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.     

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.     

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.     

Gross-beta activity in ground water: natural sources and artifacts of sampling and laboratory analysis

Gross-beta activity has been used as an indicator of beta-emitting isotopes in water since at least the early 1950s. Originally designed for detection of radioactive releases from nuclear facilities and weapons tests, analysis of gross-beta activity is widely used in studies of naturally occurring radioactivity in ground water. Analyses of about 800 samples from 5 ground-water regions of the United States provide a basis for evaluating the utility of this measurement. The data suggest that measured gross-beta activities are due to (1) long-lived radionuclides in ground water, and (2) ingrowth of beta-emitting radionuclides during holding times between collection of samples and laboratory measurements.Although⁴⁰K and²²⁸Ra appear to be the primary sources of beta activity in ground water, the sum of⁴⁰K plus²²⁸Ra appears to be less than the measured gross-beta activity in most ground-water samples. The difference between the contribution from these radionuclides and gross-beta activity is most pronounced in ground water with gross-beta activities > 10 pCi/L, where these 2 radionuclides account for less than one-half the measured ross-beta activity. One exception is groundwater from the Coastal Plain of New Jersey, where⁴⁰K plus²²⁸Ra generally contribute most of the gross-beta activity. In contrast,⁴⁰K and²²⁸Ra generally contribute most of beta activity in ground water with gross-beta activities < 1 pCi/L.The gross-beta technique does not measure all beta activity in ground water. Although³H contributes beta activity to some ground water, it is driven from the sample before counting and therefore is not detected by gross-beta measurements. Beta-emitting radionuclides with half-lives shorter than a few days can decay to low values between sampling and counting. Although little is known about concentrations of most short-lived beta-emitting radionuclides in environmental ground water (water unaffected by direct releases from nuclear facilities and weapons tests), their activities are expected to be low.Ingrowth of beta-emitting radionuclides during sample holding times can contribute to gross-beta activity, particularly in ground water with gross-beta activities > 10 pCi/L. Ingrowth of beta-emitting progeny of²³⁸U, specifically²³⁴Pa and²³⁴Th, contributes much of the measured gross-beta activity in ground water from 4 of the 5 areas studied. Consequently, gross-beta activity measurements commonly overestimate the abundance of beta-emitting radionuclides actually present in ground water. Differing sample holding times before analysis lead to differing amounts of ingrowth of the two progeny. Therefore, holding times can affect observed gross-beta measurements, particularly in ground water with²³⁸U activities that are moderate to high compared with the activity of⁴⁰K plus²²⁸Ra. Uncertainties associated with counting efficiencies for beta particles with different energies further complicate the interpretation of gross-beta measurements.     

Radiochemical separation and determination of radium-228 in bottled mineral waters by low level gamma spectrometry and its committed effective dose

?The gross beta and ²²⁸Ra radioactivity measurements in mineral waters were performed by proportional counter and gamma spectrometry, respectively, in this study. The natural mineral water samples were collected from various regions of Turkey for this study. Gross beta activities have been determined according to the United States Environmental Protection Agency standard method (EPA 900). In the case that the gross beta activity was determined to be greater than 1 Bq/L, then the ²²⁸Ra activity concentration in the related mineral water sample was specifically measured. ²²⁸Ra activity in mineral water samples was determined by high-purity germanium (HPGe) detector. The photopeak efficiencies were calculated by modeling the sample geometry and the detector in Canberra software LabSOCS. The gross beta activities in the eight of 32 bottled mineral water samples were greater than 1 Bq/L. ²²⁸Ra activity concentrations in bottled mineral waters were determined within 0.100–1.04 Bq/L. The committed effective doses were calculated for three different scenarios according to mineral water consumption rates.     

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.     

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.     

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.     

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.     

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.     

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.     

Radium and radon content in the carbonate-rock aquifer of the southern Italian region of Apulia

High concentrations of ²²²Rn have been found throughout the waters of the coastal carbonate-rock Mesozoic aquifer located in the region of Apulia in southern Italy. Studies undertaken have determined that such concentrations are due to the radioisotopic features of terra rossa, a type of paleosol that is generated as a residual byproduct of carbonate dissolution and is found to be widespread throughout the aquifers fissures and karst cavities.These special types of soil feature a rather high clay content (80–95%) and, although variable, their specific ²²⁶Ra activity (70–147 Bq/kg) is nonetheless considerably greater than that of limestone (~50 Bq/kg). In fact, there are substantial differences in ²²²Rn concentrations found in waters that come into contact with this type of rock and paleosol.The partial dissolution of some carbonate rock samples in the laboratory confirmed that the ²²⁶Ra released by the dissolved rock primarily accumulates in the residual soil deposits, especially in ones containing finer granules. This has also been the result of experiments conducted on 15 terra rossa samples collected from the region, which indicates that there is a close correlation between the specific ²²⁶Ra activity and the clay content of such paleosols, which varies with the stage of weathering.It has been found that the ²²²Rn concentrations in the regions waters, depend on the specific terra rossa ²²⁶Ra activity rather than on the quantity of terra rossa.Field checks have confirmed the possibility of using ²²⁶Ra and ²²²Rn as natural tracers in order to define hydrogeological problems in special environments such as karst. They can be used to distinguish the different water bearing zones in the carbonate-rock aquifer; analyze the influence of tides on coastal springs; determine the flow direction in the proximity of a well; recognize, recharge and the progressive decline of the groundwater level; derive indications of underground flow paths; and the occurrence of fissures and karstic cavities in the carbonate-rock aquifer.

