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A synthesis of global barite sulfate isotope data from approximately 635 million years ago, at the end of a global glaciation, undermines the hypothesis that river sulfate was the primary carrier of the distinctive 17O-depleted atmospheric O2 signature of the time. Instead, an aqueous H2S oxidation model on the shelf emerges as a compelling alternative, though it demands extensive validation across multiple fronts by the scientific community., (© The Author(s) 2024. Published by Oxford University Press on behalf of China Science Publishing & Media Ltd.)

Rationale: The Δ 36 S 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 36 SF 5 + 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 SF 6 working gas and SF 6 gases converted from IAEA-S1/2/3 Ag 2 S reference materials., Results: We found that there are two resolvable peaks to the right of the 36 SF 5 + peak when a new filament was installed, which are 186 WF 4 2+ followed by 12 C 3 F 5 + . However, only the 12 C 3 F 5 + interference peak was observed after more than three days of filament use. 12 C 3 F 5 + is generated inside the instrument during the ionization process. Avoiding the interfering signals, we were able to achieve a Δ 36 S standard deviation of 0.046‰ (n = 8) for SF 6 zero-enrichment and 0.069‰ (n = 8) for overall measurement start from silver sulfide IAEA-S1., Conclusions: Aging the filament with SF 6 gas can avoid the interference of 186 WF 4 2+ . Minimizing the presence of carbon-bearing compounds and avoiding the interfering signals of 12 C 3 F 5 + from 36 SF 5 + , we can improve Δ 36 S measurement accuracy and precision, which helps to open new territories for research using quadruple sulfur isotope composition., (© 2024 John Wiley & Sons Ltd.)

The oxygen isotope composition of phosphate is a useful tool for studying biogeochemical phosphorus cycling. However, the current Ag 3 PO 4 method is not only tedious in PO 4 3- 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, δ 18 O, of dissolved phosphate at the nanomole level using electrospray ionization Orbitrap mass spectrometry (ESI-Orbitrap-MS). We compared the reproducibility of δ 18 O measurements using the H 2 PO 4 - ions ( m / z = 97 and 99 for H 2 P 16 O 4 - and H 2 P 18 O 16 O 3 - , respectively) and using the PO 3 - fragment ions ( m / z = 79 and 81 for P 16 O 3 - and P 18 O 16 O 2 - , respectively) generated by source fragmentation and by higher-energy collisional dissociation, respectively. The results demonstrate that phosphate δ 18 O can be more reliably measured by the PO 3 - ions than by the H 2 PO 4 - ions. PO 3 - generated by source fragmentation at 40 V achieved the highest reproducibility for δ 18 O based on precision tests. Furthermore, the mass spectrum for a 50:50 μM mixed solution of phosphate and sulfate revealed that PO 3 - ions resulting from source fragmentation at 40 V are the predominant species in the Orbitrap analyzer. Notably, P 16 O 3 - ions ( m / z : 79) are not interfered with by 32 S 16 O 3 - ( m / z : 80) ions. This is in contrast to the case for 1 H 2 P 16 O 4 - ions, which share the same m / z value with 1 H 32 S 16 O 4 - ions and exhibit much lower signal intensity than HSO 4 - ions. Using the PO 3 - fragment method and six phosphate standards with a wide range of δ 18 O values, we obtained a calibration line with a slope of 0.94 ( R 2 = 0.98). The overall uncertainty for ESI-Orbitrap-MS phosphate δ 18 O measurement was 0.8‰ ( n = 30; 1 SD). With much room for improvement, the PO 3 - fragment method presents a better approach to measuring the phosphate oxygen isotope composition, applicable to nanomole sample sizes in a liquid phase.

Rationale: The oxygen isotope composition of phosphate (δ 18 O PO4 ) 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 δ 18 O PO4 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, KH 2 PO 4 , and (NH 4 ) 2 HPO 4 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 δ 18 O PO4 within analytical uncertainty (2σ = 0.6‰). We applied the purification and precipitation method on five igneous rocks and IWPs, and obtained δ 18 O PO4 values ranging from 6.4‰ to 8.0‰. Duplicate phosphate extractions yielded δ 18 O PO4 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 δ 18 O PO4 value., (© 2023 John Wiley & Sons Ltd.)

