U234U238 Ratios in limestone cave seepage waters and speleothem from West Virginia

Speleothem from West Virginia, ranging in age from 2000 to 200,000 yr B.P. contains uranium with $\text{U}{}^{234}\text{U}{}^{238}$ ratios significantly greater than unity. This ratio varies from one speleothem to another, as does average U content. Initial ratios, corrected for age, are remarkably constant for a given speleothem. By contrast, $\text{U}{}^{234}\text{U}{}^{238}$ ratios in seepage waters vary significantly from month to month at a given drip site, and their average values differ from that of the speleothem which they are depositing. This discrepancy is attributed either to long-term averaging-out of fluctuations, or fractional precipitation on the speleothem of a chemical species of uranium with a more constant ratio. Constancy of initial $\text{U}{}^{234}\text{U}{}^{238}$ ratios from $\text{Th}{}^{230}\text{U}{}^{234}$. datable portions of speleothems should permit $\text{U}{}^{234}\text{U}{}^{238}$-dating of older portions of the same speleothem, back to about 10⁶ yr B.P., with estimated precision of ±5 per cent.     

State of disequilibrium between 238U, 234U, 226Ra and 222Rn in groundwater from bedrock

Approximately one thousand drilled wells were investigated for their natural radioactivity. The determinations of ²³⁸U, ²³⁴U, ²²⁶Ra and ²²²Rn from 310 samples showed a high state of radioactive disequilibrium between the members of the uranium series present in water. The ${}^{238}\text{U}{}^{226}\text{Ra}$ activity ratio usually fell in the range 1–20 and the ${}^{238}\text{U}{}^{222}\text{Rn}$ activity ratio in the range 1–20 × 10^?4, the highest activity ratios being from samples with an elevated uranium content. The ${}^{234}\text{U}{}^{238}\text{U}$ activity ratio varied between 0.76 and 4.67, the most frequent values showing a 60% excess of ²³⁴U in the samples. Most of the ${}^{234}\text{U}{}^{238}\text{U}$ activity ratios near unity were found in samples with a high uranium content. Several drilled wells with anomalously high uranium contents were found in southern Finland. The average ²²⁶Ra and ²²²Rn contents of these wells were not exceptionally high, which suggests high mobility of uranium in groundwater from the areas involved.     

Uranium in submarine metalliferous deposits

Hydrothermal submarine metalliferous deposits, common in areas of the ocean floor with high heat flow, contain generally about 10 ppm U as an order of magnitude. The $\text{U}{}^{234}\text{U}{}^{238}$ ratio is in the majority of cases close to that of seawater; only in a few cases is it anomalously high. Anomalous $\text{U}{}^{234}\text{U}{}^{238}$ ratios are coupled with low U concentrations. These data are explained by a model where thermal water (essentially heated seawater) in its sub-bottom circulation often is unable to leach U from the basaltic oceanic crust; in fact, these thermal waters may in some cases lose U. When leaching of U from the basalt does take place, probably during shallow stages of the sub-bottom circulation, the resulting anomalous $\text{U}{}^{234}\text{U}{}^{238}$ ratio can be preserved in the hydrothermal deposit only if mixing with ‘seawater’ U is prevented.     

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.     

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.     

The geochemical coherence of Pu and Nd and the 244Pu238U ratio of the early solar system

Two very different sets of ${}^{244}\text{Pu}{}^{238}\text{U}$ ratios have been reported for early solar system materials. One group of samples yields high (0.015–0.016) ratios (Podosek, 1970a, 1972; Drozd et al., 1977) and calculations based on another group of analyses yield low ratios (~0.004) (Marti et al., 1977). Recently measured partition coefficients for Pu and Sm are used to evaluate the data of Marti et al. and $\text{sol}{}^{244}\text{Pu}{}^{238}\text{U}$ ratios from other sources are also considered. A low $\text{sol}{}^{244}\text{Pu}{}^{238}\text{U}$ ratio (~0.005) is favored, and some implications of this low ratio to galactic nucleosynthesis and meteorite age dating are briefly discussed.     

