Non-exponential return time distributions for vorticity extremes explained by fractional Poisson processes

Serial correlation of extreme midlatitude cyclones observed at the storm track exits is explained by deviations from a Poisson process. To model these deviations, we apply fractional Poisson processes (FPPs) to extreme midlatitude cyclones, which are defined by the 850 hPa relative vorticity of the ERA interim reanalysis during boreal winter (DJF) and summer (JJA) seasons. Extremes are defined by a 99% quantile threshold in the grid-point time series. In general, FPPs are based on long-term memory and lead to non-exponential return time distributions. The return times are described by a Weibull distribution to approximate the Mittag–Leffler function in the FPPs. The Weibull shape parameter yields a dispersion parameter that agrees with results found for midlatitude cyclones. The memory of the FPP, which is determined by detrended fluctuation analysis, provides an independent estimate for the shape parameter. Thus, the analysis exhibits a concise framework of the deviation from Poisson statistics (by a dispersion parameter), non-exponential return times and memory (correlation) on the basis of a single parameter. The results have potential implications for the predictability of extreme cyclones.

Re-evaluation of pulmonary titanium dioxide nanoparticle distribution using the "relative deposition index": Evidence for clearance through microvasculature

ABSTRACT: BACKGROUND: Translocation of nanoparticles (NP) from the pulmonary airways into other pulmonary compartments or the systemic circulation is controversially discussed in the literature. In a previous study it was shown that titanium dioxide (TiO2) NP were "distributed in four lung compartments (air-filled spaces, epithelium/endothelium, connective tissue, capillary lumen) in correlation with compartment size". It was concluded that particles can move freely between these tissue compartments. To analyze whether the distribution of TiO2 NP in the lungs is really random or shows a preferential targeting we applied a newly developed method for comparing NP distributions. METHODS: Rat lungs exposed to an aerosol containing TiO2 NP were prepared for light and electron microscopy at 1 h and at 24 h after exposure. Numbers of TiO2 NP associated with each compartment were counted using energy filtering transmission electron microscopy. Compartment size was estimated by unbiased stereology from systematically sampled light micrographs. Numbers of particles were related to compartment size using a relative deposition index and chi-squared analysis. RESULTS: Nanoparticle distribution within the four compartments was not random at 1 h or at 24 h after exposure. At 1 h the connective tissue was the preferential target of the particles. At 24 h the NP were preferentially located in the capillary lumen. CONCLUSION: We conclude that TiO2 NP do not move freely between pulmonary tissue compartments, although they can pass from one compartment to another with relative ease. The residence time of NP in each tissue compartment of the respiratory system depends on the compartment and the time after exposure. It is suggested that a small fraction of TiO2 NP are rapidly transported from the airway lumen to the connective tissue and subsequently released into the systemic circulation.

Using 18O/2H, 3H/3He, 85Kr and CFCs to determine mean residence times and water origin in the Grazer and Leibnitzer Feld groundwater bodies (Austria)

