Source Isotope Ratio Mass Spectrometry Research Articles

Barite, Anhydrite and Gypsum Reference Materials for In Situ Oxygen and Sulfur Isotope Ratio Measurements

Secondary ion mass spectrometry was used to test the δ18O and δ34S nanogram‐scale homogeneity of a suite of candidate sulfate minerals, ultimately selecting three barite, two anhydrite, and two gypsum samples from the Royal Ontario Museum that have repeatabilities for their SIMS measurements of better than ±0.39‰ and ±0.37‰ (1s) for oxygen and sulfur isotope ratios, respectively. Metrological splits of each of the seven materials were sent to multiple gas source isotope ratio mass spectrometry laboratories in order to establish their absolute 18O/16O and 34S/32S ratios. The inter‐laboratory results of GS‐IRMS analyses yielded reasonably narrow ranges in δ18OVSMOW, whereas larger variations in δ34SVCDT values were found between the results from the gas source laboratories. All samples have good reproducibility within laboratories of GS‐IRMS 103δ18O values of between ±0.24‰ and ±0.44‰ (1s). The reproducibility within laboratories of GS‐IRMS 103δ34S values range from ±0.07‰ to ±0.99‰ (1s). Here we also discuss some of the current analytical limitations affecting these isotope‐mineral systems. A total of 256 metrological splits have been prepared from each of these seven materials; these aliquots will be made available to the global geochemical community.

Analysis of intramolecular carbon isotope distributions in alanine by electrospray ionization Orbitrap mass spectrometry

The ability to detect intramolecular isotopic differences within a single molecule can answer questions about molecule synthesis and alteration across numerous scientific fields. Until recently, intramolecular (i.e., position-specific isotope analysis, PSIA) isotope measurements were laborious, requiring large amounts of analyte or specialized instrumentation. Orbitrap™ mass spectrometers are capable of fragmenting molecules and have the high mass resolution needed to constrain position-specific isotopic differences among the resulting fragment ions. Orbitrap mass spectrometers with electrospray ionization accurately measured the molecular average isotope composition of acetate, nitrate, sulfate, phosphate, and the amino acid methionine, as well as the position-specific isotopic structure of methionine. Here, we document the ability of this method to measure the position-specific carbon isotope structure of the amino acid alanine. Data include measurements of 13C-enriched materials to assign specific atoms in fragments to the original molecular structure and detect any recombination of atoms in resultant fragments. We further demonstrate high-precision intramolecular isotope analyses for standards with independently determined position-specific carbon isotope compositions. Isotope data from ESI-Orbitrap-MS agrees with values obtained using gas source isotope ratio mass spectrometry, giving further confidence to this novel approach to PSIA. The carbon isotope analyses by Orbitrap-MS were rapid and required ∼5 μg of analyte to obtain both molecular average and position-specific values in triplicate with precision ≤1‰.

New Potential Sphalerite, Chalcopyrite, Galena and Pyrite Reference Materials for Sulfur Isotope Determination by Laser Ablation‐MC‐ICP‐MS

The sulfur isotope system is important in tracing a variety of geochemical processes. However, the availability of matrix‐matched reference materials for in situ sulfur isotope ratio measurement is limited. This study analysed four sulfide specimens to investigate their potential as reference materials for in situ sulfur isotope determination, including three natural sulfide minerals (sphalerite SPH‐1, chalcopyrite GC‐1 and galena NWU‐GN), and one resin preserved pyrite powder (RPPY). These four sulfides were analysed independently in four laboratories using both bulk and microbeam analysis techniques, all of which gave equivalent results within uncertainty with comparable accuracy and precision. The sulfur isotopes of these four sulfides are homogeneous based on a large number of isotope determinations by solution nebulisation multi‐collector inductively coupled plasma‐mass spectrometry (MC‐ICP‐MS) and laser ablation (LA) MC‐ICP‐MS. The mean δ34S values for SPH‐1, RPPY, GC‐1 and NWU‐GN determined by gas source isotope ratio mass spectrometry (GS‐IRMS) and solution nebulisation MC‐ICP‐MS are −7.13 ± 0.41‰ (2s), 3.66 ± 0.24‰ (2s), −0.65 ± 0.28‰ (2s), 28.21 ± 0.17‰ (2s) relative to the Vienna‐Canyon Diablo troilite (V‐CDT) reference value, respectively, and which are proposed as potential preferred values. Over 400 spot analyses performed on randomly selected fragments of each sulfide by LA‐MC‐ICP‐MS yielded highly consistent δ34S values with the preferred values. Thus, SPH‐1, GC‐1, NWU‐GN and RPPY are considered a set of candidate matrix‐matched sulfide reference materials for in situ sulfur isotope determination.