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 17 O anomalies (Δ' 17 O CAS values down to -0.53‰) during the SE. Furthermore, the Δ' 17 O CAS varies in correlation with its corresponding δ 34 S CAS and δ 18 O CAS as well as the carbonate δ 13 C carb , 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 17 O-depleted atmospheric O 2 in marine sulfate formation and thus a primary global oceanic oxygenation event during the SE., (© 2023. The Author(s).)

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: O 2 and CO 2 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 O 2 gas could be as large as 1‰ for δ 18 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 (α 18 O) for O 2 leaking ranges from 0.99911 to 0.99982 and the characteristic relationship of α 17 O and α 18 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., (© 2022 John Wiley & Sons Ltd.)

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 13 C-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 17 O-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.

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 [PM 2.5 ] (concentration of particulate matter with an aerodynamic diameter less than 2.5 μm) as well as relative humidity during the periods of rising [PM 2.5 ]. Our modeling results showed that CDW added additional average 4.6 μg m -3 PM 2.5 during severely polluted conditions in the GZB, which corresponded to an average 5.1% of local anthropogenic [PM 2.5 ] (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.

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., (Copyright © 2020 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works. Distributed under a Creative Commons Attribution NonCommercial License 4.0 (CC BY-NC).)

Diogenites are a group of meteorites that are derived from the interior of the largest protoplanet Vesta. They provide a unique opportunity to understanding together the internal structure and dynamic evolution of this protoplanet. Northwest Africa (NWA) 8321 was suggested to be an unbrecciated noritic diogenite meteorite, which is confirmed by our oxygen and chromium isotopic data. Here, we find that olivine in this sample has been partly replaced by orthopyroxene, troilite, and minor metal. The replacement texture of olivine is unambiguous evidence of sulfur-involved metasomatism in the interior of Vesta. The presence of such replacement texture suggests that in NWA 8321, the olivine should be of xenolith origin while the noritic diogenite was derived from partial melting of pre-existing rocks and had crystallized in the interior of Vesta. The post-Rheasilvia craters in the north-polar region on Vesta could be the potential source for NWA 8321.

Both nanocrystals and carbon materials have attracted considerable attention in lithium-ion batteries (LIBs) because of their fast kinetics for lithium storage or long-life cycles. However, the easy aggregation of nanocrystals and high-temperature doping process of carbon materials seriously hindered their application in LIBs. Here, we report the development of unprecedented TiO 2- x @C nanocomposite electrodes through a unique "melting low-temperature pyrolysis" strategy. It is found that the continuous and interconnected three-dimensional amorphous carbon frameworks (3DCFs) in the composites are closely connected with TiO 2 nanocrystals by Ti-O-C covalent bonding, forming robust 3D framework architectures. Interestingly, we find that TiO 2 nanocrystals can greatly improve the pseudocapacitance of TiO 2- x @C nanocomposite electrodes with increasing cycles, which significantly exceeds previously reported TiO 2 -based anodes and carbon materials. Furthermore, for the first time, the unusual improvement of pseudocapacitance of TiO 2- x @C electrodes is carefully investigated by means of d Q /d V curves and electrochemical kinetic analysis to reveal the extra contribution of lithium storage. 3DCF, a "lithium-ion reservoir", possesses an unexpected capacity enhancement behavior that is triggered by TiO 2 nanocrystals and exhibits bicontinuous pathways for both rapid ion and electron transport. In this case, TiO 2 nanocrystals stabilizing the 3DCF acted as a conductive agent during charge and discharge. Our findings confirm that the 3DCF triggered by TiO 2 nanocrystals boosted the electrochemical performance of TiO 2- x @C nanocomposite electrodes, especially the pseudocapacitance enhancement. The unique characteristics of ingenious combination of TiO 2 nanocrystals and amorphous carbon materials make them attain superior electrochemical properties in all known TiO 2 - and carbon-based anodes (289 mA h g -1 at 5 A g -1 after 4000 cycles). Above all, our findings reveal previously ignored fundamental aspects of pseudocapacitance improvement of nanocomposite electrodes and offer new hope for structural design and carbon coating process of high-performance anode materials.

