Uranium isotopes as a tracer of sources of dissolved solutes in the Han River,South Korea

The uranium (U) content and ²³⁴U/²³⁸U activity ratio were determined for water samples collected from Korea's Han River in spring, summer, and winter 2006 to provide data that might constrain the origin of U isotope fractionation in river water and the link between U isotope systematics in river waters and the lithological nature of the corresponding bedrock. The large difference in the major dissolved loads between the two major branches of the Han River, the North Han River (NHR) and South Han River (SHR), is reflected in the contrasting U content and ²³⁴U/²³⁸U activity ratio between the tributaries: low U content (0.08–0.75 nM; average, 0.34 nM) and small ²³⁴U/²³⁸U activity ratio (1.03–1.22; average, 1.09) in the NHR; and high U content (0.65–1.98 nM; average, 1.44 nM) and large ²³⁴U/²³⁸U activity ratio (1.05–1.45; average, 1.24) in the SHR. The large spatial differences in U content and ²³⁴U/²³⁸U activity ratio are closely related to both lithological differences between the two tributaries and groundwater input. The low U content and small ²³⁴U/²³⁸U activity ratio in the NHR arise mainly from a combination of surface and meteoric weathering of the dominant silicate rocks in this branch and congruent dissolution of already weathered (secular equilibrium) materials. In contrast, the high U content and large ²³⁴U/²³⁸U activity ratio in the SHR are ascribed to the dissolution of carbonates and black shales along with significant inputs of deep groundwater.     

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.     

Activity disequilibrium of Th, U, and U in old stilbite: Effects of young U mobility and α-recoil

Stilbite from Malmberget and Svappavara is part of hydrothermal mineral assemblages occupying regionally occurring open Palaeoproterozoic fractures in northern Sweden. At these locations, stilbite is characterized by Pb_rad excess relative to U and by activity ratios of [²³⁴U]/[²³⁸U] > 1 and [²³⁰Th]/[²³⁸U] > 1. The activity disequilibrium requires a disturbance of the U-Th systematics within the last one million years. Leaching and infiltration experiments on Malmberget stilbite demonstrate: (i) preferential leaching in the order Pb >U >Th and uptake in the order Pb > U, and (ii) isotopic fractionation of U by preferential mobilization of ²³⁸U and ²³⁵U relative to ²³⁴U. Stepwise-leaching further indicates that the bulk of U is hosted in the channel sites of stilbite. The Th-U disequilibrium systematics observed in untreated Malmberget and Svappavara stilbite can be explained by: (1) addition of U with [²³⁴U]/[²³⁸U] > 1 from a fluid, or alternatively (2) loss of U from a two-component system, consisting of a component that is “open” or accessible and a component that is “closed” or inaccessible to mobilization. U addition requires a multistage history involving multiple gain or loss of U and/or Pb. In contrast, U loss does not necessarily require multistage processes but can also be explained by preferential removal of ²³⁸U (and ²³⁵U) relative to recoiled daughter isotopes such as ²³⁴U, ²³⁰Th, and ²⁰⁶Pb (and ²⁰⁷Pb) during a single event. Such a behavior could be obtained if the recoiled daughter isotopes of channel-sited uranium are implanted into the crystal lattice and, in such a way, become less mobile than their parent isotopes. This case implies an open-system behavior for ions in the channel sites and a closed-system behavior for ions in the silicate framework of stilbite. Each α-recoil directly or indirectly, i.e., through its recoil cascade, damages the silicate framework. Subsequent (continuous) low-temperature annealing of the damaged stilbite lattice could trap the recoiled daughter isotopes in the repaired crystal lattice or sealed-off channels. Such immobile recoiled material can, in part, represent the “closed” component of the system. This model can account for all observations regarding the Th-U-Pb systematics, including the Th-U disequilibrium systematics, the similarity in Th/U as deduced from Th-U disequilibrium and Pb isotope data, and the excess of radiogenic Pb (²⁰⁸Pb-parents also had been multiply recoiled). These two contrasting explanations involve either multistage or multicomponent systems. They do not permit the derivation of an accurate age.     

