Removal of phosphate from aqueous solutions and sewage using natural and surface modified coir pith.

PubMed

Krishnan, K Anoop; Haridas, Ajit

2008-04-01

Iron impregnated coir pith (CP-Fe-I) can be effectively used for the removal of phosphate from aqueous streams and sewage. Iron impregnation on natural coir pith was carried out by drop by drop addition method. The effect of various factors such as pH, initial concentration of phosphate, contact time and adsorbent dose on phosphate adsorption was studied by batch technique. The pH at 3.0 favored the maximum adsorption of phosphate from aqueous solutions. The effect of pH on phosphate adsorption was explained by pH(zpc), phosphate speciation in solution and affinity of anions towards the adsorbent sites. A comparative study of the adsorption of phosphate using CP-Fe-I and CP (coir pith) was made and results show that the former one is five to six times more effective than the latter. Kinetic studies revealed that the adsorption process followed a pseudo-second order kinetic model. Adsorption followed Langmuir isotherm model. Column studies were conducted to examine the utility of the investigated adsorbent for the removal of phosphate from continuously flowing aqueous solutions.

EFFECTS OF IRON CONTENT IN COAL COMBUSTION FLY ASHES ON SPECIATION OF MERCURY

EPA Science Inventory

The paper discusses the effects of iron content in coal combustion fly ashes on speciation of mercury. (NOTE: The chemical form of mercury species in combustion flue gases is an important influence on the control of mercury emissions from coal combustion). The study focused on th...

Chemically and geographically distinct solid-phase iron pools in the Southern Ocean.

PubMed

von der Heyden, B P; Roychoudhury, A N; Mtshali, T N; Tyliszczak, T; Myneni, S C B

2012-11-30

Iron is a limiting nutrient in many parts of the oceans, including the unproductive regions of the Southern Ocean. Although the dominant fraction of the marine iron pool occurs in the form of solid-phase particles, its chemical speciation and mineralogy are challenging to characterize on a regional scale. We describe a diverse array of iron particles, ranging from 20 to 700 nanometers in diameter, in the waters of the Southern Ocean euphotic zone. Distinct variations in the oxidation state and composition of these iron particles exist between the coasts of South Africa and Antarctica, with different iron pools occurring in different frontal zones. These speciation variations can result in solubility differences that may affect the production of bioavailable dissolved iron.

The variability in iron speciation in size fractionated residual oil fly ash particulate matter (ROFA PM).

PubMed

Pattanaik, Sidhartha; Huggins, Frank E; Huffman, Gerald P

2016-08-15

Ambient particulate matter (PM) containing iron can catalyze Fenton reaction leading to the production of reactive oxygen species in cells. It can also catalyze atmospheric redox reaction. These reactions are governed by the physicochemical characteristics of iron in ambient PM. As a surrogate for ambient PM, we prepared residual oil fly ash PM (ROFA PM) in a practical fire tube boiler firing residual oils with varying sulfur and ash contents. The ROFA particles were resolved into fine PM or PM2.5 (aerodynamic diameter (AD)<2.5μm) and coarse PM or PM2.5+ (AD between 2.5μm and 50μm). The iron speciation in PM2.5+ was ascertained using X-ray absorption spectroscopy and leaching method while that in PM2.5 was reported earlier. The results of both studies are compared to get an insight into the variability in the iron speciation in different size fractions. The results show the predominance of ferric sulfate, with a minor spinal ferrite in both PM (i.e. ZnxNi1-xFe2O4 in PM2.5, ZnFe2O4 in PM2.5+). The iron solubility in ROFA PM depends on its speciation, mode of incorporation of iron into particle's carbonaceous matrix, the grade and composition of oils, and pH of the medium. The soluble fraction of iron in PM is critical in assessing its interaction with the biological systems and its toxic potential. Copyright © 2016 Elsevier B.V. All rights reserved.

Modeling Non-Steady Isotopologue and Isotopomer Speciation and Fractionation during Denitrification in Soils

NASA Astrophysics Data System (ADS)

Maggi, F.; Riley, W. J.

2009-12-01

The composition and location of 15N atoms on N2O isotopomers and isotopologues during isotope speciation has been used to characterize soil biological N cycling and N2O surface emissions. Although there exist few experimental observations, no attempt has been made to model N2O isotopomer speciation. The mathematical treatment of biological kinetic reactions in isotopic applications normally makes use of first-order and quasi steady-state complexation assumptions without taking into account changes in enzyme concentration, reaction stoichiometry, and isotopologue and isotopomer speciation. When multiatomic isotopically-labeled reactants are used in a multi-molecurar reaction, these assumptions may fail since they always lead to a constant fractionation factor and cannot describe speciation of isotopologues and isotopomers. We have developed a mathematical framework that is capable of describing isotopologue and isotopmer speciation and fractionation under the assumption of non-steady complexation during biological kinetic reactions that overcome the limitations mentioned above. This framework was applied to a case study of non-steady (variable and inverse) isotopic effects observed during N2O production and consumption in soils. Our mathematical treatment has led to generalized kinetic equations which replicate experimental observations with high accuracy and help interpret non-steady isotopic effects and isotopologue and isotopomer speciation. The kinetic equations introduced and applied here have general validity in describing isotopic effects in any biochemical reactions by considering: changing enzyme concentrations, mass and isotope conservation, and reaction stoichiometry. The equations also describe speciation of any isotopologue and isotopomer product from any isotopologue and isotopmer reactant.

Modeling Anaerobic Soil Organic Carbon Decomposition in Arctic Polygon Tundra: Insights into Soil Geochemical Influences on Carbon Mineralization: Modeling Archive

DOE Data Explorer

Zheng, Jianqiu; Thornton, Peter; Painter, Scott; Gu, Baohua; Wullschleger, Stan; Graham, David

2018-06-13

This anaerobic carbon decomposition model is developed with explicit representation of fermentation, methanogenesis and iron reduction by combining three well-known modeling approaches developed in different disciplines. A pool-based model to represent upstream carbon transformations and replenishment of DOC pool, a thermodynamically-based model to calculate rate kinetics and biomass growth for methanogenesis and Fe(III) reduction, and a humic ion-binding model for aqueous phase speciation and pH calculation are implemented into the open source geochemical model PHREEQC (V3.0). Installation of PHREEQC is required to run this model.

The effects of metamorphism on iron mineralogy and the iron speciation redox proxy

NASA Astrophysics Data System (ADS)

Slotznick, Sarah P.; Eiler, John M.; Fischer, Woodward W.

2018-03-01

As the most abundant transition metal in the Earth's crust, iron is a key player in the planetary redox budget. Observations of iron minerals in the sedimentary record have been used to describe atmospheric and aqueous redox environments over the evolution of our planet; the most common method applied is iron speciation, a geochemical sequential extraction method in which proportions of different iron minerals are compared to calibrations from modern sediments to determine water-column redox state. Less is known about how this proxy records information through post-depositional processes, including diagenesis and metamorphism. To get insight into this, we examined how the iron mineral groups/pools (silicates, oxides, sulfides, etc.) and paleoredox proxy interpretations can be affected by known metamorphic processes. Well-known metamorphic reactions occurring in sub-chlorite to kyanite rocks are able to move iron between different iron pools along a range of proxy vectors, potentially affecting paleoredox results. To quantify the effect strength of these reactions, we examined mineralogical and geochemical data from two classic localities where Silurian-Devonian shales, sandstones, and carbonates deposited in a marine sedimentary basin with oxygenated seawater (based on global and local biological constraints) have been regionally metamorphosed from lower-greenschist facies to granulite facies: Waits River and Gile Mountain Formations, Vermont, USA and the Waterville and Sangerville-Vassalboro Formations, Maine, USA. Plotting iron speciation ratios determined for samples from these localities revealed apparent paleoredox conditions of the depositional water column spanning the entire range from oxic to ferruginous (anoxic) to euxinic (anoxic and sulfidic). Pyrrhotite formation in samples highlighted problems within the proxy as iron pool assignment required assumptions about metamorphic reactions and pyrrhotite's identification depended on the extraction techniques utilized. The presence of diagenetic iron carbonates in many samples severely affected the proxy even at low grade, engendering an interpretation of ferruginous conditions in all lithologies, but particularly in carbonate-bearing rocks. Increasing metamorphic grades transformed iron in carbonates into iron in silicate minerals, which when combined with a slight increase in the amount of pyrrhotite, drove the proxy toward more oxic and more euxinic conditions. Broad-classes of metamorphic reactions (e.g. decarbonation, silicate formation) occurred at distinct temperatures-pressures in carbonates versus siliciclastics, and could be either abrupt between metamorphic facies or more gradual in nature. Notably, these analyses highlighted the importance of trace iron in phases like calcite, which otherwise might not be included in iron-focused research i.e. ore-system petrogenesis, metamorphic evolution, or normative calculations of mineral abundance. The observations show that iron is mobile and reactive during diagenesis and metamorphism, and these post-depositional processes can readily overprint primary redox information held by iron speciation. However, in principle, additional mineralogical and petrographic approaches can be combined with iron speciation data to help untangle many of these post-depositional processes and arrive at more accurate estimates of paleoenvironmental redox conditions and processes, even for metamorphosed samples.

Kinetic model to explain the effect of ocean warming and acidification on the Fe(II) oxidation rate in oligotrophic and eutrophic natural waters

NASA Astrophysics Data System (ADS)

González-Dávila, M.; Samperio-Ramos, G.; Santana-Casiano, J. M.; Gonzallez, A. G.; Pérez-Almeida, N.

2016-12-01

The speciation of inorganic Fe(II) as a function of the pH and temperature have been modeled in order to elucidate the inorganic Fe(II) redox behavior over a wide range of scenarios of acidification and global warming of the upper ocean, as well as, changes due to natural ambient fluctuations of pH and temperature. In addition, a kinetic modeling approach has been carried out to elucidate the fractional contribution of most kinetically active Fe(II) species to the overall oxidation rate to improve our future and present knowledge with respect to redox iron chemistry in the marine systems. The kinetic model considers the interactions of Fe(II) with the major ions in seawater, including phosphate and silicate and the competition with copper with the ROS. The model has been applied to the experimental results in order to describe the effect of temperature and pH in the speciation of Fe(II) and to compute the fractional contribution of each Fe(II)-specie to the overall oxidation rate. The oxidation rates (kapp) of nanomolar levels of Fe(II) have been studied in seawater enriched with nutrients (SWEN) in air saturated conditions. The nutrient effect (nitrate, phosphate and silicate), on the oxidation of Fe(II), has been evaluated as a function of pH (7.2-8.2), temperature (5-35 ºC) and salinity (10-37.09). The oxidation of Fe(II) was faster in the presence of nutrient with the change in the Fe(II) oxidation rates (Δlogkapp) more intensive at higher temperatures over the entire pH range studied. From the model it can be observed that the inorganic speciation of Fe(II) is controlled largely by pH, either in SW or in SWEN. A greater presence of Fe-nutrient reactive species (FeH3SiO4+ and FePO4-) in SWEN at higher temperatures explained the changes in the oxidation process. The individual oxidation rates by oxygen, for the Fe(II) most kinetically active species (Fe2+, FeOH+, Fe(OH)2, FeCO3(OH)-, FeCO3, Fe(CO3)22-, FeH3SiO3+, FePO4-), were fitted as a function of the temperature.

Effects of iron on arsenic speciation and redox chemistry in acid mine water

USGS Publications Warehouse

Bednar, A.J.; Garbarino, J.R.; Ranville, J.F.; Wildeman, T.R.

2005-01-01

Concern about arsenic is increasing throughout the world, including areas of the United States. Elevated levels of arsenic above current drinking-water regulations in ground and surface water can be the result of purely natural phenomena, but often are due to anthropogenic activities, such as mining and agriculture. The current study correlates arsenic speciation in acid mine drainage and mining-influenced water with the important water-chemistry properties Eh, pH, and iron(III) concentration. The results show that arsenic speciation is generally in equilibrium with iron chemistry in low pH AMD, which is often not the case in other natural-water matrices. High pH mine waters and groundwater do not always hold to the redox predictions as well as low pH AMD samples. The oxidation and precipitation of oxyhydroxides deplete iron from some systems, and also affect arsenite and arsenate concentrations through sorption processes. ?? 2004 Elsevier B.V. All rights reserved.

Iron Speciation in the Subtropical Waters East of New Zealand using Multi Detection Window CLE-AdCSV Titrations.

NASA Astrophysics Data System (ADS)

Chandrasekhar, Anoop; Sander, Sylvia; Milnes, Angie; Boyd, Philip

2015-04-01

Iron plays a significant role in the ocean productivity as a micro nutrient that facilitates the growth of marine phytoplankton and microbes. The bioavailability of iron in the ocean depends on it speciation. Iron is bio available in its dissolved form and about 99.9% of dissolved iron in seawater is organically complexed with natural ligands. The competitive ligand equilibration - adsorptive cathodic stripping voltammetry (CLE-AdCSV) is the widely used technique to examine Fe speciation. The method has its own limitations. The analytical window employed in this technique has a distinct impact on Fe speciation results (Buck, Moffett et al. 2012). Recently, (Pizeta, Sander et al. in preparation) have shown that the accuracy of complexometric titrations improve if multiple analytical windows (MAW) are solved as a united dataset. Several programs are now available that enable this approach with the KMS (Kineteql.xls , Hudson 2014), which is based on an Excel application based on speciation calculation (Hudson, Rue et al. 2003, Sander, Hunter et al. 2011), being one of them. In the present work, the unified MAW data analysis method is applied to determine iron speciation by CLE-AdCSV with salicyl aldoxime (SA) (Abualhaija and van den Berg 2014) in real seawater samples from the Spring bloom FeCycle III voyage, which took place in an anticyclonic eddy in subtropical waters east of New Zealand in spring 2012. Two different analytical windows (5 and 15µM SA) were applied to samples from depth profiles taken during this cruise. The data obtained was analysed using the program KMS (Kineteql.xls). Most samples only returned one Fe-binding ligands class. Higher ligand concentrations were observed in the upper water column and the stability constants were above 22 (e.g. 22.25 ± 0.21 for station 63). Our results will be discussed in the context of microbial community distribution as well as other biogeochemical parameters. Abualhaija, M. M. and C. M. G. van den Berg (2014). "Chemical speciation of iron in seawater using catalytic cathodic stripping voltammetry with ligand competition against salicylaldoxime." Marine Chemistry 164(0): 60-74. Buck, K. N., J. Moffett, K. A. Barbeau, R. M. Bundy, Y. Kondo and J. Wu (2012). "The organic complexation of iron and copper: an intercomparison of competitive ligand exchange-adsorptive cathodic stripping voltammetry (CLE-ACSV) techniques " Limnology and Oceanography: Methods 10: 496-515. Hudson, R. J. M., E. L. Rue and K. W. Bruland (2003). "Modeling Complexometric Titrations of Natural Water Samples." Environ. Sci. Tech. 37: 1553-1562. Pizeta, I., S. G. Sander, O. Baars, K. Buck, R. Bundy, G. Carrasco, P. Croot, C. Garnier, L. Gerringa, M. Gledhill, K. Hirose, D. R. Hudson, Y. Kondo-Jacquot, L. Laglera, D. Omanovic, M. Rijkenberg, B. Twining and M. Wells (in preparation). "Intercomparison of estimating metal binding ligand parameters from simulated titration data using different fitting approaches." for Limnology and Oceanography: Methods. Sander, S. G., K. A. Hunter, H. Harms and M. Wells (2011). "Numerical approach to speciation and estimation of parameters used in modeling trace metal bioavailability." Environmental Science and Technology 45(15): 6388-6395.

Changes in iron, sulfur, and arsenic speciation associated with bacterial sulfate reduction in ferrihydrite-rich systems.

PubMed

Saalfield, Samantha L; Bostick, Benjamin C

2009-12-01

Biologically mediated redox processes have been shown to affect the mobility of iron oxide-bound arsenic in reducing aquifers. This work investigates how dissimilatory sulfate reduction and secondary iron reduction affect sulfur, iron, and arsenic speciation. Incubation experiments were conducted with As(III/V)-bearing ferrihydrite in carbonate-buffered artificial groundwater enriched with lactate (10 mM) and sulfate (0.08-10 mM) and inoculated with Desulfovibrio vulgaris (ATCC 7757, formerly D. desulfuricans), which reduces sulfate but not iron or arsenic. Sulfidization of ferrihydrite led to formation of magnetite, elemental sulfur, and trace iron sulfides. Observed reaction rates imply that the majority of sulfide is recycled to sulfate, promoting microbial sulfate reduction in low-sulfate systems. Despite dramatic changes in Fe and S speciation, and minimal formation of Fe or As sulfides, most As remained in the solid phase. Arsenic was not solubilized in As(V)-loaded incubations, which experienced slow As reduction by sulfide, whereas As(III)-loaded incubations showed limited and transient As release associated with iron remineralization. This suggests that As(III) production is critical to As release under reducing conditions, with sulfate reduction alone unlikely to release As. These data also suggest that bacterial reduction of As(V) is necessary for As sequestration in sulfides, even where sulfate reduction is active.

Chemistry of Marine Ligands and Siderophores

PubMed Central

Vraspir, Julia M.; Butler, Alison

2011-01-01

Marine microorganisms are presented with unique challenges to obtain essential metal ions required to survive and thrive in the ocean. The production of organic ligands to complex transition metal ions is one strategy to both facilitate uptake of specific metals, such as iron, and to mitigate the potential toxic effects of other metal ions, such as copper. A number of important trace metal ions are complexed by organic ligands in seawater, including iron, cobalt, nickel, copper, zinc, and cadmium, thus defining the speciation of these metal ions in the ocean. In the case of iron, siderophores have been identified and structurally characterized. Siderophores are low molecular weight iron-binding ligands produced by marine bacteria. Although progress has been made toward the identity of in situ iron-binding ligands, few compounds have been identified that coordinate the other trace metals. Deciphering the chemical structures and production stimuli of naturally produced organic ligands and the organisms they come from is fundamental to understanding metal speciation and bioavailability. The current evidence for marine ligands, with an emphasis on siderophores, and discussion of the importance and implications of metal-binding ligands in controlling metal speciation and cycling within the world’s oceans are presented. PMID:21141029

Quantification of trace elements and speciation of iron in atmospheric particulate matter

NASA Astrophysics Data System (ADS)

Upadhyay, Nabin

Trace metal species play important roles in atmospheric redox processes and in the generation of oxidants in cloud systems. The chemical impact of these elements on atmospheric and cloud chemistry is dependent on their occurrence, solubility and speciation. First, analytical protocols have been developed to determine trace elements in particulate matter samples collected for carbonaceous analysis. The validated novel protocols were applied to the determination of trace elements in particulate samples collected in the remote marine atmosphere and urban areas in Arizona to study air pollution issues. The second part of this work investigates on solubility and speciation in environmental samples. A detailed study on the impact of the nature and strength of buffer solutions on solubility and speciation of iron lead to a robust protocol, allowing for comparative measurements in matrices representative of cloud water conditions. Application of this protocol to samples from different environments showed low iron solubility (less than 1%) in dust-impacted events and higher solubility (5%) in anthropogenically impacted urban samples. In most cases, Fe(II) was the dominant oxidation state in the soluble fraction of iron. The analytical protocol was then applied to investigate iron processing by fogs. Field observations showed that only a small fraction (1%) of iron was scavenged by fog droplets for which each of the soluble and insoluble fraction were similar. A coarse time resolution limited detailed insights into redox cycling within fog system. Overall results suggested that the major iron species in the droplets was Fe(1I) (80% of soluble iron). Finally, the occurrence and sources of emerging organic pollutants in the urban atmosphere were investigated. Synthetic musk species are ubiquitous in the urban environment (less than 5 ng m-3) and investigations at wastewater treatment plants showed that wastewater aeration basins emit a substantial amount of these species to the atmosphere.

Hybrid biosorbents for removal of pollutants and remediation

NASA Astrophysics Data System (ADS)

Burlakovs, Juris; Klavins, Maris; Robalds, Artis; Ansone, Linda

2014-05-01

For remediation of soils and purification of polluted waters, wastewaters, biosorbents might be considered as prospective groups of materials. Amongst them peat have a special role due to low cost, biodegradability, high number of functional groups, well developed surface area and combination of hydrophilic/hydrophobic structural elements. Peat as sorbent have good application potential for removal of trace metals, and we have demonstrated peat sorption capacities, sorption kinetics, thermodynamics in respect to metals with different valencies - Tl(I), Cu(II), Cr(III). However, peat sorption capacity in respect to nonmetallic (anionic species) elements is low. Also peat mechanical properties do not support application in large scale column processes thereby, to expand peat application sphere, the approach of biomass based hybrid sorbents has been elaborated. The concept "hybrid sorbent" in understanding of biosorbent means natural, biomass based modified material, covered with another sorbent material, thus combining properties of both such as sorbent functionalities, surface properties etc. As the "covering layer" both inorganic substances, mineral phases (iron oxohydroxides, oxyappatite) and organic polymers (using graft polymerization) were used. The obtained sorbents were characterised by their spectral properties, surface area and elemental composition. The obtained hybrid sorbents were tested for sorption of compounds in anionic speciation forms, for example of arsenic, antimony, tellurium and phosphorous compounds in comparison with weakly basic anionites. The highest sorption capacity was observed when peat sorbents modified with iron compounds were used. Sorption of different arsenic speciation forms onto iron-modified peat sorbents was investigated as a function of pH and temperature. It was established that sorption capacity increases with a rise in temperature as the calculation of sorption process thermodynamic parameters indicates the spontaneity of sorption process and its endothermic nature. The recycling options of obtained compounds after their saturation with metal or non-metallic species are suggested.

A STUDY OF GAS-PHASE MERCURY SPECIATION USING DETAILED CHEMICAL KINETICS

EPA Science Inventory

Mercury (Hg) speciation in combustion-generated flue gas is modeled using a detailed chemical mechanism consisting of 60 reactions and 21 species. This speciation model accounts for chlorination and oxidation of key flue-gas components, including elemental mercury. Results indica...

Vivianite as an important iron phosphate precipitate in sewage treatment plants.

PubMed

Wilfert, P; Mandalidis, A; Dugulan, A I; Goubitz, K; Korving, L; Temmink, H; Witkamp, G J; Van Loosdrecht, M C M

2016-11-01

Iron is an important element for modern sewage treatment, inter alia to remove phosphorus from sewage. However, phosphorus recovery from iron phosphorus containing sewage sludge, without incineration, is not yet economical. We believe, increasing the knowledge about iron-phosphorus speciation in sewage sludge can help to identify new routes for phosphorus recovery. Surplus and digested sludge of two sewage treatment plants was investigated. The plants relied either solely on iron based phosphorus removal or on biological phosphorus removal supported by iron dosing. Mössbauer spectroscopy showed that vivianite and pyrite were the dominating iron compounds in the surplus and anaerobically digested sludge solids in both plants. Mössbauer spectroscopy and XRD suggested that vivianite bound phosphorus made up between 10 and 30% (in the plant relying mainly on biological removal) and between 40 and 50% of total phosphorus (in the plant that relies on iron based phosphorus removal). Furthermore, Mössbauer spectroscopy indicated that none of the samples contained a significant amount of Fe(III), even though aerated treatment stages existed and although besides Fe(II) also Fe(III) was dosed. We hypothesize that chemical/microbial Fe(III) reduction in the treatment lines is relatively quick and triggers vivianite formation. Once formed, vivianite may endure oxygenated treatment zones due to slow oxidation kinetics and due to oxygen diffusion limitations into sludge flocs. These results indicate that vivianite is the major iron phosphorus compound in sewage treatment plants with moderate iron dosing. We hypothesize that vivianite is dominating in most plants where iron is dosed for phosphorus removal which could offer new routes for phosphorus recovery. Copyright © 2016 Elsevier Ltd. All rights reserved.

Activation of Persulfate by Nanosized Zero-Valent Iron (NZVI): Mechanisms and Transformation Products of NZVI.

PubMed

Kim, Cheolyong; Ahn, Jun-Young; Kim, Tae Yoo; Shin, Won Sik; Hwang, Inseong

2018-03-20

The mechanisms involved in the activation of persulfate by nanosized zero-valent iron (NZVI) were elucidated and the NZVI transformation products identified. Two distinct reaction stages, in terms of the kinetics and radical formation mechanism, were found when phenol was oxidized by the persulfate/NZVI system. In the initial stage, lasting 10 min, Fe 0 (s) was consumed rapidly and sulfate radicals were produced through activation by aqueous Fe 2+ . The second stage was governed by Fe catalyzed activation in the presence of aqueous Fe 3+ and iron (oxyhydr)oxides in the NZVI shells. The second stage was 3 orders of magnitude slower than the initial stage. An electron balance showed that the sulfate radical yield per mole of persulfate was more than two times higher in the persulfate/NZVI system than in the persulfate/Fe 2+ system. Radicals were believed to be produced more efficiently in the persulfate/NZVI system because aqueous Fe 2+ was supplied slowly, preventing sulfate radicals being scavenged by excess aqueous Fe 2+ . In the second stage, the multilayered shell conducted electrons, and magnetite in the shell provided electrons for the activation of persulfate. Iron speciation analysis (including X-ray absorption spectroscopy) results indicated that a shrinking core/growing shell model explained NZVI transformation during the persulfate/NZVI process.

Photochemical changes in cyanide speciation in drainage from a precious metal ore heap

USGS Publications Warehouse

Johnson, C.A.; Leinz, R.W.; Grimes, D.J.; Rye, R.O.

2002-01-01

In drainage from an inactive ore heap at a former gold mine, the speciation of cyanide and the concentrations of several metals were found to follow diurnal cycles. Concentrations of the hexacyanoferrate complex, iron, manganese, and ammonium were higher at night than during the day, whereas weak-acid-dissociable cyanide, silver, gold, copper, nitrite, and pH displayed the reverse behavior. The changes in cyanide speciation, iron, and trace metals can be explained by photodissociation of iron and cobalt cyanocomplexes as the solutions emerged from the heap into sunlight-exposed channels. At midday, environmentally significant concentrations of free cyanide were produced in a matter of minutes, causing trace copper, silver, and gold to be mobilized as cyanocomplexes from solids. Whether rapid photodissociation is a general phenomenon common to other sites will be important to determine in reaching a general understanding of the environmental risks posed by routine or accidental water discharges from precious metal mining facilities.

Internal iron biomineralization in Imperata cylindrica, a perennial grass: chemical composition, speciation and plant localization.

PubMed

Rodríguez, N; Menéndez, N; Tornero, J; Amils, R; de la Fuente, V

2005-03-01

* The analysis of metal distribution in Imperata cylindrica, a perennial grass isolated from the banks of Tinto River (Iberian Pyritic Belt), an extreme acidic environment with high content in metals, has shown a remarkable accumulation of iron. This property has been used to study iron speciation and its distribution among different tissues and structures of the plant. * Mossbauer (MS) and X-ray diffraction (XRD) were used to determine the iron species, scanning electron microscopy (SEM) to locate iron biominerals among plant tissue structures, and energy-dispersive X-ray microanalysis (EDAX), X-ray fluorescence (TXRF) and inductively coupled plasma emission spectroscopy (ICP-MS) to confirm their elemental composition. * The MS spectral analysis indicated that iron accumulated in this plant mainly as jarosite and ferritin. The presence of jarosite was confirmed by XRD and the distribution of both minerals in structures of different tissues was ascertained by SEM-EDAX analysis. * The convergent results obtained by complementary techniques suggest a complex iron management system in I. cylindrica, probably as a consequence of the environmental conditions of its habitat.

VARIATION OF ELEMENT SPECIATION IN COAL COMBUSTION AEROSOLS WITH PARTICLE SIZE

EPA Science Inventory

The speciation of sulfur, iron and key trace elements (Cr, As, Se, Zn) in combustion ash aerosols has been examined as a function of size from experimental combustion units burning Utah and Illinois bituminous coals. Although predominantly present as sulfate, sulfur was also pre...

THE DISTRIBUTION, SOLID-PHASE SPECIATION, AND DESORPTION/DISSOLUTION OF AS IN IRON-BASED DRINKING WATER TREATMENT MEDIA 1

EPA Science Inventory

Arsenic concentrations (Total Recoverable As by EPA Method 3051, soluble, Toxicity Characteristic Leaching Procedure extractable) and solid-phase speciation (by X-ray Absorption Near-Edge Spectroscopy-XANES) were assessed as a function of depth through Fe-media beds for two comme...

THE DISTRIBUTION, SOLID-PHASE SPECIATION, AND DESORPTION/DISSOLUTION OF AS IN IRON-BASED TREATMENT MEDIA

EPA Science Inventory

Arsenic concentrations (Total Recoverable As by EPA Method 3051) and solid-phase speciation (by X-ray Absorption Near-Edge Spectroscopy-XANES) were assessed as a function of depth through Fe-media beds for two commercially available products from pilot-scale field tests. These re...

THE DISTRIBUTION, SOLID-PHASE SPECIATION, AND DESORPTION/DISSOLUTION OF AS IN IRON-BASED DRINKING WATER TREATMENT MEDIA - JOURNAL

EPA Science Inventory

Arsenic concentrations (Total Recoverable As by EPA Method 3051, soluble, Toxicity Characteristic Leaching Procedure extractable) and solid-phase speciation (by X-ray Absorption Near-Edge Spectroscopy-XANES) were assessed as a function of depth through Fe-media beds for two comme...

THE DISTRIBUTION AND SOLID-PHASE SPECIATION OF AS IN IRON-BASED TREATMENT MEDIA

EPA Science Inventory

Arsenic concentrations (Total Recoverable As by EPA Method 3051) and solid-phase speciation (by X-ray Absorption Near-Edge Spectroscopy-XANES) were assessed as a function of depth through Fe-media beds for two commercially available products from pilot-scale field tests. These r...

Sulfur-binding in recent environments: II. Speciation of sulfur and iron and implications for the occurrence of organo-sulfur compounds

NASA Astrophysics Data System (ADS)

Hartgers, Walter A.; Lòpez, Jordi F.; Sinninghe Damsté, Jaap S.; Reiss, Christine; Maxwell, James R.; Grimalt, Joan O.

1997-11-01

Speciation of iron and sulfur species was determined for two recent sediments (La Trinitat and Lake Cisó) which were deposited in environments with a high biological productivity and sulfate-reducing activity. In sediments from calcite ponds of La Trinitat an excess of reactive iron species (iron monosulfides, iron hydroxides) results in a depletion of reactive sulfur which is accompanied by a virtual absence of organo-sulfur compounds, both in low (LMW) and high molecular-weight (HMW) fractions. Small amounts of phytanyl and highly branched isoprenoid (HBI) thiophenes in the extract demonstrate that these molecules exhibit a higher reactivity towards reduced sulfur species as compared to detrital iron. Euxinic sediments from Lake Cisó are characterised by an excess of reduced sulfur species which can rapidly trap reactive iron. High concentrations of H 2S results in the formation of organo-sulfur compounds which were encountered in both LMW and HMW fractions. The major part of the organic sulfur is bound to the carbohydrate portion of woody tissues, whose presence was revealed by a specific alkylthiophene distribution in the flash pyrolysate and by Li/EtNH 2 desulfurisation of the kerogen which resulted in the solubilisation of the sulfur-enriched hemicellulose fraction. Relatively high amounts of sulfurised C 25 HBI compounds in the sediment extract of Lake Cisó reflect the incorporation of sulfur into algal derived organic matter upon early diagenesis. The combined approach of the speciation of iron and sulfur species and the molecular analysis of sedimentary fractions demonstrates that abiotic sulfur binding to organic matter occurs at the earliest stages of diagenesis under specific depositional conditions (anoxic, stratified water column) in which an excess of reduced sulfur species relative to the amount of reactive iron is a controlling factor.

Disassembling Iron Availability to Phytoplankton

PubMed Central

Shaked, Yeala; Lis, Hagar

2012-01-01

The bioavailability of iron to microorganisms and its underlying mechanisms have far reaching repercussions to many natural systems and diverse fields of research, including ocean biogeochemistry, carbon cycling and climate, harmful algal blooms, soil and plant research, bioremediation, pathogenesis, and medicine. Within the framework of ocean sciences, short supply and restricted bioavailability of Fe to phytoplankton is thought to limit primary production and curtail atmospheric CO2 drawdown in vast ocean regions. Yet a clear-cut definition of bioavailability remains elusive, with elements of iron speciation and kinetics, phytoplankton physiology, light, temperature, and microbial interactions, to name a few, all intricately intertwined into this concept. Here, in a synthesis of published and new data, we attempt to disassemble the complex concept of iron bioavailability to phytoplankton by individually exploring some of its facets. We distinguish between the fundamentals of bioavailability – the acquisition of Fe-substrate by phytoplankton – and added levels of complexity involving interactions among organisms, iron, and ecosystem processes. We first examine how phytoplankton acquire free and organically bound iron, drawing attention to the pervasiveness of the reductive uptake pathway in both prokaryotic and eukaryotic autotrophs. Turning to acquisition rates, we propose to view the availability of various Fe-substrates to phytoplankton as a spectrum rather than an absolute “all or nothing.” We then demonstrate the use of uptake rate constants to make comparisons across different studies, organisms, Fe-compounds, and environments, and for gaging the contribution of various Fe-substrates to phytoplankton growth in situ. Last, we describe the influence of aquatic microorganisms on iron chemistry and fate by way of organic complexation and bio-mediated redox transformations and examine the bioavailability of these bio-modified Fe species. PMID:22529839

Peat hybrid sorbents for treatment of wastewaters and remediation of polluted environment

NASA Astrophysics Data System (ADS)

Klavins, Maris; Burlakovs, Juris; Robalds, Artis; Ansone-Bertina, Linda

2015-04-01

For remediation of soils and purification of polluted waters, wastewaters, sorbents might be considered as an prospective group of materials and amongst them peat have a special role due to low cost, biodegradability, high number of functional groups, well developed surface area and combination of hydrophilic/hydrophobic structural elements. Peat as sorbent have good application potential for removal of trace metals, and we have demonstrated peat sorption capacities, sorption kinetics, thermodynamics in respect to metals with different valencies - Tl(I), Cu(II), Cr(III). However peat sorption capacity in respect to nonmetallic (anionic species) elements is low. Also peat mechanical properties do not support application in large scale column processes. To expand peat application possibilities the approach of biomass based hybrid sorbents has been elaborated. The concept "hybrid sorbent" in our understanding means natural, biomass based sorbent modified, covered with another sorbent material, thus combining two types of sorbent properties, sorbent functionalities, surface properties etc. As the "covering layer" both inorganic substances, mineral phases (iron oxohydroxides, oxyapatite) both organic polymers (using graft polymerization) were used. The obtained sorbents were characterised by their spectral properties, surface area, elemental composition. The obtained hybrid sorbents were tested for sorption of compounds in anionic speciation forms, for example of arsenic, antimony, tellurium and phosphorous compounds in comparison with weakly basic anionites. The highest sorption capacity was observed when peat sorbents modified with iron compounds were used. Sorption of different arsenic speciation forms onto iron-modified peat sorbents was investigated as a function of pH and temperature. It was established that sorption capacity increases with a rise in temperature, and the calculation of sorption process thermodynamic parameters indicates the spontaneity of sorption process and its endothermic nature. The recycling options of obtained compounds after their saturation with metal or non-metallic species are suggested. Acknowledgement: Support from a project 2014/0009/1DP/1.1.1.2.0/13/APIA/VIAA/044

Sorptive Uptake Studies of an Aryl-Arsenical with Iron Oxide Composites on an Activated Carbon Support

PubMed Central

Kwon, Jae H.; Wilson, Lee D.; Sammynaiken, Ramaswami

2014-01-01

Sorption uptake kinetics and equilibrium studies for 4-hydroxy-3-nitrobenzene arsonic acid (roxarsone) was evaluated with synthetic magnetite (Mag-P), commercial magnetite (Mag-C), magnetite 10%, 19%, and 32% composite material (CM-10, -19, -32) that contains granular activated carbon (GAC), and synthetic goethite at pH 7.00 in water at 21 °C for 24 h. GAC showed the highest sorptive removal of roxarsone and the relative uptake for each sorbent material with roxarsone are listed in descending order as follows: GAC (471 mg/g) > goethite (418 mg/g) > CM-10 (377 mg/g) CM-19 (254 mg/g) > CM-32 (227 mg/g) > Mag-P (132 mg/g) > Mag-C (29.5 mg/g). The As (V) moiety of roxarsone is adsorbed onto the surface of the iron oxide/oxyhydrate and is inferred as inner-sphere surface complexes; monodentate-mononuclear, bidentate-mononuclear, and bidentate-binuclear depending on the protolytic speciation of roxarsone. The phenyl ring of roxarsone provides the primary driving force for the sorptive interaction with the graphene surface of GAC and its composites. Thus, magnetite composites are proposed as multi-purpose adsorbents for the co-removal of inorganic and organic arsenicals due to the presence of graphenic and iron oxide active adsorption sites. PMID:28788545

Organic Exudates Enhance Iron Bioavailability to Trichodesmium (IMS101) by Modifying Fe Speciation

NASA Astrophysics Data System (ADS)

Tohidi Farid, H.; Rose, A.; Schulz, K.

2016-02-01

Although ferrous iron (Fe (II)) is believed to be the most readily absorbed form of Fe by cells, under alkaline and oxygenated conditions typical of marine environments, the thermodynamically stable Fe(III) state dominates. In marine environments, this Fe(III) is primarily presents as organic Fe(III)L complexes whose bioavailability is highly variable. However, it has been demonstrated that some eukaryotic marine algae are able to release organic ligands into their surrounding environments that change Fe bioavailability through complexation and/or redox reactions. Nevertheless, it is unclear how Fe(II) oxidation and Fe(III) reduction rates might be modified by these exudates and how this might increase or decrease iron bioavailability to microorganisms. Here, the role of natural organic ligands excreted by the cyanobacterium Trichodesmium erythraeum on the oxidation kinetics of Fe(II) was studied using the luminol chemiluminescence technique. The oxidation kinetics of Fe(II) were examined at nanomolar Fe concentrations in presence of different concentrations of EDTA and dissolved organic carbon exuded by Trichodesmium cells. The results indicated that an increase in the concentration of exuded organic matter, and consequently L:Fe(II) ratio, resulted in decreasing rates of Fe(II) oxidation by oxygen, primarily due to formation of Fe(II) complexes. Moreover, the results demonstrated that the exudates from Trichodesmium may be able to reduce Fe(III) to the more bioavailable Fe(II) state under some circumstances. This study therefore supports the ability of microorganisms to manipulate Fe bioavailability by releasing organic compounds into the extracellular environment that retard Fe(II) oxidation rates or reducing Fe(III) species to Fe(II). It also provides new insight into the potential mechanism(s) by which Trichdesmium may acquire Fe under conditions where Fe bioavailability is otherwise limited.

Influence of Organic Matter - Mineral Interfacial Reactions on Metal(loid) Speciation and Bioaccessibility

NASA Astrophysics Data System (ADS)

Chorover, J.; Kong, S.; Root, R. A.; Thomas, A.

2015-12-01

Bioaccessibility of contaminant metals in geomedia is often measured on the basis of kinetic release to solution during in vitro reaction with biofluid simulants. We postulate that development of a predictive-mechanistic understanding of bioaccessibility requires knowledge of metal(loid) molecular speciation upon sample introduction, as well as its change over the course of the in vitro reaction. Our results - including data from batch, column, mesocosm and field studies pertaining to arsenic, lead, and zinc contaminated materials - indicate the strong influence of organic matter and associated biological activity on metal(loid) speciation in mine tailings and related model systems. Furthermore, presence/absence of organic matter during bioassays affects the kinetics of metal(loid) release into biofluid simulants through multiple mechanisms.

Iron Mineralogy and Speciation in Clay-Sized Fractions of Chinese Desert Sediments

NASA Astrophysics Data System (ADS)

Lu, Wanyi; Zhao, Wancang; Balsam, William; Lu, Huayu; Liu, Pan; Lu, Zunli; Ji, Junfeng

2017-12-01

Iron released from Asian desert dust may be an important source of bioavailable iron for the North Pacific Ocean and thereby may stimulate primary productivity. However, the Fe species of the fine dusts from this source region are poorly characterized. Here we investigate iron species and mineralogy in the clay-sized fractions (<2 μm), the size fraction most prone to long-distance transport as dust. Samples were analyzed by sequential chemical extraction, X-ray diffraction, and diffuse reflectance spectrometry. Our results show that Fe dissolved from easily reducible iron phases (ferrihydrite and lepidocrocite) and reducible iron oxides (dominated by goethite) are 0.81 wt % and 2.39 wt %, respectively, and Fe dissolved from phyllosilicates extracted by boiling HCl (dominated by chlorite) is 3.15 wt %. Dusts originating from deserts in northwestern China, particularly the Taklimakan desert, are relatively enriched in easily reducible Fe phases, probably due to abundant Fe contained in fresh weathering products resulting from the rapid erosion associated with active uplift of mountains to the west. Data about Fe speciation and mineralogy in Asian dust sources will be useful for improving the quantification of soluble Fe supplied to the oceans, especially in dust models.

Iron Speciation and Mixing in Single Aerosol Particles from the Asian Continental Outflow

DOE Office of Scientific and Technical Information (OSTI.GOV)

Moffet, Ryan C.; Furutani, Hiroshi; Rodel, Tobias

2012-04-04

Bioavailable iron from atmospheric aerosol is an essential nutrient that can control oceanic productivity, thereby impacting the global carbon budget and climate. Particles collected on Okinawa Island during an atmospheric pollution transport event from China were analyzed using complementary single particle techniques to determine the iron source and speciation. Comparing the spatial distribution of iron within ambient particles and standard Asian mineral dust, it was determined that field-collected atmospheric Fe-containing particles have numerous sources, including anthropogenic sources such as coal combustion. Fe-containing particles were found to be internally mixed with secondary species such as sulfate, soot, and organic carbon. Themore » mass weighted average Fe(II) fraction (defined as Fe(II)/[Fe(II)+Fe(III)]) was determined to be 0.33 {+-} 0.08. Within the experimental uncertainty, this value lies close to the range of 0.26-0.30 determined for representative Asian mineral dust. Previous studies have indicated that the solubility of iron from combustion is much higher than that from mineral dust. Therefore, chemical and/or physical differences other than oxidation state may help explain the higher solubility of iron in atmospheric particles.« less

Culturing Selenastrum capricornutum (Chlorophyta) in a synthetic algal nutrient medium with defined mineral particulates

USGS Publications Warehouse

Kuwabara, J.S.; Davis, J.A.; Chang, Cecily C.Y.

1985-01-01

Algal nutrient studies in chemically-defined media typically employ a synthetic chelator to prevent iron hydroxide precipitation. Micronutrient-particulate interactions may, however, significantly affect chemical speciation and hence biovailability of these nutrients in natural waters. A technique is described by which Selenastrum capricornutum Printz (Chlorophyta) may be cultured in a medium where trace metal speciation (except iron) is controlled, not by organic chelation, but by sorption onto titanium dioxide. Application of this culturing protocol in conjunction with results from sorption studies of nutrient ions on mineral particles provides a means of studying biological impacts of sorptive processes in aquatic environments. ?? 1985 Dr W. Junk Publishers.

Hydroquinone-Mediated Redox Cycling of Iron and Concomitant Oxidation of Hydroquinone in Oxic Waters under Acidic Conditions: Comparison with Iron-Natural Organic Matter Interactions.

PubMed

Jiang, Chao; Garg, Shikha; Waite, T David

2015-12-15

Interactions of 1,4-hydroquinone with soluble iron species over a pH range of 3-5 in the air-saturated and partially deoxygenated solution are examined here. Our results show that 1,4-hydroquinone reduces Fe(III) in acidic conditions, generating semiquinone radicals (Q(•-)) that can oxidize Fe(II) back to Fe(III). The oxidation rate of Fe(II) by Q(•-)increases with increase in pH due to the speciation change of Q(•-) with its deprotonated form (Q(•-)) oxidizing Fe(II) more rapidly than the protonated form (HQ(•)). Although the oxygenation of Fe(II) is negligible at pH < 5, O2 still plays an important role in iron redox transformation by rapidly oxidizing Q(•-) to form benzoquinone (Q). A kinetic model is developed to describe the transformation of quinone and iron under all experimental conditions. The results obtained here are compared with those obtained in our previous studies of iron-Suwannee River fulvic acid (SRFA) interactions in acidic solutions and support the hypothesis that hydroquinone moieties can reduce Fe(III) in natural waters. However, the semiquinone radicals generated in pure hydroquinone solution are rapidly oxidized by dioxygen, while the semiquinone radicals generated in SRFA solution are resistant to oxidation by dioxygen, with the result that steady-state semiquinone concentrations in SRFA solutions are 2-3 orders of magnitude greater than in solutions of 1,4-hydroquinone. As a result, semiquinone moieties in SRFA play a much more important role in iron redox transformations than is the case in solutions of simple quinones such as 1,4-hydroquinone. This difference in the steady-state concentration of semiquinone species has a dramatic effect on the cycling of iron between the +II and +III oxidation states, with iron turnover frequencies in solutions containing SRFA being 10-20 times higher than those observed in solutions of 1,4-hydroquinone.

Voltammetric determination of arsenic in high iron and manganese groundwaters.

PubMed

Gibbon-Walsh, Kristoff; Salaün, Pascal; Uroic, M Kalle; Feldmann, Joerg; McArthur, John M; van den Berg, Constant M G

2011-09-15

Determination of the speciation of arsenic in groundwaters, using cathodic stripping voltammetry (CSV), is severely hampered by high levels of iron and manganese. Experiments showed that the interference is eliminated by addition of EDTA, making it possible to determine the arsenic speciation on-site by CSV. This work presents the CSV method to determine As(III) in high-iron or -manganese groundwaters in the field with only minor sample treatment. The method was field-tested in West-Bengal (India) on a series of groundwater samples. Total arsenic was subsequently determined after acidification to pH 1 by anodic stripping voltammetry (ASV). Comparative measurements by ICP-MS as reference method for total As, and by HPLC for its speciation, were used to corroborate the field data in stored samples. Most of the arsenic (78±0.02%) was found to occur as inorganic As(III) in the freshly collected waters, in accordance with previous studies. The data shows that the modified on-site CSV method for As(III) is a good measure of water contamination with As. The EDTA was also found to be effective in stabilising the arsenic speciation for longterm sample storage at room temperature. Without sample preservation, in water exposed to air and sunlight, the As(III) was found to become oxidised to As(V), and Fe(II) oxidised to Fe(III), removing the As(V) by adsorption on precipitating Fe(III)-hydroxides within a few hours. Copyright © 2011 Elsevier B.V. All rights reserved.

Influence of a soil enzyme on iron-cyanide complex speciation and mineral adsorption.

PubMed

Zimmerman, Andrew R; Kang, Dong-Hee; Ahn, Mi-Youn; Hyun, Seunghun; Banks, M Katherine

2008-01-01

Cyanide is commonly found as ferrocyanide [Fe(II)(CN)(6)](-4) and in the more mobile form, ferricyanide [Fe(III)(CN)(6)](-3) in contaminated soils and sediments. Although soil minerals may influence ferrocyanide speciation, and thus mobility, the possible influence of soil enzymes has not been examined. In a series of experiments conducted under a range of soil-like conditions, laccase, a phenoloxidase enzyme derived from the fungi Trametes versicolor, was found to exert a large influence on iron-cyanide speciation and mobility. In the presence of laccase, up to 93% of ferrocyanide (36-362ppm) was oxidized to ferricyanide within 4h. No significant effect of pH (3.6 and 6.2) or initial ferrocyanide concentration on the extent or rate of oxidation was found and ferrocyanide oxidation did not occur in the absence of laccase. Relative to iron-cyanide-mineral systems without laccase, ferrocyanide adsorption to aluminum hydroxide and montmorillonite decreased in the presence of laccase and was similar to or somewhat greater than that of ferricyanide without laccase. Laccase-catalyzed conversion of ferrocyanide to ferricyanide was extensive though up to 33% of the enzyme was mineral-bound. These results demonstrate that soil enzymes can play a major role in ferrocyanide speciation and mobility. Biotic soil components must be considered as highly effective oxidation catalysts that may alter the mobility of metals and metal complexes in soil. Immobilized enzymes should also be considered for use in soil metal remediation efforts.

Impacts of amount of impregnated iron in granular activated carbon on arsenate adsorption capacities and kinetics.

PubMed

Chang, Qigang; Lin, Wei; Ying, Wei-Chi

2012-06-01

Iron-impregnated granular activated carbons (Fe-GAC) can remove arsenic effectively from water. In this study, Fe-GACs with iron content of 1.64 to 28.90% were synthesized using a new multi-step procedure for the investigation of effects of iron amount on arsenic adsorption capacities and kinetics. Langmuir model satisfactorily fit arsenic adsorption on Fe-GACs. The maximum arsenic adsorption capacity (q(m)) increased significantly with iron impregnation and reached 1,867 to 1,912 microg/g with iron content of 9.96 to 13.59%. Further increase of iron content (> 13.59%) caused gradual decrease of q(m). It was found that the amount of impregnated iron showed little impact on the affinity for arsenate. Kinetic study showed that the amount of impregnated iron affected the arsenic intraparticle diffusion rate greatly. The pseudo-second-order kinetic model fit arsenic adsorption kinetics on Fe-GACs better than the pseudo-first-order model. The arsenic adsorption rate increased with increasing of iron content from 1.64% to 13.59%, and then decreased with more impregnated iron (13.59 to 28.90%).

The Organic Complexation of Iron in the Marine Environment: A Review

PubMed Central

Gledhill, Martha; Buck, Kristen N.

2012-01-01

Iron (Fe) is an essential micronutrient for marine organisms, and it is now well established that low Fe availability controls phytoplankton productivity, community structure, and ecosystem functioning in vast regions of the global ocean. The biogeochemical cycle of Fe involves complex interactions between lithogenic inputs (atmospheric, continental, or hydrothermal), dissolution, precipitation, scavenging, biological uptake, remineralization, and sedimentation processes. Each of these aspects of Fe biogeochemical cycling is likely influenced by organic Fe-binding ligands, which complex more than 99% of dissolved Fe. In this review we consider recent advances in our knowledge of Fe complexation in the marine environment and their implications for the biogeochemistry of Fe in the ocean. We also highlight the importance of constraining the dissolved Fe concentration value used in interpreting voltammetric titration data for the determination of Fe speciation. Within the published Fe speciation data, there appear to be important temporal and spatial variations in Fe-binding ligand concentrations and their conditional stability constants in the marine environment. Excess ligand concentrations, particularly in the truly soluble size fraction, seem to be consistently higher in the upper water column, and especially in Fe-limited, but productive, waters. Evidence is accumulating for an association of Fe with both small, well-defined ligands, such as siderophores, as well as with larger, macromolecular complexes like humic substances, exopolymeric substances, and transparent exopolymers. The diverse size spectrum and chemical nature of Fe ligand complexes corresponds to a change in kinetic inertness which will have a consequent impact on biological availability. However, much work is still to be done in coupling voltammetry, mass spectrometry techniques, and process studies to better characterize the nature and cycling of Fe-binding ligands in the marine environment. PMID:22403574

Microanalysis of iron oxidation state in iron oxides using X Ray Absorption Near Edge Structure (XANES)

NASA Technical Reports Server (NTRS)

Sutton, S. R.; Delaney, J.; Bajt, S.; Rivers, M. L.; Smith, J. V.

1993-01-01

An exploratory application of x ray absorption near edge structure (XANES) analysis using the synchrotron x ray microprobe was undertaken to obtain Fe XANES spectra on individual sub-millimeter grains in conventional polished sections. The experiments concentrated on determinations of Fe valence in a suite of iron oxide minerals for which independent estimates of the iron speciation could be made by electron microprobe analysis and x ray diffraction.

Spatio-temporal Distribution and Chemical Speciation of Iron and Manganese in Sediments from Lake Aha, China

NASA Astrophysics Data System (ADS)

Liu, Feng; Hu, Jiwei; Qin, Fanxin; Jiang, Cuihong; Huang, Xianfei; Deng, Jiajun; Li, Cunxiong

2010-11-01

This paper reports an investigation on pollution and potential risk on elements of iron (Fe) and manganese (Mn) in sediments from Lake Aha, which is a drinking-water source for Guiyang City, the capital of Guizhou Province in southwestern China. In the present research, chemical speciation of Fe and Mn in sediments from the lake was studied based on the sequential extraction procedure developed by Tessier et al.. The results obtained from the study are as follows. The average values of total Fe were 47617 mg/kg and 70325 mg/kg in sediments from the lake in summer and winter respectively, and its speciation consisted mainly of residual and Fe-Mn oxides fractions. The amounts of total Fe and the distribution of its speciation in the sediments should be affected by effluents from a large quantity of deserted coal mines in the lake basin in summer and winter. The average values of total Mn were 7996 mg/kg and 1753 mg/kg in summer and winter respectively, and its speciation is primarily comprised of carbonate and Fe-Mn oxides fractions. The amounts of total Mn and its distribution in different fractions in the sediments were believed to be primarily influenced by effluents from those deserted coal mines in summer and by the condition of redox interface in winter.

MINERALOGY AND CHARACTERIZATION OF ARSENIC, IRON, AND LEAD IN A MINE WASTE-DERIVED FERTILIZER

EPA Science Inventory

The solid-state speciation of arsenic (As), iron (Fe), and lead (Pb) was studied in the mine waste-derived fertilizer Ironite using X-ray absorption spectroscopy, Mössbauer spectroscopy, and aging studies. Arsenic was primarily associated with ferrihydrite (60-70%) with the rema...

Oxidative Remobilization of Technetium Sequestered by Sulfide-Transformed Nano Zerovalent Iron

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fan, Dimin; Anitori, Roberto; Tebo, Bradley M.

2014-06-02

The dissolution of Tc(IV) sulfide and concurrent transformation of sulfidated ZVI during 2 oxidation were examined. Kinetic data obtained with 10 mL batch reactors showed that Tc(VII) 3 reduced by sulfidated nZVI has significantly slower reoxidation rates than Tc(VII) reduced by 4 nZVI only. In a 50 mL batch reactor, initial inhibition of Tc(IV) dissolution was apparent and 5 lasted until 120 hours at S/Fe = 0.112, presumably due to the redox buffer capacity of FeS. This 6 is evidenced by the parallel trends in oxidation-reduction potentials (ORP) and Tc dissolution 7 kinetics. Mӧssbauer spectra and micro X-ray diffraction ofmore » S/Fe = 0.112 suggested the 8 persistence of FeS after 24-h oxidation although X-ray photoelectron spectroscopy indicated 9 substantial surface oxidation. After 120-h oxidation, all characterizations showed complete 10 oxidation of FeS, which further indicates that FeS inhibits Tc oxidation. X-ray absorption 11 spectroscopy for S/Fe = 0.011 showed significantly increasing percentage of TcS2 in the solid 12 phase after 24-h oxidation, indicating TcS2 is more resistant to oxidation than TcO2. At S/Fe = 13 0.112, the XAS results revealed significant transformation of Tc speciation from TcS2 to TcO2 14 after 120-h oxidation at S/Fe = 0.112. Given that no apparent Tc dissolution occurred during this 15 period, the speciation transformation might play a secondary role in hindering Tc oxidation, 16 especially as redox buffer capacity approached depletion.« less

Iron overload diseases: the chemical speciation of non-heme iron deposits in iron loaded mammalian tissues

NASA Astrophysics Data System (ADS)

St. Pierre, T. G.; Chua-Anusorn, W.; Webb, J.; Macey, D. J.

2000-07-01

57Fe Mössbauer spectra of iron overloaded human spleen, rat spleen and rat liver tissue samples at 78 K were found to consist of a quadrupole doublet (major component) with magnetic sextet (minor component with fractional spectral area F s). The distributions of F s for spleen tissue from two different clinically identifiable groups (n = 7 and n = 12) of thalassemic patients were found to be significantly different. The value of F s for dietary-iron loaded rat liver was found to rise significantly with age/duration (up to 24 months) of iron loading.

Solubility of iron from combustion source particles in acidic media linked to iron speciation.

PubMed

Fu, Hongbo; Lin, Jun; Shang, Guangfeng; Dong, Wenbo; Grassian, Vichi H; Carmichael, Gregory R; Li, Yan; Chen, Jianmin

2012-10-16

In this study, iron solubility from six combustion source particles was investigated in acidic media. For comparison, a Chinese loess (CL) dust was also included. The solubility experiments confirmed that iron solubility was highly variable and dependent on particle sources. Under dark and light conditions, the combustion source particles dissolved faster and to a greater extent relative to CL. Oil fly ash (FA) yielded the highest soluble iron as compared to the other samples. Total iron solubility fractions measured in the dark after 12 h ranged between 2.9 and 74.1% of the initial iron content for the combustion-derived particles (Oil FA > biomass burning particles (BP) > coal FA). Ferrous iron represented the dominant soluble form of Fe in the suspensions of straw BP and corn BP, while total dissolved Fe presented mainly as ferric iron in the cases of oil FA, coal FA, and CL. Mössbauer measurements and TEM analysis revealed that Fe in oil FA was commonly presented as nanosized Fe(3)O(4) aggregates and Fe/S-rich particles. Highly labile source of Fe in corn BP could be originated from amorphous Fe form mixed internally with K-rich particles. However, Fe in coal FA was dominated by the more insoluble forms of both Fe-bearing aluminosilicate glass and Fe oxides. The data presented herein showed that iron speciation varies by source and is an important factor controlling iron solubility from these anthropogenic emissions in acidic solutions, suggesting that the variability of iron solubility from combustion-derived particles is related to the inherent character and origin of the aerosols themselves. Such information can be useful in improving our understanding on iron solubility from combustion aerosols when they undergo acidic processing during atmospheric transport.

Factors influencing sorption of ciprofloxacin onto activated sludge: experimental assessment and modelling implications.

PubMed

Polesel, Fabio; Lehnberg, Kai; Dott, Wolfgang; Trapp, Stefan; Thomas, Kevin V; Plósz, Benedek Gy

2015-01-01

Many of the pharmaceuticals and personal care products occurring in municipal sewage are ionizing substances, and their partitioning behaviour is affected by ionic interactions with solid matrices. In activated sludge systems, such interactions have currently not been adequately understood and described, particularly for zwitterionic chemicals. Here we present an assessment of the effects of pH and iron salt dosing on the sorption of ciprofloxacin onto activated sludge using laboratory experiments and full-scale fate modelling. Experimental results were described with Freundlich isotherms and showed that non-linear sorption occurred under all the conditions tested. The greatest sorption potential was measured at pH=7.4, at which ciprofloxacin is speciated mostly as zwitterion. Iron salt dosing increased sorption under aerobic and, to a lesser extent, anoxic conditions, whereas no effect was registered under anaerobic conditions. The activated sludge model for xenobiotics (ASM-X) was extended with Freundlich-based sorption kinetics and used to predict the fate of ciprofloxacin in a wastewater treatment plant (WWTP). Scenario simulations, using experimental Freundlich parameters, were used to identify whether the assessed factors caused a significant increase of aqueous ciprofloxacin concentration in full-scale bioreactors. Simulation results suggest that a pH increase, rather than a reduction in iron salt dosing, could be responsible for a systematic deterioration of sorption of ciprofloxacin in the WWTP. Copyright © 2014 Elsevier Ltd. All rights reserved.

Speciation and Release Kinetics of Cadmium in an Alkaline Paddy Soil Under Various Flooding Periods and Draining Conditions

DOE Office of Scientific and Technical Information (OSTI.GOV)

S Khaokaew; R Chaney; G Landrot

2011-12-31

This study determined Cd speciation and release kinetics in a Cd-Zn cocontaminated alkaline paddy soil, under various flooding periods and draining conditions, by employing synchrotron-based techniques, and a stirred-flow kinetic method. Results revealed that varying flooding periods and draining conditions affected Cd speciation and its release kinetics. Linear least-squares fitting (LLSF) of bulk X-ray absorption fine structure (XAFS) spectra of the air-dried, and the 1 day-flooded soil samples, showed that at least 50% of Cd was bound to humic acid. Cadmium carbonates were found as the major species at most flooding periods, while a small amount of cadmium sulfide wasmore » found after the soils were flooded for longer periods. Under all flooding and draining conditions, at least 14 mg/kg Cd was desorbed from the soil after a 2-hour desorption experiment. The results obtained by micro X-ray fluorescence ({mu}-XRF) spectroscopy showed that Cd was less associated with Zn than Ca, in most soil samples. Therefore, it is more likely that Cd and Ca will be present in the same mineral phases rather than Cd and Zn, although the source of these two latter elements may originate from the same surrounding Zn mines in the Mae Sot district.« less

Development of a mercury speciation, fate, and biotic uptake (BIOTRANSPEC) model: Application to Lahontan Reservoir (Nevada, USA)

USGS Publications Warehouse

Gandhi, N.; Bhavsar, S.P.; Diamond, M.L.; Kuwabara, J.S.; Marvin-DiPasquale, M.; Krabbenhoft, D.P.

2007-01-01

A mathematically linked mercury transport, speciation, kinetic, and simple biotic uptake (BIOTRANSPEC) model has been developed. An extension of the metal transport and speciation (TRANSPEC) model, BIOTRANSPEC estimates the fate and biotic uptake of inorganic (Hg(II)), elemental (Hg(0)) and organic (MeHg) forms of mercury and their species in the dissolved, colloidal (e.g., dissolved organic matter [DOM]), and particulate phases of surface aquatic systems. A pseudo-steady state version of the model was used to describe mercury dynamics in Lahontan Reservoir (near Carson City, NV, USA), where internal loading of the historically deposited mercury is remobilized, thereby maintaining elevated water concentrations. The Carson River is the main source of total mercury (THg), of which more than 90% is tightly bound in a gold-silver-mercury amalgam, to the system through loadings in the spring, with negligible input from the atmospheric deposition. The speciation results suggest that aqueous species are dominated by Hg-DOM, Hg(OH)2, and HgClOH. Sediment-to-water diffusion of MeHg and Hg-DOM accounts for approximately 10% of total loadings to the water column. The water column acts as a net sink for MeHg by reducing its levels through two competitive processes: Uptake by fish, and net MeHg demethylation. Although reservoir sediments produce significant amounts of MeHg (4 g/d), its transport from sediment to water is limited (1.6 g/d), possibly because of its adsorption on metal oxides of iron and manganese at the sediment-water interface. Fish accumulate approximately 45% of the total MeHg mass in the water column, and 9% of total MeHg uptake by fish leaves the system because of fishing. Results from this new model reiterate the previous conclusion that more than 90% of THg input is retained in sediment, which perpetuates elevated water concentrations. ?? 2007 SETAC.

Influence of Iron Speciation on Redox Cycling and Reactivity with Persistent Organic Contaminants

ERIC Educational Resources Information Center

Kim, Dongwook

2009-01-01

Although a number of past studies have been aimed at characterizing iron's redox properties in aqueous systems and its contribution to natural attenuation processes of groundwater contaminants, many questions remain. It is especially important to understand the molecular properties that control the reactivity of both Fe[superscript II] and…

Performance of a Zerovalent Iron Reactive Barrier for the Treatment of Arsenic in Groundwater: Part 2. Geochemical Modeling and Solid Phase Studies

EPA Science Inventory

Arsenic uptake processes were evaluated in a zerovalent iron reactive barrier installed at a lead smelting facility using geochemical modeling, solid-phase analysis, and X-ray absorption spectroscopy techniques. Aqueous speciation of arsenic plays a key role in directing arsenic...

Modeling low-temperature geochemical processes: Chapter 2

USGS Publications Warehouse

Nordstrom, D. Kirk; Campbell, Kate M.

2014-01-01

This chapter provides an overview of geochemical modeling that applies to water–rock interactions under ambient conditions of temperature and pressure. Topics include modeling definitions, historical background, issues of activity coefficients, popular codes and databases, examples of modeling common types of water–rock interactions, and issues of model reliability. Examples include speciation, microbial redox kinetics and ferrous iron oxidation, calcite dissolution, pyrite oxidation, combined pyrite and calcite dissolution, dedolomitization, seawater–carbonate groundwater mixing, reactive-transport modeling in streams, modeling catchments, and evaporation of seawater. The chapter emphasizes limitations to geochemical modeling: that a proper understanding and ability to communicate model results well are as important as completing a set of useful modeling computations and that greater sophistication in model and code development is not necessarily an advancement. If the goal is to understand how a particular geochemical system behaves, it is better to collect more field data than rely on computer codes.

Modeling bromide effects on yields and speciation of dihaloacetonitriles formed in chlorinated drinking water.

PubMed

Roccaro, Paolo; Chang, Hyun-shik; Vagliasindi, Federico G A; Korshin, Gregory V

2013-10-15

This study examined effects of bromide on yields and speciation of dihaloacetonitrile (DHAN) species that included dichloro-, bromochloro- and dibromoacetonitriles generated in chlorinated water. Experimental data obtained using two water sources, varying concentrations and characters of Natural Organic Matter (NOM), bromide concentrations, reaction times, chlorine doses, temperatures and pHs were interpreted using a semi-phenomenological model that assumed the presence of three kinetically distinct sites in NOM (denoted as sites S1, S2 and S3) and the occurrence of sequential incorporation of bromine and chlorine into them. One site was found to react very fast with the chlorine and bromine but its contribution in the DHAN generation was very low. The site with the highest contribution to the yield of DHAN (>70%) has the lowest reaction rates. The model introduced dimensionless coefficients (denoted as φ1(DHAN), φ2(DHAN) and φ3(DHAN)) applicable to the initial DHAN generation sites and their monochlorinated and monobrominated products, respectively. These parameters were used to quantify the kinetic preference to bromine incorporation over that of chlorine. Values of these coefficients optimized for DHAN formation were indicative of the strongly preferential incorporation of bromine into the engaged NOM sites. The same set of φ(i)(DHAN) coefficients could be used to model the speciation of DHAN released from their kinetically different precursors. The dimensionless speciation coefficients φ(i)(DHAN) were determined to be site specific and dependent on the NOM content and character as well as pH. The presented model of DHAN formation and speciation can help quantify in more detail the generation of DHAN and provide more insight necessary for further assessment of their potential health effects. Copyright © 2013 Elsevier Ltd. All rights reserved.

Effects of aqueous uranyl speciation on the kinetics of microbial uranium reduction

DOE PAGES

Belli, Keaton M.; DiChristina, Thomas J.; Van Cappellen, Philippe; ...

2015-02-16

The ability to predict the success of the microbial reduction of soluble U(VI) to highly insoluble U(IV) as an in situ bioremediation strategy is complicated by the wide range of geochemical conditions at contaminated sites and the strong influence of aqueous uranyl speciation on the bioavailability and toxicity of U(VI) to metal-reducing bacteria. In order to determine the effects of aqueous uranyl speciation on uranium bioreduction kinetics, incubations and viability assays with Shewanella putrefaciens strain 200 were conducted over a range of pH and dissolved inorganic carbon (DIC), Ca 2+, and Mg 2+ concentrations. A speciation-dependent kinetic model was developedmore » to reproduce the observed time series of total dissolved uranium concentration over the range of geochemical conditions tested. The kinetic model yielded the highest rate constant for the reduction of uranyl non-carbonate species (i.e., the ‘free’ hydrated uranyl ion, uranyl hydroxides, and other minor uranyl complexes), indicating that they represent the most readily reducible fraction of U(VI) despite being the least abundant uranyl species in solution. In the presence of DIC, Ca 2+, and Mg 2+ is suppressed during the formation of more bioavailable uranyl non-carbonate species and resulted in slower bioreduction rates. At high concentrations of bioavailable U(VI), however, uranium toxicity to S. putrefaciens inhibited bioreduction, and viability assays confirmed that the concentration of non-carbonate uranyl species best predicts the degree of toxicity. The effect of uranium toxicity was accounted for by incorporating the free ion activity model of metal toxicity into the bioreduction rate law. These results demonstrate that, in the absence of competing terminal electron acceptors, uranium bioreduction kinetics can be predicted over a wide range of geochemical conditions based on the bioavailability and toxicity imparted on U(VI) by solution composition. Finally, these findings also imply that the concentration of uranyl non-carbonate species, despite being extremely low, is a determining factor controlling uranium bioreduction at contaminated sites.« less

Speciation and Health Risks of Atmospheric Nanoparticulates

NASA Astrophysics Data System (ADS)

Nguyen, Kennedy

Exposure to air pollution causes several adverse health effects such as asthma, respiratory disease, cardiovascular disease, cancer, and premature death; and the San Joaquin Valley is one of the most heavily polluted regions in the US. The mountains that surround the valley allow air pollution, including particulate matter, to remain stagnant, prolonging the exposure of valley populations to it. The primary sources of particulate matter for this region are aluminosilicate dust from agricultural activities, and soot emissions from diesel trucks and vehicular traffic. A substantial fraction of emitted material is nanoparticulate matter (<100 nm), which contains trace iron and polycyclic aromatic hydrocarbons that can traverse into human organs via the lungs, initiate inflammation, and lead to disease. The traditional approach of reducing the total mass of emitted material is beginning to reach its limit of effectiveness for mitigating the negative health impacts of particulate matter. There is a need for chemical speciation of particulate matter that will allow the identification of the chemical and physical properties of particulates by source, the creation of well-controlled proxy particles with those properties for testing in cell culture studies, and correlation of particulate properties and sources with their negative health impacts. These results can help identify the sources of air pollution to prioritize for mitigation for the greatest health benefit. In addition, further chemical speciation can help monitor the results of such mitigation efforts. Here, natural particulate matter samples from Merced and Fresno, two cities in the San Joaquin Valley, were analyzed. Ultrafine particles present were 40 to 50 nm in diameter and mostly composed of aluminum, silicon, oxygen, and iron hydroxide. XAS data confirmed the presence of the aluminosilicate as smectite clay and the iron hydroxide as ferrihydrite. Furthermore, a chemical speciation study investigated industrial emissions of air particulate matter. Samples were analyzed using electron microscopy for elemental composition and size distribution, and found to contain fine metal particulates (lead and iron) that can lead to lung inflammation. From characterization data, in order to create a simplified proxy particle system for cell culture studies, amorphous silica particles were synthesized using a modified Stober Synthesis and coated with iron hydroxide. A range of iron hydroxide concentrations (0.06 to 1.63 mmol of iron per gram of silica) were used to test the effect of iron contamination on THP-1 cells, and higher concentrations of iron with silica (0.43 and 1.63 mmol of iron per gram of silica) were found to increase production of pro-inflammatory mediators compared to silica alone. Iron alone did not induce an effect relative to the control, demonstrating a synergistic effect when iron is combined with silica at low doses. It was found that crystalline silica was more toxic than amorphous silica (70% vs 80% respectively at 100 mug/ml). In addition, mesoporous silica was found to be more toxic than solid silica (73% vs 82% respectively at 100 mug/ml), likely due to a higher surface area (60.2 m2/g for mesoporous external surface area without internal pores vs 1.72 m 2/g for solid 2 mum silica and 54.5 m2/g for 50 nm silica) and increased particle loading at the same dose. Finally, a preliminary investigation of Printex 90 as a proxy material for soot, with and without the addition of iron and quinones, was conducted.

Mercury speciation and mobilization in a wastewater-contaminated groundwater plume

USGS Publications Warehouse

Lamborg, Carl H.; Kent, Doug B.; Swarr, Gretchen J.; Munson, Kathleen M.; Kading, Tristan; O'Connor, Alison E.; Fairchild, Gillian M.; LeBlanc, Denis R.; Wiatrowski, Heather A.

2013-01-01

We measured the concentration and speciation of mercury (Hg) in groundwater down-gradient from the site of wastewater infiltration beds operated by the Massachusetts Military Reservation, western Cape Cod, Massachusetts. Total mercury concentrations in oxic, mildly acidic, uncontaminated groundwater are 0.5–1 pM, and aquifer sediments have 0.5–1 ppb mercury. The plume of impacted groundwater created by the wastewater disposal is still evident, although inputs ceased in 1995, as indicated by anoxia extending at least 3 km down-gradient from the disposal site. Solutes indicative of a progression of anaerobic metabolisms are observed vertically and horizontally within the plume, with elevated nitrate concentrations and nitrate reduction surrounding a region with elevated iron concentrations indicating iron reduction. Mercury concentrations up to 800 pM were observed in shallow groundwater directly under the former infiltration beds, but concentrations decreased with depth and with distance down-gradient. Mercury speciation showed significant connections to the redox and metabolic state of the groundwater, with relatively little methylated Hg within the iron reducing sector of the plume, and dominance of this form within the higher nitrate/ammonium zone. Furthermore, substantial reduction of Hg(II) to Hg0 within the core of the anoxic zone was observed when iron reduction was evident. These trends not only provide insight into the biogeochemical factors controlling the interplay of Hg species in natural waters, but also support hypotheses that anoxia and eutrophication in groundwater facilitate the mobilization of natural and anthropogenic Hg from watersheds/aquifers, which can be transported down-gradient to freshwaters and the coastal zone.

Photometric flow analysis system for biomedical investigations of iron/transferrin speciation in human serum.

PubMed

Strzelak, Kamil; Rybkowska, Natalia; Wiśniewska, Agnieszka; Koncki, Robert

2017-12-01

The Multicommutated Flow Analysis (MCFA) system for the estimation of clinical iron parameters: Serum Iron (SI), Unsaturated Iron Binding Capacity (UIBC) and Total Iron Binding Capacity (TIBC) has been proposed. The developed MCFA system based on simple photometric detection of iron with chromogenic agent (ferrozine) enables a speciation of transferrin (determination of free and Fe-bound protein) in human serum. The construction of manifold was adapted to the requirements of measurements under changing conditions. In the course of studies, a different effect of proteins on SI and UIBC determination has been proven. That was in turn the reason to perform two kinds of calibration methods. For measurements in acidic medium for SI/holotransferrin determination, the calibration curve method was applied, characterized by limit of determination and limit of quantitation on the level of 3.4 μmol L -1 and 9.1 μmol L -1 , respectively. The determination method for UIBC parameter (related to apotransferrin level) in physiological medium of pH 7.4 forced the use of standard addition method due to the strong influence of proteins on obtaining analytical signals. These two different methodologies, performed in the presented system, enabled the estimation of all three clinical iron/transferrin parameters in human serum samples. TIBC corresponding to total transferrin level was calculated as a sum of SI and UIBC. Copyright © 2017 Elsevier B.V. All rights reserved.

Experimental constrain of hydrogen production during early serpentinization stages

NASA Astrophysics Data System (ADS)

Clément, M.; Munoz, M.; Vidal, O.; Parra, T.

2009-04-01

Hydrothermal alteration of mantellic peridotites and ultramafic rocks along axial valleys of low spread oceanic ridges plays a key role in different fundamental domains like, 1) energetic gaz production (H2 and hydrocarbons) representing a potential source of energy for future generations, 2) formation of organic pre-biotic molecules in potential relation with the origin of life. Moreover, such complex volcanic-related alteration processes play fundamental role in economic geology, being widely associated to important polymetallic sulphides ore deposits. Recent researches proposed an initial hydrogen production due to the integration of ferric iron in Fe,Mg-serpentine. To better understand the early stages of hydrogen production, a series of natural peridotite rocks have been experimentally exposed to hydrothermal conditions, up to 300°C, 300 bars during different time scales. Experiments have been performed in using autoclaves with a sampling gas system. A systematic mineralogical characterization of the new products was carried out using classical spectroscopic tools. In particular, we focused on the iron behaviour using a redox and structural micro-XANES investigation. Redox information has been accurately derived from the pre-peak features previously calibrated from model compounds, while structural information about short and medium range order around iron has been extracted from the XANES region of the spectra, based both on experimental standards and ab-initio theoretical calculations. Two processes of oxidation emerged. Before two month experiment duration, serpentine displays a not negligible oxidation of ferrous iron in his structure (up to 60%), while after two months, iron oxides and hydroxides appear in the system. These results seem to correspond to natural observations. The iron coordination decreases linearly with time. It means that iron also integrates the serpentine tetrahedral sites. Moreover, high resolution µ-XAS maps on experimental samples were collected on the iron K-edge (7712 eV). These maps give valuable information concerning both kinetic of mineral phases transformation and spatial speciation of iron through the altered part of the samples. Finally, these results allow us to define a non linear model of "Fe3+ in serpentine vs hydrogen production" as a function of time.

The Iron Metallome in Eukaryotic Organisms

PubMed Central

Dlouhy, Adrienne C.; Outten, Caryn E.

2013-01-01

This chapter is focused on the iron metallome in eukaryotes at the cellular and subcellular level, including properties, utilization in metalloproteins, trafficking, storage, and regulation of these processes. Studies in the model eukaryote Saccharomyces cerevisiae and mammalian cells will be highlighted. The discussion of iron properties will center on the speciation and localization of intracellular iron as well as the cellular and molecular mechanisms for coping with both low iron bioavailability and iron toxicity. The section on iron metalloproteins will emphasize heme, iron-sulfur cluster, and non-heme iron centers, particularly their cellular roles and mechanisms of assembly. The section on iron uptake, trafficking, and storage will compare methods used by yeast and mammalian cells to import iron, how this iron is brought into various organelles, and types of iron storage proteins. Regulation of these processes will be compared between yeast and mammalian cells at the transcriptional, post-transcriptional, and post-translational levels. PMID:23595675

Evidence for ferritin as dominant iron-bearing species in the rhizobacterium Azospirillum brasilense Sp7 provided by low-temperature/in-field Mössbauer spectroscopy.

PubMed

Kovács, Krisztina; Kamnev, Alexander A; Pechoušek, Jiří; Tugarova, Anna V; Kuzmann, Ernő; Machala, Libor; Zbořil, Radek; Homonnay, Zoltán; Lázár, Károly

2016-02-01

For the ubiquitous diazotrophic rhizobacterium Azospirillum brasilense, which has been attracting the attention of researchers worldwide for the last 35 years owing to its significant agrobiotechnological and phytostimulating potential, the data on iron acquisition and its chemical speciation in cells are scarce. In this work, for the first time for azospirilla, low-temperature (at 80 K, 5 K, as well as at 2 K without and with an external magnetic field of 5 T) transmission Mössbauer spectroscopic studies were performed for lyophilised biomass of A. brasilense (wild-type strain Sp7 grown with (57)Fe(III) nitrilotriacetate complex as the sole source of iron) to enable quantitative chemical speciation analysis of the intracellular iron. In the Mössbauer spectrum at 80 K, a broadened quadrupole doublet of high-spin iron(III) was observed with a few percent of a high-spin iron(II) contribution. In the spectrum measured at 5 K, a dominant magnetically split component appeared with the parameters typical of ferritin species from other bacteria, together with a quadrupole doublet of a superparamagnetic iron(III) component and a similarly small contribution from the high-spin iron(II) component. The Mössbauer spectra recorded at 2 K (with or without a 5 T external field) confirmed the assignment of ferritin species. About 20% of total Fe in the dry cells of A. brasilense strain Sp7 were present in iron(III) forms superparamagnetic at both 5 and 2 K, i.e. either different from ferritin cores or as ferritin components with very small particle sizes.

Effect of Mineralogy on Dissolution and Speciation of Iron Containing Mineral Oxides in Atmospheric Aerosol Dust

NASA Astrophysics Data System (ADS)

Hettiarachchi, E.; Rubasinghege, G. R. S.; Reynolds, R. L.; Goldstein, H. L.; Moskowitz, B. M.

2017-12-01

Iron is one of the important trace elements for the life. Though it is the fourth most abundant element in the terrestrial crust, given higher pH ( 8.5) in the ocean, the direct dissolution of iron from the Earth crust is limited. Despite this limitation, ocean contains about 2 nM of dissolved iron that is 20-fold greater. Therefore, it is hypothesized most iron comes to the ocean via atmosphere, and dissolution occurs in the acidic atmospheric environments. The current work focuses on the effect of minerology on atmospheric processing of Fe-containing mineral dust using four authentic dust samples, collected from different parts of the world, along with three model systems, hematite (α-Fe2O3), magnetite (Fe3O4) and ilmenite (FeTiO3). Here, spectroscopic methods are combined with batch reactor studies to investigate total iron dissolution and speciation, with a specific focus on source material i.e. particle size, mineralogy, and environmental conditions, i.e. pH, temperature and solar flux. Our data suggests that the presence of Ti metal enhances the dissolution of iron regardless the total %Fe in the mineral. The surface area normalized total iron dissolution in ilmenite, under the dark conditions, in the presence of nitric acid (HNO3) is 3-fold higher than that of hematite. In authentic samples, similar effects were observed for samples containing %Ti. Further, 74% of the dissolved iron in ilmenite remained as Fe(II), bioavailable iron, whereas it was only 60% for magnetite and 8% for hematite. In this study, these results were used to interpret similar trends observed for authentic dust samples with high magnetite content. Thus, the findings of the current study highlight important, yet unconsidered, factors in the atmospheric processing of iron-containing mineral dust aerosol.

Synchrotron speciation data for zero-valent iron nanoparticles

EPA Pesticide Factsheets

This data set encompasses a complete analysis of synchrotron speciation data for 5 iron nanoparticle samples (P1, P2, P3, S1, S2, and metallic iron) to include linear combination fitting results (Table 6 and Figure 9) and ab-initio extended x-ray absorption fine structure spectroscopy fitting (Figure 10 and Table 7).Table 6: Linear combination fitting of the XAS data for the 5 commercial nZVI/ZVI products tested. Species proportions are presented as percentages. Goodness of fit is indicated by the chi^2 value.Figure 9: Normalised Fe K-edge k3-weighted EXAFS of the 5 commercial nZVI/ZVIproducts tested. Dotted lines show the best 4-component linear combination fit ofreference spectra.Figure 10: Fourier transformed radial distribution functions (RDFs) of the five samplesand an iron metal foil. The black lines in Fig. 10 represent the sample data and the reddotted curves represent the non-linear fitting results of the EXAFS data.Table 7: Coordination parameters of Fe in the samples.This dataset is associated with the following publication:Chekli, L., B. Bayatsarmadi, R. Sekine, B. Sarkar, A. Maoz Shen, K. Scheckel , W. Skinner, R. Naidu, H. Shon, E. Lombi, and E. Donner. Analytical Characterisation of Nanoscale Zero-Valent Iron: A Methodological Review. Richard P. Baldwin ANALYTICA CHIMICA ACTA. Elsevier Science Ltd, New York, NY, USA, 903: 13-35, (2016).

Effect of chaotropes on the kinetics of iron release from ferritin by flavin nucleotides.

PubMed

Johnson, Lindsay E; Wilkinson, Tyler; Arosio, Paolo; Melman, Artem; Bou-Abdallah, Fadi

2017-12-01

Ferritins are ubiquitous multi-subunit iron storage and detoxification proteins that play a critical role in iron homeostasis. Ferrous ions that enter the protein's shell through hydrophilic channels are rapidly oxidized at dinuclear centers on the H-subunit before transfer to the protein's cavity for storage. The mechanisms of iron loading have been extensively studied, but little is known about iron mobilization. Fe(III) reduction can occur via rapid reduction by suitable reducing agents followed by chelation of Fe(II) ions or via direct and slow Fe(III) chelation. Here, the iron release kinetics from ferritin by FMNH 2 in the presence of various chaotropic agents are studied and their in-vivo physiological significance discussed. The iron release kinetics from horse and human ferritins by FMNH 2 were monitored at 522nm where the Fe(II)-bipyridine complex absorbs. The experiments were performed in the presence of different concentrations of three chaotropic agents, urea, guanidine HCl, and triton. Under our experimental conditions, iron reductive mobilization by the non-enzymatic FMN/NAD(P)H system is limited by the concentration of FMNH 2 and is independent on the type or amount of chaotropes present. Diffusion of FMNH 2 through the ferritin pores is an unlikely mechanism for ferritin iron reduction. An iron mobilization mechanism involving rapid electron transfer through the protein shell is discussed. Caution must be exercised when interpreting the kinetics of iron mobilization from ferritin using the FMN/NAD(P)H system. The kinetics are highly dependent on the amount of dissolved oxygen and the concentration of reagents used. Copyright © 2017 Elsevier B.V. All rights reserved.

The life cycle of iron Fe(III) oxide: impact of fungi and bacteria

NASA Astrophysics Data System (ADS)

Bonneville, Steeve

2014-05-01

Iron oxides are ubiquitous reactive constituents of soils, sediments and aquifers. They exhibit vast surface areas which bind a large array of trace metals, nutrients and organic molecules hence controlling their mobility/reactivity in the subsurface. In this context, understanding the "life cycle" of iron oxide in soils is paramount to many biogeochemical processes. Soils environments are notorious for their extreme heterogeneity and variability of chemical, physical conditions and biological agents at play. Here, we present studies investigating the role of two biological agents driving iron oxide dynamics in soils, root-associated fungi (mycorrhiza) and bacteria. Mycorrhiza filaments (hypha) grow preferentially around, and on the surface of nutrient-rich minerals, making mineral-fungi contact zones, hot-spots of chemical alteration in soils. However, because of the microscopic nature of hyphae (only ~ 5 µm wide for up to 1 mm long) and their tendency to strongly adhere to mineral surface, in situ observations of this interfacial micro-environment are scarce. In a microcosm, ectomycorrhiza (Paxillus involutus) was grown symbiotically with a pine tree (Pinus sylvestris) in the presence of freshly-cleaved biotite under humid, yet undersaturated, conditions typical of soils. Using spatially-resolved ion milling technique (FIB), transmission electron microscopy and spectroscopy (TEM/STEM-EDS), synchrotron based X-ray microscopy (STXM), we were able to quantify the speciation of Fe at the biotite-hypha interface. The results shows that substantial oxidation of biotite structural-Fe(II) into Fe(III) subdomains occurs at the contact zone between mycorrhiza and biotite. Once formed, iron(III) oxides can reductively dissolve under suboxic conditions via several abiotic and microbial pathways. In particular, they serve as terminal electron acceptors for the oxidation of organic matter by iron reducing bacteria. We aimed here to understand the role of Fe(III) mineral properties, in particular the influence of solubility, in the kinetics of microbial iron reduction. We used the facultative anaerobic gram-positive bacterium Shewanella putrefaciens as model iron reducing bacterium, with several ferrihydrite, hematite, goethite or lepidocrocite as electron acceptor, and lactate as electron donor. Maximum microbial Fe(III) reduction rates and solubility of Fe(III) phases were found to positively correlated in a Linear Free Energy Relationship suggesting a rate limitation by the electron transfer between iron reductases and a Fe(III) center, or by the subsequent desorption of Fe2+ from the iron oxide mineral surface.

Degassing of reduced carbon from planetary basalts.

PubMed

Wetzel, Diane T; Rutherford, Malcolm J; Jacobsen, Steven D; Hauri, Erik H; Saal, Alberto E

2013-05-14

Degassing of planetary interiors through surface volcanism plays an important role in the evolution of planetary bodies and atmospheres. On Earth, carbon dioxide and water are the primary volatile species in magmas. However, little is known about the speciation and degassing of carbon in magmas formed on other planets (i.e., Moon, Mars, Mercury), where the mantle oxidation state [oxygen fugacity (fO2)] is different from that of the Earth. Using experiments on a lunar basalt composition, we confirm that carbon dissolves as carbonate at an fO2 higher than -0.55 relative to the iron wustite oxygen buffer (IW-0.55), whereas at a lower fO2, we discover that carbon is present mainly as iron pentacarbonyl and in smaller amounts as methane in the melt. The transition of carbon speciation in mantle-derived melts at fO2 less than IW-0.55 is associated with a decrease in carbon solubility by a factor of 2. Thus, the fO2 controls carbon speciation and solubility in mantle-derived melts even more than previous data indicate, and the degassing of reduced carbon from Fe-rich basalts on planetary bodies would produce methane-bearing, CO-rich early atmospheres with a strong greenhouse potential.

Molecular Speciation of Trace Metal Organic Complexes in the Pacific Ocean

NASA Astrophysics Data System (ADS)

Repeta, D.; Boiteau, R. M.; Bundy, R. M.; Babcock-Adams, L.

2017-12-01

Microbial production across approximately one third of the surface ocean is limited by extraordinarily low (picomolar) concentrations of dissolved iron, essentially all of which is complexed to strong organic ligands of unknown composition. Other biologically important trace metals (cobalt, copper, zinc, nickel) are also complexed to strong organic ligands, which again have not been extensively characterized. Nevertheless, organic ligands exert a strong influence on metal bioavailability and toxicity. For example, amendment experiments using commercially available siderophores, organic compounds synthesized by microbes to facilitate iron uptake, show these ligands can both facilitate or impede iron uptake depending on the siderophore composition and available uptake pathways. Over the past few years we have developed analytical techniques using high pressure liquid chromatography interfaced with inductively coupled plasma and electrospray ionization mass spectrometry to identify and quantify trace metal organic complexes in laboratory cultures of marine microbes and in seawater. We found siderophores to be widely distributed in the ocean, particularly in regions characterized by low iron concentrations. We also find chemically distinct complexes of copper, zinc, colbalt and nickel that we have yet to fully characterize. We will discuss some of our recent work on trace metal organic speciation in seawater and laboratory cultures, and outline future efforts to better understand the microbial cycling of trace metal organic complexes in the sea.

