Depository of Reference for Earth and Analytical Materials
The following research papers were published through research activities of the Institute for Planetary Materials, Okayama University. By clicking the title of a paper, you can refer to the information on the substance sample that the paper targeted. It may take some time to display if the paper handles many samples.
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For decades, deep sea hydrothermal vents have been a preferred setting for the Origin of Life, but “The Water Problem” as relates to polymerization of organic molecules, together with a propensity to dilute critical prebiotic elements as well as a number of other crucial factors, suggests that a terrestrial hot spring field with the capacity for wet–dry cycling and element concentration may represent a more likely candidate. Here, we investigate a 3.5 billion-year-old, anoxic hot spring setting from the Pilbara Craton (Australia) and show that its hydrothermal veins and compositionally varied pools and springs concentrated all of the essential elements required for prebiotic chemistry (including B, Zn, Mn, and K, in addition to C, H, N, O, P, and S). Temporal variability (seasonal to decadal), together with the known propensity of hot springs for wet–dry cycling and information exchange, would lead to innovation pools with peaks of fitness for developing molecules. An inference from the chemical complexity of the Pilbara analogue is that life could perhaps get started quickly on planets with volcanoes, silicate rocks, an exposed land surface, and water, ingredients that should form the backbone in the search for life in the Universe.
• The fine-sized mica in Allophanic Andosols is not originated from volcanic ashes. • The δ18O values of fine-quartz in the Andosols is similar to those of Asian dust. • The quartz content associatively increased with mica as further away from a volcano. • Asian-dust-derived mica is crucial to increase RCs retention ability in Andosols. Deposition of Asian dust, i.e. mica-bearing aeolian particles, throughout geological times has contributed greatly to the increased ability of soil to specifically retain radiocesium (137Cs), particularly in soils derived from mica-deficient parent materials. Allophanic Andosols, volcanic mica-deficient soils, in Japan were hypothesized to contain fewer micaceous minerals proximal to volcanoes due to the dilution of Asian dust by thicker volcanic ash depositions. To test this hypothesis, we collected soils from stratified horizons mainly composed of mafic volcanic ash at four sites near the volcanic crater of Mt. Aso, Japan. The profiles were in volcanic ash soil dominated by poorly ordered clay minerals, and classified as Allophanic Andosols. Radiocesium interception potential (RIP) and mineral content were determined on soil particles fractionated to < 20 µm effective spherical diameter. The RIP for these particles ranged widely from < 0.1 to 4.5 mol kg soil−1, showed a strong-positive correlation with mica and quartz content, and increased with distance away from the crater. Isolated quartz grains, ranging from 2 to 20 µm, were analyzed for oxygen isotopic ratio (δ18O) as an indicator of Asian dust contribution. The average δ18O was 16.0 ± 0.4‰, very close to those of fine quartz in the Gobi Desert, while clearly differentiated from high temperature formation environments of SiO2 grains from volcanic origins, δ18O < 10‰. Results showed that RIP of Allophanic Andosols is primarily controlled by the proportion of Asian dust incorporated into volcanic ashes, which increased with distance from the main volcanoes. These findings improve predictions of the spatial distribution patterns soil radio cesium (RC) and the soil-to-plant transfer of RCs in Andosols in Japan.
The first experimental data were obtained on the distribution of boron isotopes between gas and liquid at 100–350°С and the pressure of saturated water vapor, and the effect of pH on this distribution at 100°С was studied. The results showed that the value of δ11Bgas – δ11Bliquid was 5.9, 3.7, 1.1, 0.8, and –1.3 ‰ at 100, 200, 250, 300, and 350°С. In an alkaline solution, the boron distribution coefficient between gas and liquid decreases, and the isotopic shift increases; at 100°C and pH 9.1 it is 17.0. The isotopic composition of the boron of thermal waters of the Mutnovsky geothermal system (Kamchatka Peninsula, Russia) was investigated. In thermal springs, a large spread of δ11B values from 2.8 to 18‰ was determined. A wide range of isotopic compositions can be explained by the fractionation of boron between gas and liquid.
Southwest Japan is an island arc formed by subduction of the Philippine Sea (PHS) plate. The Quaternary magmatism in this region is characterized by eruptions of high‐Sr andesites and dacites, considered to have been derived by melting of the PHS plate. The loci of these volcanoes spatially coincide with seismic discontinuities of the subducted PHS plate. Thus the magmatism is interpreted as the result of slab melting at the plate tears. However, the processes that promote slab tearing remain unclear. In this study, we applied geochronological and geochemical analyses to late Cenozoic volcanic rocks in southwest Japan as tracers of slab morphology. Two different magma types, ocean‐island basalt (OIB) and island‐arc basalt (IAB), have occurred over 12 million years (Myrs). These two magmas are attributed to different integrations of melts extracted from an originally fertile mantle; the OIB from high temperature melt (1300–1400 °C) extracted at a depth of 40–80 km, whereas the IAB were extracted from a shallower, lower temperature region (30–60 km, 1200–1350 °C). Secular change in Sr enrichment of IAB likely arose due to a transition of slab‐derived fluids, incorporated into magmas as they formed, from water‐ to melt‐dominant one. Progressive shallowing of the subducted PHS plate is responsible for secular change in the properties of slab‐derived fluids as well as rollback of OIB volcanoes. Production of chemically variable magmas in the Chugoku district is the surface expression of distorting slab morphology by interaction between mantle and the subducting plate.
In a recent article in this journal, Ghoshmaulik et al (2020) described technical modifications to a long‐established laser‐assisted fluorination procedure for extracting and purifying molecular oxygen from silicates, prior to triple‐isotope ratio analysis. Although the reported respective measurement precisions for δ17O and δ18O values, at 0.040‰ and 0.080‰, are identical to those reported more than 20 years ago, Miller MF et al (1999) using a similar (but not identical) system and protocol, the very tight coupling of δ17O and δ18O measurement errors in the new method permits the determination of Δ′17O values * to a precision of 4 ppm, or even less. All precision values discussed herein refer to one standard deviation (σ). The description of how Ghoshmaulik et al (2020) achieved such precise Δ′17O values is a welcome contribution to the increasing number of reports quantifying small but distinctive variations between the relative abundances of 17O and 18O in terrestrial silicate rocks and minerals.
Subduction processes introduce crustal materials into the mantle, while mantle plumes return them back to the surface. However, when and how the subducted materials were recorded in the plume-related basalts remains unclear. Here we investigated geochronology, bulk-rock composition, and Sr-Nd-Pb isotopes of Cenozoic basalts from Southeast China, occurring near the west Pacific subduction zone and the seismically detected Hainan plume. Volcanism beginning in the late Oligocene in the continental margin of SE China consistently becomes younger landward. Together with a compilation of published results of the synchronous basalts from the South China Sea seamounts and the Indochina peninsula, the volcanoes close to the Pacific subduction zone exhibit more radiogenic Pb and Sr isotopes associated with less radiogenic Nd isotopes compared to those of the inland volcanoes. Such spatiotemporal variations in radiogenic isotopes imply oceanic crusts of different ages in the source, each corresponding to a different geographical volcanic belt. Major-element features such as low CaO, high TiO2 and high Fe/Mn ratios imply that pyroxenite/eclogite could serve as a source lithology of the SE China basalts. Specific trace element signatures reveal the important roles of recycled oceanic crust along with surface sediment, which was inconsistently dehydrated during subduction. A geologically, geochemically, and geophysically plausible scenario is proposed to illustrate the time-space-source correlation of the late Cenozoic basaltic lavas in SE Asia. The Hainan plume delivered the ancient subducted crust (1.5 Ga) from the core-mantle boundary and, subsequently, the subducted Pacific plate crustal materials from the mantle transition zone to the shallow mantle as a result of mantle convection induced by continuous subduction of the Pacific plate. Such recycled materials of different ages contributed to the geographic compositional heterogeneities of the late Cenozoic basaltic lavas in SE Asia.
The Hayabusa2 mission successfully collected samples from the asteroid Ryugu last year and will return these to Earth in December 2020. It is anticipated that the samples will enable the analysis of terrestrially uncontaminated organic matter and minerals. Such analyses are in turn expected to elucidate the evolution of organic matter through Solar System history, including the origination and processing of biogenically important molecules, which could have been utilized by the first organisms on Earth. In anticipation, studies have made predictions concerning the properties of Ryugu, including its composition. The spectral characteristics of Ryugu, such as albedo, have been employed to relate the asteroid to members of the carbonaceous chondrite group that have been identified on Earth. However, the recent Hayabusa2 touchdown highlights a disparity between the color of surfaces of displaced platy fragments, indicating a brightening trend for the surface exposed to space compared to that facing into the body. Here we present a mass balance calculation with reference to data from the literature, which indicates that Ryugu may contain a significantly higher abundance of organic matter (likely >50%) than the currently most accepted meteorite analogues. A high organic content may result in high levels of extractable organic matter for the second touchdown site, where the spacecraft sampled freshly exposed material. However, high abundances of insoluble aromatic/graphitic rich organic matter may be present in the first touchdown site, which sampled the surface of Ryugu that had been exposed to space. Moreover, we suggest that the potentially high organic abundance and the rubble-pile nature of Ryugu may originate from the capture of rocky debris by a comet nucleus and subsequent water-organic-mineral interactions and sublimation of water ice.
Carbonaceous chondrites contain many abiotic organic compounds, some of which are found in life on Earth. Both the mineral and organic matter phases, of these meteorites, have been affected by aqueous alteration processes. Whilst organic matter is known to be associated with phyllosilicate phases, no such relationship has yet been identified for specific organic compound classes. Furthermore, ongoing sample return missions, Hyabusa 2 and OSIRIS-Rex, are set to return potentially organic rich C-type asteroid samples to the Earth. Consequently, strategies to investigate organic-mineral relationships are required. Here we report spatial data for free/soluble organic matter (FOM/SOM) components (akylimidazole and alkylpyridine homologues) and mineral phases. Low and intermediate molecular weight alkylimidazole homologues are more widely distributed than higher molecular weight members, likely due to their affinity for the aqueous phase. On aqueous alteration of anhydrous mineral phases, transported FOM is adsorbed onto the surface or into the interlayers of the resulting phyllosilicates and thus concentrated and protected from oxidising fluids. Therefore, aiding the delivery of biologically relevant molecules to earth, shortly preceding the origin of life.
Felsic magmas produced at subduction zones have played an important role in the generation and evolution of the continental crust. For the origin of felsic magmas, processes such as fractional crystallization of mafic magmas, partial melting of crustal materials, partial melting of subducting slabs, and partial melting of pyroxenitic mantle wedge components have been proposed. Recent experimental studies have predicted that felsic melt can also be produced in the mantle wedge by the separation of slab-derived supercritical liquid beyond depths corresponding to the critical point. To date, however, the presence of felsic magma of this origin has not yet been reported. In this study, we investigated dacitic lavas and preceding calc-alkaline andesite lavas from the Rishiri Volcano, located at the rear of the Kuril arc. We show that hydrous felsic melt and aqueous fluid were separated from slab-derived supercritical liquid in the mantle wedge. The former erupted as dacitic magma whilst the aqueous fluid induced the generation of primary basaltic magma involved in creating calc-alkaline andesite magma. We infer that slab-derived supercritical liquid is an efficient transport medium for moving silicate-rich components from subducting slabs to the Earth’s surface, and that this process may have contributed to the growth of the continental crust.
The geochemical variabilities in intraplate basalts (IB) from the West African passive margin (WAPM) region, have generally been employed to indicate the presence of recycled materials in an associated upwelling mantle plume. However, the absence of time-progressive linear hotspot tracks in WAPM-IB make it difficult to explain their genesis solely by the mantle plume hypothesis. Here, we show that the Sr–Nd–Hf–Pb isotopic variations in basalts from most of the WAPM-IB could have mainly attributed to the derivation from two types of fusible regions of the refertilized subcontinental lithospheric mantle (SCLM) and the sub-lithospheric mantle. The locations and magma genesis of WAPM-IB are strongly related to the distance from the Mesozoic rift axis and the structure of the rifted SCLM. The melting of the source region can possibly be attributed to small-scale mantle convection at the base of the SCLM without the involvement of a mantle plume.
New K-Ar ages, major and trace element concentrations, and Sr-Nd-Pb isotope data are presented for Oligocene to recent mafic volcanic rocks from the Ethiopian Plateau, the Main Ethiopian Rift (MER), and the Afar depression. Chronological and geochemical data from this study are combined with previously published data sets to reveal secular variations in magmatism throughout the entire Ethiopian volcanic region. The mafic lavas in these regions show variability in terms of silica-saturation (i.e., alkaline and sub-alkaline series) and extent of differentiation (mafic through intermediate to felsic). The P-T conditions of melting, estimated using the least differentiated basalts, reveal a secular decrease in the mantle potential temperature, from when the flood basalt magmas erupted (up to 1550 °C) to the time of the rift-related magmatism ( < 1500 °C). Variations in the Sr-Nd-Pb isotopic compositions of the mafic lavas can account for the involvement of multiple end-member components. The relative contributions of these end-member components vary in space and time owing to changes in the thermal condition of the asthenosphere and the thickness of the lithosphere. The evolution of the Ethiopian rift is caused by a transition from plume-driven to plate-driven mantle upwelling, although the present-day mantle beneath the MER and the Afar depression is still warmer than normal asthenosphere.
Platinum-group element (PGE) geochemistry may be used to constrain the timing of sulfide saturation in magmas, which influences the Cu and Au fertility of evolving magmatic systems. We report new geochronological and geochemical data, with emphasis on PGE geochemistry, for a suite of regional porphyritic hornblende–diorite intrusions and ore-bearing porphyries from the super-giant Escondida and smaller Zaldivar Cu deposits of Northern Chile. The regional dioritic intrusions have zircon U–Pb ages between 39.6 to 37.1 Ma, which overlap with the ages of the ore-bearing Escondida and Zaldivar porphyries (38.1 to 35.0Ma). Whole-rock major and trace element, and Sr–Nd–Pb and zircon O–Hf isotope geochemistry indicate that the regional diorites and ore-bearing porphyries are co-magmatic and originated from the same mantle-derived magma by fractional crystallization, with minor contamination by Paleozoic crust (∼10%). The low concentrations of PGE in the regional diorites show that they reached sulfide saturation before the MgO content of the melt fell to 4.7wt %, the MgO content of the most primitive sample analysed. The fraction of sulfide melt which separated from the melts that formed the regional diorites is estimated to be ∼0.12wt %; this resulted in the partitioning of highly chalcophile elements (Au and PGE) into a sulfide phase that was retained in cumulus rocks at depth. However, the fraction of sulfide melt was too low to have a significant effect on the Cu content of the fractionating melt. As a consequence, when the evolving melt eventually reached volatile saturation, it contained enough Cu (40 ± 10 ppm) to form a super-giant Cu deposit. In contrast, Au was largely stripped from the melt by sulfide precipitation, with the result that the mineralization at Escondida is Cu dominant, with only minor Au. The Zaldivar deposit, on the other hand, contains even less Au, which is attributed to a longer fractionation interval between sulfide and volatile saturation. This study provides evidence to support previously proposed models which suggest that the timing of sulfide saturation, the amount of sulfide melt produced, the water content and oxidation state of the melt, and the magma volume are critical factors in determining the potential to form a porphyry Cu deposit. Plots of Pd/MgO against Y can be used as empirical indicators of magma fertility for porphyry mineralization, and to discriminate between Cu–Au and Cu-dominated systems, but cannot predict the size of the deposit. The super-giant status of the Escondida deposit is attributed to it being underlain by a large batholith with a calculated minimum mass of 1012 tonnes (∼400km3).
Northwest Africa (NWA) 6704 is a unique achondrite characterized by a near-chondritic major element composition with a remarkably intact igneous texture. To investigate the origin of this unique achondrite, we have conducted a combined petrologic, chemical, and 187Re–187Os, O, and Ti isotopic study. The meteorite consists of orthopyroxene megacrysts (En55–57Wo3–4Fs40–42; Fe/Mn=1.4) up to 1.7cm in length with finer interstices of olivine (Fa50–53; Fe/Mn=1.1–2.1), chromite (Cr# ∼0.94), awaruite, sulfides, plagioclase (Ab92An5Or3) and merrillite. The results of morphology, lattice orientation analysis, and mineral chemistry indicate that orthopyroxene megacrysts were originally hollow dendrites that most likely crystallized under high super-saturation and super-cooling conditions (1–102°C/h), whereas the other phases crystallized between branches of the dendrites in the order of awaruite, chromite→olivine→merrillite→plagioclase. In spite of the inferred high super-saturation, the remarkably large size of orthopyroxene can be explained as a result of crystallization from a melt containing a limited number of nuclei that are preserved as orthopyroxene megacryst cores having high Mg# or including vermicular olivine. The Re–Os isotope data for bulk and metal fractions yield an isochron age of 4576±250 Ma, consistent with only limited open system behavior of highly siderophile elements (HSE) since formation. The bulk chemical composition is characterized by broadly chondritic absolute abundances and only weakly fractionated chondrite-normalized patterns for HSE and rare earth elements (REE), together with substantial depletion of highly volatile elements relative to chondrites. The HSE and REE characteristics indicate that the parental melt and its protolith had not undergone significant segregation of metals, sulfides, or silicate minerals. These combined results suggest that a chondritic precursor to NWA 6704 was heated well above its liquidus temperature so that highly volatile elements were lost and the generated melt initially contained few nuclei of relict orthopyroxene, but the melting and subsequent crystallization took place on a timescale too short to allow magmatic differentiation. Such rapid melting and crystallization might occur as a result of impact on an undifferentiated asteroid. The O–Ti isotope systematics (Δ17O=−1.052±0.004, 2 SD; ε50Ti=2.28±0.23, 2 SD) indicate that the NWA 6704 parent body sampled the same isotopic reservoirs in the solar nebula as the carbonaceous chondrite parent bodies. This is consistent with carbonaceous chondrite-like refractory element abundances and oxygen fugacity (FMQ=−2.6) in NWA 6704. Yet, the Si/Mg ratio of NWA 6704 is remarkably higher than those of carbonaceous chondrites, suggesting significant nebular fractionation of forsterite in its provenance.
To precisely determine the abundances of fifty-two elements found within natural water samples, with mass fractions down to fg g-1 level, we have developed a method which combines freeze-drying pre-concentration (FDC) and isotope dilution internal standardisation (ID-IS). By sublimation of H2O, the sample solution was reduced to < 1/50 of the original volume. To determine element abundance with accuracy better than 10%, we found that for solutions being analysed by mass spectrometry the HNO3 concentration should be > 0.3 mol l-1 to avoid hydrolysis. Matrix-affected signal suppression was not significant for the solutions with NaCl concentrations lower than 0.2 cg g-1 and 0.1 cg g-1 for quadrupole ICP-MS and sector field ICP-MS, respectively. The recovery yields of elements after FDC were 97-105%. The detection limits for the sample solutions prepared by FDC were ≤10 pg g-1, except for Na, K and Ca. Blanks prepared using FDC were at pg-1 level, except for eleven elements (Na, Mg, Al, P, Ca, Mn, Fe, Co, Ni, Cu and Zn). The abundances of fifty-two elements in bottled drinking water were determined from five different geological sources with mass fractions ranging from the fg g-1 to µg g-1 level with high accuracy.
We report in situ ion-microprobe analyses of Li- and O-isotope compositions for olivine, low-Ca pyroxene, high-Ca pyroxene, and chondrule mesostasis/plagioclase in nine chondrules from the Allende CV3 chondrite. Based on their mineralogy and O-isotope compositions, we infer that the chondrule mesostasis/plagioclase and ferroan olivine rims were extensively modified or formed during metasomatic alteration and metamorphism on the Allende parent asteroid. We excluded these minerals in order to determine the correlations between Li and both O and the chemical compositions of olivines and low-Ca pyroxenes in the chondrules and their igneous rims. Based on the O-isotope composition of the olivines, nine chondrules were divided into three groups. Average Δ17O of olivines (Fo>65) in group 1 and 2 chondrules are −5.3±0.4 and −6.2±0.4‰, respectively. Group 3 chondrules are characterized by the presence of 16O-rich relict grains and the Δ17O of their olivines range from −23.7 to −6.2‰. In group 1 olivines, as Fa content increases, variation of δ7Li becomes smaller and δ7Li approaches the whole-rock value (2.4‰; Seitz et al., 2012), suggesting nearly complete Li-isotope equilibration. In group 2 and 3 olivines, variation of δ7Li is limited even with a significant range of Fa content. We conclude that Li-isotope compositions of olivine in group 1 chondrules were modified not by an asteroidal process but by an igneous-rim formation process, thus chondrule olivines retained Li-isotope compositions acquired in the protosolar nebula. In olivines of the group 3 chondrule PO-8, we observed a correlation between O and Li isotopes: In relict 16O-rich olivine grains with Δ17O of −25 to −20‰, δ7Li ranges from −23 to −3‰; in olivine grains with Δ17O >−20‰, δ7Li is nearly constant (−8±4‰). Based on the Li-isotope composition of low-Ca pyroxenes, which formed from melt during the crystallization of host chondrules and igneous rims, the existence of a gaseous reservoir with a δ7Li ∼ −11‰ is inferred.
Seawater injection into chalk-reservoirs on the Norwegian Continental Shelf has increased the oil recovery and reduced seabed subsidence, but not eliminated it. Therefore, understanding rock–fluid interactions is paramount to optimize water injection, predict and control water-induced compaction. Laboratory experiments on onshore and reservoir chalks have shown the need to simplify the aqueous chemistry of the brine, and also the importance of studying the effect of primary mineralogy of chalk to understand which ions interact with the minerals present. In this study, the mineralogy of the samples tested, are simplified. These experiments are carried out on pure calcite powder (99.95%), compressed to cylinders, flooded with MgCl2, at 130°C and 0.5MPa effective stress, for 27 and 289 days. The tested material was analysed by scanning and transmission electron microscopy, along with whole-rock geochemistry. The results show dissolution of calcite followed by precipitation of magnesite. The occurrence and shape of new-grown crystals depend on flooding time and distance from the flooding inlet of the cylinder. Crystals vary in shape and size, from a few nanometres up to 2μm after 27 days, and to over 10μm after 289 days of flooding and may crystallize as a single grain or in clusters. The population and distribution of new-grown minerals are found to be controlled by nucleation- and growth-rates along with advection of the injected fluid through the cores. Our findings are compared with in-house experiments on chalks, and allow for insight of where, when, and how crystals preferentially grow.
A comprehensive geochemical study of the Chelyabinsk meteorite reveals further details regarding its history of impact-related fragmentation and melting, and later aqueous alteration, during its transit toward Earth. We confirmed an ∼30 Ma age for the impact-related melting, based on Rb-Sr dating of a melt domain. An irregularly shaped olivine with a distinct O isotope composition similar to R-chondrite, in a melt domain, appears to be a fragment of a silicate-rich impactor. Hydrogen and Li concentrations and isotopic compositions, textures of Fe oxyhydroxides, and the presence of organic materials located in fractures, are together consistent with aqueous alteration. Evaluation of H and Li isotope systematics suggests that the component of this alteration could have pre-dated interaction with the Earth’s atmosphere and surface reservoirs. As one model in which the alteration could reflect recent pre-terrestrial processes, we suggest that hypervelocity capture of the impact related debris by a comet nucleus could have led to shock-wave-induced supercritical aqueous fluids dissolving the silicate, metallic, and organic matter, with later ice sublimation yielding a rocky rubble pile sampled by the meteorite.
|How a comet turns into a rubble pile asteroid (a) By collision, a pre-existing asteroid gets shocked, melted, and fragmented within the last 30 million years. A comet captures the fragments of rock. (b) Because of the relative velocity, the kinetic energy is turned into heat. On impact, ice turns into water and the rock fragment gets submerged in water. (c,d) Ice on the comet is sublimated by radial heat from the Sun. (e) At the end, only rock fragments, dust, and organic materials remain. They are weakly bound by gravity and the aggregate looks like a rubble pile asteroid. The Chelyabinsk meteorite should have been delivered from such small body on the current Solar system.|
Radiocesium (RCs) is selectively adsorbed on interlayer sites of weathered micaceous minerals, which can reduce the mobility of RCs in soil. Therefore, soils developed from mica-deficient materials (e.g. serpentine soils) may have a higher risk of soil-to-plant transfer of RCs. Soils were collected from three serpentine soil profiles; Udepts in Oeyama, Japan, and Udepts and Udox in Kinabalu, Malaysia. Soil was sampled every 3cm from 0 to 30cm depth and sieved to isolate soil particles of ≤20μm diameter for the assessment of radiocesium interception potential (RIP) after a series of pretreatments. One subset was treated with H2O2 to remove organic matter (OM). Another subset was further treated with hot sodium citrate to remove hydroxy-Al polymers (Al(OH)x). RIPuntreated was <0.4molkg−1 whereas mica-K content was <0.02% by weight for ≤20-μm soil particles from Udepts and Udox in Kinabalu, Malaysia, values as low as those of non-micaceous minerals (e.g. kaolinite and smectite). Neither OM nor Al(OH)x removal resulted in a large increase in RIP value for these soils. These results clearly indicated that serpentine soils in Malaysia have very few RCs selective adsorption sites due to the absence of micaceous minerals. In contrast, soil from Udepts in Oeyama, Japan showed average RIPuntreated of 5.6molkg−1 and mica-K content of 0.72% by weight for the ≤20-μm particles. Furthermore, the RIP value was significantly increased to an average of 22.5molkg−1 after removing both OM and Al(OH)x. These results strongly suggest that weathered micaceous minerals primarily control the ability to retain RCs. These micaceous minerals cannot originate from serpentine minerals, and are probably incorporated as an exotic material, such as Asian dust. This hypothesis is supported by the δ18O value of quartz isolated from the ≤20-μm soil particles from Oeyama, Japan (+16.13‰±0.11‰), very similar to that of Asian dust. In conclusion, serpentine soils in Japan may exhibit a reduced risk of soil-to-plant transfer of RCs due to the historical deposition of Asian dust.
The RNA World hypothesis requires the synthesis of RNA to allow the emergence of life on Earth. Hydrothermal systems have been proposed as potential candidates for constructing complex biomolecules. However, in order to successfully form RNA, it is necessary to stabilize ribose, a RNA carbohydrate component. Borate has been found to stabilize ribose. Therefore, boron rich hydrothermal systems are important environments concerning the origin of life on Earth. The 3.2-Ga Dixon Island Formation of the West Pilbara Superterrane, Western Australia, is a volcano-sedimentary sequence. The Formation represents a Mesoarchean pelagic hydrothermal system, which formed adjacent to an immature island arc. Fine-grained tourmaline, in addition to biogenic carbonaceous matter and spherulitic and tubular bacteriomorphs, are found in black chert. A boron-rich environment was responsible for the formation of these deposits. To explore the implications of such a boron enriched environment on microbial activity, modes of occurrence and chemical compositions of the tourmaline were examined. The tourmaline is schorl or dravite of the alkali tourmaline group and the boron isotope compositions range in δ11B from − 7.3 to + 2.6‰ . The tourmaline occurs in microcrystalline quartz matrix of black chert veins that cross cut a volcanic unit and also in a bedded black chert, which overlays the volcanic unit. The volcanic unit contains highly altered zones with hydrothermal veins. The associated lithologic and stratigraphic features suggest that the black chert veins were the conduits for upward moving hydrothermal fluids, which reached the sea floor. Subsequently, the volcanic unit was covered by organic matter-rich cherty sediments that in part were fed, and/or altered, by the hydrothermal fluids. These results suggest that the origin of boron enrichment to form Dixon Island tourmaline is not the associated sedimentary mineral assemblage, which includes diagenetic clay, low-grade metamorphic mica, and organic matter. Instead, the tourmaline was directly precipitated from hydrothermal fluid, enriched in boron. Furthermore, the hydrothermal fluids had already concentrated the boron, in the Mesoarchean pelagic system, prior to the apex of organic matter production and microbial activity. Our findings support a hypothesis that the boron-enriched hydrothermal environment aided the survival and evolution of early life.
Boron is associated with several Archean stromatolite deposits, including the tourmaline-rich Barberton stromatolites in South Africa and tourmaline-bearing pyritic laminae associated with stromatolites of the 3.48 Ga Dresser Formation in the Pilbara Craton, Australia. Boron is also a critical element in prebiotic organic chemistry, including in the formation of ribose, a crucial component in RNA. As geological evidence and advances in prebiotic chemistry are now suggesting that hot spring activity may be associated with the origins of life, an understanding of boron and its mobility and isotopic fractionation in geothermal settings may provide important insights into the setting for the origin of life. Here, we report on the boron isotopic compositions and elemental concentrations in a range of fluid, sediment, and mineral samples from the active, boron-rich Puga geothermal system in the Himalayas, India. This includes one of the lowest boron isotope values ever recorded in modern settings: diatom-rich sediments (δ11B=−41.0‰) in a multiphase fractionation system where evaporation is not the dominant form of isotope fractionation. Instead, the extreme boron isotopic fractionation is ascribed to the incorporation of tetrahedral 10B borate anions in precipitating amorphous silica. These findings expand the known limits and drivers of boron isotope fractionation, as well as provide insight into the concentration and fractionation of boron in Archean hot spring environments.
Triple oxygen isotope systematics of ancient hydrothermally altered rocks has been previously used to constrain environmental conditions of the Precambrian. To validate those studies, we report high-precision triple oxygen isotope measurements (expressed as Δ′17O with reference slope 0.528) of quartz, epidote and well fluids from modern geothermal areas of Iceland, Krafla and Reykjanes, as well as measurements from the extinct 6 Ma Geitafell hydrothermal system. At these systems, basalts reacted with distinct fluid sources at temperatures ranging from 250 to 400 °C. Resolvable difference between isotope compositions of surface waters and rocks enables novel insights into boiling, isotope exchange at variable water-rock ratios, and remelting of altered rock. Our measurements of δD, Δ′17O, and δ′18O in well fluids show that the reactions proceeded at water-rock ratios of 0.1 to 2, and reveal the addition of meteoric water in the Reykjanes system, and near-surface boiling and steam-liquid separation at Krafla. The δ′18O and Δ′17O values of fluids shift due to exchange with rocks at high temperature following the slope 0.51 in the triple isotope space. Near-surface boiling and steam-liquid separation cause shifts in δD and δ′18O values of the fluids. Their Δ′17O values do not change significantly owning to the shallow slope of liquid-vapor equilibrium fractionation relative to the reference line slope. Epidote δ′18O and Δ′17O values in all three localities closely resemble the isotope composition of local fluid sources. The measured slope of triple oxygen isotope fractionation between quartz and epidote at 250–400 °C is 0.526 ± 0.001. We suggest that triple oxygen isotope composition of epidote can be used as a direct first-order proxy for the equilibrium fluid δ′18O and Δ′17O values. The calibrated quartz-water equilibrium fractionation for triple oxygen isotopes yields general agreement with the local fluid sources, within ±1.5‰ of their δ18O values, while the Δ′17O agree within ±0.02‰. We present in situ δ18O measurements in a quartz crystal from Krafla that show several ‰ heterogeneities which may affect the reconstructed equilibrium fluid values. We tested the effect of shallow crustal contamination on the Δ′17O values of rhyolitic glasses from Krafla, including those quenched and extracted by drilling, that likely formed by assimilation of low-δ18O hydrothermally altered crust. Our Δ′17O measurements constrain the degree of crustal assimilation to 10–20 %. Our study shows that the Δ′17O values measured in geothermal fluids, secondary minerals and low δ18O contaminated magmas can provide key information on the conditions of water-rock reaction and magma genesis, and contain additional details that were not accessible through conventional analyses of δD and δ18O.
Sample decomposition using inverse aqua regia at elevated temperatures and pressures (e.g., Carius tube or high‐pressure asher) is the most common method used to extract highly siderophile elements (HSEs: Ru, Rh, Pd, Re, Os, Ir, Pt and Au) from geological samples. Recently, it has been recognised that additional HF desilicification is necessary to better recover HSEs, potentially contained within silicate or oxide minerals in mafic samples, which cannot be dissolved solely by inverse aqua regia. However, the abundance of interfering elements tends to increase in the eluent when conventional ion‐exchange purification procedures are applied to desilicified samples. In this study, we developed an improved purification method to determine HSEs in desilicified samples. This method enables the reduction of the ratios of isobaric and polyatomic interferences, relative to the measured intensities of HSE isotope masses, to less than a few hundred parts per million. Furthermore, the total procedural blanks are either comparable to or lower than conventional methods. Thus, this method allows accurate and precise HSE measurements in mafic and ultramafic geological samples, without the need for interference corrections. Moreover, the problem of increased interfering elements, such as Zr for Pd and Cr for Ru, is circumvented for the desilicified samples.
Trace element variability in oceanic basalts is commonly used to constrain the physics of mantle melting and the chemistry of Earth's deep interior. However, the geochemical properties of mantle melts are often overprinted by mixing and crystallisation processes during ascent and storage. Studying primitive melt inclusions offers one solution to this problem, but the fidelity of the melt-inclusion archive to bulk magma chemistry has been repeatedly questioned. To provide a novel check of the melt inclusion record, we present new major and trace element analyses from olivine macrocrysts in the products of two geographically proximal, yet compositionally distinct, primitive eruptions from the Reykjanes Peninsula of Iceland. By combining these macrocryst analyses with new and published melt inclusion analyses we demonstrate that olivines have similar patterns of incompatible trace element (ITE) variability to the inclusions they host, capturing chemical systematics on intra- and inter-eruption scales. ITE variability (element concentrations, ratios, variances and variance ratios) in olivines from the ITE-enriched Stapafell eruption is best accounted for by olivine-dominated fractional crystallisation. In contrast, ITE variability in olivines and inclusions from the ITE-depleted Háleyjabunga eruption cannot be explained by crystallisation alone, and must have originated in the mantle. Compatible trace element (CTE) variability is best described by crystallisation processes in both eruptions. Modest correlations between host and inclusion ITE contents in samples from Háleyjabunga suggest that melt inclusions can be faithful archives of melting and magmatic processes. It also indicates that degrees of ITE enrichment can be estimated from olivines directly when melt inclusion and matrix glass records of geochemical variability are poor or absent. Inter-eruption differences in olivine ITE systematics between Stapafell and Háleyjabunga mirror differences in melt inclusion suites, and confirm that the Stapafell eruption was fed by lower degree melts from greater depths within the melting region than the Háleyjabunga eruption. Although olivine macrocrysts from Stapafell are slightly richer in Ni than those from Háleyjabunga, their overall CTE systematics (e.g., Ni/(Mg/Fe), Fe/Mn and Zn/Fe) are inconsistent with being derived from olivine-free pyroxenites. However, the major element systematics of Icelandic basalts require lithological heterogeneity in their mantle source in the form of Fe-rich and hence fusible domains. We thus conclude that enriched heterogeneities in the Icelandic mantle are composed of modally enriched, yet nonetheless olivine-bearing, lithologies and that olivine CTE contents provide an incomplete record of lithological heterogeneity in the mantle. Modally enriched peridotites may therefore play a more important role in oceanic magma genesis than previously inferred.
We present K‐Ar ages, major and trace element concentrations, and Sr‐Nd‐Pb isotope data for late Cenozoic volcanic rocks from the Chugoku district, southwest Japan arc. Andesite and dacite lavas in this region are enriched in Sr (mostly > 800 μg g−1) and show geochemical characteristics of volcanic rocks commonly referred to as “adakite.” K‐Ar dating of these lavas revealed that the eruption of high‐Sr andesitic to dacitic magmas occurred during the last 2 Myr, following or concurrent with the eruption of basalt in adjacent regions. Trace‐element characteristics of high‐Sr andesites and dacites are consistent with the formation of their parent magmas by partial melting of the basaltic layer of the subducting Shikoku Basin Plate. Mass balance modeling of trace element concentrations and isotopic compositions suggests that the parental magmas of high‐Sr andesites and dacites are best explained by mixing of partial melts from oceanic crust (F = 5–15%) and sediment (F = 30%) at 80:20 to 55:45 ratios. Spatial coincidence of the occurrences of high-Sr andesites and dacites and seismic gaps of the subducting slab demonstrates the causal link between slab melting and mantle upwelling at slab tears. We speculate that these tears could have been formed by subduction of ridges on the plate. A warm mantle upwelled through tears, preventing the solidification of the siliceous slab melts in the mantle and facilitating the transportation of these melts to the surface.
The chemical compositions of the residues of the mantle melting that produces mid-ocean ridge basalt can be altered by fluid-rock interactions at spreading ridges and, possibly, during seawater penetration along bending-related faults in plates approaching trenches. This chemically modified rock, if subducted deeply and after long-term residence within the deep Earth, is a potential source of chemical heterogeneity in the mantle. Here, we demonstrate that peridotites from the Horoman massif preserve the chemical signatures of sub-seafloor hydrothermal (SSH) alteration at a mid-ocean ridge approximately one billion years ago. These rocks have evolved chemically subsequent to this SSH alteration; however, they retain the SSH-associated enrichments in fluid mobile elements and H2O despite their long-term residence within the mantle. Our results indicate that ancient SSH alteration resulting in the production of sulfide leads to Pb enrichment that could affect the present-day Pb isotopic evolution of the silicate earth. Evidence from the Horoman massif of the recycling of hydrous refractory domains into the mantle suggests that both the flux of H2O content into the mantle and the size of the mantle H2O reservoir are higher than have been estimated recently.
Massive to lobate volcanic flows and brecciated hyaloclastite units in the Abitibi greenstone belt allow investigation of Late Archæan seafloor alteration and associated incorporation into these rocks of nitrogen (N) biogeochemical signatures. In this suite (the Blake River Group), hyaloclastite units containing putative microbial ichnofossils are particularly enriched in large-ion lithophile elements (K, Rb, Ba, Cs), B, and Li, consistent with their having experienced the greatest fluid–rock interaction during subseafloor hydrothermal alteration. Similarly, silicate-δ18O and δ15N values for samples from the hyaloclastites show the greatest shifts from plausible magmatic values. The chemical and isotopic patterns in these tholeiitic igneous rocks greatly resemble those in modern altered seafloor basalts, consistent with the preservation of an Archæan seafloor alteration signature. The N enrichments and shifts in δ15N appear to reflect stabilization of illite and interaction with fluids carrying sedimentary/organic signatures. Enrichments of N (and the δ15N of this N) in altered glass volcanic rocks on Earth's modern and ancient seafloor point to the potential utility of N for tracing past and present biogeochemical processes in similar rocks at/near the Mars surface.
Observed enrichments of N (and the δ15N of this N) in volcanic glasses altered on Earth's modern and ancient seafloor are relevant in considerations of modern global N subduction fluxes and ancient life on Earth, and similarly altered glasses on Mars and other extraterrestrial bodies could serve as valuable tracers of biogeochemical processes. Palagonitized glasses and whole-rock samples of volcanic rocks on the modern seafloor (ODP Site 1256D) contain 3–18 ppm N with δ15Nair values of up to +4.5‰. Variably altered glasses from Mesozoic ophiolites (Troodos, Cyprus; Stonyford volcanics, USA) contain 2–53 ppm N with δ15N of −6.3 to +7‰. All of the more altered glasses have N concentrations higher than those of fresh volcanic glass (for MORB, <2 ppm N), reflecting significant N enrichment, and most of the altered glasses have δ15N considerably higher than that of their unaltered glass equivalents (for MORB, −5 ± 2‰). Circulation of hydrothermal fluids, in part induced by nearby spreading-center magmatism, could have leached NH4+ from sediments then fixed this NH4+ in altering volcanic glasses. Glasses from each site contain possible textural evidence for microbial activity in the form of microtubules, but any role of microbes in producing the N enrichments and elevated δ15N remains uncertain. Petrographic analysis, and imaging and chemical analyses by scanning electron microscopy and scanning transmission electron microscopy, indicate the presence of phyllosilicates (smectite, illite) in both the palagonitized cracks and the microtubules. These phyllosilicates (particularly illite), and possibly also zeolites, are the likely hosts for N in these glasses.
Rift to drift: witness the breakup of African continent
The Ethiopian Rift is the extensional basin developed on African continent during the last 30 million years. Seismic studies reveal that the crust beneath the current rift axis is predominantly mafic materials, and akin to the oceanic region. Such feature suggests that the eastern part of Africa will eventually drift apart and becomes ocean.
The use of temporal geochemical variations of Ethiopian volcanic rocks has lagged behind, despite that it would provide important constraints on thermal and compositional evolution of crust and mantle beneath the incipient continental rift. In this study, we present ages and geochemical compositions of mafic lavas, collected from Main Ethiopian Rift (MER), to document the evolution of this rift. Melting condition, estimated from rare-earth element enrichments in mafic lavas, has been constant during the last 27 million years. This result can be accounted for by late Cenozoic MER magmatism driven primarily by plate divergence, as that occurs in mid-ocean ridge. We also reveal that the contribution of lithosphere to MER magmas decreases with time, probably due to continuous thermal erosion and dehydration of lithosphere.