Comparison of 230Th-238U disequilibrium systematics in lavas from three hot spot regions: Hawaii,Prince Edward and Samoa

²³⁰Th-²³⁸U disequilibrium systematics reveal several important characteristics of the mantle source regions and petrogenesis of volcanic rocks in the presumed hot spots of Hawaii, Marion Island (Prince Edward hot spot), and Samoa. The (${}^{230}\text{Th}{}^{232}\text{Th}$) activity ratios of lavas from these three hot spots (1.06 ± 0.07, 1.04 ± 0.08, and 0.81 ± 0.06, respectively) imply that the source regions are each nearly homogeneous with $\text{Th}\text{U}$ weight ratios of 2.9, 3.0, and 3.8. For Marion Island and Mauna Kea, Hawaii, negligible secular variation occurs in the (${}^{230}\text{Th}{}^{232}\text{Th}$) initial ratios. This supports other evidence for very short transfer time between source and surface. Significant residence time at depth prior to eruption cannot be ruled out for the Samoan lavas we have studied; however, the data for one of these flows deviate from the proposed (${}^{230}\text{Th}{}^{232}\text{Th}$)-${}^{87}\text{Sr}{}^{86}\text{Sr}$ correlation (Condomineset al., 1981a) in the opposite sense from that expected for such residence. If it is assumed that the measured (${}^{230}\text{Th}{}^{232}\text{Th}$) ratios of the young lavas reflect $\text{Th}\text{U}$ in their mantle sources, then the observed variations among these three hot spots, combined with those reported by other workers for Iceland, the Azores and Tristan de Cunha, suggest that these sources are characterized by $\text{Th}\text{U}$ ratios ranging from values similar to that of MORB source (~2.5) to values similar to those of bulk earth (~3.8). Mixing of different proportions of depleted and enriched mantle may be responsible for the observed range.     

Initial Pb of the Amîtsoq gneiss,West Greenland,and implications for the age of the Earth

Pb isotopic abundances and U-Th-Pb concentrations are reported for feldspar megacrysts from the 3.59 AE old Amîtsoq gneisses, Godthaab District, West Greenland. The distinctive Pb in the feldspars is the most primitive terrestrial Pb so far observed. It is observed in feldspars which are from different geographic localities and which exhibit varying degrees of deformation and recrystallization. This appear to be either the initial Pb in the Amîtsoq gneiss or the initial Pb only slightly modified by subsequent metamorphism in a low ${}^{238}\text{U}{}^{204}\text{Pb}$ environment. ${}^{238}\text{U}{}^{204}\text{Pb}$ in the feldspars is low and the corrections for in situ produced Pb are only 0.4% for ${}^{207}\text{Pb}{}^{206}\text{Pb}$ and 0.6% for ${}^{204}\text{Pb}{}^{206}\text{Pb}$. The mean corrected isotopic abundances are ${}^{204}\text{Pb}{}^{206}\text{Pb}\text{= 0.08720}$, ${}^{207}\text{Pb}{}^{206}\text{Pb}\text{= 1.1513}$, and ${}^{208}\text{Pb}{}^{206}\text{Pb}\text{= 2.7350}$. The feldspars contain a very small amount of easily leachable radiogenic Pb which is correlated with U and which indicates the formation of U-rich phases at about 2.7 AE. The matrix surrounding the feldspar megacrysts contains Pb which is much evolved relative to the megacrysts and this matrix does not appear to have behaved as a simple closed system. Element redistribution and open system behavior at about 2.7 AE is also suggested by Pb in feldspar from a dike cutting across the gneiss. Assuming that the Amîtsoq gneiss feldspar Pb corrected for in situ U decay was the initial Pb in the gneiss at 3.59 AE (Baadsgaard, 1973), a single-stage “age of the earth” is determined as 4.47 ± 0.05 AE and μ is 8.5. This is indistinguishable from the single-stage age for modern rocks and is distinctly younger than the 4.55 AE age of some meteorites. If the feldspar Pb was modified by metamorphism at 2.7 AE the model age of the earth is calculated as 4.53 AE which is similar to the 4.55 AE age of some meteorites. Two-stage models using the nominal 3.59 AE initial Pb indicate that if the earth is ~4.55 AE old then μ values were low in the early Earth's history and differentiation occurred within a few hundred million years after the planet formed.     

Lead isotopic compositions of South Sandwich Island volcanic rocks and their bearing on magmagenesis in intra-oceanic island arcs

