Carbonatization of oceanic crust by the seafloor hydrothermal activity and its significance as a CO2 sink in the Early Archean

Early Archean (3.46 Ga) hydrothermally altered basaltic rocks exposed near Marble Bar, eastern Pilbara Craton, have been studied in order to reveal geological and geochemical natures of seafloor hydrothermal carbonatization and to estimate the CO₂ flux sunk into the altered oceanic crust by the carbonatization. The basaltic rocks are divided into basalt and dolerite, and the basalt is further subdivided into type I, having original igneous rock textures, and type II, lacking these textures due to strong hydrothermal alteration. Primary clinopyroxene phenocrysts are preserved in some part of the dolerite samples, and the alteration mineral assemblage of dolerite (chlorite + epidote + albite + quartz ± actinolite) indicates that the alteration condition was typical greenschist facies. In other samples, all primary minerals were completely replaced by secondary minerals, and the alteration mineral assemblage of the type I and type II basalts (chlorite + K-mica + quartz + carbonate minerals ± albite) is characterized by the presence of K-mica and carbonate minerals and the absence of Ca-Al silicate minerals such as epidote and actinolite, suggesting the alteration condition of high CO₂ fugacity. The difference of the alteration mineral assemblages between basalt and dolerite is probably attributed to the difference of water/rock ratio that, in turn, depends on their porosity.Carbonate minerals in the carbonatized basalt include calcite, ankerite, and siderite, but calcite is quite dominant. The δ¹³C values of the carbonate minerals are −0.3 ± 1.2‰ and mostly within the range of marine carbonate, indicating that the carbonate minerals were formed by seafloor hydrothermal alteration and that carbonate carbon in the altered basalt was derived from seawater. Whole-rock chemical composition of the basaltic rocks is essentially similar to that of modern mid-ocean ridge basalt (MORB) except for highly mobile elements such as K₂O, Rb, Sr, and Ba. Compared to the least altered dolerite, all altered basalt samples are enriched in K₂O, Rb, and Ba, and are depleted in Na₂O, reflecting the presence of K-mica replacing primary plagioclase. In addition, noticeable CO₂ enrichment is recognized in the basalt due to the ubiquitous presence of carbonate minerals, but there was essentially neither gain nor loss of CaO. This suggests that the CO₂ in the hydrothermal fluid (seawater) was trapped by using Ca originally contained in the basalt. The CaO/CO₂ ratios of the basalt are generally the same as that of pure calcite, indicating that Ca in the basalt was almost completely converted to calcite during the carbonatization, although Mg and Fe were mainly redistributed into noncarbonate minerals such as chlorite.The carbon flux into the Early Archean oceanic crust by the seafloor hydrothermal carbonatization is estimated to be 3.8 × 10¹³ mol/yr, based on the average carbon content of altered oceanic crust of 1.4 × 10^-3 mol/g, the alteration depth of 500 m, and the spreading rate of 1.8 × 10¹¹ cm²/yr. This flux is equivalent to or greater than the present-day total carbon flux. It is most likely that the seafloor hydrothermal carbonatization played an important role as a sink of atmospheric and oceanic CO₂ in the Early Archean.     

A comparison of progressive hydrothermal carbonate alteration in Archean metabasalts and metaperidotites

Because of major differences in both bulk chemical composition and silicate mineralogy between metabasalts and metaperidotites, valid comparison of the degree or intensity of carbonate alteration cannot be made in terms of weight per cent CO₂. Molar CO₂/CaO is preferred as an index of the intensity of carbonate alteration in metabasalts; molar CO₂/CaO in carbonatized metabasalts is independent of CaO/MgO and only mildly sensitive to bulk composition and to the proportions of tremolite and clinozoisite. Molar CO₂/CaO reflect the proportions of calcite and dolomite in metabasalts and the proportions of dolomite and magnesite in metaperidotites. However, neither molar CO₂/CaO nor the proportions of dolomite and magnesite are reliable measures of carbonate alteration in metaperidotites of variable composition because both are strongly dependent on MgO/CaO in the whole rock. The preferred alteration index in metaperidotites is m CO₂/m (CaO + MgO + FeO), which represents the proportion of total relevant cations that exist in carbonate form. An empirical equation relating molar CO₂/CaO in metabasalts (x) and MCO₂/m(CaO+MgO+FeO) in metaperidotites (y) is: y=0.16+0.30 x.     

