Geology topics

Haiping Qi

Publications and source records attributed to Haiping Qi.

At least 19 recordsLinked to original sources

USGS2026

Reaffirming the consistency of the original stock of NBS 19 limestone and its byproduct with finer grain size for δ13C and δ18O calibrations—Both distributed internationally

Rationale Approximately 3–4 kg of NBS 19 limestone, prepared in 1982 by the U.S. Geological Survey (USGS), serves as a primary reference for the carbon isotope scales VPDB and VPDB-LSVEC and the oxygen isotope scale VPDB. Its consensus values are +1.95‰ for δ 13 C and −2.2‰ for δ 18 O measurements. After more than three decades of distribution, the number of units labeled “NBS 19” shrunk substantially, and the remaining material was quarantined, with a small fraction retained at the USGS and a larger fraction entrusted to the International Atomic Energy Agency (IAEA) for secure storage. Given the critical role of NBS 19, verifying the integrity of its δ 13 C and δ 18 O values across these storage locations is essential. Method Samples from IAEA and USGS stock materials were selected to ensure traceability of carbon and oxygen isotopes to NBS 19 distribution units from various storage locations. To achieve this, distribution units labeled as NBS 19 from both the IAEA and the National Institute of Standards and Technology (NIST) were included. During evaluation, two distinct grain sizes were identified within these units. Grain size was assessed using sieves on five selected samples. The δ 13 C and δ 18 O values of finer and coarser fractions (both labeled NBS 19) were measured at USGS using continuous-flow isotope-ratio mass spectrometry on 100- and 200-μg samples. Results Expanded 95% measurement uncertainties ( k = 2) for δ 13 C and δ 18 O determinations are 0.027‰ and 0.038‰ or better, respectively, for quarantined NBS 19 stocks and finer byproduct calcite, which we term “NBS-19 byproduct,” regardless of storage location. Between the 1990s and circa 2011, NBS-19 byproduct labeled “NBS 19,” distributed by NIST and the IAEA, shows these findings. Conclusions NBS 19 primary isotopic reference material should be used for calibration of new isotopic reference materials rather than NBS-19 byproduct secondary isotopic reference material.

Rapid Communications in Mass Spectrometry↗

USGS2026

Three new calcium formate reference materials for δ13C measurements and a redetermination of the R(13C/12C) ratio for VPDB based on proton nuclear magnetic resonance measurements

Rationale Isotope ratio mass spectrometry (IRMS) and proton nuclear magnetic resonance ( 1 H NMR) spectroscopy are independent techniques for determining the isotope ratio R ( 13 C/ 12 C) in organic compounds. However, the lack of suitable reference materials has limited intercalibration of results from these methods. Methods Three high-purity calcium formate isotopic reference materials were developed, each ideal for accurate isotope ratio measurements by both 1 H NMR and isotope-ratio mass spectrometry (IRMS). For each material, R ( 13 C/ 12 C) was determined by 1 H NMR, and the relative isotope abundance ( δ 13 C VPDB-LSVEC ) by IRMS. The combined IRMS and NMR results were used to determine the R ( 13 C/ 12 C) value of Vienna Peedee belemnite (VPDB). Results The combined datasets yield a value for R ( 13 C/ 12 C) of 0.0111050 ± 0.0000047 ( k = 2) for VPDB, which is 6.7‰ lower than the commonly cited value of 0.011180, but similar to other recent determinations. These three calcium formate reference materials exhibit high accuracy across both analytical methods and provide robust tools for instrument calibration, method validation, and inter-laboratory comparison in carbon stable isotope ratio analysis. Conclusions An accurate R ( 13 C/ 12 C) value for VPDB strengthens the link between relative ( δ 13 C VPDB-LSVEC ) values from IRMS and R ( 13 C/ 12 C) isotope ratios from NMR and other techniques. These three calcium formate isotopic reference materials (USGS106, USGS107, and USGS108) are available from the US Geological Survey and provide reference materials for calibration, method validation, and inter-laboratory comparison in carbon isotope ratio analysis.

