High-precision laser spectroscopy D/H and 18O/16O measurements of microliter natural water samples

Newly available gas analyzers based on off-axis integrated cavity output spectroscopy (OA-ICOS) lasers have been advocated as an alternative to conventional isotope-ratio mass spectrometers (IRMS) for the stable isotopic analysis of water samples. In the case of H2O, OA-ICOS is attractive because it has comparatively low capital and maintenance costs, the instrument is small and field laboratory portable, and provides simultaneous D/H and 16O/18O ratio measurements directly on H2O molecules with no conversion of H2O to H2, CO, or H2/CO2-water equilibration required. Here we present a detailed assessment of the performance of a liquid-water isotope analyzer, including instrument precision, estimates of sample memory and sample mass effects, and instrumental drift. We provide a recommended analysis procedure to achieve optimum results using OA-ICOS. Our results show that, by using a systematic sample analysis and data normalization procedure routine, measurement accuracies of +/-0.8 per thousand for deltaD and +/-0.1 per thousand delta18O are achievable on nanoliter water samples. This is equivalent or better than current IRMS-based methods and at a comparable sample throughput rate.     

Wood cellulose preparation methods and mass spectrometric analyses of delta13C, delta18O, and nonexchangeable delta2H values in cellulose, sugar, and starch: an interlaboratory comparison

Interlaboratory comparisons involving nine European stable isotope laboratories have shown that the routine methods of cellulose preparation resulted in data that generally agreed within the precision of the isotope ratio mass spectrometry (IRMS) method used: +/-0.2 per thousand for carbon and +/-0.3 per thousand for oxygen. For carbon, the results suggest that holocellulose is enriched up to 0.39 per thousand in 13C relative to the purified alpha-cellulose. The comparisons of IRMS measurements of carbon on cellulose, sugars, and starches showed low deviations from -0.23 to +0.23 per thousand between laboratories. For oxygen, IRMS measurements varied between means from -0.39 to 0.58 per thousand, -0.89 to 0.42 per thousand, and -1.30 to 1.16 per thousand for celluloses, sugars, and starches, respectively. This can be explained by different effects arising from the use of low- or high-temperature pyrolysis and by the variation between laboratories in the procedures used for drying and storage of samples. The results of analyses of nonexchangeable hydrogen are very similar in means with standard deviations between individual methods from +/-2.7 to +/-4.9 per thousand. The use of a one-point calibration (IAEA-CH7) gave significant positive offsets in delta2H values up to 6 per thousand. Detailed analysis of the results allows us to make the following recommendations in order to increase quality and compatibility of the common data bank: (1) removal of a pretreatment with organic solvents, (2) a purification step with 17% sodium hydroxide solution during cellulose preparation procedure, (3) measurements of oxygen isotopes under an argon hood, (4) use of calibration standard materials, which are of similar nature to that of the measured samples, and (5) using a two-point calibration method for reliable result calculation.     

On-line technique for measuring stable oxygen and hydrogen isotopes from microliter quantities of water.

Detailed here is a method for extracting and analyzing oxygen and hydrogen isotopes from 10 microL-sized water samples. Based on the traditional CO2-H2O equilibration technique, the oxygen isotope exchange reaction is done exclusively in sealed 6-mm (o.d.) Pyrex tubes at 25 degrees C, with full isotope exchange completed in at least 28 h. Using the same water sample employed in the 18O equilibration, D/H extractions are done in separate sealed 6-mm (o.d.) Pyrex tubes by reaction with Zn at 450 degrees C to form H2(g). Provided that a correction factor is applied to 18O analyses, accuracy and precision for both 18O and D/H are comparable to standard techniques using much larger samples.     

