Using stable oxygen isotope dual-inlet isotope-ratio mass spectrometry to elucidate uranium transport and mixed Th/U calcite formation ages at the seminal Devils Hole, Nevada, natural laboratory.

Rationale: Vein calcite in Devils Hole has been precipitating continuously in oxygen-isotope equilibrium at a constant temperature for over 500 000 years, providing an unmatched δO paleoclimate time series. A substantial issue is that coeval calcite (based on matching δO values) has uranium-series ages differing by 12 000 years.

Methods: An unparalleled high-accuracy δO chronology series from continuously submerged calcite was used to correct the published uranium-series ages of non-continuously formed calcite in two cores, cyclically exposed by water-table decline during glacial-interglacial transitions.

Equilibrated Gas and Carbonate Standard-Derived Dual (Δ47 and Δ48) Clumped Isotope Values.

Carbonate clumped isotope geochemistry has primarily focused on mass spectrometric determination of 47 CO for geothermometry, but theoretical calculations and recent experiments indicate paired analysis of the 47 (COO) and 48 (COO) isotopologues (referred to as and ) can be used to study non-equilibrium isotope fractionations and refine temperature estimates. We utilize 5,448 and 3,400 replicate measurements of carbonate samples and standards, and 183 and 195 replicate measurements of gas standards from 2015 to 2021 from a multi-year and multi-instrument data set to constrain and values for 27 samples and standards, including Devils Hole cave calcite, and study equilibrium -, -temperature, and -temperature relationships. We compare results to previously published findings and calculate equilibrium regressions based on data from multiple laboratories.

Insights on Geochemical, Isotopic, and Volumetric Compositions of Produced Water from Hydraulically Fractured Williston Basin Oil Wells.

Tracing produced water origins from wells hydraulically fractured with freshwater-based fluids is sometimes predicated on assumptions that (1) each geological formation contains compositionally unique brine and (2) produced water from recently hydraulically fractured wells resembles fresher meteoric water more so than produced water from older wells. These assumptions are not valid in Williston Basin oil wells sampled in this study. Although distinct average Ra/Ra ratios were found in water produced from the Bakken and Three Forks Formations, average δH, δO, specific gravity, and conductivity were similar but exhibited significant variability across five oil fields within each formation.

USGS44, a new high-purity calcium carbonate reference material for δ C measurements.

Rationale: The stable carbon isotopic (δ C) reference material (RM) LSVEC Li CO has been found to be unsuitable for δ C standardization work because its δ C value increases with exposure to atmospheric CO . A new CaCO RM, USGS44, has been prepared to alleviate this situation.

Methods: USGS44 was prepared from 8 kg of Merck high-purity CaCO .

Food Matrix Reference Materials for Hydrogen, Carbon, Nitrogen, Oxygen, and Sulfur Stable Isotope-Ratio Measurements: Collagens, Flours, Honeys, and Vegetable Oils.

An international project developed, quality-tested, and measured isotope-delta values of 10 new food matrix reference materials (RMs) for hydrogen, carbon, nitrogen, oxygen, and sulfur stable isotope-ratio measurements to support food authenticity testing and food provenance verification. These new RMs, USGS82 to USGS91, will enable users to normalize measurements of samples to isotope-delta scales. The RMs include (i) two honeys from Canada and tropical Vietnam, (ii) two flours from C3 (rice) and C4 (millet) plants, (iii) four vegetable oils from C3 (olive, peanut) and C4 (corn) plants, and (iv) two collagen powders from marine fish and terrestrial mammal origins.

Dual clumped isotope thermometry resolves kinetic biases in carbonate formation temperatures.

Surface temperature is a fundamental parameter of Earth's climate. Its evolution through time is commonly reconstructed using the oxygen isotope and the clumped isotope compositions of carbonate archives. However, reaction kinetics involved in the precipitation of carbonates can introduce inaccuracies in the derived temperatures.

The Table of Standard Atomic Weights-An exercise in consensus.

The present Table of Standard Atomic Weights (TSAW) of the elements is perhaps one of the most familiar data sets in science. Unlike most parameters in physical science whose values and uncertainties are evaluated using the "Guide to the Expression of Uncertainty in Measurement" (GUM), the majority of standard atomic-weight values and their uncertainties are consensus values, not GUM-evaluated values. The Commission on Isotopic Abundances and Atomic Weights of the International Union of Pure and Applied Chemistry (IUPAC) regularly evaluates the literature for new isotopic-abundance measurements that can lead to revised standard atomic-weight values, A °(E) for element E.

Investigation of recent decadal-scale cyclical fluctuations in salinity in the lower Colorado River.

Beginning in the late 1970s, 10- to 15-year cyclical oscillations in salinity were observed at lower Colorado River monitoring sites, moving upstream from the international border with Mexico, above Imperial Dam, below Hoover Dam, and at Lees Ferry. The cause of these cyclical trends in salinity was unknown. These salinity cycles complicate the U.

