Proposal for International Agreement on Ca Notation Resulting from Discussions at Workshops on Stable Isotope Measurements Held in Davos (Goldschmidt 2002) and Nice (EGS-AGU-EUG 2003)

A proposal is made to standardise the reporting of Ca isotope data to the δ⁴⁴Ca/⁴⁰Ca notation (or δ⁴⁴Ca/42Ca) and to adopt NIST SRM 915a as the reference standard.     

The Calcium Isotope Composition of Modern Seawater Determined by Thermal Ionisation Mass Spectrometry

The Ca isotopic composition of modern seawater has been determined using a ⁴³Ca-⁴⁸Ca double spike, which was calibrated using a ⁴²Ca/⁴⁴Ca seawater ratio of 0.30587 ± 0.00026. This ratio was determined from a total evaporation experiment in which the ion beam was measured from the beginning to the end of the emission. With integration of the peak intensities, the fractionation effects can be minimised, since total evaporation of the reservoir cancels out the effect of vapour enrichment in the light isotopes. This experiment avoids the gravimetric uncertainty inherent in the double spike calibration. This calibration allows the precise redetermination of the seawater isotopic composition of Ca. A mean ⁴⁰Ca/⁴⁴Ca ratio for two Atlantic water samples of 45.143 (2s_mean= 0.003) was found. The good reproducibility of the Ca isotope ratios in present seawater and the very strong isotopic homogeneity of Ca in the oceans illustrate the advantage of using seawater as the common standard, with the advantage of decreasing interlaboratory bias.     

High Precision Determination of 48Ca/42Ca Ratio by TIMS for Ca Isotope Fractionation Studies

For studies of mass-dependent fractionation of calcium isotopes in natural materials, the ⁴⁸Ca/⁴²Ca ratio is a superior choice to the conventionally measured ⁴⁴Ca/⁴⁰Ca ratio for two important reasons. These are (1) mass-dependent fractionation can be determined free from the effects of inherited or ingrown radiogenic ⁴⁰Ca and (2) this ratio increases the spread of measured isotopic masses by 50%, resulting in statistically better resolution of fractionation, assuming similar precision. A third, though strictly technical, advantage is the inherent ability of a mass spectrometer to measure ratios close to unity (⁴⁸Ca/⁴²Ca) more precisely than very small or large ratios (⁴⁴Ca/⁴⁰Ca). However, because of the very low natural abundance of both ⁴⁸Ca and ⁴²Ca, their ratio has been very difficult to measure, the only attempt so far being on a high mass resolution MC-ICP-MS with a precision of 0.33%. We report here determination of the ⁴⁸Ca/⁴²Ca ratio by the more commonly available and user-friendly multi-collector TIMS using a ⁴³Ca-⁴⁶Ca double-spike, with a significantly better precision of 0.18% (2s). The ⁴⁸Ca/⁴⁰Ca or ⁴⁴Ca/⁴⁰Ca ratio can also be measured in the same mass spectrometer run to provide complementary information on any radiogenic component.     

The Calcium Isotope Composition (δ44/40Ca) of NIST SRM 915b and NIST SRM 1486

The calcium isotopic composition of NIST SRM 915b and 1486 provided by the National Institute of Standards and Technology was analysed. The δ^44/40Ca values of the two reference materials relative to NIST SRM 915a were: NIST SRM 915b =+0.72 ± 0.04‰ and NIST SRM 1486 =?1.01 ± 0.02‰. NIST SRM 1486 did not require any chemical separation prior to measurement.     

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.     

Very high 18o enrichment in Archean cherts from South India: implications for Archean ocean temperature

Stable carbon and oxygen isotopic compositions of essentially unmetamorphosed Archean (> 2.6 Gyr old) cherts and carbonates of the Dharwar Sequence of southern India, from the northernmost part of the Dharwar-Shimoga supracrustal belt (Kalche and Nagargali), have been determined. The cherts from the Nagargali area, which preserve oolitic texture and cryptocrystalline silica, show highly enriched δ¹⁸O values ranging from 28 to 31.4%o relative to SMOW. Such values are the highest yet reported from Archean nondetrital sediments, but are similar to those of modern marine cherts. On the assumption of a seawater δ¹⁸O of 0%₀, calculation of temperature based on the maximum δ¹⁸O value of 31.4%₀ yields a value of 40°C. This is significantly less than 70–80°C reported for the Archean oceans based on cherts and chert-phosphate pairs. Diagenetically recrystallized microcrystalline chert-dolomite pairs of Kalche area exhibit a range of oxygen isotopic ratios similar to those reported for Archean cherts and carbonates from other parts of the world. The temperature of diagenesis is estimated to be about 68°C.     

