Distribution and relationship of radionuclides to streambed gravels in a small watershed

In White Oak Creek watershed in eastern Tennessee, the radionuclides⁶⁰Co,⁹⁰Sr, and¹³⁷Cs were retained by streambed gravels on different sites:⁶⁰Co was associated with manganese in the hydrous oxide coatings on rocks and minerals;⁹⁰Sr occurred primarily as an exchangeable cation although small amounts were held in a nonexchangeable form; and¹³⁷Cs was held very selectively, presumably by illite in shale fragments composing the sediment. The distribution of radionuclides on sediments was size dependent: the 0.85–3.35 mm fine-gravel fraction was higher in radionuclide concentration than the sand fraction. An areal survey of radionuclide concentrations on streambed gravels from throughout the watershed, located numerous contamination sources. These radionuclide concentrations, when combined with both distribution coefficients of radionuclides between gravel and water and drainage area, were used to rank subsections of the watershed by their relative contribution to the overall contamination of the watershed. For⁹⁰Sr, this ranking procedure agreed with the measured discharges of subsections of the watershed which are routinely monitored. Research sponsored by the Oak Ridge National Laboratory (operated by U.S. Department of Energy under contract W-7405-eng-26 with Union Carbide Corporation. Publication No. 2017, Environmental Sciences Division, ORNL.     

An analysis of naturally occurring radionuclides and <Superscript>137</Superscript>Cs in the soils of urban areas using gamma-ray spectrometry

This study of environmental radioactivity was carried out in the soils of an urban area. Naturally occurring gamma-emitting radionuclides and man-made ¹³⁷Cs were found in the soil profiles collected from four parks in the central Belgrade city area and the soil layer was examined every 10 cm and to a depth of 50 cm. Radioisotope activity concentrations (Bq kg^?1) in the samples of urban soil using the gamma-ray spectrometry method were in the range of 14–46 for ²³⁸U, 33–50 for ²²⁶Ra, 29–63 for ²¹⁰Pb, 1.2–3.4 for ²³⁵U, 28–50 for ²³²Th, 424–576 for ⁴⁰K and 0.7–35.8 for ¹³⁷Cs. Some of the basic physicochemical soil properties (pH, organic matter content, calcium-carbonate content, particle size distribution) were determined to investigate the impact on the vertical distribution of radionuclides. The results of this investigation showed that variations of activity concentration ratios of radionuclides that belong to the same (²³⁸U/²²⁶Ra) or different radioactive series (²³²Th/²²⁶Ra; ²³⁵U/²³⁸U), including ²¹⁰Pb/¹³⁷Cs ratios could well be explained by the properties of the soil. Alkaline pH reaction, the accumulation of organic matter in the uppermost and of carbonates in the deepest layers of urban soil had an effect on ²³⁸U/²²⁶Ra, and ²¹⁰Pb/¹³⁷Cs activity concentration ratio values, while ²³²Th/²²⁶Ra and partially ²³⁵U/²³⁸U ratios were associated with the particle sizes vertical distribution. A study of radionuclides in the samples of leaves of two deciduous tree species common for these parks was also conducted and ²¹⁰Pb and ⁴⁰K were found concentrated in leaves rather than other investigated radionuclides.     

Experimental and modelling studies of caesium sorption on illite

A natural illite (illite du Puy) was purified and converted to the homo-ionic Na form. The conditioned Na–illite was characterised in terms of its mineralogy, chemical inventory, and surface properties. The structural formula was determined from EDS analyses (SEM/TEM) and bulk chemistry. A cation exchange capacity of 127 mEq/kg was determined by the Na isotope dilution method at neutral pH.The sorption of Cs was measured as a function of NaClO₄ background electrolyte concentration (1.0, 0.1 and 0.01 M), Cs concentration and pH in the range ≈3 to ≈10. Before obtaining these measurements the kinetics of Cs uptake were determined at initial concentrations of 2 × 10⁻⁸ M and 7 × 10⁻⁵ M, representing the extremes of the range investigated, and was found to be concentration dependent. The supernatant solutions after centrifugation were analysed for major cations in all of the sorption tests.A two-site cation exchange model was developed to describe the sorption of Cs over the whole range of experimental conditions. The two-site types were termed frayed edge sites, FES (high affinity/low capacity) and type II sites (low affinity/high capacity). At low NaClO₄ concentrations, Cs sorption decreased at pH values less than neutral. This was interpreted in terms of competitive effects from H, and K released by the partial dissolution of illite, which cannot be avoided at low and high pH values. Selectivity coefficient values for Cs–Na, Cs–K, K–Na, and H–Na exchange equilibria on the FES sites, and Cs–Na exchange on the type II sites are given for illite together with the corresponding site capacities.     