Two groundwater bodies, Grazer Feld and Leibnitzer Feld, with surface areas of 166 and 103 km2 respectively are characterised for the first time by measuring the combination of d18O/d2H, 3H/3He, 85Kr, CFC-11, CFC-12 and hydrochemistry in 34 monitoring wells in 2009/2010. The timescales of groundwater recharge have been characterised by 131 d18O measurements of well and surface water sampled on a seasonal basis. Most monitoring wells show a seasonal variation or indicate variable contributions of the main river Mur (0–30%, max. 70%) and/or other rivers having their recharge areas in higher altitudes. Combined d18O/d2H-measurements indicate that 65–75% of groundwater recharge in the unusual wet year of 2009 was from precipitation in the summer based on values from the Graz meteorological station. Monitoring wells downstream of gravel pit lakes show a clear evaporation trend. A boron–nitrate differentiation plot shows more frequent boron-rich water in the more urbanised Grazer Feld and more frequent nitrate-rich water in the more agricultural used Leibnitzer Feld indicating that a some of the nitrate load in the Grazer Feld comes from urban sewer water. Several lumped parameter models based on tritium input data from Graz and monthly data from the river Mur (Spielfeld) since 1977 yield a Mean Residence Time (MRT) for the Mur-water itself between 3 and 4 years in this area. Data from d18O, 3H/3He measurements at the Wagna lysimeter station supports the conclusion that 90% of the groundwaters in the Grazer Feld and 73% in the Leibnitzer Feld have MRTs of <5 years. Only in a few groundwaters were MRTs of 6–10 or 11–25 years as a result of either a long-distance water inflow in the basins or due to longer flow path in somewhat deeper wells (>20 m) with relative thicker unsaturated zones. The young MRT of groundwater from two monitoring wells in the Leibnitzer Feld was confirmed by 85Kr-measurements. Most CFC-11 and CFC-12 concentrations in the groundwater exceed the equilibration concentrations of modern concentrations in water and are therefore unsuitable for dating purposes. An enrichment factor up to 100 compared to atmospheric equilibrium concentrations and the obvious correlation of CFC-12 with SO4, Na, Cl and B in the ground waters of the Grazer Feld suggest that waste water in contact with CFC-containing material above and below ground is the source for the contamination. The dominance of very young groundwater (<5 years) indicates a recent origin of the contamination by nitrate and many other components observed in parts of the groundwater bodies. Rapid measures to reduce those sources are needed to mitigate against further deterioration of these waters.

Strain-specific spleen remodelling in Plasmodium yoelii infections in Balb/c mice facilitates adherence and spleen macrophage-clearance escape

Knowledge of the dynamic features of the processes driven by malaria parasites in the spleen is lacking. To gain insight into the function and structure of the spleen in malaria, we have implemented intravital microscopy and magnetic resonance imaging of the mouse spleen in experimental infections with non-lethal (17X) and lethal (17XL) Plasmodium yoelii strains. Noticeably, there was higher parasite accumulation, reduced motility, loss of directionality, increased residence time and altered magnetic resonance only in the spleens of mice infected with 17X. Moreover, these differences were associated with the formation of a strain-specific induced spleen tissue barrier of fibroblastic origin, with red pulp macrophage-clearance evasion and with adherence of infected red blood cells to this barrier. Our data suggest that in this reticulocyte-prone non-lethal rodent malaria model, passage through the spleen is different from what is known in other Plasmodium species and open new avenues for functional/structural studies of this lymphoid organ in malaria.

Sensitivity of atmospheric CO2 and climate to explosive volcanic eruptions

Impacts of low-latitude, explosive volcanic eruptions on climate and the carbon cycle are quantified by forcing a comprehensive, fully coupled carbon cycle-climate model with pulse-like stratospheric aerosol optical depth changes. The model represents the radiative and dynamical response of the climate system to volcanic eruptions and simulates a decrease of global and regional atmospheric surface temperature, regionally distinct changes in precipitation, a positive phase of the North Atlantic Oscillation, and a decrease in atmospheric CO2 after volcanic eruptions. The volcanic-induced cooling reduces overturning rates in tropical soils, which dominates over reduced litter input due to soil moisture decrease, resulting in higher land carbon inventories for several decades. The perturbation in the ocean carbon inventory changes sign from an initial weak carbon sink to a carbon source. Positive carbon and negative temperature anomalies in subsurface waters last up to several decades. The multi-decadal decrease in atmospheric CO2 yields a small additional radiative forcing that amplifies the cooling and perturbs the Earth System on longer time scales than the atmospheric residence time of volcanic aerosols. In addition, century-scale global warming simulations with and without volcanic eruptions over the historical period show that the ocean integrates volcanic radiative cooling and responds for different physical and biogeochemical parameters such as steric sea level or dissolved oxygen. Results from a suite of sensitivity simulations with different magnitudes of stratospheric aerosol optical depth changes and from global warming simulations show that the carbon cycle-climate sensitivity γ, expressed as change in atmospheric CO2 per unit change in global mean surface temperature, depends on the magnitude and temporal evolution of the perturbation, and time scale of interest. On decadal time scales, modeled γ is several times larger for a Pinatubo-like eruption than for the industrial period and for a high emission, 21st century scenario.