Stable carbon and oxygen isotopic analysis of atmospheric carbon monoxide using continuous-flow isotope ratio MS by isotope ratio monitoring of CO

We have developed a rapid and simple measurement system for both content and stable isotopic compositions (13C and 18O) of atmospheric CO, using continuous-flow isotope ratio mass spectrometry by simultaneously monitoring the CO+ ion currents at masses 28, 29, and 30. The analytical system consisted sequentially of a sample trapping port (liquid nitrogen temperature silica gel and molecular sieve 5A), a gas dryer, a CO purification column (molecular sieve 5A), a cryofocusing unit, and a final purification column using a GC capillary. Analytical precision of 0.2 per thousand for 13C and 0.4 per thousand for 18O can be realized for samples that contain as little as 300 pmol of CO within 40 min for one sample analysis. Analytical blanks associated with the method are less than 1 pmol. The extent of analytical error in delta13C due to mass-independent fractionation of oxygen in natural CO is estimated to be less than 0.3 per thousand. Based on this system, we report herein a kinetic isotopic effect during CO consumption in soil.     

Isotope (18)O/(16)O Ratio Measurements of Water Vapor by use of Photoacoustic Spectroscopy

We applied a photoacoustic spectroscopy technique to isotope ratio measurements of (16)O and (18)O in water-vapor samples, using a pulsed tunable dye laser pumped by a Nd:YAG laser. The fourth overtone bands (4nu(OH)) of water molecules near 720 nm were investigated. We identified the absorption lines of H(2)(16)O and H(2)(18)O in the photoacoustic spectra that we measured by using an (18)O-enriched water sample and the HITRAN database. We measured the difference in the (18)O/(16)O isotope ratios for normal distilled water and Antarctic ice, using the photoacoustic method. The value obtained for the difference between the two samples is delta(18)O = -32 ? 16 per thousand, where the indicated deviation was a 1varsigma value among 240-s measurements, whereas the value measured with a conventional isotope mass spectrometer was delta(18)O = -28 ? 2 per thousand. This method is demonstrated to have the potential of a transportable system for in situ and quick measurements of the H(2)(18)O/H(2)(16)O ratio in the environment.     

IR laser extraction technique applied to oxygen isotope analysis of small biogenic silica samples

An IR-laser fluorination technique is reported here for analyzing the oxygen isotope composition (delta18O) of microscopic biogenic silica grains (phytoliths and diatoms). Performed after a controlled isotopic exchanged (CIE) procedure, the laser fluorination technique that allows one to visually check the success of the fluorination reaction is faster than the conventional fluorination technique and allows analyzing delta18O of small to minute samples (1.6-0.3 mg) as required for high-resolution paleoenvironmental reconstructions. The long-term reproducibility achieved with the IR laser-heating fluorination/O2 delta18O analysis is lower than or equal to +/-0.26 per thousand (1 SD; n = 99) for phytoliths and +/-0.17 per thousand (1 SD; n = 47) for diatoms. When several CIE are taken into account in the SD calculation, the resulting reproducibility is lower than or equal to +/-0.51 per thousand for phytoliths (1 SD; n = 99; CIE > 5) and +/-0.54 per thousand (1 SD; n = 47; CIE = 13) for diatoms. A minimum reproducibility of +/-0.5 per thousand leads to an estimated uncertainty on delta18Osilica close to +/-0.5 per thousand. Resulting uncertainties on reconstructed temperature and delta18Oforming water are, respectively, +/-2 degrees C and +/-0.5 per thousand and fit in the precisions required for intertropical paleoenvironmental reconstructions. Several methodological points such as optimal extraction protocols and the necessity or not of performing two CIE prior to oxygen extraction are assessed.     

Determination of the hydrogen isotopic compositions of organic materials and hydrous minerals using thermal combustion laser spectroscopy

Hydrogen isotopic compositions of hydrous minerals and organic materials were measured by combustion to water, followed by optical isotopic analysis of the water vapor by off-axis integrated cavity output spectroscopy. Hydrogen and oxygen isotopic compositions were calculated by numerical integration of the individual isotopologue concentrations measured by the optical spectrometer. Rapid oxygen isotope exchange occurs within the combustion reactor between water vapor and molecular oxygen so that only hydrogen isotope compositions may be determined. Over a wide range in sample sizes, precisions were ±3-4 per mil. This is comparable but worse than continuous flow-isotope ratio mass spectroscopy (CF-IRMS) methods owing to memory effects inherent in water vapor transfer. Nevertheless, the simplicity and reduced cost of this analysis compared to classical IRMS or CF-IRMS methods make this an attractive option to determine the hydrogen isotopic composition of organic materials where the utmost precision or small sample sizes are not needed.     

