Ra-partitioning between phlogopite and silicate melt and 226Ra/Ba–230Th/Ba isochrons

In this study we experimentally determine phlogopite/melt partition coefficients of Ra and other trace elements in a lamproitic system. This work was achieved using an analytical technique (LA-ICP-MS) with low detection limits (~ 0.01 fg) permitting the measurement of the very low Ra concentrations feasible in experiments (~ 1 ppb). D_Ra^{phlogopite/melt} was determined to 2.28 ± 0.44 and 2.84 ± 0.47 in two experiments, the ratio D_Ra/D_Ba is around 1.6. The compatibility of Ra in phlogopite results from an ionic radius being close to the apex of the lattice strain parabola for earth alkalis in the large XII-coordinated interlayer site of phlogopite. A re-evaluation of D_Ra and D_Ra/D_Ba for magmatic minerals containing appreciable Ra, yields D_Ra^mineral/melt ranging from ~ 2.6 for phlogopite down to 2–3 ? 10^? 5 for pyroxenes, and D_Ra/D_Ba^mineral/melt from ~ 4 for leucite to 2 ? 10^? 2 for orthopyroxene. The influence of melt composition on D_Ra/D_Ba is less than 10%. All investigated minerals have different D_Ra/D_Ba, strongly fractionating Ra from Ba. Thus, for magmatic systems, (²²⁶Ra)/Ba in the various minerals is not constant, these minerals do not form a straight line in the (²²⁶Ra)/Ba–(²³⁰Th)/Ba system at the time of crystallization and thus, there is no (²²⁶Ra)/Ba–(²³⁰Th)/Ba isochron at t₀. ²²⁶Ra–²³⁰Th–Ba mineral dating is thus applicable only to model ages calculated from mineral–glass pairs with known D_Ra.     

A method for coupled ESR/U-series dating of teeth showing post-depositional U-loss

An additional method of coupled ESR/U-series dating is developed for teeth showing post-depositional U-loss. The fundamental parameter for the dose rate calculation is the present-day ²³⁰Th-activity because of the geochemical immobility of thorium. Uranium and thorium concentrations are measured by thermal ionization mass spectrometry (TIMS). Due to the unknown uranium history an average saturation uptake of uranium is assumed leading to an average development of U-series activities. Therewith an internal dose rate and the age T can be calculated on condition that the modelled ²³⁰Th-activity at time T corresponds with the measured value. Using this new method, teeth, found in archaeological sites in France (Gramat, Bramefond), could be dated even though they show U-loss after U-uptake. Two teeth from Gramat could be dated to 128.3±8.6 and 130.5±10 ka. Two teeth from Bramefond have ages of 104.4±8.4 and 115.1±10.2 ka. Both sites can be ascribed to oxygen isotope stage 5.     

Precise U–Pb and Th–Pb age determination of kimberlitic perovskites by secondary ion mass spectrometry

Perovskite, a common Th- and U-enriched accessory mineral crystallised from kimberlitic magmas, has long been thought to be an important geochronometer for dating the emplacement of kimberlite. However, it also contains variably high levels of common Pb, which makes it difficult to obtain a precise measurement of radiogenic Pb/U and Pb/Th isotopic compositions using microbeam techniques such as SIMS and LA-ICP-MS. We present calibration protocols for in situ U–Pb and Th–Pb age determination of kimberlitic perovskite using the large double-focusing Cameca IMS 1280. Linear relationships are found between ln(²⁰⁶Pb?⁺/U⁺) and ln(UO₂⁺/U⁺), and between ln(²⁰⁸Pb?⁺/Th⁺) and ln(ThO⁺/Th⁺), based on which the inter-element fractionation in unknown samples during SIMS analyses can be precisely calibrated against a perovskite standard. The well-characterized Ice River perovskite is chosen as the U–Pb and Th–Pb age standard in this study. The ²⁰⁴Pb-correction method was used to estimate the fraction of common Pb, which is consistent with the results obtained using the ²⁰⁷Pb-based correction method for the dated perovskites of Phanerozoic age.A Tazheran perovskite with unusually high U but rather low Th yielded a Concordia U–Pb age of 462.8 ± 2.5 Ma and a Th–Pb age of 462 ± 4 Ma. Two perovskite samples from the Iron Mountain kimberlite have identical Concordia U–Pb ages of 410.8 ± 3.4 Ma and 411.0 ± 2.6 Ma, which are consistent within errors with their corresponding Th–Pb ages of 409.2 ± 7.2 Ma and 412.3 ± 3.3 Ma, respectively. Two perovskite samples from the Wesselton Mine of South Africa yielded indistinguishable ²⁰⁶Pb/²³⁸U ages of 91.5 ± 2.2 Ma and 90.3 ± 2.9 Ma, and Th–Pb ages of 90.5 ± 0.8 Ma and 88.4 ± 1.6 Ma, respectively. Accuracy and precision of 1–2% (95% confidence level) for these measurements have been demonstrated by the consistency of their U–Pb and Th–Pb ages with the recommended U–Pb ages of previous works.     

