Determination of the Absolute Hydrogen Isotopic Ratio of V-SMOW and SLAP

By mixing ¹H₂O and ²H₂O, both with accurately known purity, samples were prepared with ²H/¹H ratios close to those of the international isotopic water standards: V-SMOW and SLAP. A mass spectrometrical comparison of these calibration samples with the actual water standards revealed:
²H/¹H of V-SMOW = (155.95 ± 0.08) × 10^−6
2H/¹H of SLAP = (89.12 ± 0.07) × 10⁻⁶
δ²H_V-SMOW(SLAP) =−428.5 ± 0.5 %     

Horizontal Strain Rate in Relation to Vein Formation of the Hishikari Gold Deposits, Southern Kyushu, Japan

Abstract: The Hishikari deposits comprise the Honko (Main), Yamada, and Sanjin deposits. The horizontal strain in the direction (approx. N40°W normal to the general NE-SW strike of the Hishikari vein system was calculated, based on the measured total vein widths to the distance along three crosscuts. Veins were assumed to accompany no significant fault displacement in the calculation. Veins in the eastern and the middle parts of the Honko-Sanjin deposits spatially occupy 3. 2% and 1. 3%, respectively, and veins in the Yamada deposit occupy 6. 7%. Significant local variation of strain is observed in some areas. Reported K-Ar ages on adularia-quartz veins indicate the duration of vein opening to be 2. 6 × 10⁵ yr in the Honko-Sanjin deposits and 5. 9 × 10⁵ yr in the Yamada deposit. Horizontal strain rates were calculated to be 5. 0–12 × 10^-8 yr^-1through the Hishikari deposits. The calculated strain rates at the Hishikari deposits are roughly comparable to the regional horizontal strain rate in the Recent. Widespread extensional movement in southern Kyushu seems to have been able to provide sufficient strain for the formation of the Hishikari deposits, rather than contribution of local movements.     

Diffusion-controlled corona reaction and overstepping of equilibrium in a garnet granulite, Yenisey Ridge, Siberia

Diffusion modelling is applied to layered garnet–pyroxene–quartz coronas, formed by a pressure-induced reaction between plagioclase and primary pyroxene in a metabasic granulite. The reconstructed reaction involves some change in composition of reactant minerals. The distribution of minerals between layers is satisfactorily explained by diffusion-controlled reaction with local equilibrium, in which the diffusion coefficient for Al was smaller than those for Fe, Mg and Ca by a factor of approximately four. Diffusion of Mg towards plagioclase implies a chemical-potential gradient for MgO component in a direction opposite to the changing Mg content of garnet; this is explained by the influence of Al₂O₃ on the chemical potential of the pyrope end-member. Grain-boundary diffusion is suggested to have operated, possibly with composition gradients different from those in the bulk minerals. Chemical-potential differences across the corona are estimated from the variation in garnet composition, enabling affinity (the free energy change driving the reaction) to be estimated as 6.9±1.8  kJ per 24-oxygen mole of garnet produced. This implies that the pressure for equilibrium among the minerals was overstepped by 1.4±0.4  kbar. The probable P–T conditions of reaction were in the range 650–790  °C, 8–10  kbar. Assuming a timescale of reaction between 10⁶ and 10⁸ years, estimated diffusion coefficients for Fe, Mg and Ca are in the range 9×10⁻²³ to 5×10⁻²⁰ m² s⁻¹. These are consistent with experimental values in the literature for solid-state diffusion, including grain-boundary diffusion.     

Eemian and Weichselian correlation problems in Finland

The Quaternary stratigraphy in Finland is discussed on the basis of an example from the Oulainen area of Ostrobothnia. Organogenic deposits found beneath till at this site are correlated with the Eemian Interglacial on biostratigraphical evidence. This is confirmed by TL dates of 97,000 ± 18,000 B.P. and 150,000 ± 30,000 B.P., whereas a finite radiocarbon date of 63,200 +⁵⁵⁰⁰ -₃₂₀₀ B.P. is probably too young. Correlation of the Weichselian stratigraphy is based on deep-sea oxygen isotope data, in which the variations in isotope ratios are assumed to reflect global changes in climate and fluctuations in the volume of the ice-caps. It is concluded on the latter grounds that Finland must have been free of ice at two periods during the Early Weichselian but at least for the most part covered by ice thereafter up to the final deglaciation. The sediments attributed to the only known Weichselian interstadial in Finland, the Perapohjola Interstadial, are taken to correspond most probably to the Brørup, although some may represent the Odderade, Information on the Weichselian till stratigraphy in the Oulainen area is largely confined to the deglaciation phase, the relatively complex nature of which suggests that complete reconstruction of the earlier phases of the Weichselian in an area such as Finland, located towards the centre of the ice sheet, is scarcely feasible by the methods currently available.     

