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1.
Three tourmaline reference materials sourced from the Harvard Mineralogical and Geological Museum (schorl 112566, dravite 108796 and elbaite 98144), which are already widely used for the calibration of in situ boron isotope measurements, are characterised here for their oxygen and lithium isotope compositions. Homogeneity tests by secondary ion mass spectrometry (SIMS) showed that at sub‐nanogram test portion masses, their 18O/16O and 7Li/6Li isotope ratios are constant within ± 0.27‰ and ± 2.2‰ (1s), respectively. The lithium mass fractions of the three materials vary over three orders of magnitude. SIMS homogeneity tests showed variations in 7Li/28Si between 8% and 14% (1s), which provides a measure of the heterogeneity of the Li contents in these three materials. Here, we provide recommended values for δ18O, Δ’17O and δ7Li for the three Harvard tourmaline reference materials based on results from bulk mineral analyses from multiple, independent laboratories using laser‐ and stepwise fluorination gas mass spectrometry (for O), and solution multi‐collector inductively coupled plasma‐mass spectroscopy (for Li). These bulk data also allow us to assess the degree of inter‐laboratory bias that might be present in such data sets. This work also re‐evaluates the major element chemical composition of the materials by electron probe microanalysis and investigates these presence of a chemical matrix effect on SIMS instrumental mass fractionation with regard to δ18O determinations, which was found to be < 1.6‰ between these three materials. The final table presented here provides a summary of the isotope ratio values that we have determined for these three materials. Depending on their starting mass, either 128 or 512 splits have been produced of each material, assuring their availability for many years into the future.  相似文献   

2.
Measurement of Ba isotope ratios of widely available reference materials is required for interlaboratory comparison of data. Here, we present new Ba isotope data for thirty‐four geological reference materials, including silicates, carbonates, river/marine sediments and soils. These reference materials (RMs) cover a wide range of compositions, with Ba mass fractions ranging from 6.4 to 1900 µg g?1, SiO2 from 0.62% to 90.36% m/m and MgO from 0.08% to 41.03% m/m. Accuracy and precision of our data were assessed by the analyses of duplicate samples and USGS rock RMs. Barium isotopic compositions for all RMs were in agreement with each other within uncertainty. The variation of δ138/134Ba in these RMs was up to 0.7‰. The shale reference sample, affected by a high degree of chemical weathering, had the highest δ138/134Ba (0.37 ± 0.03‰), while the stream sediment obtained from a tributary draining carbonate rocks was characterised by the lowest δ138/134Ba (?0.30 ± 0.05‰). Geochemical RMs play a fundamental role in the high‐precision and accurate determination of Ba isotopic compositions for natural samples with similar matrices. Analyses of these RMs could provide universal comparability for Ba isotope data and enable assessment of accuracy for interlaboratory data.  相似文献   

3.
A HF‐free sample preparation method was used to purify silicon in twelve geological RMs. Silicon isotope compositions were determined using a Neptune instrument multi‐collector‐ICP‐MS in high‐resolution mode, which allowed separation of the silicon isotope plateaus from their interferences. A 1 μg g‐1 Mg spike was added to each sample and standard solution for online mass bias drift correction. δ30Si and δ29Si values are expressed in per mil (‰), relative to the NIST SRM 8546 (NBS‐28) international isotopic RM. The total variation of δ30Si in the geological reference samples analysed in this study ranged from ‐0.13‰ to ‐0.29‰. Comparison with δ29Si values shows that these isotopic fractionations were mass dependent. IRMM‐17 yielded a δ30Si value of ‐1.41 ± 0.07‰ (2s, n = 12) in agreement with previous data. The long‐term reproducibility for natural samples obtained on BHVO‐2 yielded δ30Si = ‐0.27 ± 0.08‰ (2s, n = 42) on a 12 month time scale. An in‐house Si reference sample was produced to check for the long‐term reproducibility of a mono‐elemental sample solution; this yielded a comparable uncertainty of ± 0.07‰ (2s, n = 24) over 5 months.  相似文献   