Inter‐laboratory Characterisation of Apatite Reference Materials for Oxygen Isotope Analysis and Associated Methodological Considerations

Here we report on the oxygen isotope compositions of four proposed apatite reference materials (chlorapatite MGMH#133648 and fluorapatite specimens MGMH#128441A, MZ‐TH and ES‐MM). The samples were initially screened for 18O/16O homogeneity using secondary ion mass spectrometry (SIMS) followed by δ18O determinations in six gas source isotope ratio mass spectrometry laboratories (GS‐IRMS) using a variety of analytical protocols for determining either phosphate‐bonded or “bulk” oxygen compositions. We also report preliminary δ17O and Δ’17O data, major and trace element compositions collected using EPMA, as well as CO32− and OH− contents in the apatite structure assessed using thermogravimetric analysis and infrared spectroscopy. The repeatability of our SIMS measurements was better than ± 0.25 ‰ (1s) for all four materials that cover a wide range of 103δ18O values between +5.8 and +21.7. The GS‐IRMS results show, however, a significant offset of 103δ18O values between the “phosphate” and “bulk” analyses that could not be correlated with chemical characteristics of the studied samples. Therefore, we provide two sets of working values specific to these two classes of analytical methodologies as well as current working values for SIMS data calibration.

Cassiterite oxygen isotopes in magmatic-hydrothermal systems: in situ microanalysis, fractionation factor, and applications

Tin and tungsten are important metals for the industrializing society. Deciphering the origin and evolution of hydrothermal fluids responsible for their formation is critical to underpin genetic models of ore formation. Traditional approaches obtain isotopic information mainly from bulk analysis of both ore and gangue minerals, or less frequently from in situ analysis of gangue minerals, which either bear inherited complexities and uncertainties or are indirect constraints. Hence, directly obtaining isotopic information from ore minerals such as cassiterite by in situ techniques is warranted. However, this has been hampered by challenges from both analytical and applicational aspects. In this study, we first demonstrate a lack of crystallographic orientation effects during cassiterite ion microprobe oxygen isotope analysis. Along with our newly developed matrix-matched reference material, the Yongde-Cst, which has a recommended δ18O value of 1.36 ± 0.16‰ (VSMOW) as defined by gas source isotope ratio mass spectrometry, in situ oxygen isotope analysis of cassiterite now is possible. We further refine the oxygen isotope fractionation (1000 ln α) for quartz-cassiterite by first-principles calculations, which is given by the equation of 1.259 × 106/T2 + 8.15 × 103/T − 4.72 (T is temperature in Kelvin). The 1000 ln α for quartz-cassiterite has a sensitive response to temperature, and makes cassiterite-quartz an excellent mineral pair in oxygen isotope thermometry, as described by the equation of T (℃) = 2427 × (δ18Oqtz − δ18Ocst)−0.4326 − 492.4. Using the well-established 1000 ln α of quartz-water, 1000 ln α of cassiterite-water is derived as 2.941 × 106/T2 − 11.45 × 103/T + 4.72 (T in Kelvin), which shows a weak response to temperature. This makes cassiterite an ideal mineral from which to derive δ18O of fluids as robust temperature estimates are no longer a prerequisite. We have applied oxygen isotope analysis to cassiterite samples from six Sn(-W) deposits in China. The results show considerable variability in δ18O values both within a single deposit and among studied deposits. Combining the δ18O of cassiterite samples and the equilibrium oxygen isotope fractionation, we find that the δ18O values of ore-forming fluids show a strong magmatic affinity with variable but mostly no to low degree involvements (~0-10%) of meteoric water, hence our results invite a reassessment on the extent and role of meteoric water in Sn-W mineralization. This study demonstrates that in situ oxygen isotope analysis of cassiterite is a promising tool to refine sources of ore-forming fluids, and to decode hydrothermal dynamics controlling tin and tungsten mineralization.

NJUCal‐1: A New Calcite Oxygen Isotope Reference Material for Microbeam Analysis

Calcite is a common mineral in various types of rocks and mineral deposits, and its oxygen isotopic compositions are widely used to reconstruct palaeotemperature and to trace rock genesis and ore‐forming processes. However, the availability of high‐quality matrix‐matched calcite reference materials for oxygen isotope microanalysis is limited. A new natural calcite specimen (NJUCal‐1) was analysed in this study to investigate its potential as a reference material for microbeam oxygen isotope measurement. Detailed textural and major elemental examinations reveal no internal zoning of ground grains. During six measurement sessions, a total of 463 spot analyses of oxygen isotope ratios were applied on ~ 200 randomly selected grains using secondary ion mass spectrometry, Nanjing. Taking all six sessions together, the spot‐to‐spot repeatability is 0.28‰ (2s), and the repeatability is better than 0.31‰ (2s) for individual sessions, indicating that the NJUCal‐1 calcite is quite homogeneous in its oxygen isotopic compositions and can be used as a new reference material for microbeam oxygen isotope measurement. The mean δ18OVPDB value determined by gas source isotope ratio mass spectrometry is −22.58 ± 0.16‰ (2s, n = 22), which is proposed as the recommended value for this potential reference material.