Intra-subject variability in attention-deficit hyperactivity disorder

BACKGROUND: This study is based on a comprehensive survey of the neuropsychological attention-deficit hyperactivity disorder (ADHD) literature and presents the first psychometric analyses of different parameters of intra-subject variability (ISV) in patients with ADHD compared to healthy controls, using the Continuous Performance Test, a Go-NoGo task, a Stop Signal Task, as well as N-back tasks. METHODS: Data of 57 patients with ADHD and 53 age- and gender-matched controls were available for statistical analysis. Different parameters were used to describe central tendency (arithmetic mean, median), dispersion (standard deviation, coefficient of variation, consecutive variance), and shape (skewness, excess) of reaction time distributions, as well as errors (commissions and omissions). RESULTS: Group comparisons revealed by far the strongest effect sizes for measures of dispersion, followed by measures of central tendency, and by commission errors. Statistical control of ISV reduced group differences in the other measures substantially. One (patients) or two (controls) principal components explained up to 67% of the inter-individual differences in intra-individual variability. CONCLUSIONS: Results suggest that, across a variety of neuropsychological tests, measures of ISV contribute best to group discrimination, with limited incremental validity of measures of central tendency and errors. Furthermore, increased ISV might be a unitary construct in ADHD.

Stereoselective pharmacokinetics of ketamine and norketamine after racemic ketamine or S-ketamine administration in Shetland ponies sedated with xylazine

The pharmacokinetics of ketamine and norketamine enantiomers after administration of intravenous (IV) racemic ketamine (R-/S-ketamine; 2.2mg/kg) or S-ketamine (1.1mg/kg) to five ponies sedated with IV xylazine (1.1mg/kg) were compared. The time intervals to assume sternal and standing positions were recorded. Arterial blood samples were collected before and 1, 2, 4, 6, 8 and 13min after ketamine administration. Arterial blood gases were evaluated 5min after ketamine injection. Plasma concentrations of ketamine and norketamine enantiomers were determined by capillary electrophoresis and were evaluated by non-linear least square regression analysis applying a monocompartmental model. The first-order elimination rate constant was significantly higher and elimination half-life and mean residence time were lower for S-ketamine after S-ketamine compared to R-/S-ketamine administration. The maximum concentration of S-norketamine was higher after S-ketamine administration. Time to standing position was significantly diminished after S-ketamine compared to R-/S-ketamine. Blood gases showed low-degree hypoxaemia and hypercarbia.

Effect of 6-month supervised exercise on low-density lipoprotein apolipoprotein B kinetics in patients with type 2 diabetes mellitus

Although low-density lipoprotein (LDL) cholesterol is often normal in patients with type 2 diabetes mellitus, there is evidence for a reduced fractional catabolic rate and consequently an increased mean residence time (MRT), which can increase atherogenic risk. The dyslipidemia and insulin resistance of type 2 diabetes mellitus can be improved by aerobic exercise, but effects on LDL kinetics are unknown. The effect of 6-month supervised exercise on LDL apolipoprotein B kinetics was studied in a group of 17 patients with type 2 diabetes mellitus (mean age, 56.8 years; range, 38-68 years). Patients were randomized into a supervised group, who had a weekly training session, and an unsupervised group. LDL kinetics were measured with an infusion of 1-(13)C leucine at baseline in all groups and after 6 months of exercise in the patients. Eight body mass index-matched nondiabetic controls (mean age, 50.3 years; range, 40-67 years) were also studied at baseline only. At baseline, LDL MRT was significantly longer in the diabetic patients, whereas LDL production rate and fractional clearance rates were significantly lower than in controls. Percentage of glycated hemoglobin A(1c), body mass index, insulin sensitivity measured by the homeostasis model assessment, and very low-density lipoprotein triglyceride decreased (P < .02) in the supervised group, with no change in the unsupervised group. After 6 months, LDL cholesterol did not change in either the supervised or unsupervised group; but there was a significant change in LDL MRT between groups (P < .05) that correlated positively with very low-density lipoprotein triglyceride (r = 0.51, P < .04) and negatively with maximal oxygen uptake, a measure of fitness (r = -0.51, P = .035), in all patients. The LDL production and clearance rates did not change in either group. This study suggests that a supervised exercise program can reduce deleterious changes in LDL MRT.