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.     

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.     

Calcium Isotopic Compositions of Sixteen USGS Reference Materials

Calcium isotopic compositions of sixteen Ca‐bearing USGS geological reference materials including igneous and sedimentary rocks are reported. Calcium isotopic compositions were determined in two laboratories (GPMR, State Key Laboratory of Geological Processes and Mineral Resources, China University of Geosciences, Wuhan; and CIG, Centre for Isotope Geochemistry, University of California, Berkeley) using the ⁴²Ca‐⁴⁸Ca double‐spike technique by thermal ionisation mass spectrometry. As opposed to common cation exchange resin, a micro‐column filled with Ca‐selective resin (DGA resin) was used in order to achieve high recovery (> 96%) and efficient separation of Ca from the sample matrix. The intermediate measurement precision was evaluated at 0.14‰ (2s) for δ^44/40Ca_SRM915a at GPMR, based on replicate measurements of pure Ca reference material NIST SRM 915a, NIST SRM 915b and seawater. Overall, the measurement uncertainties in both laboratories were better than 0.15‰ at the 2s level. Result validation was carried out for all available data sets. The Ca isotopic compositions of USGS reference materials are not only in agreement between GPMR and CIG, but also in agreement with previously published data within quoted uncertainties. The comprehensive data set reported in this study serves as a reference for both quality assurance and interlaboratory comparison of high precision Ca isotopic study.     

Chemostratigraphy of Neoproterozoic carbonates: implications for 'blind dating'

The δ¹³C_carb and ⁸⁷Sr/⁸⁶Sr secular variations in Neoproteozoic seawater have been used for the purpose of 'isotope stratigraphy' but there are a number of problems that can preclude its routine use. In particular, it cannot be used with confidence for 'blind dating'. The compilation of isotopic data on carbonate rocks reveals a high level of inconsistency between various carbon isotope age curves constructed for Neoproteozoic seawater, caused by a relatively high frequency of both global and local δ¹³C_carb fluctuations combined with few reliable age determinations. Further complication is caused by the unresolved problem as to whether two or four glaciations, and associated negative δ¹³C_carb excursions, can be reliably documented. Carbon isotope stratigraphy cannot be used alone for geological correlation and 'blind dating'. Strontium isotope stratigraphy is a more reliable and precise tool for stratigraphic correlations and indirect age determinations. Combining strontium and carbon isotope stratigraphy, several discrete ages within the 590–544 Myr interval, and two age-groups at 660–610 and 740–690 Myr can be resolved.     

Calcium Isotopes (δ44/40Ca) in MPI-DING Reference Glasses, USGS Rock Powders and Various Rocks: Evidence for Ca Isotope Fractionation in Terrestrial Silicates