Revisiting apatite SIMS oxygen isotope analysis and Qinghu-AP reference material

Oxygen is one of the most abundant elements in the universe and ubiquitously participates in geological and biological processes which play a critical role in shaping and maintaining habitability of the Earth. Its isotope composition is a key parameter to decode these geological and biological processes. For example, oxygen isotope composition of biogenic and abiogenic apatite are ideal proxies to reconstruct sea surface temperature and to tackle elemental cycling respectively, in which accurate and precise apatite oxygen isotope analysis is a basic requirement. Our robust evaluation demonstrates a lack of crystallographic orientation effects for Secondary Ion Mass Spectrometry (SIMS) apatite oxygen isotope analysis (expressed as δ18O). Apatite grains separated from the Qinghu monzonite were extensively analyzed by SIMS in the past decade in our laboratory, and 2041 individual δ18O measurements yield a two-standard-deviation of 0.47‰ (per mil, V-SMOW), or 0.16‰ when these measurements were integrated into 195 sessions. Homogenous oxygen isotope composition of Qinghu apatite (Qinghu-AP) at the micrometer level makes it a suitable reference material with a recommended δ18O value of 5.59 ± 0.19‰, as measured by Gas Source Isotope Ratio Mass Spectrometry with further validation from oxygen isotope thermometry. For seven randomly selected IGG (Institute of Geology and Geophysics)-Durango apatite crystals, our SIMS measurements suggest that they also have homogenous δ18O values (9.70 ± 0.22‰, 2 SD, n = 241, using Qinghu-AP as standard) without the presence of inter-grain and intra-grain heterogeneity. We documented a Y-coordinate related artificial effect, with measured δ18O values gradually increasing by ~1‰ from bottom to top of the mount over a distance of ~1.2 cm. This artifact is most likely caused by the presence of a slope (imperfect sample preparation and loading) or a gradient of accelerating voltage (conductivity of holder and sample) on the sample surface along the Y direction, which leads to an imperfect centering of the trajectory of the secondary ions. This effect can be reduced through applying a DTFA (dynamic transfer field aperture)-X correction. The presence of position-specific oxygen isotope fractionation could cause an artificial bias up to −6.7‰ when analyzing carbonated hydroxyapatite, and can reconcile the offset (e.g., −0.9 to 3.3‰) between δ18O values of conodonts measured by SIMS and IRMS. When working on hydrous systems (e.g., ore deposits) and low temperature environment (e.g., conodonts), where apatite is known to be water-rich and could be carbonated, a rigorous evaluation on this artificial bias is warranted. Since position-specific oxygen isotope fractionation is a common phenomenon observed in a variety of minerals (e.g., goethite, tourmaline and muscovite), attention should be paid in future studies. Our study highlights that SIMS is capable of providing accurate and precise δ18O measurements at the ~0.2‰ level, but high-quality reference materials and rigorous evaluations of potential artificial effects (e.g., topography, position, matrix, orientation, sample holder and position-specific oxygen isotope fractionation) degrading analytical accuracy are prerequisites.

Influences of oxidation ability on precision in nitrogen isotope measurements of organic reference materials using elemental analysis-isotope ratio mass spectrometry.

The precision of the standard measurements of reference materials (RMs) is critical to normalize the raw δ15 N values of samples to the international scale. Because the measurement configuration is required to moderate the properties of both RMs and samples for obtaining an ideal measurement precision, it is important to determine the appropriate measurement configurations of RMs to achieve accurate nitrogen isotope compositions of samples. Therefore, it is critical to systematically examine RMs for optimizing the configurations and further improve the measurement precision. Gas source isotope ratio mass spectrometry (IRMS) coupled with an online elemental analyzer (EA) equipped with a single-quartz reactor was performed to analyze the nitrogen isotope compositions. Some adjustments were made as follows: (a) as the in-house working standard, urea was used to investigate the influences of combustion through moderating the different oxygen injections (0-20 mL) and sample delay times (10-12 s) and optimize the combustion conditions to enhance oxidation ability; (b) CO2 from the sample gas stream was removed to prevent interferences between CO2 and N2 ; (c) international RMs, including USGS40 (l-glutamic), IAEA600 (caffeine), and soil standard (B2153) with a low organic content, were systematically analyzed under the optimized configurations, and the precisions of the δ15 N values were further examined. Our results showed that sufficient oxygen should be injected to improve the sample combustion when analyzing δ15 N in natural samples such as soil or marine sediment with low organic content. In addition, the measurement precision of δ15 N was affected by the tailing of the CO2 peak from the gas chromatography column into the subsequent sample measurement if the EA is equipped with a single-quartz reactor column. Our adjustments can produce an optimized repeatability and accuracy of the δ15 N value, especially for RMs with low organic content, and the uncertainty of the measurements is improved to be better than 0.1‰ under optimized configurations. The analytical conditions such as the oxygen flow rate and injection time or sample introduction time into the EA need to be adjusted depending on the combustion conditions of the RMs and samples to obtain a reliable accuracy of measurement. We recommend that when analyzing δ15 N of natural samples such as soil or marine sediment samples with low organic content, more oxygen should be injected to improve the combustion of the samples. In addition, CO2 should be removed from the sample gas stream before being introduced into the isotope ratio mass spectrometer when the EA is equipped with a single-quartz reactor.

