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T.B. Coplen

Publications and source records attributed to T.B. Coplen.

At least 37 records · Page 2Linked to original sources

Evaluation of the 34S/32S ratio of Soufre de Lacq elemental sulfur isotopic reference material by continuous flow isotope-ratio mass spectrometry

Soufre de Lacq elemental sulfur reference material (IAEA-S-4) isotopically is homogeneous in amounts as small as 41 ??g as determined by continuous flow isotope-ratio mass spectrometry. The ??34S value for this reference material is +16.90 ?? 0.12??? (1??) on a scale (Vienna Can??on Diablo troilite, VCDT) where IAEA-S-1 Ag2S is -0.3??? and IAEA-S-2 Ag2S is +22.67???. Published by Elsevier Science B.V.

Chemical Geology↗

Improvements in the gaseous hydrogen-water equilibration technique for hydrogen isotope ratio analysis

Improved precision in the H 2 -H 2 O equilibration method for δD analysis has been achieved in an automated system. Reduction in 1- σ standard deviation of a single mass-spectrometer analysis to 1.3 ‰ is achieved by (1) bonding catalyst to glass rods and assigning use to specific equilibration chambers to monitor performance of catalyst, (2) improving the apparatus design, and (3) reducing the H 3 + contribution of the mass-spectrometer ion source. For replicate analysis of a water sample, the standard deviation improved to 0.8 ‰ . H 2 S-bearing samples and samples as small as 0.1 mL can be analyzed routinely with this method.

Analytical Chemistry↗

Multisample conversion of water to hydrogen by zinc for stable isotope determination

Two techniques for the conversion of water to hydrogen for stable isotope ratio determination have been developed that are especially suited for automated multisample analysis. Both procedures involve reaction of zinc shot with a water sample at 450 ??C. in one method designed for water samples in bottles, the water is put in capillaries and is reduced by zinc in reaction vessels; overall savings in sample preparation labor of 75% have been realized over the standard uranium reduction technique. The second technique is for waters evolved under vacuum and is a sealed-tube method employing 9 mm o.d. quartz tubing. Problems inherent with zinc reduction include surface inhomogeneity of the zinc and exchange of hydrogen both with the zinc and with the glass walls of the vessels. For best results, water/zinc and water/glass surface area ratios of vessels should be kept as large as possible.

Analytical Chemistry↗

Compilation of minimum and maximum isotope ratios of selected elements in naturally occurring terrestrial materials and reagents

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-abundance variations in materials of natural terrestrial 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. There are no internationally distributed isotopic reference materials for the elements zinc, selenium, molybdenum, palladium, and tellurium. Preparation of such materials will help to make isotope ratio measurements among laboratories comparable. The minimum and maximum concentrations of a selected isotope in naturally occurring terrestrial materials for selected chemical elements reviewed in this report are given below: Isotope Minimum mole fraction Maximum mole fraction -------------------------------------------------------------------------------- 2H 0 .000 0255 0 .000 1838 7Li 0 .9227 0 .9278 11B 0 .7961 0 .8107 13C 0 .009 629 0 .011 466 15N 0 .003 462 0 .004 210 18O 0 .001 875 0 .002 218 26Mg 0 .1099 0 .1103 30Si 0 .030 816 0 .031 023 34S 0 .0398 0 .0473 37Cl 0 .240 77 0 .243 56 44Ca 0 .020 82 0 .020 92 53Cr 0 .095 01 0 .095 53 56Fe 0 .917 42 0 .917 60 65Cu 0 .3066 0 .3102 205Tl 0 .704 72 0 .705 06 The numerical values above have uncertainties that depend upon the uncertainties of the determinations of the absolute isotope-abundance variations of reference materials of the elements. Because reference materials used for absolute isotope-abundance measurements have not been included in relative isotope abundance investigations of zinc, selenium, molybdenum, palladium, and tellurium, ranges in isotopic composition are not listed for these elements, although such ranges may be measurable with state-of-the-art mass spectrometry. This report is available at the url: http://pubs.water.usgs.gov/wri014222.

