Sulfur Isotope Geochemistry of the Supergiant Xikuangshan Sb Deposit, Central Hunan, China: Constraints on Sources of Ore Constituents

Abstract. The supergiant Xikuangshan Sb deposit is located in the Middle to Upper Devonian limestone of central Hunan, China. Primary ores are composed of early-stage stibnite and calcite with rare pyrite, early main-stage stibnite and quartz, and late main-stage stibnite and calcite. New sulfur isotope data reveal the clustering of δ³⁴S values (+5 ∼ +8 %) for both early and late main-stage stibnite; a single early-stage stibnite exhibits δ³⁴S value (+7.5 %) identical to its main ore-stage counterparts and the coexisting calcite has almost unmodified carbon isotope composition (-4.4 %). The data suggest a probable common source of sulfur for stibnite that was deposited at different paragenetic stages. A much wider variation in δ³⁴S values for early main-stage stibnite (+3.5 to +16.3 %, av. +7.5 %) compared to that for late main-stage stibnite (+5.3 to +8.1 %, av. +6.2 %) can be interpreted to be due to local interaction of earlier ore fluid with Devonian host rocks. The previous studies show that the Precambrian basement contains elevated Sb concentrations, and two distinctive sulfur reservoirs with δ³⁴S_pyrite values at ca. +11 ∼ +24 % and -7.0 ∼-11 %. The homogenizing effect for sulfur hydrothermally leached from the two reservoirs might have provided ore constituents for the Xikuangshan fluids.     

Boron Isotopic Composition and Concentration of Ten Geological Reference Materials

We present boron isotope and concentration data from magmatic (komatiitic to rhyolitic) and sedimentary geological silicate and artificial glass reference materials that cover a wide spectrum of boron isotope compositions and boron concentrations. Boron isotope compositions were determined by TIMS (Cs₂BO₂⁺ -graphite and BO₂^- method) and boron concentrations by ICP-AES. Boron concentrations ranged from 7 to 159μ g^-1 and agree within 14% with published values. Based on replicate analyses of individually prepared sample aliquots an overall external reproducibility of better than 10% was determined. The obtained δ¹¹B values ranged from -12.6 to +13.6% and were reproducible within 1.1 % (2 RSD; excluding NTIMS) on the basis of individually prepared sample aliquots. The δ¹¹B values of JA-1 (+5.3%), JB-3 (+5.9%) and JR-2 (+2.9%) overlap the published data within analytical uncertainty. For the first time δ¹¹B values for the TB (-12.6%) and the MPI-DING glasses GOR-128-G (+13.6%), GOR-132-G (+7.1 %) and StHs6/80-G (-4.5%) are reported. The δ¹¹B values obtained by the Cs₂BO₂⁺ -graphite and the BO₂^- method as well as the majority of δ¹¹B values obtained using different sample preparation methods agree within analytical uncertainty. Therefore, we conclude that none of these analytical methods introduce any systematic error on the obtained δ¹¹B values.     

Climate variability in the SE Alps of Italy over the past 17 000 years reconstructed from a stalagmite record

Stalagmite SV1 from Grotta Savi, located at the SE margin of the European Alps (Italy), is the first Alpine speleothem that continuously spans the past c . 17kyr. Extension rate and δ¹⁸O_c record for the Lateglacial probably reflect a combination of temperature and rainfall, with rainfall exerting the dominant effect. Low speleothem calcite δ¹⁸ O_c values were recorded from c . 14.5 and 12.35 kyr, during GI-1 (Bølling— Allerød) interstadial, which in our interpretation, was warm and wet. The GS-1 (Younger Dryas) was characterized by a shift to heavier δ¹⁸ O_c, coinciding with δ¹³C_c enrichment and extremely low extension rate (<8 μm/year). These characteristics indicate that GS-1 climate was cool and dry in the SE Alps. Calibration using historical data revealed that there is a positive δ¹⁸O_c/dT relationship. A 1°C rise in mean annual temperature should correspond to c . 2.85% increase of SV-1 δc¹⁸O_c. We reconstructed a slow and steady temperature rise of c . 0.5°C since 10 kyr BP, in broad agreement with reconstructions from pollen data for SE Europe. Stalagmite SV1 indicates that climate variability in the SE Alps has been influenced by the Mediterranean Sea for the past c . 17 kyr.     

