Diffusion of HTO,Br, I,Cs, Sr and Co in a clay formation: Results and modelling from an in situ experiment in Opalinus Clay

The migration of radioactive and chemical contaminants in clay materials and argillaceous host rocks is characterised by diffusion and retention processes. Valuable information on such processes can be gained by combining diffusion studies at laboratory scale with field migration tests. In this work, the outcome of a multi-tracer in situ migration test performed in the Opalinus Clay formation in the Mont Terri underground rock laboratory (Switzerland) is presented. Thus, 1.16 × 10⁵ Bq/L of HTO, 3.96 × 10³ Bq/L of ⁸⁵Sr, 6.29 × 10² Bq/L of ⁶⁰Co, 2.01 × 10⁻³ mol/L Cs, 9.10 × 10⁻⁴ mol/L I and 1.04 × 10⁻³ mol/L Br were injected into the borehole. The decrease of the radioisotope concentrations in the borehole was monitored using in situ γ-spectrometry. The other tracers were analyzed with state-of-the-art laboratory procedures after sampling of small water aliquots from the reservoir. The diffusion experiment was carried out over a period of one year after which the interval section was overcored and analyzed. Based on the experimental data from the tracer evolution in the borehole and the tracer profiles in the rock, the diffusion of tracers was modelled with the numerical code CRUNCH.     

Activation energies of the self-diffusion of HTO, 22Na+ and 36Cl− in a highly compacted argillaceous rock (Opalinus Clay)

The temperature dependence of the self-diffusion of HTO, ²²Na⁺ and ³⁶Cl⁻ in Opalinus Clay (OPA) was studied using a through-diffusion technique, in which the temperature was gradually increased in the steady state phase of the diffusion. The measurements were done on samples from two different geological locations. The dependence of the effective diffusion coefficient on temperature was found to be of an Arrhenius type in the temperature range between 0 and 70 °C. A slight difference between the two locations could be observed. The average value of the activation energy of the self-diffusion of HTO in OPA was 21.1 ± 1.6 kJ mol⁻¹, and 21.0 ± 3.5 and 19.4 ± 1.5 kJ mol⁻¹ for ²²Na⁺ and ³⁶Cl⁻, respectively. The measured values for HTO are slightly higher than the values found for the bulk liquid water (HTO: 18.8 ± 0.4 kJ mol⁻¹). This indicates that the structure of the confined water in OPA might be slightly different from that of bulk liquid water. Also for Na⁺ and Cl⁻, slightly higher values than in bulk liquid water (Na⁺: 18.4 kJ mol⁻¹; Cl⁻: 17.4 kJ mol⁻¹) were observed.The Stokes–Einstein relationship, based on the temperature dependency of the viscosity of bulk water, could not be used to describe the temperature dependence of the diffusion of HTO in OPA. This additionally indicates the slightly different structure of the pore water in OPA.     

Comparative study of tracer diffusion of HTO, Na and Cl in compacted kaolinite, illite and montmorillonite

The through-diffusion of HTO, ²²Na⁺ and ³⁶Cl⁻ in kaolinite, homo-ionic Na-illite and homo-ionic Na-montmorillonite was measured at a high degree of compaction as a function of the salt concentration in the ‘external solution’, i.e. in the solution in contact with the clay sample. The clays were chosen for this study because of their differences in the number and nature of ion exchange sites leading to different proportions of interlayer-, inter-particle and free pore water. It was found that the diffusive mass transfer of Na⁺ in Na-montmorillonite and Na-illite increased with decreasing external salt concentration, while the opposite trend was observed for the diffusion of Cl⁻. These trends are more pronounced in the case of Na-montmorillonite than in Na-illite, while almost no salt effect was observed for kaolinite. Similarly no salt effect was observed for the diffusion of HTO through all of the clays tested. These observations are in agreement with a conceptual model where it is assumed that cations diffuse preferentially in the interlayer or diffuse double-layer porosity, while anions are almost completely excluded from these regions. In the case of Na⁺ diffusion, the salt effects can be explained by an influence on the concentration gradient of diffusing cations, while in the case of Cl⁻ the external salt concentration has an effect on the accessible porosity. Effective diffusion coefficients of Cl⁻ fulfil the same relationship to porosity as those of the uncharged HTO, when using accessible porosities for such a comparison. Furthermore it is shown that pore diffusion coefficients for the three tracers are fairly well correlated with the respective diffusion coefficients in bulk water, if the effective diffusion coefficients for Na⁺ are derived from calculated tracer concentration gradients in the interlayer or diffuse double-layer porosities.     

