Removal of Pb2+ from aqueous solutions using two Brazilian rocks containing zeolites

The removal of Pb²⁺ from aqueous solution by two Brazilian rocks that contain zeolites—amygdaloidal dacite (ZD) and sandstone (ZS)—was examined by batch experiments. ZD contains mordenite and ZS, stilbite. The effects of contact time, concentration of metal in solution and capacity of Na⁺ to recover the adsorbed metals were evaluated at room temperature (20°C). The sorption equilibrium was reached in the 30 min of agitation time. Both materials removed 100% of Pb²⁺ from solutions at concentrations up to 50 mg/L, and at concentrations larger than 100 mg/L of Pb²⁺, the adsorption capacity of sandstone was more efficient than that of amygdaloidal dacite due to the larger quantities and the type of zeolites (stilbite) in the cement of this rock. All adsorbed Pb²⁺ was easily replaced by Na⁺ in both samples. The analysis of the adsorption models using nonlinear regression revealed that the Sips and the Freundlich isotherms provided the best fit for the ZS and ZD experimental data, respectively, indicating the heterogeneous adsorption surfaces of these zeolites.     

Heterogeneous condensation of presolar titanium carbide core‐graphite mantle spherules

Abstract— We investigate heterogeneous nucleation and growth of graphite on precondensed TiC grains in the gas outflows from carbon‐rich asymptotic giant branch (AGB) stars employing a newly‐derived heterogeneous nucleation rate taking into account of the chemical reactions at condensation. Competition between heterogeneous and homogeneous nucleations and growths of graphite is investigated to reveal the formation conditions of the TiC core‐graphite mantle spherules found in the Murchison meteorite. It is shown that no homogeneous graphite grain condenses whenever TiC condenses prior to graphite in the plausible ranges of the stellar parameters. Heterogeneous condensation of graphite occurs on the surfaces of growing TiC grains, and prevents the TiC cores from reaching the sizes realized if all available Ti atoms were incorporated into TiC grains. The physical conditions at the formation sites of the TiC core‐graphite mantle spherules observed in the Murchison meteorite are expressed by the relation 0.2 < n?_0.1 (M₅/ζ)^?1/2L₄^1/4 < 0.7, where v_0.1 is the gas outflow velocity at the formation site in units of 0.1 km s^?1, M₅ the mass loss rate in 10^?5 M⊙ year^?1, L₄ the stellar luminosity in 10⁴ L⊙, and M/ζ is the effective mass loss rate taking account of non‐spherical symmetry of the gas outflows. The total gas pressures P_c at the formation sites for the effective mass loss rates M/ζ = 10^?5‐10^?3 M⊙ year^?1 correspond to 0.01 < P_c < 0.9 dyn cm^?2, implying that the observed TiC core‐graphite mantle spherules are formed not only at the superwind stage but also at the earlier stage of low mass loss rates. The constraint on the C/O abundance ratio, 1 < ? ? 1.03, is imposed to reproduce the observed sizes of the TiC cores. The derived upper limit of the C/O ratio is lower than the values estimated from the calculations without taking into account of heterogeneous condensation of graphite, and is close to the lower end of the C/O ratios inferred from the astronomical observations of carbon‐rich AGB stars. Brief discussion is given on other types of graphite spherules.     

The relationships between drastic changes in Sr isotope ratios of magma sources beneath the NE Japan arc and the spreading of the Japan sea back-arc basin

