Action of copper (3) in periodate complex on hexavalent neptunium and plutonium in alkaline medium

International Nuclear Information System (INIS)

Shatokhina, O.B.; Alekseeva, D.P.; Peretrukhin, B.F.; Krot, N.N.

1977-01-01

A complex of trivalent copper connected with periodate has been studied in order to determine its possible use for oxidizing hexavalent transuranium elements. Proceeding from the dependence of formal potentials of the pairs Cusup((3))-Cusup((2)), Npsup((7))-Npsup((6)), Pusup((7))-Pusup((6)) on alkali concentration, it has been established that beginning with concentration 1M the potential of the pair Cusup((3))-Cusup((2)) is higher than that of the pair Npsup((7))-Npsup((6)) by approximately 50 mV. This means that a rather complete oxidation of hexavalent neptunium to heptavalent is possible by the action of copper (3) excess on neptunium (6) when KOH concentration is 1M and higher. Oxidation close to quantitative is attained in 1M KOH when excess of copper(3) is used and the ratio Npsup((6)): Cusup((3)) is 1:4 and higher. When KOH concentration is more than 1M a sufficiently complete oxidation (96-97%) of neptunium (6) is attained at Npsup((6)):Cusup((3))=1:2 or 1:3. Optimum conditions for oxidizing plutonium are 11M KOH and 2-3-fold excess of copper (3) reagent. At 9M KOH and a ratio Pusup((6)):Cusup((3))=1:2 the yield of Pu (7) is 33 %

[New perspectives in biomonitoring of metallic elements: the example of hexavalent chromium].

Science.gov (United States)

Mutti, A; De Palma, G; Goldoni, M

2012-01-01

Plating industry is an important productive sector in all the national territory, because of its contribution to a high number of industrial products and crafts. In the chrome plating sector there is a specific chemical risk due to the exposure to compounds containing hexavalent Chromium [Cr(VI)]. Exhaled breath condensate (EBC) has been used to study both acute and long term exposure to Cr(VI) in chrome plating workers. Cr-EBC correlates with specific oxidative stress biomarkers. Moreover, both total Cr and its hexavalent fraction can be measured in EBC, which therefore is a promising biological fluid to assess the absorbed dose at the target organ level, the pulmonary reduction kinetics of Cr(VI) and in general its local pneumotoxic effects. EBC collection and analysis could give additional information to the traditional measures performed during biomonitoring.

Hexavalent Chromium Compounds

Science.gov (United States)

Learn about chromium, exposure to which can increase your risk of lung cancer and cancer of the paranasal sinuses and nasal cavity. Hexavalent chromium compounds have been used as corrosion inhibitors in a wide variety of products and processes.

NASA and ESA Collaboration on Hexavalent Chrome Alternatives - Pretreatments with Primers Screening Final Test Report

Science.gov (United States)

Rothgeb, Matthew J.; Kessel, Kurt R.

2015-01-01

Hexavalent chromium (hex chrome or Cr(VI)) is a widely used element within applied coating systems because of its self-healing and corrosion-resistant properties. The replacement of hex chrome in the processing of aluminum for aviation and aerospace applications remains a goal of great significance. Aluminum is the major manufacturing material of structures and components in the space flight arena. The National Aeronautics and Space Administration (NASA) and the European Space Agency (ESA) are engaged in a collaborative effort to test and evaluate alternatives to hexavalent chromium containing corrosion coating systems. NASA and ESA share common risks related to material obsolescence associated with hexavalent chromium used in corrosion-resistant coatings. In the United States, Occupational Safety and Health Administration (OSHA) studies have concluded that hexavalent chromium is carcinogenic and poses significant risk to human health. On May 5, 2011, amendments to the Defense Federal Acquisition Regulation Supplement (DFARS) were issued in the Federal Register. Subpart 223.73 prohibits contracts from requiring hexavalent chromium in deliverables unless certain exceptions apply. Subpart 252.223-7008 provides the contract clause prohibiting contractors and subcontractors from using or delivering hexavalent chromium in a concentration greater than 0.1 percent by weight for all new contracts associated with supplies, maintenance and repair services, and construction materials. ESA faces its own increasingly stringent regulations within European directives such as Registration, Evaluation, Authorization and Restriction of Chemical (REACH) substances and the Restriction of Hazardous Substances Directive (RoHS) which have set a mid-2017 sunset date for hexavalent chromium. NASA and ESA continue to search for an alternative to hexavalent chromium in coatings applications that meet their performance requirements in corrosion protection, cost, operability, and health and

Hexavalent Chromium IV-Free Primer Development

Science.gov (United States)

Alldredge, Michael J.; Buck, Amy L.

2015-01-01

Primer materials provide corrosion protection for metal parts as well as an increased adhesion between metallic substrates and thermal protection systems (TPSs). Current primers for use in cryogenic applications contain hexavalent chromium. This hexavalent chromium provides excellent corrosion protection even in a cryogenic environment, but it is a carcinogen that requires special equipment and waste control procedures to use. The hazardous nature of hexavalent chromium makes it an obsolescence risk in the future. This study included two phases of evaluation. Thirteen primers were initially identified as candidates and twelve of those primers were tested in phase 1. Four of the best performing candidates from phase 1 continued into phase 2 testing. Phase 1 testing consisted mostly of liquid constituent and physical property testing. Cryoflex and salt fog testing were included in phase 1 because of their importance to the overall success of a candidate material. Phase 2 consisted of physical, thermal, and mechanical properties for nominally processed and fabricated specimens.

Hexavalent and trivalent chromium in leather: What should be done?

Science.gov (United States)

Moretto, Angelo

2015-11-01

Trivalent chromium compounds are used for leather tanning, and chromium may be released during use of leather goods. In certain instances, small amounts of hexavalent chromium can be formed and released. Both trivalent and hexavalent chromium can elicit allergic skin reaction in chromium sensitised subjects, the latter being significantly more potent. Induction of sensitisation only occurs after exposure to hexavalent chromium. A minority of subjects are sensitised to chromium, and in a fraction of these subjects allergic skin reaction have been described after wearing leather shoes or, less frequently, other leather goods. The evidence that in all these cases the reaction is related to hexavalent chromium is not always strong. The content of hexavalent chromium in leather is regulated in European Union, but rate of release rather than content is relevant for allergic skin reaction. The role of trivalent chromium appear much less relevant if at all. Modern tanning procedure do not pose significant risk due to either hexavalent or trivalent chromium. Dismissing bad quality and worn-off leather goods is relevant in reducing or eliminating the skin reaction. It should also be pointed out that shoe components or substances other than chromium in leather may cause allergic/irritative skin reactions. Copyright © 2015 Elsevier Inc. All rights reserved.

76 FR 71926 - Defense Federal Acquisition Regulation Supplement: Applicability of Hexavalent Chromium Policy to...

Science.gov (United States)

2011-11-21

... 0750-AH39 Defense Federal Acquisition Regulation Supplement: Applicability of Hexavalent Chromium... the use of materials containing hexavalent chromium. DATES: Comment Date: Comments on the proposed... human health and environmental risks related to the use of hexavalent chromium. Hexavalent chromium is a...

The survey of biological absorption of hexavalent chromium from aqueous solutions by Wastewater stabilization pond algae

Directory of Open Access Journals (Sweden)

Mohammad Nourisepehr

2016-06-01

Full Text Available Background: Contamination of aquatic habitats due to toxicity and accumulation of heavy metals leading to serious damage to organisms and their advance to the food chain. Chrome is one of these heavy metals for the three and six-valence oxides used in industry. Health risks such as carcinogenic hexavalent chromium have been For this reason, removal and reduction of environment is essential. Target of this study hexavalent chromium biosorption by waste stabilization pond algae is of the aquatic environment. Methods: This study was a fundamental applied; In this batch reactor, variables Was investigated pH(3,5,7,9,11, Contact time(30,60,120,180,240,300min, The concentration of hexavalent chromium(0.5,1,5mg And the concentration of algae(0.25, 0.5, 1, 3g. Liquid mixed municipal wastewater treatment stabilization pond was used for insemination. For the investigate the effects of variables pH, contact time, the concentration of hexavalent chromium values in a 250 ml Erlenmeyer flask prepared and various amounts of dried algae (0.25-0.5-1- 3 g were added to it. Then became the shakers. After mixing, the filter paper was passed. The lab temperature was centrifuged for min10-5 rpm 2700 rpm. Then it was read at a wavelength absorbed by 540 nm. . Then collected was data to Excel and SPSS software. Finally was used for hexavalent chromium adsorption isotherm model equation of Langmuir and Freundlich. Results: This study shows that PH, contact time, the concentration of hexavalent chromium and chromium concentrations of algae optimal absorption by algae concentrations, respectively, in5 mg / l, min 120, 0.5 mg / l and is 1gr. Average maximum absorption of chromium Wastewater stabilization ponds by algae 97/2%, respectively. Correlation coefficients absorption curves of these models showed that Cr (VI adsorption isotherm on wastewater stabilization pond algae follows (= R.  Conclusion: The results showed that wastewater stabilization pond algae as a

[Occupational exposure to hexavalent chromium during aircraft painting].

Science.gov (United States)

Gherardi, M; Gatto, M P; Gordiani, A; Paci, E; Proietto, A

2007-01-01

Hygienists are interested in hexavalent chromium due to its genotoxic and carcinogenic effect on humans. The use of products containing hexavalent chromium is decreasing in many industrial fields because of the substitution with less-toxic compounds. In the aeronautical industry, however, the chromate are added to primer paint as a corrosion inhibitor of aircrafts surfaces: so hexavalent chromium compounds are available in many primers with a composition ranging from 10% to 13%. The application of these primers by using electrostatic guns potentially exposes painting and coating workers at high concentrations of aerosols containing Cr(VI). The aim of the present study is the evaluation of professional exposure to hexavalent chromium during aircraft painting, by adopting both environmental personal sampling and biological monitoring. To valuate workers exposure levels the personal measurements results have been compared with the exposure limit values (TLV-TWA) and the urinary chromium contents with the biological exposure indices (IBE). Moreover the strategy of coupling environmental sampling with biological monitoring seems to be a useful instrument to measure the validity of the individual protection devices.

Removal of chromium hexavalent of residual water from tannery using hydrotalcite

International Nuclear Information System (INIS)

Martinez G, S.; Martinez, V.; Bulbulian, S.

2000-01-01

One of the main problems of leather tanned is the treatment that must be give to the waste water polluted with chrome which stays in trivalent form, but it is easily oxidated at chromium hexavalent. This work pretends to find an elimination media for chromium (VI) from water using the original synthetic hydrotalcite and calcined as sorbent by its anion exchange and memory effect properties. The tannery water was characterized by X-ray diffraction, thermal gravimetric analysis, specific surface and infrared spectroscopy. (Author)

Hexavalent Chrome Free Coatings for Electronics: Electromagnetic Interference (EMI) Shielding Effectiveness (SE)

Science.gov (United States)

Kessel, Kurt R.

2016-01-01

Determine the suitability of trivalent chromium conversion coatings that meet the requirements of MIL-DTL-5541, Type II, for use in applications where high-frequency electrical performance is important. Evaluate the ability of hexavalent chrome free pretreated aluminum to form adequate EMI seals, and maintain that seal while being subjected to harsh environmental conditions. Assess the performance of trivalent chromium pretreatments against a known control hexavalent chrome pretreatment before and after they have been exposed to a set of environmental conditions. It is known that environmental testing causes a decrease in shielding effectiveness when hexavalent chrome pretreatments are used (Alodine 1200s). Need to determine how shielding effectiveness will be affected with the use of hexavalent chrome free pretreatments. Performance will be assessed by evaluating shielding effectiveness (SE) test data from a variety of test samples comprised of different aluminum types and/or conversion coatings. The formation of corrosion will be evaluated between the mating surfaces and gasket to assess the corrosion resistant properties of the pretreatments, comparing the hexavalent control to the hexavalent chrome free pretreatments.

Electrodeposited tungsten-nickel-boron: A replacement for hexavalent chromium

International Nuclear Information System (INIS)

Steffani, C.; Meltzer, M.

1995-04-01

Chromium, deposited from acidic solutions of its hexavalent ion, has been the rule for wear resistant, corrosion resistant coatings for many years. Although chromium coatings are durable, the plating process generates air emissions, effluent rinse waters, and process solutions that are toxic, suspected carcinogens, and a risk to human health and the environment. Tungsten-nickel-boron (W-Ni-B) alloy deposition is a potential substitute for hexavalent chrome. It has excellent wear, corrosion, and mechanical properties and also may be less of an environmental risk. This study examines the electroplating process and deposit properties of W-Ni-B and compares them with those of hexavalent chrome

Field screening for hexavalent chromium in soil: A fast-turnaround field method based on water extraction

International Nuclear Information System (INIS)

McCain, R.G.; Baechler, M.A.

1994-01-01

Sodium dichromate has been identified as a contaminant of concern at several waste sites on the Hanford Site. Although chromium standards for soil are typically stated in terms of total chrome, much of the toxicity and carcinogenicity are attributed to the hexavalent state, which typically exists as a relatively mobile anion. Investigation and removal of crushed drums potentially containing residual sodium dichromate required a field test for hexavalent chromium to support characterization and remediation activities. Previous experience with a commercially available field test kit had been unsuccessful. This stimulated an effort to determine potential sources of error in the field test and led to a number of modifications that significantly improved the reliability of the test

75 FR 18041 - Defense Federal Acquisition Regulation Supplement; Minimizing Use of Hexavalent Chromium (DFARS...

Science.gov (United States)

2010-04-08

...-AG35 Defense Federal Acquisition Regulation Supplement; Minimizing Use of Hexavalent Chromium (DFARS... Regulation Supplement (DFARS) to address requirements for minimizing the use of hexavalent chromium in... of items containing hexavalent chromium under DoD contracts unless an exception applies. DATES...

Reduction Rates for Higher Americium Oxidation States in Nitric Acid

Energy Technology Data Exchange (ETDEWEB)

Grimes, Travis Shane [Idaho National Lab. (INL), Idaho Falls, ID (United States); Mincher, Bruce Jay [Idaho National Lab. (INL), Idaho Falls, ID (United States); Schmitt, Nicholas C [Idaho National Lab. (INL), Idaho Falls, ID (United States)

2015-09-30

The stability of hexavalent americium was measured using multiple americium concentrations and nitric acid concentrations after contact with the strong oxidant sodium bismuthate. Contrary to our hypotheses Am(VI) was not reduced faster at higher americium concentrations, and the reduction was only zero-order at short time scales. Attempts to model the reduction kinetics using zero order kinetic models showed Am(VI) reduction in nitric acid is more complex than the autoreduction processes reported by others in perchloric acid. The classical zero-order reduction of Am(VI) was found here only for short times on the order of a few hours. We did show that the rate of Am(V) production was less than the rate of Am(VI) reduction, indicating that some Am(VI) undergoes two electron-reduction to Am(IV). We also monitored the Am(VI) reduction in contact with the organic diluent dodecane. A direct comparison of these results with those in the absence of the organic diluent showed the reduction rates for Am(VI) were not statistically different for both systems. Additional americium oxidations conducted in the presence of Ce(IV)/Ce(III) ions showed that Am(VI) is reduced without the typical growth of Am(V) observed in the systems sans Ce ion. This was an interesting result which suggests a potential new reduction/oxidation pathway for Am in the presence of Ce; however, these results were very preliminary, and will require additional experiments to understand the mechanism by which this occurs. Overall, these studies have shown that hexavalent americium is fundamentally stable enough in nitric acid to run a separations process. However, the complicated nature of the reduction pathways based on the system components is far from being rigorously understood.

Review article. Adverse hematological effects of hexavalent chromium: an overview

Directory of Open Access Journals (Sweden)

Ray Rina Rani

2016-06-01

Full Text Available Workers of tanneries, welding industries, factories manufacturing chromate containing paints are exposed to hexavalent chromium that increas¬es the risk of developing serious adverse health effects. This review elucidates the mode of action of hexavalent chromium on blood and its adverse effects. Both leukocyte and erythrocyte counts of blood sharply decreased in Swiss mice after two weeks of intraperitoneal treatment with Cr (VI, with the erythrocytes transforming into echinocytes. The hexavalent chromium in the blood is readily reduced to trivalent form and the reductive capacity of erythrocytes is much greater than that of plasma. Excess Cr (VI, not reduced in plasma, may enter erythrocytes and lymphocytes and in rodents it induces microcytic anemia. The toxic effects of chromium (VI include mitochondrial injury and DNA damage of blood cells that leads to carcinogenicity. Excess Cr (VI increases cytosolic Ca2+ activity and ATP depletion thereby inducing eryptosis. Se, vitamin C, and quercetin are assumed to have some protective effect against hexavalent chromium induced hematological disorders.

Hexavalent Chrome Free Coatings for Electronics Applications: Joint Test Report

Science.gov (United States)

Rothgeb, Matt; Kessel, Kurt

2013-01-01

The overall objective of the Hexavalent Chrome Free Coatings for Electronics Applications project is to evaluate and test pretreatments not containing hexavalent chrome in avionics and electronics housing applications. This objective will be accomplished by testing strong performing coating systems from prior NASA and DoD testing or new coating systems as determined by the stakeholders.

RDT&E Progress and Plansfor Hexavalent Chromium (Cr6+)

Science.gov (United States)

2011-05-12

RDT&E Progress and Plans for Hexavalent Chromium (Cr6+) Bruce Sartwell Weapons Systems and Platforms Program Manager E2S2 Conference May 12, 2011...2011 2. REPORT TYPE 3. DATES COVERED 00-00-2011 to 00-00-2011 4. TITLE AND SUBTITLE RDT&E Progress and Plansfor Hexavalent Chromium (Cr6+) 5a...Development of Accelerated Corrosion Test Protocols Alternatives to Hex Chrome and Cadmium Plating Alternatives to Hex Chrome Pretreatments

Electrochemical removal of hexavalent chromium from wastewater using Platinum-Iron/Iron-carbon nanotubes and bipolar Electrodes

Directory of Open Access Journals (Sweden)

Hoshyar Hossini

2015-01-01

Full Text Available Background: In recent decades, electrocoagulation (EC has engrossed much attention as an environmental-friendly and effectiveness process. In addition, the EC process is a potential suitable way for treatment of wastewater with concern to costs and environment. The object of this study was electrochemical evaluation of chromium removal from industrial wastewater using Platinum and carbon nanotubes electrodes. Materials and Methods: The effect of key variables including pH (3–9, hexavalent chromium concentration (50–300 mg/l, supporting electrolyte (NaCl, KCl, Na2CO3 and KNO3 and its dosage, Oxidation-Reduction variations, sludge generation rate and current density (2–20 mA/cm2 was determined. Results: Based on experimental data, optimum conditions were determined in 20, 120 min, pH 3, NaCl 0.5% and 100 mg/L initial concentration of chromium. Conclusions: Removal of hexavalent chromium from the wastewater could be successfully performanced using Platinum-Iron/Iron-carbon nanotubes and bipolar Electrodes.

Electrochemical reduction of hexavalent chromium in ground water

Energy Technology Data Exchange (ETDEWEB)

Bansal, S. [Lawrence Livermore National Lab., CA (United States)

1994-12-01

Electrochemical reduction of hexavalent chromium (Cr{sup +6}) to its trivalent state (Cr{sup +3}) is showing promising results in treating ground water at Lawrence Livermore National Laboratory`s (LLNL`s) Main Site. An electrolytic cell using stainless-steel and brass electrodes has been found to offer the most efficient reduction while yielding the least amount of precipitate. Trials have successfully lowered concentrations of Cr{sup +6} to below 11 parts per billion (micrograms/liter), the California state standard. We ran several trials to determine optimal voltage for running the cell; each trial consisted of applying a voltage between 6V and 48V for ten minutes through samples obtained at Treatment Facility C(TFC). No conclusive data has been obtained yet.

Development of Surface Complexation Models of Cr(VI) Adsorption on Soils, Sediments and Model Mixtures of Kaolinite, Montmorillonite, γ-Alumina, Hydrous Manganese and Ferric Oxides and Goethite

Energy Technology Data Exchange (ETDEWEB)

Koretsky, Carla [Western Michigan University

2013-11-29

Hexavalent chromium is a highly toxic contaminant that has been introduced into aquifers and shallow sediments and soils via many anthropogenic activities. Hexavalent chromium contamination is a problem or potential problem in the shallow subsurface at several DOE sites, including Hanford, Idaho National Laboratory, Los Alamos National Laboratory and the Oak Ridge Reservation (DOE, 2008). To accurately quantify the fate and transport of hexavalent chromium at DOE and other contaminated sites, robust geochemical models, capable of correctly predicting changes in chromium chemical form resulting from chemical reactions occurring in subsurface environments are needed. One important chemical reaction that may greatly impact the bioavailability and mobility of hexavalent chromium in the subsurface is chemical binding to the surfaces of particulates, termed adsorption or surface complexation. Quantitative thermodynamic surface complexation models have been derived that can correctly calculate hexavalent chromium adsorption on well-characterized materials over ranges in subsurface conditions, such pH and salinity. However, models have not yet been developed for hexavalent chromium adsorption on many important constituents of natural soils and sediments, such as clay minerals. Furthermore, most of the existing thermodynamic models have been developed for relatively simple, single solid systems and have rarely been tested for the complex mixtures of solids present in real sediments and soils. In this study, the adsorption of hexavalent chromium was measured as a function of pH (3-10), salinity (0.001 to 0.1 M NaNO3), and partial pressure of carbon dioxide(0-5%) on a suite of naturally-occurring solids including goethite (FeOOH), hydrous manganese oxide (MnOOH), hydrous ferric oxide (Fe(OH)3), γ-alumina (Al2O3), kaolinite (Al2Si2O5(OH)4), and montmorillonite (Na3(Al, Mg)2Si4O10(OH)2-nH2O). The results show that all of these materials can bind substantial quantities of

The controlled-potential coulometric determination of plutonium based upon cerium oxidation and the Pu022+/Pu4+ valency change

International Nuclear Information System (INIS)

Phillips, G.; Crossley, D.; Venkataramana, P.

1977-09-01

Conditions have been established enabling plutonium to be oxidised quantitatively to the hexavalent state in the working compartment of a controlled-potential coulometric cell using electrogenerated ceric ion or excess ceric nitrate. The excess ceric ion is reduced in situ electrochemically without reduction of the hexavalent plutonium. The plutonium is then determined controlled-potential coulometrically by reduction to Pu 3+ followed by oxidation to Pu 4+ . The first oxidation step is conducted in molar nitric acid solution containing sulphamic acid but the coulometric determination step is conducted in molar sulphuric acid solution. The results obtained in the coulometric determination step were less satisfactory following oxidation with electrogenerated ceric ion rather than with chemically added ceric nitrate. Using the recommended conditions, 6 mg quantities of plutonium can be determined with an accuracy of 100.06% and a precision of 0.12% (coefficient of variation). The behaviour of chromium, manganese and vanadium impurity is reported. (author)

REMOVAL OF HEXAVALENT CHROMIUM FROM AQUEOUS ...

African Journals Online (AJOL)

a

be used again to adsorb heavy metal ions. ... Among these heavy metals are chromium, copper and ... poisoning can result from high exposure to hexavalent chromium [2]. Most of the ..... At low pH, the sorbent is positively charged because of.

NASA and ESA Collaboration on Hexavalent Chrome Free Coatings

Science.gov (United States)

Greene, Brian

2017-01-01

Presentation on the NASA and ESA Collaboration on Hexavalent Chrome Free Coatings project. Project is in response to a Memorandum of Understanding between NASA and ESA Concerning Cooperation in the Field of Space Transportation - signed September 11, 2009. The National Aeronautics and Space Administration (NASA) and the European Space Agency (ESA) have expressed mutual interest in pursuing cooperation in the areas of evaluating hexavalent chrome-free coatings, environmentally-preferable coatings for maintenance of launch facilities and ground support equipment, citric acid as an alternative to nitric acid for passivation of stainless steel alloys.

GSDO Program Hexavalent Chrome Alternatives: Final Pretreatments Test Report

Science.gov (United States)

Kessel, Kurt

2013-01-01

Hexavalent chrome free pretreatments should be considered for use on Ground Support Equipment (OSE) and Electrical Ground Support Equipment (EOSE). Both of the hexavalent chrome free pretreatments (Metalast TCP HF and SurTec 650C) evaluated by this project met, and in some instances exceeded, the requirements ofMIL-DTL-5541 "Chemical Conversion Coatings on Aluminum and Aluminum Alloys". For DC resistance measurements, both Metalast TCP HF and SurTec (!50C met initial requirements following assembly and in many cases continued to maintain passing readings for the duration of testing.

Origin of hexavalent chromium in groundwater

DEFF Research Database (Denmark)

Kazakis, N.; Kantiranis, N.; Kalaitzidou, K.

2017-01-01

Hexavalent chromium constitutes a serious deterioration factor for the groundwater quality of several regions around the world. High concentrations of this contaminant have been also reported in the groundwater of the Sarigkiol hydrological basin (near Kozani city, NW Greece). Specific interest w...

Effective bioreduction of hexavalent chromium–contaminated water ...

African Journals Online (AJOL)

AFRICAN JOURNALS ONLINE (AJOL) · Journals · Advanced Search · USING ... Evaluation after reactor termination with SEM-EDX and XRD confirmed the ... Keywords: Bioreduction, fixed-film reactor, hexavalent chromium, microbial diversity ...

Investigation of alternative phosphating treatments for nickel and hexavalent chromium elimination

International Nuclear Information System (INIS)

Jazbinsek, Luiz Antonio Rossi

2014-01-01

The phosphating processes are widely used in industry as surface treatments for metals, especially for low thickness plates, improving the adhesion between the metallic surface and the paint coating, and increasing the durability of paint systems against corrosion attacks. The tricationic phosphates containing zinc, nickel and manganese are commonly applied on steel. There is much discussion about the replacement of nickel by another element in order to have an environmentally friendly phosphating process. Niobium as a replacement for nickel has been evaluated. The most significant environmental impacts of phosphating processes are related to the presence of nickel and hexavalent chromium used in the process, this last as a passivation treatment. Nickel and hexavalent chromium are harmful to human and environment leading to contamination of water and soil. In the present study phosphate layers containing zinc, manganese and niobium have been evaluated and characterized on galvanized steel, and the results were compared with phosphates containing zinc, manganese and nickel, or a bicationic phosphate layer with zinc and manganese. Although the use of hexavalent chromium is not recommended worldwide, it is still used in processes for sealing the porosity of phosphate layers. This element is carcinogenic and has been associated with various diseases. Due to the passivation characteristics of niobium, this study also evaluated the tricationic bath containing niobium ammonium oxalate as a passivation treatment. The results showed that it could act as a replacement for the hexavalent chromium. The results of the present study showed that formulations containing niobium are potential replacements for hexavalent chromium and similar corrosion protection was obtained for the phosphate containing nickel or that with niobium. The morphology observed by scanning electron microscopy, gravimetric tests, porosity and adhesion evaluation results indicated that the phosphate

A gravimetric method for the determination of oxygen in uranium oxides and ternary uranium oxides by addition of alkaline earth compounds

International Nuclear Information System (INIS)

Fujino, Takeo; Tagawa, Hiroaki; Adachi, Takeo; Hashitani, Hiroshi

1978-01-01

A simple gravimetric determination of oxygen in uranium oxides and ternary uranium oxides is described. In alkaline earth uranates which are formed by heating in air at 800-1100 0 C, uranium is in the hexavalent state over certain continuous ranges of alkaline earth-to-uranium ratios. Thus, if an alkaline earth uranate or a compound containing an alkaline earth element, e.g. MgO, is mixed with the oxide sample and heated in air under suitable conditions, oxygen can be determined from the weight change before and after the reaction. The standard deviation of the O:U ratio for a UOsub(2+x) test sample is +-0.0008-0.001, if a correction is applied for atmospheric moisture absorbed during mixing. (Auth.)

NASA and ESA Collaboration on Hexavalent Chrome Alternatives: Pretreatments Only Final Test Report

Science.gov (United States)

Kessel, Kurt R.

2015-01-01

Hexavalent chromium (hex chrome or CR(VI)) is a widely used element within applied coating systems because of its self-healing and corrosion-resistant properties. The replacement of hex chrome in the processing of aluminum for aviation and aerospace applications remains a goal of great significance. Aluminum is the major manufacturing material of structures and components in the space flight arena. The National Aeronautics and Space Administration (NASA) and the European Space Agency (ESA) are engaged in a collaborative effort to test and evaluate alternatives to hexavalent chromium containing corrosion coating systems. NASA and ESA share common risks related to material obsolescence associated with hexavalent chromium used in corrosion-resistant coatings.

REMOVAL OF HEXAVALENT CHROMIUM FROM DRINKING WATER

Directory of Open Access Journals (Sweden)

A. R. Asgari ، F. Vaezi ، S. Nasseri ، O. Dördelmann ، A. H. Mahvi ، E. Dehghani Fard

2008-10-01

Full Text Available Removal of chromium can be accomplished by various methods but none of them is cost-effective in meeting drinking water standards. For this study, granular ferric hydroxide was used as adsorbent for removal of hexavalent chromium. Besides, the effects of changing contact time, pH and concentrations of competitive anions were determined for different amounts of granular ferric hydroxide. It was found that granular ferric hydroxide has a high capacity for adsorption of hexavalent chromium from water at pH≤7 and in 90 min contact time. Maximum adsorption capacity was determined to be 0.788 mg Cr+6/g granular ferric hydroxide. Although relatively good adsorption of sulfate and chloride had been specified in this study, the interfering effects of these two anions had not been detected in concentrations of 200 and 400 mg/L. The absorbability of hexavalent chromium by granular ferric hydroxide could be expressed by Freundlich isotherm with R2>0.968. However, the disadvantage was that the iron concentration in water was increased by the granular ferric hydroxide. Nevertheless, granular ferric hydroxide is a promising adsorbent for chromium removal, even in the presence of other interfering compounds, because granular ferric hydroxide treatment can easily be accomplished and removal of excess iron is a simple practice for conventional water treatment plants. Thus, this method could be regarded as a safe and convenient solution to the problem of chromium-polluted water resources.

Treatment of hexavalent chrome by bacteria. Saikin ni yoru rokka kuromu no shori

Energy Technology Data Exchange (ETDEWEB)

Otake, H [Hiroshima University, Hiroshima (Japan). Faculty of Engineering

1993-08-01

A biological reduction method in which hazardous hexavalent chrome is reduced by bacteria is explained as one of the bioremediation technologies. Those bacteria are separated from active sludge in the urban sewage treatment plant. The hexavalent chrome-reducing bacteria were isolated by cultivating the sludge. They were Enterobacter cloacae which are intestinal bacteria. Then, they were named HO1 stock. As a result of analyzing the reduction mechanism, it was made clear that the function is localized in the cellular endosporium and that the reduction is made by utilizing the electronic transfer system of endosporium. Under both aerobic and anaerobic conditions, they convert the hexavalent chrome into the trivalent chrome outside the cells. As a result of test, it was known that 5mM hexavalent chrome can be treated in one day. A quick reduction was confirmed also through an experiment in which carbon source was added to the industrial wastewater. If used for the treatment of sludge/water contaminated by hexavalent chrome, the present reduction by bacteria has the following advantages: The highest reduction rate is given near pH=7 at ordinary temperatures. It is not necessary to add chemicals. Energy is not needed. It is a disadvantageous fact that the present bacteria, if exposed to oxygen, become inactive. 18 refs., 5 figs.

Hexavalent chromium induces chromosome instability in human urothelial cells

Energy Technology Data Exchange (ETDEWEB)

Wise, Sandra S. [Wise Laboratory of Environmental and Genetic Toxicology, Maine Center for Toxicology and Environmental Health, Department of Applied Medical Science, University of Southern Maine, Science Building, 96 Falmouth Street, Portland, ME 04103 (United States); Holmes, Amie L. [Wise Laboratory of Environmental and Genetic Toxicology, Maine Center for Toxicology and Environmental Health, Department of Applied Medical Science, University of Southern Maine, Science Building, 96 Falmouth Street, Portland, ME 04103 (United States); Department of Radiation Oncology, Dana Farber Cancer Institute, 450 Brookline Ave., Boston, MA 02215 (United States); Liou, Louis [Department of Pathology, Boston University School of Medicine, 670 Albany St., Boston, MA 02118 (United States); Adam, Rosalyn M. [Department of Surgery, Harvard Medical School, Boston, MA 02115 (United States); Wise, John Pierce Sr., E-mail: john.wise@louisville.edu [Wise Laboratory of Environmental and Genetic Toxicology, Maine Center for Toxicology and Environmental Health, Department of Applied Medical Science, University of Southern Maine, Science Building, 96 Falmouth Street, Portland, ME 04103 (United States)

2016-04-01

Numerous metals are well-known human bladder carcinogens. Despite the significant occupational and public health concern of metals and bladder cancer, the carcinogenic mechanisms remain largely unknown. Chromium, in particular, is a metal of concern as incidences of bladder cancer have been found elevated in chromate workers, and there is an increasing concern for patients with metal hip implants. However, the impact of hexavalent chromium (Cr(VI)) on bladder cells has not been studied. We compared chromate toxicity in two bladder cell lines; primary human urothelial cells and hTERT-immortalized human urothelial cells. Cr(VI) induced a concentration- and time-dependent increase in chromosome damage in both cell lines, with the hTERT-immortalized cells exhibiting more chromosome damage than the primary cells. Chronic exposure to Cr(VI) also induced a concentration-dependent increase in aneuploid metaphases in both cell lines which was not observed after a 24 h exposure. Aneuploidy induction was higher in the hTERT-immortalized cells. When we correct for uptake, Cr(VI) induces a similar amount of chromosome damage and aneuploidy suggesting that the differences in Cr(VI) sensitivity between the two cells lines were due to differences in uptake. The increase in chromosome instability after chronic chromate treatment suggests this may be a mechanism for chromate-induced bladder cancer, specifically, and may be a mechanism for metal-induced bladder cancer, in general. - Highlights: • Hexavalent chromium is genotoxic to human urothelial cells. • Hexavalent chromium induces aneuploidy in human urothelial cells. • hTERT-immortalized human urothelial cells model the effects seen in primary urothelial cells. • Hexavalent chromium has a strong likelihood of being carcinogenic for bladder tissue.

Oxidation of Cr(III)-Fe(III) Mixed-phase Hydroxides by Chlorine: Implications on the Control of Hexavalent Chromium in Drinking Water.

Science.gov (United States)

Chebeir, Michelle; Liu, Haizhou

2018-05-17

The occurrence of chromium (Cr) as an inorganic contaminant in drinking water is widely reported. One source of Cr is its accumulation in iron-containing corrosion scales of drinking water distribution systems as Cr(III)-Fe(III) hydroxide, i.e., FexCr(1-x)(OH)3(s), where x represents the Fe(III) molar content and typically varies between 0.25 and 0.75. This study investigated the kinetics of inadvertent hexavalent chromium Cr(VI) formation via the oxidation of FexCr(1-x)(OH)3(s) by chlorine as a residual disinfectant in drinking water, and examined the impacts of Fe(III) content and drinking water chemical parameters including pH, bromide and bicarbonate on the rate of Cr(VI) formation. Data showed that an increase in Fe(III) molar content resulted in a significant decrease in the stoichiometric Cr(VI) yield and the rate of Cr(VI) formation, mainly due to chlorine decay induced by Fe(III) surface sites. An increase in bicarbonate enhanced the rate of Cr(VI) formation, likely due to the formation of Fe(III)-carbonato surface complexes that slowed down the scavenging reaction with chlorine. The presence of bromide significantly accelerated the oxidation of FexCr(1-x)(OH)3(s) by chlorine, resulting from the catalytic effect of bromide acting as an electron shuttle. A higher solution pH between 6 and 8.5 slowed down the oxidation of Cr(III) by chlorine. These findings suggested that the oxidative conversion of chromium-containing iron corrosion products in drinking water distribution systems can lead to the occurrence of Cr(VI) at the tap, and the abundance of iron, and a careful control of pH, bicarbonate and bromide levels can assist the control of Cr(VI) formation.

Chemical states of molybdenum in radioactive waste glass

International Nuclear Information System (INIS)

Ishiguro, Katsuhiko; Kawanishi, Nobuo; Nagaki, Hiroshi; Naito, Aritsune

1982-01-01

In order to confirm an expectation that the chemical state of molybdenum in glass reflects the phase separation tendency of the yellow solid from the melt of borosilicate glass, simulated waste glasses were prepared, and ESCA analysis was performed using a commercially available electron spectrometer (PHI550 E) with an excitation source consisting of Mg Kα-ray. The effects of the concentration of Mo and FE 2 O 3 and the melting atmosphere (oxidizing or reducing) in which the samples were prepared on the chemical state of Mo and the solubility of MoO 3 were examined. From the observation of Mo spectra, it was shown that Mo in waste glass had several valencies, e.g., Mo(3), Mo(4), Mo(5) and Mo(6), while Mo in the yellow solid separated from the melts exhibited hexa-valent state, the peak intensity of higher valencies increased relatively with the increase of MoO 3 concentration, but the chemical state of Mo did not change remarkably around the solubility limit of MoO 3 , the melting atmosphere influenced on the Mo state in the waste glass, the peak intensity of Mo(6) increased relatively with the increasing Fe 2 O 3 concentration, and Mo in devitrified glass exhibited hexa-valent state. (Yoshitake, I.)

Development of a hexavalent chromium ISFET sensor with a polymeric membrane including tributylphosphate

International Nuclear Information System (INIS)

Zazoua, A.; Zougar, S.; Kherrat, R.; Samar, M.H.; Jaffrezic-Renault, N.; Errachid, A.; Abbaci, A.

2006-01-01

This paper presents a first report on chromium ISFET (ion-sensitive field effect transistor) based on a polymeric membrane (siloprene) including an ionophore (tributylphosphate) sensitive for hexavalent chromium. The sensor sensitivity as a function of the pH was studied; its value is minimum in a pH interval from 5.5 to 7.5. The sensitivity for hexavalent chromium was found to be 15 mV/loga Cr 6+ in the range of 10 -4 to 10 -2 M. The detection limit was found to be 10 -5 M. The studied interfering ions are Pb(II) and Cd(II) that do not represent a great perturbation upon the response for hexavalent chromium

Development of a hexavalent chromium ISFET sensor with a polymeric membrane including tributylphosphate

Energy Technology Data Exchange (ETDEWEB)

Zazoua, A. [Universite de Annaba, BP 12, El-Hadjar, Annaba (Algeria); Zougar, S. [Universite de Annaba, BP 12, El-Hadjar, Annaba (Algeria); Kherrat, R. [Universite de Annaba, BP 12, El-Hadjar, Annaba (Algeria); Samar, M.H. [Universite de Annaba, BP 12, El-Hadjar, Annaba (Algeria); Jaffrezic-Renault, N. [CEGELY-UMR 5005 CNRS, Ecole centrale de Lyon, 69134 Ecully cedex (France)]. E-mail: Nicole.Jaffrezic@ec-lyon.fr; Errachid, A. [Center of Reference for Bioengineering in Catalonia (CREBEC), Laboratory of Nanobioengineering, Parc Cientific de Barcelona, Universidad de Barcelona C/ Josep Samitier 1-5, 08028 Barcelona (Spain); Abbaci, A. [Universite de Annaba, BP 12, El-Hadjar, Annaba (Algeria)

2006-03-15

This paper presents a first report on chromium ISFET (ion-sensitive field effect transistor) based on a polymeric membrane (siloprene) including an ionophore (tributylphosphate) sensitive for hexavalent chromium. The sensor sensitivity as a function of the pH was studied; its value is minimum in a pH interval from 5.5 to 7.5. The sensitivity for hexavalent chromium was found to be 15 mV/loga {sub Cr{sup 6+}} in the range of 10{sup -4} to 10{sup -2} M. The detection limit was found to be 10{sup -5} M. The studied interfering ions are Pb(II) and Cd(II) that do not represent a great perturbation upon the response for hexavalent chromium.

Genotoxicity of Tri- and Hexavalent Chromium Compounds In Vivo and Their Modes of Action on DNA Damage In Vitro

Science.gov (United States)

Fang, Zhijia; Zhao, Min; Zhen, Hong; Chen, Lifeng; Shi, Ping; Huang, Zhiwei

2014-01-01

Chromium occurs mostly in tri- and hexavalent states in the environment. Hexavalent chromium [Cr(VI)] compounds are extensively used in diverse industries, and trivalent chromium [Cr(III)] salts are used as micronutrients and dietary supplements. In the present work, we report that they both induce genetic mutations in yeast cells. They both also cause DNA damage in both yeast and Jurkat cells and the effect of Cr(III) is greater than that of Cr(VI). We further show that Cr(III) and Cr(VI) cause DNA damage through different mechanisms. Cr(VI) intercalates DNA and Cr(III) interferes base pair stacking. Based on our results, we conclude that Cr(III) can directly cause genotoxicity in vivo. PMID:25111056

Adsorption of hexavalent chromium by graphite–chitosan binary ...

Indian Academy of Sciences (India)

Hexavalent chromium; graphite–chitosan composite; adsorption kinetics. 1. Introduction ... [2], while Cr(III) is less toxicity and relatively innocuous. Cr(VI) generates in ..... Human Environments (New York: Wiley Inter-Science) p 3. [4] U.S. EPA ...

Combination of synchrotron radiation X-ray microprobe and nuclear microprobe for chromium and chromium oxidation states quantitative mapping in single cells

International Nuclear Information System (INIS)

Ortega, Richard; Deves, Guillaume; Fayard, Barbara; Salome, Murielle; Susini, Jean

2003-01-01

Hexavalent chromium compounds are established carcinogens but their mechanism of cell transformation has not been elucidated yet. In this study, chromium oxidation state distribution maps in cells exposed to soluble (Na 2 CrO 4 ), or insoluble (PbCrO 4 ), Cr(VI) compounds have been obtained by use of the ESRF ID-21 X-ray microscope. In addition, the quantitative maps of element distributions in cells have been determined using the nuclear microprobe of Bordeaux-Gradignan. Nuclear microprobe quantitative analysis revealed interesting features on chromium, and lead, cellular uptake. It is suggested that cells can enhance PbCrO 4 solubility, resulting in chromium, but not lead uptake. The differential carcinogenic potential of soluble and insoluble Cr(VI) compounds is discussed with regard to chromium intracellular quantitative distribution

Americium-curium separation by means of selective extraction of hexavalent americium using a centrifugal contactor

International Nuclear Information System (INIS)

Musikas, C.; Germain, M.; Bathellier, A.

1979-01-01

This paper deals with Am (VI) - Cm (III) separation in nitrate media. The kinetics of oxidation of Am (III) by sodium persulfate in the presence of Ag + ions were reinvestigated by studying the effect of additions of small amounts of reagents which do not drastically change the distribution coefficients of Am (VI) or Cm (III) ions. Organo phosphorus solvents were selected because they are radiation resistant, possess weak reductant properties and that their affinity for hexavalent ion is high. The operating procedure was selected by consideration of the results of the two previous investigations. This can be done by using a centrifugal contactor enabling in to set organic-aqueous phase contact time in accordance with the kinetics of extraction of Am (VI), oxidation of Am (III) in aqueous phase, and reduction of Am (VI) in organic phase

Characterization and recovery of hexavalent chromium salts of an environmental liability

International Nuclear Information System (INIS)

Rangel C, A. A.; Isarain C, E.; Maldonado V, M.

2015-01-01

The purpose of this study was to examine a diverse group of washing solutions for its use in the recovery of the industrial waste hexavalent chromium, in compliance with the Mexican regulation NOM-147-SEMARNAT/SSA1-2004. The recovery process consisted of a simple random sampling and a physical-chemical characterization with consideration to the high solubility of hexavalent chromium compounds. A test was performed which implemented five different washing solutions (water, sulfuric acid, citric acid, sodium hydroxide, calcium and hydroxide). This was followed by a factorial experimental design to optimize resources with a removal efficiency of 80% and hence a recovery of 33 g/kg as CaCrO 4 (calcium chromate). Chromium hexavalent concentration in the leachate was quantified using UV-Vis spectrometry at a wavelength λ = 540 nm, while the salts recovered by evaporation were characterized using X-ray fluorescence analysis, leading to the conclusion that precipitate can be used as raw material, the main elements are Cr, Ca, Fe and Mg, and their concentration depends on the washing solution. (Author)

Hexavalent Chromium reduction by Trichoderma inhamatum

Energy Technology Data Exchange (ETDEWEB)

Morales-Battera, L.; Cristiani-Urbina, E.

2009-07-01

Reduction of hexavalent chromium [Cr(VI)] to trivalent chromium [Cr(III)] is a useful and attractive process for remediation of ecosystems and industrial effluents contaminated with Cr(VI). Cr(VI) reduction to Cr(II) can be achieved by both chemical and biological methods; however, the biological reduction is more convenient than the chemical one since costs are lower, and sludge is generated in smaller amounts. (Author)

IRIS Toxicological Review of Hexavalent Chromium (Peer Review Plan)

Science.gov (United States)

EPA is conducting a peer review of the scientific basis supporting the human health hazard and dose-response assessment of hexavalent chromium that will appear on the Integrated Risk Information System (IRIS) database.

Hexavalent Chrome Free Coatings for Electronics Applications: Joint Test Report

Science.gov (United States)

Kessel, Kurt

2012-01-01

Regardless of the corrosivity of the environment, all metals require periodic maintenance activity to guard against the insidious effects of corrosion and thus ensure that alloys meet or exceed design or performance life. The standard practice for protecting metallic substrates is the application of a coating system. Applied coating systems work via a variety of methods (barrier, galvanic, and/or inhibitor) and adhere to the substrate through a combination of chemical and physical bonds. For years hexavalent chromium has been a widely used element within applied coating systems because of its self healing and corrosion resistant properties. Occupational Safety and Health Administration (OSHA) studies have concluded that hexavalent chromium (hex chrome) is carcinogenic and poses significant risk to human health. On May 5, 2011 amendments to the Defense Federal Acquisition Regulation Supplement (DFARS) were issued in the Federal Register. Subpart 223.73 prohibits contracts from requiring hexavalent chromium in deliverables unless certain exceptions apply. These exceptions include authorization from a general or flag officer and members of the Senior Executive Service from a Program Executive Office, and unmodified legacy systems. Otherwise, Subpart 252.223-7008 provides the contract clause prohibiting contractors from using or delivering hexavalent chromium in a concentration greater than 0.1 percent by weight for all new contracts and to be included down to subcontractors for supplies, maintenance and repair services, and construction materials. National Aeronautics and Space Administration (NASA), Department of Defense (DoD), and industry stakeholders continue to search for alternatives to hex chrome in coatings applications that meet their performance requirements in corrosion protection, cost, operability, and health and safety, while typically specifying that performance must be equal to or greater than existing systems.

Chemometrics models for assessment of oxidative stress risk in chrome-electroplating workers.

Science.gov (United States)

Zendehdel, Rezvan; Shetab-Boushehri, Seyed Vahid; Azari, Mansoor R; Hosseini, Vajihe; Mohammadi, Hamidreza

2015-04-01

Oxidative stress is the main cause of hexavalant chromium-induced damage in chrome electroplating workers. The main goal of this study is toxicity analysis and the possibility of toxicity risk categorizing in the chrome electroplating workers based on oxidative stress parameters as prognostic variables. We assessed blood chromium levels and biomarkers of oxidative stress such as lipid peroxidation, thiol (SH) groups and antioxidant capacity of plasma. Data were subjected to principle component analysis (PCA) and artificial neuronal network (ANN) to obtain oxidative stress pattern for chrome electroplating workers. Blood chromium levels increased from 4.42 ppb to 10.6 ppb. Induction of oxidative stress was observed by increased in lipid peroxidation (22.38 ± 10.47 μM versus 14.74 ± 4.82 μM, p chrome electroplaters. The result showed multivariate modeling can be interpreted as the induced biochemical toxicity in the workers exposed to hexavalent chromium. Different occupation groups were assessed on the basis of risk level of oxidative stress which could further justify proceeding engineering control measures.

Laboratory Validation and Demonstrations of Non-Hexavalent Chromium Conversion Coatings for Steel Substrates (Briefing Charts)

Science.gov (United States)

2011-02-01

UNCLASSIFIED: Approved for public release; distribution unlimited. Laboratory Validation and Demonstrations of Non- Hexavalent Chromium Conversion...00-00-2011 4. TITLE AND SUBTITLE Laboratory Validation and Demonstrations of Non- Hexavalent Chromium Conversion Coatings for Steel Substrates 5a...to MRAP II Acquisition Pretreatment /conversion coatings omitted: • Hex- chrome pretreatments prohibited for new ground vehicles • Hydrogen

Reduction of hexavalent chromium by Rhizopus Oryzae

African Journals Online (AJOL)

EJIRO

reduction data and the specific growth rate constant value was calculated as 0.082 and the ... Key words: Hexavalent chromium, Rhizopus Oryzae, leather tanning, Monod and Haldane models. ... composition; Glucose 1 g; K2HPO4 0.5 g; NaCl 0.5 g; MgCl2 1.0 g; ... ficantly, because of the inhibitor role of high concentration.

Removal of Hexavalent Chromium from Aqueous Solutions using ...

African Journals Online (AJOL)

The hexavalent chromium exists in aquatic media as water soluble complex anions and persist. These are concentrated in industrial waste water especially from the tannery industries and release of effluents from industries adversely affects the environment. The removal of heavy metals from aqueous solutions is carried ...

Sampling and analysis considerations for the determination of hexavalent chromium in workplace air; Reflexions sur le prelevement et l'analyse du chrome hexavalent dans l'air des lieux de travail

Energy Technology Data Exchange (ETDEWEB)

Ashley, K.E. [CDC/NIOSH, Cincinnati, Ohio (United States); Howe, A.M. [HSL, Sheffield (United Kingdom); Demange, M. [INRS - Centre de Lorraine, Departement Metrologie des polluants, 54 - Vandoeuvre-les-Nancy (France); Nygren, O. [NIWL, Umea (Sweden)

2004-07-01

Airborne hexavalent chromium Cr(VI) is a known human respiratory carcinogen and allergen. Workers in a variety of industries may be exposed to airborne hexavalent chromium, with exposures frequently occurring via inhalation and/or dermal contact. Analytical methods for the measurement of Cr(VI) compounds in workplace samples, rather than for the determination of total elemental chromium in workplace air, are often desired because exposure limit values for Cr(VI) compounds are much lower than for total Cr. For years, sampling and analytical test methods for airborne Cr(VI) have been investigated so as to provide means for occupational exposure assessment to this highly toxic species. Inter-conversion of trivalent chromium Cr(III) and Cr(VI) can sometimes occur during sampling and sample preparation, and efforts to minimize unwanted redox reactions involving these chromium valences have been sought. Because of differences in toxicity, there is also interest in the ability to differentiate between water soluble and insoluble forms of Cr(VI), and procedures that provide solubility information concerning Cr(VI) compounds have been developed. This paper reviews the state of the art concerning the measurement of airborne Cr(VI) compounds in workplace aerosols and related samples. (authors)

Thermochemistry of rare earth doped uranium oxides LnxU1-xO2-0.5x+y (Ln = La, Y, Nd)

Science.gov (United States)

Zhang, Lei; Navrotsky, Alexandra

2015-10-01

Lanthanum, yttrium, and neodymium doped uranium dioxide samples in the fluorite structure have been synthesized, characterized in terms of metal ratio and oxygen content, and their enthalpies of formation measured by high temperature oxide melt solution calorimetry. For oxides doped with 10-50 mol % rare earth (Ln) cations, the formation enthalpies from constituent oxides (LnO1.5, UO2 and UO3 in a reaction not involving oxidation or reduction) become increasingly exothermic with increasing rare earth content, while showing no significant dependence on the varying uranium oxidation state. The oxidation enthalpy of LnxU1-xO2-0.5x+y is similar to that of UO2 to UO3 for all three rare earth doped systems. Though this may suggest that the oxidized uranium in these systems is energetically similar to that in the hexavalent state, thermochemical data alone can not constrain whether the uranium is present as U5+, U6+, or a mixture of oxidation states. The formation enthalpies from elements calculated from the calorimetric data are generally consistent with those from free energy measurements.

Adsorption of hexavalent chromium by graphite–chitosan binary

Indian Academy of Sciences (India)

Graphite chitosan binary (GCB) composite was prepared for hexavalent chromium adsorption from studied water. GCB was characterized by TGA, FTIR, SEM and X-ray diffraction techniques.Wide porous sorptive surface of 3.89 m 2 g − 1 and absorptive functionalities of GCB was due to 20% (w/w) graphite support on ...

Development of a site-specific water quality criterion for hexavalent chromium

International Nuclear Information System (INIS)

McIntyre, D.O.; Sticko, J.P.; Reash, R.J.

1995-01-01

The effluent of treated fly ash from a coal-fired power plant located on the Ohio River periodically exceeds its NPDES acute permit limit for hexavalent chromium of 15 microg/L. The increased levels of hexavalent chromium in the effluent are a recent occurrence which are likely due to changes in coal blends burned in the generating units. Ohio EPA determined the use designation of the receiving stream (Limited Resource Water) was being attained and a one-year biomonitoring program of the effluent detected no acute toxicity to Ceriodaphnia dubia or Daphnia magna. The water-effect ratio (WER) procedure was selected to develop a site-specific criterion maximum concentration for hexavalent chromium for the effluent's receiving stream. WER procedures followed those described in EPA's ''Interim Guidance on Determination and Use of Water-Effect Ratios for Metals'' (1994). Site water used in the WER determinations was undiluted effluent since the receiving stream originates at the discharge point of the outfall. 48-hour acute D. magna and 96-hour acute fathead minnow toxicity tests were selected as the primary and secondary tests, respectively for use in three seasonal WER determinations. The results of the three WER determinations and the status of the regulatory process will be presented

Mitigation of Hexavalent Chromium in Storm Water Resulting from Demolition of Large Concrete Structure at the East Tennessee Technology Park - 12286

Energy Technology Data Exchange (ETDEWEB)

Britto, Ronnie; Brown, Bridget; Hale, Timothy B.; Hensley, Janice L.; Johnson, Robert T.; Patel, Madhu [Tetra Tech, Inc. (United States); Emery, Jerry A. [Energy Solutions, Inc. (United States); Gaston, Clyde [LATA-SHARP Remediation Services - LSRS (United States); Queen, David C. [U.S. DOE-ORO (United States)

2012-07-01

American Recovery and Reinvestment Act (ARRA) funding was provided to supplement the environmental management program at several DOE sites, including the East Tennessee Technology Park (ETTP) in Oak Ridge, Tennessee. Demolition of the ETTP K-33 Building, the largest building to be demolished to date in Oak Ridge, was awarded to LSRS in FY-2010 under the ARRA program. The K-33 building was an 82 foot tall 2-story structure covering approximately 32 acres. Once this massive building was brought down to the ground, the debris was segregated and consolidated into piles of concrete rubble and steel across the remaining pad. The process of demolishing the building, tracking across concrete debris with heavy equipment, and stockpiling the concrete rubble caused it to become pulverized. During and after storm events, hexavalent chromium leached from the residual cement present in the large quantities of concrete. Storm water control measures were present to preclude migration of contaminants off-site, but these control measures were not designed to control hexavalent chromium dissolved in storm water from reaching nearby receiving water. The following was implemented to mitigate hexavalent chromium in storm water: - Steel wool was distributed around K-33 site catch basins and in water pools as an initial step in addressing hexavalent chromium. - Since the piles of concrete were too massive and unsafe to tarp, they were placed into windrows in an effort to reduce total surface area. - A Hach colorimetric field meter was acquired by the K-33 project to provide realtime results of hexavalent chromium in site surface water. - Three hexavalent chromium treatment systems were installed at three separate catch basins that receive integrated storm water flow from the K-33 site. Sodium bisulfite is being used as a reducing agent for the immobilization of hexavalent chromium while also assisting in lowering pH. Concentrations initially were 310 - 474 ppb of hexavalent chromium in

Removal of chromium hexavalent of residual water from tannery using hydrotalcite; Remocion de cromo hexavalente de aguas residuales de teneria utilizando hidrotalcita

Energy Technology Data Exchange (ETDEWEB)

Martinez G, S.; Martinez, V.; Bulbulian, S. [Instituto nacional de Investigaciones Nucleares, A.P. 18-1027, C.P. 11801 Mexico D.F. (Mexico)

2000-07-01

One of the main problems of leather tanned is the treatment that must be give to the waste water polluted with chrome which stays in trivalent form, but it is easily oxidated at chromium hexavalent. This work pretends to find an elimination media for chromium (VI) from water using the original synthetic hydrotalcite and calcined as sorbent by its anion exchange and memory effect properties. The tannery water was characterized by X-ray diffraction, thermal gravimetric analysis, specific surface and infrared spectroscopy. (Author)

Molecular and cellular mechanisms of hexavalent chromium-induced lung cancer: an updated perspective.

Science.gov (United States)

Urbano, A M; Ferreira, L M R; Alpoim, M C

2012-03-01

For over a century, chromium (Cr) has found widespread industrial and commercial use, namely as a pigment, in the production of stainless steel and in chrome plating. The adverse health effects to the skin and respiratory tract of prolonged exposure to Cr have been known or suspected for a long time, but it was much more recently that the toxicity of this element was unequivocally attributed to its hexavalent state. Based on the combined results of extensive epidemiological studies, animal carcinogenicity studies and several types of other relevant data, authoritative regulatory agencies have found sufficient evidence to classify hexavalent chromium [Cr(VI)] compounds as encountered in the chromate production, chromate pigment production and chromium plating industries as carcinogenic to humans. Crucial for the development of novel strategies to prevent, detect and/or treat Cr(VI)-induced cancers is a detailed knowledge of the molecular and cellular mechanisms underlying these pathologies. Unfortunately, in spite of a considerable research effort, crucial facets of these mechanisms remain essentially unknown. This review is intended to provide a concise, integrated and critical perspective of the current state of knowledge concerning multiple aspects of Cr(VI) carcinogenesis. It will present recent theories of Cr(VI)-induced carcinogenesis and will include aspects not traditionally covered in other reviews, such as the possible involvement of the energy metabolism in this process. A brief discussion on the models that have been used in the studies of Cr(VI)-induced carcinogenicity will also be included, due to the impact of this parameter on the relevance of the results obtained.

Study on anaerobic treatment of wastewater containing hexavalent chromium.

Science.gov (United States)

Xu, Yan-bin; Xiao, Hua-hua; Sun, Shui-yu

2005-06-01

A self-made anaerobic bio-filter bed which was inoculated with special sludge showed high efficiency in removing hexavalent chromium. When pump flow was 47 ml/min and COD(Cr) of wastewater was about 140 mg/L, it took 4 h to decrease the Cr6+ concentrations from about 60 mg/L to under 0.5 mg/L, compared with 14 h without carbon source addition. Cr6+ concentrations ranged from 64.66 mg/L to 75.53 mg/L, the system efficiency was excellent. When Cr6+ concentration reached 95.47 mg/L, the treatment time was prolonged to 7.5 h. Compared with the contrast system, the system with trace metals showed clear superiority in that the Cr6+ removal rate increased by 21.26%. Some analyses also showed that hexavalent chromium could probably be bio-reduced to trivalent chromium, and that as a result, the chrome hydroxide sediment was formed on the surface of microorganisms.

Study on anaerobic treatment of wastewater containing hexavalent chromium*

Science.gov (United States)

Xu, Yan-bin; Xiao, Hua-hua; Sun, Shui-yu

2005-01-01

A self-made anaerobic bio-filter bed which was inoculated with special sludge showed high efficiency in removing hexavalent chromium. When pump flow was 47 ml/min and CODCr of wastewater was about 140 mg/L, it took 4 h to decrease the Cr6+ concentrations from about 60 mg/L to under 0.5 mg/L, compared with 14 h without carbon source addition. Cr6+ concentrations ranged from 64.66 mg/L to 75.53 mg/L, the system efficiency was excellent. When Cr6+ concentration reached 95.47 mg/L, the treatment time was prolonged to 7.5 h. Compared with the contrast system, the system with trace metals showed clear superiority in that the Cr6+ removal rate increased by 21.26%. Some analyses also showed that hexavalent chromium could probably be bio-reduced to trivalent chromium, and that as a result, the chrome hydroxide sediment was formed on the surface of microorganisms. PMID:15909347

Hexavalents in spermatocytes of Robertsonian heterozygotes between Mus m. domesticus 2n=26 from the Vulcano and Lipari Islands (Aeolian Archipelago, Italy).

Science.gov (United States)

Berríos, Soledad; Fernández-Donoso, Raúl; Page, Jesús; Ayarza, Eliana; Capanna, Ernesto; Solano, Emanuela; Castiglia, Riccardo

2018-02-20

The size and shape of the chromosomes, as well as the chromosomal domains that compose them, are determinants in the distribution and interaction between the bivalents within the nucleus of spermatocytes in prophase I of meiosis. Thus the nuclear architecture characteristic of the karyotype of a species can be modified by chromosomal changes such as Rb chromosomes. In this study we analysed the meiotic prophase nuclear organization of the heterozygous spermatocytes from Mus musculus domesticus 2n=26, and the synaptic configuration of the hexavalent formed by the dependent Rb chromosomes Rbs 6.16, 16.10, 10.15, 15.17 and the telocentric chromosomes 6 and 17. Spreads of 88 pachytene spermatocytes from two males were studied and in all of them five metacentric bivalents, four telocentric bivalents, one hexavalent and the XY bivalent were observed. About 48% of the hexavalents formed a chain or a ring of synapsed chromosomes, the latter closed by synapsis between the short arms of telocentric chromosomes 6 and 17.  About 52% of hexavalents formed an open chain of 10 synapsed chromosomal arms belonging to 6 chromosomes.  In about half of the unsynapsed hexavalents one of the telocentric chromosome short arms appears associated with the X chromosome single axis, which was otherwise normally paired with the Y chromosome.  The cluster of pericentromeric heterochromatin mostly determines the hexavalent's nuclear configuration, dragging the centromeric regions and all the chromosomes towards the nuclear envelope similar to an association of five telocentric bivalents. These reiterated encounters between these chromosomes restrict the interactions with other chromosomal domains and might favour eventual rearrangements within the metacentric, telocentric or hexavalent chromosome subsets. The unsynapsed short arms of telocentric chromosomes frequently bound to the single axis of the X chromosome could further complicate the already complex segregation of hexavalent

Groundwater remediation of hexavalent chromium along the Columbia River at the Hanford site in Washington state, USA - 59030

International Nuclear Information System (INIS)

Foss, Dyan L.; Charboneau, Briant L.

2012-01-01

The U.S. Department of Energy Hanford Site, formerly used for nuclear weapons production, encompasses 1500 square kilometers in southeast Washington State along the Columbia River. A principle threat to the river are the groundwater plumes of hexavalent chromium (Cr(VI)), which affect approximately 9.8 square kilometers, and 4.1 kilometers of shoreline. Cleanup goals are to stop Cr(VI) from entering the river by the end of 2012 and remediate the groundwater plumes to the drinking water standards by the end of 2020. Five groundwater pump-and-treat systems are currently in operation for the remediation of Cr(VI). Since the 1990's, over 13.6 billion L of groundwater have been treated; over 1, 435 kg of Cr(VI) have been removed. This paper describes the unique aspects of the site, its environmental setting, hydrogeology, groundwater-river interface, riverine hydraulic effects, remediation activities completed to date, a summary of the current and proposed pump-and-treat operations, the in situ redox manipulation barrier, and the effectiveness of passive barriers, resins, and treatability testing results of calcium polysulfide, bio-stimulation, and electrocoagulation, currently under evaluation. (authors)

Voltametric determination of O:U relation in uranium oxide

International Nuclear Information System (INIS)

Carvalho, F.M.S. de; Abrao, A.

1988-07-01

Uranium oxide samples are dissolved in hot concentrated H 3 PO 4 - H 2 SO 4 mixture and the solution diluted with 1M H 2 SO 4 . One aliquot of such solution (A) is used to record the first voltamogram which gives the U(VI) content. To a second aliquot HNO 3 and H 2 O 2 is added to oxidise uranium to the hexavalent state (B) and the second voltamogram is recorded from 0.0 to 0.4 V X SCE. The O:U ratio in the original sample is calculated by the expression: O/U = 2.000 + [U (VI) soln.A/% U(VI) soln. B]. The method provides an accurate means for determining O to U ratios in high-purity uranium dioxide, fuel pellets and a variety of oxides prepared for developmental work on ceramic fuel materials. (author) [pt

Iron oxides nanoparticles for heavy metals removing from industrial waters

Energy Technology Data Exchange (ETDEWEB)

SORA, Sergiu; Mariana, Ion Rodica [Valahia University, Targoviste (Russian Federation); Raluca, Van-Staden; Jacobus-Frederick, Van-Staden [Laboratory of Electrochemistry and PATLAB Bucharest, National Institute of Research for Electrochemistry and Condensed Matter, Bucharest (Romania)

2011-07-01

In the environment, the iron oxides may be useful for depollution process by means of a wide range of redox reactions. Hexavalent chromium (CrVI) is a toxic form of chromium, whereas the trivalent form is not. Reduction of CrVI to CrIII is, thus, a detoxifying process and takes place in soils and sediments under anoxic conditions. Hexavalent Cr reacts with magnetite to form CrIII. The reaction yields to a surficial transformation of magnetite into maghemite. Substitution of a large range of cations can be easily induced in magnetite and maghemite because tetrahedral as well as octahedral positions are available. Dissolution curves indicated that Co, Ni and Zn were randomly distributed within the structure and replaced octahedral Fe. In contrast, Cu, Mn and Cd appear to be concentrated near the surface of the crystals. Trace amounts of chromate ions adsorbed on magnetite are reduced to Cr (III) at the surface of Fe ions. A solid state reaction in which the surface layers of magnetite are converted into maghemite appears to be involved: as more chromate is adsorbed, further reduction is halted. Key words: magnetite nanoparticles.

Removal and transformation of hexavalent chromium in sequencing ...

African Journals Online (AJOL)

The objectives of this study are to evaluate the efficiency of removal of hexavalent chromium (Cr(VI)) in a sequencing batch reactor (SBR) and to ascertain the fate of Cr(VI) in the treatment process. An SBR was operated with the FILL, REACT, SETTLE, DRAW and IDLE periods in the time ratio of 2:12:2:1.5:6.5 for a cycle ...

On the valency state of radiogenic lead in zircon and its consequences

DEFF Research Database (Denmark)

Kramers, J.; Frei, Robert; Newville, M.

2009-01-01

nucleus comes to rest. Further, a zircon grain, being small, should remain highly oxidizing in its interior by the constant loss of ß-particles, maintaining the 4+ state of radiogenic Pb. From its effective ion radius, similar to that of Zr4+, and its charge, Pb4+ has to be compatible in the zircon...... not resemble that of PbO2. The arguments why radiogenic Pb should be tetravalent are based on analogies with studies relating to the tetravalent state of 234Th and the hexavalent state of 234U, which show that a-recoil in silicates generates a strongly oxidizing environment at the site where the recoiling......-recoil damaged sites could be leached out by any electrolyte solution that reduces it to the divalent state, making it both incompatible and soluble. Thus, discordia can be generated in weathering. The curious observation that discordant Archaean zircon suites generally define trends to lower intercepts at up...

[Hexavalent chromium pollution and exposure level in electroplating workplace].

Science.gov (United States)

Zhang, Xu-hui; Zhang, Xuan; Yang, Zhang-ping; Jiang, Cai-xia; Ren, Xiao-bin; Wang, Qiang; Zhu, Yi-min

2012-08-01

To investigate the pollution of hexavalent chromium in the electroplating workplace and screen the biomarkers of chromium exposure. Field occupational health investigation was conducted in 25 electroplating workplaces. 157 electroplating workers and 93 healthy unexposed controls were recruited. The epidemiological information was collected with face to face interview. Chromium in erythrocytes was determined by graphite furnace atomic absorption spectrophotometer. The median of short-term exposure concentration of chromium in the air at electroplating workplace was 0.06 mg/m(3) (median) and ranging from 0.01 (detect limit) to 0.53 mg/m(3)). The median concentration of Cr (VI) in erythrocytes in electroplating workers was 4.41 (2.50 ∼ 5.29) µg/L, which was significantly higher than that in control subjects [1.54 (0.61 ∼ 2.98) µg/L, P electroplating workers and control subjects, except for the subjects of age less than 30 years old (P = 0.11). There was hexavalent chromium pollution in electroplating workplace. Occupational hazards prevention measures should be taken to control the chromium pollution hazards.

The electrochemical aspect of the corrosion of austenitic stainless steels, in nitric acid and in the presence of hexavalent chromium (1961); Aspect electrochimique de la corrosion d'aciers inoxydables austenitiques en milieu nitrique et en presence de chrome hexavalent (1961)

Energy Technology Data Exchange (ETDEWEB)

Coriou, H; Hure, J; Plante, G [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

1961-07-01

The corrosion of austenitic stainless steels in boiling nitric acid markedly increases when the medium contains hexavalent chromium ions. Because of several redox phenomena, the potential of the steel generally changes in course of time. Measurements show a relation between the weight loss and the potential of specimens. Additions of Mn(VII) and Ce(IV) are compared with that of Cr(VI), and show that the relation is a general one. The attack cf the metal in oxidizing media is largely intergranular, leading to exfoliation of the grains, although the steel studied is not sensitive to the classical Huey and Strauss tests. Also even in the absence of any other oxidizing reaction, the current density observed when the steel is anodically polarized under potentiostatic conditions does not correspond to the actual weight loss of the metal. (authors) [French] La corrosion d'aciers inoxydables austenitiques en milieu nitrique bouillant augmente notablement quand le milieu contient des ions chrome a l'etat hexavalent. Par suite de divers phenomenes d'oxydo-reduction, le potentiel de l'acier evolue generalement au cours du temps. Les mesures effectuees permettent d'etablir une relation entre les pertes de poids et le potentiel des echantillons. L'addition de Mn(VI) et Ce(IV) est compare a celle de Cr(VI) et montre que la relation precedente s'applique de facon generale. L'attaque du metal en milieu oxydant est en grande, partie due a une corrosion intergranulaire conduisant a un dechaussement des grains bien que l'acier etudie ne soit pas sensible aux tests classiques de Huey et de Strauss. Aussi, meme en l'absence de toute autre reaction d'oxydation l'intensite qu l'on observerait en soumettant l'acier a un potentiel anodique dans un montage potentiostatique ne correspondrait pas a la perte de poids reelle du metal. (auteurs)

Thermodynamics of synergistic extraction of hexavalent plutonium with HPMBP and neutral donors: monodentate versus bidentate

International Nuclear Information System (INIS)

Lohithakshan, K.V.; Mithapara, P.D.; Pai, S.A.; Aggarwal, S.K.; Jain, H.C.

