an LA-ICP-MS system, whole-rock major and trace element geochemistry and Sr–Nd isotope geochemistry were conducted on the volcanic host rocks of the Tongyu copper deposit on the basis of further understanding of its geological characteristics. Three zircon samples from the volcanic host rocks yielded 206Pb/238 U weighted average ages ranging from 436±4 Ma to 440±5 Ma, which are statistically indistinguishable and coeval with the ca. 440 Ma northward subduction event of the Paleo-Qinling oceanic slab. The volcanic host rocks were products of magmatic differentiation that evolved from basalt to andesite to dacite to rhyolite, forming an integrated tholeiitic island arc volcanic rock suite. The primitive mantle-normalized trace element patterns for most samples show characteristics of island arc volcanic rocks, such as relative enrichment of LILE(e.g. Th, U, Pb and La) and depletion of HFSE(e.g. Nb, Ta, Ti, Zr and Hf). Discrimination diagrams of Ta/Yb vs Th/Yb, Ta vs Th, Yb vs Th/Ta, Ta/Hf vs Th/Hf, Hf/3 vs Th vs Nb/16, La vs La/Nb and Nb vs Nb/Th all suggest that both the volcanic host rocks from the Tongyu copper deposit and the volcanic rocks from the regional Xieyuguan Group were formed in an island arc environment related to subduction of an oceanic slab. Values of ISr(0.703457 to 0.708218) and εNd(t)(-2 to 5.8) indicate that the source materials of volcanic rocks from the Tongyu copper deposit and the Xieyuguan Group originated from the metasomatised mantle wedge with possible crustal material assimilation. Most of the volcanic rock samples show good agreement with the values of typical island arc volcanic rocks in the ISr-εNd(t) diagram. The involvement of crustal-derived material in the magma of the volcanic rocks from the Tongyu copper deposit was also reflected in the zircon εHf(t) values, which range from-3.08 to 10.7, and the existence of inherited ancient xenocrystic zircon cores(2616±39 Ma and 1297±22 Ma). The mineralization of the Tongyu copper deposit shows syn-volcanic characteristics such as layered orebodies interbedded with the volcanic rock strata, thus, the zircon U-Pb age of the volcanic host rocks can approximately represent the mineralization age of the Tongyu copper deposit. Both the Meigou pluton and the volcanic host rocks were formed during the ca. 440 Ma northward subduction of the Paleo-Qinling Ocean when high oxygen fugacity aqueous hydrothermal fluid released by dehydration of the slab and the overlying sediments fluxed into the mantle wedge, triggered partial melting of the mantle wedge, and activated and extracted Cu and other ore-forming elements. The magma and ore-bearing fluid upwelled and erupted, and consequently formed the island arc volcanic rock suite and the Tongyu VHMS-type copper deposit.     

Decompression and H<Subscript>2</Subscript>O exsolution driven crystallization and fractionation: development of a new model for low-pressure fractional crystallization in calc-alkaline magmatic systems

Magma ascent, decompression-induced H₂O exsolution and crystallization is now recognized as an important process in hydrous subduction zone magmas. During the course of such a process calculations suggest that the ascent rate of a degassing and crystallizing mafic magma will be greater than crystal settling velocities. Thus, any crystals formed as a consequence of volatile exsolution will remain suspended in the magma. If the magma erupts before the percentage of suspended crystals reaches the critical crystallinity value for mafic magma (~55 vol.%) it will produce the commonly observed crystal rich island arc basalt lava. If the magma reaches its critical crystallinity before it erupts then it will stall within the crust. Extension of compaction experiments on a 55 vol.% sand-Karo syrup suspension at different temperatures (and liquid viscosities) to the likely viscosities of interstitial andesitic to dacitic liquid within such a stalled magma suggest that small amounts (up to ~10%) can be expelled on a time scale of 1–10 years. The expelled liquid can create a new intermediate to silicic body of magma that is related to the original mafic magma via fractional crystallization. The short time scale for liquid expulsion indicate that decompression-induced H₂O exsolution and crystallization can be an important mechanism for fractional crystallization. Based on this assumption a general model of decompression-induced crystallization and fractionation is proposed that explains many of the compositional, mineralogical and textural features of Aleutian (and other andesites).     

