Rate constants for the reactions of the NO3 radical with HCOOH/HCOO− and CH3COOH/CH3COO− in aqueous solution between 278 and 328 K

The kinetics of the aqueous phase reactions of NO₃ radicals with HCOOH/HCOO^– and CH₃COOH/CH₃COO^– have been investigated using a laser photolysis/long-path laser absorption technique. NO₃ was produced via excimer laser photolysis of peroxodisulfate anions (S₂O ₈ ^2– ) at 351 nm followed by the reactions of sulfate radicals (SO ₄ ^– ) with excess nitrate. The time-resolved detection of NO₃ was achieved by long-path laser absorption at 632.8 nm. For the reactions of NO₃ with formic acid (1) and formate (2) rate coefficients ofk ₁=(3.3±1.0)×10⁵ l mol^–1 s^–1 andk ₂=(5.0±0.4)×10⁷ l mol^–1 s^–1 were found atT=298 K andI=0.19 mol/l. The following Arrhenius expressions were derived:k ₁(T)=(3.4±0.3)×10¹⁰ exp[–(3400±600)/T] l mol^–1 s^–1 andk ₂(T)=(8.2±0.8)×10¹⁰ exp[–(2200±700)/T] l mol^–1 s^–1. The rate coefficients for the reactions of NO₃ with acetic acid (3) and acetate (4) atT=298 K andI=0.19 mol/l were determined as:k ₃=(1.3±0.3)×10⁴ l mol^–1 s^–1 andk ₄=(2.3±0.4)×10⁶ l mol^–1 s^–1. The temperature dependences for these reactions are described by:k ₃(T)=(4.9±0.5)×10⁹ exp[–(3800±700)/T] l mol^–1 s^–1 andk ₄(T)=(1.0±0.2)×10¹² exp[–(3800±1200)/T] l mol^–1 s^–1. The differences in reactivity of the anions HCOO^– and CH₃COO^– compared to their corresponding acids HCOOH and CH₃COOH are explained by the higher reactivity of NO₃ in charge transfer processes compared to H atom abstraction. From a comparison of NO₃ reactions with various droplets constituents it is concluded that the reaction of NO₃ with HCOO^– may present a dominant loss reaction of NO₃ in atmospheric droplets.     

Subarcsec 10μm imaging of bipolar flow sources

We have started a program of high-resolution (0.4/pixel) 10m imaging of bipolar outflow sources using the 10m camera CAMIRAS. We present recent results obtained at the Canada France Hawaii Telescope which reveal extended emission or IR companions in several luminous objects. The extended emission we detected probably arises from transiently heated very small grains, while the newly discovered companions could contribute significantly to the outflow activity and extended far-IR emission usually attributed to the main optical source.     

Sub-arcsec 10 μm imaging of β pictoris and other star disk candidates

We have used the ESO 10 m camera, TIMMI, to image with a very high angular resolution (PFoV: 0.3; FWHM:0.9) several main-sequence star disk candidates. Information on the -Pictoris dust disk has been obtained in a region largely inaccessible to previous observations: 0–80 AU, with a resolution of about 5 AU after deconvolution. Another promising target for 10 m imaging, 51 Ophiuchi, appears point-like.based on data collected at the European Southern Observatory (ESO), La Silla, Chile     

The “Zero-order Model” revisited: Paul Schindler's influence on the development of trace metal scavenging models

In 1975 Paul Schindler produced the first oceanic trace metal scavenging model to explicitly include the role of surface chemistry as a control on trace metal water column residence times. The eighteen years that have elapsed since the publication of Schindler's seminal paper have seen the development of a variety of oceanic scavenging models; yet, the fundamental insight of his Zero-order Model remains the benchmark. This paper describes the role of Paul Schindler's work on surface chemistry in providing a framework for the current generation of trace element scavenging models.     

寒武系古流体地球化学特征及其对页岩气保存的指示意义 ——以中扬子地区寒武系页岩气发现井宜地2井为例

保存条件是中扬子地区页岩气富集的关键因素之一，宜地2井是中扬子寒武系页岩气发现井，通过对该井全井段岩芯裂缝古流体的地球化学分析，探讨了寒武系古流体成因和对水井沱组页岩气保存条件的指示意义。结果认为：① 覃家庙组膏岩层之上方解石脉缺少Fe2+、Mn2+，且δ13C和δ18O值较围岩偏负，指示其形成于氧化的环境，石牌组方解石脉δ13C偏负，黄铁矿脉δ34S值与膏盐相似，表明其成因与TSR密切相关；水井沱组脉体δ13C和δ18O与围岩相似，形成于封闭的环境。② 方解石脉包裹体群SO42-、Ca2+、Mg2+含量整体上由覃家庙组向上向下分别递减，钠氯系数以水井沱组最低，整体上向上升高，表明覃家庙组是高盐度卤水的主要来源，水井沱组受外来流体影响弱；包裹体水溶液δD和δ18O也指示娄山关组、石牌组方解石脉成因分别与大气水、TSR相关。③ 古流体地球化学研究表明宜昌地区页岩气保存条件整体较好，页岩气散失的主要通道是垂直裂缝，页岩气保存条件好与膏盐盖层发育、后期构造破坏弱、脉体对裂缝的及时封闭以及白垩系盖层等因素密切相关。     

