A transient peak in marine sulfate after the 635-Ma snowball Earth.

SignificanceEarth system's response to major perturbations is of paramount interest. On the basis of multiple isotope compositions for pyrite, carbonate-associated sulfate, carbonates, and organics within, we inferred that the much-debated, enigmatic, extremely 13C-depleted calcite cements in the ∼635-Ma cap carbonates in South China preserve geochemical evidence for marine microbial sulfate reduction coupled to anaerobic oxidation of methane. This interpretation implies the existence of a brief interval of modern-level marine sulfate. We determined that this interval coincides with the earliest Ediacaran 17O-depletion episode, and both likely occurred within ∼50 ky since the onset of the 635-Ma meltdown, revealing an astonishing pace of transformation of the Earth system in the aftermath of Earth's latest snowball glaciation.

Oxygen Isotope Analysis of Nanomole Phosphate Using PO3- Fragment in ESI-Orbitrap-MS.

The oxygen isotope composition of phosphate is a useful tool for studying biogeochemical phosphorus cycling. However, the current Ag3PO4 method is not only tedious in PO43- extraction and purification but also requires a large-sized sample at the micromole level, thereby limiting its application. Here, we present an approach to measuring the oxygen isotope composition, δ18O, of dissolved phosphate at the nanomole level using electrospray ionization Orbitrap mass spectrometry (ESI-Orbitrap-MS). We compared the reproducibility of δ18O measurements using the H2PO4- ions (m/z = 97 and 99 for H2P16O4- and H2P18O16O3-, respectively) and using the PO3- fragment ions (m/z = 79 and 81 for P16O3- and P18O16O2-, respectively) generated by source fragmentation and by higher-energy collisional dissociation, respectively. The results demonstrate that phosphate δ18O can be more reliably measured by the PO3- ions than by the H2PO4- ions. PO3- generated by source fragmentation at 40 V achieved the highest reproducibility for δ18O based on precision tests. Furthermore, the mass spectrum for a 50:50 µM mixed solution of phosphate and sulfate revealed that PO3- ions resulting from source fragmentation at 40 V are the predominant species in the Orbitrap analyzer. Notably, P16O3- ions (m/z: 79) are not interfered with by 32S16O3- (m/z: 80) ions. This is in contrast to the case for 1H2P16O4- ions, which share the same m/z value with 1H32S16O4- ions and exhibit much lower signal intensity than HSO4- ions. Using the PO3- fragment method and six phosphate standards with a wide range of δ18O values, we obtained a calibration line with a slope of 0.94 (R2 = 0.98). The overall uncertainty for ESI-Orbitrap-MS phosphate δ18O measurement was 0.8‰ (n = 30; 1 SD). With much room for improvement, the PO3- fragment method presents a better approach to measuring the phosphate oxygen isotope composition, applicable to nanomole sample sizes in a liquid phase.

High-accuracy measurement of 36SF5 + signal using an ultrahigh-resolution isotope ratio mass spectrometer.

RATIONALE: The Δ36S standard deviation measured in a conventional isotope ratio mass spectrometer such as MAT 253 is ca 0.1‰ to 0.3‰. At this precision, it is difficult to resolve the origin of non-mass-dependent sulfur isotope fractionation in tropospheric sulfate aerosol and in Martian meteorites or small deviations from the canonical mass-dependent fractionation laws. Interfering ions with m/z at 131 of 36SF5 + are suggested by the community as the cause of the poor precision, but the exact ion species has not been identified or confirmed. METHODS: Here we examined the potential interfering ions by using a Thermo Scientific ultrahigh-resolution isotope ratio mass spectrometer to measure SF6 working gas and SF6 gases converted from IAEA-S1/2/3 Ag2S reference materials. RESULTS: We found that there are two resolvable peaks to the right of the 36SF5 + peak when a new filament was installed, which are 186WF4 2+ followed by 12C3F5 +. However, only the 12C3F5 + interference peak was observed after more than three days of filament use. 12C3F5 + is generated inside the instrument during the ionization process. Avoiding the interfering signals, we were able to achieve a Δ36S standard deviation of 0.046‰ (n = 8) for SF6 zero-enrichment and 0.069‰ (n = 8) for overall measurement start from silver sulfide IAEA-S1. CONCLUSIONS: Aging the filament with SF6 gas can avoid the interference of 186WF4 2+. Minimizing the presence of carbon-bearing compounds and avoiding the interfering signals of 12C3F5 + from 36SF5 +, we can improve Δ36S measurement accuracy and precision, which helps to open new territories for research using quadruple sulfur isotope composition.

