ABSTRACT
Many efforts have been made to illuminate the nature of past hydroclimates in semi-arid and arid regions, where current and future shifts in water availability have enormous consequences on human subsistence. Deep desert aquifers, where groundwater is stored for prolonged periods, might serve as a direct record of major paleo-recharge events. To date, groundwater-based paleoclimate reconstructions have mainly focused on a relatively narrow timescale (up to â¼40 kyr), limited by the relatively short half-life of the widely used radiocarbon (5.73 kyr). Here we demonstrate the usage of deep regional aquifers in the arid southeastern Mediterranean as a hydroclimate archive for earlier Mid-to-Late Pleistocene epochs. State-of-the-art dating tools, primarily the 81Kr radioisotope (t1/2â¯=â¯229 kyr), were combined with other atmosphere-derived tracers to illuminate the impact of four distinguishable wetter episodes over the past 400 kyr, with differences in climatic conditions and paleo-recharge locations. Variations in stable water isotope composition suggest moisture transport from more proximal (Mediterranean) and distal (Atlantic) sources to different parts of the region at distinct times. Large variability in the computed noble gas-based recharge temperature (NGT), ranging ~15-30⯰C, cannot be explained by climate variations solely, and points to different recharge pathways, including geothermal heating in the deep unsaturated zone and recharge from high-elevation (colder) regions. The obtained groundwater record complements and enhances the interpretation of other terrestrial archives in the arid region, including a contribution of valuable information regarding the moisture source origin as reflected in the deuterium-excess values, which is unattainable from the common practice analysis of calcitic cave deposits. We conclude that similar applications in other deep (hundred-m-order) regional groundwater systems (e.g., the Sahara desert aquifers) can significantly advance our understanding of long-term (up to 1 Myr) paleo-hydroclimate in arid regions, including places where no terrestrial remnants, such as cave, lake, and spring sediments, are available.
ABSTRACT
Rare earth elements (REEs) have been found to have numerous uses to trace geological and cosmochemical processes through analyses of elemental patterns, radioactive decay, nucleosynthetic anomalies, and cosmogenic effects. Stable isotopic fractionation is one aspect of REE geochemistry that has been seldom studied, with most publications focusing on the development of analytical methodologies for individual REEs, and most applications concerning terrestrial igneous rocks. In this study, we present a method to systematically analyze stable isotopic fractionations of 8 REEs, including Ce, Nd, Sm, Eu, Gd, Dy, Er, and Yb, using sample-standard bracketing (SSB) and double-spike (DS) approaches. All REEs are separated and purified using a fluoropolymer pneumatic liquid chromatography (FPLC) system. We introduce procedures for identifying and correcting some isobaric interferences in double-spike data reduction. Several geostandards, including igneous rocks and sediments, are analyzed using SSB and DS methods. The results indicate that REE isotopic fractionation in igneous processes is limited, except for Eu. Other REEs can still be isotopically fractionated by low-temperature processes and kinetic effects at a high temperature.
ABSTRACT
The near-Earth carbonaceous asteroid (162173) Ryugu is expected to contain volatile chemical species that could provide information on the origin of Earth's volatiles. Samples of Ryugu were retrieved by the Hayabusa2 spacecraft. We measured noble gas and nitrogen isotopes in Ryugu samples and found that they are dominated by presolar and primordial components, incorporated during Solar System formation. Noble gas concentrations are higher than those in Ivuna-type carbonaceous (CI) chondrite meteorites. Several host phases of isotopically distinct nitrogen have different abundances among the samples. Our measurements support a close relationship between Ryugu and CI chondrites. Noble gases produced by galactic cosmic rays, indicating a ~5 million year exposure, and from implanted solar wind record the recent irradiation history of Ryugu after it migrated to its current orbit.
ABSTRACT
The Hayabusa2 spacecraft returned to Earth from the asteroid 162173 Ryugu on 6 December 2020. One day after the recovery, the gas species retained in the sample container were extracted and measured on-site and stored in gas collection bottles. The container gas consists of helium and neon with an extraterrestrial 3He/4He and 20Ne/22Ne ratios, along with some contaminant terrestrial atmospheric gases. A mixture of solar and Earth's atmospheric gas is the best explanation for the container gas composition. Fragmentation of Ryugu grains within the sample container is discussed on the basis of the estimated amount of indigenous He and the size distribution of the recovered Ryugu grains. This is the first successful return of gas species from a near-Earth asteroid.
