Dating groundwater in the Bohemian Cretaceous Basin: Understanding tracer variations in the subsurface

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.

Thermal neutron capture effects in radioactive and stable nuclide systems

Neutron capture effects in meteorites and lunar surface samples have been successfully used in the past to study exposure histories and shielding conditions. In recent years, however, it turned out that neutron capture effects produce a nuisance for some of the short-lived radionuclide systems. The most prominent example is the 182Hf-182W system in iron meteorites, for which neutron capture effects lower the 182W/184W ratio, thereby producing too old apparent ages. Here, we present a thorough study of neutron capture effects in iron meteorites, ordinary chondrites, and carbonaceous chondrites, whereas the focus is on iron meteorites. We study in detail the effects responsible for neutron production, neutron transport, and neutron slowing down and find that neutron capture in all studied meteorite types is not, as usually expected, exclusively via thermal neutrons. In contrast, most of the neutron capture in iron meteorites is in the epithermal energy range and there is a significant contribution from epithermal neutron capture even in stony meteorites. Using sophisticated particle spectra and evaluated cross section data files for neutron capture reactions we calculate the neutron capture effects for Sm, Gd, Cd, Pd, Pt, and Os isotopes, which all can serve as neutron-dose proxies, either in stony or in iron meteorites. In addition, we model neutron capture effects in W and Ag isotopes. For W isotopes, the GCR-induced shifts perfectly correlate with Os and Pt isotope shifts, which therefore can be used as neutron-dose proxies and permit a reliable correction. We also found that GCR-induced effects for the 107Pd-107Ag system can be significant and need to be corrected, a result that is in contrast to earlier studies.

The dating of dipterocarp tree rings: establishing a record of carbon cycling and climatic change in the tropics

In a first step to obtain a proxy record of past climatic events (including the El Ni (n) over tildeo-Southern Oscillation) in the normally aseasonal tropical environment of Sabah, a radial segment from a recently fallen dipterocarp (Shorea Superba) was radiocarbon dated and subjected to carbon isotope analysis. The high-precision radiocarbon results fell into the ambiguous modern plateau where several calibrated dates can exist for each sample. Dating was achieved by wiggle matching using a Bayesian approach to calibration. Using the defined growth characteristics of Shorea superba, probability density distributions were calculated and improbable dates rejected. It was found that the tree most likely started growing around AD 1660-1685. A total of 173 apparent growth increments were measured and, therefore, it could be determined that the tree formed one ring approximately every two years. Stable carbon isotope values were obtained from resin-extracted wholewood from each ring. Carbon cycling is evident in the `juvenile effect', resulting from the assimilation of respired carbon dioxide and lower light levels below the canopy, and in the `anthropogenic effect' caused by increased industrial activity in the late-nineteenth and twentieth centuries. This study demonstrates that palaeoenvironmental information can be obtained from trees growing in aseasonal environments, where climatic conditions prevent the formation of well-defined annual rings.

Dating polygenetic metamorphic assemblages along a transect across the Western Alps

Multichronometric analyses were performed on samples from a transect in the French-Italian Western Alps crossing nappes derived from the Briançonnais terrane and the Piemonte-Liguria Ocean, in an endeavour to constrain the high-pressure (HP) metamorphism and the retrogression history. 12 samples of white mica were analysed by 39Ar-40Ar stepwise heating, complemented by 2 samples from the Monte Rosa 100 km to the NE and also attributed to the Briançonnais terrane. One Sm-Nd and three Lu-Hf garnet ages from eclogites were also obtained. White mica ages decrease from ca. 300 Ma in the westernmost samples (Zone Houillère), reaching ca. 300 °C during Alpine metamorphism, to < 48 Ma in the internal units to the East, which reached ca. 500 °C during Alpine orogeny. The conventional “thermochronological” interpretation postulates Cretaceous Eo-Alpine HP metamorphism and younger “cooling ages” in the higher-temperature samples. However, Eocene Lu-Hf and Sm-Nd ages from the same samples cannot be interpreted as post-metamorphic cooling ages, which makes a Cretaceous eclogitization untenable. The age date from this transect require instead to replace conventional “thermochronology” by an approach combining age dating with detailed geochemical, petrological and microstructural investigations. Petrology reveals important mineralogical differences along the transect. Samples from the Zone Houillère mostly contain detrital mica. White mica with Si > 6.45 atoms per formula unit becomes more abundant eastward. Across the whole traverse, HP phengitic mica forms the D1 foliation. Syn-D2 mica is Si-poorer and associated with nappe stacking, exhumation, and hydrous retrogression under greenschist facies conditions. D1 phengite is very often corroded, overgrown or intergrown by syn-D2 muscovite. Most importantly, syn-D2 recrystallization is not limited to S2 schistosity domains; microchemical fingerprinting shows that it also can form pseudomorphs after crystals that could be mistaken to have formed during D1 based on microstructural arguments alone. Thereby the Cl concentration in white mica is a useful discriminator, since D2 retrogression was associated with a less saline fluid than eclogitization. Once the petrological stage is set, geochronology is straightforward. All samples contain mixtures of detrital, syn-D1 and syn-D2 mica, and retrogression phases (D3) in greatly varying proportions according to local pressure-temperature-fluid activity-deformation conditions. The correlation of age vs. Cl/K clearly identifies 47 ± 1 Ma as the age of formation of syn-D1 mica along the entire transect, including the Monte Rosa nappe samples. The inferred age of the greenschist-facies low-Si syn-D2 mica generation ranges within 39-43 Ma, with local variations. Coexistence of D1 and D2 ages, and the constancy of non-reset D1 ages along the entire transect, are strong evidence that the D1 white mica ages are very close to formation ages. Volume diffusion of Ar in white mica (activation energy E = 250 kJ/mol; pressure-adjusted diffusion coefficient D’0 < 0.03 cm2 s-1) has a subordinate effect on mineral ages compared to both prograde and retrograde recrystallization in most samples. Eocene Lu-Hf and Sm-Nd garnet ages are prograde and predate the HP peak.