Triple oxygen isotope evidence for limited mid-Proterozoic primary productivity.

The global biosphere is commonly assumed to have been less productive before the rise of complex eukaryotic ecosystems than it is today1. However, direct evidence for this assertion is lacking. Here we present triple oxygen isotope measurements (∆17O) from sedimentary sulfates from the Sibley basin (Ontario, Canada) dated to about 1.4 billion years ago, which provide evidence for a less productive biosphere in the middle of the Proterozoic eon. We report what are, to our knowledge, the most-negative ∆17O values (down to -0.88‰) observed in sulfates, except for those from the terminal Cryogenian period2. This observation demonstrates that the mid-Proterozoic atmosphere was distinct from what persisted over approximately the past 0.5 billion years, directly reflecting a unique interplay among the atmospheric partial pressures of CO2 and O2 and the photosynthetic O2 flux at this time3. Oxygenic gross primary productivity is stoichiometrically related to the photosynthetic O2 flux to the atmosphere. Under current estimates of mid-Proterozoic atmospheric partial pressure of CO2 (2-30 times that of pre-anthropogenic levels), our modelling indicates that gross primary productivity was between about 6% and 41% of pre-anthropogenic levels if atmospheric O2 was between 0.1-1% or 1-10% of pre-anthropogenic levels, respectively. When compared to estimates of Archaean4-6 and Phanerozoic primary production7, these model solutions show that an increasingly more productive biosphere accompanied the broad secular pattern of increasing atmospheric O2 over geologic time8.

A new phosphate purification method for igneous weathering profiles.

RATIONALE: The oxygen isotope composition of phosphate (δ18 OPO4 ) is widely employed for reconstructing paleotemperature and tracing biogeochemical phosphorus cycling. However, existing phosphate purification protocols do not work well for igneous rocks and igneous weathering profiles (IWPs). A reliable purification method is needed for measuring δ18 OPO4 in these materials. METHODS: Our phosphate purification method includes two steps of cation exchange resin treatment separated by a step of calcium phosphate precipitation (R-Ca-R method). In addition, the silver phosphate precipitation in our procedure is featured by slow evaporation to crystallization until the appearance of ammonium nitrate or silver nitrate crystals. We evaluated our methods on weathered and pristine igneous rocks, phosphorite rocks, KH2 PO4 , and (NH4 )2 HPO4 solutions. RESULTS: Our purification method converted over 99.9% phosphate in solution to calcium phosphate, which can be easily decalcified by cation resin. The improved silver phosphate precipitation method produced high phosphate yields (97.1%-99.5%) and retained original δ18 OPO4 within analytical uncertainty (2σ = 0.6‰). We applied the purification and precipitation method on five igneous rocks and IWPs, and obtained δ18 OPO4 values ranging from 6.4‰ to 8.0‰. Duplicate phosphate extractions yielded δ18 OPO4 values differing by less than 0.3‰. CONCLUSIONS: We developed a new phosphate purification method that is applicable to phosphate extraction in igneous rocks and IWPs. We also proposed a reliable indicator for the termination of silver phosphate precipitation. Our method can achieve high phosphate yield and reproducible δ18 OPO4 value.

Vapor isotopic evidence for the worsening of winter air quality by anthropogenic combustion-derived water.