Pb isotope ratios have been measured in 12 volcanic rocks from the South Sandwich Islands. The ranges are ${}^{206}\text{Pb}{}^{204}\text{Pb}\text{= 18.51–18.66;}{}^{207}\text{Pb}{}^{204}\text{Pb}\text{= 15.55–15.64;}{}^{208}\text{Pb}{}^{204}\text{Pb}\text{= 38.42–38.64}$. In ${}^{207}\text{Pb}{}^{204}\text{Pb}\text{-}{}^{206}\text{Pb}{}^{204}\text{Pb}$ and ${}^{208}\text{Pb}{}^{204}\text{Pb}\text{-}{}^{206}\text{Pb}{}^{204}\text{Pb}$ correlation diagrams, the South Sandwich data plot distinctly above the fields for ocean ridge basalts, and yield trends showing apparent mixing with a sedimentary end member similar to South Atlantic pelagic sediments as reported by Chow and Patterson (1962) and this study. Armstrong and Cooper (1971) have likewise shown that volcanics from the Lesser Antilles show mixing trends with North Atlantic sediments in Pb isotope correlation diagrams. The North Atlantic sediments have distinctly higher ${}^{206}\text{Pb}{}^{204}\text{Pb}$ and ${}^{208}\text{Pb}{}^{204}\text{Pb}$ ratios compared to the South Atlantic sediments. The parallel relationships between sediments and volcanic island arc rocks of the North and South Atlantic provide strong evidence for a component of Pb from subducted sediments in the lavas of the west Atlantic basin. In contrast to these data, lavas from the Mariana Arc in the western Pacific show little or no component of Pb from pelagic sediments. The reason for the different behaviors in the two settings is speculative.     

Strontium isotope geology of the South Mountain batholith,Nova Scotia

The South Mountain batholith of southwestern Nova Scotia is a large, peraluminous, granodiorite-granite complex which intrudes mainly greenschist facies metasediments of the Cambro-Ordovician Meguma Group. Using Rb-Sr isochrons constructed from whole rocks and mineral separates, the present study shows a variation in age and initial ratios of the intrusive phases of the batholith as follows: biotite granodiorite (371.8 ± 2.2 Ma, (${}^{87}\text{Sr}{}^{86}\text{Sr}\text{)}{}_{\mathrm{i}}$ ranges from 0.7076 ± 0.0003 to 0.7090 ± 0.0003, with the average = 0.7081); adamellite (364.3 ± 1.3 Ma, $\text{(}{}^{87}\text{Sr}{}^{86}\text{Sr}\text{)}{}_{\mathrm{i}}\text{= 0.70942 ± 35}$); porphyry (361.2 ± 1.4 Ma, $\text{(}{}^{87}\text{Sr}{}^{86}\text{Sr}\text{)}{}_{\mathrm{i}}\text{= 0.71021 ± 119}$); using λ⁸⁷Rb = 1.42 × 10^?11yr^?1.A suite of Meguma country rock samples showed a variation of ${}^{87}\text{Sr}{}^{86}\text{Sr}\text{= 0.7113?0.7177}$ at the time of intrusion of the batholith. A number of xenoliths of this material occurring in the marginal granodiorite had partially equilibrated isotopically with the granodiorite at a higher ${}^{87}\text{Sr}{}^{86}\text{Sr}$ ratio than elsewhere in the granodiorites. This evidence demonstrates that isotopic (and probably some accompanying bulk chemical) contamination by the Meguma rocks has been an important factor in determining the ultimate chemical composition and mineralogy of the South Mountain batholith.The $\text{(}{}^{87}\text{Sr}{}^{86}\text{Sr}\text{)}{}_{372}\text{= 0.7081}$ of the early granodiorites indicates that the parent magma of the South Mountain batholith was derived from a source unlike the Meguma Group. The precise nature of the source region cannot be determined by Rb-Sr work unless the degree of contamination with Megumalike material is known.     

Application of the 227Th230Th method to dating Pleistocene carbonates and comparison with other dating methods

The ${}^{227}\text{Th}{}^{230}\text{Th}$ dating method is described in detail and its usefulness investigated by comparing ages of sixteen Pleistocene carbonates (mainly cave deposits) with those determined by the ${}^{231}\text{Pa}{}^{235}\text{U}$ and ${}^{230}\text{Th}{}^{234}\text{U}$ methods. The ${}^{227}\text{Th}{}^{230}\text{Th}$ ages are found to be critically dependent on corrections for decay of ²²⁷Th prior to alpha counting and ingrowth of daughter isotopes of ²³²Th derived from clastic detritus. Of nineteen sets of ages determined for the sixteen samples, good agreement is found for only seven sets. Differences are attributed to low U content of some samples and the possibility of excess ²²⁷Th in the calcite of samples younger than ~50 ky, possibly due to the coprecipitation of ²³¹Pa during formation. Calculated “negative” ${}^{227}\text{Th}{}^{230}\text{Th}$ ages may be a direct result of this process and the fact that, unlike the other methods, the activity ratio is non-zero at zero age. Nevertheless, the ${}^{227}\text{Th}{}^{230}\text{Th}$ is found to be a useful alternative dating technique for carbonates which are between ~50 and 300 ky, because no spiking is required. It also serves as a check for partial concordancy with ages dated by the other methods.     