Sulfur isotope behavior during metamorphism and anatexis of Archean sedimentary rocks: A case study from the Ghost Lake batholith, Ontario, Canada

Recycling of surface-derived sulfur into the deep earth can impart distinct sulfur isotope signatures to magmas. The details of sulfur transfer from sedimentary rocks to magmas (and ultimately igneous rocks) through metamorphism and devolatilization and/or partial melting, however, is difficult to trace. To understand this process in detail we studied multiple-sulfur isotope compositions of sulfides in the Archean (c. 2685 Ma) Ghost Lake batholith (GLB) and its surrounding host metasedimentary rocks of the Superior Craton (Ontario, Canada) by high spatial resolution secondary ion mass spectrometry, complemented by high-precision gas source isotope ratio mass spectrometry measurements. The GLB comprises strongly peraluminous biotite+cordierite, biotite+muscovite, and muscovite+garnet+tourmaline granites to leucogranites, which are thought to represent the partial melts of surrounding metagreywackes and metapelites. The metasedimentary rocks display a range of metamorphic grades increasing from biotite-chlorite (280-380°C) at ∼5 km away from the GLB to sillimanite-K-feldspar grade (∼660°C) immediately adjacent to the batholith, thus providing a natural experiment to understand sulfur isotope variations from low- to high-grade Archean sedimentary rocks, as well as granites representative of their partial melts.We find that metasedimentary sulfide δ34S values increase with progressive metamorphism at most 2-3‰ (from −1‰ up to +1 to +2‰). An increase in δ34S values in pyrrhotite during prograde metamorphism can be explained through Rayleigh fractionation during pyrite desulfidation reactions. Pyrite from all but one of the granite samples preserve δ34S values similar to that of the high-grade metasedimentary rocks, indicating that partial melting did not result in significant fractionation of δ34S. The exception to this is one granite sample from a part of the batholith characterized by abundant metasedimentary inclusions. This sample contains pyrite with heterogeneous and low δ34S values (down to −16‰) which likely resulted from incomplete homogenization of sulfur between the granitic melt and metasedimentary inclusions. Small (several tenths of a permil), mostly positive Δ33S are observed in both the metasedimentary rocks and granites.Our results suggest that Archean strongly peraluminous granites could be a high-fidelity archive to quantify the bulk sulfur isotope composition of the Archean siliciclastic sediments. Further, our findings indicate that subduction of reduced sulfur-bearing sediments in the Archean with δ34S at or near 0‰ should result in release of sulfur-bearing fluids in the mantle wedge with similar values (within a few permil). S-MIF (if initially present in Archean surface material) may be preserved during this process. However, the absence of S-MIF in igneous rocks does not preclude assimilation of Archean sedimentary material as either S-MIF may not be originally present in the Archean sedimentary sulfur and/or homogenization or dilution could obscure any S-MIF originally present in assimilated Archean sediments.

A Potential New Chalcopyrite Reference Material for Secondary Ion Mass Spectrometry Sulfur Isotope Ratio Analysis

Chalcopyrite is an important sulfide mineral in many types of ore deposits, but matrix‐matched chalcopyrite reference materials for microanalysis are lacking. A new natural chalcopyrite‐bearing specimen (HTS4‐6) was analysed in this study to investigate its potential as a reference material for microbeam sulfur isotope ratio measurement. Detailed textural examination and major element determination showed that the HTS4‐6 chalcopyrite grains have no growth rim or zoning. A total of 607 sulfur isotope ratio spot measurements with secondary ion mass spectrometry (SIMS) conducted on the cruciform sections, and over 120 randomly selected grains yielded highly consistent sulfur isotope ratio. The intermediate measurement precision for four measurement sessions of the 34S/32S measurement results was better than 0.39‰ (2s). Randomly selected chalcopyrite grains of HTS4‐6 were further analysed by LA‐MC‐ICP‐MS, which gave a mean δ34S value of +0.58 ± 0.38‰ (2s, n = 95). The maximum variance (expressed as intermediate precision from SIMS and LA‐MC‐ICP‐MS measurements) is not worse than 0.39‰ (the SIMS value), indicating that HTS4‐6 chalcopyrite is a potential reference material for in situ microbeam sulfur isotope measurements. The mean δ34S value determined by gas source isotope ratio mass spectrometry (GS‐IRMS) is +0.63 ± 0.16‰ (2s, n = 23), consistent with that derived by LA‐MC‐ICP‐MS, and can represent the recommended value for this potential reference material.