Rapid Communications in Mass Spectrometry↗

USGS2026

Rhyolitic and basaltic reference materials for TC/EA analysis: Investigation of water extraction and D/H ratios

Increasingly, water and D/H ratios of silicic and basaltic glasses are used to investigate magmatic degassing and secondary hydration, as well as for study these parameters in the mantle and crustal magmas. The advent of the High Temperature Conversion Element Analyzer (TC/EA) continuous flow mass spectrometry made the determination of hydrogen isotopes relatively quick and precise (±0.04 wt% H 2 O and 1–3‰ δ 2 H). Many labs around the world have such systems, thus there is a need to develop both silicic and basaltic volcanic glass reference materials (RMs) that can be used for interlaboratory comparison by bulk and microanalytical methods. Here, we report results of such investigation run against solid RMs (USGS micas) and water RMs (including VSMOW) in three different labs and describe analytical protocols. We report on the effects of glass size fraction, the mass of aliquots measured, and yield dependency for two glasses: UOR (drill cutting of IDDP-1 rhyolite, Iceland) and UOB (an E -MORB basalt from the East Pacific Rise). Proposed RM values are: UOB rhyolitic glass ( n = 31): H 2 O = 1.84 ± 0.06 wt% (1 s.d.), and δ 2 H = −115.5 ± 2.6‰ (1 s.d.). UOB basaltic glass ( n = 60): H 2 O = 0.37 ± 0.03 wt% (1 s.d.), and δ 2 H = −82.1 ± 5.7‰ (1 s.d.). Glass reference materials are available in 100 mg quantities from the Stable Isotope Laboratory at the University of Oregon for a nominal fee.

Chemical Geology↗

USGS2025

Correction to “Stable isotope reference materials and scale definitions – outcomes of the 2024 IAEA experts meeting”

This article corrects the following: Camin, F., Besic, D., Brewer, P., Allison, C., Coplen, T., Dunn, P., Gehre, M., Gröning, M., Meijer, H.-A.-J, Hélie, J.-F., Iacumin, P., Kraft, R., Krajnc, B., Kümmel, S., Lee, S., Meija, J., Mester, Z., Mohn, J., Moossen, H., Qi, H., Skrzypek, G., Sperlich, P., Viallon, J., Wassenaar, L. and Wielgosz, R. (2025). Stable Isotope Reference Materials and Scale Definitions—Outcomes of the 2024 IAEA Experts Meeting. Rapid Commun Mass Spectrom, 39: e10018, https://doi.org/10.1002/rcm.10018. In the above article, the text of note 3 in Section 4.2 is incorrect. The correct text is shown below: 3. Whilst limited amounts of the original VSMOW and SLAP scale-defining reference materials may still be available, to enable continuous wide distribution of RMs for VSMOW-SLAP scale realization (normalization, calibration) the scale-maintaining reference materials VSMOW2 and SLAP2 are available. VSMOW2 and SLAP2 have δ(18O) values identical to VSMOW and SLAP, respectively, but with an uncertainty with respect to VSMOW and SLAP. We apologize for this error. The CIAAW-IUPAC endorsed all isotope delta scale definitions appearing in Camin et al. (2025) and agreed to publish the current and all future updates and corrections to these definitions on its website (www.ciaaw.org).

Rapid Communications in Mass Spectrometry↗

USGS2025

Isotopic compositions of modern seawater at the Mariana and Yap trenches

The isotopic composition of ocean water is crucial in studying water masses and mixing in deep oceans, isotope mass balance in ocean water regulated by high-temperature and low-temperature hydrothermal alterations, and the exchange of water among crust-ocean-mantle reservoirs. We collected 40 water samples from Challenger Deep and the water column above at the Mariana Trench (down to 10,923 m) and 12 from the Yap Trench (down to 6,300 m) in the western Pacific Ocean in three hadal cruises from 2016 to 2018. The δ 2 H values at the Mariana and Yap Trenches average 0.1 ± 0.2 ‰ (1σ error). The δ 2 H records from this study, together with existing databases, manifest that deep waters have δ 2 H values varying between −2 and +2 ‰ (except for the Weddell Sea, the Greenland, Iceland, and Norwegian Seas, and the Mediterranean Sea), with increasing values from the Southern Ocean to the Pacific and Indian Oceans, and to the Atlantic Ocean. The average δ 18 O value of water samples from both trenches is –0.04 ± 0.03 ‰ (1σ error). The correlation between δ 18 O and salinity distinguishes abyssal water masses at the study region, UCDW (Upper Circumpolar Deep Water) and LCDW (Lower Circumpolar Deep Water). These water samples from the Mariana and Yap Trenches gave an average 17 O excess value of −6 ± 1 ppm (1σ error). Our 52 data records of 17 O excess expand the 38 existing records for the deep ocean. Both δ 2 H and 17 O excess of modern ocean have rolled as anchor points to reconstruct compositions of Earth’s early ocean.

