A mineral-based origin of Earth's initial hydrogen peroxide and molecular oxygen.

Terrestrial reactive oxygen species (ROS) may have played a central role in the formation of oxic environments and evolution of early life. The abiotic origin of ROS on the Archean Earth has been heavily studied, and ROS are conventionally thought to have originated from H2O/CO2 dissociation. Here, we report experiments that lead to a mineral-based source of oxygen, rather than water alone. The mechanism involves ROS generation at abraded mineral-water interfaces in various geodynamic processes (e.g., water currents and earthquakes) which are active where free electrons are created via open-shell electrons and point defects, high pressure, water/ice interactions, and combinations of these processes. The experiments reported here show that quartz or silicate minerals may produce reactive oxygen-containing sites (≡SiO•, ≡SiOO•) that initially emerge in cleaving Si-O bonds in silicates and generate ROS during contact with water. Experimental isotope-labeling experiments show that the hydroxylation of the peroxy radical (≡SiOO•) is the predominant pathway for H2O2 generation. This heterogeneous ROS production chemistry allows the transfer of oxygen atoms between water and rocks and alters their isotopic compositions. This process may be pervasive in the natural environment, and mineral-based production of H2O2 and accompanying O2 could occur on Earth and potentially on other terrestrial planets, providing initial oxidants and free oxygen, and be a component in the evolution of life and planetary habitability.

New constraints of terrestrial and oceanic global gross primary productions from the triple oxygen isotopic composition of atmospheric CO2 and O2.

Representations of the changing global carbon cycle under climatic and environmental perturbations require highly detailed accounting of all atmosphere and biosphere exchange. These fluxes remain unsatisfactory, as a consequence of only having data with limited spatiotemporal coverage and precision, which restrict accurate assessments. Through the nature of intimate coupling of global carbon and oxygen cycles via O2 and CO2 and their unique triple oxygen isotope compositions in the biosphere and atmosphere, greater insight is available. We report analysis of their isotopic compositions with the widest geographical and temporal coverage (123 new measurements for CO2) and constrain, on an annual basis, the global CO2 recycling time (1.5 ± 0.2 year) and gross primary productivities of terrestrial (~ 170-200 PgC/year) and oceanic (~ 90-120 PgC/year) biospheres. Observed inter-annual variations in CO2 triple oxygen isotopic compositions were observed at a magnitude close to the largest contrast set by the terrestrial and oceanic biospheres. The seasonal cycles between the east and west Pacific Ocean were found to be drastically different. This intra-annual variability implies that the entire atmospheric CO2 turnover time is not much longer than the tropospheric mixing time (less than ~ 5 months), verifying the derived recycling time. The new measurements, analyses, and incorporation of other global data sets allow development of an independent approach, providing a strong constraint to biogeochemical models.

Isotopic Insights into Organic Composition Differences between Supermicron and Submicron Sea Spray Aerosol.

To elucidate the seawater biological and physicochemical factors driving differences in organic composition between supermicron and submicron sea spray aerosol (SSAsuper and SSAsub), carbon isotopic composition (δ13C) measurements were performed on size-segregated, nascent SSA collected during a phytoplankton bloom mesocosm experiment. The δ13C measurements indicate that SSAsuper contains a mixture of particulate and dissolved organic material in the bulk seawater. After phytoplankton growth, a greater amount of freshly produced carbon was observed in SSAsuper with the proportional contribution being modulated by bacterial activity, emphasizing the importance of the microbial loop in controlling the organic composition of SSAsuper. Conversely, SSAsub exhibited no apparent relationship with biological activity but tracked closely with surface tension measurements probing the topmost ∼0.2-1.5 µm of the sea surface microlayer. This probing depth is similar to a bubble's film thickness at the ocean surface, suggesting that SSAsub organic composition may be influenced by the presence of surfactants at the air-sea interface that are transferred into SSAsub by bubble bursting. Our findings illustrate the substantial impact of seawater dynamics on the pronounced organic compositional differences between SSAsuper and SSAsub and demonstrate that these two SSA populations should be considered separately when assessing their contribution to marine aerosols and climate.

