Ra/Ra and Ra/Ba ratios to track barite formation and transport in the water column

We measured ²²⁸Ra_ex/²²⁶Ra_ex and ²²⁶Ra_ex/Ba_ex ratios in suspended and sinking particles collected at the Oceanic Flux Program (OFP) time-series site in the western Sargasso Sea and compared them to seawater ratios to provide information on the origin and transport of barite (BaSO₄) in the water column. The ²²⁸Ra_ex/²²⁶Ra_ex ratios of the suspended particles down to 2000 m are nearly identical to those of seawater at the same water depth. These ratios are much lower than expected if suspended barite was produced in surface waters and indicate that barite is produced throughout the mesopelagic layer. The ²²⁸Ra_ex/²²⁶Ra_ex activity ratios of sinking particles collected at 1500 and 3200 m varied mostly between 0.1 and 0.2, which is intermediate between the seawater ratio at these depths (<0.03) and the seawater ratios found in the upper 250 m (0.31-0.42). This suggests that excess Ba (i.e., Ba_ex = Ba_total − Ba_lithogenic), considered to be mainly barite, present in the sinking flux is a mixture of crystals formed recently in the upper water column, formed several years earlier in the upper water column, or formed recently in deeper waters. We observe a sizeable temporal variability in the ²²⁸Ra_ex/²²⁶Ra_ex ratios of sinking particles, which indicates temporal variability in the relative proportion of barite crystals originating from surface (with a high ²²⁸Ra_ex/²²⁶Ra_ex ratio) and mesopelagic (with a low ²²⁸Ra_ex/²²⁶Ra_ex ratio) sources. However, we could not discern a clear pattern that would elucidate the factors that control this variability. The ²²⁶Ra/Ba ratios measured in seawater are consistent with the value reported from the GEOSECS expeditions (2.3 dpm μmol⁻¹) below 500 m depth, but are significantly lower in the upper 500 m. High ²²⁶Ra_ex/Ba_ex ratios and elevated Sr concentrations in suspended particles from the upper water column suggest preferential uptake of ²²⁶Ra over Ba during formation of SrSO₄ skeletons by acantharians, which must contribute to barite formation in shallow waters. Deeper in the water column the ²²⁶Ra_ex/Ba_ex ratios of suspended particles are lower than those of seawater. Since ²²⁸Ra_ex/²²⁶Ra_ex ratios demonstrate that suspended barite at these depths has been produced recently and in situ, their low ²²⁶Ra_ex/Ba_ex ratios indicate preferential uptake of Ba over Ra in barite formed in mesopelagic water.     

Raexcess/Ba growth rates and U-Th-Ra-Ba systematic of Baltic Mn/Fe crusts

We analyzed ²³⁸U, ²³⁴U, ²³²Th, ²³⁰Th, and ²²⁶Ra by thermal ionization mass spectrometry (TIMS) and Ba by inductively coupled plasma optical emission spectrometry (ICP-OES) on eight Mn/Fe crusts from the Mecklenburg Bay (SW Baltic) and on one from the Bothnian Bay (N Baltic) to test the ²²⁶Ra_ex/Ba ratio as potential geochronometer. ²²⁶Ra_ex/Ba ratios decrease as a function of depth within the concretions in all analyzed profiles. Calculated diffusion coefficients are relatively low (∼9 · 10⁻⁷ cm²/yr for Ra and 5 · 10⁻⁷ cm²/yr for Ba) and suggest that diffusion is negligible for the Ra and Ba record. In addition, ²²⁶Ra_ex/Ba ages are consistent and independent from the growth rate and growth direction within a crust. Thus, the decline in ²²⁶Ra_ex/Ba ratio is most likely due to radioactive decay of ²²⁶Ra_ex, although the influence of varying oxic conditions has still to be evaluated. ²²⁶Ra_ex/Ba growth rates range from 0.021 to 0.0017 mm/yr and tend to be lower than those calculated and based on stratigraphic methods (1 to 0.013 mm/yr). ²²⁶Ra_ex/Ba ages of concretions from shallow water environment (20 m depth, Mecklenburg Bay/SW Baltic) cover a time interval from 990 ± 140 yr to 4310 ± 310 yr BP corresponding to the stabilization of the sea level close to the present position about 5500 to 4500 yr ago. One sample from greater depth (70 m, Bothnian Bay-/N Baltic) showed a higher ²²⁶Ra_ex/Ba age of 6460 ± 520 yr BP.     