Anthropogenic combustion-derived water (CDW) may accumulate in an airshed due to stagnant air, which may further enhance the formation of secondary aerosols and worsen air quality. Here we collected three-winter-season, hourly resolution, water-vapor stable H and O isotope compositions together with atmospheric physical and chemical data from the city of Xi'an, located in the Guanzhong Basin (GZB) in northwestern China, to elucidate the role of CDW in particulate pollution. Based on our experimentally determined water vapor isotope composition of the CDW for individual and weighted fuels in the basin, we found that CDW constitutes 6.2% of the atmospheric moisture on average and its fraction is positively correlated with [PM2.5] (concentration of particulate matter with an aerodynamic diameter less than 2.5 µm) as well as relative humidity during the periods of rising [PM2.5]. Our modeling results showed that CDW added additional average 4.6 µg m-3 PM2.5 during severely polluted conditions in the GZB, which corresponded to an average 5.1% of local anthropogenic [PM2.5] (average at ∼91.0 µg m-3). Our result is consistent with the proposed positive feedback between the relative humidity and a moisture sensitive air-pollution condition, alerting to the nontrivial role of CDW when considering change of energy structure such as a massive coal-to-gas switch in household heating in winter.

Isotope fractionation during capillary leaking in an isotope ratio mass spectrometer.

RATIONALE: When isotope composition is measured in dual-inlet mode with an isotope ratio mass spectrometer (IRMS), reference gas may be gradually enriched in heavy isotopes due to preferential loss of light ones from the bellows over time. Quantifying the degree of isotopic enrichment of the reference gas is imperative for high-precision isotopic analysis (i.e. at per meg level). METHODS: O2 and CO2 leaking experiments were performed with the dual-inlet system of an IRMS (Thermo Fisher® MAT 253 Plus). During each experiment, the drop of gas pressure in the bellows with time was recorded and isotope ratios of residual gas at various time intervals were analyzed. RESULTS: Isotopic enrichment of residual O2 gas could be as large as 1‰ for δ18 O when a large fraction (>75%) of initial gas was lost. The evolution of isotope compositions of the remaining gas can be well described by a pressure-dependent Rayleigh fractionation equation. When the pressure in the bellows is within 10-50 mBar, the isotope fractionation factor (α18 O) for O2 leaking ranges from 0.99911 to 0.99982 and the characteristic relationship of α17 O and α18 O is from 0.5123 to 0.5124. CONCLUSIONS: Isotope fractionation associated with capillary leaking from bellows is pressure-dependent. We recommend that the reference gas should be reloaded frequently, especially after a measurement with a low analyzing pressure for the analysis of small amounts of sample.

Identifying apparent local stable isotope equilibrium in a complex non-equilibrium system.

RATIONALE: Although being out of equilibrium, biomolecules in organisms have the potential to approach isotope equilibrium locally because enzymatic reactions are intrinsically reversible. A rigorous approach that can describe isotope distribution among biomolecules and their apparent deviation from equilibrium state is lacking, however. METHODS: Applying the concept of distance matrix in graph theory, we propose that apparent local isotope equilibrium among a subset of biomolecules can be assessed using an apparent fractionation difference (|Δα|) matrix, in which the differences between the observed isotope composition (δ') and the calculated equilibrium fractionation factor (1000lnß) can be more rigorously evaluated than by using a previous approach for multiple biomolecules. We tested our |Δα| matrix approach by re-analyzing published data of different amino acids (AAs) in potato and in green alga. RESULTS: Our re-analysis shows that biosynthesis pathways could be the reason for an apparently close-to-equilibrium relationship inside AA families in potato leaves. Different biosynthesis/degradation pathways in tubers may have led to the observed isotope distribution difference between potato leaves and tubers. The analysis of data from green algae does not support the conclusion that AAs are further from equilibrium in glucose-cultured green algae than in the autotrophic ones. CONCLUSIONS: Application of the |Δα| matrix can help us to locate potential reversible reactions or reaction networks in a complex system such as a metabolic system. The same approach can be broadly applied to all complex systems that have multiple components, e.g. geochemical or atmospheric systems of early Earth or other planets.

Assessing Pyrite-Derived Sulfate in the Mississippi River with Four Years of Sulfur and Triple-Oxygen Isotope Data.