Iron-Titanium Oxide Geothermometry and Petrogenesis of Lava Flows and Dykes from Mandla Lobe of the Eastern Deccan Volcanic Province, India

Compositional studies on different forms of magnetite, ulvospinel, ilmenite and hematite mineral phases occurring in 37 lava flows and 6 dykes of the Mandla lobe are presented in this paper. Ilmenite (0001) in equilibrium with titanomanetite show high values of temperature of equilibration, ranging from 1172–974°C, for high alumina quartz normative tholeiitic lava flows of Chemical Type - A; 1129–1229°C for low alumina quartz normative tholeiitic lava flows of Chemical Type - B; 1283–1124°C for tholeiitic lava flows of Chemical Type - F and 1243°C and 99O°C for two diopside olivine normative tholeiite flows of Chemical Type D. High olivine normative flows of Chemical Type - G and H show 1095°C and 1092°C respectively. Whereas, high hypersthene normative tholeiite flow of Chemical me C shows temperature of 1187°C. Data plots disposition over iron-titanium oxide equilibration temperature vs – logfo₂, diagram for Mandla lava flows and other parts of the Deccan (Igatpuri, Mahabaleshwer, Nagpur and Sagar areas) revealed that tholeiitic (evolved) basalt of the eastern Deccan volcanic province formed at high temperatures whereas, picritic (primitive) lavas of Igatpuri and tholeiitic basalt of Mahabaleshwar areas were formed at low temperatures. Mahabaleshwer basalts follow FMQ (fayalite-magnetite-quartz) buffer curve but, plots of the Mandla basalts lie above this curve indicating higher temperatures of crystallisation of ilmenite-titanomagnetite than that of the lava flows from other parts of Deccan 'Raps. The eastern Deccan Traps are most evolved types of lava as characterised by its low Mg-number and Ni content whereas, Igatpuri lava flows are picritic (primitive), having high Mg-number and Ni contents. Temperature vs FeO + Fe₂O₃ / FeO + Fe₂O₃ + MgO ratio data plots for Mandla and other Deccan lava flows and liquidus data for Hawaiian tholeiites, indicated that Igatpuri basalts lie parallel to the liquidus line of Hawaiian tholeiite but at lower temperatures. Large data plots of Mandla lava flows lie along the liquidus line of the Hawaiian lava. The highly vesicular nature of compound lava flows having large amount of volatile is responsible for low temperature values whereas, lava flows represented by high temperatures show high modal values of glass and opaque minerals.     

Basalt magmatism along the passive continental margin of SE Brazil (Campos basin)

The SE-Brazil passive continental margin is characterized by tholeiitic magmatism that is particularly widespread in the marginal Campos basin, facing the inland flood basalts of the adjacent Paranà basin. Campos magmatism is represented by Early Cretaceous (EC; 134–122 Ma) flood basalts and minor Upper Cretaceous-Early Tertiary basalt flows and intrusives, which were emplaced in a basin with attenuated crustal thickness (20 km). Petrography, mineral chemistry, wholerock geochemistry and Sr–Nd isotope composition emphasize that the EC-Campos basalts have suffered extensive seawater interaction which caused enrichment in MgO, FeO total, K₂O, Rb and Ba, and depletion in SiO₂ and CaO, while Zr, Nb, Y and REE remained virtually constant in samples with loss-on-ignition values less than 4 wt%. In general, Campos basalts have bulkrock chemistry similar to those of the inland Parana tholeiites (140–130 Ma) with relatively low concentrations of incompatible elements and TiO₂ (<2 wt%). Batch-melting calculations suggest that Campos basalt genesis requires a garnet-peridotite source and variable degree of melting (9–25%) in order to explain the rare-earth-element (REE) patterns with chondrite normalised La/Yb_(N) ratio ranging from 0.9–1.0 to 4.4–7.1. The Sr–Nd isotopic data for the slightly altered Campos basalts, of both Early Cretaceous and Upper Cretaceous-Early Tertiary age, plot close to bulk earth, or in the enriched quadrant of the mantle array. Inter-element (La, Zr, Nb, Ba) ratios preclude for the Campos (and Paranà) basalt genesis any significant participation of N-type (Zr/Nb>16) MORB (mid-ocean-ridge basalt) mantle in simple binary mixing models. On the whole, the Early Cretaceous Campos basalts appear as an easterly, younger extension of the northern Paranà volcanism and probably erupted during early stages of the major riftingprocesses which caused continental thinning. It is notable that in the Campos marginal basin both the basalt magmatism contemporaneous with the continental break-up, as well as that which occurred after the S. America-Africa separation, appears substantially related to subcontinental lithosphere and a Dupal-like OIB (ocean-island basalt) (e.g. Tristan da Cunha) source components.     