4.
Tourmalinization associated with peraluminous granitic intrusions in metapelitic host-rocks has been widely recorded in the Iberian Peninsula, given the importance of tourmaline as a tracer of granite magma evolution and potential indicator of Sn-W mineralizations. In the Penamacor-Monsanto granite pluton (Central Eastern Portugal, Central Iberian Zone), tourmaline occurs: (1) as accessory phase in two-mica granitic rocks, muscovite-granites and aplites, (2) in quartz (±mica)-tourmaline rocks (tourmalinites) in several exocontact locations, and (3) as a rare detrital phase in contact zone hornfels and metapelitic host-rocks. Electron microprobe and stable isotope (δ18O, δD, δ11B) data provide clear distinctions between tourmaline populations from these different settings: (a) schorl–oxyschorl tourmalines from granitic rocks have variable foititic component (X□ = 17–57 %) and Mg/(Mg + Fe) ratios (0.19–0.50 in two-mica granitic rocks, and 0.05–0.19 in the more differentiated muscovite-granite and aplites); granitic tourmalines have constant δ18O values (12.1 ± 0.1 ‰), with wider-ranging δD (?78.2 ± 4.7 ‰) and δ11B (?10.7 to ?9.0 ‰) values; (b) vein/breccia oxyschorl [Mg/(Mg + Fe) = 0.31–0.44] results from late, B- and Fe-enriched magma-derived fluids and is characterized by δ18O = 12.4 ‰, δD = ?29.5 ‰, and δ11B = ?9.3 ‰, while replacement tourmalines have more dravitic compositions [Mg/(Mg + Fe) = 0.26–0.64], close to that of detrital tourmaline in the surrounding metapelitic rocks, and yield relatively constant δ18O values (13.1–13.3 ‰), though wider-ranging δD (?58.5 to ?36.5 ‰) and δ11B (?10.2 to ?8.8 ‰) values; and (c) detrital tourmaline in contact rocks and regional host metasediments is mainly dravite [Mg/(Mg + Fe) = 0.35–0.78] and oxydravite [Mg/(Mg + Fe) = 0.51–0.58], respectively. Boron contents of the granitic rocks are low (<650 ppm) compared to the minimum B contents normally required for tourmaline saturation in granitic melts, implying loss of B and other volatiles to the surrounding host-rocks during the late-magmatic stages. This process was responsible for tourmalinization at the exocontact of the Penamacor-Monsanto pluton, either as direct tourmaline precipitation in cavities and fractures crossing the pluton margin (vein/breccia tourmalinites), or as replacement of mafic minerals (chlorite or biotite) in the host-rocks (replacement tourmalinites) along the exocontact of the granite. Thermometry based on 18O equilibrium fractionation between tourmaline and fluid indicates that a late, B-enriched magmatic aqueous fluid (av. δ18O ~12.1 ‰, at ~600 °C) precipitated the vein/breccia tourmaline (δ18O ~12.4 ‰) at ~500–550 °C, and later interacted with the cooler surrounding host-rocks to produce tourmaline at lower temperatures (400–450 °C), and an average δ18O ~13.2 ‰, closer to the values for the host-rock. Although B-metasomatism associated with some granitic plutons in the Iberian Peninsula seems to be relatively confined in space, extending integrated studies such as this to a larger number of granitic plutons may afford us a better understanding of Variscan magmatism and related mineralizations.  相似文献   

5.
东秦岭地区是我国重要的花岗伟晶岩区及稀有金属成矿区.电气石在东秦岭各类花岗伟晶岩中广泛发育,通常在无矿化伟晶岩、铍矿化及锂矿化伟晶岩中呈黑色-深蓝色.本文旨在通过各类伟晶岩中电气石的对比研究揭示电气石地球化学特征对东秦岭伟晶岩矿化类型的指示作用.本文所研究电气石为作为东秦岭各类伟晶岩贯通矿物的黑电气石系列.在双峰村、碾...  相似文献   

