Combined experimental and theoretical studies on methane photolysis at 121.6 and 248 nm—implications on a program of laboratory simulations of Titan’s atmosphere

Methane is, together with N₂, the main precursor of Titan’s atmospheric chemistry. In our laboratory, we are currently developing a program of laboratory simulations of Titan’s atmosphere, where methane is intended to be dissociated by multiphotonic photolysis at 248 nm. A preliminary study has shown that multiphotonic absorption of methane at 248 nm is efficient and leads to the production of hydrocarbons such as C₂H₂ (Romanzin et al., 2008). Yet, at this wavelength, little is known about the branching ratios of the hydrocarbon radicals (CH₃, CH₂ and CH) and their following photochemistry. This paper thus aims at investigating methane photochemistry at 248 nm by comparing the chemical evolution observed after irradiation of CH₄ at 248 and at 121.6 nm (Ly-α). It is indeed important to see if the chemistry is driven the same way at both wavelengths in particular because, on Titan, methane photolysis mainly involves Ly-α photons. An approach combining experiments and theoretical analysis by means of a specifically adapted 0-D model has thus been developed and is presented in this paper. The results obtained clearly indicate that the chemistry is different depending on the wavelength. They also suggest that at 248 nm, methane dissociation is in competition with ionisation, which could occur through a three-photon absorption process. As a consequence, 248 nm photolysis appears to be unsuitable to study methane neutral photochemistry alone. The implications of this result on our laboratory simulation program and new experimental developments are discussed. Additional information on methane photochemistry at 121.6 nm are also obtained.     

1624年“扬州地震”震中的新认识

公元1624年2月10日,即明代天启三年12月22日,在现今江苏省范围内发生了一次破坏性地震。在历次出版的地震目录中,扬州被确定为本次地震的震中,其主要依据为“扬州倒卸城垣三百八十余垛、城铺二十余处”的历史记述。《地震亘江南北疏》的发现为本次地震的研究提供了新的资料。本文分析已有资料的可靠性;选择相对可靠的历史资料划定Ⅵ度等烈度线;采用新划定的Ⅵ度等烈度线,按历史地震影响烈度的衰减关系确定本次地震的震级为6 1/4级;综合Ⅵ度等烈度线范围内的地震地质条件以及历史地震资料中人的感受、地表变形和各地地声方向记录,综合确定了震中位置大致在32.2°N、119.5°E,与1913年4月3日镇江5 1/2级地震(参考地名“江苏镇江”)震中相距不远。此外,本文还描述了本次地震的地震序列。     

矿物表面基团与表面作用

矿物的表面或界面过程存在于一切地质过程中,并在材料和环境科学领域得到广泛应用。矿物的表面结构、表面基团与表面作用之间存在着一定的内在联系,矿物结构的多样性决定了表面基团类型的多种性和表面作用的多样性。本文较系统地介绍了矿物表面功能基、表面配位反应、表面配合反应、表面氧化还原反应、表面异位催化反应和表面离子交换反应的类型及作用机制。     

Copper Speciation in a Collection of Geochemical Reference Materials Using Sequential Extraction and Evaluation of the Validity Using XANES Spectroscopy

Copper speciation in a collection of Japanese geochemical reference materials (JSO‐1, JLk‐1, JSd‐1, ‐2, ‐3 and ‐4, JMs‐1 and JMs‐2) was achieved by sequential extraction and characterised using X‐ray absorption near‐edge structure spectroscopy. In the first step of the extraction, referred to as the acid fraction, between 1% and 20% total Cu within the reference materials was extracted. Such a result is typically accounted for by absorption of Cu onto clay minerals. However, the presence of Cu sulfate (an oxidation product of chalcopyrite) was observed in some of the stream sediments affected by mining activity (JSd‐2 and JSd‐3) instead. Copper was extracted in the reducible fraction (targeting Fe hydroxide and Mn oxide) (2–49% total Cu). Between 2% and 51% Cu was extracted in the oxidised fraction (targeting sulfides and organic matter). X‐ray absorption near‐edge structure spectroscopy clarified that the reducible fraction consisted of Cu bound to Fe hydroxide, whereas the oxidised fraction was a mixture of Cu bound to humic acid (HA) and Cu sulfide. In the oxidisable fraction, chalcopyrite was the predominant species identified in JSd‐2, and Cu bound to HA was the major species identified in JSO‐1 (a soil sample).     