Cosmogenic radiosulfur tracking of solar activity and the strong and long-lasting El Niño events.

Reconstruction of past solar activity or high-energy events of our space environment using cosmogenic radionuclides allows evaluation of their intensities, frequencies, and potential damages to humans in near space, modern satellite technologies, and ecosystems. This approach is limited by our understanding of cosmogenic radionuclide production, transformation, and transport in the atmosphere. Cosmogenic radiosulfur (35S) provides additional insights due to its ideal half-life (87.4 d), extensively studied atmospheric chemistry (gas and solid), and ubiquitous nature. Here, we report multiyear measurements of atmospheric 35S and show the sensitivity of 35S in tracking solar activity in Solar Cycle 24 and regional atmospheric circulation changes during the 2015/2016 El Niño. Incorporating 35S into a universal cosmogenic radionuclide model as an independent parameter facilitates better modeling of production and transport of other long-lived radionuclides with different atmospheric chemistries used for reconstructing past astronomical, geomagnetic, and climatic events.

Superconductivity found in meteorites.

Meteorites can contain a wide range of material phases due to the extreme environments found in space and are ideal candidates to search for natural superconductivity. However, meteorites are chemically inhomogeneous, and superconducting phases in them could potentially be minute, rendering detection of these phases difficult. To alleviate this difficulty, we have studied meteorite samples with the ultrasensitive magnetic field modulated microwave spectroscopy (MFMMS) technique [J. G. Ramírez, A. C. Basaran, J. de la Venta, J. Pereiro, I. K. Schuller, Rep. Prog. Phys. 77, 093902 (2014)]. Here, we report the identification of superconducting phases in two meteorites, Mundrabilla, a group IAB iron meteorite [R. Wilson, A. Cooney, Nature 213, 274-275 (1967)] and GRA 95205, a ureilite [J. N. Grossman, Meteorit. Planet. Sci. 33, A221-A239 (1998)]. MFMMS measurements detected superconducting transitions in samples from each, above 5 K. By subdividing and remeasuring individual samples, grains containing the largest superconducting fraction were isolated. The superconducting grains were then characterized with a series of complementary techniques, including vibrating-sample magnetometry (VSM), energy-dispersive X-ray spectroscopy (EDX), and numerical methods. These measurements and analysis identified the likely phases as alloys of lead, indium, and tin.

Measurements of 129I in the Pacific Ocean at Scripps Pier and Pacific Northwest sites: A search for effects from the 2011 Fukushima Daiichi Nuclear Power Plant accident and Hanford.

Radionuclides from the Fukushima Daiichi Nuclear Power Plant were released directly into the ocean as a result of the Great East Japan Earthquake on March 11, 2011. This material became entrained in surface ocean currents and subsequently transported for great distances. In June 2011, a few months after the disaster, we began a surface ocean 129I monitoring program, with samples from Scripps Pier, La Jolla, California, USA, with the expectation that surface currents originating off the east coast of Japan would eventually carry radionuclides to the La Jolla site. After 7 years of ocean transport, a distinct signal has not yet arrived at Scripps Pier. We have however, recorded an interesting systematic seasonal 129I time series record that stems from surface circulation variations along the California coast. To provide a more comprehensive picture of the 129I budget in coastal surface waters off the west coast of the U.S., we also include 129I data from the Columbia River, and offshore sites along the coast of Washington State. Anthropogenic nuclides are carried by the Columbia River into the Pacific Ocean from the vicinity of the decommissioned Hanford nuclear facility. We find highly elevated 129I/127I values in the Columbia River, downstream from the Hanford site, but this anthropogenic 129I becomes significantly diluted once it reaches the Pacific Ocean. Nonetheless, its imprint persists in surface seawater off the west coast of the U.S. that has significantly higher 129I/127I levels than other surface sites in the Pacific Ocean.

Use of Isotope Effects To Understand the Present and Past of the Atmosphere and Climate and Track the Origin of Life.