6.
The Hattu schist belt is located in the western part of the Archaean Karelian domain of the Fennoscandian Shield. The orogenic gold deposits with Au–Bi–Te geochemical signatures are hosted by NE–SW, N–S and NW–SE oriented shear zones that deform 2.76–2.73 Ga volcanic and sedimentary sequences, as well as 2.75–2.72 Ga tonalite–granodiorite intrusions and diverse felsic porphyry dykes. Mo–W mineralization is also present in some tonalite intrusions, both separate from, and associated with Au mineralization. Somewhat younger, unmineralized leucogranite intrusions (2.70 Ga) also intrude the belt. Lower amphibolite facies peak metamorphism at 3–5 kbar pressures and at 500–600 °C temperatures affected the belt at around 2.70 Ga and post-date hydrothermal alteration and ore formation. In this study, we investigated the potential influence of magmatic-hydrothermal processes on the formation of orogenic gold deposits on the basis of multiple stable isotope (B, S, Cu) studies of tourmaline and sulphide minerals by application of in situ SIMS and LA ICP MS analytical techniques.Crystal chemistry of tourmaline from a Mo–W mineralization hosted by a tonalite intrusion in the Hattu schist belt is characterized by Fe3 +–Al3 +-substitution indicating relatively oxidizing conditions of hydrothermal processes. The range of δ11B data for this kind of tourmaline is from − 17.2‰ to − 12.2‰. The hydrothermal tourmaline from felsic porphyry dyke swith gold mineralization has similar crystal chemistry (e.g. dravite–povondraite compositional trend with Fe3 +–Al3 + substitution) and δ11B values between − 19.0‰ and − 9.6‰. The uvite–foitite compositional trend and δ11B ‰ values between − 24.1% and − 13.6% characterize metasomatic–hydrothermal tourmaline from the metasediment-hosted gold deposits. Composition of hydrothermal vein-filling and disseminated tourmaline from the gold-bearing shear zones in metavolcanic rocks is transitional between the felsic intrusion and metasedimentary rock hosted hydrothermal tourmaline but the range of average boron isotope data is essentially identical with that of the metasediment-hosted tourmaline. Rock-forming (magmatic) tourmaline from leucogranite has δ11B values between − 14.5‰ and − 10.8‰ and the major element composition is similar to that of the metasediment-hosted tourmaline.The range of δ34SVCDT values measured in pyrite, chalcopyrite and pyrrhotite is from − 9.1 to + 8.5‰, which falls within the typical range of sulphur isotope data for Archaean orogenic gold deposits. In the Hattu schist belt, positive δ34SVCDT values characterize metasediment-hosted gold ores with sulphide parageneses dominated by pyrrhotite and arsenopyrite. The δ34SVCDT values are both positive and negative in ore mineral parageneses within felsic intrusive rocks in which variable amounts of pyrrhotite are associated with pyrite. Purely negative values were only recorded from the pyrite-dominated gold mineralization within metavolcanic units. Therefore the shift of δ34SVCDT values to the negative values reflects precipitation of sulphide minerals from relatively oxidizing fluids. The range of measured δ65CuNBS978 values from chalcopyrite is from − 1.11 to 1.19‰. Positive values are common for mineralization in felsic intrusive rocks and negative values are more typical for deposits confined to metasedimentary rocks. Positive and negative δ65CuNBS978 values occur in the ores hosted by metavolcanic rocks. There is no correlation between sulphur and copper isotope data obtained in the same chalcopyrite grains.Evaluation of sulphur and boron isotope data together and comparisons with other Archaean orogenic gold provinces supports the hypothesis that the metasedimentary rocks were the major sources of sulphur and boron in the orogenic gold deposits in the Hattu schist belt. Variations in major element and boron isotope compositions in tourmaline, as well as in the δ34SVCDT values in sulphide minerals are attributed to localized involvement of magmatic fluids in the hydrothermal processes. The results of copper isotope studies indicate that local sources of copper in orogenic gold deposits may potentially be recognized if the original, distinct signatures of the sources have not been homogenized by widespread interaction of fluids with a large variety of rocks and provided that local chemical variations have been too small to trigger changes in the oxidation state of copper during hydrothermal processes.  相似文献   

7.
To enable quality control of measurement procedures for determinations of Mg isotope amount ratios, expressed as δ26Mg and δ25Mg values, in Earth‐surface studies, the δ26Mg and δ25Mg values of eight reference materials (RMs) were determined by interlaboratory comparison between five laboratories and considering published data, if available. These matrix RMs, including river water SLRS‐5, spring water NIST SRM 1640a, Dead Sea brine DSW‐1, dolomites JDo‐1 and BCS‐CRM 512, limestone BCS‐CRM 513, soil NIST SRM 2709a and vegetation NIST SRM 1515, are representative of a wide range of Earth‐surface materials from low‐temperature environments. The interlaboratory variability, 2s (twice the standard deviation), of all eight RMs ranges from 0.05 to 0.17‰ in δ26Mg. Thus, it is suggested that all these materials are suitable for validation of δ26Mg and δ25Mg determinations in Earth‐surface geochemical studies.  相似文献   

