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.     

The Use of Multiple Reference Samples for the Monitoring of Ion Microprobe Performance During Zircon 207Pb/206Pb Age Determinations

Data from a series of extended analytical sessions using a range of different zircon reference samples have been used to investigate the periodic derivation of abnormal ²⁰⁷Pb/²⁰⁶Pb ages during microbeam analysis%For the Canberra SHRIMP II, this phenomenon probably results from the presence of a signal at mass 204 that is alien to the Pb spectrum; isotopic fractionation is unlikely to be a significant contributor. In contrast, abnormal ²⁰⁷Pb/²⁰⁶Pb ages obtained from SHRIMP I at the same research centre require a different, but as yet unknown explanation. Assessment of the reasons for atypical ^207Pb/²⁰⁶Pb measurements and the means of correcting for them should therefore be independently assessed for individual analytical instruments. The use of reference samples with very different ages is an effective way of doing this, because older reference samples are more useful for documenting isotopic fractionation, whereas younger ones are more sensitive indicators of isobaric interference.     

Natural Cadmium Isotopic Variations in Eight Geological Reference Materials (NIST SRM 2711, BCR 176, GSS-1, GXR-1, GXR-2, GSD-12, Nod-P-1, Nod-A-1) and Anthropogenic Samples, Measured by MC-ICP-MS

In this study, the Cd isotopic composition of various geological reference materials and anthropogenic samples was investigated. The measurements were made by multicollector ICP-MS and instrumental mass fractionation was controlled using a "sample-standard bracketing" technique. Cadmium isotopic data are reported relative to an internal Cd solution (Cd Spex) and expressed as the ¹¹⁴ Cd/¹¹⁰Cd delta value. Two other Cd solutions (Prolabo and JMC) were analysed and yielded the same 0% delta value. A fractionated Cd metal sample (Münster Cd) was used as a secondary reference material for Cd isotopic measurements and we obtained a ¹¹⁴ Cd/¹¹⁰ Cd delta value of 4.48% relative to Cd Spex solution. As opposed to multi-stage Cd purification previously published in the literature, a new one step anionic exchange purification using dilute HCl for the analysis of Cd isotopes in geological samples was developed. This method enabled a high recovery (> 95%) and effective separation of the sample matrix to be achieved. The long-term external reproducibility was evaluated at 0.12% (2 standard deviations) for the ¹¹⁴ Cd/¹¹⁰Cd ratio, based on reference solutions and replicated measurements of samples over one year. The variation of Cd isotopic composition of natural terrestrial samples is restricted to a small range of 0.4%, which is similar to previously reported results. In contrast, large variations of Cd isotopic composition were found for anthropogenic samples with values as low as −0.64% for a dust sample issued from a lead smelter and values as high as +0.50% for NIST SRM 2711 (metal-rich soil). These variations are 10 times larger than the reproducibility and suggest that Cd isotopes can be useful as tracers of anthropogenic sources of Cd in the environment.     

Effective Correction of Mass Bias for Rhenium Measurements by MC-ICP-MS

The geochemistry of Re-Os and the recent use of Re as a non-traditional stable isotope both need accurate and precise quantification of ¹⁸⁷Re/¹⁸⁵Re ratios. This paper reports rhenium isotopic data obtained from the analysis of a standard solution and geological samples by MC-ICP-MS. We show that measured isotopic ratios are modified by matrix effects that cannot be accounted for by the standard solution bracketing technique. The bias resulting from measurements on a spiked (¹⁸⁵Re-enriched) sample is shown to alter the apparent Re concentration by several percent. When spiking samples and calibrators with tungsten, simultaneous measurement of tungsten and rhenium isotopes compensates for the matrix-induced modification of mass bias. Rhenium and tungsten are shown to have different fractionation factors. This may be due to the fact that the two elements fractionate in a different but systematic way, or that the reference isotopic ratios used for elemental Re and W are incoherent with one another. The consistency of fractionation through time can be used to obtain an empirical relationship between W and Re measured ratios from a standard solution to obtain a sample's fractionation-corrected ¹⁸⁷Re/¹⁸⁵Re spiked ratio on samples containing pg g⁻¹ levels of Re, even if some matrix capable of affecting mass bias remains in the final solution.     