Radioelements,radiogenic helium and age relationships for groundwaters from the granites at Stripa,Sweden

The solution of radioelements and radiogenic ⁴He by groundwaters in fractured rocks is dependent upon the radioelement distribution in the rock matrix and the extent of the rock-water interface. The ${}^{234}\text{U}{}^{238}\text{U}$ activity ratio and the dissolved U, Rn and He contents of such groundwaters respond to changes in the flow regime with time. Although ${}^{234}\text{U}{}^{238}\text{U}$ activity ratios change with groundwater residence time as a consequence of ²³⁴Th-recoil induced solution of ²³⁴U, the activity ratio is strongly influenced by the U distribution within fractures, by the extent of the rock-water interface and by the amount of ²³⁸U in solution. A model for the quantitative evaluation of these effects is presented.Groundwaters from depths up to 880 m in the Stripa granite have variable dissolved uranium contents and ${}^{234}\text{U}{}^{238}\text{U}$ activity ratios. The uranium geochemistry is primarily determined by variations in flow path rather than by groundwater age.Dissolved radiogenic ⁴He in the groundwaters increases with their depth of origin, and is dependent upon the U content of the granite and upon its fracture porosity. It increases with groundwater residence time but movement of ⁴He by diffusion and transport processes make the actual groundwater age indeterminate.     

234U/238U evidence for local recharge and patterns of ground-water flow in the vicinity of Yucca Mountain,Nevada, USA

Uranium concentrations and ²³⁴U/²³⁸U ratios in saturated-zone and perched ground water were used to investigate hydrologic flow and downgradient dilution and dispersion in the vicinity of Yucca Mountain, a potential high-level radioactive waste disposal site. The U data were obtained by thermal ionization mass spectrometry on more than 280 samples from the Death Valley regional flow system. Large variations in both U concentrations (commonly 0.6–10 μg l⁻¹) and ²³⁴U/²³⁸U activity ratios (commonly 1.5–6) are present on both local and regional scales; however, ground water with ²³⁴U/²³⁸U activity ratios from 7 up to 8.06 is restricted largely to samples from Yucca Mountain. Data from ground water in the Tertiary volcanic and Quaternary alluvial aquifers at and adjacent to Yucca Mountain plot in 3 distinct fields of reciprocal U concentration versus ²³⁴U/²³⁸U activity ratio correlated to different geographic areas. Ground water to the west of Yucca Mountain has large U concentrations and moderate ²³⁴U/²³⁸U whereas ground water to the east in the Fortymile flow system has similar ²³⁴U/²³⁸U, but distinctly smaller U concentrations. Ground water beneath the central part of Yucca Mountain has intermediate U concentrations but distinctive ²³⁴U/²³⁸U activity ratios of about 7–8. Perched water from the lower part of the unsaturated zone at Yucca Mountain has similarly large values of ²³⁴U/²³⁸U. These U data imply that the Tertiary volcanic aquifer beneath the central part of Yucca Mountain is isolated from north-south regional flow. The similarity of ²³⁴U/²³⁸U in both saturated- and unsaturated-zone ground water at Yucca Mountain further indicates that saturated-zone ground water beneath Yucca Mountain is dominated by local recharge rather than regional flow. The distinctive ²³⁴U/²³⁸U signatures also provide a natural tracer of downgradient flow. Elevated ²³⁴U/²³⁸U in ground water from two water-supply wells east of Yucca Mountain are interpreted as the result of induced flow from 40 a of ground-water withdrawal. Elevated ²³⁴U/²³⁸U in a borehole south of Yucca Mountain is interpreted as evidence that natural downgradient flow is more likely to follow southerly paths in the structurally anisotropic Tertiary volcanic aquifer where it becomes diluted by regional flow in the Fortymile system.     

Transport of radionuclides in an unconfined chalk aquifer inferred from U-series disequilibria

