U,U andTh in seawater

We have developed techniques to determine²³⁸U,²³⁴U and²³²Th concentrations in seawater by isotope dilution mass spectrometry. U measurements are made using a²³³U²³⁶U double spike to correct for instrumental fractionation. Measurements on uranium standards demonstrate that²³⁴U/²³⁸U ratios can be measured accurately and reproducibly.²³⁴U/²³⁸U can be measured routinely to ± 5‰ (2σ) for a sample of 5 × 10⁹ atoms of²³⁴U (3 × 10⁻⁸ g of total U, 10 ml of seawater). Data acquisition time is 1 hour. The small sample size, high precision and short data acquisition time are superior to-counting techniques.²³⁸U is measured to ± 2‰ (2σ) for a sample of 8 × 10¹² atoms of²³⁸U ( 3 × 10⁻⁹ g of U, 1 ml of seawater).²³²Th is measured to ± 20‰ with 3 × 10¹¹²³²Th atoms (10⁻¹⁰ g²³²Th, 1 1 of seawater). This small sample size will greatly facilitate investigation of the²³²Th concentration in the oceans. Using these techniques, we have measured²³⁸U,²³⁴U and²³²Th in vertical profiles of unfiltered, acidified seawater from the Atlantic and²³⁸U and²³⁴U in vertical profiles from the Pacific. Determinations of²³⁴U/²³⁸U at depths ranging from 0 to 4900 m in the Atlantic (7°44′N, 40°43′W) and the Pacific (14°41′N, 160°01′W) Oceans are the same within experimental error (± 5‰,2σ). The average of these²³⁴U/²³⁸U measurements is 144 ± 2‰ (2σ) higher than the equilibrium ratio of 5.472 × 10⁻⁵. U concentrations, normalized to 35‰ salinity, range from 3.162 to 3.281 ng/g, a range of 3.8%. The average concentration of the Pacific samples (31°4′N, 159°1′W) is 1% higher than that of the Atlantic (7°44′N, 40°43′W and 31°49′N, 64°6′W).²³²Th concentrations from an Atlantic profile range from 0.092 to 0.145 pg/g. The observed constancy of the²³⁴U/²³⁸U ratio is consistent with the predicted range of²³⁴U/²³⁸U using a simple two-☐ model and the residence time of deep water in the ocean determined from¹⁴C. The variation in salinity-normalized U concentrations suggests that U may be much more reactive in the marine environment than previously thought.     

Neodymium isotopic study of Baffin Bay water: sources of REE from very old terranes

Water samples were collected from Baffin Bay and surrounding areas in order to evaluate this region as a potential source of Nd from old continental material to Atlantic water. The isotopic data ranged from ε_Nd(0) = −9.0 to −26 with most of the data around ε_Nd(0) = −20 compared with values of North Atlantic Deep Water (NADW) with ε_Nd(0) = −13.5. The concentration of Nd in Baffin Bay waters was as high as 6 × 10⁻¹² g/g compared with 2.5 × 10⁻¹² g/g for NADW. The combination of low ε_Nd and high Nd concentration indicates that Baffin Bay may be a significant source of Nd from very old crustal material. A simple box model was used to evaluate the contribution to the Nd budget of NADW and it was concluded that a substantial fraction of the Nd from ancient crustal sources that is required to maintain the isotopic composition of NADW could be supplied by Baffin Bay outflow.     

Nd and Sr isotopic compositions of tektite material from Barbados and their relationship to North American tektites

Isotopic analyses of Nd and Sr on individual microtektites and a bulk microtektite sample from Barbados show them to have a very well defined isotopic composition. These data plot on an ε_Srε_Nd diagram precisely within the narrow field determined by North American tektites (ε_Sr ≈ 111; ε_Nd ≈ ?6.2). They yield an Nd model age of 0.6 AE. These results show that the microtektites from the Oceanic beds of late Eocene age are derived from the same target as the North American tektites and should be associated with the same event. Samples of the deep sea sediments in which the Barbados microtektites occur are found to have isotopic signatures which appear to reflect ambient sea water and detrital sediments. They cannot be the source of Sr or Nd in the tektites. Following the arguments of Shaw and Wasserburg (1982) we conclude that the target area which produced the North American tektite field was composed of sediments (Eocambrian or younger) derived from very late Precambrian crust. Glass beads from Lake Wanapitei Crater are isotopically different from all other tektites (ε_Sr ≈ 960; ε_Nd ≈ ?31.4) and cannot be related to the North American tektites.     

