Uranium-series disequilibrium in tuffs from Yucca Mountain,Nevada, as evidence of pore-fluid flow over the last million years

Samples of tuff from boreholes drilled into fault zones in the Exploratory Studies Facility (ESF) and relatively unfractured rock of the Cross Drift tunnels, at Yucca Mountain, Nevada, have been analysed by U-series methods. This work is part of a project to verify the finding of fast flow-paths through the tuff to ESF level, indicated by the presence of ‘bomb’ ³⁶Cl in pore fluids. Secular radioactive equilibrium in the U decay series, (i.e. when the radioactivity ratios ²³⁴U/²³⁸U, ²³⁰Th /²³⁴U and ²²⁶Ra/²³⁰Th all equal 1.00) might be expected if the tuff samples have not experienced radionuclide loss due to rock-water interaction occurring within the last million years. However, most fractured and unfractured samples were found to have a small deficiency of ²³⁴U (weighted mean ²³⁴U/²³⁸U=0.95±0.01) and a small excess of ²³⁰Th (weighted mean ²³⁰Th/²³⁴U 1.10±0.02). The ²²⁶Ra/²³⁰Th ratios are close to secular equilibrium (weighted mean=0.94±0.07). These data indicate that ²³⁴U has been removed from the rock samples in the last ∼350 ka, probably by pore fluids. Within the precision of the measurement, it would appear that ²²⁶Ra has not been mobilized and removed from the tuff, although there may be some localised ²²⁶Ra redistribution as suggested by a few ratio values that are significantly different from 1.0. Because both fractured and unfractured tuffs show approximately the same deficiency of ²³⁴U, this indicates that pore fluids are moving equally through fractured and unfractured rock. More importantly, fractured rock appears not to be a dominant pathway for groundwater flow (otherwise the ratio would be more strongly affected and the Th and Ra isotopic ratios would likely also show disequilibrium). Application of a simple mass-balance model suggests that surface infiltration rate is over an order of magnitude greater than the rate indicated by other infiltration models and that residence time of pore fluids at ESF level is about 400 a. Processes of U sorption, precipitation and re-solution are believed to be occurring and would account for these anomalous results but have not been included in the model. Despite the difficulties, the U-series data suggest that fractured rock, specifically the Sundance and Drill Hole Wash faults, are not preferred flow paths for groundwater flowing through the Topopah Spring tuff and, by implication, rapid-flow, within 50 a, from the surface to the level of the ESF is improbable.     

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.     

U-Th chronology and paleoceanographic record in a Fe-Mn crust from the NE Atlantic over the last 700 ka

Hydrogenetic ferromanganese crusts (Fe-Mn crusts) provide a secular record of the variations of seawater composition responding to changes in ocean circulation and erosion processes. In this respect, the acquisition of an absolute and reliable chronology in Fe-Mn crusts is a prerequisite. Here we combine four different and complementary chronometers (¹⁰Be, ²³⁰Th_ex, ²³⁰Th_ex/²³²Th, ²³⁴U/²³⁸U) in a Fe-Mn crust dredged at ∼2000 m depth in the east Atlantic to first establish a reliable chronology over the Quaternary period. Then, we use EDS chemical analysis to look for correlation between major element chemistry and climate changes. (²³⁰Th_ex), (²³⁰Th_ex/²³²Th), and Be data give very consistent growth rates. In particular, the good match between (²³⁰Th_ex) and (²³⁰Th_ex/²³²Th) data indicates that at the location of crust 121DK, ²³⁰Th and ²³²Th fluxes in the water column change simultaneously and suggests that the normalization of ²³⁰Th_ex to ²³²Th makes (²³⁰Th_ex/²³²Th) a better chronometer. Our best-fit model suggests that crust 121DK experienced changes in growth rates at ∼122 and 312 ka and a growth with a constant ²³⁰Th initial flux. This chronology returns an age of 680 ka for the uppermost 1.5 mm. The (²³⁴U/²³⁸U) depth profile, however, was clearly affected by diffusion of ²³⁴U in the porous crust and can therefore not be used to derive a reliable chronology. One part of the crust seems isolated from pore water diffusion and can be physically recognized as a zone of very small porosity. On the basis of the (²³⁰Th_ex/²³²Th) chronology, major element chemistry is shown to be linked to climate change. Mn/Fe variations compare well with those in a Fe-Mn crust from the Pacific, showing systematic maxima during glacial stages 2 and 4. High Mn/Fe are tentatively interpreted to reflect expansion of the oxygen minimum zone during glacial periods, resulting from higher bioproductivity. In addition we note that the surface (²³⁰Th/²³²Th) activity ratio of crust 121DK is entirely consistent with advection of deep water from the western toward the eastern Atlantic basin.     