A model of radionuclide transfer by groundwater on the territory of the Russian Research Centre Kurchatov Institute

The convective transfer of ¹³⁷Cs and ⁹⁰Sr by groundwater on the territory of the Russian Research Centre Kurchatov Institute (RRCKI) was modeled. Geological data on the RRCKI site and possible sources of radionuclides show that the uppermost aquifer, composed of Quaternary sediments, is the most probable region of spreading of radioactive contamination. Since the lateral migration of radionuclides is predominant, a 2D horizontal model was used for the forecasting of spreading of radioactive contaminants in the subsurface medium. Transient or long-term repositories of radioactive materials at the RRCKI site (concentrated sources) and aquifer rocks contaminated in the course of removal of radionuclides from these repositories (distributed source) are responsible for groundwater pollution. The initial ¹³⁷Cs and ⁹⁰Sr distributions used in the forecasting of radionuclide migration were determined from their contents in core samples taken from wells drilled in contaminated areas of the RRCKI site. The zone of radionuclide migration is limited by poorly permeable moraine loam from below and by the water table from above. To determine the upper and lower boundaries, these surfaces were mapped in plan view. The data of meteorological observations over a long period were used to map the intensity of precipitation in the studied territory. The density of rocks in the uppermost aquifer and partition coefficients of radionuclides between rocks and groundwater were estimated from the data of laboratory examination of the core samples. The available data on the permeability of rock samples and the results of test pumping out of some wells were involved in the consideration. The results obtained and the data on the water table allowed us to define a gauge problem for determining the distribution of the filtration coefficient in the uppermost aquifer. This problem was solved taking the intensity of precipitation into account. The properties of the uppermost aquifer and the initial radionuclide distribution therein were used as initial data for modeling ¹³⁷Cs and ⁹⁰Sr migration on the territory of the RRCKI over 50 years.     

Naturally occurring radionuclides and their geochemical interactions at a geothermal site in the North German Basin

The activities of the most common, naturally occurring radionuclides ²³⁸U, ²²⁶Ra, ²¹⁰Pb, ²²⁸Ra, ²²⁸Th, and ⁴⁰K were measured by gamma-ray spectrometry in samples from reservoir rocks, geothermal fluids, and mineral precipitates at the geothermal research site Groß Schönebeck (North German Basin). Results demonstrated that the specific activity of the reservoir rock is within the range of the mean concentration in the upper earth crust of <800 Bq/kg for ⁴⁰K and <60 Bq/kg for radionuclides of the ²³⁸U and ²³²Th series, respectively. The geothermal fluid showed elevated activity concentrations (up to 100 Bq/l) for ²²⁶Ra, ²¹⁰Pb, and ²²⁸Ra, as compared to concentrations found in natural groundwater. Their concentration in filter residues even increased up to 100 Bq/g. These residues contain predominantly two different mineral phases: a Sr-rich barite (Sr, BaSO₄) and laurionite (PbOHCl), which both precipitate upon cooling from the geothermal fluid. Thereby they presumably enrich the radionuclides of Ra (by substitution of Ba) and Pb. Analysis of these precipitates further showed an increased ²²⁶Ra/²²⁸Ra ratio from around 1–1.7 during the initial months of fluid production indicating a change in fluid composition over time which can be explained by different contributions of stimulated reservoir rock areas to the overall produced fluid.     