Radiocarbon dating of subfossil Scots pine (Pinus sylvestris L.) in the southern Swedish Scandes

Wood samples from above the present-day pine limit were collected from within a limited area in central Sweden. New dates from an intensively investigated part of that area all fall within the period 8550 ± 110 to 4270 ± 90 ¹⁴C years B. P. No evidence at present exists to suggest that any drastic change, or fluctuations, in the pine tree-limit, took place within that period. Some dates support the view that the present-day altitude of the pine tree-limit was established during the historic period and perhaps is still declining.     

Preparation and Certification of Re-Os Dating Reference Materials: Molybdenites HLP and JDC

Two Re-Os dating reference material molybdenites were prepared. Molybdenite JDC and molybdenite HLP are from a carbonate vein-type molybdenum-(lead)-uranium deposit in the Jinduicheng-Huanglongpu area of Shaanxi province, China. The samples proved to be homogeneous, based on the coefficient of variation of analytical results and an analysis of variance test. The sampling weight was 0.1 g for JDC and 0.025 g for HLP. An isotope dilution method was used for the determination of Re and Os. Sample decomposition and pre-concentration of Re and Os prior to measurement were accomplished using a variety of methods: acid digestion, alkali fusion, ion exchange and solvent extraction. Negative thermal ionisation mass spectrometry and inductively coupled plasma-mass spectrometry were used for the determination of Re and ¹⁸⁷Os concentration and isotope ratios. The certified values include the contents of Re and Os and the model ages. For HLP, the Re content was 283.8 ± 6.2 μg g⁻¹, ¹⁸⁷Os was 659 ± 14 ng g⁻¹ and the Re-Os model age was 221.4 ± 5.6 Ma. For JDC, the Re content was 17.39 ± 0.32 μg g⁻¹, ¹⁸⁷Os was 25.46 ± 0.60 ng g⁻¹ and the Re-Os model age was 139.6 ± 3.8 Ma. Uncertainties for both certified reference materials are stated at the 95% level of confidence. Three laboratories (from three countries: PR. China, USA, Sweden) joined in the certification programme. These certified reference materials are primarily useful for Re-Os dating of molybdenite, sulfides, black shale, etc.     

New Constraints on Ages of Glasses Proposed as Reference Materials for Fission-Track Dating

New analyses have been performed in order to enhance the data-set on the independent ages of four glasses that have been proposed as reference materials for fission-track dating. The results are as follows. Moldavite - repeated ⁴⁰Ar/³⁹Ar age determinations on samples from deposits from Bohemia and Moravia yielded an average of 14.34 ± 0.08 Ma. This datum agrees with other recent determinations and is significantly younger than the ⁴⁰Ar/³⁹Ar age of 15.21 ± 0.15 Ma determined in the early 1980s. Macusanite (Peru) -four K-Ar ages ranging from 5.44 ± 0.06 to 5.72 ± 0.12 Ma have been published previously. New ⁴⁰Ar/³⁹Ar ages gave an average of 5.12 ± 0.04 Ma. Plateau fission-track ages determined using the IRMM-540 certified glass and U and Th thin films for neutron fluence measurements agree better with these new ⁴⁰Ar/³⁹Ar ages than the previously published ages. Roccastrada glass (Italy) - a new ⁴⁰Ar/³⁹Ar age, 2.45 ± 0.04 Ma, is consistent with previous determinations. The Quiron obsidian (Argentina) is a recently discovered glass that has been proposed as an additional reference material for its high spontaneous track density (around 100 000 cm^-2). Defects that might produce "spurious" tracks are virtually absent. An independent ⁴⁰Ar/³⁹Ar age of 8.77 ± 0.09 Ma was determined and is recommended for this glass. We believe that these materials, which will be distributed upon request to fission-track groups, will be very useful for testing system calibrations and experimental procedures.     

