Incorporation of U,Pb and Rare Earth Elements in Calcite through Crystallisation from Amorphous Calcium Carbonate: Simple Preparation of Reference Materials for Microanalysis

Uncertainty for elemental and isotopic measurements in calcite by LA‐ICP‐MS is largely controlled by the homogeneity of the reference materials (RMs) used for calibration and validation. In order to produce calcite RMs with homogeneous elemental and isotopic compositions, we incorporated elements including U, Pb and rare earth elements into calcite through heat‐ and pressure‐induced crystallisation from amorphous calcium carbonate that was precipitated from element‐doped reagent solution. X‐ray absorption spectra showed that U was present as U(VI) in the synthesised calcite, probably with a different local structure from that of aqueous uranyl ions. The uptake rate of U by our calcite was higher in comparison with synthetic calcite of previous studies. Variations of element mass fractions in the calcite were better than 12% 2RSD, mostly within 7%. The ²⁰⁷Pb/²⁰⁶Pb ratio in the calcite showed < 1% variations, while the ²³⁸U/²⁰⁶Pb ratio showed 3–24% variations depending on element mass fractions. Using the synthetic calcite as primary RMs, we could date a natural calcite RM, WC‐1, with analytical uncertainty as low as < 3%. The method presented can be useful to produce calcite with controlled and homogeneous element mass fractions and is a promising alternative to natural calcite RMs for U‐Pb geochronology.     

The variogram method for a fractal model of a rock joint surface

The variogram method can be used to make a fractal model of a rock joint surface. However, it has been found that the range of lag satisfying the power law is very small, that is, less than about 10% of the profile length. The cause of this has been investigated mathematically. The main cause of this problem is due to the fact that the profile length is assumed infinite for the theory, but it is finite for the actual calculation. This discrepancy between the actual calculation and the theory yields a significant error and causes the problem when the lag is large. To confirm the validity of this conclusion, it has been demonstrated that the range of lag satisfying the power law increases with an increase in the profile length by applying the variogram method to profiles cut from a long profile. In addition, the range of lag was investigated mathematically and it has been clarified that the range of lag increases with an increase in the fractal dimension. These results suggest that the profile length, the sampling interval and the removal of the linear trend are items to which we must pay attention when we use the variogram method.     

Geochemical characteristics of sediment as indicators of post-glacial environmental changes off the Shandong Peninsula in the Yellow Sea

Core NYS-101, which was recovered at a water depth of 49 m northeast of the Shandong Peninsula in the North Yellow Sea, penetrates the Holocene subaqueous clinoform that wraps around the Shandong Peninsula. The uppermost 18 m of this well-dated core was deposited after about 13 cal kyr BP during the post-glacial transgression. We focused on trace and rare earth element (REE) chemistries of the core sediments in the uppermost 18 m to investigate the sediment provenance and factors controlling the sediment composition. On the basis of down-core distributions of REE fractionation parameters and of ratios among REEs and other immobile elements, we divided the uppermost 18 m into three distinct compositional intervals: Interval 1 (above 6.08 m, from the time tens of years earlier than 6500 cal yr BP up to the present), Interval 2 (13.90–6.08 m, from about 8200 cal yr BP to the boundary between Intervals 1 and 2), and Interval 3 (below 13.90 m, from about 13,000 to 10,400 cal yr BP). The chondrite- and upper continental crust (UCC)-normalized REE fractionation patterns of Intervals 3 and 2 are similar to those of Yellow River sediments, but the patterns in Interval 1 are obviously different.     

Diel Vertical Migration of the Marine Cladoceran Podon Leuckarti: Variations with Reproductive Stage

Diel vertical migration (DVM) of the marine cladoceran Podon leuckarti was investigated with reference to their reproductive stages and size. Males and females, except for gamogenic females with an advanced resting egg (GA), aggregated at the near-bottom layer or at the surface during the day and dispersed into the water column at night. Both the near-bottom aggregation and the surface aggregation during daytime are suggested to be behavior that reduces the predation risk from visual predators. However, GA aggregated in the near-bottom layer during daytime and avoided the surface layer. The near-bottom aggregation might be more effective behavior for GAs to reduce risk of visual predation than the surface aggregation because of the conspicuous resting egg they carried. These results show that carrying an advanced resting egg influenced the DVM of P. leuckarti.     