Pleistocene climatic change in Southern Australia and its effect on speleothem deposition in some Nullarbor caves

Activity ratios of ²³⁴U/²³⁸U, ²³⁰Th/²³⁴U, and ²³⁰Th/²³²Th have been determined for calcite, gypsum and halite speleothems from caves of the Nullarbor Plain, mostly in the area N and NW of Mundrabilla Station, for the purpose of U-series dating. All calcite speleothems contain adequate amounts of uranium for dating, but some show an excess of ²³⁰Th. Stratigraphic relationships indicate that there were at least three phases of calcium carbonate deposition in the Nullarbor caves. The calcite samples, with one possible exception, have ages in excess of ca. 400000 yrs BP. This suggests that no significant amounts of calcium carbonate deposition have taken place during the last 400ka. At present, active deposition of speleothems is restricted almost entirely to gypsum and halite. The only gypsum speleothem dated was found to have a finite age of ca. 185 ka. Six dates on a small halite speleothem containing insect and arachnid remains indicate that it formed rapidly during Holocene time.     

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.     

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.     

U/Th systematics and ages of authigenic carbonates from Hydrate Ridge, Cascadia Margin: recorders of fluid flow variations

Uranium (U) concentrations and activity ratios (δ²³⁴U) of authigenic carbonates are sensitive recorders of different fluid compositions at submarine seeps of hydrocarbon-rich fluids (“cold seeps”) at Hydrate Ridge, off the coast of Oregon, USA. The low U concentrations (mean: 1.3 ± 0.4 μg/g) and high δ²³⁴U values (165-317‰) of gas hydrate carbonates reflect the influence of sedimentary pore water indicating that these carbonates were formed under reducing conditions below or at the seafloor. Their ²³⁰Th/²³⁴U ages span a time interval from 0.8 to 6.4 ka and cluster around 1.2 and 4.7 ka. In contrast, chemoherm carbonates precipitate from marine bottom water marked by relatively high U concentrations (mean: 5.2 ± 0.8 μg/g) and a mean δ²³⁴U ratio of 166 ± 3‰. Their U isotopes reflect the δ²³⁴U ratios of the bottom water being enriched in ²³⁴U relative to normal seawater. Simple mass balance calculations based on U concentrations and their corresponding δ²³⁴U ratios reveal a contribution of about 11% of sedimentary pore water to the bottom water. From the U pore water flux and the reconstructed U pore water concentration a mean flow rate of about 147 ± 68 cm/a can be estimated. ²³⁰Th/²³⁴U ages of chemoherm carbonates range from 7.3 to 267.6 ka. ²³⁰Th/²³⁴U ages of two chemoherms (Alvin and SE-Knoll chemoherm) correspond to time intervals of low sealevel stands in marine isotope stages (MIS) 2, 4, 5, 6, 7 and 8. This observation indicates that fluid flow at cold seep sites sensitively reflects pressure changes of the hydraulic head in the sediments. The δ¹⁸O_PDB ratios of the chemoherm carbonates support the hypothesis of precipitation during glacial times. Deviations of the chemoherm δ¹⁸O values from the marine δ¹⁸O record can be interpreted as to reflect temporally and spatially varying bottom water and/or vent fluid temperatures during carbonate precipitation between 2.6 and 8.6°C.     

