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.

Pile-dwellings of the Neolithic and the Bronze Age in Switzerland. Long-term research and future tasks

Swiss lake-side settlements dating between 4300 and 800 BC were first recognized in the early 19th century and between 1854 and 1880 early research boomed due to the first scientific studies and the artificial lowering of lakes in Western Switzerland. In the 20th century underwater and wetland archaeology experienced an enormous surge not only because of large rescue excavations, due to extensive motorway construction projects but also due to the evolution of modern IT technology in the 1970s. For the first time huge quantities of ancient wooden structures could be dated by dendrochronology. This produced a quantum leap in the 150 years of pile-dwelling research. In 2011, the UNESCO World Heritage Committee recognized the outstanding universal value of these sites. This article presents an overview about Swiss pile-dwellings of the Neolithic and the Bronze Age and the results of two recent diploma works (case study Sutz-Lattrigen Haupstation innen and case study Seedorf Lobsigensee) as examples of research and cooperation between universities and government agencies for cultural heritage management.

Tracer applications of noble gas radionuclides in the geosciences

Noble gas radionuclides, including 81Kr (t1/2 = 229,000 years), 85Kr (t1/2 = 10.8 years), and 39Ar (t1/2 = 269 years), possess nearly ideal chemical and physical properties for studies of earth and environmental processes. Recent advances in Atom Trap Trace Analysis (ATTA), a laser-based atom counting method, have enabled routine measurements of the radiokrypton isotopes, as well as the demonstration of the ability to measure 39Ar in environmental samples. Here we provide an overview of the ATTA technique, and a survey of recent progress made in several laboratories worldwide.We review the application of noble gas radionuclides in the geosciences and discuss how ATTA can help advance these fields, specifically: determination of groundwater residence times using 81Kr, 85Kr, and 39Ar; dating old glacial ice using 81Kr; and an 39Ar survey of the main water masses of the oceans, to study circulation pathways and estimate mean residence times. Other scientific questions involving a deeper circulation of fluids in the Earth's crust and mantle are also within the scope of future applications. We conclude that the geoscience community would greatly benefit from an ATTA facility dedicated to this field, with instrumentation for routine measurements, as well as for research on further development of ATTA methods.

Prevalence and severity of dental fluorosis among students from João Pessoa, PB, Brazil

The aim of this study was to determine the prevalence and severity of dental fluorosis among 12-15-year-old students from João Pessoa, PB, Brazil before starting a program of artificial fluoridation of drinking water. The use of fluoridated dentifrice was also surveyed. A sample of 1,402 students was randomly selected. However, 31 students refused to participate and 257 were not permanent residents in João Pessoa, thus leaving a final sample of 1,114 students. Clinical exams were carried out by two calibrated dentists (Kappa = 0.78) under natural indirect light. Upper and lower front teeth were cleaned with gauze and dried, and then examined using the TF index for fluorosis. A questionnaire on dentifrice ingestion and oral hygiene habits was applied to the students. The results revealed that fluorosis prevalence in this age group was higher than expected (29.2%). Most fluorosis cases were TF = 1 (66.8%), and the most severe cases were TF = 4 (2.2%). The majority of the students reported that they had been using fluoridated dentifrices since childhood; 95% of the participants preferred brands with a 1,500 ppm F concentration, and 40% remembered that they usually ingested or still ingest dentifrice during brushing. It was concluded that dental fluorosis prevalence among students in João Pessoa is higher than expected for an area with non-fluoridated water. However, although most students use fluoridated dentifrices, and almost half ingest slurry while brushing, the majority of cases had little aesthetic relevance from the professionals' point of view, thus suggesting that fluorosis is not a public health problem in the locality.