Fluorite (U–Th)/He thermochronology: Constraints on the low temperature history of Yucca Mountain,Nevada

Fluorite is one of the secondary minerals precipitated in pore spaces at the future nuclear waste repository site at Yucca Mountain, Nevada. The authors have conducted (U–Th)/He dating of this fluorite in an attempt to constrain the temperature and timing of paleo-fluid flux into the site. Repeated analysis of colourless fluorite yielded a weighted average age of 9.7 ± 0.15 Ma (2σ), younger than previously determined sanidine ⁴⁰Ar/³⁹ Ar ages (12.8 Ma) for deposition of the tuff.Laboratory He-diffusion experiments conducted on the Yucca fluorite yield a preliminary He closure temperature (T_c) of 90 ± 10 °C (cooling rate of 10 °C/Ma) and previous studies have determined that the fluorite precipitated from warm fluids (65–80 °C) at depths of <400 m. However, minerals can experience partial He loss at temperatures well below the T_c and therefore the (U–Th)/He age of 9.7 Ma is interpreted to be a cooling age. This result implies that the last period of elevated temperature fluid circulation through the Yucca site was approximately 9.7 Ma ago.It was observed that the purple coloured outer portion of the fluorite nodule yielded non-reproducible and invariably older ages than colourless fluorite. Several possible reasons are suggested.     

Variation of initial Th/Th and limits of high precision U-Th dating of shallow-water corals

One hundred eighty U-Th data, including 23 isochrons on 24 pristine modern and Holocene corals and 33 seawater samples, were analyzed using sector-field mass spectrometry to understand the variability of initial ²³⁰Th/²³²Th (²³⁰Th/²³²Th₀). This dataset allows us to further assess the accuracy and precision of coral ²³⁰Th dating method. By applying quality control, including careful sampling and subsampling protocols and the use of contamination-free storage and workbench spaces, the resulting low procedural blanks give an equivalent uncertainty in age of only ±0.2-0.3 yr for 1-2 g of coral sample. Using site-specific ²³⁰Th/²³²Th₀ values or isochron techniques, our study demonstrates that corals with an age less than 100 yrs can be ²³⁰Th-dated with precisions of ±1 yr. Six living subtidal coral samples were collected from two continental shelf sites, Nanwan off southern Taiwan in the western Pacific and Son Tra off central Vietnam in the South China Sea; one coral core was drilled from an open-ocean site, Santo Island, Vanuatu, in the western tropical Pacific; and modern and fossil intertidal coral slabs, 17 in total, were cut from six sites around the islands of Simeulue, Lago, North Pagai and South Pagai of Sumatra in the eastern Indian Ocean. The results indicate that the main source of thorium is the dissolved phase of seawater, with variation of ²³⁰Th/²³²Th₀ depending on local hydrology. With intense input of terrestrial material, low ²³⁰Th/²³²Th₀ atomic ratios of 4.9 × 10⁻⁶ and 3.2 × 10⁻⁶ with a 10% variation are observed in Nanwan and Son Tra, respectively. At the Santo site, we find a value of 5.6 × 10⁻⁶ at 4 horizons and one high value of 24 × 10⁻⁶ in a sample from AD 1974.6 ± 0.5, likely due to the upwelling of cold water during a La Niña event between AD 1973 and 1976. The natural dynamics of ²³⁰Th/²³²Th₀ recorded in the intertidal corals at sites in the Sumatran islands are complicated so that this value varies significantly from 3.0 to 9.4 × 10⁻⁶. Three of the 141 modern coral ²³⁰Th ages differ from their true ages by −23 to +4, indicating the presence of detrital material with anomalous ²³⁰Th/²³²Th values. Duplicate measurement of coeval subsamples is therefore recommended to verify the age accuracy. This improved high precision coral ²³⁰Th dating method raises the prospects of refining the age models for band-counted and tracer-tuned chronologies and of advancing coral paleoclimate research.     

On the limits of using combined U-series/ESR method to date fossil teeth from two Early Pleistocene archaeological sites of the Orce area (Guadix-Baza basin,Spain)

The combined U-series/electron spin resonance (ESR) dating method was applied to nine teeth from two Early Pleistocene archaeological sites located in the Orce area (Guadix-Baza Basin, Southern Spain): Fuente Nueva-3 (FN-3) and Barranco León (BL). The combination of biostratigraphy and magnetostratigraphy places both sites between the Olduvai and Jaramillo subchrons (1.78–1.07 Ma).Our results highlight the difficulty of dating such old sites and point out the limits of the combined U-series/ESR dating method based on the US model. We identified several sources of uncertainties that may lead to inaccurate age estimates. Seven samples could not be dated because the dental tissues had (²³⁰Th/²³⁴U) activity ratios higher than equilibrium, indicating that uranium had probably leached from these tissues. It was however possible to calculate numerical estimates for two of the teeth, both from FN-3. One yielded a Middle Pleistocene age that seems to be strongly underestimated; the other provided an age of 1.19 ± 0.21 Ma, in agreement with data obtained from independent methods. The latter result gives encouragement that there are samples that can be used for routine dating of old sites.     

