Mass-independent Isotopic Composition Research Articles

NWA 11562: A Unique Ureilite with Extreme Mg-rich Constituents

A comprehensive study of an ungrouped achondrite meteorite, North West Africa (NWA) 11562, was conducted, involving petrology, mineralogy, and mass-independent chromium isotopic composition. NWA 11562 comprises 34.9 vol% olivine, 56.1 vol% pyroxenes, 6.7 vol% Fe–Ni metal and oxides, 2.2 vol% carbon, and 0.2 vol% anhydrite. The oxygen isotopic composition (δ 18O = 6.24‰ ± 0.13‰ and Δ17O = −1.81‰ ± 0.03‰; Meteoritical Bulletin Database) and chromium isotopic compositions (ε 54Cr = −0.82 ± 0.10, 2SE) are consistent with NWA 11562 being a ureilite, and petrographic observations show features similar to those of the common ureilite group meteorites. Olivine (core: Fo99.0 ± 0.1; rim: Fo98.9 ± 0.1) and pyroxene (orthopyroxene: Mg# 99.0 ± 0.2; clinopyroxene: Mg# 99.1 ± 0.7) core compositions are more magnesian than in any previously known ureilite and lack the characteristic reduction rims of ureilites. Rounded small olivine grains within NWA 11562 indicate that the meteorite experienced impact and associated melting. Combined with the characteristic Fe/Mn ratio (3.84 ± 0.16) and Mg# (99.0 ± 0.1) of olivine cores, we suggest that NWA 11562 represents a more Mg-rich ureilite than any previously reported. NWA 11562 has a high 55Mn/52Cr ratio, and when combined with literature data, it plots on a well-defined 53Mn–53Cr isochron, providing a more accurate age, i.e., 4566.7 ± 0.8 Ma, overlapping previous work. This age may represent the result of early partial melting of the ureilite parent body.

Origin and abundances of volatiles on Mars from the zinc isotopic composition of Martian meteorites

Volatile elements are key to understanding the accretion and differentiation processes that formed the terrestrial planets. Relative to the solar photosphere or carbonaceous Ivuna-type (CI) chondrites, the terrestrial planets are depleted in moderately volatile elements (MVEs), with the Earth being more depleted in MVEs than Mars. Mass-dependent and mass-independent stable isotope variations of MVEs, such as Zn, can be used to determine the origin of volatile depletion on Mars. Here we present Zn isotopic compositions of ten Martian meteorites, spanning the major petrologic groups, and show that the Zn isotope composition of the Martian mantle, representative of the Bulk Silicate Mars (BSM), has a δ66Zn (per mille deviation of the 66Zn/64Zn from the JMC-Lyon standard) of +0.50 ± 0.18. This is distinctly heavier than that of the Earth (+0.16 ± 0.06‰). The BSM Zn isotope composition could partly reflect fractionation during volatile loss by evaporation consistent with the isotopic composition of other volatile elements (e.g., K). The mass-independent Zn isotopic composition of Mars, ε66Zn (per 10,000 deviation of the 66Zn/64Zn from the terrestrial standard JMC-Lyon, normalized to 68Zn/64Zn) is intermediate between carbonaceous chondrites (CC) and non-carbonaceous chondrites (NC), but with stronger affinity to the NC compared to that of the Earth. Therefore, planets further from the Sun are not necessarily made from a higher fraction of CC-like material.

Genetics, age, and crystallization history of group IC iron meteorites

The IC iron meteorite group is characterized utilizing nucleosynthetic mass-independent isotopic compositions and 182W age constraints, coupled with siderophile element concentration measurements and modeling of crystal-liquid fractionation processes. The six IC irons analyzed, Arispe, Bendego, Chihuahua City, Nocoleche, NWA 2743, and Winburg have indistinguishable Mo and W genetic isotopic compositions and are consistent with derivation from the same parent body, which formed in the non-carbonaceous (NC) nebular reservoir. A pre-exposure µ182W value (parts-per-million deviations in isotopic ratios from terrestrial standards) for the six IC irons of −337 ± 5 corresponds to a metal-silicate segregation age of 1.0 ± 0.4 Myr after calcium-aluminum-rich inclusion (CAI) formation. This age is similar to those determined for other NC iron groups. Siderophile element abundances of the IC irons are generally similar and characterized by minor depletions in the more volatile siderophile elements. Highly siderophile element (HSE) distributions among the IC group suggest that the initial parent body core was S-rich, with preferred model results indicating an initial melt composition with ∼ 18 wt% S, 2 wt% P and 0.03 wt% C. Processes in addition to fractional crystallization, such as late-stage parent body modification, possibly as a result of impacts, and subsequent metal-melt mixing, are required within the first 100 Myr of Solar System history to explain the range of HSE abundances.