ABSTRACT
Measurements of the long-lived 81Kr and 36Cl radioisotopes in groundwater from the Negev Desert (Israel) were used to assess the 36Cl/Cl input ratios and Cl- contents for paleorecharge into the Nubian Sandstone Aquifer (NSA). The reconstructed Cl- content of the recharge flux was on the order of 300-400 mg/L. An initial 36Cl/Cl ratio of 50 × 10-15 was assessed for the groundwater replenishment in the Negev Desert since the late Pleistocene, in agreement with the 36Cl/Cl ratios in recent local rainwater. This is despite possible changes in the climatic conditions and the 36Cl production rates in the atmosphere over this timeframe. This similarity in values is explained by the major role played by the erosion and weathering of near-surface materials in the desert environment that dominate the hydrochemistry of rains, floods, and the consequent groundwater recharge. Spatial variation in the reconstructed initial 36Cl/Cl ratio is accounted for by the differences in the mineral aerosol sources for specific recharge areas of the NSA. Accordingly, regional variations in the 36Cl/Cl input in groundwater reservoirs surrounding the Mediterranean Sea indicate various processes that govern the 36Cl/Cl system. Finally, the results of this study highlight the great advantage of integrating 81Kr age information in evaluating the initial 36Cl/Cl and Cl- input, which is essential for the calibration of 36Cl radioisotope as an available long-term dating tool for a given basin.
ABSTRACT
In arid regions, groundwater is a vital resource that can also provide a long-term record of the regional water cycle. However, the use of groundwater as a paleoclimate proxy has been limited by the complex hydrology and the lack of appropriate chronometers to determine the recharge time without complication. Applying 81Kr, a long-lived radioisotope tracer, we investigate the paleohydroclimate and subsurface water storage properties of the Nubian Sandstone Aquifer in the Negev Desert, Israel. Based on the spatial distributions of stable isotopes and the abundance of 81Kr, we resolve subsurface mixing and identify two distinct moisture sources of the recharge: one recent (<38 ky ago) from the Mediterranean and the other 361 ± 30 ky ago from the tropical Atlantic, both of which occurred under conditions of low orbital eccentricity comparable to that of the present. The recent recharge provided by the moisture from Mediterranean cyclones can be attributed to the southward shift of the storm track during the Last Glacial Maximum, and the earlier recharge can be attributed to moisture from the Atlantic delivered as tropical plumes under a climate colder than the present. Furthermore, the residence time of the latter reveals that tectonically active terrain can store groundwater for an unexpectedly long period, likely due to strongly attenuated groundwater flow across the fault zones. With this tracer, groundwater can now serve as a direct record of paleoprecipitation over land and of subsurface water storage from the mid-Pleistocene and onward.
ABSTRACT
The Waste Isolation Pilot Plant (WIPP) in New Mexico is the first geologic repository for disposal of transuranic nuclear waste from defense-related programs of the US Department of Energy. It is constructed within halite beds of the Permian-age Salado Formation. The Culebra Dolomite, confined within Rustler Formation evaporites overlying the Salado Formation, is a potential pathway for radionuclide transport from the repository to the accessible environment in the human-disturbed repository scenario. Although extensive subsurface characterization and numerical flow modeling of groundwater has been done in the vicinity of the WIPP, few studies have used natural isotopic tracers to validate the flow models and to better understand solute transport at this site. The advent of Atom-Trap Trace Analysis (ATTA) has enabled routine measurement of cosmogenic (81)Kr (half-life 229,000 yr), a near-ideal tracer for long-term groundwater transport. We measured (81)Kr in saline groundwater sampled from two Culebra Dolomite monitoring wells near the WIPP site, and compared (81)Kr model ages with reverse particle-tracking results of well-calibrated flow models. The (81)Kr model ages are ~130,000 and ~330,000 yr for high-transmissivity and low-transmissivity portions of the formation, respectively. Compared with flow model results which indicate a relatively young mean hydraulic age (~32,000 yr), the (81)Kr model ages imply substantial physical attenuation of conservative solutes in the Culebra Dolomite and provide limits on the effective diffusivity of contaminants into the confining aquitards.
Subject(s)
Groundwater/analysis , Krypton Radioisotopes/analysis , Krypton/analysis , Water Pollutants, Chemical/analysis , Models, Theoretical , New Mexico , Water MovementsABSTRACT
Radiokrypton isotopes ((81)Kr and (85)Kr) are ideal tracers and chronometers of various environmental processes. Atom trap trace analysis (ATTA) is capable of determining the ultralow isotopic abundances of radiokryptons (<10(-12)) provided that 50 microL of pure Kr is available. The analysis by using ATTA of (81)Kr in naturally occurring gases of interest, e.g., dissolved gases in hydrological reservoirs, requires separation of parts-per-million (ppm) level Kr from chemically airlike bulk gas. A newly developed Kr purification system is based on conventional cryogenic distillation and gas chromatography to which continuous monitoring of gas effluent composition using a quadrupole mass spectrometer brings significant advantages. Simple cryogenic distillation is controlled based on the evolution of N2/Ar ratio that is relatively constant in naturally occurring, inorganic gas. Gas chromatographic separation of parts-per-million by volume (ppmv) level Kr from up to a few liters of bulk gas can be achieved by concentrating the Kr under the chromatographic tails of major components. The system described here is capable of extracting Kr of >98% purity from 5-125 L STP (standard temperature and pressure) of bulk gas with >90% yield within several hours. This system is generally useful for separation of microliter amounts of unreactive trace volatile compounds from large-volume gas samples.