水－岩反应的铀系不平衡判别

天然体系中水－岩反应的铀系不平衡判别,是基于水－岩反应使岩石中天然铀衰变系子体核素＾２３４Ｕ,＾２２６Ｒｂ和六价铀的选择性溶失,造成原始放射性平衡遭到不同程度破坏,因而可利用现今测得的岩石中３组核素放射性活度比值Ａ（＾２３４Ｕ）／Ａ（＾２３８Ｕ）,Ａ（＾２３０Ｔｈ）／Ａ（＾２３４Ｕ）和Ａ（＾２２６Ｒａ）／Ａ（＾２３０Ｔｈ）反演判别该岩石曾经历了近代水－岩反应的大致强度和出现,持续时间,这是近十余年     

History of actinide and minor element mobility in an Archean granitic batholith in Manitoba,Canada

Surface and borehole core samples from the Lac du Bonnet granite, Manitoba, Canada, have been analysed for major element concentrations,Fe³⁺/Fe (total) ratios, rare earth element (REE) content and actinide isotopic abundances. This work forms part of the geological investigations of the Canadian Nuclear Fuel Waste Management Program, performed by Atomic Energy of Canada Limited (AECL). The study attempts to understand the history of, and processes governing, mobilisation of elements and naturally occurring radionuclides during high- and low-temperature alteration events in fluid-bearing fractures in the granite.One surface sample and two core samples (from ∼ 150 m and 730 m) are each in contact with fractures in the granite and show evidence of alteration events that penetrated the rock matrix over distances of at least 3 cm. Loss of Ca and Na is seen in cores from a depth of ∼ 150 m from the highly altered, hematite-rich rock adjacent to sub-horizontal fracture zones at the Underground Research Laboratory (URL) of AECL, near Lac du Bonnet. In contrast, K, Fe,Fe³⁺/Fe and U concentrations increase towards the fracture surface due to formation of illite and association of U with hematite and the illite. At the fracture surface, U continues to increase, but Fe and theFe³⁺/Fe ratio decrease indicating Fe removal by reduction. The REE also show some enrichment in more altered rock at intermediate depths, but the total REE concentration is lower than in the surface and deep core samples. No clear trends are visible for parent and fracture-surface REE in surface and deep core samples, however.Disequilibrium values of²³⁴U/²³⁸U and ²³⁰Th/²³⁴U ratios in surface and intermediate depth core samples indicate that U has been mobilised in recent geological time (the last Ma), but Th has remained relatively immobile. High Th/U and²³⁰Th/²³⁴U ratios in surface samples are indicative of rapid leaching of U but little isotopic fractionation, probably within the last 10⁵ a. Apparently unaltered rock, several centimetres distant from the fracture in surface and intermediate- depth samples, has lost appreciable U, but evidence from U-series disequilibrium studies suggests that this process occurred more than one million years ago, perhaps during deuteric or hydrothermal alteration. Core from a fracture at depth in the granite shows little hematite or clay formation and lacks evidence of REE and recent or ancient actinide mobilisation.The U-series results are correlated with the observed concentrations and isotope activity ratios of U in groundwaters sampled from the same or adjacent fractures. Analyses of samples of highly altered rubble recovered from centre portions of fracture zones at the URL show both excesses and deficiencies of²³⁴U and²³⁰Th in neighbouring locations, possibly due to the presence of a redox front whose position is controlled by modern groundwater composition.The implications of these results are discussed for the concept of disposal of nuclear fuel waste at depth in plutonic rock on the Canadian Shield.     

