Lessons learnt on the impact of an unprecedented soil decontamination program in Fukushima on contaminant fluxes.

In the context of elevated concerns related to nuclear accidents and warfare, the lessons learnt from the Fukushima Daiichi Nuclear Power Plant accident in 2011 are important. In particular, Japanese authorities implemented an ambitious decontamination program to reduce the air dose rate in order to facilitate the return of the local inhabitants to previously evacuated areas. This approach contrasts the strategy adopted in Chernobyl, where the most contaminated areas remain off limits. Nonetheless, the effectiveness of the Japanese decontamination strategy on the dispersion of radioactive contaminant fluxes across mountainous landscapes exposed to typhoons has not been quantified. Based on the unique combination of river monitoring and modeling in a catchment representative of the most impacted area in Japan, we demonstrate that decontamination of 16% of the catchment area resulted in a decrease of 17% of sediment-bound radioactive fluxes in rivers. Decontamination operations were therefore relatively effective, although they could only be conducted in a small part of the area due to the dominance of steep forested slopes. In fact, 67% of the initial radiocesium contamination was calculated to remain stored in forested landscapes, which may contribute to future downstream radiocesium dispersion during erosive events. Given that only a limited proportion of the initial population had returned in 2019 (~30%), it raises the question as to whether decontaminating a small percentage of the contaminated area was worth the effort, the price, and the amount of waste generated?

Innovative ICP-MS/MS Method To Determine the 135Cs/137Cs Ratio in Low Activity Environmental Samples.

The 135Cs/137Cs isotopic ratio is a powerful tool for tracing the origin of radioactive contamination. Since the Fukushima accident, this ratio has been measured by mass spectrometry in several highly contaminated environmental matrices mainly collected near nuclear accident exclusion zones and former nuclear test areas. However, few data were reported at 137Cs environmental levels (<1 kBq kg-1). This is explained by the occurrence of analytical challenges related to the very low radiocesium content at the environmental level with the large presence of mass interferences, making 135Cs and 137Cs measurements difficult. To overcome these difficulties, a highly selective procedure for Cs extraction/separation combined with an efficient mass spectrometry measurement must be applied on a quantity of ca. 100 g of soil. In the current research, an innovative inductively coupled plasma-tandem mass spectrometry (ICP-MS/MS) method has been developed for the 135Cs/137Cs ratio measurement in low activity environmental samples. The use of ICP-MS/MS led to a powerful suppression of 135Cs and 137Cs interferences by introducing N2O, He, and, for the first time, NH3, into the collision-reaction cell. By adjusting the flow rates of these gases, the best compromise between a maximum signal in Cs and an effective interference elimination was achieved allowing a high Cs sensitivity of more than 1.105 cps/(ng g-1) and low background levels at m/z 135 and 137 lower than 0.6 cps. The accuracy of the developed method was successfully verified by analyzing two certified reference materials (IAEA-330 and IAEA-375) commonly used in the literature as validation samples and three sediment samples collected in the Niida River catchment (Japan) impacted by the Fukushima fallout.

Improving the design and implementation of sediment fingerprinting studies: summary and outcomes of the TRACING 2021 Scientific School.

Purpose: Identifying best practices for sediment fingerprinting or tracing is important to allow the quantification of sediment contributions from catchment sources. Although sediment fingerprinting has been applied with reasonable success, the deployment of this method remains associated with many issues and limitations. Methods: Seminars and debates were organised during a 4-day Thematic School in October 2021 to come up with concrete suggestions to improve the design and implementation of tracing methods. Results: First, we suggest a better use of geomorphological information to improve study design. Researchers are invited to scrutinise all the knowledge available on the catchment of interest, and to obtain multiple lines of evidence regarding sediment source contributions. Second, we think that scientific knowledge could be improved with local knowledge and we propose a scale of participation describing different levels of involvement of locals in research. Third, we recommend the use of state-of-the-art sediment tracing protocols to conduct sampling, deal with particle size, and examine data before modelling and accounting for the hydro-meteorological context under investigation. Fourth, we promote best practices in modelling, including the importance of running multiple models, selecting appropriate tracers, and reporting on model errors and uncertainty. Fifth, we suggest best practices to share tracing data and samples, which will increase the visibility of the fingerprinting technique in geoscience. Sixth, we suggest that a better formulation of hypotheses could improve our knowledge about erosion and sediment transport processes in a more unified way. Conclusion: With the suggested improvements, sediment fingerprinting, which is interdisciplinary in nature, could play a major role to meet the current and future challenges associated with global change. Supplementary information: The online version contains supplementary material available at 10.1007/s11368-022-03203-1.