Diffusive equilibration of N2, O2 and CO2 mixing ratios in a 1.5-million-years-old ice core

In the framework of the International Partnerships in Ice Core Sciences, one of the most important targets is to retrieve an Antarctic ice core that extends over the last 1.5 million years (i.e. an ice core that enters the climate era when glacial–interglacial cycles followed the obliquity cycles of the earth). In such an ice core the annual layers of the oldest ice would be thinned by a factor of about 100 and the climatic information of a 10 000 yr interval would be contained in less than 1 m of ice. The gas record in such an Antarctic ice core can potentially reveal the role of greenhouse gas forcing on these 40 000 yr cycles. However, besides the extreme thinning of the annual layers, also the long residence time of the trapped air in the ice and the relatively high ice temperatures near the bedrock favour diffusive exchanges. To investigate the changes in the O2 / N2 ratio, as well as the trapped CO2 concentrations, we modelled the diffusive exchange of the trapped gases O2, N2 and CO2 along the vertical axis. However, the boundary conditions of a potential drilling site are not yet well constrained and the uncertainties in the permeation coefficients of the air constituents in the ice are large. In our simulations, we have set the drill site ice thickness at 2700 m and the bedrock ice temperature at 5–10 K below the ice pressure melting point. Using these conditions and including all further uncertainties associated with the drill site and the permeation coefficients, the results suggest that in the oldest ice the precessional variations in the O2 / N2 ratio will be damped by 50–100%, whereas CO2 concentration changes associated with glacial–interglacial variations will likely be conserved (simulated damping 5%). If the precessional O2 / N2 signal will have disappeared completely in this future ice core, orbital tuning of the ice-core age scale will be limited.

Noble gas, CFC and other geochemical evidence for the age and origin of the Bath thermal waters, UK

The city of Bath is a World Heritage site and its thermal waters, the Roman Baths and new spa development rely on undisturbed flow of the springs (45 °C). The current investigations provide an improved understanding of the residence times and flow regime as basis for the source protection. Trace gas indicators including the noble gases (helium, neon, argon, krypton and xenon) and chlorofluorocarbons (CFCs), together with a more comprehensive examination of chemical and stable isotope tracers are used to characterise the sources of the thermal water and any modern components. It is shown conclusively by the use of 39Ar that the bulk of the thermal water has been in circulation within the Carboniferous Limestone for at least 1000 years. Other stable isotope and noble gas measurements confirm previous findings and strongly suggest recharge within the Holocene time period (i.e. the last 12 kyr). Measurements of dissolved 85Kr and chlorofluorocarbons constrain previous indications from tritium that a small proportion (<5%) of the thermal water originates from modern leakage into the spring pipe passing through Mesozoic valley fill underlying Bath. This introduces small amounts of O2 into the system, resulting in the Fe precipitation seen in the King’s Spring. Silica geothermometry indicates that the water is likely to have reached a maximum temperature of between 69–99 °C, indicating a most probable maximum circulation depth of ∼3 km, which is in line with recent geological models. The rise to the surface of the water is sufficiently indirect that a temperature loss of >20 °C is incurred. There is overwhelming evidence that the water has evolved within the Carboniferous Limestone formation, although the chemistry alone cannot pinpoint the geometry of the recharge area or circulation route. For a likely residence time of 1–12 kyr, volumetric calculations imply a large storage volume and circulation pathway if typical porosities of the limestone at depth are used, indicating that much of the Bath-Bristol basin must be involved in the water storage.

