Plutonium and americium in anoxic marine sediments: Evidence against remobitization     

R. Carpenter  T.M. Beasley 《Geochimica et cosmochimica acta》1981,45(10):1917-1930

^{239 + 240}Pu activities of 100–450dpm/kg are found down to 15–18 cm in anoxic Saanich Inlet sediments, with a subsurface maximum in undisturbed deposits. Integrated ^{239 + 240}Pu inventories which overlap delivery estimates are present both in two cores of anoxic sediments from Saanich Inlet and in one core of oxic sediments 65 km away in Dabob Bay, Washington. ${}^{241}\text{Am}{}^{\mathrm{239\; +\; 240}}\text{Pu}$ ratios in Saanich Inlet sediments overlap ratios in unfractionated midnorthern latitude fallout, in oxic sediments from the Washington continental shelf, and in anoxic sediments from two basins off southern California and Mexico. The ${}^{\mathrm{239\; +\; 240}}\text{Pu}{}^{137}\text{Cs}$ ratios in three intervals of Saanich Inlet sediments are also in agreement with ratios previously reported for oxic coastal marine sediments. The Pu inventories, the $\text{Am}\text{Pu}$ and $\text{Pu}\text{Cs}$ ratios, and the Saanich Inlet Dabob Bay comparison all argue that Pu is not rapidly remobilized in anoxic sediments.The subsurface ^{239 + 240}Pu activity maximum is not in agreement with the historical record of peak Pu fallout in 1963–1964 unless our ²¹⁰Pb-derived sedimentation rates are incorrectly high. However, they are in good agreement with previous ²¹⁰Pb and varve chronologies in Saanich Inlet, and also give reasonable dates for times when ^{239 + 240}Pu and SNAP-9A supplied ²³⁸Pu first appear in the sediments. We conclude they properly date the maximum in sedimentary ^{239 + 240}Pu activity at 1970–1973, and seek explanations for the 7–10yr time lag after peak fallout.^{239 + 240}Pu inventories in one core from the eastern basin of the Cariaco Trench and in two cores from Golfo Dulce. an anoxic basin off the Pacific coast of Costa Rica, are also in reasonable agreement with fallout delivery to these latitudes when excess ²¹⁰Pb inventories and fluxes are used to verify recovery of at least a major fraction of the most recently deposited sediments.  相似文献   

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

J.H. Jones  D.S. Burnett 《Geochimica et cosmochimica acta》1979,43(12):1895-1905

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.  相似文献   

The geochemical coherence of Pu and Nd and the ${}^{244}\text{Pu}{}^{238}\text{U}$ ratio of the early solar system     

John H. Jones 《Geochimica et cosmochimica acta》1982,46(10):1793-1804

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.  相似文献   

Influence of an americium solid phase on americium concentrations in solutions     

Dhanpat Rai  R.G. Strickert  D.A. Moore  R.J. Serne 《Geochimica et cosmochimica acta》1981,45(11):2257-2265

Americium-241 concentrations in solutions contacting contaminated sediments for up to 2 yr were measured as a function of pH. Steady-state concentrations were reached within a few days. The solubility-limited Am concentration was found to decrease approximately 10-fold with one unit increase in pH. The log equilibrium constant for the solubility of Am_(soil) solid $\text{[Am}{}_{\mathrm{(soil)}}\text{+ H}{}^{\mathrm{+}}\text{? Am}{}_{\mathrm{(aq\; complex)}}{}^{\mathrm{+}}\text{]}$ was found to be ?4.12. The predictions based upon thermodynamic data suggest that Am_{(aq complex)}⁺ is likely to be Am(OH)₂⁺. Although the chemical formula of Am_(soil) was not determined, it does not appear to be Am(OH)₃(a).Published data on sorption coefficients of Am by different rocks, soils, and minerals were critically evaluated. Final Am solution concentrations calculated from the sorption coefficients of a variety of earth materials with several solutions agreed well with the concentrations predicted from the solubility of Am_(soil) solid, indicating that the sorption coefficient data are controlled by Am precipitation.  相似文献   