The influence of citric acid,EDTA, and fulvic acid on U(VI) sorption onto kaolinite

Uranium(VI) sorption onto kaolinite was investigated as a function of pH (3–12), sorbate/sorbent ratio (1 × 10^?6–1 × 10^?4 M U(VI) with 2 g/L kaolinite), ionic strength (0.001–0.1 M NaNO₃), and pCO₂ (0–5%) in the presence or absence of 1 × 10^?2–1 × 10^?4 M citric acid, 1 × 10^?2–1 × 10^?4 M EDTA, and 10 or 20 mg/L fulvic acid. Control experiments without-solids, containing 1 × 10^?6–1 × 10^?4 M U(VI) in 0.01 M NaNO₃ were used to evaluate sorption to the container wall and precipitation of U phases as a function of pH. Control experiments demonstrate significant loss (up to 100%) of U from solution. Although some loss, particularly in 1 × 10^?5 and 1 × 10^?4 M U experiments, is expected due to precipitation of schoepite, adsorption on the container walls is significant, particularly in 1 × 10^?6 M U experiments. In the absence of ligands, U(VI) sorption on kaolinite increases from pH ～3 to 7 and decreases from pH ～7.5 to 12. Increasing ionic strength from 0.001 to 0.1 M produces only a slight decrease in U(VI) sorption at pH < 7, whereas 10% pCO₂ greatly diminishes U(VI) sorption between pH ～5.5 and 11. Addition of fulvic acid produces a small increase in U(VI) sorption at pH < 5; in contrast, between pH 5 and 10 fulvic acid, citric acid, and EDTA all decrease U(VI) sorption. This suggests that fulvic acid enhances U(VI) sorption slightly via formation of ternary ligand bridges at low pH, whereas EDTA and citric acid do not form ternary surface complexes with the U(VI), and that all three ligands, as well as carbonate, form aqueous uranyl complexes that keep U(VI) in solution at higher pH.     

Radon emanation of heterogeneous basin deposits in Kathmandu Valley,Nepal

Effective radium-226 concentration (EC_Ra) has been measured in soil samples from seven horizontal and vertical profiles of terrace scarps in the northern part of Kathmandu Valley, Nepal. The samples belong to the Thimi, Gokarna, and Tokha Formations, dated from 50 to 14 ky BP, and represent a diverse fluvio-deltaic sedimentary facies mainly consisting of gravelly to coarse sands, black, orange and brown clays. EC_Ra was measured in the laboratory by radon-222 emanation. The samples (n = 177) are placed in air-tight glass containers, from which, after an accumulation time varying from 3 to 18 days, the concentration of radon-222, radioactive decay product of radium-226 and radioactive gas with a half-life of 3.8 days, is measured using scintillation flasks. The EC_Ra values from the seven different profiles of the terrace deposits vary from 0.4 to 43 Bq kg^?1, with profile averages ranging from 12 ± 1 to 27 ± 2 Bq kg^?1. The values have a remarkable consistency along a particular horizon of sediment layers, clearly demonstrating that these values can be used for long distance correlations of the sediment horizons. Widely separated sediment profiles, representing similar stratigraphic positions, exhibit consistent EC_Ra values in corresponding stratigraphic sediment layers. EC_Ra measurements therefore appear particularly useful for lithologic and stratigraphic discriminations. For comparison, EC_Ra values of soils from different localities having various sources of origin were also obtained: 9.2 ± 0.4 Bq kg^?1 in soils of Syabru–Bensi (Central Nepal), 23 ± 1 Bq kg^?1 in red residual soils of the Bhattar-Trisuli Bazar terrace (North of Kathmandu), 17.1 ± 0.3 Bq kg^?1 in red residual soils of terrace of Kalikasthan (North of Trisuli Bazar) and 10 ± 1 Bq kg^?1 in red residual soils of a site near Nagarkot (East of Kathmandu). The knowledge of EC_Ra values for these various soils is important for modelling radon exhalation at the ground surface, in particular in the vicinity of active faults. Importantly, the study also reveals that, above numerous sediments of Kathmandu Valley, radon concentration in dwellings can potentially exceed the level of 300 Bq m^?3 for residential areas; a fact that should be seriously taken into account by the governmental and non-governmental agencies as well as building authorities.     

