Uranium and thorium diffusion in diopside

This paper presents new experimental data on the tracer diffusion rates of U and Th in diopside at 1 atm and 1150–1300°C. Diffusion couples were prepared by depositing a thin layer of U–Th oxide onto the polished surface of a natural diopside single crystal, and diffusion profiles were measured by ion microprobe depth profiling. For diffusion parallel to [001] the following Arrhenius relations were obtained: log₁₀D_U=(−5.75±0.98)−(418±28 kJ/mol)/2.303RT log₁₀D_Th=(−7.77±0.92)−(356±26 kJ/mol)/2.303RT. The diffusion data are used to assess the extent to which equilibrium is obtained during near fractional melting of a high-Ca pyroxene bearing mantle peridotite. We find that the diffusion rates for both elements are slow and that disequilibrium between solid and melt will occur under certain melting conditions. For near-fractional adiabatic decompression melting at ascent rates >3 cm/yr, high-Ca pyroxene will exhibit disequilibrium effects. High-Ca pyroxene will become zoned in U and Th and the melts extracted will be depleted in these incompatible elements relative to melts produced by equilibrium fractional melting. U and Th diffusivities in high-Ca pyroxene are similar, and diffusive fractionation of these elements will be limited. Numerical solutions to a dynamic melting model with diffusion-controlled chemical equilibration indicate that the activity ratio [²³⁰Th/²³⁸U] in a partial melt of spinel peridotite will be slightly less than 1 for a broad range of melting parameters. This result reinforces the already widely accepted conclusion that melting of spinel peridotite cannot account for ²³⁰Th excesses in mid-ocean ridge and ocean island basalts, and that garnet must therefore be present over part of the melting column.     

Uranium and thorium in the volcanic processes

Distribution of radioactive elements in the Quaternary alkaline volcanites of Northern Latium has been studied and conclusions of volcanological interest, both as to differentiation of magma in the more superficial levels of the crust and as to the relationship between volcanic eruption and concentration of particular elements, have been drawn. The following principal results are emphasized:

1. i)
   There are two well defined types of distribution of U and Th corresponding to fractional crystallization differentiation and to pneumatolytic (gaseous transfer) differentiation. From the volcanological viewpoint, this double distribution mirrors the hypomagma or pyromagma conditions of the melt, thus allowing the physico-chemical characters of the magma to be defined, in respect to the different magma chambers considered and to the different levels of the same magma chamber, before an eruption.     
   
   

The thorium isotope content of ocean water

²³²Th concentrations of surface and deep Pacific Ocean waters are 0.01–0.02 dpm/1000 kg (60 pgm/kg). The²³⁰Th activity is 0.03–0.13 dpm/1000 kg in surface waters and 0.3–2.7 dpm/1000 kg in deep waters. Chemical residence times based on in situ production from parent isotopes are about the same for²³⁰Th and²²⁸Th in surface waters (1–5 years) but are ten times greater for²³⁰Th in deep waters (10–100 years). Apparently there are additional sources of²³⁰Th into deep waters. At MANOP site S manganese nodule tops are enriched in Th isotopes by adsorption of Th from seawater and not by incorporation of Th-rich particulates.     

Uranium and thorium in paleozoic basalts of Nova Scotia (Canada)

In the Paleozoic basalts of Nova Scotia (Canada) metamorphosed to a greenschist facies grade, U and Th are closely associated with immobile elements (e.g. Zr and Nb). The coherence of these elements with K, typical of igneous rocks is, however, absent, U and Th are apparently not affected by greenschist facies metamorphism as are alkali and alkali earth elements and their variation thus reflects primary magmatic processes. It seems that during the early stages of metamorphism, U and Th were retained together with several other incompatible elements (Zr, Nb, La and Ce) in stable secondary phases or alternatively these elements may be held in primary accessory minerals such as zircon and apatite.     