We report δ^44/40Ca_{(SRM 915a)} values for eight fused MPI‐DING glasses and the respective original powders, six USGS igneous rock reference materials, the U‐Th disequilibria reference material TML, IAEA‐CO1 (Carrara marble) and several igneous rocks (komatiites and carbonatites). Sample selection was guided by three considerations: (1) to address the need for information values on reference materials that are widely available in support of interlaboratory comparison studies; (2) support the development of in situ laser ablation and ion microprobe techniques, which require isotopically homogenous reference samples for ablation; and (3) provide Ca isotope values on a wider range of igneous and metamorphic rock types than is currently available in the scientific literature. Calcium isotope ratios were measured by thermal ionisation mass spectrometry in two laboratories (IFM‐GEOMAR and Saskatchewan Isotope Laboratory) using ⁴³Ca/⁴⁸Ca‐ and ⁴²Ca/⁴³Ca‐double spike techniques and reported relative to the calcium carbonate reference material NIST SRM 915a. The measurement uncertainty in both laboratories was better than 0.2‰ at the 95% confidence level. The impact of different preparation methods on the δ^44/40Ca_{(SRM 915a)} values was found to be negligible. Except for ML3‐B, the original powders and the respective MPI‐DING glasses showed identical δ^44/40Ca_{(SRM 915a)} values; therefore, possible variations in the Ca isotope compositions resulting from the fusion process are excluded. Individual analyses of different glass fragments indicated that the glasses are well homogenised on the mm scale with respect to Ca. The range of δ^44/40Ca_{(SRM 915a)} values in the igneous rocks studied was larger than previously observed, mostly owing to the inclusion of ultramafic rocks from ophiolite sections. In particular, the dunite DTS‐1 (1.49 ± 0.06‰) and the peridotite PCC‐1 (1.14 ± 0.07‰) are enriched in ⁴⁴Ca relative to volcanic rocks (0.8 ± 0.1‰). The Carrara marble (1.32 ± 0.06‰) was also found to be enriched in ⁴⁴Ca relative to the values of assumed precursor carbonates (< 0.8‰). These findings suggest that the isotopes of Ca are susceptible to fractionation at high temperatures by, as yet, unidentified igneous and metamorphic processes.     

Mass‐Independent and Mass‐Dependent Ca Isotopic Compositions of Thirteen Geological Reference Materials Measured by Thermal Ionisation Mass Spectrometry

We report mass‐independent and mass‐dependent Ca isotopic compositions for thirteen geological reference materials, including carbonates (NIST SRM 915a and 915b), Atlantic seawater as well as ten rock reference materials ranging from peridotite to sandstone, using traditional ε and δ values relative to NIST SRM 915a, respectively. Isotope ratio determinations were conducted by independent unspiked and ⁴³Ca‐⁴⁸Ca double‐spiked measurements using a customised Triton Plus TIMS. The mean of twelve measurement results gave ε^40/44Ca values within ± 1.1, except for GSP‐2 that had ε^40/44Ca = 4.04 ± 0.15 (2SE). Significant radiogenic ⁴⁰Ca enrichment was evident in some high K/Ca samples. At an uncertainty level of ± 0.6, all reference materials had the same ε^43/44Ca and ε^48/44Ca values. We suggest the use of δ^44/42Ca to report mass‐dependent Ca isotopic compositions. The precision under intermediate measurement conditions for δ^44/42Ca over eight months in our laboratory was ± 0.03‰ (with n ≥ 8 repeat measurements). Measured igneous reference materials gave δ^44/42Ca values ranging from 0.27‰ to 0.54‰. Significant Ca isotope fractionation may occur during magmatic and metasomatism processes. Studied reference materials with higher (Dy_n/Yb_n) tend to have lower δ^44/42Ca, implying a potential role of garnet in producing magmas with low δ^44/42Ca. Sandstone GBW07106 had a δ^44/42Ca value of 0.22‰, lower than all igneous rocks studied so far.     

Laser Ablation and Solution ICP-MS Determination of Rare Earth Elements in USGS BIR-1G, BHVO-2G and BCR-2G Glass Reference Materials

Data are reported for rare earth elements (REE) in three geological glass reference materials (BIR-1G, BHVO-2G and BCR-2G) using a UV (266 nm) laser ablation ICP-MS system and the classical (HF-HClO₄) acid decomposition method, followed by conventional nebulisation ICP-MS. External calibration of laser ablation analyses was performed using NIST SRM reference materials with internal standardisation using ²⁹Si and ⁴⁴Ca. Replicate analyses of reference basaltic glasses yielded an analytical precision of 1-5% (RSD) for all the elements by solution ICP-MS and 1-8% (RSD) by laser ablation ICP-MS. The relative differences between the REE concentrations measured by solution and laser ablation ICP-MS compared with the reference values were generally less than 11 % for most elements. The largest deviations occurred for La determined by solution ICP-MS in BIR-1G. The results of both solution and laser ablation ICP-MS agreed well, generally better than 7%, with the exception of La, Pr and Sm in BIR-1G. The measured REE laser ablation data for BIR-1G, BHVO-2G and BCR-2G agreed with the previously published data on these basaltic reference glasses, within a range of 0-10% for most elements. No significant influences were observed for the predicted spectral interferences on some REE isotopes in the analysis of basaltic glasses.     

