High-precision measurements of 17O/16O and 18O/16O of O2 and O2/Ar ratio in air

A method for high-precision and high-accuracy mass spectrometric measurements of the ratios among the three oxygen isotopes, and of the O(2)/Ar ratio, is presented. It involves separation of the O(2)-Ar mixture from air and includes a fully automated system that ensures highly reliable sample processing. Repeated measurements of atmospheric oxygen yield the repeatability (+/-SE x t, standard error of the mean (n = 12) multiplied by Student's t-factor for a 95% confidence limit) of 0.004, 0.003 and 0.2 per thousand for delta(18)O, delta(17)O and delta O(2)/Ar, respectively.     

Determination of the 2H/1H, 17O/16O,and 18O/16O isotope ratios in water by means of tunable diode laser spectroscopy at 1.39 microm

We demonstrate the feasibility of the accurate and simultaneous measurement of the 2H/1H, 17O/16O, and 18O/16O isotope ratios in water vapor by means of tunable diode laser spectroscopy. The absorptions are due to the v1 + v3 combination band, observed using a room temperature, distributed feedback (DFB) diode laser at 1.39 microm. The precision of the instrument is approximately 3, 1, and 0.5/1000 for the 2H, 17O, and 18O isotope ratios, respectively, and is at present limited by residual optical feedback to the laser. The signal-to-noise, however, is superior to that obtained in a similar experiment using a color center laser at 2.7 microm. Replacing the current laser with a better unit, we are confident that a precision well below 1/1000 is attainable for all three isotope ratios. The diode laser apparatus is ideally suited for applications demanding a reliable, cheap, and/or portable instrument, such as the biomedical doubly labeled water method and atmospheric sensing.     

Continuous flow 2H/1H and 18O/16O analysis of water samples with dual inlet precision

A method for isotope ratio analysis of water samples is described comprising an on-line high-temperature reduction technique in a helium carrier gas. Using a gas-tight syringe, injection of 0.5 to 1 microL sample is made through a heated septum into a glassy carbon reactor at temperatures in excess of 1300 degrees C. More than 150 injections can be made per day and both isotope ratios of interest, delta2H and delta18O, can be measured with the same setup. The technique has the capability to transfer high-precision stable isotope ratio analysis of water samples from a specialized to a routine laboratory task compatible with other common techniques (automated injection for GC, LC, etc.). Experiments with an emphasis on the reactor design were made in two different laboratories using two different commercially available high-temperature elemental analyser (EA) systems.In the Jena TC/EA unit, sample-to-sample memory (single injection) has been reduced to approximately 1% and high precision of about 0.1 per thousand for delta18O and < 1 per thousand for delta2H has been achieved by a redesign of the glassy carbon reactor and by redirecting the gas flow of the commercial TC/EA unit. With the modified reactor, the contact of water vapour with surfaces other than glassy carbon is avoided completely. The carrier gas is introduced at the bottom of the reactor thereby flushing the outer tube compartment of the tube-in-tube assembly before entering the active heart of the reactor.With the Leipzig high-temperature reactor (HTP) similar precision was obtained with a minor modification (electropolishing) of the injector metal sleeve. With this system, the temperature dependence of the reaction has been studied between 1100 and 1450 degrees C. Complete yield and constant isotope ratio information has been observed only for temperatures above 1325 degrees C. For temperatures above 1300 degrees C the reactor produces an increasing amount of CO background from reaction of glass carbon with the ceramic tube. This limits the usable temperature to a maximum of 1450 degrees C. Relevant gas permeation through the Al2O3 walls has not been detected up to 1600 degrees C.     

Diffusivity fractionations of H2(16)O/H2(17)O and H2(16)O/H2(18)O in air and their implications for isotope hydrology

We have determined the isotope effects of (17)O and (18)O substitution of (16)O in H(2)O on molecular diffusivities of water vapor in air by the use of evaporation experiments. The derived diffusion fractionation coefficients (17)alpha(diff) and (18)alpha(diff) are 1.0146 +/- 0.0002 and 1.0283 +/- 0.0003, respectively. We also determined, for the first time, the ratio ln((17)alpha(diff))/ln((18)alpha(diff)) as 0.5185 +/- 0.0002. This ratio, which is in excellent agreement with the theoretical value of 0.5184, is significantly smaller than the ratio in vapor-liquid equilibrium (0.529). We show how this new experimental information gives rise to (17)O excess in meteoric water, and how it can be applied in isotope hydrology.     