Measurements of the 17O excess in water with the equilibration method

The equilibration method is the present-day standard method for measuring delta18O in water samples. The mass-to-charge ratio of 45 is measured at the same time but generally not used for further analysis. We show that an improved equilibration method can be used for precise determination of delta17O in addition to that of delta18O, and therefore can estimate 17O excess values to a precision of better than 0.1 per thousand. To control the masking effect of the 14 times more abundant 13C on mass 45, we propose to use a chemical buffer in the water samples to keep the pH value and therefore the fractionation during the equilibration process of the 13C constant. With this improved method, the precision for the delta18O value could also be slightly improved from 0.05 to 0.03 per thousand. Furthermore, we discuss the influences of the amount of water, the temperature, the CO2 gas pressures, and changes in the pH during the measuring procedure on oxygen and carbon isotopes. We noticed that measured delta45 values are a good control for delta18O measurements. This study tries to fathom the possibilities and limitations of the equilibration method for measuring 17O excess values of water samples.     

High-precision position-specific isotope analysis of 13C/12C in leucine and methionine analogues

We report an automated method for high-precision position-specific isotope analysis (PSIA) of carbon in amino acid analogues. Carbon isotope ratios are measured for gas-phase pyrolysis fragments from multiple sources of 3-methylthiopropylamine (3MTP) and isoamylamine (IAA), the decarboxylated analogues of methionine and leucine, using a home-built gas chromatography (GC)-pyrolysis-GC preparation system coupled to a combustion-isotope ratio mass spectrometry system. Over a temperature range of 620-900 degrees C, the characteristic pyrolysis products for 3MTP were CH4, C2H6, HCN, and CH3CN and for IAA products were propylene, isobutylene, HCN, and CH3CN. Fragment origin was confirmed by 13C-labeling, and fragments used for isotope analysis were generated from unique moieties with > 95% structural fidelity. Isotope ratios for the fragments were determined with an average precision of SD(delta13C) < 0.3% per thousand, and relative isotope ratios of fragments from different sources were determined with an average precision of SD(delta(delta)13C) < 0.5% per thousand. Delta(delta)13C values of fragments were invariant over a range of pyrolysis temperatures. The delta(delta)13C of complementary fragments in IAA was within 0.8% per thousand of the delta(delta)13C of the parent compounds, indicating that pyrolysis-induced isotopic fractionation is effectively taken into account with this calibration procedure. Using delta(delta)13C values of fragments, delta(delta)13C values were determined for all four carbon positions of 3MTP and for C1, C2, and the propyl moiety of IAA, either directly or indirectly by mass balance. Large variations in position-specific isotope ratios were observed in samples from different commercial sources. Most dramatically, two 3MTP sources differed by 16.30% per thousand at C1, 48.33% per thousand at C2, 0.37% per thousand at C3, and 5.36% per thousand at C(methyl). These PSIA techniques are suitable for studying subtle changes in intramolecular isotope ratios due to natural processes.     

Sulfur isotope analysis of sulfide and sulfate minerals by continuous flow-isotope ratio mass spectrometry

A continuous flow method (CF-IRMS) for the rapid determination of the sulfur isotope composition of sulfide and sulfate minerals has significant advantages over the classic extraction method in terms of the reduced sample quantity and a rapid analytical cycle of less than 8 min/ analysis. For optimum performance, the technique is sensitive to a number of operating parameters, including sample weight and the O2 saturation of the Cu-reduction reactor. Raw data are corrected using a calibration based on five international and internal standards ranging from -17.3 to +20.3 per thousand, which requires monitoring in order to correct the effect of changing delta18O of the sample gas on the measured mass 66 values. Measured sulfur contents are within 1-1.5% of expected values and the reproducibility of delta34S values is +/-0.1 per thousand (1sigma). The technique has been used successfully for more than 1000 analyses of geological samples with a wide range of delta34S from -20 to +20 per thousand.     

