Radiocarbon integrity of dissolved inorganic carbon (DIC) samples stored in plastic and glass bottles: implications for reliable groundwater age dating.

Various approaches based on the natural variations of carbon isotopes (14C and 13C) in dissolved inorganic carbon (DIC) are routinely used to study groundwater dynamics and to estimate recharge rates by deriving groundwater ages. However, differences in 14C activities in groundwater samples collected repeatedly from the same wells and discordantly young 14C groundwater ages compared to noble gases led some authors to question the validity of radiocarbon dating. Poor sampling protocols and storage effects (14C contamination) for radiocarbon analysis are a critical factor in explaining age determination discrepancies. We evaluated the impact of storage protocols on carbon isotope exchange with atmospheric carbon dioxide by comparing glass versus standard plastic field sampling bottles for various storage times before radiocarbon and 13C analyses. The 14C bias after 12 months in pre-evacuated glass vials was minimal and within analytical precision. However, storage of DIC samples in plastic sampling bottles led to marked changes in 14C and 13C contents (up to ∼15 pmC and ∼ 5 ‰, respectively, after 12 months), meaning contamination led to younger groundwater age estimations than it should have been. Protocols for sampling and storing DIC samples for radiocarbon using pre-evacuated glass bottles help avoid atmospheric 14CO2 contamination and microbial activity.

Global and local meteoric water lines for δ17O/δ18O and the spatiotemporal distribution of Δ'17O in Earth's precipitation.

Recently, δ17O and its excess (Δ'17O) have become increasingly significant "triple-oxygen-isotope" indicators of distinctive hydrological processes in hydrology and climatology. This situation mirrors the research regarding δ18O and δ2H in the 1960s towards a solid theoretical base and a surge in application examples and field studies worldwide. Currently, systematic global measurements for δ17O in precipitation are still lacking. As a result, attempts have been made to define a Global δ17O/δ18O Meteoric Water Line (GMWL), often by using regional or local datasets of varying systematicity. Different definitions of the global reference slope (λref) for determining Δ'17O values have been proposed, by ongoing debate around a proposed consensus value of 0.528. This study used worldwide samples archived in the IAEA Global Network of Isotopes in Precipitation (GNIP) to (a) derive a δ17O/δ18O GMWL based on four-year monthly records from 66 GNIP stations, (b) formulate local δ17O/δ18O meteoric water lines (LMWL) for these stations' areas, and (c) evaluate regional and seasonal variations of Δ'17O in precipitation. The GMWL for δ17O/δ18O was determined to be δ'17O = 0.5280 ± 0.0002 δ'18O + 0.0153 ± 0.0013, in keeping with the consensus value. Furthermore, our results suggested that using a line-conditioned 17O-excess is a viable alternative over the global λref in the context of regional hydrology and paleoclimatology interpretations; however, without challenging the global λref as such.

Balancing precision and throughput of δ 17O and Δ'17O analysis of natural waters by Cavity Ringdown Spectroscopy.

δ 17O and Δ'17O are emerging tracers increasingly used in isotope hydrology, climatology, and biochemistry. Differentiating small relative abundance changes in the rare 17O isotope from the strong covariance with 18O imposes ultra-high precision requirements for this isotope analysis. Measurements of δ 17O by Cavity Ringdown Spectroscopy (CRDS) are attractive due to the ease of sample preparation, automated throughput, and avoidance of chemical conversions needed for isotope-ratio mass spectrometry. However, the CRDS approach requires trade-offs in measurement precision and uncertainty. In this protocol document, we present the following:•New analytical procedures and a software tool for conducting δ 17O and Δ'17O measurements by CRDS.•Outline a robust uncertainty framework for Δ'17O determinations.•Description of a CRDS performance framework for optimizing throughput, instrumental stability, and Δ'17O measurement precision and accuracy.

Nitrate isotopes reveal N-cycled waters in a spring-fed agricultural catchment.

Nitrate stable isotopes provide information about nitrate contamination and cycling by microbial processes. The Fischa-Dagnitz (Austria) spring and river system in the agricultural catchment of the Vienna basin shows minor annual variance in nitrate concentrations. We measured nitrate isotopes (δ15N, δ18O) in the source spring and river up to the confluence with the Danube River (2019-2020) with chemical and water isotopes to assess mixing and nitrate transformation processes. The Fischa-Dagnitz spring showed almost stable nitrate concentration (3.3 ± 1.0 mg/l as NO3--N) year-round but surprisingly variable δ15N, δ18O-NO3- values ranging from +5.5 to +11.1‰ and from +0.5 to +8.1‰, respectively. The higher nitrate isotope values in summer were attributed to release of older denitrified water from the spring whose isotope signal was dampened downstream by mixing. A mixing model suggested denitrified groundwater contributed > 50 % of spring discharge at baseflow conditions. The isotopic composition of NO3- in the gaining streams was partly controlled by nitrification during autumn and winter months and assimilation during the growing season resulting in low and high δ15N-NO3- values, respectively. NO3- isotope variation helped disentangle denitrified groundwater inputs and biochemical cycling processes despite minor variation of NO3- concentration.

