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Tyler B. Coplen

Publications and source records attributed to Tyler B. Coplen.

At least 91 records · Page 5Linked to original sources

Atomic weights of the elements 2009 (IUPAC technical report)

The biennial review of atomic-weight determinations and other cognate data has resulted in changes for the standard atomic weights of 11 elements. Many atomic weights are not constants of nature, but depend upon the physical, chemical, and nuclear history of the material. The standard atomic weights of 10 elements having two or more stable isotopes have been changed to reflect this variability of atomic-weight values in natural terrestrial materials. To emphasize the fact that these standard atomic weights are not constants of nature, each atomic-weight value is expressed as an interval. The interval is used together with the symbol [a; b] to denote the set of atomic-weight values, A r (E), of element E in normal materials for which a ≤ A r (E) ≤ b. The symbols a and b denote the bounds of the interval [a; b]. The revised atomic weight of hydrogen, A r (H), is [1.007 84; 1.008 11] from 1.007 94(7); lithium, A r (Li), is [6.938; 6.997] from 6.941(2); boron, A r (B), is [10.806; 10.821] from 10.811(7); carbon, A r (C), is [12.0096; 12.0116] from 12.0107(8); nitrogen, A r (N), is [14.006 43; 14.007 28] from 14.0067(2); oxygen, A r (O), is [15.999 03; 15.999 77] from 15.9994(3); silicon, A r (Si), is [28.084; 28.086] from 28.0855(3); sulfur, A r (S), is [32.059; 32.076] from 32.065(2); chlorine, A r (Cl), is [35.446; 35.457] from 35.453(2); and thallium, A r (Tl), is [204.382; 204.385] from 204.3833(2). This fundamental change in the presentation of the atomic weights represents an important advance in our knowledge of the natural world and underscores the significance and contributions of chemistry to the well-being of humankind in the International Year of Chemistry 2011. The standard atomic weight of germanium, A r (Ge), was also changed to 72.63(1) from 72.64(1).

Pure and Applied Chemistry↗

Caution on the use of liquid nitrogen traps in stable hydrogen isotope-ratio mass spectrometry

An anomalous stable hydrogen isotopic fractionation of 4 ‰ in gaseous hydrogen has been correlated with the process of adding liquid nitrogen (LN 2 ) to top off the dewar of a stainless-steel water trap on a gaseous hydrogen-water platinum equilibration system. Although the cause of this isotopic fractionation is unknown, its effect can be mitigated by (1) increasing the capacity of any dewars so that they do not need to be filled during a daily analytic run, (2) interspersing isotopic reference waters among unknowns, and (3) applying a linear drift correction and linear normalization to isotopic results with a program such as Laboratory Information Management System (LIMS) for Light Stable Isotopes. With adoption of the above guidelines, measurement uncertainty can be substantially improved. For example, the long-term (months to years) δ 2 H reproducibility (1& sigma; standard deviation) of nine local isotopic reference waters analyzed daily improved substantially from about 1‰ to 0.58 ‰. This isotopically fractionating mechanism might affect other isotope-ratio mass spectrometers in which LN 2 is used as a moisture trap for gaseous hydrogen

Analytical Chemistry↗

Applying the silver-tube introduction method for thermal conversion elemental analyses and a new δ 2 H value for NBS 22 oil

The δ 2 H VSMOW–SLAP value of total hydrogen of the international measurement standard NBS 22 oil was determined by a new method of sealing water in silver tubes for use in a thermal conversion elemental analysis (TC/EA) reduction unit. The isotopic fractionation of water due to evaporation is virtually non-existent in this silver-tube method. A new value for the δ 2 H VSMOW–SLAP of NBS 22 oil, calibrated with isotopic reference waters, was determined to be −116.9 ± 0.8‰ (1σ and n = 31).

