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-TH-PA-RA study of the Kamchatka arc: new constraints on the genesis of arc lavas

The ²³⁸U-²³⁰Th-²²⁶Ra and ²³⁵U-²³¹Pa disequilibria have been measured by mass spectrometry in historic lavas from the Kamchatka arc. The samples come from three closely located volcanoes in the Central Kamchatka Depression (CKD), the most active region of subducted-related volcanism in the world. The large excesses of ²²⁶Ra over ²³⁰Th found in the CKD lavas are believed to be linked to slab dehydration. Moreover, the samples show the uncommon feature of (²³⁰Th/²³⁸U) activity ratios both lower and higher than 1. The U-series disequilibria are characterized by binary trends between activity ratios, with (²³¹Pa/²³⁵U) ratios all >1. It is shown that these correlations cannot be explained by a simple process involving a combination of slab dehydration and melting. We suggest that they are more likely to reflect mixing between two end-members: a high-magnesia basalt (HMB) end-member with a clear slab fluid signature and a high-alumina andesite (HAA) end-member reflecting the contribution of a slab-derived melt. The U-Th-Ra characteristics of the HMB end-member can be explained either by a two-step fluid addition with a time lag of 150 ka between each event or by continuous dehydration. The inferred composition for the dehydrating slab is a phengite-bearing eclogite. Equilibrium transport or dynamic melting can both account for ²³¹Pa excess over ²³⁵U in HMB end-member. Nevertheless, dynamic melting is preferred as equilibrium transport melting requires unrealistically high upwelling velocities to preserve fluid-derived ²²⁶Ra/²³⁰Th. A continuous flux melting model is also tested. In this model, ²³¹Pa-²³⁵U is quickly dominated by fluid addition and, for realistic extents of melting, this process cannot account for (²³¹Pa/²³⁵U) ratios as high as 1.6, as observed in the HMB end-member.The involvement of a melt derived from the subducted oceanic crust is more likely for explaining the HAA end-member compositions than crustal assimilation. Melting of the oceanic crust is believed to occur in presence of residual phengite and rutile, resulting in no ²²⁶Ra-²³⁰Th disequilibrium and low ²³¹Pa excess over ²³⁵U in the high-alumina andesites. Consequently, it appears that high-alumina andesites and high-magnesia basalts have distinct origins: the former being derived from melting of the subducted oceanic crust and the latter from hydrated mantle. It seems that there is no genetic link between these two magma types, in contrast with what was previously believed.     

Ra and Th adsorption coefficients in lakes—Lake Kinneret (Sea of Galilee) “natural experiment”

The adsorption rate constants of Ra and Th were estimated from empirical data from a freshwater lake and its feeding saline springs. We utilized the unique setting of Lake Kinneret (Sea of Galilee, northern Israel) in which most of the Ra and Th nuclides are introduced into the lake by saline springs with high ²²⁶Ra activities and a high ²²⁴Ra/²²⁸Ra ratio of 1.5. The mixing of the Ra enriched saline waters and freshwater in the lake causes the ²²⁴Ra/²²⁸Ra ratio to drop down to 0.1 in the Kinneret due to preferential adsorption of ²²⁸Th. These conditions constitute a “natural experiment” for estimating adsorption rates. We developed a simple mass-balance model for the radionuclides in Lake Kinneret that accurately predicted the Ra isotope ratios and the ²²⁶Ra activity in the lake. The model is comprised of simultaneous equations; one for each radionuclide. The equations have one input term: supply of radionuclides from the saline springs; and three output terms: adsorption on particles in the lake, radioactive decay and outflow from the lake. The redundancy in the analytical solutions to the mass balance equations for the relevant nuclides constrained the values of Ra and Th adsorption rate constants to a very narrow range. Our results indicate that the adsorption rate constant for Ra is between 0.005 d⁻¹ and 0.02 d⁻¹. The rate constant for Th is between 0.5 d⁻¹ and 1 d⁻¹, about fifty to a hundred times higher. The estimated desorption rate coefficient for Ra is about 50-100 times larger than its adsorption rate constant. The mass-balance equations show that the residence times of all Ra isotopes (²²⁶Ra, ²²⁸Ra,²²³Ra, ²²⁴Ra) and of ²²⁸Th in the lake are about 95, 92, 14, 6 and 1 d, respectively. These residence times are much shorter than the residence time of water in the lake (about 5.5 y). The steady state activity ratios in Lake Kinneret depend mainly on the adsorption rate constants, decay constants, the outflow rate from the lake and the activity ratios in the saline springs. The activity ratios are independent of the saline springs flow rate.     

