Tracing sources of atmospheric methane using clumped isotopes.

We apply a recently developed measurement technique for methane (CH4) isotopologues* (isotopic variants of CH4-13CH4, 12CH3D, 13CH3D, and 12CH2D2) to identify contributions to the atmospheric burden from fossil fuel and microbial sources. The aim of this study is to constrain factors that ultimately control the concentration of this potent greenhouse gas on global, regional, and local levels. While predictions of atmospheric methane isotopologues have been modeled, we present direct measurements that point to a different atmospheric methane composition and to a microbial flux with less clumping (greater deficits relative to stochastic) in both 13CH3D and 12CH2D2 than had been previously assigned. These differences make atmospheric isotopologue data sufficiently sensitive to variations in microbial to fossil fuel fluxes to distinguish between emissions scenarios such as those generated by different versions of EDGAR (the Emissions Database for Global Atmospheric Research), even when existing constraints on the atmospheric CH4 concentration profile as well as traditional isotopes are kept constant.

Fully resolved high-precision measurement of 36S for sulfur reference materials.

RATIONALE: Advances in sulfur isotope measurement techniques have led to increased analytical precision. However, accurate measurement of 36S remains a challenge. This difficulty arises primarily from unresolved isobaric interferences of 36SF5 + at m/z = 131 u, 186WF4 2+ and 12C3F5 +, which lead to scale compression. Theoretically, unresolved interference with 2% relative intensity could cause 1‰ underestimation in a sample with real δ36S = +60‰. METHODS: Our study develops an interference-free four-sulfur isotope measurement method by using the high-resolution mass spectrometer Panorama. The mass resolving power of Panorama allows the distinction of 186WF4 2+ and 12C3F5 + from 36SF5 +. RESULTS: The 186WF4 2+ relative intensity was initially 9.4% that of 36SF5 + but reduced to 1.5% through tuning, while 12C3F5 + relative intensity dropped from 74% to 40% after flushing with air. Three IAEA standards were analyzed with both Panorama and MAT 253. We obtained Δ36SIAEA-S-2 = 1.238 ± 0.040‰ and Δ36SIAEA-S-3 = -0.882 ± 0.030‰, relative to IAEA-S-1, from Panorama, and Δ36SIAEA-S-2 = 0.18 ± 0.02‰ and Δ36SIAEA-S-3 = 0.11 ± 0.14‰ from MAT 253, while δ34S values from the two instruments are consistent. CONCLUSION: The measurement discrepancies on 36S between Panorama and MAT 253 highlight the impact of scale compression due to unresolved isobaric interferences. Resolving this problem is crucial for accurate 36S analysis. We recommend replacing the filament material with rhenium, tuning the filament voltage, and avoiding carbon in instruments to eliminate or mitigate interferences. We propose future systematic efforts to calibrate the δ33S, δ34S, and δ36S of IAEA-S-1, IAEA-S-2, and IAEA-S-3 and advise bracketing all three reference materials in the measurement sequences, to enable calibration.

Isotopic links between atmospheric chemistry and the deep sulphur cycle on Mars.

The geochemistry of Martian meteorites provides a wealth of information about the solid planet and the surface and atmospheric processes that occurred on Mars. The degree to which Martian magmas may have assimilated crustal material, thus altering the geochemical signatures acquired from their mantle sources, is unclear. This issue features prominently in efforts to understand whether the source of light rare-earth elements in enriched shergottites lies in crustal material incorporated into melts or in mixing between enriched and depleted mantle reservoirs. Sulphur isotope systematics offer insight into some aspects of crustal assimilation. The presence of igneous sulphides in Martian meteorites with sulphur isotope signatures indicative of mass-independent fractionation suggests the assimilation of sulphur both during passage of magmas through the crust of Mars and at sites of emplacement. Here we report isotopic analyses of 40 Martian meteorites that represent more than half of the distinct known Martian meteorites, including 30 shergottites (28 plus 2 pairs, where pairs are separate fragments of a single meteorite), 8 nakhlites (5 plus 3 pairs), Allan Hills 84001 and Chassigny. Our data provide strong evidence that assimilation of sulphur into Martian magmas was a common occurrence throughout much of the planet's history. The signature of mass-independent fractionation observed also indicates that the atmospheric imprint of photochemical processing preserved in Martian meteoritic sulphide and sulphate is distinct from that observed in terrestrial analogues, suggesting fundamental differences between the dominant sulphur chemistry in the atmosphere of Mars and that in the atmosphere of Earth.