ACS Earth and Space Chemistry↗

USGS2025

Stable isotope reference materials and scale definitions – Outcomes of the 2024 IAEA experts meeting

The participants of the 12 th International Atomic Energy Agency (IAEA) meeting on stable isotope reference materials reached a consensus, acknowledging the existence and use of two carbon isotope delta scales: the VPDB (Vienna Peedee belemnite) scale and the VPDB-LSVEC (LSVEC - lithium carbonate prepared by H. J. Svec). Conversion models between the two scales can be established and used but introduce uncertainty. A format for isotope delta scale definition was agreed upon and was used to define the two carbon isotope delta scales and the two main oxygen isotope delta scales, VSMOW-SLAP (Vienna Standard Mean Ocean Water–Standard Light Antarctic Precipitation) and VPDB. Confirmation or identification of a second-scale–defining point is still necessary for the nitrogen and sulfur isotope delta scales. Efforts are encouraged to improve consistency among laboratories in the isotopic analysis of “non-exchangeable hydrogen” in bulk organic materials and oxygen in carbonates using the phosphoric acid reaction. Additional topics discussed include (1) need for improvement in reference materials for accurate greenhouse gas isotopic analyses; (2) reference materials under production by the IAEA, the US Geological Survey (USGS), and the US National Institute of Standards and Technology (NIST); (3) methods for value and uncertainty assignment of reference materials; and (4) calculation of carbon-13 isotope delta and oxygen-18 isotope delta of CO 2 measured by dual-inlet isotope ratio mass spectrometry.

Rapid Communications in Mass Spectrometry↗

USGS2022

Final report on pilot study CCQM-P211: Carbon isotope delta measurements of vanillin

This pilot study was conducted in parallel to the key comparison CCQM-K167. Vials containing 0.25 mg of vanillin were prepared at NRC and distributed to four participating institutes. Institutes could choose any suitable reference materials and methodology to perform carbon isotope delta measurements. Participants reported analysis details, and a carbon isotope delta value and associated uncertainty for the vanillin sample. Each of the carbon isotope delta results of vanillin were compared to the KCRV established from CCQM-K167, and metrological compatibility to the KCRV was determined. Three expert laboratories participated in this study, and their reported results serve as a benchmark to compare the performance of all other participants to these world-class institutes.

Metrologia↗

USGS2021

USGS44, a new high-purity calcium carbonate reference material for δ13C measurements

Rationale The stable carbon isotopic ( δ 13 C) reference material (RM) LSVEC Li 2 CO 3 has been found to be unsuitable for δ 13 C standardization work because its δ 13 C value increases with exposure to atmospheric CO 2 . A new CaCO 3 RM, USGS44, has been prepared to alleviate this situation. Methods USGS44 was prepared from 8 kg of Merck high-purity CaCO 3 . Two sets of δ 13 C values of USGS44 were determined. The first set of values was determined by online combustion, continuous-flow (CF) isotope-ratio mass spectrometry (IRMS) of NBS 19 CaCO 3 ( δ 13 C VPDB = +1.95 milliurey (mUr) exactly, where mUr = 0.001 = 1‰), and LSVEC Li 2 CO 3 ( δ 13 C VPDB = −46.6 mUr exactly), and normalized to the two-anchor δ 13 C VPDB-LSVEC isotope-delta scale. The second set of values was obtained by dual-inlet (DI)-IRMS of CO 2 evolved by reaction of H 3 PO 4 with carbonates, corrected for cross contamination, and normalized to the single-anchor δ 13 C VPDB scale. Results USGS44 is stable and isotopically homogeneous to within 0.02 mUr in 100-μg amounts. It has a δ 13 C VPDB-LSVEC value of −42.21 ± 0.05 mUr. Single-anchor δ 13 C VPDB values of −42.08 ± 0.01 and −41.99 ± 0.02 mUr were determined by DI-IRMS with corrections for cross contamination. Conclusions The new high-purity, well-homogenized calcium carbonate isotopic reference material USGS44 is stable and has a δ 13 C VPDB-LSVEC value of −42.21 ± 0.05 mUr for both EA/IRMS and DI-IRMS measurements. As a carbonate relatively depleted in 13 C, it is intended for daily use as a secondary isotopic reference material to normalize stable carbon isotope delta measurements to the δ 13 C VPDB-LSVEC scale. It is useful in quantifying drift with time, determining mass-dependent isotopic fractionation (linearity correction), and adjusting isotope-ratio-scale contraction. Due to its fine grain size (smaller than 63 μm), it is not suitable as a δ 18 O reference material. A δ 13 C VPDB-LSVEC value of −29.99 ± 0.05 mUr was determined for NBS 22 oil.