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.     

A Simplified, Accurate and Fast Method for Lithium Isotope Analysis of Rocks and Fluids, and δ7Li Values of Seawater and Rock Reference Materials

We report a new approach to conduct fast and accurate lithium isotope ratio measurements by MC-ICP mass spectrometry after wet chemical sample preparation. In contrast to most previously published methods our MC-ICP-MS set-up did not use a desolvating system to achieve appropriate ion beam intensities and, therefore, was less affected by matrix-induced shifts of the instrumental mass bias. As the total lithium background and build-up in the sample introduction system was low, previous sample residues could be washed out by an extended uptake of the new sample. Elimination of a nitric acid rinse step increased the sample throughput by a factor of two and allowed the instrumental mass bias drift to be tracked more precisely. δ⁷Li values of powdered silicate rock reference materials and seawater obtained in this study revealed good accuracy and an overall analytical uncertainty of typically 0.5‰ (2s). On the basis of a comparison between our lithium isotope data and compiled literature data, we recommend preliminary average δ⁷Li values for seawater (+30.8‰) and several silicate rock reference materials (BHVO-1: +5.0‰; JA-1: +5.6‰; JB-2: +4.8‰). The compilation of published δ⁷Li values for seawater suggests that the observed large lithium isotope differences are due to inter-method and/or interlaboratory bias. Most recently published δ⁷Li values for seawater show little variation and confirm a constant lithium isotope composition (at the sub ‰ level) of seawater in well mixed ocean basins.     

Trace Fossils and Sulfur Isotopes in Mudstones around the Kuroko Deposits in the Hokuroku Basin, Northeast Japan: An Attempt to Delineate the Depositional Environment

Abstract. A comprehensive investigation was carried out on the distribution of both trace fossils and sulfur isotopes in mud-stones in the Hokuroku district, northeast Japan, in the hope of delineating the depositional environment of the mudstones in which the Kuroko deposits are embedded. The mudstones are generally massive in structure and usually contain large trace fossils, being indicative of an aerobic biofacies. On the other hand, some mudstones in and above the Kuroko ore horizon are partly laminated and usually contain smaller trace fossils, being assignable to an anaerobic or dysaerobic biofacies. The δ³⁴S values of sulfides in the mudstones above and below the ore horizon range from -40 to -12 %o, indicating mostly oxic depositional conditions in equilibrium with the inferred aerobic biofacies. In the mudstones in the ore horizon, the δ³⁴S values exhibit regionally discriminated variations: -44 to -12 %o in areas far (>1 km) from the known Kuroko deposits and -24 to +6 %o in areas closer to them. The latter high δ³⁴S group implies the temporal occurrence of local anoxic basins in the vicinity of the known Kuroko deposits. At the time of late Nishikurosawa Stage (i.e. the currently assumed Kuroko metallogenic epoch), an intense oceanic stagnation is suggested to have taken place to form the local anoxic basins responsible for the formation and preservation of Kuroko deposits. This oceanic environmental event is considered to be most likely due to increasing biological productivity primarily triggered and enhanced by upwelling of NADW in the paleo-Sea of Japan at that time.     

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.     

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.     

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.     

40Ar-39Ar Spectra of Alunite from Phreatic Craters in the Muine Volcano, Hokkaido, Japan

Abstract. ⁴⁰Ar-³⁹Ar analyses of two alunite samples from phreatic craters in the Pliocene Muine volcano in southwest Hokkaido, Japan, were carried out. The alunite with 17.4 permil δ³⁴S_{V_CDT} value in hydrothermal breccia from the Nagaoyama crater and that with 14.3 permil δ³⁴S_{V_CDT} value in silicified andesite from the Konuma crater give total fusion ages of 1.40 ± 0.04 Ma (la uncertainty) and 1.24 ± 0.08 Ma, respectively. However, the spectra of these samples indicate they have been effected by thermal overprinting and/or the existence of excess argon. These preliminary ⁴⁰Ar-³⁹A analyses suggest that the alunite underwent multiple hydrothermal activity by magmatic gas and vapor subsequent to the main hydrothermal activity.