Understanding melt generation beneath the slow-spreading Kolbeinsey Ridge using U, Th, and Pa excesses

To examine the petrogenesis and sources of basalts from the Kolbeinsey Ridge, one of the shallowest locations along the global ridge system, we present new measurements of Nd, Sr, Hf, and Pb isotopes and U-series disequilibria on 32 axial basalts. Young Kolbeinsey basalts (full-spreading rate = 1.8 cm/yr; 67°05′-70°26′N) display (²³⁰Th/²³⁸U) < 1 and (²³⁰Th/²³⁸U) > 1 with (²³⁰Th/²³⁸U) from 0.95 to 1.30 and have low U (11.3-65.6 ppb) and Th (33.0 ppb-2.40 ppm) concentrations. Except for characteristic isotopic enrichment near the Jan Mayen region, the otherwise depleted Kolbeinsey basalts (e.g. ⁸⁷Sr/⁸⁶Sr = 0.70272-0.70301, ε_Nd = 8.4-10.5, ε_Hf = 15.4-19.6 (La/Yb)_N = 0.28-0.84) encompass a narrow range of (²³⁰Th/²³²Th) (1.20-1.32) over a large range in (²³⁸U/²³²Th) (0.94-1.32), producing a horizontal array on a (²³⁰Th/²³²Th) vs. (²³⁸U/²³²Th) diagram and a large variation in (²³⁰Th/²³⁸U). However, the (²³⁰Th/²³⁸U) of the Kolbeinsey Ridge basalts (0.96-1.30) are inversely correlated with (²³⁴U/²³⁸U) (1.001-1.031). Samples with low (²³⁰Th/²³⁸U) and elevated (²³⁴U/²³⁸U) reflect alteration by seawater or seawater-derived materials. The unaltered Kolbeinsey lavas with equilibrium ²³⁴U/²³⁸U have high (²³⁰Th/²³⁸U) values (?1.2), which are consistent with melting in the presence of garnet. This is in keeping with the thick crust and anomalously shallow axial depth for the Kolbeinsey Ridge, which is thought to be the product of large degrees of melting in a long melt column. A time-dependent, dynamic melting scenario involving a long, slowly upwelling melting column that initiates well within the garnet peridotite stability zone can, in general, reproduce the (²³⁰Th/²³⁸U) and (²³¹Pa/²³⁵U) ratios in uncontaminated Kolbeinsey lavas, but low (²³¹Pa/²³⁵U) ratios in Eggvin Bank samples suggest eclogite involvement in the source for that ridge segment.     

Natural radionuclide mobility and its influence on U-Th-Pb dating of secondary minerals from the unsaturated zone at Yucca Mountain, Nevada

Extreme U and Pb isotope variations produced by disequilibrium in decay chains of ²³⁸U and ²³²Th are found in calcite, opal/chalcedony, and Mn-oxides occurring as secondary mineral coatings in the unsaturated zone at Yucca Mountain, Nevada. These very slowly growing minerals (mm my⁻¹) contain excess ²⁰⁶Pb and ²⁰⁸Pb formed from excesses of intermediate daughter isotopes and cannot be used as reliable ²⁰⁶Pb/²³⁸U geochronometers. The presence of excess intermediate daughter isotopes does not appreciably affect ²⁰⁷Pb/²³⁵U ages of U-enriched opal/chalcedony, which are interpreted as mineral formation ages.Opal and calcite from outer (younger) portions of coatings have ²³⁰Th/U ages from 94.6 ± 3.7 to 361.3 ± 9.8 ka and initial ²³⁴U/²³⁸U activity ratios (AR) from 4.351 ± 0.070 to 7.02 ± 0.12, which indicate ²³⁴U enrichment from percolating water. Present-day ²³⁴U/²³⁸U AR is ∼1 in opal/chalcedony from older portions of the coatings. The ²⁰⁷Pb/²³⁵U ages of opal/chalcedony samples range from 0.1329 ± 0.0080 to 9.10 ± 0.21 Ma, increase with microstratigraphic depth, and define slow long-term average growth rates of about 1.2-2.0 mm my⁻¹, in good agreement with previous results. Measured ²³⁴U/²³⁸U AR in Mn-oxides, which pre-date the oldest calcite and opal/chalcedony, range from 0.939 ± 0.006 to 2.091 ± 0.006 and are >1 in most samples. The range of ⁸⁷Sr/⁸⁶Sr ratios (0.71156-0.71280) in Mn-oxides overlaps that in the late calcite. These data indicate that Mn-oxides exchange U and Sr with percolating water and cannot be used as a reliable dating tool.In the U-poor calcite samples, measured ²⁰⁶Pb/²⁰⁷Pb ratios have a wide range, do not correlate with Ba concentration as would be expected if excess Ra was present, and reach a value of about 1400, the highest ever reported for natural Pb. Calcite intergrown with opal contains excesses of both ²⁰⁶Pb and ²⁰⁷Pb derived from Rn diffusion and from direct α-recoil from U-rich opal. Calcite from coatings devoid of opal/chalcedony contains ²⁰⁶Pb and ²⁰⁸Pb excesses, but no appreciable ²⁰⁷Pb excesses. Observed Pb isotope anomalies in calcite are explained by Rn-produced excess Pb. The Rn emanation may strongly affect ²⁰⁶Pb-²³⁸U ages of slow-growing U-poor calcite, but should be negligible for dating fast-growing U-enriched speleothem calcite.     

