Experimental impact shock chemistry on planetary icy satellites

We present new experimental results on impact shock chemistry into icy satellites of the outer planets. Icy mixtures of pure water ice with CO₂, Na₂CO₃, CH₃OH, and CH₃OH/(NH₄)₂SO₄ at 77 K were ablated with a powerful pulsed laser—a new technique used to simulate shock processes which can occur during impacts. New products were identified by GC-MS and FTIR analyses after laser ablation. Our results show that hydrogen peroxide is formed in irradiated H₂O/CO₂ ices with a final concentration of 0.23%. CO and CH₃OH were also detected as main products. The laser ablation of frozen H₂O/Na₂CO₃ generates only CO and CO₂ as destruction products from the salt. Pulsed irradiation of water ice containing methanol leads also to the formation of CO and CO₂, generates methane and more complex molecules containing carbonyl groups like acetaldehyde, acetone, methyl formate, and a diether, dimethyl formal. The last three compounds are also produced when adding ammonium sulfate to H₂O/CH₃OH ice, but acetone is more abundant. The formation of two hydrocarbons, CH₄ and C₂H₆ is observed as well as the production of three nitrogen compounds, nitrous oxide, hydrogen cyanide, and acetonitrile.     

Temperature profiling measurements by sea turtles improve ocean state estimation in the Kuroshio-Oyashio Confluence region

Ocean Dynamics - We demonstrate that assimilation of water temperature measurements by sea turtles into an operational ocean nowcast/forecast system improves representation of mesoscale eddies and...     

Evolution of the composition of seawater through geologic time, and its influence on the evolution of life

The redox state of the surface environment of the early Earth is still controversial, and a detailed and quantitative estimate is still lacking. We carried out in-situ analyses of major, trace, and rare-earth elements of carbonate minerals in rocks with primary sedimentary structures in shallow and deep sea-deposits, in order to eliminate secondary carbonate and contamination of detrital materials, and to estimate the redox condition of seawater through time. Based on the Ce content and anomalies of the carbonate minerals at given parameters of atmospheric CO₂ content (pCO₂) and Ca content of seawater, we calculated the oxygen contents of shallow and deep seawater, respectively. The results show that the oxygen content of the deep sea was low and constant until at least 1.9 Ga. The oxygen content of shallow seawater increased after 2.7 Ga, but fluctuated. It became quite high at 2.5 and 2.3 Ga, but eventually increased after the Phanerozoic. In addition, the calculation of a high pCO₂ condition shows that seawater was more oxic even in the Archean than at present, suggesting a relatively low pCO₂ through geologic time.Our detailed calculations from compositions of carbonate minerals in Three Gorge area, south China show a low oxygen content of seawater after the Snowball Earth until the late Ediacaran, an increase in the late Ediacaran, and a significant decrease around the Precambrian–Cambrian and Nemakit/Daldynian–Tommotian boundaries. These variations were possibly caused by global regression and dissolution of methane hydrates.     

Progressive sequence of reactions of the Ryoke metamorphism in the Yanai district, southwest Japan: the formation of cordierite

The compositions of biotite and muscovite were examined in terms of the paragenesis and the metamorphic grade in low- to medium-grade pelitic rocks of the Ryoke metamorphism in the Yanai district, southwest Japan. The biotite and muscovite that coexist with K-feldspar have a higher K component in an A'KF diagram than those in rocks lacking K-feldspar. This fact reflects an increase in the K₂O content in muscovite, but in biotite it reflects an increase of not only the K₂O content but also of the octahedral vacancy.
At higher metamorphic grade beyond the cordierite isograd, where cordierite coexists with neither chlorite nor K-feldspar, the biotite shows an increase in illite, K Aliv □xii−1 Si−1, and Tschermak components, Alvi Aliv R+−1 Si−1, where □xii and R+ denote the interlayer vacancy and (Fe+Mg+Mn), respectively. A reaction to define the cordierite isograd is proposed by treating this chemical change as being responsible for the first appearance of cordierite, i.e. K,Al-poor biotite+phengitic muscovite=K,Al-rich biotite+cordierite+quartz+water .By treating this as a key reaction in medium-grade metamorphism, a set of reaction in a progressive metamorphism is established for the Ryoke metamorphism, a typical low-pressure type metamorphism. Some textures in one of the high-grade areas, the K-feldspar-cordierite zone, suggest that a further two prograde reactions have taken place, i.e. andalusite+biotite+quartz=cordierite+K-feldspar+water
and   andalusite=sillimanite.quartz=cordierite+K-feldspar+water
This implies that this zone probably has a P–T  path involving isobaric heating.     