U-series disequilibria measured in waters and rocks from a chalk aquifer in France have been used as an analog for long-term radionuclide migration. Drill core samples from a range of depths in the vadose zone and in the saturated zone, as well as groundwater samples were analyzed for ²³⁸U, ²³⁴U, ²³²Th and ²³⁰Th to determine transport mechanisms at the water/rock interface and to quantify parameters controlling the migration of radionuclides. Isotope measurements in rocks were done by TIMS, whereas (²³⁴U/²³⁸U) and (²³⁰Th/²³²Th) activity ratios in water samples were measured by multi-collector-ICP-MS. Both depletion and enrichment in ²³⁴U relative to ²³⁸U were observed in carbonate rock samples resulting from chemical weathering in the unsaturated zone and calcite precipitation in the zone of water-table oscillation, respectively. The correlation between (²³⁰Th/²³²Th) activity ratios and ⁸⁷Sr/⁸⁶Sr ratios found in the chalk samples indicates that thorium is mainly contained in a minor silicate phase whose abundance is variable in chalk samples. Water samples are all characterized by (²³⁴U/²³⁸U) > 1 resulting from α-recoil effect of ²³⁴Th. Groundwaters are characterized by a more radiogenic signature in ⁸⁷Sr/⁸⁶Sr than the rocks. Moreover, (²³⁰Th/²³²Th) activity ratios in the waters are lower than in the rocks, and increase with distance from the water divide, which suggests that Th transport is controlled by colloids formed during water infiltration in the soil. A 1-D transport model has been developed in order to constrain the U-series nuclide transport considering a transient behavior of radionuclides in the aquifer and a time-dependent composition for the solid phase. This model permits a prediction of the time scale of equilibration of the system, and an estimation of parameters such as weathering rate, distribution coefficients and α-recoil fractions. Retardation factors of 10-35 and from 1 × 10⁴ to 2 × 10⁵ were predicted for U and Th, respectively, and can be used to predict the migration of radionuclides released as contaminants in the environment. At the scale of our watershed (∼32 km²), a characteristic migration time from recharge to riverine discharge of 200-600 yr for U and 0.2-3.7 Myr for Th was obtained.     

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.     

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.     

A study of234U/238U ratios in groundwaters of Taiyuan area,Shanxi Province

Uranium contents and²³⁴U/²³⁸U ratios have been determined on 29 water samples from the Taiyuan area, Shanxi Province. The results show that the same artesian aquifer has similar uranium contents and²³⁴U/²³⁸U activity ratios, and the deeper aquifers have higher A. R. values but lower uranium contents. The A. R. values increase slightly towards groundwater flow in the artesian aquifers dominated by oxidizing ground waters. The Lancun Spring and the famous Jinci Spring belong to two different karst groundwater systems, i.e., the east and west karst groundwater systems. The recharge area of the Lancun Spring should cover the wide limestone outcrops of middle Ordovician in the northeast. The Ordovician fissure-karst ground water to the Jinci Spring is extensively mixed with fissure water in Carboniferous-Jurassic formations and seepage water from the Fenhe River.     

Uranium isotopic disequilibrium for groundwater classification: first results on complexe terminal and continental intercalaire aquifers in Southern Tunisia

A fractionation of uranium (U) series into parent–daughter pairs – ²³⁴U and ²³⁸U – always occurs in natural waters, and the disequilibria between these is commonly used as a tracer of groundwater flow. We report here an interpretation of the U-content and U isotope disequilibria in groundwater sampled from the deep Complexe Terminal and Continental Intercalaire aquifers of southern Tunisia. Variations in both the contents of these isotopes (0.006–2.4 ppb) and ²³⁴U/²³⁸U activity ratios (ARs) (1.7–15.4) were observed. The data could be plotted in two distinct fields of reciprocal U concentration versus ²³⁴U/²³⁸U AR according to groundwater flow and regional bedrock differences. An initial assessment aimed at verifying whether the results of this investigation support those of previous hydrogeological and isotope studies, thereby suggesting that the disequilibrium between U isotopes in groundwater may represent a useful tool for hydrogeological investigations of deep and fossil groundwater. In addition, the disequilibrium can be used for quantifying the recharge or mixing rates between different formations with the aim of delineating the preferential outflow pattern or determining residence times of waters.     

Identification of He sources and estimation of He ages in groundwater of the North China Plain

Dissolved helium concentrations and ³He/⁴He ratios were measured for 18 groundwater samples collected from the Quaternary confined aquifers in the North China Plain (NCP). The dissolved helium concentrations ranged from 1 × 10⁻⁷ to 1 × 10⁻⁶ cm³STP·g⁻¹ in the 14 samples from the central plain, but was approximately two orders of magnitude higher, between 6 × 10⁻⁶ and 9 × 10⁻⁵ cm³STP·g⁻¹, in 4 samples from the coastal plain. Based on these concentrations and the corresponding ³He/⁴He ratios varying from 0.09 to 0.55 R_a (where R_a is the ³He/⁴He ratio of air), the dissolved helium in groundwater in the central plain was identified to be primarily a mixture of atmospheric helium with radiogenic helium and a representative radiogenic helium ratio was estimated to be 0.035 R_a. Despite the high fraction of terrigenic ⁴He in the samples from the coastal plain, their ³He/⁴He ratios were found to be significantly above this radiogenic value, ranging between 0.20 and 0.37 R_a, indicating the presence of a mantle-derived He component in this area. About 2–4% mantle helium was estimated to be present in the groundwater of the coastal plain, which probably is associated with the regional Cangdong fault and tectonic activities. Based on the radiogenic He component, ⁴He ages of the groundwater in the central plain were calculated by assuming either pure in situ production or an external helium flux J₀ of 4.7 × 10⁻⁸ cm³STPcm⁻²a⁻¹. The estimated ⁴He ages fall between 9.5 and 51.4 ka and are comparable to the ¹⁴C ages, suggesting that the results of ⁴He dating are reasonable and can be an effective tool to estimate groundwater residence times under suitable conditions.     

