Actinide crystal-liquid partitioning for clinopyroxene and Ca3(PO4)2

Using fission and alpha track radiography techniques, we have measured partition coefficients (D) for the actinide elements Th, U and Pu between diopsidic clinopyroxene, whitlockite [β-Ca₃ (PO₄)₂] and silicate liquid at 20kbar. Equilibrium partitioning at the crystal-liquid interface is assumed, and corrections for actinide zoning have been applied to the measured D values. Reproducibility for both actinide and minor element D values is carefully examined as a criterion for crystal-liquid interface equilibrium. The data are mostly compatible with interface equilibrium except for experiments at high cooling rates ( ? 30 deg/hr). Partition coefficients for Th/U/Pu of about 0.002/0.002/0.06 are measured for clinopyroxene and 1.2/0.5/3.4 for whitlockite. At an oxygen fugacity of 10^?8.5, Pu is much more readily incorporated into the crystalline phases than is U or Th because of the importance of trivalent Pu. The D_Pu(cpx) is similar to D(cpx) of the light rare earths supporting the concept of Pu/(rare earth) dating.     

Experimental geochemistry of Pu and Sm and the thermodynamics of trace element partitioning

The partitioning of Pu and Sm between diopside/liquid and whitlockite/liquid has been investigated experimentally to evaluate the geochemical coherence of Pu and the light REEs. ${}^{\mathrm{Pu}}\text{D}{}^{\mathrm{Sm}}\text{D}$ is 2̃ for both diopsidic pyroxene and whitlockite. This small amount of fractionation would be decreased further if Pu were compared to Ce or Nd. Our experimental results thus validate the suggestion that Pu behaves as a LREE during igneous processes in reducing environments.Our data and the data of Ray et al. (1983) indicate that temperature rather than melt composition is the most important control on elemental partitioning. This is true even though we demonstrate that additions of only 1–2 wt.% of P₂O₅ to the diopside-anorthite-albite system change ^PuD_cpx by a factor of two. Our data suggest that P₂O₅ in aluminosilicate melts serves as a complexing agent for the actinides and lanthanides.     

Fission-track ages of four meteorites

A method for selective annealing of cosmic-ray tracks has been developed, permitting determination of fission-track ages in the presence of a large background of cosmic-ray tracks. The mesosiderite Bondoc contains 41 fission tracks/cm², of which about 75% are due to neutron-induced fission of U²³⁵ during cosmic-ray exposure. Its net fission-track age is 140 ± 40 Myr, nearly identical to its cosmic-ray exposure age of 150 Myr. The mesosiderite Mincy has a fission-track age of 1500 ± 400 Myr.Nakhla (nakhlite) contains an excess of apparent fission tracks, which may be either genuine fission tracks from Pu²⁴⁴ or etch pits mimicking fission tracks in length, thermal stability, random orientation, and other characteristics. On the assumption that they are fission tracks, the Pu²⁴⁴/U²³⁸ ratio at the onset of track retention in Nakhla was (3.1 ± 1.3) × 10^?3, nearly an order of magnitude lower than the initial solar system ratio. This may reflect a chemical fractionation of Pu and U, or a late impact or magmatic event. Different minerals of the Washougal howardite have different Pu²⁴⁴/U²³⁸ ratios, from (24 ± 7) × 10^?3 to (2.3 ± 0.7) × 10^?3. This may imply a succession of impacts over a period of time. Additionally, Pu and U may have been chemically fractionated from each other in this meteorite.Shocked meteorites show no consistent pattern in the retentivity of fission tracks and of fissiogenic or radiogenic noble gases. Some meteorites, e.g. Bondoc, Serra de Magé, and Mincy, retain gases more completely than tracks; others, e.g. Nakhla and Allende, retain them less completely.Uranium was determined in feldspar and/or pyroxene from 19 Ca-rich achondrites and mesosiderites. For most, only upper limits of 0.01–0.03 ppb were obtained. Apparently the uranium in these meteorites resides almost exclusively in minor phases, as in terrestrial and lunar rocks.     