Particle mixing rates in sediments of the eastern equatorial Pacific: Evidence from ²¹⁰Pb, ^239,240Pu and ¹³⁷Cs distributions at MANOP sites     

J.Kirk Cochran 《Geochimica et cosmochimica acta》1985,49(5):1195-1210

Particle mixing rates (D_B) calculated from excess ²¹⁰Pb gradients in sediments of the east equatorial Pacific range from 0.04 to 0.5 cm²/y, with variation of a factor of 3–4 at a single site. Diffusion of the ²³⁶Ra daughter ²²²Rn may affect ²¹⁰Pb distributions under conditions of slow mixing and low ²¹⁰Pb flux to the seafloor, as shown by a siliceous ooze-clay core which contained the fallout radionuclides ^239,240Pu and ¹³⁷Cs but no excess ²¹⁰Pb (relative to ²²⁶Ra). There is no clear relationship between ²¹⁰Pbderived mixing rates and sediment type, accumulation rate or organic carbon flux to the sediments. Comparison of ²¹⁰Pb mixing rates with those calculated from ^239,240Pu and ¹³⁷Cs distributions reveals better agreement for a pulse input of the fallout radionuclides (D_B = 0.03?0.4 cm²/y) than for continuous input at a constant rate (D_B = 0.1?1.6 cm²/y), although the Pu and ¹³⁷Cs data are better fit by the latter model. The agreement may be fortuitous because ^239,240Pu and ¹³⁷Cs appear significantly deeper than ²¹⁰Pb in at least one core. Tracer separation could be caused by particle size-selective mixing by the benthic fauna or by chemical mobilization. If the fallout radionuclides are scavenged from surface waters by large, organic-rich particles such as fecal pellets, their release and migration may result from decomposition of the carrier in surface sediments. Either a relatively unreactive form of Pu (e.g. oxidized Pu) has been released by this process or a one-dimensional model is inadequate to explain its observed penetration into the sediments. Activity ratios of ${}^{\mathrm{239,240}}\text{Pu}{}^{137}\text{Cs}$ in the sediments decrease with increasing north latitude, and the trend reflects higher fluxes of ^239,240Pu near the weapons test site at Christmas Island (2°N). The ${}^{\mathrm{239,240}}\text{Pu}{}^{137}\text{Cs}$ ratios and fluxes to the sediment (assuming constant input) at the siliceous ooze-red clay site are consistent with published sediment trap data from a nearby site. Thus if fallout radionuclide fluxes to the sea floor were higher in the past, both ^239,240Pu and ¹³⁷Cs have been released from sinking particles.  相似文献   

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

B.L Dickson 《Geochimica et cosmochimica acta》1985,49(2):361-368

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.  相似文献   

Sources and vertical distribution of 137Cs, 238Pu, 239+240Pu and 241Am in peat profiles from southwest Spitsbergen     

《Applied Geochemistry》2013

This paper presents a detailed survey of the activities of selected man-made radionuclides in peat deposits located in SW Spitsbergen. Peat cores from the High Arctic (SW Spitsbergen) were analyzed by gamma spectrometry (¹³⁷Cs), alpha spectrometry (²³⁸Pu, ^239,240Pu, ²⁴¹Am activities) and by ICPMS (²⁴⁰Pu/²³⁹Pu atom ratios). Maximum activities evident in the peats correspond to the 1963/1964 global maximum fallout from atmospheric testing of nuclear weapons; some of the activity profiles have been altered post-deposition by water infiltration. Activity ratios of ²³⁸Pu/^239+240Pu, ²⁴¹Am/^239+240Pu, ^239+240Pu/¹³⁷Cs and ²⁴⁰Pu/²³⁹Pu atom ratios indicate mixing between global (stratospheric) and regional (tropospheric) sources of these radionuclides in the Svalbard area. The ²³⁸Pu/^239+240Pu activity ratios varied from 0.02 ± 0.01 to 0.09 ± 0.03, suggesting global fallout as the dominant source of Pu. The ^239+240Pu/¹³⁷Cs activity ratios varied from 0.01 ± 0.01 to 0.42 ± 0.11, which apparently arises from the post-depositional mobility of ¹³⁷Cs. The ²⁴¹Am/^239+240Pu activity ratios ranged between 0.10 ± 0.02 and 1.5 ± 0.3 and exceed the published global fallout ratio for Svalbard of 0.37 due to the relatively higher geochemical mobility of Pu vs. Am and/or ingrowth of Am from the decay of ²⁴¹Pu. The atom ratio ²⁴⁰Pu/²³⁹Pu ranged from 0.142 ± 0.006 to 0.241 ± 0.027; however, the vast majority of peat samples exhibited ²⁴⁰Pu/²³⁹Pu atom ratios similar to the stratospheric fallout (∼0.18).  相似文献   

