XPS spectra of uranyl minerals and synthetic uranyl compounds. I: The U 4f spectrum

The occurrence and binding energies of the U⁶⁺, U⁵⁺ and U⁴⁺ bands in the U 4f_7/2 peak of 19 uranyl minerals of different composition and structure were measured by XPS. The results suggest that these minerals can be divided into the following four groups: (1) Uranyl-hydroxy-hydrate compounds with no or monovalent interstitial cations; (2) Uranyl-hydroxy-hydrate minerals with divalent interstitial cations; (3) Uranyl-oxysalt minerals with (TO_n) groups (T = Si, P, and C) in which all equatorial O-atoms of the uranyl-polyhedra are shared with (TO_n) groups; (4) Uranyl-oxysalt minerals with (TO_n) groups (T = S and Se), in which some equatorial O-atoms are shared only between uranyl polyhedra. The average binding energies of the U⁶⁺and U⁴⁺ bands shift to lower values with (1) incorporation of divalent cations and (2) increase in the Lewis basicity of the anion group bonded to U. The first observation is a consequence of an increase in the bond-valence transfer from the interstitial species (cations, H₂O) groups to the O-atoms of the uranyl-groups, which results in an electron transfer from O to U⁶⁺. The second trend correlates with an increase in the covalency of the UO bonds with increase in Lewis basicity of the anion group, which results in a shift of the electron density from O to U. The presence of U⁴⁺ on the surface of uranyl minerals can be detected by the shape of the U 4f_7/2 peak, and the occurrence of the U 5f peak and satellite peaks belonging to the U 4f_5/2 peak. The presence of U⁴⁺ in some of the uranyl minerals and synthetics examined may be related to the conditions during their formation. A charge-balance mechanism is proposed for the incorporation of lower-valence U in the structure of uranyl minerals. Exposure of a Na-substituted metaschoepite crystal in air and to Ultra-High Vacuum results in dehydration of its surface structure associated with a shift of the U⁶⁺ bands to higher binding energies. The latter observation indicates a shift in electron density from U to O, which must be related to structural changes inside the upper surface layers of Na-substituted metaschoepite.     

Selection of optimum frequency of a wind scatterometer

The problem of selecting the optimum operating frequency of a scatterometer, used for remote sensing of sea surface wind speed has been addressed by applying the criteria of maximum sensitivity of backscattering coefficient to wind speed as well as its correlation with wind speed. The backscattering coefficient values for sea surface were computed by the two-scale scattering theory. To compute the atmospheric transmittance, 753 clear sky atmospheres over Indian Ocean were used. While the correlation coefficient was uniform (0.94) throughout the frequency range of 1 to 30GHz, only frequencies above 5GHz were found sensitive enough to yield a wind speed accuracy of ±2msec⁻¹ and better, the accuracy improving with frequency.     

Temperature and Salinity Effects on Alkenone Ratios Measured in Surface Sediments from the Indian Ocean

We compare alkenone unsaturation ratios measured on recent sediments from the Indian Ocean (20°N–45°S) with modern sea oceanographic parameters. For each of the core sites we estimated average seasonal cycles of sea surface temperature (SST) and salinity, which we then weighted with the seasonal productivity cycle derived from chlorophyll satellite imagery. The unsaturation index (U₃₇^K′) ranges from 0.2 to 1 and correlates with water temperature but not with salinity. TheU₃₇^K′versus SST relationship for Indian Ocean sediments (U₃₇^K′= 0.033 SST + 0.05) is similar to what has been observed for core tops from the Pacific and Atlantic oceans and the Black Sea. A global compilation for core tops givesU₃₇^K′= 0.031 T + 0.084 (R= 0.98), which is close to a previously reported calibration based on particulate organic matter from the water column. For temperatures between 24° and 29°C, however, the slope seems to decrease to about 0.02U₃₇^K′unit/°C. For Indian Ocean core tops, the ratios of total C₃₇alkenones/total C₃₈alkenones and the slope of theU₃₇^K′-SST relationship are similar to those previously observed for cultures ofEmiliania huxleyibut different from those previously published forGephyrocapsa oceanica.EitherE. huxleyiis a major producer of alkenones in the Indian Ocean or strains ofG. oceanicaliving in the northern Indian Ocean behave differently from the one cultured. In contrast with coccolithophorid assemblages, the ratios of C₃₇alkenones to total C₃₈alkenones lack clear geographic pattern in the Indian Ocean.     

