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Haiping Qi

Publications and source records attributed to Haiping Qi.

At least 37 records · Page 2Linked to original sources
USGS2015

Isotopic disproportionation during hydrogen isotopic analysis of nitrogen-bearing organic compounds

Rationale High-precision hydrogen isotope ratio analysis of nitrogen-bearing organic materials using high-temperature conversion (HTC) techniques has proven troublesome in the past. Formation of reaction products other than molecular hydrogen (H 2 ) has been suspected as a possible cause of incomplete H 2 yield and hydrogen isotopic fractionation. Methods The classical HTC reactor setup and a modified version including elemental chromium, both operated at temperatures in excess of 1400 °C, have been compared using a selection of nitrogen-bearing organic compounds, including caffeine. A focus of the experiments was to avoid or suppress hydrogen cyanide (HCN) formation and to reach quantitative H 2 yields. The technique also was optimized to provide acceptable sample throughput. Results The classical HTC reaction of a number of selected compounds exhibited H 2 yields from 60 to 90 %. Yields close to 100 % were measured for the experiments with the chromium-enhanced reactor. The δ 2 H values also were substantially different between the two types of experiments. For the majority of the compounds studied, a highly significant relationship was observed between the amount of missing H 2 and the number of nitrogen atoms in the molecules, suggesting the pyrolytic formation of HCN as a byproduct. A similar linear relationship was found between the amount of missing H 2 and the observed hydrogen isotopic result, reflecting isotopic fractionation. Conclusions The classical HTC technique to produce H 2 from organic materials using high temperatures in the presence of glassy carbon is not suitable for nitrogen-bearing compounds. Adding chromium to the reaction zone improves the yield to 100 % in most cases. The initial formation of HCN is accompanied by a strong hydrogen isotope effect, with the observed hydrogen isotope results on H 2 being substantially shifted to more negative δ 2 H values. The reaction can be understood as an initial disproportionation leading to H 2 and HCN with the HCN-hydrogen systematically enriched in 2 H by more than 50 ‰. In the reaction of HCN with chromium, H 2 and chromium-containing solid residues are formed quantitatively.

Rapid Communications in Mass Spectrometry↗
USGS2014

Biscayne aquifer drinking water (USGS45): a new isotopic reference material for δ 2 H and δ 18 O measurements of water

RATIONALE 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 drinking water collected from the Biscayne aquifer in Ft. Lauderdale, Florida. METHODS This isotopic reference water was filtered, homogenized, loaded into glass ampoules, sealed with a torch, autoclaved to eliminate biological activity, and measured by dual-inlet isotope-ratio mass spectrometry. This reference material is available by the case of 144 glass ampoules containing either 4 mL or 5 mL of water in each ampoule. RESULTS The δ 2 H and δ 18 O values of this reference material are –10.3 ± 0.4 ‰ and –2.238 ± 0.011 ‰, 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 ‰. 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 USGS45, is intended as one of two isotopic 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.

Rapid Communications in Mass Spectrometry↗
USGS2014

Caution on the use of NBS 30 biotite for hydrogen-isotope measurements with on-line high-temperature conversion systems

RATIONALE The supply of NBS 30 biotite is nearly exhausted. During measurements of NBS 30 and potential replacements, reproducible δ 2 H VSMOW-SLAP values could not be obtained by three laboratories using high-temperature conversion (HTC) systems. The cause of this issue has been investigated using the silver-tube technique for hydrogen-isotope measurements of water. METHODS The δ 2 H VSMOW-SLAP values of NBS 30 biotite, other biotites, muscovites, and kaolinite with different particle sizes, along with IAEA-CH-7 polyethylene, and reference waters and NBS 22 oil that were sealed in silver-tube segments, were measured. The effect of absorbed water on mineral surfaces was investigated with waters both enriched and depleted in 2 H. The quantitative conversion of hydrogen from biotite into gaseous hydrogen as a function of mass and particle size was also investigated. RESULTS The δ 2 H VSMOW-SLAP values of NBS 30 obtained by three laboratories were as much as 21 ‰ too high compared with the accepted value of −65.7 ‰, determined by conventional off-line measurements. The experiments showed a strong correlation between grain size and the δ 2 H VSMOW-SLAP value of NBS 30 biotite, but not of biotites with lower iron content. The δ 2 H VSMOW-SLAP values of NBS 30 as a function of particle size show a clear trend toward −65.7 ‰ with finer grain size. CONCLUSIONS Determination of the δ 2 H VSMOW-SLAP values of hydrous minerals and of NBS 30 biotite by on-line HTC systems coupled to isotope-ratio mass spectrometers may be unreliable because hydrogen in this biotite may not be converted quantitatively into molecular hydrogen. Extreme caution in the use and interpretation of δ 2 H VSMOW-SLAP on-line measurements of hydrous minerals is recommended.