Biogeochemical controls on mercury methylation in the Allequash Creek wetland.

PubMed

Creswell, Joel E; Shafer, Martin M; Babiarz, Christopher L; Tan, Sue-Zanne; Musinsky, Abbey L; Schott, Trevor H; Roden, Eric E; Armstrong, David E

2017-06-01

We measured mercury methylation potentials and a suite of related biogeochemical parameters in sediment cores and porewater from two geochemically distinct sites in the Allequash Creek wetland, northern Wisconsin, USA. We found a high degree of spatial variability in the methylation rate potentials but no significant differences between the two sites. We identified the primary geochemical factors controlling net methylmercury production at this site to be acid-volatile sulfide, dissolved organic carbon, total dissolved iron, and porewater iron(II). Season and demethylation rates also appear to regulate net methylmercury production. Our equilibrium speciation modeling demonstrated that sulfide likely regulated methylation rates by controlling the speciation of inorganic mercury and therefore its bioavailability to methylating bacteria. We found that no individual geochemical parameter could explain a significant amount of the observed variability in mercury methylation rates, but we found significant multivariate relationships, supporting the widely held understanding that net methylmercury production is balance of several simultaneously occurring processes.

Organic iron (III) complexing ligands during an iron enrichment experiment in the western subarctic North Pacific

NASA Astrophysics Data System (ADS)

Kondo, Yoshiko; Takeda, Shigenobu; Nishioka, Jun; Obata, Hajime; Furuya, Ken; Johnson, William Keith; Wong, C. S.

2008-06-01

Complexation of iron (III) with natural organic ligands was investigated during a mesoscale iron enrichment experiment in the western subarctic North Pacific (SEEDS II). After the iron infusions, ligand concentrations increased rapidly with subsequent decreases. While the increases of ligands might have been partly influenced by amorphous iron colloids formation (12-29%), most in-situ increases were attributable to the <200 kDa fraction. Dilution of the fertilized patch may have contributed to the rapid decreases of the ligands. During the bloom decline, ligand concentration increased again, and the high concentrations persisted for 10 days. The conditional stability constant was not different between inside and outside of the fertilized patch. These results suggest that the chemical speciation of the released iron was strongly affected by formation of the ligands; the production of ligands observed during the bloom decline will strongly impact the iron cycle and bioavailability in the surface water.

Iron-Mediated Oxidation of Methoxyhydroquinone under Dark Conditions: Kinetic and Mechanistic Insights.

PubMed

Yuan, Xiu; Davis, James A; Nico, Peter S

2016-02-16

Despite the biogeochemical significance of the interactions between natural organic matter (NOM) and iron species, considerable uncertainty still remains as to the exact processes contributing to the rates and extents of complexation and redox reactions between these important and complex environmental components. Investigations on the reactivity of low-molecular-weight quinones, which are believed to be key redox active compounds within NOM, toward iron species, could provide considerable insight into the kinetics and mechanisms of reactions involving NOM and iron. In this study, the oxidation of 2-methoxyhydroquinone (MH2Q) by ferric iron (Fe(III)) under dark conditions in the absence and presence of oxygen was investigated within a pH range of 4-6. Although Fe(III) was capable of stoichiometrically oxidizing MH2Q under anaerobic conditions, catalytic oxidation of MH2Q was observed in the presence of O2 due to further cycling between oxygen, semiquinone radicals, and iron species. A detailed kinetic model was developed to describe the predominant mechanisms, which indicated that both the undissociated and monodissociated anions of MH2Q were kinetically active species toward Fe(III) reduction, with the monodissociated anion being the key species accounting for the pH dependence of the oxidation. The generated radical intermediates, namely semiquinone and superoxide, are of great importance in reaction-chain propagation. The kinetic model may provide critical insight into the underlying mechanisms of the thermodynamic and kinetic characteristics of metal-organic interactions and assist in understanding and predicting the factors controlling iron and organic matter transformation and bioavailability in aquatic systems.

Interactions between microbial iron reduction and metal geochemistry: effect of redox cycling on transition metal speciation in iron bearing sediments.

PubMed

Cooper, D Craig; Picardal, Flynn F; Coby, Aaron J

2006-03-15

Microbial iron reduction is an important biogeochemical process that can affect metal geochemistry in sediments through direct and indirect mechanisms. With respectto Fe(III) (hydr)oxides bearing sorbed divalent metals, recent reports have indicated that (1) microbial reduction of goethite/ferrihydrite mixtures preferentially removes ferrihydrite, (2) this process can incorporate previously sorbed Zn(II) into an authigenic crystalline phase that is insoluble in 0.5 M HCl, (3) this new phase is probably goethite, and (4) the presence of nonreducible minerals can inhibit this transformation. This study demonstrates that a range of sorbed transition metals can be selectively sequestered into a 0.5 M HCl insoluble phase and that the process can be stimulated through sequential steps of microbial iron reduction and air oxidation. Microbial reduction experiments with divalent Cd, Co, Mn, Ni, Pb, and Zn indicate that all metals save Mn experienced some sequestration, with the degree of metal incorporation into the 0.5 M HCl insoluble phase correlating positively with crystalline ionic radius at coordination number = 6. Redox cycling experiments with Zn adsorbed to synthetic goethite/ferrihydrite or iron-bearing natural sediments indicate that redox cycling from iron reducing to iron oxidizing conditions sequesters more Zn within authigenic minerals than microbial iron reduction alone. In addition, the process is more effective in goethite/ferrihydrite mixtures than in iron-bearing natural sediments. Microbial reduction alone resulted in a -3x increase in 0.5 M HCl insoluble Zn and increased aqueous Zn (Zn-aq) in goethite/ferrihydrite, but did not significantly affect Zn speciation in natural sediments. Redox cycling enhanced the Zn sequestration by approximately 12% in both goethite/ferrihydrite and natural sediments and reduced Zn-aq to levels equal to the uninoculated control in goethite/ferrihydrite and less than the uninoculated control in natural sediments. These data suggest that in situ redox cycling may serve as an effective method for

ATOMIC-SCALE DESIGN OF IRON FISCHER-TROPSCH CATALYSTS: A COMBINED COMPUTATIONAL CHEMISTRY, EXPERIMENTAL, AND MICROKINETIC MODELING APPROACH

DOE Office of Scientific and Technical Information (OSTI.GOV)

Manos Mavrikakis; James A. Dumesic; Amit A. Gokhale

2005-03-22

Efforts during this first year focused on four areas: (1) searching/summarizing published FTS mechanistic and kinetic studies of FTS reactions on iron catalysts; (2) construction of mass spectrometer-TPD and Berty CSTR reactor systems; (3) preparation and characterization of unsupported iron and alumina-supported iron catalysts at various iron loadings (4) Determination of thermochemical parameters such as binding energies of reactive intermediates, heat of FTS elementary reaction steps, and kinetic parameters such as activation energies, and frequency factors of FTS elementary reaction steps on a number of model surfaces. Literature describing mechanistic and kinetic studies of Fischer-Tropsch synthesis on iron catalysts wasmore » compiled in a draft review. Construction of the mass spectrometer-TPD system is 90% complete and of a Berty CSTR reactor system 98% complete. Three unsupported iron catalysts and three alumina-supported iron catalysts were prepared by nonaqueous-evaporative deposition (NED) or aqueous impregnation (AI) and characterized by chemisorption, BET, extent-of-reduction, XRD, and TEM methods. These catalysts, covering a wide range of dispersions and metal loadings, are well-reduced and relatively thermally stable up to 500-600 C in H{sub 2}, thus ideal for kinetic and mechanistic studies. The alumina-supported iron catalysts will be used for kinetic and mechanistic studies. In the coming year, adsorption/desorption properties, rates of elementary steps, and global reaction rates will be measured for these catalysts, with and without promoters, providing a database for understanding effects of dispersion, metal loading, and support on elementary kinetic parameters and for validation of computational models that incorporate effects of surface structure and promoters. Furthermore, using state-of-the-art self-consistent Density Functional Theory (DFT) methods, we have extensively studied the thermochemistry and kinetics of various elementary steps on three different model surfaces: (1) Fe(110), (2) Fe(110) modified by subsurface C, and (3) Fe surface modified with Pt adatoms. These studies have yielded valuable insights into the reactivity of Fe surfaces for FTS, and provided accurate estimates for the effect of Fe modifiers such as subsurface C and surface Pt.« less

Iron speciation and isotope fractionation during silicate weathering and soil formation in an alpine glacier forefield chronosequence

NASA Astrophysics Data System (ADS)

Kiczka, Mirjam; Wiederhold, Jan G.; Frommer, Jakob; Voegelin, Andreas; Kraemer, Stephan M.; Bourdon, Bernard; Kretzschmar, Ruben

2011-10-01

The chemical weathering of primary Fe-bearing minerals, such as biotite and chlorite, is a key step of soil formation and an important nutrient source for the establishment of plant and microbial life. The understanding of the relevant processes and the associated Fe isotope fractionation is therefore of major importance for the further development of stable Fe isotopes as a tracer of the biogeochemical Fe cycle in terrestrial environments. We investigated the Fe mineral transformations and associated Fe isotope fractionation in a soil chronosequence of the Swiss Alps covering 150 years of soil formation on granite. For this purpose, we combined for the first time stable Fe isotope analyses with synchrotron-based Fe-EXAFS spectroscopy, which allowed us to interpret changes in Fe isotopic composition of bulk soils, size fractions, and chemically separated Fe pools over time in terms of weathering processes. Bulk soils and rocks exhibited constant isotopic compositions along the chronosequence, whereas soil Fe pools in grain size fractions spanned a range of 0.4‰ in δ 56Fe. The clay fractions (<2 μm), in which newly formed Fe(III)-(hydr)oxides contributed up to 50% of the total Fe, were significantly enriched in light Fe isotopes, whereas the isotopic composition of silt and sand fractions, containing most of the soil Fe, remained in the range described by biotite/chlorite samples and bulk soils. Iron pools separated by a sequential extraction procedure covered a range of 0.8‰ in δ 56Fe. For all soils the lightest isotopic composition was observed in a 1 M NH 2OH-HCl-25% acetic acid extract, targeting poorly-crystalline Fe(III)-(hydr)oxides, compared with easily leachable Fe in primary phyllosilicates (0.5 M HCl extract) and Fe in residual silicates. The combination of the Fe isotope measurements with the speciation data obtained by Fe-EXAFS spectroscopy permitted to quantitatively relate the different isotope pools forming in the soils to the mineral weathering reactions which have taken place at the field site. A kinetic isotope effect during the Fe detachment from the phyllosilicates was identified as the dominant fractionation mechanism in young weathering environments, controlling not only the light isotope signature of secondary Fe(III)-(hydr)oxides but also significantly contributing to the isotope signature of plants. The present study further revealed that this kinetic fractionation effect can persist over considerable reaction advance during chemical weathering in field systems and is not only an initial transient phenomenon.

Preparation of trout liver microsomes for iron speciation in P-450 enzymes by AE-FPLC with ICP-(ORS)MS detection.

PubMed

Rodríguez-Cea, Andrés; de la Campa, María Rosario Fernández; Sanz-Medel, Alfredo

2005-01-01

Cytochromes P-450 are members of a superfamily of hemoproteins involved in the oxidative metabolism of various physiological and xenobiotic compounds in eukaryotes and prokaryotes. The multiplicity of this group of enzymes has been widely studied by chromatographic techniques, mainly high-performance liquid chromatography (HPLC). Because these enzymes are membrane-bound proteins, sample preparation for chromatographic separation of P-450 enzymes requires a solubilization step. The sample-preparation procedures are critical, because detergents affect not only the efficiency of protein solubilization but also their further chromatographic resolution. Trout liver microsomes have been taken here as a model sample to investigate iron speciation in cytochrome P-450. Trouts were treated intraperitoneally with beta-naphthoflavone, a potent inducer of some P-450 enzymes, and a microsomal suspension containing 7.4+/-0.1 nmol mL(-1) P-450 enzymes was obtained by ultracentrifugation. Lubrol PX was selected as detergent for solubilization, resulting in about 90% solubilization recovery. The solubilized cytochromes P-450 were further separated by AE-FPLC, with UV detection, or coupled to ICP-MS with an octapole reaction system, ICP-(ORS)MS (monitoring Fe signals at masses 54, 56, and 57). A sampling procedure and chromatographic conditions are developed and were successfully applied to iron speciation in trout liver P-450 enzymes. ICP-(ORS)MS detection of P-450 enzymes is Fe-specific and so will give accurate information on the prosthetic group of the protein, which can constitute an advantageous alternative to classical methods for detection of these hemoproteins.

Effects of Cloud Formation on the Speciation of Glyoxal and Methylglyoxal Hydrates and Polymers in Aerosols

NASA Astrophysics Data System (ADS)

Houghton, K. A.; Goh, P.; Spangler, R.; Schweitzer, W.; Khaled, K. A., Jr.; Berry, J.; Van Wyngarden, A. L.

2017-12-01

During cloud formation, atmospheric aerosols take up large quantities of water; the ensuing, rapid changes in water content and acidity may cause organic species within these aerosols to undergo various reactions such as hydration, hydrolysis, and/or polymerization. Glyoxal and methylglyoxal are among the most common organic molecules found within atmospheric aerosols, and prior experimental work has demonstrated that their speciation is altered during cloud processing. Due to the low water content of atmospheric aerosols, organics such as glyoxal and methylglyoxal are suspected to be significantly polymerized before cloud formation, as supported by the observation of polymers in ambient aerosols. Some of these polymerization reactions may be reversible; thus, these polymers may be subject to decomposition during cloud formation. The subsequent changes in the speciation of glyoxal and methylglyoxal polymers following cloud processing may alter the climate forcing properties of that aerosol population. The details of which polymers decompose and whether these decomposition reactions occur with sufficient speed to achieve equilibrium during the average lifetime of a cloud droplet remain unclear. Here, we use high resolution quadrupole mass spectrometry to investigate the kinetics of glyoxal and methylglyoxal speciation reactions after dilution, simulating the effects of cloud droplet formation on aerosol particles. Our data reveal that after dilution, polymers (up to the pentamer and octamer for glyoxal and methylglyoxal, respectively) persist in solution for more than 90 minutes. Furthermore, polymer speciation continues to change for hours after dilution, indicating that kinetics of at least some polymer interconversion reactions are slow with respect to a typical cloud droplet lifetime.

Composition, speciation and distribution of iron minerals in Imperata cylindrica.

PubMed

Amils, Ricardo; de la Fuente, Vicenta; Rodríguez, Nuria; Zuluaga, Javier; Menéndez, Nieves; Tornero, Jesús

2007-05-01

A comparative study of the roots, rhizomes and leaves of an iron hyperaccumulator plant, Imperata cylindrica, isolated from the banks of an extreme acidic environment, using complementary techniques: Mösbauer spectroscopy (MS), X-ray diffraction (XRD), scanning electron microscopy (SEM) coupled to energy-dispersive X-ray microanalysis (EDAX) and transmission electron microscopy (TEM), has shown that two main biominerals, jarosite and ferrihydrate-ferritin, accumulate in the different tissues. Jarosite accumulates mainly in roots and rhizomes, while ferritin has been detected in all the structures. A model of iron management in I. cylindrica is presented.

UNDERSTANDING CHLORINE AND CHLORAMINE DECAY KINETICS IN OLD CAST IRON PIPES, 2. CONVERSION FROM CONVENTIONAL TREATMENT TO MICROFILTRATION IN A SMALL WATER SYSTEM

EPA Science Inventory

This insitu pipe loop study was designed to determine the disinfectant kinetics associated with very old unlined cast iron pipelines with both chlorine and chloramination residuals. An abandoned 90-year-old unlined cast iron pipeline about 2000 ft long was acclimated to conduct a...

Mercury transformation and speciation in flue gases from anthropogenic emission sources: a critical review

NASA Astrophysics Data System (ADS)

Zhang, Lei; Wang, Shuxiao; Wu, Qingru; Wang, Fengyang; Lin, Che-Jen; Zhang, Leiming; Hui, Mulin; Yang, Mei; Su, Haitao; Hao, Jiming

2016-02-01

Mercury transformation mechanisms and speciation profiles are reviewed for mercury formed in and released from flue gases of coal-fired boilers, non-ferrous metal smelters, cement plants, iron and steel plants, waste incinerators, biomass burning and so on. Mercury in coal, ores, and other raw materials is released to flue gases in the form of Hg0 during combustion or smelting in boilers, kilns or furnaces. Decreasing temperature from over 800 °C to below 300 °C in flue gases leaving boilers, kilns or furnaces promotes homogeneous and heterogeneous oxidation of Hg0 to gaseous divalent mercury (Hg2+), with a portion of Hg2+ adsorbed onto fly ash to form particulate-bound mercury (Hgp). Halogen is the primary oxidizer for Hg0 in flue gases, and active components (e.g., TiO2, Fe2O3, etc.) on fly ash promote heterogeneous oxidation and adsorption processes. In addition to mercury removal, mercury transformation also occurs when passing through air pollution control devices (APCDs), affecting the mercury speciation in flue gases. In coal-fired power plants, selective catalytic reduction (SCR) system promotes mercury oxidation by 34-85 %, electrostatic precipitator (ESP) and fabric filter (FF) remove over 99 % of Hgp, and wet flue gas desulfurization system (WFGD) captures 60-95 % of Hg2+. In non-ferrous metal smelters, most Hg0 is converted to Hg2+ and removed in acid plants (APs). For cement clinker production, mercury cycling and operational conditions promote heterogeneous mercury oxidation and adsorption. The mercury speciation profiles in flue gases emitted to the atmosphere are determined by transformation mechanisms and mercury removal efficiencies by various APCDs. For all the sectors reviewed in this study, Hgp accounts for less than 5 % in flue gases. In China, mercury emission has a higher Hg0 fraction (66-82 % of total mercury) in flue gases from coal combustion, in contrast to a greater Hg2+ fraction (29-90 %) from non-ferrous metal smelting, cement and iron and/or steel production. The higher Hg2+ fractions shown here than previous estimates may imply stronger local environmental impacts than previously thought, caused by mercury emissions in East Asia. Future research should focus on determining mercury speciation in flue gases from iron and steel plants, waste incineration and biomass burning, and on elucidating the mechanisms of mercury oxidation and adsorption in flue gases.

Mercury transformation and speciation in flue gases from anthropogenic emission sources: a critical review

NASA Astrophysics Data System (ADS)

Zhang, L.; Wang, S. X.; Wu, Q. R.; Wang, F. Y.; Lin, C.-J.; Zhang, L. M.; Hui, M. L.; Hao, J. M.

2015-11-01

Mercury transformation mechanisms and speciation profiles are reviewed for mercury formed in and released from flue gases of coal-fired boilers, non-ferrous metal smelters, cement plants, iron and steel plants, municipal solid waste incinerators, and biomass burning. Mercury in coal, ores and other raw materials is released to flue gases in the form of Hg0 during combustion or smelting in boilers, kilns or furnaces. Decreasing temperature from over 800 °C to below 300 °C in flue gases leaving boilers, kilns or furnaces promotes homogeneous and heterogeneous oxidation of gaseous elemental mercury (Hg0) to gaseous divalent mercury (Hg2+), with a portion of Hg2+ adsorbed onto fly ash to form particulate-bound mercury (Hgp). Halogen is the primary oxidizer for Hg0 in flue gases, and active components (e.g.,TiO2, Fe2O3, etc.) on fly ash promote heterogeneous oxidation and adsorption processes. In addition to mercury removal, mercury transformation also occurs when passing through air pollution control devices (APCDs), affecting the mercury speciation in flue gases. In coal-fired power plants, selective catalytic reduction (SCR) system promotes mercury oxidation by 34-85 %, electrostatic precipitator (ESP) and fabric filter (FF) remove over 99 % of Hgp, and wet flue gas desulfurization system (WFGD) captures 60-95 % of Hg2+. In non-ferrous metal smelters, most Hg0 is converted to Hg2+ and removed in acid plants (APs). For cement clinker production, mercury cycling and operational conditions promote heterogeneous mercury oxidation and adsorption. The mercury speciation profiles in flue gases emitted to the atmosphere are determined by transformation mechanisms and mercury removal efficiencies by various APCDs. For all the sectors reviewed in this study, Hgp accounts for less than 5 % in flue gases. In China, mercury emission has a higher fraction (66-82 % of total mercury) in flue gases from coal combustion, in contrast to a greater Hg2+ fraction (29-90 %) from non-ferrous metal smelting, cement and iron/steel production. The higher Hg2+ fractions shown here than previous estimates may imply stronger local environmental impacts than previously thought, caused by mercury emissions in East Asia. Future research should focus on determining mercury speciation in flue gases from iron and steel plants, waste incineration and biomass burning, and on elucidating the mechanisms of mercury oxidation and adsorption in flue gases.

Importance of reduced sulfur for the equilibrium chemistry and kinetics of Fe(II), Co(II) and Ni(II) supplemented to semi-continuous stirred tank biogas reactors fed with stillage.

PubMed

Shakeri Yekta, Sepehr; Lindmark, Amanda; Skyllberg, Ulf; Danielsson, Asa; Svensson, Bo H

2014-03-30

The objective of the present study was to assess major chemical reactions and chemical forms contributing to solubility and speciation of Fe(II), Co(II), and Ni(II) during anaerobic digestion of sulfur (S)-rich stillage in semi-continuous stirred tank biogas reactors (SCSTR). These metals are essential supplements for efficient and stable performance of stillage-fed SCSTR. In particular, the influence of reduced inorganic and organic S species on kinetics and thermodynamics of the metals and their partitioning between aqueous and solid phases were investigated. Solid phase S speciation was determined by use of S K-edge X-ray absorption near-edge spectroscopy. Results demonstrated that the solubility and speciation of supplemented Fe were controlled by precipitation of FeS(s) and formation of the aqueous complexes of Fe-sulfide and Fe-thiol. The relatively high solubility of Co (∼ 20% of total Co content) was attributed to the formation of compounds other than Co-sulfide and Co-thiol, presumably of microbial origin. Nickel had lower solubility than Co and its speciation was regulated by interactions with FeS(s) (e.g. co-precipitation, adsorption, and ion substitution) in addition to precipitation/dissolution of discrete NiS(s) phase and formation of aqueous Ni-sulfide complexes. Copyright © 2014 Elsevier B.V. All rights reserved.

A model of Fe speciation and biogeochemistry at the Tropical Eastern North Atlantic Time-Series Observatory site

NASA Astrophysics Data System (ADS)

Ye, Y.; Völker, C.; Wolf-Gladrow, D. A.

2009-10-01

A one-dimensional model of Fe speciation and biogeochemistry, coupled with the General Ocean Turbulence Model (GOTM) and a NPZD-type ecosystem model, is applied for the Tropical Eastern North Atlantic Time-Series Observatory (TENATSO) site. Among diverse processes affecting Fe speciation, this study is focusing on investigating the role of dust particles in removing dissolved iron (DFe) by a more complex description of particle aggregation and sinking, and explaining the abundance of organic Fe-binding ligands by modelling their origin and fate. The vertical distribution of different particle classes in the model shows high sensitivity to changing aggregation rates. Using the aggregation rates from the sensitivity study in this work, modelled particle fluxes are close to observations, with dust particles dominating near the surface and aggregates deeper in the water column. POC export at 1000 m is a little higher than regional sediment trap measurements, suggesting further improvement of modelling particle aggregation, sinking or remineralisation. Modelled strong ligands have a high abundance near the surface and decline rapidly below the deep chlorophyll maximum, showing qualitative similarity to observations. Without production of strong ligands, phytoplankton concentration falls to 0 within the first 2 years in the model integration, caused by strong Fe-limitation. A nudging of total weak ligands towards a constant value is required for reproducing the observed nutrient-like profiles, assuming a decay time of 7 years for weak ligands. This indicates that weak ligands have a longer decay time and therefore cannot be modelled adequately in a one-dimensional model. The modelled DFe profile is strongly influenced by particle concentration and vertical distribution, because the most important removal of DFe in deeper waters is colloid formation and aggregation. Redissolution of particulate iron is required to reproduce an observed DFe profile at TENATSO site. Assuming colloidal iron is mainly composed of inorganic colloids, the modelled colloidal to soluble iron ratio is lower that observations, indicating the importance of organic colloids.

Degassing of reduced carbon from planetary basalts

PubMed Central

Wetzel, Diane T.; Rutherford, Malcolm J.; Jacobsen, Steven D.; Hauri, Erik H.; Saal, Alberto E.

2013-01-01

Degassing of planetary interiors through surface volcanism plays an important role in the evolution of planetary bodies and atmospheres. On Earth, carbon dioxide and water are the primary volatile species in magmas. However, little is known about the speciation and degassing of carbon in magmas formed on other planets (i.e., Moon, Mars, Mercury), where the mantle oxidation state [oxygen fugacity (fO2)] is different from that of the Earth. Using experiments on a lunar basalt composition, we confirm that carbon dissolves as carbonate at an fO2 higher than -0.55 relative to the iron wustite oxygen buffer (IW-0.55), whereas at a lower fO2, we discover that carbon is present mainly as iron pentacarbonyl and in smaller amounts as methane in the melt. The transition of carbon speciation in mantle-derived melts at fO2 less than IW-0.55 is associated with a decrease in carbon solubility by a factor of 2. Thus, the fO2 controls carbon speciation and solubility in mantle-derived melts even more than previous data indicate, and the degassing of reduced carbon from Fe-rich basalts on planetary bodies would produce methane-bearing, CO-rich early atmospheres with a strong greenhouse potential. PMID:23569260

Microbial Sulfate Reduction Enhances Arsenic Mobility Downstream of Zerovalent-Iron-Based Permeable Reactive Barrier.

PubMed

Kumar, Naresh; Couture, Raoul-Marie; Millot, Romain; Battaglia-Brunet, Fabienne; Rose, Jérôme

2016-07-19

We assessed the potential of zerovalent-iron- (Fe(0)) based permeable reactive barrier (PRB) systems for arsenic (As) remediation in the presence or absence of microbial sulfate reduction. We conducted long-term (200 day) flow-through column experiments to investigate the mechanisms of As transformation and mobility in aquifer sediment (in particular, the PRB downstream linkage). Changes in As speciation in the aqueous phase were monitored continuously. Speciation in the solid phase was determined at the end of the experiment using X-ray absorption near-edge structure (XANES) spectroscopy analysis. We identified thio-As species in solution and AsS in solid phase, which suggests that the As(V) was reduced to As(III) and precipitated as AsS under sulfate-reducing conditions and remained as As(V) under abiotic conditions, even with low redox potential and high Fe(II) content (4.5 mM). Our results suggest that the microbial sulfate reduction plays a key role in the mobilization of As from Fe-rich aquifer sediment under anoxic conditions. Furthermore, they illustrate that the upstream-downstream linkage of PRB affects the speciation and mobility of As in downstream aquifer sediment, where up to 47% of total As initially present in the sediment was leached out in the form of mobile thio-As species.

Effect of iron oxide reductive dissolution on the transformation and immobilization of arsenic in soils: New insights from X-ray photoelectron and X-ray absorption spectroscopy.

PubMed

Fan, Jian-Xin; Wang, Yu-Jun; Liu, Cun; Wang, Li-Hua; Yang, Ke; Zhou, Dong-Mei; Li, Wei; Sparks, Donald L

2014-08-30

The geochemical behavior and speciation of arsenic (As) in paddy soils is strongly controlled by soil redox conditions and the sequestration by soil iron oxyhydroxides. Hence, the effects of iron oxide reductive dissolution on the adsorption, transformation and precipitation of As(III) and As(V) in soils were investigated using batch experiments and synchrotron based techniques to gain a deeper understanding at both macroscopic and microscopic scales. The results of batch sorption experiments revealed that the sorption capacity of As(V) on anoxic soil was much higher than that on control soil. Synchrotron based X-ray fluorescence (μ-XRF) mapping studies indicated that As was heterogeneously distributed and was mainly associated with iron in the soil. X-ray absorption near edge structure (XANES), micro-X-ray absorption near edge structure (μ-XANES) and X-ray photoelectron spectroscopy (XPS) analyses revealed that the primary speciation of As in the soil is As(V). These results further suggested that, when As(V) was introduced into the anoxic soil, the rapid coprecipitation of As(V) with ferric/ferrous ion prevented its reduction to As(III), and was the main mechanism controlling the immobilization of As. This research could improve the current understanding of soil As chemistry in paddy and wetland soils. Copyright © 2014 Elsevier B.V. All rights reserved.

Iron speciation in peats: Chemical and spectroscopic evidence for the co-occurrence of ferric and ferrous iron in organic complexes and mineral precipitates

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bhattacharyya, Amrita; Schmidt, Michael P.; Stavitski, Eli

The speciation of iron (Fe) in organic matter (OM)-rich environments under in situ variable redox conditions is largely unresolved. Peatlands provide a natural setting to study Fe–OM interactions. Utilizing chemical, spectroscopic and theoretical modeling approaches, we report the chemical forms, oxidation states and local coordination environment of naturally occurring Fe in the vertically redox-stratified Manning peatlands of western New York. In addition, we report dominant carbon, sulfur and nitrogen species that can potentially stabilize the various Fe species present in these peatlands. Our results provide clear direct and indirect evidence for the co-occurrence of ferrous (Fe 2+) and ferric (Femore » 3+) iron species in peats under both oxic and anoxic conditions. Iron is mostly present within the operationally defined organic and amorphous (i.e., short range ordered, SRO) fractions; ferric iron primarily as magnetically isolated paramagnetic Fe 3+ in Fe(III)-organic complexes, but also in mineral forms such as ferrihydrite; ferrous iron in tetrahedral coordination in Fe(II)-organic complexes with minor contribution from pyrite. All of the Fe species identified stabilize Fe(III) and/or Fe(II) in anoxic and oxic peats. Fundamental differences are also observed in the relative proportion of C, S and N functionalities of OM in oxic and anoxic peats. Aromatic C=C, ester, phenol and anomeric C (R-O-C-O-R), as well as thiol, sulfide and heterocyclic N functionalities are more prevalent in anoxic peats. Collectively, our experimental evidence suggests iron forms coordination complexes with O-, S- and N-containing functional groups of OM. We posit the co-occurrence of organic and mineral forms of Fe(II) and Fe(III) in both oxic and anoxic peat layers results from dynamic complexation and hydrolysis-precipitation reactions that occur under variable redox conditions. In conclusion, our findings aid in understanding the crucial role OM plays in determining Fe species in soils and sediments.« less

Iron speciation in peats: Chemical and spectroscopic evidence for the co-occurrence of ferric and ferrous iron in organic complexes and mineral precipitates

DOE PAGES

Bhattacharyya, Amrita; Schmidt, Michael P.; Stavitski, Eli; ...

2017-10-31

The speciation of iron (Fe) in organic matter (OM)-rich environments under in situ variable redox conditions is largely unresolved. Peatlands provide a natural setting to study Fe–OM interactions. Utilizing chemical, spectroscopic and theoretical modeling approaches, we report the chemical forms, oxidation states and local coordination environment of naturally occurring Fe in the vertically redox-stratified Manning peatlands of western New York. In addition, we report dominant carbon, sulfur and nitrogen species that can potentially stabilize the various Fe species present in these peatlands. Our results provide clear direct and indirect evidence for the co-occurrence of ferrous (Fe 2+) and ferric (Femore » 3+) iron species in peats under both oxic and anoxic conditions. Iron is mostly present within the operationally defined organic and amorphous (i.e., short range ordered, SRO) fractions; ferric iron primarily as magnetically isolated paramagnetic Fe 3+ in Fe(III)-organic complexes, but also in mineral forms such as ferrihydrite; ferrous iron in tetrahedral coordination in Fe(II)-organic complexes with minor contribution from pyrite. All of the Fe species identified stabilize Fe(III) and/or Fe(II) in anoxic and oxic peats. Fundamental differences are also observed in the relative proportion of C, S and N functionalities of OM in oxic and anoxic peats. Aromatic C=C, ester, phenol and anomeric C (R-O-C-O-R), as well as thiol, sulfide and heterocyclic N functionalities are more prevalent in anoxic peats. Collectively, our experimental evidence suggests iron forms coordination complexes with O-, S- and N-containing functional groups of OM. We posit the co-occurrence of organic and mineral forms of Fe(II) and Fe(III) in both oxic and anoxic peat layers results from dynamic complexation and hydrolysis-precipitation reactions that occur under variable redox conditions. In conclusion, our findings aid in understanding the crucial role OM plays in determining Fe species in soils and sediments.« less

Revision of iron(III)-citrate speciation in aqueous solution. Voltammetric and spectrophotometric studies.

PubMed

Vukosav, Petra; Mlakar, Marina; Tomišić, Vladislav

2012-10-01

A detailed study of iron (III)-citrate speciation in aqueous solution (θ=25°C, I(c)=0.7 mol L(-1)) was carried out by voltammetric and UV-vis spectrophotometric measurements and the obtained data were used for reconciled characterization of iron (III)-citrate complexes. Four different redox processes were registered in the voltammograms: at 0.1 V (pH=5.5) which corresponded to the reduction of iron(III)-monocitrate species (Fe:cit=1:1), at about -0.1 V (pH=5.5) that was related to the reduction of FeL(2)(5-), FeL(2)H(4-) and FeL(2)H(2)(3-) complexes, at -0.28 V (pH=5.5) which corresponded to the reduction of polynuclear iron(III)-citrate complex(es), and at -0.4V (pH=7.5) which was probably a consequence of Fe(cit)(2)(OH)(x) species reduction. Reversible redox process at -0.1 V allowed for the determination of iron(III)-citrate species and their stability constants by analyzing E(p) vs. pH and E(p) vs. [L(4-)] dependence. The UV-vis spectra recorded at varied pH revealed four different spectrally active species: FeLH (logβ=25.69), FeL(2)H(2)(3-) (log β=48.06), FeL(2)H(4-) (log β=44.60), and FeL(2)(5-) (log β=38.85). The stability constants obtained by spectrophotometry were in agreement with those determined electrochemically. The UV-vis spectra recorded at various citrate concentrations (pH=2.0) supported the results of spectrophotometric-potentiometric titration. Copyright © 2012 Elsevier B.V. All rights reserved.

Kinetics of heavy metal adsorption and desorption in soil: Developing a unified model based on chemical speciation

NASA Astrophysics Data System (ADS)

Peng, Lanfang; Liu, Paiyu; Feng, Xionghan; Wang, Zimeng; Cheng, Tao; Liang, Yuzhen; Lin, Zhang; Shi, Zhenqing

2018-03-01

Predicting the kinetics of heavy metal adsorption and desorption in soil requires consideration of multiple heterogeneous soil binding sites and variations of reaction chemistry conditions. Although chemical speciation models have been developed for predicting the equilibrium of metal adsorption on soil organic matter (SOM) and important mineral phases (e.g. Fe and Al (hydr)oxides), there is still a lack of modeling tools for predicting the kinetics of metal adsorption and desorption reactions in soil. In this study, we developed a unified model for the kinetics of heavy metal adsorption and desorption in soil based on the equilibrium models WHAM 7 and CD-MUSIC, which specifically consider metal kinetic reactions with multiple binding sites of SOM and soil minerals simultaneously. For each specific binding site, metal adsorption and desorption rate coefficients were constrained by the local equilibrium partition coefficients predicted by WHAM 7 or CD-MUSIC, and, for each metal, the desorption rate coefficients of various binding sites were constrained by their metal binding constants with those sites. The model had only one fitting parameter for each soil binding phase, and all other parameters were derived from WHAM 7 and CD-MUSIC. A stirred-flow method was used to study the kinetics of Cd, Cu, Ni, Pb, and Zn adsorption and desorption in multiple soils under various pH and metal concentrations, and the model successfully reproduced most of the kinetic data. We quantitatively elucidated the significance of different soil components and important soil binding sites during the adsorption and desorption kinetic processes. Our model has provided a theoretical framework to predict metal adsorption and desorption kinetics, which can be further used to predict the dynamic behavior of heavy metals in soil under various natural conditions by coupling other important soil processes.

Arsenite and Ferrous Iron Oxidation Linked to Chemolithotrophic Denitrification for the Immobilization of Arsenic in Anoxic Environments

PubMed Central

Sun, Wenjie; Sierra-Alvarez, Reyes; Milner, Lily; Oremland, Ron; Field, Jim A.

2014-01-01

The objective of this study was to explore a bioremediation strategy based on injecting NO3− to support the anoxic oxidation of ferrous iron (Fe(II)) and arsenite (As(III)) in the subsurface as a means to immobilize As in the form of arsenate (As(V)) adsorbed onto biogenic ferric (Fe(III)) (hydr)oxides. Continuous flow sand filled columns were used to simulate a natural anaerobic groundwater and sediment system with co-occurring As(III) and Fe(II) in the presence (SF1) or absence (SF2) of nitrate, respectively. During operation for 250 days, the average influent arsenic concentration of 567 µg l−1 was reduced to 10.6 (±9.6) µg l−1 in the effluent of column SF1. The cumulative removal of Fe(II) and As(III) in SF1 was 6.5–10-fold higher than that in SF2. Extraction and measurement of the mass of iron and arsenic immobilized on the sand packing of the columns was close to the iron and arsenic removed from the aqueous phase during column operation. The dominant speciation of the immobilized iron and arsenic was Fe(III) and As(V) in SF1, compared with Fe(II) and As(III) in SF2. The speciation was confirmed by XRD and XPS. The results indicate that microbial oxidation of As(III) and Fe(II) linked to denitrification resulted in the enhanced immobilization of aqueous arsenic in anaerobic environments by forming Fe(III) (hydr)oxides coated sands with adsorbed As(V). PMID:19764221

Storm water runoff measurements of copper from a naturally patinated roof and from a parking space. Aspects on environmental fate and chemical speciation.

PubMed

Odnevall Wallinder, I; Hedberg, Y; Dromberg, P

2009-12-01

Release of copper from a naturally aged copper roof on a shopping centre building in a suburban site of Stockholm has been measured during different rain events after its interaction with the internal drainage system and storm drains made of cast iron and concrete. Concentrations of copper removed by means of urban storm water from a nearby parking space have been determined for comparison. Predictions and measurements of the chemical speciation of released copper are discussed compared to the total concentration, and to threshold values for freshwater and drinking water. The results clearly illustrate that the major part of the released copper from the roof is readily retained already during transport through the internal drainage system of the building, a pathway that also changes the chemical speciation of released copper and its bioavailable fraction. Most copper, not retained by cast iron and concrete surfaces, was strongly complexed to organic matter. The median concentration of free cupric ions and weak copper complexes was less than, or within the range of reported no effect concentrations, NOECs, of copper in surface waters. The parking space contributed with significantly higher and time-dependent concentrations of total copper compared to measured concentrations of copper from the roof after the interaction with the drainage system. Most copper in the surface runoff water was strongly complexed with organic matter, hence reducing the bioavailable fraction significantly to concentrations within the NOEC range. Dilution with other sources of urban storm water will reduce the released concentration of copper even further. The results illustrate that already the internal drainage system and the storm drains made of cast iron and concrete act as efficient sinks for released copper which means that any installation of additional infiltration devices is redundant.

Speciation in the Fe(III)-Cl(I)-H2O System at 298.15 K, 313.15 K, and 333.15 K (25 °C, 40 °C, and 60 °C)

NASA Astrophysics Data System (ADS)

Jamett, Nathalie E.; Hernández, Pía C.; Casas, Jesús M.; Taboada, María E.

2018-02-01

This article presents the results on speciation of ferric iron generated by the dissolution of chemical reagent hydromolysite (ferric chloride hexahydrate, FeCl3:6H2O) in water at 298.15 K, 313.15 K, and 333.15 K (25 °C, 40 °C, and 60 °C). Experiments were performed with a thermoregulated system up to the equilibrium point, as manifested by solution pH. Solution samples were analyzed in terms of concentration, pH, and electrical conductivity. Measurements of density and refractive index were obtained at different temperatures and iron concentrations. A decrease of pH was observed with the increase in the amount of dissolved iron, indicating that ferric chloride is a strong electrolyte that reacts readily with water. Experimental results were modeled using the hydrogeochemical code PHREEQC in order to obtain solution speciation. Cations and neutral and anion complexes were simultaneously present in the system at the studied conditions according to model simulations, where dominant species included Cl-, FeCl2+, FeCl2 +, FeOHCl 2 0 , and H+. A decrease in the concentration of Cl- and Fe3+ ions took place with increasing temperature due to the association of Fe-Cl species. Standard equilibrium constants for the formation of FeOHCl 2 0 obtained in this study were log Kf0 = -0.8 ± 0.01 at 298.15 K (25 °C), -0.94 ± 0.02 at 313.15 K (40 °C), and -1.03 ± 0.01 at 333.15 K (60 °C).

The analysis of forms of sulfur in ancient sediments and sedimentary rocks: comments and cautions

USGS Publications Warehouse

Rice, C.A.; Tuttle, M.L.; Reynolds, R.L.

1993-01-01

Assumptions commonly made during analysis of the amount of monosulfides [acid-volatile sulfides (AVS)] and disulfides in modern sediments, may not be valid for ancient sedimentary rocks. It is known that ferric iron can oxidize H2S during AVS analysis unless a reducing agent such as stannous chloride is added to the treatment. In addition, some monosulfides such as greigite and pyrrhotite require heat during the AVS analysis in order to dissolve completely. However, the use of heat and/or stannous chloride in the AVS treatment may partially dissolve disulfides and it is generally recommended that stannous chloride not be used in the AVS treatment for modern sediments. Most of the monosulfides are assumed to be recovered as AVS without the addition of stannous chloride. This study investigates the recovery of monosulfides during sulfur speciation analysis with application to ancient sedimentary rocks. Sulfur in samples containing naturally occurring greigite and mackinawite or pyrite was measured using variations of a common sulfur-speciation scheme. The sulfur-speciation scheme analyzes for monosulfide sulfur, disulfide sulfur, elemental sulfur, inorganic sulfate and organically bound sulfur. The effects of heat, stannous chloride and ferric iron on the amounts of acid-volatile sulfide and disulfide recovered during treatment for AVS were investigated. Isotopic compositions of the recovered sulfur species along with yields from an extended sulfur-speciation scheme were used to quantify the effects. Hot 6 N HCl AVS treatment recovers > 60% of the monosulfides as AVS in samples containing pure greigite and mackinawite. The remaining monosulfide sulfur is recovered in a subsequent elemental sulfur extraction. Hot 6 N HCl plus stannous chloride recovers 100% of the monosulfides as AVS. The addition of ferric iron to pure greigite and mackinawite samples during AVS treatment without stannous chloride decreased the amount of monosulfides recovered as AVS and, if present in great enough concentration, oxidized some of the AVS to a form not recovered in later treatments. The hot stannous chloride AVS treatments dissolve <5% of well-crystallized pyrite in this study. The amount of pyrite dissolved depends on grain size and crystallinity. Greigite in ancient sedimentary rocks was quantitatively recovered as AVS only with hot 6 N HCl plus stannous chloride. Hot 6 N HCl AVS treatment of these rocks did not detect any monosulfides in most samples. A subsequent elemental sulfur extraction did not completely recover the oxidized monosulfides. Therefore, the use of stannous chloride plus heat is recommended in the AVS treatment of ancient sedimentary rocks if monosulfides are present and of interest. All assumptions about the amount of monosulfides and disulfides recovered with the sulfur-speciation scheme used should be verified by extended sulfur-speciation and/or isotopic analysis of the species recovered. ?? 1993.

Iron isotope fractionation during microbially stimulated Fe(II) oxidation and Fe(III) precipitation

USGS Publications Warehouse

Balci, N.; Bullen, T.D.; Witte-Lien, K.; Shanks, Wayne C.; Motelica, M.; Mandernack, K.W.

2006-01-01

Interpretation of the origins of iron-bearing minerals preserved in modern and ancient rocks based on measured iron isotope ratios depends on our ability to distinguish between biological and non-biological iron isotope fractionation processes. In this study, we compared 56Fe/54Fe ratios of coexisting aqueous iron (Fe(II)aq, Fe(III)aq) and iron oxyhydroxide precipitates (Fe(III)ppt) resulting from the oxidation of ferrous iron under experimental conditions at low pH (<3). Experiments were carried out using both pure cultures of Acidothiobacillus ferrooxidans and sterile controls to assess possible biological overprinting of non-biological fractionation, and both SO42- and Cl- salts as Fe(II) sources to determine possible ionic/speciation effects that may be associated with oxidation/precipitation reactions. In addition, a series of ferric iron precipitation experiments were performed at pH ranging from 1.9 to 3.5 to determine if different precipitation rates cause differences in the isotopic composition of the iron oxyhydroxides. During microbially stimulated Fe(II) oxidation in both the sulfate and chloride systems, 56Fe/54Fe ratios of residual Fe(II)aq sampled in a time series evolved along an apparent Rayleigh trend characterized by a fractionation factor ??Fe(III)aq-Fe(II)aq???1.0022. This fractionation factor was significantly less than that measured in our sterile control experiments (???1.0034) and that predicted for isotopic equilibrium between Fe(II)aq and Fe(III)aq (???1.0029), and thus might be interpreted to reflect a biological isotope effect. However, in our biological experiments the measured difference in 56Fe/54Fe ratios between Fe(III)aq, isolated as a solid by the addition of NaOH to the final solution at each time point under N2-atmosphere, and Fe(II)aq was in most cases and on average close to 2.9??? (??Fe(III)aq-Fe(II)aq ???1.0029), consistent with isotopic equilibrium between Fe(II)aq and Fe(III)aq. The ferric iron precipitation experiments revealed that 56Fe/54Fe ratios of Fe(III)aq were generally equal to or greater than those of Fe(III)ppt, and isotopic fractionation between these phases decreased with increasing precipitation rate and decreasing grain size. Considered together, the data confirm that the iron isotope variations observed in our microbial experiments are primarily controlled by non-biological equilibrium and kinetic factors, a result that aids our ability to interpret present-day iron cycling processes but further complicates our ability to use iron isotopes alone to identify biological processing in the rock record. ?? 2005 Elsevier Inc. All rights reserved.

Linear Combination Fitting (LCF)-XANES analysis of As speciation in selected mine-impacted materials

EPA Pesticide Factsheets

This table provides sample identification labels and classification of sample type (tailings, calcinated, grey slime). For each sample, total arsenic and iron concentrations determined by acid digestion and ICP analysis are provided along with arsenic in-vitro bioaccessibility (As IVBA) values to estimate arsenic risk. Lastly, the table provides linear combination fitting results from synchrotron XANES analysis showing the distribution of arsenic speciation phases present in each sample along with fitting error (R-factor).This dataset is associated with the following publication:Ollson, C., E. Smith, K. Scheckel, A. Betts, and A. Juhasz. Assessment of arsenic speciation and bioaccessibility in mine-impacted materials. Diana Aga, Wonyong Choi, Andrew Daugulis, Gianluca Li Puma, Gerasimos Lyberatos, and Joo Hwa Tay JOURNAL OF HAZARDOUS MATERIALS. Elsevier Science Ltd, New York, NY, USA, 313: 130-137, (2016).

ARSENIC PARTITIONING TO IRON OXIDES AND SULFIDES: LOCAL ENVIRONMENT AND OXIDATION STATE

EPA Science Inventory

his document summarizes research activities conducted at the Advanced Photon Source at Argonne National Laboratory, Argonne, IL during FY2003. The analytical data collected using X-ray absorption spectroscopy was used to evaluated the chemical speciation of arsenic associated wi...

Kinetics of Fe Release from Organic Ligand Complexes: Implications for Fe Isotopes?

NASA Astrophysics Data System (ADS)

Nuester, J.; Liermann, L. J.; Brantley, S. L.

2006-12-01

Although iron is the fourth most abundant element in the earth's surface, its bioavailability is limited by its natural tendency to form insoluble iron (oxyhydr)oxides in terrestrial and marine environments. Paradoxically, iron is an essential nutrient for virtually all living cells, so in order to survive, organisms must develop mechanisms to solubilize iron. To acquire iron, organisms synthesize and release iron-specific chelators called siderophores. These siderophores facilitate the transformation of insoluble crystal-bound iron to organically ligand-bound dissolved iron. The reverse process whereby ferric iron is released from siderophores resulting in the precipitation of iron (oxyhydr)oxides or complexation by other iron chelators is an important but not well studied process in the B-horizon of soils. Fe mobility is documented in soils where Fe is often extracted at the top and precipitated at depth. Both the concentration and isotopic signature of Fe varies with depth due to dissolution, precipitation, sorption, and biological processes. Our study is focused on measurement of isotopic fractionation during this reverse process. In a first approach to understand iron liberation form organic ligands, we mimic this process using a reductive mechanism. We use acetohydroxamic acid (aha), EDTA and desferrioxamine B (DFMB) as test ligands to investigate iron release by sodium ascorbate at varying pH. Our first kinetic measurements showed significant differences in iron release depending on pH and stability of the iron complex. Within one hour all iron is released from aha with a small pH effect in the pH range between 4 and 6. In contrast, the pH has a major influence on the iron release from EDTA and DFMB. Depending on pH, total iron is released from EDTA within 24 hours, while only an incomplete iron release from DFMB could be observed within two weeks. These strong kinetic differences in iron release as a consequence of iron reduction are expected to result in significant iron isotope effects, and we are testing for these effects. For example, we expect to see enrichment of light isotopes in the early released fractions as iron is reduced (like effects observed by Wiederhold et al. (2006) for ligand-controlled and reductive dissolution of goethite). Such kinetic isotope effects should be particularly strong for iron release from siderophores with high Fe affinities like DFMB (log ß_(Fe(III)) = 30.60). We are also investigating other mechanisms to liberate iron from organic ligands including a pathway with extracellular iron reductases.

Iron oxide nanoparticle-based magnetic resonance method to monitor release kinetics from polymeric particles with high resolution.

PubMed

Chan, Minnie; Schopf, Eric; Sankaranarayanan, Jagadis; Almutairi, Adah

2012-09-18

A new method to precisely monitor rapid release kinetics from polymeric particles using super paramagnetic iron oxide nanoparticles, specifically by measuring spin-spin relaxation time (T(2)), is reported. Previously, we have published the formulation of logic gate particles from an acid-sensitive poly-β-aminoester ketal-2 polymer. Here, a series of poly-β-aminoester ketal-2 polymers with varying hydrophobicities were synthesized and used to formulate particles. We attempted to measure fluorescence of released Nile red to determine whether the structural adjustments could finely tune the release kinetics in the range of minutes to hours; however, this standard technique did not differentiate each release rate of our series. Thus, a new method based on encapsulation of iron oxide nanoparticles was developed, which enabled us to resolve the release kinetics of our particles. Moreover, the kinetics matched the relative hydrophobicity order determined by octanol-water partition coefficients. To the best of our knowledge, this method provides the highest resolution of release kinetics to date.

The importance of ligand speciation in environmental research: a case study.

PubMed

Sillanpää, M; Orama, M; Rämö, J; Oikari, A

2001-02-21

The speciations of EDTA and DTPA in process, waste and river waters are modelled and simulated, specifically to the mode of occurrence in the pulp and paper mill effluents and subsequently in receiving waters. Due to relatively short residence times in bleaching process and waste water treatment and slow exchange kinetics, it is expected that the thermodynamic equilibrium is not necessarily reached. Therefore, the initial speciation plays a key role. As such, the simulations have been extended to the process waters of the pulp and paper industry taking into account estimated average conditions. The results reveal that the main species are; Mn and Ca complexes of EDTA and DTPA in pulp mill process waters; Fe(III) and Mn complexes of EDTA and DTPA in waste waters; Fe(III) and Zn complexes of EDTA and DTPA in receiving waters. It is also shown how the increasing concentration of complexing agents effects the speciation. Alkaline earth metal chelation plays a significant role in the speciation of EDTA and DTPA when there is a noticeable molar excess of complexing agents compared with transition metals.

Nanoscale zero-valent iron for metal/metalloid removal from model hydraulic fracturing wastewater.

PubMed

Sun, Yuqing; Lei, Cheng; Khan, Eakalak; Chen, Season S; Tsang, Daniel C W; Ok, Yong Sik; Lin, Daohui; Feng, Yujie; Li, Xiang-Dong

2017-06-01

Nanoscale zero-valent iron (nZVI) was tested for the removal of Cu(II), Zn(II), Cr(VI), and As(V) in model saline wastewaters from hydraulic fracturing. Increasing ionic strength (I) from 0.35 to 4.10 M (Day-1 to Day-90 wastewaters) increased Cu(II) removal (25.4-80.0%), inhibited Zn(II) removal (58.7-42.9%), slightly increased and then reduced Cr(VI) removal (65.7-44.1%), and almost unaffected As(V) removal (66.7-75.1%) by 8-h reaction with nZVI at 1-2 g L -1 . The removal kinetics conformed to pseudo-second-order model, and increasing I decreased the surface area-normalized rate coefficient (k sa ) of Cu(II) and Cr(VI), probably because agglomeration of nZVI in saline wastewaters restricted diffusion of metal(loid)s to active surface sites. Increasing I induced severe Fe dissolution from 0.37 to 0.77% in DIW to 4.87-13.0% in Day-90 wastewater; and Fe dissolution showed a significant positive correlation with Cu(II) removal. With surface stabilization by alginate and polyvinyl alcohol, the performance of entrapped nZVI in Day-90 wastewater was improved for Zn(II) and Cr(VI), and Fe dissolution was restrained (3.20-7.36%). The X-ray spectroscopic analysis and chemical speciation modelling demonstrated that the difference in removal trends from Day-1 to Day-90 wastewaters was attributed to: (i) distinctive removal mechanisms of Cu(II) and Cr(VI) (adsorption, (co-)precipitation, and reduction), compared to Zn(II) (adsorption) and As(V) (bidentate inner-sphere complexation); and (ii) changes in solution speciation (e.g., from Zn 2+ to ZnCl 3 - and ZnCl 4 2- ; from CrO 4 2- to CaCrO 4 complex). Bare nZVI was susceptible to variations in wastewater chemistry while entrapped nZVI was more stable and environmentally benign, which could be used to remove metals/metalloids before subsequent treatment for reuse/disposal. Copyright © 2017 Elsevier Ltd. All rights reserved.

Silica Precipitation from Geothermal Brines: Effects of Iron Addition, Kinetics, Temperature, pH, and Brine Concentration

DOE Data Explorer

Jay Renew

2016-02-06

This document provides results of experiments aimed at removing silica from geothermal brines. All experiments were conducted with simulated brines. The data presented shows the effect of iron addition, kinetics, temperature, pH and brine concentration.

Transient state kinetic investigation of ferritin iron release

NASA Astrophysics Data System (ADS)

Ciasca, G.; Papi, M.; Chiarpotto, M.; Rodio, M.; Campi, G.; Rossi, C.; De Sole, P.; Bianconi, A.

2012-02-01

Increased iron concentration in tissues appears to be a factor in the genesis and development of inflammatory and degenerative diseases. By means of real-time small angle x-ray scattering measurements, we studied the kinetics of iron release from the ferritin inorganic core as a function of time and distance from the iron core centre. Accordingly, the iron release process follows a three step model: (i) a defect nucleation in the outer part of the mineral core, (ii) the diffusion of the reducing agent towards the inner part of the core, and (iii) the erosion of the core from the inner to the outer part.

Characteristics and Kinetic Analysis of AQS Transformation and Microbial Goethite Reduction:Insight into "Redox mediator-Microbe-Iron oxide" Interaction Process.

PubMed

Zhu, Weihuang; Shi, Mengran; Yu, Dan; Liu, Chongxuan; Huang, Tinglin; Wu, Fengchang

2016-03-29

The characteristics and kinetics of redox transformation of a redox mediator, anthraquinone-2-sulfonate (AQS), during microbial goethite reduction by Shewanella decolorationis S12, a dissimilatory iron reduction bacterium (DIRB), were investigated to provide insights into "redox mediator-iron oxide" interaction in the presence of DIRB. Two pre-incubation reaction systems of the "strain S12- goethite" and the "strain S12-AQS" were used to investigate the dynamics of goethite reduction and AQS redox transformation. Results show that the concentrations of goethite and redox mediator, and the inoculation cell density all affect the characteristics of microbial goethite reduction, kinetic transformation between oxidized and reduced species of the redox mediator. Both abiotic and biotic reactions and their coupling regulate the kinetic process for "Quinone-Iron" interaction in the presence of DIRB. Our results provide some new insights into the characteristics and mechanisms of interaction among "quinone-DIRB- goethite" under biotic/abiotic driven.

Kinetics of Transferrin and Transferrin-Receptor during Iron Transport through Blood Brain Barrier

NASA Astrophysics Data System (ADS)

Khan, Aminul; Liu, Jin; Dutta, Prashanta

2017-11-01

Transferrin and its receptors play an important role during the uptake and transcytosis of iron by blood brain barrier (BBB) endothelial cells to maintain iron homeostasis in BBB endothelium and brain. In the blood side of BBB, ferric iron binds with the apo-transferrin to form holo-transferrin which enters the endothelial cell via transferrin receptor mediated endocytosis. Depending on the initial concentration of iron inside the cell endocytosed holo-transferrin can either be acidified in the endosome or exocytosed through the basolateral membrane. Acidification of holo-transferrin in the endosome releases ferrous irons which may either be stored and used by the cell or transported into brain side. Exocytosis of the holo-transferrin through basolateral membrane leads to transport of iron bound to transferrin into brain side. In this work, kinetics of internalization, recycling and exocytosis of transferrin and its receptors are modeled by laws of mass action during iron transport in BBB endothelial cell. Kinetic parameters for the model are determined by least square analysis. Our results suggest that the cell's initial iron content determines the extent of the two possible iron transport pathways, which will be presented in this talk Research reported in this publication was supported by the National Institute of General Medical Sciences of the National Institutes of Health under Award Number R01GM122081.

The Speciation of Sulfur in an Ocean on Europa

NASA Technical Reports Server (NTRS)

Zolotov, M. Yu.; Shock, E. L.

2002-01-01

Stability of native sulfur, iron sulfides, and aqueous sulfur compounds is evaluated at assumed P-T conditions of the Europa's ocean floor. Pyrite, gypsum, and ferric hydroxides can coexist in contact with sulfate-rich oceanic water. Additional information is contained in the original extended abstract.

Water management impacts on arsenic speciation and iron-reducing bacteria in contrasting rice-rhizosphere compartments.

PubMed

Somenahally, Anil C; Hollister, Emily B; Yan, Wengui; Gentry, Terry J; Loeppert, Richard H

2011-10-01

Rice cultivated on arsenic (As) contaminated-soils will accumulate variable grain-As concentrations, as impacted by varietal differences, soil variables, and crop management. A field-scale experiment was conducted to study the impact of intermittent and continuous flooding on As speciation and microbial populations in rice rhizosphere compartments of soils that were either historically amended with As pesticide or unamended with As. Rhizosphere-soil, root-plaque, pore-water and grain As were quantified and speciated, and microbial populations in rhizosphere soil and root-plaque were characterized. Total-As concentrations in rhizosphere and grain were significantly lower in intermittently flooded compared to the continuously flooded plots (86% lower in pore-water, 55% lower in root-plaque and 41% lower in grain samples). iAs(V), iAs(III), and DMAs(V) were the predominant As species detected in rhizosphere-soil and root-plaque, pore-water and grain samples, respectively. Relative proportions of Archaea and iron-reducing bacteria (FeRB) were higher in rhizosphere soil compared to root-plaque. In rhizosphere soil, the relative abundance of FeRB was lower in intermittently flooded compared to continuously flooded plots, but there were no differences between root-plaque samples. This study has demonstrated that reductions in dissolved As concentrations in the rhizosphere and subsequent decreases in grain-As concentration can be attained through water management.

Coal fly ash as a source of iron in atmospheric dust.

PubMed

Chen, Haihan; Laskin, Alexander; Baltrusaitis, Jonas; Gorski, Christopher A; Scherer, Michelle M; Grassian, Vicki H

2012-02-21

Anthropogenic coal fly ash (FA) aerosol may represent a significant source of bioavailable iron in the open ocean. Few measurements have been made that compare the solubility of atmospheric iron from anthropogenic aerosols and other sources. We report here an investigation of iron dissolution for three FA samples in acidic aqueous solutions and compare the solubilities with that of Arizona test dust (AZTD), a reference material for mineral dust. The effects of pH, simulated cloud processing, and solar radiation on iron solubility have been explored. Similar to previously reported results on mineral dust, iron in aluminosilicate phases provides the predominant component of dissolved iron. Iron solubility of FA is substantially higher than of the crystalline minerals comprising AZTD. Simulated atmospheric processing elevates iron solubility due to significant changes in the morphology of aluminosilicate glass, a dominant material in FA particles. Iron is continuously released into the aqueous solution as FA particles break up into smaller fragments. These results suggest that the assessment of dissolved atmospheric iron deposition fluxes and their effect on the biogeochemistry at the ocean surface should be constrained by the source, environmental pH, iron speciation, and solar radiation.

Erythroblast transferrin receptors and transferrin kinetics in iron deficiency and various anemias

DOE Office of Scientific and Technical Information (OSTI.GOV)

Muta, K.; Nishimura, J.; Ideguchi, H.

1987-06-01

To clarify the role of transferrin receptors in cases of altered iron metabolism in clinical pathological conditions, we studied: number of binding sites; affinity; and recycling kinetics of transferrin receptors on human erythroblasts. Since transferrin receptors are mainly present on erythroblasts, the number of surface transferrin receptors was determined by assay of binding of /sup 125/I-transferrin and the percentage of erythroblasts in bone marrow mononuclear cells. The number of binding sites on erythroblasts from patients with an iron deficiency anemia was significantly greater than in normal subjects. Among those with an aplastic anemia, hemolytic anemia, myelodysplastic syndrome, and polycythemia veramore » compared to normal subjects, there were no considerable differences in the numbers of binding sites. The dissociation constants (Kd) were measured using Scatchard analysis. The apparent Kd was unchanged (about 10 nmol/L) in patients and normal subjects. The kinetics of endocytosis and exocytosis of /sup 125/I-transferrin, examined by acid treatment, revealed no variations in recycling kinetics among the patients and normal subjects. These data suggest that iron uptake is regulated by modulation of the number of surface transferrin receptors, thereby reflecting the iron demand of the erythroblast.« less

[Iron from soil to plant products].

PubMed

Briat, Jean-François

2005-11-01

As an essential mineral, iron plays an important role in fundamental biological processes such as photosynthesis, respiration, nitrogen fixation and assimilation, and DNA synthesis. Iron is also a co-factor of many enzymes involved in the synthesis of plant hormones. The latter are involved in many pathways controling plant development or adaptative responses to environmental conditions. Iron reactivity with oxygen leads to its insolubility (responsible for deficiency) and potential toxicity, and complicates iron use by aerobic organisms. If plants lacked an active root system with which to acquire iron from the soil, most would experience iron deficiency and show physiological changes. In contrast, an excess of soluble iron, which can occur in flooded acidic soils, can lead to ferrous iron toxicity due to iron reactivity with reduced forms of oxygen and subsequent free radical production. An optimal iron concentration is thus required for a plant to grow and develop normally. This concentration depends on multiple regulatory mechanisms controlling iron uptake from soil by the roots, as well as iron transport and distribution to the various plant organs. Optimized seed iron content is a major biotechnological challenge identified by the World Health Organization, and it is therefore crucial to understand the underlying mechanisms. Iron delivery to seeds is tightly controlled, and depends on the nature of iron speciation in specific chelates, and their transport.

Kinetic and thermodynamic parameters for heat denaturation of human recombinant lactoferrin from rice.

PubMed

Castillo, Eduardo; Pérez, María Dolores; Franco, Indira; Calvo, Miguel; Sánchez, Lourdes

2012-06-01

Heat denaturation of recombinant human lactoferrin (rhLf) from rice with 3 different iron-saturation degrees, holo rhLf (iron-saturated), AsIs rhLf (60% iron saturation), and apo rhLf (iron-depleted), was studied. The 3 forms of rhLf were subjected to heat treatment, and the kinetic and thermodynamic parameters of the denaturation process were determined. Thermal denaturation of rhLf was assessed by measuring the loss of reactivity against specific antibodies. D(t) values (time to reduce 90% of immunoreactivity) decreased with increasing temperature of treatment for apo and holo rhLf, those values being higher for the iron-saturated form, which indicates that iron confers thermal stability to rhLf. However, AsIs rhLf showed a different behaviour with an increase in resistance to heat between 79 °C and 84 °C, so that the kinetic parameters could not be calculated. The heat denaturation process for apo and holo rhLf was best described assuming a reaction order of 1.5. The activation energy of the denaturation process was 648.20 kJ/mol for holo rhLf and 406.94 kJ/mol for apo rhLf, confirming that iron-depleted rhLf is more sensitive to heat treatment than iron-saturated rhLf.

Redox speciation of dissolved iron in the northeastern atlantic ocean.

NASA Astrophysics Data System (ADS)

Ussher, S. J.; Achterberg, E. P.; Worsfold, P. J.

2003-04-01

Dissolved iron (<0.2 micron) and iron(II) (<0.2 micron) distributions were determined during the Iron from Below and Iron from Above research cruises in the North Eastern Atlantic Ocean. The cruises were part of the EU Ironages project. Iron(II) was measured on-board ship using an iron(II) specific, automated flow injection analyser with luminol chemiluminescence detection [1]. Total dissolved iron (DFe) was determined in a land-based laboratory, using the same FI technique but with prior reduction of iron(III) to iron(II) [2]. The limits of detection for the methods were 5 -15 pM and 35 pM respectively, the analysis time was 8 - 10 minutes per sample (minimum of 3 replicates). The Iron from Below expedition took place over the European Continental Shelf, 200 km South West of Brittany (France) in March 2002. A transect between 47.61°N, 4.24°W and 46.00°N, 8.01°W was completed. Over the transect, the depth increased from 100 m to 5000 m. Iron(II) concentrations ranged between 10 and 100 pM and DFe between 0.2 and 1 nM, with the higher concentrations (Fe(II) ca. > 50 pM and DFe ca. > 0.8 nM) generally found in the shallow shelf waters. These observations imply that benthic inputs and sediment resuspension may form important inputs of dissolved iron and iron(II) in the shelf waters. Iron speciation measurements were also made for underway surface and shallow cast samples during the Iron from Above cruise October 2002. Fe(II) and DFe concentrations were typically 5 to 50 pM and 0.2 to 0.6 nM, respectively. Sampling was carried out within a grid in the Canary Basin around 5 degrees W of the Canary Islands, an area assumed to be strongly influenced by the Saharan dust plume. Observed Fe(II) concentrations are compared and ratioed to the DFe concentrations, and indicate that iron(II) forms an important fraction (between 5 and 15%) of the total dissolved iron concentration in the study areas. Data plots for surface samples are presented with the corresponding physical oceanographic and solar irradiance data. The concentrations of Fe(II) observed during our studies exceed the values predicted from thermodynamic equilibrium modelling. This indicates that there is a steady supply of Fe(II) (possibly from photoreduction and/or biological origins) and/or Fe(II) is prevented from oxidation through stabilisation mechanisms (possibly by organic ligands). [1] A. R. Bowie, E. P. Achterberg, P. N. Sedwick, S. Ussher, P. J. Worsfold, Environ. Sci. Technol., 36, (2002) 4600. [2] A. R. Bowie, E. P. Achterberg, R. F. C. Mantoura, P. J. Worsfold, Anal. Chim. Acta, 377, (1998) 113.

Arsenite and ferrous iron oxidation linked to chemolithotrophic denitrification for the immobilization of arsenic in anoxic environments

USGS Publications Warehouse

Sun, W.; Sierra-Alvarez, R.; Milner, L.; Oremland, R.; Field, J.A.

2009-01-01

The objective of this study was to explore a bioremediation strategy based on injecting NO3- to support the anoxic oxidation of ferrous iron (Fe(II)) and arsenite (As(III)) in the subsurface as a means to immobilize As in the form of arsenate (As(V)) adsorbed onto biogenic ferric (Fe(III)) (hydr)oxides. Continuous flows and filled columns were used to simulate a natural anaerobic groundwater and sediment system with co-occurring As(III) and Fe(II) in the presence (column SF1) or absence (column SF2) of nitrate, respectively. During operation for 250 days, the average influent arsenic concentration of 567 ??g L-1 was reduced to 10.6 (??9.6) ??g L-1 in the effluent of column SF1. The cumulative removal of Fe(II) and As(III) in SF1 was 6.5 to 10-fold higher than that in SF2. Extraction and measurement of the mass of iron and arsenic immobilized on the sand packing of the columns were close to the iron and arsenic removed from the aqueous phase during column operation. The dominant speciation of the immobilized iron and arsenic was Fe(III) and As(V) in SF1, compared with Fe(II) and As(III) in SF2. The speciation was confirmed by X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The results indicate that microbial oxidation of As(III) and Fe(II) linked to denitrification resulted in the enhanced immobilization of aqueous arsenic in anaerobic environments by forming Fe(III) (hydr)oxide coated sands with adsorbed As(V). ?? 2009 American Chemical Society.

Assessing the Selectivity of Extractant Solutions for Recovering Labile Arsenic Associated with Iron (Hydr)oxides and Sulfides in Sediments

EPA Science Inventory

Sequential extractions can provide analytical constraints on the identification of mineral phases that control arsenic speciation in sediments. Model solids were used in this study to evaluate different solutions designed to extract arsenic from relatively labile solid phases. ...

CD SPECIATION ASSOCIATED WITH IRON OXIDES AND BIOSOLIDS

EPA Science Inventory

The environmental impact and potential hazards of metals in biosolids to plants, animals and the human food chain have been studied for decades. From this body of work, it has been concluded the addition of biosolids to the soil alters the chemical phases in the soil system beyon...

Iron Drinking Water Pipe Corrosion Products: Concentrators of Toxic Metals

DTIC Science & Technology

2013-01-01

health risk. In addition Pb corrosion products may be sinks for other metals such as chromium (Cr), copper (Cu), manganese (Mn), and zinc (Zn). These...Vanadium K-Edge X-ray Absorption Near-Edge Structure Interpretation: Application to the Speciation of Vanadium in Oxide Phases from Steel Slag ’, Journal

Experimental determination of iron isotope fractionations among Fe aq 2 + -FeSaq-Mackinawite at low temperatures: Implications for the rock record

NASA Astrophysics Data System (ADS)

Wu, Lingling; Druschel, Greg; Findlay, Alyssa; Beard, Brian L.; Johnson, Clark M.

2012-07-01

The Fe isotope fractionation factors among aqueous ferrous iron (Fe aq 2 +), aqueous FeS clusters (FeSaq), and nanoparticulate mackinawite under neutral and mildly acidic and alkaline pH conditions have been determined using the three-isotope method. Combined voltammetric analysis and geochemical modeling were used to determine the Fe speciation in the experimental systems. The equilibrium 56Fe/54Fe fractionation factor at 20 °C and pH 7 has been determined to be -0.32 ± 0.29 (2σ)‰ between Fe aq 2 + (minor FeSaq also present in the experiment) and mackinawite. This fractionation factor was essentially constant when pH was changed to 6 or 8. When equal molarity of HS- and Fe aq 2 + were added to the system, however, the isotopic fractionation at pH 7 changed to -0.64 ± 0.36 (2σ)‰, correlating with a significant increase in the proportion of FeHS+ and FeSaq. These results highlight a more important role of aqueous Fe-S speciation in the equilibrium Fe isotope fractionation factor than recognized in previous studies. The isotopic fractionation remained constant when temperature was increased from 20 °C to 35 °C for fractionation factors between Fe aq 2 + , and mackinawite and between dominantly FeHS+ and mackinawite. Synthesis experiments similar to those of Butler et al. (2005) and Guilbaud et al. (2010) at pH 4 show consistent results: over time, the aqueous Fe-mackinawite fractionation decreases but even after 38 days of aging the fractionation factor is far from the equilibrium value inferred using the three-isotope method. In contrast, at near-neutral pH the fractionation factor for the synthesis experiment reached the equilibrium value in 38 days. These differences are best explained by noting that at low pH the FeS mackinawite particles coarsen more rapidly via particle aggregation, which limits isotopic exchange, whereas at higher pH mackinawite aggregation is limited, and Fe isotope exchange occurs more rapidly, converging on the equilibrium value. These results suggest that mackinawite formed in natural environments at near-neutral or alkaline pH are unlikely to retain kinetic isotope fractionations, but are more likely to reflect equilibrium isotope compositions. This in turn has important implications for interpreting iron isotope compositions of Fe sulfides in natural systems.

Effects of Dissolved Carbonate on Arsenate Adsorption and Surface Speciation at the Hematite-Water Interface

USGS Publications Warehouse

Arai, Y.; Sparks, D.L.; Davis, J.A.

2004-01-01

Effects of dissolved carbonate on arsenate [As(V)] reactivity and surface speciation at the hematite-water interface were studied as a function of pH and two different partial pressures of carbon dioxide gas [PCO2 = 10 -3.5 atm and ???0; CO2-free argon (Ar)] using adsorption kinetics, pseudo-equilibrium adsorption/titration experiments, extended X-ray absorption fine structure spectroscopic (EXAFS) analyses, and surface complexation modeling. Different adsorbed carbonate concentrations, due to the two different atmospheric systems, resulted in an enhanced and/or suppressed extent of As(V) adsorption. As(V) adsorption kinetics [4 g L -1, [As(V)]0 = 1.5 mM and / = 0.01 M NaCl] showed carbonate-enhanced As(V) uptake in the air-equilibrated systems at pH 4 and 6 and at pH 8 after 3 h of reaction. Suppressed As(V) adsorption was observed in the air-equilibrated system in the early stages of the reaction at pH 8. In the pseudo-equilibrium adsorption experiments [1 g L-1, [As(V)] 0 = 0.5 mM and / = 0.01 M NaCl], in which each pH value was held constant by a pH-stat apparatus, effects of dissolved carbonate on As(V) uptake were almost negligible at equilibrium, but titrant (0.1 M HCl) consumption was greater in the air-equilibrated systems (PCO2 = 10-3.5 atm)than in the CO2-free argon system at pH 4-7.75. The EXAFS analyses indicated that As(V) tetrahedral molecules were coordinated on iron octahedral via bidentate mononuclear (???2.8 A??) and bidentate binuclear (???3.3 A??) bonding at pH 4.5-8 and loading levels of 0.46-3.10 ??M m-2. Using the results of the pseudoequilibrium adsorption data and the XAS analyses, the pH-dependent As(V) adsorption under the PCO2 = 10-3.5 atm and the CO2-free argon system was modeled using surface complexation modeling, and the results are consistent with the formation of nonprotonated bidentate surface species at the hematite surfaces. The results also suggest that the acid titrant consumption was strongly affected by changes to electrical double-layer potentials caused by the adsorption of carbonate in the air-equilibrated system. Overall results suggest that the effects of dissolved carbonate on As(V) adsorption were influenced by the reaction conditions [e.g., available surface sites, initial As(V) concentrations, and reaction times]. Quantifying the effects of adsorbed carbonate may be important in predicting As(V) transport processes in groundwater, where iron oxide-coated aquifer materials are exposed to seasonally fluctuating partial pressures of CO2(g).

Speciation and distribution of arsenic and localization of nutrients in rice grains

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lombi, E.; Scheckel, K.G.; Pallon, J.

2012-09-05

Arsenic (As) contamination of rice grains and the generally low concentration of micronutrients in rice have been recognized as a major concern for human health. Here, we investigated the speciation and localization of As and the distribution of (micro)nutrients in rice grains because these are key factors controlling bioavailability of nutrients and contaminants. Bulk total and speciation analyses using high-pressure liquid chromatography (HPLC)-inductively coupled plasma mass spectrometry (ICP-MS) and X-ray absorption near-edge spectroscopy (XANES) was complemented by spatially resolved microspectroscopic techniques ({mu}-XANES, {mu}-X-ray fluorescence ({mu}-XRF) and particle induced X-ray emission (PIXE)) to investigate both speciation and distribution of As andmore » localization of nutrients in situ. The distribution of As and micronutrients varied between the various parts of the grains (husk, bran and endosperm) and was characterized by element-specific distribution patterns. The speciation of As in bran and endosperm was dominated by As(III)-thiol complexes. The results indicate that the translocation from the maternal to filial tissues may be a bottleneck for As accumulation in the grain. Strong similarities between the distribution of iron (Fe), manganese (Mn) and phosphorus (P) and between zinc (Zn) and sulphur (S) may be indicative of complexation mechanisms in rice grains.« less

Alginate-Iron Speciation and Its Effect on In Vitro Cellular Iron Metabolism

PubMed Central

Horniblow, Richard D.; Dowle, Miriam; Iqbal, Tariq H.; Latunde-Dada, Gladys O.; Palmer, Richard E.

2015-01-01

Alginates are a class of biopolymers with known iron binding properties which are routinely used in the fabrication of iron-oxide nanoparticles. In addition, alginates have been implicated in influencing human iron absorption. However, the synthesis of iron oxide nanoparticles employs non-physiological pH conditions and whether nanoparticle formation in vivo is responsible for influencing cellular iron metabolism is unclear. Thus the aims of this study were to determine how alginate and iron interact at gastric-comparable pH conditions and how this influences iron metabolism. Employing a range of spectroscopic techniques under physiological conditions alginate-iron complexation was confirmed and, in conjunction with aberration corrected scanning transmission electron microscopy, nanoparticles were observed. The results infer a nucleation-type model of iron binding whereby alginate is templating the condensation of iron-hydroxide complexes to form iron oxide centred nanoparticles. The interaction of alginate and iron at a cellular level was found to decrease cellular iron acquisition by 37% (p < 0.05) and in combination with confocal microscopy the alginate inhibits cellular iron transport through extracellular iron chelation with the resulting complexes not internalised. These results infer alginate as being useful in the chelation of excess iron, especially in the context of inflammatory bowel disease and colorectal cancer where excess unabsorbed luminal iron is thought to be a driver of disease. PMID:26378798

Plasma Assisted Combustion: Flame Regimes and Kinetic Studies

DTIC Science & Technology

2015-01-05

Kinetic model Fuel: Dimethyl ether Oxidizer= (1-x)O2 + xO3, x=0 - 0.1, p=1 atm Ozone chemistry & Dimethyl ether model ...diffusional cool flames • A heated counterflow burner integrated with vaporization system1 • n-heptane/nitrogen vs. oxygen/ ozone • Ozone generator...micro-DBD) produces 2- 5 % of ozone in oxygen stream, depending on oxygen flow rate • Speciation profiles by using a micro-probe sampling with a

ULTRASOUND PRETREATMENT OF ELEMENTAL IRON: KINETIC STUDIES OF DEHALOGENATION REACTION ENHANCEMENT AND SURFACE EFFECTS. (R828598C743)

EPA Science Inventory

This work presents data showing the kinetic improvement afforded by ultrasound pretreatment and illustrates the physical and chemical changes that take place at the iron surface. First-order rate constants improved as much as 78% with 2 h of ultrasound pretreatment. Scann...

Ligand exchange in ionic systems and its effect on silver nucleation and growth.

PubMed

Abbott, Andrew P; Azam, Muhammad; Frisch, Gero; Hartley, Jennifer; Ryder, Karl S; Saleem, Saima

2013-10-28

The electrodeposition of metals from ionic solutions is intrinsically linked to the reactivity of the solute ions. When metal salts dissolve, the exchange of the anion with the molecular and ionic components from solution affects the speciation and therefore the characteristics of metal reduction. This study investigates the nucleation mechanism, deposition kinetics, metal speciation and diffusion coefficients of silver salts dissolved in Deep Eutectic Solvents. The electrochemical reduction of AgCl, AgNO3 and Ag2O is studied in 1 : 2 choline chloride : ethylene glycol and 1 : 2 choline chloride : urea. Cyclic voltammetry is used to evaluate electrochemical kinetics. Detailed analysis of chronoamperometric data shows that silver deposits form via multiple 3D nucleation with mass transport controlled hemispherical growth. The nucleation mechanism was found to be potential dependent, varying from progressive to instantaneous as the reduction potential becomes more cathodic. Diffusion coefficients are determined using three different methods. Trends are rationalised in terms of solvent viscosity and silver speciation analysis with EXAFS. The morphology of electroreduced silver is investigated with scanning electron microscopy and shows that deposits from the urea based liquid form more dense morphologies than those from the ethylene glycol based liquid.

Dissolved sulfides in the oxic water column of San Francisco Bay, California

USGS Publications Warehouse

Kuwabara, J.S.; Luther, G.W.

1993-01-01

Trace contaminants enter major estuaries such as San Francisco Bay from a variety of point and nonpoint sources and may then be repartitioned between solid and aqueous phases or altered in chemical speciation. Chemical speciation affects the bioavailability of metals as well as organic ligands to planktonic and benthic organisms, and the partitioning of these solutes between phases. Our previous, work in south San Francisco Bay indicated that sulfide complexation with metals may be of particular importance because of the thermodynamic stability of these complexes. Although the water column of the bay is consistently well-oxygenated and typically unstratified with respect to dissolved oxygen, the kinetics of sulfide oxidation could exert at least transient controls on metal speciation. Our initial data on dissolved sulfides in the main channel of both the northern and southern components of the bay consistently indicate submicromolar concenrations (from <1 nM to 162 nM), as one would expect in an oxidizing environment. However, chemical speciation calculations over the range of observed sulfide concentrations indicate that these trace concentrations in the bay water column can markedly affect chemical speciation of ecologically significant trace metals such as cadmium, copper, and zinc.

Iron solubility related to particle sulfur content in source emission and ambient fine particles.

PubMed

Oakes, M; Ingall, E D; Lai, B; Shafer, M M; Hays, M D; Liu, Z G; Russell, A G; Weber, R J

2012-06-19

The chemical factors influencing iron solubility (soluble iron/total iron) were investigated in source emission (e.g., biomass burning, coal fly ash, mineral dust, and mobile exhaust) and ambient (Atlanta, GA) fine particles (PM2.5). Chemical properties (speciation and mixing state) of iron-containing particles were characterized using X-ray absorption near edge structure (XANES) spectroscopy and micro-X-ray fluorescence measurements. Bulk iron solubility (soluble iron/total iron) of the samples was quantified by leaching experiments. Major differences were observed in iron solubility in source emission samples, ranging from low solubility (<1%, mineral dust and coal fly ash) up to 75% (mobile exhaust and biomass burning emissions). Differences in iron solubility did not correspond to silicon content or Fe(II) content. However, source emission and ambient samples with high iron solubility corresponded to the sulfur content observed in single particles. A similar correspondence between bulk iron solubility and bulk sulfate content in a series of Atlanta PM2.5 fine particle samples (N = 358) further supported this trend. In addition, results of linear combination fitting experiments show the presence of iron sulfates in several high iron solubility source emission and ambient PM2.5 samples. These results suggest that the sulfate content (related to the presence of iron sulfates and/or acid-processing mechanisms by H(2)SO(4)) of iron-containing particles is an important proxy for iron solubility.

The placenta: the forgotten essential organ of iron transport

PubMed Central

Cao, Chang

2016-01-01

Optimal iron nutrition in utero is essential for development of the fetus and helps establish birth iron stores adequate to sustain growth in early infancy. In species with hemochorial placentas, such as humans and rodents, iron in the maternal circulation is transferred to the fetus by directly contacting placental syncytiotrophoblasts. Early kinetic studies provided valuable data on the initial uptake of maternal transferrin, an iron-binding protein, by the placenta. However, the remaining steps of iron trafficking across syncytiotrophoblasts and through the fetal endothelium into the fetal blood remain poorly characterized. Over the last 20 years, identification of transmembrane iron transporters and the iron regulatory hormone hepcidin has greatly expanded the knowledge of cellular iron transport and its regulation by systemic iron status. In addition, emerging human and animal data demonstrating comprised fetal iron stores in severe maternal iron deficiency challenge the classic dogma of exclusive fetal control over the transfer process and indicate that maternal and local signals may play a role in regulating this process. This review compiles current data on the kinetic, molecular, and regulatory aspects of placental iron transport and considers new questions and knowledge gaps raised by these advances. PMID:27261274

Iron persistence in a distal hydrothermal plume supported by dissolved-particulate exchange

NASA Astrophysics Data System (ADS)

Fitzsimmons, Jessica N.; John, Seth G.; Marsay, Christopher M.; Hoffman, Colleen L.; Nicholas, Sarah L.; Toner, Brandy M.; German, Christopher R.; Sherrell, Robert M.

2017-02-01

Hydrothermally sourced dissolved metals have been recorded in all ocean basins. In the oceans' largest known hydrothermal plume, extending westwards across the Pacific from the Southern East Pacific Rise, dissolved iron and manganese were shown by the GEOTRACES program to be transported halfway across the Pacific. Here, we report that particulate iron and manganese in the same plume also exceed background concentrations, even 4,000 km from the vent source. Both dissolved and particulate iron deepen by more than 350 m relative to 3He--a non-reactive tracer of hydrothermal input--crossing isopycnals. Manganese shows no similar descent. Individual plume particle analyses indicate that particulate iron occurs within low-density organic matrices, consistent with its slow sinking rate of 5-10 m yr-1. Chemical speciation and isotopic composition analyses reveal that particulate iron consists of Fe(III) oxyhydroxides, whereas dissolved iron consists of nanoparticulate Fe(III) oxyhydroxides and an organically complexed iron phase. The descent of plume-dissolved iron is best explained by reversible exchange onto slowly sinking particles, probably mediated by organic compounds binding iron. We suggest that in ocean regimes with high particulate iron loadings, dissolved iron fluxes may depend on the balance between stabilization in the dissolved phase and the reversibility of exchange onto sinking particles.

High-Iron Biosolids Compost-Induced Changes in Lead and Arsenic Speciation and Bioaccessibility in Co-contaminated Soils

EPA Science Inventory

The safety of urban farming has been questioned due to the potential for contamination in urban soils. A laboratory incubation, a field trial, and a second laboratory incubation were conducted to test the ability of high-Fe biosolids–based composts to reduce the bioaccessibil...

Speciation And Distribution Of Vanadium In Drinking Water Iron Pipe Corrosion By-Products

EPA Science Inventory

Vanadium (V) when ingested from drinking water in high concentrations (> 15 µg L^-1) is a potential health risk and is on track to becoming a regulated contaminant. High concentrations of V have been documented in lead corrosion by-products as Pb₅(V⁵⁺

Shock tube and chemical kinetic modeling study of the oxidation of 2,5-dimethylfuran.

PubMed

Sirjean, Baptiste; Fournet, René; Glaude, Pierre-Alexandre; Battin-Leclerc, Frédérique; Wang, Weijing; Oehlschlaeger, Matthew A

2013-02-21

A detailed kinetic model describing the oxidation of 2,5-dimethylfuran (DMF), a potential second-generation biofuel, is proposed. The kinetic model is based upon quantum chemical calculations for the initial DMF consumption reactions and important reactions of intermediates. The model is validated by comparison to new DMF shock tube ignition delay time measurements (over the temperature range 1300-1831 K and at nominal pressures of 1 and 4 bar) and the DMF pyrolysis speciation measurements of Lifshitz et al. [ J. Phys. Chem. A 1998 , 102 ( 52 ), 10655 - 10670 ]. Globally, modeling predictions are in good agreement with the considered experimental targets. In particular, ignition delay times are predicted well by the new model, with model-experiment deviations of at most a factor of 2, and DMF pyrolysis conversion is predicted well, to within experimental scatter of the Lifshitz et al. data. Additionally, comparisons of measured and model predicted pyrolysis speciation provides validation of theoretically calculated channels for the oxidation of DMF. Sensitivity and reaction flux analyses highlight important reactions as well as the primary reaction pathways responsible for the decomposition of DMF and formation and destruction of key intermediate and product species.

Controls on the Fate and Speciation of Np(V) During Iron (Oxyhydr)oxide Crystallization.

PubMed

Bots, Pieter; Shaw, Samuel; Law, Gareth T W; Marshall, Timothy A; Mosselmans, J Frederick W; Morris, Katherine

2016-04-05

The speciation and fate of neptunium as Np(V)O2(+) during the crystallization of ferrihydrite to hematite and goethite was explored in a range of systems. Adsorption of NpO2(+) to iron(III) (oxyhydr)oxide phases was reversible and, for ferrihydrite, occurred through the formation of mononuclear bidentate surface complexes. By contrast, chemical extractions and X-ray absorption spectroscopy (XAS) analyses showed the incorporation of Np(V) into the structure of hematite during its crystallization from ferrihydrite (pH 10.5). This occurred through direct replacement of octahedrally coordinated Fe(III) by Np(V) in neptunate-like coordination. Subsequent analyses on mixed goethite and hematite crystallization products (pH 9.5 and 11) showed that Np(V) was incorporated during crystallization. Conversely, there was limited evidence for Np(V) incorporation during goethite crystallization at the extreme pH of 13.3. This is likely due to the formation of a Np(V) hydroxide precipitate preventing incorporation into the goethite particles. Overall these data highlight the complex behavior of Np(V) during the crystallization of iron(III) (oxyhydr)oxides, and demonstrate clear evidence for neptunium incorporation into environmentally important mineral phases. This extends our knowledge of the range of geochemical conditions under which there is potential for long-term immobilization of radiotoxic Np in natural and engineered environments.

