Noble gases and nitrogen in samples of asteroid Ryugu record its volatile sources and recent surface evolution.

The near-Earth carbonaceous asteroid (162173) Ryugu is expected to contain volatile chemical species that could provide information on the origin of Earth's volatiles. Samples of Ryugu were retrieved by the Hayabusa2 spacecraft. We measured noble gas and nitrogen isotopes in Ryugu samples and found that they are dominated by presolar and primordial components, incorporated during Solar System formation. Noble gas concentrations are higher than those in Ivuna-type carbonaceous (CI) chondrite meteorites. Several host phases of isotopically distinct nitrogen have different abundances among the samples. Our measurements support a close relationship between Ryugu and CI chondrites. Noble gases produced by galactic cosmic rays, indicating a ~5 million year exposure, and from implanted solar wind record the recent irradiation history of Ryugu after it migrated to its current orbit.

First asteroid gas sample delivered by the Hayabusa2 mission: A treasure box from Ryugu.

The Hayabusa2 spacecraft returned to Earth from the asteroid 162173 Ryugu on 6 December 2020. One day after the recovery, the gas species retained in the sample container were extracted and measured on-site and stored in gas collection bottles. The container gas consists of helium and neon with an extraterrestrial 3He/4He and 20Ne/22Ne ratios, along with some contaminant terrestrial atmospheric gases. A mixture of solar and Earth's atmospheric gas is the best explanation for the container gas composition. Fragmentation of Ryugu grains within the sample container is discussed on the basis of the estimated amount of indigenous He and the size distribution of the recovered Ryugu grains. This is the first successful return of gas species from a near-Earth asteroid.

Last glacial temperature reconstructions using coupled isotopic analyses of fossil snails and stalagmites from archaeological caves in Okinawa, Japan.

We applied a new geoarchaeological method with two carbonate archives, which are fossil snails from Sakitari Cave and stalagmites from Gyokusen Cave, on Okinawa Island, Japan, to reconstruct surface air temperature changes over the northwestern Pacific since the last glacial period. Oxygen isotope ratios (δ18O) of modern and fossil freshwater snail shells were determined to infer seasonal temperature variations. The observational and analytical data confirm that δ18O values of fluid inclusion waters in the stalagmite can be regarded as those of spring waters at the sites where snails lived. Our results indicate that the annual mean, summer, and winter air temperatures were lower by 6-7 °C at ca. 23 thousand years ago (ka) and 4-5 °C at ca. 16-13 ka than those of the present day. Our reconstruction implies that surface air cooling was possibly two times greater than that of seawater around the Ryukyu Islands during the Last Glacial Maximum, which potentially enhanced the development of the East Asian summer monsoon during the last deglaciation. Considering the potential uncertainties in the temperature estimations, the climatic interpretations of this study are not necessarily definitive due to the limited number of samples. Nevertheless, our new geoarchaeological approach using coupled δ18O determinations of fossil snails and stalagmite fluid inclusion waters will be useful for reconstructing snapshots of seasonally resolved time series of air temperatures during the Quaternary.

Isotopic evidence for acidity-driven enhancement of sulfate formation after SO2 emission control.

After the 1980s, atmospheric sulfate reduction is slower than the dramatic reductions in sulfur dioxide (SO2) emissions. However, a lack of observational evidence has hindered the identification of causal feedback mechanisms. Here, we report an increase in the oxygen isotopic composition of sulfate ([Formula: see text]) in a Greenland ice core, implying an enhanced role of acidity-dependent in-cloud oxidation by ozone (up to 17 to 27%) in sulfate production since the 1960s. A global chemical transport model reproduces the magnitude of the increase in observed [Formula: see text] with a 10 to 15% enhancement in the conversion efficiency from SO2 to sulfate in Eastern North America and Western Europe. With an expected continued decrease in atmospheric acidity, this feedback will continue in the future and partially hinder air quality improvements.

