Oxygen isotope systematics of chondrules in the Allende CV3 chondrite: High precision ion microprobe studies

The oxygen three-isotope systematics of 36 chondrules from the Allende CV3 chondrite are reported using high precision secondary ion mass spectrometer (CAMECA IMS-1280). Twenty-six chondrules have shown internally homogenous Δ¹⁷O values among olivine, pyroxene, and spinel within a single chondrule. The average Δ¹⁷O values of 19 FeO-poor chondrules (13 porphyritic chondrules, 2 barred olivine chondrules, and 4 chondrule fragments) show a peak at −5.3 ± 0.6‰ (2SD). Another 5 porphyritic chondrules including both FeO-poor and FeO-rich ones show average Δ¹⁷O values between −3‰ and −2‰, and 2 other FeO-poor barred olivine chondrules show average Δ¹⁷O values of −3.6‰ and 0‰. These results are similar to those for Acfer 094 chondrules, showing bimodal Δ¹⁷O values at −5‰ and −2‰. Nine porphyritic chondrules contain olivine grains with heterogeneous Δ¹⁷O values as low as −18‰, indicating that they are relict olivine grains and some of them were derived from precursors related to refractory inclusions. However, most relict olivine grains show oxygen isotope ratios that overlap with those in homogeneous chondrules. The Δ¹⁷O values of four barred olivine chondrules range from −5‰ to 0‰, indicating that not all BO chondrules plot near the terrestrial fractionation line as suggested by previous bulk chondrule analyses. Based on these data, we suggest the presence of multiple oxygen isotope reservoirs in local dust-rich protoplanetary disk, from which the CV3 parent asteroid formed.A compilation of 225 olivine and low-Ca pyroxene isotopic data from 36 chondrules analyzed in the present study lie between carbonaceous chondrite anhydrous mineral (CCAM) and Young and Russell lines. These data define a correlation line of δ¹⁷O = (0.982 ± 0.019) × δ¹⁸O − (2.91 ± 0.10), which is similar to those defined by chondrules in CV3 chondrites and Acfer 094 in previous studies. Plagioclase analyses in two chondrules plot slightly below the CCAM line with Δ¹⁷O values of −2.6‰, which might be the result of oxygen isotope exchange between chondrule mesostasis and aqueous fluid in the CV parent body.     

Volatile characteristics of peralkaline rhyolites from Kenya: an ion microprobe,infrared spectroscopic and hydrogen isotope study

Peralkaline rhyolites of the Greater Olkaria Volcanic Complex, Kenya Rift Valley, were derived from separated, though closely related, magma chambers. Ion microprobe analyses of glass inclusions in quartz phenocrysts show pre-eruptive water contents of up to 3.4 wt% contrasting with previous estimates that the magmas were anhydrous. The values approach predicted solubility levels corresponding to water saturation at low crustal pressures (1 kbar). The glass matrices of the rhyolites have low water contents, ranging from 0.07 to 0.46 wt%, suggesting significant degassing during, or prior to, eruption. Infrared measurements of the matrix glasses show variation in the relative proportions of the two hydrous species dissolved in the glasses. The amount of molecular water, determined semi-quantitatively, apparently increases with increased fluorine content and peralkalinity. This suggests a competition between hydroxyl groups and fluoride ions for similar sites within the melt structure. The mechanism of degassing has been investigated using hydrogen isotopes. The range of D values in most rocks can be produced by varied degrees of open-system degassing of rhyolite melt initially in equilibrium with water of a fixed, or limited, D value. There is evidence to suggest that closed-system degassing may also have been a significant component in some rhyolites. The exact mechanisms of degassing remain uncertain. Particular problems include the relative contribution of open-and closed-system degassing during eruption and the initial vapour compositions and solubility relationships.     

Ophiolitic magmatism in the Ligurian Tethys: an ion microprobe study of basaltic clinopyroxenes

Ion microprobe data (REE, Na, Sc, Ti, V, Cr, Sr, Zr) of unaltered clinopyroxenes in the ophiolitic basalts from the Northern Apennines have been used in a epx-based geochemical modelling of MORB magmatism from both External (EL) and Internal (IL) sectors of the Ligurian Tethys (i.e. Jurassic Ligure-Piemontese basin), alternative to the more common whole-rock approach. Clinopyroxenes from EL basalts display slightly fractionated LREE (Ce_N/Sm_N0.5) and HREE (Gd_N/ Yb_N1.5) patterns and large variations in the REE composition (up to 6 times from microphenocryst cores to interstitial clinopyroxenes). Interstitial clinopyroxenes in IL basalts are similar to the microphenocrysts from the most primitive EL basalts. By contrast, IL microphenocrysts are characterized by greater LREE (Ce_N/Sm_N 0.3) and lesser HREE (Gd_N/Yb_N<1.2) fractionation. The comparison of trace element variations in wholerocks and clinopyroxenes clearly shows that the olivine and plagioclase portion of the fractionation sequence is poorly represented by the EL and IL basalts. In fact, ophiolitic basalts mainly consist of a minor interstitial glass (now deeply altered) associated with a prevailing plagioclase-clinopyroxene assemblage crystallized from liquids significantly evolved along the olivine-plagioclase-clinopyroxene saturation boundary. Thus, bulk rock chemistry is largely governed by clinopyroxene composition. This, in addition to alteration, indicates that the bulk rock chemistry does not provide reliable chemical information to constrain the composition and the generation of the parental magmas. Unfortunately, most clinopyroxenes are characterized by complex zoning, probably caused by disequilibrium partitioning during crystal growth as a result of kinetic factors. On this ground, estimation of melt chemistry and inferences about the origins of these basalts are only allowed by the core compositions of microphenocrystic clinopyroxenes. Modelling of (Nd/Yb)_N and Ti/Zr in the parental magmas, as deduced from the clinopyroxene compositions, indicates thata EL and IL basalts do not represent products of different mantle source composition. Rather, they were generated by varying degrees of fractional melting in the spinel stability field, lower for the EL (a few percent) relative to IL, totalling no more than 10% of an asthenospheric MORB source, and leaving in the residua clinopyroxene with REE patterns similar to those shown by IL suboceanic type peridotites. Accordingly, these latter are interpreted as refractory residua after MORB-generating fractional melting occurred during rifting and opening of the Ligure-Piemontese basin. By contrast, residual clinopyroxenes from the EL subcontinental type peridotites are not consistent with low degrees of fractional melting in agreement with the current interpretation that EL peridotites are unrelated to the MORB magmatism in the Ligure-Piemontese basin and represent lithospheric mantle material already emplaced towards the surface by a tectonic denudation mechanism during the early stages of oceanic rifting.     