Role of Dust and Iron Solubility in Sulfate Formation during the Long-Range Transport in East Asia Evidenced by 17O-Excess Signatures.

Numerical models have been developed to elucidate air pollution caused by sulfate aerosols (SO42–). However, typical models generally underestimate SO42–, and oxidation processes have not been validated. This study improves the modeling of SO42– formation processes using the mass-independent oxygen isotopic composition [17O-excess; Δ17O(SO42–)], which reflects pathways from sulfur dioxide (SO2) to SO42–, at the background site in Japan throughout 2015. The standard setting in the Community Multiscale Air Quality (CMAQ) model captured SO42– concentration, whereas Δ17O(SO42–) was underestimated, suggesting that oxidation processes were not correctly represented. The dust inline calculation improved Δ17O(SO42–) because dust-derived increases in cloud-water pH promoted acidity-driven SO42– production, but Δ17O(SO42–) was still overestimated during winter as a result. Increasing solubilities of the transition-metal ions, such as iron, which are a highly uncertain modeling parameter, decreased the overestimated Δ17O(SO42–) in winter. Thus, dust and high metal solubility are essential factors for SO42– formation in the region downstream of China. It was estimated that the remaining mismatch of Δ17O(SO42–) between the observation and model can be explained by the proposed SO42– formation mechanisms in Chinese pollution. These accurately modeled SO42– formation mechanisms validated by Δ17O(SO42–) will contribute to emission regulation strategies required for better air quality and precise climate change predictions over East Asia.

Evidence of a primordial isotopic gradient in the inner region of the solar protoplanetary disc

Not only do the sampled terrestrial worlds (Earth, Mars, and asteroid 4 Vesta) differ in their mass-independent (nucleosynthetic) isotopic compositions of many elements (e.g. ε48Ca, ε50Ti, ε54Cr, ε92Mo), the magnitudes of some of these isotopic anomalies also appear to correlate with heliocentric distance. While the isotopic differences between the Earth and Mars may be readily accounted for by the accretion of mostly local materials in distinct regions of the protoplanetary disc, it is unclear whether this also applies to asteroid Vesta. Here we analysed the available data from our numerical simulation database to determine the formation location of Vesta in the framework of three planet-formation models: classical, Grand Tack, and Depleted Disc. We find that Vesta has a high probability of forming locally in the asteroid belt in models where material mixing in the inner disc is limited; this limited mixing is implied by the isotopic differences between the Earth and Mars. Based on our results, we propose several criteria to explain the apparent correlation between the different nucleosynthetic isotopic compositions of the Earth, Mars, and Vesta: (1) these planetary bodies accreted their building blocks in different regions of the disc, (2) the inner disc is characterised by an isotopic gradient, and (3) the isotopic gradient was preserved during the formation of these planetary bodies and was not diluted by material mixing in the disc (e.g. via giant planet migration).

Mass-independent and mass-dependent Cr isotopic composition of the Rumuruti (R) chondrites: Implications for their origin and planet formation

Mass-independent and mass-dependent Cr isotopic composition of the Rumuruti (R) chondrites: Implications for their origin and planet formation

Evidence from achondrites for a temporal change in Nd nucleosynthetic anomalies within the first 1.5 million years of the inner solar system formation

