scholarly journals Laboratory study of spectral induced polarization responses of magnetite — Fe2+ redox reactions in porous media

Geophysics ◽  
2014 ◽  
Vol 79 (1) ◽  
pp. D21-D30 ◽  
Author(s):  
Christopher G. Hubbard ◽  
L. Jared West ◽  
Juan Diego Rodriguez-Blanco ◽  
Samuel Shaw
Keyword(s):  
Redox Reactions ◽  
Induced Polarization ◽  
Phase Response ◽  
Field Surveys ◽  
Spectral Induced Polarization ◽  
Reducing Conditions ◽  
Redox Active ◽  
Large Phase ◽  
Ph Range

Spectral induced polarization (SIP) phase anomalies in field surveys at contaminated sites have previously been shown to correlate with the occurrence of chemically reducing conditions and/or semiconductive minerals, but the reasons for this are not fully understood. We report a systematic laboratory investigation of the role of the semiconductive mineral magnetite and its interaction with redox-active versus redox-inactive ions in producing such phase anomalies. The SIP responses of quartz sand with 5% magnetite in solutions containing redox-inactive [Formula: see text] and [Formula: see text] versus redox-active [Formula: see text] were measured across the pH ranges corresponding to adsorption of these metals to magnetite. With redox inactive ions [Formula: see text] and [Formula: see text], SIP phase response showed no changes across the pH range 4–10, corresponding to their adsorption, showing [Formula: see text] anomalies peaking at [Formula: see text]–74 Hz. These large phase anomalies are probably caused by polarization of the magnetite-solution interfaces. With the redox-active ion [Formula: see text], frequency of peak phase response decreased progressively from [Formula: see text] to [Formula: see text] as effluent pH increased from four to seven, corresponding to progressive adsorption of [Formula: see text] to the magnetite surface. The latter frequency (3 Hz) corresponds approximately with those of phase anomalies detected in field surveys reported elsewhere. We conclude that pH sensitivity arises from redox reactions between [Formula: see text] and magnetite surfaces, with transfer of electrical charge through the bulk mineral, as reported in other laboratory investigations. Our results confirm that SIP measurements are sensitive to redox reactions involving charge transfers between adsorbed ions and semiconductive minerals. Phase anomalies seen in field surveys of groundwater contamination and biostimulation may therefore be indicative of iron-reducing conditions, when semiconductive iron minerals such as magnetite are present.

Induced‐polarization response of zeolitic conglomerate and carbonaceous siltstone

Geophysics ◽  
1982 ◽  
Vol 47 (1) ◽  
pp. 71-88 ◽  
Author(s):  
P. H. Nelson ◽  
W. H. Hansen ◽  
M. J. Sweeney
Keyword(s):  
Electrical Response ◽  
Induced Polarization ◽  
Phase Response ◽  
Electrical Measurements ◽  
Intimate Contact ◽  
Thin Sections ◽  
Field Surveys ◽  
Core Samples ◽  
Rock Types ◽  
Geologic Materials

Three case studies investigating induced‐polarization (IP) responses of a zeolite‐bearing conglomerate and of two carbonaceous siltstones are presented. The IP response of these noneconomic geologic materials can either mask or mimic the response from sulfide mineralization which is sought by electrical field surveys. The nonsulfide rock types which produced unusually high responses on IP field surveys were sampled by core drilling for chemical, mineralogical, and electrical laboratory study. The electrical response of core samples was measured in a four‐electrode sample holder over the 0.03–1000 Hz range. Geologic description of the core, petrographic examination of thin sections, mineral identification by x‐ray diffraction (XRD), and chemical analysis of samples supplemented the electrical measurements. A surface phase response of 20 mrad was obtained from field surveys over the Gila conglomerate at an Arizona location. Core samples of the Gila were examined in thin section, and clast surfaces were found to be coated with a thin layer of zeolites. These zeolites project into pore spaces in the conglomerate, and thus are in intimate contact with formation waters. A series of laboratory experiments suggests that zeolites cause most of the observed IP response. Phase responses as high as 100 mrad were measured with field surveys over siltstone and limestone sequences in western Nevada. Samples recovered from the Luning and Gabbs‐Sunrise formations include siltstones containing small amounts of amorphous carbon. These siltstones are very conductive electrically, and the high‐phase response is attributed to polarization of the carbon‐pore water interface. Low porosity in these carbonaceous siltstones enhances the phase response.