Most Earth-surface calcites precipitate out of isotopic equilibrium.

Oxygen-isotope thermometry played a critical role in the rise of modern geochemistry and remains extensively used in (bio-)geoscience. Its theoretical foundations rest on the assumption that O/O partitioning among water and carbonate minerals primarily reflects thermodynamic equilibrium. However, after decades of research, there is no consensus on the true equilibrium O/O fractionation between calcite and water (α).

Preliminary assessment of stable nitrogen and oxygen isotopic composition of USGS51 and USGS52 nitrous oxide reference gases and perspectives on calibration needs.

Rationale: Despite a long history and growing interest in isotopic analyses of N O, there is a lack of isotopically characterized N O isotopic reference materials (standards) to enable normalization and reporting of isotope-delta values. Here we report the isotopic characterization of two pure N O gas reference materials, USGS51 and USGS52, which are now available for laboratory calibration (https://isotopes.usgs.

Seeking excellence: An evaluation of 235 international laboratories conducting water isotope analyses by isotope-ratio and laser-absorption spectrometry.

Rationale: Water stable isotope ratios (δ H and δ O values) are widely used tracers in environmental studies; hence, accurate and precise assays are required for providing sound scientific information. We tested the analytical performance of 235 international laboratories conducting water isotope analyses using dual-inlet and continuous-flow isotope ratio mass spectrometers and laser spectrometers through a water isotope inter-comparison test.

Methods: Eight test water samples were distributed by the IAEA to international stable isotope laboratories.

Optimization of on-line hydrogen stable isotope ratio measurements of halogen- and sulfur-bearing organic compounds using elemental analyzer-chromium/high-temperature conversion isotope ratio mass spectrometry (EA-Cr/HTC-IRMS).

Rationale: Accurate hydrogen isotopic analysis of halogen- and sulfur-bearing organics has not been possible with traditional high-temperature conversion (HTC) because the formation of hydrogen-bearing reaction products other than molecular hydrogen (H ) is responsible for non-quantitative H yields and possible hydrogen isotopic fractionation. Our previously introduced, new chromium-based EA-Cr/HTC-IRMS (Elemental Analyzer-Chromium/High-Temperature Conversion Isotope Ratio Mass Spectrometry) technique focused primarily on nitrogen-bearing compounds. Several technical and analytical issues concerning halogen- and sulfur-bearing samples, however, remained unresolved and required further refinement of the reactor systems.

Comment on "Reconciliation of the Devils Hole climate record with orbital forcing".

Moseley et al's (Reports, 8 January 2016, p. 165) preferred-Termination-II age is subjective, as evidenced by variation in their Termination-II ages of 2500 years per meter. Termination-II-age bias decreases to zero at ~1.

A revision in hydrogen isotopic composition of USGS42 and USGS43 human-hair stable isotopic reference materials for forensic science.

The hydrogen isotopic composition (δ(2)HVSMOW-SLAP) of USGS42 and USGS43 human hair stable isotopic reference materials, normalized to the VSMOW (Vienna-Standard Mean Ocean Water)-SLAP (Standard Light Antarctic Precipitation) scale, was originally determined with a high temperature conversion technique using an elemental analyzer (TC/EA) with a glassy carbon tube and glassy carbon filling and analysis by isotope-ratio mass spectrometer (IRMS). However, the TC/EA IRMS method can produce inaccurate δ(2)HVSMOW-SLAP results when analyzing nitrogen-bearing organic substances owing to the formation of hydrogen cyanide (HCN), leading to non-quantitative conversion of a sample into molecular hydrogen (H2) for IRMS analysis. A single-oven, chromium-filled, elemental analyzer (Cr-EA) coupled to an IRMS substantially improves the measurement quality and reliability of hydrogen isotopic analysis of hydrogen- and nitrogen-bearing organic material because hot chromium scavenges all reactive elements except hydrogen.

Organic Reference Materials for Hydrogen, Carbon, and Nitrogen Stable Isotope-Ratio Measurements: Caffeines, n-Alkanes, Fatty Acid Methyl Esters, Glycines, L-Valines, Polyethylenes, and Oils.

An international project developed, quality-tested, and determined isotope-δ values of 19 new organic reference materials (RMs) for hydrogen, carbon, and nitrogen stable isotope-ratio measurements, in addition to analyzing pre-existing RMs NBS 22 (oil), IAEA-CH-7 (polyethylene foil), and IAEA-600 (caffeine). These new RMs enable users to normalize measurements of samples to isotope-δ scales. The RMs span a range of δ(2)H(VSMOW-SLAP) values from -210.

A new organic reference material, l-glutamic acid, USGS41a, for δ(13) C and δ(15) N measurements - a replacement for USGS41.

