Prebiotic organic synthesis in early Earth and Mars atmospheres: Laboratory experiments with quantitative determination of products formed in a cold plasma flow reactor

The goal of this study was to explore prebiotic chemistry in a range of plausible early Earth and Mars atmospheres. To achieve this laboratory continuous flow plasma irradiation experiments were performed on N₂/H₂/CO/CO₂ gas mixtures chosen to represent mildly reducing early Earth and Mars atmospheres derived from a secondary volcanic outgassing of volatiles in chemical equilibrium with magmas near present day oxidation state. Under mildly reducing conditions (91.79% N₂, 5.89% H₂, 2.21% CO, and 0.11% CO₂), simple nitriles are produced in the gas phase with yield (G in molecules per 100 eV), for the key prebiotic marker molecule HCN at G∼1×¹⁰⁻³ (0.1 nmol J⁻¹). In this atmosphere localized HCN concentrations possibly could approach the 10⁻² M needed for HCN oligomerization. Yields under mildly oxidizing conditions (45.5% N₂, 0.1% H₂, 27.2% CO, 27.2% CO₂) are significantly less as expected, with HCN at G∼3×¹⁰⁻⁵ (). Yields in a Triton atmosphere which can be plausibly extrapolated to represent what might be produced in trace CH₄ conditions (99.9% N₂, 0.1% CH₄) are significant with HCN at G∼1×¹⁰⁻² (1 nmol J⁻¹) and tholins produced. Recently higher methane abundance atmospheres have been examined for their greenhouse warming potential, and higher abundance hydrogen atmospheres have been proposed based on a low early Earth exosphere temperature. A reducing (64.04% N₂, 28.8% H₂, 3.60% CO₂, and 3.56% CH₄), representing a high CH₄ and H₂ abundance early Earth atmosphere had HCN yields of G∼5×¹⁰⁻³ (0.5 nmol J⁻¹). Tholins generated in high methane hydrogen gas mixtures is much less than in a similar mixture without hydrogen. The same mixture with the oxidizing component CO₂ removed (66.43% N₂, 29.88% H₂, 0% CO₂, and 3.69% CH₄) had HCN yields of G∼1×¹⁰⁻³ (0.1 nmol J⁻¹) but more significant tholin yields.     

安徽庐枞盆地罗河铁矿水岩反应化学动力学实验

选择罗河铁矿含矿围岩云辉粗安岩为研究对象,使用叠层反应器,进行了在22MPa、100～400℃的条件下水岩相互作用地球化学动力学实验,系统地研究了不同温度、不同流速下元素的溶解情况并计算出其溶解速率。实验发现,元素在溶液中的浓度随着流速、温度的变化而变化。大多数元素在溶液中的浓度随着温度的升高而增加,一般在300～400℃时浓度达到最大。溶解速率随温度的不断升高而发生变化,各种元素达到最大溶解速率的温度大多在200～400℃之间。但是各个元素的最大溶解速率对应的温度并不相同。流体的流速影响着元素的溶解速率,元素的最大溶解速率并不都是在最大流速时产生的。     

A photochemical model of Titan's atmosphere and ionosphere

A global-mean model of coupled neutral and ion chemistry on Titan has been developed. Unlike the previous coupled models, the model involves ambipolar diffusion and escape of ions, hydrodynamic escape of light species, and calculates the H₂ and CO densities near the surface that were assigned in some previous models. We tried to reduce the numbers of species and reactions in the model and remove all species and reactions that weakly affect the observed species. Hydrocarbon chemistry is extended to C₁₂H₁₀ for neutrals and C₁₀H⁺₁₁ for ions but does not include PAHs. The model involves 415 reactions of 83 neutrals and 33 ions, effects of magnetospheric electrons, protons, and cosmic rays. UV absorption by Titan's haze was calculated using the Huygens observations and a code for the aggregate particles. Hydrocarbon, nitrile, and ion chemistries are strongly coupled on Titan, and attempt to calculate them separately (e.g., in models of ionospheric composition) may result in significant error. The model densities of various species are typically in good agreement with the observations except vertical profiles in the stratosphere that are steeper than the CIRS limb data. (A model with eddy diffusion that facilitates fitting to the CIRS limb data is considered as well.) The CO densities are supported by the O⁺ flux from Saturn's magnetosphere. The ionosphere includes a peak at 80 km formed by the cosmic rays, steplike layers at 500-700 and 700-900 km and a peak at 1060 km (SZA = 60°). Nighttime densities of major ions agree with the INMS data. Ion chemistry dominates in the production of bicyclic aromatic hydrocarbons above 600 km. The model estimates of heavy positive and negative ions are in reasonable agreement with the Cassini results. The major haze production is in the reactions C₆H + C₄H₂, C₃N + C₄H₂, and condensation of hydrocarbons below 100 km. Overall, precipitation rate of the photochemical products is equal to 4-7 kg cm⁻² Byr⁻¹ (50-90 m Byr⁻¹ while the global-mean depth of the organic sediments is ∼3 m). Escape rates of methane and hydrogen are 2.9 and 1.4 kg cm⁻² Byr⁻¹, respectively. The model does not support the low C/N ratio observed by the Huygens ACP in Titan's haze.     