Heterogeneity in isotopic compositions within the protoplanetary disc has been demonstrated for a number of elements measured in extra-terrestrial materials, mostly based on chondrite meteorite analyses. However, precise 182Hf-182W and 26Al-26Mg ages of iron meteorites, achondrites, and chondrules show that chondrites accreted later than achondrites and therefore do not strictly represent the early (<2 Ma) solar system composition. Here we present the Nd mass-independent stable isotopic compositions of a suite of diverse achondrites to better constrain the Nd isotope evolution of the early solar system. Carbonaceous (C) achondrites are indistinguishable from their chondritic counterpart. However, early formed planetesimals as sampled by silicate-rich non-carbonaceous (NC) achondrite meteorites have higher 145Nd/144Nd and 148Nd/144Nd ratios (3.9 <μ145Nd < 11.0 and 9.1 <μ148Nd < 17.9 in part per million deviation, or μiNd) compared to NC chondrites (2.7 <μ145Nd < 3.3 and 2.2 <μ148Nd < 8.1). Moreover, the three terrestrial planets for which we have samples available (Earth, Mars, and the Moon) as well as the silicate inclusions from the non-magmatic IIE iron meteorite Miles present a systematic deficit in μ145Nd and μ148Nd compared to early-formed NC achondrites. Unlike chondrites, the Nd anomalies in achondrites are not correlated to the heliocentric distance of accretion of their respective parent bodies as inferred from redox conditions. Chronological constraints on planetesimal accretion suggest that Nd (and other elements such as Mo and Zr) nucleosynthetic compositions of the inner part of the protoplanetary disc significantly changed around 1.5 Ma after Solar System formation due to thermal processing of dust in the protoplanetary disc. This relatively late event coincides with the beginning of chondrule formation or at least their preservation. Terrestrial planets formed subsequently by a complex accretion regime during several million years. Therefore, two scenarios are envisioned considering the reported Nd isotope composition of early planetesimals: 1) Terrestrial planets accreted mostly chondritic material similar in composition to enstatite chondrites, or 2) early planetesimals constitute substantial parts of terrestrial planets building blocks mixed with highly thermally processed material enriched in s-process, still unsampled by meteorites.

Mass-independent and mass-dependent Cr isotopic composition of the Rumuruti (R) chondrites: Implications for their origin and planet formation

Chromium (Cr) isotopes play an important role in cosmochemistry and planetary science because they are powerful tools for dating (53Mn–53Cr short-lived chronometry), tracing (54Cr nucleosynthetic anomalies) the origins of the materials, and studying the processes involved in volatile element fractionation and planetary differentiation (Cr stable isotopic fractionation). To use Cr isotopes for these purposes, it is essential to precisely know the compositions of the various chondritic reservoirs. However, the Cr isotope composition of Rumuruti (R) chondrites remains unknown. Here, we report high-precision mass-independent (average 2SE uncertainty of ∼0.02 and ∼0.06 for ε53Cr and ε54Cr, respectively; ε indicates 10,000 deviation) and mass-dependent (uncertainty of average 0.03‰ for δ53Cr; δ indicates 1000 deviation) Cr isotope data for 12 bulk R chondrites of petrologic types 3–6 (including R chondrite breccias), and one R chondrite-like clast (MS-CH) in the Almahata Sitta polymict ureilite. All the R chondrites show homogeneous bulk ε54Cr values, −0.06 ± 0.08 (2SD), similar only to those of the Earth–Moon system and enstatite chondrites. This first ε54Cr dataset for R chondrites provides significant addition to the ε54Cr–Δ17O diagram, and positions them as a potential endmember for planetary precursors. The R chondrites possess a higher 55Mn/52Cr of 0.68 ± 0.04 relative to most of carbonaceous chondrites and higher ε53Cr values 0.23 ± 0.05 (2SD) relative to most of chondrite groups. This likely results from the lower chondrule abundance in R chondrites compared to that of ordinary and enstatite chondrites. The stable Cr isotope composition of R chondrites is homogeneous with a δ53Cr = −0.12 ± 0.03‰ (2SD). Combined with previous data of other groups of chondrites, we show that the stable Cr isotopic composition of all the chondrites is homogeneous with δ53Cr of −0.12 ± 0.04‰ (2SD, N = 42) and is independent of the petrologic type and redox conditions. The lack of mass-dependent fractionation between all groups of chondrites suggests that the average chondrite δ53Cr value is also representative for the initial composition of all differentiated planets in the Solar System. Finally, the MS–CH clast in Almahata Sitta has a Cr isotopic composition (ε53Cr = 0.18 ± 0.04, ε54Cr = −0.16 ± 0.07, and δ53Cr = −0.11 ± 0.05‰) that is consistent (within error) with it being an R chondrite-like clast.

