Origin of brines in the Upper Silesian Coal Basin (Poland) inferred from stable isotope and chemical data

Brines in the Miocene formations of the Upper Silesian Coal Basin have isotopic composition close to SMOW, which identifies them as the connate marine water. However, controversies exist on the origin of brines in the Carboniferous formations. Isotopic and hydrochemical data exclude any relationship to marine water and enrichment by evaporation. The most common brine which occurs at great depths can be identified as the oldest infiltration in a very hot climate (δ¹⁸O ⋟ −2‰, δD ⋟ −20‰, Cl⁻ content 34 to 140 g/L). This brine is free of SO₄²⁻ and U, and rich in Ba²⁺ and²²⁶Ra. Its salinity is probably related to the leaching of evaporites and intensive weathering of rocks during the Rotliegendes.Other brines are difficult to identify because their isotopic contents are within the range of mixing between the oldest brine and the Quaternary waters (δ¹⁸O ⋟ 10‰, δD ⋟ 70‰). Isotopic and hydrochemical data allow identification of several occurrences of brine formed by meteoric water of a warm Tertiary climate, after the last marine transgression in the Tortonian. That brine is rich in SO₄²⁻ and contains moderate contents of²²⁶Ra and U. Its salinity is thought to result from leaching of Miocene evaporites. Two other identified types of brines can be related to some infiltration periods before the last marine transgression. The sources in salinity of these 2 types remain unknown. Mining activity results in a common occurrence of mixed brines. When the Quaternary component dominates, its identification is easy from the isotopic composition, whereas the end brine component can ususally be identified by chosen ion ratios and the presence or lack of sulphates.     

Release ofRa from uranium mill tailings by microbial Fe(III) reduction

Uranium mill tailings were anaerobically incubated in the presence of H₂ with Alteromonas putrefaciens, a bacterium known to couple the oxidation of H₂ and organic compounds to the reduction of Fe(III) oxides. There was a direct correlation between the extent of Fe(III) reduction and the accumulation of dissolved²²⁶Ra. In sterile tailings in which Fe(III) was not reduced, there was negligible leaching of²²⁶Ra. The behavior of Ba was similar to that of Ra in inoculated and sterile systems. These results demonstrate that under anaerobic conditions, microbial reduction of Fe(III) may result in the release of dissolved²²⁶Ra from uranium mill tailings.     

Geochemistry of radium in soils of the Eastern United States

The abundance and chemical/mineralogical form of ²²⁶Ra, ²³⁸U and ²³²Th were determined on samples of soil and associated vegetation at 12 sites in the eastern United States. Progressive, selective chemical extraction plus size fractionation determined the abundance and radiometric equilibrium condition of these nuclides in 6 operationally defined soil fractions: exchangeable cations, organic matter, “free” Fe-oxides, sand, silt, and clay.In soils, profile-averaged ²²⁶Ra/²³⁸U activity ratios (AR) are within 10% of unity for most sites, implying little fractionation of U and Ra when the entire soil profile is considered. However, ²²⁶Ra greatly exceeds ²³⁸U activity in most surface soil (AR up to 1.8, av 1.22), in vegetation (AR up to 65, av. 2.8), in the exchangeable+organic fraction (AR up to 30, av. 13), in some soil Fe oxides (AR up to 3.5, av. 0.83) and in the C horizons of deeply weathered soils (AR up to 1.5).A major factor in Ra behavior is uptake by vegetation, which concentrates Ra>U and moves Ra from deeper soil to surface soil. Vegetation is capable of creating the observed Ra excess in typical surface soil horizons (AR up to 1.8, av. 1.22) in about 1000 a. Of the total Ra in an average A horizon, 42% occurs as exchangeable ions and in organic matter, but only 6–8% of the parent U and Th occur in these soil forms. In contrast, U is slightly enriched relative to Ra in Fe-oxides of A horizons, implying rapid chemical partition of vegetation-cycled U and Ra.In deeper horizons, transfer by vegetation and/or direct chemical partitioning of Ra into organic and exchangeable forms provides a source for unsupported ²²⁶Ra in Ra-rich organic matter, and leaves all soil minerals Ra-poor (AR=0.73). Organic matter evidently has a strong affinity for Ra.The phenomena discussed above are relevant to evaluation of indoor Rn hazard, and behavior of Ra at sites affected by radioactive waste disposal, phosphate tailings, Ra-rich brine, and uraniferous fertilizer.     