Biological regulation of atmospheric chemistry en route to planetary oxygenation.

Emerging evidence suggests that atmospheric oxygen may have varied before rising irreversibly ∼2.4 billion years ago, during the Great Oxidation Event (GOE). Significantly, however, pre-GOE atmospheric aberrations toward more reducing conditions-featuring a methane-derived organic-haze-have recently been suggested, yet their occurrence, causes, and significance remain underexplored. To examine the role of haze formation in Earth's history, we targeted an episode of inferred haze development. Our redox-controlled (Fe-speciation) carbon- and sulfur-isotope record reveals sustained systematic stratigraphic covariance, precluding nonatmospheric explanations. Photochemical models corroborate this inference, showing Δ36S/Δ33S ratios are sensitive to the presence of haze. Exploiting existing age constraints, we estimate that organic haze developed rapidly, stabilizing within ∼0.3 ± 0.1 million years (Myr), and persisted for upward of ∼1.4 ± 0.4 Myr. Given these temporal constraints, and the elevated atmospheric CO2 concentrations in the Archean, the sustained methane fluxes necessary for haze formation can only be reconciled with a biological source. Correlative δ13COrg and total organic carbon measurements support the interpretation that atmospheric haze was a transient response of the biosphere to increased nutrient availability, with methane fluxes controlled by the relative availability of organic carbon and sulfate. Elevated atmospheric methane concentrations during haze episodes would have expedited planetary hydrogen loss, with a single episode of haze development providing up to 2.6-18 × 1018 moles of O2 equivalents to the Earth system. Our findings suggest the Neoarchean likely represented a unique state of the Earth system where haze development played a pivotal role in planetary oxidation, hastening the contingent biological innovations that followed.

Redox chemistry changes in the Panthalassic Ocean linked to the end-Permian mass extinction and delayed Early Triassic biotic recovery.

The end-Permian mass extinction represents the most severe biotic crisis for the last 540 million years, and the marine ecosystem recovery from this extinction was protracted, spanning the entirety of the Early Triassic and possibly longer. Numerous studies from the low-latitude Paleotethys and high-latitude Boreal oceans have examined the possible link between ocean chemistry changes and the end-Permian mass extinction. However, redox chemistry changes in the Panthalassic Ocean, comprising ∼85-90% of the global ocean area, remain under debate. Here, we report multiple S-isotopic data of pyrite from Upper Permian-Lower Triassic deep-sea sediments of the Panthalassic Ocean, now present in outcrops of western Canada and Japan. We find a sulfur isotope signal of negative Δ33S with either positive δ34S or negative δ34S that implies mixing of sulfide sulfur with different δ34S before, during, and after the end-Permian mass extinction. The precise coincidence of the negative Δ33S anomaly with the extinction horizon in western Canada suggests that shoaling of H2S-rich waters may have driven the end-Permian mass extinction. Our data also imply episodic euxinia and oscillations between sulfidic and oxic conditions during the earliest Triassic, providing evidence of a causal link between incursion of sulfidic waters and the delayed recovery of the marine ecosystem.

Anomalous sulphur isotopes in plume lavas reveal deep mantle storage of Archaean crust.