Evidence of Chlordecone Resurrection by Glyphosate in French West Indies.

The widespread use of pesticides in agriculture during the last several decades has contaminated soils and different Critical Zone (CZ) compartments, defined as the area extended from the top of the vegetation canopy to the groundwater table, and it integrates interactions of the atmosphere, lithosphere, biosphere, and hydrosphere. However, the long-term fate, storage, and transfer dynamics of persistent pesticides in CZ in a changing world remain poorly understood. In the French West Indies, chlordecone (CLD), a toxic organochlorine insecticide, was extensively applied to banana fields to control banana weevil from 1972 to 1993 after which it was banned. Here, to understand CZ trajectories we apply a retrospective observation based on marine sediment core analyses to monitor long-term CLD transfer, fate, and consequences in Guadeloupe and Martinique islands. Both CLD profiles show synchronous chronologies. We hypothesized that the use of glyphosate, a postemergence herbicide, from the late 1990s onward induced CZ modification with an increase in soil erosion and led to the release of the stable CLD stored in the soils of polluted fields. CLD fluxes drastically increased when glyphosate use began, leading to widespread ecosystem contamination. As glyphosate is used globally, ecotoxicological risk management strategies should consider how its application affects persistent pesticide storage in soils, transfer dynamics, and widespread contamination.

Sediment source fingerprinting: benchmarking recent outputs, remaining challenges and emerging themes.

PURPOSE: This review of sediment source fingerprinting assesses the current state-of-the-art, remaining challenges and emerging themes. It combines inputs from international scientists either with track records in the approach or with expertise relevant to progressing the science. METHODS: Web of Science and Google Scholar were used to review published papers spanning the period 2013-2019, inclusive, to confirm publication trends in quantities of papers by study area country and the types of tracers used. The most recent (2018-2019, inclusive) papers were also benchmarked using a methodological decision-tree published in 2017. SCOPE: Areas requiring further research and international consensus on methodological detail are reviewed, and these comprise spatial variability in tracers and corresponding sampling implications for end-members, temporal variability in tracers and sampling implications for end-members and target sediment, tracer conservation and knowledge-based pre-selection, the physico-chemical basis for source discrimination and dissemination of fingerprinting results to stakeholders. Emerging themes are also discussed: novel tracers, concentration-dependence for biomarkers, combining sediment fingerprinting and age-dating, applications to sediment-bound pollutants, incorporation of supportive spatial information to augment discrimination and modelling, aeolian sediment source fingerprinting, integration with process-based models and development of open-access software tools for data processing. CONCLUSIONS: The popularity of sediment source fingerprinting continues on an upward trend globally, but with this growth comes issues surrounding lack of standardisation and procedural diversity. Nonetheless, the last 2 years have also evidenced growing uptake of critical requirements for robust applications and this review is intended to signpost investigators, both old and new, towards these benchmarks and remaining research challenges for, and emerging options for different applications of, the fingerprinting approach.

Residence rule flexibility and descent groups dynamics shape uniparental genetic diversities in South East Asia.

OBJECTIVES: Social organization plays a major role in shaping human population genetic diversity. In particular, matrilocal populations tend to exhibit less mitochondrial diversity than patrilocal populations, and the other way around for Y chromosome diversity. However, several studies have not replicated such findings. The objective of this study is to understand the reasons for such inconsistencies and further evaluate the influence of social organization on genetic diversity. MATERIALS AND METHODS: We explored uniparental diversity patterns using mitochondrial HV1 sequences and 17 Y-linked short tandem repeats (STRs) in 12 populations (n = 619) from mainland South-East Asia exhibiting a wide range of social organizations, along with quantitative ethno-demographic information sampled at the individual level. RESULTS: MtDNA diversity was lower in matrilocal than in multilocal and patrilocal populations while Y chromosome diversity was similar among these social organizations. The reasons for such asymmetry at the genetic level were understood by quantifying sex-specific migration rates from our ethno-demographic data: while female migration rates varied between social organizations, male migration rates did not. This unexpected lack of difference in male migrations resulted from a higher flexibility in residence rule in patrilocal than in matrilocal populations. In addition, our data suggested an impact of clan fission process on uniparental genetic patterns. CONCLUSIONS: The observed lack of signature of patrilocality on Y chromosome patterns might be attributed to the higher residence flexibility in the studied patrilocal populations, thus providing a potential explanation for the apparent discrepancies between social and genetic structures. Altogether, this study highlights the need to quantify the actual residence and descent patterns to fit social to genetic structures.