U-series dating of co-seismic gypsum and submarine paleoseismology of active faults in Northern Chile (23°S)

The convergence of the Nazca and South American plates along the subduction margin of the central Andes results in large subduction earthquakes and tectonic activity along major fault systems. Despite its relevance, the paleoseismic record of this region is scarce, hampering our understanding about the relationship between the Andes building and earthquake occurrence. In this study, we used the U-series disequilibrium method to obtain absolute ages of paleoearthquake events associated with normal displacements along the active Mejillones and Salar del Carmen faults in the Coastal Range of the Atacama Desert of northern Chile. The ²³⁰Th–²³⁴U disequilibrium ages in co-seismic gypsum salts sampled along the fault traces together with marine evidences indicate that earthquakes occurred at ca. 29.7 ± 1.7 ka, 11 ± 4 ka and 2.4 ± 0.8 ka. When coupled with paleoseismic marine and radiocarbon (¹⁴C) records in the nearby Mejillones Bay evidencing large dislocations along the Mejillones Fault, the geochronological dataset presented here is consistent with the notion that gypsum salts formed during large earthquakes as a result of co-seismic dilatancy pumping of saline waters along the major faults. Based on maximum observed cumulative vertical offsets in the studied faults, this phenomena could have occurred episodically at a rate in the order of 1:40 to 1:50 with respect to the very large subduction earthquakes during the latest Pleistocene–Holocene period. The results presented here reveal that the U-series disequilibrium method can be successfully applied to date the gypsum salts deposited along faults during seismic events, and therefore directly constrain the age of large paleoearthquakes in hyperarid and seismically active zones.     

Zircon geochemistry of two contrasting types of eclogite: Implications for the tectonic evolution of the North Qaidam UHPM belt,northern Tibet

Compared to the extensively documented ultrahigh-pressure metamorphism at North Qaidam, the pre-metamorphic history for both continental crust and oceanic crust is poorly constrained. Trace element compositions, U–Pb ages, O and Lu–Hf isotopes obtained for distinct zircon domains from eclogites metamorphosed from both continental and oceanic mafic rocks are linked to unravel the origin and multi-stage magmatic/metamorphic evolution of eclogites from the North Qaidam ultrahigh-pressure metamorphic (UHPM) belt, northern Tibet.For continental crust-derived eclogite, magmatic zircon cores from two samples with U–Pb ages of 875–856 Ma have both very high δ¹⁸O (10.6 ± 0.5‰) and mantle-like δ¹⁸O (averaging at 5.2 ± 0.7‰), high Th/U and ¹⁷⁶Lu/¹⁷⁷Hf ratios, and steep MREE-HREE distribution patterns (chondrite-normalized) with negative Eu anomalies. Combined with positive ε_Hf (t) of 3.9–14.3 and T_DM (1.2–0.8 Ga and 1.3–1.0 Ga, respectively), they are interpreted as being crystallized from either subduction-related mantle wedge or recycled material in the mantle. While the metamorphic rims from the eclogites have U–Pb ages of 436–431 Ma, varying (inherited, lower, and elevated) oxygen isotopes compared with cores, low Th/U and ¹⁷⁶Lu/¹⁷⁷Hf ratios, and flat HREE distribution patterns with no Eu anomalies. These reflect both solid-state recrystallization from the inherited zircon and precipitation from external fluids at metamorphic temperatures of 595–622 °C (T_Ti-in-zircon).For oceanic crust-derived eclogite, the magmatic cores (510 ± 19 Ma) and metamorphic rims (442.0 ± 3.7 Ma) also show distinction for Th/U and ¹⁷⁶Lu/¹⁷⁷Hf ratios, and the REE patterns and Eu anomalies. Combined with the mantle-like δ¹⁸O signature of 5.1 ± 0.3 ‰ and two groups of model age (younger T_DM close to the apparent ages and older > 700 Ma), two possible pools, juvenile and inherited, were involved in mixing of mantle-derived magma with crustal components. The relatively high δ¹⁸O of 6.6 ± 0.3‰ for metamorphic zircon rims suggests either the protolith underwent hydrothermal alteration prior to the ~ 440 Ma oceanic crust subduction, or external higher δ¹⁸O fluid activities during UHP metamorphism at ~ 440 Ma.Therefore, the North Qaidam UHPM belt witnesses multiple tectonic evolution from Late Mesoproterozoic–Neoproterozoic assembly/breakup of the Rodinia supercontinent with related magmatic emplacement, then Paleozoic oceanic subduction, and finally transition of continental subduction/collision related to UHP metamorphism.     