Basaltic lavas erupted at some oceanic intraplate hotspot volcanoes are thought to sample ancient subducted crustal materials. However, the residence time of these subducted materials in the mantle is uncertain and model-dependent, and compelling evidence for their return to the surface in regions of mantle upwelling beneath hotspots is lacking. Here we report anomalous sulphur isotope signatures indicating mass-independent fractionation (MIF) in olivine-hosted sulphides from 20-million-year-old ocean island basalts from Mangaia, Cook Islands (Polynesia), which have been suggested to sample recycled oceanic crust. Terrestrial MIF sulphur isotope signatures (in which the amount of fractionation does not scale in proportion with the difference in the masses of the isotopes) were generated exclusively through atmospheric photochemical reactions until about 2.45 billion years ago. Therefore, the discovery of MIF sulphur in these young plume lavas suggests that sulphur--probably derived from hydrothermally altered oceanic crust--was subducted into the mantle before 2.45 billion years ago and recycled into the mantle source of Mangaia lavas. These new data provide evidence for ancient materials, with negative Δ(33)S values, in the mantle source for Mangaia lavas. Our data also complement evidence for recycling of the sulphur content of ancient sedimentary materials to the subcontinental lithospheric mantle that has been identified in diamond-hosted sulphide inclusions. This Archaean age for recycled oceanic crust also provides key constraints on the length of time that subducted crustal material can survive in the mantle, and on the timescales of mantle convection from subduction to upwelling beneath hotspots.

Early inner solar system origin for anomalous sulfur isotopes in differentiated protoplanets.

Achondrite meteorites have anomalous enrichments in (33)S, relative to chondrites, which have been attributed to photochemistry in the solar nebula. However, the putative photochemical reactions remain elusive, and predicted accompanying (33)S depletions have not previously been found, which could indicate an erroneous assumption regarding the origins of the (33)S anomalies, or of the bulk solar system S-isotope composition. Here, we report well-resolved anomalous (33)S depletions in IIIF iron meteorites (<-0.02 per mil), and (33)S enrichments in other magmatic iron meteorite groups. The (33)S depletions support the idea that differentiated planetesimals inherited sulfur that was photochemically derived from gases in the early inner solar system (<∼2 AU), and that bulk inner solar system S-isotope composition was chondritic (consistent with IAB iron meteorites, Earth, Moon, and Mars). The range of mass-independent sulfur isotope compositions may reflect spatial or temporal changes influenced by photochemical processes. A tentative correlation between S isotopes and Hf-W core segregation ages suggests that the two systems may be influenced by common factors, such as nebular location and volatile content.

Pathways for Neoarchean pyrite formation constrained by mass-independent sulfur isotopes.

It is generally thought that the sulfate reduction metabolism is ancient and would have been established well before the Neoarchean. It is puzzling, therefore, that the sulfur isotope record of the Neoarchean is characterized by a signal of atmospheric mass-independent chemistry rather than a strong overprint by sulfate reducers. Here, we present a study of the four sulfur isotopes obtained using secondary ion MS that seeks to reconcile a number of features seen in the Neoarchean sulfur isotope record. We suggest that Neoarchean ocean basins had two coexisting, significantly sized sulfur pools and that the pathways forming pyrite precursors played an important role in establishing how the isotopic characteristics of each of these pools was transferred to the sedimentary rock record. One of these pools is suggested to be a soluble (sulfate) pool, and the other pool (atmospherically derived elemental sulfur) is suggested to be largely insoluble and unreactive until it reacts with hydrogen sulfide. We suggest that the relative contributions of these pools to the formation of pyrite depend on both the accumulation of the insoluble pool and the rate of sulfide production in the pyrite-forming environments. We also suggest that the existence of a significant nonsulfate pool of reactive sulfur has masked isotopic evidence for the widespread activity of sulfate reducers in the rock record.

Sulfur isotope variability of oceanic DMSP generation and its contributions to marine biogenic sulfur emissions.

Oceanic dimethylsulfoniopropionate (DMSP) is the precursor to dimethylsulfide (DMS), which plays a role in climate regulation through transformation to methanesulfonic acid (MSA) and non-seasalt sulfate (NSS-SO(4)(2-)) aerosols. Here, we report measurements of the abundance and sulfur isotope compositions of DMSP from one phytoplankton species (Prorocentrum minimum) and five intertidal macroalgal species (Ulva lactuca, Ulva linza, Ulvaria obscura, Ulva prolifera, and Polysiphonia hendryi) in marine waters. We show that the sulfur isotope compositions (δ(34)S) of DMSP are depleted in (34)S relative to the source seawater sulfate by ∼1-3‰ and are correlated with the observed intracellular content of methionine, suggesting a link to metabolic pathways of methionine production. We suggest that this variability of δ(34)S is transferred to atmospheric geochemical products of DMSP degradation (DMS, MSA, and NSS-SO(4)(2-)), carrying implications for the interpretation of variability in δ(34)S of MSA and NSS-SO(4)(2-) that links them to changes in growth conditions and populations of DMSP producers rather than to the contributions of DMS and non-DMS sources.