Do forests represent a long-term source of contaminated particulate matter in the Fukushima Prefecture?

The Fukushima Daiichi Nuclear Power Plant (FDNPP) accident resulted in radiocesium fallout contaminating coastal catchments of the Fukushima Prefecture. As the decontamination effort progresses, the potential downstream migration of radiocesium contaminated particulate matter from forests, which cover over 65% of the most contaminated region, requires investigation. Carbon and nitrogen elemental concentrations and stable isotope ratios are thus used to model the relative contributions of forest, cultivated and subsoil sources to deposited particulate matter in three contaminated coastal catchments. Samples were taken from the main identified sources: cultivated (n = 28), forest (n = 46), and subsoils (n = 25). Deposited particulate matter (n = 82) was sampled during four fieldwork campaigns from November 2012 to November 2014. A distribution modelling approach quantified relative source contributions with multiple combinations of element parameters (carbon only, nitrogen only, and four parameters) for two particle size fractions (<63 µm and <2 mm). Although there was significant particle size enrichment for the particulate matter parameters, these differences only resulted in a 6% (SD 3%) mean difference in relative source contributions. Further, the three different modelling approaches only resulted in a 4% (SD 3%) difference between relative source contributions. For each particulate matter sample, six models (i.e. <63 µm and <2 mm from the three modelling approaches) were used to incorporate a broader definition of potential uncertainty into model results. Forest sources were modelled to contribute 17% (SD 10%) of particulate matter indicating they present a long term potential source of radiocesium contaminated material in fallout impacted catchments. Subsoils contributed 45% (SD 26%) of particulate matter and cultivated sources contributed 38% (SD 19%). The reservoir of radiocesium in forested landscapes in the Fukushima region represents a potential long-term source of particulate contaminated matter that will require diligent management for the foreseeable future.

Novel insights into Fukushima nuclear accident from isotopic evidence of plutonium spread along coastal rivers.

The Fukushima Dai-ichi Nuclear Power Plant (FDNPP) accident led to important releases of radionuclides into the environment, and trace levels of plutonium (Pu) were detected in northeastern Japan. However, measurements of Pu isotopic atom and activity ratios are required to differentiate between the contributions of global nuclear test fallout and FDNPP emissions. In this study, we used a double-focusing sector field ICP-MS to measure Pu atom and activity ratios in recently deposited sediment along rivers draining the most contaminated part of the inland radioactive plume. Results showed that plutonium isotopes (i.e., (239)Pu, (240)Pu, (241)Pu, and (242)Pu) were detected in all samples, although in extremely low concentrations. The (241)Pu/(239)Pu atom ratios measured in sediment deposits (0.0017-0.0884) were significantly higher than the corresponding values attributed to the global fallout (0.00113 ± 0.00008 on average for the Northern Hemisphere between 31°-71° N: Kelley, J. M.; Bond, L. A.; Beasley, T. M. Global distribution of Pu isotopes and (237)Np. Sci. Total. Env. 1999, 237/238, 483-500). The results indicated the presence of Pu from FDNPP, in slight excess compared to the Pu background from global fallout that represented up to ca. 60% of Pu in the analyzed samples. These results demonstrate that this radionuclide has been transported relatively long distances (∼45 km) from FDNPP and been deposited in rivers representing a potential source of Pu to the ocean. In future, the high (241)Pu/(239)Pu atom ratio of the Fukushima accident sourced-Pu should be measured to quantify the supply of continental-originating material from Fukushima Prefecture to the Pacific Ocean.

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.

240Pu/239Pu isotopic ratio measurements in micrometric Pu and MOX particles using Secondary Ion Mass Spectrometry.

