FeO activity and oxygen potential in magnesian magmas

An equation for the excess free energy of melts containing all major components is derived from published experimental data on equilibria between silicate liquids with either metallic iron or spinel at controlled oxygen partial pressure. The FeO activities in mafic and ultramafic magmas calculated with this equation were used to develop an oxygen barometer (geoxometer) for the association spinel + melt. Data derived with the application of the geoxometer confirm that meymechite magmas in the Siberian trap province had oxygen fugacities higher than in other magmatic systems. The origin of lower lithospheric domains with elevated redox potential can be explained by the intense diffusion of hydrogen from zones in which water-rich near-solidus melts from asthenospheric sources were emplaced into harzburgites, which had lost water and other incompatible elements in the course of earlier large-scale melting.     

北祁连桦树沟铜矿床矿物学和硫同位素特征及其成矿意义

桦树沟铜矿床位于北祁连加里东造山带西段。铜矿体赋存于镜铁山BIF型铁矿床桦树沟矿区FeⅤ矿体下盘,矿体受断裂构造控制,矿化岩石主要为铁碧玉岩、石英绢云母千枚岩和碳质千枚岩,围岩蚀变可见硅化、碳酸盐化、绢云母化和绿泥石化。文章对块状铜矿石(富铜矿体)和脉状铜矿石(千枚岩型铜矿体)进行了野外地质特征、矿物学和硫同位素对比研究。富铜矿体与地层产状基本一致,块状矿石矿物组合为黄铜矿+少量黄铁矿+石英+碳酸盐矿物+重晶石,黄铜矿低S、Cu,高Fe。脉状矿石主要表现为石英-碳酸盐-硫化物脉沿千枚理或裂隙产出,矿石矿物组合为黄铜矿+黄铁矿+黝铜矿+镜铁矿+石英+碳酸盐矿物+绢云母+绿泥石,黄铜矿低S高Fe。块状铜矿石中黄铜矿的δ34S变化范围为15.6‰~17.4‰,暗示硫主要来自同期海水。脉状矿石中硫化物的δ34S值低于块状矿石中黄铜矿的δ34S值,黄铜矿、黄铁矿的δ34S值变化范围分别为13.2‰~16.2‰和9.3‰~13.4‰,暗示硫可能主要来自受还原的硫化物和硫酸盐矿物。以上研究表明块状铜矿石和脉状铜矿石可能为不同热事件的产物,结合前人研究成果,笔者认为桦树沟铜矿床为海底喷流沉积叠加后期热液改造成因。绿泥石温度计指示后期热液成矿温度为222℃左右。     

The Baffin Bay lavas and the value of picrites as analogues of primary magmas

The Baffin Bay picrites have been the focal point of a controversy concerning the MgO content of primary magmas derived from the upper mantle. A sample population of 48 lava chilled margins collected across the Baffin Bay volcanic succession at the northeastern tip of Padloping Island exhibits a prominent compositional mode between 14 and 16 weight percent MgO (19–22 Mg, cation units = Mg/100 cations). The petrography of these samples, however, requires that the Padloping magmas were mixtures of olivine crystals and liquid at their eruption. Olivine phenocrysts constituted 15 to 30 volume percent of these magmas and retain compositions requiring coexisting liquid compositions with only 10 to 13.5 weight percent MgO (14–18.5 Mg). However, highly magnesian, olivine xenocrysts (up to Fo 93) found in the most magnesian lavas require the former existence of liquids with at least 18 weight percent MgO (24 Mg). If these xenocrysts represent early cumulates, then the primary liquids of the Padloping suite must have been at least this MgO rich with temperatures greater than 1,425° C. Such primary liquids could have evolved by olivine crystallization to a steady state, equilibrated crystal — liquid mixtures in a shallow reservoir system prior to eruption. The compositions of the liquids of these mixtures appear to have been perched at the point of plagioclase saturation at approximately 1,275° C.Despite the complications of mechanical sorting of olivine crystals, the virtual compositional reciprocity of olivine addition and olivine fractionation requires that the bulk compositions of picritic lavas provide compositional analogues of their primary magmas. A comparison of Phanerozoic picrite suites indicates that the Fe contents of terrestrial primary magmas of tholeiitic affinity have a restricted range from 6–9 Fe. Primary magmas associated with intra-plate volcanism appear to be distinctly more Fe-rich than those associated with inter-plate volcanism. The Al/Si ratios of Phanerozoic picrite suites could suggest that the primary magmas of MORB volcanism have equilibrated with relatively Fe-poor source regions at deeper levels in the Earth's mantle than those of other tholeiitic primary magmas.     