Omphacite replacing after relic edenitic pargasite has been found in an omphacite–bearing jadeitite block of the Itoigawa–Omi area in the Hida–Gaien belt. Omphacite occurs sporadically as fine–grained aggregate reaching a few cm in length in a jadeite–albite matrix, and sometimes contains edenitic pargasite as a core. The edenitic pargasite is chemically and optically homogeneous and does not show direct contact with jadeite and albite. An irregular shaped omphacite–diopside mixed area occurs near edenitic pargasite in a coarse omphacite aggregate. The texture suggests that the breakdown of edenitic pargasite was triggered by the addition of a hydrothermal fluid, from which jadeite and albite were precipitated later, passing through diopside and omphacite by the reaction: NaCa2Mg5(AlSi7)O22(OH)2 → (NaAlSi2O6 + CaMgSi2O6) + CaMgSi2O6 + Mg3SiO5 + H2O. At the periphery of pseudomorphic omphacite, a hydrothermal fluid removed the breakdown components of the reaction other than omphacite. New in–situ LA–ICP–MS U–Pb dating revealed that zircons in edenitic pargasite yield apparent age up to ~ 590 Ma, with mean ages of 560 ± 16 Ma, interpreted as the minimum age of a precursor rock. A zircon age of 519 ± 21 Ma from jadeitite without omphacite corresponds to a timing of crystallization of omphacite, jadeite, and albite. The studied jadeitite is a typical R–type jadeitite, and the nearly total replacement from a precursor rock to the omphacite–bearing jadeitite has been attributed to hydrothermal activity at Middle Cambrian times.
The formation of planetesimals and planetary embryos during the earliest stages of the solar protoplanetary disk largely determined the composition and structure of the terrestrial planets. Within a few million years of the birth of the Solar System, chondrule formation and the accretion of the parent bodies of differentiated achondrites and the terrestrial planets took place in the inner protoplanetary disk. Here we show that, for chondrules in unequilibrated enstatite chondrites, high-precision Δ17O values (where Δ17O is the deviation of the δ17O value from a terrestrial silicate fractionation line) vary significantly (ranging from −0.49 to +0.84‰) and fall on an array with a steep slope of 1.27 on a three-oxygen-isotope plot. This array can be explained by the reaction between an olivine-rich chondrule melt and an SiO-rich gas derived from vaporized dust and nebular gas. Our study suggests that a large proportion of the building blocks of planetary embryos formed by successive silicate–gas interaction processes: silicate–H2O followed by silicate–SiO interactions under more oxidized and reduced conditions, respectively, within a few million years of the formation of the Solar System.
The paper presents new data on the isotopic age and chemical composition of volcanic rocks from the Tytyl’veem and Mangazeika basins of western Chukotka superposed on Mesozoides of the Verkhoyansk–Chukotka Tectonic Region. The results of SIMS U–Pb zircon dating (121.4 ± 2.8 and 118.0 ± 2.0 Ma) corroborate the Aptian age of the Tytyl’veem Formation. This age, in turn, indicates its formation after closure of the South Anyui ocean (Neocomian), but before origination of the Okhotsk–Chukotka Belt (Albian–Campanian). Post-collisional Aptian igneous rocks are widespread in the northern Verkhoyansk–Chukotka Tectonic Region; the length of the corresponding igneous province is no less than 1400 km. In geochemical characteristics, the post-collisional volcanic rocks occurring in Western Chukotka are similar with the rocks from Andean-type igneous belts.
Rationale The precise determination of Δ'17O values in terrestrial material is becoming increasingly important to understand the mass‐dependent fractionation processes that cause variations in oxygen isotope ratios. San Carlos olivine is widely used as the reference material for oxygen isotope measurements of terrestrial and extraterrestrial materials. We report new Δ'17O values for San Carlos olivine that were independently determined in two different laboratories (Geoscience Center [GZG], University of Göttingen) and Institute for Study of the Earth's Interior [ISEI], Okayama University, Misasa) in direct comparison with VSMOW2 and SLAP2 water standards. Methods The δ17O and δ18O values of VSMOW2, SLAP2, GISP, and San Carlos olivine were determined relative to reference gas. In both laboratories, water and San Carlos olivine samples were prepared by BrF5 fluorination. In both laboratories, the O2 released from water and olivine samples was passed through the same purification system and measured using the same mass spectrometer relative to the same reference gas. Results In both laboratories, the δ17OVSMOW2 and δ18OVSMOW2 scales were slightly compressed with respect to the recommended composition of VSMOW2 and SLAP2. The new Δ'17O0.528 value (calculated from the VSMOW2‐SLAP2 scaled δ values) of San Carlos olivine from GZG was −36 ± 9 ppm and, from ISEI, a value of −40 ± 7 ppm (1σ standard deviation) was determined. These values are ~50 ppm higher than previously reported from the same laboratories. Possible causes for the observed discrepancies are discussed. Conclusions The results of this study in comparison with previous data from the same laboratories demonstrated that for high accuracy determination of Δ'17O values: (i) calibration of the reference gas relative to O2 released from primary standards (VSMOW2, SLAP2) in the same laboratory is highly recommended, (ii) non‐linearity of the mass spectrometer may not only affect δ17O and δ18O values but also Δ'17O values, and (iii) the VSMOW2‐SLAP2 scaling should also be applied to analyses of rocks and minerals. Studies that are concerned with small differences in Δ'17O at similar δ18O values, however, are not affected by non‐linearity of the mass spectrometer.
Results of a comprehensive geochemical study (major and trace elements, and isotopes of Sr, Nd, Pb, Hf) of Cretaceous volcanic rocks from the Chukotka area in northeastern Russia are presented. Synthesis of available geological and geochronological data suggests diachronous onset of activity of the Okhotsk-Chukotka volcanic belt (OCVB), the largest magmatic province in the region. The OCVB consists of ca. 106 km3 of volcanic rocks. At 106-105 Ma, subduction-related magmatism initiated in the southern and central segments of the OCVB. In the Central and Northern Chukotka areas, where the northern OCVB is exposed, onset of arc magmatism occurred ca. 10 m.y. after extension-related magmatism of the Chaun igneous province at 109-104 Ma. Mafic rocks from the OCVB yield (87Sr/86Sr)80 Ma of 0.7033 to 0.7047, εNd80 Ma of 0.0 to 7.10, εHf80 Ma of 4.12 to 12.88, (206Pb/204Pb)80 Ma of 18.11 to 18.42, and (208Pb/204Pb)80 Ma of 37.96 to 38.21. Volcanic rocks from the Chaun province, as well as OCVB rocks from Northern Chukotka, originate from a relatively enriched source and have (87Sr/86Sr)80 Ma of 0.7088 to 0.7100, εNd80 Ma of - 5.81 to - 3.42, εHf80 Ma of - 3.40 to - 0.25, (206Pb/204Pb)80 Ma of 18.69 to 18.90, and (208Pb/204Pb)80 Ma of 38.65 to 38.86. No definitive across-arc elemental or isotopic zonation of the OCVB has been revealed, probably because of wide-scale crustal melting and subsequent contamination of mantle-derived melts. However, there is a clear along-arc isotopic zonation. In our interpretation, this results from heterogeneity of the subcontinental lithospheric mantle, which likely was a major contributor to the magma source. The similar isotopic signatures of silicic (dominantly crust-derived) and mafic (mantle-derived) volcanic rocks in each OCVB segment imply that remelting of juvenile mafic underplated material was the main process responsible for the crust-derived magma generation. These data from the major Cretaceous magmatic provinces of northeast Asia are synthesized in context of existing plate tectonic reconstructions.
Factors controlling the abilities of Allophanic Andosols (representative of Japanese volcanic ash soils) to retain radiocesium (RCs) were assessed. The hypothesis was that retention is largely controlled by traces of micaceous minerals deposited as components of aeolian dust. The radiocesium interception potentials (RIPs), mica K contents were determined in the 2- to 20- and < 2.0-μm particle fractions of 23 soil samples from agricultural fields in areas representative of Japanese Allophanic Andosols. Quartz contents were determined in the 2- to 20-μm particle fractions of the same soil samples. The oxygen isotope ratio (δ18O) in the quartz isolated from each 2- to 20-μm particle fraction was determined to identify the origin of the quartz in each soil sample. The mean RIP for the 2- to 20- and < 2-μm particles was 1.7 ± 0.8 and 2.6 ± 1.3 mol kg‐1, respectively, and the mica K contents were 3.2 ± 1.3 and 3.4 ± 1.7 g kg‐1, respectively, corresponding to micaceous mineral contents of < 5% by mass in each size fraction. In spite of their rather low values, the RIPs and mica K contents in each fraction positively correlated (p < 0.01), indicating that the abilities of the soils to retain RCs were mainly controlled by the micaceous mineral contents. The mica K content was proportional to the quartz content in the < 20-μm particles, and the mean δ18O in the quartz was +14.8‰, similar to those in fine quartz in Chinese loess. These results strongly indicate that the abilities of Allophanic Andosols to retain RCs are largely controlled by micaceous minerals probably originating in aeolian dust.
The recently published paper by Kimura et al.  reports geochemical and isotopic analyses of Quaternary adakitic dacites (ADK) from two volcanic groups, Daisen and Aonoyama, in southwest (SW) Japan. Based on Pb isotope compositions, these authors suggest that crustal assimilation played a major role in the genesis of ADK. This conclusion differs from that of an earlier study by Feineman et al. , who advocated only a minimal crustal effect and concluded that the Pb isotope array for Daisen ADK can be attributed to partial melting of the subducting slab with a significant amount of sediment. The Pb isotope trends for Daisen ADK presented in these two studies are clearly different and Kimura et al.  did not directly compare the date sets or provide any explanation for the differences. In this comment, we critically examine the differences between the Pb isotope date sets presented by Feineman et al.  and Kimura et al. . We present new date for Aonoyama ADK and we provide an explanation for the discrepancy between the date obtained in our lab and in this other recently published study.
We present a geochemical study on olivine and clinopyroxene-hosted melt inclusions (MIs) from 2001 to 2006 Etna basaltic lavas and pyroclastites. Three MI suites are distinguished on the basis of trace element fingerprinting. Type-1 MIs (from 2001 Upper South and 2002 Northeast vents) share their trace element signature with low-K lavas erupted before 1971. Critical trace element ratios (e.g., K/La, Ba/Nb), along with Pb isotope data of Type-1 MIs provide evidence for a heterogeneous mantle source resulting from mixing of three end-members with geochemical and isotopic characteristics of EM2, DMM, and HIMU components. Type-1 MIs composition does not support involvement of subduction-related components. Type-2 (from 2001 Lower and 2002 South vents) and Type-3 (2004 eruption) MIs reveal "ghost plagioclase signatures," namely lower concentrations in strongly incompatible elements, and positive Sr, Ba, and Eu anomalies. Both Type-1 and Type-2 MIs occur in 2006 olivines, which highlight the occurrence of mixing between Type-1 and Type-2 end-members. Type-2/Type-3 MIs testify to en route processes (plagioclase assimilation and volatile fluxing) peculiar for "deep dike fed" eruptions. The latter are strongly controlled by tectonics or flank instability that occasionally promote upraise of undegassed, more radiogenic primitive magma, which may interact with plagioclase-rich crystal mush/cumulates before erupting. Type-2/Type-3 MIs approach the less radiogenic Pb isotopic composition of plagioclase from prehistoric lavas, thus suggesting geochemical overprinting of present-day melts by older products released from distinct mantle sources. Our study emphasizes that MIs microanalysis offers new insights on both source characteristics and en route processes, allowing to a link between melt composition and magma dynamics.
The 238U–230Th internal isochron method has great potential for determining eruption ages of young volcanic materials if the separated groundmass phases have a sufficiently wide range of U/Th ratios. We examined the fractionation behavior of U and Th in aged (i.e., > 0.5 Ma) basaltic samples by 6 M hydrochloric acid leaching to evaluate the applicability of acid-leaching treatment for the 238U–230Th internal isochron method. Acid leaching of aged basaltic rocks in 238U–234U–230Th secular equilibrium at the bulk-rock scale results in 230Th–238U and 234U–238U radioactive disequilibria for both leachates and residues. These radioactive disequilibria can be explained by redistribution of 234Th (parent of 234U) and 230Th between acid-soluble and acid-resistant phases due to α-recoil. The number of 230Th atoms redistributed by α-recoil can be calculated by using a mass conservation equation for 234U atoms and by the relative amount of recoiled 230Th and 234Th, the latter proportional to the kinetic energy of the recoiled nuclide. When the fraction of daughter nuclide 234U remaining in either the residue or leachate, after α-recoil redistribution of 238U, is large enough (> 95%), the corrected (230Th/238U) values of leachate and residue show radioactive equilibria. This result demonstrates that preferential fractionation between U and Th does not occur during acid leaching for basaltic samples if there is no selective etching of the α-recoil track. This study implies that acid-leaching can be used in conjunction with the 238U–230Th internal isochron method for dating young volcanic rocks by evaluating the degree of the α-recoil redistribution of 234U.
A new simple and quick method has been established for separation of Cu from solutions using an extraction chromatographic resin utilizing Aliquat® 336 (commercially available as TEVA™ resin) and Cu(I). This method involves the use of a one milliliter column containing 0.33 mL TEVA™ resin on 0.67 mL Amberchrom® CG-71C acrylic resin. Copper was adsorbed on the column by forming Cu(I) with 0.15% ascorbic acid in 0.05 mol·L−1 HBr, while other major elements except Zn showed no adsorption. After removal of the major elements (Na, Mg, Al, P, K, Ca, Cr, Mn, Fe, Co and Ni), Cu was recovered using 2 mol·L−1HNO3. The recovery yield and total blank were 102% ± 2% and 0.25 ng, respectively. To evaluate the separation method, Cu isotope ratios were determined by a standard-sample-standard bracketing method using multicollector inductively coupled plasma-mass spectrometry (ICP-MS), with a repeatability of 0.04‰ and 0.25‰ (SD), for the standard solution and the solutions from low S (<0.1% S) silicate standards, respectively.
Super-eruptions that dwarf all historical volcanic episodes in erupted volume and environmental impact are abundant in the geological record. Such eruptions of silica-rich magmas form large calderas. The mechanisms that trigger these super-eruptions are elusive because the processes occurring in conventional volcanic systems cannot simply be scaled up to the much larger magma chambers beneath supervolcanoes. Over-pressurization of the magma reservoir, caused by magma recharge, is a common trigger for smaller eruptions, but is insufficient to generate eruptions from large supervolcano magma chambers. Magma buoyancy can potentially create sufficient overpressure, but the efficiency of this trigger mechanism has not been tested. Here we use synchrotron measurements of X-ray absorption to determine the density of silica-rich magmas at pressures and temperatures of up to 3.6 GPa and 1,950 K, respectively. We combine our results with existing measurements of silica-rich magma density at ambient pressures to show that magma buoyancy can generate an overpressure on the roof of a large supervolcano magma chamber that exceeds the critical overpressure of 10–40 MPa required to induce dyke propagation, even when the magma is undersaturated in volatiles. We conclude that magma buoyancy alone is a viable mechanism to trigger a super-eruption, although magma recharge and mush rejuvenation, volatile saturation or tectonic stres may have been important during specific eruptions.
Olivine-hosted melt inclusions from both Fernandina and Santiago islands in the Galapagos Archipelago have compositions indicating that plagioclase played an important role in the magmatic evolution of these volcanic islands. The major and trace element chemistry of the Santiago melt inclusions indicates simple plagioclase assimilation. In contrast, Fernandina inclusions have compositions for which the plagioclase appears to be present only as a ‘ghost’ trace element signature (i.e. ‘ghost plagioclase’ signature). Two competing hypotheses have been proposed to explain this unique signature: (1) incorporation of an ancient recycled plagioclase-rich cumulate into the mantle; (2) shallow-level interaction between melts and plagioclase-rich cumulates in the present-day lower oceanic crust. Here we present new Pb isotope measurements for olivine-hosted melt inclusions from Fernandina and Santiago islands to distinguish between the two models. The new Pb isotope data are within the range previously reported for whole-rock basalts from those islands. Melting and mixing models involving ancient (∼0.5–1 Ga) recycled plagioclase-rich cumulates cannot reproduce the observed trace element and Pb isotopic characteristics of the Fernandina melt inclusions with a ghost plagioclase signature. Shallow-level diffusive interactions between basalt and present-day plagioclase-rich cumulates provide the simplest explanation for the observed trace element compositions and Pb isotope ratios of melt inclusions from Fernandina and Santiago islands.
Oxygen isotope compositions are reported for the first time for the Himalayan metabasites of the Kaghan Valley, Pakistan in this study. The highest metamorphic grades are recorded in the north of the valley, near the India–Asia collision boundary, in the form of high-pressure (HP: Group I) and ultrahigh-pressure (UHP: Group II) eclogites. The rocks show a step-wise decrease in grade from the UHP to HP eclogites and amphibolites. The protoliths of these metabasites were the Permian Panjal Trap basalts (ca. 267 ± 2.4 Ma), which were emplaced along the northern margin of India when it was part of Gondwana. After the break-up of Gondwana, India drifted northward, subducted beneath Asia and underwent UHP metamorphism during the Eocene (ca. 45 ± 1.2 Ma). At the regional scale, amphibolites, Group I and II eclogites yielded δ18O values of + 5.84 and + 5.91‰, + 1.66 to + 4.24‰, and − 2.25 to + 0.76‰, respectively, relative to VSMOW. On a more local scale, within a single eclogite body, the δ18O values were the lowest (− 2.25 to− 1.44‰) in the central, the best preserved (least retrograded) parts, and show a systematic increase outward into more retrograded rocks, reaching up to + 0.12‰. These values are significantly lower than the typical mantle values for basalts of + 5.7 ± 0.3‰. The unusually low or negative δ18O values in Group II eclogites potentially resulted from hydrothermal alteration of the protoliths by interactions with meteoric water when the Indian plate was at southern high latitudes (~ 60°S). The stepwise increase in δ18O values, among different eclogite bodies in general and at single outcrop-scales in particular, reflects differing degrees of resetting of the oxygen isotope compositions during exhumation-related retrogression.
Metapelitic rocks of the Schistes Lustrés in the Cottian Alps, Italy (peak metamorphic conditions of 350–500 °C, 1.2–2.0 GPa) and at the UHP Lago di Cignana locality (Valtournenche, Italy; ~ 550 °C, 2.5–3.0 GPa) preserve records of prograde devolatilization in their mineral modes and chemistry, contents of volatiles and fluid-mobile elements (elements relatively mobile in aqueous fluids), and B and N isotope compositions. This suite allows study of prograde devolatilization history, across a wide range in metamorphic grade, in metasedimentary rocks that experienced high-P/T prograde paths similar to those experienced in most modern subduction zones. Across grade, whole-rock samples are in general uniform in their concentrations of relatively fluid-mobile elements N, B, Li, Cs, Ba, and Rb, normalized to the concentrations of the less mobile K2O and Al2O3, showing only hints of loss in several of the highest-grade samples. With increasing grade, ion microprobe analyses of phengites show subtle decrease in B concentration, uniformity in Ba and Cs concentrations, and increase in Li concentrations, the latter likely due to release from chlorite during its breakdown. In one Cignana sample, phengite inclusions in garnets are enriched in B relative to matrix phengite, consistent with either whole-rock B loss after garnet growth or, more likely, closed-system behavior and partitioning of B into paragonite or tourmaline stabilized after garnet growth. In samples with both paragonite and phengite, paragonite shows relative enrichment in B and Sr, and phengite is enriched in Cs, Ba, and presumably also N and Rb (the latter showing strong whole-rock correlations with K2O). Whole-rock δ15N shows a hint of shift to higher values in the highest grade rocks (Cignana) and, accordingly, calculated prograde dehydration histories for appropriate bulk compositions, using the Perple-X database, indicate that significant (~ 20%) dehydration would for some rocks occur over the temperature interval of 450 to 550 °C, largely related to the breakdown of chlorite (and to a lesser extent carpholite). Small amounts of loss of N into these fluids could have resulted in minor shift in δ15N, with decrease in whole-rock N concentration masked by heterogeneity inherent with the sedimentary protoliths. Partitioning of Cs and Li (possibly also Rb and Ba) from white micas into H2O-rich fluids largely produced by chlorite breakdown could similarly have produced the subtle decreases in the concentrations in these elements noted in several high-grade samples. Neoblastic tourmaline in higher-grade rocks likely sequestered some fraction of the B lost from micas, resulting in a lack of obvious whole-rock B loss to accompany the up-grade trend of decreasing B concentrations in phengite. This tourmaline shows core-to-rim decrease in δ11B consistent with growth during small amounts of progressive B loss from phengites. Taken together, the whole-rock and SIMS data presented here, and the whole-rock dataset of Busigny et al. (2003), demonstrate impressive retention, during prograde forearc devolatilization, of elements thought to be relatively fluid-mobile (particularly H, N, B, Li, Ba, and Cs). Retention of these elements in metasedimentary rocks subducted to depths overlapping those beneath arc volcanic fronts (~ 90 km estimated for subsolidus, peak Cignana metamorphism) implies their availability for transfer into arc source regions, in aqueous fluids or silicate melts, or into the mantle to depths beyond subarc regions.
The Quaternary Southwest Japan Arc is a product of subduction of the hot, young Philippine Sea Plate beneath the Eurasian Continental Plate. The magmas erupted from the Southwest Japan Arc belong to a category of magmas commonly referred to as "adakites" or "adakitic magmas". These magmas show trace element evidence for interaction with garnet at depth, and may be associated with partial melting of subducted altered oceanic crust. Also found throughout the southern Sea of Japan region are alkali basalts with little apparent connection to the subduction zone. We have determined major element, trace element, and Sr, Nd, Pb, and U-Th isotopic compositions for a bimodal suite of lavas erupted at the Daisen volcanic field in the Southwest Japan Arc. These magmas consist of mildly alkaline basalts and a calcalkaline intermediate suite, separated by a ~10 wt.% silica gap. The intermediate magmas show trace element and isotopic evidence for interaction with garnet, consistent with partial melting of the hot, young (~20 Ma) Philippine Sea Plate. The Daisen intermediate magmas are distinct from other adakitic magmas in their radiogenic isotopic characteristics, consistent with a significant contribution (~25%) from subducted Nankai Trough sediments. Our data suggest that the basalts erupted at the Daisen volcanic field are not parental to the intermediate magmas, and contain a small contribution of EM1-like mantle common in Sea of Japan alkali basalts but not apparent in the Daisen intermediate magmas.
A new low-blank Zn separation method employing an extraction chromatographic resin using Aliquat 336 (commercially available as TEVA resin) has been developed for Zn isotope composition determination by double spike-multiple collector-ICP-MS. The silicate sample solution containing 0.1 μg Zn in 0.5 mol L−1 HBr containing 0.15% ascorbic acid (AA) is passed through a 1 mL column with 0.33 mL TEVA resin. While Zn is absorbed, major elements are eluted with 0.5 mol L−1 HBr with AA. Afterwards, Zn was recovered with 2 mol L−1 HNO3. Recovery yield using silicate samples was 96.7 ± 6.8% (n = 10) and total blank was 0.05 ng (n = 6). The blank level is from 1/300 to 1/20 of previous studies, meaning 0.1 μg of Zn is sufficient for analysis. The 67Zn–70Zn double spike method was used in MC-ICP-MS. δ66Zn of three USGS standard silicate reference materials (BHVO-1, AGV-1 and PCC-1) and seven GSJ silicate reference materials (JB-1, -2, -3, JA-1, -2, -3 and JP-1) were determined. Reproducibility of δ66Zn of the total silicates was 0.19‰ (2SD). δ66Zn of three carbonaceous chondrites (Orgueil, Murchison and Allende) were also determined and compared with those of references.
A new, simple and fast separation method for Fe using an extraction chromatographic resin, Aliquat 336 (commercially available as TEVA resin) has been developed. A one milliliter column containing 0.33 mL TEVA resin on 0.67 mL CG-71C was used.Iron was adsorbed with 6mol·L-1 HCl + H2O2 on TEVA resin, and recovered with 2 mol·L-1HNO3. The recovery yield and total blank were 93.5 ± 6.5% and 6 ng, respectively. Theseparation method is simple, and takes < 2 hours. For evaluation of the Fe separation, Fe isotope ratios were measured by a double-spike method employing multicollector inductively coupled plasma source mass spectrometry (MC-ICP-MS) with repeatability of 0.06‰ (SD) for the standard solution and ~0.05‰ for the silicate samples. Therefore, the column chemistry developed in this study is a viable option for Fe isotope ratio measurement by MC-ICP-MS.
Saline groundwaters are common to inland Australia, but their hydrochemical evolution and origin remain largely unknown. The saline groundwaters in the alluvial aquifers of the Darling River have previously been found to exhibit broad similarity in traditional hydrochemical and isotopic tracers. By contrast, in this study the trace element isotopes (δ7Li, δ11B and 87Sr/86Sr) have illuminated more complex hydrogeochemical processes in the same aquifer system. This paper reports the first ever set of δ7Li values in any groundwater system in Australia. They varied from +5.8 to +16.2 with an average value of +9.7‰ (n = 19) in the alluvial aquifers of the Darling River catchment. The δ11B values were all higher than seawater and close to some of the highest δ11B values ever reported in the literature for a groundwater system (+44.4 to +53.9; average: +48.8, n = 17). The 87Sr/86Sr ratios ranged from 0.708 to 0.713, with an average value of 0.709 (n = 19). The differing signatures in these trace element isotope values, highlighted by discovery of the deeper older groundwater system with heavier Li isotope values and higher 87Sr/86Sr, is an important finding of this research. Simple mixing models between river water and saline groundwater cannot explain the observed variation in trace element isotopes. Hydrochemical evolution was found to be dependent on proximity to the Darling River and depth. Varying degrees of Li and B isotopic fractionation during water–sediment interaction were interpreted to account for the evolution of the saline groundwaters. The measurement of these trace element isotopes has permitted delineation of groundwater end-members that would have otherwise not been identified; in their absence an inaccurate interpretation of the hydrochemical evolution of these saline groundwaters would have been made. This study highlights the importance of a multi-tracer approach, which includes trace element isotopes, in resolving complex geochemical processes in groundwater in semi-arid to arid zone environments.
We report ion microprobe U–Th–Pb geochronology of in situ zircon from the Himalayan high- and ultrahigh-pressure eclogites, Kaghan Valley of Pakistan. Combined with the textural features, mineral inclusions, cathodoluminescence image information and the U–Th–Pb isotope geochronology, two types of zircons were recognized in Group I and II eclogites. Zircons in Group I eclogites are of considerably large size (>100 μm up to 500 μm). A few grains are euhederal and prismatic, show oscillatory zoning with distinct core–rim luminescence pattern. Several other grains show irregular morphology, mitamictization, embayment and boundary truncations. They contain micro-inclusions such as muscovite, biotite, quartz and albite. Core or middle portions of zircons from Group I eclogites yielded concordant U–Th–Pb age of 267.6 ± 2.4 Ma (MSWD = 8.5), have higher U and Th contents with a Th/U ratio > 1, indicating typical magmatic core domains. Middle and rim or outer portions of these zircons contain inclusions of garnet, omphacite, phengite and these portions show no clear zonation. They yielded discordant values ranging between 210 and 71 Ma, indicating several thermal or Pb-loss events during their growth and recrystalization prior to or during the Himalayan eclogite-facies metamorphism. Zircons in Group II eclogites are smaller in size, prismatic to oval, display patchy or sector zoning and contain abundant inclusions of garnet, omphacite, phengite, quartz, rutile and carbonates. They yielded concordant U–Th–Pb age of 44.9 ± 1.2 Ma (MSWD = 4.9). The lower U and Th contents and a lower Th/U ratio (<0.05) in these zircons suggest their formation from the recrystallization of the older zircons during the Himalayan high and ultrahigh-pressure eclogite-facies metamorphism.
The post-caldera lavas of Bratan volcano in Bali island, Indonesia were collected for whole rock chemical analyses and K-Ar analyses. Major and trace element chemistry shows that the lavas basalts to andesites and typical of subduction-related tectonic setting. The 38Ar/36Ar ratios are 0.1851 ± 3-0.1875 ± 2 and the 40Ar/36Ar, 294.3 ± 0.3-301.6 ± 0.1, which strongly suggest that the mass fractionation to light isotope enrichment took place. The effect of the groundwater on magma is common on the basis of systematic mass fractionation of the atmospheric Ar enriched in lighter isotopes. This case was under the mass fractionation law analyzed numerically, giving the mass fractionation correction ages (14 ± 15, 31 ± 6, 55 ± 22, 66 ± 23, 94 ± 32 and 125 ± 51 ka) consistent with the volcano stratigraphy though the magma composition that changed frequently in time.
This work describes two newly discovered eucrite breccias: three presumably paired meteorites, all named Northwest Africa (NWA) 6105, and NWA 6106. For each meteorite, major‐ and minor‐element compositions of minerals were determined using the electron microprobe. Pyroxene Fe‐Mn co‐variations and bulk‐rock oxygen isotope compositions confirm their classification as eucrites. Variations in mineral compositions and textures are attributed to differences in clast types present (i.e., basaltic or cumulate eucrite). The pyroxene compositions support the hypothesis that samples NWA 6105,1; 6105,2; and 6105,3 are paired polymict eucritic breccias, whereas sample NWA 6106 is a monomict basaltic eucritic breccia. Two‐pyroxene geothermometry yields temperatures too low for igneous crystallization. The variation in temperatures among samples suggests that metamorphism occurred prior to brecciation.
RATIONALE. Oxygen triple isotope compositions give key information for understanding physical processes during isotopic fractionation between the geo‐, hydro‐, bio‐, and atmosphere. For detailed discussion of these topics, it is necessary to determine precise 17O‐excess values of terrestrial silicate/oxide minerals with respect to Vienna Standard Mean Ocean Water (VSMOW). METHODS. Water was fluorinated in an electrically heated Ni‐metal tube into which water and BrF5 were loaded for the quantitative extraction of oxygen. Silicate/oxide minerals were fluorinated by heating with a CO2 laser in an atmosphere of BrF5. The extracted oxygen was purified and isotope ratios of the oxygen triple isotope compositions were determined using a Finnigan MAT253 isotope ratio mass spectrometer. RESULTS. The oxygen triple isotope compositions of meteoric water and terrestrial silicate/oxide minerals fall on statistically distinguishable fractionation lines, defined as [ln(δ17O+1)=λln(δ18O+1)+Δ], where λ and Δ correspond to the slope and intercept, respectively. The fractionation line for meteoric water has λ=0.5285±0.0005 and Δ=0.03±0.02‰ and for terrestrial silicate/oxide minerals has λ=0.5270±0.0005 and Δ=–0.070±0.005‰, at the 95% confidence limit. CONCLUSIONS. All the analyzed terrestrial silicate/oxide minerals including internationally accepted reference materials (NBS‐28, UWG‐2, and San Carlos olivine) have a negative 17O‐excess with respect to VSMOW. We propose that it is necessary to specify if the determined δ17O values of terrestrial and extraterrestrial samples are expressed as the difference from VSMOW or the terrestrial silicate mineral‐corrected value.
Software designed for analytical laboratories to guarantee traceability and accessibility of rocks with their geochemical properties has been developed. The software documents the sample origin, current sample location and the location of any sample subsets (e.g., thin sections, solutions, etc.), and archives all associated geochemical data sets. The software can be installed on a personal computer so is available for use in any laboratory and allows curation before and after publication. The software will be of use in integrating and sharing geological reference materials within and among institutes. In this article, the system design and implementation are detailed. All source codes for the software are available at http://dream.misasa.okayama-u.ac.jp/.
The oxygen isotope (δ18O) composition of quartz and the d(060) values of clay minerals were determined from four pedons of non-allophanic Andosols derived mainly from the Holocene volcanic ash on Yakushima Island. These soils contained considerable amounts of aerosol-sized (1–10 µm) and coarse (>53µm) quartz. The δ18O values for the aerosol-sized quartz ranged from 14.7‰ to 17.4‰, which was comparable to or slightly lower than known values for loess-derived Red and Yellow soils on Tanegashima Island located approximately 20 km east of Yakushima Island. The abundance and δ18O values of the aerosol-sized quartz indicated that non-allophanic Andosols on Yakushima Island were strongly influenced by aeolian dust. However, the presence of coarse quartz implied that granite-derived materials were also incorporated into non-allophanic Andosols. X-ray diffraction patterns for most clay minerals showed two broad peaks around 0.154 and 0.150 nm, respectively. The d(060) values confirmed that 2:1–2:1:1 clay minerals consisted of dioctahedral and trioctahedral clay minerals. Since aeolian dust contains little or no coarse quartz and trioctahedral clay minerals, the abundance of coarse quartz and trioctahedral minerals confirmed that the occurrence of non-allophanic Andosols on Yakushima was influenced by biotite-granite, in addition to aeolian dust.
Field, petrographic–structural and geochemical data are reported for spinel and plagioclase peridotites from the northern domain of the Lanzo peridotite massif (Western Alps). The North Lanzo peridotites are extremely heterogeneous in terms of mineral mode, texture and chemistry. They can be referred to four major groups: (1) spinel harzburgites with coarse granular to porphyroclastic structures; (2) pyroxene-depleted spinel harzburgites recording olivine-forming or pyroxene-consuming microtextures; (3) spinel lherzolites with porphyroclastic to foliated and banded structures; (4) plagioclase-enriched spinel lherzolites. Major and trace element characterization of whole-rocks and their constituent minerals allows reconstruction of the complex series of pre- to syn-rift events this mantle sector underwent. Sr, Nd and Hf isotope data provide information on the nature of infiltrating melts and time constraints. More depleted harzburgites represent refractory protoliths that after melt extraction, possibly in the presence of residual garnet, underwent a first episode of refertilization by enriched mid-ocean ridge basalt (E-MORB)-like melts, whereas harzburgites and spinel lherzolites with ocean island basalt (OIB) signatures document the successive migration of alkaline melts. The most noticeable feature of this group of rocks is their Nd–Hf decoupling, specifically the very high 176Hf/177Hf coupled with very low 143Nd/144Nd. Lu–Hf data for these peridotites define an ∼260 Ma errorchron that is interpreted as evidence of mixing during relatively recent times between old (most probably Proterozoic) refractory subcontinental mantle and OIB-type melts. This event most probably occurred during extension (Triassic times) or during the onset of exhumation (Liassic times). Plagioclase peridotites document the last refertilization episode, involving the shallow-level impregnation of harzburgite mantle by evolved MORB melts before its sea-floor emplacement. This Middle Jurassic event caused the almost complete resetting of the original trace element and 87Sr/86Sr composition. The combination of structural, petrological and geochemical information for a north–south Lanzo traverse, from the North Massif to the South Massif, notwithstanding the effects of the alpine orogeny, allows the study of the complete evolution of a sector of old (Proterozoic?) mantle since the early stages of melt removal and allows reconstruction of the tectonic and magmatic events during continental extension leading to the opening of the Jurassic Ligurian–Piedmontese basin. North Lanzo fundamentally preserves the record of pre-syn-rift ancient episodes, whereas South Lanzo better highlights the processes that deeply modified and refertilized the older lithosphere during subsequent lithosphere extension. Slow to very slow extension led to sea-floor exposure of the subcontinental lithospheric mantle (North Lanzo) at a marginal position, close to the Adria continental margin, and of the deeply melt-modified lithospheric mantle (Lanzo South) in a more distal setting of the basin. In this respect, the Lanzo traverse is closely similar to the ocean–continent transition in slow- or ultraslow-spreading oceanic basins, such as the North Atlantic.
The analytical performance of high-resolution multiple-collector inductively coupled plasma mass spectrometry (HR-MC-ICPMS), employing amplifiers with a 1012 ohm resistor, was examined. HR-MC-ICPMS showed 50 times higher detection efficiency and 100 times better precision for sulfur and 34S/32S than the single-collector high-resolution sector field type ICPMS (HR-ICP-SFMS). The 3σ detection limits for 32S and 34S were 0.2 and 6 ng mL−1, respectively. No matrix effects were observed, for up to 3000 μg g−1 of total dissolved solids (TDS), within 0.6% error. Thus when the isotope dilution (ID) technique is utilized, this method allows analyses of sulfur concentration of seven times smaller, with six times better precision, than the HR-ICP-SFMS methods. To demonstrate the applicability of this ID-HR-MC-ICPMS method, bulk sulfur concentrations in bovine serum albumin, human serum, eight silicate reference materials (JB-2, JB-3, JA-2, JA-3, JP-1, BCR-2, BHVO-1 and AGV-1), and four carbonaceous chondrites (Murchison, Allende, Dal al Gani 521 and 194) were measured.
Records of micrometeorite collisions at down to submicron scales were discovered on dust grains recovered from near-Earth asteroid 25143 (Itokawa). Because the grains were sampled from very near the surface of the asteroid, by the Hayabusa spacecraft, their surfaces reflect the low-gravity space environment influencing the physical nature of the asteroid exterior. The space environment was examined by description of grain surfaces and asteroidal scenes were reconstructed. Chemical and O isotope compositions of five lithic grains, with diameters near 50µm, indicate that the uppermost layer of the rubble-pile-textured Itokawa is largely composed of equilibrated LL-ordinary-chondrite-like material with superimposed effects of collisions. The surfaces of the grains are dominated by fractures, and the fracture planes contain not only sub-µm-sized craters but also a large number of sub-µm - to several-µm-sized adhered particles, some of the latter composed of glass. The size distribution and chemical compositions of the adhered particles, together with the occurrences of the sub-µm-sized craters, suggest formation by hypervelocity collisions of micrometeorites at down to nm scales, a process expected in the physically hostile environment at an asteroid's surface. We describe impact-related phenomena, ranging in scale from 10-9 to 104 meters, demonstrating the central role played by impact processes in the long-term evolution of planetary bodies. Impact appears to be an important process shaping the exteriors of not only large planetary bodies, such as the moon, but also low-gravity bodies such as asteroids.
See visual analysis.
Asteroids are intermediate products of the growth of planetary bodies. Similar to what is observed on the Moon, the surfaces of airless bodies such as asteroids retain accumulated histories of solid-to-solid interactions. Meteorites that fall to Earth are fragments of asteroids; however, their entry into Earth’s atmosphere erases much of the evidence for the processes affecting their surfaces in space. For this reason, observations of the surfaces of low-gravity celestial bodies have been limited to those made remotely. In this study, we examined microscopic grains collected from the outermost surface of an asteroid called Itokawa and returned to Earth by the Hayabusa spacecraft. A nanometer-scale study of these grains in our laboratory provides a glimpse of the asteroid surface that is physically and chemically modified by repeated high-velocity collisions with micrometeorites, or tiny meteorites that enter Earth’s atmosphere.
We have devoted the past 25 years to the development of the Comprehensive Analytical System for Terrestrial and Extraterrestrial Materials (CASTEM), an exclusive laboratory for materials science. CASTEM facilities allow for the determination of elemental and isotopic abundances of geochemically significant elements in multi-scale ranges.CASTEM research targets are not limited to lithic rocks. We have successfully analyzed a variety of materials including human tissue. Utilizing CASTEM, we conducted the“initial analysis”of grains collected from the outermost surface of the asteroid Itokawa that were subsequently returned to Earth by the Hayabusa spacecraft. These analyses involved processing the grains, describing surface morphology, and the determination of elemental and isotopic abundances. The history of the asteroid was unveiled through comprehensive geochemical examinations of the microscopic grains suggesting a physically hostile environment at the asteroid’s surface. Our results reveal that impact processes play a central role in the long-term evolution of planetary bodies in the solar system.
Eclogites are generally considered as derived from basaltic or gabbroic rocks which have either been intensely metamorphosed during subduction-obduction related processes or, associated with continental crust and affected by major crustal thrusting. The advantage of petrological, geochemical, and geochronological study of eclogitic rocks is twofold. First, metabasic rocks are capable of preserving the original magmatic characteristics of igneous formations. Second, the study of eclogites enables us to appreciate the behaviour of isotopic tracers during high-grade metamorphism.
Dislocation textures of olivine grains and Pb isotopic compositions (207Pb/206Pb and 208Pb/206Pb) of olivine-hosted melt inclusions in basaltic lavas from three Hawaiian volcanoes (Kilauea, Mauna Loa, and Koolau) were examined. More than 70% of the blocky olivine grains in the studied samples have a regular-shaped dislocation texture with their dislocation densities exceeding 106cm−2, and can be considered as deformed olivine. The size distribution of blocky olivine grains shows that more than 99% of blocky olivines coarser than 1.2 mm are identified as deformed olivine. These deformed olivine grains are identified as antecrysts, which originally crystallized from previous stages of magmatism in the same shield, followed by plastic deformation prior to entrainment in the erupted host magmas. This study revealed that entrainment of mantle-derived crystallization products by younger batches of magma is an important part of the evolution of magnesium-rich Hawaiian magma. Lead isotopic compositions of melt inclusions hosted in the olivine antecrysts provide information of the evolutionary history of Hawaiian volcanoes which could not have been accessed if only whole rock analyses were carried out. Antecryst-hosted melt inclusions in Kilauea and Koolau lavas demonstrate that the source components in the melting region changed during shield formation. In particular, evidence of interaction of plume-derived melts and upper mantle was observed in the earliest stage of Koolau magmatism.
We studied the elemental and isotopic (Pb, B and Li isotopes) composition of melt inclusions hosted in highly forsteritic (Fo83–91) olivines that were collected from San Bartolo lava and pumice (ST79p, ST82p and ST531p) samples erupted by Stromboli in historical times. The studied melt inclusions have primitive calcalkaline to shoshonitic basaltic compositions. They cover a compositional range far wider than that exhibited by the whole-rocks and differ in key trace element ratios. San Bartolo melt inclusions are characterized by lower incompatible trace element abundances, higher ratios between fluid-mobile (B, Pb, U and LILE) and less fluid-mobile (REE, Th, HFSE) elements and lower La/Yb ratios relative to the pumice-hosted melt inclusions and pumiceous melts erupted during paroxysmal events. Trace elements, along with different Pb, B and Li isotopic signatures, attest to source heterogeneity on the small scale and provide new insights into subducted components beneath Stromboli. Results of a mixing model suggest that metasomatism of the mantle source of pumice-hosted melt inclusions was driven by solute-rich high-pressure fluids (<20%) expelled from the deep portion of the slab. Heterogeneous Pb isotopic composition together with light δ11B (−8.6 to −13.7‰) and δ7Li (+2.3 to −1.7‰) indicates that high-pressure liquids were released in variable proportions from highly dehydrated metabasalts and metasediments. On the other hand, the elemental and isotopic (δ11B ~ −1.9 to −5.9‰) composition of San Bartolo melt inclusions is better explained by the addition of a prevalent aqueous component (~2 to 4%) escaped at shallower depths from sediments and altered basaltic crust in almost equivalent proportions, with a smaller contribution by high-pressure fluids. Owing to the high-angle dip of the subducted cold Ionian slab, aqueous fluids and high-pressure fluids would rise through the mantle wedge and locally superimpose on each other, thus giving origin to variously metasomatized mantle domains.
