Temporal trajectories of artificial radiocaesium 137Cs in French rivers over the nuclear era reconstructed from sediment cores.

137Cs is a long-lived man-made radionuclide introduced in the environment worldwide at the early beginning of the nuclear Era during atmospheric nuclear testing's followed by the civil use of nuclear energy. Atmospheric fallout deposition of this major artificial radionuclide was reconstructed at the scale of French large river basins since 1945, and trajectories in French nuclearized rivers were established using sediment coring. Our results show that 137Cs contents in sediments of the studied rivers display a large spatial and temporal variability in response to the various anthropogenic pressures exerted on their catchment. The Loire, Rhone, and Rhine rivers were the most affected by atmospheric fallout from the global deposition from nuclear tests. Rhine and Rhone also received significant fallout from the Chernobyl accident in 1986 and recorded significant 137Cs concentrations in their sediments over the 1970-1985 period due to the regulatory releases from the nuclear industries. The Meuse River was notably impacted in the early 1970s by industrial releases. In contrast, the Seine River display the lowest 137Cs concentrations regardless of the period. All the rivers responded similarly over time to atmospheric fallout on their catchment, underlying a rather homogeneous resilience capacity of these river systems to this source of contamination.

Spatial and temporal variation of tritium concentrations during a dam flushing operation.

Tritium is a radionuclide commonly observed worldwide in riverine systems. In the Rhône River downstream the Lake Geneva (Switzerland and France), its occurrence is also related to its use for its luminescent properties in watchmaking paints. In fact, tritium is regularly observed at anomalous levels in this river and extreme events such as flushing operations might conduct to its transport downstream. In the Rhône River, characterized by 21 dams downstream the Geneva Lake, such operations are regularly organized to remove the sediments and limit problematic consequences such as siltation and increased flooding hazards. The consequences of dam flushing operations on tritium concentrations were thus investigated. Samples of Suspended Particulate Matter (SPM) and water were collected in the Rhone River downstream of Geneva in June 2012, during a planned flushing operation of three upstream reservoirs (Verbois, Chancy-Pougny and Génissiat). The concentrations of tritiated water (HTO) and organically bound Tritium (OBT) were measured and compared to reference concentrations. The flushing operations had no impact on the HTO concentration while the increases observed were related to the authorized releases of HTO from a nuclear power plant located downstream the dams. High increases of OBT concentrations in SPM were observed at two stations (Creys-Malville and Jons) without clear spatial or temporal trends. These anomalous peaks could be explained by the heterogeneous spatial distribution of technogenic tritium leading to large variations of tritium concentrations within the samples even though collected in areas close to each other. The results highlight the need to investigate the amount of such technogenic tritium currently stored in the upstream Rhone River as it might be significant.

A brief history of origins and contents of Organically Bound Tritium (OBT) and 14C in the sediments of the Rhône watershed.

Tritium (3H) and Carbon-14 (14C) are radionuclides of natural (cosmogenic) origin that have also been introduced into the environment by humans since the middle of the last century. They are therefore not compounds that have only recently been released into the environment and they do not pose a recognized health threat due to their low radiotoxicity. However, they hold an important place among current concerns because they are being discharged into the environment by the nuclear industry in large quantities compared to other radionuclides. Those both radionuclides partly integrate organic matter during metabolic processes (i.e., photosynthesis) leading to organically bound forms that can be found in sediments. Organically bound tritium (OBT) analyses carried out on the sediments of the Rhône and its tributaries indicate a significant and historical tritium labelling of sedimentary particles all along the Rhône river, as well as in several northern tributaries, in particular the Ognon and the Tille rivers (tributaries of the Saone), the Doubs River and the Loue River (a tributary of the Doubs) and the Arve river. The recorded levels (10 to over 20,000 Bq/L) are very likely to be related to the presence of synthetic tritiated particles (technogenic tritium), which were used in the past in watchmaking workshops. Although overall contamination levels decrease from north to south in the Rhône watershed and fade over time, particularly due to the radioactive decay of tritium, this contamination source of technogenic tritium in the Rhône watersheds is currently still not negligible. Carbon-14 analyses show that the Rhône sediments generally display 14C levels close to the atmospheric reference values (231 Bq·kg-1 of C in 2015) or even lower in most of cases, and show sporadic and weak labelling near nuclear facilities. The low 14C levels in the Rhône sediments are most likely related to the solid contributions from tributaries draining areas that are rich in fossil organic matter, and therefore devoid of 14C. In the Rhône watershed, the presence in solid particles of tritium in a form organically bound to synthetic compounds and of petrogenic (fossil) organic carbon, can potentially alter the apparent assimilation rates to the food chain of these two radionuclides.