Timescales and mechanisms of fluid infiltration in a marble: an ion microprobe study

Using a recently developed ion microprobe technique, a detailed oxygen isotope map of calcite grains in a coarse-grained marble has been constructed, supported by trace element (Mn, Sr, Fe) analysis and cathodoluminescence (CL) imaging, in order to constrain scales of oxygen isotope equilibrium, timescales and mechanisms of metamorphic fluid infiltration, and fluid sources and pathways. Results are compared with a previous study of this sample (Wada 1988) carried out using a cryo-microtome technique and conventional oxygen isotope analysis. The marble, from the high temperature/low pressure Hida metamorphic belt in north-central Japan, underwent granulite facies followed by amphibolite facies metamorphic events, the latter associated with regional granite intrusion. The CL imaging indicates two types of calcite, a yellow luminescing (YLC) and a purple luminescing (PLC) variety. The YLC, which occupies grain boundaries, fractures, replacement patches, and most of the abundant deformation twin lamellae, post-dates the dominant PLC calcite and maps out fluid pathways. Systematic relationships were established between oxygen isotope and trace element composition, calcite type and texture, based on 74 ¹⁸O/¹⁶O and 17 trace element analyses with 20–30 μ m spatial resolution. The YLC is enriched in Mn and Fe, and depleted in ¹⁸O and Sr compared to PLC, and is much more ¹⁸O depleted than is indicated from conventional analyses. Results are interpreted to indicate infiltration of ¹⁸O-depleted (metamorphic or magmatic) fluid (initial δ¹⁸O = 9‰–10.5‰) along grain boundaries, fractures and deformation twin lamellae, depleting calcite grains in Sr and enriching them in Mn and Fe. The sample is characterised by gross isotopic and elemental disequilibrium, with important implications for the application of chromatographic theory to constrain fluid fluxes in metacarbonate rocks. Areas of PLC unaffected by “short-circuiting” fluid pathways contain oxygen diffusion profiles of ∼10‰/∼200 μm in grain boundary regions or adjacent to fractures/patches. When correction is made for estimated grain boundary/fracture and profile orientation in 3D, profiles are indistinguishable within error. Modelling of these profiles gives consistent estimates of Dt (where D is the diffusion coefficient and t is time) of ∼0.8 × 10⁻⁸ m², from which, using experimental data for oxygen diffusion in calcite, timescales of fluid transport along grain boundaries at amphibolite facies temperatures of ∼10³ to ∼10⁴ years are obtained. These short timescales, which are much shorter than plausible durations of metamorphism, imply that rock permeabilities may be transiently much higher during fluid flow than those calculated from time integrated fluid fluxes or predicted from laboratory measurements. The preservation of ¹⁸O/¹⁶O profiles requires either rapid cooling rates (∼100–600 °C/million years), or, more plausibly, loss of grain boundary fluid such that a dry cooling history followed the transient passage of fluid. The δ¹⁸O/trace element correlations are also consistent with volume diffusion-controlled transport in the PLC. Fluid transport and element exchange occurred by two inter-related mechanisms on short timescales and on different lengthscales – long-distance flow along cracks, grain boundaries and twin lamellae coupled to ∼200 μm-scale volume diffusion of oxygen. Received: 8 December 1997 / Accepted: 18 May 1998     

Sulfur isotope systematics in icelandic geothermal systems and influence of seawater circulation at Reykjanes

Pyrite from altered basalts from Nàmafjall and Krafla high-temperature fields and deep zones at Reykir, Leira and other low-temperature fields, and aqueous sulfides from Nàmafjall, have δ³⁴S values of 0 to 2.6%. These values are close to those for postglacial basaltic lavas from the Reykjanes Peninsula. The major source of sulfur in these meteoric hydrothermal systems is the upper-mantle or basalt. At the low-temperature fields, however, the δ³⁴S values of sulfide decrease with decreasing depth, suggesting the presence of a light sulfur source in the shallower aquifers.In contrast, in the Reykjanes and Svartsengi geothermal fields, where seawater contributes to the hydrothermal systems, sulfide sulfur is distinctly enriched in ³⁴S at all depths except for one Reykjanes pyrite from 84 m depth. The enrichment is about 8%. at the deepest core (1734 m) of Reykjanes and decreases with decreasing depth. These enrichments are most likely due to seawater sulfate being involved in the hydrothermal systems. However, in the Reykjanes fluid, dissolved heavy sulfates are not in isotopic equilibrium with sulfide. Disequilibrium between sulfate and sulfide is also demonstrated in all other Icelandic geothermal systems studied.     

