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Tyler B. Coplen

Publications and source records attributed to Tyler B. Coplen.

At least 73 records · Page 4Linked to original sources
USGS2014

USGS48 Puerto Rico precipitation - A new isotopic reference material for δ 2 H and δ 18 O 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−2.0±0.4 and−2.224±0.012 ‰, respectively, relative to Vienna Standard Mean Ocean Water on scales normalised such that the δ 2 H and δ 18 O values of Standard Light Antarctic Precipitation reference water are−428 and−55.5 ‰, respectively. Each uncertainty is an estimated expanded uncertainty ( U =2 u c ) about the reference value that provides an interval that has about a 95 % probability of encompassing the true value. This isotopic reference water is available by the case of 144 glass ampoules containing 5 mL of water in each ampoule.

Puerto Rico↗
USGS2014

Oxygen isotope systematics in the aragonite-CO2-H2O-NaCl system up to 0.7 mol/kg ionic strength at 25 °C

To investigate the oxygen isotope systematics in the aragonite-CO2-H2O-NaCl system, witherite (BaCO3) was precipitated quasi-instantaneously and quantitatively from Na-Cl-Ba-CO2 solutions of seawater-like ionic strength (I = 0.7 mol/kg) at two pH values (~7.9 and ~10.6) at 25 °C. The oxygen isotope composition of the witherite and the dissolved inorganic carbon speciation in the starting solution were used to estimate the oxygen isotope fractionations between HCO3¯ and H2O as well as between CO3 2 and H2O. Given the analytical error on the oxygen isotope composition of the witherite and uncertainties of the parent solution pH and speciation, oxygen isotope fractionation between NaHCO3° and HCO3¯, as well as between NaCO3¯ and CO3 2, is negligible under the experimental conditions investigated. The influence of dissolved NaCl concentration on the oxygen isotope fractionation in the aragonite-CO2-H2O-NaCl system also was investigated at 25 °C. Aragonite was precipitated from Na-Cl-Ca-Mg-(B)-CO2 solutions of seawater-like ionic strength using passive CO2 degassing or constant addition methods. Based upon our new experimental observations and published experimental data from lower ionic strength solutions by Kim et al. (2007b), the equilibrium aragonite-water oxygen isotope fractionation factor is independent of the ionic strength of the parent solution up to 0.7 mol/kg. Hence, our study also suggests that the aragonite precipitation mechanism is not affected by the presence of sodium and chloride ions in the parent solution over the range of concentrations investigated.

Geochimica et Cosmochimica Acta↗
USGS2014

Assessment of international reference materials for isotope-ratio analysis (IUPAC Technical Report)

Since the early 1950s, the number of international measurement standards for anchoring stable isotope delta scales has mushroomed from 3 to more than 30, expanding to more than 25 chemical elements. With the development of new instrumentation, along with new and improved measurement procedures for studying naturally occurring isotopic abundance variations in natural and technical samples, the number of internationally distributed, secondary isotopic reference materials with a specified delta value has blossomed in the last six decades to more than 150 materials. More than half of these isotopic reference materials were produced for isotope-delta measurements of seven elements: H, Li, B, C, N, O, and S. The number of isotopic reference materials for other, heavier elements has grown considerably over the last decade. Nevertheless, even primary international measurement standards for isotope-delta measurements are still needed for some elements, including Mg, Fe, Te, Sb, Mo, and Ge. It is recommended that authors publish the delta values of internationally distributed, secondary isotopic reference materials that were used for anchoring their measurement results to the respective primary stable isotope scale.

Pure and Applied Chemistry↗
USGS2014

A 19-year record of chemical and isotopic composition of water from springs of the Shenandoah National Park, Virginia, 1995-2014