Modeling non-steady state radioisotope transport in the vadose zone - A case study using uranium isotopes at Peña Blanca, Mexico

Current models using U- and Th-series disequilibria to study radioisotope transport in groundwater systems mostly consider a steady-state situation. These models have limited applicability to the vadose zone (UZ) where the concentration and migratory behavior of radioisotopes in fluid are often transitory. We present here, as a first attempt of its kind, a model simulating the non-steady state, intermittent fluid transport in vadose layers. It provides quantitative constraints on in-situ migration of dissolved and colloidal radioisotopes in terms of retardation factor and rock-water interaction (or water transit) time. For uranium, the simulation predicts that intermittent flushing in the UZ leads to a linear relationship between reciprocal U concentration and ²³⁴U/²³⁸U ratio in percolating waters, with the intercept and slope bearing information on the rates of dissolution and α-recoil of U isotopes, respectively. The general validity of the model appears to be borne out by the measurement of uranium isotopes in UZ waters collected at various times over a period during 1995-2006 from a site in the Peña Blanca mining district, Mexico, where the Nopal I uranium deposit is located. Enhanced ²³⁴U/²³⁸U ratios in vadose-zone waters resulting from lengthened non-flushing time as prescribed by the model provide an interpretative basis for using ²³⁴U/²³⁸U in cave calcites to reconstruct the regional changes in hydrology and climate. We also provide a theoretical account of the model’s potential applications using radium isotopes.     

The mineral dissolution rate conundrum: Insights from reactive transport modeling of U isotopes and pore fluid chemistry in marine sediments

Pore water chemistry and ²³⁴U/²³⁸U activity ratios from fine-grained sediment cored by the Ocean Drilling Project at Site 984 in the North Atlantic were used as constraints in modeling in situ rates of plagioclase dissolution with the multicomponent reactive transport code Crunch. The reactive transport model includes a solid-solution formulation to enable the use of the ²³⁴U/²³⁸U activity ratios in the solid and fluid as a tracer of mineral dissolution. The isotopic profiles are combined with profiles of the major element chemistry (especially alkalinity and calcium) to determine whether the apparent discrepancy between laboratory and field dissolution rates still exists when a mechanistic reactive transport model is used to interpret rates in a natural system. A suite of reactions, including sulfate reduction and methane production, anaerobic methane oxidation, CaCO₃ precipitation, dissolution of plagioclase, and precipitation of secondary clay minerals, along with diffusive transport and fluid and solid burial, control the pore fluid chemistry in Site 984 sediments. The surface area of plagioclase in intimate contact with the pore fluid is estimated to be 6.9 m²/g based on both grain geometry and on the depletion of ²³⁴U/²³⁸U in the sediment via α-recoil loss. Various rate laws for plagioclase dissolution are considered in the modeling, including those based on (1) a linear transition state theory (TST) model, (2) a nonlinear dependence on the undersaturation of the pore water with respect to plagioclase, and (3) the effect of inhibition by dissolved aluminum. The major element and isotopic methods predict similar dissolution rate constants if additional lowering of the pore water ²³⁴U/²³⁸U activity ratio is attributed to isotopic exchange via recrystallization of marine calcite, which makes up about 10-20% of the Site 984 sediment. The calculated dissolution rate for plagioclase corresponds to a rate constant that is about 10² to 10⁵ times smaller than the laboratory-measured value, with the value depending primarily on the deviation from equilibrium. The reactive transport simulations demonstrate that the degree of undersaturation of the pore fluid with respect to plagioclase depends strongly on the rate of authigenic clay precipitation and the solubility of the clay minerals. The observed discrepancy is greatest for the linear TST model (10⁵), less substantial with the Al-inhibition formulation (10³), and decreases further if the clay minerals precipitate more slowly or as highly soluble precursor minerals (10²). However, even several orders of magnitude variation in either the clay solubility or clay precipitation rates cannot completely account for the entire discrepancy while still matching pore water aluminum and silica data, indicating that the mineral dissolution rate conundrum must be attributed in large part to the gradual loss of reactive sites on silicate surfaces with time. The results imply that methods of mineral surface characterization that provide direct measurements of the bulk surface reactivity are necessary to accurately predict natural dissolution rates.     