UThPb systematics of the eucrite “Juvinas”: Precise age determination and evidence for exotic lead

The U-Th-Pb isotope systematics of the eucrite “Juvinas” have been studied in whole rock fragments as well as in plagioclases and pyroxenes. The results show that this monomict breccia crystallized with a very high $\text{U}\text{Pb}$ initial ratio at T = 4.539 ± 0.004 AE ago. There is evidence for a less radiogenic Pb component (${}^{206}\text{Pb}{}^{204}\text{Pb}\text{= 13.0}$; ${}^{207}\text{Pb}{}^{204}\text{Pb}\text{= 13.5}$; ${}^{208}\text{Pb}{}^{204}\text{Pb}\text{= 32.71}$) interpreted as “exotic lead” induced by a meteoritical impact at the surface of the Juvinas parent body, 1.92 ± 0.06 AE ago.     

The distribution of U and Pu in the St. Severin chondrite

A detailed study of the U distribution of the St. Severin chondrite has been made by fission track radiography in order to clarify the interpretation of fission Xe thermal release data in terms of the mineralogical location of the fission Xe within the meteorite. This is of importance because the ${}^{244}\text{Pu}{}^{238}\text{U}$ ratio for St. Severin has been widely adopted as the average solar system value. The U contents of the constituent minerals cannot account for the total rock U which, instead, appears to be primarily localized on grain boundaries. The greatest localizations of U are in olivine-poor, orthopyroxene-rich ‘clasts’. Our data coupled with those of Podosek (1970a) show that ²⁴⁴Pu in St. Severin was also located on grain boundaries and that the bulk of Pu and U are unfractionated within this meteorite. Due to recoil, the ²⁴⁴Pu fission Xe is found in 10 micron surface layers on major phases. Assuming that the grain boundaries (on which the Pu was located) was formed during metamorphism, the ${}^{244}\text{Pu}{}^{238}\text{U}$ ratio for St. Severin applies to a time subsequent to the textural recrystallization of the meteorite. Our data support the interpretation of Podosek and our best estimate of the solar system ${}^{244}\text{Pu}{}^{238}\text{U}$ is 0.015.     

Anomalously high concentrations of uranium,radium and radon in water from drilled wells in the Helsinki region

The concentrations of uranium. ²²⁶Ra and ²²²Rn were determined in 308 drilled and 58 dug wells in the Helsinki region. The study area was about 400 km² and geologically highly variable, with granites, amphibolites and migmatites the dominant rocks. The radioactivity of water in the dug wells was on a “normal” level, but in numerous drilled wells it was anomalously high. In 14 drilled wells the concentration of uranium exceeded 1000 μg/l, the highest concentration being 14,870 μg/l. For ²²²Rn the maximum concentration was 880,000 pCi/l. The ${}^{226}\text{Ra}{}^{228}\text{Ra}$ and ${}^{230}\text{Th}{}^{232}\text{Th}$ activity ratios showed the isotopes of the uranium series to be dominant in the study area. A state of disequilibrium between ²³⁸U and ²³⁴U was very common in the samples. The ${}^{234}\text{U}{}^{238}\text{U}$ activity ratios varied in the range 1.0–4.0 regardless of the amount of uranium in the water. The conclusion can be drawn from the isotopic data that the high radioactivity of water is in some cases caused by primary uranium mineralizations, but mostly by uranium deposited in fissures of the bedrock. The paper includes a summary of the results of two studies carried out between 1967 and 1977.     

A routine method for the determination of the 234U238U ratio in natural water

A simple method to determine the ${}^{234}\text{U}{}^{238}\text{U}$ ratio in water by α-spectrometry is presented. The thiocyanate complex of uranium is extracted from the water by anion exchange. After elution of the U from the resin it is further purified by extraction from nitrate medium into ether. The source for α-spectrometry is prepared by oxalate electrodeposition. The overall yield is 70%.     

Micromanganese nodules in deep-sea sediments: Uranium-isotopic evidence for post-depositional origin

Micromanganese nodules from three deep-sea cores are found to contain less U than average nodules dredged from the sea floor. The ${}^{234}\text{U}{}^{238}\text{U}$ ratio in these micronodules is higher than any previously reported in deep-sea sediments. We interpret these data to mean that at least some micronodules form well after deposition of the enclosing sediments, in particular where conditions are less oxidizing than average.     