Willy: A prize noble Ur-Fremdling—Its history and implications for the formation of Fremdlinge and CAI

A detailed mineralogic and chemical study of Willy, a very large (150 μm diameter) Fremdling from the Allende CAI 5241, was performed and compared to other Fremdlinge from Allende CAI's 5241 and TS-34 in an attempt to understand the nature and mode of formation of these exotic and complex objects. Willy is composed primarily of V-rich magnetite, V-rich fassaite, and Ni-Fe metal containing Co and Pt. Minor phases include an Fe-Ni-sulfide, V-rich spinel, scheelite (the first reported occurrence in a meteorite), and Cl-apatite. Phases found in trace amounts include nuggets of Os-Ru-Re metal, molybdenite, an unidentified Fe-, Mg-molybdate, and diopside. The Fremdling is concentrically zoned and contains a complex porous core of magnetite, metal, sulfide, scheelite, and other minor phases surrounded by a compact mantle of magnetite with minor apatite. The mantle is surrounded by a dense rim composed of fassaite with minor spinel that appears to be a typical occurrence around oxide-containing Fremdlinge. At the boundary between the fassaite-rim and the magnetite-mantle of Willy is a thin zone (<20 μm wide) of an apparent reaction assemblage consisting of V-rich MgAl₂O₄, FeAl₂O₄, and a third V-rich spinel, possibly FeV₂O₄, in intimate intergrowth.From the observed chemistry and texture, a multistage sequence of formation of Willy, possibly occurring in the solar nebula and involving major changes in T and $\text{?O}{}_2$, can be deduced. The first phases that may have formed in the interior are magnetite and an Fe or Ca tungstate. Refractory metal nuggets and sulfide were introduced after this stage followed by two stages of Ni-Fe formation during which Pt was dissolved in the metal. This was followed by formation of the magnetite mantle, introduction of apatite and possible alteration of ferberite to scheelite. Finally, the V-rich fassaite rim formed, accompanied or followed by reaction forming the complex Fe-, V-rich spinels. All of these steps preceded introduction of the Fremdling into the CAI precursor which in turn appears to have occurred prior to formation of spinel and the major silicate phases in the CAI.The concentric mineral zoning and texture of Willy may indicate that it is one of the few Fremdlinge that was not substantially recrystallized after having been captured in the CAI. It thus may represent the precursor material for many of the other Fremdlinge, since numerous Fremdlinge studied exhibit many of the mineral and chemical features observed in Willy. The co-existence of magnetite, sulfide, and Ni-Fe metal in the interior of Willy and the co-existence of metal, hercynite spinel and magnetite at the rimmantle boundary suggests that the maximum temperature at which Willy could have existed for long periods of time in its present state was about 500–600°C. Similarly, the existence of highly heterogeneous V-, Ti-rich fassaite rims around Willy and other Fremdlinge implies rapid cooling rates for the CAI's.     

The isotopic composition of silver and lead in two iron meteorites: Cape York and Grant

Silver in the metal phases of Cape York (IIIA) and Grant (IIIB) has been determined after an extensive surface cleaning process. The ${}^{107}\text{Ag}{}^{109}\text{Ag}$ was found to be enriched over that found in terrestrial Ag by ~7%. to 19%., demonstrating the presence of excess ¹⁰⁷Ag (¹⁰⁷Ag¹) in this class of meteorites. An effort was made to find schreibersite with a distinctive ¹⁰⁸Pd/¹⁰⁹Ag ratio in order to establish a three-point isochron, but the results are not markedly different from those obtained for the bulk metal. The Ag isotopic ratio of sulfides from the same meteorites were nearly normal in composition. These results demonstrate correlations of ${}^{107}\text{Ag}{}^{109}\text{Ag}$ with ${}^{108}\text{Pd}{}^{109}\text{Ag}$ between coexisting phases of two iron meteorites that are associated with planetary differentiation processes. The ratios ${}^{107}\text{Ag}{}^1{}^{108}\text{Pd}$ were found to be 1.7 × 10^?5 and 1.2 × 10^?5 for Cape York and Grant, respectively. These observations are in support of the widespread presence of ¹⁰⁷Pd in the early solar system. The difference in isotopic composition between metal and sulfide phases demonstrates that silver diffusion was small (over 6.5 × 10⁶ y) indicating a cooling rate much greater than 150°C/my for meteorites which have been attributed to small planetary cores. Uranium determinations were carried out on the metal phases and concentrations of ~ $\text{1 × 10}{}^{12}$ g U/g and 2 × 10^?10g U/g were found for Cape York and Grant, respectively. The Pb in these meteorites was determined using the improved cleaning procedures and chemical separations with low blank levels. The results confirm the presence of variable proportions of radiogenic Pb in both the metal and sulfide phases of iron meteorites. No simple explanation for the presence of radiogenic lead is apparent; while terrestrial contamination may appear to be the obvious explanation, it is possible that this effect could result from relatively recent metamorphism in the meteorite parent body.     