Fe isotope variations in natural materials measured using high mass resolution multiple collector ICPMS

We present the first measurements of Fe isotope variations in chemically purified natural samples using high mass resolution multiple-collector inductively coupled plasma source mass spectrometry (MC-ICPMS). High mass resolution allows polyatomic interferences at Fe masses to be resolved (especially, (40)Ar(14)N(+), (40)Ar(16)O(+), and (40)Ar(16)OH(+)). Simultaneous detection of Fe isotope ion beams using multiple Faraday collectors facilitates high-precision isotope ratio measurements. Fe in basalt and paleosol samples was extracted and purified using a simple, single-stage anion chemistry procedure. A Cu "element spike" was used as an internal standard to correct for variations in mass bias. Using this procedure, we obtained data with an external precision of 0.03-0.11 per thousand and 0.04-0.15 per thousand for delta(56/54)Fe and delta(57/54)Fe, respectively (2sigma). Use of Cu was necessary for such reproducibility, presumably because of subtle effects of residual sample matrix on mass bias. These findings demonstrate the utility of high-resolution MC-ICPMS for high-precision Fe isotope analysis in geologic and other natural materials. They also highlight the importance of internal monitoring of mass bias, particularly when using routine methods for Fe extraction and purification.     

A technique for the determination of 18O/16O and 17O/16O isotopic ratios in water from small liquid and solid samples

We have developed a new technique in which a solid reagent, cobalt(III) fluoride, is used to prepare oxygen gas for isotope ratio measurement from water derived either from direct injection or from the pyrolysis of solid samples. The technique uses continuous flow, isotope ratio monitoring, gas chromatography/mass spectrometry (irmGC/MS) to measure the delta18O and delta17O of the oxygen gas. Water from appropriate samples is evolved by a procedure of stepped pyrolysis (0-1000 degrees C, typically in 50 degrees C increments) under a flowing stream of helium carrier gas. The method has considerable advantages over others used for water analysis in that it is quick; requires only small samples, typically 1-50 mg of whole rock samples (corresponding to approximately 0.2 micromol of H2O); and the reagent is easy and safe to handle. Reproducibility in isotope ratio measurement obtained from pyrolysis of samples of a terrestrial solid standard are delta18O +/- 0.54, delta17O +/- 0.33, and delta17O +/- 0.10/1000, 1sigma in all cases. The technique was developed primarily for the analysis of meteorites, and the efficiency of the method is illustrated herein by results from water standards, solid reference materials, and a sample of the Murchison CM2 meteorite.     

Comparison of delta18O measurements in nitrate by different combustion techniques

Three different KNO3 salts with delta18O values ranging from about -31 to +54 per thousand relative to VSMOW were used to compare three off-line, sealed glass tube combustion methods (widely used for isotope studies) with a more recently developed on-line carbon combustion technique. All methods yielded roughly similar isotope ratios for KNO3 samples with delta18O values in the midpoint of the delta18O scale near that of the nitrate reference material IAEA-NO-3 (around +21 to +25 per thousand). This reference material has been used previously for one-point interlaboratory and intertechnique calibrations. However, the isotope ratio scale factors by all of the off-line combustion techniques are compressed such that they are between 0.3 and 0.7 times that of the on-line combustion technique. The contraction of the 6180 scale in the off-line preparations apparently is caused by O isotope exchange between the sample and the glass combustion tubes. These results reinforce the need for nitrate reference materials with delta18O values far from that of atmospheric O2, to improve interlaboratory comparability.     