The Paleozoic Ozbak-Kuh carbonate-hosted Pb-Zn deposit of East Central Iran: Isotope (C,O, S,Pb) geochemistry and ore genesis

Lead and zinc mineralization occurs in dolostones of the Middle Devonian Sibzar Formation at Ozbak-Kuh, which is located 150 km north of Tabas city in East Central Iran. The ore is composed of galena, sphalerite and calcite, with subordinate dolomite and bitumen. Wall-rock alterations include carbonate recrystallization and dolomitization. Microscopic studies reveal that the host rock is replaced by galena and sphalerite. The Pb–Zn mineralization is epigenetic and stratabound. The δ¹³C values of hydrothermal calcite samples fall in the narrow range between ?0.3‰ and 0.8‰. The δ¹⁸O values in calcite display a wider range, between ?14.5‰ and ?11.9‰. The δ¹³C and δ¹⁸O values overlap with the oxygen and carbon isotopic compositions of Paleozoic seawater, indicating the possible important participation of Paleozoic seawater in the ore-forming fluid. The δ¹⁸O signature corresponds to a spread in temperature of about 70 °C in the ore-bearing fluid. The δ¹³C values indicate that the organic materials within the host rocks did not contribute significantly in the hydrothermal fluid. The δ³⁴S values of galena and sphalerite samples occupy the ranges of 12.2‰–16.0‰ and 12.1–16.8‰, respectively. These values reveal that the seawater sulfate is the most probable source of sulfur. The reduced sulfur was most likely supplied through thermochemical sulfate reduction. The sulfur isotope ratios of co-precipitated sphalerite–galena pairs suggest that deposition of the sulfide minerals took place under chemical disequilibrium conditions. The ²⁰⁶Pb/²⁰⁴Pb, ²⁰⁷Pb/²⁰⁴Pb, and ²⁰⁸Pb/²⁰⁴Pb ratios of the galena samples represent average values of 18.08, 15.66, and 38.50, respectively. These ratios indicate that galena Pb likely originated from an orogenic source in which supracrustal rocks with high ²³⁸U/²⁰⁴Pb and ²³²Th/²⁰⁴Pb ratios are dominant. The average lead isotope model age portrays Cambrian age. This model age is not coeval with the host rocks, which are of middle Devonian age. It is probable that the pre-Middle Devonian model age shows the derivation of Pb from older sources either from host rocks of Cambrian age or from deposits previously formed in these rock units. The Pb isotopic composition of galena accords with the occurrence of an orogenic activity from Late Neoproterozoic to Lower Cambrian in Central Iran. The proposed genetic model considers the fact that mineralization formed in fractured and brecciated host rocks along shear zones and faults from metal-bearing connate waters that were discharged due to deformational dewatering of sediments.     

Evidence of long-lived I and Pu isotopes enrichment in vegetation samples around the Marcoule Nuclear Reprocessing Plant (France)

Iodine-129 and ²³⁸Pu, ²³⁹Pu and ²⁴⁰Pu are radionuclides posing a long-term safety concern due to their potential integration in bio and geo-chemical cycles and their significant half-lives. They are present throughout the environment at very low levels, and more particularly, nuclear fuel reprocessing plants (NRP) have been identified as local sources of these radionuclides. However, due to measurement difficulties, published data concerning their activity levels in terrestrial environments around NRP facilities remain scarce. The aim of the present paper is to communicate ¹²⁹I, ²³⁸Pu and ^239+240Pu measurements results from the area surrounding the Marcoule NRP, which is situated in SE France. Several vegetation samples were collected around the nuclear installation in 1999 and 2000, in order to examine the possible impacts of its atmospheric I and Pu discharges. Based on ²³⁸Pu/^239+240Pu activity ratios and ¹²⁹I/¹²⁷I isotopic ratios, local increases in Pu and ¹²⁹I were detected and related to industrial activity.     