Determination of the triple oxygen and carbon isotopic composition of CO2 from atomic ion fragments formed in the ion source of the 253 Ultra high-resolution isotope ratio mass spectrometer.

RationaleDetermination of δ17O values directly from CO2 with traditional gas source isotope ratio mass spectrometry is not possible due to isobaric interference of 13C16O16O on 12C17O16O. The methods developed so far use either chemical conversion or isotope equilibration to determine the δ17O value of CO2. In addition, δ13C measurements require correction for the interference from 12C17O16O on 13C16O16O since it is not possible to resolve the two isotopologues.MethodsWe present a technique to determine the δ17O, δ18O and δ13C values of CO2 from the fragment ions that are formed upon electron ionization in the ion source of the Thermo Scientific 253 Ultra high‐resolution isotope ratio mass spectrometer (hereafter 253 Ultra). The new technique is compared with the CO2‐O2 exchange method and the 17O‐correction algorithm for δ17O and δ13C values, respectively.ResultsThe scale contractions for δ13C and δ18O values are slightly larger for fragment ion measurements than for molecular ion measurements. The δ17O and Δ17O values of CO2 can be measured on the 17O+ fragment with an internal error that is a factor 1–2 above the counting statistics limit. The ultimate precision depends on the signal intensity and on the total time that the 17O+ beam is monitored; a precision of 14 ppm (parts per million) (standard error of the mean) was achieved in 20 hours at the University of Göttingen. The Δ17O measurements with the O‐fragment method agree with the CO2‐O2 exchange method over a range of Δ17O values of −0.3 to +0.7‰.ConclusionsIsotope measurements on atom fragment ions of CO2 can be used as an alternative method to determine the carbon and oxygen isotopic composition of CO2 without chemical processing or corrections for mass interferences.

Sulfur isotope signatures in the lower crust: A SIMS study on S-rich scapolite of granulites

Scapolite is an important reservoir for volatiles in the deep crust and provides unique insights into the S isotope signatures at the mantle/crust interface. Here we document the first scapolite reference material (herein referred to as CB1) for in situ S isotope analysis. The chemical and isotopic composition of this euhedral, S-rich scapolite megacryst was characterized via LA-ICP-MS, EPMA, SIMS, and bulk fluorination gas source isotope ratio mass spectrometry. The CB1 scapolite is isotopically homogeneous and our results show that crystal orientation does not affect in situ S isotope SIMS analysis. This makes CB1 an ideal primary calibration standard for in situ analysis of S isotope ratios (36S/32S, 34S/32S and 33S/32S) in scapolite. With this reference material in hand, we then applied in situ SIMS analysis of S isotopes for the first time on scapolite in granulite samples from the lower crust/upper mantle. The analysed sample suite comprises rocks from classic granulite xenolith locations in southeastern Australia, as well as a sample from the high-grade suture zone of the Dahomeyides in south-eastern Ghana. The results show that scapolites in the lower crust have δ34S values between ~−0.5 and +4 (‰ VCDT). These values fall within the range of S isotope signatures present in mantle rocks and provide no evidence for the recycling of seawater-derived S into the lower crust. We propose that scapolite formed during granulite facies metamorphism of igneous cumulates, where S was sourced from precursor igneous sulfides. Sulfur isotope heterogeneities between individual scapolite grains in some of the studied samples may reflect non-uniform S-isotope compositions of igneous S-phases, which precipitated from mantle-derived melt.

Chemical and oxygen isotope composition of gem-quality apatites: Implications for oxygen isotope reference materials for secondary ion mass spectrometry (SIMS)

Oxygen isotope ratios (δ18O) of biogenic apatite have become a widely used tool for reconstructing palaeoenvironmental conditions in the past. Ongoing improvements in secondary ion mass spectrometry (SIMS) technology have made in situ δ18O analyses on sub-nanogram domains within single microfossil samples possible; however this method requires calibration with reference materials (RMs) with a matrix “similar” to that of the samples. Here we evaluated five sources of gem-quality, abiogenic apatites to assess their potentials as SIMS RMs. Our results show that all these gem-quality apatites are low-REEs calcium fluorapatites with δ18OVSMOW values between 6.6 and 11.4‰. Large variations in δ18O have been found for between crystals from a single deposit as well as within individual crystals. Durango apatite has an inter-crystal δ18O range of 4.4‰ (6.6–11.0‰, N=9 crystals). Madagascar Green apatite, Madagascar 1st Mine apatite and Ipira apatite have inter-crystal variations in δ18O of 4.1‰ (7.3–11.4‰, N=15 crystals), 3.5‰ (7.6–11.1‰, N=9 crystals) and 3.1‰ (7.1–10.2‰, N=11 crystals), respectively. South Africa Blue apatite has a smaller inter-crystal δ18O range of only 0.9‰ (8.7–9.6‰, N=6 crystals), though this might be an artefact due to the restricted number of samples studied. Intra-crystal δ18O variations of studied crystals generally range from 0.8 to 1.8‰. However, several gem apatite crystals from Madagascar have minor δ18O variation within 0.5‰ and represent most promising candidate RM.Gem-quality abiogenic apatites can be used as RMs for calibrating SIMS δ18O analyses, however these require homogeneity testing at sub-millimetre scale in advance. Durango crystals, commonly used as RMs in earlier SIMS-based studies, display a conspicuous heterogeneity in δ18O, with intra-crystal variations ranging from 0.7 to 2‰ as detected by both gas source isotope ratio mass spectrometry and large geometry SIMS. Thus, Durango apatite cannot be considered as suitable for SIMS calibration and alternative reference materials need to be sought.

