Geology ReportsSearch

USGS · 70262816

Using stable oxygen isotope dual-inlet isotope-ratio mass spectrometry to elucidate uranium transport and mixed 230Th/U calcite formation ages at the seminal Devils Hole, Nevada, natural laboratory

Abstract

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 δ 18 O paleoclimate time series. A substantial issue is that coeval calcite (based on matching δ 18 O values) has uranium-series ages differing by 12 000 years. Methods An unparalleled high-accuracy δ 18 O 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. This method relies on the premise that the δ 18 O values of coevally precipitated calcite are identical, allowing matching calcite δ 18 O values to establish formation ages. Results Exposed calcite can have apparent ages that are 12 000 years too young due to unrecognized uranium mobility and resulting mixed ages identified in over 50 mixed uranium-series ages from previous studies. Secondary uranium in fluids, sourced from the formation or dissolution of porous carbonate deposits (folia) with high uranium-238 ( 238 U) concentrations, has migrated up to 10 mm into vein calcite. Conclusions The continuously submerged Devils Hole δ 18 O chronology is not explained by orbital forcing. Rather, this chronology represents a regional climate record in the southern Great Basin of sea-surface-temperature (SST) variations off California, variations that preceded the last and penultimate deglaciations by 5000 to approximately 10 000 years. Temporal discrepancies between the continuously submerged Devils Hole chronology and other regional δ 18 O records (e.g., the Leviathan chronology) can be explained by unrecognized cryptic, pernicious uranium mobility, leading to model estimations that may be thousands of years younger than actual ages. Consequently, paleo-moisture availability, water-table, and groundwater recharge models based on these mixed uranium-series ages are too young by as much as 12 000 years. The potential for post-formation uranium addition in subaerial cores and speleothems underscores the need for caution in uranium-series dating, highlighting δ 18 O time-series comparisons as a method for identifying mixed ages.

Explore related subjects

90° N90° S · 180° W ← longitude → 180° E
Source-reported bounding extent: 35.9796450622334° to 40.12275342984714° latitude; -116.79795852135467° to -113.93379652706551° longitude. This indicates report coverage, not an exact sampling location. View area on OpenStreetMap.

Keep this discovery

BibTeXRIS

Tyler B. Coplen, Robert R. Seal,, Lauren T Reid, James A. Jordan, Adam C. Mumford. 2024-11-23. Using stable oxygen isotope dual-inlet isotope-ratio mass spectrometry to elucidate uranium transport and mixed 230Th/U calcite formation ages at the seminal Devils Hole, Nevada, natural laboratory. https://doi.org/10.1002/rcm.9926

Cite the original work for its findings. Save a collection to share your selection of sources.

Discover connections

Connections use source metadata and explicit phrase matches, not verified experimental comparisons.

KEEP EXPLORING

Related USGS reports

lasertram: A Python library for time resolved analysis of laser ablation inductively coupled plasma mass spectrometry data

Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) data has a wide variety of uses in the geosciences for in-situ chemical analysis of complex natural materials. Improvements to instrument capabilities and operating software have drastically reduced the time required to generate large volumes of data relative to previous methodologies. Raw data from LA-ICP-MS, however, is in counts per unit time (typically counts per second), not elemental concentrations and converting these count ratesto concentrations requires additional processing. For complex materials where the ablated volume may contain a range of material compositions, a moderate amount of user input is also required if appropriate concentrations are to be accurately calculated. In geologic materials such as glasses and minerals that potentially have numerous heterogeneities (e.g., microlites or other inclusions) within them, this is typically determiningwhether the total ablation signal should be filtered to remove these heterogeneities. This necessitates that the LA-ICP-MS data processing pipeline is one that is not automated, but is also designed to enable rapid and efficient processing of large volumes of data. Here we introduce , a Python library for the time resolved analysis of LA-ICP-MS data. We outline its mathematical theory, code structure, and provide an example of how it can be used to provide the time resolved analysis necessitated by LA-ICP-MS data of complex geologic materials. Throughout the pipeline we show how metadata and data are incrementally added to the objects created such that virtually any aspect of an experiment may be interrogated and its quality assessed. We also show, that when combined with other Python libraries for building graphical user interfaces, it can be utilized outside of a pure scripting environment. can be found at https://doi.org/10.5066/P1DZUR3Z

Applied Computing and Geosciences

Determination of per- and polyfluoroalkyl substances in water by direct injection of matrix-modified centrifuge supernatant and liquid chromatography/tandem mass spectrometry with isotope dilution

A direct-injection liquid chromatography/tandem mass spectrometry method was developed to determine 34 per- and polyfluoroalkyl substances (PFAS), including selected branched isomers, in centrifuge supernatant of matrix-modified (amended with approximately 50 percent methanol) water samples. The method has been validated in reagent water, surface water, groundwater, and wastewater effluent. Other water types (for example, drinking water, untreated wastewater, and landfill leachate) have been analyzed by the method but not systematically validated. Recovery of isotope-dilution standards, added to each sample, may be used to assess method performance in nonvalidated matrices on a sample-by-sample basis. Using this method, PFAS concentrations were determined in the range of 2–2,000 nanograms per liter in water samples. This range can be extended by diluting concentrated samples. At circumneutral pH, most compounds are present in the environment in their ionized form, and data are reported as such (for example, perfluorooctanoic acid is referred to as “perfluorooctanoate” [PFOA], perfluorooctane sulfonic acid is referred to as “perfluorooctane sulfonate” [PFOS]). Sample preparation procedures were designed without the use of filtration and with minimum sample handling steps to mitigate procedural losses of target compounds due to sorption to surfaces. Further, isotope-dilution quantification allowed for the correction of bias that may result from procedural losses, matrix-induced signal suppression or enhancement, and other factors. Validation experiments to characterize bias and variability, method detection level, and holding time were done in four distinct water matrices—reagent water, surface water, treated wastewater effluent, and groundwater—at multiple concentration levels. Mean PFAS recoveries met data quality objectives of bias and variability studies in all four validation matrices except for two compounds with low and variable recovery in the reagent water matrix only. Isotope-dilution standards, treated as surrogate compounds, were analyzed in more than 1,500 customer-submitted environmental samples with aggregate recovery of 102.5±6.5 percent (mean±standard deviation). Maximum holding times for all target compounds in the four validation matrices were 28 days for refrigerated samples and 90 days for frozen samples.

Techniques and Methods

Re-Os geochronology of molybdenite by LA-ICP-MS/MS

Re-Os geochronology is a powerful tool to directly date sulphide mineralisation using phases such as molybdenite, pyrite and chalcopyrite. We present a snapshot of a method in development utilizing laser ablation inductively coupled-plasma ‘triple quad’ mass spectrometry (LA-ICP-MS/MS) for Re-Os geochronology of molybdenite. While traditional LA-(MC)-ICP-MS measurements are limited by the >90% isobaric interference correction of parent radioactive 187 Re on radiogenic daughter 187 Os, the MS/MS technology minimizes this correction through careful instrument tuning and use of a (CH 4 + H 2 + He) reaction gas mixture to mass shift 187 Os away from 187 Re. We demonstrate the potential of the MS/MS technique by presenting robust Re-Os dates for three different molybdenite samples ranging in age from ~28 to 1520 Ma.

Conference Paper