中国东部全新世火山的镭-钍同位素年代学

活火山是指1万年来有过喷发历史的全新世火山。火山的高分辨年代学对火山灾害评估和火山分类具有重要意义。对于缺乏历史记载的全新世火山,直接对火山岩进行同位素定年很困难。本文利用具有高时间分辨率的镭-钍-铀非平衡确定中国东部年轻火山的年龄。根据镭-钍-铀同位素,海南岛的马鞍岭和雷虎岭是全新世火山（马鞍岭：4.3ka;雷虎岭：4.7ka）;镜泊湖火山（4.9ka）也是全新世火山;龙岗火山存在晚更新世和全新世活动（7.0ka,15.0ka）;大兴安岭阿尔山和诺敏河Ra/Th非平衡消失但²³⁰Th/²³⁸U非平衡显著,属于晚更新世喷发（阿尔山：63ka;诺敏河：71ka）。海南岛的马鞍岭火山、雷虎岭火山和东北地区的龙岗火山、镜泊湖火山,是4座活火山。至于东北地区的阿尔山和诺敏河火山是否是活火山,有待测试更多样品的Ra/Th同位素。五大连池老黑山和火烧山有历史喷发记录,这与它们都存在显著Ra/Th非平衡一致。五大连池老黑山和火烧山的岩浆滞留年龄分别小于4.2ka和3.2ka,岩浆上升速率>18~23m/y。

     

Open system alkaline magmatism in northern Kenya: evidence from U-series disequilibria and radiogenic isotopes

U-series activity ratios, Sr-Nd-Pb isotopic ratios and major and trace element compositions have been determined on young basalts (<10 ka) and trachytes from the volcano Emuruangogolak in the Kenya Rift Valley. The basalts are mildly alkaline and are associated with small volumes of hawaiite. The mafic rocks are characterised by high (²³⁰Th/²³²Th) (≥1.06) with low (²³⁸U/²³⁰Th) ratios (≤0.72). They have variable incompatible trace element ratios (e.g. Zr/Nb, Ba/Zr), indicating that they represent a number of magmatic lineages. The trachytes, which comprise both comenditic and pantelleritic varieties, have significantly lower (²³⁰Th/²³²Th) ratios than the basalts, with clear differences between pantelleritic and comenditic types. The (²³⁸U/²³⁰Th) ratios in the pantellerites range from less, to greater, than 1. The variations in composition and isotopic diversity must represent different sources for the trachytes. Internal isochrons for the trachytes give U-Th ages of 14 to 40 ka, similar to single crystal laser fusion ⁴⁰Ar/³⁹Ar ages from sanidine phenocrysts (16–38 ka) for the same rocks. Post-crystallisation residence times of the trachytes were very short, implying relatively rapid movement of trachyte from magma chamber to the surface. Variations in the initial (²³⁰Th/²³²Th)₀ ratios (0.69–1.14) of both basalts and trachytes indicate that Emuruangogolak has erupted a large range of isotopically diverse magmas over a very short period of time (38 ka), from conduits closely spaced around the summit of the volcano. Received: 29 May 1996 / Accepted: 24 November 1997     

U and Th concentrations and isotope ratios in modern carbonates and waters from the Bahamas