Geochemical synthesis for the Effingen Member in boreholes at Oftringen, Gösgen and Küttigen

The Effingen Member is a low-permeability rock unit of Oxfordian age (ca. 160 Ma) that occurs across northern Switzerland. It comprises sandy calcareous marls and (argillaceous) limestones. This report describes the hydrogeochemistry, mineralogy and supporting physical properties of the Effingen Member in three boreholes in the Jura-Südfuss area: Oftringen, Gösgen and Küttigen, where it is 220–240 m thick. The top of the Effingen Member is at 420, 66 and 32 m depths at the three sites. Core materials are available from Oftringen and Gösgen, whereas information from Küttigen is limited to cuttings, in-situ hydrogeological testing and geophysical logging. Hydrogeological boundaries of the Effingen Member vary between locations. Ground-water flows were identified during drilling at the top (Geissberg Member), but not at the base, of the Effingen Member at Oftringen, at the base (Hauptrogenstein Formation) of the Effingen Member at Gösgen, and in a limestone layer (Gerstenhübel unit) within the Effingen Member at Küttigen. The marls and limestones of the Effingen Member have carbonate contents of 46–91 wt.-% and clay-mineral contents of 5–37 wt.-%. Pyrite contents are up to 1.6 wt.-%, but no sulphate minerals were detected by routine analyses. Clay minerals are predominantly mixed-layer illite-smectite, illite and kaolinite, with sporadic traces of chlorite and smectite. Veins filled with calcite ± celestite occur through the Effingen Member at Oftringen but not at Gösgen or Küttigen. They formed at 50–70 ºC from externally derived fluids, probably of Miocene age. Water contents are 0.7–4.2 wt.-%, corresponding to a water-loss porosity range of 1.9–10.8 vol.-%. Specific surface areas, measured by the BET method, are 2–30 m2/g, correlating with clay-mineral contents. Water activity has been measured and yielded surprisingly low values down to 0.8. These cannot be explained by pore-water salinity alone and include other effects, such as changes in the fabric due to stress release or partial saturation. Observed variations in measurements are not fully understood. Cation exchange capacity (CEC) and exchangeable cation populations have been studied by the Ni-en method. CEC, derived from the consumption of the index cation Ni, is 9–99 meq/kgrock at a solid:liquid ratio of 1, correlating with the clay-mineral content. Cation concentrations in Ni-en extract solutions are in the order Na+≥Ca2+>Mg2+>K+>Sr2+. However, the analytical results from the Ni-en extractions have additional contributions from cations originating from pore water and from mineral dissolution reactions that occurred during extraction, and it was not possible to reliably quantify these contributions. Therefore, in-situ cation populations and selectivity coefficients could not be derived. A suite of methods have been used for characterising the chemical compositions of pore waters in the Effingen Member. Advective displacement was used on one sample from each Oftringen and Gösgen and is the only method that produces results that approach complete hydrochemical compositions. Aqueous extraction was used on core samples from these two boreholes and gives data only for Cl- and, in some cases, Br-. Out-diffusion was used on core samples from Oftringen and similarly gives data for Cl- and Br- only. For both aqueous extraction and out-diffusion, reaction of the experimental water with rock affected concentrations of cations, SO42 and alkalinity in experimental solutions. Another method, centrifugation, failed to extract pore water. Stable isotope ratios (δ18O and δ2H) of pore waters in core samples from Oftringen were analysed by the diffusive exchange method and helium contents of pore water in Oftringen samples were extracted for mass spectrometric analysis by quantitative outgassing of preserved core samples. Several lines of evidence indicate that drillcore samples might not have been fully saturated when opened and subsampled in the laboratory. These include comparisons of water-loss porosities with physical porosities, water-activity measurements, and high contents of dissolved gas as inferred from ground-water samples. There is no clear proof of partial saturation and it is unclear whether this might represent in-situ conditions or is due to exsolution of gas due to the pressure release since drilling. Partial saturation would have no impact on the recalculation of pore-water compositions from aqueous extraction experiments using water-loss porosity data. The largest uncertainty in the pore-water Cl- concentrations recalculated from aqueous extraction and out-diffusion experiments is the magnitude of the anion-accessible fraction of water-loss porosity. General experience of clay-mineral rich formations suggests that the anion-accessible porosity fraction is very often about 0.5 and generally in a range of 0.3 to 0.6 and tends to be inversely correlated with clay-mineral contents. Comparisons of the Cl- concentration in pore water obtained by advective displacement with that recalculated from aqueous extraction of an adjacent core sample suggests a fraction of 0.27 for an Oftringen sample, whereas the same procedure for