During October 1995 through March 2014, the U.S. Geological Survey in cooperation with the National Park Service, Luray, Virginia Station collected and analyzed samples of selected springs, air and unsaturated-zone gases in Shenandoah National Park, Virginia. The 19-year record of measurements of chemical and isotopic composition of water discharging from 34 springs located along the crest of the Blue Ridge Mountains in Shenandoah National Park, Virginia, is reported. These data include field measurements of water temperature, specific conductance, concentrations of dissolved oxygen (O 2 ), and pH. Laboratory measurements included major-, minor-, and trace-element chemistry; concentrations of dissolved gases (nitrogen, [N 2 ] argon [Ar], oxygen, and carbon dioxide [CO 2 ]); concentrations of dissolved trace atmospheric gases, including trichlorofluoromethane (CFC-11), dichlorodifluoromethane (CFC-12), and trichlorotrifluoroethane (CFC-113) and sulfur hexafluoride (SF 6 ); and hydrogen stable isotopic composition (δ 2 H) and oxygen isotopic composition (δ 18 O) of water. The data include an up to 14-year time series record of monthly sampling at five springs collected between 1995 and 2013. The measurements included temperature, specific conductance, pH, and discharge recorded at 30-minute intervals. Atmospheric mixing ratios of CFC-11, CFC-12, CFC-113, trifluorobromomethane (CF 3 Br), SF 6 , and trifluoromethyl sulfur pentafluoride (SF 5 CF 3 ) in air from the Big Meadows Air Monitoring Station, Shenandoah National Park, were measured at approximately weekly intervals from September 1995 through March 2014. Additional data include monthly (between May 2001 and August 2003) measurements of temperature, N 2 , O 2 , Ar, CO 2 , CFC-12, CFC-11, CFC-113, and SF 6 concentrations in unsaturated-zone air from seven multilevel piezometers in Shenandoah National Park and at the U.S. Geological Survey National Center in Reston, Virginia. All samples were analyzed at the U.S. Geological Survey Laboratories in Reston, Virginia.

Virginia↗
USGS2013

Lake Louise Water (USGS47): A new isotopic reference water for stable hydrogen and oxygen isotope measurements

"RATIONALE: Because of the paucity of isotopic reference waters for daily use, a new secondary isotopic reference material has been prepared from Lake Louise water from Alberta, Canada for international distribution. MOTHODS: This 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. This isotopic reference water is available by the case of 144 glass ampoules containing 5 mL of water in each ampoule. RESULTS: The δ2H and δ18O values of this reference water are –150.2 ± 0.5 ‰ and –19.80 ± 0.02 ‰, respectively, relative to VSMOW on scales normalized such that the δ2H and δ18O values of SLAP reference water are, respectively, –428 and –55.5 ‰. Each uncertainty is an estimated expanded uncertainty (U = 2uc) about the reference value that provides an interval that has about a 95-percent probability of encompassing the true value. CONCLUSION: This isotopic reference material, designated as USGS47, is intended as one of two isotopic reference waters for daily normalization of stable hydrogen and stable oxygen isotopic analysis of water with a mass spectrometer or a laser absorption spectrometer. "

Rapid Communications in Mass Spectrometry↗
USGS2013

USGS46 Greenland ice core water – A new isotopic reference material for δ2H and δ18O measurements of water

Ice core from Greenland was melted, filtered, homogenised, loaded into glass ampoules, sealed, autoclaved to eliminate biological activity, and calibrated by dual-inlet isotope-ratio mass spectrometry. This isotopic reference material (RM), USGS46, is intended as one of two secondary 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 measured δ 2 H and δ 18 O values of this reference water were −235.8 ± 0.7‰ and −29.80 ± 0.03‰, respectively, relative to VSMOW on scales normalised such that the δ 2 H and δ 18 O values of SLAP reference water are, respectively, −428 and −55.5‰. Each uncertainty is an estimated expanded uncertainty ( U = 2 u c ) about the reference value that provides an interval that has about a 95-percent probability of encompassing the true value. This reference water is available in cases containing 144 glass ampoules that are filled with either 4 ml or 5 ml of water per ampoule.

Geostandards and Geoanalytical Research↗
USGS2013

Evidence for high salinity of Early Cretaceous sea water from the Chesapeake Bay crater

High salinity groundwater more than 1000 metres deep in the Atlantic Coastal Plain of the United States has been documented in several locations1,2, most recently within the 35 million-year-old Chesapeake Bay impact crater3,4,5. Suggestions for the origin of increased salinity in the crater have included evaporite dissolution6, osmosis6, and evaporation from heating7 associated with the bolide impact. Here we present chemical, isotopic and physical evidence that together indicate that groundwater in the Chesapeake crater is remnant Early Cretaceous North Atlantic (ECNA) seawater. We find that the seawater is likely 100-145 million years old and that it has an average salinity of about 70 per mil, which is twice that of modern seawater and consistent with the nearly closed ECNA basin8. Previous evidence for temperature and salinity levels of ancient oceans have been estimated indirectly from geochemical, isotopic and paleontological analyses of solid materials in deep sediment cores. In contrast, our study identifies ancient seawater in situ and provides a direct estimate of its age and salinity. Moreover, we suggest that it is likely that remnants of ECNA seawater persist in deep sediments at many locations along the Atlantic margin.