1996-01-01

Synergistic extraction of hexavalent plutonium was studied from HNO 3 medium (0.05 M) with 1-phnyl, 3-methyl, 4-benzoyl, pyrazolone-5 (HPMBP) and different monodentate neutral donors viz. diphenyl sulphoxide (DPSO), tri-n-butyl phosphate (TBP) and tri-n-octyl phosphine oxide (TOPO) using benzene as a diluent. Thermodynamic parameters (ΔG, ΔH, ΔS) evaluated by performing the experiments at various fixed temperatures (288 K to 318 K) were compared with those reported previously for the bidentate neutral donors (DBDECMP, DHDECMP and CMPO). The net enthalpy changes were negative and comparable. The monodentate neutral donors, however, showed a larger decrease in the entropy values. Further, the negative values of enthalpy and entropy changes indicated that the organic adduct formation is an addition reaction as reported ealier for the bidentate donors. (orig.)

Hexavalent chrome: threshold concept for carcinogenicity.

Science.gov (United States)

Jones, R E

1990-03-01

Certain hexavalent chromium (Cr6+) compounds when administered via inhalation at high doses have the potential to induce lung tumors in humans and experimental animals. Trivalent chromium (Cr3+) is an essential human and animal nutrient at levels of 50 to 200 micrograms/day. Recent data have shown that the human body is able to reduce Cr6+ to Cr3+. This reduction occurs in bodily fluids such as gastric juice, epithelial lining fluid of the respiratory tract, blood, and other fluids. Secondary reduction occurs at the cellular level by the cytosol, mitochondria, and microsomes. Thus, at low levels of exposure hexavalent chromium ions are reduced before the 6+ ions can interact with DNA unless the dose is sufficient to overwhelm the body's reduction capacity. This paper summarizes the available data concerning the reducing ability of the body and formulates the steps in the mechanism of cancer induction. These steps include: (1) only certain Cr6+ compounds have the capacity to interact with cellular components; (2) Cr6+ is reduced by body fluids and excess Cr6+ enters the cell (Cr3+ is poorly absorbed across membranes); (3) cellular organelles and the cytoplasm reduce Cr6+ to Cr3+; (4) excess Cr6+ can enter the nucleus; (5) Cr6+ reduction through 5+ and 4+ to 3+ has a potential to interact with the DNA molecule; and (6) if unrepaired, this DNA damage can lead to cancer induction. On the basis of current evidence Cr6+ has a threshold for carcinogenic potential in humans that is greater than the current TLV.

Hexavalents in spermatocytes of Robertsonian heterozygotes between Mus m. domesticus 2n 26 from the Vulcano and Lipari Islands (Aeolian Archipelago, Italy)

Science.gov (United States)

Berríos, Soledad; Fernández-Donoso, Raúl; Page, Jesús; Ayarza, Eliana; Capanna, Ernesto; Solano, Emanuela; Castiglia, Riccardo

2018-01-01

The size and shape of the chromosomes, as well as the chromosomal domains that compose them, are determinants in the distribution and interaction between the bivalents within the nucleus of spermatocytes in prophase I of meiosis. Thus the nuclear architecture characteristic of the karyotype of a species can be modified by chromosomal changes such as Robertsonian (RB) chromosomes. In this study we analysed the meiotic prophase nuclear organization of the heterozygous spermatocytes from Mus musculus domesticus 2n=26, and the synaptic configuration of the hexavalent formed by the dependent Rb chromosomes Rbs 6.16, 16.10, 10.15, 15.17 and the telocentric chromosomes 6 and 17. Spreads of 88 pachytene spermatocytes from two males were studied and in all of them five metacentric bivalents, four telocentric bivalents, one hexavalent and the XY bivalent were observed. About 48% of the hexavalents formed a chain or a ring of synapsed chromosomes, the latter closed by synapsis between the short arms of telocentric chromosomes 6 and 17. About 52% of hexavalents formed an open chain of 10 synapsed chromosomal arms belonging to 6 chromosomes. In about half of the unsynapsed hexavalents one of the telocentric chromosome short arms appears associated with the X chromosome single axis, which was otherwise normally paired with the Y chromosome. The cluster of pericentromeric heterochromatin mostly determines the hexavalent’s nuclear configuration, dragging the centromeric regions and all the chromosomes towards the nuclear envelope similar to an association of five telocentric bivalents. These reiterated encounters between these chromosomes restrict the interactions with other chromosomal domains and might favour eventual rearrangements within the metacentric, telocentric or hexavalent chromosome subsets. The unsynapsed short arms of telocentric chromosomes frequently bound to the single axis of the X chromosome could further complicate the already complex segregation of

Hexavalents in spermatocytes of Robertsonian heterozygotes between Mus m. domesticus 2n=26 from the Vulcano and Lipari Islands (Aeolian Archipelago, Italy

Directory of Open Access Journals (Sweden)

Soledad Berríos

2018-02-01

Full Text Available The size and shape of the chromosomes, as well as the chromosomal domains that compose them, are determinants in the distribution and interaction between the bivalents within the nucleus of spermatocytes in prophase I of meiosis. Thus the nuclear architecture characteristic of the karyotype of a species can be modified by chromosomal changes such as Rb chromosomes. In this study we analysed the meiotic prophase nuclear organization of the heterozygous spermatocytes from Mus musculus domesticus 2n=26, and the synaptic configuration of the hexavalent formed by the dependent Rb chromosomes Rbs 6.16, 16.10, 10.15, 15.17 and the telocentric chromosomes 6 and 17. Spreads of 88 pachytene spermatocytes from two males were studied and in all of them five metacentric bivalents, four telocentric bivalents, one hexavalent and the XY bivalent were observed. About 48% of the hexavalents formed a chain or a ring of synapsed chromosomes, the latter closed by synapsis between the short arms of telocentric chromosomes 6 and 17.  About 52% of hexavalents formed an open chain of 10 synapsed chromosomal arms belonging to 6 chromosomes.  In about half of the unsynapsed hexavalents one of the telocentric chromosome short arms appears associated with the X chromosome single axis, which was otherwise normally paired with the Y chromosome.  The cluster of pericentromeric heterochromatin mostly determines the hexavalent’s nuclear configuration, dragging the centromeric regions and all the chromosomes towards the nuclear envelope similar to an association of five telocentric bivalents. These reiterated encounters between these chromosomes restrict the interactions with other chromosomal domains and might favour eventual rearrangements within the metacentric, telocentric or hexavalent chromosome subsets. The unsynapsed short arms of telocentric chromosomes frequently bound to the single axis of the X chromosome could further complicate the already complex segregation

Comparative Study of Portland Cement-based and Zeolite-based Concretes in Terms of Hexavalent Chromium Leaching

Directory of Open Access Journals (Sweden)

Oravec Jozef

2016-12-01

Full Text Available The paper presents the results of the leaching study of Portland cement-based and zeolite-based concretes regarding water soluble hexavalent chromium. Three leaching water media (distilled water, rain water, and Britton-Robinson buffer of various pH values were under investigation. The correlation between pH and leached-out concentrations of chromium was not confirmed. The content of hexavalent water-soluble chromium in leachates of zeolite-based concretes was found to be higher than that in leachates of Portland cement-based samples.

Hexavalent Chromium: Analysis of the Mechanism of Groundwater Contamination in a Former Industrial Site in the Province of Vicenza (Northern Italy

Directory of Open Access Journals (Sweden)

Valentina Accoto

2017-01-01

Full Text Available The study consisted in the analysis of the mobilization mechanisms of hexavalent chromium (Cr(VI into groundwater from a decommissioned contaminated factory. The site is located in the Province of Vicenza and formerly was a chrome-plating plant. The subsoil consists predominantly of gravelly deposits with a thickness of at least one hundred meters. An unconfined aquifer is present with water table at about 23 m depth bgl. During the seven years of monitoring (2008-2014, the fluctuation of groundwater level was more than 6 m; hydraulic conductivity is about 1.0E-03 m/s and groundwater seepage velocity about 12 m/day. At the area of the source of contamination, the unsaturated soil is contaminated by hexavalent chromium throughout the thickness: concentrations range from 200 to 500 mg/kg. At the bottom of zone of groundwater level fluctuation, the hexavalent chromium concentration decreases to below the detection limit. The available data (e.g. hexavalent chromium concentrations in groundwater, groundwater level, local rainfall give the opportunity to assess the effects, on the magnitude of groundwater contamination, of the effective infiltration versus the fluctuation of groundwater level. The main analysis was performed on a statistical basis, in order to find out which of the two factors was most likely related to the periodic peaks of hexavalent chromium concentration in groundwater. Statistical analysis results were verified by a mass balance. Data show that at the site both the effective infiltration through the unsaturated zone and the leaching of soil contaminated by groundwater, when it exceeds a certain piezometric level, lead to peak concentrations of hexavalent chromium, even if with characteristics and effects different.

The electrochemical aspect of the corrosion of austenitic stainless steels, in nitric acid and in the presence of hexavalent chromium (1961)

International Nuclear Information System (INIS)

Coriou, H.; Hure, J.; Plante, G.

1961-01-01

The corrosion of austenitic stainless steels in boiling nitric acid markedly increases when the medium contains hexavalent chromium ions. Because of several redox phenomena, the potential of the steel generally changes in course of time. Measurements show a relation between the weight loss and the potential of specimens. Additions of Mn(VII) and Ce(IV) are compared with that of Cr(VI), and show that the relation is a general one. The attack cf the metal in oxidizing media is largely intergranular, leading to exfoliation of the grains, although the steel studied is not sensitive to the classical Huey and Strauss tests. Also even in the absence of any other oxidizing reaction, the current density observed when the steel is anodically polarized under potentiostatic conditions does not correspond to the actual weight loss of the metal. (authors) [fr

Soil humic acids may favour the persistence of hexavalent chromium in soil

International Nuclear Information System (INIS)

Leita, Liviana; Margon, Alja; Pastrello, Arnold; Arcon, Iztok; Contin, Marco; Mosetti, Davide

2009-01-01

The interaction between hexavalent chromium Cr(VI), as K 2 CrO 4 , and standard humic acids (HAs) in bulk solution was studied using three complementary analytical methods: UV-Visible spectroscopy, X-ray absorption spectroscopy and differential pulse stripping voltammetry. The observed UV-Vis and X-ray absorption spectra showed that, under our experimental conditions, HAs did not induce reduction of Cr(VI) to its trivalent chemical form. The interaction between Cr(VI) and HAs has rather led to the formation of Cr(VI)-HAs micelles via supramolecular chemical processes. The reported results could contribute towards explaining the relative persistence of ecotoxic hexavalent chromium in soils. - Humic acids (HAs) did not induce reduction of Cr(VI) to its trivalent chemical form, as the interaction between Cr(VI) and HAs rather led to the formation of Cr(VI)-HAs micelles via supramolecular chemical processes.

False-positive result when a diphenylcarbazide spot test is used on trivalent chromium-passivated zinc surfaces

DEFF Research Database (Denmark)

Reveko, Valeriia; Lampert, Felix; Din, Rameez Ud

2018-01-01

chromium passivation on zinc; however, subsequent analysis by XPS could not confirm the presence of chromium in a hexavalent state. Conclusions Unintended oxidation of DPC induced by atmospheric corrosion is suggested as a possible reason for the false-positive reaction of the DPC test on a trivalent......A colorimetric 1,5-diphenylcarbazide (DPC)-based spot test can be used to identify hexavalent chromium on various metallic and leather surfaces. DPC testing on trivalent chromium-passivated zinc surfaces has unexpectedly given positive results in some cases, apparently indicating the presence...... of hexavalent chromium; however, the presence of hexavalent chromium has never been confirmed with more sensitive and accurate test methods. Objectives To examine the presence of hexavalent chromium on trivalent chromium-passivated zinc surfaces with a DPC-based spot test. Methods A colorimetric DPC spot test...

Biodegradation of hexavalent chromium (Cr+6) in wastewater using Pseudomonas sp. and Bacillus sp. bacterial strains

Energy Technology Data Exchange (ETDEWEB)

Qasim, Muhammad [Department of Chemical Engineering, American University of Sharjah (United Arab Emirates)

2013-07-01

The recovery of toxic metal compounds is a deep concern in all industries. Hexavalent chromium is particularly worrying because of its toxic influence on human health. In this paper, biodegradation of hexavalent chromium (Cr+6) present in wastewater has been studied using two different bacterial strains; Pseudomonas sp. and Bacillus sp. A chemostat (with and without recycle of cells) with 10 L liquid culture volume was used to study the substrate and the biomass cell concentrations with time. Also, the degree of substrate conversion was studied by the varying the dilution rate as an independent parameter. The dilution rate (ratio of feed flow rate to the culture volume) was varied by varying the feed volumetric rate from 110-170 mL/h for inlet hexavalent chromium concentrations of 70 mg/dm3. The results show that a chemostat with recycle gives a better performance in terms of substrate conversion than a chemostat without a recycle. Moreover, the degree of substrate conversion decreases as the dilution rate is increased. Also, Bacillus sp. was found to give higher conversions compared to pseudomonas sp.

An assessment of the environmental toxicity of hexavalent chromium in fish

NARCIS (Netherlands)

Putte, van der I.

1981-01-01

At present chromium is a common contaminant in surface waters in many countries. In water the metal may be present in the trivalent form (CrIII) or in the hexavalent form (CrVI), the latter of which is more toxic to aquatic organisms.
The investigations presented in this thesis

Oral ingestion of hexavalent chromium through drinking water and cancer mortality in an industrial area of Greece - An ecological study

Directory of Open Access Journals (Sweden)

Stoltidis Melina

2011-05-01

Full Text Available Abstract Background Hexavalent chromium is a known carcinogen when inhaled, but its carcinogenic potential when orally ingested remains controversial. Water contaminated with hexavalent chromium is a worldwide problem, making this a question of significant public health importance. Methods We conducted an ecological mortality study within the Oinofita region of Greece, where water has been contaminated with hexavalent chromium. We calculated gender, age, and period standardized mortality ratios (SMRs for all deaths, cancer deaths, and specific cancer types of Oinofita residents over an 11-year period (1999 - 2009, using the greater prefecture of Voiotia as the standard population. Results A total of 474 deaths were observed. The SMR for all cause mortality was 98 (95% CI 89-107 and for all cancer mortality 114 (95% CI 94-136. The SMR for primary liver cancer was 1104 (95% CI 405-2403, p-value Conclusions Elevated cancer mortality in the Oinofita area of Greece supports the hypothesis of hexavalent chromium carcinogenicity via the oral ingestion pathway of exposure. Further studies are needed to determine whether this association is causal, and to establish preventive guidelines and public health recommendations.

Relationships among oxidation-reduction and acid-base properties of the actinides in high oxidation states

International Nuclear Information System (INIS)

Morss, L.R.

1992-01-01

The first chemical identification of plutonium, its subsequent isolation on the macroscopic scale, and more recent chemical separation schemes were achieved by taking advantage of the differences among the oxidation states of uranium, neptunium, and plutonium. Many acid-base properties modify the relative stabilities of oxidation states of the actinides. In the solid state, strongly basic compounds such as Cs 2 O yield complex oxides with oxidation states of Np(VII), Pu(VI), and Am(VI) whereas more acidic compounds such as CsF yield complex fluorides with lower oxidation states. In aqueous solution, high basicity and strongly covalent complexes favor high oxidation states. In nonaqueous solvent systems, high acidity generally favors low oxidation states. This paper elucidates and attempts to interpret the effects of these acid-base properties in a systematic fashion

The effect of oxidation state on the absorption of ingested or inhaled plutonium

International Nuclear Information System (INIS)

Sullivan, M.F.; Gorham, L.S.; Ryan, J.L.

1980-01-01

Rats received plutonium nitrate (as 239 Pu(IV) or 239 Pu(VI) by gavage or nose-only exposure. Some of the animals were deprived of food before and/or after exposure. Results obtained indicate that there was increased retention of plutonium after exposure to 239 Pu(VI) in comparison with 239 Pu(IV). The absence of food either before and/or after inhalation exposure had no effect on the amount of 239 Pu retained by the liver and carcass. It was concluded that plutonium in its hexavalent state may under certain conditions be more readily absorbed from the GI tract, but that these conditions are unlikely to occur in human exposure. (H.K.)

The electrochemical aspect of the corrosion of austenitic stainless steels, in nitric acid and in the presence of hexavalent chromium (1961); Aspect electrochimique de la corrosion d'aciers inoxydables austenitiques en milieu nitrique et en presence de chrome hexavalent (1961)

Energy Technology Data Exchange (ETDEWEB)

Coriou, H.; Hure, J.; Plante, G. [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

1961-07-01

The corrosion of austenitic stainless steels in boiling nitric acid markedly increases when the medium contains hexavalent chromium ions. Because of several redox phenomena, the potential of the steel generally changes in course of time. Measurements show a relation between the weight loss and the potential of specimens. Additions of Mn(VII) and Ce(IV) are compared with that of Cr(VI), and show that the relation is a general one. The attack cf the metal in oxidizing media is largely intergranular, leading to exfoliation of the grains, although the steel studied is not sensitive to the classical Huey and Strauss tests. Also even in the absence of any other oxidizing reaction, the current density observed when the steel is anodically polarized under potentiostatic conditions does not correspond to the actual weight loss of the metal. (authors) [French] La corrosion d'aciers inoxydables austenitiques en milieu nitrique bouillant augmente notablement quand le milieu contient des ions chrome a l'etat hexavalent. Par suite de divers phenomenes d'oxydo-reduction, le potentiel de l'acier evolue generalement au cours du temps. Les mesures effectuees permettent d'etablir une relation entre les pertes de poids et le potentiel des echantillons. L'addition de Mn(VI) et Ce(IV) est compare a celle de Cr(VI) et montre que la relation precedente s'applique de facon generale. L'attaque du metal en milieu oxydant est en grande, partie due a une corrosion intergranulaire conduisant a un dechaussement des grains bien que l'acier etudie ne soit pas sensible aux tests classiques de Huey et de Strauss. Aussi, meme en l'absence de toute autre reaction d'oxydation l'intensite qu l'on observerait en soumettant l'acier a un potentiel anodique dans un montage potentiostatique ne correspondrait pas a la perte de poids reelle du metal. (auteurs)

Polarography applied to the determination of uranium oxide composition; Application de la polarographie a la determination de la composition d'oxydes d'uranium

Energy Technology Data Exchange (ETDEWEB)

Nens, C; Canton, C; Molina, R [Commissariat a l' Energie Atomique, Fontenay-aux-Roses (France). Centre d' Etudes Nucleaires, Departement de Chimie, Services d' Etudes Chimiques et d' Analyse, Service d' Etudes Analytiques, Section de Chimie Analytique du Plutonium et d' Electroanalyse

1967-03-01

An analytical method based on conventional polarography has been developed, for the determination of the O/U ratio in uranium oxides. The dissolution of the samples is effected by means of molten ammonium bifluoride. After a transfer to aqueous solution, polarography is used to determine the oxide composition by measurement of both the hexavalent and the total uranium. (author) [French] Une methode d'analyse utilisamt la polarographie conventionnelle a ete mise au point pour la determination du rapport O/U dans les oxydes d'uranium. La mise en solution des echgantillons est realisee en milieu de bifluorure d'ammonium fondu. Apres passage en salution aqueuse, la polarographie permet d'atteindre la composition de l'oxyde par determination de l'uranium hexavalent et de l'uranium total. (auteur)

Ferrous sulphate mono and heptahydrate reduction of hexavalent chromium in cement: effectiveness and storability

Directory of Open Access Journals (Sweden)

Valverde, J. L.

2005-09-01

Full Text Available In Community legislation, substances containing hexavalent chromium are classified as carcinogenic, mutagenic and sensitizing. In cement, hexavalent chromium intensifies sensitization and may set off severe allergic reactions in workers in routine contact with the product, whether in the factory or on construction sites. The allergic or contact dermatitis causes is a very painful disease that may lead to permanent worker disability. According to Directive 2003/53/EC of the European Parliament and the Council, Governments of all member countries will be required to prohibit the marketing and use, as of 17 January 2005, of any cement or cement preparation containing more than 2 ppm of chromium (VI. Hexavalent chromium can be reduced with ferrous sulphate to trivalent chromium, which is water-insoluble and therefore innocuous to the skin. The present paper reports the effects of adding ferrous sulphate mono- or heptahydrate to a commercial cement and the storage time of the mix on the concentration of hexavalent chromium. The salts studied were found to effectively reduce hexavalent chromium in cement for at least three months.

Las sustancias que contienen cromo hexavalente están clasificadas en la legislación comunitaria como sustancias carcinogénicas, mutagénicas y sensibilizantes. El cromo hexavalente del cemento potencia la sensibilización y provoca graves reacciones alérgicas que sufren bastante a menudo los trabajadores que lo manipulan habitualmente, ya sea en fábrica o en el sector de la construcción. La dermatitis alérgica o de contacto que produce es muy dolorosa y puede dejar a los trabajadores en estado de discapacidad. La Directiva 2003/53/CE del Parlamento Europeo y del Consejo, exige a los Gobiernos de los países miembros, que a partir del 17 de enero de 2005, prohiban el uso y la comercialización de todos aquellos cementos y preparados que contengan cemento, cuyo contenido en cromo (VI soluble, una vez hidratados

On the removal of hexavalent chromium from a Class F fly ash.

Science.gov (United States)

Huggins, F E; Rezaee, M; Honaker, R Q; Hower, J C

2016-05-01

Coarse and fine samples of a Class F fly ash obtained from commercial combustion of Illinois bituminous coal have been exposed to two long-term leaching tests designed to simulate conditions in waste impoundments. ICP-AES analysis indicated that the coarse and fine fly ash samples contained 135 and 171mg/kg Cr, respectively. Measurements by XAFS spectroscopy showed that the ash samples originally contained 5 and 8% of the chromium, respectively, in the hexavalent oxidation state, Cr(VI). After exposure to water for more than four months, the percentage of chromium as Cr(VI) in the fly-ash decreased significantly for the coarse and fine fly-ash in both tests. Combining the XAFS data with ICP-AES data on the concentration of chromium in the leachates indicated that, after the nineteen-week-long, more aggressive, kinetic test on the coarse fly ash, approximately 60% of the Cr(VI) had been leached, 20% had been reduced to Cr(III) and retained in the ash, and 20% remained as Cr(VI) in the ash. In contrast, during the six-month-long baseline test, very little Cr was actually leached from either the coarse or the fine fly-ash (ash was retained in the ash in that form, while the remainder, 34% and 80%, respectively, was reduced and retained in the ash as Cr(III). The results are interpreted as indicating that Cr(VI) present in Class F fly-ash can be reduced to Cr(III) when in contact with water and that such chemical reduction can compete with physical removal of Cr(VI) from the ash by aqueous leaching. Copyright © 2016 Elsevier Ltd. All rights reserved.

Mechanisms of hexavalent chromium resistance and removal by microorganisms.

Science.gov (United States)

Joutey, Nezha Tahri; Sayel, Hanane; Bahafid, Wifak; El Ghachtouli, Naïma

2015-01-01

Chromium has been and is extensively used worldwide in multiple industrial processes and is routinely discharged to the environment from such processes. Therefore, this heavy metal is a potential threat to the environment and to public health, primarily because it is non-biodegradable and environmentally persistent. Chromium exists in several oxidation states, the most stable of which are trivalent Cr(Ill) and hexavalent Cr(VI) species. Each species possesses its own individual chemical characteristics and produces its own biological effects. For example, Cr (Ill) is an essential oligoelement for humans, whereas Cr(VI) is carcinogenic and mutagenic. Several chemical methods are used to remove Cr(VI) from contaminated sites. Each of these methods has advantages and disadvantages. Currently, bioremediation is often the preferred method to deal with Cr contaminated sites, because it is eco-friendly, cost-effective and is a "natural" technology. Many yeast, bacterial and fungal species have been assessed for their suitability to reduce or remove Cr(VI) contamination. The mechanisms by which these microorganisms resist and reduce Cr(VI) are variable and are species dependent. There are several Cr-resistance mechanisms that are displayed by microorganisms. These include active efflux of Cr compounds, metabolic reduction of Cr(VI) to Cr (ill), and either intercellular or extracellular prec1p1tation. Microbial Cr (VI) removal typically involves three stages: binding of chromium to the cell surface, translocation of chromium into the cell, and reduction of Cr(VI) to Cr (ill). Cr(VI) reduction by microorganisms may proceed on the cell surface, outside the cell, or intracellularly, either directly via chromate reductase enzymes, or indirectly via metabolite reduction of Cr(VI). The uptake of chromium ions is a biphasic process. The primary step is known as biosorption, a metabolic energyindependent process. Thereafter, bioaccumulation occurs, but is much slower, and is

Non-equilibrium oxidation states of zirconium during early stages of metal oxidation

International Nuclear Information System (INIS)

Ma, Wen; Yildiz, Bilge; Herbert, F. William; Senanayake, Sanjaya D.

2015-01-01

The chemical state of Zr during the initial, self-limiting stage of oxidation on single crystal zirconium (0001), with oxide thickness on the order of 1 nm, was probed by synchrotron x-ray photoelectron spectroscopy. Quantitative analysis of the Zr 3d spectrum by the spectrum reconstruction method demonstrated the formation of Zr 1+ , Zr 2+ , and Zr 3+ as non-equilibrium oxidation states, in addition to Zr 4+ in the stoichiometric ZrO 2 . This finding resolves the long-debated question of whether it is possible to form any valence states between Zr 0 and Zr 4+ at the metal-oxide interface. The presence of local strong electric fields and the minimization of interfacial energy are assessed and demonstrated as mechanisms that can drive the formation of these non-equilibrium valence states of Zr

Genesis and transport of hexavalent chromium in the system ophiolitic rocks - groundwater

Science.gov (United States)

Shchegolikhina, Anastasia; Guadagnini, Laura; Guadagnini, Alberto

2015-04-01

Our study aims at contributing to the quantification and characterization of chromium transport processes from host rocks and soil matrices to groundwater. We focus on dissolved hexavalent chromium detected in groundwaters of geological regions with ophiolitic rocks (ophiolites and serpentinites) inclusions due to its critical ecological impact. (Oze et al., 2004). Despite the large number of analyses on the occurrence of high concentrations of hazardous hexavalent chromium ions in natural waters, only few studies were performed with the objective of identifying and investigating the geochemical reactions which could occur in the natural system rock - groundwater - dissolved chromium (Fantoni et al., 2002, Stephen and James, 2004, Lelli et al., 2013). In this context, there is a need for integration of results obtained from diverse studies in various regions and settings to improve our knowledge repository. Our theoretical analyses are grounded and driven by practical scenarios detected in subsurface reservoirs exploited for civil and industrial use located in the Emilia-Romagna region (Italy). Available experimental datasets are complemented with data from other international regional-scale settings (Altay mountains region, Russia). Modeling of chromium transformation and migration particularly includes characterization of the multispecies geochemical system. A key aspect of our study is the analysis of the complex competitive sorption processes governing heavy metal evolution in groundwater. The results of the research allow assessing the critical qualitative features of the mechanisms of hexavalent chromium ion mobilization from host rocks and soils and the ensuing transformation and migration to groundwater under the influence of diverse environmental factors. The study is then complemented by the quantification of the main sources of uncertainty associated with prediction of heavy metal contamination levels in the groundwater system explored. Fantoni, D

No hexavalent half-arc-transitive graphs of order twice a prime ...

Indian Academy of Sciences (India)

Mi-Mi Zhang

2018-03-19

Mar 19, 2018 ... Wang and Feng (Discrete. Math. 310 (2010) 1721–1724) proved that there exists no tetravalent half-arc-transitive graphs of order 2p2. In this paper, we extend this result to prove that no hexavalent half-arc-transitive graphs of order 2p2 exist. Keywords. Half-arc-transitive; bi-Cayley graph; vertex transitive; ...

Hexavalent chromium reduction by a hypocrea tawa fungal strain

International Nuclear Information System (INIS)

Morales-Battera, L.; Guillen-Jimenez, F. M.; Cristiani-Urbina, E.

2009-01-01

Microbial transformation of the highly toxic, water-soluble and mobile hexavalent chromium [Cr(VI)], to the less toxic, insoluble and immobile trivalent chromium [Cr(III)], is an economically feasible alternative for the treatment of wastewaters contaminated with Cr(VI). The main purpose of this work was to isolate, identify and characterize a microbial strain water by batch enrichment culture techniques, and further identified as Hypocrea tawa by its D1/D2 domain sequence of the 26S rRNA gene with 99,44% similarity. (Author)

Chromium III histidinate exposure modulates antioxidant gene expression in HaCaT human keratinocytes exposed to oxidative stress

Science.gov (United States)

While the toxicity of hexavalent chromium is well established, trivalent Cr (Cr(III)) is an essential nutrient involved in insulin and glucose homeostasis. Recently, antioxidant effects of chromium (III) histidinate (Cr(III)His) were reported in HaCaT human keratinocytes exposed to oxidative stress...

Study by mass spectrometry of the formation of cluster ions generated by laser ablation/ionization of inorganic compounds: application to the differentiation of trivalent and hexavalent chromium compounds

International Nuclear Information System (INIS)

Aubriet, Frederic

1999-01-01

The introduction of new ionization techniques allows a fast growth of mass spectrometry applications in an increasing number of fields. More particularly, the introduction of laser ablation/ionization process and the design of new instruments (laser microprobes), has been very important for a better knowledge of inorganic compound mass spectrometry. The purposes of this work were mainly focussed firstly in the understanding of cluster ions formation process by laser ablation/ionization and secondly in the development of a new mass spectrometry technique for the speciation between trivalent and hexavalent chromium compounds. We show that cluster ion formation are multiple. The difficulty to identify clearly the processes involved is due to the superposition of many mechanisms. Mostly, these processes are representative of the complexity of the gas-phase chemistry between the various species generated by laser ablation/ionization. Thus, four mechanisms for the cluster ion formation have been highlighted. The most frequently met correspond to aggregative processes of neutral molecules on precursor ions. The knowledge of the processes of cluster ion formation allows us to explain why it is possible to distinguish the oxidation number of chromium. The organigram of chromium valence speciation proposed is based on the calculation of the ratio of negative cluster ion intensities after systematic analysis of nearly twenty chromium reference compounds using the same instrumental conditions. The examination of mixtures between 1) calcium. silicon, trivalent iron or zinc oxides and 2) the standard chromium compound allows us to observe the influence of these oxides on the fingerprints of the pure chromium compounds and to determine up to which point and with which limitations, the methodology suggested, could be applied to the analysis of trivalent and hexavalent chromium compounds in complex and polyphasic matrices

Carbon monoxide oxidation over three different states of copper: Development of a model metal oxide catalyst

Energy Technology Data Exchange (ETDEWEB)

Jernigan, Glenn Geoffrey [California Univ., Berkeley, CA (United States). Dept. of Chemistry

1994-10-01

Carbon monoxide oxidation was performed over the three different oxidation states of copper -- metallic (Cu), copper (I) oxide (Cu₂O), and copper (II) oxide (CuO) as a test case for developing a model metal oxide catalyst amenable to study by the methods of modern surface science and catalysis. Copper was deposited and oxidized on oxidized supports of aluminum, silicon, molybdenum, tantalum, stainless steel, and iron as well as on graphite. The catalytic activity was found to decrease with increasing oxidation state (Cu > Cu₂O > CuO) and the activation energy increased with increasing oxidation state (Cu, 9 kcal/mol < Cu₂O, 14 kcal/mol < CuO, 17 kcal/mol). Reaction mechanisms were determined for the different oxidation states. Lastly, NO reduction by CO was studied. A Cu and CuO catalyst were exposed to an equal mixture of CO and NO at 300--350 C to observe the production of N₂ and CO₂. At the end of each reaction, the catalyst was found to be Cu₂O. There is a need to study the kinetics of this reaction over the different oxidation states of copper.

PHOTOCATALYTIC REMOVAL OF TR I- AND HEXA-VALENT CHROMIUM IONS FROM CHROME-ELECTROPL ATING WASTEWATER

Directory of Open Access Journals (Sweden)

Puangrat Kajitvichyanukul

2017-11-01

Full Text Available A novel technique based on photocatalysis was applied to eliminate chromium ions, a toxic hazardous environmental pollutant. The photoreduction of each species of chromium (total, hexavalent, and trivalent chromiums from chrome-electroplating wastewater was investigated using a titanium dioxide suspension under irradiation by a low-pressure mercury lamp. The initial concentration of total chromium was 300 mg/l. The applied conditions were the direct photocatalytic reduction process at pH 3.65 and the indirect photocatalytic reduction with added hole scavengers at the same solution pH. Results from both processes were comparatively discussed. Result show that chromium was not efficiently removed by direct photoreduction. In contrast, with the adding of hole scavengers, which were formate ions, the photoreduction of chromium was very favorable. Both hexavalent and trivalent chromiums were efficiently removed. The photocatalytic mechanism is purposed in this study.

Hexavalent Chromium Is Cytotoxic and Genotoxic to American Alligator Cells

OpenAIRE

Wise, Sandra S.; Wise, Catherine; Xie, Hong; Guillette, Louis J.; Zhu, Cairong; Wise, John Pierce; Wise, John Pierce

2015-01-01

Metals are a common pollutant in the aquatic ecosystem. With global climate change, these levels are anticipated to rise as lower pH levels allow sediment bound metals to be released. The American alligator (Alligator mississippiensis) is an apex predator in the aquatic ecosystem and is considered a keystone species; as such it serves as a suitable monitor for localized pollution. One metal of increasing concern is hexavalent chromium (Cr(VI)). It is present in the aquatic environment and is ...

Evaluation of chromium speciation and transport characteristics in the Hanford Site 100D and 100H areas

International Nuclear Information System (INIS)

Thornton, E.C.; Amonette, J.E.; Olivier, J.

1995-08-01

Field and laboratory investigations have been conducted to define the fate and transport characteristics of chromium contamination present in the 100D/H Areas of the Hanford Site. This information is relevant to assessing the impact of the release of hexavalent chromium to the Columbia River. Included in this study was the determination of the concentration and aqueous speciation of chromium in the unconfined acquifer and an assessment of potential changes in speciation as groundwater passes through the river/acquifer transition zone and mixes with the Columbia River. The results of this study indicate that chromium present within the Hanford acquifer is predominantly in the oxidized hexavalent state. Chromium is apparently stable in the oxidized form owing to its lack of organic matter within the acquifer. A portion of the chromium is removed as groundwater passes through the transition zone due to reduction and precipitation associated with sediment/water interaction processes. Chemical data collected from seep water samples, however, suggests, that most of the hexavalent chromium ultimately discharges into the Columbia River. Dilution of hexavalent chromium subsequently occurs during the mixing of groundwater and river water, with relatively little change taking place in speciation

Investigation of alternative phosphating treatments for nickel and hexavalent chromium elimination; Investigacao de tratamentos alternativos de fosfatizacao para eliminacao do niquel e cromo hexavalente

Energy Technology Data Exchange (ETDEWEB)

Jazbinsek, Luiz Antonio Rossi

2014-07-01

The phosphating processes are widely used in industry as surface treatments for metals, especially for low thickness plates, improving the adhesion between the metallic surface and the paint coating, and increasing the durability of paint systems against corrosion attacks. The tricationic phosphates containing zinc, nickel and manganese are commonly applied on steel. There is much discussion about the replacement of nickel by another element in order to have an environmentally friendly phosphating process. Niobium as a replacement for nickel has been evaluated. The most significant environmental impacts of phosphating processes are related to the presence of nickel and hexavalent chromium used in the process, this last as a passivation treatment. Nickel and hexavalent chromium are harmful to human and environment leading to contamination of water and soil. In the present study phosphate layers containing zinc, manganese and niobium have been evaluated and characterized on galvanized steel, and the results were compared with phosphates containing zinc, manganese and nickel, or a bicationic phosphate layer with zinc and manganese. Although the use of hexavalent chromium is not recommended worldwide, it is still used in processes for sealing the porosity of phosphate layers. This element is carcinogenic and has been associated with various diseases. Due to the passivation characteristics of niobium, this study also evaluated the tricationic bath containing niobium ammonium oxalate as a passivation treatment. The results showed that it could act as a replacement for the hexavalent chromium. The results of the present study showed that formulations containing niobium are potential replacements for hexavalent chromium and similar corrosion protection was obtained for the phosphate containing nickel or that with niobium. The morphology observed by scanning electron microscopy, gravimetric tests, porosity and adhesion evaluation results indicated that the phosphate

Determination of the oxidation states of metals and metalloids: An analytical review

Science.gov (United States)

Vodyanitskii, Yu. N.

2013-12-01

The hazard of many heavy metals/metalloids in the soil depends on their oxidation state. The problem of determining the oxidation state has been solved due to the use of synchrotron radiation methods with the analysis of the X-ray absorption near-edge structure (XANES). The determination of the oxidation state is of special importance for some hazardous heavy elements (arsenic, antimony, selenium, chromium, uranium, and vanadium). The mobility and hazard of each of these elements depend on its oxidation state. The mobilities are higher at lower oxidation states of As, Cr, V, and Se and at higher oxidation states of Sb and U. The determination of the oxidation state of arsenic has allowed revealing its fixation features in the rhizosphere of hydrophytes. The known oxidation states of chromium and uranium are used for the retention of these elements on geochemical barriers. Different oxidation states have been established for vanadium displacing iron in goethite. The determination of the oxidation state of manganese in the rhizosphere and the photosynthetic apparatus of plants is of special importance for agricultural chemists.

Natural occurrence of hexavalent chromium in a sedimentary aquifer in Urânia, State of São Paulo, Brazil

Directory of Open Access Journals (Sweden)

Christine Bourotte

2009-06-01

Full Text Available Anomalous concentrations of hexavalent chromium have been detected in ground-water of the Adamantina Aquifer inat least 54 municipalities located in the northwestern region of the State of São Paulo, southeast Brazil, occasionallyexceeding the permitted limit for human consumption (0.05 mg.L-1. An investigation was conducted in the municipality of Urânia, where the highest concentrations of chromium were detected regionally. It was defined that the originof this contamination is natural, since high concentrations of chromium were detected in aquifer sandstones (averageof 221 ppm and also in pyroxenes (6000 ppm, one of the main heavy minerals found in the sediments. Besides, noother possible diffuse or point sources of contamination were observed in the study area. Stratification of ground-waterquality was observed and the highest concentrations of Cr6+ were detected at the base of the aquifer (0.12 mg.L-1,where ground-water shows elevated values for redox potential (472.5 mV and pH (8.61. The origin of Cr6+ in water may be associated with the weathering of pyroxene (augite, followed by the oxidation of Cr3+ by manganese oxides. The highest concentrations of Cr6+ are probably related to desorption reactions, due to the anomalous alkaline pHfound in ground-water at the base of the aquifer.Concentrações anômalas de cromo hexavalente foram detectadas em águas subterrâneas do Aqüífero Adamantina em pelo menos 54 municipalidades localizadas na região noroeste do Estado de São Paulo, sudeste do Brasil, algumas vezes ultrapassando o limite máximo permitido para consumo humano (0,05 mg.L-1. Um estudo foi realizado no município de Urânia, onde as mais elevadas concentrações de cromo da região foram detectadas. A origem da contaminação foi definida como natural, pois foram detectadas concentrações de cromonos arenitos do aqüífero (média 221 ppm e em piroxênios (6000 ppm, um dos principais minerais pesados encontrados nos sedimentos

Determination of the oxygen-metal-ratio of uranium-americium mixed oxides

International Nuclear Information System (INIS)

Bartscher, W.

1982-01-01

During the dissolution of uranium-americium mixed oxides in phosphoric acid under nitrogen tetravalent uranium is oxidized by tetravalent americium. The obtained hexavalent uranium is determined by constant potential coulometry. The coulombs measured are equivalent to the oxygen in excess of the minimum composition of UO 2 x AmO 1 . 5 . The total uranium content of the sample is determined in a subsequent coulometric titration. The oxygen-metal ratio of the sample can be calculated for a given uranium-americium ratio. An excess of uranium dioxide is necessary in order to suppress the oxidation of water by tetravalent americium. The standard deviation of the method is 0.0017 O/M units. (orig.) [de

An evaluation of in vivo models for toxicokinetics of hexavalent chromium in the stomach

Energy Technology Data Exchange (ETDEWEB)

Sasso, A.F., E-mail: sasso.alan@epa.gov; Schlosser, P.M., E-mail: schlosser.paul@epa.gov

2015-09-15

Hexavalent chromium (Cr6) is a drinking water contaminant that has been detected in most of the water systems throughout the United States. In 2-year drinking water bioassays, the National Toxicology Program (NTP) found clear evidence of carcinogenic activity in male and female rats and mice. Because reduction of Cr6 to trivalent chromium (Cr3) is an important detoxifying step in the gastrointestinal (GI) tract prior to systemic absorption, models have been developed to estimate the extent of reduction in humans and animals. The objective of this work was to use a revised model of ex vivo Cr6 reduction kinetics in gastric juice to analyze the potential reduction kinetics under in vivo conditions for mice, rats and humans. A published physiologically-based pharmacokinetic (PBPK) model was adapted to incorporate the new reduction model. This paper focuses on the toxicokinetics of Cr6 in the stomach compartment, where most of the extracellular Cr6 reduction is believed to occur in humans. Within the range of doses administered by the NTP bioassays, neither the original nor revised models predict saturation of stomach reducing capacity to occur in vivo if applying default parameters. However, both models still indicate that mice exhibit the lowest extent of reduction in the stomach, meaning that a higher percentage of the Cr6 dose may escape stomach reduction in that species. Similarly, both models predict that humans exhibit the highest extent of reduction at low doses. - Highlights: • We outline a new in vivo model for hexavalent chromium reduction in the stomach. • We examine in vivo reduction for mice, rats, and humans under varying conditions. • Species differences in toxicokinetics may explain susceptibility. • We show that a simplified stomach reduction model is adequate for extrapolation. • Internal dose uncertainties still exist.

Isolation of Electrogenic Microorganisms with Potential to Reduce Hexavalent Chromium

Directory of Open Access Journals (Sweden)

Alexander Mora Collazos

2017-01-01

Full Text Available Isolation of cultivable microorganisms was made from the biofilm formed on the anode of a microbial fuel cell put into operation for 30 days; isolated microorganisms were evaluated for their ability to produce energy and reduce the hexavalent chromium Cr (VI. Five microorganisms were isolated, which were characterized by analysis of 16S rRNA gene, placing them in four bacterial genera: Exiguobacterium (CrMFC1, Acinetobacter (CrMFC2, Aeromonas (CrMFC3 and CrMFC5 and Serratia (CrMFC4. All isolates showed electrogenic activity and ability to reduce hexavalent chromium; the Acinetobacter CrMFC1 strain showed the best electrochemical performance registering a maximum power density of 18.61 mW/m2; the other strains showed values of maximum power density between 4.6 mW/m2and 7.1 mW/m2. Strains Aeromonas CrMFC5 and Exiguobacterium CrMFC1 showed the best rates of chromium reduction being able to reduce 100 % of the Cr (VI in less than 24 hours, the Aeromonas CrMFC5 strain was the most efficient, reducing 100 % of Cr (VI in 10 hours; the other strains reduced 100% of the contaminant after 28 to 30 hours. The microorganisms isolated in this study are hardly known for their electrogenic capacity and for reducing Cr (VI; however, show promise for their use in combined systems involving energy production system coupled to bioremediation of chromium contaminated water.

Quaternized wood as sorbent for hexavalent chromium.

Science.gov (United States)

Low, K S; Lee, C K; Lee, C Y

2001-01-01

The potential of quaternized wood (QW) chips in removing hexavalent chromium from synthetic solution and chrome waste under both batch and continuous-flow conditions was investigated. Sorption was found to be dependent on pH, metal concentration, and temperature. QW chips provide higher sorption capacity and wider pH range compared with untreated wood chips. The equilibrium data could be fitted into the Langmuir isotherm model, and maximum sorption capacities were calculated to be 27.03 and 25.77 mg/g in synthetic chromate solution and chrome waste, respectively. The presence of sulfate in high concentration appeared to suppress the uptake of chromium by QW chips. Column studies showed that bed depth influenced the breakthrough time greatly whereas flow rate of influent had little effect on its sorption on the column.

Hexavalent uranium reduction from solid phase by thermophilic bacterium Thermoterrabacterium ferrireducens

International Nuclear Information System (INIS)

Khijniak, T.V.; Slobodkin, A.I.; Bonch-Osmolovskaya, E.A.; Medvedeva-Lyalikova, N.N.; Coker, V.; Lloyd, J.R.; Birkeland, N.K.

2005-01-01

Full text of publication follows: It has been reported that in uranium-contaminated sites, solid-phase U(VI) present in sediments is resistant to microbial reduction. Also, it was demonstrated that mesophilic iron and sulfate-reducing bacteria can reduce hexavalent uranium and sulphate-reducing bacteria were able to grow via uranium reduction. Among thermophilic microorganisms reduction of hexavalent uranium has been demonstrated only for cell suspensions of two genera: Pyrobaculum and Thermus. In the present study, Thermoterrabacterium ferrireducens was tested for reduction of U(VI), a thermophilic, gram-positive anaerobic bacterium capable for growth with the reduction of various electron acceptors including Fe(III). Kinetic of bacterial growth, uranium reduction and influence of different uranium concentrations were investigated at 65 deg. C. Due to presence of phosphate in the basal medium yellow uranium phosphate precipitate was formed after addition of uranyl acetate. After 68 h of incubation control tubes without bacteria were contained yellow precipitate whereas in presence of bacteria precipitate turned to the grey color. In the control tubes uranium phosphates and other elements formed a uniform mixture of crystals, but in presence of bacteria the round shape particles, containing uranium, were found by Environmental Scan Electron Microscopy of air-dried or frozen samples. To determine valent state speciation spectroscopic investigations were performed also. Initial yellow uranium phosphate precipitate was separated and identified as uramphite - (NH 4 )(UO 2 )(PO 4 )*3H 2 O by X-Ray Powder Diffraction. Grey precipitate, which was formed by bacterial reduction, was identified as ningyoite - CaU(PO 4 ) 2 *H 2 O. The fact that final grey precipitate contain U(IV) was also confirmed by EXAFS investigation. High concentration of uranium has toxic effect. 1 and 2.5 mM of uranium (VI) support bacterial growth and bacterial biomass was accumulated, but if 5 or 10

Detoxification of hexavalent chromium by Leucobacter sp. uses a reductase with specificity for dihydrolipoamide.

Science.gov (United States)

Sarangi, Abhipsa; Krishnan, Chandraraj

2016-02-01

Leucobacter sp. belongs to the metal stressed community and possesses higher tolerance to metals including chromium and can detoxify toxic hexavalent chromium by reduction to less toxic trivalent chromium. But, the mechanism of reduction of hexavalent chromium by Leucobacter sp. has not been studied. Understanding the enzyme catalyzing reduction of chromium is important to improve the species for application in bioremediation. Hence, a soluble reductase catalyzing the reduction of hexavalent chromium was purified from a Leucobacter sp. and characterized. The pure chromate reductase was obtained from the cell-free extract through hydrophobic interaction and gel filtration column chromatographic methods. It was a monomeric enzyme and showed similar molecular weights in both gel filtration (∼68 KDa) and SDS-PAGE (64 KDa). It reduced Cr(VI) using both NADH and NADPH as the electron donor, but exhibited higher activity with NADH. The optimal activity was found at pH 5.5 and 30 °C. The K(m) and V(max) for Cr(VI) reduction with NADH were 46.57 μM and 0.37 μmol min(-1) (mg protein) (-1), respectively. The activity was inhibited by p-hydroxy mercury benzoate, Ag(2+) and Hg(2+) indicating the role of thiol groups in the catalysis. The spectrophotometric analysis of the purified enzyme showed the absence of bound flavin in the enzyme. The N-terminal amino acid sequence and LC/MS analysis of trypsin digested purified enzyme showed similarity to dihydrolipoyl dehydrogenase. The purified enzyme had dihydrolipoyl dehydrogenase activity with dihydrolipoamide as the substrate, which suggested that Leucobacter sp. uses reductase with multiple substrate specificity for reduction of Cr(VI) detoxification. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

NASA TEERM Hexavalent Chrome Alternatives Projects

Science.gov (United States)

Kessel, Kurt; Rothgeb, Matt

2011-01-01

This slide presentation reviews the NASA project to select an alternative to hexavalent chrome in the aerospace industry. Included is a recent historic testing and research that the Agency has performed on (1) the external tank, (2) the shuttle orbiter, (3) the Shuttle Rocket Booster, and (4) the Space Shuttle Main Engine. Other related Technology Evaluation for Environmental Risk Mitigation (TEERM) projects are reviewed. The Phase I process of the project performed testing of alternatives the results are shown in a chart for different coating systems. International collaboration was also reviewed. Phase II involves further testing of pretreatment and primers for 6 and 12 months of exposure to conditions at Launch Pad and the beach. Further test were performed to characterize the life cycle corrosion of the space vehicles. A new task is described as a joint project with the Department of Defense to identify a Hex Chrome Free Coatings for Electronics.

Oxidative dissolution of spent fuel and release of nuclides from a copper/iron canister. Model developments and applications

Energy Technology Data Exchange (ETDEWEB)

Longcheng Liu

2001-12-01

Three models have been developed and applied in the performance assessment of a final repository. They are based on accepted theories and experimental results for known and possible mechanisms that may dominate in the oxidative dissolution of spent fuel and the release of nuclides from a canister. Assuming that the canister is breached at an early stage after disposal, the three models describe three sub-systems in the near field of the repository, in which the governing processes and mechanisms are quite different. In the model for the oxidative dissolution of the fuel matrix, a set of kinetic descriptions is provided that describes the oxidative dissolution of the fuel matrix and the release of the embedded nuclides. In particular, the effect of autocatalytic reduction of hexavalent uranium by dissolved H{sub 2}, using UO{sub 2} (s) on the fuel pellets as a catalyst, is taken into account. The simulation results suggest that most of the radiolytic oxidants will be consumed by the oxidation of the fuel matrix, and that much less will be depleted by dissolved ferrous iron. Most of the radiolytically produced hexavalent uranium will be reduced by the autocatalytic reaction with H{sub 2} on the fuel surface. It will reprecipitate as UO{sub 2} (s) on the fuel surface, and thus very little net oxidation of the fuel will take place. In the reactive transport model, the interactions of multiple processes within a defective canister are described, in which numerous redox reactions take place as multiple species diffuse. The effect of corrosion of the cast iron insert of the canister and the reduction of dissolved hexavalent uranium by ferrous iron sorbed onto iron corrosion products and by dissolved H{sub 2} are particularly included. Scoping calculations suggest that corrosion of the iron insert will occur primarily under anaerobic conditions. The escaping oxidants from the fuel rods will migrate toward the iron insert. Much of these oxidants will, however, be consumed

Influence of attrition scrubbing, ultrasonic treatment, and oxidant additions on uranium removal from contaminated soils

International Nuclear Information System (INIS)

Timpson, M.E.; Elless, M.P.; Francis, C.W.

1994-01-01

As part of the Uranium in Soils Integrated Demonstration Project being conducted by the US Department of Energy, bench-scale investigations of selective leaching of uranium from soils at the Fernald Environmental Management Project site in Ohio were conducted at Oak Ridge National Laboratory. Two soils (storage pad soil and incinerator soil), representing the major contaminant sources at the site, were extracted using carbonate- and citric acid-based lixiviants. Physical and chemical processes were used in combination with the two extractants to increase the rate of uranium release from these soils. Attrition scrubbing and ultrasonic dispersion were the two physical processes utilized. Potassium permanganate was used as an oxidizing agent to transform tetravalent uranium to the hexavalent state. Hexavalent uranium is easily complexed in solution by the carbonate radical. Attrition scrubbing increased the rate of uranium release from both soils when compared with rotary shaking. At equivalent extraction times and solids loadings, however, attrition scrubbing proved effective only on the incinerator soil. Ultrasonic treatments on the incinerator soil removed 71% of the uranium contamination in a single extraction. Multiple extractions of the same sample removed up to 90% of the uranium. Additions of potassium permanganate to the carbonate extractant resulted in significant changes in the extractability of uranium from the incinerator soil but had no effect on the storage pad soil

Acute toxicity of sodium chloride, pentachlorophenol, Guthion, and hexavalent chromium to fathead minnows (Pimephales promelas) and goldfish (Carassius auratus)

Energy Technology Data Exchange (ETDEWEB)

Adelman, I.R.; Smith, L.L. Jr.; Siesennop, G.D.

1976-02-01

The 96-h LC50's for sodium chloride were 7650 and 7341 mg/liter, for pentachlorophenol 0.21 and 0.22 mg/liter, for Guthion 1.9 and 2.4 mg/liter, and for hexavalent chromium 48 and 120 mg/liter, for fathead minnows (Pimephales promelas) and goldfish (Carassius auratus), respectively. Threshold LC50's were reached in 6 days for sodium chloride (7650 and 7322 mg/liter for fathead minnows and goldfish, respectively), and pentachlorophenol (0.21 and 0.21 mg/liter), but were not attained in 11 days (termination of testing) with Guthion (0.76 and 0.80 mg/liter) and hexavalent chromium (18 and 33 mg/liter). With pentachlorophenol and Guthion goldfish were initially more resistant, but by termination there was no significant difference in LC50's between the two species. With hexavalent chromium the goldfish were more resistant throughout the 11-day test, and with sodium chloride goldfish were initially more resistant but at attainment of a threshold LC50 were less resistant. Use of toxicity curves for assessment of acute mortality permits interpretation not possible in 96-h tests where LC50's are computed at 24-h intervals.

Influence of vanadium oxidation states on the performance of V-Mg-Al mixed-oxide catalysts for the oxidative dehydrogenation of propane

International Nuclear Information System (INIS)

Schacht, L.; Navarrete, J.; Schacht, P.; Ramirez, M. A.

2010-01-01

V-Mg-Al mixed-oxide catalysts for oxidative dehydrogenation of propane were prepared by thermal decomposition of Mg-Al-layered double hydroxides with vanadium interlayer doping. The obtained catalysts were tested for the oxidative dehydrogenation of propane, obtaining good results in catalytic activity (conversion 16.55 % and selectivity 99.97 %) Results indicated that catalytic performance of these materials depends on how vanadium is integrated in the layered structure, which is determined by the Mg/Al ratio. Vanadium interlayer doping modifies the oxidation state of vanadium and consequently catalytic properties. Surface properties were studied by X-ray photoelectron spectroscopic and diffuse reflectance, UV-visible spectroscopy, and temperature programmed reduction. The analyses provided information about the oxidation state, before and after the reaction. From these results, it is suggested that selectivity to propylene and catalytic activity depend mainly of vanadium oxidation state. (Author)

Influence of vanadium oxidation states on the performance of V-Mg-Al mixed-oxide catalysts for the oxidative dehydrogenation of propane

Energy Technology Data Exchange (ETDEWEB)

Schacht, L. [IPN, Escuela Superior de Fisica y Matematicas, Departamento de Ciencia de Materiales, Av. IPN s/n, Edificio 9, Col. Lindavista, 07738 Mexico D. F. (Mexico); Navarrete, J.; Schacht, P.; Ramirez, M. A., E-mail: pschacha@imp.m [Instituto Mexicano del Petroleo, Programa de Ingenieria Molecular, Eje Central Lazaro Cardenas No. 152, 07730 Mexico D. F. (Mexico)

2010-07-01

V-Mg-Al mixed-oxide catalysts for oxidative dehydrogenation of propane were prepared by thermal decomposition of Mg-Al-layered double hydroxides with vanadium interlayer doping. The obtained catalysts were tested for the oxidative dehydrogenation of propane, obtaining good results in catalytic activity (conversion 16.55 % and selectivity 99.97 %) Results indicated that catalytic performance of these materials depends on how vanadium is integrated in the layered structure, which is determined by the Mg/Al ratio. Vanadium interlayer doping modifies the oxidation state of vanadium and consequently catalytic properties. Surface properties were studied by X-ray photoelectron spectroscopic and diffuse reflectance, UV-visible spectroscopy, and temperature programmed reduction. The analyses provided information about the oxidation state, before and after the reaction. From these results, it is suggested that selectivity to propylene and catalytic activity depend mainly of vanadium oxidation state. (Author)

Determination of oxygen in ternary uranium oxides by a gravimetric alkaline earth addition method

International Nuclear Information System (INIS)

Fujino, T.; Tagawa, H.

1979-01-01

The applicability of a gravimetric method based on alkaline earth metal addition for the determination of oxygen in ternary uranium oxides of the tupe M-U-O (M=La, Ce and Th) is described. The oxide sample is mixed with MgO or Basub(2.8)UOsub(5.8) and heated in air under suitable conditions. Because uranium is completely oxidized to the hexavalent state during the reaction, oxygen can be determined from the weight change. Oxygen in Lasub(y)Usub(1-y)Osub(2+x) is determined up to y = 0.8 with a standard deviation for x of +- 0.006 with MgO. For Thsub(y)Usub(1-y)Osub(2+x) the value of x is determined with Basub(2.8)UOsub(5.8) with a standard deviation of +- 0.01 at y = 0.8. For Cesub(y)Usub(1-y)Osub(2+x), the method can be applied only for low cerium concentrations where y = 0-0.2; the value for x with Basub(2.8)UOsub(5.8) at y = 0.2 showed a standard deviation of +- 0.002. (Auth.)

An Investigation on the Extraction and Quantitation of a Hexavalent Chromium in Acrylonitrile Butadiene Styrene Copolymer (ABS) and Printed Circuit Board (PCB) by Ion Chromatography Coupled with Inductively Coupled Plasma Atomic Emission Spectrometry

Energy Technology Data Exchange (ETDEWEB)

Nam, Sang Ho; Kim, Yu Na [Mokpo National University, Muan (Korea, Republic of)

2012-06-15

A hexavalent chromium (Cr (VI)) is one of the hazardous substances regulated by the RoHS. The determination of Cr (VI) in various polymers and printed circuit board (PCB) has been very important. In this study, the three different analytical methods were investigated for the determination of a hexavalent chromium in Acrylonitrile Butadiene Styrene copolymer (ABS) and PCB. The results by three analytical methods were obtained and compared. An analytical method by UV-Visible spectrometer has been generally used for the determination of Cr (VI) in a sample, but a hexavalent chromium should complex with diphenylcarbazide for the detection in the method. The complexation did make an adverse effect on the quantitative analysis of Cr (VI) in ABS. The analytical method using diphenylcarbazide was also not applicable to printed circuit board (PCB) because PCB contained lots of irons. The irons interfered with the analysis of hexavalent chromium because those also could complex with diphenylcarbazide. In this study, hexavalent chromiums in PCB have been separated by ion chromatography (IC), then directly and selectively detected by inductively coupled plasma atomic emission spectrometry (ICP-AES). The quantity of Cr (VI) in PCB was 0.1 mg/kg

The Survey of Melia Azaderach L. ash in Removal of Hexavalent Chromium from Synthetic Electroplating Industry Wastewater

Directory of Open Access Journals (Sweden)

MT Ghaneian

2014-11-01

Conclusion: Melia azedarach ash is an effective adsorbent in removal of hexavalent chromium from synthetic electroplating industries wastewater. In addition, the use of this biosorbent in preparation and application aspects is simple and cheap compared to many other natural and man-made adsorbent.

Kinetics of tetravalent plutonium oxidation by cerium (4)

Energy Technology Data Exchange (ETDEWEB)

Nikitina, G P; Shumakov, V G; Egorova, V P

1975-01-01

Stoichiometry and kinetics of the Pu(4) + Ce(4) reaction is studied by spectrophotometric method at 5-30 deg C in nitric acid solutions (..mu..=(HNO/sub 3/)+(NaNO/sub 3/) = 1.0 - 5.7; (Ce(4)) = 5.10/sup -5/ - 1.2.10/sup -3/ g-ion/1, (Pu(4)) =1.10/sup -5/ - 8.5.10/sup -4/ g-ion/1. Oxidation of one Pu(4) ion to a hexavalent state requires two Ce(4) ions. The plutonium oxidation is not complicated by by-processes. Reverse Ce(3) + PuO/sub 2//sup +/ reaction does not contribute essentially to the process at (Ce(3)) 2.6.10/sup -2/ g-ion/1. The reaction rate obeys the kinetic equation - d(Pu(4))/dt = ksub(eff)(Pu(4))(Ce(4))/a sub(+-HNO/sub 3/). The thermodynamical activation parameters are found for solutions at the varied nitric acid concentrations:..delta..Gsup(not equal) = 17.0+-0.2 and ..delta..Hsup(not equal) = 21.8+-2 kcal/mole(..mu..=1.0); ..delta..Gsup(not equal) = 19.1+-0.1 and ..delta..Hsup(not equal) = 23.1+-1 kcal/mole(..mu..=4.9). The reaction mechanism is discussed in terms of the theory of absolute reaction rates and the model of long-range charge transfer.

Environmental biochemistry of chromium.

Science.gov (United States)

Losi, M E; Amrhein, C; Frankenberger, W T

1994-01-01

Chromium is a d-block transitional element with many industrial uses. It occurs naturally in various crustal materials and is discharged to the environment as industrial waste. Although it can occur in a number of oxidation states, only 3+ and 6+ are found in environmental systems. The environmental behavior of Cr is largely a function of its oxidation state. Hexavalent Cr compounds (mainly chromates and dichromates) are considered toxic to a variety of terrestrial and aquatic organisms and are mobile in soil/water systems, much more so than trivalent Cr compounds. This is largely because of differing chemical properties: Hexavalent Cr compounds are strong oxidizers and highly soluble, while trivalent Cr compounds tend to form relatively inert precipitates at near-neutral pH. The trivalent state is generally considered to be the stable form in equilibrium with most soil/water systems. A diagram of the Cr cycle in soils and water is given in Fig. 6 (Bartlett 1991). This illustration provides a summary of environmentally relevant reactions. Beginning with hexavalent Cr that is released into the environment as industrial waste, there are a number of possible fates, including pollution of soil and surface water and leaching into groundwater, where it may remain stable and, in turn, can be taken up by plants or animals, and adsorption/precipitation, involving soil colloids and/or organic matter. Herein lies much of the environmental concern associated with the hexavalent form. A portion of the Cr(VI) will be reduced to the trivalent form by inorganic electron donors, such as Fe2+ and S2-, or by bioprocesses involving organic matter. Following this conversion, Cr3+ can be expected to precipitate as oxides and hydroxides or to form complexes with numerous ligands. This fraction includes a vast majority of global Cr reserves. Soluble Cr3+ complexes, such as those formed with citrate, can undergo oxidation when they come in contact with manganese dioxide, thus reforming

Characterization and recovery of hexavalent chromium salts of an environmental liability; Caracterizacion y recuperacion de sales de cromo hexavalente de un pasivo ambiental

Energy Technology Data Exchange (ETDEWEB)

Rangel C, A. A.; Isarain C, E. [Centro de Innovacion Aplicada en Tecnologias Competitivas, Omega 201, Fracc. Industrial Delta, 37545 Leon, Guanajuato (Mexico); Maldonado V, M., E-mail: r.cordova.alexander@gmail.com [Hospital Regional de Alta Especialidad del Bajio, Bulevard Milenio No. 130, San Carlos la Roncha, 37660 Leon, Guanajuato (Mexico)

2015-07-01

The purpose of this study was to examine a diverse group of washing solutions for its use in the recovery of the industrial waste hexavalent chromium, in compliance with the Mexican regulation NOM-147-SEMARNAT/SSA1-2004. The recovery process consisted of a simple random sampling and a physical-chemical characterization with consideration to the high solubility of hexavalent chromium compounds. A test was performed which implemented five different washing solutions (water, sulfuric acid, citric acid, sodium hydroxide, calcium and hydroxide). This was followed by a factorial experimental design to optimize resources with a removal efficiency of 80% and hence a recovery of 33 g/kg as CaCrO{sub 4} (calcium chromate). Chromium hexavalent concentration in the leachate was quantified using UV-Vis spectrometry at a wavelength λ = 540 nm, while the salts recovered by evaporation were characterized using X-ray fluorescence analysis, leading to the conclusion that precipitate can be used as raw material, the main elements are Cr, Ca, Fe and Mg, and their concentration depends on the washing solution. (Author)

Charge state of oxide layer of SIMOX-structures

CERN Document Server

Askinazi, A Y; Dmitriev, V A; Miloglyadova, L V

2001-01-01

The charge state of the oxide layer of the SIMOX-structures, obtained in the course of forming the oxide layers, bricked up in the silicon volume, through the oxygen ions implantation into the Si, is studied. The charge state of the given structures is studied through the method of the layer-by-layer profiling, which makes it possible to obtain the dependence of the plane zones potential on the oxide layer thickness. It is established, that during the process of the SIMOX-structures formation in the oxide layer near the boundary with the Si there appear defects, responsible for the charge. The radiation from the near-the-ultraviolet (NUV) area without the applied electric field neutralizes the given charge. The simultaneous impact of the NUV-radiation and electric field leads to the formation of significantly positive charge

Environmentally Friendly Zirconium Oxide Pretreatment

Science.gov (United States)

2013-05-01

Society for Testing and Materials AVCRAD Aviation Classification Repair Activity Depot Chrome (VI) Hexavalent Chromium CRS Cold Rolled Steel...are being used commercially in automotive and other industrial operations as replacements to hexavalent chromium-based and zinc phosphate...application over CRS and aluminum with water-borne and solvent-borne Mil-Spec primers gave results in corrosion performance similar to the chrome

Effect of microorganisms on the plutonium oxidation states

International Nuclear Information System (INIS)

Lukšienė, Benedikta; Druteikienė, Rūta; Pečiulytė, Dalia; Baltrūnas, Dalis; Remeikis, Vidmantas; Paškevičius, Algimantas

2012-01-01

Particular microbes from substrates at the low-level radioactive waste repository in the Ignalina NPP territory were exposed to 239 Pu (IV) at low pH under aerobic conditions. Pu(III) and Pu(IV) were separated and quantitatively evaluated using the modified anion exchange method and alpha spectrometry. Tested bacteria Bacillus mycoides and Serratia marcescens were more effective in Pu reduction than Rhodococcus fascians. Fungi Paecillomyces lilacinus and Absidia spinosa var. spinosa as well as bacterium Rhodococcus fascians did not alter the plutonium oxidation state. - Highlights: ► Particular microbes from low-level radioactive waste repository were exposed to Pu (IV). ► Some tested bacteria induced slight Pu (IV) reduction at low pH under aerobic conditions. ► Tested fungi did not show peculiarities to alter Pu oxidation state. ► The modified radiochemical method was applied to differentiate Pu oxidation states.

Application of EIS to In Situ Characterization of Hydrothermal Sealing of Anodized Aluminum Alloys: Comparison between Hexavalent Chromium-Based Sealing, Hot Water Sealing and Cerium-Based Sealing

OpenAIRE

Carangelo, Anna; Curioni, Michele; Acquesta, Annalisa; Monetta, Tullio; Bellucci, Francesco

2016-01-01

Chromic acid anodizing has been used for almost a century to enhance corrosion protection of aerospace alloys. For some applications,hydrothermal sealing in hexavalent chromium-containing solution is required to enhance further the corrosion resistance but, due toenvironmental concerns, the use of hexavalent chromium must be discontinued. Good progress has been made to replace chromatesduring anodizing but comparatively less effort has focused on the sealing process. In this work, for the fir...

Combined nano-biotechnology for in-situ remediation of mixed contamination of groundwater by hexavalent chromium and chlorinated solvents

Czech Academy of Sciences Publication Activity Database

Němeček, J.; Pokorný, P.; Lhotský, O.; Knytl, V.; Najmanová, P.; Steinová, J.; Černík, M.; Filipová, Alena; Filip, J.; Cajthaml, Tomáš

2016-01-01

Roč. 563, SEP 1 (2016), s. 822-834 ISSN 0048-9697 R&D Projects: GA TA ČR TE01020218 Institutional support: RVO:61388971 Keywords : Chlorinated solvents * Hexavalent chromium * NZVI Subject RIV: EE - Microbiology, Virology Impact factor: 4.900, year: 2016

Effect of microorganisms on the plutonium oxidation states

Energy Technology Data Exchange (ETDEWEB)

Luksiene, Benedikta, E-mail: bena@ar.fi.lt [Center for Physical Sciences and Technology, Savanoriu ave 231, LT-02300 Vilnius (Lithuania); Druteikiene, Ruta [Center for Physical Sciences and Technology, Savanoriu ave 231, LT-02300 Vilnius (Lithuania); Peciulyte, Dalia [Nature Research Centre, Akademijos street 2, LT-08412 Vilnius (Lithuania); Baltrunas, Dalis; Remeikis, Vidmantas [Center for Physical Sciences and Technology, Savanoriu ave 231, LT-02300 Vilnius (Lithuania); Paskevicius, Algimantas [Nature Research Centre, Akademijos street 2, LT-08412 Vilnius (Lithuania)

2012-03-15

Particular microbes from substrates at the low-level radioactive waste repository in the Ignalina NPP territory were exposed to {sup 239}Pu (IV) at low pH under aerobic conditions. Pu(III) and Pu(IV) were separated and quantitatively evaluated using the modified anion exchange method and alpha spectrometry. Tested bacteria Bacillus mycoides and Serratia marcescens were more effective in Pu reduction than Rhodococcus fascians. Fungi Paecillomyces lilacinus and Absidia spinosa var. spinosa as well as bacterium Rhodococcus fascians did not alter the plutonium oxidation state. - Highlights: Black-Right-Pointing-Pointer Particular microbes from low-level radioactive waste repository were exposed to Pu (IV). Black-Right-Pointing-Pointer Some tested bacteria induced slight Pu (IV) reduction at low pH under aerobic conditions. Black-Right-Pointing-Pointer Tested fungi did not show peculiarities to alter Pu oxidation state. Black-Right-Pointing-Pointer The modified radiochemical method was applied to differentiate Pu oxidation states.

Shifts in oxidation states of cerium oxide nanoparticles detected inside intact hydrated cells and organelles

Energy Technology Data Exchange (ETDEWEB)

Szymanski, Craig J.; Munusamy, Prabhakaran; Mihai, Cosmin; Xie, Yumei; Hu, Dehong; Gilles, Marry K.; Tyliszczak, T.; Thevuthasan, Suntharampillai; Baer, Donald R.; Orr, Galya

2015-09-01

Cerium oxide nanoparticles (CNPs) have been shown to induce diverse biological effects, ranging from toxic to beneficial. The beneficial effects have been attributed to the potential antioxidant activity of CNPs via certain redox reactions, depending on their oxidation state or Ce3+/Ce4+ ratio. However, this ratio is strongly dependent on the environment and age of the nanoparticles and it is unclear whether and how the complex intracellular environment impacts this ratio and the possible redox reactions of CNPs. To identify any changes in the oxidation state of CNPs in the intracellular environment and better understand their intracellular reactions, we directly quantified the oxidation states of CNPs outside and inside intact hydrated cells and organelles using correlated scanning transmission x-ray and super resolution fluorescence microscopies. By analyzing hundreds of small CNP aggregates, we detected a shift to a higher Ce3+/Ce4+ ratio in CNPs inside versus outside the cells, indicating a net reduction of CNPs in the intracellular environment. We further found a similar ratio in the cytoplasm and in the lysosomes, indicating that the net reduction occurs earlier in the internalization pathway. Together with oxidative stress and toxicity measurements, our observations identify a net reduction of CNPs in the intracellular environment, which is consistent with their involvement in potentially beneficial oxidation reactions, but also point to interactions that can negatively impact the health of cells.