Sulfur isotope composition of metasomatised mantle xenoliths from the Bultfontein kimberlite (Kimberley, South Africa): Contribution from subducted sediments and the effect of sulfide alteration on S isotope systematics

Abstract Sulfur isotopes are a powerful geochemical tracer in high-temperature processes, but have rarely been applied to the study of mantle metasomatism. In addition, there are very limited S isotope data on sub-continental lithospheric mantle (SCLM) material. For cratonic regions, these data are restricted to sulfide inclusions in diamonds. To provide new constraints on the S isotope composition of the SCLM and on the source(s) of mantle metasomatic fluids beneath the diamondiferous Kimberley region (South Africa), we investigated the S isotope systematics of five metasomatised mantle xenoliths from the Bultfontein kimberlite. Pentlandite and chalcopyrite in these xenoliths were analysed by in situ secondary-ion mass spectrometry (SIMS), with bulk-rock material measured by gas source isotope ratio mass spectrometry techniques. Based on previous studies, the xenoliths experienced different types of metasomatism to one another at distinct times (∼180 and ∼90–80 Ma). Contained pentlandite grains show variable alteration to heazlewoodite (i.e. Ni sulfide) + magnetite. The in situ S isotope analyses of pentlandite exhibit a relatively restricted range between −5.9 and − 1.4 ‰ δ 34 S (compared to VCDT), with no statistically meaningful differences between samples. Chalcopyrite only occurs in one sample and shows δ 34 S values between −5.4 and − 1.0 ‰ . The bulk-rock Ssulfide isotope analyses vary between −3.4 and + 0.8 ‰ δ 34 S . Importantly, the only sample hosting dominantly fresh sulfides shows a bulk-rock δ 34 S value consistent with the mean value for the sulfides, whereas the other samples exhibit higher bulk 34S/32S ratios. The differences between bulk-rock and average in situ δ 34 S values are directly correlated with the degree of sulfide alteration. This evidence indicates that the elevated 34S/32S ratios in the bulk samples are not due to the introduction of heavy S (commonly as sulfates) and are best explained by isotopic fractionation coupled with the removal of light S during serpentinisation, when pentlandite is altered to S-poor mixtures of heazlewoodite and magnetite. Available bulk Ssulfide isotopic data for SCLM peridotite xenoliths are dominated by positive δ 34 S values, which contrasts with the negative values of the sulfides. These results imply that the mantle S isotope values from bulk peridotite samples are commonly modified by isotopic fractionation during serpentinisation. Therefore, the S isotopic composition of the SCLM may require revision. The limited isotopic variability shown by sulfides in the Bultfontein mantle xenoliths is probably due to intermittent tapping of a mantle source with a relatively restricted S isotope composition. While the asthenospheric mantle ( δ 34 S ≤ − 1.4 ‰ ) is a viable candidate, δ 34 S values as low as − 5.9 ‰ require input from recycled crustal material, possibly represented by the sulfur reservoir with negative δ 34 S signature that is missing in the >500 Ma sedimentary record and could have been subducted and stored in the Earth's mantle.

Improved analysis of micro- and nanomole-scale sulfur multi-isotope compositions by gas source isotope ratio mass spectrometry.

Multiple sulfur isotope compositions are usually measured on relatively large samples (in the range of micromoles); however, sometimes only small amounts are available and thus it is necessary to analyze small (sub-micromole) samples. We report an improved method to measure multiple sulfur isotope compositions: δ(33) S, δ(34) S and δ(36) S values on the SF6 molecule (m/z 127, 128, 129, 131) for quantities down to 0.1 micromole, and δ(33) S and δ(34) S values for quantities down to 20 nanomoles. Multiple sulfur isotope analyses including fluorination and purification of two international Ag2 S standards, IAEA-S1 and IAEA-S3, were carried out at various low concentrations on a dual-inlet isotope ratio mass spectrometer using a microvolume and modified resistor capacities. The analyses yielded a narrow range of δ(34) S values vs CDT (the international standard), with an overall standard deviation of ±0.2 ‰, which was within the range of certified values. This demonstrates the feasibility of determining both Δ(33) S and Δ(36) S values on the sub-micromole scale, and Δ(33) S values on the nanomole scale with similar accuracy to conventional dual-inlet analyses. The analysis of the three S-isotope ratios on the SF6 molecule using the so-called conventional fluorination method and dual-inlet ion ratio mass spectrometry is reliable for sample sizes down to ~20 nanomoles. Despite being close to the theoretical limits for maintaining the viscous flow regime of gas in the capillary, errors were not limited by counting statistics, but probably relate to sample gas purification. Copyright © 2016 John Wiley & Sons, Ltd.