Riverine dissolved sulfate (SO42-) sulfur and oxygen isotope variations reflect their controls such as SO42- reduction and reoxidation, and source mixing. However, unconstrained temporal variability of riverine SO42- isotope compositions due to short sampling durations may lead to mischaracterization of SO42- sources, particularly for the pyrite-derived sulfate load. We measured the sulfur and triple-oxygen isotopes (δ34S, δ18O, and Δ'17O) of Mississippi River SO42- with biweekly sampling between 2009 and 2013 to test isotopic variability and constrain sources. Sulfate δ34S and δ18O ranged from -6.3‰ to -0.2‰ and -3.6‰ to +8.8‰, respectively. Our sampling period captured the most severe flooding and drought in the Mississippi River basin since 1927 and 1956, respectively, and a first year of sampling that was unrepresentative of long-term average SO42-. The δ34SSO4 data indicate pyrite-derived SO42- sources are 74 ± 10% of the Mississippi River sulfate budget. Furthermore, pyrite oxidation is implicated as the dominant process supplying SO42- to the Mississippi River, whereas the Δ'17OSO4 data shows 18 ± 9% of oxygen in this sulfate is sourced from air O2.

Massive volcanic SO(2) oxidation and sulphate aerosol deposition in Cenozoic North America.

Volcanic eruptions release a large amount of sulphur dioxide (SO(2)) into the atmosphere. SO(2) is oxidized to sulphate and can subsequently form sulphate aerosol, which can affect the Earth's radiation balance, biologic productivity and high-altitude ozone concentrations, as is evident from recent volcanic eruptions. SO(2) oxidation can occur via several different pathways that depend on its flux and the atmospheric conditions. An investigation into how SO(2) is oxidized to sulphate-the oxidation product preserved in the rock record-can therefore shed light on past volcanic eruptions and atmospheric conditions. Here we use sulphur and triple oxygen isotope measurements of atmospheric sulphate extracted from tuffaceous deposits to investigate the specific oxidation pathways from which the sulphate was formed. We find that seven eruption-related sulphate aerosol deposition events have occurred during the mid-Cenozoic era (34 to 7 million years ago) in the northern High Plains, North America. Two extensively sampled ash beds display a similar sulphate mixing pattern that has two distinct atmospheric secondary sulphates. A three-dimensional atmospheric sulphur chemistry and transport model study reveals that the observed, isotopically discrete sulphates in sediments can be produced only in initially alkaline cloudwater that favours an ozone-dominated SO(2) oxidation pathway in the troposphere. Our finding suggests that, in contrast to the weakly acidic conditions today, cloudwater in the northern High Plains may frequently have been alkaline during the mid-Cenozoic era. We propose that atmospheric secondary sulphate preserved in continental deposits represents an unexploited geological archive for atmospheric SO(2) oxidation chemistry linked to volcanism and atmospheric conditions in the past.

Dynamic model constraints on oxygen-17 depletion in atmospheric O2 after a snowball Earth.

A large perturbation in atmospheric CO2 and O2 or bioproductivity will result in a drastic pulse of (17)O change in atmospheric O2, as seen in the Marinoan Oxygen-17 Depletion (MOSD) event in the immediate aftermath of a global deglaciation 635 Mya. The exact nature of the perturbation, however, is debated. Here we constructed a coupled, four-box, and quick-response biosphere-atmosphere model to examine both the steady state and dynamics of the MOSD event. Our model shows that the ultra-high CO2 concentrations proposed by the "snowball' Earth hypothesis produce a typical MOSD duration of less than 10(6) y and a magnitude of (17)O depletion reaching approximately -35‰. Both numbers are in remarkable agreement with geological constraints from South China and Svalbard. Moderate CO2 and low O2 concentration (e.g., 3,200 parts per million by volume and 0.01 bar, respectively) could produce distinct sulfate (17)O depletion only if postglacial marine bioproductivity was impossibly low. Our dynamic model also suggests that a snowball in which the ocean is isolated from the atmosphere by a continuous ice cover may be distinguished from one in which cracks in the ice permit ocean-atmosphere exchange only if partial pressure of atmospheric O2 is larger than 0.02 bar during the snowball period and records of weathering-derived sulfate are available for the very first few tens of thousands of years after the onset of the meltdown. In any case, a snowball Earth is a precondition for the observed MOSD event.

Sedimentary constraints on the duration of the Marinoan Oxygen-17 Depletion (MOSD) event.

