The chemistry of aqueous iron

Zusammenfassung Bei der Berechnung der L?slichkeiten des zwei-und des dreiwertigen Eisens müssen neben den Fe⁺² und Fe⁺³ Ionen auch die Eisen(II)- und Eisen(III)-Hydroxokomplexe ([Fe(OH)]⁺, [Fe(OH)]²⁺, [Fe(OH)₂]⁺, [Fe(OH)₃] (d), und [Fe(OH)₄]⁻) berücksichtigt werden. Die L?slichkeit des zweiwertigen Eisens in natürlichen (Bikarbonat enthaltenden) W?ssern ist in der Regel durch die L?slichkeitsgleichgewichte des Eisenkarbonats beschr?nkt, w?hrend die L?slichkeit des dreiwertigen Eisens durch die L?slichkeitsgleichgewichte des Eisen(III)-Hydroxyds bestimmt wird (Abbildungen 2 und 4). Die L?slichkeitsverh?ltnisse k?nnen durch Komplexbildung, vor allem mit organischen Basen, ver?ndert werden. Dreiwertiges Eisen hat eine viel st?rkere Tendenz, Hydroxokomplexe zu bilden, as zweiwertiges Eisen. Dementsprechend ist das hydratisierte Eisen-(III)-Ion eine so?rkere S?ure (im SinneBr?nsteds) als das Eisen-(II)-Ion. Die Oxydation von Eisen-(II) zu Eisen-(III) ist deshalb von einer Erniedrigung des pH-Wertes begleitet. Die Hydroxoeisen-(III)-Komplexe haben eine starke Tendenz, Polymerisationsreaktionen einzugehen, wobei im schwach sauren oder neutralen Bereich positiv geladene im alkalischen Bereich hingegen negative geladene Kolloidpartikel entstehen k?nnen. Die allf?llige Koagulation dieser Kolloide zu Eisenoxydhydrat ist vom Elektrolytgehalt abh?ngig und kann durch hydrophile organische Schutzkolloide verhindert werden. Zweiwertiges Eisen ist in Gegenwart von gel?stem Sauerstoff unbest?ndig und wird zu dreiwertigem Eisen oxydiert. Die Oxydationsgeschwindigkeit nimmt mit zunehmendem pH stark zu. Kupfer-, Platinsalze und Aktivkohle als Katalysatoren sowie Komplexbildner, welche mit dreiwertigem Eisen Komplexe bilden,beschleunigen die Autoxidation. Elektrodenpotential-pH-Diagramme (Abbildung 5) erm?glichen einen zusammenfassenden überblick über den Einfluss von Potential und pH auf die L?slichkeitsverh?ltnisse. Im Eisenkreislauf der Seen (Abbildung 7) kommt das Wechselspiel von Oxydation und Reduktion sowie von F?llung und L?sung eindrücklich zur Geltung.      

Stability of arsenopyrite and As(III) in low-temperature acidic solutions

Arsenopyrite is one of the most important pri-mary arsenic mineral. In the Eh-pH diagram of the As-O2-S-H2O system, if the total arsenic concentration (TAs) is taken to be 0.75 mg/L, the total sulfur con-centration, 32 mg/L, the temperature, 25℃and the pressure, one atmosphere pressure for the discrimina-tion of arsenic species, it may be found that under hy-pergene conditions, arsenopyrite is a moderately stable mineral. Only in the strongly alkaline and reducing environment can arsenopy…     

Selective Separation and Preconcentration of Fe(III) and Zn(II) Ions by Solvent Extraction Using a New Triketone Reagent

A simple, rapid, and accurate method was developed for separation and preconcentration of trace levels of iron(III) and zinc(II) ions in environmental samples. Methyl‐2‐(4‐methoxy‐benzoyl)‐3‐(4‐methoxyphenyl)‐3‐oxopropanoylcarbamate (MMPC) has been proposed as a new complexing agent for Fe(III) and Zn(II) ions using solvent extraction prior to their determination by flame atomic absorption spectrometry (FAAS). Fe(III) and Zn(II) ions can be selectively separated from Fe(II), Pb(II), Co(II), Cu(II), Mn(II), Cr(III), Ni(II), Cd(II), Ag(I), Au(III), Pd(II), Cr(VI), and Al(III) ions in the solution by using the MMPC reagent. The analytical parameters such as pH, sample volume, shaking time, amount of MMPC reagent, volume of methyl isobutyl ketone (MIBK), effect of ionic strength, and type of back extractant were investigated. The recovery values for Fe(III) and Zn(II) ions were greater than 95% and the detection limits for Fe(III) and Zn(II) ions were 0.26 and 0.32 µg L^?1, respectively. The precision of the method as the relative standard deviation changed between 1.8 and 2.1%. Calibration curves have a determination coefficient (r²) of at least 0.997 or higher. The preconcentration factor was found to be 100. Accuracy of the method was checked by analyzing of a certified reference material and spiked samples. The developed method was applied to several matrices such as water, hair, and food samples.     