Rates of reaction of pyrite and marcasite with ferric iron at pH 2     

C.L Wiersma  J.D Rimstidt 《Geochimica et cosmochimica acta》1984,48(1):85-92

The relative reactivities of pulverized samples (100–200 mesh) of 3 marcasite and 7 pyrite specimens from various sources were determined at 25°C and pH 2.0 in ferric chloride solutions with initial ferric iron concentrations of 10^?3 molal. The rate of the reaction: was determined by calculating the rate of reduction of aqueous ferric ion from measured oxidation-reduction potentials. The reaction follows the rate law: where m_Fe³⁺ is the molal concentration of uncomplexed ferric iron, k is the rate constant and $\text{A}\text{M}$ is the surface area of reacting solid to mass of solution ratio. The measured rate constants, k, range from 1.0 × 10^?4 to 2.7 × 10^?4 sec^?1 ± 5%, with lower-temperature/early diagenetic pyrite having the smallest rate constants, marcasite intermediate, and pyrite of higher-temperature hydrothermal and metamorphic origin having the greatest rate constants. Geologically, these small relative differences between the rate constants are not significant, so the fundamental reactivities of marcasite and pyrite are not appreciably different.The activation energy of the reaction for a hydrothermal pyrite in the temperature interval of 25 to 50°C is 92 kJ mol^?1. This relatively high activation energy indicates that a surface reaction controls the rate over this temperature range. The BET-measured specific surface area for lower-temperature/early diagenetic pyrite is an order of magnitude greater than that for pyrite of higher-temperature origin. Consequently, since the lower-temperature types have a much greater $\text{A}\text{M}$ ratio, they appear to be more reactive per unit mass than the higher temperature types.  相似文献   

Prediction of Gibbs free energies of calcite-type carbonates and the equilibrium distribution of trace elements between carbonates and aqueous solutions     

Dimitri A Sverjensky 《Geochimica et cosmochimica acta》1984,48(5):1127-1134

A linear correlation exists between the standard Gibbs free energies of formation of calcite-type carbonates (MCO3) and the corresponding conventional standard Gibbs free energies of formation of the aqueous divalent cations (M2+) at 25 °C and 1 bar ΔGMCO30 = m(ΔGf,M2+0) ? 141,200 cal · mole?1 where m is equal to 0.9715. This relationship enables prediction of the standard free energies of formation of numerous hypothetical carbonates with the calcite structure. Associated uncertainties typically range from about ± 250 to 600 cal · mole?1. An important consequence of the above correlation is that the thermodynamic equilibrium constant for the distribution of two trace elements M and N between carbonate mineral and aqueous solution at 25 °C and 1 bar is proportional to the free energy difference between the corresponding two aqueous ions: In Combination of predicted standard free energies, entropies and volumes of carbonate minerals at 25°C and 1 bar with standard free energies of aqueous ions and the equation of state in Helgesonet al. (1981) enables prediction of the thermodynamic equilibrium constant for trace element distribution between carbonates and aqueous solutions at elevated temperatures and pressures. Interpretation of the thermodynamic equilibrium constant in terms of concentration ratios in the aqueous phase is considerably simplified if pairs of divalent trace elements are considered that have very similar ionic radii (e.g., $\text{Sr}{}^{\mathrm{2+}}\text{Pb}{}^{\mathrm{2+}}$, $\text{Mg}{}^{\mathrm{2+}}\text{Zn}{}^{\mathrm{2+}}$). In combination with data for the stabilities of complex ions in aqueous solutions, the above calculations enable useful limits to be placed on the concentrations of trace elements in hydrothermal solutions.  相似文献   