U-Sr isotopic speedometer: Fluid flow and chemical weathering rates in aquifers

Both chemical weathering rates and fluid flow are difficult to measure in natural systems. However, these parameters are critical for understanding the hydrochemical evolution of aquifers, predicting the fate and transport of contaminants, and for water resources/water quality considerations. ⁸⁷Sr/⁸⁶Sr and (²³⁴U/²³⁸U) activity ratios are sensitive indicators of water-rock interaction, and thus provide a means of quantifying both flow and reactivity. The ⁸⁷Sr/⁸⁶Sr values in ground waters are controlled by the ratio of the dissolution rate to the flow rate. Similarly, the (²³⁴U/²³⁸U) ratio of natural ground waters is a balance between the flow rate and the dissolution of solids, and α-recoil loss of ²³⁴U from the solids. By coupling these two isotope systems it is possible to constrain both the long-term (ca. 100’s to 1000’s of years) flow rate and bulk dissolution rate along the flow path. Previous estimates of the ratio of the dissolution rate to the infiltration flux from Sr isotopes (⁸⁷Sr/⁸⁶Sr) are combined with a model for (²³⁴U/²³⁸U) to constrain the infiltration flux and dissolution rate for a 70-m deep vadose zone core from Hanford, Washington. The coupled model for both (²³⁴U/²³⁸U) ratios and the ⁸⁷Sr/⁸⁶Sr data suggests an infiltration flux of 5 ± 2 mm/yr, and bulk silicate dissolution rates between 10^−15.7 and 10^−16.5 mol/m²/s. The process of α-recoil enrichment, while primarily responsible for the observed variation in (²³⁴U/²³⁸U) of natural systems, is difficult to quantify. However, the rate of this process in natural systems affects the interpretation of most U-series data. Models for quantifying the α-recoil loss fraction based on geometric predictions, surface area constraints, and chemical methods are also presented. The agreement between the chemical and theoretical methods, such as direct measurement of (²³⁴U/²³⁸U) of the small grain size fraction and geometric calculations for that size fraction, is quite good.     

Timescales of magma differentiation from basalt to andesite beneath Hekla Volcano, Iceland: Constraints from U-series disequilibria in lavas from the last quarter-millennium flows

Measurements of ²³⁸U-²³⁰Th-²²⁶Ra disequilibria, Sr-Nd-Pb-Hf isotopes and major-trace elements have been conducted for lavas erupted in the last quarter-millennium at Hekla volcano, Iceland. The volcanic rocks range from basalt to dacite. Most of the lavas (excluding dacitic samples) display limited compositional variations in radiogenic Sr-Nd-Pb-Hf isotopes (⁸⁷Sr/⁸⁶Sr = 0.70319-0.70322; ¹⁴³Nd/¹⁴⁴Nd = 0.51302-0.51305; ²⁰⁶Pb/²⁰⁴Pb = 19.04-19.06; ²⁰⁷Pb/²⁰⁴Pb = 15.53-15.54; ²⁰⁸Pb/²⁰⁴Pb = 38.61-38.65; ¹⁷⁶Hf/¹⁷⁷Hf = 0.28311-0.28312). All the samples possess (²³⁰Th/²³⁸U) disequilibrium with ²³⁰Th excesses, and they show systematic variations in (²³⁰Th/²³²Th) and (²³⁸U/²³²Th) ratios. The highest ²²⁶Ra excesses occur in the basalt and most differentiated andesite lavas, while some basaltic-andesite lavas have (²²⁶Ra/²³⁰Th) ratio that are close to equilibrium. The ²³⁸U-²³⁰Th-²²⁶Ra disequilibria variations cannot be produced by simple closed-system fractional crystallization with radioactive decay of ²³⁰Th and ²²⁶Ra in a magma chamber. A closed-system fractional crystallization model and assimilation and fractional crystallization (AFC) model indicate that the least differentiated basaltic andesites were derived from basalt by fractional crystallization with a differentiation age of ∼24 ± 11 kyr, whereas the andesites were formed by assimilation of crustal material and fractionation of the basaltic-andesites within 2 kyr. Apatite is inferred to play a key role in fractionating the parent-daughter nuclides in ²³⁰Th-²³⁸U and ²²⁶Ra-²³⁰Th to make the observed variations. Our proposed model is that several batches of basaltic-andesite magmas that formed by fractional crystallization of a basaltic melt from a deeper reservoir, were periodically injected into the shallow crust to form individual magma pockets, and subsequently modifying the original magma compositions via simultaneous assimilation and fractional crystallization. The assimilant is the dacitic melt, which formed by partial melting of the crust.     

Weathering rates from top to bottom in a carbonate environment

This study investigates U-series, Sr isotopes, major and trace elements in a chalk aquifer system located in Eastern France. Soil and rock samples were collected along depth profiles down to 45 m in four localities as an attempt to investigate the weathering processes in the soil, the unsaturated zone and the saturated zone of the aquifer. Interstitial water was extracted from soils and rocks by a centrifugation technique. U-series offer a powerful tool to calculate weathering rates because the relative mobility of the U- and Th-isotopes can be precisely measured and it does not require the determination of a reference state as in other approaches. As expected, the data show very large mobile element depletion in the soil with large ²³⁰Th excess relative to ²³⁸U, while the rocks show more limited but not insignificant mobile element depletion. The U-series data have been used to constrain weathering rates based on a 1-D reactive transport model. Weathering rates in the near surface are about 10–100 times faster than at depth. However, when integrated over the depth of the cores, including the unsaturated and the saturated zones, this underground weathering represents more than 30% of the total weathering flux, assuming congruent dissolution of carbonates. The (²³⁴U/²³⁸U) ratios in interstitial water are consistent with solid samples showing ²³⁴U depletion near the surface and an excess ²³⁴U at depth. A leaching experiment performed on chalk shows that the excess ²³⁴U in natural waters percolating through carbonate rocks results both from preferential ²³⁴U leaching and direct recoil in the interstitial water. A new approach was used to derive the recoil ejection factor based on BET measurements and the fractal dimension of chalk surface. Consideration of preferential leaching and recoil allows a more accurate modeling of weathering rates.     