Seasonal cycle of suspended barite in the mediterranean sea

Biogenic barium (Ba_xs) was measured in suspended particles at the DYFAMED site in the northwestern Mediterranean Sea, on a monthly basis between February and June 2003. The barium content of barite (BaSO₄) micro-crystals was investigated using Scanning Electron Microscopy (SEM). Suspended particles were collected by filtration of small volumes of seawater (∼10 L), as well as large volumes up to 2400 L in March and in May. The Ba_xs profiles obtained from small-volume filtration display the typical mesopelagic maximum reported by earlier studies at ∼200 m depth, with concentrations up to 595 pmol L⁻¹. In addition, suspended Ba_xs was found almost exclusively in the form of micro-crystalline barite, except in February. The Ba_xs profiles obtained from large-volume filtration are consistent with the small-volume filtration findings, but reveal a significant Ba_xs peak of 1698 pmol L⁻¹ in the surface waters in May. Seasonal sampling at the DYFAMED site shows a net increase in barite concentration during phytoplanktonic blooms, confirming the involvement of biological systems in barite formation, as well as the potential role of barite as a primary productivity tracer. In addition, the coincidence between the mesopelagic barite maximum and the oxygen minimum layer suggests that barite is primarily found at depths of intense remineralization, in agreement with the hypothesis that barite forms within microenvironments of decaying organic matter.     

Precise two chronometer dating of Pleistocene travertine: The Th/U and Raex/Ra(0) approach

In order to determine the geochemical evolution of a freshwater limestone cave system located in central Switzerland (Hell Grottoes at Baar/Zug,) young postglacial tufaceous limestone and travertine precipitates were investigated using the ²³⁰Th/²³⁴U ingrowth system. Additional analyses of further radionuclides within the ²³⁸U decay chain, i.e. ²²⁶Ra and ²¹⁰Pb, showed that the Th/U chronometer started with insignificant inherited ²³⁰Th over the entire formation period of the travertine setting (i.e. ²³⁰Th(0)=0). A contribution from detrital impurities with ²³⁰Th/²³⁴U in secular equilibrium could be precisely subtracted by applying isochron dating of cogenetic phases and recently formed travertine. The resulting precise ²³⁰Th/²³⁴U formation ages were found to be consistent with the geological stratigraphy and were furthermore used to demonstrate the applicability of the next geologically important chronometer in the ²³⁸U-decay series, based on decay of excess ²²⁶Ra normalized to the initial, i.e.²²⁶Ra_ex/²²⁶Ra(0). This system is suitable for dating phases younger than 7000 yr when the correction of a detritus component increasingly limits the precision of the ²³⁰Th/²³⁴U chronometer. Analytical solutions of the coupled ²³⁴U/²³⁰Th/²²⁶Ra radionuclide system predicted that the ²²⁶Ra_ex/²²⁶Ra(0) chronometer is independent of the actual ²³⁰Th activity build up from decay of ²³⁴U, if the systems starts with zero inherited ²³⁰Th(0). The data set confirmed this hypothesis and showed furthermore that the initially incorporated ²²⁶Ra excess must have remained almost uniform in all limestone over a period of at least 7000 yr, i.e. 4–5 half-lives of ²²⁶Ra. This is concluded because (i) the ²²⁶Ra_ex/²²⁶Ra(0) ages agreed well with those derived from ²³⁰Th/²³⁴U, (ii) all data plot within uncertainty on the ²²⁶Ra_ex/²²⁶Ra(0) decay curve and (iii) the atomic Ba/Ca ratio was found to be constant in the travertine material independent of the sample ages. Provided that such boundary conditions hold, ²²⁶Ra_ex/²²⁶Ra(0) should be applicable to materials which are suitable for ²³⁰Th/²³⁴U dating in sedimentology and oceanography, i.e. travertine, corals, phosphorites, etc., and should strongly support ²³⁰Th/²³⁴U for samples that have been formed a few thousand years ago.     