Application of precise 142Nd/144Nd analysis of small samples to inclusions in diamonds (Finsch,South Africa) and Hadean Zircons (Jack Hills,Western Australia)

¹⁴⁶Sm–¹⁴²Nd and ¹⁴⁷Sm–¹⁴³Nd systematics were investigated in garnet inclusions in diamonds from Finsch (S. Africa) and Hadean zircons from Jack Hills (W. Australia) to assess the potential of these systems as recorders of early Earth evolution. The study of Finsch inclusions was conducted on a composite sample of 50 peridotitic pyropes with a Nd model age of 3.3 Ga. Analysis of the Jack Hills zircons was performed on 790 grains with ion microprobe ²⁰⁷Pb/²⁰⁶Pb spot ages from 3.95 to 4.19 Ga. Finsch pyropes yield 100 × ?¹⁴²Nd = ? 6 ± 12 ppm, ?¹⁴³Nd = ? 32.5, and ¹⁴⁷Sm/¹⁴⁴Nd = 0.1150. These results do not confirm previous claims for a 30 ppm ¹⁴²Nd excess in South African cratonic mantle. The lack of a ¹⁴²Nd anomaly in these inclusions suggests that isotopic heterogeneities created by early mantle differentiation were remixed at a very fine scale prior to isolation of the South African lithosphere. Alternatively, this result may indicate that only a fraction of the mantle experienced depletion during the first 400 Myr of its history. Analysis of the Jack Hills zircon composite yielded 100 × ?¹⁴²Nd = 8 ± 10 ppm, ?¹⁴³Nd = 45 ± 1, and ¹⁴⁷Sm/¹⁴⁴Nd = 0.5891. Back-calculation of this present-day ?¹⁴³Nd yields an unrealistic estimate for the initial ?¹⁴³Nd of ? 160 ?-units, clearly indicating post-crystallization disturbance of the ¹⁴⁷Sm–¹⁴³Nd system. Examination of ^146,147Sm–^142,143Nd data reveals that the Nd budget of the Jack Hills sample is dominated by non-radiogenic Nd, possibly contained in recrystallized zircon rims or secondary subsurface minerals. This secondary material is characterized by highly discordant U–Pb ages. Although the mass fraction of altered zircon is unlikely to exceed 5–10% of total sample, its high LREE content precludes a reliable evaluation of ¹⁴⁶Sm–¹⁴²Nd systematics in Jack Hills zircons.     

Soil pH governs production rate of calcium carbonate secreted by the earthworm Lumbricus terrestris

Lumbricus terrestris earthworms exposed to 11 soils of contrasting properties produced, on average, 0.8 ± 0.1 mg_CaCO3 earthworm^?1 day^?1 in the form of granules up to 2 mm in diameter. Production rate increased with soil pH (r² = 0.68, p < 0.01). Earthworms could be a significant source of calcite in soils.     

Hydrosulfide/sulfide complexes of zinc to 250 °C and the thermodynamic properties of sphalerite

The solubility of synthetic ZnS_(cr) was measured at 25–250 °C and P = 150 bars as a function of pH in aqueous sulfide solutions (~ 0.015–0.15 m of total reduced sulfur). The solubility determinations were performed using a Ti flow-through hydrothermal reactor. The solubility of ZnS_(cr) was found to increase slowly with temperature over the whole pH range from 2 to ~ 10. The values of the Zn–S–HS complex stability constant, β, were determined for Zn(HS)₂⁰_(aq), Zn(HS)₃^?, Zn(HS)₄^2?, and ZnS(HS)^?. Based on the experimental values the Ryzhenko–Bryzgalin electrostatic model parameters for these stability constants were calculated, and the ZnS_(cr) solubility and the speciation of Zn in sulfide-containing hydrothermal solutions were evaluated. The most pronounced solubility increase, about 3 log units at m(S_total) = 0.1 for the temperatures from 25 to 250 °C, was found in acidic solutions (pH ~ 3 to 4) in the Zn(HS)₂⁰_(aq) predominance field. In weakly alkaline solutions, where Zn(HS)₃^? and Zn(HS)₄^2? are the dominant Zn–S–HS complexes, the ZnS_(cr) solubility increases by 1 log unit at the same conditions. It was found that ZnS(HS)^? and especially Zn(HS)₄^2? become less important in high temperature solutions. At 25 °C and m(S_total) = 0.1, these species dominate Zn speciation at pH > 7. At 100 °C and m(S_total) = 0.1, the maximum fraction of Zn(HS)₄^2? is only 20% of the total Zn concentration (i.e. at pH_t ~ 7.5), whereas at 350 °C and 3 <pH_t <10, the fraction of Zn(HS)₄^2? and ZnS(HS)^? is less than 0.05% and 2.5% respectively, of the total Zn concentration and Zn(HS)₂⁰ and Zn(HS)₃^? predominate. The measured equilibrium formation constants were combined with the literature data on the stability of Zn–Cl complexes in order to evaluate the concentration and speciation of Zn in chloride solutions. It was found that at acidic pH, and in more saline fluids having total chloride > 0.05 m, Zn–Cl complexes are responsible for hydrothermal Zn transport with no significant contribution of Zn–S–HS complexes. The hydrosulfide/sulfide complexes will play a more important role in lower salinity (< 0.05 m chloride) hydrothermal solutions which are characteristic of many epithermal ore depositing environments. The value of Δ_fG° (β-ZnS_(cr)) = ? 198.6 ± 0.2 kJ/mol at 25 °C was determined via solubility measurements of natural low-iron Santander (Spain) sphalerite.     