Water-Resources Investigations Report↗

Use of deuterated water as a conservative artificial ground water tracer

Conservative tracers are necessary to obtain groundwater transport velocities at the field scale. Deuterated water is an effective tracer for this purpose due to its similarity to water, chemical stability, non-reactivity, ease of handling and sampling, relatively neutral buoyancy, and reasonable price. Reliable detection limits of 0.1 mg deuterium/L may be obtained in field tests. A field example is presented in which deuterated water, bromide, and pentafluorobenzoic acid are used as groundwater tracers. Deuterated water appeared to be transported conservatively, producing almost identical breakthrough curves as that of other soluble tracers. ?? Springer-Verlag 2001.

Hydrogeology Journal↗

An interlaboratory study to test instrument performance of hydrogen dual-inlet isotope-ratio mass spectrometers

An interlaboratory comparison of forty isotope-ratio mass spectrometers of different ages from several vendors has been performed to test 2 H/ 1 H performance with hydrogen gases of three different isotopic compositions. The isotope-ratio results (unsufficiently corrected for H 3 + contribution to the m/z = 3 collector, uncorrected for valve leakage in the change-over valves, etc.) expressed relative to one of these three gases covered a wide range of values: –630‰ to –790‰ for the second gas and –368‰ to –462‰ for the third gas. After normalizing the isotopic abundances of these test gases (linearly adjusting the δ values so that the gases with the lowest and highest 2 H content were identical for all laboratories), the standard deviation of the 40 measurements of the intermediate gas was a remarkably low 0.85‰. It is concluded that the use of scaling factors is mandatory for providing accurate internationally comparable isotope-abundance values. Linear scaling for the isotope-ratio scales of gaseous hydrogen mass spectrometers is completely adequate.

Fresenius' Journal of Analytical Chemistry↗

Atomic weights of the elements 1999

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: 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. ?? 2001 American Institute of Physics.

Journal of Physical and Chemical Reference Data↗

Sources and haloacetic acid/trihalomethane formation potentials of aquatic humic substances in the Wakarusa River and Clinton Lake near Lawrence, Kansas

Gram quantities of aquatic humic substances (AHS) were extracted from the Wakarusa River−Clinton Lake Reservoir system, near Lawrence, KS, to support nuclear magnetic resonance (NMR) experimental studies, report concentrations of dissolved organic carbon (DOC) and AHS, define sources of the AHS, and determine if the AHS yield sufficient quantities of haloacetic acids (HAA5) and trihalomethanes (THM4) that exceed U.S. Environmental Protection Agency (EPA) Maximum Contaminant Levels (MCL) in drinking water. AHS from the Wakarusa River and Clinton Lake originated from riparian forest vegetation, reflected respective effects of soil organic matter and aquatic algal/bacterial sources, and bore evidence of biological degradation and photodegradation. AHS from the Wakarusa River showed the effect of terrestrial sources, whereas Clinton Lake humic acid also reflected aquatic algal/bacterial sources. Greater amounts of carbon attributable to tannin-derived chemical structures may correspond with higher HAA5 and THM4 yields for Clinton Lake fulvic acid. Prior to appreciable leaf-fall from deciduous trees, the combined (humic and fulvic acid) THM4 formation potentials for the Wakarusa River approached the proposed EPA THM4 Stage I MCL of 80 μg/L, and the combined THM4 formation potential for Clinton Lake slightly exceeded the proposed THM4 Stage II MCL of 40 μg/L. Finally, AHS from Clinton Lake could account for most (>70%) of the THM4 concentrations in finished water from the Clinton Lake Water Treatment Plant based on September 23, 1996, THM4 results.