Chemical Separation and Isotopic Variations of Cu and Zn From Five Geological Reference Materials

This paper presents an adapted anion exchange column chemistry protocol which allowed separation of high-purity fractions of Cu and Zn from geological materials. Isobaric and non-spectral interferences were virtually eliminated for consequent multiple-collector ICP-MS analysis of the isotopic composition of these metals. The procedure achieved ∼ 100% recoveries, thus ensuring the absence of column-induced isotopic fractionation. By employing these techniques, we report isotopic analyses for Cu and Zn from five geological reference materials: BCR-027 blende ore (BCR), δ⁶⁵Cu = 0.52 ± 0.15‰ (n = 10) and δ⁶⁶Zn = 0.33 ± 0.07‰ (n = 8); BCR-030 calcined calamine ore (BCR), δ⁶⁶Zn = -0.06 ± 0.09‰ (n = 8); BCR-1 basalt (USGS), δ⁶⁶Zn = 0.29 ± 0.12‰ (n = 8); NOD-P-1 manganese nodule (USGS), δ⁶⁵Cu = 0.46 ± 0.08‰ (n = 10) and δ⁶⁶Zn = 0.78 ± 0.09‰ (n = 9); SU-1 Cu-Co ore (CCRMP), δ⁶⁵Cu = -0.018 ± 0.08‰ (n = 10) and δ⁶⁶Zn = 0.13 ± 0.17‰ (n = 6). All uncertainties are ± 2s; copper isotope ratios are reported relative to NIST SRM-976, and zinc isotope ratios relative to the Lyon-group Johnson Matthey metal (batch 3-0749 L) solution, JMC Zn. These values agree well with the limited data previously published, and with results reported for similar natural sample types. Samples were measured using a GVi IsoProbe MC-ICP-MS, based at the Natural History Museum, London. Long-term measurement reproducibility has been assessed by repeat analyses of both single element and complex matrix samples, and was commonly better than ± 0.07‰ for both δ⁶⁶Zn and δ⁶⁵Cu.     

Heavy Sulfur-isotope Enrichment in Middle Miocene Onnagawa Mudstones in the Green Tuff Region, Northeastern Japan

Abstract. Sulfur isotope ratios are analyzed for a series of mudstones in a successive section in the Taiheizan area in the central Green Tuff region, northeast Japan. The δ³⁴S values for the Uyashinai Mudstone Member (Nishikurosawa stage), the Onnagawa Formation and the Funakawa Formation range from -45 to -14%, -20 to +4% and -30 to -10%, respectively. There is a marked positive shift in δ³⁴S values at the Nishikurosawa/Onnagawa boundary and an upward δ³⁴S-decreasing trend in the Onnagawa and Funakawa Formations. The present data provides evidence for environmental change in the form of stratification of the seawater, initiated at the Nishikurosawa/Onnagawa boundary and persisting during deposition of the Onnagawa Formation, followed by gradual oxygenation during deposition of the Funakawa Formation.     

The isotopic composition of oxygen and carbon in the subfossil mollusc shells of the Baltic Sea as an indicator of palaeosalinity

The carbon (δ¹³ C) and oxygen (δ¹⁸O) isotopic composistion in mollusc shells in mainly determined by the isotopic composition of water and dissolved bicarbonate. The δ¹⁸O values of water show a good correlation with the salinity of the Baltic. This correlation served as a basis for reconstructing palaeosalinity and for stratifying the marine sediments according to the δ¹⁸O values of the carbonate skeletons of subfossil shells. The δ¹³C values in shells are mainly determined by the isotopic composition of land-originating bicarbonate, especially in the carbonate skeleton of Lymnaea balthica , which inhabits the immediate coastal zone. According to the δ¹⁸O data, salinity in the investigated area (the coastal area of W and NW Estonia) was highest (about 9–11%) during the Littorina stage. The Limnae a stage had, in general, a salinity similar to the contemporary one, but during some phases possibly exceeding it by 2–3%.     