Reduction of Hexavalent Chromium and Detection of Chromate Reductase (ChrR in Stenotrophomonas maltophilia

Directory of Open Access Journals (Sweden)

Rosa Baldiris

2018-02-01

Full Text Available An Gram negative strain of S. maltophilia, indigenous to environments contaminated by Cr(VI and identified by biochemical methods and 16S rRNA gene analysis, reduced chromate by 100%, 98–99% and 92% at concentrations in the 10–70, 80–300, and 500 mg/L range, respectively at pH 7 and temperature 37 °C. Increasing concentrations of Cr(VI in the medium lowered the growth rate but could not be directly correlated with the amount of Cr(VI reduced. The strain also exhibited multiple resistance to antibiotics and tolerance and resistance to various heavy metals (Ni, Zn and Cu, with the exception of Hg. Hexavalent chromium reduction was mainly associated with the soluble fraction of the cell evaluated with crude cell-free extracts. A protein of molecular weight around 25 kDa was detected on SDS-PAGE gel depending on the concentration of hexavalent chromium in the medium (0, 100 and 500 mg/L. In silico analysis in this contribution, revealed the presence of the chromate reductase gene ChrR in S. maltophilia, evidenced through a fragment of around 468 bp obtained experimentally. High Cr(VI concentration resistance and high Cr(VI reducing ability of the strain make it a suitable candidate for bioremediation.

Extraction chromatogrpahy of actinides, ch. 7

International Nuclear Information System (INIS)

Mueller, W.

1975-01-01

This review on extraction chromatography of actinides emphasizes the important usage of neutral (Tributylphosphate), basic (substituted ammonium salts), and acidic (HDEHP) extractants, and their application to separations of actinides in the di-to hexavalent oxidation state. Furthermore, the actinide extraction by ketones, ethers, alcohols and β-diketones is discussed

Separation method for uranium, plutonium, and neptunium with each other from spent nuclear fuel

International Nuclear Information System (INIS)

Uchiyama, Gunzo; Hotoku, Shinobu; Fujine, Sachio; Maeda, Mitsuru.

1994-01-01

In a nuclear fuel reprocessing step of the present invention, an Np oxidation step is provided on a high level side of a co-contamination step, and an Np separation step and a U/Pu recovering step provided preceding to a U/Pu distribution step. Np oxidation step uses an oxidizer which is not extracted by an organic solvent such as ammonium vanadate for oxidizing Np from pentavalence to hexavalence. The Np separation step uses n-butylaldehyde for selectively reducing only hexavalent Np into pentavalent Np in a system in which hexavalent Np and tetravalent Pu are present together. In the U/Pu recovering step, pentavalent U and tetravalent Pu which shift by so much as distribution equilibrium are extracted together with pentavalent Np by using an organic solvent. The U/Pu distribution step uses iso-butylaldehyde as a reagent for selectively reducing only tetravalent Pu present together with hexavalent U into trivalent. With such procedures, U, Pu and Np can be separated with each other by more simplified fuel processing process. (T.M.)

Simultaneously photocatalytic treatment of hexavalent chromium (Cr(VI)) and endocrine disrupting compounds (EDCs) using rotating reactor under solar irradiation

International Nuclear Information System (INIS)

Kim, Youngji; Joo, Hyunku; Her, Namguk; Yoon, Yeomin; Sohn, Jinsik; Kim, Sungpyo; Yoon, Jaekyung

2015-01-01

Highlights: • Self-rotating reactor including TiO 2 NTs is applied under solar irradiation. • Simultaneously photocatalysis of Cr(VI) and EDCs is observed to be up to 95%. • Photocatalytic reactions of Cr(VI) and EDCs are favorable under acidic pH. • Charge interaction and hole scavenge between TiO 2 and pollutants are synergy factors. - Abstract: In this study, simultaneous treatments, reduction of hexavalent chromium (Cr(VI)) and oxidation of endocrine disrupting compounds (EDCs), such as bisphenol A (BPA), 17α-ethinyl estradiol (EE2) and 17β-estradiol (E2), were investigated with a rotating photocatalytic reactor including TiO 2 nanotubes formed on titanium mesh substrates under solar UV irradiation. In the laboratory tests with a rotating type I reactor, synergy effects of the simultaneous photocatalytic reduction and oxidation of inorganic (Cr(VI)) and organic (BPA) pollutants were achieved. Particularly, the concurrent photocatalytic reduction of Cr(VI) and oxidation of BPA was higher under acidic conditions. The enhanced reaction efficiency of both pollutants was attributed to a stronger charge interaction between TiO 2 nanotubes (positive charge) and the anionic form of Cr(VI) (negative charge), which are prevented recombination (electron–hole pair) by the hole scavenging effect of BPA. In the extended outdoor tests with a rotating type II reactor under solar irradiation, the experiment was extended to examine the simultaneous reduction of Cr(VI) in the presence of additional EDCs, such as EE2 and E2 as well as BPA. The findings showed that synergic effect of both photocatalytic reduction and oxidation was confirmed with single-component (Cr(VI) only), two-components (Cr(VI)/BPA, Cr(VI)/EE2, and Cr(VI)/E2), and four-components (Cr(VI)/BPA/EE2/E2) under various solar irradiation conditions

A new method in estimation of total hexavalent chromium in Portland pozzolan cement; Un nuevo método en la determinación del cromo hexavalente total en cemento Portland puzolánico.

Energy Technology Data Exchange (ETDEWEB)

Sharma, R.; Sharma, D.

2017-07-01

Variamine blue was used first time for the detection of hexavalent chromium from cement samples. In present method, cement was treated sequentially with water, sulphate and carbonate buffer to extract soluble, sparingly soluble and insoluble hexavalent chromium respectively. Extracted Cr (VI) was determined using variamine blue as chromogenic reagent. The determination is based on the reaction of hexavalent chromium with potassium iodide in an acid medium to liberate iodine. This oxidizes variamine blue to form a violet coloured species having an absorption to maximum at 556 nm. Energy-dispersive X-ray spectroscopy (EDX) and Infrared Spectroscopy (IR) confirmed the complete extraction of hexavalent chromium by sequential extraction process. SRM 2701 (Reference material from NIST, USA) was used for revalidating the results. The percentage of recovery for proposed and reference method (diphelycarbazide method) varied from 98.5 to 101 and 97.5 to 100.5. Whereas, their relative error percentage varied from -1.5 to 0.33 and -2.5 to 0.5. [Spanish] El azul de variamina se utilizó por primera vez para la detección de cromo hexavalente en muestras de cemento. En el presente método, el cemento se trató secuencialmente con agua, y tampones sulfato y carbonato para extraer el cromo hexavalente soluble, poco soluble e insoluble, respectivamente. El Cr (VI) extraído se determinó utilizando azul de variamina como reactivo cromógeno, por reacción del cromo hexavalente con yoduro de potasio en un medio ácido para liberar yodo. Esto oxida al azul de variamina para formar una especie de color violeta con una absorción máxima a 556 nm. El análisis por energía dispersiva de rayos X (EDX) y la espectroscopía de infrarrojos (IR) confirmaron la extracción completa de cromo hexavalente mediante el proceso de extracción secuencial. Se utilizó SRM 2701 (material de referencia de NIST, EE.UU.) para validar los resultados. El porcentaje de recuperación para el m

Influence of oxidation state on the pH dependence of hydrous iridium oxide films

International Nuclear Information System (INIS)

Steegstra, Patrick; Ahlberg, Elisabet

2012-01-01

Many electrochemical reactions taking place in aqueous solution consume or produce protons. The pH in the diffusion layer can therefore be significantly altered during the reaction and there is a need for in situ pH measurements tracing this near surface pH. In the present paper the rotating ring disc technique was used to measure near surface pH changes during oxygen reduction, utilising hydrous iridium oxide as the pH sensing probe. Before such experiments a good understanding of the pH sensing properties of these films is required and the impact of the oxidation state of the film on the pH sensing properties was investigated as well as the influence of solution redox species. The pH sensitivity (depicted by dE/dpH) was found to depend on the average oxidation state of the film in a manner resembling the cyclic voltammetry response. In all cases the pH response is “supernernstian” with more than one proton per electron. The origin of this behaviour is discussed in the context of acid-base properties of the film and the existence of both hydrous and anhydrous oxide phases. The pH response depends also on the redox properties of the solution but can be optimised for various purposes by conditioning the film at different potentials. This was clearly illustrated by adding hydrogen peroxide, an intermediate in the oxygen reduction reaction, to the solution. It was shown that hydrous iridium oxide can be used as a reliable in situ pH sensor provided that care is taken to optimise the oxidation state of the film.

Study on Leaching of Hexavalent Chromium from Hardened Concretes Using Tank Leaching Test

OpenAIRE

Takahashi, Shigeru; Sakai, Etsuo; Sugiyama, Takafumi

2007-01-01

Tank leaching tests were carried out to investigate the behavior of leaching trace elements from monolith samples. This study consists of two series, and the trace element used was hexavalent chromium. In Series I, the influence of the leachant/surface area of the specimen (L/S ratio) on the leaching amount was investigated. The leaching amount was found to increase with the amount of worked water. This shows that any L/S ratio can be selected in the tank leaching test. In Series II, th...

Utilization of cross-linked carboxymethyl κ-carrageenan as adsorbent for hexavalent chromium (Cr+6) ion

International Nuclear Information System (INIS)

Antonio, Princess Joyce R.; Punzalan, Mark Emile H.; Saturno, Rochelle Anne B.; Bayquen, Aristea V.

2009-01-01

The sorption behavior of cross-linked carboxymethyl κ-carrageenan as an alternative adsorbent for hexavalent chromium was studies. The κ-carrageenan had been carboxymethylated three times with 40% NaOH and monochloroacetic acid (MCA) in 80% isopropyl alcohol at 40 0 C. Carboxymethylated κ-carrageenan was crosslinked using Co 60 irradiation facility at PNRI. Batch experiments were conducted using prepared stock solution of Cr 6+ (70 ppm) under different sorption parameters at room temperature. These parameters include effects of pH, initial metal ion concentration, and contact time. Carboxymethylation and cross-linking was successfully achieved under optimum parameters. It was observed that cross-linked carboxymethyl κ-carrageenan best adsorbs chromium (VI) ion at pH 6, removing 41.59% of the metal ions present in the solution. Freundlich isotherm gave the highest correlation, R 2 , which is equal to 0.9880. This suggests the existence of mutilayer adsorption of the hexavalent chromium ions. Maximum adsorption was found to be at contact time of 2.5 hours and the concentration of the solution remains almost constant after 5 hours. The adsorption kinetics could be approximated favorably by the Lagergren pseudo-second-order kinetic model giving a correlation, R 2 , of 0.9985 and adsorption capacity, qmax, equal to 27.88 mg g +1 . (author)

Use of Cork Waste as Biosorbent for Hexavalent Chromium

International Nuclear Information System (INIS)

Sfaksi, Z.; Azzouz, N.; Abdelwahab, A.

2011-01-01

The biosorption by cork powder is considered as a new method for heavy metal removal from industrial waste waters such as chromium tanning factories. The aim of this study is to evaluate the efficiency extent of this method using a cork powder as biosorbent for hexavalent chromium Cr(VI). The Fourier Transform Infrared spectroscopy (FTIR) analysis permits to distinguish the type of functional groups likely to participate in metal binding. A linear form of BET isotherms for all the three used temperatures (25, 35 and 45 0 C) and a pseudo-second-order Lagergren equation of adsorption kinetics are obtained. Other experimental results highlight the meaningful influence of parameters such as contact time, pH and concentrations of the solution, on chromium adsorption rate that reach a 97% value under definite conditions particularly a pH of 2-3 values. (author)

Study of uranium oxidation states in geological material.

Science.gov (United States)

Pidchenko, I; Salminen-Paatero, S; Rothe, J; Suksi, J

2013-10-01

A wet chemical method to determine uranium (U) oxidation states in geological material has been developed and tested. The problem faced in oxidation state determinations with wet chemical methods is that U redox state may change when extracted from the sample material, thereby leading to erroneous results. In order to quantify and monitor U redox behavior during the acidic extraction in the procedure, an analysis of added isotopic redox tracers, (236)U(VI) and (232)U(IV), and of variations in natural uranium isotope ratio ((234)U/(238)U) of indigenous U(IV) and U(VI) fractions was performed. Two sample materials with varying redox activity, U bearing rock and U-rich clayey lignite sediment, were used for the tests. The Fe(II)/Fe(III) redox-pair of the mineral phases was postulated as a potentially disturbing redox agent. The impact of Fe(III) on U was studied by reducing Fe(III) with ascorbic acid, which was added to the extraction solution. We observed that ascorbic acid protected most of the U from oxidation. The measured (234)U/(238)U ratio in U(IV) and U(VI) fractions in the sediment samples provided a unique tool to quantify U oxidation caused by Fe(III). Annealing (sample heating) to temperatures above 500 °C was supposed to heal ionizing radiation induced defects in the material that can disturb U redox state during extraction. Good agreement between two independent methods was obtained for DL-1a material: an average 38% of U(IV) determined by redox tracer corrected wet chemistry and 45% for XANES. Copyright © 2013 Elsevier Ltd. All rights reserved.

Remediation of hexavalent chromium spiked soil by using synthesized iron sulfide particles.

Science.gov (United States)

Li, Yujie; Wang, Wanyu; Zhou, Liqiang; Liu, Yuanyuan; Mirza, Zakaria A; Lin, Xiang

2017-02-01

Carboxymethyl cellulose (CMC) stabilized microscale iron sulfide (FeS) particles were synthesized and applied to remediate hexavalent chromium (Cr(VI)) spiked soil. The effects of parameters including dosage of FeS particles, soil moisture, and natural organic matter (NOM) in soil were investigated with comparison to iron sulfate (FeSO 4 ). The results show that the stabilized FeS particles can reduce Cr(VI) and immobilize Cr in soil quickly and efficiently. The soil moisture ranging from 40% to 70% and NOM in soil had no significant effects on Cr(VI) remediation by FeS particles. When molar ratio of FeS to Cr(VI) was 1.5:1, about 98% of Cr(VI) in soil was reduced by FeS particles in 3 d and Cr(VI) concentration decreased from 1407 mg kg -1 to 16 mg kg -1 . The total Cr and Cr(VI) in Toxicity Characteristic Leaching Procedure (TCLP) leachate were reduced by 98.4% and 99.4%, respectively. In FeS particles-treated soil, the exchangeable Cr fraction was mainly converted to Fe-Mn oxides bound fraction because of the precipitation of Cr(III)-Fe(III) hydroxides. The physiologically based extraction test (PBET) bioaccessibility of Cr was decreased from 58.67% to 6.98%. Compared to FeSO 4 , the high Cr(VI) removal and Cr immobilization efficiency makes prepared FeS particles a great potential in field application of Cr(VI) contaminated soil remediation. Copyright © 2016 Elsevier Ltd. All rights reserved.

A magnetic route to measure the average oxidation state of mixed-valent manganese in manganese oxide octahedral molecular sieves (OMS).

Science.gov (United States)

Shen, Xiong-Fei; Ding, Yun-Shuang; Liu, Jia; Han, Zhao-Hui; Budnick, Joseph I; Hines, William A; Suib, Steven L

2005-05-04

A magnetic route has been applied for measurement of the average oxidation state (AOS) of mixed-valent manganese in manganese oxide octahedral molecular sieves (OMS). The method gives AOS measurement results in good agreement with titration methods. A maximum analysis deviation error of +/-7% is obtained from 10 sample measurements. The magnetic method is able to (1) confirm the presence of mixed-valent manganese and (2) evaluate AOS and the spin states of d electrons of both single oxidation state and mixed-valent state Mn in manganese oxides. In addition, the magnetic method may be extended to (1) determine AOS of Mn in manganese oxide OMS with dopant "diamagnetic" ions, such as reducible V5+ (3d0) ions, which is inappropriate for the titration method due to interference of redox reactions between these dopant ions and titration reagents, such as KMnO4, (2) evaluate the dopant "paramagnetic" ions that are present as clusters or in the OMS framework, and (3) determine AOS of other mixed-valent/single oxidation state ion systems, such as Mo3+(3d3)-Mo4+(3d2) systems and Fe3+ in FeCl3.

PHOTOCATALYTIC REMOVAL OF TR I- AND HEXA-VALENT CHROMIUM IONS FROM CHROME-ELECTROPL ATING WASTEWATER

OpenAIRE

Puangrat Kajitvichyanukul; Chulaluck Changul

2017-01-01

A novel technique based on photocatalysis was applied to eliminate chromium ions, a toxic hazardous environmental pollutant. The photoreduction of each species of chromium (total, hexavalent, and trivalent chromiums) from chrome-electroplating wastewater was investigated using a titanium dioxide suspension under irradiation by a low-pressure mercury lamp. The initial concentration of total chromium was 300 mg/l. The applied conditions were the direct photocatalytic reduction process at pH 3.6...

NASA TEERM Hexavalent Chrome Alternatives Projects

Science.gov (United States)

Kessel, Kurt R.; Rothgeb, Matthew

2011-01-01

The overall objective of the Hex Chrome Free Coatings for Electronics project is to evaluate and test pretreatment coating systems not containing hexavalent chrome in avionics and electronics housing applications. This objective will be accomplished by testing strong performing coating systems from prior NASA and DoD testing or new coating systems as determined by the stakeholders. The technical stakeholders have agreed that this protocol will focus specifically on Class 3 coatings. Original Equipment Manufacturers (OEMs), depots, and support contractors have to be prepared to deal with an electronics supply chain that increasingly provides parts with lead-free finishes, some labeled no differently and intermingled with their SnPb counterparts. Allowance of lead-free components presents one of the greatest risks to the reliability of military and aerospace electronics. The introduction of components with lead-free terminations, termination finishes, or circuit boards presents a host of concerns to customers, suppliers, and maintainers of aerospace and military electronic systems such as: 1. Electrical shorting due to tin whiskers 2. Incompatibility of lead-free processes and parameters (including higher melting points of lead-free alloys) with other materials in the system 3. Unknown material properties and incompatibilities that could reduce solder joint reliability

Origin of interface states and oxide charges generated by ionizing radiation

International Nuclear Information System (INIS)

Sah, C.T.

1976-01-01

The randomly located trivalent silicon atoms are shown to account for the thermally generated interface states at the SiO 2 -Si interface. The interface state density is greatly reduced in water containing ambients at low temperatures (450 0 C) by forming trivalent silicon hydroxide bonds. Interface states are regenerated when the /triple bond/Si-OH bonds are broken by ionizing radiation and the OH ions are drifted away. In the bulk of the oxide film, the trivalent silicon and the interstitial oxygen donor centers are shown to be responsible for the heat and radiation generated positive space charge build-up (oxide charge) in thermally grown silicon oxide

Laboratory and field evaluations of a methodology for determining hexavalent-chromium emissions from stationary sources. Final report

International Nuclear Information System (INIS)

Carver, A.C.

1991-10-01

The study was initiated to determine whether chromium emissions should be regulated under Section 112 of the Clean Air Act National Emissions Standards for Hazardous Air Pollutants (NESHAP). To support stationary source regulations, it is important that (1) the sampling procedure not change the chromium valence state during sampling and (2) an analytical technique for measuring low concentration levels of chromium be available. These goals are achieved with the current EPA 'Draft Method for Sampling and Analysis of Hexavalent Chromium at Stationary Sources.' The draft method utilizes a recirculating system to flush impinger reagent into the sampling nozzle during sample collection. Immediate contact of the stack gas with impinger reagent 'fixes' the chromium valence state. Ion chromatography coupled with post column derivatization and ultraviolet visible detector is used to analyze Cr(VI) in the parts per trillion range. Field tests were conducted at metal plating facilities, industrial cooling towers, municipal waste incinerators, sewage sludge incinerators, and hazardous waste incinerators. It was at the hazardous waste facility that the new method was proven to have acceptable precision and essentially no conversion in the sample train

Oxidative Stress and Heart Failure in Altered Thyroid States

Directory of Open Access Journals (Sweden)

Pallavi Mishra

2012-01-01

Full Text Available Increased or reduced action of thyroid hormone on certain molecular pathways in the heart and vasculature causes relevant cardiovascular derangements. It is well established that hyperthyroidism induces a hyperdynamic cardiovascular state, which is associated with a faster heart rate, enhanced left ventricular systolic and diastolic function whereas hypothyroidism is characterized by the opposite changes. Hyperthyroidism and hypothyroidism represent opposite clinical conditions, albeit not mirror images. Recent experimental and clinical studies have suggested the involvement of ROS tissue damage under altered thyroid status. Altered-thyroid state-linked changes in heart modify their susceptibility to oxidants and the extent of the oxidative damage they suffer following oxidative challenge. Chronic increase in the cellular levels of ROS can lead to a catastrophic cycle of DNA damage, mitochondrial dysfunction, further ROS generation and cellular injury. Thus, these cellular events might play an important role in the development and progression of myocardial remodeling and heart failure in altered thyroid states (hypo- and hyper-thyroidism. The present review aims at elucidating the various signaling pathways mediated via ROS and their modulation under altered thyroid state and the possibility of antioxidant therapy.

Adsorption properties versus oxidation states of rutile TiO2(110)

DEFF Research Database (Denmark)

Martinez, Umberto; Hammer, Bjørk

2011-01-01

Using density functional theory we have studied the adsorption properties of different atoms and molecules deposited on a stoichiometric, reduced, and oxidized rutile TiO2(110) surface. Depending on the oxidation state of the surface, electrons can flow from or to the substrate and, therefore...... of the charge flow depends on the oxidation state of the rutile surface and on the adsorption site. Generally, the charging effect leads to more stable complexes. However, the increase in the binding energy of the adsorbates is highly dependent on the electronic states of the surface prior to the adsorption...... event. In this work we have analyzed in details these mechanisms and we have also established a direct correlation between the enhanced binding energy of the adsorbates and the induced gap states...

Lithium salts as leachable corrosion inhibitors and potential replacement for hexavalent chromium in organic coatings for the protection of aluminum alloys

NARCIS (Netherlands)

Visser, P; Liu, Y; Terryn, H.A.; Mol, J.M.C.

2016-01-01

Lithium salts are being investigated as leachable corrosion inhibitor and potential replacement for hexavalent chromium in organic coatings. Model coatings loaded with lithium carbonate or lithium oxalate demonstrated active corrosion inhibition and the formation of a protective layer in a

Thermochemistry of rare earth doped uranium oxides Ln{sub x}U{sub 1−x}O{sub 2−0.5x+y} (Ln = La, Y, Nd)

Energy Technology Data Exchange (ETDEWEB)

Zhang, Lei; Navrotsky, Alexandra, E-mail: anavrotsky@ucdavis.edu

2015-10-15

Lanthanum, yttrium, and neodymium doped uranium dioxide samples in the fluorite structure have been synthesized, characterized in terms of metal ratio and oxygen content, and their enthalpies of formation measured by high temperature oxide melt solution calorimetry. For oxides doped with 10–50 mol % rare earth (Ln) cations, the formation enthalpies from constituent oxides (LnO{sub 1.5}, UO{sub 2} and UO{sub 3} in a reaction not involving oxidation or reduction) become increasingly exothermic with increasing rare earth content, while showing no significant dependence on the varying uranium oxidation state. The oxidation enthalpy of Ln{sub x}U{sub 1−x}O{sub 2−0.5x+y} is similar to that of UO{sub 2} to UO{sub 3} for all three rare earth doped systems. Though this may suggest that the oxidized uranium in these systems is energetically similar to that in the hexavalent state, thermochemical data alone can not constrain whether the uranium is present as U{sup 5+}, U{sup 6+}, or a mixture of oxidation states. The formation enthalpies from elements calculated from the calorimetric data are generally consistent with those from free energy measurements. - Highlights: • We synthesize, characterize Ln{sub x}U{sub 1−x}O{sub 2−0.5x+y} solid solutions (Ln = La, Y, Nd). • Formation enthalpies become more exothermic with increasing rare earth content. • Oxidation enthalpy of Ln{sub x}U{sub 1−x}O{sub 2−0.5x+y} is similar to that of UO{sub 2} to UO{sub 3}. • Direct calorimetric measurements are in good agreement with free energy data.

Photochemical oxidants: state of the science.

Science.gov (United States)

Kley, D; Kleinmann, M; Sanderman, H; Krupa, S

1999-01-01

Atmospheric photochemical processes resulting in the production of tropospheric ozone (O(3)) and other oxidants are described. The spatial and temporal variabilities in the occurrence of surface level oxidants and their relationships to air pollution meteorology are discussed. Models of photooxidant formation are reviewed in the context of control strategies and comparisons are provided of the air concentrations of O(3) at select geographic locations around the world. This overall oxidant (O(3)) climatology is coupled to human health and ecological effects. The discussion of the effects includes both acute and chronic responses, mechanisms of action, human epidemiological and plant population studies and briefly, efforts to establish cause-effect relationships through numerical modeling. A short synopsis is provided of the interactive effects of O(3) with other abiotic and biotic factors. The overall emphasis of the paper is on identifying the current uncertainties and gaps in our understanding of the state of the science and some suggestions as to how they may be addressed.

Recycling of ferrous sulfate by the synthesis of a new super oxidant material 'Referox'

Energy Technology Data Exchange (ETDEWEB)

Evrard, O. [Universite Henri Poincare, Vandoeuvre (France); Dupre, B.; Jeannot, C.; Kanari, N.; Gaballah, I.; Ninane, L.; Verstraete, W.; Denomme, S.; Belsue, M.

2001-07-01

This European Union-sponsored project was initiated to develop a process to recycle industrial ferrous sulfate by the synthesis of a superoxidant containing hexavalent (FeVI) iron. Hexavalent iron, also called ferrates, can be used in decontamination of industrial effluents, decolorisation and purification of effluents from the textile and tanning industries, oxidation of cyanide to cyanates, soil remediation, water treatment and in a variety of other processes. Dry synthesis of potassium ferrate, using calcium hypochlorite as the oxidizing agent, was successful. By using chlorine instead of calcium hypochlorite and by partially substituting sodium hydroxide for potassium hydroxide the cost of the synthesis was significantly reduced. Recycling of ferrous sulfate at room temperature by the synthesis of potassium ferrate (FeVI) using gaseous chlorine instead of solid calcium hypochlorite was also successful. The yield of the synthesis was about 65 per cent for the used industrial ferrous sulfate samples. Large scale experimentation of the potassium ferrate synthesis was also carried out, obtaining potassium ferrate that remained stable for several months. The ferrates were used in the treatment of drinking water, wastewater, soil remediation, and effluent decontamination. Encouraging results were obtained. An additional benefit found was that use of the ferrates as bactericide for water treatment instead of chlorine gas eliminates the generation of halo-organic compounds which are suspected to be carcinogenic. 2 figs.

Hexavalent Chrome Free Coatings for Electronics; Electromagnetic Interference (EMI) Shielding Effectiveness (SE)

Science.gov (United States)

Kessel, Kurt R.

2014-01-01

The purpose of this testing is to determine the suitability of trivalent chromium conversion coatings that meet the requirements of MIL-DTL-5541, Type II, for use in applications where high-frequency electrical performance is important. This project will evaluate the ability of coated aluminum to form adequate EMI seals. Testing will assess performance of the trivalent chromium coatings against the known control hexavalent chromium MIL-DTL-5541 Type I Class 3 before and after they have been exposed to a set of environmental conditions. Performance will be assessed by evaluating shielding effectiveness (SE) test data from a variety of test samples comprised of different aluminum types and/or conversion coatings.

The intracellular redox stress caused by hexavalent chromium is selective for proteins that have key roles in cell survival and thiol redox control

International Nuclear Information System (INIS)

Myers, Judith M.; Antholine, William E.; Myers, Charles R.

2011-01-01

Hexavalent chromium [Cr(VI)] compounds (e.g. chromates) are strong oxidants that readily enter cells where they are reduced to reactive Cr intermediates that can directly oxidize some cell components and can promote the generation of reactive oxygen and nitrogen species. Inhalation is a major route of exposure which directly exposes the bronchial epithelium. Previous studies with non-cancerous human bronchial epithelial cells (BEAS-2B) demonstrated that Cr(VI) treatment results in the irreversible inhibition of thioredoxin reductase (TrxR) and the oxidation of thioredoxins (Trx) and peroxiredoxins (Prx). The mitochondrial Trx/Prx system is somewhat more sensitive to Cr(VI) than the cytosolic Trx/Prx system, and other redox-sensitive mitochondrial functions are subsequently affected including electron transport complexes I and II. Studies reported here show that Cr(VI) does not cause indiscriminant thiol oxidation, and that the Trx/Prx system is among the most sensitive of cellular protein thiols. Trx/Prx oxidation is not unique to BEAS-2B cells, as it was also observed in primary human bronchial epithelial cells. Increasing the intracellular levels of ascorbate, an endogenous Cr(VI) reductant, did not alter the effects on TrxR, Trx, or Prx. The peroxynitrite scavenger MnTBAP did not protect TrxR, Trx, Prx, or the electron transport chain from the effects of Cr(VI), implying that peroxynitrite is not required for these effects. Nitration of tyrosine residues of TrxR was not observed following Cr(VI) treatment, further ruling out peroxynitrite as a significant contributor to the irreversible inhibition of TrxR. Cr(VI) treatments that disrupt the TrxR/Trx/Prx system did not cause detectable mitochondrial DNA damage. Overall, the redox stress that results from Cr(VI) exposure shows selectivity for key proteins which are known to be important for redox signaling, antioxidant defense, and cell survival.

[Nose disease caused by occupational exposure to chromium in the electroplating industry: cytomorphological aspects].

Science.gov (United States)

Bolla, I; Gariboldi, L M; Gabrielli, M; Baldo, D; Romanelli, A; Tuberti, E; Magnani, F

1990-01-01

Twenty-six workers were studied (9 chrome-platers exposed to chromium dioxide and 17 workers exposed to metallic chromium dust) in order to investigate the macroscopic and cytological changes of the nasal mucosa due to exposure to water-soluble hexavalent chromium or to metallic chromium dust in the electroplating industry and the role of different valencies in the onset of nasal disease. Experimental and epidemiological data have shown that hexavalent chromium, which has strong oxidative power, induces more noticeable toxic effects on tissues and mucous membranes than other compounds. The correlation between the degree of local toxic effects and the chemical state of chromium was demonstrated in both the macro- and the microscopic investigations and in particular in the cytological examinations: cases of atypia were found only in workers exposed to hexavalent chromium. Evidence of atypia raises the question of whether hexavalent chromium may act as a carcinogenic agent on the rhinosinusal mucosa. For this reason, the introduction of cytological nasal examination in health surveillance programmes for this category of workers acquires considerable importance. Sample collection from the nasal mucosa by brushing is the method of choice since it is simple, non-invasive and gives good diagnostic results.

Stabilization of chromium: an alternative to make safe leathers.

Science.gov (United States)

Gong, Ying; Liu, Xiaoling; Huang, Li; Chen, Wuyong

2010-07-15

In this study, the original causes for hexavalent chromium presence in the leather were first evaluated by ageing of chromium(III) solutions and chrome tanned hide powder (50 degrees C, UV lightening at 340 nm, 0-36 h). The results showed that the trivalent chromium at instable coordination state was easy to convert into hexavalent chromium in high pH environment, and the probability of the oxidation increased in this order: multi-coordinate chromium, mono-coordinate chromium, and free chromium. For this reason, the process for stabilizing chromium in the leather was designed with the specific material, which was mostly consisted of the reducers and the chelating agents. After treated with the developed process, these leathers were aged (50 degrees C, UV irradiance as 0.68 W/m(2) at 340 nm, 0-72 h) to estimate chromium(VI) presence. Hexavalent chromium was not found in these treated leathers even if the leathers were aged for 72 h. Moreover, the physical and mechanical properties for the leathers varied little after treating. In a word, an inherent safe and effective process was proved to avoid the formation of hexavalent chromium in the leather. 2010 Elsevier B.V. All rights reserved.

Nanoscale zero-valent iron application for in situ reduction of hexavalent chromium and its effects on indigenous microorganism populations

Czech Academy of Sciences Publication Activity Database

Němeček, J.; Lhotský, O.; Cajthaml, Tomáš

485-486, č. 2 (2014), s. 739-747 ISSN 0048-9697 R&D Projects: GA TA ČR TE01020218; GA MŠk ED0005/01/01; GA TA ČR TA01021792 Institutional support: RVO:61388971 Keywords : nanoparticles * hexavalent chromium * bioremediation Subject RIV: EE - Microbiology, Virology Impact factor: 4.099, year: 2014

Thermodynamic Ground States of Complex Oxide Heterointerfaces

DEFF Research Database (Denmark)

Gunkel, F.; Hoffmann-Eifert, S.; Heinen, R. A.

2017-01-01

The formation mechanism of 2-dimensional electron gases (2DEGs) at heterointerfaces between nominally insulating oxides is addressed with a thermodynamical approach. We provide a comprehensive analysis of the thermodynamic ground states of various 2DEG systems directly probed in high temperature...

Effet des polyamines sur la réduction du chrome hexavalent par des souches bactériennes et leur résistance

Directory of Open Access Journals (Sweden)

Tahri Joutey, N.

2014-01-01

Full Text Available Effect of polyamines on the reduction of hexavalent chromium by bacterial strains and their resistance. Polyamines are involved in several functions in bacteria. In this study, we examined the role of polyamines in hexavalent chromium (Cr[VI] reduction by three bacterial strains isolated from sites contaminated by tannery effluents. The strains were identified as Serratia proteamaculans, Leucobacter chromiireducens and Brevibacterium frigoritolerans. The inhibition of polyamine synthesis by α-difluoromethylornithine (DFMO caused a decrease in Cr(VI tolerance in the bacterial isolates, indicating the role of endogenous polyamines in resistance to Cr(VI. The exogenous application of polyamines (putrescine, spermidine, cadaverine was found to stimulate growth and Cr(VI reduction by the bacterial strains in Luria-Bertani medium. The results show the importance of polyamines in response to heavy metal stresses, especially Cr(VI toxicity.

Efficiencies and Optimization of Weak Base Anion Ion-Exchange Resin for Groundwater Hexavalent Chromium Removal at Hanford

International Nuclear Information System (INIS)

Nesham, Dean O.; Ivarson, Kristine A.; Hanson, James P.; Miller, Charles W.; Meyers, P.; Jaschke, Naomi M.

2014-01-01

The U.S. Department of Energy's (DOE's) contractor, CH2M HILL Plateau Remediation Company, has successfully converted a series of groundwater treatment facilities to use a new treatment resin that is delivering more than $3 million in annual cost savings and efficiency in treating groundwater contamination at the DOE Hanford Site in southeastern Washington State. During the production era, the nuclear reactors at the Hanford Site required a continuous supply of high-quality cooling water during operations. Cooling water consumption ranged from about 151,417 to 378,541 L/min (40,000 to 100,000 gal/min) per reactor, depending on specific operating conditions. Water from the Columbia River was filtered and treated chemically prior to use as cooling water, including the addition of sodium dichromate as a corrosion inhibitor. Hexavalent chromium was the primary component of the sodium dichromate and was introduced into the groundwater at the Hanford Site as a result of planned and unplanned discharges from the reactors starting in 1944. Groundwater contamination by hexavalent chromium and other contaminants related to nuclear reactor operations resulted in the need for groundwater remedial actions within the Hanford Site reactor areas. Beginning in 1995, groundwater treatment methods were evaluated, leading to the use of pump-and-treat facilities with ion exchange using Dowex 21K, a regenerable, strong-base anion exchange resin. This required regeneration of the resin, which was performed offsite. In 2008, DOE recognized that regulatory agreements would require significant expansion for the groundwater chromium treatment capacity. As a result, CH2M HILL performed testing at the Hanford Site in 2009 and 2010 to demonstrate resin performance in the specific groundwater chemistry at different waste sites. The testing demonstrated that a weak-base anion, single-use resin, specifically ResinTech SIR-700 ®, was effective at removing chromium, had a significantly higher

AN IN SITU PERMEABLE REACTIVE BARRIER FOR THE TREATMENT OF HEXAVALENT CHROMIUM AND TRICHLOROETHYLENE IN GROUNDWATER:VOLUME 2 PERFORMANCE MONITORING

Science.gov (United States)

A 46 m long, 7.3 m deep, and 0.6 m wide permeable subsurface reactive wall was installed at the U.S. Coast Guard (USCG) Support Center, near Elizabeth City, North Carolina, in June 1996. The reactive wall was designed to remediate hexavalent chromium [Cr(VI)] contaminated ground ...

Stabilization of Plutonium in Subsurface Environments via Microbial Reduction and Biofilm Formation

International Nuclear Information System (INIS)

Hakim Boukhalfa; Gary A. Icopini; Sean D. Reilly; Mary P. Neu

2007-01-01

Plutonium has a long half-life (2.4 x 10 4 years) and is of concern because of its chemical and radiological toxicity, high-energy alpha radioactive decay. A full understanding of its speciation and interactions with environmental processes is required in order to predict, contain, or remediate contaminated sites. Under aerobic conditions Pu is sparingly soluble, existing primarily in its tetravalent oxidation state. To the extent that pentavalent and hexavalent complexes and small colloidal species form they will increase the solubility and resultant mobility from contamination sources. There is evidence that in both marine environments and brines substantial fractions of the plutonium in solution is present as hexavalent plutonyl, PuO 2 2+

Special Advanced Studies for Pollution Prevention. Delivery Order 0065: The Monitor - Spring 2001

Science.gov (United States)

2001-06-01

coating) baths by remov- ing trace contaminant metals as well as restoring and maintaining the hexavalent chromium or ferric species. The oxidizing...power for the process acid is restored by oxidation (trivalent chromium to hexavalent chromium or ferrous to ferric) at the anode. Other sources of...selection to the application. UF membranes are suitable for particles in the molecular range of 0.1-0.01microns. Microfiltration membranes are similar

A microbial-mineralization-inspired approach for synthesis of manganese oxide nanostructures with controlled oxidation states and morphologies

Energy Technology Data Exchange (ETDEWEB)

Oba, Manabu; Oaki, Yuya; Imai, Hiroaki [Department of Applied Chemistry, Faculty of Science and Technology, Keio University, 3-14-1 Hiyoshi, Kohoku-ku, Yokohama 223-8522 (Japan)

2010-12-21

Manganese oxide nanostructures are synthesized by a route inspired by microbial mineralization in nature. The combination of organic molecules, which include antioxidizing and chelating agents, facilitates the parallel control of oxidation states and morphologies in an aqueous solution at room temperature. Divalent manganese hydroxide (Mn(OH){sub 2}) is selectively obtained as a stable dried powder by using a combination of ascorbic acid as an antioxidizing agent and other organic molecules with the ability to chelate to manganese ions. The topotactic oxidation of the resultant Mn(OH){sub 2} leads to the selective formation of trivalent manganese oxyhydroxide ({beta}-MnOOH) and trivalent/tetravalent sodium manganese oxide (birnessite, Na{sub 0.55}Mn{sub 2}O{sub 4}.1.5H{sub 2}O). For microbial mineralization in nature, similar synthetic routes via intermediates have been proposed in earlier works. Therefore, these synthetic routes, which include in the present study the parallel control over oxidation states and morphologies of manganese oxides, can be regarded as new biomimetic routes for synthesis of transition metal oxide nanostructures. As a potential application, it is demonstrated that the resultant {beta}-MnOOH nanostructures perform as a cathode material for lithium ion batteries. (Copyright copyright 2010 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Application of dolochar in the removal of cadmium and hexavalent chromium ions from aqueous solutions

Energy Technology Data Exchange (ETDEWEB)

Panda, L. [Council of Scientific and Industrial Research, Institute of Minerals and Materials Technology, Bhubaneswar 751013 (India); Das, B., E-mail: bdas@immt.res.in [Council of Scientific and Industrial Research, Institute of Minerals and Materials Technology, Bhubaneswar 751013 (India); Rao, D.S.; Mishra, B.K. [Council of Scientific and Industrial Research, Institute of Minerals and Materials Technology, Bhubaneswar 751013 (India)

2011-08-30

Graphical abstract: Dolochar - a waste material from sponge iron industry, is put to test as an adsorbent for removal of cadmium and hexavalent chromium ions from aqueous solutions. The sample consists of lots of voids and pores. Batch adsorption experiments have indicated that, higher pH and temperature enhances sorption for cadmium ions. The adsorption for chromium is found better at acidic pH in comparison to alkaline pH. The adsorption is well fitted to Langmuir isotherm model compared to the Freundlich model indicating monolayer adsorption. The kinetics of adsorption better fit to pseudo second order model.. Display Omitted Highlights: {yields} Dolochar, a waste material is generated during the production of sponge iron. {yields} Dolochar consists of metallic iron, carbon, and lime bearing phases along with lots of voids and pores. {yields} It was found to be an good adsorbent for the removal of cadmium and hexavalent chromium ions from aqueous solutions. {yields} The adsorption follows Langmuir isotherm and kinetics of adsorption better fit of pseudo second order model. - Abstract: Dolochar, a waste material generated in sponge iron industry, is processed and put to test as an adsorbent for removal of Cd(II) and Cr(VI) ions from aqueous solutions. The dolochar samples were characterised to determine the different phases and their distribution by reflection microscopy. The analysis indicated that the sample consists of metallic iron, fused carbon, and Ca-Mg bearing phases (Ca-Mg-silicate-oxide) along with lots of voids and pores. The fixed carbon (FC) content of the material is 13.8% with a Langmuir surface area of 81.6 m{sup 2}/g and micropore area of 34.1 m{sup 2}/g. Batch adsorption experiments have been conducted to study the sorption behaviour of Cd(II) and Cr(VI) ions on dolochar as a function of particle size, contact time, adsorbent dosages, pH and temperature. It is observed that higher pH and temperature enhances sorption of Cd(II) ions. In contrast

Application of dolochar in the removal of cadmium and hexavalent chromium ions from aqueous solutions

International Nuclear Information System (INIS)

Panda, L.; Das, B.; Rao, D.S.; Mishra, B.K.

2011-01-01

Graphical abstract: Dolochar - a waste material from sponge iron industry, is put to test as an adsorbent for removal of cadmium and hexavalent chromium ions from aqueous solutions. The sample consists of lots of voids and pores. Batch adsorption experiments have indicated that, higher pH and temperature enhances sorption for cadmium ions. The adsorption for chromium is found better at acidic pH in comparison to alkaline pH. The adsorption is well fitted to Langmuir isotherm model compared to the Freundlich model indicating monolayer adsorption. The kinetics of adsorption better fit to pseudo second order model.. Display Omitted Highlights: → Dolochar, a waste material is generated during the production of sponge iron. → Dolochar consists of metallic iron, carbon, and lime bearing phases along with lots of voids and pores. → It was found to be an good adsorbent for the removal of cadmium and hexavalent chromium ions from aqueous solutions. → The adsorption follows Langmuir isotherm and kinetics of adsorption better fit of pseudo second order model. - Abstract: Dolochar, a waste material generated in sponge iron industry, is processed and put to test as an adsorbent for removal of Cd(II) and Cr(VI) ions from aqueous solutions. The dolochar samples were characterised to determine the different phases and their distribution by reflection microscopy. The analysis indicated that the sample consists of metallic iron, fused carbon, and Ca-Mg bearing phases (Ca-Mg-silicate-oxide) along with lots of voids and pores. The fixed carbon (FC) content of the material is 13.8% with a Langmuir surface area of 81.6 m 2 /g and micropore area of 34.1 m 2 /g. Batch adsorption experiments have been conducted to study the sorption behaviour of Cd(II) and Cr(VI) ions on dolochar as a function of particle size, contact time, adsorbent dosages, pH and temperature. It is observed that higher pH and temperature enhances sorption of Cd(II) ions. In contrast, the adsorption for Cr

Titanium dioxide–gold nanocomposite materials embedded in silicate sol–gel film catalyst for simultaneous photodegradation of hexavalent chromium and methylene blue

International Nuclear Information System (INIS)

Pandikumar, Alagarsamy; Ramaraj, Ramasamy

2012-01-01

Graphical abstract: Aminosilicate sol–gel supported TiO 2 –Au nanocomposite material photocatalyst was prepared by deposition–precipitation method and used for the simultaneous oxidation and reduction of methyelene blue dye and Cr(VI) ions. Highlights: ► The EDAS/(TiO 2 –Au) nps is used to design the solid-phase thin film photocatalyst. ► Au promotes the interfacial electron transfer from TiO 2 to Cr(VI) to form Cr(III). ► The holes produced at the TiO 2 oxidize the MB dye. ► The EDAS/(TiO 2 –Au) nps film was used for the simultaneous oxidation and reduction of toxic molecules. ► The photoinduced simultaneous redox process provides dual benefit for the environment remediation. - Abstract: Aminosilicate sol–gel supported titanium dioxide–gold (EDAS/(TiO 2 –Au) nps ) nanocomposite materials were synthesized by simple deposition–precipitation method and characterized. The photocatalytic oxidation and reduction activity of the EDAS/(TiO 2 –Au) nps film was evaluated using hexavalent chromium (Cr(VI)) and methylene blue (MB) dye under irradiation. The photocatalytic reduction of Cr(VI) to Cr(III) was studied in the presence of hole scavengers such as oxalic acid (OA) and methylene blue (MB). The photocatalytic degradation of MB was investigated in the presence and absence of Cr(VI). Presence of Au nps on the (TiO 2 ) nps surface and its dispersion in the silicate sol-gel film (EDAS/(TiO 2 –Au) nps ) improved the photocatalytic reduction of Cr(VI) and oxidation of MB due to the effective interfacial electron transfer from the conduction band of the TiO 2 to Au nps by minimizing the charge recombination process when compared to the TiO 2 and (TiO 2 –Au) nps in the absence of EDAS. The EDAS/(TiO 2 –Au) nps nanocomposite materials provided beneficial role in the environmental remediation and purification process through synergistic photocatalytic activity by an advanced oxidation–reduction processes.

Oxidatively generated DNA/RNA damage in psychological stress states

DEFF Research Database (Denmark)

Jørgensen, Anders

2013-01-01

age-related somatic disorders. The overall aim of the PhD project was to investigate the relation between psychopathology, psychological stress, stress hormone secretion and oxidatively generated DNA and RNA damage, as measured by the urinary excretion of markers of whole-body DNA/RNA oxidation (8...... between the 24 h urinary cortisol excretion and the excretion of 8-oxodG/8-oxoGuo, determined in the same samples. Collectively, the studies could not confirm an association between psychological stress and oxidative stress on nucleic acids. Systemic oxidatively generated DNA/RNA damage was increased......Both non-pathological psychological stress states and mental disorders are associated with molecular, cellular and epidemiological signs of accelerated aging. Oxidative stress on nucleic acids is a critical component of cellular and organismal aging, and a suggested pathogenic mechanism in several...

Safety and immunogenicity of the RIVM hexavalent meningococcal B vesicle vaccine for Rotterdam children aged 2-3 and 7-8

NARCIS (Netherlands)

Labadie J; Kleijn ED de; Lafeber AB; Mees MMM; Booy K; Groot R de; Omme GW van; Dijken H van; Kuipers AJ; Dobbelsteen G van den; Juttmann RE; Wala M; Alphen AJW van; Rumke HC; Sophia Kinderziekenhuis /; LVO

2000-01-01

This report documents the results of a randomised controlled phase-II clinical study into the safety and immunogenicity of the RIVM hexavalent MenB vesicle vaccine among 189 children aged 2-3 and 168 children aged 7-8 in the city of Rotterdam, the Netherlands. Two concentrations of the MenB vesicle

The problem of oxidation state stabilisation and some regularities of a Periodic system of the elements

International Nuclear Information System (INIS)

Kiselev, Yurii M; Tretyakov, Yuri D

1999-01-01

The general principles of the concept of oxidation state stabilisation are formulated. Problems associated with the preparation and provision of the highest valent forms of transition elements are considered. The empirical data concerning the synthesis of new compounds of rare-earth elements and d elements in unusually high oxidation states are analysed. The possibility of occurrence of the oxidation states + 9 and + 10 for some elements (for example, for iridium and platinum in tetraoxo ions) are discussed. Approaches to the realisation of these states are outlined and it is demonstrated that solid phases or matrices containing alkali metal cations are the most promising systems for the stabilisation of these high oxidation states. Selected thermodynamic features typical of metal halides and oxides and the regularities of the changes in the extreme oxidation states of d elements are considered. The bibliography includes 266 references.

Oxidation of Fe(II) in rainwater.

Science.gov (United States)

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.

Heterogeneous Oxidation of Atmospheric Organic Aerosol: Kinetics of Changes to the Amount and Oxidation State of Particle-Phase Organic Carbon.

Science.gov (United States)

Kroll, Jesse H; Lim, Christopher Y; Kessler, Sean H; Wilson, Kevin R

2015-11-05

Atmospheric oxidation reactions are known to affect the chemical composition of organic aerosol (OA) particles over timescales of several days, but the details of such oxidative aging reactions are poorly understood. In this study we examine the rates and products of a key class of aging reaction, the heterogeneous oxidation of particle-phase organic species by the gas-phase hydroxyl radical (OH). We compile and reanalyze a number of previous studies from our laboratories involving the oxidation of single-component organic particles. All kinetic and product data are described on a common basis, enabling a straightforward comparison among different chemical systems and experimental conditions. Oxidation chemistry is described in terms of changes to key ensemble properties of the OA, rather than to its detailed molecular composition, focusing on two quantities in particular, the amount and the oxidation state of the particle-phase carbon. Heterogeneous oxidation increases the oxidation state of particulate carbon, with the rate of increase determined by the detailed chemical mechanism. At the same time, the amount of particle-phase carbon decreases with oxidation, due to fragmentation (C-C scission) reactions that form small, volatile products that escape to the gas phase. In contrast to the oxidation state increase, the rate of carbon loss is nearly uniform among most systems studied. Extrapolation of these results to atmospheric conditions indicates that heterogeneous oxidation can have a substantial effect on the amount and composition of atmospheric OA over timescales of several days, a prediction that is broadly in line with available measurements of OA evolution over such long timescales. In particular, 3-13% of particle-phase carbon is lost to the gas phase after one week of heterogeneous oxidation. Our results indicate that oxidative aging represents an important sink for particulate organic carbon, and more generally that fragmentation reactions play a major

Precursor preparation for Ca-Al layered double hydroxide to remove hexavalent chromium coexisting with calcium and magnesium chlorides

Energy Technology Data Exchange (ETDEWEB)

Zhong, Lihua; He, Xiaoman; Qu, Jun; Li, Xuewei; Lei, Zhiwu; Zhang, Qiwu [School of Resources and Environment Engineering, Wuhan University of Technology, Wuhan 430070 (China); Liu, Xinzhong [College of Ecological Environment and Urban Construction, Fujian University of Technology, Fuzhou 350118 (China)

2017-01-15

Al(OH){sub 3} and Ca(OH){sub 2} powders are co-ground to prepare a precursor which hydrates into a layered double hydroxide (LDH) phase by agitation in aqueous solution with target hexavalent chromium (Cr(VI)) at room temperature, to achieve an obvious improvement in removal efficiency of Cr(VI) through an easy incorporation into the structure. Although the prepared precursor transforms into LDH phases also when agitated in the solutions of calcium and magnesium chlorides, it incorporates Cr(VI) preferentially to the chloride salts when they coexist. The adsorption isotherm and kinetic studies show that the phenomena occurring on the Al-Ca precursor fit a pseudo-second-order kinetics with a Langmuir adsorption capacity of 59.45 mg/g. Besides, characterizations of the prepared precursor and the samples after adsorption are also performed by X-ray diffraction (XRD), Fourier transform infrared (FT-IR), Transmission electron microscope (TEM) to understand the reason of the preferential incorporation of Cr(VI) to the coexisting chloride salts during the LDH phase formation. - Graphical abstract: Activated Ca-Al hydroxides (C{sub 3}A) transformed into Ca-Al-OH compound when agitated in water. Ca-Al precursor (C{sub 3}A) was agitated in a hexavalent chromium (Cr(VI)) solution to form Al-Ca-CrO{sub 4} LDH product. Ca-Al-CrO{sub 4} LDH phase occurred preferentially to Ca-Al-MCl{sub 2} LDH phases in the solutions of calcium and magnesium chlorides, it incorporates Cr(VI) preferentially to the chloride salts when they coexist. - Highlights: • Activated Ca-Al hydroxides transformed into LDH when agitated in water with some inorganic substances. • Hexavalent Cr was incorporated in the LDH structure at high adsorption capacity. • Ca-Al-Cr LDH phase occurred preferentially to Ca-Al-MCl{sub 2} LDH phases with coexistence. • The prepared Ca-Al hydroxides had high performance as adsorbent even with high salinity of the solution.

Precursor preparation for Ca-Al layered double hydroxide to remove hexavalent chromium coexisting with calcium and magnesium chlorides

International Nuclear Information System (INIS)

Zhong, Lihua; He, Xiaoman; Qu, Jun; Li, Xuewei; Lei, Zhiwu; Zhang, Qiwu; Liu, Xinzhong

2017-01-01

Al(OH) 3 and Ca(OH) 2 powders are co-ground to prepare a precursor which hydrates into a layered double hydroxide (LDH) phase by agitation in aqueous solution with target hexavalent chromium (Cr(VI)) at room temperature, to achieve an obvious improvement in removal efficiency of Cr(VI) through an easy incorporation into the structure. Although the prepared precursor transforms into LDH phases also when agitated in the solutions of calcium and magnesium chlorides, it incorporates Cr(VI) preferentially to the chloride salts when they coexist. The adsorption isotherm and kinetic studies show that the phenomena occurring on the Al-Ca precursor fit a pseudo-second-order kinetics with a Langmuir adsorption capacity of 59.45 mg/g. Besides, characterizations of the prepared precursor and the samples after adsorption are also performed by X-ray diffraction (XRD), Fourier transform infrared (FT-IR), Transmission electron microscope (TEM) to understand the reason of the preferential incorporation of Cr(VI) to the coexisting chloride salts during the LDH phase formation. - Graphical abstract: Activated Ca-Al hydroxides (C 3 A) transformed into Ca-Al-OH compound when agitated in water. Ca-Al precursor (C 3 A) was agitated in a hexavalent chromium (Cr(VI)) solution to form Al-Ca-CrO 4 LDH product. Ca-Al-CrO 4 LDH phase occurred preferentially to Ca-Al-MCl 2 LDH phases in the solutions of calcium and magnesium chlorides, it incorporates Cr(VI) preferentially to the chloride salts when they coexist. - Highlights: • Activated Ca-Al hydroxides transformed into LDH when agitated in water with some inorganic substances. • Hexavalent Cr was incorporated in the LDH structure at high adsorption capacity. • Ca-Al-Cr LDH phase occurred preferentially to Ca-Al-MCl 2 LDH phases with coexistence. • The prepared Ca-Al hydroxides had high performance as adsorbent even with high salinity of the solution.

Characterization of Interface State in Silicon Carbide Metal Oxide Semiconductor Capacitors

Science.gov (United States)

Kao, Wei-Chieh

Silicon carbide (SiC) has always been considered as an excellent material for high temperature and high power devices. Since SiC is the only compound semiconductor whose native oxide is silicon dioxide (SiO2), it puts SiC in a unique position. Although SiC metal oxide semiconductor (MOS) technology has made significant progress in recent years, there are still a number of issues to be overcome before more commercial SiC devices can enter the market. The prevailing issues surrounding SiC MOSFET devices are the low channel mobility, the low quality of the oxide layer and the high interface state density at the SiC/SiO2 interface. Consequently, there is a need for research to be performed in order to have a better understanding of the factors causing the poor SiC/SiO2 interface properties. In this work, we investigated the generation lifetime in SiC materials by using the pulsed metal oxide semiconductor (MOS) capacitor method and measured the interface state density distribution at the SiC/SiO2 interface by using the conductance measurement and the high-low frequency capacitance technique. These measurement techniques have been performed on n-type and p-type SiC MOS capacitors. In the course of our investigation, we observed fast interface states at semiconductor-dielectric interfaces in SiC MOS capacitors that underwent three different interface passivation processes, such states were detected in the nitrided samples but not observed in PSG-passivated samples. This result indicate that the lack of fast states at PSG-passivated interface is one of the main reasons for higher channel mobility in PSG MOSFETs. In addition, the effect of mobile ions in the oxide on the response time of interface states has been investigated. In the last chapter we propose additional methods of investigation that can help elucidate the origin of the particular interface states, enabling a more complete understanding of the SiC/SiO2 material system.

Elevated Frequencies of Micronuclei and other Nuclear Abnormalities of Chrome Plating Workers Occupationally Exposed to Hexavalent Chromium

OpenAIRE

Sudha, S; Kripa, SK; Shibily, P; Shyn, J

2011-01-01

Background Biomonitoring provides a useful tool to estimate the genetic risk from exposure to genotoxic agents. The aim of this study was to assess the potential cytogenetic damage associated with occupational exposure to hexavalent chromium by using micronuclei (MN) as a biomarker. Methods This was a cross-sectional study and all participants were males. Both the exposed and control individuals were selected from Coimbatore, Southern India. Exfoliated buccal cells from 44 chrome plating work...

Enrichment mechanisms of tellurium in ferromanganese crusts

Science.gov (United States)

Sakaguchi, A.; Sugiyama, T.; Usui, A.; Takahashi, Y.

2012-04-01

Marine ferromanganese crusts (FMCs) consist of iron (Fe) hydroxides and manganese (Mn) oxides with various minor and trace elements. Especially for tellurium (Te), which is recognized as one of the rare metals, it has been reported that this element is concentrated about 105 times in FMCs compared with earth's crust, and the host phase might be Fe (oxy)hydroxide (Hein et al., 2003). Actually, in our previous study, the high concentration of Te in very surface layers of FMCs was found from the top to halfway down of a seamount in the Pacific Ocean. However, the concentration of Te in surface layers through the seamount showed good correlation with that of Mn instead of Fe. In this study, we attempted to clarify the enrichment mechanism of Te in FMCs with some methods including X-ray absorption fine structure (XAFS) technique for synthesised /natural samples. Seventeen FMC samples were collected from the Takuyo-Daigo seamount, from 950 m (summit) to 3000 m in water depth, with hyper-dolphin (remotely operated vehicle) equipped with live video camera and manipulators. The growth rates of all FMC samples were estimated to be about 3 mm/Ma. Very surface layer (less than 1 mm) of all FMC was analyzed with XRD and XAFS to confirm the mineral composition and speciation of Te. Furthermore, to serve as an aid to clarify the adsorption mechanism of Te on FMCs, distribution coefficients (Kd) and oxidation states were determined through the adsorption experiments of Te(IV) and Te(VI) on ferrihydrite and δ-MnO2. In all the experiments, pH and ionic strength were adjusted to pH 7.5 and 0.7 M, respectively. The oxidation state of Te in water phase was determined with HPLC-ICP-MS. As for the analysis of oxidation and adsorption states on the solid phase, XAFS was employed. The major mineral composition of Fe and Mn had no significant variation through the water depth of Takuyo-Daigo seamount. The oxidation state of Te in all samples showed hexavalent, and there was no significant

Extracellular redox state: refining the definition of oxidative stress in aging.

Science.gov (United States)

Jones, Dean P

2006-01-01

Oxidative stress in aging can result from an imbalance of prooxidants and antioxidants with excessive, destructive free radical chemistry. Thiol systems are important in the control of these processes, both by protecting against damage and serving in redox signaling mechanisms to sense danger and repair the damage. Studies by a number of research groups in collaboration with the Emory Clinical Biomarkers Laboratory show that the redox state of the central tissue antioxidant, glutathione (GSH), can be measured in human plasma and provides a quantitative systemic indicator of oxidative stress. Plasma GSH/GSSG redox in humans becomes oxidized with age, in response to chemotherapy, as a consequence of cigarette smoking, and in association with common age-related diseases (e.g., type 2 diabetes, cardiovascular disease). However, the GSH/GSSG redox is not equilibrated with the larger plasma cysteine/cystine (Cys/CySS) pool, and the Cys/CySS redox varies with age in a pattern that is distinct from that of GSH/GSSG redox. Furthermore, in vitro studies show that variation in Cys/CySS redox over the range found in vivo affects signaling pathways, which control cell proliferation and oxidant-induced apoptosis. The results point to the conclusion that free radical scavenging antioxidants are of increased importance when thiol/disulfide redox states are oxidized. Because thiol/disulfide redox states, per se, function in redox signaling and control as well as antioxidant protection, GSH/GSSG and Cys/CySS redox states may provide central parameters to link environmental influences and progression of changes associated with aging.

How different oxidation states of crystalline myoglobin are influenced by X-rays.

Science.gov (United States)

Hersleth, Hans-Petter; Andersson, K Kristoffer

2011-06-01

X-ray induced radiation damage of protein crystals is well known to occur even at cryogenic temperatures. Redox active sites like metal sites seem especially vulnerable for these radiation-induced reductions. It is essential to know correctly the oxidation state of metal sites in protein crystal structures to be able to interpret the structure-function relation. Through previous structural studies, we have tried to characterise and understand the reactions between myoglobin and peroxides. These reaction intermediates are relevant because myoglobin is proposed to take part as scavenger of reactive oxygen species during oxidative stress, and because these intermediates are similar among the haem peroxidases and oxygenases. We have in our previous studies shown that these different myoglobin states are influenced by the X-rays used. In this study, we have in detail investigated the impact that X-rays have on these different oxidation states of myoglobin. An underlying goal has been to find a way to be able to determine mostly unreduced states. We have by using single-crystal light absorption spectroscopy found that the different oxidation states of myoglobin are to a different extent influenced by the X-rays (e.g. ferric Fe(III) myoglobin is faster reduced than ferryl Fe(IV)═O myoglobin). We observe that the higher oxidation states are not reduced to normal ferrous Fe(II) or ferric Fe(III) states, but end up in some intermediate and possibly artificial states. For ferric myoglobin, it seems that annealing of the radiation-induced/reduced state can reversibly more or less give the starting point (ferric myoglobin). Both scavengers and different dose-rates might influence to which extent the different states are affected by the X-rays. Our study shows that it is essential to do a time/dose monitoring of the influence X-rays have on each specific redox-state with spectroscopic techniques like single-crystal light absorption spectroscopy. This will determine to which

Optoelectronic properties of valence-state-controlled amorphous niobium oxide

Science.gov (United States)

Onozato, Takaki; Katase, Takayoshi; Yamamoto, Akira; Katayama, Shota; Matsushima, Koichi; Itagaki, Naho; Yoshida, Hisao; Ohta, Hiromichi

2016-06-01

In order to understand the optoelectronic properties of amorphous niobium oxide (a-NbO x ), we have investigated the valence states, local structures, electrical resistivity, and optical absorption of a-NbO x thin films with various oxygen contents. It was found that the valence states of Nb ion in a-NbO x films can be controlled from 5+  to 4+  by reducing oxygen pressure during film deposition at room temperature, together with changing the oxide-ion arrangement around Nb ion from Nb2O5-like to NbO2-like local structure. As a result, a four orders of magnitude reduction in the electrical resistivity of a-NbO x films was observed with decreasing oxygen content, due to the carrier generation caused by the appearance and increase of an oxygen-vacancy-related subgap state working as an electron donor. The tunable optoelectronic properties of a-NbO x films by valence-state-control with oxygen-vacancy formation will be useful for potential flexible optoelectronic device applications.

Chronic exposure to sublethal hexavalent chromium affects organ histopathology and serum cortisol profile of a teleost, Channa punctatus (Bloch)

International Nuclear Information System (INIS)

Mishra, Ashish K.; Mohanty, Banalata

2009-01-01

Effects of chronic exposures (one and two months) to sublethal doses of hexavalent chromium (2 and 4 mg/L potassium dichromate) on organ histopathology and serum cortisol profile were investigated and their overall impact on growth and behavior of a teleost fish, Channa punctatus was elucidated. Histopathological lesions were distinct in the vital organs gill, kidney and liver. The gill lamellae became lifted, fused, and showed oedema. Hyperplasia and hypertrophy of lamellar epithelial cells were distinct with desquamation. Hypertrophy of epithelial cells of renal tubules and reduction in tubular lumens were observed in the trunk kidney. The atrophy of the head kidney interrenal cells and decreased serum cortisol level indicated exhaustion of interrenal activity. Hepatocyte vacuolization and shrinkage, nuclear pyknosis and increase of sinusoidal spaces were observed in the liver. Abnormal behavioral patterns and reduced growth rate were also noticed in the exposed fish. The chronic hexavalent chromium exposure thus by affecting histopathology of gill, kidney (including interrenal tissue) and liver could impair the vital functions of respiration, excretion, metabolic regulation and maintenance of stress homeostasis which in the long-run may pose serious threat to fish health and affect their population.

Chronic exposure to sublethal hexavalent chromium affects organ histopathology and serum cortisol profile of a teleost, Channa punctatus (Bloch)

Energy Technology Data Exchange (ETDEWEB)

Mishra, Ashish K. [Department of Zoology, University of Allahabad, Allahabad-211002 (India); Mohanty, Banalata, E-mail: drbana_mohanty@rediffmail.com [Department of Zoology, University of Allahabad, Allahabad-211002 (India)

2009-09-01

Effects of chronic exposures (one and two months) to sublethal doses of hexavalent chromium (2 and 4 mg/L potassium dichromate) on organ histopathology and serum cortisol profile were investigated and their overall impact on growth and behavior of a teleost fish, Channa punctatus was elucidated. Histopathological lesions were distinct in the vital organs gill, kidney and liver. The gill lamellae became lifted, fused, and showed oedema. Hyperplasia and hypertrophy of lamellar epithelial cells were distinct with desquamation. Hypertrophy of epithelial cells of renal tubules and reduction in tubular lumens were observed in the trunk kidney. The atrophy of the head kidney interrenal cells and decreased serum cortisol level indicated exhaustion of interrenal activity. Hepatocyte vacuolization and shrinkage, nuclear pyknosis and increase of sinusoidal spaces were observed in the liver. Abnormal behavioral patterns and reduced growth rate were also noticed in the exposed fish. The chronic hexavalent chromium exposure thus by affecting histopathology of gill, kidney (including interrenal tissue) and liver could impair the vital functions of respiration, excretion, metabolic regulation and maintenance of stress homeostasis which in the long-run may pose serious threat to fish health and affect their population.

Oxidation of extracellular cysteine/cystine redox state in bleomycin-induced lung fibrosis.

Science.gov (United States)

Iyer, Smita S; Ramirez, Allan M; Ritzenthaler, Jeffrey D; Torres-Gonzalez, Edilson; Roser-Page, Susanne; Mora, Ana L; Brigham, Kenneth L; Jones, Dean P; Roman, Jesse; Rojas, Mauricio

2009-01-01

Several lines of evidence indicate that depletion of glutathione (GSH), a critical thiol antioxidant, is associated with the pathogenesis of idiopathic pulmonary fibrosis (IPF). However, GSH synthesis depends on the amino acid cysteine (Cys), and relatively little is known about the regulation of Cys in fibrosis. Cys and its disulfide, cystine (CySS), constitute the most abundant low-molecular weight thiol/disulfide redox couple in the plasma, and the Cys/CySS redox state (E(h) Cys/CySS) is oxidized in association with age and smoking, known risk factors for IPF. Furthermore, oxidized E(h) Cys/CySS in the culture media of lung fibroblasts stimulates proliferation and expression of transitional matrix components. The present study was undertaken to determine whether bleomycin-induced lung fibrosis is associated with a decrease in Cys and/or an oxidation of the Cys/CySS redox state and to determine whether these changes were associated with changes in E(h) GSH/glutathione disulfide (GSSG). We observed distinct effects on plasma GSH and Cys redox systems during the progression of bleomycin-induced lung injury. Plasma E(h) GSH/GSSG was selectively oxidized during the proinflammatory phase, whereas oxidation of E(h) Cys/CySS occurred at the fibrotic phase. In the epithelial lining fluid, oxidation of E(h) Cys/CySS was due to decreased food intake. Thus the data show that decreased precursor availability and enhanced oxidation of Cys each contribute to the oxidation of extracellular Cys/CySS redox state in bleomycin-induced lung fibrosis.

Lipid peroxidation in workers exposed to hexavalent chromium.

Science.gov (United States)

Huang, Y L; Chen, C Y; Sheu, J Y; Chuang, I C; Pan, J H; Lin, T H

1999-02-26

The aim of this study was to investigate whether exposure to hexavalent chromium induces lipid peroxidation in human. This study involved 25 chrome-plating factory workers and a reference group of 28 control subjects. The whole-blood and urinary chromium concentrations were determined by graphite furnace atomic absorption spectrophotometry. Malondialdehyde (MDA), the product of lipid peroxidation, was determined by high-performance liquid chromatography, and the activities of protective enzymes were measured by ultraviolet-visible spectrophotometry. In the chrome-plating workers, the mean concentrations of chromium in blood and urine were 5.98 microg/L and 5.25 microg/g creatinine, respectively; the mean concentrations of MDA in blood and urine were 1.7 micromol/L and 2.24 micromol/g creatinine. The concentrations of both chromium and MDA in blood and urine were significantly higher in the chromium-exposed workers. The activities of superoxide dismutase (SOD), glutathione peroxidase (GPX), and catalase (CAT) were not markedly different between control and exposed workers. Data suggest that MDA may be used as a biomarker for occupational chromium exposure. Antioxidant enzymic activities are not a suitable marker for chromium exposure.

Oxidation state analyses of uranium with emphasis on chemical speciation in geological media

International Nuclear Information System (INIS)

Ervanne, H.