Effects of fluorine on the solubilities of Nb,Ta, Zr and Hf minerals in highly fluxed water-saturated haplogranitic melts

The effect of fluorine on the solubilities of Mn-columbite (MnNb₂O₆), Mn-tantalite (MnTa₂O₆), zircon (ZrSiO₄) and hafnon (HfSiO₄) were determined in highly fluxed, water-saturated haplogranitic melts at 800 to 1000 °C and 2 kbar. The melt composition corresponds to the intersection of the granite minimum with the albite–orthoclase tieline (Ab₇₂Or₂₈) in the quartz–albite–orthoclase system (Q–Ab–Or), which is representative of a highly fluxed melt, from which high field strength element minerals may crystallize. The melt contains 1.7 wt.% P₂O₅, 1.05 wt.% Li₂O and 1.83 wt.% B₂O₃. The main purpose of this study is to examine the effect of F on columbite, tantalite, zircon and hafnon solubility for a melt with this composition. Up to 6 wt.% fluorine was added as AgF in order to keep the aluminum saturation index (ASI, molar Al/[Na + K]) of the melt constant. In an additional experiment F was added as AlF₃ to make a glass peraluminous. The nominal ASI of the melts are close to 1 for the minimum composition and approximately 1.32 in peraluminous glasses, but if Li is considered as an alkali, the molar ratio Al/[Na + K + Li] of the melts are alkaline (0.87) and subaluminous (1.09), respectively.The molar solubility products [MnO] 1 [Nb₂O₅] and [MnO] 1 [Ta₂O₅] are nearly independent of the F content of the melt, at approximately 18.19 ± 1.2 and 43.65 ± 2.5 × 10^− 4 (mol²/kg²), respectively for the minimum composition. By contrast, there is a positive dependence of zircon and hafnon solubilities on the fluorine content in the minimum composition, which increases from 2.03 ± 0.03 × 10^− 4 (mol/kg) ZrO₂ and 4.04 ± 0.2 × 10^− 4 (mol/kg) HfO₂ for melts with 0 wt.% F to 3.81 ± 0.3 × 10^− 4 (mol/kg) ZrO₂ and 6.18 ± 0.04 × 10^− 4 (mol/kg) HfO₂ for melts with 8 wt.% F. Comparison of the data from this work and previous studies indicates that ASI of the melt seems to have a stronger effect than the contents of fluxing elements in the melt and the overall conclusion is that fluorine is less important (relative to melt compositions) than previously thought for the control on the behavior of high field strength elements in highly evolved granitic melts. Moreover, this study confirms that although Nb, Ta, Zr and Hf are all high field strength elements, Nb–Ta and Zr–Hf are complexed differently in the melt.     

Dehydration and melting during continental collision: Constraints from element and isotope geochemistry of low-T/UHP granitic gneiss in the Dabie orogen

A combined study of petrography, whole-rock major and trace elements as well as Rb?Sr and Sm?Nd isotopes, and mineral oxygen isotopes was carried out for two groups of low-T/UHP granitic gneiss in the Dabie orogen. The results demonstrate that metamorphic dehydration and partial melting occurred during exhumation of deeply subducted continent. Zircon δ¹⁸O values of ? 2.8 to + 4.7‰ for the gneiss are all lower than normal mantle values of 5.3 ± 0.3‰, consistent with ¹⁸O depletion of protolith due to high-T meteoric-hydrothermal alteration at mid-Neoproterozoic. Most samples have extremely low ⁸⁷Sr/⁸⁶Sr ratios at t₁ = 780 Ma, but very high ⁸⁷Sr/⁸⁶Sr ratios at t₂ = 230 Ma. This suggests intensive fluid disturbance due to the hydrothermal alteration of protoliths during Neoproterozoic magma emplacement and the metamorphic dehydration during Triassic continental collision. Rb–Sr isotopes, Th/Ta vs. La/Ta and Th/Hf vs. La/Nb relationships suggest that Group I gneiss experienced lower degrees of hydrothermal alteration, but higher degrees of dehydration, than Group II gneiss. The two groups of gneiss have similar patterns of REE and trace element partition. Group I gneiss displays good correlations between Nb and LREEs but no correlations between Nb and LILEs (Rb, Ba, Pb, Th and U), indicating differential mobilities of LILEs during the dehydration. Thus the correlation between Nb and LREEs is inherited from protolith rather than caused by metamorphic modification. Relative to Group I gneiss, Group II gneiss has stronger negative Eu anomaly, lower contents of Sr and Ba but higher contents of Rb, Th and U. In particular, Nb correlates with LILEs (e.g., Rb, Sr, Ba, Th and U), but not with LREEs (La and Ce). This may indicate decoupling between the dehydration and LILEs transport during continental collision. Furthermore, dehydration melting may have occurred due to breakdown of muscovite during “hot” exhumation. Group II gneiss has extremely low contents of FeO + MgO + TiO₂ (1.04 to 2.08 wt.%), high SiO₂ contents of 75.33 to 78.23 wt%, and high total alkali (Na₂O + K₂O) contents (7.52 to 8.92 wt.%), comparable with compositions predicted from partial melting of felsic rocks by experimental studies. Almost no UHP metamorphic minerals survived; felsic veins of fine-grain minerals occurs locally between coarse-grain minerals, resulting in a kind of metatexite migmatites due to dehydration melting without considerable escape of felsic melts from the host gneiss. In contrast, Group I gneiss only shows metamorphic dehydration. Therefore, the two groups of gneiss show contrasting behaviors of fluid–rock interaction during the continental collision.     