Radiological monitoring and statistical approach of primordial and anthropogenic radionuclides in surface soil of Mami-water site in the Western Cameroon

The study referred to measure activity concentrations of some primordial radionuclides and anthropogenic of ¹³⁷Cs in soil samples of Mami-water in the Menoua subdivision, Dschang employing gamma-ray spectrometry-based characterized Broad Energy Germanium (BE6350) detector and a comparison of radiological and safety impact parameters on human due to primordial radioactivity in soil with some internationally approved values. In addition, statistical analysis of primordial radionuclides of ²²⁶Ra, ²³²Th and ⁴⁰K was performed to evaluate the distribution and the interrelation of radionuclides. Samples were randomly collected from a depth of about 0 to 5 cm from the top surface layer. Each of the sampling points was considered as being overlaid with a grid and subdivided into cells. The observed radioactivity level of ²²⁶Ra, ²³²Th and ⁴⁰K in the investigated soil samples was compared with some published data available in some countries including Cameroon and observed varying within some reported data of radioactivity in soil from bauxite ore deposit. ²³⁵U and ¹³⁷Cs were found in very few samples with a very low average of activity concentrations. In the majority of the samples, the observed radiological safety parameters seem to be greater than the internationally approved values. Consequently, using bricks made of soil as building materials might lead to an increase in radiation risk for the population. Multivariate statistical analysis of activity concentrations of primordial radionuclides performed showed an asymmetrical distribution with more peaked than Gaussian distribution and relatively flatter distribution of radionuclides in soil. In addition, a good positive interrelation between ²²⁶Ra and ²³²Th was observed and a weak negative one observed between ⁴⁰K and ²²⁶Ra–²³²Th.     

Formation of freshwater Fe-Mn coatings on gravel and the behavior of 60Co, 90Sr,and 137Cs in a small watershed

Iron and manganese oxide coatings are actively forming on stream substrates in the White Oak Creek watershed in East Tennessee. Although oxidizing conditions are required for Fe-Mn oxide precipitation, coatings accumulate only if dissolved iron and manganese exceed 50 μg/L. Below this, coatings are lost by abrasion as fast as or faster than they form. Annual rates of formation of 3 mg/g on substrate (gravel) were observed. Manganese is dissolved from coatings between Eh values of 100 to 300 mV and below 1 mg/L dissolved O₂ at pH 6.5 to 7.5. Iron oxides can be precipitated under these conditions.Uncontaminated gravels with oxide coatings (composed of illite, quartz, and feldspar) adsorbed radionuclides rapidly from waters below MPC (Maximum Permissible Concentration) levels. Contaminated gravels placed in uncontaminated waters lost ⁶⁰Co by abrasion in oxidizing conditions and by dissolution of manganese coatings in reducing conditions. Exchangeable ⁹⁰Sr was completely lost after one month whereas nonexchangeable ⁹⁰Sr was lost more slowly; ¹³⁷Cs was totally retained by the gravels. Gravels such as these can be used to monitor the radionuclide content of waters in the environment.     

Sensitivity assessment of strontium isotope as indicator of polluted groundwater for hydraulic fracturing flowback fluids produced in the Dameigou Shale of Qaidam Basin

Hydrogeochemical processes that would occur in polluted groundwater and aquifer system, may reduce the sensitivity of Sr isotope being the indicator of hydraulic fracturing flowback fluids(HFFF) in groundwater. In this paper, the Dameigou shale gas field in the northern Qaidam Basin was taken as the study area, where the hydrogeochemical processes affecting Sr isotope was analysed. Then, the model for Sr isotope in HFFF-polluted groundwater was constructed to assess the sensitivity of Sr isotope as HFFF indicator. The results show that the dissolution can release little Sr to polluted groundwater and cannot affect the εSr(the deviation of the 87 Sr/86 Sr ratio) of polluted groundwater. In the meantime, cation exchange can considerably affect Sr composition in the polluted groundwater. The Sr with low εSr is constantly released to groundwater from the solid phase of aquifer media by cation exchange with pollution of Quaternary groundwater by the HFFF and it accounts for 4.6% and 11.0% of Sr in polluted groundwater when the HFFF flux reaches 10% and 30% of the polluted groundwater, respectively. However, the Sr from cation exchange has limited impact on Sr isotope in polluted groundwater. Addition of Sr from cation exchange would only cause a 0.2% and 1.2% decrease in εSr of the polluted groundwater when the HFFF flux reaches 10% and 30% of the polluted groundwater, respectively. These results demonstrate that hydrogeochemical processes have little effect on the sensitivity of Sr isotope being the HFFF indicator in groundwater of the study area. For the scenario of groundwater pollution by HFFF, when the HFFF accounts for 5%(in volume percentage) of the polluted groundwater, the HFFF can result in detectable shifts of εSr(ΔεSr=0.86) in natural groundwater. Therefore, after consideration of hydrogeochemical processes occurred in aquifer with input of the HFFF, Sr isotope is still a sensitive indicator of the Quaternary groundwater pollution by the HFFF produced in the Dameigou shale of Qaidam Basin.     