Behaviour of actinides (Th,U, Np and Pu) and rare earths (La,Ce and Nd) during aqueous leaching of a nuclear glass under geological disposal conditions

Leaching experiments in aqueous media were carried out on non-radioactive and radioactive nuclear waste glasses to investigate the release behaviour of 4 actinides (Th, U, Np and Pu) and 3 lanthanides (La, Ce and Nd) from the solid into solution. The experiments were conducted under flowing conditions using synthetic aqueous solutions. The lanthanide and actinide concentrations were measured in the leachates before and after filtration to 0.45 μm and 1.8 nm.Over 98.5% of the lanthanides and Th released from the glass were retained in the alteration products on the glass surface, probably coprecipitated with a siliceous gel. The retention was enhanced by the presence in the gel of 20 wt% P oxides from the initial 5 × 10⁻³ M PO₄ solution. In the leachates, more than 90% of the lanthanides and Th were associated with colloidal particles.Uranium and Np retention varied from 40% in a 5 × 10⁻³ M CO₃ medium to 95% in a 5 × 10⁻³ M PO₄ medium. In the CO₃ medium, U and Np formed stable CO₃ complexes that diminished the formation of precipitates; in the PO₄ medium, precipitation of PO₄ or more complex phases may have occurred.Pu exhibited atypical behaviour to the extent that it was strongly bonded to colloidal particles in solution, concentrated in the fraction exceeding 0.45 μm, and modifyed the calculated Pu leach rates. These particles may be the result of limited disaggregation of the alteration film. As most of the Pu was found at valence IV, it may be strongly retained in the alteration layer by precipitation or coprecipitation.Under oxidizing conditions, Np and U are found at high valences as Np(V) and U(VI), yielding charged forms in solution (NpO₂⁺ and UO₂⁺). The lanthanides, Th and Pu were present at lower valences as Ln(III), Th(IV) and Pu(IV), yielding Ln³⁺, Th⁴⁺ and Pu⁴⁺ in oxidizing media. The different behaviour of U and Np compared with the lanthanides, Th or Pu, observed during these experiments shows that the valence is the determining factor, and must be taken into account in assessing the evolution of radionuclides during the alteration of nuclear waste glass.     

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.     

Partitioning of trace elements between rutile and silicate melts: Implications for subduction zones

Mineral/melt trace element partition coefficients were determined for rutile (TiO₂) for a large number of trace elements (Zr, Hf, Nb, Ta, V, Co, Cu, Zn, Sr, REE, Cr, Sb, W, U, Th). Whilst the high field strength elements (Zr, Hf, Nb, Ta) are compatible in rutile, other studied trace elements are incompatible (Sr, Th, REE). In all experiments we found D_Ta > D_Nb, D_Hf > D_Zr and D_U > D_Th. Partition coefficients for some polyvalent elements (Sb, W, and Co) were sensitive to oxygen fugacity. Melt composition exerts a strong influence on HFSE partition coefficients. With increasing polymerization of the melt, rutile/melt partition coefficients for the high field strength elements Zr, Hf, Nb and Ta increase about an order of magnitude. However, D_Nb/D_Ta and D_Hf/D_Zr are not significantly affected by melt composition. Because D_U ? D_Th, partial melting of rutile-bearing eclogite in subducted lithosphere may cause excesses of ²³⁰Th over ²³⁸U in some island arc lavas, whereas dehydration of subducted lithosphere may cause excesses of ²³⁸U over ²³⁰Th. From our partitioning results we infer partition coefficients for protactinium (Pa) which we predict to be much lower than previously anticipated. Contrary to previous studies, our data imply that rutile should not significantly influence observed ²³¹Pa-²³⁵U disequilibria in certain volcanic rocks.     