XPS spectra of uranyl minerals and synthetic uranyl compounds. II: The O 1s spectrum

The O 1s spectrum is examined for 19 uranyl minerals of different composition and structure. Spectra from single crystals were measured with a Kratos Axis Ultra X-ray Photoelectron Spectrometer with a magnetic-confinement charge-compensation system. Well-resolved spectra with distinct maxima, shoulders and inflections points, in combination with reported and measured binding energies for specific O²⁻ species and structural data of the uranyl minerals are used to resolve the fine structure of the O 1s envelope. The resolution of the O 1s spectra includes, for the first time, different O²⁻ bands, which are assigned to O atoms linking uranyl with uranyl polyhedra (UOU) and O atoms of uranyl groups (OUO). The resolved bands in the O 1s spectrum occur at distinct ranges in binding energy: bands for (UOU) occur at 529.6-530.4 eV, bands for (OUO) occur at 530.6-531.4 eV, bands for O²⁻ in the equatorial plane of the uranyl polyhedra linking uranyl polyhedra with (TO_n) groups (T = Si, S, C, P, Se) (TO) occur at 530.9-532.2 eV; bands for (OH) groups in the equatorial plane of the uranyl polyhedra (OH) occur at 532.0-532.5 eV, bands of (H₂O) groups in the interstitial complex of the uranyl minerals (H₂O_interst) occur at 533.0-533.8 eV and bands of physisorbed (H₂O) groups on the surface of uranyl minerals (H₂O_adsorb) occur at 534.8-535.2 eV. Treatment of uranyl minerals with acidic solutions results in a decrease in UOU and an increase in OH. Differences in the ratio of OH : OUO between the surface and bulk structure is larger for uranyl minerals with a high number of UOU and TO species in the bulk structure which is explained by protonation of underbonded UO, UOU and TO terminations on the surface. The difference in the ratio of H₂O_interst : OUO between the bulk and surface structures is larger for uranyl minerals with higher percentages of H₂O_interst as well as, with a higher number of interstitial H₂O groups that are not bonded to interstitial cations, resulting in easier dehydration of interstitial H₂O groups in uranyl minerals during exposure to a vacuum.     

The application of foraminifera to reconstruct the rate of 20th century sea level rise, Morbihan Golfe, Brittany, France

Foraminiferal assemblages preserved within salt-marsh sediment can provide an accurate and precise means to reconstruct relative sea level due to a strong relationship with elevation, which can be quantified using a transfer function. We collected a set of surface samples from two salt marshes in the Morbihan Golfe, France to determine foraminiferal distribution patterns. Dominant taxa included Jadammina macrescens, Trochammina inflata, Haplophragmoides spp. and Miliammina fusca. We developed a foraminifera-based transfer function using a modern training set of 36 samples and 23 species. The strong relationship between observed and predicted values (r²_jack = 0.7) indicated that foraminiferal distribution is primarily controlled by elevation with respect to the tidal frame and precise reconstructions of former sea level are possible (RMSEP_jack = 0.07 m). The application of the transfer function to a short salt-marsh core (0.32 m) allowed the reconstruction of former sea levels, which were placed in a chronological framework using short-lived radionuclides (²¹⁰Pb and ¹³⁷Cs). The agreement between the foraminifera-based sea level curve and the Brest tide-gauge record confirms the reliability of transfer function estimates and the validity of this methodology to extend sea level reconstructions back into the pre-instrumental period. Both instrumental and microfossil records suggest an acceleration of sea level rise during the 20th century.     