Multiple sulfur isotopes fractionations associated with abiotic sulfur transformations in Yellowstone National Park geothermal springs.

BACKGROUND: The paper presents a quantification of main (hydrogen sulfide and sulfate), as well as of intermediate sulfur species (zero-valent sulfur (ZVS), thiosulfate, sulfite, thiocyanate) in the Yellowstone National Park (YNP) hydrothermal springs and pools. We combined these measurements with the measurements of quadruple sulfur isotope composition of sulfate, hydrogen sulfide and zero-valent sulfur. The main goal of this research is to understand multiple sulfur isotope fractionation in the system, which is dominated by complex, mostly abiotic, sulfur cycling. RESULTS: Water samples from six springs and pools in the Yellowstone National Park were characterized by pH, chloride to sulfate ratios, sulfide and intermediate sulfur species concentrations. Concentrations of sulfate in pools indicate either oxidation of sulfide by mixing of deep parent water with shallow oxic water, or surface oxidation of sulfide with atmospheric oxygen. Thiosulfate concentrations are low (<6 µmol L(-1)) in the pools with low pH due to fast disproportionation of thiosulfate. In the pools with higher pH, the concentration of thiosulfate varies, depending on different geochemical pathways of thiosulfate formation. The δ(34)S values of sulfate in four systems were close to those calculated using a mixing line of the model based on dilution and boiling of a deep hot parent water body. In two pools δ(34)S values of sulfate varied significantly from the values calculated from this model. Sulfur isotope fractionation between ZVS and hydrogen sulfide was close to zero at pH < 4. At higher pH zero-valent sulfur is slightly heavier than hydrogen sulfide due to equilibration in the rhombic sulfur-polysulfide - hydrogen sulfide system. Triple sulfur isotope ((32)S, (33)S, (34)S) fractionation patterns in waters of hydrothermal pools are more consistent with redox processes involving intermediate sulfur species than with bacterial sulfate reduction. Small but resolved differences in ∆(33)S among species and between pools are observed. CONCLUSIONS: The variation of sulfate isotopic composition, the origin of differences in isotopic composition of sulfide and zero-valent sulfur, as well as differences in ∆(33)S of sulfide and sulfate are likely due to a complex network of abiotic redox reactions, including disproportionation pathways.

Evidence of magnetic isotope effects during thermochemical sulfate reduction.

Thermochemical sulfate reduction experiments with simple amino acid and dilute concentrations of sulfate reveal significant degrees of mass-independent sulfur isotope fractionation. Enrichments of up to 13‰ for (33)S are attributed to a magnetic isotope effect (MIE) associated with the formation of thiol-disulfide, ion-radical pairs. Observed (36)S depletions in products are explained here by classical (mass-dependent) isotope effects and mixing processes. The experimental data contrasts strongly with multiple sulfur isotope trends in Archean samples, which exhibit significant (36)S anomalies. These results support an origin other than thermochemical sulfate reduction for the mass-independent signals observed for early Earth samples.

Isotopic evidence for Mesoarchaean anoxia and changing atmospheric sulphur chemistry.

The evolution of the Earth's atmosphere is marked by a transition from an early atmosphere with very low oxygen content to one with an oxygen content within a few per cent of the present atmospheric level. Placing time constraints on this transition is of interest because it identifies the time when oxidative weathering became efficient, when ocean chemistry was transformed by delivery of oxygen and sulphate, and when a large part of Earth's ecology changed from anaerobic to aerobic. The observation of non-mass-dependent sulphur isotope ratios in sedimentary rocks more than approximately 2.45 billion years (2.45 Gyr) old and the disappearance of this signal in younger sediments is taken as one of the strongest lines of evidence for the transition from an anoxic to an oxic atmosphere around 2.45 Gyr ago. Detailed examination of the sulphur isotope record before 2.45 Gyr ago also reveals early and late periods of large amplitude non-mass-dependent signals bracketing an intervening period when the signal was attenuated. Until recently, this record has been too sparse to allow interpretation, but collection of new data has prompted some workers to argue that the Mesoarchaean interval (3.2-2.8 Gyr ago) lacks a non-mass-dependent signal, and records the effects of earlier and possibly permanent oxygenation of the Earth's atmosphere. Here we focus on the Mesoarchaean interval, and demonstrate preservation of a non-mass-dependent signal that differs from that of preceding and following periods in the Archaean. Our findings point to the persistence of an anoxic early atmosphere, and identify variability within the isotope record that suggests changes in pre-2.45-Gyr-ago atmospheric pathways for non-mass-dependent chemistry and in the ultraviolet transparency of an evolving early atmosphere.