Rapid Communications in Mass Spectrometry↗

USGS2020

Food matrix reference materials for hydrogen, carbon, nitrogen, oxygen, and sulfur stable isotope-ratio measurements: Collagens, flours, honeys, and vegetable oils

An international project developed, quality-tested, and measured isotope–delta values of 10 new food matrix reference materials (RMs) for hydrogen, carbon, nitrogen, oxygen, and sulfur stable isotope-ratio measurements to support food authenticity testing and food provenance verification. These new RMs, USGS82 to USGS91, will enable users to normalize measurements of samples to isotope–delta scales. The RMs include (i) two honeys from Canada and tropical Vietnam, (ii) two flours from C3 (rice) and C4 (millet) plants, (iii) four vegetable oils from C3 (olive, peanut) and C4 (corn) plants, and (iv) two collagen powders from marine fish and terrestrial mammal origins. An errors-in-variables regression model included the uncertainty associated with the measured and assigned values of the RMs, and it was applied centrally to normalize results and obtain consensus values and measurement uncertainties. Utilization of these new RMs should facilitate mutual compatibility of stable isotope data if accepted normalization procedures are applied and documented.

Journal of Agricultural and Food Chemistry↗

USGS2017

Weathering of oil in a surficial aquifer

The composition of crude oil in a surficial aquifer was determined in two locations at the Bemidji, MN, spill site. The abundances of 71 individual hydrocarbons varied within 16 locations sampled. Little depletion of these hydrocarbons (relative to the pipeline oil) occurred in the first 10 years after the spill, whereas losses of 25% to 85% of the total measured hydrocarbons occurred after 30 years. The C 6‐30 n ‐alkanes, toluene, and o ‐xylene were the most depleted hydrocarbons. Some hydrocarbons, such as the n‐ C 10–24 cyclohexanes, tri‐ and tetra‐ methylbenzenes, acyclic isoprenoids, and naphthalenes were the least depleted. Benzene was detected at every sampling location 30 years after the spill. Degradation of the oil led to increases in the percent organic carbon and in the δ 13 C of the oil. Another method of determining hydrocarbon loss was by normalizing the total measured hydrocarbon concentrations to that of the most conservative analytes. This method indicated that the total measured hydrocarbons were depleted by 47% to 77% and loss of the oil mass over 30 years was 18% to 31%. Differences in hydrocarbon depletion were related to the depth of the oil in the aquifer, local topography, amount of recharge reaching the oil, availability of electron acceptors, and the presence of less permeable soils above the oil. The results from this study indicate that once crude oil has been in the subsurface for a number of years there is no longer a “starting oil concentration” that can be used to understand processes that affect its fate and the transport of hydrocarbons in groundwater.