Long-term climate change commitment and reversibility: An EMIC Intercomparison

This paper summarizes the results of an intercomparison project with Earth System Models of Intermediate Complexity (EMICs) undertaken in support of the Intergovernmental Panel on Climate Change (IPCC) Fifth Assessment Report (AR5). The focus is on long-term climate projections designed to 1) quantify the climate change commitment of different radiative forcing trajectories and 2) explore the extent to which climate change is reversible on human time scales. All commitment simulations follow the four representative concentration pathways (RCPs) and their extensions to year 2300. Most EMICs simulate substantial surface air temperature and thermosteric sea level rise commitment following stabilization of the atmospheric composition at year-2300 levels. The meridional overturning circulation (MOC) is weakened temporarily and recovers to near-preindustrial values in most models for RCPs 2.6-6.0. The MOC weakening is more persistent for RCP8.5. Elimination of anthropogenic CO2 emissions after 2300 results in slowly decreasing atmospheric CO2 concentrations. At year 3000 atmospheric CO2 is still at more than half its year-2300 level in all EMICs for RCPs 4.5-8.5. Surface air temperature remains constant or decreases slightly and thermosteric sea level rise continues for centuries after elimination of CO2 emissions in all EMICs. Restoration of atmospheric CO2 from RCP to preindustrial levels over 100-1000 years requires large artificial removal of CO2 from the atmosphere and does not result in the simultaneous return to preindustrial climate conditions, as surface air temperature and sea level response exhibit a substantial time lag relative to atmospheric CO2.

A novel phosphorylation-independent interaction between SMG6 and UPF1 is essential for human NMD

Eukaryotic mRNAs with premature translation-termination codons (PTCs) are recognized and eliminated by nonsense-mediated mRNA decay (NMD). NMD substrates can be degraded by different routes that all require phosphorylated UPF1 (P-UPF1) as a starting point. The endonuclease SMG6, which cleaves mRNA near the PTC, is one of the three known NMD factors thought to be recruited to nonsense mRNAs via an interaction with P-UPF1, leading to eventual mRNA degradation. By artificial tethering of SMG6 and mutants thereof to a reporter mRNA combined with knockdowns of various NMD factors, we demonstrate that besides its endonucleolytic activity, SMG6 also requires UPF1 and SMG1 to reduce reporter mRNA levels. Using in vivo and in vitro approaches, we further document that SMG6 and the unique stalk region of the UPF1 helicase domain, along with a contribution from the SQ domain, form a novel interaction and we also show that this region of the UPF1 helicase domain is critical for SMG6 function and NMD. Our results show that this interaction is required for NMD and for the capability of tethered SMG6 to degrade its bound RNA, suggesting that it contributes to the intricate regulation of UPF1 and SMG6 enzymatic activities.

Natural Tracers in recent groundwaters from different Alpine aquifers

Groundwater with underground residence times between days and a few years have been investigated over more than 20 years from 487 remote sites located in different aquifer types in the Alpine belt. Analysis of the data reveals that groundwaters evolved in crystalline, evaporite, carbonate, molasse, and flysch aquifers can be clearly distinguished based on their major and trace element composition and degree of mineralisation. A further subdivision can be made even within one aquifer type based on the trace element compositions, which are characteristic for the lithologic environment. Major and trace element concentrations can be quantitatively described by interaction of the groundwater with the aquifer- specific mineralogy along the flow path. Because all investigated sites show minimal anthropogenic influences, the observed concentration ranges represent the natural background concentrations and can thus serve as a “geo-reference” for recent groundwaters from these five aquifer types. This “geo-reference” is particularly useful for the identification of groundwater contamination. It further shows that drinking water standards can be grossly exceeded for critical elements by purely natural processes

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.