Open-system degassing of sulfur from Krakatau 1883 magma

We present the first sulfur and oxygen isotopic data for tephra from the catastrophic 1883 eruption of Krakatau. Sulfur isotopic ratios in unaltered Krakatau tephra erupted August 26–27, 1883 are markedly enriched in ³⁴S relative to mantle sulfur. High δ³⁴S values of +6.3 to +16.4‰ can best be explained by open-system or multi-stage degassing of SO₂ from the oxidized rhyodacitic and gray dacitic magmas with ³⁴S enrichment of SO²⁻₄ remaining in the melt. Lower whole-rock δ³⁴S values of +2.6‰ and +4.0‰ in two oxidized gray dacitic samples indicate more primitive subarc mantle sulfur in the 1883 magma chamber. Initial δ³⁴S of the rhyodacitic magma was probably in the +1.5‰ to +4.0‰ range and similar to δ³⁴S values measured in arc volcanic rocks from the Mariana Arc.     

Enrichment of adsorbed methane in authigenic carbonate concretions of the Japan Trench

Substantial amounts of adsorbed methane were detected in authigenic carbonate concretions recovered from sedimentary layers from depths between 245 and 1,108 m below seafloor during Ocean Drilling Program Leg 186 to ODP sites 1150 and 1151 on the deep-sea terrace of the Japan Trench. Methane contents were almost two orders of magnitude higher in the concretions (291–4,528 nmol/g wet wt) than in the surrounding bulk sediments (5–93 nmol/g wet wt), whereas methane/ethane ratios and stable carbon isotopic compositions were very similar. Carbonate content of surrounding bulk sediments (0.02–3.2 wet wt%) and methane content of the surrounding bulk sediments correlated positively. Extrapolation of the carbonate contents of bulk sediments suggests that 100 wt% carbonate would correspond to 1,886±732 nmol methane per g bulk sediment, which is similar to the average value observed in the carbonate concretions (1,321±1,067 nmol/g wet wt, n = 13). These data support the hypothesis that, in sediments, adsorbed hydrocarbon gases are strongly associated with authigenic carbonates.     

Downward carbon transport by diel vertical migration of the copepods Metridia pacifica and Metridia okhotensis in the Oyashio region of the western subarctic Pacific Ocean

Seasonal change in the downward carbon transport due to respiration and mortality through diel vertical migration (DVM) of the calanoid copepods Metridia pacifica and Metridia okhotensis was estimated in the Oyashio region, western subarctic Pacific during six cruises from June 2001 to June 2002. M. pacifica (C4, C5 and adult females) was an active migratory species throughout the year though its DVM amplitude varied among seasons and stages. The mean distribution depths of adult females during the daytime were positively related with the illumination level in the water column, being shallowest in April and deepest in January. M. okhotensis generally showed less-extensive migrations than M. pacifica. Therefore, together with their lower abundance, this species is considered to be a less-important mechanism of downward transport of carbon except for April when their DVM was more active and descended deeper than M. pacifica, which remained in the upper 150 m even during the daytime. The mean migrating biomass of the two Metridia species was 558 mg C m⁻² d⁻¹ and was high during summer to winter (263–1676 mg C m⁻² d⁻¹) and low during spring (59–63 mg C m⁻² d⁻¹). Total downward flux through DVM fluctuated between 1.0 and 20.0 mg C m⁻² d⁻¹ with an annual mean of 8.0 mg C m⁻² d⁻¹. Contribution of the respiratory flux was greater than the mortality flux and accounted for 64–98% of total migratory flux throughout the year except for January when contribution of both fluxes was equal. Overall the annual carbon transport by DVM of Metridia spp. was estimated as 3.0 g C m⁻² year⁻¹, corresponding to 15% of the annual total POC flux at 150 m at the study site, suggesting that DVM is a significant process for carbon export in the subarctic region as well as that in tropical and subtropical oceanic regions. Since DVM in M. pacifica is more active during the non-bloom season when the gravitational flux of particulate matter is low, this species plays an important role in driving the biological pump in the subarctic Pacific during summer to winter.     