Electrochemical spectral induced polarization modeling of artificial sulfide-sand mixtures

Geophysics ◽  
2014 ◽  
Vol 79 (6) ◽  
pp. EN91-EN106 ◽  
Author(s):  
Edmundo Placencia-Gómez ◽  
Lee D. Slater
Keyword(s):  
Mine Drainage ◽  
Mine Waste ◽  
Induced Polarization ◽  
Phase Response ◽  
Silica Sand ◽  
Model Parameters ◽  
Oxidation Degree ◽  
Spectral Induced Polarization ◽  
Current Densities ◽  
The Stability

We examined the sensitivity of the electrochemical spectral induced polarization (SIP) model developed by Wong to the oxidation extent of pyrite and pyrrhotite minerals disseminated in silica sand. The sensitivity of this model to the oxidation of sulfide minerals was mainly related to the model parameters defining the ratio of the active to the inactive passive ions [Formula: see text] dissolved in the pore water, and the variation of the current reaction parameters [Formula: see text] and [Formula: see text]. The increase in these parameters as well as in the associated exchange current densities, [Formula: see text] and [Formula: see text] was consistent with an increase in the activation of the charge transfer at the metal-electrolyte interface, resulting in the decrease in polarization of such an interface, which was reflected by a decrease in the SIP phase response as previously argued by Wong. Under this premise, the model described fairly well measurements below 500 Hz from a laboratory experiment, being consistent with the depletion of the SIP phase response associated with the oxidation degree promoted on the disseminate sulfides analyzed here. This suggested that electrochemical modeling of SIP measurements can provide information to assess the oxidation state of sulfides and also to infer the formation of passivating layers coating the metal minerals during oxidation-dissolution processes. Our results suggested a possible alternative for the monitoring of mine waste deposits producing acid mine drainage and the stability of sequestered harmful metals during remedial treatments by means of the SIP method.

scholarly journals Electron Inventory of the Iron-Sulfur Scaffold Complex HypCD Essential in [NiFe]-Hydrogenase Cofactor Assembly

2021 ◽  
Author(s):  
Sven T. Stripp ◽  
Jonathan Oltmanns ◽  
Christina S. Müller ◽  
David Ehrenberg ◽  
Ramona Schlesinger ◽  
...  
Keyword(s):  
Redox Reactions ◽  
Expression And Purification ◽  
Metal Centers ◽  
E Coli ◽  
Iron Sulfur ◽  
Reducing Conditions ◽  
Redox Active ◽  
Purification System ◽  
Efficient Expression

The [4Fe-4S] cluster containing scaffold complex HypCD is the central construction site for the assembly of the [Fe](CN)2CO cofactor precursor of [NiFe]-hydrogenase. While the importance of the HypCD complex is well established, not much is known about the mechanism by which the CN– and CO ligands are transferred and attached to the iron ion. We report an efficient expression and purification system producing the HypCD complex from E. coli with complete metal content. This enabled in-depth spectroscopic characterizations. The results obtained by EPR and Mössbauer spectroscopy demonstrate that the [Fe](CN)2CO cofactor and the [4Fe-4S] cluster of the HypCD complex are redox active. The data indicate a potential-dependent interconversion of the [Fe]2+/3+ and [4Fe-4S]2+/+ couple, respectively. Moreover, ATR FTIR spectroscopy reveals potential-dependent disulfide formation, which hints at an electron confurcation step between the metal centers. MicroScale thermophoresis indicates preferable binding between the HypCD complex and its in vivo interaction partner HypE under reducing conditions. Together, these results provide comprehensive evidence for an electron inventory fit to drive multi-electron redox reactions required for the assembly of the CN– and CO ligands on the scaffold complex HypCD.