Rapid Communications in Mass Spectrometry↗

Novel silver tubing method for quantitative introduction of water into high temperature conversion systems for stable hydrogen and oxygen isotopic measurements

A new method to seal water in silver tubes for use in a TC/EA reduction unit using a semi-automated sealing apparatus can yield reproducibilities (1 standard deviation) of δ 2 H and &delta 18 O measurements of 1.0 ‰ and 0.06 ‰, respectively. These silver tubes containing reference waters may be preferred for calibration of H- and O-bearing materials analyzed with a TC/EA reduction unit. The new sealing apparatus employs a computer controlled stepping motor to produce silver tubes identical in length. The reproducibility of mass of water sealed in tubes (in a range of 200 to 400 µg) can be as good as 1 percent. Although silver tubes sealed with reference waters are robust and can be shaken or heated to 110 °C with no loss of integrity, they should not be frozen because the expansion during the phase transition of water to ice will break the cold seals and all water will be lost. They should be shipped in insulated containers. This new method eliminates air inclusions and isotopic fractionation of water associated with the loading of water into capsules using a syringe. The method is also more than an order of magnitude faster than preparing water samples in ordinary Ag capsules. Nevertheless, some laboratories may prefer loading water into silver capsules because expensive equipment is not needed, but they are cautioned to apply the necessary corrections for evaporation, back exchange with laboratory atmospheric moisture, and blank.

Rapid Communications in Mass Spectrometry↗

Correction for the 17O interference in δ(13C) measurements when analyzing CO2 with stable isotope mass spectrometry

Measurements of δ( 13 C) determined on CO 2 with an isotope-ratio mass spectrometer (IRMS) must be corrected for the amount of 17 O in the CO 2 . For data consistency, this must be done using identical methods by different laboratories. This report aims at unifying data treatment for CO 2 IRMS by proposing (i) a unified set of numerical values, and (ii) a unified correction algorithm, based on a simple, linear approximation formula. Because the oxygen of natural CO 2 is derived mostly from the global water pool, it is recommended that a value of 0.528 be employed for the factor λ, which relates differences in 17 O and 18 O abundances. With the currently accepted N( 13 C)/N( 12 C) of 0.011 180(28) in VPDB (Vienna Peedee belemnite) reevaluation of data yields a value of 0.000 393(1) for the oxygen isotope ratio N( 17 O)/N( 16 O) of the evolved CO 2 . The ratio of these quantities, a ratio of isotope ratios, is essential for the 17 O abundance correction: [N( 17 O)/N( 16 O)]/[N( 13 C)/N( 12 C)] = 0.035 16(8). The equation [δ( 13 C) ≈ 45 δ VPDB-CO2 + 2 17 R/ 13 R ( 45 δ VPDB-CO2 – λ 46 δ VPDB-CO2 )] closely approximates δ( 13 C) values with less than 0.010 ‰ deviation for normal oxygen-bearing materials and no more than 0.026 ‰ in extreme cases. Other materials containing oxygen of non-mass-dependent isotope composition require a more specific data treatment. A similar linear approximation is also suggested for δ( 18 O). The linear approximations are easy to implement in a data spreadsheet, and also help in generating a simplified uncertainty budget.

Pure and Applied Chemistry↗

Isotope reference materials

Measurement of the same isotopically homogeneous sample by any laboratory worldwide should yield the same isotopic composition within analytical uncertainty. International distribution of light element isotopic reference materials by the International Atomic Energy Agency and the U.S. National Institute of Standards and Technology enable laboratories to achieve this goal.