Amphibole stability in primitive arc magmas: effects of temperature,H<Subscript>2</Subscript>O content,and oxygen fugacity

The water-saturated phase relations have been determined for a primitive magnesian andesite (57 wt% SiO₂, 9 wt% MgO) from the Mt. Shasta, CA region over the pressure range 200–800 MPa, temperature range of 915–1,070 °C, and oxygen fugacities varying from the nickel–nickel oxide (NNO) buffer to three log units above NNO (NNO+3). The phase diagram of a primitive basaltic andesite (52 wt% SiO₂, 10.5 wt% MgO) also from the Mt. Shasta region (Grove et al. in Contrib Miner Petrol 145:515–533; 2003) has been supplemented with additional experimental data at 500 MPa. Hydrous phase relations for these compositions allow a comparison of the dramatic effects of dissolved H₂O on the crystallization sequence. Liquidus mineral phase stability and appearance temperatures vary sensitively in response to variation in pressure and H₂O content, and this information is used to calibrate magmatic barometers-hygrometers for primitive arc magmas. H₂O-saturated experiments on both compositions reveal the strong dependence of amphibole stability on the partial pressure of H₂O. A narrow stability field is identified where olivine and amphibole are coexisting phases in the primitive andesite composition above 500 MPa and at least until 800 MPa, between 975–1,025 °C. With increasing H₂O pressure (\({P}_{\text {H}_2{\rm O}}\)), the temperature difference between the liquidus and amphibole appearance decreases, causing a change in chemical composition of the first amphibole to crystallize. An empirical calibration is proposed for an amphibole first appearance barometer-hygrometer that uses Mg# of the amphibole and \(f_{\text {O}_2}\):

$$ P_{\text{H}_{2}{\rm O}}({\rm MPa})=\left[{\frac{{\rm Mg\#}}{52.7}}-0.014 * \Updelta {\rm NNO}\right]^{15.12} $$

This barometer gives a minimum \({P}_{\text{H}_{2}{\rm O}}\) recorded by the first appearance of amphibole in primitive arc basaltic andesite and andesite. We apply this barometer to amphibole antecrysts erupted in mixed andesite and dacite lavas from the Mt. Shasta, CA stratocone. Both high H₂O pressures (500–900 MPa) and high pre-eruptive magmatic H₂O contents (10–14 wt% H₂O) are indicated for the primitive end members of magma mixing that are preserved in the Shasta lavas. We also use these new experimental data to explore and evaluate the empirical hornblende barometer of Larocque and Canil (2010).

     

The volcanic succession of Baoligaomiao,central Inner Mongolia: Evidence for Carboniferous continental arc in the central Asian orogenic belt

The Baoligaomiao Formation, within the Hegenshan ophiolite-arc-accretion complex is an important segment to understand the tectonic evolution of the Central Asian Orogenic Belt (CAOB), world's largest Phanerozoic orogenic belt. In this study, we present an integrated study of zircon U-Pb isotopic ages, whole rock major-trace elements, and Sr-Nd-Pb isotopic data from the volcanic succession in the Baoligaomiao Formation. The volcanic succession can be divided into the lower sequence with zircon U-Pb ages in the range of 326.3 Ma–307.4 Ma and the upper sequence of 305.3 Ma. The succession belongs to two suites: calc-alkaline volcanics and high-Si rhyolites. The calc-alkaline volcanic rocks include basaltic andesite through andesite and dacite to rhyolite and their pyroclastic equivalents. These rocks exhibit a well-defined compositional trend from basaltic to rhyolitic magma, reflecting continuous fractional crystallization. These rocks show obvious enrichment in LILEs and LREEs and relative depletion of HFSEs, typical of subduction-related magma. The calc-alkaline rocks have low initial ⁸⁷Sr/⁸⁶Sr (0.7023–0.7052), positive ɛNd(t) values (2.75–4.80), and their initial Pb isotopic compositions are 17.875–18.485 of ²⁰⁶Pb/²⁰⁴Pb, 15.481–15.520 of ²⁰⁷Pb/²⁰⁴Pb and 37.467–37.764 of ²⁰⁸Pb/²⁰⁴Pb, respectively. Geochemical and isotopic results suggest that the volcanic succession represents Carboniferous subduction-related, mature, continental arc volcanism. The outcrops of high-Si rhyolites are restricted to the northern edge of the continental arc, marking a transition zone between volcanic arc and back-arc basin, where they are interbedded with the calc-alkaline rocks in the lower sequence, and the upper sequence is composed only of high-Si rhyolites. The high-Si rhyolites have high SiO₂ (71.12–81.76 wt%) and varied total alkali contents (K₂O + Na₂O = 5.46–10.58 wt%), low TiO₂ (0.06–0.27 wt%), MgO (0.09–0.89 wt%) and CaO (0.08–0.72 wt%). Based on the presence of mafic alkali phenocrysts, such as arfvedsonite and siderophyllite, high Zr/Nb ratios (> 10) and peralkalinity index (PI) near unity, the high-Si rhyolites can be classified as peralkaline comendites. The high-Si rhyolites are characterized by unusually low Sr and Ba, and high abundance of Zr, Th, Nb, HREEs and Y. They show geochemical characteristics similar to those of typical A₂-type granites including their high K₂O + Na₂O, Nb, Zr and Y, and high ratios of FeO^T/MgO, Ga/Al and Y/Nb. Our study suggests that the high-Si rhyolites were derived from discrete trachytic parent magma with fractional crystallization within shallow magma reservoirs. Their Nd-Pb isotopic characteristics are similar to those of the calc-alkaline arc rocks and are compatible with partial melting of pre-existing juvenile continental arc crust. We observe that the widespread eruptions of A₂-rhyolitic magmas (305.3 Ma–303.4 Ma) following a short period of magmatic quiescence was temporally and spatially associated with voluminous intrusion of the bimodal magmas (304.3 Ma–299.3 Ma) in the pre-existing arc volcanic-plutonic belt (329 Ma–307 Ma). We envisage northward subduction and slab breakoff process resulting in an obvious change of the regional stress field to extensional setting within the Carboniferous continental arc running E-W for thousands of kilometers. Therefore, we propose the existence of an east-west-trending Carboniferous continental arc in the Hegenshan ophiolite-arc-accretion complex, with the slab breakoff event suggesting that the age of the upper sequence (305.3 ± 5.5 Ma) likely indicates the maximum age for the cessation of the northward subduction of the Hegenshan oceanic lithosphere.     