Uranium-series disequilibrium in Australian soils and its effect on aerial gamma-ray surveys

Measurements of U and ²²⁶Ra in 445 soil samples collected from areas throughout Australia show that these soils have a mean U content of 2.0 mg kg⁻¹ and activity ratio (U/²²⁶Ra) of 1.09. There is a wide spread in individual values but, overall, more soils are U-rich than ²²⁶Ra-rich. Some indications of regional disequilibrium were found, with ²²⁶Ra-rich soils being noted in the Southern Cross-Kambalda area (WA), in south-eastern Eyre Peninsula (SA) and in an area north of Cobar (NSW). Uranium-rich soils were found in two Carboniferous volcanic terrains in north-eastern Queensland. The spread in activity ratio values indicates that disequilibrium will contribute to the noise in U channel data obtained by aerial gamma-ray surveying. The combination of statistical noise from low count rates (reflecting the low U concentrations in soils) and U-²²⁶Ra disequilibrium combine to give variances of 40–60% in typical U channel data. Data appearance can be improved to some extent by appropriate filtering.     

Application of226Ra,228Ra,223Ra, and224Ra in coastal waters to assessing coastal mixing rates and groundwater discharge to oceans

The fate of dissolved material delivered to the coastal ocean depends on its reactivity and the rate at which it is mixed offshore. To measure the rate of exchange of coastal waters, we employ two short-lived radium isotopes,²²³Ra and²²⁴Ra. Along the coast of South Carolina, shore-perpendicular profiles of²²³Ra and²²⁴Ra in surface waters show consistent gradients which may be modeled to yield eddy diffusion coefficients of 350–540 m²s⁻¹. Coupling the exchange rate with offshore concentration gradients yields estimates of offshore fluxes of dissolved materials. For systems in steady state, the offshore fluxes must be balanced by new inputs from rivers, groundwater, sewers or other sources. Two tracers that show promise in evaluating groundwater input are barium and²²⁶Ra. These tracers have high relative concentrations in the fluids and low-reactivity in the coastal ocean. Applying the eddy diffusion coefficients to the offshore gradient of²²⁶Ra concentration provides an estimate of the offshore flux of²²⁶Ra. Measuring the concentrations of²²⁶Ra in subsurface fluids provides an estimate of the fluid flux necessary to provide the²²⁶Ra. These estimates indicate that the volume of groundwater required to support these fluxes is of the order of 40% of the surface water flow.     

Assessment of natural radioactivity in aquifer medium bearing uranium ores in Koprubasi,Turkey

Koprubasi, located within Manisa Province near the Izmir, is the biggest uranium mine where uranium ores originate from Neogene aged altered sandstone and conglomerate layers. The main objective of this study is to determine the radiation hazard associated with radioactivity levels of uranium ores, and the rocks and sediments around Koprubasi. In this regard, measured activity levels of ²²⁶Ra, ²³²Th and ⁴⁰K were compared with world averages. The average activity levels of ²²⁶ Ra, ²³²Th and ⁴⁰K were measured to be 5369.75, 124.78 and 10.0 Bq/kg in uranium ores, 24.32, 52.94 and 623.38 Bq/kg in gneiss, 46.24, 45.13 and 762.26 Bq/kg in sandstone and conglomerate, 73.11, 43.15 and 810.65 Bq/kg in sediments, respectively. All samples have high ²²⁶Ra and ⁴⁰K levels according to world average level. As these sediments are used as construction materials and in agricultural activities within the study area, the radiation hazard are calculated by using dose rate (D), annual effective dose rate (He), radium equivalent activity (Ra_eq) and radiation hazard index (I_yr). All the samples have Ra_eq levels that are lower than the world average limit of 370 Bq/kg. On the other hand, D, He and I_yr values are higher than world average values. These results indicate that the uranium ores in the Koprubasi is the most important contributor to the natural radiation level. The radioactivity levels of sediments and rocks make them unsuitable for use as agricultural soil and as construction materials. Moreover, it is determined that shallow groundwater in sediments and deep groundwater in conglomerate rocks and also surface water sources in the Koprubasi have high ²²⁶Ra content. According to environmental radioactive baseline, some environmental protection study must be taken in Koprubasi uranium site and the environment.     