Optically continuous silcrete quartz cements of the St. Peter Sandstone: High precision oxygen isotope analysis by ion microprobe

A detailed oxygen isotope study of detrital quartz and authigenic quartz overgrowths from shallowly buried (<1 km) quartz arenites of the St. Peter Sandstone (in SW Wisconsin) constrains temperature and fluid sources during diagenesis. Quartz overgrowths are syntaxial (optically continuous) and show complex luminescent zonation by cathodoluminescence. Detrital quartz grains were separated from 53 rocks and analyzed for oxygen isotope ratio by laser fluorination, resulting in an average δ¹⁸O of 10.0 ± 0.2‰ (1SD, n = 109). Twelve thin sections were analyzed by CAMECA-1280 ion microprobe (6-10 μm spot size, analytical precision better than ±0.2‰, 1SD). Detrital quartz grains have an average δ¹⁸O of 10.0 ± 1.4‰ (1SD, n = 91) identical to the data obtained by laser fluorination. The ion microprobe data reveal true variability that is otherwise lost by homogenization of powdered samples necessary for laser fluorination. Laser fluorination uses samples that are one million times larger than the ion microprobe. Whole rock (WR) samples from the 53 rocks were analyzed by laser fluorination, giving δ¹⁸O between 9.8‰ and 16.7‰ (n = 110). Quartz overgrowths in thin sections from 10 rocks were analyzed by ion microprobe and average δ¹⁸O = 29.3 ± 1.0‰ (1SD, n = 161).Given the similarity, on average, of δ¹⁸O for all detrital quartz grains and for all quartz overgrowths, samples with higher δ¹⁸O(WR) values can be shown to have more cement. The quartz cement in the 53 rocks, calculated by mass balance, varies from <1 to 21 vol.% cement, with one outlier at 33 vol.% cement. Eolian samples have an average of 11% cement compared to marine samples, which average 4% cement.Two models for quartz cementation have been investigated: high temperature (50-110 °C) formation from ore-forming brines related to Mississippi Valley Type (MVT) mineralization and formation as silcretes at low temperature (10-30 °C). The homogeneity of δ¹⁸O for quartz overgrowths determined by ion microprobe rules out a systematic regional variation of temperature as predicted for MVT brines and there are no other known heating events in these sediments that were never buried to depths >1 km. The data in this study suggest that quartz overgrowths formed as silcretes in the St. Peter Sandstone from meteoric water with δ¹⁸O values of −10‰ to −5‰ at 10-30 °C. This interpretation runs counter to conventional wisdom based on fibrous or opaline silica cements suggesting that the formation of syntaxial quartz overgrowths requires higher temperatures. While metastable silica cements commonly form at high degrees of silica oversaturation following rapid break-down reactions of materials such as of feldspars or glass, the weathering of a clean quartz arenite is slower facilitating chemical equilibrium and precipitation of crystallographically oriented overgrowths of α-quartz.     

Pyroxene in enclaves and syenites of the Red Hill complex,New Hampshire: an ion and electron microprobe study

The Red Hill complex, New Hampshire, contains both silica-undersaturated and silica-saturated to oversaturated syenites. Ion microprobe analyses of pyroxene from the Nepheline Sodalite Syenite (NSS) and its enclaves reveal that the REE abundances increase in a systematic manner from low values in the enclave pyroxenes to higher values in the NSS host rock pyroxenes. This variation is interpreted to have resulted from differentiation and coupled with previously published mineral and bulk-rock compositions, suggests that the enclaves represent samples of NSS parental liquids that intruded into residual, syenitic liquids in a zoned magma chamber. Pyroxene analyses of the Garland Peak Syenite (GPS) and its enclaves indicate that the enclaves are of several populations: some may be related to the GPS, others are not. The GPS itself is heterogeneous and pyroxene trace element zoning is difficult to explain by fractionation processes. The silica-oversaturated Outer Coarse Syenite (OCS) contains pyroxenes with trace element characteristics that are distinct from the NSS. The low V concentrations suggest that the OCS exprienced magnetite fractionation prior to pyroxene growth. It is proposed that high f O₂in the OCS magma caused Fe-Ti oxide crystallization, which in turn, influenced magmatic silica activity. The chondrite normalized REE patterns of OCS pyroxenes are also suggestive of titanite crystallization, another indication of high f O₂. In contrast to the influence of magnetite crystallization, the high and rimwardly increasing Y and Yb concentrations in both the NSS and the OCS pyroxenes suggest that amphibole fractionation was not the major influence on silica activity. Therefore, it is unlikely that the OCS was derived by amphibole fractionation from a NSS precursor magma.     

The Stability of Igneous Anhydrite: Experimental Results and Implications for Sulfur Behavior in the 1982 El Chichon Trachyandesite and Other Evolved Magmas