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.     

Preferential solution of234U from recoil tracks and234U/238U radioactive disequilibrium in natural waters

A mathematical model to calculate the²³⁴U/²³⁸U activity ratio (AR) in an aqueous phase in contact with rock/soil is presented. The model relies on the supply of²³⁸U by dissolution and that of²³⁴U by dissolution and preferential release from radiation damaged regions (recoil tracks). The model predicts that values of²³⁴U/²³⁸U AR>1 in the aqueous phase can be obtained only from weathering “virgin” surfaces. Thus, to account for the observed steady-state supply of²³⁴U excess to the oceans by the preferential leaching model, ‘virgin’ rock/soil surfaces would have to be continually exposed and weathered. The²³⁸U concentration and²³⁴U/²³⁸U AR in continental waters allow us to estimate the exposure rates of “virgin” rock/soil surfaces.     

Isotope hydrology of the Chalk River Laboratories site,Ontario, Canada

This paper presents results of hydrochemical and isotopic analyses of groundwater (fracture water) and porewater, and physical property and water content measurements of bedrock core at the Chalk River Laboratories (CRL) site in Ontario. Density and water contents were determined and water-loss porosity values were calculated for core samples. Average and standard deviations of density and water-loss porosity of 50 core samples from four boreholes are 2.73 ± 12 g/cc and 1.32 ± 1.24 percent. Respective median values are 2.68 and 0.83 indicating a positive skewness in the distributions. Groundwater samples from four deep boreholes were analyzed for strontium (⁸⁷Sr/⁸⁶Sr) and uranium (²³⁴U/²³⁸U) isotope ratios. Oxygen and hydrogen isotope analyses and selected solute concentrations determined by CRL are included for comparison. Groundwater from borehole CRG-1 in a zone between approximately +60 and −240 m elevation is relatively depleted in δ¹⁸O and δ²H perhaps reflecting a slug of water recharged during colder climatic conditions. Porewater was extracted from core samples by centrifugation and analyzed for major dissolved ions and for strontium and uranium isotopes. On average, the extracted water contains 15 times larger concentration of solutes than the groundwater. ²³⁴U/²³⁸U and correlation of ⁸⁷Sr/⁸⁶Sr with Rb/Sr values indicate that the porewater may be substantially older than the groundwater. Results of this study show that the Precambrian gneisses at Chalk River are similar in physical properties and hydrochemical aspects to crystalline rocks being considered for the construction of nuclear waste repositories in other regions.     

Experimental evidence for U-U fractionation during granite weathering with implications for U/U in natural waters

The daughter to parent (²³⁴U/²³⁸U) activity ratio in natural waters is often out of secular radioactive equilibrium. The major reason for this disequilibrium is related to the energetic α-decay of ²³⁸U and differential release of ²³⁴U relative to ²³⁸U. This disequilibrium originates from (1) preferential release of more loosely bound ²³⁴U from damaged mineral lattice sites or; (2) direct recoil of ²³⁴Th into surrounding media from near mineral surface boundaries, however, it is unclear which of the two mechanisms is most important in nature. To better quantify the effects of preferential release of ²³⁴U, two continuous laboratory granite leaching experiments conducted over 1100 h were performed. The leachates were characterized by declining U concentrations with time and (²³⁴U/²³⁸U) initially greater than unity (up to 1.15), which changed to below unity during leaching (∼0.95). The early elevated (²³⁴U/²³⁸U) suggests that additional ²³⁴U is released into solution by preferential release of ²³⁴U from mineral phases. However, the excess ²³⁴U constitutes a finite pool of easy leachable ²³⁴U and the (²³⁴U/²³⁸U) values become lower than unity when this pool is used up. A model based on first-order kinetics, dissolution rates and preferential release of ²³⁴U from damaged lattice sites was developed and is able to quantitatively predict the observed pattern of (²³⁴U/²³⁸U) values and U concentrations for the two granite leaching experiments. Extending the modeling to longer time scales more comparable to natural systems shows that the production of waters with high (²³⁴U/²³⁸U) ratios can be achieved in two distinct regimes (1) slow weathering where the rate of directly recoiled ²³⁴U near mineral surfaces into waters is high; (2) fast weathering where the role of incipient chemical weathering and preferential release of loosely bound ²³⁴U are important. The model is able to explain apparent opposite correlations between physical erosion rates and (²³⁴U/²³⁸U) in waters and it provides a new framework that will be useful for examining weathering regimes, their timescales and their coupling with physical erosion.     