Empirical equations to predict the sulfur content of mafic magmas at sulfide saturation and applications to magmatic sulfide deposits

Empirical equations to predict the sulfur content of a mafic magma at the time of sulfide saturation have been developed based on several sets of published experimental data. The S content at sulfide saturation (SCSS) can be expressed as:

Geochemical variations in lavas from Kahoolawe volcano,Hawaii: evidence for open system evolution of plume-derived magmas

The Kahoolawe shield volcano produced precaldera and caldera-filling tholeiites and mildly alkalic post-caldera lavas that petrographically and compositionally resemble such lavas from other Hawaiian shield volcanoes. However, Kahoolawe tholeiites display wide ranges in incompatible trace element ratios (e.g., Nb/Th=9–24, Th/Ta=0.6–1.3), ⁸⁷Sr/⁸⁶Sr (0.70379–0.70440), ¹⁴³Nd/¹⁴⁴Nd (0.51273–0.51298), and ²⁰⁶Pb/²⁰⁴Pb (17.92–18.37). The isotopic variation exceeds that at any other Hawaiian shield volcano, and spans about half the range for all Hawaiian tholeiites. Quasi-cyclic temporal evolution of Kahoolawe tholeiites is consistent with combined fractional crystallization and periodic recharge by primitive magmas. Ratios of highly incompatible trace elements and Sr, Nd, and Pb isotopic ratios from coherent sub-trends that reflect recurrent interactions between variably evolved magmas and two other mantle components whose compositions are constrained by intersections between these trends. The most MgO-rich Kahoolawe tholeiites are partial melts of a high Nb/Th (23.5) ascending plume, possibly comprising ancient subducted oceanic lithosphere. Slightly evolved tholeiites experienced combined crystal fractionation and assimilation (AFC) of material derived from a distinct reservoir (Nb/Th 9) of asthenospheric derivation. The most evolved tholeiites display compositional shifts toward a third component, having mid ocean ridge basalt-like isotopic ratios but enriched OIB-like trace element ratios, representing part of the lithospheric mantle (or melts thereof). Periodic recurrence of all three magma variants suggests that eruptions may have tapped coeval reservoirs distributed over a large depth range. Kahoolawe provides new evidence concerning the nature of the Hawaiian plume, the distribution of compositional heterogeneities in the suboeanic mantle, and the processes by which Hawaiian tholeiites form and evolve.     

Chalcophile element geochemistry and petrogenesis of high-Ti and low-Ti magmas in the Permian Emeishan large igneous province,SW China