Sur la présence de tholéiites à l'île Saint-Paul (Océan Indien)

The basalts and dolerites from Saint-Paul island, located on the east section of the Indian ridge, are reinvestigated. New chemical rock analysis show that they are caracterized by high Fe, low Mg, and various Al contents; they belong to quartz tholeiites and olivine tholeiites of Yoder and Tilley's classification. Two clinopyroxene analysis allow to confirm this tholeiitic relationship. Compared with abyssal tholeiites, those of Saint-Paul are dissimilar in respect to Al₂O₃/CaO and FeO/MgO ratios, Sr and Rb contents (231–308 ppm and 6 to 29 ppm respectively) and 87 Sr/86 Sr values (0,7041–0,7065). Bearing in mind the structural position of the island, this differences are discussed in light of experimental data. Saint-Paul's basalts and dolerites are products a magma fractionated according to a Fernner trend and probably issued from deeper part of the upper mantle than abyssal tholeiites.     

Description and interpretation of the composition of fluid and alteration mineralogy in the geothermal system,at Svartsengi,Iceland

The bulk composition and mineralogy of hydrothermally altered tholeiite, along with the composition and speciation of fluid, have been determined for a well-defined alteration zone at 240°C and 110 bars at Svartsengi, Iceland. Mass balances between the geothermal fluid and altered tholeiite, relative to a seawater/fresh water mixture and unaltered tholeiite, indicate the overall reaction per 1000 cm³ is: 1325 gm plagioclase + 1228 gm pyroxene + 215 gm oxide-minerals break down to form 685 gm chlorite + 636 gm albite + 441 gm quartz + 249 gm epidote + 266 gm calcite + 201 gm oxide-minerals + 15 gm pyrite, requiring an influx of 123 gm CO₂, 10 gm H₂S and 4 gm Na₂O and a release of 57 gm SiO₂, 35 gm FeO, 21 gm CaO, 8 gm MgO and 4 gm K₂O.Principal reactions, deduced from textural evidence, include Na-Ca exchange in plagioclase, precipitation of quartz, calcite and anhydrite, and formation of chlorite and epidote by reactions between groundmass minerals and fluid.Thermodynamic analyses of authigenic minerals and downhole fluid indicate that the fluid maintains a state close to equilibrium with the secondary mineral phases chlorite, epidote, albite, quartz, calcite, prehnite, anhydrite, pyrite and magnetite, whereas remnant primary labradorite and augite are out of equilibrium with the fluid.Water/rock ratios for the system are determined under a variety of assumptions. However, the open nature of the system makes comparisons with experimental and theoretical closed system studies ambiguous.     

Ocean floor metamorphism in the Betts Cove ophiolite,Newfoundland

The mineralogical and geochemical features of the lower Ordovician Betts Cove ophiolite of northeastern Newfoundland indicate that hydrothermal circulation of seawater near a mid-ocean ridge has been involved in the metamorphism of the complex. The degree of greenschist facies metamorphism increases with stratigraphie depth in the ophioli te. Calcite, hematite and epidote distributions show that the metamorphosing fluid penetrated downward and was reduced with depth. The mobilities of major and trace elements support the hypothesis of the interaction of seawater and basalt: Fe₂O₃, MgO, Na₂O and H₂O increase whereas CaO and Cu decrease in the rock after alteration; SiO₂, total iron, K₂O, Ba and Rb can either be depleted or enhanced in the altered material; TiO₂, P₂O₅, Zr, Y, Cr and Ni remain stable during the metamorphic episode. Finally, the occurrence of massive sulphides and incipient rodingitic gabbro is explicable in a circulatory seawater system.     

Pumpellyites and coexisting minerals in different low-grade metamorphic facies of Liguria, Italy

Pumpellyite from four-phase assemblages (pumpellyite + epidote + prehnite + chlorite; pumpellyite + epidote + actinolite + chlorite; pumpellyite + epidote + Na-amphibole + chlorite, together with common excess phases), considered to be low variance in a CaO-(MgO + FeO)-Al₂O₃-Fe₂O₃ (+Na₂O + SiO₂+ H₂O) system, have been examined in areas which underwent metamorphism in the prehnite-pumpellyite, pumpellyite-actinolite and low-temperature blueschist facies respectively. The analysed mineral assemblages are compared for nearly constant (basaltic) chemical composition at varying metamorphic grade and for varying chemical composition (basic, intermediate, acidic) at constant metamorphic conditions (low-temperature blueschist facies). In the studied mineral assemblages, coexisting phases approached near chemical equilibrium. At constant (basaltic) bulk rock composition the MgO content of pumpellyite increases, and the X_Fe3+ of both pumpellyite and epidote decreases with increasing metamorphic grade, the Fe³⁺ being preferentially concentrated in epidote. Both pumpellyite and epidote compositions vary with the bulk rock composition at isofacial conditions; pumpellyite becomes progressively enriched in Fe and depleted in Mg from basic to intermediate and acidic bulk rock compositions. The compositional comparison of pumpellyites from high-variance (1–3 phases) assemblages in various bulk rock compositions (basic, intermediate, acidic rocks, greywackes, gabbros) shows that the compositional fields of both pumpellyite and epidote are wide and variable, broadly overlapping the compositional effects observed at varying metamorphic grade in low-variance assemblages. The intrinsic stability of both Fe- and Al-rich pumpellyites extends across the complete range of the considered metamorphic conditions. Element partitioning between coexisting phases is the main control on the mineral composition at different P-T conditions.     