Transport of U in the Opalinus Clay on centimetre to decimetre scales

The Opalinus Clay formation in North Switzerland is a potential host rock for a deep underground radioactive waste repository. The distribution of ²³⁸U, ²³⁴U and ²³⁰Th was studied in rock samples of the Opalinus Clay from an exploratory borehole at Benken (Canton of Zurich) using MC-ICP-MS. The aim was to assess the in situ, long-term migration behaviour of ²³⁴U in this rock. Very low hydraulic conductivities of the Opalinus Clay, reducing potential of the pore water and its chemical equilibrium with the host rock are expected to render both ²³⁸U and ²³⁰Th immobile. If U is heterogeneously distributed in the Opalinus Clay, gradients in the supply of ²³⁴U from the rock matrix to the pore water by the decay of ²³⁸U will be established. Diffusive redistribution separates ²³⁴U from its immobile parent ²³⁸U resulting in bulk rock ²³⁴U/²³⁸U activity disequilibria. These may provide a means of estimating the mobility of ²³⁴U in the rock if the diffusion rate of ²³⁴U is significant compared to its decay rate. Sampling was carried out on two scales. Drilling of cm-spaced samples from the drill-core was done to study mobility over short distances and elucidate possible small-scale lithological control. Homogenized 25-cm-long portions of a 2-m-long drill-core section were prepared to provide information on transport over a longer distance. Variations in U and/or Th content on the cm-scale between clays and carbonate-sandy layers are revealed by β-scanning, which shows that the (dominant) clay is richer in both elements.     

Scavenging and particle residence times determined from 234Th/238U disequilibria in the coastal waters of Mecklenburg Bay

Activities of the naturally occurring radionuclide ²³⁴Th were determined in water samples of Mecklenburg Bay (SW Baltic Sea) using a new Th-specific diatomite adsorption technique followed by liquid scintillation spectrometry. Activities of “dissolved” (operationally defined as Th in the centrifugate) and particulate ²³⁴Th varied in the range of 1.4–6.9 and 0.9–9.3 mBq l⁻¹, respectively. A significant correlation between K_d and SPM concentration was found. From this particle-concentration effect, the “colloidal pumping” model predicts that 98% of the “dissolved” Th is associated with colloids rather than being truly dissolved. Relative to calculated activities of the parent nuclide ²³⁸U in the Bay, the ²³⁴Th data yielded mean ²³⁴Th scavenging residence times in the range of 1.2–9.7 days. Particulate ²³⁴Th activities are inversely correlated to SPM concentrations. Particle residence times ranged from a few days in winter up to 20 days in spring characterized by less intense bottom currents. The hydrodynamic regime is the master variable controlling scavenging of Th and other similarly particle-reactive elements in Mecklenburg Bay.     

Extreme fractionation of 234U238U and 230Th234U in spring waters,sediments, and fossils at the Pomme de Terre Valley,southwestern Missouri

Isotopic fractionation as great as 1600% exists between ²³⁴U and ²³⁸U in spring waters, sediments, and fossils in the Pomme de Terre Valley, southwestern Missouri. The activity ratios of ${}^{234}\text{U}{}^{238}\text{U}$ in five springs range from 7.2 to 16 in water which has been discharged for at least the past 30,000 years. The anomalies in ${}^{234}\text{U}{}^{238}\text{U}$ ratio in deep water have potential usefulness in hydrologic investigations in southern Missouri. Clayey units overlying the spring bog sediments of Trolinger Spring are enriched in ²³⁰Th relative to their parent ²³⁴U by as much as 720%. The results indicate that both preferential displacement via alpha recoil ejection and the preferential emplacement via recoiling and physical entrapment are significant processes that are occurring in the geologic environment.