Helium transfer from water into quartz crystals: A new approach for porewater dating

Several important fundamental and applied problems require a quantification of slow rates of groundwater flow. To resolve these problems helium appears to be a promising tracer. In this contribution we discuss a new approach, which gives the helium inventory in a rock – pore water system by using the relevant mineral record, i.e., without extraction and investigation of the porewater samples. Some U- and Th-poor minerals such as quartz (quartz separates from Permo-Carboniferous Formation, sandstone–shale interlayering, Molasses Basin, Northern Switzerland, hereafter PCF, are used in this study) contain excessive helium having migrated into their internal helium-accessible volume (HAV) from the surrounding porewater [I.N. Tolstikhin, B.E. Lehmann, H.H. Loosli, A. Gautschi, Helium and argon isotopes in rocks, minerals and related groundwaters: a case study in Northern Switzerland, Geochim. Cosmochim. Acta 60 (1996) 1497–1514]. These volumes are estimated by using helium as a nano-size penetrating tool, i.e., by saturation of the minerals with helium under controlled pressure–temperature conditions and subsequent measurements of the helium-saturated concentrations. In the quartz separates HAV/total volume ratios vary from 0.017% to 0.16%; along with the measured initial (unsaturated) He concentration the HAV gives the internal helium pressure, the mean value obtained for 7 samples (25 sample aliquots) is P=0.45F0.15 atm (1 r). The product of helium pressure and solubility (7.35_10_3 cc STP He/cc H2O for the temperature and salinity of PCF aquifers reported in [F.J. Pearson, W. Balderer, H.H. Loosli, B.E. Lehmann, A. Matter, T. Peters, H. Schmassmann, A. Gautschi, Applied Isotope Hydrogeology–A Case Study in Northern Switzerland, Elsevier Amsterdam, 1991, 439 pp.]) is the mineral-derived He concentration in the respective porewater, CPW=0.0035F0.0017 cc He/cc H2O. This value is in full accord with measured He concentrations in PCF aquifers, CPCF, varying from 0.0045 to 0.0016 cc He/cc H2O. This agreement validates the proposed approach and also shows that the mineral–porewater helium–concentration equilibrium has been established. Indeed, estimates of the He-migration rates through our quartz samples show that in ~6000 years the internal pressure should equilibrate with He-concentration in related porewater of PCF, and this time interval is short compared to independent estimates [I.N. Tolstikhin, B.E. Lehmann, H.H. Loosli, A. Gautschi, Helium and argon isotopes in rocks, minerals and related groundwaters: a case study in Northern Switzerland, Geochim. Cosmochim. Acta 60 (1996) 1497–1514]. The helium inventory in the rock–porewater assemblage shows that helium abundance in pore waters is indeed important. In shale samples (with ~15% porosity) porewaters contain more helium than the host minerals altogether. Porewater heliumconcentration profiles, available from the mineral record, along with helium production rates are input parameters allowing model(s) of helium migration through a hydrological structure to be developed. Quite high helium concentrations in PCF porewaters imply slow removal mechanisms, which will be discussed elsewhere.