Diel changes in metal concentrations in a geogenically acidic river: Rio Agrio,Argentina

Rio Agrio in Patagonia, Argentina is a geogenically acidic stream that derives its low-pH waters from condensation of acidic gases near its headwaters on the flanks of the active Copahue Volcano. This study reports the results of three diel (24-h) water samplings in three different pH regimes (3.2, 4.4 and 6.3) along the river. Changes in the concentration and speciation of Fe dominated the diel chemical changes at all three sites, although the timing and intensity of these cycles were different in each reach. At the two acidic sampling sites, total dissolved Fe and dissolved Fe(III) concentrations decreased during the day and increased at night, whereas dissolved Fe(II) showed the reverse pattern. These cycles are explained by Fe(III) photoreduction, as well as enhanced rates of precipitation of hydrous ferric oxide (HFO) during the warm afternoon hours. A strong correlation was observed between Fe(III) and As at the furthest upstream (pH 3.2) site, most likely due to co-precipitation of As with HFO. At the downstream (pH 6.3) location, Fe(II) concentrations increased at night, as did concentrations of rare earth elements and dissolved Al. Photoreduction does not appear to be an important process at pH 6.3, although it may be indirectly responsible for the observed diel cycle of Fe(II) due to advection of photochemically produced Fe(II) from acidic upstream waters.     

Microbial iron reduction during passive in situ remediation of an acidic mine pit lake mesocosm

Ferric iron reduction was studied in a pilot-scale enclosure experiment for passive biological remediation of an acidic mine pit lake in Lusatia, Germany. The metabolic properties of prokaryotes involved in Fe(III) reduction may be important for the outcome of biological remediation, as chemolithotrophic Fe(III) reduction can counteract the desired pH increase, but heterotrophic Fe(III) reduction will provide the necessary Fe(II) for precipitation of sulfide minerals following sulfate reduction. Therefore, vertical profiles of sediment parameters related to iron and sulfur cycling were determined in conjunction with viable counts of different ferric iron-reducing micro-organisms using selective media. Findings were compared to an untreated reference site. The addition of organic matter stimulated ferric iron reduction and sulfate reduction in the enclosure and led to elevated pH and accumulations of ferrous iron and reduced sulfur compounds. Numbers of neutrophilic heterotrophic Fe(III) reducers increased during treatment, those of acidophilic heterotrophic Fe(III) reducers remained similar, and those of acidophilic chemolithotrophic Fe(III) reducers decreased. Zones of ferric iron-reducing activity corresponded well with microbial depth profiles; however, viable counts of neutrophilic or acid-tolerant Fe(III) reducers must have been underestimated based on the corresponding observed activity levels. Ferric iron reduction by chemolithotrophic acidophiles seemed to be of minor importance, so a lowering of pH values due to Fe(III) reducing activity is unlikely.     

Quantitative Separation of As(III) and As(V) from a Synthetic Water Solution Using Ion Exchange Columns in the Presence of Fe and Mn Ions

The quantitative separation of As(III) from a water sample containing As(III) and As(V) in the presence of Fe and Mn in an ion exchange resin (AG1 X8) column for the speciation of arsenic is described. Individual and combined effects of Fe and Mn on the separation of As(III) from the solution have been studied separately. In absence of Fe and Mn, the ratio between the As(T) concentration in the eluent and the As(III) concentration in the original sample has been found to be 0.9717 under optimum process conditions. The presence of Fe(II) in the water sample increased the As(T) concentration in the eluent whereas Mn(II) decreased it. Combined effects of Fe and Mn on the percentage increment in the eluent arsenic concentration have been expressed by additive and interactive models. The interactive model has been developed by a statistical software with a 95 % confidence level. In most of the cases the error on the determination of the As(III) concentration had a minimum when using the interactive model.     

