Present status of 222Rn in groundwater in Extremadura

Radon-222 was measured in groundwater sources of Extremadura (Spain), analyzing 350 samples from private and public springs, wells, and spas by liquid scintillation counting (LSC) and gamma spectrometry. The (222)Rn activity concentrations ranged from 0.24 to 1168BqL(-1). The statistical analysis showed a log-normal distribution with a mean of (111+/-7)BqL(-1) and a median of (36+/-3)BqL(-1). A hydrogeological study revealed correlations between the activity concentration and the aquifer material's characteristics. A map of (222)Rn in groundwater was elaborated and compared with the natural gamma radiation map for this region. About 35% of the samples showed (222)Rn activity concentrations above the Euratom recommended limit of 100BqL(-1). Three uranium series radionuclides ((238)U, (234)U, and (226)Ra) were also assayed by alpha-particle spectrometry, estimating the annual effective dose due to the presence of these natural radionuclides in drinking water.     

Present status of Rn in groundwater in Extremadura

Radon-222 was measured in groundwater sources of Extremadura (Spain), analyzing 350 samples from private and public springs, wells, and spas by liquid scintillation counting (LSC) and gamma spectrometry. The ²²²Rn activity concentrations ranged from 0.24 to 1168 Bq L⁻¹. The statistical analysis showed a log-normal distribution with a mean of (111 ± 7) Bq L⁻¹ and a median of (36 ± 3) Bq L⁻¹. A hydrogeological study revealed correlations between the activity concentration and the aquifer material's characteristics. A map of ²²²Rn in groundwater was elaborated and compared with the natural gamma radiation map for this region. About 35% of the samples showed ²²²Rn activity concentrations above the Euratom recommended limit of 100 Bq L⁻¹. Three uranium series radionuclides (²³⁸U, ²³⁴U, and ²²⁶Ra) were also assayed by alpha-particle spectrometry, estimating the annual effective dose due to the presence of these natural radionuclides in drinking water.     

Determination of uranium and radon in potable water samples

In this work, potable water samples collected from boreholes of the Migdonia valley, located NE of the city of Thessaloniki, were analyzed for the determination of uranium (238U) and radon (222Rn) concentrations. The objective of the present work is to examine if there is any correlation between radon and uranium concentrations in the water samples. For the determination of traces of uranium in water samples, an analytical technique was developed based on the selective adsorption of uranium on the chelating resin, SRAFION NMRR, and the in situ determination of the retained uranium by instrumental neutron activation analysis (INAA). By the described procedure, it was possible to determine uranium amounts in the range of microg/l. For measuring radon in water, a liquid scintillation counting system, using the Packard protocol was employed. The measured 222Rn activity concentrations are from background level up to 160 Bq l (-1).     

Determination of U, Pu and Am isotopes in Irish Sea sediment by a combination of AMS and radiometric methods

Samples from a marine sediment core from the Irish Sea (54.416 N, 3.563 W) were analyzed for the isotopic composition of uranium, plutonium and americium by a combination of radiometric methods and AMS. The radiochemical procedure consisted of a Pu separation step by anion exchange, subsequent U separation by extraction chromatography using UTEVA^® and finally Am separation with TRU^® Resin.Additionally to radiometric determination of these isotopes by alpha spectrometry, the separated samples were also used for the determination of ²³⁶U/²³⁸U and plutonium isotope ratios by Accelerator Mass Spectrometry (AMS) at the VERA facility.     

Characterisation of projectiles composed of depleted uranium

Projectiles suspected to be composed of depleted uranium (DU) were found in Kosovo. Their properties were analysed using alpha and gamma ray spectrometry, mass spectrometry and electron microscopy. They were found to be composed of DU with small amounts of other elements such as Ti. 236U was detected in the penetrators, reflecting the use of reprocessed fuel. No transuranium elements were detected. The typical external dose rate meter is not the best option for mapping the location of penetrators from the ground. Monte Carlo calculations were performed in estimating possible skin doses. Penetrators in long-lasting contact with skin may cause a notable equivalent dose to skin.     