2004-01-01

This thesis focuses on chemical methods suitable for the determination of uranium redox species in geological materials. Nd-coprecipitation method was studied for the determination of uranium oxidation states in ground waters. This method is ideally suited for the separation of uranium oxidation states in the field, which means that problems associated with the instability of U(IV) during transport are avoided. An alternative method, such as ion exchange, is recommended for the analysis of high saline and calcium- and iron-rich ground waters. U(IV)/Utot was 2.8-7.2% in ground waters in oxidizing conditions and 60-93% in anoxic conditions. From thermodynamic model calculations applied to results from anoxic ground waters it was concluded that uranium can act as redox buffer in granitic ground waters. An ion exchange method was developed for the analysis of uranium oxidation states in different solid materials of geological origin. These included uranium minerals, uraniumbearing minerals, fracture coatings and bulk rock. U(IV)/Utot was 50-70% in uraninites, 5.8-8.7% in secondary uranium minerals, 15-49% in different fracture coatings and 64- 77% in samples from deep bedrock. In the uranium-bearing minerals, U(IV)/Utot was 33-43% (allanites), 5.9% (fergusonite) and 93% (monazite). Although the ion exchange method gave reliable results, there is a risk for the conversion of uranium oxidation states during analysis of heterogeneous samples due to the redox reactions that take place in the presence of some iron compounds. This risk was investigated in a study of several common iron-bearing minerals. The risk for conversion of uranium oxidation states can be screened by sample selection and minimized with use of a redox buffer compound such as polyacrylic acid (PAA). In studies of several carboxylic acids, PAA was found to be the most suitable for extending the application of the method. The stability of uranium oxidation states during analysis and the selectivity

AN IN-SITU PERMEABLE REACTIVE BARRIER FOR THE TREATMENT OF HEXAVALENT CHROMIUM AND TRICHLOROETHYLENE IN GROUND WATER: VOLUME 1 DESIGN AND INSTALLATION

Science.gov (United States)

A 46 m long, 7.3 m deep, and 0.6 m wide permeable subsurface reactive wall was installed at the U.S. Coast Guard (USCG) Support Center, near Elizabeth City, North Carolina, in June 1996. The reactive wall was designed to remediate hexavalent chromium [Cr(VI)] contaminated ground ...

Corrosion-product transport, oxidation state and remedial measures

International Nuclear Information System (INIS)

Sawicki, J.A.; Brett, M.E.; Tapping, R.L.

1998-10-01

The issues associated with monitoring and controlling corrosion-product transport (CPT) in the balance-of-plant (BOP) and steam generators (SG) of CANDU stations are briefly reviewed. Efforts are focused on minimizing corrosion of carbon steel, which is used extensively in the CANDU primary and secondary systems. Emphasis is placed on the corrosion-product oxidation state as a monitor of water chemistry effectiveness and as a monitor of system corrosion effects. The discussion is based mostly on the results of observations from Ontario Hydro plants, and their comparisons with pressurized-water reactors. The effects of low oxygen and elevated hydrazine chemistry are reviewed, as well as the effects of layup and various startup conditions. Progress in monitoring electrochemical potential (ECP) at Ontario Hydro plants and its relationship to the oxidation state of corrosion products is reviewed. Observations on CPT on the primary side of SGs are also discussed. (author)

Generalized molybdenum oxide surface chemical state XPS determination via informed amorphous sample model

Energy Technology Data Exchange (ETDEWEB)

Baltrusaitis, Jonas, E-mail: job314@lehigh.edu [Department of Chemical Engineering, Lehigh University, B336 Iacocca Hall, 111 Research Drive, Bethlehem, PA 18015 (United States); PhotoCatalytic Synthesis group, MESA+ Institute for Nanotechnology, Faculty of Science and Technology, University of Twente, Meander 229, P.O. Box 217, 7500 AE Enschede (Netherlands); Mendoza-Sanchez, Beatriz [CRANN, Chemistry School, Trinity College Dublin, Dublin (Ireland); Fernandez, Vincent [Institut des Matériaux Jean Rouxel, 2 rue de la Houssinière, BP 32229, F-44322 Nantes Cedex 3 (France); Veenstra, Rick [PhotoCatalytic Synthesis group, MESA+ Institute for Nanotechnology, Faculty of Science and Technology, University of Twente, Meander 229, P.O. Box 217, 7500 AE Enschede (Netherlands); Dukstiene, Nijole [Department of Physical and Inorganic Chemistry, Kaunas University of Technology, Radvilenu pl. 19, LT-50254 Kaunas (Lithuania); Roberts, Adam [Kratos Analytical Ltd, Trafford Wharf Road, Wharfside, Manchester, M17 1GP (United Kingdom); Fairley, Neal [Casa Software Ltd, Bay House, 5 Grosvenor Terrace, Teignmouth, Devon TQ14 8NE (United Kingdom)

2015-01-30

Highlights: • We analyzed and modeled spectral envelopes of complex molybdenum oxides. • Molybdenum oxide films of varying valence and crystallinity were synthesized. • MoO{sub 3} and MoO{sub 2} line shapes from experimental data were created. • Informed amorphous sample model (IASM) developed. • Amorphous molybdenum oxide XPS envelopes were interpreted. - Abstract: Accurate elemental oxidation state determination for the outer surface of a complex material is of crucial importance in many science and engineering disciplines, including chemistry, fundamental and applied surface science, catalysis, semiconductors and many others. X-ray photoelectron spectroscopy (XPS) is the primary tool used for this purpose. The spectral data obtained, however, is often very complex and can be subject to incorrect interpretation. Unlike traditional XPS spectra fitting procedures using purely synthetic spectral components, here we develop and present an XPS data processing method based on vector analysis that allows creating XPS spectral components by incorporating key information, obtained experimentally. XPS spectral data, obtained from series of molybdenum oxide samples with varying oxidation states and degree of crystallinity, were processed using this method and the corresponding oxidation states present, as well as their relative distribution was elucidated. It was shown that monitoring the evolution of the chemistry and crystal structure of a molybdenum oxide sample due to an invasive X-ray probe could be used to infer solutions to complex spectral envelopes.

Analytical determination of plutonium in the presence of complexing agents

International Nuclear Information System (INIS)

Nebel', D.

1975-01-01

The complexing of Pu(4) and Pu(6) with citrate and lactate were studied to establish possibilities which are provided by the complexing for analytical determination of plutonium in a solution. Plutonium in the sample analyzed is preliminarily reduced up to trivalent state. Then trivalent plutonium is oxidized up to tetravalent on the platinum electrode at +1.05 V. To avoid further oxidation complexing agents are added. The value of pH=2-4 is maintained to stabilize the oxidation degree. If hexavalent plutonium should be obtained, the oxidation is performed at the voltage of +1.5 V in the absence of complexing agents. Based on a detailed study of absorption spectra of plutonium complexes of various oxidation degrees it is stated that the most suitable for analytical purposes is the oxidation degree of Pu=4

The oxidation states of elements in pure and Ca-doped BiCuSeO thermoelectric oxides

International Nuclear Information System (INIS)

Hsiao, Chun-Lung; Qi, Xiaoding

2016-01-01

Bi 1−x Ca x CuSeO (x = 0–0.3) was synthesized at 650 °C in an air-tight system flowing with pure argon. The Ca doping resulted in an increase in the thermoelectric figure of merit (ZT) as the consequence of increased carrier concentration. X-ray photoelectron spectroscopy (XPS) was carried out to check the oxidation states in Bi 1−x Ca x CuSeO. The results indicated that in addition to the expected Bi 3+ and Cu 1+ , there existed Bi 2+ and Cu 2+ in the undoped BiCuSeO, whereas in the Ca-doped BiCuSeO, Bi 4+ , Cu 3+ and Cu 2+ were observed. The Ca dopant was confirmed to be in the 2+ oxidation state. Two broad peaks centered at 54.22 and 58.59 eV were recorded in the vicinity around the binding energy of Se 3d. The former is often observed in the Se-containing intermetallics while the latter is often found in the Se-containing oxides, indicating that along with the expected Se–Cu bonding, a bonding between Se and O may also exist. Based on the XPS results, the charge compensation mechanisms were proposed for Bi 1−x Ca x CuSeO, which may shed some light on the origins of charge carriers. BiCuSeO based oxides have recently be discovered to have a large ZT comparable to the best alloys currently in use, because of the large Seebeck coefficient and small thermal conductivity. However, their electrical conductivity is lower compared to the best thermoelectrics. This work may provide some hints for the further improvement of ZT in BiCuSeO based oxides. - Graphical abstract: The oxidation states, charge compensation mechanisms, and origins of charge carriers in Bi 1−x Ca x CuSeO thermoelectrics. Display Omitted

Treatment of hexavalent chromium Cr (VI) in tanning effluent

International Nuclear Information System (INIS)

Ahmed, I.; Ali, S.

1999-01-01

Most common chemical used in chrome tanning is basic chromium sulphate (BCS). Manufacturing of BCS involves many steps producing liquid waste. Waste generated at every stage contains Cr (VI), which must be reduced to Cr (III) before being disposed to the environment. Different methods were studied for the reduction of toxic Cr (III). Pickle liquor (waste of electroplating industry) can also be used for the reduction of hexavalent chromium Cr (vi) along with other reducing materials / chemicals. In an electroplating process metal is treated with HCl or H/sub 2/SO/sub 4/ to remove scales and rust, the pickled items are then washed with water, washing contains FeCl/sub 2/ or fees/sub 4/ respectively called pickle liquor. During waste treatment pH adjustment to 6.0 - 9.0 and settling the sludge, is discharged to the lagoon. The sludge obtained is dried and disposed off in landfills. Other reducing agents like sodium bisulphite and sulfur dioxide were also studied, but pickle liquor was found to be more effective and economical. (author)

Hexavalent chromium is cytotoxic and genotoxic to American alligator cells.

Science.gov (United States)

Wise, Sandra S; Wise, Catherine; Xie, Hong; Guillette, Louis J; Zhu, Cairong; Wise, John Pierce; Wise, John Pierce

2016-02-01

Metals are a common pollutant in the aquatic ecosystem. With global climate change, these levels are anticipated to rise as lower pH levels allow sediment bound metals to be released. The American alligator (Alligator mississippiensis) is an apex predator in the aquatic ecosystem and is considered a keystone species; as such it serves as a suitable monitor for localized pollution. One metal of increasing concern is hexavalent chromium (Cr(VI)). It is present in the aquatic environment and is a known human carcinogen and reproductive toxicant. We measured the cytotoxicity and genotoxicity of Cr(VI) in American alligator cells derived from scute tissue. We found that particulate and soluble Cr(VI) are both cytotoxic and genotoxic to alligator cells in a concentration-dependent manner. These data suggest that alligators may be used as a model for assessing the effects of environmental Cr(VI) contamination as well as for other metals of concern. Copyright © 2015 Elsevier B.V. All rights reserved.

A study of the process of desorption of hexavalent chromium

Directory of Open Access Journals (Sweden)

W.B. Amorim

2003-09-01

Full Text Available In this work the process of desorption of hexavalent chromium, a toxic metal ion, from the marine algae Sargassum sp, following biosorption experiments 2³ factorial design was studied. A technique was applied to three eluents: HCl, H2SO4 and EDTA. Three factors of importance were evaluated: concentration of eluent, the ratio between mass of biosorbent and volume of eluent (S/L and process time. A statistical analysis of the experimental results showed that the three variables evaluated are significant for all three eluents. The models for chromium desorption were validated, as the results agreed well with the observed values. Through use of the response surface methodology, a factorial design based optimization technique; it was possible to identify the most suitable eluent and the interval of values for the process variables that resulted in the most significant desorption of chromium, which is relevant information for work aiming at process optimization.

Reduction of Hexavalent Chromium Using Sorbaria sorbifolia Aqueous Leaf Extract

Directory of Open Access Journals (Sweden)

Shashi Prabha Dubey

2017-07-01

Full Text Available Aqueous plant leaves extract (PLE of an abundant shrub, Sorbaria sorbifolia, was explored for the reduction of hexavalent chromium, Cr(VI, to trivalent chromium, Cr(III. The effect of contact time, pH, PLE quantity, ionic strength, hardness, temperature and effective initial Cr(VI ion concentration were tested; Cr(VI reduction followed the pseudo-first order rate kinetics and maximum reduction was observed at pH 2. Significantly, Cr(VI reduction efficacies varied from 97 to 66% over the pH range of 2 to 10, which bodes well for PLE to be used for the reduction of Cr(VI also at a higher pH. PLE-mediated Cr(VI reduction displays considerable efficiency at various ionic strengths; however, hardness strongly affects the reduction ability. Higher temperature significantly enhances the Cr(VI reduction. This study reveals the potential use of PLE as a green reducing agent in aqueous extract for the efficient reduction of Cr(VI to Cr(III.

A Novel Early Warning System Based on a Sediment Microbial Fuel Cell for In Situ and Real Time Hexavalent Chromium Detection in Industrial Wastewater.

Science.gov (United States)

Zhao, Shuai; Liu, Pu; Niu, Yongyan; Chen, Zhengjun; Khan, Aman; Zhang, Pengyun; Li, Xiangkai

2018-02-22

Hexavalent chromium (Cr(VI)) is a well-known toxic heavy metal in industrial wastewater, but in situ and real time monitoring cannot be achieved by current methods used during industrial wastewater treatment processes. In this study, a Sediment Microbial Fuel Cell (SMFC) was used as a biosensor for in situ real-time monitoring of Cr(VI), which was the organic substrate is oxidized in the anode and Cr(VI) is reduced at the cathode simultaneously. The pH 6.4 and temperature 25 °C were optimal conditions for the operation. Under the optimal conditions, linearity (R² = 0.9935) of the generated voltage was observed in the Cr(VI) concentration range from 0.2 to 0.7 mg/L. The system showed high specificity for Cr(VI), as other co-existing ions such as Cu 2+ , Zn 2+ , and Pb 2+ did not interfere with Cr(VI) detection. In addition, when the sediment MFC-based biosensor was applied for measuring Cr(VI) in actual wastewater samples, a low deviation (real time in situ detection of Cr(VI) in industrial wastewaters.

Corrosion-product transport, oxidation state and remedial measures

International Nuclear Information System (INIS)

Sawicki, J.A.; Brett, M.E.; Tapping, R.L.

1998-01-01

The issues associated with monitoring and controlling corrosion-product transport (CPT) in the balance-of-plant (BOP) and steam generators (SG) of CANDU stations are briefly reviewed. The efforts are focused on minimizing corrosion of carbon steel, which is used extensively in the CANDU primary and secondary systems. Emphasis is placed on the corrosion-product oxidation state as a monitor of water chemistry effectiveness, and as a monitor of system corrosion effects. The discussion is based mostly on the results and observations from Ontario Hydro plants, and their comparisons with PWRs. The effects of low oxygen and elevated hydrazine chemistry are reviewed, as well as the effects of lay-up and various start-up conditions. Progress in monitoring electrochemical potential (ECP) at Ontario Hydro plants and its relationship to the oxidation state of corrosion products is reviewed. Observations on corrosion-product transport on the primary side of steam generators are also discussed. (author)

Reproductive toxicological aspects of chromium in males

International Nuclear Information System (INIS)

Ernst, E.

1994-01-01

To expand our present understanding of the effects of chromium on male fertility a number of studies were designed to achieve this through the use of chromium intoxicated experimental animals and through investigation of sexual hormones and sperm quality in welders. Also in view of the lack of an experimental model for effects of noxious substance on the epididymal spermatozoa the main objectives of the series of studies reviewed here were: A. To establish a model for evaluation of epididymal sperm count and motility in the rat. B. To investigate and compare the effects of tri- and hexavalent chromium on epididymal spermatozoa. Further to describe the effects of low-dose long-time exposure of rats to the most toxicological interesting chromium oxidative state - hexavalent chromium. C. By the use of autoradiography and γ-countinuing to expand the present knowledge on the distribution of chromium in the body with special reference to the male reproductive organs. D. To describe the effects of exposure to hexavalent chromium in welding fume on levels of sexual hormones and semen parameters in welders. (EG)

Combined abiotic and biotic in-situ reduction of hexavalent chromium in groundwater using nZVI and whey: A remedial pilot test

Czech Academy of Sciences Publication Activity Database

Němeček, J.; Pokorný, P.; Lacinová, L.; Černík, M.; Masopustová, Z.; Lhotský, O.; Filipová, Alena; Cajthaml, Tomáš

2015-01-01

Roč. 300, DEC 2015 (2015), s. 670-679 ISSN 0304-3894 R&D Projects: GA TA ČR TE01020218 Grant - others:Advanced Technologies and Innovation (CZ) CZ.1.05/2.1.00/01.0005 Institutional support: RVO:61388971 Keywords : Hexavalent chromium * nZVI * Geofixation Subject RIV: EE - Microbiology, Virology Impact factor: 4.836, year: 2015

Uranium Immobilization through Fe(II) bio-oxidation: A Column study

Energy Technology Data Exchange (ETDEWEB)

Coates, John D.

2009-09-14

Current research on the bioremediation of heavy metals and radionuclides is focused on the ability of reducing organisms to use these metals as alternative electron acceptors in the absence of oxygen and thus precipitate them out of solution. However, many aspects of this proposed scheme need to be resolved, not the least of which is the time frame of the treatment process. Once treatment is complete and the electron donor addition is halted, the system will ultimately revert back to an oxic state and potentially result in the abiotic reoxidation and remobilization of the immobilized metals. In addition, the possibility exists that the presence of more electropositive electron acceptors such as nitrate or oxygen will also stimulate the biological oxidation and remobilization of these contaminants. The selective nitrate-dependent biooxidation of added Fe(II) may offer an effective means of “capping off” and completing the attenuation of these contaminants in a reducing environment making the contaminants less accessible to abiotic and biotic reactions and allowing the system to naturally revert to an oxic state. Our previous DOE-NABIR funded studies demonstrated that radionuclides such as uranium and cobalt are rapidly removed from solution during the biogenic formation of Fe(III)-oxides. In the case of uranium, X-ray spectroscopy analysis indicated that the uranium was in the hexavalent form (normally soluble) and was bound to the precipitated Fe(III)-oxides thus demonstrating the bioremediative potential of this process. We also demonstrated that nitrate-dependent Fe(II)- oxidizing bacteria are prevalent in the sediment and groundwater samples collected from sites 1 and 2 and the background site of the NABIR FRC in Oakridge, TN. However, all of these studies were performed in batch experiments in the laboratory with pure cultures and although a significant amount was learned about the microbiology of nitrate-dependent bio-oxidation of Fe(II), the effects of

Synergistic extraction of hexavalent plutonium by HTTA and HPMBP using mono- and bi- functional neutral donors: a comparative study

International Nuclear Information System (INIS)

Lohithakshan, K.V.; Mithapara, P.D.; Pai, S.A.; Aggarwal, S.K.

1997-01-01

Thermodynamics and synergistic extraction of hexavalent plutonium were studied from HNO 3 medium (0.05M) with HTTA and HPMBP and various neutral donors viz. DPSO, TBP, TOPO (monofunctional) and DBDECMP, DHDECMP, CMPO (bifunctional) using benzene as a diluent. The net enthalpy and entropy changes were interpreted in terms of different organic phase adduct formation reaction mechanisms i.e. substitution in HTTA vs addition in HPMBP. (author). 4 refs., 2 figs

Photocatalytic Reduction of Hexavalent Chromium Induced by Photolysis of Ferric/tartrate Complex

Energy Technology Data Exchange (ETDEWEB)

Feng, Xianghua; Ding, Shimin; Zhang, Lixian [Yangtze Normal Univ., Fuling (China)

2012-11-15

Photocatalytic reduction of hexavalent chromium (Cr(VI)) in ferric-tartrate system under irradiation of visible light was investigated. Effects of light resources, initial pH value and initial concentration of various reactants on Cr(VI) photocatalytic reduction were studied. Photoreaction kinetics was discussed and a possible photochemical pathway was proposed. The results indicate that Fe(III)-tartrate system is able to rapidly and effectively photocatalytically reduce Cr(VI) utilizing visible light. Initial pH variations results in the concentration changes of Fe(III)-tartrate complex in this system, and pH at 3.0 is optimal for Cr(VI) photocatalytic reduction. Efficiency of Cr(VI) photocatalytic reduction increases with increasing initial concentrations of Cr(VI), Fe(III) and tartrate. Kinetics analysis indicates that initial Fe(III) concentration affects Cr(VI) photoreduction most significantly.

Photocatalytic Reduction of Hexavalent Chromium Induced by Photolysis of Ferric/tartrate Complex

International Nuclear Information System (INIS)

Feng, Xianghua; Ding, Shimin; Zhang, Lixian

2012-01-01

Photocatalytic reduction of hexavalent chromium (Cr(VI)) in ferric-tartrate system under irradiation of visible light was investigated. Effects of light resources, initial pH value and initial concentration of various reactants on Cr(VI) photocatalytic reduction were studied. Photoreaction kinetics was discussed and a possible photochemical pathway was proposed. The results indicate that Fe(III)-tartrate system is able to rapidly and effectively photocatalytically reduce Cr(VI) utilizing visible light. Initial pH variations results in the concentration changes of Fe(III)-tartrate complex in this system, and pH at 3.0 is optimal for Cr(VI) photocatalytic reduction. Efficiency of Cr(VI) photocatalytic reduction increases with increasing initial concentrations of Cr(VI), Fe(III) and tartrate. Kinetics analysis indicates that initial Fe(III) concentration affects Cr(VI) photoreduction most significantly

99Tc and Re incorporated into metal oxide polyoxometalates: oxidation state stability elucidated by electrochemistry and theory.

Science.gov (United States)

McGregor, Donna; Burton-Pye, Benjamin P; Mbomekalle, Israel M; Aparicio, Pablo A; Romo, Susanna; López, Xavier; Poblet, Josep M; Francesconi, Lynn C

2012-08-20

The radioactive element technetium-99 ((99)Tc, half-life = 2.1 × 10(5) years, β(-) of 253 keV), is a major byproduct of (235)U fission in the nuclear fuel cycle. (99)Tc is also found in radioactive waste tanks and in the environment at National Lab sites and fuel reprocessing centers. Separation and storage of the long-lived (99)Tc in an appropriate and stable waste-form is an important issue that needs to be addressed. Considering metal oxide solid-state materials as potential storage matrixes for Tc, we are examining the redox speciation of Tc on the molecular level using polyoxometalates (POMs) as models. In this study we investigate the electrochemistry of Tc complexes of the monovacant Wells-Dawson isomers, α(1)-P(2)W(17)O(61)(10-) (α1) and α(2)-P(2)W(17)O(61)(10-) (α2) to identify features of metal oxide materials that can stabilize the immobile Tc(IV) oxidation state accessed from the synthesized Tc(V)O species and to interrogate other possible oxidation states available to Tc within these materials. The experimental results are consistent with density functional theory (DFT) calculations. Electrochemistry of K(7-n)H(n)[Tc(V)O(α(1)-P(2)W(17)O(61))] (Tc(V)O-α1), K(7-n)H(n)[Tc(V)O(α(2)-P(2)W(17)O(61))] (Tc(V)O-α2) and their rhenium analogues as a function of pH show that the Tc-containing derivatives are always more readily reduced than their Re analogues. Both Tc and Re are reduced more readily in the lacunary α1 site as compared to the α2 site. The DFT calculations elucidate that the highest oxidation state attainable for Re is VII while, under the same electrochemistry conditions, the highest oxidation state for Tc is VI. The M(V)→ M(IV) reduction processes for Tc(V)O-α1 are not pH dependent or only slightly pH dependent suggesting that protonation does not accompany reduction of this species unlike the M(V)O-α2 (M = (99)Tc, Re) and Re(V)O-α1 where M(V/IV) reduction process must occur hand in hand with protonation of the terminal M═O to

Studies of Tc oxidation states in humic acid solutions

International Nuclear Information System (INIS)

Wang Bo; Liu Dejun; Yao Jun

2011-01-01

The oxidation state of Tc is an important aspect of the speciation in groundwater which contained organic substances due to it control the precipitation, complexation, sorption and colloid formation behavior of the Tc under HWL geological disposal conditions. In present work, the oxidation states of Tc were investigated using the LaCl 3 coagulation method and solution extraction method in aqueous solutions in which the humic acid concentration range is from 0 to 20 mg/L and the Tc (VII) concentration is about 10 -8 mol/L. The radiocounting of 99 Tc was determined using liquid scintillation spectrometry. The humic acid will influence the radiocounting ratio of 99 Tc apparently, however, the quenching effect can be restrained once keep the volume of the cocktail to about twenty times of the sample volume. The LaCl 3 coagulation method was carried out for the investigation of Tc oxidation states in humic acid aqueous systems at about pH 8. The tetraphenylarsonium chloride (TPA)-chloroform extraction method was used also simultaneously to investigation the concentrations of Tc (IV) and Tc (VII) for the availability of the LaCl 3 precipitation method, and the experimental results demonstrate that tetravalent technetium and pertechnetate concentration are well agreement with the LaCl 3 precipitation method. These two experimental results demonstrated that Tc (VII) is very stable in the Tc (VII)-humic acid system during a 350 days experimental period, and the Tc (IV) concentrations are very lower, that is indicate that there didn't oxidizing reactions between the Fluka humic acid and Tc (VII) in aqueous solutions under anaerobic conditions. That means the presence of humic acids even in anaerobic groundwater is disadvantage for the retardance of radionuclides. (authors)

Predicting spent fuel oxidation states in a tuff repository

International Nuclear Information System (INIS)

Einziger, R.E.; Woodley, R.E.

1987-01-01

Nevada Nuclear Waste Storage Investigations Project (NNWSI) is studying the suitability of the tuffaceous rocks at Yucca Mountain as a waste repository for spent fuel disposal. The oxidation state of the LWR spent fuel in the moist air environment of a tuff repository could be a significant factor in determining its leaching and dissolution characteristics. Predictions as to which oxidation states would be present are important in analyzing such a repository and thus the present study was undertaken. A set of TGA (thermogravimetric analysis) tests were conducted on well-controlled samples of irradiated PWR fuel with time and temperature as the only variables. The tests were conducted between 140 and 225 0 C for a duration up to 2200 hours. The weight gain curves were analyzed in terms of diffusion through a layer of U 3 O 7 , diffusion into the grains to form a solid solution, a simplified empirical representation of a combination of grain boundary diffusion and bulk grain oxidation. Reaction rate constants were determined in each case, but analysis of these data could not establish a definitive mechanism. 21 refs., 10 figs., 3 tabs

Antidotal impact of extra virgin olive oil against genotoxicity, cytotoxicity and immunotoxicity induced by hexavalent chromium in rat

Directory of Open Access Journals (Sweden)

Samah Khalil

2013-12-01

Full Text Available An in vivo study was carried out to verify whether extra-virgin olive oil (EVOO has the potential to modulate alterations resulted from exposure to hexavalent chromium (CrVI as potassium dichromate in rats. For this purpose, CrVI was injected intraperitoneally (i.p. at a dose of 0.4 mg/kg bw/day, EVOO was given orally at a dose of 300 μl daily either a lone or co-treated with CrVI at the same doses, routes and duration (26 days. At the end of the experiment, blood and spleen samples were collected. Genotoxicity, cytotoxicity and immunotoxicity biomarkers induced by CrVI were evaluated. Also, histopathological and immunohistochemical investigations of spleen tissue were conducted. A significant increase in genotoxicity and cytotoxicity biomarkers (micronucleus frequency, 8-hydroxy-2-deoxyguanosine level and lactate dehydrogenase activity were recorded in CrVI treated rats. In addition, the immunotoxicity biomarkers showed a significant decrease in phagocytic%, stimulated nitric oxide production and decrease in the serum lysozyme activity. Histopathological and immunohistochemical studies support the cytotoxicity study. Oral administration of EVOO can ameliorate those effects but not restored to control level. Thus, authors recommend that regular consumption of this oil in the diet provides a constant supply of potential antioxidants that could reduce these alterations.

Technical Issues Associated with Air Ingression During Core Degradation

International Nuclear Information System (INIS)

Powers, Dana A.

2000-01-01

This paper has shown that it is possible to get significant air intrusion into a ruptured reactor vessel even from a reactor cavity with restricted access. This suggests that there is some importance to considering the consequences of air intrusion following vessel penetration by core debris. The consequences will depend on the nature of core degradation in air and other oxidizing gases. If, indeed, fuel becomes exposed to strongly oxidizing gases, significant releases of ruthenium and hexavalent urania can be expected. Hexavalent urania could alter the nature of cesium release and cesium revaporization from the reactor coolant system. Hexavalent urania could destabilize CSI and enhance the formation of gaseous iodine unless there are other materials that will react readily with atomic iodine along the flow path to the reactor containment

The determination of hexavalent chromium (Cr6+) in electronic and electrical components and products to comply with RoHS regulations

International Nuclear Information System (INIS)

Hua, L.; Chan, Y.C.; Wu, Y.P.; Wu, B.Y.

2009-01-01

Toxicity of hexavalent chromium (Cr 6+ ) was focused on with a publication of EU RoHS directive, a novel method to determine hexavalent chromium is developed. It is a combination of energy dispersion X-ray fluorescence spectrometry (EDXRF), spot test, alkali digestion and UV-vis spectrophotometric analysis. First, by EDXRF screening, the presence or absence of element Cr was established. Spot test was followed to identify the valent state of chromium because Cr 6+ and Cr 3+ normally coexist. After alkali digestion, Cr(VI) was separated without an undersired Cr(VI)-Cr(III) interconversions. With a color reagent (DPC) to chelated with Cr(VI), the solution was finally detected by a UV-vis spectrophotometer at a wavelength of 540 nm which is the basis of analyzing Cr(VI) quantitatively. Some parameters affecting analyses were studied. It was found that when pH in the final solution was 2.0, the extraction time was 60 min, the extraction temperature was 90 deg. C, pH during the extraction process was 7.5-8.5, and a mixed buffer solution (0.5 M K 2 HPO 4 /0.5 M KH 2 PO 4 ) was added up to 1 ml, colorimetric reagent was added to 2 ml, it is optimal for extraction. Under this condition, interferences from Fe 3+ , Pb 2+ , Ag + , etc., were overcome. It was also found that the curves are rectilinear in the range of 0-500 μg l -1 , the correlation coefficient is up to 0.999924, and the recovery rates are more than 85%, the Cr(III)-DPCO complex can be kept stable for 24 h with a relative humidity (RH) range of 60-90%, and a temperature range of 5-40 deg. C. So it can be concluded that the proposed method has a good sensitivity and high precision. It is a more convincing and reliable method due to its relative standard deviation (R.S.D.) <1% after six replicate determinations of Cr(VI) in an Fe-Ni alloy sample

Investigation of the Mode of Action Underlying the Tumorigenic Response Induced in B6C3F1 Mice Exposed Orally to Hexavalent Chromium

Science.gov (United States)

Thompson, Chad M.; Proctor, Deborah M.; Haws, Laurie C.; Hébert, Charles D.; Grimes, Sheila D.; Shertzer, Howard G.; Kopec, Anna K.; Hixon, J.Gregory; Zacharewski, Timothy R.; Harris, Mark A.

2011-01-01

Chronic ingestion of high concentrations of hexavalent chromium [Cr(VI)] in drinking water induces intestinal tumors in mice. To investigate the mode of action (MOA) underlying these tumors, a 90-day drinking water study was conducted using similar exposure conditions as in a previous cancer bioassay, as well as lower (heretofore unexamined) drinking water concentrations. Tissue samples were collected in mice exposed for 7 or 90 days and subjected to histopathological, biochemical, toxicogenomic, and toxicokinetic analyses. Described herein are the results of toxicokinetic, biochemical, and pathological findings. Following 90 days of exposure to 0.3–520 mg/l of sodium dichromate dihydrate (SDD), total chromium concentrations in the duodenum were significantly elevated at ≥ 14 mg/l. At these concentrations, significant decreases in the reduced-to-oxidized glutathione ratio (GSH/GSSG) were observed. Beginning at 60 mg/l, intestinal lesions were observed including villous cytoplasmic vacuolization. Atrophy, apoptosis, and crypt hyperplasia were evident at ≥ 170 mg/l. Protein carbonyls were elevated at concentrations ≥ 4 mg/l SDD, whereas oxidative DNA damage, as assessed by 8-hydroxydeoxyguanosine, was not increased in any treatment group. Significant decreases in the GSH/GSSG ratio and similar histopathological lesions as observed in the duodenum were also observed in the jejunum following 90 days of exposure. Cytokine levels (e.g., interleukin-1β) were generally depressed or unaltered at the termination of the study. Overall, the data suggest that Cr(VI) in drinking water can induce oxidative stress, villous cytotoxicity, and crypt hyperplasia in the mouse intestine and may underlie the MOA of intestinal carcinogenesis in mice. PMID:21712504

Investigation of the oxidation states of Pu isotopes in a hydrochloric acid solution

Energy Technology Data Exchange (ETDEWEB)

Lee, M.H. [Nuclear Chemistry Research Division, Korea Atomic Energy Research Institute, P. O. Box 105, Yuseong, Daejeon 305-353 (Korea, Republic of)], E-mail: mhlee@kaeri.re.kr; Kim, J.Y.; Kim, W.H.; Jung, E.C.; Jee, K.Y. [Nuclear Chemistry Research Division, Korea Atomic Energy Research Institute, P. O. Box 105, Yuseong, Daejeon 305-353 (Korea, Republic of)

2008-12-15

The characteristics of the oxidation states of Pu in a hydrochloric acid solution were investigated and the results were applied to a separating of Pu isotopes from IAEA reference soils. The oxidation states of Pu(III) and Pu(IV) were prepared by adding hydroxylamine hydrochloride and sodium nitrite to a Pu stock solution, respectively. Also, the oxidation state of Pu(VI) was adjusted with concentrated HNO{sub 3} and HClO{sub 4}. The stability of the various oxidation states of plutonium in a HCl solution with elapsed time after preparation were found to be in the following order: Pu(III){approx}Pu(VI)>Pu(IV)>Pu(V). The chemical recoveries of Pu(IV) in a 9 M HCl solution with an anion exchange resin were similar to those of Pu(VI). This method for the determination of Pu isotopes with an anion exchange resin in a 9 M HCl medium was applied to IAEA reference soils where the activity concentrations of {sup 239,240}Pu and {sup 238}Pu in IAEA-375 and IAEA-326 were consistent with the reference values reported by the IAEA.

Precursor preparation for Ca-Al layered double hydroxide to remove hexavalent chromium coexisting with calcium and magnesium chlorides

Science.gov (United States)

Zhong, Lihua; He, Xiaoman; Qu, Jun; Li, Xuewei; Lei, Zhiwu; Zhang, Qiwu; Liu, Xinzhong

2017-01-01

Al(OH)3 and Ca(OH)2 powders are co-ground to prepare a precursor which hydrates into a layered double hydroxide (LDH) phase by agitation in aqueous solution with target hexavalent chromium (Cr(VI)) at room temperature, to achieve an obvious improvement in removal efficiency of Cr(VI) through an easy incorporation into the structure. Although the prepared precursor transforms into LDH phases also when agitated in the solutions of calcium and magnesium chlorides, it incorporates Cr(VI) preferentially to the chloride salts when they coexist. The adsorption isotherm and kinetic studies show that the phenomena occurring on the Al-Ca precursor fit a pseudo-second-order kinetics with a Langmuir adsorption capacity of 59.45 mg/g. Besides, characterizations of the prepared precursor and the samples after adsorption are also performed by X-ray diffraction (XRD), Fourier transform infrared (FT-IR), Transmission electron microscope (TEM) to understand the reason of the preferential incorporation of Cr(VI) to the coexisting chloride salts during the LDH phase formation. Ca-Al precursor (C3A) was agitated in a hexavalent chromium (Cr(VI)) solution to form Al-Ca-CrO4 LDH product. Ca-Al-CrO4 LDH phase occurred preferentially to Ca-Al-MCl2 LDH phases in the solutions of calcium and magnesium chlorides, it incorporates Cr(VI) preferentially to the chloride salts when they coexist.

In-situ Substrate Addition to Create Reactive Zones for Treatment of Chlorinated Aliphatic Hydrocarbons: Hanscom Air Force Base

Science.gov (United States)

2003-04-04

e.g., hexavalent chromium, lead, arsenic, nickel, mercury and cadmium) is also widespread at military facilities due to the use of these metals in...innovative remedies for CAH contamination in groundwater include chemical oxidation, phytoremediation and vacuum enhanced recovery. The primary...pesticides, trichlorofluoromethane, and perchlorate; Hexavalent chromium, nickel, lead, cadmium, mercury , and uranium. Appendix A to the IRZ

In situ oxidation state profiling of nickel hexacyanoferrate derivatized electrodes using line-imaging Raman spectroscopy and multivariate calibration

International Nuclear Information System (INIS)

Haight, S.M.; Schwartz, D.T.

1999-01-01

Metal hexacyanoferrate compounds show promise as electrochemically switchable ion exchange materials for use in the cleanup of radioactive wastes such as those found in storage basins and underground tanks at the Department of Energy's Hanford Nuclear Reservation. Reported is the use of line-imaging Raman spectroscopy for the in situ determination of oxidation state profiles in nickel hexacyanoferrate derivatized electrodes under potential control in an electrochemical cell. Line-imaging Raman spectroscopy is used to collect 256 contiguous Raman spectra every ∼5 microm from thin films (ca. 80 nm) formed by electrochemical derivatization of nickel electrodes. The cyanide stretching region of the Raman spectrum of the film is shown to be sensitive to iron oxidation state and is modeled by both univariate and multivariate correlations. Although both correlations fit the calibration set well, the multivariate (principle component regression or PCR) model's predictions of oxidation state are less sensitive to noise in the spectrum, yielding a much smoother oxidation state profile than the univariate model. Oxidation state profiles with spatial resolution of approximately 5 microm are shown for a nickel hexacyanoferrate derivatized electrode in reduced, intermediate, and oxidized states. In situ oxidation state profiles indicate that the 647.1 nm laser illumination photo-oxidizes the derivatized electrodes. This observation is confirmed using photoelectrochemical methods

Solid oxide fuel cells fueled with reducible oxides

Science.gov (United States)

Chuang, Steven S.; Fan, Liang Shih

2018-01-09

A direct-electrochemical-oxidation fuel cell for generating electrical energy includes a cathode provided with an electrochemical-reduction catalyst that promotes formation of oxygen ions from an oxygen-containing source at the cathode, a solid-state reduced metal, a solid-state anode provided with an electrochemical-oxidation catalyst that promotes direct electrochemical oxidation of the solid-state reduced metal in the presence of the oxygen ions to produce electrical energy, and an electrolyte disposed to transmit the oxygen ions from the cathode to the solid-state anode. A method of operating a solid oxide fuel cell includes providing a direct-electrochemical-oxidation fuel cell comprising a solid-state reduced metal, oxidizing the solid-state reduced metal in the presence of oxygen ions through direct-electrochemical-oxidation to obtain a solid-state reducible metal oxide, and reducing the solid-state reducible metal oxide to obtain the solid-state reduced metal.

Chronic occupational exposure to hexavalent chromium causes DNA damage in electroplating workers.

Science.gov (United States)

Zhang, Xu-Hui; Zhang, Xuan; Wang, Xu-Chu; Jin, Li-Fen; Yang, Zhang-Ping; Jiang, Cai-Xia; Chen, Qing; Ren, Xiao-Bin; Cao, Jian-Zhong; Wang, Qiang; Zhu, Yi-Min

2011-04-12

Occupational exposure to chromium compounds may result in adverse health effects. This study aims to investigate whether low-level hexavalent chromium (Cr(VI)) exposure can cause DNA damage in electroplating workers. 157 electroplating workers and 93 control subjects with no history of occupational exposure to chromium were recruited in Hangzhou, China. Chromium levels in erythrocytes were determined by graphite furnace atomic absorption spectrophotometer. DNA damage in peripheral lymphocytes was evaluated with the alkaline comet assay by three parameters: Olive tail moment, tail length and percent of DNA in the comet tail (tail DNA%). Urinary 8-OHdG levels were measured by ELISA. Chromium concentration in erythrocytes was about two times higher in electroplating workers (median: 4.41 μg/L) than that in control subjects (1.54 μg/L, P electroplating workers. Low-level occupational chromium exposure induced DNA damage.

Assessment of Hexavalent Chromium Natural Attenuation for the Hanford Site 100 Area

Energy Technology Data Exchange (ETDEWEB)

Truex, Michael J. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Szecsody, James E. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Qafoku, Nikolla P. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Sahajpal, Rahul [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Zhong, Lirong [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Lawter, Amanda R. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Lee, Brady D. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

2015-09-01

Hexavalent chromium (Cr(VI)) plumes are present in the 100 Area at the Hanford Site. Remediation efforts are under way with objectives of restoring the groundwater to meet the drinking-water standard (48 µg/L) and protecting the Columbia River by ensuring that discharge of groundwater to the river is below the surface-water quality standard (10 µg/L). Current remedies include application of Pump-and-Treat (P&T) at the 100-D, 100-H, and 100-K Areas and Monitored Natural Attenuation (MNA) at the 100-F/IU Area. Remedy selection is still under way at the other 100 Areas. Additional information about the natural attenuation processes for Cr(VI) is important in all of these cases. In this study, laboratory experiments were conducted to demonstrate and quantify natural attenuation mechanisms using 100 Area sediments and groundwater conditions.

Acute and chronic activity of perchlorate and hexavalent chromium contamination on the survival and development of Culex quinquefasciatus Say (Diptera: Culicidae)

International Nuclear Information System (INIS)

Sorensen, Mary A.; Jensen, Peter D.; Walton, William E.; Trumble, John T.

2006-01-01

Effects of water contamination with perchlorate and hexavalent chromium [Cr (VI)] on the mosquito Culex quinquefasciatus were assessed. The chronic (10-day) LC 5 s values for perchlorate and chromium were 74 ± 8.0 mg/L and 0.41 ± 0.15 mg/L, respectively. Relative Growth Index, a measure of growth and mortality rates in a population, was significantly reduced within 5 days for levels of perchlorate as low as 25 mg/L and for levels of chromium as low as 0.16 mg/L. Neither compound altered wing length of surviving adults. In combination, contaminants were synergistic, causing 14% more mortality than predicted. Acute (24-h) LC 5 values for perchlorate and Cr (VI) were 17,000 ± 3200 and 38 ± 1.3 mg/L, respectively. Effects on mosquito larvae in contaminated environments are likely to be observed for Cr (VI) but not for perchlorate, which generally does not occur at levels as high as those shown here to affect larval mosquitoes. - While pollution with hexavalent chromium may adversely affect Culex quinquefasciatus larvae, levels of perchlorate currently in the environment will not impact these insects

Acute and chronic activity of perchlorate and hexavalent chromium contamination on the survival and development of Culex quinquefasciatus Say (Diptera: Culicidae)

Energy Technology Data Exchange (ETDEWEB)

Sorensen, Mary A. [Department of Entomology, University of California, Riverside, CA 92521 (United States)]. E-mail: mary.sorensen@email.ucr.edu; Jensen, Peter D. [Department of Entomology, University of California, Riverside, CA 92521 (United States); Walton, William E. [Department of Entomology, University of California, Riverside, CA 92521 (United States); Trumble, John T. [Department of Entomology, University of California, Riverside, CA 92521 (United States)

2006-12-15

Effects of water contamination with perchlorate and hexavalent chromium [Cr (VI)] on the mosquito Culex quinquefasciatus were assessed. The chronic (10-day) LC{sub 5}s values for perchlorate and chromium were 74 {+-} 8.0 mg/L and 0.41 {+-} 0.15 mg/L, respectively. Relative Growth Index, a measure of growth and mortality rates in a population, was significantly reduced within 5 days for levels of perchlorate as low as 25 mg/L and for levels of chromium as low as 0.16 mg/L. Neither compound altered wing length of surviving adults. In combination, contaminants were synergistic, causing 14% more mortality than predicted. Acute (24-h) LC{sub 5} values for perchlorate and Cr (VI) were 17,000 {+-} 3200 and 38 {+-} 1.3 mg/L, respectively. Effects on mosquito larvae in contaminated environments are likely to be observed for Cr (VI) but not for perchlorate, which generally does not occur at levels as high as those shown here to affect larval mosquitoes. - While pollution with hexavalent chromium may adversely affect Culex quinquefasciatus larvae, levels of perchlorate currently in the environment will not impact these insects.

Studies on Se-Cr interactions in mungbean using radiotracers

Energy Technology Data Exchange (ETDEWEB)

Shanker, Karuna; Mishra, Seema; Srivastava, Shalini; Srivastava, Rohit; Dass, Sahab; Prakash, Satya; Srivastava, M M [Dayalbagh Educational Institute, Agra (India). Dept. of Chemistry

1995-09-01

The paper describes a preliminary report of hydroponic experiment on the effect of selenium (selenite and selenate) treatments on the absorption of trivalent and hexavalent chromium by mung bean (Phaseolus mungo) plant. The studies are mainly confined to animal system and little attention has been paid on Se-metal interactions, particularly with those of different oxidation states of selenium and chromium in plant system. (author). 8 refs., 1 tab.

Studies on Se-Cr interactions in mungbean using radiotracers

International Nuclear Information System (INIS)

Shanker, Karuna; Mishra, Seema; Srivastava, Shalini; Srivastava, Rohit; Dass, Sahab; Prakash, Satya; Srivastava, M.M.

1995-01-01

The paper describes a preliminary report of hydroponic experiment on the effect of selenium (selenite and selenate) treatments on the absorption of trivalent and hexavalent chromium by mung bean (Phaseolus mungo) plant. The studies are mainly confined to animal system and little attention has been paid on Se-metal interactions, particularly with those of different oxidation states of selenium and chromium in plant system. (author). 8 refs., 1 tab

Effective Removal of Hexavalent Chromium from Aqueous Solutions Using Ionic Liquid Modified Graphene Oxide Sorbent

Directory of Open Access Journals (Sweden)

A. Nasrollahpour

2017-10-01

Full Text Available Ionic liquid modified reduced graphene oxide (IL-rGO was prepared and examined for chromate removal. The sorbent was characterized by N2 adsorption-desorption measurement (BET, transmission electron microscopy (TEM, powder X-ray diffraction (XRD, and X-ray photoelectron spectroscopy (XPS analysis. The sorption behavior of chromate on the ionic liquid modified reduced graphene oxide sorbent from an aqueous medium was studied by varying the parameters such as contact time, initial chromate concentration, pH, and agitation speed. The results showed that sorption kinetics of chromate by IL-rGO follows the pseudo second order, which indicates that the sorption mechanism is both chemical and physical interaction. The sorption isotherm studies revealed that Langmuir model provided the best fit to all the experimental data with an adsorption capacity of 232.55 mg g–1 for IL-rGO. Thermodynamic parameters, such as Gibbs free energy (–2.85 kJ mol–1 at 298 K, enthalpy (55.41 kJ mol–1, and entropy (11.64 J mol–1 K–1 of sorption of the chromate on ionic liquid modified reduced graphene oxide was evaluated, and it was found that the reaction was spontaneous and endothermic in nature.

Automated Ground-Water Sampling and Analysis of Hexavalent Chromium using a “Universal” Sampling/Analytical System

Directory of Open Access Journals (Sweden)

Richard J. Venedam

2005-02-01

Full Text Available The capabilities of a “universal platform” for the deployment of analyticalsensors in the field for long-term monitoring of environmental contaminants were expandedin this investigation. The platform was previously used to monitor trichloroethene inmonitoring wells and at groundwater treatment systems (1,2. The platform was interfacedwith chromium (VI and conductivity analytical systems to monitor shallow wells installedadjacent to the Columbia River at the 100-D Area of the Hanford Site, Washington. Agroundwater plume of hexavalent chromium is discharging into the Columbia River throughthe gravels beds used by spawning salmon. The sampling/analytical platform was deployedfor the purpose of collecting data on subsurface hexavalent chromium concentrations atmore frequent intervals than was possible with the previous sampling and analysis methodsemployed a the Site.

Characterization of TBP containing polysiloxane membrane/insulator/semiconductor structures for hexavalent chromium detection

Energy Technology Data Exchange (ETDEWEB)

Zazoua, A. [Universite de Jijel, BP 98, Ouled Aissa, 18000 Jijel (Algeria); Universite de Annaba, BP 12, El-Hadjar, Annaba (Algeria); Kherrat, R.; Samar, M.H. [Universite de Annaba, BP 12, El-Hadjar, Annaba (Algeria); Errachid, A. [Laboratori de Nanobioenginyeria-IBEC, CIBER, Parc Cientific de Barcelona (PCB)-Departament d' Electronica. Universitat de Barcelona, C/Marti i Franques 1, 08028 Barcelona (Spain); Jaffrezic-Renault, N. [LSA - UMR 5180 CNRS - Universite Claude Bernard Lyon 1, 69622 Villeurbanne cedex (France)], E-mail: nicole.jaffrezic@univ-lyon1.fr; Bessueille, F.; Leonard, D. [LSA - UMR 5180 CNRS - Universite Claude Bernard Lyon 1, 69622 Villeurbanne cedex (France)

2008-07-01

A hexavalent chromium-sensitive EMIS sensor (electrolyte membrane insulator semiconductor sensor) is prepared by deposition of a tributylphosphate (TBP) ionophore-containing siloprene membrane on a Si/SiO{sub 2}/Si{sub 3}N{sub 4} structure. The developed EMIS sensor was studied by means of impedance spectroscopy, capacitance-voltage, X-ray photoelectron spectrometry and FT-IR spectroscopy. From the flat-band shift of the EMIS structure, the nersntian response to the anionic species Cr{sub 2}O{sub 7}{sup -} was demonstrated. The linear range of detection is 10{sup -4} M to 10{sup -1} M and the detection limit is 10{sup -5} M. Sulfate and chloride anions are shown not to be interfering whereas carbonate ions present a pK{sup pot} equal to 0.19.

Transient gestational exposure to drinking water containing excess hexavalent chromium modifies insulin signaling in liver and skeletal muscle of rat progeny.

Science.gov (United States)

Shobana, Navaneethabalakrishnan; Aruldhas, Mariajoseph Michael; Tochhawng, Lalmuankimi; Loganathan, Ayyalu; Balaji, Sadhasivam; Kumar, Mani Kathiresh; Banu, Liaquat Alikhan Sheerin; Navin, Ajit Kumar; Mayilvanan, Chinnaiyan; Ilangovan, Ramachandran; Balasubramanian, Karundevi

2017-11-01

Chromium (Cr), an essential micronutrient potentiates insulin action, whereas excess hexavalent Cr (CrVI) acts as an endocrine disruptor. Pregnant mothers living in areas abutting industries using the metal and chromite ore dumps are exposed to ground water contaminated with Cr. Nevertheless, the impact of prenatal exposure to excess CrVI on insulin signaling in the progeny remains obscure. We tested the hypothesis "transient gestational exposure to drinking water containing excess CrVI may modify insulin signaling during postnatal life". Pregnant Wistar rats were given drinking water containing 50, 100 and 200 ppm CrVI (K 2 Cr 2 O 7 ) from gestational day 9-14 encompassing the period of organogenesis; the male progenies were tested at postnatal day 60. Neither fasting blood glucose nor oral glucose tolerance was altered in CrVI treated progeny. Nevertheless, western blot detection pointed out attenuated expression level of insulin receptor (IR), its downstream signaling molecules (IRS-1, pIRS-1 Tyr632 , Akt and pAkt Ser473 ) and organ specific glucose transporters (GLUT2 in liver and GLUT4 in gastrocnemius muscle), along with a significant increase in serum insulin level in male progenies exposed to CrVI. While 14 C-2-deoxy glucose uptake increased in the liver, the same decreased in the skeletal muscle whereas, 14 C-glucose oxidation recorded a consistent decrease in both tissues of CrVI exposed rats. These findings support our hypothesis and suggest that transient gestational exposure to excess CrVI may affect insulin signaling and glucose oxidation in the progeny, predictably rendering them vulnerable to insulin resistance. Copyright © 2017 Elsevier B.V. All rights reserved.

Plutonium uptake by Scenedesmus obliquus as a function of isotope and oxidation state

International Nuclear Information System (INIS)

Tkacik, M.F.; Giesy, J.P.; Wilhite, E.L.; Corey, J.C.

1979-01-01

Uptake of 238 Pu 4+ , 238 Pu 6+ , 239 Pu 4+ and 239 Pu 6+ by the green alga Scenedesmus obliquus (Turp) Kutz was studied to determine whether isotope or oxidation state differences affect Pu uptake from aqueous medium by algal cells. At equivalent 238 Pu and 239 PU concentrations, even when initial oxidation states differed, accumulations of these isotopes by S.obliquus were not significantly (p>0.05) different. Plutonium accumulation by S.obliquus was log-linear. (author)

Oxidation states of Fe in LaNi1-xFexO3

International Nuclear Information System (INIS)

Goeta, A.E.; Falcon, H.; Carbonio, R.

1994-01-01

The distribution of oxidation states in perovskites of the type LaA 1-x B x O 3 (A and B transition metal ions) can be ''tailored'' by x variation. In particular, in LaNiO 3 it has been shown that Fe substitution for Ni foces some Ni 3+ into Ni 2+ , while some Fe 3+ changes into the unusual Fe 4+ state. In addition, the existence of mixed oxidation states of Fe and/or Ni in LaNi 1-x Fe x O 3 has been related to its catalytic activity in hydrogen peroxide decomposition. The Fe 4+ population, obtained using Moessbauer spectroscopy, was found to be constant for all the analyzed annealing temperatures for x = 0.25 concentration, where the isomer shift difference for both states is the highest and the catalytic activity is maximum. (orig.)

The oxidation state of sulfur in apatite: A new oxybarometer?

Science.gov (United States)

Fiege, A.; Konecke, B.; Kim, Y.; Simon, A. C.; Becker, U.; Parat, F.

2016-12-01

Oxygen fugacity (fO2) of magmatic and hydrothermal systems influences, for instance, crystallization and degassing processes as well as metal solubilities in melts and fluids. Apatite is a ubiquitous mineral in magmatic and hydrothermal environments that can record and preserve volatile zonation. It can contain several thousand μg/g of the redox sensitive element sulfur (S), making S-in-apatite a potential fO2 sensor. Despite the polyvalent properties of S (e.g., S2-, S4+, S6+), the oxidation state and incorporation mechanisms of S in the apatite structure are poorly understood. In this study, the oxidation state of S-in-apatite as a function of fO2 is investigated using X-ray absorption near-edge structures (XANES) spectroscopy at the S K-edge. Apatites crystallized from lamproitic melts at 1000°C, 300 MPa and over a broad range of fO2 and sulfur fugacities (fS2) were measured. Peaks corresponding to S6+ ( 2482 eV), S4+ ( 2478 eV) and S2- ( 2470 eV) were identified in apatite. The integrated S6+/STotal (STotal = S6+ + S4+ + S2-) peak area ratios show a distinct positive correlation with fO2, increasing from 0.17 at FMQ+0 to 0.96 at FMQ+3. Ab-initio calculations were performed to further understand the energetics and geometry of incorporation of S6+, S4+ and S2- into the apatite (F-, Cl-, OH-) end-members. The results confirm that apatite can contain three different oxidations states of S (S6+, S4+, S2-) as a function of fO2. This makes apatite probably the first geologically relevant mineral to incorporate reduced (S2-), intermediate (S4+), and oxidized (S6+) S in variable proportions. We emphasize that the strong dependence of the S oxidation state in apatite as a function of fO2 is also coupled with changing S content of apatite and co-existing melt (i.e., with changing fS2), resulting in a complex correlation between [1] apatite-melt (or fluid) partitioning, [2] redox conditions and [3] the melt and/or fluid composition, making the application of previously

SEPARATION OF URANIUM, PLUTONIUM, AND FISSION PRODUCTS

Science.gov (United States)

Spence, R.; Lister, M.W.

1958-12-16

Uranium and plutonium can be separated from neutron-lrradiated uranium by a process consisting of dissolvlng the lrradiated material in nitric acid, saturating the solution with a nitrate salt such as ammonium nitrate, rendering the solution substantially neutral with a base such as ammonia, adding a reducing agent such as hydroxylamine to change plutonium to the trivalent state, treating the solution with a substantially water immiscible organic solvent such as dibutoxy diethylether to selectively extract the uranium, maklng the residual aqueous solutlon acid with nitric acid, adding an oxidizing agent such as ammonlum bromate to oxidize the plutonium to the hexavalent state, and selectlvely extracting the plutonium by means of an immlscible solvent, such as dibutoxy dlethyletber.

Studies of the Tc oxidation states in humic acid solutions

International Nuclear Information System (INIS)

Wang Bo; Liu Dejun; Yao Jun

2010-01-01

The oxidation state is an important aspect of the speciation of Tc in groundwater that contained organic substances due to it control the precipitation, complexation, sorption and colloid formation behavior of the Tc under HWL geological disposal conditions. In present work, the oxidation states of Tc were investigated using the LaCl 3 coagulation method and solution extraction method in aqueous solutions in which the humic acid concentration range is from 0 to 20 mg L -1 and the Tc (Ⅶ) concentration range is about 10 -8 mol l -1 . The radiocounting of 99 Tc was determined using liquid scintillation spectrometry. The humic acid will influence the radiocounting ratio of 99 Tc apparently, however, the quenching effect can be restrained once keep the volume of the cocktail to about twenty times of the sample volume. The LaCl 3 coagulation methods were carried out for the investigation of Tc oxidation states in humic acid aqueous systems at about pH 8. The tetraphenylarsonium chloride (IPA)-chloroform extraction method was used also simultaneously to investigation the concentrations of Tc (Ⅳ) and Tc (Ⅶ) for the availability of the LaCl 3 precipitation method, and the experimental results demonstrate that tetravalent technetium and pertechnetate concentrations are well agreement with the LaCl 3 precipitation method. These two experimental results demonstrated that Tc (Ⅶ) is very stable in the Tc (Ⅶ)-humic acid system during a 350 days experimental period, and the Tc (Ⅳ) concentrations are very lower, that is indicate that there didn't oxidizing reactions between the Fluka humic acid and Tc (Ⅶ) in aqueous solutions under anaerobic conditions. That is means the presence of humic acids even in anaerobic groundwater is disadvantage for the retardance of radionuclides. (authors)

Influence of microorganisms on the oxidation state distribution of multivalent actinides under anoxic conditions

International Nuclear Information System (INIS)

Reed, Donald Timothy; Borkowski, Marian; Lucchini, Jean-Francois; Ams, David; Richmann, M.K.; Khaing, H.; Swanson, J.S.

2010-01-01

The fate and potential mobility of multivalent actinides in the subsurface is receiving increased attention as the DOE looks to cleanup the many legacy nuclear waste sites and associated subsurface contamination. Plutonium, uranium and neptunium are the near-surface multivalent contaminants of concern and are also key contaminants for the deep geologic disposal of nuclear waste. Their mobility is highly dependent on their redox distribution at their contamination source as well as along their potential migration pathways. This redox distribution is often controlled, especially in the near-surface where organic/inorganic contaminants often coexist, by the direct and indirect effects of microbial activity. Under anoxic conditions, indirect and direct bioreduction mechanisms exist that promote the prevalence of lower-valent species for multivalent actinides. Oxidation-state-specific biosorption is also an important consideration for long-term migration and can influence oxidation state distribution. Results of ongoing studies to explore and establish the oxidation-state specific interactions of soil bacteria (metal reducers and sulfate reducers) as well as halo-tolerant bacteria and Archaea for uranium, neptunium and plutonium will be presented. Enzymatic reduction is a key process in the bioreduction of plutonium and uranium, but co-enzymatic processes predominate in neptunium systems. Strong sorptive interactions can occur for most actinide oxidation states but are likely a factor in the stabilization of lower-valent species when more than one oxidation state can persist under anaerobic microbiologically-active conditions. These results for microbiologically active systems are interpreted in the context of their overall importance in defining the potential migration of multivalent actinides in the subsurface.

Evaluating the Impact of the U.S. National Toxicology Program: A Case Study on Hexavalent Chromium.

Science.gov (United States)

Xie, Yun; Holmgren, Stephanie; Andrews, Danica M K; Wolfe, Mary S

2017-02-01

Evaluating the impact of federally funded research with a broad, methodical, and objective approach is important to ensure that public funds advance the mission of federal agencies. We aimed to develop a methodical approach that would yield a broad assessment of National Toxicology Program's (NTP's) effectiveness across multiple sectors and demonstrate the utility of the approach through a case study. A conceptual model was developed with defined activities, outputs (products), and outcomes (proximal, intermediate, distal) and applied retrospectively to NTP's research on hexavalent chromium (CrVI). Proximal outcomes were measured by counting views of and requests for NTP's products by external stakeholders. Intermediate outcomes were measured by bibliometric analysis. Distal outcomes were assessed through Web and LexisNexis searches for documents related to legislation or regulation changes. The approach identified awareness of NTP's work on CrVI by external stakeholders (proximal outcome) and citations of NTP's research in scientific publications, reports, congressional testimonies, and legal and policy documents (intermediate outcome). NTP's research was key to the nation's first-ever drinking water standard for CrVI adopted by California in 2014 (distal outcome). By applying this approach to a case study, the utility and limitations of the approach were identified, including challenges to evaluating the outcomes of a research program. This study identified a broad and objective approach for assessing NTP's effectiveness, including methodological needs for more thorough and efficient impact assessments in the future. Citation: Xie Y, Holmgren S, Andrews DMK, Wolfe MS. 2017. Evaluating the impact of the U.S. National Toxicology Program: a case study on hexavalent chromium. Environ Health Perspect 125:181-188; http://dx.doi.org/10.1289/EHP21.

Hexavalent chromium, a lung carcinogen, confers resistance to thermal stress and interferes with heat shock protein expression in human bronchial epithelial cells.

Science.gov (United States)

Abreu, Patrícia L; Cunha-Oliveira, Teresa; Ferreira, Leonardo M R; Urbano, Ana M

2018-03-16

Exposure to hexavalent chromium [Cr(VI)], a lung carcinogen, triggers several types of cellular stresses, namely oxidative, genotoxic and proteotoxic stresses. Given the evolutionary character of carcinogenesis, it is tempting to speculate that cells that survive the stresses produced by this carcinogen become more resistant to subsequent stresses, namely those encountered during neoplastic transformation. To test this hypothesis, we determined whether pre-incubation with Cr(VI) increased the resistance of human bronchial epithelial cells (BEAS-2B cells) to the antiproliferative action of acute thermal shock, used here as a model for stress. In line with the proposed hypothesis, it was observed that, at mildly cytotoxic concentrations, Cr(VI) attenuated the antiproliferative effects of both cold and heat shock. Mechanistically, Cr(VI) interfered with the expression of two components of the stress response pathway: heat shock proteins Hsp72 and Hsp90α. Specifically, Cr(VI) significantly depleted the mRNA levels of the former and the protein levels of the latter. Significantly, these two proteins are members of heat shock protein (Hsp) families (Hsp70 and Hsp90, respectively) that have been implicated in carcinogenesis. Thus, our results confirm and extend previous studies showing the capacity of Cr(VI) to interfere with the expression of stress response components.

Conformational Toggling of Yeast Iso-1-Cytochrome c in the Oxidized and Reduced States

Science.gov (United States)

Yang, Zhongzheng; Zhu, Jing; Ying, Tianlei; Jiang, Xianwang; Zhang, Xu; Wu, Houming; Liu, Maili; Tan, Xiangshi; Cao, Chunyang; Huang, Zhong-Xian

2011-01-01

To convert cyt c into a peroxidase-like metalloenzyme, the P71H mutant was designed to introduce a distal histidine. Unexpectedly, its peroxidase activity was found even lower than that of the native, and that the axial ligation of heme iron was changed to His71/His18 in the oxidized state, while to Met80/His18 in the reduced state, characterized by UV-visible, circular dichroism, and resonance Raman spectroscopy. To further probe the functional importance of Pro71 in oxidation state dependent conformational changes occurred in cyt c, the solution structures of P71H mutant in both oxidation states were determined. The structures indicate that the half molecule of cyt c (aa 50–102) presents a kind of “zigzag riveting ruler” structure, residues at certain positions of this region such as Pro71, Lys73 can move a big distance by altering the tertiary structure while maintaining the secondary structures. This finding provides a molecular insight into conformational toggling in different oxidation states of cyt c that is principle significance to its biological functions in electron transfer and apoptosis. Structural analysis also reveals that Pro71 functions as a key hydrophobic patch in the folding of the polypeptide of the region (aa 50–102), to prevent heme pocket from the solvent. PMID:22087268

Synthesis and characterization of ruthenium fluorides and oxide fluorides with high oxidation states

International Nuclear Information System (INIS)

Meublat, L.

1989-10-01

The synthesis of ruthenium fluorides and oxide fluorides with high oxidation states was attempted from dioxide RuO 2 and tetroxide RuO 4 . Three fluorinating agents were used: fluorine, chlorine trifluoride and krypton difluoride. The reactions were achieved in anhydrous hydrogen fluoride at room temperature. Thus, the reaction of RuO 4 with CIF 3 enabled us to prepare chloryl hexafluororuthenate (V), CIO 2 + RuF 6 - , a new compound well identified by vibrational spectroscopy (infra-red and Raman), the structure of which was determined. The reaction of KrF 2 with RuO 4 gave the oxide tetrafluoride RuOF 4 , the previously published syntheses and properties of which were not in agreement with each other. This compound was definitely characterized here by chemical analysis, infra-red spectroscopy and X-ray powder diffraction. The product of thermal decomposition (70 0 C) of RuOF 4 is presumably RuF 4 since only oxygen is liberated during this decomposition. At last, the reaction of KrF 2 with RuO 2 probably leads to the formation of the new oxide fluoride RuO 2 F 4 . Indeed, no oxygen is given off during this reaction, the chemical analysis of the red-orange coloured solid residue is almost in agreement with the one proposed and its infra-red absorption spectrum indicates the presence of ruthenium-oxygen and ruthenium-terminal and bridging fluorine bonds [fr

Synthesis and characterization of ruthenium fluorides and oxide fluorides with high oxidation states

International Nuclear Information System (INIS)

Meublat, L.

1989-01-01

The synthesis of ruthenium fluorides and oxide fluorides with high oxidation states was attempted from dioxide RuO 2 and tetroxide RuO 4 . Three fluorinating agents were used: fluorine, chlorine trifluoride and krypton difluoride. The reactions were achieved in anhydrous hydrogen fluoride at room temperature. Thus, the reaction of RuO 4 with CIF 3 enabled us to prepare chloryl hexafluororuthenate (V), ClO 2 + RuF 6 - , a new compound well idendified by vibrational spectroscopy (infra-red and Raman), the structure of which was determined. The reaction of KrF 2 with RuO 4 gave the oxide tetrafluoride RuOF 4 , the previously published syntheses and properties of which were not in agreement with each other. This compound was definitely characterized here by chemical analysis, infra-red spectroscopy and X-ray powder diffraction. The product of thermal decomposition (70 0 C) of RuOF 4 is presumably RuF 4 since only oxygen is liberated during this decomposition. At last, the reaction of KrF 2 with RuO 2 probably leads to the formation of the new oxide fluoride RuO 2 F 4 . Indeed, no oxygen is given off during this reaction, the chemical analysis of the red-orange coloured solid residue is almost in agreement with the one proposed and its infra-red absorption spectrum indicates the presence of ruthenium-oxygen and ruthenium-terminal and bridging fluorine bonds [fr

Evolution of the Oxidation State of the Earth's Mantle

Science.gov (United States)

Danielson, L. R.; Righter, K.; Keller, L.; Christoffersen, E.; Rahman, Z.

2015-01-01

The oxidation state of the Earth's mantle during formation remains an unresolved question, whether it was constant throughout planetary accretion, transitioned from reduced to oxidized, or from oxidized to reduced. We investigate the stability of Fe3(+) at depth, in order to constrain processes (water, late accretion, dissociation of FeO) which may reduce or oxidize the Earth's mantle. In our previous experiments on shergottite compositions, variable fO2, T, and P less than 4 GPa, Fe3(+)/sigma Fe decreased slightly with increasing P, similar to terrestrial basalt. For oxidizing experiments less than 7GPa, Fe3(+)/sigma Fe decreased as well, but it's unclear from previous modelling whether the deeper mantle could retain significant Fe3(+). Our current experiments expand our pressure range deeper into the Earth's mantle and focus on compositions and conditions relevant to the early Earth. Preliminary multi-anvil experiments with Knippa basalt as the starting composition were conducted at 5-7 GPa and 1800 C, using a molybdenum capsule to set the fO2 near IW, by buffering with Mo-MoO3. TEM and EELS analyses revealed the run products quenched to polycrystalline phases, with the major phase pyroxene containing approximately equal to Fe3(+)/2(+). Experiments are underway to produce glassy samples that can be measured by EELS and XANES, and are conducted at higher pressures.

Removal of hexavalent chromium from wastewater using a new composite chitosan biosorbent.

Science.gov (United States)

Boddu, Veera M; Abburi, Krishnaiah; Talbott, Jonathan L; Smith, Edgar D

2003-10-01

A new composite chitosan biosorbent was prepared by coating chitosan, a glucosamine biopolymer, onto ceramic alumina. The composite bioadsorbent was characterized by high-temperature pyrolysis, porosimetry, scanning electron microscopy, and X-ray photoelectron spectroscopy. Batch isothermal equilibrium and continuous column adsorption experiments were conducted at 25 degrees C to evaluate the biosorbent for the removal of hexavalent chromium from synthetic as well as field samples obtained from chrome plating facilities. The effect of pH, sulfate, and chloride ion on adsorption was also investigated. The biosorbent loaded with Cr(VI) was regenerated using 0.1 M sodium hydroxide solution. A comparison of the results of the present investigation with those reported in the literature showed that chitosan coated on alumina exhibits greater adsorption capacity for chromium(VI). Further, experimental equilibrium data were fitted to Langmuir and Freundlich adsorption isotherms, and values of the parameters of the isotherms are reported. The ultimate capacity obtained from the Langmuir model is 153.85 mg/g chitosan.

Chronic occupational exposure to hexavalent chromium causes DNA damage in electroplating workers

Directory of Open Access Journals (Sweden)

Ren Xiao-Bin

2011-04-01

Full Text Available Abstract Background Occupational exposure to chromium compounds may result in adverse health effects. This study aims to investigate whether low-level hexavalent chromium (Cr(VI exposure can cause DNA damage in electroplating workers. Methods 157 electroplating workers and 93 control subjects with no history of occupational exposure to chromium were recruited in Hangzhou, China. Chromium levels in erythrocytes were determined by graphite furnace atomic absorption spectrophotometer. DNA damage in peripheral lymphocytes was evaluated with the alkaline comet assay by three parameters: Olive tail moment, tail length and percent of DNA in the comet tail (tail DNA%. Urinary 8-OHdG levels were measured by ELISA. Results Chromium concentration in erythrocytes was about two times higher in electroplating workers (median: 4.41 μg/L than that in control subjects (1.54 μg/L, P P P P Conclusion The findings in this study indicated that there was detectable chromium exposure in electroplating workers. Low-level occupational chromium exposure induced DNA damage.