Sulfate-coated dust particles in the free troposphere over Japan

Airborne aerosol collections were performed over Wakasa bay (36°00′N, 135°30′E) in March and Kumano open sea (34°00′N, 136°50′E) and Seto (35°10′N, 137°10′E) in July 2001 at altitudes between 1.0 and 5.8 km. The particles were individually analyzed using transmission electron microscopy (TEM). Relatively large mineral-dust (mostly clay) particles were abundant in the March samples. They also dominated in July in the mid-troposphere higher than 4 km altitude, whereas sea salt and ammonium sulfate were more abundant at lower altitudes. Ca-coated grid samples show many traces of aqueous sulfate droplets. The proportions of former sulfate droplets to the total collected particles apparently increased with increasing relative humidity at the time of sampling. TEM analysis revealed that a significant fraction of these former droplets enclose mineral-dust particles as well as sea salt, soot, and fly ash. Some enclose mixtures of mineral-dust, sea-salt, soot, and fly ash particles. The results provide evidence that mineral dust from the Asian continent could acquire coatings of sulfate while being transported in the free troposphere. The mineral-dust particles probably acquired the sulfate coatings either through heterogeneous uptake of gaseous SO₂ and subsequent oxidation or through coagulation with cloud or fog droplets. The presence of the mixed particles in sulfate droplets also indicates that aggregation of particles of different origins occurred through cloud processing. Such sulfate-coated dust particles would affect cloud formation, precipitation, and chemistry of the free troposphere.     

High‐resolution lithostratigraphy and organic carbon isotope stratigraphy of the Lower Triassic pelagic sequence in central Japan

After the severest mass extinction event in the Phanerozoic, biotic recovery from the extinction at the Permian–Triassic boundary required approximately 5 my, which covers the entire Early Triassic. It is important to obtain information on the superocean Panthalassa, which occupied most of the world ocean, to explore paleoenvironmental changes during the Early Triassic at the global scale. In order to establish the continuous lithostratigraphy of pelagic sediments in Panthalassa during the Early Triassic, high‐resolution reconstruction of the Lower Triassic pelagic sequence in Japan was conducted for the first time based on detailed field mapping and lithostratigraphic correlation in the Inuyama area, central Japan. The reconstructed Early Triassic sequence is approximately 9.5 m thick, consists of five rock types, and is divided into eight lithological units. For the reconstructed continuous sequence, measurement of carbon isotopic composition of sedimentary organic matter (δ¹³C_org) was carried out. Stratigraphic variation of the δ¹³C_org value shows large‐amplitude fluctuations between ?34.4 and ?21.0‰ throughout the sequence. In order to establish a higher resolution age model for the reconstructed Lower Triassic pelagic sequence, we correlated δ¹³C_org records in the Inuyama area with high‐resolution isotopic profiles of carbonate carbon (δ¹³C_carb) from shallow‐marine carbonate sequences in southern China based on the similarity in general variation patterns with age constraints by radiolarian and conodont biostratigraphy. The result provides a high‐resolution time scale for the pelagic sequence of Panthalassa during the Smithian and Spathian. The age model suggests a drastic increase in sedimentation rate during the late Smithian, which should have been caused by the increase in terrigenous input to this site.     

Sr isotope excursion across the Precambrian–Cambrian boundary in the Three Gorges area, South China

The Precambrian/Cambrian (PC/C) boundary is one of the most important intervals for the evolution of life. However, the scarcity of well-preserved outcrops across the boundary leaves an obstacle in decoding surface environmental changes and patterns of biological evolution.In south China, strata through the PC/C boundary are almost continuously exposed and contain many fossils, suitable for study of environmental and biological change across the PC/C boundary. We undertook deep drilling at four sites in the Three Gorges area to obtain continuous and fresh samples without surface alteration and oxidation. ⁸⁷Sr/⁸⁶Sr ratios of the fresh carbonate rocks, selected based on microscopic observation and geochemical signatures of Mn/Sr and Rb/Sr ratios, aluminum and silica contents, and δ¹³C and δ¹⁸O values, were measured with multiple collector-inductively coupled plasma–mass spectrometric techniques.The chemostratigraphy of ⁸⁷Sr/⁸⁶Sr ratios of the drilled samples displays a smooth curve and a large positive anomaly just below the PC/C boundary between the upper part of Baimatuo Member of the Dengying Formation and the lower part of the Yanjiahe Formation. The combination of chemostratigraphies of δ¹³C and ⁸⁷Sr/⁸⁶Sr indicates that the ⁸⁷Sr/⁸⁶Sr excursions preceded the δ¹³C negative excursion, and suggests that global regression or formation of the Gondwana supercontinent, possibly together with a high atmospheric pCO₂, caused biological depression.     