Distribution of the C37 tetra-unsaturated alkenone in Lake Qinghai, China: A potential lake salinity indicator

The alkenone unsaturation index U^K′₃₇ has been applied to reconstruct past temperature changes in both marine and lacustrine systems. However, few studies have addressed whether the relative abundance of the C_37:4 alkenone to the total C₃₇ production (%C_37:4) can reflect surface salinity changes in lacustrine systems. Here we present long-chain C₃₇ alkenone distribution patterns in surface sediments from Lake Qinghai, China. Surface sediments were sampled over a large range of surface salinity changes (1.7-25 g/l) within Lake Qinghai and its surrounding lakes, while temperature differences at these sampling locations should be relatively small. We have found that %C_37:4 varies from 15% to 49% as surface salinity decreases. We tentatively describe this %C_37:4-salinity link with a general linear regression: %C_37:4 = 53.4 (±7.8) − 1.73 (±0.45) × S (n = 28, r² = 0.62), although step-wise %C_37:4 changes in response to salinity variation may exist. U^K′₃₇ values vary between 0.10 and 0.16 at these sites and the inferred range of lake water temperature changes is ∼2-3 °C, suggesting that U^K′₃₇ largely reflects temperature signal across a large salinity range, consistent with previous findings that U^K′₃₇ can indicate temperature changes over a large diversity of environmental settings. We have also found that U^K′₃₇ values are correlated with salinity changes (r² = 0.4), and thus cannot exclude potential temperature effect on %C_37:4 and salinity effect on U^K′₃₇ in this study. However, even extreme estimates of temperature differences within the lake are still unable to explain the observed %C_37:4 changes. We therefore suggest that %C_37:4 could be used to infer past lake salinity changes at a regional scale.     

Shock compression of zirconia ZrO2 and zircon ZrSiO4 in the pressure range up to 150 GPa

The shock compression state of zirconia ZrO₂ and zircon ZrSiO₄ in the pressure range up to 150 GPa (1.5 Mbar) are studied on the basis of the measurements of shock velocities, particle-velocity histories, free surface motions, and electrical conductivities. Zircon transforms, and zirconia probably does, to high pressure phases up to 90 GPa. The shock velocity (U _s ) — particle velocity (U _p ) Hugoniots can be described as U _s =4.38+1.37 U _p km/s above 90 GPa for ZrO₂, and U _s =6.50+0.49 U _p km/s (mixed phase region), and U _s =1.54+2.30 U _p km/s (high pressure phase region) for ZrSiO₄. The corrected isothermal densities of the high pressure phase ZrSiO₄ are roughly consistent with the isothermal ones of mixtures of ZrO₂ and SiO₂. Bulk sound velocities in the high-pressure phase region of these oxides are discussed in comparison with other dioxides. Electrical conductivities of these oxides increase from lower than 10^?12 S/m to greater than 10⁰ S/m in the shock-stress range up to 70 GPa, and remain as constant values up to higher than 100 GPa.     

Controls on alkenone unsaturation ratios along the salinity gradient between the open ocean and the Baltic Sea

Alkenone unsaturation ratios of sedimentary lipids are used as a geochemical proxy for sea surface temperatures, and interest is growing in their potential as indicators of different water masses and possibly of salinity. We analyzed the abundance of unsaturated C₃₇ to C₃₈ ketones in lipid extracts of 57 surface sediment (0-1 cm) samples along a salinity gradient from 8 to 33 psu in the transition from the Skagerrak to the Baltic Sea (NW Europe). In addition to surface sediments, we analyzed alkenones in suspended particulate matter at 13 stations—over a gradient in salinity from 25 to 33 psu—during a bloom of the coccolithophore Emiliania huxleyi. Alkenones were detected in all samples (suspended matter and sediment) with variable contributions of the tetra-unsaturated C₃₇ alkenone compound (%C_37:4; range from 2 to 10% of total C₃₇ alkenone content). Comparing the alkenone unsaturation index (U₃₇^K′) and %C_37:4 data to climatological sea surface temperature and sea surface salinity data sets revealed that SST estimated from U₃₇^K′ of saline end members (samples from the Skagerrak) is in the general range of modern SST during bloom periods of haptophytes. At salinities below ∼30 psu %C_37:4 increases to above 5% and the unsaturation ratios cease to be related to climatological annual or seasonal sea surface temperatures. On the other hand, the %C_37:4 appears to be inversely and significantly correlated to salinity: Highest C_37:4 proportions in the inner Baltic Sea are caused by an unidentified organism, but in the transition area at salinities down to 10 psu, the producer apparently is E. huxleyi. The suspended matter data together with those from the water column support the hypothesis of changing biosynthesis of alkenones under salt stress by the coccolithophore E. huxleyi, but constrain the maximum of %C_37:4 attributable to salt stress to 10% of all C₃₇ alkenones.     