Effect of Transport and Aging Processes on Metal Speciation in Iron Oxyhydroxide Aggregates, Tar Creek Superfund Site, Oklahoma

NASA Astrophysics Data System (ADS)

Estes, E. R.; Schaider, L. A.; Shine, J. P.; Brabander, D. J.

2010-12-01

Following the cessation of mining activity in the late 20th century, Tar Creek Superfund Site was left highly contaminated by Pb, Zn, and Cd. Tar Creek, which flows through the site and into the Neosho River, has been studied extensively because of its potential to transport metals from the mining site to downstream communities. Previous research identified aggregated iron oxyhydroxide material, which forms when mine seepage mixes with Tar Creek surface water, as a major transport vector of metals. Frequent flooding in Tar Creek deposits aggregates on downstream floodplains, where wetting and drying processes alter the speciation of iron and other metals. This study seeks to better quantify those changes and to determine how transport and aging affects the human and ecological health risk. Sequential extractions of aggregate samples collected from the creek demonstrate that Fe is present in both amorphous (10-35% of Fe extracted) and more crystalline (8-23% of Fe extracted) phases. Substantial portions of heavy metals sorb to amorphous iron oxyhydroxide phases (accounting for 10-30% of Pb and Zn extracted) but are not associated with more crystalline iron oxide phases (representing only 1% or less of the Pb and Zn extracted). Samples have a high organic matter content (18-25% mass loss on ignition), but only Fe was significantly extracted by the oxidizing step targeting organic matter (1-2% of Pb and Zn extracted, but 10-26% of Fe extracted). The majority of metals were extracted by the soluble or residual steps. If metals and organic matter inhibit transformation of amorphous iron oxyhydroxide material to nano and crystalline iron oxides, then a steady-state volume of amorphous iron oxyhydroxide material with a high total sorption capacity may exist within Tar Creek, enhancing the metal flux accommodated by this transport mechanism. Once transported downstream and deposited on floodplains, however, it is hypothesized that repeated changes in soil matrix composition and thermodynamic conditions could facilitate a transformation to more crystalline iron phases and increase metal bioavailability. While preliminary data from in-creek aggregates show no clear trend in mineralogical composition with downstream transport, only the furthest downstream samples have 2-line ferrihydrite in amounts detectable by XRD.

Synthesis of phase-pure and monodisperse iron oxide nanoparticles by thermal decomposition

NASA Astrophysics Data System (ADS)

Hufschmid, Ryan; Arami, Hamed; Ferguson, R. Matthew; Gonzales, Marcela; Teeman, Eric; Brush, Lucien N.; Browning, Nigel D.; Krishnan, Kannan M.

2015-06-01

Superparamagnetic iron oxide nanoparticles (SPIONs) are used for a wide range of biomedical applications requiring precise control over their physical and magnetic properties, which are dependent on their size and crystallographic phase. Here we present a comprehensive template for the design and synthesis of iron oxide nanoparticles with control over size, size distribution, phase, and resulting magnetic properties. We investigate critical parameters for synthesis of monodisperse SPIONs by organic thermal decomposition. Three different, commonly used, iron containing precursors (iron oleate, iron pentacarbonyl, and iron oxyhydroxide) are evaluated under a variety of synthetic conditions. We compare the suitability of these three kinetically controlled synthesis protocols, which have in common the use of iron oleate as a starting precursor or reaction intermediate, for producing nanoparticles with specific size and magnetic properties. Monodisperse particles were produced over a tunable range of sizes from approximately 2-30 nm. Reaction parameters such as precursor concentration, addition of surfactant, temperature, ramp rate, and time were adjusted to kinetically control size and size-distribution, phase, and magnetic properties. In particular, large quantities of excess surfactant (up to 25 : 1 molar ratio) alter reaction kinetics and result in larger particles with uniform size; however, there is often a trade-off between large particles and a narrow size distribution. Iron oxide phase, in addition to nanoparticle size and shape, is critical for establishing magnetic properties such as differential susceptibility (dm/dH) and anisotropy. As an example, we show the importance of obtaining the required size and iron oxide phase for application to Magnetic Particle Imaging (MPI), and describe how phase purity can be controlled. These results provide much of the information necessary to determine which iron oxide synthesis protocol is best suited to a particular application.

Migration and speciation of heavy metal in salinized mine tailings affected by iron mining.

PubMed

Zhang, Xu; Yang, Huanhuan; Cui, Zhaojie

2017-10-01

The negative effects of heavy metals have aroused much attention due to their high toxicity to human beings. Migration and transformation trend of heavy metals have a close relationship with soil safety. Researching on migration and transformation of heavy metals in tailings can provide a reliable basis for pollution management and ecosystem restoration. Heavy metal speciation plays an important role in risk assessment. We chose Anshan tailings for our study, including field investigations and laboratory research. Four typical heavy metal elements of mine tailings {Fe (373.89 g/kg), Mn (2,303.80 mg/kg), Pb (40.99 mg/kg) and Cr (199.92 mg/kg)} were studied via Tessier test in vertical and horizontal direction. The main speciation of heavy metals in Anshan tailings was the residual. However, heavy metals have a strong ability for migration and transformation in vertical and horizontal directions. Its tendency to change from stable to unstable speciation results in increasing bioavailability and potential bioavailability. Fe, Mn, Pb and Cr showed different ability in the migration and transformation process (Mn > Pb > Fe > Cr) depending on the characteristics of heavy metals and physicochemical properties of the environment.

Influence of organic substrates on the kinetics of bacterial As(III) oxidation

NASA Astrophysics Data System (ADS)

Lescure, T.; Joulian, C.; Bauda, P.; Hénault, C.; Battaglia-Brunet, F.

2012-04-01

Soil microflora plays a major role on the behavior of metals and metalloids. Arsenic speciation, in particular, is related to the activity of bacteria able to oxidize, reduce or methylate this element, and determines mobility, bioavailability and toxicity of As. Arsenite (AsIII) is more toxic and more mobile than arsenate (AsV). Bacterial As(III)-oxidation tends to reduce the toxicity of arsenic in soils and the risk of transfer toward underlying aquifers, that would affect the quality of water resources. Previous results suggest that organic matter may affect kinetics or efficiency of bacterial As(III)-oxidation in presence of oxygen, thus in conventional physico-chemical conditions of a surface soil. Different hypothesis can be proposed to explain the influence of organic matter on As(III) oxidation. Arsenic is a potential energy source for bacteria. The presence of easily biodegradable organic matter may inhibit the As(III) oxidation process because bacteria would first metabolize these more energetic substrates. A second hypothesis would be that, in presence of organic matter, the Ars system involved in bacterial resistance to arsenic would be more active and would compete with the Aio system of arsenite oxidation, decreasing the global As(III) oxidation rate. In addition, organic matter influences the solubility of iron oxides which often act as the main pitfalls of arsenic in soils. The concentration and nature of organic matter could therefore have a significant influence on the bioavailability of arsenic and hence on its environmental impact. The influence of organic matter on biological As(III) oxidation has not yet been determined in natural soils. In this context, soil amendment with organic matter during operations of phytostabilization or, considering diffuse pollutions, through agricultural practices, may affect the mobility and bio-availability of the toxic metalloid. The objective of the present project is to quantify the influence of organic matter on the bacterial speciation of arsenic in contaminated soils. Moreover, the biogeochemical consequences of this phenomenon on the mobility and ecotoxicity of this metalloid will be studied. The first task of this program is the precise and systematic investigation of the influence of different types and concentrations of organic matters on the activity of As(III)-oxidizing pure strains. Influence of aspartate, succinate (simple substrates) and yeast extract (complex substrate) on As(III)-oxidation kinetics has been studied. For each experiment, the bacterial growth and the expression of genes involved in the speciation of arsenic, i.e. aio and ars genes, has been monitored. A direct perspective of this work will be to perform experiments with humic and fulvic acids (complex organic matter commonly found in soils), and with water-extracted organic matter from polluted soils. Then the As(III)-oxidation activity of bacterial communities extracted from contaminated soils will be followed. These assays should allow the screening of conditions which will be applied in subsequent experiments with several real contaminated soils, including a former mining site, impacted industrial sites, and a forest soil heavily contaminated after arsenical ammunitions storage. This work is co-funded by BRGM and ADEME (convention TEZ 11-16).

Kinetics and Mechanism of Iodide Oxidation by Iron(III): A Clock Reaction Approach

ERIC Educational Resources Information Center

Bauer, Jurica; Tomisic, Vladislav; Vrkljan, Petar B. A.

2008-01-01

A simple method for studying the kinetics of a chemical reaction is described and the significance of reaction orders in deducing reaction mechanisms is demonstrated. In this student laboratory experiment, oxidation of iodide by iron(III) ions in an acidic medium is transformed into a clock reaction. By means of the initial rates method, it is…

PVDF membranes containing hybrid nanoparticles for adsorbing cationic dyes: physical insights and mechanism

NASA Astrophysics Data System (ADS)

Sharma, Maya; Madras, Giridhar; Bose, Suryasarathi

2016-07-01

In this study, Fe (iron) and Ag (silver) based adsorbents were synthesized using solution combustion and in situ reduction techniques. The synthesized adsorbents were comprehensively characterized by different techniques including electron microscopy, BET, XRD, Zeta potential etc. Three chlorinated cationic dyes used were malachite green, methyl violet and pyronin Y. These dyes were adsorbed on various synthesized adsorbents [iron III oxide (Fe2O3)], iron III oxide decorated silver nanoparticles by combustion synthesis technique [Fe2O3-Ag(C)] and iron III oxide decorated silver nanoparticles using in situ reduction, [Fe2O3-Ag (S)]. The isotherm and the adsorption kinetics have been studied systematically. The kinetic data can be explained by the pseudo second order model and the adsorption equilibrium followed Langmuir isotherm. The equilibrium and kinetics results suggest that Fe2O3-Ag(S) nanoparticles showed the maximum adsorption among all the adsorbents. Hence, Polyvinylidene fluoride based membranes containing Fe2O3-Ag(S) nanoparticles were prepared via phase inversion (precipitation immersion using DMF/water) technique. The adsorption kinetics were studied in detail and it was observed that the composite membrane showed synergistic improvement in dye adsorption. Such membranes can be used for water purification.

Following iron speciation in the early stages of magnetite magnetosome biomineralization

DOE PAGES

Firlar, Emre; Perez-Gonzalez, Teresa; Olszewska, Agata; ...

2016-02-26

Understanding magnetosome magnetite biomineralization is of fundamental interest to devising the strategies for bioinspired synthesis of magnetic materials at the nanoscale. Thus, we investigated the early stages of magnetosome formation in this work and correlated the size and emergent crystallinity of magnetosome nanoparticles with the changes in chemical environment of iron and oxygen by utilizing advanced analytical electron microscopy techniques. We observed that magnetosomes in the early stages of biomineralization with the sizes of 5–10 nm were amorphous, with a majority of iron present as Fe 3+, indicative of ferric hydroxide. The magnetosomes with intermediate sizes showed partially crystalline structuremore » with a majority of iron present as Fe 3+ and trace amounts of Fe 2+. The fully maturated magnetosomes were indexed to magnetite. Furthermore, our approach provides spatially resolved structural and chemical information of individual magnetosomes with different particle sizes, attributed to magnetosomes at different stages of biomineralization.« less

Atmospheric Processing and Iron Mobilization of Ilmenite: Iron-Containing Ternary Oxide in Mineral Dust Aerosol.

PubMed

Hettiarachchi, Eshani; Hurab, Omar; Rubasinghege, Gayan

2018-02-08

Over the last several decades, iron has been identified as a limiting nutrient in about half of the world's oceans. Its most significant source is identified as deposited iron-containing mineral dust that has been processed during atmospheric transportation. The current work focuses on chemical and photochemical processing of iron-containing mineral dust particles in the presence of nitric acid, and an organic pollutant dimethyl sulfide under atmospherically relevant conditions. More importantly, ilmenite (FeTiO 3 ) is evaluated as a proxy for the iron-containing mineral dust. The presence of titanium in its lattice structure provides higher complexity to mimic mineral dust, yet it is simple enough to study reaction pathways and mechanisms. Here, spectroscopic methods are combined with dissolution measurements to investigate atmospheric processing of iron in mineral dust, with specific focus on particle mineralogy, particle size, and their environmental conditions (i.e., pH and solar flux). Our results indicate that the presence of titanium elemental composition enhances iron dissolution from mineral dust, at least by 2-fold comparison with its nontitanium-containing counterparts. The extent of iron dissolution and speciation is further influenced by the above factors. Thus, our work highlights these important, yet unconsidered, factors in the atmospheric processing of iron-containing mineral dust aerosol.

Effects of Iron Deficiency on Iron Binding and Internalization into Acidic Vacuoles in Dunaliella salina1[W][OA

PubMed Central

Paz, Yakov; Shimoni, Eyal; Weiss, Meira; Pick, Uri

2007-01-01

Uptake of iron in the halotolerant alga Dunaliella salina is mediated by a transferrin-like protein (TTf), which binds and internalizes Fe3+ ions. Recently, we found that iron deficiency induces a large enhancement of iron binding, which is associated with accumulation of three other plasma membrane proteins that associate with TTf. In this study, we characterized the kinetic properties of iron binding and internalization and identified the site of iron internalization. Iron deficiency induces a 4-fold increase in Fe binding, but only 50% enhancement in the rate of iron uptake and also increases the affinity for iron and bicarbonate, a coligand for iron binding. These results indicate that iron deprivation leads to accumulation and modification of iron-binding sites. Iron uptake in iron-sufficient cells is preceded by an apparent time lag, resulting from prebound iron, which can be eliminated by unloading iron-binding sites. Iron is tightly bound to surface-exposed sites and hardly exchanges with medium iron. All bound iron is subsequently internalized. Accumulation of iron inhibits further iron binding and internalization. The vacuolar inhibitor bafilomycin inhibits iron uptake and internalization. Internalized iron was localized by electron microscopy within vacuolar structures that were identified as acidic vacuoles. Iron internalization is accompanied by endocytosis of surface proteins into these acidic vacuoles. A novel kinetic mechanism for iron uptake is proposed, which includes two pools of bound/compartmentalized iron separated by a rate-limiting internalization stage. The major parameter that is modulated by iron deficiency is the iron-binding capacity. We propose that excessive iron binding in iron-deficient cells serves as a temporary reservoir for iron that is subsequently internalized. This mechanism is particularly suitable for organisms that are exposed to large fluctuations in iron availability. PMID:17513481

ARSENIC SPECIATION, SEASONAL TRANSFORMATIONS, AND CO-DISTRIBUTION WITH IRON IN A MINE WASTE-INFLUENCED PALUSTRINE EMERGENT WETLAND. (R825399)

EPA Science Inventory

Arsenic is commonly associated with mined ores and thus may be detrimental to naturally occurring wetlands that reside in mine waste-impacted regions. Understanding the relationship between Fe and As in both the aqueous and solid phase is critical for assessing the risk As impose...

A systematic investigation of aluminium ion speciation at high temperature. Part 1. Solution studies.

PubMed

Shafran, Kirill L; Perry, Carole C

2005-06-21

Speciation diagrams of aluminium ions in aqueous solution (0.2 M) at high temperature (90 degrees C) have been obtained from 48 h time-resolved multi-batch titration experiments monitored by 27Al NMR spectroscopy, potentiometry and dynamic light scattering. The quantitative speciation patterns and kinetic data obtained offer a dynamic picture of the distribution of soluble and insoluble Al species as a function of hydrolysis ratio h(h=[OH-]/[Al3+]) over a very broad range of conditions (-1.0 < or =h < or = 4.0). Monomeric, small oligomeric, tridecameric (the 'Al13-mer') and the recently characterised 30-meric aluminium species (the 'Al30-mer') as well as aluminium hydroxide have been identified and quantified. The Al13-mer species dominates over a relatively broad range of hydrolysis ratios (1.5 < or =h< or = 2.7) during the first 6 h of experiment, but are gradually replaced by Al30-mers at longer reaction times. Kinetic profiles indicate that the formation of the Al30-mer is limited by the disappearance of the Al13 species at mildly acidic conditions. The estimated rate constants of both hydrolytic processes show good internal correlation at h> or = 1.5. The effect of local perturbations leading to the formation of aluminium hydroxide below the electroneutrality point (h= 3.0) has been estimated quantitatively.

Iron isotope biogeochemistry of Neoproterozoic marine shales

NASA Astrophysics Data System (ADS)

Kunzmann, Marcus; Gibson, Timothy M.; Halverson, Galen P.; Hodgskiss, Malcolm S. W.; Bui, Thi Hao; Carozza, David A.; Sperling, Erik A.; Poirier, André; Cox, Grant M.; Wing, Boswell A.

2017-07-01

Iron isotopes have been widely applied to investigate the redox evolution of Earth's surface environments. However, it is still unclear whether iron cycling in the water column or during diagenesis represents the major control on the iron isotope composition of sediments and sedimentary rocks. Interpretation of isotopic data in terms of oceanic redox conditions is only possible if water column processes dominate the isotopic composition, whereas redox interpretations are less straightforward if diagenetic iron cycling controls the isotopic composition. In the latter scenario, iron isotope data is more directly related to microbial processes such as dissimilatory iron reduction. Here we present bulk rock iron isotope data from late Proterozoic marine shales from Svalbard, northwestern Canada, and Siberia, to better understand the controls on iron isotope fractionation in late Proterozoic marine environments. Bulk shales span a δ 56Fe range from -0.45 ‰ to +1.04 ‰ . Although δ 56Fe values show significant variation within individual stratigraphic units, their mean value is closer to that of bulk crust and hydrothermal iron in samples post-dating the ca. 717-660 Ma Sturtian glaciation compared to older samples. After correcting for the highly reactive iron content in our samples based on iron speciation data, more than 90% of the calculated δ 56Fe compositions of highly reactive iron falls in the range from ca. -0.8 ‰ to +3 ‰ . An isotope mass-balance model indicates that diagenetic iron cycling can only change the isotopic composition of highly reactive iron by < 1 ‰ , suggesting that water column processes, namely the degree of oxidation of the ferrous seawater iron reservoir, control the isotopic composition of highly reactive iron. Considering a long-term decrease in the isotopic composition of the iron source to the dissolved seawater Fe(II) reservoir to be unlikely, we offer two possible explanations for the Neoproterozoic δ 56Fe trend. First, a decreasing supply of Fe(II) to the ferrous seawater iron reservoir could have caused the reservoir to decrease in size, allowing a higher degree of partial oxidation, irrespective of increasing environmental oxygen levels. Alternatively, increasing oxygen levels would have led to a higher proportion of Fe(II) being oxidized, without decreasing the initial size of the ferrous seawater iron pool. We consider the latter explanation as the most likely. According to this hypothesis, the δ 56Fe record reflects the redox evolution of Earth's surface environments. δ 56Fe values in pre-Sturtian samples significantly heavier than bulk crust and hydrothermal iron imply partial oxidation of a ferrous seawater iron reservoir. In contrast, mean δ 56Fe values closer to that of hydrothermal iron in post-Sturtian shales reflects oxidation of a larger proportion of the ferrous seawater iron reservoir, and by inference, higher environmental oxygen levels. Nevertheless, significant iron isotopic variation in post-Sturtian shales suggest redox heterogeneity and possibly a dominantly anoxic deep ocean, consistent with results from recent studies using iron speciation and redox sensitive trace metals. However, the interpretation of generally increasing environmental oxygen levels after the Sturtian glaciation highlights the need to better understand the sensitivity of different redox proxies to incremental changes in oxygen levels to enable us to reconcile results from different paleoredox proxies.

Controlling the degradation kinetics of porous iron by poly(lactic-co-glycolic acid) infiltration for use as temporary medical implants

PubMed Central

Yusop, Abdul Hakim Md; Daud, Nurizzati Mohd; Nur, Hadi; Kadir, Mohammed Rafiq Abdul; Hermawan, Hendra

2015-01-01

Iron and its alloy have been proposed as biodegradable metals for temporary medical implants. However, the formation of iron oxide and iron phosphate on their surface slows down their degradation kinetics in both in vitro and in vivo scenarios. This work presents new approach to tailor degradation behavior of iron by incorporating biodegradable polymers into the metal. Porous pure iron (PPI) was vacuum infiltrated by poly(lactic-co-glycolic acid) (PLGA) to form fully dense PLGA-infiltrated porous iron (PIPI) and dip coated into the PLGA to form partially dense PLGA-coated porous iron (PCPI). Results showed that compressive strength and toughness of the PIPI and PCPI were higher compared to PPI. A strong interfacial interaction was developed between the PLGA layer and the iron surface. Degradation rate of PIPI and PCPI was higher than that of PPI due to the effect of PLGA hydrolysis. The fast degradation of PIPI did not affect the viability of human fibroblast cells. Finally, this work discusses a degradation mechanism for PIPI and the effect of PLGA incorporation in accelerating the degradation of iron. PMID:26057073

DETERMINATION OF FERRITIN AND HEMOSIDERIN IRON IN PATIENTS WITH NORMAL IRON STORES AND IRON OVERLOAD BY SERUM FERRITIN KINETICS

PubMed Central

SAITO, HIROSHI; TOMITA, AKIHIRO; OHASHI, HARUHIKO; MAEDA, HIDEAKI; HAYASHI, HISAO; NAOE, TOMOKI

2012-01-01

ABSTRACT We attempted to clarify the storage iron metabolism from the change in the serum ferritin level. We assumed that the nonlinear decrease in serum ferritin was caused by serum ferritin increase in iron mobilization. Under this assumption, we determined both ferritin and hemosiderin iron levels by computer-assisted simulation of the row of decreasing assay-dots of serum ferritin in 11 patients with normal iron stores free of both iron deficiency and iron overload; chronic hepatitis C (CHC) and iron deficiency anemia after treatment, and 11 patients with iron overload; hereditary hemochromatosis (HH) and transfusion-dependent anemias (TD). We determined the iron removal rates of 20 and 17 mg/day by administering mean doses of deferasirox at 631 and 616 mg/day in 2 TD during the period of balance of iron addition and removal as indicated by the serum ferritin returned to the previous level. The ferritin-per-hemosiderin ratio was almost the same in both HH and CHC. This matched the localized hepatic hemosiderin deposition in CHC with normal iron stores. We detected the ferritin increased by utilizing the hemosiderin iron in iron removal and the ferritin reduced by transforming ferritin into hemosiderin in iron additions. The iron storing capacity of hemosiderin was limitless, while that of ferritin was suppressed when ferritin iron exceeded around 5 grams. We confirmed the pathway of iron from hemosiderin to ferritin in iron mobilization, and that from ferritin to hemosiderin in iron deposition. Thus, serum ferritin kinetics enabled us to be the first to clinically clarify storage iron metabolism. PMID:22515110

Arsenic speciation dynamics in paddy rice soil-water environment: sources, physico-chemical, and biological factors - A review.

PubMed

Kumarathilaka, Prasanna; Seneweera, Saman; Meharg, Andrew; Bundschuh, Jochen

2018-04-21

Rice is the main staple carbohydrate source for billions of people worldwide. Natural geogenic and anthropogenic sources has led to high arsenic (As) concentrations in rice grains. This is because As is highly bioavailable to rice roots under conditions in which rice is cultivated. A multifaceted and interdisciplinary understanding, both of short-term and long-term effects, are required to identify spatial and temporal changes in As contamination levels in paddy soil-water systems. During flooding, soil pore waters are elevated in inorganic As compared to dryland cultivation systems, as anaerobism results in poorly mobile As(V), being reduced to highly mobile As(III). The formation of iron (Fe) plaque on roots, availability of metal (hydro)oxides (Fe and Mn), organic matter, clay mineralogy and competing ions and compounds (PO 4 3- and Si(OH) 4 ) are all known to influence As(V) and As(III) mobility in paddy soil-water environments. Microorganisms play a key role in As transformation through oxidation/reduction, and methylation/volatilization reactions, but transformation kinetics are poorly understood. Scientific-based optimization of all biogeochemical parameters may help to significantly reduce the bioavailability of inorganic As. Copyright © 2018 Elsevier Ltd. All rights reserved.

KINETICS OF ARSENATE REDUCTION BY DISSOLVED SULFIDE. (R825399)

EPA Science Inventory

Arsenic toxicity and mobility in soil and aquatic environments depends on its
speciation, with reducing environments generally leading to more hazardous
conditions with respect to this element. Aqueous sulfide (H₂S or
HS^-) is a strong reductan...

TETRAVALENT LEAD: A HITHERTO UNRECOGNIZED CONTROL OF TAP WATER LEAD CONTAMINATION

EPA Science Inventory

Almost all of the theoretical framework underlying the control of plumbosolvency and lead release has been based on the presumption that the lead release is explicable by Pb(II) solubility, aqueous speciation, and reaction kinetics. Utilities struggling to comply with the Lead an...

An improved leaping detector for flow analysis applied to iron speciation in drugs

PubMed Central

Santos, Sérgio R. B.; Araújo, Mário C. U.; Honorato, Ricardo S.; Zagatto, Elias A. G.; Lima, José F. C.; Lapa, Rui A. S.

2000-01-01

A low inner volume (ca. 64 ml) probe was built up in an injector-commutator in order to behave as a photometric leaping detector in flow analysis. It comprises a bicolour light-emitting diode (BLED), as a source of pulsed radiation in the red and green visible region, and two phototransistors as transducers. Sample injection, detector relocation, analytical signal recording, data treatment and definition of the spectral working range were computer-controlled. The feasibility of the system was initially demonstrated in the flow-injection speciation of iron, and the overall standard deviation of results was estimated as ± 1.6 and ± 1.4% for 1.6–4.0 mg l−1 Fe(II) or total iron after eightfold processing of synthetic samples. The system was further applied to drug analysis: the mean deviations of results for typical samples were estimated as ± 5.2 and ± 3.3%, and the relative standard deviation as ± 1.6 and ± 1.3% for Fe(II) and total iron, respectively. Results were compared with those obtained by a conventional spectrophotometric procedure and no statistic differences at the 95% confidence level were found. In relation to an earlier system with multi-site detection, the proposed system is more stable, presenting low drift with a relative standard deviation of 0.026% and 0.039% for measurements (n=120 during 4 h of observation) with green and red emission. It is also faster with a sampling rate of 133 h−1 and carryover problems are not found. The possibility of compensating the Schlieren noise by dual-wavelength spectrophotometry is discussed. PMID:18924860

The role of iron-sulfides on cycling of organic carbon in the St Lawrence River system: Evidence of sulfur-promoted carbon sequestration?

NASA Astrophysics Data System (ADS)

Balind, K.; Barber, A.; Gélinas, Y.

2017-12-01

The biogeochemical cycle of sulfur is intimately linked with that of carbon, as well as with that of iron through the formation of iron-sulfur complexes. Iron-sulfide minerals such as mackinawite (FeS) and greigite (Fe3S4) form below the oxic/anoxic redox boundary in marine and lacustrine sediments and soils. Reactive iron species, abundant in surface sediments, can undergo reductive dissolution leading to the formation of soluble Fe(II) which can then precipitate in the form of iron sulfur species. While sedimentary iron-oxides have been thoroughly explored in terms of their ability to sorb and sequester organic carbon (OC) (Lalonde et al.; 2012), the role of FeS in the long-term preservation of OC remains undefined. In this study, we present depth profiles for carbon, iron, and sulfur in the aqueous-phase, along with data from sequential extractions of sulfur speciation in the solid-phase collected from sediment cores from the St Lawrence River and estuarine system, demonstrating the transition from fresh to saltwater sediments. Additionally, we present synthetic iron sulfur sorption experiments using both model and natural organic molecules in order to assess the importance of FeS in sedimentary carbon storage.

The global record of local iron geochemical data from Proterozoic through Paleozoic basins

NASA Astrophysics Data System (ADS)

Sperling, E. A.; Wolock, C.; Johnston, D. T.; Knoll, A. H.

2013-12-01

Iron-based redox proxies represent one of the most mature tools available to sedimentary geochemists. These techniques, which benefit from decades of refinement, are based on the fact that rocks deposited under anoxic conditions tend to be enriched in highly-reactive iron. However, there are myriad local controls on the development of anoxia, and no local section is an exemplar for the global ocean. The global signal must thus be determined using techniques like those developed to solve an analogous problem in paleobiology: the inference of global diversity patterns through time from faunas seen in local stratigraphic sections. Here we analyze a dataset of over 4000 iron speciation measurements (including over 600 de novo analyses) to better understand redox changes from the Proterozoic through the Paleozoic Era. Preliminary database analyses yield interesting observations. We find that although anoxic water columns in the middle Proterozoic were dominantly ferruginous, there was a statistical tendency towards euxinia not seen in early Neoproterozoic or Ediacaran data. Also, we find that in the Neoproterozoic oceans, oxic depositional environments-the likely home for early animals-have exceptionally low pyrite contents, and by inference low levels of porewater sulfide. This runs contrary to notions of sulfide stress on early metazoans. Finally, the current database of iron speciation data does not support an Ediacaran or Cambrian oxygenation event. This conclusion is of course only as sharp as the ability of the Fe-proxy database to track dissolved oxygen and does not rule out the possibility of a small-magnitude change in oxygen. It does suggest, however, that if changing pO2 facilitated animal diversification it did so by a limited rise past critical ecological thresholds, such as seen in the modern Oxygen Minimum Zones benthos. Oxygen increase to modern levels thus becomes a Paleozoic problem, and one in need of better sampling if a database approach is to be employed.

Iron Speciation in Minerals and Melts at High Pressure: Implications for the Redox Evolution of the Early Mantle

NASA Astrophysics Data System (ADS)

Armstrong, K.; Frost, D. J.; McCammon, C. A.; Rubie, D. C.; Boffa Ballaran, T.; Miyajima, N.

2016-12-01

During the differentiation of the early Earth, the silicates of the mantle must have been in equilibrium with core-forming metal iron, as indicated by the depletion of siderophile elements from the mantle. Studies of ancient rocks suggest that by at least 3.9 Ga, the upper mantle was 4-5 log units more oxidized than metal saturation implies (Delano 2001). The process(es) by which the mantle was oxidized is unclear, but has implications for the timing of accretion, differentiation, and volatile delivery to the early Earth, as well as evolution of the early atmosphere. One plausible oxidation mechanism is suggested by the tendency of high-pressure silicate minerals to favor Fe3+ over Fe2+ in their structures, even at metal saturation. This preference in the lower mantle mineral bridgmanite has been proposed to drive the disproportionation reaction of FeO to form Fe­2O3 and iron metal (Frost and McCammon 2008). We have performed experiments at the Ru-RuO2 fO2 buffer which show that silicate melts may mirror this behavior and Fe3+ may be stabilized with pressure for a constant fO2; by 21 GPa, the previously observed trend of Fe3+ decreasing with pressure (O'Neill, 2006) reverses and ferric iron content had increased. If this is also the case at lower oxygen fugacities, FeO disproportionation may have occurred at the base of an early magma ocean, establishing a redox gradient similar to what is presumed for the mantle today. Here we report results of further multianvil and diamond anvil cell experiments exploring the plausibility of FeO disproportionation driving mantle oxidation. Experiments investigating Fe speciation in high pressure melts at variable fO2 will be discussed along with results of diamond anvil cell experiments investigating ferric iron content of lower mantle minerals at metal saturation.

Detailed Modelling of Kinetic Biodegradation Processes in a Laboratory Mmicrocosm

NASA Astrophysics Data System (ADS)

Watson, I.; Oswald, S.; Banwart, S.; Mayer, U.

2003-04-01

Biodegradation of organic contaminants in soil and groundwater usually takes places via different redox processes happening sequentially as well as simultaneously. We used numerical modelling of a long-term lab microcosm experiment to simulate the dynamic behaviour of fermentation and respiration in the aqueous phase in contact with the sandstone material, and to develop a conceptual model describing these processes. Aqueous speciation, surface complexation, mineral dissolution and precipitation were taken into account also. Fermentation can be the first step of the degradation process producing intermediate species, which are subsequently consumed by TEAPs. Microbial growth and substrate utilisation kinetics are coupled via a formulation that also includes aqueous speciation and other geochemical reactions including surface complexation, mineral dissolution and precipitation. Competitive exclusion between TEAPs is integral to the conceptual model of the simulation, and the results indicate that exclusion is not complete, but some overlap is found between TEAPs. The model was used to test approaches like the partial equilibrium approach that currently make use of hydrogen levels to diagnose prevalent TEAPs in groundwater. The observed pattern of hydrogen and acetate concentrations were reproduced well by the simulations, and the results show the relevance of kinetics, lag times and inhibition, and especially that intermediate products play a key role.

Transdermal Delivery of Iron Using Soluble Microneedles: Dermal Kinetics and Safety.

PubMed

Modepalli, Naresh; Shivakumar, H Nanjappa; McCrudden, Maeliosa T C; Donnelly, Ryan F; Banga, Ajay; Murthy, S Narasimha

2016-03-01

Currently, the iron compounds are administered via oral and parenteral routes in patients of all ages, to treat iron deficiency. Despite continued efforts to supplement iron via these conventional routes, iron deficiency still remains the most prevalent nutritional disorder all over the world. Transdermal replenishment of iron is a novel, potential approach of iron replenishment. Ferric pyrophosphate (FPP) was found to be a suitable source of iron for transdermal replenishment. The safety of FPP was assessed in this project by challenging the dermal fibroblast cells with high concentration of FPP. The cell viability assay and reactive oxygen species assay were performed. The soluble microneedle array was developed, incorporated with FPP and the kinetics of free iron in the skin; extracellular fluid following dermal administration of microneedle array was investigated in hairless rats. From the cell based assays, FPP was selected as one of the potential iron sources for transdermal delivery. The microneedles were found to dissolve in the skin fluid within 3 hours of administration. The FPP concentration in the dermal extracellular fluid declined after complete dissolution of the microneedle array. Overall, the studies demonstrated the safety of FPP for dermal delivery and the feasibility of soluble microneedle approach for transdermal iron replenishment therapy. Copyright © 2016 American Pharmacists Association®. Published by Elsevier Inc. All rights reserved.

Smelting reduction and kinetics analysis of magnetic iron in copper slag using waste cooking oil.

PubMed

Li, Bo; Wang, Xubin; Wang, Hua; Wei, Yonggang; Hu, Jianhang

2017-05-25

To improve the recovery of copper, the viscosity of copper molten slag is decreased by the reduction of magnetic iron, which, in turn, accelerates the settling and separation of copper droplets from the slag. A new technology is proposed in which waste cooking oil is used as a reductant to reduce magnetic iron in the copper smelting slag and consequently reduce carbon emissions in the copper smelting process. A kinetic model of the reduction of magnetic iron in copper slag by waste cooking oil was built using experimental data, and the accuracy of the model was verified. The results indicated that the magnetic iron content in the copper slag decreased with increasing reduction time and an increase in temperature more efficiently reduced magnetic iron in the copper slag. The magnetic iron in the copper slag gradually transformed to fayalite, and the viscosity of the copper molten slag decreased as the magnetic iron content decreased during the reduction process. The reduction of magnetic iron in the copper molten slag using waste cooking oil was a first-order reaction, and the rate-limiting step was the mass transfer of Fe 3 O 4 through the liquid boundary layer.

Understanding Uranium Behavior in a Reduced Aquifer

NASA Astrophysics Data System (ADS)

Janot, N.; Lezama-Pacheco, J. S.; Williams, K. H.; Bernier-Latmani, R.; Long, P. E.; Davis, J. A.; Fox, P. M.; Yang, L.; Giammar, D.; Cerrato, J. M.; Bargar, J.

2012-12-01

Uranium contamination of groundwater is a concern at several US Department of Energy sites, such Old Rifle, CO. Uranium transport in the environment is mainly controlled by its oxidation state, since oxidized U(VI) is relatively mobile, whereas U(IV) is relatively insoluble. Bio-remediation of contaminated aquifers aims at immobilizing uranium in a reduced form. Previous laboratory and field studies have shown that adding electron donor (lactate, acetate, ethanol) to groundwater stimulates the activity of metal- and sulfate-reducing bacteria, which promotes U(VI) reduction in contaminated aquifers. However, obtaining information on chemical and physical forms of U, Fe and S species for sediments biostimulated in the field, as well as kinetic parameters such as U(VI) reduction rate, is challenging due to the low concentration of uranium in the aquifers (typically < 10 ppm) and the expense of collecting large number of cores. An in-situ technique has been developed for studying uranium, iron and sulfur reduction dynamics during such bioremediation episodes. This technique uses in-well columns to obtain direct access to chemical and physical forms of U(IV) produced in the aquifer, evolving microbial communities, and trace and major ion groundwater constituents. While several studies have explored bioreduction of uranium under sulfate-reducing conditions, less attention has been paid to the initial iron-reducing phase, noted as being of particular importance to uranium removal. The aim of this work was to assess the formation of U(IV) during the early stages of a bio-remediation experiment at the Old Rifle site, CO, from early iron-reducing conditions to the transition to sulfate-reducing conditions. Several in-well chromatographic columns packed with sediment were deployed and were sampled at different days after the start of bio-reduction. X-ray absorption spectroscopy and X-ray microscopy were used to obtain information on Fe, S and U speciation and distribution. Chemical extractions of the reduced sediments have also been performed, to determine the rate of Fe(II) and U(IV) accumulation.

HYPOXIA EFFECT ON THE TRANSFORMATION, SPECIATION, BIOAVAILABILITY AND TOXICITY OF CHEMICAL CONTAMINANTS IN THE HYPOXIC ZONE

EPA Science Inventory

This Symposium seeks to understand the direct effect of hypoxia on aquatic biota at the individual population, and the ecosystem levels. Another concern, however, is the indirect effect of varying oxygen levels on the thermodynamics and kinetics of biogeochemical processes and ...

Characterisation of zinc in slags originated from a contaminated sediment by coupling /μ-PIXE, /μ-RBS, /μ-EXAFS and powder EXAFS spectroscopy

NASA Astrophysics Data System (ADS)

Isaure, M. P.; Laboudigue, A.; Manceau, A.; Sarret, G.; Tiffreau, C.; Trocellier, P.

2001-07-01

Depositing dredged sediments on soils is usual but it is a hazardous practice for the local environment when these sediments are polluted by heavy metals. This chemical hazard can be assessed by determining the speciation of metals. In this study, slags highly polluted with Zn and originated from a contaminated dredged sediment were investigated. Zn speciation was studied by laterally resolved techniques such as μ-particle induced X-ray emission (μ-PIXE), μ-Rutherford backscattering spectrometry (μ-RBS), μ-extended X-ray absorption fine structure (μ-EXAFS), and bulk analyses such as powder EXAFS spectroscopy. μ-PIXE and μ-RBS results showed that high concentrations of Zn were associated with S in localised areas at the surface of the slags while moderate amounts of Zn were mainly associated with Fe in the matrix. EXAFS results allowed to identify ZnS and Zn sorbed on ferrihydrite (5Fe 2O 3·9H 2O), proxy for iron oxy-hydroxides, as the main Zn-bearing phases. The occurrence of this Zn-iron oxy-hydroxide is interpreted as a mobilisation of Zn released from ZnS oxidation.

Theoretical speciation of ethylenediamine-N-(o-hydroxyphenylacetic)-N'-(p-hydroxyphenylacetic) acid (o,p-EDDHA) in agronomic conditions.

PubMed

Yunta, Felipe; García-Marco, Sonia; Lucena, Juan J

2003-08-27

The presence of ethylenediamine-N-(o-hydroxyphenylacetic)-N'-(p-hydroxyphenylacetic) acid (o,p-EDDHA) as the second largest component in commercial EDDHA iron chelates has recently been demonstrated. Here is reported the speciation of o,p-EDDHA by the application of a novel methodology through the determination of the complexing capacity, protonation, and Ca(2+), Mg(2+), Cu(2+), and Fe(3+) stability constants. The pM values and species distribution in solution, hydroponic, and soil conditions were obtained. Due to the para position of one phenol group in o,p-EDDHA, the protonation constants and Ca and Mg stability constants have different values from those of o,o-EDDHA and p,p-EDDHA regioisomers. o,p-EDDHA/Fe(3+) stability constants are higher than those of EDTA/Fe(3+) but lower than those of o,o-EDDHA/Fe(3+). The sequence obtained for pFe is o,o-EDDHA/Fe(3+) >/= o,p-EDDHA/Fe(3+) > EDTA/Fe(3+). o,p-EDDHA/Fe(3+) can be used as an iron chelate in hydroponic conditions. Also, it can be used in soils with limited Cu availability.

Nanoscale oxidation and complex oxide growth on single crystal iron surfaces and external electric field effects.

PubMed

Jeon, Byoungseon; Van Overmeere, Quentin; van Duin, Adri C T; Ramanathan, Shriram

2013-02-14

Oxidation of iron surfaces and oxide growth mechanisms have been studied using reactive molecular dynamics. Oxide growth kinetics on Fe(100), (110), and (111) surface orientations has been investigated at various temperatures and/or an external electric field. The oxide growth kinetics decreases in the order of (110), (111), and (100) surfaces at 300 K over 1 ns timescale while higher temperature increases the oxidation rate. The oxidation rate shows a transition after an initial high rate, implying that the oxide formation mechanism evolves, with iron cation re-ordering. In early stages of surface oxide growth, oxygen transport through iron interstitial sites is dominant, yielding non-stoichiometric wüstite characteristics. The dominant oxygen inward transport decreases as the oxide thickens, evolving into more stoichiometric oxide phases such as wüstite or hematite. This also suggests that cation outward transport increases correspondingly. In addition to oxidation kinetics simulations, formed oxide layers have been relaxed in the range of 600-1500 K to investigate diffusion characteristics, fitting these results into an Arrhenius relation. The activation energy of oxygen diffusion in oxide layers formed on Fe(100), (110), and (111) surfaces was estimated to be 0.32, 0.26, and 0.28 eV, respectively. Comparison between our modeling results and literature data is then discussed. An external electric field (10 MV cm(-1)) facilitates initial oxidation kinetics by promoting oxygen transport through iron lattice interstitial sites, but reaches self-limiting thickness, showing that similar oxide formation stages are maintained when cation transport increases. The effect of the external electric field on iron oxide structure, composition, and oxide activation energy is found to be minimal, whereas cation outward migration is slightly promoted.

Atomic-Scale Design of Iron Fischer-Tropsch Catalysts; A Combined Computational Chemistry, Experimental, and Microkinetic Modeling Approach

DOE Office of Scientific and Technical Information (OSTI.GOV)

Manos Mavrikakis; James Dumesic; Rahul Nabar

2008-09-29

This work focuses on (1) searching/summarizing published Fischer-Tropsch synthesis (FTS) mechanistic and kinetic studies of FTS reactions on iron catalysts; (2) preparation and characterization of unsupported iron catalysts with/without potassium/platinum promoters; (3) measurement of H{sub 2} and CO adsorption/dissociation kinetics on iron catalysts using transient methods; (3) analysis of the transient rate data to calculate kinetic parameters of early elementary steps in FTS; (4) construction of a microkinetic model of FTS on iron, and (5) validation of the model from collection of steady-state rate data for FTS on iron catalysts. Three unsupported iron catalysts and three alumina-supported iron catalysts weremore » prepared by non-aqueous-evaporative deposition (NED) or aqueous impregnation (AI) and characterized by chemisorption, BET, temperature-programmed reduction (TPR), extent-of-reduction, XRD, and TEM methods. These catalysts, covering a wide range of dispersions and metal loadings, are well-reduced and relatively thermally stable up to 500-600 C in H{sub 2} and thus ideal for kinetic and mechanistic studies. Kinetic parameters for CO adsorption, CO dissociation, and surface carbon hydrogenation on these catalysts were determined from temperature-programmed desorption (TPD) of CO and temperature programmed surface hydrogenation (TPSR), temperature-programmed hydrogenation (TPH), and isothermal, transient hydrogenation (ITH). A microkinetic model was constructed for the early steps in FTS on polycrystalline iron from the kinetic parameters of elementary steps determined experimentally in this work and from literature values. Steady-state rate data were collected in a Berty reactor and used for validation of the microkinetic model. These rate data were fitted to 'smart' Langmuir-Hinshelwood rate expressions derived from a sequence of elementary steps and using a combination of fitted steady-state parameters and parameters specified from the transient measurements. The results provide a platform for further development of microkinetic models of FTS on Fe and a basis for more precise modeling of FTS activity of Fe catalysts. Calculations using periodic, self-consistent Density Functional Theory (DFT) methods were performed on various realistic models of industrial, Fe-based FTS catalysts. Close-packed, most stable Fe(110) facet was analyzed and subsequently carbide formation was found to be facile leading to the choice of the FeC(110) model representing a Fe facet with a sub-surface C atom. The Pt adatom (Fe{sup Pt}(110)) was found to be the most stable model for our studies into Pt promotion and finally the role of steps was elucidated by recourse to the defected Fe(211) facet. Binding Energies(BEs), preferred adsorption sites and geometries for all FTS relevant stable species and intermediates were evaluated on each model catalyst facet. A mechanistic model (comprising of 32 elementary steps involving 19 species) was constructed and each elementary step therein was fully characterized with respect to its thermochemistry and kinetics. Kinetic calculations involved evaluation of the Minimum Energy Pathways (MEPs) and activation energies (barriers) for each step. Vibrational frequencies were evaluated for the preferred adsorption configuration of each species with the aim of evaluating entropy-changes, pre exponential factors and serving as a useful connection with experimental surface science techniques. Comparative analysis among these four facets revealed important trends in their relative behavior and roles in FTS catalysis. Overall the First Principles Calculations afforded us a new insight into FTS catalysis on Fe and modified-Fe catalysts.« less

Reactive solute transport in an acidic stream: Experimental pH increase and simulation of controls on pH, aluminum, and iron

USGS Publications Warehouse

Broshears, R.E.; Runkel, R.L.; Kimball, B.A.; McKnight, Diane M.; Bencala, K.E.

1996-01-01

Solute transport simulations quantitatively constrained hydrologic and geochemical hypotheses about field observations of a pH modification in an acid mine drainage stream. Carbonate chemistry, the formation of solid phases, and buffering interactions with the stream bed were important factors in explaining the behavior of pH, aluminum, and iron. The precipitation of microcrystalline gibbsite accounted for the behavior of aluminum; precipitation of Fe(OH)3 explained the general pattern of iron solubility. The dynamic experiment revealed limitations on assumptions that reactions were controlled only by equilibrium chemistry. Temporal variation in relative rates of photoreduction and oxidation influenced iron behavior. Kinetic limitations on ferrous iron oxidation and hydrous oxide precipitation and the effects of these limitations on field filtration were evident. Kinetic restraints also characterized interaction between the water column and the stream bed, including sorption and desorption of protons from iron oxides at the sediment-water interface and post-injection dissolution of the precipitated aluminum solid phase.

Reduction of iron-bearing lunar minerals for the production of oxygen

NASA Technical Reports Server (NTRS)

Massieon, Charles; Cutler, Andrew; Shadman, Farhang

1992-01-01

The kinetics and mechanism of the reduction of simulants of the iron-bearing lunar minerals olivine ((Fe,Mg)2SiO4), pyroxene ((Fe,Mg,Ca)SiO3), and ilmenite (FeTiO3) are investigated, extending previous work with ilmenite. Fayalite is reduced by H2 at 1070 K to 1480 K. A layer of mixed silica glass and iron forms around an unreacted core. Reaction kinetics are influenced by permeation of hydrogen through this layer and a reaction step involving dissociated hydrogen. Reaction mechanisms are independent of Mg content. Augite, hypersthene, and hedenbergite are reduced in H2 at the same temperatures. The products are iron metal and lower iron silicates mixed throughout the mineral. Activation energy rises with calcium content. Ilmenite and fayalite are reduced with carbon deposited on partially reduced minerals via the CO disproportionation reaction. Reduction with carbon is rapid, showing the carbothermal reduction of lunar minerals is possible.

Iron-impregnated granular activated carbon for arsenic removal from drinking water

NASA Astrophysics Data System (ADS)

Chang, Qigang

A new multi-step iron impregnation method was developed in this study to impregnate GAC with a high amount of iron that possesses desired characteristics: stable, even distribution, and high arsenic adsorption capacity. Research was carried out to investigate the impact of the amount of impregnated iron on arsenic adsorption properties: capacity, affinity, and kinetics. Fe-GACs were characterized in terms of the amount, stability, distribution, morphology, and species of impregnated iron. It was found that a high amount of iron was stably impregnated in GAC. Scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDS) analysis demonstrated that the impregnated iron was evenly distributed on the internal surface of GAC. Impregnated iron formed nano-size particles and existed in both crystalline (akaganeite) and amorphous iron. Arsenic adsorption tests were conducted using Fe-GACs with iron content of 1.64--28.90% in a low arsenic concentration that is typical for drinking water treatment. The amount of impregnated iron affects arsenic maximum adsorption capacity (qm) but has little impact on the Langmuir constant h (the affinity of adsorbent for adsorbate). The qm for both As(V) and As(III) adsorptions increased significantly with increase of the amount of impregnated iron up to 13.59%. Further increase of iron amounts caused a gradual decrease of qm for As(V). BET analysis indicated impregnated iron possesses the highest surface area at iron content of 13.59%. A new second-order kinetic model was developed to investigate the impact of the amounts of impregnated iron on arsenic adsorption kinetics. With iron content increased from 1.64% to 28.90%, the intrinsic adsorption rate constants reduced from 4.6x10-2 1/hr to 1.18x10 -3 1/hr, which indicates that impregnated iron slows arsenic intraparticle diffusion rate in Fe-GAC. The decreased arsenic intraparticle diffusion rate was most likely caused by reduced pore size of Fe-GACs. Column tests were conducted to investigate the performance of Fe-GACs in real implementations using groundwater taken from a former superfund site in North Dakota. Fe-GACs can remove arsenic below 10 microg/L and the performance of Fe-GACs was significantly enhanced with increasing empty bed contact time.

Thermodynamic and kinetic studies of biosorption of iron and manganese from aqueous medium using rice husk ash

NASA Astrophysics Data System (ADS)

Adekola, F. A.; Hodonou, D. S. S.; Adegoke, H. I.

2016-11-01

The adsorption behavior of rice husk ash with respect to manganese and iron has been studied by batch methods to consider its application for water and waste water treatment. The optimum conditions of adsorption were determined by investigating the effect of initial metal ion concentration, contact time, adsorbent dose, pH value of aqueous solution and temperature. Adsorption equilibrium time was observed at 120 min. The adsorption efficiencies were found to be pH dependent. The equilibrium adsorption experimental data were found to fit the Langmuir, Freundlich and Temkin isotherms for iron, but fitted only Langmuir isotherm for manganese. The pseudo-second order kinetic model was found to describe the manganese and iron kinetics more effectively. The thermodynamic experiment revealed that the adsorption processes involving both metals were exothermic. The adsorbent was finally applied to typical raw water with initial manganese and iron concentrations of 3.38 mg/l for Fe and 6.28 mg/l, respectively, and the removal efficiency was 100 % for Mn and 70 % for Fe. The metal ions were desorbed from the adsorbent using 0.01 M HCl, it was found to quantitatively remove 67 and 86 % of Mn and Fe, respectively, within 2 h. The results revealed that manganese and iron are considerably adsorbed on the adsorbent and could be an economic method for the removal of these metals from aqueous solutions.

Atomic-Scale Design of Iron Fischer-Tropsch Catalysts: A Combined Computational Chemistry, Experimental, and Microkinetic Modeling Approach

DOE Office of Scientific and Technical Information (OSTI.GOV)

Manos Mavrikakis; James A. Dumesic; Amit A. Gokhale

2006-03-03

Efforts during this second year focused on four areas: (1) continued searching and summarizing of published Fischer-Tropsch synthesis (FTS) mechanistic and kinetic studies of FTS reactions on iron catalysts; (2) investigation of CO adsorption/desorption and temperature programmed hydrogenation (TPH) of carbonaceous species after FTS on unsupported iron and alumina-supported iron catalysts; (3) activity tests of alumina-supported iron catalysts in a fixed bed reactor; (4) sequential design of experiments, for the collection of rate data in a Berty CSTR reactor, and nonlinear-regression analysis to obtain kinetic parameters. Literature sources describing mechanistic and kinetic studies of Fischer-Tropsch synthesis on iron catalysts weremore » compiled in a review. Temperature-programmed desorption/reaction methods (the latter using mass-spectrometry detection and also thermogravimetric analyzer (TGA)) were utilized to study CO adsorption/-desorption on supported and unsupported iron catalysts. Molecular and dissociative adsorptions of CO occur on iron catalysts at 25-150 C. The amounts adsorbed and bond strengths of adsorption are influenced by supports and promoters. That CO adsorbs dissociatively on polycrystalline Fe at temperatures well below those of FT reaction indicates that CO dissociation is facile and unlikely to be the rate-limiting step during FTS. Carbonaceous species formed after FT reaction for only 5 minutes at 200 C were initially hydrogenated under mild, isothermal condition (200 C and 1 atm), followed by TPH to 800 C. During the mild, isothermal hydrogenation, only about 0.1-0.2 mL of atomic carbon is apparently removed, while during TPH to 800 C multilayer equivalents of atomic, polymeric, carbidic, and graphitic carbons are removed. Rates of CO conversion on alumina-supported iron catalysts at 220-260 C and 20 atm are correlated well by a Langmuir-Hinshelwood expression, derived assuming carbon hydrogenation to CH and OH recombination to water to be rate-determining steps. In the coming year, studies will focus on quantitative determination of the rates of kinetically-relevant elementary steps on Fe catalysts with/without K and Pt promoters and at various levels of Al{sub 2}O{sub 3} support, providing a database for understanding (1) effects of promoter and support on elementary kinetic parameters and (2) for validation of computational models that incorporate effects of surface structure and promoters. Kinetic parameters will be incorporated into a microkinetics model, enabling prediction of rate without invoking assumptions, e.g. of a rate-determining step or a most-abundant surface intermediate. Calculations using periodic, self-consistent Density Functional Theory (DFT) methods were performed on two model surfaces: (1) Fe(110) with 1/4 ML subsurface carbon, and (2) Fe(110) with 1/4 ML Pt adatoms. Reaction networks for FTS on these systems were characterized in full detail by evaluating the thermodynamics and kinetics of each elementary step. We discovered that subsurface C stabilizes all the reactive intermediates, in contrast to Pt, which destabilizes most of them. A comparative study of the reactivities of the modified-Fe surfaces against pure Fe is expected to yield a more comprehensive understanding of promotion mechanisms for FTS on Fe.« less

A comprehensive iso-octane combustion model with improved thermochemistry and chemical kinetics

DOE Office of Scientific and Technical Information (OSTI.GOV)

Atef, Nour; Kukkadapu, Goutham; Mohamed, Samah Y.

Iso-Octane (2,2,4-trimethylpentane) is a primary reference fuel and an important component of gasoline fuels. Furthermore, it is a key component used in surrogates to study the ignition and burning characteristics of gasoline fuels. This paper presents an updated chemical kinetic model for iso-octane combustion. Specifically, the thermodynamic data and reaction kinetics of iso-octane have been re-assessed based on new thermodynamic group values and recently evaluated rate coefficients from the literature. The adopted rate coefficients were either experimentally measured or determined by analogy to theoretically calculated values. New alternative isomerization pathways for peroxy-alkyl hydroperoxide (more » $$\\dot{O}$$OQOOH) radicals were added to the reaction mechanism. The updated kinetic model was compared against new ignition delay data measured in rapid compression machines (RCM) and a high-pressure shock tube. Our experiments were conducted at pressures of 20 and 40 atm, at equivalence ratios of 0.4 and 1.0, and at temperatures in the range of 632–1060 K. The updated model was further compared against shock tube ignition delay times, jet-stirred reactor oxidation speciation data, premixed laminar flame speeds, counterflow diffusion flame ignition, and shock tube pyrolysis speciation data available in the literature. Finally, the updated model was used to investigate the importance of alternative isomerization pathways in the low temperature oxidation of highly branched alkanes. When compared to available models in the literature, the present model represents the current state-of-the-art in fundamental thermochemistry and reaction kinetics of iso-octane; and thus provides the best prediction of wide ranging experimental data and fundamental insights into iso-octane combustion chemistry.« less

A comprehensive iso-octane combustion model with improved thermochemistry and chemical kinetics

DOE PAGES

Atef, Nour; Kukkadapu, Goutham; Mohamed, Samah Y.; ...

2017-02-05

Iso-Octane (2,2,4-trimethylpentane) is a primary reference fuel and an important component of gasoline fuels. Furthermore, it is a key component used in surrogates to study the ignition and burning characteristics of gasoline fuels. This paper presents an updated chemical kinetic model for iso-octane combustion. Specifically, the thermodynamic data and reaction kinetics of iso-octane have been re-assessed based on new thermodynamic group values and recently evaluated rate coefficients from the literature. The adopted rate coefficients were either experimentally measured or determined by analogy to theoretically calculated values. New alternative isomerization pathways for peroxy-alkyl hydroperoxide (more » $$\\dot{O}$$OQOOH) radicals were added to the reaction mechanism. The updated kinetic model was compared against new ignition delay data measured in rapid compression machines (RCM) and a high-pressure shock tube. Our experiments were conducted at pressures of 20 and 40 atm, at equivalence ratios of 0.4 and 1.0, and at temperatures in the range of 632–1060 K. The updated model was further compared against shock tube ignition delay times, jet-stirred reactor oxidation speciation data, premixed laminar flame speeds, counterflow diffusion flame ignition, and shock tube pyrolysis speciation data available in the literature. Finally, the updated model was used to investigate the importance of alternative isomerization pathways in the low temperature oxidation of highly branched alkanes. When compared to available models in the literature, the present model represents the current state-of-the-art in fundamental thermochemistry and reaction kinetics of iso-octane; and thus provides the best prediction of wide ranging experimental data and fundamental insights into iso-octane combustion chemistry.« less

Fatigue crack layer propagation in silicon-iron

NASA Technical Reports Server (NTRS)

Birol, Y.; Welsch, G.; Chudnovsky, A.

1986-01-01

Fatigue crack propagation in metal is almost always accompanied by plastic deformation unless conditions strongly favor brittle fracture. The analysis of the plastic zone is crucial to the understanding of crack propagation behavior as it governs the crack growth kinetics. This research was undertaken to study the fatigue crack propagation in a silicon iron alloy. Kinetic and plasticity aspects of fatigue crack propagation in the alloy were obtained, including the characterization of damage evolution.

Characteristics and kinetic analysis of AQS transformation and microbial goethite reduction: Insight into “redox mediator-microbe-iron oxide” interaction process

DOE PAGES

Zhu, Weihuang; Shi, Mengran; Yu, Dan; ...

2016-03-29

Here, the characteristics and kinetics of redox transformation of a redox mediator, anthraquinone-2-sulfonate (AQS), during microbial goethite reduction by Shewanella decolorationis S12, a dissimilatory iron reduction bacterium (DIRB), were investigated to provide insights into “redox mediator-iron oxide” interaction in the presence of DIRB. Two pre-incubation reaction systems of the “strain S12-goethite” and the “strain S12-AQS” were used to investigate the dynamics of goethite reduction and AQS redox transformation. Results show that the concentrations of goethite and redox mediator, and the inoculation cell density all affect the characteristics of microbial goethite reduction, kinetic transformation between oxidized and reduced species of themore » redox mediator. Both abiotic and biotic reactions and their coupling regulate the kinetic process for “Quinone-Iron” interaction in the presence of DIRB. Our results provide some new insights into the characteristics and mechanisms of interaction among “quinone-DIRB- goethite” under biotic/abiotic driven.« less

Effects of chloride ions on corrosion of ductile iron and carbon steel in soil environments.

PubMed

Song, Yarong; Jiang, Guangming; Chen, Ying; Zhao, Peng; Tian, Yimei

2017-07-31

Chloride is reported to play a significant role in corrosion reactions, products and kinetics of ferrous metals. To enhance the understanding of the effects of soil environments, especially the saline soils with high levels of chloride, on the corrosion of ductile iron and carbon steel, a 3-month corrosion test was carried out by exposing ferrous metals to soils of six chloride concentrations. The surface morphology, rust compositions and corrosion kinetics were comprehensively studied by visual observation, scanning electron microscopy (SEM), X-Ray diffraction (XRD), weight loss, pit depth measurement, linear polarization and electrochemical impedance spectroscopy (EIS) measurements. It showed that chloride ions influenced the characteristics and compositions of rust layers by diverting and participating in corrosion reactions. α-FeOOH, γ-FeOOH and iron oxides were major corrosion products, while β-Fe 8 O 8 (OH) 8 Cl 1.35 rather than β-FeOOH was formed when high chloride concentrations were provided. Chloride also suppressed the decreasing of corrosion rates, whereas increased the difficulty in the diffusion process by thickening the rust layers and transforming the rust compositions. Carbon steel is more susceptible to chloride attacks than ductile iron. The corrosion kinetics of ductile iron and carbon steel corresponded with the probabilistic and bilinear model respectively.

Surficial weathering of iron sulfide mine tailings under semi-arid climate.

PubMed

Hayes, Sarah M; Root, Robert A; Perdrial, Nicolas; Maier, Raina; Chorover, Jon

2014-09-15

Mine wastes introduce anthropogenic weathering profiles to the critical zone that often remain unvegetated for decades after mining cessation. As such, they are vulnerable to wind and water dispersion of particulate matter to adjacent ecosystems and residential communities. In sulfide-rich ore tailings, propagation to depth of the oxidative weathering front controls the depth-variation in speciation of major and trace elements. Despite the prevalence of surficial mine waste deposits in arid regions of the globe, few prior studies have been conducted to resolve the near-surface profile of sulfide ore tailings weathered under semi-arid climate. We investigated relations between gossan oxidative reaction-front propagation and the molecular speciation of iron and sulfur in tailings subjected to weathering under semi-arid climate at an EPA Superfund Site in semi-arid central Arizona (USA). Here we report a multi-method data set combining wet chemical and synchrotron-based X-ray diffraction (XRD) and X-ray absorption near-edge spectroscopy (XANES) methods to resolve the tight coupling of iron (Fe) and sulfur (S) geochemical changes in the top 2 m of tailings. Despite nearly invariant Fe and S concentration with depth (130-140 and 100-120 g kg -1 , respectively), a sharp redox gradient and distinct morphological change was observed within the top 0.5 m, associated with a progressive oxidative alteration of ferrous sulfides to (oxyhydr)oxides and (hydroxy)sulfates. Transformation is nearly complete in surficial samples. Trends in molecular-scale alteration were co-located with a decrease in pH from 7.3 to 2.3, and shifts in Fe and S lability as measured via chemical extraction. Initial weathering products, ferrihydrite and gypsum, transform to schwertmannite, then jarosite-group minerals with an accompanying decrease in pH. Interestingly, thermodynamically stable phases such as goethite and hematite were not detected in any samples, but ferrihydrite was observed even in the lowest pH samples, indicating its metastable persistence in these semiarid tailings. The resulting sharp geochemical speciation gradients in close proximity to the tailings surface have important implications for plant colonization, as well as mobility and bioavailability of co-associated toxic metal(loid)s.

Surficial weathering of iron sulfide mine tailings under semi-arid climate

PubMed Central

Hayes, Sarah M.; Root, Robert A.; Perdrial, Nicolas; Maier, Raina; Chorover, Jon

2014-01-01

Mine wastes introduce anthropogenic weathering profiles to the critical zone that often remain unvegetated for decades after mining cessation. As such, they are vulnerable to wind and water dispersion of particulate matter to adjacent ecosystems and residential communities. In sulfide-rich ore tailings, propagation to depth of the oxidative weathering front controls the depth-variation in speciation of major and trace elements. Despite the prevalence of surficial mine waste deposits in arid regions of the globe, few prior studies have been conducted to resolve the near-surface profile of sulfide ore tailings weathered under semi-arid climate. We investigated relations between gossan oxidative reaction-front propagation and the molecular speciation of iron and sulfur in tailings subjected to weathering under semi-arid climate at an EPA Superfund Site in semi-arid central Arizona (USA). Here we report a multi-method data set combining wet chemical and synchrotron-based X-ray diffraction (XRD) and X-ray absorption near-edge spectroscopy (XANES) methods to resolve the tight coupling of iron (Fe) and sulfur (S) geochemical changes in the top 2 m of tailings. Despite nearly invariant Fe and S concentration with depth (130–140 and 100–120 g kg−1, respectively), a sharp redox gradient and distinct morphological change was observed within the top 0.5 m, associated with a progressive oxidative alteration of ferrous sulfides to (oxyhydr)oxides and (hydroxy)sulfates. Transformation is nearly complete in surficial samples. Trends in molecular-scale alteration were co-located with a decrease in pH from 7.3 to 2.3, and shifts in Fe and S lability as measured via chemical extraction. Initial weathering products, ferrihydrite and gypsum, transform to schwertmannite, then jarosite-group minerals with an accompanying decrease in pH. Interestingly, thermodynamically stable phases such as goethite and hematite were not detected in any samples, but ferrihydrite was observed even in the lowest pH samples, indicating its metastable persistence in these semiarid tailings. The resulting sharp geochemical speciation gradients in close proximity to the tailings surface have important implications for plant colonization, as well as mobility and bioavailability of co-associated toxic metal(loid)s. PMID:25197102

Derivation of Pitzer Interaction Parameters for an Aqueous Species Pair of Sodium and Iron(II)-Citrate Complex

NASA Astrophysics Data System (ADS)

Jang, J. H.; Nemer, M.

2015-12-01

The U.S. DOE Waste Isolation Pilot Plant (WIPP) is a deep underground repository for the permanent disposal of transuranic (TRU) radioactive waste. The WIPP is located in the Permian Delaware Basin near Carlsbad, New Mexico, U.S.A. The TRU waste includes, but is not limited to, iron-based alloys and the complexing agent, citric acid. Iron is also present from the steel used in the waste containers. The objective of this analysis is to derive the Pitzer activity coefficients for the pair of Na+ and FeCit- complex to expand current WIPP thermodynamic database. An aqueous model for the dissolution of Fe(OH)2(s) in a Na3Cit solution was fitted to the experimentally measured solubility data. The aqueous model consists of several chemical reactions and related Pitzer interaction parameters. Specifically, Pitzer interaction parameters for the Na+ and FeCit- pair (β(0), β(1), and Cφ) plus the stability constant for species of FeCit- were fitted to the experimental data. Anoxic gloveboxes were used to keep the oxygen level low (<1 ppm) throughout the experiments due to redox sensitivity. EQ3NR, a computer program for geochemical aqueous speciation-solubility calculations, packaged in EQ3/6 v.8.0a, calculates the aqueous speciation and saturation index using an aqueous model addressed in EQ3/6's database. The saturation index indicates how far the system is from equilibrium with respect to the solid of interest. Thus, the smaller the sum of squared saturation indices that the aqueous model calculates for the given number of experiments, the more closely the model attributes equilibrium to each individual experiment with respect to the solid of interest. The calculation of aqueous speciation and saturation indices was repeated by adjusting stability constant of FeCit-, β(0), β(1), and Cφ in the database until the values are found that make the sum of squared saturation indices the smallest for the given number of experiments. Results will be presented at the time of conference.

Surficial weathering of iron sulfide mine tailings under semi-arid climate

NASA Astrophysics Data System (ADS)

Hayes, Sarah M.; Root, Robert A.; Perdrial, Nicolas; Maier, Raina M.; Chorover, Jon

2014-09-01

Mine wastes introduce anthropogenic weathering profiles to the critical zone that often remain unvegetated for decades after mining cessation. As such, they are vulnerable to wind and water dispersion of particulate matter to adjacent ecosystems and residential communities. In sulfide-rich ore tailings, propagation to depth of the oxidative weathering front controls the depth-variation in speciation of major and trace elements. Despite the prevalence of surficial mine waste deposits in arid regions of the globe, few prior studies have been conducted to resolve the near-surface profile of sulfide ore tailings weathered under semi-arid climate. We investigated relations between gossan oxidative reaction-front propagation and the molecular speciation of iron and sulfur in tailings subjected to weathering in a semi-arid climate at an EPA Superfund Site in central Arizona (USA). Here we report a multi-method data set combining wet chemical and synchrotron-based X-ray diffraction (XRD) and X-ray absorption near-edge spectroscopy (XANES) methods to resolve the tight coupling of iron (Fe) and sulfur (S) geochemical changes in the top 2 m of tailings. Despite nearly invariant Fe and S concentration with depth (130-140 and 100-120 g kg-1, respectively), a sharp redox gradient and distinct morphological change was observed within the top 0.5 m, associated with a progressive oxidative alteration of ferrous sulfides to (oxyhydr)oxides and (hydroxy)sulfates. Transformation is nearly complete in surficial samples. Trends in molecular-scale alteration were co-located with a decrease in pH from 7.3 to 2.3, and shifts in Fe and S lability as measured via chemical extraction. Initial weathering products, ferrihydrite and gypsum, transform to schwertmannite, then jarosite-group minerals with an accompanying decrease in pH. Interestingly, thermodynamically stable phases such as goethite and hematite were not detected in any samples, but ferrihydrite was observed even in samples with the lowest pH, indicating its metastable persistence in these semiarid tailings. The resulting sharp geochemical speciation gradients in close proximity to the tailings surface have important implications for plant colonization, as well as mobility and bioavailability of co-associated toxic metal(loid)s.

Enhanced ferrihydrite dissolution by a unicellular, planktonic cyanobacterium: a biological contribution to particulate iron bioavailability.

PubMed

Kranzler, Chana; Kessler, Nivi; Keren, Nir; Shaked, Yeala

2016-12-01

Iron (Fe) bioavailability, as determined by its sources, sinks, solubility and speciation, places severe environmental constraints on microorganisms in aquatic environments. Cyanobacteria are a widespread group of aquatic, photosynthetic microorganisms with especially high iron requirements. While iron exists predominantly in particulate form, little is known about its bioavailability to cyanobacteria. Some cyanobacteria secrete iron solubilizing ligands called siderophores, yet many environmentally relevant strains do not have this ability. This work explores the bioavailability of amorphous synthetic Fe-oxides (ferrihydrite) to the non-siderophore producing, unicellular cyanobacterium, Synechocystis sp PCC 6803. Iron uptake assays with 55 ferrihydrite established dissolution as a critical prerequisite for iron transport. Dissolution assays with the iron binding ligand, desferrioxamine B, demonstrated that Synechocystis 6803 enhances ferrihydrite dissolution, exerting siderophore-independent biological influence on ferrihydrite bioavailability. Dissolution mechanisms were studied using a range of experimental conditions; both cell-particle physical proximity and cellular electron flow were shown to be important determinants of bio-dissolution by Synechocystis 6803. Finally, the effects of ferrihydrite stability on bio-dissolution rates and cell physiology were measured, integrating biological and chemical aspects of ferrihydrite bioavailability. Collectively, these findings demonstrate that Synechocystis 6803 actively dissolves ferrihydrite, highlighting a significant biological component to mineral phase iron bioavailability in aquatic environments. © 2016 Society for Applied Microbiology and John Wiley & Sons Ltd.

Nickel speciation in several serpentine (ultramafic) topsoils via bulk synchrotron-based techniques

DOE Office of Scientific and Technical Information (OSTI.GOV)

Siebecker, Matthew G.; Chaney, Rufus L.; Sparks, Donald L.

2017-07-01

Serpentine soils have elevated concentrations of trace metals including nickel, cobalt, and chromium compared to non-serpentine soils. Identifying the nickel bearing minerals allows for prediction of potential mobility of nickel. Synchrotron-based techniques can identify the solid-phase chemical forms of nickel with minimal sample treatment. Element concentrations are known to vary among soil particle sizes in serpentine soils. Sonication is a useful method to physically disperse sand, silt and clay particles in soils. Synchrotron-based techniques and sonication were employed to identify nickel species in discrete particle size fractions in several serpentine (ultramafic) topsoils to better understand solid-phase nickel geochemistry. Nickel commonlymore » resided in primary serpentine parent material such as layered-phyllosilicate and chain-inosilicate minerals and was associated with iron oxides. In the clay fractions, nickel was associated with iron oxides and primary serpentine minerals, such as lizardite. Linear combination fitting (LCF) was used to characterize nickel species. Total metal concentration did not correlate with nickel speciation and is not an indicator of the major nickel species in the soil. Differences in soil texture were related to different nickel speciation for several particle size fractionated samples. A discussion on LCF illustrates the importance of choosing standards based not only on statistical methods such as Target Transformation but also on sample mineralogy and particle size. Results from the F-test (Hamilton test), which is an underutilized tool in the literature for LCF in soils, highlight its usefulness to determine the appropriate number of standards to for LCF. EXAFS shell fitting illustrates that destructive interference commonly found for light and heavy elements in layered double hydroxides and in phyllosilicates also can occur in inosilicate minerals, causing similar structural features and leading to false positive results in LCF.« less

Assessment of bioavailability of iron delivered to marine phytoplankton in different mineralogical forms

NASA Astrophysics Data System (ADS)

Ammar, Rawaa; Delmelle, Pierre; Journet, Emilie

2017-04-01

Iron (Fe) is an essential element in cellular biochemical processes and its availability in the surface ocean limits phytoplankton-mediated fixation of C, i.e. the biological pump. In vast regions of the open ocean, atmospheric deposition of Fe-bearing continental dust and volcanic ash to the surface ocean acts as an important source of bioavailable Fe to phytoplankton. The capacity of dust and ash to alleviate Fe limitation is usually discussed in terms of Fe solubility, which has been shown to be controlled by speciation/mineralogy. However, little information exists on the relationship between Fe bioavailability and Fe speciation/mineralogy in dust and ash. In this study, Fe-bearing materials of known mineralogy, including three volcanic ash samples from different eruptions (Eyjafjallajökull 2010, Chaitén 2008 and Tungurahua 2012), two continental dust specimens (Douz and Banizoumbou) and three Fe-bearing minerals (illite/smectite, ferrihydrite, and goethite) were added to Fe-stressed cultures of Dunaliella tertiolecta, a marine algae commonly found in high-nutrient, low chlorophyll waters. Photosynthetic activity, chlorophyll content and cell population growth were measured at regular intervals during 168 h after Fe addition. Our results indicate that all the tested Fe-bearing materials induced a similar biological response; and were able to alleviate Fe stress in D. tertiolecta within 2 h from the beginning of the experiment and to induce cell growth up to 168 h. This unexpected finding contrasts with the traditional view that Fe speciation/mineralogy in dust and ash plays a key role in governing Fe bioavailability to phytoplankton. Supplementary measurements on the fractional solubility of Fe in dust and ash will be presented.

Aluminum and Fenton reaction: how can the reaction be modulated by speciation? A computational study using citrate as a test case.

PubMed

Mujika, Jon I; Dalla Torre, Gabriele; Lopez, Xabier

2018-06-13

The pro-oxidant ability of aluminum is behind many of the potential toxic effects of this exogenous element in the human organism. Although the overall process is still far from being understood at the molecular level, the well known ability of aluminum to promote the Fenton reaction is mediated through the formation of stable aluminum-superoxide radical complexes. However, the properties of metal complexes are highly influenced by the speciation of the metal. In this paper, we investigate the effect that speciation could have on the pro-oxidant activity of aluminum. We choose citrate as a test case, because it is the main low-molecular-mass chelator of aluminum in blood serum, forming very stable aluminum-citrate complexes. The influence of citrate in the interaction of aluminum with the superoxide radical is investigated, determining how the formation of aluminum-citrate complexes affects the promotion of the Fenton reaction. The results indicate that citrate increases the stability of the aluminum-superoxide complexes through the formation of ternary compounds, and that the Fenton reaction is even more favorable when aluminum is chelated to citrate. Nevertheless, our results demonstrate that overall, citrate may prevent the pro-oxidant activity of aluminum: on one hand, in an excess of citrate, the formation of 1 : 2 aluminum-citrate complexes is expected. On the other hand, the chelation of iron by citrate makes the reduction of iron thermodynamically unfavorable. In summary, the results suggest that citrate can have both a promotion and protective role, depending on subtle factors, such as initial concentration, non-equilibrium behavior and the exchange rate of ligands in the first shell of the metals.

The relationship between dissolved humic acids and soluble iron in estuaries

NASA Technical Reports Server (NTRS)

Fox, L. E.

1984-01-01

Dissolved humic acid and soluble iron appear to be chemically unassociated in estuaries despite their coincident removal. This conclusion is supported by differences in the aggregation kinetics of soluble iron and dissolved humic acid, the inability of extracted humic acid to stabilize laboratory preparations of ferric hydroxide, and decreasing ratios of humic acid carbon to soluble iron along the axes of some estuaries.

Novel Flaxseed Gum Nanocomposites Are Slow Release Iron Supplements.

PubMed

Liang, Shan; Huang, Yu; Shim, Youn Young; Ma, Xiang; Reaney, Martin J T; Wang, Yong

2018-05-23

Nanocomposites, based on iron salts and soluble flaxseed gum (FG), were prepared as potential treatments of iron deficiency anemia (IDA). FG was extracted, characterized, and formulated into iron-loading nanocomposites via ion-exchange against FeCl 3 , Fe 2 (SO 4 ) 3 , FeCl 2 , and FeSO 4 ·7H 2 O. FG-iron nanocomposites preparation condition was optimized, and physicochemical properties of the nanocomposites were investigated. In vitro release kinetics of iron in simulated gastric fluid (SGF) was also evaluated. FG heteropolysaccharide, consisting of rhamnose (33.73%), arabinose (24.35%), xylose (14.23%), glucose (4.54%), and galactose (23.15%) monosaccharides, linked together via varieties of glycosidic bonds, was a good recipient for both ferric and ferrous irons under screened conditions (i.e., 80 °C, 2 h, I/G = 1:2). Iron loaded contents in the nanocomposites prepared from FG-FeCl 3 , FG-Fe 2 (SO 4 ) 3 , FG-FeCl 2 , and FG-FeSO 4 ·7H 2 O were 25.51%, 10.36%, 5.83%, and 22.83%, respectively. Iron in these nanocomposites was mostly in a bound state, especially in FG-FeCl 3 , due to chelation forming bonds between iron and polysaccharide hydroxyl or carboxyl groups and formed stable polysaccharide-iron crystal network structures. Free iron ions were effectively removed by ethanol treatments. Because of chelation, the nanocomposites delayed iron release in SGF and the release kinetics were consistent with Korsmeyer-Peppas model. This indicates that such complexes might reduce side effects of free iron in human stomach. Altogether, this study indicates that these synthetic FG-iron nanocomposites might be developed as novel iron supplements for iron deficiency, in which FG-FeCl 3 is considered as the best option.

Ascorbate Efflux as a New Strategy for Iron Reduction and Transport in Plants*

PubMed Central

Grillet, Louis; Ouerdane, Laurent; Flis, Paulina; Hoang, Minh Thi Thanh; Isaure, Marie-Pierre; Lobinski, Ryszard; Curie, Catherine; Mari, Stéphane

2014-01-01

Iron (Fe) is essential for virtually all living organisms. The identification of the chemical forms of iron (the speciation) circulating in and between cells is crucial to further understand the mechanisms of iron delivery to its final targets. Here we analyzed how iron is transported to the seeds by the chemical identification of iron complexes that are delivered to embryos, followed by the biochemical characterization of the transport of these complexes by the embryo, using the pea (Pisum sativum) as a model species. We have found that iron circulates as ferric complexes with citrate and malate (Fe(III)3Cit2Mal2, Fe(III)3Cit3Mal1, Fe(III)Cit2). Because dicotyledonous plants only transport ferrous iron, we checked whether embryos were capable of reducing iron of these complexes. Indeed, embryos did express a constitutively high ferric reduction activity. Surprisingly, iron(III) reduction is not catalyzed by the expected membrane-bound ferric reductase. Instead, embryos efflux high amounts of ascorbate that chemically reduce iron(III) from citrate-malate complexes. In vitro transport experiments on isolated embryos using radiolabeled 55Fe demonstrated that this ascorbate-mediated reduction is an obligatory step for the uptake of iron(II). Moreover, the ascorbate efflux activity was also measured in Arabidopsis embryos, suggesting that this new iron transport system may be generic to dicotyledonous plants. Finally, in embryos of the ascorbate-deficient mutants vtc2-4, vtc5-1, and vtc5-2, the reducing activity and the iron concentration were reduced significantly. Taken together, our results identified a new iron transport mechanism in plants that could play a major role to control iron loading in seeds. PMID:24347170

Ascorbate efflux as a new strategy for iron reduction and transport in plants.

PubMed

Grillet, Louis; Ouerdane, Laurent; Flis, Paulina; Hoang, Minh Thi Thanh; Isaure, Marie-Pierre; Lobinski, Ryszard; Curie, Catherine; Mari, Stéphane

2014-01-31

Iron (Fe) is essential for virtually all living organisms. The identification of the chemical forms of iron (the speciation) circulating in and between cells is crucial to further understand the mechanisms of iron delivery to its final targets. Here we analyzed how iron is transported to the seeds by the chemical identification of iron complexes that are delivered to embryos, followed by the biochemical characterization of the transport of these complexes by the embryo, using the pea (Pisum sativum) as a model species. We have found that iron circulates as ferric complexes with citrate and malate (Fe(III)3Cit2Mal2, Fe(III)3Cit3Mal1, Fe(III)Cit2). Because dicotyledonous plants only transport ferrous iron, we checked whether embryos were capable of reducing iron of these complexes. Indeed, embryos did express a constitutively high ferric reduction activity. Surprisingly, iron(III) reduction is not catalyzed by the expected membrane-bound ferric reductase. Instead, embryos efflux high amounts of ascorbate that chemically reduce iron(III) from citrate-malate complexes. In vitro transport experiments on isolated embryos using radiolabeled (55)Fe demonstrated that this ascorbate-mediated reduction is an obligatory step for the uptake of iron(II). Moreover, the ascorbate efflux activity was also measured in Arabidopsis embryos, suggesting that this new iron transport system may be generic to dicotyledonous plants. Finally, in embryos of the ascorbate-deficient mutants vtc2-4, vtc5-1, and vtc5-2, the reducing activity and the iron concentration were reduced significantly. Taken together, our results identified a new iron transport mechanism in plants that could play a major role to control iron loading in seeds.

Mathematical treatment of isotopologue and isotopomer speciation and fractionation in biochemical kinetics

DOE Office of Scientific and Technical Information (OSTI.GOV)

Maggi, F.M.; Riley, W.J.

2009-11-01

We present a mathematical treatment of the kinetic equations that describe isotopologue and isotopomer speciation and fractionation during enzyme-catalyzed biochemical reactions. These equations, presented here with the name GEBIK (general equations for biochemical isotope kinetics) and GEBIF (general equations for biochemical isotope fractionation), take into account microbial biomass and enzyme dynamics, reaction stoichiometry, isotope substitution number, and isotope location within each isotopologue and isotopomer. In addition to solving the complete GEBIK and GEBIF, we also present and discuss two approximations to the full solutions under the assumption of biomass-free and enzyme steady-state, and under the quasi-steady-state assumption as applied tomore » the complexation rate. The complete and approximate approaches are applied to observations of biological denitrification in soils. Our analysis highlights that the full GEBIK and GEBIF provide a more accurate description of concentrations and isotopic compositions of substrates and products throughout the reaction than do the approximate forms. We demonstrate that the isotopic effects of a biochemical reaction depend, in the most general case, on substrate and complex concentrations and, therefore, the fractionation factor is a function of time. We also demonstrate that inverse isotopic effects can occur for values of the fractionation factor smaller than 1, and that reactions that do not discriminate isotopes do not necessarily imply a fractionation factor equal to 1.« less

Updated atmospheric speciated mercury emissions from iron and steel production in China during 2000-2015

NASA Astrophysics Data System (ADS)

Wu, Qingru; Gao, Wei; Wang, Shuxiao; Hao, Jiming

2017-09-01

Iron and steel production (ISP) is one of the significant atmospheric Hg emission sources in China. Atmospheric mercury (Hg) emissions from ISP during 2000-2015 were estimated by using a technology-based emission factor method. To support the application of this method, databases of Hg concentrations in raw materials, technology development trends, and Hg removal efficiencies of air pollution control devices (APCDs) were constructed through national sampling and literature review. Hg input to ISP increased from 21.6 t in 2000 to 94.5 t in 2015. In the various types of raw materials, coking coal and iron concentrates contributed 35-46 and 25-32 % of the total Hg input. Atmospheric Hg emissions from ISP increased from 11.5 t in 2000 to 32.7 t in 2015 with a peak of 35.6 t in 2013. Pollution control promoted the increase in average Hg removal efficiency, from 47 % in 2000 to 65 % in 2015. During the study period, sinter/pellet plants and blast furnaces were the largest two emission processes. However, emissions from roasting plants and coke ovens cannot be ignored, which accounted for 22-34 % of ISP's emissions. Overall, Hg speciation shifted from 50/44/6 (gaseous elemental Hg (Hg0)/gaseous oxidized Hg (HgII)/particulate-bound Hg (Hgp)) in 2000 to 40/59/1 in 2015, which indicated a higher proportion of Hg deposition around the emission points. Future emissions of ISP were expected to decrease based on the comprehensive consideration crude-steel production, steel scrap utilization, energy saving, and pollution control measures.

Functional Characterization of the FoxE Iron Oxidoreductase from the Photoferrotroph Rhodobacter ferrooxidans SW2*

PubMed Central

Saraiva, Ivo H.; Newman, Dianne K.; Louro, Ricardo O.

2012-01-01

Photoferrotrophy is presumed to be an ancient type of photosynthetic metabolism in which bacteria use the reducing power of ferrous iron to drive carbon fixation. In this work the putative iron oxidoreductase of the photoferrotroph Rhodobacter ferrooxidans SW2 was cloned, purified, and characterized for the first time. This protein, FoxE, was characterized using spectroscopic, thermodynamic, and kinetic techniques. It is a c-type cytochrome that forms a trimer or tetramer in solution; the two hemes of each monomer are hexacoordinated by histidine and methionine. The hemes have positive reduction potentials that allow downhill electron transfer from many geochemically relevant ferrous iron forms to the photosynthetic reaction center. The reduction potentials of the hemes are different and are cross-assigned to fast and slow kinetic phases of ferrous iron oxidation in vitro. Lower reactivity was observed at high pH and may contribute to prevent ferric iron precipitation inside or at the surface of the cell. These results help fill in the molecular details of a metabolic process that likely contributed to the deposition of precambrian banded iron formations, globally important sedimentary rocks that are found on every continent today. PMID:22661703

Oxidation of Fe(II) in rainwater.

PubMed

Willey, J D; Whitehead, R F; Kieber, R J; Hardison, D R

2005-04-15

Photochemically produced Fe(II) is oxidized within hours under environmentally realistic conditions in rainwater. The diurnal variation between photochemical production and reoxidation of Fe(II) observed in our laboratory accurately mimics the behavior of ferrous iron observed in field studies where the highest concentrations of dissolved Fe(ll) occur in afternoon rain during the period of maximum sunlight intensity followed by gradually decreasing concentrations eventually returning to early morning pre-light values. The experimental work presented here, along with the results of kinetics studies done by others, suggests thatthe primary process responsible for the decline in photochemically produced Fe(II) concentrations is oxidation by hydrogen peroxide. This reaction is first order with respect to both the concentrations of Fe(II) and H2O2. The second-order rate constant determined for six different authentic rain samples varied over an order of magnitude and was always less than or equal to the rate constant determined for this reaction in simple acidic solutions. Oxidation of photochemically produced ferrous iron by other oxidants including molecular oxygen, ozone, hydroxyl radical, hydroperoxyl/superoxide radical, and hexavalent chromium were found to be insignificant under the conditions present in rainwater. This study shows that Fe(II) occurs as at least two different chemical species in rain; photochemically produced Fe(II) that is oxidized over time periods of hours, and a background Fe(II) that is protected against oxidation, perhaps by organic complexation, and is stable against oxidation for days. Because the rate of oxidation of photochemically produced Fe(II) does not increase with increasing rainwater pH, the speciation of this more labile form of Fe(II) is also not controlled by simple hydrolysis reactions.

Microfluidic Experiments Studying Pore Scale Interactions of Microbes and Geochemistry

NASA Astrophysics Data System (ADS)

Chen, M.; Kocar, B. D.