Anti-toxicant Properties of Saffron and Relevance to Protection from Toxins and Drugs

2020 ◽  
Vol 16 (3) ◽  
pp. 265-283
Author(s):  
Kyriaki Hatziagapiou ◽  
George I. Lambrou
Keyword(s):  
Redox Reactions ◽  
Case Reports ◽  
Meta Analysis ◽  
Reactive Oxygen ◽  
Crocus Sativus ◽  
Protective Effects ◽  
Nitrogen Species ◽  
Eligibility Criteria ◽  
Crocus Sativus L

Background: Reactive oxygen species and reactive nitrogen species, which are collectively called reactive oxygen nitrogen species, are inevitable by-products of cellular metabolic redox reactions, such as oxidative phosphorylation in the mitochondrial respiratory chain, phagocytosis, reactions of biotransformation of exogenous and endogenous substrata in endoplasmic reticulum, eicosanoid synthesis, and redox reactions in the presence of metal with variable valence. Among medicinal plants there is a growing interest in Crocus sativus L. It is a perennial, stemless herb, belonging to Iridaceae family, cultivated in various countries such as Greece, Italy, Spain, Israel, Morocco, Turkey, Iran, India, China, Egypt and Mexico. Objective: The present study aims to address the anti-toxicant role of Crocus sativus L. in the cases of toxin and drug toxification. Materials and Methods: An electronic literature search was conducted by the two authors from 1993 to August 2017. Original articles and systematic reviews (with or without meta-analysis), as well as case reports were selected. Titles and abstracts of papers were screened by a third reviewer to determine whether they met the eligibility criteria, and full texts of the selected articles were retrieved. Results: The authors focused on literature concerning the role of Crocus Sativus L. as an anti-toxicant agent. Literature review showed that Saffron is a potent anti-toxicant agent with a plethora of applications ranging from anti-oxidant properties, to chemotherapy protective effects. Conclusion: Literature findings represented in current review herald promising results for using Crocus Sativus L. and/or its active constituents as anti-toxicant, chemotherapy-induced protection and toxin protection.

Kinetics and mechanism of the reaction between oxidized cytochrome c and ascorbic acid

1991 ◽  
Vol 56 (2) ◽  
pp. 478-490 ◽  
Author(s):  
Joaquin F. Perez-Benito ◽  
Conchita Arias
Keyword(s):  
Ascorbic Acid ◽  
Cytochrome C ◽  
Redox Reactions ◽  
Arrhenius Equation ◽  
Horse Heart Cytochrome ◽  
First Order ◽  
Acidic Form ◽  
Ph Range ◽  
Horse Heart Cytochrome C ◽  
Mechanism Of The Reaction

The reaction between horse-heart cytochrome c and ascorbic acid has been investigated in the pH range 5.5 – 7.1 and at 10.0 – 25.0 °C. The rate shows a first-order dependence on the concentration of cytochrome c, it increases in a non-linear way as the concentration of ascorbic acid increases, it increases markedly with increasing pH and, provided that the ionic strength of the medium is high enough, it fulfills the Arrhenius equation. The apparent activation energy increases as the pH of the solution increases. The results have been explained by means of a mechanism that includes the existence of an equilibrium between two forms (acidic and basic) of oxidized cytochrome c: cyt-H+ -Fe3+ + OH- cyt -Fe3+ + H2O, whose equilibrium constant is (6.7 ± 1.4). 108 at 25.0 °C, the acidic form being more reducible than the basic one. It is suggested that there is a linkage of hydrogenascorbate ion to both forms of cytochrome c previous to the redox reactions. Two possibilities for the oxidant-reductant linkage (binding and adsorption) are discussed in detail.

scholarly journals Spectral Induced Polarization Survey with Distributed Array System for Mineral Exploration: Case Study in Saudi Arabia

Minerals ◽  
2020 ◽  
Vol 10 (9) ◽  
pp. 769 ◽  
Author(s):  
Fouzan A. Alfouzan ◽  
Abdulrahman M. Alotaibi ◽  
Leif H. Cox ◽  
Michael S. Zhdanov
Keyword(s):  
Effective Medium Theory ◽  
Coupling Effect ◽  
Pilot Project ◽  
Drill Hole ◽  
Induced Polarization ◽  
Effective Medium ◽  
Inductive Coupling ◽  
Geothermal Resources ◽  
Spectral Induced Polarization ◽  
Distributed Array