Compression near collisional plate boundaries causes lithospheric folding which results in the decrease of the pressure beneath the ridge of the fold while the pressure beneath the trough increases. The decompression beneath the lithosphere is likely to bring on basaltic magmatism along and below the ridge. We investigate the subsurface structure beneath Jeju (Cheju) volcanic island and its vicinity, and propose an alternative hypothesis that the basaltic magma beneath the island could be caused by (episodic) lithospheric folding. Unlike the prevailing hypothesis of the intraplate basaltic magmatism that requires extending lithosphere, our hypothesis can explain how the basaltic magma could be generated at the back‐arc regions without the extension.
The Cretaceous Okhotsk–Chukotka volcanic belt (OCVB) is a prominent subduction-related magmatic province, having the remarkably high proportion of silicic rocks (ca. 53% of the present-day crop area, and presumably over 70% of the total volcanic volume). Its estimated total extrusive volume ranges between 5.5 × 105 km3 (the most conservative estimate) and over 106 km3. This article presents a brief outline of the geology of OCVB, yet poorly described in international scientific literature, and results of a geochronological study on the northern part of the volcanic belt. On the base of new and published U–Pb and 40Ar/39Ar age determinations, a new chronological model is proposed. Our study indicates that the activity of the volcanic belt was highly discontinuous and comprised at least five main episodes at 106–98 Ma, 94–91 Ma, 89–87 Ma, 85.5–84 Ma, and 82–79 Ma. The new data allow a semi-quantitative estimate of the volcanic output rate for the observed part of the OCVB (area and volume approximately 105 km2 and 2.5 × 105 km3, respectively). The average extrusion rate for the entire lifetime of the volcanic belt ranges between 1.6 and 3.6 × 10−5 km3yr−1 km−1, depending on the assumed average thickness of the volcanic pile; the optimal value is 2.6 × 10−5 km3yr−1 km−1. Despite imprecise, such estimates infer the time-averaged volcanic productivity of the OCVB is similar to that of silicic LIPs and most active recent subduction-related volcanic areas of the Earth. However, the most extensive volcanic flare-ups at 89–87 and 85.5-84 Ma had higher rates of over 9.0 × 10−5 km3yr−1 km−1. The main volumetric, temporal and compositional parameters of the OCVB are similar to those of silicic LIPs. This gives ground for discussion about the geodynamic setting of the latters, because the widely accepted definition of a LIP implies a strictly intraplate environment. Considering the genesis of the OCVB and other large provinces of silicic volcanism, we propose that residual thermal energy preserved in the continental crust after a previous major magmatic event may have been one of major reasons for high proportion of felsic rocks in a volcanic pile. In this scenario, underplating of mantle-derived basalts causes fast and extensive melting of still hot continental crust and generation of voluminous silicic magmas.
Partially crystalline hornblende gabbro inclusions from the Little Glass Mountain Rhyolite contain euhedral plagioclase, orthopyroxene, hornblende, and apatite crystals in contact with interstitial rhyolitic (71–76% SiO2) glass. Textural and mineral compositional data indicate that the gabbros crystallized sufficiently slowly that surface equilibrium was closely approached at the interface between crystals and the liquid. This rare occurrence represents a natural dynamic crystallization experiment with a “run time” that is not realistically achievable in the laboratory. SIMS analysis of mineral rim-glass pairs have permitted the determination of high-quality, equilibrium trace-element partition coefficients for all four minerals. These data augment the limited partition coefficient database for minerals in high-SiO2 rhyolitic systems. For all minerals, the D values are consistent with those anticipated from crystal-chemical considerations. These data further support a liquid SiO2 control on the REEs (and presumably other elements) partitioning wherein D values systematically increase with increasing liquid SiO2 content.
Science results from the Genesis Mission illustrate the major advantages of sample return missions. (i) Important results not otherwise obtainable except by analysis in terrestrial laboratories: the isotopic compositions of O, N, and noble gases differ in the Sun from other inner solar system objects. The N isotopic composition is the same as that of Jupiter. Genesis has resolved discrepancies in the noble gas data from solar wind implanted in lunar soils. (ii) The most advanced analytical instruments have been applied to Genesis samples, including some developed specifically for the mission. (iii) The N isotope result has been replicated with four different instruments.
Measurements of 238U-230Th-226Ra disequilibria, Sr-Nd-Hf isotopes and major-trace elements have been conducted for lavas erupted in the last quarter-millennium at Hekla volcano, Iceland. The volcanic rocks range from basalt to dacite. Most of the lavas (excluding dactic samples) display limited compositional variation in radiogenic Sr-Nd-Pb-Hf isotopes (87Sr/86Sr = 0.70319-0.70322; 143Nd/144Nd = 0.51302-0.51305; 206Pb/204Pb = 19.04-19.06; 207Pb/204Pb = 15.53-15.54; 208Pb/204Pb = 38.61-38.65; 176Hf/177Hf = 0.28311-0.28312). All the samples possess (230Th/238U) disequilibrium with 230Th excesses, and they show systematic variation in (230Th/232Th) ratios. The highest 226Ra excesses occur in the basalt and most differentiated andesite lavas, while some basaltic-andesite lavas have (226Ra/230Th) ratio that are close to equilibrium. The 238U-230Th-226Ra disequilibria variations cannot be produced by simple closed-system fractional crystallization with radioactive decay of 230Th and 226Ra in a magma chamber. A closed-system fractional crystallization model and assimilation and fractional crystallization (AFC) model indicate that the least differentiated basaltic andesites were derived from basalt by fractional crystallization with a differentiation age of ~24 ± 11 kyr, whereas the andesites were formed by assimilation of crustal materials and fractionation of the basaltic-andesites within 2 kyr. Apatite is inferred to play a key role in fractionating the parent-daughter nuclides in 230Th-238U and 226Ra-230Th to make the observed variations. Our proposed model is that several batches of basaltic-andesite magmas that formed by fractional crystallization of a basaltic melt from a deeper reservoir, were periodically injected into the shallow crust to form individual magma pockets, and subsequently modifying the original magma compositions via simultaneous assimilation and fractional crystallization. The assimilant is the dacitic melt, which formed by partial melting of the crust.
In order to facilitate the understanding of the geological evolution of the Kalahari Craton and its relation to South America, the provenance of the first large-scale cratonic cover sequence of the craton, namely the Ordovician to Carboniferous Cape Supergroup was studied through geochemical analyses of the siliciclastics, and age determinations of detrital zircon. The Cape Supergroup comprises mainly quartz-arenites and a Hirnantian tillite in the basal Table Mountain Group, subgreywackes and mudrocks in the overlying Bokkeveld Group, while siltstones, interbedded shales and quartz-arenites are typical for the Witteberg Group at the top of the Cape Supergroup. Palaeocurrent analyses indicate transport of sediment mainly from northerly directions, off the interior of the Kalahari Craton with subordinate transport from a westerly source in the southwestern part of the basin near Cape Town. Geochemical provenance data suggest mainly sources from passive to active continental margin settings. The reconnaissance study of detrital zircons reveals a major contribution of Mesoproterozoic sources throughout the basin, reflecting the dominance of the Namaqua-Natal Metamorphic Belt, situated immediately north of the preserved strata of Cape Supergroup, as a source with Archaean-aged zircons being extremely rare. We interpret the Namaqua-Natal Metamorphic Belt to have been a large morphological divide at the time of deposition of the Cape Supergroup that prevented input of detrital zircons from the interior early Archaean Kaapvaal cratonic block of the Kalahari Craton. Neoproterozoic and Cambrian zircons are abundant and reflect the basement geology of the outcrops of Cape strata. Exposures close to Cape Town must have received sediment from a cratonic fragment that was situated off the Kalahari Craton to the west and that has subsequently drifted away. This cratonic fragment predominantly supplied Meso- to Neoproterozoic, and Cambrian-aged zircon grains in addition to minor Silurian to Lower Devonian zircons and very rare Archaean (2.5 Ga) and late Palaeoproterozoic (1.8-2.0 Ga) ones. No Siluro-Devonian source has yet been identified on the Kalahari Craton, but there are indications for such a source in southern Patagonia. Palaeozoic successions in eastern Argentina carry a similar detrital zircon population to that found here, including evidence of a Silurian to Lower Devonian magmatic event. The Kalahari and Río de la Plata Cratons were thus in all likelihood in close proximity until at least the Carboniferous.
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.
All planetary materials sampled thus far vary in their relative abundance of the major isotope of oxygen, 16O, such that it has not been possible to define a primordial solar system composition. We measured the oxygen isotopic composition of solar wind captured and returned to Earth by NASA’s Genesis mission. Our results demonstrate that the Sun is highly enriched in 16O relative to the Earth, Moon, Mars, and bulk meteorites. Because the solar photosphere preserves the average isotopic composition of the solar system for elements heavier than lithium, we conclude that essentially all rocky materials in the inner solar system were enriched in 17O and 18O, relative to 16O, by ~7%, probably via non–mass-dependent chemistry before accretion of the first planetesimals.
A method for the simultaneous determination of Cd with In, Tl and Bi by isotope dilution‐internal standardisation (ID‐IS) ICP‐QMS using the same aliquot for rare earth element and other trace element determinations was developed. Samples mixed with an enriched 149Sm spike were decomposed using a HF‐HClO4 mixture, which was evaporated and then diluted with HNO3. After determination of Sm by ID‐ICP‐QMS and Cd, In, Tl and Bi concentrations were determined using the 149Sm intensity as an internal standard. The interference of MoO+ on Cd+ was corrected using the MoO+/Mo+ ratio separately measured using a Mo standard solution, and the validity of the externally determined oxide‐forming ratio correction was evaluated. The MoO+/Mo+ ratios measured using the standard solution and samples were ∼ 0.0002 and <0.002, respectively. Detection limits for Cd, In, Tl and Bi in silicate samples were at levels of <1ng*g−1 with a total uncertainty of <7%. Cadmium in the carbonaceous chondrites, Orgueil (CI1), Murchison (CM2) and Allende (CV3) as well as Cd, In, Tl and Bi in the reference materials, JB‐2, JB‐3, JA‐1, JA‐2, JA‐3, JP‐1 (GSJ), BHVO‐1, AGV‐1, PCC‐1 and DTS‐1 (USGS) and NIST SRM 610, 612, 614 and 616 were determined to show the applicability of this method.
It is widely acknowledged that olivine-hosted melt inclusions retain compositional information unavailable from the study of bulk-rock samples alone. Whether or not the compositions of melt inclusions are truly representative of geologically significant melt bodies has, however, been called into question; isotopic data are critical to resolving this debate but the rare existing data are contradictory. Previous studies of Pb isotope ratios suggest that large compositional variations are preserved by melt inclusions whereas Sr isotope data apparently do not. A new and extensive laser ablation Pb-isotope database is presented here and displays a degree of isotopic heterogeneity in key samples from Mangaia and the Pitcairn seamounts significantly less than previously reported. More than 95% of the inclusions analysed, including results for the low abundance Pb-isotope, 204Pb, which has previously proven difficult to measure, are within error of bulk-rock analyses from these locations. Trace element measurements on two inclusions of different isotopic character from the Pitcairn Seamounts are closely similar to each other, and do not easily support models in which melt inclusions from this locality represent mixing between the Pitcairn mantle plume and the local MORB magmas or lithosphere. Instead, a second component, likely derived from within the plume, is required to explain the isotope and trace element variations observed. In terms of isotopic compositions then, melt inclusions may in most cases be representative of geochemical conditions prevailing within the magmatic plumbing system. The range of isotopic compositions found in a single sample likely includes the composition of the transporting melt (groundmass of the rock) and compositions previously trapped in crystals in the magmatic plumbing system.
Elemental and Li–Sr–Nd isotopic data of minerals in spinel peridotites hosted by Cenozoic basalts allow us to refine the existing models for Li isotopic fractionation in mantle peridotites and constrain the melt/fluid-peridotite interaction in the lithospheric mantle beneath the North China Craton. Highly elevated Li concentrations in cpx (up to 24 ppm) relative to coexisting opx and olivine ( < 4 ppm) indicate that the peridotites experienced metasomatism by mafic silicate melts and/or fluids. The mineral δ7Li vary greatly, with olivine (+0.7 to +5.4‰) being isotopically heavier than coexisting opx (−4.4 to −25.9‰) and cpx (−3.3 to −21.4‰) in most samples. The δ7Li in pyroxenes are considerably lower than the normal mantle values and show negative correlation with their Li abundances, likely due to recent Li ingress attended by diffusive fractionation of Li isotopes. Two exceptional samples have olivine δ7Li of −3.0 and −7.9‰, indicating the existence of low δ7Li domains in the mantle, which could be transient and generated by meter-scale diffusion of Li during melt/fluid-peridotite interaction. The 143Nd/144Nd (0.5123–0.5139) and 87Sr/86Sr (0.7018–0.7062) in the pyroxenes also show a large variation, in which the cpx are apparently lower in 87Sr/86Sr and slightly higher in 143Nd/144Nd than coexisting opx, implying an intermineral Sr–Nd isotopic disequilibrium. This is observed more apparently in peridotites having low 87Sr/86Sr and high 143Nd/144Nd ratios than in those with high 87Sr/86Sr and low 143Nd/144Nd, suggesting that a relatively recent interaction existed between an ancient metasomatized lithospheric mantle and asthenospheric melt, which transformed the refractory peridotites with highly radiogenic Sr and unradiogenic Nd isotopic compositions to the fertile lherzolites with unradiogenic Sr and radiogenic Nd isotopic compositions. Therefore, we argue that the lithospheric mantle represented by the peridotites has been heterogeneously refertilized by multistage melt/fluid-peridotite interactions.
Low-temperature and high-pressure eclogites with an oceanic affinity in the western part of the Dabie orogen have been investigated with combined Lu–Hf and U–Pb geochronology. These eclogites formed over a range of temperatures (482–565°C and 1.9–2.2 GPa). Three eclogites, which were sampled from the Gaoqiao country, yielded Lu–Hf ages of 240.7 ± 1.2 Ma, 243.3 ± 4.1 Ma and 238.3 ± 1.2 Ma, with a corresponding lower-intercept U–Pb zircon age of 232 ± 26 Ma. Despite the well-preserved prograde major- and trace-element zoning in garnets, these Lu–Hf ages mostly reflect the high-pressure eclogite-facies metamorphism instead of representing the early phase of garnet growth due to the occurrence of omphacite inclusions from core to rim and the shell effect. An upper-intercept zircon U–Pb age of 765 ± 24 Ma is defined for the Gaoqiao eclogite, which is consistent with the weighted-mean age of 768 ± 21 Ma for the country gneiss. However, the gneiss has not been subjected to successive high-pressure metamorphism. The new Triassic ages are likely an estimate of the involvement of oceanic fragments in the continental subduction.
The Timor–Tanimbar region constitutes part of the non-volcanic outer Banda Arc of Eastern Indonesia. Here, the world's youngest ‘A’-type high-pressure metamorphic belt crops out with different stages of evolution. Whereas an advanced domal uplift stage is seen in Timor island, the high-pressure (HP) metamorphic belt is still in the first stage of tectonic extrusion on the eastern small islands of Kisar, Leti, Moa, Sermata and Laibobar. The metamorphic rocks on Leti are among the best exposed in the islands. They are tectonically juxtaposed against overlying ultramafic rocks and underlying unmetamorphosed continental shelf sediments, bound by normal and reverse faults, respectively. The Leti metapelites display four progressive metamorphic zones: chlorite–biotite, garnet, chloritoid–staurolite and kyanite zones, with increasing grade. Zonation in Leti metabasite unit is comparable, and progressively changes from blueschist–greenschist transition (BS/GS), through epidote–amphibolite (EA), to amphibolite (AM) facies, with increasing grade. The highest-grade metapelites and metabasites occupy structurally intermediate levels. Overprinting mineral relationships in BS/GS transition schists indicate that decompression occurred from 5.5–7 kbar to < 4 kbar within the temperature range 300–400°C. P–T estimates of the EA and AM units are 6.3–7.6 kbar and 461–521°C, and 9.7–10.3 kbar and 580–626°C respectively. The protoliths of Leti metamorphic rocks are originally Permo-Triassic. The younger sediments and igneous rocks at the margin of the northward advancing Australian continent entered the subduction zone immediately prior to the commencement of the Banda Arc–Australia collision in the Pliocene. Burial reached a maximum depth of 30–35 km at the main stage of peak P–T conditions, and was related to the main stage of the collisional event. Slab break-off at depth in the collision zone facilitated rapid uplift by wedge extrusion and active erosion during the exhumation stage. The tectonic juxtaposition of the schist units at mid-crustal levels and hydration may correspond to the final stage of Barrovian overprinting which continued through transportation from depth. The Leti Island belongs to the eastern portion of the world's youngest blueshist belt which has not yet entered the second-stage mountain building, and is slightly younger than the western Timor which evolved to the extensive mountain-building stage by doming.
A new determination method for Cr, Mn, Fe, Co and Ni in silicate samples by an isotope dilution–internal standardization method (ID–IS)–high resolution (HR)–MC–ICP–MS has been developed. A silicate sample is dissolved into solution, and a Cr-spike solution is added into an aliquot of the sample solution. Then the solution is introduced into HR–MC–ICP–MS without chemical separation. Concentration of Cr is determined by ID, and those of Mn, Fe, Co and Ni are by ID–IS. Matrix effects were examined in detail, and negligible down to a dilution factor (DF; the weight of the sample solution over that of the sample in the solution) of ∼ 3000 for basalt, and ∼ 104 for peridotite and chondrite within an error range of ± 1%. ID–IS–HR–MC–ICP–MS showed intermediate precision of ∼ 1% for basalt and chondrite, which is comparable to ID–TIMS for Cr, Fe and Ni, and > 10 times better than HR–ICP–MS, suggesting that this method is suitable for precise Mn–Cr and Fe–Ni chronometers.
Precise isotopic determination methods for Hf and Pb at sub-nano gram levels have been undertaken for this contribution utilizing the Neptune multiple collector ICP-MS (MC-ICP-MS) with a newly designed sample cone (the Jet cone) and a new pre-amplifier with a highly-resistive register of 1012 ohm. The Jet cone enhanced sensitivities 1.6 and 3 times for Hf and Pb, respectively. The Jet cone showed no significant improvements in reproducibility of Hf isotope analysis at > 1 ng compared to the normal cone, but the reproducibility improved considerably by half when Hf concentration of < 1 ng was measured. Thus, 0.3 and 0.8 ng of Hf can yield reproducibility (2SD in ε-unit) of 3 and 1.7, respectively. Reproducibility (RSD) of 207Pb/206Pb, 206Pb/204Pb, 207Pb/204Pb and 208Pb/204Pb were 0.026, 0.28, 0.33 and 0.36% using total Pb of 0.025 ng, and 0.02, 0.10, 0.10 and 0.08% using 0.05 ng, respectively. Thus, the Jet cone with the new pre-amplifier showed the best performance compared to the normal cone and pre-amplifier and are similar or even better than those obtained by the 202Pb-205Pb double-spike TIMS or multi-ion counting ICP-MS techniques.
An investigation of the petrology and geochemistry of peridotites and gabbros in the Horoman massif, Hokkaido, Japan was undertaken to constrain geochemical processes in the upper mantle. Two types of sample were studied: one type comprises peridotites and gabbros forming thin layers varying from a few millimeters to centimeters in scale (thin-layer peridotites and gabbros); the other comprises thick layers (>1 m scale; massive peridotites and gabbros). There is no clear trace element evidence for metasomatism in the thin-layer peridotites. Instead, they have melt-rock reaction textures interpreted in terms of the formation of secondary pyroxene at the expense of primary porphyroclastic olivine and dissolution of primary porphyroclastic pyroxene to form secondary olivine. The thin-layer gabbros also exhibit no metasomatic effects; they have incompatible element depleted trace element characteristics and mid-ocean ridge basalt (MORB)-like isotopic signatures consistent with the presence of a new type of gabbro that previously has not been described from the Horoman Massif. The whole-rock chemistry of the thin-layer peridotites and thin-layer gabbros can be explained by melt-peridotite reactions between isotopically highly depleted MORB mantle (represented by the thin-layer peridotites) and melt with geochemical affinity to Pacific MORB (represented by the thin-layer gabbros). Sm-Nd and Lu-Hf isotope systematics suggest that these reactions might have occurred at ~300 Ma. Some of the plagioclase lherzolites and all of the spinel lherzolites and harzburgites within the massive peridotites show enrichment in incompatible trace elements and more radiogenic Hf-Nd-Pb isotopic compositions than the incompatible-element depleted thin-layer peridotites. The analyzed massive gabbros are interpreted as subduction-related magmas formed in a MORB-source mantle wedge, which have subsequently interacted with a fluid or melt in the Hidaka subduction zone. Hf-Nd-Pb isotope systematics reveal that this interaction may have occurred at an age younger than ~50 Ma. Melt- and fluid-related processes occurring in the upper mantle are systematically identified from the samples of the Horoman Massif based on petrography, major and trace element, and Sr-Nd-Pb-Hf isotope geochemistry. These processes occurred in different tectonic settings such as the convecting oceanic mantle and supra-subduction zone mantle wedge and have variably modified the original chemistry of residual mantle protolith, formed by partial melting of a depleted MORB source mantle at ~1 Ga.
The contribution of subducted carbonate sediments to the genesis of the Southwestern Colombian arc magmas was investigated using a comprehensive petrography and geochemical analysis, including determination of major and trace element contents and Sr, Nd, Hf and Pb isotope compositions. These data have been used to constrain the depth of decarbonation in the subducted slab, indicating that the decarbonation process continues into the sub-arc region, and ultimately becomes negligible in the rear arc. We propose on the basis of multi-isotope approach and mass balance calculations, that the most important mechanism to induce the slab decarbonation is the infiltration of chemically reactive aqueous fluids from the altered oceanic crust, which decreasingly metasomatize the mantle wedge, triggering the formation of isotopically different primary magmas from the volcanic front (VF) with relatively high 176Hf/177Hf, high 87Sr/86Sr, negative values of εNd and lower Pb isotopes compared to the rear arc (RA). The presence of more aqueous fluids at the volcanic front may increase the degree of decarbonation into carbonate-bearing lithologies. Moreover, with increasing pressure and temperature in the subduction system, the decrease in dehydration of the slab, leads to cessation of fluid-induced decarbonation reactions at the rear arc. This development allows the remaining carbonate materials to be recycled into the deep mantle.
In this paper, Late Miocene blueschist and eclogite belts, including the world's youngest blueschist belt in Timor–Tanimbar Island chain, eastern Indonesia, and the world's youngest coesite-bearing eclogite, Papua New Guinea, together with selected Cenozoic high-pressure and ultrahigh-pressure metamorphic rocks are reviewed. From a synthesis of the geology, metamorphism and chronology of these rocks, the formation and exhumation process are evaluated and the significance on tectonics at convergent plate boundaries is discussed.
During its 1800-year-long persistent activity the Stromboli volcano has erupted a highly porphyritic (HP) volatile-poor scoriaceous magma and a low porphyritic (LP) volatile-rich pumiceous magma. The HP magma is erupted during normal Strombolian explosions and lava effusions, while the LP one is related to more energetic paroxysms. During the March–April 2003 explosive activity, Stromboli ejected two typologies of juvenile glassy ashes, namely highly vesicular LP shards and volatile-poor HP shards. Their textural and in situ chemical characteristics are used to unravel mutual relationships between HP and LP magmas, as well as magma dynamics within the shallow plumbing system. The mantle-normalized trace element patterns of both ash types show the typical arc-lava pattern; however, HP glasses possess incompatible element concentrations higher than LP glasses, along with Sr and Eu negative anomalies. HP shards are generally characterized by higher Li contents (to ~20 ppm) and lower δ7Li values (+1.2 to −3.8‰) with respect to LP shards (Li contents of 7–14 ppm and δ7Li ranging between +4.6 and +0.9‰). Fractional crystallization models based on major and trace element compositions, combined with a degassing model based on open-system Rayleigh distillation and on the assumption that melt/fluidDLi > 1, show that abundant (~30%) plagioclase precipitation and variable degrees of degassing can lead the more primitive LP magma to evolve toward a differentiated (isotopically lighter) HP magma ponding in the upper conduit and undergoing slow continuous degassing-induced crystallization. This study also evidences that in March 2003 Stromboli volcano poured out a small early volume of LP magma that traveled slower within the conduit with respect to later and larger volumes of fast ascending LP magma erupted during the April 5 paroxysm. The different ascent rates and cooling rates of the two LP magma batches (i.e., pre- and post-paroxysm) resulted in small, but detectable, differences in their chemical signatures. Finally, this study highlights the high potential of in situ investigations of juvenile glassy ashes in petrologic and geochemical monitoring the volcanic activity and of Li isotopes as tracers of degassing processes within the shallow plumbing system.
A method to determine F and Cl in silicate materials by employing pyrohydrolysis and ion chromatography (IC) is described. Pyrohydrolysis involved mixing a pulverised sample (∼40 mg) with V2O5 (∼160mg) and heating to 1100°C under a wet oxygen flow in a quartz tube. Recovery yields of F and Cl were ∼97% using a NaF+NaCl standard solution. Detection limits of the pyrohydrolysis‐IC method for silicate samples were 0.36 and 0.69μg*g‐1 for F and Cl, respectively. Fluorine and Cl concentrations were determined in the reference materials JB‐2, JB‐3 and JA‐1 from the GSJ; BCR‐2, BHVO‐1, BHVO‐2, AGV‐1 and AGV‐2 from the USGS; and NIST SRM 610, 612 and 614 glasses. Precisions (RSD) for determinations of F were 1–13% (except NIST SRM 614) and 2–19% for Cl, and were dependent on the concentration and blank correction. Most results obtained in this study were in good agreement with those of previous studies. In comparison, the Na2CO3+ZnO fusion method at 900°C showed that the yields of F and Cl by alkaline fusion systematically decreased with fusion duration time. The yields were 84% and 83% for JB‐3, inferring that F and Cl were lost in this alkaline fusion.
The standard planetary formation models assume that primitive materials, such as carbonaceous chondrites, are the precursor materials of evolved planetesimals. Past chronological studies have revealed that planetesimals of several hundred kilometers in size, such as the Howardite-Eucrite-Diogenite (HED) parent body (Vesta) and angrite parent body, began their differentiation as early as ~3 million years of the solar system formation, and continued for at least several million years. However, the timescale of planetesimal formation in distinct regions of the inner solar system, as well as the isotopic characteristics of the reservoirs from which they evolved, remains unclear. Here we present the first report for the precise 53Mn-53Cr ages of monomict ureilites. Chemically separated phases from one monomict ureilite (NWA 766) yielded the Mn-Cr age of 4564.60 ± 0.67 Ma, identical within error to the oldest age preserved in other achondrites, such as angrites and eucrites. The 54Cr isotopic data for this and seven additional bulk ureilites show homogeneous ε54Cr of ~–0.9, a value distinct from other achondrites and chondrites. Using the ε54Cr signatures of Earth, Mars, and Vesta (HED), we noticed a linear decrease in the ε54Cr value with the heliocentric distance in the inner region of the solar system. If this trend can be extrapolated into the outer asteroid belt, the ε54Cr signatures of monomict ureilites will place the position of the ureilite parent body at ~2.8 AU. These observations imply that the differentiation of achondrite parent bodies began nearly simultaneously at ~4565 Ma in different regions of the inner solar system. The distinct ε54Cr value between ureilite and carbonaceous chondrite also implies that a genetic link commonly proposed between the two is unlikely.
High-precision Cr isotope ratios for chondrules and metal grain separated from CB chondrite Gujba were determined. The ε54Cr values (εiCr = [(iCr/52Cr)sample/(iCr/52Cr)standard – 1] × 104) for all samples were identical within the analytical uncertainty, with a mean value of +1.29 ± 0.02. Uniform ε54Cr signatures of both chondrules and metal grains imply that the Cr isotope systematics of the meteorite was once completely equilibrated. The ε53Cr values of the chondrules and metal grain, on the other hand, display a strong correlation with the 55Mn/52Cr ratio. The 53Mn/55Mn calculated from the slope of the isochron is (3.18 ± 0.52) × 10–6. This corresponds to absolute ages of 4563.7 ± 1.2 Ma and 4563.5 ± 1.1 Ma using angrites D'Orbigny and LEW 86010, respectively, as time anchors. These ages are consistent with the ages obtained using other short- and long-lived radio nuclides, supporting the uniform distribution of 53Mn in the early solar nebula.
A rare composite xenolith and abundant cumulative pyroxenites obtained from the Mesozoic Fangcheng basalts on the eastern North China Craton record a complex history of melt percolation and circulation in the subcontinental lithospheric mantle. The composite xenolith has a dunite core and an olivine clinopyroxenite rim. The dunite is of cumulative origin and has a granular recrystallized texture and extremely low Mg# [100 Mg/(Mg + Fe) = 81–82] contents in olivines. The olivine clinopyroxenite contains larger clinopyroxene and/or orthopyroxene with a few fine-grained olivine and tiny phlogopite, feldspar, and/or carbonate minerals interstitial to clinopyroxene. The clinopyroxene has low Mg# (83–85). Compositional similarity between dunitic olivine and pyroxenitic one indicates a sequential crystallization of dunite and pyroxenite from a precursor melt. Pyroxenite xenoliths include olivine websterites and clinopyroxenites, both are of cumulative origin. Estimation of the melt from major oxides in olivines and REE concentrations in clinopyroxenes in these composite and pyroxenite xenoliths suggests a derivation from subducted crustal materials, consistent with the highly enriched EMII-like Sr and Nd isotopic ratios observed in the pyroxenites. Occurrence of phlogopite, feldspar and carbonate minerals in some xenoliths requires the melt rich in alkalis (K, Na), silica and volatiles (water and CO2) at the latest stage as well, similar to highly silicic and potassic melts. Thus, the occurrence of these composite and pyroxenite xenoliths provides an evidence for voluminous injection of recycled crustal melts into the lithosphere beneath the southeastern North China Craton at the Late Mesozoic, a reason for the rapid lithospheric enrichment in both elemental and isotopic compositions.
We investigated the oceanic-type Xiongdian high-pressure eclogites in the western part of the Dabie orogen with combined U–Pb, Lu–Hf, Sm–Nd and Ar–Ar geochronology. Three groups of weighted-mean 206Pb/238U ages at 315 ± 5, 373 ± 4 and 422 ± 7 Ma are largely consistent with previous dates. In contrast, Lu–Hf and Sm–Nd isochron dates yield identical ages of 268.9 ± 6.9 and 271.3 ± 5.3 Ma. Phengite and amphibole Ar–Ar total fusion analyses give Neoproterozoic apparent ages, which are geologically meaningless due to the presence of excess 40Ar. Plagioclase inclusions in zircon cores suggest that the Silurian ages likely represent protolith ages, whereas the Carboniferous ages correspond to prograde metamorphism, based on the compositions of garnet inclusions. Despite weakly-preserved prograde major- and trace element zoning in garnet, a combined textural and compositional study reveals that the consistent Lu–Hf and Sm–Nd ages of ca. 270 Ma record a later event of garnet growth and thus mark the termination of high-pressure eclogite–facies metamorphism. The new U–Pb, Lu–Hf and Sm–Nd ages suggest a model of continuous processes from oceanic to continental subduction, pointing to the onset of prograde metamorphism prior to ca. 315 Ma for the subduction of oceanic crust, while the peak eclogite–facies metamorphic episode is constrained to between ca. 315 and 270 Ma. Thus, the initiation of continental subduction is not earlier than ca. 270 Ma.
Previous studies on the atoll-shaped garnets in ultrahigh-pressure (UHP) metamorphic eclogites from the Dabie orogen, east-central China, suggest a fluid-enhanced overgrowth origin at the onset of exhumation. The atoll-garnets bearing eclogite place better constraints on the timing of the retrograde fluid activity and are a straightforward target to gain insight into the isotopic equilibrium and/or disequilibrium during exhumation. Comprehensive textural, chemical and Lu–Hf geochronological analyses on the atoll garnet-bearing eclogite show that the retrograde fluid activity event likely occurred at ca. 221 Ma. The Lu–Hf age of 221.0±2.3 Ma marks the last garnet overgrowth episode during exhumation rather than prograde metamorphism. This somewhat restricted study suggests that dating the prograde-zoning-preserved garnets may bias results towards a particular metamorphic event rather than the prograde timing, as previously thought. The general assumption that larger garnet crystals in metamorphic rocks are older should be made with caution, and it is likely invalid in atoll garnet-bearing metamorphic eclogites because the preliminary garnet cores have been largely consumed. These observations highlight that linking textural and chemical analyses is crucial for interpreting geochronological data.
Paleocene (55–58 Ma) adakitic andesites from the Yanji area of NE China are subdivided into clinopyroxene andesites and amphibole andesites. Relative to the clinopyroxene andesites, the amphibole andesites contain higher SiO2, K2O and lower MgO, FeOT, Al2O3, CaO, TiO2, Cr, Ni, Sr, Y and Nb, and have evolved Sr–Nd–Pb isotope compositions. Compositional variation between the clinopyroxene andesites and amphibole andesites involves systematic decreases in MgO, Sr/Nd and εNd(t) accompanied by increases in 87Sr/86Sr(i) and 206Pb/204Pb(i), and suggests a role for crustal contamination. The compositional variations recorded in clinopyroxene and amphibole phenocrysts indicate that the primary mantle-derived adakitic magma experienced complex crustal-level processes, including magma mixing, fractional crystallization and crustal contamination or assimilation. The low Na2O contents and adakitic trace element features (high Sr/Y and Nd/Yb) in Mg-rich parts of clinopyroxene phenocrysts, and negative Sr and Eu anomalies in the Fe-rich clinopyroxene cores, suggest that all clinopyroxenes crystallized in equilibrium with little or no garnet, and argues against magmatic evolution involving differentiation of basaltic magmas. Combined mineralogical and geochemical data indicate that the clinopyroxene andesites were generated by magma mixing, clinopyroxene fractionation and limited degrees of crustal assimilation; whereas the amphibole andesites underwent magma mixing, fractionation of clinopyroxene + amphibole +/− plagioclase and higher degree of crustal assimilation. The difference in mineralogical assemblage between the two rock types was influenced by magma temperature, i.e., 900–950 °C for the amphibole andesites and > 950 °C for the clinopyroxene andesites. Our results provide the following important constraints on high-MgO adakitic magma (or low-SiO2 adakite) petrogenesis: (1) the primary magma of such adakites is probably produced through melting of slab melt-modified mantle rather than being a slab melt variably hybridized by peridotite: (2) The complex magmatic evolution recorded in the Yanji adakitic andesites suggests that such adakitic rocks are far from melts in equilibrium with mantle, and magmatic process needs to be carefully examined before the petrogenetic or geodynamic significance can be assessed: (3) The perquisites for creating high-MgO or low-SiO2 adakites include slab melt–mantle interaction during oceanic slab subduction and melting of this metasomatized mantle, but this melting event need not necessarily be related in time to the subduction event.
A method for the determination of Ge, As, Se and Te in silicate samples using isotope dilution‐internal standardisation (ID‐IS) octopole reaction cell (ORC) ICP‐QMS by normal sample nebulisation was developed. The method does not involve either hydride generation or ion exchange. Germanium, Se and Te were determined by isotope dilution (ID), and As was determined by ID‐IS. A silicate sample with an added Ge‐Se‐Te spike was digested with an HF‐HNO3‐HBr mixture, dried, re‐dissolved with HF and the supernatant liquid was directly aspirated into an ORC‐ICP‐QMS instrument with He or H2 gas. No matrix effects were observed down to a dilution factor (DF) of ∼ 70 for Ge, Se and Te and DF of ∼ 1000 for As, which resulted in 3s detection limits in silicates of 2, 1, 0.1 and 4 ng g−1, respectively. Advantages of the method are the simple sample introduction as well as a capability of determining S, Ti, Zr, Nb, Mo, Sn, Sb, Hf and Ta by ID‐IS‐ICP‐QMS/SFMS from the same solution. Furthermore, the total sample solution consumption was only 0.253 ml with DF = 2000. Therefore, only a 0.13 mg test portion was required. To demonstrate the applicability of this technique, Ge, As, Se and Te in eight silicate reference materials were determined, as well as S, Ti, Zr, Nb, Mo, Sn, Sb, Hf and Ta in four carbonaceous chondrites.
In this review, a new classification of elements based on behavior in hydrofluoric acid (HF) solution is presented for the precise quantitative analysis of each element by inductively coupled plasma mass spectrometry (ICP-MS). The elements are divided into 7 groups: (1) "fluorophile" elements; (2) insoluble fluoride-forming elements; (3) "bromophile" or "iodophile" elements; (4) "oxophile" elements; (5) "aquaphile" elements; (6) bare cation elements; and (7) other elements. Especially, the importance of fluorophile and insoluble fluoride-forming elements in elemental analysis is described. Due to the elemental characteristics, these two groups of elements cannot be dissolved simultaneously in the same solution, and thus cannot be measured together. In addition, coprecipitation of the fluorophile elements with the insoluble fluorides occurs in some conditions and hinders accurate analysis. The peculiar conditions when the coprecipitation occurs are discussed, and the "Al-addition" and "Mg-addition" methods for overcoming these problems are described. In addition, some state-of-the-art analytical techniques in ICP-MS are shown, and future directions of the element analysis are presented.
Elemental and isotopic abundances of lithium in chondrule constituents in the Allende CV3 meteorite were determined using secondary ion mass spectrometry. Olivines and mesostasis dominated by a feldspathic phase are depleted in Li (< 1 µg g-1 and 0.1–0.6 µg g-1, respectively). In contrast, low-Ca pyroxenes and mesostasis dominated by a Na-rich phase are enriched in Li (∼ 1-8 µg g-1 and 0.4-3.5 µg g-1, respectively) and the interchondrule matrix is generally enriched in Li (∼ 2.0 µg g-1 on average). The Li isotopic abundance of olivine ranges from d 7Li ∼ -32 to 21. The spatial distributions of elemental and isotopic abundances of Li in olivines within individual chondrules exhibit no systematic pattern. This suggests that the distribution of Li in olivine was not disturbed during aqueous alteration or thermal metamorphism on the Allende meteorite parent body. Although mesostasis is the last crystallizing phase from a chondrule melt and is expected to be enriched in Li, in the Allende meteorite it is generally depleted in Li. We suggest that during aqueous alteration on the CV asteroid, Li in mesostasis was leached out by aqueous fluids. The Li-enriched Na-rich mesostasis was probably produced later by infiltration of Na-rich fluids. It seems likely that aqueous fluids sequestered alkali elements from the Allende–chondrite region in the CV parent asteroid, although significant amounts of Li are preserved in ferrous olivine in the interchondrule matrix.
While exposure to fibers and particles has been proposed to be associated with several different lung malignancies including mesothelioma, the mechanism for the carcinogenesis is not fully understood. Along with mineralogical observation, we have analyzed forty-four major and trace elements in extracted asbestos bodies (fibers and proteins attached to them) with coexisting fiber-free ferruginous protein bodies from extirpative lungs of individuals with malignant mesothelioma. These observations together with patients’ characteristics suggest that inhaled iron-rich asbestos fibers and dust particles, and excess iron deposited by continuous cigarette smoking would induce ferruginous protein body formation resulting in ferritin aggregates in lung tissue. Chemical analysis of ferruginous protein bodies extracted from lung tissues reveals anomalously high concentrations of radioactive radium, reaching millions of times higher concentration than that of seawater. Continuous and prolonged internal exposure to hotspot ionizing radiation from radium and its daughter nuclides could cause strong and frequent DNA damage in lung tissue, initiate different types of tumour cells, including malignant mesothelioma cells, and may cause cancers.
In view of the requirement of a well-characterized and easily available aquatic sediment reference material, a comprehensive analysis comprising of fifty major, minor and trace elements as well as Sr–Nd–Pb–Hf isotopes were carried out in the stream sediment reference material, JSd-1, issued by the Geological Survey of Japan. The data for marine sediment reference material, MAG-1, issued by U.S. Geological Survey is also obtained for comparison. The elements were divided into two groups: Group I and Group II. Elements in Group I form stable soluble ions in HNO3; and those in Group II form soluble oxo- and fluoro-complexes in HF, such as Zr, Nb, Hf, Ta, etc. For Group I, the sample was decomposed with HF ina tetra fluoro ethylene (TFE) bomb at 245°C for 96 hrs with Mg addition. The elemental concentration was measured by quadrupole type inductively coupled plasma source mass spectrometry (ICP-QMS) and sector field type ICP-MS (ICP-SFMS) using isotope dilution-internal standardization (ID-IS) methods. The aliquot of the sample solution was passed through 3-step column chemistry for isotope ratio determination of Pb by multiple collector (MC) ICP-MS and thermalionization mass spectrometry (TIMS), and Sr and Nd by TIMS. For Group II elements, the sample was decomposed withHF in a TFE bomb with the same time and temperature settings. Zr, Mo, Sn, Sb and Hf were determined by ID, and Nb and Ta by ID-IS using ICP-QMS. The original JSd-1 powder showed heterogeneity for Group II elements, indicating insufficient pulverization and distribution. Thus, we further pulverized the powder and measured the concentration, which showed improved homogeneity. The aliquot for the re-pulverized powder was passed through 2-step column chemistry, and the Hf isotope ratio was determined by MC-ICP-MS. Thus a new data on the trace elements as well as Sr–Nd–Pb–Hf isotope ratios is provided for JSd-1 and MAG-1 in this paper.