a Gösgen sample suggests a value of 0.64. The former value for anion-accessible porosity fraction is presumed to be unrepresentative given the local mineralogical heterogeneity at that depth. Through-diffusion experiments with HTO and 36Cl- suggest that the anion-accessible porosity fraction in the Effingen Member at Oftringen and Gösgen is around 0.5. This value is proposed as a typical average for rocks of the Effingen Member, bearing in mind that it varies on a local scale in response to the heterogeneity of lithology and pore-space architecture. The substantial uncertainties associated with the approaches to estimating anion-accessible porosity propagate into the calculated values of in-situ pore-water Cl- concentrations. On the basis of aqueous extraction experiments, and using an anion-accessible porosity fraction of 0.5, Cl- concentrations in the Effingen Member at Oftringen reach a maximum of about 14 g/L in the centre. Cl- decreases upwards and downwards from that, forming a curved depth profile. Cl- contents in the Effingen Member at Gösgen increase with depth from about 3.5 g/L to about 14 g/L at the base of the cored profile (which corresponds to the centre of the formation). Out-diffusion experiments were carried out on four samples from Oftringen, distributed through the Effingen Member. Recalculated Cl- concentrations are similar to those from aqueous extraction for 3 out of the 4 samples, and somewhat lower for one sample. Concentrations of other components, i.e. Na+, K+, Ca2+, Mg2+, Sr2+, SO42- and HCO3- cannot be obtained from the aqueous extraction and out-diffusion experimental data because of mineral dissolution and cation exchange reactions during the experiments. Pore-water pH also is not constrained by those extraction experiments. The only experimental approach to obtain complete pore-water compositions for samples from Oftringen and Gösgen is advective displacement of pore water. The sample from Oftringen used for this experiment is from 445 m depth in the upper part of the Effingen Member and gave eluate with 16.5 g/L Cl- whereas aqueous extraction from a nearby sample indicated about 9 g/L Cl-. The sample from Gösgen used for advective displacement is from 123 m depth in the centre of the Effingen Member sequence and gave eluate with about 9 g/L Cl- whereas aqueous extraction gave 11.5 g/L Cl-. In both cases the pore waters have Na-(Ca)-Cl compositions and SO42- concentrations of about 1.1 g/L. The Gösgen sample has a Br/Cl ratio similar to that of sea water, whereas this ratio is lower for the Oftringen sample. Taking account of uncertainties in the applied experimental approaches, it is reasonable to place an upper limit of ca. 20 g/L on Cl- concentration for pore water in the Effingen Member in this area. There are major discrepancies between pore-water SO42- concentrations inferred from aqueous extraction or out-diffusion experiments and those obtained from advective displacement in both the Oftringen and Gösgen cases. A general conclusion is that all or at least part of the discrepancies are attributable to perturbation of the sulphur system and enhancement of SO42- by sulphate mineral dissolution and possibly minor pyrite oxidation during aqueous extraction and out-diffusion. Therefore, data for SO42- calculated from those pore-water sampling methods are considered not to be representative of in-situ conditions. A reference pore-water composition was defined for the Effingen Member in the Jura Südfuss area. It represents the probable upper limits of Cl- contents and corresponding anion and cation concentrations that are reasonably constrained by experimental data. Except for Cl- and possibly Na+ concentrations, this composition is poorly constrained especially with respect to SO42- and Ca2+ concentrations, and pH and alkalinity. Stable isotope compositions, δ18O and δ2H, of pore waters in the Effingen Member at Oftringen plot to the right of the meteoric water line, suggesting that 18O has been enriched by water-rock exchange, which indicates that the pore waters have a long residence time. A long residence time of pore water is supported by the level of dissolved 4He that has accumulated in pore water of the Effingen Member at Oftringen. This is comparable with, or slightly higher than, the amounts of 4He in the Opalinus Clay at Benken. Ground waters were sampled from flowing zones intersected by boreholes at the three locations. The general interpretation is that pore waters and ground-water solutes may have similar origins in Mesozoic and Cenozoic brackish-marine formations waters, but ground-water solutes have been diluted rather more than pore waters by ingress of Tertiary and Quaternary meteoric waters. The available hydrochemical data for pore waters from the Effingen Member at these three locations in the Jura-Südfuss area suggest that the geochemical system evolved slowly over geological periods of time, in which diffusion was an important mechanism of solute transport. The irregularity of Cl- and δ18O profiles and spatial variability of advective ground-water flows in the Malm-Dogger system suggests that palaeohydrogeological and hydrochemical responses to changing tectonic and surface environmental conditions were complex.