Reduction of Hexavalent Chromium Using L-Cysteine Capped Nickel Nanocatalysts

Directory of Open Access Journals (Sweden)

Razium Ali Soomro

2013-06-01

Full Text Available The aim of this study was to reduce the highly toxic hexavalent chromium Cr(VI into less toxic chromium Cr(III species by using nickel nanoparticles (Ni NPs as catalysts in order to provide safety to the aqueous environment. In the first phase Ni NPs were synthesized in ethylene glycol and capped with l-cysteine by a modified microwave irradiation method using NaOH as the accelerator. The formed Ni NPs were characterized by various techniques such as UV-Visible spectroscopy, Fourier Transform Infra-red (FTIR spectroscopy and Scanning Electron Microscopy (SEM. In the second phase the formed Ni NPs were immobilized on glass surfaces and employed as catalyst for the reduction of Cr(VI ions. According to observations, 99% reduction of Cr(VI ions was achieved in the presence of 0.5 mg of Ni NPs catalyst in just five minutes as compared to nickel powder that showed only 16% reduction in 15 minutes. The study has a great impact on the aqueous pollution control of Cr(VI especially caused by the discharge of waste water from several industries utilizing Cr(VI containing salt as one of the essential gradients.

Immunogenicity and safety of monovalent RIVM meningococcal B OMP vesicle F91 vaccine administered to children that received hexavalent meningococcal B vaccine 2.5 years ago

NARCIS (Netherlands)

Lafeber AB; Limpt CJP van; Berbers GAM; Labadie J; Kleijn ED de; Groot R de; Rumke HC; Alphen AJW van; Sophia Kinderziekenhuis /; LVO

2000-01-01

This report describes the results with respect to immunogenicity as well as reactogenicity of a monovalent P1.7h,4 OMV vaccine (MonoMen) used as booster vaccination in children previously vaccinated with a hexavalent MenB vaccine. The participants in this study were immunised in 1995-1996 with

Arsenic (+3 oxidation state) methyltransferase and the inorganic arsenic methylation phenotype

International Nuclear Information System (INIS)

Li Jiaxin; Waters, Stephen B.; Drobna, Zuzana; Devesa, Vicenta; Styblo, Miroslav; Thomas, David J.

2005-01-01

Inorganic arsenic is enzymatically methylated; hence, its ingestion results in exposure to the parent compound and various methylated arsenicals. Both experimental and epidemiological evidences suggest that some of the adverse health effects associated with chronic exposure to inorganic arsenic may be mediated by these methylated metabolites. If i As methylation is an activation process, then the phenotype for inorganic arsenic methylation may determine risk associated with exposure to this metalloid. We examined inorganic arsenic methylation phenotypes and arsenic (+3 oxidation state) methyltransferase genotypes in four species: three that methylate inorganic arsenic (human (Homo sapiens), rat (Rattus norwegicus), and mouse (Mus musculus)) and one that does not methylate inorganic arsenic (chimpanzee, Pan troglodytes). The predicted protein products from arsenic (+3 oxidation state) methyltransferase are similar in size for rat (369 amino acid residues), mouse (376 residues), and human (375 residues). By comparison, a 275-nucleotide deletion beginning at nucleotide 612 in the chimpanzee gene sequence causes a frameshift that leads to a nonsense mutation for a premature stop codon after amino acid 205. The null phenotype for inorganic arsenic methylation in the chimpanzee is likely due to the deletion in the gene for arsenic (+3 oxidation state) methyltransferase that yields an inactive truncated protein. This lineage-specific loss of function caused by the deletion event must have occurred in the Pan lineage after Homo-Pan divergence about 5 million years ago

Approaches to Determining the Oxidation State of Nitrogen and Carbon Atoms in Organic Compounds for High School Students

Science.gov (United States)

Jurowski, Kamil; Krzeczkowska, Malgorzata Krystyna; Jurowska, Anna

2015-01-01

The concept of oxidation state (or oxidation number) and related issues have always been difficult for students. In addition, there are misunderstandings and obscurities, which can cause improper balancing of the chemical equations (mostly in organic reactions). In particular, these problems are related to determination of the oxidation state of…

On matrix stabilisation of d- and f-transition metal ions in unstable oxidation states

Energy Technology Data Exchange (ETDEWEB)

Kiselev, Yurii M [Department of Chemistry, M.V. Lomonosov Moscow State University, Moscow (Russian Federation)

2009-01-31

The state-of-the-art in matrix stabilisation of d- and f-transition metal ions in unstable oxidation states is analysed. Main aspects of this problem concerning the genealogy of appropriate matrix systems are classified. Relevant examples are given and the data that contradict the scheme proposed are discussed. The thermodynamics of the matrix stabilisation effect is considered using the concept of isomorphic miscibility. The influence of defects and non-equilibrium on the matrix stabilisation effect is discussed. The problem of identification of the oxidation states in matrix systems is examined and various types of matrix systems are considered.

On matrix stabilisation of d- and f-transition metal ions in unstable oxidation states

International Nuclear Information System (INIS)

Kiselev, Yurii M

2009-01-01

The state-of-the-art in matrix stabilisation of d- and f-transition metal ions in unstable oxidation states is analysed. Main aspects of this problem concerning the genealogy of appropriate matrix systems are classified. Relevant examples are given and the data that contradict the scheme proposed are discussed. The thermodynamics of the matrix stabilisation effect is considered using the concept of isomorphic miscibility. The influence of defects and non-equilibrium on the matrix stabilisation effect is discussed. The problem of identification of the oxidation states in matrix systems is examined and various types of matrix systems are considered.

Facile solid-state synthesis of oxidation-resistant metal nanoparticles at ambient conditions

Science.gov (United States)

Lee, Kyu Hyung; Jung, Hyuk Joon; Lee, Ju Hee; Kim, Kyungtae; Lee, Byeongno; Nam, Dohyun; Kim, Chung Man; Jung, Myung-Hwa; Hur, Nam Hwi

2018-05-01

A simple and scalable method for the synthesis of metal nanoparticles in the solid-state was developed, which can produce nanoparticles in the absence of solvents. Nanoparticles of coinage metals were synthesized by grinding solid hydrazine and the metal precursors in their acetates and oxides at 25 °C. The silver and gold acetates converted completely within 6 min into Ag and Au nanoparticles, respectively, while complete conversion of the copper acetate to the Cu sub-micrometer particles took about 2 h. Metal oxide precursors were also converted into metal nanoparticles by grinding alone. The resulting particles exhibit distinctive crystalline lattice fringes, indicating the formation of highly crystalline phases. The Cu sub-micrometer particles are better resistant to oxidation and exhibit higher conductivity compared to conventional Cu nanoparticles. This solid-state method was also applied for the synthesis of platinum group metals and intermetallic Cu3Au, which can be further extended to synthesize other metal nanoparticles.

Properties of magnetic iron oxides used as materials for wastewater treatment

Energy Technology Data Exchange (ETDEWEB)

Matei, E; Predescu, A; Predescu, A [Politehnica University of Bucharest, Faculty of Science and Engineering Materials, 313 Splaiul Independentei, 060042, Bucharest (Romania); Vasile, E, E-mail: ecaterina.matei@ecomet.pub.ro [METAV CD, 31 C.A. Rosetti Street, 020011, Bucharest (Romania)

2011-07-06

The paper describes the properties of some nanopowders obtained by coprecipitation and used as adsorbent for wastewater treatment. The Fe{sub 3}O{sub 4} and {gamma}-Fe{sub 2}O{sub 3} nanopowders were obtained using iron salts and NaOH as precipitation agents. D-sorbitol was used to prevent the agglomeration between the nanoparticles. The particle size and distribution were detected using a transmission electron microscopy (TEM) and a scanning electron microscope (SEM) equipped with dispersive analyze system in X radiation energy (EDS). The structure of the iron oxide nanoparticles was characterized by X-ray powder diffraction. Thus, the nanoparticles were characterized and compare in terms of particle size and chemical composition and used for adsorption studies in order to removal hexavalent chromium from waste waters.

Evaluation of extraction methods for hexavalent chromium determination in dusts, ashes, and soils

Science.gov (United States)

Wolf, Ruth E.; Wilson, Stephen A.

2010-01-01

One of the difficulties in performing speciation analyses on solid samples is finding a suitable extraction method. Traditional methods for extraction of hexavalent chromium, Cr(VI), in soils, such as SW846 Method 3060A, can be tedious and are not always compatible with some determination methods. For example, the phosphate and high levels of carbonate and magnesium present in the U.S. Environmental Protection Agency (USEPA) Method 3060A digestion for Cr(VI) were found to be incompatible with the High Performance Liquid Chromatography-Inductively Coupled Plasma-Mass Spectrometry (HPLC-ICP-MS) detection method used by our laboratory. Modification of Method 3060A by eliminating the use of the phosphate buffer provided improved performance with the detection method, however dilutions are still necessary to achieve good chromatographic separation and detection of Cr(VI). An ultrasonic extraction method using a 1 mM Na2CO3 - 9 mM NaHCO3 buffer solution, adapted from Occupational Safety and Health Administration (OSHA) Method ID215, has been used with good results for the determination of Cr(VI) in air filters. The average recovery obtained for BCR-545 - Welding Dust Loaded on Filter (IRMM, Belgium) using this method was 99 percent (1.2 percent relative standard deviation) with no conversion of Cr(VI) to Cr(III) during the extraction process. This ultrasonic method has the potential for use with other sample matrices, such as ashes and soils. Preliminary investigations using NIST 2701 (Hexavalent Chromium in Contaminated Soil) loaded onto quartz filters showed promising results with approximately 90 percent recovery of the certified Cr(VI) value. Additional testing has been done using NIST 2701 and NIST 2700 using different presentation methods. Extraction efficiency of bulk presentation, where small portions of the sample are added to the bottom of the extraction vessel, will be compared with supported presentation, where small portions of the sample are loaded onto a

Hexavalent Chromium: Analysis of the Mechanism of Groundwater Contamination in a Former Industrial Site in the Province of Vicenza (Northern Italy)

OpenAIRE

Valentina Accoto; Pierluigi Bullo; Ruben Faccio; Leonardo Mason; Andrea Sottani

2017-01-01

The study consisted in the analysis of the mobilization mechanisms of hexavalent chromium (Cr(VI)) into groundwater from a decommissioned contaminated factory. The site is located in the Province of Vicenza and formerly was a chrome-plating plant. The subsoil consists predominantly of gravelly deposits with a thickness of at least one hundred meters. An unconfined aquifer is present with water table at about 23 m depth bgl. During the seven years of monitoring (2008-2014), the fluctuation of ...

Investigation of extraction of actinyl ions with inorganic ligands Pt. 1

International Nuclear Information System (INIS)

Fucks, L.; Lis, S.; Fidelis, I.

1979-01-01

Extraction coefficients (D) of hexavalent actinide ions have been determined by extraction chromatography, utilizing the selectivity of the TBP - HNO 3 system towards oxidation states. Plots logD against nitric acid concentration and logD against the atomic number of actinides show the decrease of extractability with Z, and a distinctly smaller difference between the extractability of uranyl and neptunyl than that of neptunyl and plutonyl ions. This latter fact is connected with the double-double effect. (A.L.)

Arsenic K-edge X-ray absorption near-edge spectroscopy to determine oxidation states of arsenic of a coastal aquifer–aquitard system

International Nuclear Information System (INIS)

Wang, Ya; Jiao, Jiu Jimmy; Zhu, Sanyuan; Li, Yiliang

2013-01-01

Determination of oxidation states of solid-phase arsenic in bulk sediments is a valuable step in the evaluation of its bioavailability and environmental fate in deposits, but is difficult when the sediments have low arsenic contents and heterogeneous distribution of arsenic species. As K-edge X-ray absorption near-edge spectroscopy (XANES) was used to determine quantitatively the oxidation states of arsenic in sediments collected from different depths of boreholes in the Pearl River Delta, China, where the highest aquatic arsenic concentration is 161.4 μg/L, but the highest solid arsenic content only 39.6 mg/kg. The results demonstrated that XANES is efficient in determining arsenic oxidation states of the sediments with low arsenic contents and multiple arsenic species. The study on the high-resolution vertical variations of arsenic oxidation states also indicated that these states are influenced strongly by groundwater activities. With the help of geochemical data, solid arsenic speciation, toxicity and availability were further discussed. -- Highlights: •XANES is efficient in determining arsenic oxidation states of the bulk sediments. •Distribution of arsenic oxidation states is consistent with geochemical conditions. •Arsenic oxidation states are influenced strongly by groundwater activities. -- As K-edge X-ray absorption near-edge spectroscopy is efficient in determining arsenic oxidation states of the bulk sediments with low arsenic contents and heterogeneous distribution of arsenic species

DetOx: a program for determining anomalous scattering factors of mixed-oxidation-state species.

Science.gov (United States)

Sutton, Karim J; Barnett, Sarah A; Christensen, Kirsten E; Nowell, Harriott; Thompson, Amber L; Allan, David R; Cooper, Richard I

2013-01-01

Overlapping absorption edges will occur when an element is present in multiple oxidation states within a material. DetOx is a program for partitioning overlapping X-ray absorption spectra into contributions from individual atomic species and computing the dependence of the anomalous scattering factors on X-ray energy. It is demonstrated how these results can be used in combination with X-ray diffraction data to determine the oxidation state of ions at specific sites in a mixed-valance material, GaCl(2).

Carbon oxidation state as a metric for describing the chemistry of atmospheric organic aerosol

Energy Technology Data Exchange (ETDEWEB)

Massachusetts Institute of Technology; Kroll, Jesse H.; Donahue, Neil M.; Jimenez, Jose L.; Kessler, Sean H.; Canagaratna, Manjula R.; Wilson, Kevin R.; Altieri, Katye E.; Mazzoleni, Lynn R.; Wozniak, Andrew S.; Bluhm, Hendrik; Mysak, Erin R.; Smith, Jared D.; Kolb, Charles E.; Worsnop, Douglas R.

2010-11-05

A detailed understanding of the sources, transformations, and fates of organic species in the environment is crucial because of the central roles that organics play in human health, biogeochemical cycles, and Earth's climate. However, such an understanding is hindered by the immense chemical complexity of environmental mixtures of organics; for example, atmospheric organic aerosol consists of at least thousands of individual compounds, all of which likely evolve chemically over their atmospheric lifetimes. Here we demonstrate the utility of describing organic aerosol (and other complex organic mixtures) in terms of average carbon oxidation state (OSC), a quantity that always increases with oxidation, and is readily measured using state-of-the-art analytical techniques. Field and laboratory measurements of OSC , using several such techniques, constrain the chemical properties of the organics and demonstrate that the formation and evolution of organic aerosol involves simultaneous changes to both carbon oxidation state and carbon number (nC).

Hexavalent chromium reduction under fermentative conditions with lactate stimulated native microbial communities.

Science.gov (United States)

Somenahally, Anil C; Mosher, Jennifer J; Yuan, Tong; Podar, Mircea; Phelps, Tommy J; Brown, Steven D; Yang, Zamin K; Hazen, Terry C; Arkin, Adam P; Palumbo, Anthony V; Van Nostrand, Joy D; Zhou, Jizhong; Elias, Dwayne A

2013-01-01

Microbial reduction of toxic hexavalent chromium (Cr(VI)) in-situ is a plausible bioremediation strategy in electron-acceptor limited environments. However, higher [Cr(VI)] may impose stress on syntrophic communities and impact community structure and function. The study objectives were to understand the impacts of Cr(VI) concentrations on community structure and on the Cr(VI)-reduction potential of groundwater communities at Hanford, WA. Steady state continuous flow bioreactors were used to grow native communities enriched with lactate (30 mM) and continuously amended with Cr(VI) at 0.0 (No-Cr), 0.1 (Low-Cr) and 3.0 (High-Cr) mg/L. Microbial growth, metabolites, Cr(VI), 16S rRNA gene sequences and GeoChip based functional gene composition were monitored for 15 weeks. Temporal trends and differences in growth, metabolite profiles, and community composition were observed, largely between Low-Cr and High-Cr bioreactors. In both High-Cr and Low-Cr bioreactors, Cr(VI) levels were below detection from week 1 until week 15. With lactate enrichment, native bacterial diversity substantially decreased as Pelosinus spp., and Sporotalea spp., became the dominant groups, but did not significantly differ between Cr concentrations. The Archaea diversity also substantially decreased after lactate enrichment from Methanosaeta (35%), Methanosarcina (17%) and others, to mostly Methanosarcina spp. (95%). Methane production was lower in High-Cr reactors suggesting some inhibition of methanogens. Several key functional genes were distinct in Low-Cr bioreactors compared to High-Cr. Among the Cr resistant microbes, Burkholderia vietnamiensis, Comamonas testosterone and Ralstonia pickettii proliferated in Cr amended bioreactors. In-situ fermentative conditions facilitated Cr(VI) reduction, and as a result 3.0 mg/L Cr(VI) did not impact the overall bacterial community structure.

Hexavalent chromium reduction under fermentative conditions with lactate stimulated native microbial communities.

Directory of Open Access Journals (Sweden)

Anil C Somenahally

Full Text Available Microbial reduction of toxic hexavalent chromium (Cr(VI in-situ is a plausible bioremediation strategy in electron-acceptor limited environments. However, higher [Cr(VI] may impose stress on syntrophic communities and impact community structure and function. The study objectives were to understand the impacts of Cr(VI concentrations on community structure and on the Cr(VI-reduction potential of groundwater communities at Hanford, WA. Steady state continuous flow bioreactors were used to grow native communities enriched with lactate (30 mM and continuously amended with Cr(VI at 0.0 (No-Cr, 0.1 (Low-Cr and 3.0 (High-Cr mg/L. Microbial growth, metabolites, Cr(VI, 16S rRNA gene sequences and GeoChip based functional gene composition were monitored for 15 weeks. Temporal trends and differences in growth, metabolite profiles, and community composition were observed, largely between Low-Cr and High-Cr bioreactors. In both High-Cr and Low-Cr bioreactors, Cr(VI levels were below detection from week 1 until week 15. With lactate enrichment, native bacterial diversity substantially decreased as Pelosinus spp., and Sporotalea spp., became the dominant groups, but did not significantly differ between Cr concentrations. The Archaea diversity also substantially decreased after lactate enrichment from Methanosaeta (35%, Methanosarcina (17% and others, to mostly Methanosarcina spp. (95%. Methane production was lower in High-Cr reactors suggesting some inhibition of methanogens. Several key functional genes were distinct in Low-Cr bioreactors compared to High-Cr. Among the Cr resistant microbes, Burkholderia vietnamiensis, Comamonas testosterone and Ralstonia pickettii proliferated in Cr amended bioreactors. In-situ fermentative conditions facilitated Cr(VI reduction, and as a result 3.0 mg/L Cr(VI did not impact the overall bacterial community structure.

Hexavalent Chromium Reduction under Fermentative Conditions with Lactate Stimulated Native Microbial Communities

Energy Technology Data Exchange (ETDEWEB)

Somenahally, Anil C [ORNL; Mosher, Jennifer J [ORNL; Yuan, Tong [University of Oklahoma; Phelps, Tommy Joe [ORNL; Brown, Steven D [ORNL; Yang, Zamin Koo [ORNL; Hazen, Terry C [ORNL; Arkin, Adam [Lawrence Berkeley National Laboratory (LBNL); Palumbo, Anthony Vito [ORNL; Van Nostrand, Dr. Joy D. [Oklahoma University; Zhou, Jizhong [University of Oklahoma; Elias, Dwayne A [ORNL

2013-01-01

Microbial reduction of toxic hexavalent chromium (Cr(VI)) in-situ is a plausible bioremediation strategy in electron-acceptor limited environments. However, higher [Cr(VI)] may impose stress on syntrophic communities and impact community structure and function. The study objectives were to understand the impacts of Cr(VI) concentrations on community structure and on the Cr(VI)-reduction potential of groundwater communities at Hanford, WA. Steady state continuous flow bioreactors were used to grow native communities enriched with lactate (30 mM) and continuously amended with Cr(VI) at 0.0 (No-Cr), 0.1 (Low-Cr) and 3.0 (High-Cr) mg/L. Microbial growth, metabolites, Cr(VI), 16S rRNA gene sequences and GeoChip based functional gene composition were monitored for 15 weeks. Temporal trends and differences in growth, metabolite profiles, and community composition were observed, largely between Low-Cr and High-Cr bioreactors. In both High-Cr and Low-Cr bioreactors, Cr(VI) levels were below detection from week 1 until week 15. With lactate enrichment, native bacterial diversity substantially decreased as Pelosinus spp., and Sporotalea spp., became the dominant groups, but did not significantly differ between Cr concentrations. The Archaea diversity also substantially decreased after lactate enrichment from Methanosaeta (35%), Methanosarcina (17%) and others, to mostly Methanosarcina spp. (95%). Methane production was lower in High-Cr reactors suggesting some inhibition of methanogens. Several key functional genes were distinct in Low-Cr bioreactors compared to High-Cr. Among the Cr resistant microbes, Burkholderia vietnamiensis, Comamonas testosterone and Ralstonia pickettii proliferated in Cr amended bioreactors. In-situ fermentative conditions facilitated Cr(VI) reduction, and as a result 3.0 mg/L Cr(VI) did not impact the overall bacterial community structure.

Regulation of Ca2+ release from mitochondria by the oxidation-reduction state of pyridine nucleotides

Science.gov (United States)

Lehninger, Albert L.; Vercesi, Anibal; Bababunmi, Enitan A.

1978-01-01

Mitochondria from normal rat liver and heart, and also Ehrlich tumor cells, respiring on succinate as energy source in the presence of rotenone (to prevent net electron flow to oxygen from the endogenous pyridine nucleotides), rapidly take up Ca2+ and retain it so long as the pyridine nucleotides are kept in the reduced state. When acetoacetate is added to bring the pyridine nucleotides into a more oxidized state, Ca2+ is released to the medium. A subsequent addition of a reductant of the pyridine nucleotides such as β-hydroxybutyrate, glutamate, or isocitrate causes reuptake of the released Ca2+. Successive cycles of Ca2+ release and uptake can be induced by shifting the redox state of the pyridine nucleotides to more oxidized and more reduced states, respectively. Similar observations were made when succinate oxidation was replaced as energy source by ascorbate oxidation or by the hydrolysis of ATP. These and other observations form the basis of a hypothesis for feedback regulation of Ca2+-dependent substrate- or energy-mobilizing enzymatic reactions by the uptake or release of mitochondrial Ca2+, mediated by the cytosolic phosphate potential and the ATP-dependent reduction of mitochondrial pyridine nucleotides by reversal of electron transport. Images PMID:25436

Investigations on the nephrotoxicity and hepatotoxicity of trivalent and hexavalent chromium compounds.

Science.gov (United States)

Dartsch, P C; Hildenbrand, S; Kimmel, R; Schmahl, F W

1998-09-01

In contrast to trivalent chromium (Cr(III)) compounds, hexavalent chromium ((Cr(VI)) compounds are oxidizing agents capable of directly inducing tissue damage and possessing carcinogenic, mutagenic and teratogenic potency. After oral or dermal absorption of Cr(VI), the kidney is the main target organ for chromium accumulation, which might result in acute tubular necrosis in humans. In contrast, an acute toxic effect of Cr(VI) on the liver has not yet been described. Therefore, we used two established epithelial cell lines from the kidney (Opossum kidney cells) and the liver (Hep G2 cells) to design an in vitro-assay which is able to examine acute toxic effects of chromium compounds. Cells of both cell lines were treated with various concentrations of Cr(III) and Cr(VI) ranging from 0.01 micromol/l to 1 mmol/l for 24 h. Thereafter, cell morphology, organization of the intracellular cytoskeleton, number of viable cells and mean cell volume were examined. The results show that Cr(VI), but not Cr(III), has an acute cytotoxic effect and causes a dose-dependent loss in cell viability. The effective dose that caused 50% of cell death was 5 micromol/l for kidney epithelial cells and 50 micromol/l for liver epithelial cells. This means that kidney epithelial cells are 10 times more sensitive towards Cr(VI) treatment than liver epithelial cells and this might explain the known nephrotoxicity in vivo. The loss in cell viability was accompanied by a rounding and detachment of the cells and a marked reduction of intracellular F-actin-containing stress fibers. Microtubules and intermediate-sized filaments were observed to be unaffected. Only in the case of kidney epithelial cells, a dose-dependent cell volume increase was observed after Cr(VI) treatment at concentrations up to 50 micromol/l. At higher concentrations, the cell volume decreased due to the high number of cells undergoing lysis and the appearance of cellular fragments. Various chloride channel blockers with

On-line dynamic extraction and automated determination of readily bioavailable hexavalent chromium in solid substrates using micro-sequential injection bead-injection lab-on-valve hyphenated with electrothermal atomic absorption spectrometry

DEFF Research Database (Denmark)

Long, Xiangbao; Miró, Manuel; Hansen, Elo Harald

2006-01-01

A novel and miniaturized micro-sequential injection bead injection lab-on-valve (μSI-BI-LOV) fractionation system was developed for in-line microcolumn soil extraction under simulated environmental scenarios and accurate monitoring of the content of easily mobilisable hexavalent chromium in soil...... environments at the sub-low parts-per-million level. The flow system integrates dynamic leaching of hexavalent chromium using deionized water as recommended by the German Standard DIN 38414-S4 method; on-line pH adjustment of the extract by a 0.01 mol L-1 Tris-HNO3 buffer solution; isolation of the chromate...... polluted agricultural soil material (San Joaquin Soil-Baseline Trace Element Concentrations) with water-soluble Cr(VI) salts at different concentration levels. The potential of the μSI-BI-LOV set-up with renewable surfaces for flame-AAS determination of high levels of readily bioavailable chromate...

Study on the solid state chemistry of ternary uranium oxides

International Nuclear Information System (INIS)

Yamashita, Toshiyuki

1988-03-01

With the increase of burnup of uranium oxide fuels, various kinds of fission products are formed, and the oxygen atoms combined with the consumed heavy atoms are freed. The solid state chemical and/or thermodynamic properties of these elements at high temperatures are complex, and have not been well clarified. In the present report, an approach was taken that the chemical interactions between UO 2 and these fission products can be regarded as causing overlapped effects of composing ternary uranium oxides, and formation reactions and phase behavior were studied for several ternary uranium oxides with typical fission product elements such as alkaline earth metals and rare earth elements. Precise determination methods for the composition of ternary uranium oxides were developed. The estimated accuracies for x and y values in M y U 1-y O 2+x were ± 0.006 and ± 0.004, respectively. The thermodynamic properties and the lattice parameters of the phases in the Ca-U-O and Pr-U-O systems were discussed in relation to the composition determined by the methods. Crystal structure analyses of cadmium monouranates were made with X-ray diffraction method. (author) 197 refs

A Randomized, Controlled Study of DTaP-IPV-HB-PRP-T, a Fully Liquid Hexavalent Vaccine, Administered in a 3-, 5- and 11- to 12-month Schedule.

Science.gov (United States)

Vesikari, Timo; Silfverdal, Sven-Arne; Jordanov, Emilia; Feroldi, Emmanuel

2017-01-01

To assess the immunogenicity and safety of a fully liquid, ready-to-use hexavalent DTaP-IPV-HB-PRP-T vaccine when administered in a 2 + 1 schedule at 3, 5 and 11-12 months of age. Phase III, randomized, active-controlled, observer-blind, multicenter study. Infants were randomized to receive DTaP-IPV-HB-PRP-T (N = 275) or a licensed control hexavalent vaccine (DTaP-IPV-HB//PRP~T: N = 275), both given in coadministration with Prevenar 13. Serum was analyzed for immune responses to all vaccine antigens. Noninferiority of DTaP-IPV-HB-PRP-T to the control vaccine was tested at completion of the primary series using predefined seroprotection (SP) rate and vaccine response (VR) rates. Safety was assessed using parental reports. Noninferiority of DTaP-IPV-HB-PRP-T to the control vaccine was demonstrated postdose 3 for each antigen, and the SP (for D, T, poliovirus 1, 2 and 3, hepatitis B and polyribosylribitol phosphate) and VR rates (for pertussis toxin and filamentous hemagglutinin) were high in each group. SP rates for D, T, polio 1, 2, 3 and VR rates for pertussis toxin and filamentous hemagglutinin were similar in each group. For hepatitis B, SP rate was slightly higher for DTaP-IPV-HB//PRP~T (99.6%) than DTaP-IPV-HB-PRP-T (96.4%), and for PRP, SP rate was higher for DTaP-IPV-HB-PRP-T (93.5%) than DTaP-IPV-HB//PRP~T (85.2%). For Prevenar 13, the SP rate was high for each serotype and similar for both groups. All vaccines were well tolerated. These study findings confirm the safety and immunogenicity and thus the suitability of this fully liquid hexavalent vaccine for administration in a 2 + 1 schedule.

Potentiometric determination of uranium with cobalt (3) acetate as oxidimetric titrant

International Nuclear Information System (INIS)

Muhammad, H.; Ishrat, P.; Zyka, J.

1972-01-01

A potentiometric method for the determination of uranium through the reduction of hexavalent to tetravalent state and its potentiometric oxidation in 8 N sulphuric acid with standard cobalt (3)-acetate has been worked out. The method is quite accurate with the error not exceeding 1% for mg amounts. Moreover an apparatus for preservation of reduced solution of uranium and its delivery for titrations has been designed. The same apparatus can be used for reducing and preserving solutions of strong reducing titrants. (author)

Early renal effects of occupational exposure to low-level hexavalent chromium

Energy Technology Data Exchange (ETDEWEB)

Nagaya, Teruo (Dept. of Public Health, Gifu Univ. School of Medicine, Tsukasa-machi (Japan)); Ishikawa, Noriko (Occupational Hygiene Center, Gifu Labour Standards Association, Hikie (Japan)); Hata, Hideo (Occupational Hygiene Center, Gifu Labour Standards Association, Hikie (Japan)); Takahashi, Akemi (Gifu-shi Central Public Health Center, Miyako-dori (Japan)); Yoshida, Izumi (Gifu-shi Central Public Health Center, Miyako-dori (Japan)); Okamoto, Yoshinari (Gifu-shi Central Public Health Center, Miyako-dori (Japan))

1994-05-01

To detect early renal effects of occupational exposure to hexavalent chromium (Cr), urinary total proteins (U-TP), urinary albumin (U-Alb) and urinary retinol-binding protein (U-RBP) were determined in 166 male Cr platers and 106 male controls. The mean employment time in Cr plating for the platers was 12.6 years. Urinary Cr (U-Cr), which was determined as an index of Cr exposure, ranged from ''not detected'' to 19.91 [mu]g/g creatinine in the platers. The U-Cr level was lower than those in other previous studies. Age-adjusted U-TP, U-Alb or U-RBP levels were not different between the platers and the controls. In the platers, a significant positive correlation was found between age-adjusted U-TP and U-Cr, but U-Cr had no significant relation to age-adjusted U-Alb or U-RBP level. Employment time had no effect on any age-adjusted urinary proteins. The Cr exposure may have been too low to induce definite renal dysfunction. Early renal effects of low-level Cr exposure may be mild, and may not be specific to renal function. (orig.)

Adsorption and desorption for dynamics transport of hexavalent chromium Cr(Ⅵ) in soil column

Science.gov (United States)

Tong, J.

2017-12-01

Batch experiments have been carried out to study the adsorption of heavy metals in soils, and the migration and transformation of hexavalent chromium Cr(Ⅵ) in the soil of a vegetable base were studied by dynamic adsorption and desorption soil column experiments. The aim of this study was to investigate the effect of initial concentration and pH value on the adsorption process of Cr(Ⅵ). Breakthrough curve were used to evaluate the capacity of Cr(Ⅵ) adsorption in soil columns. The results show that the higher the initial concentration, the worse the adsorption capacity of Cr(Ⅵ). The adsorption of Cr(Ⅵ) was strongly sensitive to pH value. The capacity of Cr(Ⅵ) adsorption is maximized at very low pH value. This may be due to changes in pH that cause a series of complex reactions in Cr(Ⅵ). In a strongly acidic environment, the reaction of Cr(Ⅵ) with hydrogen ions is accompanied by the formation of Cr3+, which reacts with the soil free iron-aluminum oxide to produce hydroxide in the soil. The results of the desorption experiments indicate that Cr(Ⅵ) is more likely to leach from this soil, but if the eluent is strong acid solution, the leaching process will be slow and persistent. The program CXTFIT was used to fit the breakthrough curve to estimate parameters. The results of the calculation of the dispersion coefficient (D) can be obtained by this program. The two-site model fit the breakthrough curve data of Cr(Ⅵ) well, and the parameters calculated by CXTFIT can be used to explain the behavior of Cr(Ⅵ) migration and transformation in soil columns. When pH=2, the retardation factor (R) reach at 79.71 while the value of the R is generally around 10 in other experiments. The partitioning coefficient β shows that more than half of the adsorption sites are rate-limited in this adsorption process and non-equilibrium effects the Cr(Ⅵ) transport process in this soil.

Short review of high-pressure crystal growth and magnetic and electrical properties of solid-state osmium oxides

Energy Technology Data Exchange (ETDEWEB)

Yamaura, Kazunari, E-mail: YAMAURA.Kazunari@nims.go.jp [Superconducting Properties Unit, National Institute for Materials Science, 1-1 Namiki, Tsukuba, Ibaraki 305-0044 (Japan); Graduate School of Chemical Sciences and Engineering, Hokkaido University, North 10 West 8, Kita-ku, Sapporo, Hokkaido 060-0810 (Japan)

2016-04-15

High-pressure crystal growth and synthesis of selected solid-state osmium oxides, many of which are perovskite-related types, are briefly reviewed, and their magnetic and electrical properties are introduced. Crystals of the osmium oxides, including NaOsO{sub 3}, LiOsO{sub 3}, and Na{sub 2}OsO{sub 4}, were successfully grown under high-pressure and high-temperature conditions at 6 GPa in the presence of an appropriate amount of flux in a belt-type apparatus. The unexpected discovery of a magnetic metal–insulator transition in NaOsO{sub 3}, a ferroelectric-like transition in LiOsO{sub 3}, and high-temperature ferrimagnetism driven by a local structural distortion in Ca{sub 2}FeOsO{sub 6} may represent unique features of the osmium oxides. The high-pressure and high-temperature synthesis and crystal growth has played a central role in the development of solid-state osmium oxides and the elucidation of their magnetic and electronic properties toward possible use in multifunctional devices. - Graphical Abstract: Flux-grown crystals of NaOsO{sub 3} under high-pressure and high-temperature conditions in a belt-type apparatus. The crystal shows a magnetically driven metal–insulator transition at a temperature of 410 K. - Highlights: • Short review of high-pressure crystal growth of solid-state osmium oxides. • Wide variety of magnetic properties of solid-state osmium oxides. • Perovskite and related dense structures stabilized at 3–17 GPa.

Correlations between the electrochemical behaviour and surface film composition of TZM alloy exposed to divertor water coolant environments

International Nuclear Information System (INIS)

Maday, M.-F.; Giorgi, R.; Dikonimos-Makris, T.

1997-01-01

X-ray photoelectron spectroscopy (XPS) has been carried out on TZM alloy surfaces after short and long immersion tests in high temperature (250 C) aqueous environments simulating possible fusion reactor coolant conditions during operation. Phase identification by XPS was used in connection with the open circuit potential trends to suggest plausible hypotheses about TZM corrosion behaviour in the various chemical environments considered in this study. It was proposed that exposure of TZM to oxidizing water conditions produced poorly protective layers, which consist essentially of low (IV) and intermediate (V) valency Mo oxides/hydroxides. Conversely the results obtained in deaerated and reducing water conditions suggested that barrier films could develop in these environments: the phases exhibit a bilayered structure and consisted of an inner tetravalent Mo oxide/hydroxide and an outer hexavalent Mo oxide. The protective properties of such layers were attributed to the hexavalent Mo species. (orig.)

Determination of plutonium in nitric acid solutions - Method by oxidation by cerium(IV), reduction by iron(II) ammonium sulfate and amperometric back-titration with potassium dichromate

International Nuclear Information System (INIS)

1987-01-01

This International Standard specifies a precise and accurate analytical method for determining plutonium in nitric acid solutions. Plutonium is oxidized to plutonium(VI) in a 1 mol/l nitric acid solution with cerium(IV). Addition of sulfamic acid prevents nitrite-induced side reactions. The excess of cerium(IV) is reduced by adding a sodium arsenite solution, catalysed by osmium tetroxide. A slight excess of arsenite is oxidized by adding a 0.2 mol/l potassium permanganate solution. The excess of permanganate is reduced by adding a 0.1 mol/l oxalic acid solution. Iron(III) is used to catalyse the reduction. A small excess of oxalic acid does not interfere in the subsequent plutonium determination. These reduction and oxidation stages can be followed amperometrically and the plutonium is left in the hexavalent state. The sulfuric acid followed by a measured amount of standardized iron(II) ammonium sulfate solution in excess of that required to reduce the plutonium(VI) to plutonium(IV) is added. The excess iron(II) and any plutonium(III) formed to produce iron(III) and plutonium(IV) is amperometrically back-titrated using a standard potassium dichromate solution. The method is almost specifically for plutonium. It is suitable for the direct determination of plutonium in materials ranging from pure product solutions, to fast reactor fuel solutions with a uranium/plutonium ratio of up to 10:1, either before or after irradiation

Acid Dissolution of Depleted Uranium from Catalyst using Microwave

Energy Technology Data Exchange (ETDEWEB)

Sung, Jin Hyun; Jeong, Seong Gi; Park, Kwang Heon [Kyunghee University, Yongin (Korea, Republic of)

2011-05-15

The separation process of uranium is one of the most important fields in nuclear industry because uranium is used primary in nuclear power plants. Uranium ores are treated by either acid or alkaline reagents. Uranium can be dissolved by acid or alkaline solutions. There are two oxidation states in which the hexavalent form, the oxide of which is UO{sub 3}, and the tetravalent form, the oxide of which is UO{sub 2}. However, depleted uranium(DU) has also been used as a catalyst in specialized chemical reaction such as ammoxidation. The preferred catalyst for propylene oxidation with ammonia was a uranium oxide-antimony oxide composition. The active phase of catalyst was known as USbO{sub 5} and USb{sub 3}O{sub 10}. There is pentavalent form. Waste catalyst containing DU was generated and stored in chemical industry. In this work, we removed DU from catalyst by acid dissolution

Study on Cr(VI) Leaching from Cement and Cement Composites

Science.gov (United States)

Palascakova, Lenka; Kanuchova, Maria

2018-01-01

This paper reports an experimental study on hexavalent chromium leaching from cement samples and cement composites containing silica fume and zeolite additions that were subjected to various leaching agents. The water-soluble Cr(VI) concentrations in cements ranged from 0.2 to 3.2 mg/kg and represented only 1.8% of the total chromium content. The presence of chromium compounds with both chromium oxidation states of III and VI was detected in the cement samples by X-ray photoelectron spectroscopy (XPS). Leaching tests were performed in a Britton-Robinson buffer to simulate natural conditions and showed increased dissolution of Cr(VI) up to 6 mg/kg. The highest amount of leached hexavalent chromium was detected after leaching in HCl. The findings revealed that the leaching of chromium from cements was higher by 55–80% than that from the cement composites. A minimum concentration was observed for all cement samples when studying the relationship between the soluble Cr(VI) and the cement storage time. PMID:29690550

Microbial utilization of low molecular weight organic substrates in soil depends on their carbon oxidation state

Science.gov (United States)

Gunina, Anna; Smith, Andrew; Jones, Davey; Kuzyakov, Yakov

2017-04-01

Removal of low molecular weight organic substances (LMWOS), originating from plants and microorganisms, from soil solution is regulated by microbial uptake. In addition to the concentration of LMWOS in soil solution, the chemical properties of each substance (e.g. C oxidation state, number of C atoms, number of -COOH groups) can affect their uptake and subsequent partitioning of C within the soil microbial community. The aim of this study was to trace the initial fate of three dominant classes of LMWOS in soil (sugars, carboxylic and amino acids), including their removal from solution and utilization by microorganisms, and to reveal the effect of substance chemical properties on these processes. Soil solution, spiked at natural abundance levels with 14C-labelled glucose, fructose, malate, succinate, formate, alanine or glycine, was added to the soil and 14C was traced in the dissolved organic carbon (DOC), CO2, cytosol and soil organic carbon (SOC) over 24 hours. The half-life time of all LMWOS in the DOC (T1 /2-solution) varied between 0.6-5.0 min showing extremely fast initial uptake of LMWOS. The T1 /2-solution of substances was dependent on C oxidation state, indicating that less oxidized organic substances (with C oxidation state "0") were retained longer in soil solution than oxidized substances. The LMWOS-C T1 /2-fast, characterizing the half-life time of 14C in the fast mineralization pool, ranged between 30 and 80 min, with the T1 /2-fast of carboxylic acids (malic acid) being the fastest and the T1 /2-fast of amino acids (glycine) being the slowest. An absence of correlation between T1 /2-fast and either C oxidation state, number of C atoms, or number of -COOH groups suggests that intercellular metabolic pathways are more important for LMWOS transformation in soil than their basic chemical properties. The CO2 release during LMWOS mineralization accounted for 20-90% of 14C applied. Mineralization of LMWOS was the least for sugars and the greatest for

Influence of steam generator surface state on corrosion and oxide formation

International Nuclear Information System (INIS)

Mazenc, Arnaud; Leclercq, Stephanie; Seyeux, Antoine; Galtayries, Anouk; Marcus, Philippe

2012-09-01

The corrosion and release of nickel-based alloy Steam Generator tubes are partly due to their surface state. Among the most important parameters influencing the corrosion, the effect of grain size and the effect of grain crystallographic orientation have been chosen to be studied. The aim of this study is to determine how these parameters have an impact on the corrosion of Steam Generator tubes. Thermal treatments (700 deg. C and 1050 deg. C) have been performed on several samples in Alloy 690 to obtain homogeneous grain sizes, varying from 25 μm to 110 μm. Two samples have been oxidised for four days in a recirculating autoclave, reproducing primary conditions. The changes of oxide composition and thickness were examined by ToF-SIMS on samples exposed to primary water conditions. The intensity profiles versus thicknesses of characteristic oxide anions, such as CrO - , NiO - or FeO - enable us to evaluate the effect of grain size and crystallographic orientation on the formation of an enriched inner chromium layer. As regards to the grain size, there was no effect on the growth, but smaller grains led to a chromium-rich oxide layer. The effect of crystallographic orientation was observed on the oxidation kinetics and the composition of oxide scales. (authors)

Adsorption of CO, CO2, H2, and H2O on titania surfaces with different oxidation states

International Nuclear Information System (INIS)

Raupp, G.B.; Dumesic, J.A.

1985-01-01

The adsorptive properties of titania surfaces with different oxidation states were proved by temperature-programmed desorption (TPD) of CO, H 2 , CO 2 , and H 2 O. Auger electron spectroscopy and X-ray photoelectron spectroscopy revealed that vacuum annealing an oxidized titanium foil at temperatures from 300 to 800 K was an effective means of systematically varying the average surface oxidation state from Ti 4+ to Ti 2+ . Carbon monoxide weakly adsorbed (desorption energy of 44-49 kJ x mol -1 ) in a carbonyl fashion on coordinatively unsaturated cation sites. Titania surfaces were inert with respect to H 2 adsorption and dissociation. Carbon dioxide adsorbed in a linear molecular fashion. Water adsorbed both molecularly and dissociatively. Results are discussed in terms of the role of titania oxidation state in CO hydrogenation over titania-supported metal catalysts. 74 references, 7 figures

Chelation and stabilization of berkelium in oxidation state +IV

Science.gov (United States)

Deblonde, Gauthier J.-P.; Sturzbecher-Hoehne, Manuel; Rupert, Peter B.; An, Dahlia D.; Illy, Marie-Claire; Ralston, Corie Y.; Brabec, Jiri; de Jong, Wibe A.; Strong, Roland K.; Abergel, Rebecca J.

2017-09-01

Berkelium (Bk) has been predicted to be the only transplutonium element able to exhibit both +III and +IV oxidation states in solution, but evidence of a stable oxidized Bk chelate has so far remained elusive. Here we describe the stabilization of the heaviest 4+ ion of the periodic table, under mild aqueous conditions, using a siderophore derivative. The resulting Bk(IV) complex exhibits luminescence via sensitization through an intramolecular antenna effect. This neutral Bk(IV) coordination compound is not sequestered by the protein siderocalin—a mammalian metal transporter—in contrast to the negatively charged species obtained with neighbouring trivalent actinides americium, curium and californium (Cf). The corresponding Cf(III)-ligand-protein ternary adduct was characterized by X-ray diffraction analysis. Combined with theoretical predictions, these data add significant insight to the field of transplutonium chemistry, and may lead to innovative Bk separation and purification processes.

Composition and oxidation state of sulfur in atmospheric particulate matter

Directory of Open Access Journals (Sweden)

A. F. Longo

2016-10-01

Full Text Available The chemical and physical speciation of atmospheric sulfur was investigated in ambient aerosol samples using a combination of sulfur near-edge x-ray fluorescence spectroscopy (S-NEXFS and X-ray fluorescence (XRF microscopy. These techniques were used to determine the composition and oxidation state of sulfur in common primary emission sources and ambient particulate matter collected from the greater Atlanta area. Ambient particulate matter samples contained two oxidation states: S0 and S+VI. Ninety-five percent of the individual aerosol particles (> 1 µm analyzed contain S0. Linear combination fitting revealed that S+VI in ambient aerosol was dominated by ammonium sulfate as well as metal sulfates. The finding of metal sulfates provides further evidence for acidic reactions that solubilize metals, such as iron, during atmospheric transport. Emission sources, including biomass burning, coal fly ash, gasoline, diesel, volcanic ash, and aerosolized Atlanta soil, and the commercially available bacterium Bacillus subtilis, contained only S+VI. A commercially available Azotobacter vinelandii sample contained approximately equal proportions of S0 and S+VI. S0 in individual aerosol particles most likely originates from primary emission sources, such as aerosolized bacteria or incomplete combustion.

Oxidized Nitrogen Balance over 15 Months at Rural and Urban New York State Locations

Science.gov (United States)

Schwab, J. J.; Ninneman, M.; Marto, J.; Edgerton, E. S.; Blanchard, C. L.; Shaw, S. L.

2017-12-01

Continuous measurements of oxidized nitrogen species (NO, NO2, and HNO3), families of species (NOy, alkyl nitrates [or ANs], and peroxyacetyl nitrates [or PANs]), and particle nitrate (pNO3) were carried out for a fifteen-month period from August 2016 through October 2017 at two locations in New York State. The two sites were a rural research station at Pinnacle State Park in Addison, NY and an urban research station at Queens College in New York City. Four different chemiluminescence analyzers with various converters and denuders were employed to make these measurements. Instrumentation used for the study will be described, as well as some of the challenges created by combining data from these independent analyzers to address the oxidized nitrogen budget at the two sites. The Pinnacle State Park site often experiences quite clean air with low ppb levels of total NOy and a greater fraction of oxidized nitrogen products (NOz species). This contrasts with the urban Queens College location, which experiences stronger NOx sources. Seasonal differences in the NOx/NOy and NOz/NOy ratios, and the makeup of the NOz species, are also significant and will be explored in the presentation.

Multifunctional organophosphorus extractants: a status report on development and applications

International Nuclear Information System (INIS)

Schulz, W.W.; Horwitz, E.P.

1988-01-01

Up-to-date state of the development of science and technology of multifunctional organophosphorus extractants is considered. The detailed classification of these extractants is presented. They attracted pasticular interest because of affinity of some bifunctional phosphonates, phosphine oxides, carbamoylalkylphosphonates to trivalent Am, tetravalent and hexavalent actinides, trivalent lanthanides in strong mineral acids, and because of ability of some alkylpyrophosphoric acids to extract effectively U(4) from concentrated solutions of phosphoric acid. Application of these extractants for analytic purposes and in the field of nuclear technology is considered

Punica granatum L. protects mice against hexavalent chromium-induced genotoxicity

Directory of Open Access Journals (Sweden)

Renato Ivan de Ávila

2013-12-01

Full Text Available This study investigated the chemoprotective effects of Punica granatum L. (Punicaceae fruits alcoholic extract (PGE on mice exposed to hexavalent chromium [Cr(VI]. Animals were pretreated with PGE (25, 50 or 75 mg/kg/day for 10 days and subsequently exposed to a sub-lethal dose of Cr(VI (30 mg/kg. The frequency of micronucleated polychromatic erythrocytes in the bone marrow was investigated and the Cr(VI levels were measured in the kidneys, liver and plasm. For the survival analysis, mice were previously treated with PGE for 10 days and exposed to a single lethal dose of Cr(VI (50 mg/kg. Exposure to a sub-lethal dose of Cr(VI induced a significant increase in the frequency of micronucleated cells. However, the prophylactic treatment with PGE led to a reduction of 44.5% (25 mg/kg, 86.3% (50 mg/kg and 64.2% (75 mg/kg in the incidence of micronuclei. In addition, the 50 mg/kg dose of PGE produced a higher chemoprotective effect, since the survival rate was 90%, when compared to that of the non-treated group. In these animals, reduced amounts of chromium were detected in the biological materials, in comparison with the other groups. Taken together, the results demonstrated that PGE exerts a protective effect against Cr(VI-induced genotoxicity.

Quantitative chemical state XPS analysis of first row transition metals, oxides and hydroxides

International Nuclear Information System (INIS)

Biesinger, M C; Payne, B P; McIntryre, N S; Hart, B R; Lau, L Wm; Grosvenor, A P; Smart, R StC

2008-01-01

Practical quantitative chemical state X-ray photoelectron spectroscopy (XPS) analysis of first row transition metals, oxides and hydroxides is challenging due to the complexity of their M 2p spectra. Complex multiplet splitting, shake-up and plasmon loss structure can play a role in the interpretation of the chemical states present. This paper will show practical curve fitting procedures for the quantitative measurement of different chemical states for metal oxides and hydroxides from a survey of transition metals. It will also discuss some of the limitations and pitfalls present as well as give practical examples of their successful use. These curve-fitting procedures are based on 1) standard spectra from quality reference samples, 2) a survey of appropriate literature databases and/or a compilation of literature references, 3) fitting of multiplet split spectra based on spectra of numerous reference materials and theoretical modelling, 4) spectral subtractions routines, again using reference spectra, and 5) specific literature references where fitting procedures are available

Quantitative chemical state XPS analysis of first row transition metals, oxides and hydroxides

Energy Technology Data Exchange (ETDEWEB)

Biesinger, M C; Payne, B P; McIntryre, N S [Department of Chemistry, University of Western Ontario, London, Ontario, N6A 5B7 (Canada); Hart, B R; Lau, L Wm [Surface Science Western, Room G1, Western Science Centre, University of Western Ontario, London, Ontario, N6A 5B7 (Canada); Grosvenor, A P [Department of Chemistry, Gunning/Lemieux Chemistry Centre, University of Alberta, Edmonton, Alberta, T6G 2G2 (Canada); Smart, R StC [ACeSSS, Applied Centre for Structural and Synchrotron Studies, University of South Australia, Mawson Lakes, SA 5095 (Australia)], E-mail: biesingr@uwo.ca

2008-03-15

Practical quantitative chemical state X-ray photoelectron spectroscopy (XPS) analysis of first row transition metals, oxides and hydroxides is challenging due to the complexity of their M 2p spectra. Complex multiplet splitting, shake-up and plasmon loss structure can play a role in the interpretation of the chemical states present. This paper will show practical curve fitting procedures for the quantitative measurement of different chemical states for metal oxides and hydroxides from a survey of transition metals. It will also discuss some of the limitations and pitfalls present as well as give practical examples of their successful use. These curve-fitting procedures are based on 1) standard spectra from quality reference samples, 2) a survey of appropriate literature databases and/or a compilation of literature references, 3) fitting of multiplet split spectra based on spectra of numerous reference materials and theoretical modelling, 4) spectral subtractions routines, again using reference spectra, and 5) specific literature references where fitting procedures are available.

Towards the improvement of the oxidation resistance of Nb-silicides in situ composites: A solid state diffusion approach

International Nuclear Information System (INIS)

Mathieu, S.; Knittel, S.; François, M.; Portebois, L.; Mathieu, S.; Vilasi, M.

2014-01-01

Highlights: •Local equilibrium is attained during oxidation at phase boundaries (steady state conditions). •A solid state diffusion model explains the oxidation mechanism of Nb-silicides composites. •The Nb ss fraction is not the only parameters governing the oxidation rate of Nb-silicides. •Aluminium increases the thermodynamic activity of Si in the Nb-silicides composites. •The results indicate the need to develop a Nb–Ti–Hf–Al–Cr–Si thermodynamic database. -- Abstract: The present study focuses on the oxidation mechanism of Nb-silicide composites and on the effect of the composition on the oxidation rate at 1100 °C. A theoretical approach is proposed based on experimental results and used to optimise the oxidation resistance. The growth model based on multiphase diffusion was experimentally tested and confirmed by manufacturing seven composites with different compositions. It was also found that the effect of the composition has to be evaluated at 1100 °C within a short time duration (50 h), where the oxide scale and the internal oxidation zone both grow according to parabolic kinetics

Effect of surface state on the oxidation behavior of welded 308L in simulated nominal primary water of PWR

Science.gov (United States)

Ming, Hongliang; Zhang, Zhiming; Wang, Jiazhen; Zhu, Ruolin; Ding, Jie; Wang, Jianqiu; Han, En-Hou; Ke, Wei

2015-05-01

The oxidation behavior of 308L weld metal (WM) with different surface state in the simulated nominal primary water of pressurized water reactor (PWR) was studied by scanning electron microscopy (SEM) equipped with energy dispersive X-ray spectroscopy (EDS), X-ray diffraction (XRD) analyzer and X-ray photoelectron spectroscopy (XPS). After 480 h immersion, a duplex oxide film composed of a Fe-rich outer layer (Fe3O4, Fe2O3 and a small amount of NiFe2O4, Ni(OH)2, Cr(OH)3 and (Ni, Fe)Cr2O4) and a Cr-rich inner layer (FeCr2O4 and NiCr2O4) can be formed on the 308L WM samples with different surface state. The surface state has no influence on the phase composition of the oxide films but obviously affects the thickness of the oxide films and the morphology of the oxides (number & size). With increasing the density of dislocations and subgrain boundaries in the cold-worked superficial layer, the thickness of the oxide film, the number and size of the oxides decrease.

Pentavalent Uranium Chemistry - Synthetic Pursuit Of A Rare Oxidation State

Energy Technology Data Exchange (ETDEWEB)

Graves, Christopher R [Los Alamos National Laboratory; Kiplinger, Jaqueline L [Los Alamos National Laboratory

2009-01-01

This feature article presents a comprehensive overview of pentavalent uranium systems in non-aqueous solution with a focus on the various synthetic avenues employed to access this unusual and very important oxidation state. Selected characterization data and theoretical aspects are also included. The purpose is to provide a perspective on this rapidly evolving field and identify new possibilities for future developments in pentavalent uranium chemistry.

Bonding structure and morphology of chromium oxide films grown by pulsed-DC reactive magnetron sputter deposition

Energy Technology Data Exchange (ETDEWEB)

Gago, R., E-mail: rgago@icmm.csic.es [Instituto de Ciencia de Materiales de Madrid, Consejo Superior de Investigaciones Científicas, E-28049 Madrid (Spain); Vinnichenko, M. [Fraunhofer-Institut für Keramische Technologien und Systeme IKTS, D-01277 Dresden (Germany); Hübner, R. [Helmholtz-Zentrum Dresden – Rossendorf, Institute of Ion Beam Physics and Materials Research, Bautzner Landstraße 400, 01328 Dresden (Germany); Redondo-Cubero, A. [Departamento de Física Aplicada and Centro de Microanálisis de Materiales, Universidad Autónoma de Madrid, E-28049 Madrid (Spain)

2016-07-05

Chromium oxide (CrO{sub x}) thin films were grown by pulsed-DC reactive magnetron sputter deposition in an Ar/O{sub 2} discharge as a function of the O{sub 2} fraction in the gas mixture (ƒ) and for substrate temperatures, T{sub s}, up to 450 °C. The samples were analysed by Rutherford backscattering spectrometry (RBS), spectroscopic ellipsometry (SE), atomic force microscopy (AFM), scanning (SEM) and transmission (TEM) electron microscopy, X-ray diffraction (XRD), and X-ray absorption near-edge structure (XANES). On unheated substrates, by increasing ƒ the growth rate is higher and the O/Cr ratio (x) rises from ∼2 up to ∼2.5. Inversely, by increasing T{sub s} the atomic incorporation rate drops and x falls to ∼1.8. XRD shows that samples grown on unheated substrates are amorphous and that nanocrystalline Cr{sub 2}O{sub 3} (x = 1.5) is formed by increasing T{sub s}. In amorphous CrO{sub x}, XANES reveals the presence of multiple Cr environments that indicate the growth of mixed-valence oxides, with progressive promotion of hexavalent states with ƒ. XANES data also confirms the formation of single-phase nanocrystalline Cr{sub 2}O{sub 3} at elevated T{sub s}. These structural changes also reflect on the optical and morphological properties of the films. - Highlights: • XANES of CrO{sub x} thin films grown by pulsed-DC reactive magnetron sputtering. • Identification of mixed-valence amorphous CrO{sub x} oxides on unheated substrates. • Promotion of amorphous chromic acid (Cr{sup VI}) by increasing O{sub 2} partial pressure. • Production of single-phase Cr{sub 2}O{sub 3} films by increasing substrate temperature. • Correlation of bonding structure with morphological and optical properties.

The influence of iridium chemical oxidation state on the performance and durability of oxygen evolution catalysts in PEM electrolysis

Science.gov (United States)

Siracusano, S.; Baglio, V.; Grigoriev, S. A.; Merlo, L.; Fateev, V. N.; Aricò, A. S.

2017-10-01

Nanosized Ir-black (3 nm) and Ir-oxide (5 nm) oxygen evolution electrocatalysts showing high performance in polymer electrolyte membrane (PEM) water electrolysis based on Aquivion® short-side chain ionomer membrane are investigated to understand the role of the Ir oxidation state on the electrocatalytic activity and stability. Despite the smaller mean crystallite size, the Ir-black electrocatalyst shows significantly lower initial performance than the Ir-oxide. During operation at high current density, the Ir-black shows a decrease of cell potential with time whereas the Ir-oxide catalyst shows increasing cell potential resulting in a degradation rate of about 10 μV/h, approaching 1000 h. The unusual behaviour of the Ir-black results from the oxidation of metallic Ir to IrOx. The Ir-oxide catalyst shows instead a hydrated structure on the surface and a negative shift of about 0.5 eV for the Ir 4f binding energy after 1000 h electrolysis operation. This corresponds to the formation of a sub-stoichiometric Ir-oxide on the surface. These results indicate that a hydrated IrO2 with high oxidation state on the surface is favourable in decreasing the oxygen evolution overpotential. Modifications of the Ir chemical oxidation state during operation can affect significantly the catalytic activity and durability of the electrolysis system.

Measurement of soil carbon oxidation state and oxidative ratio by 13C nuclear magnetic resonance

Science.gov (United States)

Hockaday, W.C.; Masiello, C.A.; Randerson, J.T.; Smernik, R.J.; Baldock, J.A.; Chadwick, O.A.; Harden, J.W.

2009-01-01

The oxidative ratio (OR) of the net ecosystem carbon balance is the ratio of net O2 and CO2 fluxes resulting from photosynthesis, respiration, decomposition, and other lateral and vertical carbon flows. The OR of the terrestrial biosphere must be well characterized to accurately estimate the terrestrial CO2 sink using atmospheric measurements of changing O2 and CO2 levels. To estimate the OR of the terrestrial biosphere, measurements are needed of changes in the OR of aboveground and belowground carbon pools associated with decadal timescale disturbances (e.g., land use change and fire). The OR of aboveground pools can be measured using conventional approaches including elemental analysis. However, measuring the OR of soil carbon pools is technically challenging, and few soil OR data are available. In this paper we test three solid-state nuclear magnetic resonance (NMR) techniques for measuring soil OR, all based on measurements of the closely related parameter, organic carbon oxidation state (Cox). Two of the three techniques make use of a molecular mixing model which converts NMR spectra into concentrations of a standard suite of biological molecules of known C ox. The third technique assigns Cox values to each peak in the NMR spectrum. We assess error associated with each technique using pure chemical compounds and plant biomass standards whose Cox and OR values can be directly measured by elemental analyses. The most accurate technique, direct polarization solid-state 13C NMR with the molecular mixing model, agrees with elemental analyses to ??0.036 Cox units (??0.009 OR units). Using this technique, we show a large natural variability in soil Cox and OR values. Soil Cox values have a mean of -0.26 and a range from -0.45 to 0.30, corresponding to OR values of 1.08 ?? 0.06 and a range from 0.96 to 1.22. We also estimate the OR of the carbon flux from a boreal forest fire. Analysis of soils from nearby intact soil profiles imply that soil carbon losses associated

The Impact of Environmental Factors in Influencing Epigenetics Related to Oxidative States in the Cardiovascular System

Directory of Open Access Journals (Sweden)

Francesco Angelini

2017-01-01

Full Text Available Oxidative states exert a significant influence on a wide range of biological and molecular processes and functions. When their balance is shifted towards enhanced amounts of free radicals, pathological phenomena can occur, as the generation of reactive oxygen species (ROS in tissue microenvironment or in the systemic circulation can be detrimental. Epidemic chronic diseases of western societies, such as cardiovascular disease, obesity, and diabetes correlate with the imbalance of redox homeostasis. Current advances in our understanding of epigenetics have revealed a parallel scenario showing the influence of oxidative stress as a major regulator of epigenetic gene regulation via modification of DNA methylation, histones, and microRNAs. This has provided both the biological link and a potential molecular explanation between oxidative stress and cardiovascular/metabolic phenomena. Accordingly, in this review, we will provide current insights on the physiological and pathological impact of changes in oxidative states on cardiovascular disorders, by specifically focusing on the influence of epigenetic regulation. A special emphasis will highlight the effect on epigenetic regulation of human’s current life habits, external and environmental factors, including food intake, tobacco, air pollution, and antioxidant-based approaches. Additionally, the strategy to quantify oxidative states in humans in order to determine which biological marker could best match a subject’s profile will be discussed.

Homoleptic Ce(III) and Ce(IV) Nitroxide Complexes: Significant Stabilization of the 4+ Oxidation State

Energy Technology Data Exchange (ETDEWEB)

Bogart, Justin A.; Lewis, Andrew J.; Medling, Scott A.; Piro, Nicholas A.; Carroll, Patrick J.; Booth, Corwin H.; Schelter, Eric J.

2014-06-25

Electrochemical experiments performed on the complex Ce-IV[2-((BuNO)-Bu-t)py](4), where [2-((BuNO)-Bu-t)py](-) = N-tert-butyl-N-2-pyridylnitroxide, indicate a 2.51 V stabilization of the 4+ oxidation state of Ce compared to [(Bu4N)-Bu-n](2)[Ce(NO3)(6)] in acetonitrile and a 2.95 V stabilization compared to the standard potential for the ion under aqueous conditions. Density functional theory calculations suggest that this preference for the higher oxidation state is a result of the tetrakis(nitroxide) ligand framework at the Ce cation, which allows for effective electron donation into, and partial covalent overlap with, vacant 4f orbitals with delta symmetry. The results speak to the behavior of CeO2 and related solid solutions in oxygen uptake and transport applications, in particular an inherent local character of bonding that stabilizes the 4+ oxidation state. The results indicate a cerium(IV) complex that has been stabilized to an unprecedented degree through tuning of its ligand-field environment.

Bioaccumulation studies in a benthic marine species in different radioactivity concentrations

International Nuclear Information System (INIS)

Stamouli, M.; Papadopoulou, C.

1992-07-01

The accumulation of trivalent and hexavalent 51Cr by the mollusc Venus verrucosa in three different radioactivity concentrations was studied. The bioavailability of the trivalent 51Cr was found to be much higher than that of the hexavalent 51Cr. Also the uptake patterns of 51Cr(III) and 51Cr(VI) were different. This distribution of the accumulated trivalent and hexavalent 51Cr in the body of Venus verrucosa was investigated and appeared to be influenced by the valence state of 51Cr. The elimination of the accumulated radioactivity was also investigated and the effective and biological half lives for the two year valence states of 51Cr were determined

Investigations on the oxidation of nitric acid plutonium solutions with ozone

International Nuclear Information System (INIS)

Boehm, M.

1983-01-01

The reaction of ozone with nitric acid Pu solutions was studied as a function of reaction time, acid concentration and Pu concentration. Strong nitric acid Pu solutions are important in nuclear fuel element production and reprocessing. The Pu must be converted into hexavalent Pu before precipitation from the homogeneous solution together with uranium-IV, ammonia and CO 2 in the form of ammonium uranyl/plutonyl carbonate (AUPuC). Formation of a solid phase during ozonation was observed for the first time. The proneness to solidification increases with incrasing plutonium concentrations and with decreasing acid concentrations. If the formation of a solid phase during ozonation of nitric acid Pu solutions cannot be prevented, the PU-IV oxidation process described is unsuitable for industrial purposes as Pu solutions in industrial processes have much higher concentrations than the solutions used in the present investigation. (orig./EF) [de

The effect of interfaces on solid-state reactions between oxides

International Nuclear Information System (INIS)

Johnson, M.T.; Carter, C.B.

1998-01-01

A thin-film geometry has been used to study fundamental solid-state reaction processes occurring at interfaces in two spinel-forming oxide systems. In the first system, NiO/Al 2 O 3 , epitactic NiO films were deposited on various orientations of single-crystal α-Al 2 O 3 . In this case, the reaction kinetics were studied and correlated with the interfacial structure (or substrate orientation). In the second, In 2 O 3 /MgO, solid-state reactions were studied under the influence of an electric field. The electric field provides a driving force for mass transport that affects both the reaction process and the morphological stability of an interface

Oxidation of an aluminium-magnesium alloy in liquid state. Methodology of determination of mechanisms from not necessarily repeatable experiments

International Nuclear Information System (INIS)

Surla, Karine

1998-01-01

This research thesis reports the study of the oxidation of an aluminium-5 pc magnesium alloy in its liquid state in an oxygen environment, using thermogravimetric analysis and that of magnesium in its solid state. In a first part, the author reports a thermodynamic and bibliographical study on magnesium transformation in its solid state (Mg/O 2 and Mg/H 2 O systems, transformation with dry and humid synthetic air, oxidation inhibitors) and on Al-Mg alloy transformation in presence of oxygen (thermodynamic properties of aluminium-rich Al-Mg alloys, Al-Mg/O 2 /N 2 and Al-Mg/O 2 /N 2 /H 2 O systems). The next parts address the selection of reaction systems for the different cases (oxidation of solid magnesium in oxygen, oxidation of the Al-Mg alloy in oxygen), the modelling of the formation of magnesia from solid magnesium and from the Al-Mg alloy, and the modelling of the liquid Al-Mg A5182 alloy oxidation in oxygen [fr

Coupled interactions between volatile activity and Fe oxidation state during arc crustal processes

Science.gov (United States)

Humphreys, Madeleine C.S.; Brooker, R; Fraser, D.C.; Burgisser, A; Mangan, Margaret T.; McCammon, C

2015-01-01

Arc magmas erupted at the Earth’s surface are commonly more oxidized than those produced at mid-ocean ridges. Possible explanations for this high oxidation state are that the transfer of fluids during the subduction process results in direct oxidation of the sub-arc mantle wedge, or that oxidation is caused by the effect of later crustal processes, including protracted fractionation and degassing of volatile-rich magmas. This study sets out to investigate the effect of disequilibrium crustal processes that may involve coupled changes in H2O content and Fe oxidation state, by examining the degassing and hydration of sulphur-free rhyolites. We show that experimentally hydrated melts record strong increases in Fe3+/∑Fe with increasing H2O concentration as a result of changes in water activity. This is relevant for the passage of H2O-undersaturated melts from the deep crust towards shallow crustal storage regions, and raises the possibility that vertical variations in fO2 might develop within arc crust. Conversely, degassing experiments produce an increase in Fe3+/∑Fe with decreasing H2O concentration. In this case the oxidation is explained by loss of H2 as well as H2O into bubbles during decompression, consistent with thermodynamic modelling, and is relevant for magmas undergoing shallow degassing en route to the surface. We discuss these results in the context of the possible controls on fO2 during the generation, storage and ascent of magmas in arc settings, in particular considering the timescales of equilibration relative to observation as this affects the quality of the petrological record of magmatic fO2.

Removal of hexavalent chromium by using red mud activated with cetyltrimethylammonium bromide.

Science.gov (United States)

Li, Deliang; Ding, Ying; Li, Lingling; Chang, Zhixian; Rao, Zhengyong; Lu, Ling

2015-01-01

The removal of hexavalent chromium [Cr(VI)] from aqueous solution by using red mud activated with cetyltrimethylammonium bromide (CTAB) was studied. The optimum operation parameters, such as CTAB concentration, pH values, contact time, and initial Cr(VI) concentration, were investigated. The best concentration of CTAB for modifying red mud was found to be 0.50% (mCTAB/VHCl,0.6 mol/L). The lower pH (mud activated with CTAB can greatly improve the removal ratio of Cr(VI) as high as four times than that of original red mud. Adsorption equilibrium was reached within 30 min under the initial Cr(VI) concentration of 100 mg L(-1). The isotherm data were analysed using Langmuir and Freundlich models. The adsorption of Cr(VI) on activated red mud fitted well to the Langmuir isotherm model, and the maximum adsorption capacity was estimated as 22.20 mg g(-1) (Cr/red mud). The adsorption process could be well described using the pseudo-second-order model. The result shows that activated red mud is a promising agent for low-cost water treatment.

Biotransformation of hexavalent chromium into extracellular chromium(III) oxide nanoparticles using Schwanniomyces occidentalis.

Science.gov (United States)

Mohite, Pallavi T; Kumar, Ameeta Ravi; Zinjarde, Smita S

2016-03-01

To demonstrate biotransformation of toxic Cr(VI) ions into Cr2O3 nanoparticles by the yeast Schwanniomyces occidentalis. Reaction mixtures containing S. occidentalis NCIM 3459 and Cr(VI) ions that were initially yellow turned green after 48 h incubation. The coloration was due to the synthesis of chromium (III) oxide nanoparticles (Cr2O3NPs). UV-Visible spectra of the reaction mixtures showed peaks at 445 and 600 nm indicating (4)A2g → (4)T1g and (4)A2g → (4)T2g transitions in Cr2O3, respectively. FTIR profiles suggested the involvement of carboxyl and amide groups in nanoparticle synthesis and stabilization. The Cr2O3NPs ranged between 10 and 60 nm. Their crystalline nature was evident from the selective area electron diffraction and X-ray diffraction patterns. Energy dispersive spectra confirmed the chemical composition of the nanoparticles. These biogenic nanoparticles could find applications in different fields. S. occidentalis mediated biotransformation of toxic Cr(VI) ions into crystalline extracellular Cr2O3NPs under benign conditions.