High spatial resolution prediction of tritium (3H) in contemporary global precipitation.

Tritium (3H) in Earth's precipitation is vigilantly monitored since historical nuclear bomb tests because of radiological protection considerations and its invaluable role as a tracer of the global water cycle in quantifying surface, groundwater, and oceanic fluxes. For hydrological applications, accurate knowledge of 3H in contemporary local precipitation is prerequisite for dating of critical zone water and calibrating hydrogeologic transport and groundwater protection models. However, local tritium input in precipitation is hard to constrain due to few 3H observation sites. We present new high-spatial resolution global prediction maps of multi-year mean 3H in contemporary "post-bomb" (2008-2018) precipitation by using a robust regression model based on environmental and geospatial covariates. The model accurately predicted the mean annual 3H in precipitation, which allowed us to produce global 3H input maps for applications in hydrological and climate modelling. The spatial patterns revealed natural 3H in contemporary precipitation sufficient for practical hydrological applications (1-25 TU) but variable across continental regions and higher latitudes due to cumulative influences of cyclical neutron fluxes, stratospheric inputs, and distance from tropospheric moisture sources. The new 3H maps provide a foundational resource for improved calibration of groundwater flow models and critical zone vulnerability assessment and provides an operational baseline for quantifying the potential impact of future anthropogenic nuclear activities and hydroclimatic changes.

Comparative evaluation of 2H- versus 3H-based enrichment factor determination on the uncertainty and accuracy of low-level tritium analyses of environmental waters.

Analysis of low-level tritium (3H) in environmental waters requires pre-concentration using electrolytic enrichment prior to decay counting. Accurate and precise electrolytic enrichment factors (EF) are required to determine the sample's environmental 3H concentration. Two methods are used to determine EFs: i) the Spike Proxy Method (SPM) and ii) the Deuterium Method (DM) with each having several modalities. We conducted a comparative assessment of four EF strategies using 250 mL and 500 mL electrolytic enrichment of three low-level 3H proficiency water standards (0.5-7 TU) to see which strategy gave the most accurate 3H results based on z- and Zeta-scores. Our comparative evaluation revealed the DM offers consistently superior 3H results, with more precise EF determinations compared to the three SPM strategies. The DM gave the best z-scores with an EF relative combined uncertainty of about 0.5‰ and a negligible contribution to the overall uncertainty budget due to the EF determination. Moreover, the DM can improve productivity by eliminating the spike and gravimetric procedures from routine analyses and can give rapid cell enrichment performance feedback prior to decay counting. We recommend low-level tritium laboratories consider adopting the DM into their 3H sample enrichment and analysis operations.

Using isotope data to characterize and date groundwater in the southern sector of the Guaraní Aquifer System.

The Guaraní Aquifer System (SAG) is the largest transboundary aquifer in Latin America, extending beneath parts of Brazil, Paraguay, Argentina, and Uruguay. This paper presents the results of recent hydrogeological studies in the southern portion of the SAG. Locally, the abundance of surface water bodies precluded the use of conventional hydrological tools to characterize groundwater flows. Geological, hydrochemical and environmental isotope investigations were integrated to postulate a revised hydrogeological conceptual model. The revised geological model has provided a better definition of the geometry of the aquifer units and outlined the relevance of regional faults in controlling flow patterns. The new potentiometric map is consistent with groundwater flow from the SAG outcrops to the centre of the Corrientes Province, where upwards flows were identified. Hydrochemical and isotope data confirmed the widespread occurrence of mixing. Noble gas isotopes dissolved in groundwater (4He and 81Kr/Kr) provided residence times ranging from recent recharge up to 770 ± 130 ka. Groundwater age modelling confirmed the role of the geological structures in controlling groundwater flow. The southern sector of the SAG is a multilayer aquifer system with vertical flows and deep regional discharge near the Esteros del Iberá wetland area and along the Paraná and Uruguay rivers.

Proficiency testing of 78 international laboratories measuring tritium in environmental waters by decay counting and mass spectrometry for age dating and water resources assessment.