Stable isotopic signature of a palaeoaquifer, Mississippian Alamogordo Member limestones, Sacramento Mountains, New Mexico, USA

Nine stratigraphic sections, each ≈5 m thick, were sampled from the Alamogordo Member limestones of the Lake Valley Formation, Sacramento Mountains, New Mexico, USA. Four stratigraphic sections consist entirely of lime mudstone and wackestone, whereas the other five sections have a prominent layer of crinoidal packstone about 1 m thick at their base. Stable isotopic analyses reveal that the lime muds in the sections with basal packstone layers show a downward decrease in δ¹⁸O and constant δ¹³C values, whereas those in the sections solely composed of lime mudstone and wackestone have, in general, relatively uniform δ¹⁸O and δ¹³C values. The diagenesis of the Alamogordo Member limestones was previously believed to have been governed by the downward percolation of meteoric water from a regional pre-Pennsylvanian exposure surface ≈100 m above this unit. However, the uniform δ¹³C and downward decrease in δ¹⁸O values in the lime muds in the sections with basal packstones indicate that the meteoric water ascended within the Alamogordo Member, rather than descended from the overlying exposure surface. This indicates that the basal packstones were probably a conduit for meteoric water. This is further supported indirectly by the relatively uniform δ¹⁸O and δ¹³C values of the lime mud in the sections without basal packstones. The implications are that the oxygen isotopic gradients may be used to identify palaeoaquifers, flow directions within these aquifers and that meteoric diagenesis below an exposure surface could be governed by flow through a palaeoaquifer.     

Stable isotope study of carbonate sediments from the Coorong Area, South Australia

ABSTRACT
The mineralogy and isotope geochemistry of carbonate minerals in the Coorong area are determined by the water chemistry of different depositional environments ranging from seawater to evaporitically modified continental water. The different isotopic compositions of coexisting calcite and dolomite suggest that each of the above two minerals was formed from water of composition and origin unique to that specific mineral. In addition, the dolomite was not formed by simple solid state cation exchange.
The occurrence of two types of dolomite was shown by isotope analysis and SEM observations. The dolomite, which is isotopically light (δ¹³C = -1 to -2% 0 ; δ¹⁸O=+3 to +5%₀) and of fine grain size (˜ 0·5 μm) probably precipitated under the influence of evaporitically modified continental water. Coarser grained dolomite (up to 4 μm) is isotopically heavier (δ¹³C=+3 to +4%₀; δ¹⁸O=+5 to + 6%₀) contains Mg in excess of Ca and was formed in or close to equilibrium with atmospheric CO² probably by the dolomitization of aragonite.     

Genesis of Kanggur Gold Deposit in Eastern Tianshan Orogenic Belt, NW China: Fluid Inclusion and Oxygen and Hydrogen Isotope Constraints

Abstract. Primary fluid inclusions in quartz and carbonates from the Kanggur gold deposit are dominated by aqueous inclusions, with subsidiary CO₂-H₂O inclusions that have a constant range in CO₂ content (10–20 vol %). Microthermometric results indicate that total homogenization temperatures have a wide but similar range for both aqueous inclusions (120 to 310C) and CO₂-H₂O inclusions (140 to 340C). Estimates of fluid salinity for CO₂-H₂O inclusions are quite restricted (5.9∼10.3 equiv. wt% NaCl), whereas aqueous inclusions show much wider salinity ranging from 2.2 to 15.6 equivalent wt %NaCl.
The 6D values of fluid inclusions in carbonates vary from -45 to -61 %, in well accord with the published δD values of fluid inclusions in quartz (-46 to -66 %). Most of the δ¹⁸O and δD values of the ore-forming fluids can be achieved by exchanged meteoric water after isotopic equilibration with wall rock by fluid/rock interaction at a low water/rock ratio. However, the exchanged meteoric water alone cannot explain the full range of δ¹⁸O and δD values, magmatic and/or meta-morphic water should also be involved. The wide salinity in aqueous inclusions may also result from mixing of meteoric water and magmatic and/or metamorphic water.     

