Numerical study of the oxidation process of dimethylsulfide in the marine atmosphere

A box model, involving simple heterogeneous reaction processes associated with the production of non-sea-salt sulfate (nss-SO ₄ ^2– ) particles, is used to investigate the oxidation processes of dimethylsulfide (DMS or CH₃SCH₃) in the marine atmosphere. The model is applied to chemical reactions in the atmospheric surface mixing layer, at intervals of 15 degrees latitude between 60° N and 60° S. Given that the addition reaction of the hydroxyl radical (OH) to the sulfur atom in the DMS molecule is faster at lower temperature than at higher temperature and that it is the predominant pathway for the production of methanesulfonic acid (MSA or CH₃SO₃H), the results can well explain both the increasing tendency of the molar ratio of MSA to nss-SO ₄ ^2– toward higher latitudes and the uniform distribution with latitude of sulfur dioxide (SO₂). The predicted production rate of MSA increases with increasing latitude due to the elevated rate constant of the addition reaction at lower temperature. Since latitudinal distributions of OH concentration and DMS reaction rate with OH are opposite, a uniform production rate of SO₂ is realized over the globe. The primary sink of DMS in unpolluted air is caused by the reaction with OH. Reaction of DMS with the nitrate radical (NO₃) also reduces DMS concentration but it is less important compared with that of OH. Concentrations of SO₂, MSA, and nss-SO ₄ ^2– are almost independent of NO _x concentration and radiation field. If dimethylsulfoxide (DMSO or CH₃S(O)CH₃) is produced by the addition reaction and further converted to sulfuric acid (H₂SO₄) in an aqueous solution of cloud droplets, the oxidation process of DMSO might be important for the production of aerosol particles containing nss-SO ₄ ^2– at high latitudes.     

Seasonal variations of spectra of wind speed and air temperature in the mesoscale frequency range

Seasonal variations of the spectra of wind speed and air temperature in the mesoscale frequency range from 1.3 × 10^-4 to 1.5 × 10^-3 Hz (10 min to 2 h periods) have been studied through observations over land for one year. Spectrographs [time series of isopleths of spectral densities, f · S(f) vs f] of wind speed and air temperature contain occasional peaks that are attributed to short-lived mesoscale atmospheric activity with narrow frequency bands. Significant spectral peaks of wind speed were found in 19% of the total observations in winter, and in 15–16% in the other seasons; for air temperature, they occured in 12% of observations in autumn, and in 16–19% in the other seasons. The peaks most often occurred in the period range from 30 min to 1 h; most had durations less than 24 h. Mesoscale fluctuations of wind speed and air temperature were highly correlated, and in most cases, phase differences were 90–180 ° with air temperature leading wind speed. Significant spectral peaks of wind speed often occurred during northerly seasonal cold winds in winter, and accompanied tropical and/or mid-latitude cyclones in the other seasons. When the peaks occurred, wind speed was usually relatively high and the atmospheric surface layer was unstable.     

Symmetrical fft technique and its applications to earthquake engineering

The objective of this paper is to propose an FFT technique symmetrical for time and frequency, in which the symmetrization is done by introducing generating functions. By the symmetrical treatment, it becomes possible to derive several complementary relations in the time and frequency domains. Based on the idea of the symmetrical FFT technique, the phase problem of seismic waves is discussed not only in the frequency domain but also in the time domain. Furthermore, the deconvolution technique to evaluate the minimum-phase-shift and all-pass functions of seismic waves, which is not discussed sufficiently in earthquake engineering, is developed in the two domains. Numerical examples to present these basic ideas are also illustrated in the symmetrical framework.     

Pressure-temperature dependent compositional variation of phlogopitic micas in upper mantle peridotites

Compositional variation of phlogopitic micas in upper mantle peridotites is reviewed. Phlogopitic micas in garnet peridotites are systematically lower in Al (or eastonite component) than those in spinel peridotites. The core of phlogopite megacryst and phenocryst of kimberlite is always lower in Al than the rim. It is apparent that Al/(Al + Si) ratio or eastonite component in phlogopitic micas in ultramafic rocks is controlled by the equilibrium pressure and temperature. In the upper mantle peridotites containing garnet or spinel, the Al/(Al + Si) ratio of phlogopitic mica decreases with increasing pressure at constant temperature. Phlogopitic mica is a potential thermo-barometer in both garnet- and spinel-peridotite facies.     