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.     

Radium content and the 226Ra228Ra activity ratio in groundwater from bedrock

The relative abundance of ²²⁶Ra and ²²⁸Ra were determined in the groundwater from 125 drilled wells containing from < 0.1 to 51.3 pCi/l of ²²⁶Ra. The determination of ²²⁸Ra was carried out with a liquid scintillation counter by measuring only the weakly energetic β particles emitted from ²²⁸Ra. Thus the interference from the daughter nuclides of ²²⁶Ra was avoided, without specific separation of ²²⁸Ac. The direct measurement of ²²⁸Ra made the method decisively simpler and faster in terms of the chemistry involved.The concentration of ²²⁸Ra was found to be independent of the amount of ²²⁶Ra present in the samples. The concentrations of ²²⁸Ra were nearly the same over the whole range of ²²⁶Ra concentrations and the average $\text{sol}{}^{226}\text{Ra}{}^{228}\text{Ra}$ ratio sharply increased as the ²²⁶Ra content of water increased. The ${}^{226}\text{Ra}{}^{228}\text{Ra}$ ratio in the drilled wells varied from 0.3 to 26. Abnormally high ${}^{226}\text{Ra}{}^{228}\text{Ra}$ ratios were found in areas with known uranium deposits as well as in several drilled wells at other locations. The abnormally high ${}^{226}\text{Ra}{}^{228}\text{Ra}$ ratios present in groundwater suggest that the radioactivity anomaly is caused by uranium deposits and not by common rocks. In samples with a low radioactivity level the average ${}^{226}\text{Ra}{}^{228}\text{Ra}$ ratio was slightly below unity, corresponding to the typical U/Th ratio of granite, the most common kind of rock in the study area. The samples from the rapakivi area proved to be exceptional in that they had a low ${}^{226}\text{Ra}{}^{228}\text{Ra}$ ratio independent of the concentration of ²²⁶Ra.     

Ba, Ra, Th, and U in marine mollusc shells and the potential of Ra/Ba dating of Holocene marine carbonate shells

The geochemistry of Ba, Ra, Th, and U and the potential of using ²²⁶Ra/Ba ratios as an alternative dating method are explored in modern and Holocene marine mollusc shells. Five modern shells of the Antarctic scallop Adamussium colbecki collected from the present day beach and six radiocarbon dated specimens from Holocene beach terraces of the Ross Sea region (Antarctic) between 700 and 6100 calibrated yr BP old have been analysed by mass spectrometry. In clean shells ²²⁶Ra concentrations and ²²⁶Ra/Ba ratios show a clear decrease with increasing age, suggesting the possibility of ²²⁶Ra dating. Limiting factors for such dating are Ba and ²²⁶Ra present in surface contaminants, and ingrowth of ²²⁶Ra from U present within the shell. Surface contamination is difficult to clean off entirely, but moderate levels of residual contamination can be corrected using ²³²Th. Sub-samples from the same shell with different proportions of contamination form a mixing line in a ²²⁶Ra/Ba-²³²Th/Ba graph, and the ²²⁶Ra/Ba of the pure shell can be derived from the intercept on the ²²⁶Ra/Ba axis. Contaminant corrected ²²⁶Ra/Ba ratios of late-Holocene ¹⁴C-dated samples fall close to that expected from simple ²²⁶Ra excess decay from seawater ²²⁶Ra/Ba values. ²²⁶Ra ingrowth from U incorporated into the shell during the lifetime of the mollusc can be corrected for. However, the unknown timing of post mortem U uptake into the shell makes a correction for ²²⁶Ra ingrowth from secondary U difficult to achieve. In the A. colbecki shells, ²²⁶Ra ingrowth from such secondary U becomes significant only when ages exceed ∼2500 yr. In younger shells, ²²⁶Ra/Ba ratios corrected for surface contamination provide chronological information. If evidence for a constant oceanic relationship between ²²⁶Ra and Ba in the ocean can be confirmed for that time scale, the ²²⁶Ra/Ba chronometer may enable the reconstruction of variability in sea surface ¹⁴C reservoir ages from mollusc shells and allow its use as a paleoceanographic tracer.     