Hydrogen, Oxygen and Sulfur Isotope Studies of Seafloor Hydrothermal System at the Desmos Caldera, Manus Back-arc Basin, Papua New Guinea: An Analogue of Terrestrial Acid Hot Crater-lake

Abstract. The Onsen site is an active submarine hydrothermal system hosted by the Desmos caldera in the Eastern Manus Basin, Papua New Guinea. The hydrothermal fluid is very acidic (pH=1.5) and abundant native sulfur is deposited around the vent. The δ³⁴S values of native sulfur range from -6.5 to -9.3 %o. δ³⁴S values of H₂S and SO₄ in the hydrothermal fluid are -4.3 to -9.9 %o and +18.6 to +20.0 %o, respectively. These δ³⁴S values are significantly lower than those of the other hydrothermal systems so far reported. These low δ³⁴S values and the acidic nature of the vent fluids suggest that volcanic SO₂ gas plays an important role on the sulfur isotope systematic of the Onsen hydrothermal system. Relationship among the δ³⁴S values of S-bearing species can be successively explained by the model based on the disproportionation reaction starting from the volcanic SO₂ gas. The predicted δ³⁴S values of SO₂ agree with the measured whole rock δ³⁴S values. δD and δ¹⁸O values of clay minerals separated from the altered rock samples also suggest the contribution of the magmatic fluid to the hydrothermal system. Present stable isotopic study strongly suggests that the Onsen hydrothermal site in the Desmos caldera is a magmatic submarine hydrothermal system.     

Refinements in BaSO4 to CO2 Preparation and δ18 O Calibration of the Sulfate Reference Materials NBS-127, IAEA SO-5 and IAEA SO-6

Refinements have been made to achieve over 99% yield in the conversion of CO to CO₂ in order to improve the reproducibility and accuracy of δ¹⁸ O measurements in sulfates. BaSO₄ (10-15 mg) was mixed with an identical amount of spectrographic-grade graphite and loaded into a Pt boat. The mixture was gradually heated to 1100 °C to reduce sulfate to CO and CO₂; the former gas was simultaneously converted to CO₂ by a glow discharge between Pt electrodes immersed in a magnetic field (produced by a pair of external neodymium magnets). A small memory effect was noticed during the analysis (less than 0.3‰ per 10‰ difference in δ¹⁸ O between two subsequently analysed samples). The memory effect, however, was suppressed by repetitive preparation of the same specimen. CO₂ produced in this way from sulfate reference samples was analysed on a dual inlet and triple collector mass spectrometer along with CO₂ equilibrated with VSMOW, GISP and SLAP water reference samples. To avoid large departures of measured isotope ratios from ¹⁸O/¹⁶O of the working calibrator we used CO₂ gas prepared from ocean water sulfate for this purpose. The calibrated δ¹⁸ O values (in ‰) obtained in this way for NBS-127, IAEA SO-5 and IAEA SO-6 reference materials were 8.73 ± 0.05, 12.20 ± 0.07 and -10.43 ± 0.12, respectively.     

U-Pb Zircon Geochronology with an Integrated LA-ICP-MS Microanalytical Workstation: Achievements in Precision and Accuracy

Laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) is a microanalytical tool especially suitable for providing fast and precise U-Pb geochronological results on zircon grains. A new 193 nm excimer laser adapted to a micromachining workstation, equipped with a newly designed two-volume ablation cell and coupled with a quadrupole ICP-MS, is presented here. The system was tuned routinely to achieve sensitivities in the range of 3000 cps/μg g⁻¹ for ²³⁸U (< 2% RSD), with a 34 μm spot size, at 5 Hz and ∼ 8 J cm⁻², while ablating the NIST SRM 612 glass reference material. The system was capable of providing fast (< 1.5 minutes each analysis) and precise (generally < 1.5% 1s errors) ²⁰⁶Pb/²³⁸U zircon ages. The ages of widely used reference material zircons (Plesovice, 337 Ma; Temora, 416 Ma; R33, 418 Ma; Sri Lanka, 564 Ma; 91500, 1065 Ma) could be precisely matched, with an accuracy on isotopic ratios that ranged from ∼ 2 to ∼ 6%, depending on the homogeneity of the natural reference materials.     