Hydrothermal experiments on natural samples of trachyandesiteand dacite bulk composition show that anhydrite (CaSO₄) mayoccur as a stable phenocryst phase at oxygen fugacities greaterthan or equal to 1.0 to 1.5 log f_O2 units above the Ni–NiOequilibrium. The dissolved sulfur concentration in anhydritesaturated melts from MnO–Mn₃O₄ buffered experiments decreaseswith decreasing temperature, from approximately 2300 p.p.m.Sat 1025?C to 250 p.p.m.S at 850?C (all at 2 kb P_fluid = P_total).In FeS-saturated melts equilibrated at the Ni–NiO bufferand 2 kb pressure, the concentration of dissolved sulfur alsodecreases with decreasing temperature, varying from approximately400 p.p.m. S at 1025?C to less than 100 p.p.m. S at 850?C. AtNNO or lowerf_O2s, decreasing melt FeO content due to crystalfractionation may explain the observed decrease in sulfur solubilitywith decreasing temperature. Sulfur solubility values equivalent to the approximately 0.6wt. per cent S present in fresh bulk pumice samples from the1982 eruptions of El Chichon volcano are not readily achievedunder any reasonable combinations of pressure, temperature,and oxidation state. Dissolved sulfur contents approaching 0.6wt. per cent might occur if the source regions of melts parentalto the El Chichon trachyandesite were at an f_O2 several logunits above the Ni–NiO equilibrium. Because such elevatedoxidation states are far greater than the generally acceptedvalues for mantle-derived partial melts we believe the highsulfur content of the El Chichon pumices is not a primary feature;it reflects reaction with sulfur enriched material at some unknowndepth beneath the volcano. Published sulfur isotopic and petrologicdata suggest that hydrothermally altered rocks similar to thepyrite- and anydritebearing lithic fragments found in the 1982pumices could have provided a source of sulfur for crystallizationof magmatic anhydrite. The anhydrite was an important sourceof sulfur for evolution of a sulfur-rich vapor phase duringeruption of the magma. Although many calc-alkaline dacites and rhyolites appear toattain oxidation states high enough to stabilize anhydrite,the characteristically low bulk sulfur contents of these rockswill limit anhydrite abundances to less than approximately 0.1wt. per cent, assuming sufficient sulfur is present to achievesaturation. Such small amounts of a water soluble mineral couldbe easily removed by subaerial weathering processes, dissolvedduring vapor exsolution from a magma, or simply overlooked duringroutine petrographic examination.     

Studies in diffusion—III. Oxygen in feldspars: an ion microprobe determination

Self-diffusion of oxygen in adularia, anorthite, albite, oligoclase and labradorite has been measured by isotope exchange of oxygen between natural feldspars and hydrothermal water enriched in ¹⁸O. The analysis consisted of measuring the ¹⁸O/¹⁶O gradient inward from the feldspar surface using an ion microprobe, and fitting a solution of the diffusion equation to the data. Depth of the sputtered hole was measured with an optical interferometer. Linear Arrhenius plots were obtained:

     

11.

Sulfur isotope study of Quaternary volcanic rocks from the Japanese Islands Arc     

Akira Ueda  Hitoshi Sakai 《Geochimica et cosmochimica acta》1984,48(9):1837-1848

The sulfide and sulfate contents and their δ³⁴S values were determined in Quaternary volcanic rocks from the Japanese Islands Arc. The total sulfur contents are much lower (less than 40 ppm) and the δ³⁴S values are higher (+4.4 ± 2.1) than those of ocean-floor basalts (800 ± 100 ppm and +0.8 ± 0.5, respectively; Moore and Fabbi, 1971; Sakaiet al., 1982). Lateral variations of both sulfur content and δ³⁴S values were observed in the four volcanic belts in Japan. In the Northeast Japan belt, the sulfur content (30 ± 10 ppm) of the rocks in the inner zone (the Japan Sea side) is 3 to 5 times that in the outer zone (the Pacific side), although the δ³⁴S values of the two zones are almost the same (+4.3 ± 1.0). The δ³⁴S values for the two belts in West Japan are on the average 2%. higher than those of East Japan.This study suggests that the primary magmas that formed the island arc volcanic rocks are initially depleted in sulfur (<120 ppm) and enriched in ³⁴S ($\text{δ}{}^{34}\text{S: +5 ～ +7}$) compared to ocean-floor tholeiitic basalts which formed at mantle under oceanic region. This indicates that the upper-mantle is heterogeneous in sulfur content and isotope composition.     

12.

Environmental isotope systematics of the groundwater system of southern Kuwait     

Khaled Hadi  U. Saravana Kumar  M. Al-Senafy  H. Bhandary 《Environmental Earth Sciences》2016,75(14):1096

     

13.

Re-Os isotope systematics of sediments of the Brahmaputra River system     

Sunil K. Singh  Christian France-Lanord 《Geochimica et cosmochimica acta》2003,67(21):4101-4111

Re-Os analyses were performed on suspended loads and coarser grained bank sediments of the Brahmaputra River system. Re and Os concentrations of these sediments vary from 7 to 1154 ppt and from 3 to 173 ppt, respectively. ¹⁸⁷Os/¹⁸⁸Os ratios range from 0.178 to 6.8, and thus vary from nearly mantle to very radiogenic crustal values. Nevertheless, most of the sediments have ¹⁸⁷Os/¹⁸⁸Os ratios less than 1.5, and nearly all of the samples of the Brahmaputra main channel have ratios less than 1.2. Thus, as previously suggested, the Brahmaputra is much less radiogenic than the Ganga. The Siang River, the northern extension of the Brahmaputra, is quite radiogenic in Os despite receiving sediments from the Tsangpo River, which flows along a suture zone with ultramafic outcrops. The Brahmaputra main channel has a fairly constant ¹⁸⁷Os/¹⁸⁸Os ratio even though its tributaries contribute sediments with very heterogeneous Os isotopic compositions. These data, along with the corresponding Nd isotopic compositions, suggest that about 60-90% of the sediment in the Brahmaputra system is derived from Himalayan formations (Higher Himalaya and Lesser Himalaya) whereas 10-40% comes from ophiolite-bearing sequences, perhaps eastern equivalents of those of the Transhimalayan Plutonic Belt. Os data also confirm previously published Sr and Nd results, indicating that about half of the sediments delivered to the Brahmaputra are supplied by the Siang River, while the Himalayan and the eastern tributaries account for 40 and 10%, respectively.The lower ¹⁸⁷Os/¹⁸⁸Os of the Brahmaputra River compared to that of the Ganga is due to two factors. One is the more limited presence of the Lesser Himalaya and hence the lower black shale content of the eastern Himalaya. The other is the non-radiogenic Os supplied by the eastern and southern tributaries, reflecting the presence of mantle-derived lithologies in this region. Despite the lower sediment supply from these tributaries, they contribute greatly to the Os budget of the Brahmaputra River. This study indicates that the Brahmaputra River has little effect on the present-day seawater Os budget. However, reconsideration of this budget suggests that the Ganga, which provides the most radiogenic Os of major rivers studied to date, may have significant impact on the marine Os isotopic composition. The Indo-Asian collision cannot be excluded as an important cause of the increase in the marine ¹⁸⁷Os/¹⁸⁸Os over the past 16 million years until the contributions of all of the rivers draining the Himalayan Tibetan Plateau are known.     

