Comparison of different advanced degradation processes for the removal of the pharmaceutical compounds diclofenac and carbamazepine from liquid solutions.

PubMed

Capodaglio, Andrea G; Bojanowska-Czajka, Anna; Trojanowicz, Marek

2018-04-18

Carbamazepine and diclofenac are two examples of drugs with widespread geographical and environmental media proliferation that are poorly removed by traditional wastewater treatment processes. Advanced oxidation processes (AOPs) have been proposed as alternative methods to remove these compounds in solution. AOPs are based on a wide class of powerful technologies, including UV radiation, ozone, hydrogen peroxide, Fenton process, catalytic wet peroxide oxidation, heterogeneous photocatalysis, electrochemical oxidation and their combinations, sonolysis, and microwaves applicable to both water and wastewater. Moreover, processes rely on the production of oxidizing radicals (•OH and others) in a solution to decompose present pollutants. Water radiolysis-based processes, which are an alternative to the former, involve the use of concentrated energy (beams of accelerated electrons or γ-rays) to split water molecules, generating strong oxidants and reductants (radicals) at the same time. In this paper, the degradation of carbamazepine and diclofenac by means of all these processes is discussed and compared. Energy and byproduct generation issues are also addressed.

Facile Routes To Improve Performance of Solution-Processed Amorphous Metal Oxide Thin Film Transistors by Water Vapor Annealing.

PubMed

Park, Won-Tae; Son, Inyoung; Park, Hyun-Woo; Chung, Kwun-Bum; Xu, Yong; Lee, Taegweon; Noh, Yong-Young

2015-06-24

Here, we report on a simple and high-rate oxidization method for producing solution-based compound mixtures of indium zinc oxide (IZO) and indium gallium zinc oxide (IGZO) metal-oxide semiconductors (MOS) for thin-film transistor (TFT) applications. One of the issues for solution-based MOS fabrication is how to sufficiently oxidize the precursor in order to achieve high performance. As the oxidation rate of solution processing is lower than vacuum-based deposition such as sputtering, devices using solution-processed MOS exhibit relatively poorer performance. Therefore, we propose a method to prepare the metal-oxide precursor upon exposure to saturated water vapor in a closed volume for increasing the oxidization efficiency without requiring additional oxidizing agent. We found that the hydroxide rate of the MOS film exposed to water vapor is lower than when unexposed (≤18%). Hence, we successfully fabricated oxide TFTs with high electron mobility (27.9 cm(2)/V·s) and established a rapid process (annealing at 400 °C for 5 min) that is much shorter than the conventional as-deposited long-duration annealing (at 400 °C for 1 h) whose corresponding mobility is even lower (19.2 cm(2)/V·s).

Post-treatment of reclaimed waste water based on an electrochemical advanced oxidation process

NASA Technical Reports Server (NTRS)

Verostko, Charles E.; Murphy, Oliver J.; Hitchens, G. D.; Salinas, Carlos E.; Rogers, Tom D.

1992-01-01

The purification of reclaimed water is essential to water reclamation technology life-support systems in lunar/Mars habitats. An electrochemical UV reactor is being developed which generates oxidants, operates at low temperatures, and requires no chemical expendables. The reactor is the basis for an advanced oxidation process in which electrochemically generated ozone and hydrogen peroxide are used in combination with ultraviolet light irradiation to produce hydroxyl radicals. Results from this process are presented which demonstrate concept feasibility for removal of organic impurities and disinfection of water for potable and hygiene reuse. Power, size requirements, Faradaic efficiency, and process reaction kinetics are discussed. At the completion of this development effort the reactor system will be installed in JSC's regenerative water recovery test facility for evaluation to compare this technique with other candidate processes.

Comparision of photocatalysis and photolysis processes for arsenic oxidation in water.

PubMed

Fontana, Klaiani B; Lenzi, Giane G; Seára, Eriton C R; Chaves, Eduardo S

2018-04-30

The oxidation of As(III) to As(V) in aqueous solution was evaluated using heterogeneous photocatalysis and photolysis. The influence of TiO 2 as catalyst in different crystalline (rutile, anatase) and commercial forms was evaluated in a batch reactor and an insignificant difference was observed between them. The process by photocatalysis reached up to 97% As(III) oxidation and no significant difference was observed comparing to results obtained by photolysis. The photolysis experiments (UV radiation only), also carried out in a batch system, showed a high oxidation rate of As(III) (90% in 20min). The influence of different matrices (well water, river water and public water supply) were evaluated. Additionally, the effect of As(V) concentration, generated during the oxidation process, was studied. Continuous photolysis experiments using only UV radiation were performed, resulting in a high As(III) oxidation rate. Using a flow rate of 5mLmin -1 and an initial concentration of As(III) 200µgL -1 , gave an oxidation percentage of As(III) of up to 72%, showing a simple and economical alternative to the oxidation step of As(III) to As(V) in the treatment of water contaminated with arsenic. Copyright © 2018 Elsevier Inc. All rights reserved.

Supercritical water oxidation for wastewater treatment Preliminary study of urea destruction

NASA Technical Reports Server (NTRS)

Timberlake, S. H.; Hong, G. T.; Simson, M.; Modell, M.

1982-01-01

Supercritical water oxidation is being investigated as a method of treating spacecraft wastewater for recycle. In this process, oxidation is conducted in an aqueous phase maintained above the critical temperature (374 C) and pressure (215 bar) of water. Organic materials are oxidized with efficiencies greater than 99.99 percent in residence times of less than 1 minute. This paper presents preliminary results for urea destruction. Above 650 C, urea can be completely broken down to nitrogen gas, carbon dioxide and water by supercritical water oxidation, without the use of a specific catalyst.

Oxidation of artificial sweetener sucralose by advanced oxidation processes: a review.

PubMed

Sharma, Virender K; Oturan, Mehmet; Kim, Hyunook

2014-01-01

Sucralose, a chlorinated carbohydrate, has shown its increased use as an artificial sweetener and persistently exists in wastewater treatment plant effluents and aquatic environment. This paper aims to review possible degradation of sucralose and related carbohydrates by biological, electrochemical, chemical, and advanced oxidation processes. Biodegradation of sucralose in waterworks did not occur significantly. Electrochemical oxidation of carbohydrates may be applied to seek degradation of sucralose. The kinetics of the oxidation of sucralose and the related carbohydrates by different oxidative species is compared. Free chlorine, ozone, and ferrate did not show any potential to degrade sucralose in water. Advanced oxidation processes, generating highly strong oxidizing agent hydroxyl radicals ((•)OH), have demonstrated effectiveness in transforming sucralose in water. The mechanism of oxidation of sucralose by (•)OH is briefly discussed.

Advanced oxidation processes for the removal of natural organic matter from drinking water sources: A comprehensive review.

PubMed

Sillanpää, Mika; Ncibi, Mohamed Chaker; Matilainen, Anu

2018-02-15

Natural organic matter (NOM), a key component in aquatic environments, is a complex matrix of organic substances characterized by its fluctuating amounts in water and variable molecular and chemical properties, leading to various interaction schemes with the biogeosphere and hydrologic cycle. These factors, along with the increasing amounts of NOM in surface and ground waters, make the effort of removing naturally-occurring organics from drinking water supplies, and also from municipal wastewater effluents, a challenging task requiring the development of highly efficient and versatile water treatment technologies. Advanced oxidation processes (AOPs) received an increasing amount of attention from researchers around the world, especially during the last decade. The related processes were frequently reported to be among the most suitable water treatment technologies to remove NOM from drinking water supplies and mitigate the formation of disinfection by products (DBPs). Thus, the present work overviews recent research and development studies conducted on the application of AOPs to degrade NOM including UV and/or ozone-based applications, different Fenton processes and various heterogeneous catalytic and photocatalytic oxidative processes. Other non-conventional AOPs such as ultrasonication, ionizing radiation and plasma technologies were also reported. Furthermore, since AOPs are unlikely to achieve complete oxidation of NOM, integration schemes with other water treatment technologies were presented including membrane filtration, adsorption and others processes. Copyright © 2017 Elsevier Ltd. All rights reserved.

Iron oxidation kinetics and phosphate immobilization along the flow-path from groundwater into surface water

NASA Astrophysics Data System (ADS)

van der Grift, B.; Rozemeijer, J. C.; Griffioen, J.; van der Velde, Y.

2014-11-01

The retention of phosphorus in surface waters through co-precipitation of phosphate with Fe-oxyhydroxides during exfiltration of anaerobic Fe(II) rich groundwater is not well understood. We developed an experimental field set-up to study Fe(II) oxidation and P immobilization along the flow-path from groundwater into surface water in an agricultural experimental catchment of a small lowland river. We physically separated tube drain effluent from groundwater discharge before it entered a ditch in an agricultural field. Through continuous discharge measurements and weekly water quality sampling of groundwater, tube drain water, exfiltrated groundwater, and surface water, we investigated Fe(II) oxidation kinetics and P immobilization processes. The oxidation rate inferred from our field measurements closely agreed with the general rate law for abiotic oxidation of Fe(II) by O2. Seasonal changes in climatic conditions affected the Fe(II) oxidation process. Lower pH and lower temperatures in winter (compared to summer) resulted in low Fe oxidation rates. After exfiltration to the surface water, it took a couple of days to more than a week before complete oxidation of Fe(II) is reached. In summer time, Fe oxidation rates were much higher. The Fe concentrations in the exfiltrated groundwater were low, indicating that dissolved Fe(II) is completely oxidized prior to inflow into a ditch. While the Fe oxidation rates reduce drastically from summer to winter, P concentrations remained high in the groundwater and an order of magnitude lower in the surface water throughout the year. This study shows very fast immobilization of dissolved P during the initial stage of the Fe(II) oxidation process which results in P-depleted water before Fe(II) is completely depleted. This cannot be explained by surface complexation of phosphate to freshly formed Fe-oxyhydroxides but indicates the formation of Fe(III)-phosphate precipitates. The formation of Fe(III)-phosphates at redox gradients seems an important geochemical mechanism in the transformation of dissolved phosphate to structural phosphate and, therefore, a major control on the P retention in natural waters that drain anaerobic aquifers.

Cyclic thermochemical process for producing hydrogen using cerium-titanium compounds

DOEpatents

Bamberger, Carlos E.

1980-01-01

A thermochemical cyclic process for producing hydrogen employs the reaction between ceric oxide and titanium dioxide to form cerium titanate and oxygen. The titanate is treated with an alkali metal hydroxide to give hydrogen, ceric oxide, an alkali metal titanate and water. Alkali metal titanate and water are boiled to give titanium dioxide which, along with ceric oxide, is recycled.

Cyclic thermochemical process for producing hydrogen using cerium-titanium compounds

DOEpatents

Bamberger, C.E.

A thermochemical cyclic process for producing hydrogen employs the reaction between ceric oxide and titanium dioxide to form cerium titanate and oxygen. The titanate is treated with an alkali metal hydroxide to give hydrogen, ceric oxide, an alkali metal titanate and water. Alkali metal titanate and water are boiled to give titanium dioxide which, along with ceric oxide, is recycled.

Specific features of aluminum nanoparticle water and wet air oxidation

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

Lozhkomoev, Aleksandr S., E-mail: asl@ispms.tsc.ru; Glazkova, Elena A., E-mail: eagl@ispms.tsc.ru; Svarovskaya, Natalia V., E-mail: nvsv@ispms.tsc.ru

2015-10-27

The oxidation processes of the electrically exploded aluminum nanopowders in water and in wet air are examined in the paper. The morphology of the intermediate reaction products of aluminum oxidation has been studied using the transmission electron microscopy. It was shown that the aluminum nanopowder water oxidation causes the formation of the hollow spheres with mesoporous boehmite nanosheets coating. The wedge-like bayerite particles are formed during aluminum nanopowder wet air oxidation.

Thermochemical cyclic system for splitting water and/or carbon dioxide by means of cerium compounds and reactions useful therein

DOEpatents

Bamberger, C.E.; Robinson, P.R.

A thermochemical cyclic process for producing hydrogen from water comprises reacting ceric oxide with monobasic or dibasic alkali metal phosphate to yield a solid reaction product, oxygen and water. The solid reaction product, alkali metal carbonate or bicarbonate, and water, are reacted to yield hydrogen, ceric oxide, carbon dioxide and trialkali metal phosphate. Ceric oxide is recycled. Trialkali metal phosphate, carbon dioxide and water are reacted to yield monobasic or dibasic alkali metal phosphate and alkali metal bicarbonate, which are recycled. The cyclic process can be modified for producing carbon monoxide from carbon dioxide by reacting the alkali metal cerous phosphate and alkali metal carbonate or bicarbonate in the absence of water to produce carbon monoxide, ceric oxide, carbon dioxide and trialkali metal phosphate. Carbon monoxide can be converted to hydrogen by the water gas shift reaction.

Thermochemical cyclic system for splitting water and/or carbon dioxide by means of cerium compounds and reactions useful therein

DOEpatents

Bamberger, Carlos E.; Robinson, Paul R.

1980-01-01

A thermochemical cyclic process for producing hydrogen from water comprises reacting ceric oxide with monobasic or dibasic alkali metal phosphate to yield a solid reaction product, oxygen and water. The solid reaction product, alkali metal carbonate or bicarbonate, and water, are reacted to yield hydrogen, ceric oxide, carbon dioxide and trialkali metal phosphate. Ceric oxide is recycled. Trialkali metal phosphate, carbon dioxide and water are reacted to yield monobasic or dibasic alkali metal phosphate and alkali metal bicarbonate, which are recycled. The cylic process can be modified for producing carbon monoxide from carbon dioxide by reacting the alkali metal cerous phosphate and alkali metal carbonate or bicarbonate in the absence of water to produce carbon monoxide, ceric oxide, carbon dioxide and trialkali metal phosphate. Carbon monoxide can be converted to hydrogen by the water gas shift reaction.

Green and Mild Oxidation: An Efficient Strategy toward Water-Dispersible Graphene.

PubMed

You, Xiaofei; Yang, Siwei; Li, Jipeng; Deng, Yuan; Dai, Lianqi; Peng, Xiong; Huang, Haoguang; Sun, Jing; Wang, Gang; He, Peng; Ding, Guqiao; Xie, Xiaoming

2017-01-25

Scalable fabrication of water-dispersible graphene (W-Gr) is highly desirable yet technically challenging for most practical applications of graphene. Herein, a green and mild oxidation strategy to prepare bulk W-Gr (dispersion, slurry, and powder) with high yield was proposed by fully exploiting structure defects of thermally reduced graphene oxide (TRGO) and oxidizing radicals generated from hydrogen peroxide (H 2 O 2 ). Owing to the increased carboxyl group from the mild oxidation process, the obtained W-Gr can be redispersed in low-boiling solvents with a reasonable concentration. Benefiting from the modified surface chemistry, macroscopic samples processed from the W-Gr show good hydrophilicity (water contact angle of 55.7°) and excellent biocompatibility, which is expected to be an alternative biomaterial for bone, vessel, and skin regeneration. In addition, the green and mild oxidation strategy is also proven to be effective for dispersing other carbon nanomaterials in a water system.

Electrochemical advanced oxidation processes as decentralized water treatment technologies to remediate domestic washing machine effluents.

PubMed

Dos Santos, Alexsandro Jhones; Costa, Emily Cintia Tossi de Araújo; da Silva, Djalma Ribeiro; Garcia-Segura, Sergi; Martínez-Huitle, Carlos Alberto

2018-03-01

Water scarcity is one of the major concerns worldwide. In order to secure this appreciated natural resource, management and development of water treatment technologies are mandatory. One feasible alternative is the consideration of water recycling/reuse at the household scale. Here, the treatment of actual washing machine effluent by electrochemical advanced oxidation processes was considered. Electrochemical oxidation and electro-Fenton technologies can be applied as decentralized small-scale water treatment devices. Therefore, efficient decolorization and total organic abatement have been followed. The results demonstrate the promising performance of solar photoelectro-Fenton process, where complete color and organic removal was attained after 240 min of treatment under optimum conditions by applying a current density of 66.6 mA cm -2 . Thus, electrochemical technologies emerge as promising water-sustainable approaches.

Monitoring Interfacial Lipid Oxidation in Oil-in-Water Emulsions Using Spatially Resolved Optical Techniques.

PubMed

Banerjee, Chiranjib; Westberg, Michael; Breitenbach, Thomas; Bregnhøj, Mikkel; Ogilby, Peter R

2017-06-06

The oxidation of lipids is an important phenomenon with ramifications for disciplines that range from food science to cell biology. The development and characterization of tools and techniques to monitor lipid oxidation are thus relevant. Of particular significance in this regard are tools that facilitate the study of oxidations at interfaces in heterogeneous samples (e.g., oil-in-water emulsions, cell membranes). In this article, we establish a proof-of-principle for methods to initiate and then monitor such oxidations with high spatial resolution. The experiments were performed using oil-in-water emulsions of polyunsaturated fatty acids (PUFAs) prepared from cod liver oil. We produced singlet oxygen at a point near the oil-water interface of a given PUFA droplet in a spatially localized two-photon photosensitized process. We then followed the oxidation reactions initiated by this process with the fluorescence-based imaging technique of structured illumination microscopy (SIM). We conclude that the approach reported herein has attributes well-suited to the study of lipid oxidation in heterogeneous samples.

Water exchange in manganese-based water-oxidizing catalysts in photosynthetic systems: from the water-oxidizing complex in photosystem II to nano-sized manganese oxides.

PubMed

Najafpour, Mohammad Mahdi; Isaloo, Mohsen Abbasi; Eaton-Rye, Julian J; Tomo, Tatsuya; Nishihara, Hiroshi; Satoh, Kimiyuki; Carpentier, Robert; Shen, Jian-Ren; Allakhverdiev, Suleyman I

2014-09-01

The water-oxidizing complex (WOC), also known as the oxygen-evolving complex (OEC), of photosystem II in oxygenic photosynthetic organisms efficiently catalyzes water oxidation. It is, therefore, responsible for the presence of oxygen in the Earth's atmosphere. The WOC is a manganese-calcium (Mn₄CaO₅(H₂O)₄) cluster housed in a protein complex. In this review, we focus on water exchange chemistry of metal hydrates and discuss the mechanisms and factors affecting this chemical process. Further, water exchange rates for both the biological cofactor and synthetic manganese water splitting are discussed. The importance of fully unveiling the water exchange mechanism to understand the chemistry of water oxidation is also emphasized here. This article is part of a special issue entitled: photosynthesis research for sustainability: keys to produce clean energy. Copyright © 2014 Elsevier B.V. All rights reserved.

High-voltage nano-oxidation in deionized water and atmospheric environments by atomic force microscopy.

PubMed

Huang, Jen-Ching; Chen, Chung-Ming

2012-01-01

This study used atomic force microscopy (AFM), metallic probes with a nanoscale tip, and high-voltage generators to investigate the feasibility of high-voltage nano-oxidation processing in deionized water (DI water) and atmospheric environments. Researchers used a combination of wire-cutting and electrochemical etching to transform a 20-μm-thick stainless steel sheet into a conductive metallic AFM probe with a tip radius of 60 nm, capable of withstanding high voltages. The combination of AFM, high-voltage generators, and nanoscale metallic probes enabled nano-oxidation processing at 200 V in DI water environments, producing oxides up to 66.6 nm in height and 467.03 nm in width. Oxides produced through high-voltage nano-oxidation in atmospheric environments were 117.29 nm in height and 551.28 nm in width, considerably exceeding the dimensions of those produced in DI water. An increase in the applied bias voltage led to an apparent logarithmic increase in the height of the oxide dots in the range of 200-400 V. The performance of the proposed high-voltage nano-oxidation technique was relatively high with seamless integration between the AFM machine and the metallic probe fabricated in this study. © Wiley Periodicals, Inc.

Effects of the polarizability and packing density of transparent oxide films on water vapor permeation.

PubMed

Koo, Won Hoe; Jeong, Soon Moon; Choi, Sang Hun; Kim, Woo Jin; Baik, Hong Koo; Lee, Sung Man; Lee, Se Jong

2005-06-09

The tin oxide and silicon oxide films have been deposited on polycarbonate substrates as gas barrier films, using a thermal evaporation and ion beam assisted deposition process. The oxide films deposited by ion beam assisted deposition show a much lower water vapor transmission rate than those by thermal evaporation. The tin oxide films show a similar water vapor transmission rate to the silicon oxide films in thermal evaporation but a lower water vapor transmission rate in IBAD. These results are related to the fact that the permeation of water vapor with a large dipole moment is affected by the chemistry of oxides and the packing density of the oxide films. The permeation mechanism of water vapor through the oxide films is discussed in terms of the chemical interaction with water vapor and the microstructure of the oxide films. The chemical interaction of water vapor with oxide films has been investigated by the refractive index from ellipsometry and the OH group peak from X-ray photoelectron spectroscopy, and the microstructure of the composite oxide films was characterized using atomic force microscopy and a transmission electron microscope. The activation energy for water vapor permeation through the oxide films has also been measured in relation to the permeation mechanism of water vapor. The diffusivity of water vapor for the tin oxide films has been calculated from the time lag plot, and its implications are discussed.

Simultaneous oxidation of arsenic and antimony at low and circumneutral pH, with and without microbial catalysis

USGS Publications Warehouse

Asta, Maria P.; Nordstrom, D. Kirk; McCleskey, R. Blaine

2012-01-01

Arsenic and Sb are common mine-water pollutants and their toxicity and fate are strongly influenced by redox processes. In this study, simultaneous Fe(II), As(III) and Sb(III) oxidation experiments were conducted to obtain rates under laboratory conditions similar to those found in the field for mine waters of both low and circumneutral pH. Additional experiments were performed under abiotic sterile conditions to determine the biotic and abiotic contributions to the oxidation processes. The results showed that under abiotic conditions in aerated Fe(III)–H2SO4 solutions, Sb(III) oxidizes slightly faster than As(III). The oxidation rates of both elements were accelerated by increasing As(III), Sb(III), Fe(III), and Cl− concentrations in the presence of light. For unfiltered circumneutral water from the Giant Mine (Yellowknife, NWT, Canada), As(III) oxidized at 15–78 μmol/L/h whereas Sb(III) oxidized at 0.03–0.05 μmol/L/h during microbial exponential growth. In contrast, As(III) and Sb(III) oxidation rates of 0.01–0.03 and 0.01–0.02 μmol/L/h, respectively, were obtained in experiments performed with acid unfiltered mine waters from the Iberian Pyritic Belt (SW Spain). These results suggest that the Fe(III) formed from microbial oxidation abiotically oxidized As(III) and Sb(III). After sterile filtration of both mine water samples, neither As(III), Sb(III), nor Fe(II) oxidation was observed. Hence, under the experimental conditions, bacteria were catalyzing As and Sb oxidation in the Giant Mine waters and Fe oxidation in the acid waters of the Iberian Pyrite Belt.

Proposed mechanisms for water oxidation by Photosystem II and nanosized manganese oxides.

PubMed

Najafpour, Mohamad Mahdi; Heidari, Sima; Balaghi, S Esmael; Hołyńska, Małgorzata; Sadr, Moayad Hossaini; Soltani, Behzad; Khatamian, Maasoumeh; Larkum, Anthony W; Allakhverdiev, Suleyman I

2017-02-01

Plants, algae and cyanobacteria capture sunlight, extracting electrons from H 2 O to reduce CO 2 into sugars while releasing O 2 in the oxygenic photosynthetic process. Because of the important role of water oxidation in artificial photosynthesis and many solar fuel systems, understanding the structure and function of this unique biological catalyst forms a requisite research field. Herein the structure of the water-oxidizing complex and its ligand environment are described with reference to the 1.9Å resolution X-ray-derived crystallographic model of the water-oxidizing complex from the cyanobacterium Thermosynechococcus vulcanus. Proposed mechanisms for water oxidation by Photosystem II and nanosized manganese oxides are also reviewed and discussed in the paper. Copyright © 2016 Elsevier B.V. All rights reserved.

Simulation of uranium and plutonium oxides compounds obtained in plasma

NASA Astrophysics Data System (ADS)

Novoselov, Ivan Yu.; Karengin, Alexander G.; Babaev, Renat G.

2018-03-01

The aim of this paper is to carry out thermodynamic simulation of mixed plutonium and uranium oxides compounds obtained after plasma treatment of plutonium and uranium nitrates and to determine optimal water-salt-organic mixture composition as well as conditions for their plasma treatment (temperature, air mass fraction). Authors conclude that it needs to complete the treatment of nitric solutions in form of water-salt-organic mixtures to guarantee energy saving obtainment of oxide compounds for mixed-oxide fuel and explain the choice of chemical composition of water-salt-organic mixture. It has been confirmed that temperature of 1200 °C is optimal to practice the process. Authors have demonstrated that condensed products after plasma treatment of water-salt-organic mixture contains targeted products (uranium and plutonium oxides) and gaseous products are environmental friendly. In conclusion basic operational modes for practicing the process are showed.

Solar or UVA-Visible Photocatalytic Ozonation of Water Contaminants.

PubMed

Beltrán, Fernando J; Rey, Ana

2017-07-14

An incipient advanced oxidation process, solar photocatalytic ozonation (SPO), is reviewed in this paper with the aim of clarifying the importance of this process as a more sustainable water technology to remove priority or emerging contaminants from water. The synergism between ozonation and photocatalytic oxidation is well known to increase the oxidation rate of water contaminants, but this has mainly been studied in photocatalytic ozonation systems with lamps of different radiation wavelength, especially of ultraviolet nature (UVC, UVB, UVA). Nowadays, process sustainability is critical in environmental technologies including water treatment and reuse; the application of SPO systems falls into this category, and contributes to saving energy and water. In this review, we summarized works published on photocatalytic ozonation where the radiation source is the Sun or simulated solar light, specifically, lamps emitting radiation to cover the UVA and visible light spectra. The main aspects of the review include photoreactors used and radiation sources applied, synthesis and characterization of catalysts applied, influence of main process variables (ozone, catalyst, and pollutant concentrations, light intensity), type of water, biodegradability and ecotoxicity, mechanism and kinetics, and finally catalyst activity and stability.

Removal of estrogens through water disinfection processes and formation of by-products.

PubMed

Pereira, Renata Oliveira; Postigo, Cristina; de Alda, Miren López; Daniel, Luiz Antonio; Barceló, Damià

2011-02-01

Estrogens constitute a recognized group of environmental emerging contaminants which have been proven to induce estrogenic effects in aquatic organisms exposed to them. Low removal efficiency in wastewater treatment plants results in the presence of this type of contaminants in surface waters and also even in finished drinking water. This manuscript reviews the environmental occurrence of natural (estrone, estradiol and estriol) and synthetic (ethynyl estradiol) estrogens in different water matrices (waste, surface, ground and drinking water), and their removal mainly via chemical oxidative processes. Oxidative treatments have been observed to be very efficient in eliminating estrogens present in water; however, disinfection by-products (DBPs) are generated during the process. Characterization of these DBPs is essential to assess the risk that drinking water may potentially pose to human health since these DBPs may also have endocrine disrupting properties. This manuscript reviews the DBPs generated during oxidative processes identified so far in the literature and the estrogenicity generated by the characterized DBPs and/or by the applied disinfection technology. Copyright © 2010 Elsevier Ltd. All rights reserved.

Ceramic coating system or water oxidation environments

DOEpatents

Hong, Glenn T.

1996-01-01

A process for water oxidation of combustible materials in which during at least a part of the oxidation corrosive material is present and makes contact with at least a portion of the apparatus over a contact area on the apparatus. At least a portion of the contact surface area comprises titanium dioxide coated onto a titanium metal substrate. Such ceramic composites have been found to be highly resistant to environments encountered in the process of supercritical water oxidation. Such environments typically contain greater than 50 mole percent water, together with oxygen, carbon dioxide, and a wide range of acids, bases, and salts. Pressures are typically about 27.5 to about 1000 bar while temperatures range as high as 700.degree. C. The ceramic composites are also resistant to degradation mechanisms caused by thermal stresses.

Hydrogen-Rich Water Intake Accelerates Oral Palatal Wound Healing via Activation of the Nrf2/Antioxidant Defense Pathways in a Rat Model

PubMed Central

Orihuela-Campos, Rita Cristina; Fukui, Makoto; Ito, Hiro-O

2016-01-01

The wound healing process attempts to restore the integrity and function of the injured tissue. Additionally, proinflammatory cytokines, growth factors, and oxidative stress play important roles in wound healing. The aim of this study was to determine whether hydrogen-rich water intake induces the activation of the Nrf2/antioxidant defense pathway in rat palatal tissue, thereby reducing systemic oxidative stress and proinflammatory cytokine levels and promoting healing-associated genes. A circular excisional wound was created in the oral palatal region, and the wound healing process was observed. The rats were divided into two experimental groups in which either hydrogen-rich water or distilled water was consumed. In the drinking hydrogen-rich water, the palatal wound healing process was accelerated compared to that in the control group. As molecular hydrogen upregulated the Nrf2 pathway, systemic oxidative stresses were decreased by the activation of antioxidant activity. Furthermore, hydrogen-rich water intake reduced proinflammatory cytokine levels and promoted the expression of healing-associated factors in rat palatal tissue. In conclusion, hydrogen-rich water intake exhibited multiple beneficial effects through activation of the Nrf2/antioxidant defense pathway. The results of this study support the hypothesis that oral administration of hydrogen-rich water benefits the wound healing process by decreasing oxidative stress and inflammatory responses. PMID:26798423

Hydrogen-Rich Water Intake Accelerates Oral Palatal Wound Healing via Activation of the Nrf2/Antioxidant Defense Pathways in a Rat Model.

PubMed

Tamaki, Naofumi; Orihuela-Campos, Rita Cristina; Fukui, Makoto; Ito, Hiro-O

2016-01-01

The wound healing process attempts to restore the integrity and function of the injured tissue. Additionally, proinflammatory cytokines, growth factors, and oxidative stress play important roles in wound healing. The aim of this study was to determine whether hydrogen-rich water intake induces the activation of the Nrf2/antioxidant defense pathway in rat palatal tissue, thereby reducing systemic oxidative stress and proinflammatory cytokine levels and promoting healing-associated genes. A circular excisional wound was created in the oral palatal region, and the wound healing process was observed. The rats were divided into two experimental groups in which either hydrogen-rich water or distilled water was consumed. In the drinking hydrogen-rich water, the palatal wound healing process was accelerated compared to that in the control group. As molecular hydrogen upregulated the Nrf2 pathway, systemic oxidative stresses were decreased by the activation of antioxidant activity. Furthermore, hydrogen-rich water intake reduced proinflammatory cytokine levels and promoted the expression of healing-associated factors in rat palatal tissue. In conclusion, hydrogen-rich water intake exhibited multiple beneficial effects through activation of the Nrf2/antioxidant defense pathway. The results of this study support the hypothesis that oral administration of hydrogen-rich water benefits the wound healing process by decreasing oxidative stress and inflammatory responses.

An overview on the removal of synthetic dyes from water by electrochemical advanced oxidation processes.

PubMed

Nidheesh, P V; Zhou, Minghua; Oturan, Mehmet A

2018-04-01

Wastewater containing dyes are one of the major threats to our environment. Conventional methods are insufficient for the removal of these persistent organic pollutants. Recently much attention has been received for the oxidative removal of various organic pollutants by electrochemically generated hydroxyl radical. This review article aims to provide the recent trends in the field of various Electrochemical Advanced Oxidation Processes (EAOPs) used for removing dyes from water medium. The characteristics, fundamentals and recent advances in each processes namely anodic oxidation, electro-Fenton, peroxicoagulation, fered Fenton, anodic Fenton, photoelectro-Fenton, sonoelectro-Fenton, bioelectro-Fenton etc. have been examined in detail. These processes have great potential to destroy persistent organic pollutants in aqueous medium and most of the studies reported complete removal of dyes from water. The great capacity of these processes indicates that EAOPs constitute a promising technology for the treatment of the dye contaminated effluents. Copyright © 2018 Elsevier Ltd. All rights reserved.

System and process for producing fuel with a methane thermochemical cycle

DOEpatents

Diver, Richard B.

2015-12-15

A thermochemical process and system for producing fuel are provided. The thermochemical process includes reducing an oxygenated-hydrocarbon to form an alkane and using the alkane in a reforming reaction as a reducing agent for water, a reducing agent for carbon dioxide, or a combination thereof. Another thermochemical process includes reducing a metal oxide to form a reduced metal oxide, reducing an oxygenated-hydrocarbon with the reduced metal oxide to form an alkane, and using the alkane in a reforming reaction as a reducing agent for water, a reducing agent for carbon dioxide, or a combination thereof. The system includes a reformer configured to perform a thermochemical process.

Photocatalytic Oxidation of Oil Contaminated Water Using TiO2/UV

NASA Astrophysics Data System (ADS)

Vargas Solla, Monica; Romero Rojas, Jairo

2017-04-01

Currently, oil is one of the most used energy sources all around the world, for example to make motor engines work. That prevailing usage of oil is the reason why water sources are under serious pollution risks with compounds that are hard to remove, such as hydrocarbons. There are a few water treatment processes known as Advanced Oxidation Processes, which search for a way to treat polluted water with toxic refractory compounds, to make its reuse more feasible and to avoid or at least appease the injurious effects of pollution over ecosystems. A heterogeneous photocatalysis water treatment technology, sorted as an Advanced Oxidation Process, which is intended to treat refractory compound polluted water by the use of TiO2 and UV light, is presented in this investigation. The evidence about its efficiency in hydrocarbon removal from used motor oil polluted water, since it is an extremely important pollutant due to its complexity, toxicity and recalcitrant characteristics, is also presented through COD, Oil and Grease and Hydrocarbons analysis.

Supercritical water oxidation - Microgravity solids separation

NASA Technical Reports Server (NTRS)

Killilea, William R.; Hong, Glenn T.; Swallow, Kathleen C.; Thomason, Terry B.

1988-01-01

This paper discusses the application of supercritical water oxidation (SCWO) waste treatment and water recycling technology to the problem of waste disposal in-long term manned space missions. As inorganic constituents present in the waste are not soluble in supercritical water, they must be removed from the organic-free supercritical fluid reactor effluent. Supercritical water reactor/solids separator designs capable of removing precipitated solids from the process' supercritical fluid in zero- and low- gravity environments are developed and evaluated. Preliminary experiments are then conducted to test the concepts. Feed materials for the experiments are urine, feces, and wipes with the addition of reverse osmosis brine, the rejected portion of processed hygiene water. The solid properties and their influence on the design of several oxidation-reactor/solids-separator configurations under study are presented.

DETOX{sup SM} catalyzed wet oxidation as a highly suitable pretreatment for vitrification

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

Rogers, T.W.; Dhooge, P.M.; Goldblatt, S.D.

1995-11-01

A catalyzed wet oxidation process has been developed which uses ferric iron in an acidic water solution to oxidize organic compounds in the presence of platinum ion and/or ruthenium ion catalysts. The process is capable of oxidizing a wide range of organic compounds to carbon dioxide and water with great efficiency. The process has been tested in the bench-scale with many different types of organics. Conceptual engineering for application of the process to treatment of liquid and solid organic waste materials has been followed by engineering design for a demonstration unit. Fabrication of the unit and demonstration on hazardous andmore » mixed wastes at two Department of Energy sites is planned in 1995 through 1997.« less

Characterization of interfacial reactions and oxide films on 316L stainless steel in various simulated PWR primary water environments

NASA Astrophysics Data System (ADS)

Chen, Junjie; Xiao, Qian; Lu, Zhanpeng; Ru, Xiangkun; Peng, Hao; Xiong, Qi; Li, Hongjuan

2017-06-01

The effect of water chemistry on the electrochemical and oxidizing behaviors of 316L SS was investigated in hydrogenated, deaerated and oxygenated PWR primary water at 310 °C. Water chemistry significantly influenced the electrochemical impedance spectroscopy parameters. The highest charge-transfer resistance and oxide-film resistance occurred in oxygenated water. The highest electric double-layer capacitance and constant phase element of the oxide film were in hydrogenated water. The oxide films formed in deaerated and hydrogenated environments were similar in composition but different in morphology. An oxide film with spinel outer particles and a compact and Cr-rich inner layer was formed in both hydrogenated and deaerated water. Larger and more loosely distributed outer oxide particles were formed in deaerated water. In oxygenated water, an oxide film with hematite outer particles and a porous and Ni-rich inner layer was formed. The reaction kinetics parameters obtained by electrochemical impedance spectroscopy measurements and oxidation film properties relating to the steady or quasi-steady state conditions in the time-period of measurements could provide fundamental information for understanding stress corrosion cracking processes and controlling parameters.

Porous graphene-based membranes for water purification from metal ions at low differential pressures.

PubMed

Park, Jaewoo; Bazylewski, Paul; Fanchini, Giovanni

2016-05-14

A new generation of membranes for water purification based on weakly oxidized and nanoporous few-layer graphene is here introduced. These membranes dramatically decrease the high energy requirements of water purification by reverse osmosis. They combine the advantages of porous and non-oxidized single-layer graphene, offering energy-efficient water filtration at relatively low differential pressures, and highly oxidized graphene oxide, exhibiting high performance in terms of impurity adsorption. In the reported fabrication process, leaks between juxtaposed few-layer graphene flakes are sealed by thermally annealed colloidal silica, in a treatment that precedes the opening of (sub)nanometre-size pores in graphene. This process, explored for the first time in this work, results in nanoporous graphene flakes that are water-tight at the edges without occluding the (sub)nanopores. With this method, removal of impurities from water occurs through a combination of size-based pore rejection and pore-edge adsorption. Thinness of graphene flakes allows these membranes to achieve water purification from metal ions in concentrations of few parts-per-million at differential pressures as low as 30 kPa, outperforming existing graphene or graphene oxide purification systems with comparable flow rates.

Porous graphene-based membranes for water purification from metal ions at low differential pressures

NASA Astrophysics Data System (ADS)

Park, Jaewoo; Bazylewski, Paul; Fanchini, Giovanni

2016-05-01

A new generation of membranes for water purification based on weakly oxidized and nanoporous few-layer graphene is here introduced. These membranes dramatically decrease the high energy requirements of water purification by reverse osmosis. They combine the advantages of porous and non-oxidized single-layer graphene, offering energy-efficient water filtration at relatively low differential pressures, and highly oxidized graphene oxide, exhibiting high performance in terms of impurity adsorption. In the reported fabrication process, leaks between juxtaposed few-layer graphene flakes are sealed by thermally annealed colloidal silica, in a treatment that precedes the opening of (sub)nanometre-size pores in graphene. This process, explored for the first time in this work, results in nanoporous graphene flakes that are water-tight at the edges without occluding the (sub)nanopores. With this method, removal of impurities from water occurs through a combination of size-based pore rejection and pore-edge adsorption. Thinness of graphene flakes allows these membranes to achieve water purification from metal ions in concentrations of few parts-per-million at differential pressures as low as 30 kPa, outperforming existing graphene or graphene oxide purification systems with comparable flow rates.

Ground Water Sample Preservation at In-Situ Chemical Oxidation Sites – Recommended Guidelines

EPA Pesticide Factsheets

This issue paper describes the recommended processes for sampling at in Situ Chemical Oxidation sites. Care must be taken because the oxidizing chemicals used for the remediation process can create an erroneously low sampling result.

Atomic origins of water-vapour-promoted alloy oxidation

NASA Astrophysics Data System (ADS)

Luo, Langli; Su, Mao; Yan, Pengfei; Zou, Lianfeng; Schreiber, Daniel K.; Baer, Donald R.; Zhu, Zihua; Zhou, Guangwen; Wang, Yanting; Bruemmer, Stephen M.; Xu, Zhijie; Wang, Chongmin

2018-06-01

The presence of water vapour, intentional or unavoidable, is crucial to many materials applications, such as in steam generators, turbine engines, fuel cells, catalysts and corrosion1-4. Phenomenologically, water vapour has been noted to accelerate oxidation of metals and alloys5,6. However, the atomistic mechanisms behind such oxidation remain elusive. Through direct in situ atomic-scale transmission electron microscopy observations and density functional theory calculations, we reveal that water-vapour-enhanced oxidation of a nickel-chromium alloy is associated with proton-dissolution-promoted formation, migration, and clustering of both cation and anion vacancies. Protons derived from water dissociation can occupy interstitial positions in the oxide lattice, consequently lowering vacancy formation energy and decreasing the diffusion barrier of both cations and anions, which leads to enhanced oxidation in moist environments at elevated temperatures. This work provides insights into water-vapour-enhanced alloy oxidation and has significant implications in other material and chemical processes involving water vapour, such as corrosion, heterogeneous catalysis and ionic conduction.

Atomic origins of water-vapour-promoted alloy oxidation.

PubMed

Luo, Langli; Su, Mao; Yan, Pengfei; Zou, Lianfeng; Schreiber, Daniel K; Baer, Donald R; Zhu, Zihua; Zhou, Guangwen; Wang, Yanting; Bruemmer, Stephen M; Xu, Zhijie; Wang, Chongmin

2018-06-01

The presence of water vapour, intentional or unavoidable, is crucial to many materials applications, such as in steam generators, turbine engines, fuel cells, catalysts and corrosion 1-4 . Phenomenologically, water vapour has been noted to accelerate oxidation of metals and alloys 5,6 . However, the atomistic mechanisms behind such oxidation remain elusive. Through direct in situ atomic-scale transmission electron microscopy observations and density functional theory calculations, we reveal that water-vapour-enhanced oxidation of a nickel-chromium alloy is associated with proton-dissolution-promoted formation, migration, and clustering of both cation and anion vacancies. Protons derived from water dissociation can occupy interstitial positions in the oxide lattice, consequently lowering vacancy formation energy and decreasing the diffusion barrier of both cations and anions, which leads to enhanced oxidation in moist environments at elevated temperatures. This work provides insights into water-vapour-enhanced alloy oxidation and has significant implications in other material and chemical processes involving water vapour, such as corrosion, heterogeneous catalysis and ionic conduction.

Effect of water vapor on evolution of a thick Pt-layer modified oxide on the NiCoCrAl alloy at high temperature

NASA Astrophysics Data System (ADS)

Song, Peng; He, Xuan; Xiong, Xiping; Ma, Hongqing; Song, Qunling; Lü, Jianguo; Lu, Jiansheng

2018-03-01

To investigate the effect of water vapor on the novel Pt-containing oxide growth behavior, Pt-addition within the oxide layer on the surface of NiCoCrAl coating and furnace cycle tests were carried out at 1050 °C in air and air plus water vapor. The thick Pt-containing oxide layer on NiCoCrAl exhibits a different oxidation growth behavior compared to the conventional Pt-diffusion metallic coatings. The Pt-containing oxide after oxidation in air plus water vapor showed a much thicker oxide layer compare to the ones without Pt addition, and also presented a much better coating adhesion. During the oxidation process in air, Pt promotes the spinel (NiCr2O4) formation. However, the Cr2O3 formed in air with water vapor and fixed Pt within the complex oxide layer. The water vapor promoted the Ni and Co outer-diffusion, and combined with Pt to form CoPt compounds on the surface of the NiCoCrAl coating system.

Chemical, electrochemical and photochemical molecular water oxidation catalysts.

PubMed

Bofill, Roger; García-Antón, Jordi; Escriche, Lluís; Sala, Xavier

2015-11-01

Hydrogen release from the splitting of water by simply using sunlight as the only energy source is an old human dream that could finally become a reality. This process involves both the reduction and oxidation of water into hydrogen and oxygen, respectively. While the first process has been fairly overcome, the conversion of water into oxygen has been traditionally the bottleneck process hampering the development of a sustainable hydrogen production based on water splitting. Fortunately, a revolution in this field has occurred during the past decade, since many research groups have been conducting an intense research in this area. Thus, while molecular, well-characterized catalysts able to oxidize water were scarce just five years ago, now a wide range of transition metal based compounds has been reported as active catalysts for this transformation. This review reports the most prominent key advances in the field, covering either examples where the catalysis is triggered chemically, electrochemically or photochemically. Copyright © 2014 Elsevier B.V. All rights reserved.

HANDBOOK ON ADVANCED PHOTOCHEMICAL OXIDATION ...

EPA Pesticide Factsheets

This handbook summarizes commercial-scale system performance and cost data for advanced photochemical oxidation (APO) treatment of contaminated water, air, and solids. Similar information from pilot- and bench-scale evaluations of APO processes is also included to supplement the commercial-scale data. Performance and cost data is summarized for various APO processes, including vacuum ultraviolet (VUV) photolysis, ultraviolet (UV)/oxidation, photo-Fenton, and dye- or semiconductor-sensitized APO processes. This handbook is intended to assist engineering practitioners in evaluating the applicability of APO processes and in selecting one or more such processes for site-specific evaluation.APO has been shown to be effective in treating contaminated water and air. Regarding contaminated water treatment, UV/oxidation has been evaluated for the most contaminants, while VUV photolysis has been evaluated for the fewest. Regarding contaminated air treatment, the sensitized APO processes have been evaluated for the most contaminants, while VUV photolysis has been evaluated for the fewest.APO processes for treating contaminated solids generally involve treatment of contaminated slurry or leachate generated using an extraction process such as soil washing. APO has been shown to be effective in treating contaminated solids, primarily at the bench-scale level. Information

Development and testing of a wet oxidation waste processing system. [for waste treatment aboard manned spacecraft

NASA Technical Reports Server (NTRS)

Weitzmann, A. L.

1977-01-01

The wet oxidation process is considered as a potential treatment method for wastes aboard manned spacecraft for these reasons: (1) Fecal and urine wastes are processed to sterile water and CO2 gas. However, the water requires post-treatment to remove salts and odor; (2) the residual ash is negligible in quantity, sterile and easily collected; and (3) the product CO2 gas can be processed through a reduction step to aid in material balance if needed. Reaction of waste materials with oxygen at elevated temperature and pressure also produces some nitrous oxide, as well as trace amounts of a few other gases.

Iron oxidation kinetics and phosphate immobilization along the flow-path from groundwater into surface water

NASA Astrophysics Data System (ADS)

van der Grift, B.; Rozemeijer, J. C.; Griffioen, J.; van der Velde, Y.

2014-06-01

The retention of phosphorus in surface waters though co-precipitation of phosphate with Fe-oxyhydroxides during exfiltration of anaerobic Fe(II) rich groundwater is not well understood. We developed an experimental field set-up to study Fe(II) oxidation and P immobilization along the flow-path from groundwater to surface water in an agricultural experimental catchment of a small lowland river. We physically separated tube drain effluent from groundwater discharge before it entered a ditch in an agricultural field. Through continuous discharge measurements and weekly water quality sampling of groundwater, tube drain water, exfiltrated groundwater, and ditch water, we investigated Fe(II) oxidation kinetics and P immobilization processes. The oxidation rate inferred from our field measurements closely agreed with the general rate law for abiotic oxidation of Fe(II) by O2. Seasonal changes in climatic conditions affected the Fe(II) oxidation process. Lower pH and lower temperatures in winter (compared to summer) resulted in low Fe oxidation rates. After exfiltration to the surface water, it took a couple of days to more than one week before complete oxidation of Fe(II) is reached. In summer time, Fe oxidation rates were much higher. The Fe concentrations in the exfiltrated groundwater were low, indicating that dissolved Fe(II) is completely oxidized prior to inflow into a ditch. While the Fe oxidation rates reduce drastically from summer to winter, P concentrations remained high in the groundwater and an order of magnitude lower in the surface water throughout the year. This study shows very fast immobilisation of dissolved P during the initial stage of the Fe(II) oxidation proces which results in P-depleted water before Fe(II) is competly depleted. This cannot be explained by surface complexation of phosphate to freshly formed Fe-oxyhydroxides but indicates the formation of Fe(III)-phosphate precipitates. The formation of Fe(III)-phosphates at redox gradients seems an important geochemical mechanism in the transformation of dissolved phosphate to particulate phosphate and, therefore, a major control on the P retention in natural waters that drain anaerobic aquifers.

ADVANCED OXIDATION PROCESSES (AOPS) FOR DESTRUCTION OF METHYL TERTIARY BUTYL ETHER (MTBE -AN UNREGULATED CONTAMINANT) IN DRINKING WATER

EPA Science Inventory

Advanced oxidation processes (AOPs) provide a promising treatment option for the destruction of MTBE directly in surface and ground waters. An ongoing study is evaluating the ability of three AOPs; hydrogen peroxide/ozone (H2O2/ O3), ultraviolet irradiation/ozone (UV/O3) and ultr...

Water disinfection: A relationship between ozone and aldehyde production

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

Gilli, G.; Scursatone, E.; Palin, L.

In the water potabilization plant of Turin city (Italy), the oxidation process is carried out with ozone. Due to its well-known insufficient performance, it is necessary to add alternative oxidants (hypochlorite ion and chlorine dioxide). In this paper, the authors discuss the formation of linear carbonyl groups during surface water treatment in Turni. The results obtained in the field confirm the synthesis of some aliphatic carbonyl compounds of low molecular weight. This phenomenon happens preeminently during the ozone disinfection process and, secondarily, during the other disinfection processes. Experimental results show that, in this last event, chlorine reacts with organic substances,more » and in a second moment, after organics consumption, if chlorine is still in a sufficient concentration, oxidizing them.« less

Physical/chemical closed-loop water-recycling

NASA Technical Reports Server (NTRS)

Herrmann, Cal C.; Wydeven, Theodore

1991-01-01

Water needs, water sources, and means for recycling water are examined in terms appropriate to the water quality requirements of a small crew and spacecraft intended for long duration exploration missions. Inorganic, organic, and biological hazards are estimated for waste water sources. Sensitivities to these hazards for human uses are estimated. The water recycling processes considered are humidity condensation, carbon dioxide reduction, waste oxidation, distillation, reverse osmosis, pervaporation, electrodialysis, ion exchange, carbon sorption, and electrochemical oxidation. Limitations and applications of these processes are evaluated in terms of water quality objectives. Computerized simulation of some of these chemical processes is examined. Recommendations are made for development of new water recycling technology and improvement of existing technology for near term application to life support systems for humans in space. The technological developments are equally applicable to water needs on Earth, in regions where extensive water recycling is needed or where advanced water treatment is essential to meet EPA health standards.

Oxidation of carbon monoxide, hydrogen peroxide and water at a boron doped diamond electrode: the competition for hydroxyl radicals.

PubMed

Kisacik, Izzet; Stefanova, Ana; Ernst, Siegfried; Baltruschat, Helmut

2013-04-07

Boron doped diamond (BDD) electrodes have an extremely high over-voltage for oxygen evolution from water, which favours its use in oxidation processes of other compounds at high potentials. We used a rotating ring disc (RRDE) assembly and differential electrochemical mass spectrometry (DEMS) in order to monitor the consumption or the production of species in the course of the electrode processes. By intercepting the intermediate of the electrochemical water oxidation with chemical reactions we demonstrate clearly, albeit indirectly, that in the water oxidation process at BDD above 2.5 V the first step is the formation of ˙OH radicals. The electro-oxidation of CO to CO2 at BDD electrodes proceeds only via a first attack by ˙OH radicals followed by a further electron transfer to the electrode. At potentials below the onset of oxygen evolution from water, H2O2 is oxidised by a direct electron transfer to the BDD electrode, while at higher potentials, two different reactions paths compete for the ˙OH radicals formed in the first electron transfer from water: one, where these ˙OH radicals react with each other followed by further electron transfers leading to O2 on the one hand and one, where ˙OH radicals react with other species like H2O2 or CO with subsequent electron transfers on the other hand.

Using digital flow cytometry to assess the degradation of three cyanobacteria species after oxidation processes.

PubMed

Wert, Eric C; Dong, Mei Mei; Rosario-Ortiz, Fernando L

2013-07-01

Depending on drinking water treatment conditions, oxidation processes may result in the degradation of cyanobacteria cells causing the release of toxic metabolites (microcystin), odorous metabolites (MIB, geosmin), or disinfection byproduct precursors. In this study, a digital flow cytometer (FlowCAM(®)) in combination with chlorophyll-a analysis was used to evaluate the ability of ozone, chlorine, chlorine dioxide, and chloramine to damage or lyse cyanobacteria cells added to Colorado River water. Microcystis aeruginosa (MA), Oscillatoria sp. (OSC) and Lyngbya sp. (LYN) were selected for the study due to their occurrence in surface water supplies, metabolite production, and morphology. Results showed that cell damage was observed without complete lysis or fragmentation of the cell membrane under many of the conditions tested. During ozone and chlorine experiments, the unicellular MA was more susceptible to oxidation than the filamentous OSC and LYN. Rate constants were developed based on the loss of chlorophyll-a and oxidant exposure, which showed the oxidants degraded MA, OSC, and LYN according to the order of ozone > chlorine ~ chlorine dioxide > chloramine. Digital and binary images taken by the digital flow cytometer provided qualitative insight regarding cell damage. When applying this information, drinking water utilities can better understand the risk of cell damage or lysis during oxidation processes. Copyright © 2013 Elsevier Ltd. All rights reserved.

A method for recovery of iron, titanium, and vanadium from vanadium-bearing titanomagnetite

NASA Astrophysics Data System (ADS)

Zhang, Yi-min; Wang, Li-na; Chen, De-sheng; Wang, Wei-jing; Liu, Ya-hui; Zhao, Hong-xin; Qi, Tao

2018-02-01

An innovative method for recovering valuable elements from vanadium-bearing titanomagnetite is proposed. This method involves two procedures: low-temperature roasting of vanadium-bearing titanomagnetite and water leaching of roasting slag. During the roasting process, the reduction of iron oxides to metallic iron, the sodium oxidation of vanadium oxides to water-soluble sodium vanadate, and the smelting separation of metallic iron and slag were accomplished simultaneously. Optimal roasting conditions for iron/slag separation were achieved with a mixture thickness of 42.5 mm, a roasting temperature of 1200°C, a residence time of 2 h, a molar ratio of C/O of 1.7, and a sodium carbonate addition of 70wt%, as well as with the use of anthracite as a reductant. Under the optimal conditions, 93.67% iron from the raw ore was recovered in the form of iron nugget with 95.44% iron grade. After a water leaching process, 85.61% of the vanadium from the roasting slag was leached, confirming the sodium oxidation of most of the vanadium oxides to water-soluble sodium vanadate during the roasting process. The total recoveries of iron, vanadium, and titanium were 93.67%, 72.68%, and 99.72%, respectively.

A self-improved water-oxidation catalyst: is one site really enough?

PubMed

López, Isidoro; Ertem, Mehmed Z; Maji, Somnath; Benet-Buchholz, Jordi; Keidel, Anke; Kuhlmann, Uwe; Hildebrandt, Peter; Cramer, Christopher J; Batista, Victor S; Llobet, Antoni

2014-01-03

The homogeneous catalysis of water oxidation by transition-metal complexes has experienced spectacular development over the last five years. Practical energy-conversion schemes, however, require robust catalysts with large turnover frequencies. Herein we introduce a new oxidatively rugged and powerful dinuclear water-oxidation catalyst that is generated by self-assembly from a mononuclear catalyst during the catalytic process. Our kinetic and DFT computational analysis shows that two interconnected catalytic cycles coexist while the mononuclear system is slowly and irreversibly converted into the more stable dinuclear system: an extremely robust water-oxidation catalyst that does not decompose over extended periods of time. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Catalytic processes for space station waste conversion

NASA Technical Reports Server (NTRS)

Schoonover, M. W.; Madsen, R. A.

1986-01-01

Catalytic techniques for processing waste products onboard space vehicles were evaluated. The goal of the study was the conversion of waste to carbon, wash water, oxygen and nitrogen. However, the ultimate goal is conversion to plant nutrients and other materials useful in closure of an ecological life support system for extended planetary missions. The resulting process studied involves hydrolysis at 250 C and 600 psia to break down and compact cellulose material, distillation at 100 C to remove water, coking at 450 C and atmospheric pressure, and catalytic oxidation at 450 to 600 C and atmospheric pressure. Tests were conducted with a model waste to characterize the hydrolysis and coking processes. An oxidizer reactor was sized based on automotive catalytic conversion experience. Products obtained from the hydrolysis and coking steps included a solid residue, gases, water condensate streams, and a volatile coker oil. Based on the data obtained, sufficient component sizing was performed to make a preliminary comparison of the catalytic technique with oxidation for processing waste for a six-man spacecraft. Wet oxidation seems to be the preferred technique from the standpoint of both component simplicity and power consumption.

An alternative process to treat boiler feed water for reuse.

PubMed

Guirgis, Adel; Ghosh, Jyoti P; Achari, Gopal; Langford, Cooper H; Banerjee, Daliya

2012-09-01

A bench-scale process to treat boiler feed water for reuse in steam generation was developed. Industrial water samples from a steam-assisted gravity drainage plant in northern Alberta, Canada, were obtained and samples characterized. The technology, which consists of coagulation-settling to remove oil/grease and particulates followed by an advanced oxidative treatment, led to clean water samples with negligible organic carbon. Coagulation followed by settling removed most particulates and some insoluble organics. The advanced oxidative treatment removed any remaining color in the samples, decreased the organic content to near-zero, and provided water ready for reuse.

Experimental Study on Treatment of Dyeing Wastewater by Activated Carbon Adsorption, Coagulation and Fenton Oxidation

NASA Astrophysics Data System (ADS)

Xiaoxu, SUN; Jin, XU; Xingyu, LI

2017-12-01

In this paper dyeing waste water was simulated by reactive brilliant blue XBR, activated carbon adsorption process, coagulation process and chemical oxidation process were used to treat dyeing waste water. In activated carbon adsorption process and coagulation process, the water absorbance values were measured. The CODcr value of water was determined in Fenton chemical oxidation process. Then, the decolorization rate and COD removal rate were calculated respectively. The results showed that the optimum conditions of activated carbon adsorption process were as follows: pH=2, the dosage of activated carbon was 1.2g/L, the adsorption reaction time was 60 min, and the average decolorization rate of the three parallel experiments was 85.30%. The optimum conditions of coagulation experiment were as follows: pH=8~9, PAC dosage was 70mg/L, stirring time was 20min, standing time was 45min, the average decolorization rate of the three parallel experiments was 74.48%. The optimum conditions for Fenton oxidation were Fe2+ 0.05g/L, H2O2 (30%) 14mL/L, pH=3, reaction time 40min. The average CODcr removal rate was 69.35% in three parallel experiments. It can be seen that in the three methods the activated carbon adsorption treatment of dyeing wastewater was the best one.

Principles, efficiency, and blueprint character of solar-energy conversion in photosynthetic water oxidation.

PubMed

Dau, Holger; Zaharieva, Ivelina

2009-12-21

Photosynthesis in plants and cyanobacteria involves two protein-cofactor complexes which are denoted as photosystems (PS), PSII and PSI. These solar-energy converters have powered life on earth for approximately 3 billion years. They facilitate light-driven carbohydrate formation from H(2)O and CO(2), by oxidizing the former and reducing the latter. PSII splits water in a process driven by light. Because all attractive technologies for fuel production driven by solar energy involve water oxidation, recent interest in this process carried out by PSII has increased. In this Account, we describe and apply a rationale for estimating the solar-energy conversion efficiency (eta(SOLAR)) of PSII: the fraction of the incident solar energy absorbed by the antenna pigments and eventually stored in form of chemical products. For PSII at high concentrations, approximately 34% of the incident solar energy is used for creation of the photochemistry-driving excited state, P680*, with an excited-state energy of 1.83 eV. Subsequent electron transfer results in the reduction of a bound quinone (Q(A)) and oxidation of the Tyr(Z) within 1 micros. This radical-pair state is stable against recombination losses for approximately 1 ms. At this level, the maximal eta(SOLAR) is 23%. After the essentially irreversible steps of quinone reduction and water oxidation (the final steps catalyzed by the PSII complex), a maximum of 50% of the excited-state energy is stored in chemical form; eta(SOLAR) can be as high as 16%. Extending our considerations to a photosynthetic organism optimized to use PSII and PSI to drive H(2) production, the theoretical maximum of the solar-energy conversion efficiency would be as high as 10.5%, if all electrons and protons derived from water oxidation were used for H(2) formation. The above performance figures are impressive, but they represent theoretical maxima and do not account for processes in an intact organism that lower these yields, such as light saturation, photoinhibitory, protective, and repair processes. The overpotential for catalysis of water oxidation at the Mn(4)Ca complex of PSII may be as low as 0.3 V. To address the specific energetics of water oxidation at the Mn complex of PSII, we propose a new conceptual framework that will facilitate quantitative considerations on the basis of oxidation potentials and pK values. In conclusion, photosynthetic water oxidation works at high efficiency and thus can serve as both an inspiring model and a benchmark in the development of future technologies for production of solar fuels.

Investigation of Iron Oxide Morphology in a Cyclic Redox Water Splitting Process for Hydrogen Generation

PubMed Central

Bobek, Michael M.; Stehle, Richard C.; Hahn, David W.

2012-01-01

A solar fuels generation research program is focused on hydrogen production by means of reactive metal water splitting in a cyclic iron-based redox process. Iron-based oxides are explored as an intermediary reactive material to dissociate water molecules at significantly reduced thermal energies. With a goal of studying the resulting oxide chemistry and morphology, chemical assistance via CO is used to complete the redox cycle. In order to exploit the unique characteristics of highly reactive materials at the solar reactor scale, a monolithic laboratory scale reactor has been designed to explore the redox cycle at temperatures ranging from 675 to 875 K. Using high resolution scanning electron microscope (SEM) and electron dispersive X-ray spectroscopy (EDS), the oxide morphology and the oxide state are quantified, including spatial distributions. These images show the change of the oxide layers directly after oxidation and after reduction. The findings show a significant non-stoichiometric O/Fe gradient in the atomic ratio following oxidation, which is consistent with a previous kinetics model, and a relatively constant, non-stoichiometric O/Fe atomic ratio following reduction.

Single-step treatment of 2,4-dinitrotoluene via zero-valent metal reduction and chemical oxidation.

PubMed

Thomas, J Mathew; Hernandez, Rafael; Kuo, Chiang-Hai

2008-06-30

Many nitroaromatic compounds (NACs) are considered toxic and potential carcinogens. The purpose of this study was to develop an integrated reductive/oxidative process for treating NACs contaminated waters. The process consists of the combination of zero-valent iron and an ozonation based treatment technique. Corrosion promoters are added to the contaminated water to minimize passivation of the metallic species. Water contaminated with 2,4-dinitrotoluene (DNT) was treated with the integrated process using a recirculated batch reactor. It was demonstrated that addition of corrosion promoters to the contaminated water enhances the reduction of 2,4-DNT with zero-valent iron. The addition of corrosion promoters resulted in 62% decrease in 2,4-DNT concentration to 2,4-diaminotoluene. The data shows that iron reduced the 2,4-DNT and ozone oxidized these products resulting in a 73% removal of TOC and a 96% decrease in 2,4-DNT concentration.

Comparison of seven kinds of drinking water treatment processes to enhance organic material removal: a pilot test.

PubMed

Chen, Chao; Zhang, Xiaojian; He, Wenjie; Lu, Wei; Han, Hongda

2007-08-15

Organic matter in source water has presented many challenges in the field of water purification, especially for conventional treatment. A two-year-long pilot test comparing water treatment processes was conducted to enhance organic matter removal. The tested process combinations included the conventional process, conventional plus advanced treatment, pre-oxidation plus conventional process and pre-oxidation plus conventional plus advanced treatment. The efficiency of each kind of process was assayed with the comprehensive indices of COD(Mn), TOC, UV(254), AOC, BDOC, THMs, and HAAs and their formation potential. The results showed that the combination of the conventional process and O(3)-BAC provides integrated removal of organic matter and meets the required standards. It is the best performing treatment tested in this investigation for treating polluted source water in China. Moreover, much attention should be paid to organic removal before disinfection to control DBP formation and preserve biostability. This paper also reports the range of efficiency of each unit process to calculate the total efficiency of different process combinations in order to help choose the appropriate water treatment process.

Pathway fraction of bromate formation during O₃ and O₃/H₂O₂ processes in drinking water treatment.

PubMed

Qi, Shengqi; Mao, Yuqin; Lv, Miao; Sun, Lili; Wang, Xiaomao; Yang, Hongwei; Xie, Yuefeng F

2016-02-01

Ozone process has been widely used for drinking water treatment recently. In the oxidation process, bromate is formed by three pathways, i.e., the direct pathway, the direct-indirect pathway and the indirect-direct pathway. This study developed a method to calculate the percentage of these three pathways for bromate formation during O3 process and O3/H2O2 process. Two kinds of water, distilled water containing bromide (DW) and surface water from the Yellow River (SW) were selected as raw rater. The result showed that in natural water systems, the direct-indirect pathway was dominant for bromate formation during the oxidation process. When 3 mg L(-1) O3 was used as the only oxidant, nearly 26% of bromide ion was transferred into bromate in two kinds of water after 80 min. The dominant pathway in DW was the direct pathway (48.5%) and the direct-indirect pathway (46.5%), while that was the direct-indirect pathway (68.9%) in SW. When O3/H2O2 were used as oxidants, as the H2O2 dosage increased, the fractions of bromate formation by direct pathway and direct-indirect pathway decreased, while that by indirect-direct pathway increased. The conversion ratio from bromide to bromate first kept stable or increased, then decreased and reached its minimum when [H2O2]/[O3] ratio was 1.0 in DW and 1.5 in SW. Under this condition the indirect-direct pathway took the largest fraction of 70.7% in DW and 64.0% in SW, respectively. Copyright © 2015. Published by Elsevier Ltd.

Development of a household waste treatment subsystem, volume 1. [with water conservation features

NASA Technical Reports Server (NTRS)

Gresko, T. M.; Murray, R. W.

1973-01-01

The domestic waste treatment subsystem was developed to process the daily liquid and non-metallic solid wastes provided by a family of four people. The subsystem was designed to be connected to the sewer line of a household which contained water conservation features. The system consisted of an evaporation technique to separate liquids from solids, an incineration technique for solids reduction, and a catalytic oxidizer for eliminating noxious gases from evaporation and incineration processes. All wastes were passed through a grinder which masticated the solids and deposited them in a settling tank. The liquids were transferred through a cleanable filter into a holding tank. From here the liquids were sprayed into an evaporator and a spray chamber where evaporation occurred. The resulting vapors were processed by catalytic oxidation. Water and latent energy were recovered in a combination evaporator/condenser heat exchanger. The solids were conveyed into an incinerator and reduced to ash while the incineration gases were passed through the catalytic oxidizer along with the processed water vapor.

Oxidative processes in soybean and pea seeds: effect of light, temperature, and water content

NASA Technical Reports Server (NTRS)

Vertucci, C. W.; Leopold, A. C.

1987-01-01

Oxidative processes are probable determinants of longevity of seeds in storage. Measurements of actual oxygen uptake rates were made for soybean and pea seeds as a comparison of short and long lived seeds when light, temperature, and moisture contents were varied. In both peas and soybeans, the oxygen uptake was depressed at low temperatures (<16 degrees C) and low water contents (< 0.25 gram H2O per gram dry weight). Apparent activation energies under these conditions are very high, while apparent activation energies of seeds at higher water contents and at temperatures greater than 22 degrees C are much less. Light enhances the level of oxygen uptake in pea, but reduces the level of oxygen uptake in soybean. The complexities of the interactions of oxygen uptake with environmental conditions in soybean compared to pea suggest that oxidative processes occur in soybean at low water contents, but are essentially absent in pea. It is suggested that the additional oxidative processes in soybean with moisture contents between 0.10 and 0.24 gram per gram may contribute to the poorer longevity of soybean seed compared to pea seed.

Process for treating effluent from a supercritical water oxidation reactor

DOEpatents

Barnes, Charles M.; Shapiro, Carolyn

1997-01-01

A method for treating a gaseous effluent from a supercritical water oxidation reactor containing entrained solids is provided comprising the steps of expanding the gas/solids effluent from a first to a second lower pressure at a temperature at which no liquid condenses; separating the solids from the gas effluent; neutralizing the effluent to remove any acid gases; condensing the effluent; and retaining the purified effluent to the supercritical water oxidation reactor.

Catalytic methods using molecular oxygen for treatment of PMMS and ECLSS waste streams, volume 2

NASA Technical Reports Server (NTRS)

Akse, James R.

