Flow reactor and triple quadrupole mass spectrometer investigations of negative ion reactions involving nitric acid: Implications for atmospheric HNO3 detection by chemical ionization mass spectrometry

Atmospheric nitric acid measurements by ACIMS (Active Chemical Ionization Mass Spectrometry) are based on ion-molecule reactions of CO₃ ^-(H₂O) _n and NO₃ ^-(H₂O) _n with HNO₃. We have studied these reactions in the laboratory using a flow tube apparatus with mass spectrometric detection of reactant and product ions. Both product ion distributions and rate coefficients were measured. All reactions were investigated in an N₂-buffer (1–3 hPa) at room temperature. The reaction rate coefficients of OH^-, O₂ ^-, O₃ ^-, CO₄ ^-, CO₃ ^-, CO₃ ^-H₂O, NO₃ ^-, and NO₃ ^-H₂O were measured relative to the known rate k=3.0×10^-9 cm³ s^-1 for the reaction of O^- with HNO₃. The main product ion of the reaction of CO₃ ^-H₂O with HNO₃ was found to be (CO₃HNO₃)^- supporting a previous suggestion made on the basis of balloon-borne ACIMS measurements. For the reaction of bare CO₃ ^- with HNO₃ three product ions were observed, namely NO₃ ^-, (NO₃OH)^-, and (CO₃HNO₃)^-. The reaction rate coefficients for CO₃ ^-H₂O (1.7×10^-9 cm³ s^-1) and NO₃ ^-H₂O (1.6×10^-9 cm³ s^-1) were found to be close to the collision rate. The measured k values for bare CO₃ ^- (1.3×10^-9 cm³ s^-1) and NO₃ ^- (0.7×10^-9 cm³ s^-1) are somewhat smaller. The collisional dissociations of CO₃ ^-(H₂O) _n , NO₃ ^-(H₂O) _n (n=1, 2), (CO₃HNO₃)^- and (NO₃HNO₃)^-, occasionally influencing ACIMS measurements, were also studied. Fragment ion distributions were measured using a triple quadrupole mass spectrometer. The results showed that previous stratospheric nitric acid measurements were unimpaired from collisional dissociation processes whereas these processes played a major role during previous tropospheric measurements leading to an underestimation of nitric acid concentrations. Previous ACIMS HNO₃ detection was also affected by the conversion of CO₃ ^-(H₂O) _n to NO₃ ^-(H₂O) _n due to ion source-produced neutral radicals. A novel ACIMS ion source was developed in order to avoid these problems and to improve the ACIMS method.     

Response of selected binomial coefficients to varying degrees of matrix sparseness and to matrices with known data interrelationships

Numerous departures from ideal relationships are revealed by Monte Carlo simulations of widely accepted binomial coefficients. For example, simulations incorporating varying levels of matrix sparseness (presence of zeros indicating lack of data) and computation of expected values reveal that not only are all common coefficients influenced by zero data, but also that some coefficients do not discriminate between sparse or dense matrices (few zero data). Such coefficients computationally merge mutually shared and mutually absent information and do not exploit all the information incorporated within the standard 2 × 2 contingency table; therefore, the commonly used formulae for such coefficients are more complicated than the actual range of values produced. Other coefficients do differentiate between mutual presences and absences; however, a number of these coefficients do not demonstrate a linear relationship to matrix sparseness. Finally, simulations using nonrandom matrices with known degrees of row-by-row similarities signify that several coefficients either do not display a reasonable range of values or are nonlinear with respect to known relationships within the data. Analyses with nonrandom matrices yield clues as to the utility of certain coefficients for specific applications. For example, coefficients such as Jaccard, Dice, and Baroni-Urbani and Buser are useful if correction of sparseness is desired, whereas the Russell-Rao coefficient is useful when sparseness correction is not desired.     

