Hydroxyl Radical Concentrations Estimated from Measurements of Trichloroethylene during the EASE/ACSOE Campaign at Mace Head, Ireland during July 1996

During the EASE/OXICOA campaign of the NERC ACSOE programme, trichloroethylene and a wide range of man-made halocarbons and radiatively-active trace gases were monitored with high precision and high frequency throughout July 1996 at Mace Head on the Atlantic Ocean coast of Ireland. Trichloroethylene concentrations in concert with many other trace gases became elevated as regionally-polluted and photochemically-aged air masses reached Mace Head. However, as the anticyclonic air masses retreated during 19 and 20 July, trace gas concentrations remained elevated for a significant period. During this 2–4 day period, trichloroethylene concentrations decayed significantly, though the concentrations of the other more chemically-inert trace gases did not. A detailed interpretation of this behaviour using a Lagrangian dispersion model has allowed the estimation of average and peak OH radical concentrations of 3 and 9×10⁶ molecule cm^-3, respectively, during the travel from the source areas in the U.K. and the low countries out to Mace Head. Using a simple box model, the available Mace Head measurements, when combined into a detailed chemical mechanism, generated OH radical concentrations which peaked at 7×10⁶ molecule cm^-3, in close agreement with the estimates based on trichloroethylene decay.     

The single-crystal,polarized-light,FTIR spectrum of stoppaniite,the Fe analogue of beryl

We report here a single-crystal polarized-light study of stoppaniite, ideally (Fe,Al,Mg)₄(Be₆Si₁₂O₃₆)(H₂O)₂(Na,□), from Capranica (Viterbo). Polarized-light FTIR spectra were collected on an oriented (hk0) section, doubly polished to 15 μm. The spectrum shows two main bands at 3,660 and 3,595 cm⁻¹; the former is strongly polarized for E ⊥c, while the latter is polarized for E //c. A sharp and very intense band at 1,620 cm⁻¹, plus minor features at 4,000 and 3,228 cm⁻¹ are also polarized for E //c. On the basis of literature data and considering the pleochroic behavior of the absorptions, the 3,660 cm⁻¹ band is assigned to the ν₃ stretching mode and the 1,620 cm⁻¹ (associated with an overtone 2*ν₂ at 3,230 cm⁻¹) band to the ν₂ bending mode of “type II” water molecules within the structural channels of the studied beryl. The sharp band at 3,595 cm⁻¹ is not associated with a corresponding ν₂ bending mode; thus it is assigned to the stretching vibration of O–H groups in the sample. The minor 4,000 cm⁻¹ feature can be assigned to the combination of the O–H bond parallel to c with a low-frequency metal-oxygen mode such as the Na–O stretching mode. The present results suggest that the interpretation of the FTIR spectrum of Na-rich beryl needs to be carefully reconsidered.     

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”。     

海水中超低含量活性磷酸盐的Mg(OH)2共沉淀法测定研究

活性磷(正磷酸盐)是海洋浮游植物生长所必需的物质基础[1-8],磷的生物可利用性直接影响全球的初级生产力水平.磷在特定的海洋环境中还可能限制固氮作用,成为限制海洋初级生产力的重要因素[1,3,6].海水中磷酸盐含量的测定也是海洋污染调查的重要指标之一[4,9].农业和工业废水中磷的过度排放导致河口和近岸海水富营养化,引起浮游植物异常繁殖,造成“赤潮”现象[4].因此,海水中磷的准确测定对深入理解生物地球化学过程及海洋环境保护具有重要理论和实际意义[4-6,9].磷钼蓝分光光度法是海水中活性磷的经典测定方法,检测限为324 nmo1/dm3[5],但在一些寡营养盐海域,例如在南海、地中海     