Termination of the terminal Cryogenian Marinoan snowball Earth glaciation (~650-635 Ma) is associated with the worldwide deposition of a cap carbonate. Modeling studies suggest that, during and immediately following deglaciation, the ocean may have experienced a rapid rise in pH and physical stratification followed by oceanic overturn. Testing these predictions requires the establishment of a high-resolution sequence of events within sedimentary records. Here we report the conspicuous occurrence of pyrite concretions in the topmost Nantuo Formation (South China) that was deposited in the Marinoan glacial deposits. Sedimentary facies and sulfur isotope data indicate pyrite precipitation in the sediments with H 2 S diffusing from the overlying sulfidic/euxinic seawater and Fe (II) from diamictite sediments. These observations suggest a transient but widespread presence of marine euxinia in an ocean characterized by redox stratification, high bioproductivity, and high-fluxes of sulfate from chemical weathering before the deposition of the cap carbonate.

The global biosphere is commonly assumed to have been less productive before the rise of complex eukaryotic ecosystems than it is today 1 . However, direct evidence for this assertion is lacking. Here we present triple oxygen isotope measurements (∆ 17 O) 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 ∆ 17 O values (down to -0.88‰) observed in sulfates, except for those from the terminal Cryogenian period 2 . 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 CO 2 and O 2 and the photosynthetic O 2 flux at this time 3 . Oxygenic gross primary productivity is stoichiometrically related to the photosynthetic O 2 flux to the atmosphere. Under current estimates of mid-Proterozoic atmospheric partial pressure of CO 2 (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 O 2 was between 0.1-1% or 1-10% of pre-anthropogenic levels, respectively. When compared to estimates of Archaean 4-6 and Phanerozoic primary production 7 , these model solutions show that an increasingly more productive biosphere accompanied the broad secular pattern of increasing atmospheric O 2 over geologic time 8 .

Riverine dissolved sulfate (SO 4 2- ) sulfur and oxygen isotope variations reflect their controls such as SO 4 2- reduction and reoxidation, and source mixing. However, unconstrained temporal variability of riverine SO 4 2- isotope compositions due to short sampling durations may lead to mischaracterization of SO 4 2- sources, particularly for the pyrite-derived sulfate load. We measured the sulfur and triple-oxygen isotopes (δ 34 S, δ 18 O, and Δ' 17 O) of Mississippi River SO 4 2- with biweekly sampling between 2009 and 2013 to test isotopic variability and constrain sources. Sulfate δ 34 S and δ 18 O 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 SO 4 2- . The δ 34 S SO4 data indicate pyrite-derived SO 4 2- sources are 74 ± 10% of the Mississippi River sulfate budget. Furthermore, pyrite oxidation is implicated as the dominant process supplying SO 4 2- to the Mississippi River, whereas the Δ' 17 O SO4 data shows 18 ± 9% of oxygen in this sulfate is sourced from air O 2 .

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 (1000lnβ) 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., (Copyright © 2017 John Wiley & Sons, Ltd.)

Due to the adverse impact of DDTs on ecosystems and humans, a full fate assessment deems a comprehensive study on their occurrence in soils over a large region. Through a sampling campaign across China, we measured the concentrations, enantiomeric fractions (EFs), compound-specific carbon isotope composition of DDT and its metabolites, and the microbial community in related arable soils. The geographically total DDT concentrations are higher in eastern than western China. The EFs and δ 13 C of o,p'-DDT in soils from western China show smaller deviations from those of racemic/standard compound, indicating the DDT residues there mainly result from atmospheric transport. However, the sources of DDT in eastern China are mainly from historic application of technical DDTs and dicofol. The inverse dependence of o,p'-DDT and p,p'-DDE on temperature evidences the transformation of parent DDT to its metabolites. Initial usage, abiotic parameters and microbial communities are found to be the main factors influencing the migration and transformation of DDT isomers and their metabolites in soils. In addition, a prediction equation of DDT concentrations in soils based on stepwise multiple regression analysis is developed. Results from this study offer insights into the migration and transformation pathways of DDTs in Chinese arable soils, which will allow data-based risk assessment on their use.