Summary Based on Sr isotopic data for Tertiary and Quaternary basaltic rocks from the NE Japan arc, relationships are discussed between the temporal variation of magma source characteristics and the opening of the Japan Sea. The basaltic rocks from the trench side and from the transitional zone show initial⁸⁷Sr/⁸⁶Sr ratios (Sr_i ratios) in the range of 0.70411–0.70546 but no temporal variation in Sr_i ratios. The back-arc side basaltic rocks with ages of 29.8 to 15 Ma have Sr_i ratios similar to those of the trench side and the transitional zone, and these values also show no temporal change. In contrast, the basaltic rocks from the back-arc side, with ages younger than 15 Ma, show significantly lower Sri ratios (0.70396 to 0.70290), which are slightly higher than those of N-type MORB. These Sr isotopic features may imply that at least before 15 Ma the magma source regions (the sub-continental mantle) beneath the NE Japan arc had an enriched chemical character and that after 15 Ma, the magma sources for volcanic rocks from the back-arc side show a drastic change in Sr isotopic character, from an enriched nature to a depleted one. The depleted magmas may have been formed as a result of injection of depleted asthenosphere (or of a depleted mantle diapir) into the subcontinental mantle under the back-arc side of the NE Japan arc, during the spreading of the Japan Sea back-arc basin. The middle Miocene basaltic rocks from the back-arc side are characterized by lower contents of LIL elements such as K₂O and Rb compared with those from the trench side, suggesting that during the middle Miocene (syn-opening stage of the Japan Sea) the degree of partial melting may have been higher in the back-arc side mantle than in the trench side mantle. High degree of partial melting in the back-arc side mantle can be attributed to an increasing geothermal gradient in the mantle due to the injection of hot asthenosphere. This injection might also have caused the melting of the lower crust from which the voluminous middle Miocene acidic volcanics in the back-arc side and transitional zone may have been produced.

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Drastische Veränderungen der Sr-Isotopenverhältnisse von Magmenquellen unterhalb des NE japanischen Vulkanbogens und ihre Beziehung zum Spreading des japanischen Back-Arc-Beckens

Zusammenfassung Die Beziehungen zwischen der zeitlichen Veränderung der Charakteristika von Magmenquellen und der Öffnung des Japanischen Meeres werden anhand von Sr-Isotopendaten tertiärer und quartärer basaltischer Gesteine diskutiert. Basaltische Gesteine von der Grabenseite und aus der Übergangszone ergaben initiale⁸⁷Sr/⁸⁶Sr Verhältnisse (Sr_i-Verhältnisse) von 0.70411–0.70546 und lassen keine zeitabhängige Änderung erkennen. Basaltische Besteine aus dem Back-Arc-Bereich mit Altern zwischen 29.8 und ca. 15 Ma zeigen ähnliche Sr_i-Verhältnisse und ebenfalls keine zeitliche Veränderung. Im Gegensatz dazu sind basaltische Gesteine aus dem Back-Arc-Bereich, die jünger als ca. 15 Ma sind, signifikant in ihren Sr_i-Verhältnissen (0.70396–0.70290) erniedrigt. Diese Verhältnisse liegen etwas höher als die von N-MORB. Die Sr-Isotopenergebnisse lassen vermuten, daß zumindest vor ca. 15 Ma der Herkunftsbereich der Magmen (subkontinentaler Mantel) unter dem NE japanischen Vulkanbogen chemisch angereichert war, während die Magmenquellen der jüngeren vulkanischen Gesteine des Back-Arc-Bereiches durch eine drastische Abreicherung charakterisiert sind. Die abgereicherten Magmen könnten, während der Öffnung des japanischen Back-Arc-Beckens, als Folge der Injektion abgereicherter Asthenosphäre (oder eines abgereicherten Manteldiapirs) in subkontinentalen Mantel unterhalb des Back-Arcs des NE japanischen Vulkanbogens, gebildet worden sein. Die miozänen basaltischen Gesteine des Back-Arc-Bereiches sind außerdem durch niedrigere Gehalte an LIL-Elementen, wie z.B. K₂O und Rb charakterisiert. Dies wird als Hinweis auf eine erhöhte Aufschmelzungsrate in diesem Bereich im mittleren Miozän (im Zuge der gleichzeitigen Öffnung des japanischen Meeres) verstanden. Die erhöhte Aufschmelzrate im Mantel des Back-Arc-Breiches wird auf einer Erhöhung des geothermischen Gradienten infolge der Injektion von heißer Asthenosphäre zurückgeführt. Diese Injektion von Asthenosphäre könnte auch der Grund für die Aufschmelzung von Unterkruste und für die Produktion weitverbreiteter saurer miozäner Vulkanite im Back-Arc-Bereich und der Übergangszone sein.