川西高原炉霍-道孚裂谷带丘洛地区科马提质岩的发现及其地质意义

川西高原炉霍-道孚裂谷带丘洛地区首次发现科马提岩,呈透镜状或团块状,具鬣刺结构,产于三江造山系巴颜喀拉地块之炉霍-道孚裂谷的三叠系如年各组玄武岩中。科马提岩由玄武质科马提岩、玄武岩、辉长岩、橄榄辉石岩等组成。岩石具富Mg O,贫Ca O、Al2O3和Fe2O3的特征,其Si O2含量为39.78%~49.85%,Mg O含量为23.28%~32.65%,Ti O2含量为0.21%~0.85%,K2O含量为0.04%~0.98%,P2O5含量为0.04%~0.12%,(Fe O+Fe2O3)/Mg O值为0.41~0.77,符合过渡型(T型)洋脊玄武岩特征,亦符合科马提岩各类元素的地球化学特征。原始地幔标准化的过渡元素配分型式表现为不对称的"W"型,Th元素形成一个明显的正异常"峰",Sr元素形成一个明显的负异常"谷",表明科马提岩系列可能来自于洋脊中心热幔柱,形成于低压高温条件下的部分熔融。岩石中鬣刺结构可能是叶蛇纹石高压分解的结果,表明研究区某些变质橄榄岩岩块曾经受过熔融物质喷发的影响。丘洛地区黄金资源丰富,研究具鬣刺结构的科马提岩岩石系列及其与矿产的关系,具有重要的经济价值。     

基于结构体的峨眉山玄武岩风化程度评价（Ⅳ）：风化指数FF

提要：岩石化学风化程度评价指标应该同时满足以下三个基本条件,即与风化程度之间的关系简单明确、对风化程度变化具有足够的敏感性和易于确定和不易受到人为因素影响。作为铁镁质岩石的主要代表,（峨眉山）玄武岩风化程度评价除考虑可引起组分淋失与富集的水解反应外,还应充分考虑二价铁的氧化反应。新鲜峨眉山玄武岩中并存的二价铁和三价铁的含量总体稳定,910个样品的FeO、Fe₂O₃平均含量分别为8.45%和5.15%,以均匀、随机的方式赋存于辉石、橄榄石、杏仁体中的绿泥石、磁铁矿及火山玻璃中。风化玄武岩、玄武岩斜坡地下水及新鲜玄武岩浸泡液的地球化学研究结果表明,FeO及Fe₂O₃含量对峨眉山玄武岩风化程度的敏感性明显高于其他组分,同时铁又是玄武岩风化过程中活动性最差的元素之一。三价铁和二价铁的摩尔数比值（FF）适合于峨眉山玄武岩整个风化过程的风化程度判别,比既有风化指数具有更高的分辨率,尤其是对风化初期玄武岩。     

Structural control and hydrothermal alteration at the BIF-hosted Raposos lode-gold deposit, Quadrilátero Ferrífero, Brazil

In the Raposos orogenic gold deposit, hosted by banded iron-formation (BIF) of the Archean Rio das Velhas greenstone belt, the hanging wall rocks to BIF are hydrothermally-altered ultramafic schists, whereas metamafic rocks and their hydrothermal schistose products represent the footwall. Planar and linear structures at the Raposos deposit define three ductile to brittle deformational events (D₁, D₂ and D₃). A fourth group of structures involve spaced cleavages that are considered to be a brittle phase of D₃. The orebodies constitute sulfide-bearing D₁-related shear zones of BIF in association with quartz veins, and result from the sulfidation of magnetite and/or siderite. Pyrrhotite is the main sulfide mineral, followed by lesser arsenopyrite and pyrite. At level 28, the hydrothermal alteration of the mafic and ultramafic wall rocks enveloping BIF define a gross zonal pattern surrounding the ore zones. Metabasalt comprises albite, epidote, actinolite and lesser Mg/Fe–chlorite, calcite and quartz. The incipient stage includes the chlorite and chlorite-muscovite alteration zone. The least-altered ultramafic schist contains Cr-bearing Mg-chlorite, actinolite and talc, with subordinate calcite. The incipient alteration stage is subdivided into the talc–chlorite and chlorite–carbonate zone. For both mafic and ultramafic wall rocks, the carbonate–albite and carbonate–muscovite zones represent the advanced alteration stage.Rare earth and trace element analyses of metabasalt and its alteration products suggest a tholeiitic protolith for this wall rock. In the case of the ultramafic schists, the precursor may have been peridotitic komatiite. The Eu anomaly of the Raposos BIF suggests that it was formed proximal to an exhalative hydrothermal source on the ocean floor. The ore fluid composition is inferred by hydrothermal alteration reactions, indicating it to having been H₂O-rich containing CO₂ + Na⁺ and S. Since the distal alteration halos are dominated by hydrated silicate phases (mainly chlorite), with minor carbonates, fixation of H₂O is indicated. The CO₂ is consumed to form carbonates in the intermediate alteration stage, in halos around the chlorite-dominated zones. These characteristics suggest variations in the H₂O to CO₂-ratio of the sulfur-bearing, aqueous-carbonic ore fluid, which interacted at varying fluid to rock ratios with progression of the hydrothermal alteration.     