Hydrogeology of a fractured shale (Opalinus Clay): Implications for deep geological disposal of radioactive wastes

As part of the Swiss programme for high-level radioactive-waste disposal, a Jurassic shale (Opalinus Clay) is being investigated as a potential host rock. Observations in clay pits and the results of a German research programme focusing on hazardous waste disposal have demonstrated that, at depths of 10–30 m, the permeability of the Opalinus Clay decreases by several orders of magnitude. Hydraulic tests in deeper boreholes (test intervals below 300 m) yielded hydraulic conductivities <10^–12 m/s, even though joints and faults were included in some of the test intervals. These measurements are consistent with hydrogeological data from Opalinus Clay sections in ten tunnels in the Folded Jura of northern Switzerland. Despite extensive faulting, only a few indications of minor water inflow were encountered in more than 6,600 m of tunnel. All inflows were in tunnel sections where the overburden is less than 200 m. The hydraulic data are consistent with clay pore-water hydrochemical and isotopic data. The extensive hydrogeological data base – part of which derives from particularly unfavourable geological environments – provides arguments that advective transport through faults and joints is not a critical issue for the suitability of Opalinus Clay as a host rock for deep geological waste disposal. Electronic Publication     

Determination of Halogens (F, Cl, Br, I), Sulfur and Water in Seventeen Geological Reference Materials

Fluorine, chlorine, bromine, iodine and sulfur were determined in seventeen geological reference materials after extraction by pyrohydrolysis. Fluorine, Cl and S (as sulfate ions) were determined in the extraction solution by ion chromatography with detection limits of around 0.2 mg l⁻¹. Bromine and I were measured by ICP-MS with detection limits of 1 μg l⁻¹ for Br and 0.1 μg l⁻¹ for I. For rock samples, using normal extraction conditions (500 mg of sample and 100 ml of final solution) detection limits were 40 mg kg⁻¹ for F and Cl, 15 mg kg⁻¹ for S, 0.2 mg kg⁻¹ for Br and 0.02 mg kg⁻¹ for I. These detection limits may be improved by increasing the amount of sample and hence the concentration of the final solution. Water was also determined using an extraction technique based on H₂O degassing, reduction on zinc at 1000 °C and H₂ manometry. Our results for fluorine, chlorine, sulfur and water are in good agreement with literature data. Very few reference materials have recommended values for bromine and especially for iodine. Among the analysed samples, three are new reference materials: BHVO-2, BCR-2 and AGV-2.     

Isotopic composition (H,O, Cl,Sr) of ground brines of the Siberian Platform

New data on the geochemistry and isotopic composition of chloride brines of the Siberian Platform are presented. The distribution of stable isotopes (²H, ¹⁸O, and ³⁷Cl) in brines of the Tunguska, Angara-Lena, western part of the Yakutian and Olenek artesian basins and ⁸⁷Sr/⁸⁶Sr in brines of the western part of the Olenek artesian basin was studied in the context of the problem of genesis of highly mineralized groundwaters. Results of the study and comparative analysis of the geochemical and isotopic peculiarities of the Siberian Platform brines conform to the theory of brine formation through the interaction of connate waters with enclosing rocks.     

Diffusion of HTO,Cl and I in Upper Toarcian argillite samples from Tournemire: Effects of initial iodide concentration and ionic strength