Minnesota↗

USGS2017

Optimization of on-line hydrogen stable isotope ratio measurements of halogen- and sulfur-bearing organic compounds using elemental analyzer–chromium/high-temperature conversion isotope ratio mass spectrometry (EA-Cr/HTC-IRMS)

Rationale: Accurate hydrogen isotopic analysis of halogen- and sulfur-bearing organics has not been possible with traditional high-temperature conversion (HTC) because the formation of hydrogen-bearing reaction products other than molecular hydrogen (H2) is responsible for non-quantitative H2 yields and possible hydrogen isotopic fractionation. Our previously introduced, new chromium-based EA-Cr/HTC-IRMS (Elemental Analyzer–Chromium/High-Temperature Conversion Isotope Ratio Mass Spectrometry) technique focused primarily on nitrogen-bearing compounds. Several technical and analytical issues concerning halogen- and sulfur-bearing samples, however, remained unresolved and required further refinement of the reactor systems. Methods: The EA-Cr/HTC reactor was substantially modified for the conversion of halogen- and sulfur-bearing samples. The performance of the novel conversion setup for solid and liquid samples was monitored and optimized using a simultaneously operating dual-detection system of IRMS and ion trap MS. The method with several variants in the reactor, including the addition of manganese metal chips, was evaluated in three laboratories using EA-Cr/HTC-IRMS (on-line method) and compared with traditional uranium-reduction-based conversion combined with manual dual-inlet IRMS analysis (off-line method) in one laboratory. Results: The modified EA-Cr/HTC reactor setup showed an overall H2-recovery of more than 96% for all halogen- and sulfur-bearing organic compounds. All results were successfully normalized via two-point calibration with VSMOW-SLAP reference waters. Precise and accurate hydrogen isotopic analysis was achieved for a variety of organics containing F-, Cl-, Br-, I-, and S-bearing heteroelements. The robust nature of the on-line EA-Cr/HTC technique was demonstrated by a series of 196 consecutive measurements with a single reactor filling. Conclusions: The optimized EA-Cr/HTC reactor design can be implemented in existing analytical equipment using commercially available material and is universally applicable for both heteroelement-bearing and heteroelement-free organic-compound classes. The sensitivity and simplicity of the on-line EA-Cr/HTC-IRMS technique provide a much needed tool for routine hydrogen-isotope source tracing of organic contaminants in the environment. Copyright © 2016 John Wiley & Sons, Ltd.

Rapid Communications in Mass Spectrometry↗

USGS2017

New biotite and muscovite isotopic reference materials, USGS57 and USGS58, for δ2H measurements–A replacement for NBS 30

The advent of continuous-flow isotope-ratio mass spectrometry (CF-IRMS) coupled with a high temperature conversion (HTC) system enabled faster, more cost effective, and more precise δ 2 H analysis of hydrogen-bearing solids. Accurate hydrogen isotopic analysis by on-line or off-line techniques requires appropriate isotopic reference materials (RMs). A strategy of two-point calibrations spanning δ 2 H range of the unknowns using two RMs is recommended. Unfortunately, the supply of the previously widely used isotopic RM, NBS 30 biotite, is exhausted. In addition, recent measurements have shown that the determination of δ 2 H values of NBS 30 biotite on the VSMOW-SLAP isotope-delta scale by on-line HTC systems with CF-IRMS may be unreliable because hydrogen in this biotite may not be converted quantitatively to molecular hydrogen. The δ 2 H VSMOW-SLAP values of NBS 30 biotite analyzed by on-line HTC systems can be as much as 21 mUr (or ‰) too positive compared to the accepted value of − 65.7 mUr, determined by only a few conventional off-line measurements. To ensure accurate and traceable on-line hydrogen isotope-ratio determinations in mineral samples, we here propose two isotopically homogeneous, hydrous mineral RMs with well-characterized isotope-ratio values, which are urgently needed. The U.S. Geological Survey (USGS) has prepared two such RMs, USGS57 biotite and USGS58 muscovite. The δ 2 H values were determined by both glassy carbon-based on-line conversion and chromium-based on-line conversion, and results were confirmed by off-line conversion. The quantitative conversion of hydrogen from the two RMs using the on-line HTC method was carefully evaluated in this study. The isotopic compositions of these new RMs with 1-σ uncertainties and mass fractions of hydrogen are: USGS57 (biotite) δ 2 H VSMOW-SLAP = − 91.5 ± 2.4 mUr ( n = 24) Mass fraction hydrogen = 0.416 ± 0.002% ( n = 4) Mass fraction water = 3.74 ± 0.02% ( n = 4) USGS58 (muscovite) δ 2 H VSMOW-SLAP = − 28.4 ± 1.6 mUr ( n = 24) Mass fraction hydrogen = 0.448 ± 0.002% ( n = 4) Mass fraction water = 4.03 ± 0.02% ( n = 4). These δ 2 H VSMOW-SLAP values encompass typical ranges for solid unknowns of crustal and mantle origin and are available to users for recommended two-point calibration.

