Dissolution of hausmannite (Mn3O4) in the presence of the trihydroxamate siderophore desferrioxamine B

That microbial siderophores may be mediators of Mn(III) biogeochemistry is suggested by recent studies showing that these well known Fe(III)-chelating ligands form very stable Mn(III) aqueous complexes. In this study, we examine the influence of desferrioxamine B (DFOB), a trihydroxamate siderophore, on the dissolution of hausmannite, a mixed valence Mn(II, III) oxide found in soils and freshwater sediments. Batch dissolution experiments were conducted both in the absence (pH 4-9) and in the presence of 100 μM DFOB (pH 5-9). In the absence of the ligand, there is a sharp decrease in the extent of proton-promoted dissolution above pH 5 and no appreciable dissolution above pH 8. The resulting aqueous Mn²⁺ activities were in good agreement with previous studies, indirectly supporting the accepted two-step mechanism involving the formation of manganite and reprecipitation of hausmannite. Desferrioxamine B enhanced hausmannite dissolution over the entire pH range investigated, both via the formation of a Mn(III) complex and through surface-catalyzed reductive dissolution. Above pH 8, non-reductive ligand-promoted dissolution dominated, whereas below pH 8, dissolution was non-stoichiometric with respect to DFOB. Concurrent proton-promoted, ligand-promoted, reductive, and induced dissolution was observed, with Mn release by either reductive or induced dissolution increasing linearly with decreasing pH. The fast kinetics of the DFOB-promoted dissolution of hausmannite, as compared to iron oxides, suggest that the siderophore-promoted dissolution of Mn(III)-bearing minerals may compete with the siderophore-promoted dissolution of Fe(III)-bearing minerals.     

Stability constants for the formation of lead chloride complexes as a function of temperature and ionic strength

The stability constants for the formation of lead (Pb²⁺) with chloride

     

Reactions of aqueous iron-DFOB (desferrioxamine B) complexes with flavin mononucleotide in the absence of strong iron(II) chelators

The mechanisms controlling microbial uptake of Fe^III-siderophore complexes and subsequent release of the metal for cellular use have been extensively studied in recent years. Reduction of the Fe^III center is believed to be necessary to labilize the coordinated Fe and facilitate exchange with cellular ligands. Previous studies report reduction of Fe^III-DFOB by various reducing agents in solutions containing Fe^II-chelating colorimetric agents for monitoring reaction progress, but the importance of these findings is unclear because the colorimetric agents themselves stabilize and enhance the reactions being monitored. This study examines the reduction of Fe^III complexes with DFOB (desferrioxamine B), a trihydroxamate siderophore, by the fully reduced hydroquinone form of flavin mononucleotide (FMN_HQ) in the absence of strong Fe^II-chelating agents, and Fe redox cycling in solutions containing DFOB and oxidized and reduced FMN species. Experimental results demonstrate that the rate and extent of Fe^III-DFOB reduction is strongly dependent on pH and FMN_HQ concentration. At pH ? 5, incomplete Fe^III reduction is observed due to two processes that re-oxidize Fe^II, namely, the autodecomposition of Fe^II-DFOB complexes (Fe^II oxidation is coupled with reduction of a protonated hydroxamate moiety) and reaction of Fe^II-DFOB complexes with the fully oxidized flavin mononucleotide product (FMN_OX). Chemical speciation-dependent kinetic models for the forward reduction process and both reverse Fe^II oxidation processes are developed, and coupling kinetic models for all three Fe redox processes leads to successful predictions of steady-state Fe^II concentrations observed over a range of pH conditions in the presence of excess FMN_HQ and FMN_OX. The observed redox reactions are also in agreement with thermodynamic constraints imposed by the combination of Fe^III/Fe^II and FMN_OX/FMN_HQ redox couples. Quantitative comparison between kinetic trends and changing Fe speciation reveals that FMN species react predominantly with diprotonated Fe^III-DFOB and Fe^II-DFOB complexes, where protonation of one hydroxamate group opens up two Fe coordination positions. This finding suggests that ternary complex formation (FMN-Fe-DFOB) facilitates inner-sphere electron transfer reactions between the flavin and Fe center.     