Non-traditional stable isotopes have increasingly been applied to studies of igneous processes including planetary differentiation. Equilibrium isotope fractionation of these elements in silicates is expected to be negligible at magmatic temperatures (δ(57)Fe difference often less than 0.2 per mil). However, an increasing number of data has revealed a puzzling observation, e.g., the δ(57)Fe for silicic magmas ranges from 0‰ up to 0.6‰, with the most positive δ(57)Fe almost exclusively found in A-type granitoids. Several interpretations have been proposed by different research groups, but these have so far failed to explain some aspects of the observations. Here we propose a dynamic, diffusion-induced isotope fractionation model that assumes Si-melts are growing and ascending immiscibly in a Fe-rich bulk magma chamber. Our model offers predictions on the behavior of non-traditional stable isotope such as Fe, Mg, Si, and Li that are consistent with observations from many A-type granitoids, especially those associated with layered intrusions. Diffusion-induced isotope fractionation may be more commonly preserved in magmatic rocks than was originally predicted.

The Antarctic ice cap significantly affects global ocean circulation and climate. Continental glaciogenic sedimentary deposits provide direct physical evidence of the glacial history of the Antarctic interior, but these data are sparse. Here we investigate a new indicator of ice sheet evolution: sulfates within the glaciogenic deposits from the Lewis Cliff Ice Tongue of the central Transantarctic Mountains. The sulfates exhibit unique isotope signatures, including δ(34)S up to +50‰ for mirabilite evaporites, Δ(17)O up to +2.3‰ for dissolved sulfate within contemporary melt-water ponds, and extremely negative δ(18)O as low as -22.2‰. The isotopic data imply that the sulfates formed under environmental conditions similar to today's McMurdo Dry Valleys, suggesting that ice-free cold deserts may have existed between the South Pole and the Transantarctic Mountains since the Miocene during periods when the ice sheet size was smaller than today, but with an overall similar to modern global hydrological cycle.

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.

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.

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.

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., (Copyright © 2011 John Wiley & Sons, Ltd.)

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., (Copyright © 2010 John Wiley & Sons, Ltd.)

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.

The oxygen isotope composition of terrestrial sulfate is affected measurably by many Earth-surface processes. During the Neoproterozoic, severe "snowball" glaciations would have had an extreme impact on the biosphere and the atmosphere. Here, we report that sulfate extracted from carbonate lenses within a Neoproterozoic glacial diamictite suite from Svalbard, with an age of approximately 635 million years ago, falls well outside the currently known natural range of triple oxygen isotope compositions and indicates that the atmosphere had either an exceptionally high atmospheric carbon dioxide concentration or an utterly unfamiliar oxygen cycle during deposition of the diamictites.

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.

Philippot et al. (Reports, 14 September 2007, p. 1534) interpreted multiple-sulfur isotopic compositions of approximately 3.5-billion-year-old marine sulfide deposits as evidence that early Archaean microorganisms were not sulfate reducers but instead metabolized elemental sulfur. However, their data can be better explained by a scenario involving poor mixing of photochemical and surface sulfide sources.

Abundant graphite particles occur in amphibolite-grade quartzite of the Archean-Paleoproterozoic Wutai Metamorphic Complex in the Wutaishan area of North China. Petrographic thin section observations suggest that the graphite particles occur within and between quartzite clasts and are heterogeneous in origin. Using HF maceration techniques, the Wutai graphite particles were extracted for further investigation. Laser Raman spectroscopic analysis of a population of extracted graphite discs indicated that they experienced a maximum metamorphic temperature of 513 +/- 50 degrees C, which is consistent with the metamorphic grade of the host rock and supports their indigenicity. Scanning and transmission electron microscopy revealed that the particles bear morphological features (such as hexagonal sheets of graphite crystals) related to metamorphism and crystal growth, but a small fraction of them (graphite discs) are characterized by a circular morphology, distinct marginal concentric folds, surficial wrinkles, and complex nanostructures. Ion microprobe analysis of individual graphite discs showed that their carbon isotope compositions range from -7.4 per thousand to -35.9 per thousand V-PDB (Vienna Pee Dee Belemnite), with an average of -20.3 per thousand, which is comparable to bulk analysis of extracted carbonaceous material. The range of their size, ultrastructures, and isotopic signatures suggests that the morphology and geochemistry of the Wutai graphite discs were overprinted by metamorphism and their ultimate carbon source probably had diverse origins that included abiotic processes. We considered both biotic and abiotic origins of the carbon source and graphite disc morphologies and cannot falsify the possibility that some circular graphite discs characterized by marginal folds and surficial wrinkles represent deflated, compressed, and subsequently graphitized organic-walled vesicles. Together with reports by other authors of acanthomorphic acritarchs from greenschist-amphibolite-grade metamorphic rocks, this study suggests that it is worthwhile to examine carbonaceous materials preserved in highly metamorphosed rocks for possible evidence of ancient life.