Ra and Th adsorption coefficients in lakes—Lake Kinneret (Sea of Galilee) “natural experiment”

The adsorption rate constants of Ra and Th were estimated from empirical data from a freshwater lake and its feeding saline springs. We utilized the unique setting of Lake Kinneret (Sea of Galilee, northern Israel) in which most of the Ra and Th nuclides are introduced into the lake by saline springs with high ²²⁶Ra activities and a high ²²⁴Ra/²²⁸Ra ratio of 1.5. The mixing of the Ra enriched saline waters and freshwater in the lake causes the ²²⁴Ra/²²⁸Ra ratio to drop down to 0.1 in the Kinneret due to preferential adsorption of ²²⁸Th. These conditions constitute a “natural experiment” for estimating adsorption rates. We developed a simple mass-balance model for the radionuclides in Lake Kinneret that accurately predicted the Ra isotope ratios and the ²²⁶Ra activity in the lake. The model is comprised of simultaneous equations; one for each radionuclide. The equations have one input term: supply of radionuclides from the saline springs; and three output terms: adsorption on particles in the lake, radioactive decay and outflow from the lake. The redundancy in the analytical solutions to the mass balance equations for the relevant nuclides constrained the values of Ra and Th adsorption rate constants to a very narrow range. Our results indicate that the adsorption rate constant for Ra is between 0.005 d⁻¹ and 0.02 d⁻¹. The rate constant for Th is between 0.5 d⁻¹ and 1 d⁻¹, about fifty to a hundred times higher. The estimated desorption rate coefficient for Ra is about 50-100 times larger than its adsorption rate constant. The mass-balance equations show that the residence times of all Ra isotopes (²²⁶Ra, ²²⁸Ra,²²³Ra, ²²⁴Ra) and of ²²⁸Th in the lake are about 95, 92, 14, 6 and 1 d, respectively. These residence times are much shorter than the residence time of water in the lake (about 5.5 y). The steady state activity ratios in Lake Kinneret depend mainly on the adsorption rate constants, decay constants, the outflow rate from the lake and the activity ratios in the saline springs. The activity ratios are independent of the saline springs flow rate.     

Radium uptake during barite recrystallization at 23 ± 2 °C as a function of solution composition: An experimental Ba and Ra tracer study