Petrogenesis of picrite and associated basalts from the southern Mid-Atlantic Ridge

Basalts dredged from the south wall of a fracture zone transecting the southern Mid-Atlantic Ridge (SMAR) at 54° S are unusual in that they include a suite of highly olivine phyric basalts, sampled along with more normal sparsely plagioclase phyric basalts, and a highly plagioclase phyric basalt. Four basalt types (olivine phyric, sparsely plagioclase phyric, evolved sparsely plagioclase phyric and highly plagioclase phyric) are readily distinguished on the basis of petrography, mineralogy and bulk composition. They range from primitive to evolved, with the olivine phyric basalts having elevated MgO (up to 15.5%) and the plagioclase phyric basalt having elevated Al₂O₃ (19.3%) and CaO (13.1%) contents. Compositional variations are extremely consistant, with the olivine phyric basalts and the sparsely plagioclase phyric basalts defining coherent linear trends. On the basis of the ratios and covariation of the incompatible trace elements Zr, Nb, Y and Ba, distinct parental magmas for each basalt type are required. An investigation of Fe-Mg and Mg-Ni distribution coefficients between olivine and magma indicates that olivines from the olivine phyric basalts are on average too forsteritic and too Ni poor to have crystallized in a magma corresponding to the host bulk rock composition. This implies that these basalts are enriched in xenocrystic olivine. Olivines from the other basalt types are mostly of equilibrium composition, although there are some exceptions. Petrogenetic models for the formation of the different basalt types are quantitatively evaluated in terms of fractional crystallization/crystal accumulation processes. These indicate that (1) the olivine phyric basalts are the products of olivine and minor Cr-spinel accumulation and do not represent analogues of primary magma, or a liquid fractionation trend; (2) that the sparsely plagioclase phyric basalts were formed by polybaric fractional crystallization of olivine, plagioclase and clinopyroxene; and (3) that the evolved sparsely plagioclase phyric basalts are not readily related to one another. The single highly plagioclase phyric basalt is unrelated to the other basalt types and is cumulus enriched in plagioclase.The different basalt types are unrelated to one another and document the presence of at least four distinct magma types erupted in close proximity at this ridge/transform intersection on the southern end of the Mid-Atlantic Ridge.     

Iron/manganese ratio and manganese content in shield lavas from Ko’olau Volcano, Hawai’i

Precise Fe/Mn ratios and MnO contents have been determined for basalts from the Hawaiian shields of Ko’olau and Kilauea by inductively coupled plasma mass spectrometry. It is well known that the youngest Ko’olau (Makapu’u-stage) shield lavas define a geochemical endmember for Hawaiian lavas in terms of CaO and SiO₂ contents and isotopic ratios of O, Sr, Nd, Hf, Pb, and Os. We find that their MnO content is also distinct. Despite the small range in MnO, 0.146 to 0.176 wt%, the precision of our data is sufficient to show that among unaltered Ko’olau lavas MnO content is correlated with Nd-Hf-Pb isotopic ratios, La/Nb and Al₂O₃/CaO elemental ratios, and contents of SiO₂, MgO and Na₂O + K₂O adjusted for olivine fractionation. These trends are consistent with two-component mixing; one endmember is a SiO₂-rich, MnO-, and MgO-poor dacite or andesite melt, generated by low degree (10-20%) partial melting of eclogite. Since this low-MgO endmember (dacite or andesite melt) has very low FeO and MnO contents, mixing of high Fe/Mn dacite or andesite melt with a MgO-rich picritic melt, the other endmember, does not significantly increase the Fe/Mn in mixed magmas; consequently, Ko’olau and Kilauea lavas have similar Fe/Mn. We conclude that the high Fe/Mn in Hawaiian lavas relative to mid-ocean ridge basalt originates from the high MgO endmember in Hawaiian lavas.     