Complexing of silica by iron(III) in natural waters     

E.J. Reardon 《Chemical Geology》1979,25(4):339-345

Determination of amorphous silica solubility in acidified ferric nitrate solutions confirms the presence of ferric silicate complexing. A dissociation constant for the reaction: of 10^?9.8 ± 0.3 pK units at room temperature (22 ± 3°C) is obtained, in close agreement with reported values at 25°C corrected to zero ionic strength of 10^?9.9 by Weber and Stumm and 10^?9.5 by Olson and O'Melia. Iron-silicate complexing may be of significance to the mobilization of silica in acid waters associated with oxidizing sulphide deposits and coal strip mining and the precipitation of secondary silicate mineral phases.  相似文献   

Uranium isotopes in rivers,estuaries and adjacent coastal sediments of western India: their weathering,transport and oceanic budget   总被引：1，自引：0，他引：1  

D.V Borole  S Krishnaswami  B.L.K Somayajulu 《Geochimica et cosmochimica acta》1982,46(2):125-137

The two major river systems on the west coast of India, Narbada and Tapti, their estuaries and the coastal Arabian sea sediments have been extensively studied for their uranium concentrations and ${}^{238}\text{U}{}^{238}\text{U}$ activity ratios.The ²³⁸U concentrations in the aqueous phase of these river systems exhibit a strong positive correlation with the sum of the major cations, σ Na + K + Mg + Ca, and with the HCO₃^? ion contents. The abundance ratio of dissolved U to the sum of the major cations in these waters is similar to their ratio in typical crustal rocks. These findings lead us to conclude that ²³⁸U is brought into the aqueous phase along with major cations and bicarbonate. The strong positive correlation between ²³⁸U and total dissolved salts for selected rivers of the world yield an annual dissolved ²³⁸U flux of 0.88 × 10¹⁰g/yr to the oceans, a value very similar to its removal rate from the oceans, 1.05 × 10¹⁰g/yr, estimated based on its correlation with HCO₃^? contents of rivers.In the estuaries, both ²³⁸U and its great-grand daughter ²³⁴U behave conservatively beyond chlorosities 0.14 g/l. These data confirm our earlier findings in other Indian estuaries. The behavior of uranium isotopes in the chlorosity zone 0.02–0.14 g/l, was studied in the Narbada estuary in some detail. The results, though not conclusive, seem to indicate a minor removal of these isotopes in this region. Reexamination of the results for the Gironde and Zaire estuaries (Martin et al., 1978a and b) also appear to confirm the conservative behavior of U isotopes in unpolluted estuaries. It is borne out from all the available data that estuaries beyond 0.14 g/l chlorosities act neither as a sink nor as a source for uranium isotopes, the behavior in the low chlorosity zones warrants further detailed investigation.A review of the uranium isotope measurements in river waters yield a discharge weighted-average ²³⁸U concentration of 0.22 μg/l with a ${}^{234}\text{U}{}^{238}\text{U}$ activity ratio of 1.20 ± 0.06ismissing. The residence time of uranium isotopes in the oceans estimated from the ²³⁸U concentration and the ${}^{234}\text{U}{}^{238}\text{U}$ A. R. of the rivers yield conflicting results; the material balance of uranium isotopes in the marine environment still remains a paradox. If the disparity between the results is real, then an additional ²³⁴U flux of about 0.25 dpm/cm₂·10³ yr into the oceans (about 20% of its river supply) is necessitated.  相似文献   

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

Matti Asikainen 《Geochimica et cosmochimica acta》1981,45(2):201-206

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.  相似文献   

Constantes de formation des complexes hydroxydés de l'aluminium en solution aqueuse de 20 a 70°C     

Yves Couturier  Gil Michard  Gérard Sarazin 《Geochimica et cosmochimica acta》1984,48(4):649-659