1992-01-01

Catalytic oxidation has proven to be an effective addition to the baseline sorption, ion exchange water reclamation technology which will be used on Space Station Freedom (SSF). Low molecular weight, polar organics such as alcohols, aldehydes, ketones, amides, and thiocarbamides which are poorly removed by the baseline multifiltration (MF) technology can be oxidized to carbon dioxide at low temperature (121 C). The catalytic oxidation process by itself can reduce the Total Organic Carbon (TOC) to below 500 ppb for solutions designed to model these waste waters. Individual challenges by selected contaminants have shown only moderate selectivity towards particular organic species. The combined technology is applicable to the more complex waste water generated in the Process Materials Management System (PMMS) and Environmental Control and Life Support System (ECLSS) aboard SSF. During the phase 3 Core Module Integrated Facility (CMIF) water recovery tests at NASA MSFC, real hygiene waste water and humidity condensate were processed to meet potable specifications by the combined technology. A kinetic study of catalytic oxidation demonstrates that the Langmuir-Hinshelwood rate equation for heterogeneous catalysts accurately represent the kinetic behavior. From this relationship, activation energy and rate constants for acetone were determined.

WORKSHOP ON MONITORING OXIDATION-REDUCTION PROCESSES FOR GROUND-WATER RESTORATION

EPA Science Inventory

Redox conditions are among the most important parameters for controlling contaminant transport and fate in ground-water systems. Oxidation-reduction (redox) reactions mediate the chemical behavior of both inorganic and organic chemical constituents by affecting solubility, rea...

SULFATE RADICAL-BASED ADVANCED OXIDATION PROCESSES- ACS MEETING

EPA Science Inventory

This paper will present an overview of sulfate radical-based advanced oxidation technologies for the destruction of environmentally toxic chemicals in wastewater, industrial water, groundwater and sources of water supply. The paper will include fundamental aspects of the generati...

Intense Electrochemical Oxidation on Graphitized Carbon Electrodes in the Presence of Ozone

NASA Astrophysics Data System (ADS)

Klochikhin, V. L.; Potapova, G. F.; Putilov, A. V.

2018-06-01

A new intense oxidation process for water treatment in which oxidation with ozone is coupled to electrochemical processes is described, and the results from its application to water purification are presented along with the discussion of its practical implementation. The use of graphitized carbon materials for this process is explained and tested experimentally. The use of glassy carbon for the anode enables us to achieve very high (up to 25 vol %) concentrations of ozone in the generated ozone-oxygen mixture. The material used for the cathode—graphitized carbon cloth (GCC) reinforced with Ni allows different electrocatalytic processes to proceed on its developed surface, and combines the high sorption capacity of this cathode and potentialcontrolled selectivity of cathodic electrochemical processes.

Supercritical waste oxidation of aqueous wastes

NASA Technical Reports Server (NTRS)

Modell, M.

1986-01-01

For aqueous wastes containing 1 to 20 wt% organics, supercritical water oxidation is less costly than controlled incineration or activated carbon treatment and far more efficient than wet oxidation. Above the critical temperature (374 C) and pressure (218 atm) of water, organic materials and gases are completely miscible with water. In supercritical water oxidation, organics, air and water are brought together in a mixture at 250 atm and temperatures above 400 C. Organic oxidation is initiated spontaneously at these conditions. The heat of combustion is released within the fluid and results in a rise in temperature 600 to 650 C. Under these conditions, organics are destroyed rapidly with efficiencies in excess of 99.999%. Heteroatoms are oxidized to acids, which can be precipitated out as salts by adding a base to the feed. Examples are given for process configurations to treat aqueous wastes with 10 and 2 wt% organics.

Process for preparing active oxide powders

DOEpatents

Berard, Michael F.; Hunter, Jr., Orville; Shiers, Loren E.; Dole, Stephen L.; Scheidecker, Ralph W.

1979-02-20

An improved process for preparing active oxide powders in which cation hydroxide gels, prepared in the conventional manner are chemically dried by alternately washing the gels with a liquid organic compound having polar characteristics and a liquid organic compound having nonpolar characteristics until the mechanical water is removed from the gel. The water-free cation hydroxide is then contacted with a final liquid organic wash to remove the previous organic wash and speed drying. The dried hydroxide treated in the conventional manner will form a highly sinterable active oxide powder.

In situ metrology to characterize water vapor delivery during atomic layer deposition

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

Ahmido, Tariq, E-mail: tariq.ahmido@nist.gov; Kimes, William A.; Sperling, Brent A.

Water is often employed as the oxygen source in metal oxide atomic layer deposition (ALD) processes. It has been reported that variations in the amount of water delivered during metal oxide ALD can impact the oxide film properties. Hence, one contribution to optimizing metal oxide ALD processes would be to identify methods to better control water dose. The development of rapid, quantitative techniques for in situ water vapor measurements during ALD processes would be beneficial to achieve this goal. In this report, the performance of an in situ tunable diode laser absorption spectroscopy (TDLAS) scheme for performing rapid, quantitative watermore » partial pressure measurements in a representative quarter-inch ALD delivery line is described. This implementation of TDLAS, which utilizes a near-infrared distributed-feedback diode laser and wavelength modulation spectroscopy, provides measurements of water partial pressure on a timescale comparable to or shorter than the timescale of the gas dynamics in typical ALD systems. Depending on the degree of signal averaging, this TDLAS system was capable of measuring the water partial pressure with a detection limit in the range of ∼0.80 to ∼0.08 Pa. The utility of this TDLAS scheme was demonstrated by using it to identify characteristics of a representative water delivery system that otherwise would have been difficult to predict. Those characteristics include (1) the magnitude and time dependence of the pressure transient that can occur during water injection, and (2) the dependence of the steady-state water partial pressure on the carrier gas flow rate and the setting of the water ampoule flow restriction.« less

Process for treating effluent from a supercritical water oxidation reactor

DOEpatents

Barnes, C.M.; Shapiro, C.

1997-11-25

A method for treating a gaseous effluent from a supercritical water oxidation reactor containing entrained solids is provided comprising the steps of expanding the gas/solids effluent from a first to a second lower pressure at a temperature at which no liquid condenses; separating the solids from the gas effluent; neutralizing the effluent to remove any acid gases; condensing the effluent; and retaining the purified effluent to the supercritical water oxidation reactor. 6 figs.

Atomic origins of water-vapour-promoted alloy oxidation

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

Luo, Langli; Su, Mao; Yan, Pengfei

The presence of water vapor, intentional or unavoidable, is crucial to many materials applications, such as steam generator, turbine engine, fuel cell, catalyst, and corrosion 1-6. Phenomenologically, water vapor has been noticed to accelerate oxidation of metals/alloys 7,8, however, the atomistic mechanisms remain elusive. Herein, through direct in situ atomic-scale transmission electron microscopy observation and density functional theory calculation, we reveal that water vapor enhanced oxidation of Ni-Cr alloy is associated with proton dissolution promoted vacancy formation, migration and clustering. Protons derived from water dissociation occupy interstitial position in the oxide lattice, which consequently leads to the lowering of bothmore » vacancy formation energy and the cation diffusion barrier. The atomic scale observations reveal a water vapor derived proton mediated oxide growth mechanism, which provides insights for reckoning many technological processes concerning materials in moist environment at elevated temperatures.« less

A comparison of disinfection by-products formation during sequential or simultaneous disinfection of surface waters with chlorine dioxide and chlor(am)ine.

PubMed

Shi, Yanwei; Ling, Wencui; Qiang, Zhimin

2013-01-01

The effect of chlorine dioxide (ClO2) oxidation on the formation of disinfection by-products (DBPs) during sequential (ClO2 pre-oxidation for 30 min) and simultaneous disinfection processes with free chlorine (FC) or monochloramine (MCA) was investigated. The formation of DBPs from synthetic humic acid (HA) water and three natural surface waters containing low bromide levels (11-27 microg/L) was comparatively examined in the FC-based (single FC, sequential ClO2-FC, and simultaneous ClO2/FC) and MCA-based (single MCA, ClO2-MCA, and ClO2/MCA) disinfection processes. The results showed that much more DBPs were formed from the synthetic HA water than from the three natural surface waters with comparative levels of dissolved organic carbon. In the FC-based processes, ClO2 oxidation could reduce trihalomethanes (THMs) by 27-35% and haloacetic acids (HAAs) by 14-22% in the three natural surface waters, but increased THMs by 19% and HAAs by 31% in the synthetic HA water after an FC contact time of 48 h. In the MCA-based processes, similar trends were observed although DBPs were produced at a much lower level. There was an insignificant difference in DBPs formation between the sequential and simultaneous processes. The presence of a high level of bromide (320 microg/L) remarkably promoted the DBPs formation in the FC-based processes. Therefore, the simultaneous disinfection process of ClO2/MCA is recommended particularly for waters with a high bromide level.

Cryptosporidium-contaminated water disinfection by a novel Fenton process.

PubMed

Matavos-Aramyan, Sina; Moussavi, Mohsen; Matavos-Aramyan, Hedieh; Roozkhosh, Sara

2017-05-01

Three novel modified advanced oxidation process systems including ascorbic acid-, pro-oxidants- and ascorbic acid-pro-oxidants-modified Fenton system were utilized to study the disinfection efficiency on Cryptosporidium-contaminated drinking water samples. Different concentrations of divalent and trivalent iron ions, hydrogen peroxide, ascorbic acid and pro-oxidants at different exposure times were investigated. These novel systems were also compared to the classic Fenton system and to the control system which comprised of only hydrogen peroxide. The complete in vitro mechanism of the mentioned modified Fenton systems are also provided. The results pointed out that by considering the optimal parameter limitations, the ascorbic acid-modified Fenton system decreased the Cryptosporidium oocytes viability to 3.91%, while the pro-oxidant-modified and ascorbic acid-pro-oxidant-modified Fenton system achieved an oocytes viability equal to 1.66% and 0%, respectively. The efficiency of the classic Fenton at optimal condition was observed to be 20.12% of oocytes viability. The control system achieved 86.14% of oocytes viability. The optimum values of the operational parameters during this study are found to be 80mgL -1 for the divalent iron, 30mgL -1 for ascorbic acid, 30mmol for hydrogen peroxide, 25mgL -1 for pro-oxidants and an exposure time equal to 5min. The ascorbic acid-pro-oxidants-modified Fenton system achieved a promising complete water disinfection (0% viability) at the optimal conditions, leaving this method a feasible process for water disinfection or decontamination, even at industrial scales. Copyright © 2017 Elsevier Inc. All rights reserved.

Physical/chemical closed-loop water-recycling for long-duration missions

NASA Technical Reports Server (NTRS)

Herrmann, Cal C.; Wydeven, Ted

1990-01-01

Water needs, water sources, and means for recycling water are examined in terms appropriate to the water quality requirements of a small crew and spacecraft intended for long duration exploration missions. Inorganic, organic, and biological hazards are estimated for waste water sources. Sensitivities to these hazards for human uses are estimated. The water recycling processes considered are humidity condensation, carbon dioxide reduction, waste oxidation, distillation, reverse osmosis, pervaporation, electrodialysis, ion exchange, carbon sorption, and electrochemical oxidation. Limitations and applications of these processes are evaluated in terms of water quality objectives. Computerized simulation of some of these chemical processes is examined. Recommendations are made for development of new water recycling technology and improvement of existing technology for near term application to life support systems for humans in space. The technological developments are equally applicable to water needs on earth, in regions where extensive water ecycling is needed or where advanced water treatment is essential to meet EPA health standards.

Advanced oxidation process-mediated removal of pharmaceuticals from water: A review.

PubMed

Kanakaraju, Devagi; Glass, Beverley D; Oelgemöller, Michael

2018-08-01

Pharmaceuticals, which are frequently detected in natural and wastewater bodies as well as drinking water have attracted considerable attention, because they do not readily biodegrade and may persist and remain toxic. As a result, pharmaceutical residues pose on-going and potential health and environmental risks. To tackle these emerging contaminants, advanced oxidation processes (AOPs) such as photo-Fenton, sonolysis, electrochemical oxidation, radiation and ozonation etc. have been applied to remove pharmaceuticals. These processes utilize the high reactivity of hydroxyl radicals to progressively oxidize organic compounds to innocuous products. This review provides an overview of the findings from recent studies, which have applied AOPs to degrade pharmaceutical compounds. Included is a discussion that links various factors of TiO 2 -mediated photocatalytic treatment to its effectiveness in degrading pharmaceutical residues. This review furthermore highlights the success of AOPs in the removal of pharmaceuticals from different water matrices and recommendations for future studies are outlined. Copyright © 2018 Elsevier Ltd. All rights reserved.

Dark ambient degradation of Bisphenol A and Acid Orange 8 as organic pollutants by perovskite SrFeO₃-δ metal oxide.

PubMed

Leiw, Ming Yian; Guai, Guan Hong; Wang, Xiaoping; Tse, Man Siu; Ng, Chee Mang; Tan, Ooi Kiang

2013-09-15

Current advanced oxidation processes (AOPs) are chemically and energetically intensive processes, which are undesirable for cost-effective and large-scale system water treatment and wastewater recycling. This study explored the Strontium Ferrite (SFO) metal oxide on the degradation of highly concentrated organic pollutants under dark ambient condition without any external stimulants. The SFO particles with single perovskite structure were successfully synthesized with a combined high temperature and high-energy ball milling process. An endocrine disruptor, Bisphenol A (BPA) and an azo dye, Acid Orange 8 (AO8) were used as probe organic pollutants. BPA was completely degraded with 83% of mineralization in 24 h while rapid decoloration of AO8 was achieved in 60 min and complete breakdown into primary intermediates and aliphatic acids occurred in 24 h under the treatment of dispersed SFO metal oxide in water. Such efficient degradation could be attributed to the enhanced adsorption of these anionic pollutants on positively charged ball-milled SFO metal oxide surface, resulted in higher degradation activity. Preliminary degradation mechanisms of BPA and AO8 under the action of SFO metal oxide were proposed. These results showed that the SFO metal oxide could be an efficient alternative material as novel advanced oxidation technology for low cost water treatment. Copyright © 2013 Elsevier B.V. All rights reserved.

Oxidation reactions of solid carbonaceous and resinous substances in supercritical water

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

Koda, S.

Recent kinetic studies, particularly those by means of shadowgraphy and X-ray radiography, for supercritical water oxidation of solid carbonaceous and resinous substances have revealed the importance of the O{sub 2} mass transfer process over the intrinsic surface reaction at higher temperatures. The mass transfer processes, internal and external one, should be incorporated in designing SCWO processes for solid substances and related processes such as catalytic SCWO. Some model calculation efforts of late are briefly described. Finally, fundamental information required for future development is itemed.

Polymer-assisted aqueous deposition of metal oxide films

DOEpatents

Li, DeQuan [Los Alamos, NM; Jia, Quanxi [Los Alamos, NM

2003-07-08

An organic solvent-free process for deposition of metal oxide thin films is presented. The process includes aqueous solutions of necessary metal precursors and an aqueous solution of a water-soluble polymer. After a coating operation, the resultant coating is fired at high temperatures to yield optical quality metal oxide thin films.

Downhole steam generator using low-pressure fuel and air supply

DOEpatents

Fox, R.L.

1981-01-07

For tertiary oil recovery, an apparatus for downhole steam generation is designed in which water is not injected directly onto the flame in the combustor, the combustion process is isolated from the reservoir pressure, the fuel and oxidant are supplied to the combustor at relatively low pressures, and the hot exhaust gases is prevented from entering the earth formation but is used to preheat the fuel and oxidant and water. The combustion process is isolated from the steam generation process. (DLC)

Microbial fuel cell treatment of ethanol fermentation process water

DOEpatents

Borole, Abhijeet P [Knoxville, TN

2012-06-05

The present invention relates to a method for removing inhibitor compounds from a cellulosic biomass-to-ethanol process which includes a pretreatment step of raw cellulosic biomass material and the production of fermentation process water after production and removal of ethanol from a fermentation step, the method comprising contacting said fermentation process water with an anode of a microbial fuel cell, said anode containing microbes thereon which oxidatively degrade one or more of said inhibitor compounds while producing electrical energy or hydrogen from said oxidative degradation, and wherein said anode is in electrical communication with a cathode, and a porous material (such as a porous or cation-permeable membrane) separates said anode and cathode.

Biological efficacy and toxic effect of emergency water disinfection process based on advanced oxidation technology.

PubMed

Tian, Yiping; Yuan, Xiaoli; Xu, Shujing; Li, Rihong; Zhou, Xinying; Zhang, Zhitao

2015-12-01

An innovative and removable water treatment system consisted of strong electric field discharge and hydrodynamic cavitation based on advanced oxidation technologies was developed for reactive free radicals producing and waterborne pathogens eliminating in the present study. The biological efficacy and toxic effects of this advanced oxidation system were evaluated during water disinfection treatments. Bench tests were carried out with synthetic microbial-contaminated water, as well as source water in rainy season from a reservoir of Dalian city (Liaoning Province, China). Results showed that high inactivation efficiency of Escherichia coli (>5 log) could be obtained for synthetic contaminated water at a low concentration (0.5-0.7 mg L(-1)) of total oxidants in 3-10 s. The numbers of wild total bacteria (108 × 10(3) CFU mL(-1)) and total coliforms (260 × 10(2) MPN 100 mL(-1)) in source water greatly reduced to 50 and 0 CFU mL(-1) respectively after treated by the advanced oxidation system, which meet the microbiological standards of drinking water, and especially that the inactivation efficiency of total coliforms could reach 100%. Meanwhile, source water qualities were greatly improved during the disinfection processes. The values of UV254 in particular were significantly reduced (60-80%) by reactive free radicals. Moreover, the concentrations of possible disinfection by-products (formaldehyde and bromide) in treated water were lower than detection limits, indicating that there was no harmful effect on water after the treatments. These investigations are helpful for the ecotoxicological studies of advanced oxidation system in the treatments of chemical polluted water or waste water. The findings of this work suggest that the developed water treatment system is ideal in the acute phases of emergencies, which also could offer additional advantages over a wide range of applications in water pollution control.

Acetone and Water on TiO₂(110): H/D Exchange

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

Henderson, Michael A.

2005-04-12

Isotopic H/D exchange between coadsorbed acetone and water on the TiO?(110) surface was examined using temperature programmed desorption (TPD) as a function of coverage and two surface pretreatments (oxidation and reduction). Coadsorbed acetone and water interact repulsively on reduced TiO?(110) based on results from the companion paper to this study, with water exerting a greater influence in destabilizing acetone and acetone having only a nominal influence on water. Despite the repulsive interaction between these coadsorbates, about 0.02 ML of a 1 ML d6-acetone on the reduced surface exhibits H/D exchange with coadsorbed water, with the exchange occurring exclusively in themore » high temperature region of the d?-acetone TPD spectrum at {approx}340 K. The effect was confirmed with combinations of d?-acetone and D?O. The extent of exchange decreased on the reduced surface with water coverages above {approx}0.3 ML due to the ability of water to displace coadsorbed acetone from first layer sites to the multilayer. In contrast, the extent of exchange increased by a factor of 3 when the surface was pre-oxidized prior to coadsorption. In this case, there was no evidence for the negative influence of high water coverages on the extent of H/D exchange. Comparison of the TPD spectra from the exchange products (either d?- or d?-acetone depending on the coadsorption pairing) suggests that, in addition to the 340 K exchange process seen on the reduced surface, a second exchange process was observed on the oxidized surface at {approx}390 K. In both cases (oxidized and reduced), desorption of the H/D exchange products appeared to be reaction limited and to involve the influence of OH/OD groups (or water formed during recombinative desorption of OH/OD groups) instead of molecularly adsorbed water. The 340 K exchange process is assigned to reaction at step sites and the 390 K exchange process is attributed to the influence of oxygen adatoms deposited during surface oxidation. The H/D exchange mechanism likely involves an enolate or propenol surface intermediate formed transiently during the desorption of oxygen-stabilized acetone molecules.« less

HANDBOOK ON ADVANCED PHOTOCHEMICAL OXIDATION PROCESSES

EPA Science Inventory

This handbook summarizes commercial-scale system performance and cost data for advanced photochemical oxidation (APO) treatment of contaminated water, air, and solids. Similar information from pilot- and bench-scale evaluations of APO processes is also included to supplement the...

CONTAMINANT ADSORPTION AND OXIDATION VIA FENTON REACTION

EPA Science Inventory

A ground water treatment process is proposed involving two cgemical processes: adsorption and oxidation. Adsorption of an organic compound onto granulated activated carbon (GAC) containing iron conveniently results in immobilizing and concentrating contaminants from the ground w...

Erratum to ;Coastal water column ammonium and nitrite oxidation are decoupled in summer;

NASA Astrophysics Data System (ADS)

Heiss, Elise M.; Fulweiler, Robinson W.

2017-07-01

Water column nitrification is a key process in the nitrogen cycle as it links reduced and oxidized forms of nitrogen and also provides the substrate (nitrate) needed for reactive nitrogen removal by denitrification. We measured potential water column ammonium and nitrite oxidation rates at four sites along an estuary to continental shelf gradient over two summers. In most cases, nitrite oxidation rates outpaced ammonium oxidation rates. Overall, ammonium and nitrite oxidation rates were higher outside of the estuary, and this trend was primarily driven by higher oxidation rates in deeper waters. Additionally, both ammonium and nitrite oxidation rates were impacted by different in situ variables. Ammonium oxidation rates throughout the water column as a whole were most positively correlated to depth and salinity and negatively correlated to dissolved oxygen, light, and temperature. In contrast, nitrite oxidation rates throughout the water column were negatively correlated with temperature, light and pH. Multivariate regression analysis revealed that surface (<20 m) ammonium oxidation rates were most strongly predicted by substrate (NH4+), salinity, and light, while deep (>20 m) rates were regulated by temperature, light, and [H+] (i.e. pH). In addition, surface (<20 m) nitrite oxidation rates were best explained by [H+] alone, while [H+], temperature, and dissolved oxygen all played a role in predicting deep (>20 m) nitrite oxidation rates. These results support the growing body of evidence that ammonium oxidation and nitrite oxidation are not always coupled, should be measured separately, and are influenced by different environmental conditions.

Light-driven water oxidation for solar fuels

PubMed Central

Young, Karin J.; Martini, Lauren A.; Milot, Rebecca L.; III, Robert C. Snoeberger; Batista, Victor S.; Schmuttenmaer, Charles A.; Crabtree, Robert H.; Brudvig, Gary W.

2014-01-01

Light-driven water oxidation is an essential step for conversion of sunlight into storable chemical fuels. Fujishima and Honda reported the first example of photoelectrochemical water oxidation in 1972. In their system, TiO2 was irradiated with ultraviolet light, producing oxygen at the anode and hydrogen at a platinum cathode. Inspired by this system, more recent work has focused on functionalizing nanoporous TiO2 or other semiconductor surfaces with molecular adsorbates, including chromophores and catalysts that absorb visible light and generate electricity (i.e., dye-sensitized solar cells) or trigger water oxidation at low overpotentials (i.e., photocatalytic cells). The physics involved in harnessing multiple photochemical events for multielectron reactions, as required in the four-electron water oxidation process, has been the subject of much experimental and computational study. In spite of significant advances with regard to individual components, the development of highly efficient photocatalytic cells for solar water splitting remains an outstanding challenge. This article reviews recent progress in the field with emphasis on water-oxidation photoanodes inspired by the design of functionalized thin film semiconductors of typical dye-sensitized solar cells. PMID:25364029

[Anoxic bioremediation of urban polluted river water with biofilm].

PubMed

Zhang, Yong-Ming; Hu, Yi-Zhen; Yan, Rong; Liu, Fang

2009-07-15

Reactor like oxidation ditch was used for anaerobic bioremediation of urban river water, in which biofilm formed on ceramic honeycomb carrier was used instated of activated sludge. The dissolved oxygen in the wastewater was controlled under 0.5 mg/L for anoxic oxidation, and ammonia nitrogen was removed 40 to 60 percent, and total nitrogen removed 40 to 45 percent, that is ammonia nitrogen and total nitrogen were removed at the same time, also, nitrite was not any accumulated during the process. The biofilm was taken into flask to culture under anoxic oxidation condition in order to prove if anaerobic ammonium oxidation (ANAMMOX) occurred in the process, and ammonia and nitrite nitrogen were also removed at the same time in the experiment, which suggested that nitrification-denitrification and ANAMMOX occurred in bioremediation of urban surface water with low ratio of carbon and nitrogen at the same time. The anammox bacteria were existed in the biofilm according to molecular biological analysis. The experiment will be significant for bioremediation of eutrophication water body.

[Microcystin safety study during Cyanobacteria removal by pressure enhanced coagulation process].

PubMed

Jiang, Xin-Yue; Luan, Qing; Cong, Hai-Bing; Xu, Si-Tao; Liu, Yu-Jiao; Zhu, Xue-Yuan

2014-11-01

Pressure enhanced coagulation and sedimentation technique is an effective way for blue algae treatment. It is not clear whether Cyanobacteria balloon rupture will cause Cyanobacteria cells rupture, resulting in high intracellular concentrations of microcystin LR leak into the water, affecting drinking water safety. Therefore, in this study experimental comparative study of pressure and pre-oxidation of water containing Cyanobacteria was carried out to examine the microcystin LR concentration changes and Cyanobacteria removal efficiency. The results showed that microcystin concentration increase was not significant by the pre-treatment with Cyanobacteria water pressure, while the pre-oxidation process caused a significant increase in the concentration of microcystin. After 0.5-0.8 MPa pressure coagulation and sedimentation, removal of Cyanobacteria basically was over 90%, up to 93.5%, while the removal rate by pre-oxidation was low and unstable. Effluent turbidity is also significantly better in the pre-pressure method than the pre-oxidation. The results indicated that pressure enhanced coagulation is a safe and reliable method for Cyanobacteria removal.

Low temperature ozone oxidation of solid waste surrogates

NASA Astrophysics Data System (ADS)

Nabity, James A.; Lee, Jeffrey M.

2015-09-01

Solid waste management presents a significant challenge to human spaceflight and especially, long-term missions beyond Earth orbit. A six-month mission will generate over 300 kg of solid wastes per crewmember that must be dealt with to eliminate the need for storage and prevent it from becoming a biological hazard to the crew. There are several methods for the treatment of wastes that include oxidation via ozone, incineration, microbial oxidation or pyrolysis and physical methods such as microwave drying and compaction. In recent years, a low temperature oxidation process using ozonated water has been developed for the chemical conversion of organic wastes to CO2 and H2O. Experiments were conducted to evaluate the rate and effectiveness with which ozone oxidized several different waste materials. Increasing the surface area by chopping or shredding the solids into small pieces more than doubled the rate of oxidation. A greater flow of ozone and agitation of the ozonated water system also increased processing rates. Of the materials investigated, plastics have proven the most difficult to oxidize. The processing of plastics above the glass transition temperatures caused the plastics to clump together which reduced the exposed surface area, while processing at lower temperatures reduced surface reaction kinetics.

Graphene-based materials supported advanced oxidation processes for water and wastewater treatment: a review.

PubMed

Nidheesh, Puthiya Veetil

2017-12-01

Advanced oxidation processes (AOPs) received much attention in the field of water and wastewater treatment due to its ability to mineralize persistent organic pollutants from water medium. The addition of graphene-based materials increased the efficiency of all AOPs significantly. The present review analyzes the performance of graphene-based materials that supported AOPs in detail. Recent developments in this field are highlighted. A special focus has been awarded for the performance enhancement mechanism of AOPs in the presence of graphene-based materials.

Bacterial oxidation of methyl bromide in Mono Lake, California

USGS Publications Warehouse

Connell, T.L.; Joye, S.B.; Miller, L.G.; Oremland, R.S.

1997-01-01

The oxidation of methyl bromide (MeBr) in the water column of Mono Lake, CA, was studied by measuring the formation of H14CO3 from [14C]MeBr. Potential oxidation was detected throughout the water column, with highest rates occurring in the epilimnion (5-12 m depth). The oxidation of MeBr was eliminated by filter-sterilization, thereby demonstrating the involvement of bacteria. Vertical profiles of MeBr activity differed from those obtained for nitrification and methane oxidation, indicating that MeBr oxidation is not simply a co-oxidation process by either nitrifiers or methanotrophs. Furthermore, specific inhibitors of methane oxidation and/or nitrification (e.g., methyl fluoride, acetylene, allyl sulfide) had no effect upon the rate of MeBr oxidation in live samples. Of a variety of potential electron donors added to Mono Lake water, only trimethylamine resulted in the stimulation of MeBr oxidation. Cumulatively, these results suggest that the oxidation of MeBr in Mono Lake waters is attributable to trimethylamine-degrading methylotrophs. Neither methyl chloride nor methanol inhibited the oxidation of [14C]MeBr in live samples, indicating that these bacteria directly oxidized MeBr rather than the products of MeBr nucleophilic substitution reactions.

HANDBOOK ON ADVANCED NONPHOTOCHEMICAL OXIDATION PROCESSES

EPA Science Inventory

The purpose of this handbook is to summarize commercial-scale system performance and cost data for advanced nonphotochemical oxidation (ANPO) treatment of contaminated water, air, and soil. Similar information from pilot-and bench-scale evaluations of ANPO processes is also inclu...

Chemical and Isotopic Characterization of Waters in Rio Tinto, Spain, Shows Possible Origin of the Blueberry Haematite Nodules in Meridiani Planum, Mars

NASA Astrophysics Data System (ADS)

Coleman, M. L.; Hubbard, C. G.; Mielke, R. E.; Black, S.

2005-12-01

Meridiani Planum sediments formed in an acid environment and include jarosite and other evaporitic sulfate minerals. Nodular spheroidal concretions appear to have grown in situ and are predominantly hematite. The source of the Rio Tinto, S. Spain, drains an area of extensive sulfide mineralization and is dominated by acid mine drainage processes. The system is not a Mars analog but potentially similar processes of sulfide oxidation produce sulfate rich waters which feed into the river and precipitate a large range of evaporitic sulfates including jarosite. Iron oxide minerals associated with the evaporites are either dispersed or bedded but not nodular. The water compositions appear to be mixtures of a few discreet end-members: the two most significant occur in undiluted form as inputs to the river and are relevant to many such systems. They both have all sulfur totally oxidized as sulfate. The first is a bright red water, pH ~1.5, Fe/S 0.5 and 23 g/L iron which is greater than 95% Fe3+. Its sulfate oxygen isotope composition is +2‰SMOW and about +7‰, relative to the water O isotope composition. These data indicate pyrite oxidation by Fe3+ with O in sulfate coming mainly from water. The second end-member is a pale green water, pH ~0.7, Fe/S 0.7, 50 g/L iron present mainly as Fe2+ and O isotope composition of sulfate about +6‰SMOW , about +12.5‰ relative to the water O value. Oxygen in sulfate comes mainly from atmospheric oxygen resulting from pyrite oxidation by molecular oxygen dissolved in water. Although the Rio Tinto system reactions probably are microbiologically mediated (relevant genera have been identified there) similar processes could occur abiotically but more slowly. Meridiani Planum sediments and nodules can be described by a plausible set of similar end-member processes. The primary source of sulfate is oxidation of sulfides present in basalt (pyrite, FeS2 or pyrrhotite, FeS) and weathering would have produced oxidized sulfate rich solutions at low pH. Ground water migration could produce evaporitic ponds where various bedded sulfate mineral sediments could form. The intergranular pore-spaces would be water filled. Most terrestrial spheroidal nodular concretions form by radial diffusion in pore-water of a chemical component of a very different oxidation state from that of the surrounding water. A nodular concretion is most usually formed by the reaction of the diffusive component with others in the pore-water. There are two main possible reaction sets for formation of the Blueberries that are consistent with all current data. 1. Local concentrations of organic matter (pre-biotic or biotic) formed reduction spots in which a small amount of Fe3+ either in solution or from evaporite mineral salts, was reduced to Fe2+ and then diffused radially to form an iron oxide nodule by reaction with inwardly diffusing dissolved oxygen. 2. Similar local concentrations of organic matter could also have engendered sulfate reduction and consequent outward diffusion of dissolved sulfide reacted with iron in solution to produce an iron sulfide nodule, subsequently oxidized in situ to hematite (maybe via goethite). Our current work is successfully identifying chemical and stable isotopic characteristics for both microbial and abiotic modes of all relevant reactions.

Oxidative removal of selected endocrine-disruptors and pharmaceuticals in drinking water treatment systems, and identification of degradation products of triclosan.

PubMed

Wu, Qihua; Shi, Honglan; Adams, Craig D; Timmons, Terry; Ma, Yinfa

2012-11-15

The potential occurrences of endocrine-disrupting compounds (EDCs), as well as pharmaceuticals, are considered to be emerging environmental problems due to their persistence and continuous input into the aquatic ecosystem, even at only trace concentrations. This study systematically investigated the oxidative removal of eight specially selected ECDs and pharmaceuticals by comparing their relative reactivity as a function of different oxidative treatment processes (i.e., free chlorine, ozone, monochloramine, and permanganate) under various pH conditions. For the oxidative removal study, EDC and pharmaceutical standards were spiked into both deionized water and natural water, followed by treatment using common oxidants at typical water treatment concentrations. Liquid chromatography-tandem mass spectrometry (LC-MS/MS) was used for identification and quantification. The removal efficiency of the EDCs and pharmaceuticals varied significantly between oxidation processes. Free chlorine, permanganate, and ozone treatments were all highly effective at the elimination of triclosan and estrone, while they were not effective for removing ibuprofen, iopromide, and clofibric acid. Monochloramine (at a dose of 3mg/L) was mostly ineffective in eliminating any of the selected EDCs and pharmaceuticals under the tested conditions. pH also played an important role in the removal efficiency of the EDCs and pharmaceuticals during free chlorine, permanganate, and ozone treatments. Additionally, the study identified the oxidation products of triclosan by permanganate, and 2,4-dichlorophenol was identified as the major oxidation product of triclosan by permanganate in drinking water system treatment. Furthermore, 2,4-dichlorophenol was further degradated to 4,5-dichloro-2-(2,4-dichlorophenoxy)phenol and/or 5,6-dichloro-2-(2,4-dichlorophenoxy)phenol. The kinetics for this reaction indicated that the reaction was first order in the drinking water system. Copyright © 2012 Elsevier B.V. All rights reserved.

Catalytic process for formaldehyde oxidation

NASA Technical Reports Server (NTRS)

Kielin, Erik J. (Inventor); Brown, Kenneth G. (Inventor); D'Ambrosia, Christine M. (Inventor)

1996-01-01

Disclosed is a process for oxidizing formaldehyde to carbon dioxide and water without the addition of energy. A mixture of formaldehyde and an oxidizing agent (e.g., ambient air containing formaldehyde) is exposed to a catalyst which includes a noble metal dispersed on a metal oxide which possesses more than one oxidation state. Especially good results are obtained when the noble metal is platinum, and the metal oxide which possesses more than one oxidation state is tin oxide. A promoter (i.e., a small amount of an oxide of a transition series metal) may be used in association with the tin oxide to provide very beneficial results.

Oxidation of Alloy 600 and Alloy 690: Experimentally Accelerated Study in Hydrogenated Supercritical Water

NASA Astrophysics Data System (ADS)

Moss, Tyler; Cao, Guoping; Was, Gary S.

2017-04-01

The objective of this study is to determine whether the oxidation of Alloys 600 and 690 in supercritical water occurs by the same mechanism in subcritical water. Coupons of Alloys 690 and 600 were exposed to hydrogenated subcritical and supercritical water from 633 K to 673 K (360 °C to 400 °C) and the oxidation behavior was observed. By all measures of oxide character and behavior, the oxidation process is the same above and below the supercritical line. Similar oxide morphologies, structures, and chemistries were observed for each alloy across the critical point, indicating that the oxidation mechanism is the same in both subcritical and supercritical water. Oxidation results in a multi-layer oxide structure composed of particles of NiO and NiFe2O4 formed by precipitation on the outer surface and a chromium-rich inner oxide layer formed by diffusion of oxygen to the metal-oxide interface. The inner oxide on Alloy 600 is less chromium rich than that observed on Alloy 690 and is accompanied by preferential oxidation of grain boundaries. The inner oxide on Alloy 690 initially forms by internal oxidation before a protective layer of chromium-rich MO is formed with Cr2O3 at the metal-oxide interface. Grain boundaries in Alloy 690 act as fast diffusion paths for chromium that forms a protective Cr2O3 layer at the surface, preventing grain boundary oxidation from occurring.

Reduce oil and grease content in wastewater

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

Capps, R.W.; Matelli, G.N.; Bradford, M.L.

Poor water quality is often blamed on biological oxidation unit malfunction. However, poorly treated water entering the bio-unit is more often the problem. At the microscopic level, oil/water-separation dynamics are influenced by pH, fluid velocity, temperature, and unit volumes. Oily water's physical and chemical properties affect pretreatment systems such as API separators, corrugated plate interception (CPI) separators, air flotation and equalization systems. A better understanding of pretreatment systems' limits and efficiencies can improve wastewater quality before it upsets the biological oxidation (BIOX). Oil contamination in refinery wastewater originates from desalting, steam stripping, product treating, tank drains, sample drains and equipmentmore » washdown. The largest volumetric contributors are cooling tower blowdowns and contaminated stormwater. The paper describes the BIOX process; oil/water separation; oil/water emulsions and colloidal solutions; air flotation; surfactants; DAF (dissolved air flotation) process; IAF (induced air flotation) process; equalization; load factors; salts; and system design.« less

Mechanism analysis on finishing of reaction-sintered silicon carbide by combination of water vapor plasma oxidation and ceria slurry polishing

NASA Astrophysics Data System (ADS)

Shen, Xinmin; Tu, Qunzhang; Deng, Hui; Jiang, Guoliang; Yamamura, Kazuya

2015-05-01

Reaction-sintered silicon carbide (RS-SiC), which is considered as a promising mirror material for space telescope systems, requires a high surface property. An ultrasmooth surface with a Ra surface roughness of 0.480 nm was obtained after water vapor plasma oxidation for 90 min followed by ceria slurry polishing for 40 min. The oxidation process of RS-SiC by water vapor plasma was analyzed based on the Deal-Grove model, and the theoretical calculation results are consistent with the measured data obtained by scanning white light interferometer (SWLI), scanning electron microscopy/energy-dispersive x-ray, and atomic force microscope. The polishing process of oxidized RS-SiC by ceria slurry was investigated according to the Preston equation, which would theoretically forecast the evolutions of RS-SiC surfaces along with the increasing of polishing time, and it was experimentally verified by comparing the surface roughnesses obtained by SWLI and the surface morphologies obtained by SEM. The mechanism analysis on the finishing of RS-SiC would be effective for the optimization of water vapor plasma oxidation parameters and ceria slurry polishing parameters, which will promote the application of RS-SiC substrates by improving the surface property obtained by the oxidation-assisted polishing method.

Oxidation of ammonia and methane in an alkaline, saline lake

USGS Publications Warehouse

Joye, S.B.; Connell, T.L.; Miller, L.G.; Oremland, R.S.; Jellison, R.S.

1999-01-01

The oxidation of ammonia (NH3) and methane (CH4) was investigated in an alkaline saline lake, Mono Lake, California (U.S.A.). Ammonia oxidation was examined in April and July 1995 by comparing dark 14CO2 fixation rates in the presence or absence of methyl fluoride (MeF), an inhibitor of NH3 oxidation. Ammonia oxidizer-mediated dark 14CO2 fixation rates were similar in surface (5-7 m) and oxycline (11-15 m) waters, ranging between 70-340 and 89-186 nM d-1, respectively, or 1-7% of primary production by phytoplankton. Ammonia oxidation rates ranged between 580-2,830 nM d-1 in surface waters and 732-1,548 nM d-1 in oxycline waters. Methane oxidation was examined using a 14CH4 tracer technique in July 1994, April 1995, and July 1995. Methane oxidation rates were consistently higher in July, and rates in oxycline and anaerobic bottom waters (0.5-37 and 7-48 nM d-1, respectively) were 10-fold higher than those in aerobic surface waters (0.04-3.8 nM d-1). The majority of CH4 oxidation, in terms of integrated activity, occurred within anoxic bottom waters. Water column oxidation reduced the potential lake-atmosphere CH4 flux by a factor of two to three. Measured oxidation rates and water column concentrations were used to estimate the biological turnover times of NH3 and CH4. The NH3 pool turns over rapidly, on time scales of 0.8 d in surface waters and 10 d within the oxycline, while CH4 is cycled on 103-d time scales in surface waters and 102-d time scales within oxycline and bottom waters. Our data suggest an important role for NH3 oxidation in alkaline, saline lakes since the process converts volatile NH3 to soluble NO2-, thereby reducing loss via lake-atmosphere exchange and maintaining nitrogen in a form that is readily available to phytoplankton.

Photochemical charge separation in zeolites: Electron transfer dynamics, nanocrystals and zeolitic membranes. Final technical report

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

Dutta, Prabir K.

2001-09-30

Aluminosilicate zeolites provide an excellent host for photochemical charge separation. Because of the constraints provided by the zeolite, the back electron transfer from the reduced acceptor to the oxidized sensitizer is slowed down. This provides the opportunity to separate the charge and use it in a subsequent reaction for water oxidation and reduction. Zeolite-based ruthenium oxide catalysts have been found to be efficient for the water splitting process. This project has demonstrated the usefulness of zeolite hosts for photolytic splitting of water.

Explicit modeling of volatile organic compounds partitioning in the atmospheric aqueous phase

NASA Astrophysics Data System (ADS)

Mouchel-Vallon, C.; Bräuer, P.; Camredon, M.; Valorso, R.; Madronich, S.; Herrmann, H.; Aumont, B.

2012-09-01

The gas phase oxidation of organic species is a multigenerational process involving a large number of secondary compounds. Most secondary organic species are water-soluble multifunctional oxygenated molecules. The fully explicit chemical mechanism GECKO-A (Generator of Explicit Chemistry and Kinetics of Organics in the Atmosphere) is used to describe the oxidation of organics in the gas phase and their mass transfer to the aqueous phase. The oxidation of three hydrocarbons of atmospheric interest (isoprene, octane and α-pinene) is investigated for various NOx conditions. The simulated oxidative trajectories are examined in a new two dimensional space defined by the mean oxidation state and the solubility. The amount of dissolved organic matter was found to be very low (<2%) under a water content typical of deliquescent aerosols. For cloud water content, 50% (isoprene oxidation) to 70% (octane oxidation) of the carbon atoms are found in the aqueous phase after the removal of the parent hydrocarbons for low NOx conditions. For high NOx conditions, this ratio is only 5% in the isoprene oxidation case, but remains large for α-pinene and octane oxidation cases (40% and 60%, respectively). Although the model does not yet include chemical reactions in the aqueous phase, much of this dissolved organic matter should be processed in cloud drops and modify both oxidation rates and the speciation of organic species.

Explicit modeling of volatile organic compounds partitioning in the atmospheric aqueous phase

NASA Astrophysics Data System (ADS)

Mouchel-Vallon, C.; Bräuer, P.; Camredon, M.; Valorso, R.; Madronich, S.; Herrmann, H.; Aumont, B.

2013-01-01

The gas phase oxidation of organic species is a multigenerational process involving a large number of secondary compounds. Most secondary organic species are water-soluble multifunctional oxygenated molecules. The fully explicit chemical mechanism GECKO-A (Generator of Explicit Chemistry and Kinetics of Organics in the Atmosphere) is used to describe the oxidation of organics in the gas phase and their mass transfer to the aqueous phase. The oxidation of three hydrocarbons of atmospheric interest (isoprene, octane and α-pinene) is investigated for various NOx conditions. The simulated oxidative trajectories are examined in a new two dimensional space defined by the mean oxidation state and the solubility. The amount of dissolved organic matter was found to be very low (yield less than 2% on carbon atom basis) under a water content typical of deliquescent aerosols. For cloud water content, 50% (isoprene oxidation) to 70% (octane oxidation) of the carbon atoms are found in the aqueous phase after the removal of the parent hydrocarbons for low NOx conditions. For high NOx conditions, this ratio is only 5% in the isoprene oxidation case, but remains large for α-pinene and octane oxidation cases (40% and 60%, respectively). Although the model does not yet include chemical reactions in the aqueous phase, much of this dissolved organic matter should be processed in cloud drops and modify both oxidation rates and the speciation of organic species.

Effects of electrolyzed oxidizing water on reducing Listeria monocytogenes contamination on seafood processing surfaces.

PubMed

Liu, Chengchu; Duan, Jingyun; Su, Yi-Cheng

2006-02-15

The effects of electrolyzed oxidizing (EO) water on reducing Listeria monocytogenes contamination on seafood processing surfaces were studied. Chips (5 x 5 cm(2)) of stainless steel sheet (SS), ceramic tile (CT), and floor tile (FT) with and without crabmeat residue on the surface were inoculated with L. monocytogenes and soaked in tap or EO water for 5 min. Viable cells of L. monocytogenes were detected on all chip surfaces with or without crabmeat residue after being held at room temperature for 1 h. Soaking contaminated chips in tap water resulted in small-degree reductions of the organism (0.40-0.66 log cfu/chip on clean surfaces and 0.78-1.33 log cfu/chip on dirty surfaces). Treatments of EO water significantly (p<0.05) reduced L. monocytogenes on clean surfaces (3.73 log on SS, 4.24 log on CT, and 5.12 log on FT). Presence of crabmeat residue on chip surfaces reduced the effectiveness of EO water on inactivating Listeria cells. However, treatments of EO water also resulted in significant reductions of L. monocytogenes on dirty surfaces (2.33 log on SS and CT and 1.52 log on FT) when compared with tap water treatments. The antimicrobial activity of EO water was positively correlated with its chlorine content. High oxidation-reduction potential (ORP) of EO water also contributed significantly to its antimicrobial activity against L. monocytogenes. EO water was more effective than chlorine water on inactivating L. monocytogenes on surfaces and could be used as a chlorine alternative for sanitation purpose. Application of EO water following a thorough cleaning process could greatly reduce L. monocytogenes contamination in seafood processing environments.

Removal of diclofenac by conventional drinking water treatment processes and granular activated carbon filtration.

PubMed

Rigobello, Eliane Sloboda; Dantas, Angela Di Bernardo; Di Bernardo, Luiz; Vieira, Eny Maria

2013-06-01

This study was carried out to evaluate the efficiency of conventional drinking water treatment processes with and without pre-oxidation with chlorine and chlorine dioxide and the use of granular activated carbon (GAC) filtration for the removal of diclofenac (DCF). Water treatment was performed using the Jar test with filters on a lab scale, employing nonchlorinated artesian well water prepared with aquatic humic substances to yield 20HU true color, kaolin turbidity of 70 NTU and 1mgL(-1) DCF. For the quantification of DCF in water samples, solid phase extraction and HPLC-DAD methods were developed and validated. There was no removal of DCF in coagulation with aluminum sulfate (3.47mgAlL(-1) and pH=6.5), flocculation, sedimentation and sand filtration. In the treatment with pre-oxidation and disinfection, DCF was partially removed, but the concentration of dissolved organic carbon (DOC) was unchanged and byproducts of DCF were observed. Chlorine dioxide was more effective than chorine in oxidizing DCF. In conclusion, the identification of DCF and DOC in finished water indicated the incomplete elimination of DCF through conventional treatments. Nevertheless, conventional drinking water treatment followed by GAC filtration was effective in removing DCF (⩾99.7%). In the oxidation with chlorine, three byproducts were tentatively identified, corresponding to a hydroxylation, aromatic substitution of one hydrogen by chlorine and a decarboxylation/hydroxylation. Oxidation with chlorine dioxide resulted in only one byproduct (hydroxylation). Copyright © 2013 Elsevier Ltd. All rights reserved.

Selective removal of organics for water reclamation

NASA Technical Reports Server (NTRS)

Murphy, Oliver J.; Hitchens, G. Duncan; Kaba, Lamine; Verostko, Charles E.

1990-01-01

Electrooxidation is a means of removing organic solutes directly from waste waters without the use of chemical expendables. The feasibility of the concept for oxidation of organic impurities common to urine, shower waters and space habitat humidity condensates was demonstrated. Electrooxidation of urine and waste water ersatz was experimentally demonstrated. The electrooxidation principle, reaction kinetics, efficiency, power, size, experimental test results and water reclamation applications are described. Process operating potentials and the use of anodic oxidation potentials that are sufficiently low to avoid oxygen formation and chloride oxidation are also described. The design of a novel electrochemical system that incorporates a proton exchange membrane (PEM) electrolyte is presented based on parametric test data and current fuel cell technology.

Catalytic Destruction Of Toxic Organic Compounds

NASA Technical Reports Server (NTRS)

Voecks, Gerald E.

1990-01-01

Proposed process disposes of toxic organic compounds in contaminated soil or carbon beds safely and efficiently. Oxidizes toxic materials without producing such other contaminants as nitrogen oxides. Using air, fuel, catalysts, and steam, system consumes less fuel and energy than decontamination processes currently in use. Similar process regenerates carbon beds used in water-treatment plants.

Nanotechnology Applications

EPA Science Inventory

This book chapter discusses various nanotechnologies for water sustainability. Detailed information on catalysis as an advanced oxidation process, nanofiltration, adsorption, water disinfection, and groundwater remediation is provided for water treatment. These nanomaterials effe...

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

Luo, Langli; Su, Mao; Yan, Pengfei

The presence of water vapor, intentional or unavoidable, is crucial to many materials applications, such as steam generator, turbine engine, fuel cell, catalyst, and corrosion 1-6. Phenomenologically, water vapor has been noticed to accelerate oxidation of metals/alloys 7,8, however, the atomistic mechanisms remain elusive. Herein, through direct in situ atomic-scale transmission electron microscopy observation and density functional theory calculation, we reveal that water vapor enhanced oxidation of Ni-Cr alloy is associated with proton dissolution promoted vacancy formation, migration and clustering. Protons derived from water dissociation occupy interstitial position in the oxide lattice, which consequently leads to the lowering of bothmore » vacancy formation energy and the cation diffusion barrier. The atomic scale observations reveal a water vapor derived proton mediated oxide growth mechanism, which provides insights for reckoning many technological processes concerning materials in moist environment at elevated temperatures.« less

Permanganate oxidation of sulfur compounds to prevent poisoning of Pd catalysts in water treatment processes.

PubMed

Angeles-Wedler, Dalia; Mackenzie, Katrin; Kopinke, Frank-Dieter

2008-08-01

The practical application of Pd-catalyzed water treatment processes is impeded by catalyst poisoning by reduced sulfur compounds (RSCs). In this study, the potential of permanganate as a selective oxidant for the removal of microbially generated RSCs in water and as a regeneration agent for S-poisoned catalysts was evaluated. Hydrodechlorination using Pd/Al2O3 was carried out as a probe reaction in permanganate-pretreated water. The activity of the Pd catalysts in the successfully pretreated reaction medium was similar to that in deionized water. The catalyst showed no deactivation behavior in the presence of permanganate at a concentration level < or = 0.07 mM. With a residual oxidant concentration of > or = 0.08 mM, a significant but temporary inhibition of the catalytic dechlorination was observed. Unprotected Pd/Al2O3, which had been completely poisoned by sulfide, was reactivated by a combined treatment with permanganate and hydrazine. However, the anthropogenic water pollutants thiophene and carbon disulfide were resistant against permanganate. Together with the preoxidation of catalyst poisons, hydrophobic protection of the catalysts was studied. Pd/zeolite and various hydrophobically coated catalysts showed a higher stability against ionic poisons and permanganate than the uncoated catalyst. By means of a combination of oxidative water pretreatment and hydrophobic catalyst protection, we provide a new tool to harness the potential of Pd-catalyzed hydrodehalogenation for the treatment of real waters.

Supercritical water oxidation treatment of textile sludge.

PubMed

Zhang, Jie; Wang, Shuzhong; Li, Yanhui; Lu, Jinling; Chen, Senlin; Luo, XingQi

2017-08-01

In this work, we studied the supercritical water oxidation (SCWO) of the textile sludge, the hydrothermal conversion of typical textile compounds and the corrosion properties of stainless steel 316. Moreover, the influence mechanisms of NaOH during these related processes were explored. The results show that decomposition efficiency for organic matter in liquid phase of the textile sludge was improved with the increment of reaction temperature or oxidation coefficient. However, the organic substance in solid phase can be oxidized completely in supercritical water. Serious coking occurred during the high pressure water at 250-450°C for the Reactive Orange 7, while at 300 and 350°C for the polyvinyl alcohol. The addition of NaOH not only accelerated the destruction of organic contaminants in the SCWO reactor, but effectively inhibited the dehydration conversion of textile compounds during the preheating process, which was favorable for the treatment system of textile sludge. The corrosion experiment results indicate that the stainless steel 316 could be competent for the body materials of the reactor and the heat exchangers. Furthermore, there was prominent enhancement of sodium hydroxide for the corrosion resistance of 316 in subcritical water. On the contrary the effect was almost none during SCWO.

Pilot-scale laboratory waste treatment by supercritical water oxidation.

PubMed

Oshima, Yoshito; Hayashi, Rumiko; Yamamoto, Kazuo

2006-01-01

Supercritical water oxidation (SCWO) is a reaction in which organics in an aqueous solution can be oxidized by O2 to CO2 and H2O at a very high reaction rate. In 2003, The University of Tokyo constructed a facility for the SCWO process, the capacity of which is approximately 20 kl/year, for the purpose of treating organic laboratory waste. Through the operation of this facility, we have demonstrated that most of the organics in laboratory waste including halogenated organic compounds can be successfully treated without the formation of dioxines, suggesting that SCWO is useful as an alternative technology to the conventional incineration process.

Nitrogen removal in Northern peatlands treating mine wastewaters

NASA Astrophysics Data System (ADS)

Palmer, Katharina; Karlsson, Teemu; Turunen, Kaisa; Liisa Räisänen, Marja; Backnäs, Soile

2015-04-01

Natural peatlands can be used as passive purification systems for mine wastewaters. These treatment peatlands are well-suited for passive water treatment as they delay the flow of water, and provide a large filtration network with many adsorptive surfaces on plant roots or soil particles. They have been shown to remove efficiently harmful metals and metalloids from mine waters due to variety of chemical, physical and biological processes such as adsorption, precipitation, sedimentation, oxidation and reduction reactions, as well as plant uptake. Many factors affect the removal efficiency such as inflow water quality, wetland hydrology, system pH, redox potential and temperature, the nature of the predominating purification processes, and the presence of other components such as salts. However, less attention has been paid to nitrogen (N) removal in peatlands. Thus, this study aimed to assess the efficiency of N removal and seasonal variation in the removal rate in two treatment peatlands treating mine dewatering waters and process effluent waters. Water sampling from treatment peatland inflow and outflow waters as well as pore waters in peatland were conducted multiple times during 2012-2014. Water samples were analysed for total N, nitrate-N and ammonium-N. Additionally, an YSI EXO2 device was used for continuous nitrate monitoring of waters discharged from treatment peatlands to the recipient river during summer 2014. The results showed that the oxic conditions in upper peat layer and microbial activity in treatment peatlands allowed the efficient oxidation of ammonium-N to nitrite-N and further to nitrate-N during summer time. However, the slow denitrification rate restricts the N removal as not all of the nitrate produced during nitrification is denitrified. In summer time, the removal rate of total N varied between 30-99 % being highest in late summer. N removal was clearly higher for treatment peatland treating process effluent waters than for peatland treating dewatering waters probably due to more oxidizing conditions. During winter time there is not enough microbial activity to maintain oxidation of ammonium-N to nitrate-N. However, almost 20 % of N may be removed during winter season due to nitrate denitrification.

Microwave-assisted synthesis of carbon supported metal/metal oxide nanocomposites and their application in water purification

NASA Astrophysics Data System (ADS)

Gunawan, Gunawan

A novel, easy, and cost effective method for synthesizing carbon supported metal/metal oxide nanocomposites has been studied. Carbon supported metal/metal oxide nanocomposites have niche applications in the area of catalysis, fuel cells, electrodes, and more. The method utilizes a commercial microwave and features the addition of a developed graphite-jacket technique with renewable carbon resources, tannin and lignin. The method has been successfully used to synthesize carbon/nickel, carbon/iron oxide, and carbon/nickel phosphide nanocomposites. The method has shown its versatility in the synthesis of carbon nanocomposites. The process is much simpler when compared with the available methods for synthesizing carbon nanocomposites. The synthesized nanocomposites were classified using several characterization techniques, such as electron microscopy, X-ray powder diffraction, surface area analysis, thermogravimetric analysis, and spectrophotometric studies. One application of the carbon nanocomposite is in wastewater remediation. The synthesized carbon/iron oxide nanocomposite was noted as being useful for removing arsenic (As) and phosphorus (P) from contaminated water. The adsorption process of the nanocomposite was critically studied in order to understand the process of removing pollutants from contaminated water. The study shows that the nanocomposites are capable of removing As and P from contaminated water. Kinetic and adsorption isotherm studies were applied to understand the adsorption of As and P onto the adsorbent. Several methods, such as pseudo-first and second order kinetic models, Elovich's equation, and the Weber-Morris intraparticle diffusion model were used to explain the kinetic aspects of the adsorption process. For the adsorption isotherm study, Langmuir and Freundlich isotherm models were applied.

Inactivation of dinoflagellate Scripsiella trochoidea in synthetic ballast water by advanced oxidation processes.

PubMed

Yang, Zhishan; Jiang, Wenju; Zhang, Yi; Lim, T M

2015-01-01

Ship-borne ballast water contributes significantly to the transfer of non-indigenous species across aquatic environments. To reduce the risk of bio-invasion, ballast water should be treated before discharge. In this study, the efficiencies of several conventional and advanced oxidation processes were investigated for potential ballast water treatment, using a marine dinoflagellate species, Scripsiella trochoidea, as the indicator organism. A stable and consistent culture was obtained and treated by ultraviolet (UV) light, ozone (O3), hydrogen peroxide (H2O2), and their various combinations. UV apparently inactivated the cells after only 10 s of irradiation, but subsequently photo-reactivation of the cells was observed for all methods involving UV. O3 exhibited 100% inactivation efficiency after 5 min treatment, while H2O2 only achieved maximum 80% inactivation in the same duration. Combined methods, e.g. UV/O3 and UV/H2O2, were found to inhibit photo-reactivation and improve treatment efficiency to some degree, indicating the effectiveness of using combined treatment processes. The total residual oxidant (TRO) levels of the methods were determined, and the results indicated that UV and O3 generated the lowest and highest TRO, respectively. The synergic effect of combined processes on TRO generation was found to be insignificant, and thus UV/O3 was recommended as a potentially suitable treatment process for ballast water.

Solar-Enhanced Advanced Oxidation Processes for Water Treatment: Simultaneous Removal of Pathogens and Chemical Pollutants.

PubMed

Tsydenova, Oyuna; Batoev, Valeriy; Batoeva, Agniya

2015-08-14

The review explores the feasibility of simultaneous removal of pathogens and chemical pollutants by solar-enhanced advanced oxidation processes (AOPs). The AOPs are based on in-situ generation of reactive oxygen species (ROS), most notably hydroxyl radicals •OH, that are capable of destroying both pollutant molecules and pathogen cells. The review presents evidence of simultaneous removal of pathogens and chemical pollutants by photocatalytic processes, namely TiO2 photocatalysis and photo-Fenton. Complex water matrices with high loads of pathogens and chemical pollutants negatively affect the efficiency of disinfection and pollutant removal. This is due to competition between chemical substances and pathogens for generated ROS. Other possible negative effects include light screening, competitive photon absorption, adsorption on the catalyst surface (thereby inhibiting its photocatalytic activity), etc. Besides, some matrix components may serve as nutrients for pathogens, thus hindering the disinfection process. Each type of water/wastewater would require a tailor-made approach and the variables that were shown to influence the processes-catalyst/oxidant concentrations, incident radiation flux, and pH-need to be adjusted in order to achieve the required degree of pollutant and pathogen removal. Overall, the solar-enhanced AOPs hold promise as an environmentally-friendly way to substitute or supplement conventional water/wastewater treatment, particularly in areas without access to centralized drinking water or sewage/wastewater treatment facilities.

ADVANCED OXIDATION PROCESS TECHNOLOGY (ULTRAVIOLET RADIATION/OZONE TREATMENT) FOR REMOVAL OF METHYL TERTIARY BUTYL ETHER (MTBE) IN GROUND WATER SUPPLIES.

EPA Science Inventory

U.S. EPA’s Office of Research and Development in Cincinnati, Ohio has been testing and evaluating MTBE removal in dechlorinated tap water using three oxidant combinations: hydrogen peroxide/ozone, ultraviolet irradiation (UV)/ozone, and UV/ozone/hydrogen peroxide. Pilot-scale st...

Ubiquitous anaerobic ammonium oxidation in inland waters of China: an overlooked nitrous oxide mitigation process

PubMed Central

Zhu, Guibing; Wang, Shanyun; Zhou, Leiliu; Wang, Yu; Zhao, Siyan; Xia, Chao; Wang, Weidong; Zhou, Rong; Wang, Chaoxu; Jetten, Mike S. M.; Hefting, Mariet M.; Yin, Chengqing; Qu, Jiuhui

2015-01-01

Denitrification has long been regarded as the only pathway for terrestrial nitrogen (N) loss to the atmosphere. Here we demonstrate that large-scale anaerobic ammonium oxidation (anammox), an overlooked N loss process alternative to denitrification which bypasses nitrous oxide (N2O), is ubiquitous in inland waters of China and contributes significantly to N loss. Anammox rates in aquatic systems show different levels (1.0–975.9 μmol N m−2 h−1, n = 256) with hotspots occurring at oxic-anoxic interfaces and harboring distinct biogeochemical and biogeographical features. Extrapolation of these results to the China-national level shows that anammox could contribute about 2.0 Tg N yr−1, which equals averagely 11.4% of the total N loss from China’s inland waters. Our results indicate that a significant amount of the nitrogen lost from inland waters bypasses denitrification, which is important for constructing more accurate climate models and may significantly reduce potential N2O emission risk at a large scale. PMID:26610807

Superlubricating graphene and graphene oxide films

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

Sumant, Anirudha V.; Erdemir, Ali; Choi, Junho

A system and method for forming at least one of graphene and graphene oxide on a substrate and an opposed wear member. The system includes graphene and graphene oxide formed by an exfoliation process or solution processing method to dispose graphene and/or graphene oxide onto a substrate. The system further includes an opposing wear member disposed on another substrate and a gas atmosphere of an inert gas like N2, ambient, a humid atmosphere and a water solution.

Improved Electrolytic Hydrogen Peroxide Generator

NASA Technical Reports Server (NTRS)

James, Patrick I.

2005-01-01

An improved apparatus for the electrolytic generation of hydrogen peroxide dissolved in water has been developed. The apparatus is a prototype of H2O2 generators for the safe and effective sterilization of water, sterilization of equipment in contact with water, and other applications in which there is need for hydrogen peroxide at low concentration as an oxidant. Potential applications for electrolytic H2O2 generators include purification of water for drinking and for use in industrial processes, sanitation for hospitals and biotechnological industries, inhibition and removal of biofouling in heat exchangers, cooling towers, filtration units, and the treatment of wastewater by use of advanced oxidation processes that are promoted by H2O2.

Hydrogeochemistry of prairie pothole region wetlands: Role of long-term critical zone processes

USGS Publications Warehouse

Goldhaber, Martin B.; Mills, Christopher T.; Morrison, Jean M.; Stricker, Craig A.; Mushet, David M.; LaBaugh, James W.

2014-01-01

Results from the CWLSA were scaled up to a 9700 km2 area surrounding CWLSA using ~ 1800 drill logs and literature data on wetland water chemistry for 178 wetlands within this larger area. The oxidized brown zone depth and wetland water compositional trends are very similar to the CWLSA. Additionally, surface water data from 176 southern Canadian pothole wetlands that conform to the same wetland water geochemical trends as those recorded in the CWLSA further corroborate that SO42 − accumulation driven by pyrite oxidation is a nearly ubiquitous process in the prairie pothole region and distinguishes PPR wetlands from other wetlands worldwide that have a similar overall hydrology.

Isotope geochemistry of waters affected by acid mine drainage in old labour sites (SE, Spain).

NASA Astrophysics Data System (ADS)

Pérez-Sirvent, Carmen; Martinez-Sanchez, Maria Jose; Garcia-Lorenzo, Maria Luz; Agudo, Ines; Hernandez-Cordoba, Manuel; Recio, Clemente

2015-04-01

The ore deposits of this zone have iron, lead and zinc as the main metal components. Iron is present in oxides, hydroxides, sulfides, sulfates, carbonates, and silicates; lead and zinc occur in sulfides (galena and sphalerite, respectively), carbonates, sulfates, and lead or zinc-bearing (manganese, iron) oxides. Mining started with the Romans and activity peaked in the second half of the 19th century and throughout the 20th century until the 1980's. From 1940 to 1957, mineral concentration was made by froth flotation and, prior to this, by gravimetric techniques. The mining wastes, or tailings, with a very fine particle size were deposited inland (tailings dams) and, since 1957, huge releases were made in directly the sea coast. The objective of this work was to evaluate processes affecting waters from abandoned mine sites by way of stable isotopic analysis, particularly H and O stable isotopes from water and S and O from dissolved sulfates. Several common chemical and physical processes, such as evaporation, water-rock interaction and mixing could alter water isotopic composition. Evaporation, which causes an enrichment in δD and δ18O in the residual water, is an important process in semiarid areas. The results obtained indicate that, for sites near the coast, waters are meteoric, and marine infiltration only takes place in the deepest layers near the shore or if water remains stagnated in sediments with low permeability. The main source of sulfate was the oxidation of sulfides, resulting in the liberation of acid, sulfate and metals. In order to assess the mechanism responsible for sulfide oxidation, the stoichiometric isotope balance model and the general isotope balance model were tested, suggesting that the oxidation via Fe3+ was predominant in the surface, and controlled by A. ferrooxidans, while at depth, sulfate reduction occurred.

Removal of antibiotic cloxacillin by means of electrochemical oxidation, TiO2 photocatalysis, and photo-Fenton processes: analysis of degradation pathways and effect of the water matrix on the elimination of antimicrobial activity.

PubMed

Serna-Galvis, Efraim A; Giraldo-Aguirre, Ana L; Silva-Agredo, Javier; Flórez-Acosta, Oscar A; Torres-Palma, Ricardo A

2017-03-01

This study evaluates the treatment of the antibiotic cloxacillin (CLX) in water by means of electrochemical oxidation, TiO 2 photocatalysis, and the photo-Fenton system. The three treatments completely removed cloxacillin and eliminated the residual antimicrobial activity from synthetic pharmaceutical wastewater containing the antibiotic, commercial excipients, and inorganic ions. However, significant differences in the degradation routes were found. In the photo-Fenton process, the hydroxyl radical was involved in the antibiotic removal, while in the TiO 2 photocatalysis process, the action of both the holes and the adsorbed hydroxyl radicals degraded the pollutant. In the electrochemical treatment (using a Ti/IrO 2 anode in sodium chloride as supporting electrolyte), oxidation via HClO played the main role in the removal of CLX. The analysis of initial by-products showed five different mechanistic pathways: oxidation of the thioether group, opening of the central β-lactam ring, breakdown of the secondary amide, hydroxylation of the aromatic ring, and decarboxylation. All the oxidation processes exhibited the three first pathways. Moreover, the aromatic ring hydroxylation was found in both photochemical treatments, while the decarboxylation of the pollutant was only observed in the TiO 2 photocatalysis process. As a consequence of the degradation routes and mechanistic pathways, the elimination of organic carbon was different. After 480 and 240 min, the TiO 2 photocatalysis and photo-Fenton processes achieved ∼45 and ∼15 % of mineralization, respectively. During the electrochemical treatment, 100 % of the organic carbon remained even after the antibiotic was treated four times the time needed to degrade it. In contrast, in all processes, a natural matrix (mineral water) did not considerably inhibit pollutant elimination. However, the presence of glucose in the water significantly affected the degradation of CLX by means of TiO 2 photocatalysis.

Development of Advanced ISS-WPA Catalysts for Organic Oxidation at Reduced Pressure/Temperature

NASA Technical Reports Server (NTRS)

Yu, Ping; Nalette, Tim; Kayatin, Matthew

2016-01-01

The Water Processor Assembly (WPA) at International Space Station (ISS) processes a waste stream via multi-filtration beds, where inorganic and non-volatile organic contaminants are removed, and a catalytic reactor, where low molecular weight organics not removed by the adsorption process are oxidized at elevated pressure in the presence of oxygen and elevated temperature above the normal water boiling point. Operation at an elevated pressure requires a more complex system design compared to a reactor that could operate at ambient pressure. However, catalysts currently available have insufficient activity to achieve complete oxidation of the organic load at a temperature less than the water boiling point and ambient pressure. Therefore, it is highly desirable to develop a more active and efficient catalyst at ambient pressure and a moderate temperature that is less than water boiling temperature. This paper describes our efforts in developing high efficiency water processing catalysts. Different catalyst support structures and coating metals were investigated in subscale reactors and results were compared against the flight WPA catalyst. Detailed improvements achieved on alternate metal catalysts at ambient pressure and 200 F will also be presented in the paper.