Neoproterozoic hydrothermally altered basaltic rocks from Rajasthan, northwest India: Implications for late Precambrian tectonic evolution of the Aravalli Craton

The isolated volcano-sedimentary sequences of the Punagarh and Sindreth Groups occur along the western flank of the Delhi Fold Belt in northwest India, and include mafic rocks (pillow basalts and dolerite dykes) that are dominantly olivine tholeiites with minor quartz-normative and alkali basalts. Sindreth samples appear to have higher primary TiO₂ and P₂O₅ abundances relative to those from Punagarh. Both suites of mafic rocks show variable, but profound hydrothermal alteration effects, with loss on ignition (LOI) values up to 10.3 wt.%, and extensive secondary minerals including albite, sericite, chlorite and calcite. Despite this, there is excellent preservation of magmatic textures, but there has been extensive albitization of plagioclase phenocrysts, a hallmark of hydrothermal alteration processes in oceanic crust. Supporting evidence for such hydrothermal alteration comes from correlations of LOI abundances with CaO/Na₂O, and evidence for U mobility is apparent on diagrams of Nb/Th vs. Nb/U. Felsic volcanic rocks (rhyolite, dacite) interlayered with the Sindreth basalts yield U–Pb zircon ages (TIMS method) between 761 ± 16 and 767 ± 3 Ma, which we interpret as representing the time of primary magmatic activity. We infer that the volcano-sedimentary rocks of the Punagarh also formed at this time, on the basis of similarities in lithology, stratigraphy, field relations and geochemistry. Intermediate granitoid rocks yield older U–Pb ages of 800 ± 2 and 873 ± 3 Ma, which we correlate with the post-Delhi Supergroup Erinpura Granites. Taken together, the features of the Punagarh and Sindreth Groups are consistent with their formation in a back-arc basin setting. Their coevality with other magmatic systems in NW India (Malani Igneous Suite), the Seychelles and Madagascar, for which a continental arc setting has also been proposed, supports the notion of an extensive convergent margin in western Rodinia at 750–770 Ma.     

Synthesis of Fe-pumpellyite and its stability relations with epidote

Hydrothermal synthesis of Fe-pum-pellyites was conducted using high pressure cold-seal apparatus and solid oxygen buffering techniques at temperatures between 250°C and 550°C and 2.0–9.1 kbar P_fluid. Fe-pumpellyites were synthesized from partially crystalline gel mixtures of compositions: 4CaO - 2.1Al₂O₃_1.5FeO - 0.3MgO - 6SiO₂ (II) and 3CaO - 1.5 Al₂O₃ - 2.7FeO - 0.3MgO - 6SiO₂ (III) in the presence of excess H₂O at P_fluid of 5–9.1 Kbar, temperatures between 275°C and 325°C, and f_O2 defined by the QFM and HM buffers; for both of these compositions (II and III), the condensed synthetic run products included minor 7Å chlorite ± garnet ± Fe-oxide. The cell dimensions and aggregate refractive index (a= 19.13(2)Å, b= 5.940(4)Å, c= 8.847(5)Å, ±= 97.37(6)±, and n= 1.702(2)) of the pum-pellyite synthesized from the bulk composition II mix are compatible with those of natural pumpellyites containing similar total Fe contents. Attempts at synthesizing Fe-pumpellyites from a Mg-free bulk composition were not successful; these results are consistent with the total absence of natural Mg-free pumpellyites. The higher temperature, higher oxygen fugacity assemblages of the equivalent bulk compositions (II and III) consist of epidote ± minor amounts of chlorite, garnet, quartz, hematite, and magnetite. The results of these synthesis experiments accord with the mineral parageneses observed in low-grade metabasites which imply that Fe-pumpellyites are replaced by epidote with increasing temperature and/or f_O2 and that Fe³⁺ is preferentially partitioned into epidote with respect to coexisting pum-pellyite. In addition, these synthesis experiments indicate that Fe-bearing pumpellyites crystallize at and are stable to lower temperatures than more aluminous pumpellyites—a result also consistent with natural systems.     

Geochemistry of the Siberian Trap of the Noril'sk area,USSR, with implications for the relative contributions of crust and mantle to flood basalt magmatism