Radiological characterization of granitoid outcrops and dimension stones of the Variscan Corsica-Sardinia Batholith

This study focuses on the radiological characterization of granitoid outcrops and dimension stones using in situ gamma-ray spectrometry. Extensive measurements were performed on 210 granitoid outcrops of the Corsica-Sardinia Batholith. The large statistical sample allowed us to improve the analysis by considering a log-normal distribution of radioelements and propagating the uncertainties using Monte Carlo method. The activity concentrations of ⁴⁰K, ²²⁶Ra (²³⁸U) and ²³²Th in C-SB area were 1,177 _?304 ⁺⁴⁰⁸ , 60 _?23 ⁺³⁶ and 69 _?25 ⁺³⁸  Bq/kg (at 1σ uncertainty). The median abundance of K, U and Th on the Variscan C-SB was higher than the average values of the upper continental crust and was comparable with Variscan belt. This corresponds to an outdoor absorbed dose rate of 124 _?26 ⁺³³  nGy/h at 1σ uncertainty which is 3σ higher than the population-weighted average absorbed dose rate (60 nGy/h). Seven commercial granites (Rosa Beta, Ghiandone, Giallo San Giacomo, Rosa Cinzia, Grigio Malaga, Bianco Sardo and Grigio Perla) were investigated to characterize their radiological hazard through 147 measurements taken in 73 extractive quarries. All of the commercial granites were categorized as A2 material based on their activity concentration indices, excluding (at the 3σ level) any restriction on their utilization as superficial materials. Rosa Beta, Grigio Malaga, Grigio Perla and Bianco Sardo can also be used as bulk materials as they can be included in the A1 category. In the case of Ghiandone, Giallo San Giacomo and Rosa Cinzia, we are confident of an A1 classification only at the 1σ level.     

Trace element partitioning and substitution mechanisms in calcium perovskites

We have determined the partition coefficients of a large number of trace elements between CaTiO₃ perovskite and anhydrous silicate melts at atmospheric pressure and 3 GPa. Determination of the concentration limits of Henrys law behaviour in the CaO-Al₂O₃–SiO₂–TiO₂ system reveals that the incorporation of rare earth elements (REE) and tetravalent large ion lithophile elements (LILE⁴⁺ such as U and Th) at the Ca-site of CaTiO₃ perovskite occurs with charge compensation through Ca-vacancy formation rather than by coupled substitution of Al for Ti. When melt composition is varied, we find that partition coefficients for REE and Th are strong functions of the CaO content of the melt. The observed trends are in excellent agreement with those predicted from the Ca-vacancy model. Given that they adopt the same crystal structure and have similar trace element partitioning behaviour, CaTiO₃ perovskite and the deep mantle phase CaSiO₃ perovskite can be considered analogous to one another. When the analogy is pursued in detail, we find that partitioning into both phases follows the composition-dependence predicted by the Ca-vacancy model. Thus, substitution of REE, U⁴⁺ and Th into CaSiO₃ in the lower mantle also occurs with Ca-vacancy formation to balance charge. Furthermore when 2+, 3+ and 4+ partition coefficients for both phases are plotted as functions of CaO melt content, the trends for CaSiO₃ and CaTiO₃ appear to be continuous. This surprising result means that partitioning into Ca-perovskite is independent of pressure and temperature and also of whether or not the host is CaSiO₃ or CaTiO₃. One implication is that CaSiO₃ crystallising from a peridotitic magma ocean may have partition coefficients for Th and U up to about 400. Crystallisation and sequestration of as little as 0.25 volume% of this phase in the lower mantle early in earth history would make a significant contribution to current mantle heat production.Electronic Supplementary Material Supplementary material is available for this article at     

The mobility of U and Th in subduction zone fluids: an indicator of oxygen fugacity and fluid salinity

The solubility of U and Th in aqueous solutions at P-T-conditions relevant for subduction zones was studied by trapping uraninite or thorite saturated fluids as synthetic fluid inclusions in quartz and analyzing their composition by Laser Ablation-ICPMS. Uranium is virtually insoluble in aqueous fluids at Fe-FeO buffer conditions, whereas its solubility increases both with oxygen fugacity and with salinity to 960 ppm at 26.1 kbar, Re-ReO₂ buffer conditions and 14.1 wt% NaCl in the fluid. At 26.1 kbar and 800°C, uranium solubility can be reproduced by the equation: log\textU = 2.681 + 0.1433logf\textO₂ + 0.594\textCl, \log {\text{U}} = 2.681 + 0.1433\log f{\text{O}}_{2} + 0.594{\text{Cl,}} where fO₂ is the oxygen fugacity, and Cl is the chlorine content of the fluid in molality. In contrast, Th solubility is generally low (<10 ppm) and independent of oxygen fugacity or fluid salinity. The solubility of U and Th in clinopyroxene in equilibrium with uraninite and thorite was found to be in the order of 10 ppm. Calculated fluid/cpx partition coefficients of Th are close to unity for all conditions. In contrast, D^fluid/cpx for uranium increases strongly both with oxygen fugacity and with salinity. We show that reducing or NaCl-free fluids cannot produce primitive arc magmas with U/Th ratio higher than MORB. However, the dissolution of several wt% of oxidized, saline fluids in arc melts can produce U/Th ratios several times higher than in MORB. We suggest that observed U/Th ratios in arc magmas provide tight constraints on both the salinity and the oxidation state of subduction zone fluids.     