The Keepit arc: provenance of sedimentary rocks in the central Tablelands Complex,southern New England Orogen,Australia, as recorded by detrital zircon

Detrital zircon from the Carboniferous Girrakool Beds in the central Tablelands Complex of the southern New England Orogen, Australia, is dominated by ca 350–320 Ma grains with a peak at ca 330 Ma; there are very few Proterozoic or Archean grains. A maximum deposition age for the Girrakool Beds of ca 309 Ma is identified. These data overlap the age of the Carboniferous Keepit arc, a continental volcanic arc along the western margin of the Tamworth Belt. Zircon trace-element and isotopic compositions support petrographic evidence of a volcanic arc provenance for sedimentary and metasedimentary rocks of the central Tablelands Complex. Zircon Hf isotope data for ca 350–320 Ma detrital grains become less radiogenic over the 30 million-year record. This pattern is observed with maturation of continental volcanic arcs but is opposite to the longer-term pattern documented in extensional accretionary orogens, such as the New England Orogen. Volcanic activity in the Keepit arc is inferred to decrease rapidly at ca 320 Ma, based on a major change in the detrital zircon age distribution. Although subduction continues, this decrease is inferred to coincide with the onset of trench retreat, slab rollback and the eastward migration of the magmatic arc that led to the Late Carboniferous to early Permian period of extension, S-type granite production and intrusion into the forearc basin, high-temperature–low-pressure metamorphism, and development of rift basins such as the Sydney–Gunnedah–Bowen system.     

The systematics of chlorine, fluorine, and water in Izu arc front volcanic rocks: Implications for volatile recycling in subduction zones