The ~635 Ma Marinoan glaciation is marked by dramatic Earth system perturbations. Deposition of nonmass-dependently (17)O-depleted sulfate (SO4(2-)) in worldwide postglacial sediments is, thus far, unique to this glaciation. It is proposed that an extremely high-pCO2 atmosphere can result in highly (17)O-depleted atmospheric O2, or the Marinoan Oxygen-17 Depletion (MOSD) event. This anomalous (17)O signal was imparted to sulfate of oxidative weathering origin. However, (17)O-depleted sulfate occurs in limited sedimentary intervals, suggesting that Earth surface conditions conducive to the MOSD had a finite duration. An MOSD duration can, therefore, provide much needed constraint on modeling Earth system responses at that time. Unfortunately, the sulfate (17)O record is often sparse or lacks radiometric dates. Here, we report 11 barite layers from a post-Marinoan dolostone sequence at Wushanhu in the South China Block. The (17)O depletion fluctuates in magnitude in lower layers but is persistently absent up section, providing the most confident first and last sedimentary appearance of the anomaly. δ(13)C chemostratigraphy is used to correlate the Wushanhu section to two proximal sections on the same shallow platform that lack barite layers but have published U-Pb dates that occur in dolostone and shale. Assuming a similar pattern and rate for carbonate and shale deposition among the different sections, we estimate the MOSD duration at 0-0.99 My. This number can be further constrained by new radiometric dates from equivalent sequences worldwide, thus underpinning models on the nonsteady-state Earth system response in the immediate aftermath of the Marinoan meltdown.

Significant human impact on the flux and δ(34)S of sulfate from the largest river in North America.

Riverine dissolved sulfate (SO4(2-)) flux and sulfur stable isotope composition (δ(34)S) yield information on the sources and processes affecting sulfur cycling on different spatial and temporal scales. However, because pristine preindustrial natural baselines of riverine SO4(2-) flux and δ(34)S cannot be directly measured, anthropogenic impact remains largely unconstrained. Here we quantify natural and anthropogenic SO4(2-) flux and δ(34)S for North America's largest river, the Mississippi, by means of an exhaustive source compilation and multiyear monitoring. Our data and analysis show that, since before industrialization to the present, Mississippi River SO4(2-) has increased in flux from 7.0 to 27.8 Tg SO4(2-) yr(-1), and in mean δ(34)S from -5.0‰, within 95% confidence limits of -14.8‰ to 4.1‰ (assuming normal distribution for mixing model input parameters), to -2.7 ± 1.6‰, reflecting an impressive footprint of bedrocks particular to this river basin and human activities. Our first-order modern Mississippi River sulfate partition is 25 ± 6% natural and 75% ± 6% anthropogenic sources. Furthermore, anthropogenic coal usage is implicated as the dominant source of modern Mississippi River sulfate, with an estimated 47 ± 5% and 13% of total Mississippi River sulfate due to coal mining and burning, respectively.

Triple oxygen isotope evidence for elevated CO2 levels after a Neoproterozoic glaciation.

Understanding the composition of the atmosphere over geological time is critical to understanding the history of the Earth system, as the atmosphere is closely linked to the lithosphere, hydrosphere and biosphere. Although much of the history of the lithosphere and hydrosphere is contained in rock and mineral records, corresponding information about the atmosphere is scarce and elusive owing to the lack of direct records. Geologists have used sedimentary minerals, fossils and geochemical models to place constraints on the concentrations of carbon dioxide, oxygen or methane in the past. Here we show that the triple oxygen isotope composition of sulphate from ancient evaporites and barites shows variable negative oxygen-17 isotope anomalies over the past 750 million years. We propose that these anomalies track those of atmospheric oxygen and in turn reflect the partial pressure of carbon dioxide (P(CO2)) in the past through a photochemical reaction network linking stratospheric ozone to carbon dioxide and to oxygen. Our results suggest that P(CO2) was much higher in the early Cambrian than in younger eras, agreeing with previous modelling results. We also find that the (17)O isotope anomalies of barites from Marinoan (approximately 635 million years ago) cap carbonates display a distinct negative spike (around -0.70 per thousand), suggesting that by the time barite was precipitating in the immediate aftermath of a Neoproterozoic global glaciation, the P(CO2) was at its highest level in the past 750 million years. Our finding is consistent with the 'snowball Earth' hypothesis and/or a massive methane release after the Marinoan glaciation.