Abrupt ice-age shifts in southern westerly winds and Antarctic climate forced from the north.

The mid-latitude westerly winds of the Southern Hemisphere play a central role in the global climate system via Southern Ocean upwelling1, carbon exchange with the deep ocean2, Agulhas leakage (transport of Indian Ocean waters into the Atlantic)3 and possibly Antarctic ice-sheet stability4. Meridional shifts of the Southern Hemisphere westerly winds have been hypothesized to occur5,6 in parallel with the well-documented shifts of the intertropical convergence zone7 in response to Dansgaard-Oeschger (DO) events- abrupt North Atlantic climate change events of the last ice age. Shifting moisture pathways to West Antarctica8 are consistent with this view but may represent a Pacific teleconnection pattern forced from the tropics9. The full response of the Southern Hemisphere atmospheric circulation to the DO cycle and its impact on Antarctic temperature remain unclear10. Here we use five ice cores synchronized via volcanic markers to show that the Antarctic temperature response to the DO cycle can be understood as the superposition of two modes: a spatially homogeneous oceanic 'bipolar seesaw' mode that lags behind Northern Hemisphere climate by about 200 years, and a spatially heterogeneous atmospheric mode that is synchronous with abrupt events in the Northern Hemisphere. Temperature anomalies of the atmospheric mode are similar to those associated with present-day Southern Annular Mode variability, rather than the Pacific-South American pattern. Moreover, deuterium-excess records suggest a zonally coherent migration of the Southern Hemisphere westerly winds over all ocean basins in phase with Northern Hemisphere climate. Our work provides a simple conceptual framework for understanding circum-Antarctic temperature variations forced by abrupt Northern Hemisphere climate change. We provide observational evidence of abrupt shifts in the Southern Hemisphere westerly winds, which have previously documented1-3 ramifications for global ocean circulation and atmospheric carbon dioxide. These coupled changes highlight the necessity of a global, rather than a purely North Atlantic, perspective on the DO cycle.

Asynchrony between Antarctic temperature and CO2 associated with obliquity over the past 720,000 years.

The δD temperature proxy in Antarctic ice cores varies in parallel with CO2 through glacial cycles. However, these variables display a puzzling asynchrony. Well-dated records of Southern Ocean temperature will provide crucial information because the Southern Ocean is likely key in regulating CO2 variations. Here, we perform multiple isotopic analyses on an Antarctic ice core and estimate temperature variations at this site and in the oceanic moisture source over the past 720,000 years, which extend the longest records by 300,000 years. Antarctic temperature is affected by large variations in local insolation that are induced by obliquity. At the obliquity periodicity, the Antarctic and ocean temperatures lag annual mean insolation. Further, the magnitude of the phase lag is minimal during low eccentricity periods, suggesting that secular changes in the global carbon cycle and the ocean circulation modulate the phase relationship among temperatures, CO2 and insolation in the obliquity frequency band.

Sulphate-climate coupling over the past 300,000 years in inland Antarctica.

Sulphate aerosols, particularly micrometre-sized particles of sulphate salt and sulphate-adhered dust, can act as cloud condensation nuclei, leading to increased solar scattering that cools Earth's climate. Evidence for such a coupling may lie in the sulphate record from polar ice cores, but previous analyses of melted ice-core samples have provided only sulphate ion concentrations, which may be due to sulphuric acid. Here we present profiles of sulphate salt and sulphate-adhered dust fluxes over the past 300,000 years from the Dome Fuji ice core in inland Antarctica. Our results show a nearly constant flux of sulphate-adhered dust through glacial and interglacial periods despite the large increases in total dust flux during glacial maxima. The sulphate salt flux, however, correlates inversely with temperature, suggesting a climatic coupling between particulate sulphur and temperature. For example, the total sulphate salt flux during the Last Glacial Maximum averages 5.78 mg m(-2) yr(-1), which is almost twice the Holocene value. Although it is based on a modern analogue with considerable uncertainties when applied to the ice-core record, this analysis indicates that the glacial-to-interglacial decrease in sulphate would lessen the aerosol indirect effects on cloud lifetime and albedo, leading to an Antarctic warming of 0.1 to 5 kelvin.