Kinetics of gypsum crystal growth from high ionic strength solutions: A case study of Dead Sea - seawater mixtures

Gypsum precipitation kinetics were examined from a wide range of chemical compositions , ionic strengths (4.75-10 m) and saturation state with respect to gypsum (1.16-1.74) in seeded batch experiments of mixtures of Ca²⁺-rich Dead Sea brine and -rich seawater. Despite the variability in the experimental solutions, a single general rate law was formulated to describe the heterogeneous precipitation rate of gypsum from these mixtures:

     

Evaluation of ionic strength and salinity of groundwaters: effect of the ionic composition

An improved method has been used for rapid determination of the ionic strength (I) and the salinity of Apulian groundwaters. The parameters required are the electrolytic conductivity (EC) and the total solute concentration (C_T) of the solutions. A simple empirical relation between I, EC and C_T is presented. The relation holds over a wide concentration and composition range. The combined use of C_T and of the ratio $\text{I}\text{C}{}_{\mathrm{T}}$ is shown to be effective in defining the salinity of groundwaters.     

Effects of temperature and ionic strength on the stabilities of the first and second fluoride complexes of yttrium and the rare earth elements

The stability constants for the formation of yttrium and rare earth elements (YREEs) with fluoride

(A1)     

用有限元强度折减法对某岸坡进行稳定性分析

有限元强度折减法是近年来岩土工程界广受关注的一种边坡稳定性分析方法。通过对岩体结构面强度折减,使斜坡达到不稳定状态,有限元计算不再收敛,此时的折减系数就是斜坡的安全稳定性系数。本文对某岸坡进行非线性有限元接触分析,计算表明,与传统刚体极限平衡法计算的稳定性系数很接近,而且有助于对滑体破坏的机制的理解。工程实例证明,有限元强度折减法在斜坡的稳定性评价中是切实可行的。     

强度指标对滑坡稳定性的影响

讨论了粘性土在不同固结状态下的强度指标变化规律,阐述了土的强度指标对滑坡稳定性的影响,以及雨水对滑坡崩塌滑动的诱发作用.     

基于强度折减弹塑性有限元法的抗滑桩加固边坡稳定性分析

以大型通用有限元分析软件ABAQUS作为平台,以迭代不收敛联合坡面特征点位移陡增作为抗滑桩加固边坡失稳判据,通过二次开发建立了能够自动搜索安全系数的抗滑桩加固边坡稳定性强度折减弹塑性有限元分析模型,结合典型算例的对比分析验证了这一判据的有效性。在此基础上,针对一实例边坡进行了稳定性数值分析。研究表明,对于抗滑桩加固边坡,以强度折减有限元法所确定的潜在滑动面,一般地比极限平衡法、极限分析上限方法要浅。     

Effect of collector, pH and ionic strength on the cationic flotation of kaolinite

The effect of amine collector type, pH, and ionic strength on the flotation behaviour of kaolinite was investigated in a series of laboratory batch flotation tests. In distilled water, ether diamine, a strong collector for silica, does not induce any flotation or only very weak flotation of kaolinite over a wide pH range from pH 3 to pH 10.5. Ether monoamine causes strong flotation of kaolinite in distilled water, especially in acidic solutions, but high dosages of the collector are required. Such observations are in contrast to the flotation behaviour of oxide minerals such as silica for which ether diamine shows stronger collecting power than ether monoamine. The pH dependence of kaolinite flotation is also opposite to that of oxides, with lower flotation recovery obtained at higher pH. In contrast to oxides, the flotation recovery of kaolinite increases with ionic strength. It was demonstrated that the enhanced flotation of kaolinite in NaCl solutions cannot be attributed to the frothing ability of NaCl or the intercalation of kaolinite by alkylamines. It is proposed that the screened zeta potential of kaolinite particles in a high ionic strength environment causes random aggregation of kaolinite particles exposing hydrophobic (001) silica plane in the presence of ether amines.     