In the laboratory, barite precipitated from a solution with a high nitrate/sulfate ratio can have a significant amount (up to 28% by weight) of nitrate occluded in barite crystals that cannot be simply washed away. The impurity poses a serious problem for an accurate measurement of the oxygen isotope compositions for atmospheric sulfate, since atmospheric nitrate bears extremely positive Delta17O and delta18O values. Currently available methods for removing the occluded nitrate are either ineffective or not tested for oxygen isotope exchange. Here, I report a DTPA (a chelating solution) dissolution and reprecipitation (DDARP) method that is simple and effective in removing nitrate and other contaminants in barite. A series of barite dissolution and reprecipitation experiments that utilize 17O-anomalous solutions or barite crystals is conducted to examine the effect on oxygen isotopes during various treatments. It is established that no oxygen isotope exchange occurs between sulfate and water during DDARP treatment at two experimental temperatures (21 and 70 degrees C). Occlusion of DTPA itself in barite is negligible. Upon acidification, barite reprecipitation from a DTPA solution is quantitative (approximately 100%). Partially extracted barite may have slightly lower delta18O or delta34S values than the originals but no effect on Delta17O values. It is also demonstrated that heavily nitrate-contaminated barite samples are free of nitrate occlusion after two dissolution-reprecipitation cycles.

A microchip CE-amperometric detection (AD) system has been fabricated by integrating a two-dimensionally adjustable CE microchip and an AD cell containing a one-dimensionally adjustable disk detection electrode in a Plexiglas holder. It facilitates the precise 3-D alignment between the channel outlet and the detection electrode without a complicated 3-D manipulator. The performance of this unique system was demonstrated by separating five aromatic amines (1,4-phenyldiamine, aniline, 2-methylaniline, 4-chloroaniline, and 1-naphthylamine) of environmental concern. Factors influencing their separation and detection processes were examined and optimized. The five analytes have been well separated within 140 s in a 74 cm long separation channel at a separation voltage of +2500 V using a 10 mM phosphate buffer (pH 3.5). Highly linear response is obtained for the five analytes over the range 20-200 microM with the detection limits ranging from 0.46 to 1.44 microM, respectively. The present system demonstrated long-term stability and reproducibility with RSDs of less than 5% for the peak current (n = 9). The new approach for the microchannel-electrode alignment should find a wide range of applications in CE, flowing injection analysis, and other microfluidic analysis systems.

Perchlorate is known to be a minor component of the hyperarid Atacama Desert salts, and its origin has long been a subject of speculation. Here we report the first measurement of the triple-oxygen isotope ratios (18O/16O and 17O/16O) for both man-made perchlorate from commercial sources and natural perchlorate extracted from Atacama soils. We found that the delta 18O values (i.e., normalized 18O/ 16O ratios) of man-made perchlorate were at -18.4+/-1.2%, whereas natural perchlorate has a variable delta 18O value, ranging from -4.5% to -24.8%. The delta 18O and delta 17O values followed the bulk Earth's oxygen isotope fractionation line for man-made perchlorate, but all Atacama perchlorates deviated from this line, with a distinctly large and positive 170 anomaly ranging from +4.2% to +9.6%. These findings provide a tool for the identification and forensics of perchlorate contamination in the environment. Additionally, they confirm an early speculation that the oxidation of volatile chlorine by 03 and the formation of HClO4 can be a sink (albeit a minor one) for atmospheric chlorine.