Book chapter↗

The stable isotope amount effect: New insights from NEXRAD echo tops, Luquillo Mountains, Puerto Rico

The stable isotope amount effect has often been invoked to explain patterns of isotopic composition of rainfall in the tropics. This paper describes a new approach, correlating the isotopic composition of precipitation with cloud height and atmospheric temperature using NEXRAD radar echo tops, which are a measure of the maximum altitude of rainfall within the clouds. The seasonal differences in echo top altitudes and their corresponding temperatures are correlated with the isotopic composition of rainfall. These results offer another factor to consider in interpretation of the seasonal variation in isotopic composition of tropical rainfall, which has previously been linked to amount or rainout effects and not to temperature effects. Rain and cloud water isotope collectors in the Luquillo Mountains in northeastern Puerto Rico were sampled monthly for three years and precipitation was analyzed for δ 18 O and δ 2 H. Precipitation enriched in 18 O and 2 H occurred during the winter dry season (approximately December–May) and was associated with a weather pattern of trade wind showers and frontal systems. During the summer rainy season (approximately June–November), precipitation was depleted in 18 O and 2 H and originated in low pressure systems and convection associated with waves embedded in the prevailing easterly airflow. Rain substantially depleted in 18 O and 2 H compared to the aforementioned weather patterns occurred during large low pressure systems. Weather analysis showed that 29% of rain input to the Luquillo Mountains was trade wind orographic rainfall, and 30% of rainfall could be attributed to easterly waves and low pressure systems. Isotopic signatures associated with these major climate patterns can be used to determine their influence on streamflow and groundwater recharge and to monitor possible effects of climate change on regional water resources.

Water Resources Research↗

Comprehensive inter-laboratory calibration of reference materials for δ18O 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) 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‰, an artificially enriched reference water ( δ 18 O of +78.91‰) and two barium sulfates (one depleted and one enriched in 18 O) were prepared and calibrated relative to VSMOW2 and SLAP reference waters. These materials were used to calibrate the other isotopic reference materials in this study, which yielded: Reference material δ 18 O and estimated combined uncertainty IAEA-602 benzoic acid +71.28 ± 0.36‰ USGS35 sodium nitrate +56.81 ± 0.31‰ IAEA-NO-3 potassium nitrate +25.32 ± 0.29‰ IAEA-601 benzoic acid +23.14 ± 0.19‰ IAEA-SO-5 barium sulfate +12.13 ± 0.33‰ NBS 127 barium sulfate +8.59 ± 0.26‰ VSMOW2 water 0‰ IAEA-600 caffeine −3.48 ± 0.53‰ IAEA-SO-6 barium sulfate −11.35 ± 0.31‰ USGS34 potassium nitrate −27.78 ± 0.37‰ SLAP water −55.5‰ 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 δ 18 O should be analyzed with internationally distributed isotopic nitrates, and likewise for sulfates and organics. Authors reporting relative differences of oxygen-isotope ratios ( δ 18 O) of nitrates, sulfates, or organic material should explicitly state in their reports the δ 18 O values of two or more internationally distributed nitrates (USGS34, IAEA-NO-3, and USGS35), 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 δ 18 O values at a later time should it become necessary. The high-temperature reduction technique for analyzing δ 18 O and δ 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.

Rapid Communications in Mass Spectrometry↗

Reporting of nitrogen-isotope abundances (Technical Report)

To eliminate possible confusion in the reporting of nitrogen-isotope analyses, the Commission on Atomic Weights and Isotopic Abundances recommends that the value 272 be employed for the 14 N/ 15 N value of N 2 in air for calculating atom percent 15 N from measured δ 15 N values.

Pure and Applied Chemistry↗

Determination of the delta(2H/1H)of Water: RSIL Lab Code 1574

Reston Stable Isotope Laboratory (RSIL) lab code 1574 describes a method used to determine the relative hydrogen isotope-ratio delta(2H,1H), abbreviated hereafter as d2H of water. The d2H measurement of water also is a component of the National Water Quality Laboratory (NWQL) schedules 1142 and 1172. The water is collected unfiltered in a 60-mL glass bottle and capped with a Polyseal cap. In the laboratory, the water sample is equilibrated with gaseous hydrogen using a platinum catalyst (Horita, 1988; Horita and others, 1989; Coplen and others, 1991). The reaction for the exchange of one hydrogen atom is shown in equation 1.