On the chondrite—achondrite transition: mineralogy and chemistry of Yamato 74160 (LL7)

We report on the petrology, mineralogic properties and contents of major elements and trace elements Ag, Au, Bi, Cd, Co, Cs, Ga, In, Rb, Se, Te, Tl, U and Zn (determined by radiochemical neutron activation analysis) in Yamato 74160, interpreted as an LL7 chondrite. All properties are consistent with this meteorite having been recrystallized and partially melted locally once at temperatures well above 1090°C under conditions such that some minerals (e.g. plagioclase, euhedral pyroxene, tetrataenite) grew from melt pockets and siderophilic and chalcophilic elements were lost by extraction into eutectic melt that drained away. Inhomogeneous plagioclase compositions and mobile element loss suggest shock as the most likely heat source. Yamato 74160, while inferentially chondritic, is a larval achondrite: even higher temperatures and longer times would have been required to cause the separations necessary to transform it to an identifiable achondrite type.     

Fine structure beneath the Tohoku district, northeastern Japan arc, as derived by an inversion of P-wave arrival times from local earthquakes

Three dimensional P-wave velocity structure beneath the Tohoku district, northeastern Japan arc, is investigated by an inversion of arrival times from local earthquakes using the method originally due to Aki and Lee (1976).In the crust (0–32 km depth) a low-velocity region is found along the volcanic front and its vicinity. Velocities at depths of 32–65 km are low beneath the regions where many Quaternary volcanoes and geothermal areas are distributed. In the region deeper than 65 km, the subduction of the Pacific plate is clearly revealed, and the mantle structure above the descending plate is rather uniform. These features suggest that volcanic activities have relation to the upper mantle structure. The results obtained in this study will be helpful in investigating the mechanism of magma generation in a subduction zone.     

Field survey of the East Java earthquake and tsunami of June 3, 1994

A field survey of the June 3, 1994 East Java earthquake tsunami was conducted within three weeks, and the distributions of the seismic intensities, tsunami heights, and human and house damages were surveyed. The seismic intensities on the south coasts of Java and Bali Islands were small for an earthquake with magnitudeM 7.6. The earthquake caused no land damage. About 40 minutes after the main shock, a huge tsunami attacked the coasts, several villages in East Java Province were damaged severely, and 223 persons perished. At Pancer Village about 70 percent of the houses were swept away and 121 persons were killed by the tsunami. The relationship between tsunami heights and distances from the source shows that the Hatori's tsunami magnitude wasm=3, which seems to be larger for the earthquake magnitude. But we should not consider this an extraordinary event because it was pointed out byHatori (1994) that the magnitudes of tsunamis in the Indonesia-Philippine region generally exceed 1–2 grade larger than those of other regions.     

Antiferromagnetic transition of fayalite under high pressure studied by Mössbauer spectroscopy

Néel temperature (Tm _N of α-Fe₂SiO₄ (fayalite) was measured as a function of pressure by means of Mössbauer spectroscopy in the pressure range 0–16 Gpa. High pressure was generated using a clamp-type miniature diamond anvil cell which was inserted into a cryostat. The Néel temperature increased linearly with increasing pressure at a rate of dT _N /dp=2.2±0.2 K/GPa. The result is discussed on the basis of the model proposed for the magnetic structure of fayalite by Santoro et al. (1966). The observed dT _N /dp suggests that the superexchange interactions vary as the ?10/3 power of the volume while the volume dependence of the direct exchange interactions is positive and small.     

Kinetics of reactions between aqueous sulfates and sulfides in hydrothermal systems

The rates of chemical reactions between aqueous sulfates and sulfides are essentially identical to sulfur isotopic exchange rates between them, because both the chemical and isotopic reactions involve simultaneous oxidation of sulfide-sulfur atoms and reduction of sulfate-sulfur. The rate of reaction can be expressed as a second order rate law: R = k·[∑SO₄^2?]·[∑S^2?], where R is the overall rate, k is the rate constant and [∑SO₄^2?] and [∑S^2?] are molal concentrations. We have computed the rate constants from the available experimental data on the partial exchange of sulfur isotopes between aqueous sulfates and sulfides using the rate law established by us: $\text{ln(}\text{α}{}^{\mathrm{e}}\text{? α}\text{α}{}^{\mathrm{e}}\text{? α}{}^0\text{) = ? kt([∑SO}{}_4{}^{\mathrm{2?}}\text{] + [∑S}{}^{\mathrm{2?}}\text{])}$, where t is time and α⁰, α, and α^e are, respectively, the fractionation factors at t = 0 (the initial condition), at the end of experiment, and at equilibrium. The equilibrium fractionation factor can be expressed as: $\text{1000 ln α}{}^{\mathrm{e}}\text{=}\text{6.463 × 10}{}^6\text{T}{}^2\text{+ 0.56 (±.5)}$ (T in Kelvin).The rate constants are strongly dependent on T and pH, but not in as simple a manner as suggested by Igumnov (1976). Our rate constants in Na-bearing hydrothermal solutions decrease by 1 order of magnitude with an increase in pH by 1 unit at pH's less than ~3, remain constant in the pH range of ~4 to ~7, and again decrease at pH >7. The activation energy for the reaction also depends on pH: 18.4 ± 1 kcal/mole at pH = 2, 29.6 ± 1 kcal/mole at pH = 4 to 7, and between 40 and 47 kcal/mole at pH around 9. The observed pH dependence of the rate constant and of the activation energy can be best explained by a model involving thiosulfate molecules as reaction intermediates, in which the intramolecular exchange of sulfur atoms in thiosulfates becomes the rate determining step.The rate constants obtained in this study were used to compute the changes in the isotopic fractionation factors between aqueous sulfates and sulfides during cooling of fluids. Comparisons with data of coexisting sulfate-sulfide minerals in hydrothermal deposits, suggest that simple cooling was not a likely mechanism for coprecipitation of sulfate and sulfide minerals at temperatures below 350°C. Mixing of sulfide-rich solutions with sulfate-rich solutions at or near the depositional sites is a more reasonable process for explaining the observed fractionation.The degree of attainment of chemical equilibrium between aqueous sulfates and sulfides in a hydrothermal system, and the applicability of a_O2-pH type diagrams to mineral deposits, depends on the ∑S content and the thermal history of the fluid, which in turn is controlled by the flow rate and the thermal gradient in the system.The rates of sulfate reduction by non-bacterial processes involving a variety of reductants are also dependent on T, pH, [∑SO₄^2?], and [∑S^2?], and appear to be fast enough to become geochemically important at temperatures above about 200°C.     