Clay mineral weathering and contaminant dynamics in a caustic aqueous system: I. Wet chemistry and aging effects

Caustic high level radioactive waste induces mineral weathering reactions that can influence the fate of radionuclides released in the vicinity of leaking storage tanks. The uptake and release of Cs^I and Sr^II were studied in batch reactors of 2:1 layer-type silicates—illite (Il), vermiculite (Vm) and montmorillonite (Mt)—under geochemical conditions characteristic of leaking tank waste at the Hanford Site in WA (0.05 m Al_T, 2 m Na⁺, 1 m NO₃⁻, pH ∼14, Cs and Sr present as co-contaminants). Time series (0 to 369 d) experiments were conducted at 298 K, with initial [Cs]₀ and [Sr]₀ concentrations from 10⁻⁵ to 10⁻³ mol kg⁻¹. Clay mineral type affected the rates of (i) hydroxide promoted dissolution of Si, Al and Fe, (ii) precipitation of secondary solids and (iii) uptake of Cs and Sr. Initial Si release to solution followed the order Mt > Vm > Il. An abrupt decrease in soluble Si and/or Al after 33 d for Mt and Vm systems, and after 190 d for Il suspensions was concurrent with accumulation of secondary aluminosilicate precipitates. Strontium uptake exceeded that of Cs in both rate and extent, although sorbed Cs was generally more recalcitrant to subsequent desorption and dissolution. After 369 d reaction time, reacted Il, Vm and Mt solids retained up to 17, 47 and 14 mmol kg⁻¹ (0.18, 0.24 and 0.02 μmol m⁻²) of Cs, and 0, 27 and 22 mmol kg⁻¹ (0, 0.14 and 0.03 μmol m⁻²) Sr, respectively, which were not removed in subsequent Mg exchange or oxalic acid dissolution reactions. Solubility of Al and Si decreased with initial Cs and Sr concentration in Mt and Il, but not in Vm. High co-contaminant sorption to the Vm clay, therefore, appears to diminish the influence of those ions on mineral transformation rates.     

The geochemistry of Ca,Sr, Ba and Ra sulfates in some deep brines from the Palo Duro Basin,Texas

The geochemistry of Ca, Sr, Ba and Ra sulfates in some deep brines from the Palo Duro Basin of north Texas, was studied to define geochemical controls on radionuclides such as ⁹⁰Sr and ²²⁶Ra. Published solubility data for gypsum, anhydrite, celestite, barite and RaSO₄ were first reevaluated, in most cases using the ion interaction approach of Pitzer, to determine solubility products of the sulfates as a function of temperature and pressure. Ionic strengths of the brines were from 2.9 to 4.8 m, their temperatures and pressures up to 40°C and 130 bars. Saturation indices of the sulfates were computed with the ion-interaction approach in one brine from the arkosic granite wash fades and four from the carbonate Wolfcamp Formation. All five brines are saturated with respect to gypsum, anhydrite and celestite, and three of the five with respect to barite. All are undersaturated by from 5 to 6 orders of magnitude with respect to pure RaSO₄. ²²⁶Ra concentrations in the brines, which ranged from 10^?11.3 to 10^?12.7 m, are not controlled by RaSO₄ solubility or adsorption, but possibly by the solubility of trace Ra solid solutions in sulfates including celestite and barite.     