2016-12-01

Understanding how physical phenomena, chemical reactions, and microbial behavior interact at the pore-scale is crucial to understanding larger scale trends in groundwater chemistry. Recent studies illustrate the utility of microfluidic devices for illuminating pore-scale physical-biogeochemical processes and their control(s) on the cycling of iron, uranium, and other important elements 1-3. These experimental systems are ideal for examining geochemical reactions mediated by microbes, which include processes governed by complex biological phenomenon (e.g. biofilm formation, etc.)4. We present results of microfluidic experiments using a model metal reducing bacteria and varying pore geometries, exploring the limitations of the microorganisms' ability to access tight pore spaces, and examining coupled biogeochemical-physical controls on the cycling of redox sensitive metals. Experimental results will provide an enhanced understanding of coupled physical-biogeochemical processes transpiring at the pore-scale, and will constrain and compliment continuum models used to predict and describe the subsurface cycling of redox-sensitive elements5. 1. Vrionis, H. A. et al. Microbiological and geochemical heterogeneity in an in situ uranium bioremediation field site. Appl. Environ. Microbiol. 71, 6308-6318 (2005). 2. Pearce, C. I. et al. Pore-scale characterization of biogeochemical controls on iron and uranium speciation under flow conditions. Environ. Sci. Technol. 46, 7992-8000 (2012). 3. Zhang, C., Liu, C. & Shi, Z. Micromodel investigation of transport effect on the kinetics of reductive dissolution of hematite. Environ. Sci. Technol. 47, 4131-4139 (2013). 4. Ginn, T. R. et al. Processes in microbial transport in the natural subsurface. Adv. Water Resour. 25, 1017-1042 (2002). 5. Scheibe, T. D. et al. Coupling a genome-scale metabolic model with a reactive transport model to describe in situ uranium bioremediation. Microb. Biotechnol. 2, 274-286 (2009).

Novel electrochemical-enzymatic model which quantifies the effect of the solution Eh on the kinetics of ferrous iron oxidation with Acidithiobacillus ferrooxidans.

PubMed

Meruane, G; Salhe, C; Wiertz, J; Vargas, T

2002-11-05

The influence of solution Eh on the rate of ferrous iron oxidation by Acidithiobacillus ferrooxidans is characterized. The experimental approach was based on the use of a two-chamber bioelectrochemical cell, which can determine the ferrous iron oxidation rate at controlled potential. Results enabled the formulation of a novel kinetic model, which incorporates the effect of solution Eh in an explicit form but still integrates the effect of ferrous iron concentration and ferric inhibition. The results showed that at Eh values below 650 mV (standard hydrogen electrode, SHE) the bacterial oxidative activity is mainly dependent on ferrous iron concentration. At Eh values between 650 and 820 mV (SHE) the oxidation rate is mainly controlled by ferric inhibition. Over 820 mV (SHE) the bacterial oxidative activity is strongly inhibited by the Eh increase, being completely inhibited at Eh = 840 mV (SHE). Copyright 2002 Wiley Periodicals, Inc. Biotechnol Bioeng 80: 280-288, 2002.

Capturing the onset of the common cold and its effects on iron absorption.

PubMed

Hoppe, M; Hulthén, L

2007-08-01

Hypoferremia is a well-known response to infections and inflammatory disorders. It seems to be managed by the key mediator of iron kinetics, hepcidin. There are several studies on induced-acute phase reactions. However, to our best knowledge there are no previous published reports on the outbreak of a common cold and its initial effect on iron kinetics. The objective of this case report is to describe such an observation. From an apparently healthy state in the morning we observed, in a 28-year-old male, every hour for 6 h the outbreak of a common cold and the modulations in the levels of serum iron (S-Fe) and interleukin-6 (IL-6). Despite a 100 mg oral iron loading there was a substantial reduction in S-Fe, which seemed to precede the IL-6 peak. Interestingly, this observed succession is in conflict with the proposed infection chain of order in which IL-6 stimulates hepcidin induction.

Syntheses of organic compounds in the presence of the fused iron catalyst and their mechanisms and kinetics

NASA Astrophysics Data System (ADS)

Glebov, L. S.; Kliger, G. A.

1989-10-01

New synthetic possibilities of the reduced promoted fused iron catalyst in intermolecular and intramolecular amination, cyanation, hydrogenation-dehydrogenation, and hydrodeoxygenation reactions and intermolecular and intramolecular dehydration, polymerisation, and isotope exchange are examined. The mechanisms and kinetics of the reactions leading to the synthesis of amines, alcohols, hydrocarbons, and other organic compunds are discussed. A laser Raman spectroscopic method is described for the investigation of heterogeneous organic catalysis in situ. The bibliography includes 148 references.

The impact of particle size, relative humidity, and sulfur dioxide on iron solubility in simulated atmospheric marine aerosols.

PubMed

Cartledge, Benton T; Marcotte, Aurelie R; Herckes, Pierre; Anbar, Ariel D; Majestic, Brian J

2015-06-16

Iron is a limiting nutrient in about half of the world's oceans, and its most significant source is atmospheric deposition. To understand the pathways of iron solubilization during atmospheric transport, we exposed size segregated simulated marine aerosols to 5 ppm sulfur dioxide at arid (23 ± 1% relative humidity, RH) and marine (98 ± 1% RH) conditions. Relative iron solubility increased as the particle size decreased for goethite and hematite, while for magnetite, the relative solubility was similar for all of the fine size fractions (2.5-0.25 μm) investigated but higher than the coarse size fraction (10-2.5 μm). Goethite and hematite showed increased solubility at arid RH, but no difference (p > 0.05) was observed between the two humidity levels for magnetite. There was no correlation between iron solubility and exposure to SO2 in any mineral for any size fraction. X-ray absorption near edge structure (XANES) measurements showed no change in iron speciation [Fe(II) and Fe(III)] in any minerals following SO2 exposure. SEM-EDS measurements of SO2-exposed goethite revealed small amounts of sulfur uptake on the samples; however, the incorporated sulfur did not affect iron solubility. Our results show that although sulfur is incorporated into particles via gas-phase processes, changes in iron solubility also depend on other species in the aerosol.

Aging of Dissolved Copper and Copper-based Nanoparticles in Five Different Soils: Short-term Kinetics vs. Long-term Fate

EPA Science Inventory

With the growing availability and use of copper-based nanomaterials (Cu-NMs), there is increasing concern regarding their release and potential impact on the environment. In this study, the short term (≤5 d) aging profile and the long-term (135 d) speciation of dissolved Cu, cop...

Real-time redox speciation of iron in estuarine and coastal surface waters.

PubMed

Huang, Yongming; Yuan, Dongxing; Zhu, Yong; Feng, Sichao

2015-03-17

An automated, shipboard-use system was developed for real-time speciation of iron in coastal surface waters. It comprised a towed Fish underway sampler and a modified reverse flow injection analysis system with a liquid waveguide capillary flow cell-spectrophotometric detection device. The detection was based on the reaction between ferrozine and Fe(II). The detection limits of 0.3 and 0.7 nM were achieved for Fe(II) and Fe(II+III), together with their respective dynamic linear ranges of 0.5-250 and 0.9-250 nM. The system was successfully deployed and run consecutively for about 1 week during a cruise in August 2009 to the East China Sea off the Changjiang Estuary. The distribution of operationally defined field dissolvable Fe(II) and Fe(II+III) (expressed as Fea(II) and Fea(II+III)) in these areas was obtained, which showed that both Fea(II) and Fea(II+III) concentrations decreased with salinity when there were relatively high Fea(II) concentrations (up to about 120 nM) near shore. A distinct distribution of Fea(II) to Fea(II+III) ratios was also revealed, with a ratio of 0.58 in the water off Changjiang Estuary and 0.19 in the open ocean.

Sequestration of arsenic in ombrotrophic peatlands

NASA Astrophysics Data System (ADS)

Rothwell, James; Hudson-Edwards, Karen; Taylor, Kevin; Polya, David; Evans, Martin; Allott, Tim

2014-05-01

Peatlands can be important stores of arsenic but we are lacking spectroscopic evidence of the sequestration pathways of this toxic metalloid in peatland environments. This study reports on the solid-phase speciation of anthropogenically-derived arsenic in atmospherically contaminated peat from the Peak District National Park (UK). Surface and sub-surface peat samples were analysed by synchrotron X-ray absorption spectroscopy on B18 beamline at Diamond Light Source (UK). The results suggest that there are contrasting arsenic sequestration mechanisms in the peat. The bulk arsenic speciation results, in combination with strong arsenic-iron correlations at the surface, suggest that iron (hydr)oxides are key phases for the immobilisation of arsenic at the peat surface. In contrast, the deeper peat samples are dominated by arsenic sulphides (arsenopyrite, realgar and orpiment). Given that these peats receive inputs solely from the atmosphere, the presence of these sulphide phases suggests an in-situ authigenic formation. Redox oscillations in the peat due to a fluctuating water table and an abundant store of legacy sulphur from historic acid rain inputs may favour the precipitation of arsenic sequestering sulphides in sub-surface horizons. Oxidation-induced loss of these arsenic sequestering sulphur species by water table drawdown has important implications for the mobility of arsenic and the quality of waters draining peatlands.

BEARKIMPE-2: A VBA Excel program for characterizing granular iron in treatability studies

NASA Astrophysics Data System (ADS)

Firdous, R.; Devlin, J. F.

2014-02-01

The selection of a suitable kinetic model to investigate the reaction rate of a contaminant with granular iron (GI) is essential to optimize the permeable reactive barrier (PRB) performance in terms of its reactivity. The newly developed Kinetic Iron Model (KIM) determines the surface rate constant (k) and sorption parameters (Cmax &J) which were not possible to uniquely identify previously. The code was written in Visual Basic (VBA), within Microsoft Excel, was adapted from earlier command line FORTRAN codes, BEARPE and KIMPE. The program is organized with several user interface screens (UserForms) that guide the user step by step through the analysis. BEARKIMPE-2 uses a non-linear optimization algorithm to calculate transport and chemical kinetic parameters. Both reactive and non-reactive sites are considered. A demonstration of the functionality of BEARKIMPE-2, with three nitroaromatic compounds showed that the differences in reaction rates for these compounds could be attributed to differences in their sorption behavior rather than their propensities to accept electrons in the reduction process.

Processes and kinetics of Cd2+ sorption by a calcareous aquifer sand

USGS Publications Warehouse

Fuller, C.C.; Davis, J.A.

1987-01-01

The rate of Cd2+ sorption by a calcareous aquifer sand was characterized by two reaction steps, with the first step reaching completion in 24 hours. The second step proceeded at a slow and nearly constant rate for at least seven days. The first step includes a fast adsorption reaction which is followed by diffusive transport into either a disordered surface film of hydrated calcium carbonate or into pore spaces. After 24 hours the rate of Cd2+ sorption was constant and controlled by the rate of surface coprecipitation, as a solid solution of CdCO3 in CaCO3 formed in recrystallizing material. Desorption of Cd2+ from the sand was slow. Clean grains of primary minerals, e.g. quartz and aluminosilicates. sorbed much less Cd2+ than grains which had surface patches of secondary minerals, e.g. carbonates, iron and manganese oxides. Calcite grains sorbed the greatest amount of Cd2+ on a weight-normalized basis despite the greater abundance of quartz. A method is illustrated for determining empirical binding constants for trace metals at in situ pH values without introducing the experimental problem of supersaturation. The binding constants are useful for solute transport models which include a computation of aqueous speciation. ?? 1987.

EFFECTS OF NATURAL ORGANIC MATTER, ANTHROPOGENIC SURFACTANTS, AND MODEL QUINONES ON THE REDUCTION OF CONTAMINANTS BY ZERO-VALENT IRON. (R827117)

EPA Science Inventory

Recent studies of contaminant reduction by zero-valent iron metal (Fe⁰) have highlighted the role of iron oxides at the metal–water interface and the effect that sorption has at the oxide–water interface on contaminant reduction kinetics. The results s...

Rapid kinetics of iron responsive element (IRE) RNA/iron regulatory protein 1 and IRE-RNA/eIF4F complexes respond differently to metal ions.

PubMed

Khan, Mateen A; Ma, Jia; Walden, William E; Merrick, William C; Theil, Elizabeth C; Goss, Dixie J

2014-06-01

Metal ion binding was previously shown to destabilize IRE-RNA/IRP1 equilibria and enhanced IRE-RNA/eIF4F equilibria. In order to understand the relative importance of kinetics and stability, we now report rapid rates of protein/RNA complex assembly and dissociation for two IRE-RNAs with IRP1, and quantitatively different metal ion response kinetics that coincide with the different iron responses in vivo. kon, for FRT IRE-RNA binding to IRP1 was eight times faster than ACO2 IRE-RNA. Mn(2+) decreased kon and increased koff for IRP1 binding to both FRT and ACO2 IRE-RNA, with a larger effect for FRT IRE-RNA. In order to further understand IRE-mRNA regulation in terms of kinetics and stability, eIF4F kinetics with FRT IRE-RNA were determined. kon for eIF4F binding to FRT IRE-RNA in the absence of metal ions was 5-times slower than the IRP1 binding to FRT IRE-RNA. Mn(2+) increased the association rate for eIF4F binding to FRT IRE-RNA, so that at 50 µM Mn(2+) eIF4F bound more than 3-times faster than IRP1. IRP1/IRE-RNA complex has a much shorter life-time than the eIF4F/IRE-RNA complex, which suggests that both rate of assembly and stability of the complexes are important, and that allows this regulatory system to respond rapidly to change in cellular iron. © The Author(s) 2014. Published by Oxford University Press on behalf of Nucleic Acids Research.

Metal Speciation in Landfill Leachates with a Focus on the Influence of Organic Matter

DOE Office of Scientific and Technical Information (OSTI.GOV)

F Claret; C Tournassat; C Crouzet

This study characterizes the heavy-metal content in leachates collected from eight landfills in France. In order to identify heavy metal occurrence in the different size fractions of leachates, a cascade filtration protocol was applied directly in the field, under a nitrogen gas atmosphere to avoid metal oxidation. The results of analyses performed on the leachates suggest that most of the metals are concentrated in the <30 kDa fraction, while lead, copper and cadmium show an association with larger particles. Initial speciation calculations, without considering metal association with organic matter, suggest that leachate concentrations in lead, copper, nickel and zinc aremore » super-saturated with respect to sulphur phases. Speciation calculations that account for metal complexation with organic matter, considered as fulvic acids based on C1(s) NEXAFS spectroscopy, show that this mechanism is not sufficient to explain such deviation from equilibrium conditions. It is therefore hypothesized that the deviation results also from the influence of biological activity on the kinetics of mineral phase precipitation and dissolution, thus providing a dynamic system. The results of chemical analyses of sampled fluids are compared with speciation calculations and some implications for the assessment of metal mobility and natural attenuation in a context of landfill risk assessment are discussed.« less

Metal speciation and potential bioavailability changes during discharge and neutralisation of acidic drainage water.

PubMed

Simpson, Stuart L; Vardanega, Christopher R; Jarolimek, Chad; Jolley, Dianne F; Angel, Brad M; Mosley, Luke M

2014-05-01

The discharge of acid drainage from the farm irrigation areas to the Murray River in South Australia represents a potential risk to water quality. The drainage waters have low pH (2.9-5.7), high acidity (up to 1190 mg L(-1) CaCO3), high dissolved organic carbon (10-40 mg L(-1)), and high dissolved Al, Co, Ni and Zn (up to 55, 1.25, 1.30 and 1.10 mg L(-1), respectively) that represent the greatest concern relative to water quality guidelines (WQGs). To provide information on bioavailability, changes in metal speciation were assessed during mixing experiments using filtration (colloidal metals) and Chelex-lability (free metal ions and weak inorganic metal complexes) methods. Following mixing of drainage and river water, much of the dissolved aluminium and iron precipitated. The concentrations of other metals generally decreased conservatively in proportion to the dilution initially, but longer mixing periods caused increased precipitation or adsorption to particulate phases. Dissolved Co, Mn and Zn were typically 95-100% present in Chelex-labile forms, whereas 40-70% of the dissolved nickel was Chelex-labile and the remaining non-labile fraction of dissolved nickel was associated with fine colloids or complexed by organic ligands that increased with time. Despite the different kinetics of precipitation, adsorption and complexation reactions, the dissolved metal concentrations were generally highly correlated for the pooled data sets, indicating that the major factors controlling the concentrations were similar for each metal (pH, dilution, and time following mixing). For dilutions of the drainage waters of less than 1% with Murray River water, none of the metals should exceed the WQGs. However, the high concentrations of metals associated with fine precipitates within the receiving waters may represent a risk to some aquatic organisms. Crown Copyright © 2013. Published by Elsevier Ltd. All rights reserved.

Predicting toxic effects of copper on aquatic biota in mineralized areas by using the Biotic Ligand Model

USGS Publications Warehouse

Smith, Kathleen S.; Ranville, James F.; Adams, M.; Choate, LaDonna M.; Church, Stan E.; Fey, David L.; Wanty, Richard B.; Crock, James G.

2006-01-01

The chemical speciation of metals influences their biological effects. The Biotic Ligand Model (BLM) is a computational approach to predict chemical speciation and acute toxicological effects of metals on aquatic biota. Recently, the U.S. Environmental Protection Agency incorporated the BLM into their regulatory water-quality criteria for copper. Results from three different laboratory copper toxicity tests were compared with BLM predictions for simulated test-waters. This was done to evaluate the ability of the BLM to accurately predict the effects of hardness and concentrations of dissolved organic carbon (DOC) and iron on aquatic toxicity. In addition, we evaluated whether the BLM and the three toxicity tests provide consistent results. Comparison of BLM predictions with two types of Ceriodaphnia dubia toxicity tests shows that there is fairly good agreement between predicted LC50 values computed by the BLM and LC50 values determined from the two toxicity tests. Specifically, the effect of increasing calcium concentration (and hardness) on copper toxicity appears to be minimal. Also, there is fairly good agreement between the BLM and the two toxicity tests for test solutions containing elevated DOC, for which the LC50 is 3-to-5 times greater (less toxic) than the LC50 for the lower-DOC test water. This illustrates the protective effects of DOC on copper toxicity and demonstrates the ability of the BLM to predict these protective effects. In contrast, for test solutions with added iron there is a decrease in LC50 values (increase in toxicity) in results from the two C. dubia toxicity tests, and the agreement between BLM LC50 predictions and results from these toxicity tests is poor. The inability of the BLM to account for competitive iron binding to DOC or DOC fractionation may be a significant shortcoming of the BLM for predicting site- specific water-quality criteria in streams affected by iron-rich acidic drainage in mined and mineralized areas.

Arsenic mobilization and immobilization in paddy soils

NASA Astrophysics Data System (ADS)

Kappler, A.; Hohmann, C.; Zhu, Y. G.; Morin, G.

2010-05-01

Arsenic is oftentimes of geogenic origin and in many cases bound to iron(III) minerals. Iron(III)-reducing bacteria can harvest energy by coupling the oxidation of organic or inorganic electron donors to the reduction of Fe(III). This process leads either to dissolution of Fe(III)-containing minerals and thus to a release of the arsenic into the environment or to secondary Fe-mineral formation and immobilisation of arsenic. Additionally, aerobic and anaerobic iron(II)-oxidizing bacteria have the potential to co-precipitate or sorb arsenic during iron(II) oxidation at neutral pH that is usually followed by iron(III) mineral precipitation. We are currently investigating arsenic immobilization by Fe(III)-reducing bacteria and arsenic co-precipitation and immobilization by anaerobic iron(II)-oxidizing bacteria in batch, microcosm and rice pot experiments. Co-precipitation batch experiments with pure cultures of nitrate-dependent Fe(II)-oxidizing bacteria are used to quantify the amount of arsenic that can be immobilized during microbial iron mineral precipitation, to identify the minerals formed and to analyze the arsenic binding environment in the precipitates. Microcosm and rice pot experiments are set-up with arsenic-contaminated rice paddy soil. The microorganisms (either the native microbial population or the soil amended with the nitrate-dependent iron(II)-oxidizing Acidovorax sp. strain BoFeN1) are stimulated either with iron(II), nitrate, or oxygen. Dissolved and solid-phase arsenic and iron are quantified. Iron and arsenic speciation and redox state in batch and microcosm experiments are determined by LC-ICP-MS and synchrotron-based methods (EXAFS, XANES).

Characterization by thermoelectric power of a commercial aluminum-iron-silicon alloy (8011) during isothermal precipitation

NASA Astrophysics Data System (ADS)

Luiggi, Ney José A.

1998-11-01

We have characterized a commercial 8011 (Al-Fe-Si) alloy by studying samples under different initial states of strain hardening and iron and silicon supersaturation using thermoelectric power as a measurement technique. Isothermal kinetics of precipitation are obtained in the temperature range between 225 °C and 600 °C. We determine the atom fraction precipitated for each microstructural condition, identifying the dominant alloying additions and evaluating the typical parameters of the precipitated phases, such as, for example, the apparent activation energy. Finally, we determine the time-temperature-transformation (TTT) diagrams. Our results prove that iron is the alloying addition that controls the precipitation kinetics of the 8011 alloy in the temperature range studied.

Computational approaches for deciphering the equilibrium and kinetic properties of iron transport proteins.

PubMed

Abdizadeh, H; Atilgan, A R; Atilgan, C; Dedeoglu, B

2017-11-15

With the advances in three-dimensional structure determination techniques, high quality structures of the iron transport proteins transferrin and the bacterial ferric binding protein (FbpA) have been deposited in the past decade. These are proteins of relatively large size, and developments in hardware and software have only recently made it possible to study their dynamics using standard computational resources. We review computational techniques towards understanding the equilibrium and kinetic properties of iron transport proteins under different environmental conditions. At the level of detail that requires quantum chemical treatments, the octahedral geometry around iron has been scrutinized and it has been established that the iron coordinating tyrosines are in an unusual deprotonated state. At the atomistic level, both the N-lobe and the full bilobal structure of transferrin have been studied under varying conditions of pH, ionic strength and binding of other metal ions by molecular dynamics (MD) simulations. These studies have allowed questions to be answered, among others, on the function of second shell residues in iron release, the role of synergistic anions in preparing the active site for iron binding, and the differences between the kinetics of the N- and the C-lobe. MD simulations on FbpA have led to the detailed observation of the binding kinetics of phosphate to the apo form, and to the conformational preferences of the holo form under conditions mimicking the environmental niches provided by the periplasmic space. To study the dynamics of these proteins with their receptors, one must resort to coarse-grained methodologies, since these systems are prohibitively large for atomistic simulations. A study of the complex of human transferrin (hTf) with its pathogenic receptor by such methods has revealed a potential mechanistic explanation for the defense mechanism that arises in evolutionary warfare. Meanwhile, the motions in the transferrin receptor bound hTf have been shown to disfavor apo hTf dissociation, explaining why the two proteins remain in complex during the recycling process from the endosome to the cell surface. Open problems and possible technological applications related to metal ion binding-release in iron transport proteins that may be handled by hybrid use of quantum mechanical, MD and coarse-grained approaches are discussed.

Immobilization of selenate by iron in aqueous solution under anoxic conditions and the influence of uranyl

NASA Astrophysics Data System (ADS)

Puranen, Anders; Jonsson, Mats; Dähn, Rainer; Cui, Daqing

2009-08-01

In proposed high level radioactive waste repositories a large part of the spent nuclear fuel (SNF) canisters are commonly composed of iron. Selenium is present in spent nuclear fuel as a long lived fission product. This study investigates the influence of iron on the uptake of dissolved selenium in the form of selenate and the effect of the presence of dissolved uranyl on the above interaction of selenate. The iron oxide, and selenium speciation on the surfaces was investigated by Raman spectroscopy. X-ray Absorption Spectroscopy was used to determine the oxidation state of the selenium and uranium on the surfaces. Under the simulated groundwater conditions (10 mM NaCl, 2 mM NaHCO 3, <0.1 ppm O 2) the immobilized selenate was found to be reduced to oxidation states close to zero or lower and uranyl was found to be largely reduced to U(IV). The near simultaneous reduction of uranyl was found to greatly enhance the rate of selenate reduction. These findings suggest that the presence of uranyl being reduced by an iron surface could substantially enhance the rate of reduction of selenate under anoxic conditions relevant for a repository.

The impact of steeping, germination and hydrothermal processing of wheat (Triticum aestivum L.) grains on phytate hydrolysis and the distribution, speciation and bio-accessibility of iron and zinc elements.

PubMed

Lemmens, Elien; De Brier, Niels; Spiers, Kathryn M; Ryan, Chris; Garrevoet, Jan; Falkenberg, Gerald; Goos, Peter; Smolders, Erik; Delcour, Jan A

2018-10-30

Chelation of iron and zinc in wheat as phytates lowers their bio-accessibility. Steeping and germination (15 °C, 120 h) lowered phytate content from 0.96% to only 0.81% of initial dry matter. A multifactorial experiment in which (steeped/germinated) wheat was subjected to different time (2-24 h), temperature (20-80 °C) and pH (2.0-8.0) conditions showed that hydrothermal processing of germinated (15 °C, 120 h) wheat at 50 °C and pH 3.8 for 24 h reduced phytate content by 95%. X-ray absorption near-edge structure imaging showed that it indeed abolished chelation of iron to phytate. It also proved that iron was oxidized during steeping, germination and hydrothermal processing. It was further shown that zinc and iron bio-accessibility were respectively 3 and 5% in wheat and 27 and 37% in hydrothermally processed wheat. Thus, hydrothermal processing of (germinated) wheat paves the way for increasing elemental bio-accessibility in whole grain-based products. Copyright © 2018 Elsevier Ltd. All rights reserved.

Emission characteristics and chemical components of size-segregated particulate matter in iron and steel industry

NASA Astrophysics Data System (ADS)

Jia, Jia; Cheng, Shuiyuan; Yao, Sen; Xu, Tiebing; Zhang, Tingting; Ma, Yuetao; Wang, Hongliang; Duan, Wenjiao

2018-06-01

As one of the highest energy consumption and pollution industries, the iron and steel industry is regarded as a most important source of particulate matter emission. In this study, chemical components of size-segregated particulate matters (PM) emitted from different manufacturing units in iron and steel industry were sampled by a comprehensive sampling system. Results showed that the average particle mass concentration was highest in sintering process, followed by puddling, steelmaking and then rolling processes. PM samples were divided into eight size fractions for testing the chemical components, SO42- and NH4+ distributed more into fine particles while most of the Ca2+ was concentrated in coarse particles, the size distribution of mineral elements depended on the raw materials applied. Moreover, local database with PM chemical source profiles of iron and steel industry were built and applied in CMAQ modeling for simulating SO42- and NO3- concentration, results showed that the accuracy of model simulation improved with local chemical source profiles compared to the SPECIATE database. The results gained from this study are expected to be helpful to understand the components of PM in iron and steel industry and contribute to the source apportionment researches.

Influence of silicon treatment on antimony uptake and translocation in rice genotypes with different radial oxygen loss.

PubMed

Zhang, Liping; Yang, Qianqian; Wang, Shiliang; Li, Wanting; Jiang, Shaoqing; Liu, Yan

2017-10-01

Antimony (Sb) pollution in soil may have a negative impact on the health of people consuming rice. This study investigated the effect of silicon (Si) application on rice biomass, iron plaque formation, and Sb uptake and speciation in rice plants with different radial oxygen loss (ROL) using pot experiments. The results demonstrated that Si addition increased the biomass of straw and grain, but had no obvious impact on the root biomass. Indica genotypes with higher ROL underwent greater iron plaque formation and exhibited more Sb sequestration in iron plaque. Silicon treatments increased iron levels in iron plaque from the different genotypes but decreased the total Sb concentration in root, straw, husk, and grain. In addition, Si treatment reduced the inorganic Sb concentrations but slightly increased the trimethylantimony (TMSb) concentrations in rice straw. Moreover, rice straw from hybrid genotypes accumulated higher concentrations of TMSb and inorganic Sb than that from indica genotypes. The conclusions from this study indicate that Sb contamination in rice can be efficiently reduced by applying Si treatment and selecting genotypes with high ROL. Copyright © 2017 Elsevier Inc. All rights reserved.

Glacial influence on the geochemistry of riverine iron fluxes to the Gulf of Alaska and effects of deglaciation

USGS Publications Warehouse

Schroth, A.W.; Crusius, John; Chever, F.; Bostick, B.C.; Rouxel, O.J.

2011-01-01

Riverine iron (Fe) derived from glacial weathering is a critical micronutrient source to ecosystems of the Gulf of Alaska (GoA). Here we demonstrate that the source and chemical nature of riverine Fe input to the GoA could change dramatically due to the widespread watershed deglaciation that is underway. We examine Fe size partitioning, speciation, and isotopic composition in tributaries of the Copper River which exemplify a long-term GoA watershed evolution from one strongly influenced by glacial weathering to a boreal-forested watershed. Iron fluxes from glacierized tributaries bear high suspended sediment and colloidal Fe loads of mixed valence silicate species, with low concentrations of dissolved Fe and dissolved organic carbon (DOC). Iron isotopic composition is indicative of mechanical weathering as the Fe source. Conversely, Fe fluxes from boreal-forested systems have higher dissolved Fe concentrations corresponding to higher DOC concentrations. Iron colloids and suspended sediment consist of Fe (hydr)oxides and organic complexes. These watersheds have an iron isotopic composition indicative of an internal chemical processing source. We predict that as the GoA watershed evolves due to deglaciation, so will the source, flux, and chemical nature of riverine Fe loads, which could have significant ramifications for Alaskan marine and freshwater ecosystems.

Leaching of Arsenic from Granular Ferric Hydroxide Residuals under Mature Landfill Conditions

PubMed Central

Ghosh, Amlan; Mukiibi, Muhammed; Sáez, A. Eduardo; Ela, Wendell P.

2008-01-01

Most arsenic bearing solid residuals (ABSR) from water treatment will be disposed in non-hazardous landfills. The lack of an appropriate leaching test to predict arsenic mobilization from ABSR creates a need to evaluate the magnitude and mechanisms of arsenic release under landfill conditions. This work studies the leaching of arsenic and iron from a common ABSR, granular ferric hydroxide, in a laboratory-scale column that simulates the biological and physicochemical conditions of a mature, mixed solid waste landfill. The column operated for approximately 900 days and the mode of transport as well as chemical speciation of iron and arsenic changed with column age. Both iron and arsenic were readily mobilized under the anaerobic, reducing conditions. During the early stages of operation, most arsenic and iron leaching (80% and 65%, respectively) was associated with suspended particulate matter and iron was lost proportionately faster than arsenic. In later stages, while the rate of iron leaching declined, the arsenic leaching rate increased greater than 7-fold. The final phase was characterized by dissolved species leaching. Future work on the development of standard batch leaching tests should take into account the dominant mobilization mechanisms identified in this work: solid associated transport, reductive sorbent dissolution, and microbially mediated arsenic reduction. PMID:17051802

Leaching of arsenic from granular ferric hydroxide residuals under mature landfill conditions.

PubMed

Ghosh, Amlan; Mukiibi, Muhammed; Sáez, A Eduardo; Ela, Wendell P

2006-10-01

Most arsenic bearing solid residuals (ABSR) from water treatment will be disposed in nonhazardous landfills. The lack of an appropriate leaching test to predict arsenic mobilization from ABSR creates a need to evaluate the magnitude and mechanisms of arsenic release under landfill conditions. This work studies the leaching of arsenic and iron from a common ABSR, granular ferric hydroxide, in a laboratory-scale column that simulates the biological and physicochemical conditions of a mature, mixed solid waste landfill. The column operated for approximately 900 days and the mode of transport as well as chemical speciation of iron and arsenic changed with column age. Both iron and arsenic were readily mobilized under the anaerobic, reducing conditions. During the early stages of operation, most arsenic and iron leaching (80% and 65%, respectively) was associated with suspended particulate matter, and iron was lost proportionately faster than arsenic. In later stages, while the rate of iron leaching declined, the arsenic leaching rate increased greater than 7-fold. The final phase was characterized by dissolved species leaching. Future work on the development of standard batch leaching tests should take into account the dominant mobilization mechanisms identified in this work: solid associated transport, reductive sorbent dissolution, and microbially mediated arsenic reduction.

Fenton and Fenton-like oxidation of pesticide acetamiprid in water samples: kinetic study of the degradation and optimization using response surface methodology.

PubMed

Mitsika, Elena E; Christophoridis, Christophoros; Fytianos, Konstantinos

2013-11-01

The aims of this study were (a) to evaluate the degradation of acetamiprid with the use of Fenton reaction, (b) to investigate the effect of different concentrations of H2O2 and Fe(2+), initial pH and various iron salts, on the degradation of acetamiprid and (c) to apply response surface methodology for the evaluation of degradation kinetics. The kinetic study revealed a two-stage process, described by pseudo- first and second order kinetics. Different H2O2:Fe(2+) molar ratios were examined for their effect on acetamiprid degradation kinetics. The ratio of 3 mg L(-1) Fe(2+): 40 mg L(-1) H2O2 was found to completely remove acetamiprid at less than 10 min. Degradation rate was faster at lower pH, with the optimal value at pH 2.9, while Mohr salt appeared to degrade acetamiprid faster. A central composite design was selected in order to observe the effects of Fe(2+) and H2O2 initial concentration on acetamiprid degradation kinetics. A quadratic model fitted the experimental data, with satisfactory regression and fit. The most significant effect on the degradation of acetamiprid, was induced by ferrous iron concentration followed by H2O2. Optimization, aiming to minimize the applied ferrous concentration and the process time, proposed a ratio of 7.76 mg L(-1) Fe(II): 19.78 mg L(-1) H2O2. DOC is reduced much more slowly and requires more than 6h of processing for 50% degradation. The use to zero valent iron, demonstrated fast kinetic rates with acetamiprid degradation occurring in 10 min and effective DOC removal. Copyright © 2013 Elsevier Ltd. All rights reserved.

Stoichio-Kinetic Modeling of Fenton Chemistry in a Meat-Mimetic Aqueous-Phase Medium.

PubMed

Oueslati, Khaled; Promeyrat, Aurélie; Gatellier, Philippe; Daudin, Jean-Dominique; Kondjoyan, Alain

2018-05-31

Fenton reaction kinetics, which involved an Fe(II)/Fe(III) oxidative redox cycle, were studied in a liquid medium that mimics meat composition. Muscle antioxidants (enzymes, peptides, and vitamins) were added one by one in the medium to determine their respective effects on the formation of superoxide and hydroxyl radicals. A stoichio-kinetic mathematical model was used to predict the formation of these radicals under different iron and H 2 O 2 concentrations and temperature conditions. The difference between experimental and predicted results was mainly due to iron reactivity, which had to be taken into account in the model, and to uncertainties on some of the rate constant values introduced in the model. This stoichio-kinetic model will be useful to predict oxidation during meat processes, providing it can be completed to take into account the presence of myoglobin in the muscle.

Electromagnetic studies of redox systems for energy storage

NASA Technical Reports Server (NTRS)

Wu, C. D.; Scherson, D.; Yeager, E.

1981-01-01

Both chromium and iron couples were studied on various electrode surfaces in acidic perchlorate solution by using rotating ring-disk techniques. It was found that chloride which forms inner sphere coordination complexes with the redox species enhances the electrode kinetics dramatically. The effects of lead underpotential deposition and surface alloy formation on the kinetics of the chromium couple on gold were studied using both linear sweep voltammetry and potential step techniques. The lad underpotential deposition was found to slow down the kinetics of the reduction of the Cr species on gold surfaces although increase the hydrogen overvoltage. The effect on the chromium kinetics can be explained in terms of principally a double layer effect. The underpotential deposition lead species with its positive charge results in a decrease in the concentration of the Cr species at the electrode surface. Similar phenomena were also observed with bismuth underpotential deposition on gold for the iron couple.

User's guide to PHREEQC (Version 2) : a computer program for speciation, batch-reaction, one-dimensional transport, and inverse geochemical calculations

USGS Publications Warehouse

Parkhurst, David L.; Appelo, C.A.J.

1999-01-01

PHREEQC version 2 is a computer program written in the C programming language that is designed to perform a wide variety of low-temperature aqueous geochemical calculations. PHREEQC is based on an ion-association aqueous model and has capabilities for (1) speciation and saturation-index calculations; (2) batch-reaction and one-dimensional (1D) transport calculations involving reversible reactions, which include aqueous, mineral, gas, solid-solution, surface-complexation, and ion-exchange equilibria, and irreversible reactions, which include specified mole transfers of reactants, kinetically controlled reactions, mixing of solutions, and temperature changes; and (3) inverse modeling, which finds sets of mineral and gas mole transfers that account for differences in composition between waters, within specified compositional uncertainty limits.New features in PHREEQC version 2 relative to version 1 include capabilities to simulate dispersion (or diffusion) and stagnant zones in 1D-transport calculations, to model kinetic reactions with user-defined rate expressions, to model the formation or dissolution of ideal, multicomponent or nonideal, binary solid solutions, to model fixed-volume gas phases in addition to fixed-pressure gas phases, to allow the number of surface or exchange sites to vary with the dissolution or precipitation of minerals or kinetic reactants, to include isotope mole balances in inverse modeling calculations, to automatically use multiple sets of convergence parameters, to print user-defined quantities to the primary output file and (or) to a file suitable for importation into a spreadsheet, and to define solution compositions in a format more compatible with spreadsheet programs. This report presents the equations that are the basis for chemical equilibrium, kinetic, transport, and inverse-modeling calculations in PHREEQC; describes the input for the program; and presents examples that demonstrate most of the program's capabilities.

Spectral-kinetic characteristics of luminescence of pentaerythritol tetranitrate with inclusions of iron nanoparticles upon explosion induced by laser pulses

NASA Astrophysics Data System (ADS)

Aduev, B. P.; Nurmukhametov, D. R.; Belokurov, G. M.; Nelyubina, N. V.; Gudilin, A. V.

2017-03-01

Spectral-kinetic characteristics of luminescence of tetranitropentaeritrite with inclusions of iron nanoparticles upon an explosion induced by laser pulses are measured with high temporal resolution. It is shown that the luminescence occurring during exposure to the laser pulse is a result of initiating a chemical reaction in tetranitropentaeritrite and is chemiluminescence. The glow is presumably associated with the excited nitrogen dioxide, NO2, which is formed by the rupture of O-NO2 bond in the tetranitropentaeritrite molecule.

IroN, a Novel Outer Membrane Siderophore Receptor Characteristic of Salmonella enterica

PubMed Central

Bäumler, Andreas J.; Norris, Tracy L.; Lasco, Todd; Voigt, Wolfgang; Reissbrodt, Rolf; Rabsch, Wolfgang; Heffron, Fred

1998-01-01

Speciation in enterobacteria involved horizontal gene transfer. Therefore, analysis of genes acquired by horizontal transfer that are present in one species but not its close relatives is expected to give insights into how new bacterial species were formed. In this study we characterize iroN, a gene located downstream of the iroBC operon in the iroA locus of Salmonella enterica serotype Typhi. Like iroBC, the iroN gene is present in all phylogenetic lineages of S. enterica but is absent from closely related species such as Salmonella bongori or Escherichia coli. Comparison of the deduced amino acid sequence of iroN with other proteins suggested that this gene encodes an outer membrane siderophore receptor protein. Mutational analysis in S. enterica and expression in E. coli identified a 78-kDa outer membrane protein as the iroN gene product. When introduced into an E. coli fepA cir fiu aroB mutant on a cosmid, iroN mediated utilization of structurally related catecholate siderophores, including N-(2,3-dihydroxybenzoyl)-l-serine, myxochelin A, benzaldehyde-2,3-dihydroxybenzhydrazone, 2-N,6-N-bis(2,3-dihydroxybenzoyl)-l-lysine, 2-N,6-N-bis(2,3-dihydroxybenzoyl)-l-lysine amide, and enterochelin. These results suggest that the iroA locus functions in iron acquisition in S. enterica. PMID:9515912

Oil-in-water emulsions for encapsulated delivery of reactive iron particles.

PubMed

Berge, Nicole D; Ramsburg, C Andrew

2009-07-01

Treatment of dense nonaqueous phase liquid (DNAPL) source zones using suspensions of reactive iron particles relies upon effective transport of the nano- to submicrometer scale iron particles within the subsurface. Recognition that poor subsurface transport of iron particles results from particle-particle and particle-soil interactions permits development of strategies which increase transport. In this work, experiments were conducted to assess a novel approach for encapsulated delivery of iron particles within porous media using oil-in-water emulsions. Objectives of this study included feasibility demonstration of producing kinetically stable, iron-containing, oil-in-water emulsions and evaluating the transport of these iron-containing, oil-in-water emulsions within water-saturated porous media. Emulsions developed in this study have mean droplet diameters between 1 and 2 microm, remain kinetically stable for > 1.5 h, and possess densities (0.996-1.00 g/mL at 22 degrees C) and dynamic viscosities (2.4-9.3 mPa x s at 22 degrees C and 20 s(-1)) that are favorable to transport within DNAPL source zones. Breakthrough curves and post-experiment extractions from column experiments conducted with medium and fine sands suggest little emulsion retention (< 0.20% wt) at a Darcy velocity of 0.4 m/day. These findings demonstrate that emulsion encapsulation is a promising method for delivery of iron particles and warrants further investigation.

Effect of electrolyte nature on kinetics of remazol yellow G removal by electrocoagulation

NASA Astrophysics Data System (ADS)

Rajabi, M.; Bagheri-Roochi, M.; Asghari, A.

2011-10-01

The present study describes an electrocoagulation process for the removal of remazol yellow G from dye solutions using Iron as the anode and Steel as the cathode. Pseudo-first-order, pseudo-second-order and intraparticle diffusion models were used to analyze the kinetic data obtained at different concentrations in different conditions. The adsorption kinetics was well described by the pseudo-second-order kinetic model.

Chromium in urban sediment particulates: an integrated micro-chemical and XANES study

NASA Astrophysics Data System (ADS)

Taylor, Kevin; Byrne, Patrick; Hudson-Edwards, Karen

2015-04-01

Chromium is generally common within the urban sediment cascade as a result of abundant industrial and transport-related sources. The risks that Cr-bearing particles pose to ecosystems and humans depend on the solid phase chemical speciation of Cr in the particles. In this study, we use bulk chemical digests, sequential chemical extraction analysis, electron microscopy, electron microprobe and microfocus XANES analysis to describe the solid-phase speciation of Cr in urban particulate matter from both aquatic sediment and road dust sediment (RDS) in Manchester, UK. Cr-bearing grains within RDS are predominantly iron oxide grains, commonly of goethite or haematite mineralogy, but Cr-bearing silicate glass grains are also present. Iron oxide glass grains most likely have sorbed Cr, and derive from the rusting of Cr-steel particles from vehicles. Electron microprobe analysis indicates concentrations of Cr up to 3200 μg/g in these grains, and XANES analysis indicates that Cr(III) is the dominant oxidation state, with some trace amounts of Cr(VI). Cr-bearing grains within aquatic sediments are dominated by alumino-silicate glass grains derived from industrial waste. These grains contain Cr-rich areas with up to 19% Cr2O3 and XANES analysis indicates that Cr is present as Cr(III). The dominance of Cr(III) in these urban particulate grains suggests limited bioavailability or toxicity. However, the presence within two markedly different grain types (iron oxides and silicate glasses) indicates that the long-term geochemical behaviour and environmental risk of RDS and the aquatic sediments studied are likely to be quite different. These findings highlight the importance of understanding sources of metal contaminants in urban environments and the geochemical processes that affect their transfer through the urban sediment cascade and the wider river basin.

Iron translocation into and out of Listeria innocua Dps and size distribution of the protein-enclosed nanomineral are modulated by the electrostatic gradient at the 3-fold "ferritin-like" pores.

PubMed

Bellapadrona, Giuliano; Stefanini, Simonetta; Zamparelli, Carlotta; Theil, Elizabeth C; Chiancone, Emilia

2009-07-10

Elucidating pore function at the 3-fold channels of 12-subunit, microbial Dps proteins is important in understanding their role in the management of iron/hydrogen peroxide. The Dps pores are called "ferritin-like" because of the structural resemblance to the 3-fold channels of 24-subunit ferritins used for iron entry and exit to and from the protein cage. In ferritins, negatively charged residues lining the pores generate a negative electrostatic gradient that guides iron ions toward the ferroxidase centers for catalysis with oxidant and destined for the mineralization cavity. To establish whether the set of three aspartate residues that line the pores in Listeria innocua Dps act in a similar fashion, D121N, D126N, D130N, and D121N/D126N/D130N proteins were produced; kinetics of iron uptake/release and the size distribution of the iron mineral in the protein cavity were compared. The results, discussed in the framework of crystal growth in a confined space, indicate that iron uses the hydrophilic 3-fold pores to traverse the protein shell. For the first time, the strength of the electrostatic potential is observed to modulate kinetic cooperativity in the iron uptake/release processes and accordingly the size distribution of the microcrystalline iron minerals in the Dps protein population.

Iron speciation of airborne subway particles by the combined use of energy dispersive electron probe X-ray microanalysis and Raman microspectrometry.

PubMed

Eom, Hyo-Jin; Jung, Hae-Jin; Sobanska, Sophie; Chung, Sang-Gwi; Son, Youn-Suk; Kim, Jo-Chun; Sunwoo, Young; Ro, Chul-Un

2013-11-05

Quantitative energy-dispersive electron probe X-ray microanalysis (ED-EPMA), known as low-Z particle EPMA, and Raman microspectrometry (RMS) were applied in combination for an analysis of the iron species in airborne PM10 particles collected in underground subway tunnels. Iron species have been reported to be a major chemical species in underground subway particles generated mainly from mechanical wear and friction processes. In particular, iron-containing particles in subway tunnels are expected to be generated with minimal outdoor influence on the particle composition. Because iron-containing particles have different toxicity and magnetic properties depending on their oxidation states, it is important to determine the iron species of underground subway particles in the context of both indoor public health and control measures. A recently developed analytical methodology, i.e., the combined use of low-Z particle EPMA and RMS, was used to identify the chemical species of the same individual subway particles on a single particle basis, and the bulk iron compositions of airborne subway particles were also analyzed by X-ray diffraction. The majority of airborne subway particles collected in the underground tunnels were found to be magnetite, hematite, and iron metal. All the particles collected in the tunnels of underground subway stations were attracted to permanent magnets due mainly to the almost ubiquitous ferrimagnetic magnetite, indicating that airborne subway particles can be removed using magnets as a control measure.

A Microstructural and Kinetic Investigation of the KCl-Induced Corrosion of an FeCrAl Alloy at 600 °C

DOE PAGES

Israelsson, Niklas; Unocic, Kinga A.; Hellström, K.; ...

2015-03-18

In this paper, the corrosion behaviour of a FeCrAl alloy was investigated at 600 °C in O 2 + H 2O with solid KCl applied. A kinetics and microstructural investigation showed that KCl accelerates corrosion and that potassium chromate formation depletes the protective scale in Cr, thus triggering the formation of a fast-growing iron-rich scale. Iron oxide was found to grow both inward and outward, on either side of the initial oxide. A chromia layer is formed with time underneath the iron oxide. Finally, it was found that although the alloy does not form a continuous pure alumina scale atmore » the investigated temperature, aluminium is, however, always enriched at the oxide/alloy interface.« less

Sulfur and iron speciation in gas-rich impact-melt glasses from basaltic shergottites determined by microXANES

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sutton, S.R.; Rao, M.N.; Nyquist, L.E.

2008-04-28

Sulfur and iron K XANES measurements were made on GRIM glasses from EET 79001. Iron is in the ferrous state. Sulfur speciation is predominately sulfide coordination but is Fe coordinated in Lith B and, most likely, Ca coordinated in Lith A. Sulfur is abundantly present as sulfate near Martian surface based on chemical and mineralogical investigations on soils and rocks in Viking, Pathfinder and MER missions. Jarosite is identified by Moessbauer studies on rocks at Meridian and Gusev, whereas MgSO{sub 4} is deduced from MgO-SO{sub 3} correlations in Pathfinder MER and Viking soils. Other sulfate minerals such as gypsum andmore » alunogen/S-rich aluminosilicates and halides are detected only in martian meteorites such as shergottites and nakhlites using SEM/FE-SEM and EMPA techniques. Because sulfur has the capacity to occur in multiple valence states, determination of sulfur speciation (sulfide/sulfate) in secondary mineral assemblages in soils and rocks near Mars surface may help us understand whether the fluid-rock interactions occurred under oxidizing or reducing conditions. On Earth, volcanic rocks contain measurable quantities of sulfur present as both sulfide and sulfate. Carroll and Rutherford showed that oxidized forms of sulfur may comprise a significant fraction of total dissolved sulfur, if the oxidation state is higher than {approx}2 log fO{sub 2} units relative to the QFM buffer. Terrestrial samples containing sulfates up to {approx}25% in fresh basalts from the Galapagos Rift on one hand and high sulfide contents present in oceanic basalts on the other indicate that the relative abundance of sulfide and sulfate varies depending on the oxygen fugacity of the system. Basaltic shergottites (bulk) such as Shergotty, EET79001 and Zagami usually contain small amounts of sulfur ({approx}0.5%) as pyrrhotite. But, in isolated glass pockets containing secondary salts (known as GRIM glasses) in these meteorites, sulfur is present in high abundance ({approx}1-12%). To determine sulfur speciation (sulfide, sulfate or elemental sulfur) in these glasses, Gooding et al. and Burgess et al. carried out vacuum pyrolysis experiments on these GRIM glasses (also called Lith C) using quadrupole mass-spectrometric methods. They found that the evolved S-bearing gases from these samples consisted of both SO{sub 2} (from sulfate) and H{sub 2}S (from sulfide) in varying proportions. However, as mass-spectrometric studies do not provide details about spatial association of these S-species in these samples, we have studied the spatial distribution of sulfides and sulfates in GRIM glasses using sulfur K micro-XANES techniques in the present study. The microscale speciation of S may have important implications for the Rb-Sr isotope systematics of EET79001 Lith C glasses. In reference to oxidative weathering of surface basalts on Mars yielding secondary iron sulfates, Solberg and Burns examined a GRIM glass in EET79001 by Moessbauer spectroscopic techniques and showed that the percentage of Fe{sup 3+} in Lith C is <2%. They suggested that the Lith C contains very little Fe{sup 3+} despite the occurrence of oxidized sulfate in them, indicating that the conditions leading to the formation of these glasses were insufficiently oxidizing to produce Fe{sup 3+} from Fe{sup 2+} in these glasses. To understand the implications of these observations for the formation of the GRIM glasses, we determined the oxidation state of Fe in the GRIM glasses using Fe K micro-XANES techniques. The S and Fe K micro-XANES measurements were performed on thin sections from EET79001: 506 from Lith A and 507 from Lith B.« less

Variability of the health effects of crystalline silica: Fe speciation in industrial quartz reagents and suspended dusts—insights from XAS spectroscopy

NASA Astrophysics Data System (ADS)

Di Benedetto, Francesco; D'Acapito, Francesco; Capacci, Fabio; Fornaciai, Gabriele; Innocenti, Massimo; Montegrossi, Giordano; Oberhauser, Werner; Pardi, Luca A.; Romanelli, Maurizio

2014-03-01

We investigated the speciation of Fe in bulk and in suspended respirable quartz dusts coming from ceramic and iron-casting industrial processes via X-ray absorption spectroscopy, with the aim of contributing to a better understanding of the variability of crystalline silica toxicity. Four different bulk industrial quartz powders, nominally pure quartz samples with Fe contents below 200 ppm, and three respirable dusts filters were selected. Fe speciation was determined in all samples through a coupled study of the X-ray absorption near-edge structure and extended X-ray absorption fine structure regions, operating at the Fe-K edge. Fe speciation revealed common features at the beginning of the different production processes, whereas significant differences were observed on both respirable dusts and bulk dusts exiting from the production process. Namely, a common pollution of the raw quartz dusts by elemental Fe was evidenced and attributed to residuals of the industrial production of quartz materials. Moreover, the respirable samples indicated that reactivity occurs after the suspension of the powders in air. The gravitational selection during the particle suspension consistently allowed us to clearly discriminate between suspended and bulk dusts. On the basis of the obtained results, we provide an apparent spectroscopic discrimination between the raw materials used in the considered industrial processes, and those that are effectively inhaled by workers. In particular, an amorphous FeIII oxide, with an unsaturated coordination sphere, can be related to silica reactivity (and health consequences).

Nitrate reduction and its effects on trichloroethylene degradation by granular iron.

PubMed

Lu, Qiong; Jeen, Sung-Wook; Gui, Lai; Gillham, Robert W

2017-04-01

Laboratory column experiments and reactive transport modeling were performed to evaluate the reduction of nitrate and its effects on trichloroethylene (TCE) degradation by granular iron. In addition to determining degradation kinetics of TCE in the presence of nitrate, the columns used in this study were equipped with electrodes which allowed for in situ measurements of corrosion potentials of the iron material. Together with Raman spectroscopic measurements the mechanisms of decline in iron reactivity were examined. The experimental results showed that the presence of nitrate resulted in an increase in corrosion potential and the formation of thermodynamically stable passive films on the iron surface which impaired iron reactivity. The extent of the decline in iron reactivity was proportional to the nitrate concentration. Consequently, significant decreases in TCE and nitrate degradation rates and migration of degradation profiles for both compounds occurred. Furthermore, the TCE degradation kinetics deviated from the pseudo-first-order model. The results of reactive transport modeling, which related the amount of a passivating iron oxide, hematite (α-Fe 2 O 3 ), to the reactivity of iron, were generally consistent with the patterns of migration of TCE and nitrate profiles observed in the column experiments. More encouragingly, the simulations successfully demonstrated the differences in performances of three columns without changing model parameters other than concentrations of nitrate in the influent. This study could be valuable in the design of iron permeable reactive barriers (PRBs) or in the development of effective maintenance procedures for PRBs treating TCE-contaminated groundwater with elevated nitrate concentrations. Copyright © 2017 Elsevier Ltd. All rights reserved.

Solid-State Kinetic Investigations of Nonisothermal Reduction of Iron Species Supported on SBA-15

PubMed Central

2017-01-01

Iron oxide catalysts supported on nanostructured silica SBA-15 were synthesized with various iron loadings using two different precursors. Structural characterization of the as-prepared FexOy/SBA-15 samples was performed by nitrogen physisorption, X-ray diffraction, DR-UV-Vis spectroscopy, and Mössbauer spectroscopy. An increasing size of the resulting iron species correlated with an increasing iron loading. Significantly smaller iron species were obtained from (Fe(III), NH4)-citrate precursors compared to Fe(III)-nitrate precursors. Moreover, smaller iron species resulted in a smoother surface of the support material. Temperature-programmed reduction (TPR) of the FexOy/SBA-15 samples with H2 revealed better reducibility of the samples originating from Fe(III)-nitrate precursors. Varying the iron loading led to a change in reduction mechanism. TPR traces were analyzed by model-independent Kissinger method, Ozawa, Flynn, and Wall (OFW) method, and model-dependent Coats-Redfern method. JMAK kinetic analysis afforded a one-dimensional reduction process for the FexOy/SBA-15 samples. The Kissinger method yielded the lowest apparent activation energy for the lowest loaded citrate sample (Ea ≈ 39 kJ/mol). Conversely, the lowest loaded nitrate sample possessed the highest apparent activation energy (Ea ≈ 88 kJ/mol). For samples obtained from Fe(III)-nitrate precursors, Ea decreased with increasing iron loading. Apparent activation energies from model-independent analysis methods agreed well with those from model-dependent methods. Nucleation as rate-determining step in the reduction of the iron oxide species was consistent with the Mampel solid-state reaction model. PMID:29230346

The role of nonconserved residues of Archaeoglobus fulgidus ferritin on its unique structure and biophysical properties.

PubMed

Sana, Barindra; Johnson, Eric; Le Magueres, Pierre; Criswell, Angela; Cascio, Duilio; Lim, Sierin

2013-11-08

Archaeoglobus fulgidus ferritin (AfFtn) is the only tetracosameric ferritin known to form a tetrahedral cage, a structure that remains unique in structural biology. As a result of the tetrahedral (2-3) symmetry, four openings (∼45 Å in diameter) are formed in the cage. This open tetrahedral assembly contradicts the paradigm of a typical ferritin cage: a closed assembly having octahedral (4-3-2) symmetry. To investigate the molecular mechanism affecting this atypical assembly, amino acid residues Lys-150 and Arg-151 were replaced by alanine. The data presented here shed light on the role that these residues play in shaping the unique structural features and biophysical properties of the AfFtn. The x-ray crystal structure of the K150A/R151A mutant, solved at 2.1 Å resolution, indicates that replacement of these key residues flips a "symmetry switch." The engineered molecule no longer assembles with tetrahedral symmetry but forms a typical closed octahedral ferritin cage. Small angle x-ray scattering reveals that the overall shape and size of AfFtn and AfFtn-AA in solution are consistent with those observed in their respective crystal structures. Iron binding and release kinetics of the AfFtn and AfFtn-AA were investigated to assess the contribution of cage openings to the kinetics of iron oxidation, mineralization, or reductive iron release. Identical iron binding kinetics for AfFtn and AfFtn-AA suggest that Fe(2+) ions do not utilize the triangular pores for access to the catalytic site. In contrast, relatively slow reductive iron release was observed for the closed AfFtn-AA, demonstrating involvement of the large pores in the pathway for iron release.

Effects of Pressure and Temperature on the Kinetics of Iron-magnesite Redox Reaction: Implication for the Genesis of Ultradeep Diamonds

NASA Astrophysics Data System (ADS)

Zhu, F.; Li, J.; Liu, J.; Lai, X.; Chen, B.; Meng, Y.

2016-12-01

Diamonds may be the products of redox reaction between carbonates in the subducted slabs and iron metal in the mantle [1]. Given the relatively low temperatures of the subducted slabs, however, it remains to be shown that such reaction can occur at sufficiently fast rate. To examine the influence of pressure and temperature (P-T) on the kinetics of iron-carbonate redox reaction, we performed in-situ synchrotron X-ray diffraction (XRD) experiments at the Advanced Photon Source, Argonne National Laboratory, using laser-heated diamond anvil cells. The starting material consists of an iron foil sandwiched between two magnesite pellets. Data were collected between 1050 and 1800 K at 50-100 K intervals, at seven pressures between 12 and 40 GPa, corresponding the depths where most ultradeep diamonds originated [2]. We obtained constraints on the Fe-MgCO3reaction boundary, which was located between the estimated temperatures on the surface of cold slabs near 1400 K and inside their interiors near 1000 K, and it had a similar slope as the slab geotherm [3]. Furthermore, the experiments revealed a significant effect of pressure on the extent and rate of the reaction. The XRD patterns showed that below 15 GPa the initial reaction products were iron carbides, which reacted with magnesite to form diamonds when the reaction completed in 60 minutes at 1300 to 1500 K. Above 18 GPa only iron carbides were observed in the XRD patterns even when all the iron was consumed, and iron carbides still coexisted with magnesite after 100 to 160 minutes at 1600 to 1800 K. Our results suggest that diamonds can be produced from iron-carbonate redox reaction at slab-mantle boundary conditions at the deeper part of the upper mantle, but diamond growth through this reaction is slow or kinetically hindered in the lower mantle. References[1] Palyanov, Y. N. et al. (2013). Proc. Nat. Aca. Sci., 110(51), 20408-20413. [2] Stachel, T. et al. (2005). Elements, 1(2), 73-78. [3] Eberle et al. (2002). Phys. Earth Planet. Int., 134(3), 191-202.

Speciation of strontium-90 in NIST natural matrix standard reference materials

DOE Office of Scientific and Technical Information (OSTI.GOV)

Thomas, J.W.L.; Inn, K.G.W.; Garcia, M.E.

1995-12-31

A sequential leaching, radiochemical separating, and low-level beta-particle counting procedure was designed to study the speciation of radionuclides in natural matrix standard reference materials, SRMs 4350B (Columbia River Sediment) and 4353 (Rocky Flats Soil-1). Strontium-90 is the first radionuclide studied because of the difficulty experienced with this nuclide in natural-matrix SRMs. The nine-step procedure extracted {sup 90}Sr from the following fractions: water solubles, exchangeables, carbonates, reducibles, organics, iron and manganese oxides, acid leachables, micas, and silicates. The majority of {sup 90}Sr in the soil samples was found in the exchangeable fraction. By contrast, the {sup 90}Sr in the sediment ismore » more evenly distributed among the various leached fractions. Information on the leach distribution of radionuclides in environmental SRMs, based on the procedure described, should lead to more cost-effective restoration strategies and more confidence in risk assessments of human health hazards.« less

Expanding the Therapeutic Potential of the Iron Chelator Deferasirox in the Development of Aqueous Stable Ti(IV) Anticancer Complexes.

PubMed

Loza-Rosas, Sergio A; Vázquez-Salgado, Alexandra M; Rivero, Kennett I; Negrón, Lenny J; Delgado, Yamixa; Benjamín-Rivera, Josué A; Vázquez-Maldonado, Angel L; Parks, Timothy B; Munet-Colón, Charlene; Tinoco, Arthur D

2017-07-17

The recent X-ray structure of titanium(IV)-bound human serum transferrin (STf) exhibiting citrate as a synergistic anion reveals a difference in Ti(IV) coordination versus iron(III), the metal endogenously delivered by the protein to cells. This finding enriches our bioinspired drug design strategy for Ti(IV)-based anticancer therapeutics, which applies a family of Fe(III) chelators termed chemical transferrin mimetic (cTfm) ligands to inhibit Fe bioavailability in cancer cells. Deferasirox, a drug used for iron overload disease, is a cTfm ligand that models STf coordination to Fe(III), favoring Fe(III) binding versus Ti(IV). This metal affinity preference drives deferasirox to facilitate the release of cytotoxic Ti(IV) intracellularly in exchange for Fe(III). An aqueous speciation study performed by potentiometric titration from pH 4 to 8 with micromolar levels of Ti(IV) deferasirox at a 1:2 ratio reveals exclusively Ti(deferasirox) 2 in solution. The predominant complex at pH 7.4, [Ti(deferasirox) 2 ] 2- , exhibits the one of the highest aqueous stabilities observed for a potent cytotoxic Ti(IV) species, demonstrating little dissociation even after 1 month in cell culture media. UV-vis and 1 H NMR studies show that the stability is unaffected by the presence of biomolecular Ti(IV) binders such as citrate, STf, and albumin, which have been shown to induce dissociation or regulate cellular uptake and can alter the activity of other antiproliferative Ti(IV) complexes. Kinetic studies on [Ti(deferasirox) 2 ] 2- transmetalation with Fe(III) show that a labile Fe(III) source is required to induce this process. The initial step of this process occurs on the time scale of minutes, and equilibrium for the complete transmetalation is reached on a time scale of hours to a day. This work reveals a mechanism to deliver Ti(IV) compounds into cells and trigger Ti(IV) release by a labile Fe(III) species. Cellular studies including other cTfm ligands confirm the Fe(III) depletion mechanism of these compounds and show their ability to induce early and late apoptosis.

Fabrication of Iron-Containing Carbon Materials From Graphite Fluoride

NASA Technical Reports Server (NTRS)

Hung, Ching-cheh

1996-01-01

Carbon materials containing iron alloy, iron metal, iron oxide or iron halide were fabricated. Typical samples of these metals were estimated to contain 1 iron atom per 3.5 to 5 carbon atoms. Those carbon materials containing iron alloy, iron metal, and/or Fe3O4 were magnetic. The kinetics of the fabrication process were studied by exposing graphite fluoride (CF(0.68)) to FeCl3 over a 280 to 420 C temperature range. Between 280 and 295 C, FeCl3 quickly entered the structure of CF(0.68), broke the carbon-fluorine bonds, and within 10 to 30 min, completely converted it to carbon made up of graphite planes between which particles of crystalline FeF3 and noncrystalline FeCl3 were located. Longer reaction times (e.g., 28 hr) or higher reaction temperatures (e.g., 420 C) produced materials containing graphite, a FeCl3-graphite intercalation compound, FeCl2(center dot)4H2O, and FeCl2(center dot)2H2O. These products were further heat treated to produce iron-containing carbon materials. When the heating temperature was kept in the 750 to 850 C range, and the oxygen supply was kept at the optimum level, the iron halides in the carbon structure were converted to iron oxides. Raising the heat to temperatures higher than 900 C reduced such iron oxides to iron metal. The kinetics of these reactions were used to suggest processes for fabricating carbon materials containing iron alloy. Such processes were then tested experimentally. In one of the successful trial runs, commercially purchased CF(0.7) powder was used as the reactant, and NiO was added during the final heating to 1200 C as a source of both nickel and oxygen. The product thus obtained was magnetic and was confirmed to be a nickel-iron alloy in carbon.

Solid surface photochemistry of montmorillonite: mechanisms for the arsenite oxidation under UV-A irradiation.

PubMed

Yuan, Yanan; Wang, Yajie; Ding, Wei; Li, Jinjun; Wu, Feng

2016-01-01

Transformation of inorganic arsenic species has drawn great concern in recent decades because of worldwide and speciation-dependent pollution and the hazards that they pose to the environment and to human health. As(III) photooxidation in aquatic systems has received much attention, but little is known about photochemical transformation of arsenic species on top soil. As(III) photooxidation on natural montmorillonite under UV-A radiation was investigated by using a moisture- and temperature-controlled photochemical chamber with two black-light lamps. Initial As(III) concentration, pH, layer thickness, humic acid (HA) concentration, the presence of additional iron ions, and the contribution of reactive oxygen species (ROS) were examined. The results show that pH values of the clay layers greatly influenced As(III) photooxidation on montmorillonite. As(III) photooxidation followed the Langmuir-Hinshelwood model. HA and additional iron ions greatly promoted photooxidation, but excess Fe(II) competed with As(III) for oxidation by ROS. Scavenging experiments revealed that natural montmorillonite induced the conversion of As(III) to As(V) by generating ROS (mainly HO(•) and HO2(•)/O2(•-)) and that HO(•) radical was the predominant oxidant in this system. Our work demonstrates that photooxidation on the surface of natural clay minerals in top soil can be important to As(III) transformation. This allows understanding and predicting the speciation and behavior of arsenic on the soil surface.

Do radial oxygen loss and external aeration affect iron plaque formation and arsenic accumulation and speciation in rice?

PubMed Central

Wu, Chuan; Ye, Zhihong; Li, Hui; Wu, Shengchun; Deng, Dan; Zhu, Yongguan; Wong, Minghung

2012-01-01

Hydroponic experiments were conducted to investigate the effect of radial oxygen loss (ROL) and external aeration on iron (Fe) plaque formation, and arsenic (As) accumulation and speciation in rice (Oryza sativa L.). The data showed that there were significant correlations between ROL and Fe concentrations in Fe plaque produced on different genotypes of rice. There were also significant differences in the amounts of Fe plaque formed between different genotypes in different positions of roots and under different aeration conditions (aerated, normal, and stagnant treatments). In aerated treatments, rice tended to have a higher Fe plaque formation than in a stagnant solution, with the greatest formation at the root tip decreasing with increasing distances away, in accordance with a trend of spatial ROL. Genotypes with higher rates of ROL induced higher degrees of Fe plaque formation. Plaques sequestered As on rice roots, with arsenate almost double that with arsenite, leading to decreased As accumulation in both roots and shoots. The major As species detected in roots and shoots was arsenite, ranging from 34 to 78% of the total As in the different treatments and genotypes. These results contribute to our understanding of genotypic differences in As uptake by rice and the mechanisms causing rice genotypes with higher ROL to show lower overall As accumulation. PMID:22345639

Size-separated particle fractions of stainless steel welding fume particles - A multi-analytical characterization focusing on surface oxide speciation and release of hexavalent chromium.

PubMed

Mei, N; Belleville, L; Cha, Y; Olofsson, U; Odnevall Wallinder, I; Persson, K-A; Hedberg, Y S

2018-01-15

Welding fume of stainless steels is potentially health hazardous. The aim of this study was to investigate the manganese (Mn) and chromium (Cr) speciation of welding fume particles and their extent of metal release relevant for an inhalation scenario, as a function of particle size, welding method (manual metal arc welding, metal arc welding using an active shielding gas), different electrodes (solid wires and flux-cored wires) and shielding gases, and base alloy (austenitic AISI 304L and duplex stainless steel LDX2101). Metal release investigations were performed in phosphate buffered saline (PBS), pH 7.3, 37°, 24h. The particles were characterized by means of microscopic, spectroscopic, and electroanalytical methods. Cr was predominantly released from particles of the welding fume when exposed in PBS [3-96% of the total amount of Cr, of which up to 70% as Cr(VI)], followed by Mn, nickel, and iron. Duplex stainless steel welded with a flux-cored wire generated a welding fume that released most Cr(VI). Nano-sized particles released a significantly higher amount of nickel compared with micron-sized particle fractions. The welding fume did not contain any solitary known chromate compounds, but multi-elemental highly oxidized oxide(s) (iron, Cr, and Mn, possibly bismuth and silicon). Copyright © 2017 The Authors. Published by Elsevier B.V. All rights reserved.

Electrochemistry and speciation of Au(+) in a deep eutectic solvent: growth and morphology of galvanic immersion coatings.

PubMed

Ballantyne, Andrew D; Forrest, Gregory C H; Frisch, Gero; Hartley, Jennifer M; Ryder, Karl S

2015-11-11

In this study we compare the electrochemical and structural properties of three gold salts AuCl, AuCN and KAu(CN)2 in a Deep Eutectic Solvent (DES) electrolyte (Ethaline 200) in order to elucidate factors affecting the galvanic deposition of gold coatings on nickel substrates. A chemically reversible diffusion limited response was observed for AuCl, whereas AuCN and KAu(CN)2 showed much more complicated, kinetically limited responses. Galvanic exchange reactions were performed on nickel substrates from DES solutions of the three gold salts; the AuCN gave a bright gold coating, the KAu(CN)2 solution give a visibly thin coating, whilst the coating from AuCl was dull, friable and poorly adhesive. This behaviour was rationalised by the differing speciation for each of these compounds, as evidenced by EXAFS methods. Analysis of EXAFS data shows that AuCl forms the chlorido-complex [AuCl2](-), AuCN forms a mixed [AuCl(CN)](-) species, whereas KAu(CN)2 maintains its [Au(CN)2](-) structure. The more labile Cl(-) enables easier reduction of Au when compared to the tightly bound cyanide species, hence leading to slower kinetics of deposition and differing electrochemical behaviour. We conclude that metal speciation in DESs is a function of the initial metal salt and that this has a strong influence on the mechanism and rate of growth, as well as on the morphology of the metal deposit obtained. In addition, these coatings are also extremely promising from a technological perspective as Electroless Nickel Immersion Gold (ENIG) finishes in the printed circuit board (PCB) industry, where the elimination of acid in gold plating formulation could potentially lead to more reliable coatings. Consequently, these results are both significant and timely.

Habitat Availability and Heterogeneity and the Indo-Pacific Warm Pool as Predictors of Marine Species Richness in the Tropical Indo-Pacific

PubMed Central

Sanciangco, Jonnell C.; Carpenter, Kent E.; Etnoyer, Peter J.; Moretzsohn, Fabio

2013-01-01

Range overlap patterns were observed in a dataset of 10,446 expert-derived marine species distribution maps, including 8,295 coastal fishes, 1,212 invertebrates (crustaceans and molluscs), 820 reef-building corals, 50 seagrasses, and 69 mangroves. Distributions of tropical Indo-Pacific shore fishes revealed a concentration of species richness in the northern apex and central region of the Coral Triangle epicenter of marine biodiversity. This pattern was supported by distributions of invertebrates and habitat-forming primary producers. Habitat availability, heterogeneity, and sea surface temperatures were highly correlated with species richness across spatial grains ranging from 23,000 to 5,100,000 km2 with and without correction for autocorrelation. The consistent retention of habitat variables in our predictive models supports the area of refuge hypothesis which posits reduced extinction rates in the Coral Triangle. This does not preclude support for a center of origin hypothesis that suggests increased speciation in the region may contribute to species richness. In addition, consistent retention of sea surface temperatures in models suggests that available kinetic energy may also be an important factor in shaping patterns of marine species richness. Kinetic energy may hasten rates of both extinction and speciation. The position of the Indo-Pacific Warm Pool to the east of the Coral Triangle in central Oceania and a pattern of increasing species richness from this region into the central and northern parts of the Coral Triangle suggests peripheral speciation with enhanced survival in the cooler parts of the Coral Triangle that also have highly concentrated available habitat. These results indicate that conservation of habitat availability and heterogeneity is important to reduce extinction of marine species and that changes in sea surface temperatures may influence the evolutionary potential of the region. PMID:23457533

Habitat availability and heterogeneity and the indo-pacific warm pool as predictors of marine species richness in the tropical Indo-Pacific.

PubMed

Sanciangco, Jonnell C; Carpenter, Kent E; Etnoyer, Peter J; Moretzsohn, Fabio

2013-01-01

Range overlap patterns were observed in a dataset of 10,446 expert-derived marine species distribution maps, including 8,295 coastal fishes, 1,212 invertebrates (crustaceans and molluscs), 820 reef-building corals, 50 seagrasses, and 69 mangroves. Distributions of tropical Indo-Pacific shore fishes revealed a concentration of species richness in the northern apex and central region of the Coral Triangle epicenter of marine biodiversity. This pattern was supported by distributions of invertebrates and habitat-forming primary producers. Habitat availability, heterogeneity, and sea surface temperatures were highly correlated with species richness across spatial grains ranging from 23,000 to 5,100,000 km(2) with and without correction for autocorrelation. The consistent retention of habitat variables in our predictive models supports the area of refuge hypothesis which posits reduced extinction rates in the Coral Triangle. This does not preclude support for a center of origin hypothesis that suggests increased speciation in the region may contribute to species richness. In addition, consistent retention of sea surface temperatures in models suggests that available kinetic energy may also be an important factor in shaping patterns of marine species richness. Kinetic energy may hasten rates of both extinction and speciation. The position of the Indo-Pacific Warm Pool to the east of the Coral Triangle in central Oceania and a pattern of increasing species richness from this region into the central and northern parts of the Coral Triangle suggests peripheral speciation with enhanced survival in the cooler parts of the Coral Triangle that also have highly concentrated available habitat. These results indicate that conservation of habitat availability and heterogeneity is important to reduce extinction of marine species and that changes in sea surface temperatures may influence the evolutionary potential of the region.

Studies of concentration and temperature dependences of precipitation kinetics in iron-copper alloys using kinetic Monte Carlo and stochastic statistical simulations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Khromov, K. Yu.; Vaks, V. G., E-mail: vaks@mbslab.kiae.ru; Zhuravlev, I. A.

2013-02-15

The previously developed ab initio model and the kinetic Monte Carlo method (KMCM) are used to simulate precipitation in a number of iron-copper alloys with different copper concentrations x and temperatures T. The same simulations are also made using an improved version of the previously suggested stochastic statistical method (SSM). The results obtained enable us to make a number of general conclusions about the dependences of the decomposition kinetics in Fe-Cu alloys on x and T. We also show that the SSM usually describes the precipitation kinetics in good agreement with the KMCM, and using the SSM in conjunction withmore » the KMCM allows extending the KMC simulations to the longer evolution times. The results of simulations seem to agree with available experimental data for Fe-Cu alloys within statistical errors of simulations and the scatter of experimental results. Comparison of simulation results with experiments for some multicomponent Fe-Cu-based alloys allows making certain conclusions about the influence of alloying elements in these alloys on the precipitation kinetics at different stages of evolution.« less

Kinetics of solution crystal growth of strengite, FePO4,2H2O

NASA Astrophysics Data System (ADS)

Lundager Madsen, Hans E.; Koch, Christian Bender

2018-01-01

The iron(III) phosphate strengite, FePO4,2H2O, has been precipitated at 25 °C by mixing solutions of iron alum and ammonium phosphate. The rate of crystallization has been determined by pH recording. Three stages of crystal growth kinetics could be distinguished: (1) mononuclear growth, (2) polynuclear growth and, in a few cases, (3) spiral growth (BCF mechanism). From the first two, the value of edge free energy λ = 87 ± 1 pJ/m was found. The identity of the precipitate was verified by SEM, XRD and Mössbauer spectroscopy.

Assessment of reduction behavior of hematite iron ore pellets in coal fines for application in sponge ironmaking

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kumar, M.; Patel, S.K.

2009-07-01

Studies on isothermal reduction kinetics (with F grade coal) in fired pellets of hematite iron ores, procured from four different mines of Orissa, were carried out in the temperature range of 850-1000C to provide information for the Indian sponge iron plants. The rate of reduction in all the fired iron ore pellets increased markedly with a rise of temperature up to 950C, and thereafter it decreased at 1000C. The rate was more intense in the first 30 minutes. All iron ores exhibited almost complete reduction in their pellets at temperatures of 900 and 950C in 2 hours' heating time duration,more » and the final product morphologies consisted of prominent cracks. The kinetic model equation 1-(1-a){sup 1/3}=kt was found to fit best to the experimental data, and the values of apparent activation energy were evaluated. Reductions of D. R. Pattnaik and M. G. Mohanty iron ore pellets were characterized by higher activation energies (183 and 150 kJ mol{sup -1}), indicating carbon gasification reaction to be the rate-controlling step. The results established lower values of activation energy (83 and 84 kJ mol{sup -1}) for the reduction of G. M. OMC Ltd. and Sakaruddin iron ore pellets, proposing their overall rates to be controlled by indirect reduction reactions.« less

Respiratory enzymes of Thiobacillus ferrooxidans. Kinetic properties of an acid-stable iron:rusticyanin oxidoreductase.

PubMed

Blake, R C; Shute, E A

1994-08-09

Rusticyanin is an acid-stable, soluble blue copper protein found in abundance in the periplasmic space of Thiobacillus ferrooxidans, an acidophilic bacterium capable of growing autotrophically on soluble ferrous sulfate. An acid-stable iron:rusticyanin oxidoreductase activity was partially purified from cell-free extracts of T. ferrooxidans. The enzyme-catalyzed, iron-dependent reduction of the rusticyanin exhibited three kinetic properties characteristic of aerobic iron oxidation by whole cells. (i) A survey of 14 different anions indicated that catalysis by the oxidoreductase occurred only in the presence of sulfate or selenate, an anion specificity identical to that of whole cells. (ii) Saturation with both sulfatoiron(II) and the catalyst produced a concentration-independent rate constant of 3 s-1 for the reduction of the rusticyanin, which is an electron transfer reaction sufficiently rapid to account for the flux of electrons through the iron respiratory chain. (iii) Values for the enzyme-catalyzed pseudo-first-order rate constants for the reduction of the rusticyanin showed a hyperbolic dependence on the concentration of sulfatoiron(II) with a half-maximal effect at 300 microM, a value similar to the apparent KM for iron shown by whole cells. On the basis of these favorable comparisons between the behavior patterns of isolated biomolecules and those of whole cells, this iron:rusticyanin oxidoreductase is postulated to be the primary cellular oxidant of ferrous ions in the iron respiratory electron transport chain of T. ferrooxidans.

Sorption and speciation of selenium in boreal forest soil.

PubMed

Söderlund, Mervi; Virkanen, Juhani; Holgersson, Stellan; Lehto, Jukka

2016-11-01

Sorption and speciation of selenium in the initial chemical forms of selenite and selenate were investigated in batch experiments on humus and mineral soil samples taken from a 4-m deep boreal forest soil excavator pit on Olkiluoto Island, on the Baltic Sea coast in southwestern Finland. The HPLC-ICP-MS technique was used to monitor any possible transformations in the selenium liquid phase speciation and to determine the concentrations of selenite and selenate in the samples for calculation of the mass distribution coefficient, K d , for both species. Both SeO 3 2- and SeO 4 2- proved to be resistant forms in the prevailing soil conditions and no changes in selenium liquid phase speciation were seen in the sorption experiments in spite of variations in the initial selenium species, incubation time or conditions, pH, temperature or microbial activity. Selenite sorption on the mineral soil increased with time in aerobic conditions whilst the opposite trend was seen for the anaerobic soil samples. Selenite retention correlated with the contents of organic matter and weakly crystalline oxides of aluminum and iron, solution pH and the specific surface area. Selenate exhibited poorer sorption on soil than selenite and on average the K d values were 27-times lower. Mineral soil was more efficient in retaining selenite and selenate than humus, implicating the possible importance of weakly crystalline aluminum and iron oxides for the retention of oxyanions in Olkiluoto soil. Sterilization of the soil samples decreased the retention of selenite, thus implying some involvement of soil microbes in the sorption processes or a change in sample composition, but it produced no effect for selenate. There was no sorption of selenite by quartz, potassium feldspar, hornblende or muscovite. Biotite showed the best retentive properties for selenite in the model soil solution at about pH 8, followed by hematite, plagioclase and chlorite. The K d values for these minerals were 18, 14, 8 and 7 L/kg, respectively. It is proposed that selenite sorption is affected by the structural Fe(II) in biotite, which is capable of inducing the reduction of SeO 3 2- to Se(0). Selenite probably forms a surface complex with Fe(III) atoms on the surface of hematite, thus explaining its retention on this mineral. None of the minerals retained selenate to any extent. Copyright © 2016 Elsevier Ltd. All rights reserved.

Sulfidization of Organic Freshwater Flocs from a Minerotrophic Peatland: Speciation Changes of Iron, Sulfur, and Arsenic.

PubMed

ThomasArrigo, Laurel K; Mikutta, Christian; Lohmayer, Regina; Planer-Friedrich, Britta; Kretzschmar, Ruben

2016-04-05

Iron-rich organic flocs are frequently observed in surface waters of wetlands and show a high affinity for trace metal(loid)s. Under low-flow stream conditions, flocs may settle, become buried, and eventually be subjected to reducing conditions facilitating trace metal(loid) release. In this study, we reacted freshwater flocs (704-1280 mg As/kg) from a minerotrophic peatland (Gola di Lago, Switzerland) with sulfide (5.2 mM, S(-II)spike/Fe = 0.75-1.62 mol/mol) at neutral pH and studied the speciation changes of Fe, S, and As at 25 ± 1 °C over 1 week through a combination of synchrotron X-ray techniques and wet-chemical analyses. Sulfidization of floc ferrihydrite and nanocrystalline lepidocrocite caused the rapid formation of mackinawite (52-81% of Fesolid at day 7) as well as solid-phase associated S(0) and polysulfides. Ferrihydrite was preferentially reduced over lepidocrocite, although neoformation of lepidocrocite from ferrihydrite could not be excluded. Sulfide-reacted flocs contained primarily arsenate (47-72%) which preferentially adsorbed to Fe(III)-(oxyhydr)oxides, despite abundant mackinawite precipitation. At higher S(-II)spike/Fe molar ratios (≥1.0), the formation of an orpiment-like phase accounted for up to 35% of solid-phase As. Despite Fe and As sulfide precipitation and the presence of residual Fe(III)-(oxyhydr)oxides, mobilization of As was recorded in all samples (Asaq = 0.45-7.0 μM at 7 days). Aqueous As speciation analyses documented the formation of thioarsenates contributing up to 33% of Asaq. Our findings show that freshwater flocs from the Gola di Lago peatland may become a source of As under sulfate-reducing conditions and emphasize the pivotal role Fe-rich organic freshwater flocs play in trace metal(loid) cycling in S-rich wetlands characterized by oscillating redox conditions.

Human calprotectin affects the redox speciation of iron.

PubMed

Nakashige, Toshiki G; Nolan, Elizabeth M

2017-08-16

We report that the metal-sequestering human host-defense protein calprotectin (CP, S100A8/S100A9 oligomer) affects the redox speciation of iron (Fe) in bacterial growth media and buffered aqueous solution. Under aerobic conditions and in the absence of an exogenous reducing agent, CP-Ser (S100A8(C42S)/S100A9(C3S) oligomer) depletes Fe from three different bacterial growth media preparations over a 48 h timeframe (T = 30 °C). The presence of the reducing agent β-mercaptoethanol accelerates this process and allows CP-Ser to deplete Fe over a ≈1 h timeframe. Fe-depletion assays performed with metal-binding-site variants of CP-Ser show that the hexahistidine (His 6 ) site, which coordinates Fe(ii) with high affinity, is required for Fe depletion. An analysis of Fe redox speciation in buffer containing Fe(iii) citrate performed under aerobic conditions demonstrates that CP-Ser causes a time-dependent increase in the [Fe(ii)]/[Fe(iii)] ratio. Taken together, these results indicate that the hexahistidine site of CP stabilizes Fe(ii) and thereby shifts the redox equilibrium of Fe to the reduced ferrous state under aerobic conditions. We also report that the presence of bacterial metabolites affects the Fe-depleting activity of CP-Ser. Supplementation of bacterial growth media with an Fe(iii)-scavenging siderophore (enterobactin, staphyloferrin B, or desferrioxamine B) attenuates the Fe-depleting activity of CP-Ser. This result indicates that formation of Fe(iii)-siderophore complexes blocks CP-mediated reduction of Fe(iii) and hence the ability of CP to coordinate Fe(ii). In contrast, the presence of pyocyanin (PYO), a redox-cycling phenazine produced by Pseudomonas aeruginosa that reduces Fe(iii) to Fe(ii), accelerates Fe depletion by CP-Ser under aerobic conditions. These findings indicate that the presence of microbial metabolites that contribute to metal homeostasis at the host/pathogen interface can affect the metal-sequestering function of CP.

The role of iron species on the turbidity of oxidized phenol solutions in a photo-Fenton system.

PubMed

Villota, Natalia; Camarero, Luis M; Lomas, Jose M; Perez-Arce, Jonatan

2015-01-01

This work aims at establishing the contribution of the iron species to the turbidity of phenol solutions oxidized with photo-Fenton technology. During oxidation, turbidity increases linearly with time till a maximum value, according to a formation rate that shows a dependence of second order with respect to the catalyst concentration. Next, the decrease in turbidity shows the evolution of second-order kinetics, where the kinetics constant is inversely proportional to the dosage of iron, of order 0.7. The concentration of iron species is analysed at the point of maximum turbidity, as a function of the total amount of iron. Then, it is found that using dosages FeT=0-15.0 mg/L, the majority iron species was found to be ferrous ions, indicating that its concentration increases linearly with the dosage of total iron. This result may indicate that the photo-reaction of ferric ion occurs leading to the regeneration of ferrous ion. The results, obtained by operating with initial dosages FeT=15.0 and 25.0 mg/L, suggest that ferrous ion concentration decreases while ferric ion concentration increases in a complementary manner. This fact could be explained as a regeneration cycle of the iron species. The observed turbidity is generated due to the iron being added as a catalyst and the organic matter present in the system. Later, it was found that at the point of maximum turbidity, the concentration of ferrous ions is inversely proportional to the concentration of phenol and its dihydroxylated intermediates.

Physical and Chemical Characterization of Therapeutic Iron Containing Materials: A Study of Several Superparamagnetic Drug Formulations with the β-FeOOH or Ferrihydrite Structure

NASA Astrophysics Data System (ADS)

Funk, Felix; Long, Gary J.; Hautot, Dimitri; Büchi, Ruth; Christl, Iso; Weidler, Peter G.

2001-03-01

The effectiveness of therapeutically used iron compounds is related to their physical and chemical properties. Four different iron compounds used in oral, intravenous, and intramuscular therapy have been examined by X-ray powder diffraction, iron-57 Mössbauer spectroscopy, transmission electron microscopy, BET surface area measurement, potentiometric titration and studied through dissolution kinetics determinations using acid, reducing and chelating agents. All compounds are nanosized with particle diameters, as determined by X-ray diffraction, ranging from 1 to 4.1 nm. The superparamagnetic blocking temperatures, as determined by Mössbauer spectroscopy, indicate that the relative diameters of the aggregates range from 2.5 to 4.1 nm. Three of the iron compounds have an akaganeite-like structure, whereas one has a ferrihydrite-like structure. As powders the particles form large and dense aggregates which have a very low surface area on the order of 1 m2 g-1. There is evidence, however, that in a colloidal solution the surface area is increased by two to three orders of magnitude, presumably as a result of the break up of the aggregates. Iron release kinetics by acid, chelating and reducing agents reflect the high surface area, the size and crystallinity of the particles, and the presence of the protective carbohydrate layer coating the iron compound. Within a physiologically relevant time period, the iron release produced by acid or large chelating ligands is small. In contrast, iron is rapidly mobilized by small organic chelating agents, such as oxalate, or by chelate-forming reductants, such as thioglycolate.

Increased iron bioavailability from lactic-fermented vegetables is likely an effect of promoting the formation of ferric iron (Fe(3+)).

PubMed

Scheers, Nathalie; Rossander-Hulthen, Lena; Torsdottir, Inga; Sandberg, Ann-Sofie

2016-02-01

Lactic fermentation of foods increases the availability of iron as shown in a number of studies throughout the years. Several explanations have been provided such as decreased content of inhibitory phytate, increased solubility of iron, and increased content of lactic acid in the fermented product. However, to our knowledge, there are no data to support that the bioavailability of iron is affected by lactic fermentation. The objective of the present study was to investigate whether the bioavailability of iron from a vegetable mix was affected by lactic fermentation and to propose a mechanism for such an event, by conducting human and cell (Caco-2, HepG2) studies and iron speciation measurements (voltammetry). We also investigated whether the absorption of zinc was affected by the lactic fermentation. In human subjects, we observed that lactic-fermented vegetables served with both a high-phytate and low-phytate meal increased the absorption of iron, but not zinc. In vitro digested fermented vegetables were able to provoke a greater hepcidin response per ng Fe than fresh vegetables, indicating that Fe in the fermented mixes was more bioavailable, independent on the soluble Fe content. We measured that hydrated Fe(3+) species were increased after the lactic fermentation, while there was no significant change in hydrated Fe(2+). Furthermore, lactate addition to Caco-2 cells did not affect ferritin formation in response to Fe nor did lactate affect the hepcidin response in the Caco-2/HepG2 cell system. The mechanism for the increased bioavailability of iron from lactic-fermented vegetables is likely an effect of the increase in ferric iron (Fe(3+)) species caused by the lactic fermentation. No effect on zinc bioavailability was observed.