Characteristics of alkenones synthesized by a bloom of emiliania huxleyi in the Bering Sea

We investigated the characteristics of the alkenones produced by a bloom of Emiliania huxleyi in the eastern Bering Sea in 2000. Alkenones were detected in surface waters between 57°N and 63°N, where phosphate concentrations were low and the ammonium/nitrate ratio was high. The total alkenone content (C_37:2, C_37:3, and C_37:4) ranged from 22.0 to 349 μg g⁻¹ in suspended particles and from 0.109 to 1.42 μg g⁻¹ in surface sediments. This suggests that a large proportion of the particulate alkenones synthesized in the surface water rapidly degraded within the water column and/or at the water-sediment interface of the Bering Shelf. The change in the stable carbon isotopic composition (δ¹³C) of C_37:3 alkenone could not be explained only by variation in [CO₂(aq)] in the surface water but also depended on the growth rate of E. huxleyi. The alkenone unsaturation index (U^K′₃₇) was converted into an alkenone “temperature” with three equations [Prahl et al 1988], [Sikes et al 1997] and [Müller et al 1998]; Sikes et al.’s (1997) equation gave the best correlation with the observed sea surface temperature (SST) in the eastern Bering Sea. However, some temperatures estimated by Sikes et al.’s (1997) equation from the U^K′₃₇ varied from the observed SST, possibly because of the rapidly changing rate of alkenone synthesis in the logarithmic growth stage or the low rate of alkenone synthesis when nutrients were limiting. Temperatures estimated from U^K′₃₇ in the surface sediments (6.8-8.2°C) matched the observed SST in September (7-8°C) but differed from the annual average SST of 4 to 5°C, suggesting that most of the alkenone in the eastern Bering Sea was synthesized during limited periods, for instance, in September. The relative amounts of C_37:4 alkenone as proportions of the total alkenones (referred to as C_37:4%) were high, ranging from 18.3 to 41.4%. Low-salinity water (<32 psu) within the study area would have contributed to the high C_37:4% because a negative linear relationship between C_37:4% and salinity was found in this study.     

Seawater temperature proxies based on DSr, DMg, and DU from culture experiments using the branching coral Porites cylindrica

In order to investigate the incorporation of Sr, Mg, and U into coral skeletons and its temperature dependency, we performed a culture experiment in which specimens of the branching coral (Porites cylindrica) were grown for 1 month at three seawater temperatures (22, 26, and 30 °C). The results of this study showed that the linear extension rate of P. cylindrica has little effect on the skeletal Sr/Ca, Mg/Ca, and U/Ca ratios. The following temperature equations were derived: Sr/Ca (mmol/mol) = 10.214(±0.229) − 0.0642(±0.00897) × T (°C) (r² = 0.59, p < 0.05); Mg/Ca (mmol/mol) = 1.973(±0.302) + 0.1002(±0.0118) × T (°C) (r² = 0.67, p < 0.05); and U/Ca (μmol/mol) = 1.488(±0.0484) − 0.0212(±0.00189) × T (°C) (r² = 0.78, p < 0.05). We calculated the distribution coefficient (D) of Sr, Mg, and U relative to seawater temperature and compared the results with previous data from massive Porites corals. The seawater temperature proxies based on D calibrations of P. cylindrica established in this study are generally similar to those for massive Porites corals, despite a difference in the slope of D_U calibration. The calibration sensitivity of D_Sr, D_Mg, and D_U to seawater temperature change during the experiment was 0.64%/°C, 1.93%/°C, and 1.97%/°C, respectively. These results suggest that the skeletal Sr/Ca ratio (and possibly the Mg/Ca and/or U/Ca ratio) of the branching coral P. cylindrica can be used as a potential paleothermometer.     