Sector field inductively coupled plasma mass spectrometry, another tool for plutonium isotopes and plutonium isotope ratios determination in environmental matrices

The transfer of radio nuclides into the different compartments of the environment are widely studied and leads to the elaboration of transfer models in order to evaluate potential impact onto the environment and humans. Accurate experimental data are needed to validate these models for all types of matrices (air, water, sediments, soils, biota and food...). Among these radionuclides, 238Pu, 239Pu, 240Pu and 241Pu, are often mentioned. They have been released into the environment by nuclear weapon tests, nuclear facilities, reactors or satellite accidents. These different sources have different 240Pu/239Pu ratios and therefore this ratio is used to provide information on the source of contamination into the environment. The most conventional analytical tools used for plutonium isotope determination are liquid scintillation and alpha spectrometry, and thermal ionisation mass spectrometry (TIMS) is still considered as the primary method for determination of plutonium isotope ratios. During the last decade, mass spectrometers equipped with plasma ion sources and sector field analysers were developed and can offer now another alternative method for the accurate determination of isotope content and ratios of long-lived radionuclides in environmental samples. This paper presents and discusses the results obtained for 239Pu, 240Pu and 241Pu content and isotope ratios by sector field ICP-MS in different environmental matrices.     

The use of isotope dilution mass spectrometry for the certification of standard reference materials

Isotope dilution mass spectrometry (IDMS) has been used extensively at the U.S. National Bureau of Standards as an accurate method to determine trace element concentrations in natural materials. Thermal ionization mass spectrometry is a single element technique capable of high accuracy and precision, and has been used for “definitive” measurements of trace elements in sera with 95% confidence limits less than 0.25%. Spark source mass spectrometry is a complementary multielement, high-sensitivity technique that has been used to determine up to 20 elements in a sample, with typical accuracies of 2%–5%. Together with appropriate chemical separations, such as anion and cation exchange, chelate resins, electrodeposition, and chemical extraction, IDMS has been applied to elemental concentration measurements ranging over eight orders of magnitude, from decigrams/gram to picograms/gram. Many of these applications have been used for the certification of a broad spectrum of biological and environmental Standard Reference Materials, including lead in Trace Elements in Water (SRM 1643), 15 elements in Coal Fly Ash (SRM 1633a), uranium in Bovine Liver (SRM 1577a), and mercury in water (SRM 1642).     

Natural radioactivity in phosphates, phosphogypsum and natural waters in Morocco

The contents of natural radionuclides (uranium, actinium and thorium series) were measured in sedimentary phosphate rock samples using high-resolution gamma spectrometry. Data obtained for uranium content (ppm) were compared with the results obtained by a method based on the measurements using solid-state nuclear track detectors (SSNTD) in the same samples. The potential leaching of radionuclides from sedimentary phosphate rock during the industrial production of the phosphoric acid was studied. The process of leaching of the radioisotopes from phosphogypsum was discussed. A method for the direct alpha counting of 226Ra thin source, elaborated by the deposition of Ra from aqueous solutions on manganese oxides film deposited on polyvinyl support, have been developed and applied for the determination of 226Ra in natural water samples. The results show that only the water sample from the mine area reveals the presence of 226Ra at a level of about 0.2 Bq l-1.     

Determination of extremely low (236)U/(238)U isotope ratios in environmental samples by sector-field inductively coupled plasma mass spectrometry using high-efficiency sample introduction

A method by inductively coupled plasma mass spectrometry (ICP-MS) was developed which allows the measurement of (236)U at concentration ranges down to 3 x 10(-14)g g(-1) and extremely low (236)U/(238)U isotope ratios in soil samples of 10(-7). By using the high-efficiency solution introduction system APEX in connection with a sector-field ICP-MS a sensitivity of more than 5,000 counts fg(-1) uranium was achieved. The use of an aerosol desolvating unit reduced the formation rate of uranium hydride ions UH(+)/U(+) down to a level of 10(-6). An abundance sensitivity of 3 x 10(-7) was observed for (236)U/(238)U isotope ratio measurements at mass resolution 4000. The detection limit for (236)U and the lowest detectable (236)U/(238)U isotope ratio were improved by more than two orders of magnitude compared with corresponding values by alpha spectrometry. Determination of uranium in soil samples collected in the vicinity of Chernobyl nuclear power plant (NPP) resulted in that the (236)U/(238)U isotope ratio is a much more sensitive and accurate marker for environmental contamination by spent uranium in comparison to the (235)U/(238)U isotope ratio. The ICP-MS technique allowed for the first time detection of irradiated uranium in soil samples even at distances more than 200 km to the north of Chernobyl NPP (Mogilev region). The concentration of (236)U in the upper 0-10 cm soil layers varied from 2 x 10(-9)g g(-1) within radioactive spots close to the Chernobyl NPP to 3 x 10(-13)g g(-1) on a sampling site located by >200 km from Chernobyl.     