Deglacial volcanism and reoxygenation in the aftermath of the Sturtian Snowball Earth.

The Cryogenian Sturtian and Marinoan Snowball Earth glaciations bracket a nonglacial interval during which Demosponge and green-algal biomarkers first appear. To understand the relationships between environmental perturbations and early animal evolution, we measured sulfur and mercury isotopes from the Datangpo Formation from South China. Hg enrichment with positive Δ199Hg excursion suggests enhanced volcanism, potentially due to depressurization of terrestrial magma chambers during deglaciation. A thick stratigraphic interval of negative Δ33Spy indicates that the nonglacial interlude was characterized by low but rising sulfate levels. Model results reveal a mechanism to produce the Δ33S anomalies down to -0.284‰ through Rayleigh distillation. We propose that extreme temperatures and anoxia contributed to the apparent delay in green algal production in the aftermath of the Sturtian glaciation and the subsequent reoxygenation of the iron-rich and sulfate-depleted ocean paved the way for evolution of animals.

Animal evolution, bioturbation, and the sulfate concentration of the oceans.

As recognized already by Charles Darwin, animals are geobiological agents. Darwin observed that worms aerate and mix soils on a massive scale, aiding in the decomposition of soil organic matter. A similar statement can be made about marine benthic animals. This mixing, also known as bioturbation, not only aides in the decomposition of sedimentary organic material, but as contended here, it has also significantly influenced the chemistry of seawater. In particular, it is proposed that sediment mixing by bioturbating organisms resulted in a severalfold increase in seawater sulfate concentration. For this reason, the evolution of bioturbation is linked to the significant deposition of sulfate evaporate minerals, which is largely a phenomena of the Phanerozoic, the last 542 million years and the time over which animals rose to prominence.

Geological constraints on the origin of oxygenic photosynthesis.

This article examines the geological evidence for the rise of atmospheric oxygen and the origin of oxygenic photosynthesis. The evidence for the rise of atmospheric oxygen places a minimum time constraint before which oxygenic photosynthesis must have developed, and was subsequently established as the primary control on the atmospheric oxygen level. The geological evidence places the global rise of atmospheric oxygen, termed the Great Oxidation Event (GOE), between ~2.45 and ~2.32 Ga, and it is captured within the Duitschland Formation, which shows a transition from mass-independent to mass-dependent sulfur isotope fractionation. The rise of atmospheric oxygen during this interval is closely associated with a number of environmental changes, such as glaciations and intense continental weathering, and led to dramatic changes in the oxidation state of the ocean and the seawater inventory of transition elements. There are other features of the geologic record predating the GOE by as much as 200-300 million years, perhaps extending as far back as the Mesoarchean-Neoarchean boundary at 2.8 Ga, that suggest the presence of low level, transient or local, oxygenation. If verified, these features would not only imply an earlier origin for oxygenic photosynthesis, but also require a mechanism to decouple oxygen production from oxidation of Earth's surface environments. Most hypotheses for the GOE suggest that oxygen production by oxygenic photosynthesis is a precondition for the rise of oxygen, but that a synchronous change in atmospheric oxygen level is not required by the onset of this oxygen source. The potential lag-time in the response of Earth surface environments is related to the way that oxygen sinks, such as reduced Fe and sulfur compounds, respond to oxygen production. Changes in oxygen level imply an imbalance in the sources and sinks for oxygen. Changes in the cycling of oxygen have occurred at various times before and after the GOE, and do not appear to require corresponding changes in the intensity of oxygenic photosynthesis. The available geological constraints for these changes do not, however, disallow a direct role for this metabolism. The geological evidence for early oxygen and hypotheses for the controls on oxygen level are the basis for the interpretation of photosynthetic oxygen production as examined in this review.