Tritium and 14C background levels in pristine aquatic systems and their potential sources of variability.

Tritium and (14)C are currently the two main radionuclides discharged by nuclear industry. Tritium integrates into and closely follows the water cycle and, as shown recently the carbon cycle, as does (14)C (Eyrolle-Boyer et al., 2014a, b). As a result, these two elements persist in both terrestrial and aquatic environments according to the recycling rates of organic matter. Although on average the organically bound tritium (OBT) activity of sediments in pristine rivers does not significantly differ today (2007-2012) from the mean tritiated water (HTO) content on record for rainwater (2.4 ± 0.6 Bq/L and 1.6 ± 0.4 Bq/L, respectively), regional differences are expected depending on the biomass inventories affected by atmospheric global fallout from nuclear testing and the recycling rate of organic matter within watersheds. The results obtained between 2007 and 2012 for (14)C show that the levels varied between 94.5 ± 1.5 and 234 ± 2.7 Bq/kg of C for the sediments in French rivers and across a slightly higher range of 199 ± 1.3 to 238 ± 3.1 Bq/kg of C for fish. This variation is most probably due to preferential uptake of some organic carbon compounds by fish restraining (14)C dilution with refractory organic carbon and/or with old carbonates both depleted in (14)C. Overall, most of these ranges of values are below the mean baseline value for the terrestrial environment (232.0 ± 1.8 Bq/kg of C in 2012, Roussel-Debet, 2014a) in relation to dilution by the carbonates and/or fossil organic carbon present in aquatic systems. This emphasises yet again the value of establishing regional baseline value ranges for these two radionuclides in order to account for palaeoclimatic and lithological variations. Besides, our results obtained from sedimentary archive investigation have confirmed the delayed contamination of aquatic sediments by tritium from the past nuclear tests atmospheric fallout, as recently demonstrated from data chronicles (Eyrolle-Boyer et al., 2014a,b). Thus Sedimentary archives can be successfully used to reconstruct past (14)C and OBT levels. Additionally, sediment repositories potentially represent significant storages of OBT that may account for in case of further remobilisation. We finally show that floods can significantly affect the OBT and (14)C levels within suspended particles or sediments depending on the origin of particles reinforcing the need to acquire baseline value range at a regional scale.

Tracing the origin of suspended sediment in a large Mediterranean river by combining continuous river monitoring and measurement of artificial and natural radionuclides.

Delivery of suspended sediment from large rivers to marine environments has important environmental impacts on coastal zones. In France, the Rhone River (catchment area of 98,000 km(2)) is by far the main supplier of sediment to the Mediterranean Sea and its annual solid discharge is largely controlled by flood events. This study investigates the relevance of alternative and original fingerprinting techniques based on the relative abundances of a series of radionuclides measured routinely at the Rhone River outlet to quantify the relative contribution of sediment supplied by the main tributaries during floods. Floods were classified according to the relative contribution of the main subcatchments (i.e., Oceanic, Cevenol, extensive Mediterranean and generalised). Between 2000 and 2012, 221 samples of suspended sediment were collected at the outlet and were shown to be representative of all flood types that occurred during the last decade. Three geogenic radionuclides (i.e., (238)U, (232)Th and (40)K) were used as fingerprints in a multivariate mixing model in order to estimate the relative contribution of the main subcatchment sources-characterised by different lithologies-in sediment samples collected at the outlet. Results showed that total sediment supply originating from Pre-Alpine, Upstream, and Cevenol sources amounted to 10, 7 and 2.10(6)tons, respectively. These results highlight the role of Pre-Alpine tributaries as the main sediment supplier (53%) to the Rhone River during floods. Other fingerprinting approaches based on artificial radionuclide activity ratios (i.e., (137)Cs/(239+240)Pu and (238)Pu/(239+240)Pu) were tested and provided a way to quantify sediment remobilisation or the relative contributions of the southern tributaries. In the future, fingerprinting methods based on natural radionuclides should be further applied to catchments with heterogeneous lithologies. Methods based on artificial radionuclides should be further applied to catchments characterised by heterogeneous post-Chernobyl (137)Cs deposition or by specific releases of radioactive effluents.

Apparent enrichment of organically bound tritium in rivers explained by the heritage of our past.