Membrane-organized Chemical Photoredox Systems

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

Britt, R. David

2016-09-01

The key photoredox process in photosynthesis is the accumulation of oxidizing equivalents on a tetranuclear manganese cluster that then liberates electrons and protons from water and forms oxygen gas. Our primary goal in this project is to characterize inorganic systems that can perform this same water-splitting chemistry. One such species is the dinuclear ruthenium complex known as the blue dimer. Starting at the Ru(III,III) oxidation state, the blue dimer is oxidized up to a putative Ru(V,V) level prior to O-O bond formation. We employ electron paramagnetic resonance spectroscopy to characterize each step in this reaction cycle to gain insight intomore » the molecular mechanism of water oxidation.« less

Treatment of municipal sewage sludge in supercritical water: A review.

PubMed

Qian, Lili; Wang, Shuzhong; Xu, Donghai; Guo, Yang; Tang, Xingying; Wang, Laisheng

2016-02-01

With increasing construction of wastewater treatment plants and stricter policies, municipal sewage sludge (MSS) disposal has become a serious problem. Treatment of MSS in supercritical water (SCW) can avoid the pre-drying procedure and secondary pollution of conventional methods. SCW treatment methods can be divided into supercritical water gasification (SCWG), supercritical water partial oxidation (SCWPO) and supercritical water oxidation (SCWO) technologies with increasing amounts of oxidants. Hydrogen-rich gases can be generated from MSS by SCWG or SCWPO technology using oxidants less than stoichiometric ratio while organic compounds can be completely degraded by SCWO technology with using an oxidant excess. For SCWG and SCWPO technologies, this paper reviews the influences of different process variables (MSS properties, moisture content, temperature, oxidant amount and catalysts) on the production of gases. For SCWO technology, this paper reviews research regarding the removal of organics with or without hydrothermal flames and the changes in heavy metal speciation and risk. Finally, typical systems for handling MSS are summarized and research needs and challenges are proposed. Copyright © 2015 Elsevier Ltd. All rights reserved.

Plutonium Oxide Containment and the Potential for Water-Borne Transport as a Consequence of ARIES Oxide Processing Operations

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

Wayne, David Matthew; Rowland, Joel C.

2015-02-01

The question of oxide containment during processing and storage has become a primary concern when considering the continued operability of the Plutonium Facility (PF-4) at Los Alamos National Laboratory (LANL). An Evaluation of the Safety of the Situation (ESS), “Potential for Criticality in a Glovebox Due to a Fire” (TA55-ESS-14-002-R2, since revised to R3) first issued in May, 2014 summarizes these concerns: “The safety issue of fire water potentially entering a glovebox is: the potential for the water to accumulate in the bottom of a glovebox and result in an inadvertent criticality due to the presence of fissionable materials inmore » the glovebox locations and the increased reflection and moderation of neutrons from the fire water accumulation.” As a result, the existing documented safety analysis (DSA) was judged inadequate and, while it explicitly considered the potential for criticality resulting from water intrusion into gloveboxes, criticality safety evaluation documents (CSEDs) for the affected locations did not evaluate the potential for fire water intrusion into a glovebox.« less

Combined processes of ozonation and supercritical water oxidation for landfill leachate degradation.

PubMed

Scandelai, Ana Paula Jambers; Cardozo Filho, Lúcio; Martins, Danielly Cruz Campos; Freitas, Thabata Karoliny Formicoli de Souza; Garcia, Juliana Carla; Tavares, Célia Regina Granhen

2018-04-25

Leachate is a highly variable, heterogeneous and recalcitrant wastewater generated in landfills which may contain high concentrations of many organic and inorganic compounds, hampering the application of a single technique in its treatment. Therefore, this paper assessed leachate degradation through supercritical water oxidation (ScWO) as well as combined processes of ozonation and supercritical water oxidation (O 3 /ScWO and ScWO/O 3 ), a yet innovative combination. Ozonation was carried out at different reaction times (30-120 min). ScWO was developed at 600 °C, 23 MPa, and spatial time (τ) from 29 to 52 s. A combination of ozonation (30 min) and supercritical water oxidation process (O 3 -30'/ScWO) was the most efficient technique for the degradation of the leachate assessed. These conditions enabled to remove high values of apparent and true color (92% and 97%, respectively), biochemical oxygen demand (BOD 5,20 ) (95%), chemical oxygen demand (COD) (92%), total organic carbon (TOC) (79%), nitrite (78%), nitrate (84%), total (96%), dissolved (96%) and suspended (94%) solids. In addition, the combined process presented significant decrease in electric conductivity (EC) (68%) and less leachate turbidity removal (43%). Except for ammonia and nitrite, all parameters of the leachate treated by O 3 -30'/ScWO met the specifications of Brazilian legislation (CONAMA Resolutions No. 357/2005 and No. 430/2011) for the disposal of wastewater in water bodies. Besides, both processes are considered to be clean technologies. This shows the great possibility of applying the O 3 /ScWO combination to landfills leachates. Copyright © 2018 Elsevier Ltd. All rights reserved.

Enhanced graphene oxide membranes and methods for making same

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

Shin, Yongsoon; Gotthold, David W.; Fifield, Leonard S.

A method for making a graphene oxide membrane and a resulting free-standing graphene oxide membrane that provides desired qualities of water permeability and selectivity at larger sizes, thinner cross sections, and with increased ruggedness as compared to existing membranes and processes.

Electrooxidation of organics in waste water

NASA Technical Reports Server (NTRS)

Hitchens, G. D.; Murphy, Oliver J.; Kaba, Lamine; Verostko, Charles E.

1990-01-01

Electrooxidation is a means of removing organic solutes directly from waste waters without the use of chemical expendables. Research sponsored by NASA is currently being pursued to demonstrate the feasibility of the concept for oxidation of organic impurities common to urine, shower waters and space-habitat humidity condensates. Electrooxidation of urine and waste water ersatz was experimentally demonstrated. This paper discusses the electrooxidation principle, reaction kinetics, efficiency, power, size, experimental test results and water-reclamation applications. Process operating potentials and the use of anodic oxidation potentials that are sufficiently low to avoid oxygen formation and chloride oxidation are described. The design of an electrochemical system that incorporates a membrane-based electrolyte based on parametric test data and current fuel-cell technology is presented.

Zinc oxide nanocolloids prepared by picosecond pulsed laser ablation in water at different temperatures

NASA Astrophysics Data System (ADS)

D'Urso, Luisa; Spadaro, Salvatore; Bonsignore, Martina; Santangelo, Saveria; Compagnini, Giuseppe; Neri, Fortunato; Fazio, Enza

2018-01-01

Zinc oxide with wide direct band gap and high exciton binding energy is one of the most promising materials for ultraviolet (UV) light-emitting devices. It further exhibits good performance in the degradation of non-biodegradable pollutants under UV irradiation. In this work, zinc oxide (ZnO) and zinc oxide/gold (ZnO/Au) nanocolloids are prepared by picosecond pulsed laser ablation (ps-PLA), using a Zn and Au metallic targets in water media at room temperature (RT) and 80°C. ZnO and Au nanoparticles (NPs) with size in the 10-50 nm range are obtained at RT, while ZnO nanorods (NRs) are formed when water is maintained at 80°C during the ps-PLA process. Au NPs, added to ZnO colloids after the ablation process, decorate ZnO NRs. The crystalline phase of all ZnO nanocolloids is wurtzite. Methylene blue dye is used to investigate the photo-catalytic activity of all the synthesised nanocolloids, under UV light irradiation.

Advanced oxidation and disinfection processes for onsite net-zero greywater reuse: A review.

PubMed

Gassie, Lucien W; Englehardt, James D

2017-11-15

Net-zero greywater (NZGW) reuse, or nearly closed-loop recycle of greywater for all original uses, can recover both water and its attendant hot-water thermal energy, while avoiding the installation and maintenance of a separate greywater sewer in residential areas. Such a system, if portable, could also provide wash water for remote emergency health care units. However, such greywater reuse engenders human contact with the recycled water, and hence superior treatment. The purpose of this paper is to review processes applicable to the mineralization of organics, including control of oxidative byproducts such as bromate, and maintenance of disinfection consistent with potable reuse guidelines, in NZGW systems. Specifically, TiO 2 -UV, UV-hydrogen peroxide, hydrogen peroxide-ozone, ozone-UV advanced oxidation processes, and UV, ozone, hydrogen peroxide, filtration, and chlorine disinfection processes were reviewed for performance, energy demand, environmental impact, and operational simplicity. Based on the literature reviewed, peroxone is the most energy-efficient process for organics mineralization. However, in portable applications where delivery of chemicals to the site is a concern, the UV-ozone process appears promising, at higher energy demand. In either case, reverse osmosis, nanofiltration, or ED may be useful in controlling the bromide precursor in make-up water, and a minor side-stream of ozone may be used to prevent microbial regrowth in the treated water. Where energy is not paramount, UV-hydrogen peroxide and UV-TiO 2 can be used to mineralize organics while avoiding bromate formation, but may require a secondary process to prevent microbial regrowth. Chlorine and ozone may be useful for maintenance of disinfection residual. Copyright © 2017 Elsevier Ltd. All rights reserved.

Process for the displacement of cyanide ions from metal-cyanide complexes

DOEpatents

Smith, Barbara F.; Robinson, Thomas W.

1997-01-01

The present invention relates to water-soluble polymers and the use of such water-soluble polymers in a process for the displacement of the cyanide ions from the metal ions within metal-cyanide complexes. The process waste streams can include metal-cyanide containing electroplating waste streams, mining leach waste streams, mineral processing waste streams, and related metal-cyanide containing waste streams. The metal ions of interest are metals that give very strong complexes with cyanide, mostly iron, nickel, and copper. The physical separation of the water-soluble polymer-metal complex from the cyanide ions can be accomplished through the use of ultrafiltration. Once the metal-cyanide complex is disrupted, the freed cyanide ions can be recovered for reuse or destroyed using available oxidative processes rendering the cyanide nonhazardous. The metal ions are released from the polymer, using dilute acid, metal ion oxidation state adjustment, or competing chelating agents, and collected and recovered or disposed of by appropriate waste management techniques. The water-soluble polymer can then be recycled. Preferred water-soluble polymers include polyethyleneimine and polyethyleneimine having a catechol or hydroxamate group.

Waste Water Management and Infectious Disease. Part II: Impact of Waste Water Treatment

ERIC Educational Resources Information Center

Cooper, Robert C.

1975-01-01

The ability of various treatment processes, such as oxidation ponds, chemical coagulation and filtration, and the soil mantle, to remove the agents of infectious disease found in waste water is discussed. The literature concerning the efficiency of removal of these organisms by various treatment processes is reviewed. (BT)

Oxidation of the antibacterial agent norfloxacin during sodium hypochlorite disinfection of marine culture water.

PubMed

Zhang, Yuanyuan; Rong, Chuan; Song, Yanqun; Wang, Yinghui; Pei, Jiying; Tang, Xinying; Zhang, Ruijie; Yu, Kefu

2017-09-01

Chlorination disinfection and antibiotic addition are two universal processes of marine culture. The generation of disinfection byproducts (DBPs) is unavoidable. Antibiotic residue not only pollutes water but also acts as a precursor to the production of new DBPs. The fate of antibiotic norfloxacin (NOR) in chlorination disinfection was investigated. It was observed that NOR could be oxidized by disinfection agent sodium hypochlorite, but the oxidation rate varied considerably with the type of disinfected water. For fresh water, marine culture water and sea water, the reaction rate constant was 0.066 min -1 , 0.466 min -1 and 1.241 min -1 , respectively. The difference was primarily attributed to the promotion role of bromide ions in seawater and marine culture water. Moreover, the bromide ions could result in the generation of brominated DBPs (Br-DBPs). The kinetics, products, reaction centers and mechanisms were investigated. The active site of NOR was found to be the N4 atom on piperazinyl in fresh water. During marine culture water and sea water disinfection, the carboxyl on NOR was oxidized and two Br-DBPs were formed. This was attributed to the lowering of the reaction's required activation energy when performed in the presence of bromide ions. The Br-DBPs were also confirmed in real shrimp pond brackish water. Quantitative structure activity relationships and the total organic halogen analysis showed that the DBPs in marine culture water possessed stronger toxicological properties than the DBPs in fresh water. The toxicity increase was attributed to the production of Br-DBPs in the disinfection process of marine culture water. Copyright © 2017 Elsevier Ltd. All rights reserved.

DESTRUCTION OF PAHS AND PCBS IN WATER USING SULFATE RADICAL-BASED CATALYTIC ADVANCED OXIDATION PROCESSES

EPA Science Inventory

A new class of advanced oxidation processes (AOPs) based on sulfate radicals is being tested for the degradation of polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs) in aqueous solution. These AOPs are based on the generation of sulfate radicals through...

Chemical analysis of extracting transition metal oxides from polymetallic ore by sulphate process

NASA Astrophysics Data System (ADS)

Enkh-Uyanga, Otgon-Uul; Munkhtsetseg, Baatar; Urangoo, Urtnasan; Tserendulam, Enkhtur; Agiimaa, Davaadorj

2017-06-01

In this research work we attempt to improve the purity of polymetallic ores in Mongolia whilst developing practical applications of its refinement processes and this paper presents the results of chemical research of extracting transition metal titanium oxides, ferrous oxide and rare earth oxides from polymetallic ore. Thereby, chemical and mineral analysis of polymetallic ore is carried out basis of responses to the support process at various degrees of water whereas transition metal sulphates solubility differ. As a result of sulphate and resulphurization process we have extracted anatase with 62.5 percent titanium dioxide and brookite mineral with 89.6 percent of titanium dioxide as well as mineral with 83.8 percent of ferrous oxide hematite and rare earth oxides with 57.6 percent of cerium oxide. These oxides are identified under various conditions in the thermal processing. The morphology structure and chemical content compound of the mineral has been verified as a result of the XRF, XRD, SEM-EDX analysis.

Chemical and toxicological evaluation of transformation products during advanced oxidation processes.

PubMed

vom Eyser, C; Börgers, A; Richard, J; Dopp, E; Janzen, N; Bester, K; Tuerk, J

2013-01-01

The entry of pharmaceuticals into the water cycle from sewage treatment plants is of growing concern because environmental effects are evident at trace levels. Ozonation, UV- and UV/H(2)O(2)-treatment were tested as an additional step in waste water treatment because they have been proven to be effective in eliminating aqueous organic contaminants. The pharmaceuticals carbamazepine, ciprofloxacin, diclofenac, metoprolol and sulfamethoxazole as well as the personal care products galaxolide and tonalide were investigated in terms of degradation efficiency and by-product formation in consideration of toxic effects. The substances were largely removed from treatment plant effluent by ozonation, UV- and UV/H(2)O(2)-treatment. Transformation products were detected in all tested treatment processes. Accompanying analysis showed no genotoxic, cytotoxic or estrogenic potential for the investigated compounds after oxidative treatment of real waste waters. The results indicate that by-product formation from ozonation and advanced oxidation processes does not have any negative environmental impact.

The important role of water in growth of monolayer transition metal dichalcogenides

NASA Astrophysics Data System (ADS)

Kastl, Christoph; Chen, Christopher T.; Kuykendall, Tevye; Shevitski, Brian; Darlington, Thomas P.; Borys, Nicholas J.; Krayev, Andrey; Schuck, P. James; Aloni, Shaul; Schwartzberg, Adam M.

2017-06-01

2D transition metal dichalcogenides (TMDs) are commonly grown by chemical vapor deposition using transition metal oxides as solid precursors. Despite the widespread use of this technique, challenges in reproducibility, coverage, and material quality are pervasive, suggestive of unknown and uncontrolled process parameters. In this communication, we demonstrate the impact of water vapor on this growth process. Our results show a direct correlation between gas phase water content and the morphology of TMD films. In particular, we show that the presence of water enhances volatilization, and therefore the vapor transport of tungsten and molybdenum oxide. Surprisingly, we find that water not only plays an important role in volatilization but is also compatible with TMD growth. In fact, carefully controlled humidity can consistently produce high quality, luminescent materials.

Transformation of pharmaceuticals during oxidation/disinfection processes in drinking water treatment.

PubMed

Postigo, Cristina; Richardson, Susan D

2014-08-30

Pharmaceuticals are emerging contaminants of concern and are widespread in the environment. While the levels of these substances in finished drinking waters are generally considered too low for human health concern, there are now concerns about their disinfection by-products (DBPs) that can form during drinking water treatment, which in some cases have been proven to be more toxic than the parent compounds. The present manuscript reviews the transformation products of pharmaceuticals generated in water during different disinfection processes, i.e. chlorination, ozonation, chloramination, chlorine dioxide, UV, and UV/hydrogen peroxide, and the main reaction pathways taking place. Most of the findings considered for this review come from controlled laboratory studies involving reactions of pharmaceuticals with these oxidants used in drinking water treatment. Copyright © 2014 Elsevier B.V. All rights reserved.

Synergistic effects of water addition and step heating on the formation of solution-processed zinc tin oxide thin films: towards high-mobility polycrystalline transistors

NASA Astrophysics Data System (ADS)

Huang, Genmao; Duan, Lian; Zhao, Yunlong; Zhang, Yunge; Dong, Guifang; Zhang, Deqiang; Qiu, Yong

2016-11-01

Thin-film transistors (TFTs) with high mobility and good uniformity are attractive for next-generation flat panel displays. In this work, solution-processed polycrystalline zinc tin oxide (ZTO) thin film with well-ordered microstructure is prepared, thanks to the synergistic effect of water addition and step heating. The step heating treatment other than direct annealing induces crystallization, while adequate water added to precursor solution further facilitates alloying and densification process. The optimal polycrystalline ZTO film is free of hierarchical sublayers, and featured with an increased amount of ternary phases, as well as a decreased fraction of oxygen vacancies and hydroxides. TFT devices based on such an active layer exhibit a remarkable field-effect mobility of 52.5 cm2 V-1 s-1, a current on/off ratio of 2 × 105, a threshold voltage of 2.32 V, and a subthreshold swing of 0.36 V dec-1. Our work offers a facile method towards high-performance solution-processed polycrystalline metal oxide TFTs.

Comparison of various advanced oxidation processes used in remediation of industrial wastewater laden with recalcitrant pollutants

NASA Astrophysics Data System (ADS)

Krishnan, S.; Rawindran, H.; Sinnathambi, C. M.; Lim, J. W.

2017-06-01

Due to the scarcity of water, it has become a necessity to improve the quality of wastewater that is discharged into the environment. Conventional wastewater treatment can be either a physical, chemical, and/or biological processes, or in some cases a combination of these operations. The main purpose of wastewater treatment is to eliminate nutrients, solids, and organic compounds from effluents. Current wastewater treatment technologies are deemed ineffective in the complete removal of pollutants, particularly organic matter. In many cases, these organic compounds are resistant to conventional treatment methods, thus creating the necessity for tertiary treatment. Advanced oxidation process (AOP), constitutes as a promising treatment technology for the management of wastewater. AOPs are characterised by a common chemical feature, where they utilize the highly reactive hydroxyl radicals for achieving complete mineralization of the organic pollutants into carbon dioxide and water. This paper delineates advanced oxidation processes currently used for the remediation of water and wastewater. It also provides the cost estimation of installing and running an AOP system. The costs are separated into three categories: capital, operational, and operating & maintenance.

Reactor Experiments at the University of Minnesota.

DTIC Science & Technology

1987-07-15

metallurgy; zinc, zinc oxide; solar thermal,’ solar Pi% thermoelectrochemical’ water splitting, separation devices; reactors e, ? 20. AeSiRACT (Continue oe...reported. Water splitting, recovery of hydrogen 4. and sulfur from hydrogen sulfide, electrolysis of zinc oxide in vapor and liquid phases, oil...CH4-CO2 reforming process. 2. Hydrogen production from water and the production of hydrogen and sulfur (or ammonia and sulfuric acid) from H2S. 3

Water oxidation catalysed by manganese compounds: from complexes to 'biomimetic rocks'.

PubMed

Wiechen, Mathias; Berends, Hans-Martin; Kurz, Philipp

2012-01-07

One of the most fundamental processes of the natural photosynthetic reaction sequence is the light-driven oxidation of water to molecular oxygen. In vivo, this reaction takes place in the large protein ensemble Photosystem II, where a μ-oxido-Mn(4)Ca- cluster, the oxygen-evolving-complex (OEC), has been identified as the catalytic site for the four-electron/four-proton redox reaction of water oxidation. This Perspective presents recent progress for three strategies which have been followed to prepare functional synthetic analogues of the OEC: (1) the synthesis of dinuclear manganese complexes designed to act as water-oxidation catalysts in homogeneous solution, (2) heterogeneous catalysts in the form of clay hybrids of such Mn(2)-complexes and (3) the preparation of manganese oxide particles of different compositions and morphologies. We discuss the key observations from the studies of such synthetic manganese systems in order to shed light upon the catalytic mechanism of natural water oxidation. Additionally, it is shown how research in this field has recently been motivated more and more by the prospect of finding efficient, robust and affordable catalysts for light-driven water oxidation, a key reaction of artificial photosynthesis. As manganese is an abundant and non-toxic element, manganese compounds are very promising candidates for the extraction of reduction equivalents from water. These electrons could consecutively be fed into the synthesis of "solar fuels" such as hydrogen or methanol.

Towards the rational design of the Py5-ligand framework for ruthenium-based water oxidation catalysts.

PubMed

Schilling, Mauro; Böhler, Michael; Luber, Sandra

2018-05-21

In order to rationally design water oxidation catalysts (WOCs), an in-depth understanding of the reaction mechanism is essential. In this study we showcase the complexity of catalytic water oxidation, by elucidating how modifications of the pentapyridyl (Py5) ligand-framework influence the thermodynamics and kinetics of the process. In the reaction mechanism the pyridine-water exchange was identified as a key reaction which appears to determine the reactivity of the Py5-WOCs. Exploring the capabilities of in silico design we show which modifications of the ligand framework appear promising when attempting to improve the catalytic performance of WOCs derived from Py5.

Efficient photocatalytic oxidation of arsenite from contaminated water by Fe2O3-Mn2O3 nanocomposite under UVA radiation and process optimization with experimental design.

PubMed

Eslami, Hadi; Ehrampoush, Mohammad Hassan; Esmaeili, Abbas; Ebrahimi, Ali Asghar; Salmani, Mohammad Hossein; Ghaneian, Mohammad Taghi; Falahzadeh, Hossein

2018-09-01

The efficiency of photocatalytic oxidation process in arsenite (As(III)) removal from contaminated water by a new Fe 2 O 3 -Mn 2 O 3 nanocomposite under UV A radiation was investigated. The effect of nanocomposite dosage, pH and initial As(III) concentration on the photocatalytic oxidation of As(III) were studied by experimental design. The synthesized nanocomposite had a uniform and spherical morphological structure and contained 49.83% of Fe 2 O 3 and 29.36% of Mn 2 O 3 . Based on the experimental design model, in photocatalytic oxidation process, the effect of pH was higher than other parameters. At nanocomposite concentrations of more than 12 mg L -1 , pH 4 to 6 and oxidation time of 30 min, photocatalytic oxidation efficiency was more than 95% for initial As(III) concentration of less than 500 μg L -1 . By decreasing pH and increasing the nanocomposite concentration, the photocatalytic oxidation efficiency was increased. Furthermore, by increasing the oxidation time from 10 to 240 min, in addition to oxidation of As(III) to arsenate (As(V)), the residual As(V) was adsorbed on the Fe 2 O 3 -Mn 2 O 3 nanocomposite and total As concentration was decreased. Therefore, Fe 2 O 3 -Mn 2 O 3 nanocomposite as a bimetal oxide, at low doses and short time, can enhance and improve the efficiency of the photocatalytic oxidation and adsorption of As(III) from contaminated water resources. Furthermore, the energy and material costs of the UV A /Fe 2 O 3 -Mn 2 O 3 system for photocatalytic oxidation of 1  mg L -1 As(III) in the 1 L laboratory scale reactor was 0.0051 €. Copyright © 2018 Elsevier Ltd. All rights reserved.

Time resolved study of hydroxyl radical oxidation of oleic acid at the air-water interface

NASA Astrophysics Data System (ADS)

Zhang, Xinxing; Barraza, Kevin M.; Upton, Kathleen T.; Beauchamp, J. L.

2017-09-01

The ubiquity of oleic acid (OA) renders it a poster child for laboratory investigations of environmental oxidation chemistry. In the current study, mechanistic details of the oxidation of OA by hydroxyl radicals at the air-water interface are investigated using field-induced droplet ionization mass spectrometry (FIDI-MS). Products from OH oxidation of both unsaturated and saturated carbon atoms are identified, and mechanisms for both types of oxidation processes are proposed. Uptake of oxygen in the interfacial layer increases linearly with time, consistent with Langmuir-Hinshelwood reaction kinetics. These results provide fundamental knowledge relating to OH initiated degradation of fatty acids in atmospheric aerosols.

Removal of ammonia from urine vapor by a dual-catalyst system

NASA Technical Reports Server (NTRS)

Budininkas, P.

1977-01-01

The feasibility of removing ammonia from urine vapor by a low-temperature dual-catalyst system has been demonstrated. The process is based on the catalytic oxidation of ammonia to a mixture of nitrogen, nitrous oxide, and water, followed by a catalytic decomposition of the nitrous oxide into its elements. Potential ammonia oxidation and nitrous oxide decomposition catalysts were first screened with artificial gas mixtures, then tested with the actual urine vapor produced by boiling untreated urine. A suitable dual-catalyst bed arrangement was found that achieved the removal of ammonia and also organic carbon, and recovered water of good quality from urine vapor.

Electron injection dynamics in high-potential porphyrin photoanodes.

PubMed

Milot, Rebecca L; Schmuttenmaer, Charles A

2015-05-19

There is a growing need to utilize carbon neutral energy sources, and it is well known that solar energy can easily satisfy all of humanity's requirements. In order to make solar energy a viable alternative to fossil fuels, the problem of intermittency must be solved. Batteries and supercapacitors are an area of active research, but they currently have relatively low energy-to-mass storage capacity. An alternative and very promising possibility is to store energy in chemical bonds, or make a solar fuel. The process of making solar fuel is not new, since photosynthesis has been occurring on earth for about 3 billion years. In order to produce any fuel, protons and electrons must be harvested from a species in its oxidized form. Photosynthesis uses the only viable source of electrons and protons on the scale needed for global energy demands: water. Because artificial photosynthesis is a lofty goal, water oxidation, which is a crucial step in the process, has been the initial focus. This Account provides an overview of how terahertz spectroscopy is used to study electron injection, highlights trends from previously published reports, and concludes with a future outlook. It begins by exploring similarities and differences between dye-sensitized solar cells (DSSCs) for producing electricity and a putative device for splitting water and producing a solar fuel. It then identifies two important problems encountered when adapting DSSC technology to water oxidation-improper energy matching between sensitizer energy levels with the potential for water oxidation and the instability of common anchoring groups in water-and discusses steps to address them. Emphasis is placed on electron injection from sensitizers to metal oxides because this process is the initial step in charge transport. Both the rate and efficiency of electron injection are analyzed on a sub-picosecond time scale using time-resolved terahertz spectroscopy (TRTS). Bio-inspired pentafluorophenyl porphyrins are promising sensitizers because their high reduction potentials are compatible with the energy requirements of water oxidation. TRTS of free-base and metalated pentafluorophenyl porphyrins reveal inefficient electron injection into TiO2 nanoparticles but more efficient electron injection into SnO2 nanoparticles. With SnO2, injection time scales depend strongly on the identity of the central substituent and are affected by competition with excited-state deactivation processes. Heavy or paramagnetic metal ions increase the electron injection time scale by roughly one order of magnitude relative to free-base or Zn(2+) porphyrins due to the possibility of electron injection from longer-lived, lower-lying triplet states. Furthermore, electron injection efficiency loosely correlates with DSSC performance. The carboxylate anchoring group is commonly used to bind DSSC sensitizers to metal oxide surfaces but typically is not stable under the aqueous and oxidative conditions required for water oxidation. Electron injection efficiency of several water-stable alternatives, including phosphonic acid, hydroxamic acid, acetylacetone, and boronic acid, were evaluated using TRTS, and hydroxamate was found to perform as well as the carboxylate. The next challenge is incorporating a water oxidation catalyst into the design. An early example, in which an Ir-based precatalyst is cosensitized with a fluorinated porphyrin, reveals decreased electron injection efficiency despite an increase in photocurrent. Future research will seek to better understand and address these difficulties.

One- or two-electron water oxidation, hydroxyl radical, or H 2O 2 evolution

DOE PAGES

Siahrostami, Samira; Li, Guo -Ling; Viswanathan, Venkatasubramanian; ...

2017-02-23

Electrochemical or photoelectrochemcial oxidation of water to form hydrogen peroxide (H 2O 2) or hydroxyl radicals (•OH) offers a very attractive route to water disinfection, and the first process could be the basis for a clean way to produce hydrogen peroxide. A major obstacle in the development of effective catalysts for these reactions is that the electrocatalyst must suppress the thermodynamically favored four-electron pathway leading to O 2 evolution. Here, we develop a thermochemical picture of the catalyst properties that determine selectivity toward the one, two, and four electron processes leading to •OH, H 2O 2, and O 2.

Nitrification of raw or used water using expanded bed biofilm reactor technology.

PubMed

Dempsey, M J

2011-01-01

Excessive ammonia in raw water increases the consumption of chlorine for disinfection during production of potable water, through oxidation to produce chloramines. Excessive ammonia in used water results in pollution of the aquatic environment, where it is particularly toxic to fish. Furthermore, nitrifying prokaryotes in the receiving water will consume dissolved oxygen equivalent to 4.6 g oxygen per g ammonia-nitrogen oxidized to nitrate. This places a considerable oxygen demand on the receiving water and can result in anoxic conditions. One solution to these problems is to nitrify the ammonia in a dedicated biological process. As nitrifiers are particularly slow growing, they are easily washed out of conventional water and wastewater treatment processes; hence, the use of immobilized biomass in an expanded bed biofilm reactor. This solution typically allows at least 10-times the biomass concentration of conventional systems, with a similar decrease in bioreactor size or increase in bioreactor productivity. This chapter describes expanded bed technology for nitrification of water, and methods for studying biomass and process performance. Copyright © 2011 Elsevier Inc. All rights reserved.

Treatment of slaughter wastewater by coagulation sedimentation-anaerobic biological filter and biological contact oxidation process

NASA Astrophysics Data System (ADS)

Sun, M.; Yu, P. F.; Fu, J. X.; Ji, X. Q.; Jiang, T.

2017-08-01

The optimal process parameters and conditions for the treatment of slaughterhouse wastewater by coagulation sedimentation-AF - biological contact oxidation process were studied to solve the problem of high concentration organic wastewater treatment in the production of small and medium sized slaughter plants. The suitable water temperature and the optimum reaction time are determined by the experiment of precipitation to study the effect of filtration rate and reflux ratio on COD and SS in anaerobic biological filter and the effect of biofilm thickness and gas water ratio on NH3-N and COD in biological contact oxidation tank, and results show that the optimum temperature is 16-24°C, reaction time is 20 min in coagulating sedimentation, the optimum filtration rate is 0.6 m/h, and the optimum reflux ratio is 300% in anaerobic biological filter reactor. The most suitable biological film thickness range of 1.8-2.2 mm and the most suitable gas water ratio is 12:1-14:1 in biological contact oxidation pool. In the coupling process of continuous operation for 80 days, the average effluent’s mass concentrations of COD, TP and TN were 15.57 mg/L, 40 mg/L and 0.63 mg/L, the average removal rates were 98.93%, 86.10%, 88.95%, respectively. The coupling process has stable operation effect and good effluent quality, and is suitable for the industrial application.

The change of steel surface chemistry regarding oxygen partial pressure and dew point

NASA Astrophysics Data System (ADS)

Norden, Martin; Blumenau, Marc; Wuttke, Thiemo; Peters, Klaus-Josef

2013-04-01

By investigating the surface state of a Ti-IF, TiNb-IF and a MnCr-DP after several series of intercritical annealing, the impact of the annealing gas composition on the selective oxidation process is discussed. On behalf of the presented results, it can be concluded that not the general oxygen partial pressure in the annealing furnace, which is a result of the equilibrium reaction of water and hydrogen, is the main driving force for the selective oxidation process. It is shown that the amounts of adsorbed gases at the strip surface and the effective oxygen partial pressure resulting from the adsorbed gases, which is mainly dependent on the water content of the annealing furnace, is driving the selective oxidation processes occurring during intercritical annealing. Thus it is concluded, that for industrial applications the dew point must be the key parameter value for process control.

Evaluating fluorescence spectroscopy as a tool to characterize cyanobacteria intracellular organic matter upon simulated release and oxidation in natural water.

PubMed

Korak, Julie A; Wert, Eric C; Rosario-Ortiz, Fernando L

2015-01-01

Intracellular organic matter (IOM) from cyanobacteria may be released into natural waters following cell death in aquatic ecosystems and during oxidation processes in drinking water treatment plants. Fluorescence spectroscopy was evaluated to identify the presence of IOM from three cyanobacteria species during simulated release into natural water and following oxidation processes (i.e. ozone, free chlorine, chloramine, chlorine dioxide). Peak picking and the fluorescence index (FI) were explored to determine which IOM components (e.g., pigments) provide unique and persistent fluorescence signatures with minimal interferences from the background dissolved organic matter (DOM) found in Colorado River water (CRW). When IOM was added to ultrapure water, the fluorescence signature of the three cyanobacteria species showed similarities to each other. Each IOM exhibited a strong protein-like fluorescence and fluorescence at Ex 370 nm and Em 460 nm (FDOM), where commercial fluorescence sensors monitor. All species also had strong phycobiliprotein fluorescence (i.e. phycocyanin or phycoerythrin) in the higher excitation range (500-650 nm). All three IOM isolates had FI values greater than 2. When IOM was added to CRW, phycobiliprotein fluorescence was quenched through interactions between IOM and CRW-DOM. Mixing IOM and CRW demonstrated that protein-like and FDOM intensity responses were not a simple superposition of the starting material intensities, indicating that interactions between IOM and CRW-DOM fluorescing moieties were important. Fluorescence intensity in all regions decreased with exposure to ozone, free chlorine, and chlorine dioxide, but the FI still indicated compositional differences compared to CRW-DOM. The phycobiliproteins in IOM are not promising as a surrogate for IOM release, because their fluorescence intensity is quenched by interactions with DOM and decreased during oxidation processes. Increases in both FDOM intensity and FI are viable qualitative indicators of IOM release in natural waters and following oxidation and may provide a more robust real-time indication of the presence of IOM than conventional dissolved organic carbon or UV absorbance measurements.

Comparative study of the degradation of carbamazepine in water by advanced oxidation processes.

PubMed

Dai, Chao-Meng; Zhou, Xue-Fei; Zhang, Ya-Lei; Duan, Yan-Ping; Qiang, Zhi-Min; Zhang, Tian C

2012-06-01

Degradation of carbamazepine (CBZ) using ultraviolet (UV), UV/H2O2, Fenton, UV/Fenton and photocatalytic oxidation with TiO2 (UV/TiO2) was studied in deionized water. The five different oxidation processes were compared for the removal kinetics of CBZ. The results showed that all the processes followed pseudo-first-order kinetics. The direct photolysis (UV alone) was found to be less effective than UV/H2O2 oxidation for the degradation of CBZ. An approximate 20% increase in the CBZ removal efficiency occurred with the UV/Fenton reaction as compared with the Fenton oxidation. In the UV/TiO2 system, the kinetics of CBZ degradation in the presence of different concentrations of TiO2 followed the pseudo-first order degradation, which was consistent with the Langmuir-Hinshelwood (L-H) model. On a time basis, the degradation efficiencies ofCBZ were in the following order: UV/Fenton (86.9% +/- 1.7%) > UV/TiO2 (70.4% +/- 4.2%) > Fenton (67.8% +/- 2.6%) > UV/H2O2 (40.65 +/- 5.1%) > UV (12.2% +/- 1.4%). However, the lowest cost was obtained with the Fenton process.

Performance characterization of water recovery and water quality from chemical/organic waste products

NASA Technical Reports Server (NTRS)

Moses, W. M.; Rogers, T. D.; Chowdhury, H.; Cullingford, H. S.

1989-01-01

The water reclamation subsystems currently being evaluated for the Space Shuttle Freedom are briefly reviewed with emphasis on a waste water management system capable of processing wastes containing high concentrations of organic/inorganic materials. The process combines low temperature/pressure to vaporize water with high temperature catalytic oxidation to decompose volatile organics. The reclaimed water is of potable quality and has high potential for maintenance under sterile conditions. Results from preliminary experiments and modifications in process and equipment required to control reliability and repeatability of system operation are presented.

Oxidation of As(III) to As(V) using ozone microbubbles.

PubMed

Khuntia, Snigdha; Majumder, Subrata Kumar; Ghosh, Pallab

2014-02-01

The use of ozone in the treatment of water and wastewater is rapidly increasing due to its high oxidizing power. Arsenic is one the most toxic elements found in water. As(III) and As(V) are the major sources of arsenic poisoning. It is known that As(V) can be more easily removed from water by adsorptive methods than As(III). In this work, oxidation of more toxic As(III) to less toxic As(V) was studied in a pilot-plant by using ozone microbubbles. The microbubbles were effective in dissolving ozone in water. The oxidation was fast over a wide range of pH (e.g., 4-9). The role of hydroxyl radical in the oxidation of As(III) under acidic conditions was investigated by using 2-propanol as the hydroxyl radical scavenger. Under acidic conditions, the addition of 2-propanol slowed down the oxidation, which proves that hydroxyl radicals were involved in the oxidation process. The effect of carbonate ions on the rate of oxidation was investigated. It was found that the generation of carbonate ion radical from the carbonate ion accelerated the oxidation of As(III). The kinetics of oxidation of As(III) by ozone was studied. Copyright © 2013 Elsevier Ltd. All rights reserved.

Comprehensive study on effects of water matrices on removal of pharmaceuticals by three different kinds of advanced oxidation processes.

PubMed

Tokumura, Masahiro; Sugawara, Asato; Raknuzzaman, Mohammad; Habibullah-Al-Mamun, Md; Masunaga, Shigeki

2016-09-01

Simple semi-theoretical models were developed to estimate the performance of three different kinds of advanced oxidation processes (AOPs) in the degradation of pharmaceuticals. The AOPs included the photo-Fenton process as an example of a liquid-liquid reaction, the TiO2 photocatalytic oxidation process as a solid-liquid reaction, and the combined ozone and hydrogen peroxide oxidation process as a gas-liquid reaction; the effects of the aqueous matrices (CESs: co-existing substances) of actual wastewater on the removal of pharmaceuticals (carbamazepine and diclofenac) was taken into account. By comparing the characteristic parameters of the models, obtained from the experiments using pure water and actual wastewater, the effects of CESs on the respective removal mechanisms could be separately and quantitatively evaluated. As a general tendency, the AOPs proceeded less effectively (were inhibited) in the matrices containing CESs, as observed with the use of a lower initial concentration of pharmaceuticals. The inhibition mechanisms differed for the three types of AOPs. In the photo-Fenton process, the Fenton reaction was improved by the incorporation of CESs, while the photo-reduction reaction was significantly inhibited. In the TiO2 photocatalytic oxidation process, competition between the pharmaceuticals and CESs for adsorption on the catalyst surface was a less significant inhibitory factor than the scavenger effects of the CESs. The combined ozone and hydrogen peroxide oxidation process was most strongly inhibited by CESs among the AOPs investigated in this study. Copyright © 2016 Elsevier Ltd. All rights reserved.

Solar-Enhanced Advanced Oxidation Processes for Water Treatment: Simultaneous Removal of Pathogens and Chemical Pollutants

PubMed Central

Tsydenova, Oyuna; Batoev, Valeriy; Batoeva, Agniya

2015-01-01

The review explores the feasibility of simultaneous removal of pathogens and chemical pollutants by solar-enhanced advanced oxidation processes (AOPs). The AOPs are based on in-situ generation of reactive oxygen species (ROS), most notably hydroxyl radicals •OH, that are capable of destroying both pollutant molecules and pathogen cells. The review presents evidence of simultaneous removal of pathogens and chemical pollutants by photocatalytic processes, namely TiO2 photocatalysis and photo-Fenton. Complex water matrices with high loads of pathogens and chemical pollutants negatively affect the efficiency of disinfection and pollutant removal. This is due to competition between chemical substances and pathogens for generated ROS. Other possible negative effects include light screening, competitive photon absorption, adsorption on the catalyst surface (thereby inhibiting its photocatalytic activity), etc. Besides, some matrix components may serve as nutrients for pathogens, thus hindering the disinfection process. Each type of water/wastewater would require a tailor-made approach and the variables that were shown to influence the processes—catalyst/oxidant concentrations, incident radiation flux, and pH—need to be adjusted in order to achieve the required degree of pollutant and pathogen removal. Overall, the solar-enhanced AOPs hold promise as an environmentally-friendly way to substitute or supplement conventional water/wastewater treatment, particularly in areas without access to centralized drinking water or sewage/wastewater treatment facilities. PMID:26287222

Molecular water oxidation catalyst

DOEpatents

Gratzel, Michael; Munavalli, Shekhar; Pern, Fu-Jann; Frank, Arthur J.

1993-01-01

A dimeric composition of the formula: ##STR1## wherein L', L", L'", and L"" are each a bidentate ligand having at least one functional substituent, the ligand selected from bipyridine, phenanthroline, 2-phenylpyridine, bipyrimidine, and bipyrazyl and the functional substituent selected from carboxylic acid, ester, amide, halogenide, anhydride, acyl ketone, alkyl ketone, acid chloride, sulfonic acid, phosphonic acid, and nitro and nitroso groups. An electrochemical oxidation process for the production of the above functionally substituted bidentate ligand diaqua oxo-bridged ruthenium dimers and their use as water oxidation catalysts is described.

Probing equilibrium of molecular and deprotonated water on TiO 2 (110)

DOE PAGES

Wang, Zhi-Tao; Wang, Yang-Gang; Mu, Rentao; ...

2017-02-06

Understanding water structure and its deprotonation dynamics on oxide surfaces is key to understanding many physical and chemical processes. In this study, we directly measure the energy barriers associated with the protonation equilibrium of water on the prototypical oxide surface, rutile-TiO2(110) by a combination of a supersonic molecular beam, scanning tunneling microscopy, and ab initio molecular dynamics simulations. We show that long-range electrostatic fields emanating from the oxide lead to steering and reorientation of the molecules approaching the surface, activating the O-H bonds and inducing deprotonation. The incident energy dependent studies allow for a direct determination of the dissociation barrier.more » Temperature dependent imaging yields the reverse barrier and the equilibrium constant. Molecularly bound water is preferred by 0.035 eV over the surface-bound hydroxyls. The techniques developed in this work are readily extended to other systems where the understanding of bond-activation processes is critical.« less

Probing equilibrium of molecular and deprotonated water on TiO 2(110)

DOE PAGES

Wang, Zhi -Tao; Wang, Yang -Gang; Mu, Rentao; ...

2017-02-06

Understanding water structure and its deprotonation dynamics on oxide surfaces is key to understanding many physical and chemical processes. In this study, we directly measure the energy barriers associated with the protonation equilibrium of water on the prototypical oxide surface, rutile-TiO 2(110) by a combination of a supersonic molecular beam, scanning tunneling microscopy, and ab initio molecular dynamics simulations. We show that long-range electrostatic fields emanating from the oxide lead to steering and reorientation of the molecules approaching the surface, activating the O-H bonds and inducing deprotonation. The incident energy dependent studies allow for a direct determination of the dissociationmore » barrier. Temperature dependent imaging yields the reverse barrier and the equilibrium constant. Molecularly bound water is preferred by 0.035 eV over the surface-bound hydroxyls. In conclusion, the techniques developed in this work are readily extended to other systems where the understanding of bond-activation processes is critical.« less

Magnetic graphene oxide for adsorption of organic dyes from aqueous solution

NASA Astrophysics Data System (ADS)

Drashya, Lal, Shyam; Hooda, Sunita

2018-05-01

Graphene oxide (GO), a 2-D carbon nanomaterial, large surface area, oxygen-containing groups (like: hydroxyl, epoxy and carboxyl) and excellent water dispersibility due to it is good adsorbent dye removal from pollutant water1. But it's difficult to separate GO from water after adsorption. Therefore, Iron oxide was introduced in Graphene oxide by decorating method to make separation more efficient2. We present herein a one step process to prepare Magnetic Graphene oxide (MGO). The Fourier transform infrared spectrometer (FT-IR), X-ray diffraction (XRD) and Raman Spectroscopy characterized the chemical structure of the MGO composite. The adsorption of dyes onto MGO was studied in relation to initial concentration of Dyes, contact time, adsorbent dose, temperature and pH value of solution. We have studied adsorption capacity of different dyes (Methylene blue and crystal violet) by MGO.

Field-analysis of potable water quality and ozone efficiency in ozone-assisted biological filtration systems for surface water treatment.

PubMed

Zanacic, Enisa; Stavrinides, John; McMartin, Dena W

2016-11-01

Potable water treatment in small communities is challenging due to a complexity of factors starting with generally poor raw water sources, a smaller tax and consumption base that limit capital and operating funds, and culminating in what is typically a less sophisticated and robust water treatment plant for production and delivery of safe, high quality potable water. The design and optimization of modular ozone-assisted biological filtration systems can address some of these challenges. In surface water treatment, the removal of organic matter (e.g., dissolved organic carbon - DOC), inorganic nutrients and other exposure-related contaminants (e.g., turbidity and dissolved solids) from the raw water source is essential. Thus, a combination of chemical and biological oxidation processes can produce an effective and efficient water treatment plant design that is also affordable and robust. To that end, the ozone-assisted biological filtration water treatment plants in two communities were evaluated to determine the efficacy of oxidation and contaminant removal processes. The results of testing for in-field system performance indicate that plant performance is particularly negatively impacted by high alkalinity, high organics loading, and turbidity. Both bicarbonate and carbonate alkalinity were observed to impede ozone contact and interaction with DOC, resulting in lower than anticipated DOC oxidation efficiency and bioavailability. The ozone dosage at both water treatment plants must be calculated on a more routine basis to better reflect both the raw water DOC concentration and presence of alkalinities to ensure maximized organics oxidation and minimization of trihalomethanes production. Copyright © 2016 The Authors. Published by Elsevier Ltd.. All rights reserved.

Process-based reactive transport model to quantify arsenic mobility during aquifer storage and recovery of potable water.

PubMed

Wallis, Ilka; Prommer, Henning; Pichler, Thomas; Post, Vincent; Norton, Stuart B; Annable, Michael D; Simmons, Craig T

2011-08-15

Aquifer storage and recovery (ASR) is an aquifer recharge technique in which water is injected in an aquifer during periods of surplus and withdrawn from the same well during periods of deficit. It is a critical component of the long-term water supply plan in various regions, including Florida, USA. Here, the viability of ASR as a safe and cost-effective water resource is currently being tested at a number of sites due to elevated arsenic concentrations detected during groundwater recovery. In this study, we developed a process-based reactive transport model of the coupled physical and geochemical mechanisms controlling the fate of arsenic during ASR. We analyzed multicycle hydrochemical data from a well-documented affected southwest Floridan site and evaluated a conceptual/numerical model in which (i) arsenic is initially released during pyrite oxidation triggered by the injection of oxygenated water (ii) then largely complexes to neo-formed hydrous ferric oxides before (iii) being remobilized during recovery as a result of both dissolution of hydrous ferric oxides and displacement from sorption sites by competing anions.

Final report on the oxidation of energetic materials in supercritical water. Final Air Force report

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

Buelow, S.J.; Allen, D.; Anderson, G.K.

1995-04-03

The objective of this project was to determine the suitability of oxidation in supercritical fluids (SCO), particularly water (SCWO), for disposal of propellants, explosives, and pyrotechnics (PEPs). The SCO studies of PEPs addressed the following issues: The efficiency of destruction of the substrate. The products of destruction contained in the effluents. Whether the process can be conducted safely on a large scale. Whether energy recovery from the process is economically practicable. The information essential for process development and equipment design was also investigated, including issues such as practical throughput of explosives through a SCWO reactor, reactor materials and corrosion, andmore » models for process design and optimization.« less

Summary Report: Pilot Study of an Innovative Biological Treatment Process for the Removal of Ammonia from a Small Drinking Water System

EPA Science Inventory

The use of biologically active filtration to oxidize ammonia as a full-scale drinking water treatment process has not been thoroughly considered in the United States. A number of concerns with biological water treatment exist including the potential release of excessive numbers o...

Comparison of microbial community shifts in two parallel multi-step drinking water treatment processes.

PubMed

Xu, Jiajiong; Tang, Wei; Ma, Jun; Wang, Hong

2017-07-01

Drinking water treatment processes remove undesirable chemicals and microorganisms from source water, which is vital to public health protection. The purpose of this study was to investigate the effects of treatment processes and configuration on the microbiome by comparing microbial community shifts in two series of different treatment processes operated in parallel within a full-scale drinking water treatment plant (DWTP) in Southeast China. Illumina sequencing of 16S rRNA genes of water samples demonstrated little effect of coagulation/sedimentation and pre-oxidation steps on bacterial communities, in contrast to dramatic and concurrent microbial community shifts during ozonation, granular activated carbon treatment, sand filtration, and disinfection for both series. A large number of unique operational taxonomic units (OTUs) at these four treatment steps further illustrated their strong shaping power towards the drinking water microbial communities. Interestingly, multidimensional scaling analysis revealed tight clustering of biofilm samples collected from different treatment steps, with Nitrospira, the nitrite-oxidizing bacteria, noted at higher relative abundances in biofilm compared to water samples. Overall, this study provides a snapshot of step-to-step microbial evolvement in multi-step drinking water treatment systems, and the results provide insight to control and manipulation of the drinking water microbiome via optimization of DWTP design and operation.

Microfabrication of SrRuO3 thin films on various oxide substrates using LaAlO3/BaOx sacrificial bilayers

NASA Astrophysics Data System (ADS)

Harada, Takayuki; Tsukazaki, Atsushi

2018-02-01

Oxides provide various fascinating physical properties that could find use in future device applications. However, the physical properties of oxides are often affected by formation of oxygen vacancies during device fabrication processes. In this study, to develop a damage-free patterning process for oxides, we focus on a lift-off process using a sacrificial template layer, by which we can pattern oxide thin films without severe chemical treatment or plasma bombardment. As oxides need high thin-film growth temperature, a sacrificial template needs to be made of thermally stable and easily etchable materials. To meet these requirements, we develop a sacrificial template with a carefully designed bilayer structure. Combining a thermally and chemically stable LaAlO3 and a water-soluble BaOx, we fabricated a LaAlO3/BaOx sacrificial bilayer. The patterned LaAlO3/BaOx sacrificial bilayers were prepared on oxide substrates by room-temperature pulsed laser deposition and standard photolithography process. The structure of the sacrificial bilayer can be maintained even in rather tough conditions needed for oxide thin film growth: several hundred degrees Celsius under high oxygen pressure. Indeed, the LaAlO3/BaOx bilayer is easily removable by sonication in water. We applied the lift-off method using the LaAlO3/BaOx sacrificial bilayer to a representative oxide conductor SrRuO3 and fabricated micron-scale Hall-bar devices. The SrRuO3 channels with the narrowest line width of 5 μm exhibit an almost identical transport property to that of the pristine film, evidencing that the developed process is beneficial for patterning oxides. We show that the LaAlO3/BaOx lift-off process is applicable to various oxide substrates: SrTiO3, MgO, and Al2O3. The new versatile patterning process will expand the range of application of oxide thin films in electronic and photonic devices.

4-chlorophenol removal from water using graphite and graphene oxides as photocatalysts.

PubMed

Bustos-Ramírez, Karina; Barrera-Díaz, Carlos Eduardo; De Icaza-Herrera, Miguel; Martínez-Hernández, Ana Laura; Natividad-Rangel, Reyna; Velasco-Santos, Carlos

2015-01-01

Graphite and graphene oxides have been studied amply in the last decade, due to their diverse properties and possible applications. Recently, their functionality as photocatalytic materials in water splitting was reported. Research in these materials is increasing due to their band gap values around 1.8-4 eV, and therefore, these are comparable with other photocatalysts currently used in heterogeneous photocatalytic processes. Thus, this research reports the photocatalytic effectiveness of graphite oxide (GO) and graphene oxide (GEO) in the degradation of 4-chlorophenol (4-CP) in water. Under the conditions defined for this research, 92 and 97% of 4-CP were degraded with GO and GEO respectively, also 97% of total organic carbon was removed. In addition, by-products of 4-CP that produce a yellow solution obtained only using photolysis are eliminated by photocatalyst process with GO and GEO. The degradation of 4-CP was monitored by UV-Vis spectroscopy, High Performance Liquid Chromatography (HPLC) and Chemical Oxygen Demand (COD). Thus, photocatalytic activity to remove 4-CP from water employing GO and GEO without doping is successfully showed, and therefore, a new gate in research for these materials is opened.

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

Lee, B.D.; Apel, W.A.; Walton, M.R.

Conceptually, biofilters are vapor phase bioreactors that rely on microorganisms in the bed medium to oxidize contaminants in off-gases flowing through the bed to less hazardous compounds. In the most studied and utilized systems reduced compounds such as fuel hydrocarbons are enzymatically oxidized to compounds such as carbon dioxide and water. In these types of reactions the microorganisms in the bed oxidize the contaminant and transfer the electrons to oxygen which is the terminal electron acceptor in the process. In essence the contaminant is the carbon and energy source for the microorganisms in the bed medium and through this catabolicmore » process oxygen is reduced to water. An example of this oxidation process can be seen during the degradation of benzene and similar aromatic compounds. Aromatics are initially attacked by a dioxygenase enzyme which oxidizes the compounds to a labile dihydrodiole which is spontaneously converted to a catechol. The dihydroxylated aromatic rings is then opened by oxidative {open_quotes}ortho{close_quotes} or {open_quotes}meta{close_quotes} cleavage yielding cis, cis-muconic acid or 2-hydroxy-cis, cis-muconic semialdehyde, respectively. These organic compounds are further oxidized to carbon dioxide or are assimilated for cellular material. This paper describes the conversion of carbon tetrachloride using methanol as the primary carbon and energy source.« less

Water depollution using metal-organic frameworks-catalyzed advanced oxidation processes: A review.

PubMed

Sharma, Virender K; Feng, Mingbao

2017-09-28

This paper presents a review on the environmental applications of metal-organic frameworks (MOFs), which are inorganic-organic hybrid highly porous crystalline materials, prepared from metal ion/clusters and multidentate organic ligands. The emphases are made on the enhancement of the performance of advanced oxidation processes (AOPs) (photocatalysis, Fenton reaction methods, and sulfate radical (SO 4 - )-mediated oxidations) using MOFs materials. MOFs act as adsorption and light absorbers, leading to superior performance of photocatalytic processes. More recent examples of photocatalytic degradation of dyes are presented. Additionally, it is commonly shown that Fe-based MOFs exhibited excellent catalytic performance on the Fenton-based and SO 4 •- -mediated oxidations of organic pollutants (e.g., dyes, phenol and pharmaceuticals). The significantly enhanced generation of reactive species such as OH and/or SO 4 - by both homogeneous and heterogeneous catalysis was proposed as the possible mechanism for water depollution. Based on the existing literature, the challenge and future perspectives in MOF-based AOPs are addressed. Copyright © 2017 Elsevier B.V. All rights reserved.

Development of Cold Spray Coatings for Accident-Tolerant Fuel Cladding in Light Water Reactors

NASA Astrophysics Data System (ADS)

Maier, Benjamin; Yeom, Hwasung; Johnson, Greg; Dabney, Tyler; Walters, Jorie; Romero, Javier; Shah, Hemant; Xu, Peng; Sridharan, Kumar

2018-02-01

The cold spray coating process has been developed at the University of Wisconsin-Madison for the deposition of oxidation-resistant coatings on zirconium alloy light water reactor fuel cladding with the goal of improving accident tolerance during loss of coolant scenarios. Coatings of metallic (Cr), alloy (FeCrAl), and ceramic (Ti2AlC) materials were successfully deposited on zirconium alloy flats and cladding tube sections by optimizing the powder size, gas preheat temperature, pressure and composition, and other process parameters. The coatings were dense and exhibited excellent adhesion to the substrate. Evaluation of the samples after high-temperature oxidation tests at temperatures up to 1300°C showed that the cold spray coatings significantly mitigate oxidation kinetics because of the formation of thin passive oxide layers on the surface. The results of the study indicate that the cold spray coating process is a viable near-term option for developing accident-tolerant zirconium alloy fuel cladding.

Effective Reuse of Electroplating Rinse Wastewater by Combining PAC with H2O2/UV Process.

PubMed

Yen, Hsing Yuan; Kang, Shyh-Fang; Lin, Chen Pei

2015-04-01

This study evaluated the performance of treating electroplating rinse wastewater by powder activated carbon (PAC) adsorption, H2O2/UV oxidation, and their combination to remove organic compounds and heavy metals. The results showed that neither the process of PAC adsorption nor H2O2/UV oxidation could reduce COD to 100 mg/L, as enforced by the Taiwan Environmental Protection Agency. On the other hand, the water sample treated by the combined approach of using PAC (5 g/L) pre-adsorption and H2O2/UV post-oxidation (UV of 64 W, H2O2 of 100 mg/L, oxidation time of 90 min), COD and DOC were reduced to 8.2 mg/L and 3.8 mg/L, respectively. Also, the combined approach reduced heavy metals to meet the effluent standards and to satisfy the in-house water reuse criteria for the electroplating factory. The reaction constant analysis indicated that the reaction proceeded much more rapidly for the combined process. Hence, it is a more efficient, economic and environmentally friendly process.

Technology for High Pure Aluminum Oxide Production from Aluminum Scrap

NASA Astrophysics Data System (ADS)

Ambaryan, G. N.; Vlaskin, M. S.; Shkolnikov, E. I.; Zhuk, A. Z.

2017-10-01

In this study a simple ecologically benign technology of high purity alumina production is presented. The synthesis process consists of three steps) oxidation of aluminum in water at temperature of 90 °C) calcinations of Al hydroxide in atmosphere at 1100 °C) high temperature vacuum processing of aluminum alpha oxide at 1750 °C. Oxidation of aluminum scrap was carried out under intensive mixing in water with small addition of KOH as a catalyst. It was shown that under implemented experimental conditions alkali was continuously regenerated during oxidation reaction and synergistic effect of low content alkali aqueous solution and intensive mixing worked. The product of oxidation of aluminum scrap is the powder of Al(OH)3. Then it can be preliminary granulated or directly subjected to thermal treatment deleting the impurities from the product (aluminum oxide). It was shown the possibility to produce the high-purity aluminum oxide of 5N grade (99.999 %). Aluminum oxide, synthesized by means of the proposed method, meets the requirements of industrial manufacturers of synthetic sapphire (aluminum oxide monocrystals). Obtained high pure aluminum oxide can be also used for the manufacture of implants, artificial joints, microscalpels, high-purity ceramics and other refractory shapes for manufacture of ultra-pure products.

Molybdenum oxide nanocolloids prepared by an external field-assisted laser ablation in water

NASA Astrophysics Data System (ADS)

Spadaro, Salvatore; Bonsignore, Martina; Fazio, Enza; Cimino, Francesco; Speciale, Antonio; Trombetta, Domenico; Barreca, Francesco; Saija, Antonina; Neri, Fortunato

2018-01-01

he synthesis of extremely stable molybdenum oxide nanocolloids by pulsed laser ablation was studied. This green technique ensures the formation of contaminant-free nanostructures and the absence of by-products. A focused picosecond pulsed laser beam was used to ablate a solid molybdenum target immersed in deionized water. Molybdenum oxide nearly spherical nanoparticles with dimensions within few nanometers (20-100 nm) are synthesized when the ablation processes were carried out, in water, at room temperature and 80°C. The application of an external electric field during the ablation process induces a nanostructures reorganization, as indicated by Scanning-Transmission Electron Microscopy images analysis. The ablation products were also characterized by some spectroscopic techniques: conventional UV-vis optical absorption, atomic absorption, dynamic light scattering, micro-Raman and X-ray photoelectron spectroscopies. Finally, NIH/3T3 mouse fibroblasts were used to evaluate cell viability by the sulforhodamine B assay

Domestic applications for aerospace waste and water management technologies

NASA Technical Reports Server (NTRS)

Disanto, F.; Murray, R. W.

1972-01-01

Some of the aerospace developments in solid waste disposal and water purification, which are applicable to specific domestic problems are explored. Also provided is an overview of the management techniques used in defining the need, in utilizing the available tools, and in synthesizing a solution. Specifically, several water recovery processes will be compared for domestic applicability. Examples are filtration, distillation, catalytic oxidation, reverse osmosis, and electrodialysis. Solid disposal methods will be discussed, including chemical treatment, drying, incineration, and wet oxidation. The latest developments in reducing household water requirements and some concepts for reusing water will be outlined.

Inhibition of trihalomethane formation in city water by radiation-ozone treatment and rapid composting of radiation disinfected sewage sludge

NASA Astrophysics Data System (ADS)

Takehisa, M.; Arai, H.; Arai, M.; Miyata, T.; Sakumoto, A.; Hashimoto, S.; Nishimura, K.; Watanabe, H.; Kawakami, W.; Kuriyama, I.

Humic acid and Fulvic acid in natural water are precursors of carcinogenic THM which is formed during chlorine disinfection in city water processing. The radiation-oxidation process in the presence of ozone is effective to remove the precursors. The THM formation was reduced more than the decrease in TOC by the combination treatment. This is mainly due to a change in the chemical structure of the oxidation products. A composting of radiation disinfected sludge cake for agricultural reuse could be achieved within 3 days primary fermentation in a sewage plant. The rapid fermentation with use of radiation is effective to scale down of a fermentor of composting plant and the process reduces a health risk from the workers as well as final users.

Using Iron-Manganese Co-Oxide Filter Film to Remove Ammonium from Surface Water

PubMed Central

Zhang, Ruifeng; Huang, Tinglin; Wen, Gang; Chen, Yongpan; Cao, Xin; Zhang, Beibei

2017-01-01

An iron-manganese co-oxide filter film (MeOx) has been proven to be a good catalyst for the chemical catalytic oxidation of ammonium in groundwater. Compared with groundwater, surface water is generally used more widely and has characteristics that make ammonium removal more difficult. In this study, MeOx was used to remove ammonium from surface water. It indicated that the average ammonium removal efficiency of MeOx was greater than 90%, even though the water quality changed dramatically and the water temperature was reduced to about 6–8 °C. Then, through inactivating microorganisms, it showed that the removal capability of MeOx included both biological (accounted for about 41.05%) and chemical catalytic oxidation and chemical catalytic oxidation (accounted for about 58.95%). The investigation of the characterizations suggested that MeOx was formed by abiotic ways and the main elements on the surface of MeOx were distributed homogenously. The analysis of the catalytic oxidation process indicated that ammonia nitrogen may interact with MeOx as both ammonia molecules and ammonium ions and the active species of O2 were possibly •O and O2−. PMID:28753939

Using Iron-Manganese Co-Oxide Filter Film to Remove Ammonium from Surface Water.

PubMed

Zhang, Ruifeng; Huang, Tinglin; Wen, Gang; Chen, Yongpan; Cao, Xin; Zhang, Beibei

2017-07-19

An iron-manganese co-oxide filter film (MeO x ) has been proven to be a good catalyst for the chemical catalytic oxidation of ammonium in groundwater. Compared with groundwater, surface water is generally used more widely and has characteristics that make ammonium removal more difficult. In this study, MeO x was used to remove ammonium from surface water. It indicated that the average ammonium removal efficiency of MeO x was greater than 90%, even though the water quality changed dramatically and the water temperature was reduced to about 6-8 °C. Then, through inactivating microorganisms, it showed that the removal capability of MeO x included both biological (accounted for about 41.05%) and chemical catalytic oxidation and chemical catalytic oxidation (accounted for about 58.95%). The investigation of the characterizations suggested that MeO x was formed by abiotic ways and the main elements on the surface of MeO x were distributed homogenously. The analysis of the catalytic oxidation process indicated that ammonia nitrogen may interact with MeO x as both ammonia molecules and ammonium ions and the active species of O₂ were possibly • O and O₂ - .

Relation between electron- and photon-caused oxidation in EUVL optics

NASA Astrophysics Data System (ADS)

Malinowski, Michael E.; Steinhaus, Charles A.; Meeker, Donald E.; Clift, W. Miles; Klebanoff, Leonard E.; Bajt, Sasa

2003-06-01

Extreme ultraviolet (EUV)-induced oxidation of silicon-capped, [Mo/Si] multilayer mirrors in the presence of background levels of water vapor is recognized as one of the most serious threats to multilayer lifetime since oxidation of the top silicon layer is an irreversible process. The current work directly compares the oxidation on a silicon-capped, [Mo/Si] multilayers caused by EUV photons with the oxidation caused by 1 keV electrons in the presence of the same water vapor environment (2 x 10-6 Torr). Similar, 4 nm, silicon-capped, [Mo/Si] multilayer mirror samples were exposed to photons (95.3 eV) + water vapor at the ALS, LBNL, and also to a 1 keV electron beam + water vapor in separate experimental systems. The results of this work showed that the oxidation produced by ~1 µA of e-beam current was found to be equivalent to that produced by ~1 mW of EUV exposure. These results will help allow the use of 1 keV electrons beams, instead of EUV photons, to perform environmental testing of multilayers in a low-pressure water environment and to more accurately determine projected mirror lifetimes based on the electron beam exposures.

Relation between electron- and photon-caused oxidation in EUVL optics

NASA Astrophysics Data System (ADS)

Malinowski, Michael E.; Steinhaus, Charles A.; Meeker, Donald E.; Clift, W. Miles; Klebanoff, Leonard E.; Bajt, Sasa

2003-06-01

Extreme ultraviolet (EUV)-induced oxidation of silicon-capped, [Mo/Si] multilayer mirrors in the presence of background levels of water vapor is recognized as one of the most serious threats to multilayer lifetime since oxidation of the top silicon layer is an irreversible process. The current work directly compares the oxidation on a silicon-capped, [Mo/Si] multilayers caused by EUV photons with the oxidation caused by 1 keV electrons in the presence of the same water vapor environment (2 x 10-6 Torr). Similar, 4 nm, silicon-capped, [Mo/Si] multilayer mirror samples were exposed to photons (95.3 eV) + water vapor at the ALS, LBNL, and also to a 1 keV electron beam + water vapor in separate experimental systems. The results of this work showed that the oxidation produced by ~1 ´A of e-beam current was found to be equivalent to that produced by ~1 mW of EUV exposure. These results will help allow the use of 1 keV electrons beams, instead of EUV photons, to perform environmental testing of multilayers in a low-pressure water environment and to more accurately determine projected mirror lifetimes based on the electron beam exposures.

Atmospheric Capture On Mars (and Processing)

NASA Technical Reports Server (NTRS)

Muscatello, Tony

2017-01-01

The ultimate destination of NASA's human exploration program is Mars. In Situ Resource Utilization (ISRU) is a key technology required to enable such missions, as first proposed by Prof. Robert Ash in 1976. This presentation will review progress in the systems required to produce rocket propellant, oxygen, and other consumables on Mars using the carbon dioxide atmosphere and other potential resources. For many years, NASA, commercial companies, and academia have been developing, and demonstrating techniques to capture and purify Martian atmospheric gases for their utilization for the production of hydrocarbons, oxygen, and water in ISRU systems. Other gases will be required to be separated from Martian atmospheric gases to provide pure CO2 for processing elements. Significant progress has been demonstrated in CO2 collection via adsorption by molecular sieves, freezing, and direct compression. Early stage work in adsorption in Ionic Liquids followed by electrolysis to oxygen is also underway. In addition, other Martian gases, such as nitrogen and argon, occur in concentrations high enough to be useful as buffer gas and could be captured as well. Gas separation requirements include, but are not limited to the selective separation of: (1) methane and water from unreacted carbon oxides (CO2-CO) and hydrogen typical of a Sabatier-type process, (2) carbon oxides and water from unreacted hydrogen from a Reverse Water-Gas Shift process, and (3) carbon oxides from oxygen from a trash/waste processing reaction.