Genetics, age and crystallization history of group IIC iron meteorites

The eight iron meteorites currently classified as belonging to the IIC group were characterized with respect to the compositions of 21 siderophile elements. Several of these meteorites were also characterized for mass independent isotopic compositions of Mo, Ru and W. Chemical and isotopic data for one, Wiley, indicate that it is not a IIC iron meteorite and should be reclassified as ungrouped. The remaining seven IIC iron meteorites exhibit broadly similar bulk chemical and isotopic characteristics, consistent with an origin from a common parent body. Variations in highly siderophile element (HSE) abundances among the members of the group can be well accounted for by a fractional crystallization model with all the meteorites crystallizing between ∼10 and ∼26% of the original melt, assuming initial S and P concentrations of 8 wt.% and 2 wt.%, respectively. Abundances of HSE estimated for the parental melt suggest a composition with chondritic relative abundances of HSE ∼6 times higher than in bulk carbonaceous chondrites, consistent with the IIC irons sampling a parent body core comprising ∼17% of the mass of the body.Radiogenic 182W abundances of two group IIC irons, corrected for a nucleosynthetic component, indicate a metal-silicate segregation age of 3.2 ± 0.5 Myr subsequent to the formation of Calcium-Aluminum-rich Inclusions (CAI). When this age is coupled with thermal modeling, and assumptions about the Hf/W of precursor materials, a parent body accretion age of 1.4 ± 0.5 Myr (post-CAI) is obtained.The IIC irons and Wiley have 100Ru mass independent “genetic” isotopic compositions that are identical to other irons with so-called carbonaceous chondrite (CC) type genetic affinities, but enrichments in 94,95,97Mo and 183W that indicate greater s-process deficits relative to most known CC iron meteorites. If the IIC irons and Wiley are of the CC type, this indicates variable s-process deficits within the CC reservoir, similar to the s-process variability within the NC reservoir observed for iron meteorites. Nucleosynthetic models indicate that Mo and 183W s-process variability should correlate with Ru isotopic variability, which is not observed. This may indicate the IIC irons and Wiley experienced selective thermal processing of nucleosynthetic carriers, or are genetically distinct from the CC and NC precursor materials.

Large mass-independent sulphur isotope anomalies link stratospheric volcanism to the Late Ordovician mass extinction

Volcanic eruptions are thought to be a key driver of rapid climate perturbations over geological time, such as global cooling, global warming, and changes in ocean chemistry. However, identification of stratospheric volcanic eruptions in the geological record and their causal link to the mass extinction events during the past 540 million years remains challenging. Here we report unexpected, large mass-independent sulphur isotopic compositions of pyrite with Δ33S of up to 0.91‰ in Late Ordovician sedimentary rocks from South China. The magnitude of the Δ33S is similar to that discovered in ice core sulphate originating from stratospheric volcanism. The coincidence between the large Δ33S and the first pulse of the Late Ordovician mass extinction about 445 million years ago suggests that stratospheric volcanic eruptions may have contributed to synergetic environmental deteriorations such as prolonged climatic perturbations and oceanic anoxia, related to the mass extinction.

New implications for the origin of the IAB main group iron meteorites and the isotopic evolution of the noncarbonaceous (NC) reservoir