The sequence investigated of the Siberian Trap at Noril'sk, USSR, consists of at least 45 flows that have been divided into six lava suites. The lower three suites consist of alkalic to subalkalic basalts (the Ivakinsky suite), overlain by nonporphyritic basalts (the Syverminsky suite), and porphyritic and picritic basalts (the Gudchikhinsky suite). The upper three suites are tholeiitic. The uppermost 750 m of dominantly non-porphyritic basalt belong to the Mokulaevsky suite and are characterized by a nearly constant Mg number (0.54–0.56), SiO₂ (48.2–49.1 wt%), Ce (12–18 ppm), and Ce/Yb (5–8). The underlying 1100 m of dominantly porphyritic basalt belong to the Morongovsky and Nadezhdinsky suites. There is a continuous increase in SiO₂ (48.1–55.2 wt%), Ce (12–41 ppm), and Ce/Yb (5–18) from the top of the Mokulaevsky to the base of the Nadezhdinsky with little change in the Mg number (0.53–0.59). Mokulaevsky magmas have trace element signatures similar to slightly contaminated transitional type mid-ocean ridge basalts. The change in major and trace element geochemistry in the upper three suites is consistent with a decline in the degree of anatexis and assimilation of tonalitic upper crust by Mokulaevsky magma. The Nadezhdinsky and underlaying lavas thicken within and thus appear to be related to an elongate basin centred on the Noril'sk-Talnakh mining camp. The Mokulaevsky and Morongovsky lavas thicken to the east and appear to be related to a basin centred more than 100 km to the east of the Noril'sk region; these magmas may have risen up out of a different conduit system.     

Mangerite magmatism associated with a probable Late-Permian to Triassic Hongseong–Odesan collision belt in South Korea

The Odesan area in the eastern Gyeonggi Massif, South Korea, consists principally of migmatitic and porphyroblastic gneisses intruded by mangerite. Mafic mangerites with SiO₂ contents from 52.40 to 54.20 wt.% have higher FeO* + MgO (14.98–18.28 wt.%) and CaO contents (5.80–7.84 wt.%) but lower total alkali contents (4.74 < Na₂O + K₂O < 5.80 wt.%) than felsic mangerites (55.9 < SiO₂ < 60.61 wt.%, 9.51< FeO* + MgO < 11.62 wt.%, 3.28 < CaO < 5.68 wt.%, 6.72 < Na₂O + K₂O < 8.05 wt.%). Fe-numbers (FeO* / [MgO + FeO*]) are 0.44–0.47 for mafic mangerites and 0.38–0.42 for felsic mangerites. The mangerites show calc-alkaline affinities in an AFM plot and resemble high-Ba–Sr granitoids with low Rb / Sr ratios of 0.25–0.10. Their MORB-normalized compositions show enrichment in LILE (decoupled LIL/HFS pattern) and negative anomalies in Ti–Nb–Ta. Their geochemical characters are consistent with their formation by partial melting of a basaltic source at temperatures higher than 1025 °C. The mangerites of the present study differ from mangerite formed in a typical within-plate tectonic setting in their high mg# and Sr concentrations and negative Nb and Ta anomalies. Their LILE enrichment and negative Ti–Nb–Ta anomalies could well have been inherited from a pre-collision subduction event. A mean U–Pb zircon age of 257 Ma for the mangerite demonstrates that the tectonic belt connecting the Hongseong and Odesan areas represents a probable extension of the late Permian–Triassic collision belt between the North China and South China blocks into South Korea, with collision occurred earlier in South Korea.     

Composition and age of tertiary sills and dykes, Jameson Land Basin, East Greenland: relation to regional flood volcanism

The Paleozoic–Mesozoic Jameson Land Basin (East Greenland) is intruded by a sill complex and by a swarm of ESE trending dykes. Together with dykes of the inner Scoresby Sund fjord, they form a regional Early Tertiary intrusive complex located 200–400 km inland of the East Greenland rifted continental margin. Most of the intrusive rocks in the Jameson Land Basin are geochemically coherent and consist of evolved plagioclase–augite–olivine saturated, uncontaminated high-Ti basalt with 48.5–50.2 wt.% SiO₂, 2.2–3.2 wt.% TiO₂, 5.1–7.4 wt.% MgO, 9–17 ppm Nb and La/Yb_N=2.8–3.6. Minor tholeiitic rock types are: (a) low-Ti basalt (49.7 wt.% SiO₂, 1.7 wt.% TiO₂, 6.8 wt.% MgO, 2.6 ppm Nb and La/Yb_N=0.5) akin to oceanic basalts; (b) very-high-Ti basalt (48.6 wt.% SiO₂, 4.1 wt.% TiO₂, 5.1 wt.% MgO and 21 ppm Nb); and (c) plagioclase ultraphyric basalt. The tholeiitic dolerites are cut by alkali basalt (43.7–47.3 wt.% SiO₂, 4.1–5.1 wt.% TiO₂, 4.9–6.2 wt.% MgO, 29–46 ppm Nb and La/Yb_N=16–17) sills and dykes.Modelling of high-field-strength and rare-earth elements indicate that the high-Ti basalts formed from 6–10% melting of approximately equal proportions of garnet- and spinel-bearing mantle of slightly depleted composition beneath thick continental lithosphere. Conversely, dolerite intrusions and flood basalts of similar compositional kindred from adjacent but more rift-proximal occurrences in Northeast Greenland formed from shallower melting of dominantly spinel-bearing mantle beneath extended and thinned continental lithosphere. These variations in lithospheric thickness suggest the continent–ocean transition of the East Greenland rifted volcanic margin is sharp and narrow.⁴⁰Ar–³⁹Ar dating and paleomagnetism show that the high-Ti dolerites were emplaced at 53–52 Ma (most likely during C23r) and hence surprisingly postdate the main flood volcanism by 2–5 Ma and the inception of seafloor spreading between Greenland and Europe by 1–2 Ma. The formation of tholeiitic and alkaline magmas emplaced into the Jameson Land Basin corroborates to the importance of post-breakup magmatism along the East Greenland volcanic rifted margin. Upwelling of the ancestral Iceland mantle plume under central Greenland at 53–52 Ma (rather than under the active rift), perhaps accompanied by a failed attempt to shift the rift zone westward towards the plume axis, may have triggered post-breakup continental magmatism of the Jameson Land Basin and the inner Scoresby Sund region, along preexisting structural lineaments.     