We studied the systematics of Cl, F and H₂O in Izu arc front volcanic rocks using basaltic through rhyolitic glass shards and melt inclusions (Izu glasses) from Oligocene to Quaternary distal fallout tephra. These glasses are low-K basalts to rhyolites that are equivalent to the Quaternary lavas of the Izu arc front (Izu VF). Most of the Izu glasses have Cl ∼400-4000 ppm and F ∼70-400 ppm (normal-group glasses). Rare andesitic melt inclusions (halogen-rich andesites; HRA) have very high abundances of Cl (∼6600-8600 ppm) and F (∼780-910 ppm), but their contents of incompatible large ion lithophile elements (LILE) are similar to the normal-group glasses. The preeruptive H₂O of basalt to andesite melt inclusions in plagioclase is estimated to range from ∼2 to ∼10 wt% H₂O. The Izu magmas should be undersaturated in H₂O and the halogens at their preferred levels of crystallization in the middle to lower crust (∼3 to ∼11 kbar, ∼820° to ∼1200°C). A substantial portion of the original H₂O is lost due to degassing during the final ascent to surface. By contrast, halogen loss is minor, except for loss of Cl from siliceous dacitic and rhyolitic compositions. The behavior of Cl, F and H₂O in undegassed melts resembles the fluid mobile LILE (e.g.; K, Rb, Cs, Ba, U, Pb, Li). Most of the Cl (>99%), H₂O (>95%) and F (>53%) in the Izu VF melts appear to originate from the subducting slab. At arc front depths, the slab fluid contains Cl = 0.94 ± 0.25 wt%, F = 990 ± 270 ppm and H₂O = 25 ± 7 wt%. If the subducting sediment and the altered basaltic crust were the only slab sources, then the subducted Cl appears to be almost entirely recycled at the Izu arc (∼77-129%). Conversely, H₂O (∼13-22% recycled at arc) and F (∼4-6% recycled) must be either lost during shallow subduction or retained in the slab to greater depths. If a seawater-impregnated serpentinite layer below the basaltic crust were an additional source of Cl and H₂O, the calculated percentage of Cl and H₂O recycled at arc would be lower. Extrapolating the Izu data to the total length of global arcs (∼37,000 km), the global arc outflux of fluid-recycled Cl and H₂O at subduction zones amounts to Cl ∼2.9-3.8 × 10¹² g/yr and H₂O ∼0.7-1.0 × 10¹⁴ g/yr, respectively—comparable to previous estimates. Further, we obtain a first estimate of global arc outflux of fluid-recycled F of ∼0.3-0.4 × 10¹²g/yr. Despite the inherent uncertainties, our results support models suggesting that the slab becomes strongly depleted in Cl and H₂O in subduction zones. In contrast, much of the subducted F appears to be returned to the deep mantle, implying efficient fractionation of Cl and H₂O from F during the subduction process. However, if slab devolatilization produces slab fluids with high Cl/F (∼9.5), slab melting will still produce components with low Cl/F ratios (∼0.9), similar to those characteristic of the upper continental crust (Cl/F ∼0.3-0.9).     

Thermodynamic properties,low-temperature heat-capacity anomalies,and single-crystal X-ray refinement of hydronium jarosite, (H<Subscript>3</Subscript>O)Fe<Subscript>3</Subscript>(SO<Subscript>4</Subscript>)<Subscript>2</Subscript>(OH)<Subscript>6</Subscript>

Crystals of hydronium jarosite were synthesized by hydrothermal treatment of Fe(III)–SO₄ solutions. Single-crystal XRD refinement with R₁=0.0232 for the unique observed reflections (|F_o| > 4_F) and wR₂=0.0451 for all data gave a=7.3559(8) Å, c=17.019(3) Å, V^o=160.11(4) cm³, and fractional positions for all atoms except the H in the H₃O groups. The chemical composition of this sample is described by the formula (H₃O)_0.91Fe_2.91(SO₄)₂[(OH)_5.64(H₂O)_0.18]. The enthalpy of formation (H^o_f) is –3694.5 ± 4.6 kJ mol^–1, calculated from acid (5.0 N HCl) solution calorimetry data for hydronium jarosite, -FeOOH, MgO, H₂O, and -MgSO₄. The entropy at standard temperature and pressure (S^o) is 438.9±0.7 J mol^–1 K^–1, calculated from adiabatic and semi-adiabatic calorimetry data. The heat capacity (C_p) data between 273 and 400 K were fitted to a Maier-Kelley polynomial C_p(T in K)=280.6 + 0.6149T–3199700T^–2. The Gibbs free energy of formation is –3162.2 ± 4.6 kJ mol^–1. Speciation and activity calculations for Fe(III)–SO₄ solutions show that these new thermodynamic data reproduce the results of solubility experiments with hydronium jarosite. A spin-glass freezing transition was manifested as a broad anomaly in the C_p data, and as a broad maximum in the zero-field-cooled magnetic susceptibility data at 16.5 K. Another anomaly in C_p, below 0.7 K, has been tentatively attributed to spin cluster tunneling. A set of thermodynamic values for an ideal composition end member (H₃O)Fe₃(SO₄)₂(OH)₆ was estimated: G^o_f= –3226.4 ± 4.6 kJ mol^–1, H^o_f=–3770.2 ± 4.6 kJ mol^–1, S^o=448.2 ± 0.7 J mol^–1 K^–1, C_p (T in K)=287.2 + 0.6281T–3286000T^–2 (between 273 and 400 K).     