Uranium-series dating of pedogenic silica and carbonate, Crater Flat, Nevada

A ²³⁰Th-²³⁴U-²³⁸U dating study on pedogenic silica-carbonate clast rinds and matrix laminae from alluvium in Crater Flat, Nevada was conducted using small-sample thermal-ionization mass spectrometry (TIMS) analyses on a large suite of samples. Though the ²³²Th content of these soils is not particularly low (mostly 0.1-9 ppm), the high U content of the silica component (mostly 4-26 ppm) makes them particularly suitable for ²³⁰Th/U dating on single, 10 to 200 mg totally-digested samples using TIMS. We observed that (1) both micro- (within-rind) and macro-stratigraphic (mappable deposit) order of the ²³⁰Th/U ages were preserved in all cases; (2) back-calculated initial ²³⁴U/²³⁸U fall in a restricted range (typically 1.67±0.19), so that ²³⁴U/²³⁸U ages with errors of about 100 kyr (2σ) could be reliably determined for the oldest, 400 to 1000 ka rinds; and (3) though 13 of the samples were >350 ka, only three showed evidence for an open-system history, even though the sensitivity of such old samples to isotopic disruption is very high. An attempt to use leach-residue techniques to separate pedogenic from detrital U and Th failed, yielding corrupt ²³⁰Th/U ages. We conclude that ²³⁰Th/U ages determined from totally dissolved, multiple sub-mm size subsamples provide more reliable estimates of soil chronology than methods employing larger samples, chemical enhancement of ²³⁸U/²³²Th, or isochrons.     

Geochemical evolution of a shallow magma plumbing system during the last 500 years, Miyakejima volcano, Japan: Constraints from U-Th-Ra systematics

In order to unravel magma processes and the geochemical evolution of shallow plumbing systems beneath active volcanoes, we investigated U-series disequilibria of rocks erupted over the past 500 years (1469-2000 AD) from Miyakejima volcano, Izu arc, Japan. Miyakejima volcanic rocks show ²³⁸U-²³⁰Th-²²⁶Ra disequilibria with excess ²³⁸U and ²²⁶Ra, due to the addition of slab-derived fluids to the mantle wedge. Basaltic bombs of the 2000 AD eruption have the lowest (²³⁰Th/²³²Th) ratio compared to older Miyakejima eruptives, yielding the youngest ²³⁸U-²³⁰Th model age of 2 kyr. This reinforces our previous model that fluid release from the slab and subsequent magma generation in the mantle wedge beneath Miyakejima occur episodically on a several-kyr timescale. In the last 500 years, Miyakejima eruptives show: (1) a vertical trend in a (²³⁰Th/²³²Th)-(²³⁸U/²³²Th) diagram and (2) a positive linear correlation in a (²²⁶Ra/²³⁰Th)₀ − 1/²³⁰Th diagram, which is also observed in lavas from some of the single eruptions (e.g., 1940, 1962, and 1983 AD). The variations cannot be produced by simple fractional crystallization in a magma chamber with radioactive decay of ²³⁰Th and ²²⁶Ra, but it is possibly produced by synchronous generation of melts in the mantle wedge with different upwelling rate or addition of multiple slab-derived fluids. A much more favorable scenario is that some basaltic magmas were intermittently supplied from deep in the mantle and injected into the crust, subsequently modifying the original magma composition and producing variations in (²³⁰Th/²³²Th) and (²²⁶Ra/²³⁰Th)₀ ratios via assimilation and fractional crystallization (AFC). The assimilant of the AFC process would be a volcanic edifice of previous Miyakejima magmatism. Due to the relatively short timescales involved, the interaction between the assimilant and recent Miyakejima magmatism has not been recorded by the Sr-Nd-Pb isotopic systems. In such cases, Th isotopes and (²²⁶Ra/²³⁰Th) ratio are excellent geochemical tracers of magmatic evolution.     

Migration of Some Elements and Radionuclides across aGranite-Granite Contact Zone: A Natural Analoguefor Safe Disposal of High-Level Radwastes

Elements and natural radionuclides in the contact zone of two granites with different ages would migrate from one to the other because of the difference in their chemical contents and later water-rock interactions. This migration could serve as an analogue for the near-field process of radwastes in a high-level radwaste deep geological disposal repository.In the contact between the Indosinian granite (whole-rock Rb-Sr isochron age at 214@3 Ma) and Hercynian granite (zircon U-Pb isochron age at 296@31 Ma) located in Ziyuan County, Guangxi, the O and Pb isotope characteristics and the activity ratios of 234U/238U, 230Th/238U, 230Th/234U and 226Ra/230Th show that, based on the whole-rock chemical contents, both of the two granites have maintained a relatively open chemical system in their evolution processes. However, as there is no obvious open fault, the migration of major elements, trace elements and natural U-series nu-clides takes place within only 1-2 m in the contact zone, and water-rock interaction     