Sulfide-poor mafic layered intrusions, sills/dykes and lava flows in the Funing region, SW China, are part of the ~260 Ma Emeishan large igneous province. They belong to either a high-Ti group (TiO₂ = 1.6–4.4 wt%) with elevated Ti/Y ratios (351–1,018), or a low-Ti group (TiO₂ < 1.2 wt%) with low Ti/Y ratios (133–223). This study investigates the role of fractionation of olivine, chromite and sulfide on the distributions of chalcophile elements, Ni, Cu and PGE, of the high-Ti and low-Ti group rocks at Funing. The high-Ti group rocks contain 1.6–5.3 ppb Pt + Pd, 0.06–0.43 ppb Ir and 0.01–0.13 ppb Ru, and show relative constant (Cu/Pd)_PM ratios (4.0–9.7) and a negative correlation between Ni/Pd and Cu/Ir ratios. Fractionated IPGE/PPGE patterns and very negative Ru anomalies of the high-Ti group rocks, together with low Fo values (59–62 mol%) of olivine, indicate that the high-Ti magmas may have experienced fractionation of olivine and chromite under S-undersaturated condition. Based on the PGE concentrations, the low-Ti group rocks can be further divided into two subgroups; a high-PGE low-Ti subgroup and a low-PGE low-Ti subgroup. The high-PGE low-Ti group rocks are rich in MgO (10–20 wt%), but Fo values of olivine from the rocks are low (74–76 mol%). The rocks contain highly variable PGE (Pt + Pd = 1.7–88 ppb, Ir = 0.05–1.3 ppb), Ni (179 –1,380 ppm) and Cu (59–568 ppm). They have Cu/Zr ratios >1, low (Y/Pd)_PM ratios (0.2–7.1) and nearly constant (Cu/Pd)_PM ratios (1.5–3.8). The even and parallel chalcophile element patterns of the high-PGE low-Ti subgroup rocks are likely a result of olivine-dominated fractionation under S-undersaturated condition. The low-PGE low-Ti group rocks have low MgO (4.5–8.9 wt%) and very poor PGE (Pt + Pd 0.5–1.6 ppb, Ir 0.004–0.02 ppb) with low Cu/Zr ratios (0.1–0.5), high (Y/Pd)_PM (26–70) and variable (Cu/Pd)_PM ratios (2.8–14). The trough-like chalcophile element patterns of the low-PGE low-Ti subgroup rocks indicate that the magmas were sulfide saturation and sulfide melts were extracted from the magmas. The extracted sulfide melts might be potential Ni–Cu sulfide ores at depth in the Funing region.     

Dependence of clinopyroxene composition on cooling rate in basaltic magmas: Implications for thermobarometry

The compositional variation of clinopyroxene and the partitioning of major elements between clinopyroxene and melt are estimated as a function of the cooling rate. Clinopyroxenes were crystallized under variable cooling regimes (15, 9.4, 3, 2.1, and 0.5 °C/min from 1250 down to 1000 °C) and at isothermal conditions of 1000 °C from a basaltic composition at a pressure of 500 MPa under anhydrous and hydrous (H₂O = 1.3 wt.%) conditions. The clinopyroxene chemistry shows that, as the cooling rate increases, crystals are progressively depleted in Ca, Mg, Fe²⁺ and Si and enriched in Na, Fe³⁺, Al (mainly Al^IV), and Ti. Di and Hd versus CaTs and CaFeTs form a continuous binary solid solution characterized by higher amounts of tschermakitic components with increasing cooling rate. Two parameters (DH = Di + Hd and TE = CaTs + CaFeTs + En) are calculated to describe the effect of cooling rate on the clinopyroxene composition. The variation of DH/TE with increasing cooling rate evidences the kinetic process induced by rapid cooling in basic rocks under hydrous and anhydrous conditions.Dynamic crystallization conditions affect the partitioning of major elements between clinopyroxene and melt; with increasing cooling rate, the value of crystal–melt partition coefficient departs from that obtained at the isothermal condition. However, in spite of these variations, the values of ^cpx–meltKd_Fe–Mg remain almost constant. Therefore, the Fe²–Mg exchange between clinopyroxene and melt is not suitable to prove the (dis)equilibrium conditions in basaltic cooling magmas, giving rise to possible mismatches in the application of thermobarometers. The results of our study are consistent with that observed at the margin of dikes or in the exterior portions of lavas, where the cooling rate is maximized and disequilibrium compositions of clinopyroxene have been found.     