Decrease in fruit moisture content heralds and might launch the onset of ripening processes.

PubMed

Frenkel, Chaim; Hartman, Thomas G

2012-10-01

It is known that fruit ripening is a genetically programmed event but it is not entirely clear what metabolic cue(s) stimulate the onset of ripening, ethylene action notwithstanding. Here, we examined the conjecture that fruit ripening might be evoked by an autonomously induced decrease in tissue water status. We found decline in water content occurring at the onset of ripening in climacteric and nonclimacteric fruit, suggesting that this phenomenon might be universal. This decline in water content persisted throughout the ripening process in some fruit, whereas in others it reversed during the progression of the ripening process. Applied ethylene also induced a decrease in water content in potato (Solanum tuberosum) tubers. In ethylene-mutant tomato (Solanum lycopersicum) fruit (antisense to1-aminocyclopropane carboxylate synthase), cold-induced decline in water content stimulated onset of ripening processes apparently independently of ethylene action, suggesting cause-and-effect relationship between decreasing water content and onset of ripening. The decline in tissue water content, occurring naturally or induced by ethylene, was strongly correlated with a decrease in hydration (swelling) efficacy of cell wall preparations suggesting that hydration dynamics of cell walls might account for changes in tissue moisture content. Extent of cell wall swelling was, in turn, related to the degree of oxidative cross-linking of wall-bound phenolic acids, suggesting that oxidant-induced wall restructuring might mediate cell wall and, thus, fruit tissue hydration status. We propose that oxidant-induced cell wall remodeling and consequent wall dehydration might evoke stress signaling for the onset of ripening processes. This study suggests that decline in fruit water content is an early event in fruit ripening. This information may be used to gauge fruit maturity for appropriate harvest date and for processing. Control of fruit hydration state might be used to regulate the onset of fruit ripening. © 2012 Institute of Food Technologists®

Experimental and theoretical study on chemical reactions and species diffusion by a nano-pulse discharged bubble for water treatment

NASA Astrophysics Data System (ADS)

He, Yuchen; Uehara, Satoshi; Takana, Hidemasa; Nishiyama, Hideya

2018-01-01

Advanced oxidation processes using hydroxyl radicals (ṡOH) generated inside bubbles in water has drawn widely interest for the high oxidation potential of OH radical to decompose persistent organic pollutants such as dioxins and humic acid for water purification. In this study, a two-dimensional diffusion model for a nano-pulse discharged bubble in water is established. Based on the experimental results of streamer propagation inside a bubble, the diffusion processes around the bubble interface and reactions of chemical species in liquids are simulated. The simulation results show that OH radicals can diffuse only several micrometers away from the bubble interface in water. Furthermore, the optimal operating voltage and frequency conditions for OH generation is obtained by comparing the OH concentration in water obtained from numerical simulation with that measured by spectroscopy in experiment.

Microbial Manganese and Sulfate Reduction in Black Sea Shelf Sediments

PubMed Central

Thamdrup, Bo; Rosselló-Mora, Ramón; Amann, Rudolf

2000-01-01

The microbial ecology of anaerobic carbon oxidation processes was investigated in Black Sea shelf sediments from mid-shelf with well-oxygenated bottom water to the oxic-anoxic chemocline at the shelf-break. At all stations, organic carbon (Corg) oxidation rates were rapidly attenuated with depth in anoxically incubated sediment. Dissimilatory Mn reduction was the most important terminal electron-accepting process in the active surface layer to a depth of ∼1 cm, while SO42− reduction accounted for the entire Corg oxidation below. Manganese reduction was supported by moderately high Mn oxide concentrations. A contribution from microbial Fe reduction could not be discerned, and the process was not stimulated by addition of ferrihydrite. Manganese reduction resulted in carbonate precipitation, which complicated the quantification of Corg oxidation rates. The relative contribution of Mn reduction to Corg oxidation in the anaerobic incubations was 25 to 73% at the stations with oxic bottom water. In situ, where Mn reduction must compete with oxygen respiration, the contribution of the process will vary in response to fluctuations in bottom water oxygen concentrations. Total bacterial numbers as well as the detection frequency of bacteria with fluorescent in situ hybridization scaled to the mineralization rates. Most-probable-number enumerations yielded up to 105 cells of acetate-oxidizing Mn-reducing bacteria (MnRB) cm−3, while counts of Fe reducers were <102 cm−3. At two stations, organisms affiliated with Arcobacter were the only types identified from 16S rRNA clone libraries from the highest positive MPN dilutions for MnRB. At the third station, a clone type affiliated with Pelobacter was also observed. Our results delineate a niche for dissimilatory Mn-reducing bacteria in sediments with Mn oxide concentrations greater than ∼10 μmol cm−3 and indicate that bacteria that are specialized in Mn reduction, rather than known Mn and Fe reducers, are important in this niche. PMID:10877783

Chlorination of bromide-containing waters: enhanced bromate formation in the presence of synthetic metal oxides and deposits formed in drinking water distribution systems.

PubMed

Liu, Chao; von Gunten, Urs; Croué, Jean-Philippe

2013-09-15

Bromate formation from the reaction between chlorine and bromide in homogeneous solution is a slow process. The present study investigated metal oxides enhanced bromate formation during chlorination of bromide-containing waters. Selected metal oxides enhanced the decay of hypobromous acid (HOBr), a requisite intermediate during the oxidation of bromide to bromate, via (i) disproportionation to bromate in the presence of nickel oxide (NiO) and cupric oxide (CuO), (ii) oxidation of a metal to a higher valence state in the presence of cuprous oxide (Cu2O) and (iii) oxygen formation by NiO and CuO. Goethite (α-FeOOH) did not enhance either of these pathways. Non-charged species of metal oxides seem to be responsible for the catalytic disproportionation which shows its highest rate in the pH range near the pKa of HOBr. Due to the ability to catalyze HOBr disproportionation, bromate was formed during chlorination of bromide-containing waters in the presence of CuO and NiO, whereas no bromate was detected in the presence of Cu2O and α-FeOOH for analogous conditions. The inhibition ability of coexisting anions on bromate formation at pH 8.6 follows the sequence of phosphate > sulfate > bicarbonate/carbonate. A black deposit in a water pipe harvested from a drinking water distribution system exerted significant residual oxidant decay and bromate formation during chlorination of bromide-containing waters. Energy dispersive spectroscopy (EDS) analyses showed that the black deposit contained copper (14%, atomic percentage) and nickel (1.8%, atomic percentage). Cupric oxide was further confirmed by X-ray diffraction (XRD). These results indicate that bromate formation may be of concern during chlorination of bromide-containing waters in distribution systems containing CuO and/or NiO. Copyright © 2013 Elsevier Ltd. All rights reserved.

Water vapor diffusion membrane development. [for water recovery purposes onboard manned spacecraft

NASA Technical Reports Server (NTRS)

Tan, M. K.

1974-01-01

The phase separator component used as a membrane in the vapor diffusion process (VRD) for the recovery of potable water from urine on manned space missions of extended duration was investigated, with particular emphasis on cation-selective membranes because of their noted mechanical strength, superior resistance to acids, oxidants, and germicides, and their potential resistance to organic foulants. Two of the membranes were tested for 700 hours continuously, and were selected on the basis of criteria deemed important to an effective water reclamation system onboard spacecraft. The samples of urine were successfully processed by removing 93 percent of their water content in 70 hours using the selected membranes. Pretreatment with an acid-oxidant formulation improved product quality. Cation exchange membranes were shown to possess superior mechanical strength and chemical resistance, as compared to cellulosic membranes.

Light-Dependent Aerobic Methane Oxidation Reduces Methane Emissions from Seasonally Stratified Lakes

PubMed Central

Oswald, Kirsten; Milucka, Jana; Brand, Andreas; Littmann, Sten; Wehrli, Bernhard; Kuypers, Marcel M. M.; Schubert, Carsten J.

2015-01-01

Lakes are a natural source of methane to the atmosphere and contribute significantly to total emissions compared to the oceans. Controls on methane emissions from lake surfaces, particularly biotic processes within anoxic hypolimnia, are only partially understood. Here we investigated biological methane oxidation in the water column of the seasonally stratified Lake Rotsee. A zone of methane oxidation extending from the oxic/anoxic interface into anoxic waters was identified by chemical profiling of oxygen, methane and δ13C of methane. Incubation experiments with 13C-methane yielded highest oxidation rates within the oxycline, and comparable rates were measured in anoxic waters. Despite predominantly anoxic conditions within the zone of methane oxidation, known groups of anaerobic methanotrophic archaea were conspicuously absent. Instead, aerobic gammaproteobacterial methanotrophs were identified as the active methane oxidizers. In addition, continuous oxidation and maximum rates always occurred under light conditions. These findings, along with the detection of chlorophyll a, suggest that aerobic methane oxidation is tightly coupled to light-dependent photosynthetic oxygen production both at the oxycline and in the anoxic bottom layer. It is likely that this interaction between oxygenic phototrophs and aerobic methanotrophs represents a widespread mechanism by which methane is oxidized in lake water, thus diminishing its release into the atmosphere. PMID:26193458

METHOD OF MAINTAINING PLUTONIUM IN A HIGHER STATE OF OXIDATION DURING PROCESSING

DOEpatents

Thompson, S.G.; Miller, D.R.

1959-06-30

This patent deals with the oxidation of tetravalent plutonium contained in an aqueous acid solution together with fission products to the hexavalent state, prior to selective fission product precipitation, by adding to the solution bismuthate or ceric ions as the oxidant and a water-soluble dichromate as a holding oxidant. Both oxidant and holding oxidant are preferably added in greater than stoichiometric quantities with regard to the plutonium present.

Topotactic redox chemistry of NaFeAs in water and air and superconducting behavior with stoichiometry change.

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

Todorov, I.; Chung, D. Y.; Claus, H.

2010-07-13

We report experimental evidence that shows superconductivity in NaFeAs occurs when it is Na deficient. The oxidation of NaFeAs progresses differently in water and in air. In water the material oxidizes slowly and slightly retaining the original anti-PbFCl structure. In air NaFeAs oxidizes topotactically quickly and extensively transforming to the ThCr{sub 2}Si{sub 2} structure type. Water acts as a mild oxidizing agent on the FeAs layer by extracting electrons and Na{sup +} cations from the structure, while oxidation in air is more extensive and leads to change in structure type from NaFeAs to NaFe{sub 2}As{sub 2}. The superconducting transition temperaturemore » moves dramatically during the oxidation process. Exposed to water for an extended time period NaFeAs shows a substantial increase in T{sub c} up to 25 K with contraction of unit cell volume. NaFe{sub 2}As{sub 2}, the air oxidized product, shows T{sub c} of 12 K. We report detailed characterization of the redox chemistry and transformation of NaFeAs in water and air using single crystal and powder X-ray diffraction, magnetization studies, transmission electron microscopy, Moessbauer spectroscopy, pOH and elemental analysis.« less

Naphthenic acids removal from high TDS produced water by persulfate mediated iron oxide functionalized catalytic membrane, and by nanofiltration.

PubMed

Aher, Ashish; Papp, Joseph; Colburn, Andrew; Wan, Hongyi; Hatakeyama, Evan; Prakash, Prakhar; Weaver, Ben; Bhattacharyya, Dibakar

2017-11-01

Oil industries generate large amounts of produced water containing organic contaminants, such as naphthenic acids (NA) and very high concentrations of inorganic salts. Recovery of potable water from produced water can be highly energy intensive is some cases due to its high salt concentration, and safe discharge is more suitable. Here, we explored catalytic properties of iron oxide (Fe x O y nanoparticles) functionalized membranes in oxidizing NA from water containing high concentrations of total dissolved solids (TDS) using persulfate as an oxidizing agent. Catalytic decomposition of persulfate by Fe x O y functionalized membranes followed pseudo-first order kinetics with an apparent activation energy of 18 Kcal/mol. Fe x O y functionalized membranes were capable of lowering the NA concentrations to less than discharge limits of 10 ppm at 40 °C. Oxidation state of iron during reaction was quantified. Membrane performance was investigated for extended period of time. A coupled process of advanced oxidation catalyzed by membrane and nanofiltration was also evaluated. Commercially available nanofiltration membranes were found capable of retaining NA from water containing high concentrations of dissolved salts. Commercial NF membranes, Dow NF270 (Dow), and NF8 (Nanostone) had NA rejection of 79% and 82%, respectively. Retentate for the nanofiltration was further treated with advanced oxidation catalyzed by Fe x O y functionalized membrane for removal of NA.

Development studies of a novel wet oxidation process

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

Rogers, T.W.; Dhooge, P.M.

1995-10-01

Many DOE waste streams and remediates contain complex and variable mixtures of organic compounds, toxic metals, and radionuclides. These materials are often dispersed in organic or inorganic matrices, such as personal protective equipment, various sludges, soils, and water. Incineration and similar combustive processes do not appear to be viable options for treatment of these waste streams due to various considerations. The objective of this project is to develop a novel catalytic wet oxidation process for the treatment of multi-component wastes. The DETOX process uses a unique combination of metal catalysts to increase the rate of oxidation of organic materials.

How to make an efficient and robust molecular catalyst for water oxidation.

PubMed

Garrido-Barros, Pablo; Gimbert-Suriñach, Carolina; Matheu, Roc; Sala, Xavier; Llobet, Antoni

2017-10-16

Energy has been a central subject for human development from Homo erectus to date. The massive use of fossil fuels during the last 50 years has generated a large CO 2 concentration in the atmosphere that has led to the so-called global warming. It is very urgent to come up with C-neutral energy schemes to be able to preserve Planet Earth for future generations to come and still preserve our modern societies' life style. One of the potential solutions is water splitting with sunlight (hν-WS) that is also associated with "artificial photosynthesis", since its working mode consists of light capture followed by water oxidation and proton reduction processes. The hydrogen fuel generated in this way is named as "solar fuel". For this set of reactions, the catalytic oxidation of water to dioxygen is one of the crucial processes that need to be understood and mastered in order to build up potential devices based on hν-WS. This tutorial describes the different important aspects that need to be considered to come up with efficient and oxidatively robust molecular water oxidation catalysts (Mol-WOCs). It is based on our own previous work and completed with essential contributions from other active groups in the field. We mainly aim at describing how the ligands can influence the properties of the Mol-WOCs and showing a few key examples that overall provide a complete view of today's understanding in this field.

Removal of natural organic matter from drinking water by advanced oxidation processes.

PubMed

Matilainen, Anu; Sillanpää, Mika

2010-06-01

Over the past 10-20years the amount of the natural organic matter (NOM) has been increased in raw water supplies on several areas. The presence of NOM causes many problems in drinking water treatment processes, including: (i) negative effect on water quality by colour, taste and odor problems, (ii) increased coagulant and disinfectant dose requirements (which in turn results increased sludge and potential harmful disinfection by-product formation), (iii) promoted biological growth in distribution system, and (iv) increased levels of complexed heavy metals and adsorbed organic pollutants. Thus, more efficient methods for the removal of NOM have emerged. Among these are advanced oxidation processes (AOPs). These include O(3)/H(2)O(2), O(3)/UV, UV/H(2)O(2), TiO(2)/UV, H(2)O(2)/catalyst, Fenton and photo-Fenton prosesses as well as ultrasound. In the present work, an overview of the recent research studies dealing with AOP methods for the removal of NOM and related compounds from drinking water is presented.

Influence of drinking water treatments on chlorine dioxide consumption and chlorite/chlorate formation.

PubMed

Sorlini, Sabrina; Gialdini, Francesca; Biasibetti, Michela; Collivignarelli, Carlo

2014-05-01

Disinfection is the last treatment stage of a Drinking Water Treatment Plant (DWTP) and is carried out to maintain a residual concentration of disinfectant in the water distribution system. Chlorine dioxide (ClO2) is a widely used chemical employed for this purpose. The aim of this work was to evaluate the influence of several treatments on chlorine dioxide consumption and on chlorite and chlorate formation in the final oxidation/disinfection stage. A number of tests was performed at laboratory scale employing water samples collected from the DWTP of Cremona (Italy). The following processes were studied: oxidation with potassium permanganate, chlorine dioxide and sodium hypochlorite, coagulation/flocculation with ferric chloride and aluminum sulfate, filtration and adsorption onto activated carbon. The results showed that the chlorine dioxide demand is high if sodium hypochlorite or potassium permanganate are employed in pre-oxidation. On the other hand, chlorine dioxide leads to the highest production of chlorite and chlorate. The coagulation/flocculation process after pre-oxidation shows that chlorine dioxide demand decreases if potassium permanganate is employed as an oxidant, both with ferric chloride and aluminum sulfate. Therefore, the combination of these processes leads to a lower production of chlorite and chlorate. Aluminum sulfate is preferable in terms of the chlorine dioxide demand reduction and minimization of the chlorite and chlorate formation. Activated carbon is the most effective solution as it reduced the chlorine dioxide consumption by about 50% and the DBP formation by about 20-40%. Copyright © 2014 Elsevier Ltd. All rights reserved.

Application of electrochemical technology for removing petroleum hydrocarbons from produced water using lead dioxide and boron-doped diamond electrodes.

PubMed

Gargouri, Boutheina; Gargouri, Olfa Dridi; Gargouri, Bochra; Trabelsi, Souhel Kallel; Abdelhedi, Ridha; Bouaziz, Mohamed

2014-12-01

Although diverse methods exist for treating polluted water, the most promising and innovating technology is the electrochemical remediation process. This paper presents the anodic oxidation of real produced water (PW), generated by the petroleum exploration of the Petrobras plant-Tunisia. Experiments were conducted at different current densities (30, 50 and 100 mA cm(-2)) using the lead dioxide supported on tantalum (Ta/PbO2) and boron-doped diamond (BDD) anodes in an electrolytic batch cell. The electrolytic process was monitored by the chemical oxygen demand (COD) and the residual total petroleum hydrocarbon [TPH] in order to know the feasibility of electrochemical treatment. The characterization and quantification of petroleum wastewater components were performed by gas chromatography mass spectrometry. The COD removal was approximately 85% and 96% using PbO2 and BDD reached after 11 and 7h, respectively. Compared with PbO2, the BDD anode showed a better performance to remove petroleum hydrocarbons compounds from produced water. It provided a higher oxidation rate and it consumed lower energy. However, the energy consumption and process time make useless anodic oxidation for the complete elimination of pollutants from PW. Cytotoxicity has shown that electrochemical oxidation using BDD could be efficiently used to reduce more than 90% of hydrocarbons compounds. All results suggest that electrochemical oxidation could be an effective approach to treat highly concentrated organic pollutants present in the industrial petrochemical wastewater and significantly reduce the cost and time of treatment. Copyright © 2014 Elsevier Ltd. All rights reserved.

Photocatalytic post-treatment in waste water reclamation systems

NASA Technical Reports Server (NTRS)

Cooper, Gerald; Ratcliff, Matthew A.; Verostko, Charles E.

1989-01-01

A photocatalytic water purification process is described which effectively oxidizes organic impurities common to reclaimed waste waters and humidity condensates to carbon dioxide at ambient temperatures. With this process, total organic carbon concentrations below 500 ppb are readily achieved. The temperature dependence of the process is well described by the Arrhenius equation and an activation energy barrier of 3.5 Kcal/mole. The posttreatment approach for waste water reclamation described here shows potential for integration with closed-loop life support systems.

Sliding Speed-Dependent Tribochemical Wear of Oxide-Free Silicon

NASA Astrophysics Data System (ADS)

Chen, Lei; Qi, Yaqiong; Yu, Bingjun; Qian, Linmao

2017-06-01

Fundamental understanding of tribochemical wear mechanism of oxide-free single crystalline silicon (without native oxide layer) is essential to optimize the process of ultra-precision surface manufacturing. Here, we report sliding speed-dependent nanowear of oxide-free silicon against SiO2 microspheres in air and in deionized water. When contact pressure is too low to induce Si yield, tribochemical wear occurs with the existence of water molecules and wear volume decreases logarithmically to constant as sliding speed increased. TEM and Raman observations indicate that the dynamics of rupture and reformation of interfacial bonding bridges result in the variation of tribochemical wear of the oxide-free Si with the increase of sliding speed.

Metal oxide porous ceramic membranes with small pore sizes

DOEpatents

Anderson, Marc A.; Xu, Qunyin

1992-01-01

A method is disclosed for the production of metal oxide ceramic membranes of very small pore size. The process is particularly useful in the creation of titanium and other transition metal oxide membranes. The method utilizes a sol-gel process in which the rate of particle formation is controlled by substituting a relatively large alcohol in the metal alkoxide and by limiting the available water. Stable, transparent metal oxide ceramic membranes are created having a narrow distribution of pore size, with the pore diameter being manipulable in the range of 5 to 40 Angstroms.

Metal oxide porous ceramic membranes with small pore sizes

DOEpatents

Anderson, Marc A.; Xu, Qunyin

1991-01-01

A method is disclosed for the production of metal oxide ceramic membranes of very small pore size. The process is particularly useful in the creation of titanium and other transition metal oxide membranes. The method utilizes a sol-gel process in which the rate of particle formation is controlled by substituting a relatively large alcohol in the metal alkoxide and by limiting the available water. Stable, transparent metal oxide ceramic membranes are created having a narrow distribution of pore size, with the pore diameter being manipulable in the range of 5 to 40 Angstroms.

Computational Modeling of Cobalt-Based Water Oxidation: Current Status and Future Challenges

PubMed Central

Schilling, Mauro; Luber, Sandra

2018-01-01

A lot of effort is nowadays put into the development of novel water oxidation catalysts. In this context, mechanistic studies are crucial in order to elucidate the reaction mechanisms governing this complex process, new design paradigms and strategies how to improve the stability and efficiency of those catalysts. This review is focused on recent theoretical mechanistic studies in the field of homogeneous cobalt-based water oxidation catalysts. In the first part, computational methodologies and protocols are summarized and evaluated on the basis of their applicability toward real catalytic or smaller model systems, whereby special emphasis is laid on the choice of an appropriate model system. In the second part, an overview of mechanistic studies is presented, from which conceptual guidelines are drawn on how to approach novel studies of catalysts and how to further develop the field of computational modeling of water oxidation reactions. PMID:29721491

Computational Modeling of Cobalt-based Water Oxidation: Current Status and Future Challenges

NASA Astrophysics Data System (ADS)

Schilling, Mauro; Luber, Sandra

2018-04-01

A lot of effort is nowadays put into the development of novel water oxidation catalysts. In this context mechanistic studies are crucial in order to elucidate the reaction mechanisms governing this complex process, new design paradigms and strategies how to improve the stability and efficiency of those catalysis. This review is focused on recent theoretical mechanistic studies in the field of homogeneous cobalt-based water oxidation catalysts. In the first part, computational methodologies and protocols are summarized and evaluated on the basis of their applicability towards real catalytic or smaller model systems, whereby special emphasis is laid on the choice of an appropriate model system. In the second part, an overview of mechanistic studies is presented, from which conceptual guidelines are drawn on how to approach novel studies of catalysts and how to further develop the field of computational modeling of water oxidation reactions.

Effects of a modular two-step ozone-water and annealing process on silicon carbide graphene

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

Webb, Matthew J., E-mail: matthew.webb@cantab.net; Lundstedt, Anna; Grennberg, Helena

By combining ozone and water, the effect of exposing epitaxial graphene on silicon carbide to an aggressive wet-chemical process has been evaluated after high temperature annealing in ultra high vacuum. The decomposition of ozone in water produces a number of oxidizing species, however, despite long exposure times to the aqueous-ozone environment, no graphene oxide was observed after the two-step process. The systems were comprehensively characterized before and after processing using Raman spectroscopy, core level photoemission spectroscopy, and angle resolved photoemission spectroscopy together with low energy electron diffraction, low energy electron microscopy, and atomic force microscopy. In spite of the chemicalmore » potential of the aqueous-ozone reaction environment, the graphene domains were largely unaffected raising the prospect of employing such simple chemical and annealing protocols to clean or prepare epitaxial graphene surfaces.« less

Numerical Simulation of Hydrothermal Salt Separation Process and Analysis and Cost Estimating of Shipboard Liquid Waste Disposal

DTIC Science & Technology

2007-06-01

possible means to improve a variety of processes: supercritical water in steam Rankine cycles (fossil-fuel powered plants), supercritical carbon ... dioxide and supercritical water in advanced nuclear power plants, and oxidation in supercritical water for use in destroying toxic military wastes and...destruction technologies are installed in a class of ship. Additionally, the properties of one waste water destruction medium, supercritical

Solar-rechargeable battery based on photoelectrochemical water oxidation: Solar water battery

PubMed Central

Kim, Gonu; Oh, Misol; Park, Yiseul

2016-01-01

As an alternative to the photoelectrochemical water splitting for use in the fuel cells used to generate electrical power, this study set out to develop a solar energy rechargeable battery system based on photoelectrochemical water oxidation. We refer to this design as a “solar water battery”. The solar water battery integrates a photoelectrochemical cell and battery into a single device. It uses a water oxidation reaction to simultaneously convert and store solar energy. With the solar water battery, light striking the photoelectrode causes the water to be photo-oxidized, thus charging the battery. During the discharge process, the solar water battery reduces oxygen to water with a high coulombic efficiency (>90%) and a high average output voltage (0.6 V). Because the reduction potential of oxygen is more positive [E0 (O2/H2O) = 1.23 V vs. NHE] than common catholytes (e.g., iodide, sulfur), a high discharge voltage is produced. The solar water battery also exhibits a superior storage ability, maintaining 99% of its specific discharge capacitance after 10 h of storage, without any evidence of self-discharge. The optimization of the cell design and configuration, taking the presence of oxygen in the cell into account, was critical to achieving an efficient photocharge/discharge. PMID:27629362

Solar-rechargeable battery based on photoelectrochemical water oxidation: Solar water battery.

PubMed

Kim, Gonu; Oh, Misol; Park, Yiseul

2016-09-15

As an alternative to the photoelectrochemical water splitting for use in the fuel cells used to generate electrical power, this study set out to develop a solar energy rechargeable battery system based on photoelectrochemical water oxidation. We refer to this design as a "solar water battery". The solar water battery integrates a photoelectrochemical cell and battery into a single device. It uses a water oxidation reaction to simultaneously convert and store solar energy. With the solar water battery, light striking the photoelectrode causes the water to be photo-oxidized, thus charging the battery. During the discharge process, the solar water battery reduces oxygen to water with a high coulombic efficiency (>90%) and a high average output voltage (0.6 V). Because the reduction potential of oxygen is more positive [E(0) (O2/H2O) = 1.23 V vs. NHE] than common catholytes (e.g., iodide, sulfur), a high discharge voltage is produced. The solar water battery also exhibits a superior storage ability, maintaining 99% of its specific discharge capacitance after 10 h of storage, without any evidence of self-discharge. The optimization of the cell design and configuration, taking the presence of oxygen in the cell into account, was critical to achieving an efficient photocharge/discharge.

Determination of Ammonia Oxidizing Bacteria and Nitrate Oxidizing Bacteria in Wastewater and Bioreactors

NASA Technical Reports Server (NTRS)

Francis, Somilez Asya

2014-01-01

The process of water purification has many different physical, chemical, and biological processes. One part of the biological process is the task of ammonia oxidizing bacteria (AOB) and nitrite oxidizing bacteria (NOB). Both play critical roles in the treatment of wastewater by oxidizing toxic compounds. The broad term is nitrification, a naturally occurring process that is carried out by AOB and NOB by using oxidation to convert ammonia to nitrite and nitrite to nitrate. To monitor this biological activity, bacterial staining was performed on wastewater contained in inoculum tanks and biofilm samples from bioreactors. Using microscopy and qPCR, the purpose of this experiment was to determine if the population of AOB and NOB in wastewater and membrane bioreactors changed depending on temperature and hibernation conditions to determine the optimal parameters for AOB/NOB culture to effectively clean wastewater.

Novel Co(II) phthalocyanines of extended periphery and their water-soluble derivatives. Synthesis, spectral properties and catalytic activity

NASA Astrophysics Data System (ADS)

Filippova, Anna; Vashurin, Artur; Znoyko, Serafima; Kuzmin, Ilya; Razumov, Mikhail; Chernova, Alena; Shaposhnikov, Gennady; Koifman, Oscar

2017-12-01

Novel complexes of cobalt and copper with substituted phthalocyanines were synthesized and characterized. Their water-soluble derivatives were obtained by sulfonation under mild conditions and structurally proved. Aggregation equilibrium in water mediums was shown and influence of geometrical and electron parameters of macroheterocycle peripheral substituents on these processes was established. Catalytic activity upon liquid-phase oxidation of N,N-diethylcarbamodithiolate to thiuram E was studied. Kinetic parameters of substrate oxidation in presence of cobalt phthalocyanines were considered.

Development of Energy-Efficient Single-Electron Transistors with Oxide Nanoelectronics

DTIC Science & Technology

2011-05-01

Eom, and J. Levy, "“ Water - cycle ” mechanism for writing and erasing nanostructures at the LaAlO3/SrTiO3 interface," Appl. Phys. Lett. 97, 173110 (2010...process as a “ water cycle ” because it permits multiple writing and erasing without physical modification of the oxide heterostructure. Figure 8...test of the “ water cycle ” mechanism outlined above replaces atmospheric conditions with gas environments that lack H2O. Figure 9(a-c) shows the

Removal of the cyanotoxin anatoxin-a by drinking water treatment processes: a review.

PubMed

Vlad, Silvia; Anderson, William B; Peldszus, Sigrid; Huck, Peter M

2014-12-01

Anatoxin-a (ANTX-a) is a potent alkaloid neurotoxin, produced by several species of cyanobacteria and detected throughout the world. The presence of cyanotoxins, including ANTX-a, in drinking water sources is a potential risk to public health. This article presents a thorough examination of the cumulative body of research on the use of drinking water treatment technologies for extracellular ANTX-a removal, focusing on providing an analysis of the specific operating parameters required for effective treatment and on compiling a series of best-practice recommendations for owners and operators of systems impacted by this cyanotoxin. Of the oxidants used in drinking water treatment, chlorine-based processes (chlorine, chloramines and chlorine dioxide) have been shown to be ineffective for ANTX-a treatment, while ozone, advanced oxidation processes and permanganate can be successful. High-pressure membrane filtration (nanofiltration and reverse osmosis) is likely effective, while adsorption and biofiltration may be effective but further investigation into the implementation of these processes is necessary. Given the lack of full-scale verification, a multiple-barrier approach is recommended, employing a combination of chemical and non-chemical processes.

Water soluble nano-scale transient material germanium oxide for zero toxic waste based environmentally benign nano-manufacturing

NASA Astrophysics Data System (ADS)

Almuslem, A. S.; Hanna, A. N.; Yapici, T.; Wehbe, N.; Diallo, E. M.; Kutbee, A. T.; Bahabry, R. R.; Hussain, M. M.

2017-02-01

In the recent past, with the advent of transient electronics for mostly implantable and secured electronic applications, the whole field effect transistor structure has been dissolved in a variety of chemicals. Here, we show simple water soluble nano-scale (sub-10 nm) germanium oxide (GeO2) as the dissolvable component to remove the functional structures of metal oxide semiconductor devices and then reuse the expensive germanium substrate again for functional device fabrication. This way, in addition to transiency, we also show an environmentally friendly manufacturing process for a complementary metal oxide semiconductor (CMOS) technology. Every year, trillions of complementary metal oxide semiconductor (CMOS) electronics are manufactured and billions are disposed, which extend the harmful impact to our environment. Therefore, this is a key study to show a pragmatic approach for water soluble high performance electronics for environmentally friendly manufacturing and bioresorbable electronic applications.

Aluminum/water reactions under extreme conditions

NASA Astrophysics Data System (ADS)

Hooper, Joseph

2013-03-01

We discuss mechanisms that may control the reaction of aluminum and water under extreme conditions. We are particularly interested in the high-temperature, high-strain regime where the native oxide layer is destroyed and fresh aluminum is initially in direct contact with liquid or supercritical water. Disparate experimental data over the years have suggested rapid oxidation of aluminum is possible in such situations, but no coherent picture has emerged as to the basic oxidation mechanism or the physical processes that govern the extent of reaction. We present theoretical and computational analysis of traditional metal/water reaction mechanisms that treat diffusion through a dynamic oxide layer or reaction limited by surface kinetics. Diffusion through a fresh solid oxide layer is shown to be far too slow to have any effect on the millisecond timescale (even at high temperatures). Quantum molecular dynamics simulations of liquid Al and water surface reactions show rapid water decomposition at the interface, catalyzed by adjacent water molecules in a Grotthus-like relay mechanism. The surface reaction barriers are far too low for this to be rate-limiting in any way. With these straightforward mechanisms ruled out, we investigate two more complex possibilities for the rate-limiting factor; first, we explore the possibility that newly formed oxide remains a metastable liquid well below its freezing point, allowing for diffusion-limited reactions through the oxide shell but on a much faster timescale. The extent of reaction would then be controlled by the solidification kinetics of alumina. Second, we discuss preliminary analysis on surface erosion and turbulent mixing, which may play a prominent role during hypervelocity penetration of solid aluminum projectiles into water.

Energy Conservation at the West Dover, Vermont, Water Pollution Control Facility.

DTIC Science & Technology

1982-11-01

chlorination of oxidation ditch effluent ---- 8 Discontinue aerobic digestion --------------------------- 8 Discharge contents of holding pond into...Immediate Discontinue aerobic digestion Instead of aerobically digesting the waste activated sludge, it may be possible to mix it directly with pond...elimi- nated by replacing the oxidation ditches with facultative ponds. Also, this would eliminate the need for aerobic digestion , in-plant process water

Efficient oxidation and sorption of arsenite using a novel titanium(IV)-manganese(IV) binary oxide sorbent.

PubMed

Zhang, Wei; Liu, Caihong; Zheng, Tong; Ma, Jun; Zhang, Gaosheng; Ren, Guohui; Wang, Lu; Liu, Yulei

2018-04-19

Owing to the high toxicity and mobility, the removal of arsenite (As(III)) is significantly more difficult than arsenate (As(V)), thus representing a major challenge in arsenite-contaminated water treatment. For efficient elimination of As(III), we successfully fabricated a novel Ti-Mn binary oxide via a simultaneous oxidation and coprecipitation process. The amorphous oxide was aggregated from nanosized particles with a high specific surface area of 349.5 m 2 /g. It could effectively oxidize As(III) to As(V) and had a high As(III) sorption capacity of 107.0 mg/g. As(III) sorption occurred rapidly and equilibrium was achieved within 24 h. The kinetic data was well fitted by the pseudo-second-order equation, indicating a chemical sorption process. The material was almost independent upon the presence of competitive ions. The As(III) removal by the sorbent is a combined process coupled oxidation with sorption, where the MnO 2 content is mainly responsible for oxidizing As(III) to As(V) and the formed As(V) is then adsorbed onto the surface of amorphous TiO 2 content, through replacing the surface hydroxyl group or the adsorbed As(III) and forming inner-sphere surface complexes. Furthermore, the arsenic-containing oxide could be effectively regenerated and reused. The bi-functional sorbent could be used as a potentially attractive sorbent for As(III) removal in drinking water treatment and environmental remediation. Copyright © 2018. Published by Elsevier B.V.

Degradation of estrone in water and wastewater by various advanced oxidation processes.

PubMed

Sarkar, Shubhajit; Ali, Sura; Rehmann, Lars; Nakhla, George; Ray, Madhumita B

2014-08-15

A comprehensive study was conducted to determine the relative efficacy of various advanced oxidation processes such as O3, H2O2, UV, and combinations of UV/O3, UV/H2O2 for the removal of estrone (E1) from pure water and secondary effluent. In addition to the parent compound (E1) removal, performance of the advanced oxidation processes was characterized using removal of total organic carbon (TOC), and estrogenicity of the effluent. Although E1 removal was high for all the AOPs, intermediates formed were more difficult to degrade leading to slow TOC removal. Energy calculations and cost analysis indicated that, although UV processes have low electricity cost, ozonation is the least cost option ($ 0.34/1000 gallons) when both capital and operating costs were taken into account. Ozonation also is superior to the other tested AOPs due to higher removal of TOC and estrogenicity. The rate of E1 removal decreased linearly with the background TOC in water, however, E1 degradation in the secondary effluent from a local wastewater treatment plant was not affected significantly due to the low COD values in the effluent. Copyright © 2014 Elsevier B.V. All rights reserved.

Aqueous Processing of Atmospheric Organic Particles in Cloud Water Collected via Aircraft Sampling

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

Boone, Eric J.; Laskin, Alexander; Laskin, Julia

2015-07-21

Cloud water and below-cloud atmospheric particle samples were collected onboard a research aircraft during the Southern Oxidant and Aerosol Study (SOAS) over a forested region of Alabama in June 2013. The organic molecular composition of the samples was studied to gain insights into the aqueous-phase processing of organic compounds within cloud droplets. High resolution mass spectrometry with nanospray desorption electrospray ionization and direct infusion electrospray ionization were utilized to compare the organic composition of the particle and cloud water samples, respectively. Isoprene and monoterpene-derived organosulfates and oligomers were identified in both the particles and cloud water, showing the significant influencemore » of biogenic volatile organic compound oxidation above the forested region. While the average O:C ratios of the organic compounds were similar between the atmospheric particle and cloud water samples, the chemical composition of these samples was quite different. Specifically, hydrolysis of organosulfates and formation of nitrogen-containing compounds were observed for the cloud water when compared to the atmospheric particle samples, demonstrating that cloud processing changes the composition of organic aerosol.« less

Energy recovery system

DOEpatents

Moore, Albert S.; Verhoff, Francis H.

1980-01-01

The present invention is directed to an improved wet air oxidation system and method for reducing the chemical oxygen demand (COD) of waste water used from scrubbers of coal gasification plants, with this COD reduction being sufficient to effectively eliminate waste water as an environmental pollutant. The improvement of the present invention is provided by heating the air used in the oxidation process to a temperature substantially equal to the temperature in the oxidation reactor before compressing or pressurizing the air. The compression of the already hot air further heats the air which is then passed in heat exchange with gaseous products of the oxidation reaction for "superheating" the gaseous products prior to the use thereof in turbines as the driving fluid. The superheating of the gaseous products significantly minimizes condensation of gaseous products in the turbine so as to provide a substantially greater recovery of mechanical energy from the process than heretofore achieved.

Effect of Organic Substances on the Efficiency of Fe(Ii) to Fe(Iii) Oxidation and Removal of Iron Compounds from Groundwater in the Sedimentation Process

NASA Astrophysics Data System (ADS)

Krupińska, Izabela

2017-09-01

One of the problems with iron removal from groundwater is organic matter. The article presents the experiments involved groundwater samples with a high concentration of total iron - amounting to 7.20 mgFe/dm3 and an increased amount of organic substances (TOC from 5.50 to 7.50 mgC/dm3). The water samples examined differed in terms of the value of the ratio of the TOC concentration and the concentration of total iron (D). It was concluded that with increase in the coexistence ratio of organic substances and total iron in water (D = [TOC]/[Fetot]), efficiency of Fe(II) to Fe(III) oxidization with dissolved oxygen decreased, while the oxidation time was increasing. This rule was not demonstrated for potassium manganate (VII) when used as an oxidizing agent. The application of potassium manganate (VII) for oxidation of Fe(II) ions produced the better results in terms of total iron concentration reduction in the sedimentation process than the oxidation with dissolved oxygen.

Combining micelle-clay sorption to solar photo-Fenton processes for domestic wastewater treatment.

PubMed

Brienza, Monica; Nir, Shlomo; Plantard, Gael; Goetz, Vincent; Chiron, Serge

2018-06-08

A tertiary treatment of effluent from a biological domestic wastewater treatment plant was tested by combining filtration and solar photocatalysis. Adsorption was carried out by a sequence of two column filters, the first one filled with granular activated carbon (GAC) and the second one with granulated nano-composite of micelle-montmorillonite mixed with sand (20:100, w/w). The applied solar advanced oxidation process was homogeneous photo-Fenton photocatalysis using peroxymonosulfate (PMS) as oxidant agent. This combination of simple, robust, and low-cost technologies aimed to ensure water disinfection and emerging contaminants (ECs, mainly pharmaceuticals) removal. The filtration step showed good performances in removing dissolved organic matter and practically removing all bacteria such as Escherichia coli and Enterococcus faecalis from the secondary treated water. Solar advanced oxidation processes were efficient in elimination of trace levels of ECs. The final effluent presented an improved sanitary level with acceptable chemical and biological characteristics for irrigation.

Diagram of Lake Stratification on Mars

NASA Image and Video Library

2017-06-01

This diagram presents some of the processes and clues related to a long-ago lake on Mars that became stratified, with the shallow water richer in oxidants than deeper water was. The sedimentary rocks deposited within a lake in Mars' Gale Crater more than three billion years ago differ from each other in a pattern that matches what is seen in lakes on Earth. As sediment-bearing water flows into a lake, bedding thickness and particle size progressively decrease as sediment is deposited in deeper and deeper water as seen in examples of thick beds (PIA19074) from shallowest water, thin beds (PIA19075) from deeper water and even thinner beds (PIA19828) from deepest water. At sites on lower Mount Sharp, inside the crater, measurements of chemical and mineral composition by NASA's Curiosity Mars rover reveal a clear correspondence between the physical characteristics of sedimentary rock from different parts of the lake and how strongly oxidized the sediments were. Rocks with textures indicating that the sediments were deposited near the edge of a lake have more strongly oxidized composition than rocks with textures indicating sedimentation in deep water. For example, the iron mineral hematite is more oxidized than the iron mineral magnetite. An explanation for why such chemical stratification occurs in a lake is that the water closer to the surface is more exposed to oxidizing effects of oxygen in the atmosphere and ultraviolet light. On Earth, a stratified lake with a distinct boundary between oxidant-rich shallows and oxidant-poor depths provides a diversity of environments suited to different types of microbes. If Mars has ever hosted microbial live, the stratified lake at Gale Crater may have similarly provided a range of different habitats for life. https://photojournal.jpl.nasa.gov/catalog/PIA21500

Mars Atmospheric Capture and Gas Separation

NASA Technical Reports Server (NTRS)

Muscatello, Anthony; Santiago-Maldonado, Edgardo; Gibson, Tracy; Devor, Robert; Captain, James

2011-01-01

The Mars atmospheric capture and gas separation project is selecting, developing, and demonstrating techniques to capture and purify Martian atmospheric gases for their utilization for the production of hydrocarbons, oxygen, and water in ISRU systems. Trace gases will be required to be separated from Martian atmospheric gases to provide pure C02 to processing elements. In addition, other Martian gases, such as nitrogen and argon, occur in concentrations high enough to be useful as buffer gas and should be captured as welL To achieve these goals, highly efficient gas separation processes will be required. These gas separation techniques are also required across various areas within the ISRU project to support various consumable production processes. The development of innovative gas separation techniques will evaluate the current state-of-the-art for the gas separation required, with the objective to demonstrate and develop light-weight, low-power methods for gas separation. Gas separation requirements include, but are not limited to the selective separation of: (1) methane and water from un-reacted carbon oxides (C02- CO) and hydrogen typical of a Sabatier-type process, (2) carbon oxides and water from unreacted hydrogen from a Reverse Water-Gas Shift process, (3) carbon oxides from oxygen from a trash/waste processing reaction, and (4) helium from hydrogen or oxygen from a propellant scavenging process. Potential technologies for the separations include freezers, selective membranes, selective solvents, polymeric sorbents, zeolites, and new technologies. This paper and presentation will summarize the results of an extensive literature review and laboratory evaluations of candidate technologies for the capture and separation of C02 and other relevant gases.

Analysis of polymer/oxide interfaces under ambient conditions - An experimental perspective

NASA Astrophysics Data System (ADS)

González-Orive, A.; Giner, I.; de los Arcos, T.; Keller, A.; Grundmeier, G.

2018-06-01

In many different hybrid materials and materials composites polymers adhere to bulk oxides or oxide covered metal. The formed polymer/oxide interfaces are of crucial importance for the functionality and durability of such complex materials. Especially, under humid and corrosive conditions such interfaces tend to degrade due to permeability of polymers for water, the high adsorption energy of water on oxide surfaces and even corrosion processes of the metal. Different experimental studies considered such interfaces ranging from spectroscopy to electrochemical analysis. However, it is still a challenge to understand the complex interaction especially under non-ideal ambient conditions. The perspective article presents an overview on the existing experimental approaches and considers most recent experimental developments with regard to their potential applications in the area of polymer/oxide interfaces in the future.

Decolorization of brilliant green dye using immersed lamp sonophotocatalytic reactor

NASA Astrophysics Data System (ADS)

Gole, Vitthal L.; Priya, Astha; Danao, Sanjay P.

2017-12-01

The textile and dye industries require an enormous amount of water for processing and produce a large volume of wastewater. Generated wastewater had potential hazards and a threat to the aquatic biota. The present work investigates the decolorization of brilliant green dye using a combination of two advanced oxidation techniques viz sonocatalysis and photocatalysis (immersed lamp) known as sonophotocatalysis (3 L capacity). The efficiency of decolorization is further improved in the presence of various additives viz. copper oxide, zinc oxide, and sodium chloride. The maximum decolorization of brilliant green (BG) (94.8% in 120 min) obtained in the presence of zinc oxide. The total organic carbon of the treated samples was measured to monitor complete mineralization of BG. The sonophotocatalytic process (in the presence of zinc oxide) shows maximum mineralization. Synergic combination of two oxidation processes increased the production of oxidizing radicals. Continuous cleaning of catalyst surface (due to sonolysis effect) improves the activity of the catalyst for photolysis operation. The present work is highly useful for the development of a sonophotocatalytic process.

Pulsed Electron Beam Water Radiolysis for Sub-Microsecond Hydroxyl Radical Protein Footprinting

PubMed Central

Watson, Caroline; Janik, Ireneusz; Zhuang, Tiandi; Charvátová, Olga; Woods, Robert J.; Sharp, Joshua S.

2009-01-01

Hydroxyl radical footprinting is a valuable technique for studying protein structure, but care must be taken to ensure that the protein does not unfold during the labeling process due to oxidative damage. Footprinting methods based on sub-microsecond laser photolysis of peroxide that complete the labeling process faster than the protein can unfold have been recently described; however, the mere presence of large amounts of hydrogen peroxide can also cause uncontrolled oxidation and minor conformational changes. We have developed a novel method for sub-microsecond hydroxyl radical protein footprinting using a pulsed electron beam from a 2 MeV Van de Graaff electron accelerator to generate a high concentration of hydroxyl radicals by radiolysis of water. The amount of oxidation can be controlled by buffer composition, pulsewidth, dose, and dissolved nitrous oxide gas in the sample. Our results with ubiquitin and β-lactoglobulin A demonstrate that one sub-microsecond electron beam pulse produces extensive protein surface modifications. Highly reactive residues that are buried within the protein structure are not oxidized, indicating that the protein retains its folded structure during the labeling process. Time-resolved spectroscopy indicates that the major part of protein oxidation is complete in a timescale shorter than that of large scale protein motions. PMID:19265387

Transformation of Contaminant Candidate List (CCL3) compounds during ozonation and advanced oxidation processes in drinking water: Assessment of biological effects.

PubMed

Mestankova, Hana; Parker, Austa M; Bramaz, Nadine; Canonica, Silvio; Schirmer, Kristin; von Gunten, Urs; Linden, Karl G

2016-04-15

The removal of emerging contaminants during water treatment is a current issue and various technologies are being explored. These include UV- and ozone-based advanced oxidation processes (AOPs). In this study, AOPs were explored for their degradation capabilities of 25 chemical contaminants on the US Environmental Protection Agency's Contaminant Candidate List 3 (CCL3) in drinking water. Twenty-three of these were found to be amenable to hydroxyl radical-based treatment, with second-order rate constants for their reactions with hydroxyl radicals (OH) in the range of 3-8 × 10(9) M(-1) s(-1). The development of biological activity of the contaminants, focusing on mutagenicity and estrogenicity, was followed in parallel with their degradation using the Ames and YES bioassays to detect potential changes in biological effects during oxidative treatment. The majority of treatment cases resulted in a loss of biological activity upon oxidation of the parent compounds without generation of any form of estrogenicity or mutagenicity. However, an increase in mutagenic activity was detected by oxidative transformation of the following CCL3 parent compounds: nitrobenzene (OH, UV photolysis), quinoline (OH, ozone), methamidophos (OH), N-nitrosopyrolidine (OH), N-nitrosodi-n-propylamine (OH), aniline (UV photolysis), and N-nitrosodiphenylamine (UV photolysis). Only one case of formation of estrogenic activity was observed, namely, for the oxidation of quinoline by OH. Overall, this study provides fundamental and practical information on AOP-based treatment of specific compounds of concern and represents a framework for evaluating the performance of transformation-based treatment processes. Copyright © 2016 Elsevier Ltd. All rights reserved.

An analytical method for 14C in environmental water based on a wet-oxidation process.

PubMed

Huang, Yan-Jun; Guo, Gui-Yin; Wu, Lian-Sheng; Zhang, Bing; Chen, Chao-Feng; Zhang, Hai-Ying; Qin, Hong-Juan; Shang-Guan, Zhi-Hong

2015-04-01

An analytical method for (14)C in environmental water based on a wet-oxidation process was developed. The method can be used to determine the activity concentrations of organic and inorganic (14)C in environmental water, or total (14)C, including in drinking water, surface water, rainwater and seawater. The wet-oxidation of the organic component allows the conversion of organic carbon to an inorganic form, and the extraction of the inorganic (14)C can be achieved by acidification and nitrogen purging. Environmental water with a volume of 20 L can be used for the wet-oxidation and extraction, and a detection limit of about 0.02 Bq/g(C) can be achieved for water with carbon content above 15 mg(C)/L, obviously lower than the natural level of (14)C in the environment. The collected carbon is sufficient for measurement with a low level liquid scintillation counter (LSC) for typical samples. Extraction or recovery experiments for inorganic carbon and organic carbon from typical materials, including analytical reagents of organic benzoquinone, sucrose, glutamic acid, nicotinic acid, humic acid, ethane diol, et cetera., were conducted with excellent results based on measurement on a total organic carbon analyzer and LSC. The recovery rate for inorganic carbon ranged tween 98.7%-99.0% with a mean of 98.9(± 0.1)%, for organic carbon recovery ranged between 93.8% and 100.0% with a mean of 97.1(± 2.6)%. Verification and an uncertainty budget of the method are also presented for a representative environmental water. The method is appropriate for (14)C analysis in environmental water, and can be applied also to the analysis of liquid effluent from nuclear facilities. Copyright © 2015 Elsevier Ltd. All rights reserved.

Contaminant Removal from Oxygen Production Systems for In Situ Resource Utilization

NASA Technical Reports Server (NTRS)

Anthony, Stephen M.; Santiago-Maldonado, Edgardo; Captain, James G.; Pawate, Ashtamurthy S.; Kenis, Paul J. A.

2012-01-01

The In Situ Resource Utilization (ISRU) project has been developing technologies to produce oxygen from lunar regolith to provide consumables to a lunar outpost. The processes developed reduce metal oxides in the regolith to produce water, which is then electrolyzed to produce oxygen. Hydrochloic and hydrofluoric acids are byproducts of the reduction processes, as halide minerals are also reduced at oxide reduction conditions. Because of the stringent water quality requirements for electrolysis, there is a need for a contaminant removal process. The Contaminant Removal from Oxygen Production Systems (CROPS) team has been developing a separation process to remove these contaminants in the gas and liquid phase that eliminates the need for consumables. CROPS has been using Nafion, a highly water selective polymeric proton exchange membrane, to recover pure water from the contaminated solution. Membrane thickness, product stream flow rate, and acid solution temperature and concentration were varied with the goal of maximizing water permeation and acid rejection. The results show that water permeation increases with increasing solution temperature and product stream flow rate, while acid rejection increases with decreasing solution temperature and concentration. Thinner membranes allowed for higher water flux and acid rejection than thicker ones. These results were used in the development of the hardware built for the most recent Mars ISRU demonstration project.

Fuel processing for PEM fuel cells: transport and kinetic issues of system design

NASA Astrophysics Data System (ADS)

Zalc, J. M.; Löffler, D. G.

In light of the distribution and storage issues associated with hydrogen, efficient on-board fuel processing will be a significant factor in the implementation of PEM fuel cells for automotive applications. Here, we apply basic chemical engineering principles to gain insight into the factors that limit performance in each component of a fuel processor. A system consisting of a plate reactor steam reformer, water-gas shift unit, and preferential oxidation reactor is used as a case study. It is found that for a steam reformer based on catalyst-coated foils, mass transfer from the bulk gas to the catalyst surface is the limiting process. The water-gas shift reactor is expected to be the largest component of the fuel processor and is limited by intrinsic catalyst activity, while a successful preferential oxidation unit depends on strict temperature control in order to minimize parasitic hydrogen oxidation. This stepwise approach of sequentially eliminating rate-limiting processes can be used to identify possible means of performance enhancement in a broad range of applications.

Degradation of ketoprofen by sulfate radical-based advanced oxidation processes: Kinetics, mechanisms, and effects of natural water matrices.

PubMed

Feng, Yiping; Song, Qingyun; Lv, Wenying; Liu, Guoguang

2017-12-01

Ketoprofen (KET) is a mostly used nonsteroidal anti-inflammatory drug that has been frequently detected in wastewater effluents and surface waters. In this study, we investigated the degradation of KET by sulfate radical (SO 4 - ) based advanced oxidation processes (SR-AOPs) in aqueous solution. The degradation kinetics, mechanisms, and effects of natural water matrices on thermally activated persulfate (TAP) oxidation of KET were systematically investigated. Increasing the temperature and persulfate (PS) concentrations greatly enhanced the degradation of KET. KET degradation is pH-dependent with an optimum pH of 5.0. Reactions in the presence of radical quenchers revealed the dominant role of SO 4 - in oxidizing KET. Water matrix significantly influenced the degradation of KET. The common inorganic anions present in natural waters exhibited inhibitory effect on KET degradation, and the inhibition followed the order of Cl -  > CO 3 2-  > HCO 3 -  > NO 3 - ; however, no significant inhibition of KET degradation was observed in the presence of Ca 2+ and Mg 2+ cations. The presence of natural organic matter (NOM) suppressed KET degradation, and the suppression increased as NOM concentration increase. Products identification and mineralization experiments revealed that KET and its degradation intermediates were finally transformed into CO 2 and H 2 O. The results of this study indicated that applying SR-AOPs for the remediation of KET contaminated water matrix is technically possible. Copyright © 2017 Elsevier Ltd. All rights reserved.

Reprint of "How do components of real cloud water affect aqueous pyruvate oxidation?"

NASA Astrophysics Data System (ADS)

Boris, Alexandra J.; Desyaterik, Yury; Collett, Jeffrey L.

2015-01-01

Chemical oxidation of dissolved volatile or semi-volatile organic compounds within fog and cloud droplets in the atmosphere could be a major pathway for secondary organic aerosol (SOA) formation. This proposed pathway consists of: (1) dissolution of organic chemicals from the gas phase into a droplet; (2) reaction with an aqueous phase oxidant to yield low volatility products; and (3) formation of particle phase organic matter as the droplet evaporates. The common approach to simulating aqueous SOA (aqSOA) reactions is photo-oxidation of laboratory standards in pure water. Reactions leading to aqSOA formation should be studied within real cloud and fog water to determine whether additional competing processes might alter apparent rates of reaction as indicated by rates of reactant loss or product formation. To evaluate and identify the origin of any cloud water matrix effects on one example of observed aqSOA production, pyruvate oxidation experiments simulating aqSOA formation were monitored within pure water, real cloud water samples, and an aqueous solution of inorganic salts. Two analysis methods were used: online electrospray ionization high-resolution time-of-flight mass spectrometry (ESI-HR-ToF-MS), and offline anion exchange chromatography (IC) with quantitative conductivity and qualitative ESI-HR-ToF-MS detection. The apparent rate of oxidation of pyruvate was slowed in cloud water matrices: overall measured degradation rates of pyruvate were lower than in pure water. This can be at least partially accounted for by the observed formation of pyruvate from reactions of other cloud water components. Organic constituents of cloud water also compete for oxidants and/or UV light, contributing to the observed slowed degradation rates of pyruvate. The oxidation of pyruvate was not significantly affected by the presence of inorganic anions (nitrate and sulfate) at cloud-relevant concentrations. Future bulk studies of aqSOA formation reactions using simplified simulated cloud solutions and model estimates of generated aqSOA mass should take into account possible generation of, or competition for, oxidant molecules by organic components found in the complex matrices typically associated with real atmospheric water droplets. Additionally, it is likely that some components of real atmospheric waters have not yet been identified as aqSOA precursors, but could be distinguished through further simplified bulk oxidations of known atmospheric water components.

Oxidation of adsorbed ferrous iron: kinetics and influence of process conditions.

PubMed

Buamah, R; Petrusevski, B; Schippers, J C

2009-01-01

For the removal of iron from groundwater, aeration followed with rapid (sand) filtration is frequently applied. Iron removal in this process is achieved through oxidation of Fe(2 + ) in aqueous solution followed by floc formation as well as adsorption of Fe(2 + ) onto the filter media. The rate of oxidation of the adsorbed Fe(2 + ) on the filter media plays an important role in this removal process. This study focuses on investigating the effect of pH on the rate of oxidation of adsorbed Fe(2 + ). Fe(2 + ) has been adsorbed, under anoxic conditions, on iron oxide coated sand (IOCS) in a short filter column and subsequently oxidized by feeding the column with aerated water. Ferrous ions adsorbed at pH 5, 6, 7 and 8 demonstrated consumption of oxygen, when aerated water was fed into the column. The oxygen uptake at pH 7 and 8 was faster than at pH 5 and 6. However the difference was less pronounced than expected. The difference is attributed to the pH buffering effect of the IOCS. At feedwater pH 5, 6 and 7 the pH in the effluent was higher than in the influent, while a pH drop should occur because of oxidation of adsorbed Fe(2 + ). At pH 8, the pH dropped. These phenomena are attributed to the presence of calcium and /or ferrous carbonate in IOCS.

Dual effects of water vapor on ceria-supported gold clusters.

PubMed

Li, Zhimin; Li, Weili; Abroshan, Hadi; Ge, Qingjie; Li, Gao; Jin, Rongchao

2018-04-05

Atomically precise nanocatalysts are currently being intensely pursued in catalysis research. Such nanocatalysts can serve as model catalysts for gaining fundamental insights into catalytic processes. In this work we report a discovery that water vapor provokes the mild removal of surface long-chain ligands on 25-atom Au25(SC12H25)18 nanoclusters in a controlled manner. Using the resultant Au25(SC12H25)18-x/CeO2 catalyst and CO oxidation as a probe reaction, we found that the catalytic activity of cluster/CeO2 is enhanced from nearly zero conversion of CO (in the absence of water) to 96.2% (in the presence of 2.3 vol% H2O) at the same temperature (100 °C). The cluster catalysts exhibit high stability during the CO oxidation process under moisture conditions (up to 20 vol% water vapor). Water vapor plays a dual role in gold cluster-catalyzed CO oxidation. FT-IR and XPS analyses in combination with density functional theory (DFT) simulations suggest that the "-SC12H25" ligands are easier to be removed under a water vapor atmosphere, thus generating highly active sites. Moreover, the O22- peroxide species constitutes the active oxygen species in CO oxidation, evidenced by Raman spectroscopy analysis and isotope experiments on the CeO2 and cluster/CeO2. The results also indicate the perimeter sites of the interface of Au25(SC12H25)18-x/CeO2 to be active sites for catalytic CO oxidation. The controlled exposure of active sites under mild conditions is of critical importance for the utilization of clusters in catalysis.

Oxidative elimination of cyanotoxins: comparison of ozone, chlorine, chlorine dioxide and permanganate.

PubMed

Rodríguez, Eva; Onstad, Gretchen D; Kull, Tomas P J; Metcalf, James S; Acero, Juan L; von Gunten, Urs

2007-08-01

As the World Health Organization (WHO) progresses with provisional Drinking Water Guidelines of 1 microg/L for microcystin-LR and a proposed Guideline of 1 microg/L for cylindrospermopsin, efficient treatment strategies are needed to prevent cyanotoxins such as these from reaching consumers. A kinetic database has been compiled for the oxidative treatment of three cyanotoxins: microcystin-LR (MC-LR), cylindrospermopsin (CYN), and anatoxin-a (ANTX) with ozone, chlorine, chlorine dioxide and permanganate. This kinetic database contains rate constants not previously reported and determined in the present work (e.g. for permanganate oxidation of ANTX and chlorine dioxide oxidation of CYN and ANTX), together with previously published rate constants for the remaining oxidation processes. Second-order rate constants measured in pure aqueous solutions of these toxins could be used in a kinetic model to predict the toxin oxidation efficiency of ozone, chlorine, chlorine dioxide and permanganate when applied to natural waters. Oxidants were applied to water from a eutrophic Swiss lake (Lake Greifensee) in static-dose testing and dynamic time-resolved experiments to confirm predictions from the kinetic database, and to investigate the effects of a natural matrix on toxin oxidation and by-product formation. Overall, permanganate can effectively oxidize ANTX and MC-LR, while chlorine will oxidize CYN and MC-LR and ozone is capable of oxidizing all three toxins with the highest rate. The formation of trihalomethanes (THMs) in the treated water may be a restriction to the application of sufficiently high-chlorine doses.

THE EFFECT OF WATER CHEMISTRY AND IRON PARTICLE PROPERTIES ON THE REMOVAL OF ARSENIC FOLLOWING THE OXIDATION OF FERROUS IRON

EPA Science Inventory

The current MCL for arsenic is being revised to a lower level by the USEPA. Many new utilities, particularly small utilities, will be forced to add an arsenic removal process or fine tune their curent water treatment process to meet the new MCL. Many arsenic removal processes rel...

[Complex technology for water and wastewater disinfection and its industrial realization in prototype unit].

PubMed

Arakcheev, E N; Brunman, V E; Brunman, M V; Konyashin, A V; Dyachenko, V A; Petkova, A P

Usage of complex automated electrolysis unit for drinking water disinfection and wastewater oxidation and coagulation is scoped, its ecological and energy efficiency is shown. Properties of technological process of anolyte production using membrane electrolysis of brine for water disinfection in municipal pipelines and potassium ferrate production using electrochemical dissolution of iron anode in NaOH solution for usage in purification plants are listed. Construction of modules of industrial prototype for anolyte and ferrate production and applied aspects of automation of complex electrolysis unit are proved. Results of approbation of electrolytic potassium ferrate for drinking water disinfection and wastewater, rain water and environmental water oxidation and coagulation are shown.

Performance Assessment of the Exploration Water Recovery System

NASA Technical Reports Server (NTRS)

Carter. D. Layne; Tabb, David; Perry, Jay

2008-01-01

A new water recovery system architecture designed to fulfill the National Aeronautics and Space Administration s (NASA) Space Exploration Policy has been tested at the Marshall Space Flight Center (MSFC). This water recovery system architecture evolved from the current state-of-the-art system developed for the International Space Station (ISS). Through novel integration of proven technologies for air and water purification, this system promises to elevate existing system optimization. The novel aspect of the system is twofold. First, volatile organic compounds (VOC) are removed from the cabin air via catalytic oxidation in the vapor phase, prior to their absorption into the aqueous phase. Second, vapor compression distillation (VCD) technology processes the condensate and hygiene waste streams in addition to the urine waste stream. Oxidation kinetics dictate that removing VOCs from the vapor phase is more efficient. Treating the various waste streams by VCD reduces the load on the expendable ion exchange and adsorption media which follows, as well as the aqueous-phase catalytic oxidation process further downstream. This paper documents the results of testing this new architecture.

Decomposition of 3,5-dinitrobenzamide in aqueous solution during UV/H2O2 and UV/TiO2 oxidation processes.

PubMed

Yan, Yingjie; Liao, Qi-Nan; Ji, Feng; Wang, Wei; Yuan, Shoujun; Hu, Zhen-Hu

2017-02-01

3,5-Dinitrobenzamide has been widely used as a feed additive to control coccidiosis in poultry, and part of the added 3,5-dinitrobenzamide is excreted into wastewater and surface water. The removal of 3,5-dinitrobenzamide from wastewater and surface water has not been reported in previous studies. Highly reactive hydroxyl radicals from UV/hydrogen peroxide (H 2 O 2 ) and UV/titanium dioxide (TiO 2 ) advanced oxidation processes (AOPs) can decompose organic contaminants efficiently. In this study, the decomposition of 3,5-dinitrobenzamide in aqueous solution during UV/H 2 O 2 and UV/TiO 2 oxidation processes was investigated. The decomposition of 3,5-dinitrobenzamide fits well with a fluence-based pseudo-first-order kinetics model. The decomposition in both two oxidation processes was affected by solution pH, and was inhibited under alkaline conditions. Inorganic anions such as NO 3 - , Cl - , SO 4 2- , HCO 3 - , and CO 3 2- inhibited the degradation of 3,5-dinitrobenzamide during the UV/H 2 O 2 and UV/TiO 2 oxidation processes. After complete decomposition in both oxidation processes, approximately 50% of 3,5-dinitrobenzamide was decomposed into organic intermediates, and the rest was mineralized to CO 2 , H 2 O, and other inorganic anions. Ions such as NH 4 + , NO 3 - , and NO 2 - were released into aqueous solution during the degradation. The primary decomposition products of 3,5-dinitrobenzamide were identified using time-of-flight mass spectrometry (LCMS-IT-TOF). Based on these products and ions release, a possible decomposition pathway of 3,5-dinitrobenzamide in both UV/H 2 O 2 and UV/TiO 2 processes was proposed.

Sorption and desorption of arsenic to ferrihydrite in a sand filter.

PubMed

Jessen, Soren; Larsen, Flemming; Koch, Christian Bender; Arvin, Erik

2005-10-15

Elevated arsenic concentrations in drinking water occur in many places around the world. Arsenic is deleterious to humans, and consequently, As water treatment techniques are sought. To optimize arsenic removal, sorption and desorption processes were studied at a drinking water treatment plant with aeration and sand filtration of ferrous iron rich groundwater at Elmevej Water Works, Fensmark, Denmark. Filter sand and pore water were sampled along depth profiles in the filters. The sand was coated with a 100-300 microm thick layer of porous Si-Ca-As-contaning iron oxide (As/Fe = 0.17) with locally some manganese oxide. The iron oxide was identified as a Si-stabilized abiotically formed two-line ferrihydrite with a magnetic hyperfine field of 45.8 T at 5 K. The raw water has an As concentration of 25 microg/L, predominantly as As(II). As the water passes through the filters, As(III) is oxidized to As(V) and the total concentrations drop asymptotically to a approximately 15 microg/L equilibrium concentration. Mn is released to the pore water, indicating the existence of reactive manganese oxides within the oxide coating, which probably play a role for the rapid As(III) oxidation. The As removal in the sand filters appears controlled by sorption equilibrium onto the ferrihydrite. By addition of ferrous chloride (3.65 mg of Fe(II)/L) to the water stream between two serially connected filters, a 3 microg/L As concentration is created in the water that infiltrates into the second sand filter. However, as water flow is reestablished through the second filter, As desorbs from the ferrihydrite and increases until the 15 microg/L equilibrium concentration. Sequential chemical extractions and geometrical estimates of the fraction of surface-associated As suggest that up to 40% of the total As can be remobilized in response to changes in the water chemistry in the sand filter.