Diffusion parameters for HTO, ³⁶Cl⁻_, and ¹²⁵I⁻ were determined on Upper Toarcian argillite samples from the Tournemire Underground Research Laboratory (Aveyron, France) using the through diffusion technique. The direction of diffusion was parallel to the bedding plane. The purpose of the present study was 3-fold; it was intended (i) to confirm the I⁻ interaction with Upper Toarcian argillite and to verify the effects of initial I⁻ concentration on this affinity, as previously observed by means of radial diffusion experiments, (ii) to highlight any discrepancy between Cl⁻ and I⁻ diffusivity, and (iii) to investigate the effect of an increase of the ionic strength of the solution on the anionic tracers’ diffusive behaviour. The results show that the effective diffusion coefficient (D_e) and diffusion accessible porosity (ε_a) values obtained with an ionic strength (I.S.) synthetic pore water of 0.01 eq L⁻¹ are: D_e = 2.35–2.50 × 10⁻¹¹ m² s⁻¹ and ε_a = 12.0–15.0% for HTO, and D_e = 14.5–15.5 × 10⁻¹³ m² s⁻¹ and ε_a = 2.5–2.9% for ³⁶Cl⁻. Because of anionic exclusion effects, anions diffuse slower and exhibit smaller diffusion accessible porosities than HTO, taken as a water tracer. The associated effective diffusion coefficient (D_e) and rock capacity factor (α) obtained for ¹²⁵I are: D_e = 7.00–8.60 × 10⁻¹³ m² s⁻¹ and α = 4.3–7.2%. Such values make it possible to calculate low ¹²⁵I distribution ratios (0.0057 < R_D < 0.0192 mL g⁻¹) which confirm the trend indicating that the ¹²⁵I rock capacity factor increases with the decrease of the initial I⁻ concentration. Additional through-diffusion experiments were carried out with a higher ionic strength synthetic pore water (I.S. = 0.11 eq L⁻¹). No evolution of HTO diffusion parameters was observed. The anionic tracers’ effective diffusion coefficient increased by a factor of two but no clear evolution of their accessible porosity was observed. Such a paradox could be related to the particularly small mean pore size of the Upper Toarcian argillite of Tournemire. The most significant finding of this study is the large discrepancy (factor of two) between the values of the effective diffusion coefficient for ¹²⁵I and ³⁶Cl. Whatever the ionic strength of the synthetic solution used, ¹²⁵I exhibited D_e values two times lower than those of ³⁶Cl. A detailed explanation for this difference cannot be given at present even if a hypothesis based on ion-pairing or on steric-exclusion cannot be excluded. This makes questionable the assumption usually made for quantifying ¹²⁵I sorption and postulating that ³⁶Cl and ¹²⁵I would diffuse in the same porosity. In other terms, at Tournemire, ¹²⁵I sorption could be more pronounced than previously indicated.     

Origin of fluids in iron oxide–copper–gold deposits: constraints from δ 37Cl, 87Sr/86Sri and Cl/Br

The origin of the hypersaline fluids (magmatic or basinal brine?), associated with iron oxide (Cu–U–Au–REE) deposits, is controversial. We report the first chlorine and strontium isotope data combined with Cl/Br ratios of fluid inclusions from selected iron oxide–copper–gold (IOCG) deposits (Candelaria, Raúl–Condestable, Sossego), a deposit considered to represent a magmatic end member of the IOCG class of deposit (Gameleira), and a magnetite–apatite deposit (El Romeral) from South America. Our data indicate mixing of a high δ ³⁷Cl magmatic fluid with near 0‰ δ ³⁷Cl basinal brines in the Candelaria, Raúl–Condestable, and Sossego IOCG deposits and leaching of a few weight percent of evaporites by magmatic-hydrothermal (?) fluids at Gameleira and El Romeral. The Sr isotopic composition of the inclusion fluids of Candelaria, Raúl–Condestable, and El Romeral confirms the presence of a non-magmatic fluid component in these deposits. The heavy chlorine isotope signatures of fluids from the IOCG deposits (Candelaria, Raúl–Condestable, Sossego), reflecting the magmatic-hydrothermal component of these fluids, contrast with the near 0‰ δ ³⁷Cl values of porphyry copper fluids known from the literature. The heavy chlorine isotope compositions of fluids of the investigated IOCG deposits may indicate a prevailing mantle Cl component in contrast to porphyry copper fluids, an argument also supported by Os isotopes, or could result from differential Cl isotope fractionation processes (e.g. phase separation) in fluids of IOCG and porphyry Cu deposits.     

Diffusion and sorption of Cs, I and HTO in samples of the argillaceous Wakkanai Formation from the Horonobe URL, Japan: Clay-based modeling approach