Toxicity assessments of nanoscale zerovalent iron and its oxidation products in medaka (Oryzias latipes) fish

Iron-based nanotechnologies are increasingly used for environmental remediation; however, toxicologic impacts of iron nanoparticles on the aquatic ecosystem remain poorly understood. We treated larvae of medaka fish (Oryzias latipes) with thoroughly characterized solutions containing carboxymethyl cellulose (CMC)-stabilized nanoscale zerovalent iron (nZVI), aged nanoscale iron oxides (nFe-oxides) or ferrous ion (Fe[II]) for 12-14 days' aqueous exposure to assess the causal toxic effect(s) of iron NPs on the fish. With the CMC-nZVI solution, the dissolved oxygen level decreased, and a burst of reactive oxygen species (ROS) was generated as Fe(II) oxidized to ferric ion (Fe[III]); with the other two iron solutions, these parameters did not significantly change. CMC-nZVI and Fe(II) solutions caused acute lethally and sublethally toxic effects in medaka larvae, with nFe-oxide-containing solutions causing the least toxic effects. We discuss modes of toxic action of iron NPs and chronic toxic effects in terms of hypoxia, Fe(II) toxicity and ROS-mediated oxidative damage.     

Biogeochemistry of iron in an acidic lake

In this paper, the fate of iron in Lake Cristallina, an acidic lake in the Alps of Switzerland, is discussed. A simple conceptual model is developed in order to explain the observed diel variation in dissolved iron(II) concentration. Biotite weathering provides reduced iron that is oxidized and subsequently precipitated in the lake. The amorphous Fe(III)hydroxide (FeOOH xH₂O), found in the sediments of Lake Cristallina, is an Fe(II) oxidation product. This oxygenation reaction is most probably catalyzed by bacteria surfaces, as indicated by the relatively high estimated oxidation rate compared to the oxidation rate of the homogeneous oxidation of inorganic Fe(II) species at the ambient pH of Lake Cristallina (pH 5.4 at 4 °C) and by the scanning electron micrograph pictures. Under the influence of light, these amorphous iron(III)hydroxide phases are reductively dissolved. The net concentration of Fe(II) reflects the balance of the reductive dissolution and the oxidation/precipitation reactions and tends to parallel the light intensity, leading to a diurnal variation in the Fe(II) concentration. The rate of the photochemical reductive dissolution of Lake Cristallina iron(III)hydroxides is greatly enhanced in situ and in the laboratory by addition of oxalate to the lake water.     

Coprecipitation with Cu(II)‐4‐(2‐Pyridylazo)‐resorcinol for Separation and Preconcentration of Fe(III) and Ni(II) in Water and Food Samples

The coprecipitation method is widely used for the preconcentration of trace metal ions prior to their determination by flame atomic absorption spectrometry (FAAS). A simple and sensitive method based on coprecipitation of Fe(III) and Ni(II) ions with Cu(II)‐4‐(2‐pyridylazo)‐resorcinol was developed. The analytical parameters including pH, amount of copper (II), amount of reagent, sample volume, etc., were examined. It was found that the metal ions studied were quantitatively coprecipitated in the pH range of 5.0–6.5. The detection limits (DL) (n = 10, 3s/b) were found to be 0.68 µg L^?1 for Fe(III) and 0.43 µg L^?1 for Ni(II) and the relative standard deviations (RSD) were ≤4.0%. The proposed method was validated by the analysis of three certified reference materials (TMDA 54.4 fortified lake water, SRM 1568a rice flour, and GBW07605 tea) and recovery tests. The method was successfully applied to sea water, lake water, and various food samples.     

Growth history of hydrothermal chimneys at EPR 9-10°N: A structural and mineralogical study

Based on structural and mineralogical characteristics of four hydrothermal chimney samples collected by submersible Alvin, growth history and formation environment of hydrothermal chimney at EPR 9-10°N are established. It is shown that there occur two types of hydrothermal chimney with different deposition environments at EPR 9-10°N according to differences in their shape, structure and mineral assemblage: type I chimney forms in an environment with high temperature, low pH and strong reducing hydrothermal focus flow and type II chimney forms in a relatively low temperature, high pH and rich Zn hydrothermal environment. Growth of type I chimney begins with the formation of anhydrite. Subsequently deposition of Cu-Fe-Zn sulphide in various directions of chimneys decides the final structure of this type of chimney. According to observation and analysis of mineral assemblages, the formation process of type I chimney could be divided into three stages from early, middle to late. Changes of temperature and major chemical reaction type in the process of hydrothermal chimney formation are also deduced. Different from type I chimney, quenching crystalline of pyrite and/or crystalline of sphalerite provide the growth foundation of type II chimney in the early stage of chimney forma-tion.     