Ventilation of the North Pacific subtropical pycnocline and mode water formation

The annual subduction rate of the North Pacific was calculated based on isopycnally averaged hydrographic climatology (HydroBase), high-resolution winter mixed-layer climatology (NWMLC), and various wind stress climatologies from ship reports, numerical weather prediction products, and satellite products. The calculation was performed using Lagrangian coordinates in the same manner as in previous works, except a less smoothed oceanic climatology (HydroBase and NWMLC) was used instead of a World Ocean Atlas. Differences in the wind stress climatologies have very little effect on subduction rate estimates. The subduction rate census for density classes showed peaks corresponding to subtropical mode water (STMW), central mode water (CMW), and eastern subtropical mode water (ESTMW). The deeper mixed layer and the associated sharper mixed-layer fronts in the present climatology resulted in a larger lateral induction, which boosted the subduction rate, especially for the potential density anomaly (σ_θ) range of the lighter STMW (25.0 < σ_θ < 25.2 kg m⁻³) and lighter CMW (26.0 < σ_θ < 26.2 kg m⁻³), compared to previous estimates. The renewal time of permanent pycnocline water was estimated as the volume of water divided by the subduction rate for each σ_θ class: 2–4 years for ESTMW (24.5 < σ_θ < 25.2 kg m⁻³), 2 years for the lighter STMW (25.0 < σ_θ < 25.3 kg m⁻³), 5–9 years for the denser STMW (25.3 < σ_θ < 25.6 kg m⁻³), 10–20 years for the lighter CMW (26.0 < σ_θ < 26.2 kg m⁻³), 20–30 years for the middle CMW (26.2 < σ_θ < 26.3 kg m⁻³), and 60 years or longer for the denser CMW (26.3 < σ_θ < 26.6 kg m⁻³). A comparison of the water volume and subduction rate in potential temperature–salinity (θ–S) space indicated that the upper permanent pycnocline water (25.0 < σ_θ < 26.2 kg m⁻³) was directly maintained by nondiffusive subduction of winter surface water, including STMW and lighter CMW. The lower permanent pycnocline water (26.2 < σ_θ < 26.6 kg m⁻³) may be maintained through the subduction of fresher and colder water from the subarctic–subtropical transition region and subsequent mixing with saltier and warmer water. Diagnosis of the potential vorticity (PV) of the subducted water demonstrated that the low PV of STMW was mainly due to the large subduction rate, whereas that of both ESTMW and CMW was due mainly to the small density advection rate (cross-isopycnal flow). Additionally, a relatively large subduction rate probably contributes to the low PV of part of the lighter CMW (ESTMW) formed in the region around 38°N and 170°W (28°N and 145°W), which is characterized by a relatively thick winter mixed layer and an associated mixed-layer front, causing a large lateral induction rate.     

Hybridization of a Shallow 'I-type' Granitoid Pluton and its Host Migmatite by Magma-Chamber Wall Collapse: the Tokuwa Pluton, Central Japan

The Miocene Tokuwa pluton of ‘I-type’ granitoidaffinity was emplaced discordantly into a Cretaceous to Paleogeneaccretionary complex and induced a contact aureole in whichvarious thermally metamorphosed rocks were developed, includinghornfels, metatexite, diatexite and cordierite-bearing tonalite(Crd-tonalite) of ‘S-type’ granite affinity. Thethermally metamorphosed rocks show low-pressure reaction texturesculminating in partial melting. Peak P–T conditions of3 kbar at 780°C are estimated on the basis of the TWQ thermobarometerfor the garnet-bearing rocks. The rocks in the contact aureoleexhibit a gradual transition from hornfels, through metatexiteand diatexite to Crd-tonalite. The Sr-isotopic composition atthe time of Tokuwa pluton emplacement at 12 Ma decreases systematicallyfrom metatexite (0·7100–0·7112) throughdiatexite (0·7078–0·7094) to Crd-tonalite(0·7067–0·7068); this trend is interpretedin terms of mixing between the Tokuwa magma and the aureolemigmatites. The field relationships, geochemical data, and isotopicdata collectively suggest that the emplacement of the Tokuwapluton triggered partial melting of the surrounding metasedimentaryrocks. Subsequent hybridization of the Tokuwa magma with themetatexite in variable proportions produced the Crd-tonaliteand diatexite. The hybridization was caused by invasion of theTokuwa magma into the migmatite zone, accompanied by gravitationalcollapse of the previously crystallized wall of the magma chamber.The data presented demonstrate that even a relatively low-temperature,shallow, ‘I-type’ granitoid pluton can induce contactanatexis and hybrid ‘S-type’ granitoid formationat the intrusive contact. KEY WORDS: contact metamorphism; hybridization; magma–host-rock interaction; migmatite; ‘S-type’ granitoid