Nappes in the southern sector of the Southern Brasilia Belt record suturing of the Paranapanema Block and Socorro–Guaxupe Arc with a subducted passive margin on the western side of the Sao Francisco Craton. We report secondary ion mass spectrometry U–Pb zircon ages that for the first time constrain the age of: (1) retrograded eclogite from a block along the tectonic contact beneath the uppermost nappe in a stack of passive margin-derived nappes; (2) high-pressure granulite-facies metamorphism in the uppermost passive margin-derived nappe; (3) high-pressure granulite-facies metamorphism in the overlying arc-derived nappe. Rare zircons from a retrograded eclogite yield a 206Pb/ 238U age of 678 ± 29 Ma, which we interpret as most likely to date close-to-peak-P metamorphism and to provide a minimum age for detachment of the overlying passive margin-derived nappe from the subducting plate. Zircon associated with ilmenite in samples from two structural levels in the passive margin-derived high-pressure granulite nappe yields 206Pb/ 238U ages of 648 ± 12 and 647 ± 11 Ma, and Ti-in-zircon crystallization temperatures from c. 860 °C down to c. 785 °C, but skewed toward the lower part of the range. These data indicate zircon formation during cooling from around peak T to the solidus, consistent with the high-T retrograde P–T path deduced from microstructures linked to phase assemblage fields in isochemical phase diagrams. Rb–Sr multi-mineral–whole-rock isochrons from two samples from close to the bottom of this nappe date formation of a retrograde sillimanite-bearing penetrative fabric to c. 590 Ma at temperatures of c. 750 °C (based on Ti-in-quartz thermometry). Rare zircons from leucosome in high-pressure granulite from the overlying arc-derived nappe yield a 206Pb/ 238U ages of 622 ± 28 Ma and Ti-in-zircon crystallization temperatures from c. 970 °C down to c. 820 °C, which we interpret to record formation of zircon during cooling from peak high-pressure granulite-facies conditions. These ages indicate that the first stage of craton amalgamation in West Gondwana may have occurred earlier than previously inferred.
Abyssal peridotites, the depleted solid residues of ocean ridge melting, are the most direct samples available to assess upper oceanic mantle composition. We present detailed isotope and trace element analyses of pyroxene mineral separates from Southwest Indian Ridge abyssal peridotites and pyroxenites in order to constrain the size and length scale of mantle heterogeneity. Our results demonstrate that the mantle can be highly heterogeneous to <1 km and even <0.1 m length scales. Examination of Nd isotopes in relation to modal, trace, and major element compositions indicate that the length scales and amplitudes of heterogeneities in abyssal peridotites reflect both ancient mantle heterogeneity and recent modification by melting, melt‐rock reaction and melt crystallization. The isotopic and trace element compositions of pyroxenite veins in this study indicate that they are not direct remnants of recycled oceanic crust, but instead are formed by recent melt crystallization. Combined with existing data sets, the results show that the average global isotopic composition of peridotites is similar to that of mid‐ocean ridge basalts, though peridotites extend to significantly more depleted 143Nd/144Nd and 87Sr/86Sr. Standard isotope evolution models of upper mantle composition do not predict the full isotopic range observed among abyssal peridotites, as they do not account adequately for the complexities of ancient and recent melting processes.
A sequential chemical separation technique for Cr, Fe, Ni, Zn, and Cu in terrestrial and extraterrestrial silicate rocks was developed for precise and accurate determination of elemental concentration by the isotope dilution method (ID). The technique uses a combination of cation−anion exchange chromatography and Eichrom nickel specific resin. The method was tested using a variety of matrixes including bulk meteorite (Allende), terrestrial peridotite (JP-1), and basalt (JB-1b). Concentrations of each element was determined by thermal ionization mass spectrometry (TIMS) using W filaments and a Si−B−Al type activator for Cr, Fe, Ni, and Zn and a Re filament and silicic acid−H3PO4 activator for Cu. The method can be used to precisely determine the concentrations of these elements in very small silicate samples, including meteorites, geochemical reference samples, and mineral standards for microprobe analysis. Furthermore, the Cr mass spectrometry procedure developed in this study can be extended to determine the isotopic ratios of 53Cr/52Cr and 54Cr/52Cr with precision of ∼0.05ε and ∼0.10ε (1ε = 0.01%), respectively, e nabling cosmochemical applications such as high precision Mn−Cr chronology and investigation of nucleosynthetic isotopic anomalies in meteorites.
From previously published 14C and K–Ar data, the age of formation of Lake Nyos maar in Cameroon is still in dispute. Lake Nyos exploded in 1986, releasing CO2 that killed 1750 people and over 3000 cattle. Here we report results of the first measurements of major elements, trace elements and U-series disequilibria in ten basanites/trachy-basalts and two olivine tholeiites from Lake Nyos. It is the first time tholeiites are described in Lake Nyos. But for the tholeiites which are in 238U–230Th equilibrium, all the other samples possess238U–230Th disequilibrium with 15 to 28% enrichment of 230Th over238U. The (226Ra/230Th) activity ratios of these samples indicate small (2 to 4%) but significant 226Ra excesses. U–Th systematics and evidence from oxygen isotopes of the basalts and Lake Nyos granitic quartz separates show that the U-series disequilibria in these samples are source-based and not due to crustal contamination or post-eruptive alteration. Enrichment of 230Th is strong prima facie evidence that Lake Nyos is younger than 350 ka. The 230Th–226Ra age of Nyos samples calculated with the (226Ra/230Th) ratio for zero-age Mt. Cameroon samples is 3.7 ± 0.5 ka, although this is a lower limit as the actual age is estimated to be older than 5 ka, based on the measured mean 230Th/238U activity ratio. The general stability of the Lake Nyos pyroclastic dam is a cause for concern, but judging from its230Th–226Ra formation age, we do not think that in the absence of a big rock fall or landslide into the lake, a big earthquake or volcanic eruption close to the lake, collapse of the dam from erosion alone is as imminent and alarming as has been suggested.
Atmospheric oxygen concentrations in the Earth’s atmosphere rose from negligible levels in the Archaean Era to about 21% in the present day. This increase is thought to have occurred in six steps, 2.65, 2.45, 1.8, 0.6, 0.3 and 0.04 billion years ago, with a possible seventh event identified at 1.2 billion years ago. Here we show that the timing of these steps correlates with the amalgamation of Earth’s land masses into supercontinents. We suggest that the continent–continent collisions required to form supercontinents produced supermountains. In our scenario, these supermountains eroded quickly and released large amounts of nutrients such as iron and phosphorus into the oceans, leading to an explosion of algae and cyanobacteria, and thus a marked increase in photosynthesis, and the photosynthetic production of O2. Enhanced sedimentation during these periods promoted the burial of a high fraction of organic carbon and pyrite, thus preventing their reaction with free oxygen, and leading to sustained increases in atmospheric oxygen.
Crystal-size and spatial distributions of minerals in metamorphic rocks provide insight into their nucleation, growth environment, and the metamorphic evolution of their host rocks. Episodic nucleation and growth histories for garnets in eclogites from the Dabie orogen are revealed by variations in crystal size, geochemical zoning, and mineralogy of inclusions in garnets. The studied garnets show pseudo-lognormal crystal-size distributions (CSDs), prograde chemical zoning patterns indexed by mineral inclusions, and are mainly distributed at random. Constant growth rate for each episode is proposed based on the mineralogy of inclusions in garnets and the chemical zoning patterns. The CSD shapes were evaluated in terms of a size-dependent proportionate growth model and a thermally accelerated, diffusion-controlled model but neither is consistent with the geochemical data and the concordant occurrence of mineral inclusions in garnet. Initial increasing nucleation rate followed by a subsequent, medial stage of nearly constant growth and finally declining nucleation rate is inferred from the CSD data. This study suggests that linking chemical analysis with textural analysis is crucial to avoid misleading interpretation solely through CSD shapes of minerals in metamorphic rocks.
Ultra‐high‐pressure eclogites from the Dabie orogen that formed over a range in temperatures (∼600 to > 700 °C) have been investigated with combined Lu–Hf and Sm–Nd geochronology. Three eclogites, sampled from Zhujiachong, Huangzhen and Shima, yield Lu–Hf ages of 240.0 ± 5.0, 224.4 ± 1.9 and 230.8 ± 5.0 Ma and corresponding Sm–Nd ages of 222.5 ± 5.0, 217.6 ± 6.1 and 224.2 ± 2.1 Ma respectively. Well‐preserved prograde major‐ and trace‐element zoning in garnet in the Zhujiachong eclogite suggests that the Lu–Hf age mostly reflects an early phase of garnet growth that continued over a time interval of c. 17.5 Myr. For the Huangzhen eclogite, despite preserved elemental growth zoning in garnet, textural study reveals that the Lu–Hf age is biased towards a later garnet growth episode rather than representing early growth. The narrow time interval of <6.6 Myr defined by the difference between Lu–Hf and Sm–Nd ages indicates a short final garnet growth episode and suggests a rapid cooling stage. By contrast, the rather flat element zoning in garnet in the Shima eclogite suggests that Lu–Hf and Sm–Nd ages for this sample have been reset by diffusion and are cooling ages. The new Lu–Hf ages point to an initiation of prograde metamorphism prior to c. 240 Ma for the Dabie orogen, while the exact peak metamorphic timing experienced by specific samples ranges between c. 230 to c. 220 Ma.
Multi-stage formation of tourmaline occurs in the Hnilec granite-related hydrothermal tin mineralisation system from the Western Carpathians, Slovakia. The tourmalines belong to the schorl–dravite series and have two major stages of formation: the majority crystallized during the first stage (defined as M-stage), forming zoned tourmaline crystals with the cores being generally more Fe, Al, and Mn rich than the rims. During the second stage (defined as L-stage), tourmaline formed as small veins or irregular patches along fractures and cracks in the M-stage tourmaline grains. In the contact metapelites near the granite body, the L-stage tourmalines are more Mg-rich and Fe, Al, Mn depleted than the M-stage tourmalines. In the granites, the L-stage tourmalines have generally similar compositions to those of the M-stage tourmaline rims. The boron isotopic compositions of the M-stage tourmalines vary from − 10.3‰ to − 15.4‰; with no clear variation between the cores and the rims, however, some of the tourmaline grains from the contact metapelites show a slightly higher δ11B in the cores than in the rims. The L-stage tourmalines have lower δ11B value of − 16.0‰ to − 17.1‰. We suggest that these trends reflect a changing fluid source from a dominant magmatic–hydrothermal fluid derived from the granites to a late-stage metamorphic fluid derived from the regional metamorphism (chlorite and biotite zone) in the metapelites. The significantly higher Fe3+ in the L-stage than the M-stage tourmalines reflect changing redox conditions towards a more oxidising environment. This redox condition change may have important implications for the hydrothermal tin mineralisation in the area.
We present major and trace element concentrations and Sr-Nd-Hf-Pb isotope data for the c. 13-2 Ma Tertiary lavas from eastern Iceland. Our new geochemical results, together with published geological, geochronological, geochemical and geophysical data, are used to evaluate temporal changes in mantle sources contributing to the Tertiary Icelandic magmatism and the relative roles of these sources in magma productivity. The trace element and radiogenic isotopic compositions clearly distinguish three distinct end-member components in the Tertiary magmatism. Temporal variations in lava geochemistry can be attributed to changes in the relative contributions of these three end-member components to the erupted magmas and correlated with temporal variations in magma productivity. The extrusion of lavas with geochemically and isotopically enriched compositions was particularly pronounced at ~13-12 and 8-7 Ma, coincident in time with higher magma productivity. However, the geochemical characteristics of the lavas are different during these two periods: the 13-12 Ma lavas have more radiogenic 176Hf/177Hf and less radiogenic 206Pb/204Pb than those erupted from 8 to 7 Ma. The eruption of relatively depleted lavas, at around 10 Ma and younger than 6.5 Ma, is coincident with lower magma productivity. The correlation between the composition and productivity of the Tertiary lavas from eastern Iceland is probably due to periodic changes in the involvement of the enriched end-member component, followed by a gradation to periods dominated by the signature of the depleted end-member component and lower magma productivity, at an approximate frequency of 5 Myr.
Magma generation processes were investigated for alkali basalt lavas from Rishiri Volcano, located at the rear of the Kurile arc, using major and trace elements and Sr, Nd, Pb and Th isotopic data. The Numaura and the Araragiyama lava flows, investigated in this study, show a significant variation in TiO2 contents (1.0–1.4 wt %) despite a limited variation in SiO2 content (48.5–50.0 wt %); TiO2 contents correlate positively with 143Nd/144Nd and negatively with 87Sr/86Sr, 206Pb/204Pb, 207Pb/204Pb and 208Pb/204Pb. The compositional variations of the lavas cannot be explained by magma chamber processes, such as fractional crystallization, crustal assimilation and magma mixing, and they are suggested to have formed principally during magma generation. The variation of the TiO2 contents essentially reflects a variation of the degree of partial melting (from ∼2 to ∼3%) of the source mantle, and it is inferred that the melting degree correlated positively with amounts of slab-derived materials influxed into the melting region. The melting appears to have occurred progressively under isothermal and isobaric conditions, as slab-derived materials were continuously supplied. The geochemical variations in the lavas can be explained by mixing of depleted mid-ocean ridge basalt source mantle with slab-derived materials consisting of an altered oceanic crust component and a sediment component. The slab-derived materials are likely to have contained not only Sr, Ba, Pb and U, but also significant amounts of Nd and Th that are not highly soluble in aqueous fluids. The materials are thus suggested to have been supercritical liquids, and it is suggested that magma generation occurred at depths greater than that at which supercritical liquids were decomposed into aqueous fluid and silicate melt components. The lava samples show 238U–230Th disequilibrium with 10–20% of 230Th excess; this 230Th enrichment resulted primarily from the high-Th nature of the slab-derived materials.
A new preconcentration technique of Zr, Nb, Mo, Hf, Ta and W has been invented employing coprecipiation with Ti compounds. Silicate samples were digested by HF with addition of Ti. Subsequent drying with HClO4 resulting in complete elimination of fluorine produces Ti compounds (oxide/hydroxides). The sample was then dissolved with dilute nitric acid and centrifuged, and the residual Ti compounds were collected. The Ti compounds forming from 2 mg of Ti without matrix elements concentrate 84-98% of Zr, Nb, Mo, Hf, Ta and W. In 20 mg basaltic and 50 mg peridotitic matrices, the addition of 1 mg of Ti was appropriate and gave yields of 46-69 and 54-79%, respectively, for Zr, Nb, Mo, Hf, Ta and W. Exploiting this preconcentration, sequential separation protocols of Hf, Pb, Sr, Lu, Nd and Sm for isotope analysis are developed with total blanks of 16, 11, 60, 2.4, 3 and 0.4 pg, respectively. The method is suitable for Lu-Hf system studies with capability of simultaneous separation of Pb, Sr, Nd and Sm from the same sample digest as well as isotopic anomaly studies of Zr, Mo and W. As application examples, accurate Lu-Hf data and Pb isotope ratios were obtained for basalt (JB-3) and peridotite (JP-1) by MC-ICP-MS.
A new 3-step sequential separation chemistry for Sr, Nd and Pb from silicate samples, which is suitable for isotope analysis by MC-ICP-MS as well as TIMS, has been developed. The chemistry is designed to minimize the number of evaporation steps, enabling high throughput especially when MC-ICP-MS is employed. The sample solution in 0.5 mol l-1 HNO3 after digestion with HF-HClO4, which is prepared for trace element analysis, can be directly used in the new chemistry. In the first column using Sr resin, Sr and Pb are collected. The recovered solution for Sr can be directly aspirated into MC-ICP-MS. The Pb solution is dried, re-dissolved, separated into two aliquots and measured by double spike MC-ICP-MS. Subsequently, LREEs are collected by the second column packed with cation exchange resin. Finally, Nd was purified from Sm using Ln resin in the third column. The recovered Nd solution can also be directly nebulized into MC-ICP-MS. The Sr and Nd isotope ratios for the standard material JB-3 (basalt) from the Geological Survey of Japan by MC-ICP-MS and TIMS were reported to verify the chemistry and mass spectrometry developed in this study.
A precise method of measuring 228Ra/226Ra for 226Ra determination used in U-series disequilibrium studies has been developed using the total integration method with simultaneous 228Th isobaric interference correction by multicollector ICP-MS with multiple ion counters (MIC). A sample solution of 0.2 ml was separately taken into a test tube, and all 226Ra+ and 228Ra+ signals as well as 229Th+ and 228Th16O+ from beginning to end were integrated simultaneously using four channeltrons, IC1, IC3, IC4 and IC5, respectively. Gains between IC1 and IC3 and the mass discrimination factor for 228Ra/226Ra determination were canceled out by measurement of a Ra spike solution with an accurately known Ra isotope ratio determined by TIMS, with which samples were bracketed. The isobaric interferences of 228Th+ were simultaneously corrected from the signal of 228Th16O+ and the oxide forming ratio of 228Th, which was separately determined by simultaneous measurements of 229Th+ and 229Th16O+ by IC3 and IC5. The gains between IC3 and IC5 for the Th correction were also canceled out. The ion yield of Ra in MIC-ICP-MS was ∼1.5%. The intermediate precision using 6.6, 3.3, 1.7, 0.83 and 0.41fg of 226Ra with 228Ra/226Ra = ∼5 was 0.33, 0.93, 0.76, 1.6 and 1.5%, respectively. The 228Ra/226Ra ratio showed no systematic change dependent on 228Ra/226Ra up to 0.25, indicating the validity of the 228Th correction. At similar amounts of Ra, our method gives intermediate precision values similar to or better than previous MC-ICP-MS and TIMS studies. The precision of the method was verified using another Ra spike with 228Ra/226Ra = ∼1 determined by TIMS. The analytical performance of the method was further investigated using the silicate samples JB-2 and JB-3 basalts issued by GSJ.
Basalts at mid-ocean ridges are generated by partial melting of the Earth's upper mantle. As a result of this process, the upper mantle has become depleted over time in elements that are preferentially removed by melting. Although mid-ocean-ridge basalts have traditionally been thought to reflect the chemical composition of such depleted mantle, recent work has revealed the existence of domains in the upper mantle that are apparently not sampled by the basalts. Here we present the lead (Pb), neodymium (Nd) and hafnium (Hf) isotope compositions of peridotites from the Horoman orogenic massif in Japan, which is considered to represent the residues of melting of the upper mantle. These peridotites exhibit the lowest Pb isotope ratios reported from any known mantle material, along with high Nd and Hf isotope ratios. These data suggest that chemical depletion of the peridotites occurred around a billion years ago, and that they represent ancient mantle domains that have escaped convective stirring and homogenization. We suggest that such domains-if abundant in the mantle-may constitute a hitherto unrecognized reservoir with highly unradiogenic lead.
A strong gravitational field resulted in the gravity-induced diffusion (sedimentation) of isotope atoms in monoatomic solid Se. The layer crystalline morphology consisting of three zones of the fine-grained crystals, the long crystals and feather-shaped crystals grown parallel to gravity direction appeared in the specimen ultracentrifuged at (0.8–1)×106 G and at 190 °C. Change in the concentration ratio 82Se/76Se of >0.8% was observed in the grown crystalline region. These results show an evidence for the sedimentation of substitutional atoms in solids via self-diffusion, and suggest the possibility of application to the control of impurity and crystalline states as well as to isotope separation.
The sedimentation of isotope atoms has been realized in monoatomic liquid and solid Se. It was observed that the concentration ratio 82Se/76Se increased by % level in the specimen ultracentrifuged at 0.7–0.9 million G under liquid and solid states. The present result is evidence of sedimentation of substitutional atoms in condensed matter via self-diffusion, and suggests its possible application to isotope separation by condensed matter centrifugation.
Devolatilization of volatile‐bearing minerals caused by hypervelocity impacts is believed to have played important roles in atmosphere formation and the evolution of surface environments of terrestrial planets. The threshold shock pressure required for devolatilization is one of the most important parameters. In this study, we show a new experimental method to directly measure impact Devolatilization of volatile‐bearing minerals using a laser gun, which can avoid the problems of previous studies. We applied this method to the devolatilization of calcite. The results show that the shock pressure required for incipient devolatilization of calcite is lower than 24.9 ± 2.6 GPa which is significantly lower than previous experimental studies.
Pressure–temperature conditions of tourmaline breakdown in a metapelite were determined by high-pressure experiments at 700–900°C and 4–6 GPa. These experiments produced an eclogite–facies assemblage of garnet, clinopyroxene, phengite, coesite, kyanite and rare rutile. The modal proportions of tourmaline clearly decreased between 4.5 and 5 GPa at 700°C, between 4 and 4.5 GPa at 800°C, and between 800 and 850°C at 4 GPa, with tourmaline that survived the higher temperature conditions appearing corroded and thus metastable. Decreases in the modal abundance of tourmaline are accompanied by decreasing modal abundance of coesite, and increasing that of clinopyroxene, garnet and kyanite; the boron content of phengite increases significantly. These changes suggest that, with increasing pressure and temperature, tourmaline reacts with coesite to produce clinopyroxene, garnet, kyanite, and boron-bearing phengite and fluid. Our results suggest that: (1) tourmaline breakdown occurs at lower pressures and temperatures in SiO2- saturated systems than in SiO2-undersaturated systems. (2) In even cold subduction zones, subducting sediments should release boron-rich fluids by tourmaline breakdown before reaching depths of 150 km, and (3) even after tourmaline breakdown, a significant amount of boron partitioned into phengite could be stored in deeply subducted sediments.
Subduction of lithosphere, involving surficial materials, into the deep mantle is fundamental to the chemical evolution of the Earth. However, the chemical evolution of the lithosphere during subduction to depth remains equivocal. In order to identify materials subjected to geological processes near the surface and at depths in subduction zones, we examined B and Li isotopes behavior in a unique diamondiferous, K-rich tourmaline (K-tourmaline) from the Kokchetav ultrahigh-pressure metamorphic belt. The K-tourmaline, which includes microdiamonds in its core, is enriched in 11B relative to 10B (δ11B = −1.2 to +7.7) and 7Li relative to 6Li (δ7Li = −1.1 to +3.1). It is suggested that the K-tourmaline crystallized at high-pressure in the diamond stability field from a silicate melt generated at high-pressure and temperature conditions of the Kokchetav peak metamorphism. The heavy isotope signature of this K-tourmaline differs from that of ordinary Na-tourmalines in crustal rocks, enriched in the light B isotope (δ11B = −16.6 to −2.3), which experienced isotope fractionation through metamorphic dehydration reactions. A possible source of the heavy B-isotope signature is serpentine in the subducted lithospheric mantle. Serpentinization of the lithospheric mantle, with enrichment of heavy B-isotope, can be produced by normal faulting at trench-outer rise or trench slope regions, followed by penetration of seawater into the lithospheric mantle. Serpentine breakdown in the lithospheric mantle subducted in subarc regions likely provided fluids with the heavy B-isotope signature, which was acquired during the serpentinization prior to subduction. The fluids could ascend and cause partial melting of the overlying crustal layer, and the resultant silicate melt could inherit the heavy B-isotope signature. The subducting lithospheric mantle is a key repository for modeling the flux of fluids and associated elements acquired at a near the surface into the deep mantle.
The atomic-scale graded structure of In-Pb alloy was formed by an ultracentrifuge experiment under conditions that a gravitational field of 0.81 × 106G for 100 hours at 150°C (solid state) in our previous study. The isotope fluctuation on this sample was measured using secondary ion mass spectrometer (SIMS). The 115In/113In isotope ratio changed with positive gradient in the direction of centrifugal force approximately 1.2%. The isotope ratio fluctuation of centrifuged sample was 4 times larger than that of starting sample (<0.3%). This showed that the isotope fractionation effect was induced by solid centrifugation in this alloy, although achieved concentration gradients were small.
Eclogites of the Kaghan valley, Pakistan Himalaya were investigated petrographically and geochemically. Based on petrography, geochemistry and mineral compositions, metamorphic history and a reasonable tectonic model are proposed. Eclogites exposed in the Kaghan valley are classified into two groups. Group I eclogites appear as massive and Group II are lens-type. Group I eclogites have a mineral assemblage of garnet, omphacitic clinopyroxene, quartz, symplectite with rare epidote and phengite. Accessory minerals include abundant zircon, rutile, ilmenite, and rare apatite. Group II eclogites have a mineral assemblage of garnet, omphacitic clinopyroxene, phengite, quartz/coesite, epidote, and symplectite. In accessory minerals rutile and ilmenite are common while zircon and apatite are rare. Different types of protolith are proposed for these eclogites. Group I eclogites have higher FeO and TiO2 contents and trace element contents, and seem to be derived from gabbroic protolith. Group II eclogites have lower FeO and TiO2 and trace element contents and were derived from basalts. Pressure-temperature-time path was constructed for the Kaghan valley eclogites using various mineral assemblages along with textural relationship and inclusions study. At least three distinct metamorphic stages were identified. The first stage is the prograde garnet growth stage deduced from the inclusion paragenesis in garnet core. The second stage records the ultrahigh-pressure metamorphic stage deduced from the presence of coesite inclusions in omphacitic clinopyroxene. The third stage is the decompression stage and is deduced from the quartz-albite-amphibole symplectite portions. These petrological and geochemical results combined with isotopic ages reported elsewhere indicate that basalts and associated gabbroic dikes were emplaced at about 267 Ma when the Indian plate was moving northward and passing above an unknown hot spot. The closure of the Tethys and initiation of collision of the Indian plate with the Kohistan-Ladakh Island Arc is reported from 65-50 Ma. After that the leading-edge of the Indian plate underwent eclogite facies metamorphism at 49 Ma and when it reached to depths of about 100 km, the ultrahigh-pressure metamorphic event took place at 46 Ma.
The two parallel loci of recent Hawaiian volcanoes, Kea and Loa, have been regarded as the best targets to interpret the chemical structure of an upwelling mantle plume derived from the lower mantle. Here we show that the Sr–Nd–Hf–Pb isotopic data of the shield-building lavas along the Loa locus form a systematic trend from the main shield stage of Koolau (> 2.9 Ma) to the active Loihi volcanoes. During the growth of the Koolau volcano, the dominant material in the melting region successively changed from the proposed KEA, DMK (depleted Makapuu), to EMK (enriched Makapuu) components. The proportion of EMK, dominated by a recycled mafic component, is typified by some Koolau Makapuu-stage and some Lanai lavas. Subsequently, the EMK component decreased and LOIHI component increased toward the Loihi lavas. The temporal coincidence between the episodically elevated magma production rate and the abrupt appearance of the typical Loa-type lavas that is restricted to the last 3 Myr should be linked to magma genesis. We suggest that the abrupt appearance of Loa-type magmatism should be attributed to the transient incorporation of the relatively dense recycled material and surrounding less degassed lower mantle material that accumulated near the core–mantle boundary into the upwelling plume. This episodic involvement could have been trigged by episodic thermal pulses and buoyancy increases in the plume. The continuous appearance of Kea-type lavas during the long history of Hawaiian-chain magmatism and the larger magma volume of Kea-type lavas relative to that of the Loa-type lavas in the last 3 Myr indicate that the Kea locus is closer to the thermal centre of the Hawaiian plume relative to that of the Loa locus.
The Cretaceous Okhotsk-Chukotka volcanic belt (OCVB) is one of the largest subduction-related volcanic provinces of the Earth. It is thought to be related with the subduction of paleo-Pacific plates under the collage of terranes of NE Asia accreted during Jurassic and Early Cretaceous time. The OCVB comprises a remarkably high portion of silicic rocks, up to 80-90% in some segments. Within the Central Chukotka segment of the belt, volcanic sequences reveal a rather uniform 40Ar/39Ar and U-Pb isotopic age of near 89-87 Ma. But the felsic volcanic unit with coeval subsurface intrusives named the 'Berlozhya magmatic assemblage' (BMA) yields much older zircon U-Pb ages (146.0 ± 2.4 for rhyolitic tuff and 145.5 ± 1.8 Ma for related granodiorite). The relationship of the BMA with the active boundary between the Chukotka-Arctic Alaska microcontinent and the Anyui-Angayucham oceanic basin is suggested. BMA rocks seem to be undeformed, and their age puts constraints on the timing of main compressional events in the North Chukotka area. We present analytical data for both BMA and OCVB silicic magmatic rocks, including the first isotopic compositions of Sr, Nd, Pb, and Hf for the 1500 km long northern part of the OCVB. We infer that felsic magmas of both BMA and OCVB were produced by the melting of the continental crust, without a significant direct contribution from mantle sources. However, the crustal protolith could contain some ancient island arc complexes, which affected the chemical and isotopic composition of magmatic derivatives. The BMA exhibits a relatively uniform isotopic composition (87Sr/86Sri = 0.7057 to 0.7070, εNdi = - 0.51 to - 0.12, εHfi = 4.41 to 4.92, 206Pb/204Pbi = 18.50 to 18.57, and 208Pb/204Pbi = 38.23 to 38.31), and its chemical diversity likely results from crystal fractionation. The protolith of OCVB rhyolites has more variable isotopic characteristics (87Sr/86Sri = 0.7032 to 0.7082, εNdi = - 4.06 to - 2.84, εHfi = - 1.56 to 3.77, 206Pb/204Pbi = 18.56 to 18.81, and 208Pb/204Pbi = 38.21 to 38.63), and reveals at least three end-members. Each of them is distinct from the source of the Berlozhya assemblage, thus suggestive of compositional layering of the crust. Nd and Hf model ages of all studied rocks correspond to Neoproterozoic. The estimated Nd model age of the OCVB protolith is slightly older than that for the BMA, but both fall into the Neoproterozoic interval (1000 to 800 Ma).
Detailed electron- and ion-microprobe analyses were carried out on atoll-shaped and normal garnets in ultrahigh-pressure (UHP) metamorphic eclogite from Dabie, east-central China. Compositional profiles of both normal garnets and rings of atoll garnets show well-preserved growth zoning with a decrease in Mn, Ca, and heavy rare earth elements (HREEs), and an increase in Mg toward rims. Manganese and middle rare earth element (MREE) enrichments are observed near garnet rims. Island- and peninsula-shaped garnet inside atolls are homogeneous in major elements and show the same composition as garnet rims, whereas the HREE concentrations are similar to those of the normal garnet cores. Electron back-scatter diffraction (EBSD) analyses show that the island- and peninsula-shaped garnet fractions inside atolls have crystallographic orientations identical to that of the atoll rings. These observations suggest that the atoll garnets were formed by the consumption of earlier-formed cores by fluid released from both hydroxyl exsolution from the nominally anhydrous minerals (NAMs) and lawsonite decomposition at the onset of exhumation, (i.e., garnet breakdown was from the inside and re-growth from outside to inside). Though somewhat restricted, this study reveals that because garnet and zircon act as sinks for HREEs and Zr, respectively, the majority of released HREEs and Zr were likely re-incorporated into newly grown garnet and zircon during the Dabie UHP metamorphic slab exhumation.
Palaeocene (c. 55–58 Ma) adakitic andesites from the Yanji area, NE China, are typically clinopyroxene-bearing sodic andesites containing 60.9–62.2% SiO2 and 4.02–4.36% MgO, with high Mg-number [100 Mg/(Mg + ΣFe) atomic ratio] from 65.5 to 70.1. Whole-rock geochemical features include high Cr (128–161 ppm) and Ni (86–117 ppm) concentrations, extremely high Sr (2013–2282 ppm), low Y (10–11 ppm) and heavy rare earth elements (HREE; e.g. Yb = 0.79–1.01 ppm), and mid-ocean ridge basalt (MORB)-like Sr–Nd–Pb isotopic compositions [e.g. 87Sr/ 86Sr(i) = 0.70298–0.70316, εNd(t) = +3.8 to +6.3 and 206Pb/ 204Pb = 17.98 – 18.06], analogous to high-Mg adakites occurring in modern subduction zones. However, mineralogical evidence from clinopyroxene phenocrysts and microcrystalline plagioclase clearly points to magma mixing during magma evolution. Iron-rich clinopyroxene (augite) cores with low Sr, high Y and heavy REE contents, slightly fractionated REE patterns and large negative Eu anomalies probably crystallized along with low-Ca plagioclase from a lower crustal felsic magma. In contrast, high Mg-number clinopyroxene (diopside and endiopside) mantles and rims have higher Sr and lower HREE and Y concentrations, highly fractionated REE patterns (high La/Yb) and negligible Eu anomalies, similar to those found in adakites from subduction zones. The Yanji adakitic andesites can be interpreted as a mixture between a crust-derived magma having low Mg-number and Sr, and high Y and HREE, and a mantle-derived high Mg-number adakite having high Sr and low Y and HREE concentrations. During storage and/or ascent, the mixed magma experienced further crustal contamination to capture zircons, of a range of ages, from the wall rocks. The absence of coeval arc magmatism and an extensional tectonic regime in the Yanji area and surrounding regions suggest that these Palaeocene adakitic andesites were formed during post-subduction extension that followed the late Cretaceous Izanagi–Farallon ridge subduction. Generation of these adakitic andesites does not require contemporaneous subduction of a young, hot oceanic ridge or delamination of eclogitic lower crust as suggested by previous models.
We investigated mafic–ultramafic rocks distributed in the Timor–Tanimbar region as a possible modern analogue for the Mediterranean-type ophiolites in the Tethyan system. The geological occurrence suggests that the buoyant subduction of Australian continent uplifted the fragments of newly formed mantle–crust section, which extends to the neighboring preemplaced forearc marginal basins. However, we recognized a large variety of igneous features, which is consistent with the lack of complete succession and the presence of abundant crosscutting structures. All peridotite masses in Timor (Mutis, Atapupu and Dili) are mostly fertile (lherzolitic) in compositions. In addition, we found depleted harzburgite, highly refractory dunite and olivine websterite to occur as minor constituents, which display compositional contrast to those of the lherzolites. Structurally overlying Ocussi volcanics resemble island–arc tholeiite in terms of trace element characteristics, apparently inconsistent with genetic relationship with Timor lherzolite masses. In eastern small islands (Moa and Dai), all types of ophiolitic rocks display varying degrees of island–arc affinities. Cumulate origin of wehrlite and gabbroic rocks in Dai is marked by early crystallization of clinopyroxene and common occurrence of high-calcic plagioclase. Dikes cutting the gabbro sequence have weak island–arc signatures relative to those of Ocussi volcanics. Mildly depleted lherzolite–harzburgite in Moa was intruded by high-Mg andesitic magma, which crystallized hornblende gabbro containing high-Mg orthopyroxene. These petrological and geochemical variations can be best explained by the combination of (1) a temporal change of igneous activity possibly associated with development of forearc basin and (2) the emplacement of spatially different forearc regions in each locality. Unusual occurrence of fertile lherzolite in the forearc setting, generation of high-Mg andesite magmatism, inverted metamorphic grade recorded from associated metamorphic rocks, and formation of marginal basins may be linked to the injection of high-temperature asthenospheric materials into the mantle wedge.
We present a Sr, Nd, Hf and Pb isotope investigation of a set of garnet clinopyroxenite xenoliths from Malaita, Solomon Islands in order to constrain crustal recycling in the Pacific mantle. Geological, thermobarometric and petrochemical evidence from previous studies strongly support an origin as a series of high-pressure (> 3 GPa) melting residues of basaltic material incorporated in peridotite, which was derived from Pacific convective mantle related to the Ontong Java Plateau magmatism. The present study reveals isotopic variations in the pyroxenites that are best explained by different extents of chemical reaction with ambient peridotite in the context of a melting of composite source mantle. Isotopic compositions of bimineralic garnet clinopyroxenites affected by ambient peridotite fall within the oceanic basalt array, similar to those of Ontong Java Plateau lavas. In contrast, a quartz-garnet clinopyroxenite, whose major element compositions remain intact, has lower 206Pb/204Pb–143Nd/144Nd and higher 87Sr/86Sr–207Pb/204Pb ratios than most oceanic basalts. These isotopic signatures show some affinity with proposed recycled sources such as the so-called EM-1 or DUPAL types. Constraints from major and trace element characteristics of the quartz-garnet clinopyroxenite, the large extent of Hf–Nd isotopic decoupling and the good coincidence of Pb isotopes to the Stacey–Kramers curve, all indicate that pollution of southern Pacific mantle occurred by the subduction or delamination of Neoproterozoic granulitic lower crust (0.5–1 Ga). This crustal recycling could have taken place around the suture of Rodinia supercontinent, a part of which resurfaced during mantle upwelling responsible for creating the Cretaceous Ontong Java Plateau.
The B and Pb isotope systems are widely applied tracers of recycling processes occurring during subduction. Studies examining these complementary systems as a pair enjoy considerable success, where B primarily records the thermal and fluid evolution of the subducting slab, whereas the tripartite Pb system constrains the source of subducted material returned to volcanic arcs. However, interpretations derived from the arc volcanic record critically depend upon assumptions regarding compositions of unmetamorphosed inputs to subduction zones. Few studies have directly addressed potential fractionation of B isotopes and U–Th–Pb by analysis of high-pressure (HP) and ultrahigh-pressure (UHP) metamorphic suites, despite that fractionation in these systems during subduction-zone metamorphism has been inferred in many studies of volcanic arcs and ocean–island basalts. Here, we address the metamorphic evolution of subducted material with B and Pb isotope determinations for the mélange matrix of the Catalina Schist, CA.
Rates of magmatic processes in a cooling magma chamber were investigated for alkali basalt and trachytic andesite lavas erupted sequentially from Rishiri Volcano, northern Japan, by dating of these lavas using 238U–230Th radioactive disequilibrium and 14C dating methods, in combination with theoretical analyses. We obtained the eruption age of the basaltic lavas to be 29.3 ± 0.6 ka by 14C dating of charcoals. The eruption age of the andesitic lavas was estimated to be 20.2 ± 3.1 ka, utilizing a whole-rock isochron formed by U–Th fractionation as a result of degassing after lava emplacement. Because these two lavas represent a series of magmas produced by assimilation and fractional crystallization in the same magma chamber, the difference of the ages (i.e. ∼9 kyr) is a timescale of magmatic evolution. The thermal and chemical evolution of the Rishiri magma chamber was modeled using mass and energy balance constraints, as well as quantitative information obtained from petrological and geochemical observations on the lavas. Using the timescale of ∼9 kyr, the thickness of the magma chamber is estimated to have been about 1.7 km. The model calculations show that, in the early stage of the evolution, the magma cooled at a relatively high rate (>0.1°C/year), and the cooling rate decreased with time. Convective heat flux from the main magma body exceeded 2 W/m2 when the magma was basaltic, and the intensity diminished exponentially with magmatic evolution. Volume flux of crustal materials to the magma chamber and rate of convective melt exchange (compositional convection) between the main magma and mush melt also decreased with time, from ∼0.1 m/year to ∼10−3 m/year, and from ∼1 m/year to ∼10−2 m/year, respectively, a s the magmas evolved from basaltic to andesitic compositions. Although the mechanism of the cooling (i.e. thermal convection and/or compositional convection) of the main magma could not be constrained uniquely by the model, it is suggested that compositional convection was not effective in cooling the main magma, and the magma chamber is considered to have been cooled by thermal convection, in addition to heat conduction.
We examined the coprecipitation behavior of Ti, Mo, Sn and Sb in Ca–Al–Mg fluorides under two different fluoride forming conditions: at < 70 °C in an ultrasonic bath (denoted as the ultrasonic method) and at 245 °C using a Teflon bomb (denoted as the bomb method). In the ultrasonic method, small amounts of Ti, Mo and Sn coprecipitation were observed with 100% Ca and 100% Mg fluorides. No coprecipitation of Ti, Mo, Sn and Sb in Ca–Al–Mg fluorides occurred when the sample was decomposed by the bomb method except for 100% Ca fluoride. Based on our coprecipitation observations, we have developed a simultaneous determination method for B, Ti, Zr, Nb, Mo, Sn, Sb, Hf and Ta by Q-pole type ICP-MS (ICP-QMS) and sector field type ICP-MS (ICP-SFMS). 9–50 mg of samples with Zr–Mo–Sn–Sb–Hf spikes were decomposed by HF using the bomb method and the ultrasonic method with B spike. The sample was then evaporated and re-dissolved into 0.5 mol l− 1 HF, followed by the removal of fluorides by centrifuging. B, Zr, Mo, Sn, Sb and Hf were measured by ID method. Nb and Ta were measured by the ID-internal standardization method, based on Nb/Mo and Ta/Mo ratios using ICP-QMS, for which pseudo-FI was developed and applied. When 100% recovery yields of Zr and Hf are expected, Nb/Zr and Ta/Hf ratios may also be used. Ti was determined by the ID-internal standardization method, based on the Ti/Nb ratio from ICP-SFMS. Only 0.053 ml sample solution was required for measurement of all 9 elements. Dilution factors of ≤ 340 were aspirated without matrix effects. To demonstrate the applicability of our method, 4 carbonaceous chondrites (Ivuna, Orgueil, Cold Bokkeveld and Allende) as well as GSJ and USGS silicate reference materials of basalts, andesites and peridotites were analyzed. Our analytical results are consistent with previous studies, and the mean reproducibility of each element is 1.0–4.6% for basalts and andesites, and 6.7–11% for peridotites except for TiO2.