Chronology of deglaciation based on 10Be dates of glacial erosional features in the Grimsel Pass region, central Swiss Alps

Surface exposure dating, using in situ produced cosmogenic ¹⁰Be, is applied to determine the time since deglaciation of bedrock surfaces in the Grimsel Pass region. Nine ¹⁰Be dates from bedrock surfaces corrected for cover by snow are minimum ages for deglaciation of the pass. Four ¹⁰Be dates from surfaces below 2500 meters above sea level (m a.s.l.) on Nägelisgrätli, east of Grimsel Pass, yield ages that range from about 14 000 to 11 300 years. Three ¹⁰Be dates from locations above 2600 m a.s.l. on Nägelisgrätli are between about 11 700 and 10 400 years. Two ¹⁰Be dates from locations at 2560 m a.s.l. below Juchlistock are about 12 100 and 11 000 years. The geographical distribution of ¹⁰Be dates on Nägelisgrätli either may show the timing of progressive deglaciation of Grimsel Pass or may reflect differences in subglacial erosion of bedrock in the pass region. All dates are discussed in the context of deglaciation of the late Würmian Alpine ice cap and deglaciation from Last Glacial Maximum (LGM) ice extents in other regions.     

Deglaciation history of the southwestern Fennoscandian Ice Sheet between 15 and 13 14C ka BP

Analysis of 2D and 3D seismic records from the continental shelf off western Norway, in combination with chronological constraints from ¹⁴C dates, has led to a model for the glacial development in these shelf areas between c. 15 and 13 ¹⁴C ka BP. On the shallow Måløy Plateau adjacent to the Norwegian Channel, iceberg scours are preserved below a prominent moraine ridge, which by correlation to the Norwegian Channel indicate ice retreat at c. 15 ¹⁴C ka BP. Subsequently, the ice advanced across the scoured surface and deposited a till sheet before stabilizing to deposit a prominent moraine, termed the Bremanger Moraine. Based on location on the shelf, seismic stratigraphy, morphology and C dates the Bremanger Moraine is correlated with a significant moraine on the continental shelf off Trøndelag. We suggest that these features are products of a regional glacial event, the Bremanger Event, dated to <15–13.3 ¹⁴C ka BP. The Bremanger Event is probably a result of the deteriorating climatic conditions in the NE Atlantic during Heinrich event 1.     

Measurement of SIMS Instrumental Mass Fractionation of Pb Isotopes During Zircon Dating

An igneous zircon reference material (OG1) was characterised for U-Pb isotopes by ID-TIMS, and utilised to evaluate SIMS (SHRIMP) instrumental mass fractionation (IMF) of radiogenic Pb isotopes (²⁰⁷Pb*/²⁰⁶Pb*). The TIMS ²⁰⁷Pb*/²⁰⁶Pb* reference value for OG1 was 0.29907 ± 0.00011 (95% confidence limit), 3465.4 ± 0.6 Ma. The high ²⁰⁷Pb* (∼ 30 μg g⁻¹), negligible common Pb, and isotopic homogeneity permitted precise (± 1–2‰) ²⁰⁷Pb*/²⁰⁶Pb* measurements within the analytical sessions. External reproducibility of mean ²⁰⁷Pb*/²⁰⁶Pb* ratios between sessions was demonstrated for one instrument, yielding a mean IMF of +0.87 ± 0.49‰. The mean ²⁰⁷Pb*/²⁰⁶Pb* ratios between instruments were dispersed beyond uncertainties, with session IMF values from +3.6 ± 1.7‰ to −2.4 ± 1.3‰, and a grand mean IMF value (twenty-six sessions) of +0.70 ± 0.52‰, indicating a tendency towards elevated ²⁰⁷Pb*/²⁰⁶Pb*. The specific causes of variability in IMF are unclear, but generally reflect subtle differences in analytical conditions. The common practice in SIMS of assuming that IMF for Pb⁺ is insignificant could result in systematic age biases and underestimated uncertainties, of critical importance for precise correlation of Precambrian events. Nevertheless, a zircon RM such as OG1 can be readily incorporated into routine dating to improve ²⁰⁷Pb*/²⁰⁶Pb* accuracy and external reproducibility.     