The origin of the IAB main group (MG) iron meteorites is explored through consideration of 182W isotopic compositions, thermal modeling of 26Al decay, and mass independent (nucleosynthetic) Mo isotopic compositions of planetesimals formed in the noncarbonaceous (NC) protosolar isotopic reservoir. A refined 182W model age for the meteorites Campo del Cielo, Canyon Diablo, and Nantan suggests that the IAB-MG parent body underwent some form of metal-silicate segregation as early as 5.3 ± 0.4 Myr after calcium-aluminum rich inclusion (CAI) formation or as late as 13.8 ± 1.4 Myr after CAI formation. If melting of the IAB-MG occurred prior to 7 Myr after CAI formation, it was likely driven by 26Al decay for a parent body radius >40 km. Otherwise, additional heat from impact is required for melting metal this late in Solar System history. If melting was partially or wholly the result of internal heating, a thermal model of 26Al decay heat production constrains the accretion age of the IAB-MG parent body to ∼1.7 ± 0.4 Myr after CAI formation. If melting was, instead, dominantly caused by impact heating, thermal modeling suggests the parent body accreted more than 2 Myr after CAI formation. Comparison of Mo mass independent isotopic compositions of the IAB-MG to other NC bodies with constrained accretion ages suggests that the Mo isotopic composition of the NC reservoir changed with time, and that the IAB-MG parent body accreted between 2 to 3 Myr after CAI formation, thus requiring an origin by impact. The relationship between nucleosynthetic Mo isotopic compositions and accretion ages of planetesimals from the NC reservoir suggests that isotopic heterogeneity developed from either addition of s-process material to, or removal of coupled r-/p-process material from the NC reservoir.

Fingerprints of the Protosolar Cloud Collapse in the Solar System. II. Nucleosynthetic Anomalies in Meteorites

Abstract The isotopic heterogeneity of the solar system shown by meteorite analyses is more pronounced for its earliest objects, the calcium–aluminum-rich inclusions (CAIs). This suggests that it was inherited from spatial variations in stardust populations in the protosolar cloud. We model the formation of the solar protoplanetary disk following its collapse and find that the solid-weighted standard deviation of different nucleosynthetic contributions in the disk is reduced by one order of magnitude compared to the protosolar cloud, whose successive isotopic signatures are fossilized by CAIs. The enrichment of carbonaceous chondrites in r-process components, whose proportions are inferred to have diminished near the end of infall, is consistent with their formation at large heliocentric distances, where the early signatures would have been preferentially preserved after outward advection. We also argue that thermal processing had little effect on the (mass-independent) isotopic composition of bulk meteorites for refractory elements.

Combined mass-dependent and nucleosynthetic isotope variations in refractory inclusions and their mineral separates to determine their original Fe isotope compositions.

Calcium-aluminum-rich inclusions (CAIs) are the oldest dated materials that provide crucial information about the isotopic reservoirs present in the early Solar System. For a variety of elements, CAIs have isotope compositions that are uniform yet distinct from later formed solid material. However, despite being the most abundant metal in the Solar System, the isotopic composition of Fe in CAIs is not well constrained. In an attempt to determine the Fe isotopic compositions of CAIs, we combine extensive work from a previously studied CAI sample set with new isotopic work characterizing mass-dependent and mass-independent (nucleosynthetic) signatures in Mg, Ca, and Fe. This investigation includes work on three mineral separates of the Allende CAI Egg 2. For all isotope systems investigated, we find that in general, fine-grained CAIs exhibit light mass-dependent isotopic signatures relative to terrestrial standards, whereas igneous CAIs have heavier isotopic compositions relative to the fine-grained CAIs. Importantly, the mass-dependent Fe isotope signatures of bulk CAIs show a range of both light (fine-grained CAIs) and heavy (igneous CAIs) isotopic signatures relative to bulk chondrites, suggesting that Fe isotope signatures in CAIs largely derive from mass fractionation events such as condensation and evaporation occurring in the nebula. Such signatures show that a significant portion of the secondary alteration experienced by CAIs, particularly prevalent in fine-grained inclusions, occurred in the nebula prior to accretion into their respective parent bodies. Regarding nucleosynthetic Fe isotope signatures, we do not observe any variation outside of analytical uncertainty in bulk CAIs compared to terrestrial standards. In contrast, all three Egg 2 mineral separates display resolved mass-independent excesses in 56Fe compared to terrestrial standards. Furthermore, we find that the combined mass-dependent and nucleosynthetic Fe isotopic compositions of the Egg 2 mineral separates are well correlated, likely indicating that Fe indigenous to the CAI is mixed with less anomalous Fe, presumably from the solar nebula. Thus, these reported nucleosynthetic anomalies may point in the direction of the original Fe isotope composition of the CAI-forming region, but they likely only provide a minimum isotopic difference between the original mass-independent Fe isotopic composition of CAIs and that of later formed solids.

