Geology topics

H. Qi

Publications and source records attributed to H. Qi.

4 recordsLinked to original sources

USGS2012

USGS42 and USGS43: Human-hair stable hydrogen and oxygen isotopic reference materials and analytical methods for forensic science and implications for published measurement results

Because there are no internationally distributed stable hydrogen and oxygen isotopic reference materials of human hair, the U.S. Geological Survey (USGS) has prepared two such materials, USGS42 and USGS43. These reference materials span values commonly encountered in human hair stable isotope analysis and are isotopically homogeneous at sample sizes larger than 0.2 mg. USGS42 and USGS43 human-hair isotopic reference materials are intended for calibration of δ(2)H and δ(18)O measurements of unknown human hair by quantifying (1) drift with time, (2) mass-dependent isotopic fractionation, and (3) isotope-ratio-scale contraction. While they are intended for measurements of the stable isotopes of hydrogen and oxygen, they also are suitable for measurements of the stable isotopes of carbon, nitrogen, and sulfur in human and mammalian hair. Preliminary isotopic compositions of the non-exchangeable fractions of these materials are USGS42(Tibetan hair)δ(2)H(VSMOW-SLAP) = -78.5 ± 2.3‰ (n = 62) and δ(18)O(VSMOW-SLAP) = +8.56 ± 0.10‰ (n = 18) USGS42(Indian hair)δ(2)H(VSMOW-SLAP) = -50.3 ± 2.8‰ (n = 64) and δ(18)O(VSMOW-SLAP) = +14.11 ± 0.10‰ (n = 18). Using recommended analytical protocols presented herein for δ(2)H(VSMOW-SLAP) and δ(18)O(VSMOW-SLAP) measurements, the least squares fit regression of 11 human hair reference materials is δ(2)H(VSMOW-SLAP) = 6.085δ(2)O(VSMOW-SLAP) - 136.0‰ with an R-square value of 0.95. The δ(2)H difference between the calibrated results of human hair in this investigation and a commonly accepted human-hair relationship is a remarkable 34‰. It is critical that readers pay attention to the δ(2)H(VSMOW-SLAP) and δ(18)O(VSMOW-SLAP) of isotopic reference materials in publications, and they need to adjust the δ(2)H(VSMOW-SLAP) and δ(18)O(VSMOW-SLAP) measurement results of human hair in previous publications, as needed, to ensure all results on are on the same scales.

Forensic Science International↗

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↗

USGS2009

Nicotine, acetanilide and urea multi-level 2 H-, 13 C- and 15 N-abundance reference materials for continuous-flow isotope ratio mass spectrometry

Accurate determinations of stable isotope ratios require a calibration using at least two reference materials with different isotopic compositions to anchor the isotopic scale and compensate for differences in machine slope. Ideally, the S values of these reference materials should bracket the isotopic range of samples with unknown S values. While the practice of analyzing two isotopically distinct reference materials is common for water (VSMOW-SLAP) and carbonates (NBS 19 and L-SVEC), the lack of widely available organic reference materials with distinct isotopic composition has hindered the practice when analyzing organic materials by elemental analysis/isotope ratio mass spectrometry (EA-IRMS). At present only L-glutamic acids USGS40 and USGS41 satisfy these requirements for ?? 13 C and ?? 13 N, with the limitation that L-glutamic acid is not suitable for analysis by gas chromatography (GC). We describe the development and quality testing of (i) four nicotine laboratory reference materials for on-line (i.e. continuous flow) hydrogen reductive gas chromatography-isotope ratio mass-spectrometry (GC-IRMS), (ii) five nicotines for oxidative C, N gas chromatography-combustion-isotope ratio mass-spectrometry (GC-C-IRMS, or GC-IRMS), and (iii) also three acetanilide and three urea reference materials for on-line oxidative EA-IRMS for C and N. Isotopic off-line calibration against international stable isotope measurement standards at Indiana University adhered to the 'principle of identical treatment'. The new reference materials cover the following isotopic ranges: ?? 2 H nicotine -162 to -45%o, ?? 13 C nicotine -30.05 to +7.72%, ?? 15 N nicotine -6.03 to +33.62%; ?? 15 N acetanilide +1-18 to +40.57%; ?? 13 C urea -34.13 to +11.71%, ?? 15 N urea +0.26 to +40.61% (recommended ?? values refer to calibration with NBS 19, L-SVEC, IAEA-N-1, and IAEA-N-2). Nicotines fill a gap as the first organic nitrogen stable isotope reference materials for GC-IRMS that are available with different ?? 13 N values. Comparative ?? 13 C and ?? 15 N on-line EA-IRMS data from 14 volunteering laboratories document the usefulness and reliability of acetanilides and ureas as EA-IRMS reference materials.

Rapid Communications in Mass Spectrometry↗

USGS2009

Quality assurance and quality control in light stable isotope laboratories: A case study of Rio Grande, Texas, water samples

New isotope laboratories can achieve the goal of reporting the same isotopic composition within analytical uncertainty for the same material analysed decades apart by (1) writing their own acceptance testing procedures and putting them into their mass spectrometric or laser-based isotope-ratio equipment procurement contract, (2) requiring a manufacturer to demonstrate acceptable performance using all sample ports provided with the instrumentation, (3) for each medium to be analysed, prepare two local reference materials substantially different in isotopic composition to encompass the range in isotopic composition expected in the laboratory and calibrated them with isotopic reference materials available from the International Atomic Energy Agency (IAEA) or the US National Institute of Standards and Technology (NIST), (4) using the optimum storage containers (for water samples, sealing in glass ampoules that are sterilised after sealing is satisfactory), (5) interspersing among sample unknowns local laboratory isotopic reference materials daily (internationally distributed isotopic reference materials can be ordered at three-year intervals, and can be used for elemental analyser analyses and other analyses that consume less than 1 mg of material) – this process applies to H, C, N, O, and S isotope ratios, (6) calculating isotopic compositions of unknowns by normalising isotopic data to that of local reference materials, which have been calibrated to internationally distributed isotopic reference materials, (7) reporting results on scales normalised to internationally distributed isotopic reference materials (where they are available) and providing to sample submitters the isotopic compositions of internationally distributed isotopic reference materials of the same substance had they been analysed with unknowns, (8) providing an audit trail in the laboratory for analytical results – this trail commonly will be in electronic format and might include a laboratory information management system, (9) making at regular intervals a complete backup of laboratory analytical data (both of samples logged into the laboratory and of mass spectrometric analyses), being sure to store one copy of this backup offsite, and (10) participating in interlaboratory comparison exercises sponsored by the IAEA and other agencies at regular intervals.

Isotopes in Environmental and Health Studies↗