Uranium and thorium isotopes in the rivers of the Amazonian basin: hydrology and weathering processes

Two expeditions (October 1989 and May 1992) were carried out to two points of the main Amazon River channel and four tributaries. The Solimões and Madeira rivers, taking their origin in the Andes, are whitewater rivers. The Negro River is a typical acid, blackwater river. The Trombetas River flows through bauxite‐rich areas, and is characterized by low concentrations of dissolved humic substances. The ²³⁸U, ²³⁴U, ²³²Th and ²³⁰Th activities were recorded from dissolved, suspended particulate phases and river bank sediments. The latter were analysed for their ²²⁶Ra, ²²⁸Ra and ²¹⁰Pb contents, and also subjected to leaching with 0·2 M hydroxylamine–hydrochloride solution to determine the concentrations of radionuclides bound to amorphous Fe hydroxides and Mn oxides and hydroxides. The dissolved U average concentration in the Amazon system is ten times lower than the mean world river concentration. The uranium concentration observed at Óbidos in the lower Amazon (0·095 µg L^?1), where the U content in the river bank sediments and suspended matter is lowest, suggests U release from the solid phase during river transport. About 485 t of U are transported annually to the Amazon delta area in dissolved form, and 1943 t bound to suspended particulate matter. Total U and Th concentrations in the river bank sediments ranged from 1·59 to 7·14 µg g^?1 and from 6·74 to 32 µg g^?1, respectively. The highest concentrations were observed in the Trombetas River. The proportion extracted by means of the hydroxylamine solution (HL) was relatively high for U in the Trombetas river bank sediment (31%) and for Th in the Solimões sediment (30%). According to the alpha recoil effects, the ²³⁴U/²³⁸U activity ratios of the Andean river waters and downstream Amazon water (Óbidos) were >1, but were <1 in the Negro River (at Manaus). The activity ratios of dissolved U correlate with pH and also with the U activity ratios in the river bank sediment hydroxylamine extracts. As expected, the ²³⁴U/²³⁸U activity ratios in river bank sediments were <1 in the Andean rivers and in the downstream Amazon, but they were >1 in the Trombetas and Negro rivers. Such ratios probably result from the binding of dissolved uranium to solid sediment. The ²²⁸Th/²³²Th ratios of river bank sediments were close to unity (except for the Negro River, where it is lower), suggesting no significant Th exchanges between the river water and the sediment. The ²²⁶Ra/²³²Th activity ratios were <1, and the ²²⁶Ra/²²⁸Ra activity ratios generally were significantly higher than the activity ratios of their respective parents. This perhaps is the result of easier leaching of the ²²⁶Ra parent, ²³⁰Th, from solid material (owing to the alpha recoil effect) than of the ²²⁸Ra parent. Uranium and thorium isotopes were used as tools to evaluate the chemical weathering rate of rocks in the Amazon system, which was estimated to be 2·7 cm 1000 year^?1 s^?1. Copyright © 2002 John Wiley & Sons, Ltd.     

Uranium and thorium series nuclides in oriented ferromanganese nodules: growth rates,turnover times and nuclide behavior

Three ferromanganese nodules handpicked from the tops of 2500 cm² area box cores taken from the north equatorial Pacific have been analysed for their U-Th series nuclides.²³⁰Th_exc concentrations in the surface 1–2 mm of the top side of the nodules indicate growth rates of 1.8–4.6 mm/10⁶ yr. In two of the nodules a significant discontinuity in the²³⁰Th_exc depth profile has been observed at ～0.3 m.y. ago, suggesting that the nodule growth has been episodic. The concentration profiles of²³¹Pa_exc (measured via²²⁷Th) yield growth rates similar to the²³⁰Th_exc data. The bottom sides of the nodules display exponential decrease of²³⁰Th_exc/²³²Th activity ratio with depth, yielding growth rates of 1.5–3.3 mm/10⁶ yr.The²³⁰Th_exc and²³¹Pa_exc concentrations in the outermost layer of the bottom face are significantly lower than in the outermost layer of the top face. Comparison of the extrapolated²³⁰Th_exc/²³²Th and²³⁰Th_exc/²³¹Pa_exc activity ratios for the top and bottom surfaces yields an “age” of (5?15) × 10⁴ yr for the bottom relative to the top. This “age” most probably represents the time elapsed since the nodules have attained the present orientation.The²¹⁰Pb concentration in the surface ～0.1 mm of the top side is in large excess over its parent²²⁶Ra. Elsewhere in the nodule, up to ～1 mm depth in both top and bottom sides,²¹⁰Pb is deficient relative to²²⁶Ra, probably due to²²²Rn loss. The absence of²¹⁰Pb_exc below the outermost layer of the top face rules out the possibility of a sampling artifact as the cause of the observed exponentially decreasing²³⁰Th_exc and²³¹Pa_exc concentration profiles. The flux of²¹⁰Pb_exc to the nodules ranges between 0.31 and 0.58 dpm/cm² yr. The exhalation rate of²²²Rn, estimated from the²²⁶Ra-²¹⁰Pb disequilibrium is ～570 dpm/cm² yr from the top side and >2000 dpm/cm² yr from the bottom side.²²⁶Ra is deficient in the top side relative to²³⁰Th up to ～0.5–1 mm and is in large excess throughout the bottom. The data indicate a net gain of²²⁶Ra into the nodule, corresponding to a flux of (24?46) × 10^?3 dpm/cm² yr. On a total area basis the gain of²²⁶Ra into the nodules is <20% of the²²⁶Ra escaping from the sediments. A similar gain of²²⁸Ra into the bottom side of the nodules is reflected by the high²²⁸Th/²³²Th activity ratios observed in the outermost layer in contact with sediments.     