14.

Sulfur isotope biogeochemistry of the Proterozoic McArthur Basin     

David T. Johnston  James Farquhar  Yanan Shen  Andrew L. Masterson 《Geochimica et cosmochimica acta》2008,72(17):4278-4290

Previous geochemical and biomarker studies of the late Paleo-Mesoproterozoic propose a stratified world, with strongly reducing (possibly sulfidic) deep-ocean conditions overlain by an oxygenated surface-ocean and atmosphere. To investigate such a scenario, we look to the structure of the biogeochemical sulfur cycle. We present sulfur (³²S, ³³S, ³⁴S, and ³⁶S in sulfides) isotope data from the McArthur Basin (Barney Creek, Reward, Velkerri, and McMinn formations) that allows for a direct evaluation of the surface biosphere. We are interested in investigating the types of information that can be gained by including ³³S and ³⁶S. When the ³⁴S/³²S fractionations are small, the inclusion of ³³S and ³⁶S provides little additional information, but does provide ancillary evidence for relative isotopic homogeneity (with the internal consistency of ³³S/³²S and ³⁶S/³²S). When the ³⁴S/³²S fractionations are large, direct information about the fractionation mechanisms can be obtained, with the potential to distinguish the biological from abiological processes. For example, the reconstruction of the Roper Group suggests that seawater sulfate concentrations were high enough to buffer against spatial heterogeneities. Overall, our findings agree with previously proposed redox structure of the Proterozoic ocean, highlight contributions from the oxidative sulfur cycle, and outline a new tool for interpreting the state of the surface sulfur cycle.     

15.

Petrogenesis of the Apollo 14 high-alumina basalts: Implications from ion microprobe analyses     

Justin J. Hagerty  Charles K. Shearer 《Geochimica et cosmochimica acta》2005,69(24):5831-5845

In this study, ion microprobe analyses of individual minerals are used to investigate the petrogenesis of the Apollo 14 high-Al basalts. We use trace element concentrations from individual minerals in the Apollo 14 high-Al basalts to evaluate both endogenic and exogenic models. The data show that if the Apollo 14 high-Al basalts were produced by melting within the lunar mantle, these basalts cannot be related to one another by closed-system fractional crystallization of a single basaltic melt. Rather, the trace element data show that variable amounts of a KREEP component were added to the basalts by either assimilation, mixing into mantle sources, or impact melting. Single-stage assimilation-fractional crystallization models can only explain the data from this study if an excessively large mass of urKREEP is assimilated into the parent magma before olivine crystallization. Alternatively, the trace element data can be explained if the Apollo 14 high-Al basalts were produced by melting multiple Al-rich mantle sources that contain different amounts of urKREEP. Finally, for impact melting to be a relevant process, the data require that multiple large impact melts be formed from mixed KREEP-rich target lithologies. The resulting impact melts must then crystallize to produce basalts with igneous textures, high Al₂O₃ concentrations, uniform major element compositions, and a wide range of incompatible trace element concentrations.     

16.

Ion microprobe Sr isotope analysis of carbonates with about 5 μm spatial resolution: An example from an ayu otolith     

Yuji Sano  Kotaro Shirai  Naoto Takahata  Hiroshi Amakawa  Tsuguo Otake 《Applied Geochemistry》2008,23(8):2406-2413

     

17.

Oxygen isotope analyses of fine silica grains using laser-extraction technique: Comparison with oxygen isotope data obtained from ion microprobe analyses and application to quartzite and silcrete cement investigation   总被引：1，自引：0，他引：1  

Anne Alexandre  Isabelle Basile-Doelsch  Corinne Sonzogni  Claude Parron  Fabrice Colin 《Geochimica et cosmochimica acta》2006,70(11):2827-2835

The laser fluorination technique reported here for analyzing the oxygen isotope composition (δ¹⁸O) of fine quartz size fractions 50-20, 20-10, 10-5, 5-2, 2-1 and <1 μm has been validated by comparison with the ion microprobe technique. It yields accurate δ¹⁸O data with an external precision better than 0.15‰. This is a significant methodological improvement for isotopic studies dealing with materials such as soil or biogenic oxides and silicates: particles are often too small and recovered in insufficient amount to be easily handled for ion microprobe analysis. Both techniques were used to investigate δ¹⁸O composition of a Cretaceous quartzite and silcrete sequence from the South-East of France. Quartzite cements average 31.04 ± 1.93‰. They formed from Mid-Cretaceous seawater. Higher in the series, silcretes cements average 26.66 ± 1.36‰. They formed from Upper- or post-Upper-Cretaceous soil water and groundwater. Oxygen isotope data show that the silicification steps from one mineralogical phase to another and from one layer to another (including from an upper pedogenic silcrete to a lower groundwater silcrete) occurred in a closed or weakly evaporating hydrological system.     

18.