8.
The Houxianyu borate deposit in northeastern China is one of the largest boron sources of China, hosted mainly in the Paleoproterozoic meta-volcanic and sedimentary rocks (known as the Liaohe Group) that are characterized by high boron concentrations. The borate ore-body has intimate spatial relationship with the Mg-rich carbonates/silicates of the Group, with fine-grained gneisses (meta-felsic volcanic rocks) as main country rocks. The presence of abundant tourmalinites and tourmaline-rich quartz veins in the borate orebody provides an opportunity to study the origin of boron, the nature of ore-forming fluids, and possible mineralization mechanism. We report the chemical and boron isotopic compositions of tourmalines from the tourmaline-rich rocks in the borate deposit and from the tourmaline-bearing fine-grained gneisses.Tourmalines from the fine-grained gneisses are chemically homogeneous, showing relatively high Fe and Na and low Mg, with δ11B values in a narrow range from +1.22‰ to +2.63‰. Tourmalines from the tourmaline-rich rocks, however, commonly show compositional zoning, with an irregular detrital core and a euhedral overgrowth, and have significantly higher Mg, REE (and more pronounced positive Eu anomalies), V (229–1852 ppm) and Sr (208–1191 ppm) than those from the fine-grained gneisses. They show varied B isotope values ranging from +4.51‰ to +12.43‰, which plot intermediate between those of the terrigenous sediments and arc rocks with low boron isotope values (as represented by the δ11B = +1.22‰ to +2.63‰ of the fine-grained gneisses of this study) and those of marine carbonates and evaporates with high boron isotope values. In addition, the rim of the zoned tourmaline shows notably higher Mg, Ti, V, Sn, and Pb, and REE (particularly LREEs), but lower Fe, Co, Cr, Ni, Zn, Mn, and lower δ11B values than the core. These data suggest that (1) the sources of boron of the borate ore-body are mainly the Paleoproterozoic meta-volcanic and sedimentary rocks, and (2) the ore-forming fluids should be the high temperature metamorphic fluids related to the amphibolite-facies metamorphism of the Paleoproterozoic foldbelt, which leach boron from the boron-rich meta-volcanic and sedimentary rocks of the Liaohe Group, and the boron-rich metamorphic fluids subsequently interacted with the marine Mg-rich carbonates and evaporates, forming borate deposit, the tourmaline overgrowth in the rim and the tourmaline-rich rocks.  相似文献   

9.
Two quartz samples of igneous origin, UNIL‐Q1 (Torres del Paine Intrusion, Chile) and BGI‐Q1 (Shandong province, China), were calibrated for their oxygen isotope composition for SIMS measurements. UNIL‐Q1 and BGI‐Q1 were evaluated for homogeneity using SIMS. Their reference δ18O values were determined by CO2 laser fluorination. The average δ18O value found for UNIL‐Q1 is 9.8 ± 0.06‰ and that for BGI‐Q1 is 7.7 ± 0.11‰ (1s). The intermediate measurement precision of SIMS oxygen isotope measurements was 0.32–0.41‰ (2s; UNIL‐Q1) and 0.40–0.48‰ (2s; BGI‐Q1), respectively. While less homogeneous in its oxygen isotope composition, BGI‐Q1 is also suitable for SIMS trace element measurements.  相似文献   