Uranium-238 and thorium-232 series concentrations in soil, radon-222 indoor and drinking water concentrations and dose assessment in the city of Aldama, Chihuahua, Mexico

High-resolution gamma spectrometry was used to determine the concentration of 40K, 238U and 232Th series in soil samples taken from areas surrounding the city of Aldama, in Chihuahua. Results of indoor air short-time sampling, with diffusion barrier charcoal detectors, revealed relatively high indoor radon levels, ranging from 29 to 422 Bq/m3; the radon concentrations detected exceeded 148 Bq/m3 in 76% of the homes tested. Additionally, liquid scintillation counting showed concentrations of radon in drinking water ranging from 4.3 to 42 kBq/m3. The high activity of 238U in soil found in some places may be a result of the uranium milling process performed 20 years ago in the area. High radon concentrations indoor and in water may be explained by assuming the presence of uranium-bearing rocks underneath of the city, similar to a felsic dike located near Aldama. The estimated annual effective dose of gamma radiation from the soil and radon inhalation was 3.83 mSv.     

Determination of depleted uranium in environmental samples by gamma-spectroscopic techniques

The military use of depleted uranium initiated the need for an efficient and reliable method to detect and quantify DU contamination in environmental samples. This paper presents such a method, based on the gamma spectroscopic determination of 238U and 235U. The main advantage of this method is that it allows for a direct determination of the U isotope ratio, while requiring little sample preparation and being significantly less labor intensive than methods requiring radiochemical treatment. Furthermore, the fact that the sample preparation is not destructive greatly simplifies control of the quality of measurements. Low energy photons are utilized, using Ge detectors efficient in the low energy region and applying appropriate corrections for self-absorption. Uranium-235 in particular is determined directly from its 185.72 keV photons, after analyzing the 235U-226Ra multiplet. The method presented is applied to soil samples originating from two different target sites, in Southern Yugoslavia and Montenegro. The analysis results are discussed in relation to the natural radioactivity content of the soil at the sampling sites. A mapping algorithm is applied to examine the spatial variability of the DU contamination.     

A complimentary tool in the determination of activity concentrations of naturally occurring radionuclides

The determination of activity concentrations of radionuclides requires a reliable gamma spectrometry system, which also depends on the compulsory attainment of secular equilibrium amongst the progenies of the radionuclide of interest. This is often difficult to attain and hence a helium particle induced x-ray emission technique, not requiring the compulsory attainment of secular equilibrium, was used to determine the actual concentrations of the elemental content of tailings from the high background radiation tin mining area, Jos, Nigeria. The activity concentrations of the radionuclides of ⁴⁰K, ²³²Th and ²³⁸U were also calculated based on their elemental analyses, providing reliable information about the heads of uranium (²³⁸U) and thorium (²³²Th) series on the study area.     

Rapid screening of 90Sr activity in water and milk samples using Cherenkov radiation

A method for screening 90Sr in milk samples is proposed. This method is based on a liquid scintillation technique taking advantage of Cherenkov radiation, which is produced in a liquid medium and then detected by the photomultipliers of a Liquid Scintillation Counter (LSC). Twenty millilitres of water and milk samples spiked with various concentrations of 90Sr/90Y in equilibrium were added in plastic vials and then were measured with an LSC (TriCarb 3170 TR/SL). The derived efficiencies were 49% for water samples and 14% for milk samples. The detection limit was 470 mBq L(-1)(90)Sr for water, without any pretreatment. Milk contains potassium, which also produces Cherenkov radiation due to the presence of 40K. For this reason, the interference of 40K in the measurements of 90Sr in milk samples was also investigated. The detection limit for milk was 1.7 Bq L(-1)90Sr.     