Kinetics of silica oligomerization and nanocolloid formation as a function of pH and ionic strength at 25°C

Rate laws reported for the oligomerization of silica in natural environments are often contradictory, and the kinetics of monosilicic acid condensation are poorly understood. Here we present rate expressions that systematically describe the initial oligomerization of silica in terms of concentration of initial silica, ionic strength, and pH for a natural brine solution. The oligomerization of silica in dilute aqueous solutions was examined in solutions with ionic strengths of 0.01 and 0.24 molal, from pH 3 to 11, and with initial silica concentrations of 4.2, 12.5, and 20.8 millimolal (250, 750, and 1250 ppm SiO₂ respectively). The decrease in concentration of molybdate-reactive silica was monitored over time to determine the extent of oligomerization. This decrease in concentration of molybdate-reactive silica is accompanied by the appearance of a transient population of nanocolloidal particles with diameter ∼3 nm, as determined by atomic force microscopy (AFM). The oligomerization rate increases as pH approaches near neutral and as ionic strength increases. Early in the reaction where the concentration of molybdate-reactive silica, [SiO₂]_n≤3, is assumed to equal the concentration of monosilicic acid, [H₄SiO₄], the rate of change of monosilicic acid as a function of time, R, shows a fourth-order dependence:

R=k₄⁴[H₄SiO₄]     

金沙江金安桥水电站左岸B2崩塌体稳定性分析

对金安桥水电站左岸下游B2崩塌堆积体的工程特性进行研究,重点分析了凝灰岩夹层分布形式、分布特点,并提出了其对崩塌体的稳定性产生的影响以及可能导致崩塌体的破坏类型。运用2D有限元及极限平衡分析法分别对崩塌体的稳定性进行分析,由此得出：B2崩塌体按松动体底面和凝灰岩夹层组合滑动面的安全系数满足工程要求;地震作用对崩塌堆积体的影响较天然状态下大,根据极限平衡理论的最弱面搜索结果及计算结果,沿崩塌堆积体底面和凝灰岩夹层组合的整体性平面滑动破坏可能性存在。同时提出了对浸水后凝灰岩夹层特性进行研究及及时监控反馈分析的合理化建议。     

The effects of magnesium-to-calcium ratios in artificial seawater,at different ionic products,upon the induction time,and the mineralogy of calcium carbonate: a laboratory study

The effects of the Mg²⁺ ion concentration and the ionic products of carbonate upon the induction time for the onset of precipitation and the different mineralogies of calcium carbonates were studied. It was shown that Mg²⁺ ions delay the spontaneous precipitation of calcium carbonate from supersaturated solutions (e.g. seawater) with respect to calcium carbonate mineral to such an extent that only biogenic removal of skeletal calcium carbonate is possible from the open ocean. Low concentrations of magnesium ions in solution favor calcite formation while aragonite is formed at high magnesium concentrations. The mole% of MgCO₃ in magnesian calcite increases with the increase of (Mg²⁺) in solution and with the increase of (CO₃ ^2–) in the presence of (Mg²⁺) in solution.Therefore, one would expect that high Mg-calcite is formed in wormed coastal regions, where high temperature and or the increase of photosynthesis activities tend to expel CO₂ and increase supersaturation, and low-magnesian calcite is favored in meteoric-vadose environment where low concentration of magnesium ions or in burial environment where respiration and oxidation is high and decrease supersaturation.

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Zusammenfassung Die Wirkung der Mg²⁺-Ionenkonzentration und des Ionenprodukts von Karbonaten wurde in Abhängigkeit von der Induktionszeit für den Beginn der Ausfällung und der unterschiedlichen Mineralogie von Kalziumkarbonaten untersucht. Es konnte gezeigt werden, daß Mg²⁺-Ionen die spontane Ausfällung von Kalziumkarbonat aus einer übersättigten Lösung (z. B. Meerwasser), im Vergleich zu Kalziumkarbonatmineralien derart verzögert, daß nur noch der biogene Entzug für skelettbildendes Kalziumkarbonat aus dem Meerwasser möglich ist. Niedrige Konzentrationen von Magnesiumionen in der Lösung fördern die Kalzitbildung, während Aragonit bei hohen Magnesiumkonzentrationen gebildet wird. Die Mol% MgCO₃ in Magnesiumkalzit steigen mit der Zunahme von (Mg²⁺) und mit der Zunahme von (CO₃ ^2–) bei Gegenwart von (Mg²⁺) in der Lösung.Daher würde man erwarten, daß Hochmagnesiumkalzit in erwärmten Küstengebieten gebildet wird, wo hohe Temperaturen, und/oder die Zunahme der Photosyntheseaktivität dazu führen, daß CO₂ frei wird, und damit die Übersättigung ansteigen lassen. Niedrigmagnesiumkalzit wird bevorzugt in meteorische-vadosen Gebieten mit niedriger Magnesiumionenkonzentration oder in Versenkungsgebieten gebildet, wo die Respiration und die Oxidation hoch ist, bei sinkender Übersättigung.