Titan's atmospheric engine: an overview

Heating occurs in Titan's stratosphere from the absorption of incident solar radiation by methane and aerosols. About 10% of the incident sunlight reaches Titan's surface and causes heating there. Thermal radiation redistributes heat within the atmosphere and cools to space. The resulting vertical temperature profile is stable against convection and a state of radiative equilibrium is established. Equating theoretical and observed temperature profiles enables an empirical determination of the vertical distribution of thermal opacity. A uniformly mixed aerosol is responsible for most of the opacity in the stratosphere, whereas collision-induced absorption of gases is the main contributor in the troposphere. Occasional clouds are observed in the troposphere in spite of the large degrees of methane supersaturation found there. Photochemistry converts CH₄ and N₂ into more complex hydrocarbons and nitriles in the stratosphere and above. Thin ice clouds of trace organics are formed in the winter and early spring polar regions of the lower stratosphere. Precipitating ice particles serve as condensation sites for supersaturated methane vapor in the troposphere below, resulting in lowered methane degrees of supersaturation in the polar regions. Latitudinal variations of stratospheric temperature are seasonal, and lag instantaneous response to solar irradiation by about one season for two reasons: (1) an actual instantaneous thermal response to a latitudinal distribution of absorbing gases, themselves out of phase with the sun by about one season, and (2) a sluggish dynamical response of the stratosphere to the latitudinal transport of angular momentum, induced by radiative heating and cooling. Mean vertical abundances of stratospheric organics and aerosols are determined primarily by atmospheric chemistry and condensation, whereas latitudinal distributions are more influenced by meridional circulations. In addition to preferential scavenging by precipitating ice particles from above, the polar depletion of supersaturated methane results from periodic scavenging by short-lived tropospheric clouds, coupled with the steady poleward march of the continuously drying atmosphere due to meridional transport.     

Titan's surface at 2.2-cm wavelength imaged by the Cassini RADAR radiometer: Calibration and first results

The first comprehensive calibration and mapping of the thermal microwave emission from Titan's surface is reported based on radiometric data obtained at 2.2-cm wavelength by the passive radiometer included in the Cassini Radar instrument. The data reported were accumulated from 69 separate observational segments in Titan passes from Ta (October 2004) through T30 (May 2007) and include emission from 94% of Titan's surface. They are diverse in the key observing parameters of emission angle, polarization, and spatial resolution, and their reduction into calibrated global mosaic maps involved several steps. Analysis of the polarimetry obtained at low to moderate resolution (50+ km) enabled integration of the radiometry into a single mosaic of the equivalent brightness temperature at normal incidence with a relative precision of about 1 K. The Huygens probe measurement of Titan's surface temperature and radiometry obtained on Titan's dune fields allowed us to infer an absolute calibration estimated to be accurate to a level approaching 1 K. The results provide evidence for a surface that is complex and varied on large scales. The radiometry primarily constrains physical properties of the surface, where we see strong evidence for subsurface (volume) scattering as a dominant mechanism that determines the emissivity, with the possibility of a fluffy or graded-density surface layer in many regions. The results are consistent with, but not necessarily definitive of a surface composition resulting from the slow deposition and processing of organic compounds from the atmosphere.     

Determining a tilt in Titan’s north-south albedo asymmetry from Cassini images

Analysis of Titan’s hemispheric brightness asymmetry from mapped Cassini images reveals an axis of symmetry that is tilted with respect to the rotational axis of the solid body. Twenty images taken from 2004 through 2007 show a mean axial offset of 3.8 ± 0.9° relative to the solid body’s pole, directed 79 ± 24° to the west of the sub-solar longitude. These values are consistent with recent measurements of an implied atmospheric spin axis determined from isothermal mapping by [Achterberg, R.K., Conrath, B.J., Gierasch, P.J., Flasar, F.M., Nixon, C.A., 2008. Icarus 197, 549-555].     

Element Abundances of China‘s Continental Crust and Its Sedimentary Layer and Upper Continental Crust

China’s continental crust (CCC) has an average thickness of 47km, with the upper continental crust (CUCC) being 31 km and the sedimentary layer(CSL) 5 km in thickness. The CCC, CUCC and CSL measure 12.437 × 10⁻¹⁷, 8.005 × 10⁻¹⁷ and 1.146 × 10¹⁷ metric tons in mass, respectively. The mass ratio of the upper continental crust to the lower one is 1.8:1. The element abundances were calculated for the CCC, CUCC and CSL respectively in terms of the chemical compositions of 2246 samples of various types and some complementary trace element data. The total abundance of 13 major elements accounts for 99.6% of the CCC mass while the other minor elements only account for 0.4%. REE characteristics, the abundance ratios of element pairs and the amounts of ore-forming elements are also discussed in the present paper.     

Palynofacies classification of submarine fan depositional environments: Outcrop examples from the Marnoso-Arenacea Formation,Italy

Basin floor fans contain some of the largest deep-water hydrocarbon accumulations discovered, however they also demonstrate extremely complex stratigraphic architecture, understanding of which is crucial for maximum recovery. Here we develop a new method, based upon palynofacies analysis, for the distinction of the different depositional environments that are commonly associated with basin floor fans. Previous studies and our sedimentological analysis allow good confidence in the discrimination of the different depositional environments of the outcropping Marnoso-Arenacea Formation fan system. One hundred and thirty-five samples were collected from mudstones in conjunction with sedimentary logging of 871 m of outcrops. Six lithofacies associations are described and interpreted to represent lobe axis, lobe fringe, fan fringe, contained interlobe, basin plain, and starved high depositional sub-environments. Palynofacies of these elements demonstrate turbidites to be rich in terrestrial organic matter, with sixteen categories of matter recognised. The abundances and proportions of particles varies between sub-environments, with lobe axis deposits containing the largest, densest particles, with a transition to ever smaller and lighter particles moving toward the basin plain. Fuzzy C-means statistical analysis was used to explore this trend. Distribution of organic matter is not random, but is dominated by hydrodynamic sorting and sequential fall-out of particles as turbidity currents passed across the basin. This allows a palynofacies classification scheme to be constructed to assist the identification of depositional environments of submarine fans, which may be combined with subsurface data to assist reservoir characterisation.