Geochemical and strontium isotopic characteristics of parental Aleutian arc magmas: evidence from the basaltic lavas of Atka

Eighteen flows from a basal stratigraphic sequence on the Aleutian Island of Atka were analyzed for major elements, trace elements and initial ⁸⁷Sr/⁸⁶Sr ratios. Petrographically, these lavas contain abundant plagioclase (24–45%) and lesser amounts of olivine (<7%), magnetite and clinopyroxene phenocrysts. Compositionally, the lavas are high-alumina (20wt%) basalts (48–51 wt% SiO₂) with low TiO₂ (<1%) and MgO (<5%). Within the section, compositional variations for all major elements are quite small. While MgO content correlates with olivine phenocryst contents, no such relationship exists between the other oxides and phenocryst content. These lavas are characterized by 8–10 ppm Rb, high Sr (610–669 ppm), 308–348 ppm Ba and very constant Zr (23–29 ppm) and Sc (23–29 ppm) abundances. Ni and Cr display extremely large compositional ranges, 12–118 ppm and 12–213 ppm, respectively. No correlation exists between trace element concentrations and phenocryst contents. Strontium isotopic ratios show a small but significant range (0.70314–0.70345) and are slightly elevated with respect to typical MORB. No systematic correlation between stratigraphic position and petrography or geochemistry is evident. REE abundances measured on six samples are LREE enriched ((La/ Yb)_N = 2.20–2.81) and display similar chondrite normalized patterns. One sample has a slight positive Eu anomaly but the other lavas do not. Compared to other Aleutian basalts of similar silica content, these lavas are less LREE enriched and have lower overall abundances. The geochemical characteristics of these basalts suggest they represent true liquid compositions despite their highly porphyritic nature. Published phase relations indicate fractionation of a more MgO-rich magma could not have produced these lavas. The high Al₂O₃ and low MgO and compatible element abundances suggest a predominantly oceanic crustal source for parental high-alumina basalts.     

The evolution of young silicic lavas at Medicine Lake Volcano,California: Implications for the origin of compositional gaps in calc-alkaline series lavas

At Medicine Lake Volcano, California, the compositional gap between andesite (57–62 wt.% SiO₂) and rhyolite (73–74 wt.% SiO₂) has been generated by fractional crystallization. Assimilation of silicic crust has also occurred along with fractionation. Two varieties of inclusions found in Holocene rhyolite flows, hornblende gabbros and aphyric andesites, provide information on the crystallization path followed by lavas parental to the rhyolite. The hornblende gabbros are magmatic cumulate residues and their mineral assemblages are preserved evidence of the phases that crystallized from an andesitic precursor lava to generate the rhyolite lavas. The andesitic inclusions represent samples of a parental andesite and record the early part of the differentiation history. Olivine, plagioclase and augite crystallization begins the differentiation history, followed by the disappearance of olivine and augite through reaction with the liquid to form orthopyroxene and amphibole. Further crystallization of the assemblage plagioclase, amphibole, orthopyroxene, magnetite, and apatite from a high-SiO₂ andesite leads to rhyolite. This final crystallization process occurs on a cotectic that is nearly horizontal in temperature-composition space. Since a large amount of crystallization occurs over a limited temperature interval, a compositional gap develops between rhyolite and high SiO₂ andesite.Liquidus surfaces with shallow slopes in temperature-composition space are characteristic of several late-stage crystallization assemblages in the andesite to rhyolite compositional range. Experimentally produced plagioclase+ amphibole+orthopyroxene+magnetite and plagioclase+ augite+low-Ca pyroxene+magnetite cotectics have liquidus slopes that are nearly flat. At other calc-alkaline volcanic centers crystallization processes involving large compositional changes over small temperature intervals may also be important in the development of bimodal volcanism (i.e. the existence of a composition gap). At Mt. Mazama and Mt. St. Helens, USA and Aso Caldera and Shikotsu, Japan the amphibole-bearing assemblage was important. At Krakatau, Indonesia and Katmai, USA, an augite+orthopyroxene-bearing assemblage was important. In addition to its role in the production of a compositional gap between intermediate and rhyolitic lavas, the crystallization process increases the H₂O content of the residual liquid. This rapid increase in residual liquid volatile content which results from the precipitation of a large proportion of crystalline solids may be an important factor among several that lead to explosive silicic eruptions.     