Diffusion and sorption behaviors of cationic Cs⁺, anionic I⁻ and neutral HTO in samples of the Wakkanai Formation from the Horonobe underground research laboratory (URL), Japan, were investigated as a function of ionic strength (I) of synthetic groundwater by through-diffusion and batch sorption experiments and mechanistic modeling. The effective diffusivities (D_e) measured by through-diffusion experiments showed cation excess and anion exclusion effects, which were strongly dependent on I; D_e for Cs⁺ decreased as I increased, D_e for I⁻ showed the opposite dependency and D_e for HTO showed no dependence. The sorption of Cs⁺ measured by through-diffusion and batch sorption experiments were described by Freundlich isotherms with consistent parameters and decreased with I as a result of competitive ion exchange.Diffusion and sorption behaviors were interpreted by assuming the clay components of illite and smectite control diffusion and sorption mechanisms. The component additive (CA) sorption model, which includes illite and smectite contents and their ion exchange constants, provided a reasonable account of the Cs⁺ sorption trends measured as functions of I and Cs concentration. The diffusion model was developed by coupling the electrical double layer (EDL) model, describing the change of ionic concentrations (cation excess and anion deficit) and viscoelectric effects caused by electrostatic interaction at negatively charged clay surfaces, and a simplified pore model assuming one type of pore shape and includes their size distribution. When averaging the electrostatic effects by using the pore surface area distribution, the model could predict the cation excess and anion exclusion effects, and its dependence on I reasonably well. This result implies the nanoscale pores dominating the pore surface area can strongly impact on ionic diffusion in argillaceous rocks. The clay-based modeling approach described here provides a useful tool to predict ionic diffusion and sorption in argillaceous rocks.     

Large-scale tracer profiles in a deep claystone formation (Opalinus Clay at Mont Russelin,Switzerland): Implications for solute transport processes and transport properties of the rock

Natural tracers (Cl^? and stable water isotopes) in pore water of the Opalinus Clay and adjacent formations were studied in the motorway tunnel at Mont Russelin, Switzerland. The Opalinus Clay occurs in the core of an anticline which is cut by a complex system of thrust faults. Concentration profiles of natural tracers were taken from 17 boreholes along a 363 m long section. Pore waters of drillcore samples were analysed with indirect and direct methods. The Cl^? and stable water isotope distribution in the pore water shows a regular and well defined profile, with a conspicuous decrease towards the overlying Dogger limestone aquifer. The highest Cl^? values (approximately 23,000 mg/L) are found in the core of the anticline in Liassic claystones underlying the Opalinus Clay. To quantify the large-scale transport properties of the Opalinus Clay formation, a 2D transport model was constructed and used to reproduce the observed concentration profiles. The calculations indicate that the observed tracer distributions are consistent with diffusion as the dominant transport process. Groundwater flow in the overlying Dogger aquifer was initiated about 2–4 Ma ago, which is long after the folding of the Jura Mountains and probably coincides with the exposure of the aquifer to freshwater recharge following continued erosion of the anticline. The calculations suggest that tracer distributions are controlled by 1) the timing of freshwater recharge in the overlying limestone aquifer, 2) the shape of the anticline and 3) the magnitude and the anisotropy ratio of diffusion coefficients.     

Quantification of Cl,Br and I in Geological Materials by NH4F Digestion: Comparison with Rapid Acid Digestion

The lack of analytical techniques for halogens in geological materials is mainly due to the loss of analytes during sample preparation. This study describes a rapid bulk rock digestion method (NH₄F digestion) for determination of the abundances of Cl, Br and I in geological materials by SF-ICP-MS. During high temperature (200–240 °C) digestion, NH₃ released from the decomposition of molten NH₄F can effectively prevent the loss of halogens released from geological samples. Chlorine, Br and I were not lost during NH₄F digestion at 220 °C for 0.25–6 h. The limits of quantitation for NH₄F digestion were 2.8, 0.018 and 0.003 μg g^-1 Cl, Br and I, respectively. Most results for halogens in geological reference materials by NH₄F digestion were in agreement with their certified values, confirming that the high-performance rapid bulk rock NH₄F digestion has sufficient digestion capability to extract Cl, Br and I from rocks, sediments and soils. In comparison, results obtained following acid digestion showed that HNO₃ + HF digestion could effectively extract Br and I from soil and sediment samples, and that HNO₃ acid digestion is only suitable to use for the determination of Br and I in soil samples.     