Boron and Oxygen Isotope Composition of Certified Reference Materials NIST SRM 610/612 and Reference Materials JB-2 and JR-2

We present data on the concentration, the isotope composition and the homogeneity of boron in NIST silicate glass reference materials SRM 610 and SRM 612, and in powders and glasses of geological reference materials JB-2 (basalt) and JR-2 (rhyolite). Our data are intended to serve as references for both microanalytical and wet-chemical techniques. The δ¹¹ B compositions determined by N-TIMS and P-TIMS agree within 0.5% and compare with SIMS data within 2.5%. SIMS profiles demonstrate boron isotope homogeneity to better than δ¹¹ B = 2% for both NIST glasses, however a slight boron depletion was detected towards the outermost 200 μm of the rim of each sample wafer. The boron isotope compositions of SRM 610 and SRM 612 were indistinguishable. Glasses produced in this study by fusing JB-2 and JR-2 powder also showed good boron isotope homogeneity, both within and between different glass fragments. Their major element abundance as well as boron isotope compositions and concentrations were identical to those of the starting composition. Hence, reference materials (glasses) for the in situ measurement of boron isotopes can be produced from already well-studied volcanic samples without significant isotope fractionation. Oxygen isotope ratios, both within and between wafers, of NIST reference glasses SRM 610 and SRM 612 are uniform. In contrast to boron, significant differences in oxygen isotope compositions were found between the two glasses, which may be due to the different amounts of trace element oxides added at ten-fold different concentration levels to the silicate matrix.     

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.     

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.     

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%.     

Accurate Isotopic and Concentration Analyses of Small Amounts of Pb Using Isotope Dilution Coupled with the Double Spike Technique

A new method has been developed for the simultaneous determination of Pb abundance and Pb isotopic composition with high precision and accuracy for small test portion masses by thermal ionisation mass spectrometry. In this method, a ²⁰⁵pb-²⁰⁴pb double spike is added to samples prior to the chemical separation of Pb, and the isotopic composition of the spike-sample mixture is determined rigorously by the double spike technique using a ²⁰⁷Pb-²⁰⁴Pb spike. The isotopic composition and concentration of Pb in the sample are then obtained by utilising the principle of isotope dilution. Using this technique, replicate determinations of Pb from NIST SRM 981 and GSJ JP-1 (peridotite; 0.07 μg g⁻¹ Pb) were performed. The measured concentration and isotopic data were identical, within uncertainty, to published data or to data that were determined independently in this study. The application of this method to U-Pb dating and the determination of the "initial" Pb isotopic composition was also tested. Lead isotopic compositions and the concentrations of Pb, Th and U were determined for a single batch of samples, through the addition of ²⁰⁵pb-²⁰⁴pb, ²³⁰Th and ²³⁵U spikes to samples prior to chemical separation. Also in these experiments, we confirmed that this routine gives accurate data for Pb, Th and U concentrations and Pb isotopic compositions.     

Three Secondary Reference Materials for Lithium Isotope Measurements: Li7-N, Li6-N and LiCl-N Solutions

The CRPG (Nancy, France) has prepared secondary reference materials for Li isotope measurements by mixing ⁷Li or ⁶Li spikes and either L-SVEC or IRMM-016 certified reference materials to produce solutions having a known Li concentration and isotopic composition. The Li7-N and Li6-N solution samples (1.5 mol l⁻¹ HNO₃) have nominal δ⁷Li isotopic compositions of 30.1‰ and -9.7‰ respectively relative to L-SVEC and concentrations of 100 mg l⁻¹. Repeated measurement of these samples using the QUAD-ICP-MS at the CRPG yielded δ⁷Li of 30.4 ± 1.1‰ (n = 13) and -8.9 ± 0.9‰ (n = 9) at the 2s level of confidence. An additional LiCl-N solution was measured and yielded a delta value of 9.5 ± 0.6‰ (n = 3). Identical results were obtained at the BRGM (Orléans, France) from determinations performed with a Neptune MC-ICP-MS (30.2 ± 0.3‰, n = 89 for the Li7-N, -8.0 ± 0.3‰, n = 38 for the Li6-N and 10.1 ± 0.2‰, n = 46 for LiCl-N at the 2s level of confidence). The deviation of measured composition relative to the nominal value for the Li6-N solution might be explained by either contamination during preparation or an error during sample weighing. These secondary reference materials, previously passed through ion exchange resin or directly analysed, may be used for checking the accuracy of Li isotopic measurements over a range of almost 40‰ and will be available to the scientific community upon request to J. Carignan or N. Vigier, CRPG.     