Modeling hyporheic zone processes

USGS Publications Warehouse

Runkel, Robert L.; McKnight, Diane M.; Rajaram, Harihar

2003-01-01

Stream biogeochemistry is influenced by the physical and chemical processes that occur in the surrounding watershed. These processes include the mass loading of solutes from terrestrial and atmospheric sources, the physical transport of solutes within the watershed, and the transformation of solutes due to biogeochemical reactions. Research over the last two decades has identified the hyporheic zone as an important part of the stream system in which these processes occur. The hyporheic zone may be loosely defined as the porous areas of the stream bed and stream bank in which stream water mixes with shallow groundwater. Exchange of water and solutes between the stream proper and the hyporheic zone has many biogeochemical implications, due to differences in the chemical composition of surface and groundwater. For example, surface waters are typically oxidized environments with relatively high dissolved oxygen concentrations. In contrast, reducing conditions are often present in groundwater systems leading to low dissolved oxygen concentrations. Further, microbial oxidation of organic materials in groundwater leads to supersaturated concentrations of dissolved carbon dioxide relative to the atmosphere. Differences in surface and groundwater pH and temperature are also common. The hyporheic zone is therefore a mixing zone in which there are gradients in the concentrations of dissolved gasses, the concentrations of oxidized and reduced species, pH, and temperature. These gradients lead to biogeochemical reactions that ultimately affect stream water quality. Due to the complexity of these natural systems, modeling techniques are frequently employed to quantify process dynamics.

Influence of oxidation state on water solubility of Si nanoparticles prepared by laser ablation in water

NASA Astrophysics Data System (ADS)

Ryabchikov, Yu. V.; Al-Kattan, A.; Chirvony, V.; Sanchez-Royo, J. F.; Sentis, M.; Timoshenko, V. Yu.; Kabashin, A. V.

2017-02-01

Femtosecond laser fragmentation from preliminarily prepared water-dispersed Si microcolloids was used to synthesize bare (ligand-free) spherical silicon nanoparticles (Si-NPs) with low size dispersion and controllable mean size from a few nm to several tens of nm. In order to control the oxidation state of Si-NPs, the fragmentation was performed in normal oxygen-saturated water (oxygen-rich conditions) or in water disoxygenated by pumping with noble gases (Ag, He) before and during the experiment (oxygen-free conditions). XPS and TEM studies revealed that Si-NPs were composed of Si nanocrystals with inclusions of silicon oxide species, covered by SiOx (1 < x < 2) shell, while the total oxide content depended whether Si-NPs were prepared in oxygen-rich or oxygen-free conditions. When placed into a dialysis box, waterdispersed Si-NPs rapidly dissolved, which was evidenced by TEM data. In this case, NPs prepared under oxygen-rich conditions demonstrated much faster dissolution kinetics and their complete disappearance after 7-10 days, while the dissolution process of less oxidized counterparts could last much longer (25-30 days). Much fast dissolution kinetics of more oxidized Si-NPs was attributed to more friable structure of nanoparticle core due to the presence of numerous oxidation-induced defects. Laser-synthesized Si-NPs are of paramount importance for biomedical applications.

Electron, proton and hydrogen-atom transfers in photosynthetic water oxidation.

PubMed Central

Tommos, Cecilia

2002-01-01

When photosynthetic organisms developed so that they could use water as an electron source to reduce carbon dioxide, the stage was set for efficient proliferation. Algae and plants spread globally and provided the foundation for our atmosphere and for O(2)-based chemistry in biological systems. Light-driven water oxidation is catalysed by photosystem II, the active site of which contains a redox-active tyrosine denoted Y(Z), a tetramanganese cluster, calcium and chloride. In 1995, Gerald Babcock and co-workers presented the hypothesis that photosynthetic water oxidation occurs as a metallo-radical catalysed process. In this model, the oxidized tyrosine radical is generated by coupled proton/electron transfer and re-reduced by abstracting hydrogen atoms from substrate water or hydroxide-ligated to the manganese cluster. The proposed function of Y(Z) requires proton transfer from the tyrosine site upon oxidation. The oxidation mechanism of Y(Z) in an inhibited and O(2)-evolving photosystem II is discussed. Domino-deprotonation from Y(Z) to the bulk solution is shown to be consistent with a variety of data obtained on metal-depleted samples. Experimental data that suggest that the oxidation of Y(Z) in O(2)-evolving samples is coupled to proton transfer in a hydrogen-bonding network are described. Finally, a dielectric-dependent model for the proton release that is associated with the catalytic cycle of photosystem II is discussed. PMID:12437877

Development of a novel wet oxidation process for hazardous and mixed wastes

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

Dhooge, P.M.

1994-12-31

Many DOE waste streams and remediates contain complex and variable mixtures of organic compounds, toxic metals, and radionuclides. These materials are often dispersed in organic or inorganic matrices, such as personal protective equipment, various sludges, soils, and water. The over all objective of the effort described here is to develop a novel catalytic wet oxidation process for the treatment of these multi-component wastes, with the aim of providing a versatile, non-thermal method which will destroy hazardous organic compounds while simultaneously containing and concentrating toxic and radioactive metals for recovery or disposal in a readily stabilized matrix. The DETOX process usesmore » a unique combination of metal catalysts to increase the rate of oxidation of organic materials. The metal catalysts are in the form of salts dissolved in a dilute acid solution. A typical catalyst composition is 60% ferric chloride, 3--4% hydrochloric acid, 0.13% platinum ions, and 0.13% ruthenium ions in a water solution. The catalyst solution is maintained at 423--473 K. Wastes are introduced into contact with the solution, where their organic portion is oxidized to carbon dioxide and water. If the organic portion is chlorinated, hydrogen chloride will be produced as a product. The process is a viable alternative to incineration for the treatment of organic mixed wastes. Estimated costs for waste treatment using the process are from $2.50/kg to $25.00/kg, depending on the size of the unit and the amount of waste processed. Process units can be mobile for on-site treatment of wastes. Results from phase 1 and 2, design and engineering studies, are described.« less

Solid waste treatment processes for space station

NASA Technical Reports Server (NTRS)

Marrero, T. R.

1983-01-01

The purpose of this study was to evaluate the state-of-the-art of solid waste(s) treatment processes applicable to a Space Station. From the review of available information a source term model for solid wastes was determined. An overall system is proposed to treat solid wastes under constraints of zero-gravity and zero-leakage. This study contains discussion of more promising potential treatment processes, including supercritical water oxidation, wet air (oxygen) oxidation, and chemical oxidation. A low pressure, batch-type treament process is recommended. Processes needed for pretreatment and post-treatment are hardware already developed for space operations. The overall solid waste management system should minimize transfer of wastes from their collection point to treatment vessel.

Method of making metal oxide ceramic membranes with small pore sizes

DOEpatents

Anderson, Marc A.; Xu, Qunyin

1992-01-01

A method for the production of metal oxide ceramic membranes is composed of very small pore size. The process is particularly useful in the creation of titanium and other transition metal oxide membranes. The method utilizes a sol-gel process in which the rate of particle formation is controlled by substituting a relatively large alcohol in the metal alkoxide and by limiting the available water. Stable, transparent metal oxide ceramic membranes are created having a narrow distribution of pore size, with the pore diameter being manipulable in the range of 5 to 40 Angstroms.

Direct in Situ Measurement of Charge Transfer Processes During Photoelectrochemical Water Oxidation on Catalyzed Hematite

DOE PAGES

Qiu, Jingjing; Hajibabaei, Hamed; Nellist, Michael R.; ...

2017-08-17

Electrocatalysts improve the efficiency of light-absorbing semiconductor photoanodes driving the oxygen evolution reaction, but the precise function(s) of the electrocatalysts remains unclear. We directly measure, for the first time, the interface carrier transport properties of a prototypical visible-light-absorbing semiconductor, α-Fe 2O 3, in contact with one of the fastest known water oxidation catalysts, Ni 0.8Fe 0.2O x, by directly measuring/controlling the current and/or voltage at the Ni 0.8Fe 0.2O x catalyst layer using a second working electrode. The measurements demonstrate that the majority of photogenerated holes in α-Fe 2O 3 directly transfer to the catalyst film over a wide rangemore » of conditions and that the Ni 0.8Fe 0.2O x is oxidized by photoholes to an operating potential sufficient to drive water oxidation at rates that match the photocurrent generated by the α-Fe 2O 3. The Ni 0.8Fe 0.2O x therefore acts as both a hole-collecting contact and a catalyst for the photoelectrochemical water oxidation process. Separate measurements show that the illuminated junction photovoltage across the α-Fe 2O 3|Ni 0.8Fe 0.2O x interface is significantly decreased by the oxidation of Ni 2+ to Ni 3+ and the associated increase in the Ni 0.8Fe 0.2O x electrical conductivity. Finally, in sum, the results illustrate the underlying operative charge-transfer and photovoltage generation mechanisms of catalyzed photoelectrodes, thus guiding their continued improvement.« less

Improvement of bias-stability in amorphous-indium-gallium-zinc-oxide thin-film transistors by using solution-processed Y{sub 2}O{sub 3} passivation

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

An, Sungjin; Mativenga, Mallory; Kim, Youngoo

2014-08-04

We demonstrate back channel improvement of back-channel-etch amorphous-indium-gallium-zinc-oxide (a-IGZO) thin-film transistors by using solution-processed yttrium oxide (Y{sub 2}O{sub 3}) passivation. Two different solvents, which are acetonitrile (35%) + ethylene glycol (65%), solvent A and deionized water, solvent B are investigated for the spin-on process of the Y{sub 2}O{sub 3} passivation—performed after patterning source/drain (S/D) Mo electrodes by a conventional HNO{sub 3}-based wet-etch process. Both solvents yield devices with good performance but those passivated by using solvent B exhibit better light and bias stability. Presence of yttrium at the a-IGZO back interface, where it occupies metal vacancy sites, is confirmed by X-ray photoelectronmore » spectroscopy. The passivation effect of yttrium is more significant when solvent A is used because of the existence of more metal vacancies, given that the alcohol (65% ethylene glycol) in solvent A may dissolve the metal oxide (a-IGZO) through the formation of alkoxides and water.« less

Formation of aqueous-phase sulfate during the haze period in China: Kinetics and atmospheric implications

NASA Astrophysics Data System (ADS)

Zhang, Haijie; Chen, Shilu; Zhong, Jie; Zhang, Shaowen; Zhang, Yunhong; Zhang, Xiuhui; Li, Zesheng; Zeng, Xiao Cheng

2018-03-01

Sulfate is one of the most important components in the aerosol due to its key role in air pollution and global climate change. Recent work has suggested that reactive nitrogen chemistry in aqueous water can explain the missing source of sulfate in the aqueous water. Herein, we have mapped out the energy profile of the oxidization process of SO2 leading from NO2 and two feasible three-step mechanisms have been proposed. For the oxidation of HOSO2- and HSO3- by the dissolved NO2 in weakly acidic and neutral aerosol (pH ≤ 7), the main contribution to the missing sulfate production comes from the oxidation of HOSO2-. The whole process is a self-sustaining process. For the oxidation of SO32- in alkaline aerosol (pH > 7), the third step - decomposition step of H2O or hydrolysis of SO3 step which are two parallel processes are the rate-limiting steps. The present results are of avail to better understand the missing source of sulfate in the aerosol and hence may lead to better science-based solutions for resolving the severe haze problems in China.

Process for thermochemically producing hydrogen

DOEpatents

Bamberger, Carlos E.; Richardson, Donald M.

1976-01-01

Hydrogen is produced by the reaction of water with chromium sesquioxide and strontium oxide. The hydrogen producing reaction is combined with other reactions to produce a closed chemical cycle for the thermal decomposition of water.

Investigation of impact of post-metallization annealing on reliability of 65 nm NOR floating-gate flash memories

NASA Astrophysics Data System (ADS)

Chiu, Shengfen; Xu, Yue; Ji, Xiaoli; Yan, Feng

2016-12-01

This paper investigates the impact of post-metallization annealing (PMA) in pure nitrogen ambient on the reliability of 65 nm NOR-type floating-gate flash memory devices. The experimental results show that, with PMA process, the cycling performance of flash cells, especially for the erasing speed is obviously degraded compared to that without PMA. It is found that the bulk oxide traps and tunnel oxide/Si interface traps are significantly increased with PMA treatment. The water/moisture residues left in the interlayer dielectric layers diffuse to tunnel oxide during PMA process is considered to be responsible for these traps generation, which further enhances the degradation of erase performance. Skipping PMA treatment is proposed to suppress the water diffusion effect on erase performance degradation of flash cells.

Development of a prototype experiment for treating CELSS and PCELSS wastes to produce nutrients for plant growth

NASA Technical Reports Server (NTRS)

1983-01-01

Future long term spaceflights require extensive recycling of wastes to minimize the need for resupplying the vessel. The recycling occurs in a fully or partially closed environment life support system (CELSS or PCELSS). The National Aeronautics and Space Administration (NASA) is interested in converting wastewater into potable water or water for hydroponic farming as part of a CELSS. The development of technologies for wastewater treatment that produce a minimum of by-products is essential. One process that achieves good conversion of moderately concentrated organic wastes in water (1 to 20% by weight) completely to carbon dioxide and water is oxidation in supercritical water. Both air (or oxygen) and many organics are completely miscible with supercritical water, so there are no interphase mass transport resistances that limits the overall oxidation reaction. The temperature of supercritical water, which must be above 374 C, is also sufficient to have rapid reaction kinetics for the oxidations.

Bench-scale evaluation of ferrous iron oxidation kinetics in drinking water: effect of corrosion control and dissolved organic matter.

PubMed

Rahman, Safiur; Gagnon, Graham A

2014-01-01

Corrosion control strategies are important for many utilities in maintaining water quality from the water treatment plant to the customers' tap. In drinking water with low alkalinity, water quality can become significantly degraded in iron-based pipes if water utilities are not diligent in maintaining proper corrosion control. This article reports on experiments conducted in bicarbonate buffered (5 mg-C/L) synthetic water to determine the effects of corrosion control (pH and phosphate) and dissolved organic matter (DOM) on the rate constants of the Fe(II) oxidation process. A factorial design approach elucidated that pH (P = 0.007, contribution: 42.5%) and phosphate (P = 0.025, contribution: 22.7%) were the statistically significant factors in the Fe(II) oxidation process at a 95% confidence level. The comprehensive study revealed a significant dependency relationship between the Fe(II) oxidation rate constants (k) and phosphate-to- Fe(II) mole ratio. At pH 6.5, the optimum mole ratio was found to be 0.3 to reduce the k values. Conversely, the k values were observed to increase for the phosphate-to- Fe(II) mole ratio > 1. The factorial design approach revealed that chlorine and DOM for the designated dosages did not cause a statistically significant (α = 0.05, P > 0.05)change in rate constants. However, an increment of the chlorine to ferrous iron mole ratio by a factor of ∼ 2.5 resulted in an increase k values by a factor of ∼ 10. This study conclusively demonstrated that the lowest Fe(II) oxidation rate constant was obtained under low pH conditions (pH ≤ 6.5), with chlorine doses less than 2.2 mg/L and with a phosphate-to-Fe(II) mole ratio ≈ 0.3 in the iron water systems.

Heptanuclear CoII5CoIII2 Cluster as Efficient Water Oxidation Catalyst.

PubMed

Xu, Jia-Heng; Guo, Ling-Yu; Su, Hai-Feng; Gao, Xiang; Wu, Xiao-Fan; Wang, Wen-Guang; Tung, Chen-Ho; Sun, Di

2017-02-06

Inspired by the transition-metal-oxo cubical Mn 4 CaO 5 in photosystem II, we herein report a disc-like heptanuclear mixed-valent cobalt cluster, [Co II 5 Co III 2 (mdea) 4 (N 3 ) 2 (CH 3 CN) 6 (OH) 2 (H 2 O) 2 ·4ClO 4 ] (1, H 2 mdea = N-methyldiethanolamine), for photocatalytic oxygen evolution. The topology of the Co 7 core resembles a small piece of cobaltate protected by terminal H 2 O, N 3 - , CH 3 CN, and multidentate N-methyldiethanolamine at the periphery. Under the optimal photocatalytic conditions, 1 exhibits water oxidation activity with a turnover number (TON) of 210 and a turnover frequency (TOF initial ) of 0.23 s -1 . Importantly, electrospray mass spectrometry (ESI-MS) was used to not only identify the possible main active species in the water oxidation reaction but also monitor the evolutions of oxidation states of cobalt during the photocatalytic reactions. These results shed light on the design concept of new water oxidation catalysts and mechanism-related issues such as the key active intermediate and oxidation state evolution in the oxygen evolution process. The magnetic properties of 1 were also discussed in detail.

Distance-dependent radiation chemistry: Oxidation versus hydrogenation of CO in electron-irradiated H2O/CO/H2O ices

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

Petrik, Nikolay G.; Monckton, Rhiannon J.; Koehler, Sven

Electron-stimulated oxidation of CO in layered H2O/CO/H2O ices was investigated with infrared reflection-absorption spectroscopy (IRAS) as function of the distance of the CO layer from the water/vacuum interface. The results show that while both oxidation and reduction reactions occur within the irradiated water films, there are distinct regions where either oxidation or reduction reactions are dominant. At depths less than ~ 15 ML, CO oxidation dominates over the sequential hydrogenation of CO to methanol (CH3OH), and CO2 is the major product of CO oxidation, consistent with previous observations. At its highest yield, CO2 accounts for ~45% of all the reactedmore » CO. Another oxidation product is identified as the formate anion (HCO2-). In contrast, for CO buried more than ~ 35 ML below the water/vacuum interface, the CO-to-methanol conversion efficiency is close to 100%. Production of CO2 and formate are not observed for the more deeply buried CO layers, where hydrogenation dominates. Experiments with CO dosed on pre-irradiated ASW samples suggest that OH radicals are primarily responsible for the oxidation reactions. Possible mechanisms of CO oxidation, involving primary and secondary processes of water radiolysis at low temperature, are discussed. The observed distance-dependent radiation chemistry results from the higher mobility of hydrogen atoms that are created by the interaction of the 100 eV electrons with the water films. These hydrogen atoms, which are primarily created at or near the water/vacuum interface, can desorb from or diffuse into the water films, while the less-mobile OH radicals remain in the near-surface zone resulting in preferential oxidation reactions there. The diffusing hydrogen atoms are responsible for the hydrogenation reactions that are dominant for the more deeply buried CO layers.« less

Self-Propelled Micromotors for Cleaning Polluted Water

PubMed Central

2013-01-01

We describe the use of catalytically self-propelled microjets (dubbed micromotors) for degrading organic pollutants in water via the Fenton oxidation process. The tubular micromotors are composed of rolled-up functional nanomembranes consisting of Fe/Pt bilayers. The micromotors contain double functionality within their architecture, i.e., the inner Pt for the self-propulsion and the outer Fe for the in situ generation of ferrous ions boosting the remediation of contaminated water.The degradation of organic pollutants takes place in the presence of hydrogen peroxide, which acts as a reagent for the Fenton reaction and as main fuel to propel the micromotors. Factors influencing the efficiency of the Fenton oxidation process, including thickness of the Fe layer, pH, and concentration of hydrogen peroxide, are investigated. The ability of these catalytically self-propelled micromotors to improve intermixing in liquids results in the removal of organic pollutants ca. 12 times faster than when the Fenton oxidation process is carried out without catalytically active micromotors. The enhanced reaction–diffusion provided by micromotors has been theoretically modeled. The synergy between the internal and external functionalities of the micromotors, without the need of further functionalization, results into an enhanced degradation of nonbiodegradable and dangerous organic pollutants at small-scale environments and holds considerable promise for the remediation of contaminated water. PMID:24180623

UV/TiO₂ photocatalytic oxidation of recalcitrant organic matter: effect of salinity and pH.

PubMed

Muthukumaran, Shobha; Song, Lili; Zhu, Bo; Myat, Darli; Chen, Jin-Yuan; Gray, Stephen; Duke, Mikel

2014-01-01

Photocatalytic oxidation processes have interest for water treatment since these processes can remove recalcitrant organic compounds and operate at mild conditions of temperature and pressure. However, performance under saline conditions present in many water resources is not well known. This study aims to explore the basic effects of photocatalysis on the removal of organic matter in the presence of salt. A laboratory-scale photocatalytic reactor system, employing ultraviolet (UV)/titanium dioxide (TiO₂) photocatalysis was evaluated for its ability to remove the humic acid (HA) from saline water. The particle size and zeta potential of TiO₂ under different conditions including solution pH and sodium chloride (NaCl) concentrations were characterized. The overall degradation of organics over the NaCl concentration range of 500-2,000 mg/L was found to be 80% of the non-saline equivalent after 180 min of the treatment. The results demonstrated that the adsorption of HA onto the TiO₂ particles was dependent on both the pH and salinity due to electrostatic interaction and highly unstable agglomerated dispersion. This result supports UV/TiO₂ as a viable means to remove organic compounds, but the presence of salt in waters to be treated will influence the performance of the photocatalytic oxidation process.

Visible light water splitting using dye-sensitized oxide semiconductors.

PubMed

Youngblood, W Justin; Lee, Seung-Hyun Anna; Maeda, Kazuhiko; Mallouk, Thomas E

2009-12-21

Researchers are intensively investigating photochemical water splitting as a means of converting solar to chemical energy in the form of fuels. Hydrogen is a key solar fuel because it can be used directly in combustion engines or fuel cells, or combined catalytically with CO(2) to make carbon containing fuels. Different approaches to solar water splitting include semiconductor particles as photocatalysts and photoelectrodes, molecular donor-acceptor systems linked to catalysts for hydrogen and oxygen evolution, and photovoltaic cells coupled directly or indirectly to electrocatalysts. Despite several decades of research, solar hydrogen generation is efficient only in systems that use expensive photovoltaic cells to power water electrolysis. Direct photocatalytic water splitting is a challenging problem because the reaction is thermodynamically uphill. Light absorption results in the formation of energetic charge-separated states in both molecular donor-acceptor systems and semiconductor particles. Unfortunately, energetically favorable charge recombination reactions tend to be much faster than the slow multielectron processes of water oxidation and reduction. Consequently, visible light water splitting has only recently been achieved in semiconductor-based photocatalytic systems and remains an inefficient process. This Account describes our approach to two problems in solar water splitting: the organization of molecules into assemblies that promote long-lived charge separation, and catalysis of the electrolysis reactions, in particular the four-electron oxidation of water. The building blocks of our artificial photosynthetic systems are wide band gap semiconductor particles, photosensitizer and electron relay molecules, and nanoparticle catalysts. We intercalate layered metal oxide semiconductors with metal nanoparticles. These intercalation compounds, when sensitized with [Ru(bpy)(3)](2+) derivatives, catalyze the photoproduction of hydrogen from sacrificial electron donors (EDTA(2-)) or non-sacrificial donors (I(-)). Through exfoliation of layered metal oxide semiconductors, we construct multilayer electron donor-acceptor thin films or sensitized colloids in which individual nanosheets mediate light-driven electron transfer reactions. When sensitizer molecules are "wired" to IrO(2).nH(2)O nanoparticles, a dye-sensitized TiO(2) electrode becomes the photoanode of a water-splitting photoelectrochemical cell. Although this system is an interesting proof-of-concept, the performance of these cells is still poor (approximately 1% quantum yield) and the dye photodegrades rapidly. We can understand the quantum efficiency and degradation in terms of competing kinetic pathways for water oxidation, back electron transfer, and decomposition of the oxidized dye molecules. Laser flash photolysis experiments allow us to measure these competing rates and, in principle, to improve the performance of the cell by changing the architecture of the electron transfer chain.

Detailed electrochemical studies of the tetraruthenium polyoxometalate water oxidation catalyst in acidic media: identification of an extended oxidation series using Fourier transformed alternating current voltammetry.

PubMed

Lee, Chong-Yong; Guo, Si-Xuan; Murphy, Aidan F; McCormac, Timothy; Zhang, Jie; Bond, Alan M; Zhu, Guibo; Hill, Craig L; Geletii, Yurii V

2012-11-05

The electrochemistry of the water oxidation catalyst, Rb(8)K(2)[{Ru(4)O(4)(OH)(2)(H(2)O)(4)}(γ-SiW(10)O(36))(2)] (Rb(8)K(2)-1(0)) has been studied in the presence and absence of potassium cations in both hydrochloric and sulfuric acid solutions by transient direct current (dc) cyclic voltammetry, a steady state dc method in the rotating disk configuration and the kinetically sensitive technique of Fourier transformed large-amplitude alternating current (ac) voltammetry. In acidic media, the presence of potassium ions affects the kinetics (apparent rate of electron transfer) and thermodynamics (reversible potentials) of the eight processes (A'/A to H/H') that are readily detected under dc voltammetric conditions. The six most positive processes (A'/A to F/F'), each involve a one electron ruthenium based charge transfer step (A'/A, B'/B are Ru(IV/V) oxidation and C/C' to F/F' are Ru(IV/III) reduction). The apparent rate of electron transfer of the ruthenium centers in sulfuric acid is higher than in hydrochloric acid. The addition of potassium cations increases the apparent rates and gives rise to a small shift of reversible potential. Simulations of the Fourier transformed ac voltammetry method show that the B'/B, E/E', and F/F' processes are quasi-reversible, while the others are close to reversible. A third Ru(IV/V) oxidation process is observed just prior to the positive potential limit via dc methods. Importantly, the ability of the higher harmonic components of the ac method to discriminate against the irreversible background solvent process allows this (process I) as well as an additional fourth reversible ruthenium based process (J) to be readily identified. The steady-state rotating disk electrode (RDE) method confirmed that all four Ru-centers in Rb(8)K(2)-1(0) are in oxidation state IV. The dc and ac data indicate that reversible potentials of the four ruthenium centers are evenly spaced, which may be relevant to understanding of the water oxidation electrocatalysis. A profound effect of the potassium cation is observed for the one-electron transfer process (G/G') assigned to Ru(III/II) reduction and the multiple electron transfer reduction process (H/H') that arise from the tungstate polyoxometalate framework. A significant shift of E°' to a more positive potential value for process H/H' was observed on removal of K(+) (~100 mV in H(2)SO(4) and ~50 mV in HCl).

Iron Oxide Films Prepared by Rapid Thermal Processing for Solar Energy Conversion

PubMed Central

Wickman, B.; Bastos Fanta, A.; Burrows, A.; Hellman, A.; Wagner, J. B.; Iandolo, B.

2017-01-01

Hematite is a promising and extensively investigated material for various photoelectrochemical (PEC) processes for energy conversion and storage, in particular for oxidation reactions. Thermal treatments during synthesis of hematite are found to affect the performance of hematite electrodes considerably. Herein, we present hematite thin films fabricated via one-step oxidation of Fe by rapid thermal processing (RTP). In particular, we investigate the effect of oxidation temperature on the PEC properties of hematite. Films prepared at 750 °C show the highest activity towards water oxidation. These films show the largest average grain size and the highest charge carrier density, as determined from electron microscopy and impedance spectroscopy analysis. We believe that the fast processing enabled by RTP makes this technique a preferred method for investigation of novel materials and architectures, potentially also on nanostructured electrodes, where retaining high surface area is crucial to maximize performance. PMID:28091573

Reduction Dynamics of Doped Ceria, Nickel Oxide, and Cermet Composites Probed Using In Situ Raman Spectroscopy

PubMed Central

Shearing, Paul R.; Brightman, Edward; Brett, Dan J. L.; Brandon, Nigel P.; Cohen, Lesley F.

2016-01-01

The redox properties of gadolinium doped ceria (CGO) and nickel oxide (NiO) composite cermets underpin the operation of solid oxide electrochemical cells. Although these systems have been widely studied, a full comprehension of the reaction dynamics at the interface of these materials is lacking. Here, in situ Raman spectroscopic monitoring of the redox cycle is used to investigate the interplay between the dynamic and competing processes of hydrogen spillover and water dissociation on the doped ceria surface. In order to elucidate these mechanisms, the redox process in pure CGO and NiO is studied when exposed to wet and dry hydrogen and is compared to the cermet behavior. In dry hydrogen, CGO reduces relatively rapidly via a series of intermediate phases, while NiO reduces via a single‐step process. In wet reducing atmospheres, however, the oxidation state of pure CGO is initially stabilized due to the dissociation of water by reduced Ce(III) and subsequent incorporation of oxygen into the structure. In the reduction process involving the composite cermet, the close proximity of the NiO improves the efficiency and speed of the composite reduction process. Although NiO is already incorporated into working cells, these observations suggest direct routes to further improve cell performance. PMID:27595058

Reduction Dynamics of Doped Ceria, Nickel Oxide, and Cermet Composites Probed Using In Situ Raman Spectroscopy.

PubMed

Maher, Robert C; Shearing, Paul R; Brightman, Edward; Brett, Dan J L; Brandon, Nigel P; Cohen, Lesley F

2016-01-01

The redox properties of gadolinium doped ceria (CGO) and nickel oxide (NiO) composite cermets underpin the operation of solid oxide electrochemical cells. Although these systems have been widely studied, a full comprehension of the reaction dynamics at the interface of these materials is lacking. Here, in situ Raman spectroscopic monitoring of the redox cycle is used to investigate the interplay between the dynamic and competing processes of hydrogen spillover and water dissociation on the doped ceria surface. In order to elucidate these mechanisms, the redox process in pure CGO and NiO is studied when exposed to wet and dry hydrogen and is compared to the cermet behavior. In dry hydrogen, CGO reduces relatively rapidly via a series of intermediate phases, while NiO reduces via a single-step process. In wet reducing atmospheres, however, the oxidation state of pure CGO is initially stabilized due to the dissociation of water by reduced Ce(III) and subsequent incorporation of oxygen into the structure. In the reduction process involving the composite cermet, the close proximity of the NiO improves the efficiency and speed of the composite reduction process. Although NiO is already incorporated into working cells, these observations suggest direct routes to further improve cell performance.

IMPROVED MAGNESIUM OXIDE SLIP CASTING METHOD

DOEpatents

Stoddard, S.D.; Nuckolls, D.E.

1963-12-31

A process for making an aqueous magnesium oxide slip casting slurry comprising the steps of mixing finely ground fused magnesium oxide with water, milling the slurry for at least 30 hours at a temperature of 2-10 deg C (the low temperature during milling inhibiting the formation of hydrated magnesium oxide), discharging the slurry from the mill, adding hydrochloric acid as a deflocculent, and adding a scum inhibitor is presented. (AEC)

Rate and extent NOM removal during oxidation and biofiltration.

PubMed

Black, Kerry E; Bérubé, Pierre R

2014-04-01

The presence of natural organic matter (NOM) in drinking water treatment presents many challenges. Integrated treatment processes combining oxidation and biofiltration have been demonstrated to be very effective at reducing NOM, specifically biodegradable organics. Laboratory bench-scale experiments were carried out to investigate the effect of oxidation by ozonation or UV/H2O2 on NOM. Specifically the rate of biodegradation was studied by performing bench-scale biodegradation experiments using acclimatized biological activated carbon (BAC). For the source water investigated, oxidation did not preferentially react with the biodegradable or non-biodegradable NOM. In addition, the type or dose of oxidation applied did not affect the observed rate of biodegradation. The rate kinetics for biodegradation were constant for all oxidation conditions investigated. Oxidation prior to biofiltration increased the overall removal of organic matter, but did not affect the rate of biodegradation of NOM. Copyright © 2013 Elsevier Ltd. All rights reserved.

Investigation of DBS electro-oxidation reaction in the aqueous-organic solution of LiClO4.

PubMed

Darlewski, Witold; Popiel, Stanisław; Nalepa, Tomasz; Gromotowicz, Waldemar; Szewczyk, Rafał; Stankiewicz, Romuald

2010-03-15

A process of dibutyl sulphide (DBS) electro-oxidation using electrolysis and cyclic voltamperometry was investigated in water-methanol solution using different electrodes (platinum, boron doped diamond, graphite and glassy carbon). Obtained results indicate that the DBS electro-oxidation process is irreversible in voltamperometric conditions. It was shown that during DBS electrolytic oxidation on Pt, at the low anode potential (1.8 V), DBS was oxidized to sulphoxide and sulphone. Electrolysis at higher potential (up to 3.0 V) resulted in complete DBS oxidation and formation of various products, including: butyric acid, sulphuric acid, butanesulphinic acid, butanesulphonic acid, identified using gas chromatography (GC-AED) and mass spectrometry (GC-MS) methods. (c) 2009 Elsevier B.V. All rights reserved.

Compositional evolution of particle-phase reaction products and water in the heterogeneous OH oxidation of model aqueous organic aerosols

NASA Astrophysics Data System (ADS)

Chim, Man Mei; Cheng, Chiu Tung; Davies, James F.; Berkemeier, Thomas; Shiraiwa, Manabu; Zuend, Andreas; Nin Chan, Man

2017-12-01

Organic compounds present at or near the surface of aqueous droplets can be efficiently oxidized by gas-phase OH radicals, which alter the molecular distribution of the reaction products within the droplet. A change in aerosol composition affects the hygroscopicity and leads to a concomitant response in the equilibrium amount of particle-phase water. The variation in the aerosol water content affects the aerosol size and physicochemical properties, which in turn governs the oxidation kinetics and chemistry. To attain better knowledge of the compositional evolution of aqueous organic droplets during oxidation, this work investigates the heterogeneous OH-radical-initiated oxidation of aqueous methylsuccinic acid (C5H8O4) droplets, a model compound for small branched dicarboxylic acids found in atmospheric aerosols, at a high relative humidity of 85 % through experimental and modeling approaches. Aerosol mass spectra measured by a soft atmospheric pressure ionization source (Direct Analysis in Real Time, DART) coupled with a high-resolution mass spectrometer reveal two major products: a five carbon atom (C5) hydroxyl functionalization product (C5H8O5) and a C4 fragmentation product (C4H6O3). These two products likely originate from the formation and subsequent reactions (intermolecular hydrogen abstraction and carbon-carbon bond scission) of tertiary alkoxy radicals resulting from the OH abstraction occurring at the methyl-substituted carbon site. Based on the identification of the reaction products, a kinetic model of oxidation (a two-product model) coupled with the Aerosol Inorganic-Organic Mixtures Functional groups Activity Coefficients (AIOMFAC) model is built to simulate the size and compositional changes of aqueous methylsuccinic acid droplets during oxidation. Model results show that at the maximum OH exposure, the droplets become slightly more hygroscopic after oxidation, as the mass fraction of water is predicted to increase from 0.362 to 0.424; however, the diameter of the droplets decreases by 6.1 %. This can be attributed to the formation of volatile fragmentation products that partition to the gas phase, leading to a net loss of organic species and associated particle-phase water, and thus a smaller droplet size. Overall, fragmentation and volatilization processes play a larger role than the functionalization process in determining the evolution of aerosol water content and droplet size at high-oxidation stages.

Phylogenetic Structure and Metabolic Properties of Microbial Communities in Arsenic-Rich Waters of Geothermal Origin

PubMed Central

Crognale, Simona; Zecchin, Sarah; Amalfitano, Stefano; Fazi, Stefano; Casentini, Barbara; Corsini, Anna; Cavalca, Lucia; Rossetti, Simona

2017-01-01

Arsenic (As) is a toxic element released in aquatic environments by geogenic processes or anthropic activities. To counteract its toxicity, several microorganisms have developed mechanisms to tolerate and utilize it for respiratory metabolism. However, still little is known about identity and physiological properties of microorganisms exposed to natural high levels of As and the role they play in As transformation and mobilization processes. This work aims to explore the phylogenetic composition and functional properties of aquatic microbial communities in As-rich freshwater environments of geothermal origin and to elucidate the key microbial functional groups that directly or indirectly may influence As-transformations across a natural range of geogenic arsenic contamination. Distinct bacterial communities in terms of composition and metabolisms were found. Members of Proteobacteria, affiliated to Alpha- and Betaproteobacteria were mainly retrieved in groundwaters and surface waters, whereas Gammaproteobacteria were the main component in thermal waters. Most of the OTUs from thermal waters were only distantly related to 16S rRNA gene sequences of known taxa, indicating the occurrence of bacterial biodiversity so far unexplored. Nitrate and sulfate reduction and heterotrophic As(III)-oxidization were found as main metabolic traits of the microbial cultivable fraction in such environments. No growth of autotrophic As(III)-oxidizers, autotrophic and heterotrophic As(V)-reducers, Fe-reducers and oxidizers, Mn-reducers and sulfide oxidizers was observed. The ars genes, involved in As(V) detoxifying reduction, were found in all samples whereas aioA [As(III) oxidase] and arrA genes [As(V) respiratory reductase] were not found. Overall, we found that As detoxification processes prevailed over As metabolic processes, concomitantly with the intriguing occurrence of novel thermophiles able to tolerate high levels of As. PMID:29312179

Phylogenetic Structure and Metabolic Properties of Microbial Communities in Arsenic-Rich Waters of Geothermal Origin.

PubMed

Crognale, Simona; Zecchin, Sarah; Amalfitano, Stefano; Fazi, Stefano; Casentini, Barbara; Corsini, Anna; Cavalca, Lucia; Rossetti, Simona

2017-01-01

Arsenic (As) is a toxic element released in aquatic environments by geogenic processes or anthropic activities. To counteract its toxicity, several microorganisms have developed mechanisms to tolerate and utilize it for respiratory metabolism. However, still little is known about identity and physiological properties of microorganisms exposed to natural high levels of As and the role they play in As transformation and mobilization processes. This work aims to explore the phylogenetic composition and functional properties of aquatic microbial communities in As-rich freshwater environments of geothermal origin and to elucidate the key microbial functional groups that directly or indirectly may influence As-transformations across a natural range of geogenic arsenic contamination. Distinct bacterial communities in terms of composition and metabolisms were found. Members of Proteobacteria , affiliated to Alpha - and Betaproteobacteria were mainly retrieved in groundwaters and surface waters, whereas Gammaproteobacteria were the main component in thermal waters. Most of the OTUs from thermal waters were only distantly related to 16S rRNA gene sequences of known taxa, indicating the occurrence of bacterial biodiversity so far unexplored. Nitrate and sulfate reduction and heterotrophic As(III)-oxidization were found as main metabolic traits of the microbial cultivable fraction in such environments. No growth of autotrophic As(III)-oxidizers, autotrophic and heterotrophic As(V)-reducers, Fe-reducers and oxidizers, Mn-reducers and sulfide oxidizers was observed. The ars genes, involved in As(V) detoxifying reduction, were found in all samples whereas aioA [As(III) oxidase] and arrA genes [As(V) respiratory reductase] were not found. Overall, we found that As detoxification processes prevailed over As metabolic processes, concomitantly with the intriguing occurrence of novel thermophiles able to tolerate high levels of As.

Degradation kinetics and transformation products of chlorophene by aqueous permanganate.

PubMed

Xu, Xinxin; Chen, Jing; Wang, Siyuan; Ge, Jiali; Qu, Ruijuan; Feng, Mingbao; Sharma, Virender K; Wang, Zunyao

2018-07-01

This paper evaluates the oxidation of an antibacterial agent, chlorophene (4-chloro-2-(phenylmethyl)phenol, CP), by permanganate (Mn(VII)) in water. Second-order rate constant (k) for the reaction between Mn(VII) and CP was measured as (2.05 ± 0.05) × 10 1  M -1  s -1 at pH 7.0 for an initial CP concentration of 20.0 μM and Mn(VII) concentration of 60.0 μM. The value of k decreased with increasing pH in the pH range of 5.0-7.0, and then increased with an increase in solution pH from 7.0 to 10.0. The presence of MnO 2 and Fe 3+ in water generally enhanced the removal of CP, while the effect of humic acid was not obvious. Fourteen oxidation products of CP were identified by an electrospray time-of-flight mass spectrometer, and direct oxidation, ring-opening, and decarboxylation were mainly observed in the reaction process. The initial reaction sites of CP by Mn(VII) oxidation were rationalized by density functional theory calculations. Toxicity changes of the reaction solutions were assessed by the luminescent bacteria P. phosphoreum, and the intermediate products posed a relatively low ecological risk during the degradation process. The efficient removal of CP in secondary clarifier effluent and river water demonstrated the potential application of this Mn(VII) oxidation method in water treatment. Copyright © 2018 Elsevier Ltd. All rights reserved.

The comparison of greenhouse gas emissions in sewage treatment plants with different treatment processes.

PubMed

Masuda, Shuhei; Sano, Itsumi; Hojo, Toshimasa; Li, Yu-You; Nishimura, Osamu

2018-02-01

Greenhouse gas emissions from different sewage treatment plants: oxidation ditch process, double-circulated anoxic-oxic process and anoxic-oxic process were evaluated based on the survey. The methane and nitrous oxide characteristics were discussed based on the gaseous and dissolved gas profiles. As a result, it was found that methane was produced in the sewer pipes and the primary sedimentation tank. Additionally, a ventilation system would promote the gasification of dissolved methane in the first treatment units. Nitrous oxide was produced and emitted in oxic tanks with nitrite accumulation inside the sewage treatment plant. A certain amount of nitrous oxide was also discharged as dissolved gas through the effluent water. If the amount of dissolved nitrous oxide discharge is not included, 7-14% of total nitrous oxide emission would be overlooked. Based on the greenhouse gas calculation, electrical consumption and the N 2 O emission from incineration process were major sources in all the plants. For greenhouse gas reduction, oxidation ditch process has an advantage over the other advanced systems due to lower energy consumption, sludge production, and nitrogen removal without gas stripping. Copyright © 2017 Elsevier Ltd. All rights reserved.

Subtropical freshwater storages: a major source of nitrous oxide and methane?

NASA Astrophysics Data System (ADS)

Sturm, Katrin; Grinham, Alistair; Yuan, Zhiguo

2013-04-01

Studies of greenhouse gas cycling in subtropical water bodies, particularly in the Southern Hemisphere, are very limited. This represents an important gap in our understanding of global emissions as the higher temperatures experienced in the subtropics will likely accelerate greenhouse gas production and consumption. Critical to understanding the net impact of these accelerated rates are detailed studies of representative systems within this region. In this paper we present a model artificial freshwater storage: Gold Creek Dam in South East Queensland, Australia. Freshwater storages are commonplace for drinking water and irrigation purposes in Australia as unpredictable rainfall patterns make river and ground water sources unreliable. Over 85 % of Australian rivers are modified with weirs and dams providing permanent inundation of previously terrestrial environments. The higher temperatures experienced at these latitudes drive thermal stratification of these systems as well as rapidly deoxygenate bottom waters. High organic matter availability in the sediment zone as well as the anoxic overlying water provide ideal conditions for reduced products (including methane and ammonia) from microbial processing to be formed and diffuse into bottom waters. A mid-water metalimnion is generally associated with large gradients in dissolved oxygen availability and reduced metabolites undergo oxidation prior to their emission from water surface. An intensive field study was undertaken to improve understanding of production and transformation rates of methane and nitrous oxide from the sediments, through the water column and to the atmosphere. Sediment nutrient (ammonia, nitrite/nitrate and filterable reactive phosphorus) and greenhouse gas (methane and nitrous oxide) porewater samples were collected at selected sites. To determine the magnitude of the benthic sediment contribution of methane and nitrous oxide to the water column sediment incubations were conducted in the laboratory. To determine the likely atmospheric flux from this water body surface floating chambers were used to collect gas. Results showed maximum methane concentrations in the sediment porewaters and deeper water column, both anoxic environments. However, nitrous oxide had highest concentrations at the oxycline zone of the water column. Sediment incubations showed clear methane efflux demonstrating the sediments to be a consistent source of methane. Sediments were either a source or sink of nitrous oxide depending on overlying dissolved oxygen concentration. Floating chamber incubations clearly demonstrated Gold Creek Dam was a source of both methane and nitrous oxide with methane an order of magnitude higher expressed as CO2 equivalents. Diffusive atmospheric fluxes of methane ranged from 20 to 450 mg m-2 d-1 and were comparable to tropical reservoirs rather than temperate reservoirs (LOUIS et al., 2000). Results are likely to be globally relevant as an increasing number of large dams are being constructed to meet growing water demand and under a warming climate process occurring in subtropical systems can give insights into future changes likely to occur in temperate systems.

An effective method of UV-oxidation of dissolved organic carbon in natural waters for radiocarbon analysis by accelerator mass spectrometry

NASA Astrophysics Data System (ADS)

Xue, Yuejun; Ge, Tiantian; Wang, Xuchen

2015-12-01

Radiocarbon (14C) measurement of dissolved organic carbon (DOC) is a very powerful tool to study the sources, transformation and cycling of carbon in the ocean. The technique, however, remains great challenges for complete and successful oxidation of sufficient DOC with low blanks for high precision carbon isotopic ratio analysis, largely due to the overwhelming proportion of salts and low DOC concentrations in the ocean. In this paper, we report an effective UV-Oxidation method for oxidizing DOC in natural waters for radiocarbon analysis by accelerator mass spectrometry (AMS). The UV-oxidation system and method show 95%±4% oxidation efficiency and high reproducibility for DOC in both river and seawater samples. The blanks associated with the method was also low (about 3 µg C) that is critical for 14C analysis. As a great advantage of the method, multiple water samples can be oxidized at the same time so it reduces the sample processing time substantially compared with other UV-oxidation method currently being used in other laboratories. We have used the system and method for 14C studies of DOC in rivers, estuaries, and oceanic environments and have received promise results.

Monitoring the Reaction Process During the S2 → S3 Transition in Photosynthetic Water Oxidation Using Time-Resolved Infrared Spectroscopy.

PubMed

Sakamoto, Hiroki; Shimizu, Tatsuki; Nagao, Ryo; Noguchi, Takumi

2017-02-08

Photosynthetic water oxidation performed at the Mn 4 CaO 5 cluster in photosystem II plays a crucial role in energy production as electron and proton sources necessary for CO 2 fixation. Molecular oxygen, a byproduct, is a source of the oxygenic atmosphere that sustains life on earth. However, the molecular mechanism of water oxidation is not yet well-understood. In the reaction cycle of intermediates called S states, the S 2 → S 3 transition is particularly important; it consists of multiple processes of electron transfer, proton release, and water insertion, and generates an intermediate leading to O-O bond formation. In this study, we monitored the reaction process during the S 2 → S 3 transition using time-resolved infrared spectroscopy to clarify its molecular mechanism. A change in the hydrogen-bond interaction of the oxidized Y Z • radical, an immediate electron acceptor of the Mn 4 CaO 5 cluster, was clearly observed as a ∼100 μs phase before the electron-transfer phase with a time constant of ∼350 μs. This observation provides strong experimental evidence that rearrangement of the hydrogen-bond network around Y Z • , possibly due to the movement of a water molecule located near Y Z • to the Mn site, takes place before the electron transfer. The electron transfer was coupled with proton release, as revealed by a relatively high deuterium kinetic isotope effect of 1.9. This proton release, which decreases the redox potential of the Mn 4 CaO 5 cluster to facilitate electron transfer to Y Z • , was proposed to determine, as a rate-limiting step, the relatively slow electron-transfer rate of the S 2 → S 3 transition.

Giardia duodenalis: Number and Fluorescence Reduction Caused by the Advanced Oxidation Process (H2O2/UV)

PubMed Central

Guimarães, José Roberto; Franco, Regina Maura Bueno; Guadagnini, Regiane Aparecida; dos Santos, Luciana Urbano

2014-01-01

This study evaluated the effect of peroxidation assisted by ultraviolet radiation (H2O2/UV), which is an advanced oxidation process (AOP), on Giardia duodenalis cysts. The cysts were inoculated in synthetic and surface water using a concentration of 12 g H2O2 L−1 and a UV dose (λ = 254 nm) of 5,480 mJcm−2. The aqueous solutions were concentrated using membrane filtration, and the organisms were observed using a direct immunofluorescence assay (IFA). The AOP was effective in reducing the number of G. duodenalis cysts in synthetic and surface water and was most effective in reducing the fluorescence of the cyst walls that were present in the surface water. The AOP showed a higher deleterious potential for G. duodenalis cysts than either peroxidation (H2O2) or photolysis (UV) processes alone. PMID:27379301

Effects of UV/Ag-TiO2/O3 advanced oxidation on unicellular green alga Dunaliella salina: implications for removal of invasive species from ballast water.

PubMed

Wu, Donghai; You, Hong; Du, Jiaxuan; Chen, Chuan; Jin, Darui

2011-01-01

The UV/Ag-TiO2/O3 process was investigated for ballast water treatment using Dunaliella salina as an indicator. Inactivation curves were obtained, and the toxicity of effluent was determined. Compared with individual unit processes using ozone or UV/Ag-TiO2, the inactivation efficiency of D. salina by the combined UV/Ag-TiO2/O3 process was enhanced. The presence of ozone caused an immediate decrease in chlorophyll a (chl-a) concentration. Inactivation efficiency and ch1-a removal efficiency were positively correlated with ozone dose and ultraviolet intensity. The initial total residual oxidant (TRO) concentration of effluent increased with increasing ozone dose, and persistence of TRO resulted in an extended period of toxicity. The results suggest that UV/Ag-TiO2/O3 has potential for ballast water treatment.

Studies on the treatment of urine by the biological purification-UV photocatalytic oxidation

NASA Astrophysics Data System (ADS)

Liu, Ch. Ch; Liu, R. D.; Liu, X. S.; Chen, M.; Bian, Z. L.; Hu, J. Ch.

The water-consuming amount in a long-term astro-navigation is large In order to reduce the burden of water supply from Earth ground the space station needs to resolve the problems of water supply For this reason the recovery and regeneration of urine solution of spacemen and its utilization possess a key importance Many investigations on this aspect have been reported Our research based on biological absorption-purification-UV photocatalytic oxidation techniques with a relevant treating equipment that for a comprehensive treatment to fresh urine of spacemen has been created In this equipment the urine solution was used as the nutrient solution for the biological parts in ecological life ensurant system after absorbing the nutrient it was decomposed metabolized and purified in some distance and created a favorable condition for the follow-up oxidation treatment by UV-Photocatalytic Oxidation After these two processes the treated urine solution reached the GB5749-85 standard of water quality

Studies on urine treatment by biological purification using Azolla and UV photocatalytic oxidation

NASA Astrophysics Data System (ADS)

Liu, Xiaofeng; Chen, Min; Bian, Zuliang; Liu, Chung-Chu

The amount of water consumed in space station operations is very large. In order to reduce the amount of water which must be resupplied from Earth, the space station needs to resolve the problems of water supply. For this reason, the recovery, regeneration and utilization of urine of astronauts are of key importance. Many investigations on this subject have been reported. Our research is based on biological absorption and, purification using UV photocatalytic oxidation techniques to achieve comprehensive treatment for urine. In the treatment apparatus we created, the urine solution is used as part of the nutrient solution for the biological components in our bioregenerative life support system. After being absorbed, the nutrients from the urine were then decomposed, metabolized and purified which creates a favorable condition for the follow-up oxidation treatment by UV photocatalytic oxidation. After these two processes, the treated urine solution reached Chinese national standards for drinking water quality (GB5749-1985).

Hydrogen Treatment Protects against Cell Death and Senescence Induced by Oxidative Damage.

PubMed

Han, A Lum; Park, Seong-Hoon; Park, Mi Sung

2017-02-28

Hydrogen has potential for preventive and therapeutic applications as an antioxidant. However, micro- and macroparticles of hydrogen in water disappear easily over time. In order to eliminate reactive oxygen species (ROS) related with the aging process, we used functional water containing nanoparticle hydrogen. Nanoparticle hydrogen does not disappear easily and collapse under water after long periods of time. We used murine embryonic fibroblasts that were isolated from 12.5-day embryos of C57BL/6 mice. We investigated the ability of nanoparticle hydrogen in water to suppress hydroxyurea-induced ROS production, cytotoxicity, and the accumulation of β-galactosidase (an indicator of aging), and promote cell proliferation. The accumulation of β-galactosidase in the cytoplasm and the appearance of abnormal nuclei were inhibited by daily treatment of cells with hydrogen water. When the aging process was accelerated by hydroxyurea-induced oxidative stress, the effect of hydrogen water was even more remarkable. Thus, this study showed the antioxidant and anti-senescence effects of hydrogen water. Nanoparticle hydrogen water is potentially a potent anti-aging agent.

Metagenomic Evidence for the Presence of Comammox Nitrospira-Like Bacteria in a Drinking Water System.

PubMed

Pinto, Ameet J; Marcus, Daniel N; Ijaz, Umer Zeeshan; Bautista-de Lose Santos, Quyen Melina; Dick, Gregory J; Raskin, Lutgarde

2016-01-01

We report metagenomic evidence for the presence of a Nitrospira-like organism with the metabolic potential to perform the complete oxidation of ammonia to nitrate (i.e., it is a complete ammonia oxidizer [comammox]) in a drinking water system. This metagenome bin was discovered through shotgun DNA sequencing of samples from biologically active filters at the drinking water treatment plant in Ann Arbor, MI. Ribosomal proteins, 16S rRNA, and nxrA gene analyses confirmed that this genome is related to Nitrospira-like nitrite-oxidizing bacteria. The presence of the full suite of ammonia oxidation genes, including ammonia monooxygenase and hydroxylamine dehydrogenase, on a single ungapped scaffold within this metagenome bin suggests the presence of recently discovered comammox potential. Evaluations based on coverage and k-mer frequency distribution, use of two different genome-binning approaches, and nucleic acid and protein similarity analyses support the presence of this scaffold within the Nitrospira metagenome bin. The amoA gene found in this metagenome bin is divergent from those of canonical ammonia and methane oxidizers and clusters closely with the unusual amoA gene of comammox Nitrospira. This finding suggests that previously reported imbalances in abundances of nitrite- and ammonia-oxidizing bacteria/archaea may likely be explained by the capacity of Nitrospira-like organisms to completely oxidize ammonia. This finding might have significant implications for our understanding of microbially mediated nitrogen transformations in engineered and natural systems. IMPORTANCE Nitrification plays an important role in regulating the concentrations of inorganic nitrogen species in a range of environments, from drinking water and wastewater treatment plants to the oceans. Until recently, aerobic nitrification was considered to be a two-step process involving ammonia-oxidizing bacteria or archaea and nitrite-oxidizing bacteria. This process requires close cooperation between these two functional guilds for complete conversion of ammonia to nitrate, without the accumulation of nitrite or other intermediates, such as nitrous oxide, a potent greenhouse gas. The discovery of a single organism with the potential to oxidize both ammonia and nitrite adds a new dimension to the current understanding of aerobic nitrification, while presenting opportunities to rethink nitrogen management in engineered systems.

Microwave alkaline roasting-water dissolving process for germanium extraction from zinc oxide dust and its analysis by response surface methodology (RSM)

NASA Astrophysics Data System (ADS)

Wang, Wankun; Wang, Fuchun; Lu, Fanghai

2017-12-01

Microwave alkaline roasting-water dissolving process was proposed to improve the germanium (Ge) extraction from zinc oxide (ZnO) dust. The effects of important parameters were investigated and the process conditions were optimized using response surface methodology (RSM). The Ge extraction is consistent with the linear polynomial model type. Alkali-material ratio, microwave heating temperature and leaching temperature are the significant factors for this process. The optimized conditions are obtained as follows, alkali-material ratio of 0.9 kg/kg, aging time of 1.12 day, microwave heating at 658 K for 10 min, liquid-solid ratio of 4.31 L/kg, leaching temperature at 330 K, leaching time of 47 min with the Ge extraction about 99.38%. It is in consistence with the predictive value of 99.31%. Compared to the existed alkaline roasting process heated by electric furnace in literature, the alkaline roasting temperature and holding time. It shows a good prospect on leaching Ge from ZnO dust with microwave alkaline roasting-water dissolving process.

Water purification by electrical discharges

NASA Astrophysics Data System (ADS)

Arif Malik, Muhammad; Ghaffar, Abdul; Akbar Malik, Salman

2001-02-01

There is a continuing need for the development of effective, cheap and environmentally friendly processes for the disinfection and degradation of organic pollutants from water. Ozonation processes are now replacing conventional chlorination processes because ozone is a stronger oxidizing agent and a more effective disinfectant without any side effects. However, the fact that the cost of ozonation processes is higher than chlorination processes is their main disadvantage. In this paper recent developments targeted to make ozonation processes cheaper by improving the efficiency of ozone generation, for example, by incorporation of catalytic packing in the ozone generator, better dispersion of ozone in water and faster conversion of dissolved ozone to free radicals are described. The synthesis of ozone in electrical discharges is discussed. Furthermore, the generation and plasma chemical reactions of several chemically active species, such as H2O2, Obullet, OHbullet, HO2bullet, O3*, N2*, e-, O2-, O-, O2+, etc, which are produced in the electrical discharges are described. Most of these species are stronger oxidizers than ozone. Therefore, water treatment by direct electrical discharges may provide a means to utilize these species in addition to ozone. Much research and development activity has been devoted to achieve these targets in the recent past. An overview of these techniques and important developments that have taken place in this area are discussed. In particular, pulsed corona discharge, dielectric barrier discharge and contact glow discharge electrolysis techniques are being studied for the purpose of cleaning water. The units based on electrical discharges in water or close to the water level are being tested at industrial-scale water treatment plants.}

Conversion of hazardous materials using supercritical water oxidation

DOEpatents

Rofer, Cheryl K.; Buelow, Steven J.; Dyer, Richard B.; Wander, Joseph D.

1992-01-01

A process for destruction of hazardous materials in a medium of supercritical water without the addition of an oxidant material. The harzardous material is converted to simple compounds which are relatively benign or easily treatable to yield materials which can be discharged into the environment. Treatment agents may be added to the reactants in order to bind certain materials, such as chlorine, in the form of salts or to otherwise facilitate the destruction reactions.

Aerobic oxidation in nanomicelles of aryl alkynes, in water at room temperature.

PubMed

Handa, Sachin; Fennewald, James C; Lipshutz, Bruce H

2014-03-24

On the basis of the far higher solubility of oxygen gas inside the hydrocarbon core of nanomicelles, metal and peroxide free aerobic oxidation of aryl alkynes to β-ketosulfones has been achieved in water at room temperature. Many examples are offered that illustrate broad functional group tolerance. The overall process is environmentally friendly, documented by the associated low E Factors. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Water-Rock Reactions on Non-Planetary Bodies in the Early Solar System

NASA Astrophysics Data System (ADS)

Zolotov, M. Y.

2005-12-01

Reactions of aqueous fluids with rocks shortly after formation of the solar system affected the oxidation states, mineralogy, organic speciation, ice composition, and surface/atmospheric chemistry of asteroids, icy satellites of giant plants, and possibly Kuiper belt objects. Water condensed as ice in the solar nebula, was incorporated into the composition of these bodies together with rocky components represented by extremely reduced and anhydrous nebular condensates (e.g., Fe-rich metal, forsterite, low-Ca pyroxene, troilite, Ca-Mg-Al oxides, phosphides), presolar grains (SiC, graphite, diamond, Al-, Mg-, Ti-oxides) and organic compounds and polymers. Radioactive decay of short-lived radionuclides on small bodies, and accretionary heat and decay of long-lived radionuclides on large bodies provided energy to melt ice. On smaller bodies, low gravity precluded separation of water from rocks and restricted fluid dynamics. On larger bodies, water was separated from descending rocks, limiting the duration of water-rock reactions. Competitive oxidation and hydration by water affected both inorganic and organic compounds in rocks. Oxidation of minerals led to formation of ferrous silicates, magnetite, pyrrhotite, Ni sulfides, Ni-rich metal alloys, chromite, phosphates, carbonates and sulfates. Hydration caused formation of phyllosilicates (serpentine, chlorites, smectite clays, amphiboles, and micas), hydroxides, and hydrated sulfides and salts. High water/rock ratios, elevated temperatures and low pressures favored oxidation. Low temperatures supported hydration. In some icy satellites (Europa, Ganymede) high water content and hydrothermal processes during differentiation may have caused profound oxidation leading to carbonates and even sulfates. Since water was the only early oxidizing agent, the elevated oxidation state of Io implies its early aqueous history. Hydrogen was produced in all oxidation reactions and preferentially separated into the gas phase. Escape of H2 into space promoted oxidation, consistent with the high oxidation state of highly porous CI and CM carbonaceous chondrites. Low porosity and permeability, filling of pore space with secondary minerals, and sealing of outer zones with ice restricted H2 escape, retarded some oxidation reactions and caused incomplete reduction of minerals formed earlier by oxidation. For example, magnetite was partially converted to ferrous silicates. The limited oxidation and signs of reduction in some meteorite types (unequilibrated ordinary and CV3 carbonaceous chondrites) is consistent with low amounts of incorporated water ice and low porosity of parent asteroids. Although prolonged heating of bodies caused dehydration and some reduction, water-rock reactions led to net oxidation of primary rocky components, consistent with the elevated oxidation states of metamorphosed chondrites and Io. Interaction of water with organic compounds and carbon grains caused disproportionation of carbon leading to O-bearing organic compounds and CO2, as well as to hydrogenated organic compounds and methane. In small bodies, organic matter was only partially altered. In some icy satellites, prolonged reactions and elevated pressures favored formation of light hydrocarbons and methane, consistent with observations (e.g., Titan, Triton). In most bodies, net oxidation of organic compounds can be attributed to preservation of CO2 and O-bearing organics in solution, ices and carbonates, and escape of H2 formed through oxidation reactions.

Nitride Fuel Development Using Cryo-process Technique

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

O'Brien, Brandi M; Windes, William E

A new cryo-process technique has been developed for the fabrication of advanced fuel for nuclear systems. The process uses a new cryo-processing technique whereby small, porous microspheres (<2000 µm) are formed from sub-micron oxide powder. A simple aqueous particle slurry of oxide powder is pumped through a microsphere generator consisting of a vibrating needle with controlled amplitude and frequency. As the water-based droplets are formed and pass through the microsphere generator they are frozen in a bath of liquid nitrogen and promptly vacuum freeze-dried to remove the water. The resulting porous microspheres consist of half micron sized oxide particles heldmore » together by electrostatic forces and mechanical interlocking of the particles. Oxide powder microspheres ranging from 750 µm to 2000 µm are then converted into a nitride form using a high temperature fluidized particle bed. Carbon black can be added to the oxide powder before microsphere formation to augment the carbothermic reaction during conversion to a nitride. Also, the addition of ethyl alcohol to the aqueous slurry reduces the surface tension energy of the droplets resulting in even smaller droplets forming in the microsphere generator. Initial results from this new process indicate a lower impurity contamination in the final nitrides due to the single feed stream of particles, material handling and conversion are greatly simplified, a minimum of waste and personnel exposure are anticipated, and finally the conversion kinetics may be greatly increased because of the small oxide powder size (sub-micron) forming the porous microsphere. Thus far the fabrication process has been successful in demonstrating all of these improvements with surrogate ZrO2 powder. Further tests will be conducted in the future using the technique on UO2 powders.« less

Identification of ozonation by-products of 4- and 5-methyl-1H-benzotriazole during the treatment of surface water to drinking water.

PubMed

Müller, Alexander; Weiss, Stefan C; Beisswenger, Judith; Leukhardt, H Georg; Schulz, Wolfgang; Seitz, Wolfram; Ruck, Wolfgang K L; Weber, Walter H

2012-03-01

During the treatment of surface water to drinking water, ozonation is often used for disinfection and to remove organic trace substances, whereby oxidation by-products can be formed. Here we use the example of tolyltriazole to describe an approach for identifying relevant oxidation by-products in the laboratory and subsequently detecting them in an industrial-scale process. The identification process involves ozonation experiments with pure substances at laboratory level (concentration range mg L(-1)). The reaction solutions from different ozone contact times were analyzed by high performance liquid chromatography - quadrupole time-of-flight mass spectrometry (HPLC-QTOF-MS) in full scan mode. Various approaches were used to detect the oxidation by-products: (i) target searches of postulated oxidation by-products, (ii) comparisons of chromatograms (e.g., UV/VIS) of the different samples, and (iii) color-coded abundance time courses (kinetic) of all detected compounds were illustrated in a kind of a heat map. MS/MS, H/D exchange, and derivatization experiments were used for structure elucidation for the detected by-product. Due to the low contaminant concentrations (ng L(-1)-range) of contaminants in the untreated water, the conversion of results from laboratory experiments to an industrial-scale required the use of HPLC-MS/MS with sample enrichment (e.g., solid phase extraction.) In cases where reference substances were not available or oxidation by-products without clear structures were detected, reaction solutions from laboratory experiments were used to optimize the analytical method to detect ng L(-1) in the samples of the industrial processes. We exemplarily demonstrated the effectiveness of the methodology with the industrial chemicals 4- and 5-methyl-1H-benzotriazole (4- and 5-MBT) as an example. Moreover, not only did we identify several oxidation by-products in the laboratory experiments tentatively, but also detected three of the eleven reaction products in the outlet of the full-scale ozonation unit. Copyright © 2011 Elsevier Ltd. All rights reserved.

Selection of representative emerging micropollutants for drinking water treatment studies: a systematic approach.

PubMed

Jin, Xiaohui; Peldszus, Sigrid

2012-01-01

Micropollutants remain of concern in drinking water, and there is a broad interest in the ability of different treatment processes to remove these compounds. To gain a better understanding of treatment effectiveness for structurally diverse compounds and to be cost effective, it is necessary to select a small set of representative micropollutants for experimental studies. Unlike other approaches to-date, in this research micropollutants were systematically selected based solely on their physico-chemical and structural properties that are important in individual water treatment processes. This was accomplished by linking underlying principles of treatment processes such as coagulation/flocculation, oxidation, activated carbon adsorption, and membrane filtration to compound characteristics and corresponding molecular descriptors. A systematic statistical approach not commonly used in water treatment was then applied to a compound pool of 182 micropollutants (identified from the literature) and their relevant calculated molecular descriptors. Principal component analysis (PCA) was used to summarize the information residing in this large dataset. D-optimal onion design was then applied to the PCA results to select structurally representative compounds that could be used in experimental treatment studies. To demonstrate the applicability and flexibility of this selection approach, two sets of 22 representative micropollutants are presented. Compounds in the first set are representative when studying a range of water treatment processes (coagulation/flocculation, oxidation, activated carbon adsorption, and membrane filtration), whereas the second set shows representative compounds for ozonation and advanced oxidation studies. Overall, selected micropollutants in both lists are structurally diverse, have wide-ranging physico-chemical properties and cover a large spectrum of applications. The systematic compound selection approach presented here can also be adjusted to fit individual research needs with respect to type of micropollutants, treatment processes and number of compounds selected. Copyright © 2011 Elsevier B.V. All rights reserved.

Degradation alternatives for a commercial fungicide in water: biological, photo-Fenton, and coupled biological photo-Fenton processes.

PubMed

López-Loveira, Elsa; Ariganello, Federico; Medina, María Sara; Centrón, Daniela; Candal, Roberto; Curutchet, Gustavo

2017-11-01

Imazalil (IMZ) is a widely used fungicide for the post-harvest treatment of citrus, classified as "likely to be carcinogenic in humans" for EPA, that can be only partially removed by conventional biological treatment. Consequently, specific or combined processes should be applied to prevent its release to the environment. Biological treatment with adapted microorganism consortium, photo-Fenton, and coupled biological photo-Fenton processes were tested as alternatives for the purification of water containing high concentration of the fungicide and the coadjutants present in the commercial formulation. IMZ-resistant consortium with the capacity to degrade IMZ in the presence of a C-rich co-substrate was isolated from sludge coming from a fruit packaging company wastewater treatment plant. This consortium was adapted to resist and degrade the organics present in photo-Fenton-oxidized IMZ water solution. Bacteria colonies from the consortia were isolated and identified. The effect of H 2 O 2 initial concentration and dosage on IMZ degradation rate, average oxidation state (AOS), organic acid concentration, oxidation, and mineralization percentage after photo-Fenton process was determined. The application of biological treatment to the oxidized solutions notably decreased the total organic carbon (TOC) in solution. The effect of the oxidation degree, limited by H 2 O 2 concentration and dosage, on the percentage of mineralization obtained after the biological treatment was determined and explained in terms of changes in AOS. The concentration of H 2 O 2 necessary to eliminate IMZ by photo-Fenton and to reduce TOC and chemical oxygen demand (COD) by biological treatment, in order to allow the release of the effluents to rivers with different flows, was estimated.

Solar light-induced production of reactive oxygen species by single walled carbon nanotubes in water

EPA Science Inventory

Photosensitizing processes of engineered nanomaterials (ENMs) which include photo-induced production of reactive oxygen species (ROS) convert light energy into oxidizing chemical energy that mediates transformations of nanomaterials. The oxidative stress associated with ROS may p...

A new sono-electrochemical method for enhanced detoxification of hydrophilic chloroorganic pollutants in water.