Injection mechanisms of short-lived radionuclides and their homogenization

The supernova injection model for the origin of the short-lived radionuclides (SLRs) in the early solar system is reviewed. First, the meteoritic evidence supporting the model is discussed. Based on the presence of ⁶⁰Fe it is argued that a supernova must have been in close proximity to the nascent Solar System. Then, two models of supernova injection, the supernova trigger model and the aerogel model, are described in detail. Both these injection model provide a mechanism for incorporating SLRs into the early solar system. Following this, the mechanisms present in the disk to homogenize the freshly injected radionuclides, and the timescales associated with these mechanisms, are described. It is shown that the SLRs can be homogenized on very short timescales, from a thousand years up to ∼1 million years. Finally, the SLR ratios expected from a supernova injection are compared to the ratios measured in meteorites. A single supernova can inject enough radionuclides to explain the radionuclide abundances present in the early solar system.     

Ba/Sr,Ca/Sr and 87Sr/86Sr ratios in soil water and groundwater: implications for relative contributions to stream water discharge

Barium/Sr and Ca/Sr ratios have been used to model the relative importance of different sources of stream water. Major and trace element concentrations together with ⁸⁷Sr/⁸⁶Sr ratios were measured in precipitation, soil water, groundwater and stream water in a small (9.4 km²) catchment in northern Sweden. The study catchment is drained by a first order stream and mainly covered with podzolized Quaternary till of granitic composition. It is underlain by a 1.8 Ga granite. A model with mixing equations used in an iterative mode was developed in order to separate the stream water into 3 subsurface components: soil water, shallow groundwater, and deep groundwater. Contributions from precipitation are thus not included in the model. This source may be significant for the stream water generation, but it does not interfere with the calculations of the relative contributions from the subsurface components. The results show that the deep groundwater constitutes between 5 and 20% of the subsurface water discharge into the stream water. The highest values of the deep groundwater fraction occur during base flow. Soil water dominates during snowmelt seasons, whereas during base flow it is the least important fraction. Soil water accounts for 10–100% of the subsurface water discharge into the stream water. Shallow groundwater accounts for up to 80% of the subsurface water discharge with the lowest values at peak discharge during snowmelt seasons and the highest values during base flow. The validity of the model was tested by comparing the measured ⁸⁷Sr/⁸⁶Sr ratios in the stream water with the ⁸⁷Sr/⁸⁶Sr ratios predicted by the model. There was a systematic difference between the measured and modelled ⁸⁷Sr/⁸⁶Sr ratios which suggests that the fraction of soil water is overestimated by the model, especially during spring flood. As a consequence of this overestimation of soil water the amount of shallow groundwater is probably underestimated during this period. However, it is concluded that the differences between measured and predicted values are relatively small, and that element ratios are potentially effective tracers for different subsurface water flowpaths in catchments.     

Re-os isotope systematics of the Taklimakan Desert sands, moraines and river sediments around the taklimakan desert, and of Tibetan soils

Reported here are the first ¹⁸⁷Os/¹⁸⁸Os ratios and abundances of Os and Re for Taklimakan Desert sands and glacial moraines from the Kunlun Mountains. Osmium isotopic data are also reported for river sediments around the Taklimakan Desert, river sediments from the Kunlun and Tianshan Mountains, Tibetan soils and loesses from the Loess Plateau, as well as Sr and Nd isotopic data for these samples. The Taklimakan Desert sands from various regions show surprisingly homogeneous Os isotopic ratios (¹⁸⁷Os/¹⁸⁸Os = 1.29 ± 0.08) and abundances (Os = 11 ppt), with some variations in Re abundances (Re = 130 to 260 ppt) and ¹⁸⁷Re/¹⁸⁸Os ratios (60 to 140). The ¹⁸⁷Os/¹⁸⁸Os ratios for the Taklimakan Desert sands are close to the average for Kunlun moraines, river sediments around the Taklimakan Desert sands, and the Tibetan soils, supporting the idea that the Taklimakan Desert sands are derived from moraines and river sediments around the desert or from Tibetan soils and are homogenized by aeolian activity in the desert. Furthermore, the Os isotopic data for the sediments studied here are compared with those (¹⁸⁷Os/¹⁸⁸Os = 1.04, Os = 32 ppt, Re = 206 ppt, ¹⁸⁷Re/¹⁸⁸Os = 35) of loesses from the Loess Plateau reported elsewhere, and it is concluded that the Re-Os data for the loess can be used as proxy for the upper continental crust.     