Geochemical Process of Gas Hydrate Formation in the Nankai Trough Based on Chloride and Isotopic Anomalies in Interstitial Water

Abstract: Interstitial water expelled from gas hydrate-bearing and -free sediments in the Nankai Trough are analyzed in terms of Cl-, SO₄²-, δ¹⁸O and δD. The baselines for the Cl- concentration and δ¹⁸O value are close to seawater values (530 mM and 0%), indicating that the interstitial water is of seawater origin. The δD values decrease with depth, implying isotopic exchange of hydrogen between upwelling biogenic methane depleted in D and interstitial water. The Cl- concentrations in gas hydrate-bearing sediments are anomalously low, while the δ¹⁸O and δD values are both high, suggesting that the water forming these gas hydrates was poor in Cl- and enriched in ¹⁸O and D during gas hydrate formation. Calculation of the gas hydrate saturations using Cl "and δ¹⁸O anomalies gives results of up to 80 % in sand, and shows that the δ¹⁸O baseline is not consistent with the Cl" baseline. The δ¹⁸O baseline increases by +1% in gas hydrate-free clay and silt. This is considered to be caused by clustering of water molecules after gas hydrate dissociation in response to the upward migration of the base of gas hydrate stability, as indicated by the presence of a double bottom-simulating reflector at this site. The water clusters enriched in ¹⁸O are responsible for the increase in the δ¹⁸O baseline with normal Cl". The abrupt shallowing of the base of gas hydrate stability may induce the dissociation of gas hydrates and the accumulation of gases in the new stability zone, representing a geological process that increases gas hydrate saturation.     

Isotope geochemistry, petrology and depositional environments of the diatomite-dominated Tripoli Formation (Lower Messinian), Sicily

ABSTRACT The Tripoli Formation (Lower Messinian) in Sicily includes diatomites irregularly alternating with marl and carbonate beds and lies, stratigraphically, between the Tortonian pelagic marls and the evaporitic Calcare di base. The relationships between mineralogy, textural features and oxygen-carbon isotopic compositions of carbonate components point to a wide variability of depositional conditions and suggest that Tripoli sedimentation occurred in small basins characterized by periodic and marked restriction from the open sea.
The isotopic values of calcite and dolomite in the diatomites suggest an evolution from normal marine towards more restricted environments. Evaporating conditions are also indicated by the occurrence of anhydrite, length-slow chalcedonic quartz and moulds of gypsum. In a more advanced stage, the precipitation of heavy δ¹⁸0 dolomite in the interstitial pores of fossil-poor diatomites denotes an environment with highly evaporated water. Mixing of meteoric and marine waters, on the other hand, might have favoured the precipitation of a dolomite characterized by relatively low δ¹⁸0 and δ¹³C values.
The deposition of marl and carbonate beds alternating with or overlying the diatomites took place in an environment with highly evaporated marine waters on the basis of δl¹⁸O values of dolomite (up to + 9.10‰) and aragonite (up to + 5.83‰), occurrence of evaporitic minerals and lack of fossils. The presence at these levels of calcite with extremely negative δ¹³C values (down to - 38.40‰), filling gypsum moulds, suggests activity of sulphate-reducing bacteria. Some aragonitic marls, however, bear evidence of deposition in relatively normal marine conditions.     