Stable isotope ratio measurements have been used as a measure of a wide variety of processes, including solar system evolution, geological formational temperatures, tracking of atmospheric gas and aerosol chemical transformation, and is the only means by which past global temperatures may be determined over long time scales. Conventionally, isotope effects derive from differences of isotopically substituted molecules in isotope vibrational energy, bond strength, velocity, gravity, and evaporation/condensation. The variations in isotope ratio, such as 18 O/16 O (δ18 O) and 17 O/16 O (δ17 O) are dependent upon mass differences with δ17 O/δ18 O=0.5, due to the relative mass differences (1 amu vs. 2 amu). Relations that do not follow this are termed mass independent and are the focus of this Minireview. In chemical reactions such as ozone formation, a δ17 O/δ18 O=1 is observed. Physical chemical models capture most parameters but differ in basic approach and are reviewed. The mass independent effect is observed in atmospheric species and used to track their chemistry at the modern and ancient Earth, Mars, and the early solar system (meteorites).

Linking atmospheric pollution to cryospheric change in the Third Pole region: current progress and future prospects.

The Tibetan Plateau and its surroundings are known as the Third Pole (TP). This region is noted for its high rates of glacier melt and the associated hydrological shifts that affect water supplies in Asia. Atmospheric pollutants contribute to climatic and cryospheric changes through their effects on solar radiation and the albedos of snow and ice surfaces; moreover, the behavior and fates within the cryosphere and environmental impacts of environmental pollutants are topics of increasing concern. In this review, we introduce a coordinated monitoring and research framework and network to link atmospheric pollution and cryospheric changes (APCC) within the TP region. We then provide an up-to-date summary of progress and achievements related to the APCC research framework, including aspects of atmospheric pollution's composition and concentration, spatial and temporal variations, trans-boundary transport pathways and mechanisms, and effects on the warming of atmosphere and changing in Indian monsoon, as well as melting of glacier and snow cover. We highlight that exogenous air pollutants can enter into the TP's environments and cause great impacts on regional climatic and environmental changes. At last, we propose future research priorities and map out an extended program at the global scale. The ongoing monitoring activities and research facilitate comprehensive studies of atmosphere-cryosphere interactions, represent one of China's key research expeditions to the TP and the polar regions and contribute to the global perspective of earth system science.

Five-S-isotope evidence of two distinct mass-independent sulfur isotope effects and implications for the modern and Archean atmospheres.

The signature of mass-independent fractionation of quadruple sulfur stable isotopes (S-MIF) in Archean rocks, ice cores, and Martian meteorites provides a unique probe of the oxygen and sulfur cycles in the terrestrial and Martian paleoatmospheres. Its mechanistic origin, however, contains some uncertainties. Even for the modern atmosphere, the primary mechanism responsible for the S-MIF observed in nearly all tropospheric sulfates has not been identified. Here we present high-sensitivity measurements of a fifth sulfur isotope, stratospherically produced radiosulfur, along with all four stable sulfur isotopes in the same sulfate aerosols and a suite of chemical species to define sources and mechanisms on a field observational basis. The five-sulfur-isotope and multiple chemical species analysis approach provides strong evidence that S-MIF signatures in tropospheric sulfates are concomitantly affected by two distinct processes: an altitude-dependent positive 33S anomaly, likely linked to stratospheric SO2 photolysis, and a negative 36S anomaly mainly associated with combustion. Our quadruple stable sulfur isotopic measurements in varying coal samples (formed in the Carboniferous, Permian, and Triassic periods) and in SO2 emitted from combustion display normal 33S and 36S, indicating that the observed negative 36S anomalies originate from a previously unknown S-MIF mechanism during combustion (likely recombination reactions) instead of coal itself. The basic chemical physics of S-MIF in both photolytic and thermal reactions and their interplay, which were not explored together in the past, may be another ingredient for providing deeper understanding of the evolution of Earth's atmosphere and life's origin.

Atmospheric sulfur isotopic anomalies recorded at Mt. Everest across the Anthropocene.