Reduction of Iron-Oxide-Carbon Composites: Part I. Estimation of the Rate Constants

NASA Astrophysics Data System (ADS)

Halder, S.; Fruehan, R. J.

2008-12-01

A new ironmaking concept using iron-oxide-carbon composite pellets has been proposed, which involves the combination of a rotary hearth furnace (RHF) and an iron bath smelter. This part of the research focuses on studying the two primary chemical kinetic steps. Efforts have been made to experimentally measure the kinetics of the carbon gasification by CO2 and wüstite reduction by CO by isolating them from the influence of heat- and mass-transport steps. A combined reaction model was used to interpret the experimental data and determine the rate constants. Results showed that the reduction is likely to be influenced by the chemical kinetics of both carbon oxidation and wüstite reduction at the temperatures of interest. Devolatilized wood-charcoal was observed to be a far more reactive form of carbon in comparison to coal-char. Sintering of the iron-oxide at the high temperatures of interest was found to exert a considerable influence on the reactivity of wüstite by virtue of altering the internal pore surface area available for the reaction. Sintering was found to be predominant for highly porous oxides and less of an influence on the denser ores. It was found using an indirect measurement technique that the rate constants for wüstite reduction were higher for the porous iron-oxide than dense hematite ore at higher temperatures (>1423 K). Such an indirect mode of measurement was used to minimize the influence of sintering of the porous oxide at these temperatures.

The glacial iron cycle from source to export

NASA Astrophysics Data System (ADS)

Hawkings, J.; Wadham, J. L.; Tranter, M.; Raiswell, R.; Benning, L. G.; Statham, P. J.; Tedstone, A. J.; Nienow, P. W.; Telling, J.; Bagshaw, E.; Simmons, S. L.

2014-12-01

Nutrient availability limits primary production in large sectors of the world's oceans. Iron is the major limiting nutrient in around one third of the oceanic euphotic zone, most significantly in the Southern Ocean proximal to Antarctica. In these areas the availability of bioavailable iron can influence the amount of primary production, and thus the strength of the biological pump and associated carbon drawdown from the atmosphere. Despite experiencing widespread iron limitation, the Polar oceans are among the most productive on Earth. Due to the extreme cold, remoteness and their perceived "stasis", ice sheets have previously been though of as insignificant in global biogeochemical cycles. However, large marine algal blooms have been observed in iron-limited areas where glacial influence is large, and it is possible that these areas are stimulated by glacial bioavailable iron input. Here we discuss the importance of the Greenland and Antarctic ice sheets in the global iron cycle. Using field collected trace element data, bulk meltwater chemistry and mineralogical analysis, including photomicrographs, EELS and XANES, we present, for the first time, a conceptual model of the glacial iron cycle from source to export. Using this data we discuss the sources of iron in glacial meltwater, transportation and alteration through the glacial system, and subsequent export to downstream environments. Data collected in 2012 and 2013 from two different Greenlandic glacial catchments are shown, with the most detailed breakdown of iron speciation and concentrations in glacial areas yet reported. Furthermore, the first data from Greenlandic icebergs is presented, allowing meltwater-derived and iceberg-derived iron export to be compared, and the influence of both in marine productivity to be estimated. Using our conceptual model and flux estimates from our dataset, glacial iron delivery in both the northern and southern hemisphere is discussed. Finally, we compare our flux estimates to other major iron sources to the polar regions such as aeolian dust, and discuss potential implications of increased melting of the ice sheets on the global iron cycle in the future.

Iron chelates: a challenge to chemists and Mössbauer spectroscopists

NASA Astrophysics Data System (ADS)

Homonnay, Z.; Szilágyi, P. Á.; Vértes, A.; Kuzmann, E.; Sharma, V. K.; Molnár, G.; Bousseksou, A.; Grenèche, J.-M.; Brausam, A.; Meier, R.; van Eldik, R.

2008-02-01

The speciation of iron in aqueous solutions containing Fe3 + and selected chelates such as EDTA, EDDA, CDTA and HEDTA has been studied using transmission 57Fe Mössbauer spectrometry in frozen solutions. The protonation of various complexes as well as binuclear complex formation could be detected as a function of pH. Autoreduction of Fe3 + to Fe2 + was observed in several cases. Reaction with hydrogen peroxide proved to be rather different for the four ligands, while the dihapto complex [XFe( η 2-O2)]3 - had surprisingly identical Mössbauer parameters for X = EDTA, CDTA or HEDTA. Paramagnetic spin relaxation observed in the Mössbauer spectra was found to be strongly influenced by the identity of the chelating ligand, despite the basically spin-spin origin of the phenomenon.

Thermodynamic Characterization of Iron Oxide-Aqueous Fe(2+) Redox Couples.

PubMed

Gorski, Christopher A; Edwards, Rebecca; Sander, Michael; Hofstetter, Thomas B; Stewart, Sydney M

2016-08-16

Iron is present in virtually all terrestrial and aquatic environments, where it participates in redox reactions with surrounding metals, organic compounds, contaminants, and microorganisms. The rates and extent of these redox reactions strongly depend on the speciation of the Fe2+ and Fe3+ phases, although the underlying reasons remain unclear. In particular, numerous studies have observed that Fe2+ associated with iron oxide surfaces (i.e., oxide-associated Fe2+) often reduces oxidized contaminants much faster than aqueous Fe2+ alone. Here, we tested two hypotheses related to this observation by determining if solutions containing two commonly studied iron oxides—hematite and goethite—and aqueous Fe2+ reached thermodynamic equilibrium over the course of a day. We measured reduction potential (EH) values in solutions containing these oxides at different pH values and aqueous Fe2+ concentrations using mediated potentiometry. This analysis yielded standard reduction potential (EH0) values of 768 ± 1 mV for the aqueous Fe2+–goethite redox couple and 769 ± 2 mV for the aqueous Fe2+–hematite redox couple. These values were in excellent agreement with those calculated from existing thermodynamic data, and the data could be explained by the presence of an iron oxide lowering EH values of aqueous Fe3+/Fe2+ redox couples.

Schwertmannite stability in acidified coastal environments

NASA Astrophysics Data System (ADS)

Collins, Richard N.; Jones, Adele M.; Waite, T. David

2010-01-01

A combination of analytical and field measurements has been used to probe the speciation and cycling of iron in coastal lowland acid sulfate soils. Iron K-edge EXAFS spectroscopy demonstrated that schwertmannite dominated (43-77%) secondary iron mineralization throughout the oxidized and acidified soil profile, while pyrite and illite were the major iron-bearing minerals in the reduced potential acid sulfate soil layers. Analyses of contemporary precipitates from shallow acid sulfate soil groundwaters indicated that 2-line ferrihydrite, in addition to schwertmannite, is presently controlling secondary Fe(III) mineralization. Although aqueous pH values and concentrations of Fe(II) were seasonally high, no evidence was obtained for the Fe(II)-catalyzed crystallization of either mineral to goethite. The results of this study indicate that: (a) schwertmannite is likely to persist in coastal lowland acid sulfate soils on a much longer time-scale than predicted by laboratory experiments; (b) this mineral is less reactive in these types of soils due to surface-site coverage by components such as silicate and possibly, to a lesser extent, natural organic matter and phosphate and; (c) active water table management to promote oxic/anoxic cycles around the Fe(II)-Fe(III) redox couple, or reflooding of these soils, will be ineffective in promoting the Fe(II)-catalyzed transformation of either schwertmannite or 2-line ferrihydrite to crystalline iron oxyhydroxides.

Ferric iron-bearing sediments as a mineral trap for CO2 sequestration: Iron reduction using sulfur-bearing waste gas

USGS Publications Warehouse

Palandri, J.L.; Kharaka, Y.K.

2005-01-01

We present a novel method for geologic sequestration of anthropogenic CO2 in ferrous carbonate, using ferric iron present in widespread redbeds and other sediments. Iron can be reduced by SO2 that is commonly a component of flue gas produced by combustion of fossil fuel, or by adding SO2 or H2S derived from other industrial processes to the injected waste gas stream. Equilibrium and kinetically controlled geochemical simulations at 120 bar and 50 and 100 ??C with SO2 or H2S show that iron can be transformed almost entirely to siderite thereby trapping CO2, and simultaneously, that sulfur can be converted predominantly to dissolved sulfate. If there is an insufficient amount of sulfur-bearing gas relative to CO2 as for typical flue gas, then some of the iron is not reduced, and some of the CO2 is not sequestered. If there is an excess of sulfur-bearing gas, then complete iron reduction is ensured, and some of the iron precipitates as pyrite or other solid iron sulfide, depending on their relative precipitation kinetics. Gas mixtures with insufficient sulfur relative to CO2 can be used in sediments containing Ca, Mg, or other divalent metals capable of precipitating carbonate minerals. For quartz arenite with an initial porosity of 21% and containing 0.25 wt.% Fe2O3, approximately 0.7 g of CO2 is sequestered per kg of rock, and the porosity decrease is less than 0.03%. Sequestration of CO2 using ferric iron has the advantage of disposing of SO2 that may already be present in the combustion gas. ?? 2005 Published by Elsevier B.V.

Hafnium-Based Bulk Metallic Glasses for Kinetic Energy Penetrators

DTIC Science & Technology

2004-12-01

uranium -based (DU) and tungsten- nickel -iron (W-Ni-Fe) composite kinetic energy (KE) munitions is primarily ascribed to their high densities (U: ρ...based on an invariant point identified in the hafnium- copper- nickel ternary system. They are denser than zirconium-based glass-forming compositions...depleted- uranium penetrators. 1. INTRODUCTION 1.1 Criterion for Effective Kinetic Energy Penetrator Performance The lethality of depleted

EFFECTS OF FERRIC HYDROXIDE ON THE ANAEROBIC BIODEGRADATION KINETICS AND TOXICITY OF VEGETABLE OIL IN FRESHWATER SEDIMENTS

EPA Science Inventory

Biodegradation of vegetable oil in freshwater sediments exhibits self-inhibitory characteristics when it occurs under methanogenic conditions but not under iron-reducing conditions. The basis of the protective effect of iron was investigated by comparing its effects on oil biodeg...

KINETICS OF SOLUBLE CHROMIUM REMOVAL FROM CONTAMINATED WATER BY ZEROVALENT IRON MEDIA: CORROSION INHIBITION AND PASSIVE OXIDE EFFECTS. (R825223)

EPA Science Inventory

Permeable reactive barriers containing zerovalent iron are being increasingly
employed for in situ remediation of groundwater contaminated with redox active
metals and chlorinated organic compounds. This research investigated the effect
of chromate concentration on...

Steady-state kinetics of substrate binding and iron release in tomato ACC oxidase.

PubMed

Thrower, J S; Blalock, R; Klinman, J P

2001-08-14

1-Aminocyclopropane-1-carboxylate oxidase (ACC oxidase) catalyzes the last step in the biosynthetic pathway of the plant hormone, ethylene. This unusual reaction results in the oxidative ring cleavage of 1-aminocyclopropane carboxylate (ACC) into ethylene, cyanide, and CO2 and requires ferrous ion, ascorbate, and molecular oxygen for catalysis. A new purification procedure and assay method have been developed for tomato ACC oxidase that result in greatly increased enzymatic activity. This method allowed us to determine the rate of iron release from the enzyme and the effect of the activator, CO2, on this rate. Initial velocity studies support an ordered kinetic mechanism where ACC binds first followed by O2; ascorbate can bind after O2 or possibly before ACC. This kinetic mechanism differs from one recently proposed for the ACC oxidase from avocado.

Uptake Kinetics and Trophic Transfer of Tungsten from Cabbage to a Herbivorous Animal Model

DOE PAGES

Lindsay, James H.; Kennedy, Alan J.; Seiter-Moser, Jennifer M.; ...

2017-10-20

This paper builds on previous studies on military-relevant tungsten (W) to more thoroughly explore environmental pathways and bioaccumulation kinetics during direct soil exposure versus trophic transfer and elucidate its relative accumulation and speciation in different snail organs. The modeled steady-state concentration and bioaccumulation factor (BAF) of W from soil into cabbage were 302 mg/kg and 0.55, respectively. Steady-state concentrations (34 mg/kg) and BAF values (0.05) obtained for the snail directly exposed to contaminated soil were lower than trophic transfer by consumption of W-contaminated cabbage (tissue concentration of 86 mg/kg; BAF of 0.36). Thus, consumption of contaminated food is the mostmore » important pathway for W mobility in this food chain. The highest concentrations of W compartmentalization were in the snail’s hepatopancreas based on wet chemistry and synchrotron-based investigations. Chemical speciation via inductively couple plasma mass spectrometry showed a higher degree of polytungstate partitioning in the hepatopancreas relative to the rest of the body. Based on synchrotron analysis, W was incorporated into the shell matrix during exposure, particularly during the regeneration of damaged shell. Finally, this offers the potential for application of the shell as a longer-term biomonitoring and forensics tool for historic exposure.« less

Uptake Kinetics and Trophic Transfer of Tungsten from Cabbage to a Herbivorous Animal Model

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lindsay, James H.; Kennedy, Alan J.; Seiter-Moser, Jennifer M.

This paper builds on previous studies on military-relevant tungsten (W) to more thoroughly explore environmental pathways and bioaccumulation kinetics during direct soil exposure versus trophic transfer and elucidate its relative accumulation and speciation in different snail organs. The modeled steady-state concentration and bioaccumulation factor (BAF) of W from soil into cabbage were 302 mg/kg and 0.55, respectively. Steady-state concentrations (34 mg/kg) and BAF values (0.05) obtained for the snail directly exposed to contaminated soil were lower than trophic transfer by consumption of W-contaminated cabbage (tissue concentration of 86 mg/kg; BAF of 0.36). Thus, consumption of contaminated food is the mostmore » important pathway for W mobility in this food chain. The highest concentrations of W compartmentalization were in the snail’s hepatopancreas based on wet chemistry and synchrotron-based investigations. Chemical speciation via inductively couple plasma mass spectrometry showed a higher degree of polytungstate partitioning in the hepatopancreas relative to the rest of the body. Based on synchrotron analysis, W was incorporated into the shell matrix during exposure, particularly during the regeneration of damaged shell. Finally, this offers the potential for application of the shell as a longer-term biomonitoring and forensics tool for historic exposure.« less

Constraints on Meteoric Smoke Composition and Meteoric Influx Using SOFIE Observations With Models

NASA Astrophysics Data System (ADS)

Hervig, Mark E.; Brooke, James S. A.; Feng, Wuhu; Bardeen, Charles G.; Plane, John M. C.

2017-12-01

The composition of meteoric smoke particles in the mesosphere is constrained using measurements from the Solar Occultation For Ice Experiment (SOFIE) in conjunction with models. Comparing the multiwavelength observations with models suggests smoke compositions of magnetite, wüstite, magnesiowüstite, or iron-rich olivine. Smoke compositions of pure pyroxene, hematite, iron-poor olivine, magnesium silicate, and silica are excluded, although this may be because these materials have weak signatures at the SOFIE wavelengths. Information concerning smoke composition allows the SOFIE extinction measurements to be converted to smoke volume density. Comparing the observed volume density with model results for varying meteoric influx (MI) provides constraints on the ablated fraction of incoming meteoric material. The results indicate a global ablated MI of 3.3 ± 1.9 t d-1, which represents only iron, magnesium, and possibly silica, given the smoke compositions indicated here. Considering the optics and iron content of individual smoke compositions gives an ablated Fe influx of 1.8 ± 0.9 t d-1. Finally, the global total meteoric influx (ablated plus surviving) is estimated to be 30 ± 18 t d-1, when considering the present results and a recent description of the speciation of meteoric material.

Spectroscopic and Kinetic Properties of the Molybdenum-containing, NAD+-dependent Formate Dehydrogenase from Ralstonia eutropha*

PubMed Central

Niks, Dimitri; Duvvuru, Jayant; Escalona, Miguel; Hille, Russ

2016-01-01

We have examined the rapid reaction kinetics and spectroscopic properties of the molybdenum-containing, NAD+-dependent FdsABG formate dehydrogenase from Ralstonia eutropha. We confirm previous steady-state studies of the enzyme and extend its characterization to a rapid kinetic study of the reductive half-reaction (the reaction of formate with oxidized enzyme). We have also characterized the electron paramagnetic resonance signal of the molybdenum center in its MoV state and demonstrated the direct transfer of the substrate Cα hydrogen to the molybdenum center in the course of the reaction. Varying temperature, microwave power, and level of enzyme reduction, we are able to clearly identify the electron paramagnetic resonance signals for four of the iron/sulfur clusters of the enzyme and find suggestive evidence for two others; we observe a magnetic interaction between the molybdenum center and one of the iron/sulfur centers, permitting assignment of this signal to a specific iron/sulfur cluster in the enzyme. In light of recent advances in our understanding of the structure of the molybdenum center, we propose a reaction mechanism involving direct hydride transfer from formate to a molybdenum-sulfur group of the molybdenum center. PMID:26553877

Kinetic Study on the Removal of Iron from Gold Mine Tailings by Citric Acid

NASA Astrophysics Data System (ADS)

Mashifana, T.; Mavimbela, N.; Sithole, N.

2018-03-01

The Gold mining generates large volumes of tailings, with consequent disposal and environmental problems. Iron tends to react with sulphur to form pyrite and pyrrhotite which then react with rain water forming acid rain. The study focuses on the removal of iron (Fe) from Gold Mine tailings; Fe was leached using citric acid as a leaching reagent. Three parameters which have an effect on the removal of Fe from the gold mine tailings, namely; temperature (25 °C and 50 °C), reagent concentration (0.25 M, 0.5 M, 0.75 M and 1 M) and solid loading ratio (20 %, 30 % and 40 %) were investigated. It was found that the recovery of Fe from gold mine tailings increased with increasing temperature and reagent concentration, but decreased with increasing solid loading ratio. The optimum conditions for the recovery of Fe from gold mine tailings was found to be at a temperature of 50 ºC, reagent concentration of 1 M and solid loading of 20 %. Three linear kinetic models were investigated and Prout-Tompkins kinetic model was the best fit yielding linear graphs with the highest R2 values.

Reduction Kinetics of Wüstite Scale on Pure Iron and Steel Sheets in Ar and H2 Gas Mixture

NASA Astrophysics Data System (ADS)

Mao, Weichen; Sloof, Willem G.

2017-10-01

A dense and closed Wüstite scale is formed on pure iron and Mn alloyed steel after oxidation in Ar + 33 vol pct CO2 + 17 vol pct CO gas mixture. Reducing the Wüstite scale in Ar + H2 gas mixture forms a dense and uniform iron layer on top of the remaining Wüstite scale, which separates the unreduced scale from the gas mixture. The reduction of Wüstite is controlled by the bulk diffusion of dissolved oxygen in the formed iron layer and follows parabolic growth rate law. The reduction kinetics of Wüstite formed on pure iron and on Mn alloyed steel are the same. The parabolic rate constant of Wüstite reduction obeys an Arrhenius relation with an activation energy of 104 kJ/mol if the formed iron layer is in the ferrite phase. However, at 1223 K (950 °C) the parabolic rate constant of Wüstite reduction drops due to the phase transformation of the iron layer from ferrite to austenite. The effect of oxygen partial pressure on the parabolic rate constant of Wüstite reduction is negligible when reducing in a gas mixture with a dew point below 283 K (10 °C). During oxidation of the Mn alloyed steel, Mn is dissolved in the Wüstite scale. Subsequently, during reduction of the Wüstite layer, Mn diffuses into the unreduced Wüstite. Ultimately, an oxide-free iron layer is obtained at the surface of the Mn alloyed steel, which is beneficial for coating application.

Iron-catalyzed halogenation of alkanes: modeling of nonheme halogenases by experiment and DFT calculations.

PubMed

Comba, Peter; Wunderlich, Steffen

2010-06-25

When the dichloroiron(II) complex of the tetradentate bispidine ligand L=3,7-dimethyl-9-oxo-2,4-bis(2-pyridyl)-3,7-diazabicyclo[3.3.1]nonane-1,5-dicarboxylate methyl ester is oxidized with H(2)O(2), tBuOOH, or iodosylbenzene, the high-valent Fe=O complex efficiently oxidizes and halogenates cyclohexane. Kinetic D isotope effects and the preference for the abstraction of tertiary over secondary carbon-bound hydrogen atoms (quantified in the halogenation of adamantane) indicate that C-H activation is the rate-determining step. The efficiencies (yields in stoichiometric and turnover numbers in catalytic reactions), product ratios (alcohol vs. bromo- vs. chloroalkane), and kinetic isotope effects depend on the oxidant. These results suggest different pathways with different oxidants, and these may include iron(IV)- and iron(V)-oxo complexes as well as oxygen-based radicals.

Reaction of iron with hydrogen chloride-oxygen mixtures at 550 C

NASA Technical Reports Server (NTRS)

Jacobson, N. S.

1986-01-01

The reaction of iron with 1 percent HCl/0-50 percent O2/Ar has been studied at 550 C with thermogravimetry to monitor kinetics and scanning electron microscopy to characterize product morphologies. In addition, the volatile species were identified with an atmospheric pressure sampling mass spectrometer. The reaction of 1 percent HCl/Ar produces FeCl2. The reactions of 1 percent HCl/1, 10, 50 percent O2/Ar produce Fe2O3, Fe3O4, FeCl2, and FeCl3. In each case condensed phase chlorides form at the oxide/metal interface where the oxygen potential is low. The 10 and 50 percent oxygen mixtures have kinetics in the first 3 hr similar to pure oxidation with some deviations due to iron-chloride formation. The 1 percent oxygen mixture shows enhanced reaction rates over oxidation, very likely due to the formation of a porous scale.

Li{sub 4}FeH{sub 6}: Iron-containing complex hydride with high gravimetric hydrogen density

DOE Office of Scientific and Technical Information (OSTI.GOV)

Saitoh, Hiroyuki, E-mail: cyto@spring8.or.jp; Takagi, Shigeyuki; Matsuo, Motoaki

2014-07-01

Li{sub 4}FeH{sub 6}, which has the highest gravimetric hydrogen density of iron-containing complex hydrides reported so far, is synthesized by hydrogenation of a powder mixture of iron and LiH above 6.1 GPa at 900 °C. In situ synchrotron radiation X-ray diffraction measurements reveal that while kinetics require high temperature and thus high pressure for the synthesis, Li{sub 4}FeH{sub 6} is expected to be thermodynamically stable slightly below room temperature at ambient pressure; further synthetic studies to suppress the kinetic effects may enable us to synthesize Li{sub 4}FeH{sub 6} at moderate pressures. Li{sub 4}FeH{sub 6} can be recovered at ambient conditions wheremore » Li{sub 4}FeH{sub 6} is metastable.« less

Dechlorination Kinetics Of Monochlorobiphenyls By Fe/Pd: Effects Of Solvent, Temperature, And PCB Concentration

EPA Science Inventory

Well-known, yet undefined, changes in the conditions and activity of palladized zerovalent iron (Fe/Pd) over an extended period of time hindered a careful study of dechlorination kinetics in long-term experiments. A short-term experimental method was, therefore, developed to stud...

Hydrogen Plasma Processing of Iron Ore

NASA Astrophysics Data System (ADS)

Sabat, Kali Charan; Murphy, Anthony B.

2017-06-01

Iron is currently produced by carbothermic reduction of oxide ores. This is a multiple-stage process that requires large-scale equipment and high capital investment, and produces large amounts of CO2. An alternative to carbothermic reduction is reduction using a hydrogen plasma, which comprises vibrationally excited molecular, atomic, and ionic states of hydrogen, all of which can reduce iron oxides, even at low temperatures. Besides the thermodynamic and kinetic advantages of a hydrogen plasma, the byproduct of the reaction is water, which does not pose any environmental problems. A review of the theory and practice of iron ore reduction using a hydrogen plasma is presented. The thermodynamic and kinetic aspects are considered, with molecular, atomic and ionic hydrogen considered separately. The importance of vibrationally excited hydrogen molecules in overcoming the activation energy barriers, and in transferring energy to the iron oxide, is emphasized. Both thermal and nonthermal plasmas are considered. The thermophysical properties of hydrogen and argon-hydrogen plasmas are discussed, and their influence on the constriction and flow in the of arc plasmas is considered. The published R&D on hydrogen plasma reduction of iron oxide is reviewed, with both the reduction of molten iron ore and in-flight reduction of iron ore particles being considered. Finally, the technical and economic feasibility of the process are discussed. It is shown that hydrogen plasma processing requires less energy than carbothermic reduction, mainly because pelletization, sintering, and cokemaking are not required. Moreover, the formation of the greenhouse gas CO2 as a byproduct is avoided. In-flight reduction has the potential for a throughput at least equivalent to the blast furnace process. It is concluded that hydrogen plasma reduction of iron ore is a potentially attractive alternative to standard methods.

MASS TRANSPORT EFFECTS ON THE KINETICS OF NITROBENZENE REDUCTION BY IRON METAL. (R827117)

EPA Science Inventory

To evaluate the importance of external mass transport on the overall rates of
contaminant reduction by iron metal (Fe⁰), we have compared measured
rates of surface reaction for nitrobenzene (ArNO₂) to estimated rates
of external mass transport...

Kinetic studies on the oxidation of oxyhemoglobin by biologically active iron thiosemicarbazone complexes: relevance to iron-chelator-induced methemoglobinemia.

PubMed

Basha, Maram T; Rodríguez, Carlos; Richardson, Des R; Martínez, Manuel; Bernhardt, Paul V

2014-03-01

The oxidation of oxyhemoglobin to methemoglobin has been found to be facilitated by low molecular weight iron(III) thiosemicarbazone complexes. This deleterious reaction, which produces hemoglobin protein units unable to bind dioxygen and occurs during the administration of iron chelators such as the well-known 3-aminopyridine-2-pyridinecarbaldehyde thiosemicarbazone (3-AP; Triapine), has been observed in the reaction with Fe(III) complexes of some members of the 3-AP structurally-related thiosemicarbazone ligands derived from di-2-pyridyl ketone (HDpxxT series). We have studied the kinetics of this oxidation reaction in vitro using human hemoglobin and found that the reaction proceeds with two distinct time-resolved steps. These have been associated with sequential oxidation of the two different oxyheme cofactors in the α and β protein chains. Unexpected steric and hydrogen-bonding effects on the Fe(III) complexes appear to be the responsible for the observed differences in the reaction rate across the series of HDpxxT ligand complexes used in this study.

Key Roles of Size and Crystallinity of Nanosized Iron Hydr(oxides) Stabilized by Humic Substances in Iron Bioavailability to Plants.

PubMed

Kulikova, Natalia A; Polyakov, Alexander Yu; Lebedev, Vasily A; Abroskin, Dmitry P; Volkov, Dmitry S; Pankratov, Denis A; Klein, Olga I; Senik, Svetlana V; Sorkina, Tatiana A; Garshev, Alexey V; Veligzhanin, Alexey A; Garcia Mina, Jose M; Perminova, Irina V

2017-12-27

Availability of Fe in soil to plants is closely related to the presence of humic substances (HS). Still, the systematic data on applicability of iron-based nanomaterials stabilized with HS as a source for plant nutrition are missing. The goal of our study was to establish a connection between properties of iron-based materials stabilized by HS and their bioavailability to plants. We have prepared two samples of leonardite HS-stabilized iron-based materials with substantially different properties using the reported protocols and studied their physical chemical state in relation to iron uptake and other biological effects. We used Mössbauer spectroscopy, XRD, SAXS, and TEM to conclude on iron speciation, size, and crystallinity. One material (Fe-HA) consisted of polynuclear iron(III) (hydr)oxide complexes, so-called ferric polymers, distributed in HS matrix. These complexes are composed of predominantly amorphous small-size components (<5 nm) with inclusions of larger crystalline particles (the mean size of (11 ± 4) nm). The other material was composed of well-crystalline feroxyhyte (δ'-FeOOH) NPs with mean transverse sizes of (35 ± 20) nm stabilized by small amounts of HS. Bioavailability studies were conducted on wheat plants under conditions of iron deficiency. The uptake studies have shown that small and amorphous ferric polymers were readily translocated into the leaves on the level of Fe-EDTA, whereas relatively large and crystalline feroxyhyte NPs were mostly sorbed on the roots. The obtained data are consistent with the size exclusion limits of cell wall pores (5-20 nm). Both samples demonstrated distinct beneficial effects with respect to photosynthetic activity and lipid biosynthesis. The obtained results might be of use for production of iron-based nanomaterials stabilized by HS with the tailored iron availability to plants. They can be applied as the only source for iron nutrition as well as in combination with the other elements, for example, for industrial production of "nanofortified" macrofertilizers (NPK).

[Performance Study of Bromochloracetonitrile Degradation in Drinking Water by Fe/Cu Catalytic Reduction].

PubMed

Ding, Chun-sheng; Ma, Hai-long; Fu, Yang-ping; Zhao, Shi-du; Li, Dong-bing

2015-06-01

The paper used the method of iron copper catalyst reduction to degrade low concentrations of bromochloracetonitrile (BCAN) to lighten the damage to human being, which is a kind of disinfection by-products (DBPs) produced during the chlorination process of drinking water. The removal efficiency of BCAN and its influencing factors were investigated. The mechanism of degradation and kinetics were also explored. The results indicated that iron copper had a greater degradation ability towards BCAN, and the degradation rate of iron copper (mass ratio of 10:1) was 1.5 times that of the zero-valent iron. The removal of BCAN increased obviously with the increase of Fe/Cu dosage. When the initial concentration was set at 20 microg x L(-1), after a reaction time of 150 min, removal of BCAN was improved from 51.1% to 89.5% with the increase of iron copper (mass ratio of 10:1) dosage from 5 g x L(-1) to 10 g x L(-1). The temperature also had great impact on BCAN removal and the removal increased with the increase of temperature. However, BCAN removal did not change a lot with the variation of the initial concentration of BCAN when it was at a low level. The BCAN degradation by iron copper catalytic-reduction followed the first-order kinetics model.

Enhanced Fenton-like removal of nitrobenzene via internal microelectrolysis in nano zerovalent iron/activated carbon composite.

PubMed

Hu, Sihai; Wu, Yaoguo; Yao, Hairui; Lu, Cong; Zhang, Chengjun

2016-01-01

The efficiency of Fenton-like catalysis using nano zerovalent iron (nZVI) is limited by nZVI aggregation and activity loss due to inactive ferric oxide forming on the nZVI surface, which hinders electron transfer. A novel iron-carbon composite catalyst consisting of nZVI and granular activated carbon (GAC), which can undergo internal iron-carbon microelectrolysis spontaneously, was successfully fabricated by the adsorption-reduction method. The catalyst efficiency was evaluated in nitrobenzene (NB) removal via the Fenton-like process (H2O2-nZVI/GAC). The results showed that nZVI/GAC composite was good for dispersing nZVI on the surface of GAC, which permitted much better removal efficiency (93.0%) than nZVI (31.0%) or GAC (20.0%) alone. Moreover, iron leaching decreased from 1.28 to 0.58 mg/L after reaction of 240 min and the oxidation kinetic of the Fenton-like reaction can be described well by the second-order reaction kinetic model (R2=0.988). The composite catalyst showed sustainable catalytic ability and GAC performed as a medium for electron transfer in internal iron-carbon microelectrolysis to promote Fe2+ regeneration and Fe3+/Fe2+ cycles. Therefore, this study represents an important method to design a low cost and high efficiency Fenton-like catalyst in practical application.

Spectroscopic evidence for the role of a site of the di-iron catalytic center of ferritins in tuning the kinetics of Fe(ii) oxidation.

PubMed

Ebrahimi, Kourosh Honarmand; Bill, Eckhard; Hagedoorn, Peter-Leon; Hagen, Wilfred R

2016-11-15

Ferritin is a nanocage protein made of 24 subunits. Its major role is to manage intracellular concentrations of free Fe(ii) and Fe(iii) ions, which is pivotal for iron homeostasis across all domains of life. This function of the protein is regulated by a conserved di-iron catalytic center and has been the subject of extensive studies over the past 50 years. Yet, it has not been fully understood how Fe(ii) is oxidized in the di-iron catalytic center and it is not known why eukaryotic and microbial ferritins oxidize Fe(ii) with different kinetics. In an attempt to obtain a new insight into the mechanism of Fe(ii) oxidation and understand the origin of the observed differences in the catalysis of Fe(ii) oxidation among ferritins we studied and compared the mechanism of Fe(ii) oxidation in the eukaryotic human H-type ferritin (HuHF) and the archaeal ferritin from Pyrococcus furiosus (PfFtn). The results show that the spectroscopic characteristics of the intermediate of Fe(ii) oxidation and the Fe(iii)-products are the same in these two ferritins supporting the proposal of unity in the mechanism of Fe(ii) oxidation among eukaryotic and microbial ferritins. Moreover, we observed that a site in the di-iron catalytic center controls the distribution of Fe(ii) among subunits of HuHF and PfFtn differently. This observation explains the reported differences between HuHF and PfFtn in the kinetics of Fe(ii) oxidation and the amount of O 2 consumed per Fe(ii) oxidized. These results provide a fresh understanding of the mechanism of Fe(ii) oxidation by ferritins.

Route and Regulation of Zinc, Cadmium, and Iron Transport in Rice Plants (Oryza sativa L.) during Vegetative Growth and Grain Filling: Metal Transporters, Metal Speciation, Grain Cd Reduction and Zn and Fe Biofortification

PubMed Central

Yoneyama, Tadakatsu; Ishikawa, Satoru; Fujimaki, Shu

2015-01-01

Zinc (Zn) and iron (Fe) are essential but are sometimes deficient in humans, while cadmium (Cd) is toxic if it accumulates in the liver and kidneys at high levels. All three are contained in the grains of rice, a staple cereal. Zn and Fe concentrations in rice grains harvested under different levels of soil/hydroponic metals are known to change only within a small range, while Cd concentrations show greater changes. To clarify the mechanisms underlying such different metal contents, we synthesized information on the routes of metal transport and accumulation in rice plants by examining metal speciation, metal transporters, and the xylem-to-phloem transport system. At grain-filling, Zn and Cd ascending in xylem sap are transferred to the phloem by the xylem-to-phloem transport system operating at stem nodes. Grain Fe is largely derived from the leaves by remobilization. Zn and Fe concentrations in phloem-sap and grains are regulated within a small range, while Cd concentrations vary depending on xylem supply. Transgenic techniques to increase concentrations of the metal chelators (nicotianamine, 2′-deoxymugineic acid) are useful in increasing grain Zn and Fe concentrations. The elimination of OsNRAMP5 Cd-uptake transporter and the enhancement of root cell vacuolar Cd sequestration reduce uptake and root-to-shoot transport, respectively, resulting in a reduction of grain Cd accumulation. PMID:26287170

Route and Regulation of Zinc, Cadmium, and Iron Transport in Rice Plants (Oryza sativa L.) during Vegetative Growth and Grain Filling: Metal Transporters, Metal Speciation, Grain Cd Reduction and Zn and Fe Biofortification.

PubMed

Yoneyama, Tadakatsu; Ishikawa, Satoru; Fujimaki, Shu

2015-08-13

Zinc (Zn) and iron (Fe) are essential but are sometimes deficient in humans, while cadmium (Cd) is toxic if it accumulates in the liver and kidneys at high levels. All three are contained in the grains of rice, a staple cereal. Zn and Fe concentrations in rice grains harvested under different levels of soil/hydroponic metals are known to change only within a small range, while Cd concentrations show greater changes. To clarify the mechanisms underlying such different metal contents, we synthesized information on the routes of metal transport and accumulation in rice plants by examining metal speciation, metal transporters, and the xylem-to-phloem transport system. At grain-filling, Zn and Cd ascending in xylem sap are transferred to the phloem by the xylem-to-phloem transport system operating at stem nodes. Grain Fe is largely derived from the leaves by remobilization. Zn and Fe concentrations in phloem-sap and grains are regulated within a small range, while Cd concentrations vary depending on xylem supply. Transgenic techniques to increase concentrations of the metal chelators (nicotianamine, 2'-deoxymugineic acid) are useful in increasing grain Zn and Fe concentrations. The elimination of OsNRAMP5 Cd-uptake transporter and the enhancement of root cell vacuolar Cd sequestration reduce uptake and root-to-shoot transport, respectively, resulting in a reduction of grain Cd accumulation.

Heterogeneity in horse ferritins. A comparative study of surface charge, iron content and kinetics of iron uptake.

PubMed Central

Russell, S M; Harrison, P M

1978-01-01

Horse ferritins from different organs show heterogeneity on electrofocusing in Ampholine gradients. Both ferritin and apoferritin from liver and spleen could be fractionated with respect to surface charge by serial precipitation with (NH4)2SO4. In the ferritin fractions, increasing iron content parallels increasing isoelectric point. After removal of their iron, those fractions which originally contained most iron accumulated added iron at the fastest rates. When unfractionated ferritins from different organs were compared the average isoelectric point increased in order spleen less than liver less than kidney less than heart. The order of initial rates of iron uptake by the apoferritins was spleen greater than kidney greater than heart and initial average iron contents also followed this order. The relatively low rates of iron accumulation by iron-poor molecules may have been due to structural alteration, to degradation, to activation of the iron-rich molecules or to other factors. Images Fig. 1. Fig. 2. PMID:736908

Synthesis, chemical and biological studies on new Fe(3+)-glycosilated beta-diketo complexes for the treatment of iron deficiency.

PubMed

Arezzini, Beatrice; Ferrali, Marco; Ferrari, Erika; Frassineti, Chiara; Lazzari, Sandra; Marverti, Gaetano; Spagnolo, Ferdinando; Saladini, Monica

2008-11-01

A simple synthetic pathway to obtain glycosilated beta-diketo derivatives is proposed. These compounds show a good iron(III) affinity therefore we may suggest the use of their Fe(3+)-complexes as oral iron supplements in the treatment of anaemia. The glycosilated compounds (6-GlcH, 6-GlcOH and 6-GlcOCH(3)) are characterized by means of spectroscopic (UV, (1)H and (13)C NMR) and potentiometric techniques; they have a good water solubility, are kinetically stable in physiological condition (t(1/2)>100h) and show a low cytotoxicity also in high concentrations (IC(50)>400 microM). They are able to bind Fe(3+) ion in acid condition (pH approximately 2) forming complex species thermodynamically more stable than those of other ligands commonly used in the treatment of iron deficiency. The iron complexes show also a good kinetic stability both in acidic and physiological pH and have a good lypophilicity (logP>-0.7) that suggests an efficient gastrointestinal absorption in view of their possible use in oral therapy. In addition they demonstrate a poor affinity for competitive biological metal ion such as Ca(2+), and in particular 6-GlcOCH(3) is able to inhibit lipid peroxidation.

Magnetic activated carbon-Fe3O4 nanocomposites--synthesis and applications in the removal of acid yellow dye 17 from water.

PubMed

Ranjithkumar, V; Hazeen, A Nizarul; Thamilselvan, M; Vairam, S

2014-07-01

In this work, synthesis of activated carbon-Fe3O4 composites using activated carbon and iron benzoate/oxalate precursors by simple pyrolytic method and its utility for the removal of acid yellow dye from water are presented. Iron carboxylates held up into the pores of carbon dissociate at their decomposition temperatures form dispersed Fe3O4 nanoparticles in carbon matrix. The composites were characterized by FTIR, PXRD, SEM, TEM, EDX and magnetization measurements. The size of the nano iron oxides are in the range of 21-33 nm formed from iron benzoate precursor and 6-11 nm from iron oxalate precursor. The oxides are magnetic and their saturation magnetization in the range of 0.08-0.16 emu/g and Coercivity (H(c)) 474-600, being lower and higher than that of bare bulk Fe3O4 are due to the nano size of oxides. Composites find application in the removal of acid yellow dye 17 from the synthetic aqueous solution at pH 5. The adsorption data are found to fit well for Langmuir adsorption isotherm. Kinetics data of adsorption of dyes indicate that the adsorption follows pseudo-second order kinetic model.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Smith, Euan; Kempson, Ivan; Juhasz, Albert L.

The consumption of arsenic (As) contaminated rice is an important exposure route for humans in countries where rice cultivation employs As contaminated irrigation water. Arsenic toxicity and mobility are a function of its chemical-speciation. The distribution and identification of As in the rice plant are hence necessary to determine the uptake, transformation and potential risk posed by As contaminated rice. In this study we report on the distribution and chemical-speciation of As in rice (Oryza sativa Quest) by X-ray fluorescence (XRF) and X-ray absorption near edge structure (XANES) measurements of rice plants grown in As contaminated paddy water. Investigations ofmore » {mu}XRF images from rice tissues found that As was present in all rice tissues, and its presence correlated with the presence of iron at the root surface and copper in the rice leaf. X-ray absorption near edge structure analysis of rice tissues identified that inorganic As was the predominant form of As in all rice tissues studied, and that arsenite became increasingly dominant in the aerial portion of the rice plant.« less

Abundance and Speciation of Water and Sulfate at Gusev Crater and Meridiani Planum

NASA Technical Reports Server (NTRS)

Ming, D. W.; Clark, B. C.; Klingelhoefer, G.; Gellert, R.; Rodionov, D.; Schroeder, C.; deSouza, P.; Yen, A.

2005-01-01

A major science goal of the Mars Exploration Rover (MER) mission is to search for evidence of water activity, and direct mineralogical evidence for aqueous activity has been reported for Meridiani Planum in the form of the iron sulfate hydroxide mineral jarosite and at Gusev crater in the form of goethite. The Spirit and Opportunity rovers have each collected 110+ Moessbauer (MB) and 75+ Alpha Particle X-Ray Spectrometer (APXS) spectra from Gusev crater and Meridiani Planum [1 - 4]. In this abstract, we use mineralogical and elemental data, primarily from the Moessbauer and APXS instruments, to infer the speciation and estimate the abundance of sulfate and water (as either the H2O molecule or the hydroxyl anion) at Gusev crater and Meridiani Planum. Throughout the abstract, we adopt a format for mineral formulas that shows water explicitly rather than the usual practice of structure-based formulas (e.g., for goethite we write Fe2O3xH2O instead of FeOOH).

Concentrations and speciation of arsenic along a groundwater flow-path in the Upper Floridan aquifer, Florida, USA

NASA Astrophysics Data System (ADS)

Haque, S. E.; Johannesson, K. H.

2006-05-01

Arsenic (As) concentrations and speciation were determined in groundwaters along a flow-path in the Upper Floridan aquifer (UFA) to investigate the biogeochemical “evolution“ of As in this relatively pristine aquifer. Dissolved inorganic As species were separated in the field using anion-exchange chromatography and subsequently analyzed by inductively coupled plasma mass spectrometry. Total As concentrations are higher in the recharge area groundwaters compared to down-gradient portions of UFA. Redox conditions vary from relatively oxic to anoxic along the flow-path. Mobilization of As species in UFA groundwaters is influenced by ferric iron reduction and subsequent dissolution, sulfate reduction, and probable pyrite precipitation that are inferred from the data to occur along distinct regions of the flow-path. In general, the distribution of As species are consistent with equilibrium thermodynamics, such that arsenate dominates in more oxidizing waters near the recharge area, and arsenite predominates in the progressively reducing groundwaters beyond the recharge area.

Sulfur and Iron Speciation in Gas-rich Impact-melt Glasses from Basaltic Shergottites Determined by Microxanes

NASA Technical Reports Server (NTRS)

Sutton, S. R.; Rao, M. N.; Nyquist, L. E.

2008-01-01

Sulfur is abundantly present as sulfate near Martian surface based on chemical and mineralogical investigations on soils and rocks in Viking, Pathfinder and MER missions. Jarosite is identified by Mossbauer studies on rocks at Meridian and Gusev, whereas MgSO4 is deduced from MgO - SO3 correlations in Pathfinder MER and Viking soils. Other sulfate minerals such as gypsum and alunogen/ S-rich aluminosilicates and halides are detected only in martian meteorites such as shergottites and nakhlites using SEM/FE-SEM and EMPA techniques. Because sulfur has the capacity to occur in multiple valence states, determination of sulfur speciation (sulfide/ sulfate) in secondary mineral assemblages in soils and rocks near Mars surface may help us understand whether the fluid-rock interactions occurred under oxidizing or reducing conditions. To understand the implications of these observations for the formation of the Gas-rich Impact-melt (GRIM) glasses, we determined the oxidation state of Fe in the GRIM glasses using Fe K micro-XANES techniques.

Toxic metal(loid) speciation during weathering of iron sulfide mine tailings under semi-arid climate

PubMed Central

Root, Robert A.; Hayes, Sarah M.; Hammond, Corin M.; Maier, Raina M.; Chorover, Jon

2015-01-01

Toxic metalliferous mine-tailings pose a significant health risk to ecosystems and neighboring communities from wind and water dispersion of particulates containing high concentrations of toxic metal(loid)s (e.g., Pb, As, Zn). Tailings are particularly vulnerable to erosion before vegetative cover can be reestablished, i.e., decades or longer in semi-arid environments without intervention. Metal(loid) speciation, linked directly to bioaccessibility and lability, is controlled by mineral weathering and is a key consideration when assessing human and environmental health risks associated with mine sites. At the semi-arid Iron King Mine and Humboldt Smelter Superfund site in central Arizona, the mineral assemblage of the top 2 m of tailings has been previously characterized. A distinct redox gradient was observed in the top 0.5 m of the tailings and the mineral assemblage indicates progressive transformation of ferrous iron sulfides to ferrihydrite and gypsum, which, in turn weather to form schwertmannite and then jarosite accompanied by a progressive decrease in pH (7.3 to 2.3). Within the geochemical context of this reaction front, we examined enriched toxic metal(loid)s As, Pb, and Zn with surficial concentrations 41.1, 10.7, 39.3 mM kg-1 (3080, 2200, and 2570 mg kg-1), respectively. The highest bulk concentrations of As and Zn occur at the redox boundary representing a 1.7 and 4.2 fold enrichment relative to surficial concentrations, respectively, indicating the translocation of toxic elements from the gossan zone to either the underlying redox boundary or the surface crust. Metal speciation was also examined as a function of depth using X-ray absorption spectroscopy (XAS). The deepest sample (180 cm) contains sulfides (e.g., pyrite, arsenopyrite, galena, and sphalerite). Samples from the redox transition zone (25-54 cm) contain a mixture of sulfides, carbonates (siderite, ankerite, cerrusite, and smithsonite) and metal(loid)s sorbed to neoformed secondary Fe phases, principally ferrihydrite. In surface samples (0-35 cm), metal(loid)s are found as sorbed species or incorporated into secondary Fe hydroxysulfate phases, such as schwertmannite and jarosites. Metal-bearing efflorescent salts (e.g., ZnSO4·nH2O) were detected in the surficial sample. Taken together, these data suggest the bioaccessibility and lability of metal(loid)s are altered by mineral weathering, which results in both the downward migration of metal(loid)s to the redox boundary, as well as the precipitation of metal salts at the surface. PMID:26549929

Reduction and Oxidation of the Active Site Iron in Tyrosine Hydroxylase: Kinetics and Specificity†

PubMed Central

Frantom, Patrick A.; Seravalli, Javier; Ragsdale, Stephen W.; Fitzpatrick, Paul F.

2006-01-01

Tyrosine hydroxylase (TyrH) is a pterin-dependent enzyme that catalyzes the hydroxylation of tyrosine to form dihydroxyphenylalanine. The oxidation state of the active site iron atom plays a central role in the regulation of the enzyme. The kinetics of reduction of ferric TyrH by several reductants were determined by anaerobic stopped-flow spectroscopy. Anaerobic rapid freeze–quench EPR confirmed that the change in the near-UV absorbance of TyrH upon adding reductant corresponded to iron reduction. Tetrahydrobiopterin reduces wild-type TyrH following a simple second-order mechanism with a rate constant of 2.8 ± 0.1 mM−1 s−1. 6-Methyltetrahydropterin reduces the ferric enzyme with a second-order rate constant of 6.1 ± 0.1 mM−1 s−1 and exhibits saturation kinetics. No EPR signal for a radical intermediate was detected. Ascorbate, glutathione, and 1,4-benzoquinone all reduce ferric TyrH, but much more slowly than tetrahydrobiopterin, suggesting that the pterin is a physiological reductant. E332A TyrH, which has an elevated Km for tetrahydropterin in the catalytic reaction, is reduced by tetrahydropterins with the same kinetic parameters as those of the wild-type enzyme, suggesting that BH4 does not bind in the catalytic conformation during the reduction. Oxidation of ferrous TyrH by molecular oxygen can be described as a single-step second-order reaction, with a rate constant of 210 mM−1 s−1. S40E TyrH, which mimics the phosphorylated state of the enzyme, has oxidation and reduction kinetics similar to those of the wild-type enzyme, suggesting that phosphorylation does not directly regulate the interconversion of the ferric and ferrous forms. PMID:16475826

Recovery of nickel and cobalt as MHP from limonitic ore leaching solution: Kinetics analysis and precipitate characterization

NASA Astrophysics Data System (ADS)

Safitri, Nina; Mubarok, M. Zaki; Winarko, Ronny; Tanlega, Zela

2018-05-01

In the present study, precipitation of nickel and cobalt as mixed hydroxide precipitate (MHP) from pregnant leach solution of nickel limonite ore from Soroako after iron removal stage was carried out. A series of MHP precipitation experiments was conducted by using MgO slurry as neutralizing agent and the effects of pH, temperature, duration of precipitation and the addition of MHP seed on the precipitation behavior of nickel, cobalt, as well as iron and manganese was studied. Characterization of MHP product was performed by particle size analyzer (PSA) as well as X-Ray Fluorescence (XRF), X-Ray Diffractometer (XRD) and Scanning Electron Microscope (SEM) analyses. Kinetics analysis was made by using differential-integral method for the rate of homogenous reaction. Precipitation at pH 7, temperature 50°C for 30 minute, without seed addition resulted in nickel and cobalt recoveries of 82.8% and 92%, respectively with co-precipitated iron and manganese of 70% and 24.2%, respectively. The seed addition increases nickel and cobalt precipitations significantly to 99.9% and 99.1%, respectively. However, the addition of seed into led to a significant increase of manganese co-precipitation from 24.2% without seed addition to 39.5% at the addition of 1 g seed per 200 mL of PLS. Kinetics analysis revealed that Ni precipitation to form MHP follows the second-order reaction kinetics with activation energy of 94.6 kJ/mol.

Fractionation of Fe isotopes during granite weathering, soil formation, and plant uptake in an Alpine glacier forefield

NASA Astrophysics Data System (ADS)

Kretzschmar, R.; Kiczka, M.; Wiederhold, J. G.; Voegelin, A.; Kraemer, S.; Bourdon, B.

2010-12-01

Iron (Fe) is not only an essential element for almost all organisms, but is also involved in many biogeochemical processes including silicate weathering and soil formation. The aim of this study was to gain a better understanding of Fe isotope fractionation during initial silicate weathering and soil formation processes. Therefore, we investigated changes in Fe speciation and Fe isotope signatures in total soils and selected Fe pools along a weathering chronosequence within an Alpine glacier forefield on granite. The sampling sites along the dated chronosequence were deglaciated since up to 150 years, and we included two additional sites which were ice-free since several thousands of years. Changes in Fe speciation were investigated using Fe K-edge X-ray absorption spectroscopy (XAS) and also qualitatively documented by optical microscopy of soil thin sections. Iron in the unweathered rock was mainly present as structural Fe in biotite, with smaller amounts in chlorite, epidote, and magnetite. Within 150 years of deglaciation, the fraction of Fe(III) relative to total Fe increased from 34 to 53%, clearly documenting oxidation of Fe(II) in primary phyllosilicates. After 100 years of deglaciation, secondary Fe(III)-oxyhydroxides were detected by XAS and were also clearly evident in soil thin sections. Elemental analysis and Fe isotope analysis of particle size fractions by MC-ICP-MS showed that the clay fractions were significantly enriched in Fe and their δ56Fe signatures were up to 0.35‰ lower than those of the bulk soils (<2 mm). In addition, the hydroxylamine-hydrochloride extractable Fe pool (1 M HA-HCl in 25% acetic acid, pH 1.5), representing mainly poorly-crystalline Fe(III)-oxyhydroxides, increased with time of deglaciation and also had a significantly (by up to 0.7‰) lighter δ56Fe signature than the respective bulk soils. Thus, our data show that weathering of primary silicates, mainly biotite and chlorite, preferentially releases light Fe isotopes during oxidative weathering, which are subsequently enriched in secondary Fe(III)-oxyhydroxides with a rather constant isotopic offset of -0.7‰ in δ56Fe relative to the bulk soils. These findings are consistent with previous laboratory experiments on silicate weathering by proton- and ligand-promoted dissolution. The data suggest a kinetic isotope effect during Fe release from primary silicates, combined with quantitative oxidation and precipitation of Fe(III) as poorly-crystalline oxyhydroxides. Analysis of plants collected along the chronosequence revealed additional fractionation towards light Fe isotopes, but the plant contribution to total Fe cycling in this young ecosystem was still minor.

Kinetic study of nickel laterite reduction roasting by palm kernel shell charcoal

NASA Astrophysics Data System (ADS)

Sugiarto, E.; Putera, A. D. P.; Petrus, H. T. B. M.

2017-05-01

Demand to process nickel-bearing laterite ore increase as continuous depletion of high-grade nickel-bearing sulfide ore takes place. Due to its common nickel association with iron, processing nickel laterite ore into nickel pig iron (NPI) has been developed by some industries. However, to achieve satisfying nickel recoveries, the process needs massive high-grade metallurgical coke consumption. Concerning on the sustainability of coke supply and positive carbon emission, reduction of nickel laterite ore using biomass-based reductor was being studied.In this study, saprolitic nickel laterite ore was being reduced by palm kernel shell charcoal at several temperatures (800-1000 °C). Variation of biomass-laterite composition was also conducted to study the reduction mechanism. X-ray diffraction and gravimetry analysis were applied to justify the phenomenon and predict kinetic model of the reduction. Results of this study provide information that palm kernel shell charcoal has similar reducing result compared with the conventional method. Reduction, however, was carried out by carbon monoxide rather than solid carbon. Regarding kinetics, Ginstling-Brouhnstein kinetic model provides satisfying results to predict the reduction phenomenon.

Unraveling the complexity of iron oxides at high pressure and temperature: Synthesis of Fe 5O 6

DOE PAGES

Lavina, Barbara; Meng, Yue

2015-06-26

The iron-oxygen system is the most important reference of rocks’ redox state. Even as minor components, iron oxides can play a critical role in redox equilibria, which affect the speciation of the fluid phases chemical differentiation, melting, and physical properties. Until our recent finding of Fe 4O 5, iron oxides were assumed to comprise only the polymorphs of FeO, Fe 3O 4, and Fe 2O 3. Combining synthesis at high pressure and temperature with micro- diffraction mapping, we have identified yet another distinct iron oxide, Fe 5O 6. The new compound, which has an orthorhombic structure, was obtained in themore » pressure range from 10 to 20 GPa upon laser heating mixtures of iron and hematite at ~2000 K, and is recoverable to ambient conditions. The high-pressure orthorhombic iron oxides Fe 5O 6, Fe 4O 5, and h-Fe 3O 4 display similar iron coordination geometries and structural arrangements, and indeed exhibit coherent systematic behavior of crystallographic parameters and compressibility. Fe 5O 6, along with FeO and Fe 4O 5, is a candidate key minor phase of planetary interiors; as such, it is of major petrological and geo- chemical importance. Here, we are revealing an unforeseen complexity in the Fe-O system with four different compounds—FeO, Fe 5O 6, Fe 4O 5, and h-Fe 3O 4—in a narrow compositional range (0.75 < Fe/O < 1.0). New, finely spaced oxygen buffers at conditions of the Earth’s mantle can be defined.« less

Effect of nanoscale zero-valent iron and magnetite (Fe3O4) on the fate of metals during anaerobic digestion of sludge.

PubMed

Suanon, Fidèle; Sun, Qian; Mama, Daouda; Li, Jiangwei; Dimon, Biaou; Yu, Chang-Ping

2016-01-01

Anaerobic digestion (AD) is one of the most widely used processes to stabilize waste sewage sludge and produce biogas renewable energy. In this study, two different iron nanoparticles [nanoscale zero-valent iron (nZVI) and magnetite (Fe3O4)] were used in the mesophilic AD processes (37 ± 1 °C) to improve biogas production. In addition, changes of heavy metal (Cd, Co, Cu, Zn, Ni and Cr) speciation during AD of sludge with and without iron nanoparticles have been investigated. Concentrations of metals in the initial sludge were as follows: 63.1, 73.4, 1102.2, 2060.3, 483.9 and 604.1 mg kg(-1) (dry sludge basis) for Cd, Co, Cu, Zn, Ni and Cr, respectively. Sequential fractionation showed that metals were predominantly bonded to organic matter and carbonates in the initial sludge. Compared with AD without iron nanoparticles, the application of iron nanoparticles (at dose of 0.5% in this study) showed positive impact not only on biogas production, but also on improvement of metals stabilization in the digestate. Metals were found concentrated in Fe-Mn bound and residual fractions and little was accumulated in the liquid digestate and most mobile fractions of solid digestate (water soluble, exchangeable and carbonates bound). Therefore, iron nanoparticles when properly used, could improve not only biogas yield, but also regulate and control the mobilization of metals during AD process. However, our study also observed that iron nanoparticles could promote the immobilization of phosphorus within the sludge during AD, and more research is needed to fully address the mechanism behind this phenomenon and the impact on future phosphorus reuse. Copyright © 2015 Elsevier Ltd. All rights reserved.

ARSENATE AND ARSENITE REMOVAL BY ZERO-VALENT IRON: EFFECTS OF PHOSPHATE, SILICATE, CARBONATE, BORATE, SULFATE, CHROMATE, MOLYBDATE, AND NITRATE, RELATIVE TO CHLORIDE

EPA Science Inventory

Batch tests were performed to evaluate the effects of inorganic anion competition on the kinetics of arsenate (As(V)) and arsenite (As(III)) removal by zerovalent iron (Peerless Fe0) in aqueous solution. The oxyanions underwent either sorption-dominated reactions (phosphate, sil...

Insights into solar photo-Fenton reaction parameters in the oxidation of a sanitary landfill leachate at lab-scale.

PubMed

Silva, Tânia F C V; Ferreira, Rui; Soares, Petrick A; Manenti, Diego R; Fonseca, Amélia; Saraiva, Isabel; Boaventura, Rui A R; Vilar, Vítor J P

2015-12-01

This work evaluates the effect of the main photo-Fenton (PF) reaction variables on the treatment of a sanitary landfill leachate collected at the outlet of a leachate treatment plant, which includes aerated lagooning followed by aerated activated sludge and a final coagulation-flocculation step. The PF experiments were performed in a lab-scale compound parabolic collector (CPC) photoreactor using artificial solar radiation. The photocatalytic reaction rate was determined while varying the total dissolved iron concentration (20-100 mg Fe(2+)/L), solution pH (2.0-3.6), operating temperature (10-50 °C), type of acid used for acidification (H2SO4, HCl and H2SO4 + HCl) and UV irradiance (22-68 W/m(2)). This work also tries to elucidate the role of ferric hydroxides, ferric sulphate and ferric chloride species, by taking advantage of ferric speciation diagrams, in the efficiency of the PF reaction when applied to leachate oxidation. The molar fraction of the most photoactive ferric species, FeOH(2+), was linearly correlated with the PF pseudo-first order kinetic constants obtained at different solution pH and temperature values. Ferric ion speciation diagrams also showed that the presence of high amounts of chloride ions negatively affected the PF reaction, due to the decrease of ferric ions solubility and scavenging of hydroxyl radicals for chlorine radical formation. The increment of the PF reaction rates with temperature was mainly associated with the increase of the molar fraction of FeOH(2+). The optimal parameters for the photo-Fenton reaction were: pH = 2.8 (acidification agent: H2SO4); T = 30 °C; [Fe(2+)] = 60 mg/L and UV irradiance = 44 WUV/m(2), achieving 72% mineralization after 25 kJUV/L of accumulated UV energy and 149 mM of H2O2 consumed. Copyright © 2015 Elsevier Ltd. All rights reserved.

Particles, sweat, and tears: a comparative study on bioaccessibility of ferrochromium alloy and stainless steel particles, the pure metals and their metal oxides, in simulated skin and eye contact.

PubMed

Hedberg, Yolanda; Midander, Klara; Wallinder, Inger Odnevall

2010-07-01

Ferrochromium alloys are manufactured in large quantities and placed on the global market for use as master alloys (secondary raw materials), primarily for stainless steel production. Any potential human exposure to ferrochromium alloy particles is related to occupational activities during production and use, with 2 main exposure routes, dermal contact and inhalation and subsequent digestion. Alloy and reference particles exposed in vitro in synthetic biological fluids relevant for these main exposure routes have been investigated in a large research effort combining bioaccessibility; chemical speciation; and material, surface, and particle characteristics. In this paper, data for the dermal exposure route, including skin and eye contact, will be presented and discussed. Bioaccessibility data have been generated for particles of a ferrochromium alloy, stainless steel grade AISI 316L, pure Fe, pure Cr, iron(II,III)oxide, and chromium(III)oxide, upon immersion in artificial sweat (pH 6.5) and artificial tear (pH 8.0) fluids for various time periods. Measured released amounts of Fe, Cr, and Ni are presented in terms of average Fe and Cr release rates and amounts released per amount of particles loaded. The results are discussed in relation to bulk and surface composition of the particles. Additional information, essential to assess the bioavailability of Cr released, was generated by determining its chemical speciation and by providing information on its complexation and oxidation states in both media investigated. The effect of differences in experimental temperature, 30 degrees C and 37 degrees C, on the extent of metal release in artificial sweat is demonstrated. Iron was the preferentially released element in all test media and for all time periods and iron-containing particles investigated. The extent of metal release was highly pH dependent and was also dependent on the medium composition. Released amounts of Cr and Fe were very low (close to the limit of detection, <0.008% of particles released or dissolved as iron or chromium) for the alloy particles (ferrochromium alloy and stainless steel), the pure Cr particles, and the metal oxide particles. The released fraction of Cr (Cr/[Cr + Fe]) varied with the material investigated, the test medium, and the exposure time and cannot be predicted from either the bulk or the surface composition. Chromium was released as noncomplexed Cr(III) and in addition in very low concentrations (<3 microg/L). Nickel released was under the limit of detection (0.5 microg/L), except for ultrafine stainless steel particles (<10 microg/L). It is evident that media chemistry and material properties from a bulk and surface perspective, as well as other particle characteristics, and the chemical speciation of released metals have to be considered when assessing any potential hazard or risk induced by sparingly soluble metal or alloy particles. (c) 2010 SETAC.

Kinetic Modelling and Experimental Studies for the Effects of Fe 2+ Ions on Xylan Hydrolysis with Dilute-Acid Pretreatment and Subsequent Enzymatic Hydrolysis

DOE PAGES

Wei, Hui; Chen, Xiaowen; Shekiro, Joseph; ...

2018-01-20

High-temperature (150-170 degrees C) pretreatment of lignocellulosic biomass with mineral acids is well established for xylan breakdown. Fe 2+ is known to be a cocatalyst of this process although kinetics of its action remains unknown. The present work addresses the effect of ferrous ion concentration on sugar yield and degradation product formation from corn stover for the entire two-step treatment, including the subsequent enzymatic cellulose hydrolysis. The feedstock was impregnated with 0.5% acid and 0.75 mM iron cocatalyst, which was found to be optimal in preliminary experiments. The detailed kinetic data of acid pretreatment, with and without iron, was satisfactorilymore » modelled with a four-step linear sequence of first-order irreversible reactions accounting for the formation of xylooligomers, xylose and furfural as intermediates to provide the values of Arrhenius activation energy. Based on this kinetic modelling, Fe 2+ turned out to accelerate all four reactions, with a significant alteration of the last two steps, that is, xylose degradation. Consistent with this model, the greatest xylan conversion occurred at the highest severity tested under 170 ⁰C/30 min with 0.75 mM Fe 2+, with a total of 8% xylan remaining in the pretreated solids, whereas the operational conditions leading to the highest xylose monomer yield, 63%, were milder, 150 degrees C with 0.75 mM Fe 2+ for 20 min. Furthermore, the subsequent enzymatic hydrolysis with the prior addition of 0.75 mM of iron(II) increased the glucose production to 56.3% from 46.3% in the control (iron-free acid). The detailed analysis indicated that conducting the process at lower temperatures yet long residence times benefits the yield of sugars. The above kinetic modelling results of Fe 2+ accelerating all four reactions are in line with our previous mechanistic research showing that the pretreatment likely targets multiple chemistries in plant cell wall polymer networks, including those represented by the C-O-C and C-H bonds in cellulose, resulting in enhanced sugar solubilization and digestibility.« less

Kinetic Modelling and Experimental Studies for the Effects of Fe 2+ Ions on Xylan Hydrolysis with Dilute-Acid Pretreatment and Subsequent Enzymatic Hydrolysis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wei, Hui; Chen, Xiaowen; Shekiro, Joseph

High-temperature (150-170 degrees C) pretreatment of lignocellulosic biomass with mineral acids is well established for xylan breakdown. Fe 2+ is known to be a cocatalyst of this process although kinetics of its action remains unknown. The present work addresses the effect of ferrous ion concentration on sugar yield and degradation product formation from corn stover for the entire two-step treatment, including the subsequent enzymatic cellulose hydrolysis. The feedstock was impregnated with 0.5% acid and 0.75 mM iron cocatalyst, which was found to be optimal in preliminary experiments. The detailed kinetic data of acid pretreatment, with and without iron, was satisfactorilymore » modelled with a four-step linear sequence of first-order irreversible reactions accounting for the formation of xylooligomers, xylose and furfural as intermediates to provide the values of Arrhenius activation energy. Based on this kinetic modelling, Fe 2+ turned out to accelerate all four reactions, with a significant alteration of the last two steps, that is, xylose degradation. Consistent with this model, the greatest xylan conversion occurred at the highest severity tested under 170 ⁰C/30 min with 0.75 mM Fe 2+, with a total of 8% xylan remaining in the pretreated solids, whereas the operational conditions leading to the highest xylose monomer yield, 63%, were milder, 150 degrees C with 0.75 mM Fe 2+ for 20 min. Furthermore, the subsequent enzymatic hydrolysis with the prior addition of 0.75 mM of iron(II) increased the glucose production to 56.3% from 46.3% in the control (iron-free acid). The detailed analysis indicated that conducting the process at lower temperatures yet long residence times benefits the yield of sugars. The above kinetic modelling results of Fe 2+ accelerating all four reactions are in line with our previous mechanistic research showing that the pretreatment likely targets multiple chemistries in plant cell wall polymer networks, including those represented by the C-O-C and C-H bonds in cellulose, resulting in enhanced sugar solubilization and digestibility.« less

Low-oxygen and chemical kinetic constraints on the geochemical niche of neutrophilic iron(II) oxidizing microorganisms

NASA Astrophysics Data System (ADS)

Druschel, Gregory K.; Emerson, David; Sutka, R.; Suchecki, P.; Luther, George W., III

2008-07-01

Neutrophilic iron oxidizing bacteria (FeOB) must actively compete with rapid abiotic processes governing Fe(II) oxidation and as a result have adapted to primarily inhabit low-O 2 environments where they can more successfully compete with abiotic Fe(II) oxidation. The spatial distribution of these microorganisms can be observed through the chemical gradients they affect, as measured using in situ voltammetric analysis for dissolved Fe(II), Fe(III), O 2, and FeS (aq). Field and laboratory determination of the chemical environments inhabited by the FeOB were coupled with detailed kinetic competition studies for abiotic and biotic oxidation processes using a pure culture of FeOB to quantify the geochemical niche these organisms inhabit. In gradient culture tubes, the maximum oxygen levels, which were associated with growth bands of Sideroxydans lithotrophicus (ES-1, a novel FeOB), were 15-50 μM. Kinetic measurements made on S. lithotrophicus compared biotic/abiotic (killed control) Fe oxidation rates. The biotic rate can be a significant and measurable fraction of the total Fe oxidation rate below O 2 concentrations of approximately 50 μM, but biotic Fe(II) oxidation (via the biotic/abiotic rate comparison) becomes difficult to detect at higher O 2 levels. These results are further supported by observations of conditions supporting FeOB communities in field settings. Variablity in cell densities and cellular activity as well as variations in hydrous ferrous oxide mineral quantities significantly affect the laboratory kinetic rates. The microbial habitat (or geochemical niche) where FeOB are active is thus largely controlled by the competition between abiotic and biotic kinetics, which are dependent on Fe(II) concentration, P O2, temperature and pH in addition to the surface area of hydrous ferric oxide minerals and the cell density/activity of FeOB. Additional field and lab culture observations suggest a potentially important role for the iron-sulfide aqueous molecular cluster, FeS (aq), in the overall cycling of iron associated with the environments these microorganisms inhabit.

A Histidine Aspartate Ionic Lock Gates the Iron Passage in Miniferritins from Mycobacterium smegmatis*

PubMed Central

Williams, Sunanda Margrett; Chandran, Anu V.; Vijayabaskar, Mahalingam S.; Roy, Sourav; Balaram, Hemalatha; Vishveshwara, Saraswathi; Vijayan, Mamannamana; Chatterji, Dipankar

2014-01-01

Dps (DNA-binding protein from starved cells) are dodecameric assemblies belonging to the ferritin family that can bind DNA, carry out ferroxidation, and store iron in their shells. The ferritin-like trimeric pore harbors the channel for the entry and exit of iron. By representing the structure of Dps as a network we have identified a charge-driven interface formed by a histidine aspartate cluster at the pore interface unique to Mycobacterium smegmatis Dps protein, MsDps2. Site-directed mutagenesis was employed to generate mutants to disrupt the charged interactions. Kinetics of iron uptake/release of the wild type and mutants were compared. Crystal structures were solved at a resolution of 1.8–2.2 Å for the various mutants to compare structural alterations vis à vis the wild type protein. The substitutions at the pore interface resulted in alterations in the side chain conformations leading to an overall weakening of the interface network, especially in cases of substitutions that alter the charge at the pore interface. Contrary to earlier findings where conserved aspartate residues were found crucial for iron release, we propose here that in the case of MsDps2, it is the interplay of negative-positive potentials at the pore that enables proper functioning of the protein. In similar studies in ferritins, negative and positive patches near the iron exit pore were found to be important in iron uptake/release kinetics. The unique ionic cluster in MsDps2 makes it a suitable candidate to act as nano-delivery vehicle, as these gated pores can be manipulated to exhibit conformations allowing for slow or fast rates of iron release. PMID:24573673

Kinetic behavior of Fe(o,o-EDDHA)-humic substance mixtures in several soil components and in calcareous soils.

PubMed

Cerdán, Mar; Alcañiz, Sara; Juárez, Margarita; Jordá, Juana D; Bermúdez, Dolores

2007-10-31

Ferric ethylenediamine- N, N'-bis-(o-hydroxyphenylacetic)acid chelate (Fe(o, o-EDDHA)) is one of the most effective Fe fertilizers in calcareous soils. However, humic substances are occasionally combined with iron chelates in drip irrigation systems in order to lower costs. The reactivity of iron chelate-humic substance mixtures in several soil components and in calcareous soils was investigated through interaction tests, and their behavior was compared to the application of iron chelates and humic substances separately. Two commercial humic substances and two Fe(o, o-EDDHA) chelates (one synthesized in the laboratory and one commercial) were used to prepare iron chelate-humic substance mixtures at 50% (w/w). Various soil components (calcium carbonate, gibbsite, amorphous iron oxide, hematite, tenorite, zincite, amorphous Mn oxide, and peat) and three calcareous soils were shaken for 15 days with the mixtures and with iron chelate and humic substance solutions. The kinetic behavior of Fe(o, o-EDDHA) and Fe non-(o,o-EDDHA) (Fe bonded to (o,p-EDDHA) and other polycondensated ligands) and of the different nutrients solubilized after the interaction assay was determined. The results showed that the mixtures did not significantly reduce the retention of Fe(o, o-EDDHA) and Fe non-(o,o-EDDHA) in the soil components and the calcareous soils compared to the iron chelate solutions, but they did produce changes in the retention rate. Moreover, the competition between humic substances and synthetic chelating agents for complexing metal cations limited the effectiveness of the mixtures to mobilize nutrients from the substrates. The presence of Fe(o, p-EDDHA) and other byproducts in the commercial iron chelate had an important effect on the evolution of Fe(o, o-EDDHA) and the nutrient solubilization process.

Kinetic modeling of electron transfer reactions in photosystem I complexes of various structures with substituted quinone acceptors.

PubMed

Milanovsky, Georgy E; Petrova, Anastasia A; Cherepanov, Dmitry A; Semenov, Alexey Yu

2017-09-01

The reduction kinetics of the photo-oxidized primary electron donor P 700 in photosystem I (PS I) complexes from cyanobacteria Synechocystis sp. PCC 6803 were analyzed within the kinetic model, which considers electron transfer (ET) reactions between P 700 , secondary quinone acceptor A 1 , iron-sulfur clusters and external electron donor and acceptors - methylviologen (MV), 2,3-dichloro-naphthoquinone (Cl 2 NQ) and oxygen. PS I complexes containing various quinones in the A 1 -binding site (phylloquinone PhQ, plastoquinone-9 PQ and Cl 2 NQ) as well as F X -core complexes, depleted of terminal iron-sulfur F A /F B clusters, were studied. The acceleration of charge recombination in F X -core complexes by PhQ/PQ substitution indicates that backward ET from the iron-sulfur clusters involves quinone in the A 1 -binding site. The kinetic parameters of ET reactions were obtained by global fitting of the P 700 + reduction with the kinetic model. The free energy gap ΔG 0 between F X and F A /F B clusters was estimated as -130 meV. The driving force of ET from A 1 to F X was determined as -50 and -220 meV for PhQ in the A and B cofactor branches, respectively. For PQ in A 1A -site, this reaction was found to be endergonic (ΔG 0  = +75 meV). The interaction of PS I with external acceptors was quantitatively described in terms of Michaelis-Menten kinetics. The second-order rate constants of ET from F A /F B , F X and Cl 2 NQ in the A 1 -site of PS I to external acceptors were estimated. The side production of superoxide radical in the A 1 -site by oxygen reduction via the Mehler reaction might comprise ≥0.3% of the total electron flow in PS I.

Bacterial oxidation of ferrous iron at low temperatures.

PubMed

Kupka, Daniel; Rzhepishevska, Olena I; Dopson, Mark; Lindström, E Börje; Karnachuk, Olia V; Tuovinen, Olli H

2007-08-15

This study comprises the first report of ferrous iron oxidation by psychrotolerant, acidophilic iron-oxidizing bacteria capable of growing at 5 degrees C. Samples of mine drainage-impacted surface soils and sediments from the Norilsk mining region (Taimyr, Siberia) and Kristineberg (Skellefte district, Sweden) were inoculated into acidic ferrous sulfate media and incubated at 5 degrees C. Iron oxidation was preceded by an approximately 3-month lag period that was reduced in subsequent cultures. Three enrichment cultures were chosen for further work and one culture designated as isolate SS3 was purified by colony isolation from a Norilsk enrichment culture for determining the kinetics of iron oxidation. The 16S rRNA based phylogeny of SS3 and two other psychrotolerant cultures, SS5 from Norilsk and SK5 from Northern Sweden, was determined. Comparative analysis of amplified 16S rRNA gene sequences showed that the psychrotolerant cultures aligned within Acidithiobacillus ferrooxidans. The rate constant of iron oxidation by growing cultures of SS3 was in the range of 0.0162-0.0104 h(-1) depending on the initial pH. The oxidation kinetics followed an exponential pattern, consistent with a first order rate expression. Parallel iron oxidation by a mesophilic reference culture of Acidithiobacillus ferrooxidans was extremely slow and linear. Precipitates harvested from the 5 degrees C culture were identified by X-ray diffraction as mixtures of schwertmannite (ideal formula Fe(8)O(8)(OH)(6)SO(4)) and jarosite (KFe(3)(SO(4))(2)(OH)(6)). Jarosite was much more dominant in precipitates produced at 30 degrees C. (c) 2007 Wiley Periodicals, Inc.

Effects of medium and trace metals on kinetics of carbon tetrachloride transformation by Pseudomonas sp. strain KC.

PubMed Central

Tatara, G M; Dybas, M J; Criddle, C S

1993-01-01

Under denitrifying conditions, Pseudomonas sp. strain KC transforms carbon tetrachloride (CT) to carbon dioxide via a complex but as yet undetermined mechanism. Transformation rates were first order with respect to CT concentration over the CT concentration range examined (0 to 100 micrograms/liter) and proportional to protein concentration, giving pseudo-second-order kinetics overall. Addition of ferric iron (1 to 20 microM) to an actively transforming culture inhibited CT transformation, and the degree of inhibition increased with increasing iron concentration. By removing iron from the trace metals solution or by removing iron-containing precipitate from the growth medium, higher second-order rate coefficients were obtained. Copper also plays a role in CT transformation. Copper was toxic at neutral pH. By adjusting the medium pH to 8.2, soluble iron and copper levels decreased as a precipitate formed, and CT transformation rates increased. However, cultures grown at high pH without any added trace copper (1 microM) exhibited slower growth rates and greatly reduced rates of CT transformation, indicating that copper is required for CT transformation. The use of pH adjustment to decrease iron solubility, to avoid copper toxicity, and to provide a selective advantage for strain KC was evaluated by using soil slurries and groundwater containing high levels of iron. In samples adjusted to pH 8.2 and inoculated with strain KC, CT disappeared rapidly in the absence or presence of acetate or nitrate supplements. CT did not disappear in pH-adjusted controls that were not inoculated with strain KC. PMID:8357248

The effect of silicon on iron plaque formation and arsenic accumulation in rice genotypes with different radial oxygen loss (ROL).

PubMed

Wu, Chuan; Zou, Qi; Xue, Sheng-Guo; Pan, Wei-Song; Huang, Liu; Hartley, William; Mo, Jing-Yu; Wong, Ming-Hung

2016-05-01

Rice is one of the major pathways of arsenic (As) exposure in human food chain, threatening over half of the global population. Greenhouse pot experiments were conducted to examine the effects of Si application on iron (Fe) plaque formation, As uptake and rice grain As speciation in indica and hybrid rice genotypes with different radial oxygen loss (ROL) ability. The results demonstrated that Si significantly increased root and grain biomass. Indica genotypes with higher ROL induced greater Fe plaque formation, compared to hybrid genotypes and sequestered more As in Fe plaque. Silicon applications significantly increased Fe concentrations in iron plaque of different genotypes, but it decreased As concentrations in the roots, straws and husks by 28-35%, 15-35% and 32-57% respectively. In addition, it significantly reduced DMA accumulation in rice grains but not inorganic As accumulation. Rice of indica genotypes with higher ROL accumulated lower concentrations of inorganic As in grains than hybrid genotypes with lower ROL. Copyright © 2016 Elsevier Ltd. All rights reserved.

Redox process catalysed by growing crystal-strengite, FePO4,2H2O, crystallizing from solution with iron(II) and hydroxylamine

NASA Astrophysics Data System (ADS)

Lundager Madsen, Hans Erik

2014-09-01

In an attempt to grow pure crystals of the iron(II) phosphate vivianite, Fe3(PO4)2,8H2O, from a solution of Mohr's salt, Fe(NH4)2(SO4)2,6H2O, added to a solution of ammonium phosphate, hydroxylammonium chloride, NH3OHCl, was added to the iron(II) stock solution to eliminate oxidation of iron(II) by oxygen from the air. However, the effect turned out to be the opposite of the expected: whereas hydroxylamine reduces iron(III) in bulk solution, it acted as a strong oxidant in the presence of growing iron phosphate crystals, causing the crystallization of the iron(III) phosphate strengite, FePO4,2H2O, as the only solid phase. Evidently the crystal surface catalyses oxidation of iron(II) by hydroxylamine. The usual composite kinetics of spiral growth and surface nucleation was found. The surface-nucleation part yielded edge free energy λ in the range 12-45 pJ/m, virtually independent of temperature and in the range typical for phosphates of divalent metals. The scatter of values for λ presumably arises from contributions from different crystal forms to the overall growth rate. The low mean value points to strong adsorption of iron(II), which is subsequently oxidized at the crystal surface, forming strengite. The state of the system did not tend to thermodynamic equilibrium, but to a metastable state, presumably controlled by the iron(II) rich surface layer of the crystal. In addition to crystal growth, it was possible to measure nucleation kinetics by light scattering (turbidimetry). A point of transition from heterogeneous to homogeneous nucleation was found, and from the results for the homogeneous domain a rather precise value of crystal surface free energy γ=55 mJ/m2 was found. This is a relatively low value as well, indicating that the redox process plays a role already at the nucleation stage.

Kinetics of steel slag leaching: Batch tests and modeling

DOE Office of Scientific and Technical Information (OSTI.GOV)

De Windt, Laurent, E-mail: laurent.dewindt@mines-paristech.fr; Chaurand, Perrine; Rose, Jerome

2011-02-15

Reusing steel slag as an aggregate for road construction requires to characterize the leaching kinetics and metal releases. In this study, basic oxygen furnace (BOF) steel slag were subjected to batch leaching tests at liquid to solid ratios (L/S) of 10 and 100 over 30 days; the leachate chemistry being regularly sampled in time. A geochemical model of the steel slag is developed and validated from experimental data, particularly the evolution with leaching of mineralogical composition of the slag and trace element speciation. Kinetics is necessary for modeling the primary phase leaching, whereas a simple thermodynamic equilibrium approach can bemore » used for secondary phase precipitation. The proposed model simulates the kinetically-controlled dissolution (hydrolysis) of primary phases, the precipitation of secondary phases (C-S-H, hydroxide and spinel), the pH and redox conditions, and the progressive release of major elements as well as the metals Cr and V. Modeling indicates that the dilution effect of the L/S ratio is often coupled to solubility-controlled processes, which are sensitive to both the pH and the redox potential. A sensitivity analysis of kinetic uncertainties on the modeling of element releases is performed.« less

Speciation and characterization of arsenic in Ketza River mine tailings using X-ray absorption spectroscopy.

PubMed

Paktunc, Dogan; Foster, Andrea; Laflamme, Gilles

2003-05-15

Ketza River mine tailings deposited underwater and those exposed near the tailings impoundment contain approximately 4 wt % As. Column-leaching tests indicated the potential for high As releases from the tailings. The tailings are composed dominantly of iron oxyhydroxides, quartz, calcite, dolomite, muscovite, ferric arsenates, and calcium-iron arsenates. Arsenopyrite and pyrite are trace constituents. Chemical compositions of iron oxyhydroxide and arsenate minerals are highly variable. The XANES spectra indicate that arsenic occurs as As(V) in tailings, but air-drying prior to analysis may have oxidized lower-valent As. The EXAFS spectra indicate As-Fe distances of 3.35-3.36 A for the exposed tailings and 3.33-3.35 A for the saturated tailings with coordination numbers of 0.96-1.11 and 0.46-0.64, respectively. The As-Ca interatomic distances ranging from 4.15 to 4.18 A and the coordination numbers of 4.12-4.58 confirm the presence of calcium-iron arsenates in the tailings. These results suggest that ferric arsenates and inner-sphere corner sharing or bidentate-binuclear attachment of arsenate tetrahedra onto iron hydroxide octahedra are the dominant form of As in the tailings. EXAFS spectra indicate that the exposed tailings are richer in arsenate minerals whereas the saturated tailings are dominated by the iron oxyhydroxides, which could help explain the greater release of As from the exposed tailings during leaching tests. It is postulated that the dissolution of ferric arsenates during flow-through experiments caused the high As releases from both types of tailings. Arsenic tied to iron oxyhydroxides as adsorbed species are considered stable; however, iron oxyhydroxides having low Fe/As molar ratios may not be as stable. Continued As releases from the tailings are likely due to dissolution of both ferric and calcium-iron arsenates and desorption of As from high-As bearing iron oxyhydroxides during aging.

Speciation and characterization of arsenic in Ketza River mine tailings using x-ray absorption spectroscopy

USGS Publications Warehouse

Paktunc, D.; Foster, A.; Laflamme, G.

2003-01-01

Ketza River mine tailings deposited underwater and those exposed near the tailings impoundment contain approximately 4 wt % As. Column-leaching tests indicated the potential for high As releases from the tailings. The tailings are composed dominantly of iron oxyhydroxides, quartz, calcite, dolomite, muscovite, ferric arsenates, and calcium-iron arsenates. Arsenopyrite and pyrite are trace constituents. Chemical compositions of iron oxyhydroxide and arsenate minerals are highly variable. The XANES spectra indicate that arsenic occurs as As(V) in tailings, but air-drying prior to analysis may have oxidized lower-valent As. The EXAFS spectra indicate As-Fe distances of 3.35-3.36 A?? for the exposed tailings and 3.33-3.35 A?? for the saturated tailings with coordination numbers of 0.96-1.11 and 0.46-0.64, respectively. The As-Ca interatomic distances ranging from 4.15 to 4.18 A?? and the coordination numbers of 4.12-4.58 confirm the presence of calcium-iron arsenates in the tailings. These results suggest that ferric arsenates and inner-sphere corner sharing or bidentatebinuclear attachment of arsenate tetrahedra onto iron hydroxide octahedra are the dominant form of As in the tailings. EXAFS spectra indicate that the exposed tailings are richer in arsenate minerals whereas the saturated tailings are dominated by the iron oxyhydroxides, which could help explain the greater release of As from the exposed tailings during leaching tests. It is postulated that the dissolution of ferric arsenates during flow-through experiments caused the high As releases from both types of tailings. Arsenic tied to iron oxyhydroxides as adsorbed species are considered stable; however, iron oxyhydroxides having low Fe/As molar ratios may not be as stable. Continued As releases from the tailings are likely due to dissolution of both ferric and calcium-iron arsenates and desorption of As from high-As bearing iron oxyhydroxides during aging.

Speciation and Localization of Arsenic in White and Brown Rice Grains

DOE Office of Scientific and Technical Information (OSTI.GOV)

Meharg, Andrew A.; Lombi, Enzo; Williams, Paul N.

2008-06-30

Synchrotron-based X-ray fluorescence (S-XRF) was utilized to locate arsenic (As) in polished (white) and unpolished (brown) rice grains from the United States, China, and Bangladesh. In white rice As was generally dispersed throughout the grain, the bulk of which constitutes the endosperm. In brown rice As was found to be preferentially localized at the surface, in the region corresponding to the pericarp and aleurone layer. Copper, iron, manganese, and zinc localization followed that of arsenic in brown rice, while the location for cadmium and nickel was distinctly different, showing relatively even distribution throughout the endosperm. The localization of As inmore » the outer grain of brown rice was confirmed by laser ablation ICP?MS. Arsenic speciation of all grains using spatially resolved X-ray absorption near edge structure (?-XANES) and bulk extraction followed by anion exchange HPLC?ICP?MS revealed the presence of mainly inorganic As and dimethylarsinic acid (DMA). However, the two techniques indicated different proportions of inorganic:organic As species. A wider survey of whole grain speciation of white (n = 39) and brown (n = 45) rice samples from numerous sources (field collected, supermarket survey, and pot trials) showed that brown rice had a higher proportion of inorganic arsenic present than white rice. Furthermore, the percentage of DMA present in the grain increased along with total grain arsenic.« less

A counterflow diffusion flame study of branched octane isomers

DOE PAGES

Sarathy, S. Mani; Niemann, Ulrich; Yeung, Coleman; ...

2012-09-25

Conventional petroleum, Fischer–Tropsch (FT), and other alternative hydrocarbon fuels typically contain a high concentration of lightly methylated iso-alkanes. However, until recently little work has been done on this important class of hydrocarbon components. In order to better understand the combustion characteristics of real fuels, this study presents new experimental data for 3-methylheptane and 2,5-dimethylhexane in counterflow diffusion flames. This new dataset includes flame ignition, extinction, and speciation profiles. The high temperature oxidation of these fuels has been modeled using an extended transport database and a high temperature skeletal chemical kinetic model. The skeletal model is generated from a detailed modelmore » reduced using the directed relation graph with expert knowledge (DRG-X) methodology. The proposed skeletal model contains sufficient chemical fidelity to accurately predict the experimental speciation data in flames. The predictions are compared to elucidate the effects of number and location of the methyl substitutions. The location is found to have little effect on ignition and extinction in these counterflow diffusion flames. However, increasing the number of methyl substitutions was found to inhibit ignition and promote extinction. Chemical kinetic modelling simulations were used to correlate a fuel’s extinction propensity with its ability to populate the H radical concentration. In conclusion, species composition measurements indicate that the location and number of methyl substitutions was found to particularly affect the amount and type of alkenes observed.« less

Combustion Chemistry of Fuels: Quantitative Speciation Data Obtained from an Atmospheric High-temperature Flow Reactor with Coupled Molecular-beam Mass Spectrometer.