The Saudi Arabian Glass Earth Pilot Project is a geophysical exploration program to explore the upper crust of the Kingdom for minerals, groundwater, and geothermal resources as well as strictly academic investigations. The project began with over 8000 km2 of green-field area. Airborne geophysics including electromagnetic (EM), magnetics, and gravity were used to develop several high priority targets for ground follow-up. Based on the results of airborne survey, a spectral induced polarization (SIP) survey was completed over one of the prospective targets. The field data were collected with a distributed array system, which has the potential for strong inductive coupling. This was examined in a synthetic study, and it was determined that with the geometries and conductivities in the field survey, the inductive coupling effect may be visible in the data. In this study, we also confirmed that time domain is vastly superior to frequency domain for avoiding inductive coupling, that measuring decays from 50 ms to 2 s allow discrimination of time constants from 1 ms to 5 s, and the relaxation parameter C is strongly coupled to intrinsic chargeability. We developed a method to fully include all 3D EM effects in the inversion of induced polarization (IP) data. The field SIP data were inverted using the generalized effective-medium theory of induced polarization (GEMTIP) in conjunction with an integral equation-based modeling and inversion methods. These methods can replicate all inductive coupling and EM effects, which removes one significant barrier to inversion of large bandwidth spectral IP data. The results of this inversion were interpreted and compared with results of drill hole set up in the survey area. The drill hole intersected significant mineralization which is currently being further investigated. The project can be considered a technical success, validating the methods and effective-medium inversion technique used for the project.

Ozone-induced acute phase response in lung versus liver: the role of adrenal-derived stress hormones

2020 ◽  
pp. 1-14
Author(s):  
Devin I. Alewel ◽  
Andres R. Henriquez ◽  
Catherine H. Colonna ◽  
Samantha J. Snow ◽  
Mette C. Schladweiler ◽  
...  
Keyword(s):  
Acute Phase ◽  
Acute Phase Response ◽  
Stress Hormones ◽  
Phase Response

scholarly journals The Role of the Disulfide Bridge in the Copper (II) Binding by the Cyclic His4-Peptide

2021 ◽  
Vol 22 (12) ◽  
pp. 6458
Author(s):  
Aleksandra Pieniężna ◽  
Weronika Witak ◽  
Aneta Szymańska ◽  
Justyna Brasuń
Keyword(s):  
Metal Ions ◽  
Coordination Mode ◽  
Transition Metal Ions ◽  
Disulfide Bridge ◽  
Chain Flexibility ◽  
Vis Spectroscopy ◽  
Ph Range ◽  
Cd Studies ◽  
Metal Ratios

In this paper, we present studies on the influence of the disulfide bridge on the copper (II) ions’ binding abilities by the cyclic His4-peptide. The studied ligand HKHPHRHC-S-S-C consists of nine amino acids. The cyclic structure was obtained through a disulfide bridge between two cysteinyl groups. Moreover, this peptide is characterized by the presence of four His residues in the sequence, which makes it an interesting ligand for transition metal ions. The potentiometric and spectroscopic (UV-Vis spectroscopy and circular dichroism spectroscopy (CD)) studies were carried out in various molar ligand to metal ratios: 2:1, 1:1, and 1:2, in the pH range of 2.5–11 at 25 °C. The results showed that the cyclic His4-peptide promotes dinuclear complexes in each of these systems and forms the final dinuclear species with the {NIm, 3N-amide}{NIm, 3N-amide} coordination mode. The obtained data shows that cyclization by the formation of the disulfide bond has an impact on the peptide chain flexibility and appearance of additional potential donors for metal ions and influences the copper (II) ions’ coordination.

scholarly journals The Unusual Role of Pro in Cu(II) Binding by His2-Cyclopentapeptide

2021 ◽  
Vol 22 (12) ◽  
pp. 6628
Author(s):  
Aleksandra Pieniężna ◽  
Aleksandra Kotynia ◽  
Justyna Brasuń
Keyword(s):  
Amino Acid ◽  
Potentiometric Titration ◽  
Amino Acid Residue ◽  
Strong Impact ◽  
Mononuclear Complexes ◽  
Study Results ◽  
Metal Ratio ◽  
Ph Range ◽  
L1 And L2

In this paper, we present findings from studying the interaction of copper(II) ions with the His2-cyclopentapeptide and the role of proline used for the purpose of potentiometric titration and UV-Vis, CD and EPR spectroscopic measurements. Experiments of two homodetic peptides differing by one amino acid residue were conducted for a ligand to metal ratio of 1:1 in the pH range 2.5–11.0. The presented studies reveal that peptides form only mononuclear complexes, and the CuH2L complex appears in the system first (for both L1 and L2). Study results show that the presence of Pro influences the structure of formed complexes and their stabilities and has a strong impact on the efficiency of copper(II) coordination.

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