Chemical Geology↗

USGS2016

Antarctic ice-core water (USGS49) – A new isotopic reference material for δ2H and δ18O measurements of water

As a result of the scarcity of isotopic reference waters for daily use, a new secondary isotopic reference material for international distribution has been prepared from ice-core water from the Amundsen–Scott South Pole Station. This isotopic reference material, designated as USGS49, was filtered, homogenised, loaded into glass ampoules, sealed with a torch, autoclaved to eliminate biological activity and measured by dual-inlet isotope-ratio mass spectrometry. The δ 2 H and δ 18 O values of USGS49 are −394.7 ± 0.4 and −50.55 ± 0.04 mUr (where mUr = 0.001 = ‰), 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 mUr. 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 material is intended as one of two isotopic reference waters for daily normalisation of stable hydrogen and oxygen isotopic analysis of water with an isotope-ratio mass spectrometer or a laser absorption spectrometer. It is available by the case of 144 glass ampoules or as a set of sixteen glass ampoules containing 5 ml of water in each ampoule.

Geostandards and Geoanalytical Research↗

USGS2016

New organic reference materials for hydrogen, carbon, and nitrogen stable isotope-ratio measurements: caffeines, n-alkanes, fatty acid methyl esters, glycines, L-valines, polyethylenes, and oils

An international project developed, quality-tested, and determined isotope−δ values of 19 new organic reference materials (RMs) for hydrogen, carbon, and nitrogen stable isotope-ratio measurements, in addition to analyzing pre-existing RMs NBS 22 (oil), IAEA-CH-7 (polyethylene foil), and IAEA-600 (caffeine). These new RMs enable users to normalize measurements of samples to isotope−δ scales. The RMs span a range of δ 2 H VSMOW-SLAP values from −210.8 to +397.0 mUr or ‰, for δ 13 C VPDB-LSVEC from −40.81 to +0.49 mUr and for δ 15 N Air from −5.21 to +61.53 mUr. Many of the new RMs are amenable to gas and liquid chromatography. The RMs include triads of isotopically contrasting caffeines, C 16 n -alkanes, n -C 20 -fatty acid methyl esters (FAMEs), glycines, and l -valines, together with polyethylene powder and string, one n -C 17 -FAME, a vacuum oil (NBS 22a) to replace NBS 22 oil, and a 2 H-enriched vacuum oil. A total of 11 laboratories from 7 countries used multiple analytical approaches and instrumentation for 2-point isotopic normalization against international primary measurement standards. The use of reference waters in silver tubes allowed direct normalization of δ 2 H values of organic materials against isotopic reference waters following the principle of identical treatment. Bayesian statistical analysis yielded the mean values reported here. New RMs are numbered from USGS61 through USGS78, in addition to NBS 22a. Because of exchangeable hydrogen, amino acid RMs currently are recommended only for carbon- and nitrogen-isotope measurements. Some amino acids contain 13 C and carbon-bound organic 2 H-enrichments at different molecular sites to provide RMs for potential site-specific isotopic analysis in future studies.

Analytical Chemistry↗

USGS2016

A new organic reference material, L-glutamic acid, USGS41a, for δ 13 C and δ 15 N measurements − a replacement for USGS41

