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We present the radioanalytical strategies used for the determination of strontium radioisotopes in routine and emergency samples. While in routine monitoring, the main goal is to achieve limits of detection as low as possible. In emergency, priority is given to the rapid procurement of data about a contamination. The parameters accuracy, precision and detection limit of the radiochemical methods are shown. We present the results obtained over the past 22 years in proficiency tests and in the analysis of reference materials.

This paper presents the results of

Liquid scintillation counting (LSC) is one of the most widely used methods for determining the activity of 241Pu. One of the main challenges of this counting method is the efficiency calibration of the system for the low beta energies of 241Pu (E max = 20.8 keV). In this paper we compare the two most frequently used methods, the CIEMAT/NIST efficiency tracing (CNET) method and the experimental quench correction curve method. Both methods proved to be reliable, and agree within their uncertainties, for the expected quenching conditions of the sources.

An assessment of the radioactive and chemical contamination of the water resources at the former uranium mines and processing sites of Mailuu-Suu, in Kyrgyzstan, was carried out. A large number of water samples were collected from the drinking water distribution system (DWDS), rivers, shallow aquifers and drainage water from the mine tailings. Radionuclides and trace metal contents in water from the DWDS were low in general, but were extremely high for Fe, Al and Mn. These elements were associated with the particle fractions in the water and strongly correlated with high turbidity levels. Overall, these results suggest that water from the DWDS does not represent a serious radiological hazard to the Mailuu Suu population. However, due to the high turbidities and contents of some elements, this water is not good quality drinking water. Water from artesian and dug wells were characterized by elevated levels of U (up to 10 μg/L) and some trace elements (e.g. As, Se, Cr, V and F) and anions (e.g. Cl(-), NO3(-), SO4(2-)). In two artesian wells, the WHO guideline value of 10 μg/L for As in water was exceeded. As the artesian wells are used as a source of drinking water by a large number of households, special care should be taken in order to stay within the WHO recommended guidelines. Drainage water from the mine tailings was as expected highly contaminated with many chemicals (e.g. As) and radioactive contaminants (e.g. U). The concentrations of U were more than 200 times the WHO guideline value of 30 μg/L for U in drinking water. A large variation in (234)U/(238)U isotopic ratios in water was observed, with values near equilibrium at the mine tailings and far from equilibrium outside this area (reaching ratios of 2.3 in the artesian well). This result highlights the potential use of this ratio as an indicator of the origin of U contamination in Mailuu Suu.

The northern section of the Bohemian Cretaceous Basin has been the site of intensive U exploitation with harmful impacts on groundwater quality. The understanding of groundwater flow and age distribution is crucial for the prediction of the future dispersion and impact of the contamination. State of the art tracer methods (3H, 3He, 4He, 85Kr, 39Ar and 14C) were, therefore, used to obtain insights to ageing and mixing processes of groundwater along a north–south flow line in the centre of the two most important aquifers of Cenomanian and middle Turonian age. Dating of groundwater is particularly complex in this area as: (i) groundwater in the Cenomanian aquifer is locally affected by fluxes of geogenic and biogenic gases (e.g. CO2, CH4, He) and by fossil brines in basement rocks rich in Cl and SO4; (ii) a thick unsaturated zone overlays the Turonian aquifer; (iii) a periglacial climate and permafrost conditions prevailed during the Last Glacial Maximum (LGM), and iv) the wells are mostly screened over large depth intervals. Large disagreements in 85Kr and 3H/3He ages indicate that processes other than ageing have affected the tracer data in the Turonian aquifer. Mixing with older waters (>50 a) was confirmed by 39Ar activities. An inverse modelling approach, which included time lags for tracer transport throughout the unsaturated zone and degassing of 3He, was used to estimate the age of groundwater. Best fits between model and field results were obtained for mean residence times varying from modern up to a few hundred years. The presence of modern water in this aquifer is correlated with the occurrence of elevated pollution (e.g. nitrates). An increase of reactive geochemical indicators (e.g. Na) and radiogenic 4He, and a decrease in 14C along the flow direction confirmed groundwater ageing in the deeper confined Cenomanian aquifer. Radiocarbon ages varied from a few hundred years to more than 20 ka. Initial 14C activity for radiocarbon dating was calibrated by means of 39Ar measurements. The 14C age of a sample recharged during the LGM was further confirmed by depleted stable isotope signatures and near freezing point noble gas temperature. Radiogenic 4He accumulated in groundwater with concentrations increasing linearly with 14C ages. This enabled the use of 4He to validate the dating range of 14C and extend it to other parts of this aquifer. In the proximity of faults, 39Ar in excess of modern concentrations and 14C dead CO2 sources, elevated 3He/4He ratios and volcanic activity in Oligocene to Quaternary demonstrate the influence of gas of deeper origin and impeded the application of 4He, 39Ar and 14C for groundwater dating.