PubMed

Yasman, Yakov; Bulatov, Valery; Gridin, Vladimir V; Agur, Sabina; Galil, Noah; Armon, Robert; Schechter, Israel

2004-09-01

A new method for detoxification of hydrophilic chloroorganic pollutants in effluent water was developed, using a combination of ultrasound waves, electrochemistry and Fenton's reagent. The advantages of the method are exemplified using two target compounds: the common herbicide 2,4-dichlorophenoxyacetic acid (2,4-D) and its derivative 2,4-dichlorophenol (2,4-DCP). The high degradation power of this process is due to the large production of oxidizing hydroxyl radicals and high mass transfer due to sonication. Application of this sono-electrochemical Fenton process (SEF) treatment (at 20 kHz) with quite a small current density, accomplished almost 50% oxidation of 2,4-D solution (300 ppm, 1.2 mM) in just 60 s. Similar treatments ran for 600 s resulted in practically full degradation of the herbicide; sizable oxidation of 2,4-DCP also occurs. The main intermediate compounds produced in the SEF process were identified. Their kinetic profile was measured and a chemical reaction scheme was suggested. The efficiency of the SEF process is tentatively much higher than the reference degradation methods and the time required for full degradation is considerably shorter. The SEF process maintains high performance up to concentrations which are higher than reference methods. The optimum concentration of Fe2+ ions required for this process was found to be of about 2 mM, which is lower than that in reference techniques. These findings indicate that SEF process may be an effective method for detoxification of environmental water.

Hormetic response triggers multifaceted anti-oxidant strategies in immature king penguins (Aptenodytes patagonicus).

PubMed

Rey, Benjamin; Dégletagne, Cyril; Bodennec, Jacques; Monternier, Pierre-Axel; Mortz, Mathieu; Roussel, Damien; Romestaing, Caroline; Rouanet, Jean-Louis; Tornos, Jeremy; Duchamp, Claude

2016-08-01

Repeated deep dives are highly pro-oxidative events for air-breathing aquatic foragers such as penguins. At fledging, the transition from a strictly terrestrial to a marine lifestyle may therefore trigger a complex set of anti-oxidant responses to prevent chronic oxidative stress in immature penguins but these processes are still undefined. By combining in vivo and in vitro approaches with transcriptome analysis, we investigated the adaptive responses of sea-acclimatized (SA) immature king penguins (Aptenodytes patagonicus) compared with pre-fledging never-immersed (NI) birds. In vivo, experimental immersion into cold water stimulated a higher thermogenic response in SA penguins than in NI birds, but both groups exhibited hypothermia, a condition favouring oxidative stress. In vitro, the pectoralis muscles of SA birds displayed increased oxidative capacity and mitochondrial protein abundance but unchanged reactive oxygen species (ROS) generation per g tissue because ROS production per mitochondria was reduced. The genes encoding oxidant-generating proteins were down-regulated in SA birds while mRNA abundance and activity of the main antioxidant enzymes were up-regulated. Genes encoding proteins involved in repair mechanisms of oxidized DNA or proteins and in degradation processes were also up-regulated in SA birds. Sea life also increased the degree of fatty acid unsaturation in muscle mitochondrial membranes resulting in higher intrinsic susceptibility to ROS. Oxidative damages to protein or DNA were reduced in SA birds. Repeated experimental immersions of NI penguins in cold-water partially mimicked the effects of acclimatization to marine life, modified the expression of fewer genes related to oxidative stress but in a similar way as in SA birds and increased oxidative damages to DNA. It is concluded that the multifaceted plasticity observed after marine life may be crucial to maintain redox homeostasis in active tissues subjected to high pro-oxidative pressure in diving birds. Initial immersions in cold-water may initiate an hormetic response triggering essential changes in the adaptive antioxidant response to marine life. Copyright © 2016 Elsevier Inc. All rights reserved.

Terrestrial Fe-oxide Concretions and Mars Blueberries: Comparisons of Similar Advective and Diffusive Chemical Infiltration Reaction Mechanisms

NASA Astrophysics Data System (ADS)

Park, A. J.; Chan, M. A.

2006-12-01

Abundant iron oxide concretions occurring in Navajo Sandstone of southern Utah and those discovered at Meridiani Planum, Mars share many common observable physical traits such as their spheriodal shapes, occurrence, and distribution patterns in sediments. Terrestrial concretions are products of interaction between oxygen-rich aquifer water and basin-derived reducing (iron-rich) water. Water-rock interaction simulations show that diffusion of oxygen and iron supplied by slow-moving water is a reasonable mechanism for producing observed concretion patterns. In short, southern Utah iron oxide concretions are results of Liesegang-type diffusive infiltration reactions in sediments. We propose that the formation of blueberry hematite concretions in Mars sediments followed a similar diagenetic mechanism where iron was derived from the alteration of volcanic substrate and oxygen was provided by the early Martian atmosphere. Although the terrestrial analog differs in the original host rock composition, both the terrestrial and Mars iron-oxide precipitation mechanisms utilize iron and oxygen interactions in sedimentary host rock with diffusive infiltration of solutes from two opposite sources. For the terrestrial model, slow advection of iron-rich water is an important factor that allowed pervasive and in places massive precipitation of iron-oxide concretions. In Mars, evaporative flux of water at the top of the sediment column may have produced a slow advective mass-transfer mechanism that provided a steady source and the right quantity of iron. The similarities of the terrestrial and Martian systems are demonstrated using a water-rock interaction simulator Sym.8, initially in one-dimensional systems. Boundary conditions such as oxygen content of water, partial pressure of oxygen, and supply rate of iron were varied. The results demonstrate the importance of slow advection of water and diffusive processes for producing diagenetic iron oxide concretions.

Effect of water on hydrogen permeability. [Stirling engines

NASA Technical Reports Server (NTRS)

Hulligan, D. D.; Tomazic, W. A.

1984-01-01

Doping of hydrogen with CO or CO2 was developed to reduce hydrogen permeation in Stirling engines by forming low permeability oxide coatings in the heater tubes. An end product of this process is water - which can condense in the cold parts of the engine system. If the water vapor is reduced to a low enough level, the hydrogen can reduce the oxide coating resulting in increased permeability. The equilibrium level of water (oxygen bearing gas) required to avoid reduction of the oxide coating was investigated. Results at 720 C and 13.8 MPa have shown that: (1) pure hydrogen will reduce the coating; (2) 500 ppm CO (500 ppm water equivalent) does not prevent the reduction; and (3) 500 ppm CO2 (1000 ppm water) appears to be close to the equilibrium level. Further tests are planned to define the equilibrium level more precisely and to extend the data to 820 C and 3.4, 6.9, and 13.8 MPa.

Electrochemical advanced oxidation processes: today and tomorrow. A review.

PubMed

Sirés, Ignasi; Brillas, Enric; Oturan, Mehmet A; Rodrigo, Manuel A; Panizza, Marco

2014-01-01

In recent years, new advanced oxidation processes based on the electrochemical technology, the so-called electrochemical advanced oxidation processes (EAOPs), have been developed for the prevention and remediation of environmental pollution, especially focusing on water streams. These methods are based on the electrochemical generation of a very powerful oxidizing agent, such as the hydroxyl radical ((•)OH) in solution, which is then able to destroy organics up to their mineralization. EAOPs include heterogeneous processes like anodic oxidation and photoelectrocatalysis methods, in which (•)OH are generated at the anode surface either electrochemically or photochemically, and homogeneous processes like electro-Fenton, photoelectro-Fenton, and sonoelectrolysis, in which (•)OH are produced in the bulk solution. This paper presents a general overview of the application of EAOPs on the removal of aqueous organic pollutants, first reviewing the most recent works and then looking to the future. A global perspective on the fundamentals and experimental setups is offered, and laboratory-scale and pilot-scale experiments are examined and discussed.

Microbial oxidation and reduction of manganese: consequences in groundwater and applications.

PubMed

Gounot, A M

1994-08-01

In the natural environment, manganese is found as reduced soluble or adsorbed Mn(II) and insoluble Mn(III) and Mn(IV) oxides. Mn oxidation has been reported in various microorganisms. Several possible pathways, indirect or direct, have been proposed. A wider variety of Mn-reducing microorganisms, from highly aerobic to strictly anaerobic, has been described. The mechanisms of Mn reduction can be either an indirect process resulting from interactions with organic or inorganic compounds, or a direct enzymatic (electron-transfer) reaction. The role of microorganisms in Mn cycle is now well demonstrated by various methods in superficial natural environments, and research has been initiated on subsurface sediments. Observations in vivo (Rhône valley) and under in vitro suggested that bacterial activities are the main processes that promote manganese evolution and migration in shallow aquifers. After the building of hydroelectric dams, the stream of the Rhône was modified, giving rise to mud deposition on the bank. In the mud, bacteria are stimulated by the high organic content and consume oxygen. The redox potential drops. The manganese oxides previously formed under aerobic conditions are reduced and soluble manganese (Mn(II)) migrates into the aquifer. If the subsurface sediments are coarse-grained, the aquifer is well aerated, allowing the re-oxidation of Mn(II) by the oligotrophic attached bacteria in aquifer sediments. If the aquifer is confined, aeration is not sufficient for Mn-reoxidation. Mn(II) remains in a reduced state and migrates to the wells. Furthermore, the presence of organic matter in subsurface sediments results in the reduction of previously formed Mn oxides. Pseudo-amorphous manganese oxides, which were probably recently formed by bacteria, are more readily reduced than old crystalline manganese oxides. Although the concentrations of soluble manganese found in groundwaters are not toxic, it still is a problem since its oxidation results in darkening of water and plugging of pipes in drinking or industrial water systems. Soluble manganese can be removed from water by biological processes involving manganese-oxidizing bacteria, either in situ, or in sand filters after pumping. Various procedures are mentioned.

The role of polymer films on the oxidation of magnetite nanoparticles

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

Letti, C.J.; Paterno, L.G.; Pereira-da-Silva, M.A.

2017-02-15

A detailed investigation about the role of polymer films on the oxidation process of magnetite nanoparticles (∼7 nm diameter), under laser irradiation is performed employing micro Raman spectroscopy. To support this investigation, Fe{sub 3}O{sub 4}-np are synthesized by the co-precipitation method and assembled layer-by-layer with sodium sulfonated polystyrene (PSS). Polymer films (Fe{sub 3}O{sub 4}-np/PSS){sub n} with n=2,3,5,7,10 and 25 bilayers are employed as a model system to study the oxidation process under laser irradiation. Raman data are further processed by principal component analysis. Our findings suggest that PSS protects Fe{sub 3}O{sub 4}-np from oxidation when compared to powder samples, evenmore » for the sample with the greater number of bilayers. Further, the oxidation of magnetite to maghemite occurs preferably for thinner films up to 7 bilayers, while the onset for the formation of the hematite phase depends on the laser intensity for thicker films. Water takes part on the oxidation processes of magnetite, the oxidation/phase transformation of Fe{sub 3}O{sub 4}-np is intensified in films with more bilayers, since more water is included in those films. Encapsulation of Fe{sub 3}O{sub 4}-np by PSS in layer-by-layer films showed to be very efficient to avoid the oxidation process in nanosized magnetite. - Graphical abstract: Encapsulation of Fe{sub 3}O{sub 4}-np by PSS in layer-by-layer films avoids the oxidation and phase transformation of nanosized magnetite. - Highlights: • (Fe{sub 3}O{sub 4}-np/PSS){sub n} nanofilms, with n=2 up to 25, where layer-by-layer assembled. • The influence of film architecture on the Fe{sub 3}O{sub 4}-np oxidation was investigated through Raman spectroscopy. • Encapsulation of Fe{sub 3}O{sub 4}-np by PSS showed to be very efficient to avoid the Fe{sub 3}O{sub 4}-np oxidation.« less

Removal of atrazine and its by-products from water using electrochemical advanced oxidation processes.

PubMed

Komtchou, Simon; Dirany, Ahmad; Drogui, Patrick; Robert, Didier; Lafrance, Pierre

2017-11-15

Atrazine (ATZ) is one of the most common pesticides detected in surface water in Quebec (Canada). The present study was mainly focused on the degradation of ATZ and its by-products using electrochemical advanced oxidation processes such as photo-electro-Fenton (PEF), electro-Fenton (EF) and anodic-oxidation with simultaneous H 2 O 2 formation (AO - H 2 O 2 ). The comparison of these processes showed that PEF process was found to be the most effective process in removing ATZ and its by-products from both synthetic solution (ATZ 0  = 100 μg L -1 ) and real agricultural surface water enriched with ATZ (ATZ 0  = 10 μg L -1 ). Different operating parameters, including wavelength of the light, pH, current density and the presence of natural organic matter (humic acids) were investigated for PEF process using boron-doped diamond (BDD) anode and graphite cathode. The current density and the wavelength of the light were the most important parameters in the ATZ degradation efficiency. The best operating conditions were recorded for the synthetic samples at a current density of 18.2 mA cm -2 , a pH of 3.0 and treatment time of 45 min. Results showed that atrazine-desethyl-desisopropyl (DEDIA) was the most important by-product recorded. More than 99% of ATZ oxidation was recorded after 15 min of treatment and all the concentrations of major by-products were less than the limit of detection after 45 min of treatment. The PEF process was also tested for real surface water contaminated by ATZ: i) with and without addition of iron; ii) without pH adjustment (pH ∼ 6.7) and with pH adjustment (pH ∼ 3.1). In spite of the presence of radical scavenger and iron complexation the PEF process was more effective to remove ATZ from real surface water when the pH value was adjusted near to 3.0. The ATZ removal was 96.0% with 0.01 mM of iron (k app  = 0.13 min -1 ) and 100% with 0.1 mM of iron (k app  = 0.17 min -1 ). Copyright © 2017 Elsevier Ltd. All rights reserved.

Reactive molecular dynamics of the initial oxidation stages of Ni111 in pure water: effect of an applied electric field.

PubMed

Assowe, O; Politano, O; Vignal, V; Arnoux, P; Diawara, B; Verners, O; van Duin, A C T

2012-12-06

Corrosion processes occurring in aqueous solutions are critically dependent upon the interaction between the metal electrode and the solvent. In this work, the interaction of a nickel substrate with water molecules has been investigated using reactive force field (ReaxFF) molecular dynamics simulations. This approach was originally developed by van Duin and co-workers to study hydrocarbon chemistry and the catalytic properties of organic compounds. To our knowledge, this method has not previously been used to study the corrosion of nickel. In this work, we studied the interaction of 480 molecules of water (ρ = 0.99 g·cm(-3)) with Ni(111) surfaces at 300 K. The results showed that a water "bilayer" was adsorbed on the nickel surface. In the absence of an applied electric field, no dissociation of water was observed. However, the nickel atoms at the surface were charged positively, whereas the first water layer was charged negatively, indicating the formation of an electric double layer. To study the corrosion of nickel in pure water, we introduced an external electric field between the metal and the solution. The electric field intensity varied between 10 and 20 MeV/cm. The presence of this electric field led to oxidation of the metal surface. The structural and morphological differences associated with the growth of this oxide film in the presence of the electric field were evaluated. The simulated atomic trajectories were used to analyze the atomic displacement during the reactive process. The growth of the oxide scale on the nickel surface was primarily due to the movement of anions toward the interior of the metal substrate and the migration of nickel toward the free surface. We found that increasing the electric field intensity sped up the corrosion of nickel. The results also showed that the oxide film thickness increased linearly with increasing electric field intensity.

Planetary ecology; Proceedings of the Sixth International Symposium on Environmental Biogeochemistry, Santa Fe, NM, October 10-14, 1983

NASA Technical Reports Server (NTRS)

Caldwell, D. E. (Editor); Brierley, J. A. (Editor); Brierley, C. L. (Editor)

1985-01-01

Topics presented include biological evolution and planetary chemistry; C-1 compounds; transport, deposition, and weathering; sulfur transformations; ground water; transformation processes for nitrogen oxides; and soils. Papers are presented on immunological studies on the organic matrix of recent and fossil invertebrate shells; biogenic gases in sediments deposited since Miocene times on the Walvis Ridge, South Atlantic Ocean; aspects of the biogeochemistry of Big Soda Lake, NV; mesophilic manganese-oxidizing bacteria from hydrothermal discharge areas at 21 deg North on the East Pacific Rise; and autotrophic growth and iron oxidation and inhibition kinetics of Leptospirillum ferrooxidans. Consideration is also given to thermophilic archaebacteria occurring in submarine hydrothermal areas; fate of sulfate in a soft-water, acidic lake; geochemical conditions in the ground water environment; microbial transformations as sources and sinks for nitrogen oxides; and the biogeochemistry of soil phosphorus.

Light-Dependent Sulfide Oxidation in the Anoxic Zone of the Chesapeake Bay Can Be Explained by Small Populations of Phototrophic Bacteria

PubMed Central

Bennett, Alexa J.; Hanson, Thomas E.; Luther, George W.

2015-01-01

Microbial sulfide oxidation in aquatic environments is an important ecosystem process, as sulfide is potently toxic to aerobic organisms. Sulfide oxidation in anoxic waters can prevent the efflux of sulfide to aerobic water masses, thus mitigating toxicity. The contribution of phototrophic sulfide-oxidizing bacteria to anaerobic sulfide oxidation in the Chesapeake Bay and the redox chemistry of the stratified water column were investigated in the summers of 2011 to 2014. In 2011 and 2013, phototrophic sulfide-oxidizing bacteria closely related to Prosthecochloris species of the phylum Chlorobi were cultivated from waters sampled at and below the oxic-anoxic interface, where measured light penetration was sufficient to support populations of low-light-adapted photosynthetic bacteria. In 2012, 2013, and 2014, light-dependent sulfide loss was observed in freshly collected water column samples. In these samples, extremely low light levels caused 2- to 10-fold increases in the sulfide uptake rate over the sulfide uptake rate under dark conditions. An enrichment, CB11, dominated by Prosthecochloris species, oxidized sulfide with a Ks value of 11 μM and a Vmax value of 51 μM min−1 (mg protein−1). Using these kinetic values with in situ sulfide concentrations and light fluxes, we calculated that a small population of Chlorobi similar to those in enrichment CB11 can account for the observed anaerobic light-dependent sulfide consumption activity in natural water samples. We conclude that Chlorobi play a far larger role in the Chesapeake Bay than currently appreciated. This result has potential implications for coastal anoxic waters and expanding oxygen-minimum zones as they begin to impinge on the photic zone. PMID:26296727

Deactivation of wastewater-derived N-nitrosodimethylamine precursors with chlorine dioxide oxidation and the effect of pH.

PubMed

Uzun, Habibullah; Kim, Daekyun; Karanfil, Tanju

2018-09-01

In this study, the effect of chlorine dioxide (ClO 2 ) oxidation on the deactivation of wastewater (WW)-derived N-nitrosodimethylamine (NDMA) precursors was investigated under various conditions (i.e., ClO 2 application pH, dose and contact time). At pH 6.0, decreases in NDMA formation potentials (FPs) or occurrences (under uniform formation conditions [UFC]) were relatively low (<25%) with ClO 2 oxidation regardless of WW-impact. A negative removal was also observed after ClO 2 oxidation in some of the non-impacted waters. However, NDMA FP removals were significant (up to ~85%) under the same oxidation conditions in WW-impacted waters at pH 7.8. This indicates that the majority of WW-derived NDMA precursors can be deactivated with ClO 2 oxidation above neutral pH. This was attributed to the better oxidative reaction of ClO 2 with amines that have lone pair electrons to be shared at higher oxidation pH conditions. In addition, relatively short oxidation periods with ClO 2 (i.e., ≤10 min) or low Ct (concentration × time, ~10 mg ∗ min/L) values were sufficient for the deactivation of WW-derived NDMA precursors. ClO 2 oxidation was effective in freshly WW-impacted waters. Natural attenuation processes (e.g., sorption, biodegradation, etc.) can change the reactivity of WW-derived NDMA precursors for oxidation with ClO 2 . The effect of ClO 2 on the removal of THM precursors was low (<25%) and independent of oxidation conditions. Given the low formation of regulated THMs and HAAs, ClO 2 oxidation presents a viable option for the simultaneous control of NDMA and regulated DBP formation during water treatment, especially for utilities treating WW-impacted water sources. Copyright © 2018 Elsevier B.V. All rights reserved.

GLYPHOSATE REMOVAL FROM DRINKING WATER

EPA Science Inventory

Activated-carbon, oxidation, conventional-treatment, filtration, and membrane studies are conducted to determine which process is best suited to remove the herbicide glyphosate from potable water. Both bench-scale and pilot-scale studies are completed. Computer models are used ...

Degradation of cyanotoxins (microcystin) in drinking water using photoelectrooxidation.

PubMed

Garcia, A C A; Rodrigues, M A S; Xavier, J L N; Gazulla, V; Meneguzzi, A; Bernardes, A M

2015-05-01

The discharge of sewage and industrial effluents containing high concentrations of pollutants in water bodies increases eutrophication. Cyanobacteria, some of the organisms whose growth is promoted by high nutrient concentrations, are resistant and produce several types of toxins, known as cyanotoxins, highly harmful to human beings. Current water treatment systems for the public water supply are not efficient in degradation of toxins. Advanced oxidation processes (AOP) have been tested for the removal of cyanotoxins, and the results have been positive. This study examines the application of photoelectrooxidation in the degradation of cyanotoxins (microcystins). The performance of the oxidative processes involved was evaluated separately: Photocatalysis, Electrolysis and Photoelectrooxidation. Results showed that the electrical current and UV radiation were directly associated with toxin degradation. The PEO system is efficient in removing cyanotoxins, and the reduction rate reached 99%. The final concentration of toxin was less than 1 µg/L of microcystin in the treated solution.

Preparation of energy storage materials

DOEpatents

Li, Lin Song; Jia, Quanxi

2003-01-01

A process is provided for the preparation of a metallic oxide composite including mixing an aqueous solution of a water-soluble metal compound and colloidal silica, depositing the mixture upon a substrate, heating the mixture-coated substrates at temperatures from about 150.degree. C. to about 300.degree. C. for time sufficient to form a metallic oxide film, and, removing the silica from the metallic oxide film whereby a porous metal oxide structure is formed.

Preparation Of Energy Storage Materials

DOEpatents

Li, Lin Song; Jia, Quanxi

2003-12-02

A process is provided for the preparation of a metallic oxide composite including mixing an aqueous solution of a water-soluble metal compound and colloidal silica, depositing the mixture upon a substrate, heating the mixture-coated substrates at temperatures from about 150.degree. C. to about 300.degree. C. for time sufficient to form a metallic oxide film, and, removing the silica from the metallic oxide film whereby a porous metal oxide structure is formed.

Low-Temperature, Solution-Processed, Transparent Zinc Oxide-Based Thin-Film Transistors for Sensing Various Solvents.

PubMed

You, Hsin-Chiang; Wang, Cheng-Jyun

2017-02-26

A low temperature solution-processed thin-film transistor (TFT) using zinc oxide (ZnO) film as an exposed sensing semiconductor channel was fabricated to detect and identify various solution solvents. The TFT devices would offer applications for low-cost, rapid and highly compatible water-soluble detection and could replace conventional silicon field effect transistors (FETs) as bio-sensors. In this work, we demonstrate the utility of the TFT ZnO channel to sense various liquids, such as polar solvents (ethanol), non-polar solvents (toluene) and deionized (DI) water, which were dropped and adsorbed onto the channel. It is discussed how different dielectric constants of polar/non-polar solvents and DI water were associated with various charge transport properties, demonstrating the main detection mechanisms of the thin-film transistor.

Electro-oxidation of reverse osmosis concentrates generated in tertiary water treatment.

PubMed

Pérez, G; Fernández-Alba, A R; Urtiaga, A M; Ortiz, I

2010-05-01

This work investigates the application of the electro-oxidation technology provided with boron doped diamond (BDD), an electrode material which has shown outstanding properties in oxidation of organic and inorganic compounds, for the treatment of reverse osmosis (RO) concentrates generated in tertiary wastewater treatment plants (WWTP). Chemical oxygen demand (COD), ammonium and several anions were measured during the electro-oxidation process, and the influence of the applied current density (20-200A/m(2)) was analysed on process kinetics. Analytical assessment showed that several emerging pollutants (pharmaceuticals, personal care products, stimulants, etc.) were presented both in the effluent of the secondary WWTP as well as in the RO concentrate. For this reason, a group of 10 emerging pollutants, those found with higher concentrations, was selected in order to test whether electro-oxidation can be also applied for their mitigation. In the removal of emerging pollutants the electrical current density in the range 20-100A/m(2) did not show influence likely due to the mass transfer resistance developed in the process when the oxidized solutes are present in such low concentrations. Their removal rates were fitted to first order expressions, and the apparent kinetic constants for the anodic oxidation of each compound were calculated. Finally, the formation of trihalomethanes (THMs) has been checked; concluding that after selecting the appropriate operational conditions the attained concentration is lower than the standards for drinking water established in European and EPA regulations. Copyright (c) 2010 Elsevier Ltd. All rights reserved.

Removal of pharmaceutical residue in municipal wastewater by DAF (dissolved air flotation)-MBR (membrane bioreactor) and ozone oxidation.

PubMed

Choi, Miyoung; Choi, Dong Whan; Lee, Jung Yeol; Kim, Young Suk; Kim, Bun Su; Lee, Byoung Ho

2012-01-01

Growing attention is given to pharmaceutical residue in the water environment. It is known that pharmaceuticals are able to survive from a series of wastewater treatment processes. Concerns regarding pharmaceutical residues are attributed to the fact that they are being detected in water and sediment environment ubiquitously. Pharmaceutical treatment using a series of wastewater treatment processes of the DAF (dissolved air flotation)-MBR (membrane bioreactor)-ozone oxidation was conducted in the study. DAF, without addition of coagulant, could remove COD(cr) (chemical oxygen demand by Cr) up to over 70%, BOD 73%, SS 83%, T-N 55%, NH₄(+) 23%, and T-P 65% in influent of municipal wastewater. Average removal rates of water quality parameters by the DAF-MBR system were very high, e.g. COD(cr) 95.88%, BOD₅ 99.66%, COD(mn) (chemical oxygen demand by Mn) 93.63%, T-N 69.75%, NH₄-N 98.46%, T-P 78.23%, and SS 99.51%, which satisfy effluent water quality standards. Despite the high removal rate of the wastewater treatment system, pharmaceuticals were eliminated to be about 50-99% by the MBR system, depending on specific pharmaceuticals. Ibuprofen was well removed by MBR system up to over 95%, while removal rate of bezafibrate ranged between 50 and 90%. With over 5 mg/l of ozone oxidation, most pharmaceuticals which survived the DAF-MBR process were removed completely or resulted in very low survival rate within the range of few micrograms per litre. However, some pharmaceuticals such as bezafibrate and naproxen tended to be resistant to ozone oxidation.

Laboratory chalcopyrite oxidation by Acidithiobacillus ferrooxidans: Oxygen and sulfur isotope fractionation

USGS Publications Warehouse

Thurston, R.S.; Mandernack, K.W.; Shanks, Wayne C.

2010-01-01

Laboratory experiments were conducted to simulate chalcopyrite oxidation under anaerobic and aerobic conditions in the absence or presence of the bacterium Acidithiobacillus ferrooxidans. Experiments were carried out with 3 different oxygen isotope values of water (??18OH2O) so that approach to equilibrium or steady-state isotope fractionation for different starting conditions could be evaluated. The contribution of dissolved O2 and water-derived oxygen to dissolved sulfate formed by chalcopyrite oxidation was unambiguously resolved during the aerobic experiments. Aerobic oxidation of chalcopyrite showed 93 ?? 1% incorporation of water oxygen into the resulting sulfate during the biological experiments. Anaerobic experiments showed similar percentages of water oxygen incorporation into sulfate, but were more variable. The experiments also allowed determination of sulfate-water oxygen isotope fractionation, ??18OSO4-H2O, of ~ 3.8??? for the anaerobic experiments. Aerobic oxidation produced apparent ??SO4-H2O values (6.4???) higher than the anaerobic experiments, possibly due to additional incorporation of dissolved O2 into sulfate. ??34SSO4 values are ~ 4??? lower than the parent sulfide mineral during anaerobic oxidation of chalcopyrite, with no significant difference between abiotic and biological processes. For the aerobic experiments, a small depletion in ??34SSO4 of ~- 1.5 ?? 0.2??? was observed for the biological experiments. Fewer solids precipitated during oxidation under aerobic conditions than under anaerobic conditions, which may account for the observed differences in sulfur isotope fractionation under these contrasting conditions. ?? 2009 Elsevier B.V.

Pilot-scale UV/H2O2 study for emerging organic contaminants decomposition.

PubMed

Chu, Xiaona; Xiao, Yan; Hu, Jiangyong; Quek, Elaine; Xie, Rongjin; Pang, Thomas; Xing, Yongjie

2016-03-01

Human behaviors including consumption of drugs and use of personal care products, climate change, increased international travel, and the advent of water reclamation for direct potable use have led to the introduction of significant amounts of emerging organic contaminants into the aqueous environment. In addition, the lower detection limits associated with improved scientific methods of chemical analysis have resulted in a recent increase in documented incidences of these contaminants which previously were not routinely monitored in water. Such contaminants may cause known or suspected adverse ecological and/or human health effects at very low concentrations. Conventional drinking water treatment processes may not effectively remove these organic contaminants. Advanced oxidation process (AOP) is a promising treatment process for the removal of most of these emerging organic contaminants, and has been accepted worldwide as a suitable treatment process. In this study, different groups of emerging contaminants were studied for decomposition efficiency using pilot-scale UV/H2O2 oxidation setup, including EDCs, PPCPs, taste and odor (T&O), and perfluorinated compounds. Results found that MP UV/H2O2 AOP was efficient in removing all the selected contaminants except perfluorinated compounds. Study of the kinetics of the process showed that both light absorption and quantum yield of each compound affected the decomposition performance. Analysis of water quality parameters of the treated water indicated that the outcome of both UV photolysis and UV/H2O2 processes can be affected by changes in the feed water quality.

Acidophilic sulfur disproportionation

NASA Astrophysics Data System (ADS)

Hardisty, Dalton S.; Olyphant, Greg A.; Bell, Jonathan B.; Johnson, Adam P.; Pratt, Lisa M.

2013-07-01

Bacterial disproportionation of elemental sulfur (S0) is a well-studied metabolism and is not previously reported to occur at pH values less than 4.5. In this study, a sediment core from an abandoned-coal-mine-waste deposit in Southwest Indiana revealed sulfur isotope fractionations between S0 and pyrite (Δ34Ses-py) of up to -35‰, inferred to indicate intense recycling of S0 via bacterial disproportionation and sulfide oxidation. Additionally, the chemistry of seasonally collected pore-water profiles were found to vary, with pore-water pH ranging from 2.2 to 3.8 and observed seasonal redox shifts expressed as abrupt transitions from Fe(III) to Fe(II) dominated conditions, often controlled by fluctuating water table depths. S0 is a common product during the oxidation of pyrite, a process known to generate acidic waters during weathering and production of acid mine drainage. The H2S product of S0 disproportionation, fractionated by up to -8.6‰, is rapidly oxidized to S0 near redox gradients via reaction with Fe(III) allowing for the accumulation of isotopically light S0 that can then become subject to further sulfur disproportionation. A mass-balance model for S0 incorporating pyrite oxidation, S0 disproportionation, and S0 oxidation readily explains the range of observed Δ34Ses-py and emphasizes the necessity of seasonally varying pyrite weathering and metabolic rates, as indicated by the pore water chemistry. The findings of this research suggest that S0 disproportionation is potentially a common microbial process at a pH < 4.5 and can create large sulfur isotope fractionations, even in the absence of sulfate reduction.

Formation and fates of nitrosamines and their formation potentials from a surface water source to drinking water treatment plants in Southern Taiwan.

PubMed

Chen, Wei-Hsiang; Wang, Chung-Ya; Huang, Tsung-Hsien

2016-10-01

Nitrosamines are toxic and emerging disinfection byproducts. In this study, three drinking water treatment plants (DWTPs) in southern Taiwan treating the same source water in Gaoping River with comparable technologies were selected. The objective was to evaluate the formation and fates of six nitrosamines and their formation potentials (FPs) from a surface water source to drinking water. Albeit decreased further downstream in the river, four nitrosamine-FPs were observed in the source water due to anthropogenic pollution in the upstream areas. In the DWTPs, nitrosamines were formed and NDMA was the main species. While high organic carbon concentrations indicated elevated nitrosamine-FPs in the source water, NDMA formation in the DWTPs was more positively associated with reductions of water parameters that quantify organic matters with double bonded ring structures. Although precursor removal via pre-oxidation is a viable approach to limit nitrosamine formation during post-disinfection, this study clearly indicates that a great portion of NDMA in treated water has been formed in the 1st oxidation step of drinking water treatment. The pre-oxidation simulations in the lab demonstrated the impact of pre-chlorination on nitrosamine formation. Given the limited removal in conventional treatment processes, avoiding nitrosamine-FPs in sources and/or nitrosamine formation during pre-oxidation become important issues to control the threats of nitrosamines in drinking water. Under current circumstance in which pre-oxidation is widely used to optimize the treatment effectiveness in many DWTPs, its adverse effect by forming nitrosamines needs to be carefully minimized and using technologies other than pre-chlorination (e.g., pre-ozonation) may be considered. Copyright © 2016 Elsevier Ltd. All rights reserved.

The Role of Microbial Processes in the Oxidation and Removal of Arsenic from Drinking Water

EPA Science Inventory

The United States Environmental Protection Agency (EPA) recently reduced the drinking water standard for arsenic (As) in water from 0.05 to 0.010 milligrams/Liter (L) (10 micrograms/L). This reduction was prompted by new health effects research, which concluded th...

Oxidation of Oil Sands Process-Affected Water by Potassium Ferrate(VI).

PubMed

Wang, Chengjin; Klamerth, Nikolaus; Huang, Rongfu; Elnakar, Haitham; Gamal El-Din, Mohamed

2016-04-19

This paper investigates the oxidation of oil sands process-affected water (OSPW) by potassium ferrate(VI). Due to the selectivity of ferrate(VI) oxidation, two-ring and three-ring fluorescing aromatics were preferentially removed at doses <100 mg/L Fe(VI), and one-ring aromatics were removed only at doses ≥100 mg/L Fe(VI). Ferrate(VI) oxidation achieved 64.0% and 78.4% removal of naphthenic acids (NAs) at the dose of 200 mg/L and 400 mg/L Fe(VI) respectively, and NAs with high carbon number and ring number were removed preferentially. (1)H nuclear magnetic resonance ((1)H NMR) spectra indicated that the oxidation of fluorescing aromatics resulted in the opening of some aromatic rings. Electron paramagnetic resonance (EPR) analysis detected signals of organic radical intermediates, indicating that one-electron transfer is one of the probable mechanisms in the oxidation of NAs. The inhibition effect of OSPW on Vibrio fischeri and the toxicity effect on goldfish primary kidney macrophages (PKMs) were both reduced after ferrate(VI) oxidation. The fluorescing aromatics in OSPW were proposed to be an important contributor to this acute toxicity. Degradation of model compounds with ferrate(VI) was also investigated and the results confirmed our findings in OSPW study.

Remediation of water pollution caused by pharmaceutical residues based on electrochemical separation and degradation technologies: a review.

PubMed

Sirés, Ignasi; Brillas, Enric

2012-04-01

In the last years, the decontamination and disinfection of waters by means of direct or integrated electrochemical processes are being considered as a very appealing alternative due to the significant improvement of the electrode materials and the coupling with low-cost renewable energy sources. Many electrochemical technologies are currently available for the remediation of waters contaminated by refractory organic pollutants such as pharmaceutical micropollutants, whose presence in the environment has become a matter of major concern. Recent reviews have focused on the removal of pharmaceutical residues upon the application of other important methods like ozonation and advanced oxidation processes. Here, we present an overview on the electrochemical methods devised for the treatment of pharmaceutical residues from both, synthetic solutions and real pharmaceutical wastewaters. Electrochemical separation technologies such as membrane technologies, electrocoagulation and internal micro-electrolysis, which only isolate the pollutants from water, are firstly introduced. The fundamentals and experimental set-ups involved in technologies that allow the degradation of pharmaceuticals, like anodic oxidation, electro-oxidation with active chlorine, electro-Fenton, photoelectro-Fenton and photoelectrocatalysis among others, are further discussed. Progress on the promising solar photoelectro-Fenton process devised and further developed in our laboratory is especially highlighted and documented. The abatement of total organic carbon or reduction of chemical oxygen demand from contaminated waters allows the comparison between the different methods and materials. The routes for the degradation of the some pharmaceuticals are also presented. Copyright © 2011 Elsevier Ltd. All rights reserved.

Nitrous oxide emissions from one-step partial nitritation/anammox processes.

PubMed

Yang, Jingjing; Trela, Jozef; Plaza, Elzbieta

2016-12-01

Measurements of nitrous oxide were made at pilot- and full-scale plants to evaluate greenhouse gas emissions from one-step partial nitritation/anammox processes applied in moving bed biofilm reactors treating reject water. It was found that 0.51-1.29% and 0.35-1.33% of the total nitrogen loads in the pilot- and full-scale reactor, respectively, were emitted as nitrous oxide. Between 80 and 90% of nitrous oxide emissions were in gaseous form and the rest amount was found in the reactor effluent; over 90% of nitrous oxide emissions occurred in the aerated period and less than 8% in the non-aerated period in the full-scale study. Nitrous oxide productions/consumptions were closely related to aeration and the nitrogen loads applied in the system.

Architecting Graphene Oxide Rolled-Up Micromotors: A Simple Paper-Based Manufacturing Technology.

PubMed

Baptista-Pires, Luis; Orozco, Jahir; Guardia, Pablo; Merkoçi, Arben

2018-01-01

A graphene oxide rolled-up tube production process is reported using wax-printed membranes for the fabrication of on-demand engineered micromotors at different levels of oxidation, thickness, and lateral dimensions. The resultant graphene oxide rolled-up tubes can show magnetic and catalytic movement within the addition of magnetic nanoparticles or sputtered platinum in the surface of graphene-oxide-modified wax-printed membranes prior to the scrolling process. As a proof of concept, the as-prepared catalytic graphene oxide rolled-up micromotors are successfully exploited for oil removal from water. This micromotor production technology relies on an easy, operator-friendly, fast, and cost-efficient wax-printed paper-based method and may offer a myriad of hybrid devices and applications. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Assessment of the UV/Cl2 advanced oxidation process for the degradation of the emerging contaminants amitriptyline hydrochloride, methyl salicylate and 2-phenoxyethanol in water systems.

PubMed

Javier Benitez, F; Real, Francisco J; Acero, Juan L; Casas, Francisco

2017-10-01

Three emerging contaminants (amitriptyline hydrochloride (AH), methyl salicylate (MS) and 2-phenoxyethanol (PE)) frequently found in wastewaters were selected to be individually degraded in ultra-pure water by the advanced oxidation process (AOP) constituted by the combination of UV radiation and chlorine. The influence of pH, initial chlorine concentration and nature of the contaminants was firstly explored. The trend for the reactivity of the selected compounds was deduced: AH > MS > PE. A later kinetic study was carried out focused on the evaluation of the first-order rate constants and the determination of the partial contribution to the global reaction of the direct photochemical pathway and the radical pathway. In a second stage, the simultaneous oxidation of mixtures of the selected contaminants in several types of water was also performed by the same combination UV/Cl 2 . The efficiency of this combined system UV/Cl 2 was compared to other oxidants such as the UV/[Formula: see text] and UV/H 2 O 2 AOPs, and the influence of the operating variables was discussed. Results confirmed that the UV/Cl 2 system provides higher elimination efficiencies among the AOPs tested. The presence of dissolved organic matter and bicarbonate ions in the water matrix caused a decrease in the treatment efficiency.

Microbial nitrogen sinks in the water column of a large coastal hypoxic area, the Gulf of Mexico "Dead Zone"

NASA Astrophysics Data System (ADS)

Rogener, M. K.; Roberts, B. J.; Rabalais, N. N.; Stewart, F. J.; Joye, S. B.

2016-02-01

Excess nitrogen in coastal environments leads to eutrophication, harmful algal blooms, habitat loss, oxygen depletion and reductions in biodiversity. As such, biological nitrogen (N) removal through the microbially-mediated process of denitrification is a critical ecosystem function that can mitigate the negative consequences of excess nitrogen loading. However, denitrification can produce nitrous oxide, a potent greenhouse gas, as a byproduct under some environmental conditions. To understand how excess nitrogen loading impacts denitrification, we measured rates of this process in the water column of the Gulf of Mexico "Dead Zone" three times over the summer of 2015. The Dead Zone is generated by excessive nitrogen loading from the Mississippi River co-occurring with strong water column stratification, which leads to a large summer-time hypoxic/anoxic area at the mouth of the river and along the coast of Louisiana. Rates of denitrification ranged from 31 to 153 nmol L-1 d-1. Dead Zone waters are also enriched in methane and aerobic methane oxidation rates ranged from 0.1 to 4.3 nmol L-1 d-1. Maximal denitrification rates were observed at stations with the lowest oxygen concentrations and highest methane oxidation rates, suggesting a potential coupling between nitrate reduction and methane oxidation which both scrubs reactive N and methane from the system, thus performing a duel ecosystem service.

Ambient iron-mediated aeration (IMA) for water reuse.

PubMed

Deng, Yang; Englehardt, James D; Abdul-Aziz, Samer; Bataille, Tristan; Cueto, Josenrique; De Leon, Omar; Wright, Mary E; Gardinali, Piero; Narayanan, Aarthi; Polar, Jose; Tomoyuki, Shibata

2013-02-01

Global water shortages caused by rapidly expanding population, escalating water consumption, and dwindling water reserves have rendered water reuse a strategically significant approach to meet current and future water demand. This study is the first to our knowledge to evaluate the technical feasibility of iron-mediated aeration (IMA), an innovative, potentially economical, holistic, oxidizing co-precipitation process operating at room temperature, atmospheric pressure, and neutral pH, for water reuse. In the IMA process, dissolved oxygen (O₂) was continuously activated by zero-valent iron (Fe⁰) to produce reactive oxygen species (ROS) at ambient pH, temperature, and pressure. Concurrently, iron sludge was generated as a result of iron corrosion. Bench-scale tests were conducted to study the performance of IMA for treatment of secondary effluent, natural surface water, and simulated contaminated water. The following removal efficiencies were achieved: 82.2% glyoxylic acid, ~100% formaldehyde as an oxidation product of glyoxylic acid, 94% of Ca²⁺ and associated alkalinity, 44% of chemical oxygen demand (COD), 26% of electrical conductivity (EC), 98% of di-n-butyl phthalate (DBP), 80% of 17β-estradiol (E2), 45% of total nitrogen (TN), 96% of total phosphorus (TP), 99.8% of total Cr, >90% of total Ni, 99% of color, 3.2 log removal of total coliform, and 2.4 log removal of E. Coli. Removal was attributed principally to chemical oxidation, precipitation, co-precipitation, coagulation, adsorption, and air stripping concurrently occurring during the IMA treatment. Results suggest that IMA is a promising treatment technology for water reuse. Copyright © 2012 Elsevier Ltd. All rights reserved.

Photochemical route for accessing amorphous metal oxide materials for water oxidation catalysis.

PubMed

Smith, Rodney D L; Prévot, Mathieu S; Fagan, Randal D; Zhang, Zhipan; Sedach, Pavel A; Siu, Man Kit Jack; Trudel, Simon; Berlinguette, Curtis P

2013-04-05

Large-scale electrolysis of water for hydrogen generation requires better catalysts to lower the kinetic barriers associated with the oxygen evolution reaction (OER). Although most OER catalysts are based on crystalline mixed-metal oxides, high activities can also be achieved with amorphous phases. Methods for producing amorphous materials, however, are not typically amenable to mixed-metal compositions. We demonstrate that a low-temperature process, photochemical metal-organic deposition, can produce amorphous (mixed) metal oxide films for OER catalysis. The films contain a homogeneous distribution of metals with compositions that can be accurately controlled. The catalytic properties of amorphous iron oxide prepared with this technique are superior to those of hematite, whereas the catalytic properties of a-Fe(100-y-z)Co(y)Ni(z)O(x) are comparable to those of noble metal oxide catalysts currently used in commercial electrolyzers.

Possible origin and roles of nano-porosity in ZrO2 scales for hydrogen pick-up in Zr alloys

NASA Astrophysics Data System (ADS)

Lindgren, Mikaela; Geers, Christine; Panas, Itai

2017-08-01

A mechanistic understanding of Wagnerian build-up and subsequent non-Wagnerian break-down of barrier oxide upon oxidation of zirconium alloys by water is reiterated. Hydrogen assisted build-up of nano-porosity is addressed. Growth of sub-nanometer wide stalactitic pores owing to increasing aggregation of neutral oxygen vacancies offering a means to permeate hydrogen into the alloy is explored by density functional theory. The Wagnerian channel utilizes charge separation allowing charged oxygen vacancies and electrons to move separately from nominal anode to nominal cathode. This process becomes increasingly controlled by the charging of the barrier oxide resulting in sub-parabolic rate law for oxide growth. The break-down of the barrier oxide is understood to be preceded by avalanching hydrogen pick-up in the alloy. Pore mediated diffusion allows water to effectively short circuit the barrier oxide.

Assessment of wear coefficients of nuclear zirconium claddings without and with pre-oxidation

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

Qu, Jun; Cooley, Kevin M.; Shaw, Austin H.

In the cores of pressurized water nuclear reactors, water-flow induced vibration is known to cause claddings on the fuel rods to rub against their supporting grids. Such grid-to-rod-fretting (GTRF) may lead to fretting wear-through and the leakage of radioactive species. The surfaces of actual zirconium alloy claddings in a reactor are inevitably oxidized in the high-temperature pressurized water, and some claddings are even pre-oxidized. As a result, the wear process of the surface oxide film is expected to be quite different from the zirconium alloy substrate. In this paper, we attempt to measure the wear coefficients of zirconium claddings withoutmore » and with pre-oxidation rubbing against grid samples using a bench-scale fretting tribometer. Results suggest that the volumetric wear coefficient of the pre-oxidized cladding is 50 to 200 times lower than that of the untreated cladding. In terms of the linear rate of wear depth, the pre-oxidized alloy wears about 15 times more slowly than the untreated cladding. Finally, fitted with the experimentally-determined wear rates, a stage-wise GTRF engineering wear model demonstrates good agreement with in-reactor experience in predicting the trend of cladding lives.« less

Assessment of wear coefficients of nuclear zirconium claddings without and with pre-oxidation

DOE PAGES

Qu, Jun; Cooley, Kevin M.; Shaw, Austin H.; ...

2016-03-16

In the cores of pressurized water nuclear reactors, water-flow induced vibration is known to cause claddings on the fuel rods to rub against their supporting grids. Such grid-to-rod-fretting (GTRF) may lead to fretting wear-through and the leakage of radioactive species. The surfaces of actual zirconium alloy claddings in a reactor are inevitably oxidized in the high-temperature pressurized water, and some claddings are even pre-oxidized. As a result, the wear process of the surface oxide film is expected to be quite different from the zirconium alloy substrate. In this paper, we attempt to measure the wear coefficients of zirconium claddings withoutmore » and with pre-oxidation rubbing against grid samples using a bench-scale fretting tribometer. Results suggest that the volumetric wear coefficient of the pre-oxidized cladding is 50 to 200 times lower than that of the untreated cladding. In terms of the linear rate of wear depth, the pre-oxidized alloy wears about 15 times more slowly than the untreated cladding. Finally, fitted with the experimentally-determined wear rates, a stage-wise GTRF engineering wear model demonstrates good agreement with in-reactor experience in predicting the trend of cladding lives.« less

Evaluation and comparison of alternative designs for water/solid-waste processing systems for spacecraft

NASA Technical Reports Server (NTRS)

Spurlock, J. M.

1975-01-01

Promising candidate designs currently being considered for the management of spacecraft solid waste and waste-water materials were assessed. The candidate processes were: (1) the radioisotope thermal energy evaporation/incinerator process; (2) the dry incineration process; and (3) the wet oxidation process. The types of spacecraft waste materials that were included in the base-line computational input to the candidate systems were feces, urine residues, trash and waste-water concentrates. The performance characteristics and system requirements for each candidate process to handle this input and produce the specified acceptable output (i.e., potable water, a storable dry ash, and vapor phase products that can be handled by a spacecraft atmosphere control system) were estimated and compared. Recommendations are presented.

Modelling nitrite dynamics and associated feedback processes in the Benguela oxygen minimum zone

NASA Astrophysics Data System (ADS)

Mashifane, T. B.; Vichi, M.; Waldron, H. N.; Machu, E.; Garçonc, V.

2016-08-01

Understanding nitrite dynamics in oxygen minimum zones (OMZs) is a challenge as it represents an intermediary nitrogen species with a short turnover time. Nitrite is also reduced to nitrogen in OMZs, preventing its accumulation. This creates difficulties in detecting nitrite with colorimetric methods as concentrations may occur below detection limits in some regions. Nitrite concentrations are key to understanding intermediate nitrogen processes and their implication for nitrogen loss in OMZs. A coupled physical-biogeochemical model is applied in the Benguela OMZ to study nitrite dynamics and its associated feedback processes. Simulated results show occurrence of primary and secondary nitrite maxima in the Benguela shelf waters. The primary nitrite maxima in the Benguela are attributed to nitrification and nitrate assimilation as they occur in association with the nitracline. Secondary nitrite maxima accumulate in the Angola-Benguela Front (ABF) OMZ and are attributed to denitrification. The secondary nitrite maxima are consumed by anaerobic ammonium oxidation (anammox) off Walvis Bay. Nitrite maxima are restricted to the shelf off Walvis Bay and advected offshore in the ABF region. Interchanges between the poleward South Atlantic Central Water (SACW) and the equatorward, well-aerated Eastern South Atlantic Central Water (ESACW) drive the seasonality of nitrogen processes in the Benguela. Subsequent nitrite reduction in the Benguela OMZ leads to nitrous oxide production, with high concentrations occurring in the ABF region as a result of nitrification and denitrification. Off Walvis Bay, nitrous oxide production is low since nitrite is consumed by anammox. Nitrous oxide production occurs in thermocline, intermediate and deeper water masses in the ABF region. High N fluxes in the Benguela are attributed to nitrification as compared to anammox and denitrification. Results from this study demonstrate the role of intermediate nitrogen species in nitrogen feedback processes in the Benguela and can be applied in other regions.

Temperature of frozen storage affects the nature and consequences of protein oxidation in beef patties.

PubMed

Utrera, Mariana; Morcuende, David; Estévez, Mario

2014-03-01

The effect of three frozen storage temperatures (-8, -18 and -80 °C) on protein oxidation in beef patties was studied through the analysis of novel oxidation markers. Additionally, the connection between lipid and protein oxidation and the impact of the latter on particular quality traits (water holding capacity, color and texture) of subsequently processed beef patties (cooking/cold-stored) were investigated. Protein oxidation was measured as the loss of tryptophan fluorescence and formation of diverse lysine oxidation products (α-aminoadipic semialdehyde, α-aminoadipic acid and Schiff bases). Lipid oxidation was assessed by levels of thiobarbituric acid reactive substances and hexanal. A significant effect of storage temperature on protein oxidation was detected. Frozen storage increased the susceptibility of meat proteins to undergo further oxidation during processing. Timely interactions were found between lipid and protein oxidation. Plausible mechanisms by which oxidative damage to proteins may have an impact in particular quality traits are thoroughly discussed. © 2013.

Production of high concentrated cellulosic ethanol by acetone/water oxidized pretreated beech wood.

PubMed

Katsimpouras, Constantinos; Kalogiannis, Konstantinos G; Kalogianni, Aggeliki; Lappas, Angelos A; Topakas, Evangelos

2017-01-01

Lignocellulosic biomass is an abundant and inexpensive resource for biofuel production. Alongside its biotechnological conversion, pretreatment is essential to enable efficient enzymatic hydrolysis by making cellulose susceptible to cellulases. Wet oxidation of biomass, such as acetone/water oxidation, that employs hot acetone, water, and oxygen, has been found to be an attractive pretreatment method for removing lignin while producing less degradation products. The remaining enriched cellulose fraction has the potential to be utilized under high gravity enzymatic saccharification and fermentation processes for the cost-competing production of bioethanol. Beech wood residual biomass was pretreated following an acetone/water oxidation process aiming at the production of high concentration of cellulosic ethanol. The effect of pressure, reaction time, temperature, and acetone-to-water ratio on the final composition of the pretreated samples was studied for the efficient utilization of the lignocellulosic feedstock. The optimal conditions were acetone/water ratio 1:1, 40 atm initial pressure of 40 vol% O 2 gas, and 64 atm at reaction temperature of 175 °C for 2 h incubation. The pretreated beech wood underwent an optimization step studying the effect of enzyme loading and solids content on the enzymatic liquefaction/saccharification prior to fermentation. In a custom designed free-fall mixer at 50 °C for either 6 or 12 h of prehydrolysis using an enzyme loading of 9 mg/g dry matter at 20 wt% initial solids content, high ethanol concentration of 75.9 g/L was obtained. The optimization of the pretreatment process allowed the efficient utilization of beech wood residual biomass for the production of high concentrations of cellulosic ethanol, while obtaining lignin that can be upgraded towards high-added-value chemicals. The threshold of 4 wt% ethanol concentration that is required for the sustainable bioethanol production was surpassed almost twofold, underpinning the efficient conversion of biomass to ethanol and bio-based chemicals on behalf of the biorefinery concept.

Kinetics and mechanism for degradation of dichlorvos by permanganate in drinking water treatment.

PubMed

Liu, Chao; Qiang, Zhimin; Adams, Craig; Tian, Fang; Zhang, Tao

2009-08-01

The degradation kinetics and mechanism of dichlorvos by permanganate during drinking water treatment were investigated. The reaction of dichlorvos with permanganate was of second-order overall with negligible pH dependence and an activation energy of 29.5 kJ x mol(-1). At pH 7.0 and 25 degrees C, the rate constant was 25.2+/-0.4M(-1)s(-1). Dichlorvos was first degraded to trimethyl phosphate (TMP) and dimethyl phosphate (DMP) simultaneously which approximately accounted for <5% and >or=95% with respect to phosphorus mass, respectively. Further oxidation of DMP generated a final byproduct, monomethyl phosphate (MMP). MMP was for the first time identified as a major byproduct in chemical oxidation of dichlorvos. The kinetic model based on degradation mechanism and determined reaction rate constants allowed us to predict the evolution of dichlorvos and its byproduct concentrations during permanganate pre-oxidation process at water treatment plants. These results suggest that even though the dichlorvos concentration in surface water complies with the surface water quality standards of China (50 microg L(-1)), its concentration after conventional water treatment will most probably exceed the drinking water quality standards (1 microg L(-1)). Moreover, luminescent bacteria test shows that the acute toxicity of dichlorvos solution evidently increased after permanganate oxidation.

Vapor-Liquid-Solid Etch of Semiconductor Surface Channels by Running Gold Nanodroplets.

PubMed

Nikoobakht, Babak; Herzing, Andrew; Muramoto, Shin; Tersoff, Jerry

2015-12-09

We show that Au nanoparticles spontaneously move across the (001) surface of InP, InAs, and GaP when heated in the presence of water vapor. As they move, the particles etch crystallographically aligned grooves into the surface. We show that this process is a negative analogue of the vapor-liquid-solid (VLS) growth of semiconductor nanowires: the semiconductor dissolves into the catalyst and reacts with water vapor at the catalyst surface to create volatile oxides, depleting the dissolved cations and anions and thus sustaining the dissolution process. This VLS etching process provides a new tool for directed assembly of structures with sublithographic dimensions, as small as a few nanometers in diameter. Au particles above 100 nm in size do not exhibit this process but remain stationary, with oxide accumulating around the particles.

Sequential continuous flow processes for the oxidation of amines and azides by using HOF·MeCN.

PubMed

McPake, Christopher B; Murray, Christopher B; Sandford, Graham

2012-02-13

The generation and use of the highly potent oxidising agent HOF·MeCN in a controlled single continuous flow process is described. Oxidations of amines and azides to corresponding nitrated systems by using fluorine gas, water and acetonitrile by sequential gas-liquid/liquid-liquid continuous flow procedures are reported. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The enhanced removal of carbonaceous and nitrogenous disinfection by-product precursors using integrated permanganate oxidation and powdered activated carbon adsorption pretreatment.

PubMed

Chu, Wenhai; Yao, Dechang; Gao, Naiyun; Bond, Tom; Templeton, Michael R

2015-12-01

Pilot-scale tests were performed to reduce the formation of a range of carbonaceous and nitrogenous disinfection by-products (C-, N-DBPs), by removing or transforming their precursors, with an integrated permanganate oxidation and powdered activated carbon adsorption (PM-PAC) treatment process before conventional water treatment processes (coagulation-sedimentation-filtration, abbreviated as CPs). Compared with the CPs, PM-PAC significantly enhanced the removal of DOC, DON, NH3(+)-N, and algae from 52.9%, 31.6%, 71.3%, and 83.6% to 69.5%, 61.3%, 92.5%, and 97.5%, respectively. PM pre-oxidation alone and PAC pre-adsorption alone did not substantially reduce the formation of dichloroacetonitrile, trichloroacetonitrile, N-nitrosodimethylamine and dichloroacetamide. However, the PM-PAC integrated process significantly reduced the formation of both C-DBPs and N-DBPs by 60-90% for six C-DBPs and 64-93% for six N-DBPs, because PM oxidation chemically altered the molecular structures of nitrogenous organic compounds and increased the adsorption capacity of the DBP precursors, thus highlighting a synergistic effect of PM and PAC. PM-PAC integrated process is a promising drinking water technology for the reduction of a broad spectrum of C-DBPs and N-DBPs. Copyright © 2015 Elsevier Ltd. All rights reserved.

Reduction-melting combined with a Na₂CO₃ flux recycling process for lead recovery from cathode ray tube funnel glass.

PubMed

Okada, Takashi; Yonezawa, Susumu

2014-08-01

With large quantity of flux (Na2CO3), lead can be recovered from the funnel glass of waste cathode-ray tubes via reduction-melting at 1000°C. To reduce flux cost, a technique to recover added flux from the generated oxide phase is also important in order to recycle the flux recovered from the reduction-melting process. In this study, the phase separation of sodium and the crystallization of water-soluble sodium silicates were induced after the reduction-melting process to enhance the leachability of sodium in the oxide phase and to extract the sodium from the phase for the recovery of Na2CO3 as flux. A reductive atmosphere promoted the phase separation and crystallization, and the leachability of sodium from the oxide phase was enhanced. The optimum temperature and treatment time for increasing the leachability were 700°C and 2h, respectively. After treatment, more than 90% of the sodium in the oxide phase was extracted in water. NaHCO3 can be recovered by carbonization of the solution containing sodium ions using carbon dioxide gas, decomposed to Na2CO3 at 50°C and recycled for use in the reduction-melting process. Copyright © 2014 Elsevier Ltd. All rights reserved.

EFFECT OF PITTING CORROSION PROMOTERS ON THE TREATMENT OF WATERS CONTAMINATED WITH A NITROAROMATIC COMPOUNDS USING INTEGRATED REDUCTIVE/OXIDATIVE PROCESSES

EPA Science Inventory

All the reaction mechanisms developed during the proposed research activities will provide essential information during risk assessment and evaluation of remediation strategies of NACs contamination. The concept of integrated reductive/oxidative technologies. exper...

Uranium dioxide electrolysis

DOEpatents

Willit, James L [Batavia, IL; Ackerman, John P [Prescott, AZ; Williamson, Mark A [Naperville, IL

2009-12-29

This is a single stage process for treating spent nuclear fuel from light water reactors. The spent nuclear fuel, uranium oxide, UO.sub.2, is added to a solution of UCl.sub.4 dissolved in molten LiCl. A carbon anode and a metallic cathode is positioned in the molten salt bath. A power source is connected to the electrodes and a voltage greater than or equal to 1.3 volts is applied to the bath. At the anode, the carbon is oxidized to form carbon dioxide and uranium chloride. At the cathode, uranium is electroplated. The uranium chloride at the cathode reacts with more uranium oxide to continue the reaction. The process may also be used with other transuranic oxides and rare earth metal oxides.

Iridium material for hydrothermal oxidation environments

DOEpatents

Hong, Glenn T.; Zilberstein, Vladimir A.

1996-01-01

A process for hydrothermal oxidation of combustible materials in which, during at least a part of the oxidation, corrosive material is present and makes contact with at least a portion of the apparatus over a contact area on the apparatus. At least a portion of the contact surface area comprises iridium, iridium oxide, an iridium alloy, or a base metal overlaid with an iridium coating. Iridium has been found to be highly resistant to environments encountered in the process of hydrothermal oxidation. Such environments typically contain greater than 50 mole percent water, together with oxygen, carbon dioxide, and a wide range of acids, bases and salts. Pressures are typically about 27.5 to about 1000 bar while temperatures range as high as 800.degree. C.

SUPERFUND TREATABILITY CLEARINGHOUSE: PCB SEDIMENT DECONTAMINATION PROCESS-SELECTION FOR TEST AND EVALUATION

EPA Science Inventory

This document is a report describing the assessment of seven alternative treatment processes that show potential for decontaminating polychlorinated biphenyl (PCB)-contaminated sediments. The processes are KPEG, MODAR Supercritical Water Oxidation, Bio-Clean, Ultrasonics/UV, C...

Numerical modelling of methane oxidation efficiency and coupled water-gas-heat reactive transfer in a sloping landfill cover.

PubMed

Feng, S; Ng, C W W; Leung, A K; Liu, H W

2017-10-01

Microbial aerobic methane oxidation in unsaturated landfill cover involves coupled water, gas and heat reactive transfer. The coupled process is complex and its influence on methane oxidation efficiency is not clear, especially in steep covers where spatial variations of water, gas and heat are significant. In this study, two-dimensional finite element numerical simulations were carried out to evaluate the performance of unsaturated sloping cover. The numerical model was calibrated using a set of flume model test data, and was then subsequently used for parametric study. A new method that considers transient changes of methane concentration during the estimation of the methane oxidation efficiency was proposed and compared against existing methods. It was found that a steeper cover had a lower oxidation efficiency due to enhanced downslope water flow, during which desaturation of soil promoted gas transport and hence landfill gas emission. This effect was magnified as the cover angle and landfill gas generation rate at the bottom of the cover increased. Assuming the steady-state methane concentration in a cover would result in a non-conservative overestimation of oxidation efficiency, especially when a steep cover was subjected to rainfall infiltration. By considering the transient methane concentration, the newly-modified method can give a more accurate oxidation efficiency. Copyright © 2017. Published by Elsevier Ltd.

Positive and negative electrospray ionization analyses of the organic fractions in raw and oxidized oil sands process-affected water.

PubMed

Wang, Chengjin; Huang, Rongfu; Klamerth, Nikolaus; Chelme-Ayala, Pamela; Gamal El-Din, Mohamed

2016-12-01

This work investigated the oxidative transformation of the organic species in oil sands process-affected water (OSPW) using Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS) and ultra-performance liquid chromatography time-of-flight mass spectrometry (UPLC-TOF-MS) in both negative and positive electrospray ionization (ESI) modes. This is the first time to apply FTICR-MS to investigate species transformation in OSPW treatments by ferrate (VI), UV/H 2 O 2 , and molecular ozone, and also this is the first preliminary study to use positive ESI to investigate organic species in addition to naphthenic acids (NAs) in these treatment processes. The oxidation processes with potassium ferrate (VI), UV/H 2 O 2 , and ozone transformed the distribution profiles of O x , O x S y , and O x N y organic fractions (i.e., species containing oxygen, sulfur, and nitrogen, with x, y specifying the oxygen number and sulfur/nitrogen number, respectively), with O x S y distribution profiles showing the most sensitive responses to the oxidation extent and can be used as a signature fraction to evaluate the oxidation effectiveness. Negative mode UPLC-TOF-MS confirmed the transformation pattern of O x species observed with FTICR-MS, but positive mode UPLC-TOF-MS results showed severe discrepancies with FTICR-MS results and should be subjected for future further investigation, regarding the relatively low mass resolution of UPLC-TOF-MS. The investigation of the transformation patterns of different organic species using two ionization modes was a preliminary study to enhance the understanding of the efficiency, selectivity, and mechanism of different oxidation processes in OSPW remediation for both NAs and non-NA species. Copyright © 2016 Elsevier Ltd. All rights reserved.

Process for making a noble metal on tin oxide catalyst

NASA Technical Reports Server (NTRS)

Upchurch, Billy T. (Inventor); Davis, Patricia (Inventor); Miller, Irvin M. (Inventor)

1989-01-01

A quantity of reagent grade tin metal or compound, chloride-free, and high-surface-area silica spheres are placed in deionized water, followed by deaerating the mixture by boiling and adding an oxidizing agent, such as nitric acid. The nitric acid oxidizes the tin to metastannic acid which coats the spheres because the acid is absorbed on the substrate. The metastannic acid becomes tin oxide upon drying and calcining. The tin-oxide coated silica spheres are then placed in water and boiled. A chloride-free precious metal compound in aqueous solution is then added to the mixture containing the spheres, and the precious metal compound is reduced to a precious metal by use of a suitable reducing agent such as formic acid. Very beneficial results were obtained using the precious metal compound tetraammine platinum(II) hydroxide.

A hybrid water-splitting cycle using copper sulfate and mixed copper oxides

NASA Technical Reports Server (NTRS)

Schreiber, J. D.; Remick, R. J.; Foh, S. E.; Mazumder, M. M.

1980-01-01

The Institute of Gas Technology has derived and developed a hybrid thermochemical water-splitting cycle based on mixed copper oxides and copper sulfate. Similar to other metal oxide-metal sulfate cycles that use a metal oxide to 'concentrate' electrolytically produced sulfuric acid, this cycle offers the advantage of producing oxygen (to be vented) and sulfur dioxide (to be recycled) in separate steps, thereby eliminating the need of another step to separate these gases. The conceptual process flow-sheet efficiency of the cycle promises to exceed 50%. It has been completely demonstrated in the laboratory with recycled materials. Research in the electrochemical oxidation of sulfur dioxide to produce sulfuric acid and hydrogen performed at IGT indicates that the cell performance goals of 200 mA/sq cm at 0.5 V will be attainable using relatively inexpensive electrode materials.

Oxidation of microcystins by permanganate: reaction kinetics and implications for water treatment.

PubMed

Rodríguez, Eva; Majado, María E; Meriluoto, Jussi; Acero, Juan L

2007-01-01

A few genera of cyanobacteria produce toxins which contaminate drinking water resources. Microcystins (MC), widely reported cyanotoxins, cause acute and chronic toxicity effects in living beings including humans and warrant removal from drinking water. In the present study, unknown second-order rate constants for the reactions of microcystin-LR (MC-LR), -RR and -YR with potassium permanganate were determined at pH 6.2-8.2 and temperature 10-25 degrees C. The reaction of permanganate with MCs is second-order overall and first-order with respect to both permanganate and toxin. The second-order rate constant for the reaction of MC-LR with permanganate at pH 7 and 20 degrees C was 357.2+/-17.5M(-1)s(-1). The influence of pH on the oxidation process was not appreciable and the activation energy was 28.8 kJ mol(-1). Slightly higher reactivity with permanganate was found for MC-RR (418.0M(-1)s(-1)) and MC-YR (405.9M(-1)s(-1)). According to the results obtained, permanganate likely attacks the Adda moiety of the MC molecule. The oxidation of MCs in a natural surface water was also investigated. A permanganate dose of 1-1.25mgL(-1) was enough to reduce MCs concentration below the guideline value of 1microgL(-1). Permanganate oxidation is therefore a feasible option for microcystin removal during preoxidation processes. However, the oxidant dose must be carefully optimized in order to remove extracellular MCs without causing cell lysis (due to chemical stress) and further release of MCs.

Evaluation of potassium ferrate as an alternative disinfectant on cyanobacteria inactivation and associated toxin fate in various waters.