Controls on Ra during raffinate neutralization at the Key Lake uranium mill, Saskatchewan, Canada

This study was conducted to define the geochemical controls on ²²⁶Ra during raffinate (pH = 1.2) neutralization to pH 10 at the Key Lake U mill in northern Saskatchewan, Canada. High activities (120–150 Bq/L) of aqueous phase ²²⁶Ra are present in raffinate produced during milling of U ore. The solubility control of ²²⁶Ra in the SO₄-rich, hydrometallurgical raffinate solutions often involves the addition of BaCl₂ to form a radium-barite co-precipitate (Ba(Ra)SO₄). As such, neutralization experiments were conducted with samples of mill raffinate using Ca(OH)₂ or NaOH with and without the addition of BaCl₂. Radium-226 activity decreased from 150 to <4 Bq/L for all combinations of neutralizing agents with Ca(OH)₂ + BaCl₂ being the most effective combination (final activity ∼1.0 Bq/L; ∼99.3% removal). In the absence of BaCl₂, Ca(OH)₂ more efficiently removed ²²⁶Ra than NaOH between pH 4 and 8, due to the co-precipitation of ²²⁶Ra with gypsum. Overall, neutralization with the addition of BaCl₂ reduced ²²⁶Ra activities at lower pH values (by pH 4.5), due to co-precipitation of ²²⁶Ra with BaSO₄. At varying concentrations of BaCl₂, aqueous phase activities of ²²⁶Ra converged, but did not attain steady-state values during neutralization and would continue to decrease with time. Sequential extractions indicated that ²²⁶Ra in precipitates formed during neutralization of the mill raffinate is dominated by amorphous and crystalline Fe hydroxide phases, consistent with raffinate neutralization experiments that showed that adsorption onto ferrihydrite can remove most ²²⁶Ra in the raffinate. Data generated in this study are being used to define the long-term geochemical controls on ²²⁶Ra in U mill processes and tailings.     

Development of a reactive zone technology for simultaneous in situ immobilisation of radium and uranium

Simultaneous in situ immobilisation of uranium (U) and radium (²²⁶Ra) by injectible amounts of grey cast iron (gcFe), nano-scale iron (naFe) and a gcFe/MnO₂ mixture (1:1) was studied in batch and column tests. Both 0.5 g/L naFe and gcFe are effective in ²²⁶Ra and U removal from mine water, whereas MnO₂ addition clearly increased the efficiency of gcFe for ²²⁶Ra and U immobilisation. In a column test with 0.6 wt% gcFe/MnO₂ mixture (1:1), neither ²²⁶Ra nor U was detected in the effluent after replacement of 45 pore volumes. A sequential extraction under flow condition revealed ²²⁶Ra to be mostly occluded in manganese oxides. Uranium was mostly sorbed onto poorly crystalline iron hydroxides, but a significant part was found to be occluded in manganese oxides also. The results of this study suggest that MnO₂ promotes iron hydroxide formation under slightly reducing environmental conditions resulting in an increased pollutant retention capacity.     

Radionuclide partitioning across great lakes natural interfaces

Several water and surface microlayer samples from Lake St. Clair, the Niagara River, and the North Shore of Lake Ontario collected during 1983–1986 have been assayed for a variety of radionuclides. In addition, the foam accumulating in the pool just below Niagara Falls was also analyzed and found to be the most efficient aqueous phase collector of¹³⁷Cs,²¹⁰Pb, and²²⁶Ra.The order of radioisotope specific activities from highest to lowest is: Lake Ontario sediment, Niagara River suspended solids, Niagara River foam, surface microlayer water, and subsurface water. Radiological dose rates to the sediments from¹³⁷Cs,²²⁶Ra, and²²⁸Th total about 5 mGy/y.     

Radionuclides in ground water of the Carson River Basin,western Nevada and eastern California,U.S.A.