10.
Identifying evidence of oxidative weathering in the geological record is essential to trace the evolution of Earth's atmosphere oxygenation. Metamorphosed residues of lateritic weathering have been identified as two rock types in the 2.1‐Ga‐old Cercadinho Formation, Piracicaba Group, Quadrilátero Ferrífero of Minas Gerais. One is tourmaline–hematite–sillimanite–kyanite quartzite; the other is rutile–tourmaline–hematite–muscovite phyllite. Both rocks have abundant tourmaline with δ11B values between about ?17‰ and ?13‰. The Cercadinho tourmaline is roughly parallel to the povondraite–“oxy‐dravite” join of meta‐evaporitic tourmaline, in its more aluminous segment, offset to higher contents of iron. These compositional and isotopic characteristics of the Cercadinho tourmaline indicate that continental evaporitic brines interacted with aluminium‐ and iron‐rich residues of lateritic weathering. The abundance of disseminated tourmaline, a mineral poorly reported from palaeosols worldwide, implies a boron‐rich brine overprint on the lateritic profile before the onset of metamorphism, reflecting a climatic change from humid to arid conditions in a continental setting. The recognition of lateritic weathering in the Cercadinho Formation contributes to the amount of evidence for increased levels of atmospheric oxygen between 2.22 and 2.06 Ga ago.  相似文献   

11.
This study explores the effects of cation composition on mass bias (i.e., the matrix effect), which is a major component of instrumental mass fractionation (IMF) in the microanalyses of δ13C and δ18O by SIMS in carbonates of the magnesite–siderite solid‐solution series (MgCO3–FeCO3). A suite of twelve calibration reference materials (RMs) was developed and documented (calibrated range: Fe# = 0.002–0.997, where Fe# = molar Fe/[Mg + Fe]), along with empirical expressions for regressing calibration data (affording residuals < 0.5‰ relative to certified reference material NIST‐19). The calibration curves of both isotope systems are non‐linear and have, over a 2‐year period, fallen into one of two distinct but largely self‐consistent shape categories (data from ten measurement sessions), despite adherence to well‐established analytical protocols for carbonate δ13C and δ18O analyses at WiscSIMS (CAMECA IMS 1280). Mass bias was consistently most sensitive to changes in composition near the magnesite end‐member (Fe# 0–0.2), deviating by up to 4.5‰ (δ13C) and 14‰ (δ18O) with increasing Fe content. The cause of variability in calibration curve shapes is not well understood at present and demonstrates the importance of having available a sufficient number of well‐characterised RMs so that potential complexities of curvature can be adequately delineated and accounted for on a session‐by‐session basis.  相似文献   

12.
Sulfur isotope measurements in three sulfide (two pyrite and one pyrrhotite) samples on two epoxy mounts showed that the mount‐to‐mount variation of raw δ34S values was negligible when secondary ion mass spectrometry (SIMS) analytical settings remained stable. In consequence, an off‐mount calibration procedure for SIMS sulfur isotope analysis was applied in this study. YP136 is a pyrrhotite sample collected from northern Finland. Examination of thin sections with a polarising microscope, backscattered electron image analyses and wavelength dispersive spectrometry mapping showed that the sample grains display no internal growth or other zoning. A total of 318 sulfur isotope (spot) measurements conducted on more than 100 randomly selected grains yielded highly consistent sulfur isotope ratios. The repeatability of all the analytical results of 34S/32S was 0.3‰ (2s, n = 318), which is the same as that of the well‐characterised pyrite reference materials PPP‐1 and UWPy‐1. Its δ34S value determined by gas mass spectrometry was 1.5 ± 0.1‰ (2s, n = 11), which agrees with the SIMS data (1.5 ± 0.3‰, 2s) calibrated by pyrrhotite reference material Po‐10. Therefore, YP136 pyrrhotite is considered a candidate reference material for in situ sulfur isotope determination.  相似文献   

13.
In eastern Elba Island (Tuscany, Italy), a shallow crustal level felsic, tourmaline‐bearing, dyke‐sill swarm of Late Miocene age is associated with abundant tourmaline‐quartz hydrothermal veins and metasomatic masses. Development of these veins and masses in the host rocks demonstrates multiple hydro‐fracturing by magmatic, boron‐rich saline fluid. Tourmalines in felsic dykes are schorl, whereas in veins and metasomatic masses, tourmaline composition ranges from schorl‐dravite through dravite to uvite. This compositional shift is evidence for an increasing contribution to the magmatic boron‐rich fluids by a Mg‐Ca‐Ti‐rich external component represented by biotite‐rich and amphibolite host rocks. This system can be envisaged as an exposed proxy of the high temperature hydrothermal system presently active in the deepest part of the Larderello‐Travale geothermal field (Tuscany).  相似文献   

