Analyses for 81 Kr and noble gases on groundwater from the deepest aquifer system of the Baltic Artesian Basin (BAB) were performed to determine groundwater ages and uncover the flow dynamics of the system on a timescale of several hundred thousand years. We find that the system is controlled by mixing of three distinct water masses: Interglacial or recent meteoric water (δ 18 O ≈ −10.4‰) with a poorly evolved chemical and noble gas signature, glacial meltwater (δ 18 O ≤ −18 ‰) with elevated noble gas concentrations, and an old, high-salinity brine component (δ 18 O ≥ −4.5‰, ≥ 90 g Cl − /L) with strongly depleted atmospheric noble gas concentrations. The 81 Kr measurements are interpreted within this mixing framework to estimate the age of the endmembers. Deconvoluted 81 Kr ages range from 300 ka to 1.3 Ma for interglacial or recent meteoric water and glacial meltwater. For the brine component, ages exceed the dating range of the ATTA-3 instrument of 1.3 Ma. The radiogenic noble gas components 4 He* and 40 Ar* are less conclusive butalso support an age of > 1 Ma for the brine. Based on the chemical and noble gas concentrations and the dating results, we conclude that the brine originates from evaporated seawater that has been modified by later water-rock interaction. As the obtained tracer ages cover several glacial cycles, we discuss the impact of the glacial cycles on flow patterns in the studied aquifer system. Virbulis et al., 2013), the latter of which estimated the hydraulic age of groundwater in the CAS to be on the order of several hundreds of ka to 1 Ma. In the light of such long residence times, it is crucial to consider the effect of repeated glacial cycles on the long-term evolution of groundwater composition and flow. Sampling the deeper parts of the CAS on a regional scale for chemistry, noble gases, and multiple dating tracers ( 81 Kr, 85 Kr, 39 Ar, 14 C, 4 He, 40 Ar) allows us to elucidate the evolution of the brine, mixing proportions of the different groundwater components, and the flow dynamics over the last 1 Ma.

Online oxygen (δ 18 O) and hydrogen (δ 2 H) isotope analysis of fluid inclusion water entrapped in minerals is widely applied in paleo-fluid studies. In the state of the art of fluid inclusion isotope research, however, there is a scarcity of reported inter-technique comparisons to account for possible analytical offsets.Along with improving analytical precisions and sample size limitations, interlaboratory comparisons can lead to a more robust application of fluid inclusion isotope records.Methods: Mineral samples-including speleothem, travertine, and vein materialwere analyzed on two newly setup systems for fluid inclusion isotope analysis to provide an inter-platform comparison. One setup uses a crusher unit connected online to a continuous-flow pyrolysis furnace and an isotope ratio mass spectrometry (IRMS) instrument. In the other setup, a crusher unit is lined up with a cavity ringdown spectroscopy (CRDS) system, and water samples are analyzed on a continuous standard water background to achieve precisions on water injections better than 0.1‰ for δ 18 O values and 0.4‰ for δ 2 H values for amounts down to 0.2 μL.Results: Fluid inclusion isotope analyses on the IRMS setup have an average 1σ reproducibility of 0.4‰ and 2.0‰ for δ 18 O and δ 2 H values, respectively. The CRDS setup has a better 1σ reproducibility (0.3‰ for δ 18 O values and 1.1‰ for δ 2 H values) and also a more rapid sample throughput (<30 min per sample). Fluid inclusion isotope analyses are reproducible at these uncertainties for water amounts down to 0.1 μL on both setups. Fluid inclusion isotope data show no systematic offsets between the setups. Conclusions:The close match in fluid inclusion isotope results between the two setups demonstrates the high accuracy of the presented continuous-flow techniques for fluid inclusion isotope analysis. Ideally, experiments such as the one presented in this study will lead to further interlaboratory comparison efforts and the selection of suitable reference materials for fluid inclusion isotopes studies.