Stability constants of hydroxocomplexes of Al(III):Al(OH)²⁺ and A1(OH)₄^? have been measured in the 20–70°C temperature range by reactions involving only dissolved species. The stability constant ${}^1\text{K}{}_1$ of the first complex ion is studied by measuring pH of solutions of aluminium salts at several concentrations. ${}^1\text{β}{}_4$ of aluminate ion is deduced from equilibrium constants of the reaction between the trioxalato aluminium (III) complex ion and Al³⁺ in acid medium, and between the same complex ion and A1(OH)₄^? in alkaline medium. The K values and the associated ΔH are ${}^1\text{K}{}_1\text{= 10}{}^{\mathrm{?5.00}}$ and ΔH₁ = 11.8 Kcal; ${}^1\text{β}{}_4\text{= 10}{}^{\mathrm{?22.20}}$ and ΔH₄ = 42.45 Kcal. These last results are not in agreement with the values of recent tables for $\text{ΔG}{}^0\text{?}$ and $\text{ΔH}{}^0\text{?}$ of Al³⁺ and Al(OH)₄^?. We suggest a consistent set of data for dissolved and solid Al species and for some aluminosilicates.  相似文献   

Solubility product of galena at 298°K: A possible explanation for apparent supersaturation in nature     

A.D. Uhler  G.R. Helz 《Geochimica et cosmochimica acta》1984,48(6):1155-1160

The synthetic chelating agent ethylenediaminetetraacetic acid (EDTA) has been used to evaluate the stoichiometric solubility product of galena (PbS) at 298°K: $\text{K}{}_{\mathrm{s2}}\text{=}{}^{\mathrm{a}}\text{Pb}{}^{\mathrm{2+}}{}^{\mathrm{a}}\text{HS}{}^{\mathrm{?}}{}^{\mathrm{a}}\text{H}{}^{\mathrm{+}}$ This method circumvents the possible uncertainties in the stoichiometry and stability of lead sulfide complexes. At infinite dilution, $\text{Log K}{}_{\mathrm{s2}}\text{= ?12.25 ±0.17}$, and at an ionic strength corresponding to seawater ($\text{I = 0.7 M}$), $\text{Log K}{}_{\mathrm{s2}}\text{= ?11.73 ± 0.05}$. Using the value of $\text{K}{}_{\mathrm{s2}}$ at infinite dilution, and the free energies of formation of HS^? and Pb²⁺ at 298°K (literature values), the free energy of formation of PbS at 298°K is computed to be $\text{?79.1 ± 0.8 KJ/mol (?18.9 Kcal/mol)}$. Galena is shown to be more than two orders of magnitude more soluble than indicated by calculations based on previous thermodynamic data.  相似文献   

The effect of pressure on the solubility of minerals in water and seawater     

Frank J Millero 《Geochimica et cosmochimica acta》1982,46(1):11-22

The effect of presure on the solubility of minerals in water and seawater can be estimated from In where the volume (ΔV) and compressibility (ΔK) changes at atmospheric pressure (P = 0) are given by Values of the partial molal volume ($\text{V}\text{?}$) and compressibilty ($\text{K}\text{?}$) in water and seawater have been tabulated for some ions from 0 to 50°C. The compressibility change is quite large (~10 × 10^?3 cm³ bar^?1 mol^?1) for the solubility of most minerals. This large compressibility change accounts for the large differences observed between values of ΔV obtained from linear plots of In K_sp versus P and molal volume data (Macdonald and North, 1974; North, 1974). Calculated values of $\text{K}{}^{\mathrm{P}}{}_{\mathrm{sp}}\text{K}{}^{\mathrm{o}}{}_{\mathrm{sp}}$ for the solubility of CaCO₃, SrSO₄ and CaF₂ in water were found to be in good agreement with direct measurements (Macdonald and North, 1974). Similar calculations for the solubility of minerals in seawater are also in good agreement with direct measurements (Ingle, 1975) providing that the surface of the solid phase is not appreciably altered.  相似文献   

Spallation production of ³He, ²¹Ne,and ³⁸Ar from target elements in the Bruderheim chondrite     