Method for the analysis of delta18O in water

A new method has been developed for the oxygen isotopic analysis of water utilizing the exchange of oxygen atoms with nitrite followed by conversion of nitrite to nitrous oxide by hydrazoic acid. This method is analogous to that employing carbon dioxide equilibration in that the analyte is added as a reagent to the water sample and exchanges oxygen isotopes with the water. In this procedure, however, the equilibration is more rapid and less sensitive to changes in ambient temperature, as the exchange is terminated by conversion of nitrite to nitrous oxide prior to analysis. The nitrous oxide is then analyzed using an on-line purge and trap system coupled to an isotope ratio mass spectrometer. This method makes use of previously established methods for nitrite isotopic analysis and commercially available equipment. It has high throughput, relatively low standard deviation (0.1 per thousand or better), and small sample size (down to 100 microL), is simple, and is applicable to both fresh- and seawater samples.     

Determination of the total oxygen isotopic composition of nitrate and the calibration of a delta 17O nitrate reference material

A thermal decomposition method was developed and tested for the simultaneous determination of delta 18O and delta 17O in nitrate. The thermal decomposition of AgNO3 allows for the rapid and accurate determination of 18O/ 16O and 17O/16O isotopic ratios with a precision of +/- 1.5 per thousand for delta 18O and +/- 0.11 per thousand for delta 17O (delta 17O = delta 17O - 0.52 x delta 18O). The international nitrate isotope reference material IAEA-NO3 yielded a delta 18O value of +23.6 per thousand and delta 17O of -0.2 per thousand, consistent with normal terrestrial mass-dependent isotopic ratios. In contrast, a large sample of NaNO3 from the Atacama Desert, Chile, was found to have delta 17O = 21.56 +/- 0.11 per thousand and delta 18O = 54.9 +/- 1.5 per thousand, demonstrating a substantial mass-independent isotopic composition consistent with the proposed atmospheric origin of the desert nitrate. It is suggested that this sample (designated USGS-35) can be used to generate other gases (CO2, CO, N2O, O2) with the same delta 17O to serve as measurement references for a variety of applications involving mass-independent isotopic compositions in environmental studies.     

BaCe0.4Zr0.3Sn0.1Sm0.2O3-α的中温离子导电性

采用高温固相法合成了Sn4+、Sm3+双掺杂的BaCeO3-BaZrO3固溶体——BaCe0.4Zr0.3Sn0.1Sm0.2O3-α(BCZSS)固体电解质材料,并进行了XRD、SEM测试表征。采用同位素效应、浓差电池等电化学方法研究了样品在873～1073K的离子导电特性。浓差电池测试结果表明样品在湿润氧气气氛中是离子(质子+氧离子)和空穴的混合导体,样品在湿润氢气气氛下存在氧离子导电性。H2O-Ar气氛下的电导率高于相同温度下D2O-Ar气氛下的电导率,表明该样品在含水气氛中是一种优良的质子导体。     

Coupling a high-temperature catalytic oxidation total organic carbon analyzer to an isotope ratio mass spectrometer to measure natural-abundance delta13C-dissolved organic carbon in marine and freshwater samples

The stable isotope composition of dissolved organic carbon (delta(13)C-DOC) provides powerful information toward understanding carbon sources and cycling, but analytical limitations have precluded its routine measurement in natural samples. Recent interfacing of wet oxidation-based dissolved organic carbon analyzers and isotope ratio mass spectrometers has simplified the measurement of delta(13)C-DOC in freshwaters, but the analysis of salty estuarine/marine samples still proves difficult. Here we describe the coupling of the more widespread high-temperature catalytic oxidation-based total organic carbon analyzer to an isotope ratio mass spectrometer (HTC-IRMS) through cryogenic trapping of analyte gases exiting the HTC analyzer for routine analysis of delta(13)C-DOC in aquatic and marine samples. Targeted elimination of major sources of background CO2 originating from the HTC analyzer allows for the routine measurement of samples over the natural range of DOC concentrations (from 40 microM to over 2000 microM), and salinities (<0.1-36 g/kg). Because consensus reference natural samples for delta(13)C-DOC do not exist, method validation was carried out with water-soluble stable isotope standards as well as previously measured natural samples (IAEA sucrose, Suwannee River Fulvic Acids, Deep Sargasso Sea consensus reference material, and St. Lawrence River water) and result in excellent delta(13)C-DOC accuracy (+/-0.2 per thousand) and precision (+/-0.3 per thousand).     