Fe(III) mobilisation by carbonate in low temperature environments: Study of the solubility of ferrihydrite in carbonate media and the formation of Fe(III) carbonate complexes

The linkage between the iron and the carbon cycles is of paramount importance to understand and quantify the effect of increased CO₂ concentrations in natural waters on the mobility of iron and associated trace elements. In this context, we have quantified the thermodynamic stability of mixed Fe(III) hydroxo-carbonate complexes and their effect on the solubility of Fe(III) oxihydroxides. We present the results of carefully performed solubility measurements of 2-line ferrihydrite in the slightly acidic to neutral–alkaline pH ranges (3.8–8.7) under constant pCO₂ varying between (0.982–98.154 kPa) at 25 °C.The outcome of the work indicates the predominance of two Fe(III) hydroxo carbonate complexes FeOHCO₃ and Fe(CO₃)₃³⁻, with formation constants log^*β°_1,1,1 = 10.76 ± 0.38 and log β°_1,0,3 = 24.24 ± 0.42, respectively.The solubility constant for the ferrihydrite used in this study was determined in acid conditions (pH: 1.8–3.2) in the absence of CO₂ and at T = (25 ± 1) °C, as log^*K_s,0 = 1.19 ± 0.41.The relative stability of the Fe(III)-carbonate complexes in alkaline pH conditions has implications for the solubility of Fe(III) in CO₂-rich environments and the subsequent mobilisation of associated trace metals that will be explored in subsequent papers.     

Evaluation of radiation dose due to naturally occurring radionuclides in rock samples of different origins collected from Azad Kashmir

The state of Azad Kashmir is rich in three types of rocks, namely, sedimentary, metamorphic, and igneous rocks. These rocks contain extensive deposits of graphite, marble, limestone, quartzite, granite, dolerite, and sandstone, which are widely used for the construction of dwellings in Azad Kashmir and Pakistan. Therefore, knowledge about the presence of natural radioactivity in these materials is desirable to assess the radiological hazards associated with it. In this context, 30 rock samples were collected from different geologic formations of the Muzaffarabad Division, Azad Kashmir. After processing the samples, the specific activities of ²²⁶Ra, ²³²Th, and ⁴⁰ K in them were measured using a P-type coaxial high-purity germanium detector. The observed highest dose rate values for sedimentary, metamorphic, and igneous rocks have been found to be 83.16 ± 1.08, 135.87 ± 1.18, and 115.98 ± 1 nGy ⋅ h^–1, respectively. The radium equivalent activity (Ra_eq) varied from 23.76 ± 1.15 for dolerite sample (igneous rock) to 293.69 ± 2.60 Bq ⋅ kg^–1 for marble (metamorphic rock). The Ra_eq values of all rock samples are lower than the limit mentioned in the Organization for Economic Cooperation and Development (OECD, 1979) report (370 Bq ⋅ kg^–1, equivalent to γ-dose of 1.5 mSv ⋅ y^–1). The values of external (H_ex) and internal hazard indices (H_in) are less than unity. The mean outdoor and indoor annual effective dose equivalents are 0.073 mSv ⋅ y^–1 and 0.29 mSv ⋅ y^–1, respectively. The mean (over all types of rock samples) annual effective dose equivalent is reported as 0.36 mSv ⋅ y^–1.     