对OH/IR星演化的模型研究

渐近巨星分支恒星 (AGB星 )是一种晚期演化恒星 ,它是恒星作为以核反应释能为发光能源的天体的最后演化阶段。AGB星阶段的恒星具有许多有趣的性质 ,如很大的质量损失率 (因此形成很厚的拱星尘埃气体包层 ) ,光变 ,热脉动 (或He闪耀 ) ,强的红外超量发射 ,分子脉泽发射等 ,弄清AGB星的演化规律是研究恒星演化理论的重要任务。目前人们所知道的AGB星的演化图景是 ,恒星经过漫长的主序演化之后 ,将经过红巨星 (RGB)阶段 ,然后才进入AGB阶段 ,在其演化过程中AGB星的光度和质量损失率要逐渐增大 ,它的光变周期也逐渐变长 ,在其中心星经历了一系列的由He核反应不稳定性引起的热脉动之后 ,它的质量损失很快停止 ,恒星开始向行星状星云 (PN)演化 ,最后行星状星云将会变成一个白矮星 ,这将是许多初始质量不很大的恒星的最终结局。OH/IR星阶段是AGB星演化的一个阶段 ,OH/IR星是那些质量稍大的恒星在AGB阶段后期演化而成的天体。现阶段人们对OH/IR星的具体演化过程还知道得很少。我们利用了球对称包层中的尘埃辐射转移模型来研究OH/IR星的演化性质 ,并且收集了尽量多的具有可靠距离的OH/IR星来研究他们的光度和质量损失率的演化性质。在本文的研究工作中 ,我们主要讨论了OH/IR星在远红外双色图中的分布规律 ,还发现     

反应HO2+O→OH+O2对OH夜气辉辐射的贡献

本文探讨了OH Meinel夜气辉辐射的光化学模式，给出OH(ν≤9)分子数密度分布的计算通式，重点研究了化学反应HO\-2+O→OH(ν≤6)+O2对ν≤6各振动能级上OH分子数密度分布以及(ν′—ν″)(ν′≤6)振动带气辉辐射的影响.结果表明，该反应对数密度的贡献随振动能级的减小而增大，对(ν′—ν″)振动带辐射的贡献随着较高振动能级ν′的减小而增大，以春分时为例，它可使第1振动能级上的OH分子最大数密度和（1—0）带的最大辐射率增加约33%，第6振动能级上的最大数密度和（6—ν″）带的最大辐射率增加约7%，（1—0）带的辐射强度增加约30%，（6—ν″）带的强度增加约11%.该反应使各振动能级上分子数密度的高度分布剖面以及各振动带体辐射率的高度分布剖面变宽，最大数密度、最大发射率所处的高度下降1 km左右.此外，该反应的影响程度随着原子氧密度的降低而增大，随着温度的升高而增大，并且在夏至时最大，在冬至时最小.     

Mechanisms of OH defect incorporation in naturally occurring,hydrothermally formed diopside and jadeite

The IR spectrum of an alpine, hydrothermally formed diopside containing 17 wt ppm H₂O consists of three main OH absorption bands centred at 3647, 3464 and 3359 cm⁻¹. Jadeite from a Californian vein occurrence is characterised by bands at 3616 and 3557 cm⁻¹ and contains about 197 wt ppm H₂O. Based on the pleochroic scheme of the OH absorption bands in diopside, OH defect incorporation models are derived on the basis of fully occupied cation sites and under the assumption of M1 and M2 site vacancies; OH defects replacing O2 oxygen atoms are most common. The less pronounced OH pleochroism and the broad band absorption pattern of jadeite indicate a high degree of OH defect disordering. The pleochroic scheme of the main absorption bands at 3616 and 3557 cm⁻¹ implies partial replacement of O2 oxygen atoms by OH dipoles pointing to vacant Si sites. Under the assumption of M1 and M2 site vacancies, O1–H and O2–H defects are also derivable. OH incorporation modes assuming Si-vacancies should be considered for jadeite-rich clinopyroxenes formed in deep crust and upper mantle regions.     

Laboratory Study of O(1S) Formation Process in the Photolysis of O3 and its Atmospheric Implications

A high-sensitive technique to detect O(¹S) atoms using vacuum ultraviolet laser-induced fluorescence (VUV-LIF) spectroscopy has been applied to study the O(¹S) production process from the UV photodissociation of O₃, N₂O, and H₂O₂. The quantum yields for O(¹S) formation from O₃ photolysis at 215 and 220 nm are determined to be (1.4 ± 0.4) × 10⁻⁴ and (5 ± 3) × 10⁻⁵, respectively. Based on thermochemical considerations, the O(¹S) formation from O₃ photolysis at 215 and 220 nm is attributed to a spin-forbidden process of O(¹S)+O₂(X³Σ_g ⁻). Analysis of the Doppler profile of O(¹S) produced from O₃ photolysis at 193 nm also indicates that the O(¹S) atoms are produced from the spin-forbidden process. In the photolysis of N₂O and H₂O₂ at 193 nm, no discernible signal of O(¹S) atoms has been detected. The upper limit values of the quantum yields for O(¹S) production from N₂O and H₂O₂ photolysis at 193 nm are estimated to be 8 × 10⁻⁵ and 3 × 10⁻⁵, respectively. Using the experimental results, the impact of the O(¹S) formation from O₃ photolysis on the atmospheric OH radical formation through the reaction of O(¹S)+H₂O has been estimated. The calculated results show that the contribution of the O(¹S)+H₂O reaction to the OH production rate is ∼2% of that of the O(¹D)+H₂O reaction at 30 km altitude in mid-latitude. Implications of the present laboratory experimental results for the terrestrial airglow of O(¹S) at 557.7 nm have also been discussed.     