Determination of bromine stable isotopes using continuous-flow isotope ratio mass spectrometry

A new methodology for bromine stable isotope determination by continuous-flow isotope ratio mass spectrometry (CF-IRMS) was developed. The technique was tested on inorganic samples. Inorganic bromide was precipitated in the form of silver bromide by using silver nitrate in a standard methodology. Bromine stable isotope analysis was carried out on methyl bromide (CH3Br) after converting silver bromide to methyl bromide by reacting it with methyl iodide (CH3I). The system used in this study is an IsoPrime IRMS, with analytical capabilities of both dual-inlet and continuous-flow modes coupled with an Agilent 6890 GC equipped with a CTC Analytics CombiPAL autosampler. This new technique measures samples as small as 0.2 mg of AgBr (1 micromol of Br-). The bromine stable isotope analysis using continuous flow technology showed excellent precision and accuracy. The internal precision using pure methyl bromide gas is better than +/-0.03 per thousand (+/-SD); the external precision using seawater standard is better than +/-0.06 per thousand (+/-SD) for n = 12. Moreover, the sample analysis time is 16 min, as compared to 75 min needed in previous techniques. This allows for 50 samples to be analyzed in 1 day, as compared to 8 samples using the conventional techniques. A series of natural saline formation waters and brines from sedimentary and crystalline rock environments was measured by this new methodology to test the potential natural range of delta81Br. The bromine isotopic composition of the samples ranged from 0.00 to +1.80 per thousand relative to standard mean ocean bromide (SMOB). Initial trends and distinctive isotopic difference were noticed between crystalline shield brines and sedimentary formation brines.     

Moving-wire device for carbon isotopic analyses of nanogram quantities of nonvolatile organic carbon

We describe a moving-wire analyzer for measuring 13C in dissolved, involatile organic materials. Liquid samples are first deposited and dried on a continuously spooling nickel wire. The residual sample is then combusted as the wire moves through a furnace, and the evolved CO2 is analyzed by continuous-flow isotope ratio mass spectrometry. A typical analysis requires 1 microL of sample solution and produces a CO2 peak approximately 5 s wide. The system can measure "bulk" delta13C values of approximately 10 nmol of organic carbon with precision better than 0.2 per thousand. For samples containing approximately 1 nmol of C, precision is approximately 1 per thousand. Precision and sensitivity are limited mainly by background noise derived from carbon within the wire. Instrument conditions minimizing that background are discussed in detail. Accuracy is better than 0.5 per thousand for nearly all dissolved analytes tested, including lipids, proteins, nucleic acids, sugars, halocarbons, and hydrocarbons. The sensitivity demonstrated here for 13C measurements represents a approximately 1000-fold improvement relative to existing elemental analyzers and should allow the use of many new preparative techniques for collecting and purifying nonvolatile biochemicals for isotopic analysis.     

Realtime stable isotope monitoring of natural waters by parallel-flow laser spectroscopy

A parallel-flow H(2)O(liquid)-H(2)O(vapor) equilibration and laser spectroscopy method provides a new way to monitor the hydrogen and oxygen stable isotopic composition of water from rivers or lakes or in hydrologic tracer tests in real time. Two custom-built equilibrator devices and one commercial membrane device were tested to determine if they could be used to convert natural water samples (lakes, rivers, groundwater) to a H(2)O gas phase for continuous online δ(18)O and δD isotopic analysis by laser spectroscopy. Both the commercial minimodule device and the marble-filled equilibrator produced water vapor in isotopic equilibrium with the flowing liquid water, suggesting that unattended field measurement using these devices is possible. Oxygen isotope disequilibrium was indicated using the minimodule device at low temperatures.