Mercury (Hg) compounds were used in the past in primers for rifle and handgun ammunition. Despite its toxicity, little is known about the contamination of shooting-range soils with this metal. We present new data about the Hg contamination of surface soils from numerous shooting ranges of Switzerland. Our study demonstrates that Hg is measurable at high levels in surface soils from the shooting ranges. In three of the investigated ranges, concentrations above the maximum Swiss guidance value of Hg in soil of 500 µg kg−1 were measured. Since the use of mercury-containing ammunition was stopped in the 1960s, our results demonstrate the high persistence of Hg in soils and their slow recovery by natural mechanisms.

14C dating of groundwater depends on the isotopic composition of both the solid carbonate and the soil CO2 and requires the use of 14C age correction models. To better assess the variability of the 14C activity of soil CO2 (A14Csoil-CO2) and the δ13C of soil CO2 (δ13Csoil-CO2), which are two parameters used in 14C age correction models, we studied the different processes involving carbon isotopes in the soil. The approach used experimental data from two sites in France (Fontainebleau sands and Astian sands) and a steady-state transport model. In most cases, the 14C activity (A14C) of atmospheric CO2 is directly used in the 14C age correction models as the A14Csoil-CO2. However, we demonstrate that since 1950, the evolution of the A14Csoil-CO2 reflects the competition between the fluxes of root-derived CO2 and organic matter-derived CO2. Therefore, the A14Csoil-CO2 must be used to date groundwater that is younger than 60 years old. Moreover, the δ13C of soil CO2 (δ13Csoil-CO2) showed large seasonal variations that must be taken into account in selecting the δ13Csoil-CO2 for 14C age correction models.

Here we present a 30 000 years low-resolution climate record reconstructed from groundwater data. The investigated site is located in the Bohemian Cretaceous Basin, in the corridor between the Scandinavian ice sheet and the Alpine ice field. Noble gas temperatures (NGT), obtained from groundwater data, preserved multicentennial temperature variability and indicated a cooling of at least 5–7 °C during the last glacial maximum (LGM). This is further confirmed by the depleted δ 18 O and δ 2 H values at the LGM. High excess air (ΔNe) at the end of the Pleistocene is possibly related to abrupt changes in recharge dynamics due to progression and retreat of ice covers and permafrost. These results agree with the fact that during the LGM permafrost and small glaciers developed in the inner valleys of the Giant Mountains (located in the watershed of the aquifers). A temporal decrease of deuterium excess from the pre-industrial Holocene to present days is linked to an increase of the air temperatures, and probably also to an increase of water pressure at the source region of precipitation over the past few hundred years.

Since 1998 the highly polluted Havana Bay ecosystem has been the subject of a mitigation program. In order to determine whether pollution-reduction strategies were effective, we have evaluated the historical trends of pollution recorded in sediments of the Bay. A sediment core was dated radiometrically using natural and artificial fallout radionuclides. An irregularity in the 210 Pb record was caused by an episode of accelerated sedimentation. This episode was dated to occur in 1982, a year coincident with the heaviest rains reported in Havana over the XX century. Peaks of mass accumulation rates (MAR) were associated with hurricanes and intensive rains. In the past 60 years, these maxima are related to strong El Nino periods, which are known to increase rainfall in the north Caribbean region. We observed a steady increase of pollution (mainly Pb, Zn, Sn, and Hg) since the beginning of the century to the mid 90s, with enrichment factors as high as 6. MAR and pollution decreased rapidly after the mid 90s, although some trace metal levels remain high. This reduction was due to the integrated coastal zone management program introduced in the late 90s, which dismissed catchment erosion and pollution.