LA-ICP-MS UPb geochronology of wolframite by combining NIST series and common lead-bearing MTM as the primary reference material:Implications for metallogenesis of South China

Direct dating of W and WSn deposits by wolframite is more reliable relatively to gangue mineral and important for understanding their timing and genesis. However, such analysis still lacks of homogeneous wolframite standard recently. Due to containing considerable and variable common lead, and inhomogeneous in different grains, the wolframite sample of MTM, which is a promising candidate reference material proposed by previous studies, is not suitable as a primary standard for wolframite UPb dating by LA-ICP-MS using the normal normalization method as zircons. In this contribution, a modified normalization method is established for wolframite UPb dating, in which NIST612 or 614 and MTM are used for correction of PbPb and UPb ratios, respectively. Wolframite UPb dating are performed on the Langcun, Xihuashan, Piaotang, Shamai W or WSn deposits and the Baiganhu ore district, the obtained lower intercept ²⁰⁶Pb/²³⁸U ages are comparable with the ages from syngenetic molybdenite, cassiterite, muscovite and the genetically related granites, as well as wolframite by water vapor-assisted ns-LA-ICP-MS UPb dating method. The results of this analysis demonstrate that the robust age for W mineralization can be determined by LA-ICP-MS UPb dating of wolframite using this modified calibration method. Mineralization ages of 125–130 Ma by directly dating of metal minerals for the Langcun W, Jianfengpo Sn and large-size Xianglushan W deposits confirm that there exists an important WSn mineralization event in this period. The close temporal and spatial correlation indicates the granites and W-Cu-Mo-Pb-Zn-Sn mineralization have a genetic relationship with each other and are resulted from the same tectonic-magmatic-hydrothermal events during 140 to 120 Ma in South China.     

Experimental petrology of alkalic lavas: constraints on cotectics of multiple saturation in natural basic liquids

Experimental study of natural alkalic lava compositions at low pressures (pO₂QFM) reveals that crystallization of primitive lavas often occurs in the sequence olivine, plagioclase, clinopyroxene, nepheline without obvious reaction relation. Pseudoternary liquidus projections of multiply saturated liquids coexisting with plagioclase (±olivine±clinopyroxene±nepheline) have been prepared to facilitate graphical analysis of the evolution of lava compositions during hypabyssal cooling. Use of (TiAl₂)(MgSi₂)_–1 and Fe³⁺ (Al)_–1 exchange components is a key aspect of the projection procedure which is succesful in reducing a wide range of compositions to a systematic graphical representation. These projections, and the experiments on which they are based, show that low pressure fractionation plays a significant role in the petrogenesis of many alkalic lava suites from both continental and oceanic settings. However, the role of polybaric fractionation is more evident in the major element chemistry of these lava suites than in many tholeiitic suites of comparable extent. For example, the lavas of Karisimbi, East Africa, show a range of compositions reflecting a polybaric petrogenesis from primitive picrites at 1360° C/18 kb and leading to advanced low pressure differentiates. Evolved leucite-bearing potassic members of this and other suites may be treated in a nepheline-diopside-kspar (+olivine+leucite) projection. Compositional curvature on the plagioclase+clinopyroxene+olivine+leucite cotectic offers a mechanism to explain resorption of plagioclase in alkalic groundmass assemblages and the incompatibility of albite and leucite. This projection is useful for evaluating the extent of assimilation of the alkalic portions of crustal granulites. Assimilation appears to have played some role in the advanced differentiates from Karisimbi.     

An experimental study of anorthosite dissolution in lunar picritic magmas: Implications for crustal assimilation processes