武汉九峰地震台超导重力仪观测分析研究

连续重力观测和GPS的技术结合能够监测到物质迁移和地壳垂直形变之间的量化关系.和相对重力测量以及绝对重力测量技术相比,其避免了时间分辨率和观测精度低,无法精细描述观测周期内的物质迁移过程问题.本文利用武汉九峰地震台超导重力仪SGC053超过13000 h连续重力观测数据;同址观测的绝对重力仪观测结果;气压数据;周边GPS观测结果;GRACE卫星的时变重力场;全球水储量模型等资料,采用同址观测技术、调和分析法、相关分析方法在扣除九峰地震台潮汐、气压、极移和仪器漂移的基础上,利用重力残差时间序列和GPS垂直位移研究物质迁移和地壳垂直形变之间的量化关系.结果表明:在改正连续重力观测数据的潮汐、气压、极移的影响后,不仅准确观测到2009年的夏秋两季由于水负荷引起的约(6~8)×10^-8m·s^-2短期的重力变化.而且在扣除2.18×10^-8(m·s^-2)/a仪器漂移和水负荷的影响后,验证了本地区长短趋势垂直形变和重力变化之间具有一致的负相关性规律.同时长趋势表明该地区地壳处于下沉,重力处于增大过程,增加速率约为1.79×10^-8(m·s^-2)/a.武汉地区重力梯度关系约为-354×10^-8(m·s^-2)/m.     

Release of Chromium from Soils with Persulfate Chemical Oxidation

An important part of the evaluation of the effectiveness of persulfate in situ chemical oxidation (ISCO) for treating organic contaminants is to identify and understand its potential impact on metal co‐contaminants in the subsurface. Chromium is a redox‐sensitive and toxic metal the release of which poses considerable risk to human health. The objective of this study was to investigate the impact of persulfate chemical oxidation on the release of chromium from three soils varying in physical‐chemical properties. Soils were treated with unactivated and activated persulfate [activated with Fe(II), Fe(II)‐EDTA, and alkaline pH] at two different concentrations (i.e., 41 mM and 2.1 mM persulfate) for 48 h and 6 months and were analyzed for release of chromium. Results show that release of chromium with persulfate chemical oxidation depends on the soil type and the activation method. Sandy soil with low oxidant demand released more chromium compared to soils with high oxidant demand. More chromium was released with alkaline pH activation. Alkaline pH and high Eh conditions favor oxidation of Cr(III) to Cr(VI), which is the main mechanism of release of chromium with persulfate chemical oxidation. Unactivated and Fe(II)‐activated persulfate decreased pH and at low pH in absence of EDTA chromium release is not a concern. These results indicate that chromium release can be anticipated based on the given site and treatment conditions, and ISCO system can be designed to minimize potential chromium release when treating soils and groundwater contaminated with both organic and metal contaminants.     

Treatment of Arsenic Contaminated Groundwater Using Calcium Impregnated Granular Activated Carbon in a Batch Reactor: Optimization of Process Parameters

This paper is an experimental investigation into the removal of arsenic species from simulated groundwater by adsorption onto Ca²⁺ impregnated granular activated carbon (GAC‐Ca) in the presence of impurities like Fe and Mn. The effects of adsorbent concentration, pH and temperature on the percentage removal of total arsenic (As(T)), As(III) and As(V) have been discussed. Under the experimental conditions, the optimum adsorbent concentration of GAC‐Ca was found to be 8 g/L with an agitation time of 24 h, which reduced As(T) concentration from 188 to 10 μg/L. Maximum removal of As(V) and As(III) was observed in a pH range of 7–11 and 9–11, respectively. Removal of all the above arsenic species decreased slightly with increasing temperature. The presence of Fe and Mn increased the adsorption of arsenic species. Under the experimental conditions at 30°C, the maximum percentage removals of As(T), As(III), As(V), Fe, and Mn were found to be ca. 94.3, 90.6, 98.0, 100 and 63%, respectively. It was also observed that amongst the various regenerating liquids used, a 5 N H₂SO₄ solution exhibited maximum regeneration (ca. 91%) of the spent GAC‐Ca.     