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.     

Microdistribution of boron: particle-track images from samples of a Caledonian igneous complex

⁷Li recoil tracks in Lexan^R formed as a product of irradiation with thermal neutrons give an image of in sifu-microdistribution of boron in dioritic to granitic rocks of the Caledonian Ballachulish zoned complex and in a carbonate rock from its contact aureole. The images exhibit a polyphase incorporation of boron into primary and secondary minerals. The boron microdistribution is inhomogeneous. Isomorphous incorporation of boron into pyroxene and plagioclase during the main stage of crystallization cannot be established, because the boron distribution is blurred by secondary alteration. In contrast to the intracrystalline feature, the crystal interfaces are enriched in boron. Increased concentrations are also disclosed by overgrowths of primary crystals, exsolution lamellae in alkali feldspar and alteration rims of clinopyroxene. The highest amounts of boron in a siliceous dolomite marble of the contact aureole are found in the alteration products of olivine.     

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.     

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.     

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.     

Intercomparison of Boron Isotope and Concentration Measurements. Part II: Evaluation of Results

The Istituto di Geoscienze e Georisorse (IGG), on behalf and with the support of the International Atomic Energy Agency (IAEA), prepared eight geological materials (three natural waters and five rocks and minerals), intended for a blind interlaboratory comparison of measurements of boron isotopic composition and concentration. The materials were distributed to twenty seven laboratories - virtually all those performing geochemical boron isotope analyses in the world -which agreed to participate in the intercomparison exercise. Only fifteen laboratories, however, ultimately submitted the isotopic and/or concentration results they obtained on the intercomparison materials. The results demonstrate that interlaboratory reproducibility is not well reflected by the precision values reported by the individual laboratories and this observation holds true for both boron concentration and isotopic composition. The reasons for the discrepancies include fractionations due to the chemical matrix of materials, relative shift of the zero position on the δ¹¹B scale and a lack of well characterized materials for calibrating absolute boron content measurements. The intercomparison materials are now available at the IAEA (solid materials) and IGG (waters) for future distribution.     

Oxygen isotope geothermometers for metamorphic rocks

The Chicago mineral-carbonate oxygen isotope fractionation curves have been combined with mineral-water fractionation data for jadeite, zoisite and rutile and new data for grossular-water to provide a set of self-consistent mineral-pair calibrations. The A coefficients in the equation 1000 In α= A × 10⁶T^-2 of the new mineral-pair fractionations are
Jadeite Zoisite Grossular Rutile
Quartz 1.69 2.00 3.03 5.02
Jadeite 0.31 1.34 3.33
Zoisite 1.03 3.02
Grossular 1.99
The isotopic fractionation properties of natural pyralspite garnet [(Ca, Fe, Mg, Mn)₃Al₂Si₃O₁₂] can be approximated by those of the grossular end-member. Appropriate substitutions also yield coefficients for the solid-solution minerals: sodic pyroxene and epidote, e.g.
A _{quartz-sodic pyroxene}= 2.75 - 1.06X_jd,
A _{quartz-epidote}= 2.00 + 0.75X_ps
where X _Jd and X _Ps are the mole fractions of the jadeite and pistacite components, respectively.
The new data set is particularly suitable for the geothermometry of metamorphic rocks. δ¹⁸O data from minerals of the high-pressure metamorphic rocks of the Sesia Zone of Italy and Cyclades Complex of Greece yield well-constrained mean temperatures of 572 and 478 C, respectively. Type III blueschist metabasalts of the Franciscan Formation of California give mean quartz-garnet temperatures of 354 C.     