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With 6 Figures     

Removal of lead from cathode ray tube funnel glass by chloride volatilization

Cathode ray tube funnel glass is an environmentally problematic relict of old television sets. In particular, landfilling of this material is strongly discouraged because of its high lead content. However, recovery of this toxic lead could prevent its release into the environment and allow its reuse. In this research, lead was separated from the glass matrix by a chloride volatilization process. Melting of the funnel glass together with CaCl₂ resulted in the volatilization of 80 % of lead at 1,000 °C. The use of NaCl as a chlorination agent yielded less volatile lead, while poly(vinyl chloride) and gaseous HCl proved to be ineffective chlorination agents. The differences in the chlorination agent efficiencies could be attributed to differences in the corresponding formation of silicates. Energy-dispersive X-ray spectroscopy showed that diffusion plays an important role in the volatilization of PbCl₂.     

The role of Fischer-Tropsch catalysis in the origin of methane-rich Titan

Fischer-Tropsch catalysis, which converts CO and H₂ into CH₄ on the surface of iron catalyst, has been proposed to produce the CH₄ on Titan during its formation process in a circum-planetary subnebula. However, Fischer-Tropsch reaction rate under the conditions of subnebula have not been measured quantitatively yet. In this study, we conduct laboratory experiments to determine CH₄ formation rate and also conduct theoretical calculation of clathrate formation to clarify the significance of Fischer-Tropsch catalysis in a subnebula. Our experimental result indicates that the range of conditions where Fischer-Tropsch catalysis proceeds efficiently is narrow (T∼500-600 K) in a subnebula because the catalysts are poisoned at temperatures above 600 K under the condition of subnebula (i.e., H₂/CO = 1000). This suggests that an entire subnebula may not become rich in CH₄ but rather that only limited region of a subnebula may enriched in CH₄ (i.e., CH₄-rich band formation). Our experimental result also suggests that both CO and CO₂ are converted into CH₄ within time significantly shorter than the lifetime of the solar nebula at the optimal temperatures around 550 K. The calculation result of clathration shows that CO₂-rich satellitesimals are formed in the catalytically inactive outer region of subnebula. In the catalytically active inner region, CH₄-rich satellitesimals are formed. The resulting CH₄-rich satellitesimals formed in this region play an important role in the origin of CH₄ on Titan. When our experimental data are applied to a high-pressure model for subnebula evolution, it would predict that there should be CO₂ underneath the Iapetus subsurface and no thick CO₂ ice layer on Titan's icy crust. Such surface and subsurface composition, which may be observed by Cassini-Huygens mission, would provide crucial information on the origin of icy satellites.     

Development of an Automatic Echo-counting Program for HROFFT Spectrograms

Radio meteor observations by Ham-band beacon or FM radio broadcasts using “Ham-band Radio meteor Observation Fast Fourier Transform” (HROFFT) an automatic operating software have been performed widely in recent days. Previously, counting of meteor echoes on the spectrograms of radio meteor observation was performed manually by observers. In the present paper, we introduce an automatic meteor echo counting software application. Although output images of the HROFFT contain both the features of meteor echoes and those of various types of noises, a newly developed image processing technique has been applied, resulting in software that enables a useful auto-counting tool. There exists a slight error in the processing on spectrograms when the observation site is affected by many disturbing noises. Nevertheless, comparison between software and manual counting revealed an agreement of almost 90%. Therefore, we can easily obtain a dataset of detection time, duration time, signal strength, and Doppler shift of each meteor echo from the HROFFT spectrograms. Using this software, statistical analyses of meteor activities is based on the results obtained at many Ham-band Radio meteor Observation (HRO) sites throughout the world, resulting in a very useful “standard” for monitoring meteor stream activities in real time.     