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Résumé Une étude a été menée sur l'effet de la concentration en ions Mg²⁺ et des produits ioniques des carbonates sur le temps d'induction du début de la cristallisation et sur la nature minéralogique du carbonate de calcium formé. On a pû montrer que les ions Mg²⁺ retardent la précipitation spontanée du carbonate de Ca à partir de solutions sursaturées par rapport aux minéraux de CaCO₃ (par exemple l'eau de mer) et ce à un point tel que seule la précipitation biogénique du carbonate de Ca dans les squelettes est possible à partir de l'eau de mer. Les faibles concentrations en ions Mg²⁺ dans les solutions favorisent la formation de calcite, l'aragonite se formant pour des concentrations plus élevées. Le pourcentage molaire de MgCO₃ dans la calcite magnésienne augmente avec la teneur, dans la solution, de Mg²⁺ et de Co₃ ^2– enprésence de Mg²⁺.On présume donc que la calcite riche en Mg se forme dans des milieux côtiers chauds dans lesquels la haute température et/ou la forte activité photosynthétique provoquent la libération de CO₂, ce qui augmente la sursaturation. La calcite pauvre en Mg se forme de préférence dans des milieux météoriques vadoses à faible concentration en ions Mg²⁺ ou dans des milieux d'enfouissement où la respiration et l'oxydation importantes abaissent le degré de sursaturation.

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Mg²⁺ . , , (.: ), , ₃ . , . , , ₃ MgCO₃ . , , ₂ . . . , , , .

     

Adsorption of chromate on variable charge soils as influenced by ionic strength

The adsorption behavior of chromate on two variable charge soils (Oxisol and Ultisol) was investigated through batch experiments at different ionic strengths and pH values. The adsorption of chromate on the variable charge soils was found to be strongly dependent on the pH of the soil solutions. A characteristic pH was observed, which corresponds to the intersection of the chromate adsorption—pH curves at different ionic strengths. The characteristic pH values are 5.50 for Oxisol and 5.04 for Ultisol, close to the point of zero salt effect (PZSE) of these soils. The zeta potentials measured for these soils provide the evidences to support the interpretation of the effect of ionic strength on the adsorption of chromate on these variable charge soils. The adsorption behavior of chromate was interpreted by a schematic representation of chromate distribution at increasing ionic strength. The chromate desorption–pH curves were also found to intersect at pH of 5.15 and 4.89 for the Oxisol and Ultisol, respectively. It is considered that chromate adsorption by the variable charge soils was mainly determined by the electrostatic potential on the adsorption plane, which was controlled by the ionic strength of the soil solutions.     

Effect of groundwater pH and ionic strength on strontium sorption in aquifer sediments: Implications for Sr mobility at contaminated nuclear sites

Strontium-90 is a beta emitting radionuclide produced during nuclear fission, and is a problem contaminant at many nuclear facilities. Transport of ⁹⁰Sr in groundwaters is primarily controlled by sorption reactions with aquifer sediments. The extent of sorption is controlled by the geochemistry of the groundwater and sediment mineralogy. Here, batch sorption experiments were used to examine the sorption behaviour of ⁹⁰Sr in sediment–water systems representative of the UK Sellafield nuclear site based on groundwater and contaminant fluid compositions. In experiments with low ionic strength groundwaters (<0.01 mol L⁻¹), pH variation is the main control on sorption. The sorption edge for ⁹⁰Sr was observed between pH 4 and 6 with maximum sorption occurring (K_d ∼ 10³ L kg⁻¹) at pH 6–8. At ionic strengths above 10 mmol L⁻¹, and at pH values between 6 and 8, cation exchange processes reduced ⁹⁰Sr uptake to the sediment. This exchange process explains the lower ⁹⁰Sr sorption (K_d ∼ 40 L kg⁻¹) in the presence of artificial Magnox tank liquor (IS = 29 mmol L⁻¹). Strontium K-edge EXAFS spectra collected from sediments incubated with Sr²⁺ in either HCO₃-buffered groundwater or artificial Magnox tank liquor, revealed a coordination environment of ∼9 O atoms at 2.58–2.61 Å after 10 days. This is equivalent to the Sr²⁺ hydration sphere for the aqueous ion and indicates that Sr occurs primarily in outer sphere sorption complexes. No change was observed in the Sr sorption environment with EXAFS analysis after 365 days incubation. Sequential extractions performed on sediments after 365 days also found that ∼80% of solid associated ⁹⁰Sr was exchangeable with 1 M MgCl₂ in all experiments. These results suggest that over long periods, ⁹⁰Sr in contaminated sediments will remain primarily in weakly bound surface complexes. Therefore, if groundwater ionic strength increases (e.g. by saline intrusion related to sea level rise or by design during site remediation) then substantial remobilisation of ⁹⁰Sr is to be expected.     