Retention of biosignatures and mass-independent fractionations in pyrite: Self-diffusion of sulfur

Self-diffusion of sulfur in pyrite (FeS₂) was characterized over the temperature range ∼500-725 °C (∼1 bar pressure) by immersing natural specimens in a bath of molten elemental ³⁴S and characterizing the resulting diffusive-exchange profiles by Rutherford backscattering spectroscopy (RBS). The temperature dependence of the sulfur diffusivity (D_S) conforms to D_S = D_o exp(−E_a/RT), where the pre-exponential constant (D_o) and the activation energy (E_a) are constrained as follows:

     

Estimating the Density and Compressibility of Seawater to High Temperatures Using the Pitzer Equations

The density and compressibility of seawater solutions from 0 to 95 °C have been examined using the Pitzer equations. The apparent molal volumes (X = V) and compressibilities (X = κ) are in the form $$ X_{\phi } = \bar{X}^{0} + A_{X} I/(1.2 \, m)\ln (1 + 1.2 \, I^{0.5} ) + \, 2{\text{RT }}m \, (\beta^{(0)X} + \beta^{(1)X} g(y) + C^{X} m) $$ where $ \bar{X}^{0} $ is the partial molal volume or compressibility, I is the ionic strength, m is the molality of sea salt, A_X is the Debye–Hückel slope for volume (X = V) or adiabatic compressibility (X = κ _s), and g(y) = (2/y ²)[1 ? (1 + y) exp(?y)] where y = 2I ^0.5. The values of the partial molal volume and compressibility ( $ \bar{X}^{0} $ ) and Pitzer parameters (β ^(0)X , β ^(1)X and C ^X ) are functions of temperature in the form $$ Y^{X} = \sum_{i} a_{i} (T-T_{\text{R}} )^{i} $$ where a _i are adjustable parameters, T is the absolute temperature in Kelvin, and T _R = 298.15 K is the reference temperature. The standard errors of the seawater fits for the specific volumes and adiabatic compressibilities are 5.35E?06 cm³ g^?1 and 1.0E?09 bar^?1, respectively. These equations can be combined with similar equations for the osmotic coefficient, enthalpy and heat capacity to define the thermodynamic properties of sea salt to high temperatures at one atm. The Pitzer equations for the major components of seawater have been used to estimate the density and compressibility of seawater to 95 °C. The results are in reasonable agreement with the measured values (0.010E?03 g cm^?3 for density and 0.050E?06 bar^?1 for compressibility) from 0 to 80 °C and salinities from 0 to 45 g kg^?1. The results make it possible to estimate the density and compressibility of all natural waters of known composition over a wide range of temperature and salinity.     

Heterogeneous reduction of U by structural Fe from theory and experiment

Computational and experimental studies were performed to explore heterogeneous reduction of U⁶⁺ by structural Fe²⁺ at magnetite (Fe₃O₄) surfaces. Molecular Fe-Fe-U models representing a uranyl species adsorbed in a biatomic bidentate fashion to an iron surface group were constructed. Various possible charge distributions in this model surface complex were evaluated in terms of their relative stabilities and electron exchange rates using ab initio molecular orbital methods. Freshly-cleaved, single crystals of magnetite with different initial Fe²⁺/Fe³⁺ ratios were exposed to uranyl-nitrate solution (pH ∼ 4) for 90 h. X-ray photoelectron spectroscopy and electron microscopy indicated the presence of a mixed U⁶⁺/U⁵⁺ precipitate heterogeneously nucleated and grown on stoichiometric magnetite surfaces, but only the presence of sorbed U⁶⁺ and no precipitate on sub-stoichiometric magnetite surfaces. Calculated electron transfer rates indicate that sequential multi-electron uranium reduction is not kinetically limited by conductive electron resupply to the adsorption site. Both theory and experiment point to structural Fe²⁺ density, taken as a measure of thermodynamic reducing potential, and sterically accessible uranium coordination environments as key controls on uranium reduction extent and rate. Uranium incorporation in solid phases where its coordination is constrained to the uranate type should widen the stability field of U⁵⁺ relative to U⁶⁺. If uranium cannot acquire 8-fold coordination then reduction may proceed to U⁵⁺ but not necessarily U⁴⁺.     