Increased anthropogenic-induced aerosol concentrations over the Himalayas and Tibetan Plateau have affected regional climate, accelerated snow/glacier melting, and influenced water supply and quality in Asia. Although sulfate is a predominant chemical component in aerosols and the hydrosphere, the contributions from different sources remain contentious. Here, we report multiple sulfur isotope composition of sedimentary sulfates from a remote freshwater alpine lake near Mount Everest to reconstruct a two-century record of the atmospheric sulfur cycle. The sulfur isotopic anomaly is utilized as a probe for sulfur source apportionment and chemical transformation history. The nineteenth-century record displays a distinct sulfur isotopic signature compared with the twentieth-century record when sulfate concentrations increased. Along with other elemental measurements, the isotopic proxy suggests that the increased trend of sulfate is mainly attributed to enhancements of dust-associated sulfate aerosols and climate-induced weathering/erosion, which overprinted sulfur isotopic anomalies originating from other sources (e.g., sulfates produced in the stratosphere by photolytic oxidation processes and/or emitted from combustion) as observed in most modern tropospheric aerosols. The changes in sulfur cycling reported in this study have implications for better quantification of radiative forcing and snow/glacier melting at this climatically sensitive region and potentially other temperate glacial hydrological systems. Additionally, the unique Δ33S-δ34S pattern in the nineteenth century, a period with extensive global biomass burning, is similar to the Paleoarchean (3.6-3.2 Ga) barite record, potentially providing a deeper insight into sulfur photochemical/thermal reactions and possible volcanic influences on the Earth's earliest sulfur cycle.

Accurate Quantification of Radiosulfur in Chemically Complex Atmospheric Samples.

An ultralow-level liquid scintillation counting (LSC) technique has been used in measuring radiosulfur (cosmogenic 35S) in natural samples. The ideal half-life of 35S (∼87 days) renders it a new way to examine various biogeochemical problems. A major limitation of the technique is that complex chemical compositions in atmospheric samples may lead to color quenching of LSC cocktails, a serious problem prolonging the pretreatment time (>1 week) and hampering the accurate determination of 35S. For application of the technique where many of the most important atmospheric chemical processes are examined, significant interferences arise and accurate analysis in small samples is not possible. In this study, we optimized the LSC method to minimize/eliminate color quenching in high-sensitivity 35S measurements. The analytical performance of this new method was evaluated using control laboratory experiments and natural aerosol samples. Results show that the new method offers comparable accuracy as the traditional method for normal environmental samples [bias: <±0.03 disintegrations per minute (DPM)] and significantly shortens the pretreatment time to less than 3 days. For samples that were heavily contaminated by color-quenching agents, the accuracy of this new method is notably higher than that of the traditional method (maximum bias: -0.3 vs -1.5 DPM). With the growing use of radiosulfur in the field of Earth and planetary sciences, the accurate determination of 35S would provide a reliable field-based constraint for modeling 35S production in the atmosphere and allow a wide range of atmospheric, hydrological, and biogeochemical applications.

Oxygen isotope anomaly in tropospheric CO2 and implications for CO2 residence time in the atmosphere and gross primary productivity.

The abundance variations of near surface atmospheric CO2 isotopologues (primarily 16O12C16O, 16O13C16O, 17O12C16O, and 18O12C16O) represent an integrated signal from anthropogenic/biogeochemical processes, including fossil fuel burning, biospheric photosynthesis and respiration, hydrospheric isotope exchange with water, and stratospheric photochemistry. Oxygen isotopes, in particular, are affected by the carbon and water cycles. Being a useful tracer that directly probes governing processes in CO2 biogeochemical cycles, Δ17O (=ln(1 + δ17O) - 0.516 × ln(1 + δ18O)) provides an alternative constraint on the strengths of the associated cycles involving CO2. Here, we analyze Δ17O data from four places (Taipei, Taiwan; South China Sea; La Jolla, United States; Jerusalem, Israel) in the northern hemisphere (with a total of 455 measurements) and find a rather narrow range (0.326 ± 0.005‰). A conservative estimate places a lower limit of 345 ± 70 PgC year-1 on the cycling flux between the terrestrial biosphere and atmosphere and infers a residence time of CO2 of 1.9 ± 0.3 years (upper limit) in the atmosphere. A Monte Carlo simulation that takes various plant uptake scenarios into account yields a terrestrial gross primary productivity of 120 ± 30 PgC year-1 and soil invasion of 110 ± 30 PgC year-1, providing a quantitative assessment utilizing the oxygen isotope anomaly for quantifying CO2 cycling.