Constraining initial Th activity in incrementally deposited, biogenic aragonite from the Bahamas

The ²³⁰Th content of subsurface Bahamas seawater has been estimated from incrementally deposited aragonite skeletons of sclerosponges using U-series age models which imply syndepositional incorporation of ²³⁰Th. First order age models, assuming constant growth rate and zero initial ²³⁰Th activity, display an average surface age of 63 ± 18 y despite the fact that the surfaces of the organisms were known to be alive at the time collection in the 1990s. A knowledge of the initial ²³⁰Th activity is necessary to incorporate the surface age constraint into an age model. In the Bahamas, this approach estimates an initial ²³⁰Th/²³²Th activity ratio of 4.3 ± 1.1 when applied to several individuals of the Caribbean sclerosponge Ceratoporella nicholsoni. These results differ from the same approach applied to previous work on Jamaican sclerosponges accreting aragonite in an environment closer to crustal sources and with less carbonate substrate. We report new measurements of Jamaican sclerosponge suggesting initial activity ratios of ²³⁰Th/²³²Th of ∼1, albeit with a high amount of uncertainty, indicating a regional difference in initial thorium activities. The estimates of initial ²³⁰Th/²³²Th activity ratios in the Bahamas are similar to the dissolved ratio rather than the particulate ratio and can be explained by mixing of open ocean water and bank-top surface water, however no information regarding temporal changes in the amount of initial ²³⁰Th/²³²Th activity available for incorporation into biogenic aragonite can be constrained using this approach. Growth rates do not change after correction for initial thorium and they display an inverse relationship with depth. Although this paper deals uniquely with sclerosponge aragonite, it is likely that the approach can be used on any incrementally deposited biogenic aragonite, provided information is known a priori about the first order growth model and there is evidence that initial thorium incorporation is representative of ambient environment rather than individual physiology.     

Correlations of natural radionuclides in sediment from Danube

The correlation between specific activities of some natural radionuclides (²³⁸U, ²²⁶Ra, ²³²Th, ⁴⁰K) measured in sediment taken from river bottom was studied. The sediment was taken from the Serbian part of the Danube River. Good correlation between some of the isotopes is observed, so that their specific activity ratios are spread over a lower range than specific activities themselves. This suggests that evaluation of specific activity ratios of some natural radionuclides could be a more sensitive method for the determination of increased levels of some of them than the straightforward analysis of specific activities.     

Petrogenesis of isotopically unusual Pliocene olivine leucitites from Deep Springs Valley, California

High-K mafic alkalic lavas (5.4 to 3.2 wt% K₂O) from Deep Springs Valley, California define good correlations of increasing incompatible element (e.g., Sr, Zr, Ba, LREE) and compatible element contents (e.g., Ni, Cr) with increasing MgO. Strontium and Nd isotope compositions are also correlated with MgO; ⁸⁷Sr/⁸⁶Sr ratios decrease and ɛ_Nd values increase with decreasing MgO. The Sr and Nd isotope compositions of these lavas are extreme compared to most other continental and oceanic rocks; ⁸⁷Sr/⁸⁶Sr ratios range from 0.7121 to 0.7105 and ɛ_Nd values range from −16.9 to −15.4. Lead isotope ratios are relatively constant, ²⁰⁶Pb/²⁰⁴Pb ∼17.2, ²⁰⁷Pb/²⁰⁴Pb ∼15.5, and ²⁰⁸Pb/²⁰⁴Pb ∼38.6. Depleted mantle model ages calculated using Sr and Nd isotopes imply that the reservoir these lavas were derived from has been distinct from the depleted mantle reservoir since the early Proterozoic. The Sr-Nd-Pb isotope variations of the Deep Springs Valley lavas are unique because they do not plot along either the EM I or EM II arrays. For example, most basalts that have low ɛ_Nd values and unradiogenic ²⁰⁶Pb/²⁰⁴Pb ratios have relatively low ⁸⁷Sr/⁸⁶Sr ratios (the EM I array), whereas basalts with low ɛ_Nd values and high ⁸⁷Sr/⁸⁶Sr ratios have radiogenic ²⁰⁶Pb/²⁰⁴Pb ratios (the EM II array). High-K lavas from Deep Springs Valley have EM II-like Sr and Nd isotope compositions, but EM I-like Pb isotope compositions. A simple method for producing the range of isotopic and major- and trace-element variations in the Deep Springs Valley lavas is by two-component mixing between this unusual K-rich mantle source and a more typical depleted mantle basalt. We favor passage of MORB-like magmas that partially fused and were contaminated by potassic magmas derived from melting high-K mantle veins that were stored in the lithospheric mantle. The origin of the anomalously high ⁸⁷Sr/⁸⁶Sr and ²⁰⁸Pb/²⁰⁴Pb ratios and low ɛ_Nd values and ²⁰⁶Pb/²⁰⁴Pb ratios requires addition of an old component with high Rb/Sr and Th/Pb ratios but low Sm/Nd and U/Pb ratios into the mantle source region from which these basalts were derived. This old component may be sediments that were introduced into the mantle, either during Proterozoic subduction, or by foundering of Proterozoic age crust into the mantle at some time prior to eruption of the lavas. Received: 28 February 1997 / Accepted: 9 July 1998     