Trace determination of caffeine in surface water samples by liquid chromatography--atmospheric pressure chemical ionization--mass spectrometry (LC-APCI-MS)

A new method based on liquid-liquid extraction (LLE) coupled to reverse phase liquid chromatography and atmospheric pressure chemical ionization mass spectrometry (LC-APCI-MS) has been applied to determine trace amounts of caffeine (1,3,7-trimethylxanthine) in surface water samples from a near coastal ecosystem such as Biscayne Bay, Florida. The rational behind the development of such method will be to evaluate the use of unmetabolized caffeine as a potential dissolved phase tracer of human waste contamination. The method allows for the determination of caffeine at levels as low as 4.0 ng/l (ppt) in both salt and freshwater by extracting and concentrating a 1-1 water sample to a final volume of 500 microl and using HPLC separation coupled to an atmospheric pressure chemical ionization mass spectrometry (APCI-MS) system operated in selected ion monitoring (SIM) for the protonated molecular ions (M + H(+)). Samples from different portions of Biscayne Bay and the Miami River, one of its major tributaries, were analyzed and caffeine was detected in those areas previously identified for consistently exceeding the water quality criteria for fecal coliform bacteria contamination. The caffeine concentration in the samples with positive detection was generally low at levels equal or lower than 41 ng/l. However, there is a marked difference between samples collected in open bay areas and those collected from the Miami River.     

The combined effect of uranium and gamma radiation on biological responses and oxidative stress induced in Arabidopsis thaliana

Uranium never occurs as a single pollutant in the environment, but always in combination with other stressors such as ionizing radiation. As effects induced by multiple contaminants can differ markedly from the effects induced by the individual stressors, this multiple pollution context should not be neglected. In this study, effects on growth, nutrient uptake and oxidative stress induced by the single stressors uranium and gamma radiation are compared with the effects induced by the combination of both stressors. By doing this, we aim to better understand the effects induced by the combined stressors but also to get more insight in stressor-specific response mechanisms. Eighteen-day-old Arabidopsis thaliana seedlings were exposed for 3 days to 10 μM uranium and 3.5 Gy gamma radiation. Gamma radiation interfered with uranium uptake, resulting in decreased uranium concentrations in the roots, but with higher transport to the leaves. This resulted in a better root growth but increased leaf lipid peroxidation. For the other endpoints studied, effects under combined exposure were mostly determined by uranium presence and only limited influenced by gamma presence. Furthermore, an important role is suggested for CAT1/2/3 gene expression under uranium and mixed stressor conditions in the leaves.     

Polybrominated diphenyl ethers, polychlorinated biphenyls and organochlorine pesticides in sediment cores from the Western Scheldt river (Belgium): analytical aspects and depth profiles

A rapid and simple analytical method for the determination of organochlorines, such as polychlorinated biphenyls (PCBs) and selected organochlorinated pesticides (OCPs) and organobromines, such as polybrominated diphenyl ethers (PBDEs), in sediment samples was optimised using CRM 536 (PCBs in freshwater sediment). The method involved a hot Soxhlet extraction that reduced the extraction time to 2 h. Elemental sulphur, which is present in sediments and may interfere during the analysis, was removed by means of copper powder added to the sediment during extraction and into the clean-up cartridge. The analysis of PCBs and OCPs was accomplished by gas chromatography with electron capture or mass spectrometric detection. Similar quantitative results for PCB congeners in CRM 536 were obtained using a 50-m capillary column and a 10-m narrow bore column suited for fast analysis. The analysis of PBDEs was done by mass spectrometry in negative chemical ionisation mode. Concentrations of organic pollutants in two sediment cores (approximately 50 cm depth) from the Scheldt river (south of Antwerp, Belgium) showed a relative steady state for PCBs and DDTs, with a slight decrease in the top layers, suggesting a slight decline in their concentrations due to restrictions in their usage. On the contrary, PBDEs were showing an increase in their concentrations in the top layers (up to 270 and 8400 ng/g dry weight for sum of tri- to hexa-BDE congeners and for BDE 209, respectively). This suggests an increasing trend in the concentrations of PBDEs in the Belgian environment.     