Rationale The widely used l -glutamic acid isotopic reference material USGS41, enriched in both 13 C and 15 N, is nearly exhausted. A new material, USGS41a, has been prepared as a replacement for USGS41. Methods USGS41a was prepared by dissolving analytical grade l -glutamic acid enriched in 13 C and 15 N together with l -glutamic acid of normal isotopic composition. The δ 13 C and δ 15 N values of USGS41a were directly or indirectly normalized with the international reference materials NBS 19 calcium carbonate ( δ 13 C VPDB = +1.95 mUr, where milliurey = 0.001 = 1 ‰), LSVEC lithium carbonate ( δ 13 C VPDB = −46.6 mUr), and IAEA-N-1 ammonium sulfate ( δ 15 N Air = +0.43 mUr) and USGS32 potassium nitrate ( δ 15 N = +180 mUr exactly) by on-line combustion, continuous-flow isotope-ratio mass spectrometry, and off-line dual-inlet isotope-ratio mass spectrometry. Results USGS41a is isotopically homogeneous; the reproducibility of δ 13 C and δ 15 N is better than 0.07 mUr and 0.09 mUr, respectively, in 200-μg amounts. It has a δ 13 C value of +36.55 mUr relative to VPDB and a δ 15 N value of +47.55 mUr relative to N 2 in air. USGS41 was found to be hydroscopic, probably due to the presence of pyroglutamic acid. Experimental results indicate that the chemical purity of USGS41a is substantially better than that of USGS41. Conclusions The new isotopic reference material USGS41a can be used with USGS40 (having a δ 13 C VPDB value of −26.39 mUr and a δ 15 N Air value of −4.52 mUr) for (i) analyzing local laboratory isotopic reference materials, and (ii) quantifying drift with time, mass-dependent isotopic fractionation, and isotope-ratio-scale contraction for isotopic analysis of biological and organic materials. Published in 2016. This article is a U.S. Government work and is in the public domain in the USA.

Rapid Communications in Mass Spectrometry↗

USGS2016

Three whole-wood isotopic reference materials, USGS54, USGS55, and USGS56, for δ2H, δ13C, δ15N, and δ18O measurements

Comparative measurements of stable hydrogen and oxygen isotopes in wood are hampered by the lack of proper reference materials (RMs). The U.S. Geological Survey (USGS) has prepared three powdered, whole-wood RMs, USGS54 ( Pinus contorta , Canadian lodgepole pine), USGS55 ( Cordia cf. dodecandra , Mexican ziricote), and USGS56 ( Berchemia cf. zeyheri , South African red ivorywood). The stable isotopes of hydrogen, oxygen, carbon, and nitrogen in these RMs span ranges as δ 2 H VSMOW from –150.4 to –28.2 mUr or ‰, as δ 18 O VSMOW from + 17.79 to + 27.23 mUr, as δ 13 C VPDB from –27.13 to –24.34 mUr, and as δ 15 N AIR-N2 from –2.42 to + 1.8 mUr. These RMs will enable users to normalize measurements of wood samples to isotope–delta scales, and they are intended primarily for the normalization of δ 2 H and δ 18 O measurements of unknown wood samples. However, they also are suitable for normalization of stable isotope measurements of carbon and nitrogen in wood samples. In addition, these RMs are suitable for inter-laboratory calibration for the dual-water suilibration procedure for the measurements of δ 2 H VSMOW values of non-exchangeable hydrogen. The isotopic compositions with 1-σ uncertainties, mass fractions of each element, and fractions of exchangeable hydrogen of these materials are: USGS54 ( Pinus contorta , Canadian Lodgepole pine) δ 2 H VSMOW = –150.4 ± 1.1 mUr (n = 29), hydrogen mass fraction = 6.00 ± 0.04 % (n = 10) Fraction of exchangeable hydrogen = 5.4 ± 0.6 % (n = 29) δ 18 O VSMOW = + 17.79 ± 0.15 mUr (n = 18), oxygen mass fraction = 40.4 ± 0.2 % (n = 6) δ 13 C VPDB = –24.43 ± 0.02 mUr (n = 18), carbon mass fraction = 48.3 ± 0.4 % (n = 12) δ 15 N AIR- N2 = –2.42 ± 0.32 mUr (n = 17), nitrogen mass fraction = 0.05 % (n = 4) USGS55 ( Cordia cf. dodecandra , Mexican ziricote) δ 2 H VSMOW = –28.2 ± 1.7 mUr (n = 30), hydrogen mass fraction = 5.65 ± 0.06 % (n = 10) Fraction of exchangeable hydrogen = 4.1 ± 0.5 % (n = 30) δ 18 O VSMOW = + 19.12 ± 0.07 mUr (n = 18), oxygen mass fraction = 35.3 ± 0.2 % (n = 6) δ 13 C VPDB = –27.13 ± 0.02 mUr (n = 18), carbon mass fraction = 53.3 ± 0.6 % (n = 12) δ 15 N AIR-N2 = –0.3 ± 0.4 mUr (n = 16), nitrogen mass fraction = 0.25 % (n = 4) USGS56 ( Berchemia cf. zeyheri , South African red ivorywood) δ 2 H VSMOW = –44.0 ± 1.8 mUr (n = 30), hydrogen mass fraction = 5.65 ± 0.05 % (n = 10) Fraction of exchangeable hydrogen = 6.6 ± 0.3 % (n = 30) δ 18 O VSMOW = + 27.23 ± 0.03 mUr (n = 12), oxygen mass fraction = 41.1 ± 0.2 % (n = 6) δ 13 C VPDB = –24.34 ± 0.01 mUr (n = 12), carbon mass fraction = 47.3 ± 0.2 % (n = 12) δ 15 N AIR-N2 = + 1.8 ± 0.4 mUr (n = 15), nitrogen mass fraction = 0.27 % (n = 4)