Isotopic analysis of early solar system objects by an ion microprobe: Parametric studies and initial results     

J N Goswami  G Srinivasan 《Journal of Earth System Science》1994,103(1):57-82

Magnesium, potassium and calcium isotope compositions in terrestrial samples and refractory phases from primitive meteorites are determined using an ion microprobe. A thorough investigation of the different instrument parameters is carried out to ensure that conditions necessary for high mass resolution and high precision isotopic studies are adequately satisfied. The instrument can be tuned to achieve mass resolution (M/ΔM) of up to 10,000 (M≤60); it has a very good dynamic stability (ΔB/B≤10 ppm over durations of ≤40 minutes) and the counting system has an effective dead-time of ≤25 nsec and a dynamic background of ≤0·01 c/s. Reproducibility and precision of isotopic measurements are checked by analyzing magnesium and titanium isotopic compositions in terrestrial standards and isotopically doped silicate glasses. A precision of 2‰ (2σ _m ) was achieved during magnesium isotopic analysis in samples with low Mg content (200 ppm). Results from studies of magnesium and potassium isotopic compositions in several Ca−Al-rich refractory inclusions (CAIs) from the primitive meteorites Efremovka and Grosnaja, representing some of the early solar system objects, are presented. The well-behaved Mg−Al isotopic systematics confirm the pristine nature of the Efremovka CAIs inferred earlier from petrographic and trace element studies. The Grosnaja CAIs that have experienced secondary alterations show disturbed magnesium isotopic systematics. Observation of excess²⁶Mg in several of the analyzed CAIs confirms the presence of the now extinct²⁶Al (t _1/2=7×10⁵ years) in the solar nebula at the time of CAI formation. Our data also suggest a relatively uniform distribution of²⁶Al in the solar nebula. Several Efremovka CAIs with excess²⁶Mg also have excess⁴¹K resulting from the decay of⁴¹Ca (t _1/2≃10⁵ years). This observation constrains the time interval between cessation of nucleosynthetic input to the solar nebula and the formation of some of the first solar system solids (CAIs) to less than a million years.     

19.

Relationships between lithology and diagenesis in a limeston—marl facies transition: an electron microprobe study     

SARAH ANNE REECKMANN 《Sedimentology》1981,28(5):643-652

A 3 km long lateral facies transition from Oligo-Miocene skeletal grainstones into packstones and mudstones displays systematic variation in carbonate skeletal fragment alteration and secondary carbonate mineral composition. Within the skeletal grainstone end-member all aragonitic grains have dissolved, all Mg-calcite skeletal fragments have altered to calcite, and calcite has been precipitated as both void-filling spar and as syntaxial overgrowths on echinoid fragments. Within the transitional grainstone-packstone lithologies some skeletal fragments show preservation of their original mineralogy, while calcite, ferroan calcite spar and dolomite have precipitated in void spaces. Within the packstone-mudstone end-member of the transition, aragonitic grains have been preserved and Mg-calcite skeletal fragments have retained most of their magnesium. Thin, originally porous grainstone layers within the pack-stone-mudstones contain sideroplesite and ferroan calcite spar in void spaces, and iron has been incorporated in skeletal fragments which were originally Mg-calcite. In these grains iron has been incorporated at the expense of magnesium until the grains approach the composition of the surrounding ferroan calcite cement. The lateral variation in diagenetic alteration across this facies transition is a function of differing groundwater movement and composition, controlled ultimately by the composition, porosity and permeability of the host lithologies.     

20.

Constraining absolute deformation ages: the relationship between deformation mechanisms and isotope systematics     

《Journal of Structural Geology》1999,21(8-9):1255-1265

Isotope diffusion in a mineral is strongly temperature dependent but is also a function of grain size. Deformation must, therefore, be an important consideration in the interpretation of isotopic data because it provides a means of modifying grain size and shape. We illustrate the range of different deformation mechanisms common in micas and use simple models to investigate the relationship between these and isotope diffusion. We consider three different thermal scenarios with deformation taking place during: (a) the prograde heating path, (b) at the closure temperature of the deforming mineral, and (c) at temperatures significantly below the closure temperature. We have modelled these simple systems using a finite difference algorithm that simulates argon diffusion profiles and bulk ages. This modelling illustrates that obtaining deformation ages is critically dependent on an understanding and recognition of the different deformation mechanisms that have affected the sample. In the cases where deformation causes a change in grain size, it is important to characterise both the temperature at which deformation takes place and the closure temperature of grains formed during the deformation. The development of grains with T_c greater than the deformation temperature may record a deformation age. Examples of this condition include: (i) neocrystallisation; (ii) grain size reduction occurring at temperatures below T_c (of the reduced grain size) where the deformation mechanism has reset the grains; and (iii) deformation-induced grain coarsening.     

	$\text{d}{}_0\text{(}\text{cm}{}^2\text{/sec}\text{)}$	$\text{Q (}\text{kcal/g-atom O}\text{)}$	$\text{T(°C)}$
Adularia (Or98)	$\text{4.51 × 10}{}^{\mathrm{?8}}$	25.6	350–700
Albite (Ab97, Ab99)	$\text{2.31 × 10}{}^{\mathrm{?9}}$	21.3	350–800
Anorthite (An96)	$\text{1.39 × 10}{}^{\mathrm{?7}}$	26.2	350–800

Sulfur isotope study of Quaternary volcanic rocks from the Japanese Islands Arc

The sulfide and sulfate contents and their δ³⁴S values were determined in Quaternary volcanic rocks from the Japanese Islands Arc. The total sulfur contents are much lower (less than 40 ppm) and the δ³⁴S values are higher (+4.4 ± 2.1) than those of ocean-floor basalts (800 ± 100 ppm and +0.8 ± 0.5, respectively; Moore and Fabbi, 1971; Sakaiet al., 1982). Lateral variations of both sulfur content and δ³⁴S values were observed in the four volcanic belts in Japan. In the Northeast Japan belt, the sulfur content (30 ± 10 ppm) of the rocks in the inner zone (the Japan Sea side) is 3 to 5 times that in the outer zone (the Pacific side), although the δ³⁴S values of the two zones are almost the same (+4.3 ± 1.0). The δ³⁴S values for the two belts in West Japan are on the average 2%. higher than those of East Japan.This study suggests that the primary magmas that formed the island arc volcanic rocks are initially depleted in sulfur (<120 ppm) and enriched in ³⁴S ($\text{δ}{}^{34}\text{S: +5 ～ +7}$) compared to ocean-floor tholeiitic basalts which formed at mantle under oceanic region. This indicates that the upper-mantle is heterogeneous in sulfur content and isotope composition.     