US Geological Survey research on the environmental fate of uranium mining and milling wastes

Studies by the US Geological Survey (USGS) of uranium mill tailings (UMT) have focused on characterizing the forms in which radionuclides are retained and identifying factors influencing the release of radionuclides to air and water. Selective extraction studies and studies of radionuclide sorption by and leaching from components of UMT showed alkaline earth sulfate and hydrous ferric oxides to be important hosts of radium-226 (²²⁶Ra) in UMT. Extrapolating from studies of barite dissolution in anerobic lake sediments, the leaching of²²⁶Ra from UMT by sulfate-reducing bacteria was investigated; a marked increase in²²⁶Ra release to aqueous solution as compared to sterile controls was demonstrated. A similar action of iron(III)-reducing bacteria was later shown. Ion exchangers such as clay minerals can also promote the dissolution of host-phase minerals and thereby influence the fate of radionuclides such as²²⁶Ra. Radon release studies examined particle size and ore composition as variables. Aggregation of UMT particles was shown to mask the higher emanating fraction of finer particles. Studies of various ores and ore components showed that UMT cannot be assumed to have the same radon-release characteristics as their precursor ores, nor can²²⁶Ra retained by various substrates be assumed to emanate the same fraction of radon. Over the last decade, USGS research directed at offsite mobility of radionuclides from uranium mining and milling processes has focused on six areas: the Midnite Mine in Washington; Ralston Creek and Reservoir, Colorado; sites near Canon City, Colorado; the Monument Valley District of Arizona and Utah; the Cameron District of Arizona; and the Puerco River basin of Arizona and New Mexico.     

Results of Marine Radioecological Study of Fjords of Western Spitsbergen

The patterns of the distribution of technogenic radionuclides ¹³⁷Cs and ⁹⁰Sr in the water mass and bottom deposits of three fjords of Western Spitsbergen (Isfjorden and its arms Grønfjorden and Billefjorden) were studied. The hydrological processes affecting migration of radionuclides in these water bodies were described. It was shown that the ice sheet of the archipelago that accumulates atmospheric precipitation is a source of radioactive contamination of the marine environment of the coast. Technogenic isotopes were accumulated during nuclear weapon testing in the second half of the twentieth century. The current climatic changes strengthen the role of glaciers in the contamination of arctic seas. It was noted that extrema of the ¹³⁷Cs and ⁹⁰Sr specific activity is mainly concentrated in the areas of glacier runoff discharge.

     

The use of sapropels as amendments in radiocaesium and radiostrontium contaminated soils

Two issues are addressed in this paper: the solid/liquid distribution behaviour of radiocaesium (¹³⁷Cs and ¹³⁴Cs) and radiostrontium (⁹⁰Sr) in sapropels, and the potential effectiveness of sapropels as amendments to remediate soils contaminated with these radionuclides. It is shown that the solid/liquid partitioning of radiocaesium and radiostrontium in sapropels is governed by the same processes as in soils. Experimental K_D values measured in a representative solution vary between 300 and 5000 dm³ kg⁻¹ for radiocaesium and between 15 and 50 dm kg⁻¹ for radiostrontium. These K_D values can be interpreted quantitatively on the basis of the main factors which govern the solid/liquid partitioning of these radionuclides.This quantitative approach also allows predictions to be made on the potential effectiveness of sapropel amendments in contaminated soils. These predictions agree very well with experimental results from simple laboratory experiments aimed at investigating the amendment effect. Addition of 1–4 wt.% doses of 2 sapropel samples with different radiocaesium retention characteristics had no significant effect on the radiocaesium distribution coefficient in sandy soils. It is therefore expected that the addition of such sapropels will not result in a decrease of the radiocaesium soil-to-plant transfer, at least not from the point of view of the increase of the radiocaesium retention in the amended soil. Addition of 1–4 wt.% doses of a high CEC sapropel to low CEC sandy soils increased the radiostrontium distribution coefficient up to 3.5 times. It can thus be expected that addition of such high CEC sapropel will increase the radiostrontium retention in the amended soil, and thus decrease the radiostrontium soil-to-plant transfer.     

Environmental evaluation of elemental cesium and strontium contents and their isotopic activity concentrations in different soils of La Mancha (Central Spain)

Cesium and Strontium concentrations were analyzed in eight pedogenetic soil profiles developed on different rocks from a semiarid mediterranean region: La Mancha (Central Spain). Concentration activities of ¹³⁷Cs and ⁹⁰Sr, as for some soil properties, were also measured. The results are presented in this document: Cs concentrations range between 0.4 and 18.3 mg kg⁻¹ and Sr varies widely between 11.0 and 3,384 mg kg⁻¹. Therefore, it is clear that there is a broad range of concentrations and there are also values significantly higher than the average values stated by several authors. Concentrations of long-life artificial radionuclides (¹³⁷Cs, ⁹⁰Sr) were determined in some of the same soils. The activity concentration mean values (Bq kg⁻¹) were ranging between 0.82 and 21.76 for ¹³⁷Cs and ⁹⁰Sr variations range between 6.73 and 0.35. There were no significant correlations between radionuclides and stable trace elements. The data indicate that the soils do not show significant radioactivity of these elements and therefore they do not pose a danger. By the same token, no risk of contamination by this activity was detected. Finally, spatial patterns seem to be affected by the soil type and some soil properties.     