210Pb dating of the Miaoergou ice core from the eastern Tien Shan, China

In 2005, two ice cores with lengths of 58.7 and 57.6 m respectively to bedrock were recovered from the Miaoergou flat-topped glacier (43 degrees 03 ' 19 '' N, 94 degrees 19 ' 21 '' E; 4512 m a.s.l.), eastern Tien Shan. Pb-210 dating of one of the ice cores (57.6 m) was performed, and an age of AD 1851 +/- 6 at a depth of 35.2 m w.e. was determined. For the period AD 1851-2005, a mean annual net accumulation of 229 +/- 7 mm w.e. a(-1) was calculated. At the nearby oasis city of Hami (similar to 80 km from the Miaoergou flat-topped glacier) the annual precipitation rate is 38 mm w.e. a(-1), hence glacial meltwater is a major water supply for local residents. The surface activity concentration of Pb-210(ex) was found to be similar to 400 mBq kg(-1), which is higher than observed at other continental sites such as Belukha, Russia, and Tsambagarav, Mongolia, which have surface activity concentrations of 280 mBq kg(-1). The Pb-210 dating agrees well with the chronological sequence deduced from the annual-layer counting resulting from the seasonalities of delta O-18 and trace metals for the period AD 1953-2005, and beta-activity horizons resulting from atmospheric nuclear testing during the period AD 1962-63. We conclude that Pb-210 analysis is a suitable method for obtaining a continuous dating of the Miaoergou ice core for similar to 160 years, which can also be applied to other ice cores recovered from the mountains of western China.

Groundwater dating with Atom Trap Trace Analysis of 39Ar

We report on the realization of Atom Trap Trace Analysis for39Ar and its first application to dating of groundwater samples. The presented system achieves an atmospheric39Ar count rate as high as 3.58 ± 0.10 atoms/h allowing for the determination of the39Ar concentration in less than a day. We demonstrate that the measured count rates are proportional to the39Ar concentration by intercomparison with Low-Level Counting results and by measurements on prepared argon samples with defined concentration. For a geophysical application, we degas three different groundwater samples and gas chromatographically extract the argon. The39Ar ages inferred from the count rates extend over the accessible dating range and are in agreement with the Low-Level Counting results as well as with complementary isotope data.

Late Quaternary history of the Vakinankaratra volcanic field (central Madagascar): insights from luminescence dating of phreatomagmatic eruption deposits

The Quaternary Vakinankaratra volcanic field in the central Madagascar highlands consists of scoria cones, lava flows, tuff rings, and maars. These volcanic landforms are the result of processes triggered by intracontinental rifting and overlie Precambrian basement or Neogene volcanic rocks. Infrared-stimulated luminescence (IRSL) dating was applied to 13 samples taken from phreatomagmatic eruption deposits in the Antsirabe–Betafo region with the aim of constraining the chronology of the volcanic activity. Establishing such a chronology is important for evaluating volcanic hazards in this densely populated area. Stratigraphic correlations of eruption deposits and IRSL ages suggest at least five phreatomagmatic eruption events in Late Pleistocene times. In the Lake Andraikiba region, two such eruption layers can be clearly distinguished. The older one yields ages between 109 ± 15 and 90 ± 11 ka and is possibly related to an eruption at the Amboniloha volcanic complex to the north. The younger one gives ages between 58 ± 4 and 47 ± 7 ka and is clearly related to the phreatomagmatic eruption that formed Lake Andraikiba. IRSL ages of a similar eruption deposit directly overlying basement laterite in the vicinity of the Fizinana and Ampasamihaiky volcanic complexes yield coherent ages of 68 ± 7 and 65 ± 8 ka. These ages provide the upper age limit for the subsequently developed Iavoko, Antsifotra, and Fizinana scoria cones and their associated lava flows. Two phreatomagmatic deposits, identified near Lake Tritrivakely, yield the youngest IRSL ages in the region, with respective ages of 32 ± 3 and 19 ± 2 ka. The reported K-feldspar IRSL ages are the first recorded numerical ages of phreatomagmatic eruption deposits in Madagascar, and our results confirm the huge potential of this dating approach for reconstructing the volcanic activity of Late Pleistocene to Holocene volcanic provinces.