Re-Os isotope systematics of sediments of the Brahmaputra River system

Re-Os analyses were performed on suspended loads and coarser grained bank sediments of the Brahmaputra River system. Re and Os concentrations of these sediments vary from 7 to 1154 ppt and from 3 to 173 ppt, respectively. ¹⁸⁷Os/¹⁸⁸Os ratios range from 0.178 to 6.8, and thus vary from nearly mantle to very radiogenic crustal values. Nevertheless, most of the sediments have ¹⁸⁷Os/¹⁸⁸Os ratios less than 1.5, and nearly all of the samples of the Brahmaputra main channel have ratios less than 1.2. Thus, as previously suggested, the Brahmaputra is much less radiogenic than the Ganga. The Siang River, the northern extension of the Brahmaputra, is quite radiogenic in Os despite receiving sediments from the Tsangpo River, which flows along a suture zone with ultramafic outcrops. The Brahmaputra main channel has a fairly constant ¹⁸⁷Os/¹⁸⁸Os ratio even though its tributaries contribute sediments with very heterogeneous Os isotopic compositions. These data, along with the corresponding Nd isotopic compositions, suggest that about 60-90% of the sediment in the Brahmaputra system is derived from Himalayan formations (Higher Himalaya and Lesser Himalaya) whereas 10-40% comes from ophiolite-bearing sequences, perhaps eastern equivalents of those of the Transhimalayan Plutonic Belt. Os data also confirm previously published Sr and Nd results, indicating that about half of the sediments delivered to the Brahmaputra are supplied by the Siang River, while the Himalayan and the eastern tributaries account for 40 and 10%, respectively.The lower ¹⁸⁷Os/¹⁸⁸Os of the Brahmaputra River compared to that of the Ganga is due to two factors. One is the more limited presence of the Lesser Himalaya and hence the lower black shale content of the eastern Himalaya. The other is the non-radiogenic Os supplied by the eastern and southern tributaries, reflecting the presence of mantle-derived lithologies in this region. Despite the lower sediment supply from these tributaries, they contribute greatly to the Os budget of the Brahmaputra River. This study indicates that the Brahmaputra River has little effect on the present-day seawater Os budget. However, reconsideration of this budget suggests that the Ganga, which provides the most radiogenic Os of major rivers studied to date, may have significant impact on the marine Os isotopic composition. The Indo-Asian collision cannot be excluded as an important cause of the increase in the marine ¹⁸⁷Os/¹⁸⁸Os over the past 16 million years until the contributions of all of the rivers draining the Himalayan Tibetan Plateau are known.     

Sulfur isotope biogeochemistry of the Proterozoic McArthur Basin

Previous geochemical and biomarker studies of the late Paleo-Mesoproterozoic propose a stratified world, with strongly reducing (possibly sulfidic) deep-ocean conditions overlain by an oxygenated surface-ocean and atmosphere. To investigate such a scenario, we look to the structure of the biogeochemical sulfur cycle. We present sulfur (³²S, ³³S, ³⁴S, and ³⁶S in sulfides) isotope data from the McArthur Basin (Barney Creek, Reward, Velkerri, and McMinn formations) that allows for a direct evaluation of the surface biosphere. We are interested in investigating the types of information that can be gained by including ³³S and ³⁶S. When the ³⁴S/³²S fractionations are small, the inclusion of ³³S and ³⁶S provides little additional information, but does provide ancillary evidence for relative isotopic homogeneity (with the internal consistency of ³³S/³²S and ³⁶S/³²S). When the ³⁴S/³²S fractionations are large, direct information about the fractionation mechanisms can be obtained, with the potential to distinguish the biological from abiological processes. For example, the reconstruction of the Roper Group suggests that seawater sulfate concentrations were high enough to buffer against spatial heterogeneities. Overall, our findings agree with previously proposed redox structure of the Proterozoic ocean, highlight contributions from the oxidative sulfur cycle, and outline a new tool for interpreting the state of the surface sulfur cycle.     

Petrogenesis of the Apollo 14 high-alumina basalts: Implications from ion microprobe analyses

In this study, ion microprobe analyses of individual minerals are used to investigate the petrogenesis of the Apollo 14 high-Al basalts. We use trace element concentrations from individual minerals in the Apollo 14 high-Al basalts to evaluate both endogenic and exogenic models. The data show that if the Apollo 14 high-Al basalts were produced by melting within the lunar mantle, these basalts cannot be related to one another by closed-system fractional crystallization of a single basaltic melt. Rather, the trace element data show that variable amounts of a KREEP component were added to the basalts by either assimilation, mixing into mantle sources, or impact melting. Single-stage assimilation-fractional crystallization models can only explain the data from this study if an excessively large mass of urKREEP is assimilated into the parent magma before olivine crystallization. Alternatively, the trace element data can be explained if the Apollo 14 high-Al basalts were produced by melting multiple Al-rich mantle sources that contain different amounts of urKREEP. Finally, for impact melting to be a relevant process, the data require that multiple large impact melts be formed from mixed KREEP-rich target lithologies. The resulting impact melts must then crystallize to produce basalts with igneous textures, high Al₂O₃ concentrations, uniform major element compositions, and a wide range of incompatible trace element concentrations.     