A two-stage column purification method for Hf from Zr and other elements in silicate samples using the extraction chromatographic resin, UTEVA has been developed. In the first column, using an anion-exchange resin, AG 1X8, Hf, Zr and Ti were collected. In the second, using UTEVA, and after eliminating F− by evaporation with HClO4 and re-dissolution with H2O2–HNO3, Hf was purified from Ti and Zr, based on characteristic of the UTEVA resin that Hf distribution coefficient (Kd) decreases from 770 to 40, while Kd of Zr decreases less from 890 to 200, in 9 and 6 mol l−1 HNO3, respectively. The recovery yield of Hf was ∼88% and total blank was ∼4 pg. A MC-ICP-MS Hf isotope ratio determination method was also developed, which uses 179Hf spike for simultaneous determination of the Hf concentration and 176Hf/177Hf ratio. Combining the chemistry and ICP-MS techniques, 176Hf/177Hf ratios in silicate reference materials were determined with and without the spike, which gave identical results, showing the applicability of this method.
A double-spike multicollector ICP-MS (DS-MC-ICP-MS) technique for Pb isotope analysis without Tl addition is established and its analytical performance is examined in detail. This simple DS-MC-ICP-MS technique using 20 ng ml−1 gave averages of 16.9417, 15.4988 and 36.7196 with reproducibilities of 0.007, 0.008 and 0.009% (RSD, n = 35), respectively, for 206Pb/204Pb, 207Pb/204Pb and 208Pb/204Pb in NIST 981 solution, corresponding to consumption of 4 ng of Pb in a pair of spiked and non-spiked measurements. The average is consistent with those obtained by previous studies by DS-TIMS and DS-MC-ICP-MS with Tl addition. The reproducibility (RSD %) of 206Pb/204Pb, 207Pb/204Pb and 208Pb/204Pb improves from 0.26, 0.54 and 0.69% to 0.0022, 0.0030 and 0.0029% as the Pb consumption during analysis increases from 20 pg to 11 ng. The reproducibility with 11 ng is similar to or even better than those by DS-TIMS, MC-ICP-MS with Tl addition, or with DS-Tl addition. The accuracy of the simple DS-MC-ICP-MS technique for Pb, including the column chemistry, is further confirmed by analysis of actual silicate sample, JB-3.
Accurate determination methods for 234U/238U and 230Th/232Th using multiple collector (MC) ICP-MS with a single secondary electron multiplier through a retarding potential quadrupole filter (RPQ-SEM) have been developed. The RPQ-SEM yield and the instrumental mass discrimination were simultaneously corrected by the simple bracketing method which utilizes accurately determined standard solutions measured by TIMS. For the bracketing and as an evaluation of the precision of the method, four standard solutions, NBL-145 U and U-m for U, and Th-I and Th-II for Th, were prepared, and NBL-145 U and Th-I were used as bracketing standards. The U and Th amounts of 0.5–21 ng and 0.6–21 ng used in U-m and Th-II analyses gave intermediate precisions (2RSD) of 0.85–0.06 and 0.88–0.19%, respectively, and vary from TIMS measurements by <0.35 and <1.1%, respectively, which agrees with error values in TIMS analyses. To achieve similar intermediate precisions of 0.2 and 0.6% (2RSD) in the U and Th isotope analyses to that of TIMS, 3 and 2 ng of U and Th are sufficient. When only the isotope analysis is performed, the required amounts of U and Th can be reduced by half. The precision of the isotope analyses, as well as the concentration determinations, were further confirmed by analyses of U and Th separated from the GSJ standard basalt, JB-2.
The Neoarchaean Musoma-Mara Greenstone Belt (MMGB) of northern Tanzania is underlain in part by the ∼2649 Ma post-orogenic potassic-rich granites, which are the most abundant intrusive rocks in the belt. The rocks are composed of plagioclase + K-feldspar + quartz + biotite ± sphene ± zircon ± hornblende ± chlorite. They are characterized by high contents of SiO2 (68.90–77.76 wt%), K2O (3.71–5.44 wt%) and low Na2O (3.27–5.70 wt%) leading to low ratios of Na2O/K2O (0.63–1.02). The rocks are depleted in CaO (0.22–2.41 wt%) as well as in Sr (15–412 ppm), Cr (≤16 ppm) and Ni (≤5 ppm); and their major element composition are similar to those of experimental melts derived from partial melting of tonalite. On chondrite-normalized REE patterns, these rocks show fractionated patterns (La/YbCN = 1.22–41.32) that are characterised by moderate to strongly negative Eu anomalies (Eu/Eu* = 0.04–0.86). On primitive mantle-normalized spidergrams, these rocks are generally enriched in Th, U, K and Pb and depleted in Ba, Sr, Nb, Ta and Ti elative to adjacent elements. The K-rich granites have ɛNdo (at 2.649 Ga) values of +0.55 to +1.70 that compare well with those of associated volcanic rocks and TTG (ɛNd = +0.44 to +2.66) which predate the emplacement of the K-rich granitoids. Their mean crustal residence ages are 170 to 450 Ma older than their emplacement ages. The overall geochemical features of this suite of rocks, together with evidence from experimental results, are consistent with their generation by partial melting of relatively juvenile igneous rocks within the continental crust at pressures corresponding to depths <15 km where plagioclase was a stable phase. The transition from earlier TTG magmatism to potassic magmatism in the MMGB is interpreted as marking a transition from growth of the Neoarchaean continental crust through the addition of juvenile mantle-derived material to intra-crustal recycling of pre-existing material.
Geochemical data are presented for Neoarchaean metavolcanic and plutonic rocks from the Musoma-Mara Greenstone Belt (MMGB) in the northern part of the Tanzania Craton with the aim of inferring their petrogenesis and tectonic settings in which they formed. The MMGB is underlain by two unusual magmatic suites: high magnesium andesites and an adakitic suite. The high-Mg andesites are composed of intermediate volcanic rocks of andesitic composition which, when compared to normal island arc andesites, are characterised by high contents of MgO (2.42–9.47 wt%), Cr (41–797 ppm) and Ni (11–254 ppm). Ratios of Nb/Y are 0.17–0.28, La/Yb are 9.87–22.5 and Sr/Y are 16.1–48.7. These geochemical features are analogous to those shown by modern High Magnesium Andesites (HMA). The adakitic suite is composed of dacites and Na-granitoids and is characterized by Al2O3 contents of 14.75–18.54 wt%, variable contents of MgO (0.31–4.96 wt%), Cr and Ni (5.10–250 and 1.22–115 ppm, respectively). Their ratios of Nb/Y are 0.17–0.66, La/Yb are 11–80 and Sr/Y are 20–131. Compared to the HMA, rocks of the adakitic suite are characterized by lower MgO, Cr and Ni contents, higher contents of Al2O3 and Sr, higher ratios of La/Yb and Sr/Y and are compositionally similar to modern adakites. Rocks from both suites show negative anomalies of Nb, Ta and Ti and have similar ɛNd values (at 2.67 Ga) of +0.44 to +2.66. The geochemical characteristics of the HMA are consistent with the derivation of their parent magma by partial melting of mantle peridotite that has been fluxed by slab-derived aqueous fluids above a continental arc. As the slab further descended into the mantle, partial melting of the subducted oceanic crust occurred in the garnet stability field producing a melt that was depleted in HREE. The slab-derived melts percolated into the mantle wedge and reacted with mantle peridotite resulting in parental magmas of rocks of the adakitic suite. Subsequently, the parental magmas of both rock suites ascended through and were contaminated by older felsic crust forming the continental arc basement. Subsequent fractional crystallization of pyroxene and hornblende led to the range in Mg numbers, CaO, Cr and Ni contents observed in the rocks. The association of some members of the adakitic suite with locally derived clastic sedimentary rocks suggests that the latest volcanic episode in the MMGB occurred in a continental back arc basin. The rapid emplacement of volcanic and plutonic rocks in a relatively short time interval is best explained in terms of the ridge-subduction model of [Iwamori, H., 2000. Thermal effects of ridge subduction and its implication for the origin of granitic batholith and paired metamorphic belts. Earth Planet. Sci. Lett., 181, 131–144.] whereby subduction of the ridge crest results in anomalous high thermal input into the subduction zone leading to rapid arc magmatism within a few tens of kilometers from the slab–crust interface and within a time interval of 30 Ma after ridge subduction.
A strong gravitational field resulted in the sedimentation of isotope atoms in monatomic liquid. The concentration ratio 82Se/76Se increased by greater than 3.5% in specimen ultracentrifuged at (0.7–0.9)×106G and at 300°C. The recovered sample had a feather-shaped crystalline morphology. The concentration gradient was nearly twice that of the steady state analytical result (ideal gas system), indicating a nonideal system diffusion. The present result is evidence of sedimentation of substitutional atoms in condensed matter via self-diffusion and suggestes its possible application to isotope separation, crystalline control, and matter dynamics in massive star.
The Gorny Altai region in southern Siberia is one of the key areas in reconstructing the tectonic evolution of the western segment of the Central Asian Orogenic Belt (CAOB). This region features various orogenic elements of Late Neoproterozoic–Early Paleozoic age, such as an accretionary complex (AC), high-P/T metamorphic (HP) rocks, and ophiolite (OP), all formed by ancient subduction–accretion processes. This study investigated the detailed geology of the Upper Neoproterozoic to Lower Paleozoic rocks in a traverse between Gorno-Altaisk city and Lake Teletskoy in the northern part of the region, and in the Kurai to Chagan-Uzun area in the southern part. The tectonic units of the studied areas consist of (1) the Ediacaran (=Vendian)–Early Cambrian AC, (2) ca. 630 Ma HP complex, (3) the Ediacaran–Early Cambrian OP complex, (4) the Cryogenian–Cambrian island arc complex, and (5) the Middle Paleozoic fore-arc sedimentary rocks. The AC consists mostly of paleo-atoll limestone and underlying oceanic island basalt with minor amount of chert and serpentinite. The basaltic lavas show petrochemistry similar to modern oceanic plateau basalt. The 630 Ma HP complex records a maximum peak metamorphism at 660 °C and 2.0 GPa that corresponds to 60 km-deep burial in a subduction zone, and exhumation at ca. 570 Ma. The Cryogenian island arc complex includes boninitic rocks that suggest an incipient stage of arc development. The Upper Neoproterozoic–Lower Paleozoic complexes in the Gorno-Altaisk city to Lake Teletskoy and the Kurai to Chagan-Uzun areas are totally involved in a subhorizontal piled-nappe structure, and overprinted by Late Paleozoic strike-slip faulting. The HP complex occurs as a nappe tectonically sandwiched between the non- to weakly metamorphosed AC and the OP complex. These lithologic assemblages and geologic structure newly documented in the Gorny Altai region are essentially similar to those of the circum-Pacific (Miyashiro-type) orogenic belts, such as the Japan Islands in East Asia and the Cordillera in western North America. The Cryogenian boninite-bearing arc volcanism indicates that the initial stage of arc development occurred in a transient setting from a transform zone to an incipient subduction zone. The less abundant of terrigenous clastics from mature continental crust and thick deep-sea chert in the Ediacaran–Early Cambrian AC may suggest that the southern Gorny Altai region evolved in an intra-oceanic arc-trench setting like the modern Mariana arc, rather than along the continental arc of a major continental margin. Based on geological, petrochemical, and geochronological data, we synthesize the Late Neoproterozoic to Early Paleozoic tectonic history of the Gorny Altai region in the western CAOB.
Li concentrations and isotopic compositions of coexisting minerals (ol, opx, and cpx) from peridotite xenoliths entrained in the Hannuoba Tertiary basalts, North China Craton, provide insight into Li isotopic fractionation between mantle minerals during melt–rock interaction in the considerably thinned lithospheric mantle. Bulk analyses of mineral separates show significant enrichment of Li in cpx (2.4–3.6 ppm) relative to olivine (1.2–1.8 ppm), indicating that these peridotites have been affected by mantle metasomatism with mafic silicate melts. Bulk olivine separates (δ7Li ∼ +3.3‰ to +6.4‰) are isotopically heavier than coexisting pyroxenes (δ7Li ∼ −3.3‰ to −8.2‰ in cpx, and −4.0‰ to −6.7‰ in opx). Such large variation suggests Li elemental and isotopic disequilibrium. This conclusion is supported by results from in situ SIMS analyses of mineral grains where significant Li elemental and isotopic zonations exist. The olivine and opx have lower Li concentrations and heavier Li isotopes in the rims than in the cores. This reverse correlation of δ7Li with Li concentrations indicates diffusive fractionation of Li isotopes. However, the zoning patterns in coexisting cpx show isotopically heavier rims with higher Li abundances. This positive correlation between δ7Li and Li concentrations suggests a melt mixing trend. We attribute Li concentration and isotope zonation in minerals to the effects of two-stage diffusive fractionation coupled with melt–rock interaction. The earliest melts may have been derived from the subducted oceanic slab with low δ7Li values produced by isotopic fractionation during the dehydration of the seawater-altered slab. Melts at later stages were derived from the asthenosphere and interacted with the peridotites, producing the Li elemental and isotopic zoning in mineral grains. These data thus provide evidence for multiple-stage peridotite–melt interaction in the lithospheric mantle beneath the northern North China Craton.
A coesite-bearing, lawsonite-eclogite xenolith from the Colorado Plateau, interpreted as a fragment of the subducted Farallon plate, is used to characterize trace element behavior in subducted oceanic crust. The xenolith consists of almandine-rich garnet, omphacite, lawsonite, phengite, rutile, pyrite and zircon as the primary mineral assemblage. Garnet crystals are extremely zoned with respect to their Mn contents, with core to rim variation from ∼ 1.4 to ∼ 0.2 wt.%. The euhedral zoning feature of garnet crystals and its included mineral assemblages suggest that the garnet continued to grow in the coesite stability field during prograde lawsonite eclogite facies metamorphism. In the lawsonite-eclogite xenoliths, garnet dominates the heavy rare earth elements (HREE), and lawsonite dominates both light rare earth elements (LREE) and Sr inventories. Combining the mineralogical and petrographic observations with precise spatial resolution ion microprobe analyses (< 15 μm) of zoned garnet as well as lawsonite inclusions in garnet, we investigated trace element fractionation in coesite stability field during lawsonite eclogite facies metamorphism. Garnet shows progressive HREE depletion from core to rim, suggesting that HREE, which once partitioned into garnet crystal, would not be involved in postdated metamorphic reactions due to the high partition coefficients of HREE into garnet. Lawsonite inclusions in garnet, which represent lower metamorphic condition relative to lawsonite in the matrix, have LREE concentrations ∼ 10 times lower than those of matrix lawsonite. On the contrary, the concentration of Sr in the included lawsonite is (< 20 relative %) lower than that of the matrix lawsonite. Based on constraints from metamorphic history recorded in the prograde-zoned garnet and mass balance among all constituent minerals in the lawsonite-eclogite xenolith, this contrasting feature for Sr and LREE of lawsonite is most plausibly explained by the hypothesis that allanite coexisting with included lawsonite might have decomposed during prograde metamorphism. The LREE released from the decomposing allanite would have been incorporated into lawsonite crystals. Consequently, REE and Sr could be retained in subducting oceanic crust even in the coesite stability field, if the slab is sufficiently cold enough to pass though the lawsonite eclogite facies.
Precise measurements of 238U–230Th–226Ra disequilibria in lavas erupted within the last 100 yr on Mt. Cameroon are presented, together with major and trace elements, and Sr–Nd–Pb isotope ratios, to unravel the source and processes of basaltic magmatism at intraplate tectonic settings. All samples possess 238U–230Th–226Ra disequilibria with 230Th (18–24%) and 226Ra (9–21%) excesses, and there exists a positive correlation in a (226Ra/230Th)–(230Th/238U) diagram. The extent of 238U–230Th–226Ra disequilibria is markedly different in lavas of individual eruption ages, although the (230Th/232Th) ratio is constant irrespective of eruption age. When U-series results are combined with Pb isotope ratios, negative correlations are observed in the (230Th/238U)–(206Pb/204Pb) and (226Ra/230Th)–(206Pb/204Pb) diagrams. Shallow magma chamber processes like magma mixing, fractional crystallization and wall rock assimilation do not account for the correlations. Crustal contamination is not the cause of the observed isotopic variations because continental crust is considered to have extremely different Pb isotope compositions and U/Th ratios. Melting of a chemically heterogeneous mantle might explain the Mt. Cameroon data, but dynamic melting under conditions of high DU and DU/DTh, long magma ascent time, or disequilibrium mineral/melt partitioning, is required. The most plausible scenario to produce the geochemical characteristics of Mt. Cameroon samples is the interaction of melt derived from the asthenospheric mantle with overlying sub-continental lithospheric mantle which has elevated U/Pb (>0.75) and Pb isotope ratios (206Pb/204Pb > 20.47) due to late Mesozoic metasomatism.
The Hayachine–Miyamori (HM) ophiolitic complex in the Kitakami Mountains, northeastern Japan consists of ultramafic tectonite and cumulate members. The most fertile lherzolites have mineral and trace element compositions similar to those of abyssal peridotites. They show 350–430 Ma Nd depleted mantle model ages, which are within the range of the K–Ar emplacement ages obtained from intrusive gabbroic rocks, suggesting a partial melting event just before the emplacement. The measured 143Nd/144Nd ratio of clinopyroxene in the tectonite peridotites shows positive correlation with 147Sm/144Nd and decreases with increasing refractoriness, which cannot be explained by a simple melting and melt extraction to a various extent followed by radiogenic ingrowth. It clearly suggests influx of a melt/fluid enriched in highly incompatible trace elements during melting. Time corrected isotopic compositions of the HM complex exhibit a clear island arc signature with uniform initial isotopic ratio (87Sr/86Sr = 0.7035–0.7041, εNd = + 7.8–+ 5.0). Application of an open-system melting model to the observed trace element abundances in clinopyroxene suggests influx of three distinct agents to the HM mantle with the following characteristics: (1) moderate enrichment in highly incompatible elements with negative anomalies of Sr and Zr; (2) extensive enrichment of highly incompatible elements with positive Sr and negative Zr anomalies; and (3) extensive enrichment of highly incompatible elements with positive anomalies of Sr and Zr. These characteristics cover a variety of slab-derived components proposed in the literatures, suggesting the agents responsible for the open-system melting in the HM ophiolite might represent full spectrum of slab-derived components from back-arc to fore-arc regions of the Ordovician island arc system.
A highly fertile mantle xenolith entrained in the Upper Cretaceous Daxizhuang basalt, Shandong Province, China provides petrological evidence for reaction between basaltic melt and refractory peridotite in Mesozoic lithospheric mantle beneath the eastern North China craton. The xenolith is zoned with a lherzolite core, a sheared wehrlite mantle, and a reactant rim. The lherzolite has a medium-grained granular texture and contains olivine, orthopyroxene, clinopyroxene, and spinel with low Mg# values (≤87). This is the lowest value observed globally in mantle xenoliths entrained in both kimberlites and basalts from old cratons, but is close to low-Mg# spinel lherzolites entrained in adjacent region of the eastern North China craton. The wehrlite mantle shows clear orientation and foliation of constituent olivine and clinopyroxene. The reactant rim displays a symplectite texture of fine-grained olivine, clinopyroxene, and spinel, and is characterized by LREE-enriched patterns. Orthopyroxene is lacking from the sheared mantle and reactant rim. Clear zoning and systematic core-rim variations in major and trace elements of the constituent minerals demonstrate the occurrence of the refertilization through the melt-peridotite reaction in the xenolith. This reaction may have produced the low-Mg# peridotite from a high-Mg# protolith and could be an important mechanism for the change of the subcontinental lithospheric mantle from a Paleozoic refractory mantle to a Late Mesozoic fertile mantle.
We present major and trace element concentrations in conjunction with Sr–Nd isotope ratios to investigate the geochemical characteristics of mélange formation along the subduction zone slab–mantle interface. Mélange matrix of the Catalina Schist formed within an active subduction zone of the southern California borderland in Cretaceous time. Mélange formed through the synergistic effects of deformation and metasomatic fluid flow affecting peridotite, basaltic, and sedimentary protoliths to form hybridized bulk compositions not typical of seafloor “input” lithologies. In general, all elemental concentrations primarily reflect mechanical mixing processes, while fluid flow mediates all elemental systematics to a varying extent that is largely a function of inferred “mobility” for a particular element or the stability of suitable mineral hosts. Elemental data reveal that mineral stabilities defined by the evolution of bulk composition within mélange zones are probably the most important control of solid, liquid, or fluid geochemistry within the subduction system. Sr–Nd isotope ratios are highly variable and reflect contributions of mélange protoliths to varying extents. A weak mechanical mixing array present in Sr isotope data is strongly overprinted by a fluid signal that dominates mélange Sr systematics. Nd isotope data suggest that Nd is more conservative during metamorphism and is largely controlled by mechanical mixing. We argue that mélange formation is an intrinsic process to all subduction zones and that the geochemistry of mélange will impart the strongest control on the geochemistry of metasomatic agents (hydrous fluids, silicate melts, or miscible supercritical liquids) progressing to arc magmatic source regions in the mantle wedge. Mélange formation processes suggest that comparisons of subduction “inputs” to arc volcanic “outputs” as a means to infer recycling at subduction zones dangerously over-simplify the physics of the mass transfer in subduction zones, as subducted mass is consistently redistributed into novel bulk compositions. Such mélange zones along the slab–mantle interface simultaneously bear characteristic elemental or isotopic signals of several distinct input lithologies, while experiencing phase equilibria not typical of any input. We recommend that future studies explore the phase equilibria of hybridized systems and mineral trace element residency, as these processes provide for a physical baseline from which it will be possible to follow the path of subducted mass through the system.
Trachytic lavas of Rishiri Volcano, northern Japan, show a peculiar geochemical variation across lava flow units. Samples collected systematically in a vertical cross section from a lava flow unit with a thickness of about 20 m are nearly homogeneous in major element compositions. However, some trace elements, including Li, B and Cs, are considerably depleted in samples collected from the main part of the flow unit, compared to those obtained from the surface of the lava flow (clinker layer). In particular, Cs content of the main flow unit is as low as ∼30% of the clinker layer. 11B /10B ratios of samples from the main flow unit are also slightly lower than those of the clinker samples, and the isotope compositions positively correlate with boron concentrations. These geochemical variations cannot be explained by magmatic processes in magma chambers, post-eruptive weathering, or alteration process. Rather, we infer these systematics resulted from escape of these elements from the lava flow unit during post-eruptive degassing. Vapor phases in which Li, B and Cs dissolved are suggested to have been transported through veins formed in the main flow unit as fractures due to slight shearing along the flow planes after lava emplacement. In the Tanetomi lava, only rocks of the clinker layer preserve original composition of magmas, although they are porous and brownish due to extensive oxidization. On the other hand, rocks of the main flow unit do not retain original magma compositions, although they are dense and grayish, and seem to be much fresher compared to the clinkers. A similar geochemical modification of lavas can occur in other volcanic systems, especially for lavas consisting of relatively thick flow units.
A new method has been developed for the simultaneous determination of Pb abundance and Pb isotopic composition with high precision and accuracy for small test portion masses by thermal ionisation mass spectrometry. In this method, a 205Pb-204Pb double spike is added to samples prior to the chemical separation of Pb, and the isotopic composition of the spike-sample mixture is determined rigorously by the double spike technique using a 207Pb-204Pb spike. The isotopic composition and concentration of Pb in the sample are then obtained by utilising the principle of isotope dilution. Using this technique, replicate determinations of Pb from NIST SRM 981 and GSJ JP-1 (peridotite; 0.07 µg g -1 Pb) were performed. The measured concentration and isotopic data were identical, within uncertainty, to published data or to data that were determined independently in this study. The application of this method to U-Pb dating and the determination of the “initial” Pb isotopic composition was also tested. Lead isotopic compositions and the concentrations of Pb, Th and U were determined for a single batch of samples, through the addition of 205Pb-204Pb, 230Th and 235U spikes to samples prior to chemical separation. Also in these experiments, we confirmed that this routine gives accurate data for Pb, Th and U concentrations and Pb isotopic compositions.
A precise and accurate determination method of 187Os/188Os, 189Os/188Os, and 185Re/187Re ratios of down to 0.2 pg of Os and 0.08 pg of Re using multicollector inductively coupled plasma mass spectrometry (MC-ICPMS) with multiple ion counting has been developed. Os and Re were introduced into MC-ICPMS as 0.5 mol L-1 HF solutions through the desolvator, and 185Re, 187Os, 188Os, and 189Os ions were detected simultaneously by four channeltrons. The Os and Re ratios were determined by the standard bracketing method, in which channeltron yields and mass discrimination factors are corrected together. Os and Re memories after 800-s wash were <0.1% and negligible, typically 0.02 and 0.03%, respectively. Isotope ratios of 187Os/188Os, 189Os/188Os, and 185Re/187Re were constant within error in the concentration ranges of 1−100, 1−40, and 0.4−5 pg mL-1 with reproducibility (1σ) of 2.7−0.14, 0.33−0.10, and 0.41−0.19%, respectively. For analysis of larger amounts of Os and Re, the Faraday cup measurement was employed. The precision and reproducibility obtained in this study are comparable to those of N-TIMS and better than MC-ICPMS achieved so far with a capability of higher sample throughput with simpler sample preparation.
A method for the determination of major, minor and trace elements in silicate samples by ICP-QMS and ICP-SFMS applying isotope dilution-internal standardisation (ID-IS) and multi-stage internal standardisation has been developed. Samples with an enriched isotope of 149 Sm (spike) were decomposed by a HF/HClO4 mixture and stepwise drying and finally diluted. In ID-IS for trace element analyses by Q-pole type ICP-MS (ICP-QMS), the Sm concentration was determined by ID, while other trace elements (Li, Be, Rb, Sr, Y, In, Cs, Ba, La, Ce, Pr, Nd, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Tl, Pb, Bi, Th and U) were determined using the 149 Sm intensity as an internal standard. Major and minor elements were determined by multi-stage internal standardisation, with Na, Mg, Al, P, Ca, V, Mn, Fe and Co measured by sector magnetic field type ICP-MS (ICP-SFMS) at middle resolution (MR; M/∆M = ~ 3000) using Sr determined by ICP-QMS in the sample as the internal standard. Potassium, Sc, Ni, Cu, Zn and Ga were measured at high resolution (HR; M/∆M ~ 7500) using the Sr concentration obtained by ICP-QMS or the Mn concentration obtained by ICP-SFMS at MR as internal standard. The merit of ID-IS is that accurate dilution of the sample is not required. Matrix effects on elemental ratios down to a dilution factor (DF) of 600 were not observed in either types of mass spectrometry. Pseudo-flow injection (FI), where transient signals were integrated, was used in ICP-QMS, while conventional continuous sample introduction was used in ICP-SFMS, resulting in total required sample solutions of 0.026 ml and 0.08 ml, respectively. Detection limits were low enough to determine these elements in depleted ultramafic rocks, and typical reproducibilities for basalts were 3% (Li-Be), 1% (Rb-U), 5% (In, Tl and Bi), 7% (Sc-Ga) and 3% (major elements). Carbonaceous chondrites including Orgueil (CI1), Murchison (CM2) and Allende (CV3), as well as reference materials, JB-1, -2, -3, JA-1, -2, -3 and JP-1 (GSJ), BHVO-1, AGV-1, PCC-1 and DTS-1 (USGS), were analysed to show the applicability of this method.
Ion microprobe zircon U–Pb ages from metavolcanic and associated granitic rocks of the late Archaean Musoma-Mara Greenstone Belt (MMGB) of northeast Tanzania reveal that the oldest mafic volcanism in the belt occurred at 2676–2669 Ma followed by felsic volcanism at ∼2668 Ma. The felsic volcanism was coeval with the emplacement of the oldest pulse of massive granitoids that is dated at 2668 Ma. The youngest volcanic episode, represented by a volcanic horizon in the largely sedimentary Kavirondian Supergroup that overlies the greenstone sequence with a marked unconformity, occurred at ∼2667 Ma. A younger phase of post-orogenic granites concluded the magmatic evolution of the MMGB at ∼2649 Ma. Our age data suggests that the entire volcano-sedimentary sequence in MMGB was emplaced in a relatively short time interval between ∼2676 and ∼2667 Ma. It also shows that contrary to arguments based on the degree of deformation, the foliated granites and some amphibolite rafts enclosed in them do not constitute the basement to the greenstone sequence. The data further shows that volcanism in the MMGB was younger than the ∼2820 Ma age of volcanism in the Sukumaland Greenstone Belt (SGB) to the far southwest and the ∼2720 Ma age of volcanism in the nearby Kilimafedha Greenstone Belt (KGB) to the south. The age of granitic magmatism (ca. 2.69–2.55 Ga) in the three belts was, however, largely coeval. Granitic magmatism of this age has also been reported in different parts of the Tanzania Craton suggesting that it was responsible for the late Archaean crustal growth and marks the beginning of a period of stability (or of cratonization).
Lawsonite eclogites preserve a record of very-low-temperature conditions in subduction zones. All occur at active margin settings, typically characterized by accretionary complexes lithologies and as tectonic blocks within serpentinite-matrix mélange. Peak lawsonite-eclogite facies mineral assemblages (garnet + omphacite + lawsonite + rutile) typically occur in prograde-zoned garnet porphyroblasts. Their matrix is commonly overprinted by higher-temperature epidote-bearing assemblages; greenschist- or amphibolite-facies conditions erase former lawsonite-eclogite relics. Various pseudomorphs after lawsonite occur, particularly in some blueschist/eclogite transitional facies rocks. Coesite-bearing lawsonite-eclogite xenoliths in kimberlitic pipes and lawsonite pseudomorphs in some relatively low-temperature ultrahigh-pressure eclogites are known. Using inclusion assemblages in garnet, lawsonite eclogites can be classified into two types: L-type, such as those from Guatemala and British Columbia, contain garnet porphyroblasts that grew only within the lawsonite stability field and E-type, such as from the Dominican Republic, record maximum temperature in the epidote-stability field. Formation and preservation of lawsonite eclogites requires cold subduction to mantle depths and rapid exhumation. The earliest occurrences of lawsonite-eclogite facies mineral assemblages are Early Paleozoic in Spitsbergen and the New England fold belt of Australia; this suggests that since the Phanerozoic, secular cooling of Earth and subduction-zone thermal structures evolved the necessary high pressure/temperature conditions. Buoyancy of serpentinite and oblique convergence with a major strike-slip component may facilitate the exhumation of lawsonite eclogites from mantle depths.
Eclogite xenoliths from the Colorado Plateau, interpreted as fragments of the subducted Farallon plate, are used to constrain the trace element and Sr–Nd–Pb isotopic compositions of oceanic crust subducted into the upper mantle. The xenoliths consist of almandine-rich garnet, Na-clinopyroxene, lawsonite and zoisite with minor amounts of phengite, rutile, pyrite and zircon. They have essentially basaltic bulk-rock major element compositions; their Na2O contents are significantly elevated, but K2O contents are similar to those of unaltered mid-ocean ridge basalt (MORB). These alkali element characteristics are explained by spilitization or albitization processes on the sea floor and during subduction-zone metasomatism in the fore-arc region. The whole-rock trace element abundances of the xenoliths are variable relative to sea-floor-altered MORB, except for the restricted Zr/Hf ratios (36.9–37.6). Whole-rock mass balances for two Colorado Plateau eclogite xenoliths are examined for 22 trace elements, Rb, Cs, Sr, Ba, Y, rare earth elements, Pb, Th and U. Mass balance considerations and mineralogical observations indicate that the whole-rock chemistries of the xenoliths were modified by near-surface processes after emplacement and limited interaction with their host rock, a serpentinized ultramafic microbreccia. To avoid these secondary effects, the Sr, Nd and Pb isotopic compositions of minerals separated from the xenoliths were measured, yielding 0.70453–0.70590 for 87Sr/86Sr, −3.1 to 0.5 for εNd and 18.928–19.063 for 206Pb/204Pb. These isotopic compositions are distinctly more radiogenic for Sr and Pb and less radiogenic for Nd than those of altered MORB. Our results suggest that the MORB-like protolith of the xenoliths was metasomatized by a fluid equilibrated with sediment in the fore-arc region of a subduction zone and that this metasomatic fluid produced continental crust-like isotopic compositions of the xenoliths.
In the petrogenesis of the recent magmas erupted at Stromboli volcano (Aeolian Arc, Italy) the role of mantle and crust components as well as that of magma dynamics and residence at shallow level are still largely debated. New constraints on source processes and magma dynamics are provided by geochemical and isotopic investigations of olivine-hosted melt inclusions (MI). The trace element compositions of MI, analyzed by SIMS and LA-ICPMS, are similar and reveal typical IAB signatures. However, peculiar of the pumice-hosted MI are significantly higher trace element concentration levels and slightly lower LILE/HFSE and LILE/REE ratios. Pb isotope ratios, measured by HR-SIMS, reveal a decoupling between chemistry and isotope values. MI from pumices are characterized by more evolved chemical compositions and lower 207Pb/206Pb and 208Pb/206Pb values than reported for present Stromboli lavas, pointing to FOZO-like compositions. Such compositions are similar to bulk lavas from other Aeolian volcanoes. In contrast, more primitive MI from S. Bartolo lavas closely approach 207Pb/206Pb and 208Pb/206Pb values of Stromboli (De Astis, 2000) bulk lavas, plotting in proximity of EM2. These new data are discussed in terms of possible source heterogeneity, changes in magma sources through time and mechanisms of magma dynamics within the deep and shallow plumbing system.
In order to unravel magma processes and the geochemical evolution of shallow plumbing systems beneath active volcanoes, we investigated U-series disequilibria of rocks erupted over the past 500 years (1469–2000 AD) from Miyakejima volcano, Izu arc, Japan. Miyakejima volcanic rocks show 238U–230Th–226Ra disequilibria with excess 238U and 226Ra, due to the addition of slab-derived fluids to the mantle wedge. Basaltic bombs of the 2000 AD eruption have the lowest (230Th/232Th) ratio compared to older Miyakejima eruptives, yielding the youngest 238U–230Th model age of 2 kyr. This reinforces our previous model that fluid release from the slab and subsequent magma generation in the mantle wedge beneath Miyakejima occur episodically on a several-kyr timescale. In the last 500 years, Miyakejima eruptives show: (1) a vertical trend in a (230Th/232Th)–(238U/232Th) diagram and (2) a positive linear correlation in a (226Ra/230Th)0 − 1/230Th diagram, which is also observed in lavas from some of the single eruptions (e.g., 1940, 1962, and 1983 AD). The variations cannot be produced by simple fractional crystallization in a magma chamber with radioactive decay of 230Th and 226Ra, but it is possibly produced by synchronous generation of melts in the mantle wedge with different upwelling rate or addition of multiple slab-derived fluids. A much more favorable scenario is that some basaltic magmas were intermittently supplied from deep in the mantle and injected into the crust, subsequently modifying the original magma composition and producing variations in (230Th/232Th) and (226Ra/230Th)0 ratios via assimilation and fractional crystallization (AFC). The assimilant of the AFC process would be a volcanic edifice of previous Miyakejima magmatism. Due to the relatively short timescales involved, the interaction between the assimilant and recent Miyakejima magmatism has not been recorded by the Sr–Nd–Pb isotopic systems. In such cases, Th isotopes and (226Ra/230Th) ratio are excellent geochemical tracers of magmatic evolution.
Mantle plumes are columns of hot, solid material that originate deep in the mantle, probably at the core–mantle boundary. Laboratory and numerical models replicating conditions appropriate to the mantle show that mantle plumes have a regular and predictable shape that allows a number of testable predictions to be made. New mantle plumes are predicted to consist of a large head, 1000 km in diameter, followed by a narrower tail. Initial eruption of basalt from a plume head should be preceded by ~1000 m of domal uplift. High-temperature magmas are expected to dominate the first eruptive products of a new plume and should be concentrated near the centre of the volcanic province. All of these predictions are confirmed by observations.
Zircons from a granodiorite porphyry at the Wushan copper deposit in the Lower Changjiang Metallogenic Belt, east central China, were dated using a Cameca IMS 1270 secondary ion mass spectrometer (SIMS); their chemical compositions and Hf isotopes were analyzed using a JEOL JX A8800 electron microprobe (EMPA) and a Neptune LA-MC-ICP-MS, respectively. The U–Pb dating of zircon reveals two age groups for the granodiorite porphyry; i.e. 144.6 ± 3.9 Ma and 121.0 ± 2.5 Ma. Zircons of the two age populations display distinct chemical compositional characteristics with respect to UO2/HfO2 ratios, and show a negative correlation of (UO2 + Y2O3 + ThO2) and HfO2. The older age group of ∼145 Ma, defined by the majority of the zircons, is interpreted as the magmatic emplacement age, whereas the younger age group of ∼121 Ma is interpreted as rejuvenation due to subsequent thermal or hydrothermal events. Other interpretations such as presence of two distinct magmatic crystallization stages or inheritance of the older zircons are also discussed in the paper. The ∼145 Ma magmatism at Wushan is consistent with the ages of most of the granitods in the Lower Changjiang Metallogenic Belt. The Hf isotope composition of zircons (ɛHf = −2.1 and −7.0; TDM Hf ages = 0.87 and 1.05 Ga), together with other available geochemical and Sr–Nd isotope data suggest that the granodioritic magma was derived from mixing of juvenile mantle with older crustal material. Due to the close spatial and temporal relationship of the granodiorite porphyry and the skarn mineralization at Wushan, the magamatic hydrothermal mineralization likely took place between 145 Ma and 121 Ma, likely around 121 Ma.
The least metasomatized xenoliths of spinel lherzolite and gabbro recovered from alnöite intruding crust of the southern Ontong Java Plateau on the island of Malaita yield an Sm-Nd age of ca. 160 Ma and an initial εNd value of ∼+8. In contrast, the plateau basement is ca. 120 Ma with initial εNd between +3.7 and +6.5. The xenoliths appear to represent normal Pacific oceanic lithosphere (uppermost mantle and lower crust) formed ∼40 m.y. before the plateau, indicating that the southern part of the plateau was emplaced off axis on mature seafloor. The closest 160 Ma seafloor to Malaita is >1800 km to the north, off the northeastern margin of the plateau, implying the presence of either an intervening large-offset fracture zone or a triple junction. The presence of significantly older oceanic lithosphere beneath the plateau places restrictions on proposed origins for the plateau.
We report experimentally determined self-diffusion coefficients for carbon in a type-IaA diamond at pressure and temperature conditions within diamond stability field at 10GPa and 2075–2375K. The activation energy of diffusion is 6.8±1.6eV and a preexponent constant is of 4.1×10−5m2/s [ln(−10.1±2.0)m2/s]. The activation energy is approximately 30% lower than results predicted previously from ab initio calculations.
Mechanisms of fractional crystallization with simultaneous crustal assimilation (AFC) are examined for the Kutsugata and Tanetomi lavas, an alkali basalt–dacite suite erupted sequentially from Rishiri Volcano, northern Japan. The major element variations within the suite can be explained by boundary layer fractionation; that is, mixing of a magma in the main part of the magma body with a fractionated interstitial melt transported from the mushy boundary layer at the floor. Systematic variations in SiO2 correlate with variations in the Pb, Sr and Nd isotopic compositions of the lavas. The geochemical variations of the lavas are explained by a constant and relatively low ratio of assimilated mass to crystallized mass (‘r value’). In the magma chamber in which the Kutsugata and Tanetomi magmas evolved, a strong thermal gradient was present and it is suggested that the marginal part of the reservoir was completely solidified. The assimilant was transported by crack flow from the partially fused floor crust to the partially crystallized floor mush zone through fractures in the solidified margin, formed mainly by thermal stresses resulting from cooling of the solidified margin and heating of the crust. The crustal melt was then mixed with the fractionated interstitial melt in the mushy zone, and the mixed melt was further transported by compositional convection to the main magma, causing its geochemical evolution to be characteristic of AFC. The volume flux of the assimilant from the crust to the magma chamber is suggested to have decreased progressively with time (proportional to t−1/2), and was about 3 × 10−2 m/year at t = 10 years and 1 × 10−2 m/year at t = 100 years. It has been commonly considered that the heat balance between magmas and the surrounding crust controls the coupling of assimilation and fractional crystallization processes (i.e. absolute value of r). However, it is inferred from this study that the ratio of assimilated mass to crystallized mass can be controlled by the transport process of the assimilant from the crust to magma chambers.
The evolution of the late Archean Belingwe greenstone belt, Zimbabwe, is discussed in relation to the geochemistry of the ultramafic to mafic volcanic rocks. Four volcanic types (komatiite, komatiitic basalt, D-basalt and E-basalt) are distinguished in the 2.7 Ga Ngezi volcanic sequence using a combination of petrography and geochemistry. The komatiites and D-basalts are rocks in which isotopic systems and trace elements are depleted. Chemical variations in komatiites and D-basalts can be explained by fractional crystallization from the parental komatiite. In contrast, komatiitic basalts and E-basalts are siliceous and display enriched isotopic and trace element compositions. Their chemical trends are best explained by assimilation with fractional crystallization (AFC) from the primary komatiite. AFC calculations indicate that the komatiitic basalts and E-basalts are derived from komatiites contaminated with ∼20% and ∼30% crustal material, respectively. The volcanic stratigraphy of the Ngezi sequence, which is based on field relationships and the trace element compositions of relict clinopyroxenes, shows that the least contaminated komatiite lies between highly contaminated komatiitic basalt flows, and has limited exposure near the base of the succession. Above these flows, D- and E-basalts alternate. The komatiite appears to have erupted on the surface only in the early stages, when plume activity was high. As activity decreased with time, komatiite magmas may have stagnated to form magma chambers within the continental crust. Subsequent komatiitic magmas underwent fractional crystallization and were contaminated with crust to form D-basalts or E-basalts.