Subduction—Modified Subcontinental Mantle in South China：Trace Element and Isotope Evidence in Basalts from Hainan Island

Cenozoic lavas from Hainan Island,South China,comprise quartz tholeiite,olivine tholeiite,alkali basalt,and basanite and form a continuous,tholeiite-dominated,compositional spectrum.Highly incompatible elements and their relationships with isotopes in these lavas are shown to be useful in evaluating mantle-source composition,whereas modeling suggests that ratios of elements with bulk partition coefficients significantly larger than those of Nb and Ta may be sensitive to partial melting.Th/Ta and La/Nb ratios of alkali basalts are lower than those of tholeiites,and they are all lower than those of the primitive mantle,These ratios correlate positively with ^207Pb/^204Pb and ^87Sr/^86Sr ratios.Such relationships can be explained by mixing of depleted and enriched source components.A depleted component is indicated by alkali basalt compositions and is similar to some depleted OIB (PREMA).The enriched component,similar to sediment compositions,is indicated by tholeiites with high LILE/HFSE,^207Pb/^204Pb,and ^87Sr/^86Sr ratios.In general,basalts from Hainan and the South China Basin(SCB)share common geochemical characters.e.g.high Rb/Sr,Th/Ta,^207Pb/^206Pb,and low Ba/Th ratios.Such a geochemical trend is comparable to that of EMII-type OIB and best explained as the result of subduction.Occurrence of these characteristics in both continental Hainan basalts and SCB seamout basalts indicates the presence of a South China geochemical domain that exists in the mantle region below the lithosphere.     

A theoretical approach to understanding the isotopic heterogeneity of mid-ocean ridge basalt

We have developed an idealized mathematical model to understand the isotopic variability of the mantle and its relation to the observed variations in isotopic ratios ¹⁴³Nd/¹⁴⁴Nd, ⁸⁷Sr/⁸⁶Sr, ¹⁷⁶Hf/¹⁷⁷Hf, ²⁰⁸Pb/²⁰⁴Pb, ²⁰⁶Pb/²⁰⁴Pb, and ²⁰⁷Pb/²⁰⁴Pb measured on mid-ocean ridge basalt (MORB). We consider a simple box model of mantle processes. A single melt region produces a melt fraction F of melt, and the average time since a given parcel of mantle material last visited this region is given by the time scale τ_melt. The melt region fractionates the parent/daughter ratios. Over time this leads to variations in the mantle isotopic ratios as the parent decays to the daughter. Key assumptions are that the half-life of the parent isotope is large compared with τ_melt, that the flow is strongly stirring, and that the mantle has reached a statistical steady state. This enables us to neglect the specifics of the underlying flow. Sampling from our model mantle is dealt with by averaging over a large number N of samples to represent the mixing after melting.The model predicts a probability density for isotopic ratios in MORB which, with exception of the Pb isotopes, are consistent with measurements. Fitting the MORB data to this model gives estimates of the model parameters F, τ_melt, and N. Small melt fractions with F around 0.5% are essential for a good fit, whereas τ_melt and N are less well constrained. τ_melt is estimated at around 1.4 to 2.4 Ga, and N is of the order of hundreds. The model predicts a larger variability for the Pb isotopes than that observed. As has been stated by many previous authors, it appears that fundamental differences exist between the dynamics of Pb isotopes and those of Nd, Sr and Hf isotopes.     