Origin and evolution of reactive and noble gases dissolved in matrix pore water

Reactive and noble gases dissolved in matrix pore water of low permeable crystalline bedrock were successfully extracted and characterized for the fist time based on drillcore samples from the Olkiluoto investigation site (SW Finland). Interaction between matrix pore water and fracture groundwater occurs predominately by diffusion. Changes in the chemical and isotopic composition of gases dissolved in fracture groundwater are transmitted and preserved in the pore water. Absolute concentrations, their ratios and the stable carbon isotope signature of hydrocarbon gases dissolved in pore water give valuable indications about the evolution of these gases in the nearby-flowing fracture groundwaters. Inert noble gases dissolved in matrix pore water and their isotopes combined with their in-situ production and accumulation rates deliver information about the residence time of pore water.

A 13,600-year diatom oxygen isotope record from the South Carpathians (Romania): Reflection of winter conditions and possible links with North Atlantic circulation changes

This study provides a continuous lateglacial and Holocene record of diatom silica oxygen isotope changes (delta O-18(DIAT)) in a subalpine lake sediment sequence obtained from the Retezat Mts (Taul dintre Brazi, 1740 m a.s.l.). This through-flow, shallow, high-altitude lake with a surface area of only 0.4 ha has short water residence time and is predominantly fed by snowmelt and rainwater. Its delta O-18(DIAT) record principally reflects the oxygen isotope composition of the winter and spring precipitation, as diatom blooms occur mainly in the spring and early summer. Hence, changes in delta O-18(DIAT) are interpreted as seasonal scale changes: in the amount of winter precipitation. Low oxygen isotope values (27-28.5 parts per thousand) occurred during the lateglacial until 12,300 cal BP, followed by a sharp increase thereafter. In the Holocene delta O-18(DIAT) values ranged from 29 to 31 parts per thousand until 3200 cal BP, followed by generally lower values during the late Holocene (27-30 parts per thousand). Short-term decreases in the isotopic values were found between 10,140-9570, 9000-8500, 7800-7300, 6300-5800, 5500-5000 and at 8015, 4400, 4000 cal BP. After 3200 cal BP a decreasing trend was visible with the lowest values between 3100-2500 and after 2100 cal BP The general trend in the record suggests that contribution of winter precipitation was generally lower between 11,680 and 3200 cal BP, followed by increased contribution during the last millennia. The late Holocene decrease in delta O-18(DIAT) shows good agreement with the speleothem delta O-18, lake level and testate amoebae records from the Carpathian Mountains that also display gradual delta O-18 decrease and lake level/mire water table level rise after 3200 cal BR Strong positive correlation with North Atlantic circulation and solar activity proxies, such as the Austrian and Hungarian speleothem records, furthermore suggested that short-term increases in the isotopic ratios in the early and mid Holocene are likely connectable to high solar activity phases and high frequency of positive North Atlantic Oscillation indexes that may have resulted in decreased winter precipitation in this region.