Rationale: The widely used l-glutamic acid isotopic reference material USGS41, enriched in both (13) C and (15) N, is nearly exhausted. A new material, USGS41a, has been prepared as a replacement for USGS41.

Methods: USGS41a was prepared by dissolving analytical grade l-glutamic acid enriched in (13) C and (15) N together with l-glutamic acid of normal isotopic composition.

LIMS for Lasers 2015 for achieving long-term accuracy and precision of δ(2)H, δ(17)O, and δ(18)O of waters using laser absorption spectrometry.

Rationale: Although laser absorption spectrometry (LAS) instrumentation is easy to use, its incorporation into laboratory operations is not easy, owing to extensive offline manipulation of comma-separated-values files for outlier detection, between-sample memory correction, nonlinearity (δ-variation with water amount) correction, drift correction, normalization to VSMOW-SLAP scales, and difficulty in performing long-term QA/QC audits.

Methods: A Microsoft Access relational-database application, LIMS (Laboratory Information Management System) for Lasers 2015, was developed. It automates LAS data corrections and manages clients, projects, samples, instrument-sample lists, and triple-isotope (δ(17)O, δ(18)O, and δ(2)H values) instrumental data for liquid-water samples.

A new isotopic reference material for stable hydrogen and oxygen isotope-ratio measurements of water - USGS50 Lake Kyoga Water.

Rationale: As a result of the need for isotopic reference waters having high δ(2) HVSMOW-SLAP and δ(18) OVSMOW-SLAP values for daily use, especially for tropical and equatorial-zone freshwaters, a new secondary isotopic reference material for international distribution was prepared from water collected from Lake Kyoga, Uganda.

Methods: This isotopic reference lakewater was filtered through a membrane with 0.2-µm pore size, homogenized, loaded into glass ampoules that were sealed with a torch and autoclaved to eliminate biological activity, and measured by dual-inlet isotope-ratio mass spectrometry.

Isotopic disproportionation during hydrogen isotopic analysis of nitrogen-bearing organic compounds.

Rationale: High-precision hydrogen isotope ratio analysis of nitrogen-bearing organic materials using high-temperature conversion (HTC) techniques has proven troublesome in the past. Formation of reaction products other than molecular hydrogen (H(2)) has been suspected as a possible cause of incomplete H(2) yield and hydrogen isotopic fractionation.

Methods: The classical HTC reactor setup and a modified version including elemental chromium, both operated at temperatures in excess of 1400 °C, have been compared using a selection of nitrogen-bearing organic compounds, including caffeine.

On-line hydrogen-isotope measurements of organic samples using elemental chromium: an extension for high temperature elemental-analyzer techniques.

The high temperature conversion (HTC) technique using an elemental analyzer with a glassy carbon tube and filling (temperature conversion/elemental analysis, TC/EA) is a widely used method for hydrogen isotopic analysis of water and many solid and liquid organic samples with analysis by isotope-ratio mass spectrometry (IRMS). However, the TC/EA IRMS method may produce inaccurate δ(2)H results, with values deviating by more than 20 mUr (milliurey = 0.001 = 1‰) from the true value for some materials.

Biscayne aquifer drinking water (USGS45): a new isotopic reference material for δ2H and δ18O measurements of water.

Rationale: As a result of the scarcity of isotopic reference waters for daily use, a new secondary isotopic reference material for international distribution has been prepared from drinking water collected from the Biscayne aquifer in Ft. Lauderdale, Florida.

Methods: This isotopic reference water was filtered, homogenized, loaded into glass ampoules, sealed with a torch, autoclaved to eliminate biological activity, and measured by dual-inlet isotope-ratio mass spectrometry.

Caution on the use of NBS 30 biotite for hydrogen-isotope measurements with on-line high-temperature conversion systems.

Rationale: The supply of NBS 30 biotite is nearly exhausted. During measurements of NBS 30 and potential replacements, reproducible δ(2)HVSMOW-SLAP values could not be obtained by three laboratories using high-temperature conversion (HTC) systems. The cause of this issue has been investigated using the silver-tube technique for hydrogen-isotope measurements of water.

USGS48 Puerto Rico precipitation - a new isotopic reference material for δ2H and δ18O measurements of water.

A new secondary isotopic reference material has been prepared from Puerto Rico precipitation, which was filtered, homogenised, loaded into glass ampoules, sealed with a torch, autoclaved to eliminate biological activity, and calibrated by dual-inlet isotope-ratio mass spectrometry. This isotopic reference material, designated as USGS48, is intended to be one of two isotopic reference waters for daily normalisation of stable hydrogen (δ(2)H) and stable oxygen (δ(18)O) isotopic analysis of water with a mass spectrometer or a laser absorption spectrometer. The δ(2)H and δ(18)O values of this reference water are-2.