Neotethys seawater chemistry and temperature at the dawn of the end Permian mass extinction

The end of the Permian was a time of great death and massive upheaval in the biosphere, atmosphere and hydrosphere. Over the last decades, many causes have been suggested to be responsible for that catastrophe such as global warming, anoxia and acidification. The Gyanyima limestone block was an open ocean seamount in the southern Neotethys at subtropical latitude, and it affords us insight into open-ocean oceanographic changes during the end of the Permian. After careful screening using multiple tests, we reconstructed carbonate/seawater curves from the geochemical data stored in pristine brachiopod shell archives from the shallow water limestone of the Changhsingian Gyanyima Formation of Tibet. The reconstructed strontium isotope curve and data for the late Changhsingian are relatively invariant about 0.707013, but in the upper part of the succession the values become more radiogenic climaxing at about 0.707244. The ⁸⁷Sr/⁸⁶Sr curve and trend are similar to those observed for the Upper Permian succession in northern Italy, but dissimilar (less radiogenic) to whole rock results from Austria, Iran, China and Spitsbergen. The Ce/Ce* anomaly results ranging from 0.310 to 0.577 for the brachiopods and from 0.237 to 0.655 for the coeval whole rock before the event, and of 0.276 for whole rock during the extinction event, suggest normal redox conditions. These Ce* values are typical of normal open-ocean oxic water quality conditions observed in modern and other ancient counterparts. The biota and Ce* information clearly discounts global anoxia as a primary cause for the end-Permian biotic crisis. Carbon isotopes from brachiopod shells and whole rock are relatively invariant for most of the latest Permian interval, which is in stark contrast to the distinct negative carbon isotope excursion observed near and about the event. Estimates of seawater temperature at shallow depth fluctuated from 22.2 to 29.0 °C up to unit 8–2, and then gradually rise from 29.7 °C in unit 8–13 to values exceeding 35 °C at a stratigraphic level about 120 ky before the Permian–Triassic boundary, and just before the onset of the extinction interval. This dramatic increase in seawater temperature has been observed in global successions from tropical to mid latitude and from restricted to open ocean localities (e.g., northern Italy, Iran). The brachiopod archive and its geochemical proxies from Tibet support the paradigm that global warming must have been an important factor of the biotic crisis for the terrestrial and marine faunas and floras of the late Paleozoic world.     

The ionic strength dependence of lead (II) carbonate complexation in perchlorate media

Lead speciation in many aqueous geochemical systems is dominated by carbonate complexation. However, direct observations of Pb²⁺ complexation by carbonate ions are few in number. This work represents the first investigation of the equilibrium over a range of ionic strength. Through spectrophotometric observations of formation at 25 °C in NaHCO₃-NaClO₄ solutions, formation constants of the form were determined between 0.001 and 5.0 molal ionic strength. Formation constant results were well represented by the equation:

     

考虑抗剪强度衰减特性的膨胀土边坡稳定性分析

针对传统膨胀土边坡稳定性分析中无法考虑膨胀土在降雨入渗过程中抗剪强度动态衰减的问题,本文开展了室内直剪试验,系统研究了干密度和含水量变化对膨胀土抗剪强度指标的影响;同时,以试验抗剪强度结果为参数,开展了基于强度折减法的膨胀土边坡稳定性分析,获得了抗剪强度动态衰减过程中边坡稳定性的变化规律。结果表明,含水量的增加和干密度降低会造成膨胀土黏聚力和内摩擦角的衰减,黏聚力衰减显著,内摩擦角衰减较少;膨胀土边坡稳定性主要受风化层土体含水量控制,随着膨胀土含水量的增加,膨胀土边坡逐渐由稳定状态演变为欠稳定状态;干密度对膨胀土边坡稳定性的影响则相对较小。