Ce(III) and Ce(IV) (re)distribution and fractionation in a laterite profile from Madagascar: Insights from in situ XANES spectroscopy at the Ce LIII-edge

The distribution of trivalent and tetravalent cerium, Ce(III) and Ce(IV) respectively, in a lateritic profile from Madagascar, has been characterized by X-ray-absorption near-edge structure (XANES) spectroscopy at the Ce LIII-edge on the LUCIA beamline (SOLEIL synchrotron, France). XANES spectra were acquired on bulk-rock samples as well as on specific lateritic minerals or polymineral zones (in-situ measurements) of the tonalite bedrock and the three overlying weathered horizons (C-, B- and A-horizons). Geochemically, the bedrock, and the A- and C-horizons show similar rare earth element content (REE = 363–405 mg/kg). They also display the same positive Ce-anomaly (CeCN/Ce∗ = 1.12–1.45), which is therefore likely to be inherited from the bedrock. In the B-horizon, the higher REE content (REE = 2194 mg/kg) and the larger Ce-anomaly (CeCN/Ce∗ = 4.26) are consistent with an accumulation zone caused by the evaporation of groundwater during the dry season. There is a good agreement between the Ce(III)/Cetotal ratio (XCe(III)) deduced from the positive Ce-anomaly (bulk-rock geochemical data) and that derived from XANES spectroscopy on the same bulk-rock samples (BR-XCe(III)-XANES) in the bedrock, and the C- and B-horizons. In the A-horizon, XANES measurements on bulk rock and minerals revealed a higher BR-XCe(III)-XANES (up to 100%) compared to the XCe(III) deduced from geochemical data (XCe(III) = 79%). The preservation of a positive Ce-anomaly in the A-horizon suggests that the Ce mobilization and redistribution during weathering occurred with no significant Ce fractionation from other trivalent REE. Remarkably, the only investigated sample where cerianite is observed belongs to the B-horizon. Within this horizon, Ce oxidation state varies depending on the microstructural position (porosity, cracks, clay-rich groundmass). The highest Ce(IV) concentrations are measured in cerianite (and aluminophosphates) localized in pores at the vicinity of Mn-rich domains (XCe(III)-XANES = 30–51%). Therefore, Ce fractionation from other REE is attributed to a Ce oxidation and precipitation potentially assisted by oxyhydroxide scavenging. In the C-horizon, Ce(III) and Ce(IV) are mainly distributed in REE-minerals of the rhabdophane group found in pores and cracks. The similarity between the Ce(III) proportion of rhabdophane grains (XCe(III)-XANES = 74–89%) with that of the bedrock (BR-XCe(III)-XANES = 79%) suggests no significant fractionation of Ce(III) and Ce(IV) between solution and mineral during the successive stages of primary REE-mineral alteration, transport in solution and secondary precipitation in the incipient stages of weathering. Overall, our novel spectroscopic approach shows that Ce is not necessarily oxidized nor fractionated from other REE during weathering in lateritic conditions. This implies that like Ce(III), Ce(IV) can be mobilized in aqueous fluids during weathering, possibly thanks to complexation with organic molecules, and can precipitate together with Ce(III) in secondary REE-bearing minerals. The corollary is that (paleo)redox reconstructions in soils and/or sediments based on Ce-anomaly in weathered rocks or minerals must be interpreted with caution.

Natural anti-FcepsilonRIalpha autoantibodies may interfere with diagnostic tests for autoimmune urticaria.

IgG autoantibodies against the alpha-chain of the high affinity IgE receptor are claimed to play a pathogenetic role in autoimmune urticaria. The best methods for detection of functional autoantibodies are currently the autologous serum skin test and the basophil histamine release assay. A simplified and feasible screening test would facilitate the diagnosis of autoimmune urticaria. Here we offer an explanation for the difficulties in establishing a screening test for autoantibodies directed against the alpha-chain of the high affinity IgE receptor in autoimmune urticaria. Identical autoantibodies in chronic urticaria patients and healthy donors belonging to the natural autoantibody repertoire were found by sequence analysis of anti-alpha-chain autoantibodies isolated by repertoire cloning from antibody libraries. These natural autoantibodies bound to the receptor and triggered histamine release but only if IgE was previously removed from the receptor. Diagnostic assays used for detection of antibodies directed against the IgE receptor may require signal comparison with and without the artificial removal of IgE, immune complexes, and complement in order to avoid false positive or negative results. After IgE removal diagnostic tests will detect natural autoantibodies against the high affinity IgE receptor regardless of whether they are pathogenic or not.