High resolution spectral features of a series of aromatic hydrocarbons and BrO: Potential interferences in atmospheric OH-measurements

Naphthalene (C₁₀H₈), several other hydrocarbons, mostly derivates of naphthalene, and bromine oxide (BrO) were analyzed for narrow band (0.01 nm) absorption lines in the wavelength range between 307.7 and 308.3 nm to study their potential impact on OH radical measurements by differential absorption spectroscopy.Only naphthalene showed narrow band absorption lines in this wavelength region. From nine naphthalene lines the differential absorption cross-section was determined.The strongest naphthalene line at 308.002 nm is close to the Q ₁(2) OH line, but about a factor of 200 weaker (=(65.2±15.3)×10^-20 cm²/molec). The corresponding detection limit for naphthalene is about 15 ppt. We re-evaluated some spectra of our OH measurement campaign in July 1987 with respect to naphthalene and obtained an upper limit of 30 ppt for its concentration.BrO was recorded in the larger wavelength interval between 307.7 and 308.7 nm. Structured absorptions were only observed at wavelengths above 308.2 nm and no significant structures were found in the vicinity of the Q ₁(2) and Q ₁(3) OH lines.     

Relative-rate study of the gas-phase reaction of hydroxy radicals with difunctional organic nitrates at 298 K and atmospheric pressure

Rate coefficients for the reactions of difunctional nitrates with atmospherically important OH radicals are not currently available in the literature. This study represents the first determination of rate coefficients for a number of C(3) and C(4) carbonyl nitrates and dinitrates with OH radicals in a 38 l glass reaction chamber at 1000 mbar total pressure of synthetic air by 298±2 K using a relative kinetic technique.The following rate coefficients (in units of 10^-12 cm³ molecule^-1 s^-1) were obtained: 1,2-propandiol dinitrate, <0.31; 1,2-butandiol dinitrate, 1.70±0.32; 2,3-butandiol dinitrate, 1.07±0.26; -nitrooxyacetone, <0.43; 1-nitrooxy-2-butanone, 0.91±0.16; 3-nitrooxy-2-butanone, 1.27±0.14; 1,4-dinitrooxy-2-butene, 15.10±1.45; 3,4-dinitrooxy-1-butene, 10.10±0.50.The possible importance of reaction of OH as an atmospheric sink for the compounds compared to other loss processes is considered.     

Boron isotopic fractionation in laboratory inorganic carbonate precipitation: evidence for the incorporation of B(OH)<Subscript>3</Subscript> into carbonate

A laboratory inorganic carbonate precipitation experiment at high pH of 8.96 to 9.34 was conducted, and the boron isotopic fractionations of the precipitated carbonate were measured. The data show that boron isotopic fractionation factors (α_carb-3) between carbonate and B(OH)₃ in seawater range 0.937 and 0.965, with an average value of 0.953. Our results together with those reported by Sanyal and collaborators show that the α_carb-3 values between carbonate and B(OH)₃ in solution are not constant but are negatively correlated with the pH of seawater. The measured boron isotopic compositions of carbonate precipitation (δ¹¹B_carb) do not exactly lie on the best-fit theoretical δ¹¹B₄-pH curves and neither do they exactly parallel any theoretical δ¹¹B₄-pH curves. Therefore, it is reasonable to argue that a changeable proportion of B(OH)₃ with pH of seawater should also be incorporated into carbonate except for the dominant incorporation of B(OH)₄ ⁻ in carbonate. Hence, in the reconstruction of the paleo-pH of seawater from boron isotopes in marine biogenic carbonates, the use of theoretical boron isotopic fractionation factor (α₄₋₃) between B(OH)₄ ⁻ and B(OH)₃ is not suitable. Instead, an empirical equation should be established. Supported by National Natural Science Foundation of China (Nos. 40573013 and 40776071), State Key Laboratory of Loess and Quaternary Geology, Institute of Earth Environment, Chinese Academy of Sciences (Grant No SKLLQG0502) and State Key Laboratory of Environmental Geochemistry, Institute of Geochemistry, Chinese Academy of Sciences     

On a Property of Gravitational Systems

If one attributes to each component i of a gravitational system a dimensionless parameter ψ _i equal to the ratio of its relative mass (with respect to the mass of the system) to its relative position (with respect to a generally defined radius) and sums up the ψ _i values of all components outside the central core, one obtains a mass distribution index Σψ of the order of unity irrespective of the size or the type of the system. In the case of spiral galaxies (and probable other galactic systems) this property applies not only to the whole galaxy, but also to the matter inside any radius larger than the core radius. The mass distribution index in these systems has a maximum Σψ_* at a certain radius r _*, which strongly correlates with the surface brightness at r _* in galaxies with similar mass to light ratio. The gravitational acceleration of all galaxies at r _* divided by (Σψ_*)² is constant and approximately equal to MOND acceleration parameter. Also, at this radius all galaxies have a surface temperature of the order of the temperature of the cosmic microwave background radiation. This revised version was published online in July 2006 with corrections to the Cover Date.     

Megamasers: Molecular Diagnostics of the Nuclear Ism

Molecular emissions are powerful tracers of intense heating and star-formation processes in galactic nuclei. In this paper we consider the characteristics of molecular Megamaser emission among the population of (Ultra-) Luminous Infrared Galaxies that are powered by intense star-formation or accretion onto a massive compact object. In addition, we consider the systematic behavior of the line emission of high-density tracer molecules. An evolutionary scenario is presented for ULIRGs that may explain the molecular line ratios observed in the population of FIR galaxies.     

