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.     

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

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.     

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.     

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.     

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.     

Thorium and radium isotopic relationships in manganese nodules and sediments at MANOP Site S

Relationships among Th and Ra isotopes in nodule, sediment and water phases at MANOP Site S establish the most likely source for Th in the nodules, the frequency of nodule turning, and the similarity of micro and macro nodules. Manganese nodules and bottom waters have ${}^{230}\text{Th}{}^{232}\text{Th}$ activity ratios considerably higher than other phases at this site suggesting that sea water is the likely source of Th for the nodules. Similar ${}^{230}\text{Th}{}^{232}\text{Th}$ activity ratios in nodule tops and bottoms and in certain cases departure from expected ${}^{226}\text{Ra}{}^{230}\text{Th}$ activity ratios in nodule tops and bottoms indicate that the nodules rotate every one to ten thousand years. The micro nodules have diffusion coefficients of Ra similar to macro nodule bottoms. I suggest that they may act as a carrier phase for transporting metals through oxic sediments to nodules.     

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

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

Aqueous oxidation-reduction kinetics associated with coupled electron-cation transfer from iron-containing silicates at 25°C

Mechanisms and kinetics of aqueous $\text{Fe}{}^{\mathrm{+2}}\text{Fe}{}^{\mathrm{+3}}$ oxidation-reduction and dissolved O₂ interaction in the presence of augite, biotite and hornblende were studied in oxic and anoxic solutions at pH 1–9 at 25°C. Oxidation of surface iron on the minerals coincided with both surface release of Fe⁺² and by reduction of Fe⁺³ in solution. Reaction with iron silicates consumed dissolved oxygen at a rate that increased with decreasing pH. Both Fe⁺³ and O₂ consumption were shown to be controlled by coupled electron-cation transfer reactions of the form;

$\text{[}\text{Fe}{}^{\mathrm{+2}}\text{,}\text{1}\text{zM}{}^{\mathrm{+z}}\text{]}{}_{\mathrm{silicate}}\text{+}\text{Fe}{}^{\mathrm{+3}}\text{→ [}\text{Fe}{}^{\mathrm{+3}}\text{]}{}_{\mathrm{silicate}}\text{+}\text{Fe}{}^{\mathrm{+2}}\text{+}\text{1}\text{zM}{}^{\mathrm{+z}}$

and

$\text{[}\text{Fe}{}^{\mathrm{+2}}\text{,}\text{1}\text{zM}{}^{\mathrm{+z}}\text{]}{}_{\mathrm{silicate}}\text{+}\text{H}{}^{\mathrm{+}}\text{+}\text{1}\text{4}\text{O}{}_2\text{→ [}\text{Fe}{}^{\mathrm{+3}}\text{]}{}_{\mathrm{silicate}}\text{+}\text{1}\text{zM}{}^{\mathrm{+z}}\text{+}\text{1}\text{2}\text{H}{}_2\text{O}$

where M is a cation of charge +z. The spontaneous reduction of aqueous Fe⁺³in the presence of precipitated Fe(OH)₃bracketed the surface oxidation standard half cell between +0.33 and +0.52 volts. Concurrent hydrolysis reactions involving cation release from the iron silicates were suppressed by the above reactions. Calculated oxidation depths in the minerals varied between 12 and 80Å and were apparently controlled by rates of solid-state cation diffusion.     

Fission track studies of xenolithic chondrites: implications regarding brecciation and metamorphism