PubMed

Fan, Jiajia; Lin, Bo-Hung; Chang, Che-Wei; Zhang, Yuqing; Lin, Tsair-Fuh

2018-02-01

Potassium ferrate (K 2 FeO 4 ) is an effective oxidant that may be used as a pre- or post-oxidant in the purification of source water with cyanobacterial issues. To provide a better basis for the application of this oxidant during water treatment processes, the impacts of K 2 FeO 4 on the cell viability of Microcystis aeruginosa and the fate of associated microcystins (MCs) were investigated in various water matrices. The results showed that a water matrix can significantly affect the effectiveness of K 2 FeO 4 on cyanobacteria inactivation. 10 mg L -1 K 2 FeO 4 induced significant cell lysis of M. aeruginosa in Ran Yi Tan Reservoir (RYTR) water while the membrane integrity was relatively unaffected in ASM-1 media and Cheng Kung Lake (CKL) water. The reduced efficiency of K 2 FeO 4 oxidation may be attributed to the manganese (Mn 2+ ) and organic matter (Ethylenediaminetetraacetic acid, EDTA) in the ASM-1 media and high concentrations of natural organic matters (NOMs) in the CKL water. A delayed Chick-Watson model was applied to simulate the experimental data for cyanobacterial cell rupture, and the cell lysis rates of the M. aeruginosa samples were determined to be 128-242 M -1  s -1 (mol L -1  s -1 ). Generally, no significant increases in extracellular MCs were observed in the three different waters, even in the RYTR water where the membrane integrity of the cyanobacterial cells was severely disrupted. Therefore, K 2 FeO 4 could be a potential pre-oxidant to enhance subsequent treatments for cyanobacteria removal without affecting the cell integrity, or could serve as a post-oxidant to inactivate cyanobacterial cells and degrade MCs effectively, depending on the specific water matrix. Copyright © 2017 Elsevier Ltd. All rights reserved.

Arsenic removal from water by coupling photocatalysis and complexation-ultrafiltration processes: A preliminary study.

PubMed

Molinari, R; Argurio, P

2017-02-01

Inorganic As removal from contaminated water has been studied by off-line coupling of photocatalysis and complexation-ultrafiltration (CP-UF), showing that this combination permits to obtain a quite complete arsenic removal from the treated water. Two commercial polymers, poly(dimethylamine-coepichlorohydrin-coethylenediamine) (PDEHED) and poly(diallyl dimethyl amnmonium chloride) (PolyDADMAC) have been tested in the CP-UF process. The operating conditions (pH and polymer/As weight ratio) for As(V) complexation were determined finding values of 7.5/20 and 9.2/30 for PDEHED and polyDADMAC, respectively. The UF tests were performed by continuous diafiltration and diafiltration with volume reduction modes. The latter method permits to save the volume of washing solution during polymer regeneration. As(III) was not complexed, operating under the As(V) complexation conditions, thus a pre-oxidation step by using the photocatalytic approach was carried out to remove As(III) species. As(III) conversion to As(V) was evaluated by As speciation by using the CP-UF process for analytical purposes. Photocatalytic oxidation was successfully performed under UV radiation by using TiO 2 (0.05 mg L -1 ), O 2 and pH = 9. The oxidation was very fast during the first 10 min following a zero order kinetics (k = 0.83 mg L -1  min -1 ) and reaching 90% As(III) oxidation. A conceptual scheme coupling photocatalysis and CP-UF and some criteria to operate the CP-UF process, useful to address it towards application, are reported. Copyright © 2016 Elsevier Ltd. All rights reserved.

Technologies for deposition of transition metal oxide thin films: application as functional layers in “Smart windows” and photocatalytic systems

NASA Astrophysics Data System (ADS)

Gesheva, K.; Ivanova, T.; Bodurov, G.; Szilágyi, I. M.; Justh, N.; Kéri, O.; Boyadjiev, S.; Nagy, D.; Aleksandrova, M.

2016-02-01

“Smart windows” are envisaged for future low-energy, high-efficient architectural buildings, as well as for the car industry. By switching from coloured to fully bleached state, these windows regulate the energy of solar flux entering the interior. Functional layers in these devices are the transition metals oxides. The materials (transitional metal oxides) used in smart windows can be also applied as photoelectrodes in water splitting photocells for hydrogen production or as photocatalytic materials for self-cleaning surfaces, waste water treatment and pollution removal. Solar energy utilization is recently in the main scope of numerous world research laboratories and energy organizations, working on protection against conventional fuel exhaustion. The paper presents results from research on transition metal oxide thin films, fabricated by different methods - atomic layer deposition, atmospheric pressure chemical vapour deposition, physical vapour deposition, and wet chemical methods, suitable for flowthrough production process. The lower price of the chemical deposition processes is especially important when the method is related to large-scale glazing applications. Conclusions are derived about which processes are recently considered as most prospective, related to electrochromic materials and devices manufacturing.

Methane oxidation coupled to oxygenic photosynthesis in anoxic waters

PubMed Central

Milucka, Jana; Kirf, Mathias; Lu, Lu; Krupke, Andreas; Lam, Phyllis; Littmann, Sten; Kuypers, Marcel MM; Schubert, Carsten J

2015-01-01

Freshwater lakes represent large methane sources that, in contrast to the Ocean, significantly contribute to non-anthropogenic methane emissions to the atmosphere. Particularly mixed lakes are major methane emitters, while permanently and seasonally stratified lakes with anoxic bottom waters are often characterized by strongly reduced methane emissions. The causes for this reduced methane flux from anoxic lake waters are not fully understood. Here we identified the microorganisms and processes responsible for the near complete consumption of methane in the anoxic waters of a permanently stratified lake, Lago di Cadagno. Interestingly, known anaerobic methanotrophs could not be detected in these waters. Instead, we found abundant gamma-proteobacterial aerobic methane-oxidizing bacteria active in the anoxic waters. In vitro incubations revealed that, among all the tested potential electron acceptors, only the addition of oxygen enhanced the rates of methane oxidation. An equally pronounced stimulation was also observed when the anoxic water samples were incubated in the light. Our combined results from molecular, biogeochemical and single-cell analyses indicate that methane removal at the anoxic chemocline of Lago di Cadagno is due to true aerobic oxidation of methane fuelled by in situ oxygen production by photosynthetic algae. A similar mechanism could be active in seasonally stratified lakes and marine basins such as the Black Sea, where light penetrates to the anoxic chemocline. Given the widespread occurrence of seasonally stratified anoxic lakes, aerobic methane oxidation coupled to oxygenic photosynthesis might have an important but so far neglected role in methane emissions from lakes. PMID:25679533

Biofilms and Oxidizing Biocides; Evaluation of Disinfection and Removal Effects by Using Established Microbial Systems.

PubMed

Tachikawa, Mariko

2017-01-01

The formation of bacterial biofilms and their disinfection and removal have been important subjects in the maintenance of water quality in areas such as public spas, swimming pools, food processing lines, industrial water systems, and in the hygienic control of medical devices, hospital procedures, etc. Presented here is an outline of biofilm formation, as well as studies on the disinfection and removal of biofilms by oxidizing biocides using established biofilms. These studies using established biofilms may increase the understanding of the variable response of biofilms to planktonic bacteria, and the unique aspects of oxidizing biocides in the disinfection and removal of biofilms.

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

Lombardo, N.J.; Marseille, T.J.; White, M.D.

TRUMP-BD (Boil Down) is an extension of the TRUMP (Edwards 1972) computer program for the analysis of nuclear fuel assemblies under severe accident conditions. This extension allows prediction of the heat transfer rates, metal-water oxidation rates, fission product release rates, steam generation and consumption rates, and temperature distributions for nuclear fuel assemblies under core uncovery conditions. The heat transfer processes include conduction in solid structures, convection across fluid-solid boundaries, and radiation between interacting surfaces. Metal-water reaction kinetics are modeled with empirical relationships to predict the oxidation rates of steam-exposed Zircaloy and uranium metal. The metal-water oxidation models are parabolic inmore » form with an Arrhenius temperature dependence. Uranium oxidation begins when fuel cladding failure occurs; Zircaloy oxidation occurs continuously at temperatures above 13000{degree}F when metal and steam are available. From the metal-water reactions, the hydrogen generation rate, total hydrogen release, and temporal and spatial distribution of oxide formations are computed. Consumption of steam from the oxidation reactions and the effect of hydrogen on the coolant properties is modeled for independent coolant flow channels. Fission product release from exposed uranium metal Zircaloy-clad fuel is modeled using empirical time and temperature relationships that consider the release to be subject to oxidation and volitization/diffusion ( bake-out'') release mechanisms. Release of the volatile species of iodine (I), tellurium (Te), cesium (Ce), ruthenium (Ru), strontium (Sr), zirconium (Zr), cerium (Cr), and barium (Ba) from uranium metal fuel may be modeled.« less

Catalyst for Oxidation of Volatile Organic Compounds

NASA Technical Reports Server (NTRS)

Wood, George M. (Inventor); Upchurch, Billy T. (Inventor); Schryer, David R. (Inventor); Davis, Patricia P. (Inventor); Kielin, Erik J. (Inventor); Brown, Kenneth G. (Inventor); Schyryer, Jacqueline L. (Inventor); DAmbrosia, Christine M. (Inventor)

2000-01-01

Disclosed is a process for oxidizing volatile organic compounds to carbon dioxide and water with the minimal addition of energy. A mixture of the volatile organic compound and an oxidizing agent (e.g. ambient air containing the volatile organic compound) is exposed to a catalyst which includes a noble metal dispersed on a metal oxide which possesses more than one oxidation state. Especially good results are obtained when the noble metal is platinum, and the metal oxide which possesses more than one oxidation state is tin oxide. A promoter (i.e., a small amount of an oxide of a transition series metal) may be used in association with the tin oxide to provide very beneficial results.

Sol-gel zinc oxide humidity sensors integrated with a ring oscillator circuit on-a-chip.

PubMed

Yang, Ming-Zhi; Dai, Ching-Liang; Wu, Chyan-Chyi

2014-10-28

The study develops an integrated humidity microsensor fabricated using the commercial 0.18 μm complementary metal oxide semiconductor (CMOS) process. The integrated humidity sensor consists of a humidity sensor and a ring oscillator circuit on-a-chip. The humidity sensor is composed of a sensitive film and branch interdigitated electrodes. The sensitive film is zinc oxide prepared by sol-gel method. After completion of the CMOS process, the sensor requires a post-process to remove the sacrificial oxide layer and to coat the zinc oxide film on the interdigitated electrodes. The capacitance of the sensor changes when the sensitive film adsorbs water vapor. The circuit is used to convert the capacitance of the humidity sensor into the oscillation frequency output. Experimental results show that the output frequency of the sensor changes from 84.3 to 73.4 MHz at 30 °C as the humidity increases 40 to 90%RH.

Treatment of high salt oxidized modified starch waste water using micro-electrolysis, two-phase anaerobic aerobic and electrolysis for reuse

NASA Astrophysics Data System (ADS)

Yi, Xuenong; Wang, Yulin

2017-06-01

A combined process of micro-electrolysis, two-phase anaerobic, aerobic and electrolysis was investigated for the treatment of oxidized modified starch wastewater (OMSW). Optimum ranges for important operating variables were experimentally determined and the treated water was tested for reuse in the production process of corn starch. The optimum hydraulic retention time (HRT) of micro-electrolysis, methanation reactor, aerobic process and electrolysis process were 5, 24, 12 and 3 h, respectively. The addition of iron-carbon fillers to the acidification reactor was 200 mg/L while the best current density of electrolysis was 300 A/m2. The biodegradability was improved from 0.12 to 0.34 by micro-electrolysis. The whole treatment was found to be effective with removal of 96 % of the chemical oxygen demand (COD), 0.71 L/day of methane energy recovery. In addition, active chlorine production (15,720 mg/L) was obtained by electrolysis. The advantage of this hybrid process is that, through appropriate control of reaction conditions, effect from high concentration of salt on the treatment was avoided. Moreover, the process also produced the material needed in the production of oxidized starch while remaining emission-free and solved the problem of high process cost.

Occurrence and Removal of Organic Micropollutants in Landfill Leachates Treated by Electrochemical Advanced Oxidation Processes.

PubMed

Oturan, Nihal; van Hullebusch, Eric D; Zhang, Hui; Mazeas, Laurent; Budzinski, Hélène; Le Menach, Karyn; Oturan, Mehmet A

2015-10-20

In recent years, electrochemical advanced oxidation processes have been shown to be an effective alternative for the removal of refractory organic compounds from water. This study is focused on the effective removal of recalcitrant organic matter (micropollutants, humic substances, etc.) present in municipal solid waste landfill leachates. A mixture of eight landfill leachates has been studied by the electro-Fenton process using a Pt or boron-doped diamond (BDD) anode and a carbon felt cathode or by the anodic oxidation process with a BDD anode. These processes exhibit great oxidation ability due to the in situ production of hydroxyl radicals ((•)OH), a highly powerful oxidizing species. Both electrochemical processes were shown to be efficient in the removal of dissolved total organic carbon (TOC) from landfill leachates. Regarding the electro-Fenton process, the replacement of the classical anode Pt by the anode BDD allows better performance in terms of dissolved TOC removal. The occurrence and removal yield of 19 polycyclic aromatic hydrocarbons, 15 volatile organic compounds, 7 alkylphenols, 7 polychlorobiphenyls, 5 organochlorine pesticides, and 2 polybrominated diphenyl ethers in landfill leachate were also investigated. Both electrochemical processes allow one to reach a quasicomplete removal (about 98%) of these organic micropollutants.

Catechol Removal from Aqueous Media Using Laccase Immobilized in Different Macro- and Microreactor Systems.

PubMed

Tušek, Ana Jurinjak; Šalić, Anita; Zelić, Bruno

2017-08-01

Laccase belongs to the group of enzymes that are capable to catalyze the oxidation of phenols. Since the water is only by-product in laccase-catalyzed phenol oxidations, it is ideally "green" enzyme with many possible applications in different industrial processes. To make the oxidation process more sustainable in terms of biocatalyst consumption, immobilization of the enzyme is implemented in to the processes. Additionally, when developing a process, choice of a reactor type plays a significant role in the total outcome.In this study, the use of immobilized laccase from Trametes versicolor for biocatalytic catechol oxidation was explored. Two different methods of immobilization were performed and compared using five different reactor types. In order to compare different systems used for catechol oxidation, biocatalyst turnover number and turnover frequency were calculated. With low consumption of the enzyme and good efficiency, obtained results go in favor of microreactors with enzyme covalently immobilized on the microchannel surface.

Electropulse treatment of water solution of humic substances in a layer iron granules in process of water treatment

NASA Astrophysics Data System (ADS)

Lobanova, G. L.; Yurmazova, T. A.; Shiyan, L. N.; Machekhina, K. I.

2016-02-01

The present work is a part of a continuations study of the physical and chemical processes complex in natural waters containing humic-type organic substances at the influence of pulsed electrical discharges in a layer of iron pellets. The study of humic substances processing in the iron granules layer by means of pulsed electric discharge for the purpose of water purification from organic compounds humic origin from natural water of the northern regions of Russia is relevant for the water treatment technologies. In case of molar humate sodium - iron ions (II) at the ratio 2:3, reduction of solution colour and chemical oxygen demand occur due to the humate sodium ions and iron (II) participation in oxidation-reduction reactions followed by coagulation insoluble compounds formation at a pH of 6.5. In order to achieve this molar ratio and the time of pulsed electric discharge, equal to 10 seconds is experimentally identified. The role of secondary processes that occur after disconnection of the discharge is shown. The time of contact in active erosion products with sodium humate, equal to 1 hour is established. During this time, the value of permanganate oxidation and iron concentration in solution achieves the value of maximum permissible concentrations and further contact time increase does not lead to the controlled parameters change.

Water quality assessment using the AREc32 reporter gene assay indicative of the oxidative stress response pathway.

PubMed

Escher, Beate I; Dutt, Mriga; Maylin, Erin; Tang, Janet Y M; Toze, Simon; Wolf, C Roland; Lang, Matti

2012-11-01

The reporter gene assay AREc32 is based on the induction of the Nrf2 mediated oxidative stress response pathway in the human breast cancer cell line MCF7, where eight copies of the antioxidant response element (ARE) are linked to a reporter gene encoding for luciferase. The Nrf2-ARE pathway is responsive to many chemicals that cause oxidative stress, among them a large number of pesticides and skin irritants. We adopted and validated the AREc32 bioassay for water quality testing. tert-Butylhydroquinone served as the positive control, phenol as the negative control and other reactive chemicals were assessed for their specificity. An environmentally relevant reference chemical, benzo(a)pyrene was the most potent inducer of all tested chemicals. The concentration causing an induction ratio (IR) of 1.5 (EC(IR1.5)) was chosen as the effect benchmark value. The assay was applied to 21 water samples ranging from sewage to drinking water, including secondary treatment and various tertiary treatment options (ozonation, biologically activated carbon filtration, membrane filtration, reverse osmosis, advanced oxidation, chlorination, chloramination). The samples were enriched by solid phase extraction. In most samples the oxidative stress response was far more sensitive than cytotoxicity. The primary and secondary treated effluent exceeded the effect threshold IR 1.5 at a relative enrichment factor (REF) of 1, i.e., the native samples were active. All tertiary treated samples were less potent and their EC(IR1.5) lay between REF 1 and 10. The Nrf2 pathway was induced at a REF of approximately 10 for surface waters and drinking water, and above this enrichment cytotoxicity took over in most samples and quenched the induction. The blank (ultrapure water run through the sample enrichment process) was cytotoxic at an REF of 100, which is the limit of concentrations range that can be evaluated. Treatment typically decreased both the cytotoxicity and oxidative stress response apart from drinking water treatment where chlorination caused an increase in oxidative stress response, presumably due to the formation of disinfection by-products. This study demonstrates the relevance and applicability of the oxidative stress response pathway for water quality monitoring.

Static and Dynamic Water Motion-Induced Instability in Oxide Thin-Film Transistors and Its Suppression by Using Low-k Fluoropolymer Passivation.

PubMed

Choi, Seungbeom; Jo, Jeong-Wan; Kim, Jaeyoung; Song, Seungho; Kim, Jaekyun; Park, Sung Kyu; Kim, Yong-Hoon

2017-08-09

Here, we report static and dynamic water motion-induced instability in indium-gallium-zinc-oxide (IGZO) thin-film transistors (TFTs) and its effective suppression with the use of a simple, solution-processed low-k (ε ∼ 1.9) fluoroplastic resin (FPR) passivation layer. The liquid-contact electrification effect, in which an undesirable drain current modulation is induced by a dynamic motion of a charged liquid such as water, can cause a significant instability in IGZO TFTs. It was found that by adopting a thin (∼44 nm) FPR passivation layer for IGZO TFTs, the current modulation induced by the water-contact electrification was greatly reduced in both off- and on-states of the device. In addition, the FPR-passivated IGZO TFTs exhibited an excellent stability to static water exposure (a threshold voltage shift of +0.8 V upon 3600 s of water soaking), which is attributed to the hydrophobicity of the FPR passivation layer. Here, we discuss the origin of the current instability caused by the liquid-contact electrification as well as various static and dynamic stability tests for IGZO TFTs. On the basis of our findings, we believe that the use of a thin, solution-processed FPR passivation layer is effective in suppressing the static and dynamic water motion-induced instabilities, which may enable the realization of high-performance and environment-stable oxide TFTs for emerging wearable and skin-like electronics.

EVALUATION OF A PILOT-SCALE ULTRAVIOLET (UV) LIGHT AND OZONE TREATMENT SYSTEM FOR REMOVAL OF MTBE FROM DRINKING WATER SOURCES

EPA Science Inventory

The U.S. Environmental Protection Agency (EPA) is currently evaluating package plant advanced oxidation process (AOP) systems to treat methyl tertiary butyl ether (MTBE) in drinking water supplies (e.g., surface water, groundwater). MTBE has been identified as a potential carcin...

Orientation-dependent hydration structures at yttria-stabilized cubic zirconia surfaces

DOE PAGES

Hou, Binyang; Kim, Seunghyun; Kim, Taeho; ...

2016-11-30

Water interaction with surfaces is very important and plays key roles in many natural and technological processes. Because the experimental challenges that arise when studying the interaction water with specific crystalline surfaces, most studies on metal oxides have focused on powder samples, which averaged the interaction over different crystalline surfaces. As a result, studies on the crystal orientation-dependent interaction of water with metal oxides are rarely available in the literature. In this work, water adsorption at 8 mol % yttria-stabilized cubic single crystal zirconia (100) and (111) surfaces was studied in terms of interfacial hydration structures using high resolution X-raymore » reflectivity measurements. The interfacial electron density profiles derived from the structure factor analysis of the measured data show the existence of multiple layers of adsorbed water with additional peculiar metal adsorption near the oxide surfaces.Surface relaxation, depletion, and interaction between the adsorbed layers and bulk water are found to vary greatly between the two surfaces and are also different when compared to the previously studied (110) surface. The fractional ratio between chemisorbed and physisorbed water species were also quantitatively estimated, which turned out to vary dramatically from surface to surface. Finally, the result gives us a unique opportunity to reconsider the simplified 2:1 relation between chemisorption and physisorption, originally proposed by Morimoto et al. based on the adsorption isotherms of water on powder metal oxide samples.« less

Engineering aspects of rate-related processes in food manufacturing.

PubMed

Adachi, Shuji

2015-01-01

Many rate-related phenomena occur in food manufacturing processes. This review addresses four of them, all of which are topics that the author has studied in order to design food manufacturing processes that are favorable from the standpoint of food engineering. They include chromatographic separation through continuous separation with a simulated moving adsorber, lipid oxidation kinetics in emulsions and microencapsulated systems, kinetic analysis and extraction in subcritical water, and water migration in pasta.

Hydrogen production by the decomposition of water

DOEpatents

Hollabaugh, Charles M.; Bowman, Melvin G.

1981-01-01

How to produce hydrogen from water was a problem addressed by this invention. The solution employs a combined electrolytical-thermochemical sulfuric acid process. Additionally, high purity sulfuric acid can be produced in the process. Water and SO.sub.2 react in electrolyzer (12) so that hydrogen is produced at the cathode and sulfuric acid is produced at the anode. Then the sulfuric acid is reacted with a particular compound M.sub.r X.sub.s so as to form at least one water insoluble sulfate and at least one water insoluble oxide of molybdenum, tungsten, or boron. Water is removed by filtration; and the sulfate is decomposed in the presence of the oxide in sulfate decomposition zone (21), thus forming SO.sub.3 and reforming M.sub.r X.sub.s. The M.sub.r X.sub.s is recycled to sulfate formation zone (16). If desired, the SO.sub.3 can be decomposed to SO.sub.2 and O.sub.2 ; and the SO.sub.2 can be recycled to electrolyzer (12) to provide a cycle for producing hydrogen.

Study of the possibility of thermal utilization of contaminated water in low-power boilers

NASA Astrophysics Data System (ADS)

Roslyakov, P. V.; Proskurin, Y. V.; Zaichenko, M. N.

2017-09-01

The utilization of water contaminated with oil products is a topical problem for thermal power plants and boiler houses. It is reasonable to use special water treatment equipment only for large power engineering and industry facilities. Thermal utilization of contaminated water in boiler furnaces is proposed as an alternative version of its utilization. Since there are hot-water fire-tube boilers at many enterprises, it is necessary to study the possibility of thermal utilization of water contaminated with oil products in their furnaces. The object of this study is a KV-GM-2.0 boiler with a heating power of 2 MW. The pressurized burner developed at the Moscow Power Engineering Institute, National Research University, was used as a burner device for supplying liquid fuel. The computational investigations were performed on the basis of the computer simulation of processes of liquid fuel atomization, mixing, ignition, and burnout; in addition, the formation of nitrogen oxides was simulated on the basis of ANSYS Fluent computational dynamics software packages, taking into account radiative and convective heat transfer. Analysis of the results of numerical experiments on the combined supply of crude oil and water contaminated with oil products has shown that the thermal utilization of contaminated water in fire-tube boilers cannot be recommended. The main causes here are the impingement of oil droplets on the walls of the flame tube, as well as the delay in combustion and increased emissions of nitrogen oxides. The thermal utilization of contaminated water combined with diesel fuel can be arranged provided that the water consumption is not more than 3%; however, this increases the emission of nitrogen oxides. The further increase in contaminated water consumption will lead to the reduction of the reliability of the combustion process.

Water-assisted growth of graphene-carbon nanotube hybrids in plasma

NASA Astrophysics Data System (ADS)

Tewari, Aarti; Ghosh, Santanu; Srivastava, Pankaj

2018-04-01

The enhanced growth of graphene-carbon nanotube (CNT) hybrids in a hydrocarbon and hydrogen plasma assisted by water is numerically formulated. The catalyst activity and agglomeration of catalyst particles are the rate determining factors in the growth of hybrids and their constituents, i.e., the CNT and graphene. The water vapor concentration is varied to investigate its effect on the growth process. The enhanced catalyst activity on account of oxidation by hydroxyl ions of water to impede the agglomeration of catalyst particles and the removal of amorphous carbon through etching by hydrogen ions of water are seen to be the main driving forces behind the many fold increase in the dimensions of constituent nanostructures and the hybrids with water vapor concentration. Importantly, beyond a certain specific water vapor concentration, the growth rates dropped due to active oxidation of the catalyst particle.

Adsorption of dodecylamine hydrochloride on graphene oxide in water

NASA Astrophysics Data System (ADS)

Chen, Peng; Li, Hongqiang; Song, Shaoxian; Weng, Xiaoqing; He, Dongsheng; Zhao, Yunliang

Cationic surfactants in water are difficult to be degraded, leading to serious water pollution. In this work, graphene oxide (GO) was used as an adsorbent for removing Dodecylamine Hydrochloride (DACl), a representative cationic surfactant. X-ray diffraction (XRD), FT-IR spectroscopy and atomic force microscope (AFM) were used to characterize the prepared GO. The adsorption of DACl on GO have been investigated through measurements of adsorption capacity, zeta potential, FTIR, and X-ray photoelectron spectroscopy (XPS). The experimental results have shown that the adsorption kinetics could be described as a rate-limiting pseudo second-order process, and the adsorption isotherm agreed well with the Freundlich model. GO was a good adsorbent for DACl removal, compared with coal fly ash and powdered activated carbon. The adsorption process was endothermic, and could be attributed to electrostatic interaction and hydrogen bonding between DACl and GO.

Low-Temperature, Solution-Processed, Transparent Zinc Oxide-Based Thin-Film Transistors for Sensing Various Solvents

PubMed Central

You, Hsin-Chiang; Wang, Cheng-Jyun

2017-01-01

A low temperature solution-processed thin-film transistor (TFT) using zinc oxide (ZnO) film as an exposed sensing semiconductor channel was fabricated to detect and identify various solution solvents. The TFT devices would offer applications for low-cost, rapid and highly compatible water-soluble detection and could replace conventional silicon field effect transistors (FETs) as bio-sensors. In this work, we demonstrate the utility of the TFT ZnO channel to sense various liquids, such as polar solvents (ethanol), non-polar solvents (toluene) and deionized (DI) water, which were dropped and adsorbed onto the channel. It is discussed how different dielectric constants of polar/non-polar solvents and DI water were associated with various charge transport properties, demonstrating the main detection mechanisms of the thin-film transistor. PMID:28772592

Compositional evolution of particle-phase reaction products and water in the heterogeneous OH oxidation of model aqueous organic aerosols

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

Chim, Man Mei; Cheng, Chiu Tung; Davies, James F.

Organic compounds present at or near the surface of aqueous droplets can be efficiently oxidized by gas-phase OH radicals, which alter the molecular distribution of the reaction products within the droplet. A change in aerosol composition affects the hygroscopicity and leads to a concomitant response in the equilibrium amount of particle-phase water. The variation in the aerosol water content affects the aerosol size and physicochemical properties, which in turn governs the oxidation kinetics and chemistry. To attain better knowledge of the compositional evolution of aqueous organic droplets during oxidation, this work investigates the heterogeneous OH-radical-initiated oxidation of aqueous methylsuccinic acid (C 5Hmore » 8O 4) droplets, a model compound for small branched dicarboxylic acids found in atmospheric aerosols, at a high relative humidity of 85 % through experimental and modeling approaches. Aerosol mass spectra measured by a soft atmospheric pressure ionization source (Direct Analysis in Real Time, DART) coupled with a high-resolution mass spectrometer reveal two major products: a five carbon atom (C 5) hydroxyl functionalization product (C 5H 8O 5) and a C 4 fragmentation product (C 4H 6O 3). These two products likely originate from the formation and subsequent reactions (intermolecular hydrogen abstraction and carbon–carbon bond scission) of tertiary alkoxy radicals resulting from the OH abstraction occurring at the methyl-substituted carbon site. Based on the identification of the reaction products, a kinetic model of oxidation (a two-product model) coupled with the Aerosol Inorganic–Organic Mixtures Functional groups Activity Coefficients (AIOMFAC) model is built to simulate the size and compositional changes of aqueous methylsuccinic acid droplets during oxidation. Model results show that at the maximum OH exposure, the droplets become slightly more hygroscopic after oxidation, as the mass fraction of water is predicted to increase from 0.362 to 0.424; however, the diameter of the droplets decreases by 6.1 %. This can be attributed to the formation of volatile fragmentation products that partition to the gas phase, leading to a net loss of organic species and associated particle-phase water, and thus a smaller droplet size. Overall, fragmentation and volatilization processes play a larger role than the functionalization process in determining the evolution of aerosol water content and droplet size at high-oxidation stages.« less

Compositional evolution of particle-phase reaction products and water in the heterogeneous OH oxidation of model aqueous organic aerosols

DOE PAGES

Chim, Man Mei; Cheng, Chiu Tung; Davies, James F.; ...

2017-12-05

Organic compounds present at or near the surface of aqueous droplets can be efficiently oxidized by gas-phase OH radicals, which alter the molecular distribution of the reaction products within the droplet. A change in aerosol composition affects the hygroscopicity and leads to a concomitant response in the equilibrium amount of particle-phase water. The variation in the aerosol water content affects the aerosol size and physicochemical properties, which in turn governs the oxidation kinetics and chemistry. To attain better knowledge of the compositional evolution of aqueous organic droplets during oxidation, this work investigates the heterogeneous OH-radical-initiated oxidation of aqueous methylsuccinic acid (C 5Hmore » 8O 4) droplets, a model compound for small branched dicarboxylic acids found in atmospheric aerosols, at a high relative humidity of 85 % through experimental and modeling approaches. Aerosol mass spectra measured by a soft atmospheric pressure ionization source (Direct Analysis in Real Time, DART) coupled with a high-resolution mass spectrometer reveal two major products: a five carbon atom (C 5) hydroxyl functionalization product (C 5H 8O 5) and a C 4 fragmentation product (C 4H 6O 3). These two products likely originate from the formation and subsequent reactions (intermolecular hydrogen abstraction and carbon–carbon bond scission) of tertiary alkoxy radicals resulting from the OH abstraction occurring at the methyl-substituted carbon site. Based on the identification of the reaction products, a kinetic model of oxidation (a two-product model) coupled with the Aerosol Inorganic–Organic Mixtures Functional groups Activity Coefficients (AIOMFAC) model is built to simulate the size and compositional changes of aqueous methylsuccinic acid droplets during oxidation. Model results show that at the maximum OH exposure, the droplets become slightly more hygroscopic after oxidation, as the mass fraction of water is predicted to increase from 0.362 to 0.424; however, the diameter of the droplets decreases by 6.1 %. This can be attributed to the formation of volatile fragmentation products that partition to the gas phase, leading to a net loss of organic species and associated particle-phase water, and thus a smaller droplet size. Overall, fragmentation and volatilization processes play a larger role than the functionalization process in determining the evolution of aerosol water content and droplet size at high-oxidation stages.« less

Relationship between reaction rate constants of organic pollutants and their molecular descriptors during Fenton oxidation and in situ formed ferric-oxyhydroxides.

PubMed

Jia, Lijuan; Shen, Zhemin; Su, Pingru

2016-05-01

Fenton oxidation is a promising water treatment method to degrade organic pollutants. In this study, 30 different organic compounds were selected and their reaction rate constants (k) were determined for the Fenton oxidation process. Gaussian09 and Material Studio software sets were used to carry out calculations and obtain values of 10 different molecular descriptors for each studied compound. Ferric-oxyhydroxide coagulation experiments were conducted to determine the coagulation percentage. Based upon the adsorption capacity, all of the investigated organic compounds were divided into two groups (Group A and Group B). The percentage adsorption of organic compounds in Group A was less than 15% (wt./wt.) and that in the Group B was higher than 15% (wt./wt.). For Group A, removal of the compounds by oxidation was the dominant process while for Group B, removal by both oxidation and coagulation (as a synergistic process) took place. Results showed that the relationship between the rate constants (k values) and the molecular descriptors of Group A was more pronounced than for Group B compounds. For the oxidation-dominated process, EHOMO and Fukui indices (f(0)x, f(-)x, f(+)x) were the most significant factors. The influence of bond order was more significant for the synergistic process of oxidation and coagulation than for the oxidation-dominated process. The influences of all other molecular descriptors on the synergistic process were weaker than on the oxidation-dominated process. Copyright © 2015. Published by Elsevier B.V.

Multi-Phase Equilibrium and Solubilities of Aromatic Compounds and Inorganic Compounds in Sub- and Supercritical Water: A Review.

PubMed

Liu, Qinli; Ding, Xin; Du, Bowen; Fang, Tao

2017-11-02

Supercritical water oxidation (SCWO), as a novel and efficient technology, has been applied to wastewater treatment processes. The use of phase equilibrium data to optimize process parameters can offer a theoretical guidance for designing SCWO processes and reducing the equipment and operating costs. In this work, high-pressure phase equilibrium data for aromatic compounds+water systems and inorganic compounds+water systems are given. Moreover, thermodynamic models, equations of state (EOS) and empirical and semi-empirical approaches are summarized and evaluated. This paper also lists the existing problems of multi-phase equilibria and solubility studies on aromatic compounds and inorganic compounds in sub- and supercritical water.

New perspectives for Advanced Oxidation Processes.

PubMed

Dewil, Raf; Mantzavinos, Dionissios; Poulios, Ioannis; Rodrigo, Manuel A

2017-06-15

Advanced Oxidation Processes (AOPs) are called to fill the gap between the treatability attained by conventional physico-chemical and biological treatments and the day-to-day more exigent limits fixed by environmental regulations. They are particularly important for the removal of anthropogenic pollutants and for this reason, they have been widely investigated in the last decades and even applied in the treatment of many industrial wastewater flows. However, despite the great development reached, AOPs cannot be considered mature yet and there are many new fields worthy of research. Some of them are going to be briefly introduced in this paper, including hybrid processes, heterogeneous semiconductor photocatalysis, sulphate-radical oxidation and electrochemical advanced oxidation for water/wastewater treatment. Moreover, the use of photoelectrochemical processes for energy production is discussed. The work ends with some perspectives that can be of interest for the ongoing and future research. Copyright © 2017. Published by Elsevier Ltd.

Stable isotopes as tracers of methane dynamics in Everglades marshes with and without active populations of methane oxidizing bacteria

NASA Technical Reports Server (NTRS)

Happell, James D.; Chanton, Jeffrey P.; Whiting, Gary J.; Showers, William J.

1993-01-01

The stable carbon isotopic composition of CH4 is used to study the processes that affect it during transport through plants from sediment to the atmosphere. The enhancement of CH4 flux from Cladium and Eleocharis over the flux from open water or clipped sites indicated that these plants served as gas conduits between the sediments and the atmosphere. Lowering of the water table below the sediment surface caused an Everglades sawgrass marsh to shift from emission of CH4 to consumption of atmospheric CH4. Cladium transported gases passively mainly via molecular diffusion and/or effusion instead of actively via bulk flow. Stable isotropic data gave no evidence that CH4 oxidation was occurring in the rhizosphere of Cladium. Both CH4 stable carbon isotope and flux data indicated a lack of CH4 oxidation at the sediment-water interface in Everglades marl soils and its presence in peat soils where 40 to 92 percent of the flux across the sediment-water interface was oxidized.

Conversion coatings prepared or treated with calcium hydroxide solutions

NASA Technical Reports Server (NTRS)

Maxey, Jason (Inventor); Nelson, Carl (Inventor); Eylem, Cahit (Inventor); Minevski, Zoran (Inventor); Clarke, Eric (Inventor)

2002-01-01

A conversion coating process that forms a stable and corrosion-resistant oxide layer on metal or metal oxide substrates or layers. Particularly, the conversion coating process involves contacting the metal or metal oxide substrate or layer with the aqueous calcium hydroxide solutions in order to convert the surface of the substrate to a stable metal oxide layer or coating. According to the present invention, the calcium hydroxide solution is prepared by removing carbon dioxide from water or an aqueous solution before introducing the calcium hydroxide. In this manner, formation of calcium carbonate particles is avoided and the porosity of the conversion coating produced by the calcium hydroxide solution is reduced to below about 1%.

Comparative study of the effect of pharmaceutical additives on the elimination of antibiotic activity during the treatment of oxacillin in water by the photo-Fenton, TiO2-photocatalysis and electrochemical processes.

PubMed

Serna-Galvis, Efraim A; Silva-Agredo, Javier; Giraldo, Ana L; Flórez-Acosta, Oscar A; Torres-Palma, Ricardo A

2016-01-15

Synthetic pharmaceutical effluents loaded with the β-lactam antibiotic oxacillin were treated using advanced oxidation processes (the photo-Fenton system and TiO2 photocatalysis) and chloride mediated electrochemical oxidation (with Ti/IrO2 anodes). Combinations of the antibiotic with excipients (mannitol or tartaric acid), an active ingredient (calcium carbonate, i.e. bicarbonate ions due to the pH) and a cleaning agent (sodium lauryl ether sulfate) were considered. Additionally, urban wastewater that had undergone biological treatment was doped with oxacillin and treated with the tested systems. The evolution of antimicrobial activity was monitored as a parameter of processes efficiency. Although the two advanced oxidation processes (AOPs) differ only in the way they produce OH, marked differences were observed between them. There were also differences between the AOPs and the electrochemical system. Interestingly, each additive had a different effect on each treatment. For water loaded with mannitol, electrochemical treatment was the most suitable option because the additive did not significantly affect the efficiency of the system. Due to the formation of a complex with Fe(3+), tartaric acid accelerated the elimination of antibiotic activity during the photo-Fenton process. For TiO2 photocatalysis, the presence of bicarbonate ions contributed to antibiotic activity elimination through the possible formation of carbonate and bicarbonate radicals. Sodium lauryl ether sulfate negatively affected all of the processes. However, due to the higher selectivity of HOCl compared with OH, electrochemical oxidation showed the least inhibited efficiency. For the urban wastewater doped with oxacillin, TiO2 photocatalysis was the most efficient process. These results will help select the most suitable technology for the treatment of water polluted with β-lactam antibiotics. Copyright © 2015 Elsevier B.V. All rights reserved.

Isotope signatures of N2O emitted from vegetable soil: Ammonia oxidation drives N2O production in NH4(+)-fertilized soil of North China.

PubMed

Zhang, Wei; Li, Yuzhong; Xu, Chunying; Li, Qiaozhen; Lin, Wei

2016-07-08

Nitrous oxide (N2O) is a potent greenhouse gas. In North China, vegetable fields are amended with high levels of N fertilizer and irrigation water, which causes massive N2O flux. The aim of this study was to determine the contribution of microbial processes to N2O production and characterize isotopic signature effects on N2O source partitioning. We conducted a microcosm study that combined naturally abundant isotopologues and gas inhibitor techniques to analyze N2O flux and its isotopomer signatures [δ(15)N(bulk), δ(18)O, and SP (intramolecular (15)N site preference)] that emitted from vegetable soil after the addition of NH4(+) fertilizers. The results show that ammonia oxidation is the predominant process under high water content (70% water-filled pore space), and nitrifier denitrification contribution increases with increasing N content. δ(15)N(bulk) and δ(18)O of N2O may not provide information about microbial processes due to great shifts in precursor signatures and atom exchange, especially for soil treated with NH4(+) fertilizer. SP and associated two end-member mixing model are useful to distinguish N2O source and contribution. Further work is needed to explore isotopomer signature stability to improve N2O microbial process identification.

Isotope signatures of N2O emitted from vegetable soil: Ammonia oxidation drives N2O production in NH4+-fertilized soil of North China

NASA Astrophysics Data System (ADS)

Zhang, Wei; Li, Yuzhong; Xu, Chunying; Li, Qiaozhen; Lin, Wei

2016-07-01

Nitrous oxide (N2O) is a potent greenhouse gas. In North China, vegetable fields are amended with high levels of N fertilizer and irrigation water, which causes massive N2O flux. The aim of this study was to determine the contribution of microbial processes to N2O production and characterize isotopic signature effects on N2O source partitioning. We conducted a microcosm study that combined naturally abundant isotopologues and gas inhibitor techniques to analyze N2O flux and its isotopomer signatures [δ15Nbulk, δ18O, and SP (intramolecular 15N site preference)] that emitted from vegetable soil after the addition of NH4+ fertilizers. The results show that ammonia oxidation is the predominant process under high water content (70% water-filled pore space), and nitrifier denitrification contribution increases with increasing N content. δ15Nbulk and δ18O of N2O may not provide information about microbial processes due to great shifts in precursor signatures and atom exchange, especially for soil treated with NH4+ fertilizer. SP and associated two end-member mixing model are useful to distinguish N2O source and contribution. Further work is needed to explore isotopomer signature stability to improve N2O microbial process identification.

Photodegradation of perfluorooctanoic acid by graphene oxide-deposited TiO2 nanotube arrays in aqueous phase.

PubMed

Park, Kyungmin; Ali, Imran; Kim, Jong-Oh

2018-07-15

Perfluorooctanoic acid (PFOA) is a persistent organic pollutant in the environment with serious health risks including endocrine-disrupting characteristics, immunotoxicity, and causing developmental defects. The photocatalytic deposition has proven to be an inexpensive, effective, and sustainable technology for the removal of PFOA in the aqueous phase. Most investigations are conducted in ultrapure water at concentrations higher than those detected in actual water systems. A few studies deal with the toxicity of treated water. In this research, the photocatalytic degradation of PFOA, including photo-oxidative and photo-reductive degradation, is reviewed comprehensively. Compared to photo-oxidation, photo-reduction is more suitable for PFOA removal since it favors defluorination of PFOA and complete mineralization. We used graphene oxide/TiO 2 nanotubes array for photocatalytic degradation of PFOA. The effects of key parameters on the photocatalytic degradation and defluorination processes of PFOA, such as initial PFOA concentration, initial pH of the solution, an initial temperature of the solution, and external bias constant potential, are addressed. We observed that at pH 3 the PFOA degradation was around 83% in 4 h, and at 75 °C almost complete PFOA degradation was observed in 2.5 h. In photoelectrocatalytic process at 2.0 V external bias 97% of PFOA was degraded in 4 h. The mechanisms of the PFOA photodegradation process are also discussed in detail. Copyright © 2018 Elsevier Ltd. All rights reserved.

The economic pre-treatment of coal mine drainage water with caustic and ozone.

PubMed

Boyden, B H; Nador, L; Addleman, S; Jeston, L

2017-09-01

Coal mine drainage waters are low in pH with varying amounts of iron and manganese and are generally brackish. The Austar Coal Mine in NSW, Australia, sought alternatives to their current lime dosing as the pre-treatment before the downstream reverse osmosis plant. Undesirable operating aspects of the current system include manganese and gypsum scaling/fouling, the need for anti-scalants and reduced water recovery. Thirteen processes for acid mine drainage were initially considered. The preferred process of caustic and ozone for Mn(II) oxidation was pilot tested at up to 0.74 kL/hr at the mine site. Under proper conditions and no aeration, about 81 per cent of the Fe could be removed (initially at 156 mg/L) as green rust. Supplemental aeration followed first-order kinetics and allowed 99.9 per cent Fe(II) oxidation and removal but only with a hydraulic residence time of about 47 minutes. The addition of supplemental Cu catalyst improved Fe removal. Ozone applied after caustic was effective in stoichiometrically oxidising recalcitrant Mn(II) and any remaining Fe(II). Control of the ozonation was achieved using the oxidation reduction potential during oxidation of the Mn(II) species. The use of caustic, followed by ozone, proved economically comparable to the current lime pre-treatment.

In vitro bioassays to evaluate complex chemical mixtures in recycled water

PubMed Central

Jia, Ai; Escher, Beate I.; Leusch, Frederic D.L.; Tang, Janet Y.M.; Prochazka, Erik; Dong, Bingfeng; Snyder, Erin M.; Snyder, Shane A.

2016-01-01

With burgeoning population and diminishing availability of freshwater resources, the world continues to expand the use of alternative water resources for drinking, and the quality of these sources has been a great concern for the public as well as public health professionals. In vitro bioassays are increasingly being used to enable rapid, relatively inexpensive toxicity screening that can be used in conjunction with analytical chemistry data to evaluate water quality and the effectiveness of water treatment. In this study, a comprehensive bioassay battery consisting of 36 bioassays covering 18 biological endpoints was applied to screen the bioactivity of waters of varying qualities with parallel treatments. Samples include wastewater effluent, ultraviolet light (UV) and/or ozone advanced oxidation processed (AOP) recycled water, and infiltrated recycled groundwater. Based on assay sensitivity and detection frequency in the samples, several endpoints were highlighted in the battery, including assays for genotoxicity, mutagenicity, estrogenic activity, glucocorticoid activity, aryl hydrocarbon receptor activity, oxidative stress response, and cytotoxicity. Attenuation of bioactivity was found to be dependent on the treatment process and bioassay endpoint. For instance, ozone technology significantly removed oxidative stress activity, while UV based technologies were most efficient for the attenuation of glucocorticoid activity. Chlorination partially attenuated genotoxicity and greatly decreased herbicidal activity, while groundwater infiltration efficiently attenuated most of the evaluated bioactivity with the exception of genotoxicity. In some cases, bioactivity (e.g., mutagenicity, genotoxicity, and arylhydrocarbon receptor) increased following water treatment, indicating that transformation products of water treatment may be a concern. Furthermore, several types of bioassays with the same endpoint were compared in this study, which could help guide the selection of optimized methods in future studies. Overall, this research indicates that a battery of bioassays can be used to support decision-making on the application of advanced water treatment processes for removal of bioactivity. PMID:25989591

In vitro bioassays to evaluate complex chemical mixtures in recycled water.

PubMed

Jia, Ai; Escher, Beate I; Leusch, Frederic D L; Tang, Janet Y M; Prochazka, Erik; Dong, Bingfeng; Snyder, Erin M; Snyder, Shane A

2015-09-01

With burgeoning population and diminishing availability of freshwater resources, the world continues to expand the use of alternative water resources for drinking, and the quality of these sources has been a great concern for the public as well as public health professionals. In vitro bioassays are increasingly being used to enable rapid, relatively inexpensive toxicity screening that can be used in conjunction with analytical chemistry data to evaluate water quality and the effectiveness of water treatment. In this study, a comprehensive bioassay battery consisting of 36 bioassays covering 18 biological endpoints was applied to screen the bioactivity of waters of varying qualities with parallel treatments. Samples include wastewater effluent, ultraviolet light (UV) and/or ozone advanced oxidation processed (AOP) recycled water, and infiltrated recycled groundwater. Based on assay sensitivity and detection frequency in the samples, several endpoints were highlighted in the battery, including assays for genotoxicity, mutagenicity, estrogenic activity, glucocorticoid activity, arylhydrocarbon receptor activity, oxidative stress response, and cytotoxicity. Attenuation of bioactivity was found to be dependent on the treatment process and bioassay endpoint. For instance, ozone technology significantly removed oxidative stress activity, while UV based technologies were most efficient for the attenuation of glucocorticoid activity. Chlorination partially attenuated genotoxicity and greatly decreased herbicidal activity, while groundwater infiltration efficiently attenuated most of the evaluated bioactivity with the exception of genotoxicity. In some cases, bioactivity (e.g., mutagenicity, genotoxicity, and arylhydrocarbon receptor) increased following water treatment, indicating that transformation products of water treatment may be a concern. Furthermore, several types of bioassays with the same endpoint were compared in this study, which could help guide the selection of optimized methods in future studies. Overall, this research indicates that a battery of bioassays can be used to support decision-making on the application of advanced water treatment processes for removal of bioactivity. Copyright © 2015 Elsevier Ltd. All rights reserved.

Potential Lifestyles in Ancient Environments of Gusev Crater, Mars

NASA Technical Reports Server (NTRS)

DesMarais, David J.

2006-01-01

Habitable environments must sustain liquid water at least intermittently and also provide both chemical building blocks and useful sources of energy for life. Observations by Spirit rover indicate that conditions have probably been too dry to sustain life, at least since the emplacement of the extensive basalts that underlie the plains around the Columbia Memorial Station landing site. Local evidence of relatively minor aqueous alteration probably occurred under conditions where the activity of water was too low to sustain biological processes as we know them. In contrast, multiple bedrock units in West Spur and Husband Hill in the Columbia Wills have been extensively altered, probably by aqueous processes. The Fe in several of these units has been extensively oxidized, indicating that, in principle, any microbiota present during the aqueous alteration of these rocks could have obtained energy from Fe oxidation. Spirit discovered oliving-rich ultramafic rocks during her descent from Husband Hill southward into Inner Basin. Alteration of similar ultramafic rocks on Earth can yield H2 that can provide both energy and reducing power for microorganisms. Spirit s discovery of "salty" soil horizons rich in Fe and/or Mg is consistent with the aqueous dissolution and/or alteration of olivine. Such processes can oxidize Fe and also yield H2 under appropriate conditions. Very high S concentrations in these salty deposits indicate that soluble salts were mobilized by water and/or that S oxidation, a potential energy source for life, occurred. The Athena team has not yet established whether these salt components were deposited as large beds in ancient water bodies or, for example, were concentrated by more recent groundwater activity. Collectively these observations are consistent with the possibility that habitable environments existed at least intermittently in the distant geologic past.

Direct oxidation of strong waste waters, simulating combined wastes in extended-mission space cabins

NASA Technical Reports Server (NTRS)

Ross, L. W.

1973-01-01

The applications of modern technology to the resolution of the problem of solid wastes in space cabin environments was studied with emphasis on the exploration of operating conditions that would permit lowering of process temperatures in wet oxidation of combined human wastes. It was found that the ultimate degree of degradation is not enhanced by use of a catalyst. However, the rate of oxidation is increased, and the temperature of oxidation is reduced to 400 F.

Effects of mining activities on evolution of water chemistry in coal-bearing aquifers in karst region of Midwestern Guizhou, China: evidences from δ13C of dissolved inorganic carbon and δ34S of sulfate.

PubMed

Li, Qingguang; Wu, Pan; Zha, Xuefang; Li, Xuexian; Wu, Linna; Gu, Shangyi

2018-04-24

The generation of acid mine drainage (AMD) may accelerate watershed erosion and promote the migration of heavy metals, then threaten local ecosystems such as aquatic life and even human health. Previous studies have focused primarily on influence of AMD in surface environment. In order to reveal the acidizing processes in karst high-sulfur coalfield in Southwest China, this study, by contrast, focused on the hydrogeochemical evolution process and acidification mechanism of mine water in Zhijin coalfield, western Guizhou Province. The oxidation of pyrite and other sulfides induced strong acidification of mine water according to the water chemical analysis. As a result, a series of geochemical processes such as dissolution of carbonates and silicates, hydrolysis of metal ions, and degassing of CO 2 complicated water chemical evolution. The dissolution of silicates controlled the chemical composition of mine water, but more carbonates might be dissolved during the acidification of mine water. The sources of sulfate are quite different in water samples collected from the two selected mine. According to sulfur isotope analysis, the dissolution of gypsum is the primary source of sulfate in samples from Hongfa mine, whereas sulfide oxidation contributed a large amount of sulfate to the mine water in Fenghuangshan mine. The dissolution of carbonates should be an important source of DIC in mine water and CO 2 originating from organic mineralization might also have a certain contribution. This study elucidated the groundwater chemical evolution processes in high-sulfur coal-bearing strata and provided a foundation for further study of carbonates erosion and carbon emission during acidification of mine water.

Medium pressure UV combined with chlorine advanced oxidation for trichloroethylene destruction in a model water.

PubMed

Wang, Ding; Bolton, James R; Hofmann, Ron

2012-10-01

The effectiveness of ultraviolet (UV) combined with chlorine as a novel advanced oxidation process (AOP) for drinking water treatment was evaluated in a bench scale study by comparing the rate of trichloroethylene (TCE) decay when using UV/chlorine to the rates of decay by UV alone and UV/hydrogen peroxide (H₂O₂) at various pH values. A medium pressure mercury UV lamp was used. The UV/chlorine process was more efficient than the UV/H₂O₂ process at pH 5, but in the neutral and alkaline pH range, the UV/H₂O₂ process became more efficient. The pH effect was probably controlled by the increasing concentration of OCl⁻ at higher pH values. A mechanistic kinetic model of the UV/chlorine treatment of TCE showed good agreement with the experimental data. Copyright © 2012 Elsevier Ltd. All rights reserved.

Three-dimensional three-phase model for simulation of hydrodynamics, oxygen mass transfer, carbon oxidation, nitrification and denitrification in an oxidation ditch.

PubMed

Lei, Li; Ni, Jinren

2014-04-15

A three-dimensional three-phase fluid model, supplemented by laboratory data, was developed to simulate the hydrodynamics, oxygen mass transfer, carbon oxidation, nitrification and denitrification processes in an oxidation ditch. The model provided detailed phase information on the liquid flow field, gas hold-up distribution and sludge sedimentation. The three-phase model described water-gas, water-sludge and gas-sludge interactions. Activated sludge was taken to be in a pseudo-solid phase, comprising an initially separated solid phase that was transported and later underwent biological reactions with the surrounding liquidmedia. Floc parameters were modified to improve the sludge viscosity, sludge density, oxygen mass transfer rate, and carbon substrate uptake due to adsorption onto the activated sludge. The validation test results were in very satisfactory agreement with laboratory data on the behavior of activated sludge in an oxidation ditch. By coupling species transport and biological process models, reasonable predictions are made of: (1) the biochemical kinetics of dissolved oxygen, chemical oxygen demand (COD) and nitrogen variation, and (2) the physical kinematics of sludge sedimentation. Copyright © 2014 Elsevier Ltd. All rights reserved.

Electrochemical advanced oxidation for cold incineration of the pharmaceutical ranitidine: mineralization pathway and toxicity evolution.

PubMed

Olvera-Vargas, Hugo; Oturan, Nihal; Brillas, Enric; Buisson, Didier; Esposito, Giovanni; Oturan, Mehmet A

2014-12-01

Ranitidine (RNTD) is a widely prescribed histamine H2-receptor antagonist whose unambiguous presence in water sources appointed it as an emerging pollutant. Here, the degradation of 0.1 mM of this drug in aqueous medium was studied by electrochemical advanced oxidation processes (EAOPs) like anodic oxidation with electrogenerated H2O2 and electro-Fenton using Pt/carbon-felt, BDD/carbon-felt and DSA-Ti/RuO2–IrO2/carbon-felt cells. The higher oxidation power of the electro-Fenton process using a BDD anode was demonstrated. The oxidative degradation of RNTD by the electrochemically generated OH radicals obeyed a pseudo-first order kinetics. The absolute rate constant for its hydroxylation reaction was 3.39 × 109 M−1 s−1 as determined by the competition kinetics method. Almost complete mineralization of the RNTN solution was reached by using a BDD anode in both anodic oxidation with electrogenerated H2O2 and electro-Fenton processes. Up to 11 cyclic intermediates with furan moiety were detected from the degradation of RNTD, which were afterwards oxidized to short-chain carboxylic acids before their mineralization to CO2 and inorganic ions such as NH4+, NO3− and SO42−. Based on identified products, a plausible reaction pathway was proposed for RNTD mineralization. Toxicity assessment by the Microtox® method revealed that some cyclic intermediates are more toxic than the parent molecule. Toxicity was quickly removed following the almost total mineralization of the treated solution. Overall results confirm the effectiveness of EAOPs for the efficient removal of RNTD and its oxidation by-products from water.

TEMPO-oxidized cellulose nanofibers

NASA Astrophysics Data System (ADS)

Isogai, Akira; Saito, Tsuguyuki; Fukuzumi, Hayaka

2011-01-01

Native wood celluloses can be converted to individual nanofibers 3-4 nm wide that are at least several microns in length, i.e. with aspect ratios >100, by TEMPO (2,2,6,6-tetramethylpiperidine-1-oxyl radical)-mediated oxidation and successive mild disintegration in water. Preparation methods and fundamental characteristics of TEMPO-oxidized cellulose nanofibers (TOCN) are reviewed in this paper. Significant amounts of C6 carboxylate groups are selectively formed on each cellulose microfibril surface by TEMPO-mediated oxidation without any changes to the original crystallinity (~74%) or crystal width of wood celluloses. Electrostatic repulsion and/or osmotic effects working between anionically-charged cellulose microfibrils, the ζ-potentials of which are approximately -75 mV in water, cause the formation of completely individualized TOCN dispersed in water by gentle mechanical disintegration treatment of TEMPO-oxidized wood cellulose fibers. Self-standing TOCN films are transparent and flexible, with high tensile strengths of 200-300 MPa and elastic moduli of 6-7 GPa. Moreover, TOCN-coated poly(lactic acid) films have extremely low oxygen permeability. The new cellulose-based nanofibers formed by size reduction process of native cellulose fibers by TEMPO-mediated oxidation have potential application as environmentally friendly and new bio-based nanomaterials in high-tech fields.

Novel two stage bio-oxidation and chlorination process for high strength hazardous coal carbonization effluent.

PubMed

Manekar, Pravin; Biswas, Rima; Karthik, Manikavasagam; Nandy, Tapas

2011-05-15

Effluent generated from coal carbonization to coke was characterized with high organic content, phenols, ammonium nitrogen, and cyanides. A full scale effluent treatment plant (ETP) working on the principle of single stage carbon-nitrogen bio-oxidation process (SSCNBP) revealed competition between heterotrophic and autotrophic bacteria in the bio-degradation and nitrification process. The effluent was pretreated in a stripper and further combined with other streams to treat in the SSCNBP. Laboratory studies were carried on process and stripped effluents in a bench scale model of ammonia stripper and a two stage bio-oxidation process. The free ammonia removal efficiency of stripper was in the range 70-89%. Bench scale studies of the two stage bio-oxidation process achieved a carbon-nitrogen reduction at 6 days hydraulic retention time (HRT) operating in an extended aeration mode. This paper addresses the studies on selection of a treatment process for removal of organic matter, phenols, cyanide and ammonia nitrogen. The treatment scheme comprising ammonia stripping (pretreatment) followed by the two stage bio-oxidation and chlorination process met the Indian Standards for discharge into Inland Surface Waters. This treatment process package offers a techno-economically viable treatment scheme to neuter hazardous effluent generated from coal carbonization process. Copyright © 2011 Elsevier B.V. All rights reserved.

DEMONSTRATION BULLETIN: IN-SITU THERMAL OXIDATION PROCESS - HRUBETZ ENVIRONMENTAL SERVICES

EPA Science Inventory

The HRUBOUT process is a thermal, treatment process designed to remove VOCs and semi-VOCs from contaminated soils. Heated air is injected into the soil below the contamination zone, evaporating soil moisture and removing volatile and semivolatile hydrocarbons. As the water evapor...

An Evaluation of the Vapor Phase Catalytic Ammonia Removal Process for Use in a Mars Transit Vehicle

NASA Technical Reports Server (NTRS)

Flynn, Michael; Borchers, Bruce

1998-01-01

An experimental program has been developed to evaluate the potential of the Vapor Phase Catalytic Ammonia Reduction (VPCAR) technology for use as a Mars Transit Vehicle water purification system. Design modifications which will be required to ensure proper operation of the VPCAR system in reduced gravity are also evaluated. The VPCAR system is an integrated wastewater treatment technology that combines a distillation process with high temperature catalytic oxidation. The distillation portion of the system utilizes a vapor compression distillation process to provide an energy efficient phase change separation. This portion of the system removes any inorganic salts and large molecular weight, organic contaminates, i.e., non-volatile, from the product water stream and concentrates these contaminates into a byproduct stream. To oxidize the volatile organic compounds and ammonia, a vapor phase, high temperature catalytic oxidizer is used. This catalytic system converts these compounds along with the aqueous product into CO2, H2O, and N2O. A secondary catalytic bed can then be used to reduce the N2O to nitrogen and oxygen (although not evaluated in this study). This paper describes the design specification of the VPCAR process, the relative benefits of its utilization in a Mars Transit Vehicle, and the design modification which will be required to ensure its proper operation in reduced gravity. In addition, the results of an experimental evaluation of the processors is presented. This evaluation presents the processors performance based upon product water purity, water recovery rates, and power.

Preparation, characterization and dissolution of passive oxide film on the 400 series stainless steel surfaces

NASA Astrophysics Data System (ADS)

Sathyaseelan, V. S.; Rufus, A. L.; Chandramohan, P.; Subramanian, H.; Velmurugan, S.

2015-12-01

Full system decontamination of Primary Heat Transport (PHT) system of Pressurised Heavy Water Reactors (PHWRs) resulted in low decontamination factors (DF) on stainless steel (SS) surfaces. Hence, studies were carried out with 403 SS and 410 SS that are the material of construction of "End-Fitting body" and "End-Fitting Liner tubes". Three formulations were evaluated for the dissolution of passive films formed over these alloys viz., i) Two-step process consisting of oxidation and reduction reactions, ii) Dilute Chemical Decontamination (DCD) and iii) High Temperature Process. The two-step and high temperature processes could dissolve the oxide completely while the DCD process could remove only 60%. Various techniques like XRD, Raman spectroscopy and SEM-EDX were used for assessing the dissolution process. The two-step process is time consuming, laborious while the high temperature process is less time consuming and is recommended for SS decontamination.

Method for processing aluminum spent potliner in a graphite electrode ARC furnace

DOEpatents

O'Connor, William K.; Turner, Paul C.; Addison, Gerald W.

2002-12-24

A method of processing spent aluminum pot liner containing carbon, cyanide compositions, fluorides and inorganic oxides. The spent aluminum pot liner is crushed iron oxide is added to form an agglomerated material. The agglomerated material is melted in an electric arc furnace having the electrodes submerged in the molten material to provide a reducing environment during the furnace operation. In the reducing environment, pot liner is oxidized while the iron oxides are reduced to produce iron and a slag substantially free of cyanide compositions and fluorides. An off-gas including carbon oxides and fluorine is treated in an air pollution control system with an afterburner and a scrubber to produce NaF, water and a gas vented to the atmosphere free of cyanide compositions, fluorine and CO.

Abundance and diversity of ammonia-oxidizing archaea and bacteria on granular activated carbon and their fates during drinking water purification process.

PubMed

Niu, Jia; Kasuga, Ikuro; Kurisu, Futoshi; Furumai, Hiroaki; Shigeeda, Takaaki; Takahashi, Kazuhiko

2016-01-01

Ammonia is a precursor to trichloramine, which causes an undesirable chlorinous odor. Granular activated carbon (GAC) filtration is used to biologically oxidize ammonia during drinking water purification; however, little information is available regarding the abundance and diversity of ammonia-oxidizing archaea (AOA) and bacteria (AOB) associated with GAC. In addition, their sources and fates in water purification process remain unknown. In this study, six GAC samples were collected from five full-scale drinking water purification plants in Tokyo during summer and winter, and the abundance and community structure of AOA and AOB associated with GAC were studied in these two seasons. In summer, archaeal and bacterial amoA genes on GACs were present at 3.7 × 10(5)-3.9 × 10(8) gene copies/g-dry and 4.5 × 10(6)-4.2 × 10(8) gene copies/g-dry, respectively. In winter, archaeal amoA genes remained at the same level, while bacterial amoA genes decreased significantly for all GACs. No differences were observed in the community diversity of AOA and AOB from summer to winter. Phylogenetic analysis revealed high AOA diversity in group I.1a and group I.1b in raw water. Terminal-restriction fragment length polymorphism analysis of processed water samples revealed that AOA diversity decreased dramatically to only two OTUs in group I.1a after ozonation, which were identical to those detected on GAC. It suggests that ozonation plays an important role in determining AOA diversity on GAC. Further study on the cell-specific activity of AOA and AOB is necessary to understand their contributions to in situ nitrification performance.

Synergistic efficiency of the desilication of brackish underground water in Saudi Arabia by coupling γ-radiation and Fenton process: Membrane scaling prevention in reverse osmosis process

NASA Astrophysics Data System (ADS)

Aljohani, Mohammed S.

2017-12-01

One of the main water resources in arid Saudi Arabia is underground water. However, this brackish water has high silica content which can cause a recalcitrant deposit on the membrane in the reverse osmosis units during its desalination. In this study, we examined the synergistic efficiency of the removal of silica from the Buwaib water sample, when combining two advanced oxidation processes, γ-irradiation and the Fenton process, using hydrogen peroxide and zero valent metal iron as source of Fe3+. This latter adsorbs effectively on silica and co-precipitate. The influence of absorbed dose, iron dosage and pH effect were investigated. This preliminary study showed that these attractive and effective hybrid processes are very efficient in removing silica.

Spatial and temporal variability of nitrate and nitrous oxide concentrations in the unsaturated zone at a corn field in the US Midwest

NASA Astrophysics Data System (ADS)

Gopalakrishnan, G.; Negri, C.

2011-12-01

There has been a significant increase in reactive nitrogen in the environment as a result of human activity. Reactive nitrogen of anthropogenic origin now equals that derived from natural terrestrial nitrogen fixation and is expected to exceed it by the end of the decade. Nitrogen is applied to crops as fertilizer and impacts the environment through water quality impairments (mostly as nitrate) and as greenhouse gas emissions (as nitrous oxide). Research on environmental impacts resulting from nitrogen application in the form of fertilizers has focused disproportionately on the degradation of water quality from agricultural non-point sources. The impacts of this degradation are registered both locally, with runoff and percolation of agrochemicals into local surface water and groundwater, and on a larger scale, such as the increase in the anoxic zone in the Gulf of Mexico attributed to nitrate from the Mississippi River. Impacts to the global climate from increased production of nitrous oxide as a result of increased fertilization are equally significant. Nitrous oxide is a greenhouse gas with a warming potential that is approximately 300 times greater than carbon dioxide. Direct emissions of nitrous oxide from the soil have been expressed as 1% of the applied nitrogen. Indirect emissions due to runoff, leaching and volatilization of the nitrogen from the field have been expressed as 0.75% of the applied nitrogen. Many studies have focused on processes governing nitrogen fluxes in the soil, surface water and groundwater systems. However, research on the biogeochemical processes regulating nitrogen fluxes in the unsaturated zone and consequent impacts on nitrate and nitrous oxide concentrations in groundwater are lacking. Our study explores the spatial and temporal variability of nitrate and nitrous oxide concentrations in the vadose zone at a 15 acre corn field in the US Midwest and links it to the concentrations found in the groundwater at the field site. Results indicated that nitrate concentrations in the vadose zone were an order of magnitude greater than in the groundwater. Nitrous oxide concentrations were significantly less in the vadose zone, suggesting that conditions for microbial degradation of the nitrate were not optimal. There was significant short-term variability in the nitrate concentrations as well as spatial variability over the field site. While the processes governing the linkage between nitrogen concentrations in the unsaturated and saturated zones are still unclear, our research suggests that current models may overestimate the indirect emissions of nitrous oxide produced in agricultural systems.

Removal of Hazardous Pollutants from Wastewaters: Applications of TiO 2 -SiO 2 Mixed Oxide Materials

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

Rasalingam, Shivatharsiny; Peng, Rui; Koodali, Ranjit T.

The direct release of untreated wastewaters from various industries and households results in the release of toxic pollutants to the aquatic environment. Advanced oxidation processes (AOP) have gained wide attention owing to the prospect of complete mineralization of nonbiodegradable organic substances to environmentally innocuous products by chemical oxidation. In particular, heterogeneous photocatalysis has been demonstrated to have tremendous promise in water purification and treatment of several pollutant materials that include naturally occurring toxins, pesticides, and other deleterious contaminants. In this work, we have reviewed the different removal techniques that have been employed for water purification. In particular, the application ofmore » TiO 2 -SiO 2 binary mixed oxide materials for wastewater treatment is explained herein, and it is evident from the literature survey that these mixed oxide materials have enhanced abilities to remove a wide variety of pollutants.« less

Removal of Hazardous Pollutants from Wastewaters: Applications of TiO 2 -SiO 2 Mixed Oxide Materials

DOE PAGES

Rasalingam, Shivatharsiny; Peng, Rui; Koodali, Ranjit T.

2014-01-01

The direct release of untreated wastewaters from various industries and households results in the release of toxic pollutants to the aquatic environment. Advanced oxidation processes (AOP) have gained wide attention owing to the prospect of complete mineralization of nonbiodegradable organic substances to environmentally innocuous products by chemical oxidation. In particular, heterogeneous photocatalysis has been demonstrated to have tremendous promise in water purification and treatment of several pollutant materials that include naturally occurring toxins, pesticides, and other deleterious contaminants. In this work, we have reviewed the different removal techniques that have been employed for water purification. In particular, the application ofmore » TiO 2 -SiO 2 binary mixed oxide materials for wastewater treatment is explained herein, and it is evident from the literature survey that these mixed oxide materials have enhanced abilities to remove a wide variety of pollutants.« less

Preventive Effect of Hydrogen Water on the Development of Detrusor Overactivity in a Rat Model of Bladder Outlet Obstruction.