Identification of corona discharge-induced SF6 oxidation mechanisms using SF6/18O2/H2 16O and SF6/16O2/H2 18O gas mixtures

The absolute yields of gaseous oxyfluorides SOF₂, SO₂F₂, and SOF₄ from negative, point-plane corona discharges in pressurized gas mixtures of SF₆ with O₂ and H₂O enriched with¹⁸O₂ and H₂ ¹⁸O have been measured using a gas chromatograph-mass spectrometer. The predominant SF₆ oxidation mechanisms have been revealed from a determination of the relative¹⁸O and¹⁶O isotope content of the observed oxyfluoride by-product. The results are consistent with previously proposed production mechanisms and indicate that SOF₂ and SO₂F₂ derive oxygen predominantly from H₂O and O₂, respectively, in slow, gas-phase reactions involving SF₄, SF₃, and SF₂ that occur outside of the discharge region. The species SOF₄ derives oxygen from both H₂O and O₂ through fast reactions in the active discharge region involving free radicals or ions such as OH and O, with SF₅ and SF₄.     

Freezing-point of mixtures of H 2 16 O and H 2 18 O

Freezing-point depression of mixtures of H ₂ ¹⁶ O and H ₂ ¹⁸ O were measured. The results showed that the freezing point of the mixture rose linearly with an increase in the molal concentration of H ₂ ¹⁸ O. The results suggested the formation of a solid solution of H ₂ ¹⁶ O and H ₂ ¹⁸ O by freezing, similar to that formed by H ₂ O–D ₂ O, and that H ₂ ¹⁸ O behaves as a different molecule than H ₂ ¹⁶ O.     

Determination of the 15N/14N, 17O/16O, and 18O/16O ratios of nitrous oxide by using continuous-flow isotope-ratio mass spectrometry

We developed a rapid, sensitive, and automated analytical system to determine the delta15N, delta18O, and Delta17O values of nitrous oxide (N2O) simultaneously in nanomolar quantities for a single batch of samples by continuous-flow isotope-ratio mass spectrometry (CF-IRMS) without any cumbersome and time-consuming pretreatments. The analytical system consisted of a vacuum line to extract and purify N2O, a gas chromatograph for further purification of N2O, an optional thermal furnace to decompose N2O to O2, and a CF-IRMS system. We also used pneumatic valves and pneumatic actuators in the system so that we could operate it automatically with timing software on a personal computer. The analytical precision was better than 0.12 per thousand for delta15N with >4 nmol N2O injections, 0.25 per thousand for delta18O with >4 nmol N2O injections, and 0.20 per thousand for Delta17O with >20 nmol N2O injections for a single measurement. We were also easily able to improve the precision (standard errors) to better than 0.05 per thousand for delta15N, 0.10 per thousand for delta18O, and 0.10 per thousand for Delta17O through multiple analyses with more than four repetitions with 190 nmol samples using the automated analytical system. Using the system, the delta15N, delta18O, and Delta17O values of N2O can be quantified not only for atmospheric samples, but also for other gas or liquid samples with low N2O content, such as soil gas or natural water. Here, we showed the first ever Delta17O measurements of soil N2O.     

Partial pressure dependency of 17O/16O and 18O/16O of molecular oxygen in the mass spectrometer

A method to determine both (17)O/(16)O and (18)O/(16)O ratios for molecular oxygen with high precision by direct introduction into the mass spectrometer without gas separation is presented. Because both (17)O/(16)O and (18)O/(16)O in mixed gases have good linear correlations with their mixing ratios, these isotopic compositions can be determined without a gas-separation procedure by calibration using prepared standard gases with variable mixed ratios and by monitoring the amounts of fragment ions. Analytical precision for delta(17)O and delta(18)O of 45 and 7 per meg, respectively, were obtained. The observed partial pressure dependency of isotopic composition may be caused by isotope fractionation during admission from the ionization chamber into the flight tube of the mass spectrometer.     