Thorium-uranium disequilibrium in a geothermal discharge zone at yellowstone

Whole rock samples of hydrothermally-altered Biscuit Basin rhyolite from Yellowstone drill cores Y-7 and Y-8 were analyzed for ²³⁰Th, ²³⁴U, ²³⁸U, and ²³²Th. Extreme disequilibrium was found, with (²³⁰Th/ ²³⁴U) ranging from 0.30 to 1.27. Values of (²³⁰Th/²³²Th) and (²³⁴U/²³²Th) define a linear correlation with a slope of 0.16 ± 0.01, which corresponds to a (²³⁰Th/²³⁴U) age of approximately 19 ka. The (²³⁰Th/²³⁴U) disequilibrium was apparently caused by U redistribution which occurred mostly at about 19 ka, and is not related simply to the relative degree of hydrothermal alteration and self-sealing of the rhyolite. Mass balance of U requires a large flux of U-bearing groundwater through the rhyolite at the time of U redistribution; rough estimates of minimum water/rock ratio range from 10² to 10⁴, for a range of possible groundwater U concentrations. Conservative hydraulic calculations indicate that the required groundwater flux could have occurred within a period of hundreds of years prior to self-sealing. The disequilibrium data are consistent with a model involving U redistribution during the initial stages of development of a geothermal discharge zone that formed in response to the hydrogeologic effects of glacial melting and unloading during the decline of the Pinedale Glaciation.     

U-series disequilibria in volcanic rocks from the Canary Islands: Plume versus lithospheric melting

U-series disequilibria are presented for Holocene samples from the Canary Islands and interpreted with special emphasis on the separate roles of plume vs. lithospheric melting processes. We report Th and U concentrations and (²³⁸U)/(²³²Th), (²³⁰Th)/(²³²Th), (²³⁰Th)/(²³⁸U) and (²³⁴U)/(²³⁸U) for 43 samples, most of which are minimally differentiated, along with (²²⁶Ra)/(²³⁰Th) and (²³¹Pa)/(²³⁵U) for a subset of these samples, measured by thermal ionization mass spectrometry (TIMS). Th and U concentrations range between 2 and 20 ppm and 0.5 and 6 ppm, respectively. Initial (²³⁰Th)/(²³⁸U) ranges from 1.1 to 1.6. (²²⁶Ra)/(²³⁰Th)_o ranges between 0.9 and 1.8 while (²³¹Pa)/(²³⁵U)_o ranges between 1.0 and 2.0.Our interpretation of results is based on a three-fold division of samples as a function of incompatible element ratio, such as Nb/U. The majority of samples have Nb/U = 47 ± 10, similar to most MORB and OIB. Higher ratios are found exclusively in alkali basalts and tholeiites from the eastern Canary Islands whereas lower ratios are exclusively found in differentiated rocks from the western Canary Islands. Those with ordinary Nb/U ratios are attributed to melting within the slowly ascending HIMU-dominated Canary plume.Higher Nb/U, generally found in more silica rich basalts from the eastern islands, is attributed to lithospheric contamination. Based on their trace element characteristics, two possible contaminants are amphibole veins (± other minerals) crystallized in the mantle from previous plume-derived basanite or re-melted plume-derived intrusive rocks. The high Nb/U signature of these materials is imparted on a melt of the lithosphere created either by the diffusive infiltration of alkalis or by direct reaction between basanites and peridotite. Mixing between plume-derived basanite and lithospheric melt accounts for the U-series systematics of most eastern island magmas including the well-known Timanfaya eruption. Lower Nb/U ratios in differentiated rocks from the western islands are attributed to fractional crystallization of amphibole ± phlogopite ± sphene from basanite during its ascent through the lithosphere. Based on changes in disequilibria, phonolites and tephrites are interpreted to result from rapid differentiation of primitive parents within millennia.     

U-Th systematics and Th ages of carbonate chimneys at the Lost City Hydrothermal Field

The Lost City Hydrothermal Field (LCHF) is a serpentinite-hosted vent field located 15 km west of the spreading axis of the Mid-Atlantic Ridge. In this study, uranium-thorium (U-Th) geochronological techniques have been used to examine the U-Th systematics of hydrothermal fluids and the ²³⁰Th ages of hydrothermally-precipitated carbonate chimneys at the LCHF. Fluid sample analyses indicate that endmember fluids likely contain only 0.0073 ng/g U or less compared to 3.28 ± 0.03 ng/g of U in ambient seawater. For fluid samples containing only 2-21% ambient seawater (1.1-11 mmol/kg Mg), Th concentration is 0.11-0.13 pg/g and surrounding seawater concentrations average 0.133 ± 0.016 pg/g. The ²³⁰Th/²³²Th atomic ratios of the vent fluids range from 1 (±10) × 10⁻⁶ to 11 (±5) × 10⁻⁶, are less than those of seawater, and indicate that the vent fluids may contribute a minor amount of non-radiogenic ²³⁰Th to the LCHF carbonate chimney deposits. Chimney ²³⁸U concentrations range from 1 to 10 μg/g and the average chimney corrected initial δ²³⁴U is 147.2 ± 0.8, which is not significantly different from the ambient seawater value of 146.5 ± 0.6. Carbonate ²³²Th concentrations range broadly from 0.0038 ± 0.0003 to 125 ± 16 ng/g and ²³⁰Th/²³²Th atomic ratios vary from near seawater values of 43 (±8) × 10⁻⁶ up to 530 (±25) × 10⁻³. Chimney ages, corrected for initial ²³⁰Th, range from 17 ± 6 yrs to 120 ± 13 kyrs. The youngest chimneys are at the intersection of two active, steeply-dipping normal faults that cut the Atlantis Massif; the oldest chimneys are located in the southwest portion of the field. Vent deposits on a steep, fault-bounded wall on the east side of the field are all <4 kyrs old, indicating that mass wasting in this region is relatively recent. Comparison of results to prior age-dating investigations of submarine hydrothermal systems shows that the LCHF is the most long-lived hydrothermal system known to date. It is likely that seismic activity and active faulting within the Atlantis Massif and the Atlantis Fracture Zone, coupled with volumetric expansion of the underlying serpentinized host rocks play major roles in sustaining hydrothermal activity at this site. The longevity of venting at the LCHF may have implications for ecological succession of microorganisms within serpentinite-hosted vent environments.     