D.D Bogard  P.J Cressy 《Geochimica et cosmochimica acta》1973,37(3):527-546

The concentrations of noble gas isotopes of He, Ne and Ar have been measured in eight mineral separates of the Bruderheim chondrite. The cosmic-ray-produced nuclides ²¹Ne and ³⁸Ar were correlated by a computer least-squares fitting program with the elemental composition in each separate of potential targets for nuclear production yielding the following production equations: $\text{[}{}^{21}\text{Ne, 10}{}^{\mathrm{?8}}\text{cm}{}^3\text{/g] = k(0.45[Mg] + 0.085[Si] + 0.060[S] + 0.017[Ca] + 0.0044[Fe + Ni])}$; $\text{[}{}^{38}\text{Ar, 10}{}^{\mathrm{?8}}\text{cm}{}^3\text{/g] = k(2.6[K] + 0.37[Ca] + 0.08[Ti + Cr + Mn] + 0.021[Fe + Ni])}$ with elemental concentrations in weight per cent and k equal to the reciprocal of the cosmic-ray exposure age of Bruderheim. The P(S)/P(Cr + Mn + Fe + Ni) weight production ratio for ³He was determined to be 1.53; relative productions of ³He from O, Mg and Si and ²¹Ne from Al proved to be incalculable.  相似文献   

Concentration of Mn and separation from Fe in sediments—I. Kinetics and stoichiometry of the reaction between birnessite and dissolved Fe(II) at 10°C     

Dieke Postma 《Geochimica et cosmochimica acta》1985,49(4):1023-1033

Redox reactions between Fe²⁺ in solution and Mn-oxides are proposed as a mechanism for concentration of Mn in sediments both during weathering and diagenesis in marine sediments, e.g. the formation of Mn-nodules.If such a mechanism is to be effective, then reaction rates between Fe²⁺ and Mn-oxides should be fast. The kinetics and stoichiometry of the reaction between dissolved Fe²⁺ and synthetically prepared birnessite (Mn₇O₁₃·5H₂O) were studied experimentally in the pH range 3–6.Results show a stoichiometry which at pH < 4 conforms to a simple reaction between Fe²⁺ and birnessite, releasing Mn²⁺ and Fe³⁺ to the solution. At pH > 4 FeOOH is precipitated and excess Fe²⁺ consumption compared to the theoretical stoichiometry is observed. The excess Fe²⁺ consumption is not due to a formation of a quantitative MnOOH layer but rather to adsorption.Reaction kinetics are very fast at pH < 4 and change at pH 4 to a slower mechanism. At pH > 4 the reaction is fast initially until 17% of the bimessite has dissolved and changes then to a slower stage. The later stage can be described by the equation: $\text{J = km}{}_0\text{(H}{}^{\mathrm{+}}\text{)}{}^{\mathrm{?0.45}}\text{[Fe}{}^{\mathrm{2+}}\text{]}{}^{\mathrm{\gamma }}\text{(}\text{m}\text{m}{}_0\text{)}{}^{\mathrm{\beta }}$ where J is the overall rate of Mn²⁺ release, m₀ and m the mass of birnessite at time t = 0 and t > 0, β = 6.76?0.94 pH and γ has values of 0.76 at pH 5 and 0.39 at pH 6. The rate constant k is 7.2·10^?7 moles s^?1 g^?1 (moles/1)^?0.31 at pH 5 and 9.6·10^?8 moles s^?1 g^?1 (moles/1)^0.06 at pH 6.Diffusion calculations show that the rate is controlled by surface reaction and it is tentatively proposed that the availability of vacancies in octahedral [MnO₆]sheets of the birnessite surface could be rate controlling. It is concluded that reactions between Fe(II) and birnessite, and probably other Mn-oxides, are fast enough to be important in natural environments at the earth surface.  相似文献   

An electrochemical study of Ni²⁺, Co²⁺, and Zn²⁺ ions in melts of composition CaMgSi₂O₆     

Krystyna W. Semkow  Ronald A. Rizzo  Larry A. Haskin  David J. Lindstrom 《Geochimica et cosmochimica acta》1982,46(10):1879-1889