∼3,850 Ma tonalites in the Nuuk region,Greenland: geochemistry and their reworking within an Eoarchaean gneiss complex

The Eoarchaean (>3,600 Ma) Itsaq Gneiss Complex of southern West Greenland is dominated by polyphase orthogneisses with a complex Archaean tectonothermal history. Some of the orthogneisses have c. 3,850 Ma zircons, and they vary from rare single phase metatonalites to more common complexly banded migmatites. This is due to heterogeneous strain, in situ anatexis and granitic veining superimposed during younger tectonothermal events. In the single-phase tonalites with c. 3,850 Ma zircon, oscillatory-zoned prismatic zircon is all 3,850 Ma old, but shows patchy ancient loss of radiogenic Pb. SHRIMP spot analyses and laser ablation ICP-MS depth profiling show that thin (usually < 10 μm) younger (3,660–3,590 Ma and Neoarchaean) shells of lower Th/U metamorphic zircon are present on these 3,850 Ma zircons. Several samples with this simple zircon population occur on islands near Akilia. In contrast, migmatites usually contain more complex zircon populations, with often more than one generation of igneous zircon present. Additional zircon dating of banded gneisses across the Complex shows that samples with c. 3,850 Ma igneous zircon are not just a phenomenon restricted to Akilia and adjacent islands. For example, migmatites from Itilleq (c. 65 km from Akilia) contain variable amounts of oscillatory-zoned 3,850 Ma and 3,650 Ma zircon, interpreted, respectively, as the rock age and the time of crustal melting under Eoarchaean metamorphism. With only 110–140 ppm Zr in the tonalites and likely magmatic temperatures of >850°C, zircon solubility–melt composition relationships show that they were only one-third saturated in zircon. Any zircon entrained in the precursor magmas would thus have been highly soluble. Combined with the cathodoluminesence imaging, this demonstrates that the c. 3,850 Ma oscillatory zoned zircon crystallised out of the melt and hence gives a magmatic age. Thus the rare well-preserved tonalites and palaeosome in migmatites testify that c. 3,850 Ma quartzo–feldspathic rocks are a widespread (but probably minor) component in the Itsaq Gneiss Complex. C. 3,850 Ma zircon with negative Eu anomalies (showing growth in felsic systems) also occurs as detrital grains in rare c. 3,800 Ma metaquartzites and as inherited grains in some 3,660 Ma granites (sensu stricto). These demonstrate that still more c. 3,850 Ma rocks were present, but were recycled into Eoarchaean sediments and crustally derived granites. The major and trace element characteristics (e.g. LREE enrichment, HREE depletion, low MgO) of the best-preserved c. 3,850 Ma rocks are typical of Archaean TTG suites, and thus argue for crust formation processes involving important contributions from melting of hydrated mafic crust to the earliest Archaean. Five c. 3,850 Ma tonalites were selected as the best preserved on the basis of field criteria and zircon petrology. Four of these samples have overlapping initial ɛ_Nd (3,850 Ma) values from +2.9 to +3.6± 0.5, with the fourth having a slightly lower value of +0.6. These data provide additional evidence for a markedly LREE-depleted early terrestrial mantle reservoir. The role of c. 3,850 Ma crust should be considered in interpreting isotope signatures of the younger (3,800–3,600 Ma) rocks of the Itsaq Gneiss Complex. Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.