Metastable methane clathrate particles as a source of methane to the martian atmosphere

The observations of methane made by the PFS instrument onboard Mars Express exhibit a definite correlation between methane mixing ratio, water vapor mixing ratio, and cloud optical depth. The recent data obtained from ground-based telescopes seem to confirm the correlation between methane and water vapor. In order to explain this correlation, we suggest that the source of gaseous methane is atmospheric, rather than at the solid surface of the planet, and that this source may consist of metastable submicronic particles of methane clathrate hydrate continuously released to the atmosphere from one or several clathrate layers at depth, according to the phenomenon of “anomalous preservation” evidenced in the laboratory. These particles, lifted up to middle atmospheric levels due to their small size, and therefore filling the whole atmosphere, serve as condensation nuclei for water vapor. The observed correlation between methane and water vapor mixing ratios could be the signature of the decomposition of the clathrate crystals by condensation-sublimation processes related to cloud activity. Under the effect of water condensation on crystal walls, metastability could be broken and particles be eroded, resulting in a subsequent irreversible release of methane to the gas phase. Using PFS data, and according to our hypothesis, the lifetime of gaseous methane is estimated to be smaller than an upper limit of 6 ± 3 months, much smaller than the lifetime of 300 yr calculated from atmospheric chemical models. The reason why methane has a short lifetime might be the occurrence of heterogeneous chemical decomposition of methane in the subsurface, where it is known since Viking biology experiments that oxidants efficiently decompose organic matter. If true, it is shown by using existing models of H₂O₂ penetration in the regolith that methane could prevent H₂O₂ from penetrating in the subsurface, and further oxidizing the soil, at depths larger than a few millimeters. The present source of methane clathrate, acting over the last few hundred thousand or million years, could have given rise to the thin CO₂-ice layer covering the permanent water ice south polar cap. The hypothesis proposed in this paper requires, to be validated, a number of laboratory experiments studying the stability of methane clathrates in martian atmospheric conditions, and the kinetics and amplitude of clathrate particle erosion in presence of condensing water vapor. Detailed future observations of methane, and associated modeling, will allow to more accurately quantify the production rate of methane clathrate, its temporal variability at seasonal scale, and possibly to locate the source(s) of clathrates at the surface.     

Coexisting High- and Low-Calcium Melts Identified by Mineral and Melt Inclusion Studies of a Subduction-Influenced Syn-collisional Magma from South Sulawesi, Indonesia

Mineral and melt inclusions in olivines from the most Mg-richmagma from the southern West Sulawesi Volcanic Province indicatethat two distinct melts contributed to its petrogenesis. Thecontribution that dominates the whole-rock composition comesfrom a liquid with high CaO (up to 16 wt %) and low Al₂O₃ contents(CaO/Al₂O₃ up to 1), in equilibrium with spinel, olivine (Fo_85–91;CaO 0·35–0·5 wt %; NiO 0·2–0·30wt %) and clinopyroxene. The other component is richer in SiO₂(>50 wt %) and Al₂O₃ (19–21 wt %), but contains significantlyless CaO (<4 wt %); it is in equilibrium with Cr-rich spinelwith a low TiO₂ content, olivine with low CaO and high NiO content(Fo_90–94; CaO 0·05–0·20 wt %; NiO0·35–0·5 wt %), and orthopyroxene. Boththe high- and low-CaO melts are potassium-rich (>3 wt % K₂O).The high-CaO melt has a normalized trace element pattern thatis typical for subduction-related volcanic rocks, with negativeTa–Nb and Ti anomalies, positive K, Pb and Sr anomalies,and a relatively flat heavy rare earth element (HREE) pattern.The low-CaO melt shows Y and HREE depletion (Gd_n/Yb_n 41), butits trace element pattern resembles that of the whole-rock andhigh-CaO melt in other respects, suggesting only small distinctionsin source areas between the two components. We propose thatthe depth of melting and the dominance of H₂O- or CO₂-bearingfluids were the main controls on generating these contrastingmagmas in a syn-collisional environment. The composition ofthe low-CaO magma does not have any obvious rock equivalent,and it is possible that this type of magma does not easily reachthe Earth's surface without the assistance of a water-poor carriermagma. KEY WORDS: melt inclusions; mineral chemistry; olivine; syn-collisional magmatism; ankaramites; low-Ca magma     