Th/U/U and Pa/U ages from a single fossil coral fragment by multi-collector magnetic-sector inductively coupled plasma mass spectrometry

The ²³⁰Th/²³⁴U/²³⁸U age dating of corals via alpha counting or mass spectrometry has significantly contributed to our understanding of sea level, radiocarbon calibration, rates of ocean and climate change, and timing of El Nino, among many applications. Age dating of corals by mass spectrometry is remarkably precise, but many samples exposed to freshwater yield inaccurate ages. The first indication of open-system ²³⁰Th/²³⁴U/²³⁸U ages is elevated ²³⁴U/²³⁸U_initial values, very common in samples older than 100,000 yr. For samples younger than 100,000 yr that have ²³⁴U/²³⁸U_initial values close to seawater, there is a need for age validation. Redundant ²³⁰Th/²³⁴U/²³⁸U and ²³¹Pa/²³⁵U ages in a single fossil coral fragment are possible by Multi-Collector Magnetic Sector Inductively Coupled Plasma Mass Spectrometry (MC-MS-ICPMS) and standard anion exchange column chemistry, modified to permit the separation of uranium, thorium, and protactinium isotopes from a single solution. A high-efficiency nebulizer employed for sample introduction permits the determination of both ²³⁰Th/²³⁴U/²³⁸U and ²³¹Pa/²³⁵U ages in fragments as small as 500 mg. We have obtained excellent agreement between ²³⁰Th/²³⁴U/²³⁸U and ²³¹Pa/²³⁵U ages in Barbados corals (30 ka) and suggest that the methods described in this paper can be used to test the ²³⁰Th/²³⁴U/²³⁸U age accuracy.Separate fractions of U, Th, and Pa are measured by employing a multi-dynamic procedure, whereby ²³⁸U is measured on a Faraday cup simultaneously with all minor isotopes measured with a Daly ion counting detector. The multi-dynamic procedure also permits correcting for both the Daly to Faraday gain and for mass discrimination during sample analyses. The analytical precision of ²³⁰Th/²³⁴U/²³⁸U and ²³¹Pa/²³⁵U dates is generally better than ±0.3% and ±1.5%, respectively (2 Relative Standard deviation [RSD]). Additional errors resulting from uncertainties in the decay constant for ²³¹Pa and from undetermined sources currently limit the ²³¹Pa/²³⁵U age uncertainty to about ±2.5%. U isotope data and ²³⁰Th/²³⁴U/²³⁸U ages agree with National Institute of Standards and Technology (NIST) reference materials and with measurements made by Thermal Ionization Mass Spectrometry (TIMS) in our laboratory.     

Tracing the metasomatic and magmatic evolution of continental mantle roots with Sr, Nd, Hf and and Pb isotopes: A case study of Middle Atlas (Morocco) peridotite xenoliths

We studied clinopyroxenes from spinel-facies peridotite xenoliths sampled by the Quaternary intra-plate volcanism of the Middle Atlas (Morocco) and present new trace element and Sr-Nd-Hf isotope data. However, we focus in particular on Pb isotope data and ²³⁸U/²⁰⁴Pb and ²³²Th/²⁰⁴Pb ratios of these clinopyroxenes. This data allows us to investigate: (a) the timing of metasomatic events, (b) the prevalence and persistence of elevated ²³⁸U/²⁰⁴Pb, ²³²Th/²³⁸U and ²³²Th/²⁰⁴Pb in continental mantle roots and (c) the ²³⁸U/²⁰⁴Pb and ²³²Th/²⁰⁴Pb composition of putative basaltic melts generated from such metasomatised sub-continental lithospheric mantle (SCLM).Incompatible trace element concentrations in these clinopyroxenes are elevated, marked by high-field strength element depletion and fractionated elemental ratios (e.g., U/Nb, Zr/Hf) most consistent with enrichment due to carbonatitic liquids. Sr, Nd and Hf isotopes have an affinity to HIMU.U, Th and Pb abundances in the clinopyroxenes generally exceed estimates of primitive mantle clinopyroxene. Pb isotope compositions of these clinopyroxenes are radiogenic and vary between ²⁰⁶Pb/²⁰⁴Pb = 19.93-20.25, ²⁰⁷Pb/²⁰⁴Pb = 15.63-15.66 and ²⁰⁸Pb/²⁰⁴Pb = 39.72-40.23. These Pb isotope systematics result in generally negative Δ7/4 but positive Δ8/4; setting these samples distinctly apart from typical HIMU. These Pb isotope compositions are also distinct from the associated host volcanic rocks. ²³⁸U/²⁰⁴Pb and ²³²Th/²⁰⁴Pb of these clinopyroxenes, which range from 26 to 81 and 136 to 399, respectively, are elevated and more extreme than estimates of MORB- and HIMU-source mantle.The Pb isotope evolution of the clinopyroxenes suggests that the metasomatic enrichment is younger than 200 Ma, which discounts the volcanic activity due to the opening of the Atlantic and the onset of the collision of the African and Eurasian plates as processes generating the lithophile element and isotope composition of this continental mantle root. Instead, the enrichment is thought to be associated with the Quaternary intra-plate volcanism in the Middle Atlas. However, the erupted mafic melts have unradiogenic Pb isotopes and lower ²³⁸U/²⁰⁴Pb, ²³²Th/²⁰⁴Pb and ²³²Th/²³⁸U relative to the clinopyroxene and do not seem to have equilibrated with the clinopyroxenes. The high Th abundances and the high ²³²Th/²³⁸U also suggest that the metasomatism was due to carbonatitic liquids.When literature data for Pb isotopes in mantle minerals are considered, the Pb isotope range of Archean, Proterozoic and Phanerozoic continental mantle roots is remarkable in that they are similar to the convecting mantle. This observation does not support the existence of sub-continental lithospheric mantle with high ²³⁸U/²⁰⁴Pb and ²³²Th/²⁰⁴Pb for long periods of time. Consequently, the narrow range of Pb isotopes in SCLM worldwide suggests that only the youngest metasomatic events are recorded by incompatible elements such as U, Th and Pb. Numerical modelling of putative magmas generated from Middle Atlas SCLM by fractional, non-modal melting calculations yield extremely high ²³⁸U/²⁰⁴Pb and ²³²Th/²⁰⁴Pb ratios. For example, pure SCLM magmas generated from 0.5% to 10% melting are anticipated to have ²³²Th/²⁰⁴Pb ratios exceeding those known from terrestrial basalts.     