Sulfate triple-oxygen-isotope evidence confirming oceanic oxygenation 570 million years ago.

The largest negative inorganic carbon isotope excursion in Earth's history, namely the Ediacaran Shuram Excursion (SE), closely followed by early animal radiation, has been widely interpreted as a consequence of oceanic oxidation. However, the primary nature of the signature, source of oxidants, and tempo of the event remain contested. Here, we show that carbonate-associated sulfate (CAS) from three different paleocontinents all have conspicuous negative 17O anomalies (Δ'17OCAS values down to -0.53‰) during the SE. Furthermore, the Δ'17OCAS varies in correlation with its corresponding δ34SCAS and δ18OCAS as well as the carbonate δ13Ccarb, decreasing initially followed by a recovery over the ~7-Myr SE duration. In a box-model examination, we argue for a period of sustained water-column ventilation and consequently enhanced sulfur oxidation in the SE ocean. Our findings reveal a direct involvement of mass-anomalously 17O-depleted atmospheric O2 in marine sulfate formation and thus a primary global oceanic oxygenation event during the SE.

Thermal-gradient-induced non-mass-dependent isotope fractionation.

Isotope fractionation resulting from gas diffusion along a thermal gradient has always been considered entirely mass-dependent. A previous report, however, showed that non-mass-dependent (17)O anomalies can be generated simply by subjecting O(2) gas in an enclosure to a thermal gradient. To explore the underlying mechanism for the anomalies, we tested the effect of gas pressure, duration of experiment, and geometry of the apparatus on the (17)O anomalies for O(2) as well as on the (33)S or (36)S anomalies for SF(6) gas. The results are consistent with our proposal that a previously ignored nuclear spin effect on gas diffusion coefficient may be largely responsible for generating the observed anomalies. This discovery provides clues to some of the puzzling non-mass-dependent isotope signatures encountered in experiments and in nature, including the triple oxygen or quadruple sulfur isotope heterogeneity in the solar system.

Non-mass-dependent (17) O anomalies generated by a superimposed thermal gradient on a rarefied O(2) gas in a closed system.

Cryogenic or heating methods have been widely used in experiments involving gas purification or isolation and in studying phase changes among solids, liquids, or gases for more than a century. Thermal gradients are often present in these routine processes. While stable isotopes of an element are known to fractionate under a thermal gradient, the largely diffusion-driven fractionation is assumed to be entirely mass-dependent. We report here, however, that distinct non-mass-dependent oxygen isotope fractionation can be generated when subjecting rarefied O(2) gas in a closed system to a simple thermal gradient. The Δ(17) O value, a measure of the (17) O anomaly, can be up to -0.51‰ (standard deviation (s.d.) 1σ = 0.03) in one of the temperature compartments. The magnitude of the (17) O anomalies decreased with increasing initial gas pressures. The authenticity of this phenomenon is substantiated by a series of blank tests and isotope mass-balance calculations. The observed anomalies are not the result of H(2) O contamination in samples or in isotope ratio mass spectrometry. Our finding calls attention to the importance of thermal gradient-induced isotope fractionation and to its implications in laboratory procedures, stable isotope geochemistry, and the physical chemistry of rarefied gases.

Large equatorial seasonal cycle during Marinoan snowball Earth.

In the equatorial regions on Earth today, the seasonal cycle of the monthly mean surface air temperature is <10°C. However, deep (>1 m) sand wedges were found near the paleoequator in the Marinoan glaciogenic deposits at ~635 million years ago, indicating a large seasonal cycle (probably >30°C). Through numerical simulations, we show that the equatorial seasonal cycle could reach >30°C at various continental locations if the oceans are completely frozen over, as would have been the case for a snowball Earth, or could reach ~20°C if the oceans are not completely frozen over, as would have been the case for a waterbelt Earth. These values are obtained at the maximum eccentricity of the Earth orbit, i.e., 0.0679, and will be approximately 10°C smaller if the present-day eccentricity is used. For these seasonal cycles, theoretical calculations show that the deep sand wedges form readily in a snowball Earth while hardly form in a waterbelt Earth.