Every accident affecting industrial or nuclear facilities emits micrometric fragments of material into the environment whose elemental and isotopic compositions are characteristic of the process or event. Particle analysis, mainly implemented in the framework of the Non Proliferation Treaty to detect clandestine nuclear activities, provides a powerful tool to identify the origin of the nuclear particulate matter and to assess the environmental impact of nuclear accidents. Initially, particle-scale isotopic analyses aimed at the determination of the U isotopic composition. Now, focus is increasingly given on Pu isotopic measurements to address its origin and potential use. Such measurements are more challenging because of isobaric interferences, including those induced by hydride ions, like 239PuH+ on 240Pu+ and 238UH+ on 239Pu+ in Mixed Oxide (MOX). Such ions are generated during ionization processes by Secondary Ion Mass Spectrometry. Based on a parametric study aiming at the measurement of uranium oxide, uranium carbide and uranium single and double hydride rates, we determined that Pu and U should be detected as elementary ions to limit the impact of such interferences, although mono-oxide ions are more abundant. Thus, we developed an analytical methodology to obtain accurate 240Pu/239Pu atomic ratios both for weapon grade Pu and MOX materials. Hydride rate is first measured in U oxide particles and then applied to correct 240Pu+ and 239Pu+ signals. The relative difference of corrected 240Pu/239Pu isotopic ratios with expected values is reduced by a factor of 4 when measuring weapon grade Pu particles and by a factor of 10-100 when measuring MOX particles containing 1 to 10 wt% of Pu. We also proposed a method to determine the Relative Sensitivity Factor (RSF) based on the decay of Pu in order to quantify the Pu content in MOX samples. The estimated lowest measurable 239Pu/238U atomic ratio in MOX particles is ∼1.6 × 10-3.

Identification of the origin of radiocesium released into the environment in areas remote from nuclear accident and military test sites using the 135Cs/137Cs isotopic signature.

The isotopic signature of radionuclides provides a powerful tool for discriminating radioactive contamination sources and estimating their respective contributions in the environment. In this context, the 135Cs/137Cs ratio has been tested as a very promising isotopic ratio that had not been explored yet in many countries around the world including France. To quantify the levels of radioactivity found in the environment, a new method combining a thorough radiochemical treatment of the sample and an efficient measurement by ICP-MS/MS has been recently developed. This method was successfully applied, for the first time, to soil and sediment samples collected in France in two mountainous regions preferentially impacted either by global fallout from nuclear weapons testing (i.e., the Pyrenees) or by the Chernobyl accident (i.e., the Southern Alps). The 135Cs/137Cs ratios measured on twenty-one samples ranged from 0.66 ± 0.04 and 4.29 ± 0.21 (decay-corrected to January 1st, 2022) corresponding to the characteristic signatures of the fallout from Chernobyl and global fallout associated with the nuclear weapons testing, respectively. Moreover, large variations of both the 137Cs mass activity and the studied isotopic ratio recorded by most samples from the southern Alps suggest varying proportions of these two 137Cs sources. For these samples, the contribution of each source was estimated using this new tracer (135Cs/137Cs) and compared with the mixing contribution given by activity ratio: 239+240Pu/137Cs. This work has successfully demonstrated the applicability of the 135Cs/137Cs isotopic signature to nuclear forensic studies and could be extended to better evaluate the environmental impact of nuclear facilities (i.e., NPP, waste reprocessing).

Temporal evolution of plutonium concentrations and isotopic ratios in the Ukedo - Takase Rivers draining the Difficult-To-Return zone in Fukushima, Japan (2013-2020).

In 2011, the Fukushima Dai-Ichi Nuclear Power Plant (FDNPP) accident released significant quantities of radionuclides into the environment. Japanese authorities decided to progressively reopen the Difficult-To-Return Zone after the decontamination of priority reconstruction zones. These areas include parts of the initially highly contaminated municipalities located to the north of the FDNPP, including Namie Town, an area drained by the Ukedo and Takase Rivers. Eleven years after the accident, research focused on the spatial distribution of plutonium (Pu) and radiocesium (Cs) isotopes at contrasted individual locations. To complement previous results, the current research was conducted on flood sediment deposits collected at the same locations after major flooding events during eleven fieldwork campaigns organised between 2013 and 2020 at the outlet of the Ukedo and Takase Rivers (n = 22). The results highlighted a global decrease of the Pu and 137Cs contents in sediment with time during the abandonment phase in the region, from 2013 (238.20 fg g-1) to 2020 (4.28 fg g-1). Furthermore, based on the analysis of the 240Pu/239Pu isotopic ratios, the plutonium transiting these rivers (range: 0.166 - 0.220) essentially originated from the global fallout (0.180 ± 0.014 (Kelley et al., 1999)). Sediment showed contrasted properties in the two investigated rivers, which is likely mainly the result of the occurrence of Ogaki Dam on upper sections of the Ukedo River as it strongly impacts the material supply from this river to the Pacific Ocean. A statistical analysis highlighted the strong correlation between Pu activity concentrations and 137Cs activities in both rivers, confirming that both radionuclides are transported with a similar pathway. Despite it was detected early after the accident (2011-2013), the current research demonstrates that plutonium originating from FDNPP is no longer detected in these rivers draining the Difficult-To-Return Zone at the onset of the reopening of the area to its former inhabitants.