Neodymium and Strontium Isotope Data for USGS Reference Materials BCR-1, BCR-2, BHVO-1, BHVO-2, AGV-1, AGV-2, GSP-1, GSP-2 and Eight MPI-DING Reference Glasses

We have measured ⁸⁷Sr/⁸⁶Sr and ¹⁴³ Nd/¹⁴⁴ Nd isotope ratios in different batches and aliquots of the new US Geological Survey (USGS) reference materials (RMs) BCR-2, BHVO-2, AGV-2 and GSP-2 and the original USGS RMs BCR-1, BHVO-1, AGV-1 and GSP-1 by thermal ionisation mass spectrometry. In addition, we also analysed the eight Max-Planck-Institut-Dingwell (MPI-DING) reference glasses. Nearly all isotope ratios obtained in the different aliquots and batches agree within uncertainty limits indicating excellent homogeneity of the USGS powders and the MPI-DING glasses. With the exception of GSP-2, the new USGS RMs are also indistinguishable from the ratios found in the original USGS RMs (⁸⁷Sr/⁸⁶Sr: 0.704960, 0.704958 (BCR-1, -2), 0.703436, 0.703435 (BHVO-1, -2), 0.703931, 0.703931 (AGV-1, -2); ¹⁴³ Nd/¹⁴⁴ Nd: 0.512629, 0.512633 (BCR-1, -2), 0.512957, 0.512957 (BHVO-1, -2); 0.512758, 0.512755 (AGV-1, -2)). This means that for normalisation purposes in Sr and Nd isotope geochemistry BCR-2, BHVO-2 and AGV-2 can well replace BCR-1, BHVO-1 and AGV-1 respectively.     

Sulfur Isotopic Study of the Toyoha Deposit, Hokkaido, Japan Comparison between the Earlier-Stage and the Later-Stage Veins

Abstract: The sulfur isotopic ratios (δ³⁴S) of ore minerals from the Toyoha deposit, Hokkaido, one of the largest Pb–Zn–Ag polymetallic vein-type deposits in Japan, were studied. More than 90% of the δ³⁴S values of the studied sulfide minerals collected from the Toyoha deposit range from +5 to +9%, with an average of approximately +7% irrespective of the mineral species, veins, elevations, depth, mineralization stages and mineral assemblages. Relatively uniform δ³⁴S values obtained in this study suggest that the reduced aqueous sulfur species predominated over the oxidized sulfur in the ore solution throughout the mineralization stages. Thus, the source of sulfur for the ore sulfides is postulated to be magmatic.
The temperature obtained from the fluid inclusion study and the temperature of the sulfur isotopic geothermometer are not consistent. This suggests that each mineral precipitated under disequilibrated conditions with respect to the sulfur isotope.
The change in redox conditions presumably encountered between the mineralization stages did not account for the isotopic fluctuations since the isotopic exchanges between the oxidized and reduced aqueous sulfurs are much slower than the rate of oxidation of the ore solution.     

Thermoluminescence dating of Dimlington Stadial deposits in eastern England

The loess component of a solifluction deposit of the Dimlington Stadial exposed at the inland site of Eppleworth in eastern England gave a thermoluminescence date of 17.5 ± 1.6 × 10³ years. The solifluction deposit is overlain by a slightly weathered till correlated with the Skipsea Till of coastal exposures. which lies between organic horizons with radiocarbon dates of 18,500–18,240 B.P. and 13,045 B.P. Although the till must have been deposited during the Dimlington Stadial (after 18,240 B.P. at Dimlington and after 17,500 B.P. at Epplcworth), it gave apparent TL dates of 42.1 ± 3.6 × 10³ years at Eppleworth and 102 ± 9 × 10³ years at Dimlington, indicating that the components of the till were not exposed to light immediately before deposition.