Uranium and thorium microdistributions in stony meteorites

Uranium distributions have been determined in seventeen meteorites using fission track techniques. In seven cases, Th was also determined by a new method using fast neutrons. The actinides are generally concentrated in phosphates, usually whitlockite and/or chlorapatite. Wherever whitlockite and chlorapatite coexist, chlorapatite is richer in uranium. U concentrations in a given phosphate phase are highly variable from meteorite to meteorite and sometimes also show large variations in the same meteorite. A clinopyroxene phase enriched in U (0.2–0.3 ppm) is usually found in Ca-rich achondrites. The $\text{Th}\text{U}$ ratios of phosphates differ considerably from whole rock values indicating that these elements were fractionated during the meteorite formation.     

The redox chemistry of Pu(V)O2+ interaction with common mineral surfaces in dilute solutions and seawater

It has long been recognized that the Pu⁴⁺ ion can be readily adsorbed on solid surfaces, but it has been assumed that the generally more abundant Pu(V)O₂⁺ ion should have little affinity for surfaces. Our results indicate that Pu(V)O₂⁺ can be adsorbed from dilute solutions and seawater on goethite, aragonite, calcite, and δ-MnO₂. Adsorption on δ-MnO₂ is severely depressed in seawater, probably as a result of site competition with seawater cations.The sorption behavior of PuO₂⁺ is influenced by oxidation-reduction reactions occurring on the mineral surfaces. Adsorption on δ-MnO₂ results in oxidation of adsorbed Pu(IV) and Pu(V) to Pu(VI). However, adsorption on goethite results in a reaction in which Pu(IV) and Pu(VI) are formed on the mineral surface. The Pu(VI) is slowly reduced to Pu(IV), leaving Pu(IV) as the dominant surface Pu species. This reaction can be photochemically catalyzed. PuO₂⁺ adsorbed on carbonate minerals behaves similarly to Np(V)O₂⁺ and undergoes little change in oxidation state after adsorption.     

Actinide microdistributions in the enstatite meteorites

Oldhamite is a major Th and U bearing phase in the enstatite meteorites. Oldhamite from E-6 chondrites has mean Th and U abundances of 1550 ± 80 ppb Th and 410 ± 20 ppb U, with $\text{Th}\text{U}\text{= 3.8 ± .2}$. With the exception of ferroan alabandite which contains 25 ± 1 ppb U, no other Th or U enriched phases were located in the E-6 chondrites, and nearly all of the total rock Th and U can be accounted for by oldhamite. In Khairpur (E6), excess fossil fission tracks were observed in enstatite grains in contact with oldhamite which indicates the presence of ²⁴⁴Pu in oldhamite. Oldhamite from St. Mark's (E5) and Abee (E4) also shows actinide enrichments but at levels about half the E-6 results. Niningerite in Abee contains 45 ± 5 ppb U and due to its high reported modal abundance is an important U reservoir in Abee. The U content of oldhamite from the aubrite Peña Blanca Spring is 1920 ± 100 ppb. All $\text{Th}\text{U}$ values measured in this study cluster tightly around a value of 4 which indicates a lack of ThU fractionation in both oldhamite and in the enstatite meteorites, themselves. This lack of fractionation, along with the presence of ²⁴⁴Pu in oldhamite and reported rare earth enrichments also in oldhamite, suggests that the enstatite chondrites may be well-suited for PuU chronology and for providing the initial PuU value in the early solar system.     