Petrogenesis and tectonic implications of early Carboniferous alkaline volcanic rocks in Karamay region of West Junggar,Northwest China

ABSTRACT

Zircon U–Pb geochronological and geochemical analyses are reported for a suite of the early Carboniferous volcanic rocks from West Junggar (Northwest China), southern Central Asian Orogenic Belt (CAOB), with the aim to investigate the sources, petrogenesis, and tectonic implications. Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) U–Pb analysis from an andesite yielded concordant weighted mean ²⁰⁶Pb/²³⁸U age of 345 ± 3 Ma, indicating the presence of early Carboniferous volcanic rocks in West Junggar. The early Carboniferous volcanic rocks consist of basalt, basaltic andesite, and andesite. Geochemically, all the samples bear the signature of ocean island basalt (OIB), and are characterized by alkaline affinity with minor variations in SiO₂ compositions (45.13–53.05 wt.%), high concentrations of Na₂O + K₂O (5.08–8.89 wt.%) and TiO₂ (1.71–3.35 wt.%), and LREE enrichment and HREE depletion ((La/Yb)_N = 7.1–12.4), with weak Eu anomalies (Eu/Eu* = 0.9–1.1) and no obvious Nb, Ta, and Ti negative anomalies. These features suggest that the early Carboniferous volcanic rocks were derived from an OIB-related source that consists of oceanic lithosphere with ~1–3% degree partial melting of garnet lherzolite. From these observations, in combination with previous work, we conclude that the early Carboniferous alkaline volcanic rocks in Karamay region formed by upwelling of asthenospheric mantle through a slab window in a forearc setting during consumption of the West Junggar Ocean. Meanwhile, seamounts, which formed in the Late Devonian and were accreted and subducted in Karamay arc, also brought geological effects in the subduction zone.     

Geochronology, Geochemistry, Whole Rock Sr-Nd and Zircon Hf-O Isotopes of the Early Neoproterozoic Volcanic Rocks in Jiangshan, Eastern Part of the Jiangnan Orogen: Constraints on Petrogenesis and Tectonic Implications

This paper presents the results of combined studies of geochronology, geochemistry, whole rock Sr-Nd and zircon Hf-O isotopes carried out upon the rhyodacite and ignimbrite of Shangshu village, Shangyu town and Shanghupeng village of Jiangshan City in Zhejiang Province, along the northwestern side of the Jiangshan–Shaoxing suture. SHRIMP zircon U-Pb dating of samples in the three areas yielded weighted mean 206 Pb/238 U ages of 842.8 ± 6.9 Ma and 850.0 ± 7.3 Ma, 839 ± 9 Ma and 832.2 ± 8.1 Ma, 828.3 ± 8.5 Ma and 836.9 ± 9.9 Ma, respectively. These ages are older than the volcanic rocks of the Shangshu Formation dated at around 780 Ma distributed in Fuyang City, Hangzhou City, Kaihua County, etc. The volcanic rocks generally have high SiO2(54.08–76.80 wt%) and Al2 O3(12.40–21.31 wt%), low Fe2 O3(0.68–8.92 wt%), MgO(0.29–2.49 wt%), CaO(0.12–2.86 wt%), TiO2(0.10–1.59 wt%) and P2 O5(0.01–0.39 wt%), with variable total alkalis(K2 O + Na2 O =5.42–8.29 wt%). There exists a clear negative correlation between SiO2 and P2 O5. The volcanic rocks have A/CNK ratios of 1.03–2.77 and thus are peraluminous. They are characterized by enrichment in LREE, Rb, Ba, Zr, Hf, K, Th, La, U and depletion in Nb, Sr, P, Ti, with distinct LREE and HREE fractionation of(La/Yb)N values of 5.68–11.67, and with a moderate negative Eu anomaly(Eu=0.58–0.89). Whole-rock geochemical data shows that the Jiangshan volcanic rocks are possibly I-type granitic rocks, even though they have some characteristics of AS-type granites due to the magma fractional crystallization and water-rock interaction. Zircon δ18 O values are 3.97‰–5.49‰(average 4.50‰), 2.90‰–5.21‰(average 4.32‰) for ignimbrite from Shangshu village section, and Shanghupeng village section, respectively. They are slightly lower than the average δ18 O values of igneous zircons in equilibrium with mantle magmas(5.3 ± 0.6‰(2σ)), the lower δ18 O value also demonstrating the presence of high temperature water-rock interactions. The ignimbrite rocks have positive εNd(t)(4.02, 3.37, 3.91, 4.74, 2.85, 4.39, totals from the three areas) and εNd(t)(in-situ zircon)(4.3–14.6, a weighted mean of 8.4; 6.6–12.7, a weighted mean of 9.0; 8.1–12.0, a weighted mean of 9.5, respectively, from the three areas). In conjunction with the trace element studies, they indicate that the source region of the Jiangshan volcanic rocks was mainly composed of juvenile lower crustal material, mixed with some mantle-sourced magma. Detailed elemental and isotopic data suggest that the Jiangshan volcanic rocks were formed in a continental arc setting. There is a series of ca. 860–830 Ma volcanic rocks formed in a back-arc extensional setting in the southern margin of the eastern Jiangnan Orogen, along the northwest side of the Jiangshan–Shaoxing suture. The first stage rift-related anorogenic magmatism may have occurred as early as ca. 860 Ma in the eastern Jiangnan Orogen.     