Dating ultra-deep mine waters with noble gases and Cl, Witwatersrand Basin, South Africa

Concentrations and isotopic ratios of dissolved noble gases, ³⁶Cl, δD and δ¹⁸O in water samples from the ultra-deep gold mines (0.718 to 3.3 km below the surface) in the Witwatersrand Basin, South Africa, were investigated to quantify the dynamics of these ultra deep crustal fluids. The mining activity has a significant impact on the concentrations of dissolved gases, as the associated pressure release causes the degassing of the fissure water. The observed under saturation of the atmospheric noble gases in the fissure water samples (70-98%, normalized to ASW at 20°C and 1013 mbar) is reproduced by a model that considers diffusive degassing and solubility equilibration with a gas phase at sampling temperature. Corrections for degassing result in ⁴He concentrations as high as 1.55 · 10⁻¹cm³STP⁴He g⁻¹, ⁴⁰Ar/³⁶Ar ranging between 806 and 10331, and ¹³⁴Xe/¹³²Xe and ¹³⁶Xe/¹³²Xe ratios above 0.46 and 0.44, respectively. Corrected ^134(136)Xe/¹³²Xe and ^134(136)Xe/⁴He-ratios are consistent with their production ratios, whereas the nucleogenic ⁴He/⁴⁰Ar, and ^134(136)Xe/⁴⁰Ar ratios generally indicate that these gases are produced in an environment with an average [U + Th]/K-content 2-3 times above that of crustal average. In two scenarios, one considering only accumulation of in situ produced noble gases, the other additionally crustal flux components, the model ages for 14 individual water samples range from 13 to 168 Ma and from 1 to 23 Ma, respectively.The low ³⁶Cl-ratios of (4-37) · 10⁻¹⁵ and comparatively high ³⁶Cl-concentrations of (8-350) · 10⁻¹⁵ atoms ³⁶Cl l⁻¹ reflect subsurface production in secular equilibrium indicating an age in excess of 1.5 Ma or 5 times the half-life of ³⁶Cl.In combination, the results suggest residence times of the fluids in fissures in this region (up to 3.3 km depth) are of the order of 1-100 Ma. We cannot exclude the possibility of mixing and that small quantities of younger water have been mixed with the very old bulk.     

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.     

Oxygen isotope heterogeneity in chondrules from the Mokoia CV3 carbonaceous chondrite

We report a study of the oxygen isotope ratios of chondrules and their constituent mineral grains from the Mokoia, oxidized CV3 chondrite. Bulk oxygen isotope ratios of 23 individual chondrules were determined by laser ablation fluorination, and oxygen isotope ratios of individual grains, mostly olivine, were obtained in situ on polished mounts using secondary ion mass spectrometry (SIMS). Our results can be compared with data obtained previously for the oxidized CV3 chondrite, Allende. Bulk oxygen isotope ratios of Mokoia chondrules form an array on an oxygen three-isotope plot that is subparallel to, and slightly displaced from, the CCAM (carbonaceous chondrite anhydrous minerals) line. The best-fit line for all CV3 chondrite chondrules has a slope of 0.99, and is displaced significantly (by δ¹⁷O ∼ −2.5‰) from the Young and Russell slope-one line for unaltered calcium-aluminum-rich inclusion (CAI) minerals. Oxygen isotope ratios of many bulk CAIs also lie on the CV-chondrule line, which is the most relevant oxygen isotope array for most CV chondrite components. Bulk oxygen isotope ratios of most chondrules in Mokoia have δ¹⁸O values around 0‰, and olivine grains in these chondrules have similar oxygen isotope ratios to their bulk values. In general, it appears that chondrule mesostases have higher δ¹⁸O values than olivines in the same chondrules. Our bulk chondrule data spread to lower δ¹⁸O values than any ferromagnesian chondrules that have been measured previously. Two chondrules with the lowest bulk δ¹⁸O values (−7.5‰ and −11.7‰) contain olivine grains that display an extremely wide range of oxygen isotope ratios, down to δ¹⁷O, δ¹⁸O around -50‰ in one chondrule. In these chondrules, there are no apparent relict grains, and essentially no relationships between olivine compositions, which are homogeneous, and oxygen isotopic compositions of individual grains. Heterogeneity of oxygen isotope ratios within these chondrules may be the result of incorporation of relict grains from objects such as amoeboid olivine aggregates, followed by solid-state chemical diffusion without concomitant oxygen equilibration. Alternatively, oxygen isotope exchange between an ¹⁶O-rich precursor and an ¹⁶O-poor gas may have taken place during chondrule formation, and these chondrules may represent partially equilibrated systems in which isotopic heterogeneities became frozen into the crystallizing olivine grains. If this is the case, we can infer that the earliest nebular solids from which chondrules formed had δ¹⁷O and δ¹⁸O values around -50‰, similar to those observed in refractory inclusions.     