Non-linear mixing effects on mass-47 CO2 clumped isotope thermometry: Patterns and implications.

Mass-47 CO(2) clumped isotope thermometry requires relatively large (~20 mg) samples of carbonate minerals due to detection limits and shot noise in gas source isotope ratio mass spectrometry (IRMS). However, it is unreasonable to assume that natural geologic materials are homogenous on the scale required for sampling. We show that sample heterogeneities can cause offsets from equilibrium Δ(47) values that are controlled solely by end member mixing and are independent of equilibrium temperatures. A numerical model was built to simulate and quantify the effects of end member mixing on Δ(47). The model was run in multiple possible configurations to produce a dataset of mixing effects. We verified that the model accurately simulated real phenomena by comparing two artificial laboratory mixtures measured using IRMS to model output. Mixing effects were found to be dependent on end member isotopic composition in δ(13)C and δ(18)O values, and independent of end member Δ(47) values. Both positive and negative offsets from equilibrium Δ(47) can occur, and the sign is dependent on the interaction between end member isotopic compositions. The overall magnitude of mixing offsets is controlled by the amount of variability within a sample; the larger the disparity between end member compositions, the larger the mixing offset. Samples varying by less than 2 ‰ in both δ(13)C and δ(18)O values have mixing offsets below current IRMS detection limits. We recommend the use of isotopic subsampling for δ(13)C and δ(18)O values to determine sample heterogeneity, and to evaluate any potential mixing effects in samples suspected of being heterogonous.

Kinetics of CO2(g)–H2O(1) isotopic exchange, including mass 47 isotopologues

The analysis of mass 47 isotopologues of CO2 (mainly 13C18O16O) is established as a constraint on sources and sinks of environmental CO2, complementary to δ13C and δ18O constraints, and forms the basis of the carbonate clumped isotope thermometer. This measurement is commonly reported using the Δ47 value — a measure of the enrichment of doubly substituted CO2 relative to a stochastic isotopic distribution. Values of Δ47 for thermodynamically equilibrated CO2 approach 0 (a random distribution) at high temperatures (≥ several hundred degrees C), and increase with decreasing temperature, to ≈0.9% at 25°C. While the thermodynamic properties of doubly substituted isotopologues of CO2 (and, similarly, carbonate species) are relatively well understood, there are few published constraints on their kinetics of isotopic exchange. This issue is relevant to understanding both natural processes (e.g., photosynthesis, respiration, air–sea or air–groundwater exchange, CO2 degassing from aqueous solutions, and possibly gas–sorbate exchange on cold planetary surfaces like Mars), and laboratory handling of CO2 samples for Δ47 analysis (e.g., re-equilibration in the presence of liquid water, water ice or water adsorbed on glass or metal surfaces). We present the results of an experimental study of the kinetics of isotopic exchange, including changes in Δ47 value, of CO2 exposed to liquid water between 5 and 37°C. Aliquots of CO2 gas were first heated to reach a nearly random distribution of its isotopologues and then exposed at low pressure for controlled periods of time to large excesses of liquid water in sealed glass containers. Containers were held at 5, 25 and 37°C and durations of exchange ranging from 5min to 7days. To avoid the formation of a boundary layer that might slow exchange, the tubes were vigorously shaken during the period of exchange. At the end of each experiment, reaction vessels were flash frozen in liquid nitrogen. CO2 gas was then recovered from the head space of the reaction vessel, purified and analyzed for its Δ47, δ13C and δ18O by gas source isotope ratio mass spectrometry. Equilibrium was reached for both δ18O and Δ47 after durations of a few hours to tens of hours. δ18O values at equilibrium were consistent with known fractionation factors for the CO2–H2O system. The evolution of δ18O and Δ47 with experiment duration were consistent with first-order reactions, with rate constants equal to each other (within error), averaging 0.19h−1 at 5°C, 0.38h−1 at 25°C and 0.65h−1 at 37°C. We calculate an activation energy for this isotopic exchange reaction of 26.2kJ/mol. By comparison, Mills and Urey (1940) measured the rate of 18O exchange between CO2(aq) and water to have a rate of 11h−1 at 25°C and an activation energy of 71.7kJ/mol. Our finding of a slower rate and lower activation energy is consistent with the rate limiting step of our experiment being the CO2(g)–CO2(aq) exchange, even when samples are shaken during the partial equilibration. Our results broadly resemble those from the study of (Affek, 2013), though this prior study found a lower rate constant for Δ47. We propose that the difference is due to analytical uncertainties and explore the theoretical consequences of unequal reaction rates between 12C18O16O and 13C18O16O with a forward model.