The global inventory of naturally produced tritium (3H) is estimated at 2.65 kg, whereas more than 600 kg have been released during atmospheric nuclear tests (NCRP, 1979; UNSCEAR, 2000) constituting the main source of artificial tritium throughout the Anthropocene. The behaviour of this radioactive isotope in the environment has been widely studied since the 1950s, both through laboratory experiments and, more recently, through field observations (e.g., Cline, 1953; Kirchmann et al., 1979; Daillant et al., 2004; McCubbin et al., 2001; Kim et al., 2012). In its "free" forms, [i.e. 3H gas or 3H hydride (HT); methyl 3H gas (CH3T); tritiated H2O or 3H-oxide (HTO); and Tissue Free Water 3H (TFWT)], tritium closely follows the water cycle. However, 3H bound with organic compounds, mainly during the basic stages of photosynthesis or through weak hydrogen links, is less exchangeable with water, which explains its persistence in the carbon cycle as re underlined recently by Baglan et al. (2013), Jean-Batiste and Fourré (2013), Kim et al. (2013a,b). In this paper, we demonstrate that terrestrial biomass pools, historically contaminated by global atmospheric fallout from nuclear testing, have constituted a significant delayed source of organically bound tritium (OBT) for aquatic systems, resulting in an apparent enrichment of OBT as compared to HTO. This finding helps to explain concentration factors (tritium concentration in biota/concentration in water) greater than 1 observed in areas that are not directly affected by industrial radioactive wastes, and thus sheds light on the controversies regarding tritium 'bioaccumulation'. Such apparent enrichment of OBT is expected to be more pronounced in the Northern Hemisphere where fallout was most significant, depending on the nature and biodegradability of terrestrial biomass at the regional scale. We further believe that OBT transfers from the continent to oceans have been sufficient to affect tritium concentrations in coastal marine biota (i.e., near river inputs). Our findings demonstrate that the persistence of terrestrial organic (3)H explains imbalances between organically bound tritium and free (3)H in most river systems in particular those not impacted by releases from nuclear facilities.

Radioactivity levels in major French rivers: summary of monitoring chronicles acquired over the past thirty years and current status.

Since the beginning of the 1990 s, liquid releases of gamma-emitting radionuclides from French nuclear facilities have generally fallen by almost 85%. Almost 65% of gamma-emitting liquid effluents released into freshwater rivers concerned the River Rhône (Southeast France), with around 85% of this originating from the Marcoule spent fuel reprocessing plant. Upstream of French nuclear plants, artificial radionuclides still detected by gamma spectrometry in 2006, include (137)Cs, (131)I as well as (60)Co, (58)Co and (54)Mn in the case of the Rhine (Switzerland nuclear industries). In the wake of the fallout from the Chernobyl accident, (103)Ru, (106)Rh-Ru, (110 m)Ag, (141)Ce and (129)Te were detected in rivers in the east of France. Some of these radionuclides were found in aquatic plants until 1989. In eastern France, (137)Cs activity in river sediments and mosses is still today two to three times greater than that observed in similar environments in western France. No (134)Cs has been detected upstream of nuclear plants in French rivers since 2001. Downstream of nuclear plants, the gamma emitters still detected regularly in rivers in 2006 are (137)Cs, (134)Cs, (60)Co, (58)Co, (110 m)Ag, (54)Mn, (131)I, together with (241)Am downstream of the Marcoule spent fuel reprocessing plant. Alpha and beta emitters such as plutonium isotopes and (90)Sr first entered freshwaters at the early 1950s due to the leaching of soils contaminated by atmospheric fallout from nuclear testing. These elements were also introduced, in the case of the Rhône River, via effluent from the Marcoule reprocessing plant. Until the mid 1990 s, plutonium isotope levels observed in the lower reaches of the Rhône were 10 to 1000 times higher than those observed in other French freshwaters. Data gathered over a period of almost thirty years of radioecological studies reveal that the only radionuclides detected in fish muscles are (137)Cs, (90)Sr, plutonium isotopes and (241)Am. At the scale of the French territory, there is no significant difference since the mid 1990 s between (137)Cs activity observed downstream of nuclear facilities and that observed upstream, whether in sediments, mosses and fish. Finally, this study highlights that the natural radioactivity of surface freshwaters are around 25 times greater than artificial radioactivity from gamma emitters. However, non gamma emitters released by nuclear industries, such as (3)H, may lead to artificial activity levels 2 to 20 times higher than natural levels.