No abstract

No abstract

Abstract. We present speleothem fluid inclusion δ18Of and δ2Hf values from Larga Cave, Puerto Rico, that covers the interval between 46.2 to 15.3 ka before present on millennial scale, including the Last Glacial Maximum (LGM) and several stadial and interstadial cycles. The dataset can be divided in two main clusters of stable isotope compositions of the fluid inclusion water with respect to the global meteoric water line which coincide with strong variations in the water content of the stalagmite. In particular, this clustering is found to be climate related, where the first cluster comprises samples from cold and dry periods, such as Heinrich and Greenland stadials, as well as parts of the LGM, which exhibit very high δ18Of and δ2Hf values. We interpret this enrichment as caused by evaporation inside the cave due to enhanced cave ventilation during these colder and drier times. In contrast, in most samples corresponding to warmer and wetter Greenland interstadials, but also for some from Heinrich Stadial 2 and 3, the δ18Of and δ2Hf values plot on the meteoric water line and modification of fluid inclusion water due to “in-cave” evaporation is found negligible. Consequently, variations of last glacial hydro-climate and temperature in the western tropical Atlantic can be constrained. In general, δ18Of values from fluid inclusions are up to 3 ‰ higher than those of modern drip water, which is interpreted as a weaker atmospheric convective activity during the last glacial period. In addition, reconstructed temperatures suggest an average cooling of c. 3 °C during the LGM compared to modern cave temperature. During Heinrich Stadials 2 and 3, reconstructed cave temperatures yield an additional cooling of 2.9 ± 2.6 °C and 4.4 ± 0.6 °C, respectively. Higher δ18Of values of these samples further suggest that the drip water was dominated by orographic rainfall and/or cold fronts, along with weak or even absent convective activity. In contrast, during interstadial phases, reconstructed temperatures reached nearly modern values, and convective activity was comparable or only slightly weaker than today.

Abstract. We present speleothem fluid inclusion δ18Of and δ2Hf values from Larga Cave, Puerto Rico, that cover the interval between 46.2 and 15.3 ka on the millennial scale, including the Last Glacial Maximum (LGM) and several stadial and interstadial cycles. The data set can be divided in two main clusters of stable isotope compositions of the fluid inclusion water with respect to the global meteoric water line (GMWL), which coincide with strong variations in the water content of the stalagmite. In particular, this clustering is found to be climate related, where one cluster comprises samples from cold and dry periods, such as the Heinrich and Greenland stadials (HSs and GSs), as well as parts of the LGM, which exhibit very high δ18Of and δ2Hf values. We interpret this enrichment as being caused by evaporation inside the cave due to enhanced cave ventilation during these colder and drier times. In contrast, in most samples corresponding to warmer and wetter Greenland interstadials (GIs), but also for some from HS 2 and 3, the δ18Of and δ2Hf values plot on the meteoric water line and modification of fluid inclusion water due to “in-cave” evaporation are found to be negligible. Consequently, variations of recent glacial hydro-climate and temperatures in the western tropical Atlantic can be constrained. In general, δ18Of values from fluid inclusions are up to 3 ‰ higher than those of modern drip water, which is interpreted as a weaker atmospheric convective activity during the last glacial period. In addition, reconstructed temperatures suggest an average cooling of 2–3 ∘C during the LGM compared to modern cave temperatures. Reconstructed cave temperatures yield an average cooling of −1.4 ± 2.8 ∘C for HS 2 and −3.6 ± 2.2 ∘C for HS 3. Higher δ18Of values of these samples further suggest that the drip water was dominated by orographic rainfall and/or cold fronts, along with weak or even absent convective activity. In contrast, during interstadial phases, reconstructed temperatures reached nearly modern values, and convective activity was comparable to or only slightly weaker than today.

The Viimsi peninsula is located north-east of Tallinn, capital of Estonia. The Cambrian-Vendian (Cm-V) aquifer system is a sole source of drinking water in the area. Historically, the groundwater exploitation has led to freshening of groundwater in the peninsula, but in recent years an increase in chloride concentrations and enrichment in δ18O values has been detected, but in recent years hydrochemical parameters indicate an increasing influence of a saline water source. The exact origin of this saline water has remained unclear. The aim of the current study is to elucidate whether the increase in Cl− concentrations is related to seawater intrusion or to the infiltration of saline water from the underlying crystalline basement. To identify the source of salinity, chemical composition of the groundwater and the isotope tracers (e.g., δ18O and radium isotopes) were studied in the Viimsi peninsula in the period from 1987 to 2018. Our results show that chemical composition of Cm-V groundwater in the peninsula is clearly controlled by three-component mixing between glacial palaeogroundwater, saline water from the underling crystalline basement and modern meteoric water. The concentrations of Ra are also significantly affected by the mixing, but the spatial variation of radium isotopes (226Ra and 228Ra) suggests the widespread occurrence of the U in the surrounding sedimentary sequence. Our hypothesis is that, in addition to U originating from the crystalline basement, some U could be associated with secondary U deposits in sedimentary rocks. The formation of these secondary U deposits could be related to glacial meltwater intrusion in the Pleistocene. Although the results suggest that the infiltration of saline groundwater from the underlying crystalline basement as the main source of salinity in the study area, the risk of seawater intrusion in the future cannot be ruled out. It needs to be highlighted that the present groundwater monitoring networks may not be precise enough to detect the potential seawater intrusion and subsequent changes in water quality of the Cm-V aquifer system in the Viimsi peninsula.

No abstract