Detection of a new interstellar molecule, H2CN

We have detected a new interstellar molecule, H2CN (methylene amidogen), in the cold, dark molecular cloud TMC-l. The column density of H2CN is estimated to be approximately 1.5 x 10(11) cm-2 by assuming an excitation temperature of 5 K. This column density corresponds to a fractional abundance relative to H2 of approximately 1.5 x 10(-11). This value is more than three orders of magnitude less than the abundance of the related molecule HCN in TMC-1. We also report a tentative detection of H2CN in Sgr B2(N). The formation mechanism of H2CN is discussed. Our detection of the H2CN molecule may suggest the existence of a new series of carbon-chain molecules, CH2CnN (n = 0, 1, 2,...).     

Granite subduction: Arc subduction, tectonic erosion and sediment subduction

Continental growth has been episodic, reflecting the episodic nature of mantle dynamics as well as surface dynamics of the Earth, the net result of which is exhibited by the present mantle with two huge reservoirs of TTG rocks, one on the surface continents and the other on the D″ layer on the Core-Mantle Boundary (CMB). During the early half of the Earth history, the felsic continental crust on the surface which formed in an intra-oceanic environment has mostly been subducted into the deep mantle, except in the rare case of parallel arc collision. The growth history of continental crust shows that with its simultaneous formation, a considerable amount must have also been subducted. Such ongoing subduction processes can be seen in the western Pacific region, through tectonic erosion, arc subduction, and sediment-trapped subduction.     

Changes of environments and human activity at the Sannai-Maruyama ruins in Japan during the mid-Holocene Hypsithermal climatic interval

Sannai-Maruyama is one of the most famous and best-researched mid-Holocene (mid-Jomon) archaeological sites in Japan, because of a large community of people for a long period. Archaeological studies have shown that the Jomon people inhabi1ted the Sannai-Maruyama site from 5.9 to 4.2 ± 0.1 cal kyr BP However, a continuous record of the terrestrial and marine environments around the site has not been available. Core KT05-7 PC-02, was recovered from Mutsu Bay, only 20 km from the site, for the reconstruction of high-resolution time series of environmental records, including sea surface temperature (SST). C₃₇ alkenone SSTs showed clear fluctuations, with four periods of high (8.4–7.9, 7.0–5.9, 5.1–4.1, and 2.3–1.4 cal kyr BP) and four of low (?8.4, 7.9–7.0, 5.9–5.1, and 4.1–2.3 cal kyr BP) SST. Thus, each SST cycle lasted 1.0–2.0 kyr, and the amplitude of fluctuation was about 1.5–2.0 °C. Total organic carbon (TOC) and C₃₇ alkenone contents, and the TOC/total nitrogen ratio indicate that marine biogenic production was low before 7.0 cal kyr BP, but was clearly increased between 5.9 and 4.0 cal kyr BP, because of stronger vertical mixing. During the period when the community at the site prospered (between 5.9 and 4.2 ± 0.1 cal kyr BP), the terrestrial climate was relatively warm. The high relative abundance of pollen of both Castanea and Quercus subgen. Cyclobalanopsis supports the interpretation that the local climate was optimal for human habitation. Between 5.9 and 5.1 cal kyr BP, in spite of warm terrestrial climates, the C₃₇ alkenone SST was low; this apparent discrepancy may be attributed to the water column structure in the Tsugaru Strait, which differed from the modern condition. The evidence suggests that at about 5.9 cal kyr B.P, high productivity of marine resources such as fish and shellfish and a warm terrestrial climate led to the establishment of a human community at the Sannai-Maruyama site. Then, at about 4.1 ± 0.1 cal kyr BP, abrupt marine and terrestrial cooling, indicated by a decrease of about 2 °C in the C₃₇ alkenone SST and an increase in the pollen of taxa of cooler climates, led to a reduced terrestrial food supply, causing the people to abandon the site. The timing of the abandonment is consistent with the timing (around 4.0–4.3 cal kyr BP) of the decline of civilizations in north Mesopotamia and along the Yangtze River. These findings suggest that a temperature rise of ～2 °C in this century as a result of global warming could have a great impact on the human community and especially on agriculture, despite the advances of contemporary society.