Ground water is the main source of domestic and public supply in the Carson River Basin. Ground water originates as precipitation primarily in the Sierra Nevada in the western part of Carson and Eagle Valleys, and flows down gradient in the direction of the Carson River through Dayton and Churchill Valleys to a terminal sink in the Carson Desert. Because radionuclides dissolved in ground water can pose a threat to human health, the distribution and sources of several naturally occurring radionuclides that contribute to gross-alpha and gross-beta activities in the study area were investigated. Generally, alpha and beta activities and U concentration increase from the up-gradient to down-gradient hydrographic areas of the Carson River Basin, whereas²²²Rn concentration decreases. Both²²⁶Ra and²²⁸Ra concentrations are similar throughout the study area. Alpha and beta activities and U concentration commonly exceed 100 pCi/l in the Carson Desert at the distal end of the flow system. Radon-222 commonly exceeds 2,000 pCi/l in the western part of Carson and Eagle Valleys adjacent to the Sierra Nevada. Radium-226 and²²⁸Ra concentrations are <5pCi/l. Four ground water samples were analyzed for²¹⁰Po and one sample contained a high concentration of 21 pCi/l. Seven samples were analyzed for²¹⁰Pb; six contained <3pCi/l and one contained 12 pCi/l. Thorium-230 was detected at concentrations of 0.15 and 0.20 pCi/l in two of four samples.Alpha-emitting radionuclides in the ground water originated from the dissolution of U-rich granitic rocks in the Sierra Nevada by CO₂, oxygenated water. Dissolution of primary minerals, mainly titanite (sphene) in the granitic rocks, releases U to the water. Dissolved U is probably removed from the water by adsorption on Fe- and Mn-oxide coatings on fracture surfaces and fine-grained sediment, by adsorption on organic matter, and by coprecipitation with Fe and Mn oxides. These coated sediments are transported throughout the basin by fluvial processes. Thus, U is transported as dissolved and adsorbed species. A rise in the water table in the Carson Desert because of irrigation has resulted in the oxidation of U-rich organic matter and dissolution of U-bearing coatings on sediments, producing unusually high U concentration in the ground water.Alpha activity in the ground water is almost entirely from the decay of U dissolved in the water. Beta activity in ground water samples is primarily from the decay of⁴⁰K dissolved in the water and ingrowth of²³⁸U progeny in the sample before analysis. Approximately one-half of the measured beta activity may not be present in ground water in the aquifer, but instead is produced in the sample after collection and before analysis. Potassium-40 is primarily from the dissolution of K-containing minerals, probably K-feldspar and biotite. Radon-222 is primarily from the decay of²²⁶Ra in the aquifer materials. Radium in the ground water is thought to be mainly from alpha recoil associated with the decay of Th in the aquifer material. Some Ra may be from dissolution (or desorption) or Ra-rich coatings on sediments.     

Mode of occurrence and environmental mobility of oil-field radioactive material at US Geological Survey research site B,Osage-Skiatook Project,northeastern Oklahoma

Two samples of produced-water collected from a storage tank at US Geological Survey research site B, near Skiatook Lake in northeastern Oklahoma, have activity concentrations of dissolved ²²⁶Ra and ²²⁸Ra that are about 1500 disintegrations/min/L (dpm/L). Produced-water also contains minor amounts of small (5–50 μm) suspended grains of Ra-bearing BaSO₄ (barite). Precipitation of radioactive barite scale in the storage tank is probably hindered by low concentrations of dissolved SO₄ (2.5 mg/L) in the produced-water. Sediments in a storage pit used to temporarily collect releases of produced-water have marginally elevated concentrations of “excess” Ra (several dpm/g), that are 15–65% above natural background values. Tank and pit waters are chemically oversaturated with barite, and some small (2–20 μm) barite grains observed in the pit sediments could be transferred from the tank or formed in place. Measurements of the concentrations of Ba and excess Ra isotopes in the pit sediments show variations with depth that are consistent with relatively uniform deposition and progressive burial of an insoluble Ra-bearing host (barite?). The short-lived ²²⁸Ra isotope (half-life = 5.76 a) shows greater reductions with depth than ²²⁶Ra (half-life = 1600 a), that are likely explained by radioactive decay. The ²²⁸Ra/²²⁶Ra activity ratio of excess Ra in uppermost pit sediments (1.13–1.17) is close to the ratio measured in the samples of produced-water (0.97, 1.14). Declines in Ra activity ratio (excess) with sediment depth can be used to estimate an average rate of burial of 4 cm/a for the Ra-bearing contaminant. Local shallow ground waters contaminated with NaCl from produced-water have low dissolved Ra (<20 dpm/L) and also are oversaturated with barite. Barite is a highly insoluble Ra host that probably limits the environmental mobility of Ra at site B.     

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.     

226Ra in phosphate nodules from the Peru/Chile seafloor

²²⁶Ra and other uranium-series radionuclides have been measured in a suite of marine phosphorite samples from the upwelling area off Peru/Chile by gamma-ray spectrometry and radiochemical techniques. Our results lead to the following conclusions: (1) phosphorite nodules typically show unidirectional growth at rates of 1 to 10 mm/Kyr; (2) very young samples (less than a few thousand years) contain slight excess amounts of ²²⁶Ra probably derived from pore fluids; and (3) slow but persistent leakage of ²²⁶Ra out of phosphate nodules occurs resulting in systematically lower ²²⁶Ra ages compared to ²³⁰Th ages for samples older than about twenty thousand years. Radium fluxes from these phosphate nodules appear to be 1 to 3 orders of magnitude less than those calculated for deep-sea sediments and ferromanganese nodules.     