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.     

Application of radium isotopes to determine crustal residence times of hydrothermal fluids from two sites on the Reykjanes Peninsula, Iceland

Radium isotopes were used to determine the crustal residence times of hydrothermal fluids from two geothermal wells (Svartsengi and Reykjanes) from the Reykjanes Peninsula, Iceland. The availability of rock samples from the subsurface (to depths of 2400 m) allowed direct comparison of the radium isotopic characteristics of the fluids with those of the rocks within the high temperature and pressure reaction zone. The ²²⁶Ra activity of the Svartsengi fluid was ∼one-fourth of the Reykjanes fluid and the ²²⁸Ra/²²⁶Ra ratio of the Svartsengi fluid was ∼twice that of Reykjanes. The fluid isotopic characteristics were relatively stable for both sites over the 6 years (2000-2006) of the study. It was determined, using a model that predicts the evolution of the fluid ²²⁸Ra/²²⁶Ra ratio with time, that both sites had fluid residence times, from the onset of high temperature water-rock reaction, of less than 5 years. Measurement of the short-lived ²²⁴Ra and ²²³Ra allowed estimation of the recoil input parameter used in the model. The derived timescale is consistent with results from similar studies of fluids from submarine systems, and has implications for the use of terrestrial systems in Iceland as an exploited energy resource.     

Analysis of I in groundwater samples: Direct and quantitative results below the drinking water standard

This paper highlights an analytical method based on mass measurement that can be used to directly quantify ¹²⁹I in groundwater samples at concentrations below the maximum contaminant level (MCL) without the need for sample pre-concentration or extraction. Samples were analyzed on a Perkin Elmer ELAN DRC II ICP-MS after minimal dilution using O₂ as the reaction gas. Analysis of continuing calibration verification standards indicated that the dynamic reaction cell (DRC) mode could be used for quantitative analysis of ¹²⁹I in samples below the MCL (0.0057 ng/mL or 1 pCi/L). The low analytical detection limit of ¹²⁹I analysis in the DRC mode coupled with minimal sample dilution (1.02x) resulted in a final estimated quantification limit of 0.0051 ng/mL. Subsequent analysis of three groundwater samples containing ¹²⁹I resulted in fully quantitative results in the DRC mode, and spike recovery analyses performed on all three samples confirmed that the groundwater matrix did not adversely impact the analysis of ¹²⁹I in the DRC mode. This analytical approach has been proven to be a cost-effective, high-throughput technique for the direct, quantitative analysis of ¹²⁹I in groundwater samples at environmentally relevant concentrations that reach below the current MCL.     

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.     

Geochemical evaluation of flowback brine from Marcellus gas wells in Pennsylvania,USA

Large quantities of highly saline brine flow from gas wells in the Marcellus Formation after hydraulic stimulation (“fracking”). This study assesses the composition of these flowback waters from the Marcellus shale in Pennsylvania, USA. Concentrations of most inorganic components of flowback water (Cl, Br, Na, K, Ca, Mg, Sr, Ba, Ra, Fe, Mn, total dissolved solids, and others) increase with time from a well after hydraulic stimulation. Based on results in several datasets reported here, the greatest concentration of Cl⁻ in flowback water is 151,000 mg/L. For total Ra (combined ²²⁶Ra and ²²⁸Ra) in flowback, the highest level reported is 6540 pCi/L. Flowback waters from hydraulic fracturing of Marcellus wells resemble brines produced from conventional gas wells that tap into other Paleozoic formations in the region. The Br/Cl ratio and other parameters indicate that both types of brine formed by the evaporation of seawater followed by dolomitization, sulfate reduction and subsurface mixing with seawater and/or freshwater. Trends and relationships in brine composition indicate that (1) increased salt concentration in flowback is not mainly caused by dissolution of salt or other minerals in rock units, (2) the flowback waters represent a mixture of injection waters with highly concentrated in situ brines similar to those in the other formations, and (3) these waters contain concentrations of Ra and Ba that are commonly hundreds of times the US drinking water standards.     

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.     

Alpha-emitting isotopes and chromium in a coastal California aquifer

The unadjusted 72-h gross alpha activities in water from two wells completed in marine and alluvial deposits in a coastal southern California aquifer 40 km north of San Diego were 15 and 25 picoCuries per liter (pCi/L). Although activities were below the Maximum Contaminant Level (MCL) of 15 pCi/L, when adjusted for uranium activity; there is concern that new wells in the area may exceed MCLs, or that future regulations may limit water use from the wells. Coupled well-bore flow and depth-dependent water-quality data collected from the wells in 2011 (with analyses for isotopes within the uranium, actinium, and thorium decay-chains) show gross alpha activity in marine deposits is associated with decay of naturally-occurring ²³⁸U and its daughter ²³⁴U. Radon activities in marine deposits were as high as 2230 pCi/L. In contrast, gross alpha activities in overlying alluvium within the Piedra de Lumbre watershed, eroded from the nearby San Onofre Hills, were associated with decay of ²³²Th, including its daughter ²²⁴Ra. Radon activities in alluvium from Piedra de Lumbre of 450 pCi/L were lower than in marine deposits. Chromium VI concentrations in marine deposits were less than the California MCL of 10 μg/L (effective July 1, 2014) but δ⁵³Cr compositions were near zero and within reported ranges for anthropogenic chromium. Alluvial deposits from the nearby Las Flores watershed, which drains a larger area having diverse geology, has low alpha activities and chromium as a result of geologic and geochemical conditions and may be more promising for future water-supply development.