Geochemistry and Sr-Nd-Pb Isotopes of the Granites from the Hashitu Mo Deposit of Inner Mongolia, China: Constraints on Their Origin and Tectonic Setting

The Hashitu molybdenum deposit is located in the southern part of the Great Hinggan Range,NE China.Molybdenum mineralization is hosted by and genetically associated with monzogranite and porphyritic syenogranite.Sr-Nd-Pb isotopes of the intrusions show that the porphyritic syenogranite has initial~(87)Sr/~(86)Sr ratios of 0.70418-0.70952,ε_(Nd)(t)values of 1.3 to 2.1(t=143Ma),~(206)Pb/~(204)Pb ratios of 19.191-19.573,~(207)Pb/~(204)Pb ratios of 15.551-15.572,and~(208)Pb/~(204)Pb ratios of38.826-39.143.The monzogranite has initial~(87)Sr/~(86)Sr ratios of 0.70293-0.71305,ε_(Nd)(t)values of 1.1 to2.0(t=147 Ma),~(206)Pb/~(204)Pb ratios of 19.507-20.075,~(207)Pb/~(204)Pb ratios of 15.564-15.596,and~(208)Pb/~(204)Pb ratios of 39.012-39.599.The calculated Nd model ages(T_(DM))for monzogranite and porphyritic syenogranite range from 866 to 1121 Ma and 795 to 1020 Ma,respectively.The granitic rocks in the Hashitu area have the same isotope range as granites in the southern parts of the Great Hinggan Range.The isotope composition indicates that these granites are derived from the partial melting of a juvenile lower crust originating from a depleted mantle with minor contamination by ancient continental crust.The integrating our results with published data and the Late Mesozoic regional tectonic setting of the region suggest that the granites in the Hashitu area formed in an intra-continent extensional setting,and they are related to the thinning of the thickened lithosphere and upwelling of the asthenosphere.     

Ra/Ra and Ra/Ba ratios to track barite formation and transport in the water column

We measured ²²⁸Ra_ex/²²⁶Ra_ex and ²²⁶Ra_ex/Ba_ex ratios in suspended and sinking particles collected at the Oceanic Flux Program (OFP) time-series site in the western Sargasso Sea and compared them to seawater ratios to provide information on the origin and transport of barite (BaSO₄) in the water column. The ²²⁸Ra_ex/²²⁶Ra_ex ratios of the suspended particles down to 2000 m are nearly identical to those of seawater at the same water depth. These ratios are much lower than expected if suspended barite was produced in surface waters and indicate that barite is produced throughout the mesopelagic layer. The ²²⁸Ra_ex/²²⁶Ra_ex activity ratios of sinking particles collected at 1500 and 3200 m varied mostly between 0.1 and 0.2, which is intermediate between the seawater ratio at these depths (<0.03) and the seawater ratios found in the upper 250 m (0.31-0.42). This suggests that excess Ba (i.e., Ba_ex = Ba_total − Ba_lithogenic), considered to be mainly barite, present in the sinking flux is a mixture of crystals formed recently in the upper water column, formed several years earlier in the upper water column, or formed recently in deeper waters. We observe a sizeable temporal variability in the ²²⁸Ra_ex/²²⁶Ra_ex ratios of sinking particles, which indicates temporal variability in the relative proportion of barite crystals originating from surface (with a high ²²⁸Ra_ex/²²⁶Ra_ex ratio) and mesopelagic (with a low ²²⁸Ra_ex/²²⁶Ra_ex ratio) sources. However, we could not discern a clear pattern that would elucidate the factors that control this variability. The ²²⁶Ra/Ba ratios measured in seawater are consistent with the value reported from the GEOSECS expeditions (2.3 dpm μmol⁻¹) below 500 m depth, but are significantly lower in the upper 500 m. High ²²⁶Ra_ex/Ba_ex ratios and elevated Sr concentrations in suspended particles from the upper water column suggest preferential uptake of ²²⁶Ra over Ba during formation of SrSO₄ skeletons by acantharians, which must contribute to barite formation in shallow waters. Deeper in the water column the ²²⁶Ra_ex/Ba_ex ratios of suspended particles are lower than those of seawater. Since ²²⁸Ra_ex/²²⁶Ra_ex ratios demonstrate that suspended barite at these depths has been produced recently and in situ, their low ²²⁶Ra_ex/Ba_ex ratios indicate preferential uptake of Ba over Ra in barite formed in mesopelagic water.     