Maryl;Virginia↗
USGS2013

Spatial, seasonal, and source variability in the stable oxygen and hydrogen isotopic composition of tap waters throughout the USA

To assess spatial, seasonal, and source variability in stable isotopic composition of human drinking waters throughout the entire USA, we have constructed a database of δ 18 O and δ 2 H of US tap waters. An additional purpose was to create a publicly available dataset useful for evaluating the forensic applicability of these isotopes for human tissue source geolocation. Samples were obtained at 349 sites, from diverse population centres, grouped by surface hydrologic units for regional comparisons. Samples were taken concurrently during two contrasting seasons, summer and winter. Source supply (surface, groundwater, mixed, and cistern) and system (public and private) types were noted. The isotopic composition of tap waters exhibits large spatial and regional variation within each season as well as significant at-site differences between seasons at many locations, consistent with patterns found in environmental (river and precipitation) waters deriving from hydrologic processes influenced by geographic factors. However, anthropogenic factors, such as the population of a tap’s surrounding community and local availability from diverse sources, also influence the isotopic composition of tap waters. Even within a locale as small as a single metropolitan area, tap waters with greatly differing isotopic compositions can be found, so that tap water within a region may not exhibit the spatial or temporal coherence predicted for environmental water. Such heterogeneities can be confounding factors when attempting forensic inference of source water location, and they underscore the necessity of measurements, not just predictions, with which to characterize the isotopic composition of regional tap waters. Published 2013. This article is a U.S. Government work and is in the public domain in the USA.

Hydrological Processes↗
USGS2013

Atomic weights of the elements 2011 (IUPAC Technical Report)

The biennial review of atomic-weight determinations and other cognate data has resulted in changes for the standard atomic weights of five elements. The atomic weight of bromine has changed from 79.904(1) to the interval [79.901, 79.907], germanium from 72.63(1) to 72.630(8), indium from 114.818(3) to 114.818(1), magnesium from 24.3050(6) to the interval [24.304, 24.307], and mercury from 200.59(2) to 200.592(3). For bromine and magnesium, assignment of intervals for the new standard atomic weights reflects the common occurrence of variations in the atomic weights of those elements in normal terrestrial materials.

Pure and Applied Chemistry↗
USGS2013

The δ2H and δ18O of tap water from 349 sites in the United States and selected territories

Because the stable isotopic compositions of hydrogen (δ 2 H) and oxygen (δ 18 O) of animal (including human) tissues, such as hair, nail, and urine, reflect the δ 2 H and δ 18 O of water and food ingested by an animal or a human and because the δ 2 H and δ 18 O of environmental waters vary geographically, δ 2 H and δ 18 O values of tap water samples collected in 2007-2008 from 349 sites in the United States and three selected U.S. territories have been measured in support of forensic science applications, creating one of the largest databases of tap water δ 2 H and δ 18 O values to date. The results of replicate isotopic measurements for these tap water samples confirm that the expanded uncertainties (U = 2μ c ) obtained over a period of years by the Reston Stable Isotope Laboratory from δ 2 H and δ 18 O dual-inlet mass spectrometric measurements are conservative, at ±2‰ and ±0.2 ‰, respectively. These uncertainties are important because U.S. Geological Survey data may be needed for forensic science applications, including providing evidence in court cases. Half way through the investigation, an isotope-laser spectrometer was acquired, enabling comparison of dual-inlet isotope-ratio mass spectrometric results with isotope-laser spectrometric results. The uncertainty of the laser-based δ 2 H measurement results for these tap water samples is comparable to the uncertainty of the mass spectrometric method, with the laser-based method having a slightly lower uncertainty. However, the δ 18 O uncertainty of the laser-based method is more than a factor of ten higher than that of the dual-inlet isotoperatio mass spectrometric method.