High-purity synthetic barite powder was added to pure water or aqueous solutions of soluble salts (BaCl₂, Na₂SO₄, NaCl and NaHCO₃) at 23 ± 2 °C and atmospheric pressure. After a short pre-equilibration time (4 h) the suspensions were spiked either with ¹³³Ba or ²²⁶Ra and reacted under constant agitation during 120-406 days. The pH values ranged from 4 to 8 and solid to liquid (S/L) ratios varied from 0.01 to 5 g/l. The uptake of the radiotracers by barite was monitored through repeated sampling of the aqueous solutions and radiometric analysis. For both ¹³³Ba and ²²⁶Ra, our data consistently showed a continuous, slow decrease of radioactivity in the aqueous phase.Mass balance calculations indicated that the removal of ¹³³Ba activity from aqueous solution cannot be explained by surface adsorption only, as it largely exceeded the 100% monolayer coverage limit. This result was a strong argument in favor of recrystallization (driven by a dissolution-precipitation mechanism) as the main uptake mechanism. Because complete isotopic equilibration between aqueous solution and barite was approached or even reached in some experiments, we concluded that during the reaction all or substantial fractions of the initial solid had been replaced by newly formed barite.The ¹³³Ba data could be successfully fitted assuming constant recrystallization rates and homogeneous distribution of the tracer into the newly formed barite. An alternative model based on partial equilibrium of ¹³³Ba with the mineral surface (without internal isotopic equilibration of the solid) could not reproduce the measured activity data, unless multistage recrystallization kinetics was assumed. Calculated recrystallization rates in the salt solutions ranged from 2.8 × 10⁻¹¹ to 1.9 × 10⁻¹⁰ mol m⁻² s⁻¹ (2.4-16 μmol m⁻² d⁻¹), with no specific trend related to solution composition. For the suspensions prepared in pure water, significantly higher rates (∼5.7 × 10⁻¹⁰ mol m⁻² s⁻¹ or ∼49 μmol m⁻² d⁻¹) were determined.Radium uptake by barite was determined by monitoring the decrease of ²²⁶Ra activity in the aqueous solution with alpha spectrometry, after filtration of the suspensions and sintering. The evaluation of the Ra uptake experiments, in conjunction with the recrystallization data, consistently indicated formation of non-ideal solid solutions, with moderately high Margules parameters (W_AB = 3720-6200 J/mol, a₀ = 1.5-2.5). These parameters are significantly larger than an estimated value from the literature (W_AB = 1240 J/mol, a₀ = 0.5).In conclusion, our results confirm that radium forms solid solutions with barite at fast kinetic rates and in complete thermodynamic equilibrium with the aqueous solutions. Moreover, this study provides quantitative thermodynamic data that can be used for the calculation of radium concentration limits in environmentally relevant systems, such as radioactive waste repositories and uranium mill tailings.     

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.     

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.     

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.     

Radium geochemistry of ground waters in Paleozoic carbonate aquifers,midcontinent, USA

The purpose of this study was to elucidate the processes controlling the distribution and behavior of the longer-lived Ra isotopes in continuous Paleozoic carbonate aquifers of parts of Missouri, Kansas, and Oklahoma. Activities of (²²⁸Ra) and (²²⁶Ra) were analyzed in fresh and saline ground waters, brines, and rocks. The fluids have a wide salinity range (200–250,000 mg l⁻¹ total dissolved solids). The (²²⁶Ra) activity ranges from 0.66–7660 dpm kg⁻¹ and correlates with salinity and other alkaline earth element (Ca, Sr, and Ba) concentrations. The range of (²²⁸Ra:²²⁶Ra) ratios in the fluids (0.06–1.48) is similar to that in the aquifer rocks (0.21–1.53). The relatively low mean fluid (²²⁸Ra:²²⁶Ra) ratio (0.30) reflects the low Th:U ratio of the predominant carbonate aquifer rock. Radium occurs mostly (≥77%) as Ra²⁺ species in the fluids. Salinity-dependent sorption–desorption processes (with log K values from 10⁰–10⁴ and negatively correlated with salinity), involving Th-enriched surface coatings on aquifer flow channels, can explain the rapid solid–fluid transfer of Ra isotopes in the system and the correlation of Ra with salinity.     