Oxygen isotope activities and concentrations in aqueous salt solutions at elevated temperatures: Consequences for isotope geochemistry

Studies of the effect of dissolved salts on the oxygen isotope activity ratio of water have been extended to 275°C. Dehydrated salts were added to water of known isotope composition and the solutions were equilibrated with CO₂ which was sampled for analysis. For comparison similar studies were made using pure water. Results on water nearly coincide with earlier calculations. Salt effects diminish with increasing temperature only for solutions of MgCl₂ and LiCl. Other salt solutions show complex behavior due to the temperature-dependent formation of ion pairs of changing character. Equilibrium fractionations (10³ ln α) between 1 molal solutions and pure water at 25, 100, and 275°C are: NaCl 0.0, ?1.5, +1.0; KCl 0.0, ?1.0, +2.0; LiCl ?1.0, ?0.6, ?0.5; CaCl₂ ?0.4, ?1.8, +0.8; MgCl₂ ?1.1, ?0.7, ?0.3; MgSO₄ ?1.1, +0.1, ?; NaF (0.8 m) 0.0, ?1.5, ?0.3; and NH₄Cl (0.55 m) 0.0, ?1.2, ?1.3. These effects are significant in the isotope study of hot saline fluids responsible for ore deposition and of fluids found in certain geothermal systems. Minor modification of published isotope geothermometers may be required.     

High-resolution terrestrial carbon isotope and planktic foraminiferal records of the Upper Cenomanian to the Lower Campanian in the Northwest Pacific

Making Upper Cretaceous biostratigraphic correlations between the Northwest Pacific and Tethyan–Atlantic sections have been difficult because of rare frequencies of age-diagnostic macro- and microfossils in the sequences in the Northwest Pacific region. In order to correlate these sections precisely, an integrated planktic foraminiferal and bulk wood carbon-isotope stratigraphy from the upper Cenomanian to the lower Campanian succession (the middle–upper part of the Yezo Group) of Hokkaido, northern Japan is established with an average resolution of 50 k.y. The δ¹³C curves from bulk wood of the Yezo Group and from bulk carbonate of English Chalk show remarkably similar patterns of isotopic fluctuation, allowing the correlation of 22 carbon isotopic events between these sections. This high-resolution correlation greatly improves the previous micro- and macrofossil biostratigraphic schemes in the Northwest Pacific region, and reveals that global events, such as the oxygen depletion at the OAE 2 horizon, the constant decrease in pCO₂ during the Late Cretaceous, and the eustatic sea-level falls in the late middle Turonian, Santonian/Campanian Boundary and early Campanian, are recorded in the Upper Cretaceous sequence of the Northwest Pacific.     

REE diffusion in calcite

Chemical diffusion of four rare-earth elements (La, Nd, Dy and Yb) has been measured in natural calcite under anhydrous conditions, using rare-earth carbonate powders as the source of diffusants. Experiments were run in sealed silica capsules along with finely ground calcite to ensure stability of the single-crystal samples during diffusion anneals. Rutherford backscattering spectroscopy (RBS) was used to measure diffusion profiles. The following Arrhenius relations were obtained over the temperature range 600–850°C: D_La =2.6×10⁻¹⁴ exp(−147±14 kJ mol⁻¹/RT) m² s⁻¹, D_Nd =2.4×10⁻¹⁴ exp(−150±13 kJ mol⁻¹/RT) m² s⁻¹, D_Dy =2.9×10⁻¹⁴ exp(−145±25 kJ mol⁻¹/RT) m² s⁻¹, D_Yb =3.9×10⁻¹² exp(−186±23 kJ mol⁻¹/RT) m² s⁻¹. In contrast to previous findings for refractory silicates (e.g. zircon), differences in transport rates among the REE are not pronounced over the range of temperature conditions investigated in this study. Diffusion of the REE is significantly slower than diffusion of the divalent cations Sr and Pb and slower than transport of Ca and C at temperatures above 650°C. Fine-scale zoning and isotopic and REE chemical signatures may be retained in calcites under many conditions if diffusion is the dominant process affecting alteration.     