Sorption of Eu~(3+) onto nano-size silica-water interfaces

A large amount of nuclear wastes has been pro-duced due to nuclear weapon development and nuclear electricity generation. One possible resolution for the disposal of the nuclear wastes is to seal them in an underground repository, which requires detailed knowledge on the mobility, chemical behavior and immobilization of radionuclides in underground water. In addition, toxic heavy metals are extensively present in ground and underground water, how to immobilize and remedy these toxic heavy meta…     

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.     

KSS31M型海洋重力仪在海边静态观测的结果——兼与栾锡武先生商榷

本文介绍了在海边进行的为期32 d的KSS31M海洋重力仪静态观测结果,试验数据表明：KSS31M海洋重力仪可以清晰地记录重力固体潮理论值的变化,精度优于0.1×10-5 m·s-2（即常用的0.1 mGal）;潮汐海浪对重力仪观测数据产生了很大的影响,重力观测值表现出曲线变化特征,周期与海潮周期一致,变化幅度高达1.7×10-5 m·s-2;重力仪的月漂移小于1.7×10-5 m·s-2.     

Growth history of hydrothermal chimneys at EPR 9―10°N: A structural and mineralogical study

Based on structural and mineralogical characteristics of four hydrothermal chimney samples collected by submersible Alvin, growth history and formation environment of hydrothermal chimney at EPR 9―10°N are established. It is shown that there occur two types of hydrothermal chimney with different deposition environments at EPR 9―10°N according to differences in their shape, structure and mineral assemblage: type I chimney forms in an environment with high temperature, low pH and strong reducing hydrothermal focus flow and type II chimney forms in a relatively low temperature, high pH and rich Zn hydrothermal environment. Growth of type I chimney begins with the formation of anhydrite. Subsequently deposition of Cu-Fe-Zn sulphide in various directions of chimneys decides the final structure of this type of chimney. According to observation and analysis of mineral assemblages, the formation process of type I chimney could be divided into three stages from early, middle to late. Changes of temperature and major chemical reaction type in the process of hydrothermal chimney formation are also deduced. Different from type I chimney, quenching crystalline of pyrite and/or crystalline of sphalerite provide the growth foundation of type II chimney in the early stage of chimney formation.     

Determination of Cu,Fe, and Ni in Spices after Preconcentration on Diaion‐HP 20 Resin as Their Zincon Complexes

In this work, a new separation–preconcentration method was developed for the determination of trace amounts of Cu(II), Ni(II), and Fe(III) by flame atomic absorption spectrometry (FAAS). Analytes were complexed by using zincon (2‐[2‐[alpha(2‐hydroxy‐5‐sulfophenylazo) benzylidene] hydrazino] benzoic acid sodium salt). The analyte ions were quantitatively adsorbed on a Diaion HP‐20 resin at pH 5. The retained metal ions on the resin were eluted by acetone. The analytical parameters such as pH of the sample, eluent type and volume, sample volume, and flow rates of the solution and the eluent were investigated. The influences of concomitant ions on the recoveries of the analytes were also examined. The instrumental detection limits for the analytes after application of the presented solid‐phase extraction procedure were in the range of 0.72–1.41 µg/L. The validation of the presented procedure was checked by analyzing certified reference material of SRM1515 Apple Leaves. The procedure was performed by analyzing some spice samples.     

对橄榄石相变形核率的估算

地幔主要矿物橄榄石［(Mg089Fe011)2SiO4］的相变与深源地震的解释以及俯冲带和周围地幔的相互作用相关. 其中,形核率和长大率是刻画其相变动力学的两个重要参数. 因为实验技术的原因,目前人们还没有基于实验数据给出橄榄石的形核率. 本文首先通过对挤碰物理图像的分析,对边界形核情形的相变动力学理论中表征挤碰程度的无量纲参数进行了修正. 在此基础上,根据已有的实验资料,首次对橄榄石相变的形核率进行了估计. 通过对形核率数据的拟合,可以得到形核率参数K0和γ1/3. 得到两个形核率参数的变化范围分别为K0=55×1021～87×1027s-1·m-2·K-1,γ1/3=0～020 J·m-2,最佳拟合值为：K0=69×1024s-1·m-2·K-1,γ1/3=016 J·m-2.