Investigation of young water inflow in karst aquifers using SF6–CFC–3H/He–85Kr–39Ar and stable isotope components

Karst aquifers are known for their wide distribution of water transfer velocities. From this observation, a multiple geochemical tracer approach seems to be particularly well suited to provide a significant assessment of groundwater flows, but the choice of adapted tracers is essential. In this study, several common tracers in karst aquifers such as physicochemical parameters, major ions, stable isotopes, and d13C to more specific tracers such as dating tracers – 14C, 3H, 3H–3He, CFC-12, SF6 and 85Kr, and 39Ar – were used, in a fractured karstic carbonated aquifer located in Burgundy (France). The information carried by each tracer and the best sampling strategy are compared on the basis of geochemical monitoring done during several recharge events and over longer time periods (months to years). This study’s results demonstrate that at the seasonal and recharge event time scale, the variability of concentrations is low for most tracers due to the broad spectrum of groundwater mixings. The tracers used traditionally for the study of karst aquifers, i.e., physicochemical parameters and major ions, efficiently describe hydrological processes such as the direct and differed recharge, but require being monitored at short time steps during recharge events to be maximized. From stable isotopes, tritium, and Cl� contents, the proportion of the fast direct recharge by the largest porosity was estimated using a binary mixing model. The use of tracers such as CFC-12, SF6, and 85Kr in karst aquifers provides additional information, notably an estimation of apparent age, but they require good preliminary knowledge of the karst system to interpret the results suitably. The CFC-12 and SF6 methods efficiently determine the apparent age of baseflow, but it is preferable to sample the groundwater during the recharge event. Furthermore, these methods are based on different assumptions such as regional enrichment in atmospheric SF6, excess air, and flow models among others. 85Kr and 39Ar concentrations can potentially provide a more direct estimation of groundwater residence time. Conversely, the 3H–3He method is inefficient in the karst aquifer for dating due to 3He degassing.

Continental degassing of 4He by surficial discharge of deep groundwater

Radiogenic He is produced by the decay of uranium and thorium in the Earth’s mantle and crust. From here, it is degassed to the atmosphere and eventually escapes to space. Assuming that all of the 4He produced is degassed, about 70% of the total He degassed from Earth comes from the continental crust. However, the outgoing flux of crustal He has not been directly measured at the Earth’s surface and the migration pathways are poorly understood. Here we present measurements of helium isotopes and the long-lived cosmogenic radio-isotope Kr in the deep, continental-scale Guarani aquifer in Brazil and show that crustal He reaches the atmosphere primarily by the surficial discharge of deep groundwater. We estimate that He in Guarani groundwater discharge accounts for about 20% of the assumed global flux from continental crust, and that other large aquifers may account for about 33%. Old groundwater ages suggest that He in the Guarani aquifer accumulates over half- to one-millionyear timescales. We conclude that He degassing from the continents is regulated by groundwater discharge, rather than episodic tectonic events, and suggest that the assumed steady state between crustal production and degassing of He, and its resulting atmospheric residence time, should be re-examined.