On the Nonlinear Response of Lower Stratospheric Ozone to External Forces---The Inclusion of BrOx and Radiation Processes

In this paper the bromine family and radiative effects are considered in an updated box model under the framework of ozone-temperature feedback,in order to further analyze the possible behavior of atmospheric ozone in the lower mid-latitude stratosphere.Results show that this updated photochemical system can present several different solutions,within a certain domain of parameters,with fixed-point and periodic states appearing in turn.The temperature feedback effect introduced in this box model has not changed the topology of the ozone system.This result presents nonlinear characteristics of the ozone system,and possible trends in the stratospheric atmosphere between complex chemistry and radiation processes.     

几个重要Ge同位素平衡分馏参数的理论预测

本研究基于Urey模型(或称Bigeleisen和Mayer公式),结合量子化学计算的方法,在B3LYP/6-311+G(d, p)理论水平下,计算了Ge在类似石英(包括蛋白石)、钠长石、钾长石、橄榄石结构以及水溶液(包括海水)中Ge(OH)4和GeO(OH)3-之间的Ge同位素平衡分馏系数.其中,溶液效应用"水滴法"处理,矿物结构用簇合物方法模拟.结果显示这些基本分馏参数的精度约±0.3‰;类石英(或蛋白石)结构最可能富集重Ge同位素,在25 ℃,几个Ge同位素分馏系数分别约为:Δ石英-Ge(OH)4=0.9‰、ΔGe(OH)4-GeO(OH)3-=0.3‰(海水中)、Δ石英-钠长石=0.6‰、Δ石英-钾长石=0.4‰、Δ橄榄石-Ge(OH)4=-1.2‰.类石英与类橄榄石结构之间存在较大的分馏,Δ石英-橄榄石=2.1‰.这些具有重要地质意义的基本分馏参数可以为探索未知的Ge同位素地球化学应用领域打下基础.此外,本文还用所得的分馏参数定量地解释了Siebert等(2006)和Rouxel等(2006)的一些工作,说明了这些参数的可靠性及其在地学中的重要应用意义.     

云南耿马孟定盆地高砷水成因及其危害

孟定盆地出现水砷异常由三类因素共同作用引发：汇水区砷背景高,有色金属采选冶过程排放含砷重金属导致砷二次污染,盆地地球化学环境利于砷积累。形成环境具一定的代表性,区别于我国已发生的饮水型盆地砷病病区。     

遵义后槽铝土矿的矿物学特征

现已载入<中国矿床发现史·综合卷>内的贵州遵叉后槽铝土矿,是遵义铝土矿带中矿床规模较大、矿石质量较佳和露采条件良好的主要矿区之一.文章应用矿石薄片、重砂鉴定和扫描电镜、电子探针等多种测试成果,论述了铝土矿矿石的矿物成分、矿物学特征,包括其结晶形态、粒度大小、物理光学性质和产出特征等,同时阐明了主要矿物在不同类型矿石中的含量及其组合特征.进而研究表明,不同类型矿石的矿物组合有所差异,其中一水硬铝石的含量不同,其形态各异,这在一定程度上反映了铝土矿的形成条件.     

AAS has been accepted for Coverage by the Science Citation Index in 2009

In May 2008, ScienceWatch.com named Advances in Atmospheric Sciences a Rising Star among Geosciences journals. According to Essential Science IndicatorsSM from Thomson Reuters, the journal＇s cur-rent citation record includes 764 papers cited a total of 1,658 times between January 1, 1998 and February 29 2008.