Snow shielding factors for cosmogenic nuclide dating inferred from long-term neutron detector monitoring

The depth-dependent attenuation of the secondary cosmic-ray particle flux due to snow cover and its effects on production rates of cosmogenic nuclides constitutes a potential source of uncertainty for studies conducted in regions characterized by frequent seasonal snow burial. Recent experimental and numerical modelling studies have yielded new constraints on the effect of hydrogen-rich media on the production rates of cosmogenic nuclides by low- and high-energy neutrons (<10(-3) MeV and >10(2) MeV, respectively). Here we present long-term neutron-detector monitoring data from a natural setting that we use to quantify the effect of snow cover on the attenuation of fast neutrons (0.1-10 MeV), which are responsible for the production of Ne-21 from Mg and Cl-36 from K. We use data measured between July 2001 and May 2008 at seven stations located throughout the Ecrins-Pelvoux massif (French Western Alps) and its surroundings, at elevations ranging from 200 to 2500 m a.s.l. From the cosmic-ray fluxes recorded during summer, when snow is absent, we infer an apparent attenuation length of 148 g cm(-2) in the atmosphere at a latitude of similar to 45 degrees N and for altitudes ranging from similar to 200 to 2500 m a.s.l. Using snow water-equivalent (SWE) values obtained through snow-coring campaigns that overlap in time the neutron monitoring for five stations, we show that fast neutrons are much more strongly attenuated in snow than predicted by a conventional mass-shielding formulation and the attenuation length estimated in the atmosphere. We suggest that such strong attenuation results from boundary effects at the atmosphere/snow interface induced by the high efficiency of water as a neutron moderator. Finally, we propose an empirical model that allows calculating snow-shielding correction factors as a function of SWE for studies using Ne-21 and Cl-36 analyses in Mg- and K-rich minerals, respectively. This empirical model is of interest for studies with a focus on cosmic-ray exposure dating, particularly if the target rocks are made up of mafic to ultramafic units where seasonal snow-cover is a common phenomenon.

P-T-t estimation of syn-kinematic strain in low-grade quartz-feldspar bearing rocks using thermodynamic modeling and 40Ar/39Ar dating techniques: example of the Plan-de-Phasy shear zone unit (Briançonnais Zone, Western Alps)

Pressure–Temperature–time (P–T–t) estimates of the syn-kinematic strain at the peak-pressure conditions reached during shallow underthrusting of the Briançonnais Zone in the Alpine subduction zone was made by thermodynamic modelling and 40Ar/39Ar dating in the Plan-de-Phasy unit (SE of the Pelvoux Massif, Western Alps). The dated phengite minerals crystallized syn-kinematically in a shear zone indicating top-to-the-N motion. By combining X-ray mapping with multi-equilibrium calculations, we estimate the phengite crystallization conditions at 270 ± 50 °C and 8.1 ± 2 kbar at an age of 45.9 ± 1.1 Ma. Combining this P–T–t estimate with data from the literature allows us to constrain the timing and geometry of Alpine continental subduction. We propose that the Briançonnais units were scalped on top of the slab during ongoing continental subduction and exhumed continuously until collision.

The deglaciation history of the Simplon region (southern Swiss Alps) constrained by 10Be exposure dating of ice-molded bedrock surfaces

The deglaciation history of the Swiss Alps after the Last Glacial Maximum involved the decay of several ice domes and the subsequent disintegration of valley glaciers at high altitude. Here we use bedrock exposure dating to reconstruct the temporal and spatial pattern of ice retreat at the Simplon Pass (altitude: ∼2000 m) located 40 km southwest of the ‘Rhône ice dome’. Eleven 10Be exposure ages from glacially polished quartz veins and ice-molded bedrock surfaces cluster tightly between 13.5 ± 0.6 ka and 15.4 ± 0.6 ka (internal errors) indicating that the Simplon Pass depression became ice-free at 14.1 ± 0.4 ka (external error of mean age). This age constraint is interpreted to record the melting of the high valley glaciers in the Simplon Pass region during the warm Bølling–Allerød interstadial shortly after the Oldest Dryas stadial. Two bedrock samples collected a few hundred meters above the pass depression yield older 10Be ages of 17.8 ± 0.6 ka and 18.0 ± 0.6 ka. These ages likely reflect the initial downwasting of the Rhône ice dome and the termination of the ice transfluence from the ice dome across the Simplon Pass toward the southern foreland. There, the retreat of the piedmont glacier in Val d’Ossola was roughly synchronous with the decay of the Rhône ice dome in the interior of the mountain belt, as shown by 10Be ages of 17.7 ± 0.9 ka and 16.1 ± 0.6 ka for a whaleback at ∼500 m elevation near Montecrestese in northern Italy. In combination with well-dated paleoclimate records derived from lake sediments, our new age data suggest that during the deglaciation of the European Alps the decay of ice domes was approximately synchronous with the retreat of piedmont glaciers in the foreland and was followed by the melting of high-altitude valley glaciers after the transition from the Oldest Dryas to the Bølling–Allerød, when mean annual temperatures rose rapidly by ∼3 °C.