Techniques and Methods↗

Determination of the δ 15 N of nitrate in solids; RSIL lab code 2894

The purpose of the Reston Stable Isotope Laboratory (RSIL) lab code 2894 is to determine the δ 15 N of nitrate (NO 3 - ) in solids. The nitrate fraction of the nitrogen species is dissolved by water (called leaching) and can be analyzed by the bacterial method covered in RSIL lab code 2899. After leaching, the δ 15 N of the dissolved NO 3 - is analyzed by conversion of the NO 3 - to nitrous oxide (N 2 O), which serves as the analyte for mass spectrometry. A culture of denitrifying bacteria is used in the enzymatic conversion of NO 3 - to N 2 O, which follows the pathway shown in equation 1: NO 3 - → NO 2 - → NO → 1/2 N 2 O (1) Because the bacteria Pseudomonas aureofaciens lack N 2 O reductive activity, the reaction stops at N 2 O, unlike the typical denitrification reaction that goes to N 2 . After several hours, the conversion is complete, and the N 2 O is extracted from the vial, separated from volatile organic vapor and water vapor by an automated -65 °C isopropanol-slush trap, a Nafion drier, a CO 2 and water removal unit (Costech #021020 carbon dioxide absorbent with Mg(ClO 4 ) 2 ), and trapped in a small-volume trap immersed in liquid nitrogen with a modified Finnigan MAT (now Thermo Scientific) GasBench 2 introduction system. After the N 2 O is released, it is further purified by gas chromatography before introduction to the isotope-ratio mass spectrometer (IRMS). The IRMS is a Thermo Scientific Delta V Plus continuous flow IRMS (CF-IRMS). It has a universal triple collector, consisting of two wide cups with a narrow cup in the middle; it is capable of simultaneously measuring mass/charge ( m/z ) of the N 2 O molecule 44, 45, and 46. The ion beams from these m/z values are as follows: m/z = 44 = N 2 O = 14 N 14 N 16 O; m/z = 45 = N 2 O = 14 N 15 N 16 O or 14 N 14 N 17 O; m/z = 46 = N 2 O = 14 N 14 N 18 O. The 17 O contributions to the m/z 44 and m/z 45 ion beams are accounted for before δ 15 N values are reported.

Techniques and Methods↗

Determination of the δ 15 N and δ 18 O of nitrate in solids; RSIL lab code 2897

The purpose of the Reston Stable Isotope Laboratory (RSIL) lab code 2897 is to determine the δ 15 N and δ 18 O of nitrate (NO 3 - ) in solids. The NO 3 - fraction of the nitrogen species is dissolved by water (called leaching) and can be analyzed by the bacterial method covered in RSIL lab code 2900. After leaching, the δ 15 N and δ 18 O of the dissolved NO 3 - is analyzed by conversion of the NO 3 - to nitrous oxide (N 2 O), which serves as the analyte for mass spectrometry. A culture of denitrifying bacteria is used in the enzymatic conversion of NO 3 - to N 2 O, which follows the pathway shown in equation 1: NO 3 - → NO 2 - → NO → 1/2 N 2 O (1) Because the bacteria Pseudomonas aureofaciens lack N 2 O reductive activity, the reaction stops at N 2 O, unlike the typical denitrification reaction that goes to N 2 . After several hours, the conversion is complete, and the N 2 O is extracted from the vial, separated from volatile organic vapor and water vapor by an automated -65 °C isopropanol-slush trap, a Nafion drier, a CO 2 and water removal unit (Costech #021020 carbon dioxide absorbent with Mg(ClO 4 ) 2 ), and trapped in a small-volume trap immersed in liquid nitrogen with a modified Finnigan MAT (now Thermo Scientific) GasBench 2 introduction system. After the N 2 O is released, it is further purified by gas chromatography before introduction to the isotope-ratio mass spectrometer (IRMS). The IRMS is a Thermo Scientific Delta V Plus continuous flow IRMS (CF-IRMS). It has a universal triple collector, consisting of two wide cups with a narrow cup in the middle; it is capable of simultaneously measuring mass/charge ( m/z ) of the N 2 O molecule 44, 45, and 46. The ion beams from these m/z values are as follows: m/z = 44 = N 2 O = 14 N 14 N 16 O; m/z = 45 = N 2 O = 14 N 15 N 16 O or 14 N 14 N 17 O; m/z = 46 = N 2 O = 14 N 14 N 18 O. The 17 O contributions to the m/z 44 and m/z 45 ion beams are accounted for before δ 15 N values are reported.