Étude de l’évolution de la teneur en chrome hexavalent dans le cuir, influence des conditions de fabrication et importance des facteurs environnementaux

OpenAIRE

Fontaine , Mathilde

2017-01-01

Currently, 80 to 85% of leather is tanned with chrome. This process allows to obtain excellent physico-mechanical properties with optimum economic conditions. The chromium salts in trivalent form used in the manufacturing of leather are not harmful; however under some conditions and associated with other substances, trivalent chromium can be transformed into hexavalent chromium, highly allergenic and potentially harmful to the health of the consumer. Since 1st May 2015, the presence of hexava...

Remediation of groundwater contaminated by exa valent chromium. Part 1.: Treatment technologies

International Nuclear Information System (INIS)

Sbaffoni, S.; Vaccari, M.

2009-01-01

Chromium compounds have been used in several industrial activities and they are often found in soil and groundwater of former industrial sites. Chromium exists in various oxidation states, but the trivalent and hexavalent oxidation ones are of major environmental concern due to their stability in the environment. In particular, Cr(V I) is highly soluble and mobile and is very toxic with mutagenic and carcinogenic effects. The present paper describes the main chemical, physical and toxicological properties of Cr(V I), its fate in the subsoil and both the conventional and innovative technologies for its removal from contaminated groundwater. The paper includes also a brief description of few interesting foreign case studies. [it

Ion bombardment effects on surface states in selected oxide systems: rutile and alkaline earth titanates

International Nuclear Information System (INIS)

Gruen, D.M.

1978-01-01

In this paper, the nature of the surface states of n-type TiO 2 and SrTiO 3 is discussed and the role of ion bombardment in modifying the properties of these states is elucidated. Insofar as possible, the interrelationships between oxide nonstoichiometry, surface states, ion bombardment effects and photoelectrolysis are explored

Optically induced bistable states in metal/tunnel-oxide/semiconductor /MTOS/ junctions

Science.gov (United States)

Lai, S. K.; Dressendorfer, P. V.; Ma, T. P.; Barker, R. C.

1981-01-01

A new switching phenomenon in metal-oxide semiconductor tunnel junction has been discovered. With a sufficiently large negative bias applied to the electrode, incident visible light of intensity greater than about 1 microW/sq cm causes the reverse-biased junction to switch from a low-current to a high-current state. It is believed that hot-electron-induced impact ionization provides the positive feedback necessary for switching, and causes the junction to remain in its high-current state after the optical excitation is removed. The junction may be switched back to the low-current state electrically. The basic junction characteristics have been measured, and a simple model for the switching phenomenon has been developed.

Effect of high doses of L-ascorbic acid on the antioxidative/oxidative state in the rats

DEFF Research Database (Denmark)

Niemiec, T.; Sawosz, E.; Chwalibog, André

2005-01-01

The objective of this study was to determine the effects of mega-doses of vitamin C (0.3, 0.6 and 0.9% of diet) as a dietary supplement for rats on selected indices of the antioxidative/oxidative state in 40 growing Wistar rats (4x10). It was found that L-ascorbic acid and Total Antioxidative State...... (TAS) in plasma did not increase with increasing vitamin C supply. The results indicate that high doses of L-ascorbic acid (0.3 and 0.9 but not 0.6%) increased the concentration of this antioxidant in plasma. Supplementation of vitamin C above 0.3% to the diets had pro-oxidative effects on lipid...... structures, while application of 0.9% promoted oxidative degradation of rat livers....

Visualizing chemical states and defects induced magnetism of graphene oxide by spatially-resolved-X-ray microscopy and spectroscopy.

Science.gov (United States)

Wang, Y F; Singh, Shashi B; Limaye, Mukta V; Shao, Y C; Hsieh, S H; Chen, L Y; Hsueh, H C; Wang, H T; Chiou, J W; Yeh, Y C; Chen, C W; Chen, C H; Ray, Sekhar C; Wang, J; Pong, W F; Takagi, Y; Ohigashi, T; Yokoyama, T; Kosugi, N

2015-10-20

This investigation studies the various magnetic behaviors of graphene oxide (GO) and reduced graphene oxides (rGOs) and elucidates the relationship between the chemical states that involve defects therein and their magnetic behaviors in GO sheets. Magnetic hysteresis loop reveals that the GO is ferromagnetic whereas photo-thermal moderately reduced graphene oxide (M-rGO) and heavily reduced graphene oxide (H-rGO) gradually become paramagnetic behavior at room temperature. Scanning transmission X-ray microscopy and corresponding X-ray absorption near-edge structure spectroscopy were utilized to investigate thoroughly the variation of the C 2p(π*) states that are bound with oxygen-containing and hydroxyl groups, as well as the C 2p(σ*)-derived states in flat and wrinkle regions to clarify the relationship between the spatially-resolved chemical states and the magnetism of GO, M-rGO and H-rGO. The results of X-ray magnetic circular dichroism further support the finding that C 2p(σ*)-derived states are the main origin of the magnetism of GO. Based on experimental results and first-principles calculations, the variation in magnetic behavior from GO to M-rGO and to H-rGO is interpreted, and the origin of ferromagnetism is identified as the C 2p(σ*)-derived states that involve defects/vacancies rather than the C 2p(π*) states that are bound with oxygen-containing and hydroxyl groups on GO sheets.

Exposure to Particulate Hexavalent Chromium Exacerbates Allergic Asthma Pathology

Science.gov (United States)

Schneider, Brent C.; Constant, Stephanie L.; Patierno, Steven R.; Jurjus, Rosalyn A.; Ceryak, Susan M.

2011-01-01

Airborne hexavalent chromate, Cr(VI), has been identified by the Environmental Protection Agency as a possible health threat in urban areas, due to the carcinogenic potential of some of its forms. Particulate chromates are produced in many different industrial settings, with high levels of aerosolized forms historically documented. Along with an increased risk of lung cancer, a high incidence of allergic asthma has been reported in workers exposed to certain inhaled particulate Cr(VI) compounds. However, a direct causal association between Cr(VI) and allergic asthma has not been established. We recently showed that inhaled particulate Cr(VI) induces an innate neutrophilic inflammatory response in BALB/c mice. In the current studies we investigated how the inflammation induced by inhaled particulate Cr(VI) might alter the pathology of an allergic asthmatic response. We used a well-established mouse model of allergic asthma. Groups of ovalbumin protein (OVA)-primed mice were challenged either with OVA alone, or with a combination of OVA and particulate zinc chromate, and various parameters associated with asthmatic responses were measured. Co-exposure to particulate Cr(VI) and OVA mediated a mixed form of asthma in which both eosinophils and neutrophils are present in airways, tissue pathology is markedly exacerbated, and airway hyperresponsiveness is significantly increased. Taken together these findings suggest that inhalation of particulate forms of Cr(VI) may augment the severity of ongoing allergic asthma, as well as alter its phenotype. Such findings may have implications for asthmatics in settings in which airborne particulate Cr(VI) compounds are present at high levels. PMID:22178736

Oxidative stress markers in hypertensive states of pregnancy: preterm and term disease.

Directory of Open Access Journals (Sweden)

Lesia Olha Kurlak

2014-08-01

Full Text Available Discussion continues as to whether de novo hypertension in pregnancy with significant proteinuria (pre-eclampsia; PE and non-proteinuric new hypertension (gestational hypertension; GH are parts of the same disease spectrum or represent different conditions. Non-pregnant hypertension, pregnancy and PE are all associated with oxidative stress. We have established a 6 weeks post-partum clinic for women who experienced a hypertensive pregnancy. We hypothesized that PE and GH could be distinguished by markers of oxidative stress; thiobarbituric acid reactive substances (TBARS and antioxidants (ferric ion reducing ability of plasma; FRAP. Since the severity of PE and GH is greater pre-term, we also compared pre-term and term disease. Fifty-eight women had term PE, 23 pre-term PE, 60 had term GH and 6 pre-term GH, 11 pre-existing (essential hypertension (EH without PE. Limited data were available from normotensive pregnancies (n=7 and non-pregnant controls (n=14. There were no differences in postpartum TBARS or FRAP between hypertensive states; TBARS (P=0.001 and FRAP (P=0.009 were lower in plasma of non-pregnant controls compared to recently-pregnant women. Interestingly FRAP was higher in preterm than term GH (P=0.013. In PE and GH, TBARS correlated with low density lipoprotein (LDL-cholesterol (P=0.036; this association strengthened with inclusion of EH ((P=0.011. The 10 year Framingham index for cardiovascular risk was positively associated with TBARS (P=0.003.Oxidative stress profiles do not differ between hypertensive states but appear to distinguish between recently-pregnant and non-pregnant states. This suggests that pregnancy may alter vascular integrity with changes remaining 6 weeks postpartum. LDL-cholesterol is a known determinant of oxidative stress in cardiovascular disease and we have shown this association to be present in hypertensive pregnancy further emphasizing that such a pregnancy may be revealing a pre-existing cardiovascular

Ultrathin reduced graphene oxide films as transparent top-contacts for light switchable solid-state molecular junctions

DEFF Research Database (Denmark)

Li, Tao; Jevric, Martyn; Hauptmann, Jonas Rahlf

2013-01-01

A new type of solid-state molecular junction is introduced, which employs reduced graphene oxide as a transparent top contact that permits a self-assembled molecular monolayer to be photoswitched in situ, while simultaneously enabling charge-transport measurements across the molecules. The electr......A new type of solid-state molecular junction is introduced, which employs reduced graphene oxide as a transparent top contact that permits a self-assembled molecular monolayer to be photoswitched in situ, while simultaneously enabling charge-transport measurements across the molecules...

Determination of Pu Oxidation states in the HCl Media Using with UV-Visible Absorption Spectroscopic Techniques

International Nuclear Information System (INIS)

Lee, Myung Ho; Suh, Mu Yeol; Park, Kyoung Kyun; Park, Yeong Jae; Kim, Won Ho

2006-01-01

The spectroscopic characteristics of Pu (III, IV, V, VI) in the HCl media were investigated by measuring Pu oxidation states using a UV-Vis-NIR spectrophotometer (400-1200 nm) after adjusting Pu oxidation states with oxidation/reduction reagents. Pu in stock solution was reduced to Pu(III) with NH 2 OH · HCl, and oxidized to Pu(IV) and Pu(VI) with NaNO 2 and HCIO 4 , respectively. Also, Pu(V) was adjusted in the Pu(VI) solution with NH 2 OH · HCl. The major absorption peaks of Pu (IV) and Pu(III) were measured in the 470 nm and 600 nm, respectively. The major absorption peaks of Pu (VI) and Pu(V) were measured in the 830 nm and 1135 nm, respectively. There was not found to be significant changes of UV-V is absorption spectra for Pu(III), Pu(IV) and Pu(VI) with aging time, except that an unstable Pu(V) immediately reduced to Pu(III).

Removal of Hexavalent Chromium from Aqueous Solution by Modified Holly Sawdust: A Study of Equilibrium and Kinetics

Directory of Open Access Journals (Sweden)

S. Azizian

2010-01-01

Full Text Available Introduction & Objective: Industrial wastewaters including heavy metals, are among the important sources of environmental pollution. Heavy metals such as chromium are found in plating wastewater and is harmful for human health and environment. The purpose of the present study was to investigate the absorption of heavy metals such as chromium onto modified holly sawdust as an cheaper absorbent. Materials & Methods: This study was a fundamental- application study done in Hamadan University of Medical Sciences, hygiene faculty water and wastewater chemistry laboratory. This study investigated the removal of hexavalent chromium by using modified holly sawdust with pH changes ,contact time ,absorbent dose and Cr(VI concentrations in batch system. Then the result was analyzed by Excel software.Results: The results showed that the removal efficiency decrease is accompanied by the increase of pH and initial chromium concentration. pH increase from 2 to 12(equilibrium time= 180 min, adsorbent dose= 0.6g/100CC, Cr(VI concentrations= 60 mg/L,leaded to the removal efficiency decrease from 99.67 % to 29.78 %. Also removal efficiency decreased from 99.37 % to 40.24 % after increasing the initial chromium concentrations from 20 mg/L to 100 mg/L. Moreover the results showed the removal efficiency increased after increasing the adsorbent dose and contact time. By increasing adsorbent dose from 0.2 g/100CC to 1 g/100CC, the removal efficiency increased from 34.65 % to 99.76 %.Additionally, the removal efficiency increased from 48.53%to 99.76% by increasing contact time from 5 mins to 180 mins. Experimental isotherms and kinetics models were assessed by Langmuir and Freundlich isotherms and pseudo-first-order and pseudo-second-order kinetics models. The results showed that the data were acceptably explained acceptably by Langmuir isotherms and pseudo-second-order kinetics models respectively.Conclusion: The results showed that the removal of hexavalent chromium

Using Fluorescence XANES Measurement to Correct the Content of Hexavalent Chromium in Chromate Conversion Coatings Determined by Diphenyl Carbazide Color Test

International Nuclear Information System (INIS)

Nishino, Junichi; Ofuchi, Hironori; Taniguchi, Yosuke; Honma, Tetsuo; Sekikawa, Toshikazu; Otani, Haruka; Bando, Akio

2007-01-01

The Restriction of the use of certain Hazardous Substances (RoHS) directive will take effect on July 1 of this year. From that date, the use of chromate conversion coatings containing hexavalent chromium will not be permitted. By comparing the concentration of Cr6+ determined by the diphenyl carbazide color test and by fluorescence XANES (X-Ray Absorption Near Edge Structure) measurement, we can correct for the Cr6+ content of the color test. This will enable the use of the diphenyl carbazide color test to check product shipments in compliance with the RoHS directive

The effect on phase separation of the oxidation state of molybdenum in a Na2O-B2O3-SiO2 glass

International Nuclear Information System (INIS)

Kawamoto, Y.; Clemens, K.; Tomozawa, M.; Warden, J.T.

1981-01-01

The effect of oxidation state on phase separation was studied for 13Na 2 O, 49B 2 O 3 , 38SiO 2 (mol%) glasses containing 1 mol% Mo oxide. The glasses were melted under various conditions to vary the oxidation states of Mo ions. The oxidation states of Mo ions were determined by chemical analysis and ESR. The crystallisation tendency, the immiscibility temperature, and the phase separation morphology of the glasses were examined by DTA, x-ray diffraction, opalescence method, and replica electron microscopy. Glasses containing Mo 4+ ions have a great tendency to precipitate MoO 2 crystals. The immiscibility temperature of glass goes through a minimum when the oxidation states of Mo ions are changed. It was suggested that there is an optimum oxidation state to prevent crystallisation and to suppress the phase separation tendency of this system. (author)

Obesity-Associated Oxidative Stress: Strategies Finalized to Improve Redox State

Directory of Open Access Journals (Sweden)

Valeria Gasperi

2013-05-01

Full Text Available Obesity represents a major risk factor for a plethora of severe diseases, including diabetes, cardiovascular disease, non-alcoholic fatty liver disease, and cancer. It is often accompanied by an increased risk of mortality and, in the case of non-fatal health problems, the quality of life is impaired because of associated conditions, including sleep apnea, respiratory problems, osteoarthritis, and infertility. Recent evidence suggests that oxidative stress may be the mechanistic link between obesity and related complications. In obese patients, antioxidant defenses are lower than normal weight counterparts and their levels inversely correlate with central adiposity; obesity is also characterized by enhanced levels of reactive oxygen or nitrogen species. Inadequacy of antioxidant defenses probably relies on different factors: obese individuals may have a lower intake of antioxidant- and phytochemical-rich foods, such as fruits, vegetables, and legumes; otherwise, consumption of antioxidant nutrients is normal, but obese individuals may have an increased utilization of these molecules, likewise to that reported in diabetic patients and smokers. Also inadequate physical activity may account for a decreased antioxidant state. In this review, we describe current concepts in the meaning of obesity as a state of chronic oxidative stress and the potential interventions to improve redox balance.

Obesity-Associated Oxidative Stress: Strategies Finalized to Improve Redox State

Science.gov (United States)

Savini, Isabella; Catani, Maria Valeria; Evangelista, Daniela; Gasperi, Valeria; Avigliano, Luciana

2013-01-01

Obesity represents a major risk factor for a plethora of severe diseases, including diabetes, cardiovascular disease, non-alcoholic fatty liver disease, and cancer. It is often accompanied by an increased risk of mortality and, in the case of non-fatal health problems, the quality of life is impaired because of associated conditions, including sleep apnea, respiratory problems, osteoarthritis, and infertility. Recent evidence suggests that oxidative stress may be the mechanistic link between obesity and related complications. In obese patients, antioxidant defenses are lower than normal weight counterparts and their levels inversely correlate with central adiposity; obesity is also characterized by enhanced levels of reactive oxygen or nitrogen species. Inadequacy of antioxidant defenses probably relies on different factors: obese individuals may have a lower intake of antioxidant- and phytochemical-rich foods, such as fruits, vegetables, and legumes; otherwise, consumption of antioxidant nutrients is normal, but obese individuals may have an increased utilization of these molecules, likewise to that reported in diabetic patients and smokers. Also inadequate physical activity may account for a decreased antioxidant state. In this review, we describe current concepts in the meaning of obesity as a state of chronic oxidative stress and the potential interventions to improve redox balance. PMID:23698776

Chromium VI administration induces oxidative stress in hypothalamus and anterior pituitary gland from male rats.

Science.gov (United States)

Nudler, Silvana I; Quinteros, Fernanda A; Miler, Eliana A; Cabilla, Jimena P; Ronchetti, Sonia A; Duvilanski, Beatriz H

2009-03-28

Hexavalent chromium (Cr VI)-containing compounds are known carcinogens which are present in industrial settings and in the environment. The major route of chromium exposure for the general population is oral intake. Previously we have observed that Cr VI affects anterior pituitary secretion and causes oxidative stress in vitro. The aim of the present work was to investigate if in vivo Cr VI treatment (100 ppm of Cr VI in drinking water for up 30 days) causes oxidative stress in hypothalamus and anterior pituitary gland from male rats. This treatment produced a 4-fold increase of chromium content in hypothalamus and 10-fold increase in anterior pituitary gland. Lipid peroxidation showed a significant increase in hypothalamus and anterior pituitary. Cr VI augmented superoxide dismutase activity in anterior pituitary gland and glutathione reductase activity in hypothalamus, but glutathione peroxidase and catalase activities remained unchanged in both tissues. Heme oxygenase-1 mRNA expression significantly rose in both tissues. Metallothionein 1 mRNA content increased in anterior pituitary and metallothionein 3 mRNA increased in hypothalamus. These results show, for the first time, that oral chronic administration of Cr VI produces oxidative stress on the hypothalamus and anterior pituitary gland which may affect normal endocrine function.

Oxidation states of Fe and Ti in blue sapphire

International Nuclear Information System (INIS)

Wongrawang, P; Wongkokua, W; Monarumit, N; Thammajak, N; Wathanakul, P

2016-01-01

X-ray absorption near-edge spectroscopy (XANES) can be used to study the oxidation state of a dilute system such as transition metal defects in solid-state samples. In blue sapphire, Fe and Ti are defects that cause the blue color. Inter-valence charge transfer (IVCT) between Fe 2+ and Ti 4+ has been proposed to describe the optical color’s origin. However, the existence of divalent iron cations has not been thoroughly investigated. Fluorescent XANES is therefore employed to study K-edge absorptions of Fe and Ti cations in various blue sapphire samples including natural, synthetic, diffused and heat-treated sapphires. All the samples showed an Fe absorption edge at 7124 eV, corresponding to the Fe 3+ state; and Ti at 4984 eV, corresponding to Ti 4+ . From these results, we propose Fe 3+ -Ti 4+ mixed acceptor states located at 1.75 eV and 2.14 eV above the valence band of corundum, that correspond to 710 nm and 580 nm bands of UV–vis absorption spectra, to describe the cause of the color of blue sapphire. (paper)

Solid-state electrochromic cell with anodic iridium oxide film electrodes

International Nuclear Information System (INIS)

Dautremont-Smith, W.C.; Beni, G.; Schiavone, L.M.; Shay, J.L.

1979-01-01

A new solid-state electrochromic cell has been fabricated using an anodic iridium oxide film (AIROF) display electrode. The cell has the symmetric sandwich structure AIROFvertical-barNafionvertical-barAIROF, with the Nafion solid electrolyte opacified by an in situ precipitation technique. A symmetric square-wave voltage of 1.5 V amplitude produces clearly perceivable color changes from pale to dark blue-gray in approx. =1 sec when viewed in diffuse reflection. Good open-circuit optical memory is exhibited:

Intestinal Oxidative State Can Alter Nutrient and Drug Bioavailability

Directory of Open Access Journals (Sweden)

Faria Ana

2009-01-01

Full Text Available Organic cations (OCs are substances of endogenous (e.g., dopamine, choline or exogenous (e.g., drugs like cimetidine origin that are positively charged at physiological ph. since many of these compounds can not pass the cell membrane freely, their transport in or out of cells must be mediated by specific transport systems. Transport by organic cation transporters (OCTs can be regulated rapidly by altering their trafficking and/or affinities in response to stimuli. However, for example, a specific disease could lead to modifications in the expression of OCTs. Chronic exposure to oxidative stress has been suggested to alter regulation and functional activity of proteins through several pathways. According to results from a previous work, oxidation-reduction pathways were thought to be involved in intestinal organic cation uptake modulation. The present work was performed in order to evaluate the influence of oxidative stressors, especially glutathione, on the intestinal organic cation absorption. For this purpose, the effect of compounds with different redox potential (glutathione, an endogenous antioxidant, and procyanidins, diet antioxidants was assessed on MPP+ (1-methyl-4-phenylpyridinium iodide uptake in an enterocyte cell line (Caco-2. Caco-2 cells were subcultured with two different media conditions (physiological: 5 mM glucose, referred as control cells; and high-glucose: 25 mM glucose, referred as HG cells. In HG cells, the uptake was significantly lower than in control cells. Redox changing interventions affected Mpp+ uptake, both in control and in high-glucose Caco-2 cells. Cellular glutathione levels could have an important impact on membrane transporter activity. The results indicate that modifications in the cellular oxidative state modulate MPP+ uptake by Caco-2 cells. Such modifications may reflect in changes of nutrient and drug bioavailability.

Molecular beam epitaxy growth of niobium oxides by solid/liquid state oxygen source and lithium assisted metal-halide chemistry

Science.gov (United States)

Tellekamp, M. Brooks; Greenlee, Jordan D.; Shank, Joshua C.; Doolittle, W. Alan

2015-09-01

In order to consistently grow high quality niobium oxides and lithium niobium oxides, a novel solid/liquid state oxygen source, LiClO4, has been implemented in a molecular beam epitaxy (MBE) system. LiClO4 is shown to decompose into both molecular and atomic oxygen upon heating. This allows oxidation rates similar to that of molecular oxygen but at a reduced overall beam flux, quantified by in situ Auger analysis. LiClO4 operation is decomposition limited to less than 400 °C, and other material limitations are identified. The design of a custom near-ambient NbCl5 effusion cell is presented, which improves both short and long term stability. Films of Nb oxidation state +2, +3, and +5 are grown using these new tools, including the multi-functional sub-oxide LiNbO2.

Speciation of the oxidation states of plutonium in aqueous solutions by UV/Vis spectroscopy, CE-ICP-MS and CE-RIMS

International Nuclear Information System (INIS)

Buerger, S.; Banik, N.L.; Buda, R.A.; Kratz, J.V.; Kuczewski, B.; Trautmann, N.

2007-01-01

For the speciation of the plutonium oxidation states in aqueous solutions, the online coupling of capillary electrophoresis (CE) with inductively coupled plasma mass spectrometry (ICP-MS) has been developed. Depending on the radius/electrical charge ratio, the oxidation states III, IV, V, and VI of plutonium are separated by CE, based on the different migration times through the capillary and are detected by ICP-MS. The detection limit is 20 ppb, i.e. 10 9 -10 10 atoms (10 -12 -10 -13 g) for one oxidation state with an uncertainty of the reproducibility of the migration times of ≤ 1% and ≤ 5% for the peak area. The redox kinetics of the different plutonium oxidation states in the presence of humic substances (humic and fulvic acid) have been studied. A relatively rapid reduction of Pu(VI) (10 to 1000 h) in contact with Gorleben fulvic or Aldrich humic acid could be observed, depending on the pH of the solution. Furthermore, at pH=1, a reduction to Pu(III) and Pu(IV) in a mixture of all four oxidation states in contact with Gorleben fulvic acid after one month has been observed. In order to improve the sensitivity of the CE method, the offline coupling of CE to resonance ionization mass spectrometry (RIMS) has been explored. First applications of this new speciation method are presented. (orig.)

Raman spectroscopic study of the oxidation state of Eu in molten LiCl-KCl

Energy Technology Data Exchange (ETDEWEB)

Park, Seung; Yun, Jong-Il [KAIST, Daejeon(Korea, Republic of)

2016-10-15

Spectroscopy can provide high reliability for the quantitative analysis of such system. The molar absorptivity of Eu(II) at 325 nm is reported as about 1645 M{sup -1}cm{sup -1}, which is too high to apply to higher concentration. A high-temperature Raman spectroscopy has been set and employed for analyzing the molecular structure and coordination complex and investigating the oxidation state of europium in molten LiCl-KCl. Europium can be present in divalent state while many other lanthanides exist in trivalent state. The thermodynamic properties of europium ions have been studied using electrochemical methods, spectroscopic methods, and EPR technique. Although there has been discrepancy of the reduced amount of europium in previous works, the majority of Eu(III) is thought to be reduced to Eu(II) in molten LiCl-KCl spontaneously at relatively low concentration (< 7.5 × 10{sup -4} M). Raman spectroscopy was employed to investigate the oxidation state of EuClx in LiCl-KCl at 500 .deg. C. The Raman scattering results suggest the majority of trivalent europium is reduced to divalent state with the composition change by vaporization. The Raman bands show highly asymmetric structure, quite different from regular octahedral structure.

Chemical state analysis of oxidation products on steel surface by conversion electron Moessbauer spectrometry

International Nuclear Information System (INIS)

Ujihira, Yusuke; Nomura, Kiyoshi

1978-01-01

The polished NT-70H steel (Fe: 95.97%, C: 0.56%, diameter: 5 cm, thickness: 0.5 cm) was immersed in deionized water or in solutions containing (0.25 -- 0.5) M of chloride, sulfate and nitrate ions. The chemical states of oxidation products of iron on the surface were identified through the analysis of conversion electron Moessbauer spectra (CEMS). CEMS of the steel surface, which had been dipped in deionized water, revealed that γ-FeOOH was formed on the surface. The thickness of γ-FeOOH layer increased with the increase of the duration of dipping. Dissolved oxygen in the solution played an essential role in the oxidation of iron to γ-FeOOH. Oxidation product of iron dipped in the 0.5 M sodium chloride solution was identified as γ-FeOOH. Amorphous paramagnetic iron (III) compound tended to form in the presence of hydrogen peroxide or ammonium ions in the solutions. The increase of alkalinity of the solution up to pH 12 suppressed the oxidation rate and assisted the formation of green rust, which was confirmed by the appearance of the quadrupole splitting peaks of the green rust. In the 0.25 M sodium sulfate solution, oxidation of the steel surface proceeded slowly and the quadrupole splitting peaks of Fe(OH) 2 were seen in the CEMS. The peak intensity of Fe(OH) 2 gradually decreased and that of γ-FeOOH increased by the extension of immersion of steel in the solution. Magnetite (Fe 3 O 4 ) layer was developed beneath the γ-FeOOH layer, when steel was dipped in 0.5 M sodium nitrate solution. However, the peaks of Fe 3 O 4 were not seen on CEMS of steel surface immersed in 0.5 M ammonium nitrate solution. Thus, applying the feasibility of CEMS for the characterization of oxidated compounds of iron on the steel surface formed by the immersion in solutions, the oxidation mechanism of the steel surface was discussed based upon the results of chemical state analyses. (author)

Epithelial–mesenchymal transition during oncogenic transformation induced by hexavalent chromium involves reactive oxygen species-dependent mechanism in lung epithelial cells

Energy Technology Data Exchange (ETDEWEB)

Ding, Song-Ze, E-mail: dingsongze@hotmail.com [Department of Internal Medicine, Henan Provincial People’s Hospital, Zhengzhou University, Wei-Wu Road, Zhengzhou, Henan 450000 (China); Graduate Center for Toxicology, College of Medicine, University of Kentucky, Lexington, KY 40536 (United States); Yang, Yu-Xiu; Li, Xiu-Ling [Department of Internal Medicine, Henan Provincial People’s Hospital, Zhengzhou University, Wei-Wu Road, Zhengzhou, Henan 450000 (China); Michelli-Rivera, Audrey [Graduate Center for Toxicology, College of Medicine, University of Kentucky, Lexington, KY 40536 (United States); Han, Shuang-Yin [Department of Internal Medicine, Henan Provincial People’s Hospital, Zhengzhou University, Wei-Wu Road, Zhengzhou, Henan 450000 (China); Wang, Lei; Pratheeshkumar, Poyil; Wang, Xin; Lu, Jian; Yin, Yuan-Qin; Budhraja, Amit; Hitron, Andrew J. [Graduate Center for Toxicology, College of Medicine, University of Kentucky, Lexington, KY 40536 (United States)

2013-05-15

Hexavalent chromium [Cr(VI)] is an important human carcinogen associated with pulmonary diseases and lung cancer. Exposure to Cr(VI) induces DNA damage, cell morphological change and malignant transformation in human lung epithelial cells. Despite extensive studies, the molecular mechanisms remain elusive, it is also not known if Cr(VI)-induced transformation might accompany with invasive properties to facilitate metastasis. We aimed to study Cr(VI)-induced epithelial–mesenchymal transition (EMT) and invasion during oncogenic transformation in lung epithelial cells. The results showed that Cr(VI) at low doses represses E-cadherin mRNA and protein expression, enhances mesenchymal marker vimentin expression and transforms the epithelial cell into fibroblastoid morphology. Cr(VI) also increases cell invasion and promotes colony formation. Further studies indicated that Cr(VI) uses multiple mechanisms to repress E-cadherin expression, including activation of E-cadherin repressors such as Slug, ZEB1, KLF8 and enhancement the binding of HDAC1 in E-cadherin gene promoter, but DNA methylation is not responsible for the loss of E-cadherin. Catalase reduces Cr(VI)-induced E-cadherin and vimentin protein expression, attenuates cell invasion in matrigel and colony formation on soft agar. These results demonstrate that exposure to a common human carcinogen, Cr(VI), induces EMT and invasion during oncogenic transformation in lung epithelial cells and implicate in cancer metastasis and prevention. - Graphical abstract: Epithelial–mesenchymal transition during oncogenic transformation induced by hexavalent chromium involves reactive oxygen species-dependent mechanisms in lung epithelial cells. - Highlights: • We study if Cr(VI) might induce EMT and invasion in epithelial cells. • Cr(VI) induces EMT by altering E-cadherin and vimentin expression. • It also increases cell invasion and promotes oncogenic transformation. • Catalase reduces Cr(VI)-induced EMT, invasion and

Solid state chemistry of rare earth oxides. Final report, September 1, 1950--July 31, 1977

International Nuclear Information System (INIS)

Eyring, L.

1977-07-01

Work under Contract E(11-1)-1109 and its antecedents has been primarily for the purpose of obtaining detailed thermodynamic, kinetic and structural information on the complex rare earth oxides of praseodymium and terbium. These systems exhibit homologous series of ordered phases, order-disorder transformations, wide-range nonstoichiometric phases, chemical hysteresis in two-phase regions and many other solid state reaction phenomena. Fluorite-related materials of importance to ERDA occur as nuclear fuels, radiation power sources, insulators and solid electrolytes. The rare earth oxides serve directly as model systems for such similar materials and, in a more general sense, they serve as models of solids in general since they exhibit nearly the full range of solid state properties

Assigning Oxidation States to Organic Compounds via Predictions from X-Ray Photoelectron Spectroscopy: A Discussion of Approaches and Recommended Improvements

Science.gov (United States)

Gupta, Vipul; Ganegoda, Hasitha; Engelhard, Mark H.; Terry, Jeff; Linford, Matthew R.

2014-01-01

The traditional assignment of oxidation states to organic molecules is problematic. Accordingly, in 1999, Calzaferri proposed a simple and elegant solution that is based on the similar electronegativities of carbon and hydrogen: hydrogen would be assigned an oxidation state of zero when bonded to carbon. Here, we show that X-ray photoelectron…

SOLID STATE ENERGY CONVERSION ALLIANCE (SECA) SOLID OXIDE FUEL CELL PROGRAM

Energy Technology Data Exchange (ETDEWEB)

Unknown

2003-06-01

This report summarizes the progress made during the September 2001-March 2002 reporting period under Cooperative Agreement DE-FC26-01NT41245 for the U. S. Department of Energy, National Energy Technology Laboratory (DOE/NETL) entitled ''Solid State Energy Conversion Alliance (SECA) Solid Oxide Fuel Cell Program''. The program focuses on the development of a low-cost, high-performance 3-to-10-kW solid oxide fuel cell (SOFC) system suitable for a broad spectrum of power-generation applications. The overall objective of the program is to demonstrate a modular SOFC system that can be configured to create highly efficient, cost-competitive, and environmentally benign power plants tailored to specific markets. When fully developed, the system will meet the efficiency, performance, life, and cost goals for future commercial power plants.

Solid-phase extraction of plutonium in various oxidation states from simulated groundwater using N-benzoylphenylhydroxylamine

International Nuclear Information System (INIS)

Perevalov, S.A.; Malofeeva, G.I.; Kuzovkina, E.V.; Spivakov, B.Ya.

2013-01-01

Solid-phase extraction of plutonium in different individual and mixed oxidation states from simulated groundwater (pH 8.5) was studied. The extraction of plutonium species was carried out in a dynamic mode using DIAPAK C16 cartridges modified by N-benzoylphenylhydroxylamine (BPHA). It was shown that the extent of recovery depends on the oxidation state of plutonium. The extraction of Pu(IV) was at the level of 98-99% regardless of the volume and flow-rate of the sample solution. Pu(V) was extracted by 90-95% and 75-80% from 10- and 100-mL aliquots of the samples, respectively, whereas the extraction of Pu(VI) did not exceed 45-50%. An equimolar mixture of Pu(IV), Pu(V), and Pu(VI) was extracted by 74%. The distribution coefficients (K d ) and kinetic exchange capacities (S) of plutonium in various oxidation states were measured. It was found that during the sorption process, Pu(V) was reduced to Pu(IV) by 80-90% after an hour-long contact with the solid phase. Pu(VI) is reduced to Pu(V) by 34% and to Pu(IV) by 55%. In the case of mixed-valent solution of plutonium, only Pu(V) and Pu(IV) were found in the effluents. (author)

A simple route to synthesize conductive stimuli-responsive polypyrrole nanocomposite hydrogel particles with strong magnetic properties and their performance for removal of hexavalent chromium ions from aqueous solution

Energy Technology Data Exchange (ETDEWEB)

Ahmad, Hasan, E-mail: samarhass@yahoo.com [Department of Chemistry, Rajshahi University, Rajshahi 6205 (Bangladesh); Rahman, Mohammad Mostafizar; Ali, Mohammad Azgar [Department of Chemistry, Rajshahi University, Rajshahi 6205 (Bangladesh); Minami, Hideto [Graduate School of Engineering, Kobe University, Kobe 657-8501 (Japan); Tauer, Klaus [Max Planck Institute of Colloid and Interfaces, Am Mühlenberg, 14476 Golm (Germany); Gafur, Mohammad Abdul [Pilot Plant and Process Development Centre, BCSIR, Dhaka 1205 (Bangladesh); Rahman, Mohammad Mahbubor [Department of Chemistry, Rajshahi University, Rajshahi 6205 (Bangladesh)

2016-08-15

A combination of maghemite polypyrrole (PPy/γ-Fe{sub 2}O{sub 3}) and stimuli-responsive properties in the same hydrogel microspheres is expected to enhance their application potential in various fields such as tissue engineering, regenerative medicine, biosensors, biomedical applications and removal of heavy metals from waste water, catalysis etc. In this investigation a simple two step process is used to prepare conductive stimuli-responsive polypyrrole (PPy) composite hydrogel particles with strong magnetic properties. Poly(styrene-methacrylic acid-N-isopropylacrylamide-polyethelene glycol methacrylate) or P(S-NIPAM-MAA-PEGMA) hydrogel seed particles are first prepared by soap-free precipitation copolymerization. The copolymer hydrogel particles exhibited both temperature- and pH-responsive volume phase transition. Conductive P(S-NIPAM-MAA-PEGMA)/PPy/γ-Fe{sub 2}O{sub 3} nanocomposite hydrogel particles are then prepared by seeded chemical oxidative polymerization of pyrrole in the presence of P(S-NIPAM-MAA-PEGMA) hydrogel seed particles using FeCl{sub 3} as a oxidant and p-toluene sulfonic acid ( p-TSA) as a dopant. In the reaction system FeCl{sub 3} functioned as a source of Fe(III) for the formation of γ-Fe{sub 2}O{sub 3}. This reaction also requires the initial presence of Fe(II) provided by the addition of FeCl{sub 2}. The size and size distribution, surface structure, and morphology of the prepared conductive composite hydrogel particles are confirmed by FTIR, electron micrographs, X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), and UV–visible spectroscopy. The performance of nanocomposite hydrogel particles has been evaluated for the removal of hexavalent chromium (Cr) ions from water. - Highlights: • P(S-NIPAM-MAA-PEGMA) hydrogel particles were prepared. • P(S-NIPAM-MAA-PEGMA)/PPy/γ-Fe{sub 2}O{sub 3} nanocomposite hydrogel particles were prepared. • Oxidative polymerization of pyrrole and precipitation of γ-Fe{sub 2}O{sub 3

Correlation of the oxidation state of cerium in sol-gel glasses as a function of thermal treatment via optical spectroscopy and XANES studies.

Science.gov (United States)

Assefa, Zerihun; Haire, R G; Caulder, D L; Shuh, D K

2004-07-01

Sol-gel glass matrices containing lanthanides have numerous technological applications and their formation involves several chemical facets. In the case of cerium, its ability to exist in two different oxidation states or in mixed valence state provides additional complexities for the sol-gel process. The oxidation state of cerium present during different facets of preparation of sol-gel glasses, and also as a function of the starting oxidation state of cerium added, were studied both by optical spectroscopy and X-ray absorption near-edge structures (XANES). The findings acquired by each approach were compared. The primary focus was on the redox chemistries associated with sample preparation, gelation, and thermal treatment. When Ce3+ is introduced into the starting sols, the trivalent state normally prevails in the wet and room temperature-dried gels. Heating in air at >100 degrees C can generate a light yellow coloration with partial oxidation to the tetravalent state. Above 200 degrees C and up to approximately 1000 degrees C, cerium is oxidized to its tetravalent state. In contrast, when tetravalent cerium is introduced into the sol, both the wet and room temperature-dried gels lose the yellow-brown color of the initial ceric ammonium nitrate solution. When the sol-gel is heated to 110 degrees C it turns yellowish as the cerium tends to be re-oxidized. The yellow color is believed to represent the effect of oxidation and oligomerization of the cerium-silanol units in the matrix. The luminescence properties are also affected by these changes, the details of which are reported herein.

Exploratory Characterization of Phenolic Compounds with Demonstrated Anti-Diabetic Activity in Guava Leaves at Different Oxidation States

Science.gov (United States)

Díaz-de-Cerio, Elixabet; Verardo, Vito; Gómez-Caravaca, Ana María; Fernández-Gutiérrez, Alberto; Segura-Carretero, Antonio

2016-01-01

Psidium guajava L. is widely used like food and in folk medicine all around the world. Many studies have demonstrated that guava leaves have anti-hyperglycemic and anti-hyperlipidemic activities, among others, and that these activities belong mainly to phenolic compounds, although it is known that phenolic composition in guava tree varies throughout seasonal changes. Andalusia is one of the regions in Europe where guava is grown, thus, the aim of this work was to study the phenolic compounds present in Andalusian guava leaves at different oxidation states (low, medium, and high). The phenolic compounds in guava leaves were determined by HPLC-DAD-ESI-QTOF-MS. The results obtained by chromatographic analysis reported that guava leaves with low degree of oxidation had a higher content of flavonols, gallic, and ellagic derivatives compared to the other two guava leaf samples. Contrary, high oxidation state guava leaves reported the highest content of cyanidin-glucoside that was 2.6 and 15 times higher than guava leaves with medium and low oxidation state, respectively. The QTOF platform permitted the determination of several phenolic compounds with anti-diabetic properties and provided new information about guava leaf phenolic composition that could be useful for nutraceutical production. PMID:27187352

Exploratory Characterization of Phenolic Compounds with Demonstrated Anti-Diabetic Activity in Guava Leaves at Different Oxidation States

Directory of Open Access Journals (Sweden)

Elixabet Díaz-de-Cerio

2016-05-01

Full Text Available Psidium guajava L. is widely used like food and in folk medicine all around the world. Many studies have demonstrated that guava leaves have anti-hyperglycemic and anti-hyperlipidemic activities, among others, and that these activities belong mainly to phenolic compounds, although it is known that phenolic composition in guava tree varies throughout seasonal changes. Andalusia is one of the regions in Europe where guava is grown, thus, the aim of this work was to study the phenolic compounds present in Andalusian guava leaves at different oxidation states (low, medium, and high. The phenolic compounds in guava leaves were determined by HPLC-DAD-ESI-QTOF-MS. The results obtained by chromatographic analysis reported that guava leaves with low degree of oxidation had a higher content of flavonols, gallic, and ellagic derivatives compared to the other two guava leaf samples. Contrary, high oxidation state guava leaves reported the highest content of cyanidin-glucoside that was 2.6 and 15 times higher than guava leaves with medium and low oxidation state, respectively. The QTOF platform permitted the determination of several phenolic compounds with anti-diabetic properties and provided new information about guava leaf phenolic composition that could be useful for nutraceutical production.

Exploratory Characterization of Phenolic Compounds with Demonstrated Anti-Diabetic Activity in Guava Leaves at Different Oxidation States.

Science.gov (United States)

Díaz-de-Cerio, Elixabet; Verardo, Vito; Gómez-Caravaca, Ana María; Fernández-Gutiérrez, Alberto; Segura-Carretero, Antonio

2016-05-11

Psidium guajava L. is widely used like food and in folk medicine all around the world. Many studies have demonstrated that guava leaves have anti-hyperglycemic and anti-hyperlipidemic activities, among others, and that these activities belong mainly to phenolic compounds, although it is known that phenolic composition in guava tree varies throughout seasonal changes. Andalusia is one of the regions in Europe where guava is grown, thus, the aim of this work was to study the phenolic compounds present in Andalusian guava leaves at different oxidation states (low, medium, and high). The phenolic compounds in guava leaves were determined by HPLC-DAD-ESI-QTOF-MS. The results obtained by chromatographic analysis reported that guava leaves with low degree of oxidation had a higher content of flavonols, gallic, and ellagic derivatives compared to the other two guava leaf samples. Contrary, high oxidation state guava leaves reported the highest content of cyanidin-glucoside that was 2.6 and 15 times higher than guava leaves with medium and low oxidation state, respectively. The QTOF platform permitted the determination of several phenolic compounds with anti-diabetic properties and provided new information about guava leaf phenolic composition that could be useful for nutraceutical production.

Elevated oxidative stress monitored via the albumin-thiol redox state is correlated with matrix metalloproteinase-3 elevation in patients with rheumatoid arthritis.

Science.gov (United States)

Kizaki, Kazuha; Yoshizumi, Yusuke; Takahashi, Teppei; Era, Seiichi

2015-01-01

In rheumatoid arthritis (RA), matrix metalloproteinase-3 (MMP-3) and oxidative stress contribute to joint destruction. However, little is known about the relationship between MMP-3 and oxidative stress in RA. We measured the albumin-thiol redox state as a marker of oxidative stress, MMP-3, and the DAS-28 score calculated using CRP values among forty-seven patients (9 males and 38 females) with RA. According to the serum MMP-3 levels, they were divided into two groups (group A: within normal ranges of 36.9-121.0 ng/mL for men and 17.3-59.7 ng/mL for women; group B: above normal ranges). The albumin-thiol redox state in group B was significantly oxidized compared with that in group A (p < 0.01). The percentage of oxidized albumin-thiol showed a positive correlation with serum MMP-3 (r = 0.52). DAS-28 and CRP were also correlated with the percentage of oxidized albumin-thiol (r = 0.46, r = 0.44). The albumin-thiol redox state was significantly oxidized in correlation with serum MMP-3 elevation in RA.

The Behavior of the Ru-bda Water Oxidation Catalysts at Low Oxidation States.

Science.gov (United States)

Matheu, Roc; Ghaderian, Abolfazl; Francas, Laia; Chernev, Petko; Ertem, Mehmed; Benet-Buchholz, Jordi; Batista, Victor; Haumann, Michael; Gimbert-Suriñach, Carolina; Sala, Xavier; Llobet, Antoni

2018-06-13

The Ru complex [RuII(bda-κ-N2O2)(N-NH2)2], 1, (bda2- = (2,2'-bipyridine)-6,6'-dicarboxylate; N-NH2 = 4-(pyridin-4-yl)aniline) is used as a synthetic intermediate to prepare Ru-bda complexes that contain the NO+, acetonitrile (MeCN) or H2O ligands at oxidation states II and III. Complex 1 reacts with excess NO+ to form a Ru complex where the aryl amine ligands N-NH2 in 1 are transformed into diazonium salts (N-N2+ = 4-(pyridin-4-yl)benzenediazonium)) together with the formation of a new Ru-NO group at the equatorial zone, to generate [RuII(bda-κ-N2O)(NO)(N-N2)2]3+, 23+. Similarly, complex 1 can also react with a coordinating solvent, such as MeCN, at room temperature leading to complex [RuII(bda-κ-N2O)(MeCN)(N-NH2)2], 3. Finally in acidic aqueous solutions solvent water coordinates the Ru center forming {[RuII(bda-κ-(NO)3)(H2O)(N-NH3)2](H2O)n}2+, 42+, that is strongly hydrogen bonded with additional water molecules at the second coordination sphere. We have additionally characterized the one electron oxidized complex {[RuIII(bda-κ-(NO)3.5)(H2O)(N-NH3)2](H2O)n}3+, 53+. The coordination mode of the complexes has been studied both in the solid state and in solution through single-crystal XRD, X-ray absorption spectroscopy, variable-temperature NMR and DFT calculations. While the κ-N2O is the main coordination mode for 23+ and 3, an equilibrium that involves isomers with κ-N2O and κ-NO2 coordination modes and neighboring hydrogen bonded water molecules is observed for 42+ and 53+. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Interface Controlled Oxidation States in Layered Cobalt Oxide Nanoislands on Gold

DEFF Research Database (Denmark)

Walton, Alexander; Fester, Jakob; Bajdich, Michal

2015-01-01

Layered cobalt oxides have been shown to be highly active catalysts for the oxygen evolution reaction (OER; half of the catalytic “water splitting” reaction), particularly when promoted with gold. However, the surface chemistry of cobalt oxides and in particular the nature of the synergistic effect...

Triplet-State Dissolved Organic Matter Quantum Yields and Lifetimes from Direct Observation of Aromatic Amine Oxidation.

Science.gov (United States)

Schmitt, Markus; Erickson, Paul R; McNeill, Kristopher

2017-11-21

Excited triplet state chromophoric dissolved organic matter ( 3 CDOM*) is a short-lived mixture of excited-state species that plays important roles in aquatic photochemical processes. Unlike the study of the triplet states of well-defined molecules, which are amenable to transient absorbance spectroscopy, the study of 3 CDOM* is hampered by it being a complex mixture and its low average intersystem crossing quantum yield (Φ ISC ). This study is an alternative approach to investigating 3 CDOM* using transient absorption laser spectroscopy. The radical cation of N,N,N',N'-tetramethyl-p-phenylenediamine (TMPD), formed through oxidation by 3 CDOM*, was directly observable by transient absorption spectroscopy and was used to probe basic photophysical properties of 3 CDOM*. Quenching and control experiments verified that TMPD •+ was formed from 3 CDOM* under anoxic conditions. Model triplet sensitizers with a wide range of excited triplet state reduction potentials and CDOM oxidized TMPD at near diffusion-controlled rates. This gives support to the idea that a large cross-section of 3 CDOM* moieties are able to oxidize TMPD and that the complex mixture of 3 CDOM* can be simplified to a single signal. Using the TMPD •+ transient, the natural triplet lifetime and Φ ISC for different DOM isolates and natural waters were quantified; values ranged from 12 to 26 μs and 4.1-7.8%, respectively.

Effect of particle size on iron nanoparticle oxidation state

International Nuclear Information System (INIS)

Lombardo, Jeffrey J.; Lysaght, Andrew C.; Goberman, Daniel G.; Chiu, Wilson K.S.

2012-01-01

Selecting catalyst particles is a very important part of carbon nanotube growth, although the properties of these nanoscale particles are unclear. In this article iron nanoparticles are analyzed through the use of atomic force microscopy and x-ray photoelectron spectroscopy in order to understand how the size affects the chemical composition of nanoparticles and thus their physical structure. Initially, atomic force microscopy was used to confirm the presence of iron particles, and to determine the average size of the particles. Next an analytical model was developed to estimate particle size as a function of deposition time using inputs from atomic force microscopy measurement. X-ray photoelectron spectroscopy analysis was then performed with a focus on the spectra relating to the 2p Fe electrons to study the chemical state of the particles as a function of time. It was shown that as the size of nanoparticles decreased, the oxidation state of the particles changed due to a high proportion of atoms on the surface.

High-Pressure Reactivity of Kr and F2—Stabilization of Krypton in the +4 Oxidation State

Directory of Open Access Journals (Sweden)

Dominik Kurzydłowski

2017-10-01

Full Text Available Since the synthesis of the first krypton compound, several other Kr-bearing connections have been obtained. However, in all of them krypton adopts the +2 oxidation state, in contrast to xenon which forms numerous compounds with an oxidation state as high as +8. Motivated by the possibility of thermodynamic stabilization of exotic compounds with the use of high pressure (exceeding 1 GPa = 10 kbar, we present here theoretical investigations into the chemistry of krypton and fluorine at such large compression. In particular we focus on krypton tetrafluoride, KrF4, a molecular crystal in which krypton forms short covalent bonds with neighboring fluorine atoms thus adopting the +4 oxidation state. We find that this hitherto unknown compound can be stabilized at pressures below 50 GPa. Our results indicate also that, at larger compressions, a multitude of other KrmFn fluorides should be stable, among them KrF which exhibits covalent Kr–Kr bonds. Our results set the stage for future high-pressure synthesis of novel krypton compounds.

Two fold modified chitosan for enhanced adsorption of hexavalent chromium from simulated wastewater and industrial effluents.

Science.gov (United States)

Kahu, S S; Shekhawat, A; Saravanan, D; Jugade, R M

2016-08-01

Ionic solid (Ethylhexadecyldimethylammoniumbromide) impregnated phosphated chitosan (ISPC) was synthesized and applied for enhanced adsorption of hexavalent chromium from industrial effluent. The compound obtained was extensively characterized using instrumental techniques like FT-IR, TGA-DTA, XRD, SEM, BET and EDX. ISPC showed high adsorption capacity of 266.67mg/g in accordance with Langmuir isotherm model at pH 3.0 due to the presence of multiple sites which contribute for ion pair and electrostatic interactions with Cr(VI) species. The sorption kinetics and thermodynamic studies revealed that adsorption of Cr(VI) followed pseudo-second-order kinetics with exothermic and spontaneous behaviour. Applicability of ISPC for higher sample volumes was discerned through column studies. The real chrome plating industry effluent was effectively treated with total chromium recovery of 94%. The used ISPC was regenerated simply by dilute ammonium hydroxide treatment and tested for ten adsorption-desorption cycles with marginal decrease in adsorption efficiency. Copyright © 2016 Elsevier Ltd. All rights reserved.

The Development of Bispecific Hexavalent Antibodies as a Novel Class of DOCK-AND-LOCKTM (DNLTM Complexes

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Chien-Hsing Chang

2013-05-01

Full Text Available The DOCK-AND-LOCKTM (DNLTM method provides a modular approach to develop multivalent, multifunctional complexes of defined structures, of which bispecific hexavalent antibodies (bsHexAbs are prominent examples with potential applications in targeted therapy for malignant, autoimmune, and infectious diseases. Currently, bsHexAbs are constructed by derivatizing a divalent IgG, at the carboxyl termini of either the heavy chain (the CH3-format or the light chain (the Ck-format, to contain two stabilized dimers of Fab having a different specificity from the IgG. In this review, we briefly outline the features of the DNLTM method and describe key aspects of bsHexAbs examined with diverse preclinical studies, which include binding affinity to target cells, induction of signaling pathways, effector functions, serum stability, pharmacokinetics, and antitumor activity in human tumor xenograft models. Our findings favor the selection of the CK- over the CH3-format for further exploration of bsHexAbs in clinical trials.

Operando XAS Study of the Surface Oxidation State on a Monolayer IrO_x on RuO_x and Ru Oxide Based Nanoparticles for Oxygen Evolution in Acidic Media

DEFF Research Database (Denmark)

Pedersen, Anders Filsøe; Escribano, Maria Escudero; Sebok, Bela

2018-01-01

that the average Ir oxidation state change is strongly affected by the coverage of atomic O. The observed shifts in oxidation state suggest that the surface has a high coverage of O at potentials just below the potential where oxygen evolution is exergonic in free energy. This observation is consistent...

Current status and future prospects of uranium resources

International Nuclear Information System (INIS)

Kuronuma, Chosuke

1997-01-01

Uranium is contained in various things in natural world, for example, 3 ppm in granite and 3x10 -3 ppm in seawater. Uranium exists in the state of tetra, penta and hexa-valence in nature, and in oxidizing environment, it exists as uranyl radical of hexa-valence, forms soluble complexes, and easily moves with water. In reducing environment, it becomes insoluble state of tetra-valence and precipitates. This property of uranium is deeply related to the way of forming the deposit, and it is explained. The uranium resources of the recovery cost being 80 dollars per kg U or less are 2,120,000 t, and 60% of the total exists in Australia, Kazakstan and Canada. The cumulative production of uranium in the world from 1945 to 1995 was 1,810,000 t. Of the total production, 875,000 t was used for civil purpose, and 750,000 t was used for military purpose. The uranium deposits in Canada are very high quality, and produce 1/3 of the world uranium production. There are the inventories of 150,000-200,000 t U. The diversion of military high enriched uranium to civil purpose is reported. The state of uranium market, the prospect of demand and supply of uranium, and the exploration and development of uranium resources are described. (K.I.)

Determination of Model Kinetics for Forced Unsteady State Operation of Catalytic CH4 Oxidation

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Effendy Mohammad

2016-01-01

Full Text Available The catalytic oxidation of methane for abating the emission vented from coal mine or natural gas transportation has been known as most reliable method. A reverse flow reactor operation has been widely used to oxidize this methane emission due to its capability for autothermal operation and heat production. The design of the reverse flow reactor requires a proper kinetic rate expression, which should be developed based on the operating condition. The kinetic rate obtained in the steady state condition cannot be applied for designing the reactor operated under unsteady state condition. Therefore, new approach to develop the dynamic kinetic rate expression becomes indispensable, particularly for periodic operation such as reverse flow reactor. This paper presents a novel method to develop the kinetic rate expression applied for unsteady state operation. The model reaction of the catalytic methane oxidation over Pt/-Al2O3 catalyst was used with kinetic parameter determined from laboratory experiments. The reactor used was a fixed bed, once-through operation, with a composition modulation in the feed gas. The switching time was set at 3 min by varying the feed concentration, feed flow rate, and reaction temperature. The concentrations of methane in the feed and product were measured and analysed using gas chromatography. The steady state condition for obtaining the kinetic rate expression was taken as a base case and as a way to judge its appropriateness to be applied for dynamic system. A Langmuir-Hinshelwood reaction rate model was developed. The time period during one cycle was divided into some segments, depending on the ratio of CH4/O2. The experimental result shows that there were kinetic regimes occur during one cycle: kinetic regime controlled by intrinsic surface reaction and kinetic regime controlled by external diffusion. The kinetic rate obtained in the steady state operation was not appropriate when applied for unsteady state operation

Manganese oxidation state mediates toxicity in PC12 cells

International Nuclear Information System (INIS)

Reaney, S.H.; Smith, D.R.

2005-01-01

The role of the manganese (Mn) oxidation state on cellular Mn uptake and toxicity is not well understood. Therefore, undifferentiated PC12 cells were exposed to 0-200 μM Mn(II)-chloride or Mn(III)-pyrophosphate for 24 h, after which cellular manganese levels were measured along with measures of cell viability, function, and cytotoxicity (trypan blue exclusion, medium lactate dehydrogenase (LDH), 8-isoprostanes, cellular ATP, dopamine, serotonin, H-ferritin, transferrin receptor (TfR), Mn-superoxide dismutase (MnSOD), and copper-zinc superoxide dismutase (CuZnSOD) protein levels). Exposures to Mn(III) >10 μM produced 2- to 5-fold higher cellular manganese levels than equimolar exposures to Mn(II). Cell viability and ATP levels both decreased at the highest Mn(II) and Mn(III) exposures (150-200 μM), while Mn(III) exposures produced increases in LDH activity at lower exposures (≥50 μM) than did Mn(II) (200 μM only). Mn(II) reduced cellular dopamine levels more than Mn(III), especially at the highest exposures (50% reduced at 200 μM Mn(II)). In contrast, Mn(III) produced a >70% reduction in cellular serotonin at all exposures compared to Mn(II). Different cellular responses to Mn(II) exposures compared to Mn(III) were also observed for H-ferritin, TfR, and MnSOD protein levels. Notably, these differential effects of Mn(II) versus Mn(III) exposures on cellular toxicity could not simply be accounted for by the different cellular levels of manganese. These results suggest that the oxidation state of manganese exposures plays an important role in mediating manganese cytotoxicity

Treatment of phosphorus-uraniferous solution

International Nuclear Information System (INIS)

Araujo Figueiredo, C. de.

1984-01-01

A solvent extraction process for the recovery of uranium from Itataia wet process phosphoric acid was studied. The proposed process consists of two extraction cycles. Uranium, reduced to its tetravalent state, is extracted in the first cycle using octylpyrosphoric acid (OPPA) in a kerosene type diluent. Stripping is accomplished with concentrated raffinate phosphoric acid and an oxidizing agent, in order to convert U (IV) to its hexavalent state. The strip solution from the first cycle is processed in the second cycle with the synergistic combination of di-( 2- ethylhexyl) phosphoric acid and tri-n-octylphosphine oxide (D2EHPA-TOPO). The extract is scrubbed and uranium is stripped with ammonium carbonate solution and recovered as a commercial concentrate. The results obtained from batch tests were used to set up a bench scale array of mixer settlers so as to demonstrate the process. (Author) [pt

Hexavalent chromium exposures and exposure-control technologies in American enterprise: results of a NIOSH field research study.

Science.gov (United States)

Blade, L M; Yencken, M Story; Wallace, M E; Catalano, J D; Khan, A; Topmiller, J L; Shulman, S A; Martinez, A; Crouch, K G; Bennett, J S

2007-08-01

The National Institute for Occupational Safety and Health (NIOSH) conducted 21 field surveys in selected industries to characterize workers' exposures to hexavalent chromium-containing airborne particulate and to evaluate existing technologies for controlling these exposures. Hexavalent chromium Cr(VI) is a respiratory irritant and chronic inhalation may cause lung cancer. Primary evaluation methods included collection of full work shift, personal breathing-zone (PBZ) air samples for Cr(VI), measurement of ventilation system parameters, and documentation of processes and work practices. This study emphasized evaluation of engineering exposure control measures, so PBZ exposures were measured on the outside of personal protective equipment, for example, respirators. Field surveys were conducted in two chromium electroplating facilities, including one where full-shift PBZ exposures to Cr(VI) ranged from 3.0 to 16 times the 1 micro g/m(3)NIOSH recommended exposure limit (REL) despite several engineering controls on the plating tanks. At a painting and coating facility that used Cr(VI)-containing products, full-shift exposures of painters and helpers (2.4 to 55 micro g/m(3)) exceeded the REL, but LEV effectiveness was limited. Other operations evaluated included welding in construction; metal cutting operations on chromium-containing materials in ship breaking; chromate-paint removal with abrasive blasting; atomized alloy-spray coating; foundry operations; printing; and the manufacture of refractory brick, colored glass, prefabricated concrete products, and treated wood products. NIOSH researchers concluded that, in many of the evaluated processes, Cr(VI) exposures at or below the current NIOSH REL are achievable. However, for some processes, it is unclear whether controlling exposures to this range is consistently achievable without respirator use. Some operations involving the application of coatings and finishes may be among those most difficult to control to this

Proteomic indicators of oxidation and hydration state in colorectal cancer

Directory of Open Access Journals (Sweden)

Jeffrey M. Dick

2016-07-01

Full Text Available New integrative approaches are needed to harness the potential of rapidly growing datasets of protein expression and microbial community composition in colorectal cancer. Chemical and thermodynamic models offer theoretical tools to describe populations of biomacromolecules and their relative potential for formation in different microenvironmental conditions. The average oxidation state of carbon (ZC can be calculated as an elemental ratio from the chemical formulas of proteins, and water demand per residue ( ${\\overline{n}}_{{\\mathrm{H}}_{2}\\mathrm{O}}$ n ¯ H 2 O is computed by writing the overall formation reactions of proteins from basis species. Using results reported in proteomic studies of clinical samples, many datasets exhibit higher mean ZC or ${\\overline{n}}_{{\\mathrm{H}}_{2}\\mathrm{O}}$ n ¯ H 2 O of proteins in carcinoma or adenoma compared to normal tissue. In contrast, average protein compositions in bacterial genomes often have lower ZC for bacteria enriched in fecal samples from cancer patients compared to healthy donors. In thermodynamic calculations, the potential for formation of the cancer-related proteins is energetically favored by changes in the chemical activity of H2O and fugacity of O2 that reflect the compositional differences. The compositional analysis suggests that a systematic change in chemical composition is an essential feature of cancer proteomes, and the thermodynamic descriptions show that the observed proteomic transformations in host tissue could be promoted by relatively high microenvironmental oxidation and hydration states.

Exposure to particulate hexavalent chromium exacerbates allergic asthma pathology

International Nuclear Information System (INIS)

Schneider, Brent C.; Constant, Stephanie L.; Patierno, Steven R.; Jurjus, Rosalyn A.; Ceryak, Susan M.

2012-01-01

Airborne hexavalent chromate, Cr(VI), has been identified by the Environmental Protection Agency as a possible health threat in urban areas, due to the carcinogenic potential of some of its forms. Particulate chromates are produced in many different industrial settings, with high levels of aerosolized forms historically documented. Along with an increased risk of lung cancer, a high incidence of allergic asthma has been reported in workers exposed to certain inhaled particulate Cr(VI) compounds. However, a direct causal association between Cr(VI) and allergic asthma has not been established. We recently showed that inhaled particulate Cr(VI) induces an innate neutrophilic inflammatory response in BALB/c mice. In the current studies we investigated how the inflammation induced by inhaled particulate Cr(VI) might alter the pathology of an allergic asthmatic response. We used a well-established mouse model of allergic asthma. Groups of ovalbumin protein (OVA)-primed mice were challenged either with OVA alone, or with a combination of OVA and particulate zinc chromate, and various parameters associated with asthmatic responses were measured. Co-exposure to particulate Cr(VI) and OVA mediated a mixed form of asthma in which both eosinophils and neutrophils are present in airways, tissue pathology is markedly exacerbated, and airway hyperresponsiveness is significantly increased. Taken together these findings suggest that inhalation of particulate forms of Cr(VI) may augment the severity of ongoing allergic asthma, as well as alter its phenotype. Such findings may have implications for asthmatics in settings in which airborne particulate Cr(VI) compounds are present at high levels. -- Highlights: ► Allergic asthma correlated with exposure to certain inhaled particulate chromates. ► Direct causal association between Cr(VI) and allergic asthma not established. ► Cr exacerbated pathology and airway hyperresponsiveness in an OVA-challenged mouse. ► Particulate Cr

Exposure to particulate hexavalent chromium exacerbates allergic asthma pathology

Energy Technology Data Exchange (ETDEWEB)

Schneider, Brent C. [Department of Microbiology, Immunology and Tropical Medicine, The George Washington University, Washington, DC 20037 (United States); Department of Pharmacology and Physiology, The George Washington University, Washington, DC 20037 (United States); Constant, Stephanie L. [Department of Microbiology, Immunology and Tropical Medicine, The George Washington University, Washington, DC 20037 (United States); Patierno, Steven R. [Department of Pharmacology and Physiology, The George Washington University, Washington, DC 20037 (United States); GW Cancer Institute, The George Washington University, Washington, DC 20037 (United States); Jurjus, Rosalyn A. [Department of Anatomy and Regenerative Biology, The George Washington University, Washington, DC 20037 (United States); Ceryak, Susan M., E-mail: phmsmc@gwumc.edu [Department of Pharmacology and Physiology, The George Washington University, Washington, DC 20037 (United States)

2012-02-15

Airborne hexavalent chromate, Cr(VI), has been identified by the Environmental Protection Agency as a possible health threat in urban areas, due to the carcinogenic potential of some of its forms. Particulate chromates are produced in many different industrial settings, with high levels of aerosolized forms historically documented. Along with an increased risk of lung cancer, a high incidence of allergic asthma has been reported in workers exposed to certain inhaled particulate Cr(VI) compounds. However, a direct causal association between Cr(VI) and allergic asthma has not been established. We recently showed that inhaled particulate Cr(VI) induces an innate neutrophilic inflammatory response in BALB/c mice. In the current studies we investigated how the inflammation induced by inhaled particulate Cr(VI) might alter the pathology of an allergic asthmatic response. We used a well-established mouse model of allergic asthma. Groups of ovalbumin protein (OVA)-primed mice were challenged either with OVA alone, or with a combination of OVA and particulate zinc chromate, and various parameters associated with asthmatic responses were measured. Co-exposure to particulate Cr(VI) and OVA mediated a mixed form of asthma in which both eosinophils and neutrophils are present in airways, tissue pathology is markedly exacerbated, and airway hyperresponsiveness is significantly increased. Taken together these findings suggest that inhalation of particulate forms of Cr(VI) may augment the severity of ongoing allergic asthma, as well as alter its phenotype. Such findings may have implications for asthmatics in settings in which airborne particulate Cr(VI) compounds are present at high levels. -- Highlights: ► Allergic asthma correlated with exposure to certain inhaled particulate chromates. ► Direct causal association between Cr(VI) and allergic asthma not established. ► Cr exacerbated pathology and airway hyperresponsiveness in an OVA-challenged mouse. ► Particulate Cr

Coprecipitation of aluminium with hydroxides of tetra-, penta- and hexavalent actinides

International Nuclear Information System (INIS)

Yusov, A.B.; Budantseva, N.A.; Anan'ev, A.V.; Fedoseev, A.M.

2000-01-01

By the methods of IR spectroscopy and powder x-ray diffractometry precipitates formed in alkaline medium by actinide (4, 5, 6) in the presence of aluminium are studied. It is shown that in studied conditions formation of actinide aluminates not occurs. In the same time in the process of precipitation interaction of aluminium hydroxocomplexes with U(6) and Th(4) ions probably takes place. Hypothesis is expressed that possibility of aluminium hydroxocomplexes interaction with actinides in different oxidation state is depended on peculiarities of hydrolytic behaviour of the lasts [ru

A fully liquid DTaP-IPV-Hep B-PRP-T hexavalent vaccine for primary and booster vaccination of healthy Mexican children.

Science.gov (United States)

Aquino, Amalia Guadalupe Becerra; Brito, Maricruz Gutiérrez; Doniz, Carlos E Aranza; Herrera, Juan Francisco Galán; Macias, Mercedes; Zambrano, Betzana; Plennevaux, Eric; Santos-Lima, Eduardo

2012-10-05

To evaluate an investigational, fully liquid hexavalent diphtheria-tetanus-acellular pertussis-inactivated poliovirus-hepatitis B-Haemophilus influenzae type b (DTaP-IPV-Hep B-PRP-T: Hexaxim™) vaccine for primary and booster vaccination of healthy children in Mexico. Infants (N=1189) were randomized to receive one of three lots of the DTaP-IPV-Hep B-PRP-T vaccine or a licensed hexavalent control vaccine (Infanrix™ hexa) for primary vaccination at 2, 4 and 6 months. All participants who completed the primary series and agreed to participate in the booster part of the study received a dose of the investigational vaccine at 15-18 months of age. Validated serological assays and parental reports were used to assess immunogenicity and safety, respectively. Post-primary vaccination, ≥95.8% of participants in both the DTaP-IPV-Hep B-PRP-T and control groups were seroprotected (SP) against diphtheria, tetanus, poliovirus, hepatitis B and PRP, or had seroconverted (SC) to the pertussis toxin (PT) and filamentous hemagglutinin (FHA) pertussis antigens. The SP/SC rates induced by the three DTaP-IPV-Hep B-PRP-T lots were equivalent. No differences in SP/SC rates were observed between the pooled lots of investigational vaccine and the control vaccine. Antibody persistence at 15-18 months was comparable between groups, with strong increases in all antibody concentrations post-DTaP-IPV-Hep B-PRP-T booster. Both vaccines were well tolerated for primary vaccination, as was the booster dose of DTaP-IPV-Hep B-PRP-T. These study findings confirm the suitability of the combined, fully liquid DTaP-IPV-Hep B-PRP-T vaccine for inclusion in routine childhood vaccination schedules. Copyright © 2012 Elsevier Ltd. All rights reserved.

Surface State Capture Cross-Section at the Interface between Silicon and Hafnium Oxide

Directory of Open Access Journals (Sweden)

Fu-Chien Chiu

2013-01-01

Full Text Available The interfacial properties between silicon and hafnium oxide (HfO2 are explored by the gated-diode method and the subthreshold measurement. The density of interface-trapped charges, the current induced by surface defect centers, the surface recombination velocity, and the surface state capture cross-section are obtained in this work. Among the interfacial properties, the surface state capture cross-section is approximately constant even if the postdeposition annealing condition is changed. This effective capture cross-section of surface states is about 2.4 × 10−15 cm2, which may be an inherent nature in the HfO2/Si interface.

Hexavalent chromium adsorption from aqueous solution using carbon nano-onions (CNOs).