The role of S−3 ion in thermochemical sulphate reduction: Geological and geochemical implications

Thermochemical sulphate reduction (TSR) plays a crucial role in the global sulphur cycle in the Earth's crust, and may affect current and past sulphur isotopic records. However, the extrapolation of experimental reaction rates measured at high temperature (above 200 °C) towards lower temperatures, as well as the interpretation of the sulphur isotopic fractionation recorded in natural samples, require an accurate description of the elementary steps controlling these reactions. We addressed this question through dedicated experiments. Based on in situ Raman spectroscopy measurements, we show that the trisulphur ion S−3 is the dominant intermediate sulphur valence species involved in abiogenic sulphate reduction processes initiated by H2S, over a wide range of temperature (100-350 °C) and solution compositions, whatever the electron donor considered. The in situ spectroscopic data reported here unambiguously demonstrate the presence of S−3 at temperatures as low as 100 °C. The presence of S−3 is critical to achieve rapid sulphate reduction, especially at low temperature. We propose that any dissolved constituent which decreases the dielectric constant of water, or which yields favourable S−3 coordination, will stabilise the trisulphur ion (thus promoting TSR) at T and pH conditions that are less extreme than previously thought. The importance of S−3 in these processes should also be taken into account when discussing the mass-independent sulphur isotopic compositions recorded in natural and/or experimental TSR-related samples.

Precise measurement of chromium isotopes by MC-ICPMS.

We report novel analytical procedures allowing for the concurrent determination of the stable and mass-independent Cr isotopic composition of silicate materials by multiple collector inductively coupled mass spectrometry (MC-ICPMS). In particular, we focus on improved precision of the measurement of the neutron-rich isotope 54Cr. Because nitride and oxide interferences are a major obstacle to precise and accurate 54Cr measurements by MC-ICPMS, our approach is designed to minimize these interferences. Based on repeat measurements of standards, we show that the mass-independent 53Cr and 54Cr compositions can be routinely determined with an external reproducibility better than 2.5 and 5.8 ppm (2 sd), respectively. This represents at least a two-fold improvement compared to previous studies. Although this approach uses significantly more Cr (30-60 μg) than analysis by thermal ionization mass spectrometry (TIMS), our result indicate that it is possible to obtain an external reproducibility of 19 ppm for the μ54Cr when consuming amounts similar to that typically analyzed by TIMS (1 μg). In addition, the amount of time required for analysis by MC-ICPMS is much shorter thereby enabling a higher sample throughput. As a result of the improved analytical precision, we identified small apparent mass-independent differences between different synthetic Cr standards and bulk silicate Earth (BSE) when using the kinetic law for the mass bias correction. These differences are attributed to the Cr loss by equilibrium processes during production of the synthetic standards. The stable isotope data concurrently obtained have a precision of 0.05‰ Da -1, which is comparable to earlier studies. Comparison of the measured isotopic composition of four meteorites with published data indicates that Cr isotope data measured by the technique described here are accurate to stated uncertainties. The stable Cr composition of the Bilanga and NWA 2999 achondrites suggests that the differences in the stable Cr isotope composition of Earth and chondrites may reflect heterogeneity of their precursor material rather than Cr isotope fractionation during metal-silicate segregation of Earth. Lastly, a step wise dissolution experiment of the CI chondrite Ivuna reveals previously unknown carriers of large mass-dependent Cr stable isotope variations that co-vary with the known presence of carriers of large nucleosynthetic anomalies, demonstrating one advantage of this technique.