Experimental Reversal of the Na-K Exchange Reaction Between Muscovite-Paragonite Crystalline Solutions and a 2 Molal Aqueous (Na,K)Cl Fluid

Single-phase 2M₁ muscovite-paragonite crystalline solutionsin the range 0?00–0?10 and 0?70–1?00 X_ms have beensynthesized by hydrothermal treatment of gels of appropriatecompositions at 600–700?C, and 7 to 18 kb P_H2O. The molarvolumes of these micas may be expressed as V(J/b?mol) = 13?1845+1?463X_ms+0?0160 X_ms²–0?1679 X_ms³ (?0?005), which translateto a substantial positive excess molar volume of mixing. Na-K ion exchange experiments between presynthesized 2M₁ micacrystalline solutions and 2 molal aqueous (Na,K)Cl fluids failedto proceed to completion despite 98 day runs at 500–600?C,6 kb P_total. Results of analogous exchange experiments provedencouraging however, when a much finer-grained 1M mica was usedas starting material. Applying the tie line rotation technique,reversal of ion exchange experiments could be achieved in the2-phase fields, not, however, in the 3-phase field of the ms-pg-NaCl-KClreciprocal ternary. Using gels as starting material, reversalexperiments were eventually successful both in the 2-phase andthe 3-phase fields; the results of reversal experiments withinthe two-phase fields being identical to those obtained earlierusing 1M micas. Four isobaric-isothermal sections through the ms-pg-NaCl-KClternary were reversibly determined at 450?C/5 kb, 550?C/6 kb,550?C/15 kb, and 620?C/7 kb. At 450?C, the coexisting mica compositionsin the 3-phase field (2 micas plus 1 fluid) are 0?10 and 0?77X_ms, at 550?C they are 0?10 and 0?60 X_ms, and finally, at 620?Cthese are 0?12 and 0?51 X_ms. To the extent that internal equilibriumwas accomplished between the coexisting micas, these data wouldindicate a wide solvus at 450?C, narrowing gradually with increasingtemperature to 620?C. The critical temperature will be wellin excess of 620?C, although the mica at the critical conditionwill prove to be metastable with respect to the assemblage alkalifeldspars+corundum+H₂O. The companion paper by Chatterjee & Flux (1986) presentsa thermodynamic analysis of the above experimental data.     

Sr and Nd isotopes as tracers in pedogenic studies: Evidence for Saharan dust contribution to the soils of Muravera (Sardinia,Italy)

Sr and Nd isotopes were applied to 5 soil profiles from the Muravera area, in south-eastern Sardinia.All the soils, which have developed during the Quaternary on the Lower Paleozoic metamorphic basement except for one on Eocene carbonates, are located far from major sources of pollution. Therefore, they are suitable for testing pedogenic processes and geochemical evolution to benefit for environmental studies.The Sr isotopic ratios range largely (δ⁸⁷Sr = 1.7–65.9‰), even in each soil profile. In particular, the observed increase of δ⁸⁷Sr with depth in the most of the metamorphic rock-based soils can be accounted for by the downward decrease of Sr contributions from organic matter and Saharan dust, both displaying lower isotopic ratios than the soil bedrocks. The carbonate rock-based soil exhibits δ⁸⁷Sr higher (1.7–18.1‰) than the bedrock, indicating a significant contribution of radiogenic Sr from the siliciclastic fraction of the soil, and probably from dust input. The Nd isotopic ratios are slightly variable through the profiles (ɛ_Nd from −7.8 to −14.5), confirming little mobility of Nd and Sm during the pedogenesis. Among the minerals present in the soils, phosphates, albite, and calcite are those important in providing low radiogenic Sr and Nd to organic matter of the soils.Lastly, this isotopic study has in particular allowed for evaluating the potential proportion of contribution of Saharan dust to south-eastern Sardinia, thus corroborating the findings of other studies related to soils from the central-western Mediterranean.     

Solubility of Fe2(OH)3Cl (pure-iron end-member of hibbingite) in NaCl and Na2SO4 brines

Pure-iron end-member hibbingite, Fe₂(OH)₃Cl(s), may be important to geological repositories in salt formations, as it may be a dominant corrosion product of steel waste canisters in an anoxic environment in Na–Cl- and Na–Mg–Cl-dominated brines. In this study, the solubility of Fe₂(OH)₃Cl(s), the pure-iron end-member of hibbingite (Fe^II, Mg)₂(OH)₃Cl(s), and Fe(OH)₂(s) in 0.04 m to 6 m NaCl brines has been determined. For the reactionFe₂(OH)₃Cl(s) + 3H⁺ ? 3 H₂O + 2 Fe²⁺ + Cl^?,the solubility constant of Fe₂(OH)₃Cl(s) at infinite dilution and 25 °C has been found to be log₁₀ K = 17.12 ± 0.15 (95% confidence interval using F statistics for 36 data points and 3 parameters). For the reactionFe(OH)₂(s) + 2H⁺ ? 2 H₂O + Fe²⁺,the solubility constant of Fe(OH)₂ at infinite dilution and 25 °C has been found to be log₁₀ K = 12.95 ± 0.13 (95 % confidence interval using F statistics for 36 data points and 3 parameters). For the combined set of solubility data for Fe₂(OH)₃Cl(s) and Fe(OH)₂(s), the Na⁺–Fe²⁺ pair Pitzer interaction parameter θ_{Na⁺/Fe²⁺} has been found to be 0.08 ± 0.03 (95% confidence interval using F statistics for 36 data points and 3 parameters). In nearly saturated NaCl brine we observed evidence for the conversion of Fe(OH)₂(s) to Fe₂(OH)₃Cl(s). Additionally, when Fe₂(OH)₃Cl(s) was added to sodium sulfate brines, the formation of green rust(II) sulfate was observed, along with the generation of hydrogen gas. The results presented here provide insight into understanding and modeling the geochemistry and performance assessment of nuclear waste repositories in salt formations.     