Cyclic voltammetry has been done for Ni²⁺, Co²⁺, and Zn²⁺ in melts of diopside composition in the temperature range 1425 to 1575°C. Voltammetric curves for all three ions excellently match theoretical curves for uncomplicated, reversible charge transfer at the Pt electrode. This implies that the neutral metal atoms remain dissolved in the melt. The reference electrode is a form of oxygen electrode. Relative to that reference assigned a reduction potential of 0.00 volt, the values of standard reduction potential for the ions are $\text{E}{}^1\text{(}\text{Ni}{}^{\mathrm{2+}}\text{Ni}{}^0\text{,}\text{diopside}\text{, 1500°C) = ?0.32 ± .01}\text{V}$, $\text{E}{}^1\text{(}\text{Co}{}^{\mathrm{2+}}\text{Co}{}^0\text{,}\text{diopside}\text{, 1500°C) = ?0.45 ± .02}\text{V}$, and $\text{E}{}^1\text{(}\text{Zn}{}^{\mathrm{2+}}\text{Zn}{}^0\text{,}\text{diopside}\text{, 1500°C) = ?0.53 ± .01}\text{V}$. The electrode reactions are rapid, with first order rate constants of the order of 10^?2 cm/sec. Diffusion coefficients were found to be 2.6 × 10^?6 cm²/sec for Ni²⁺, 3.4 × 10^?6 cm²/sec for Co²⁺, and 3.8 × 10^?6 cm²/sec for Zn²⁺ at 1500°C. The value of $\text{E1}$ ($\text{Ni}{}^{\mathrm{2+}}\text{Ni}{}^0$, diopside) is a linear function of temperature over the range studied, with values of ?0.35 V at 1425°C and ?0.29 V at 1575°C. At constant temperature the value of $\text{E}{}^1\text{(}\text{Ni}{}^{\mathrm{2+}}\text{Ni}{}^0\text{, 1525°C}$) was not observed to vary with composition over the range CaO · MgO · 2SiO₂ to CaO·MgO·3SiO₂ or from 1.67 CaO·0.33MgO·2SiO₂ to 0.5 CaO·1.5MgO·2SiO₂. The value for the diffusion coefficient for Ni²⁺ decreased by an order of magnitude at 1525°C over the compositional range CaO · MgO · 1.25SiO₂ to CaO · MgO · 3SiO₂. This is consistent with a mechanism by which Ni²⁺ ions diffuse by moving from one octahedral coordination site to another in the melt, with the same Ni²⁺ species discharging at the cathode regardless of the SiO₂ concentration in the melt.  相似文献   

Use of Pitzer's equations to determine the media effect on the formation of lead chloro complexes     

Frank.J. Millero  Robert H. Byrne 《Geochimica et cosmochimica acta》1984,48(5):1145-1150

The spectrophotometric measurements of chloro complexes of lead in aqueous HCl, NaCl, MgCl₂ and CaCl₂ solutions at 25°C have been analyzed using Pitzer's specific interaction equations. Parameters for activity coefficients of the complexes PbCl⁺, PbCl₂⁰ and PbCl₃^? have been determined for the various media. Values of $\text{K}{}_1\text{= 30.0 ± 0.6}$, $\text{K}{}_2\text{= 106.7 ± 2.1}$ and $\text{K}{}_3\text{= 73.0 ± 1.5}$ were obtained for the cumulative formation constants. [$\text{Pb}{}^{\mathrm{2+}}\text{+ nCl}{}^{\mathrm{?}}\text{→ PbCl}{}_{\mathrm{n}}{}^{\mathrm{2?n}}\text{)}$]. These values are in reasonable agreement with literature data. The Pitzer parameters for the PbCl ion pairs in various media were used to calculate the speciation of Pb²⁺ in an artificial seawater solution.  相似文献   

Extreme fractionation of 234U238U and 230Th234U in spring waters,sediments, and fossils at the Pomme de Terre Valley,southwestern Missouri     

Barney J Szabo 《Geochimica et cosmochimica acta》1982,46(9):1675-1679

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.  相似文献