Is a dissipation half-life of 5 years for chlordecone in soils of the French West Indies relevant?

Recently, Comte et al. (2022) re-examined the natural degradation of chlordecone (CLD) in the soils of the French West Indies (FWI) by introducing an additional 'dissipation parameter' into the WISORCH model developed by Cabidoche et al. (2009). Recent data sets of CLD concentrations in FWI soils obtained by Comte et al. enabled them optimizing the model parameters, resulting in significantly shorter estimates of pollution persistence than in the original model. Their conclusions jeopardize the paradigm of a very limited degradation of CLD in FWI soils, which may lead to an entire revision of the management of CLD contamination. However, we believe that their study is questionable on several important aspects. This includes potential biases in the data sets and in the modeling approach. It results in an inconsistency between the estimated dissipation half-life time (DT50) of five years that the authors determined for CLD and the fate of CLD in soil from the application period 1972-1993 until nowadays. Most importantly, a rapid dissipation of CLD in the field as proposed by Comte et al. is not sufficiently supported by data and estimates. Hence, the paradigm of long-term persistence of CLD in FWI soils is still to be considered.

Key factors influencing metal concentrations in sediments along Western European Rivers: A long-term monitoring study (1945-2020).

Since 1945, a large amount of heterogeneous data has been acquired to survey river sediment quality, especially concerning regulatory metals such as Cd, Cr, Cu, Hg, Ni, Pb, and Zn. Large-scale syntheses are critical to assess the effectiveness of public regulations and the resiliency of the river systems. Accordingly, this data synthesis proposes a first attempt to decipher spatio-temporal trends of metal contamination along seven major continental rivers in Western Europe (France, Belgium, Germany, and the Netherlands). A large dataset (>12,000 samples) from various sediment matrices (bed and flood deposits - BFD, suspended particulate matter - SPM, dated sediment cores - DSC) was set up based on monitoring and scientific research from the 1950s to the 2010s. This work investigates the impact of analytical protocols (matrix sampling, fractionation, extraction), location and time factors (related to geology and anthropogenic activities) on metal concentration trends. Statistical analyses highlight crossed-interactions in space and time, as well as between sediment matrices (metal concentrations in SPM ≃ DSC > BFD) and extraction procedures (also related to river lithology). Major spatio-temporal trends are found along several rivers such as (i) an increase of metal concentrations downstream of the main urban industrial areas (e.g. Paris-Rouen corridor on the Seine River, Bonn-Duisburg corridor on the Rhine River), (ii) a long-term influence of former mining areas located in crystalline zones, releasing heavily contaminated sediments for decades (Upper Loire River, Middle Meuse section), (iii) a decrease of metal concentrations since the 1970s (except for Cr and Ni, rather low and stable over time). The improvement of sediment quality in the most recent years in Europe reflects a decisive role of environment policies, such as more efficient wastewater treatments, local applications of the Water Framework Directive and urban industrial changes in the river valleys.

240Pu/239Pu signatures allow refining the chronology of radionuclide fallout in South America.

Atmospheric nuclear tests (1945-1980) have led to radioactive fallout across the globe. French tests in Polynesia (1966-1974) may influence the signature of fallout in South America in addition to those conducted by USA and former USSR until 1963 in the Northern hemisphere. Here, we compiled the 240Pu/239Pu atom ratios reported for soils of South America and conducted additional measurements to examine their latitudinal distributions across this continent. Significantly lower ratio values were found in the 20-45° latitudinal band (0.04 to 0.13) compared to the rest of the continent (up to 0.20) and attributed to the contribution of the French atmospheric tests to the ultra-trace plutonium levels found in these soils. Based on sediment cores collected in lakes of Chile and Uruguay, we show the added value of measuring 240Pu/239Pu atom ratios to refine the age models of environmental archives in this region of the world.