Cenozoic Island Arc Magmatism in Java Island (Sunda Arc, Indonesia): Clues on Relationships between Geodynamics of Volcanic Centers and Ore Mineralization

Abstract. Java island, regarded as a classic example of island arcs, is built through multi events of Cenozoic arc magmatism produced by the subduction of Indian‐Australian oceanic crusts along the southern margin of Eurasian plate. Regional crustal compositions, subducted slabs, and tectonics determined the spatial‐geochemical evolution of arc magmatism and regional metallogeny. Tertiary geodynamics of island arc was dominated by backarc‐ward migrations of volcanic centers. Only after the Miocene‐Pliocene roll‐back effects of retreating slab, slab detachment, and backarc magmatism took place in central Java. The source of arc magmas is mainly partial melting of mantle wedge, triggered by fluids released from dehydrated slabs. Increasing potassium contents of arc magmas towards the backarc‐side and younger magmas is typical for all magmas, while alkali and incompatible trace elements ratios are characteristics for different settings of volcanic centers. The oceanic nature of crust and the likely presence of hot slab subducted beneath the eastern Java determine the occurrences of adakitic magmas. Backarc magmatism has a deeper mantle source with or without contributions from subduction‐related materials. The domination of magnetite‐series magmatism determines the sulfide mineralization for the whole island. District geology, geodynamics, and magma compositions in turn control particular styles and scales of precious metals concentrations. Deep‐seated crustal faults have focused the locations of overlapping volcanic centers and metalliferous fluids into few major gold districts. Porphyry deposits are mostly concentrated within Lower Tertiary (early stage) volcanic centers in eastern Java which are not covered by younger volcanic centers, and whose sulfides are derived from partial melting of basaltic parental materials. On the other hand, high‐grade low‐sulfidation epithermal gold deposits formed in later stages of arc development and are spatially located within younger volcanic centers (Upper Miocene‐Pliocene) that overlap the older ones. Gold in low‐sulfidation epithermal system is likely to be derived from crustal materials. The overall interacting factors resulting in the petrochemical systematics that are applicable for exploration: 1) early‐stage volcanic centers with high Sr/Y and Na₂O/K₂O ratios are more prospective for porphyry mineralization, while 2) later‐stage volcanic centers with high K₂O, total alkali, and K₂O/Na₂O ratios are more prospective for low‐sulfidation epithermal mineralization.     

云县-景谷火山弧带大中河晚志留世火山岩的发现及其地质意义

云县-景谷火山弧带大中河地区新识别出一套晚志留世中基性-中酸性火山岩组合,其LA-ICPMS锆石U-Pb年龄为421.2±1.2Ma和417.6±5.1Ma。该套火山岩具有富铝(12.73%～16.63%)、富钠(K₂O/Na₂O=0.56～0.99)和高Mg^#(46.0～50.0)的特征,属于钙碱性系列岩石;同时富集轻稀土,Eu具有不同程度的弱亏损,亏损高场强元素(Nb、Ta、Ti),具有正ε_Nd(t)值(3.86～4.39)和较高的Th/Ta比值(15～17),显示与活动大陆边缘岛弧型火山岩相似的地球化学性质。大中河晚志留世火山岩很可能是俯冲沉积物流体交代地幔楔物质部分熔融的产物,并在岩浆上升过程中经历了一定的分离结晶作用和浅部地壳物质的同化混染;结合区域同期(410～420Ma)岩浆活动及相关的高压变质事件分析,应为原-古特提斯洋在早古生代末期向东俯冲消减作用的产物,从而为扬子陆块西部边缘晚古生代"三江"多岛弧盆系的形成演化提供了前锋弧发育的岩石学证据及其动力学机制。     