Environmental Science & Technology↗

The relative contributions of summer and cool-season precipitation to groundwater recharge, Spring Mountains, Nevada, USA

A comparison of the stable-isotope signatures of spring waters, snow, snowmelt, summer (July thru September) rain, and cool season (October thru June) rain indicates that the high-intensity, short-duration summer convective storms, which contribute approximately a third of the annual precipitation to the Spring Mountains, provide only a small fraction (perhaps 10%) of the recharge to this major upland in southern Nevada, USA. Late spring snowmelt is the principal means of recharging the fractured Paleozoic-age carbonate rocks comprising the central and highest portion of the Spring Mountains. Daily discharge measurements at Peak Spring Canyon Creek during the period 1978–94 show that snowpacks were greatly enhanced during El Niño events.

Hydrogeology Journal↗

Comparison of two stable hydrogen isotope-ratio measurement techniques on Antarctic surface-water and ice samples

A comparison of the new hydrogen isotope-ratio technique of Vaughn et al. ([Vaughn, B.H., White, J.W.C., Delmotte, M., Trolier, M., Cattani, O., Stievenard, M., 1998. An automated system for hydrogen isotope analysis of water. Chem. Geol. (Isot. Geosci. Sect.), 152, 309-319]; the article immediately preceding this article) for the analysis of water samples utilizing automated on-line reduction by elemental uranium showed that 94% of 165 samples of Antarctic snow, ice, and stream water agreed with the ??2H values determined by H2-H2O platinum equilibration, exhibiting a bias of +0.5??? and a 2 - ?? variation of 1.9???. The isotopic results of 10 reduction technique samples, however, gave ??2H values that differed by 3.5??? or more, and were too negative by as much as 5.4??? and too positive by as much as 4.9??? with respect to those determined using the platinum equilibration technique.

Chemical Geology↗

Data from Devils Hole Core DH-11

This report presents the stable isotope values measured in Devils Hole Core DH-11 and interpolated ages at the depth the samples were taken, as analyzed in a recent publication by Winograd and others (1997).

Nevada↗

An improved technique for the 2H/1H analysis of urines from diabetic volunteers

The H2-H2O ambient-temperature equilibration technique for the determination of 2H/1H ratios in urinary waters from diabetic subjects provides improved accuracy over the conventional Zn reduction technique. The standard deviation, ~ 1-2???, is at least a factor of three better than that of the Zn reduction technique on urinary waters from diabetic volunteers. Experiments with pure water and solutions containing glucose, urea and albumen indicate that there is no measurable bias in the hydrogen equilibration technique.The H2-H2O ambient-temperature equilibration technique for the determination of 2H/1H ratios in urinary waters from diabetic subjects provides improved accuracy over the conventional Zn reduction technique. The standard deviation, approximately 1-2%, is at least a factor of three better than that of the Zn reduction technique on urinary waters from diabetic volunteers. Experiments with pure water and solutions containing glucose, urea and albumen indicate that there is no measurable bias in the hydrogen equilibration technique.

Biological Mass Spectrometry↗

500,000-year stable carbon isotopic record from Devils Hole, Nevada

The record of carbon-13 (δ 13 C) variations in DH-11 vein calcite core from Devils Hole, Nevada, shows four prominent minima near glacial terminations (glacial-interglacial transitions) V to II. The δ 13 C time series is inversely correlated with the DH-11 oxygen isotope ratio time series and leads it by as much as 7000 years. The δ 13 C variations likely record fluctuations in the δ 13 C of dissolved inorganic carbon of water recharging the aquifer. How such variations are transported 80 kilometers to Devils Hole without obliteration by water-rock reaction remains an enigma. The record may reflect (i) global variations in the δ 13 C of atmospheric CO 2 and, hence, the δ 13 C of continental biomass or (ii) variations in extent and density of vegetation in the southern Great Basin. In the latter case, δ 13 C minima at 414, 334, 246, and 133 thousand years ago mark times of maximum vegetation.

Nevada↗

Continuous 500,000-year climate record from vein calcite in Devils Hole, Nevada

Oxygen-18 (δ 18 O) 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 δ 18 O 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.

Nevada↗