Precise two chronometer dating of Pleistocene travertine: The Th/U and Raex/Ra(0) approach

In order to determine the geochemical evolution of a freshwater limestone cave system located in central Switzerland (Hell Grottoes at Baar/Zug,) young postglacial tufaceous limestone and travertine precipitates were investigated using the ²³⁰Th/²³⁴U ingrowth system. Additional analyses of further radionuclides within the ²³⁸U decay chain, i.e. ²²⁶Ra and ²¹⁰Pb, showed that the Th/U chronometer started with insignificant inherited ²³⁰Th over the entire formation period of the travertine setting (i.e. ²³⁰Th(0)=0). A contribution from detrital impurities with ²³⁰Th/²³⁴U in secular equilibrium could be precisely subtracted by applying isochron dating of cogenetic phases and recently formed travertine. The resulting precise ²³⁰Th/²³⁴U formation ages were found to be consistent with the geological stratigraphy and were furthermore used to demonstrate the applicability of the next geologically important chronometer in the ²³⁸U-decay series, based on decay of excess ²²⁶Ra normalized to the initial, i.e.²²⁶Ra_ex/²²⁶Ra(0). This system is suitable for dating phases younger than 7000 yr when the correction of a detritus component increasingly limits the precision of the ²³⁰Th/²³⁴U chronometer. Analytical solutions of the coupled ²³⁴U/²³⁰Th/²²⁶Ra radionuclide system predicted that the ²²⁶Ra_ex/²²⁶Ra(0) chronometer is independent of the actual ²³⁰Th activity build up from decay of ²³⁴U, if the systems starts with zero inherited ²³⁰Th(0). The data set confirmed this hypothesis and showed furthermore that the initially incorporated ²²⁶Ra excess must have remained almost uniform in all limestone over a period of at least 7000 yr, i.e. 4–5 half-lives of ²²⁶Ra. This is concluded because (i) the ²²⁶Ra_ex/²²⁶Ra(0) ages agreed well with those derived from ²³⁰Th/²³⁴U, (ii) all data plot within uncertainty on the ²²⁶Ra_ex/²²⁶Ra(0) decay curve and (iii) the atomic Ba/Ca ratio was found to be constant in the travertine material independent of the sample ages. Provided that such boundary conditions hold, ²²⁶Ra_ex/²²⁶Ra(0) should be applicable to materials which are suitable for ²³⁰Th/²³⁴U dating in sedimentology and oceanography, i.e. travertine, corals, phosphorites, etc., and should strongly support ²³⁰Th/²³⁴U for samples that have been formed a few thousand years ago.     

U-Th-Pb and Lu-Hf isotopic constraints on the evolution of sub-continental lithospheric mantle, French Massif Central