珠江口盆地西江主洼油气差异分布机制

西江主洼是珠江口盆地一个低勘探程度洼陷，油气差异聚集特征明显，但其机理不清。本文在断陷盆地油气成藏理论指导下，利用研究区地质、地球物理和地球化学等资料，开展了烃源岩、断盖组合、储集体系和运聚模式等方面的研究。结果表明，裂陷期沉降、沉积中心有序迁移，造成主力烃源岩自东向西由文四段迁移至文三段、文一+二段，控制东、西部油气差异分布。恩平组区域性泥岩发育且晚期断裂缺乏，导致油气纵向上更易聚集于下构造层；区域泥岩减薄尖灭或晚期断裂切开盖层的区域，上构造层有一定油气分布。"源-汇"类型从宏观上控制储层优劣，影响下构造层油气富集程度；"仓储"运移是控制上构造层油气规模聚集的主要模式。下构造层古近系应作为重点部署方向，东部围绕文四段、西部围绕文三段、文一+二段烃源岩构成的含油气系统展开；上构造层勘探需关注珠海组，在隆起周边寻找具备"仓储"运移模式的有利区带。     

Channel overflows of the Pōhue Bay flow,Mauna Loa,Hawai'i: examples of the contrast between surface and interior lava

A number of overflows from a large lava channel and tube system on the southwest rift zone of Mauna Loa were studied. Initial overflows were very low viscosity gas-rich phoehoe evidenced by flow-unit aspect ratios and vesicle sizes and contents. Calculated volumetric flow-rates in the channel range between 80 and 890 m³/s, and those of the overflows between 35 and 110 m³/s. After traveling tens to hundreds of meters the tops of these sheet-like overflows were disrupted into a surface composed of clinker and phoehoe fragments. After these 'a' overflows came to rest, lava from the interiors was able to break out on to the surface as phoehoe. The surface structure of a lava flow records the interaction between the differential shear rate (usually correlated with the volumetric flow-rate) and viscosity-induced resistance to flow. However, the interior of a flow, being better insulated, may react differently or record a later set of emplacement conditions. Clefts of toothpaste lava occurring within fields of clinker on proximal-type 'a' flows also record different shear rates during different times of flow emplacement. The interplay between viscosity and shear rate determines the final morphological lava type, and although no specific portion of lava ever makes a transition from 'a' back to phoehoe, parts of a flow can appear to do so.     

Diagenesis of vascular plant organic matter components during burial in lake sediments

Diagenetic changes are difficult to distinguish from variations in sources of organic matter to sediments. Organic geochemical comparisons of samples of wood, bark, and needles from a white spruce (Picea glauca) living today and one buried for 10,000 years in lake sediments have been used to identify the effects of diagenesis on vascular plant matter. Important biogeochemical changes are evident in the aged spruce components, even though the cellular structures of the samples are well preserved. Concentrations of total fatty acids dramatically diminish; unsaturated and shorter chainlength components are preferentially lost from the molecular distributions. Concentrations of total alcohols are similar in the modern and 10,000-year-old wood and bark but markedly lowered in the aged needles. Hydrocarbon concentrations and distributions show little diagenetic change in the 10,000-year-old plant materials. Cellulose components in the wood decrease relative to lignin components, although both types of materials remain in high concentration in comparison to other organic components. Aromatization of abietic acid proceeds more rapidly in buried spruce wood than in bark; retene is the dominant polyaromatic hydrocarbon in the aged wood. In contrast to the variety of changes evident in molecular compositions, neither ¹³C values nor C/N ratios differ significantly in the bulk organic matter of modern and aged spruce components.     

Geochronology and geochemistry of eclogites from the Mariánské Lázně Complex,Czech Republic: Implications for Variscan orogenesis

The Mariánské Lázn complex (MLC) is located in the Bohemian Massif along the north-western margin of the Teplá-Barrandian microplate and consists of metagabbro, amphibolite and eclogite, with subordinate amounts of serpentinite, felsic gneiss and calcsilicate rocks. The MLC is interpreted as a metaophiolite complex that marks the suture zone between the Saxothuringian rocks to the north-west and the Teplá-Barrandian microplate to the south-east. Sm-Nd geochronology of garnet-omphacite pairs from two eclogite samples yields ages of 377±7, and 367±4 Ma. Samples of eclogite and amphibolite do not define a whole rock Sm-Nd isochron, even though there is a large range in Sm/Nd ratio, implying that the suite of samples may not be cogenetic. Eclogites do not have correlated _Nd values and initial ⁸⁷Sr/⁸⁶Sr ratios. Five of the eight eclogite samples have high _Nd values (+10.2 to +7.1) consistent with derivation from a MORB-like source, but variable ⁸⁷Sr/⁸⁶Sr ratios (0.7033 to 0.7059) which probably reflect hydrothermal seawater alteration. Three other eclogite samples have lower _Nd values (+ 5.4 to –0.8) and widely variable ⁸⁷Sr/⁸⁶Sr ratios (0.7033 to 0.7096). Such low _Nd values are inconsistent with derivation from a MORB, source and may reflect a subduction or oceanic island basalt component in their source. The MLC is an important petrotectonic element in the Bohemian Massif, providing evidence for Cambro-Ordovician formation of oceanic crust and interaction with seawater, Late Devonian (Frasnian-Famennian) high- and medium-pressure metamorphism related to closure of a Saxothuringian ocean basin, Early Carboniferous (Viséan) thrusting of the Teplá terrane over Saxothuringian rocks and Late Viséan extension.     

Comparison between a radiative wind model for be stars and high angular resolution data from the GI2T interferometer

I present theoretical line profiles and intensity maps from an axi-symmetric radiative wind model from a rapidly rotating Be star. The introduction of a viscosity parameter in the latitude-dependent hydrodynamic code enables us to consider the effects of the viscous force in the azimuthal component of momentum equations (Araújo et al. 1994). Both velocity field and density law derived from the hydrodynamic equations have been used for solving the statistical equilibrium equations. By adopting the Sobolev approximation, we could easily obtain a good estimate of both electronic density and hydrogen level populations throughout the envelope. The numerical calculation was performed for parameters characterisic of the Be star Cassiopeiae.