Origin of ultramafic xenoliths containing exsolved pyroxenes from Hualalai Volcano,Hawaii

Hualalai Volcano, Hawaii, is best known for the abundant and varied xenoliths included in the historic 1800 Kaupulehu alkalic basalt flow. Xenoliths, which range in composition from dunite to anorthosite, are concentrated at 915-m elevation in the flow. Rare cumulate ultramafic xenoliths, which include websterite, olivine websterite, wehrlite, and clinopyroxenite, display complex pyroxene exsolution textures that indicate slow cooling. Websterite, olivine websterite, and one wehrlite are spinel-bearing orthopyroxene +olivine cumulates with intercumulus clinopyroxene +plagioclase. Two wehrlite samples and clinopyroxenite are spinel-bearing olivine cumulates with intercumulus clinopyroxene+orthopyroxene + plagioclase. Two-pyroxene geothermometry calculations, based on reconstructed pyroxene compositions, indicate that crystallization temperatures range from 1225° to 1350° C. Migration or unmixing of clinopyroxene and orthopyroxene stopped between 1045° and 1090° C. Comparisons of the abundance of K₂O in plagioclase and the abundances of TiO₂ and Fe₂O₃in spinel of xenoliths and mid-ocean ridge basalt, and a single ⁸⁷Sr/ ⁸⁶Sr determination, indicate that these Hualalai xenoliths are unrelated to mid-ocean ridge basalt. Similarity between the crystallization sequence of these xenoliths and the experimental crystallization sequence of a Hawaiian olivine tholeiite suggest that the parental magma of the xenoliths is Hualalai tholeiitic basalt. Xenoliths probably crystallized between about 4.5 and 9 kb. The 155°–230° C of cooling which took place over about 120 ka — the age of the youngest Hualalai tholeiitic basalt — yield maximum cooling rates of 1.3×10^–3–1.91×10^–3 °C/yr. Hualalai ultramafic xenoliths with exsolved pyroxenes crystallized from Hualalai tholeiitic basalt and accumulated in a magma reservoir located between 13 and 28 km below sealevel. We suspect that this reservoir occurs just below the base of the oceanic crust at about 19 km below sealevel.     

Anhydrous PT phase relations of an Aleutian high-MgO basalt: an investigation of the role of olivine-liquid reaction in the generation of arc high-alumina basalts

We report results of anhydrous 1 atm and piston-cylinder experiments on ID16, an Aleutian high-magnesia basalt (HMB), designed to investigate potential petrogenetic links between arc high-alumina basalts (HABs) and less common HMBs. ID16 is multiply saturated with a plagioclase/spinel iherzolite mineral assemblage (olivine, plagioclase, clinopyroxene, orthopyroxene, spinel) immediately beneath the 12 kbar liquidus. Derivative liquids produced at high temperatures in the 10–20 kbar melting interval of ID16 have compositions resembling those published of many moderate-CaO HABs, although lower-temperature liquids are poorer in CaO and richer in alkalies than are typical HABs. Isomolar pseudoternary projections and numerical mass-balance modeling suggest that derivative melts of ID16 enter into a complex reaction relationship with olivine at 10 kbar and 1,200° C–1,150° C. We sought to test such a mechanism to explain the lack of liquidus olivine in anhydrous experiments on mafic high-alumina basalts such as SSS. 1.4 (Johnston 1986). These derivative liquids, however, do not resemble typical arc high-alumina basalts, suggesting that olivine-liquid reaction does not account for Johnston's (1986) observations. Instead, we suggest that olivine can be brought onto the liquidus of such compositions only through the involvement of H₂O, which will affect the influence of bulk CaO, MgO, and Al₂O₃ contents on the identity of HAB liquidus phases (olivine or plagioclase) at pressures less than 12 kbar.