The source of radium in anomalous accumulations near sandstone escarpments,Australia

The source of Ra has been determined in water samples from four areas in Australia where anomalously high surface concentrations of²²⁶Ra have accumulated from groundwaters. All four anomalies were located adjacent to sandstone formations, and the groundwaters, which were generally all acidic and low in dissolved salts, appeared to be meteoric water with short ground-residence times. Uranium,²²⁶Ra and²²⁸Ra concentrations of waters feeding the anomalous areas were comparable to those found in standing waters within the sandstones. The²²⁶Ra/²²⁸Ra isotopic ratios were distributed about a median of 1.1 which suggests that the waters are in contact with rocks with near-normal U/Th ratios and, hence, that the Ra in the anomalies was derived from within the sandstones.The presence of the short-lived Ra isotopes,²²³Ra and²²⁴Ra, in high concentrations in most spring waters feeding these anomalies suggests that Ra enters groundwaters by recoil following alpha decay of a precursor parent radionuclide within mineral grains. Thus, although three of the areas were considered prospective for U, the radioactive anomalies studied appear to be due to natural transfer of Ra from the sandstones to the surface environment. In no case were the anomalies related to nearby known or undiscovered U deposits. Accordingly, a geochemical procedure, which includes Ra isotopic measurements, is recommended for evaluating radioactive anomalies for U exploration. This procedure should enable selection of only those anomalies with the highest potential for further exploration by more expensive techniques.     

Ra/Ra and Ra/Ba ratios in the Western Mediterranean Sea: Barite formation and transport in the water column

²²⁶Ra, ²²⁸Ra and Ba distributions as well as ²²⁸Ra/²²⁶Ra and ²²⁶Ra/Ba ratios were measured in seawater, suspended and sinking particles at the DYFAMED station in the Western Mediterranean Sea at different seasons of year 2003 in order to track the build-up and fate of barite through time. The study of the ²²⁸Ra_ex/²²⁶Ra_ex ratios (Ra_ex = Ra activities corrected for the lithogenic Ra) of suspended particles suggests that Ba_ex (Ba_ex = Ba concentrations corrected for the lithogenic Ba, mostly barite) formation takes place not only in the upper 500 m of the water column but also deeper (i.e. throughout the mesopelagic layer). Temporal changes in the ²²⁸Ra_ex/²²⁶Ra_ex ratios of sinking particles collected at 1000 m depth likely reflect changes in the relative proportion of barite originating from the upper water column (with a high ²²⁸Ra/²²⁶Ra ratio) and formed in the mesopelagic layer (with a low ²²⁸Ra/²²⁶Ra ratio). ²²⁸Ra_ex/²²⁶Ra_ex ratios measured in sinking particles collected in the 1000 m-trap in April and May suggest that barite predominantly formed in the upper water column during that period, while barite found outside the phytoplankton bloom period (February and June) appears to form deeper in the water column. Combining ratios of both the suspended and sinking particles provides information on aggregation/disaggregation processes. High ²²⁶Ra_ex/Ba_ex ratios were also found in suspended particles collected in the upper 500 m of the water column. Because celestite is expected to be enriched in Ra [Bernstein R. E., Byrne R. H. and Schijf J. (1998) Acantharians: a missing link in the oceanic biogeochemistry of barium. Deep-Sea Res. II45, 491-505], acantharian skeletons may contribute to these high ratios in shallow waters. The formation of both acantharian skeletons and barite enriched in ²²⁶Ra may thus contribute to the decrease in the dissolved ²²⁶Ra activity and ²²⁶Ra/Ba ratios of surface waters observed between February and June 2003 at the DYFAMED station.     

An improved method for Ra isotope (226Ra, 228Ra, 224Ra) measurements by gamma spectrometry in natural waters: application to CO2-rich thermal waters from the French Massif Central