Separation of H<Subscript>2</Subscript>S from CH<Subscript>4</Subscript> by polymeric membranes at different H<Subscript>2</Subscript>S concentrations

In this work, permeation of mixed gases H₂S/CH₄ through commercial polyphenylene oxide (PPO) hollow fiber and poly (ester urethane) urea (PEUU) flat membranes was studied at pressures of 345–689 kPa, at ambient temperature and at 313.15 K. Various H₂S concentrations of about 100–5000 ppm in CH₄ binary synthetic gas mixtures as well as a real natural gas sample obtained from a gas refinery containing 0.3360 mol.% H₂S (equivalent to 3360 ppm) were tested. It was observed that the permeance of components was affected by the balance between competitive sorption and plasticization effects. Separation factors of H₂S/CH₄ were in the range of 1.3–2.9, 1.8–3.1 and 2.2–4.3 at pressures of 345, 517 and 689 kPa, respectively. In the range of 101–5008 ppm of H₂S in CH₄, the effect of temperature on the separation factor was nearly negligible; however, permeances of both components of the mixtures increased with temperature. Additionally, the results obtained by PEUU membrane indicated that it was a better choice for hydrogen sulfide separation from H₂S/CH₄ mixtures than PPO. For PPO membrane, removal of hydrogen sulfide from high-concentration (up to 5008 ppm) binary mixtures of H₂S/CH₄ was compared with that of low concentration (as low as 101 ppm) through PPO. At concentrations of 101–968 ppm, plasticization was dominant compared with the competitive sorption, while for the H₂S feed concentrations of 3048 ppm, the competitive sorption effect was dominant. For H₂S concentration of 5008 ppm, the balance between these two effects played an important role for explanation of its trend.     

Relationship between soil CO<Subscript>2</Subscript> flux and volcanic tremor at Mt. Etna: Implications for magma dynamics

Large variations of the CO₂ flux through the soil were observed between November 2002 and January 2006 at Mt. Etna volcano. In many cases, the CO₂ flux was strongly influenced by changes in air temperature and atmospheric pressure. A new filtering method was then developed to remove the atmospheric influences on soil CO₂ flux and, at the same time, to highlight the variations strictly related to volcanic activity. Successively, the CO₂ corrected data were quantitatively compared with the spectral amplitude of the volcanic tremor by cross correlation function, cross-wavelet spectrum and wavelet coherence. These analyses suggested that the soil CO₂ flux variations preceded those of volcanic tremor by about 50 days. Given that volcanic tremor is linked to the shallow (a few kilometer) magma dynamics and soil CO₂ flux related to the deeper (~12 km b.s.l.) magma dynamics, the “delayed similarity” between the CO₂ flux and the volcanic tremor amplitude was used to assess the average speed in the magma uprising into the crust, as about 170–260 m per day. Finally, the large amount of CO₂ released before the onset of the 2004–2005 eruption indicated a deep ingression of new magma, which might have triggered such an eruption.     

Preferential dissolution of SiO<Subscript>2</Subscript> from enstatite to H<Subscript>2</Subscript> fluid under high pressure and temperature

Stability and phase relations of coexisting enstatite and H₂ fluid were investigated in the pressure and temperature regions of 3.1–13.9 GPa and 1500–2000 K using laser-heated diamond-anvil cells. XRD measurements showed decomposition of enstatite upon heating to form forsterite, periclase, and coesite/stishovite. In the recovered samples, SiO₂ grains were found at the margin of the heating hot spot, suggesting that the SiO₂ component dissolved in the H₂ fluid during heating, then precipitated when its solubility decreased with decreasing temperature. Raman and infrared spectra of the coexisting fluid phase revealed that SiH₄ and H₂O molecules formed through the reaction between dissolved SiO₂ and H₂. In contrast, forsterite and periclase crystals were found within the hot spot, which were assumed to have replaced the initial orthoenstatite crystals without dissolution. Preferential dissolution of SiO₂ components of enstatite in H₂ fluid, as well as that observed in the forsterite H₂ system and the quartz H₂ system, implies that H₂-rich fluid enhances Mg/Si fractionation between the fluid and solid phases of mantle minerals.     