A distinct δ13C decline in organic lake sediments at the Pleistocene-Holocene transition in southern Sweden

Values of δ¹³C obtained from conventional bulk sediment radiocarbon dates encompassing the Pleistocene Holocene boundary have been compiled and plotted against ¹⁴C age. In all. 286 lake sediment dates from southern Sweden in the range 8.000 to 13.000 BP have been evaluated. A significant decrease in δ¹³C values, initiated shortly before 10.000 RP and amounting to 5%, is distinguished. This change is accompanied by increased limnic productivity. decreased erosive input and increased organic carbon content of the sediments. A probable explanation for the δ¹³C decline in organic material is decreased importance of dissolution of silicates at the transition to the Holocene. During the Late Weichselian. extensive weathering of exposed minerogenic material with subsequent input of bicarbonate to the lake water may have caused a relative enrichment of ¹³C in dissolved inorganic carbon. Furthermore, the early Holocene increase in terrestrial vegetation cover probably led to an increased supply of ¹³C depleted carbon dioxide to the lake water by root respiration. Altered limnic vegetation, presumably towards increased production of phytoplankton. could also have contributed to the observed decreasing δ¹³C trend. The importance of these processes compared to other possible influencing factors. mainly endogenic carbonate production and changes in the global carbon cycle. is discussed.     

Foraminiferal changes and geochemical profiles across the Cenomanian/Turonian boundary in central and south-east Poland

Two sections of the Upper Cenomanian and Lower Turonian in central and south-east Poland were investigated for foraminifers, CaCO₃content, carbon content insoluble in HCl (C_org) and in the carbonates (C_carb), carbon and oxygen isotopic composition of bulk-rock carbonates and elemental abundances. The Cenomanian/Turonian boundary interval is characterized by the appearance of more marly facies, a δ¹³C and δ¹⁸O stable isotope anomaly, a considerable increase in C_org content and decrease in C_carb content and substantial changes in the foraminiferal assemblages. A major carbon stable isotope excursion with a shift of +2 (PDB) occurs in the lowermost Whiteinella archaeocretacea Zone. The late Cenomanian δ¹³C anomaly is associated with heavy δ¹⁸O values. The peak value of δ¹³C corresponds to the minima in P/B ratio and in diversity of foraminiferal assemblages. A late Cenomanian anoxic event is thought to be responsible for changes in foraminiferal assemblages. However, elemental abundance analyses do not show changes in the concentrations of trace elements. This may be explained by the long distance between studied area and a source of enrichment which was probably located in the western hemisphere.     

Stable chlorine isotope evidence for non-marine chloride in Badenian evaporites, Carpathian mountain region

Routine trace-element geochemistry suggests that components in putative marine halite evaporites may be partly of nonmarine origin, but such interpretations are commonly ambiguous. Stable chlorine isotopes may provide a less-ambiguous marker of chloride origin where δ³⁷Cl departs from the range predicted for evaporite formation from seawater. Bedded halite with primary sedimentary textures preserves original δ³⁷Cl values. Measurable change in δ³⁷Cl can be generated by incongruent dissolution of halite, but only if less than half the original halite remains. Badenian (middle Miocene) halite from the Forecarpathian and from the East Slovakian and Transcarpathian basins has a δ³⁷Cl range of – 0.2 to 0.8‰. Two phenomena cannot be explained by simple evaporation of 0.0‰ seawater. At Wieliczka, the Shaft Salt has distinctive δ³⁷Cl values (– 0.2 to 0.0‰) relative to neighbouring salt beds (0.2 to  0.6‰), requiring a large, abrupt input of brine with negative δ³⁷Cl. Halite with high (0.6 – 0.8‰) δ³⁷Cl near the base of the East Slovakian and Transcarpathian evaporites requires a large input of chloride with positive δ³⁷Cl into the basins. Expulsion of basin brine with non-0‰δ³⁷Cl into the evaporite basins may account for the nonmarine chloride sources.     