A procedure was developed for determining 241Pu activity in environmental samples. This beta emitter isotope of plutonium was measured by ultra low level liquid scintillation, after several separation and purification steps that involved the use of a highly selective extraction chromatographic resin (Eichrom-TEVA). Due to the lack of reference material for 241Pu, the method was nevertheless validated using four IAEA reference sediments with information values for 241Pu. Next, the method was used to determine the 241Pu activity in alpine soils of Switzerland and France. The 241Pu/239,240Pu and 238Pu/239,240Pu activity ratios confirmed that Pu contamination in the tested alpine soils originated mainly from global fallout from nuclear weapon tests conducted in the fifties and sixties. Estimation of the date of the contamination, using the 241Pu/241Am age-dating method, further confirmed this origin. However, the 241Pu/241Am dating method was limited to samples where Pu-Am fractionation was insignificant. If any, the contribution of the Chernobyl accident is negligible.

14C dating models are limited when considering recent groundwater for which the carbon isotopic signature of the total dissolved inorganic carbon (TDIC) is mainly acquired in the unsaturated zone. Reducing the uncertainties of dating thus implies a better identification of the processes controlling the carbon isotopic composition of the TDIC during groundwater recharge. Geochemical interactions between gas, water and carbonates in the unsaturated zone were investigated for two aquifers (the carbonate-free Fontainebleau sands and carbonate-bearing Astian sands, France) in order to identify the respective roles of CO2 and carbonates on the carbon isotopic signatures of the TDIC; this analysis is usually approached using open or closed system terms. Under fully open system conditions, the seasonality of the 13C values in the soil CO2 can lead to important uncertainties regarding the so-called “initial 14C activity” used in 14C correction models. In a carbonate-bearing unsaturated zone such as in the Astian aquifer, we show that an approach based on fully open or closed system conditions is not appropriate. Although the chemical saturation between water and calcite occurs rapidly within the first metre of the unsaturated zone, the carbon isotopic contents (δ13C) of the CO2 and the TDIC evolve downward, impacted by the dissolution–precipitation of the carbonates. In this study, we propose a numerical approach to describe this evolution. The δ13C and the A14C (radiocarbon activity) of the TDIC at the base of the carbonate-bearing unsaturated zone depends on (i) the δ13C and the A14C of the TDIC in the soil determined by the soil CO2, (ii) the water’s residence time in the unsaturated zone and (iii) the carbonate precipitation–dissolution fluxes. In this type of situation, the carbonate δ13C–A14C evolutions indicate the presence of secondary calcite and permit the calculation of its accretion flux, equal to ∼4.5±0.5×10-9molgrock-1yr-1. More generally, for other sites under temperate climate and with similar properties to the Astian sands site, this approach allows for a reliable determination of the carbon isotopic composition at the base of the unsaturated zone as the indispensable “input function” data of the carbon cycle into the aquifer.

36Cl produced by thermonuclear bomb testing has been proposed as an additional tool to date or at least to identify recent groundwater components. In order to investigate the behaviour of 36Cl in shallow groundwater a multi-tracer approach (3H/3He, SF6, CFC-12 and 85Kr) was used to characterise and date the groundwater of a quaternary sands aquifer which is located on the Island of Funen near the city of Odense, Denmark. Recharge to the semi-confined shallow aquifer occurs through permeable sand windows and fractured tills at the surface. Locally, however, mixing with older pre-bomb water from the underlying limestone aquifer may occur. The integrated analyses of the available tracer data allowed a well constrained age structure determination of the investigated water system. The 36Cl/Cl ratios measured in groundwater were used to reconstruct the fallout rates for radioactive 36Cl at Odense. The calculated fallout values exceeded the fallout estimated based on data from the Dye-3 ice core in Greenland. Recycling of the bomb peak fallout seems to be the most probable reason of the high values measured. The local extent of this process is difficult to quantify, which impedes the use of 36Cl for dating.

The atmospheric nuclear testing in the 1950s and early 1960s and the burn-up of the SNAP-9A satellite led to large injections of radionuclides into the stratosphere. It is generally accepted that current levels of plutonium and caesium radionuclides in the stratosphere are negligible. Here we show that those radionuclides are present in the stratosphere at higher levels than in the troposphere. The lower content in the troposphere reveals that dry and wet deposition efficiently removes radionuclides within a period of a few weeks to months. Since the stratosphere is thermally stratified and separated from the troposphere by the tropopause, radioactive aerosols remain longer. We estimate a mean residence time for plutonium and caesium radionuclides in the stratosphere of 2.5-5 years. Our results also reveal that strong volcanic eruptions like Eyjafjallajökull in 2010 have an important role in redistributing anthropogenic radionuclides from the stratosphere to the troposphere.