δCa evolution in a carbonate aquifer and its bearing on the equilibrium isotope fractionation factor for calcite

To improve understanding of Ca isotope transport during water-rock interaction on the continents, we measured dissolved δ⁴⁴Ca values along a 236 km flow path in the Madison aquifer, South Dakota, where fluids have chemically evolved according to dolomite and anhydrite dissolution, calcite precipitation, and Ca-for-Na ion-exchange over a timescale spanning ~ 15 kyr. We used a reactive transport model employing rate data constrained from major ion mass-balances to evaluate the extent to which calcite precipitation and ion-exchange fractionate Ca isotopes. Elevated δ⁴⁴Ca values during the initial and final stages of water transport possibly result from calcite precipitation under supersaturated conditions and Ca-for-Na ion-exchange, respectively. However, for the bulk of the flow path, δ⁴⁴Ca values evolve by mixing between anhydrite and dolomite dissolution, with no fractionation during calcite precipitation under saturated conditions. We attribute the absence of Ca isotope fractionation to the long timescale of water-rock interaction and slow rate of calcite precipitation, which have enabled fluids to chemically and isotopically equilibrate with calcite. We therefore conclude that the equilibrium Ca isotope fractionation factor between calcite and water (Δ_cal–w) is very close to zero. To the extent that the Madison aquifer typifies other groundwater systems where calcite slowly precipitates from solutions at or near chemical equilibrium, this study suggests that groundwater contributions to δ⁴⁴Ca variability on the continents can be modeled according to simple mixing theory without invoking isotope discrimination.     

Uranium and thorium isotopes in minerals from the « Cetara — Serrara Fontana » tuff (Ischia Island,Italy) — A tentative radiometric dating

A cineritic level, which appears very interesting from a chronostratigraphic point of view because it is found throughout the eastern Mediterranean Sea, has been related to the « Cetara — Serrara Fontana » tuff formation (Ischia Island, Italy) by previous authors who estimated the age of this cineritic level to be about 25,000 years. A direct dating of the « Cetara — Serrara Fontana » tuff has been attempted by means of isotopic analyses of uranium and thorium in sphene, glass, clinopyroxenes and magnetite from four tuff samples. The calculated age is 41,500±3,000 years only if glass and sphene are assumed to be coeval. On the other hand, assuming as true the age of 25,000 years for the Cetara tuff, we must conclude that the sphene crystallized before the eruption. The age of the clinopyroxenes and magnetite is older than 300,000 years: therefore, they are possibly pre-existing minerals reworked by the Cetara explosion.     

Retention of cosmogenic 3He in calcite

Cosmogenic ³He can be used to date a wide range of mineral phases because it is produced from all target elements and can be readily measured above atmospheric contamination. Calcite is a particularly attractive target mineral due to its natural abundance, large crystal size (>1 mm), and low He closure temperature (<70 °C), which limit non-cosmogenic ³He components (Copeland et al., 2007). However, several recent studies have shown that some calcite may not be retentive to helium, even under surface temperatures (Cros et al., 2014; Copeland et al., 2007). This study thus explores ³He retention and production in natural calcite samples at four different sites. Samples from two high elevation sites appear retentive to ³He over 10 kyr timescales, whereas two additional sites clearly suffer from diffusive loss of ³He. Step-degassing experiments suggest that diffusion in calcite is controlled by multiple diffusion domains, with an apparent activation energy of 25–27 kcal mol⁻¹. Although minor ³He loss is expected from the smallest diffusion domains, the observed kinetics cannot explain the poor retention at all sites. We thus propose that opaque (non-transparent) calcite may be more retentive due to the presence of imperfections in the crystal lattice. We conclude that ³He dating of calcite shows promise in some settings. However, because retention depends on crystallographic variability it must be evaluated on a case-by-case basis until robust criteria for retention can be identified.     

Uranium isotopes in the Greenland ice-sheet

The²³⁴U/²³⁸U activity ratio was measured in dated strata of the Dye-3 Greenland ice-sheet. Values were generally less than unity indicating a source in weathered crustal rock debris. Three levels showed elevated ratios which are attributed to entry of debris from the aborted Russian satellite Cosmos 954 following residence in the stratosphere.     