Location of OH groups and oxidation processes in triclinic chloritoid

Triclinic Fe²⁺ and Fe³⁺-chloritoid end members, as well as Fe²⁺-Fe³⁺-chloritoid solid solutions were synthesized in order to determine the location of the OH groups in the structure and to investigate the possibility of Fe³⁺ incorporation on the M1B site and the corresponding oxidation mechanism. The samples were analyzed using transmission electron microscopy, electron energy-loss and ⁵⁷Fe Mössbauer spectroscopy, polarized single-crystal, KBr powder and in situ high-pressure infrared spectroscopy. The structure of a natural triclinic chloritoid was refined by single-crystal X-ray diffraction in order to locate the proton-accepting oxygens in the triclinic structure. The results of valence bond calculations, polarized single-crystal and in situ high-pressure IR spectroscopy revealed that the orientations of the OH dipoles are the same as those in monoclinic chloritoid. The annealing experiments in air show that the incorporation of Fe³⁺ on M1B increases with temperature. After 3?h at 530?°C all Fe²⁺ was oxidized to Fe³⁺ without decomposition of the structure. This also holds true for a heating duration of 24?h. The incorporation of Fe³⁺ at M1B sites is coupled with a dehydration process starting at about 350?°C during which the H1A protons leave first.     

An Atmospheric Chemistry Interpretation of Mass Scans Obtained from a Proton Transfer Mass Spectrometer Flown over the Tropical Rainforest of Surinam

Data on a variety of organic gases are presented, obtained with a protontransfer mass spectrometer (PTR-MS) operated during the March 1998 LBA/CLAIREairborne measurement campaign, between 60 and 12500 m over the rainforest inSurinam (2° N–5° N, 54° W–57° W). The instrumentcan detect molecules with a proton affinity greater than water, includingalkenes, dialkenes, carbonyls, alcohols, and nitriles. Many such molecules areemitted from the rainforest (e.g., isoprene) or formed from the oxidation ofprimary emissions (e.g., methylvinylketone (MVK) and methacrolein (MACR)).From a comparison with modelled data; the variation with altitude; previouslyreported biogenic emissions and the time and location of the measurement,possible and probable identities for the significant masses encountered in therange 33–140 amu have been deduced.The main observed protonated masses, postulated identities and observedaverage boundary layer mixing ratios over the rainforest were: 33 methanol(1.1 nmol/mol); 42 acetonitrile (190 pmol/mol); 43 multiple possibilities (5.9nmol/mol), 45 acetaldehyde (1.7 nmol/mol), 47 formic acid (not quantified);59 acetone (2.9 nmol/mol), 61 acetic acid (not quantified), 63 dimethylsulphide (DMS) (289 pmol/mol), 69 isoprene (1.7 nmol/mol), 71 MVK + MACR (1.3nmol/mol), 73 methyl ethyl ketone (1.8 nmol/mol), 75 hydroxyacetone (606pmol/mol), 83 C₅ isoprene hydroxy carbonylsC₅H₈O₂, methyl furan, and cis 3-hexen-1-ol(732 pmol/mol), 87 C₅ carbonyls and methacrylic acid, 95 possibly2-vinyl furan (656 pmol/mol), 97 unknown (305 pmol/mol), 99 cis hexenal (512pmol/mol) and 101 isoprene C₅ hydroperoxides (575 pmol/mol). Somespecies agreed well with those derived from an isoprene only photochemicalmodel (e.g., mass 71 MVK + MACR) while others did not and were observed athigher than previously reported mixing ratios (e.g., mass 59 acetone, mass 63DMS). Monoterpenes were not detected above the detection limit of 300pmol/mol. Several species postulated are potentially important sources ofHO_x in the free troposphere, e.g., methanol, acetone, methyl ethylketone, methyl vinyl ketone and methacrolein.