241Pu was determined in slurry samples from a nuclear reactor decommissioning project at the Paul Scherrer Institute (Switzerland). To validate the results, the 241Pu activities of five samples were determined by LSC (TriCarb and Quantulus) and ICP-MS, with each instrument at a different laboratory. In lack of certified reference materials for 241Pu, the methods were further validated using the 241Pu information values of two reference sediments (IAEA-300 and IAEA-384). Excellent agreement with the results was found between LSC and ICP-MS in the nuclear waste slurries and the reference sediments.

[1] Temperature reconstructions for recent centuries are the basis of estimations of the natural variability in the climate system before and during the onset of anthropogenic perturbation. Here we present, for the first time, an independent and physically based reconstruction of mean annual temperature over the past half millennium obtained from groundwater in France. The reconstructed noble gas temperature (NGT) record suggests cooler than present climate conditions throughout the 16th–19th centuries. Periods of warming occur in the 17th–18th and 20th century, while cooling is reconstructed in the 19th century. A noticeable coincidence with other temperature records is demonstrated. Deuterium excess varies in parallel with the NGT, and indicates variation in the seasonality of the aquifer recharge; whereas high excess air in groundwater indicates periods with high oscillations of the water table.

A tritium (H-3) profile was constructed in a long-screened well (LSW) of the Fontainebleau Sands Aquifer (France), and the data were combined with temperature logs to gain insight into the potential effects of the ambient vertical flow (AVF) of water through the well on the natural aquifer stratification. AVF is commonly taken into account in wells located in fracture aquifers or intercepting two different aquifers with distinct hydraulic heads. However, due to the vertical hydraulic gradient of the flow lines intercepted by wells, AVF of groundwater is a common process within any type of aquifer. The detection of 3H in the deeper parts of the studied well ( approximate depth 50m), where H-3-free groundwater is expected, indicates that shallow young water is being transported downwards through the well itself. The temperature logs show a nearly zero gradient with depth, far below the mean geothermal gradient in sedimentary basins. The results show that the age distribution of groundwater samples might be biased in relation to the age distribution in the surroundings of the well. The use of environmental tracers to investigate aquifer properties, particularly in LSWs, is then limited by the effects of the AVF of water that naturally occurs through the well.

[1] A multitracer (3H/3He, 85Kr, 39Ar, and 14C) approach is used to investigate the age structure of groundwater in the semiconfined Fontainebleau Sands Aquifer that is located in the shallower part of the Paris Basin (France). The hydrogeological situation, which is characterized by spatially extended recharge, large screen intervals, and possible leakage from deeper aquifers, led us to expect a wide range of residence times and pronounced mixing of different water components. Consequently, a large set of tracers with corresponding dating ranges was adopted. Commonly used tracers for young groundwater (3H, 3He, and 85Kr) can identify only those components with ages below 50 years. This approach is reliable if a large fraction of the water recharge occurs within this period. However, if a considerable fraction is older than 50 years, a tracer that covers intermediate age ranges below 1000 years is needed. We examine the use of 39Ar, a noble gas radioisotope with a half-life of 269 years, to constrain the age distribution of groundwater in this timescale range. Recharge rate, depth of water table, and the age structure of the groundwater are estimated by inverse modeling. The obtained recharge rates of 100–150 mm/yr are comparable to estimations using hydrograph data. Best agreement between the modeled and measured tracer concentrations was achieved for a thickness of the unsaturated soil zone of 30–40 m, coinciding well with the observed thicknesses of the unsaturated zone in the area. Transport times of water and gas from the soil surface to the water table range between 10 and 40 and 1 and 6 years, respectively. Reconstructed concentrations of 85Kr and 3H at the water table were used for saturated flow modeling. The exponential box model was found to reproduce the field data best. Conceptionally, this finding agrees well with the spatially extended recharge and large screened intervals in the project area. Best fits between model and field results were obtained for mean residence times of 1–129 years. The 39Ar measurements as well as the box model approach indicate the presence of older waters (3H and 85Kr free). Using 39Ar to date this old component resulted in residence times of the old water components on the order of about 100–400 years. The 14C measurements provide additional evidence for the correctness of the proposed age structure.