PubMed

Köhler, Markus; Oßwald, Patrick; Krueger, Dominik; Whitside, Ryan

2018-02-19

This manuscript describes a high-temperature flow reactor experiment coupled to the powerful molecular beam mass spectrometry (MBMS) technique. This flexible tool offers a detailed observation of chemical gas-phase kinetics in reacting flows under well-controlled conditions. The vast range of operating conditions available in a laminar flow reactor enables access to extraordinary combustion applications that are typically not achievable by flame experiments. These include rich conditions at high temperatures relevant for gasification processes, the peroxy chemistry governing the low temperature oxidation regime or investigations of complex technical fuels. The presented setup allows measurements of quantitative speciation data for reaction model validation of combustion, gasification and pyrolysis processes, while enabling a systematic general understanding of the reaction chemistry. Validation of kinetic reaction models is generally performed by investigating combustion processes of pure compounds. The flow reactor has been enhanced to be suitable for technical fuels (e.g. multi-component mixtures like Jet A-1) to allow for phenomenological analysis of occurring combustion intermediates like soot precursors or pollutants. The controlled and comparable boundary conditions provided by the experimental design allow for predictions of pollutant formation tendencies. Cold reactants are fed premixed into the reactor that are highly diluted (in around 99 vol% in Ar) in order to suppress self-sustaining combustion reactions. The laminar flowing reactant mixture passes through a known temperature field, while the gas composition is determined at the reactors exhaust as a function of the oven temperature. The flow reactor is operated at atmospheric pressures with temperatures up to 1,800 K. The measurements themselves are performed by decreasing the temperature monotonically at a rate of -200 K/h. With the sensitive MBMS technique, detailed speciation data is acquired and quantified for almost all chemical species in the reactive process, including radical species.

Steel Wool and Oxygen: A Look at Kinetics

ERIC Educational Resources Information Center

Gordon, James; Chancey, Katherine

2005-01-01

An experiment is demonstrated to determine the percentage of oxygen in air using a pretreated piece of steel wool, which is an alternative to spectroscopic kinetic analysis. Students are able to determine the order of reaction for oxygen in its reaction with the iron in steel wool, and are able to use the existing technology to collect and analyze…

KINETICS OF TRICHLOROETHENE REDUCTION BY ZEROVALENT IRON AND TIN: PRETREATMENT EFFECT, APPARENT ACTIVATION ENERGY, AND INTERMEDIATE PRODUCTS

EPA Science Inventory

The degradation of trichloroethene (TCE) at 2 mg L-1 in headspace free aqueous solution by zerovalent iron (Feo) and tin (Sno) was studied in batch tests at 10, 25, 40, and 55 degrees C and HCI-treated Feo and Sno at 25 and 55 degrees C. The HCI-washing increased metal surface a...

Manganese and iron geochemistry in sediments underlying the redox-stratified Fayetteville Green Lake

NASA Astrophysics Data System (ADS)

Herndon, Elizabeth M.; Havig, Jeff R.; Singer, David M.; McCormick, Michael L.; Kump, Lee R.

2018-06-01

Manganese and iron are redox-sensitive elements that yield clues about biogeochemistry and redox conditions both in modern environments and in the geologic past. Here, we investigated Mn and Fe-bearing minerals preserved in basin sediments underlying Fayetteville Green Lake, a redox-stratified lake that serves as a geochemical analogue for Paleoproterozoic oceans. Synchrotron-source microprobe techniques (μXRF, μXANES, and μXRD) and bulk geochemical analyses were used to examine the microscale distribution and speciation of Mn, Fe, and S as a function of depth in the top 48 cm of anoxic lake sediments. Manganese was primarily associated with calcite grains as a manganese-rich carbonate that precipitated in the chemocline of the water column and settled through the euxinic basin to collect in lake sediments. Iron was preserved in framboidal iron sulfides that precipitated in euxinic bottom waters and underwent transformation to pyrite and marcasite in the sediments. Previous studies attribute the formation of manganese-rich carbonates to the diagenetic alteration of manganese oxides deposited in basins underlying oxygenated water. Our study challenges this paradigm by providing evidence that Mn-bearing carbonates form in the water column and accumulate in sediments below anoxic waters. Consequently, manganoan carbonates preserved in the rock record do not necessarily denote the presence of oxygenated bottom waters in ocean basins.

Can sediments at hydrocarbon seep sites represent a source for marine bioavailable iron? — A case study from the South China Sea

NASA Astrophysics Data System (ADS)

Li, N.; Feng, D.; Chen, D.

2017-12-01

Niu Li1, Dong Feng1,2, and Duofu Chen2,31CAS Key Laboratory of Ocean and Marginal Sea Geology, South China Sea Institute of Oceanology, Chinese Academy of Sciences, Guangzhou 510301, China. 2Laboratory for Marine Geology, Qingdao National Laboratory for Marine Science and Technology, Qingdao 266061, China. 3Hadal Science and Technology Research Center, College of Marine Sciences, Shanghai Ocean University, Shanghai 201306, China. Iron is an essential micronutrient and commonly considered to be one of the key-limiting factors for biological productivity in many ocean regions. Seafloor Fe supply should be most efficient in suboxic conditions. Recent studies shown that widely spread anoxic environments can develop in hydrocarbon seep sediment and local bottom water, owing to the occurrence of aerobic and/or anaerobic methane oxidation. Under this condition, the iron in sediment can be reduced to dissolved Fe2+ in the ocean. However, questions remain about whether the hydrocarbon seep sediment can represent a source for bioavailable iron to the ocean, and the control factor for the transformation of iron in the sediment remains largely unexplored. For a number of hydrocarbon seeps from the northern and southern South China Sea, the iron speciation, pyrite sulfur isotope, and iron isotope, as well as the major and trace elements are used to constrain the intensity of cold seep, and its impact on transformation of iron in sediment. Samples from both areas show sediment iron lost during the high methane flux conditions, owing to the suboxic conditions cause by aerobic methane oxidation. On the other hand, high sediment iron content accompanied by high sulfur content can be seen during the conditions of high methane flux without the occurrence of aerobic methane oxidation, which is possible ascribed to the anaerobic methane oxidation and the release of iron through seep activity. This study reveals the transformation of iron in the sediment is closely related to the methane flux and the hydrocarbon seep sediment can represent a source for bioavailable iron to the ocean. Acknowledgments: Funding was provided by the NSF of China (Grants: 41422602 and 41373085).

Tungsten speciation in sulfidic waters: Stability and lability of thiotungstates

NASA Astrophysics Data System (ADS)

Cui, M.; Johannesson, K. H.

2017-12-01

Tungsten (W) is an important metal that has been widely used in industries. It normally occurs as the monomeric tungstate oxyanion in circumneutral to alkaline pH natural waters but tends to form polytungstates species at low pH and high W concentrations. A number of studies show that W is strongly correlated with dissolved sulfide in natural waters. Laboratory investigations have presented evidence that, like Mo, W undergoes sulfidation in four steps that conserve tungstate and lead to the formation of tetrathiotungstate. In addition, natural waters may be seasonally anoxic, thus W speciation is likely to be kinetically controlled. Our previous studies showed that the speciation of tungsten is important in controlling its fate and transport in natural waters. Thiotungstate and tungstate are adsorbed differently to the mineral surfaces such as goethite and pyrite. In our present study, we have observed that the sulfidation reactions of W are acid catalyzed. We suggest that in environments such as sediment porewaters, the presence of Brønsted acids, will promote conversion of tungstate to thiotungstates. However, the conversion of the predominant anion from a hard to a soft base alters W's geochemical behavior, increasing its susceptibility to scavenging. Thus, an important product of this research will be an improved understanding of the scavenging pathways of W in euxinic environments.

Multistep Reduction Kinetics of Fine Iron Ore with Carbon Monoxide in a Micro Fluidized Bed Reaction Analyzer

NASA Astrophysics Data System (ADS)

Chen, Hongsheng; Zheng, Zhong; Chen, Zhiwei; Yu, Wenzhou; Yue, Junrong

2017-04-01

The reduction kinetics of Brazilian hematite by CO is investigated in a Micro Fluidized Bed Reaction Analyzer (MFBRA) using an analyzing method based on Johnson-Mehl-Avrami (JMA) model at temperatures of 973 K (700 °C), 1023 K (750 °C), 1073 K (800 °C), and 1123 K (850 °C). The solid products at different reduction stages are evaluated by SEM/EDS and XRD technologies. Results indicate that the reduction process is better to be discussed in terms of a parallel reaction model that consists of the reactions of hematite to wüstite and wüstite to iron, rather than a stepwise route. Meanwhile, the controlling mechanism of the reduction process is found to vary with temperature and the degree of conversion. The overall process is controlled by the gas-solid reaction occurring at the iron/wüstite interface in the initial stages, and then is limited by the nucleation of wüstite, and finally shifts to diffusion control. Moreover, the reactions of hematite to wüstite and wüstite to iron take place simultaneously but with different time dependences, and the apparent activation energies of hematite to wüstite and wüstite to iron are determined as 83.61 and 80.40 KJ/mol, respectively.

Studies on the reduction kinetics of hematite iron ore pellets with noncoking coals for sponge iron plants

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kumar, M.; Mohapatra, P.; Patel, S.K.

2009-07-01

In the present investigation, fired pellets were made by mixing hematite iron ore fines of -100, -16+18, and -8+10 mesh size in different ratios and studies on their reduction kinetics in Lakhanpur, Orient OC-2 and Belpahar coals were carried out at temperatures ranging from 850{sup o}C to 1000{sup o}C with a view toward promoting the massive utilization of fines in ironmaking. The rate of reduction in all the fired iron ore pellets increased markedly with an increase in temperature up to 1000{sup o}C, and it was more intense in the first 30min. The values of activation energy, calculated from integralmore » and differential approaches, for the reduction of fired pellets (prepared from iron ore fines of -100 mesh size) in coals were found to be in the range 131-148 and 130-181 kJ mol{sup -1} (for =0.2 to 0.8), indicating the process is controlled by a carbon gasification reaction. The addition of selected larger size particles in the matrix of -100 mesh size fines up to the extent studied decreased the activation energy and slightly increased the reduction rates of resultant fired pellets. In comparison to coal, the reduction of fired pellets in char was characterized by significantly lower reduction rates and higher activation energy.« less

Role of a gas phase in the kinetics of zinc and iron reduction with carbon from slag melts

NASA Astrophysics Data System (ADS)

Chumarev, V. M.; Selivanov, E. N.

2013-03-01

The influence of the mass transfer conditions in the gas phase having formed at the carbon-slag melt interface on CO regeneration is approximately estimated in the framework of a two-stage scheme of metal reduction from slag melts by carbon. The effect of zinc vapors on the combined reduction of iron and zinc from slags is considered. The influence of the slag composition and temperature on the critical concentration of zinc oxide above which no iron forms as an individual phase is explained.

Investigation of the Iron(II) Release Mechanism of Human H-Ferritin as a Function of pH.

PubMed

Sala, Davide; Ciambellotti, Silvia; Giachetti, Andrea; Turano, Paola; Rosato, Antonio

2017-09-25

We investigated the kinetics of the release of iron(II) ions from the internal cavity of human H-ferritin as a function of pH. Extensive molecular dynamics simulations of the entire 24-mer ferritin provided atomic-level information on the release mechanism. Double protonation of His residues at pH 4 facilitates the removal of the iron ligands within the C3 channel through the formation of salt bridges, resulting in a significantly lower release energy barrier than pH 9.

Nanostructures nucleation in carbon-metal gaseous phase: A molecular dynamics study

NASA Astrophysics Data System (ADS)

Galiullina, G. M.; Orekhov, N. D.; Stegailov, V. V.

2018-01-01

We perform nonequilibrium molecular dynamics simulation of carbon nanoclusters nucleation and early stages of growth from the gaseous phase. We analyze the catalytic effect of iron atoms on the nucleation kinetics and structure of the resultant nanoparticles. Reactive Force Field (ReaxFF) is used in the simulations for the description of bond formation and dissociation during the nucleation process at the nanoscale. The catalytic effect of iron reveals itself even on nanosecond simulation times: iron atoms accelerate the process of clustering but result in less graphitized carbon structures.

Equilibrium and kinetics of adsorption of phosphate onto iron-doped activated carbon.

PubMed

Wang, Zhengfang; Nie, Er; Li, Jihua; Yang, Mo; Zhao, Yongjun; Luo, Xingzhang; Zheng, Zheng

2011-08-01

Two series of activated carbons modified by Fe (II) and Fe (III) (denoted as AC/N-Fe(II) and AC/N-Fe(III)), respectively, were used as adsorbents for the removal of phosphate in aqueous solutions. The synthesized adsorbent materials were investigated by different experimental analysis means. The adsorption of phosphate on activated carbons has been studied in kinetic and equilibrium conditions taking into account the adsorbate concentration, temperature, and solution pH as major influential factors. Maximum removals of phosphate are obtained in the pH range of 3.78-6.84 for both adsorbents. Langmuir isotherm adsorption equation well describes the experimental adsorption isotherms. Kinetic studies revealed that the adsorption process followed a pseudo-second order kinetic model. Results suggest that the main phase formed in AC/N-Fe(II) and AC/N-Fe(III) is goethite and akaganeite, respectively; the presence of iron oxides significantly affected the surface area and the pore structure of the activated carbon. Studies revealed that iron-doped activated carbons were effective in removing phosphate. AC/N-Fe(II) has a higher phosphate removal capacity than AC/N-Fe(III), which could be attributed to its better intra-particle diffusion and higher binding energy. The activation energy for adsorption was calculated to be 22.23 and 10.89 kJ mol(-1) for AC/N-Fe(II) and AC/N-Fe(III), respectively. The adsorption process was complex; both surface adsorption and intra-particle diffusion were simultaneously occurring during the process and contribute to the adsorption mechanism.

Impact of carbon, oxygen and sulfur content of microscale zerovalent iron particles on its reactivity towards chlorinated aliphatic hydrocarbons.

PubMed

Velimirovic, Milica; Larsson, Per-Olof; Simons, Queenie; Bastiaens, Leen

2013-11-01

Zerovalent iron (ZVI) abiotically degrades several chlorinated aliphatic hydrocarbons (CAHs) via reductive dechlorination, which offers perspectives for in situ groundwater remediation applications. The difference in reactivity between ZVI particles is often linked with their specific surface area. However, other parameters may influence the reactivity as well. Earlier, we reported for a set of microscale zerovalent iron (mZVI) particles the disappearance kinetic of different CAHs which were collected under consistent experimental conditions. In the present study, these kinetic data were correlated with the carbon, oxygen and sulfur content of mZVI particles. It was confirmed that not only the specific surface area affects the disappearance kinetic of CAHs, but also the chemical composition of the mZVI particles. The chemical composition, in addition, influences CAHs removal mechanism inducing sorption onto mZVI particles instead of dechlorination. Generally, high disappearance kinetic of CAHs was observed for particles containing less oxygen. A high carbon content, on the other hand, induced nonreactive sorption of the contaminants on the mZVI particles. To obtain efficient remediation of CAHs by mZVI particles, this study suggested that the carbon and oxygen content should not exceed 0.5% and 1% respectively. Finally, the efficiency of the mZVI particles may be improved to some extent by enriching them with sulfur. However, the impact of sulfur content on the reactivity of mZVI particles is less pronounced than that of the carbon and oxygen content. Copyright © 2013 Elsevier Ltd. All rights reserved.

METABOLISM OF IRON STORES

PubMed Central

SAITO, HIROSHI

2014-01-01

ABSTRACT Remarkable progress was recently achieved in the studies on molecular regulators of iron metabolism. Among the main regulators, storage iron, iron absorption, erythropoiesis and hepcidin interact in keeping iron homeostasis. Diseases with gene-mutations resulting in iron overload, iron deficiency, and local iron deposition have been introduced in relation to the regulators of storage iron metabolism. On the other hand, the research on storage iron metabolism has not advanced since the pioneering research by Shoden in 1953. However, we recently developed a new method for determining ferritin iron and hemosiderin iron by computer-assisted serum ferritin kinetics. Serum ferritin increase or decrease curves were measured in patients with normal storage iron levels (chronic hepatitis C and iron deficiency anemia treated by intravenous iron injection), and iron overload (hereditary hemochromatosis and transfusion dependent anemia). We thereby confirmed the existence of two iron pathways where iron flows followed the numbered order (1) labile iron, (2) ferritin and (3) hemosiderin in iron deposition and mobilization among many previously proposed but mostly unproven routes. We also demonstrated the increasing and decreasing phases of ferritin iron and hemosiderin iron in iron deposition and mobilization. The author first demonstrated here the change in proportion between pre-existing ferritin iron and new ferritin iron synthesized by removing iron from hemosiderin in the course of iron removal. In addition, the author disclosed the cause of underestimation of storage iron turnover rate which had been reported by previous investigators in estimating storage iron turnover rate of normal subjects. PMID:25741033

DOE Office of Scientific and Technical Information (OSTI.GOV)

Swanner, E. D.; Bayer, T.; Wu, W.

In this study, we couple iron isotope analysis to microscopic and mineralogical investigation of iron speciation during circumneutral Fe(II) oxidation and Fe(III) precipitation with photosynthetically produced oxygen. In the presence of the cyanobacterium Synechococcus PCC 7002, aqueous Fe(II) (Fe(II) aq) is oxidized and precipitated as amorphous Fe(III) oxyhydroxide minerals (iron precipitates, Fe ppt), with distinct isotopic fractionation (ε 56Fe) values determined from fitting the δ 56Fe(II) aq (1.79‰ and 2.15‰) and the δ 56Fe ppt (2.44‰ and 2.98‰) data trends from two replicate experiments. Additional Fe(II) and Fe(III) phases were detected using microscopy and chemical extractions and likely represent Fe(II)more » and Fe(III) sorbed to minerals and cells. The iron desorbed with sodium acetate (FeNaAc) yielded heavier δ 56Fe compositions than Fe(II) aq. Modeling of the fractionation during Fe(III) sorption to cells and Fe(II) sorption to Feppt, combined with equilibration of sorbed iron and with Fe(II) aq using published fractionation factors, is consistent with our resulting δ 56FeNaAc. The δ 56Fe ppt data trend is inconsistent with complete equilibrium exchange with Fe(II)aq. Because of this and our detection of microbially excreted organics (e.g., exopolysaccharides) coating Feppt in our microscopic analysis, we suggest that electron and atom exchange is partially suppressed in this system by biologically produced organics. These results indicate that cyanobacteria influence the fate and composition of iron in sunlit environments via their role in Fe(II) oxidation through O 2 production, the capacity of their cell surfaces to sorb iron, and the interaction of secreted organics with Fe(III) minerals.« less

Influence of iron redox cycling on organo-mineral associations in arctic tundra soils

NASA Astrophysics Data System (ADS)

Herndon, E.; AlBashaireh, A.; Duroe, K.; Singer, D. M.

2016-12-01

Geochemical interactions between soil organic matter and minerals influence decomposition in many environments but remain poorly understood in arctic tundra systems. In tundra soils that are periodically to persistently saturated, the accumulation of iron oxyhydroxides and organo-iron precipitates at redox interfaces may inhibit decomposition by binding organic molecules and protecting them from microbial degradation. Here, we couple synchrotron-source spectroscopic techniques with chemical sequential extractions and physical density fractionations to evaluate the spatial distribution and speciation of Fe-bearing phases and associated organic matter in organic and mineral horizons of the seasonally thawed active layer in tundra soils from northern Alaska. Mineral-associated organic matter comprised 63 ± 9% of soil organic carbon stored in the active layer of ice wedge polygons. Ferrous iron produced in anoxic mineral horizons diffused upwards and precipitated as poorly-crystalline oxyhydroxides and organic-bound Fe(III) in the organic horizons. Ferrihydrite and goethite were present as coatings on mineral grains and plant debris and in aggregates with clays and particulate organic matter. Organic matter released through acid-dissolution of iron oxides may represent a small pool of readily-degradable organic molecules temporarily stabilized by sorption to iron oxyhydroxide surfaces, while larger quantities of particulate organic carbon and humic-like substances may be physically protected from decomposition by Fe-oxide coatings and aggregation. We conclude that formation of poorly-crystalline and crystalline iron oxides at redox interfaces contributes to mineral protection of organic matter through sorption, aggregation, and co-precipitation reactions. Further study of organo-mineral associations is necessary to determine the net impact of mineral-stabilization on carbon storage in rapidly warming arctic ecosystems.

Quantification of ferritin bound iron in human serum using species-specific isotope dilution mass spectrometry.

PubMed

Ren, Yao; Walczyk, Thomas

2014-09-01

Ferritin is a hollow sphere protein composed of 24 subunits that can store up to 4500 iron atoms in its inner cavity. It is mainly found in the liver and spleen but also in serum at trace levels. Serum ferritin is considered as the best single indicator in assessing body iron stores except liver or bone marrow biopsy. However, it is confounded by other disease conditions. Ferritin bound iron (FBI) and ferritin saturation have been suggested as more robust biomarkers. The current techniques for FBI determination are limited by low antibody specificity, low instrument sensitivity and possible analyte losses during sample preparation. The need for a highly sensitive and reliable method is widely recognized. Here we describe a novel technique to detect serum FBI using species-specific isotope dilution mass spectrometry (SS-IDMS). [(57)Fe]-ferritin was produced by biosynthesis and in vitro labeling with the (57)Fe spike in the form of [(57)Fe]-citrate after cell lysis and heat treatment. [(57)Fe]-ferritin for sample spiking was further purified by fast liquid protein chromatography. Serum ferritin and added [(57)Fe]-ferritin were separated from other iron species by ultrafiltration followed by isotopic analysis of FBI using negative thermal ionization mass spectrometry. Repeatability of our assay is 8% with an absolute detection limit of 18 ng FBI in the sample. As compared to other speciation techniques, SS-IDMS offers maximum control over sample losses and species conversion during analysis. The described technique may therefore serve as a reference technique for clinical applications of FBI as a new biomarker for assessing body iron status.

Stability of oxidized iron species and the redox budget of slab-derived fluids

NASA Astrophysics Data System (ADS)

Sanchez-Valle, C.; Hin, R.; Testemale, D.; Borca, C.; Grolimund, D.

2017-12-01

The high oxidation state of subduction zone magmas compared to magmas from other locations might result from the influx of oxidized fluid from the subducted oceanic plate into the mantle wedge. However, the nature of the chemical agent(s) and the mechanism responsible for the transfer of the oxidized signature from the slab to the mantle wedge remains poorly understood. In this contribution, we will discuss the oxidizing capacity of slab-derived fluids in the light of experimental results of the solubility and speciation of iron in high-pressure fluids that mimic the slab flux. Iron-bearing mineral assemblages were equilibrated with chlorinated aqueous fluids and hydrous granitic melts at different oxygen fugacities relevant for the present day crust/mantle. The concentration of iron and the distribution of stability of oxidized iron species were monitored up to 2.5 GPa and 800 °C using a combination of diamond trap experiments and XANES measurements in diamond anvil cells. The results illustrate the role of coordination chemistry involving halogen and polymerized species in the stability of oxidized iron in the fluids. The concentration of Fe3+ in the fluids progressively decreases as temperature increases, regardless of fluid composition and pressure. This implies that the fluid capacity to transport Fe3+ at high temperature may be limited, even at the redox conditions relevant for the present day crust and mantle. With the new experimental results, we place constrains on the oxidizing capacity of Fe-bearing metasomatic fluids and discuss the transfer of the oxidizing signature and the conditions for the genesis of oxidized arc magmas.

Laser Flash Photolysis Generation of High-Valent Transition Metal-Oxo Species: Insights from Kinetic Studies in Real Time

PubMed Central

Zhang, Rui; Newcomb, Martin

2010-01-01

Conspectus High-valent transition metal-oxo species are active oxidizing species in many metal-catalyzed oxidation reactions in both Nature and the laboratory. In homogeneous catalytic oxidations, a transition metal catalyst is oxidized to a metal-oxo species by a sacrificial oxidant, and the activated transition metal-oxo intermediate oxidizes substrates. Mechanistic studies of these oxidizing species can provide insights for understanding commercially important catalytic oxidations and the oxidants in cytochrome P450 enzymes. In many cases, however, the transition metal oxidants are so reactive that they do not accumulate to detectable levels in mixing experiments, which have millisecond mixing times, and successful generation and direct spectroscopic characterization of these highly reactive transients remain a considerable challenge. Our strategy for understanding homogeneous catalysis intermediates employs photochemical generation of the transients with spectroscopic detection on time-scales as short as nanoseconds and direct kinetic studies of their reactions with substrates by laser flash photolysis (LFP) methods. This Account describes studies of high-valent manganese- and iron-oxo intermediates. Irradiation of porphyrin-manganese(III) nitrates and chlorates or corrole-manganese(IV) chlorates resulted in homolytic cleavage of the O-X bonds in the ligands, whereas irradiation of porphyrin-manganese(III) perchlorates resulted in heterolytic cleavage of O-Cl bonds to give porphyrin-manganese(V)-oxo cations. Similar reactions of corrole- and porphyrin-iron(IV) complexes gave highly reactive transients that were tentatively identified as macrocyclic ligand-iron(V)-oxo species. Kinetic studies demonstrated high reactivity of the manganese(V)-oxo species, and even higher reactivities of the putative iron(V)-oxo transients. For example, second-order rate constants for oxidations of cis-cyclooctene at room temperature were 6 × 103 M−1 s−1 for a corrole-iron(V)-oxo species and 1.6 × 106 M−1 s−1 for the putative tetramesitylporphyrin-iron(V)-oxo perchlorate species. The latter rate constant is 25,000 times larger than that for oxidation of cis-cyclooctene by iron(IV)-oxo perchlorate tetramesitylporphyrin radical cation, which is the thermodynamically favored electronic isomer of the putative iron(V)-oxo species. The LFP-determined rate constants can be used to implicate the transient oxidants in catalytic reactions under turnover conditions where high-valent species are not observable. Similarly, the observed reactivities of the putative porphyrin-iron(V)-oxo species might explain the unusually high reactivity of oxidants produced in the cytochrome P450 enzymes, heme-thiolate enzymes that are capable of oxidizing unactivated carbon-hydrogen bonds in substrates so rapidly that iron-oxo intermediates have not been detected under physiological conditions. PMID:18278877

Laser flash photolysis generation of high-valent transition metal-oxo species: insights from kinetic studies in real time.

PubMed

Zhang, Rui; Newcomb, Martin

2008-03-01

High-valenttransition metal-oxo species are active oxidizing species in many metal-catalyzed oxidation reactions in both Nature and the laboratory. In homogeneous catalytic oxidations, a transition metal catalyst is oxidized to a metal-oxo species by a sacrificial oxidant, and the activated transition metal-oxo intermediate oxidizes substrates. Mechanistic studies of these oxidizing species can provide insights for understanding commercially important catalytic oxidations and the oxidants in cytochrome P450 enzymes. In many cases, however, the transition metal oxidants are so reactive that they do not accumulate to detectable levels in mixing experiments, which have millisecond mixing times, and successful generation and direct spectroscopic characterization of these highly reactive transients remain a considerable challenge. Our strategy for understanding homogeneous catalysis intermediates employs photochemical generation of the transients with spectroscopic detection on time scales as short as nanoseconds and direct kinetic studies of their reactions with substrates by laser flash photolysis (LFP) methods. This Account describes studies of high-valent manganese- and iron-oxo intermediates. Irradiation of porphyrin-manganese(III) nitrates and chlorates or corrole-manganese(IV) chlorates resulted in homolytic cleavage of the O-X bonds in the ligands, whereas irradiation of porphyrin-manganese(III) perchlorates resulted in heterolytic cleavage of O-Cl bonds to give porphyrin-manganese(V)-oxo cations. Similar reactions of corrole- and porphyrin-iron(IV) complexes gave highly reactive transients that were tentatively identified as macrocyclic ligand-iron(V)-oxo species. Kinetic studies demonstrated high reactivity of the manganese(V)-oxo species, and even higher reactivities of the putative iron(V)-oxo transients. For example, second-order rate constants for oxidations of cis-cyclooctene at room temperature were 6 x 10(3) M(-1) s(-1) for a corrole-iron(V)-oxo species and 1.6 x 10(6) M(-1) s(-1) for the putative tetramesitylporphyrin-iron(V)-oxo perchlorate species. The latter rate constant is 25,000 times larger than that for oxidation of cis-cyclooctene by iron(IV)-oxo perchlorate tetramesitylporphyrin radical cation, which is the thermodynamically favored electronic isomer of the putative iron(V)-oxo species. The LFP-determined rate constants can be used to implicate the transient oxidants in catalytic reactions under turnover conditions where high-valent species are not observable. Similarly, the observed reactivities of the putative porphyrin-iron(V)-oxo species might explain the unusually high reactivity of oxidants produced in the cytochrome P450 enzymes, heme-thiolate enzymes that are capable of oxidizing unactivated carbon-hydrogen bonds in substrates so rapidly that iron-oxo intermediates have not been detected under physiological conditions.

Reactive Transport of Petroleum Hydrocarbon Constituents in a Shallow Aquifer: Modeling Geochemical Interactions Between Organic and Inorganic Species

NASA Astrophysics Data System (ADS)

McNab, W. W.; Narasimhan, T. N.

1995-08-01

Dissolved organic contaminants such as petroleum hydrocarbon constituents are often observed to degrade in groundwater environments through biologically mediated transformation reactions into carbon dioxide, methane, or intermediate organic compounds. Such transformations are closely tied to local geochemical conditions. Favorable degradation pathways depend upon local redox conditions through thermodynamic constraints and the availability of appropriate mediating microbial populations. Conversely, the progress of the degradation reactions may affect the chemical composition of groundwater through changes in electron donor/acceptor speciation and pH, possibly inducing mineral precipitation/dissolution reactions. Transport of reactive organic and inorganic aqueous species through open systems may enhance the reaction process by mixing unlike waters and producing a state of general thermodynamic disequilibrium. In this study, field data from an aquifer contaminated by petroleum hydrocarbons have been analyzed using a mathematical model which dynamically couples equilibrium geochemistry of inorganic constituents, kinetically dominated sequential degradation of organic compounds, and advective-dispersive chemical transport. Simulation results indicate that coupled geochemical processes inferred from field data, such as organic biodegradation, iron reduction and dissolution, and methanogenesis, can be successfully modeled using a partial-redox-disequilibrium approach. The results of this study also suggest how the modeling approach can be used to study system sensitivity to various physical and chemical parameters, such as the effect of dispersion on the position of chemical fronts and the impact of alternative buffering mineral phases (e.g., goethite versus amorphous Fe(OH)3) on water chemistry.

River-derived humic substances as iron chelators in seawater

PubMed Central

Krachler, Regina; Krachler, Rudolf F.; Wallner, Gabriele; Hann, Stephan; Laux, Monika; Cervantes Recalde, Maria F.; Jirsa, Franz; Neubauer, Elisabeth; von der Kammer, Frank; Hofmann, Thilo; Keppler, Bernhard K.

2015-01-01

The speciation of iron(III) in oxic seawater is dominated by its hydrolysis and sedimentation of insoluble iron(III)-oxyhydroxide. As a consequence, many oceanic areas have very low iron levels in surface seawater which leads to iron deficiency since phytoplankton require iron as a micronutrient in order to grow. Fortunately, iron solubility is not truly as low as Fe(III) solubility measurements in inorganic seawater would suggest, since oceanic waters contain organic molecules which tend to bind the iron and keep it in solution. Various iron-binding organic ligands which combine to stabilize dissolved iron have been detected and thoroughly investigated in recent years. However, the role of iron-binding ligands from terrestrial sources remains poorly constrained. Blackwater rivers supply large amounts of natural organic material (NOM) to the ocean. This NOM (which consists mainly of vascular plant-derived humic substances) is able to greatly enhance iron bioavailability in estuaries and coastal regions, however, breakdown processes lead to a rapid decrease of river-derived NOM concentrations with increasing distance from land. It has therefore been argued that the influence of river-derived NOM on iron biogeochemistry in offshore seawater does not seem to be significant. Here we used a standard method based on 59Fe as a radiotracer to study the solubility of Fe(III)-oxyhydroxide in seawater in the presence of riverine NOM. We aimed to address the question how effective is freshwater NOM as an iron chelator under open ocean conditions where the concentration of land-derived organic material is about 3 orders of magnitude smaller than in coastal regions, and does this iron chelating ability vary between NOM from different sources and between different size fractions of the river-borne NOM. Our results show that the investigated NOM fractions were able to substantially enhance Fe(III)-oxyhydroxide solubility in seawater at concentrations of the NOM ≥ 5 μg L− 1. Terrigenous NOM concentrations ≥ 5 μg L− 1 are in no way unusual in open ocean surface waters especially of the Arctic and the North Atlantic Oceans. River-derived humic substances could therefore play a greater role as iron carriers in the ocean than previously thought. PMID:26412934

The effects of soil liming and sewage sludge application on dynamics of copper fractions and total copper concentration.

PubMed

Malinowska, Elżbieta

2016-10-01

The paper deals with effects of liming and different doses of municipal sewage sludge (5, 10, and 15 % of soil mass) on copper speciation in soil. In all samples, pH was determined together with total copper concentration, which was measured with the ICP-AES method. Concentration of copper chemical fractions was determined using the seven-step procedure of Zeien and Brümmer. In the soil treated with the highest dose of sludge (15 %), there was, compared to the control, a twofold increase in the concentration of copper and a threefold increase in the concentration of nitrogen. Copper speciation analysis showed that in the municipal sewage sludge the easily soluble and exchangeable fractions (F1 and F2) constituted only a small share of copper with the highest amount of this metal in the organic (F4) and residual (F7) fractions. In the soil, at the beginning of the experiment, the highest share was in the organic fraction (F4), the residual fraction (F7) but also in the fraction where copper is bound to amorphous iron oxides (F5). After 420 days, at the end of the experiment, the highest amount of copper was mainly in the organic fraction (F4) and in the fraction with amorphous iron oxides (F5). Due to mineralization of organic matter in the sewage sludge, copper was released into the soil with the share of the residual fraction (F7) decreasing. In this fraction, there was much more copper in limed soil than in non-limed soil.

In-situ identification of iron electrocoagulation speciation and application for natural organic matter (NOM) removal.

PubMed

Dubrawski, Kristian L; Mohseni, Madjid

2013-09-15

In this work, iron speciation in electrocoagulation (EC) was studied to determine the impact of operating parameters on natural organic matter (NOM) removal from natural water. Two electrochemical EC parameters, current density (i) and charge loading rate (CLR), were investigated. Variation of these parameters led to a near unity current efficiency (φ = 0.957 ± 0.03), at any combination of i in a range of 1-25 mA/cm(2) and CLR in a range of 12-300 C/L/min. Higher i and CLR led to a higher bulk pH and limited the amount of dissolved oxygen (DO) reduced at the cathode surface due to mass transfer limitations. A low i (1 mA/cm(2)) and intermediate CLR (60 C/L/min) resulted in low bulk DO (<2.5 mg/L), where green rust (GR) was identified by in-situ Raman spectroscopy as the primary crystalline electrochemical product. Longer electrolysis times at higher i led to magnetite (Fe3O4) formation. Both higher (300 C/L/min) and lower (12 C/L/min) CLR values led to increased DO and/or increased pH, with lepidocrocite (γ-FeOOH) as the only crystalline species observed. The NOM removal of the three identified species was compared, with conditions leading to GR formation showing the greatest dissolved organic carbon removal, and highest removal of the low apparent molecular weight (<550 Da) chromophoric NOM fraction, determined by high performance size exclusion chromatography. Copyright © 2013 Elsevier Ltd. All rights reserved.

Evaluation of ferrolysis in arsenate adsorption on the paddy soil derived from an Oxisol.

PubMed

Jiang, Jun; Dai, Zhaoxia; Sun, Rui; Zhao, Zhenjie; Dong, Ying; Hong, Zhineng; Xu, Renkou

2017-07-01

Iron oxides are dominant effective adsorbents for arsenate in iron oxide-rich variable charge soils. Oxisol-derived paddy soils undergo intensive ferrolysis, which results in high leaching and transformation of iron oxides. However, little information is available concerning the effect of ferrolysis on arsenate adsorption by paddy soil and parent Oxisol. In the present study, we examined the arsenate affinity of soils using arsenate adsorption/desorption isotherms, zeta potential, adsorption kinetics, pH effect and phosphate competition experiments. Results showed that ferrolysis in an alternating flooding-drying Oxisol-derived paddy soil resulted in a significant decrease of free iron oxides and increase of amorphous iron oxides in the surface and subsurface layers. There were more reactive sites exposed on amorphous than on crystalline iron oxides. Therefore, disproportionate ratios of arsenate adsorption capacities and contents of free iron oxides were observed in the studied Oxisols compared with paddy soils. The Gibbs free energy values corroborated that both electrostatic and non-electrostatic adsorption mechanisms contributed to the arsenate adsorption by bulk soils, and the kinetic adsorption data further suggested that the rate-limiting step was chemisorption. The zeta potential of soil colloids decreased after arsenate was adsorbed on the surfaces, forming inner-sphere complexes and thus transferring their negative charges to the soil particle surfaces. The adsorption/desorption isotherms showed that non-electrostatic adsorption was the main mechanism responsible for arsenate binding to the Oxisol and derived paddy soils, representing 91.42-94.65% of the adsorption capacities. Further studies revealed that arsenate adsorption was greatly inhibited by increasing suspension pH and incorporation of phosphate. Copyright © 2017 Elsevier Ltd. All rights reserved.

A General Map of Iron Metabolism and Tissue-specific Subnetworks

PubMed Central

Hower, Valerie; Mendes, Pedro; Torti, Frank M.; Laubenbacher, Reinhard; Akman, Steven; Shulaev, Vladmir; Torti, Suzy V.

2009-01-01

Iron is required for survival of mammalian cells. Recently, understanding of iron metabolism and trafficking has increased dramatically, revealing a complex, interacting network largely unknown just a few years ago. This provides an excellent model for systems biology development and analysis. The first step in such an analysis is the construction of a structural network of iron metabolism, which we present here. This network was created using CellDesigner version 3.5.2 and includes reactions occurring in mammalian cells of numerous tissue types. The iron metabolic network contains 151 chemical species and 107 reactions and transport steps. Starting from this general model, we construct iron networks for specific tissues and cells that are fundamental to maintaining body iron homeostasis. We include subnetworks for cells of the intestine and liver, tissues important in iron uptake and storage, respectively; as well as the reticulocyte and macrophage, key cells in iron utilization and recycling. The addition of kinetic information to our structural network will permit the simulation of iron metabolism in different tissues as well as in health and disease. PMID:19381358

The redox state of iron in the matrix of CI, CM and metamorphosed CM chondrites by XANES spectroscopy

NASA Astrophysics Data System (ADS)

Beck, P.; De Andrade, V.; Orthous-Daunay, F.-R.; Veronesi, G.; Cotte, M.; Quirico, E.; Schmitt, B.

2012-12-01

Carbonaceous chondrites record the action of water at some point of their petrological history. These meteorites are usually connected to low albedo asteroid, which present visible/near-IR absorption explained by iron related absorption within phyllosilicates and oxides. In order to obtain quantitative insight into the mineralogy of iron-bearing phases, we have measured X-ray absorption near-edge spectroscopy at the iron K-edge of matrix from carbonaceous chondrites. This method enables to constrain the redox state and environment of iron in these meteorites. For this study, we selected seven CM chondrites and the CI Orgueil, expected to span a range of aqueous alteration degrees. Our analysis of the pre-edge features show that the redox state of Orgueil (CI) is dominated by octahedral Fe and that the Fe3+/(Fe3++Fe2+) atomic ratio is above 80%. Full-inversion of the spectra suggests that the iron budget is dominated by iron oxides, with additional contributions from phyllosilicate. In the case of the CM, the iron speciation appears different that in the case of Orgueil. Cronstedtite is identified from the inversion of the spectra, and suggested by the presence of significant amount of tetrahedral Fe3+. Within the CM chondrites, a trend of aqueous alteration appears presents, and which is roughly correlated to the scheme defined by Rubin et al. (2007). This trend is characterized by an increase in the amount of iron oxides. Two shock metamorphosed CM are present in our dataset (PCA 91008, WIS 91600). If WIS 91600 does not appear distinguishable, from the CM trend, in the case of PCA 91008, shock metamorphism did impact the pre-edge intensity and an increased amount of anhydrous silicates is found. Although the matrix was dehydrated, significant amount of Fe3+ is still present, providing a memory of the aqueous alteration.

Kinetics of the metal components of intratracheally instilled stainless steel welding fume suspensions in rats.

PubMed

Kalliomäki, P L; Hyvärinen, H K; Aitio, A; Lakoma, E L; Kalliomäki, K

1986-02-01

The kinetics of iron, chromium, nickel, and cobalt from manual metal arc and metal inert gas stainless steel welding fumes were studied. Neutron activated welding fumes, in aqueous suspensions, were instilled intratracheally into rats. The follow up continued for up to 106 days. From both fumes, approximately 10% of the injection bolus was immediately lost into the gastrointestinal tract, to be recovered in the faeces within three days. Thereafter, a pronounced difference was seen in the kinetics of the two types of fumes. After the first day, chromium, nickel, and iron were lost from the lungs with half times of about 53, 49, and 73 days after exposure to MMA/SS fumes, whereas practically no loss could be seen in the metal components of the metal inert gas welding fumes within two months. The disposition of chromium from MMA/SS fumes closely resembled that of intratracheally instilled water soluble chromates. On the other hand, the disappearance of trivalent chromium from MIS/SS fumes was considerably slower than that of the practically water insoluble chromates, or even of trivalent chromium salts. Thus the physical characteristics of the fume appreciably affect the kinetics of the clearance of chromium compounds from the lungs.

Oxone/Fe[superscript 2+] Degradation of Food Dyes: Demonstration of Catalyst-Like Behavior and Kinetic Separation of Color

ERIC Educational Resources Information Center

Nalliah, Ruth E.

2015-01-01

A demonstration of the degradation of food coloring dyes by oxidation via the Fenton reaction can be substituted with a simpler demonstration using the oxidant oxone with iron(II) ions as an activator. The addition of small amounts of solid oxone and iron(II) sulfate to solutions containing mixtures of food coloring results in successive…

Kinetics of thermal decomposition of hydrated minerals associated with hematite ore in a fluidized bed reactor

NASA Astrophysics Data System (ADS)

Beuria, P. C.; Biswal, S. K.; Mishra, B. K.; Roy, G. G.

2017-03-01

The kinetics of removal of loss on ignition (LOI) by thermal decomposition of hydrated minerals present in natural iron ores (i.e., kaolinite, gibbsite, and goethite) was investigated in a laboratory-scale vertical fluidized bed reactor (FBR) using isothermal methods of kinetic analysis. Experiments in the FBR in batch processes were carried out at different temperatures (300 to 1200°C) and residence time (1 to 30 min) for four different iron ore samples with various LOIs (2.34wt% to 9.83wt%). The operating velocity was maintained in the range from 1.2 to 1.4 times the minimum fluidization velocity ( U mf). We observed that, below a certain critical temperature, the FBR did not effectively reduce the LOI to a desired level even with increased residence time. The results of this study indicate that the LOI level could be reduced by 90% within 1 min of residence time at 1100°C. The kinetics for low-LOI samples (<6wt%) indicates two different reaction mechanisms in two temperature regimes. At lower temperatures (300 to 700°C), the kinetics is characterized by a lower activation energy (diffusion-controlled physical moisture removal), followed by a higher activation energy (chemically controlled removal of LOI). In the case of high-LOI samples, three different kinetics mechanisms prevail at different temperature regimes. At temperature up to 450°C, diffusion kinetics prevails (removal of physical moisture); at temperature from 450 to 650°C, chemical kinetics dominates during removal of matrix moisture. At temperatures greater than 650°C, nucleation and growth begins to influence the rate of removal of LOI.

Arsenic speciation in arsenic-rich Brazilian soils from gold mining sites under anaerobic incubation

USGS Publications Warehouse

De Mello, J. W. V.; Talbott, J.L.; Scott, J.; Roy, W.R.; Stucki, J.W.

2007-01-01

Background. Arsenic speciation in environmental samples is essential for studying toxicity, mobility and bio-transformation of As in aquatic and terrestrial environments. Although the inorganic species As(III) and As(V) have been considered dominant in soils and sediments, organisms are able to metabolize inorganic forms of arsenic into organo-arsenic compounds. Arsenosugars and methylated As compounds can be found in terrestrial organisms, but they generally occur only as minor constituents. We investigated the dynamics of arsenic species under anaerobic conditions in soils surrounding gold mining areas from Minas Gerais State, Brazil to elucidate the arsenic biogeochemical cycle and water contamination mechanisms. Methods. Surface soil samples were collected at those sites, namely Paracatu Formation, Banded Iron Formation and Riacho dos Machados Sequence, and incubated in CaCl2 2.5 mmol L-1 suspensions under anaerobic conditions for 1, 28, 56 and 112 days. After that, suspensions were centrifuged and supernatants analyzed for soluble As species by IC-ICPMS and HPLC-ICPMS. Results. Easily exchangeable As was mainly arsenite, except when reducible manganese was present. Arsenate was mainly responsible for the increase in soluble arsenic due to the reductive dissolution of either iron or manganese in samples from the Paracatu Formation and Riacho dos Machados Sequence. On the other hand, organic species of As dominated in samples from the Banded Iron Formation during anaerobic incubation. Discussion. Results are contrary to the expectation that, in anaerobic environments, As release due to the reductive dissolution of Fe is followed by As(V) reduction to As(III). The occurrence of organo-arsenic species was also found to be significant to the dynamics of soluble arsenic, mainly in soils from the Banded Iron Formation (BIF), under our experimental conditions. Conclusions. In general, As(V) and organic As were the dominant species in solution, which is surprising under anaerobic conditions in terrestrial environments. The unexpected occurrence of organic species of As was attributed to enrollment of ternary organic complexes or living organisms such as algae or cyanobacteria. Perspectives. These findings are believed to be useful for remediation strategies in mine-affected regions, as the organic As species are in general considered to be less toxic than inorganic ones and even As(V) is considered less mobile and toxic than As(III). ?? 2007 ecomed publishers (Verlagsgruppe Hu??thig Jehle Rehm GmbH).

Chemistry of volcanic soils used for agriculture in Brava Island (Cape Verde)

NASA Astrophysics Data System (ADS)

Prudêncio, Maria Isabel; Marques, Rosa; Waerenborgh, João Carlos; José Vieira, Bruno; Dias, Maria Isabel; Rocha, Fernando

2017-04-01

Brava is a small volcanic island located on the south-western part of the Cape Verde archipelago. It is characterized by an irregular plateau between 300 and 976 m above sea level, which is bounded by steep coastal cliffs and cut by fluvial incision in a generally radial drainage pattern. The major volcano-stratigraphic units of the island are: Lower Unit, Middle Unit, Upper Unit, and Sediments. Although Brava is one of the islands with more frequent rainy periods in Cape Verde, the climate is essentially semi-arid, which associated with the rough topography leads to incipient soils. Detailed Fe speciation and chemical composition studies of Cape Verde soils have shown that oxidation is a major weathering mechanism, and high contents of trace elements may occur originated from imbalance of elements in the volcanic parent materials, which can be a threat to the environmental health. The soils mostly used for agriculture in Brava Island are those developed on phonolitic pyroclasts on the plateau and also on sediments. In this work the whole sample (< 2 mm) and the clay-sized fraction (< 2 µm) of these soils were analysed by Mössbauer spectroscopy and neutron activation analysis, aiming to characterize the iron speciation and to determine the concentration and distribution of 30 chemical elements in Brava soils. Mössbauer spectroscopy shows that Fe is more oxidyzed in topsoils developed on sediments (84-87%) than in soils developed on pyroclasts (71-79%). In the clay sized-fraction of all the studied soils only Fe(III) was detected. Iron oxides clearly distinguish the soils derived from the two types of parent materials, hematite being the only Fe oxide present in soils developed on sediments, while maghemite is more abundant in soils developed on pyroclasts. Iron and chromium are depleted in this fine fraction suggesting their occurrence as iron oxides and ferromagnesian minerals present in coarser particles. Among the chemical elements studied, antimony was found to be particularly concentrated in the clay-sized fraction (up to 28 mg/kg) in soils located in the northern part of the island. The existence of significant Sb amounts in the fine particles may contribute to its accumulation in plants both by absorption or by dust deposition onto the plant leaves.

Nutritional Biochemistry of Space Flight

NASA Technical Reports Server (NTRS)

Smith, Scott M.

2000-01-01

Adequate nutrition is critical for maintenance of crew health during and after extended-duration space flight. The impact of weightlessness on human physiology is profound, with effects on many systems related to nutrition, including bone, muscle, hematology, fluid and electrolyte regulation. Additionally, we have much to learn regarding the impact of weightlessness on absorption, mtabolism , and excretion of nutrients, and this will ultimately determine the nutrient requirements for extended-duration space flight. Existing nutritional requirements for extended-duration space flight have been formulated based on limited flight research, and extrapolation from ground-based research. NASA's Nutritional Biochemistry Laboratory is charged with defining the nutritional requirements for space flight. This is accomplished through both operational and research projects. A nutritional status assessment program is included operationally for all International Space Station astronauts. This medical requirement includes biochemical and dietary assessments, and is completed before, during, and after the missions. This program will provide information about crew health and nutritional status, and will also provide assessments of countermeasure efficacy. Ongoing research projects include studies of calcium and bone metabolism, and iron absorption and metabolism. The calcium studies include measurements of endocrine regulation of calcium homeostasis, biochemical marker of bone metabolism, and tracer kinetic studies of calcium movement in the body. These calcium kinetic studies allow for estimation of intestinal absorption, urinary excretion, and perhaps most importantly - deposition and resorption of calcium from bone. The Calcium Kinetics experiment is currently being prepared for flight on the Space Shuttle in 2001, and potentially for subsequent Shuttle and International Space Station missions. The iron study is intended to assess whether iron absorption is down-regulated dUl1ng space flight. This is critical due to the red blood cell changes which occur, and the increase in iron storage that has been observed after space flight. The Iron Absorption and Metabolism experiment is currently planned for long-term flights on the International Space Station.

Trapping a Highly Reactive Nonheme Iron Intermediate That Oxygenates Strong C-H Bonds with Stereoretention.

PubMed

Serrano-Plana, Joan; Oloo, Williamson N; Acosta-Rueda, Laura; Meier, Katlyn K; Verdejo, Begoña; García-España, Enrique; Basallote, Manuel G; Münck, Eckard; Que, Lawrence; Company, Anna; Costas, Miquel

2015-12-23

An unprecedentedly reactive iron species (2) has been generated by reaction of excess peracetic acid with a mononuclear iron complex [Fe(II)(CF3SO3)2(PyNMe3)] (1) at cryogenic temperatures, and characterized spectroscopically. Compound 2 is kinetically competent for breaking strong C-H bonds of alkanes (BDE ≈ 100 kcal·mol(-1)) through a hydrogen-atom transfer mechanism, and the transformations proceed with stereoretention and regioselectively, responding to bond strength, as well as to steric and polar effects. Bimolecular reaction rates are at least an order of magnitude faster than those of the most reactive synthetic high-valent nonheme oxoiron species described to date. EPR studies in tandem with kinetic analysis show that the 490 nm chromophore of 2 is associated with two S = 1/2 species in rapid equilibrium. The minor component 2a (∼5% iron) has g-values at 2.20, 2.19, and 1.99 characteristic of a low-spin iron(III) center, and it is assigned as [Fe(III)(OOAc)(PyNMe3)](2+), also by comparison with the EPR parameters of the structurally characterized hydroxamate analogue [Fe(III)(tBuCON(H)O)(PyNMe3)](2+) (4). The major component 2b (∼40% iron, g-values = 2.07, 2.01, 1.95) has unusual EPR parameters, and it is proposed to be [Fe(V)(O)(OAc)(PyNMe3)](2+), where the O-O bond in 2a has been broken. Consistent with this assignment, 2b undergoes exchange of its acetate ligand with CD3CO2D and very rapidly reacts with olefins to produce the corresponding cis-1,2-hydroxoacetate product. Therefore, this work constitutes the first example where a synthetic nonheme iron species responsible for stereospecific and site selective C-H hydroxylation is spectroscopically trapped, and its catalytic reactivity against C-H bonds can be directly interrogated by kinetic methods. The accumulated evidence indicates that 2 consists mainly of an extraordinarily reactive [Fe(V)(O)(OAc)(PyNMe3)](2+) (2b) species capable of hydroxylating unactivated alkyl C-H bonds with stereoretention in a rapid and site-selective manner, and that exists in fast equilibrium with its [Fe(III)(OOAc)(PyNMe3)](2+) precursor.

High methylmercury production under ferruginous conditions in sediments impacted by sewage treatment plant discharges.

PubMed

Bravo, Andrea G; Bouchet, Sylvain; Guédron, Stéphane; Amouroux, David; Dominik, Janusz; Zopfi, Jakob

2015-09-01

Sewage treatment plants (STPs) are important point sources of mercury (Hg) to the environment. STPs are also significant sources of iron when hydrated ferric oxide (HFO) is used as a dephosphatation agent during water purification. In this study, we combined geochemical and microbiological characterization with Hg speciation and sediment amendments to evaluate the impact of STP's effluents on monomethylmercury (MMHg) production. The highest in-situ Hg methylation was found close to the discharge pipe in subsurface sediments enriched with Hg, organic matter, and iron. There, ferruginous conditions were prevailing with high concentrations of dissolved Fe(2+) and virtually no free sulfide in the porewater. Sediment incubations demonstrated that the high MMHg production close to the discharge was controlled by low demethylation yields. Inhibition of dissimilatory sulfate reduction with molybdate led to increased iron reduction rates and Hg-methylation, suggesting that sulfate-reducing bacteria (SRB) may not have been the main Hg methylators under these conditions. However, Hg methylation in sediments amended with amorphous Fe(III)-oxides was only slightly higher than control conditions. Thus, in addition to iron-reducing bacteria, other non-SRB most likely contributed to Hg methylation. Overall, this study highlights that sediments impacted by STP discharges can become local hot-spots for Hg methylation due to the combined inputs of i) Hg, ii) organic matter, which fuels bacterial activities and iii) iron, which keeps porewater sulfide concentration low and hence Hg bioavailable. Copyright © 2015 Elsevier Ltd. All rights reserved.

Comparison of colorimetry and electrothermal atomic absorption spectroscopy for the quantification of non-transferrin bound iron in human sera.

PubMed

Jittangprasert, Piyada; Wilairat, Prapin; Pootrakul, Pensri

2004-12-01

This paper describes a comparison of two analytical techniques, one employing bathophenanthrolinedisulfonate (BPT), a most commonly-used reagent for Fe (II) determination, as chromogen and an electrothermal atomic absorption spectroscopy (ETAAS) for the quantification of non-transferrin bound iron (NTBI) in sera from thalassemic patients. Nitrilotriacetic acid (NTA) was employed as the ligand for binding iron from low molecular weight iron complexes present in the serum but without removing iron from the transferrin protein. After ultrafiltration the Fe (III)-NTA complex was then quantified by both methods. Kinetic study of the rate of the Fe (II)-BPT complex formation for various excess amounts of NTA ligand was also carried out. The kinetic data show that a minimum time duration (> 60 minutes) is necessary for complete complex formation when large excess of NTA is used. Calibration curves given by colorimetric and ETAAS methods were linear over the range of 0.15-20 microM iron (III). The colorimetric and ETAAS methods exhibited detection limit (3sigma) of 0.13 and 0.14 microM, respectively. The NTBI concentrations from 55 thalassemic serum samples measured employing BPT as chromogen were statistically compared with the results determined by ETAAS. No significant disagreement at 95% confidence level was observed. It is, therefore, possible to select any one of these two techniques for determination of NTBI in serum samples of thalassemic patients. However, the colorimetric procedure requires a longer analysis time because of a slow rate of exchange of NTA ligand with BPT, leading to the slow rate of formation of the colored complex.

Kinetic Studies of Iron Deposition in Horse Spleen Ferritin Using H2O2 and O2 as Oxidants

NASA Technical Reports Server (NTRS)

Lowery, Thomas J., Jr.; Bunker, Jared; Zhang, Bo; Costen, Robert; Watt, Gerald D.

2004-01-01

The reaction of horse spleen ferritin (HoSF) with Fe(2+) at pH 6.5 and 7.5 using O2, H2O2 and 1:1 a mixture of both showed that the iron deposition reaction using H2O2 is approx. 20- to 50-fold faster than the reaction with O2 alone. When H2O2 was added during the iron deposition reaction initiated with O2 as oxidant, Fe(2+) was preferentially oxidized by H2O2, consistent with the above kinetic measurements. Both the O2 and H202 reactions were well defined from 15 to 40 C from which activation parameters were determined. The iron deposition reaction was also studied using O2 as oxidant in the presence and absence of catalase using both stopped-flow and pumped-flow measurements. The presence of catalase decreased the rate of iron deposition by approx. 1.5-fold, and gave slightly smaller absorbance changes than in its absence. From the rate constants for the O2 (0.044 per second) and H2O2 (0.67 per second) iron-deposition reactions at pH 7.5, simulations of steady-state H2O2 concentrations were computed to be 0.45 micromolar. This low value and reported Fe2(+)/O2 values of 2.0-2.5 are consistent with H2O2 rapidly reacting by an alternate but unidentified pathway involving a system component such as the protein shell or the mineral core as previously postulated.

Influence of uranyl speciation and iron oxides on uranium biogeochemical redox reactions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Stewart, B.D.; Amos, R.T.; Nico, P.S.

2010-03-15

Uranium is a pollutant of concern to both human and ecosystem health. Uranium's redox state often dictates its partitioning between the aqueous- and solid-phases, and thus controls its dissolved concentration and, coupled with groundwater flow, its migration within the environment. In anaerobic environments, the more oxidized and mobile form of uranium (UO{sub 2}{sup 2+} and associated species) may be reduced, directly or indirectly, by microorganisms to U(IV) with subsequent precipitation of UO{sub 2}. However, various factors within soils and sediments may limit biological reduction of U(VI), inclusive of alterations in U(VI) speciation and competitive electron acceptors. Here we elucidate themore » impact of U(VI) speciation on the extent and rate of reduction with specific emphasis on speciation changes induced by dissolved Ca, and we examine the impact of Fe(III) (hydr)oxides (ferrihydrite, goethite and hematite) varying in free energies of formation on U reduction. The amount of uranium removed from solution during 100 h of incubation with S. putrefaciens was 77% with no Ca or ferrihydrite present but only 24% (with ferrihydrite) and 14% (no ferrihydrite) were removed for systems with 0.8 mM Ca. Imparting an important criterion on uranium reduction, goethite and hematite decrease the dissolved concentration of calcium through adsorption and thus tend to diminish the effect of calcium on uranium reduction. Dissimilatory reduction of Fe(III) and U(VI) can proceed through different enzyme pathways, even within a single organism, thus providing a potential second means by which Fe(III) bearing minerals may impact U(VI) reduction. We quantify rate coefficients for simultaneous dissimilatory reduction of Fe(III) and U(VI) in systems varying in Ca concentration (0 to 0.8 mM), and using a mathematical construct implemented with the reactive transport code MIN3P, we reveal the predominant influence of uranyl speciation, specifically the formation of uranyl-calcium-carbonato complexes, and ferrihydrite on the rate and extent of uranium reduction in complex geochemical systems.« less

Iron binding to human heavy-chain ferritin.

PubMed

Pozzi, Cecilia; Di Pisa, Flavio; Bernacchioni, Caterina; Ciambellotti, Silvia; Turano, Paola; Mangani, Stefano

2015-09-01

Maxi-ferritins are ubiquitous iron-storage proteins with a common cage architecture made up of 24 identical subunits of five α-helices that drive iron biomineralization through catalytic iron(II) oxidation occurring at oxidoreductase sites (OS). Structures of iron-bound human H ferritin were solved at high resolution by freezing ferritin crystals at different time intervals after exposure to a ferrous salt. Multiple binding sites were identified that define the iron path from the entry ion channels to the oxidoreductase sites. Similar data are available for another vertebrate ferritin: the M protein from Rana catesbeiana. A comparative analysis of the iron sites in the two proteins identifies new reaction intermediates and underlines clear differences in the pattern of ligands that define the additional iron sites that precede the oxidoreductase binding sites along this path. Stopped-flow kinetics assays revealed that human H ferritin has different levels of activity compared with its R. catesbeiana counterpart. The role of the different pattern of transient iron-binding sites in the OS is discussed with respect to the observed differences in activity across the species.

Formation and characterization of metallic iron grains in coal-based reduction of oolitic iron ore

NASA Astrophysics Data System (ADS)

Sun, Yong-sheng; Han, Yue-xin; Li, Yan-feng; Li, Yan-jun

2017-02-01

To reveal the formation and characteristics of metallic iron grains in coal-based reduction, oolitic iron ore was isothermally reduced in various reduction times at various reduction temperatures. The microstructure and size of the metallic iron phase were investigated by scanning electron microscopy, energy-dispersive X-ray spectroscopy, and a Bgrimm process mineralogy analyzer. In the results, the reduced Fe separates from the ore and forms metallic iron protuberances, and then the subsequent reduced Fe diffuses to the protuberances and grows into metallic iron grains. Most of the metallic iron grains exist in the quasi-spherical shape and inlaid in the slag matrix. The cumulative frequency of metallic iron grain size is markedly influenced by both reduction time and temperature. With increasing reduction temperature and time, the grain size of metallic iron obviously increases. According to the classical grain growth equation, the growth kinetic parameters, i.e., time exponent, growth activation energy, and pre-exponential constant, are estimated to be 1.3759 ± 0.0374, 103.18 kJ·mol-1, and 922.05, respectively. Using these calculated parameters, a growth model is established to describe the growth behavior of metallic iron grains.

Oxidation States of Grim Glasses in EET79001 Based on Vanadium Valence

NASA Technical Reports Server (NTRS)

Sutton, S. R.; Rao, M. N.; Nyquist, L. E.

2010-01-01

Gas-rich impact-melt (GRIM) glasses in SNC meteorites are very rich in Martian atmospheric noble gases and sulfur suggesting a possible occurrence of regolith-derived secondary mineral assemblages in these samples. Previously, we have studied two GRIM glasses, 506 and 507, from EET79001 Lith A and Lith B, respectively, for elemental abundances and spatial distribution of sulfur using EMPA (WDS) and FE-SEM (EDS) techniques and for sulfur-speciation using K-edge XANES techniques. These elemental and FE-SEM micro-graph data at several locations in the GRIM glasses from Shergotty (DBS), Zagami 994 and EET79001, Lith B showed that FeO and SO3 are positively correlated (SO3 represents a mixture of sulfide and sulfate). FE-SEM (EDS) study revealed that the sulfur-rich pockets in these glasses contain numerous micron-sized iron-sulfide (Fe-S) globules sequestered throughout the volume. However, in some areas (though less frequently), we detected significant Fe-S-O signals suggesting the occurrence of iron sulfate. These GRIM glasses were studied by K-edge microXANES techniques for sulfur speciation in association with iron in sulfur-rich areas. In both samples, we found the sulfur speciation dominated by sulfide with minor oxidized sulfur mixed in with various proportions. The abundance of oxidized sulfur was greater in 506 than in 507. Based on these results, we hypothesize that sulfur initially existed as sulfate in the glass precursor materials and, on shock-impact melting of the precursor materials producing these glasses, the oxidized sulfur was reduced to predominately sulfide. In order to further test this hypothesis, we have used microXANES to measure the valence states of vanadium in GRIM glasses from Lith A and Lith B to complement and compare with previous analogous measurements on Lith C (note: 506 and 507 contain the largest amounts of martian atmospheric gases but the gas-contents in Lith C measured by are unknown). Vanadium is ideal for addressing this re-dox issue because it has multiple valence states and is a well-studied element. Ferrous-dominated iron valences determined by microXANES on the Lith A and Lith B glasses provide little redox sensitivity. Vanadium valence measurements for impact glass in Lith C at three different locations yielded valence values of 3.1, 3.2 and 3.4 with inferred fO2 values of IW-0.7, IW-0.1 and IW+0.7, respectively. This range of oxygen-fugacity values is understandable because the glasses are shock-molten impact glasses which are heterogeneous in nature. Oxygen fugacity values obtained from the analysis of Fe-Ti oxides and Eu partitioning in pyroxenes from EET79001 Lith A and Lith B (host lithologies) were in the range of IW+0.3 to IW+1.9 suggesting that V in the Lith C impact glass was reduced in the impact process. Here, we examine whether the 506 from Lith A and 507 from Lith B GRIM glasses yield similar or different fO2 values from those of Lith C using the vanadium K-edge microXANES technique.

Sulfur speciation in hydrous experimental glasses of varying oxidation state - Results from measured wavelength shifts of sulfur X-rays

NASA Technical Reports Server (NTRS)

Carroll, Michael R.; Rutherford, Malcolm J.

1988-01-01

The focusing geometry of an electron microprobe has been used to measure the wavelength shifts of sulfur X-rays from hydrous experimental melts synthesized at oxygen fugacities that range from near the iron-wustite buffer to the magnetite-hermatite buffer. It is found that the proportion of dissolved sulfur which is present as sulfate increases with increasing oxygen fugacity. It is noted that in natural melts that have equilibrated at or below fayalite-magnetite-quartz values of +1, sulfur is probably present mainly as S(2-).

The Effect of Temperature and Ionic Strength on the Oxidation of Iodide by Iron(III): A Clock Reaction Kinetic Study

ERIC Educational Resources Information Center

Bauer, Jurica; Tomisic, Vladislav; Vrkljan, Petar B. A.

2012-01-01

A laboratory exercise has recently been reported in which the students use the initial rates method based on the clock reaction approach to deduce the rate law and propose a reaction mechanism for the oxidation of iodide by iron(III) ions. The same approach is used in the exercise proposed herein; the students determine the dependence of the…

ARSENATE AND ARSENITE REMOVAL BY ZERO-VALENT IRON: KINETICS, REDOX TRANSFORMATION, AND IMPLICATIONS FOR IN SITU GROUNDWATER REMEDIATION

EPA Science Inventory

Batch tests were performed utilizing four zerovalent iron (Fe0) filings (Fisher, Peerless, Master Builders, and Aldrich) to remove As(V) and As(III) from water. One gram of metal was reacted headspace-free at 23 °C for up to 5 days in the dark with 41.5 mL of 2 mg L-1 As(V), or A...

The influence of iron oxide nanoparticles upon the adsorption of organic matter on magnetic powdered activated carbon.

PubMed

Lompe, Kim Maren; Menard, David; Barbeau, Benoit

2017-10-15

Combining powdered activated carbon (PAC) with magnetic iron oxides has been proposed in the past to produce adsorbents for natural organic matter (NOM) removal that can be easily separated using a magnetic field. However, the trade-off between the iron oxides' benefits and the reduced carbon content, porosity, and surface area has not yet been investigated systematically. We produced 3 magnetic powdered activated carbons (MPAC) with mass fractions of 10%, 38% and 54% maghemite nanoparticles and compared them to bare PAC and pure nanoparticles with respect to NOM adsorption kinetics and isotherms. While adsorption kinetics were not influenced by the presence of the iron oxide nanoparticles (IONP), as shown by calculated diffusion coefficients from the homogeneous surface diffusion model, nanoparticles reduced the adsorption capacity of NOM due to their lower adsorption capacity. Although the nanoparticles added mesoporosity to the composite materials they blocked intrinsic PAC mesopores at mass fractions >38% as measured by N 2 -adsorption isotherms. Below this mass fraction, the adsorption capacity was mainly dependent on the carbon content in MPAC and mesopore blocking was negligible. If NOM adsorption with MPAC is desired, a highly mesoporous PAC and a low IONP mass fraction should be chosen during MPAC synthesis. Copyright © 2017 Elsevier Ltd. All rights reserved.

Gamma-resonance investigation of the kinetics of the reduction of (. cap alpha. -benzil dioximato-1)(. cap alpha. -benzil dioximato-2)di(pyridine)iron(III)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Turte, K.I.; Bulgak, I.I.; Stukan, R.A.

1986-07-01

(..cap alpha..-Benzil dioximato-1)(..cap alpha..-benzil dioximato-2)di(pyridine)iron(III) in the form of the diacetone solvate (II) is spontaneously converted at room temperature into (..cap alpha..-benzil dioximato-1)(..cap alpha..-benzil dioximato-2)di(pyridine)iron(II) (III). The quantitative composition of a sample containing complexes II and III has been determined as a function of the temperature and the time by gamma-resonance spectroscopy, which made it possible to investigate the kinetics of this reaction. The changes obtained in the percentage of complex II in the sample as a function of time at a given temperature was treated with the use of the Kolmogorov-Erofeev equation for a topochemical reaction of the typemore » A/sub s/ ..-->.. B/sub s/ + C/sub g/. The rate constants of the reaction at various temperatures and the activation energy *E have been determined. In the temperature range from 293 to 304/sup 0/K *E = 25.6 kcal/mole. The possibilities of gamma-resonance spectroscopy in the investigation of topochemical reactions associated with changes in the oxidation state of iron ions have been demonstrated.« less

Source-dependent and source-independent controls on plutonium oxidation state and colloid associations in groundwater.

PubMed

Buesseler, Ken O; Kaplan, Daniel I; Dai, Minhan; Pike, Steven

2009-03-01

Plutonium (Pu) was characterized for its isotopic composition, oxidation states, and association with colloids in groundwater samples near disposal basins in F-Area of the Savannah River Site and compared to similar samples collected six years earlier. Two sources of Pu were identified, the disposal basins, which contained a 24Pu/l39Pu isotopic signature consistent with weapons grade Pu, and 244Cm, a cocontaminant that is a progenitor radionuclide of 24Pu. 24Pu that originated primarily from 244Cm tended to be appreciably more oxidized (Pu(V/VI)), less associated with colloids (approximately 1 kDa - 0.2 microm), and more mobile than 239Pu, as suggested by our prior studies at this site. This is not evidence of isotope fractionation but rather "source-dependent" controls on 240Pu speciation which are processes that are not at equilibrium, i.e., processes that appear kinetically hindered. There were also "source-independent" controls on 239Pu speciation, which are those processes that follow thermodynamic equilibrium with their surroundings. For example, a groundwater pH increase in one well from 4.1 in 1998 to 6.1 in 2004 resulted in an order of magnitude decrease in groundwater 239Pu concentrations. Similarly, the fraction of 239Pu in the reduced Pu(III/IV) and colloidal forms increased systematically with decreases in redox condition in 2004 vs 1998. This research demonstrates the importance of source-dependent and source-independent controls on Pu speciation which would impact Pu mobility during changes in hydrological, chemical, or biological conditions on both seasonal and decadal time scales, and over short spatial scales. This implies more dynamic shifts in Pu speciation, colloids association, and transport in groundwater than commonly believed.

Chromium(III)-imprinted silica gel for speciation analysis of chromium in environmental water samples with ICP-MS detection.

PubMed

Zhang, Nan; Suleiman, Jibrin Sabo; He, Man; Hu, Bin

2008-04-15

A new chromium(III)-imprinted 3-(2-aminoethylamino) propyltrimethoxysilane (AAPTS)-functionalized silica gel sorbent was synthesized by a surface imprinting technique and was employed as a selective solid-phase extraction material for speciation analysis of chromium in environmental water samples prior to its determination by inductively coupled plasma mass spectrometry (ICP-MS). The prepared Cr(III)-imprinted silica gel shows the selectivity coefficient of more than 700 for Cr(III) in the presence of Mn(II). The static adsorption capacity of the ion-imprinted and non-imprinted sorbent for Cr(III) were 30.5 mg g(-1) and 13.4 mg g(-1). It was also found that Cr(VI) could be adsorbed at low pH by the prepared imprinted silica gel, and this finding makes it feasible to enrich and determine Cr(VI) at low pH without adding reducing reagents. The imprinted silica gel sorbent offered a fast kinetics for the adsorption and desorption of both chromium species. Under the optimized conditions, the detection limits of 4.43 pg mL(-1) and 8.30 pg mL(-1) with the relative standard deviations (R.S.D.s) of 4.44% and 4.41% (C=0.5 ng mL(-1), n=7) for Cr(III) and Cr(VI) were obtained, respectively. The proposed method was successfully applied to the speciation of trace chromium in environmental water samples. To validate the proposed method, two certified reference materials were analyzed and the determined values were in a good agreement with the certified values. The developed method is rapid, selective, sensitive and applicable for the speciation of trace chromium in environmental water samples.

Metal speciation in landfill leachates with a focus on the influence of organic matter

DOE Office of Scientific and Technical Information (OSTI.GOV)

Claret, Francis, E-mail: f.claret@brgm.fr; Tournassat, Christophe; Crouzet, Catherine

Highlights: > This study characterises the heavy-metal content in leachates collected from eight landfills in France. > Most of the metals are concentrated in the <30 kDa fraction, while Pb, Cu and Cd are associated with larger particles. > Metal complexation with OM is not sufficient to explain apparent supersaturation of metals with sulphide minerals. - Abstract: This study characterises the heavy-metal content in leachates collected from eight landfills in France. In order to identify heavy metal occurrence in the different size fractions of leachates, a cascade filtration protocol was applied directly in the field, under a nitrogen gas atmospheremore » to avoid metal oxidation. The results of analyses performed on the leachates suggest that most of the metals are concentrated in the <30 kDa fraction, while lead, copper and cadmium show an association with larger particles. Initial speciation calculations, without considering metal association with organic matter, suggest that leachate concentrations in lead, copper, nickel and zinc are super-saturated with respect to sulphur phases. Speciation calculations that account for metal complexation with organic matter, considered as fulvic acids based on C1(s) NEXAFS spectroscopy, show that this mechanism is not sufficient to explain such deviation from equilibrium conditions. It is therefore hypothesized that the deviation results also from the influence of biological activity on the kinetics of mineral phase precipitation and dissolution, thus providing a dynamic system. The results of chemical analyses of sampled fluids are compared with speciation calculations and some implications for the assessment of metal mobility and natural attenuation in a context of landfill risk assessment are discussed.« less

Effect of temperature on iron leaching from bauxite residue by sulfuric acid.

PubMed

Liu, Zhi-Rong; Zeng, Kai; Zhao, Wei; Li, Ying

2009-01-01

Bauxite residue, as solid waste from alumina production, contains mainly hematite [Fe2O3]. Kinetic study of iron leaching of bauxite residue by diluted sulfuric acid at atmospheric pressure has been investigated. The results have been obtained as following: (i) Temperature play an important role in iron leaching from bauxite residue. Higher temperature is favor of Fe(III) leaching from bauxite residue. (ii) The leaching process is applicable to the intra-particle diffusion model and the apparent activation energy of model of leaching is found to be 17.32 kJ/mol.

Preserving the distribution of inorganic arsenic species in groundwater and acid mine drainage samples

USGS Publications Warehouse

Bednar, A.J.; Garbarino, J.R.; Ranville, J.F.; Wildeman, T.R.

2002-01-01

The distribution of inorganic arsenic species must be preserved in the field to eliminate changes caused by metal oxyhydroxide precipitation, photochemical oxidation, and redox reactions. Arsenic species sorb to iron and manganese oxyhydroxide precipitates, and arsenite can be oxidized to arsenate by photolytically produced free radicals in many sample matrices. Several preservatives were evaluated to minimize metal oxyhydroxide precipitation, such as inorganic acids and ethylenediaminetetraacetic acid (EDTA). EDTA was found to work best for all sample matrices tested. Storing samples in opaque polyethylene bottles eliminated the effects of photochemical reactions. The preservation technique was tested on 71 groundwater and six acid mine drainage samples. Concentrations in groundwater samples reached 720 ??g-As/L for arsenite and 1080 ??g-As/L for arsenate, and acid mine drainage samples reached 13 000 ??g-As/L for arsenite and 3700 ??g-As/L for arsenate. The arsenic species distribution in the samples ranged from 0 to 90% arsenite. The stability of the preservation technique was established by comparing laboratory arsenic speciation results for samples preserved in the field to results for subsamples speciated onsite. Statistical analyses indicated that the difference between arsenite and arsenate concentrations for samples preserved with EDTA in opaque bottles and field speciation results were analytically insignificant. The percentage change in arsenite:arsenate ratios for a preserved acid mine drainage sample and groundwater sample during a 3-month period was -5 and +3%, respectively.

Adsorption of arsenic(V) by iron-oxide-coated diatomite (IOCD).

PubMed

Pan, Yi-Fong; Chiou, Cary T; Lin, Tsair-Fuh

2010-09-01

PURPOSES AND AIMS: Economically efficient methods for removing arsenic from the drinking water supply are urgently needed in many parts of the world. Iron oxides are known to have a strong affinity for arsenic in water. However, they are commonly present in the forms of fine powder or floc, which limits their utility in water treatment. In this study, a novel granular adsorbent, iron-oxide-coated diatomite (IOCD), was developed and examined for its adsorption of arsenic from water. An industrial-grade diatomite was used as the iron oxide support. The diatomite was first acidified and dried and then coated with iron oxide up to five times. The prepared IOCD samples were characterized for their morphology, composition, elemental content, and crystal properties by various instruments. Experiments of equilibrium and kinetic adsorption of As(V) on IOCD were conducted using 0.1- and 2-L polyethylene bottles, respectively, at different pH and temperatures. Iron oxide (alpha-Fe(2)O(3) hematite) coated onto diatomite greatly improves (by about 30 times) the adsorption of As(V) from water by IOCD as compared to using raw diatomite. This improvement was attributed to increases in both surface affinity and surface area of the IOCD. The surface area of IOCD increased to an optimal value. However, as the IOCD surface area (93 m(2)/g) was only 45% higher than that of raw diatomite (51 m(2)/g), the enhanced As(V) adsorption resulted primarily from the enhanced association of negatively charged As(V) ions with the partial positive surface charge of the iron oxide. The As(V) adsorption decreased when the solution pH was increased from 3.5 to 9.5, as expected from the partial charge interaction between As(V) and IOCD. The adsorption data at pH 5.5 and 7.5 could be well fitted to the Freundlich equation. A moderately high exothermic heat was observed for the As(V) adsorption, with the calculated molar isosteric heat ranging from -4 to -9 kcal/mol. The observed heats fall between those for physical adsorption and chemisorption and are indicative of the formation of a series of ion-pair complexes of As(V) ions with iron oxide surface groups. This study demonstrated that the granular IOCD was successfully developed and employed to remove the As(V) in aqueous solution. The Freundlich isotherm well fitted the equilibrium adsorption data of As(V) onto IOCD, and both the pseudo-second-order model and the pore diffusion model simulated well the adsorption kinetics. Compared to other iron-oxide-based adsorbents reported in the literatures, the adsorption capacity of IOCD is relatively high and its kinetics is fast.

[Effect of the interaction of microorganisms and iron oxides on arsenic releasing into groundwater in Chinese Loess].

PubMed

Xie, Yun-Yun; Chen, Tian-Hu; Zhou, Yue-Fei; Xie, Qiao-Qin

2013-10-01

A large part of groundwater in the Chinese Loess Plateau area is characterized by high arsenic concentration. Anaerobic bacteria have been considered to play key roles in promoting arsenic releasing from loess to groundwater. However, this hypothesis remains unconfirmed. Based on modeling experiments, this study investigated the speciation of arsenic in loess, and then determined the release rates and quantities of arsenic with the mediation of anaerobic bacteria. The results showed that arsenic contents in loess were between 23 mg.kg-1 and 30 mg.kg-1. No obvious arsenic content difference among loess samples was observed. The ratios for specific adsorbed, iron oxides co-precipitated and silicate co-precipitated arsenic were 37.76% , 36. 15% and 25. 69% , respectively. Indigenous microorganisms, dissimilatory iron reducing bacteria (DIRB) and sulfate reducing bacteria (SRB) could all promote the release of arsenic from loess. Organic matters highly affected the release rates. More than 100 mg.L-1 sodium lactate was required for all bacterial experiments to facilitate obvious arsenic release. Considering the redox condition in loess, the contribution of SRB to arsenic release in loess area was less feasible than that of DIRB and indigenous microorganisms.

Arsenic Speciation and Extraction and the Significance of Biodegradable Acid on Arsenic Removal—An Approach for Remediation of Arsenic-Contaminated Soil

PubMed Central

Nguyen Van, Thinh; Osanai, Yasuhito; Do Nguyen, Hai; Kurosawa, Kiyoshi

2017-01-01

A series of arsenic remediation tests were conducted using a washing method with biodegradable organic acids, including oxalic, citric and ascorbic acids. Approximately 80% of the arsenic in one sample was removed under the effect of the ascorbic and oxalic acid combination, which was roughly twice higher than the effectiveness of the ascorbic and citric acid combination under the same conditions. The soils treated using biodegradable acids had low remaining concentrations of arsenic that are primarily contained in the crystalline iron oxides and organic matter fractions. The close correlation between extracted arsenic and extracted iron/aluminum suggested that arsenic was removed via the dissolution of Fe/Al oxides in soils. The fractionation of arsenic in four contaminated soils was investigated using a modified sequential extraction method. Regarding fractionation, we found that most of the soil contained high proportions of arsenic (As) in exchangeable fractions with phosphorus, amorphous oxides, and crystalline iron oxides, while a small amount of the arsenic fraction was organic matter-bound. This study indicated that biodegradable organic acids can be considered as a means for arsenic-contaminated soil remediation.

Bimetallic Porous Iron (pFe) Materials for Remediation/Removal of Tc from Aqueous Systems

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, D.

Remediation of Tc remains an unresolved challenge at SRS and other DOE sites. The objective of this project was to develop novel bimetallic porous iron (pFe) materials for Tc removal from aqueous systems. We showed that the pFe is much more effective in removing TcO 4 - (×30) and ReO 4 - (×8) from artificial groundwater than granular iron. Tc K-edge XANES spectroscopy indicated that Tc speciation on the pFe was 18% adsorbed TcO 4 -, 28% Tc(IV) in Tc dioxide and 54% Tc(IV) into the structure of Fe hydroxide. A variety of catalytic metal nanoparticles (i.e., Ni, Cu, Zn,more » Ag, Sn and Pd) were successfully deposited on the pFe using scalable chemical reduction methods. The Zn-pFe was outstanding among the six bimetallic pFe materials, with a capacity increase of >100% for TcO 4 - removal and of 50% for ReO 4 - removal, compared to the pFe. These results provide a highly applicable platform for solving critical DOE and industrial needs related to nuclear environmental stewardship and nuclear power production.« less

Co-operative intermolecular kinetics of 2-oxoglutarate dependent dioxygenases may be essential for system-level regulation of plant cell physiology.

PubMed

Kundu, Siddhartha

2015-01-01

Can the stimulus-driven synergistic association of 2-oxoglutarate dependent dioxygenases be influenced by the kinetic parameters of binding and catalysis?In this manuscript, I posit that these indices are necessary and specific for a particular stimulus, and are key determinants of a dynamic clustering that may function to mitigate the effects of this trigger. The protein(s)/sequence(s) that comprise this group are representative of all major kingdoms of life, and catalyze a generic hydroxylation, which is, in most cases accompanied by a specialized conversion of the substrate molecule. Iron is an essential co-factor for this transformation and the response to waning levels is systemic, and mandates the simultaneous participation of molecular sensors, transporters, and signal transducers. Here, I present a proof-of-concept model, that an evolving molecular network of 2OG-dependent enzymes can maintain iron homeostasis in the cytosol of root hair cells of members of the family Gramineae by actuating a non-reductive compensatory chelation by the phytosiderophores. Regression models of empirically available kinetic data (iron and alpha-ketoglutarate) were formulated, analyzed, and compared. The results, when viewed in context of the superfamily responding as a unit, suggest that members can indeed, work together to accomplish system-level function. This is achieved by the establishment of transient metabolic conduits, wherein the flux is dictated by kinetic compatibility of the participating enzymes. The approach adopted, i.e., predictive mathematical modeling, is integral to the hypothesis-driven acquisition of experimental data points and, in association with suitable visualization aids may be utilized for exploring complex plant biochemical systems.

Iron in Neisseria meningitidis: minimum requirements, effects of limitation, and characteristics of uptake.

PubMed Central

Archibald, F S; DeVoe, I W

1978-01-01

A simple defined medium (neisseria defined medium) was devised that does not require iron extraction to produce iron-limited growth of Neisseria meningitidis (SDIC). Comparison of this medium to Mueller-Hinton broth and agar showed nearly identical growth rates and yields. The defined medium was used in batch cultures to determine the disappearance of iron from the medium and its uptake by cells. To avoid a number of problems inherent in batch culture, continuous culture, in which iron and dissolved oxygen were varied independently, was used. Most of the cellular iron was found to be nonheme and associated with the particulate fraction in sonically disrupted cells. Nonheme and catalase-heme iron were reduced by iron starvation far more than cytochromes b and c and N,N,N',N'-tetramethylphenylenediamine-oxidase. The respiration rate and efficiency also decreased under iron limitation, whereas generation times increased. The iron-starved meningococcus took up iron by an energy-independent system operating in the first minute after an iron pulse and a slower energy-dependent system inhibited by respiratory poisons and an uncoupler. The energy-dependent system showed saturation kinetics and was stimulated nearly fourfold by iron privation. In addition, to determine the availability to the meningococcus of the iron in selected compounds, a sensitive assay was devised in which an iron-limited continuous culture was pulsed with the iron-containing compound. PMID:101516

Assessing bioavailability levels of metals in effluent-affected rivers: effect of Fe(III) and chelating agents on the distribution of metal speciation.

PubMed

Han, Shuping; Naito, Wataru; Masunaga, Shigeki

To assess the effects of Fe(III) and anthropogenic ligands on the bioavailability of Ni, Cu, Zn, and Pb, concentrations of bioavailable metals were measured by the DGT (diffusive gradients in thin films) method in some urban rivers, and were compared with concentrations calculated by a chemical equilibrium model (WHAM 7.0). Assuming that dissolved Fe(III) (<0.45 μm membrane filtered) was in equilibrium with colloidal iron oxide, the WHAM 7.0 model estimated that bioavailable concentrations of Ni, Cu, and Zn were slightly higher than the corresponding values estimated assuming that dissolved Fe(III) was absent. In contrast, lower levels of free Pb were predicted by the WHAM 7.0 model when dissolved Fe(III) was included. Estimates showed that most of the dissolved Pb was present as colloidal iron-Pb complex. Ethylene-diamine-tetra-acetic acid (EDTA) concentrations at sampling sites were predicted from the relationship between EDTA and the calculated bioavailable concentration of Zn. When both colloidal iron and predicted EDTA concentrations were included in the WHAM 7.0 calculations, dissolved metals showed a strong tendency to form EDTA complexes, in the order Ni > Cu > Zn > Pb. With the inclusion of EDTA, bioavailable concentrations of Ni, Cu, and Zn predicted by WHAM 7.0 were different from those predicted considering only humic substances and colloidal iron.

Mössbauer investigations to characterize Fe lattice sites in sheet silicates and Peru Basin deep-sea sediments

NASA Astrophysics Data System (ADS)

Lougear, André; König, Iris; Trautwein, Alfred X.; Suess, Erwin

A procedure to classify different Fe lattice sites, i.e., OH-group geometries, in the clay mineral content of deep-sea sediments was developed using Mössbauer spectroscopy at low temperature (77 K). This speciation is of interest with regard to the redox behavior, reactivity and color of marine sediments, since substantial iron redox transitions (associated with sediment color change) have been documented for the structural sheet silicate iron. Lattice site classification was achieved for the Fe(II) fraction, all of which is structural clay Fe(II) in the sediments under investigation. Whereas the major part of the Fe(III) is structural clay iron as well, there is a small Fe(III) fraction in oxide minerals. Therefore, further elaboration of the procedure would be required to also achieve lattice site classification for the Fe(III) fraction. Analysis of the Mössbauer spectra is based on computer fits, the input parameters of which were derived from a separate study of Fe(II)-rich pure chlorites. The procedure of classification is qualified to investigate, e.g., in laboratory experiments, the site-specific reaction rates and the effects on sediment color of iron redox transitions in the sheet silicate content of sediments. The new skills were successfully applied in environmental impact studies on the mining of polymetallic nodules from the Peru Basin deep-sea floor.

Siderophores in Cloud Waters and Potential Impact on Atmospheric Chemistry: Photoreactivity of Iron Complexes under Sun-Simulated Conditions.