元素性质和熔体成分对分配系数的影响及其意义

对现有40个元素的熔体-溶液分配系数的综合分析表明,元素性质和熔体成分是控制熔体-溶液间元素分配的重要因素。挥发组分的分配系数为K_F、K_P、>1>K_B、K_S>K_(Cl)。自Au、Ag、Cu、Pb、Zn、→Fe、Mn、Mg、Li、Rb、Cs、K、Na、Ca、Sr、Ba→Sn、Mo、W、Si、Al、∑Ce、∑Y、Nb、Ta,随元素氧化物吉布斯自由能的减小,元素分配系数逐渐增大。随熔体酸度的降低和碱度的增高,元素分配系数普遍增大。随熔体铝过饱和度的增高,Nb、Ta、Zn、REE的分配系数减小。这些变化规律有助于阐明花岗岩类的成矿专属性和成矿分带,评价火成岩的含矿性,预测未知的元素分配系数,并讨论不同熔体间元素的分配行为。     

TOGA-COARE IOP期间的海气通量观测结果

在TOGA－COAREIOP期间用涡度相关法对海气热通量进行了船载直接观测．对垂直风速、温度和湿度湍流脉动观测数据的谱分析显示它们在高频区基本满足"－2／3次方律"．对船体简谐震荡影响的讨论从理论上证明该影响在热通量计算中可被忽略．根据以此方法得到的通量求出了中性层结条件下感热和潜热的整体输送系数分别为2．25×10（－3）和1．26×10（－3）．对海气边界层特性的分析表明该海域的近海层主要呈中性或弱不稳定层结．海气通量的变化与背景环流形势密切相关,潜热通量主要受海面风场强度的影响,而感热通量变化除了风场的影响外,层结变化也是一个重要因素．用整体输送法计算TOGA－COAREIOP期间以及TOGA期间8个航次的通量结果而得到的Bowen比约为0．1,显示潜热通量是暖池大气的主要热源．     

TOGA-COARE IOP期间的海气通量观测结果

在TOGA－COAREIOP期间用涡度相关法对海气热通量进行了船载直接观测．对垂直风速、温度和湿度湍流脉动观测数据的谱分析显示它们在高频区基本满足"－2／3次方律"．对船体简谐震荡影响的讨论从理论上证明该影响在热通量计算中可被忽略．根据以此方法得到的通量求出了中性层结条件下感热和潜热的整体输送系数分别为2．25×10^－3和1．26×10^－3．对海气边界层特性的分析表明该海域的近海层主要呈中性或弱不稳定层结．海气通量的变化与背景环流形势密切相关,潜热通量主要受海面风场强度的影响,而感热通量变化除了风场的影响外,层结变化也是一个重要因素．用整体输送法计算TOGA－COAREIOP期间以及TOGA期间8个航次的通量结果而得到的Bowen比约为0．1,显示潜热通量是暖池大气的主要热源．     

A history and state-of-the-art of accommodation coefficients

This paper reviews theory and measurements of transport processes between small particles and the surrounding gas. Evaporation and condensation coefficients and gas uptake coefficients are of particular interest. There has long been a great difference in coefficients reported by different experimentalists, and much of this disagreement is considered in this overview. A brief review of the kinetic theory of gases is provided to describe molecular transport to or from a surface when the mean free path of molecules, ℓ, is large compared with the particle dimensions, that is, when the Knudsen number is large. For a sphere of radius a the Knudsen number, Kn = ℓ / a. The condition Kn >> 1 is called the free molecule regime, and for Kn << 1 continuum theory applies. It is shown that accommodation coefficients cannot be determined by experiments operating in the continuum regime. At intermediate Knudsen numbers (the Knudsen regime) transport theory is more difficult, but results based on solution of the Boltzmann equation describing the evolution of the molecular velocity distribution are reviewed. With the advent of high-speed computers transport theory has been supplemented by molecular dynamics calculations, and these calculations are often at odds with experimental measurements of accommodation coefficients. Examples are provided.Experimental methods surveyed include Knudsen cell methods, jet tensimetry, electrodynamic levitation experiments, expansion cloud chamber measurements, and vibrating orifice aerosol generator (VOAG) techniques. VOAG measurements are particularly useful for studying processes over small times, and theory and results related to VOAG experiments are presented. More recent experimental measurements of condensation coefficients involving the use of molecular beams are reported. There is a growing body of evidence that accommodation coefficients are of order unity in many cases, but coefficients smaller than 0.01 are still reported, particularly for uptake coefficients.     