Monazite and xenotime U–Th–Pb geochronology by ion microprobe: dating highly fractionated granites at Xihuashan tungsten mine, SE China

Zircon, monazite, and xenotime have proven to be valuable chronometers for various geological processes due to their commonly high-U–Th and low common Pb contents. However, zircons that have crystallized in highly fractionated granites often have such high-U contents that radiation damage can lead to scattered U–Pb ages when measured with secondary ion mass spectrometry (SIMS). In this study, monazite and xenotime were separated from a number of highly fractionated granites at the Xihuashan tungsten mine, Southeast China, for alternative dating methods by SIMS. For monazite analysis, obvious excess ²⁰⁴Pb signal (mainly from interference of ²³²Th¹⁴⁴Nd¹⁶O₂ ⁺⁺) was observed in high-Th (>2 wt%) monazite, which hinders ²⁰⁴Pb-based common Pb corrections. A ²⁰⁷Pb-based common Pb correction method was used instead. By employing power law relationships between Pb⁺/U⁺ versus UO₂ ⁺/U⁺, Pb⁺/Th⁺ versus ThO₂ ⁺/Th⁺ and suitable exponentials, monazites with ThO₂ contents in the range of ~3–19 % do not exhibit this matrix effect. Independent SIMS U–Pb ages and Th–Pb ages of three phases of Xihuashan granite samples were consistent with each other and yielded dates of 158.7 ± 0.7, 158.0 ± 0.7, and 156.9 ± 0.7 Ma, respectively. Xenotime does show marked matrix effects due to variations of U, Th, and Y [or total rare earth element (REE), referred as ΣREE hereafter] contents. Suitable correction factors require end-member standards with extremely high or low U, Th, and Y (or ΣREE) contents. No excess ²⁰⁴Pb was observed, indicating that the ²⁰⁴Pb-based common Pb correction method is feasible. Independent ²⁰⁷Pb/²⁰⁶Pb ages can be obtained, although multi-collector mode is necessary to improve precision. The main difficulties with dating xenotime are when high-Th (U) mineral inclusions are ablated. We can identify when this occurs, however, by comparing the measured UO₂ ⁺/U⁺ and ThO₂ ⁺/Th⁺ with those in xenotime standards. Three xenotime samples from the first phase of Xihuashan granite yielded a weighted mean ²⁰⁷Pb/²⁰⁶Pb date of 159.5 ± 4.4 Ma (MSWD = 1.0) and a ²⁰⁶Pb/²³⁸U date of 159.4 ± 0.9 Ma (MSWD = 1.6), which are consistent with monazite U–Pb and Th–Pb ages from the same granites. This study demonstrates that monazite and xenotime are better SIMS chronometers for highly fractionated granites than zircon, which can yield doubtful ages due to high-U contents.     

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.     

Interaction of muscovite (0 0 1) with Pu bearing solutions at pH 3 through ex-situ observations

The interaction of Pu³⁺ bearing solutions with the muscovite (0 0 1) basal plane is explored using a combination of ex-situ approaches including alpha-counting, to determine the Pu³⁺ adsorption isotherm, and X-ray reflectivity (XR) and resonant anomalous X-ray reflectivity (RAXR), to probe the interfacial structure and Pu-specific distribution, respectively. Pu uptake to the muscovite (0 0 1) surface from Pu³⁺ solutions in a 0.1 M NaClO₄ background electrolyte at pH 3 follows an approximate Langmuir isotherm with an apparent adsorption constant, K_app = 5 × 10⁴ M⁻¹, and with a maximum coverage that is consistent with the amount needed to fully compensate the surface charge by trivalent Pu. The XR results show that the muscovite surface reacted with a 10⁻³ M Pu³⁺ solution (at pH 3 with 0.1 M NaClO₄) and dried in the ambient environment, maintains a 30-40 Å thick layer, indicating the presence of a residual hydration layer (possibly including adventitious carbon). The RAXR results indicate that Pu sorbs on the muscovite surface with an intrinsically broad distribution with an average height of 18 Å, substantially larger than heights expected for any specifically adsorbed inner- or outer-sphere complexes. These results are discussed in the context of recent studies of cation adsorption trends on muscovite and the possible roles of Pu hydrolysis species in controlling the Pu-muscovite interactions.     