Guam, Puerto Rico, St. John, U.S. Virgin Islands↗
USGS2012

Stable isotope deltas: Tiny, yet robust signatures in nature

Although most of them are relatively small, stable isotope deltas of naturally occurring substances are robust and enable workers in anthropology, atmospheric sciences, biology, chemistry, environmental sciences, food and drug authentication, forensic science, geochemistry, geology, oceanography, and paleoclimatology to study a variety of topics. Two fundamental processes explain the stable isotope deltas measured in most terrestrial systems: isotopic fractionation and isotope mixing. Isotopic fractionation is the result of equilibrium or kinetic physicochemical processes that fractionate isotopes because of small differences in physical or chemical properties of molecular species having different isotopes. It is shown that the mixing of radioactive and stable isotope end members can be modelled to provide information on many natural processes, including 14C abundances in the modern atmosphere and the stable hydrogen and oxygen isotopic compositions of the oceans during glacial and interglacial times. The calculation of mixing fractions using isotope balance equations with isotope deltas can be substantially in error when substances with high concentrations of heavy isotopes (e.g. 13C, 2H, and 18O ) are mixed. In such cases, calculations using mole fractions are preferred as they produce accurate mixing fractions. Isotope deltas are dimensionless quantities. In the International System of Units (SI), these quantities have the unit 1 and the usual list of prefixes is not applicable. To overcome traditional limitations with expressing orders of magnitude differences in isotope deltas, we propose the term urey (symbol Ur), after Harold C. Urey, for the unit 1. In such a manner, an isotope delta value expressed traditionally as−25 per mil can be written as−25 mUr (or−2.5 cUr or−0.25 dUr; the use of any SI prefix is possible). Likewise, very small isotopic differences often expressed in per meg ‘units’ are easily included (e.g. either+0.015 ‰ or+15 per meg can be written as+15 μUr.

Isotopes in Environmental and Health Studies↗
USGS2012

Determination of the δ 13 C of dissolved inorganic carbon in water; RSIL lab code 1710

The purpose of the Reston Stable Isotope Laboratory (RSIL) lab code 1710 is to present a method to determine the δ 13 C of dissolved inorganic carbon (DIC) of water. The DIC of water is precipitated using ammoniacal strontium chloride (SrCl 2 ) solution to form strontium carbonate (SrCO 3 ). The δ 13 C is analyzed by reacting SrCO 3 with 100-percent phosphoric acid (H 3 PO 4 ) to liberate carbon quantitatively as carbon dioxide (CO 2 ), which is collected, purified by vacuum sublimation, and analyzed by dual inlet isotope-ratio mass spectrometry (DI-IRMS). The DI-IRMS is a DuPont double-focusing mass spectrometer. One ion beam passes through a slit in a forward collector and is collected in the rear collector. The other measurable ion beams are collected in the front collector. By changing the ion-accelerating voltage under computer control, the instrument is capable of measuring mass/charge ( m/z ) 45 or 46 in the rear collector and m/z 44 and 46 or 44 and 45, respectively, in the front collector. The ion beams from these m/z values are as follows: m/z 44 = CO 2 = 12 C 16 O 16 O, m/z 45 = CO 2 = 13 C 16 O 16 O primarily, and m/z 46 = CO 2 = 12 C 16 O 18 O primarily. The data acquisition and control software calculates δ 13 C values.

Techniques and Methods↗
USGS2012

Determination of the δ 2 H and δ 18 O of soil water and water in plant matter; RSIL lab code 1700

The purpose of the Reston Stable Isotope Laboratory lab code 1700 is to determine the δ 2 H/ 1 H), abbreviated as δ 2 H, and the δ 18 O/ 16 O), abbreviated as δ 18 O, of soil water and water in plant matter. This method is based on the observation that water and toluene form an azeotropic mixture at 84.1 °C. This temperature is substantially lower than the boiling points of water (100 °C) and toluene (110 °C), but water and toluene are immiscible at ambient temperature. The water content of a soil or plant is determined by weighing, drying, and reweighing a small amount of sample. Sufficient sample to collect 3 to 5 milliliters of water after distillation is loaded into a distillation flask. Sufficient toluene is added so that the sample is immersed throughout the entire distillation to minimize evaporation of water, which would affect the δ 2 H and δ 18 O values. The mixture of sample and toluene is heated in a flask to its boiling point (84.1 °C) so that water from the sample and toluene can distill together into a specially designed collection funnel. The temperature of 84.1 °C is maintained until the water has been quantitatively transferred to the collection funnel, at which time the temperature is raised to the boiling point of the remaining component (toluene, 110 °C). The collection funnel is maintained at ambient temperature so that the sample water and toluene can be separated physically. After separation, the sample water is purified by addition of paraffin wax to the container with the sample water, capping the container, and heating to approximately 60 °C to melt the wax. Trace amounts of toluene will dissolve in the wax, purifying the sample water for isotopic analysis. The isotopic composition of the purified water is then determined by equilibration with gaseous hydrogen or carbon dioxide, followed by dual-inlet isotope-ratio mass spectrometry. Because laser-absorption spectrometry is sensitive to organic compounds, such as trace toluene remaining in water samples, water samples should be analyzed for isotopic composition only by mass spectrometry and not by laser-absorption spectrometry.