Ground water geochemistry of 228Ra, 226Ra and 222Rn

²²⁸Ra, ²²⁶Ra, and ²²²Rn activities were determined on over 150 ground water samples collected from drilled, public water supply wells throughout South Carolina. A wide range of aquifer lithologies were sampled including the crystalline rocks of the Piedmont and sedimentary deposits of the Coastal Plain. A significant linear relationship between log ²²⁸Ra and log ²²⁶Ra (n = 182, r = 0.83) was indistinguishable between Piedmont and Coastal Plain ground water. Median ${}^{228}\text{Ra}{}^{226}\text{Ra}$ activity ratios for the Piedmont, 1.2, and Coastal Plain, 1.3, ground water are close to estimated average crustal ${}^{232}\text{Th}{}^{238}\text{U}$ activity ratios of 1.2 to 1.5 corresponding to Th/U weight ratios of 3.5 to 4.5. A linear correlation was also found between log ²²²Rn and log ²²⁶Ra for Piedmont (n = 68, r = 0.62) and Coastal Plain (n = 89, r = 0.64) ground water. However, the median ${}^{222}\text{Rn}{}^{226}\text{Ra}$ activity ratio for Piedmont ground water, 6100, was much higher than for Coastal Plain ground water, 230. Higher excess ²²²Rn activities may be due to greater retention of ²²⁶Ra by the chemically active Piedmont aquifers compared to the more inert sand aquifers sampled in the Coastal Plain. The relationship between log ²²⁸Ra and log ²²⁶Ra was used to predict total Ra (${}^{228}\text{Ra +}{}^{226}\text{Ra}$) distributions in Appalachian and Atlantic and Gulf Coastal Plain ground water. Predictions estimate that 2.4% of Appalachian and 5.3% of Atlantic and Gulf Coastal Plain ground water supplies contain total Ra activities in excess of the 5 pCi/l limit established by the U.S. Environmental Protection Agency. These predictions also indicate that 40–50% of these ground water wells may be overlooked using the presently suggested screening activity of 3.0 pCi/l of ²²⁶Ra for ²²⁸Ra analysis.     

Using short-lived nuclides of the U- and Th-series to probe the kinetics of colloid migration in forested soils

The recent chemical dynamics of a podzolic forest soil section (from the Strengbach watershed, France) was investigated using U- and Th-series nuclides. Analyses of (²³⁸U), (²³⁰Th), (²²⁶Ra), (²³²Th), (²²⁸Ra) and (²²⁸Th) activities in the soil particles, the seepage waters, and the mature leaves of the beech trees growing on this soil were performed by TIMS or gamma spectrometry. The simultaneous analysis of the different soil (sl) compartments allows to demonstrate that a preferential Th leaching over Ra must be assumed to explain the (²²⁶Ra/²³⁰Th), (²²⁸Ra/²³²Th) and (²²⁸Th/²²⁸Ra) disequilibria recorded in the soil particles. The overall Ra- and Th- transfer schemes are entirely consistent with the prevailing acido-complexolysis weathering mechanism in podzols. Using a continuous open-system leaching model, the (²²⁶Ra/²³⁰Th) and (²²⁸Ra/²³²Th) disequilibria measured in the different soil layers enable dating of the contemporary processes occurring in this soil. In this way, we have determined that a preferential Th-leaching from the shallow Ah horizon, due to a strong complexation with organic colloids, began fairly recently (18 years ago at most). The continual increase in pH recorded in precipitations over the last 20 years is assumed to be the cause of this enhanced organic complexation. A lower soil horizon (50-60 cm) is also affected by preferential Th leaching, though lasting over several centuries at least, with a much smaller leaching rate. The migration of Th isotopes through this soil section might hence be used as a tracer for the organic colloids migration and the induced radioactive disequilibria demonstrate to be useful for assessing the colloidal migration kinetics in a forested soil.Ra and Th isotopic ratios also appear to be valuable tracers of some mineral-water-plant interactions occurring in soil. The (²²⁸Ra/²²⁶Ra) ratio enables discrimination of the Ra flux originating from leaf degradation from that originating from mineral weathering in shallow −10 cm seepage soil waters. It appears that, at least in some cases, the Ra-isotopic ratio measured in forest-soil seepage waters may not be representative of the Ra-isotopic ratio released from mineral weathering, indicating that the different origins of the dissolved ²²⁶Ra and ²²⁸Ra must be taken into account.     