Techniques and Methods↗

Determination of the δ 15 N of nitrate in water; RSIL lab code 2899

The purpose of the Reston Stable Isotope Laboratory (RSIL) lab code 2899 is to determine the δ 15 N of nitrate (NO 3 - ) in water. The δ 15 N of the dissolved NO 3 - is analyzed by conversion of the NO 3 - to nitrous oxide (N 2 O), which serves as the analyte for mass spectrometry. A culture of denitrifying bacteria is used in the enzymatic conversion of the NO 3 - to N 2 O, which follows the pathway shown in equation 1: NO 3 - → NO 2 - → NO → 1/2 N 2 O (1) Because the bacteria Pseudomonas aureofaciens lack N 2 O reductive activity, the reaction stops at N 2 O, unlike the typical denitrification reaction that goes to N 2 . After several hours, the conversion is complete, and the N 2 O is extracted from the vial, separated from volatile organic vapor and water vapor by an automated -65 °C isopropanol-slush trap, a Nafion drier, a CO 2 and water removal unit (Costech #021020 carbon dioxide absorbent with Mg(ClO 4 ) 2 ), and trapped in a small-volume trap immersed in liquid nitrogen with a modified Finnigan MAT (now Thermo Scientific) GasBench 2 introduction system. After the N 2 O is released, it is further purified by gas chromatography before introduction to the isotope-ratio mass spectrometer (IRMS). The IRMS is a Thermo Scientific Delta V Plus continuous flow IRMS (CF-IRMS). It has a universal triple collector, consisting of two wide cups with a narrow cup in the middle; it is capable of simultaneously measuring mass/charge ( m/z ) of the N 2 O molecule 44, 45, and 46. The ion beams from these m/z values are as follows: m/z = 44 = N 2 O = 14 N 14 N 16 O; m/z = 45 = N 2 O = 14 N 15 N 16 O or 14 N 14 N 17 O; m/z = 46 = N 2 O = 14 N 14 N 18 O. The 17 O contributions to the m/z 44 and m/z 45 ion beams are accounted for before δ 15 N values are reported.

Techniques and Methods↗

Determination of the δ 15 N and δ 18 O of nitrate in water; RSIL lab code 2900

The purpose of the Reston Stable Isotope Laboratory (RSIL) lab code 2900 is to determine the δ 15 N and δ 18 O of nitrate (NO 3 - ) in water. The δ 15 N and δ 18 O of the dissolved NO 3 - are analyzed by converting the NO 3 - to nitrous oxide (N 2 O), which serves as the analyte for mass spectrometry. A culture of denitrifying bacteria is used in the enzymatic conversion of the NO 3 - to N 2 O, which follows the pathway shown in equation 1: NO 3 - → NO 2 - → NO → 1/2 N 2 O (1) Because the bacteria Pseudomonas aureofaciens lack N 2 O reductive activity, the reaction stops at N 2 O, unlike the typical denitrification reaction that goes to N 2 . After several hours, the conversion is complete, and the N 2 O is extracted from the vial, separated from volatile organic vapor and water vapor by an automated -65 °C isopropanol-slush trap, a Nafion drier, a CO 2 and water removal unit (Costech #021020 carbon dioxide absorbent with Mg(ClO 4 ) 2 ), and trapped in a small-volume trap immersed in liquid nitrogen with a modified Finnigan MAT (now Thermo Scientific) GasBench 2 introduction system. After the N 2 O is released, it is further purified by gas chromatography before introduction to the isotope-ratio mass spectrometer (IRMS). The IRMS is a Thermo Scientific Delta V Plus continuous flow IRMS (CF-IRMS). It has a universal triple collector, consisting of two wide cups with a narrow cup in the middle; it is capable of simultaneously measuring mass/charge ( m/z ) of the N 2 O molecule 44, 45, and 46. The ion beams from these m/z values are as follows: m/z = 44 = N 2 O = 14 N 14 N 16 O; m/z = 45 = N 2 O = 14 N 15 N 16 O or 14 N 14 N 17 O; m/z = 46 = N 2 O = 14 N 14 N 18 O. The 17 O contributions to the m/z 44 and m/z 45 ion beams are accounted for before δ 15 N values are reported.