We have studied fission tracks in phosphates from one gas-poor chondrite and three gas-rich chondrites to determine their thermal history and brecciation time scales. More than 70 percent of the tracks in whitlockites in these meteorites are due to the decay of extinct Pu²⁴⁴.Whitlockites separated from Bhola, a gas-poor chondrite, have $\text{ρ}{}_{\mathrm{Pu}}\text{ρ}{}_{\mathrm{U}}\text{= 2.6–5.2}$ and a model fission track age of 4.0 Gyr for a $\text{(}\text{Pu}\text{U}\text{)}{}_{\mathrm{4.55Gyr}}\text{= 0.045}$. Brecciation of the Bhola meteorite must have occurred at ?4.3 Gyr to account for the metal data (Scott and Rajan, 1981). A minimum cooling rate of $\text{0.9}{}_{\mathrm{–0.2}}{}^{0.3}\text{K}\text{Myr}$ in the temperature interval 800 to 300 K obtained from the track data is a factor of seven higher than the metallographic cooling rate ($\text{0.1}\text{K}\text{Myr}$).For the gas-rich chondrites, the $\text{ρ}{}_{\mathrm{Pu}}\text{ρ}{}_{\mathrm{U}}$ in whitlockites are: Weston, 32–148; Fayetteville, 21–227; and St. Mesmin, 26–137. Whitlockites from all these meteorites give model fission track ages of 4.4 Gyr assuming a $\text{(}\text{Pu}\text{U}\text{)}{}_{\mathrm{4.55\; Gyr}}\text{= 0.045}$. The final brecciation event definitely did not reset the track clock in phosphates of St. Mesmin. Our data suggest that it is also true for Weston and Fayetteville. We conclude that our observed fission track ages date the end of metamorphic cooling in the meteorite parent bodies and support the planetesimal model for the formation of xenolithic chondrites.     

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

Isotopic fractionation as great as 1600% exists between ²³⁴U and ²³⁸U in spring waters, sediments, and fossils in the Pomme de Terre Valley, southwestern Missouri. The activity ratios of ${}^{234}\text{U}{}^{238}\text{U}$ in five springs range from 7.2 to 16 in water which has been discharged for at least the past 30,000 years. The anomalies in ${}^{234}\text{U}{}^{238}\text{U}$ ratio in deep water have potential usefulness in hydrologic investigations in southern Missouri. Clayey units overlying the spring bog sediments of Trolinger Spring are enriched in ²³⁰Th relative to their parent ²³⁴U by as much as 720%. The results indicate that both preferential displacement via alpha recoil ejection and the preferential emplacement via recoiling and physical entrapment are significant processes that are occurring in the geologic environment.     

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

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

The extent of oxygen isotope exchange between clay minerals and sea water

The extent of oxygen isotopic exchange between detrital clay minerals and sea water was investigated by analyzing $\text{O}{}^{18}\text{O}{}^{16}$ ratios of separated fine-grained size fractions of deep-sea sediments from three North Pacific ocean cores. Isotopic results were interpreted according to models based on the assumption that the extent of isotopic exchange should increase with decreasing particle size and increasing time of exchange between the sediment and sea water. The data indicate that information concerning the provenance and mode of formation of detrital clay minerals can be obtained from the $\text{O}{}^{18}\text{O}{}^{16}$ ratios of the coarser-than-0.1 μm fraction of deep-sea sediments younger than several million years and the finer-than-0.1 μm fraction of deep-sea sediments younger than several tens of thousands of years. Furthermore, if the extent of chemical reaction between detrital clays and sea water is similar to the extent of oxygen isotopic exchange, such reaction may be important in regulating the chemistry of sea water.     

Interstitial water chemistry in the sediments of Saanich Inlet

Measurements of nutrients and trace metals are used to examine the processes controlling their distributions in the interstitial waters of Saanich Inlet. Samples were collected using both in situ and squeezing techniques with excellent agreement. Additional measurements of porosity, organic carbon and sedimentation rate by ²¹⁰Pb are used in conjunction with the nutrient measurements to test the equation for the diagenesis of organic matter in fine-grained, organic-rich and rapidly-accumulating sediments.Organic carbon and sulfate decrease with depth in the sediment whereas ammonia and alkalinity increase. In the zone of sulfate reduction (0–20 cm) the rate constants for sulfate reduction ($\text{k}{}_{\mathrm{s}}$), ammonia production ($\text{k}{}_{\mathrm{N}}$) and organic carbon decomposition ($\text{k}{}_{\mathrm{c}}$) agree within a factor of two. Our calculations indicate, however, that this is fortuitous since the observed decrease in paniculate organic carbon is insufficient to account for the sulfate consumption. Sulfate must also be consumed by reaction with methane diffusing up from the underlying sediments. The rate constant for sulfate reduction using particulate organic carbon is lower than a modelled rate encompassing all organic species, including methane.The rate constant for ammonia production ($\text{k}{}_{\mathrm{N}}$) decreases by an order of magnitude when sulfate is completely depleted and methane production dominates.Thermodynamic calculations suggest that the interstitial waters are saturated or supersaturated with respect to all forms of iron ‘monosulfides’, apatite and rhodochrosite.     