Comparison of the3He/16O and1H/18O prompt nuclear reactions for lattice location measurements of oxygen in niobium

Experimental data are presented for comparison of the determination of oxygen by the¹⁶O(³He, p)¹⁸F,¹⁶O(³He, α)¹⁵O and¹⁸O(p, α)¹⁵N prompt nuclear reactions, and of their use in the lattice location, by the ion-channelling technique, of oxygen atoms in single crystal targets of elements such as niobium, where oxygen contents of ≈0.1 atomic % or more can be obtained. Both reaction cross-sections and lattice-defect production rates are considered in the comparison. Details are given of an arrangement for automatic crystallographic angular scanning of nuclear reaction and backscattering yields in channelling/lattice location measurements.     

High-precision determination of 18O/16O ratios of silver phosphate by EA-pyrolysis-IRMS continuous flow technique

A high-precision, and rapid on-line method for oxygen isotope analysis of silver phosphate is presented. The technique uses high-temperature elemental analyzer (EA)-pyrolysis interfaced in continuous flow (CF) mode to an isotopic ratio mass spectrometer (IRMS). Calibration curves were generated by synthesizing silver phosphate with a 13 per thousand spread in delta(18)O values. Calibration materials were obtained by reacting dissolved potassium dihydrogen phosphate (KH(2)PO(4)) with water samples of various oxygen isotope compositions at 373 K. Validity of the method was tested by comparing the on-line results with those obtained by classical off-line sample preparation and dual inlet isotope measurement. In addition, silver phosphate precipitates were prepared from a collection of biogenic apatites with known delta(18)O values ranging from 12.8 to 29.9 per thousand (V-SMOW). Reproducibility of +/- 0.2 per thousand was obtained by the EA-Py-CF-IRMS method for sample sizes in the range 400-500 microg. Both natural and synthetic samples are remarkably well correlated with conventional (18)O/(16)O determinations. Silver phosphate is a very stable material and easy to degas and, thus, could be considered as a good candidate to become a reference material for the determination of (18)O/(16)O ratios of phosphate by high-temperature pyrolysis.     

Identification and correction of spectral contamination in 2H/1H and 18O/16O measured in leaf, stem, and soil water

Plant water extracts typically contain organic materials that may cause spectral interference when using isotope ratio infrared spectroscopy (IRIS), resulting in errors in the measured isotope ratios. Manufacturers of IRIS instruments have developed post-processing software to identify the degree of contamination in water samples, and potentially correct the isotope ratios of water with known contaminants. Here, the correction method proposed by an IRIS manufacturer, Los Gatos Research, Inc., was employed and the results were compared with those obtained from isotope ratio mass spectrometry (IRMS). Deionized water was spiked with methanol and ethanol to create correction curves for δ(18)O and δ(2)H. The contamination effects of different sample types (leaf, stem, soil) and different species from agricultural fields, grasslands, and forests were compared. The average corrections in leaf samples ranged from 0.35 to 15.73‰ for δ(2)H and 0.28 to 9.27‰ for δ(18)O. The average corrections in stem samples ranged from 1.17 to 13.70‰ for δ(2)H and 0.47 to 7.97‰ for δ(18)O. There was no contamination observed in soil water. Cleaning plant samples with activated charcoal had minimal effects on the degree of spectral contamination, reducing the corrections, by on average, 0.44‰ for δ(2)H and 0.25‰ for δ(18)O. The correction method eliminated the discrepancies between IRMS and IRIS for δ(18)O, and greatly reduced the discrepancies for δ(2)H. The mean differences in isotope ratios between IRMS and the corrected IRIS method were 0.18‰ for δ(18)O, and -3.39‰ for δ(2)H. The inability to create an ethanol correction curve for δ(2)H probably caused the larger discrepancies. We conclude that ethanol and methanol are the primary compounds causing interference in IRIS analyzers, and that each individual analyzer will probably require customized correction curves.     