Factors controlling the groundwater transport of U, Th, Ra, and Rn

A model for the groundwater transport of naturally occurring U, Th, Ra, and Rn nuclides in the²³⁸U and²³²Th decay series is discussed. The model developed here takes into account transport by advection and the physico-chemical processes of weathering, decay, α-recoil, and sorption at the water-rock interface. It describes the evolution along a flowline of the activities of the²³⁸U and²³²Th decay series nuclides in groundwater. Simple sets of relationships governing the activities of the various species in solution are derived, and these can be used both to calculate effective retardation factors and to interpret groundwater data. For the activities of each nuclide, a general solution to the transport equation has been obtained, which shows that the activities reach a constant value after a distance ϰ_i, characteristic of each nuclide. Where ϰ_i is much longer than the aquifer length, (for²³⁸U,²³⁴U, and²³²Th), the activities grow linearly with distance. Where gKⁱ is short compared to the aquifer length, (for²³⁴Th,²³⁰Th,²²⁸Th,²²⁸Ra, and²²⁴Ra), the activities rapidly reach a constant or quasi-constant activity value. For²²⁶Ra and²²²Rn, the limiting activity is reached after 1 km. High δ²³⁴U values (proportional to the ratio^ɛ234Th/^W238U) can be obtained through high recoil fraction and/or low weathering rates. The activity ratios²³⁰Th/²³²Th,²²⁸Ra/²²⁶Ra and²²⁴Ra/²²⁶Ra have been considered in the cases where either weathering or recoil is the predominant process of input from the mineral grain. Typical values for weathering rates and recoil fractions for a sandy aquifer indicate that recoil is the dominant process for Th isotopic ratios in the water. Measured data for Ra isotope activity ratios indicate that recoil is the process generally controlling the Ra isotopic composition in water. Higher isotopic ratios can be explained by different desorption kinetics of Ra. However, the model does not provide an explanation for²²⁸Ra/²²⁶Ra and²²⁴Ra/²²⁶Ra activity ratios less than unity. From the model, the highest²²²Rn emanation equals 2ɛ. This is in agreement with the hypothesis that²²²Rn activity can be used as a first approximation for input by recoil (Krishnaswamiet al 1982). However, high²²²Rn emanation cannot be explained by production from the surface layer as formulated in the model. Other possibilities involve models including surface precipitation, where the surface layer is not in steady-state.     

Coupling between Pbex and organic matter in sediments of a nutrient-enriched lake: An example from Lake Chenghai, China

Sediment cores were collected from deep-water areas of Lake Chenghai, China in June 1997. The vertical profile of ¹³⁷Cs activity gives reliable geochronological results. The results also indicate that sediment accumulation rates in deep-water areas of Lake Chenghai were relatively constant in recent decades, averaging 0.43 g cm^− 2 y^− 1, despite a variable organic carbon influx. ²¹⁰Pb_eq (= ²²⁶Ra) activity was relatively constant also, with an average value of 54.3 ± 3.2 Bq kg^− 1. Vertical profiles of ²¹⁰Pb_ex (= ²¹⁰Pb_total − ²²⁶Ra) decreased exponentially, resulting in somewhat lower sediment accumulation rates (0.3 g cm^− 2 y^− 1). These lower rates are likely less reliable, as the relatively large fluctuations in ²¹⁰Pb_ex activities correlate closely to the organic carbon (C_org) content of the sediments. For example, the vertical profile of ²¹⁰Pb_ex activity displays peaks at mass depths of 3.7-4.7 g cm^− 2 (10-12 cm) and 10-11 g cm^− 2(25-28 cm), similar to the maxima in the vertical profile of C_org. This phenomenon must be related to the delivery of particulate organic matter (POM) from the water to the sediments, or to watershed soil erosion. Since the mean atomic ratios of H_org / C_org and C_org / N_org in Lake Chenghai sediments are 5.5 and 7.0, respectively, indicating that POM was predominantly derived from the remains of authigenic algae, this eliminates watershed erosion rates as a primary control on lake sedimentation rates as resolved by ²¹⁰Pb_ex. Sedimentation fluxes (F(C_org)) of particulate organic carbon since 1970 varied between 60 to 160 g m^− 2 y^− 1, and appeared to closely influence variations in ²¹⁰Pb_ex concentrations. For example, sedimentation fluxes of ²¹⁰Pb_ex (F(²¹⁰Pb_ex)) showed maxima in the years 1972-1974 and 1986-1989, likely reflecting historical variations of lake biological productivity or carbon preservation.     