Rate-controlled calcium isotope fractionation in synthetic calcite

The isotopic composition of Ca (Δ⁴⁴Ca/⁴⁰Ca) in calcite crystals has been determined relative to that in the parent solutions by TIMS using a double spike. Solutions were exposed to an atmosphere of NH₃ and CO₂, provided by the decomposition of (NH₄)₂CO₃, following the procedure developed by previous workers. Alkalinity, pH and concentrations of CO₃²⁻, HCO₃⁻, and CO₂ in solution were determined. The procedures permitted us to determine Δ(⁴⁴Ca/⁴⁰Ca) over a range of pH conditions, with the associated ranges of alkalinity. Two solutions with greatly different Ca concentrations were used, but, in all cases, the condition [Ca²⁺]>>[CO₃²⁻] was met. A wide range in Δ(⁴⁴Ca/⁴⁰Ca) was found for the calcite crystals, extending from 0.04 ± 0.13‰ to −1.34 ± 0.15‰, generally anti-correlating with the amount of Ca removed from the solution. The results show that Δ(⁴⁴Ca/⁴⁰Ca) is a linear function of the saturation state of the solution with respect to calcite (Ω). The two parameters are very well correlated over a wide range in Ω for each solution with a given [Ca]. The linear correlation extended from Δ(⁴⁴Ca/⁴⁰Ca) = −1.34 ± 0.15‰ to 0.04 ± 0.13‰, with the slopes directly dependent on [Ca]. Solutions, which were vigorously stirred, showed a much smaller range in Δ(⁴⁴Ca/⁴⁰Ca) and gave values of −0.42 ± 0.14‰, with the largest effect at low Ω. It is concluded that the diffusive flow of CO₃²⁻ into the immediate neighborhood of the crystal-solution interface is the rate-controlling mechanism and that diffusive transport of Ca²⁺ is not a significant factor. The data are simply explained by the assumptions that: a) the immediate interface of the crystal and the solution is at equilibrium with Δ(⁴⁴Ca/⁴⁰Ca) ∼ −1.5 ± 0.25‰; and b) diffusive inflow of CO₃²⁻ causes supersaturation, thus precipitating Ca from the regions exterior to the narrow zone of equilibrium. The result is that Δ(⁴⁴Ca/⁴⁰Ca) is a monotonically increasing (from negative values to zero) function of Ω. We consider this model to be a plausible explanation of most of the available data reported in the literature. The well-resolved but small and regular isotope fractionation shifts in Ca are thus not related to the diffusion of very large hydrated Ca complexes, but rather due to the ready availability of Ca in the general neighborhood of the crystal-solution interface. The largest isotopic shift which occurs as a small equilibrium effect is then subdued by supersaturation precipitation for solutions where [Ca²⁺]>>[CO₃²⁻] + [HCO₃⁻]. It is shown that there is a clear temperature dependence of the net isotopic shifts that is simply due to changes in Ω due to the equilibrium “constants” dependence on temperature, which changes the degree of saturation and hence the amount of isotopically unequilibrated Ca precipitated. The effects that are found in natural samples, therefore, will be dependent on the degree of diffusive inflow of carbonate species at or around the crystal-liquid interface in the particular precipitating system, thus limiting the equilibrium effect.     