1Tc-Strontiohilgardit (Ca,Sr)2[B5O8(OH)2Cl] und seine Stellung in der Hilgarditgruppe X2/II[B5O8(OH)2Cl]

Zusammenfassung 1Tc-Strontiohilgardit (Ca, Sr)₂ [B₅O₈(OH)₂,Cl] mit Ca : Sr etwa 1 : 1 ist ein neues Mineral der Hilgarditgruppe. Fundpunkt: Reyersbausen (9° 59,7 E, 51° 36,6 N), Grube Königshall-Hindenburg, Flöz Staßfurt in sylvinitischer Ausbildung.Konstanten : triklin-pedial,a ₀=6,38 Å,b ₀=6,480 Å,c ₀=6,608 Å, =75,4°,=61,2°, =60,5°; tafelige-gestreckte Links- und Re chtskristalle, farblos, wasserunlöslich, piezoelektrisch. Härte 5–7, Dichte 2,99 g cm^–3;n =1,638,n =1,639,n =1,670; 2V =19°.Neue Daten für die Hilgarditgruppe : 2 M (Cc)-Calciumhilgardit (=Hilgardit) =4 Ca₂[B₅O₃(OH)₂Cl], Raumgruppe Cc.3Tc-Calciumhilgardit (=Parahilgardit) = 3 Ca₂[B₅O₃(OH)₂Cl]; trinklin-pedial, ₀=6,31 Å,b =6,484 Å,c ₀=17,50 Å; =84,0°,=79,6°, =60,9°.Die Polymorphiebeziehungen sind geometrisch deutbar durch eine spezielle Art der Polytropie (Stapelung von Links- und Rechtskristallen im Elementarbereich).     

Sr and Nd isotopes as tracers of clastic sources in Lake Le Bourget sediment (NW Alps, France) during the Little Ice Age: Palaeohydrology implications

Geochemical methods (major elements and Sr, Nd isotopes) have been used to (1) characterize Lake Le Bourget sediments in the French Alps, (2) identify the current sources of the clastic sediments and estimate the source variability over the last 600 years. Major element results indicate that Lake Le Bourget sediments consist of 45% clastic component and 55% endogenic calcite. In addition, several individual flood levels have been identified during the Little Ice Age (LIA) on the basis of their higher clastic content (> 70%).Potential sources of Lake Le Bourget clastic sediments have been investigated from Sr and Nd isotope compositions. The sediments from the Sierroz River and Leysse River which are mainly derived from the Mesozoic Calcareous Massifs are characterised by lower ⁸⁷Sr/⁸⁶Sr ratios and slightly lower ?_Nd(0) ratios than the Arve River sediments which are derived from the Palaeozoic Mont-Blanc External Crystalline Massifs. The Rhône River appears to have been the main source of clastic sediments into the lake for the last 600 years, as evidenced by a similar Sr and Nd isotopic compositions analyzed in core B16 sediments (⁸⁷Sr/⁸⁶Sr = 0.719, ?_Nd(0) = − 10) and in the sediments of the Rhône River (⁸⁷Sr/⁸⁶Sr = 0.719, ?_Nd(0) = − 9.6).The isotopic signatures of flood events and background samples from core B16 in Lake Le Bourget are also similar. This indicates that prior to ∼ 1800, the inputs into the lake have remained relatively homogeneous with the proportion of clastic component mainly being a function of the palaeohydrology of the Rhone River. Early human modification (deforestation and agriculture) of the lake catchment before the 1800s appears to have had little influence on the source of clastic sediments.