Altered rocks of the Onguren carbonatite complex in the Western Tansbaikal Region: Geochemistry and composition of accessory minerals

The paper discusses the mineralogy and geochemistry of altered rocks associated with calcite and dolomite–ankerite carbonatites of the Onguren dyke–vein complex in the Western Transbaikal Region. The alteration processes in the Early Proterozoic metamorphic complex and synmetamorphic granite hosting carbonatite are areal microclinization and riebeckitization; carbonates, phlogopite, apatite, and aegirine occur in the near-contact zones of the dolomite–ankerite carbonatite veins; and silicification is displayed within separated zones adjacent to the veins. In aluminosilicate rocks, microclinization was accompanied by an increasing content of K, Fe³⁺, Ti, Nb (up to 460 ppm), Th, Cu, and REE; Na, Ti, Fe³⁺, Mg, Nb (up to 1500 ppm), Zr (up to 2800 ppm), Ta, Th, Hf, and REE accumulated in the inner zone of the riebeckitization column. High contents of Ln _Ce (up to 11200 ppm), U (23 ppm), Sr (up to 7000 ppm), Li (up to 400 ppm), Zn (up to 600 ppm), and Th (up to 700 ppm) are typical of apatite–phlogopite–riebeckite altered rock; silicified rock contains up to (ppm): 2000 Th, 20 U, 13000 Ln _Ce, and 5000 Ва. Ilmenite and later rutile are the major Nb carriers in alkali altered rocks. These minerals contain up to 2 and 7 wt % Nb₂O₅, respectively. In addition, ferrocolumbite and aeschynite-(Ce) occur in microcline and riebeckite altered rocks. Fluorapatite containing up to 2.7 wt % (Ln _Ce)₂O₃, monazite-(Ce), cerite-(Ce), ferriallanite-(Ce), and aeschynite-(Ce) are the REE carriers in riebeckite altered rock. Bastnäsite-(Ce), rhabdophane-group minerals, and xenotime-(Y) are typical of silicified rock. Thorite, monazite-(Ce), and rhabdophane-group minerals are the Th carriers.     

Geochemistry of uranium in sediments of the Bohai Gulf,China

The following conclusions can be drawn from the work reported in this paper:

1. Sixteen samples were determined for uranium by spectrophotometric method. The uranium content in the sea floor sediments of the Bohai Gulf ranges from 1.6 to 6.3 ppm, with an average of 4.3 ppm.
2. Statistical data show close relationship between U concentration and grain size. Relatively larger amount of uranium was found accumulated in mud than in sand. The bulk of uranium is assumed to be derived from terrestrial detrital minerals.
3. A positive correlation between U and Fe is recognized. Similar relation also can be seen between U and Al. The plot of U concentration vs. Fe is linear, and can be expressed by the linear regression equation:Y=?0.37+1.35X. The plot of U against Al gives an equation ofY=?2.48+1.01X.
4. The average U/C_org. ratio for these sediments is 7×10^?4, and the average ratios of U/P, U/Mn, and U/CaCO₃ are 100×10^?4, 50×10^?4 and 2×10^?4, respectively.
5. Compared with the abundances of other shelf sediments, the average concentration of U in the area under consideration is close to that of sediments on the selves of Japan and the Gulf of Mexico, and the Black Sea. Uranium concentration in the Bohai Gulf sediments is comparable to that of the continental crust, but differs from that of deep-sea clay.

     

