Tyler B. Coplen

Continuous 500,000-Year Climate Record from Vein Calcite in Devils Hole, Nevada

Oxygen-18 (δ18O) variations in a 36-centimeter-long core (DH-11) of vein calcite from Devils Hole, Nevada, yield an uninterrupted 500,000-year paleotemperature record that closely mimics all major features in the Vostok (Antarctica) paleotemperature and marine δ18O ice-volume records. The chronology for this continental record is based on 21 replicated mass-spectrometric uranium-series dates. Between the middle and latest Pleistocene, the duration of the last four glacial cycles recorded in the calcite increased from 80,000 to 130,000 years; this variation suggests that major climate changes were aperiodic. The timing of specific climatic events indicates that orbitally controlled variations in solar insolation were not a major factor in triggering deglaciations. Interglacial climates lasted about 20,000 years. Collectively, these observations are inconsistent with the Milankovitch hypothesis for the origin of the Pleistocene glacial cycles but they are consistent with the thesis that these cycles originated from internal nonlinear feedbacks within the atmosphere-ice sheet-ocean system.

Normalization of oxygen and hydrogen isotope data

To resolve confusion due to expression of isotopic data from different laboratories on non-corresponding scales, oxygen isotope analyses of all substances can be expressed relative to VSMOW or VPDB (Vienna Peedee belemnite) on scales normalized such that the δ18O of SLAP is −55.5% relative to VSMOW. H3+ contribution in hydrogen isotope ratio analysis can be easily determined using two gaseous reference samples that differ greatly in deuterium content.

Isotope-abundance variations of selected elements (IUPAC Technical Report)

Documented variations in the isotopic compositions of some chemical elements are responsible for expanded uncertainties in the standard atomic weights published by the Commission on Atomic Weights and Isotopic Abundances of the International Union of Pure and Applied Chemistry. This report summarizes reported variations in the isotopic compositions of 20 elements that are due to physical and chemical fractionation processes (not due to radioactive decay) and their effects on the standard atomic-weight uncertainties. For 11 of those elements (hydrogen, lithium, boron, carbon, nitrogen, oxygen, silicon, sulfur, chlorine, copper, and selenium), standard atomic-weight uncertainties have been assigned values that are substantially larger than analytical uncertainties because of common isotope-abundance variations in materials of natural terrestrial origin. For 2 elements (chromium and thallium), recently reported isotope-abundance variations potentially are large enough to result in future expansion of their atomic-weight uncertainties. For 7 elements (magnesium, calcium, iron, zinc, molybdenum, palladium, and tellurium), documented isotope variations in materials of natural ter- restrial origin are too small to have a significant effect on their standard atomic-weight uncertainties. This compilation indicates the extent to which the atomic weight of an element in a given material may differ from the standard atomic weight of the element. For most elements given above, data are graphically illustrated by a diagram in which the materials are specified in the ordinate and the compositional ranges are plotted along the abscissa in scales of (1) atomic weight, (2) mole fraction of a selected isotope, and (3) delta value of a selected isotope ratio.

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

Abstract 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.

Chlorofluorocarbons (CCl3F and CCl2F2) as dating tools and hydrologic tracers in shallow groundwater of the Delmarva Peninsula, Atlantic Coastal Plain, United States

Concentrations of the chlorofluorocarbons (CFCs) CFC-11 and CFC-12 were determined in groundwater from coastal plain sediments of the Delmarva Peninsula. CFC-modeled ages were calculated independently for CFC-11 and CFC-12, and agreed to within 2-3 years in the majority of the waters. Recharge temperatures, determined from dissolved nitrogen and argon concentrations, varied from + or - 2 degrees C over most of the peninsula to 14 + or - 2 degrees C at the southernmost tip of the peninsula in Virginia. The CFC-modeled ages were examined in relation to the known hydrogeologic environment, both on regional scales and in more intensively sampled local scale networks. The CFC-modeled recharge years and measured tritium concentrations were used to reconstruct a tritium input function that was compared to the modeled tritium plus [sup 3]He distribution. Most of the present distribution of tritium in Delmarva groundwater is consistent with low dispersivities. The results of this study strongly support the use of CFCs for dating shallow, aerobic groundwater.

Atomic weights of the elements 1999 (IUPAC Technical Report)

The biennial review of atomic-weight, Ar(E), determinations and other cognate data have resulted in changes for the standard atomic weights of the following elements: element From To nitrogen 14.006 74 ± 0.000 07 14.0067 ± 0.0002 sulfur 32.066 ± 0.006 32.065 ± 0.005 chlorine 35.4527 ± 0.0009 35.453 ± 0.002 germanium 72.61 ± 0.02 72.64 ± 0.01 xenon 131.29 ± 0.02 131.293 ± 0.006 erbium 167.26 ± 0.03 167.259 ± 0.003 uranium 238.0289 ± 0.0001 238.028 91 ± 0.000 03 Presented are updated tables of the standard atomic weights and their uncertainties estimated by combining experimental uncertainties and terrestrial variabilities. In addition, this report again contains an updated table of relative atomic-mass values and half-lives of selected radioisotopes. Changes in the evaluated isotopic abundance values from those published in 1997 are so minor that an updated list will not be published for the year 1999. Many elements have a different isotopic composition in some nonterrestrial materials. Some recent data on parent nuclides that might affect isotopic abundances or atomic-weight values are included in this report for the information of the interested scientific community.