Impacts by heavy-oil spill from the Russian tanker Nakhodka on intertidal ecosystems: recovery of animal community

The impact of a heavy-oil spill from the Nakhodka on an intertidal animal community, and the recovery process of animals from the damage were surveyed from the autumn of 1997 to the spring of 2001. The field study was carried out in the rocky coast of Imago-Ura Cove, located along the Sea of Japan, where clean-up operations for oil pollution had been conducted less intensely than in other polluted areas. We have examined individual number of each animal taxon by continuously placing a quadrat of 5 m width along the entire intertidal zone of the cove. A total of 76 invertebrate taxa including 57 species of mollusks, 10 species of crustaceans were observed during the survey. The number of taxa increased from 1998 to 1999 in areas where the initial oil pollution was intense. Total individual number of benthic animals continued to increase from 1998 to 2000 in the polluted areas. The impact of oil on benthic animals was different from species to species. Some species such as Cellana toreuma and Monodonta labio confusa increased rapidly after the oil spill, whereas other species such as Patelloida saccharina lanx and Septifer virgatus did not show any apparent temporal tendencies. Population size structure of P. saccharina lanx varied greatly among years, however that of M. labio confusa did not. For P. saccharina lanx, recruitment was unsuccessful in 1997, possibly due to the effect of oil pollution. These differences in responses to oil pollution among benthic animals are considered to be caused by the differences in habitat use, susceptibility to heavy-oil, life history and migration ability. The findings suggest that it took at least 2-3 years for the intertidal animal community to recover to its original level after the oil spill.     

Contamination status of POPs and BFRs and relationship with parasitic infection in finless porpoises (Neophocaena phocaenoides) from Seto Inland Sea and Omura Bay, Japan

Contamination status of brominated flame retardants (BFRs) and persistent organic pollutants (POPs) in blubber of finless porpoises (Neophocaena phocaenoides) stranded along the coasts of Seto Inland Sea and Omura Bay in Japan were investigated. Levels of PCBs, DDTs and CHLs were significantly higher than those of HCHs, HCB, PBDEs and HBCDs. Concentrations of PBDEs and HBCDs, as well as organochlorine compounds in males increased with body length (p<0.05). Among 14 PBDE congeners analyzed, BDE-47 was the predominant, which is similar to those generally reported in biota. PBDEs, HBCDs and PCBs showed no obvious temporal trend in concentrations during the study period, suggesting continuous environmental release of these chemicals. On the other hand, levels of DDT, CHLs and HCHs have decreased. Concentrations of PCBs in liver trematode infected individuals were significantly higher than those in not infected individuals, implying there could be a relationship between contaminant levels and parasitic infection.     

Noble gases in pillow basalt glasses from the northern Mariana Trough back-arc basin

Noble gas concentrations and isotopic compositions have been measured in eight samples of pillow basalt glasses collected from seven different localities along 250 km of the Mariana Trough spreading and rifting axis. The samples have uniform and mid-ocean ridge basalt (MORB)-like ³He/⁴He values of 9–12 × 10^–6 (6.4–8.6 times atmospheric) despite large variations in ⁴He. Concentrations of the noble gases Ne, Ar, Kr, and Xe show much smaller variations between samples, but larger variations in isotopic compositions of Ne, Ar, and Xe. Excess radiogenic ²¹Ne is observed in some samples. ⁴⁰Ar/³⁶Ar varies widely (atmospheric to 1880). Kr is atmospheric in composition for all samples. Some samples show a clear excess ¹²⁹Xe, which is a well-known MORB signature. Isotopic compositions of the heavier noble gases (Ar, Kr, and Xe) in some samples, however, show more atmospheric components. These data reflect the interaction of a MORB-like magma with an atmospheric component such as seawater or of a depleted mantle source with a water-rich component that was probably derived from the subducting slab.