The short residence times of Th and Pa in seawater make them very responsive to changes in the ocean environment. We use a new multi-ion-counting technique to make Th and Pa isotope measurements in seawaters from a near-shore environment in which oceanic chemical tracers are not overwhelmed by terrestrial inputs (the Bahamas). An unusual feature of the Bahamas setting is the shallow depth of water residing on the bank tops. These waters have significantly lower ²³²Th/²³⁰Th (∼10,000) than those immediately adjacent to the banks (24,000-31,000) and a (²³¹Pa/²³⁰Th) near the production ratio (∼0.1). The change in ²³²Th/²³⁰Th and (²³¹Pa/²³⁰Th) on the bank tops is explained by almost quantitative removal of Th and Pa by scavenging, and their replacement with a mixture of ²³⁰Th and ²³¹Pa alpha-recoiled from the underlying carbonates, together with Th from dust dissolution. Analysis of a water profile in the Tongue of the Ocean, which separates the Great and Little Bahama Banks, allows us to trace the movement of bank-top water to depth. A distinct minimum in both ²³²Th/²³⁰Th (∼13,000) and (²³¹Pa/²³⁰Th) (∼0.5) is observed at ∼430 m and is interpreted to reflect density cascading of bank-top water with entrained carbonate sediment. These results suggest that Th and Pa can be used as water-mass tracers in near-shore environments. Uranium concentration measurements on the same waters demonstrate that U is conservative across a range in salinity of 2 psu, with a concentration of 3.33 ppb (at a salinity of 35).The incorporation of U and Th isotopes into marine carbonates has also been assessed by analyzing carbonate samples from the same location as these Bahamas waters. Such incorporation is critical for U-Th geochronology. U isotope analyses demonstrate that seawater δ²³⁴U averages 146.6 and does not vary by more than 2.5%o, and that carbonates capture this value. Additional high precision measurements (≈±1%o) on modern carbonates confirm that all oceans have identical δ²³⁴U. Modern marine carbonates are shown to have ²³²Th/²³⁰Th ratios that reflect the local seawater in which they formed.     

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.     

铀系组分法测定年青火山岩年龄的研究

铀系组分法是测定火山岩不同组分中的２３０Ｔｈ／２３２Ｔｈ值和２３８Ｕ／２３２Ｔｈ值、计算年龄的方法。岩石中的各组分是用磁选或浮选分离的。经过论证，组分法与等时线方法是等价的，但不需要从全岩中精选纯的单矿物，不会发生铀和钍同位素的分馏。根据组分法模式测定了云南腾冲盆地北来凤山、老龟坡山和马鞍山火山岩样品的年龄，分别为０．１１ＭａＢ．Ｐ．、５１０００。Ｂ．Ｐ．和２５０００ａＢ．Ｐ，与地层顺序相吻合。组分法对于年青火山岩定年有着极大的潜力。     

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.     

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.     

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.     

Mixing and cycling of uranium,thorium and 210Pb in Puget Sound sediments

Activity profiles of excess ²³⁴Th, excess ²¹⁰Pb, ²³²Th, ²³⁰Th, ²³⁴U and ²³⁸U, and ^228/232Th ratios determined in eight box cores of sediment from six sites in central Puget Sound provide new insights into the dynamic nature of solid phase mixing in surface sediments, the exchange of ²²⁸Ra and other soluble species across the sediment-water interface, and the cycling of U, Th and ²¹⁰Pb in this coastal zone.Comparison of excess ²³⁴Th inventories in sediments with its production rate in the overlying water column indicates a mean residence time of at most 14 days for particles in the central Puget Sound water column.Surface sediment horizons with excess ²³⁴Th have no excess ²²⁸Th which might be used to ascertain sediment accumulation rates over the past decade. Instead, deficiencies of ²²⁸Th due to loss of soluble ²²⁸Ra from pore water to the overlying water persist to 20–30 cm, revealing that exchange of soluble chemicals between pore and overlying waters reaches these depths in the extensively bioturbated sediments of Puget Sound.Solid phase U isotope concentrations tend to increase by up to a factor of two with depth in sediments, as a result of dissolved U being biologically pumped down into sediments where it is partially removed when conditions become mildly reducing. ²³²Th and ²³⁰Th activities and ^230/232Th ratios are constant with depth in sediments, indicating constant detrital phase compositions and essentially no authigenic ²³⁰Th. Steady state ²¹⁰Pb depositional activities in and fluxes to Puget Sound sediments average only about onehalf those for sediments of the open Washington coast north of the Columbia River mouth, primarily because of a much lower supply of dissolved ²¹⁰Pb in sea waters adverting into Puget Sound.Excess ²³⁴Th profiles in sediments reveal much more detail about the depth dependency, dynamic nature and recent history of solid phase mixing processes than excess ²¹⁰Pb profiles. At least six of eight ²³⁴Th profiles show that mixing within the ²¹⁰Pb-defined surface mixed layer is depth dependent. In three profiles, ²³⁴Th-derived mixing rates are fastest several centimeters below the sediment-water interface, indicating greater macro-benthic activity at these depths. Depth dependent mixing coefficients derived from the best fit of a four layer, advection-diffusion-decay model to the ²³⁴Th data are consistent with ²¹⁰Pb profiles determined for the same sediments, strongly suggesting that ²³⁴Th and ²¹⁰Pb are mixed equivalently and in a multilayered manner.     