Comprehensive inter-laboratory calibration of reference materials for delta O-18 versus VSMOW using various on-line high-temperature conversion techniques

Internationally distributed organic and inorganic oxygen isotopic reference materials have been calibrated by six laboratories carrying out more than 5300 measurements using a variety of high-temperature conversion techniques (HTC)a in an evaluation sponsored by the International Union of Pure and Applied Chemistry (IUPAC). To aid in the calibration of these reference materials, which span more than 125 per thousand, an artificially enriched reference water (delta(18)O of +78.91 per thousand) and two barium sulfates (one depleted and one enriched in (18)O) were prepared and calibrated relative to VSMOW2b and SLAP reference waters. These materials were used to calibrate the other isotopic reference materials in this study, which yielded: Reference material delta(18)O and estimated combined uncertainty IAEA-602 benzoic acid+71.28 +/- 0.36 per thousand USGS 35 sodium nitrate+56.81 +/- 0.31 per thousand IAEA-NO-3 potassium nitrate+25.32 +/- 0.29 per thousand IAEA-601 benzoic acid+23.14 +/- 0.19 per thousand IAEA-SO-5 barium sulfate+12.13 +/- 0.33 per thousand NBS 127 barium sulfate+8.59 +/- 0.26 per thousand VSMOW2 water 0 per thousand IAEA-600 caffeine-3.48 +/- 0.53 per thousand IAEA-SO-6 barium sulfate-11.35 +/- 0.31 per thousand USGS 34 potassium nitrate-27.78 +/- 0.37 per thousand SLAP water-55.5 per thousand The seemingly large estimated combined uncertainties arise from differences in instrumentation and methodology and difficulty in accounting for all measurement bias. They are composed of the 3-fold standard errors directly calculated from the measurements and provision for systematic errors discussed in this paper. A primary conclusion of this study is that nitrate samples analyzed for delta(18)O should be analyzed with internationally distributed isotopic nitrates, and likewise for sulfates and organics. Authors reporting relative differences of oxygen-isotope ratios (delta(18)O) of nitrates, sulfates, or organic material should explicitly state in their reports the delta(18)O values of two or more internationally distributed nitrates (USGS 34, IAEA-NO-3, and USGS 35), sulfates (IAEA-SO-5, IAEA-SO-6, and NBS 127), or organic material (IAEA-601 benzoic acid, IAEA-602 benzoic acid, and IAEA-600 caffeine), as appropriate to the material being analyzed, had these reference materials been analyzed with unknowns. This procedure ensures that readers will be able to normalize the delta(18)O values at a later time should it become necessary.The high-temperature reduction technique for analyzing delta(18)O and delta(2)H is not as widely applicable as the well-established combustion technique for carbon and nitrogen stable isotope determination. To obtain the most reliable stable isotope data, materials should be treated in an identical fashion; within the same sequence of analyses, samples should be compared with working reference materials that are as similar in nature and in isotopic composition as feasible.

A 250,000-Year Climatic Record from Great Basin Vein Calcite: Implications for Milankovitch Theory

A continuous record of oxygen-18 (δ18O) variations in the continental hydrosphere during the middle-to-late Pleistocene has been obtained from a uranium-series dated calcitic vein in the southern Great Basin. The vein was deposited from ground water that moved through Devils Hole—an open fault zone at Ash Meadows, Nevada—between 50 and 310 ka (thousand years ago). The configuration of the δ18O versus time curve closely resembles the marine and Antarctic ice core (Vostok) δ18O curves; however, the U-Th dates indicate that the last interglacial stage (marine oxygen isotope stage 5) began before 147 � 3 ka, at least 17,000 years earlier than indicated by the marine δ18O record and 7,000 years earlier than indicated by the less well dated Antarctic δ18O record. This discrepancy and other differences in the timing of key climatic events suggest that the indirectly dated marine δ18O chronology may need revision and that orbital forcing may not be the principal cause of the Pleistocene ice ages.

Sulphur isotope data consistency improved

The standard used for reporting relative sulphur isotope-abundance data has, historically, been troilite (FeS) derived from the Cañon Diablo meteorite, CDT. However, the isotopic inhomogeneity of this material — the variability in its sulphur-34/sulphur-32 isotope ratio is at least 0.4‰ — greatly exceeds the achievable analytical uncertainty of 0.05‰ (ref. 1). Accordingly, the International Union of Pure and Applied Chemistry (IUPAC) has recommended the setting up of a VCDT scale, which is expected to improve agreement between laboratories in measuring this ratio, δ34S.

Isotope Engineering—Using Stable Isotopes of the Water Molecule to Solve Practical Problems

This chapter discusses the use of the stable isotope ratios of hydrogen and oxygen (2H/1H and 18O/16O) to address problems related to groundwater as a sustainable resource, and in particular to recharge, delineation of flow systems and quantification of mass-balance relationships (relative amounts of water from various sources) in applied hydrologic investigations. We will attempt to cover many examples from throughout the world. This chapter is written for the hydrologist who needs to solve a problem. We present just enough theory to make this chapter a stand-alone document, followed by several real-world examples of the uses of stable H and O isotope ratios for solving practical hydrologic problems—thus, the title, isotope engineering.