Rapid Communications in Mass Spectrometry↗
USGS2014

USGS48 Puerto Rico precipitation - A new isotopic reference material for δ 2 H and δ 18 O measurements of water

A new secondary isotopic reference material has been prepared from Puerto Rico precipitation, which was filtered, homogenised, loaded into glass ampoules, sealed with a torch, autoclaved to eliminate biological activity, and calibrated by dual-inlet isotope-ratio mass spectrometry. This isotopic reference material, designated as USGS48, is intended to be one of two isotopic reference waters for daily normalisation of stable hydrogen (δ 2 H) and stable oxygen (δ 18 O) isotopic analysis of water with a mass spectrometer or a laser absorption spectrometer. The δ 2 H and δ 18 O values of this reference water are−2.0±0.4 and−2.224±0.012 ‰, respectively, relative to Vienna Standard Mean Ocean Water on scales normalised such that the δ 2 H and δ 18 O values of Standard Light Antarctic Precipitation reference water are−428 and−55.5 ‰, respectively. 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 water is available by the case of 144 glass ampoules containing 5 mL of water in each ampoule.

Puerto Rico↗
USGS2013

Lake Louise Water (USGS47): A new isotopic reference water for stable hydrogen and oxygen isotope measurements

"RATIONALE: Because of the paucity of isotopic reference waters for daily use, a new secondary isotopic reference material has been prepared from Lake Louise water from Alberta, Canada for international distribution. MOTHODS: This water was filtered, homogenized, loaded into glass ampoules, sealed with a torch, autoclaved to eliminate biological activity, and measured by dual-inlet isotope-ratio mass spectrometry. This isotopic reference water is available by the case of 144 glass ampoules containing 5 mL of water in each ampoule. RESULTS: The δ2H and δ18O values of this reference water are –150.2 ± 0.5 ‰ and –19.80 ± 0.02 ‰, respectively, relative to VSMOW on scales normalized such that the δ2H and δ18O values of SLAP reference water are, respectively, –428 and –55.5 ‰. Each uncertainty is an estimated expanded uncertainty (U = 2uc) about the reference value that provides an interval that has about a 95-percent probability of encompassing the true value. CONCLUSION: This isotopic reference material, designated as USGS47, is intended as one of two isotopic reference waters for daily normalization of stable hydrogen and stable oxygen isotopic analysis of water with a mass spectrometer or a laser absorption spectrometer. "

Rapid Communications in Mass Spectrometry↗
USGS2013

USGS46 Greenland ice core water – A new isotopic reference material for δ2H and δ18O measurements of water

Ice core from Greenland was melted, filtered, homogenised, loaded into glass ampoules, sealed, autoclaved to eliminate biological activity, and calibrated by dual-inlet isotope-ratio mass spectrometry. This isotopic reference material (RM), USGS46, is intended as one of two secondary isotopic reference waters for daily normalisation of stable hydrogen (δ 2 H) and stable oxygen (δ 18 O) isotopic analysis of water with a mass spectrometer or a laser absorption spectrometer. The measured δ 2 H and δ 18 O values of this reference water were −235.8 ± 0.7‰ and −29.80 ± 0.03‰, 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‰. Each uncertainty is an estimated expanded uncertainty ( U = 2 u c ) about the reference value that provides an interval that has about a 95-percent probability of encompassing the true value. This reference water is available in cases containing 144 glass ampoules that are filled with either 4 ml or 5 ml of water per ampoule.