Science.gov (United States)

Sakulthaew, Chainarong; Chokejaroenrat, Chanat; Poapolathep, Amnart; Satapanajaru, Tunlawit; Poapolathep, Saranya

2017-10-01

The capacity of carbon nano-onions (CNOs) to remove hexavalent chromium (Cr(VI)) from aqueous solution was investigated. Batch experiments were performed to quantify the effects of the dosage rate, pH, counter ions, and temperature. The adsorption of Cr(VI) onto CNOs was best described by a pseudo-second order rate expression. The adsorption efficiency increased with increasing adsorbent dosage and contact time and reached equilibrium in 24 h. The equilibrium data showed better compliance with a Langmuir isotherm than a Freundlich isotherm. Effective removal of Cr(VI) was demonstrated at pH values ranging from 2 to 10. The adsorption capacity of Cr(VI) was found to be highest (82%) at pH 3.4 and greatly depended on the solution pH. We found that Cr(VI) adsorption decreased with increasing pH over the pH range of 3.4-10. The adsorption capacity increased dramatically when the temperature increased from 10 °C to 50 °C regardless of the amount of CNOs used. Cr(VI) removal decreased by ∼13% when Zn(II), Cu(II), and Pb(II) were present, while there were no significant changes observed when NO 3 - or SO 4 2- was present. The overall results support that CNOs can be used as an alternative adsorbent material to remove Cr(VI) in the water treatment industry. Copyright © 2017 Elsevier Ltd. All rights reserved.

Origin of major donor states in In–Ga–Zn oxide

Energy Technology Data Exchange (ETDEWEB)

Nakashima, Motoki; Oota, Masashi; Ishihara, Noritaka; Nonaka, Yusuke; Hirohashi, Takuya; Takahashi, Masahiro; Yamazaki, Shunpei [Semiconductor Energy Laboratory Co., Ltd., 398 Hase, Atsugi, Kanagawa 243-0036 (Japan); Obonai, Toshimitsu; Hosaka, Yasuharu; Koezuka, Junichi [Advanced Film Device Inc., 161-2 Masuzuka, Tsuga-machi, Tochigi, Tochigi 328-0114 (Japan)

2014-12-07

To clarify the origin of the major donor states in indium gallium zinc oxide (IGZO), we report measurement results and an analysis of several physical properties of IGZO thin films. Specifically, the concentration of H atoms and O vacancies (V{sub O}), carrier concentration, and conductivity are investigated by hard X-ray photoelectron spectroscopy, secondary ion mass spectroscopy, thermal desorption spectroscopy, and Hall effect measurements. The results of these experiments suggest that the origin of major donor states is H occupancy of V{sub O} sites. Furthermore, we use first-principles calculations to investigate the influence of the coexistence of V{sub O} and H in crystalline InGaO{sub 3}(ZnO){sub m} (m = 1). The results indicate that when H is trapped in V{sub O}, a stable complex is created that serves as a shallow-level donor.

Persistence of oxidation state III of gold in thione coordination

Science.gov (United States)

Jääskeläinen, Sirpa; Koskinen, Laura; Kultamaa, Matti; Haukka, Matti; Hirva, Pipsa

2017-05-01

Ligands N,N'-tetramethylthiourea and 2-mercapto-1-methyl-imidazole form stable Au(III) complexes [AuCl3(N,N'-tetramethylthiourea)] (1) and [AuCl3(2-mercapto-1-methyl-imidazole)] (2) instead of reducing the Au(III) metal center into Au(I), which would be typical for the attachment of sulfur donors. Compounds 1 and 2 were characterized by spectroscopic methods and by X-ray crystallography. The spectroscopic details were explained by simulation of the UV-Vis spectra via the TD-DFT method. Additionally, computational DFT studies were performed in order to find the reason for the unusual oxidation state in the crystalline materials. The preference for Au(III) can be explained via various weak intra- and intermolecular interactions present in the solid state structures. The nature of the interactions was further investigated by topological charge density analysis via the QTAIM method.

Analysis of Electro-Oxidation Suitability for Landfill Leachate Treatment through an Experimental Study

Directory of Open Access Journals (Sweden)

Marco Ragazzi

2013-09-01

Full Text Available This paper examines the efficiency of electro-oxidation used as the single pretreatment of landfill leachate. The experiments were performed on three different types of leachate. The results obtained using this electrochemical method results were analyzed after seven days of treatment. The main characteristics of leachate and a diagram of the experimental apparatus are presented. The overall objectives were to contribute to the knowledge of electrochemical treatments for the reduction of COD, BOD5, ammonium, and total suspended solids, and also to examine whether there was any resulting hexavalent chromium in the liquid sample. The yields obtained were considered satisfactory, particularly given the simplicity of this technology. Like all processes used to treat refluent water, the applicability of this technique to a specific industrial refluent needs to be supported by feasibility studies to estimate its effectiveness and optimize the project parameters. This could be a future development of the work.

Uranium extraction history using pressure leaching

International Nuclear Information System (INIS)

Fraser, K.S.; Thomas, K.G.

2010-01-01

Over the past 60 years of uranium process development only a few commercial uranium plants have adopted a pressure leaching process in their flowsheet. The selection of acid versus alkaline pressure leaching is related to the uranium and gangue mineralogy. Tetravalent (U"+"4) uranium has to be oxidized to hexavalent (U"+"6) uranium to be soluble. Refractory tetravalent uranium requires higher temperature and pressure, as practised in pressure leaching, for conversation to soluble hexavalent uranium. This paper chronicles the history of these uranium pressure leaching facilities over the past 60 years, with specific details of each design and operation. (author)

SOLID STATE ENERGY CONVERSION ALLIANCE (SECA) SOLID OXIDE FUEL CELL PROGRAM

Energy Technology Data Exchange (ETDEWEB)

Nguyen Minh; Jim Powers

2003-10-01

This report summarizes the work performed for April 2003--September 2003 reporting period under Cooperative Agreement DE-FC26-01NT41245 for the U.S. Department of Energy, National Energy Technology Laboratory (DOE/NETL) entitled ''Solid State Energy Conversion Alliance (SECA) Solid oxide Fuel Cell Program''. During this reporting period, the conceptual system design activity was completed. The system design, including strategies for startup, normal operation and shutdown, was defined. Sealant and stack materials for the solid oxide fuel cell (SOFC) stack were identified which are capable of meeting the thermal cycling and degradation requirements. A cell module was tested which achieved a stable performance of 0.238 W/cm{sup 2} at 95% fuel utilization. The external fuel processor design was completed and fabrication begun. Several other advances were made on various aspects of the SOFC system, which are detailed in this report.

Air oxidation of Zr65Cu17.5Ni10Al7.5 in its amorphous and supercooled liquid states, studied by thermogravimetric analysis

International Nuclear Information System (INIS)

Dhawan, A.; Sharma, S.K.; Raetzke, K.; Faupel, F.

2003-01-01

The oxidation behaviour of the bulk amorphous alloy Zr 65 Cu 17.5 Ni 10 Al 7.5 was studied in air at various temperatures in the temperature range 591-732 K using a thermogravimetric analyser (TGA). The oxidation kinetics of the alloy obeys the parabolic rate law showing two different linear regions (in the plots of mass gain versus square root of oxidation time) which are attributed to the amorphous and the supercooled liquid states of the alloy. The value of the activation energy Q for the amorphous state as calculated from the temperature dependence of the rate constants is found to be 1.80±0.1 eV and the corresponding value obtained for the supercooled liquid state is 1.20±0.1 eV. It is suggested that the rate controlling process during oxidation of the amorphous state is the back-diffusion of Ni, and possibly Cu also, while the oxidation in the supercooled liquid state is dominated by the inward diffusion of oxygen. (copyright 2003 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

Biosorption of hexavalent Chromium by the agricultural wastes of the cotton and barberry plants

Directory of Open Access Journals (Sweden)

Najme Boosaeidi

2017-09-01

Full Text Available Hexavalent chromium, a highly toxic metal ion employed in industrial activities, is considered as a first priority pollutant. In this study, the capsule walls of the boll of cotton (cotton waste, CW and the waste obtained from pruning barberry bushes (barberry waste, BW were investigated as cheap and locally available adsorbents for Cr (VI removal. The adsorption behavior, equilibrium, and kinetic properties have been studied through batch experiments. Specifically, the sample pH showed a significant effect and an initial pH of 2.0 was most favorable for the effective removal of chromium. The equilibrium adsorption data were well fitted to the Langmuir adsorption equation with the maximum adsorption capacities of 20.7and 15.5mg/gfor CW and BW, respectively. The kinetic evaluations showed a rapid rate of adsorption (within 10 min that followed the pseudo-second order kinetic model. In competitive adsorption tests, Cl̶ had the least effect on the adsorption efficiency of Cr (VI, especially for CW. The results indicate the potential for the application of the studied agricultural wastes as adsorbents to reduce Cr (VI concentration in aqueous samples.

Origin of deep subgap states in amorphous indium gallium zinc oxide: Chemically disordered coordination of oxygen

International Nuclear Information System (INIS)

Sallis, S.; Williams, D. S.; Butler, K. T.; Walsh, A.; Quackenbush, N. F.; Junda, M.; Podraza, N. J.; Fischer, D. A.; Woicik, J. C.; White, B. E.; Piper, L. F. J.

2014-01-01

The origin of the deep subgap states in amorphous indium gallium zinc oxide (a-IGZO), whether intrinsic to the amorphous structure or not, has serious implications for the development of p-type transparent amorphous oxide semiconductors. We report that the deep subgap feature in a-IGZO originates from local variations in the oxygen coordination and not from oxygen vacancies. This is shown by the positive correlation between oxygen composition and subgap intensity as observed with X-ray photoelectron spectroscopy. We also demonstrate that the subgap feature is not intrinsic to the amorphous phase because the deep subgap feature can be removed by low-temperature annealing in a reducing environment. Atomistic calculations of a-IGZO reveal that the subgap state originates from certain oxygen environments associated with the disorder. Specifically, the subgap states originate from oxygen environments with a lower coordination number and/or a larger metal-oxygen separation.

Origin of deep subgap states in amorphous indium gallium zinc oxide: Chemically disordered coordination of oxygen

Energy Technology Data Exchange (ETDEWEB)

Sallis, S.; Williams, D. S. [Materials Science and Engineering, Binghamton University, Binghamton, New York 13902 (United States); Butler, K. T.; Walsh, A. [Center for Sustainable Technologies and Department of Chemistry, University of Bath, Claverton Down, Bath BA2 7AY (United Kingdom); Quackenbush, N. F. [Department of Physics, Applied Physics, and Astronomy, Binghamton University, Binghamton, New York 13902 (United States); Junda, M.; Podraza, N. J. [Department of Physics and Astronomy, University of Toledo, Toledo, Ohio 43606 (United States); Fischer, D. A.; Woicik, J. C. [Materials Science and Engineering Laboratory, National Institute of Standards and Technology, Gaithersburg, Maryland 20899 (United States); White, B. E.; Piper, L. F. J., E-mail: lpiper@binghamton.edu [Department of Physics, Applied Physics, and Astronomy, Binghamton University, Binghamton, New York 13902 (United States); Materials Science and Engineering, Binghamton University, Binghamton, New York 13902 (United States)

2014-06-09

The origin of the deep subgap states in amorphous indium gallium zinc oxide (a-IGZO), whether intrinsic to the amorphous structure or not, has serious implications for the development of p-type transparent amorphous oxide semiconductors. We report that the deep subgap feature in a-IGZO originates from local variations in the oxygen coordination and not from oxygen vacancies. This is shown by the positive correlation between oxygen composition and subgap intensity as observed with X-ray photoelectron spectroscopy. We also demonstrate that the subgap feature is not intrinsic to the amorphous phase because the deep subgap feature can be removed by low-temperature annealing in a reducing environment. Atomistic calculations of a-IGZO reveal that the subgap state originates from certain oxygen environments associated with the disorder. Specifically, the subgap states originate from oxygen environments with a lower coordination number and/or a larger metal-oxygen separation.

Electrode-Impregnable and Cross-Linkable Poly(ethylene oxide)-Poly(propylene oxide)-Poly(ethylene oxide) Triblock Polymer Electrolytes with High Ionic Conductivity and a Large Voltage Window for Flexible Solid-State Supercapacitors.

Science.gov (United States)

Han, Jae Hee; Lee, Jang Yong; Suh, Dong Hack; Hong, Young Taik; Kim, Tae-Ho

2017-10-04

We present cross-linkable precursor-type gel polymer electrolytes (GPEs) that have large ionic liquid uptake capability, can easily penetrate electrodes, have high ion conductivity, and are mechanically strong as high-performance, flexible all-solid-state supercapacitors (SC). Our polymer precursors feature a hydrophilic-hydrophobic poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (PEO-PPO-PEO) triblock main-chain structure and trifunctional silane end groups that can be multi-cross-linked with each other through a sol-gel process. The cross-linked solid-state electrolyte film with moderate IL content (200 wt %) shows a well-balanced combination of excellent ionic conductivity (5.0 × 10 -3 S cm -1 ) and good mechanical stability (maximum strain = 194%). Moreover, our polymer electrolytes have various advantages including high thermal stability (decomposition temperature > 330 °C) and the capability to impregnate electrodes to form an excellent electrode-electrolyte interface due to the very low viscosity of the precursors. By assembling our GPE-impregnated electrodes and solid-state GPE film, we demonstrate an all-solid-state SC that can operate at 3 V and provides an improved specific capacitance (112.3 F g -1 at 0.1 A g -1 ), better rate capability (64% capacity retention until 20 A g -1 ), and excellent cycle stability (95% capacitance decay over 10 000 charge/discharge cycles) compared with those of a reference SC using a conventional PEO electrolyte. Finally, flexible SCs with a high energy density (22.6 W h kg -1 at 1 A g -1 ) and an excellent flexibility (>93% capacitance retention after 5000 bending cycles) can successfully be obtained.

Effect of charge state and stoichiometry on the structure and reactivity of nickel oxide clusters with CO

Science.gov (United States)

Johnson, Grant E.; Reilly, Nelly M.; Castleman, A. W., Jr.

2009-02-01

The collision induced fragmentation and reactivity of cationic and anionic nickel oxide clusters with carbon monoxide were studied experimentally using guided-ion-beam mass spectrometry. Anionic clusters with a stoichiometry containing one more oxygen atom than nickel atom (NiO2-, Ni2O3-, Ni3O4- and Ni4O5-) were found to exhibit dominant products resulting from the transfer of a single oxygen atom to CO, suggesting the formation of CO2. Of these four species, Ni2O3- and Ni4O5- were observed to be the most reactive having oxygen transfer products accounting for approximately 5% and 10% of the total ion intensity at a maximum pressure of 15 mTorr of CO. Our findings, therefore, indicate that anionic nickel oxide clusters containing an even number of nickel atoms and an odd number of oxygen atoms are more reactive than those with an odd number of nickel atoms and an even number of oxygen atoms. The majority of cationic nickel oxides, in contrast to anionic species, reacted preferentially through the adsorption of CO onto the cluster accompanied by the loss of either molecular O2 or nickel oxide units. The adsorption of CO onto positively charged nickel oxides, therefore, is exothermic enough to break apart the gas-phase clusters. Collision induced dissociation experiments, employing inert xenon gas, were also conducted to gain insight into the structural properties of nickel oxide clusters. The fragmentation products were found to vary considerably with size and stoichiometry as well as ionic charge state. In general, cationic clusters favored the collisional loss of molecular O2 while anionic clusters fragmented through the loss of both atomic oxygen and nickel oxide units. Our results provide insight into the effect of ionic charge state on the structure of nickel oxide clusters. Furthermore, we establish how the size and stoichiometry of nickel oxide clusters influences their ability to oxidize CO, an important reaction for environmental pollution abatement.

Molecular water oxidation mechanisms followed by transition metals: state of the art.

Science.gov (United States)

Sala, Xavier; Maji, Somnath; Bofill, Roger; García-Antón, Jordi; Escriche, Lluís; Llobet, Antoni

2014-02-18

One clean alternative to fossil fuels would be to split water using sunlight. However, to achieve this goal, researchers still need to fully understand and control several key chemical reactions. One of them is the catalytic oxidation of water to molecular oxygen, which also occurs at the oxygen evolving center of photosystem II in green plants and algae. Despite its importance for biology and renewable energy, the mechanism of this reaction is not fully understood. Transition metal water oxidation catalysts in homogeneous media offer a superb platform for researchers to investigate and extract the crucial information to describe the different steps involved in this complex reaction accurately. The mechanistic information extracted at a molecular level allows researchers to understand both the factors that govern this reaction and the ones that derail the system to cause decomposition. As a result, rugged and efficient water oxidation catalysts with potential technological applications can be developed. In this Account, we discuss the current mechanistic understanding of the water oxidation reaction catalyzed by transition metals in the homogeneous phase, based on work developed in our laboratories and complemented by research from other groups. Rather than reviewing all of the catalysts described to date, we focus systematically on the several key elements and their rationale from molecules studied in homogeneous media. We organize these catalysts based on how the crucial oxygen-oxygen bond step takes place, whether via a water nucleophilic attack or via the interaction of two M-O units, rather than based on the nuclearity of the water oxidation catalysts. Furthermore we have used DFT methodology to characterize key intermediates and transition states. The combination of both theory and experiments has allowed us to get a complete view of the water oxidation cycle for the different catalysts studied. Finally, we also describe the various deactivation pathways for

Method of isolation of traces of americium by using the +6 oxidation state properties

International Nuclear Information System (INIS)

Kwinta, Jean; Michel, Jean-Jacques

1969-05-01

The authors present a method to separate traces of americium from a solution containing fission products and actinides. This method comprises the following steps: firstly, the oxidation of americium at the +6 state by ammonium persulfate and carrying over of actinides and III and IV lanthanides by lanthanum fluoride; secondly, the reduction by hydrazine of the oxidized americium and carrying over of the reduced americium by lutetium fluoride; and thirdly, the americium-lutetium separation by selective extractions either with di 2 ethyl hexyl phosphoric acid, or by fractionated elution on an anionic resin column by a mixture of nitric acid and methanol [fr

Diversity of Chemical Bonding and Oxidation States in MS4 Molecules of Group 8 Elements.

Science.gov (United States)

Huang, Wei; Jiang, Ning; Schwarz, W H Eugen; Yang, Ping; Li, Jun

2017-08-04

The geometric and electronic ground-state structures of 30 isomers of six MS 4 molecules (M=Group 8 metals Fe, Ru, Os, Hs, Sm, and Pu) have been studied by using quantum-chemical density functional theory and correlated wavefunction approaches. The MS 4 species were compared to analogous MO 4 species recently investigated (W. Huang, W.-H. Xu, W. H. E. Schwarz, J. Li, Inorg. Chem. 2016, 55, 4616). A metal oxidation state (MOS) with a high value of eight appeared in the low-spin singlet T d geometric species (Os,Hs)S 4 and (Ru,Os,Hs)O 4 , whereas a low MOS of two appeared in the high-spin septet D 2d species Fe(S 2 ) 2 and (slightly excited) metastable Fe(O 2 ) 2 . The ground states of all other molecules had intermediate MOS values, with S 2- , S 2 2- , S 2 1- (and O 2- , O 1- , O 2 2- , O 2 1- ) ligands bonded by ionic, covalent, and correlative contributions. The known tendencies toward lower MOS on going from oxides to sulfides, from Hs to Os to Ru, and from Pu to Sm, and the specific behavior of Fe, were found to arise from the different atomic orbital energies and radii of the (n-1)p core and (n-1)d and (n-2)f valence shells of the metal atoms in row n of the periodic table. The comparative results of the electronic and geometric structures of the MO 4 and MS 4 species provides insight into the periodicity of oxidation states and bonding. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electrocatalytic oxidation of methanol by the [Ru3O(OAc6(py2(CH3OH]3+cluster: improving the metal-ligand electron transfer by accessing the higher oxidation states of a multicentered system

Directory of Open Access Journals (Sweden)

Henrique E. Toma

2010-01-01

Full Text Available The [Ru3O(Ac6(py2(CH3OH]+ cluster provides an effective electrocatalytic species for the oxidation of methanol under mild conditions. This complex exhibits characteristic electrochemical waves at -1.02, 0.15 and 1.18 V, associated with the Ru3III,II,II/Ru3III,III,II/Ru 3III,III,III /Ru3IV,III,III successive redox couples, respectively. Above 1.7 V, formation of two RuIV centers enhances the 2-electron oxidation of the methanol ligand yielding formaldehyde, in agreement with the theoretical evolution of the HOMO levels as a function of the oxidation states. This work illustrates an important strategy to improve the efficiency of the oxidation catalysis, by using a multicentered redox catalyst and accessing its multiple higher oxidation states.

Elevated Frequencies of Micronuclei and other Nuclear Abnormalities of Chrome Plating Workers Occupationally Exposed to Hexavalent Chromium.

Science.gov (United States)

Sudha, S; Kripa, S K; Shibily, P; Shyn, J

2011-01-01

Biomonitoring provides a useful tool to estimate the genetic risk from exposure to genotoxic agents. The aim of this study was to assess the potential cytogenetic damage associated with occupational exposure to hexavalent chromium by using micronuclei (MN) as a biomarker. This was a cross-sectional study and all participants were males. Both the exposed and control individuals were selected from Coimbatore, Southern India. Exfoliated buccal cells from 44 chrome plating workers and 40 age and sex matched control subjects were examined for MN frequency and nuclear abnormalities (NA) other than micronuclei, such as binucleates, broken eggs, karyorrhexis, karyolysis and pyknosis. Results showed statistically significant difference between chrome plating workers and control groups. MN and NA frequencies in chrome plating workers were significantly higher than those in control groups (p chrome plating workers are under risk of significant cytogenetic damage. Therefore, there is a need to educate those who work with heavy metals about the potential hazard of occupational exposure and the importance of using protective measures.

Introducing a Simple Equation to Express Oxidation States as an Alternative to Using Rules Associated with Words Alone

Science.gov (United States)

Minkiewicz, Piotr; Darewicz, Malgorzata; Iwaniak, Anna

2018-01-01

A simple equation to calculate the oxidation states (oxidation numbers) of individual atoms in molecules and ions may be introduced instead of rules associated with words alone. The equation includes two of three categories of bonds, classified as proposed by Goodstein: number of bonds with more electronegative atoms and number of bonds with less…

Characterization of steam generated anti-corrosive oxide films on Aluminium alloys

DEFF Research Database (Denmark)

Din, Rameez Ud; Jellesen, Morten Stendahl; Ambat, Rajan

2014-01-01

of hexavalent chromium is strictly regulated due to its toxic nature and suspected carcinogenicity. So, it is highly imperative to develop other alternatives for chrome conversion coatings. Treatment of aluminium with natural water at elevated temperatures results in the formation of different forms...

Elucidating the mechanism of Cr(VI) formation upon the interaction with metal oxides during coal oxy-fuel combustion.

Science.gov (United States)

Chen, Juan; Jiao, Facun; Zhang, Lian; Yao, Hong; Ninomiya, Yoshihiko

2013-10-15

The thermodynamics underpinning the interaction of Cr-bearing species with basic metal oxides, i.e. K2O, Fe2O3, MgO and CaO, during the air and oxy-fuel combustion of coal have been examined. The synchrotron-based X-ray adsorption near-edge spectroscopy (XANES) was used for Cr speciation. For the oxides tested, Cr(VI) formation is dominated by the reduction potential of the metals. The oxides of Ca(2+) with high reduction potential favored the oxidation of Cr(III), same for K(+). The other two basic metals, Fe2O3 and MgO with lower reduction potentials reacted with Cr(III) to form the corresponding chromites at the temperatures above 600°C. Coal combustion experiments in drop-tube furnace have confirmed the rapid capture of Cr vapors, either trivalent or hexavalent, by CaO into solid ash. The existence of HCl in flue gas favored the vaporization of Cr as CrO2Cl2, which was in turn captured by CaO into chromate. Both Fe2O3 and MgO exhibited less capability on scavenging the Cr(VI) vapor. Particularly, MgO alone exhibited a low capability for capturing the vaporized Cr(III) vapors. However, its co-existence with CaO in the furnace inhibited the Cr(VI) formation. This is beneficial for minimizing the toxicity of Cr in the coal combustion-derived fly ash. Copyright © 2013 Elsevier B.V. All rights reserved.

The Effect of Precursor Ligands and Oxidation State in the Synthesis of Bimetallic Nano-Alloys

KAUST Repository

LaGrow, Alec P.; Knudsen, Kristian; AlYami, Noktan; Anjum, Dalaver H.; Bakr, Osman

2015-01-01

of variables on the characteristics of bimetallic nanomaterials are not completely understood. In this study, we used a continuous-flow synthetic strategy to explore the effects of the ligands and the oxidation state of a metal precursor in a shape

Probing the transition state region in catalytic CO oxidation on Ru

Energy Technology Data Exchange (ETDEWEB)

Ostrom, H. [Stockholm Univ. (Sweden); Oberg, H. [Stockholm Univ. (Sweden); Xin, H. [SLAC National Accelerator Lab., Menlo Park, CA (United States); LaRue, J. [SLAC National Accelerator Lab., Menlo Park, CA (United States); Stanford Univ., Stanford, CA (United States); Beye, M. [SLAC National Accelerator Lab., Menlo Park, CA (United States); Helmholtz Zentrum Berlin fur Materialien und Energie GmbH, Berlin (Germany); Dell' Angela, M. [Univ. of Hamburg and Center for Free Electron Laser Science, Hamburg (Germany); Gladh, J. [Stockholm Univ. (Sweden); Ng, M. L. [SLAC National Accelerator Lab., Menlo Park, CA (United States); Sellberg, J. A. [Stockholm Univ. (Sweden); SLAC National Accelerator Lab., Menlo Park, CA (United States); Kaya, S. [SLAC National Accelerator Lab., Menlo Park, CA (United States); Mercurio, G. [Univ. of Hamburg and Center for Free Electron Laser Science, Hamburg (Germany); Nordlund, D. [SLAC National Accelerator Lab., Menlo Park, CA (United States); Hantschmann, M. [Helmholtz Zentrum Berlin fur Materialien und Energie GmbH, Berlin (Germany); Hieke, F. [Univ. of Hamburg and Center for Free Electron Laser Science, Hamburg (Germany); Kuhn, D. [Helmholtz Zentrum Berlin fur Materialien und Energie GmbH, Berlin (Germany); Schlotter, W. F. [SLAC National Accelerator Lab., Menlo Park, CA (United States); Dakovski, G. L. [SLAC National Accelerator Lab., Menlo Park, CA (United States); Turner, J. J. [SLAC National Accelerator Lab., Menlo Park, CA (United States); Minitti, M. P. [SLAC National Accelerator Lab., Menlo Park, CA (United States); Mitra, A. [SLAC National Accelerator Lab., Menlo Park, CA (United States); Moeller, S. P. [SLAC National Accelerator Lab., Menlo Park, CA (United States); Fohlisch, A. [Helmholtz Zentrum Berlin fur Materialien und Energie GmbH, Berlin (Germany); Univ. Potsdam, Potsdam (Germany); Wolf, M. [Fritz-Haber Institute of the Max-Planck-Society, Berlin (Germany); Wurth, W. [Univ. of Hamburg and Center for Free Electron Laser Science, Hamburg (Germany); DESY Photon Science, Hamburg (Germany); Persson, M. [The Univ. of Liverpool, Liverpool (United Kingdom); Norskov, J. K. [SLAC National Accelerator Lab., Menlo Park, CA (United States); Stanford Univ., Stanford, CA (United States); Abild-Pedersen, F. [Stanford Univ., Stanford, CA (United States); Ogasawara, H. [SLAC National Accelerator Lab., Menlo Park, CA (United States); Pettersson, L. G. M. [Stockholm Univ. (Sweden); Nilsson, A. [Stockholm Univ. (Sweden); SLAC National Accelerator Lab., Menlo Park, CA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States)

2015-02-12

Femtosecond x-ray laser pulses are used to probe the CO oxidation reaction on ruthenium (Ru) initiated by an optical laser pulse. On a time scale of a few hundred femtoseconds, the optical laser pulse excites motions of CO and O on the surface, allowing the reactants to collide, and, with a transient close to a picosecond (ps), new electronic states appear in the O K-edge x-ray absorption spectrum. Density functional theory calculations indicate that these result from changes in the adsorption site and bond formation between CO and O with a distribution of OC–O bond lengths close to the transition state (TS). After 1 ps, 10% of the CO populate the TS region, which is consistent with predictions based on a quantum oscillator model.

A Semi-Analytical Extraction Method for Interface and Bulk Density of States in Metal Oxide Thin-Film Transistors.

Science.gov (United States)

Chen, Weifeng; Wu, Weijing; Zhou, Lei; Xu, Miao; Wang, Lei; Ning, Honglong; Peng, Junbiao

2018-03-11

A semi-analytical extraction method of interface and bulk density of states (DOS) is proposed by using the low-frequency capacitance-voltage characteristics and current-voltage characteristics of indium zinc oxide thin-film transistors (IZO TFTs). In this work, an exponential potential distribution along the depth direction of the active layer is assumed and confirmed by numerical solution of Poisson's equation followed by device simulation. The interface DOS is obtained as a superposition of constant deep states and exponential tail states. Moreover, it is shown that the bulk DOS may be represented by the superposition of exponential deep states and exponential tail states. The extracted values of bulk DOS and interface DOS are further verified by comparing the measured transfer and output characteristics of IZO TFTs with the simulation results by a 2D device simulator ATLAS (Silvaco). As a result, the proposed extraction method may be useful for diagnosing and characterising metal oxide TFTs since it is fast to extract interface and bulk density of states (DOS) simultaneously.

A Semi-Analytical Extraction Method for Interface and Bulk Density of States in Metal Oxide Thin-Film Transistors

Directory of Open Access Journals (Sweden)

Weifeng Chen

2018-03-01

Full Text Available A semi-analytical extraction method of interface and bulk density of states (DOS is proposed by using the low-frequency capacitance–voltage characteristics and current–voltage characteristics of indium zinc oxide thin-film transistors (IZO TFTs. In this work, an exponential potential distribution along the depth direction of the active layer is assumed and confirmed by numerical solution of Poisson’s equation followed by device simulation. The interface DOS is obtained as a superposition of constant deep states and exponential tail states. Moreover, it is shown that the bulk DOS may be represented by the superposition of exponential deep states and exponential tail states. The extracted values of bulk DOS and interface DOS are further verified by comparing the measured transfer and output characteristics of IZO TFTs with the simulation results by a 2D device simulator ATLAS (Silvaco. As a result, the proposed extraction method may be useful for diagnosing and characterising metal oxide TFTs since it is fast to extract interface and bulk density of states (DOS simultaneously.

Cellulose nanofibril/reduced graphene oxide/carbon nanotube hybrid aerogels for highly flexible and all-solid-state supercapacitors

Science.gov (United States)

Qifeng Zheng; Zhiyong Cai; Zhenqiang Ma; Shaoqin Gong

2015-01-01

A novel type of highly flexible and all-solid-state supercapacitor that uses cellulose nanofibril (CNF)/reduced graphene oxide (RGO)/carbon nanotube (CNT) hybrid aerogels as electrodes and H2SO4 poly (vinyl alcohol) PVA gel as the electrolyte was developed and is reported here. These flexible solid-state supercapacitors...

Actinide metals

Energy Technology Data Exchange (ETDEWEB)

Brown, Paul L. [Geochem Australia, Kiama, NSW (Australia); Ekberg, Christian [Chalmers Univ. of Technology, Goeteborg (Sweden). Nuclear Chemistry/Industrial Materials Recycling

2016-07-01

All isotopes of actinium are radioactive and exist in aqueous solution only in the trivalent state. There have been very few studies on the hydrolytic reactions of actinium(III). The hydrolysis reactions for uranium would only be important in alkaline pH conditions. Thermodynamic parameters for the hydrolysis species of uranium(VI) and its oxide and hydroxide phases can be determined from the stability and solubility constants. The hydrolytic behaviour of neptunium(VI) is quite similar to that of uranium(VI). The solubility constant of NpO{sub 2}OH(am) has been reported a number of times for both zero ionic strength and in fixed ionic strength media. Americium can form four oxidation states in aqueous solution, namely trivalent, tetravalent, pentavalent and hexavalent. Desire, Hussonnois and Guillaumont determined stability constants for the species AmOH{sup 2+} for the actinides, plutonium(III), americium(III), curium(III), berkelium(III) and californium(III) using a solvent extraction technique.

Actinide metals

International Nuclear Information System (INIS)

Brown, Paul L.; Ekberg, Christian

2016-01-01

All isotopes of actinium are radioactive and exist in aqueous solution only in the trivalent state. There have been very few studies on the hydrolytic reactions of actinium(III). The hydrolysis reactions for uranium would only be important in alkaline pH conditions. Thermodynamic parameters for the hydrolysis species of uranium(VI) and its oxide and hydroxide phases can be determined from the stability and solubility constants. The hydrolytic behaviour of neptunium(VI) is quite similar to that of uranium(VI). The solubility constant of NpO 2 OH(am) has been reported a number of times for both zero ionic strength and in fixed ionic strength media. Americium can form four oxidation states in aqueous solution, namely trivalent, tetravalent, pentavalent and hexavalent. Desire, Hussonnois and Guillaumont determined stability constants for the species AmOH 2+ for the actinides, plutonium(III), americium(III), curium(III), berkelium(III) and californium(III) using a solvent extraction technique.

Synchrotron Micro-XANES Measurements of Vanadium Oxidation State in Glasses as a Function of Oxygen Fugacity: Experimental Calibration of Data Relevant to Partition Coefficient Determination

Science.gov (United States)

Delaney, J. S.; Sutton, S. R.; Newville, M.; Jones, J. H.; Hanson, B.; Dyar, M. D.; Schreiber, H.

2000-01-01

Oxidation state microanalyses for V in glass have been made by calibrating XANES spectral features with optical spectroscopic measurements. The oxidation state change with fugacity of O2 will strongly influence partitioning results.

Oxidation under electron bombardment. A tool for studying the initial states of silicon oxidation

Energy Technology Data Exchange (ETDEWEB)

Carriere, B.; Deville, J.P.; El Maachi, A.

1987-06-01

The exciting beam of an Auger electron spectrometer has been used to monitor the oxidation of silicon single crystals at room temperature and very low pressures of oxygen (approx. 10/sup -7/ Torr). This process allows us to build ultra-thin layers of silica on silicon (down to 30 A) but it is mostly used to investigate the mechanisms of the initial stages of oxidation. Auger spectra recorded continuously during the oxidation process provide information on (1) the nature of the silicon-oxygen chemical bonds which are interpreted through fine structure in the Auger peak, and (2) the kinetics of oxide formation which are deduced from curves of Auger signal versus time. An account is given of the contribution of these Auger studies to the description of the intermediate oxide layer during the reaction between silicon and oxygen and the influence of surface structural disorder, induced mainly by argon-ion bombardment, is discussed in terms of reactivity and oxide coverage.

Quantum confinement-induced tunable exciton states in graphene oxide.

Science.gov (United States)

Lee, Dongwook; Seo, Jiwon; Zhu, Xi; Lee, Jiyoul; Shin, Hyeon-Jin; Cole, Jacqueline M; Shin, Taeho; Lee, Jaichan; Lee, Hangil; Su, Haibin

2013-01-01

Graphene oxide has recently been considered to be a potential replacement for cadmium-based quantum dots due to its expected high fluorescence. Although previously reported, the origin of the luminescence in graphene oxide is still controversial. Here, we report the presence of core/valence excitons in graphene-based materials, a basic ingredient for optical devices, induced by quantum confinement. Electron confinement in the unreacted graphitic regions of graphene oxide was probed by high resolution X-ray absorption near edge structure spectroscopy and first-principles calculations. Using experiments and simulations, we were able to tune the core/valence exciton energy by manipulating the size of graphitic regions through the degree of oxidation. The binding energy of an exciton in highly oxidized graphene oxide is similar to that in organic electroluminescent materials. These results open the possibility of graphene oxide-based optoelectronic device technology.

Lung injury, inflammation and Akt signaling following inhalation of particulate hexavalent chromium

International Nuclear Information System (INIS)

Beaver, Laura M.; Stemmy, Erik J.; Constant, Stephanie L.; Schwartz, Arnold; Little, Laura G.; Gigley, Jason P.; Chun, Gina; Sugden, Kent D.

2009-01-01

Certain particulate hexavalent chromium [Cr(VI)] compounds are human respiratory carcinogens that release genotoxic soluble chromate, and are associated with fibrosis, fibrosarcomas, adenocarcinomas and squamous cell carcinomas of the lung. We postulate that inflammatory processes and mediators may contribute to the etiology of Cr(VI) carcinogenesis, however the immediate (0-24 h) pathologic injury and immune responses after exposure to particulate chromates have not been adequately investigated. Our aim was to determine the nature of the lung injury, inflammatory response, and survival signaling responses following intranasal exposure of BALB/c mice to particulate basic zinc chromate. Factors associated with lung injury, inflammation and survival signaling were measured in airway lavage fluid and in lung tissue. A single chromate exposure induced an acute immune response in the lung, characterized by a rapid and significant increase in IL-6 and GRO-α levels, an influx of neutrophils, and a decline in macrophages in lung airways. Histological examination of lung tissue in animals challenged with a single chromate exposure revealed an increase in bronchiolar cell apoptosis and mucosal injury. Furthermore, chromate exposure induced injury and inflammation that progressed to alveolar and interstitial pneumonitis. Finally, a single Cr(VI) challenge resulted in a rapid and persistent increase in the number of airways immunoreactive for phosphorylation of the survival signaling protein Akt, on serine 473. These data illustrate that chromate induces both survival signaling and an inflammatory response in the lung, which we postulate may contribute to early oncogenesis

Investigation of Hexavalent Chromium Flux to Groundwater at the 100-C-7:1 Excavation Site

Energy Technology Data Exchange (ETDEWEB)

Truex, Michael J.; Vermeul, Vincent R.; Fritz, Brad G.; Mackley, Rob D.; Horner, Jacob A.; Johnson, Christian D.; Newcomer, Darrell R.

2012-11-16

Deep excavation of soil has been conducted at the 100-C-7 and 100-C-7:1 waste sites within the 100-BC Operable Unit at the Department of Energy (DOE) Hanford Site to remove hexavalent chromium (Cr(VI)) contamination with the excavations reaching to near the water table. Soil sampling showed that Cr(VI) contamination was still present at the bottom of the 100-C-7:1 excavation. In addition, Cr(VI) concentrations in a downgradient monitoring well have shown a transient spike of increased Cr(VI) concentration following initiation of excavation. Potentially, the increased Cr(VI) concentrations in the downgradient monitoring well are due to Cr(VI) from the excavation site. However, data were needed to evaluate this possibility and to quantify the overall impact of the 100-C-7:1 excavation site on groundwater. Data collected from a network of aquifer tubes installed across the floor of the 100-C-7:1 excavation and from temporary wells installed at the bottom of the entrance ramp to the excavation were used to evaluate Cr(VI) releases into the aquifer and to estimate local-scale hydraulic properties and groundwater flow velocity.

Actinide Oxidation State and O/M Ratio in Hypostoichiometric Uranium-Plutonium-Americium U0.750Pu0.246Am0.004O2-x Mixed Oxides.

Science.gov (United States)

Vauchy, Romain; Belin, Renaud C; Robisson, Anne-Charlotte; Lebreton, Florent; Aufore, Laurence; Scheinost, Andreas C; Martin, Philippe M

2016-03-07

Innovative americium-bearing uranium-plutonium mixed oxides U1-yPuyO2-x are envisioned as nuclear fuel for sodium-cooled fast neutron reactors (SFRs). The oxygen-to-metal (O/M) ratio, directly related to the oxidation state of cations, affects many of the fuel properties. Thus, a thorough knowledge of its variation with the sintering conditions is essential. The aim of this work is to follow the oxidation state of uranium, plutonium, and americium, and so the O/M ratio, in U0.750Pu0.246Am0.004O2-x samples sintered for 4 h at 2023 K in various Ar + 5% H2 + z vpm H2O (z = ∼ 15, ∼ 90, and ∼ 200) gas mixtures. The O/M ratios were determined by gravimetry, XAS, and XRD and evidenced a partial oxidation of the samples at room temperature. Finally, by comparing XANES and EXAFS results to that of a previous study, we demonstrate that the presence of uranium does not influence the interactions between americium and plutonium and that the differences in the O/M ratio between the investigated conditions is controlled by the reduction of plutonium. We also discuss the role of the homogeneity of cation distribution, as determined by EPMA, on the mechanisms involved in the reduction process.

The Growth of Gypsum in the Presence of Hexavalent Chromium: A Multiscale Study

Directory of Open Access Journals (Sweden)

Juan Morales

2016-03-01

Full Text Available The sorption of dissolved inorganic pollutants into the structure of minerals is an important process that controls the mobility and fate of these pollutants in the Earth’s crust. It also modifies the surface structure and composition of the host mineral, affecting its crystallization kinetics. Here, we investigate the effect of hexavalent chromium, Cr(VI, on the nucleation and growth of gypsum by conducting two types of experiments: (i in situ atomic force microscopy (AFM observations of the growth of gypsum {010} surfaces in the presence of Cr(VI and (ii gypsum precipitation experiments by mixing aqueous solutions containing variable amounts of Cr(VI. Gypsum precipitation is progressively delayed when occurring from solutions bearing increasing Cr(VI concentrations. Chemical analyses of gypsum precipitates show that gypsum incorporates small Cr(VI amounts that correlate with the content of this ion in the aqueous solution. Gypsum cell parameters variation reflects this incorporation. At the molecular scale, Cr(VI induces a slowdown of step advance rates on gypsum {010} surfaces accompanied by the roughening of nanostep edges and the so-called “template effect”. This effect involves the reproduction of the original nanotopography after the completion of individual advancing monolayers and appears as a general nanoscale phenomenon occurring during growth of solid solutions from aqueous solutions even in the case of compositionally-restricted solid solutions.

Preparation of Silk Sericin/Lignin Blend Beads for the Removal of Hexavalent Chromium Ions

Science.gov (United States)

Kwak, Hyo Won; Shin, Munju; Yun, Haesung; Lee, Ki Hoon

2016-01-01

In the present study, novel adsorbents having high adsorption capability and reusability were prepared using agricultural by-products: silk sericin and lignin. Silk sericin and lignin blend beads were successfully prepared using simple coagulation methods for the removal of hexavalent chromium (Cr(VI)) from aqueous solution. A 1 M lithium chloride (LiCl)/dimethyl sulfoxide (DMSO) solvent system successfully dissolved both sericin and lignin and had sufficient viscosity for bead preparation. Compared to the conventional sericin bead adsorbent, sericin/lignin blend beads showed higher Cr(VI) adsorption capacity. The amount of lignin added to the adsorbent greatly affected the adsorption capacity of the beads, and a 50:50 sericin/lignin blend ratio was optimal. Adsorption behavior followed the Freundlich isotherm, which means the adsorption of Cr(VI) occurred on the heterogeneous surface. Cr(VI) adsorption capability increased with temperature because of thermodynamic-kinetic effects. In addition, over 90% of Cr(VI) ions were recovered from the Cr(VI) adsorbed sericin/lignin beads in a 1 M NaOH solution. The adsorption-desorption recycling process was stable for more than seven cycles, and the recycling efficiency was 82%. It is expected that the sericin/lignin beads could be successfully applied in wastewater remediation especially for hazardous Cr(VI) ions in industrial wastewater. PMID:27598142

Preparation of Silk Sericin/Lignin Blend Beads for the Removal of Hexavalent Chromium Ions

Directory of Open Access Journals (Sweden)

Hyo Won Kwak

2016-09-01

Full Text Available In the present study, novel adsorbents having high adsorption capability and reusability were prepared using agricultural by-products: silk sericin and lignin. Silk sericin and lignin blend beads were successfully prepared using simple coagulation methods for the removal of hexavalent chromium (Cr(VI from aqueous solution. A 1 M lithium chloride (LiCl/dimethyl sulfoxide (DMSO solvent system successfully dissolved both sericin and lignin and had sufficient viscosity for bead preparation. Compared to the conventional sericin bead adsorbent, sericin/lignin blend beads showed higher Cr(VI adsorption capacity. The amount of lignin added to the adsorbent greatly affected the adsorption capacity of the beads, and a 50:50 sericin/lignin blend ratio was optimal. Adsorption behavior followed the Freundlich isotherm, which means the adsorption of Cr(VI occurred on the heterogeneous surface. Cr(VI adsorption capability increased with temperature because of thermodynamic-kinetic effects. In addition, over 90% of Cr(VI ions were recovered from the Cr(VI adsorbed sericin/lignin beads in a 1 M NaOH solution. The adsorption-desorption recycling process was stable for more than seven cycles, and the recycling efficiency was 82%. It is expected that the sericin/lignin beads could be successfully applied in wastewater remediation especially for hazardous Cr(VI ions in industrial wastewater.

General regularity of the oxidation potential variations and high oxidation states in the second half of the actinide series

International Nuclear Information System (INIS)

Spitsyn, V.I.; Vokhmin, V.G.; Ionova, G.V.; Pershina, V.G.

1984-01-01

Oxidation potentials (OP) PHI(4/3), PHI(5/3), PHI(6/3), PHI(5/4) and PHI(6/5) are calculated for the members of the actinide series. A semiemperic relation combining OP with explicit terms for ground level energies of actinide ions in Russell-Saunders approximation as well as known values of formal OP relative to the normal hydrogen electrode potential are used as an extrapolation function. It is shown that an increase of PHI(4/3) OP which occurs after Bsub(k) explains a low stability of the oxidation state 4 in solutions for actinides of the second half of the series. PHI(5/3) and PHI(5/4) OP in the section starting with Cm have the minimum at Cf. PHI(6/3) OP for Cm, Bk, Cf and Es are practically the same but for Cm, Bk and Es they are smaller than PHI(5/3) OP. A principle possibility of Bk(6), Cf(6) and Es(6) preparation is shown

Quantitative evaluation of the effect of H2O degassing on the oxidation state of magmas

Science.gov (United States)

Lange, R. A.; Waters, L.

2014-12-01

The extent to which degassing of the H2O component affects the oxidation state of hydrous magmas is widely debated. Several researchers have examined how degassing of mixed H-C-O-S-Cl fluids may change the Fe3+/FeT ratio of various magmas, whereas our focus is on the H2O component. There are two ways that degassing of H2O by itself may cause oxidation: (1) the reaction: H2O (melt) + 2FeO (melt) = H2 (fluid) + Fe2O3 (melt), and/or (2) if dissolved water preferentially enhances the activity of ferrous vs. ferric iron in magmatic liquids. In this study, a comparison is made between the pre-eruptive oxidation states of 14 crystal-poor, jet-black obsidian samples (obtained from two Fe-Ti oxides) and their post-eruptive values (analyzed with the Wilson 1960 titration method tested against USGS standards). The obsidians are from Medicine Lake (CA), Long Valley (CA), and the western Mexican arc; all have low FeOT (1.1-2.1 wt%), rendering their Fe2+/Fe3+ ratios highly sensitive to the possible effects of substantial H2O degassing. The Fe-Ti oxide thermometer/oxybarometer of Ghiorso and Evans, (2008) gave temperatures for the 14 samples that range for 720 to 940°C and ΔNNO values of -0.9 to +1.4. With temperature known, the plagioclase-liquid hygrometer was applied and show that ≤ 6.5 wt% H2O was dissolved in the melts prior to eruption. In addition, pre-eruptive Cl and S concentrations were constrained on the basis of apatite analyses (Webster et al., 2009) and sulfur concentrations needed for saturation with pyrrhotite (Clemente et al., 2004), respectively. Maximum pre-eruptive chlorine and sulfur contents are 6000 and 200 ppm, respectively. After eruption, the rhyolites lost nearly all of their volatiles. Our results indicate no detectable change between pre- and post-eruptive Fe2+ concentrations, with an average deviation of ± 0.1 wt % FeO. Although degassing of large concentrations of S and/or Cl may affect the oxidation state of magmas, at the pre-eruptive levels

Oxidative Stress State Is Associated with Left Ventricular Mechanics Changes, Measured by Speckle Tracking in Essential Hypertensive Patients

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Luis Antonio Moreno-Ruíz

2015-01-01

Full Text Available The oxidative stress state is characterized by an increase in oxygen reactive species that overwhelms the antioxidant defense; we do not know if these pathological changes are correlated with alterations in left ventricular mechanics. The aim was correlating the oxidative stress state with the left ventricular global longitudinal strain (GLS and the left ventricular end diastolic pressure (LVEDP. Twenty-five patients with essential hypertension and 25 controls paired by age and gender were studied. All of the participants were subjected to echocardiography and biochemical determination of oxidative stress markers. The hypertensive patients, compared with control subjects, had significantly (p<0.05 higher levels of oxidized proteins (5.03±1.05 versus 4.06±0.63 nmol/mg, lower levels of extracellular superoxide dismutase (EC-SOD activity (0.045±0.02 versus 0.082±0.02 U/mg, higher LVEDP (16.2±4.5 versus 11.3±1.6 mm Hg, and lower GLS (−12% versus −16%. Both groups had preserved ejection fraction and the results showed a positive correlation of oxidized proteins with GLS (r=0.386, p=0.006 and LVEDP (r=0.389, p=0.005; we also found a negative correlation of EC-SOD activity with GLS (r=-0.404, p=0.004 and LVEDP (r=-0.347, p=0.014.

Chemical states of fission products in irradiated uranium-plutonium mixed oxide fuel

International Nuclear Information System (INIS)

Kurosaki, Ken; Uno, Masayoshi; Yamanaka, Shinsuke

1999-01-01

The chemical states of fission products (FPs) in irradiated uranium-plutonium mixed oxide (MOX) fuel for the light water reactor (LWR) were estimated by thermodynamic equilibrium calculations on system of fuel and FPs by using ChemSage program. A stoichiometric MOX containing 6.1 wt. percent PuO 2 was taken as a loading fuel. The variation of chemical states of FPs was calculated as a function of oxygen potential. Some pieces of information obtained by the calculation were compared with the results of the post-irradiation examination (PIE) of UO 2 fuel. It was confirmed that the multicomponent and multiphase thermodynamic equilibrium calculation between fuel and FPs system was an effective tool for understanding the behavior of FPs in fuel. (author)

Hexavalent Chromium Removal from Model Water and Car Shock Absorber Factory Effluent by Nanofiltration and Reverse Osmosis Membrane

Directory of Open Access Journals (Sweden)

Amine Mnif

2017-01-01

Full Text Available Nanofiltration and reverse osmosis are investigated as a possible alternative to the conventional methods of Cr(VI removal from model water and industrial effluent. The influences of feed concentration, water recovery, pH, and the coexisting anions were studied. The results have shown that retention rates of hexavalent chromium can reach 99.7% using nanofiltration membrane (NF-HL and vary from 85 to 99.9% using reverse osmosis membrane (RO-SG depending upon the composition of the solution and operating conditions. This work was also extended to investigate the separation of Cr(VI from car shock absorber factory effluent. The use of these membranes is very promising for Cr(VI water treatment and desalting industry effluent. Spiegler-Kedem model was applied to experimental results in the aim to determine phenomenological parameters, the reflection coefficient of the membrane (σ, and the solute permeability coefficient (Ps. The convective and diffusive parts of the mass transfer were quantified with predominance of the diffusive contribution.

Self-assembly modified-mushroom nanocomposite for rapid removal of hexavalent chromium from aqueous solution with bubbling fluidized bed.

Science.gov (United States)

Xu, Fei; Liu, Xu; Chen, Yijiao; Zhang, Ke; Xu, Heng

2016-05-18

A self-assembled modified Pleurotus Cornucopiae material (SMPM) combined with improved Intermittent Bubbling Fluidized Bed (IBFB) was investigated to remove the hexavalent chromium ions in aqueous solution. After the modification, the powder-like raw material gradually self-assembled together to SMPM, which had crinkly porous structure, improved the Cr-accommodation ability in a sound manner. Optimized by Taguchi method, Cr(VI) removal efficiency was up to 75.91% and 48.01% for 100 mg/L and 500 mg/L initial concentration of Cr(VI), respectively. Results indicated that the metal removal was dependent on dosage of adsorbent, particle diameter and treatment time. The experimental data obtained from the biosorption process was successfully correlated with Freundlich isotherm model. Thermodynamic study indicated the endothermic nature of the process. The results confirmed that self-assembly modified Pleurotus Cornucopiae material could be applied for the removal of heavy metal from wastewater in continuous fluidized bed process.

Origin of stabilization and destabilization in solid-state redox reaction of oxide ions for lithium-ion batteries.

Science.gov (United States)

Yabuuchi, Naoaki; Nakayama, Masanobu; Takeuchi, Mitsue; Komaba, Shinichi; Hashimoto, Yu; Mukai, Takahiro; Shiiba, Hiromasa; Sato, Kei; Kobayashi, Yuki; Nakao, Aiko; Yonemura, Masao; Yamanaka, Keisuke; Mitsuhara, Kei; Ohta, Toshiaki

2016-12-23

Further increase in energy density of lithium batteries is needed for zero emission vehicles. However, energy density is restricted by unavoidable theoretical limits for positive electrodes used in commercial applications. One possibility towards energy densities exceeding these limits is to utilize anion (oxide ion) redox, instead of classical transition metal redox. Nevertheless, origin of activation of the oxide ion and its stabilization mechanism are not fully understood. Here we demonstrate that the suppression of formation of superoxide-like species on lithium extraction results in reversible redox for oxide ions, which is stabilized by the presence of relatively less covalent character of Mn 4+ with oxide ions without the sacrifice of electronic conductivity. On the basis of these findings, we report an electrode material, whose metallic constituents consist only of 3d transition metal elements. The material delivers a reversible capacity of 300 mAh g -1 based on solid-state redox reaction of oxide ions.

Origin of stabilization and destabilization in solid-state redox reaction of oxide ions for lithium-ion batteries

Science.gov (United States)

Yabuuchi, Naoaki; Nakayama, Masanobu; Takeuchi, Mitsue; Komaba, Shinichi; Hashimoto, Yu; Mukai, Takahiro; Shiiba, Hiromasa; Sato, Kei; Kobayashi, Yuki; Nakao, Aiko; Yonemura, Masao; Yamanaka, Keisuke; Mitsuhara, Kei; Ohta, Toshiaki

2016-01-01

Further increase in energy density of lithium batteries is needed for zero emission vehicles. However, energy density is restricted by unavoidable theoretical limits for positive electrodes used in commercial applications. One possibility towards energy densities exceeding these limits is to utilize anion (oxide ion) redox, instead of classical transition metal redox. Nevertheless, origin of activation of the oxide ion and its stabilization mechanism are not fully understood. Here we demonstrate that the suppression of formation of superoxide-like species on lithium extraction results in reversible redox for oxide ions, which is stabilized by the presence of relatively less covalent character of Mn4+ with oxide ions without the sacrifice of electronic conductivity. On the basis of these findings, we report an electrode material, whose metallic constituents consist only of 3d transition metal elements. The material delivers a reversible capacity of 300 mAh g−1 based on solid-state redox reaction of oxide ions. PMID:28008955

Study of the reaction of uranium and plutonium with bone char

International Nuclear Information System (INIS)

Silver, G.L.; Koenst, J.W.

1977-01-01

A study of the reaction of plutonium with a commercial bone char indicates that this bone char has a high capacity for removing plutonium from aqueous wastes. The adsorption of plutonium by bone char is pH dependent, and for plutonium(IV) polymer appears to be maximized near pH 7.3 for plutonium concentrations typical of some waste streams. Adsorption is affected by dissolved salts, especially calcium and phosphate salts. Freundlich isotherms representing the adsorption of uranium and plutonium have been prepared. The low potential imposed upon aqueous solutions by commercial bone char is adequate for reduction of hexavalent plutonium to a lower plutonium oxidation state

Assessment of the mode of action for hexavalent chromium-induced lung cancer following inhalation exposures

International Nuclear Information System (INIS)

Proctor, Deborah M.; Suh, Mina; Campleman, Sharan L.; Thompson, Chad M.

2014-01-01

Highlights: • No published or well recognized MOA for Cr(VI)-induced lung tumors exists. • MOA analysis for Cr(VI)-induced lung cancer was conducted to inform risk assessment. • Cr(VI) epidemiologic, toxicokinetic, toxicological, mechanistic data were evaluated. • Weight of evidence does not support a mutagenic MOA for Cr(VI)-induced lung cancer. • Non-linear approaches should be considered for evaluating Cr(VI) lung cancer risk. - Abstract: Inhalation of hexavalent chromium [Cr(VI)] is associated with increased lung cancer risk among workers in several industries, most notably chromate production workers exposed to high concentrations of Cr(VI) (≥100 μg/m 3 ), for which clear exposure–response relationships and respiratory irritation and tissue damage have been reported. Data from this industry are used to assess lung cancer risk associated with environmental and current occupational exposures, occurring at concentrations that are significantly lower. There is considerable uncertainty in the low dose extrapolation of historical occupational epidemiology data to assess risk at current exposures because no published or well recognized mode of action (MOA) for Cr(VI)-induced lung tumors exists. We conducted a MOA analysis for Cr(VI)-induced lung cancer evaluating toxicokinetic and toxicological data in humans and rodents and mechanistic data to assess plausibility, dose–response, and temporal concordance for potential MOAs. Toxicokinetic data support that extracellular reduction of Cr(VI), which limits intracellular absorption of Cr(VI) and Cr(VI)-induced toxicity, can be overwhelmed at high exposure levels. In vivo genotoxicity and mutagenicity data are mostly negative and do not support a mutagenic MOA. Further, both chronic bioassays and the epidemiologic literature support that lung cancer occurs at exposures that cause tissue damage. Based on this MOA analysis, the overall weight of evidence supports a MOA involving deposition and accumulation

Single Crystal Growth of Pure Co3+ Oxidation State Material LaSrCoO4

Directory of Open Access Journals (Sweden)

Hanjie Guo

2016-08-01

Full Text Available We report on the single crystal growth of the single-layer perovskite cobaltate LaSrCoO4 that was grown by the optical floating zone method using high oxygen pressures. Phase purity and single crystallinity were confirmed by X-ray diffraction techniques. The pure Co3+ oxidation state was confirmed by X-ray absorbtion spectroscopy measurements. A transition to a spin glass state is observed at ∼7 K in magnetic susceptibility and specific heat measurements.

Rapid Synthesis of Lead Oxide Nanorods by One-step Solid-state Chemical Reaction at Room Temperature

Institute of Scientific and Technical Information of China (English)

CAO, Ya-Li(曹亚丽); JIA, Dian-Zeng(贾殿赠); LIU, Lang(刘浪); LUO, Jian-Min(骆建敏)

2004-01-01

A simple and facile method was reported to synthesize lead oxide nanorods. Nanorods of lead oxide were obtained directly from grinding solid metal salt and sodium hydroxide in agate mortar with the assistance of a suitable nonionic surfactant in only one step, which is different from the result of hydroxide in solution. The product has been characterized by XRD, TEM and SEM. The formation mechanism of rod-like morphology is discussed and the surfactant plays an important soft-template role in modifying the interface of solid-state reaction and according process of rod-formation.

Hexavalent Chromium Is Cytotoxic and Genotoxic to Hawksbill Sea Turtle Cells

Science.gov (United States)

Wise, Sandra S.; Xie, Hong; Fukuda, Tomokazu; Thompson, W. Douglas; Wise, John Pierce

2014-01-01

Sea turtles are a charismatic and ancient ocean species and can serve as key indicators for ocean ecosystems, including coral reefs and sea grass beds as well as coastal beaches. Genotoxicity studies in the species are absent, limiting our understanding of the impact of environmental toxicants on sea turtles. Hexavalent chromium (Cr(VI)) is a ubiquitous environmental problem worldwide, and recent studies show it is a global marine pollutant of concern. Thus, we evaluated the cytotoxicity and genotoxicity of soluble and particulate Cr(VI) in hawksbill sea turtle cells. Particulate Cr(VI) was both cytotoxic and genotoxic to sea turtle cells. Concentrations of 0.1, 0.5, 1, and 5 μg/cm2 lead chromate induced 108, 79, 54, and 7 percent relative survival, respectively. Additionally, concentrations of 0, 0.1, 0.5, 1, and 5 μg/cm2 lead chromate induced damage in 4, 10, 15, 26, and 36 percent of cells and caused 4, 11, 17, 30, and 56 chromosome aberrations in 100 metaphases, respectively. For soluble Cr, concentrations of 0.25, 0.5, 1, 2.5, and 5 μM sodium chromate induced 84, 69, 46, 25, and 3 percent relative survival, respectively. Sodium chromate induced 3, 9, 9, 14, 21, and 29 percent of metaphases with damage, and caused 3, 10, 10, 16, 26, and 39 damaged chromosomes in 100 metaphases at concentrations of 0, 0.25, 0.5, 1, 2.5, and 5 μM sodium chromate, respectively. These data suggest that Cr(VI) may be a concern for hawksbill sea turtles and sea turtles in general. PMID:24952338

Low oxidation state aluminum-containing cluster anions: Cp{sup ∗}Al{sub n}H{sup −}, n = 1–3

Energy Technology Data Exchange (ETDEWEB)

Zhang, Xinxing; Ganteför, Gerd; Bowen, Kit, E-mail: AKandalam@wcupa.edu, E-mail: kbowen@jhu.edu [Department of Chemistry, Johns Hopkins University, Baltimore, Maryland 21218 (United States); Eichhorn, Bryan [Department of Chemistry, University of Maryland, College Park, Maryland 20742 (United States); Mayo, Dennis [EOD Technology Division, Naval Surface Warfare Center, Indian Head, Maryland 20640 (United States); Sawyer, William H.; Gill, Ann F.; Kandalam, Anil K., E-mail: AKandalam@wcupa.edu, E-mail: kbowen@jhu.edu [Department of Physics, West Chester University of PA, West Chester, Pennsylvania 19383 (United States); Schnöckel, Hansgeorg [Institute of Inorganic Chemistry, Karlsruhe Institute of Technology, D-76131 Karlsruhe (Germany)

2016-08-21

Three new, low oxidation state, aluminum-containing cluster anions, Cp*Al{sub n}H{sup −}, n = 1–3, were prepared via reactions between aluminum hydride cluster anions, Al{sub n}H{sub m}{sup −}, and Cp*H ligands. These were characterized by mass spectrometry, anion photoelectron spectroscopy, and density functional theory based calculations. Agreement between the experimentally and theoretically determined vertical detachment energies and adiabatic detachment energies validated the computed geometrical structures. Reactions between aluminum hydride cluster anions and ligands provide a new avenue for discovering low oxidation state, ligated aluminum clusters.

Long-living positron and positronium states in zeolites and microcrystalline oxides

International Nuclear Information System (INIS)

Kajcsos, Zs.; Liszkay, L.; Varga, L.; Lohonyai, L.; Lazar, K.

1995-01-01

Positron annihilation (PA) investigation were performed on zeolites (X, Y and ZSM-5) and on microcrystalline MgO, Al 2 O 3 and SiO 2 , providing long lifetime components attributed to o-Ps atoms. In addition to the positron lifetime (LT) measurements, the energy distribution (ED) of the annihilation gamma radiation spectrum was recorded in the 30 keV - 1.5 MeV range for different samples and was compared to reference distributions for Si and GaAs samples, where no long-living Ps states are formed. Apart from the strong correlation with the water content in the samples, the positron data collected testify much more pronounced positronium hosting features for powders of the mentioned oxides than for zeolites. Positron LT spectroscopy combined with recording of the ED of the annihilation radiation provides reliable information on the forming of long living 3γ states. (author) 15 refs.; 4 figs

Structural oxidation state studies of the manganese cluster in the oxygen evolving complex of photosystem II

Energy Technology Data Exchange (ETDEWEB)

Liang, Wenchuan [Univ. of California, Berkeley, CA (United States)

1994-11-01

X-ray absorption spectroscopy (XAS) was performed on Photosystem II (PSII)-enriched membranes prepared from spinach to explore: (1) the correlation between structure and magnetic spin state of the Mn cluster in the oxygen evolving complex (OEC) in the S₂ state; and (2) the oxidation state changes of the Mn cluster in the flash-induced S-states. The structure of the Mn cluster in the S₂ state with the g~4 electron paramagnetic resonance (EPR) signal (S₂-g4 state) was compared with that in the S₂ state with multiline signal (S₂-MLS state) and the S₁ state. The S₂-g4 state has a higher XAS inflection point energy than that of the S₁ state, indicating the oxidation of Mn in the advance from the S₁ to the S₂-g4 state. Differences in the edge shape and in the extended X-ray absorption fine structure (EXAFS) show that the structure of the Mn cluster in the S₂-g4 state is different from that in the S₂-MLS or the S₁ state. In the S₂-g4 state, the second shell of backscatterers from the Mn absorber contains two Mn-Mn distances of 2.73 Å and 2.85 Å. Very little distance disorder exists in the second shell of the S₁ or S₂-MLS states. The third shell of the S₂-g4 state at about 3.3 Å also contains increased heterogeneity relative to that of the S₂-MLS or the S₁ state. Various S-states were prepared at room-temperature by saturating, single-turnover flashes. The flash-dependent oscillation in the amplitude of the MLS was used to characterize the S-state composition and to construct "pure" S-state Mn K-edge spectra. The edge position shifts to higher energy by 1.8 eV upon the S₁ → S₂ transition.

Oxidation state of sulfur, iron and tin at the surface of float glasses

International Nuclear Information System (INIS)

Lagarde, P; Flank, A-M; Jupille, J; Montigaud, H

2009-01-01

Sulfur is an important element of glasses, not because of its amount, always very low (less than 0.4 % in weight of SO 3 ), but because of its role since it actively participates to the refinement process and, combined to other elements, it can be responsible for the coloration of the glass. Iron is also of a major importance in most of the glasses. In the case of the float glass, the two faces, because of the fabrication process, are different in terms of composition (presence of Sn for one face) and also in terms of oxidation state of these minority elements (Fe, Sn, S). There should be a subtle interplay between the concentrations and the oxidation states of these different minority elements, and anyway these variations occur over a thickness of the order of few micrometers below the surface. Using the high intensity and the focusing properties (3 x 3 μm 2 ) of the x-ray beam from the Lucia beamline, we have therefore studied the speciation of iron and sulfur near the face of a float glass in relation with the behavior of tin. This has been obtained by combining elemental x-ray fluorescence cartography and x-ray micro-absorption at the different K-edges.

Oxidation state of sulfur, iron and tin at the surface of float glasses

Energy Technology Data Exchange (ETDEWEB)

Lagarde, P; Flank, A-M [Synchrotron SOLEIL, l' Orme des Merisiers, BP 48 91192 Gif/Yvette cedex (France); Jupille, J [IMPMC, Universite P. and M. Curie, Campus de Boucicaut, 140 rue de Lourmel 75015 Paris (France); Montigaud, H [Saint-Gobain Recherche 39, quai Lucien Lefranc, BP 135 93303 Aubervilliers Cedex (France)

2009-11-15

Sulfur is an important element of glasses, not because of its amount, always very low (less than 0.4 % in weight of SO{sub 3}), but because of its role since it actively participates to the refinement process and, combined to other elements, it can be responsible for the coloration of the glass. Iron is also of a major importance in most of the glasses. In the case of the float glass, the two faces, because of the fabrication process, are different in terms of composition (presence of Sn for one face) and also in terms of oxidation state of these minority elements (Fe, Sn, S). There should be a subtle interplay between the concentrations and the oxidation states of these different minority elements, and anyway these variations occur over a thickness of the order of few micrometers below the surface. Using the high intensity and the focusing properties (3 x 3 {mu}m{sup 2}) of the x-ray beam from the Lucia beamline, we have therefore studied the speciation of iron and sulfur near the face of a float glass in relation with the behavior of tin. This has been obtained by combining elemental x-ray fluorescence cartography and x-ray micro-absorption at the different K-edges.

Effect of NaX zeolite-modified graphite felts on hexavalent chromium removal in biocathode microbial fuel cells.

Science.gov (United States)

Wu, Xiayuan; Tong, Fei; Yong, Xiaoyu; Zhou, Jun; Zhang, Lixiong; Jia, Honghua; Wei, Ping

2016-05-05

Two kinds of NaX zeolite-modified graphite felts were used as biocathode electrodes in hexavalent chromium (Cr(VI))-reducing microbial fuel cells (MFCs). The one was fabricated through direct modification, and the other one processed by HNO3 pretreatment of graphite felt before modification. The results showed that two NaX zeolite-modified graphite felts are excellent bio-electrode materials for MFCs, and that a large NaX loading mass, obtained by HNO3 pretreatment (the HNO3-NaX electrode), leads to a superior performance. The HNO3-NaX electrode significantly improved the electricity generation and Cr(VI) removal of the MFC. The maximum Cr(VI) removal rate increased to 10.39±0.28 mg/L h, which was 8.2 times higher than that of the unmodified control. The improvement was ascribed to the strong affinity that NaX zeolite particles, present in large number on the graphite felt, have for microorganisms and Cr(VI) ions. Copyright © 2016 Elsevier B.V. All rights reserved.

Control of lipid oxidation during exercise: role of energy state and mitochondrial factors

DEFF Research Database (Denmark)

Sahlin, K; Harris, R C

2008-01-01

Despite considerable progress during recent years our understanding of how lipid oxidation (LOx) is controlled during exercise remains incomplete. This review focuses on the role of mitochondria and energy state in the control of LOx. LOx increases in parallel with increased energy demand up...... to an exercise intensity of about 50-60% of VO(2max) after which the contribution of lipid decreases. The switch from lipid to carbohydrate (CHO) is of energetic advantage due to the increased ATP/O(2) yield. In the low-intensity domain (energy state will stimulate both LOx...... during high-intensity exercise. Another potential mechanism, suggested in this review, is that Acyl-CoA synthetase (ACS), an initial step in LCFA catabolism, functions as a regulator of LOx. ACS activity is suggested to be under control of CoASH and energy state. Furthermore, evidence exists...

Dynamics of Hexavalent Chromium in Four Types of Aquaculture Ponds and Its Effects on the Morphology and Behavior of Cultured Clarias gariepinus (Burchell 1822).

Science.gov (United States)

Mustapha, Moshood Keke

2017-04-01

Hexavalent chromium is a bio accumulative toxic metal in water and fish. It enters aquaculture ponds mainly through anthropogenic sources. Hexavalent chromium concentrations and its effects on the morphology and behavior of Clarias gariepinus were investigated from four aquaculture ponds for 12 weeks. Chromium was measured using diphenyl carbohdrazide method; alkalinity and hardness were measured using colometric method and analyzed with Bench Photometer. Temperature and pH were measured using pH/EC/TDS/Temp combined tester. Temporal and spatial replications of samples were done with triplicates morphological and behavioural effects of the metal on fish were observed visually. Chromium ranged from no detection to 0.05 mg/L, alkalinity 105 to 245 mg/L, hardness 80 to 165 mg/L, pH 6.35 to 8.03 and temperature 29.1 to 35.9°C. Trend in the chromium concentrations in the ponds is natural > earthen > concrete > collapsible. There was a significant difference ( P temperature among the four ponds. Significant positive correlation also existed between alkalinity, water hardness, pH, with chromium. Morphological and behavioural changes observed in the fish include irregular swimming, frequent coming to the surface, dark body colouration, mucous secretion on the body, erosion of gill epithelium, fin disintegration, abdominal distension and lethargy. High chromium concentration in natural pond was due to anthropogenic run-off of materials in to the pond. Acidic pH, low alkalinity, low water hardness also contributed to the high chromium concentration. Morphological and behavioural changes observed were attributed to the high concentrations, toxicity and bio accumulative effect of the metal. Toxicity of chromium to fish in aquaculture could threaten food security. Watershed best management practices and remediation could be adopted to reduce the effects of toxicity of chromium on pond water quality, fish flesh quality and fish welfare.