PubMed

Passananti, Monica; Vinatier, Virginie; Delort, Anne-Marie; Mailhot, Gilles; Brigante, Marcello

2016-09-06

In the present work, the photoreactivity of a mixture of iron(III)–pyoverdin (Fe(III)–Pyo) complexes was investigated under simulated cloud conditions. Pyoverdins are expected to complex ferric ions naturally present in cloudwater, thus modifying their availability and photoreactivity. The spectroscopic properties and photoreactivity of Fe(III)-Pyo were investigated, with particular attention to their fate under solar irradiation, also studied through simulations. The photolysis of the Fe(III)–Pyo complex leads to the generation of Fe(II), with rates of formation (RFe(II)f) of 6.98 and 3.96 × 10–9 M s–1 at pH 4.0 and 6.0, respectively. Interestingly, acetate formation was observed during the iron-complex photolysis, suggesting that fragmentation can occur after the ligand-to-metal charge transfer (LMCT) via a complex reaction mechanism. Moreover, photogenerated Fe(II) represent an important source of hydroxyl radical via the Fenton reaction in cloudwater. This reactivity might be relevant for the estimation of the rates of formation and steady-state concentrations of the hydroxyl radical by cloud chemistry models and for organic matter speciation in the cloud aqueous phase. In fact, the conventional models, which describe the iron photoreactivity in terms of iron–aqua and oxalate complexes, are not in accordance with our results.

Identifying Marine Copper-Binding Ligands in Seawater

NASA Astrophysics Data System (ADS)

Whitby, H.; Hollibaugh, J. T.; Maldonado, M. T.; Ouchi, S.; van den Berg, S. M.

2016-02-01

Complexation reactions are important because they affect the bioavailability of trace metals such as copper and iron. For example, organic complexation can determine whether copper is a limiting or a toxic micronutrient at natural levels. Copper competes with iron for complexing ligands, and when iron is limiting, copper can also substitute for iron in some metabolic pathways. The speciation of copper can be measured using complexing capacity titrations, which provide the concentration of individual ligand classes (L1, L2 etc.) and the complex stabilities (log K). Using methods recently developed in our laboratory, we show that the ligands within these classes can be measured independently of titrations, thus confirming the titration method and simultaneously identifying the ligands within each class. Thiols were identified as the L1 ligand class and humic compounds as the weaker L2 class in samples from coastal Georgia, USA, collected monthly from April to December. Log K values of the ligand complexes were consistent with values expected for thiols and humic substances. Recent results from culture studies and from samples collected along Line P, a coastal - oceanic transect in the HNLC region of the NE subarctic Pacific, will be presented in comparison to the estuarine results. This comparison will help to broaden our perspective on copper complexation and the ligands responsible, furthering our understanding of ligand sources and life cycles.

Magnetic susceptibility of the South African Agouron scientific drillcores quantifies iron and sulfur alteration relevant to geochemical oxygenation proxies

NASA Astrophysics Data System (ADS)

Raub, T. D.; Nayak, P. M.; Tikoo, S. M.; Johnson, J. E.; Peek, S.; Fischer, W. W.; Kirschvink, J. L.

2010-12-01

Various geochemical characteristics of sedimentary iron- and sulfur-bearing minerals motivate early- to late-oxygenation hypotheses from South African and Australian scientific drillcores. Most intervals of these drillcores appear to be remagnetized (in some cases multiple times); and ~2.0 Ga magnetic sulfide crystallization is particularly pervasive in carbonaceous siltstones of the ca. 2.7-2.2 Ga Griqualand margin of Kaapvaal craton. Robust interpretation of trace element abundances suggesting “whiffs” to “pervasive” levels of late Archean oxygen depends upon systematics of presumed depositional iron speciation; so multiple iron- and sulfur-mineral-altering events affecting existing drillcore records call straightforward interpretations into question. We report ca. 10,000 magnetic susceptibility measurements and associated detailed rock-magnetic results from all lithologies of Archean basinal and slope facies in drillcores GKP and GKF and relatively younger and shallower facies in Paleoproterozoic drillcores GEC and GTF. Specific carbonaceous siltstone and carbonate intervals are less-altered as revealed by coherent and relatively low magnetic susceptibilities: geochemical and biomarker interpretations based upon data from these intervals should be preferred to those from others. Magnetic susceptibility tracks subtle facies variation in drillcore GTF diamictite and suggests highly-structured Paleoproterozoic glacioeustatic sequence architecture consistent with assignment of Makganyene glaciation and its associated geochemical signature to a ca. 2.2 Ga “Snowball Earth” ice age.

Iron mineral structure, reactivity, and isotopic composition in a South Pacific Gyre ferromanganese nodule over 4 Ma

DOE Office of Scientific and Technical Information (OSTI.GOV)

Marcus, Matthew A.; Edwards, Katrina J.; Gueguen, Bleuenn

Deep-sea ferromanganese nodules accumulate trace elements from seawater and underlying sediment porewaters during the growth of concentric mineral layers over millions of years. These trace elements have the potential to record past ocean geochemical conditions. The goal of this study was to determine whether Fe mineral alteration occurs and how the speciation of trace elements responds to alteration over ~3.7Ma of marine ferromanganese nodule (MFN) formation, a timeline constrained by estimates from 9 Be/ 10 Be concentrations in the nodule material. We determined Fe-bearing phases and Fe isotope composition in a South Pacific Gyre (SPG) nodule. Specifically, the distribution patternsmore » and speciation of trace element uptake by these Fe phases were investigated. The time interval covered by the growth of our sample of the nodule was derived from 9 Be/ 10 Be accelerator mass spectrometry (AMS). The composition and distribution of major and trace elements were mapped at various spatial scales, using micro-X-ray fluorescence (μXRF), electron microprobe analysis (EMPA), and inductively coupled plasma mass spectrometry (ICP-MS). Fe phases were characterized by micro-extended X-ray absorption fine structure (μEXAFS) spectroscopy and micro-X-ray diffraction (μXRD). Speciation of Ti and V, associated with Fe, was measured using micro-X-ray absorption near edge structure (μXANES) spectroscopy. Iron isotope composition (δ 56/54 Fe) in subsamples of 1-3mm increments along the radius of the nodule was determined with multiple-collector ICP-MS (MC-ICP-MS). The SPG nodule formed through primarily hydrogeneous inputs at a rate of 4.0±0.4mm/Ma. The nodule exhibited a high diversity of Fe mineral phases: feroxyhite (δ-FeOOH), goethite (α-FeOOH), lepidocrocite (γ-FeOOH), and poorly ordered ferrihydrite-like phases. These findings provide evidence that Fe oxyhydroxides within the nodule undergo alteration to more stable phases over millions of years. Trace Ti and V were spatially correlated with Fe and found to be adsorbed to Fe-bearing minerals. Ti/Fe and V/Fe ratios, and Ti and V speciation, did not vary along the nodule radius. The δ 56/54 Fe values, when averaged over sample increments representing 0.25-0.75Ma, were homogeneous within uncertainty along the nodule radius, at -0.12±0.07‰ (2sd, n=10). Our results indicate that the Fe isotope composition of the nodule remained constant during nodule growth and that mineral alteration did not affect the primary Fe isotope composition of the nodule. Furthermore, the average δ 56/54 Fe value of -0.12‰ we find is consistent with Fe sourced from continental eolian particles (dust). Despite mineral alteration, the trace element partitioning of Ti and V, and Fe isotope composition, do not appear to change within the sensitivity of our measurements. These findings suggest that Fe oxyhydroxides within hydrogenetic ferromanganese nodules are out of geochemical contact with seawater once they are covered by subsequent concentric mineral layers. Even though Fe-bearing minerals are altered, trace element ratios, speciation and Fe isotope composition are preserved within the nodule.« less

Iron mineral structure, reactivity, and isotopic composition in a South Pacific Gyre ferromanganese nodule over 4 Ma

DOE PAGES

Marcus, Matthew A.; Edwards, Katrina J.; Gueguen, Bleuenn; ...

2015-09-05

Deep-sea ferromanganese nodules accumulate trace elements from seawater and underlying sediment porewaters during the growth of concentric mineral layers over millions of years. These trace elements have the potential to record past ocean geochemical conditions. The goal of this study was to determine whether Fe mineral alteration occurs and how the speciation of trace elements responds to alteration over ~3.7Ma of marine ferromanganese nodule (MFN) formation, a timeline constrained by estimates from 9 Be/ 10 Be concentrations in the nodule material. We determined Fe-bearing phases and Fe isotope composition in a South Pacific Gyre (SPG) nodule. Specifically, the distribution patternsmore » and speciation of trace element uptake by these Fe phases were investigated. The time interval covered by the growth of our sample of the nodule was derived from 9 Be/ 10 Be accelerator mass spectrometry (AMS). The composition and distribution of major and trace elements were mapped at various spatial scales, using micro-X-ray fluorescence (μXRF), electron microprobe analysis (EMPA), and inductively coupled plasma mass spectrometry (ICP-MS). Fe phases were characterized by micro-extended X-ray absorption fine structure (μEXAFS) spectroscopy and micro-X-ray diffraction (μXRD). Speciation of Ti and V, associated with Fe, was measured using micro-X-ray absorption near edge structure (μXANES) spectroscopy. Iron isotope composition (δ 56/54 Fe) in subsamples of 1-3mm increments along the radius of the nodule was determined with multiple-collector ICP-MS (MC-ICP-MS). The SPG nodule formed through primarily hydrogeneous inputs at a rate of 4.0±0.4mm/Ma. The nodule exhibited a high diversity of Fe mineral phases: feroxyhite (δ-FeOOH), goethite (α-FeOOH), lepidocrocite (γ-FeOOH), and poorly ordered ferrihydrite-like phases. These findings provide evidence that Fe oxyhydroxides within the nodule undergo alteration to more stable phases over millions of years. Trace Ti and V were spatially correlated with Fe and found to be adsorbed to Fe-bearing minerals. Ti/Fe and V/Fe ratios, and Ti and V speciation, did not vary along the nodule radius. The δ 56/54 Fe values, when averaged over sample increments representing 0.25-0.75Ma, were homogeneous within uncertainty along the nodule radius, at -0.12±0.07‰ (2sd, n=10). Our results indicate that the Fe isotope composition of the nodule remained constant during nodule growth and that mineral alteration did not affect the primary Fe isotope composition of the nodule. Furthermore, the average δ 56/54 Fe value of -0.12‰ we find is consistent with Fe sourced from continental eolian particles (dust). Despite mineral alteration, the trace element partitioning of Ti and V, and Fe isotope composition, do not appear to change within the sensitivity of our measurements. These findings suggest that Fe oxyhydroxides within hydrogenetic ferromanganese nodules are out of geochemical contact with seawater once they are covered by subsequent concentric mineral layers. Even though Fe-bearing minerals are altered, trace element ratios, speciation and Fe isotope composition are preserved within the nodule.« less

Mössbauer study of oxide films of Fe-, Sn-, Cr- doped zirconium alloys during corrosion in autoclave

NASA Astrophysics Data System (ADS)

Filippov, V. P.; Bateev, A. B.; Lauer, Yu. A.

2016-12-01

Mössbauer investigations were used to compare iron atom states in oxide films of binary Zr-Fe, ternary Zr-Fe-Cu and quaternary Zr-Fe-Cr-Sn alloys. Oxide films are received in an autoclave at a temperature of 350-360 °C and at pressure of 16.8 MPa. The corrosion process decomposes the intermetallic precipitates in alloys and forms metallic iron with inclusions of chromium atoms α-Fe(Cr), α-Fe(Cu), α-Fe 2O3 and Fe 3O4 compounds. Some iron ions are formed in divalent and in trivalent paramagnetic states. The additional doping influences on corrosion kinetics and concentration of iron compounds and phases formed in oxide films. It was shown the correlation between concentration of iron in different chemical states and corrosion resistance of alloys.

Removal of Cr(VI) from Water Using a New Reactive Material: Magnesium Oxide Supported Nanoscale Zero-Valent Iron

PubMed Central

Siciliano, Alessio

2016-01-01

The chromium pollution of water is an important environmental and health issue. Cr(VI) removal by means of metallic iron is an attractive method. Specifically, nanoscopic zero valent iron (NZVI) shows great reactivity, however, its applicability needs to be further investigated. In the present paper, NZVI was supported on MgO grains to facilitate the treatments for remediation of chromium-contaminated waters. The performances and mechanisms of the developed composite, in the removal of hexavalent chromium, were investigated by means of batch and continuous tests. Kinetic studies, under different operating conditions, showed that reduction of Cr(VI) could be expressed by a pseudo second-order reaction kinetic. The reaction rate increased with the square of Fe(0) amount, while it was inversely proportional to the initial chromium concentration. The process performance was satisfactory also under uncontrolled pH, and a limited influence of temperature was observed. The reactive material was efficiently reusable for many cycles without any regeneration treatment. The performances in continuous tests were close to 97% for about 80 pore volume of reactive material. PMID:28773785

Parametric Investigation of the Kinetics of Growth of Carbon-Nanotube Arrays on Iron Nanoparticles in the Process of Chemical Vapor Deposition of Hydrocarbons

NASA Astrophysics Data System (ADS)

Futko, S. I.; Shulitski, B. G.; Labunov, V. A.; Ermolaevaa, E. M.

2015-03-01

On the basis of the kinetic model of synthesis of carbon nanotubes on iron nanoparticles in the process of chemical vapor deposition of hydrocarbons, the parametric dependences of characteristics of arrays of vertically oriented nanotubes on the temperature of their synthesis, the concentration of acetylene in a reactor, and the diameter of the catalyst nanoparticles were investigated. It is shown that the maximum on the temperature dependence of the rate of growth of carbon nanotubes, detected in experiments at a temperature of ~700oC is due to the competing processes of increasing the catalytic activity of iron nanoparticles and decreasing the acetylene concentration because of the signifi cant gas-phase decomposition of acetylene in the reactor before it enters the substrate with the catalyst. Our calculations have shown that the indicated maximum arises near the transition point separating the low-temperature region where multiwall nanotubes are predominantly synthesized from the higher-temperature region of generation of single-wall nanotubes in the process of chemical vapor deposition of hydrocarbons.

Synthesis of magnetic activated carbon/α-Fe2O3 nanocomposite and its application in the removal of acid yellow 17 dye from water.

PubMed

Ranjithkumar, V; Sangeetha, S; Vairam, S

2014-05-30

The adsorption of acid yellow 17 dye on activated carbon/α-Fe2O3 nanocomposite prepared by simple pyrolytic method using iron(II) gluconate was investigated by batch technique. The composite was characterized by Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX), transmission electron microscopy (TEM), and vibrating sample magnetometry (VSM). The size of iron oxide nanoparticles formed from iron(II) gluconate precursor is in the range 5-17nm. The saturation magnetization (Ms), remanence (Mr) and coercivity (Hc) of the magnetic carbon nanocomposite is 5.6emu/g, 1.14emu/g and 448Oe, respectively. The adsorption data are found to fit well with Langmuir and, fairly well with Freundlich and Tempkin isotherms at higher concentration of dye (40-100mg/L). Kinetics data indicate that the adsorption of dye follows pseudo-second order kinetics model. Copyright © 2014 Elsevier B.V. All rights reserved.

Removal of Cr(VI) from Water Using a New Reactive Material: Magnesium Oxide Supported Nanoscale Zero-Valent Iron.

PubMed

Siciliano, Alessio

2016-08-06

The chromium pollution of water is an important environmental and health issue. Cr(VI) removal by means of metallic iron is an attractive method. Specifically, nanoscopic zero valent iron (NZVI) shows great reactivity, however, its applicability needs to be further investigated. In the present paper, NZVI was supported on MgO grains to facilitate the treatments for remediation of chromium-contaminated waters. The performances and mechanisms of the developed composite, in the removal of hexavalent chromium, were investigated by means of batch and continuous tests. Kinetic studies, under different operating conditions, showed that reduction of Cr(VI) could be expressed by a pseudo second-order reaction kinetic. The reaction rate increased with the square of Fe(0) amount, while it was inversely proportional to the initial chromium concentration. The process performance was satisfactory also under uncontrolled pH, and a limited influence of temperature was observed. The reactive material was efficiently reusable for many cycles without any regeneration treatment. The performances in continuous tests were close to 97% for about 80 pore volume of reactive material.

Sources and fates of heavy metals in a mining-impacted stream: Temporal variability and the role of iron oxides

PubMed Central

Schaider, Laurel A.; Senn, David B.; Estes, Emily R.; Brabander, Daniel J.; Shine, James P.

2014-01-01

Heavy metal contamination of surface waters at mining sites often involves complex interactions of multiple sources and varying biogeochemical conditions. We compared surface and subsurface metal loading from mine waste pile runoff and mine drainage discharge and characterized the influence of iron oxides on metal fate along a 0.9-km stretch of Tar Creek (Oklahoma, USA), which drains an abandoned Zn/Pb mining area. The importance of each source varied by metal: mine waste pile runoff contributed 70% of Cd, while mine drainage contributed 90% of Pb, and both sources contributed similarly to Zn loading. Subsurface inputs accounted for 40% of flow and 40-70% of metal loading along this stretch. Streambed iron oxide aggregate material contained highly elevated Zn (up to 27,000 μg g−1), Pb (up to 550 μg g−1) and Cd (up to 200 μg g−1) and was characterized as a heterogeneous mixture of iron oxides, fine-grain mine waste, and organic material. Sequential extractions confirmed preferential sequestration of Pb by iron oxides, as well as substantial concentrations of Zn and Cd in iron oxide fractions, with additional accumulation of Zn, Pb, and Cd during downstream transport. Comparisons with historical data show that while metal concentrations in mine drainage have decreased by more than an order of magnitude in recent decades, the chemical composition of mine waste pile runoff has remained relatively constant, indicating less attenuation and increased relative importance of pile runoff. These results highlight the importance of monitoring temporal changes at contaminated sites associated with evolving speciation and simultaneously addressing surface and subsurface contamination from both mine waste piles and mine drainage. PMID:24867708

Rock magnetic and geochemical evidence for authigenic magnetite formation via iron reduction in coal-bearing sediments offshore Shimokita Peninsula, Japan (IODP Site C0020)

NASA Astrophysics Data System (ADS)

Phillips, Stephen C.; Johnson, Joel E.; Clyde, William C.; Setera, Jacob B.; Maxbauer, Daniel P.; Severmann, Silke; Riedinger, Natascha

2017-06-01

Sediments recovered at Integrated Ocean Drilling Program (IODP) Site C0020, in a fore-arc basin offshore Shimokita Peninsula, Japan, include numerous coal beds (0.3-7 m thick) that are associated with a transition from a terrestrial to marine depositional environment. Within the primary coal-bearing unit (˜2 km depth below seafloor) there are sharp increases in magnetic susceptibility in close proximity to the coal beds, superimposed on a background of consistently low magnetic susceptibility throughout the remainder of the recovered stratigraphic sequence. We investigate the source of the magnetic susceptibility variability and characterize the dominant magnetic assemblage throughout the entire cored record, using isothermal remanent magnetization (IRM), thermal demagnetization, anhysteretic remanent magnetization (ARM), iron speciation, and iron isotopes. Magnetic mineral assemblages in all samples are dominated by very low-coercivity minerals with unblocking temperatures between 350 and 580°C that are interpreted to be magnetite. Samples with lower unblocking temperatures (300-400°C), higher ARM, higher-frequency dependence, and isotopically heavy δ56Fe across a range of lithologies in the coal-bearing unit (between 1925 and 1995 mbsf) indicate the presence of fine-grained authigenic magnetite. We suggest that iron-reducing bacteria facilitated the production of fine-grained magnetite within the coal-bearing unit during burial and interaction with pore waters. The coal/peat acted as a source of electron donors during burial, mediated by humic acids, to supply iron-reducing bacteria in the surrounding siliciclastic sediments. These results indicate that coal-bearing sediments may play an important role in iron cycling in subsiding peat environments and if buried deeply through time, within the subsequent deep biosphere.

How does organic matter occurrence set limit onto the use of Ce anomaly as a reliable proxy of redox conditions in shallow groundwaters?

NASA Astrophysics Data System (ADS)

Dia, A.; Gruau, G.; Davranche, M.; Vidy, A.; Henin, O.; Petitjean, P.; Le Coz-Bouhnik, M.

2003-04-01

This study is dedicated to the effects of organic matter on the hydrochemistry of Rare Earth Elements (REE) and the ability of using the Ce anomaly as a reliable proxy of redox conditions in surface waters when organic matter occurs. The data include a : i) two-year survey of SREE and Ce anomalies in organic-rich waters recovered from a catchment located in Brittany (western Europe) and (ii) experimental incubation of organic soils from this catchment set under controlled conditions, as well as, (iii) a REE speciation calculation in both the natural organic-rich waters from the wetlands and the experimental solutions. Field and experimental data appear to be extremely coherent, displaying good correlation between the SREE, the Dissolved Organic Carbon (DOC) contents and the redox state. The field data show a strong increase of the SREE and DOC concentrations in soil waters when the environment becomes more reducing. The onset of DOC and SREE contents is seen to be in phase with the increase of dissolved Fe and Mn. The role of Fe-, Mn-oxyhydroxides is confirmed by the experimental data as the maximum of DOC and SREE content is reached when Fe2+ reaches a maximum in the soil solution, suggesting that reductive dissolution of Fe, Mn-oxyhydroxides happens. Despite the strong redox changes and the known redox sensitive behaviour of Ce as compared to other REE, none Ce anomaly variation is observed during either, the experimental procedure, or the field survey through time. Speciation calculations were performed showing that in both such pH range and moderately oxidizing waters in DOC-rich waters, REE should have an organic speciation. Such an organic speciation prevents the formation of Ce(IV) and therefore the development of any Ce anomaly. However, since the studied waters are highly oxidizing (high nitrate contents), the nitrates impose the redox formation of Ce(IV) and a Ce anomaly should appear. Therefore, Ce(IV) is not formed in these waters either because (i) the reaction kinetic might be so slow that the anomaly has no time to ever happen in the field, or (ii) Ce(IV) might be linked to the organic colloidal fraction. Since the thermodynamic modelling does not help getting information, further experimental kinetics or ultrafiltration studies will be required to clarify these latter points. This has to be fixed to be able to use the Ce anomaly as a reliable proxy of redox conditions in organic-rich environment.

Kinetics of the metal components of intratracheally instilled stainless steel welding fume suspensions in rats.

PubMed Central

Kalliomäki, P L; Hyvärinen, H K; Aitio, A; Lakoma, E L; Kalliomäki, K

1986-01-01

The kinetics of iron, chromium, nickel, and cobalt from manual metal arc and metal inert gas stainless steel welding fumes were studied. Neutron activated welding fumes, in aqueous suspensions, were instilled intratracheally into rats. The follow up continued for up to 106 days. From both fumes, approximately 10% of the injection bolus was immediately lost into the gastrointestinal tract, to be recovered in the faeces within three days. Thereafter, a pronounced difference was seen in the kinetics of the two types of fumes. After the first day, chromium, nickel, and iron were lost from the lungs with half times of about 53, 49, and 73 days after exposure to MMA/SS fumes, whereas practically no loss could be seen in the metal components of the metal inert gas welding fumes within two months. The disposition of chromium from MMA/SS fumes closely resembled that of intratracheally instilled water soluble chromates. On the other hand, the disappearance of trivalent chromium from MIS/SS fumes was considerably slower than that of the practically water insoluble chromates, or even of trivalent chromium salts. Thus the physical characteristics of the fume appreciably affect the kinetics of the clearance of chromium compounds from the lungs. PMID:3947567

Investigation of the kinetic mechanism of the demanganization reaction between carbon-saturated liquid iron and CaF2-CaO-SiO2-based slags

NASA Astrophysics Data System (ADS)

Duan, Sheng-chao; Li, Chuang; Guo, Han-jie; Guo, Jing; Han, Shao-wei; Yang, Wen-sheng

2018-04-01

The demanganization reaction kinetics of carbon-saturated liquid iron with an eight-component slag consisting of CaO-SiO2-MgO-FeO-MnO-Al2O3-TiO2-CaF2 was investigated at 1553, 1623, and 1673 K in this study. The rate-controlling step (RCS) for the demanganization reaction with regard to the hot metal pretreatment conditions was studied via kinetics analysis based on the fundamental equation of heterogeneous reaction kinetics. From the temperature dependence of the mass transfer coefficient of a transition-metal oxide (MnO), the apparent activation energy of the demanganization reaction was estimated to be 189.46 kJ·mol-1 in the current study, which indicated that the mass transfer of MnO in the molten slag controlled the overall rate of the demanganization reaction. The calculated apparent activation energy was slightly lower than the values reported in the literature for mass transfer in a slag phase. This difference was attributed to an increase in the "specific reaction interface" (SRI) value, either as a result of turbulence at the reaction interface or a decrease of the absolute amount of slag phase during sampling, and to the addition of calcium fluoride to the slag.

Kinetics and Products of Chromium(VI) Reduction by Iron(II/III)-Bearing Clay Minerals.

PubMed

Joe-Wong, Claresta; Brown, Gordon E; Maher, Kate

2017-09-05

Hexavalent chromium is a water-soluble pollutant, the mobility of which can be controlled by reduction of Cr(VI) to less soluble, environmentally benign Cr(III). Iron(II/III)-bearing clay minerals are widespread potential reductants of Cr(VI), but the kinetics and pathways of Cr(VI) reduction by such clay minerals are poorly understood. We reacted aqueous Cr(VI) with two abiotically reduced clay minerals: an Fe-poor montmorillonite and an Fe-rich nontronite. The effects of ionic strength, pH, total Fe content, and the fraction of reduced structural Fe(II) [Fe(II)/Fe(total)] were examined. The last variable had the largest effect on Cr(VI) reduction kinetics: for both clay minerals, the rate constant of Cr(VI) reduction varies by more than 3 orders of magnitude with Fe(II)/Fe(total) and is described by a linear free energy relationship. Under all conditions examined, Cr and Fe K-edge X-ray absorption near-edge structure spectra show that the main Cr-bearing product is a Cr(III)-hydroxide and that Fe remains in the clay structure after reacting with Cr(VI). This study helps to quantify our understanding of the kinetics of Cr(VI) reduction by Fe(II/III)-bearing clay minerals and may improve predictions of Cr(VI) behavior in subsurface environments.

The Kinetic Mechanism for Cytochrome P450 Metabolism of Type II Binding Compounds: Evidence Supporting Direct Reduction

PubMed Central

Pearson, Joshua; Dahal, Upendra P.; Rock, Daniel; Peng, Chi-Chi; Schenk, James O.; Joswig-Jones, Carolyn; Jones, Jeffrey P.

2011-01-01

The metabolic stability of a drug is an important property that should be optimized during drug design and development. Nitrogen incorporation is hypothesized to increase the stability by coordination of nitrogen to the heme iron of cytochrome P450, a binding mode that is referred to as type II binding. However, we noticed that the type II binding compound 1 has less metabolic stability at subsaturating conditions than a closely related type I binding compound 3. Three kinetic models will be presented for type II binder metabolism; 1) Dead-end type II binding, 2) a rapid equilibrium between type I and II binding modes before reduction, and 3) a direct reduction of the type II coordinated heme. Data will be presented on reduction rates of iron, the off rates of substrate (using surface plasmon resonance) and the catalytic rate constants. These data argue against the dead-end, and rapid equilibrium models, leaving the direct reduction kinetic mechanism for metabolism of the type II binding compound 1. PMID:21530484

Impact of phenazine-1-carboxylic acid upon iron speciation and microbial biomass in the rhizosphere of wheat

NASA Astrophysics Data System (ADS)

LeTourneau, M.; Marshall, M.; Grant, M.; Freeze, P.; Cliff, J. B.; Lai, B.; Strawn, D. G.; Thomashow, L. S.; Weller, D. M.; Harsh, J. B.

2015-12-01

Phenazine-1-carboxylic acid (PCA) is a redox-active antibiotic produced by diverse bacterial taxa, and has been shown to facilitate interactions between biofilms and iron (hydr)oxides in culture systems (Wang et al. 2011, J Bacteriol 192: 365). Because rhizobacterial biofilms are a major sink for plant-derived carbon and source for soil organic matter (SOM), and Fe (hydr)oxides have reactive surfaces that influence the stability of microbial biomass and SOM, PCA-producing rhizobacteria could influence soil carbon fluxes. Large populations of Pseudomonas fluorescens strains producing PCA in concentrations up to 1 μg/g root have been observed in the rhizosphere of non-irrigated wheat fields covering 1.56 million hectares of central Washington state. This is one of the highest concentrations ever reported for a natural antibiotic in a terrestrial ecosystem (Mavrodi et al. 2012, Appl Environ Microb 78: 804). Microscopic comparisons of PCA-producing (PCA+) and non-PCA-producing (PCA-) rhizobacterial colony morphologies, and comparisons of Fe extractions from rhizosphere soil inoculated with PCA+ and PCA- strains suggest that PCA promotes biofilm development as well as dramatic Fe transformations throughout the rhizosphere (unpublished data). In order to illustrate PCA-mediated interactions between biofilms and Fe (hydr)oxides in the rhizosphere, identify the specific Fe phases favored by PCA, and establish the ramifications for stability and distribution of microbial biomass and SOM, we have collected electron micrographs, X-ray fluorescence images, X-ray absorption near-edge spectra, and secondary-ion mass spectrometry images of wheat root sections inoculated with 15N-labelled PCA+ or PCA- rhizobacteria. These images and spectra allow us to assess the accumulation, turnover, and distribution of microbial biomass, the associations between Fe and other nutrients such as phosphorus, and the redox status and speciation of iron in the presence and absence of PCA. This information provides a starting point to model the impact of PCA upon carbon fluxes in Columbia Basin agro-ecosystems and other environments where PCA-producing bacteria are prevalent.

A geochemical study of the Ediacaran discoidal fossil Aspidella preserved in limestones: Implications for its taphonomy and paleoecology.

PubMed

Bykova, N; Gill, B C; Grazhdankin, D; Rogov, V; Xiao, S

2017-07-01

The Ediacara biota features the rise of macroscopic complex life immediately before the Cambrian explosion. One of the most abundant and widely distributed elements of the Ediacara biota is the discoidal fossil Aspidella, which is interpreted as a subsurface holdfast possibly anchoring a frondose epibenthic organism. It is a morphologically simple fossil preserved mainly in siliciclastic rocks, which are unsuitable for comprehensive stable isotope geochemical analyses to decipher its taphonomy and paleoecology. In this regard, three-dimensionally preserved Aspidella fossils from upper Ediacaran limestones of the Khatyspyt Formation in the Olenek Uplift of northern Siberia offer a rare opportunity to leverage geochemistry for insights into their taphonomy and paleoecology. To take advantage of this opportunity, we analyzed δ 13 C carb , δ 18 O carb , δ 13 C org , δ 34 S pyr , and iron speciation of the Khatyspyt Aspidella fossils and surrounding sediment matrix in order to investigate whether they hosted microbial symbionts, how they were fossilized, and the redox conditions of their ecological environments. Aspidella holdfasts and surrounding sediment matrix show indistinguishable δ 13 C org values, suggesting they did not host and derive significant amount of nutrients from microbial symbionts such as methanogens, methylotrophs, or sulfide-oxidizing bacteria. δ 13 C carb , δ 18 O carb , and δ 34 S pyr data, along with petrographic observations, suggest that microbial sulfate reduction facilitated the preservation of Aspidella by promoting early authigenic calcite cementation in the holdfasts before matrix cementation and sediment compaction. Iron speciation data are equivocal, largely because of the low total iron concentrations. However, consideration of published sulfur isotope and biomarker data suggests that Aspidella likely lived in non-euxinic waters. It is possible that Aspidella was an opportunistic organism, colonizing the seafloor in large numbers when paleoenvironments were favorable. This study demonstrates that geochemical data of Ediacaran fossils preserved in limestones can offer important insights into the taphonomy and paleoecology of these enigmatic organisms living on the eve of the Cambrian explosion. © 2017 John Wiley & Sons Ltd.

Chemical transformations during aging of zerovalent iron nanoparticles in the presence of common groundwater dissolved constituents.

PubMed

Reinsch, Brian C; Forsberg, Brady; Penn, R Lee; Kim, Christopher S; Lowry, Gregory V

2010-05-01

Nanoscale zerovalent iron (NZVI) that was aged in simulated groundwater was evaluated for alterations in composition and speciation over 6 months to understand the possible transformations NZVI could undergo in natural waters. NZVI was exposed to 10 mN of various common groundwater anions (Cl(-), NO(3)(-), SO(4)(2-), HPO(4)(2-), and HCO(3)(-)) or to dissolved oxygen (saturated, approximately 9 mg/L). Fresh and exposed NZVI samples, along with Fe-oxide model compounds, were then analyzed using synchrotron radiation X-ray absorption spectroscopy (XAS) to yield both relative oxidation state, using the X-ray absorption near edge structure (XANES), and quantitative speciation information regarding the types and proportions of mineral species present, from analysis of the extended X-ray absorption fine structure (EXAFS). Over 1 month of aging the dissolved anions inhibited the oxidation of the NZVI to varying degrees. Aging for 6 months, however, resulted in average oxidation states that were similar to each other regardless of the anion used, except for nitrate. Nitrate passivated the NZVI surface such that even after 6 months of aging the particles retained nearly the same mineral and Fe(0) content as fresh NZVI. Linear least-squares combination fitting (LCF) of the EXAFS spectra for 1 month-aged samples indicated that the oxidized particles remain predominantly a binary phase system containing Fe(0) and Fe(3)O(4), while the 6 month aged samples contained additional mineral phases such as vivianite (Fe(3)(PO(4))(2).8H(2)O) and iron sulfate species, possibly schwertmannite (Fe(3+)(16)O(16)(OH,SO(4))(12-13).10-12H(2)O). The presence of these additional mineral species was confirmed using synchrotron-based X-ray diffraction (XRD). NZVI exposed to water saturated with dissolved oxygen showed a rapid (<24 h) loss of Fe(0) and evolved both magnetite and maghemite (gamma-Fe(2)O(3)) within the oxide layer. These findings have implications toward the eventual fate, transport, and toxicity of NZVI used for groundwater remediation.

Source tracing of fluvial suspended sediments by magnetic and geochemical particle characterization: example of the Canche watershed (Nord-Pas-de-Calais, France)

NASA Astrophysics Data System (ADS)

Patault, Edouard; Alary, Claire; Franke, Christine; Gauthier, Arnaud; Abriak, Nor-Edine

2016-04-01

In France, erosion by water run-off is estimated to 1.5 t ha-1yr-1 and can exceed 10 t ha-1yr-1 in large growing areas, such as the North of France (Nord-Pas-de-Calais). In this region, the Canche watershed (1294 km2) sustains heavy loss of fertile soils. The land use is mainly dominated by arable lands (80%) and in 2013, 104 kt of suspended sediment transited to the estuary. As demonstrated in literature, agricultural soil erosion leads to the gradual disappearance and depletion of fertile soil, which constitute a non-renewable resource at human time scale. Additionally, water erosion can significantly damage the aquatic habitat and can be responsible for the input of nutrients, bacteria, pesticides, heavy metals and radionuclides into surface waters. Conscious of these effects, many programs have emerged in the Nord-Pas-de-Calais to reduce erosion. This study presents a combination of environmental magnetic proxy parameters and geochemical analyses on sediments and suspended particulate matter. The aim is to develop effective tools to trace erosion by water run-off and quantify this process. In order to identify the respective sediment sources in the Canche watershed, sediment trap samples of suspended particulate matter were recovered at key positions along the Canche watershed. The preliminary results show that magnetic concentration (Mrs) shows typical values for the agricultural soils in the region, but these variations in magnetic concentrations and total irons concentrations are not always correlated, which may be explained by the iron speciation. In calculating the so-called S-ratio for each sample we can distinguish changes in magneto-mineralogy (and thus iron speciation) from magnetite-dominated assemblages in the mainstream Canche (naturel background signal) to high-coercivity-dominated assemblages in the tributaries, typical for soil erosion material rich in hematite/goethite. In combination with the element concentrations from ICP analyses, this proxy parameter may give valuable insight into the tracing of the suspended sediment sources. In perspective, the seasonal variability and the discharge in the Canche watershed have to be taken into account.

Microscale speciation of arsenic and iron in ferric-based sorbents subjected to simulated landfill conditions

PubMed Central

Root, Robert A.; Fathordoobadi, Sahar; Alday, Fernando; Ela, Wendell; Chorover, Jon

2013-01-01

During treatment for potable use, water utilities generate arsenic-bearing ferric wastes that are subsequently dispatched to landfills. The biogeochemical weathering of these residuals in mature landfills affects the potential mobilization of sorbed arsenic species via desorption from solids subjected to phase transformations driven by abundant organic matter and bacterial activity. Such processes are not simulated with the Toxicity Characteristic Leaching Procedure (TCLP) currently used to characterize hazard. To examine the effect of sulfate on As retention in landfill leachate, columns of As(V) loaded amorphous ferric hydroxide were reacted biotically at two leachate sulfate concentrations (0.064 mM and 2.1 mM). After 300 d, ferric sorbents were reductively dissolved. Arsenic released to porewaters was partially co-precipitated in mixed-valent secondary iron phases whose speciation was dependent on sulfate concentration. As and Fe XAS showed that, in the low sulfate column, 75–81% of As(V) was reduced to As(III), and 53–68% of the Fe(III) sorbent was transformed, dominantly to siderite and green rust. In the high sulfate column, Fe(III) solids were reduced principally to FeS(am), whereas As(V) was reduced to a polymeric sulfide with local atomic structure of realgar. Multi-energy micro-X-ray fluorescence (ME-μXRF) imaging at Fe and As K-edges showed that As formed surface complexes with ferrihydrite > siderite > green rust in the low sulfate column; while discrete realgar-like phases formed in the high sulfate systems. Results indicate that landfill sulfur chemistry exerts strong control over the potential mobilization of As from ferric sorbent residuals by controlling secondary As and Fe sulfide co-precipitate formation. PMID:24102155

Accumulation of Fe oxyhydroxides in the Peruvian oxygen deficient zone implies non-oxygen dependent Fe oxidation

DOE PAGES

Heller, Maija I.; Lam, Phoebe J.; Moffett, James W.; ...

2017-05-19

Oxygen minimum zones (OMZs) have been proposed to be an important source of dissolved iron (Fe) into the interior ocean. However, previous studies in OMZs have shown a sharp decrease in total dissolved Fe (dFe) and/or dissolved Fe(II) (dFe(II)) concentrations at the shelf-break, despite constant temperature, salinity and continued lack of oxygen across the shelf-break. The loss of both total dFe and dFe(II) suggests a conversion of the dFe to particulate form, but studies that have coupled the reduction-oxidation (redox) speciation of both dissolved and particulate phases have not previously been done. Here in this work, we have measured themore » redox speciation and concentrations of both dissolved and particulate forms of Fe in samples collected during the U.S. GEOTRACES Eastern tropical Pacific Zonal Transect (EPZT) cruise in 2013 (GP16). This complete data set allows us to assess possible mechanisms for loss of dFe. We observed an offshore loss of dFe(II) within the oxygen deficient zone (ODZ), where dissolved oxygen is undetectable, accompanied by an increase in total particulate Fe (pFe). Total pFe concentrations were highest in the upper ODZ. X-ray absorption spectroscopy revealed that the pFe maximum was primarily in the Fe(III) form as Fe(III) oxyhydroxides. The remarkable similarity in the distributions of total particulate iron and nitrite suggests a role for nitrite in the oxidation of dFe(II) to pFe(III). Lastly, we present a conceptual model for the rapid redox cycling of Fe that occurs in ODZs, despite the absence of oxygen.« less

Accumulation of Fe oxyhydroxides in the Peruvian oxygen deficient zone implies non-oxygen dependent Fe oxidation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Heller, Maija I.; Lam, Phoebe J.; Moffett, James W.

Oxygen minimum zones (OMZs) have been proposed to be an important source of dissolved iron (Fe) into the interior ocean. However, previous studies in OMZs have shown a sharp decrease in total dissolved Fe (dFe) and/or dissolved Fe(II) (dFe(II)) concentrations at the shelf-break, despite constant temperature, salinity and continued lack of oxygen across the shelf-break. The loss of both total dFe and dFe(II) suggests a conversion of the dFe to particulate form, but studies that have coupled the reduction-oxidation (redox) speciation of both dissolved and particulate phases have not previously been done. Here in this work, we have measured themore » redox speciation and concentrations of both dissolved and particulate forms of Fe in samples collected during the U.S. GEOTRACES Eastern tropical Pacific Zonal Transect (EPZT) cruise in 2013 (GP16). This complete data set allows us to assess possible mechanisms for loss of dFe. We observed an offshore loss of dFe(II) within the oxygen deficient zone (ODZ), where dissolved oxygen is undetectable, accompanied by an increase in total particulate Fe (pFe). Total pFe concentrations were highest in the upper ODZ. X-ray absorption spectroscopy revealed that the pFe maximum was primarily in the Fe(III) form as Fe(III) oxyhydroxides. The remarkable similarity in the distributions of total particulate iron and nitrite suggests a role for nitrite in the oxidation of dFe(II) to pFe(III). Lastly, we present a conceptual model for the rapid redox cycling of Fe that occurs in ODZs, despite the absence of oxygen.« less

Accumulation of Fe oxyhydroxides in the Peruvian oxygen deficient zone implies non-oxygen dependent Fe oxidation

NASA Astrophysics Data System (ADS)

Heller, Maija I.; Lam, Phoebe J.; Moffett, James W.; Till, Claire P.; Lee, Jong-Mi; Toner, Brandy M.; Marcus, Matthew A.

2017-08-01

Oxygen minimum zones (OMZs) have been proposed to be an important source of dissolved iron (Fe) into the interior ocean. However, previous studies in OMZs have shown a sharp decrease in total dissolved Fe (dFe) and/or dissolved Fe(II) (dFe(II)) concentrations at the shelf-break, despite constant temperature, salinity and continued lack of oxygen across the shelf-break. The loss of both total dFe and dFe(II) suggests a conversion of the dFe to particulate form, but studies that have coupled the reduction-oxidation (redox) speciation of both dissolved and particulate phases have not previously been done. Here we have measured the redox speciation and concentrations of both dissolved and particulate forms of Fe in samples collected during the U.S. GEOTRACES Eastern tropical Pacific Zonal Transect (EPZT) cruise in 2013 (GP16). This complete data set allows us to assess possible mechanisms for loss of dFe. We observed an offshore loss of dFe(II) within the oxygen deficient zone (ODZ), where dissolved oxygen is undetectable, accompanied by an increase in total particulate Fe (pFe). Total pFe concentrations were highest in the upper ODZ. X-ray absorption spectroscopy revealed that the pFe maximum was primarily in the Fe(III) form as Fe(III) oxyhydroxides. The remarkable similarity in the distributions of total particulate iron and nitrite suggests a role for nitrite in the oxidation of dFe(II) to pFe(III). We present a conceptual model for the rapid redox cycling of Fe that occurs in ODZs, despite the absence of oxygen.

Statistical analysis of iron geochemical data suggests limited late Proterozoic oxygenation

NASA Astrophysics Data System (ADS)

Sperling, Erik A.; Wolock, Charles J.; Morgan, Alex S.; Gill, Benjamin C.; Kunzmann, Marcus; Halverson, Galen P.; MacDonald, Francis A.; Knoll, Andrew H.; Johnston, David T.

2015-07-01

Sedimentary rocks deposited across the Proterozoic-Phanerozoic transition record extreme climate fluctuations, a potential rise in atmospheric oxygen or re-organization of the seafloor redox landscape, and the initial diversification of animals. It is widely assumed that the inferred redox change facilitated the observed trends in biodiversity. Establishing this palaeoenvironmental context, however, requires that changes in marine redox structure be tracked by means of geochemical proxies and translated into estimates of atmospheric oxygen. Iron-based proxies are among the most effective tools for tracking the redox chemistry of ancient oceans. These proxies are inherently local, but have global implications when analysed collectively and statistically. Here we analyse about 4,700 iron-speciation measurements from shales 2,300 to 360 million years old. Our statistical analyses suggest that subsurface water masses in mid-Proterozoic oceans were predominantly anoxic and ferruginous (depleted in dissolved oxygen and iron-bearing), but with a tendency towards euxinia (sulfide-bearing) that is not observed in the Neoproterozoic era. Analyses further indicate that early animals did not experience appreciable benthic sulfide stress. Finally, unlike proxies based on redox-sensitive trace-metal abundances, iron geochemical data do not show a statistically significant change in oxygen content through the Ediacaran and Cambrian periods, sharply constraining the magnitude of the end-Proterozoic oxygen increase. Indeed, this re-analysis of trace-metal data is consistent with oxygenation continuing well into the Palaeozoic era. Therefore, if changing redox conditions facilitated animal diversification, it did so through a limited rise in oxygen past critical functional and ecological thresholds, as is seen in modern oxygen minimum zone benthic animal communities.

Non-steady state diagenesis of organic and inorganic sulfur in lake sediments

NASA Astrophysics Data System (ADS)

Couture, Raoul-Marie; Fischer, Rachele; Van Cappellen, Philippe; Gobeil, Charles

2016-12-01

Sulfur controls the fate of many geochemical elements in lake sediments, including iron, phosphorus and environmentally important trace elements. We measured the speciation of pore-water and sediment-bound sulfur (aqueous sulfate and sulfides, elemental sulfur, iron monosulfide, pyrite, organic sulfur) and supporting geochemical variables (carbon, oxygen, iron) in the sediments of a perennially oxygenated and a seasonally anoxic basin of an oligotrophic lake in Québec, using a combination of pore-water analyses, sequential extractions and X-ray absorption near edge structure. A non-steady state early diagenetic model was developed and calibrated against this extensive dataset to help unravel the pathways and quantify the rates of S transformations. Results suggest that the main source of S to the sediments is the settling of organic ester-sulfate (R-O-SO3-H). Hydrolysis of these compounds provides an additional source of sulfate for anaerobic microbial oxidation of sedimentary organic matter, releasing sulfide to the pore-water. Reduced solid-bound S species accumulate as thiols (R-SH) and iron sulfides in the perennially oxygenated and seasonally anoxic basin, respectively. The model-estimated rate constant for R-SH formation is lower than previously estimated for this particular lacustrine site, but similar to that proposed for marine shelf sediments. The solid sediment S profiles, however, carry the imprint of the time-dependent sulfate input to the lake. Iron sulfide enrichments formed during past decades of elevated atmospheric SO4 deposition are presently dissolving. In the sediments of the perennially oxygenated basin this reaction hampers the build-up of Fe(III) (oxy)hydroxide near the sediment-water interface.

Micronutrient metal speciation is controlled by competitive organic chelation in grassland soils

DOE Office of Scientific and Technical Information (OSTI.GOV)

Boiteau, Rene M.; Shaw, Jared B.; Pasa-Tolic, Ljiljana

Many elements are scarcely soluble in aqueous conditions found in high pH environments, such as calcareous grassland soils, unless complexed to strong binding organic ligands. To overcome this limitation, some plants and microbes produce chelators that solubilize micronutrient metals such as Fe, Ni, Cu, and Zn from mineral phases. These complexes are taken up by organisms via specific membrane receptors, thereby differentially impacting the bioavailability of these metals to the plant and microbial community. Although the importance of these chelation strategies for individual organisms has been well established, little is known about which pathways coexist within rhizosphere microbiomes or howmore » they interact and compete for metal binding. Identifying these metallo-organic species within natural ecosystems has remained a formidable analytical challenge due to the vast diversity of compounds and poorly defined metabolic processes in complex soil matrix. Herein, we employed recently developed liquid chromatography (LC) mass spectrometry (MS) methods to characterize the speciation of water-soluble dissolved trace elements (Fe, Ni, Cu, and Zn) from Kansas Prairie soil. Both plant and fungal chelators were identified, revealing compound-specific patterns of chelation to biologically essential metals. Numerous metabolites typically implicated in plant iron acquisition and homeostasis, including mugineic acids, deoxymugineic acid, nicotianamine, and hydroxynicotianamine, dominated the speciation of divalent metals such as Ni, Cu, and Zn (2-57 pmol / g soil). In contrast, the fungal siderophore ferricrocine bound comparatively more trivalent Fe (9pmol / g soil). These results define biochemical pathways that underpin the regulation of metals in the grassland rhizosphere. They also raise new questions about the competition of these compounds for metal binding and their bioavailability to different members of the rhizosphere population. Even small structural differences result in significant differences in their environmental metal speciation, and likely impact metal uptake within the rhizosphere of calcareous soils.« less

Arsenic speciation and trace element analysis of the volcanic río Agrio and the geothermal waters of Copahue, Argentina.

PubMed

Farnfield, Hannah R; Marcilla, Andrea L; Ward, Neil I

2012-09-01

Surface water originating from the Copahue volcano crater-lake was analysed for total arsenic and four arsenic species: arsenite (iAs(III)), arsenate (iAs(V)), monomethylarsonic acid (MA(V)) and dimethylarsinic acid (DMA(V)) and other trace elements (Fe, Mn, V, Cr, Ni, Zn). A novel in-field technique for the preconcentration and separation of four arsenic species was, for the first time, used for the analysis of geothermal and volcanic waters. Total arsenic levels along the río Agrio ranged from <0.2-3783 μg/l As(T). The highest arsenic levels were recorded in the el Vertedero spring (3783 μg/l As(T)) on the flank of the Copahue volcano, which feeds the acidic río Agrio. Arsenite (H(3)AsO(3)) predominated along the upper río Agrio (78.9-81.2% iAs(III)) but the species distribution changed at lago Caviahue and arsenate (H(2)AsO(4)(-)) became the main species (51.4-61.4% iAs(V)) up until Salto del Agrio. The change in arsenic species is potentially a result of an increase in redox potential and the formation of iron-based precipitates. Arsenic speciation showed a statistically significant correlation with redox potential (r=0.9697, P=0.01). Both total arsenic and arsenic speciation displayed a statistically significant correlation with vanadium levels along the river (r=0.9961, P=0.01 and r=0.8488, P=0.05, respectively). This study highlights that chemical speciation analysis of volcanic waters is important in providing ideas on potential chemical toxicity. Furthermore there is a need for further work evaluating how arsenic (and other trace elements), released in volcanic and geothermal streams/vents, impacts on both biota and humans (via exposure in thermal pools or consuming commercial drinking water). Copyright © 2012 Elsevier B.V. All rights reserved.

The kinetics of the oxidation of ferrous iron in synthetic and natural waters

NASA Astrophysics Data System (ADS)

Davison, W.; Seed, G.

1983-01-01

The rate of oxidation of ferrous iron in a seasonally anoxic lake was measured on 39 occasions with respect to both depth and time. Sample disturbance was minimal as only oxygen had to be introduced to initiate the reaction. The data were consistent with the simple rate law for homogeneous chemical kinetics previously established for synthetic solutions. The rate constant for the oxidation reaction in lake water was indistinguishable from that measured in synthetic samples. It did not appear to be influenced by changes in the microbial populations or by changes in any particulate or soluble components in the water, including iron and manganese. Analysis of the errors inherent in the kinetic measurements showed that the estimation of pH was the major source of inaccuracy and that values of the rate constant determined by different workers could easily differ by a factor of six. The present data, together with a comprehensive survey of the literature, are used to suggest a 'universal' rate constant of ca. 2 × 10 13 M -2 atm -1 min -1 (range 1.5-3 × 10 13) in the rate law -d[Fe II]/dt = k[Fe II]pO 2 (OH-) 2 for natural freshwaters in the pH range 6.5-7.4. Discrepancies in the effects of ionic strength and interfering substances reported in the literature are highlighted. Generally substances have only been found to interfere at concentrations which far exceed those in most natural waters.

Evaluation of Fe-containing Li2CuO2 on CO2 capture performed at different physicochemical conditions.

PubMed

Yañez-Aulestia, Ana; Ovalle-Encinia, Oscar; Pfeiffer, Heriberto

2018-06-05

Li 2 CuO 2 and different iron-containing Li 2 CuO 2 samples were synthesized by solid state reaction. On iron-containing samples, atomic sites of copper are substituted by iron ions in the lattice (XRD and Rietveld analyses). Iron addition induces copper release from Li 2 CuO 2 , which produce cationic vacancies and CuO, due to copper (Cu 2+ ) and iron (Fe 3+ ) valence differences. Two different physicochemical conditions were used for analyzing CO 2 capture on these samples; (i) high temperature and (ii) low temperature in presence of water vapor. At high temperatures, iron addition increased CO 2 chemisorption, due to structural and chemical variations on Li 2 CuO 2 . Kinetic analysis performed by first order reaction and Eyring models evidenced that iron addition on Li 2 CuO 2 induced a faster CO 2 chemisorption but a higher thermal dependence. Conversely, CO 2 chemisorption at low temperature in water vapor presence practically did not vary by iron addition, although hydration and hydroxylation processes were enhanced. Moreover, under these physicochemical conditions the whole sorption process became slower on iron-containing samples, due to metal oxides presence.

Chromium fate in constructed wetlands treating tannery wastewaters.

PubMed

Dotro, Gabriela; Palazolo, Paul; Larsen, Daniel

2009-06-01

Nine experimental wetlands were built to determine chromium partitioning inside systems treating tannery wastewaters. Results showed 5-day biochemical oxygen demand and chromium removals of 95 to 99% and 90 to 99%, respectively. The majority of chromium was found in association with media (96 to 98%), followed by effluents (2.9 to 3.9%), and the least was found in plant parts (0.1%). Chemical speciation modeling of solutions and scanning electron microscope analysis suggest two potential chromium removal mechanisms--sorption/coprecipitation with iron hydroxides or oxyhydroxides and biomass sorption. The release of the majority of chromium in the iron- and organic-bound phases during sequential extractions supports the proposed dominant removal mechanisms. The use of a mixture of peat and gravel resulted in lower removal efficiencies and stronger partitioning in organic phases during sequential extractions. Chromium was efficiently removed by wetlands, retained through chemical and biological processes. Future research will focus on further exploring removal mechanisms and proposing management strategies for the chromium-containing wetland media.

Mathematical model of the direct reduction of dust composite pellets containing zinc and iron

NASA Astrophysics Data System (ADS)

An, Xiu-wei; Wang, Jing-song; She, Xue-feng; Xue, Qing-guo

2013-07-01

Direct reduction of dust composite pellets containing zinc and iron was examined by simulating the conditions of actual production process of a rotary hearth furnace (RHF) in laboratory. A mathematical model was constructed to study the reduction kinetics of iron oxides and ZnO in the dust composite pellets. It was validated by comparing the calculated values with experimental results. The effects of furnace temperature, pellet radius, and pellet porosity on the reduction were investigated by the model. It is shown that furnace temperature has obvious influence on both of the reduction of iron oxides and ZnO, but the influence of pellet radius and porosity is much smaller. Model calculations suggest that both of the reduction of iron oxides and ZnO are under mixed control with interface reactions and Boudouard reaction in the early stage, but only with interface reactions in the later stage.

Stability of bacterial carotenoids in the presence of iron in a model of the gastric compartment - comparison with dietary reference carotenoids.

PubMed

Sy, Charlotte; Dangles, Olivier; Borel, Patrick; Caris-Veyrat, Catherine

2015-04-15

Recently isolated spore-forming pigmented marine bacteria, Bacillus indicus HU36 and Bacillus firmus GB1 are sources of carotenoids (∼fifteen distinct yellow and orange pigments and ∼thirteen distinct pink pigments, respectively). They are glycosides of oxygenated lycopene derivatives (apo-lycopenoids) and are assumed to be more heat- and gastric-stable than common carotenoids. In this study, the oxidation by O2 of the bacterial carotenoids was initiated by free iron (Fe(II) and Fe(III)) or by heme iron (metmyoglobin) in a mildly acidic aqueous solution mimicking the gastro-intestinal compartment and compared to the oxidation of the common dietary carotenoids β-carotene, lycopene and astaxanthin. Under these conditions, all bacterial carotenoids appear more stable in the presence of heme iron vs. free iron. Carotenoid autoxidation initiated by Fe(II) is relatively fast and likely involves reactive oxygen-iron species derived from Fe(II) and O2. By contrast, the corresponding reaction with Fe(III) is kinetically blocked by the slow preliminary reduction of Fe(III) into Fe(II) by the carotenoids. The stability of carotenoids toward autoxidation increases as follows: β-carotene

Dendritic core-shell nickel-iron-copper metal/metal oxide electrode for efficient electrocatalytic water oxidation.

PubMed

Zhang, Peili; Li, Lin; Nordlund, Dennis; Chen, Hong; Fan, Lizhou; Zhang, Biaobiao; Sheng, Xia; Daniel, Quentin; Sun, Licheng

2018-01-26

Electrochemical water splitting requires efficient water oxidation catalysts to accelerate the sluggish kinetics of water oxidation reaction. Here, we report a promisingly dendritic core-shell nickel-iron-copper metal/metal oxide electrode, prepared via dealloying with an electrodeposited nickel-iron-copper alloy as a precursor, as the catalyst for water oxidation. The as-prepared core-shell nickel-iron-copper electrode is characterized with porous oxide shells and metallic cores. This tri-metal-based core-shell nickel-iron-copper electrode exhibits a remarkable activity toward water oxidation in alkaline medium with an overpotential of only 180 mV at a current density of 10 mA cm -2 . The core-shell NiFeCu electrode exhibits pH-dependent oxygen evolution reaction activity on the reversible hydrogen electrode scale, suggesting that non-concerted proton-electron transfers participate in catalyzing the oxygen evolution reaction. To the best of our knowledge, the as-fabricated core-shell nickel-iron-copper is one of the most promising oxygen evolution catalysts.

Arsenic removal using natural biomaterial-based sorbents.

PubMed

Ansone, Linda; Klavins, Maris; Viksna, Arturs

2013-10-01

Arsenic contamination of water is a major problem worldwide. A possible solution can be approached through developing new sorbents based on cost-effective and environmentally friendly natural biomaterials. We have developed new sorbents based on biomaterial impregnation with iron oxyhydroxide. In this study, raw peat material, iron-modified peat, iron-modified biomass (shingles, straw, sands, cane and moss) as well as iron humate were used for the removal of arsenate from contaminated water. The highest sorption capacity was observed in iron-modified peat, and kinetic studies indicated that the amount of arsenic sorbed on this material exceeds 90 % in 5 h. Arsenate sorption on iron-modified peat is characterised by the pseudo-second-order mechanism. The results of arsenic sorption in the presence of competing substances indicated that sulphate, nitrate, chloride and tartrate anions have practically no influence on As(V) sorption onto Fe-modified peat, whereas the presence of phosphate ions and humic acid significantly lowers the arsenic removal efficiency.

Quantification of Cation Sorption to Engineered Barrier Materials Under Extreme Conditions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Powell, Brian; Schlautman, Mark; Rao, Linfeng

The objective of this research is to examine mechanisms and thermodynamics of actinide sorption to engineered barrier materials (iron (oxyhydr)oxides and bentonite clay) for nuclear waste repositories under high temperature and high ionic strength conditions using a suite of macroscopic and microscopic techniques which will be coupled with interfacial reaction models. Gaining a mechanistic understanding of interfacial processes governing the sorption/sequestration of actinides at mineral-water interfaces is fundamental for the accurate prediction of actinide behavior in waste repositories. Although macroscale sorption data and various spectroscopic techniques have provided valuable information regarding speciation of actinides at solid-water interfaces, significant knowledge gapsmore » still exist with respect to sorption mechanisms and the ability to quantify sorption, particularly at high temperatures and ionic strengths. This objective is addressed through three major tasks: (1) influence of oxidation state on actinide sorption to iron oxides and clay minerals at elevated temperatures and ionic strengths; (2) calorimetric titrations of actinide-mineral suspensions; (3) evaluation of bentonite performance under repository conditions. The results of the work will include a qualitative conceptual model and a quantitative thermodynamic speciation model describing actinide partitioning to minerals and sediments, which is based upon a mechanistic understanding of specific sorption processes as determined from both micro-scale and macroscale experimental techniques. The speciation model will be a thermodynamic aqueous and surface complexation model of actinide interactions with mineral surfaces that is self-consistent with macroscopic batch sorption data, calorimetric and potentiometric titrations, X-ray absorption Spectroscopy (XAS, mainly Extended X-ray Absorption Fine Structure (EXAFS)), and electron microscopy analyses. The novelty of the proposed work lies largely in the unique system conditions which will be examined (i.e. elevated temperature and ionic strength) and the manner in which the surface complexation model will be developed in terms of specific surface species identified using XAS. These experiments will thus provide a fundamental understanding of the chemical and physical processes occurring at the solid-solution interface under expected repository conditions. Additionally, the focus on thermodynamic treatment of actinide ion interactions with minerals as proposed will provide information on the driving forces involved and contribute to the overall understanding of the high affinity many actinide ions have for oxide surfaces. The utility of this model will be demonstrated in this work through a series of advective and diffusive flow experiments.« less

Epidemiological and experimental aspects of metal carcinogenesis: physicochemical properties, kinetics, and the active species.

PubMed Central

Magos, L

1991-01-01

The carcinogenic properties of selected metals and their compounds are reviewed to provide a useful reference for existing knowledge on relationships between physical and chemical forms, kinetics and carcinogenic potential and between epidemiology, bioassays, and short-term tests. Extensive consideration is given to arsenic, beryllium, cadmium, chromium, lead, and nickel. Other metals such as antimony, cobalt, copper, iron, manganese, selenium, and zinc are discussed briefly. PMID:1821370

Dehalogenation of Polybrominated Diphenyl Ethers and Polychlorinated Biphenyl by Bimetallic, Impregnated, and Nanoscale Zerovalent Iron

PubMed Central

Zhuang, Yuan; Ahn, Sungwoo; Seyfferth, Angelia L.; Masue-Slowey, Yoko; Fendorf, Scott; Luthy, Richard G.

2011-01-01

Nanoscale zerovalent iron particles (nZVI), bimetallic nanoparticles (nZVI/Pd), and nZVI/Pd impregnated activated carbon (nZVI/Pd-AC) composite particles were synthesized and investigated for their effectiveness to remove polybrominated diphenyl ethers (PBDEs) and/or polychlorinated biphenyls (PCBs). Palladization of nZVI promoted the dehalogenation kinetics for mono- to tri-BDEs and 2,3,4-trichlorobiphenyl (PCB 21). Compared to nZVI, the iron-normalized rate constants for nZVI/Pd were about 2-, 3-, and 4-orders of magnitude greater for tri-, di-, and mono-BDEs, respectively, with diphenyl ether as a main reaction product. The reaction kinetics and pathways suggest an H-atom transfer mechanism. The reaction pathways with nZVI/Pd favor preferential removal of para-halogens on PBDEs and PCBs. X-ray fluorescence mapping of nZVI/Pd-AC showed that Pd mainly deposits on the outer part of particles, while Fe was present throughout the activated carbon particles. While BDE 21 was sorbed onto activated carbon composites quickly, debromination was slower compared to reaction with freely dispersed nZVI/Pd. Our XPS and chemical data suggest about 7% of the total iron within the activated carbon was zero-valent, which shows the difficulty with in-situ synthesis of a significant fraction of zero-valent iron in the micro-porous material. Related factors that likely hinder the reaction with nZVI/Pd-AC are the heterogenous distribution of nZVI and Pd on activated carbon and/or immobilization of hydrophobic organic contaminants at the adsorption sites thereby inhibiting contact with nZVI. PMID:21557574

The Effect of Pressure on Iron Speciation in Silicate Melts at a Fixed Oxygen Fugacity: The Possibility of a Redox Profile Through a Terrestrial Magma Ocean

NASA Astrophysics Data System (ADS)

Armstrong, K.; Frost, D. J.; McCammon, C. A.; Rubie, D. C.; Boffa Ballaran, T.

2017-12-01

As terrestrial planets accreted, mantle silicates equilibrated with core-forming metallic iron, which would have imposed a mantle oxygen fugacity below the iron-wüstite oxygen buffer. Throughout Earth's history, however, the oxygen fugacity of at least the accessible portions of the upper mantle has been 4-5 orders of magnitude higher. The process that caused the rapid increase in the redox state of the mantle soon after core formation is unclear. Here we test the possibility that pressure stabilises ferric iron in silicate melts, as has been observed in silicate minerals. A deep magma ocean, which would have likely existed towards the end of accretion, could then develop a gradient in oxygen fugacity for a fixed ferric-ferrous ratio as a result of pressure. We have equilibrated an andesitic melt with a Ru-RuO2 buffer in a multianvil press between 5 and 24 GPa. Further experiments were performed on the same melt in equilibrium with iron metal. The recovered melts were then analysed using Mössbauer spectroscopy to determine the ferric/ferrous ratio. The results show that for the Ru-RuO2 buffer at lower pressures, the ferric iron content decreases with pressure, due to a positive volume change of the reaction FeO + 1/4O2 = FeO1.5. Ferric iron content also appears to be sensitive to water content at lower pressures. However, above 15 GPa this trend apparently reverses and the ferric iron content increases with pressure. This reversal in pressure dependence would drive the oxygen fugacity of a deep magma ocean with a fixed ferric/ferrous ratio down with increasing depth. This would create a redox gradient, where the magma ocean could potentially be in equilibrium with metallic iron at its base but more oxidised in its shallower regions. Crystallisation of this magma ocean could render an upper mantle oxygen fugacity similar to that in the Earth's accessible mantle today.

Towards a unifying, systems biology understanding of large-scale cellular death and destruction caused by poorly liganded iron: Parkinson’s, Huntington’s, Alzheimer’s, prions, bactericides, chemical toxicology and others as examples

PubMed Central

2010-01-01

Exposure to a variety of toxins and/or infectious agents leads to disease, degeneration and death, often characterised by circumstances in which cells or tissues do not merely die and cease to function but may be more or less entirely obliterated. It is then legitimate to ask the question as to whether, despite the many kinds of agent involved, there may be at least some unifying mechanisms of such cell death and destruction. I summarise the evidence that in a great many cases, one underlying mechanism, providing major stresses of this type, entails continuing and autocatalytic production (based on positive feedback mechanisms) of hydroxyl radicals via Fenton chemistry involving poorly liganded iron, leading to cell death via apoptosis (probably including via pathways induced by changes in the NF-κB system). While every pathway is in some sense connected to every other one, I highlight the literature evidence suggesting that the degenerative effects of many diseases and toxicological insults converge on iron dysregulation. This highlights specifically the role of iron metabolism, and the detailed speciation of iron, in chemical and other toxicology, and has significant implications for the use of iron chelating substances (probably in partnership with appropriate anti-oxidants) as nutritional or therapeutic agents in inhibiting both the progression of these mainly degenerative diseases and the sequelae of both chronic and acute toxin exposure. The complexity of biochemical networks, especially those involving autocatalytic behaviour and positive feedbacks, means that multiple interventions (e.g. of iron chelators plus antioxidants) are likely to prove most effective. A variety of systems biology approaches, that I summarise, can predict both the mechanisms involved in these cell death pathways and the optimal sites of action for nutritional or pharmacological interventions. PMID:20967426

Redox sensing molecular mechanism of an iron metabolism regulatory protein FBXL5.

PubMed

Wei, Yaozhu; Yuan, Hong; Xu, Pengbiao; Tan, Xiangshi

2017-02-15

FBXL5 is a subunit of the SCF FBXL5 ubiquitin ligase complex that targets the proteasomal degradation of iron regulatory protein IRP2, which is an important regulator in iron metabolism. The degradation of FBXL5 itself is regulated in an iron- and oxygen-responsive manner through its diiron center containing Hr-like domain. Although the crystal structure of the Hr-like domain of FBXL5 and its degradation based on iron/oxygen sensing has been reported, the redox sensing molecular mechanism is still not clear. Herein the redox properties of FBXL5 were investigated via EPR, direct electrochemistry, SRCD, fluorescence emission spectroscopy, and redox kinetics. The results indicated that the conformation and function of FBXL5 are tuned by the redox states of the diiron center. The redox reactions of the diiron center are accompanied with conformational changes and iron release, which are associated with FBXL5 stability and degradation. These results provide insights into the redox sensing mechanism by which FBXL5 can serve as an iron metabolism regulator within mammalian cells. Copyright © 2017 Elsevier Inc. All rights reserved.

Effect of total solids content on methane and volatile fatty acid production in anaerobic digestion of food waste.

PubMed

Liotta, Flavia; d'Antonio, Giuseppe; Esposito, Giovanni; Fabbricino, Massimiliano; van Hullebusch, Eric D; Lens, Piet N L; Pirozzi, Francesco; Pontoni, Ludovico

2014-10-01

This work investigates the role of the moisture content on anaerobic digestion of food waste, as representative of rapidly biodegradable substrates, analysing the role of volatile fatty acid production on process kinetics. A range of total solids from 4.5% to 19.2% is considered in order to compare methane yields and kinetics of reactors operated under wet to dry conditions. The experimental results show a reduction of the specific final methane yield of 4.3% and 40.8% in semi-dry and dry conditions compared with wet conditions. A decreasing trend of the specific initial methane production rate is observed when increasing the total solids concentration. Because of lack of water, volatile fatty acids accumulation occurs during the first step of the process at semi-dry and dry conditions, which is considered to be responsible for the reduction of process kinetic rates. The total volatile fatty acids concentration and speciation are proposed as indicators of process development at different total solids content. © The Author(s) 2014.

Effect of uranium(VI) speciation on simultaneous microbial reduction of uranium(VI) and iron(III).

PubMed

Stewart, Brandy D; Amos, Richard T; Fendorf, Scott

2011-01-01

Uranium is a pollutant of concern to both human and ecosystem health. Uranium's redox state often dictates whether it will reside in the aqueous or solid phase and thus plays an integral role in the mobility of uranium within the environment. In anaerobic environments, the more oxidized and mobile form of uranium (UO2(2+) and associated species) may be reduced, directly or indirectly, by microorganisms to U(IV) with subsequent precipitation of UO. However, various factors within soils and sediments, such as U(VI) speciation and the presence of competitive electron acceptors, may limit biological reduction of U(VI). Here we examine simultaneous dissimilatory reduction of Fe(III) and U(VI) in batch systems containing dissolved uranyl acetate and ferrihydrite-coated sand. Varying amounts of calcium were added to induce changes in aqueous U(VI) speciation. The amount of uranium removed from solution during 100 h of incubation with S. putrefaciens was 77% in absence of Ca or ferrihydrite, but only 24% (with ferrihydrite) and 14% (without ferrihydrite) were removed for systems with 0.8 mM Ca. Dissimilatory reduction of Fe(III) and U(VI) proceed through different enzyme pathways within one type of organism. We quantified the rate coefficients for simultaneous dissimilatory reduction of Fe(III) and U(VI) in systems varying in Ca concecentration (0-0.8 mM). The mathematical construct, implemented with the reactive transport code MIN3P, reveals predominant factors controlling rates and extent of uranium reduction in complex geochemical systems.

Acid Sulfate Alteration in Gusev Crater, Mars

NASA Technical Reports Server (NTRS)

Morris, R. V.; Ming, D. W.; Catalano, J. G.

2016-01-01

The Mars Exploration Rover (MER) Spirit landed on the Gusev Crater plains west of the Columbia Hills in January, 2004, during the Martian summer (sol 0; sol = 1 Martian day = 24 hr 40 min). Spirit explored the Columbia Hills of Gusev Crater in the vicinity of Home Plate at the onset on its second winter (sol approximately 900) until the onset of its fourth winter (sol approximately 2170). At that time, Spirit became mired in a deposit of fined-grained and sulfate-rich soil with dust-covered solar panels and unfavorable pointing of the solar arrays toward the sun. Spirit has not communicated with the Earth since sol 2210 (January, 2011). Like its twin rover Opportunity, which landed on the opposite side of Mars at Meridiani Planum, Spirit has an Alpha Particle X-Ray Spectrometer (APXS) instrument for chemical analyses and a Moessbauer spectrometer (MB) for measurement of iron redox state, mineralogical speciation, and quantitative distribution among oxidation (Fe(3+)/sigma Fe) and coordination (octahedral versus tetrahedral) states and mineralogical speciation (e.g., olivine, pyroxene, ilmenite, carbonate, and sulfate). The concentration of SO3 in Gusev rocks and soils varies from approximately 1 to approximately 34 wt%. Because the APXS instrument does not detect low atomic number elements (e.g., H and C), major-element oxide concentrations are normalized to sum to 100 wt%, i.e., contributions of H2O, CO2, NO2, etc. to the bulk composition care not considered. The majority of Gusev samples have approximately 6 plus or minus 5 wt% SO3, but there is a group of samples with high SO3 concentrations (approximately 30 wt%) and high total iron concentrations (approximately 20 wt%). There is also a group with low total Fe and SO3 concentrations that is also characterized by high SiO2 concentrations (greater than 70 wt%). The trend labeled "Basaltic Soil" is interpreted as mixtures in variable proportions between unaltered igneous material and oxidized and SO3-rich basaltic dust. The Moessbauer parameters are not definitive for mineralogical speciation (other than octahedrally-coordinated Fe(3+) but are consistent with a schwertmannite-like phase (i.e., a nanophase ferric oxide). The high oxidation state and values of Moessbauer parameters (center shift and quadrupole splitting) for the high-SO3 samples imply ferric sulfate (i.e., oxidized sulfur), although the hydration state cannot be constrained. In no case is there an excess of SO3 over available cations (i.e., no evidence for elemental sulfur), and Fe sulfide (pyrite) has been detected in only one Gusev sample. The presence of both high-SiO2 (and low total iron and SO3) and high SO3 (and high total iron as ferric sulfate) can be accommodated by a two-step geochemical model developed with the Geochemist's Workbench. (1) Step 1 is anoxic acid sulfate leaching of Martian basalt at high water-to rock ratios (greater than 70). The result is a high-SiO2 residue0, and anoxic conditions are required to solubilize Fe as Fe(2+). (2) Step 2 is the oxic precipitation of sulfate salts from the leachate. Oxic conditions are required to produce the high concentrations of ferric sulfate with minor Mg-sulfates and no detectable Fe(2+)-sulfates.

Mercury conversion processes in Amazon soils evaluated by thermodesorption analysis.

PubMed

do Valle, Cláudia M; Santana, Genilson P; Windmöller, Cláudia C

2006-12-01

This paper reports on the speciation study and the Hg redox behavior in Amazon soils not influenced by gold mining and collected near Manaus, AM, Brazil. The samples were incubated by adding Hg(0) and HgCl(2) to dry soil. Solid phase Hg speciation analysis was carried out using a Hg thermodesorption technique with the aim of distinguishing elemental Hg(0) from Hg(II) binding forms. In the first case, we observed the conversion of Hg(0) to Hg(II) binding forms in the range of 28-68% and a correlation between the percent of oxidation and OM content. Samples incubated with Hg(II) showed the formation of Hg(I) and/or Hg(0) in the range of 19-69%. The lowest values corresponded to the samples with the lowest clay contents. The kinetics of conversion of Hg(0) as well as HgCl(2) were roughly fitted to the two first order reactions, a fast one and a slow one. It was not possible to evaluate differences between sampling sites and types of soils, but the mean half-life of the first order reaction obtained by the addition of Hg(II) was slower (t(1/2)=365d) than the one obtained by the addition of Hg(0) (t(1/2)=148d). Previous studies have shown the predominance of organically bound Hg in these samples. Thus, the kinetic difference between Hg oxidation and reduction in combination with the efficient retention processes by OM may explain the high background values found in Amazon soils.

Characterization of the kinetics of Fe (II) binding by the R2 protein subunit of E. coli ribonucleotide reductase

NASA Astrophysics Data System (ADS)

Chaudhuri, Dipankar; , Joseph Martin Bollinger, Jr.

2008-07-01

The kinetics of Fe(II) binding to Escherichia coli Ribonucleotide reductase (R2) has been studied using rapid kinetics techniques including chemical quenched flow (CQF) Mössbauer spectroscopy. Based on the stopped flow absorption (SF-Abs) and CQF Mössbauer spectroscopy results, the pre-steady kinetics of binding of Fe(II) to the two sites A and B on R2 have been established with attendant conformational changes. Fe (II) binds to Site B tighter and faster and these and other results provide important information towards the di-iron cofactor assembly mechanism in R2 and could have possible implications for the development of modified and new anticancer and antiviral drugs.

Active catalysts of sonoelectrochemically prepared iron metal nanoparticles for the electroreduction of chloroacetates

NASA Astrophysics Data System (ADS)

Sáez, V.; González-García, J.; Marken, F.

2010-01-01

A new methodology for the sonoelectro-deposition and stripping of highly reactive iron at boron-doped diamond electrodes has been studied. In aqueous 1 M NH4F iron metal readily and reversibly electro-deposits onto boron-doped diamond electrodes. The effects of deposition potential, FeF63- concentration, deposition time, and mass transport are investigated and also the influence of power ultrasound (24 kHz, 8 Wcm-2). Scanning electron microscopy images of iron nanoparticles grown to typically 20-30 nm diameters are obtained. It is shown that a strongly and permanently adhering film of iron at boron-doped diamond can be formed and transferred into other solution environments. The catalytic reactivity of iron deposits at boron-doped diamond is investigated for the reductive dehalogenation of chloroacetate. The kinetically limited multi-electron reduction of trichloroacetate is dependent on the FeF63- deposition conditions and the solution composition. It is demonstrated that a stepwise iron-catalysed dechlorination via dichloroacetate and monochloroacetate to acetate is feasible. This sonoelectrochemical methodology offers a novel, clean and very versatile electro-dehalogenation methodology. The role of fluoride in the surface electrochemistry of iron deserves further attention.

Reduction experiment of iron scale by adding waste plastics.

PubMed

Zhang, Chongmin; Chen, Shuwen; Miao, Xincheng; Yuan, Hao

2009-01-01

The special features of waste plastics in China are huge in total amount, various in type and dispersive in deposition. Therefore, it is necessary to try some new ways that are fit to Chinese situation for disposing waste plastics as metallurgical raw materials more effectively and flexibly. Owing to its high ferrous content and less impurity, the iron scale became ideal raw material to produce pure iron powder. One of the methods to produce pure iron powder is Hoganas Method, by which, after one or multistage of reduction steps, the iron scale can be reduced pure iron powder. However, combining utilization of waste plastics and iron powder production, a series of reduction experiments were arranged and investigated, which is hoped to take use of both thermal and chemical energy contained in waste plastics as well as to improve the reducing condition of iron scale, and hence to develop a new metallurgical way of disposing waste plastics. The results show that under these experimental conditions, the thermal-decomposition of water plastics can conduce to an increase of porosity in the reduction systems. Moreover, better thermodynamics and kinetics conditions for the reduction of scale can be reached. As a result, the reduction rate is increased.

Reactive extraction at liquid-liquid systems

NASA Astrophysics Data System (ADS)

Wieszczycka, Karolina

2018-01-01

The chapter summarizes the state of knowledge about a metal transport in two-phase system. The first part of this review focuses on the distribution law and main factors determination in classical solvent extraction (solubility and polarity of the solute, as well as inter- and intramolecules interaction. Next part of the chapter is devoted to the reactive solvent extraction and the molecular modeling requiring knowledge on type of extractants, complexation mechanisms, metals ions speciation and oxidation during complexes forming, and other parameters that enable to understand the extraction process. Also the kinetic data that is needed for proper modeling, simulation and design of processes needed for critical separations are discussed. Extraction at liquid-solid system using solvent impregnated resins is partially identical as in the case of the corresponding solvent extraction, therefore this subject was also presented in all aspects of separation process (equilibrium, mechanism, kinetics).

Linking Thermodynamics to Pollutant Reduction Kinetics by Fe2+ Bound to Iron Oxides.

PubMed

Stewart, Sydney M; Hofstetter, Thomas B; Joshi, Prachi; Gorski, Christopher A

2018-05-15

Numerous studies have reported that pollutant reduction rates by ferrous iron (Fe 2+ ) are substantially enhanced in the presence of an iron (oxyhydr)oxide mineral. Developing a thermodynamic framework to explain this phenomenon has been historically difficult due to challenges in quantifying reduction potential ( E H ) values for oxide-bound Fe 2+ species. Recently, our group demonstrated that E H values for hematite- and goethite-bound Fe 2+ can be accurately calculated using Gibbs free energy of formation values. Here, we tested if calculated E H values for oxide-bound Fe 2+ could be used to develop a free energy relationship capable of describing variations in reduction rate constants of substituted nitrobenzenes, a class of model pollutants that contain reducible aromatic nitro groups, using data collected here and compiled from the literature. All the data could be described by a single linear relationship between the logarithms of the surface-area-normalized rate constant ( k SA ) values and E H and pH values [log( k SA ) = - E H /0.059 V - pH + 3.42]. This framework provides mechanistic insights into how the thermodynamic favorability of electron transfer from oxide-bound Fe 2+ relates to redox reaction kinetics.

Iron Impregnated Activated Carbon as an Efficient Adsorbent for the Removal of Methylene Blue: Regeneration and Kinetics Studies

PubMed Central

Shah, Irfan; Adnan, Rohana; Wan Ngah, Wan Saime; Mohamed, Norita

2015-01-01

In this study, iron impregnated activated carbon (FeAC) was synthesized following an oxidation and iron impregnation of activated carbon (AC). Both the AC and FeAC were characterized by pHZPC and FTIR spectroscopy. The removal of Methylene Blue (MB) by AC and FeAC was examined under various experimental conditions. The FeAC showed up to 95% (higher than AC) MB removal in the pH range of 7–10. Although the reaction kinetics was pseudo–second order, the overall rate was controlled by a number of processes such as film diffusion, pore diffusion and intraparticle diffusion. The activation energy values for the MB uptake by AC and FeAC (21.79 and 14.82 kJ/mol, respectively) revealed a physisorption process. In the regeneration study, FeAC has shown consistently ≥ 90% MB removal even up to 10 repeated cycles. The reusable characteristic of the spent FeAC improved the practical use of activated carbon and can be a breakthrough for continuous flow system applications where it can work effectively without any significant reduction in its performance. PMID:25849291

Automatic control system for uniformly paving iron ore pellets

NASA Astrophysics Data System (ADS)

Wang, Bowen; Qian, Xiaolong

2014-05-01

In iron and steelmaking industry, iron ore pellet qualities are crucial to end-product properties, manufacturing costs and waste emissions. Uniform pellet pavements on the grate machine are a fundamental prerequisite to ensure even heat-transfer and pellet induration successively influences performance of the following metallurgical processes. This article presents an automatic control system for uniformly paving green pellets on the grate, via a mechanism mainly constituted of a mechanical linkage, a swinging belt, a conveyance belt and a grate. Mechanism analysis illustrates that uniform pellet pavements demand the frontend of the swinging belt oscillate at a constant angular velocity. Subsequently, kinetic models are formulated to relate oscillatory movements of the swinging belt's frontend to rotations of a crank link driven by a motor. On basis of kinetic analysis of the pellet feeding mechanism, a cubic B-spline model is built for numerically computing discrete frequencies to be modulated during a motor rotation. Subsequently, the pellet feeding control system is presented in terms of compositional hardware and software components, and their functional relationships. Finally, pellet feeding experiments are carried out to demonstrate that the control system is effective, reliable and superior to conventional methods.

Kinetic research on dechlorinating dichlorobenzene in aqueous system by nano-scale nickel/iron loaded with CMC/NFC hydrogel.

PubMed

Wan, Xiao-Fang; Guo, Congbao; Liu, Yu; Chai, Xin-Sheng; Li, Youming; Chen, Guangxue

2018-03-01

In this study, we reported on the nano-scale nickel/iron particles loaded in carboxymethyl/nanofibrillated cellulose (CMC/NFC) hydrogel for the dechlorination of o-dichlorobenzene (DCB) in aqueous solution. The biodegradable hydrogel may provide an ideal supporting material for fastening the bimetallic nano-scale particles, which was examined and characterized by TEM, SEM-EDX, FT-IR and BET. The performance of the selected bimetallic particles was evaluated by conducting the dechlorination of DCB in the solution under different reaction conditions (e.g., pH, dosage of nickel/iron nanoparticles and temperature). The results showed that about 70% of DCB could be dechlorinated at 20 °C in 8 h, which indicated that the immobilized reactive material had a high reduction activity when Ni/Fe loading dosage in the hydrogel (18 wt%) was considered. Moreover, the reduction behavior agreed to the pseudo-first order reaction, in which the dechlorination rate was irrelative to the pH aqueous solution. A kinetic model for predicting the concentration of DCB during the reduction reaction was established based on the experimental data. Copyright © 2017 Elsevier Ltd. All rights reserved.

Iron and oxygen isotope fractionation during iron UV photo-oxidation: Implications for early Earth and Mars

NASA Astrophysics Data System (ADS)

Nie, Nicole X.; Dauphas, Nicolas; Greenwood, Richard C.

2017-01-01

Banded iron formations (BIFs) contain appreciable amounts of ferric iron (Fe3+). The mechanism by which ferrous iron (Fe2+) was oxidized into Fe3+ in an atmosphere that was globally anoxic is highly debated. Of the three scenarios that have been proposed to explain BIF formation, photo-oxidation by UV photons is the only one that does not involve life (the other two are oxidation by O2 produced by photosynthesis, and anoxygenic photosynthesis whereby Fe2+ is directly used as electron donor in place of water). We experimentally investigated iron and oxygen isotope fractionation imparted by iron photo-oxidation at a pH of 7.3. The iron isotope fractionation between precipitated Fe3+-bearing lepidocrocite and dissolved Fe2+ follows a Rayleigh distillation with an instantaneous 56Fe/54Fe fractionation factor of + 1.2 ‰. Such enrichment in the heavy isotopes of iron is consistent with the values measured in BIFs. We also investigated the nature of the mass-fractionation law that governs iron isotope fractionation in the photo-oxidation experiments (i.e., the slope of the δ56Fe-δ57Fe relationship). The experimental run products follow a mass-dependent law corresponding to the high-T equilibrium limit. The fact that a ∼3.8 Gyr old BIF sample (IF-G) from Isua (Greenland) falls on the same fractionation line confirms that iron photo-oxidation in the surface layers of the oceans was a viable pathway to BIF formation in the Archean, when the atmosphere was largely transparent to UV photons. Our experiments allow us to estimate the quantum yield of the photo-oxidation process (∼0.07 iron atom oxidized per photon absorbed). This yield is used to model iron oxidation on early Mars. As the photo-oxidation proceeds, the aqueous medium becomes more acidic, which slows down the reaction by changing the speciation of iron to species that are less efficient at absorbing UV-photons. Iron photo-oxidation in centimeter to meter-deep water ponds would take months to years to complete. Oxidation by O2 in acidic conditions would be slower. Iron photo-oxidation is thus likely responsible for the formation of jarosite-hematite deposits on Mars, provided that shallow standing water bodies could persist for extended periods of time. The oxygen isotopic composition of lepidocrocite precipitated from the photo-oxidation experiment was measured and it is related to the composition of water by mass-dependent fractionation. The precipitate-fluid 18O/16O isotope fractionation of ∼ + 6 ‰ is consistent with previous determinations of oxygen equilibrium fraction factors between iron oxyhydroxides and water.

Arsenic Redistribution Between Sediments and Water Near a Highly Contaminated Source

DOE Office of Scientific and Technical Information (OSTI.GOV)

Keimowitz,A.; Zheng, Y.; Chillrud, S.

2005-01-01

Mechanisms controlling arsenic partitioning between sediment, groundwater, porewaters, and surface waters were investigated at the Vineland Chemical Company Superfund site in southern New Jersey. Extensive inorganic and organic arsenic contamination at this site (historical total arsenic >10 000 {micro}g L{sup -1} or >130 {micro}M in groundwater) has spread downstream to the Blackwater Branch, Maurice River, and Union Lake. Stream discharge was measured in the Blackwater Branch, and water samples and sediment cores were obtained from both the stream and the lake. Porewaters and sediments were analyzed for arsenic speciation as well as total arsenic, iron, manganese, and sulfur, and theymore » indicate that geochemical processes controlling mobility of arsenic were different in these two locations. Arsenic partitioning in the Blackwater Branch was consistent with arsenic primarily being controlled by sulfur, whereas in Union Lake, the data were consistent with arsenic being controlled largely by iron. Stream discharge and arsenic concentrations indicate that despite large-scale groundwater extraction and treatment, >99% of arsenic transport away from the site results from continued discharge of high arsenic groundwater to the stream, rather than remobilization of arsenic in stream sediments. Changing redox conditions would be expected to change arsenic retention on sediments. In sulfur-controlled stream sediments, more oxic conditions could oxidize arsenic-bearing sulfide minerals, thereby releasing arsenic to porewaters and streamwaters; in iron-controlled lake sediments, more reducing conditions could release arsenic from sediments via reductive dissolution of arsenic-bearing iron oxides.« less

Characterization of Fe-leonardite complexes as novel natural iron fertilizers.