Experiments characterizing the kinetics of anorthosite dissolution in lunar picritic magmas (very low-Ti, low-Ti, and high-Ti picritic glasses) were conducted at 0.6 GPa and 1250-1400 °C using the dissolution couple method. Reaction between the anorthosite and lunar picritic magmas at 1250-1300 °C produced a spinel + melt layer. Reaction between the anorthosite and an olivine-saturated low-Ti magma at 1250-1300 °C produced a crystal-free region between the spinel + melt layer and the olivine-saturated magma. The anorthosite dissolution experiments conducted at 1400 °C simply dissolved anorthosite and did not result in a crystal-bearing region. The rate of anorthosite dissolution strongly depends on temperature and composition of the reacting melt. Concentration profiles that develop during anorthosite dissolution are nonlinear and extend from the picritic glass compositions to anorthite. These profiles feature a large and continuous variation in melt density and viscosity from the anorthosite-melt interface to the initial picritic magmas. In both the low-Ti and high-Ti magmas the diffusive fluxes of TiO₂, Al₂O₃, and SiO₂ are strongly coupled to the concentration gradients of CaO and FeO. Anorthosite dissolution may play an important role in producing the chemical variability of the lunar picritic magmas, the origin of spinel in the lunar basalts and picritic glasses, and the petrogenesis of the high-Al basalts.     

Ferric/ferrous ratios in 1984 Mauna Loa lavas: a contribution to understanding the oxidation state of Hawaiian magmas

Ferric/ferrous ratios have been used to estimate the oxygen fugacity of lavas erupted in 1984 on Mauna Loa Volcano, Hawaii. Rapidly quenched lavas erupted close to vents are less oxidized than rapidly quenched lavas scooped from lava flows several kilometers away from the vents. These results demonstrate that sampling is of critical importance in determining the oxidation state of lava. The oxidation state of the vent lavas, below or at magnetite–wüstite (MW), is significantly lower than that previously reported for Hawaiian lavas (~FMQ). Similarly, rapidly quenched lavas from the ongoing Kilauea eruption and Loihi seamount, all have oxygen fugacities that are close to MW and on the low side of the range previously reported for Hawaiian lavas. From this we conclude that the initial oxygen fugacity of parental Hawaiian magmas is close to MW, not FMQ, and that previous estimates of the oxidation state of Hawaiian lavas may have been too high. This implies that the plume source of these magmas is also at or below MW, but not as reduced as the mantle source of mid-ocean ridge basalts. Additionally, Mauna Loa lavas appear to be slightly more reduced than Kilauea or Loihi lavas, perhaps indicating heterogeneous oxidation within the Hawaiian plume.     

Petrology and chemistry of recent lavas in the northern Marianas: Implications for the origin of island arc basalts

Petrologic and chemical data are presented for samples from five volcanically active islands in the northern Marianas group, an intra-oceanic island arc. The data include microprobe analyses of phenocryst and xenolith assemblages, whole rock major and trace element chemistry including REE, and Sr isotope determinations (⁸⁷Sr/⁸⁶Sr=0.7034±0.0001). Quartz-normative basalt and basaltic andesite are the most abundant lava types. These are mineralogically and chemically similar to the mafic products of other intra-oceanic islands arcs. It is suggested, however, that they are not typical of the ‘island arc tholeiitic’ series, having Fe enrichment trends and K/Rb, for example, more typical of calc-alkaline suits. Major and trace element characteristics, and the presence of cumulate xenoliths, indicate that extensive near surface (< 3 Kb) fractionation has occurred. Thus, even least fractionated basalts have low abundances of Mg, Ni and Cr, and high abundances of K and other large cation, imcompatible elements, relative to ocean ridge tholeiites. However, abundances of REE and small cation lithophile elements, such as Ti, Zr, Nb, and Hf are lower than typical ocean ridge tholeiites. The REE data and Sr isotope compositions suggest a purely mantle origin for the Marianas island arc basalts, with negligible input from subducted crustal material. Thus, subduction of oceanic lithosphere may not be a sufficient condition for initiation of island arc magmatism. Intersection of the Benioff zone with an asthenosphere under appropriate conditions may be requisite. Element ratios and abundances, combined with isotopic data, suggest that the source for the Marianas island arc basalts is more chondritic in some respects, and less depleted in large cations than the shallow (?) mantle source for ocean ridge tholeiites.     