Differences in U root-to-shoot translocation between plant species explained by U distribution in roots

Accumulation and distribution of uranium in roots and shoots of four plants species differing in their cation exchange capacity of roots (CECR) was investigated. After exposure in hydroponics for seven days to 100 μmol U L⁻¹, distribution of uranium in roots was investigated through chemical extraction of roots. Higher U concentrations were measured in roots of dicots which showed a higher CECR than monocot species. Chemical extractions indicated that uranium is mostly located in the apoplasm of roots of monocots but that it is predominantly located in the symplasm of roots of dicots. Translocation of U to shoot was not significantly affected by the CECR or distribution of U between symplasm and apoplasm. Distribution of uranium in roots was investigated through chemical extraction of roots for all species. Additionally, longitudinal and radial distribution of U in roots of maize and Indian mustard, respectively showing the lowest and the highest translocation, was studied following X-ray fluorescence (XRF) analysis of specific root sections. Chemical analysis and XRF analysis of roots of maize and Indian mustard clearly indicated a higher longitudinal and radial transport of uranium in roots of Indian mustard than in roots of maize, where uranium mostly accumulated in root tips. These results showed that even if CECR could partly explain U accumulation in roots, other mechanisms like radial and longitudinal transport are implied in the translocation of U to the shoot.     

Radionuclide and chemical concentrations in mineral waters at Saratoga Springs, New York

A project to characterize the radionuclide and chemical components in natural spring waters in the vicinity of Saratoga Springs, New York (USA) has been completed. As a result of the measured radionuclide and chemical content, eight springs were labeled as mineral waters, whereas three springs contained very low concentrations of these components. The mineral waters were highly enriched in alkaline and alkaline-earth elements, as well as chloride ions. Three isotopes of radium ((224)Ra, (226)Ra, (228)Ra) were detected in the mineral waters and reached concentrations of 1, 20, and 2 Bq/L, respectively. Overall, the (226)Ra isotope constituted about 80% of the total radioactivity measured in the water samples. Dissolved uranium concentrations in the mineral waters were very low (mean approximately 50 mBq/L).     

Distribution of uranium isotopes in surface water of the Llobregat river basin (Northeast Spain)

A study is presented on the distribution of ²³⁴U, ²³⁸U, ²³⁵U isotopes in surface water of the Llobregat river basin (Northeast Spain), from 2001 to 2006. Sixty-six superficial water samples were collected at 16 points distributed throughout the Llobregat river basin. Uranium isotopes were measured by alpha spectrometry (PIPS detectors). The test procedure was validated according to the quality requirements of the ISO17025 standard. The activity concentration for the total dissolved uranium ranges from 20 to 261 mBq L⁻¹. The highest concentrations of uranium were detected in an area with formations of sedimentary rock, limestone and lignite. A high degree of radioactive disequilibrium was noted among the uranium isotopes. The ²³⁴U/²³⁸U activity ratio varied between 1.1 and 1.9 and the waters with the lowest uranium activity registered the highest level of ²³⁴U/²³⁸U activity ratio. Correlations between uranium activity in the tested water and chemical and physical characteristics of the aquifer were found.     

An estimation of radiation doses to benthic invertebrates from sediments collected near a Canadian uranium mine.

A new method is described for calculating radiation doses to benthic invertebrates from radionuclide concentrations in freshwater sediment. Both internal and external radiation doses were estimated for all 14 principal radionuclides of the uranium-238 decay series. Sediments were collected from three sites downstream of a uranium mining operation in northern Saskatchewan, Canada. Sediments from two sites, located approximately 1.6 and 4.4 km downstream from mining operations, yielded absorbed doses to both larval midges, Chironomus tentans, and adult amphipods, Hyalella azteca, of 59-60 and 19 mGy/year, respectively, compared to 3.2 mGy/year for a nearby control site. External beta radiation from protactinium-234 (234Pa) and alpha radiation from uranium (U) contributed most of the dose at the impacted sites, whereas polonium-210 (210Po) was most important at the control site. If a weighting factor of 20 was employed for the greater biological effect of alpha vs. beta and gamma radiation, then total equivalent doses rose to 540-560 mGy/year at the site closest to uranium operations. Such equivalent doses are above the 360-mGy/year no-observed-effect level for reproductive effects in vertebrates from gamma radiation exposure. Data are not available to determine the effect of such doses on benthic organisms, but they are high enough to warrant concern. Detrimental effects have been observed in H. azteca at similar uranium concentration in laboratory toxicity tests, but it remains unclear whether the radiotoxicity or the chemotoxicity of uranium is responsible for these effects.