Evidence for differential degradation of alkenones under contrasting bottom water oxygen conditions: implication for paleotemperature reconstruction

The successful reconstruction of sea surface temperatures using alkenone paleothermometry (U₃₇^k′) has relied on the premise that there is no significant differential degradation of alkenones with different states of unsaturation during diagenetic processes. To test this assumption, we conducted a comparative study of contemporary sediments in oxic and anoxic bottom waters from the Santa Monica Basin, offshore California. Long-chain alkenones were quantified and sea surface temperature were calculated using the calibrated U₃₇^k′–T relationship of Prahl et al. (1988). Our results show that temperature record from the oxic sediments is higher by as much as 4°C compared to those from time-equivalent anoxic sediments as a result of differential degradation of long-chain unsaturated alkenones and bioturbation mixing in the oxic sediments. The differential degradation of C_37:3 vs. C_37:2 alone could account for up to 2.5°C difference between these two records. This finding has significant implication in the interpretation of paleo–sea surface temperature data using alkenone paleothermometry.     

Estimation of uranium endowment by subjective geological analysis—a comparison of methods and estimates for the San Juan Basin,New Mexico

This study investigates how estimates of uranium endowment made by a geologist using an appraisal system that is based upon a formalization of geoscience and decision rules compare with estimates made by informal and unconstrained intuitive processes. The motivation for this study derives from the premise that formalization of decisions would mitigate the heuristic biases and hedging that may result from the use of unconstrained intuitive processes. Estimates of the uranium endowment of the San Juan Basin of New Mexico by four methodologies are compared in this study. These methods, ranked from top to bottom by degree of decomposition (mitigating of heuristic bias)and control on hedging, are as follows Implicit 2 1.5 × 10⁶ s.t. of U₃O₈ Implicit 1 1.6 × 10⁶ s.t. of U₃O₈ NURE (1980) 2.4 × 10⁶ s.t. of U₃O₈ Appraisal system 3.9 × 10⁶ s.t. of U₃O₈ The magnitude of expected uranium endowment estimated by these methods, ranked from smallest to largest, is in this same order. With the exception of the NURE estimates, the magnitude of the variance (uncertainty)of uranium endowment, ranked from smallest to largest, also is in this same order. These results prompt the suggestion that the more decomposed and formalized the estimation procedure, the greater the expected value and the variance of uranium endowment. Equivalently, predicating U ₃ O ₈ endowment estimation strictly upon that part of the geologist's geoscience that is useful in making U ₃ O ₈ endowment estimates and upon his understanding of the region's history produced larger estimates than have previously been reported. However, this method of estimation also shows that uncertainty about the actual state of U ₃ O ₈ endowment is much greater than previously described.     

Stable carbon and oxygen isotope fractionation in bivalve (Placopecten magellanicus) larval aragonite

The relationship between stable isotope composition (δ¹³C and δ¹⁸O) in seawater and in larval shell aragonite of the sea scallop, Placopecten magellanicus, was investigated in a controlled experiment to determine whether isotopes in larval shell aragonite can be used as a reliable proxy for environmental conditions. The linear relationship between δ¹³C_DIC and δ¹³C_aragonite (r² = 0.97, p < 0.0001, RMSE = 0.18) was:

δ¹³C_DIC=1.15(±0.05)∗δ¹³C_aragonite-0.85(±0.04)     

Carbon isotopic fractionation during the CO2 exchange process between air and sea water under equilibrium and kinetic conditions

Carbon isotopic fractionation during the air/sea exchange process is not fully understood at present. Information on the equilibrium and kinetic fractionation factors is an essential requirement, together with the value of the CO₂ partial pressure, for understanding the carbon cycle in the atmosphere and marine environments. Using a specially designed countercurrent equilibrator system, the fractionation factors between gaseous CO₂ and dissolved inorganic carbon in sea water were determined under both kinetic and equilibrium conditions. The following results were obtained: kinetic fractionation factor for air to sea (α_as) is 0.998 at 288.2 K; kinetic fractionation factor for sea to air (α_sa) is 0.990; equilibrium fractionation factor (α_eq) is 0.991 at pH = 8.3 and 288.2 K. From these results, the carbon isotopic ratio of CO₂ passed through the air/ sea interface is estimated to be about ?10 %. for air to sea and ?8 %. for sea to air when CO₂ exchange takes place between air (δ¹³C = ?8 %.) and surface sea water (δ¹³C = 2 %.) at 288.2 K.     

