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.     

Passing through resonance: The excitation and dissipation of the lunar free libration in longitude

The acceleration of the mean lunar longitude has a small effect on the periods of most terms in a Fourier expansion of the longitude. There are several planetary perturbation terms that have small amplitudes, but whose periods are close to the resonant period of the lunar libration in longitude. Some of these terms are moving toward resonance, some are moving away from resonance, and the periods of those terms that do not include the Delaunay variables in their arguments are not moving. Because of its acceleration of longitude, the Moon is receding from the Earth, so the magnitude of the restoring torque that the Earth exerts on the rotating Moon is gradually attenuating; thus resonance itself is moving, but at a much slower rate than the periods of the accelerating planetary perturbations. There are five planetary perturbation terms from the ELP-2000 Ephemeris (with amplitudes of 0.00001 or greater) that have passed through resonance in the past two million years. One of them is of special interest because it appears to be the excitation source of a supposed free libration in longitude that has been detected by the lunar laser ranging experiment. The amplitude of the term is only 0.00021 but it could be the source of the 1 amplitude free libration term if the viscoelastic properties of the Moon are similar to those of the Earth.     

A multivariate statistical and geostatistical study on the geochemistry of allochtonous karst bauxite deposits in Hungary

A geochemical evaluation of the Szc-Halimba-Kisld area, Hungary, covering an area of more than 200 km² is presented using different statistical and geostatistical methods. The study area is a representative example of allochtonous karst bauxite accumulation. The three groups of deposits studied here have been explored and mined since 1950. Several thousand boreholes have been drilled, and bauxite cores were analyzed for the five main chemical components. A total of 80,000 pleces of analytical data were processed, followed by a geological examination of borehole logs and of mining excavations.The quantitative geochemical evaluation of the data set led to both geochemical and practical results: The geochemical behavior of the allochtonous, clastic karst bauxite deposits differs essentially from that of the autochtonous and parautochtonous ones, as well as that of the lateritic bauxite deposits. The deposits of the study area can be split into several subsequent geochemical-sedimentological units, each representing an event of bauxite transport and accumulation. Clear regional patterns can be revealed in the composition of these units. The geostatistically measured chemical variability of the geochemical units is rather different, the lowest units showing the smallest variability. The interrelations of the main chemical components are weaker and more irregular in the studied deposits than in the autochtonous lateritic bauxite deposits. Additional local genetic features, such as transport routes, can be delineated by the methods applied. Within each deposit, local changes of chemical composition and of its variability can be determined more precisely. These results can be used in bauxite prospecting and exploration, because areas of high or low bauxite quality can be predicted.     

冀西北长城纪宣龙式铁矿层中微体植物化石的发现及其意义

本文研究的是笔者等在冀西北长城系串岭沟组宣龙式铁矿层中发现的微体植物化石,这些化石都保存在铁质叠层石(肾状赤铁矿)和铁质核形石(鲕状赤铁矿)的基本层中。微化石以丝状体为主,部分为球状体。归属于原核生物蓝藻门颤藻科的两个属和色球藻科的一个属。化石层同位素年龄约在1800—1757Ma。这些化石与北美冈弗林特组微化石比较,既有些相似,又有些区别。该化石的发现为研究铁矿的成因,指示沉积环境及层位对比都很有意义。     

Visualization experiments of iron precipitates: Application for in-situ arsenic remediation

Laboratory experiments were carried out to acquire more insight and understanding of the phenomena associated with the in-situ arsenic remediation. Visualization techniques are the most informative for the detection of Fe(II) while flowing in soils. Green Rust (GR) was considered as representative of in-situ iron precipitates. In a visualization flat cell, the change in color of GR to orange, due to oxidation, was monitored by a digital camera and the images were analyzed giving the spatial and temporal distribution of Fe(II). Moreover, both oxygen and pH changes in time were recorded in two sections along the flow direction in the cell. The measured and calculated concentration profiles were compared and the actual reaction rates were predicted. The reaction rate constants measured in this study, under flowing conditions, are in a good agreement with the values obtained from batch experiments reported in the literature.     

Speciation of adsorbed arsenate on the surface of hydrous iron oxide

Adsorption of arsenate on hydrous iron oxide is an important process controlling geochemical cycling of arsenic in environment as well as the fate of arsenic-bearing mining wastes. The widely accepted view on the mechanism of adsorption is that arsenate is adsorbed via bidentate binuclear inner-sphere complexation. In this study, we characterized the arsenate-hydrous iron oxide sorption solids synthesized at pH=3-8 using Fourier transformed infrared spectroscopy （FTIR） and X-ray diffraction （XRD）. It has been determined that poorly crystalline ferric arsenate developed on the surface of iron oxide when arsenate was sorbed at acidic pH, while at alkaline pH the adsorption of arsenate was via bidentate complexation.     

XANES analysis of the mechanisms of arsenic removal in biological iron and manganese treatment unit

Biological iron and manganese removal utilizing indigenous iron and manganese oxidizing bacteria （IRB hereafter） in groundwater can also be applied to arsenic removal according to our pilot-scale test. The arsenic removal probably occurred through sorption and complexation of arsenic to iron and manganese oxides formed by enzymic action of IRB. We investigated the chemical properties of iron and manganese oxides in IRB floc and the valence state of arsenic sorbed to the floc to clarify the mechanisms of the arsenic [especially As （Ⅲ）] removal. The floc samples were collected from two drinking water plants using IRB （Jyoyo and Yamatokoriyama, Japan）, and our pilot - scale test site where arsenic and iron removal using IRB is under way （Mukoh, Japan）. The Jyoyo and Yamatokoriyama IRB floc samples were subjected to As （Ⅲ） and As（Ⅴ） sorption experiments. The elemental composition of the floc samples was measured. XANES spectra were collected on As, Fe and Mn K-edges at synchrotron radiation facility Spring 8 （Hyogo, Japan）. FT-IR and the X-ray diffraction spectra of the samples were also obtained. The IRB floc contained ca. 35 % Fe, 0.3%-3.5% Mn and 2%-6% P. The samples were highly amorphous and contained ferrihidrites and hydrated iron phosphate. According to XANES analyses of IRB, As associated with IRB was in ＋5 valence state when As （Ⅲ） （or As （Ⅴ）） was added in laboratory sorption test, Fe in ＋3 valence state, and Mn a mixture of＋3 and ＋4 valence states. Small shift was observed in the XANES spectra of IRB on As K-edge as the equilibration time of the sorption experiment was increased. Gradual oxidation of a small amount of As （Ⅲ） associated with IRB or change in arsenic binding with sorption site were the probable mechanism.     

自由测站法曲线座标计算程序设计

通过对曲线测设和测点坐标计算过程的分析，把坐标计算的程序设计归结为有向直线与X轴顺时针夹角即方位角的计算和线路转向转角的计算，弥补了测点位置和计算公式分类复杂等不足，简化了程序设计和计算过程。     

一次造成乌鲁木齐市电网瑶线铁塔倒塌事故的气象原因分析

为了解2004年11月24日乌鲁木齐市两座电网瑶线铁塔倒塌事故的气象原因，通过实地调查，并对高低空环流形势场、加密气象站信息等进行了分析。结果表明，乌鲁木齐地区不同地理位置风速差异很大，红雁池和头屯河区瞬间极大风速分别比市区大12．8m／s和18．4m／s。纠正了过去认为东南大风的强中心只出现在红雁池附近的说法，为今后制作大风分区预报提供了参考，也可为城区高层建筑及相关设计规范的修正提供借鉴。