14.
为了对西藏错那洞电气石花岗岩源区进一步约束,利用显微镜、电子探针和激光剥蚀多接收等离子质谱仪,对错那洞电气石花岗岩中电气石的形态、成分及硼同位素组成进行了研究.结果表明,错那洞电气石花岗岩中的电气石为碱族黑/铁电气石,直接结晶自富硼熔体,与熔体之间未发生明显的硼同位素分馏.电气石δ11B值主要在-6.91‰^-9.17‰之间,与大陆地壳平均δ11B值(-10‰±3‰)相近,表明错那洞电气石花岗岩主要源自变质沉积岩的部分熔融.然而,与起源于变质沉积岩的花岗岩相比,样品的δ11B值明显偏高,而与前人报道的雅拉香波淡色花岗岩(源自石榴石角闪岩部分熔融)的δ11B值相似.因此,错那洞电气石花岗岩源区中,除了变质沉积岩外,可能还混入了少量石榴石角闪岩.  相似文献   

15.
This study is Part II of a series that documents the development of a suite of calibration reference materials for in situ SIMS analysis of stable isotope ratios in Ca‐Mg‐Fe carbonates. Part I explored the effects of Fe2+ substitution on SIMS δ18O bias measured from the dolomite–ankerite solid solution series [CaMg(CO3)2–CaFe(CO3)2], whereas this complementary work explores the compositional dependence of SIMS δ13C bias (calibrated range: Fe# = 0.004–0.789, where Fe# = molar Fe/(Mg+Fe)). Under routine operating conditions for carbonate δ13C analysis at WiscSIMS (CAMECA IMS 1280), the magnitude of instrumental bias increased exponentially by 2.5–5.5‰ (session‐specific) with increasing Fe‐content in the dolomite structure, but appeared insensitive to minor Mn substitution [< 2.6 mole % Mn/(Ca+Mg+Fe+Mn)]. The compositional dependence of bias (i.e., the matrix effect) was expressed using the Hill equation, yielding calibration residual values ≤ 0.3‰ relative to CRM NBS‐19 for eleven carbonate reference materials (6‐μm‐diameter spot size measurements). Based on the spot‐to‐spot repeatability of a drift monitor material that ‘bracketed’ each set of ten sample‐spot analyses, the analytical precision was ± 0.6–1.2‰ (2s, standard deviations). The analytical uncertainty for individual sample analyses was approximated by combining the precision and calibration residual values (propagated in quadrature), suggesting an uncertainty of ± 1.0–1.5‰ (2s).  相似文献   

16.
We report here an optimisation of the demountable direct injection high efficiency nebuliser (d‐DIHEN) for isotopic measurements with a Neptune (ThermoFisher Scientific, Bremen, Germany) multi‐collector inductively coupled plasma‐mass spectrometer (MC‐ICP‐MS) and describe a method for boron isotopic ratio determination. With direct injection nebulisation 100% of the analyte was introduced into the ICP‐MS plasma and wash times were drastically reduced for elements such as boron and thorium. Compared to the classical stable introduction system (SIS: double Scott/cyclonic spray chamber), sensitivity for boron was 2–5 times higher with d‐DIHEN and wash times up to ten times shorter. Repeatability of 11B/10B sample‐calibrator bracketing measurements reached 0.25‰ (2s) for seawater and coral samples. Method accuracy and reproducibility were tested on mixed reference solutions having δ11B values in the ranges ?90 to +40‰ and ?2 to +2.5‰, demonstrating our ability to distinguish δ11B values with differences of only 0.25‰. The international seawater reference material NRCC NASS‐5 (National Research Council, Ottawa, Canada), analysed in different sessions over a 10‐month period, yielded an average δ11B value of +39.89 ± 0.25‰, in the upper range of previously published seawater values. A comparison between δ11B determined by d‐DIHEN MC‐ICP‐MS and positive‐TIMS (P‐TIMS) for four modern corals showed an excellent agreement (with bias of less than 0.4‰).  相似文献   