Boron isotopic compositions of lavas from three representative Hawaiian shield volcanoes (Kilauea, Mauna Loa, and Koolau) were analyzed by thermal ionization mass spectrometry. The boron isotopic composition of each sample was analyzed twice, once with and once without acid leaching to evaluate the effect of posteruptive boron contamination. Our acid-leaching procedure dissolved glass, olivine, secondary zeolite, and adsorbed boron; this dissolved boron was completely removed from the residue, which was comprised of plagioclase, pyroxenes, and newly formed amorphous silica. We confirmed that an appropriate acid-leaching process can eliminate adsorbed and incorporated boron contamination from all submarine samples without modifying the original 11B/10B ratio. On the other hand, when the sample was weathered, i.e., the olivine had an iddingsite rim, 11B/10B of the acid-resistant minerals are also modified, thus it is impossible to get the preeruptive 11B/10B value from the weathered samples. Through this elimination and evaluation procedure of posteruptive contamination, preeruptive δ11B values for the shield lavas are −4.5 to −5.4‰ for Koolau (N = 8), −3.6 to −4.6‰ for Kilauea (N = 11), and −3.0 to −3.8‰ for Mauna Loa (N = 6). Historical Kilauea lavas show a systematic temporal trend for B content and Nb/B coupled with other radiogenic isotopic ratios and trace element ratios, at constant δ11B, indicating little or no assimilation of crustal materials in these lavas. Uncorrelated B content and δ11B in Koolau and Mauna Loa lavas may also indicate little or no effect of crustal assimilation in these lavas. The source of KEA-component (identical to the so-called Kea end member in Hawaiian lavas) of the Hawaiian source mantle, represented by Kilauea, should be derived from lower part of subducted oceanic crust or refractory peridotite in the recycled subducted slab. The systematic trend from Kilauea to Koolau—decreasing δ11B coupled with decreasing εNd as well as increasing 87Sr/86Sr and 206Pb/204Pb—is consistent with involvement of subducted sediment components in the EMK(enriched Makapuu)-component, represented by Makapuu-stage of Koolau lavas.
Felsic veins several cm thick to bodies several hundreds of m wide are sporadically distributed in the Kamila amphibolites of the Kohistan arc sequence. Some small dikes (less than one m thick) were deformed together with ductile deformation of wall-rock amphibolites; other small undeformed dikes crosscut foliation in the amphibolites. Large granitic intrusive bodies include gneissose and massive varieties. Ion-microprobe U-Pb dating of zircon grains reveal ages as follows: three deformed dikes, 107.7 ± 1.8 Ma, 94.0 ± 1.9 Ma, 81.0 ± 1.6 Ma; a single gneissose granitic body, 89.5 ± 4.2 Ma; three undeformed dikes, 82.0 ± 2.0 Ma, 80.6 ± 4.5 Ma, 75.8 ± 1.7 Ma; a massive granitic body, 75.7 ± 2.2 Ma; and a foliated amphibolite xenolith in the massive granitic body, 110.7 ± 4.9 Ma. Ages of the deformed dikes, the gneissose granitic body, and the amphibolite xenolith indicate that ductile deformation in the lower crust of the Kohistan arc took place episodically or successively during the period from 107 to 81 Ma. Ages of the undeformed dikes and the massive granitic body indicate that ductile deformation ceased prior to 80 Ma. Collision between Asia and the Kohistan arc elsewhere was inferred to be before 80 Ma. We conclude that the ductile deformation events did not extend beyond the time of Asia-Kohistan collision.
In order to understand various magma processes occurring in the terrestrial body, highly precise isotope analyses of U, Th and Ra have been developed. In the first, an effective silicate rock decomposing method was established. Conventional acid digestion of mafic silicate rocks resulted in the precipitation of insoluble fluorides and very poor recovery yields of some trace elements. In contrast, almost 100% of the trace elements were recovered using larger amounts of HClO4 than was conventionally used and evaporating the sample to dryness in a step-wise fashion. Then, new chemical separation methods of U, Th, and Ra were developed by employing some novel extraction chromatographic resins. For U isotope analysis by TIMS, a new activator, silisic-acid and phosphoric acid mix solution was very effective to produce stable and strong UO2+ beam, resulted in excellent improvement for both precision and reproducibility. For Ra isotope analysis, a new, precise and accurate analytical method was developed by employing total evaporation TIMS technique. These new methods have been applied for Miyakejima volcano, Izu arc, Japan. 238U-230Th-226Ra disequilibria observed in lavas with large 238U and 226Ra excesses imply metasomatism of depleted mantle by fluid related processes. In the equiline diagram, the trends for two magmatic stages (Stage 1 and 2) are regarded as two different isochrons with a common initial (230Th/232Th) ratio, although the trend for Stages 3 and 4 is a mixing line. The age difference in the equiline diagram corresponds to the interval of individual fluid-release events. Thus, fluid release from the slab and subsequent magma generation occur as episodic events on a several-kyr timescale. The model calculations show a very rapid ascent time of the slab components in the mantle wedge (<7 kyr), which can be explained by nearly instantaneous material transport in the mantle wedge.
The natural variation of Mg and Ca stable isotopes of carbonates has been determined in carbonate skeletons of perforate foraminifera and reef coral together with Mg/Ca ratios to assess the influence of biomineralisation processes. The results for coral aragonite suggest its formation, in terms of stable isotope behaviour, approximates to inorganic precipitation from a seawater reservoir. In contrast, results for foraminifera calcite suggest a marked biological control on Mg isotope ratios presumably related to its low Mg content compared with seawater. The bearing of these observations on the use of Mg and Ca isotopes as proxies in paleoceanography is considered.
A varied suite of mantle xenoliths from Malaita, Solomon Islands, was investigated to constrain the evolution of the mantle beneath the Ontong Java Plateau. Comprehensive petrological and thermobarometric studies make it possible to identify the dominant processes that produced the compositional diversity and to reconstruct the lithospheric stratigraphy in the context of a paleogeotherm. P–T estimates show that both peridotites and pyroxenites can be assigned to a shallower or deeper origin, separated by a garnet-poor zone of 10 km between 90 and 100 km. This zone is dominated by refractory spinel harzburgites (Fo91–92), indicating the occurrence of an intra-lithospheric depleted zone. Shallower mantle (∼Moho to 95 km) is composed of variably metasomatized peridotite with subordinate pyroxenite derived from metacumulates. Deeper mantle (∼95–120 km) is represented by pyroxenite and variably depleted peridotites that are unevenly distributed; the least-depleted garnet lherzolite (Fo90–91) lies just below the garnet-poor depleted zone (∼100–110 km), whereas the presence of pyroxenite is restricted to the deepest region (∼110–120 km), together with relatively Fe-enriched garnet lherzolite (Fo87–88). This depth-related variation (including the depleted zone) can be explained by assuming that the degree of melting for a basalt–peridotite hybrid source was systematically different at each level of arrival depth within a single adiabatically ascending mantle plume: (1) the depleted zone at the top of the mantle plume, where garnet was totally consumed in the residual solid; (2) an intermediate part of the plume dominated by the least-depleted garnet lherzolite just above the depth of the peridotite solidus; (3) the deepest pyroxenite-rich zone, whose petrochemical variation is best explained by the interaction between peridotite and normative quartz-rich basaltic melt, below the solidus of peridotite and liquidus of basalt. We explain the obvious lack of pyroxenites at shallower depths as the effective extraction of hybrid melt from completely molten basalt through the partially molten ambient peridotite, which caused the voluminous eruption of the Ontong Java Plateau basalts. From these interpretations, we conclude that the lithosphere forms a genetically unrelated two-layered structure, comprising shallower oceanic lithosphere and deeper impinged plume material, which involved a recycled basaltic component, now present as a pyroxenitic heterogeneity. This interpretation for the present lithospheric structure may explain the seismically anomalous root beneath the Ontong Java Plateau.
We demonstrate an approach to examining the metamorphic history of subducting oceanic crust that can complement records of subduction zone chemical cycling derived from studies of igneous rocks produced at volcanic arcs. By merging methods utilizing garnet zoning to establish prograde reaction histories with in situ high‐resolution trace element geochemistry, and application to coesite‐bearing mafic eclogites representing subduction to depths beneath arcs, we are able to directly identify geochemical manifestations of reactions contributing to element mobility in the subducting slab that are only inferred in studies of volcanic arcs or theoretical metamorphic models. Specifically, we identify a prograde metamorphic reaction, based solely on the zoning of geochemistry and mineral inclusions within garnet, and infer that these features are a record of the breakdown of coexisting clinozoisite + titanite and probable liberation of trace element–laden fluid from the rock during prograde metamorphism. We are then able to assign a specific depth interval for the reaction through calculation of the P‐T dependence of the reaction for these eclogites and comparison with a published P‐T trajectory. Because of the robust preservation of records of petrologic and geochemical processes by garnet, this methodology is particularly suited for study of ultrahigh‐pressure (UHP) eclogites, in which severe retrograde alteration (generally related to exhumation) commonly obscures prograde history.
Lithium (Li), boron (B), and lead (Pb) isotopic compositions of glass inclusions in olivine phenocrysts from Hawaiian lavas, (Kilauea Iki, Mauna Loa, and Koolau volcano) were measured by high mass resolution ion probe to search for possible signatures of recycled materials in the Hawaiian plume. In order to measure the isotopic compositions, a set of synthetic glass standards with matrices similar to those of the target glass inclusions was prepared. Isotopic variations among these synthetic standards were produced by additions of spikes, and their isotopic compositions were determined by TIMS. Using this set of standards, correction factors for instrumental mass fractionation for Li, B, and Pb isotope measurement were determined with internal precisions of <1.2‰, <1.6‰, and <0.8% (2σ) uncertainties for Li, B, and Pb, respectively. Twenty-eight glass inclusions were measured after homogenization to eliminate dendritic crystals. These glass inclusions showed isotopic variations from −10.2‰ to +8.4‰ for δ7Li, from −10.5‰ to +5.2‰ for δ11B, from 0.7994 to 0.8909 for 207Pb/206Pb, and from 1.989 to 2.139 for 208Pb/206Pb, which are considerably larger than those for whole rocks. This suggests that the Hawaiian lavas are mixtures of melts derived from isotopically distinct sources, and that glass inclusions better preserve information regarding source heterogeneity than do whole rocks. In particular, significantly low δ7Li and δ11B values for the Mauna Loa and Koolau samples indicate an isotopically “light” Li and B source, perhaps containing recycled materials that experienced dehydration during subduction. The extremely low Pb isotope signature, which corresponds to HIMU, also suggests some contribution from recycled materials to the generation of the Hawaiian magma. Our results suggest that recycled materials, which experienced near-surface alteration and then dehydration during subduction, played an important role in creating geochemical heterogeneity in the Hawaiian lavas.
Magmatic differentiation processes in a cooling magma body were examined using a numerical model considering multicomponent thermodynamics and momentum, energy and species transport. The model accounts for melt transport induced by its density variation, resulting primarily from solid–liquid phase change. The equilibrium mineral assemblages, their mass fractions and their chemical compositions are determined by multicomponent thermodynamic models, and these parameters are linked with the calculations of velocity, pressure, temperature and species fields at each iteration and time step. For simplicity, solid phases are assumed to be stationary, and only olivine and plagioclase that are the earliest crystallization phases in common basaltic magmas are considered as fractionating phases. Application of the model to natural magmatic system shows that crystallization occurs selectively along the chilled boundaries soon after the cooling, and the magma body is separated into high-crystallinity mush zones and mostly crystal-free main magma. Because of the melt exchange between the mush zones and the main magma by compositional convection, the main magma evolves progressively in composition and the spatial chemical heterogeneity is grown with time. The melt segregated from the sidewall mush zone is accumulated below the roof mush zone, forming compositional stratification in the upper part of the main magma. On the other hand, the fractionated melt from the floor mush zone principally mixes with the overlying ambient magma in the middle and lower parts of the main magma body. This study shows that the direct treatment of nonlinear coupling among momentum, energy and species transport provides useful information of the thermal and chemical evolution of magma chambers as a function of time and space.
A precise and simple method for the determination of lithium concentrations in small amounts of silicate sample was developed by applying isotope dilution-inductively coupled plasma-mass spectrometry (ID-ICP-MS). Samples plus a Li spike were digested with HF-HClO4, dried and diluted with HNO3, and measured by ICP-MS. No matrix effects were observed for 7Li/6Li in rock solutions with a dilution factor (DF) of ≥ 97 at an ICP power of 1.7 kW. By this method, the determination of 0.5μg g-1Li in a silicate sample of 1 mg can be made with a blank correction of < 1%. Lithium contents of ultrabasic to acidic silicate reference materials (JP-1,JB-2, JB-3, JA-1, JA-2, JA-3, JR-1 and JR-2 from the Geological Survey of Japan, and PCC-1 from the US Geological Survey) and chondrites (three different Allende and one Murchison sample) of 8 to 81 mg were determined. The relative standard deviation(RSD) was typically < 1.7%. Lithium contents of these samples were further determined by isotope dilution-thermal ionisation mass spectrometry (ID-TIMS). The relative differences between ID-ICP-MS and ID-TIMS were typically < 2%, indicating the high accuracy of ID-ICP-MS developed in this study.
Across-arc Li–B–Pb isotope systematics, together with trace element geochemistry and phase relationships in subducting slabs are used to understand the petrogenesis of lavas from the northeastern Japan arc. Pb/Nb ratios and Pb isotope compositions of the arc lavas decrease with depth to slab whereas Li/Y, U/Nb, Th/Nb and La/Sm show an upward profile across the arc, with peaks at 180 km depth to the Wadati–Benioff zone (WBZ). The peaks in these profiles may reflect the influence of lawsonite breakdown in the slab at 180 km depth. B/Nb ratios of the arc lavas do not show clear across-arc variation and the δ11B values show a concave upward across-arc profile with minimum values at around 180 km in depth of the WBZ. These results possibly reflect the decomposition of tourmaline at ∼180 km. Our results suggest that accessory minerals and minor phases in the subducting slab play important roles in determining the chemical compositions of fluid released by dehydration, and the resulting trace element and isotope composition of arc lavas. Li isotope compositions of the lavas are MORB-like and do not show systematic across-arc variation, contrasting with Izu arc lavas, which show maximum δ7Li values at the volcanic front and a systematic decrease towards the back arc. The strikingly different results for the northeastern Japan arc and the Izu arc are likely to be caused by differing extents of Li isotope fractionation due to differing subduction zone physical characteristics, such as thermal structure of the subducting slab and subduction angle. Thus, not only chemical characteristics of the subducting slab but also the physical, as well as chemical characteristics of the subduction zone could affect the Li isotope compositions of subducting slabs, producing heterogeneity in the Li isotope composition of the mantle.
The use of light stable isotopes to elucidate Earth processes dates to the pioneering work of Harold Urey, who was awarded the Nobel prize for chemistry in 1934 for his discovery of deuterium and determination of its fractionation from hydrogen as a function of temperature. Perhaps less well known, Urey was also one of the first to delve into lithium isotope geochemistry. Taylor and Urey (1938) used ion exchange chromatography to separate 6Li from 7Li, demonstrating the extreme isotopic fractionation achievable on a resin bed. The very large mass difference (∼15%) between the two isotopes of lithium is responsible for both the potential utility and the difficulty in the application of lithium isotopes to geochemical problems. The utility stems from the very large mass fractionation that can occur due to natural processes; with the publication of this volume, up to 80‰ variation of 7Li/6Li has now been documented in terrestrial samples. The difficulty stems from the fact that, as Taylor and Urey demonstrated long ago, these fractionations are not limited to nature, and successful quantitative measurement of lithium isotopic compositions requires extraction of 100% of the lithium present in a sample during laboratory processing. In addition to the intrinsically large fractionations observed for 7Li/6Li, other properties, such as the single valence state, and the affinity of lithium for fluids, make it a potentially unique tracer for fluid–rock interaction in the Earth (see recent reviews by Elliott et al., 2004, Tomascak, 2004).
Controversy exists as to whether the 2.7 Ga Belingwe greenstone belt, Zimbabwe, is autochthonous or allochthonous. In this study we report direct evidence for an autochthonous continental setting for the Belingwe greenstone belt. Garnet and clinopyroxene xenocrysts were discovered in the fresh ultramafic komatiites. Major and trace element compositions of these xenocrysts suggest that they originated from mafic lower crust, presumably garnet granulite in composition, at a low temperature of ∼600 or ∼700 °C. Furthermore, in a komatiitic basalt sample, we have discovered orthopyroxene and clinopyroxene xenocrysts that may have originated from lithospheric mantle beneath the continental margin. Discoveries of these xenocrysts indicate that the komatiite magma was transported to the surface and quenched rapidly enough to prevent the complete melting of continental fragments.
Major and trace element mineral/melt partition coefficients are presented for phases on the liquidus of fertile peridotite at 23–23.5 GPa and 2300 °C. Partitioning models, based on lattice-strain theory, are developed for cations in the ‘8-fold’ sites of majorite and Mg-perovskite. Composition-dependant partitioning models are made for cations in the 12-fold site of Ca-perovskite based on previously published data. Dmin/melt is extremely variable for many elements in Ca-perovskite and highly correlated with certain melt compositional parameters (e.g. CaO and Al2O3 contents). The 8-fold sites in Mg-perovskite and majorite generally have ideal site radii between 0.8 and 0.9 Å for trivalent cations, such that among rare-earth-elements (REE) Dmin/melt is maximum for Lu. Lighter REE become increasingly incompatible with increasing ionic radii. The 12-fold site in Ca-perovskite is larger and has an ideal trivalent site radius of ∼1.05 Å, such that the middle REE has the maximum Dmin/melt. Trivalent cations are generally compatible to highly compatible in Ca-perovskite giving it considerable leverage in crystallization models. Geochemical models based on these phase relations and partitioning results are used to test for evidence in mantle peridotite of preserved signals of crystal differentiation in a deep, Hadean magma ocean. Model compositions for bulk silicate Earth and convecting mantle are constructed and evaluated. The model compositions for primitive convecting mantle yield superchondritic Mg/Si and Ca/Al ratios, although many refractory lithophile element ratios are near chondritic. Major element mass balance calculations effectively preclude a CI-chondritic bulk silicate Earth composition, and the super-chondritic Mg/Si ratio of the mantle is apparently a primary feature. Mass balance calculations indicate that 10–15% crystal fractionation of an assemblage dominated by Mg-perovskite, but with minor amounts of Ca-perovskite and ferropericlase, from a magma ocean with model peridotite-based bulk silicate Earth composition produces a residual magma that resembles closely the convecting mantle. Partition coefficient based crystal fractionation models are developed that track changes in refractory lithophile major and trace element ratios in the residual magma (e.g. convecting mantle). Monomineralic crystallization of majorite or Mg-perovskite is limited to less than 5% before certain ratios fractionate beyond convecting mantle values. Only trace amounts of Ca-perovskite can be tolerated in isolation due to its remarkable ability to fractionate lithophile elements. Indeed, Ca-perovskite is limited to only a few percent in a deep mantle crystal assemblage. Removal from a magma ocean of approximately 13% of a deep mantle assemblage comprised of Mg-perovskite, Ca-perovskite and ferropericlase in the proportions 93:3:4 produces a residual magma with a superchondritic Ca/Al ratio matching that of the model convecting mantle. This amount of crystal separation generates fractionations in other refractory lithophile elements ratios that generally mimic those observed in the convecting mantle. Further, the residual magma is expected to have subchondritic Sm/Nd and Lu/Hf ratios. Modeling shows that up to 15% crystal separation of the deep mantle assemblage from an early magma ocean could have yielded a convecting mantle reservoir with 143Nd/144Nd and 176Hf/177Hf isotopic compositions that remain internal to the array observed for modern oceanic volcanic rocks. If kept in isolation, the residual magma and deep crystal piles would grow model isotopic compositions that are akin to enriched mantle 1 (EM1) and HIMU reservoirs, respectively, in Nd-Hf isotopic space.
We report a new analytical technique for precise and accurate determination of the 228Ra/226Ra ratio by total evaporation thermal ionization mass spectrometry (TE-TIMS). An improved chromatographic separation method employing a new tandem column technique that enables high yield and high purity of Ra is also described. Repeated analysis of Ra standard solution (228Ra/226Ra = 1.1) yielded an analytical reproducibility for 228Ra/226Ra ranging from 0.2% to 0.9% (2σ) for 170 to 2 fg of Ra. Reproducibility was strongly controlled by counting statistics of 226Ra+ and 228Ra+ ion beam intensities collected by an ion counting detector, implying that in-run precision for Ra isotope analysis of our method can be evaluated using a counting statistics law. Determination of 226Ra abundances in silicate rock samples were examined by isotope dilution TE-TIMS, and reproducibility was 0.3% (2σ) for JR-2 (226Ra = 3700 fg g−1) and 0.6% (2σ) for JB-2 (226Ra = 81 fg g−1); the reproducibility of these measurements are 2–3 times better than previously published conventional TIMS procedures. The 226Ra/228Ra ratio in natural samples can be also measured with an analytical uncertainty of ∼1% (2σ). The accuracy of our method was confirmed by measuring (226Ra/230Th) and (228Ra/232Th) ratios for JR-2, a sample old enough (1 Ma) to be in 230Th–226Ra and 232Th–228Ra radioactive equilibria. Our method is especially effective for samples with a very low abundance of Ra.
Boron concentrations and isotope compositions of fluids and lavas from subduction-zone settings show great potential for elucidating mass flux at Earth's modern convergent margins. However, the fluid-mineral-melt behavior of B and its two stable isotopes remains relatively poorly understood. Boron isotope analyses of tourmaline in metasedimentary rocks subducted to 15–90 km depths (1) demonstrate the ability of this mineral to retain information regarding prograde devolatilization history in even highly retrograded rocks and (2) indicate the importance of tourmaline in affecting whole-rock B loss and B isotope evolution during subduction-zone metamorphism. The B lost from micas during metamorphism of subducting sedimentary rocks and altered oceanic crust is isotopically more enriched in 11B than the B retained in the micas. Beneath forearcs and volcanic arcs, the B from micas is either removed from the subduction-zone rocks via metamorphic fluids or sequestered by growing tourmaline, in which the B can be entrained to even greater depths. Here we demonstrate that these metamorphic fluids could contribute to the relatively high δ11B signatures observed in most arc lavas and the across-arc trends of decreasing δ11B observed in several arcs.
A technique for separation of Mg, with 100% yield from low-Mg biogenic carbonates has been developed suitable for high precision analysis of Mg isotopes by multiple-collector inductively coupled plasma mass spectrometry. Two separate stages of ion-exchange chromatography were carried out using cation exchange resin, AG50W-X12 with a Mg recovery >99.9%. The repeatability of the Mg isotope ratio measurement using this technique including chemistry and mass spectrometry is ±0.14‰ on δ26Mg and ±0.09‰ on δ25Mg at 95% confidence. This was demonstrated using a synthetic solution (Na∶Mg∶Ca∶Sr = 2∶1∶100∶1 in weight) over a period of six months. The robustness of the technique was further assessed by replicate analyses of three natur al samples, seawater, foraminifera and dolomite. A total variation over 4.5‰ on δ26Mg was observed and the Mg isotope composition of seawater was 2.59 ± 0.14‰ on δ26Mg and 1.33 ± 0.09‰ on δ25Mg which were the highest isotope ratios among the samples measured.
A new, simple, and practical method has been developed for the accurate and precise isotopic analysis of extremely small amounts of Pb (<∼3 ng) by thermal ionization mass spectrometry. Two different types of double spikes, one consisting of 205Pb and 204Pb and another enriched in 207Pb and 204Pb, are used to reduce “204Pb error” and to correct mass fractionation during mass spectrometry. Using this technique, replicate analyses of 1.5 ng of Pb from NBS981 were performed, and an external precision of 0.02% (2σ) was attained for the 208Pb/204Pb ratio. Compared with results for 1.5 ng of Pb by the normal double spike method using a single 207Pb–204Pb double spike, the external precision for the isotopic ratios involving 204Pb is reduced by about 60–70%, simply by addition of the 205Pb–204Pb double spike. The two double spikes method was also applied to isotopic analyses of natural rock samples, and we obtained an external precision of 0.06% (2σ) for 208Pb/204Pb in ∼1.5 ng of Pb separated from fresh peridotite, in which the Pb concentration is as low as 3.2 ppb. This new technique is superior to any previous method for precise and accurate isotopic analyses of extremely small amounts of Pb, and will be a highly powerful tool in the future of earth science and environmental science.
Pre-eruption processes are investigated for magmas erupted in 1983 from Miyake-jima volcano, which is one of the most active volcanoes in Japan. The whole-rock compositional trends of the eruptive products are principally smooth and linear. Magmas erupted from some fissures have compositions that deviate from the main linear trend. Phenocryst contents of samples displaced from the linear compositional trends are significantly lower than those of samples on the main trends. Anorthite-rich plagioclase phenocrysts, present throughout the 1983 products, are too calcic to have crystallized from the erupted magma composition, and were derived from a basaltic magma through magma mixing. Although the linear whole-rock composition trends favor simple two-component magma mixing, this cannot explain the presence of samples that deviate from the main trend. Instead, the observed composition trends were formed by mixing of a homogeneous basaltic magma with andesitic magmas exhibiting compositional diversity. The original linear composition trends of the andesitic end-member magma were rotated and shifted to the direction of the basaltic end-member magma by magma mixing. The samples out of the main trends represent magmas with less basaltic component than those on the trend. The density and viscosity of the basaltic end-member magma were comparable with those of the andesitic end-member magmas. The basaltic magma, discharged from one magma chamber at ∼2 kbar pressure, was injected into a magma chamber at lower pressure occupied by the chemically zoned andesite magma (∼1 kbar), and possibly as a fountain. To establish the characteristic mixing trend of the 1983 magma, the basaltic component must have been distributed systematically in the zoned andesite magma. A requirement is that the basaltic magma spread laterally and mixed with the andesite magma at various levels of ascent of the fountain in the host andesite magma. Analysis of compositional zoning in titanomagnetite crystals revealed that the eruption of the 1983 magmas was initiated soon after the replenishment of the basaltic magma in the 1 kbar magma chamber.
We have participated in the analytical competition related to the sample-return mission, MUSES-C of the ISAS, to be launched in May 2003 and returned in summer 2007. In this competition, we have determined major and trace element abundances and isotopes (as many as possible), both for two powdered samples provided by the ISAS and for chondrules separated from Allende meteorite as an additional demonstration of our high-spatial resolution analytical capabilities for fragment samples. 100 mg of each of the competition samples, 1C and 2C, were split into two fractions of approximately 30 and 70 mg for the determinations of elemental abundances and the isotope analyses, respectively. The bulk concentrations of 55 elements in each 30 mg sample were analyzed by quadruple-type ICP-MS and sector-type ICP-MS with analytical uncertainties better than 10 percent (1 sigma). B, Pb, Li, Rb, Sr, Sm and Nd were successively separated from the remaining 70 mg of each of the samples, using a novel integrated, multi-ion exchange column chemistry approach, and then the isotopes of these elements were successfully determined by TIMS with analytical errors similar to those for analyses of terrestrial samples. The Sr, Nd, Re and Os isotopic compositions were also analyzed using the remaining aliquots of the sample solutions for trace element analyses by ICP-MS. The results obtained in this study indicate that 1C and 2C samples are probably ordinary chondrite and the Allende meteorite, respectively. However, extreme W, Ta and Nb enrichments in the 1C were probably caused by contamination during sample preparation. Furthermore, both of the samples were extensively contaminated by B from the borosilicate glass container in which the samples were delivered. Five chondrules were separated from Allende meteorite and then sliced into three pieces using a dicing saw. The center slices were used to petrographically determine the mineral phases, compositionally map these phases by SEM-EDX, and obtain quantitative major and trace element compositions (30 elements) by SEM-EDX and ion microprobe. The two outer slices, for which sample masses were less than 1 mg, were chemically treated to obtain the bulk trace elements and isotope compositions of the chondrules. For the chondrule slices, 24 trace elements and Sr and Nd isotopic compositions were determined with extremely small analytical uncertainties by ICP-MS and TIMS (for Sr and Nd, respectively). Based on the analytical experience, including this competition, we believe that all of the analyses carried out could have been completed within 50 days if we could have concentrated on this project alone during that 50-day period. In this report, we describe the analytical techniques employed for the powdered samples and the chondrules, and we present all of the results obtained during the approximately 3-month period of the analytical competition.
We have evaluated recovery yields of Zr, Nb, Hf and Ta, which are called high field strength elements (HFSE), in the synthetic Ca–Al–Mg–HF solution system using two different methods: at < 70 °C in an ultrasonic-bath (denoted as the ultrasonic method) and at 205 °C using a TFE Teflon® bomb (denoted as the bomb method). Full recovery of HFSE into the supernatant HF solution was not achieved in cases where fluorite (CaF2) forms in the precipitate in both methods and sellaite (MgF2) forms in the ultrasonic method. In order to suppress fluorite precipitation, an ‘Al-addition method’ was developed in which Al solution is added to the sample before decomposition to change the matrix solution to a composition in which no fluorite forms. Using the Al-addition method, HFSE concentrations of Ca-rich materials were analyzed by inductively coupled plasma mass spectrometry (ICP-MS) by an isotope dilution method for Zr and Hf and by a calibration curve method for Nb and Ta. Furthermore, we found isotopic disequilibria of Zr and Hf between sample and spike without Al-addition for Ca-rich samples, and that the Al-addition method was very effective in achieving isotopic equilibria and full recovery of HFSE, resulting in high accuracy in their determination.
We present the first finding of the high-pressure mineral coesite in lawsonite-bearing eclogite xenoliths from the Colorado Plateau, United States. The presence of coesite in these xenoliths supports the hypothesis that the eclogite formed in a low-temperature–high-pressure environment such as envisaged inside subducted oceanic lithosphere. Ion-microprobe U-Pb dating of micrometer-scale zircons in the eclogites yields ages ranging from 81 Ma to 33 Ma, the two extremes in age likely indicating the age of crystallization during subduction-related metamorphism and the age of recrystallization by the host magmatic event, respectively. These observations conclusively demonstrate that certain eclogite xenoliths from the Colorado Plateau originated as fragments of the subducted Farallon plate, which had been residing in the upper mantle since the Late Cretaceous. This is the first conclusive evidence that any eclogite xenoliths can be directly linked to a known subducted plate.
238U‐230Th‐226Ra systematics in lavas from Miyakejima volcano, Japan, are presented to estimate the timescale of magmatic processes beneath an island arc. Miyakejima volcano has four recent eruptive stages (Stages 1–4) starting >7000 BP. 238U‐230Th‐226Ra disequilibria observed in lavas with large 238U and 226Ra excesses imply metasomatism of depleted mantle by fluid‐related processes. This metasomatism is also suggested by trace element and Sr‐Nd‐Pb isotopic systematics in the same lavas. In the equiline diagram, the trends for two magmatic stages (Stages 1 and 2) are regarded as two different isochrons with a common initial (230Th/232Th) ratio, although the trend for Stages 3 and 4 is a magma mixing line. Our model calculations show that slab‐derived fluids can deliver some Th and a very rapid ascent time of the slab components in the mantle wedge (< 7 kyr) is inferred. This rapid ascent can be explained by nearly instantaneous material transport in the mantle wedge by a hydrofracture model for fluid and a channel flow model for melt. Such a timescale estimate is not increased even if melting processes that enhance 226Ra are taken into account. The age difference in the equiline diagram corresponds to the interval of individual fluid‐release events (13 kyr between Stages 1 and 2, and 5 kyr between Stages 2 and 3). Thus fluid release from the slab and subsequent magma generation occur as episodic events on a several‐kiloyear timescale.
Pegmatite veins and their host rocks from the Chilas complex, N. Pakistan are dated using the Sm–Nd chronometer. The dated pegmatite veins are mainly composed of plagioclase and hornblende. The granulite-facies host rocks consist of plagioclase, clinopyroxene, orthopyroxene and hornblende. Sm–Nd mineral isochrons of the coarse-grained pegmatite veins give ages of 107 and 94 Ma for the two dated veins, respectively. In contrast, the host rocks in the vicinity of the sampled veins give ages between 69 and 72 Ma for the first sampled vein and between 60 and 76 Ma for the second sampled vein. The fact that the vein ages are apparently older than their host rocks might be explained in different ways. (1) The apparent ages may be the consequence of isotopic mixing and bear no geochronological meaning. (2) If the apparent ages are real, then there are three possible interpretations that are discussed here: (i) the vein ages may indicate that the magmatic age of the Chilas complex could have been >107 Ma, which is much older than the previously reported magmatic age of 84 Ma; (ii) vein ages may date the time span of granulite-facies metamorphism in the Chilas complex which approximately coincides with the period of the Kohistan–Asia collision (102–85 Ma); and/or: (iii) the vein ages show the effects of the variation of closure temperature with grain size as coarser minerals have higher closure temperatures and vice versa, which consequently affects the Sm–Nd mineral age. The third interpretation gains particular significance, as there is a close correlation in apparent grain size with measured absolute age in both sets of samples. This interpretation is therefore discussed in some detail.
A simple technique has been developed for the precise analysis of lead isotope in natural rock samples by thermal ionization mass spectrometry (TIMS). Two-stage column chromatography, using 100 and 10 μl columns, was used to minimize the amounts of impurities in separated lead samples. This dramatically improved the reproducibility of mass fractionation during mass spectrometry using an ion emitter made of a mixture of silicic acid and phosphoric acid. This improvement made it possible to precisely determine the Pb isotopic compositions of very small sample sizes, employing “zero-time correction” for mass discrimination, without requiring a double-spike technique. Using the present method, analytical reproducibility of 208Pb/204Pb of 0.02% and 0.06% (2σ) was attained for 100 and 1 ng of Pb, respectively, separated from natural rock samples. Furthermore, we obtained a reproducibility of 0.06% (2σ) for 208Pb/204Pb for 10 ng of Pb separated from GSJ JP-1 (peridotite), in which the Pb concentration was 0.09 ppm. The measured isotope compositions of USGS standard rocks AGV-1 and BCR-1 were comparable with the published values using the double-spike technique. These observations suggest that our simple technique is reliable in terms of both accuracy and precision for the determination of the Pb isotopic compositions of natural rock samples irrespective of rock chemistry and sample sizes from 1 to 100 ng of Pb.
Granulite-facies orthogneisses of andesitic to dacitic composition in the Usambara Mountains of north eastern Tanzania yield a Sm–Nd whole rock isochron age of 815±58 Ma and an initial ε(Nd) value of 4.1. This age is interpreted as dating Sm–Nd fractionation during extraction from the mantle and immediate subsequent crystallisation of the granulite protolith during an event of regional calc-alkaline magmatism in the area. Isotopic and geochemical characteristics of the rocks are consistent with a convergent margin setting for the magmatism with minimal contamination by older continental crust. The isotopic data from the Usambara Mountains demonstrate that Neoproterozoic crust formation in the Arabian–Nubian Shield and parts of the Mozambique Belt was broadly contemporaneous.
A simple and accurate method for the determination of Cr, Ni, Cu and Zn at μg g-1 levels in milligram-sized bulk silicate materials is reportedusing isotope dilution high-resolution inductivelycoupled plasma-mass spectrometry (HR-ICP-MS) with a flow injection system. Silicate samples with Cr, Ni, Cu and Zn spikes were digested with HF-HBr and Br2, and subsequently decomposed at 518 K in a Teflon bomb. In this procedure, all sulfides and chromite, major hosts of these elements, were completely decomposed, thus allowing for isotope equilibration between the sample and spike.Magnesium and Al fluorides formed after the digestion of the sample were removed by centrifugation, and the supernatant was directly aspirated into a HR-ICP-MS at a mass resolution of 7500, where interfering oxide ions, ArO+, CaO+,TiO+, CrO+ and VO+, were separated from Cr+ , Ni+ ,Cu+ and Zn+ . No matrix effects were observed down to a dilution factor of 50. Detection limits for these elements in silicate samples were < 0.04μg g-1. The effectiveness of the technique was demonstrated by the analysis of 13 to 40 mg test portions of USGS and GSJ silicate reference materials with a major element composition ranging from andesite to peridotite, in addition to 8-23 mg of the Smithsonian reference Allende. Both the reproducibility and the deviation from the reference value for most reference materials of various rocktypes were < 9%, and thus confirm that the method gives accurate analytical results for small sample sizes over a wide range of Cr, Ni, Cu and Zn contents. This method is, therefore, suitable for analysing small and/or precious bulk samples, such as meteorites, mantle peridotites and mineral separates, and for the characterisation of silicate and sulfide minerals for use as calibration samples in secondary ion mass spectrometry or laser ablation ICP-MS.
Makishima and Nakamura (M&N) reported a new determination method of sulfur content in geological materials by isotope dilution using high resolution ICPMS. In this paper, sulfur contents of 10 silicate reference materials, including BCR-1, which has been one of the most important reference materials for nearly 40 years, in addition to WMS-1 and the Smithsonian reference Allende powder were determined. The method seems to be theoretically robust; however, Kelly et al. claimed that the sulfur content of BCR-1 by M&N (474 ± 14 μg g-1, 1σ) is too high beyond the 95% confidence intervals of the consensus values of Gladney et al. (410 ± 50μg g-1), Watanabe (441 ± 1.5μg g-1), and new analyses of KVM (446.8 ± 2.6; 438.7 ± 2.0μg g-1) by Carius tube digestion using isotope dilution−thermal ionization mass spectrometry.
A new separation method of Ti from silicate materials is presented that is suitable for the determination of natural Ti isotope variations using multi-collector inductively coupled plasma source mass spectrometry (MC- ICP-MS). This method makes possible for the first time the separation of Ti from natural materials, with high purity, high recovery and no introduction of artificial mass fractionation. Following sample decomposition using HF, Ti is separated using a three-column procedure. In the first column using an anion-exchange resin, AG 1X8, major elements and the majority of trace elements are separated. In the second column, after eliminating F- by evaporation with HClO4 and re-dissolution with H2O2–HNO3 , Ti is separated from Zr and Hf using a liquid–liquid extraction resin, U/TEVA. In the third column, which is the same as the first column, trace amounts of Al and P are further removed. Recovery yields were almost unity, and no Ti isotope fractionation occurred from the overall chemical processing. The reproducibilities (2s) of the Ti isotope ratio measurement for a meteorite (eucrite) and a lamproite were < 0.5ε for ε47Ti, ε48Ti and ε49Ti, and < 1ε for ε50Ti, which were comparable to those for the pure Ti standard solution.
Major and trace-element and Sr, Nd, and Pb isotopic compositions have been determined for Koolau shield lavas and Nuuanu and Wailau landslide deposits, Hawaii. The Koolau shield is composed of older main shield-stage and younger Makapuu-stage lavas. Lavas of the main shield-stage are exposed low in the subaerial Nuuanu Pali and in Nuuanu landslide deposits. Main shield-stage lavas resemble Loa- or Kea-type compositions; they are characterized by lower Ba/Nb, La/Nb, Pb/Nd, Sr/Nb, Nd/Nb, Zr/Nb, and 87Sr/86Sr, and by higher 143Nd/144Nd and 206Pb/204Pb than those of Makapuu-stage lavas (Koolau-type). Sr-Nd-Pb isotope systematics suggest that Koolau shield lavas were generated from at least three endmembers, such as: Enriched Makapuu (EMK), Depleted Makapuu (DMK), and Kea (KEA) components. The proportion of these endmembers successively changed from earlier KEA-dominated to later EMK-dominated. Koolau shield-stage lavas span nearly the entire range of the isotopic compositions reported previously for shield-stage lavas from all Hawaiian islands, and reveal secular changes in the amounts of plume components.
We improved the U-Pb zircon dating method employing HR-SIMS by applying i) preparation of precise and homogeneous zircon standards by ID-TIMS, ii) simultaneous analysis of Pb isotopes by multi-collection system, and iii) use of a highly focused primary ion beam as small as 5μm in diameter. Using the improved HR-SIMS technique, U-Pb ages of zircons in an eclogite xenolith from the Colorado Plateau were determined. Zircon occurs as small inclusions ( < 20μm) in most constituent minerals. Ten zircons were measured, and the concordant analyses of these zircon data yielded a weighted mean value of 65.2±0.7Ma for the age of crystallization. Petrographic and geochemical observations suggest that this zircon age represents the age of initial subduction of basaltic oceanic crust. We conclude that the eclogite xenolith was a fragment of basaltic oceanic crust subducted to > 90km depth along a cold geotherm with a subduction rate of > 2cm/y in Tertiary.
We have developed a highly precise method for the determination of ferrous iron (Fe2+) in silicate rocks. Our new method is based on Wilson’s procedure (1955) in which surplus V5+ is used to oxidize Fe2+ into Fe3+ while equivalently reducing V5+ into V4+. Because V4+ is more resistant to atmospheric oxidation than Fe2+, Fe2+ in the sample can be determined by measuring unreacted V5+ by adding excess Fe2+ after sample decomposition and then titrating the unreacted Fe2+ with Cr6+. With our method, which involves conditioning the sample solution with 5 M H2SO4 in a relatively small beaker (7 mL), the oxidation of Fe2+ or V4+ that leads to erroneous results can be completely avoided, even in 100-h sample decompositions at 100°C. We have measured the concentration of FeO in 15 standard silicate rock powders provided by the Geological Survey of Japan (GSJ). Analytical reproducibility was better than 0.5% (1σ) for all but those samples that had small amounts of Fe2+ ( < 1.5 wt.% of FeO). Fourteen of these samples gave FeO contents significantly higher than the GSJ reference values. This likely indicates that the GSJ reference values, obtained by compiling previously published data, contain a large number of poor-quality data obtained by methods with lower recovery of Fe2+ caused by oxidation or insufficient sample decomposition during analyses. To achieve accurate determinations of Fe2+ in our method, several factors besides the oxidation must be considered, including: (1) long-term variations in the concentration of Fe2+ solution must be corrected; (2) excess use of the indicator must be avoided; and (3) the formation of inert FeF+ complex must be avoided during titration when using boric acid as a masking agent.