Clumped isotope analysis of carbonates: comparison of two different acid digestion techniques

The kinetic nature of the phosphoric acid digestion reaction enables clumped isotope analysis of carbonates using gas source isotope ratio mass spectrometry (IRMS). In most laboratories acid digestions are performed at 25°C in sealed vessels or at 90°C in a common acid bath. Here we show that different Δ47 results are obtained depending on the digestion technique employed. Several replicates of a biogenic aragonite and NBS 19 were reacted with 104% H3 PO4 in sealed vessels at 25°C and at 90°C using a common acid bath. The sample size varied between 4 mg and 14 mg. Purification methods that are standard for clumped isotope analyses were applied to the evolved CO2 before measuring the abundances of masses 44 to 49 relative to a reference gas by IRMS. A systematic trend to lower and more consistent Δ47 values is observed for reactions at 25°C if the sample size is increased. We suggest that secondary re-equilibration of evolved CO2 or reaction intermediates with free water molecules preferentially occurs for relatively small samples (4-7 mg), finally yielding elevated Δ47 values compared with >7 mg aliquots. In contrast, no such sample size effect on Δ47 values is observed for carbonates that are digested at 90°C using the common acid bath. The determination of Δ47 values of carbonate samples smaller than 7 mg becomes more precise and accurate if digestions are performed at 90°C. Based on our results we propose that the difference in phosphoric acid fractionation factor between 25°C and 90°C is 0.07‰ for both calcite and aragonite.

Resolving the Germanium Atomic Weight Disparity Using Multicollector ICPMS

Two most recent mass spectrometric measurements of natural isotopic composition germanium gave discordant Ge atomic weight values of 72.6276(64)(k=2) and 72.6390(69)(k=2), respectively, a decade ago. Each measurement was performed with a different mass spectrometry platform, gas source isotope ratio mass spectrometry and thermal ionization mass spectrometry, respectively. Herein we report results obtained by multicollector inductively coupled plasma mass spectrometry yielding an atomic weight of germanium 72.6296(19)(k=2) which is in support of the upcoming 2009 Standard Atomic Weight adjustment by IUPAC. Germanium isotope ratios were calibrated using a regression mass bias correction model and NIST SRM 994 gallium isotopic reference material. In this model, no assumptions are made regarding the mass bias differences between gallium and germanium or between the isotopes of germanium. Isotope ratios of 0.5620(21), 0.7515(16), 0.2125(7), and 0.2121(12) were obtained for n((70)Ge)/n((74)Ge), n((72)Ge)/n((74)Ge), n((73)Ge)/n((74)Ge), and n((76)Ge)/n((74)Ge), respectively, with expanded uncertainties (k = 2) estimated in accordance with the ISO/BIPM Guide to the Expression of Uncertainty in Measurements.

Energetic costs of male reproduction in a scramble competition mating system

1. The assumption that the primary limitations on reproductive success differ between the sexes is inherent in traditional sexual selection theory. Although the energy that can be allocated to reproduction is assumed to be the main limitation to females, the ability to attract and defend oestrous females is assumed to be the primary limitation to males. 2. Estimates of the energetic costs of reproduction in male mammals are, however, limited and have largely been obtained from sexually dimorphic species exhibiting female defence mating systems. These studies often reveal that the energetic cost of male reproduction is similar to or even exceeds that of females, and therefore challenge long-held assumptions of inter-sexual reproductive limitations, but their generality is little known. 3. We coupled measurements of energy expenditure with detailed behavioural observations of reproductive male North American red squirrels (Tamiasciurus hudsonicus). This species displays minimal sexual dimorphism and exhibits a scramble competition mating system, under which sexual selection favours enhanced mate searching effort by males. 4. We conducted the study over 2 years characterized by a substantial variation in upcoming natural food availability and across two study populations that experienced either natural food abundance or an ad libitum food-supplementation to investigate the influence of resource availability on male reproductive energy expenditure. 5. Under natural conditions, mean energy expenditure of males across the 2 years was high, approximating that of females during lactation. Furthermore, in the anticipation of high upcoming natural food availability and resultant offspring survival, expenditure approximately doubled (from 290 +/- 7 to 579 +/- 73 kJ day(-1)). When current food availability (and consequently the density of receptive females) was experimentally elevated, males displayed the highest levels of energy expenditure we recorded (873 +/- 98 kJ day(-1)). 6. Our results provide compelling evidence that the energy available for reproductive allocation places a strong limitation on reproduction in male North American red squirrels and contribute to previous work suggesting that high and limiting energetic costs of male reproduction may be a general feature of mammalian reproduction.