Oxygen isotopes in nitrate: new reference materials for 18O:17O:16O measurements and observations on nitrate-water equilibration

Despite a rapidly growing literature on analytical methods and field applications of O isotope-ratio measurements of NO(3)(-) in environmental studies, there is evidence that the reported data may not be comparable because reference materials with widely varying delta(18)O values have not been readily available. To address this problem, we prepared large quantities of two nitrate salts with contrasting O isotopic compositions for distribution as reference materials for O isotope-ratio measurements: USGS34 (KNO(3)) with low delta(18)O and USGS35 (NaNO(3)) with high delta(18)O and 'mass-independent' delta(17)O. The procedure used to produce USGS34 involved equilibration of HNO(3) with (18)O-depleted meteoric water. Nitric acid equilibration is proposed as a simple method for producing laboratory NO(3)(-) reference materials with a range of delta(18)O values and normal (mass-dependent) (18)O:(17)O:(16)O variation. Preliminary data indicate that the equilibrium O isotope-fractionation factor (alpha) between [NO(3)(-)] and H(2)O decreases with increasing temperature from 1.0215 at 22 degrees C to 1.0131 at 100 degrees C. USGS35 was purified from the nitrate ore deposits of the Atacama Desert in Chile and has a high (17)O:(18)O ratio owing to its atmospheric origin. These new reference materials, combined with previously distributed NO(3) (-) isotopic reference materials IAEA-N3 (=IAEA-NO-3) and USGS32, can be used to calibrate local laboratory reference materials for determining offset values, scale factors, and mass-independent effects on N and O isotope-ratio measurements in a wide variety of environmental NO(3)(-) samples. Preliminary analyses yield the following results (normalized with respect to VSMOW and SLAP, with reproducibilities of +/-0.2-0.3 per thousand, 1sigma): IAEA-N3 has delta(18)O = +25.6 per thousand and delta(17)O = +13.2 per thousand; USGS32 has delta(18)O = +25.7 per thousand; USGS34 has delta(18)O = -27.9 per thousand and delta(17)O = -14.8 per thousand; and USGS35 has delta(18)O = +57.5 per thousand and delta(17)O = +51.5 per thousand.     

Water line lists close to experimental accuracy using a spectroscopically determined potential energy surface for H2(16)O, H2(17)O, and H2(18)O

Line lists of vibration-rotation transitions for the H(2) (16)O, H(2) (17)O, and H(2) (18)O isotopologues of the water molecule are calculated, which cover the frequency region of 0-20 000 cm(-1) and with rotational states up to J=20 (J=30 for H(2) (16)O). These variational calculations are based on a new semitheoretical potential energy surface obtained by morphing a high accuracy ab initio potential using experimental energy levels. This potential reproduces the energy levels with J=0, 2, and 5 used in the fit with a standard deviation of 0.025 cm(-1). Linestrengths are obtained using an ab initio dipole moment surface. That these line lists make an excellent starting point for spectroscopic modeling and analysis of rotation-vibration spectra is demonstrated by comparison with recent measurements of Lisak and Hodges [J. Mol. Spectrosc. (unpublished)]: assignments are given for the seven unassigned transitions and the intensity of the strong lines are reproduced to with 3%. It is suggested that the present procedure may be a better route to reliable line intensities than laboratory measurements.     

Yield of 16OS18O from the 18OH initiated oxidation of CS2 in 16O2

The yield of ¹⁶OS¹⁸O from the ¹⁸OH initiated oxidation of CS₂ in ¹⁶O₂ was measured by using a discharge flow reactor coupled to a chemical ionization mass spectrometer. ¹⁶OS¹⁸O is the dominant SO₂ isotopomer produced with a yield of 0.90 ± 0.20 relative to ¹⁸OH loss. The errors are estimates for the uncertainty at the 95% confidence level. The implications of these results to the understanding of the CS₂ oxidation mechanism are discussed. © 1994 John Wiley & Sons, Inc.

1 This article is a US Government work and, as such, is in the public domain in the United States of America.