We present 238U-230Th-226Ra systematics in lavas from Miyakejima volcano, Izu arc, Japan, together with major element, trace element and Sr-Nd-Pb isotopic compositions, to estimate the timescale of magmatic processes beneath an island arc. 238U-230Th-226Ra disequilibria observed in Miyakejima lavas with large excesses of 238U and 226Ra to 230Th imply metasomatism of depleted mantle by fluid related processes. Our data reveal that fluid components released from the slab ascend rapidly through the mantle wedge (>50m/yr), and that individual stages of subaerial volcanism are induced by flushing of different fluid batches to the mantle wedge with a periodicity of 1-13kyr. This indicates that arc magmatism is controlled by pulsed release of fluid from the slab occurring on such a small timescale, which might be related to the occurrence of earthquakes in the subducting slab.
A method using multiple-collector inductively coupled plasma source mass spectrometry for the precise measurement of Ti isotope composition in natural materials has been developed. Instrumental mass discrimination is corrected using a “standard-sample bracketing” approach by expressing the isotope ratios of samples relative to those of the bracketing standard. Variations in 47Ti/46Ti, 48Ti/46Ti, 49Ti/46Ti and 50Ti/46Ti ratios of samples are expressed in ε units which are deviations in parts per 104 from the same isotope ratios of the reference material. The long-term repeatability at the 2 standard deviation level is 0.4, 0.6, 0.7 and 0.8 ε units in terms of 47Ti/46Ti, 48Ti/46Ti, 49Ti/46Ti and 50Ti/46Ti ratio measurements, respectively. The technique reported here makes it possible for the first time that both mass-dependent fractionation and isotope anomalies of Ti isotopes in natural materials can be measured to high precision.
Major and trace element, and Sr, Nd and Pb isotopic compositions were determined for whole-rock samples from the ‘isotopically anomalous’ Akagi volcano in the volcanic front of the NE Japan arc. Sr and Nd isotopic compositions of phenocrysts were also analyzed together with their major and trace element compositions. Compared with the other volcanoes from the volcanic front, the whole-rock isotope compositions of Akagi show highly enriched characteristics; 87Sr/86Sr = 0.7060–0.7088, εNd = −0.40 to −8.6, and 208Pb/204Pb = 38.4–38.8. The rare earth element (REE) patterns are characterized by heavy REE (HREE) depletions with U-shaped patterns from middle REE (MREE) to HREE, suggesting that amphibole fractionation was induced by a reaction between clinopyroxene and H2O-rich magma in the lower crust. The integrated isotope and trace elements systematics, and tectonic structure beneath Akagi volcano, suggest that lower-crustal assimilation by the H2O-rich primary magma could have been affected by the double subduction of Philippine Sea and Pacific oceanic plates. This double subduction could have supplied larger amounts of water to the magma source region in the wedge mantle than in the case of a single subduction zone. Significant differences in isotopic compositions are observed between phenocrysts and the coexisting melts. Such isotopic disequilibrium may have resulted from magma mixing between an isotopically depleted aphyric and an enriched porphyritic magma in a shallow magma chamber. The geochemical characteristics of these end-member magmas were retained in the lower crust, despite differing extents of lower-crustal assimilation by the H2O-rich magmas.
The trachytic Tanetomi lava from Rishiri Volcano, northern Japan, provides useful information concerning how a replenished mafic magma mixes with a compositionally zoned felsic magma in a magma chamber. The Tanetomi lava was erupted in the order of Lower lava 1 (LL1, 59.2–59.8 wt.% in SiO2), Lower lava 2 (LL2, 58.4–59.1 wt.%), and Upper lava (UL, 59.9–65.1 wt.%). Evidence for mixing with a mafic magma is observed only in the LL2, in which a greater amount of crystals derived from the mafic magma occurs in rocks with higher SiO2 content. The whole-rock compositional trend of the Tanetomi lavas is fairly smooth except for the LL2 lava composition, which scatter along the main composition trend. There is no reasonable composition of basaltic magma on the extrapolation of the LL2 composition trend, and the trend cannot be explained by a simple two-component magma mixing. Before the replenishment, the felsic magma was zoned in composition (58–65 wt.% in SiO2) and temperature (1030–920°C) in the magma chamber located at the pressure of ~2 kbar. The compositional variation of the main felsic magma was produced by extraction of a fractionated interstitial melt from mush zones along the chamber walls and its subsequent mixing with the main magma (boundary layer fractionation). The LL1 magma tapped the magma chamber soon after the replenishment, before the mafic magma mixed with the overall felsic magma. Then the basalt magma mixed heterogeneously with the upper part of the felsic magma by forced convection as a fountain during injection. The mixing of the basalt magma with compositionally zoned felsic magma resulted in the characteristic composition trend of the LL2. The fraction of basaltic magma in the LL2 magma is estimated to be at most 10%. Despite such a small proportion, the basalt magma was mixed completely with the felsic magma, probably because the crystallinity of undercooled basalt magma was low enough to behave as a liquid.
We have developed a new, simple, and accurate method for the determination of total sulfur at microgram per gram levels in milligram-sized silicate materials with isotope dilution high-resolution inductively coupled plasma mass spectrometry equipped with a flow injection system. In this method, sulfur can be quantitatively oxidized by bromine into sulfate with achievement of isotope equilibrium between the sample and spike. Detection limits for 32S+ and 34S+ in the ideal solution and silicate samples were 1 and 6 ng mL-1 and 0.07 and 0.3 μg g-1, respectively. The total blank was 46 ng, so that a 40-mg silicate sample containing 10 μg g-1 sulfur can be measured with a blank correction of < 10%. This total blank can be lowered to 8 ng if a low-blank air system is used for evaporations. To evaluate the applicability of this method, we analyzed not only silicate reference materials with sulfur content of 5.25−489 μg g-1 and sample sizes of 13−40 mg but also the Allende meteorite with a sulfur content of 2%. The reproducibility for various rock types was <9%, even though blank corrections in some samples of low sulfur content were up to 24%. This method is suitable for analyzing geological samples as well environmental samples such as soils, sediments, and water samples.
A new group separation method for Re and PGE (Ru, Pd, Os, Ir, Pt) is described using a novel anion exchange chromatographic resin called TEVA. Re and PGEs are converted into bromo complexes by heating with HF−HBr mixture in a Teflon bomb at 518 K, by in situ-generated Br2 formed by reaction of HBr and HNO3. Distribution coefficients (Kd) of the bromo complexes onto TEVA resin in 0.1 M HBr with heating at 353 K for one night were 2200, 16000, 1600, 5500, 4000, and 17 000 for Ru, Pd, Re, Os, Ir, and Pt, respectively, thus allowing 97% recovery of Re and PGEs in 5 mL of solution by 0.1 mL of resin. These strongly bound Re and PGE bromo complexes are stripped and recovered > 90% by the following three steps: (i) addition of 6 M HCl at 353 K and 2.2 M HCl−5 M HBr at 353 K; (ii) heating the resin in 6 M HCl at 353 K to convert the bromo complexes into the chloro complexes with weaker affinities to the resin; and (iii) sequential addition of the HCl−HBr mixture at room temperature and 7 M HI. Neither the elution profile nor the recovery yield for a 0.2-g geological sample showed significant changes, indicating minimal matrix effects for the geological samples. Total blanks were < 14 pg for Ru, Pd, and Pt and < 10 pg for Re, Os, and Ir. This new technique, therefore, is suitable for simultaneous determination of subnanogram per gram of Ru, Pd, Re, Os, Ir, and Pt and Os isotope analysis in geological, mineralogical, and environmental samples without direct addition of toxic reagents required in distillation/extraction of Os or oxidizing of Ir.
In order to understand the behavior of boron (B) and its isotope fractionation during subduction zone metamorphism, B contents and isotopic compositions together with major element compositions were determined for metasedimentary rocks and tourmalines from the Sambagawa Metamorphic Belt, central Shikoku, Japan. No systematic changes in whole-rock B content and isotope composition of the metasediments were observed among the different metamorphic grades, indicating the lack of a bulk fluid-rock B isotope fractionation as a result of devolatilization. Both modal abundance and grain size of tourmaline increase with increasing metamorphic grade. In contrast, B contents in muscovite and chlorite decrease with increasing metamorphic grade. These observations combined with mass balance calculations of B suggest the formation of tourmaline during progressive metamorphism from metamorphic fluids containing B mainly derived from muscovite and subordinately from chlorite without allowing significant net removal of B from the metasedimentary rocks. Tourmalines in the higher-grade metasedimentary rocks have zonal structure of B isotope and major element composition with decreasing δ11B and increasing Mg/(Mg+Fe) from the inner rim (core) to the outer rim. The change of Mg/(Mg+Fe) in the tourmalines with increasing grade is paralleled by similar variation in chlorite. These observations suggest that the growing tourmalines record the progressive evolution of the B isotopic composition of the metamorphic fluid, in the outermost rims preserving the isotope signature of peak metamorphic P–T-fluid conditions. Based on the above observations, the δ11B of the tourmaline is thought to have been nearly identical to that of the metamorphic fluid resulting in the “apparent” B isotopic fractionation factor between metamorphic fluid and whole-rock (α = (11B/10B)fluid /(11B/10B)whole - rock) which decreases from 1.007±0.003 to 1.001±0.003 from chlorite to biotite zone metamorphism. Such results together with the formation of tourmaline from (and sequestering of) B in metamorphic fluids may lead to less B isotopic fractionation as a result of subduction zone devolatilization than noted in suites containing less tourmaline. This, therefore, makes it possible to transport B isotopic signatures, which ultimately reflect Earth’s surface materials, to the deep mantle, perhaps resulting in mantle B isotope anomalies near convergent margins.
An aluminum fluoride, AlF3, forms during HF digestion of felsic rock samples, for trace element and isotope geochemistry, which use a Teflon bomb at high temperature and pressure. The AlF3 incorporates trace elements (Rb, Sr, Y, Cs, Ba, REE, Pb, Th, and U), and can not be decomposed by conventional methods such as evaporation with HClO4. The production of this AlF3 results in lower yields and poor accuracy in analyses of these trace elements by ICP-MS. The formation of AlF3 is controlled by the chemical composition of the rock samples, in particular, AlF3 does not form during decomposition of mafic samples with relatively high (Mg+Ca)/Al ratios. We have developed a new method to suppress the AlF3 formation, in which excess Mg is added to the sample prior to acid digestion in the bomb. This new method makes it possible to accurately determine the trace element compositions of higher-Al rock samples with lower concentrations of Mg and Ca (e.g. rhyolite and granite). In the trace element analyses by TIMS with isotope dilution techniques (ID-TIMS), AlF3 formation hinders the achievement of isotope equilibrium, resulting in erroneous results. However, the Mg-addition method removed this problem by suppression of AlF3 formation.
We have developed a new, highly precise method for U isotopic analysis using a thermal ionization mass spectrometry (TIMS) by measuring UO2+ ions emitted from a very small amount (100–10 ng) of U. A new ionization activator, a silicic acid–diluted phosphoric acid solution, was found to be effective not only for producing a strong and stable UO2+ ion beam, but also for keeping the mass fractionation during measurement small and constant. U isotope analysis was carried out by a “dynamic multi collection” method using three Faraday cup collectors and a secondary electron multiplier in ion counting mode with RPQ (RPQ-SEM). For precise isotope analysis, baselines of the Faraday cups and a conversion factor between Faraday cups and the RPQ-SEM were precisely determined simultaneously with U isotope collection. Analytical precision and reproducibility of 234U/238U ratio ranged from 0.10% to 0.38% (2σmean) and from 0.13% to 0.31% (2σ), respectively, for 100–10 ng of U extracted from a natural rhyolitic obsidian. The precision and reproducibility were improved compared with previous studies, and thus, our method is especially useful for samples with very low abundance of U.
Sr and Nd isotopes together with trace elements for ocean island basalts in the Polynesian region have been analyzed in order to investigate the origin of the HIMU and EM sources. Both whole rocks and cpx phenocrysts were analyzed for isotopic composition. Cpx samples from HIMU islands show quite uniform 87Sr/86Sr ratios (∼0.70274), while leached and unleached whole rock samples show variable and higher 87Sr/86Sr than those of cpx samples. These results suggest that even leached whole rock samples have been affected by secondary contaminations of sea water. On the other hand, cpx preserves a pristine isotopic signature with minimal secondary effects. Using only the cpx analyses, HIMU form a vertical linear trend in the Sr-Nd isotope diagram with small variation in εNd (+3.3∼+5.5) and constant 87Sr/86Sr. This trend is explained by a mixing of the HIMU end-member and the MORB source. Since εNd of the HIMU end-member is constrained to be less than +3.3, the HIMU source should include former sediment added to oceanic crust. To explain the vertical nature of the mixing trend, the HIMU end-member should have similar Rb/Sr to the MORB source, or much lower Sr/Nd ratio than the MORB source, which favors a mixing model between extensively dehydrated oceanic crust and sediment as the HIMU source. The correlation between εNd and trace element ratios such as Pb/Ta also supports the model.
An accurate method for the determination of Ti at µg g−1 levels in milligram amounts of silicate materials with isotope dilution high-resolution inductively coupled plasma mass spectrometry equipped with flow injection system (ID-FI-HR-ICP-MS) is presented. The chemical procedure requires HF digestion of the sample with the Ti spike, subsequent evaporation and dissolution of Ti with HF in order to separate from Mg and Ca fluorides formed after the digestion of the sample. A 10 mg silicate sample containing 0.002% TiO2 was measured with a blank correction of <5%. To demonstrate the applicability of this method, peridotite reference materials, PCC-1 and DTS-1, from the US Geological Survey (USGS) and JP-1 from the Geological Survey of Japan (GSJ) were analyzed (12–33 mg), to determine TiO2 content. The reproducibility was 3% for these peridotites with TiO2 contents of 0.003–0.004%. This method also gave TiO2 contents in BCR-1, BHVO-1 and AGV-1 from USGS and JB-1, -2, -3, JA-1, -2, and -3 from GSJ with reproducibility of 1–5% using test portions of 6–18 mg.
High-pressure melting experiments on primitive mantle composition material (PM1) and thoreiitic basalt (JB2) were performed from 3 to 15 GPa, and garnet (majorite)/silicate melt partition coefficients, D, were measured for major elements. In the case of PM1, garnet was the liquidus phase only at around 15 GPa, where the partitioning experiments were performed. Although experimental time of PM1 was changed from 10 to 120 min, no obvious change was found in the observed D values of major elements. The liquidus phase of JB2 was garnet under the present experimental conditions. With increase in pressure, an obvious increase in DNa and decrease in DTi were found in JB2, but D values of the other elements showed no significant pressure dependence. The observed D values of PM1 and JB2 were compared in partition coefficient (PC)-ionic radius (IR) diagram. Although the absolute D values were different, D profiles of PM1 and JB2 at 15 GPa resembled each other.
Mafic to ultramafic granulites in the northeastern part of the Jijal complex include two-pyroxene granulite, garnet-clinopyroxene granulite and garnet hornblendite. Field and textural relations indicate that two-pyroxene granulite is a relict left after formation of the garnet-clinopyroxene granulite and garnet hornblendite was an originally intrusive rock which dissected the protoliths of mafic granulites. Sm-Nd mineral isochron ages of 118 ± 12 Ma, 94.0 ± 4.7 Ma and 83 ± 10 Ma were determined for two-pyroxene granulite, garnet-clinopyroxene granulite and garnet hornblendite respectively. These ages, together with previously reported chronological data, led to the following tectonic implications: (1) crystallization of the granulite protoliths predates, or is coeval with, the tectonic accretion of the Kohistan arc to the Asian continent; (2) crustal thickening related to the accretion was probably responsible for the high-pressure granulite-facies metamorphism in the Jijal complex; (3) formation of the garnet hornblendite assemblage was probably after crystallization of garnet-clinopyroxene granulite.
Major and trace element compositions and isotopic ratios of Sr and Nd were determined for bulk rocks and their constituent clinopyroxenes from the Horoman peridotite complex, Japan. Al2O3, CaO, and heavy rare earth elements (HREE) contents of peridotites generally decrease from plagioclase lherzolite through spinel lherzolite to spinel harzburgite, indicating simple melt extraction from a single source. However, the extremely large variations in isotopic (87Sr/86Sr = 0.7019 to 0.7066, εNd = +110 to −10) and trace element compositions ([Ce/Yb]N = 0.006 to 4.0) cannot be explained by a simple melt extraction mechanism. The samples can be divided into two groups: one suite has depleted isotopic and light REE (LREE) characteristics (DP), while the other suite shows enriched isotopic and LREE signatures (EP). Sm‐Nd isotope systematics of whole‐rock DP samples yield an isochron age of 833±78 Ma with an initial 143Nd/144Nd ratio of 0.5119±2, which is identical to the isotopic composition of mid‐ocean ridge basalt (MORB) source mantle at that time. The relationship between MgO and Yb abundances of whole rocks shows that melt extraction was initiated at pressures near the garnet and spinel lherzolite transition. Peridotites that formed at different depths presently occur in close proximity to each other, sometimes within tens of meters. The chemical and isotopic signatures of the EP samples can be explained by mixing between mantle residue and an isotopically and more incompatible element enriched fluid derived from a subducted slab. These observations suggest that the small‐scale compositional layering observed in the complex may have formed in a wedge mantle by water‐enhanced thinning and folding of metasomatized peridotites which had previously developed large‐scale simple stratification as a result of melt extraction beneath a mid‐ocean ridge.
Phenocrysts in volcanic rocks are commonly used to deduce crystallization processes in magma chambers. A fundamental assumption is that the phenocrysts crystallized in the magma chambers at isobaric and nearly equilibrium conditions, on the basis of their large sizes. However, this assumption is not always true as demonstrated here for a porphyritic alkali basalt (Kutsugata lava) from Rishiri Volcano, northern Japan. All phenocryst phases in the Kutsugata lava, plagioclase, olivine, and augite, have macroscopically homogeneous distribution of textures showing features characteristic of rapid growth throughout the crystals. Rarely, a core region with distinct composition is present in all phenocryst phases. Phenocrysts, excluding this core, are occasionally in direct contact with each other, forming crystal aggregates. The equilibrium liquidus temperature of plagioclase, the dominant phase (~35 vol%) in the Kutsugata lava, can never exceed the estimated magmatic temperature, unless the liquidus temperature increases significantly due to vesiculation of the magma during ascent. This suggests that most phenocrysts in the Kutsugata lava were formed by decompression of the magma during ascent in a conduit, rather than by cooling during residence in a magma reservoir. In the magma chamber before eruption, probably located at depth of more than 7 km, only cores of the phenocrysts were present and the magma was nearly aphyric (< 5 vol% crystals), though the observed rock is highly porphyritic with up to 40 vol% crystals. The Kutsugata magma is inferred to have been rich in dissolved H2O (> 4 wt.%) in the magma chamber, and liquidus temperatures of phenocryst phases were significantly suppressed. Large undercooling caused by decompression and degassing of the magma was the driving force for significant crystallization during ascent because of the increase in liquidus temperature due to vapor exsolution. Low ascent rate of the Kutsugata magma, which is suggested by pahoehoe lava morphology and no association of pyroclastics, gave sufficient time for crystallization. Furthermore, the large degree of superheating of plagioclase in the magma chamber caused plagioclase crystallization with low population density and large crystal size, which characterizes the porphyritic nature of the Kutsugata lava. Alkali basalt is likely to satisfy these conditions and similar phenomena are suggested to occur in other volcanic systems.
A boundary layer fractionation model for the thermal and compositional evolution of a basaltic magma chamber is presented. The model utilizes a multicomponent thermodynamic approach for relating the compositional structure with the thermal structure of a cooling magma body. The magma composition in the main magma body evolves by transportation of a fractionated interstitial melt from the mushy boundary layer. The consideration of both the thermal and compositional evolution of the magma body enables a realistic simulation of magmatic differentiation as a function of time and space. The model is used to evaluate a primary magma estimation from volcanic rock series. It is shown that the common procedure of olivine addition gives an estimation which is significantly different from the true primary composition if the magma actually differentiated by boundary layer fractionation. This can cause significant errors in estimating the conditions at which the primary magma was generated.
Detailed investigation of an erupted magma with limited compositional diversity provides instantaneous information on incremental magma differentiation processes in a magma chamber. Kutsugata lava, a suitable target of such study, is a Quaternary alkali basalt (51.3–53.2 wt% in SiO2) from Rishiri Volcano, northern Japan. Despite the narrow range in the whole rock compositional variation, chemical and modal compositions of mineral phases crystallized in the magma chamber vary systematically with the whole rock composition. In the North lava (51.3–51.9 wt% in SiO2) the less differentiated portion of the Kutsugata lava, most crystals which include low‐Ni olivine and plagioclase were derived from the mushy boundary layer. The main part of the magma body was principally aphyric (<0.5 vol% crystals). Estimated chemical compositions of fractionated mineral phases during differentiation of the magma coincide with the observed compositions of low‐Ni olivine and plagioclase crystals. This indicates that the main magma was differentiated by separation of crystals grown in the mush zone. The low‐density interstitial melt is suggested to have been extracted from the floor mush zone with average crystallinity of >30 vol% by such mechanisms as compaction and compositional convection. This fractionated melt was mixed with the overlying main magma, causing differentiation of the Kutsugata magma. The average temperature of the extracted melt is 1010°C, significantly lower than 1100°C estimated for the main magma. A quantitative model of magmatic differentiation, which includes thermal and compositional evolution of a mushy boundary layer, can successfully reproduce the observed compositional trends of the North lava.
We have developed a rapid and accurate method for the determination of Mo, Sb and W in geological samples using isotope dilution inductively coupled plasma‐mass spectrometry with a flow injection system (ID‐FI‐ICP‐MS). The chemical procedure requires HF digestion of the sample with a Mo‐Sb‐W mixed spike, subsequent evaporation and dissolution of Mo, Sb and W from Mg and Ca fluorides with HF. Recovery yields of Mo, Sb and W in the extraction were > 94% for samples of peridotite, basalt and andesite composition, with the exception of W in samples of peridotite composition for which recovery was 81%. No matrix effects were observed in the determination of the isotope ratios of Mo, Sb and W in solutions prepared from peridotite, basalt and andesite samples down to a dilution factor of 100. Detection limits of Mo, Sb and W in silicate materials were at the several ng g−1 level. Analysis of the silicate reference materials PCC‐1, DTS‐1, BCR‐1, BHVO‐1, AGV‐1 from the US Geological Survey and JP‐1, JB‐1, ‐2, ‐3, JA‐1, ‐2, and ‐3 from the Geological Survey of Japan as well as the Smithsonian reference Allende powder yielded reliable Mo, Sb and W concentrations. The repeatability in the analysis of basalts and andesites was < 9%. This technique requires only 0.2 ml sample solution, and is therefore suitable for analyzing small and/or precious samples such as meteorites, mantle peridotites and their mineral separates.
We have developed a rapid and accurate method to determine Zr, Nb, Hf and Ta (denoted as HFSE) in geological samples by inductively coupled plasma‐mass spectrometry fitted with a flow injection system (FI‐ICP‐MS). The method involves sample decomposition by HF followed by HF dissolution of HFSE coprecipitated with insoluble M and Ca fluoride residues formed during the initial HF attack. This HF solution was directly nebulized into an ICP mass spectrometer. An external calibration curve method and an isotope dilution method (ID) were applied for the determination of Nb and Ta, and of Zr and Hf, respectively. Recovery yields of HFSE were > 96% for peridotite, basalt and andesite compositions, apart from Zr and Hf for peridotite (> 85%). No matrix effects for either signal intensities of HFSE or isotope ratios of Zr and Hf were observed in basalt, andesite and peridotite solutions down to a dilution factor of 100. Detection limits in silicate rocks were 40, 2, 1 and 0.1 ng g‐1 for Zr, Nb, Hf and Ta, respectively. This technique required only 0.1 ml of sample solution, and thus is suitable for analysing small and/or precious samples such as meteorites, mantle peridotites and their mineral separates. We also present newly determined data for the Zr, Nb, Hf and Ta concentrations in USGS silicate reference materials DTS‐1, PCC‐1, BCR‐1, BHVO‐1 and AGV‐1, GSJ reference materials JB‐1, ‐2, ‐3, JA‐1, ‐2 and ‐3, and the Smithsonian reference Allende powder.
A new chemical separation technique to isolate Th and U from silicate rocks was established by using two kinds of commercial extraction chromatographic resins. In the first column procedure, with U/TEVA·spec resin, almost all elements except Th and U were eluted by 4M HNO3. Th was then separated by using 5M HCl, and U was finally isolated by successive addition of 0.1M HNO3. A significant amount of Zr still remained in the Th fraction, which was then further purified in the second column stage using TEVA·spec resin. In the second procedure, Zr was eluted first by using 2M HNO3, and then Th was collected by 0.1M HNO3. Both the Th and U fractions obtained by these procedures were sufficiently pure for thermal ionization mass spectrometric (TIMS) analysis. Recovery yields of Th and U exceeded 90%, and total blanks were < 19 pg for Th and < 10 pg for U. Our method has advantages over previous methods in terms of matrix effects, tailing problems, and degree of isolation. Since Th and U are effectively separated without suffering any matrix interference from coexisting cations and anions, this technique can be used not only for the analysis of igneous rock samples but also for the analysis of soils, marine sediments, carbonates, phosphates and seawater, groundwater, and surface water.
Insoluble fluoride precipitates which form during HF digestion of mafic silicate rocks coprecipitate in their structures the trace elements such as Rb, Sr, Y, Cs, Ba, REE, Pb, Th and U, thus hindering their accurate determination. We have estimated quantitatively the coprecipitation of trace elements into such fluorides, and suggest an effective method of digestion that can suppress completely fluoride precipitation. Conventional acid digestion of three samples of mafic and ultramafic silicate rocks resulted in the precipitation of sticky material and very poor yields of certain trace element in the resultant solution. XRD analysis indicated that the precipitates were composed of fluorides such as CaAlF5, CaMg2Al2F12, Na0.88Mg0.88Al1.12(F,OH)6·H2O and MgF2, the formation of which depended on the major element composition of the rock sample. Coprecipitation of trace elements appeared to be strongly controlled by both ionic radius and valency of the elements as well as the species of the host fluoride precipitate, resulting in selective losses of the elements into these fluorides. On the other hand, almost 100% of the trace elements were recovered using larger amounts of HClO4 than is conventionally used and evaporating the sample to dryness in a step-wise fashion. Using this method, white precipitates were formed as oxides of high field strength elements after decomposition of the sample. Coprecipitation of trace elements of interest in this study with the oxides is negligible except for Th for which 0.5–3.2% by weight was coprecipitated probably as the insoluble oxide. As our method also results in negligible blank values, it can be used for both the accurate determination of trace element using ICP-MS as well as isotope analysis using TIMS.
A pyroxene andesite unit within the post-Alpine Alborán volcanic province has a Neogene extrusion age; however, its Rb–Sr isotopic relations define a regression line of 509 ± 62(2σ) Ma (Early Palaeozoic). There are two concordant data point clusters on the regression line, one of which is well constrained, defining a secondary regression line of 202 ± 30(2σ) Ma (Early Mesozoic). Considering the mineralogy of the andesites—plagioclase, Ca-poor and Ca-rich pyroxene, and Ti-magnetite—and the presence of restitic aggregates comprising these same four minerals, recent dehydration melting experiments suggest an origin by anatexis of an amphibolite-dominated source rock complex. Inherited zircon ion-microprobe ages in the range of 500–1800 Ma, an Sm–Nd isochron age of 1.5 ± 0.4(2σ) Ga, TCHURNd crustal derivation ages from ∼0.75 to 1.05 Ga and ɛNd(0) values of –4 to –7 support a complex petrogenesis, involving large-scale reworking of older material. 87Sr/86Sr vs 1/Sr and 143Nd/144Nd vs 1/Nd indicate a heterogeneous source rock complex showing two-component mixing. The data favour volcano-sedimentary source rock complex parent material which at ∼500 Ma underwent a diagenetic or hydrothermal event, which regionally reset Rb–Sr isotope systematics. Subsequently, at ∼200 Ma the complex went through local diagenetic or hydrothermal re-equilibration, which created domains with slightly different 87Sr/86Sr ratios, before undergoing Alpine high-grade metamorphism and subsequent anatexis. Roughly coeval, restite-rich cordierite dacites show similar, ∼200 Ma, high-age Rb–Sr isotopic relations, which are interpreted as the age of diagenesis of its sedimentary parent material. This is supported by inherited zircon ion-microprobe ages of 300–400 Ma upwards. Also for these rocks 87Sr/86Sr vs 1/Sr shows linear trends, which are explained analogically by sedimentary component mixing in the parent material of the anatectic source rock complex rather than by magmatic stage mixing or contamination. A sinking slab model is suggested for the regional setting of the crustal anatectic regime, melting being supported by fast uplift (of isotherms) and diapiric underplating by high-temperature asthenospheric mantle.
The evolution of basaltic magma by mushy boundary layer processes in a magma chamber is documented for an alkali basalt (Kutsugata lava) from Rishiri Volcano, northern Japan, on the basis of zoning patterns of plagioclase phenocrysts and their spatial distribution in the lava. Plagioclase phenocrysts with complex zoning patterns can be divided into four types. Type 1 is characterized by an extremely An-rich core (An71–90), which is commonly corroded and filled with sodic plagioclase. Type 2 has an Ab-rich core surrounded by a calcic mantle characteristic of partial dissolution. Type 3 is characterized by an Ab-rich core that is commonly surrounded by a reversely zoned slightly calcic mantle. Type 4 has an Ab-rich core without a calcic mantle. The An-rich cores of the Type 1 plagioclase are too calcic to have crystallized from a liquid represented by any whole-rock composition at the estimated temperatures of the Kutsugata magma system. The An-rich cores are inferred to have been formed in a mushy boundary layer along the wall of a magma chamber, where the magma was relatively cool and rich in water because of significant olivine fractionation and possibly because of addition of water expelled from the chilled margin and/or groundwater from the surrounding crust. The Ab-rich cores of Types 2–4 plagioclase phenocrysts are interpreted to have crystallized in the main magma body of the reservoir. The Types 2 and 3 Ab-rich cores were brought to the mushy layer by convection. The temporal and spatial variations of zoning patterns of plagioclase phenocrysts in basaltic lava flows give useful information on the evolution of mafic magma chambers.
Li isotope was analyzed in island arc volcanics from the Izu arc, Japan, to investigate geochemical processes in subduction zones. Li isotope ratios (δ7Li) and Li/Y of the arc lavas show clear across-arc variations, decreasing (δ7Li: +7.6 to +1.1‰, Li/Y: 0.36 to 0.25) with increasing depth to the Wadati–Benioff zone (150 to 210 km). This suggests that the amount of subduction component as a fluid added to the source region decreases with depth. δ7Li–Y/Li systematics of the arc lavas clearly indicate a simple mixing between two distinctive chemically homogenous endmembers, a slab-derived fluid and the mantle wedge. Furthermore, Li–B–Pb isotope systematics allow clear discrimination between the relative contribution of altered oceanic crust (AOC), oceanic sediment and mantle wedge to arc lavas, and suggests that AOC is the dominant subduction component, whereas the contribution of oceanic sediment is extremely small (AOC/oceanic sediment = 97/3). The contrasting physicochemical properties for Li and B in mineral structures imply that Li may be less likely to migrate from the slab into the overlying mantle wedge than B. Thus the Li isotopic composition in the Earth's surface material evolved under near-surface condition, could be more efficiently introduced into the deep mantle through subduction zones than the B isotopic signature, making Li isotopes a powerful geochemical tracer for better understanding of crust/mantle recycling.
A high-yield lithium separation technique for rock and aqueous samples has been established together with precise Li isotope analysis by thermal ionization mass spectrometry. Four separate stages of ion-exchange chromatography were carried out using organic ion-exchange resin. An ethanol-HCl solution was used for complete separation of Li from Na at the third column state. Total reagent volume for the entire chemical process was reduced to 42 ml and 33.3 ml for rock samples and seawater, respectively. The recovery yield and total procedural blank are 99.2–99.3% and 11 pg, respectively. Li3PO4 was used as an ion-source material in the mass spectrometric analysis. The in-run precision and reproducibility of measured 7Li/6Li ratios were ±0.04–0.07‰ (2σmean) and 0.37‰ (relative standard deviation; RSD) for rock and ±0.05-0.08‰ (2σmean) and 0.35‰ (RSD) for seawater. In this method, Rb, Sr, Sm, Nd, La and Ce can be collected after Li elution in the first column chromatography, then separated by the following specific procedures for these elements. Therefore, this method makes possible multi-isotope analysis for Li-poor and restricted small amounts of samples such as meteorites and mantle materials, extending to Li isotope geochemistry and cosmochemistry.
Diffusivities of geochemically important trace elements (eleven rare earth elements (REE), Rb, Sr, Ba, and Y) in jadeite and diopside melts and those of Zr, Nb, Th, and U in jadeite melt have been measured at pressures between 7.5 and 20 kbar and at temperatures 50–200° above the liquidus, using diffusion couples and ion microprobe analysis. The concentrations of these elements in the experimental charges are close to those in natural igneous rocks. In the jadeite melt which is nearly fully polymerized (NBO/T ∼ 0), (1) diffusivities of REE increase with increasing ionic radii, (2) diffusivities of tri- and tetravalent elements increase with increasing pressure at constant temperature, whereas those of mono- and divalent elements do not change significantly with pressure, and (3) diffusivities of these elements decrease with increasing their ionic charge at constant pressure and temperature. In the diopside melt which is considerably less polymerized (NBO/T ∼ 2), (1) diffusivities of these trace elements depend mainly on their ionic radii rather than ionic charges; the diffusivities of mono- and divalent ions decrease with increasing ionic radii at constant pressure and temperature, and (2) diffusivities of REE are nearly the same as that of Ca and decrease with increasing pressure at constant temperature. The behavior of these trace elements is correlated with that of major elements; in the jadeite melt, tri- and tetravalent elements behave similarly to network-forming cations Al and Si, whereas mono- and divalent elements behave as network-modifying cations similarly to Na. In the diopside melt, the diffusion behavior of all these trace elements is similar to that of network-modifying cations Ca and Mg. The results of the present experiments suggest that the abundance of some trace elements in igneous rocks may have been affected by diffusion process at the magmatic stage. In the case of REE, for example, if two different magmas with high and low REE concentrations become in contact one another by multiple intrusion, and a zoned magma chamber is formed, diffusion begins to take place between them, and near the interface, the REE-enriched magma will become more light REE-depleted, whereas REE-depleted magma will become more light REE-enriched, and in addition, if magmas are reduced, the former will show a negative Eu anomaly, whereas the latter will show a positive Eu anomaly.
Static multicollection of Cs2BO2+ ions (mz=308 and 309) for precise boron isotope analysis has been established by employing a newly developed double collector package in the modified Finnigan-MAT 261 thermal ionization mass spectrometer (TIMS). This method reduces the data acquisition time to 5 min which is approximately one order of magnitude shorter than conventional peak jumping method, and it is easier to measure small sample size as low as 0.1 μg of boron. The analytical precision for individual runs and reproducibility of measured 11B/10B ratios of NBS 951 boric acid with static multicollection, respectively, are ±0.007−0.025% (2σmean) and ±0.012% (2σmean), for 1 μg of B, and ±0.015−0.032% (2σmean) and ±0.023% (2σmean), for 0.1 μg of B. This analytical precision and reproducibility are essentially identical to those previous works with peak jumping method measuring sample amounts more than 1 μg of B.
Isotopic compositions of Sr, Nd and Pb and REE concentrations have been determined for samples from “isotopically anomalous” Akagi volcano locating on the volcanic front of Northeast Japan Arc. The Sr isotopic compositions show a large variation with highly enriched isotope character (87Sr/86Sr=0.7060 to 0.7088) compared to those from other volcanoes on the front. The Nd isotopic compositions, ranging from εNd=-0.40 to -8.6, have a negative correlation with the Sr isotopic compositions. The Pb isotopic data along with Sr and Nd isotope systematics clearly indicate that the isotopic variations of Akagi volcano were caused by a two-component mixing between an end member isotopically similar to the primary magma on the volcanic front of Northeast Japan Arc and a lower crustal component. Chondrite-normalized REE patterns of Akagi samples show U-shaped, HREE-depleted pattern with positive Eu anomaly. Such REE features may have been developed by fractionation of amphibole formed by the reaction between a fluid-rich magma and clinopyroxene in granulitic lower crust. The fluid-rich magma could be originated from a highly metasomatized mantle wedge caused by the dehydration of oceanic slabs of the Pacific plate and the overlapping Philippine Sea Plate. Such a unique tectonic setting could result in higher water supply to the source region of magma than normal circumstances and thereby generating fluid-rich magma which could enhance assimilation of lower crust beneath Akagi volcano.
We found that the suppression of signals for 88Sr,140Ce and 238U in rock solution caused by rock matrix in ICP-MS (matrix effects) was reduced at high power operation (1.7 kW) of the ICP. To make the signal suppression by the matrix negligible, minimum dilution factors (DF) of the rock solution for Sr, Ce and U were 600, 400 and 113 at 1.1, 1.4 and 1.7 kW, respectively. Based on these findings, a rapid and precise determination method for Rb, Sr, Y,Cs, Ba, REE, Pb, Th and U using FI (flow injection)-ICP-MS was developed. The amount of the sample solution required for FI-ICP-MS was 0.2 ml, so that 1.8 mg sample was sufficient for analysis with a detection limit of several ng g-1. Using this method, we determined the trace element concentrations in the USGS rock reference materials, DTS-1, PCC-1,BCR-1 and AGV-1, and the GSJ rock reference materials, JP-1, JB-1, -2, -3, JA-1, -2 and -3. The reproducibilities (RSD %) in replicate analyses (n=5) of BCR-1, AGV-1, JB-1, -2, -3, JA-1, -2, and -3 were< 6 %, and typically 2.5%. The difference between the average concentrations of this study for BCR-1 and those of the reference values were < 2%. Therefore, it was concluded that the method can give reliable data for trace elements in silicate rocks.
A rapid and precise technique for the determination of boron content in silicate rocks was developed by employing isotope dilution inductively coupled plasma mass spectrometry with a flow injection system (FI-ID-ICPMS). The sample was decomposed with HF and mannitol, dried to remove silicon as gas, and redissolved with HF to extract boron from the fluoride residue. Ultimately, the HF solution was directly aspirated into the ICPMS. The total procedural blank was 0.08−0.36 ng. No matrix-induced mass discrimination was observed in the rock solution for dilution factors of up to 110. The present method is capable of determining 1 μg g-1 boron in a 1 mg silicate rock sample with blank correction of <20%. Replicate analyses of USGS rock standards, PCC-1, BCR-1, and AGV-1, and GSJ rock standards, JB-1, JB-2, JB-3, JA-1, JA-2, and JA-3, yielded reproducibilities (RSD) of <2%. These results were identical with those obtained by ID thermal ionization mass spectrometry within the analytical errors. These results indicate that the present method allows the precise determination of the boron content in a small sample of silicate materials with simple handling, resulting in the extremely low procedural blank of boron.
Diffusivities of 11 rare earth elements (REE) and Ba in jadeite (NaAlSi2O6) and diopside (CaMgSi2O6) melts have been measured at pressures between 10 and 20 kbar. In jadeite melt, diffusivities of REE increase regularly with increasing their ionic radii, light REE (e.g., La and Ce) diffuse faster than heavy REE (e.g., Yb and Lu) by about 30%, Eu diffuses faster by factor of 8 to 12 than other REE under reducing conditions, and diffusivities of REE increase with increasing pressure at constant temperature. In diopside melt, diffusivities of REE are nearly the same as that of Ca and decrease with increasing pressure. The present study demonstrates that diffusion process in magma should change the relative abundances of REE and also generate Eu anomalies without involvement of plagioclase feldspar. This diffusion-induced process is a newly recognized mechanism of changing the relative REE abundances in magmas and generating Eu anomalies, and it must be taken into account in interpreting the REE abundance patterns of igneous rocks.
Isotopic compositions of Pb, Sr, and Nd and concentrations of trace elements were determined for Quaternary island arc basaltic rocks from northeastern Japan. Sr and Pb isotopic ratios decrease, and Nd isotopic ratios increase from the volcanic front toward the back arc. The isotopic compositions nearest the back arc side are nearly identical to those of mid‐ocean ridge basalt (MORB). The high field strength elements and heavy rare earth elements show homogeneous and MORB‐like characteristics. These observations indicate that the mantle wedge beneath northeastern Japan originally had a MORB‐type mantle composition that was homogeneous across the arc. Pb isotope compositions show a mixing relationship between mantle wedge and oceanic sediments reflecting the introduction of subduction component into the mantle wedge, Across‐arc isotopic variations were caused by interaction between MORB‐type mantle wedge and the subducting slab, and the amount of subduction component correlates with the depth to the slab. The isotopic compositions of subduction component are expressed by bulk mixing of 15 wt % of oceanic sediment and 85 wt % of altered MORB. Inversion analyses of isotopic compositions using two‐component mixing relationships show that the Sr/Nd and Pb/Nd ratios in subduction component decrease with increasing depth to the slab, while the Sr/Pb ratio is nearly constant. These changes can be explained only by a preferential discharge of the elements into the wedge mantle associated with continuous dehydration of the subducting slab. The present study further demonstrates that a very wide range of isotopic and elemental compositions in island arc magmas is a consequence of the interaction between subducting slab and mantle wedge without the involvement of an oceanic island basalts component, and the slab can carry water and supply a subduction component as a fluid to the overlying mantle wedge to depths exceeding 150 km.