A detailed Th,Sr and O isotope study of Hekla: differentiation processes in an Icelandic Volcano

²³⁸U–²³⁰Th disequilibria and Sr and O isotope ratios have been measured in a suite of samples from most of the known prehistoric and historic eruptions of Hekla volcano, Iceland. They cover the compositional range from basaltic andesite to rhyolite. Recent basalts erupted in the vicinity of the volcano and a few Pleistocene basalts have also been studied. Geochemical data indicate that the best tracers of magmatic processes in Hekla are the (²³⁰Th/²³²Th) and Th/U ratios. Whereas most geochemical parameters, including Sr, Nd and O isotopes, could be compatible with crystal fractionation, (²³⁰Th/²³²Th) and Th/U ratios differ in the basalts and basaltic andesites (1.05 and 3.2, respectively) and in the silicic rocks, dacites and rhyolites (0.98 and 3.4–3.7, respectively). This observation precludes fractional crystallization as the main differentiation process in Hekla. On the basis of these results, the following model is proposed: basaltic magmas rise in the Icelandic crust and cause partial melting of metabasic rocks, leading to the formation of a dacitic melt. The basaltic magma itself evolves by crystal fractionation and produces a basaltic andesite magma. The latter can mix with the dacitic liquid to form andesites. At higher levels in the magma chamber, the dacitic melt sometimes undergoes further differentiation by crystal fractionation and produces subordinate volumes of rhyolites. Together all these processes lead to a zoned magma chamber. However, complete zoning is achieved only when the repose time between eruptions is long enough to allow the production of significant volumes of dacitic magma by crustal melting. This situation corresponds to the large plinian eruptions. Between these eruptions, the so-called intra-cyclic activity is characterized by the eruption of andesites and basaltic andesites, with little crustal melting. The magmatic system beneath Hekla most probably was established during the Holocene. The shape and the size of the magma chamber may be inferred from the relationships between the composition of the lavas and the location of the eruption sites. In a cross-section perpendicular to Hekla's ridge, a bell-shaped reservoir 5 km wide and 7 km deep appears the most likely; its top could be at depth of 8 km according to geophysical data.     

On the possibility of determining rates of removal of uranium from crystalline igneous rocks using U-series disequilibria—2: applicability of a U-leach model to mineral separates

Preliminary U-series data are presented on the disequilibria of mineral separates of surface samples from the Eye-Dashwa lakes granite (Canada). Most analyses of the ferromagnesian, quartz-plus-feldspar, and zircon-plus-sphene grains, show that leaching of U has taken place such that²³⁴U/²³⁹U≤ 1 and ²³⁰Th/²³⁴U 1. The simple leach model presented in a companion paper was used to explain these characteristic ratios. It is suggested that the leach model may be used on zircon and sphere grains to estimate U-leach rates, and this is relevant to the suggestion of using sphene-like hosts as the primary barrier in the safe disposal of nuclear waste. A full analysis of U mobility within a given rock volume was not possible due to our limited data base and to our inability to monitor labile U directly.