Techniques and Methods↗

New guidelines for δ 13 C measurements

Consistency of δ 13 C measurements can be improved 39−47% by anchoring the δ 13 C scale with two isotopic reference materials differing substantially in 13 C/ 12 C. It is recommended that δ 13 C values of both organic and inorganic materials be measured and expressed relative to VPDB (Vienna Peedee belemnite) on a scale normalized by assigning consensus values of −46.6‰ to L-SVEC lithium carbonate and +1.95‰ to NBS 19 calcium carbonate. Uncertainties of other reference material values on this scale are improved by factors up to two or more, and the values of some have been notably shifted:  the δ 13 C of NBS 22 oil is −30.03%.

Analytical Chemistry↗

Determination of the δ 34 S of sulfate in water; RSIL lab code 1951

The purpose of the Reston Stable Isotope Laboratory (RSIL) lab code 1951 is to determine the δ( 34 S/ 32 S), abbreviated as δ 34 S, of dissolved sulfate. Dissolved sulfate is collected in the field and precipitated with BaCl 2 at pH 3 to 4 as BaSO 4 in the laboratory. However, the dissolved organic sulfur (DOS) is oxidized to SO 2 , and the carbonate is acidified to CO 2 . Both are degassed from the water sample before the sulfate is precipitated. The precipitated BaSO 4 is filtered and dried before introduction into an elemental analyzer (EA) Carlo Erba NC 2500. The EA is used to convert sulfur in a BaSO 4 solid sample into SO 2 gas, and the EA is connected to a continuous flow isotope-ratio mass spectrometer (CF-IRMS), which determines the differences in the isotope-amount ratios of stable sulfur isotopes ( 34 S/ 32 S) of the product SO 2 gas. The combustion is quantitative; no isotopic fractionation is involved. Samples are placed in a tin capsule and loaded into the Costech Zero Blank Autosampler of the EA. Under computer control, samples are dropped into a heated tube reaction tube that combines the oxidation and reduction reactions. The combustion takes place in a helium atmosphere containing an excess of oxygen gas at the oxidation zone at the top of the reaction tube. Combustion products are transported by a helium carrier through the reduction zone at the bottom of the reaction tube to remove excess oxygen and through a separate drying tube to remove any water. The gas-phase products, mainly CO 2 , N 2 , and SO 2 , are separated by a gas chromatograph. The gas is then introduced into the isotope-ratio mass spectrometer (IRMS) through a Finnigan MAT (now Thermo Scientific) ConFlo II interface, which also is used to inject SO 2 reference gas and helium for sample dilution. The IRMS is a Thermo Scientific Delta V Plus CF-IRMS. It has a universal triple collector with two wide cups and a narrow cup in the middle. It is capable of measuring mass/charge ( m/z ) 64 and 66 simultaneously. The ion beams from SO 2 are as follows: m/z 64 = SO 2 = 32 S 16 O 16 O; m/z 66 = SO 2 = 34 S 16 O 16 O primarily.

Techniques and Methods↗