Efficiency of Launching Highly Confined Polaritons by Infrared Light Incident on a Hyperbolic Material.

We investigated phonon-polaritons in hexagonal boron nitride-a naturally hyperbolic van der Waals material-by means of the scattering-type scanning near-field optical microscopy. Real-space nanoimages we have obtained detail how the polaritons are launched when the light incident on a thin hexagonal boron nitride slab is scattered by various intrinsic and extrinsic inhomogeneities, including sample edges, metallic nanodisks deposited on its top surface, random defects, and surface impurities. The scanned tip of the near-field microscope is itself a polariton launcher whose efficiency proves to be superior to all the other types of polariton launchers we studied. Our work may inform future development of polaritonic nanodevices as well as fundamental studies of collective modes in van der Waals materials.

Simple Method for High-Sensitivity Determination of Cosmogenic 35S in Snow and Water Samples Collected from Remote Regions.

Cosmogenic 35S is useful in understanding a wide variety of chemical and physical processes in the atmosphere, the hydrosphere, and the cryosphere. The 87.4-day half-life and the ubiquity of sulfur in natural environments renders it an ideal tracer of many phenomena. Measurements of 35S in snow and water samples are scarce as existing analytical methods require a large volume of sample (>20 L) due to their high analytical activity background and low counting efficiency. Here, we present a new set of snow/water sample collecting and handling procedures for high-sensitivity determination of cosmogenic 35S using a low-level liquid scintillation spectrometer. Laboratory experiments using diluted 35S standards (with activities of <5 disintegrations per minute) showed a 35S recovery percentage of ∼95%, demonstrating a relatively small deviation from the true value. Using this method, we successfully measured 35S in ∼1 L of fresh snow sample collected from a glacier on the Tibetan Plateau to be 47 ± 7 mBq/L. On the basis of 35S activities in 9 natural samples measured in this study, a first proof-of-concept approximation for age determinations and source attributions was presented. This new method will provide a powerful tool in studying 35S in small volumes of snow and water samples, especially those from remote but climatically important regions such as the polar regions and the Tibetan Plateau and Himalayas. The measurements are particularly important as the radioactive sulfur provides an actual clock of glacial melting processes. With the growing rate of glacial loss, the need for measurements from remote locations becomes all the more important.

Detection of deep stratospheric intrusions by cosmogenic 35S.

The extent to which stratospheric intrusions on synoptic scales influence the tropospheric ozone (O3) levels remains poorly understood, because quantitative detection of stratospheric air has been challenging. Cosmogenic 35S mainly produced in the stratosphere has the potential to identify stratospheric air masses at ground level, but this approach has not yet been unambiguously shown. Here, we report unusually high 35S concentrations (7,390 atoms m-3; ∼16 times greater than annual average) in fine sulfate aerosols (aerodynamic diameter less than 0.95 µm) collected at a coastal site in southern California on May 3, 2014, when ground-level O3 mixing ratios at air quality monitoring stations across southern California (43 of 85) exceeded the recently revised US National Ambient Air Quality Standard (daily maximum 8-h average: 70 parts per billion by volume). The stratospheric origin of the significantly enhanced 35S level is supported by in situ measurements of air pollutants and meteorological variables, satellite observations, meteorological analysis, and box model calculations. The deep stratospheric intrusion event was driven by the coupling between midlatitude cyclones and Santa Ana winds, and it was responsible for the regional O3 pollution episode. These results provide direct field-based evidence that 35S is an additional sensitive and unambiguous tracer in detecting stratospheric air in the boundary layer and offer the potential for resolving the stratospheric influences on the tropospheric O3 level.

Graphene-Based Platform for Infrared Near-Field Nanospectroscopy of Water and Biological Materials in an Aqueous Environment.