Geochemical Characteristics of the Akiyoshi Limestones, Japan and Their Bearing on Exploration for Blind Skarn Deposits

Abstract. Carboniferous-Permian limestones of the Akiyoshi Plateau, in the Inner Zone of southwestern Japan, are composed of essentially pure calcium carbonate containing only small amounts of other elements, and they are accompanied by marble and copper skarn deposits near the contact with late Cretaceous granitoids. The δ¹⁸O values of the Akiyoshi limestones range widely from 7.6 to 28.3% and are mostly lower than those of other areas of the same age (23–29%), whereas the differences among the δ¹³C values are small. The δ¹⁸O values are negatively correlated with Mn and Fe contents. Samples with high δ¹⁸O (>25%) and δ¹³C (>2%) values do not contain Fe, Zn, or Pb, but those with low δ¹⁸O values tend to be rich in these elements, indicating that these elements were introduced by interaction with H₂O dominant fluids, possibly of magmatic origin. Potential scores for evaluating the degree of interaction with hydro thermal fluids were calculated for δ¹⁸O, δ¹³C, Fe, Mn, Zn, Pb, and Sr. Higher scores implying much hydrothermal interaction were evident in the Mt. Hananoyama area, where there are many skarn deposits, and along faults oriented mainly NNW-SSE. Therefore, these are promising areas for exploring for blind deposits. It is likely that the hydrothermal fluid traveled through the limestones along fractures at the time of the granitic intrusions. However, the potential scores here are much smaller than those in the Pb-Zn mineralized area of the Kamioka mine, so more detailed petrological and mineralogical investigations are necessary.     

δ30Si and δ29Si Determinations on USGS BHVO-1 and BHVO-2 Reference Materials with a New Configuration on a Nu Plasma Multi-Collector ICP-MS

We report silicon isotopic determinations for USGS rock reference materials BHVO-1 and BHVO-2 using a Nu Plasma multi-collector (MC)-ICP-MS, upgraded with a new adjustable entrance slit, to obtain medium resolution, as well as a stronger primary pump and newly designed sampler and skimmer cones ("B" cones). These settings, combined with the use of collector slits, allowed a resolution to be reached that was sufficient to overcome the ¹⁴N¹⁶O and ¹⁴N₂ interferences overlying the ³⁰Si and the ²⁸Si peaks, respectively, in an earlier set-up. This enabled accurate measurement of both δ³⁰Si and δ²⁹Si. The δ value is expressed in per mil variation relative to the NBS 28 quartz reference material. Based on data acquired from numerous sessions spread over a period of six months, we propose a recommended average δ³⁰Si of −0.33 ± 0.05‰ and −0.29 ± 0.11‰ (2se) for BHVO-1 and BHVO-2, respectively. Our BHVO grand mean silicon isotope composition (δ³⁰Si =−0.31 ± 0.06‰) is significantly more negative than the only published value for BHVO-2, but is in very good agreement with the recently established average value of ocean island basalts (OIB), confirming the conclusion that the OIB reservoir has a distinct isotopic composition from the solar reservoir as sampled by chondrites.     

Calcium Isotopic Composition of Various Reference Materials and Seawater

A compilation of δ^44/40Ca (δ^44/40Ca) data sets of different calcium reference materials is presented, based on measurements in three different laboratories (Institute of Geological Sciences, Bern; Centre de Géochimie de la Surface, Strasbourg; GEOMAR, Kiel) to support the establishment of a calcium isotope reference standard. Samples include a series of international and internal Ca reference materials, including NIST SRM 915a, seawater, two calcium carbonates and a CaF₂ reference sample. The deviations in δ^44/40Ca for selected pairs of reference samples have been defined and are consistent within statistical uncertainties in all three laboratories. Emphasis has been placed on characterising both NIST SRM 915a as an internationally available high purity Ca reference sample and seawater as representative of an important and widely available geological reservoir. The difference between δ^44/40Ca of NIST SRM 915a and seawater is defined as -1.88 O.O4%o (δ^44/42Ca_{NISTSRM915a/Sw}= -0.94 0.07%o). The conversion of values referenced to NIST SRM 915a to seawater can be described by the simplified equation δ^44/40Ca_Sa/Sw=δ^44/40Ca_{Sa/NIST SRM 915a} - 1.88 (δ^44/42Ca_Sa/Sw=δ^44/42Ca_{Sa/NIST SRM 915a} - 0.94). We propose the use of NIST SRM 915a as general Ca isotope reference standard, with seawater being defined as the major reservoir with respect to oceanographic studies.