We have carried out a Pb double-spike and Lu-Hf isotope study of clinopyroxenes from spinel-facies mantle xenoliths entrained in Cenozoic intraplate continental volcanism of the French Massif Central (FMC). U-Th-Pb and Lu-Hf isotope systematics verify the existence of different lithospheric domains beneath the northern and southern FMC. Northern FMC clinopyroxenes have extreme Lu/Hf ratios and ultra-radiogenic Hf (ε_Hf = +39.6 to +2586) that reflect ∼15-25% partial melting in Variscan times (depleted mantle model ages ∼360 Ma). Zr, Hf and Th abundances in these clinopyroxenes are low and unaffected by hydrous/carbonatitic metasomatism that overprinted LILE and light REE abundances and caused decoupling of Lu/Hf-Sm/Nd ratios and Nd-Hf isotopes (ε_Nd = +2.1 to +91.2). Pb isotopes of northern FMC clinopyroxenes are radiogenic (²⁰⁶Pb/²⁰⁴Pb > 19), and typically more so than the host intraplate volcanic rocks. ²³⁸U/²⁰⁴Pb ratios range from 17 to 68, and most samples have distinctively low ²³²Th/²³⁸U (<1) and ²³²Th/²⁰⁴Pb (3-22). Clinopyroxenes from southern FMC lherzolites are generally marked by overall incompatible trace element enrichment including Zr, Hf and Th abundances, and have Pb isotopes that are similar to or less radiogenic than the host volcanic rocks. Hf isotope ratios are less radiogenic (ε_Hf = +5.4 to +41.5) than northern FMC mantle and have been overprinted by silicate-melt-dominated metasomatism that affected this part of FMC mantle. Major element and Lu concentrations of clinopyroxenes from southern FMC harzburgites are broadly similar to northern FMC clinopyroxenes and suggest they experienced similar degrees of melt extraction as northern FMC mantle. ²³⁸U/²⁰⁴Pb (53-111) and ²³²Th/²⁰⁴Pb ratios (157-355) of enriched clinopyroxenes from the southern FMC are extreme and significantly higher than the intraplate volcanic rocks. In summary, mantle peridotites from different parts of the FMC record depletion at ∼360 Ma during Variscan subduction, followed by differing styles of enrichment. Northern FMC mantle was overprinted by a fluid/carbonatitic metasomatic agent that carried elements like U, Pb, Sr and light REE. In contrast, much of the southern FMC mantle was metasomatised by a small-degree partial silicate melt resulting in enrichment of all incompatible trace elements. The extreme mantle ²³⁸U/²⁰⁴Pb (northern and southern FMC), ²³²Th/²³⁸U (northern FMC) and ²³²Th/²⁰⁴Pb ratios (southern FMC), coupled with unremarkable present-day Pb isotope ratios, constrain the timing of enrichment. Mantle metasomatism is a young feature related to melting of the upwelling mantle responsible for Cenozoic FMC volcanism, rather than subduction-related metasomatism intimately associated with mantle depletion during the Variscan orogeny. The varying metasomatic styles relate to pre-existing variations in the thickness of the continental lithospheric lid, which controlled the extent to which upwelling mantle could ascend and melt. In the northern FMC, a thicker and more refractory lithospheric lid (?80 km) only allowed incipient degrees of melting resulting in fluid/carbonatitic metasomatism of the overlying sub-continental lithospheric mantle. The thinner lithospheric lid of the southern FMC (?70 km) allowed larger degrees of melting and resulted in silicate-melt-dominated metasomatism, and also focused the location of the volcanic fields of the FMC above this region.     

Factors controlling the groundwater transport of U, Th, Ra, and Rn

A model for the groundwater transport of naturally occurring U, Th, Ra, and Rn nuclides in the²³⁸U and²³²Th decay series is discussed. The model developed here takes into account transport by advection and the physico-chemical processes of weathering, decay, α-recoil, and sorption at the water-rock interface. It describes the evolution along a flowline of the activities of the²³⁸U and²³²Th decay series nuclides in groundwater. Simple sets of relationships governing the activities of the various species in solution are derived, and these can be used both to calculate effective retardation factors and to interpret groundwater data. For the activities of each nuclide, a general solution to the transport equation has been obtained, which shows that the activities reach a constant value after a distance ϰ_i, characteristic of each nuclide. Where ϰ_i is much longer than the aquifer length, (for²³⁸U,²³⁴U, and²³²Th), the activities grow linearly with distance. Where gKⁱ is short compared to the aquifer length, (for²³⁴Th,²³⁰Th,²²⁸Th,²²⁸Ra, and²²⁴Ra), the activities rapidly reach a constant or quasi-constant activity value. For²²⁶Ra and²²²Rn, the limiting activity is reached after 1 km. High δ²³⁴U values (proportional to the ratio^ɛ234Th/^W238U) can be obtained through high recoil fraction and/or low weathering rates. The activity ratios²³⁰Th/²³²Th,²²⁸Ra/²²⁶Ra and²²⁴Ra/²²⁶Ra have been considered in the cases where either weathering or recoil is the predominant process of input from the mineral grain. Typical values for weathering rates and recoil fractions for a sandy aquifer indicate that recoil is the dominant process for Th isotopic ratios in the water. Measured data for Ra isotope activity ratios indicate that recoil is the process generally controlling the Ra isotopic composition in water. Higher isotopic ratios can be explained by different desorption kinetics of Ra. However, the model does not provide an explanation for²²⁸Ra/²²⁶Ra and²²⁴Ra/²²⁶Ra activity ratios less than unity. From the model, the highest²²²Rn emanation equals 2ɛ. This is in agreement with the hypothesis that²²²Rn activity can be used as a first approximation for input by recoil (Krishnaswamiet al 1982). However, high²²²Rn emanation cannot be explained by production from the surface layer as formulated in the model. Other possibilities involve models including surface precipitation, where the surface layer is not in steady-state.     