An improved method was developed to measure ²²⁶Ra, ²²⁸Ra and ²²⁴Ra in freshwaters by gamma spectrometry. Radium was selectively extracted from acidified samples using specific filters (3M EMPORE™ Radium Rad disks). The latter was subsequently analysed by gamma spectrometry. Simultaneous and direct determination of the activities of the three isotopes was performed by comparison of gamma rays of the Radium Rad disks with those of a calibrated standard disk. This efficient and reliable method allowed a reduction of sample processing to a few hours.This technique was applied to analyse the Ra isotope compositions of several CO₂-rich hydrothermal springs of the western border of the Limagne graben (French Massif Central). The studied springs emerge from a succession of granitic outcrops lined up along a major fault. Their chemical compositions evolve from calcic and magnesian chloro-bicarbonated to sodic bicarbonated. All the springs display high Ra activities, probably linked to high CO₂ content and/or high cation content of these waters, with various Ra isotope ratios. ²²⁶Ra activity ranges from 588 to 2287 mBq/l and ²²⁸Ra activity from 260 to 1590 mBq/l, whereas ²²⁴Ra displays an activity between 245 and 1808 mBq/l. Four of the six analysed springs have (²²⁸Ra/²²⁶Ra) activity ratios lower than 0.7, thus, significantly lower than the ratio expected from an interaction with a calc-alkaline granitoid (typically having (²³²Th/²³⁸U) activity ratio between 1 and 2). Low (²²⁸Ra/²²⁶Ra) ratio (0.27) of the northern water (Montpensier) suggests the existence in this area of a zone of U concentration, possibly resulting from U mobilization and accumulation induced by previous hydrothermal events. The (²²⁴Ra/²²⁸Ra) ratios display smaller variations. They suggest short transit times from the zone of Ra leaching to the surface (a few days) or a very shallow addition of ²²⁴Ra (e.g., from a localised zone where ²²⁸Th could be preferentially adsorbed on the mineral surfaces). In some cases, these ratios might be used to infer differences in transit times of waters between neighboring springs.     

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.     

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.     

Ra-partitioning between phlogopite and silicate melt and 226Ra/Ba–230Th/Ba isochrons

In this study we experimentally determine phlogopite/melt partition coefficients of Ra and other trace elements in a lamproitic system. This work was achieved using an analytical technique (LA-ICP-MS) with low detection limits (~ 0.01 fg) permitting the measurement of the very low Ra concentrations feasible in experiments (~ 1 ppb). D_Ra^{phlogopite/melt} was determined to 2.28 ± 0.44 and 2.84 ± 0.47 in two experiments, the ratio D_Ra/D_Ba is around 1.6. The compatibility of Ra in phlogopite results from an ionic radius being close to the apex of the lattice strain parabola for earth alkalis in the large XII-coordinated interlayer site of phlogopite. A re-evaluation of D_Ra and D_Ra/D_Ba for magmatic minerals containing appreciable Ra, yields D_Ra^mineral/melt ranging from ~ 2.6 for phlogopite down to 2–3 ? 10^? 5 for pyroxenes, and D_Ra/D_Ba^mineral/melt from ~ 4 for leucite to 2 ? 10^? 2 for orthopyroxene. The influence of melt composition on D_Ra/D_Ba is less than 10%. All investigated minerals have different D_Ra/D_Ba, strongly fractionating Ra from Ba. Thus, for magmatic systems, (²²⁶Ra)/Ba in the various minerals is not constant, these minerals do not form a straight line in the (²²⁶Ra)/Ba–(²³⁰Th)/Ba system at the time of crystallization and thus, there is no (²²⁶Ra)/Ba–(²³⁰Th)/Ba isochron at t₀. ²²⁶Ra–²³⁰Th–Ba mineral dating is thus applicable only to model ages calculated from mineral–glass pairs with known D_Ra.     

Suspended sediment sources and tributary effects in the lower reaches of a coastal plain stream as indicated by radionuclides, Loco Bayou, Texas

Characterizing the dynamics of fluvial sediment sources over space and time is often critical in identifying human impacts on fluvial systems. Upland interfluve and subsoil sources of suspended sediment at Loco Bayou, Texas, were distinguished using ²²⁶Ra/²³²Th, ²²⁶Ra/²³⁰Th and, ²²⁸Ra/²³²Th. Source contributions were apportioned at three stations during within-bank and flood flows. ¹³⁷Cs and ²¹⁰Pb_xs (excess ²¹⁰Pb) were used to determine floodplain sedimentation; suspended sediment ²¹⁰Pb_xs/¹³⁷Cs data mirrored results of Ra/Th, showing dominance of subsoil sources during within-bank flows, changing to interfluve sources during flood. This trend corresponds spatially to influx of sediment from ephemeral tributaries, reflecting mobilization of stored interfluvial sediments during flood stage. Upper basin sedimentation was similar but markedly less at the lowermost station. These results indicate (1) modified ephemeral tributaries store sediment derived from sheet wash, discharging them during flood, and (2) southernmost Loco Bayou is episodically re-worked, resulting in significantly reduced local rates of sedimentation.