Oxygen isotope analyses of fine silica grains using laser-extraction technique: Comparison with oxygen isotope data obtained from ion microprobe analyses and application to quartzite and silcrete cement investigation

The laser fluorination technique reported here for analyzing the oxygen isotope composition (δ¹⁸O) of fine quartz size fractions 50-20, 20-10, 10-5, 5-2, 2-1 and <1 μm has been validated by comparison with the ion microprobe technique. It yields accurate δ¹⁸O data with an external precision better than 0.15‰. This is a significant methodological improvement for isotopic studies dealing with materials such as soil or biogenic oxides and silicates: particles are often too small and recovered in insufficient amount to be easily handled for ion microprobe analysis. Both techniques were used to investigate δ¹⁸O composition of a Cretaceous quartzite and silcrete sequence from the South-East of France. Quartzite cements average 31.04 ± 1.93‰. They formed from Mid-Cretaceous seawater. Higher in the series, silcretes cements average 26.66 ± 1.36‰. They formed from Upper- or post-Upper-Cretaceous soil water and groundwater. Oxygen isotope data show that the silicification steps from one mineralogical phase to another and from one layer to another (including from an upper pedogenic silcrete to a lower groundwater silcrete) occurred in a closed or weakly evaporating hydrological system.     

Isotopic analysis of early solar system objects by an ion microprobe: Parametric studies and initial results

Magnesium, potassium and calcium isotope compositions in terrestrial samples and refractory phases from primitive meteorites are determined using an ion microprobe. A thorough investigation of the different instrument parameters is carried out to ensure that conditions necessary for high mass resolution and high precision isotopic studies are adequately satisfied. The instrument can be tuned to achieve mass resolution (M/ΔM) of up to 10,000 (M≤60); it has a very good dynamic stability (ΔB/B≤10 ppm over durations of ≤40 minutes) and the counting system has an effective dead-time of ≤25 nsec and a dynamic background of ≤0·01 c/s. Reproducibility and precision of isotopic measurements are checked by analyzing magnesium and titanium isotopic compositions in terrestrial standards and isotopically doped silicate glasses. A precision of 2‰ (2σ _m ) was achieved during magnesium isotopic analysis in samples with low Mg content (200 ppm). Results from studies of magnesium and potassium isotopic compositions in several Ca−Al-rich refractory inclusions (CAIs) from the primitive meteorites Efremovka and Grosnaja, representing some of the early solar system objects, are presented. The well-behaved Mg−Al isotopic systematics confirm the pristine nature of the Efremovka CAIs inferred earlier from petrographic and trace element studies. The Grosnaja CAIs that have experienced secondary alterations show disturbed magnesium isotopic systematics. Observation of excess²⁶Mg in several of the analyzed CAIs confirms the presence of the now extinct²⁶Al (t _1/2=7×10⁵ years) in the solar nebula at the time of CAI formation. Our data also suggest a relatively uniform distribution of²⁶Al in the solar nebula. Several Efremovka CAIs with excess²⁶Mg also have excess⁴¹K resulting from the decay of⁴¹Ca (t _1/2≃10⁵ years). This observation constrains the time interval between cessation of nucleosynthetic input to the solar nebula and the formation of some of the first solar system solids (CAIs) to less than a million years.     

Relationships between lithology and diagenesis in a limeston—marl facies transition: an electron microprobe study

A 3 km long lateral facies transition from Oligo-Miocene skeletal grainstones into packstones and mudstones displays systematic variation in carbonate skeletal fragment alteration and secondary carbonate mineral composition. Within the skeletal grainstone end-member all aragonitic grains have dissolved, all Mg-calcite skeletal fragments have altered to calcite, and calcite has been precipitated as both void-filling spar and as syntaxial overgrowths on echinoid fragments. Within the transitional grainstone-packstone lithologies some skeletal fragments show preservation of their original mineralogy, while calcite, ferroan calcite spar and dolomite have precipitated in void spaces. Within the packstone-mudstone end-member of the transition, aragonitic grains have been preserved and Mg-calcite skeletal fragments have retained most of their magnesium. Thin, originally porous grainstone layers within the pack-stone-mudstones contain sideroplesite and ferroan calcite spar in void spaces, and iron has been incorporated in skeletal fragments which were originally Mg-calcite. In these grains iron has been incorporated at the expense of magnesium until the grains approach the composition of the surrounding ferroan calcite cement. The lateral variation in diagenetic alteration across this facies transition is a function of differing groundwater movement and composition, controlled ultimately by the composition, porosity and permeability of the host lithologies.     

Constraining absolute deformation ages: the relationship between deformation mechanisms and isotope systematics

Isotope diffusion in a mineral is strongly temperature dependent but is also a function of grain size. Deformation must, therefore, be an important consideration in the interpretation of isotopic data because it provides a means of modifying grain size and shape. We illustrate the range of different deformation mechanisms common in micas and use simple models to investigate the relationship between these and isotope diffusion. We consider three different thermal scenarios with deformation taking place during: (a) the prograde heating path, (b) at the closure temperature of the deforming mineral, and (c) at temperatures significantly below the closure temperature. We have modelled these simple systems using a finite difference algorithm that simulates argon diffusion profiles and bulk ages. This modelling illustrates that obtaining deformation ages is critically dependent on an understanding and recognition of the different deformation mechanisms that have affected the sample. In the cases where deformation causes a change in grain size, it is important to characterise both the temperature at which deformation takes place and the closure temperature of grains formed during the deformation. The development of grains with T_c greater than the deformation temperature may record a deformation age. Examples of this condition include: (i) neocrystallisation; (ii) grain size reduction occurring at temperatures below T_c (of the reduced grain size) where the deformation mechanism has reset the grains; and (iii) deformation-induced grain coarsening.