On the pH-dependent formation constants of iron(III)-sulfur(IV) transient complexes

An experimental study is described of Fe(III)-S(IV) formation constants measured as a function of pH (1–3), ionic strength (0.2–0.5 M) and [Fe(III)] _T (2.5–5.0×10^–4 M) using a continuous-flow spectrophotometric technique to make observations 160 ms after mixing. Preliminary experiments using pulse-accelerated-flow (PAF) spectrophotometry to measure rate constants on a microsecond timescale are also described. The conditional formation constant at 25 °C can be modeled with the following equation: {ie307-1} where {ie307-2}K ₇ andK ₈ can be interpreted as intrinsic constants for the coordination of HSO ₃ ^– by FeOH²⁺ and Fe³⁺, respectively, but until further evidence is obtained they should be regarded as fitting constants. PAF spectrophotometry showed that the initial reaction of Fe(III) with S(IV) (pH 2.0) is characterized by a second-order rate constant of 4×10⁶ M^–1 s^–1 which is comparable to rate of reaction of FeOH²⁺ with SO ₄ ^2– . However, the PAF results should be regarded as preliminary since unexpected features in the initial data indicate that the reaction may be more complex than expected.     

Kinetics of redox cycling of iron coupled with fulvic acid

The kinetics of conversion of iron(III) (hydr)oxides to ferrous iron mediated by fulvic acid have been investigated in order to improve the understanding of the redox cycling of iron at the oxic-anoxic boundary in natural waters. Under the conditions similar to natural waters, fulvic acid is able to reduce the iron(III) (hydr)oxide. The kinetics of the reaction depend on the reactivity of iron(III) (hydr)oxides and the reducing power of the fulvic acid. The rate of reaction is 60 nm/h obtained under following conditions: total concentration of Fe(III) 1.0 × 10^–4 M, pH 7.5, fulvic acid 5 mg/L. The rate is considered as a net result of reduction and oxidation in the > Fe^III-OH/Fe(II) wheel coupled with fulvic acid. In a real natural water system, reductants other than fulvic acid may be of importance. The results obtained in the laboratory, however, provide evidence that the Fe(OH)₃(s)/Fe(II) redox couple is able to act as an electron-transfer mediator for the oxidation of natural organic substances, such as fulvic acid by molecular oxygen either in the absence of microorganisms or as a supplement to microbial activity.     

杠杆点评估及设计空间抗差

本分析了杠杆点的几何含义和统计特征,从杠杆点的保差性,矩阵的摄动和参数估值可靠性的观点出发讨论了杠杆点的不利和有利的两个方面,提出了一个全面的设计空间抗差方案。     

地下水非稳定流的LTFAM算法

渗流域内应用拉普拉斯变换(LT)建立相应的有限分析(FAM)方程,顾及渗流域内地下水流的初始条件和边界条件,可在LT空间构成一个封闭的以水头像函数为变量的线性方程组。将此方程组所得的解,通过Stehfest数值反演公式,可归化为时间域的解(水头)。由于时间t被隐含在数值方程内,从而克服了传统数值法按时段(△t)逐步迭代的缺陷,提高了计算效率,也为用嵌入法建立地下水流管理模型提供了一条捷径。     

基于土地适宜性评价与元胞自动机模型的城市开发边界划定方法

城市开发边界的划定可以在一定程度上引导城市空间的良性扩张。为了研究边界划定的方法,以我国某港口城市作为研究区域,在空间增长模拟的方向进行探索。研究中借助土地适宜性评价和元胞自动机边界工具,构建既符合生态资源环境要求又符合城市发展需要的边界划定,同时,为了实现城市用地健康和动态管控举措,提出了建立健全土地用地管理机制的要求。     

随钻测录井地质导向二维分解实时绘图方法

根据随钻测录井实时地质导向和大斜度、水平井评价成图技术需求，针对传统绘图方法存在的弊端，提出了将测录井信息、井眼轨迹和地质模型进行二维分解的实时绘图方法。针对二维分解绘图方法绘图时空复杂度较高的问题，给出了不同事件驱动下的局部实时计算和拷屏重绘算法，控制了对CPU和内存的消耗、提高了绘图效率，消除了实时绘图的闪烁和卡顿现象。应用实例表明，二维分解实时绘图方法能够实现大尺度随钻测录井地质导向图形的流畅、无卡顿实时绘图，可提高大斜度、水平井储层模型评价的刻画精度和时效。     

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.     

A search for ultra-high energy counterparts to gamma-ray bursts

A small air shower array operating over many years has been used to search for ultra-high energy (UHE) gamma radiation ( 50 TeV) associated with gamma-ray bursts (GRBs) detected by the BATSE instrument on the Compton Gamma-Ray Observatory (CGRO). Upper limits for a one minute interval after each burst are presented for seven GRBs located with zenith angles < 20°. A 4.3 excess over background was observed between 10 and 20 minutes following the onset of a GRB on 11 May 1991. The confidence level that this is due to a real effect and not a background fluctuation is 99.8%. If this effect is real then cosmological models are excluded for this burst because of absorption of UHE gamma rays by the intergalactic radiation fields.     

Analysis of COMPTEL gamma-ray burst locations and spectra

In its first three years of operation, the COMPTEL instrument on theCompton Gamma-Ray Observatory has measured the locations (mean accuracy 1°) and spectra (0.75-30 MeV) of 18 gamma-ray bursts and continues to observe new events at a rate of 1/month. With good angular resolution and sensitivity at MeV energies, the growing COMPTEL burst catalog is an important new piece of evidence in the on-going GRB mystery. The COMPTEL burst locations are consistent with an isotropic distribution of sources, yet the spatial coincidence of two of the bursts indicates the possibility of repetition. The COMPTEL burst spectra are in most cases consistent with a single power law model with spectral index in the range 2–3. However, two bursts show evidence of a spectral break in the MeV range. Measurement of rapid variability at MeV energies in the stronger bursts provides evidence that either the sources are nearby (within the Galaxy) or the gamma-ray emission is relativistically beamed. We present an overview of analysis results obtained from the COMPTEL burst catalog concentrating on the search for burst repetition and the implications of highly variable MeV emission.     

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.