富有机物流体中一些重要Ge同位素的平衡分馏参数

锗（Ge）同位素在地球化学领域有着潜在的应用意义,但是Ge同位素平衡分馏参数的缺乏,严重制约了其在相关研究中的应用。本研究提供了富有机物流体中物种Ge（OH）4、GeO（OH）3^-以及Ge的一些亲有机质络合物（Ge与邻苯二酚、柠檬酸以及草酸配合形成的络合物）之间的Ge同位素平衡分馏参数。用基于Urey模型（或称Bigeleisen-Mayer公式）理论,结合量子化学计算的方法,在B3LYP／6-311＋G（d,p）理论水平下计算了这些Ge同位素平衡分馏系数,其中,溶液效应用精确的“水滴法”来处理。预测这些基本分馏参数的误差约为±0．2‰。纯水溶液中,△Ge（OH）4-GeO（OH）3^-约为0．6‰,海水中稍小,约为0．3‰;而△Ge（OH）4-Ge-邻苯二酚、△Ge（OH）4-Ge-草酸、△Ge（OH）4-Ge-柠檬酸（c）和△Ge（OH）4-Ge柠檬酸（d）非常大,分别约为4．4‰、3．5‰、3．8‰和3．9‰。这些大的分馏或许可以用来示踪生物作用参与过程。结果表明,轻的Ge同位素将富集在富有机质的环境,如煤系、黑色页岩及一些缺氧的条件下,因此这些环境可能存在一个轻Ge同位素的“汇”。     

BLO 0716＋714射电和光学快速变化的相关性及其含义

本文讨论ＢＬＯ０７１６＋７１４中观测到的光学和射电快速变化（ＩＤＶ）的相关性及可能的解释。详细的分析表明，这种相关性有三个特点：（１）光学变化和５ＧＨｚ射电变化呈反相关，即光学极大和５ＧＨｚ射电极小相对应，反之亦然；（２）光学变化和射电频谱指数α＿５￣（８．３）的变化相关，具体他说，光学的增强和极大都与射电频谱反转频率向高频的位移有关；（３）光学和射电都有～１天的准周期变化，特别是射电频谱指数α８５·３的变化维持了大约７个准周期。上述相关的光学和射电快速变化可以在相对论喷流的框架下作出解释。作者提出，这类现象可能与激波在磁约束的准周期振荡的相对论喷流中的传播有关。     

Evaluation of the Salicylic Acid—Liquid Phase Scrubbing Technique to Monitor Atmospheric Hydroxyl Radicals

A novel method has been examined for monitoring tropospheric hydroxyl radicals (OH), the most important oxidant in tropospheric chemistry. Aqueous phase salicylic acid reacts with atmospheric OH to produce 2,5-dihydroxy benzoic acid (2,5-DHBA) and other products. High Performance Liquid Chromatography (HPLC) is used to separate the post-reaction solution and the products are quantified using fluorescence detection. Unlike other methods, it has been reported to be inexpensive, portable and relatively simple. Although the sensitivity was sufficient to measure typical daytime OH concentrations of 0.04–0.4 ppt., the method was hindered by numerous interferences. Successive identification and elimination of these still resulted in a signal that was much larger than expected. Tests showed that this was not likely to be due to ozone, HO₂, NOx, H₂O₂, aerosols, light or bacteria. Experimental and numerical studies suggest that the interference could be due to methyl peroxy radicals. The effect of many other components in the atmosphere, both individual and combined, must also be tested before the method can be used reliably in the field. The validity of previous reports of ambient hydroxyl measurements using this technique is therefore brought into question.     

古全球变化与非等时韵律沉积及前寒武纪条带状铁矿建造形成的终止

前寒武纪各种地质记录表明了太古代—元古代早期古全球环境具有显著的陆少洋多和大气富ＣＯ２、贫Ｏ２的特征。ＢＩＦｓ大气－海洋系统中Ｆｅ２＋的氧化是导致铁质发生沉淀的一个重要过程，在前寒武纪早期缺Ｏ２的环境，生物－无氧氧化和日光－紫外线为主的宇宙射线光致氧化作用产生的直接非生物－无氧氧化过程，在前寒武纪早期缺Ｏ２环境对Ｆｅ２＋的氧化可能起着重要的和主导的作用。ＢＩＦｓ条带状矿石的宏、微观ＳｉＯ２或Ｆｅ２Ｏ３／Ｆｅ３Ｏ４单层厚度非等厚性表征了硅、铁供给非等量性与交替淀积非等时性的韵律堆积。文章提出了一种与地球自转速率有关的日长年际变化（古ＥＬＮｉｎｏ事件）－硅铁临界饱和浓度模式，从统一的地球动力学条件和不同类型ＢＩＦｓ的成因联系解析了这种韵律堆积的机制。元古代早—中期大气－海洋系统发生了Ｏ２增多和ＣＯ２减少的古全球变化，导致了２．２～１．８Ｇａ之间大气圈平流层古臭氧层的形成。古臭氧层大幅度消减日光－紫外线对地球表面的强烈辐射，不仅使全球性由日光－紫外线光致氧化作用直接产生的Ｆｅ２＋非生物－缺氧氧化过程消失，而且也保证了生命演化的延续和生物进入多样性繁衍。与其伴随的全球性巨厚碳酸盐建造，导致了上壳岩下伏的地球早期富铁?