Scattering scanning near-field optical microscopy (s-SNOM) has emerged as a powerful nanoscale spectroscopic tool capable of characterizing individual biomacromolecules and molecular materials. However, applications of scattering-based near-field techniques in the infrared (IR) to native biosystems still await a solution of how to implement the required aqueous environment. In this work, we demonstrate an IR-compatible liquid cell architecture that enables near-field imaging and nanospectroscopy by taking advantage of the unique properties of graphene. Large-area graphene acts as an impermeable monolayer barrier that allows for nano-IR inspection of underlying molecular materials in liquid. Here, we use s-SNOM to investigate the tobacco mosaic virus (TMV) in water underneath graphene. We resolve individual virus particles and register the amide I and II bands of TMV at ca. 1520 and 1660 cm(-1), respectively, using nanoscale Fourier transform infrared spectroscopy (nano-FTIR). We verify the presence of water in the graphene liquid cell by identifying a spectral feature associated with water absorption at 1610 cm(-1).

Carbonate formation events in ALH 84001 trace the evolution of the Martian atmosphere.

Carbonate minerals provide critical information for defining atmosphere-hydrosphere interactions. Carbonate minerals in the Martian meteorite ALH 84001 have been dated to ∼ 3.9 Ga, and both C and O-triple isotopes can be used to decipher the planet's climate history. Here we report Δ(17)O, δ(18)O, and δ(13)C data of ALH 84001 of at least two varieties of carbonates, using a stepped acid dissolution technique paired with ion microprobe analyses to specifically target carbonates from distinct formation events and constrain the Martian atmosphere-hydrosphere-geosphere interactions and surficial aqueous alterations. These results indicate the presence of a Ca-rich carbonate phase enriched in (18)O that formed sometime after the primary aqueous event at 3.9 Ga. The phases showed excess (17)O (0.7‰) that captured the atmosphere-regolith chemical reservoir transfer, as well as CO2, O3, and H2O isotopic interactions at the time of formation of each specific carbonate. The carbon isotopes preserved in the Ca-rich carbonate phase indicate that the Noachian atmosphere of Mars was substantially depleted in (13)C compared with the modern atmosphere.

Nanoscale infrared spectroscopy as a non-destructive probe of extraterrestrial samples.

Advances in the spatial resolution of modern analytical techniques have tremendously augmented the scientific insight gained from the analysis of natural samples. Yet, while techniques for the elemental and structural characterization of samples have achieved sub-nanometre spatial resolution, infrared spectral mapping of geochemical samples at vibrational 'fingerprint' wavelengths has remained restricted to spatial scales >10 µm. Nevertheless, infrared spectroscopy remains an invaluable contactless probe of chemical structure, details of which offer clues to the formation history of minerals. Here we report on the successful implementation of infrared near-field imaging, spectroscopy and analysis techniques capable of sub-micron scale mineral identification within natural samples, including a chondrule from the Murchison meteorite and a cometary dust grain (Iris) from NASA's Stardust mission. Complementary to scanning electron microscopy, energy-dispersive X-ray spectroscopy and transmission electron microscopy probes, this work evidences a similarity between chondritic and cometary materials, and inaugurates a new era of infrared nano-spectroscopy applied to small and invaluable extraterrestrial samples.

Massive isotopic effect in vacuum UV photodissociation of N2 and implications for meteorite data.

Nitrogen isotopic distributions in the solar system extend across an enormous range, from -400‰, in the solar wind and Jovian atmosphere, to about 5,000‰ in organic matter in carbonaceous chondrites. Distributions such as these require complex processing of nitrogen reservoirs and extraordinary isotope effects. While theoretical models invoke ion-neutral exchange reactions outside the protoplanetary disk and photochemical self-shielding on the disk surface to explain the variations, there are no experiments to substantiate these models. Experimental results of N2 photolysis at vacuum UV wavelengths in the presence of hydrogen are presented here, which show a wide range of enriched δ(15)N values from 648‰ to 13,412‰ in product NH3, depending upon photodissociation wavelength. The measured enrichment range in photodissociation of N2, plausibly explains the range of δ(15)N in extraterrestrial materials. This study suggests the importance of photochemical processing of the nitrogen reservoirs within the solar nebula.