Coprecipitation in the barite isostructural family: 2. Numerical simulations of reactions and mass transport

Coprecipitation of barite with trace constituents was simulated with consideration of aqueous speciation and complexation, mixing properties for the binary solid solutions (Zhu, this issue), precipitation and dissolution kinetics, and advective-dispersive transport. Speciation-solubility modeling was used to reproduce BaSO₄-RaSO₄ coprecipitation experimental results, and to calculate CrO₄²⁻ aqueous concentrations in equilibrium with a Ba(SO₄,CrO₄) solid solution. Kinetic reaction path modeling was used to simulate the coprecipitation of barite with RaSO₄ to form an onion-like chemically zoned solid upon the cooling of oil field brine.A one-dimensional coupled reactive mass transport model shows a strikingly different transport pattern for the tracer Ra²⁺, when the dominant attenuation reaction is with solid solution (Ba, Ra) SO₄ as compared to the case when it is controlled by pure RaSO₄ and barite solids under local equilibrium conditions. A self-enrichment of Ra²⁺ in the groundwater and aquifer solid matrix—higher concentrations of Ra²⁺ downstream from the reaction front—results from the coprecipitation reaction and advective-dispersive transport. This self-enrichment process generates a secondary tracer source, which has tracer concentrations higher than that of the original source. On the other hand, coprecipitation reactions can reduce Ra²⁺ concentrations in groundwater to a much lower level (below ppb) than that of pure RaSO₄(c) solubility (near ppm), which has been used to establish the Ra²⁺ concentration limits in groundwater, soil, and nuclear waste repositories.     

The mobility of radium-226 and trace metals in pre-oxidized subaqueous uranium mill tailings

The exchange of ²²⁶Ra and trace metals across the tailings-water interface and the mechanisms governing their mobility were assessed via sub-centimetre resolution profiling of dissolved constituents across the tailings–water interface in Cell 14 of the Quirke Waste Management Area at Rio Algom's Quirke Mine, near Elliot Lake, Ontario, Canada. Shallow zones (<1.5 m water depth) are characterized by sparse filamentous vegetation, well-mixed water columns and fully oxygenated bottom waters. Profiles of dissolved O₂, Fe and Mn indicate that the tailings deposits in these areas are sub-oxic below tailings depths of ∼3 cm. These zones exhibit minor remobilization of Ra in the upper 5 cm of the tailings deposit; ²²⁶Ra fluxes at these sites are relatively small, and contribute negligibly to the water column activity of ²²⁶Ra. The shallow areas also exhibit minor remobilization of Ni, As, Mo and U. The release of these elements to the water cover is, however, limited by scavenging mechanisms in the interfacial oxic horizons. The presence of thick vegetation (Chara sp.) in the deeper areas (>2 m water depth) fosters stagnant bottom waters and permits the development of anoxia above the benthic boundary. These anoxic tailings are characterized by substantial remobilization of ²²⁶Ra, resulting in a relatively large flux of ²²⁶Ra from the tailings to the water column. The strong correlation between the porewater profiles of ²²⁶Ra and Ba (r²=0.99), as well as solubility calculations, indicate that the mobility of Ra is controlled by saturation with respect to a poorly ordered and/or impure barite phase [(Ra,Ba)SO₄]. In the anoxic zones, severe undersaturation with respect to barite is sustained by microbial SO₄ reduction. Flux calculations suggest that the increase in ²²⁶Ra activity in the water cover since 1995 (from <0.5 to 2.5 Bq l⁻¹) can be attributed to an increase in the spatial distribution of anoxic bottom waters caused by increased density of benthic flora. The anoxic, vegetated areas also exhibit minor remobilization with respect to dissolved As, Ni and Zn. The removal of trace metals in the anoxic bottom waters appears to be limited by the availability of free sulphide. Collectively, the data demonstrate that while the water cover over the U mill tailings minimizes sulphide oxidation and metal mobility, anoxic conditions which have developed in deeper areas have led to increased mobility of ²²⁶Ra.     

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.