Boron Isotopic Analysis of Proposed Borosilicate Mineral Reference Samples

This brief contribution presents new boron isotopic data for a set of proposed borosilicate reference minerals, most of which are described in the companion paper by Dyar et al.²⁰⁰¹. The results for a variety of minerals (tourmalines, danburite, prismatine, serendibite, ferroaxinite and a Li mica) show that it is generally possible to reproduce the ¹¹ B/¹⁰ B ratio within ± 0.5 per mil with replicate chemistry and mass spectrometry over long time spans. Because the accuracy of boron isotopic analysis is commonly determined by reference to secondary standards, it is suggested that some of the samples used in this study be adopted for interlaboratory comparisons and for quality control on boron isotopic analyses produced by a variety of analytical methods.     

The last deglaciation of the Franz Victoria Trough, northern Barents Sea

A study of two piston cores and a 3.5 kHz seismic profile from the Franz Victoria Trough provides new stratigraphic, stable isotopic and foraminiferal AMS ¹⁴C data that help constrain the timing of ice-sheet retreat in the northern Barents Sea and the nature of the deglacial marine environment. Silty diamicton at the base of each core, interpreted as till or ice-marginal debris flow, suggests that the Barents ice sheet was grounded at the core sites (470 m water depth). Eight AMS ¹⁴C dates on sediment overlying the diamicton indicate that the ice sheet retreated from both core sites by 12.9 ka and that postglacial sedimentation began 10 ka ago. These dates, combined with a recently published ¹⁴C date from a nearby core, suggest that the Franz Victoria Trough may not have been deglaciated until c . 13 ka, 2000 years later than modeled ice-sheet reconstructions indicate. In the trough, oxygen isotopic ratios in planktonic foraminifera ^N. pachyderma (sinistral) were 0.5–0.750, lower during deglaciation than after, probably as a result of ice-sheet and/or iceberg melting. Foraminiferal assemblages suggest that Atlantic-derived intermediate water may have begun to penetrate the trough c . 13 ka ago.     

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.     

Radiocarbon dating of marine shells, including a discussion of apparent age of Recent shells from Norway

General problems in determining and interpreting shell C¹⁴ dates are discussed: calculation methods, factors influencing primary activity (apparent age), and determination of contamination. It is concluded that shell dates are reliable when handled carefully. Measurements on ten shells, collected between 1898 and 1923 on the Norwegian coast, gave apparent ages from 340±75 to 550±80 years, indicating that apparent age is not a significant problem in dating of Norwegian shells.     

Re-Os Dating of Sulfides from the Volcanogenic Massive Sulfide Deposit at Gacun, Southwestern China

Abstract. The Re-Os isotopic compositions of sulfide ores were analyzed for the Gacun, a volcanogenic massive sulfide deposit in southwestern China, to constrain the timing of mineralization. Sulfide ores from the deposit have a wide range of Re and Os concentrations, varying from 80.2 to 1543.2 ppb and from 0.307 to 8.83 ppb, respectively, and yielded a limited field of high ¹⁸⁷Re/¹⁸⁸Os and high ¹⁸⁷Os/188Os ratios, ranging from 1452 to 3309 and from 5.77 to 13.24, respectively. All sulfide samples yielded an isochron with an age of 217±28 Ma and an initial ¹⁸⁷Os/¹⁸⁸Os ratio of around 0.52±0.73. The Re-Os isochron age agrees with ages previously constrained by the other isotopic dating of the host rocks and fossil strata for the deposit. The rhythmic variation in ¹⁸⁷Os/¹⁸⁸Os and ¹⁸⁷Re/¹⁸⁸Os ratios within massive sulfide zone records a complicated process for ore-forming fluids episodically vented into the brine pool on the Mesozoic seafloor.     