PubMed

Kovács, Krisztina; Czech, Viktória; Fodor, Ferenc; Solti, Adam; Lucena, Juan J; Santos-Rosell, Sheila; Hernández-Apaolaza, Lourdes

2013-12-18

Water-soluble humic substances (denoted by LN) extracted at alkaline pH from leonardite are proposed to be used as complexing agents to overcome micronutrient deficiencies in plants such as iron chlorosis. LN presents oxidized functional groups that can bind Fe(2+) and Fe(3+). The knowledge of the environment of Fe in the Fe-LN complexes is a key point in the studies on their efficacy as Fe fertilizers. The aim of this work was to study the Fe(2+)/Fe(3+) species formed in Fe-LN complexes with (57)Fe Mössbauer spectroscopy under different experimental conditions in relation to the Fe-complexing capacities, chemical characteristics, and efficiency to provide iron in hydroponics. A high oxidation rate of Fe(2+) to Fe(3+) was found when samples were prepared with Fe(2+), although no well-crystalline magnetically ordered ferric oxide formation could be observed in slightly acidic or neutral media. It seems to be the case that the formation of Fe(3+)-LN compounds is favored over Fe(2+)-LN compounds, although at acidic pH no complex formation between Fe(3+) and LN occurred. The Fe(2+)/Fe(3+) speciation provided by the Mössbauer data showed that Fe(2+)-LN could be efficient in hydroponics while Fe(3+)-LN is suggested to be used more effectively under calcareous soil conditions. However, according to the biological assay, Fe(3+)-LN proved to be effective as a chlorosis corrector applied to iron-deficient cucumber in nutrient solution.

Iron speciation and dynamics during SERIES, a mesoscale iron enrichment experiment in the NE Pacific

NASA Astrophysics Data System (ADS)

Wong, C. S.; Johnson, W. K.; Sutherland, N.; Nishioka, J.; Timothy, D. A.; Robert, M.; Takeda, S.

2006-10-01

During the Sub-arctic Ecosystem Response to Iron Enrichment Study (SERIES), the addition of ferrous iron to high-nitrate low-chlorophyll (HNLC) waters near Ocean Station PAPA (OSP: 50°N, 145°W) produced a phytoplankton bloom and CO 2 drawdown, as evidenced by decreasing CO 2 fugacity ( fCO 2). We analyzed five fractions or phases of iron: soluble (<0.03 μm), dissolved (<0.22 μm), total dissolved (acidified dissolved, <0.22 μm), labile (unfiltered), and total (acidified, unfiltered). From these, we also calculated non-labile iron, colloidal iron (0.03-0.22 μm), and both labile and non-labile particulate iron (>0.22 μm). Here, we describe iron distributions and the evolution of iron phases in the upper ocean during the experiment. We also present an iron budget accounting for horizontal and vertical dilution. At the time of our first sampling eight hours after fertilization was completed, total iron reached 8.6 nmol L -1 and dissolved iron was approximately 3 nmol L -1. Early in the experiment the dissolved iron phase decreased the most rapidly and by late day 6 the integrated dissolved iron (8.6 μmol m -2) represented less than 10% of the initial addition (90-95 μmol m -2). However at this same time the total integrated iron at the centre of the patch was still 52 μmol m -2 or almost 60% of the calculated initial addition. By day 12,45% of the added iron (from both injections) could be accounted for in the patch. The half-life of total iron in the patch for the first injection was estimated to be less than 5 days if dilution is not considered, but more than 13 days if dilution is taken into account. The most notable change in iron percentages from one form to another occurred early in the first week of the experiment where the predominant phase shift was from the colloidal portion of dissolved iron to labile particulate iron that could have been biologically induced or simply aggregation of oxyhydroxides. This was immediately followed by a physical event resulting in a reduction in the non-labile particulate iron due to sinking out of the patch. The second infusion did not change the relative concentration of the various pools of iron as might be expected, but this was likely due to the fact that it was a much smaller injection than the first. The most pronounced change after the second infusion was the reduction in the labile particulate pool which coincided with one of the largest decreases in silicate observed during the entire experiment. In general the gradual decrease in the fraction of the 10 m colloidal iron as well as episodic losses of, or shifts in, integrated colloidal iron are thought to be the result of adsorption of colloidal iron to the plankton cell surfaces as well as aggregation of oxyhydroxides but could also be the result of utilization of colloidal iron by mixotrophic phytoplankton.

Solid-Phase Speciation of Arsenic As the Primary Control on Dissolved As Concentrations in a Glacial Aquifer System: Quantifying Speciation of Arsenic in Glacial Aquifer Solids with μXAS Mapping.

NASA Astrophysics Data System (ADS)

Nicholas, S. L.; Gowan, A. S.; Knaeble, A. R.; Erickson, M. L.; Woodruff, L. G.; Marcus, M.; Toner, B. M.

2014-12-01

Western Minnesota, USA, is a regional locus of drinking-water wells with high arsenic (As) (As>10µgL-1). Arsenic concentrations vary widely among neighboring wells with otherwise similar water chemistry [1,2]. As(III) should be the most mobile As species in Minnesota well waters (median Eh in As affected wells is -50mV). This As is geogenic, sourced from glacial deposits derived from Cretaceous sedimentary bedrock (dolostone, limestone, shale). Our hypothesis is that As speciation in the solid phase is the important factor controlling the introduction of As to groundwater—more significant in this region than absolute As concentrations or landscape variability. Our previous research used micro-X-ray absorption spectroscopy (µXAS) speciation mapping [3] on archived glacial tills (stored dry at room temperature in air). µXAS results from this material showed that As in a reduced chemical state within the till aquitard is spatially correlated with iron sulfide at the micron scale. Conversley, As in aquifer sediments was mainly oxidized As(V). At the aquifer-aquitard contact As was observed as a mixture of both reduced and oxidized forms. This suggests that the aquifer-aquitard contact is a geochemically active zone in which reduced As species present within glacial till are converted to As(V) through complex redox processes, and subsequently release into aquifer sediments. Our current research applies the same methods to describe As speciation in samples collected from fresh cores of glacial sediment and frozen under argon in the field. Preliminary results are similar to our previous work in that As is, in general, more reduced in aquitard sediments, and more oxidized at the contact and in aquifer sediments. Arsenic(III) was preserved as a minor consitutent in ambient archived cores but is a more significant constituent in fresh, anaerobically preserved cores. Results will be presented comparing anaerobic samples with ambient-air aliquots of the same sample to document changes in the relative abundance of As species depending on sample preservation. This work was supported by LBNL-ALS, ANL-APS, USGS-MNWSC, MGS, and CURA. [1]Berndt & Soule (1999) Minnesota Arsenic Research Study: Report on Geochemistry. [2] Erickson & Barnes (2005) Water Research 39 4029-4039. [3] Toner et al. (2014) Env. Chem. 11 4-9.

Catalytic Activity of μ-Carbido-Dimeric Iron(IV) Octapropylporphyrazinate in the 3,5,7,2',4'-Pentahydroxyflavone Oxidation Reaction with tert-Butyl Hydroperoxide

NASA Astrophysics Data System (ADS)

Tyurin, D. V.; Zaitseva, S. V.; Kudrik, E. V.

2018-05-01

It is found for the first time that μ-carbido-dimeric iron(IV) octapropylporphyrazinate displays catalytic activity in the oxidation reaction of natural flavonol morin with tert-butyl hydroperoxide, with the catalyst being stable under conditions of the reaction. The kinetics of this reaction are studied. It is shown the reaction proceeds via tentative formation of a complex between the catalyst and the oxidant, followed by O‒O bond homolytic cleavage. The kinetics of the reaction is described in the coordinates of the Michaelis-Menten equation. A linear dependence of the apparent reaction rate constant on the concentration of the catalyst is observed, testifying to its participation in the limiting reaction step. The equilibrium constants and rates of interaction are found. A mechanism is proposed for the reaction on the basis of the experimental data.

Formation of iron sulphide in solar nebula

NASA Technical Reports Server (NTRS)

Kerridge, J. F.

1976-01-01

Noting that the iron sulfide in the Orgueil carbonaceous meteorite is an Fe-deficient monosulfide (pyrrhotite), it is suggested that such mineral chemistry is inconsistent with equilibrium condensation of the solar nebula and that the course of condensation may have been modified by kinetic effects. The effect of Ni on the reaction between Fe and S to produce FeS is examined, and possible reasons are considered for the fact that the cited meteorite differs in both crystal structure and Ni content from the predictions of equilibrium condensation. It is proposed that sulfide formation in the solar nebula may have been inhibited by sluggish diffusion, so that sulfur began to react with previously condensed troilite to form pyrrhotite. On this basis, observations of the Orgueil sulfides are shown to suggest that the course of solar-system condensation was modified by kinetic effects below about 700 K and that equilibrium may not have been achieved.

Experimental Investigation on Reduction Kinetics of Stainless Steel-Making Slag in Iron Bath Smelting Reduction

NASA Astrophysics Data System (ADS)

Zhang, Bo; Liu, Jienan; Yang, Yanfeng; Liu, Luming; Liu, Jiechao; Luo, Lijian; Ma, Yubao; Hong, Xin

Reduction kinetics of stainless steel slag in iron bath smelting reduction was studied at the temperature of 1500°C ˜ 1650°C. It was concluded that the reduction process consisted of two parts. That is to say smelting reduction was controlled by stainless steel slag melting initially and by interface reaction later. In order to increase smelting reaction rate, the melting point of slag should be decreased at the first stage and adjust the liquidity of slag at later stage. Smelting reaction rate will be accelerated by means of optimize the slag content. The optimal reduction result that all most all of the chromium in slag been recovered was obtained in temperature was 1500°C, basicity of slag was 1.0˜1.2, the value of Al2O3+MgO was 25%.

Cyanide speciation at four gold leach operations undergoing remediation

USGS Publications Warehouse

Johnson, Craig A.; Grimes, David J.; Leinz, Reinhard W.; Rye, Robert O.

2008-01-01

Analyses have been made of 81 effluents from four gold leach operations in various stages of remediation to identify the most-persistent cyanide species. Total cyanide and weak acid-dissociable (WAD) cyanide were measured using improved methods, and metals known to form stable cyanocomplexes were also measured. Typically, total cyanide greatly exceeded WAD indicating that cyanide was predominantly in strong cyanometallic complexes. Iron was generally too low to accommodate the strongly complexed cyanide as Fe(CN)63- or Fe(CN)64-, but cobalt was abundant enough to implicate Co(CN)63- or its dissociation products (Co(CN)6-x(H2O)x(3-x)-). Supporting evidence for cobalt-cyanide complexation was found in tight correlations between cobalt and cyanide in some sample suites. Also, abundant free cyanide was produced upon UV illumination. Iron and cobalt cyanocomplexes both photodissociate; however, the iron concentration was insufficient to have carried the liberated cyanide, while the cobalt concentration was sufficient. Cobalt cyanocomplexes have not previously been recognized in cyanidation wastes. Their identification at four separate operations, which had treated ores that were not especially rich in cobalt, suggests that cobalt complexation may be a common source of cyanide persistence. There is a need for more information on the importance and behavior of cobalt cyanocomplexes in ore-processing wastes at gold mines.

Cyanide speciation at four gold leach operations undergoing remediation.

PubMed

Johnson, Craig A; Grimes, David J; Leinz, Reinhard W; Rye, Robert O

2008-02-15

Analyses have been made of 81 effluents from four gold leach operations in various stages of remediation to identify the most -persistent cyanide species. Total cyanide and weak acid-dissociable (WAD) cyanide were measured using improved methods, and metals known to form stable cyanocomplexes were also measured. Typically, total cyanide greatly exceeded WAD indicating that cyanide was predominantly in strong cyanometallic complexes. Iron was generally too low to accommodate the strongly complexed cyanide as Fe(CN)6s3- or Fe(CN)6(4-), but cobalt was abundant enough to implicate Co(CN)6(3-) or its dissociation products (Co(CN)(6-x)(H2O)x((3-x)-)). Supporting evidenceforcobalt-cyanide complexationwas found in tight correlations between cobalt and cyanide in some sample suites. Also, abundant free cyanide was produced upon UV illumination. Iron and cobalt cyanocomplexes both photodissociate; however, the iron concentration was insufficient to have carried the liberated cyanide, while the cobalt concentration was sufficient. Cobalt cyanocomplexes have not previously been recognized in cyanidation wastes. Their identification atfour separate operations, which had treated ores that were not especially rich in cobalt, suggests that cobalt complexation may be a common source of cyanide persistence. There is a need for more information on the importance and behavior of cobalt cyanocomplexes in ore-processing wastes at gold mines.

Direct and indirect photodegradation of estriol in the presence of humic acid, nitrate and iron complexes in water solutions.

PubMed

Chen, Yong; Zhang, Kai; Zuo, Yuegang

2013-10-01

The photochemical behavior of a natural estrogen estriol (E3) was investigated in the presence of the natural photoreactive constituents including nitrate, iron(III), and humic acid (HA). The direct photodegradation of E3 increased with increasing incident light intensity, decreasing initial concentration of E3 and increasing pH in the range of 6.0 to 10.0. The direct photodegradation of the deprotonated speciation of E3 was much faster than that of its protonated form. The presence of NO3(-) and iron(III) promoted the photochemical loss of E3 in the aqueous solutions. The quenching experiments verified that hydroxyl radicals were predominantly responsible for the indirect photodegradation of E3. HA could act as photosensitizer, light screening agent and free radical quencher. For the first time, the enhancement or inhibition effect of HA on photodegradation was found to depend on the irradiation light intensity. HA enhanced the photodegradation of E3 under sunlight or weak irradiation of simulated sunlight. In contrast, under high irradiation light intensity, HA inhibited the photodegradation. The hydroxylation photoproducts were identified using GC-MS and the photodegradation pathway of E3 was proposed. Copyright © 2013 Elsevier B.V. All rights reserved.

Competitive and Cooperative Effects during Nickel Adsorption to Iron Oxides in the Presence of Oxalate

DOE Office of Scientific and Technical Information (OSTI.GOV)

Flynn, Elaine D.; Catalano, Jeffrey G.

Iron oxides are ubiquitous in soils and sediments and play a critical role in the geochemical distribution of trace elements and heavy metals via adsorption and coprecipitation. The presence of organic acids may potentially alter how metals associate with iron oxide minerals through a series of cooperative or competitive processes: solution complexation, ternary surface complexation, and surface site competition. The macroscopic and molecular-scale effects of these processes were investigated for Ni adsorption to hematite and goethite at pH 7 in the presence of oxalate. The addition of this organic acid suppresses Ni uptake on both minerals. Aqueous speciation suggests thatmore » this is dominantly the result of oxalate complexing and solubilizing Ni. Comparison of the Ni surface coverage to the concentration of free (uncomplexed) Ni 2+ in solution suggests that the oxalate also alters Ni adsorption affinity. EXAFS and ATR-FTIR spectroscopies indicate that these changes in binding affinity are due to the formation of Ni–oxalate ternary surface complexes. These observations demonstrate that competition between dissolved oxalate and the mineral surface for Ni overwhelms the enhancement in adsorption associated with ternary complexation. Oxalate thus largely enhances Ni mobility, thereby increasing micronutrient bioavailability and inhibiting contaminant sequestration.« less

Reactivity of catecholamine-driven Fenton reaction and its relationships with iron(III) speciation.

PubMed

Melin, Victoria; Henríquez, Adolfo; Freer, Juanita; Contreras, David

2015-03-01

Fenton reaction is the main source of free radicals in biological systems. The reactivity of this reaction can be modified by several factors, among these iron ligands are important. Catecholamine (dopamine, epinephrine, and norepinephrine) are able to form Fe(III) complexes whose extension in the coordination number depends upon the pH. Fe(III)-catecholamine complexes have been related with the development of several pathologies. In this work, the ability of catecholamines to enhance the oxidative degradation of an organic substrate (veratryl alcohol, VA) through Fenton and Fenton-like reactions was studied. The initial VA degradation rate at different pH values and its relationship to the different iron species present in solution were determined. Furthermore, the oxidative degradation of VA after 24 hours of reaction and its main oxidation products were also determined. The catecholamine-driven Fenton and Fenton-like systems showed higher VA degradation compared to unmodified Fenton or Fenton-like systems, which also showed an increase in the oxidation state of the VA degradation product. All of this oxidative degradation takes place at pH values lower than 5.50, where the primarily responsible species would be the Fe(III) mono-complex. The presence of Fe(III) mono-complex is essential in the ability of catecholamines to increase the oxidative capacity of Fenton systems.

Chemical equilibrium modeling of organic acids, pH, aluminum, and iron in Swedish surface waters.

PubMed

Sjöstedt, Carin S; Gustafsson, Jon Petter; Köhler, Stephan J

2010-11-15

A consistent chemical equilibrium model that calculates pH from charge balance constraints and aluminum and iron speciation in the presence of natural organic matter is presented. The model requires input data for total aluminum, iron, organic carbon, fluoride, sulfate, and charge balance ANC. The model is calibrated to pH measurements (n = 322) by adjusting the fraction of active organic matter only, which results in an error of pH prediction on average below 0.2 pH units. The small systematic discrepancy between the analytical results for the monomeric aluminum fractionation and the model results is corrected for separately for two different fractionation techniques (n = 499) and validated on a large number (n = 3419) of geographically widely spread samples all over Sweden. The resulting average error for inorganic monomeric aluminum is around 1 µM. In its present form the model is the first internally consistent modeling approach for Sweden and may now be used as a tool for environmental quality management. Soil gibbsite with a log *Ks of 8.29 at 25°C together with a pH dependent loading function that uses molar Al/C ratios describes the amount of aluminum in solution in the presence of organic matter if the pH is roughly above 6.0.

Oxidation of interconnect alloys in an electric field

DOE Office of Scientific and Technical Information (OSTI.GOV)

Holcomb, G.R.; Alman, D.E.; Adler, T.A.

The effect of an electric field on the oxidation of interconnect alloys was examined with a representative array of materials: an iron-base ferritic chromia former (E-brite), an iron-base ferritic chromia former with Mn and La (Crofer 22APU), a nickel-base chromia former (IN-718), and a nickelbase chromia former with Mn and La (Haynes 230). Environmental variables include temperature and oxygen partial pressure. The resulting scales were examined to determine if applied electrical current induces changes in mechanism or scale growth kinetics.

Combustion chemistry of ethanol: Ignition and speciation studies in a rapid compression facility [On the combustion chemistry of ethanol: Ignition and speciation studies in a rapid compression facility

DOE Office of Scientific and Technical Information (OSTI.GOV)

Barraza-Botet, Cesar L.; Wagnon, Scott W.; Wooldridge, Margaret S.

Here, ethanol remains the most important alternative fuel for the transportation sector. This work presents new experimental data on ethanol ignition, including stable species measurements, obtained with the University of Michigan rapid compression facility. Ignition delay times were determined from pressure histories of ignition experiments with stoichiometric ethanol–air mixtures at pressures of ~3–10 atm. Temperatures (880–1150 K) were controlled by varying buffer gas composition (Ar, N 2, CO 2). High-speed imaging was used to record chemiluminescence during the experiments, which showed homogeneous ignition events. The results for ignition delay time agreed well with trends on the basis of previous experimentalmore » measurements. Speciation experiments were performed using fast gas sampling and gas chromatography to identify and quantify ethanol and 11 stable intermediate species formed during the ignition delay period. Simulations were carried out using a chemical kinetic mechanism available in the literature, and the agreement with the experimental results for ignition delay time and the intermediate species measured was excellent for the majority of the conditions studied. From the simulation results, ethanol + HO 2 was identified as an important reaction at the experimental conditions for both the ignition delay time and intermediate species measurements. Further studies to improve the accuracy of the rate coefficient for ethanol + HO 2 would improve the predictive understanding of intermediate and low-temperature ethanol combustion.« less

Nickel (II) Preconcentration and Speciation Analysis During Transport from Aqueous Solutions Using a Hollow-fiber Permeation Liquid Membrane (HFPLM) Device.

PubMed

Bautista-Flores, Ana Nelly; De San Miguel, Eduardo Rodríguez; Gyves, Josefina de; Jönsson, Jan Åke

2011-08-18

Nickel (II) preconcentration and speciation analysis using a hollow fiber supported liquid membrane (HFSLM) device was studied. A counterflow of protons coupled to complexation with formate provided the driving force of the process, while Kelex 100 was employed as carrier. The influence of variables related to module configuration (acceptor pH and carrier concentration) and to the sample properties (donor pH) on the preconcentration factor, E, was simultaneously studied and optimized using a 3 factor Doehlert matrix response surface methodology. The effect of metal concentration was studied as well. Preconcentration factors as high as 4240 were observed  depending on the values of the different variables. The effects of the presence of inorganic anions (NO2-, SO42-, Cl-, NO3-, CO32-, CN-) and dissolved organic matter (DOM) in the form of humic acids were additionally considered in order to carry out a speciation analysis study. Nickel preconcentration was observed to be independent of both effects, except when cyanide was present in the donor phase. A characterization of the transport regime was performed through the analysis of the dependence of E on the temperature. E increases with the increase in temperature according to the equation E(K) = -8617.3 + 30.5T with an activation energy of 56.7 kJ mol-1 suggesting a kinetic-controlled regime. Sample depletion ranged from 12 to 1.2% depending on the volume of the donor phase (100 to 1000 mL, respectively).

Combustion chemistry of ethanol: Ignition and speciation studies in a rapid compression facility [On the combustion chemistry of ethanol: Ignition and speciation studies in a rapid compression facility

DOE PAGES

Barraza-Botet, Cesar L.; Wagnon, Scott W.; Wooldridge, Margaret S.

2016-08-31

Here, ethanol remains the most important alternative fuel for the transportation sector. This work presents new experimental data on ethanol ignition, including stable species measurements, obtained with the University of Michigan rapid compression facility. Ignition delay times were determined from pressure histories of ignition experiments with stoichiometric ethanol–air mixtures at pressures of ~3–10 atm. Temperatures (880–1150 K) were controlled by varying buffer gas composition (Ar, N 2, CO 2). High-speed imaging was used to record chemiluminescence during the experiments, which showed homogeneous ignition events. The results for ignition delay time agreed well with trends on the basis of previous experimentalmore » measurements. Speciation experiments were performed using fast gas sampling and gas chromatography to identify and quantify ethanol and 11 stable intermediate species formed during the ignition delay period. Simulations were carried out using a chemical kinetic mechanism available in the literature, and the agreement with the experimental results for ignition delay time and the intermediate species measured was excellent for the majority of the conditions studied. From the simulation results, ethanol + HO 2 was identified as an important reaction at the experimental conditions for both the ignition delay time and intermediate species measurements. Further studies to improve the accuracy of the rate coefficient for ethanol + HO 2 would improve the predictive understanding of intermediate and low-temperature ethanol combustion.« less

Mechanisms of Arsenic Sequestration by Prosopis juliflora during the Phytostabilization of Metalliferous Mine Tailings.

PubMed

Hammond, Corin M; Root, Robert A; Maier, Raina M; Chorover, Jon

2018-02-06

Phytostabilization is a cost-effective long-term bioremediation technique for the immobilization of metalliferous mine tailings. However, the biogeochemical processes affecting metal(loid) molecular stabilization and mobility in the root zone remain poorly resolved. The roots of Prosopis juliflora grown for up to 36 months in compost-amended pyritic mine tailings from a federal Superfund site were investigated by microscale and bulk synchrotron X-ray absorption spectroscopy (XAS) and multiple energy micro-X-ray fluorescence imaging to determine iron, arsenic, and sulfur speciation, abundance, and spatial distribution. Whereas ferrihydrite-bound As(V) species predominated in the initial bulk mine tailings, the rhizosphere speciation of arsenic was distinctly different. Root-associated As(V) was immobilized on the root epidermis bound to ferric sulfate precipitates and within root vacuoles as trivalent As(III)-(SR) 3  tris-thiolate complexes. Molar Fe-to-As ratios of root epidermis tissue were two times higher than the 15% compost-amended bulk tailings growth medium. Rhizoplane-associated ferric sulfate phases that showed a high capacity to scavenge As(V) were dissimilar from the bulk-tailings mineralogy as shown by XAS and X-ray diffraction, indicating a root-surface mechanism for their formation or accumulation.

Experiments and Modeling of Uranium Adsorption in the Presence of Other Ions in Simulated Seawater

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ladshaw, Austin; Das, Sadananda; Liao, Wei-Po

2015-11-19

Seawater contains uranium at an average concentration of 3.3 ppb, as well as a variety of other ions at either overwhelmingly higher or similar concentrations, which complicate the recovery of uranium. This report describes an investigation of the effects of various factors such as uranium speciation and presence of salts including sodium, calcium, magnesium, and bicarbonate, as well as trace elements such as vanadium on uranium adsorption kinetics in laboratory experiments. Adsorption models are also developed to describe the experimental data of uranium extraction from seawater. Results show that the presence of calcium and magnesium significantly slows down the uraniummore » adsorption kinetics. Vanadium can replace uranium from amidoxime-based adsorbent in the presence of sodium in the solution. Results also show that bicarbonate in the solution strongly competes with amidoxime for binding uranium, and thus slows down the uranium adsorption kinetics. Developed on the basis of the experimental findings, the model is capable of describing the effects of pH, ionic strength, temperature, and concentration of various species. The results of this work are useful in the understanding of the important factors that control the adsorbent capacity and kinetics of uranium uptake by amidoxime-based adsorbents.« less

Factors affecting the open-circuit voltage and electrode kinetics of some iron/titanium/redox flow cells

NASA Technical Reports Server (NTRS)

Reid, M. A.; Gahn, R. F.

1977-01-01

The effect of acid concentration on the performance of the iron-titanium redox flow cell was studied. When the acidity was increased, open-circuit voltages decreased on the titanium side but load voltages increased due to decreased polarization. The best load voltage occurs when there is high acidity on the titanium side coupled with low acidity on the iron side, but such cells show voltage losses with repeated cycling because of the diffusion of acid through the membrane. No membrane tested has been found capable of maintaining the differences in acidity. Chelating agents show some promise in reducing polarization at the Ti electrode and thus improving energy efficiency.

Selenium Speciation and Management in Wet FGD Systems

DOE Office of Scientific and Technical Information (OSTI.GOV)

Searcy, K; Richardson, M; Blythe, G

2012-02-29

This report discusses results from bench- and pilot-scale simulation tests conducted to determine the factors that impact selenium speciation and phase partitioning in wet FGD systems. The selenium chemistry in wet FGD systems is highly complex and not completely understood, thus extrapolation and scale-up of these results may be uncertain. Control of operating parameters and application of scrubber additives have successfully demonstrated the avoidance or decrease of selenite oxidation at the bench and pilot scale. Ongoing efforts to improve sample handling methods for selenium speciation measurements are also discussed. Bench-scale scrubber tests explored the impacts of oxidation air rate, tracemore » metals, scrubber additives, and natural limestone on selenium speciation in synthetic and field-generated full-scale FGD liquors. The presence and concentration of redox-active chemical species as well as the oxidation air rate contribute to the oxidation-reduction potential (ORP) conditions in FGD scrubbers. Selenite oxidation to the undesirable selenate form increases with increasing ORP conditions, and decreases with decreasing ORP conditions. Solid-phase manganese [Mn(IV)] appeared to be the significant metal impacting the oxidation of selenite to selenate. Scrubber additives were tested for their ability to inhibit selenite oxidation. Although dibasic acid and other scrubber additives showed promise in early clear liquor (sodium based and without calcium solids) bench-scale tests, these additives did not show strong inhibition of selenite oxidation in tests with higher manganese concentrations and with slurries from full-scale wet FGD systems. In bench-tests with field liquors, addition of ferric chloride at a 250:1 iron-to-selenium mass ratio sorbed all incoming selenite to the solid phase, although addition of ferric salts had no impact on native selenate that already existed in the field slurry liquor sample. As ORP increases, selenite may oxidize to selenate more rapidly than it sorbs to ferric solids. Though it was not possible to demonstrate a decrease in selenium concentrations to levels below the project'ale testing were evident at the pilot scale. Specifically, reducing oxidation air rate and ORP tends to either retain selenium as selenite in the liquor or shift selenium phase partitioning to the solid phase. Oxidation air flow rate control may be one option for managing selenium behavior in FGD scrubbers. Units that cycle load widely may find it more difficult to impact ORP conditions with oxidation air flow rate control alone. Because decreasing oxidation air rates to the reaction tank showed that all new selenium reported to the solids, the addition of ferric chloride to the pilot scrubber could not show further improvements in selenium behavior. Ferric chloride addition did shift mercury to the slurry solids, specifically to the fine particles. Several competing pathways may govern the reporting of selenium to the slurry solids: co-precipitation with gypsum into the bulk solids and sorption or co-precipitation with iron into the fine particles. Simultaneous measurement of selenium and mercury behavior suggests a holistic management strategy is best to optimize the fate of both of these elements in FGD waters. Work conducted under this project evaluated sample handling and analytical methods for selenium speciation in FGD waters. Three analytical techniques and several preservation methods were employed. Measurements of selenium speciation over time indicated that for accurate selenium speciation, it is best to conduct measurements on unpreserved, filtered samples as soon after sampling as possible. The capital and operating costs for two selenium management strategies were considered: ferric chloride addition and oxidation air flow rate control. For ferric chloride addition, as might be expected the reagent makeup costs dominate the overall costs, and range from 0.22 to 0.29 mills/kWh. For oxidation air flow rate control, a cursory comparison of capital costs and turndown capabilities for multi-stage and single-stage centrifugal blowers and several flow control methods was completed. For greenfield systems, changing the selection of blower type and flow control method may have payback periods of 4 to 5 years or more if based on energy savings alone. However, the benefits to managing redox chemistry in the scrubber could far outweigh the savings in electricity costs under some circumstances.« less

Factors affecting the open-circuit voltage and electrode kinetics of some iron/titanium redox flow cells

NASA Technical Reports Server (NTRS)

Reid, M. A.; Gahn, R. F.

1977-01-01

Performance of the iron-titanium redox flow cell was studied as a function of acid concentration. Anion permeable membranes separated the compartments. Electrodes were graphite cloth. Current densities ranged up to 25 mA/square centimeter. Open-circuit and load voltages decreased as the acidity was increased on the iron side as predicted. On the titanium side, open-circuit voltages decreased as the acidity was increased in agreement with theory, but load voltages increased due to decreased polarization with increasing acidity. High acidity on the titanium side coupled with low acidity on the iron side gives the best load voltage, but such cells show voltage losses as they are repeatedly cycled. Analyses show that the bulk of the voltage losses are due to diffusion of acid through the membrane.

Phenol adsorption on surface-functionalized iron oxide nanoparticles: modeling of the kinetics, isotherm, and mechanism

NASA Astrophysics Data System (ADS)

Yoon, Soon Uk; Mahanty, Biswanath; Ha, Hun Moon; Kim, Chang Gyun

2016-06-01

Phenol adsorption from aqueous solution was carried out using uncoated and methyl acrylic acid (MAA)-coated iron oxide nanoparticles (NPs), having size <10 nm, as adsorbents. Batch adsorption studies revealed that the phenol removal efficiency of MAA-coated NPs (950 mg g-1) is significantly higher than that of uncoated NPs (550 mg g-1) under neutral to acidic conditions. However, this improvement disappears above pH 9. The adsorption data under optimized conditions (pH 7) were modeled with pseudo-first- and pseudo-second-order kinetics and subjected to Freundlich and Langmuir isotherms. The analysis determined that pseudo-second-order kinetics and the Freundlich model are appropriate for both uncoated and MAA-coated NPs (all R 2 > 0.98). X-ray photoelectron spectroscopy analysis of pristine and phenol-adsorbed NPs revealed core-level binding energy and charge for Fe(2 s) and O(1 s) on the NP surfaces. The calculations suggest that phenol adsorption onto MAA-coated NPs is a charge transfer process, where the adsorbate (phenol) acts as an electron donor and the NP surface (Fe, O) as an electron acceptor. However, a physisorption process appears to be the relevant mechanism for uncoated NPs.

Adsorption of Azo-Dye Orange II from Aqueous Solutions Using a Metal-Organic Framework Material: Iron- Benzenetricarboxylate

PubMed Central

Rojas García, Elizabeth; López Medina, Ricardo; May Lozano, Marcos; Hernández Pérez, Isaías; Valero, Maria J.; Maubert Franco, Ana M.

2014-01-01

A Metal-Organic Framework (MOF), iron-benzenetricarboxylate (Fe(BTC)), has been studied for the adsorptive removal of azo-dye Orange II from aqueous solutions, where the effect of various parameters was tested and isotherm and kinetic models were suggested. The adsorption capacities of Fe(BTC) were much higher than those of an activated carbon. The experimental data can be best described by the Langmuir isotherm model (R2 > 0.997) and revealed the ability of Fe(BTC) to adsorb 435 mg of Orange II per gram of adsorbent at the optimal conditions. The kinetics of Orange II adsorption followed a pseudo-second-order kinetic model, indicating the coexistence of physisorption and chemisorption, with intra-particle diffusion being the rate controlling step. The thermodynamic study revealed that the adsorption of Orange II was feasible, spontaneous and exothermic process (−25.53 kJ·mol−1). The high recovery of the dye showed that Fe(BTC) can be employed as an effective and reusable adsorbent for the removal of Orange II from aqueous solutions and showed the economic interest of this adsorbent material for environmental purposes. PMID:28788289

Oxidation and deprotonation of synthetic Fe{sup II}-Fe{sup III} (oxy)hydroxycarbonate Green Rust: An X-ray photoelectron study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mullet, M.; Guillemin, Y.; Ruby, C.

X-ray photoelectron spectroscopy (XPS) was used to investigate chemical bonding and distribution of iron and oxygen species at the surface of Green Rusts (GRs). GRs with variable composition, i.e. Fe{sup II}{sub 6(1-x)}Fe{sup III}{sub 6x}O{sub 12}H{sub 2(7-3x)} CO{sub 3}.3H{sub 2}O where the Fe{sup III} molar fraction of the positively charged hydroxide sheets, x=[Fe(III)]/[Fe(total)] belongs to [1/3, 1], were synthesised under an inert atmosphere. The broadened Fe(2p{sub 3/2}) spectra were fitted using Gupta and Sen multiplets peaks and additional satellite and surface features. The [Fe(III)]/[Fe(total)] surface atomic ratios closely agree with the x ratios expected from the bulk composition, which gives amore » high degree of confidence on the validity of the proposed fitting procedure. The valence band spectra are also reported and show dependencies on iron speciation. The O(1s) spectra revealed the presence of O{sup 2-}, OH{sup -} species and adsorbed water. The hydroxyl component decreases with increasing x values, i.e. with the amount of ferric iron, while the oxide component increases. This study provides direct spectroscopic evidence of the deprotonation of hydroxyl groups that occurs simultaneously with the oxidation of ferrous iron within the GR structure. - Graphical abstract: X-ray photoelectron spectroscopy (XPS) is used to investigate chemical bonding and distribution of iron and oxygen species at the surface of Green Rust (GR) compounds. First spectroscopic evidence of the deprotonation of hydroxyls groups occurring simultaneously to the oxidation of Fe(II) into Fe(III) species is provided.« less

Gallium uptake by transferrin and interaction with receptor 1.

PubMed

Chikh, Zohra; Ha-Duong, Nguyêt-Thanh; Miquel, Geneviève; El Hage Chahine, Jean-Michel

2007-01-01

The kinetics and thermodynamics of Ga(III) exchange between gallium mononitrilotriacetate and human serum transferrin as well as those of the interaction between gallium-loaded transferrin and the transferrin receptor 1 were investigated in neutral media. Gallium is exchanged between the chelate and the C-site of human serum apotransferrin in interaction with bicarbonate in about 50 s to yield an intermediate complex with an equilibrium constant K (1) = (3.9 +/- 1.2) x 10(-2), a direct second-order rate constant k (1) = 425 +/- 50 M(-1) s(-1) and a reverse second-order rate constant k (-1) = (1.1 +/- 3) x 10(4) M(-1) s(-1). The intermediate complex loses a single proton with proton dissociation constant K (1a) = 80 +/- 40 nM to yield a first kinetic product. This product then undergoes a modification in its conformation which lasts about 500 s to produce a second kinetic intermediate, which in turn undergoes a final extremely slow (several hours) modification in its conformation to yield the gallium-saturated transferrin in its final state. The mechanism of gallium uptake differs from that of iron and does not involve the same transitions in conformation reported during iron uptake. The interaction of gallium-loaded transferrin with the transferrin receptor occurs in a single very fast kinetic step with a dissociation constant K (d) = 1.10 +/- 0.12 microM and a second-order rate constant k (d) = (1.15 +/- 0.3) x 10(10) M(-1) s(-1). This mechanism is different from that observed with the ferric holotransferrin and suggests that the interaction between the receptor and gallium-loaded transferrin probably takes place on the helical domain of the receptor which is specific for the C-site of transferrin and HFE. The relevance of gallium incorporation by the transferrin receptor-mediated iron-acquisition pathway is discussed.

Kinetics of FeII-polyaminocarboxylate oxidation by molecular oxygen

NASA Astrophysics Data System (ADS)

Wilson, Jessica M.; Farley, Kevin J.; Carbonaro, Richard F.

2018-03-01

Complexation of iron by naturally-occurring and synthetic organic ligands has a large effect on iron oxidation and reduction rates which in turn affect the aqueous geochemistry of many other chemical constituents. In this study, the kinetics of FeII oxidation in the presence of the polyaminocarboxylate synthetic chelating agents ethylene glycol tetraacetic acid (EGTA) and trimethylenediamine-N,N,N‧,N‧-tetraacetic acid (TMDTA) was investigated over the pH range 5.50-8.53. Batch oxidation experiments in the presence of molecular oxygen were conducted using a 2:1 M concentration ratio of polyaminocarboxylate (ligand, L) to FeII. The experimental data resembled first order kinetics for the oxidation of FeII-L to FeIII-L and observed rate constants at pH 6.0 were comparable to rate constants for the oxidation of inorganic FeII. Similar to other structurally-similar FeII-polyaminocarboxylate complexes, oxidation rates of FeII-EGTA and FeII-TMDTA decrease with increasing pH, which is the opposite trend for the oxidation of FeII complexed with inorganic ligands. However, the oxidation rates of FeII complexed with EGTA and TMDTA were considerably lower (4-5 orders of magnitude) than FeII complexed to ethylenediaminetetraacetic acid (EDTA). The distinguishing feature of the slower-reacting complexes is that they have a longer backbone between diamine functional groups. An analytical equilibrium model was developed to determine the contributions of the species FeIIL2- and FeII(H)L- to the overall oxidation rate of FeII-L. Application of this model indicated that the protonated FeII(H)L species are more than three orders of magnitude more reactive than FeIIL2-. These rate constants were used in a coupled kinetic equilibrium numerical model where the ligand to iron ratio (TOTL:TOTFe) and pH were varied to evaluate the effect on the FeII oxidation rate. Overall, increasing TOTL:TOTFe for EGTA and TMDTA enhances FeII oxidation rates at lower pH and inhibits FeII oxidation rates at higher pH. Finally, this work demonstrates that the rate of FeII oxidation is very sensitive to the identity and structure of the polyaminocarboxylate chelating agent, which has implications for any metal or organic chemical that reacts either directly or indirectly with iron.

Iron and its complexes in silicon

NASA Astrophysics Data System (ADS)

Istratov, A. A.; Hieslmair, H.; Weber, E. R.

This article is the first in a series of two reviews on the properties of iron in silicon. It offers a comprehensive of the current state of understanding of fundamental physical properties of iron and its complexes in silicon. The first section of this review discusses the position of iron in the silicon lattice and the electrical properties of interstitial iron. Updated expressions for the solubility and the diffusivity of iron in silicon are presented, and possible explanations for conflicting experimental data obtained by different groups are discussed. The second section of the article considers the electrical and the structural properties of complexes of interstitial iron with shallow acceptors (boron, aluminum, indium, gallium, and thallium), shallow donors (phosphorus and arsenic) and other impurities (gold, silver, platinum, palladium, zinc, sulfur, oxygen, carbon, and hydrogen). Special attention is paid to the kinetics of iron pairing with shallow acceptors, the dissociation of these pairs, and the metastability of iron-acceptor pairs. The parameters of iron-related defects in silicon are summarized in tables that include more than 30 complexes of iron as detected by electron paramagnetic resonance (EPR) and almost 20 energy levels in the band gap associated with iron. The data presented in this review illustrate the enormous complexing activity of iron, which is attributed to the partial or complete (depending on the temperature and the conductivity type) ionization of iron as well as the high diffusivity of iron in silicon. It is shown that studies of iron in silicon require exceptional cleanliness of experimental facilities and highly reproducible diffusion and temperature ramping (quenching) procedures. Properties of iron that are not yet completely understood and need further research are outlined.

Influencing factors and kinetics analysis on the leaching of iron from boron carbide waste-scrap with ultrasound-assisted method.

PubMed

Li, Xin; Xing, Pengfei; Du, Xinghong; Gao, Shuaibo; Chen, Chen

2017-09-01

In this paper, the ultrasound-assisted leaching of iron from boron carbide waste-scrap was investigated and the optimization of different influencing factors had also been performed. The factors investigated were acid concentration, liquid-solid ratio, leaching temperature, ultrasonic power and frequency. The leaching of iron with conventional method at various temperatures was also performed. The results show the maximum iron leaching ratios are 87.4%, 94.5% for 80min-leaching with conventional method and 50min-leaching with ultrasound assistance, respectively. The leaching of waste-scrap with conventional method fits the chemical reaction-controlled model. The leaching with ultrasound assistance fits chemical reaction-controlled model, diffusion-controlled model for the first stage and second stage, respectively. The assistance of ultrasound can greatly improve the iron leaching ratio, accelerate the leaching rate, shorten leaching time and lower the residual iron, comparing with conventional method. The advantages of ultrasound-assisted leaching were also confirmed by the SEM-EDS analysis and elemental analysis of the raw material and leached solid samples. Copyright © 2017 Elsevier B.V. All rights reserved.

Dendritic core-shell nickel-iron-copper metal/metal oxide electrode for efficient electrocatalytic water oxidation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Peili; Li, Lin; Nordlund, Dennis

Electrochemical water splitting requires efficient water oxidation catalysts to accelerate the sluggish kinetics of water oxidation reaction. Here in this paper, we report a promisingly dendritic core-shell nickel-iron-copper metal/metal oxide electrode, prepared via dealloying with an electrodeposited nickel-iron-copper alloy as a precursor, as the catalyst for water oxidation. The as-prepared core-shell nickel-iron-copper electrode is characterized with porous oxide shells and metallic cores. This tri-metal-based core-shell nickel-iron-copper electrode exhibits a remarkable activity toward water oxidation in alkaline medium with an overpotential of only 180 mV at a current density of 10 mA cm -2. The core-shell NiFeCu electrode exhibits pH-dependent oxygenmore » evolution reaction activity on the reversible hydrogen electrode scale, suggesting that non-concerted proton-electron transfers participate in catalyzing the oxygen evolution reaction. To the best of our knowledge, the as-fabricated core-shell nickel-iron-copper is one of the most promising oxygen evolution catalysts.« less

Dendritic core-shell nickel-iron-copper metal/metal oxide electrode for efficient electrocatalytic water oxidation

DOE PAGES

Zhang, Peili; Li, Lin; Nordlund, Dennis; ...

2018-01-26

Electrochemical water splitting requires efficient water oxidation catalysts to accelerate the sluggish kinetics of water oxidation reaction. Here in this paper, we report a promisingly dendritic core-shell nickel-iron-copper metal/metal oxide electrode, prepared via dealloying with an electrodeposited nickel-iron-copper alloy as a precursor, as the catalyst for water oxidation. The as-prepared core-shell nickel-iron-copper electrode is characterized with porous oxide shells and metallic cores. This tri-metal-based core-shell nickel-iron-copper electrode exhibits a remarkable activity toward water oxidation in alkaline medium with an overpotential of only 180 mV at a current density of 10 mA cm -2. The core-shell NiFeCu electrode exhibits pH-dependent oxygenmore » evolution reaction activity on the reversible hydrogen electrode scale, suggesting that non-concerted proton-electron transfers participate in catalyzing the oxygen evolution reaction. To the best of our knowledge, the as-fabricated core-shell nickel-iron-copper is one of the most promising oxygen evolution catalysts.« less

Adsorption of Toluene and Paraxylene from Aqueous Solution Using Pure and Iron Oxide Impregnated Carbon Nanotubes: Kinetics and Isotherms Study

PubMed Central

Abbas, Aamir; Ihsanullah; Al-Baghli, Nadhir A. H.

2017-01-01

Multiwall carbon nanotubes (CNTs) and iron oxide impregnated carbon nanotubes (CNTs-iron oxide) were investigated for the adsorption of hazardous toluene and paraxylene (p-xylene) from aqueous solution. Pure CNTs were impregnated with iron oxides nanoparticles using wet impregnation technique. Various characterization techniques including thermogravimetric analysis, scanning electron microscopy, elemental dispersion spectroscopy, X-ray diffraction, and nitrogen adsorption analysis were used to study the thermal degradation, surface morphology, purity, and surface area of the materials. Batch adsorption experiments show that iron oxide impregnated CNTs have higher degree of removal of p-xylene (i.e., 90%) compared with toluene (i.e., 70%), for soaking time 2 h, with pollutant initial concentration 100 ppm, at pH 6 and shaking speed of 200 rpm at 25°C. Pseudo-second-order model provides better fitting for the toluene and p-xylene adsorption. Langmuir and Freundlich isotherm models demonstrate good fitting for the adsorption data of toluene and p-xylene. PMID:28386208

Questa baseline and pre-mining ground-water quality investigation. 12. Geochemical and reactive-transport modeling based on tracer injection-synoptic sampling studies for the Red River, New Mexico, 2001-2002

USGS Publications Warehouse

Ball, James W.; Runkel, Robert L.; Nordstrom, D. Kirk

2005-01-01

Reactive-transport processes in the Red River, downstream from the town of Red River in north-central New Mexico, were simulated using the OTEQ reactive-transport model. The simulations were calibrated using physical and chemical data from synoptic studies conducted during low-flow conditions in August 2001 and during March/April 2002. Discharge over the 20-km reach from the town of Red River to the USGS streamflow-gaging station near the town of Questa ranged from 395 to 1,180 L/s during the 2001 tracer and from 234 to 421 L/s during the 2002 tracer. The pH of the Red River ranged from 7.4 to 8.5 during the 2001 tracer and from 7.1 to 8.7 during the 2002 tracer, and seep and tributary samples had pH values of 2.8 to 9.0 during the 2001 tracer and 3.8 to 7.2 during the 2002 tracer. Mass-loading calculations allowed identification of several specific locations where elevated concentrations of potential contaminants entered the Red River . These locations, characterized by features on the north side of the Red River that are known to be sources of low-pH water containing elevated metal and sulfate concentrations, are: the initial 2.4 km of the study reach, including Bitter Creek, the stream section from 6.2 to 7.8 km, encompassing La Bobita well and the Hansen debris fan, Sulphur Gulch, at about 10.5 km, the area near Portal Springs, from 12.2 to 12.6 km, and the largest contributors of mass loading, the 13.7 to 13.9 km stream section near Cabin Springs and the 14.7 to 17.5 km stream section from Shaft Spring to Thunder Bridge, Goathill Gulch, and Capulin Canyon. Speciation and saturation index calculations indicated that although solubility limits the concentration of aluminum above pH 5.0, at pH values above 7 and aluminum concentrations below 0.3 mg/L inorganic speciation and mineral solubility controls no longer dominate and aluminum-organic complexing may occur. The August 2001 reactive-transport simulations included dissolved iron(II) oxidation, constrained using measured concentrations of dissolved iron(II) and dissolved iron(total). Both simulations included precipitation of amorphous Al(OH)3 and hydrous ferric oxide as Fe(OH)3, and sorption of copper and zinc to the precipitated hydrous ferric oxide. Simulations revealed that hydrogen, iron, aluminum, copper, and zinc were non-conservative and that mineral precipitation can account for iron and aluminum concentrations. Copper and zinc concentrations can be accounted for by simulating their sorption to hydrous ferric oxide forming in the water column of the Red River , although hydrous manganese oxides also may be important sorption substrates.

Evaluating EDGARv4.tox2 speciated mercury emissions ex-post scenarios and their impacts on modelled global and regional wet deposition patterns

NASA Astrophysics Data System (ADS)

Muntean, Marilena; Janssens-Maenhout, Greet; Song, Shaojie; Giang, Amanda; Selin, Noelle E.; Zhong, Hui; Zhao, Yu; Olivier, Jos G. J.; Guizzardi, Diego; Crippa, Monica; Schaaf, Edwin; Dentener, Frank

2018-07-01

Speciated mercury gridded emissions inventories together with chemical transport models and concentration measurements are essential when investigating both the effectiveness of mitigation measures and the mercury cycle in the environment. Since different mercury species have contrasting behaviour in the atmosphere, their proportion in anthropogenic emissions could determine the spatial impacts. In this study, the time series from 1970 to 2012 of the EDGARv4.tox2 global mercury emissions inventory are described; the total global mercury emission in 2010 is 1772 tonnes. Global grid-maps with geospatial distribution of mercury emissions at a 0.1° × 0.1° resolution are provided for each year. Compared to the previous tox1 version, tox2 provides updates for more recent years and improved emissions in particular for agricultural waste burning, power generation and artisanal and small-scale gold mining (ASGM) sectors. We have also developed three retrospective emissions scenarios based on different hypotheses related to the proportion of mercury species in the total mercury emissions for each activity sector; improvements in emissions speciation are seen when using information primarily from field measurements. We evaluated them using the GEOS-Chem 3-D mercury model in order to explore the influence of speciation shifts, to reactive mercury forms in particular, on regional wet deposition patterns. The reference scenario S1 (EDGARv4.tox2_S1) uses speciation factors from the Arctic Monitoring and Assessment Programme (AMAP); scenario S2 ("EPA_power") uses factors from EPA's Information Collection Request (ICR); and scenario S3 ("Asia_filedM") factors from recent scientific publications. In the reference scenario, the sum of reactive mercury emissions (Hg-P and Hg2+) accounted for 25.3% of the total global emissions; the regions/countries that have shares of reactive mercury emissions higher than 6% in total global reactive mercury are China+ (30.9%), India+ (12.5%) and the United States (9.9%). In 2010, the variations of reactive mercury emissions amongst the different scenarios are in the range of -19.3 t/yr (China+) to 4.4 t/yr (OECD_Europe). However, at the sector level, the variation could be different, e.g., for the iron and steel industry in China reaches 15.4 t/yr. Model evaluation at the global level shows a variation of approximately ±10% in wet deposition for the three emissions scenarios. An evaluation of the impact of mercury speciation within nested grid sensitivity simulations is performed for the United States and modelled wet deposition fluxes are compared with measurements. These studies show that using the S2 and S3 emissions of reactive mercury, can improve wet deposition estimates near sources.

Surface carbon influences on the reductive transformation of TCE in the presence of granular iron.

PubMed

Firdous, R; Devlin, J F

2018-04-05

To gain insight into the processes of transformations in zero-valent iron systems, electrolytic iron (EI) has been used as a surrogate for the commercial products actually used in barriers. This substitution facilitates mechanistic studies, but may not be fully representative of all the relevant processes at work in groundwater remediation. To address this concern, the kinetic iron model (KIM) was used to investigate sorption and reactivity differences between EI and Connelly brand GI, using TCE as a probe compound. It was observed that retardation factors (R app ) for GI varied non-linearly with influent concentrations to the columns (C o ), and declined significantly as GI aged. In contrast, R app values for EI were small and insensitive to C o , and changed minimally with iron aging. Moreover, although declines in the rate constants (k) and increases in the sorption coefficients were observed for both iron types, they were most pronounced in the case of EI. SEM scans of the EI surface before and after aging (90 days) established the appearance of carbon on the older surface. This work provides evidence that iron with a higher surface carbon content outperforms pure iron, suggesting that the carbon is actively involved in promoting TCE reduction. Copyright © 2017 Elsevier B.V. All rights reserved.

An Isotopic Exchange Kinetic Model to Assess the Speciation of Metal Available Pool in Soil: The Case of Nickel.

PubMed

Zelano, I O; Sivry, Y; Quantin, C; Gélabert, A; Maury, A; Phalyvong, K; Benedetti, M F

2016-12-06

In this study an innovative approach is proposed to predict the relative contribution of each mineral phase to the total metal availability in soils, which, in other words, could be called the available metal fractionation. Through the use of isotopic exchange kinetics (IEK) performed on typical Ni bearing phases (i.e., two types of serpentines, chlorite, smectite, goethite, and hematite) the isotopic exchange and metal-solid interaction processes are connected, considering both the thermodynamic and kinetic aspects. Results of Ni IEK experiments on mineral phases are fitted with a pseudo-first order kinetic model. For each Ni bearing phase, this allows to (i) determine the number and size of exchangeable pools (E Ni(i) ), (ii) assess their corresponding kinetic constants (k (i) ), and (iii) discuss the mechanism of Ni isotopic exchange at mineral surfaces. It is shown that all the phases investigated, with the only exception of hematite, present at least two distinct reactive pools with significantly different k (i) values. Results suggest also that metal involved in outer-sphere complexes would display isotopic exchange between 100 and 1000 times faster than metal involved in inner-sphere complexes, and that the presence of high and low affinity sites may influence the rate of isotopic exchange up to 1 order of magnitude. Moreover, the method developed represents a tool to predict and estimate Ni mobility and availability in natural soil samples on the basis of soil mineral composition, providing information barely obtained with other techniques.

Biologically tunable reactivity of energetic nanomaterials using protein cages.

PubMed

Slocik, Joseph M; Crouse, Christopher A; Spowart, Jonathan E; Naik, Rajesh R

2013-06-12

The performance of aluminum nanomaterial based energetic formulations is dependent on the mass transport, diffusion distance, and stability of reactive components. Here we use a biologically inspired approach to direct the assembly of oxidizer loaded protein cages onto the surface of aluminum nanoparticles to improve reaction kinetics by reducing the diffusion distance between the reactants. Ferritin protein cages were loaded with ammonium perchlorate (AP) or iron oxide and assembled with nAl to create an oxidation-reduction based energetic reaction and the first demonstration of a nanoscale biobased thermite material. Both materials showed enhanced exothermic behavior in comparison to nanothermite mixtures of bulk free AP or synthesized iron oxide nanopowders prepared without the use of ferritin. In addition, by utilizing a layer-by-layer (LbL) process to build multiple layers of protein cages containing iron oxide and iron oxide/AP on nAl, stoichiometric conditions and energetic performance can be optimized.

Suspended particulate matter determines physical speciation of Fe, Mn, and trace metals in surface waters of Loire watershed.

PubMed

Baalousha, Mohamed; Stoll, Serge; Motelica-Heino, Mikaël; Guigues, Nathalie; Braibant, Gilles; Huneau, Frédéric; Le Coustumer, Philippe

2018-02-10

This study investigates the spatiotemporal variability of major and trace elements, dissolved organic carbon (DOC), total dissolved solids (TDS), and suspended particulate matter (SPM) in surface waters of several hydrosystems of the Loire River watershed in France. In particular, this study aims to delineate the impact of the abovementioned water physicochemical parameters on natural iron and manganese physical speciation (homoaggregation/heteroaggregation) among fine colloidal and dissolved (< 10 nm), colloidal (10-450 nm) and particulate (> 450 nm) phases in Loire River watershed. Results show that the chemistry of the Loire River watershed is controlled by two end members: magmatic and metamorphic petrographic context on the upper part of the watershed; and sedimentary rocks for the middle and low part of the Loire. The percentage of particulate Fe and Mn increased downstream concurrent with the increase in SPM and major cations concentration, whereas the percentage of colloidal Fe and Mn decreased downstream. Transmission electron microscopy analyses of the colloidal and particulate fractions (from the non-filtered water sample) revealed that heteroaggregation of Fe and Mn rich natural nanoparticles and natural organic matter to the particulate phase is the dominant mechanism. The heteroaggregation controls the partitioning of Fe and Mn in the different fractions, potentially due to the increase in the ionic strength, and divalent cations concentration downstream, and SPM concentration. These findings imply that SPM concentration plays an important role in controlling the fate and behavior of Fe and Mn in various sized fractions. Graphical abstract Physical speciation by heteroaggregation of (Fe-Mn) compounds: high [SPM] → [Fe-Mn] particulate faction; low {SPM] → [Fe-Mn] colloid-dissolved fraction.

Micronutrient metal speciation is driven by competitive organic chelation in grassland soils.

NASA Astrophysics Data System (ADS)

Boiteau, R.; Shaw, J. B.; Paša-Tolić, L.; Koppenaal, D.; Jansson, J.

2017-12-01

Many elements are scarcely soluble in aqueous conditions found in high pH environments, such as calcareous grassland soils, unless complexed to strong binding organic ligands. To overcome this limitation, some plants and microbes produce chelators that solubilize micronutrient metals such as Fe, Ni, Cu, and Zn from mineral phases. These complexes are taken up by organisms via specific membrane receptors, thereby differentially impacting the bioavailability of these metals to the plant and microbial community. Although the importance of these chelation strategies for individual organisms has been well established, little is known about which pathways coexist within rhizosphere microbiomes or how they interact and compete for metal binding. Identifying these metallo-organic species within natural ecosystems has remained a formidable analytical challenge due to the vast diversity of compounds and poorly defined metabolic processes in complex soil matrix. Herein, we employed recently developed liquid chromatography (LC) mass spectrometry (MS) methods to characterize the speciation of water-soluble dissolved trace elements (Fe, Ni, Cu, and Zn) from Kansas Prairie soil. Both plant and fungal chelators were identified, revealing compound-specific patterns of chelation to biologically essential metals. Numerous metabolites typically implicated in plant iron acquisition and homeostasis, including mugineic acids, deoxymugineic acid, nicotianamine, and hydroxynicotianamine, dominated the speciation of divalent metals such as Ni, Cu, and Zn (2-57 pmol / g soil). In contrast, the fungal siderophore ferricrocine bound comparatively more trivalent Fe (9pmol / g soil). These results define biochemical pathways that underpin the regulation of metals in the grassland rhizosphere. They also raise new questions about the competition of these compounds for metal binding and their bioavailability to different members of the rhizosphere population.

Distribution and speciation of trace elements in iron and manganese oxide cave deposits

DOE Office of Scientific and Technical Information (OSTI.GOV)

Frierdich, Andrew J.; Catalano, Jeffrey G.

2012-10-24

Fe and Mn oxide minerals control the distribution and speciation of heavy metals and trace elements in soils and aquatic systems through chemical mechanisms involving adsorption, incorporation, and electron transfer. The Pautler Cave System in Southwest Illinois, an analog to other temperate carbonate-hosted karst systems, contains Fe and Mn oxide minerals that form in multiple depositional environments and have high concentrations of associated trace elements. Synchrotron-based micro-scanning X-ray fluorescence ({mu}-SXRF) shows unique spatial distributions of Fe, Mn, and trace elements in mineral samples. Profile maps of Mn oxide cave stream pebble coatings show Fe- and As-rich laminations, indicating dynamic redoxmore » conditions in the cave stream. {mu}-SXRF maps demonstrate that Ni, Cu, and Zn correlate primarily with Mn whereas As correlates with both Mn and Fe; As is more enriched in the Fe phase. Zn is concentrated in the periphery of Mn oxide stream pebble coatings, and may be an indication of recent anthropogenic surface activity. X-ray absorption fine structure spectroscopy measurements reveal that As(V) occurs as surface complexes on Mn and Fe oxides whereas Zn(II) associated with Mn oxides is adsorbed to the basal planes of phyllomanganates in a tetrahedral coordination. Co(III) and Se(IV) are also observed to be associated with Mn oxides. The observation of Fe, Mn, and trace element banding in Mn oxide cave stream pebble coatings suggests that these materials are sensitive to and document aqueous redox conditions, similar to ferromanganese nodules in soils and in marine and freshwater sediments. Furthermore, speciation and distribution measurements indicate that these minerals scavenge trace elements and limit the transport of micronutrients and contaminants in karst aquifer systems while also potentially recording changes in anthropogenic surface activity and land-use.« less

Sorption, desorption, and speciation of Cd, Ni, and Fe by four calcareous soils as affected by pH.

PubMed

Tahervand, Samaneh; Jalali, Mohsen

2016-06-01

The sorption, desorption, and speciation of cadmium (Cd), nickel (Ni), and iron (Fe) in four calcareous soils were investigated at the pH range of 2-9. The results indicated that sorption of Fe by four soils was higher than 80 % at pH 2, while in the case of Cd and Ni was less than 30 %. The most common sequence of metal sorption at pH 2-9 for four soils was in the order of Fe ≫ Ni > Cd. Cadmium and Ni sorption as a function of pH showed the predictable trend of increasing metal sorption with increase in equilibrium pH, while the Fe sorption trend was different and characterized by three phases. With regard to the order of Cd, Ni, and Fe sorption on soils, Cd and Ni showed high affinity for organic matter (OM), whereas Fe had high tendency for calcium carbonate (CaCO3). Results of metal desorption using 0.01 M NaCl demonstrated that metal sorption on soils containing high amounts of CaCO3 was less reversible in comparison to soils containing high OM. In general, Cd and Ni desorption curves were characterized by three phases; (1) the greatest desorption at pH 2, (2) the low desorption at pH 3-7, and (3) the least desorption at pH > 7. The MINTEQ speciation solubility program showed that the percentage of free metals declined markedly with increase of pH, while the percentage of carbonate and hydroxyl species increased. Furthermore, MINTEQ predicted that saturation index (SI) of metals increased with increasing pH.

Geochemistry of some rare earth elements in groundwater, Vierlingsbeek, The Netherlands.

PubMed

Janssen, René P T; Verweij, Wilko

2003-03-01

Groundwater samples were taken from seven bore holes at depths ranging from 2 to 41m nearby drinking water pumping station Vierlingsbeek, The Netherlands and analysed for Y, La, Ce, Pr, Nd, Sm and Eu. Shale-normalized patterns were generally flat and showed that the observed rare earth elements (REE) were probably of natural origin. In the shallow groundwaters the REEs were light REE (LREE) enriched, probably caused by binding of LREEs to colloids. To improve understanding of the behaviour of the REE, two approaches were used: calculations of the speciation and a statistical approach. For the speciation calculations, complexation and precipitation reactions including inorganic and dissolved organic carbon (DOC) compounds, were taken into account. The REE speciation showed REE(3+), REE(SO(4))(+), REE(CO(3))(+) and REE(DOC) being the major species. Dissolution of pure REE precipitates and REE-enriched solid phases did not account for the observed REEs in groundwater. Regulation of REE concentrations by adsorption-desorption processes to Fe(III)(OH)(3) and Al(OH)(3) minerals, which were calculated to be present in nearly all groundwaters, is a probable explanation. The statistical approach (multiple linear regression) showed that pH is by far the most significant groundwater characteristic which contributes to the variation in REE concentrations. Also DOC, SO(4), Fe and Al contributed significantly, although to a much lesser extent, to the variation in REE concentrations. This is in line with the calculated REE-species in solution and REE-adsorption to iron and aluminium (hydr)oxides. Regression equations including only pH, were derived to predict REE concentrations in groundwater. External validation showed that these regression equations were reasonably successful to predict REE concentrations of groundwater of another drinking water pumping station in quite different region of The Netherlands.

Geochemical Weathering Increases Lead Bioaccessibility in Semi-Arid Mine Tailings

PubMed Central

Hayes, Sarah M.; Webb, Sam M.; Bargar, John R.; O'Day, Peggy A.; Maier, Raina M.; Chorover, Jon

2012-01-01

Mine tailings can host elevated concentrations of toxic metal(loid)s that represent a significant hazard to surrounding communities and ecosystems. Eolian transport, capable of translocating small (micrometer-sized) particles, can be the dominant mechanism of toxic metal dispersion in arid or semi-arid landscapes. Human exposure to metals can then occur via direct inhalation or ingestion of particulates. The fact that measured doses of total lead (Pb) in geomedia correlate poorly with blood Pb levels highlights a need to better resolve the precise distribution of molecularly-speciated metal-bearing phases in the complex particle mixtures. Species distribution controls bioaccessibility, thereby directly impacting health risk. This study seeks to correlate Pb-containing particle size and mineral composition with lability and bioaccessibility in mine tailings subjected to weathering in a semi-arid environment. We employed X-ray absorption spectroscopy (XAS) and X-ray fluorescence (XRF), coupled with sequential chemical extractions, to study Pb speciation in tailings from the semi-arid Arizona Klondyke State Superfund Site. Representative samples ranging in pH from 2.6 to 5.4 were selected for in-depth study of Pb solid-phase speciation. The principle lead-bearing phase was plumbojarosite (PbFe6(SO4)4(OH)12), but anglesite (PbSO4) and iron oxide-sorbed Pb were also observed. Anglesite, the most bioavailable mineral species of lead identified in this study, was enriched in surficial tailings samples, where Pb concentrations in the clay size fraction were 2–3 times higher by mass relative to bulk. A mobile and bioaccessible Pb phase accumulates in surficial tailings, with a corresponding increase in risk of human exposure to atmospheric particles. PMID:22553941

Speciation of phosphorus in the continental shelf sediments in the Eastern Arabian Sea

NASA Astrophysics Data System (ADS)

Acharya, Shiba Shankar; Panigrahi, Mruganka Kumar; Kurian, John; Gupta, Anil Kumar; Tripathy, Subhasish

2016-03-01

The distributions of various forms of phosphorus (P) and their relation with sediment geochemistry in two core sediments near Karwar and Mangalore offshore have been studied through the modified SEDEX procedure (Ruttenberg et al., 2009) and bulk chemical analysis. The present study provides the first quantitative analysis of complete phosphorus speciation in the core sediments of the Eastern Arabian shelf. The chemical index of alteration (CIA), chemical Index of Weathering (CIW) and Al-Ti-Zr ternary diagram suggest low to moderate source area weathering of granodioritic to tonalitic source rock composition, despite the intense orographic rainfall in the source area. Due to the presence of same source rock and identical oxic depositional environment, the studied sediments show the same range of variation of total phosphorus (24 to 83 μmol/g) with a down-depth depleting trend. Organic bound P and detrital P are the two major chemical forms followed by iron-bound P, exchangeable/loosely bound P and authigenic P. The authigenic P content in the sediments near Mangalore coast varies linearly with calcium (r=0.88) unlike that of Karwar coast. The different reactive-phosphorus pools exhibit identical depleting trend with depth. This indicates that the phosphorus released from the organic matter and Fe bound fractions are prevented from precipitating as authigenic phosphates in the deeper parts of the sediment column. The low concentration of total P, dominance of detrital non-reactive fraction of P and inhibition of formation of authigenic phosphate result in the absence of active phosphatization in the Eastern Arabian Shelf in the studied region. High sedimentation rate (35-58 cm/kyr) and absence of winnowing effect appear to be the dominant factor controlling the P-speciation in the studied sediments.

Fretting wear of iron, nickel, and titanium under varied environmental conditions

NASA Technical Reports Server (NTRS)

Bill, R. C.

1979-01-01

Fretting wear experiments were conducted on high-purity iron, nickel and titanium in air under conditions of varied humidity and temperature, and in nitrogen. For iron and titanium, maximum fretting occurred at 10 and 30 percent relative humidity respectively. Nickel showed a minimum in fretting wear at about 10% relative humidity. With increasing temperature, all three metals initially showed reduced fretting wear, with increasing wear observed as temperatures increased beyond 200-300 C. For titanium, dramatically reduced fretting wear was observed at temperatures above 500 C, relatable to a change in oxidation kinetics. All three metals showed much less fretting wear in N2 with the presence of moisture in N2 having a proportionally stronger effect than in air.

Fretting wear of iron, nickel, and titanium under varied environmental conditions

NASA Technical Reports Server (NTRS)

Bill, R. C.

1978-01-01

Fretting wear experiments were conducted on high purity iron, nickel and titanium in air under conditions of varied humidity and temperature, and in nitrogen. For iron and titanium, maximum fretting occurred at 10 and 30 percent relative humidity respectively. Nickel showed a minimum in fretting wear at about 10 percent relative humidity. With increasing temperature, all three metals initially showed reduced fretting wear, with increasing wear observed as temperatures increased beyond 200-300 C. For titanium, dramatically reduced fretting wear was observed at temperatures above 500 C, relatable to a change in oxidation kinetics. All three metals showed much less fretting wear in N2 with the presence of moisture in N2 having a proportionally stronger effect than in air.

Model studies in cytochrome P-450-mediated toxicity of halogenated compounds: radical processes involving iron porphyrins.

PubMed Central

Brault, D

1985-01-01

Haloalkane toxicity originates from attack on biological targets by reactive intermediates derived from haloalkane metabolism by a hemoprotein, cytochrome P-450. Carbon-centered radicals and their peroxyl derivatives are most likely involved. The reactions of iron porphyrin--a model for cytochrome P-450--with various carbon-centered and peroxyl radicals generated by pulse radiolysis are examined. Competition between iron porphyrin and unsaturated fatty acids for attack by peroxyl radicals is pointed out. These kinetic data are used to derive a model for toxicity of haloalkanes with particular attention to carbon tetrachloride and halothane. The importance of local oxygen concentration and structural arrangement of fatty acids around cytochrome P-450 is emphasized. PMID:3007100

Mathematical model of the oxidation of ferrous iron by a biofilm of Thiobacillus ferrooxidans.

PubMed

Mesa, M M; Macías, M; Cantero, D

2002-01-01

Microbial oxidation of ferrous iron may be a viable alternative method of producing ferric sulfate, which is a reagent used for removal of H(2)S from biogas. The paper introduces a kinetic study of the biological oxidation of ferrous iron by Thiobacillus ferrooxidans immobilized on biomass support particles (BSP) composed of polyurethane foam. On the basis of the data obtained, a mathematical model for the bioreactor was subsequently developed. In the model described here, the microorganisms adhere by reversible physical adsorption to the ferric precipitates that are formed on the BSP. The model can also be considered as an expression for the erosion of microorganisms immobilized due to the agitation of the medium by aeration.

Oxidation of dissolved iron under warmer, wetter conditions on Mars: Transitions to present-day arid environments

NASA Technical Reports Server (NTRS)

Burns, R. G.

1993-01-01

The copious deposits of ferric-iron assemblages littering the surface of bright regions of Mars indicate that efficient oxidative weathering reactions have taken place during the evolution of the planet. Because the kinetics of atmosphere-surface (gas-solid) reactions are considerably slower than chemical weathering reactions involving an aqueous medium, most of the oxidation products now present in the martian regolith probably formed when groundwater flowed near the surface. This paper examines how chemical weathering reactions were effected by climatic variations when warm, wet environments became arid on Mars. Analogies are drawn with hydrogeochemical and weathering environments on the Australian continent where present-day oxidation of iron is occurring in acidic ground water under arid conditions.

Kinetics of acid hydrolysis and reactivity of some antibacterial hydrophilic iron(II) imino-complexes

NASA Astrophysics Data System (ADS)

Shaker, Ali Mohamed; Nassr, Lobna Abdel-Mohsen Ebaid; Adam, Mohamed Shaker Saied; Mohamed, Ibrahim Mohamed Abdelhalim

2015-05-01

Kinetic study of acid hydrolysis of some hydrophilic Fe(II) Schiff base amino acid complexes with antibacterial properties was performed using spectrophotometry. The Schiff base ligands were derived from sodium 2-hydroxybenzaldehyde-5-sulfonate and glycine, L-alanine, L-leucine, L-isoleucine, DL-methionine, DL-serine, or L-phenylalanine. The reaction was studied in aqueous media under conditions of pseudo-first order kinetics. Moreover, the acid hydrolysis was studied at different temperatures and the activation parameters were calculated. The general rate equation was suggested as follows: rate = k obs [Complex], where k obs = k 2 [H+]. The evaluated rate constants and activation parameters are consistent with the hydrophilicity of the investigated complexes.

Effects of carbonate species on the kinetics of dechlorination of 1,1,1-trichloroethane by zero-valent iron.

PubMed

Agrawal, Abinash; Ferguson, William J; Gardner, Bruce O; Christ, John A; Bandstra, Joel Z; Tratnyek, Paul G

2002-10-15

The effect of precipitates on the reactivity of iron metal (Fe0) with 1,1,1-trichloroethane (TCA) was studied in batch systems designed to model groundwaters that contain dissolved carbonate species (i.e., C(IV)). At representative concentrations for high-C(IV) groundwaters (approximately 10(-2) M), the pH in batch reactors containing Fe0 was effectively buffered until most of the aqueous C(IV) precipitated. The precipitate was mainly FeCO3 (siderite) but may also have included some carbonate green rust. Exposure of the Fe0 to dissolved C(IV) accelerated reduction of TCA, and the products formed under these conditions consisted mainly of ethane and ethene, with minor amounts of several butenes. The kinetics of TCA reduction were first-order when C(IV)-enhanced corrosion predominated but showed mixed-order kinetics (zero- and first-order) in experiments performed with passivated Fe0 (i.e., before the onset of pitting corrosion and after repassivation by precipitation of FeCO3). All these data were described by fitting a Michaelis-Menten-type kinetic model and approximating the first-order rate constant as the ratio of the maximum reaction rate (Vm) and the concentration of TCA at half of the maximum rate (K(1/2)). The decrease in Vm/K(1/2) with increasing C(IV) exposure time was fit to a heuristic model assuming proportionality between changes in TCA reduction rate and changes in surface coverage with FeCO3.

Changes in metal availability, desorption kinetics and speciation in contaminated soils during repeated phytoextraction with the Zn/Cd hyperaccumulator Sedum plumbizincicola.

PubMed

Li, Zhu; Jia, Mingyun; Wu, Longhua; Christie, Peter; Luo, Yongming

2016-02-01

Phytoextraction is one of the most promising technologies for the remediation of metal contaminated soils. Changes in soil metal availability during phytoremediation have direct effects on removal efficiency and can also illustrate the interactive mechanisms between hyperaccumulators and metal contaminated soils. In the present study the changes in metal availability, desorption kinetics and speciation in four metal-contaminated soils during repeated phytoextraction by the zinc/cadmium hyperaccumulator Sedum plumbizincicola (S. plumbizincicola) over three years were investigated by chemical extraction and the DGT-induced fluxes in soils (DIFS) model. The available metal fractions (i.e. metal in the soil solution extracted by CaCl2 and by EDTA) decreased greatly by >84% after phytoextraction in acid soils and the deceases were dramatic at the initial stages of phytoextraction. However, the decreases in metal extractable by CaCl2 and EDTA in calcareous soils were not significant or quite low. Large decreases in metal desorption rate constants evaluated by DIFS were found in calcareous soils. Sequential extraction indicated that the acid-soluble metal fraction was easily removed by S. plumbizincicola from acid soils but not from calcareous soils. Reducible and oxidisable metal fractions showed discernible decreases in acid and calcareous soils, indicating that S. plumbizincicola can mobilize non-labile metal for uptake but the residual metal cannot be removed. The results indicate that phytoextraction significantly decreases metal availability by reducing metal pool sizes and/or desorption rates and that S. plumbizincicola plays an important role in the mobilization of less active metal fractions during repeated phytoextraction. Copyright © 2015 Elsevier Ltd. All rights reserved.

Using chromium stable isotope ratios to quantify Cr(VI) reduction: Lack of sorption effects

USGS Publications Warehouse

Ellis, A.S.; Johnson, T.M.; Bullen, T.D.

2004-01-01

Chromium stable isotope values can be effectively used to monitor reduction of Cr(VI) in natural waters. We investigate effects of sorption during transport of Cr(VI) which may also shift Cr isotopes values, complicating efforts to quantify reduction. This study shows that Cr stable isotope fractionation caused by sorption is negligible. Equilibrium fractionation of Cr stable isotopes between dissolved Cr-(VI) and Cr(VI) adsorbed onto ??-Al2O3 and goethite is less than 0.04???. (53Cr/52Cr) under environmentally relevant pH conditions. Batch experiments at pH 4.0 and pH 6.0 were conducted in series to sequentially magnify small isotope fractionations. A simple transport model suggests that adsorption may cause amplification of a small isotope fractionation along extreme fringes of a plume, leading to shifts in 53Cr/52Cr values. We therefore suggest that isotope values at extreme fringes of Cr plumes be critically evaluated for sorption effects. A kinetic effect was observed in experiments with goethite at pH 4 where apparently lighter isotopes diffuse into goethite clumps at a faster rate before eventually reaching equilibrium. This observed kinetic effect may be important in a natural system that has not attained equilibrium and is in need of further study. Cr isotope fractionation caused by speciation of Cr(VI) between HCrO4- and CrO42- was also examined, and we conclude that it is not measurable. In the absence of isotope fractionation caused by equilibrium speciation and sorption, most of the variation in ??53 Cr values may be attributed to reduction, and reliable estimates of Cr reduction can be made.

In situ investigation of supercritical CO2 assisted impregnation of drugs into a polymer by high pressure FTIR micro-spectroscopy.

PubMed

Champeau, M; Thomassin, J-M; Jérôme, C; Tassaing, T

2015-02-07

An original experimental set-up combining a FTIR micro-spectrometer with a high pressure cell has been built in order to analyze in situ the impregnation of a solute into microscopic polymer samples, such as fibers or films, subjected to supercritical CO2. Thanks to this experimental set-up, key factors governing the impregnation process can be simultaneously followed such as the swelling of the polymeric matrix, the CO2 sorption, the kinetics of impregnation and the drug loading into the matrix. Moreover, the solute/polymer interactions and the speciation of the solute can be analyzed. We have monitored in situ the impregnation of aspirin and ketoprofen into PEO (Polyethylene Oxide) platelets at T = 40 °C and P = 5; 10 and 15 MPa. The kinetics of impregnation of aspirin was quicker than the one of ketoprofen and the final drug loading was also higher in the case of aspirin. Whereas the CO2 sorption and the PEO swelling remain constant when PEO is just subjected to CO2 under isobaric conditions, we noticed that both parameters can increase while the drug impregnates PEO. Coupling these results with DSC measurements, we underlined the plasticizing effect of the drug that also leads to a decrease in the crystallinity of PEO in situ thus favoring the sorption of CO2 molecules into the matrix and the swelling of the matrix. The plasticizing effect increases with the drug loading. Finally, the speciation of drugs was investigated considering the shift of the carboxyl bands of the drugs. Both drugs were found to be mainly homogeneously dispersed into PEO.

Quantum Chemical Examination of the Sequential Halogen Incorporation Scheme for the Modeling of Speciation of I/Br/Cl-Containing Trihalomethanes.

PubMed

Zhang, Chenyang; Li, Maodong; Han, Xuze; Yan, Mingquan

2018-02-20

The recently developed three-step ternary halogenation model interprets the incorporation of chlorine, bromine, and iodine ions into natural organic matter (NOM) and formation of iodine-, bromine-, and chlorine-containing trihalomethanes (THMs) based on the competition of iodine, bromine, and chlorine species at each node of the halogenation sequence. This competition is accounted for using the dimensionless ratios (denoted as γ) of kinetic rates of reactions of the initial attack sites or halogenated intermediates with chlorine, bromine, and iodine ions. However, correlations between the model predictions made and mechanistic aspects of the incorporation of halogen species need to be ascertained in more detail. In this study, quantum chemistry calculations were first used to probe the formation mechanism of 10 species of Cl-/Br-/I- THMs. The HOMO energy (E HOMO ) of each mono-, bi-, or trihalomethanes were calculated by B3LYP method in Gaussian 09 software. Linear correlations were found to exist between the logarithms of experimentally determined kinetic preference coefficients γ reported in prior research and, on the other hand, differences of E HOMO values between brominated/iodinated and chlorinated halomethanes. One notable exception from this trend was that observed for the incorporation of iodine into mono- and di-iodinated intermediates. These observations confirm the three-step halogen incorporation sequence and the factor γ in the statistical model. The combined use of quantum chemistry calculations and the ternary sequential halogenation model provides a new insight into the microscopic nature of NOM-halogen interactions and the trends seen in the behavior of γ factors incorporated in the THM speciation models.

Influence of humic acid and dihydroxy benzoic acid on the agglomeration, adsorption, sedimentation and dissolution of copper, manganese, aluminum and silica nanoparticles - A tentative exposure scenario.

PubMed

Pradhan, Sulena; Hedberg, Jonas; Rosenqvist, Jörgen; Jonsson, Caroline M; Wold, Susanna; Blomberg, Eva; Odnevall Wallinder, Inger

2018-01-01

This work focuses on kinetic aspects of stability, mobility, and dissolution of bare Cu, Al and Mn, and SiO2 NPs in synthetic freshwater (FW) with and without the presence of natural organic matter (NOM). This includes elucidation of particle and surface interactions, metal dissolution kinetics, and speciation predictions of released metals in solution. Dihydroxy benzoic acid (DHBA) and humic acid adsorbed rapidly on all metal NPs (<1 min) via multiple surface coordinations, followed in general by rapid agglomeration and concomitant sedimentation for a large fraction of the particles. In contrast, NOM did not induce agglomeration of the SiO2 NPs during the test duration (21 days). DHBA in concentrations of 0.1 and 1 mM was unable to stabilize the metal NPs for time periods longer than 6 h, whereas humic acid, at certain concentrations (20 mg/L) was more efficient (>24 h). The presence of NOM increased the amount of released metals into solution, in particular for Al and Cu, whereas the effect for Mn was minor. At least 10% of the particle mass was dissolved within 24 h and remained in solution for the metal NPs in the presence of NOM. Speciation modeling revealed that released Al and Cu predominantly formed complexes with NOM, whereas less complexation was seen for Mn. The results imply that potentially dispersed NPs of Cu, Al and Mn readily dissolve or sediment close to the source in freshwater of low salinity, whereas SiO2 NPs are more stable and therefore more mobile in solution.

Mercury methylation dynamics in estuarine and coastal marine environments — A critical review

NASA Astrophysics Data System (ADS)

Merritt, Karen A.; Amirbahman, Aria

2009-09-01

Considerable recent research has focused on methylmercury (MeHg) cycling within estuarine and coastal marine environments. Because MeHg represents a potent neurotoxin that may magnify in marine foodwebs, it is important to understand the mechanisms and environmental variables that drive or constrain methylation dynamics in these environments. This critical review article explores the mechanisms hypothesized to influence aqueous phase and sediment solid phase MeHg concentrations and depth-specific inorganic Hg (II) (Hg i) methylation rates (MMR) within estuarine and coastal marine environments, and discusses issues of terminology or methodology that complicate mechanism-oriented interpretation of field and laboratory data. Mechanisms discussed in this review article include: 1) the metabolic activity of sulfate reducing bacteria (SRB), the microbial group thought to dominate mercury methylation in these environments; 2) the role that Hg i concentration and/or speciation play in defining depth-specific Hg i methylation rates; and 3) the depth-dependent balance between MeHg production and consumption within the sedimentary environment. As discussed in this critical review article, the hypothesis of SRB community control on the Hg i methylation rate in estuarine and coastal marine environments is broadly supported by the literature. Although Hg i speciation, as a function of porewater inorganic sulfide and/or dissolved organic matter concentration and/or pH, may also play a role in observed variations in MMR, the nature and function of the controlling ligand(s) has not yet been adequately defined. Furthermore, although it is generally recognized that the processes responsible for MeHg production and consumption overlap spatially and/or kinetically in the sedimentary environment, and likely dictate the extent to which MeHg accumulates in the aqueous and/or sediment solid phase, this conceptual interpretation requires refinement, and would benefit greatly from the application of kinetic modeling.

Influence of humic acid and dihydroxy benzoic acid on the agglomeration, adsorption, sedimentation and dissolution of copper, manganese, aluminum and silica nanoparticles – A tentative exposure scenario

PubMed Central

Pradhan, Sulena; Rosenqvist, Jörgen; Jonsson, Caroline M.; Wold, Susanna; Blomberg, Eva; Odnevall Wallinder, Inger

2018-01-01

This work focuses on kinetic aspects of stability, mobility, and dissolution of bare Cu, Al and Mn, and SiO2 NPs in synthetic freshwater (FW) with and without the presence of natural organic matter (NOM). This includes elucidation of particle and surface interactions, metal dissolution kinetics, and speciation predictions of released metals in solution. Dihydroxy benzoic acid (DHBA) and humic acid adsorbed rapidly on all metal NPs (<1 min) via multiple surface coordinations, followed in general by rapid agglomeration and concomitant sedimentation for a large fraction of the particles. In contrast, NOM did not induce agglomeration of the SiO2 NPs during the test duration (21 days). DHBA in concentrations of 0.1 and 1 mM was unable to stabilize the metal NPs for time periods longer than 6 h, whereas humic acid, at certain concentrations (20 mg/L) was more efficient (>24 h). The presence of NOM increased the amount of released metals into solution, in particular for Al and Cu, whereas the effect for Mn was minor. At least 10% of the particle mass was dissolved within 24 h and remained in solution for the metal NPs in the presence of NOM. Speciation modeling revealed that released Al and Cu predominantly formed complexes with NOM, whereas less complexation was seen for Mn. The results imply that potentially dispersed NPs of Cu, Al and Mn readily dissolve or sediment close to the source in freshwater of low salinity, whereas SiO2 NPs are more stable and therefore more mobile in solution. PMID:29420670

Kinetic Parameters of Secondary Carbide Precipitation in High-Cr White Iron Alloyed by Mn-Ni-Mo-V Complex

NASA Astrophysics Data System (ADS)

Efremenko, V. G.; Chabak, Yu. G.; Brykov, M. N.

2013-05-01

This study presents kinetics of precipitation of secondary carbides in 14.55%Cr-Mn-Ni-Mo-V white cast iron during the destabilization heat treatment. The as-cast iron was heat treated at temperatures in the range of 800-1100 °C with soaking up to 6 h. Investigation was carried out by optical and electron microscopy, dilatometric analysis, Ms temperature measurement, and bulk hardness evaluation. TTT-curve of precipitation process of secondary carbides (M7C3, M23C6, M3C2) has been constructed in this study. It was determined that the precipitation occurs at the maximum rate at 950 °C where the process is started after 10 s and completed within 160 min further. The precipitation leads to significant increase of Ms temperature and bulk hardness; large soaking times at destabilization temperatures cause coarsening of secondary carbides and decrease in particles number, followed by decrease in hardness. The results obtained are discussed in terms of solubility of carbon in the austenite and diffusion activation of Cr atoms. The precipitation was found to consist of two stages with activation energies of 196.5 kJ/g-mole at the first stage and 47.1 kJ/g-mole at the second stage.

Adsorption of low concentration ceftazidime from aqueous solutions using impregnated activated carbon promoted by Iron, Copper and Aluminum

NASA Astrophysics Data System (ADS)

Hu, Xiang; Zhang, Hua; Sun, Zhirong

2017-01-01

In this paper, three impregnated activated carbon IAC (AC-Cu, AC-Fe, and AC-Al) promoted by Iron, Copper and Aluminum were used for adsorption of ceftazidime. Iron(III), Copper(II) and Aluminum(III) nitrate were used as an impregnant. The IACs were characterized by scanning electron microscope (SEM), Brunauer-Emmett-Teller (BET) surface area analyzer, Fourier transform infrared spectroscopy (FTIR) and X-ray Photoelectron Spectroscopy (XPS).The influence of factors, such as ion strength, pH, temperature, initial concentration, and concentration of natural organic matter organic matter on the adsorption process were studied. The adsorption kinetics and isotherms of ceftazidime were studied for the three IACs. The results showed that the adsorption was accurately represented by pseudo-second order model. Under different temperature, the maximum adsorption quantity of ceftazidime on AC-Cu calculated by pseudo-second order kinetic model were 200.0 mg g-1 (298 K), 196.1 mg g-1 (303 K) and 185.2 mg g-1 (308 K). It was much higher than that of AC-Fe and AC-Al. And the process was controlled by both film diffusion and intra particle mass transport. The results also showed that, the Freundlich and Temkin isotherm fit the adsorption well.

Chemical oxidation of a malodorous compound, indole, using iron entrapped in calcium alginate beads.

PubMed

Ben Hammouda, Samia; Adhoum, Nafaâ; Monser, Lotfi

2016-01-15

Iron-alginate beads (Fe-ABs) were successfully prepared by the ion-gelation method, and applied as heterogeneous Fenton catalysts for the removal of a malodorous compound 'indole'. Similarly, copper-enriched alginate beads (Cu-ABs) were synthesized and tested as like-Fenton catalyst, however, their application proved not to be effective for this purpose. Fe-ABs catalysts were characterized by FTIR, SEM, EDS and AAS spectroscopy. Results pointed out that the parameters affecting Fenton catalysis must be carefully chosen to avoid excessive iron release. Under optimal conditions, complete indole removal and considerably high reduction of TOC, without significant leaching was achieved. Indole decay followed a pseudo-first-order kinetics. The absolute rate constant for indole hydroxylation was 3.59×10(9) M(-1) s(-1), as determined by the competition kinetics method. Four reaction intermediates (Isatin, Dioxindole, Oxindole and Anthralinic acid) were identified by ULC/MS/MS analysis. Short-chain aliphatic carboxylic acids like formic, acetic, oxalic, maleic, oxamic and pyruvic acids were identified by ion exclusion chromatography and as end-products. Based on the identified by-products, a plausible mineralization pathway was proposed. Moreover, the catalyst was recovered quantitatively by simple filtration and reused for several times without significant loss of activity. Copyright © 2015 Elsevier B.V. All rights reserved.