Chemical Geology↗

USGS2016

A revision in hydrogen isotopic composition of USGS42 and USGS43 human-hair stable isotopic reference materials for forensic science

The hydrogen isotopic composition ( δ 2 H VSMOW-SLAP ) of USGS42 and USGS43 human hair stable isotopic reference materials, normalized to the VSMOW (Vienna-Standard Mean Ocean Water)–SLAP (Standard Light Antarctic Precipitation) scale, was originally determined with a high temperature conversion technique using an elemental analyzer (TC/EA) with a glassy carbon tube and glassy carbon filling and analysis by isotope-ratio mass spectrometer (IRMS). However, the TC/EA IRMS method can produce inaccurate δ 2 H VSMOW-SLAP results when analyzing nitrogen-bearing organic substances owing to the formation of hydrogen cyanide (HCN), leading to non-quantitative conversion of a sample into molecular hydrogen (H 2 ) for IRMS analysis. A single-oven, chromium-filled, elemental analyzer (Cr-EA) coupled to an IRMS substantially improves the measurement quality and reliability of hydrogen isotopic analysis of hydrogen- and nitrogen-bearing organic material because hot chromium scavenges all reactive elements except hydrogen. USGS42 and USGS43 human hair isotopic reference materials have been analyzed with the Cr-EA IRMS method, and the δ 2 H VSMOW-SLAP values of their non-exchangeable hydrogen fractions have been revised: where mUr = 0.001 = ‰. On average, these revised δ 2 H VSMOW-SLAP values are 5.7 mUr more positive than those previously measured. It is critical that readers pay attention to the δ 2 H VSMOW-SLAP of isotopic reference materials in publications as they may need to adjust the δ 2 H VSMOW–SLAP measurement results of human hair in previous publications to ensure all results are on the same isotope-delta scale.

Forensic Science International↗

USGS2015

A new isotopic reference material for stable hydrogen and oxygen isotope-ratio measurements of water—USGS50 Lake Kyoga Water

Rationale As a result of the need for isotopic reference waters having high δ 2 H VSMOW-SLAP and δ 18 O VSMOW-SLAP values for daily use, especially for tropical and equatorial-zone freshwaters, a new secondary isotopic reference material for international distribution was prepared from water collected from Lake Kyoga, Uganda. Methods This isotopic reference lakewater was filtered through a membrane with 0.2-µm pore size, homogenized, loaded into glass ampoules that were sealed with a torch and autoclaved to eliminate biological activity, and measured by dual-inlet isotope-ratio mass spectrometry. This reference material is available in a case of 144 glass ampoules each containing 5 mL of water. Results The δ 2 H and δ 18 O values of this reference material are +32.8 ± 0.4 and +4.95 ± 0.02 mUr (milliurey = 0.001 = 1 &permil;), respectively, relative to VSMOW, on scales normalized such that the δ 2 H and δ 18 O values of SLAP reference water are, respectively, −428 and −55.5 mUr. 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. Conclusions This isotopic reference material, designated as USGS50, is intended as one of two reference waters for daily normalization of stable hydrogen and oxygen isotopic analysis of water with an isotope-ratio mass spectrometer or a laser absorption spectrometer, of use especially for isotope-hydrology laboratories analyzing freshwater samples from equatorial and tropical regions.

Lake Kyoga↗