Nickel content of basaltic magmas: identification of primary magmas and a measure of the degree of olivine fractionation

Available NiO analyses of olivine in peridotites of probable mantle origin are consistent in giving values around 0.40 weight per cent. Assuming that basaltic magma forming from the mantle was in equilibrium with such peridotitic olivine, the NiO content of primary basaltic magmas is estimated to be about 0.030–0.050 weight per cent. The fractionation behaviour of nickel in basaltic magma due to the crystallization of olivine has been calculated using constant NiMg and FeMg exchange partition coefficients between olivine and magma. It is shown that the NiO content of both magma and olivine decreases by 50 per cent after fractional crystallization of 6–12 per cent of olivine. The nickel distribution in some basaltic rocks and olivines is examined in the light of these results, and it is suggested that basaltic magmas, such as some of the ocean-floor basalt and the Hawaiian tholeiite and alkali basalts, represent primary magmas from mantle peridotites.     

Predicting phosphate saturation in silicate magmas: An experimental study of the effects of melt composition and temperature

A series of 1 atm experiments has been performed to test the influence of iron content and oxidation state on the saturation of phosphate minerals in magmatic systems. Four bulk compositions of different iron content have been studied. The experiments cover a range of temperature from 1030 to 1070 °C and oxygen fugacity from 1.5 log units below to 1.5 log units above the Fayalite-Magnetite-Quartz buffer. The results demonstrate that neither iron content of the liquid nor oxidation state play a significant role on phosphate saturation. On the other hand, SiO₂ and CaO contents of the liquid strongly influence the appearance of a crystalline phosphate. Our results are combined with data from the literature to define an equation which predicts the P₂O₅ content of silicate liquids saturated in either whitlockite or fluorapatite:

     

Windows of metamorphic sulfur liberation in the crust: Implications for gold deposit genesis

Understanding the source of metamorphic sulfur is critical to clarifying the complete cycle of ore genesis, from source to sink, for several mineral deposit types. In this study, a mass balance approach and the thermodynamic computer programs Thermocalc and PerpleX were used to constrain the P-T range of pyrite breakdown to pyrrhotite (which liberates sulfur) in common metamorphic lithologies. The results suggest that most of the continental crust’s metamorphic sulfur is liberated in a relatively narrow temperature-pressure window corresponding to the terminal breakdown of chlorite at moderate to low pressures. This is because pyrite stability is controlled partly by temperature and pressure, and partly by the amount of H₂O present. During prograde metamorphism from the greenschist to the amphibolite facies, metamorphic H₂O is produced primarily through chlorite breakdown in mafic to pelitic bulk compositions. As temperature increases, more sulfur is required from pyrite to maintain equilibrium proportions of H₂O, H₂S and SO₂ in the fluid, and in addition, progressively more sulfur is required at lower pressures. At low temperatures, little sulfur is required by metamorphic fluid released during initial chlorite breakdown, whereas at higher temperatures coinciding with the terminal breakdown of chlorite, not only is more fluid present, but the fluid’s sulfur requirement has also increased dramatically. In this way, metamorphic dehydration drives pyrite breakdown and generation of sulfur-rich hydrothermal fluids at mesothermal conditions. Beyond the chlorite stability field there is minimal metamorphic fluid production, except at low pressures and high temperatures where muscovite can break down without causing melting; conditions that are a long way from typical crustal geotherms. However, deformation also plays a key role in pyrite breakdown. Without deformation, small amounts of fluid in chemical communication with individual pyrite grains will quickly acquire equilibrium concentrations of the sulfur species and minimal pyrite breakdown is necessary. Whereas during deformation, there may be a continuous fluid flux past pyrite grains, promoting ongoing sulfur liberation. In this way, periods of deformation may be the major sulfur-liberating episodes during a metamorphic cycle. Since hydrothermal fluids are inherently buoyant and consequently tend to migrate upwards and towards cooler temperatures through the crust, these results imply that orogenic gold deposits are most likely to form at lower-amphibolite to prehnite-pumpellyite facies conditions, and unlikely to form at higher temperatures. The pressure constraint on metamorphic sulfur liberation implies that tectonic settings that allow prograde metamorphism to follow low pressure P-T-t paths in an occasionally compressional or transpressional environment are necessary. Settings that promote extensive injection of felsic magma into a mid-crust that contains a significant proportion of pyritic carbonaceous metasediment are shown to be ideal for orogenic gold deposit genesis. Inverted back-arc basins are interpreted to be the most favourable of these.     