Mobilization and transport of pesticides with runoff and suspended sediment during flooding events in an agricultural catchment of Southern Brazil.

Brazil is one of the largest consumers of pesticides in the world, and these chemicals present a high contamination risk for the country's water bodies. The mechanisms of mobilization and transport of pesticides from cropland to river systems are controlled by runoff and erosion processes occurring at the catchment scale. In addition to the excessive use of pesticides, the transport processes of these substances are also accelerated by inadequate soil management and the absence of soil conservation measures at the catchment scale. The current research relied on hydrological monitoring to investigate the transport and persistence of pesticides in response to hydrological dynamics. The study was conducted in the Conceição River watershed where runoff and suspended sediment fluxes are continuously monitored at the outlet. This study area is representative of the grain production system in southern Brazil including the application of large amounts of pesticides combined with extensive runoff and erosion problems. Sample collection in the river for pesticide analysis included the analysis of both water and suspended sediment. The sediment deposit analysis was performed in a single location at 4 depths. Results demonstrate the occurrence of pesticides including simazine, 2,4-D, carbendazim, imidacloprid, tebuconazole, propiconazole, tetraconazole, and trifloxystrobin in water, while glyphosate and AMPA were detected in suspended sediments, and AMPA and carbendazim were found in sediment deposits. The study demonstrated the strong dependence of the mechanisms of pesticide mobilization and transport in the catchment with the intra- and interevent variability of hydro-sedimentary processes. Pesticide detections can be related to several factors, including the magnitude of the rainfall event, the period of pesticide application, or the transport of suspended sediment. All these factors are correlated, and the mechanisms of transportation play an important role in the connections between sink and sources. The results suggest that pesticide monitoring should take into account the runoff and erosion pathways in each particular catchment, and it should especially include the monitoring of major rainfall events for identifying and quantifying the occurrence of pesticides in the environment. The transport of pesticides indicates to be potentiated by intensive pesticide use, the magnitude of rainfall-runoff events, and the absence of runoff control measures (e.g., terracing). These results demonstrate that water and soil conservation techniques should be planned and coordinated at the watershed scale to reduce the connectivity of water and sediment flows from agricultural areas to river systems with the implementation of effective runoff control practices. This will control the mobilization agents (runoff), as well as limit the connection between the sources and the water bodies.

Silver and thallium historical trends in the Seine River basin.

Records on pollution by metals of minor economic importance (e.g. silver and thallium) but which prove to be toxic are rarely documented in river sediment. This study used two sediment cores collected downstream of the Seine River to describe the temporal evolution of Ag and Tl concentrations in an urban catchment. Radionuclide analysis (i.e. Cs-137 and Pb-210) allowed dating sediment deposition within the cores (1933-2003). Ag concentration reached maximum values of 14.3-24.6 mg kg(-1) in the 1960s and 1970s, before gradually decreasing up to values which approximated 4 mg kg(-1) in 2003. In contrast, Tl concentrations remained roughly constant throughout the core (median value of 0.86 mg kg(-1)). Suspended solids was collected at upstream locations in the catchment to derive the background concentrations in Ag and Tl. Very high Ag concentrations were measured in the upstream Seine River sites (0.33-0.59 mg kg(-1)), compared to the values reported in the literature (0.055 mg kg(-1)). This suggests the presence of a widespread and ancient Ag pollution in the Seine River basin, as demonstrated by the very high Ag enrichment ratios recorded in the cores. Annual flux of particulate Ag in the Seine River was estimated at 1.7 t yr(-1) in 2003. In contrast, Tl concentrations remained in the same order of magnitude as the natural background signal (0.3-0.5 mg kg(-1)). This study suggests that the Seine River basin is free of Tl contamination. Future concerns should hence mostly rely on Ag contamination, in a context of increasing Ag uses and possible releases to the environment.

Plutonium aided reconstruction of caesium atmospheric fallout in European topsoils.