Prompt Iron Enrichment, Two r-Process Components, and Abundances in Very Metal-Poor Stars

We compare the structure and substructure of dark matter halos in model universes dominated by collisional, strongly self-interacting dark matter (SIDM) and collisionless, weakly interacting dark matter (CDM). While SIDM virialized halos are more nearly spherical than CDM halos, they can be rotationally flattened by as much as 20% in their inner regions. Substructure halos suffer ram-pressure truncation and drag, which are more rapid and severe than their gravitational counterparts tidal stripping and dynamical friction. Lensing constraints on the size of galactic halos in clusters are a factor of 2 smaller than predicted by gravitational stripping, and the recent detection of tidal streams of stars escaping from the satellite galaxy Carina suggests that its tidal radius is close to its optical radius of a few hundred parsecs-an order of magnitude smaller than predicted by CDM models but consistent with SIDM models. The orbits of SIDM satellites suffer significant velocity bias, sigmaSIDM&solm0;sigmaCDM=0.85, and are more circular than CDM satellites, betaSIDM approximately 0.5, in agreement with the inferred orbits of the Galaxy's satellites. In the limit of a short mean free path, SIDM halos have singular isothermal density profiles; thus, in its simplest incarnation SIDM, is inconsistent with galactic rotation curves.     

Nd and Sr isotopic evidence for the origin of tektite material from DSDP site 612 off the New Jersey coast

Abstract— Late Eocene tektite material from DSDP site 612 is composed of angular to spherical tektites and microtektites containing abundant vesicles and a few unmelted to partially melted mineral inclusions. The major element compositions of the 612-tektites are generally comparable to those of North American tektites, but the physical features suggest that the DSDP-612 tektites were formed by less severe shock melting. The ⁸⁷Sr/⁸⁶Sr and ¹⁴³Nd/¹⁴⁴Nd compositions of 612-tektites: a) show much wider ranges than the tightly constrained group of North American tektites and microtektites, and b) are significantly different from those of other groups of tektites. The existence of large isotopic variations in tektites from DSDP site 612 requires that they were formed from a chemically and isotopically heterogeneous material in a regime that is distinctive from that of other groups of tektites. T^ND_CHUR and T^Sr_UR model ages of the 612-tektites indicate that they were formed from a crustal source of late Precambrian mean age (800–1000 Ma) which in middle Palaeozoic time (?400 Ma) was further enriched in Rb/Sr during sedimentary processes. These source characteristics suggest that the impact which produced the 612-tektites occurred in rocks of the Appalachian orogeny or sediments derived from this orogenic belt. Potential source materials for both 612-tektites and North American tektites are present on the eastern and southeastern part of the North American continent and its adjacent shelf. The distinct isotopic differences between 612-tektites and North American tektites indicate that the two groups of tektites were either formed by the impact of more than one bolide in the same general area, or by a single impact event that sampled different layers.     

Dating earthquakes with high-precision thorium-230 ages of very young corals

Mass spectrometric techniques have recently yielded significant increases in precision and sensitivity over previous methods for measuring²³⁰Th abundance in corals. To assess the accuracy of²³⁰Th ages, three corals from Vanuatu, whose ages were known from counting annual growth bands, were analyzed. For each sample, the date of growth determined by²³⁰Th analysis (A.D.1969 ± 3, 1932 ± 5,and1806 ± 5; 2σ uncertainties based on analytical error) was indistinguishable from the date determined by counting bands (A.D. 1971–1973, 1935–1937, and 1804–1810), indicating that the²³⁰Th dates are accurate.²³⁰Th dates were also determined for two adjacent emerged heads from Santo Is., Vanuatu, which were thought to have died when they were raised above sea level during coseismic uplift. The dates (A.D.1864 ± 4, 1866 ± 4) were the same, indicating that the heads died at the same time and consistent with the idea that they were killed by coseismic emergence around A.D. 1865. The difference between this date and the date of the only major historically documented earthquake that caused uplift (A.D. 1973,M_s = 7.5), suggests a seismic recurrence interval of108 ± 4y for Santo. Analogous emerged corals from Malekula Is., Vanuatu yielded²³⁰Th dates that were similar to each other (A.D.1729 ± 3, 1718 ± 5) and are inferred to have died during coseismic emergence around A.D. 1729. In conjunction with the date of the only large historically documented earthquake that caused uplift (A.D. 1965,M_s = 7.5), the recurrence interval for Malekula is236 ± 3y. If similar emerged corals can be found, this appraoch may be extended back in time and to other localities because it appears that such features can now be dated both accurately and precisely.