Tritium and radiocarbon levels in the Rhône river delta and along the French Mediterranean coastline.

The Rhône is characterised by a heavy concentration of nuclear-based industries including nuclear power stations and nuclear sites housing civilian and military facilities. Here, we report the results of a four-year survey (2010-2013) of tritium and radiocarbon levels in a variety of matrices within the Rhône delta and along the French Mediterranean coastline. The aim of the study is to create a spatial reference framework of environmental levels of these two radionuclides, which are the most prevalent in radioactive effluents from nuclear power stations. Although both tritium and radiocarbon levels in the samples analysed are very low and can only be detected using ultra-sensitive analytical techniques, they clearly show the influence of the tritium and radiocarbon discharges carried by the Rhône plume along the Mediterranean coast. The tritium content of suspended matter and sediments of the Rhône is a special case, which shows elevated tritium values not seen in other French rivers with similar nuclear facilities. The north-south spatial distribution of this tritium anomaly shows that these trace values are at their highest in the upper Rhône, close to the Swiss border and upstream of Creys Malville, the northernmost nuclear power station on the Rhône. This points to a legacy of past tritium releases by the watchmaking industry. A dedicated study would be needed to clearly identify the source and the exact nature of this contamination.

Towards speciation of organically bound tritium and deuterium: Quantification of non-exchangeable forms in carbohydrate molecules.

An original methodology to quantitatively explore exchangeability of hydrogen isotopes in carbohydrate molecules is proposed. To access the speciation of organically bound hydrogen isotopes, isotopic exchanges were carried out under a soft path regime in the vapor phase at 20 °C with set (D,T/H) vapor pressure ratios. When steady states were reached, the fraction of exchangeable hydrogen of microcrystalline cellulose, alpha-cellulose and wheat grains were obtained and ranged from 13 to 31% (versus a theoretical value of 30%). In cellulose, and more specifically in microcrystalline cellulose, the molecular hydrogen bonds as well as the different conformations of the network seemed to decrease the hydroxyl groups of glucose units available for isotopic exchange. On the contrary, the assumed enzymatic hydrolysis of the constitutive molecules of wheat starch into low-molecular weight carbohydrate molecules enhanced the exchangeable pool. An average value of the activity between non-exchangeable organically bound tritium (NE-OBT) and non-exchangeable organically bound hydrogen was calculated for wheat grains, (TH)NE  = 0.55 ±â€¯0.03 Bq.g-1 of hydrogen atoms.

Measurement of the French national tritiated-water standard by helium-3 mass spectrometry.

The (3)He ingrowth technique is based on the detection of the tritium radioactive daughter, (3)He, by mass spectrometry. Over the last three decades it has been used extensively in oceanography and groundwater studies for measurements of very low to ultra-low levels of tritium. To compare it with the best available methods of radioactive counting, we applied this method to measure the massic activity of a tritiated-water primary standard prepared by the French Laboratoire National Henri Becquerel (LNHB). One liter of a low-level tritium solution was prepared from a small aliquot of the LNHB standard by two-step gravimetric dilution with tritium-free groundwater. Sixteen samples of this solution were analyzed at the LSCE-Saclay noble gas facility, using the (3)He ingrowth method. The massic activity of the prepared solution was also measured by Liquid Scintillation Counting using the Quantulus LNHB counter and an internal calibration method with the LNHB tritiated water standard. All results agree within their standard uncertainty.

Modelling tritium flux from water to atmosphere: application to the Loire River.

Tritium (³H or T) is one of the major radionuclides released by nuclear power plants (NPP) into rivers. However, tritiated water (HTO) flux from water to air is seldom considered when assessing health effects of such releases. The aim of this paper is to present the result of a research program, called LORA, conducted on the Loire River (France). To improve our understanding of HTO flux from surface water to air, three field campaigns were organised during the NPP's radioactive releases to measure simultaneously the activity concentrations in air on the riverbank, using an innovative system, and in river water. The measurements showed that during radioactive releases, water vapour was enriched in ³H. These results were used to calibrate exchange velocities. The average of these estimated exchange velocities was more than one order of magnitude higher than those calculated in the literature from indoor experiments. The variability of these values was also larger, showing that outdoor studies cover a wide range of conditions influencing HTO flux. No correlation was observed between exchanges velocities and meteorological conditions. However, there was a significant difference between day and night with a higher value observed during the day. Two approaches used to calculate HTO evaporation from water (i.e. the approach based on water evaporation and the approach considering that HTO follows its own concentration gradient) were included in a hydrodynamic model, which was used to evaluate HTO air activity along the Loire River. In conclusion, only the approach considering that HTO follows its own gradient led to a good agreement between measurements and predictions. A one-year simulation was done to estimate the contribution of this process to the dose. Its contribution can be considered as negligible in this case compared to the other pathways such as ingestion of water or foodstuffs.

(3)He mass spectrometry for very low-level measurement of organic tritium in environmental samples.

The design, setup and performance of a mass spectrometric system for the analysis of low to very low-level tritium in environmental samples are described. The tritium concentration is measured indirectly by the (3)He ingrowth from radioactive decay after complete initial degassing of the sample. The analytical system is fully computer-controlled and consists in a commercial helium isotope mass spectrometer coupled with a high vacuum inlet system. A detection limit of 0.15 Bq/kg is routinely obtainable for sample sizes of 20g of water equivalent and an accumulation time of three months. Larger samples (and/or longer accumulation time) can be used to obtain lower detection limits. In addition to the benefit of a lower detection limit, another advantage of this non-destructive method lies in the simplicity of the analytical procedure which strongly limits the risk of contamination. An inter-comparison was successfully performed with the conventional beta counting technique on lyophilized grass samples, in a range of tritium concentrations of environmental interest. It shows that the (3)He mass spectrometry method yields results that are fully consistent with the conventional liquid scintillation technique over a wide range of tritium concentrations.

The distribution of tritium in the terrestrial and aquatic environments of the Creys-Malville nuclear power plant (2002-2005).

The Creys-Malville nuclear plant, located on the left bank of the Rhône, was shut down in 1998. The facilities are currently in their initial stage of dismantling. In order to establish a baseline for tritium in the vicinity of the site prior to the main dismantling phase, we carried out a monitoring program between 2002 and 2005 in the main terrestrial and aquatic compartments of the local environment. Tritium levels in the groundwaters and in the Rhône waters correspond to the regional tritium concentration in precipitation. The data obtained for the terrestrial environment are also in good agreement with the regional background and do not show any specific signature linked to the nuclear plant. The various aquatic compartments of the Rhône (fish, plant, sediment) are significantly enriched in tritium both upstream and downstream of the power plant: although Tissue-Free Water Tritium concentrations are in equilibrium with the river water, the non-exchangeable fraction of organic bound tritium in plants and fishes shows values which outpace the river water background by one to two orders of magnitude, and up to four to five orders of magnitude in the sediments. This tritium anomaly is not related to the nuclear plant, as it is already present at the Swiss border 100km upstream of the site. Although fine particles of tritiated polystyrene entering the composition of the luminous paints used by the clock industry have been suspected on several occasions, the exact nature and the origin of this tritium source remain unknown and require further investigations.