Delivery of transuranic elements by rain to the Mediterranean Sea

The concentrations of ²³⁸Pu, ^{239 + 240}Pu, ²⁴¹Am and ¹³⁷Cs were determined in rain samples collected at Monaco in the course of 1978–1979. Based on these data, the annual deliveries of these radionuclides to the Mediterranean by rain are computed to be 0.18 ± 0.01 pCim^?2 for ²³⁸Pu, 8.1 ± 0.1 pCim^?2 for ^{239 + 240}Pu, 0.58 ± 0.02 pCim^?2 for ²⁴¹Am and 351 ± 4 pCim^?2 for ¹³⁷Cs.Comparing the delivery data with the mixed layer inventories of ^{239 + 240}Pu and ²⁴¹Am in the Mediterranean, the upper limits of the mean residence time of these radionuclides in the mixed layer were estimated to be 12.3 yr for ^{239 + 240}pu and 2.9 yr for ²⁴¹Am. These values are consistent with the conclusion deduced from the vertical distribution pattern of these transuranic elements in the Mediterranean.Based on delivery values, the annual activity ratios for ${}^{238}\text{pu}{}^{\mathrm{239\; +\; 240}}\text{Pu}$, ${}^{241}\text{Am}{}^{\mathrm{239\; +\; 240}}\text{Pu}$ and ${}^{\mathrm{239\; +\; 240}}\text{pu}{}^{137}\text{Cs}$ are found to be 0,022, 0.072 and 0.023 respectively. The ${}^{238}\text{pu}{}^{\mathrm{239\; +\; 240}}\text{pu}$ and ${}^{\mathrm{239\; +\; 240}}\text{Pu}{}^{137}\text{Cs}$ activity ratios vary within relatively narrow ranges with time, while a much wider variation was observed for the ${}^{241}\text{Am}{}^{\mathrm{239\; +\; 240}}\text{Pu}$ activity ratio. The cause of the wider variation of the ${}^{241}\text{Am}{}^{\mathrm{239\; +\; 240}}\text{Pu}$ ratio may be related to the difference in the mean age of fallout brought down in different seasons.     

Rare gases in separated whitlockite from the St. Severin chondrite: xenon and krypton from fission of extinct 244Pu

Helium, neon, argon, krypton and xenon data are presented from stepwise heating of samples of the mineral whitlockite from the chondritic meteorite St. Severin. The xenon is shown to be a uniform mixture derived from ²⁴⁴Pu fission and rare-earth element spallation. The krypton similarly contains spallation products and ⁸⁶Kr from ²⁴⁴Pu fission. Plutonium-244 fission yields of ⁸⁶Kr/¹²⁹Xe/¹³¹Xe/¹³²Xe/¹³⁴Xe/¹³⁶Xe = 1.9 ± 0.5/4.8 ± 5.5/24.6 ± 2.0/88.5 ±3.0/93.9 ± 0.8/  100 are obtained. The helium, neon and argon are dominated by spallation and radiogenic ⁴He and ⁴⁰Ar. A pile neutron irradiation experiment does not yield a unique Pu/U ratio for this mineral but yields ratios varying from 0.045 down to 0.017. Both the high concentration of ²⁴⁴Pu fission xenon and the high ratio of Pu/U previously reported by Wasserburget al. (J. Oeophys. Res. 74, 4221–4232, 1969) are thus confirmed.     

Uranium series disequilibrium in young lacustrine sediments from an arid environment at Henkries,Republic of South Africa

Uranium adsorbed on to carbonaceous material and clays, and in minerals (boltwoodite, carnotite, zippeite), is present in a lacustrine deposit from an arid environment of southern Africa. Granites in the area, which may contain up to 50 ppm U₃O₈, are believed to be the original source for the U mineralization. The U is concentrated selectively in certain strata which are characterized by high diatomaceous earth and carbonaceous contents, high moisture contents, low densities, and considerable porosity.Activities of the ²³⁸U series nuclides (²³⁸U, ²³⁴U, ²³⁰Th and ²²⁶Ra) were determined by alpha spectrometry and indicate: (1) the deposit is geologically young; and (2) disequilibrium among nuclides in the U series is prevalent at present. Because of this disequilibrium between U and its daughter products, there is no correlation between U₃O₈ determined by chemical analysis and that inferred from radiometric methods based on gamma ray spectrometry (eU₃O₈); in some cases chemical U₃O₈ is higher than eU₃O₈ inferred from gamma ray spectrometry whereas in other cases the reverse is true. In order to evaluate the deposit, all drill core, and trench and pit samples were analysed by X-ray fluorescence. At this time, movement of U and its daughter elements appears to be an active process, particularly in those layers which are porous and have a high moisture content. Paleoclimatic studies have shown that alternating pluvial and arid periods existed in the last 40 000 yr in southern Africa. These would result in fluctuations in the water table sufficient to cause selective relative migrations of ²³⁸U series nuclides thus accounting for at least some of the observed disequilibrium.