Geostandards and Geoanalytical Research↗
USGS2013

The δ2H and δ18O of tap water from 349 sites in the United States and selected territories

Because the stable isotopic compositions of hydrogen (δ 2 H) and oxygen (δ 18 O) of animal (including human) tissues, such as hair, nail, and urine, reflect the δ 2 H and δ 18 O of water and food ingested by an animal or a human and because the δ 2 H and δ 18 O of environmental waters vary geographically, δ 2 H and δ 18 O values of tap water samples collected in 2007-2008 from 349 sites in the United States and three selected U.S. territories have been measured in support of forensic science applications, creating one of the largest databases of tap water δ 2 H and δ 18 O values to date. The results of replicate isotopic measurements for these tap water samples confirm that the expanded uncertainties (U = 2μ c ) obtained over a period of years by the Reston Stable Isotope Laboratory from δ 2 H and δ 18 O dual-inlet mass spectrometric measurements are conservative, at ±2‰ and ±0.2 ‰, respectively. These uncertainties are important because U.S. Geological Survey data may be needed for forensic science applications, including providing evidence in court cases. Half way through the investigation, an isotope-laser spectrometer was acquired, enabling comparison of dual-inlet isotope-ratio mass spectrometric results with isotope-laser spectrometric results. The uncertainty of the laser-based δ 2 H measurement results for these tap water samples is comparable to the uncertainty of the mass spectrometric method, with the laser-based method having a slightly lower uncertainty. However, the δ 18 O uncertainty of the laser-based method is more than a factor of ten higher than that of the dual-inlet isotoperatio mass spectrometric method.

Guam, Puerto Rico, St. John, U.S. Virgin Islands↗
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↗
USGS2011

Improved online δ18O measurements of nitrogen‐ and sulfur‐bearing organic materials and a proposed analytical protocol

It is well known that N 2 in the ion source of a mass spectrometer interferes with the CO background during the δ 18 O measurement of carbon monoxide. A similar problem arises with the high‐temperature conversion (HTC) analysis of nitrogenous O‐bearing samples (e.g. nitrates and keratins) to CO for δ 18 O measurement, where the sample introduces a significant N 2 peak before the CO peak, making determination of accurate oxygen isotope ratios difficult. Although using a gas chromatography (GC) column longer than that commonly provided by manufacturers (0.6 m) can improve the efficiency of separation of CO and N 2 and using a valve to divert nitrogen and prevent it from entering the ion source of a mass spectrometer improved measurement results, biased δ 18 O values could still be obtained. A careful evaluation of the performance of the GC separation column was carried out. With optimal GC columns, the δ 18 O reproducibility of human hair keratins and other keratin materials was better than ±0.15 ‰ (n = 5; for the internal analytical reproducibility), and better than ±0.10 ‰ (n = 4; for the external analytical reproducibility).

Rapid Communications in Mass Spectrometry↗
USGS2011

Stable-isotope ratios of hydrogen and oxygen in precipitation at Norman, Oklahoma, 1996–2008

Precipitation samples for measurement of stable-isotope ratios of hydrogen (delta 2 H) and oxygen (delta 18 O) were collected at the Norman Landfill Research Site in Norman, Oklahoma, from May 1996 to October 2008. Rainfall amounts also were measured at the site (U.S. Geological Survey gaging station 07229053) during the collection period. The delta 2 H of precipitation samples ranged from -121.9 to +8.3 per mil, and the delta 18 O of precipitation ranged from -16.96 to +0.50 per mil. The volume-weighted average values for delta 2 H and delta 18 O of precipitation over the 12-year measurement period were -31.13 per mil for delta 2 H and -5.57 per mil for delta 18 O. Average summer-season delta 2 H and delta 18 O values of precipitation usually were more positive (enriched in the heavier isotopes) than winter values.

Oklahoma↗
USGS2010

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↗
USGS2010

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↗
USGS2009

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↗
USGS2007

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↗
USGS2007

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↗
USGS2007

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↗
USGS2007

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↗
USGS2006

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↗