Northern Hemisphere forcing of climatic cycles in Antarctica over the past 360,000 years.

The Milankovitch theory of climate change proposes that glacial-interglacial cycles are driven by changes in summer insolation at high northern latitudes. The timing of climate change in the Southern Hemisphere at glacial-interglacial transitions (which are known as terminations) relative to variations in summer insolation in the Northern Hemisphere is an important test of this hypothesis. So far, it has only been possible to apply this test to the most recent termination, because the dating uncertainty associated with older terminations is too large to allow phase relationships to be determined. Here we present a new chronology of Antarctic climate change over the past 360,000 years that is based on the ratio of oxygen to nitrogen molecules in air trapped in the Dome Fuji and Vostok ice cores. This ratio is a proxy for local summer insolation, and thus allows the chronology to be constructed by orbital tuning without the need to assume a lag between a climate record and an orbital parameter. The accuracy of the chronology allows us to examine the phase relationships between climate records from the ice cores and changes in insolation. Our results indicate that orbital-scale Antarctic climate change lags Northern Hemisphere insolation by a few millennia, and that the increases in Antarctic temperature and atmospheric carbon dioxide concentration during the last four terminations occurred within the rising phase of Northern Hemisphere summer insolation. These results support the Milankovitch theory that Northern Hemisphere summer insolation triggered the last four deglaciations.

Deuterium and oxygen-18 determination of microliter quantities of a water sample using an automated equilibrator.

We describe a modified version of the equilibration method and a correction algorithm for isotope ratio measurements of small quantities of water samples. The deltaD and the delta(18)O of the same water sample can both be analyzed using an automated equilibrator with sample sizes as small as 50 microL. Conventional equilibration techniques generally require water samples of several microL. That limitation is attributable mainly to changes in the isotope ratio ((18)O/(16)O or D/H) of water samples during isotopic exchange between the equilibration gas (CO(2) or H(2)) and water, and therefore the technique for microL quantities of water requires mass-balance correction using the water/gas (CO(2) or H(2)) mole ratio to correct this isotopic effect. We quantitatively evaluate factors controlling the variability of the isotopic effect due to sample size. Theoretical consideration shows that a simple linear equation corrects for the effects without determining parameters such as isotope fractionation factors and water/gas mole ratios. Precisions (1-sigma) of 50-microL meteoric water samples whose isotopic compositions of -1.4 to -396.2 per thousand for deltaD are +/-0.5 to +/-0.6 per thousand, and of -0.37 to -51.37 per thousand for delta(18)O are +/-0.01 to +/-0.11 per thousand.

Botanical and geographical origin identification of industrial ethanol by stable isotope analyses of C, H, and O.

The isotope ratios of carbon, hydrogen, and oxygen of rectified alcohols were determined to distinguish their botanical and geographical origins by continuous flow-isotope ratio mass spectrometry (CF-IRMS). The (13)C/(12)C and (18)O/(16)O ratios of 27 fermented alcohols with known origins showed clusters derived from each botanical origin, viz. corn, sugarcane, wheat, and tapioca. C3 and C4 plants were easily distinguishable by the (13)C/(12)C ratio. Sugarcane and corn are both C4 plants, and they showed small differences in isotope ratios. The combination plots of the D/H and (18)O/(16)O ratios enabled us to designate the geographical origins of alcohol derived from the same kind of crop, such as Chinese or American corn. The chemically synthetic and fermented alcohols were clearly distinguished by D/H and (18)O/(16)O ratios. Isotope ratios were useful for origin identification of alcohol. We plan to construct a database of alcohol isotope ratios to determine the origins of raw materials in alcohol.