Transfer and exchange equilibria in a portion of the pyroxene quadrilateral as deduced from natural and experimental data

Differences in the chemical composition of metamorphic and igneous pyroxene minerals may be attributed to a transfer reaction, which determines the Ca content of the minerals, and an exchange reaction, which determines the relative Mg:Fe²⁺ ratios. Natural data for associated Ca pyroxene (Cpx) and orthopyroxene (Opx) or pigeonite are combined with experimental data for Fe-free pyroxenes, to produce the following equations for the Cpx slope of the solvus surface: $\text{> 1080°C: T =}\text{1000}\text{(0.468 + 0.246X}{}^{\mathrm{Cpx}}\text{? 0.123 ln (1–2 [Ca]))}$$\text{< 1080°C: T =}\text{1000}\text{(0.054 + 0.608X}{}^{\mathrm{Cpx}}\text{? 0.304 ln (1–2 [Ca]))}$, and the following equation for the temperature-dependence of the Mg-Fe distribution coefficient: $\text{T =}\text{1130}\text{(}\text{ln}\text{K}{}_{\mathrm{p}}\text{+ 0.505)}$, where T is absolute temperature, X is $\text{Fe}{}^{\mathrm{2+}}\text{(Mg + Fe}{}^{\mathrm{2+}}\text{))}$, [Ca] is $\text{Ca}\text{(Ca + Mg + Fe}{}^{\mathrm{2+}}\text{)}$ in Cpx, and K_D is the distribution coefficient, defined as $\text{X}{}^{\mathrm{Opx}}\text{/(1 ? X}{}^{\mathrm{Opx}}\text{) ÷ X}{}_{\mathrm{Cpx}}\text{/(1 ?}{}^{\mathrm{Cpx}}\text{)}$.The transfer and exchange equations form useful temperature indicators, and when applied to 9 sets of well-studied rocks, yield pairs of temperatures that are in good agreement. For example, temperatures obtained for the Bushveld Complex are 1020°C (solvus equation) and 980°C (exchange equation), based on 7 specimens. The uncertainty in these numbers, due to precision and accuracy errors, is estimated to be ±60°.     

Noble gas concentrations and cosmic ray exposure ages of eight recently fallen chondrites

Abundances and isotopic compositions of He, Ne, Ar, and Xe have been measured in eight recently fallen chondrites. Ratios of concentrations of cosmic ray-produced ³He, ²¹Ne, ²²Ne and ³⁸Ar indicate that all eight samples experienced less than average cosmic ray shielding. ³He and ²¹Ne exposure ages were calculated using shielding corrected chondritic production rates and the measured ${}^{22}\text{Ne}{}^{21}\text{Ne}$. Exposure ages calculated from ${}^{22}\text{Na}{}^{22}\text{Ne}$ and ${}^{26}\text{Al}{}^{21}\text{Ne}$ ratios and constant relative production rates show a bias between the two ages due to variations in ${}^{22}\text{Na}{}^{26}\text{Al}$. Arguments are presented that this bias is due to irradiation hardness differences, and therefore the use of constant values for both the ${}^{22}\text{Na}{}^{22}\text{Ne}$ and ${}^{26}\text{Al}{}^{21}\text{Ne}$ production ratios is not permitted. Dwaleni, Swaziland, was found to be an unusual gas-rich chondrite with high concentrations of solar-derived He and Ne and planetary-type Xe.     

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

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