Electron spin resonance (ESR) and thermal ionization mass spectrometric (TIMS) 230Th/234U dating of teeth in Middle Paleolithic layers at Amud Cave,Israel

Electron spin resonance (ESR) dating and thermal ionization mass spectrometric ²³⁰Th/²³⁴U dating was conducted on six teeth from the prehistoric site of Amud Cave. By combining the ESR and ²³⁰Th/²³⁴U analyses, we obtained burial ages for teeth in various layers of the site. Layer B₁/6–7, from which the Amud I Neanderthal skeleton was recovered, is dated to 53 ± 8 ka. Layer B₂/8, which yielded other important human remains including the Amud 7 skeleton, gives a mean burial age of 61 ± 9 ka. One tooth from the lowest layer (B₄) yielded a date of 70 ± 11 ka, but another tooth from this layer gave an 113 ± 18 ka. Despite this discrepancy, these ages agree with previously published TL ages on heated flints for the corresponding layers. This agreement between ESR on tooth enamel and TL on burned flint is also seen at all other sites studied with both methods in Israel. © 2001 John Wiley & Sons, Inc.     

The transport of U- and Th-series nuclides in sandy confined aquifers

Abundances of ²³⁸U, ²³⁴U, ²³²Th, ²²⁶Ra, ²²⁸Ra, ²²⁴Ra, and ²²²Rn were measured in groundwaters of the Ojo Alamo aquifer in northwest New Mexico. This is an arid area with annual precipitation of ∼22 cm. The purpose was to investigate the transport of U-Th series nuclides and their daughter products in an old, slow-moving groundwater mass as a means of understanding water-rock interactions and to compare the results with a temperate zone aquifer. It was found that ²³²Th is approximately at saturation and supports the view of Tricca et al. (2001) that Th is precipitated irreversibly upon weathering, leaving surface coatings of ²³²Th and ²³⁰Th on aquifer grains. Uranium in the aquifer waters has very high [²³⁴U/²³⁸U] ∼ 9 and low ²³⁸U concentrations. These levels can be explained by low weathering rates in the aquifer (w_238U ∼ 2 × 10⁻¹⁸ to 2 × 10⁻¹⁷s⁻¹) using a continuous flow, water-rock interaction model. The Ra isotopes are roughly in secular equilibrium despite their very different mean lifetimes. The ²²²Rn and ²²⁸Ra isotopes in the aquifer correspond to ∼10% of the net production rate of the bulk rock. This is interpreted to reflect an earlier formed irreversible surface coating of Th that provides Ra and Rn to the aquifer waters. The surface waters that appear to be feeding the aquifer have low [²³⁴U/²³⁸U] and high ²³⁸U concentrations. The flow model shows that it is not possible to obtain the high [²³⁴U/²³⁸U] and low [²³⁸U] values in the aquifer from a source like the present vadose zone input. It follows that the old aquifer waters studied cannot be fed by the present vadose zone input unless they are greatly diluted with waters with very low U concentrations. If the present sampling of vadose zone sources is representative of the present input, then this requires that there was a major change in water input with much larger rainfall some several thousand years ago. This may represent a climatic change in the Southwest.