Best combination of promoter and micellar catalyst for the rapid conversion of sorbitol to glucose

Science.gov (United States)

Mukherjee, Kakali; Ghosh, Aniruddha; Saha, Rumpa; Sar, Pintu; Malik, Susanta; Saha, Bidyut

2014-03-01

Kinetic data for oxidation of D-sorbitol to glucose by hexavalent chromium in aqueous medium and aqueous surfactant medium (SDS, TX-100) have been reported. Effect of promoter such as PA, bipy and phenanthroline on the reaction has been investigated. The reaction is performed under pseudo first order condition with an excess of substrate over the oxidant. The reaction is first order with respect to substrate and oxidant. The micelles have a catalytic effect on the reaction. Combination of phen and TX-100 produces almost twelve times increase in rate of oxidation.

Dissolving method for nuclear fuel oxide

International Nuclear Information System (INIS)

Tomiyasu, Hiroshi; Kataoka, Makoto; Asano, Yuichiro; Hasegawa, Shin-ichi; Takashima, Yoichi; Ikeda, Yasuhisa.

1996-01-01

In a method of dissolving oxides of nuclear fuels in an aqueous acid solution, the oxides of the nuclear fuels are dissolved in a state where an oxidizing agent other than the acid is present together in the aqueous acid solution. If chlorate ions (ClO 3 - ) are present together in the aqueous acid solution, the chlorate ions act as a strong oxidizing agent and dissolve nuclear fuels such as UO 2 by oxidation. In addition, a Ce compound which generates Ce(IV) by oxidation is added to the aqueous acid solution, and an ozone (O 3 ) gas is blown thereto to dissolve the oxides of nuclear fuels. Further, the oxides of nuclear fuels are oxidized in a state where ClO 2 is present together in the aqueous acid solution to dissolve the oxides of nuclear fuels. Since oxides of the nuclear fuels are dissolved in a state where the oxidizing agent is present together as described above, the oxides of nuclear fuels can be dissolved even at a room temperature, thereby enabling to use a material such as polytetrafluoroethylene and to dissolve the oxides of nuclear fuels at a reduced cost for dissolution. (T.M.)

Solid State Electrochemical Sensors for Nitrogen Oxide (NOx) Detection in Lean Exhaust Gases

OpenAIRE

Rheaume, Jonathan Michael

2010-01-01

Solid state electrochemical sensors that measure nitrogen oxides (NOx) in lean exhaust have been investigated in order to help meet future on-board diagnostic (OBD) regulations for diesel vehicles. This impedancemetric detection technology consists of a planar, single cell sensor design with various sensing electrode materials and yttria-stabilized zirconia (YSZ) as the electrolyte. No reference to ambient air is required. An impedance analysis method yields a signal that is proportional to t...

Enhanced catalytic hydrogenation activity of Ni/reduced graphene oxide nanocomposite prepared by a solid-state method

Science.gov (United States)

Li, Yizhao; Cao, Yali; Jia, Dianzeng

2018-01-01

A simple solid-state method has been applied to synthesize Ni/reduced graphene oxide (Ni/rGO) nanocomposite under ambient condition. Ni nanoparticles with size of 10-30 nm supported on reduced graphene oxide (rGO) nanosheets are obtained through one-pot solid-state co-reduction among nickel chloride, graphene oxide, and sodium borohydride. The Ni/rGO nanohybrid shows enhanced catalytic activity toward the reduction of p-nitrophenol (PNP) into p-aminophenol compared with Ni nanoparticles. The results of kinetic research display that the pseudo-first-order rate constant for hydrogenation reaction of PNP with Ni/rGO nanocomposite is 7.66 × 10-3 s-1, which is higher than that of Ni nanoparticles (4.48 × 10-3 s-1). It also presents superior turnover frequency (TOF, 5.36 h-1) and lower activation energy ( E a, 29.65 kJ mol-1) in the hydrogenation of PNP with Ni/rGO nanocomposite. Furthermore, composite catalyst can be magnetically separated and reused for five cycles. The large surface area and high electron transfer property of rGO support are beneficial for good catalytic performance of Ni/rGO nanocomposite. Our study demonstrates a simple approach to fabricate metal-rGO heterogeneous nanostructures with advanced functions.

Modulation of histone methylation and MLH1 gene silencing by hexavalent chromium

International Nuclear Information System (INIS)

Sun Hong; Zhou Xue; Chen Haobin; Li Qin; Costa, Max

2009-01-01

Hexavalent chromium [Cr(VI)] is a mutagen and carcinogen, and occupational exposure can lead to lung cancers and other adverse health effects. Genetic changes resulting from DNA damage have been proposed as an important mechanism that mediates chromate's carcinogenicity. Here we show that chromate exposure of human lung A549 cells increased global levels of di- and tri-methylated histone H3 lysine 9 (H3K9) and lysine 4 (H3K4) but decreased the levels of tri-methylated histone H3 lysine 27 (H3K27) and di-methylated histone H3 arginine 2 (H3R2). Most interestingly, H3K9 dimethylation was enriched in the human MLH1 gene promoter following chromate exposure and this was correlated with decreased MLH1 mRNA expression. Chromate exposure increased the protein as well as mRNA levels of G9a a histone methyltransferase that specifically methylates H3K9. This Cr(VI)-induced increase in G9a may account for the global elevation of H3K9 dimethylation. Furthermore, supplementation with ascorbate, the primary reductant of Cr(VI) and also an essential cofactor for the histone demethylase activity, partially reversed the H3K9 dimethylation induced by chromate. Thus our studies suggest that Cr(VI) may target histone methyltransferases and demethylases, which in turn affect both global and gene promoter specific histone methylation, leading to the silencing of specific tumor suppressor genes such as MLH1.

Templated electrodeposition of Ag7NO11 nanowires with very high oxidation states of silver

NARCIS (Netherlands)

Rodijk, E.J.B.; Maijenburg, A.W.; Maas, M.G.; Blank, David H.A.; ten Elshof, Johan E.

2011-01-01

The templated electrodeposition of 200 nm diameter nanowires of the argentic oxynitrate Ag(Ag3O4)2NO3 phase is reported. Their high surface-to-volume ratio and the high average oxidation state of Ag make these wires promising candidates for nanoscale redox processes in which both a high volumetric

Non steady-state model for dry oxidation of nuclear wastes metallic containers in long term interim storage conditions

International Nuclear Information System (INIS)

Bertrand, Nathalie; Desgranges, Clara; Poquillon, Dominique; Monceau, Daniel

2006-01-01

oxidation tests. In a second step, in order to increase the reliability of the long term extrapolations from basic models, a non-steady state numerical model able to take into account several elementary steps is built. The aim is to get a more reliable tool to describe mechanisms that control oxide scale growth in this specific low temperature range. The paper has the following contains: Experimental results; Growth kinetics; Scale morphology; A basic model for kinetics of oxidation; Conclusion of the experimental study; EKINOX: Estimation KINetics OXidation: an advanced model; General description; Equations in the model; Results; Future developments; Conclusion. To summarize, the basic model consists in some extrapolations of available experimental data in the temperature range of interest following simple analytical laws deduced from classical oxidation theories. This leads to a very small oxide scale and thus to the loss of very small amounts of metal even for extrapolations to over 100 years. However, the reliability of this kind of basic models is very poor since it is based on the assumption that a single elementary process controls the oxidation rate. Indeed in the temperature range concerned by long term interim deposit of waste containers, several mechanisms can control the oxidation rate. A numerical model able to take in consideration several growth mechanisms is now in progress. At this stage of development, the originality of the proposed advanced model consists in explicitly calculating the vacancy profiles and treating these as non-conservative species. It is based on an original numerical treatment to correctly and easily describe elimination of vacancies at the metal/oxide interface and thus relative motion between the substrate lattice and the oxide one, even for non-stationary states. It can treat Wagner's model but without the quasi-steady state 'hypothesis or also take into account a partial control of the oxidation process by interfacial reaction. In

Magnetic susceptibility as a direct measure of oxidation state in LiFePO4 batteries and cyclic water gas shift reactors.

Science.gov (United States)

Kadyk, Thomas; Eikerling, Michael

2015-08-14

The possibility of correlating the magnetic susceptibility to the oxidation state of the porous active mass in a chemical or electrochemical reactor was analyzed. The magnetic permeability was calculated using a hierarchical model of the reactor. This model was applied to two practical examples: LiFePO4 batteries, in which the oxidation state corresponds with the state-of-charge, and cyclic water gas shift reactors, in which the oxidation state corresponds to the depletion of the catalyst. In LiFePO4 batteries phase separation of the lithiated and delithiated phases in the LiFePO4 particles in the positive electrode gives rise to a hysteresis effect, i.e. the magnetic permeability depends on the history of the electrode. During fast charge or discharge, non-uniform lithium distributionin the electrode decreases the hysteresis effect. However, the overall sensitivity of the magnetic response to the state-of-charge lies in the range of 0.03%, which makes practical measurement challenging. In cyclic water gas shift reactors, the sensitivity is 4 orders of magnitude higher and without phase separation, no hysteresis occurs. This shows that the method is suitable for such reactors, in which large changes of the magnetic permeability of the active material occurs.

The state-of-the-art and prospects of the oxidation titration method for the determination of uranium in geological samples

International Nuclear Information System (INIS)

Sun Jiayan

1986-01-01

The state-of-the-art of the oxidation titration method for the determination of uranium in geological samples is reviewed in some respects such as the prereduction of U(VI), oxidation of U(IV) and the detection of the end-point. Comments are also made on the prospects of further improvements of this method

Radiation oxidation of polypropylene: A solid-state 13C NMR study using selective isotopic labeling

International Nuclear Information System (INIS)

Mowery, Daniel M.; Assink, Roger A.; Derzon, Dora K.; Klamo, Sara B.; Bernstein, Robert; Clough, Roger L.

2007-01-01

Polypropylene samples, in which the three different carbon atoms along the chain were selectively labeled with carbon-13, were subjected to radiation under inert and air atmospheres, and to post-irradiation exposure in air at various temperatures. By using solid-state 13 C NMR measurements at room temperature, we have been able to identify and quantify the oxidation products. The isotopic labeling provides insight into chemical reaction mechanisms, since oxidation products can be traced back to their positions of origin on the macromolecule. The major products include peroxides and alcohols, both formed at tertiary carbon sites along the chain. Other products include methyl ketones, acids, esters, peresters, and hemiketals formed from reaction at the tertiary carbon, together with in-chain ketones and esters from reaction at the secondary chain carbon. No evidence is found of products arising from reactions at the methyl side chain. Significant temperature-dependent differences are apparent; for example much higher yields of chain-end methyl ketones, which are the indicator product of chain scission, are generated for both elevated temperature irradiation and for post-irradiation treatment at elevated temperatures. Time-dependent plots of yields of the various oxidation products have been obtained under a wide range of conditions, including the post-irradiation oxidation of a sample at room temperature in air that has been monitored for 2 years. Radiation-oxidation products of polypropylene are contrasted to products measured for 13 C-labeled polyethylene in an earlier investigation: the peroxides formed in irradiated polypropylene are remarkably longer lived, the non-peroxidic products are significantly different, and the overall ratios of oxidation products in polypropylene change relatively little as a function of the extent of oxidation

Studies on O/M ratio determination in uranium oxide, plutonium oxide and uranium-plutonium mixed oxide

International Nuclear Information System (INIS)

Sampath, S.; Chawla, K.L.

1975-01-01

Thermogravimetric studies were carried out in unsintered and sintered samples of uranium oxide, plutonium oxide and uranium-plutonium mixed oxide under different atmospheric conditions (air, argon and moist argon/hydrogen). Moisture loss was found to occur below 200 0 C for uranium dioxide samples, upto 700 0 C for sintered plutonium dioxide and negligible for sintered samples. The O/M ratios for non-stoichiometric uranium dioxide (sintered and unsintered), plutonium dioxide and mixed uranium and plutonium oxides (sintered) could be obtained with a precision of +- 0.002. Two reference states UOsub(2.000) and UOsub(2.656) were obtained for uranium dioxide and the reference state MOsub(2.000) was used for other cases. For unsintered plutonium dioxide samples, accurate O/M ratios could not be obtained of overlap of moisture loss with oxygen loss/gain. (author)

Comparative Cytotoxicity and Genotoxicity of Particulate and Soluble Hexavalent Chromium in Human and Sperm Whale (Physeter macrocephalus) Skin Cells

Science.gov (United States)

Li Chen, Tânia; LaCerte, Carolyne; Wise, Sandra S.; Holmes, Amie; Martino, Julieta; Wise, John Pierce; Thompson, W. Douglas; Wise, John Pierce

2014-01-01

Chromium (Cr) is a global marine pollutant, present in marine mammal tissues. Hexavalent chromium [Cr(VI)] is a known human carcinogen. In this study we compare the cytotoxic and clastogenic effects of Cr(VI) in human (Homo sapiens) and sperm whale (Physeter macrocephalus) skin fibroblasts. Our data show that increasing concentrations of both particulate and soluble Cr(VI) induce increasing amounts of cytotoxicity and clastogenicity in human and sperm whale skin cells. Furthermore, the data show that sperm whale cells are resistant to these effects exhibiting less cytotoxicity and genotoxicity than the human cells. Differences in Cr uptake accounted for some but not all of the differences in particulate and soluble Cr(VI) genotoxicity, although it did explain the differences in particulate Cr(VI) cytotoxicity. Altogether the data indicate that Cr(VI) is a genotoxic threat to whales, but also suggest that whales have evolved cellular mechanisms to protect them against the genotoxicity of environmental agents such as Cr(VI). PMID:21466859

Solid State Energy Conversion Alliance (SECA) Solid Oxide Fuel Cell Program

Energy Technology Data Exchange (ETDEWEB)

Nguyen Minh

2006-07-31

This report summarizes the work performed for Phase I (October 2001 - August 2006) under Cooperative Agreement DE-FC26-01NT41245 for the U. S. Department of Energy, National Energy Technology Laboratory (DOE/NETL) entitled 'Solid State Energy Conversion Alliance (SECA) Solid Oxide Fuel Cell Program'. The program focuses on the development of a low-cost, high-performance 3-to-10-kW solid oxide fuel cell (SOFC) system suitable for a broad spectrum of power-generation applications. During Phase I of the program significant progress has been made in the area of SOFC technology. A high-efficiency low-cost system was designed and supporting technology developed such as fuel processing, controls, thermal management, and power electronics. Phase I culminated in the successful demonstration of a prototype system that achieved a peak efficiency of 41%, a high-volume cost of $724/kW, a peak power of 5.4 kW, and a degradation rate of 1.8% per 500 hours. . An improved prototype system was designed, assembled, and delivered to DOE/NETL at the end of the program. This prototype achieved an extraordinary peak efficiency of 49.6%.

Sequential potentiometric determination of uranium and plutonium in a single aliquot

International Nuclear Information System (INIS)

Rao, V.K.; Charyulu, M.M.; Natarajan, P.R.

1983-01-01

A method is reported for sequential potentiometric determination of uranium and plutonium present is an aliquot. Plutonium is first determined by oxidizing it to the hexavalent state with perchloric acid followed by iron(II) reduction and titration of excess ferrous iron with chromium(VI). Uranium is subsequently determined by reduction to the quadrivalent state using titanium(III) and titration with vanadium(V). The interference of plutonium and iron(II) is eliminated by the addition of a mixture containing sulfamic acid, nitric acid, and molybdenum(VI). The results of the analysis of mixture containing 3-5 mg quantities of uranium and plutonium are reliable with errors less than 0.3% and 0.2%, respectively. The application of the method for the analysis of mixtures containing various amounts of uranium and plutonium has been examined. (author)

Role of the oxidation state of cerium on the ceria surfaces for silicate adsorption

Energy Technology Data Exchange (ETDEWEB)

Seo, Jihoon [WCD Department of Energy Engineering, Hanyang University, Seoul (Korea, Republic of); Moon, Jinok [WCD Department of Energy Engineering, Hanyang University, Seoul (Korea, Republic of); Clean/CMP Technology Team, Memory, Samsung Electronics, Hwaseong (Korea, Republic of); Kim, Joo Hyun; Lee, Kangchun [WCD Department of Energy Engineering, Hanyang University, Seoul (Korea, Republic of); Hwang, Junha [WCD Department of Energy Engineering, Hanyang University, Seoul (Korea, Republic of); Materials R& D Center, K.C.Tech, Anseong (Korea, Republic of); Yoon, Heesung [WCD Department of Energy Engineering, Hanyang University, Seoul (Korea, Republic of); Yi, Dong Kee, E-mail: vitalis@mju.ac.kr [Department of Chemistry, Myongji University, Yongin (Korea, Republic of); Paik, Ungyu, E-mail: upaik@hanyang.ac.kr [WCD Department of Energy Engineering, Hanyang University, Seoul (Korea, Republic of)

2016-12-15

Highlights: • We investigated the role of Ce oxidation state (Ce{sup 3+}/Ce{sup 4+}) on the CeO{sub 2} surfaces for the silicate adsorption. • As the Ce{sup 3+} concentration increased from 19.3 to 27.6%, the surface density of −OH group increased from 0.34 to 0.72 OH/nm{sup 2}. • The Freundlich constant for the relative adsorption capacity (K{sub F}) and adsorption intensity (1/n) indicated that CeO{sub 2} NPs with high Ce{sup 3+} concentration show higher adsorption affinity with silicate ions. - Abstract: In this study, we have investigated the role of the Ce oxidation state (Ce{sup 3+}/Ce{sup 4+}) on the CeO{sub 2} surfaces for silicate adsorption. In aqueous medium, the Ce{sup 3+} sites lead to the formation of −OH groups at the CeO{sub 2} surface through H{sub 2}O dissociation. Silicate ions can adsorb onto the CeO{sub 2} surface through interaction with the −OH groups (−Ce−OH− + −Si−O{sup −} ↔ −Ce−O−Si− + OH{sup −}). As the Ce{sup 3+} concentration increased from 19.3 to 27.6%, the surface density of −OH group increased from 0.34 to 0.72 OH/nm{sup 2}. To evaluate the adsorption behaviors of silicate ions onto CeO{sub 2} NPs, we carried out an adsorption isothermal analysis, and the adsorption isotherm data followed the Freundlich model. The Freundlich constant for the relative adsorption capacity (K{sub F}) and adsorption intensity (1/n) indicated that CeO{sub 2} NPs with high Ce{sup 3+} concentration show higher adsorption affinity with silicate ions. As a result, we have demonstrated that the Ce oxidation state (Ce{sup 3+}/Ce{sup 4+}) on the CeO{sub 2} surface can have a significant influence on the silicate adsorption.

Optimization of hexavalent chromium removal from aqueous solution using acid-modified granular activated carbon as adsorbent through response surface methodology

International Nuclear Information System (INIS)

Daoud, Waseem; Ebadi, Taghi; Fahimifar, Ahmad

2015-01-01

Response surface methodology (RSM) was applied to evaluate the effect of the main operational variables, including initial pH, initial chromium ion concentration, bulk density of GAC and time on the removal of hexavalent chromium Cr(Ⅵ) from contaminated groundwater by permeable reactive barriers (PRB) with acid-modified granular activated carbon (GAC) as an adsorbent material. The removal rates of Cr(Ⅵ) under different values of these parameters were investigated and results indicated high adsorption capacity at low pH and low initial metal ion concentration of Cr(Ⅵ), but the bulk density of GAC slightly influenced the process efficiency. According to the ANOVA (analysis of variance) results, the model presents high R 2 values of 94.35% for Cr(Ⅵ) removal efficiency, which indicates that the accuracy of the polynomial models was good. Also, quadratic regression models with estimated coefficients were developed to describe the pollutant removals

Optimization of hexavalent chromium removal from aqueous solution using acid-modified granular activated carbon as adsorbent through response surface methodology

Energy Technology Data Exchange (ETDEWEB)

Daoud, Waseem; Ebadi, Taghi; Fahimifar, Ahmad [Amirkabir University of Technology (Tehran Polytechnic), Tehran (Iran, Islamic Republic of)

2015-06-15

Response surface methodology (RSM) was applied to evaluate the effect of the main operational variables, including initial pH, initial chromium ion concentration, bulk density of GAC and time on the removal of hexavalent chromium Cr(Ⅵ) from contaminated groundwater by permeable reactive barriers (PRB) with acid-modified granular activated carbon (GAC) as an adsorbent material. The removal rates of Cr(Ⅵ) under different values of these parameters were investigated and results indicated high adsorption capacity at low pH and low initial metal ion concentration of Cr(Ⅵ), but the bulk density of GAC slightly influenced the process efficiency. According to the ANOVA (analysis of variance) results, the model presents high R{sup 2} values of 94.35% for Cr(Ⅵ) removal efficiency, which indicates that the accuracy of the polynomial models was good. Also, quadratic regression models with estimated coefficients were developed to describe the pollutant removals.

V6O13 films by control of the oxidation state from aqueous precursor to crystalline phase.

Science.gov (United States)

Peys, Nick; Ling, Yun; Dewulf, Daan; Gielis, Sven; De Dobbelaere, Christopher; Cuypers, Daniel; Adriaensens, Peter; Van Doorslaer, Sabine; De Gendt, Stefan; Hardy, An; Van Bael, Marlies K

2013-01-28

An aqueous deposition process for V(6)O(13) films is developed whereby the vanadium oxidation state is continuously controlled throughout the entire process. In the precursor stage, a controlled wet chemical reduction of the vanadium(V) source with oxalic acid is achieved and monitored by (51)Vanadium Nuclear Magnetic Resonance ((51)V-NMR) and Ultraviolet-Visible (UV-Vis) spectroscopy. The resulting vanadium(IV) species in the aqueous solution are identified as mononuclear citrato-oxovanadate(IV) complexes by Electron Paramagnetic Resonance (EPR) and Fourier Transform Infra-Red (FTIR) spectroscopy. This precursor is successfully employed for the deposition of uniform, thin films. The optimal deposition and annealing conditions for the formation of crystalline V(6)O(13), including the control of the vanadium oxidation state, are determined through an elaborate study of processing temperature and O(2) partial pressure. To ensure a sub 100 nm adjustable film thickness, a non-oxidative intermediate thermal treatment is carried out at the end of each deposition cycle, allowing maximal precursor decomposition while still avoiding V(IV) oxidation. The resulting surface hydrophilicity, indispensable for the homogeneous deposition of the next layer, is explained by an increased surface roughness and the increased availability of surface vanadyl groups. Crystalline V(6)O(13) with a preferential (002) orientation is obtained after a post deposition annealing in a 0.1% O(2) ambient for thin films with a thickness of 20 nm.

Solid-State Electrochromic Device Consisting of Amorphous WO3 and Various Thin Oxide Layers

Science.gov (United States)

Shizukuishi, Makoto; Shimizu, Isamu; Inoue, Eiichi

1980-11-01

A mixed oxide containing Cr2O3 was introduced into an amorphous WO3 solid-state electrochromic device (ECD) in order to improve its colour memory effect. The electrochromic characteristics were greatly affected by the chemical constituents of a dielectric layer on the a-WO3 layer. Particularly, long memory effect and low power dissipation were attained in a solid-state ECD consisting of a-WO3 and Cr2O3\\cdotV2O5(50 wt.%). Some electrochromic characteristics of the a-WO3/Cr2O3\\cdotV2O5 ECD and the role of V2O5 were investigated.

Regeneration of pilot-scale ion exchange columns for hexavalent chromium removal.

Science.gov (United States)

Korak, Julie A; Huggins, Richard; Arias-Paic, Miguel

2017-07-01

Due to stricter regulations, some drinking water utilities must implement additional treatment processes to meet potable water standards for hexavalent chromium (Cr(VI)), such as the California limit of 10 μg/L. Strong base anion exchange is effective for Cr(VI) removal, but efficient resin regeneration and waste minimization are important for operational, economic and environmental considerations. This study compared multiple regeneration methods on pilot-scale columns on the basis of regeneration efficiency, waste production and salt usage. A conventional 1-Stage regeneration using 2 N sodium chloride (NaCl) was compared to 1) a 2-Stage process with 0.2 N NaCl followed by 2 N NaCl and 2) a mixed regenerant solution with 2 N NaCl and 0.2 N sodium bicarbonate. All methods eluted similar cumulative amounts of chromium with 2 N NaCl. The 2-Stage process eluted an additional 20-30% of chromium in the 0.2 N fraction, but total resin capacity is unaffected if this fraction is recycled to the ion exchange headworks. The 2-Stage approach selectively eluted bicarbonate and sulfate with 0.2 N NaCl before regeneration using 2 N NaCl. Regeneration approach impacted the elution efficiency of both uranium and vanadium. Regeneration without co-eluting sulfate and bicarbonate led to incomplete uranium elution and potential formation of insoluble uranium hydroxides that could lead to long-term resin fouling, decreased capacity and render the resin a low-level radioactive solid waste. Partial vanadium elution occurred during regeneration due to co-eluting sulfate suppressing vanadium release. Waste production and salt usage were comparable for the 1- and 2-Stage regeneration processes with similar operational setpoints with respect to chromium or nitrate elution. Published by Elsevier Ltd.

Hexavalent chromium is cytotoxic and genotoxic to hawksbill sea turtle cells

Energy Technology Data Exchange (ETDEWEB)

Wise, Sandra S., E-mail: sandra.wise@maine.edu [Wise Laboratory of Environmental and Genetic Toxicology, University of Southern Maine, Science Building, 96 Falmouth Street, Portland, ME 04103 (United States); Maine Center for Toxicology and Environmental Health, University of Southern Maine, Science Building, 96 Falmouth Street, Portland, ME 04103 (United States); Department of Applied Medical Science, University of Southern Maine, Science Building, 96 Falmouth Street, Portland, ME 04103 (United States); Xie, Hong, E-mail: hongxie@usm.maine.edu [Wise Laboratory of Environmental and Genetic Toxicology, University of Southern Maine, Science Building, 96 Falmouth Street, Portland, ME 04103 (United States); Maine Center for Toxicology and Environmental Health, University of Southern Maine, Science Building, 96 Falmouth Street, Portland, ME 04103 (United States); Department of Applied Medical Science, University of Southern Maine, Science Building, 96 Falmouth Street, Portland, ME 04103 (United States); Fukuda, Tomokazu, E-mail: tomofukuda009@gmail.com [Graduate School of Agricultural Sciences, Tohoku University, Laboratory of Animal Breeding and Genetics, Second Research Building, Rm 112, 1-1 Amamiyamachi, Aoba-ku, Sendai 981-8555 (Japan); Douglas Thompson, W., E-mail: dougt@usm.maine.edu [Maine Center for Toxicology and Environmental Health, University of Southern Maine, Science Building, 96 Falmouth Street, Portland, ME 04103 (United States); Department of Applied Medical Science, University of Southern Maine, Science Building, 96 Falmouth Street, Portland, ME 04103 (United States); and others

2014-09-01

Sea turtles are a charismatic and ancient ocean species and can serve as key indicators for ocean ecosystems, including coral reefs and sea grass beds as well as coastal beaches. Genotoxicity studies in the species are absent, limiting our understanding of the impact of environmental toxicants on sea turtles. Hexavalent chromium (Cr(VI)) is a ubiquitous environmental problem worldwide, and recent studies show it is a global marine pollutant of concern. Thus, we evaluated the cytotoxicity and genotoxicity of soluble and particulate Cr(VI) in hawksbill sea turtle cells. Particulate Cr(VI) was both cytotoxic and genotoxic to sea turtle cells. Concentrations of 0.1, 0.5, 1, and 5 μg/cm{sup 2} lead chromate induced 108, 79, 54, and 7% relative survival, respectively. Additionally, concentrations of 0, 0.1, 0.5, 1, and 5 μg/cm{sup 2} lead chromate induced damage in 4, 10, 15, 26, and 36% of cells and caused 4, 11, 17, 30, and 56 chromosome aberrations in 100 metaphases, respectively. For soluble Cr, concentrations of 0.25, 0.5, 1, 2.5, and 5 μM sodium chromate induced 84, 69, 46, 25, and 3% relative survival, respectively. Sodium chromate induced 3, 9, 9, 14, 21, and 29% of metaphases with damage, and caused 3, 10, 10, 16, 26, and 39 damaged chromosomes in 100 metaphases at concentrations of 0, 0.25, 0.5, 1, 2.5, and 5 μM sodium chromate, respectively. These data suggest that Cr(VI) may be a concern for hawksbill sea turtles and sea turtles in general. - Highlights: • Particulate Cr(VI) is cytotoxic and clastogenic to hawksbill sea turtle cells. • Soluble Cr(VI) is cytotoxic and clastogenic to hawksbill sea turtle cells. • Cr(VI) may be a risk factor for hawksbill sea turtle health.

Hexavalent chromium is cytotoxic and genotoxic to hawksbill sea turtle cells

International Nuclear Information System (INIS)

Wise, Sandra S.; Xie, Hong; Fukuda, Tomokazu; Douglas Thompson, W.

2014-01-01

Sea turtles are a charismatic and ancient ocean species and can serve as key indicators for ocean ecosystems, including coral reefs and sea grass beds as well as coastal beaches. Genotoxicity studies in the species are absent, limiting our understanding of the impact of environmental toxicants on sea turtles. Hexavalent chromium (Cr(VI)) is a ubiquitous environmental problem worldwide, and recent studies show it is a global marine pollutant of concern. Thus, we evaluated the cytotoxicity and genotoxicity of soluble and particulate Cr(VI) in hawksbill sea turtle cells. Particulate Cr(VI) was both cytotoxic and genotoxic to sea turtle cells. Concentrations of 0.1, 0.5, 1, and 5 μg/cm 2 lead chromate induced 108, 79, 54, and 7% relative survival, respectively. Additionally, concentrations of 0, 0.1, 0.5, 1, and 5 μg/cm 2 lead chromate induced damage in 4, 10, 15, 26, and 36% of cells and caused 4, 11, 17, 30, and 56 chromosome aberrations in 100 metaphases, respectively. For soluble Cr, concentrations of 0.25, 0.5, 1, 2.5, and 5 μM sodium chromate induced 84, 69, 46, 25, and 3% relative survival, respectively. Sodium chromate induced 3, 9, 9, 14, 21, and 29% of metaphases with damage, and caused 3, 10, 10, 16, 26, and 39 damaged chromosomes in 100 metaphases at concentrations of 0, 0.25, 0.5, 1, 2.5, and 5 μM sodium chromate, respectively. These data suggest that Cr(VI) may be a concern for hawksbill sea turtles and sea turtles in general. - Highlights: • Particulate Cr(VI) is cytotoxic and clastogenic to hawksbill sea turtle cells. • Soluble Cr(VI) is cytotoxic and clastogenic to hawksbill sea turtle cells. • Cr(VI) may be a risk factor for hawksbill sea turtle health

seasonal variation in chromium hexavalent and copper

African Journals Online (AJOL)

Admin

Seasonal variation in heavy metal contamination of groundwater in the Jimeta- Yola area ... animal feedlots, industrial waste and food processing ...... and conservation of groundwater quality; a) ... significant role of hydrous Mn and Fe oxides.

Joint Test Protocol: Environmentally Friendly Zirconium Oxide Pretreatment Demonstration

Science.gov (United States)

2013-12-01

and compliance issues associated with the use of zinc phosphate and chromate/ chrome containing conversion coatings while maintaining military...safety, and occupational health risks associated with the use of zinc phosphate and chromate/ chrome -containing conversion coatings. There is a need to...zirconium-based pretreatment will be shown to be both environmentally acceptable (no hazardous air pollutants or heavy metals such as hexavalent chromium

Biological versus mineralogical chromium reduction: potential for reoxidation by manganese oxide.

Science.gov (United States)

Butler, Elizabeth C; Chen, Lixia; Hansel, Colleen M; Krumholz, Lee R; Elwood Madden, Andrew S; Lan, Ying

2015-11-01

Hexavalent chromium (Cr(vi), present predominantly as CrO4(2-) in water at neutral pH) is a common ground water pollutant, and reductive immobilization is a frequent remediation alternative. The Cr(iii) that forms upon microbial or abiotic reduction often co-precipitates with naturally present or added iron (Fe), and the stability of the resulting Fe-Cr precipitate is a function of its mineral properties. In this study, Fe-Cr solids were formed by microbial Cr(vi) reduction using Desulfovibrio vulgaris strain RCH1 in the presence of the Fe-bearing minerals hematite, aluminum substituted goethite (Al-goethite), and nontronite (NAu-2, Clay Minerals Society), or by abiotic Cr(vi) reduction by dithionite reduced NAu-2 or iron sulfide (FeS). The properties of the resulting Fe-Cr solids and their behavior upon exposure to the oxidant manganese (Mn) oxide (birnessite) differed significantly. In microcosms containing strain RCH1 and hematite or Al-goethite, there was significant initial loss of Cr(vi) in a pattern consistent with adsorption, and significant Cr(vi) was found in the resulting solids. The solid formed when Cr(vi) was reduced by FeS contained a high proportion of Cr(iii) and was poorly crystalline. In microcosms with strain RCH1 and hematite, Cr precipitates appeared to be concentrated in organic biofilms. Reaction between birnessite and the abiotically formed Cr(iii) solids led to production of significant dissolved Cr(vi) compared to the no-birnessite controls. This pattern was not observed in the solids generated by microbial Cr(vi) reduction, possibly due to re-reduction of any Cr(vi) generated upon oxidation by birnessite by active bacteria or microbial enzymes. The results of this study suggest that Fe-Cr precipitates formed in groundwater remediation may remain stable only in the presence of active anaerobic microbial reduction. If exposed to environmentally common Mn oxides such as birnessite in the absence of microbial activity, there is the potential

Applications of fluorescence techniques to the study of uranium in homogeneous and heterogeneous environments: hydrolysis and photo-reduction reactions on titanium dioxide

International Nuclear Information System (INIS)

Eliet, Veronique

1996-01-01

This thesis describes the use of Time-Resolved Fluorescence to characterise the spectroscopy of hydroxo-complexes of hexavalent Uranium, and to study photochemical reactions involving these species at mineral/water interfaces. The instrumentation used comprised of either an excimer laser coupled to an optical multichannel analyser OMA or a Nd-YAG laser coupled to a stroboscopic photomultiplier. The hydrolysis of Uranium at a constant temperature of 25 deg. C, has been studied in the pH ranges 0-5 and 9-12. Deconvolution of spectra and fluorescence decay curves for Uranium yielded individual fluorescence spectra and decay times for uranyl UO 2 2+ and its hydroxo-complexes UO 2 OH + , (UO 2 )2(OH) 2 2+ , (UO 2 ) 3 (OH) 5 + et UO 2 (OH) 3 - . The comparison of fluorescence efficiencies for the various species showed that the complex (UO 2 )2(OH) 2 2+ is up to 85 times more fluorescent than uranyl, depending on the emission wavelength. Further, investigations of fluorescence decays as a function of temperature in the pH range 0-6, yielded activation energies for the various Uranium hydroxo species. The knowledge gained in homogeneous media served in the study of the photochemical behaviour of Uranium in suspensions of the semi-conductor mineral, TiO 2 . After UV-light absorption, charge carriers formed at the mineral surface were found to reduce hexavalent Uranium to the tetravalent oxidation state. Time-Resolved Fluorescence Spectroscopy has been used to monitor the kinetics of the oxidation state change. A reaction mechanism is proposed on the basis of results obtained by studying the kinetics of the process at different values of pH The role of humic substances on the heterogeneous redox reaction has also been examined. (author) [fr

Theoretical studies of positron states and annihilation characteristics at the oxidized Cu(100) surface

Energy Technology Data Exchange (ETDEWEB)

Fazleev, N. G. [Department of Physics, Box 19059, University of Texas at Arlington, Arlington Texas 76019 (United States) and Institute of Physics, Kazan Federal University, Kremlevskaya18, Kazan 420008 (Russian Federation); Weiss, A. H. [Department of Physics, Box 19059, University of Texas at Arlington, Arlington Texas 76019 (United States)

2013-04-19

In this work we present the results of theoretical studies of positron surface and bulk states and annihilation probabilities of surface-trapped positrons with relevant core electrons at the oxidized Cu(100) surface under conditions of high oxygen coverage. An ab-initio study of the electronic properties of the Cu(100) missing row reconstructed surface at various on surface and sub-surface oxygen coverages has been performed on the basis of the density functional theory (DFT) using the Dmol3 code and the generalized gradient approximation (GGA). Surface structures in calculations have been constructed by adding oxygen atoms to various surface hollow and sub-surface octahedral sites of the 0.5 monolayer (ML) missing row reconstructed phase of the Cu(100) surface with oxygen coverages ranging from 0.5 to 1.5 ML. The charge redistribution at the surface and variations in atomic structure and chemical composition of the topmost layers associated with oxidation and surface reconstruction have been found to affect the spatial extent and localization of the positron surface state wave function and annihilation probabilities of surface trapped positrons with relevant core electrons. Theoretical results are compared with experimental data obtained from studies of oxidation of the Cu(100) surface using positron annihilation induced Auger electron spectroscopy (PAES). It has been shown that positron annihilation probabilities with Cu 3s and 3p core electrons decrease when total (on-surface and sub-surface) oxygen coverage of the Cu(100) surface increases up to 1 ML. The calculations show that for high oxygen coverage when total oxygen coverage is 1. 5 ML the positron is not bound to the surface.

Environmental impacts of Sheba tannery (Ethiopia effluents on the surrounding water bodies

Directory of Open Access Journals (Sweden)

Abraha Gebrekidan

2009-08-01

Full Text Available The levels of hexavalent chromium from direct and treated Sheba tannery effluents, downstream river and spring water samples and upstream river water samples were determined spectrophotometrically by the s-diphenylcarbazide method at 540 nm. Temporal and representative samples were collected from the untreated tannery effluent (S1, sedimentation pond (S2, chromium oxidation pond (S3, downstream river (S4, downstream spring (S5 and 5 kms upstream river (S6. The mean levels of hexavalent chromium in S1, S2, S3, S4, S5 and S6 were 10.54, 9.15, 7.82, 0.58, 0.54 and 0.015 mg/L, respectively. The levels of hexavalent chromium in the downstream river and spring water samples exceed the World Health Organization (WHO permissible limit of total chromium in drinking waters (0.05 mg/L as opposed to the levels in the upstream waters. The increased concentrations of Cr(VI in the water samples indicate the possible environmental pollution of the downstream water bodies by the Sheba tannery effluents. In view of the toxicity and related environmental hazards, the levels of hexavalent chromium from the Sheba tannery effluents must be reduced to a permissible limit before discharging into the down stream waters being used for domestic purposes by the nearby communities.

Reduction of hexavalent chromium by the thermophilic methanogen Methanothermobacter thermautotrophicus

Science.gov (United States)

Singh, Rajesh; Dong, Hailiang; Liu, Deng; Zhao, Linduo; Marts, Amy R.; Farquhar, Erik; Tierney, David L.; Almquist, Catherine B.; Briggs, Brandon R.

2015-01-01

Despite significant progress on iron reduction by thermophilic microorganisms, studies on their ability to reduce toxic metals are still limited, despite their common co-existence in high temperature environments (up to 70 °C). In this study, Methanothermobacter thermautotrophicus, an obligate thermophilic methanogen, was used to reduce hexavalent chromium. Experiments were conducted in a growth medium with H2/CO2 as substrate with various Cr6+ concentrations (0.2, 0.4, 1, 3, and 5 mM) in the form of potassium dichromate (K2Cr2O7). Time-course measurements of aqueous Cr6+ concentrations using 1,5-diphenylcarbazide colorimetric method showed complete reduction of the 0.2 and 0.4 mM Cr6+ solutions by this methanogen. However, much lower reduction extents of 43.6%, 13.0%, and 3.7% were observed at higher Cr6+ concentrations of 1, 3 and 5 mM, respectively. These lower extents of bioreduction suggest a toxic effect of aqueous Cr6+ to cells at this concentration range. At these higher Cr6+ concentrations, methanogenesis was inhibited and cell growth was impaired as evidenced by decreased total cellular protein production and live/dead cell ratio. Likewise, Cr6+ bioreduction rates decreased with increased initial concentrations of Cr6+ from 13.3 to 1.9 μM h-1. X-ray absorption near-edge structure (XANES) spectroscopy revealed a progressive reduction of soluble Cr6+ to insoluble Cr3+ precipitates, which was confirmed as amorphous chromium hydroxide by selected area electron diffraction pattern. However, a small fraction of reduced Cr occurred as aqueous Cr3+. Scanning and transmission electron microscope observations of M. thermautotrophicus cells after Cr6+ exposure suggest both extra- and intracellular chromium reduction mechanisms. Results of this study demonstrate the ability of M. thermautotrophicus cells to reduce toxic Cr6+ to less toxic Cr3+ and its potential application in metal bioremediation, especially at high temperature subsurface radioactive waste disposal

X-ray Absorption Study of Graphene Oxide and Transition Metal Oxide Nanocomposites.

Science.gov (United States)

Gandhiraman, Ram P; Nordlund, Dennis; Javier, Cristina; Koehne, Jessica E; Chen, Bin; Meyyappan, M

2014-08-14

The surface properties of the electrode materials play a crucial role in determining the performance and efficiency of energy storage devices. Graphene oxide and nanostructures of 3d transition metal oxides were synthesized for construction of electrodes in supercapacitors, and the electronic structure and oxidation states were probed using near-edge X-ray absorption fine structure. Understanding the chemistry of graphene oxide would provide valuable insight into its reactivity and properties as the graphene oxide transformation to reduced-graphene oxide is a key step in the synthesis of the electrode materials. Polarized behavior of the synchrotron X-rays and the angular dependency of the near-edge X-ray absorption fine structures (NEXAFS) have been utilized to study the orientation of the σ and π bonds of the graphene oxide and graphene oxide-metal oxide nanocomposites. The core-level transitions of individual metal oxides and that of the graphene oxide nanocomposite showed that the interaction of graphene oxide with the metal oxide nanostructures has not altered the electronic structure of either of them. As the restoration of the π network is important for good electrical conductivity, the C K edge NEXAFS spectra of reduced graphene oxide nanocomposites confirms the same through increased intensity of the sp 2 -derived unoccupied states π* band. A pronounced angular dependency of the reduced sample and the formation of excitonic peaks confirmed the formation of extended conjugated network.

Comparison of the oxidation state of Fe in comet 81P/Wild 2 and chondritic-porous interplanetary dust particles

Energy Technology Data Exchange (ETDEWEB)

Ogliore, Ryan C.; Butterworth, Anna L.; Fakra, Sirine C.; Gainsforth, Zack; Marcus, Matthew A.; Westphal, Andrew J.

2010-07-16

The fragile structure of chondritic-porous interplanetary dust particles (CP-IDPs) and their minimal parent-body alteration have led researchers to believe these particles originate in comets rather than asteroids where aqueous and thermal alterations have occurred. The solar elemental abundances and atmospheric entry speed of CP-IDPs also suggest a cometary origin. With the return of the Stardust samples from Jupiter-family comet 81P/Wild 2, this hypothesis can be tested. We have measured the Fe oxidation state of 15 CP-IDPs and 194 Stardust fragments using a synchrotron-based x-ray microprobe. We analyzed {approx}300 ng of Wild 2 material - three orders of magnitude more material than other analyses comparing Wild 2 and CP-IDPs. The Fe oxidation state of these two samples of material are > 2{sigma} different: the CP-IDPs are more oxidized than the Wild 2 grains. We conclude that comet Wild 2 contains material that formed at a lower oxygen fugacity than the parent-body, or parent bodies, of CP-IDPs. If all Jupiter-family comets are similar, they do not appear to be consistent with the origin of CP-IDPs. However, comets that formed from a different mix of nebular material and are more oxidized than Wild 2 could be the source of CP-IDPs.

State-of-the-art technologies of gallium oxide power devices

Science.gov (United States)

Higashiwaki, Masataka; Kuramata, Akito; Murakami, Hisashi; Kumagai, Yoshinao

2017-08-01

Gallium oxide (Ga2 O3 ) has gained increased attention for power devices due to its superior material properties and the availability of economical device-quality native substrates. This review illustrates recent advances in Ga2 O3 device technologies, beginning with an overview of the social circumstances that motivate the development of new-generation switching devices. Following an introduction to the material properties of Ga2 O3 from the viewpoint of power electronics, growth technologies of Ga2 O3 bulk single crystals and epitaxial thin films are discussed. The fabrication and performance of state-of-the-art Ga2 O3 transistors and diodes are then described. We conclude by identifying the directions and challenges of Ga2 O3 power device development in the near future.

Thermodynamic properties of chromium bearing slags and minerals. A review

Energy Technology Data Exchange (ETDEWEB)

Xiao Yanping; Holappa, L.

1996-12-31

In this report, the thermodynamic properties of chromium bearing slags and minerals were reviewed based on the available information in the literature. It includes the analysing methods for oxidation state of chromium in slags, oxidation state of chromium and activities of chromium oxides in slags and minerals. The phase diagrams of chromium oxide systems and chromium distributions between slag and metal phases are also covered ill this review. Concerning the analysing methods, it was found that most of the available approaches are limited to iron free slag systems and the sample preparation is very sensitive to the analysing results. In silicate slags under reducing atmosphere, divalent and trivalent chromium co-exist in the slags. It is agreed that the fraction of divalent chromium to total chromium increases with higher temperature, lower slag basicity and oxygen potential. For the slags under oxidising atmosphere, trivalent, pentavalent and hexavalent states were reported to be stable. The activities of CrO and CrO{sub 1.5} were concluded to have positive deviation from ideal solution. Slag basicity has a positive effect and temperature has a negative effect on the activities of chromium oxides. The phase diagrams of the Cr-O, binary, and ternary chromium containing oxide systems have been examined systematically. The analysis shows that the data on the quaternary and quinary systems are insufficient, and require further investigation. The most important features of the chromium containing silicate slags are the large miscibility gaps and the stability of the chromite spinel. (orig.) (76 refs.)

Electrodeposition of Nanocrystalline Co-P Coatings as a Hard Chrome Alternative (Briefing Charts)

Science.gov (United States)

2011-02-10

chrome plating utilizes chromium in the hexavalent state (Cr6+) Cr6+ is a known carcinogen and poses a health risk to operators OSHA lowered the Cr6+ PEL...from 52 µg/m3 to 5 µg/m3 8 Apr 09, Memorandum, DoD Directive Hexavalent Chromium Management Policy NAVAIR Cr6+ Authorization Process Hard Chrome ...Aerospace & Defense February 10, 2011 Electrodeposition of Nanocrystalline Co-P Coatings as a Hard Chrome Alternative Jack Benfer Co-PI NAVAIR

Adsorption of uranium(VI) to manganese oxides: X-ray absorption spectroscopy and surface complexation modeling.

Science.gov (United States)

Wang, Zimeng; Lee, Sung-Woo; Catalano, Jeffrey G; Lezama-Pacheco, Juan S; Bargar, John R; Tebo, Bradley M; Giammar, Daniel E

2013-01-15

The mobility of hexavalent uranium in soil and groundwater is strongly governed by adsorption to mineral surfaces. As strong naturally occurring adsorbents, manganese oxides may significantly influence the fate and transport of uranium. Models for U(VI) adsorption over a broad range of chemical conditions can improve predictive capabilities for uranium transport in the subsurface. This study integrated batch experiments of U(VI) adsorption to synthetic and biogenic MnO(2), surface complexation modeling, ζ-potential analysis, and molecular-scale characterization of adsorbed U(VI) with extended X-ray absorption fine structure (EXAFS) spectroscopy. The surface complexation model included inner-sphere monodentate and bidentate surface complexes and a ternary uranyl-carbonato surface complex, which was consistent with the EXAFS analysis. The model could successfully simulate adsorption results over a broad range of pH and dissolved inorganic carbon concentrations. U(VI) adsorption to synthetic δ-MnO(2) appears to be stronger than to biogenic MnO(2), and the differences in adsorption affinity and capacity are not associated with any substantial difference in U(VI) coordination.

Dual passivation of intrinsic defects at the compound semiconductor/oxide interface using an oxidant and a reductant.

Science.gov (United States)

Kent, Tyler; Chagarov, Evgeniy; Edmonds, Mary; Droopad, Ravi; Kummel, Andrew C

2015-05-26

Studies have shown that metal oxide semiconductor field-effect transistors fabricated utilizing compound semiconductors as the channel are limited in their electrical performance. This is attributed to imperfections at the semiconductor/oxide interface which cause electronic trap states, resulting in inefficient modulation of the Fermi level. The physical origin of these states is still debated mainly because of the difficulty in assigning a particular electronic state to a specific physical defect. To gain insight into the exact source of the electronic trap states, density functional theory was employed to model the intrinsic physical defects on the InGaAs (2 × 4) surface and to model the effective passivation of these defects by utilizing both an oxidant and a reductant to eliminate metallic bonds and dangling-bond-induced strain at the interface. Scanning tunneling microscopy and spectroscopy were employed to experimentally determine the physical and electronic defects and to verify the effectiveness of dual passivation with an oxidant and a reductant. While subsurface chemisorption of oxidants on compound semiconductor substrates can be detrimental, it has been shown theoretically and experimentally that oxidants are critical to removing metallic defects at oxide/compound semiconductor interfaces present in nanoscale channels, oxides, and other nanostructures.

Coordination and Oxidation States of Iron Incorporated in Mesoporous MCM41

International Nuclear Information System (INIS)

Lazar, K.; Pal-Borbely, G.; Szegedi, A.; Beyer, H. K.

2002-01-01

Mesoporous Fe-MCM41 samples (Si/Fe=25) were synthesized and characterized under evacuation and reducing/oxidizing treatments by in situ FTIR and Moessbauer spectroscopies. Both Fe(II) and Fe(III) located in low coordination states in top layers of pore walls exhibit Lewis acidity and may participate in Fe(III) ↔ Fe(II) processes at low temperatures (570 K). Furthermore, Fe(III) ↔ Fe(II) cycles can be achieved and repeated with participation of the full amount of iron at higher temperatures (670 K). The accompanying formation of oxygen vacancies and restoration of the structure in the reverse process does not result in extended damages; the MCM41 structure retains its stability under the conditions applied.

Biological reduction of hexavalent chromium and mechanism analysis of detoxification by enterobacter sp. HT1 isolated from tannery effluents, Mongolia

Directory of Open Access Journals (Sweden)

N Marjangul

2014-12-01

Full Text Available Enterobacter sp. HT1, Cr (VI resistant bacterial strain was isolated from the wastewater sample of the tannery in Mongolia. Batch experiments on hexavalent chromium removal was carried out at 10, 20, and 30 mg/L of Cr (VI added as potassium dichromate (K2Cr2O7, at pH 7 and temperature of 30 °C using pure culture of Enterobacter sp. HT1 as inoculum.  The isolated HT1 is capable of reduction nearly 100% of Cr (VI resulting in the decrease of Cr (VI from 10 to 0.2 mg/L within 20 hours. When the concentration of Cr (VI increased to 20 and 30mg/L, almost complete reduction of Cr (VI could achieve after 72 and 96 hours, respectively.DOI: http://doi.dx.org/10.5564/mjc.v15i0.322 Mongolian Journal of Chemistry 15 (41, 2014, p47-52

Stabilization and solidification of chromium-contaminated soil

Energy Technology Data Exchange (ETDEWEB)

Cherne, C.A.; Thomson, B.M. [Univ. of New Mexico, Albuquerque, NM (United States). Civil Engineering Dept.; Conway, R. [Sandia National Labs., Albuquerque, NM (United States)

1997-11-01

Chromium-contaminated soil is a common environmental problem in the United States as a result of numerous industrial processes involving chromium. Hexavalent chromium [Cr(VI)] is the species of most concern because of its toxicity and mobility in groundwater. One method of diminishing the environmental impact of chromium is to reduce it to a trivalent oxidation state [Cr(III)], in which it is relatively insoluble and nontoxic. This study investigated a stabilization and solidification process to minimize the chromium concentration in the Toxicity Characteristic Leaching Procedure (TCLP) extract and to produce a solidified waste form with a compressive strength in the range of 150 to 300 pounds per square inch (psi). To minimize the chromium in the TCLP extract, the chromium had to be reduced to the trivalent oxidation state. The average used in this study was an alluvium contaminated with chromic and sulfuric acid solutions. The chromium concentration in the in the in situ soil was 1212 milligrams per kilogram (mg/kg) total chromium and 275 mg/kg Cr(VI). The effectiveness of iron, ferrous sulfate to reduce Cr(VI) was tested in batch experiments.

Stabilization and solidification of chromium-contaminated soil

International Nuclear Information System (INIS)

Cherne, C.A.; Thomson, B.M.

1997-11-01

Chromium-contaminated soil is a common environmental problem in the United States as a result of numerous industrial processes involving chromium. Hexavalent chromium [Cr(VI)] is the species of most concern because of its toxicity and mobility in groundwater. One method of diminishing the environmental impact of chromium is to reduce it to a trivalent oxidation state [Cr(III)], in which it is relatively insoluble and nontoxic. This study investigated a stabilization and solidification process to minimize the chromium concentration in the Toxicity Characteristic Leaching Procedure (TCLP) extract and to produce a solidified waste form with a compressive strength in the range of 150 to 300 pounds per square inch (psi). To minimize the chromium in the TCLP extract, the chromium had to be reduced to the trivalent oxidation state. The average used in this study was an alluvium contaminated with chromic and sulfuric acid solutions. The chromium concentration in the in the in situ soil was 1212 milligrams per kilogram (mg/kg) total chromium and 275 mg/kg Cr(VI). The effectiveness of iron, ferrous sulfate to reduce Cr(VI) was tested in batch experiments

Effects of citrate on hexavalent chromium reduction by structural Fe(II) in nontronite

Energy Technology Data Exchange (ETDEWEB)

Liu, Xiaolei; Dong, Hailiang; Yang, Xuewei; Kovarik, Libor; Chen, Yu; Zeng, Qiang

2018-02-01

Iron-bearing clay minerals and organic matter are two important components in natural environments that influence hexavalent chromium (Cr(VI)) reduction. Previous studies have shown that organic ligands could influence Cr(VI) reduction by aqueous Fe2+ and pyrite. However, the effects of organic ligands on Cr(VI) reduction by structural Fe(II) in clays are not well understood. In this study, the effects of citrate on Cr(VI) reduction by nontronite (NAu-2) were investigated under near neutral pH condition (pH=6). Our results showed that the presence of citrate decreased the rate but increased the amount of Cr(VI) reduction by structural Fe(II) in NAu-2. The decreased reaction rate was likely due to competitive sorption of citrate and polyanionic dichromate (Cr2O7- ), because sorption of dichromate appeared to be the first step for subsequent Cr(VI) reduction. The increased amount of Cr(VI) reduction in the presence of citrate was likely because citrate provided additional reducing power through ligand-metal electron transfer in the presence of soluble Fe 3+ derived from dissolution of reduced NAu-2. Soluble Cr(III)-citrate complex was the possible form of reduced chromium when citrate was present. In contrast, nanometer-sized Cr2O3 particles were the product of Cr(VI) reduction by reduced NAu-2 without citrate. Our study highlights the importance of organic ligands on Cr(VI) reduction and immobilization when iron-bearing clay minerals are applied to treat Cr(VI) contaminant in organic matter rich environments.

Oxidation state inherited from the magma source and implications for mineralization: Late Jurassic to Early Cretaceous granitoids, Central Lhasa subterrane, Tibet

Science.gov (United States)

Cao, MingJian; Qin, KeZhang; Li, GuangMing; Evans, Noreen J.; McInnes, Brent I. A.; Li, JinXiang; Zhao, JunXing

2018-03-01

Arc magmas are more oxidized than mid-ocean ridge basalts; however, there is continuing debate as to whether this higher oxidation state is inherited from the source magma or developed during late-stage magmatic differentiation processes. Well-constrained Late Jurassic to Early Cretaceous arc-related intermediate to felsic rocks derived from distinct magma sources provide us with a good opportunity to resolve this enigma. A series of granitoids from the western Central Lhasa subterrane were analyzed for whole-rock magnetic susceptibility, Fe2O3/FeO ratios, and trace elements in zircon. Compared to Late Jurassic samples (1.8 ± 2.0 × 10-4 emu g-1 oe-1, Fe3+/Fetotal = 0.32 ± 0.07, zircon Ce4+/Ce3+* = 15.0 ± 13.4), Early Cretaceous rocks show higher whole-rock magnetic susceptibility (5.8 ± 2.5 × 10-4 emu g-1 oe-1), Fe3+/Fetotal ratios (0.43 ± 0.04), and zircon Ce4+/Ce3+* values (23.9 ± 22.3). In addition, positive correlations among whole-rock magnetic susceptibility, Fe3+/Fetotal ratios, and zircon Ce4+/Ce3+* reveal a slight increase in oxidation state from fO2 = QFM to NNO in the Late Jurassic to fO2 = ˜NNO in the Early Cretaceous. Obvious linear correlation between oxidation indices (whole-rock magnetic susceptibility, zircon Ce4+/Ce3+*) and source signatures (zircon ɛHf(t), TDM C ages) indicates that the oxidation state was predominantly inherited from the source with only a minor contribution from magmatic differentiation. Thus, the sources for both the Late Jurassic and Early Cretaceous rocks were probably influenced by mantle wedge-derived magma, contributing to the increased fO2. Compared to ore-forming rocks at giant porphyry Cu deposits, the relatively low oxidation state (QFM to NNO) and negative ɛHf(t) (-16 to 0) of the studied granitoids implies relative infertility. However, this study demonstrates two potential fast and effective indices ( fO2 and ɛHf(t)) to evaluate the fertility of granitoids for porphyry-style mineralization. In an

Removal of hexavalent chromium [Cr(VI)] from aqueous solutions by the diatomite-supported/unsupported magnetite nanoparticles

Energy Technology Data Exchange (ETDEWEB)

Yuan Peng, E-mail: yuanpeng@gig.ac.cn [Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640 (China); Liu Dong; Fan Mingde; Yang Dan [Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640 (China); Graduate School of Chinese Academy of Sciences, Beijing 100039 (China); Zhu Runliang; Ge Fei [College of Chemical Engineering, Xiangtan University, Xiangtan 411105 (China); Zhu Jianxi; He Hongping [Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640 (China)

2010-01-15

Diatomite-supported/unsupported magnetite nanoparticles were prepared by co-precipitation and hydrosol methods, and characterized by X-ray diffraction, nitrogen adsorption, elemental analysis, differential scanning calorimetry, transmission electron microscopy and X-ray photoelectron spectroscopy. The average sizes of the unsupported and supported magnetite nanoparticles are around 25 and 15 nm, respectively. The supported magnetite nanoparticles exist on the surface or inside the pores of diatom shells, with better dispersing and less coaggregation than the unsupported ones. The uptake of hexavalent chromium [Cr(VI)] on the synthesized magnetite nanoparticles was mainly governed by a physico-chemical process, which included an electrostatic attraction followed by a redox process in which Cr(VI) was reduced into trivalent chromium [Cr(III)]. The adsorption of Cr(VI) was highly pH-dependent and the kinetics of the adsorption followed a pseudo-second-order model. The adsorption data of diatomite-supported/unsupported magnetite fit well with the Langmuir isotherm equation. The supported magnetite showed a better adsorption capacity per unit mass of magnetite than unsupported magnetite, and was more thermally stable than their unsupported counterparts. These results indicate that the diatomite-supported/unsupported magnetite nanoparticles are readily prepared, enabling promising applications for the removal of Cr(VI) from aqueous solution.

Removal of hexavalent chromium [Cr(VI)] from aqueous solutions by the diatomite-supported/unsupported magnetite nanoparticles.

Science.gov (United States)

Yuan, Peng; Liu, Dong; Fan, Mingde; Yang, Dan; Zhu, Runliang; Ge, Fei; Zhu, JianXi; He, Hongping

2010-01-15

Diatomite-supported/unsupported magnetite nanoparticles were prepared by co-precipitation and hydrosol methods, and characterized by X-ray diffraction, nitrogen adsorption, elemental analysis, differential scanning calorimetry, transmission electron microscopy and X-ray photoelectron spectroscopy. The average sizes of the unsupported and supported magnetite nanoparticles are around 25 and 15 nm, respectively. The supported magnetite nanoparticles exist on the surface or inside the pores of diatom shells, with better dispersing and less coaggregation than the unsupported ones. The uptake of hexavalent chromium [Cr(VI)] on the synthesized magnetite nanoparticles was mainly governed by a physico-chemical process, which included an electrostatic attraction followed by a redox process in which Cr(VI) was reduced into trivalent chromium [Cr(III)]. The adsorption of Cr(VI) was highly pH-dependent and the kinetics of the adsorption followed a pseudo-second-order model. The adsorption data of diatomite-supported/unsupported magnetite fit well with the Langmuir isotherm equation. The supported magnetite showed a better adsorption capacity per unit mass of magnetite than unsupported magnetite, and was more thermally stable than their unsupported counterparts. These results indicate that the diatomite-supported/unsupported magnetite nanoparticles are readily prepared, enabling promising applications for the removal of Cr(VI) from aqueous solution.

Wet digestion and differential pulse stripping voltammetry determination of total chromium in the millet

Directory of Open Access Journals (Sweden)

Yaqin LIU

2015-06-01

Full Text Available The chromium content of millet is measured by HNO3-H2O2 digestion and electrochemical method. In the DTPA-HAc-NaAc system, the oxidation peak current of amalgam formed by hexavalent chrome ion is obtained in the plating mercury electrode, and the pre-treatment technology of wet digestion can meet the electrochemical determination. The optimized detection condition of electrochemical method for hexavalent chrome ion is 130 ℃ of digestion solution, 10 mL hydrogen peroxide, 38 mL nitric acid, and neutral of pH. The linear correlation coefficient of electrochemical method is 0.99, and the recovery of standard addition is 90%~110%. This method can be used to trace chromium (Ⅵ determination in millet.

Hexavalent chromium reduction by bacterial consortia and pure strains from an alkaline industrial effluent.

Science.gov (United States)

Piñón-Castillo, H A; Brito, E M S; Goñi-Urriza, M; Guyoneaud, R; Duran, R; Nevarez-Moorillon, G V; Gutiérrez-Corona, J F; Caretta, C A; Reyna-López, G E

2010-12-01

To characterize the bacterial consortia and isolates selected for their role in hexavalent chromium removal by adsorption and reduction. Bacterial consortia from industrial wastes revealed significant Cr(VI) removal after 15 days when incubated in medium M9 at pH 6·5 and 8·0. The results suggested chromium reduction. The bacterial consortia diversity (T-RFLP based on 16S rRNA gene) indicated a highest number of operational taxonomic units in an alkaline carbonate medium mimicking in situ conditions. However, incubations under such conditions revealed low Cr(VI) removal. Genomic libraries were obtained for the consortia exhibiting optimal Cr(VI) removal (M9 medium at pH 6·5 and 8·0). They revealed the dominance of 16S rRNA gene sequences related to the genera Pseudomonas/Stenotrophomonas or Enterobacter/Halomonas, respectively. Isolates related to Pseudomonas fluorescens and Enterobacter aerogenes were efficient in Cr(VI) reduction and adsorption to the biomass. Cr(VI) reduction was better at neutral pH rather than under in situ conditions (alkaline pH with carbonate). Isolated strains exhibited significant capacity for Cr(VI) reduction and adsorption. Bacterial communities from chromium-contaminated industrial wastes as well as isolates were able to remove Cr(VI). The results suggest a good potential for bioremediation of industrial wastes when optimal conditions are applied. Journal of Applied Microbiology © 2010 The Society for Applied Microbiology. No claim to Mexican Government works.

Room air versus carbon dioxide pneumoperitoneum: effects on oxidative state, apoptosis and histology of splanchnic organs.

Science.gov (United States)

Ypsilantis, Petros; Lambropoulou, Maria; Tentes, Ioannis; Chryssidou, Maria; Georgantas, Themistoklis; Simopoulos, Constantinos

2016-04-01

Although CO2 is the insufflation gas of choice in laparoscopic procedures, room air is usually used in natural orifice transluminal endoscopic surgery. The aim of the present study was to compare the safety of room air versus CO2 pneumoperitoneum in terms of their effect on the oxidative state, apoptosis and tissue injury of splanchnic organs. Eighteen Wistar rats were assigned to three groups (n = 6 per group) and were subjected to 8 mm Hg room air (group Pne-Air) or CO2 pneumoperitoneum (group Pne-CO2) or sham operation for 60 min. Forty-five minutes postdeflation, tissue samples were excised from the liver, stomach, ileum and kidneys for reduced glutathione-to-glutathione disulfide (GSH/GSSG) ratio, caspase-8 and caspase-3 and hypoxia-inducible factor-1α (HIF-1α) immunohistochemical assessment and histopathologic examination. GSH/GSSG ratio substantially declined in both pneumoperitoneum groups. No change was noted in HIF-1α expression. Mild upregulation of caspase-8 and caspase-3 was noted in both pneumoperitoneum groups being less pronounced in group Pne-Air. Histopathologic score was increased in all organs studied, but the stomach, in both pneumoperitoneum groups. Pneumoperitoneum established by either room air or CO2 induced substantial oxidative stress, mild apoptosis and mild tissue injury in splanchnic organs. While air pneumoperitoneum conferred a less pronounced apoptotic effect, the oxidative state and histopathologic profile of splanchnic organs did not differ between insufflation gases.

X-ray Absorption Study of Graphene Oxide and Transition Metal Oxide Nanocomposites

OpenAIRE

Gandhiraman, Ram P.; Nordlund, Dennis; Javier, Cristina; Koehne, Jessica E.; Chen, Bin; Meyyappan, M.

2014-01-01

The surface properties of the electrode materials play a crucial role in determining the performance and efficiency of energy storage devices. Graphene oxide and nanostructures of 3d transition metal oxides were synthesized for construction of electrodes in supercapacitors, and the electronic structure and oxidation states were probed using near-edge X-ray absorption fine structure. Understanding the chemistry of graphene oxide would provide valuable insight into its reactivity and properties...

Oxidation mechanisms occurring in wines

OpenAIRE

Oliveira, Carla Maria; Ferreira, António César Silva; Freitas, Victor De; Silva, Artur M. S.

2011-01-01

The present review aims to show the state of the art on the oxidation mechanisms occurring in wines, as well as the methods to monitor, classify and diagnose wine oxidation. Wine oxidation can be divided in enzymatic oxidation and non-enzymatic oxidation. Enzymatic oxidation almost entirely occurs in grape must and is largely correlated with the content of hydroxycinnamates, such as caffeoyltartaric acid and paracoumaroyltartaric acid, and flavan-3-ols. Non-enzymatic oxidation, al...

Comprehensive mechanism and structure-sensitivity of ethanol oxidation on platinum: new transition-state searching method for resolving the complex reaction network.

Science.gov (United States)

Wang, Hui-Fang; Liu, Zhi-Pan

2008-08-20

Ethanol oxidation on Pt is a typical multistep and multiselectivity heterogeneous catalytic process. A comprehensive understanding of this fundamental reaction would greatly benefit design of catalysts for use in direct ethanol fuel cells and the degradation of biomass-derived oxygenates. In this work, the reaction network of ethanol oxidation on different Pt surfaces, including close-packed Pt{111}, stepped Pt{211}, and open Pt{100}, is explored thoroughly with an efficient reaction path searching method, which integrates our new transition-state searching technique with periodic density functional theory calculations. Our new technique enables the location of the transition state and saddle points for most surface reactions simply and efficiently by optimization of local minima. We show that the selectivity of ethanol oxidation on Pt depends markedly on the surface structure, which can be attributed to the structure-sensitivity of two key reaction steps: (i) the initial dehydrogenation of ethanol and (ii) the oxidation of acetyl (CH3CO). On open surface sites, ethanol prefers C-C bond cleavage via strongly adsorbed intermediates (CH2CO or CHCO), which leads to complete oxidation to CO2. However, only partial oxidizations to CH3CHO and CH3COOH occur on Pt{111}. Our mechanism points out that the open surface Pt{100} is the best facet to fully oxidize ethanol at low coverages, which sheds light on the origin of the remarkable catalytic performance of Pt tetrahexahedra nanocrystals found recently. The physical origin of the structure-selectivity is rationalized in terms of both thermodynamics and kinetics. Two fundamental quantities that dictate the selectivity of ethanol oxidation are identified: (i) the ability of surface metal atoms to bond with unsaturated C-containing fragments and (ii) the relative stability of hydroxyl at surface atop sites with respect to other sites.

Poly[(ethylene oxide)-co-(methylene ethylene oxide)]: A hydrolytically-degradable poly(ethylene oxide) platform.

Science.gov (United States)

Lundberg, Pontus; Lee, Bongjae F; van den Berg, Sebastiaan A; Pressly, Eric D; Lee, Annabelle; Hawker, Craig J; Lynd, Nathaniel A

2012-11-20

A facile method for imparting hydrolytic degradability to poly(ethylene oxide) (PEO), compatible with current PEGylation strategies, is presented. By incorporating methylene ethylene oxide (MEO) units into the parent PEO backbone, complete degradation was defined by the molar incorporation of MEO, and the structure of the degradation byproducts was consistent with an acid-catalyzed vinyl-ether hydrolysis mechanism. The hydrolytic degradation of poly[(ethylene oxide)-co-(methylene ethylene oxide)] was pH-sensitive, with degradation at pH 5 being significantly faster than at pH 7.4 at 37 °C in PBS buffer while long-term stability could be obtained in either the solid-state or at pH 7.4 at 6 °C.

Uranium extraction in phosphoric acid

International Nuclear Information System (INIS)

Araujo Figueiredo, C. de

1984-01-01

Uranium is recovered from the phosphoric liquor produced from the concentrate obtained from phosphorus-uraniferous mineral from Itataia mines (CE, Brazil). The proposed process consists of two extraction cycles. In the first one, uranium is reduced to its tetravalent state and then extracted by dioctylpyrophosphoric acid, diluted in Kerosene. Re-extraction is carried out with concentrated phosphoric acid containing an oxidising agent to convert uranium to its hexavalent state. This extract (from the first cycle) is submitted to the second cycle where uranium is extracted with DEPA-TOPO (di-2-hexylphosphoric acid/tri-n-octyl phosphine oxide) in Kerosene. The extract is then washed and uranium is backextracted and precipitated as commercial concentrate. The organic phase is recovered. Results from discontinuous tests were satisfactory, enabling to establish operational conditions for the performance of a continuous test in a micro-pilot plant. (Author) [pt

Study of transition metal oxides by photoelectron spectroscopy

International Nuclear Information System (INIS)