Paleo-depths reconstruction of the last 550,000 years based on the transfer function on recent and Quaternary benthic foraminifers of the East Corsica margin

In this study, the model H(i) = 109.6103 + C₁ × F1(i) + C₂ × F₂(i) + … + C₃₃ × F₃₃(i) obtained from depth modelling based on 33 recent benthic foraminifer species distribution, has been applied to the fossil benthic foraminifers from the borehole GDEC-4-2 drilled at a water depth of 491 m, in the East-Corsica basin, covering the last 550,000 years. The obtained variations of the paleo-depths show a medium correlation with the oscillations of the relative sea level and also with the fluctuations of the oxygen isotopic ratio (δ¹⁸O G. bulloides and δ¹⁸O C. pachyderma–C. wuellerstorfi). This newly developed transfer function is accompanied by an error margin of ± 86 m, suggesting that this model will probably be more suitable for a time scale of the order of a million years where sea level variations are recorded with larger amplitudes. Without considering these problems related to amplitudes, it also turns out that the “eustatic” signal of the microfauna is accompanied by a “trophic” signal, which should not to be neglected, especially at a millennial scale time resolution. Thus, the application of this method would require taking into account the bottom trophic effects strongly controlling the distribution of benthic foraminifer assemblages.     

Solubility of Fe2(OH)3Cl (pure-iron end-member of hibbingite) in NaCl and Na2SO4 brines

Pure-iron end-member hibbingite, Fe₂(OH)₃Cl(s), may be important to geological repositories in salt formations, as it may be a dominant corrosion product of steel waste canisters in an anoxic environment in Na–Cl- and Na–Mg–Cl-dominated brines. In this study, the solubility of Fe₂(OH)₃Cl(s), the pure-iron end-member of hibbingite (Fe^II, Mg)₂(OH)₃Cl(s), and Fe(OH)₂(s) in 0.04 m to 6 m NaCl brines has been determined. For the reactionFe₂(OH)₃Cl(s) + 3H⁺ ? 3 H₂O + 2 Fe²⁺ + Cl^?,the solubility constant of Fe₂(OH)₃Cl(s) at infinite dilution and 25 °C has been found to be log₁₀ K = 17.12 ± 0.15 (95% confidence interval using F statistics for 36 data points and 3 parameters). For the reactionFe(OH)₂(s) + 2H⁺ ? 2 H₂O + Fe²⁺,the solubility constant of Fe(OH)₂ at infinite dilution and 25 °C has been found to be log₁₀ K = 12.95 ± 0.13 (95 % confidence interval using F statistics for 36 data points and 3 parameters). For the combined set of solubility data for Fe₂(OH)₃Cl(s) and Fe(OH)₂(s), the Na⁺–Fe²⁺ pair Pitzer interaction parameter θ_{Na⁺/Fe²⁺} has been found to be 0.08 ± 0.03 (95% confidence interval using F statistics for 36 data points and 3 parameters). In nearly saturated NaCl brine we observed evidence for the conversion of Fe(OH)₂(s) to Fe₂(OH)₃Cl(s). Additionally, when Fe₂(OH)₃Cl(s) was added to sodium sulfate brines, the formation of green rust(II) sulfate was observed, along with the generation of hydrogen gas. The results presented here provide insight into understanding and modeling the geochemistry and performance assessment of nuclear waste repositories in salt formations.     

Cambrian volcanism in the Lhasa terrane,southern Tibet: Record of an early Paleozoic Andean-type magmatic arc along the Gondwana proto-Tethyan margin

The present study reports new zircon LA–ICP–MS U–Pb ages, trace element and Hf isotope data, and whole-rock major and trace element data from Cambrian metarhyolites from Zhaqian and Zhakang in the central Lhasa subterrane of southern Tibet. One sample from Zhakang provides a weighted mean ²⁰⁶Pb/²³⁸U age of 510.4 ± 4.0 Ma and two samples from Zhaqian yield weighted mean ²⁰⁶Pb/²³⁸U ages of 510.6 ± 2.6 Ma and 524.8 ± 2.9 Ma, indicating that the Zhaqian and Zhakang metarhyolites were contemporaneous. Both are characterized by high SiO₂ and K₂O and low Na₂O. They are also primarily high-K calc-alkaline, are enriched in Th, U, and light rare earth elements (LREEs), and are depleted in Nb, Ta, Ti, and P. Thus, they are geochemically similar to typical arc volcanic rocks. Moreover, the Zhaqian metarhyolites exhibit varying zircon ε_Hf(t) values (−3.8 to +0.3) that are comparable to those of the Zhakang metarhyolites (−4.9 to −1.0). Both metarhyolites are interpreted as resulting from partial melting of Proterozoic metasedimentary rocks with mantle-derived magma contributions. Contemporaneous magmatism in the early Paleozoic has also been recognized in other microcontinents along the Gondwana proto-Tethyan margin. The emplacement of these magmatic rocks and the development of a Cambro–Ordovician angular unconformity in the central Lhasa subterrane can be attributed to subduction of proto-Tethys Ocean lithosphere in a Andean-type magmatic arc setting following the assembly of various continental components within the Gondwana supercontinent.