Evidence for southward subduction of the Mongol-Okhotsk oceanic plate: Implications from Mesozoic adakitic lavas from Mongolia

A combination of new ⁴⁰Ar/³⁹Ar dating results, major- and trace-element data, plus Sr-Nd-Pb-Hf isotope data, are used to investigate the petrogenesis of Triassic high-Si adakite (HSA), Cretaceous low-Si adakite-like (LSA) lavas, and Cretaceous high-K and shoshonitic trachyandesite lavas, from eastern and south-central Mongolia. All samples are light rare-earth element and large-ion lithophile element enriched but depleted in some high-field strength elements (notably Nb, Ta and Ti). Two alternative models are proposed to explain the petrogenesis of the HSA samples. (1) A southward-subducting Mongol-Okhotsk slab underwent partial melting in the Triassic during the closure of the Mongol-Okhotsk Ocean, with the resultant melts assimilating mantle and crustal material. Alternatively (2), a basaltic underplate of thickened (>50 km; >1.5 GPa), eclogitic lower crust foundered into the underlying mantle, and underwent partial melting with minor contamination from mantle material and some shallow-level crustal contamination. The LSA samples are interpreted as melts derived from a lithospheric mantle wedge that was previously metasomatised by slab melts. Similarly, the trachyandesite lavas are interpreted as melts deriving from a subduction-enriched subcontinental lithospheric mantle. The spatial distribution of these samples implies that metasomatism likely occurred due to a southward-subducting Mongol-Okhotsk slab associated with the closure of the Mongol-Okhotsk Ocean. When this interpretation is combined with previous evidence for a northward-subducting Mongol-Okhotsk slab it advocates that the Mongol-Okhotsk Ocean closed with double-sided subduction.     

Geochemical evolution of historical lavas from Askja Volcano, Iceland: Implications for mechanisms and timescales of magmatic differentiation

The mechanisms and the timescales of magmatic evolution were investigated for historical lavas from the Askja central volcano in the Dyngjufjöll volcanic massif, Iceland, using major and trace element and Sr, Nd, and Pb isotopic data, as well as ²³⁸U-²³⁰Th-²²⁶Ra systematics. Lavas from the volcano show marked compositional variation from magnesian basalt through ferrobasalt to rhyolite. In the magnesian basalt-ferrobasalt suite (5-10 wt% MgO), consisting of lavas older than 1875 A.D., ⁸⁷Sr/⁸⁶Sr increases systematically with increasing SiO₂ content; this suite is suggested to have evolved in a magma chamber located at ∼600 MPa through assimilation and fractional crystallization. On the other hand, in the ferrobasalt-rhyolite suite (1-5 wt% MgO), including 1875 A.D. basalt and rhyolite and 20th century lavas, ⁸⁷Sr/⁸⁶Sr tends to decrease slightly with increasing SiO₂ content. It is suggested that a relatively large magma chamber occupied by ferrobasalt magma was present at ∼100 MPa beneath the Öskjuvatn caldera, and that icelandite and rhyolite magmas were produced by extraction of the less and more evolved interstitial melt, respectively, from the mushy boundary layer along the margin of the ferrobasalt magma chamber, followed by accumulation of the melt to form separate magma bodies. Ferrobasalt and icelandite lavas in the ferrobasalt-rhyolite suite have a significant radioactive disequilibrium in terms of (²²⁶Ra/²³⁰Th), and its systematic decrease with magmatic evolution is considered to reflect aging, along with assimilation and fractional crystallization processes. Using a mass-balance model in which simultaneous fractional crystallization, crustal assimilation, and radioactive decay are taken into account, the timescale for the generation of icelandite magma from ferrobasalt was constrained to be <∼3 kyr which is largely dependent on Ra crystal-melt partition coefficients we used.