Decomposition of hydroxy amino acids in foraminiferal tests; kinetics,mechanism and geochronological implications

The diagenesis of the hydroxy amino acids serine and threonine in foraminiferal tests has been investigated. The decomposition pathways of these amino acids are complex; the principal reactions appear to be dehydration, aldol cleavage and decarboxylation. Stereochemical studies indicate that the α-amino-n-butyric acid (ABA) detected in foraminiferal tests is the end product of threonine dehydration pathway. Decomposition of serine and threonine in foraminiferal tests from two well-dated Caribbean deep-sea cores, P6304-8 and -9, has been found to follow irreversible first-order kinetics. Three empirical equations were derived for the disappearance of serine and threonine and the appearance of ABA. These equations can be used as a new geochronological method for dating foraminiferal tests from other deep-sea sediments. Preliminary results suggest that ages deduced from the ABA kinetics equation are most reliable because “species effect” and contamination problems are not important for this nonbiological amino acid. Because of the variable serine and threonine contents of modern foraminiferal species, it is likely that the accurate age estimates can be obtained from the serine and threonine decomposition equations only if a homogeneous species assemblage or single species sample isolated from mixed natural assemblages is used.     

Fluxes of uranium and thorium series isotopes in the Santa Barbara Basin

Samples from the MANOP Santa Barbara Basin sediment trap intercomparison were analyzed for the isotopes of uranium, thorium, radium, lead, and polonium. All of the traps showed approximately the same compositions and isotopic ratios, indicating that they trapped similar materials. The²³⁴Th flux via falling particles was very close to the flux predicted from the production and scavenging rates of²³⁴Th from the water column. The²¹⁰Pb content of the trapped particles and the surface sediments were the same, however, the measured flux of²¹⁰Pb was seven times greater than the predicted flux. Predicted and measured fluxes of²²⁸Th and²¹⁰Po were similarly out of balance. To explain this apparent inconsistency, we suggest (as others have done) that the Santa Barbara Basin is an area where scavenging from the water column is intensified and where sediments deposited initially on the margins may be physically remobilized on a short time scale. These two effects increase the apparent area from which the basin derives the longer-lived isotopes but does not increase significantly the supply of the short-lived²³⁴Th.     

Calibrations for benthic foraminiferal Mg/Ca paleothermometry and the carbonate ion hypothesis

Benthic foraminiferal magnesium/calcium ratios were determined on one hundred and forty core-top samples from the Atlantic Ocean, the Norwegian Sea, the Indian Ocean, the Arabian Sea and the Pacific Ocean, mostly at sites with bottom water temperatures below 5 °C. Mg/Ca ratios are consistently lower, by  0.2 mmol/mol, in samples cleaned using oxidative and reductive steps than using oxidative cleaning. Differences between Cibicidoides species have been identified: Mg/Ca of Cibicidoides robertsonianus > Cibicidoides kullenbergi > Cibicidoides wuellerstorfi. Comparison with bottom water temperatures support observations of lowered Mg/Ca of C. wuellerstorfi at temperature below  3 °C compared with values predicted by published calibrations and from other Cibicidoides species. Hydrographic data shows that carbonate ion saturation (Δ[CO₃²⁻]) decreases rapidly below this temperature. An empirical sensitivity of Δ[CO₃²⁻] on Mg/Ca has been established for C. wuellerstorfi of 0.0086 ± 0.0006 mmol/mol/μmol/kg. A novel application using modern temperatures and Last Glacial Maximum temperatures derived via pore fluid modelling supports a carbonate ion saturation state effect on Mg incorporation. This may significantly affect calculated δ¹⁸O_seawater obtained from foraminiferal δ¹⁸O and Mg/Ca temperature.     

Uranium and boron distributions in some oceanic ultramafic rocks

From mica fission-track maps the serpentinized and weathered portions of four ultramafic rocks from oceanic ridge systems contained 0.5 to 2.4 ppm U compared to only 2.5 ppb in clinopyroxene, 0.6 ppb in chromite and less than 7.0 ppb in olivine. Orthopyroxene grains contained 0.4 ppb U which is three orders of magnitude lower than had previously been reported.Long thin tracks from (n, α) reactions with boron were recorded in cellulose nitrate plastic and were counted like fission tracks. The track density from boron was 2×10⁴ times higher than that from uranium fission alone. Boron in serpentine was variable on a 50-μm scale attaining 155 ppm concentrations. Orthopyroxene grains, in contrast, had maximum concentrations of 0.8 ppm.Most of the uranium and boron in the rocks is believed to have been introduced during serpentinization. From known crystal-melt partitioning ratios the uranium and boron distributions are consistent with the ultramafic rocks being cumulates or residues from partial melting events.