Granitoids of two different generations occur across the Archaean-Proterozoic boundary in southeastern Tanzania. The first generation, which is confined to the Archaean Tanzania Craton, yields RbSr whole-rock isochron ages of 2600 Ma and low, mantle-like, initial 87Sr/ 86Sr ratios (0.702–0.704). These coupled with positive or near-zero ε Nd values (−0.2 to 2.0) suggest that these granitoids represent juvenile mantle material which was added to the continental crust at about 2600 Ma. The second generation of granitoids intrudes the Palaeoproterozoic Usagaran Belt and is characterised by RbSr whole-rock isochron ages of about 1900 Ma. These granitoids show SmNd crustal formation ages which are 200 to 600 Ma older than their emplacement ages and negative ε Nd values (−2.2 to −6.2). Mixing calculations suggest that the Proterozoic granitoids may have formed by partial melting of 2000 Ma (Usagaran) mantle-derived material which had incorporated between 15 and 45% of an Archaean component from the adjacent Tanzania Craton.
Structural, petrological, and geochronological data from the middle Korean peninsula indicate that the Qinling-Dabie-Sulu collisional belt of east-central China crosses the Yellow Sea and extends into the Imjingang belt. The Yeoncheon complex, first identified as the western Imjingang belt, comprises primarily north-dipping metamorphic sequences: (1) the northern Jingok unit, consisting of Barrovian-type metapelites, and (2) the southern Samgot unit, consisting of calc-silicate and amphibolitic rocks. South-vergent structures with reverse-sense shearing are dominant in the Jingok unit, whereas late normal-sense shearing is pervasive in the Samgot unit and the deformed granitoid to the south. These structural patterns are interpreted to correspond to extensional deformation associated with uplift following compression in a collisional belt. Pressure-temperature (P-T) estimates from the amphibolites suggest a high-P amphibolite-facies metamorphism (8–13 kbar and 630–790°C), possibly evolving from eclogite facies conditions along a clockwise P-T path. Sm-Nd and Rb-Sr geochronological data suggest that the amphibolites emplaced in Late Proterozoic time were metamorphosed during Permian-Triassic time.
New Sr and Nd isotopic data are presented and integrated with previous data for the Shirahama Group Mio-Pliocene medium-K volcanic are suite of south-central Honshu, Japan. Main results are: (1) The Shirahama lavas range in 87Sr/86Sr from 0.70315 to 0.70337 and in 143Nd/144Nd from 0.51298 to 0.51306; the Sr and Nd isotopic data cluster tightly within the mantle array, and all lie within an overlapping field of mid-ocean ridge basalt and ocean island basalt; (2) small differences exist among the Shirahama tholeiitic series, calc-alkaline series and mixed lavas. The present isotopic data are consistent with a previously published model, which proposes that chemical variations in magmas of coexisting tholeiitic and calc-alkaline series are produced through crystal fractionation from mantle-derived magmas of basalt and magnesian andesite, respectively. Moreover, the tholeiitic series and the calc-alkaline series are isotopically identical. Thus, both magma series can be derived from a source mantle with the same isotopic composition, supporting the hypothesis of simultaneous generation of basalt and magnesian andesite magmas from a single diapir rising through the mantle wedge above the subduction zone. The differences of water content and temperature within the diapir are again thought to have been produced through dehydration and heating of an isotopically homogeneous hydrous diapir. The isotopic data show that the high-SiO2 lavas have the same isotopic compositions as more mafic lavas. These data and liquid lines of descent of the Shirahama magmas suggest that even rhyolites can be produced by differentiation from mantle-derived magmas without crustal contamination. Analyses from 38 other arc volcanoes have been compiled to investigate the intravolcano variability of 87Sr/86Sr. Twelve of these display no intravolcano strontium isotopic variability, as is the case with the Shirahama Group, but others show greater variation of 87Sr/86Sr from individual volcanic centers, presumably reflecting crustal contamination. Most of the latter volcanoes are underlain by thick continental crust. It is noteworthy, however, that the greater variations of 87Sr/86Sr correlate with SiO2 content; andesites or dacites, not basalts, from the same volcano have the lowest 87Sr/86Sr, and these rocks are calc-alkaline in terms of FeO*/MgO and SiO2 Theoretically, assimilation of continental crust by the isotopically uniform Shirahama magmas could produce these relationships. Given that mantle-derived basalt and magnesian andesite both encounter continental crust on their ascent to the surface, the hotter basalt magma would assimilate more crustal wallrocks than the cooler andesite, resulting in the basalt being more radiogenic. Fractional crystallization, magma mixing, and/or assimilation-fractional crystallization of these magmas in crustal magma chambers could produce large compositional variations, but the derivatives of the hotter basaltic magmas (tholeiitic series in the broad sense) would display greater contamination than those derived from the cooler andesitic magmas (calc-alkaline series).
Sm–Nd mineral-isochron ages of garnet granulites in the southern part of the Kohistan complex are determined. The 91.0 ± 6.3 Ma age is obtained from a granulite body of the Jijal complex at Pattan and the 69.5 ± 9.3 Ma age is obtained from a granulite body of the Chilas complex at Zambil. These ages indicate that the granulite bodies at Pattan and at Zambil had cooled to below upper amphibolite facies by about 90 Ma and about 70 Ma respectively. The time of cooling of the granulite of the Jijal complex is comparable to the time-lapse of the Asia–Kohistan collision (102–75 Ma), although that of the Chilas complex is probably younger than the Asia–Kohistan collision and certainly older than the Asia–India collision (c50 Ma).
The 11B/10B ratios of thirty-two meteorite falls and nine lunar rocks were measured as Cs2BO2+ using thermal ionization mass-spectrometry. The 11B/10B ratios of meteorites vary from 4.011 to 4.098, i.e., their δ11B values (relative to NIST SRM 951) range from −10.5 to +19.2%; however, excluding two outliers, Mokoia and Norton County, the range of most meteorites is smaller ( −10.5 to +7.5). The average of two C11 meteorites, Ivuna and Orgueil, is -3.3, in the middle of the range. The δ11B values of the lunar rocks vary less than those of meteorites, from −6.0 to −3.9. The average δ11B of CI1 chondrites is −3.3, similar to that of terrestrial fresh mid-ocean ridge basalts (−6.5 to −1.2) and to the estimated mantle value of +0.2 (Ishikawa and Nakamura, 1992), which is the best representative of the whole Earth. The similarity of δ11B values in meteorites, lunar rocks, and those parts of the Earth unaffected by water implies that the boron isotopic composition of the Solar System is rather homogeneous. Recently, Chaussidon and Robert (1995) reported larger variation of δ11B values in chondrules of three chondrites, from −50 to +40. This degree of heterogeneity is absent from bulk meteorites.
In order to examine the behavior of elements under the control of aqueous fluid through slab-mantle interactions, a series of high-pressure and high-temperature experiments was carried out at subsolidus temperature, 850°C. The starting materials consist of two portions: metabasite from blueschist as a slab material and olivine as a mantle material. The metabasite was directly placed on the olivine and sealed within an Au tube. At 3 and 6GPa corresponding to 100 and 200km in depth, respectively, the slab material was changed from blueschist to rutile-bearing eclogite. Observed phases in the mantle side were primary olivine and enstatite formed by the reaction between olivine and SiO2-rich aqueous fluid from the slab side. At 8GPa, the slab material was further transformed to rutile-free eclogite, and phases occurred in the mantle side were titanoclinohumite in addition to olivine and enstatite. The titanoclinohumite was formed by the reaction between olivine and Ti-bearing aqueous fluid which was supplied from the slab side. The titanoclinohumite is essentially identical in chemical composition to those principally occurring in kimberlite xenoliths. Because the Ti-phase is a host reservoir of HFSE, the formation of titanoclinohumite at 8GPa corresponding to 250km in depth suggests that the aqueous fluid can be a carrier of HFSE from the subducting slab to the upper mantle, and thus the source region of kimberlite magma could be impregnated by the interaction between mantle peridotite and the HFSE-bearing aqueous fluid from the subducting slab.
Two samples from the Uluguru granulite complex yield garnet Sm-Nd ages of 633 ± 7 and 618 ± 16 Ma, similar to previously published hornblende 40Ar-39Ar and K-Ar ages. The similarity of the Sm-Nd to the K-Ar age suggests that the closure temperature of garnet to Nd diffusion is similar to that of hornblende to Ar diffusion. Assuming that published zircon U-Pb ages of about 700 Ma date peak granulite-facies metamorphism, a mean post-metamorphic cooling rate of 2–3°C/Ma can be calculated for the time interval 700 to 630 Ma. Such slow cooling rates imply thermal relaxation with a thickness length-scale greater than the thickness of average continental crust. This, in turn, implies that the thermal perturbation responsible for metamorphism was preceded by regional crustal thickening probably in a collisional orogen.
The isotope geochemical study for Iceland is reviewed. Iceland yields not only tholeiitic basalts but also tholeiitic andesites or rhyolites. Many geochemical studies were done to decipher the origin of the felsic volcanic rock which constitutes about 10% of the Icelandic crust. However, the origin was not clear. To solve this problem, the combination of Sr, Nd, Pb, He and O isotope tracers with U-Th disequilibrium has been attempted, and the involvement of the Icelandic hydrothermally altered crust into the source of the felsic rock is infered. In near future, application of new Li and B tracers will constrain the origin of the felsic rock in more detail.
In this article, the isotope geochemical study for Iceland is reviewed. Iceland is geologically unique because it is a subaerial exposure of Mid-Atlantic Ridge, which is caused by the interaction between the ridge and the Icelandic hot spot. To investigate what is happening beneath Iceland, many geochemical studies have been done. The geochemical studies using conventional Sr, Nd, Pb, He and O isotope tracers revealed the heterogeneity not only of the oceanic mantle, but also of the Icelandic hot spot mantle itself. Furthermore, the oxygen isotope studies revealed the reworking of the Icelandic crust which is altered by meteoritic water. The characterization of the Icelandic hot spot from the isotope geochemistry is very important in testing the hypothesis of the mantle-crust recycling. In near future, new tracers such as Li, B or Ce will be applied to this problem, and new constraints will be obtained.
In order to characterize the petrogenesis of the E-W trending Imjinganag belt, we studied the metamorphic rocks of the Yeoncheon Group near its type locality, Yeoncheon - Cheongok area, belonging to the southern part of this fold-thrust belt. The Samgot Formation of the Yeoncheon Group consists of calc-silicate and metapsammitic rocks together with amphibolite and amphibole gneiss. Layers of these metamorphic rocks concordantly occur in a wide area with its length greater than 15 km along their strike direction. Major mineral assemblages of the amphibolite are hornblende + plagioclase ± garnet ± diopside ± biotite ± quartz. Accessory rutile and ilmenite are characteristically replaced by titanite. Metamorphic temperatures and pressures estimated from the garnet - hornblende - plagioclase - quartz geothermo-barometers are 632-736∘C and 7.9-11.1 kbar, respectively. Thus, the regional metamorphism of the study area belongs to the upper amphibolite facies. Furthermore, Sm-Nd and Rb-Sr data of garnet, plagioclase, and whole rock of an amphibolite define mineral isochrons of 231±30 Ma and 222±24 Ma, respectively, suggesting the Triassic metamorphism. These results are consistent with P-T conditions and metamorphic ages reported in the Shandong Peninsula, and support the hypothesis that the Chinese collision belt may extend into the Imjingang belt in the Korean Peninsula.
AT convergent margins, the subducting oceanic slab is thought to dehydrate, producing fluids which metasomatize the overlying mantle wedge where island-arc magma forms. However, the nature and origin of the metasomatizing fluid, its source composition and its relation to the genesis of the chemical characteristics of arc magmas are largely controversial. Across-arc variation in the chemistry of arc lavas provides a useful key to this problem, because it may reflect the changes in the physical conditions of the subducting slab that control mass transfer from slab to mantle wedge as a function of depth. Here we report clear across-arc variations in the concentrations and isotopic compositions of boronand lead observed in lavas from the Izu arc (Japan). Our data suggest that a homogeneous slab fluid contributes to all Izu volcan-oes, but that the amount of this fluid decreases continuously with increasing depth of the subducting slab. Whereas the Izu slab fluid conies primarily from altered oceanic crust, our data for high-Mg andesites from the Setouchi volcanic belt (a nearby fore-arc) indicate a significant involvement of sediment in the fluid source.
LREE (La, Ce, Nd and Sm) concentrations, and 143Nd/144Nd and 138Ce/142Ce ratios of two powder aliquots from the bulk Allende meteorite (BAM) were measured to investigate p-isotopic anomalies of Ce. Initial Ce isotope ratios of the two aliquots were calculated assuming an age of 4.56 Ga, identical with ages of other chondrites or eucrites. From the data, we conclude that there are no recognizable p-isotopic anomalies in BAM. This suggests that the existence of p-isotopic anomalies of other REE in BAM is unlikely. Our data can not, however, rule out the possibility that this is only caused by averaging of heterogeneous distribution of p-isotopic anomalies.
Isotope ratios of Ce, Nd and Sr, and light rare-earth elements (La, Ce, Nd and Sm) concentrations were measured for sixteen N-type MORB samples from DSDP Sites 420, 421, 429, 597B and 597C (East Pacific Rise), 504B (Costa Rica Rift), and 395, 519A, 522B, 562 and 564 (Mid Atlantic Ridge). All the samples were confirmed as N-type MORB based on Nd and Sr isotope ratios, and LREE patterns. The Ce isotope ratios ranged from 0.0225616 (εCe = − 1.6) to 0.0225633 (εCe = − 1.0). Averages of εCe and εNd of N-type MORB were − 1.4 and 9.5, respectively. The average of εCe is quite different from previous estimates. We propose that εCe = − 1.4 should be used as the typical MORB Ce isotope ratio in future studies.
Recent topics on the rare-earth element (REE) geochemistry of zircon are reviewed in this article. With SIMS (secondary ion mass spectrometry), we can obtain the REE composition for a spot area ( < 40μm) of zircon. These SIMS studies have revealed that the LREE are much more depleted in zircon crystals than was previously believed as indicated by conventional bulk zircon analysis. SIMS studies also indicate that the REE patterns of terrestrial zircon generally have Ce anomaly. The implications of the Ce anomaly for the evolution of the atomosphere are discussed. Because zircon crystals are resistent to decomposition with HF in an open beaker, open beaker decomposition yields erroneous results in some cases. We discuss several examples in the case of analyses of sediments. The resistence of zircons to erosion and weathering, and its high concentration of Hf constrain sediment recycling into the mantle and the evolution of continental crust. We discuss such issues in this paper, based chiefly on Lu-Hf isotope systematics. We conclude in our “Reviews in Zirconolgy” that SIMS is the ultimate tool for U-Pb dating and the prerequisite equipment for the study of element partitioning. Therefore, we must utilize SIMS more extensively in geochemical studies in Japan in order that our ideas will not to be outdated. And furthermore, we should create new ideas.
Geochronological and geochemical studies were performed on alkali volcanic rocks from Oki-Dogo Island, locating about 60 km off the coast of Southwest Japan inside the Japan Sea. There are big differences both in age and in geochemistry between the oldest alkali rocks and the younger rocks; the former having significant Nb and Ta-deletion and Ba and K2O-enrichment erupted at 19–18 Ma when the opening of the Japan Sea was ongoing, while the latter with no Ta-depletion were active between 5.5–0.6 Ma considerably after the cessation of the rifting activity. Syn-extensional rocks should not have erupted in the active subduction zone but are probably originated from or at least contaminated by the lithosphere beneath the early Proterozoic crust. The lithosphere is considered to have suffered mantle metasomatism to form phlogopite selectively enriched in Ba and K2O by fluids, which had been released from previous subductions at the Asian continental margin. Partial meting of such lithospheric mantle during the active rifting was essential for the generation of Ba and K2O-enriched alkali basalt magmas. The younger basaltic rocks are probably originated either from the asthenosphere or the deeper plume mantle. A suite of volcanic rocks from mugearite through trachyte to alkali rhyolite gave concordant ages of 5.5–5.4 Ma. These ages suggest that a previously reported Rb-Sr whole rock age of 6.8 ± 0.3 Ma does not represent the age of eruption and is probably disturbed by magma mixing between basic and acidic end members.
Boron contents and boron isotopic compositions were determined for modern and ancient (Permian to Miocene) marine sediments, including pelagic clay, calcareous ooze, siliceous ooze and neritic clay sediments. δ11B values of modern marine sediments range from −6.6 to +4.8‰. Isotopic variation is controlled by the simple mixing of four major constituents, detritus of continental origin, marine smectite, biogenic carbonates and biogenic silica. Detritus of continental origin, with an average δ11B value of −13 to −8‰, is the low-δ11B end-member constituent of marine sediments and its boron is largely controlled by the concentration of illite which originates from wind or fluvial transport. Marine smectite, biogenic carbonate and biogenic silica, on the other hand, represent the high-δ11B end members, with δ11B values of +2.3 to +9.2‰, +8.0 to +26.2‰ and +2.1 to +4.5‰, respectively. These high δ11B values are the result of the equilibrium uptake of boron from seawater. Spatial variations in boron isotopes in the Pacific sediments are essentially due to the distribution of the above four constituents. Although ancient argillaceous sediments (shale and slate) have boron contents that are identical with those of modern equivalents, boron contents of limestone and chert are distinctly lower than those of modern calcareous and siliceous oozes. Ancient marine sediments have systematically lower δ11B values (−17.0 to −5.6‰) than those of the modern sediments. The lower δ11B values can be caused by diagenesis, which induces (1) preferential removal of high-δ11B boron in calcium carbonate and silica during recrystallization and (2) boron isotopic exchange in the course of the smectite/illite transition. The observed boron isotopic compositions of ancient argillaceous sediments are distinctly different from those of fresh and altered MORB. Therefore, boron isotope systematics will be useful in identifying components from the descending oceanic slab involved in the formation of island arc magma and in investigating mantle-crust recycling through subduction processes.
Ce and Nd isotope ratios and REE contents of one carbonaceous chondrite (Murchison), 3 ordinary chondrites (Granès, Holbrook and Barwise) and 4 achondrites (Camel Donga, Juvinas, two pieces of Millbillillie) were measured. For the Ce isotope analysis of meteorite samples the new chemistry for extracting Ce from the gel formed after decomposition of ∼1-g chondrite sample with Mg content of 20% was developed with a recovery yield of 80%. The initial Ce isotope ratio of each meteorite sample was calculated with the assumption that the age of meteorite samples is 4.56 Ga, and the average value was obtained to be 138Ce/142Ce−0.0225321 ± 0.0000007 (2σ), which is considered to be the primordial Ce isotopic composition of the solar system. The average of the present-day Ce isotope ratios of the chondrites of this study and that previously published by Shimizu et al. is 0.0225653, which suggests that the estimation of the Ce isotope ratio of the present-day bulk Earth of 0.0225652 that was published by Makishima and Nakamura is convincing. The Ce isotope ratio of the present-day bulk Earth of 0.0225652 gives the 138La/142Ce ratio of the bulk Earth to be 0.00306 ± 0.00006 (2σ), which corresponds to La/Ce = 0.375 ± 0.007 (2σ). We propose that the La/Ce ratio of 0.375 represents that of the bulk Earth or CHUR.
The saturation of Zr, P2O5 and TiO2 in felsic to intermediate silicate melts, and the REE partitioning into zircon and other accessory minerals (apatite and sphene) are reviewed in this article. As discussed in Part I, the latent primitive crust can be characterized by the study of REE in the xenocrystic cores of Archean zircons, such as the 4.2 Ga zircon from Mt Narryer. In order to better understand the geochemistry of the REE, we review the REE partitioning data for zircon, apatite, allanite and sphene in natural felsic to intermediate rock studies and in high pressure experiments. We also review the experimental results for Zr, P2O5 and TiO2 saturation conditions. The saturation of P2O5 and TiO2 is important for the discussion of the REE partitioning in zircon, because the REE contents in the silicate melt coexisting with zircon is affected by the crystallization of the other REE rich accessory minerals like apatite or sphene. Based on our reviews, we conclude that REE partitioning cannot be constrained from the studies of natural rocks because the partitioning of the REE is affected by temperature and pressure which we do not know precisely. The SiO2 content in the silicate melt also affects the partitioning of the REE because it changes the structure of the silicate melt, as briefly reviewed in this article. In addition, REE partitioning data obtained by conventional “bulk analysis” of zircon is becoming less important. This is because a bulk analysis, especially for LREE, is easily affected by inclusions in zircon, where the LREE are enriched in these inclusions. Only SIMS analyses can eliminate the effect of the inclusions and reveal the actual partitioning of REE in zircon.
In this paper (Part I), recent progress in U-Pb dating of zircon is reviewed. Rare-earth element (REE) partitioning of accessory minerals and REE geochemistry of zircon will be reviewed in separate papers, Part II and Part III, respectively. Zircon (ZrSiO4) is one of the most important minerals in geochronology because the zircon crystal is very resistant to alteration, metamorphic and magmatic events. Zircons therefore preserve their primary chemical properties, especially very high U and Th and extremely low Pb contents, in many cases, resulting in most Pb in zircon to be time-integrated radiogenic origin. For the above reasons, zircon has been extensively used in geochronology for over 30 years. Conventional U-Pb dating of zircon has been performed using a thermal ionization mass spectrometer with isotope dilution (IDTIMS). With improvements in the techniques for the elimination of discordant parts and the chemical decomposition of zircon, it is now possible to measure U-Pb age with IDTIMS not only of a sircon grain but also of fragments of a single zircon grain. Recently, the single zircon evaporation technique has been developed to analyze for U/Pb only the closed-system domains in a single grain without chemical treatment. The most outstanding advance in U-Pb dating of zircon has been achieved by the development of secondary ion mass spectrometry (SIMS). Using the SHRIMP (Sensitive High Resolution Ion Micro Probe) at Australian National University, a very small area ( < 40 μm) can be analyzed, making it possible to reveal with precise age determinations the multiple growth history in a single grain of zircon. However, one of the major problems in the SIMS analysis resides in preparation of a homogeneous zircon standard. The U and Pb concentrations and the Pb isotope ratios of the standard must be known but they can only be obtained by the conventional IDTIMS method. The conventional IDTIMS is, therefore, a prerequisite for SIMS U-Pb dating. The oldest zircons, recorded > 4.0 Ga, have been found with SHRIMP. The existence of such old zircons was confirmed by results obtained by IDTIMS and the single zircon evaporation technique with TIMS. Characterization of the latent primitive crust, based on the chemical compositions of the detrital zircons and their measured ages, has been attempted.
The β-decay constant of 138La has been geochronologically determined using Archean granites from the Yilgarn Block, Western Australia. Rb-Sr and Sm-Nd mineral isochron ages were obtained for the two granite samples, which are nearly identical with the ion microprobe U-Pb zircon ages. This agreement indicates that the closure date for these samples is the same, within analytical error, making them suitable for geochronological estimation of the β-decay constant for 138La. Applying a new method of Ce isotope analysis, with analytical reproducibility of ±0.008%, La-Ce isotope data for the studied samples resulted in precise mineral isochrons. Based on these internal mineral isochrons and ages determined by other geological clocks, the β-decay constant for 138La was estimated to be (2.33 ± 0.24)·10−12a−1 (2σ).
A high-precision Li isotope analysis was developed for determining the Li+ ion emitted from lithium phosphate as an ion source material by a Re double-filament ionization method in the thermal ionization mass spectrometry. In this method, Li isotopic fractionation is distinctly less sensitive to the filament temperature than those in the previous methods, and stable and high ion beam intensity of more than 8×10-11 A for 7Li is obtained. These advantages in determining the 7Li/6Li ratio result in the analytical reproducibility of 0.26‰ (1σ). Furthermore, the sample preparation is simple and the low temperature (850°C) required by this method ensures the analysis of the isotopic composition of small amounts of Li with less influence of Li contamination to the sample, compared with the previous methods.
Geochemical and cosmochemical studies on lithium are reviewed and the potential of lithium isotope systematics as a geological tracer is discussed in this article. Lithium, the smallest of the alkaline elements, possesses two stable isotopes, 6Li and 7Li. It also displays the following unique physicochemical characteristics: (1) an extremely high cross-section of the lithium isotope 6Li for thermal neutrons; (2) high incompatibility in the mafic silicate minerals in the magmatic processes; (3) high solubility in fluid phases; and (4) large isotopic variations in the 6Li/7Li ratio of natural samples exceeding 30‰. The content and isotopic composition of lithium in meteoritic and terrestrial materials may provide important clues to understanding nucleosynthesis theories and many geological phenomena including water/rock interactions, metamorphic and magmatic processes. However, the isotopic behavior of lithium in geologic processes is still not well understood, since only a few reliable isotopic measurements of lithium are available for natural samples due essentially to analytical difficulties; derived from the extremely large mass difference between the two isotopes and no internally-derived correction for the mass fractionation in mass spectrometry. In order to apply lithium isotope systematics for understanding geochemical and water-related processes in the Earth and other planets, the development of a high precision technique for lithium isotope analysis is urgently required so as to accumulate the much needed fundamental data set of natural samples.
23.0±1.2 Ma was obtained by Rb-Sr method for a phlogopite-bearing spinel lherzolite from the Horoman peridotite complex in the Hidaka metamorphic belt, Hokkaido, Japan. The age is essentially identical to the oldest ages of the country metamorphic rocks reported so far in the Hidaka metamorphic belt, and may indicate the time of a metasomatic event which occurred in the wedge mantle. This metasomatic event may have occurred during uplift of this mantle fragment under mantle conditions contemporaneously with elevation of the Hidaka metamorphic belt resulting from collision between the Eurasian and North American plates.
Complete separation of Sr for the isotopic analysis of Mg-rich samples, such as ultramafic rocks and their constituent minerals, was established by adopting a combination of cationexchange chromatography in H+ form and pyridinium form with a DCTA complex using extremely small volumes of cation-exchange resin (1ml and 0.5ml respectively), This method made it possible to efficiently separate nanogram sizes of Sr from coexisting large amounts of Mg and Ca with a reduced total elution volume of only 24ml. The method also resulted in the reduction of procedural blanks for Sr and Rb to 32 and 25 pg, respectively. Applying static multicollection mass spectrometry with Ta-oxide as an ionization activator on a V-shaped W single filament, the isotopic composition of 10 to 20 ng Sr samples separated from 40 to 55mg of ultramafic rock standard (PCC-1) was determined with analytical precision of < 0.005% and reproducibility of < 0.006%. These precise analyses were performed with a high 88Sr+ ion beam intensity ( > 1.5×10-11 A). Our efficient chemical separation procedure also ensured the absence of Ca and Mg interference to Sr ionization. The Ta-oxide readily eliminated Rb prior to the Sr isotopic analysis in the mass spectrometer. This improved the analytical reliability of isotope dilution mass spectrometry (IDMS) for the simultaneous determination of Sr isotopic composition and concentration. The measured isotopic compositions of spiked PCC-1 agreed within error with those obtained from unspiked measurements, Rb/Sr ratio analyses for PCC-1 using IDMS provided analytical reproducibilities of better than 2%. These achievements indicate that our IDMS technique is capable of yielding trace Rb and Sr concentrations simultaneously with Sr isotopic composition in Mg-rich samples with an analytical reliability similar to that obtained from larger samples (1 μg) of common silicate rock samples.
Boron contents and boron isotopic compositions were determined for the uppermost 1.3 km section of typical 6.2 Ma oceanic crust from DSDP/ODP Hole 504B, Costa Rica Rift, Galapagos Spreading Center. Both the boron content and the δ11B value in the oceanic crust are controlled by two types of alteration: (1) low-temperature alteration (0 to 60°C; Zones I and II) and (2) high-temperature hydrothermal alteration (200 to 400°C; Zones III and IV). Basalts subjected to the low-temperature alteration are characterized by their relatively high boron contents (0.69 to 19.3 ppm) and high δ11B values (+2.2 to +10.6%.), indicating uptake of boron into secondary phases in equilibrium with seawater or evolved seawater. Hydrothermally altered basalts contain less abundant boron (0.17 to 0.52 ppm) and relatively constant δ11B values (−0.1 to +1.0%.). Although basalts from the upper part of these hydrothermal zones (< 1300 mbsf) show equilibrated boron content and δ11B value with aqueous fluid, effective leaching of boron from basalt is predominant in the lower part (>1300 mbsf). Original boron content and δ11B value of the Hole 504B MORB were 0.35 ppm and +0.2%., respectively. The present data provide fundamental information in understanding of the distribution of boron and boron isotopes in the oceanic crust.
The origin of p-isotopes (proton rich isotopes) and their isotopic anomalies are reviewed in this article. The p-isotopes (84Sr,124Xe, 130Ba, 144Sm, 196Hg, etc.) are heavy isotopes (A≧74) which cannot be synthesized by s-process or r-process. The p-isotopes are considered to be produced by the transmutation of heavy elements into lighter p-isotopes via a series of (γ, n), (γ, p) and (γ, α) reactions in supernovae. We can constrain the site and the condition of nucleosynthesis in supernovae from abundances of the p-isotopes. The isotopic anomalies of the p-isotopes of Xe, Cd and Sn are found in acid residues of the Allende carbonaceous chondrite. The anomalies of 84Sr and 144Sm are also found in the Allende FUN inclusions. They are considered to be presolar origin. The anomalies of 196Hg are found, however, their origin still remains enigmatic. The anomaly of Mo isotopic abundances is found in the Sikhote-Alin iron meteorite. The anomaly can be explained by (γ, n) reaction chains of Mo. The further study of the Mo anomaly will give us interesting informations not only about the p-process, but also about the r-process effect on 93Nb, the double β--decay of 96Zr, and the (γ, n) reaction chain of 99Tc.
Newly developed techniques for boron chemical separation and isotopic analysis in natural silicate rocks and waters are described. Sample dissolution and the subsequent ion-exchange chromatography were conducted using hydrofluoric and hydrochloric acids in the presence of mannitol which suppresses boron volatilization and isotopic fractionation by the formation of a boron-mannitol complex. Thermal ionization mass spectrometry using the Cs2BO2+-graphite method was employed for the determination of boron isotopic composition. No boron isotopic fractionation was observed in the course of chemical separation and mass spectrometry. In the whole analytical procedure, procedural blank and recovery yield of boron were 3–4 ng and 99±1%, respectively. The analytical precision and reproducibility of measured 11B/10B ratios were ±0.1−0.1% and ±0.2‰ for the measurements of basalt and seawater, respectively. The present method enables us to determine the isotopic composition of < 1 μg B in silicate samples and in natural fluids with the above-mentioned analytical errors. This method also provides a remarkable improvement in the measurement of boron concentration by isotope dilution mass spectrometry because of the achievement of complete mixing between sample and spike during sample decomposition.
A high-precision analytical method for the measurement of ratios is reported using static multicollection mass spectrometry. This technique reduced the data acquisition time for 2 hr. for 400 ratios and improved analytical reproducibility to ±0.002% (n-16) and precision to ±0.002–0.003%. The better precision and reproducibility were established collecting a large ion beam [142Ce16O of (2–7) · 10−11 A], short data acquisition time and in situ measurement of 18O/16O ratios during the analysis. To reduce the blank effect to the Ce isotope analysis, the chemical procedure for separation of Ce was refined using a small ion-exchange resin bed column (4 cm length × 3 mm diameter) with which the procedural total blank was lowered to 0.04 ng and the recovery yield of Ce from 20 mg BCR-1 was 90%. In order to confirm the reproducibility of this technique including the chemical procedure, six Ce isotope analyses individually separated from the USGS standard BCR-1, were carried out with an analytical reproducibility of ±0.002%. With these analytical precision and reproducibility and normalization to BCR-1 in order to eliminate any inter-laboratory biases, it is now possible to apply the La-Ce isotope system to the terrestrial and extraterrestrial samples combined with other isotope systems, such as Sm-Nd and Rb-Sr.
Faraday cup efficiencies (FCE's) in the multicollector mass spectrometer were examined with a static multicollection technique. The relative Faraday cup efficiency (RFCE) was estimated by measurement of Nd-isotope ratios with five different cup configurations. The application of RFCE correction to the static multicollection technique will increase the reliability of analytical results by eliminating the errors caused by differences in FCE's, and will also enable us to distinguish which Faraday cups are damaged and should be renewed.
New results on lead isotope compositions of standard rock samples and their analytical procedures are reported. Bromide form anion exchange chromatography technique was adopted for the chemical separation of lead from rock samples. The lead contamination during whole analytical procedure was low enough to determine lead isotope composition of common natural rocks. Silica-gel activator method was applied for emission of lead ions in the mass spectrometer. Using the data reduction of "unfractionated ratios", we obtained good reproducibility, precision and accuracy on lead isotope compositions of NBS SRM. Here we present new reliable lead isotope compositions of GSJ standard rock samples and USGS standard rock, BCR-1.
143Nd/144Nd, 87Sr/86Sr , trace and major element results are reported for Cenozoic alkaline basalts and associated tholeiitic basalts from southwestern Japan, and some from Korea and China. Most of the samples plot within the mantle array with ϵNd values ranging from +5.0 to −3.2 and 87Sr/86Sr ratios ranging from 0.7037 to 0.7057. The isotopic variations observed along traverse sections of alkaline basalts from the trench to the continental sides of southwestern Japan do not suggest a direct relationship between the subduction of the Philippine Sea and Pacific plates, and the generation of alkaline basalt magmas. However, in southwestern Japan the alkaline basalts do show evidence of a subducted component and are more enriched in the mobile incompatible elements, such as Rb, Ba and K, relative to Chinese and Korean basalts. Negative correlations between ϵNd and Sm/Nd and between ϵNd and La/Th, as well as a positive correlation between 87Sr/86Sr and La/Th, are recognized in some of the basalts. These relationships indicate at least two-component magma mixing between (1) magma resulting from a small melting from a depleted mantle and (2) magma resulting from a relatively large amount of melting of an enriched mantle source. It is suggested that the Cenozoic alkaline basalts from southwestern Japan, Korea and China are product of interaction between a MORB-type mantle and a deep mantle plume. If the mantle plume has ascended from the upper mantle-lower mantle or core-mantle boundary, the subducted Pacific and Philippine Sea plates could not have extended to southwestern Japan. Had they done so they would have arrested, before they reached the melting zone, the ascent of the plumes that produced the alkaline volcanism in southwestern Japan.
Volatilization and mass fractionation of boron during evaporation of the hydrofluoric and hydrochloric acid solutions were investigated with varying mannitol/boron ratios. The degree of volatilization and mass fractionation decreases with increasing mannitol/boron mol ratio and the boron volatilization is completely suppressed when the ratio is more than unity. These results indicate that the final stable compound of boron-mannitol complex is an equimolar complex of boron and mannitol. The formation of this complex allows the use of hydrofluoric and hydrochloric acids for the dissolution of silicate rock samples and for separation of boron from the samples adopting anion exchange chromatography in F- form.
Volatilization and mass fractionation of boron during evaporation of the hydrofluoric and hydrochloric acid solutions were investigated with varying mannltol/boron ratios. The degree of volatilization and mass fractionation decreases with increasing mannltol/boron mole ratio, and the boron volatilization Is completely suppressed when the ratio Is more than unity. These results Indicate that the final stable compound is an equimolar complex of boron and mannitol. The formation of this complex In the acid solutions allows the use of hydrofluoric and hydrochloric acids for the dissolution of silicate rock samples and for the subsequent chemical separation of boron from the samples adopting anion-exchange chromatography in F- form.
Major and trace element have been analyzed from alkaline basalts from southwestern Japan, Korea, and northeastern China. No significant differences were found in the immobile incompatible element ratios, such as Zr, Y, Hf, Th, and Ti. These ratios, as well as normalized incompatible element patterns, resemble those of continental and oceanic island alkaline basalts. However, southwestern Japanese alkaline basalts show evidence of K, Ba, and Rb enrichment and a slight depletion in Ta relative to La, implying a weak island arc signature. Korean and Chinese alkaline basalts do not have such a signature. Rare earth elements (REE) show near‐constant La/Sm ratios and a crossover at the high REE end of patterns for each areas studied. The parallelism in light REE can be derived if the magmas are mixtures formed by (1) relatively large degrees of partial melting of an enriched mantle plume from deeper in the mantle and (2) a small degree of partial melting of a depleted mid‐ocean ridge basalt (MORB)‐type source. These observations when combined with seismic results suggest that the upper mantle beneath southwestern Japan has been weakly affected by metasomatism caused by dehydration and/or partial melting of subducted Pacific plate (not Philippine Sea plate). The mantle plume may have reacted with weakly metasomatized MORB‐type depleted mantle to produce alkaline basalt magmas retaining mild island arc characteristics in southwestern Japan. However, the metasomatism by the subduction of the Pacific plate has not affected the mantle beneath Korea and northeastern China. Here the interaction between plume and MORB‐type mantle produced alkaline basalt magma similar to normal continental and oceanic alkaline basalts.
Seven new K-Ar age determinations are presented on whole rock samples from alkaline and tholeiitic basalts of the Higashi-Matsuura district, northwestern Kyushu, Japan. Ages obtained range from 2.92 ± 0.03Ma to 3.01 ± 0.04Ma; these ages are essentially identical within analytical errors and yield an average age of 2.98 ± 0.03Ma (Late Pliocene). When combined on an isochron type diagram the six Higashi-Matsuura samples give an age of 3.00 ± 0.03 Ma with the composition of nonradiogenic 40Ar/36Ar = 294.2 ± 2.0. The excellent age agreement of samples with different K contents and petrographic characteristics provides strong evidence that the tholeiitic and alkaline basalts were erupted for an extremely short period in the Higashi-Matsuura district. A basalt from Ogawashima Island yields a K-Ar age of 3.58 ± 0.04Ma. This study and previously reported data support the hypothesis that alkaline volcanic activity in southwestern Japan commenced some 10Ma ago and continued intermittently until Recent times. Systematic variations of age and distribution of Cenozoic alkaline basalts are recognized in northeastern China, Korea and southwestern Japan. It is suggested that these variations are related to the initiation of “mantle plumes” resulting from convection in the mantle wedge caused or controlled by subduction of the Kula and Pacific plates.
The composition of volcanic rocks erupted in complex plate tectonic settings can provide information on the nature of the underlying mantle. We show here that the geochemistry of alkali basalts from Japan and eastern Asia varies systematically with distance from the Japanese island-arc. Samples from northeastern Japan, relatively close to the Japan Trench, are enriched in K, Sr, Ba and Rb and depleted in Ta, Nb and Ti as compared with samples from southwestern Japan. Both sets show an island-arc influence on their composition, but alkali basalts from still further west (Korea and northeastern China) have chemistries which are indistinguishable from ocean island basalts. We suggest that the northeastern island-arc type of alkali basalts were derived from a ‘normal’ upper mantle source altered by fluids or melts released from the underlying subducted Pacific plate. The extent of this island-arc-related alteration decreases with distance from the trench.
The South Sturgeon Lake sequence consists of four volcanic cycles. The lower two cycles host Cu-Zn massive sulfide mineralization. Economic mineralization has not been found in the third and fourth cycles. Trace element and rare earth analyses performed previously and in the present study indicate that the lower three cycles have a similar petrogenetic history and are cogenetic with the Beidelman Bay pluton, a subvolcanic trondhjemite sill which intrudes the base of the lower cycle. The upper cycle is distinctly different. U-Pb zircon analyses have been performed on seven rocks from the lower three cycles in an effort to resolve the ages. All age analyses agree within error, giving an average of 2,735.5 m.y., with a range of 1.5 m.y. A previously determined age of 2,733.8 (super +1.4) (sub -1.3) m.y. on the subvolcanic intrusion is marginally younger. The uppermost cycle was previously dated at 2717.9 (super +2.7) (sub -1.5) m.y., 18 m.y. younger than the lower cycles. Moreover, rare earth element data indicate that this upper cycle is not comagmatic with the lower cycles. The data indicate rapid evolution of a volcanic pile followed by a long period of quiescence and later reactivation from a different magmatic source.The younger age of the Beidelman Bay pluton indicates that it probably is not directly related to volcanism and ore-forming hydrothermal activity. However, it may occupy the magma chamber which previously fed rhyolitic volcanism and acted as a heat source driving hydrothermal convection which transported and deposited base metals. This would require the subvolcanic magma chamber to be coupled to a much larger magma system which fed eruptive and high level intrusive activity, remaining molten for about 1.7 m.y.
K-Ar ages have been determined on white micas from four Sangun pelitic schists in the Nishiki-cho and Toyoga-dake areas, Yamaguchi Prefecture. The dates from the Nishiki-cho area are 172 and 175 Ma, while those from the Toyoga-dake area are 264 and 274 Ma. They represent a wide range of time, 172 to 274 Ma, which is nearly identical with that of eight ages, 165 to 264 Ma, reported previously from the Sangun metamorphic rocks. The twelve available dates on the Sangun metamorphic rocks can be divided into two age clusters, an older age cluster around 260 Ma (middle Permian) and a younger cluster around 170 Ma (middle Jurassic). It is suggested that the two age clusters may coincide with the two stages of uplift for the Sangun metamorphic rocks. Namely, the age cluster around 260 Ma may indicate the event in which the Sangun metamorphic rocks were emplaced as nappes from the deep tectonic position of glaucophanitic metamorphism into a shallow tectonic position and the metamorphism had ceased. On the other hand, the age cluster around 170 Ma may represent an event related to the beginning of the formation of the pile nappe structure in which the Sangun metamorphic rocks tectonically overlie the Jurassic non-metamorphic equivalents of the Tamba Group.