RATIONALE: Tritium (3 H) is an important hydrological tracer that has been commonly used for over 60 years to evaluate water residence times and water dynamics in shallow/recent groundwaters, streams, lakes and the ocean. We tested the analytical performance of 78 international laboratories engaged in low-level 3 H assays for water age dating and monitoring of environmental waters. METHODS: Seven test waters were distributed by the IAEA to 78 international tritium laboratories. Set 1 included a tritium-free groundwater plus three ultra-low 3 H samples (0.5-7 TU) for meeting groundwater dating specifications. Set 2 contained three higher 3 H-content samples (40-500 TU) suitable for testing of environmental monitoring laboratories. RESULTS: Seventy of the laboratories used liquid scintillation counting with or without electrolytic enrichment, seven utilized 3 He accumulation and mass spectrometry, and one used gas-proportional counting. Only ~50% of laboratories demonstrated the ability to generate accurate 3 H data that was precise enough for water age dating purposes. CONCLUSIONS: The proficiency test helped identify recurrent weaknesses and potential solutions. Strategies for performance improvements of 3 H laboratories include: (a) improved quantification of 3 H detection limits and analytical uncertainty, (b) stricter quality control practices in routine operations along with care and recalibration of 3 H standards traceable to primary NIST standards, (c) annual assessment of tritium enrichment factors and instrumental performance, and (d) for water age dating purposes the use of electrolytic enrichment systems having the highest possible 3 H enrichment factors (e.g. >50×).

The first IAEA inter-laboratory comparison exercise in Latin America and the Caribbean for stable isotope analyses of water samples.

The use of stable isotopes (δ 2H and δ 18O) is widespread in water resources studies. In the Latin America and the Caribbean (LAC) region, the application of isotope techniques has increased in the past decade, but there remains room to gain self-reliance in environmental isotope studies, necessitating easy and fast access to good-quality isotope data. To that end, in 2018 the IAEA carried out the first regional interlaboratory comparison exercise, testing the analytical performance of 25 laboratories using isotope-ratio mass spectrometry and laser absorption spectroscopy. The three test samples covered a commonly observed range of 0 to -16 ‰ δ 18O and 0 to -115 ‰ δ 2H. z- and ζ-scores were used to benchmark laboratories' performance against a strict criterion. We found that 81% of the laboratories had satisfactory performance ( | z | ¯ ≤ 2) for δ 2H but only 54% achieved similar scores for δ 18O. Only a minor fraction of results (12% for δ 2H and 15% for δ 18O) were unsatisfactory. The larger number of questionable results for δ 18O confirmed the challenges in laser absorption spectroscopy for this isotope. Besides instrumental performance, the sample throughput, laboratory reference materials, and data post-processing were contributing factors to inaccurate or imprecise performance.

A simple polymer electrolyte membrane system for enrichment of low-level tritium (3H) in environmental water samples.

Tritium (3H) is an essential tracer of the Earth's water cycle; yet widespread adoption of tritium in hydrologic studies remains a challenge because of analytical barriers to quantification and detection of 3H by electrolytic pre-concentration. Here, we propose a simple tritium electrolytic enrichment system based on the use of solid polymer electrolyte membranes (PEMs) that can be used to enrich 3H in 250-3000 mL environmental water samples to a 10-mL final volume. The IAEA PEM-3H system reported here can produce high enrichment factors (>70-fold) and, importantly, removes some of the deterrents to conventional 3H enrichments methods, including the use of toxic electrolysis and neutralization chemicals, spike standards, a complex electrolysis apparatus that requires extensive cooling and temperature controls, and improves precision by eliminating the need for tracking recovery gravimetrics. Preliminary results with varying operating conditions show 3H enrichments to 70-fold and higher are feasible, spanning a wide range of tritium activities from 5 to 150 TU with a precision of ∼4.5 %. Further work is needed to quantify inter-sample memory and to establish lower 3H detection limits. The IAEA PEM-3H system is open source, with 3-D CAD and design files made freely available for adoption and improvement by others.

Lower groundwater ¹4C age by atmospheric CO2 uptake during sampling and analysis.

Uptake of atmospheric CO2 during sample collection and analysis, and consequent lowering of estimated ages, has rarely been considered in radiocarbon dating of groundwater. Using field and laboratory experiments, we show that atmospheric CO2 can be easily and rapidly absorbed in hyperalkaline solutions used for the extraction of dissolved inorganic carbon, resulting in elevated ¹4C measurements. Kinetic isotope fractionation during atmospheric CO2 uptake may also result in decrease of δ¹³C, leading to insufficient corrections for addition of dead carbon by geochemical processes. Consequently, measured ¹4C values of groundwater should not be used for age estimation without corresponding δ¹³C values, and historical ¹4C data in the range of 1 to 10% modern Carbon should be re-evaluated to ensure that samples with atmospheric contamination are recognized appropriately. We recommend that samples for ¹4C analysis should be collected and processed in the field and the laboratory without exposure to the atmosphere. These precautions are considered necessary even if ¹4C measurements are made with an accelerator mass spectrometer.