17.
The high‐precision δ60/58Ni values of twenty‐six geological reference materials, including igneous rocks, sedimentary rocks, stream sediments, soils and plants are reported. The δ60/58Ni values of all samples were determined by double‐spike MC‐ICP‐MS (Nu Plasma III). Isotope standard solution (NIST SRM 986) and geological reference materials (BHVO‐2, BCR‐2, JP‐1, PCC‐1, etc.) were used to evaluate the measurement bias and intermediate precision over a period of six months. Our results show that the intermediate precision of Ni isotope determination was 0.05‰ (2s, n = 69) for spiked NIST SRM 986 and typically 0.06‰ for actual samples, and the δ60/58Ni NIST SRM 986 values were in excellent agreement with previous studies. Eighteen high‐precision Ni isotope ratios of geological reference materials are first reported here, and their δ60/58Ni values varied from ?0.27‰ to 0.52‰, with a mean of 0.13 ± 0.34‰ (2s, n = 18). Additionally, SGR‐1b (0.56 ± 0.04‰, 2s), GSS‐1 (?0.27 ± 0.06‰, 2s), GSS‐7 (?0.11 ± 0.01‰, 2s), GSD‐10 (0.46 ± 0.06‰, 2s) and GSB‐12 (0.52 ± 0.06‰, 2s) could potentially serve as candidate reference materials for Ni isotope fractionation and comparison of Ni isotopic compositions among different laboratories.  相似文献   

18.
Various metacarbonate and associated calc-silicate rocks form minor but genetically significant components of the lithological units in the Bohemian Massif of the Variscan orogen in Central Europe.These rocks vary in terms of their lithostratigraphy,chemical composition and mineral assemblage(dolomite/calcite ratio,silicate abundance).Tourmaline is present in five paragenetic settings within the metacarbonate and calc-silicate units.TypeⅠcomprises individual,euhedral,prismatic grains and grain aggregates in a carbonate-dominant(calcite±dolomite)matrix poor in silicates.TypeⅡis characterized by euhedral to subhedral grains and coarse-to fine-grained aggregates in silicate-rich layers/nests within metacarbonate bodies whereas typeⅢoccurs as prismatic grains and aggregates at the contact zones between carbonate and associated silicate host rocks.TypeⅣis in veins crosscutting metacarbonate bodies,and typeⅣtourmaline occurs at the exocontacts of elbaite-subtype granitic pegmatite.Tourmaline from the different settings shows distinctive compositional features.Typical for typeⅠare Mg-rich compositions,with fluor-uvite>dravite>>magnesio-lucchesiite.Tourmalines from typeⅡsilicate-rich layers/nests are highly variable,corresponding to oxy-schorl,magnesio-foitite,Al-rich dravite and fluor-uvite.Typical for typeⅢtourmalines are Ca,Ti-bearing oxy-dravite compositions.The typeⅣveins feature dravite and fluor-uvite tourmaline compositions whereas typeⅤtourmaline is Li,F-rich dravite.Tourmaline is the only Bbearing phase in paragenetic typesⅠ-Ⅳ,where it is characterised by two principal ranges of B-isotope composition(δ^11B=-13‰to-9‰and-18‰to-14‰).These ranges correspond to regionally different units of the Moldanubian Zone.Thus,the Svratka Unit(Moldanubian Zone s.l.)contains only isotopically lighter tourmaline(δ^11B=-18‰to-14‰),whereas metacarbonates in the Poli?ka unit(Teplá-Barrandian Zone)and Olesnice unit(Moravicum of the Moravo-Silesian Zone)has exclusively isotopically heavier tourmaline(δ^11B=-9‰to-13‰).Tourmalines from metacarbonates in the Variegated Unit cover both ranges of isotope composition.The isotopically light end of the B isotope range may indicate the presence of continental evaporites within individual investigated areas.On the other hand,variations in the range of~8δ-units is consistent with the reported shift in B isotopic composition of metasedimentary rocks of the Bohemian Massif due to the prograde metamorphism from very-low grade to eclogite facies.In contrast to the metacarbonate-hosted settings,tourmaline of paragenetic type V from the exocontact of granitic pegmatites displays a significantly heavier range ofδ^11B(as low as-7.7‰to-0.6‰),which is attributed to partitioning of 10 B to cogenetic axinite and/or different B-signature of the source pegmatite containing tourmaline with heavyδ^11B signature.  相似文献   