Flow of metals into the global atmosphere

Concentrations of ¹³⁷Cs, ²¹⁰Pb, ²²⁶Ra, U, V, Pb, Cd and Hg have been measured in firn and ice deposited during the past three decades in accumulation zones of glaciers and also in pre-industrial glacier ice collected in Spitsbergen, Northern Norway, Alaska, Southern Norway, Alps, Himalayas, Ruwenzori, Peruvian Andes, and at King George Island in Antarctica. Except for Hg, the geographical distribution of mean concentrations of ²²⁶Ra, U and stable heavy metals in contemporary ice is not uniform, with the lowest concentrations found in Northern Norway, Alaska and Antarctica, and the highest in continental locations at equatorial and middle latitudes. We did not find evidence of changes in rate of metal deposition during the last three decades, as compared with pre-industrial period, however, our samples of pre-industrial ice might be contaminated in part by contemporary fallout migrating from the exposed surface of old parts of glaciers into the deeper ice layers. Using the data on annual injections of ¹³⁷Cs into the global atmosphere and mean global concentrations of radionuclides and heavy metals found in contemporary ice the global annual flows of ²²⁶Ra, ²¹⁰Pb, U,V, Pb, Cd and Hg were estimated as 6.6 kCi, 485 kCi, 12kt, 4870kt, 590 kt, 180 kt and 190 kt, respectively. These estimates are 1–2 orders of magnitude higher than estimates based on primary paniculate emissions. The anthropogenic contribution is a small fraction of the flows, which are dominated by natural processes leading to enrichment of metals in airborne dust.     

Application of Chitin and Zeolite adsorbents for treatment of low level radioactive liquid wastes

Two types of Shrimp Chitin derivatives and two types of Iranian natural Zeolite derivatives (Firuzkooh Clinoptiliolite) were studied for adsorption and treatment of low-level radioactive liquid waste (LLW). Chitin with lowers than 10% and Chtiosan with higher than 90% deacetylation factor were selected as natural organic adsorbents. Natural Cliniptilolite of Firuzkooh area and Na form derivatives of it were selected as natural inorganic adsorbents. The static and dynamic ion exchange experimental results show that the adadsorption efficiency depend on particle size, PH, adsorbent type, deacetylation factor (in Chitin adsorbents) and cation type. The best Cs adsorption occurred in Na form Clinoptilolite. Nevertheless Chitin derivatives, particularly Chitosan, are more efficient than Zeolite adsorbents for removing of radionuclides such as ¹³⁷Cs, ⁵⁴Mn, ⁹⁰Sr and ⁶⁰Co. Adsorption performance was discussed and compared with each other.     

Inventories and sorption-desorption trends of radiocesium and radiocobalt in James River estuary sediments

Anthropogenic radionuclides (¹³⁷Cs,¹³⁴Cs,⁶⁰Co) have been introduced to the James River estuary as a result of low-level releases from the Surry Reactor site since 1973 and worldwide atmospheric fallout from nuclear weapons tests since the early 1950s The total radionuclide burden in the estuary sediments has been estimated by integrating radionuclide activities in 29 box cores and extrapolating these integrated values over surface areas subdivided on the basis of sediment type, rates of accumulation, and proximity to the reactor release site. Our results indicate that 30% of the⁶⁰Co, but only 15% of the¹³⁴Cs released from the reactor site, has been retained in the estuary sediments, and about 40% of the¹³⁴Cs and⁶⁰Co sediment inventory is in areas that represent less than 5% of the total estuarine surface area. Depletion of the¹³⁴Cs in downstream sediments forms a noticeable trend in the James River estuary, and we postulate that seawater cation competition and exchange is primarily responsible.     