Continuous supply of recycled Pacific oceanic materials in the source of Cenozoic basalts in SE China: the Zhejiang case

Various enriched recycled oceanic components in the source of Cenozoic intra-plate alkaline basalts from eastern China were identified by previous studies. Due to the existence of a stagnant subducted Pacific slab in the mantle transition zone beneath eastern China, it is logical to connect the stagnant slab to the recycled oceanic materials. However, the recycled oceanic materials could also result from ancient subduction events (e.g., Paleo-Tethyan, Paleo-Asian or Izanagi plate subduction) because enriched geochemical signatures of a recycled slab can be preserved in the mantle for longer than 1 Gyr. Investigating the temporal variations of the recycled oceanic materials in the mantle source is a useful way to trace the origin of the basalts. In this article, we have conducted a detailed geochemical study, including major and trace elements and Sr–Nd–Pb isotopes, on two alkaline basalt groups from Zhejiang, SE China, which erupted 26–17 Ma and after 11 Ma, respectively. In particular, we recovered the H₂O content of the initial magmas based on the H₂O content of the clinopyroxene (cpx) phenocrysts and the partition coefficients of H₂O between cpx and basaltic melts. The H₂O contents of the Zhejiang basalts range from 1.3 to 2.6 (wt.%), which fall within the range of back-arc basin or island arc basalts. The older basalts are more alkaline and have lower Si and Al contents; higher trace element concentrations; higher La/Yb, Ce/Pb and Nb/La ratios; lower H₂O/Ce and Ba/Th ratios; and stronger negative K, Pb, Hf and Ti anomalies than the younger ones. The co-relationships between Ba/La, H₂O/Ce, Nb/La, Ce/Pb and Ba/Th in the two groups of the Zhejiang basalts indicate that a recycled dehydrated oceanic alkaline basalt component is needed in the source of the older rocks, along with a depleted mantle component. Meanwhile, an additional recycled dehydrated sediment component was required in the source of the younger rocks. The temporal change in the recycled oceanic materials in the mantle sources of Zhejiang Cenozoic basalts demonstrates that the recycled components can only originate in the stagnant Pacific slab that is the only plate subducted since 100 Ma in this area.     

The effect of alkalis and polymerization on the solubility of H<Subscript>2</Subscript>O and CO<Subscript>2</Subscript> in alkali-rich silicate melts

The effect of alkalis on the solubility of H₂O and CO₂ in alkali-rich silicate melts was investigated at 500 MPa and 1,250 °C in the systems with H₂O/(H₂O + CO₂) ratio varying from 0 to 1. Using a synthetic analog of phonotephritic magma from Alban Hills (AH1) as a base composition, the Na/(Na + K) ratio was varied from 0.28 (AH1) to 0.60 (AH2) and 0.85 (AH3) at roughly constant total alkali content. The obtained results were compared with the data for shoshonitic and latitic melts having similar total alkali content but different structural characteristics, e.g., NBO/T parameter (the ratio of non-bridging oxygens over tetrahedrally coordinated cations), as those of the AH compositions. Little variation was observed in H₂O solubility (melt equilibrated with pure H₂O fluid) for the whole compositional range in this study with values ranging between 9.7 and 10.2 wt. As previously shown, the maximum CO₂ content in melts equilibrated with CO₂-rich fluids increases strongly with the NBO/T from 0.29 wt % for latite (NBO/T = 0.17) to 0.45 wt % for shoshonite (NBO/T = 0.38) to 0.90 wt % for AH2 (NBO/T = 0.55). The highest CO₂ contents determined for AH3 and AH1 are 1.18 ± 0.05 wt % and 0.86 ± 0.12 wt %, respectively, indicating that Na is promoting carbonate incorporation stronger than potassium. At near constant NBO/T, CO₂ solubility increases from 0.86 ± 0.12 wt % in AH1 [Na/(Na + K)] = 0.28, to 1.18 ± 0.05 wt % in AH3 [Na/(Na + K)] = 0.85, suggesting that Na favors CO₂ solubility on an equimolar basis. An empirical equation is proposed to predict the maximum CO₂ solubility at 500 MPa and 1,100–1,300 °C in various silicate melts as a function of the NBO/T, (Na + K)/∑cations and Na/(Na + K) parameters: \({\text{wt}}\% \;{\text{CO}}_{2} = - 0.246 + 0.014\exp \left( {6.995 \cdot \frac{\text{NBO}}{T}} \right) + 3.150 \cdot \frac{{{\text{Na}} + {\text{K}}}}{{\varSigma {\text{cations}}}} + 0.222 \cdot \frac{\text{Na}}{{{\text{Na}} + {\text{K}}}}.\) This model is valid for melt compositions with NBO/T between 0.0 and 0.6, (Na + K)/∑cation between 0.08 and 0.36 and Na/(Na + K) ratio from 0.25 to 0.95 at oxygen fugacities around the quartz–fayalite–magnetite buffer and above.