19.
Isotopic reference materials are essential to enable reliable and comparable isotope data. In the case of boron only a very limited number of such materials is available, thus preventing adequate quality control of measurement results and validation of analytical procedures. To address this situation a unique set of two boron isotope reference materials (ERM‐AE102a and ‐AE104a) and three offset δ11B reference materials (ERM‐AE120, ‐AE121 and ‐AE122) were produced and certified. The present article describes the production and certification procedure in detail. The isotopic composition of all the materials was adjusted by mixing boron parent solutions enriched in 10B or 11B with a boron parent solution having a natural isotopic composition under full gravimetric control. All parent solutions were analysed for their boron concentration as well as their boron isotopic composition by thermal ionisation mass spectrometry (TIMS) using isotope dilution as the calibration technique. For all five reference materials the isotopic composition obtained on the basis of the gravimetric data agreed very well with the isotopic composition obtained from different TIMS techniques. Stability and homogeneity studies that were performed showed no significant influence on the isotopic composition or on the related uncertainties. The three reference materials ERM‐AE120, ERM‐AE121 and ERM‐AE122 are the first reference materials with natural δ11B values not equal to 0‰. The certified δ11B values are ?20.2‰ for ERM‐AE120, 19.9‰ for ERM‐AE121 and 39.7‰ for ERM‐AE122, each with an expanded uncertainty (k = 2) of 0.6‰. These materials were produced to cover about three‐quarters of the known natural boron isotope variation. The 10B enriched isotope reference materials ERM‐AE102a and ERM‐AE104a were produced for industrial applications utilising 10B for neutron shielding purposes. The certified 10B isotope abundances are 0.29995 for ERM‐AE102a and 0.31488 for ERM‐AE104a with expanded uncertainties (k = 2) of 0.00027 and 0.00028, respectively. Together with the formerly certified ERM‐AE101 and ERM‐AE103 a unique set of four isotope reference materials and three offset δ11B reference materials for boron isotope determination are now available from European Reference Materials.  相似文献   

20.
The Qiman Tagh W-Sn belt lies in the westernmost section of the East Kunlun Orogen, NW China, and is associated with early Paleozoic monzogranites, tourmaline is present throughout this belt. In this paper we report chemical and boron isotopic compositions of tourmaline from wall rocks, monzogranites, and quartz veins within the belt, for studying the evolution of ore-forming fluids. Tourmaline crystals hosted in the monzogranite and wall rocks belong to the alkali group, while those hosted in quartz veins belong to both the alkali and X-site vacancy groups. Tourmaline in the walk rocks lies within the schorl-dravite series and becomes increasingly schorlitic in the monzogranite and quartz veins. Detrital tourmaline in the wall rocks is commonly both optically and chemically zoned,with cores being enriched in Mg compared with the rims. In the Al-Fe-Mg and Ca-Fe-Mg diagrams,tourmaline from the wall rocks plots in the fields of Al-saturated and Ca-poor metapelite, and extends into the field of Li-poor granites, while those from the monzogranite and quartz veins lie within the field of Li-poor granites. Compositional substitution is best represented by the MgFe_(-1), Al(NaR)_(-1), and AlO(Fe(OH))_(-1) exchange vectors. A wider range of δ~(11)B values from -11.1‰ to -7.1‰ is observed in the wall-rock tourmaline crystals, the B isotopic values combining with elemental diagrams indicate a source of metasediments without marine evaporates for the wall rocks in the Qiman Tagh belt. The δ~(11)B values of monzogranite-hosted tourmaline range from -10.7‰ and-9.2‰, corresponding to the continental crust sediments, and indicate a possible connection between the wall rocks and the monzogranite. The overlap in δ~(11)B values between wall rocks and monzogranite implies that a transfer of δ~(11)B values by anataxis with little isotopic fractionation between tourmaline and melts. Tourmaline crystals from quartz veins have δ~(11)B values between -11.0‰ and-9.6‰, combining with the elemental diagrams and geological features, thus indicating a common granite-derived source for the quartz veins and little B isotopic fractionation occurred. Tourmalinite in the wall rocks was formed by metasomatism by a granite-derived hydrothermal fluid, as confirmed by the compositional and geological features.Therefore, we propose a single B-rich sedimentary source in the Qiman Tagh belt, and little boron isotopic fractionation occurred during systematic fluid evolution from the wall rocks, through monzogranite, to quartz veins and tourmalinite.  相似文献   

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