Sulfur isotopic fractionation in vacuum UV photodissociation of hydrogen sulfide and its potential relevance to meteorite analysis

Select meteoritic classes possess mass-independent sulfur isotopic compositions in sulfide and organic phases. Photochemistry in the solar nebula has been attributed as a source of these anomalies. Hydrogen sulfide (H2S) is the most abundant gas-phase species in the solar nebula, and hence, photodissociation of H2S by solar vacuum UV (VUV) photons (especially by Lyman-α radiation) is a relevant process. Because of experimental difficulties associated with accessing VUV radiation, there is a paucity of data and a lack of theoretical basis to test the hypothesis of a photochemical origin of mass-independent sulfur. Here, we present multiisotopic measurements of elemental sulfur produced during the VUV photolysis of H2S. Mass-independent sulfur isotopic compositions are observed. The observed isotopic fractionation patterns are wavelength-dependent. VUV photodissociation of H2S takes place through several predissociative channels, and the measured mass-independent fractionation is most likely a manifestation of these processes. Meteorite sulfur data are discussed in light of the present experiments, and suggestions are made to guide future experiments and models.

Uncertainties in the oxygen isotopic composition of barium sulfate induced by coprecipitation of nitrate

Coprecipitation of nitrate and sulfate by barium has probably resulted in significant error in numerous studies dealing with the oxygen isotopic composition of natural sulfates using chemical/thermal conversion of BaSO(4) and analysis by isotope ratio mass spectrometry. In solutions where NO(3) (-)/SO(4) (2-) molar ratios are above 2 the amount of nitrate coprecipitated with BaSO(4) reaches a maximum of approximately 7% and decreases roughly linearly as the molar ratio decreases. The fraction of coprecipitated nitrate appears to increase with decreasing pH and is also affected by the nature of the cations in the precipitating solution. The size of the oxygen isotope artifact in sulfate depends both on the amount of coprecipitated nitrate and the delta(18)O and Delta(17)O values of the nitrate, both of which can be highly variable. The oxygen isotopic composition of sulfate extracted from atmospheric aerosols or rain waters are probably severely biased because photochemical nitrate is usually also present and it is highly enriched in (18)O (delta(18)O approximately 50-90 per thousand) and has a large mass-independent isotopic composition (Delta(17)O approximately 20-32 per thousand). The sulfate delta(18)O error can be 2-5 per thousand with Delta(17)O artifacts reaching as high as 4.0 per thousand.

Mass-Independent Sulfur Isotopic Compositions in Stratospheric Volcanic Eruptions

The observed mass-independent sulfur isotopic composition (Delta33S) of volcanic sulfate from the Agung (March 1963) and Pinatubo (June 1991) eruptions recorded in the Antarctic snow provides a mechanism for documenting stratospheric events. The sign of Delta33S changes over time from an initial positive component to a negative value. Delta33S is created during photochemical oxidation of sulfur dioxide to sulfuric acid on a monthly time scale, which indicates a fast process. The reproducibility of the results reveals that Delta33S is a reliable tracer to chemically identify atmospheric processes involved during stratospheric volcanism.

Long term atmospheric deposition as the source of nitrate and other salts in the Atacama Desert, Chile: New evidence from mass-independent oxygen isotopic compositions

Isotopic analysis of nitrate and sulfate minerals from the nitrate ore fields of the Atacama Desert in northern Chile has shown anomalous 17O enrichments in both minerals. Δ 17O values of 14–21 ‰ in nitrate and 0.4 to 4 ‰ in sulfate are the most positive found in terrestrial minerals to date. Modeling of atmospheric processes indicates that the Δ 17O signatures are the result of photochemical reactions in the troposphere and stratosphere. We conclude that the bulk of the nitrate, sulfate and other soluble salts in some parts of the Atacama Desert must be the result of atmospheric deposition of particles produced by gas to particle conversion, with minor but varying amounts from sea spray and local terrestrial sources. Flux calculations indicate that the major salt deposits could have accumulated from atmospheric deposition in a period of 200,000 to 2.0 M years during hyper-arid conditions similar to those currently found in the Atacama Desert. Correlations between Δ 17O and δ 18O in nitrate salts from the Atacama Desert and Mojave Desert, California, indicate varying fractions of microbial and photochemical end-member sources. The photochemical nitrate isotope signature is well preserved in the driest surficial environments that are almost lifeless, whereas the microbial nitrate isotope signature becomes dominant rapidly with increasing moisture, biologic activity, and nitrogen cycling. These isotopic signatures have important implications for paleoclimate, astrobiology, and N cycling studies.

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.