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.     

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。     

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。     

TOWARD ESTABLISHING THE CONCEPT OF PHYSICAL URBAN AREA IN CHINA

I.IntroduchollWiulegeOgraphystudiestheterritoria1systemsabouttherelationsbforeenhumanbeingSandthenature[I4],urbanmpaphyfocusesspecificallyonthespatialoopltizationandprocessofurbanterritory,anditsinteraCtionwiti1Otherterritorialsystems.Usually,wedoresearch…     

预测陕西关中地区需水量的改进GM(1,1)模型

需水量评价与预测是水资源规划与管理一项重要的研究内容。本文采用定额法计算需水量。通过对陕西关中地区需水量要素组成的分析,认为需水量要素属平稳时间序列,且一阶累加生成数据系列满足指数规律,符合灰色预测条件。为了提高GM(1,1)模型的精度,采用一种改变背景值的新方法,即:中心逼近方法。通过精度检验,中心逼近式GM(1,1)模型平均误差百分比、误差平方和分别比传统的GM(1,1)模型提高了0.147和1.579。用中心逼近式GM(1,1)模型预测需水量各要素近期和中长期值,经检验,其中非农业人口、农业人口、耕地面积、工业总产值预测模型满足一级模型,等级为良好。牲畜头数预测模型为不合格模型,分析其原因,主要是因为时间序列数据不完全符合指数规律。通过定额法计算,预计75%保证率时2005年和2010年关中地区工农业需水量分别占总需水量的92.21%和89.75%,生活需水量分别占7%和9.04%。     

Statistical evaluation of methods for the calculation of static formation temperatures in geothermal and oil wells using an extension of the error propagation theory

The feasibility of using the more sophisticated weighted least-squares (WLS) model, as opposed to the traditional ordinary least-squares (OLS), in linear regressions of BHT data to estimate the static formation temperatures (SFT) was investigated. The most commonly used analytical methods (line-source; spherical and radial heat flow; and cylindrical heat source) were applied. Error propagation equations were derived to calculate errors in the time function of each method. These errors were combined with the BHT measurement errors to compute weighting factors for applying the WLS. Intercept uncertainties were estimated for all regressions using sets of synthetic and actual borehole logs taken from geothermal and oil applications. SFT computed with the spherical and radial heat flow method were generally greater than those from the other two methods.     

Stratigraphy and optically stimulated luminescence (OSL) dating of a Quaternary sequence along the Dong Nai River, southern Vietnam

The pre-Holocene Cenozoic sequence outcrops in the terrestrial part of the eastern margin of the Mekong Basin. However, the stratigraphy of the sequence is still unclear. Its detailed stratigraphy and chronology were therefore studied along the Dong Nai River, southern Vietnam, and the lithofacies and the relations among the formations were investigated from the outcrops. The ages of the deposits were determined by using optically stimulated luminescence (OSL) dating.The Ba Mieu Formation was deposited about 176±52 ka during marine isotope stage (MIS) 7–6. The Thu Duc Formation was deposited about 97±27 ka during MIS 5. Both the Ba Mieu and Thu Duc formations are composed of fluvial and tidally influenced coastal deposits. The newly proposed Nhon Trach Formation was originally an eolian (blanket) deposit, but it has been partly reworked by fluvial processes. The Nhon Trach Formation was deposited about 10.9±4.7 ka, in the last part of the Pleistocene to the beginning of the Holocene. The OSL ages for the Ba Mieu, Thu Duc, and Nhon Trach formations are younger than the ages previously assigned to these formations.     

Geochemistry and Origin of Ananai Stratiform Manganese Deposit in the Northern Chichibu Belt, Central Shikoku, Japan

Abstract. Major and trace element contents are reported for Permian manganese ore and associated greenstone from the Ananai manganese deposit in the Northern Chichibu Belt, central Shikoku, Japan. The manganese deposit occurs between greenstone and red chert, or among red chert beds. Chemical compositions of manganese ore are characterized by enrichments in Mn, Ca, P, Co, Ni, Zn, Sr and Ba, and negative Ce and positive Eu anomalies relative to post-Archean average Australian Shale (PAAS). Geochemical features of the manganese ore are similar to those of modern submarine hydrother-mal manganese deposits from volcanic arc or hotspot setting. In addition, geochemical characteristics of the greenstone closely associated with the Ananai manganese deposit are analogous to those of with-in plate alkaline basalt (WPA). Consequently, the Ananai manganese deposit was most likely formed by hydrothermal activity related to hotspot volcanism in the Panthalassa Ocean during the Middle Permian. This is the first report documenting the terrestrially-exposed manganese deposit that was a submarine precipitate at hotspot.     

Effects of magnetic interactions in anisotropy of magnetic susceptibility: Models, experiments and implications for igneous rock fabrics quantification

Besides granites of the ilmenite series, in which the anisotropy of magnetic susceptibility (AMS) is mainly controlled by paramagnetic minerals, the AMS of igneous rocks is commonly interpreted as the result of the shape-preferred orientation of unequant ferromagnetic grains. In a few instances, the anisotropy due to the distribution of ferromagnetic grains, irrespective of their shape, has also been proposed as an important AMS source. Former analytical models that consider infinite geometry of identical and uniformly magnetized and coaxial particles confirm that shape fabric may be overcome by dipolar contributions if neighboring grains are close enough to each other to magnetically interact. On these bases we present and experimentally validate a two-grain macroscopic numerical model in which each grain carries its own magnetic anisotropy, volume, orientation and location in space. Compared with analytical predictions and available experiments, our results allow to list and quantify the factors that affect the effects of magnetic interactions. In particular, we discuss the effects of (i) the infinite geometry used in the analytical models, (ii) the intrinsic shape anisotropy of the grains, (iii) the relative orientation in space of the grains, and (iv) the spatial distribution of grains with a particular focus on the inter-grain distance distribution. Using documented case studies, these findings are summarized and discussed in the framework of the generalized total AMS tensor recently introduced by Cañon-Tapia (Cañon-Tapia, E., 2001. Factors affecting the relative importance of shape and distribution anisotropy in rocks: theory and experiments. Tectonophysics, 340, 117–131.). The most important result of our work is that analytical models far overestimate the role of magnetic interaction in rock fabric quantification. Considering natural rocks as an assemblage of interacting and non-interacting grains, and that the effects of interaction are reduced by (i) the finite geometry of the interacting clusters, (ii) the relative orientation between interacting grains, (iii) their heterogeneity in orientation, shape and bulk susceptibility, and (iv) their inter-distance distribution, we reconcile analytical models and experiments with real case studies that minimize the role of magnetic interaction onto the measured AMS. Limitations of our results are discussed and guidelines are provided for the use of AMS in geological interpretation of igneous rock fabrics where magnetic interactions are likely to occur.