Global nuclear weapon testing and the Chernobyl accident have released large amounts of radionuclides into the environment. However, to date, the spatial patterns of these fallout sources remain poorly constrained. Fallout radionuclides (137Cs, 239Pu, 240Pu) were measured in soil samples (n = 160) collected at flat, undisturbed grasslands in Western Europe in the framework of a harmonised European soil survey. We show that both fallout sources left a specific radionuclide imprint in European soils. Accordingly, we used plutonium to quantify contributions of global versus Chernobyl fallout to 137Cs found in European soils. Spatial prediction models allowed for a first assessment of the global versus Chernobyl fallout pattern across national boundaries. Understanding the magnitude of these fallout sources is crucial not only to establish a baseline in case of future radionuclide fallout but also to define a baseline for geomorphological reconstructions of soil redistribution due to soil erosion processes.

A new method for determining 236U/238U isotope ratios in environmental samples by means OF ICP-MS/MS.

The 236U/238U isotope ratio is a widely used tracer, which provides information on source identification for safeguard purposes, nuclear forensic studies and environmental monitoring. This paper describes an original approach to determine 236U/238U ratios, below 10-8, in environmental samples by combination of ICP-MS/MS for 236U/238U ratio and multiple collector ICPMS measurements for 235U/238U and 234U/235U isotope ratios. Since the hydride form of UO+ (UOH+) is less prone to occur than UH+, we were focused on the oxidised forms of uranium in order to reduce hydride based-interferences in ICP-MS/MS. Then, in-cell ion-molecule reactions with O2 and CO2 were assessed to detect the uranium isotopes in mass-shift mode (Q1: U+ → Q2: UO+). The performances in terms of UO+ sensitivity and minimisation of hydride form of UO+ were evaluated using five different desolvating systems. The best conditions, using an Apex Ω or an Aridus system, produced uranium oxide hydride rate (235U16O1H+/235U16O+) of about 10-7 with O2 in the collision cell. The method was validated through measurements of two certified IRMM standards with 236U/238U isotope ratio of 1.245 × 10-7 and 1.052 × 10-8, giving results in agreement with certified reference values. The relative standard deviations on seven independent measurements for each standard were respectively of 1.5% and 6.2%. Finally, environmental samples corresponding to sediments from the radioactive contamination plume emitted by the Fukushima Daiichi Nuclear Power Plant accident were analysed after a well-established uranium chemical separation procedure. 236U/238U atomic ratios between 1.5 × 10-8 and 7 × 10-9 were obtained with a level accuracy lower than 20%.

Investigating the relationships between chemical element concentrations and discharge to improve our understanding of their transport patterns in rural catchments under subtropical climate conditions.

Solute and particulate elemental concentrations (C) exhibit different responses to changes in discharge (Q), and those relationships are not well understood in subtropical agricultural environments. The objective is to describe the transport processes of different chemical elements during a set of contrasted rainfall events (2011-2015) that occurred in a small rural catchment under subtropical climate. The study was carried out in the Lajeado Ferreira Creek catchment (1.23 km2), southern Brazil. To this end, the concentrations in dissolved organic carbon (DOC), Cl-, NO3-, SO4-, ten chemical elements (in either dissolved or particulate forms) and suspended sediment concentrations (SSC) were determined. Metric indices were then calculated to characterize their transport patterns: (i) the best fit slope between log-C and log-Q (ß), (ii) the coefficient of variation of C and Q, (iii) shape of the hysteresis loop and hysteresis index, and (iv) the flushing index. All particulate elements along with the dissolved inorganic phosphorus (PO4-3) were shown to be controlled by the sediment dynamics. Geogenic elements (Fe2+, Zn2+, Cu2+, Mn2+, Si4+) showed a dilution effect with increasing Q values, likely because they were mainly transported with subsurface and base flow. Dissolved elements that are mainly supplied with fertilizers (Na+ and Cl-) as well as DOC showed a dilution effect, although they were mainly transported by surface runoff. Finally, a chemostatic behavior was found for those chemical elements (Mg2+, K+, Ca2+, NO3- and SO42-) that are supplied by more than one flow pathways. The results demonstrate that under subtropical climate conditions, the transport of essential nutrients including PO4-3 and metals (in particulate form), are mainly transported with surface runoff. Accordingly, runoff control on cultivated hillslopes should be improved to reduce the potential contaminant supply to the river and to reduce the potentially deleterious impacts that they may cause in downstream regions.