The marine oxygen isotope record in Pleistocene coral,Barbados, West Indies

The reef-crest coral Acropora palmata from late Pleistocene reefs on Barbados has recorded the same global variations in oxygen isotopes as planktonic and benthonic foraminifera. Although the record of oxygen isotopes in Acropora palmata is discontinuous, it offers several advantages over the isotope records from deep-sea sediments: (1) the coral grows at water depths of less than 5 m; (2) the samples are unmixed; (3) specimens may be sampled from various elevations of paleo-sea level; and (4) aragonitic corals are suitable for ${}^{230}\text{Th}{}^{234}\text{U}$ and $\text{He}\text{U}$ dating techniques. The latter advantage means that direct dating of the marine oxygen isotope record is possible. Oxygen isotope stage 5e corresponds to Barbados III, dated at 125,000 ± 6000 yr BP. Petrographic and geochemical evidence from five boreholes drilled into the south coast of Barbados indicates a major eustatic lowering (greater than 100 m below present sea level) occurred between 180,000 and 125,000 yr BP. The age and isotopic data suggest correlation of this change in sea level to Emiliani's oxygen isotope stage 6. Acropora palmata deposited at various elevations of sea level during oxygen isotope stage 6 vary by 0.11 ‰ δ¹⁸O for each 10 m of change in sea level. We further hypothesize a minimum drop of 2°C in the average temperature occurred during the regressive phase of oxygen isotope stage 6. These data indicate that temperature lowering of surface water near Barbados lagged behind a major glacial buildup during this time period. Using the δ¹⁸O vs sea level calibration herein derived, we estimate the relative height of sea stands responsible for Barbados coral reef terraces in the time range 80,000 to 220,000 yr BP.     

Palaeohydraulics of a tabular,cross-stratified sand in the Brampton Esker,Ontario

Several hydraulic techniques were used to estimate the flow depth (0.3 m) associated with the deposition of a tabular set (micro-delta) of cross-stratified sand in the Brampton esker. The competency of the flow, deduced from both the grain size and structural characteristics of the set, gave a value of approximately 0.65 m/sec for the palaeo-velocity of the flow. Estimates of palaeo-depth and velocity facilitated calculation of the Froude and Reynolds numbers, about 0.38 and 1.24 · 10⁵, respectively. Extrapolation of other parameters included bed shear stress τ₀ (4.50 N/m²), shear velocity U_* (0.067 m/sec), dimensionless Chezy coefficient C/√g (9.7), slope of the energy gradient S(0.00153), Darcy-Weisbach friction factor f(0.085), Manning roughness coefficient n(0.027) and discharge of bed-material load (19 metric tons/day/m). The figures cited are reasonable estimates only. The occurrence of regressive ripples in the bottomset of the micro-delta aided in the hydraulic interpretation. These flow characteristics are only representative of the final stages of deposition at one location on the flank of the esker. The core of the esker was probably deposited under different hydraulic conditions.     

Uptake of uranium and trace elements in pyrite (FeS2) suspensions

Pyrite dissolution and interaction with Fe^(II), Co^(II), Eu^(III) and U^(VI) have been studied under anoxic conditions by solution chemistry and spectroscopic techniques. Aqueous data show a maximal cation uptake above pH 5.5. Iron (II) uptake can explain the non-stoichiometric [S]_aq/[Fe]_aq ratios often observed during dissolution experiments. Protonation data corrected for pyrite dissolution resulted in a proton site density of 9 ± 3 sites nm⁻². Concentration isotherms for Eu^(III) and U^(VI) sorption on pyrite indicate two different behaviours which can be related to the contrasted redox properties of these elements. For Eu^(III), sorption can be explained by the existence of a unique site with a saturation concentration of 1.25 × 10⁻⁶ mol g⁻¹. In the U^(VI) case, sorption seems to occur on two different sites with a total saturation concentration of 4.5 × 10⁻⁸ mol g⁻¹. At lower concentration, uranium reduction occurs, limiting the concentration of dissolved uranium to the solubility of UO₂(s).Scanning electron microscopy and micro-Raman spectrometry of U^(VI)-sorbed pyrite indicate a heterogeneous distribution of U at the pyrite surface and a close association with oxidized S. X-ray photoelectron spectroscopy confirms the partial reduction of U and the formation of a hyperstoichiometric UO_2+x(s). Our results are consistent with a chemistry of the pyrite surface governed not by Fe^(II)-bound hydroxyl groups, but by S groups which can either sorb cations and protons, or sorb and reduce redox-sensitive elements such as U^(VI).