Multi isotope systematics of precipitation to trace the sources of air pollutants in Seoul, Korea.

Multiple sulfur (δ34Ssulfate, Δ33Ssulfate, & Δ36Ssulfate), nitrogen and oxygen (δ15Nnitrate & δ18Onitrate) and strontium (87Sr/86Sr) isotope compositions of precipitation collected from Seoul, South Korea were analyzed to study the sources, transportation and deposition of air pollutants in East Asia. The δ34Ssulfate values (from 1.9 to 14.6‰ with a median of 4.7‰) and the δ15Nnitrate values (from -2.0 to 13.3‰ with a median of 1.0‰) suggest that fossil fuel use (emission from coal combustion and vehicle exhaust) is a predominant source for sulfur and nitrogen, but other natural sources including biogenic contributions of DMS also add to their total budget. The seasonal variations are observed in δ34Ssulfate and δ15Nnitrate values (both higher in winter season), which is likely to result from the increase of coal use for domestic heating in China. The δ18Onitrate values also varied seasonally depending on the NOx oxidation pathway, being about 20‰ higher in winter than in summer season. The Δ33Ssulfate and Δ36Ssulfate values are not anomalous, showing the absence of MIF signals in precipitation of Seoul. The 87Sr/86Sr ratio of the precipitation samples range from 0.70988 to 0.71487 with a median of 0.71073, indicating the influence of at least three end-member (silicate dust, carbonate dust and anthropogenic emission). Ionic ratios such as (K++NH4+)/(Ca2++Mg2+) and Cl-/Na+ suggest the overwhelming effect of anthropogenic input rather than carbonate dust on the end-member with lower 87Sr/86Sr ratios.

The origin and migration of the dissolved sulfate from precipitation in Seoul, Korea.

This study incorporated stable isotope analyses with chemical analyses to determine the origin and migration of sulfur sources in East Asia, and these findings were compared with our decadal research from 2000 to 2001 and 2002 to 2003. The multiple sulfur isotope composition (32S, 33S and 34S) of the dissolved sulfate in precipitation was first measured from 2011 to 2013 in Seoul, South Korea. The δ34Snss values were -1.1‰ to 7.9‰ (avg. 3.6‰), strongly suggesting that sulfur derived from the combustion of Chinese coal is the predominant source of sulfate in the Seoul region. Low NO3/SO42- ratios in the precipitation samples indicated an insignificant effect of sulfur from vehicle exhaust. The seasonal variation of δ34Snss values appears to be caused by increasing biogenic sulfur activity during the spring and summer seasons. The some Δ33S values (0.13‰-0.16‰) measured in the three samples were sufficiently small; thus, whether these values can be attributed to mass-independent fractionation remains unclear. Measuring the Δ33S anomalies in dissolved sulfate provides valuable insights for identifying the sources of sulfur transferred from the stratosphere to the troposphere and upper troposphere.

Large sulfur isotope fractionations associated with Neoarchean microbial sulfate reduction.

The minor extent of sulfur isotope fractionation preserved in many Neoarchean sedimentary successions suggests that sulfate-reducing microorganisms played an insignificant role in ancient marine environments, despite evidence that these organisms evolved much earlier. We present bulk, microdrilled, and ion probe sulfur isotope data from carbonate-associated pyrite in the ~2.5-billion-year-old Batatal Formation of Brazil, revealing large mass-dependent fractionations (approaching 50 per mil) associated with microbial sulfate reduction, as well as consistently negative Δ(33)S values (~ -2 per mil) indicative of atmospheric photochemical reactions. Persistent (33)S depletion through ~60 meters of shallow marine carbonate implies long-term stability of seawater sulfate abundance and isotope composition. In contrast, a negative Δ(33)S excursion in lower Batatal strata indicates a response time of ~40,000 to 150,000 years, suggesting Neoarchean sulfate concentrations between ~1 and 10 µM.