Redistribution of uranium and thorium series isotopes during isovolumetric weathering of granite

Previous studies of the distribution of U and Th in parent versus weathered granites have shown both depletion and enrichment of these elements during weathering. In this study, the distribution of U and Th decay series isotopes was determined in a weathering profile of a granitic saprolite, which showed textural preservation indicating isovolumetric weathering. Two types of dissolution methods were used: a whole-rock dissolution and a sodium-citrate dithionite leach to preferentially attack noncrystalline phases of weathering products. Using volume-based activities, 45–70 percent of the total ²³²Th was gradually removed during weathering. Although the whole-rock ${}^{228}\text{Th}{}^{232}\text{Th}$ activity ratios were in equilibrium, there were large excesses of ²²⁸Th in the leachable fraction of both parent rock (${}^{228}\text{Th}{}^{232}\text{Th}\text{= 2.06}$) and partially weathered saprolite (${}^{228}\text{Th}{}^{232}\text{Th}\text{= 3–6.5}$), due to alpha recoil and release of daughter ²²⁸Th to the weathering rind of the mineral grain. For the most weathered sample, 81 percent of the thorium was in the teachable fraction and ${}^{228}\text{Th}{}^{232}\text{Th}\text{= 1}$, indicating that even the more resistant minerals were attacked.The total U activities showed as much variation in the six parent rock samples as in the weathered profile, and ${}^{234}\text{U}{}^{238}\text{U}$ were in equilibrium in both the whole-rock and leachable fractions. ²³⁰Th was deficient relative to ²³⁴U and ²²⁶Ra in both fractions, suggesting recent addition of U and Ra to the entire profile. The large variation in U was not from absorption onto the intermediate weathering products, because only 11–23 percent of the U was in the leachable fraction.     

Unscrambling the lead model ages

A linear relation is derived for the secular evolution of ${}^{206}\text{Pb}{}^{204}\text{Pb}$, ${}^{207}\text{Pb}{}^{204}\text{Pb}$ and ${}^{208}\text{Pb}{}^{204}\text{Pb}$ ratios, that permits tests to be made for open system evolution on each system independently. Application of the method to conformable ore bodies of various geological age indicates that the available data do not demand an open system evolution for the last 3.8 b.y. ${}^{238}\text{U}{}^{204}\text{Pb}$ and ${}^{232}\text{Th}{}^{204}\text{Pb}$ of 9.66 ± 0.15 and 37.65 ± 1.14 respectively fit best the data for this time interval.A single stage evolution since 4.5 b.y. is unlikely, however, and the major events of continent formation postdate the Earth accretion by at least 400 m.y. The larger scatter of ${}^{207}\text{Pb}{}^{204}\text{Pb}$ data about the evolution line relative to the other isotopic ratios is also interpreted as resulting from a series of continental differentiation events taking place at 3.85 ± 0.15 b.y.     

Radium isotopes in saline seepages,south-western Yilgarn,Western Australia

Water samples from saline seepages in the south-western Yilgarn Block of Western Australia contain high activities of the four naturally-occurring radium isotopes. Activities of up to 310 $\text{pCi}\text{l}$ for ²²⁶Ra and 1720 $\text{pCi}\text{l}$ for ²²⁸Ra were measured and the ${}^{228}\text{Ra}{}^{226}\text{Ra}$ ratio averaged 6.1. Activities of the two short-lived radium isotopes were also high. ²²³Ra activities of up to 94 $\text{pCi}\text{l}$ were found with an average ${}^{226}\text{Ra}{}^{223}\text{Ra}$ ratio of 3.3, considerably lower than the natural abundance ratio of 21.4. Activities of up to 23 $\text{pCi}\text{l}$²²⁷Ac, the long-lived ($\text{t}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{= 22 years}$) grandparent of ²²³Ra, were also measured. The analysis of surface granite samples, the probable source rocks of the radium, gave $\text{Th}\text{U}$ activity ratios of around 1.5. The higher ${}^{228}\text{Ra}{}^{226}\text{Ra}$ ratios of the waters were attributed to readily leached ²²⁸Ra in the weathered granites as a result of thorium remaining after weathering. Leach experiments on U-Th ore by NaCl solutions showed that all four radium isotopes were equally leached. Sulphate anions reduced the ²²⁶Ra and ²²⁸Ra leaching to a greater extent than for ²²³Ra and ²²⁴Ra, suggesting that the latter isotopes were being supported in solution by parent isotopes. In particular this suggested ²²⁷Ac was leached into the sulphate solution but this does not fully account for the amount of ²²⁷Ac seen in the seepage waters.