The Fossvogur marine sediments in SW Iceland - confined to the Allerød/Younger Dryas transition by AMS 14 C dating

An exhaustive ¹⁴C dating programme of molluscs from the Fossvogur sediments in Reykjavik. Iceland is presented. For the first time all the fossiliferous units of the sediments are dated. The results confirm earlier conclusions of a widespread occurrence of marine sediments of Allerød age in Reykjavik. The set of dates from the Fossvogur sediments shows a narrow ¹⁴C age distribution (standard deviation of ±235 years) of molluscs from all localities and from successive marine units in vertical sections. The weighted mean conventional ¹⁴C age is 11,400 BP. Assuming a reservoir effect of 400 years. this corresponds to a reservoir-corrected age of I1,000 BP. i.e. the Allerød- Younger Dryas transition for the sampled units, These new ¹⁴C dates from Fossvogur confirm the need for a revision of the Upper Pleistocene chronology of the Reykjavik region. They also have a bearing on the Late Weichselian record of glacier readvances and sea-level changes in the area. The dates suggest that the marine units in Fossvogur accumulated within a restricted time-span of a few hundred years. The sediments in Fossvogur are of volcaniclastic origin and are extremely lithified, indicating local geothermal activity soon after their deposition. This may explain anomalously high D/L amino acid ratios measured in molluscs from the Fossvogur sediments. δ¹³C and δ¹⁸O results suggest that temperatures may have ranged up to 60°C.     

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.     

Ore-Forming Fluid Characteristics of the Dayingezhuang Gold Deposit, Jiaodong Gold Province, China

The Dayingezhuang gold deposit is located in the central part of the Zhaoping Fault Zone, which is one of the most important gold-hosting faults in the Jiaodong gold province of China. Dayingezhuang is a typical large-scale shear zone-hosted disseminated gold deposit with superimposed silver mineralization. Fluid inclusion (FI) petrography and microthermometry, and analysis of oxygen and hydrogen isotopes for fluid inclusions were conducted to determine the characteristics of the ore-forming fluids and the processes of silver mineralization. Microthermometry data of FI indicated that ore-forming fluids are characterized by low salinity and low density. Homogenization pressures of FI are estimated at 20 × 10⁵–220 × 10⁵ Pa. The change in ore-forming fluids from K₂SO₄ type to NaCl type indicates the superposition of two hydrothermal mineralizing events. Ore-forming fluids were dominated by magmatic components in the early mineralization period, and affected by meteoric waters in the late period. Gold may have been transported as Au-S or Au-Cl complexes, whereas silver was transported as Ag-Cl complexes. Early fluid boiling and later fluid mixing are thought to be two of the main factors causing the deposition and superimposing of gold and silver to form the large deposit.     

Younger Dryas end moraines between Hardangerfjorden and Sognefjorden, Western Norway

End moraines (called the Herdla Moraines) from the Younger Dryas Stadial arc morphologically mapped along the western coast of Norway, from Hardangerfjorden to north of Sognefjorden. The submarine position of the moraines are found by means of a conventional echo sounder. Stratigraphieal studies with many C¹⁴ datings are used for age determination, giving Late Younger Dryas (10,000–10,500 C¹⁴ years B.P.) for the Herdla Moraines. The moraines are correlated with the Ra-Salpausselkä Moraines. Isobases for the Younger Dryas are obtained from marine terraces formed contemporaneously with the moraines.     

Rate of late Quaternary ice-cap thinning on King George Island, South Shetland Islands, West Antarctica defined by cosmogenic 36Cl surface exposure dating

Glacial landforms on the Barton and Weaver peninsulas of King George Island in the South Shetland Islands, West Antarctica were mapped and dated using terrestrial cosmogenic ³⁶Cl methods to provide the first quantitative terrestrial record for late Quaternary deglaciation in the South Shetland Islands. ³⁶Cl ages on glacially eroded and striated bedrock surfaces range from 15.5±2.5 kyr to 1.0±0.7 kyr. The ³⁶Cl ages are younger with decreasing altitude, indicating progressive downwasting of the southwestern part of the Collins Ice Cap at a rate of ∼12 mm yr⁻¹ since 15.5±2.5 kyr ago, supporting the previously published marine records for the timing and estimate of the rate of deglaciation in this region.