Trace-element partitioning between garnet,clinopyroxene and Fe-rich picritic melts at 3 to 7 GPa

We have determined mineral-melt partition coefficients (D values) for 20 trace elements in garnet-pyroxenite run products, generated in 3 to 7 GPa, 1,425–1,750°C experiments on a high-Fe mantle melt (97SB68) from the Paraná-Etendeka continental-flood-basalt (CFB) province. D values for both garnet (∼Py₆₃Al₂₅Gr₁₂) and clinopyroxene (∼Ca_0.2Mg_0.6Fe_0.2Si₂O₆) show a large variation with temperature but are less dependent on pressure. At 3 GPa, D ^cpx/liq values for pyroxenes in garnet-pyroxenite run products are generally lower than those reported from Ca-rich pyroxenes generated in melting experiments on eclogites and basalts (∼Ca_0.3–0.5Mg_0.3–0.6Fe_0.07–0.2Si₂O₆) but higher than those for Ca-poor pyroxenes from peridotites (∼Ca_0.2Mg_0.7Fe_0.1Si₂O₆). D ^grt/liq values for light and heavy rare-earth elements are ≤0.07 and >0.8, respectively, and are similar to those for peridotitic garnets that have comparable grossular but higher pyrope contents (Py_70–88Al_l7–20Gr_8–14). 97SB68 D _LREE^grt/liq values are higher and D _HREE^grt/liq values lower than those for eclogitic garnets which generally have higher grossular contents but lower pyrope contents (Py_20–70Al_10–50Gr_10–55). D values agree with those predicted by lattice strain modelling and suggest that equilibrium was closely approached for all of our experimental runs. Correlations of D values with lattice-strain parameters and major-element contents suggest that the wollastonite component and pyrope:grossular ratio exert major controls on 97SB68 clinopyroxene and garnet partitioning, respectively. These are controlled by the prevailing pressure and temperature conditions for a given bulk-composition. The composition of co-existing melt was found to have a relatively minor effect on 97SB68 D values. The variations in D values displayed by different mantle lithologies are subtle and our study confirms previous investigations which have suggested that the modal proportions of garnet and clinopyroxene are by far the most influential factor in determining incompatible trace-element concentrations in mantle melts. The trace-element partition coefficients we have determined may be used to place high-pressure constraints on garnet-pyroxenite melting models.     

Effect of interface characteristics on the influence coefficients of an embedded circular footing under horizontal and moment loading

By means of a semi-analytical FE approach an embedded circular footing under monotonic horizontal and moment loading is studied. In a non-homogeneous soil whose shear modulus is characterized by a power law variation with depth, horizontal, rocking and coupled modes of displacement, expressed in terms of influence factors are thoroughly examined. The exponent α that controls the shape of the stiffness variation with depth is termed shear modulus factor. Surface influence coefficients are considered for the situations where the interface between the soil and the footing is either perfectly rough or perfectly smooth. First, results of semi-analytical FE analysis in the case of rough footing are established and compared with those of another numerical method. Results of comparison show good agreement. Then, for different values of α the surface influence coefficients are presented for an embedded footing in perfect smooth contact with soil. The metacentre is referred to as the depth at which there is no coupling between the sliding and the rocking modes of footing deformations. Expressions for location and horizontal influence coefficient corresponding to this particular depth are developed and their variations with α examined. The paper finishes by showing the effect of interface conditions on the soil normal stresses developed beneath the embedded circular footing for the case of loading applied at the footing top.     

Application of Wavelet Decomposition to Removing Barometric and Tidal Response in Borehole Water Level

Wavelet decomposition is used to analyze barometric fluctuation and earth tidal response in borehole water level changes. We apply wavelet analysis method to the decomposition of barometric fluctuation and earth tidal response into several temporal series in different frequency ranges. Barometric and tidal coefficients in different frequency ranges are computed with least squares method to remove barometric and tidal response. Comparing this method with general linear regression analysis method, we find wavelet analysis method can efficiently remove barometric and earth tidal response in borehole water level. Wavelet analysis method is based on wave theory and vibration theories. It not only considers the frequency characteristic of the observed data but also the temporal characteristic, and it can get barometric and tidal coefficients in different frequency ranges. This method has definite physical meaning.