高分辨电感耦合等离子体质谱法测定铀矿石样品中234U/238U、230Th/232Th和228Ra/226Ra同位素比值 

采用氢氟酸-硝酸-盐酸混合酸密闭消解含铀矿石样品,用阴离子交换树脂、阳离子交换树脂和锶特效树脂逐级分离富集铀、钍和镭。使用高分辨电感耦合等离子体质谱(HR-ICPMS)测定分离纯化液中234U/238U2、30Th/232Th和228Ra/226Ra同位素。比值的测量精密度取决于比值的大小和对应核素浓度的大小。对质量浓度为10 ng/mL天然铀测量液,234U/238U的测量精密度优于1.2%;对230Th质量浓度为0.6ng/mL且230Th和232Th质量浓度接近的测量液,230Th/232Th的测量精密度为1.2%;对228Ra质量浓度为0.48 pg/mL且228Ra和226Ra质量浓度接近的测量液,228Ra/226Ra的测量精密度为4.0%。     

Chronological and geochemical study of lavas from the Chaîne des Puys,Massif Central,France: Evidence for crustal contamination

Datations of ancient lavas from the Chaîne des Puys through the ²³⁰Th-²³⁸U radioactive disequilibrium method confirm the eruption of several basaltic or slightly differentiated lavas around 40,000 years ago. The study of (²³⁰Th/²³²Th)₀ initial ratios of these lava flows clearly demonstrates the influence of a crustal contamination of magmas superimposed to crystal fractionation. This contamination probably affects many trace elements, in particular, U, Th and Sr. A model based on the (²³⁰Th/²³²Th)₀ initial ratio variations of non-contaminated lavas permits to consider that the first eruptions in the Chaîne des Puys could have occurred about 100,000 years ago.     

Plume-lithosphere interaction beneath Mt. Cameroon volcano, West Africa: Constraints from U-Th-Ra and Sr-Nd-Pb isotope systematics

Precise measurements of ²³⁸U-²³⁰Th-²²⁶Ra disequilibria in lavas erupted within the last 100 yr on Mt. Cameroon are presented, together with major and trace elements, and Sr-Nd-Pb isotope ratios, to unravel the source and processes of basaltic magmatism at intraplate tectonic settings. All samples possess ²³⁸U-²³⁰Th-²²⁶Ra disequilibria with ²³⁰Th (18-24%) and ²²⁶Ra (9-21%) excesses, and there exists a positive correlation in a (²²⁶Ra/²³⁰Th)-(²³⁰Th/²³⁸U) diagram. The extent of ²³⁸U-²³⁰Th-²²⁶Ra disequilibria is markedly different in lavas of individual eruption ages, although the (²³⁰Th/²³²Th) ratio is constant irrespective of eruption age. When U-series results are combined with Pb isotope ratios, negative correlations are observed in the (²³⁰Th/²³⁸U)-(²⁰⁶Pb/²⁰⁴Pb) and (²²⁶Ra/²³⁰Th)-(²⁰⁶Pb/²⁰⁴Pb) diagrams. Shallow magma chamber processes like magma mixing, fractional crystallization and wall rock assimilation do not account for the correlations. Crustal contamination is not the cause of the observed isotopic variations because continental crust is considered to have extremely different Pb isotope compositions and U/Th ratios. Melting of a chemically heterogeneous mantle might explain the Mt. Cameroon data, but dynamic melting under conditions of high D_U and D_U/D_Th, long magma ascent time, or disequilibrium mineral/melt partitioning, is required. The most plausible scenario to produce the geochemical characteristics of Mt. Cameroon samples is the interaction of melt derived from the asthenospheric mantle with overlying sub-continental lithospheric mantle which has elevated U/Pb (>0.75) and Pb isotope ratios (²⁰⁶Pb/²⁰⁴Pb > 20.47) due to late Mesozoic metasomatism.     

Rates of silicate dissolution in deep-sea sediment: In situ measurement using U/U of pore fluids

Bulk dissolution rates for sediment from ODP Site 984A in the North Atlantic are determined using the ²³⁴U/²³⁸U activity ratios of pore water, bulk sediment, and leachates. Site 984A is one of only several sites where closely spaced pore water samples were obtained from the upper 60 meters of the core; the sedimentation rate is high (11-15 cm/ka), hence the sediments in the upper 60 meters are less than 500 ka old. The sediment is clayey silt and composed mostly of detritus derived from Iceland with a significant component of biogenic carbonate (up to 30%).The pore water ²³⁴U/²³⁸U activity ratios are higher than seawater values, in the range of 1.2 to 1.6, while the bulk sediment ²³⁴U/²³⁸U activity ratios are close to 1.0. The ²³⁴U/²³⁸U of the pore water reflects a balance between the mineral dissolution rate and the supply rate of excess ²³⁴U to the pore fluid by α-recoil injection of ²³⁴Th. The fraction of ²³⁸U decays that result in α-recoil injection of ²³⁴U to pore fluid is estimated to be 0.10 to 0.20 based on the ²³⁴U/²³⁸U of insoluble residue fractions. The calculated bulk dissolution rates, in units of g/g/yr are in the range of 4 × 10⁻⁷ to 2 × 10⁻⁶ yr⁻¹. There is significant down-hole variability in pore water ²³⁴U/²³⁸U activity ratios (and hence dissolution rates) on a scale of ca. 10 m. The inferred bulk dissolution rate constants are 100 to 10⁴ times slower than laboratory-determined rates, 100 times faster than rates inferred for older sediments based on Sr isotopes, and similar to weathering rates determined for terrestrial soils of similar age. The results of this study suggest that U isotopes can be used to measure in situ dissolution rates in fine-grained clastic materials.The rate estimates for sediments from ODP Site 984 confirm the strong dependence of reactivity on the age of the solid material: the bulk dissolution rate (R_d) of soils and deep-sea sediments can be approximately described by the expression R_d ≈ 0.1 Age⁻¹ for ages spanning 1000 to 5 × 10⁸ yr. The age of the material, which encompasses the grain size, surface area, and other chemical factors that contribute to the rate of dissolution, appears to be a much stronger determinant of dissolution rate than any single physical or chemical property of the system.