A new procedure for separating and measuring radiogenic isotopes (U, Th, Pa, Ra, Sr, Nd, Hf) in ice cores

A new method for the radiogenic isotope (U–Th–Pa–Ra, Sr, Nd, Hf) analysis of the soluble and insoluble components found within ice cores is presented. Melting experiments with rock standards in the presence of EDTA indicate that carbonates, as well as silicates, can be buffered sufficiently to preclude dissolution. The use of EDTA allows adsorbing species, such as Th and Hf, to remain in solution during melting thus fully separating the dust (insoluble) and sea salt (soluble) components of the ice after filtration. A new elemental separation scheme for low sample masses, less than 5 mg solid material, utilizes 4 primary ion exchange columns and two “clean-up” columns to fully isolate U, Th, Pa, Ra, Sr, Nd, and Hf while maintaining high yields. Elution schemes measured for USGS rock standards and a Chinese loess are presented to provide a comparison for variable matrix compositions. Mass spectrometer techniques were modified to measure small aliquots of the standards, equivalent to the amounts found in ice core samples, 10 ng and less. A MC-ICPMS was employed for the measurement of U, Th, Pa, Ra, and Hf; results of the experiments show that with ion yields up to 1%, rock standards have errors for ²³⁴U/²³⁸U of 1%, ²³⁰Th/²³²Th of 1.5%, [²²⁸Ra] of 9%, and ¹⁷⁶Hf/¹⁷⁷Hf of 100 ppm. MC-TIMS measurements of Sr and Nd show similar errors for small sample sizes: ⁸⁷Sr/⁸⁶Sr of 50 ppm and ¹⁴³Nd/¹⁴⁴Nd of 80 ppm. This new analytical method increases the number of possible tracers measured from a single sample, reducing separation times and sample consumption, as well as providing the addition of a radiometric clock, U-series, to the traditional suite of isotopic tracers, Sr, Nd, and Hf.     

Assessment of 137Cs and 90Sr fluxes in the Barents Sea

The annual balance of radionuclides inflow/outflow was assessed for ¹³⁷Cs and ⁹⁰Sr isotopes in the Barents Sea, taking into account the atmospheric precipitation, inflow from the Norwegian and the White seas, as well as riverine discharge, liquid radioactive waste disposal (LRWD), and outflow to the adjacent seas. The original and published data for the period of 1950–2009 were analyzed. According to the multiyear dynamics (1960–2009), the inflow of ¹³⁷Cs and ⁹⁰Sr into the Barents Sea was significantly preconditioned by the Norwegian Sea currents; and precipitation played a major role in the 1950s, 1960s, and in 1986. Currently, the trans-border redeposition of ⁹⁰Sr prevails over ¹³⁷Cs redeposition in the Barents Sea, and constitutes about 99% of inflow of each element.     

Coprecipitation of radionuclides with calcite: estimation of partition coefficients based on a review of laboratory investigations and geochemical data

Coprecipitation of radionuclides with secondary solids is currently neglected in safety assessments for radioactive waste repositories, although this process is thought to be important in limiting radionuclide solution concentrations. This paper provides a systematic review of laboratory data on metal coprecipitation with calcite, presented in the form of phenomenological partition coefficients. The aim of this investigation is to provide a consistent set of parameter values for the quantitative modelling of radionuclide coprecipitation with calcite, which will be the dominant alteration product in cementitious repositories accessed by carbonate-rich groundwater.From the data reviewed, empirical correlations have been derived that relate experimentally determined partition coefficients (λ_Me) to measurable chemical properties of the coprecipitated metals (ionic radii and sorption parameters of the incorporated trace metals, solubility products of the pure metal carbonates). These correlations have then been used to predict the partition coefficients of radionuclides for which no laboratory data exist.Such predictions indicate that the actinides will partition strongly into calcite under reducing conditions (λ_Me ∼200–1000 for trivalent, λ_Me ∼20–200 for tetravalent actinides). Nickel(II) incorporation will be moderate (λ_Me ∼1–10), while incorporation of ions like U(VI), Cs(I), Sr(II) and Ra(II) in calcite will be weak (λ_Me<1).In spite of substantial uncertainties, the estimated partition coefficients are sufficiently accurate to allow a semi-quantitative evaluation of the effect of radionuclide coprecipitation with calcite in limiting radionuclide solution concentrations in well characterised repository environments.