Techniques and Methods↗
USGS2011

Guidelines and recommended terms for expression of stable-isotope-ratio and gas-ratio measurement results

To minimize confusion in the expression of measurement results of stable isotope and gas-ratio measurements, recommendations based on publications of the Commission on Isotopic Abundances and Atomic Weights of the International Union of Pure and Applied Chemistry (IUPAC) are presented. Whenever feasible, entries are consistent with the Système International d'Unités, the SI (known in English as the International System of Units), and the third edition of the International Vocabulary of Basic and General Terms in Metrology (VIM, 3rd edition). The recommendations presented herein are approved by the Commission on Isotopic Abundances and Atomic Weights and are designed to clarify expression of quantities related to measurement of isotope and gas ratios to ensure that quantity equations instead of numerical value equations are used for quantity definitions. Examples of column headings consistent with quantity calculus (also called the algebra of quantities) and examples of various deprecated usages connected with the terms recommended are presented.

Rapid Communications in Mass Spectrometry↗
USGS2011

Investigation of preparation techniques for δ2H analysis of keratin materials and a proposed analytical protocol

Accurate hydrogen isotopic measurements of keratin materials have been a challenge due to exchangeable hydrogen in the sample matrix and the paucity of appropriate isotopic reference materials for calibration. We found that the most reproducible δ 2 H VSMOW‐SLAP and mole fraction of exchangeable hydrogen, x (H) ex , of keratin materials were measured with equilibration at ambient temperature using two desiccators and two different equilibration waters with two sets of the keratin materials for 6 days. Following equilibration, drying the keratin materials in a vacuum oven for 4 days at 60 °C was most critical. The δ 2 H analysis protocol also includes interspersing isotopic reference waters in silver tubes among samples in the carousel of a thermal conversion elemental analyzer (TC/EA) reduction unit. Using this analytical protocol, δ 2 H VSMOW‐SLAP values of the non‐exchangeable fractions of USGS42 and USGS43 human‐hair isotopic reference materials were determined to be –78.5 ± 2.3 ‰ and –50.3 ± 2.8 ‰, respectively. The measured x (H) ex values of keratin materials analyzed with steam equilibration and N 2 drying were substantially higher than those previously published, and dry N 2 purging was unable to remove absorbed moisture completely, even with overnight purging. The δ 2 H values of keratin materials measured with steam equilibration were about 10 ‰ lower than values determined with equilibration in desiccators at ambient temperatures when on‐line evacuation was used to dry samples. With steam equilibrations the x (H) ex of commercial keratin powder was as high as 28 %. Using human‐hair isotopic reference materials to calibrate other keratin materials, such as hoof or horn, can introduce bias in δ 2 H measurements because the amount of absorbed water and the x (H) ex values may differ from those of unknown samples. Correct δ 2 H VSMOW‐SLAP values of the non‐exchangeable fractions of unknown human‐hair samples can be determined with atmospheric moisture equilibration by normalizing with USGS42 and USGS43 human‐hair reference materials when all materials have the same powder size.

Rapid Communications in Mass Spectrometry↗
USGS2011

Improved online δ18O measurements of nitrogen‐ and sulfur‐bearing organic materials and a proposed analytical protocol

It is well known that N 2 in the ion source of a mass spectrometer interferes with the CO background during the δ 18 O measurement of carbon monoxide. A similar problem arises with the high‐temperature conversion (HTC) analysis of nitrogenous O‐bearing samples (e.g. nitrates and keratins) to CO for δ 18 O measurement, where the sample introduces a significant N 2 peak before the CO peak, making determination of accurate oxygen isotope ratios difficult. Although using a gas chromatography (GC) column longer than that commonly provided by manufacturers (0.6 m) can improve the efficiency of separation of CO and N 2 and using a valve to divert nitrogen and prevent it from entering the ion source of a mass spectrometer improved measurement results, biased δ 18 O values could still be obtained. A careful evaluation of the performance of the GC separation column was carried out. With optimal GC columns, the δ 18 O reproducibility of human hair keratins and other keratin materials was better than ±0.15 ‰ (n = 5; for the internal analytical reproducibility), and better than ±0.10 ‰ (n = 4; for the external analytical reproducibility).

Rapid Communications in Mass Spectrometry↗
USGS2011

Atomic weights: No longer constants of nature

Many of us were taught that the standard atomic weights we found in the back of our chemistry textbooks or on the Periodic Table of the Chemical Elements hanging on the wall of our chemistry classroom are constants of nature. This was common knowledge for more than a century and a half, but not anymore. The following text explains how advances in chemical instrumentation and isotopic analysis have changed the way we view atomic weights and why they are no longer constants of nature

Chemistry International↗