PubMed

Miyazaki, Nozomu; Yamaguchi, Osamu; Nomiya, Masanori; Aikawa, Ken; Kimura, Junko

2016-03-01

Bladder ischemia and oxidative stress contribute to the pathogenesis of bladder dysfunction caused by bladder outlet obstruction. H2 reportedly acts as an effective antioxidant. We investigated whether oral ingestion of H2 water would have a beneficial effect on bladder function in a rat model of bladder outlet obstruction. H2 water was made by dissolving H2 gas in ordinary drinking water using a hydrogen water producing apparatus. The bladder outlet obstruction model was surgically induced in male rats. Rats with obstruction were fed H2 water or ordinary drinking water. On week 4 postoperatively cystometry was performed. Oxidative stress markers and the bladder nerve growth factor level were determined. Bladder tissues were processed for pharmacological studies and histological analysis. The micturition interval and micturition volume significantly decreased in obstructed rats given ordinary drinking water. These decreases were significantly suppressed by oral ingestion of H2 water. Increased post-void residual volume in obstructed rats was significantly reduced by H2 water. Obstruction led to a significant increase in bladder weight, oxidative stress markers and nerve growth factor. H2 water significantly suppressed these increases without affecting bladder weight. There was no significant difference in histological findings between rats with bladder obstruction given H2 water and ordinary drinking water. Decreased responses of detrusor muscle strips from obstructed bladders to KCl, carbachol and electrical field stimulation were reversed by H2 water ingestion. Results suggest that H2 water could ameliorate bladder dysfunction secondary to bladder outlet obstruction by attenuating oxidative stress. Copyright © 2016 American Urological Association Education and Research, Inc. Published by Elsevier Inc. All rights reserved.

Application of sludge-based carbonaceous materials in a hybrid water treatment process based on adsorption and catalytic wet air oxidation.

PubMed

Julcour Lebigue, Carine; Andriantsiferana, Caroline; N'Guessan Krou; Ayral, Catherine; Mohamed, Elham; Wilhelm, Anne-Marie; Delmas, Henri; Le Coq, Laurence; Gerente, Claire; Smith, Karl M; Pullket, Suangusa; Fowler, Geoffrey D; Graham, Nigel J D

2010-12-01

This paper describes a preliminary evaluation of the performance of carbonaceous materials prepared from sewage sludges (SBCMs) in a hybrid water treatment process based on adsorption and catalytic wet air oxidation; phenol was used as the model pollutant. Three different sewage sludges were treated by either carbonisation or steam activation, and the physico-chemical properties of the resultant carbonaceous materials (e.g. hardness, BET surface area, ash and elemental content, surface chemistry) were evaluated and compared with a commercial reference activated carbon (PICA F22). The adsorption capacity for phenol of the SBCMs was greater than suggested by their BET surface area, but less than F22; a steam activated, dewatered raw sludge (SA_DRAW) had the greatest adsorption capacity of the SBCMs in the investigated range of concentrations (<0.05 mol L(-1)). In batch oxidation tests, the SBCMs demonstrated catalytic behaviour arising from their substrate adsorptivity and metal content. Recycling of SA_DRAW in successive oxidations led to significant structural attrition and a hardened SA_DRAW was evaluated, but found to be unsatisfactory during the oxidation step. In a combined adsorption-oxidation sequence, both the PICA carbon and a selected SBCM showed deterioration in phenol adsorption after oxidative regeneration, but a steady state performance was reached after 2 or 3 cycles. Copyright © 2010 Elsevier Ltd. All rights reserved.

Oxidative degradation of endotoxin by advanced oxidation process (O3/H2O2 & UV/H2O2).

PubMed

Oh, Byung-Taek; Seo, Young-Suk; Sudhakar, Dega; Choe, Ji-Hyun; Lee, Sang-Myeong; Park, Youn-Jong; Cho, Min

2014-08-30

The presence of endotoxin in water environments may pose a serious public health hazard. We investigated the effectiveness of advanced oxidative processes (AOP: O3/H2O2 and UV/H2O2) in the oxidative degradation of endotoxin. In addition, we measured the release of endotoxin from Escherichia coli following typical disinfection methods, such as chlorine, ozone alone and UV, and compared it with the use of AOPs. Finally, we tested the AOP-treated samples in their ability to induce tumor necrosis factor alpha (TNF-α) in mouse peritoneal macrophages. The production of hydroxyl radical in AOPs showed superior ability to degrade endotoxin in buffered solution, as well as water samples from Korean water treatment facilities, with the ozone/H2O2 being more efficient compared to UV/H2O2. In addition, the AOPs proved effective not only in eliminating E. coli in the samples, but also in endotoxin degradation, while the standard disinfection methods lead to the release of endotoxin following the bacteria destruction. Furthermore, in the experiments with macrophages, the AOPs-deactivated endotoxin lead to the smallest induction of TNF-α, which shows the loss of inflammation activity, compared to ozone treatment alone. In conclusion, these results suggest that AOPs offer an effective and mild method for endotoxin degradation in the water systems. Copyright © 2014 Elsevier B.V. All rights reserved.

Role of a Water Network around the Mn4CaO5 Cluster in Photosynthetic Water Oxidation: A Fourier Transform Infrared Spectroscopy and Quantum Mechanics/Molecular Mechanics Calculation Study.

PubMed

Nakamura, Shin; Ota, Kai; Shibuya, Yuichi; Noguchi, Takumi

2016-01-26

Photosynthetic water oxidation takes place at the Mn4CaO5 cluster in photosystem II. Around the Mn4CaO5 cluster, a hydrogen bond network is formed by several water molecules, including four water ligands. To clarify the role of this water network in the mechanism of water oxidation, we investigated the effects of the removal of Ca(2+) and substitution with metal ions on the vibrations of water molecules coupled to the Mn4CaO5 cluster by means of Fourier transform infrared (FTIR) difference spectroscopy and quantum mechanics/molecular mechanics (QM/MM) calculations. The OH stretching vibrations of nine water molecules forming a network between D1-D61 and YZ were calculated using the QM/MM method. On the the calculated normal modes, a broad positive feature at 3200-2500 cm(-1) in an S2-minus-S1 FTIR spectrum was attributed to the vibrations of strongly hydrogen-bonded OH bonds of water involving the vibrations of water ligands to a Mn ion and the in-phase coupled vibration of a water network connected to YZ, while bands in the 3700-3500 cm(-1) region were assigned to the coupled vibrations of weakly hydrogen-bonded OH bonds of water. All the water bands were lost upon Ca(2+) depletion and Ba(2+) substitution, which inhibit the S2 → S3 transition, indicating that a solid water network was broken by these treatments. By contrast, Sr(2+) substitution slightly altered the water bands around 3600 cm(-1), reflecting minor modification in water interactions, consistent with the retention of water oxidation activity with a decreased efficiency. These results suggest that the water network around the Mn4CaO5 cluster plays an essential role in the water oxidation mechanism particularly in a concerted process of proton transfer and water insertion during the S2 → S3 transition.

Removal of Trace Arsenic to Meet Drinking Water Standards Using Iron Oxide Coated Multiwall Carbon Nanotubes.

PubMed

Ntim, Susana Addo; Mitra, Somenath

2011-05-12

This study presents the removal of trace level arsenic to meet drinking water standards using an iron oxide-multi-walled carbon nanotube (Fe-MWCNT) hybrid as a sorbent. The synthesis was facilitated by the high degree of nanotube functionalization using a microwave assisted process, and a controlled assembly of iron oxide was possible where the MWCNT served as an effective support for the oxide. In the final product, 11 % of the carbon atoms were attached to Fe. The Fe-MWCNT was effective in arsenic removal to below the drinking water standard levels of 10 µg L(-1). The absorption capacity of the composite was 1723 µg g(-1) and 189 µg g(-1) for As(III) and As(V) respectively. The adsorption of As(V) on Fe-MWCNT was faster than that of As(III). The pseudo-second order rate equation was found to effectively describe the kinetics of arsenic adsorption. The adsorption isotherms for As(III) and As(V) fitted both the Langmuir and Freundlich models.

Accumulation of iron and arsenic in the Chandina alluvium of the lower delta plain, Southeastern Bangladesh

USGS Publications Warehouse

Zahid, A.; Hassan, M.Q.; Breit, G.N.; Balke, K.-D.; Flegr, M.

2009-01-01

Accumulations of iron, manganese, and arsenic occur in the Chandina alluvium of southeastern Bangladesh within 2.5 m of the ground surface. These distinctive orange-brown horizons are subhorizontal and consistently occur within 1 m of the contact of the aerated (yellow-brown) and water-saturated (gray) sediment. Ferric oxyhydroxide precipitates that define the horizons form by oxidation of reduced iron in pore waters near the top of the saturated zone when exposed to air in the unsaturated sediment. Hydrous Fe-oxide has a high specific surface area and thus a high adsorption capacity that absorbs the bulk of arsenic also present in the reduced pore water, resulting in accumulations containing as much as 280 ppm arsenic. The steep redox gradient that characterizes the transition of saturated and unsaturated sediment also favors accumulation of manganese oxides in the oxidized sediment. Anomalous concentrations of phosphate and molybdenum also detected in the ferric oxyhydroxide-enriched sediment are attributed to sorption processes. ?? Springer Science+Business Media B.V. 2008.

Development of a novel wet oxidation process for hazardous and mixed wastes

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

Dhooge, P.M.

1994-11-01

This article describes and evaluates the DETOX{sup sm} process for processing of mixed wastes. Many DOE waste streams and remediates contain complex and variable mixtures of organic compounds, toxic metals, and radionuclides, often dispersed in organic or inorganic matrices, such as personal protective equipment, various sludges, soils, and water. The DETOX{sup sm} process, patented by Delphi Research, uses a unique combination of metal catalysts to increase the rate of oxidation of organic materials. Included are the following subject areas: project description (phases I-IV); results of all phases; and future work. 5 figs., 1 tab.

Arsenic Removal and Its Chemistry in Batch Electrocoagulation Studies.

PubMed

Sharma, Anshul; Adapureddy, Sri Malini; Goel, Sudha

2014-04-01

The aim of this study was to evaluate the impact of different oxidizing agents like light, aeration (by mixing) and electrocoagulation (EC) on the oxidation of As (III) and its subsequent removal in an EC batch reactor. Arsenic solutions prepared using distilled water and groundwater were evaluated. Optimum pH and the effect of varying initial pH on As removal efficiency were also evaluated. MaximumAs (III) removal efficiency with EC, light and aeration was 97% from distilled water and 71% from groundwater. Other results show that EC alone resulted in 90% As removal efficiency in the absence of light and mixing from distilled water and 53.6% from groundwater. Removal with light and mixing but without EC resulted in only 26% As removal from distilled water and 29% from groundwater proving that electro-oxidation and coagulation were more effective in removing arsenic compared to the other oxidizing agents examined. Initial pH was varied from 5 to 10 in distilled water and from 3 to 12 in groundwater for evaluating arsenic removal efficiency by EC. The optimum initial pH for arsenic removal was 7 for distilled water and groundwater. For all initial pHs tested between 5 and 10 in distilled water, the final pH ranged between 7 and 8 indicating that the EC process tends towards near neutral pH under the conditions examined in this study.

Impact of prechlorination on organophosphorus pesticides during drinking water treatment: Removal and transformation to toxic oxon byproducts.

PubMed

Li, Wei; Wu, Ruiqing; Duan, Jinming; Saint, Christopher P; van Leeuwen, John

2016-11-15

Prechlorination is commonly used to minimize operational problems associated with biological growth as well as taste and odor control during drinking water treatment. However, prechlorination can also oxidise micropollutants into intermediate byproducts. This could impose profound effects on the safety of the finished water if the transformed byproducts are more toxic and less removable. This study investigated the effect of prechlorination on decomposition and subsequent removal of the four organophosphorus pesticides (OPPs): chlorpyrifos, diazinon, malathion and tolclofos-methyl using a simulated conventional water treatment process of powdered activated carbon assisted coagulation-sedimentation-filtration (PAC-CSF) and postchlorination. It was found that, following prechlorination, not only did the percentage of OPPs oxidation vary significantly, but also the concentration of transformed oxons, which are more toxic than their parent compounds, increased as the major identified oxidation byproducts in water. Removal of these oxons proved to be more difficult by the PAC-CSF than their parent OPPs, because they are more water soluble and more hydrophilic. Both the OPP oxidation and oxon formation increased with chlorine dose during prechlorination. Meanwhile, the continuing chlorination of OPPs by residual free chlorine during PAC-CSF further complicated the pesticide removal processes, generally resulting in a gradually increased formation of oxons. Moreover, in the final treatment stage of postchlorination, the more chlorine-reactive pesticides, malathion and diazinon, were completely oxidised and the formation of corresponding oxons was increased with the prechlorine dose. In contrast, a certain amount of the less chlorine-reactive pesticide tolclofos-methyl still remained in solution after postchlorination, accompanied by an increased formation of tolclofos-methyl oxon with prechlorine dose. Since the oxons are resistant to further oxidation and less adsorbable during the PAC-CSF process, the gross removal of these pesticides and their oxons decreased with increase of the prechlorine dose. This led to an accumulation of the more toxic oxons in the finished water, especially at higher chlorine doses during prechlorination. The significance of this work is the demonstration that, under circumstances where prechlorination is used and source water contains traces of OPPs, alternative practices should be prioritized to avoid the potential risks involved in consumption of the treated water. Copyright © 2016 Elsevier Ltd. All rights reserved.

Process of activation of a palladium catalyst system

DOEpatents

Sobolevskiy, Anatoly [Orlando, FL; Rossin, Joseph A [Columbus, OH; Knapke, Michael J [Columbus, OH

2011-08-02

Improved processes for activating a catalyst system used for the reduction of nitrogen oxides are provided. In one embodiment, the catalyst system is activated by passing an activation gas stream having an amount of each of oxygen, water vapor, nitrogen oxides, and hydrogen over the catalyst system and increasing a temperature of the catalyst system to a temperature of at least 180.degree. C. at a heating rate of from 1-20.degree./min. Use of activation processes described herein leads to a catalyst system with superior NOx reduction capabilities.

Effects of conventional ozonation and electro-peroxone pretreatment of surface water on disinfection by-product formation during subsequent chlorination.

PubMed

Mao, Yuqin; Guo, Di; Yao, Weikun; Wang, Xiaomao; Yang, Hongwei; Xie, Yuefeng F; Komarneni, Sridhar; Yu, Gang; Wang, Yujue

2018-03-01

The electro-peroxone (E-peroxone) process is an emerging ozone-based electrochemical advanced oxidation process that combines conventional ozonation with in-situ cathodic hydrogen peroxide (H 2 O 2 ) production for oxidative water treatment. In this study, the effects of the E-peroxone pretreatment on disinfection by-product (DBP) formation from chlorination of a synthetic surface water were investigated and compared to conventional ozonation. Results show that due to the enhanced transformation of ozone (O 3 ) to hydroxyl radicals (OH) by electro-generated H 2 O 2 , the E-peroxone process considerably enhanced dissolved organic carbon (DOC) abatement and significantly reduced bromate (BrO 3 - ) formation compared to conventional ozonation. However, natural organic matter (NOM) with high UV 254 absorbance, which is the major precursors of chlorination DBPs, was less efficiently abated during the E-peroxone process than conventional ozonation. Consequently, while both conventional ozonation and the E-peroxone process substantially reduced the formation of DBPs (trihalomethanes and haloacetic acids) during post-chlorination, higher DBP concentrations were generally observed during chlorination of the E-peroxone pretreated waters than conventional ozonation treated. In addition, because of conventional ozonation or the E-peroxone treatment, DBPs formed during post-chlorination shifted to more brominated species. The overall yields of brominated DBPs exhibited strong correlations with the bromide concentrations in water. Therefore, while the E-peroxone process can effectively suppress bromide transformation to bromate, it may lead to higher formation of brominated DBPs during post-chlorination compared to conventional ozonation. These results suggest that the E-peroxone process can lead to different DBP formation and speciation during water treatment trains compared to conventional ozonation. Copyright © 2017 Elsevier Ltd. All rights reserved.

Accelerated evaporation of water on graphene oxide.

PubMed

Wan, Rongzheng; Shi, Guosheng

2017-03-29

Using molecular dynamics simulations, we show that the evaporation of nanoscale volumes of water on patterned graphene oxide is faster than that on homogeneous graphene oxide. The evaporation rate of water is insensitive to variation in the oxidation degree of the oxidized regions, so long as the water film is only distributed on the oxidized regions. The evaporation rate drops when the water film spreads onto the unoxidized regions. Further analysis showed that varying the oxidation degree observably changed the interaction between the outmost water molecules and the solid surface, but the total interaction for the outmost water molecules only changed a very limited amount due to the correspondingly regulated water-water interaction when the water film is only distributed on the oxidized regions. When the oxidation degree is too low and some unoxidized regions are also covered by the water film, the thickness of the water film decreases, which extends the lifetime of the hydrogen bonds for the outmost water molecules and lowers the evaporation rate of the water. The insensitivity of water evaporation to the oxidation degree indicates that we only need to control the scale of the unoxidized and oxidized regions for graphene oxide to regulate the evaporation of nanoscale volumes of water.

Impacts of Human Alteration of the Nitrogen Cycle in the U.S. on Radiative Forcing

EPA Science Inventory

Nitrogen cycling processes affect radiative forcing directly through emissions of nitrous oxide (N2O) and indirectly because emissions of nitrogen oxide (NO x ) and ammonia (NH3) affect atmospheric concentrations of methane (CH4), carbon dioxide (CO2), water vapor (H2O), ozone (O...

Design, fabrication and testing of a wet oxidation waste processing system. [for manned space flight

NASA Technical Reports Server (NTRS)

1975-01-01

The wet oxidation of sewage sludge during space flight was studied for water and gas recovery, and the elimination of overboard venting. The components of the system are described. Slurry and oxygen supply modules were fabricated and tested. Recommendations for redesign of the equipment are included.

Degradation of the commercial surfactant nonylphenol ethoxylate by advanced oxidation processes.

PubMed

da Silva, Salatiel Wohlmuth; Klauck, Cláudia Regina; Siqueira, Marco Antônio; Bernardes, Andréa Moura

2015-01-23

Four different oxidation process, namely direct photolysis (DP) and three advanced oxidation processes (heterogeneous photocatalysis - HP, eletrochemical oxidation - EO and photo-assisted electrochemical oxidation - PEO) were applied in the treatment of wastewater containing nonylphenol ethoxylate (NPnEO). The objective of this work was to determine which treatment would be the best option in terms of degradation of NPnEO without the subsequent generation of toxic compounds. In order to investigate the degradation of the surfactant, the processes were compared in terms of UV/Vis spectrum, mineralization (total organic carbon), reaction kinetics, energy efficiency and phytotoxicity. A solution containing NPnEO was prepared as a surrogate of the degreasing wastewater, was used in the processes. The results showed that the photo-assisted processes degrade the surfactant, producing biodegradable intermediates in the reaction. On the other hand, the electrochemical process influences the mineralization of the surfactant. The process of PEO carried out with a 250W lamp and a current density of 10mA/cm(2) showed the best results in terms of degradation, mineralization, reaction kinetics and energy consumption, in addition to not presenting phytotoxicity. Based on this information, this process can be a viable alternative for treating wastewater containing NPnEO, avoiding the contamination of water resources. Copyright © 2014 Elsevier B.V. All rights reserved.

Health Risk Estimation for Unregulated DBPs in Chloraminated Drinking Water

EPA Science Inventory

Disinfection by-products (DBPs) are formed when natural organic matter (NOM) reacts with chemical oxidants in the water disinfection process. Halogenated DBPs are both cytotoxic and genotoxic, which have the potential to cause adverse health effects (1). Currently, 4 species of t...

REMOVAL OF SYNTHETIC ORGANIC CHEMICAL CONTAMINANTS IN DRINKING WATER: RASCO, INC. ADVANCED SIMULTANEOUS OXIDATION PROCESS (ASOP)

EPA Science Inventory

The RASco, Inc. ASOP Drinking Water Treatment Module was tested at NSF’s Laboratory for the reduction of the following chemicals of concern: aldicarb, benzene, carbofuran, chloroform, dichlorvos, dicrotophos, methomyl, mevinphos, nicotine, oxamyl, paraquat, phorate, sodium fluor...

Nitrogen removal and intentional nitrous oxide production from reject water in a coupled nitritation/nitrous denitritation system under real feed-stream conditions.

PubMed

Weißbach, Max; Thiel, Paul; Drewes, Jörg E; Koch, Konrad

2018-05-01

A Coupled Aerobic-anoxic Nitrous Decomposition Operation (CANDO) was performed over five months to investigate the performance and dynamics of nitrogen elimination and nitrous oxide production from digester reject water under real feed-stream conditions. A 93% conversion of ammonium to nitrite could be maintained for adapted seed sludge in the first stage (nitritation). The second stage (nitrous denitritation), inoculated with conventional activated sludge, achieved a conversion of 70% of nitrite to nitrous oxide after only 12 cycles of operation. The development of an alternative feeding strategy and the addition of a coagulant (FeCl 3 ) facilitated stable operation and process intensification. Under steady-state conditions, nitrite was reliably eliminated and different nitrous oxide harvesting strategies were assessed. Applying continuous removal increased N 2 O yields by 16% compared to the application of a dedicated stripping phase. These results demonstrate the feasible application of the CANDO process for nitrogen removal and energy recovery from ammonia rich wastewater. Copyright © 2018 Elsevier Ltd. All rights reserved.

Ultralight super-hydrophobic carbon aerogels based on cellulose nanofibers/poly(vinyl alcohol)/graphene oxide (CNFs/PVA/GO) for highly effective oil-water separation.

PubMed

Xu, Zhaoyang; Zhou, Huan; Tan, Sicong; Jiang, Xiangdong; Wu, Weibing; Shi, Jiangtao; Chen, Peng

2018-01-01

With the worsening of the oil-product pollution problem, oil-water separation has attracted increased attention in recent years. In this study, a porous three-dimensional (3D) carbon aerogel based on cellulose nanofibers (CNFs), poly(vinyl alcohol) (PVA) and graphene oxide (GO) was synthesized by a facile and green approach. The resulting CNF/PVA/GO aerogels were synthesized through an environmentally friendly freeze-drying process and then carbonized to yield CNF/PVA/GO carbon aerogels with low density (18.41 mg cm -3 ), high porosity (98.98%), a water contact angle of 156° (super-hydrophobic) and high oil absorption capacity (97 times its own weight). The carbonization treatment of the CNF/PVA/GO aerogel not only improved the hydrophobic properties but also enhanced the adsorption capacity and specific surface area. Given the many good performance characteristics and the facile preparation process of carbon aerogels, these materials are viable candidates for use in oil-water separation and environmental protection.

Solar Thermo-coupled Electrochemical Oxidation of Aniline in Wastewater for the Complete Mineralization Beyond an Anodic Passivation Film.

PubMed

Yuan, Dandan; Tian, Lei; Li, Zhida; Jiang, Hong; Yan, Chao; Dong, Jing; Wu, Hongjun; Wang, Baohui

2018-02-15

Herein, we report the solar thermal electrochemical process (STEP) aniline oxidation in wastewater for totally solving the two key obstacles of the huge energy consumption and passivation film in the electrochemical treatment. The process, fully driven by solar energy without input of any other energies, sustainably serves as an efficient thermoelectrochemical oxidation of aniline by the control of the thermochemical and electrochemical coordination. The thermocoupled electrochemical oxidation of aniline achieved a fast rate and high efficiency for the full minimization of aniline to CO 2 with the stability of the electrode and without formation of polyaniline (PAN) passivation film. A clear mechanism of aniline oxidation indicated a switching of the reactive pathway by the STEP process. Due to the coupling of solar thermochemistry and electrochemistry, the electrochemical current remained stable, significantly improving the oxidation efficiency and mineralization rate by apparently decreasing the electrolytic potential when applied with high temperature. The oxidation rate of aniline and chemical oxygen demand (COD) removal rate could be lifted up to 2.03 and 2.47 times magnification compared to conventional electrolysis, respectively. We demonstrate that solar-driven STEP processes are capable of completely mineralizing aniline with high utilization of solar energy. STEP aniline oxidation can be utilized as a green, sustainable water treatment.

The performance and decolourization kinetics of O3/H2O2 oxidation of reactive green 19 dye in wastewater

NASA Astrophysics Data System (ADS)

Sabri, S. N.; Abidin, C. Z. A.; Fahmi; Kow, S. H.; Razali, N. A.

2018-03-01

The degradations characteristic of azo dye Reactive Green 19 (RG19) was investigated using advanced oxidation process (AOPs). It was evaluated based on colour and chemical oxygen demand (COD) removal. The effect of operational parameters such as initial dye concentration, initial dosage of hydrogen peroxide (H2O2), contact time, and pH was also being studied. The samples were treated by ozonation (O3) and peroxone O3/H2O2 process. Advanced oxidation processes (AOPs) involve two stages of oxidation; firstly is the formation of strong oxidant and secondly the reaction of organic contaminants in water. In addition, the term advanced oxidation is referring to the processes in which oxidation of organic contaminants occurs primarily through reactions with hydroxyl radicals. There are several analyses that use to determine the efficiency of the treatment process, which are UV-Vis absorption spectra, COD, Fourier Transform Infrared (FT-IR), and pH. The results demonstrated that the ozone oxidation was efficient in decolourization and good in mineralization, based on the reduction of colour and COD. Additionally, results indicate that H2O2 is able to perform better than ozonation in order to decolourize the dye wastewater with 0.5 mL H2O2/L dye dosage of H2O2 at different initial concentration, initial pH, with contact time.

Osteoconductivity and Hydrophilicity of TiO2 Coatings on Ti Substrates Prepared by Different Oxidizing Processes

PubMed Central

Yamamoto, Dai; Kawai, Ikki; Kuroda, Kensuke; Ichino, Ryoichi; Okido, Masazumi; Seki, Azusa

2012-01-01

Various techniques for forming TiO2 coatings on Ti have been investigated for the improvement of the osteoconductivity of Ti implants. However, it is not clear how the oxidizing process affects this osteoconductivity. In this study, TiO2 coatings were prepared using the following three processes: anodizing in 0.1 M H3PO4 or 0.1 M NaOH aqueous solution; thermal oxidation at 673 K for 2 h in air; and a two-step process of anodizing followed by thermal oxidation. The oxide coatings were evaluated using SEM, XRD, and XPS. The water contact angle on the TiO2 coatings was measured as a surface property. The osteoconductivity of these samples was evaluated by measuring the contact ratio of formed hard tissue on the implanted samples (defined as the R B-I value) after 14 d implantation in rats' tibias. Anatase was formed by anodizing and rutile by thermal oxidation, but the difference in the TiO2 crystal structure did not influence the osteoconductivity. Anodized TiO2 coatings were hydrophilic, but thermally oxidized TiO2 coatings were less hydrophilic than anodized TiO2 coatings because they lacked in surface OH groups. The TiO2 coating process using anodizing without thermal oxidation gave effective improvement of the osteoconductivity of Ti samples. PMID:23316128

Aerobic Methane Oxidation in Alaskan Lakes Along a Latitudinal Transect

NASA Astrophysics Data System (ADS)

Martinez-Cruz, K. C.; Sepulveda-Jauregui, A.; Walter Anthony, K. M.; Anthony, P.; Thalasso, F.

2013-12-01

Karla Martinez-Cruz* **, Armando Sepulveda-Jauregui*, Katey M. Walter Anthony*, Peter Anthony*, and Frederic Thalasso**. * Water and Environmental Research Center, Institute of Northern Engineering, University of Alaska Fairbanks, Fairbanks, Alaska. ** Biotechnology and Bioengineering Department, Cinvestav, Mexico city, D. F., Mexico. Methane (CH4) is the third most important greenhouse gas in the atmosphere, after carbon dioxide and water vapor. Boreal lakes play an important role in the current global warming by contributing as much as 6% of global atmospheric CH4 sources annually. On the other hand, aerobic methane oxidation (methanotrophy) in lake water is a fundamental process in global methane cycling that reduces the amount of CH4 emissions to the atmosphere. Several environmental factors affect aerobic methane oxidation in the water column both directly and indirectly, including concentration of CH4 and O2, temperature and carbon budgets of lakes. We analyzed the potential of aerobic methane oxidation (PMO) rates in incubations of water collected from 30 Alaskan lakes along a north-south transect during winter and summer 2011. Our findings showed an effect of CH4 and O2 concentrations, temperature and yedoma thawing permafrost on PMO activity in the lake water. The highest PMO rates were observed in summer by lakes situated on thawing yedoma permafrost, most of them located in the interior of Alaska. We also estimated that 60-80% of all CH4 produced in Alaskan lakes could be taken up by methanotrophs in the lake water column, showing the significant influence of aerobic methane oxidation of boreal lakes to the global CH4 budget.

Accumulation of Contaminants in the Distribution System.

EPA Science Inventory

Removal of arsenic from water using iron-related processes including coagulation with iron salts, iron removal with oxidation/filtration, and specific iron resins is established. These processes are effective because iron solids including minerals and chemical floc have strong ad...

Partitioning Nitrification Between Specific Archaeal and Bacterial Clades in a Large, Nitrogen-Rich Estuary (San Francisco Bay, CA)

NASA Astrophysics Data System (ADS)

Damashek, J.; Casciotti, K. L.; Francis, C. A.

2014-12-01

Nitrification is the sole link between nitrogen inputs and losses in marine ecosystems, and understanding the microbial ecology and biogeochemistry of nitrification is therefore crucial for understanding how aquatic ecosystems process nitrogen. Recently-discovered ammonia-oxidizing archaea (AOA), rather than ammonia-oxidizing bacteria (AOB), appear to drive ammonia oxidation in many ecosystems, including much of the ocean. However, few studies have investigated these microbes in estuary waters, despite the fact nitrogen concentrations in estuaries are often far higher than the ocean, and can cause drastic ecological harm. We sought to determine the roles of AOA and AOB in driving pelagic nitrification throughout San Francisco Bay, by combining biogeochemical rate measurements with a suite of measurements of the abundance and diversity of AOA and AOB. It addition to traditional functional gene analyses and high-throughput 16S amplicon sequencing, we developed novel qPCR assays to selectively target the ammonia-oxidizing clades found in this estuary, which gave insights into clade-specific distributional patterns. Our biogeochemical data suggest a sizable fraction of ammonium in the bay is oxidized in the water column, likely by AOA, with nitrification in bottom waters also oxidizing a substantial portion of the ammonium exuded by sediments. Generally, Sacramento River waters and Suisun Bay bottom waters had the highest nitrification rates. AOA outnumbered AOB at most stations, and were present in high abundance at both the marine and freshwater ends of the estuary, while AOB abundance was highest in the low-salinity, brackish regions. Different archaeal clades were found at either end of the estuary, suggesting strong niche partitioning along the salinity gradient, with a third clade present largely in brackish waters. This work helps to assess the ability of ammonia-oxidizing microbes in estuaries to transform nitrogen prior to water discharge into the sea, and furthers our understanding of the roles of specific clades of these microbes in complex estuarine ecosystems.

Chromium cycling in soils and water: links, gaps, and methods.

PubMed

Bartlett, R J

1991-05-01

The major links in the cycling of chromium in soils and in natural waters are between chromium(III) and chromium (VI). Between the larger links are lesser links involving processes of mobilization and oxidation of CrIII and reduction of CrVI. The gaps are mainly in our understanding of the factors that control these processes. If soluble CrIII is added to an "average" soil, a portion of it will become immediately oxidized by manganese oxides to CrVI. The rest of the CrIII may remain reduced for long periods of time, even in the presence of electron-accepting manganese oxides. However, this less available CrIII can be mobilized by low molecular weight organic complexers and then oxidized where redox conditions are optimal. Usually part of any CrVI added to a soil or sediment will be reduced instantly, especially under acid conditions. On the other hand, high concentrations of polluting CrVI may quickly exhaust the readily available reducing power of the matrix material and excess CrVI, the thermodynamically stable form in air, may persist for years in soils or lagoons without reduction. Cleanup of chromium pollution must involve the surrounding of both CrIII and CrVI with excesses of slowly available reducing substances and sealing them permanently from inputs of atmospheric oxygen. Monitoring the effectiveness of the measures is mandatory, but fortunately the chemical testing for CrVI in soil and water is simple and problem free compared with most colorimetric determinations.

Partial oxidation of landfill leachate in supercritical water: Optimization by response surface methodology

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

Gong, Yanmeng; Wang, Shuzhong; Xu, Haidong

Highlights: • Partial oxidation of landfill leachate in supercritical water was investigated. • The process was optimized by Box–Behnken design and response surface methodology. • GY{sub H2}, TRE and CR could exhibit up to 14.32 mmol·gTOC{sup −1}, 82.54% and 94.56%. • Small amounts of oxidant can decrease the generation of tar and char. - Abstract: To achieve the maximum H{sub 2} yield (GY{sub H2}), TOC removal rate (TRE) and carbon recovery rate (CR), response surface methodology was applied to optimize the process parameters for supercritical water partial oxidation (SWPO) of landfill leachate in a batch reactor. Quadratic polynomial models formore » GY{sub H2}, CR and TRE were established with Box–Behnken design. GY{sub H2}, CR and TRE reached up to 14.32 mmol·gTOC{sup −1}, 82.54% and 94.56% under optimum conditions, respectively. TRE was invariably above 91.87%. In contrast, TC removal rate (TR) only changed from 8.76% to 32.98%. Furthermore, carbonate and bicarbonate were the most abundant carbonaceous substances in product, whereas CO{sub 2} and H{sub 2} were the most abundant gaseous products. As a product of nitrogen-containing organics, NH{sub 3} has an important effect on gas composition. The carbon balance cannot be reached duo to the formation of tar and char. CR increased with the increase of temperature and oxidation coefficient.« less

New perspectives on the passive treatment of ferruginous circumneutral mine waters in the UK.

PubMed

Sapsford, D J

2013-11-01

This paper examines major physico-chemical processes during the passive treatment of ferruginous circumneutral drainage from abandoned coal mines in the UK. Data collected over several years of studies on mine water treatment systems shed new light on the relative importance of hydraulics, settling velocity, Fe(II) oxidation rates and cascade aeration, which, in turn, informs the design of future systems. This paper demonstrates that (1) the complex settling behaviour of Fe(III) precipitates may be described by a first-order volumetric process and that settling rate is different for different mine waters; (2) the hydraulic efficiency (ratio of time to peak tracer concentration to nominal residence time) of the settling ponds studied was widely variable at low flow rates in comparison to constructed wetlands; (3) aeration cascades contribute dissolved oxygen and lead to a rise in pH due to CO2 degassing, which are very important in reducing the required time for iron oxidation and removal; (4) for at least 10 of the 30 sites examined, modelling of the rates of Fe(II) oxidation and particulate settling reveals that removal of iron is primarily dependent on settling rate; and (5) that substantial increases in pH can be brought about by forced aeration of mine water over several hours. Findings of this study apply to the majority of coal mine water treatment sites in the UK and may have broader application to other ferruginous waters with circumneutral pH or after treatment to increase pH.

Vapor Phase Catalytic Ammonia Reduction

NASA Technical Reports Server (NTRS)

Flynn, Michael T.; Harper, Lynn D. (Technical Monitor)

1994-01-01

This paper discusses the development of a Vapor Phase Catalytic Ammonia Reduction (VPCAR) teststand and the results of an experimental program designed to evaluate the potential of the technology as a water purification process. In the experimental program the technology is evaluated based upon product water purity, water recovery rate, and power consumption. The experimental work demonstrates that the technology produces high purity product water and attains high water recovery rates at a relatively high specific power consumption. The experimental program was conducted in 3 phases. In phase I an Igepon(TM) soap and water mixture was used to evaluate the performance of an innovative Wiped-Film Rotating-Disk evaporator and associated demister. In phase II a phenol-water solution was used to evaluate the performance of the high temperature catalytic oxidation reactor. In phase III a urine analog was used to evaluate the performance of the combined distillation/oxidation functions of the processor.

Methanogenic Pathway and Fraction of CH4 Oxidized in Paddy Fields: Seasonal Variation and Effect of Water Management in Winter Fallow Season

PubMed Central

Zhang, Guangbin; Liu, Gang; Zhang, Yi; Ma, Jing; Xu, Hua; Yagi, Kazuyuki

2013-01-01

A 2-year field and incubation experiment was conducted to investigate δ13C during the processes of CH4 emission from the fields subjected to two water managements (flooding and drainage) in the winter fallow season, and further to estimate relative contribution of acetate to total methanogenesis (Fac) and fraction of CH4 oxidized (Fox) based on the isotopic data. Compared with flooding, drainage generally caused CH4, either anaerobically or aerobically produced, depleted in 13C. There was no obvious difference between the two in transport fractionation factor (εtransport) and δ13C-value of emitted CH4. CH4 emission was negatively related to its δ13C-value in seasonal variation (P<0.01). Acetate-dependent methanogenesis in soil was dominant (60–70%) in the late season, while drainage decreased Fac-value by 5–10%. On roots however, CH4 was mostly produced through H2/CO2 reduction (60–100%) over the season. CH4 oxidation mainly occurred in the first half of the season and roughly 10–90% of the CH4 was oxidized in the rhizosphere. Drainage increased Fox-value by 5–15%, which is possibly attributed to a significant decrease in production while no simultaneous decrease in oxidation. Around 30–70% of the CH4 was oxidized at the soil-water interface when CH4 in pore water was released into floodwater, although the amount of CH4 oxidized therein might be negligible relative to that in the rhizosphere. CH4 oxidation was also more important in the first half of the season in lab conditions and about 5–50% of the CH4 was oxidized in soil while almost 100% on roots. Drainage decreased Fox-value on roots by 15% as their CH4 oxidation potential was highly reduced. The findings suggest that water management in the winter fallow season substantially affects Fac in the soil and Fox in the rhizosphere and roots rather than Fac on roots and Fox at the soil-water interface. PMID:24069259

A new mechanism-based inhibitor of photosynthetic water oxidation: Acetone hydrazone. I. Equilibrium reactions

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

Tso, J.; Dismukes, G.C.; Petrouleas, V.

1990-08-21

The process of photosynthetic water oxidation has been investigated by using a new type of water oxidation inhibitor, the alkyl hydrazones. Acetone hydrazone (AceH), (CH{sub 3}){sub 2}CNNH{sub 2}, inhibits water oxidation by a mechanism that is analogous to that of NH{sub 2}OH. This involves binding to the water-oxidizing complex (WOC), followed by photoreversible reduction of manganese (loss of the S{sub 1} {yields} S{sub 2} reaction). At higher AceH concentrations the S{sub 1} state is reduced in the dark and Mn is released, albeit to a lesser extent than with NH{sup 2}OH. Following extraction of Mn, AceH is able to donatemore » electrons rapidly to the reaction center tyrosine radical Z{sup +} ({sup 161}Tyr-D{sub 1} protein), more slowly to a reaction center radical C{sup +}, and not at all to the dark-stable tyrosine radical D{sup +} ({sup 160}Tyr-D{sub 2} protein) which must be sequestered in an inaccessible site. Unexpectedly, Cl{sup {minus}} was found not to interfere or compete with AceH for binding to the WOC in the S{sub 1} state, in contrast to the reported rate of binding of N,N-dimethylhydroxylamine (CH{sub 3}){sub 2}NOH. The authors interpret the latter behavior as due to ionic screening of the thylakoid membrane, rather than a specific Cl site involved in water oxidation. AceH appears not to bind to the acceptor side of PSII as evidenced by normal EPR signals both for Q{sub A}{sup {minus}}Fe(II), the primary electron acceptor, and for the oxidized Fe(III) acceptor (Q{sub 400} species), in contrast to that observed with NH{sub 2}OH. AceH can be oxidized in solution by a variety of oxidants including Mn(III) to form a reactive diazo intermediate, (CH{sub 3}){sub 2}CNN, which reacts with carbonyl compounds. Oxidation to this diazo intermediate is postulated to be responsible for inhibition of the WOC.« less

Hierarchical FeTiO3-TiO2 hollow spheres for efficient simulated sunlight-driven water oxidation.

PubMed

Han, Taoran; Chen, Yajie; Tian, Guohui; Wang, Jian-Qiang; Ren, Zhiyu; Zhou, Wei; Fu, Honggang

2015-10-14

Oxygen generation is the key step for the photocatalytic overall water splitting and considered to be kinetically more challenging than hydrogen generation. Here, an effective water oxidation catalyst of hierarchical FeTiO3-TiO2 hollow spheres are prepared via a two-step sequential solvothermal processes and followed by thermal treatment. The existence of an effective heterointerface and built-in electric field in the surface space charge region in FeTiO3-TiO2 hollow spheres plays a positive role in promoting the separation of photoinduced electron-hole pairs. Surface photovoltage, transient-state photovoltage, fluorescence and electrochemical characterization are used to investigate the transfer process of photoinduced charge carriers. The photogenerated charge carriers in the hierarchical FeTiO3-TiO2 hollow spheres with a proper molar ratio display much higher separation efficiency and longer lifetime than those in the FeTiO3 alone. Moreover, it is suggested that the hierarchical porous hollow structure can contribute to the enhancement of light utilization, surface active sites and material transportation through the framework walls. This specific synergy significantly contributes to the remarkable improvement of the photocatalytic water oxidation activity of the hierarchical FeTiO3-TiO2 hollow spheres under simulated sunlight (AM1.5).

Molecular-Level Transformations of Lignin During Photo-Oxidation and Biodegradation

NASA Astrophysics Data System (ADS)

Feng, X.; Hills, K.; Simpson, A. J.; Simpson, M. J.

2009-05-01

As the second most abundant component of terrestrial plant residues, lignin plays a key role in regulating plant litter decomposition, humic substance formation, and dissolved organic matter (OM) production from terrestrial sources. Biodegradation is the primary decomposition process of lignin on land. However, photo- oxidation of lignin-derived compounds has been reported in aquatic systems and is considered to play a vital role in arid and semiarid regions. With increasing ultraviolet (UV) radiation due to ozone depletion, it is important to understand the biogeochemical fate of lignin exposed to photo-oxidation in terrestrial environments. This study examines and compares the transformation of lignin in a three-month laboratory simulation of biodegradation and photo-oxidation using molecular-level techniques. Lignin-derived monomers extracted by copper oxidation were analyzed by gas chromatography/mass spectrometry (GC/MS) from the water-soluble and insoluble OM of 13C-labeled corn leaves. Biodegradation increased the solubility of lignin monomers in comparison to the control samples, and the acid-to-aldehyde (Ad/Al) ratios increased in both the water-soluble and insoluble OM, indicating a higher degree of side-chain lignin oxidation. Photo-oxidation did not produce a significant change on the solubility or Ad/Al ratios of lignin from corn leaves. However, the ratios of trans-to-cis isomers of both cinnamyl units (p-coumaric acid and ferulic acid) increased with photo-oxidation and decreased with biodegradation in the insoluble OM. We also investigated the role of photo-oxidation in lignin transformation in soils cropped with 13C-labeled corn. Interestingly, the organic carbon content increased significantly with time in the water-soluble OM from soil/corn residues under UV radiation. An increase in the concentration of lignin monomers and dimers and the Ad/Al ratios was also observed with photo-oxidation. Iso-branched fatty acids of microbial origin remained in a similar concentration in the water-soluble OM from the UV-radiated and control soils, indicating little microbial contribution to the observed increase in water-soluble carbon. These observations suggest that photo-oxidation may increase the solubility of soil organic matter (SOM) through the oxidation of lignin-derived compounds. Mechanisms of lignin oxidation (demethylation or side-chain oxidation) and molecular size distribution changes of the water-soluble and NaOH-soluble OM during photo-oxidation and biodegradation will also be examined using solution-state nuclear magnetic resonance (NMR) spectroscopy. Collectively, our experiment demonstrates that while biodegradation predominates in the decomposition of lignin in plant litter, photo- oxidation may play an important part in destabilizing lignin-derived compounds in the soil.

Molecular-level transformations of lignin during photo-oxidation and biodegradation

NASA Astrophysics Data System (ADS)

Feng, X.; Hills, K.; Simpson, A. J.; Simpson, M. J.

2009-04-01

As the second most abundant component of terrestrial plant residues, lignin plays a key role in regulating plant litter decomposition, humic substance formation, and dissolved organic matter (OM) production from terrestrial sources. Biodegradation is the primary decomposition process of lignin on land. However, photo-oxidation of lignin-derived compounds has been reported in aquatic systems and is considered to play a vital role in arid and semiarid regions. With increasing ultraviolet (UV) radiation due to ozone depletion, it is important to understand the biogeochemical fate of lignin exposed to photo-oxidation in terrestrial environments. This study examines and compares the transformation of lignin in a three-month laboratory simulation of biodegradation and photo-oxidation using molecular-level techniques. Lignin-derived monomers extracted by copper oxidation were analyzed by gas chromatography/mass spectrometry (GC/MS) from the water-soluble and insoluble OM of 13C-labeled corn leaves. Biodegradation increased the solubility of lignin monomers in comparison to the control samples, and the acid-to-aldehyde (Ad/Al) ratios increased in both the water-soluble and insoluble OM, indicating a higher degree of side-chain lignin oxidation. Photo-oxidation did not produce a significant change on the solubility or Ad/Al ratios of lignin from corn leaves. However, the ratios of trans-to-cis isomers of both cinnamyl units (p-coumaric acid and ferulic acid) increased with photo-oxidation and decreased with biodegradation in the insoluble OM. We also investigated the role of photo-oxidation in lignin transformation in soils cropped with 13C-labeled corn. Interestingly, the organic carbon content increased significantly with time in the water-soluble OM from soil/corn residues under UV radiation. An increase in the concentration of lignin monomers and dimers and the Ad/Al ratios was also observed with photo-oxidation. Iso-branched fatty acids of microbial origin remained in a similar concentration in the water-soluble OM from the UV-radiated and control soils, indicating little microbial contribution to the observed increase in water-soluble carbon. These observations suggest that photo-oxidation may increase the solubility of soil organic matter (SOM) through the oxidation of lignin-derived compounds. Mechanisms of lignin oxidation (demethylation or side-chain oxidation) and molecular size distribution changes of the water-soluble and NaOH-soluble OM during photo-oxidation and biodegradation will also be examined using solution-state nuclear magnetic resonance (NMR) spectroscopy. Collectively, our experiment demonstrates that while biodegradation predominates in the decomposition of lignin in plant litter, photo-oxidation may play an important part in destabilizing lignin-derived compounds in the soil.

Effects of operational conditions on sludge degradation and organic acids formation in low-critical wet air oxidation.

PubMed

Chung, Jinwook; Lee, Mikyung; Ahn, Jaehwan; Bae, Wookeun; Lee, Yong-Woo; Shim, Hojae

2009-02-15

Wet air oxidation processes are to treat highly concentrated organic compounds including refractory materials, sludge, and night soil, and usually operated at supercritical water conditions of high temperature and pressure. In this study, the effects of operational conditions including temperature, pressure, and oxidant dose on sludge degradation and conversion into subsequent intermediates such as organic acids were investigated at low critical wet oxidation conditions. The reaction time and temperature in the wet air oxidation process was shown an important factor affecting the liquefaction of volatile solids, with more significant effect on the thermal hydrolysis reaction rather than the oxidation reaction. The degradation efficiency of sludge and the formation of organic acids were improved with longer reaction time and higher reaction temperature. For the sludge reduction and the organic acids formation under the wet air oxidation, the optimal conditions for reaction temperature, time, pressure, and oxidant dose were shown approximately 240 degrees C, 30min, 60atm, and 2.0L/min, respectively.

Measurement of the initial phase of ozone decomposition in water and wastewater by means of a continuous quench-flow system: application to disinfection and pharmaceutical oxidation.

PubMed

Buffle, Marc-Olivier; Schumacher, Jochen; Salhi, Elisabeth; Jekel, Martin; von Gunten, Urs

2006-05-01

Due to a lack of adequate experimental techniques, the kinetics of the first 20s of ozone decomposition in natural water and wastewater is still poorly understood. Introducing a continuous quench-flow system (CQFS), measurements starting 350 ms after ozone addition are presented for the first time. Very high HO. to O3 exposures ratios (Rct=integralHO.dt/integralO3dt) reveal that the first 20s of ozonation present oxidation conditions that are similar to ozone-based advanced oxidation processes (AOP). The oxidation of carbamazepine could be accurately modeled using O3 and HO. exposures measured with CQFS during wastewater ozonation. These results demonstrate the applicability of bench scale determined second-order rate constants for wastewater ozonation. Important degrees of pharmaceutical oxidation and microbial inactivation are predicted, indicating that a significant oxidation potential is available during wastewater ozonation, even when ozone is entirely decomposed in the first 20s.

Biogenic, urban, and wildfire influences on the molecular composition of dissolved organic compounds in cloud water

NASA Astrophysics Data System (ADS)

Cook, Ryan D.; Lin, Ying-Hsuan; Peng, Zhuoyu; Boone, Eric; Chu, Rosalie K.; Dukett, James E.; Gunsch, Matthew J.; Zhang, Wuliang; Tolic, Nikola; Laskin, Alexander; Pratt, Kerri A.

2017-12-01

Organic aerosol formation and transformation occurs within aqueous aerosol and cloud droplets, yet little is known about the composition of high molecular weight organic compounds in cloud water. Cloud water samples collected at Whiteface Mountain, New York, during August-September 2014 were analyzed by ultra-high-resolution mass spectrometry to investigate the molecular composition of dissolved organic carbon, with a focus on sulfur- and nitrogen-containing compounds. Organic molecular composition was evaluated in the context of cloud water inorganic ion concentrations, pH, and total organic carbon concentrations to gain insights into the sources and aqueous-phase processes of the observed high molecular weight organic compounds. Cloud water acidity was positively correlated with the average oxygen : carbon ratio of the organic constituents, suggesting the possibility for aqueous acid-catalyzed (prior to cloud droplet activation or during/after cloud droplet evaporation) and/or radical (within cloud droplets) oxidation processes. Many tracer compounds recently identified in laboratory studies of bulk aqueous-phase reactions were identified in the cloud water. Organosulfate compounds, with both biogenic and anthropogenic volatile organic compound precursors, were detected for cloud water samples influenced by air masses that had traveled over forested and populated areas. Oxidation products of long-chain (C10-12) alkane precursors were detected during urban influence. Influence of Canadian wildfires resulted in increased numbers of identified sulfur-containing compounds and oligomeric species, including those formed through aqueous-phase reactions involving methylglyoxal. Light-absorbing aqueous-phase products of syringol and guaiacol oxidation were observed in the wildfire-influenced samples, and dinitroaromatic compounds were observed in all cloud water samples (wildfire, biogenic, and urban-influenced). Overall, the cloud water molecular composition depended on air mass source influence and reflected aqueous-phase reactions involving biogenic, urban, and biomass burning precursors.

Concerted One-Electron Two-Proton Transfer Processes in Models Inspired by the Tyr-His Couple of Photosystem II

DOE PAGES

Huynh, Mioy T.; Mora, S. Jimena; Villalba, Matias; ...

2017-05-09

Nature employs a TyrZ-His pair as a redox relay that couples proton transfer to the redox process between P680 and the water oxidizing catalyst in photosystem II. Artificial redox relays composed of different benzimidazole–phenol dyads (benzimidazole models His and phenol models Tyr) with substituents designed to simulate the hydrogen bond network surrounding the TyrZ-His pair have been prepared. Furthermore, when the benzimidazole substituents are strong proton acceptors such as primary or tertiary amines, theory predicts that a concerted two proton transfer process associated with the electrochemical oxidation of the phenol will take place. Furthermore, theory predicts a decrease in themore » redox potential of the phenol by ~300 mV and a small kinetic isotope effect (KIE). Indeed, electrochemical, spectroelectrochemical, and KIE experimental data are consistent with these predictions. Our results were obtained by using theory to guide the rational design of artificial systems and have implications for managing proton activity to optimize efficiency at energy conversion sites involving water oxidation and reduction.« less

Solar photocatalytic degradation of naphthenic acids in oil sands process-affected water.

PubMed

Leshuk, Tim; Wong, Timothy; Linley, Stuart; Peru, Kerry M; Headley, John V; Gu, Frank

2016-02-01

Bitumen mining in the Canadian oil sands creates large volumes of oil sands process-affected water (OSPW), the toxicity of which is due in part to naphthenic acids (NAs) and other acid extractable organics (AEO). The objective of this work was to evaluate the potential of solar photocatalysis over TiO2 to remove AEO from OSPW. One day of photocatalytic treatment under natural sunlight (25 MJ/m(2) over ∼14 h daylight) eradicated AEO from raw OSPW, and acute toxicity of the OSPW toward Vibrio fischeri was eliminated. Nearly complete mineralization of organic carbon was achieved within 1-7 day equivalents of sunlight exposure, and degradation was shown to proceed through a superoxide-mediated oxidation pathway. High resolution mass spectrometry (HRMS) analysis of oxidized intermediate compounds indicated preferential degradation of the heavier and more cyclic NAs (higher number of double bond equivalents), which are the most environmentally persistent fractions. The photocatalyst was shown to be recyclable for multiple uses, and thus solar photocatalysis may be a promising "green" advanced oxidation process (AOP) for OSPW treatment. Copyright © 2015 Elsevier Ltd. All rights reserved.

A pathway of nanocrystallite fabrication by photo-assisted growth in pure water

NASA Astrophysics Data System (ADS)

Jeem, Melbert; Bin Julaihi, Muhammad Rafiq Mirza; Ishioka, Junya; Yatsu, Shigeo; Okamoto, Kazumasa; Shibayama, Tamaki; Iwasaki, Tomio; Kato, Takahiko; Watanabe, Seiichi

2015-06-01

We report a new production pathway for a variety of metal oxide nanocrystallites via submerged illumination in water: submerged photosynthesis of crystallites (SPSC). Similar to the growth of green plants by photosynthesis, nanocrystallites shaped as nanoflowers and nanorods are hereby shown to grow at the protruded surfaces via illumination in pure, neutral water. The process is photocatalytic, accompanied with hydroxyl radical generation via water splitting; hydrogen gas is generated in some cases, which indicates potential for application in green technologies. Together with the aid of ab initio calculation, it turns out that the nanobumped surface, as well as aqueous ambience and illumination are essential for the SPSC method. Therefore, SPSC is a surfactant-free, low-temperature technique for metal oxide nanocrystallites fabrication.

Synthesis of microspheres of triuranium octaoxide by simultaneous water and nitrate extraction from ascorbate-uranyl sols.

PubMed

Brykala, M; Deptula, A; Rogowski, M; Lada, W; Olczak, T; Wawszczak, D; Smolinski, T; Wojtowicz, P; Modolo, G

A new method for synthesis of uranium oxide microspheres (diameter <100 μm) has been developed. It is a variant of our patented Complex Sol-Gel Process, which has been used to synthesize high-quality powders of a wide variety of complex oxides. Starting uranyl-nitrate-ascorbate sols were prepared by addition of ascorbic acid to uranyl nitrate hexahydrate solution and alkalizing by aqueous ammonium hydroxide and then emulsified in 2-ethylhexanol-1 containing 1v/o SPAN-80. Drops of emulsion were firstly gelled by extraction of water by the solvent. Destruction of the microspheres during thermal treatment, owing to highly reactive components in the gels, requires modification of the gelation step by Double Extraction Process-simultaneously extraction of water and nitrates using Primene JMT, which completely eliminates these problem. Final step was calcination in air of obtained microspheres of gels to triuranium octaoxide.

Effect of arsenic on nitrification of simulated mining water.

PubMed

Papirio, S; Zou, G; Ylinen, A; Di Capua, F; Pirozzi, F; Puhakka, J A

2014-07-01

Mining and mineral processing of gold-bearing ores often release arsenic to the environment. Ammonium is released when N-based explosives or cyanide are used. Nitrification of simulated As-rich mining waters was investigated in batch bioassays using nitrifying cultures enriched in a fluidized-bed reactor (FBR). Nitrification was maintained at 100mg AsTOT/L. In batch assays, ammonium was totally oxidized by the FBR enrichment in 48 h. As(III) oxidation to As(V) occurred during the first 3h attenuating arsenic toxicity to nitrification. At 150 and 200mg AsTOT/L, nitrification was inhibited by 25%. Candidatus Nitrospira defluvii and other nitrifying species mainly colonized the FBR. In conclusion, the FBR enriched cultures of municipal activated sludge origins tolerated high As concentrations making nitrification a potent process for mining water treatment. Copyright © 2014 Elsevier Ltd. All rights reserved.

High-Performance Capacitive Deionization Disinfection of Water with Graphene Oxide-graft-Quaternized Chitosan Nanohybrid Electrode Coating.

PubMed

Wang, Yilei; El-Deen, Ahmed G; Li, Peng; Oh, Bernice H L; Guo, Zanru; Khin, Mya Mya; Vikhe, Yogesh S; Wang, Jing; Hu, Rebecca G; Boom, Remko M; Kline, Kimberly A; Becker, David L; Duan, Hongwei; Chan-Park, Mary B

2015-10-27

Water disinfection materials should ideally be broad-spectrum-active, nonleachable, and noncontaminating to the liquid needing sterilization. Herein, we demonstrate a high-performance capacitive deionization disinfection (CDID) electrode made by coating an activated carbon (AC) electrode with cationic nanohybrids of graphene oxide-graft-quaternized chitosan (GO-QC). Our GO-QC/AC CDID electrode can achieve at least 99.9999% killing (i.e., 6 log reduction) of Escherichia coli in water flowing continuously through the CDID cell. Without the GO-QC coating, the AC electrode alone cannot kill the bacteria and adsorbs a much smaller fraction (<82.8 ± 1.8%) of E. coli from the same biocontaminated water. Our CDID process consists of alternating cycles of water disinfection followed by electrode regeneration, each a few minutes duration, so that this water disinfection process can be continuous and it only needs a small electrode voltage (2 V). With a typical brackish water biocontamination (with 10(4) CFU mL(-1) bacteria), the GO-QC/AC electrodes can kill 99.99% of the E. coli in water for 5 h. The disinfecting GO-QC is securely attached on the AC electrode surface, so that it is noncontaminating to water, unlike many other chemicals used today. The GO-QC nanohybrids have excellent intrinsic antimicrobial properties in suspension form. Further, the GO component contributes toward the needed surface conductivity of the CDID electrode. This CDID process offers an economical method toward ultrafast, contaminant-free, and continuous killing of bacteria in biocontaminated water. The proposed strategy introduces a green in situ disinfectant approach for water purification.

Effects of ozone and ozone/peroxide on trace organic contaminants and NDMA in drinking water and water reuse applications.

PubMed

Pisarenko, Aleksey N; Stanford, Benjamin D; Yan, Dongxu; Gerrity, Daniel; Snyder, Shane A

2012-02-01

An ozone and ozone/peroxide oxidation process was evaluated at pilot scale for trace organic contaminant (TOrC) mitigation and NDMA formation in both drinking water and water reuse applications. A reverse osmosis (RO) pilot was also evaluated as part of the water reuse treatment train. Ozone/peroxide showed lower electrical energy per order of removal (EEO) values for TOrCs in surface water treatment, but the addition of hydrogen peroxide increased EEO values during wastewater treatment. TOrC oxidation was correlated to changes in UV(254) absorbance and fluorescence offering a surrogate model for predicting contaminant removal. A decrease in N-nitrosodimethylamine (NDMA) formation potential (after chloramination) was observed after treatment with ozone and ozone/peroxide. However, during spiking experiments with surface water, ozone/peroxide achieved limited destruction of NDMA, while in wastewaters net direct formation of NDMA of 6-33 ng/L was observed after either ozone or ozone/peroxide treatment. Once formed during ozonation, NDMA passed through the subsequent RO membranes, which highlights the significance of the potential for direct NDMA formation during oxidation in reuse applications. Copyright © 2011 Elsevier Ltd. All rights reserved.

Understanding Surface Processes on Mars Through Study of Iron Oxides/Oxyhydroxides: Clues to Surface Alteration and Aqueous Processes

NASA Technical Reports Server (NTRS)

Bishop, J. L.; Mancinelli, R. L.; Dyar, M. D.; Parente, M.; Drief, A.; Lane, M. D.; Murad, E.

2006-01-01

We are performing oxidation and reduction reactions on hydrated ferric oxide minerals in order to investigate how these might alter under a variety of conditions on the surface of Mars. Preliminary experiments on ferrihydrite and goethite showed that heating these minerals in a dry oxidizing environment produces fine-grained hematite, while heating these minerals in a reducing environment produces fine-grained magnetite. Under Mars-like oxidation levels this magnetite then oxidizes to maghemite. These reactions are dependent on the presence of water and organic material that can act as a reductant. We are using reflectance and Mossbauer spectroscopy to characterize the reaction products and TEM to analyze the sample texture. Our preliminary results indicate that magnetite and maghemite could be formed in the soil on Mars from ferrihydrite and goethite if organics were present on early Mars.

Method of forming oxide coatings. [for solar collector heating panels

NASA Technical Reports Server (NTRS)

Mcdonald, G. E. (Inventor)

1983-01-01

This invention is concerned with an improved plating process for covering a substrate with a black metal oxide film. The invention is particularly directed to making a heating panel for a solar collector. A compound is electrodeposited from an aqueous solution containing cobalt metal salts onto a metal substrate. This compound is converted during plating into a black, highly absorbing oxide coating which contains hydrated oxides. This is achieved by the inclusion of an oxidizing agent in the plating bath. The inclusion of an oxidizing agent in the plating bath is contrary to standard electroplating practice. The hydrated oxides are converted to oxides by treatment in a hot bath, such as boiling water. An oxidizing agent may be added to the hot liquid treating bath.

Selective and Catalyst-free Oxidation of D-Glucose to D-Glucuronic acid induced by High-Frequency Ultrasound

NASA Astrophysics Data System (ADS)

Amaniampong, Prince N.; Karam, Ayman; Trinh, Quang Thang; Xu, Kai; Hirao, Hajime; Jérôme, François; Chatel, Gregory

2017-01-01

This systematic experimental investigation reveals that high-frequency ultrasound irradiation (550 kHz) induced oxidation of D-glucose to glucuronic acid in excellent yield without assistance of any (bio)catalyst. Oxidation is induced thanks to the in situ production of radical species in water. Experiments show that the dissolved gases play an important role in governing the nature of generated radical species and thus the selectivity for glucuronic acid. Importantly, this process yields glucuronic acid instead of glucuronate salt typically obtained via conventional (bio)catalyst routes, which is of huge interest in respect of downstream processing. Investigations using disaccharides revealed that radicals generated by high frequency ultrasound were also capable of promoting tandem hydrolysis/oxidation reactions.

Noncovalent magnetic control and reversible recovery of graphene oxide using iron oxide and magnetic surfactants.

PubMed

McCoy, Thomas M; Brown, Paul; Eastoe, Julian; Tabor, Rico F

2015-01-28

The unique charging properties of graphene oxide (GO) are exploited in the preparation of a range of noncovalent magnetic GO materials, using microparticles, nanoparticles, and magnetic surfactants. Adsorption and desorption are controlled by modification of pH within a narrow window of <2 pH units. The benefit conferred by using charge-based adsorption is that the process is reversible, and the GO can be captured and separated from the magnetic nanomaterial, such that both components can be recycled. Iron oxide (Fe2O3) microparticles form a loosely flocculated gel network with GO, which is demonstrated to undergo magnetic compressional dewatering in the presence of an external magnetic field. For composites formed from GO and Fe2O3 nanoparticles, it is found that low Fe2O3:GO mass ratios (<5:1) favor flocculation of GO, whereas higher ratios (>5:1) cause overcharging of the surfaces resulting in restabilization. The effectiveness of the GO adsorption and magnetic capture process is demonstrated by separating traditionally difficult-to-recover gold nanoparticles (d ≈ 10 nm) from water. The fully recyclable nature of the assembly and capture process, combined with the vast adsorption capacity of GO, presents obvious and appealing advantages for applications in decontamination and water treatment.

Dynamic Stabilization of Metal Oxide–Water Interfaces

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

McBriarty, Martin E.; von Rudorff, Guido Falk; Stubbs, Joanne E.

2017-02-08

The interaction of water with metal oxide surfaces plays a crucial role in the catalytic and geochemical behavior of metal oxides. In a vast majority of studies, the interfacial structure is assumed to arise from a relatively static lowest energy configuration of atoms, even at room temperature. Using hematite (α-Fe2O3) as a model oxide, we show through a direct comparison of in situ synchrotron X-ray scattering with density functional theory-based molecular dynamics simulations that the structure of the (1102) termination is dynamically stabilized by picosecond water exchange. Simulations show frequent exchanges between terminal aquo groups and adsorbed water in locationsmore » and with partial residence times consistent with experimentally determined atomic sites and fractional occupancies. Frequent water exchange occurs even for an ultrathin adsorbed water film persisting on the surface under a dry atmosphere. The resulting time-averaged interfacial structure consists of a ridged lateral arrangement of adsorbed water molecules hydrogen bonded to terminal aquo groups. Surface pKa prediction based on bond valence analysis suggests that water exchange will influence the proton-transfer reactions underlying the acid/base reactivity at the interface. Our findings provide important new insights for understanding complex interfacial chemical processes at metal oxide–water interfaces.« less

Role of oxygen diffusion at Ni/Cr2O3 interface in intergranular oxidation of Ni-Cr alloy

NASA Astrophysics Data System (ADS)

Medasani, Bharat; Sushko, Maria; Schreiber, Daniel; Rosso, Kevin; Bruemmer, Stephen

Certain Ni-Cr alloys used in nuclear systems experience intergranular oxidation and stress corrosion cracking when exposed to high-temperature water leading to their degradation and unexpected failure. To develop a mechanistic understanding of grain boundary oxidation processes, we proposed a mesoscale metal alloy oxidation model that combines quantum Density Functional Theory (DFT) with mesoscopic Poisson-Nernst-Planck/classical DFT. This framework encompasses the chemical specificity of elementary diffusion processes and mesoscale reactive dynamics, and allows modeling oxidation processes on experimentally relevant length scales from first principles. As a proof of concept, a preliminary model was previously employed that limited oxygen diffusion pathways to those through the oxide phase and did not allow oxygen diffusion in the alloy or across oxide/alloy interfaces. In this work, we expand the model to include oxygen diffusion pathways along Ni/Cr2O3 interfaces and demonstrate the increasing importance of such pathways for intergranular oxidation of Ni-Cr alloys with high Cr content. This work is supported by the U.S. Dept. of Energy, Office of Science, Basic Energy Sciences, Materials Sciences and Engineering Division. Simulations are performed using PNNL Institutional Computing facility.

Marine ferromanganese encrustations: Archives of changing oceans

USGS Publications Warehouse

Koschinsky, Andrea; Hein, James

2017-01-01

Marine iron–manganese oxide coatings occur in many shallow and deep-water areas of the global ocean and can form in three ways: 1) Fe–Mn crusts can precipitate from seawater onto rocks on seamounts; 2) Fe–Mn nodules can form on the sediment surface around a nucleus by diagenetic processes in sediment pore water; 3) encrustations can precipitate from hydrothermal fluids. These oxide coatings have been growing for thousands to tens of millions of years. They represent a vast archive of how oceans have changed, including variations of climate, ocean currents, geological activity, erosion processes on land, and even anthropogenic impact. A growing toolbox of age-dating methods and element and isotopic signatures are being used to exploit these archives.

A comparison study of the start-up of a MnOx filter for catalytic oxidative removal of ammonium from groundwater and surface water.

PubMed

Cheng, Ya; Li, Ye; Huang, Tinglin; Sun, Yuankui; Shi, Xinxin; Shao, Yuezong

2018-03-01

As an efficient method for ammonium (NH 4 + ) removal, contact catalytic oxidation technology has drawn much attention recently, due to its good low temperature resistance and short start-up period. Two identical filters were employed to compare the process for ammonium removal during the start-up period for ammonium removal in groundwater (Filter-N) and surface water (Filter-S) treatment. Two types of source water (groundwater and surface water) were used as the feed waters for the filtration trials. Although the same initiating method was used, Filter-N exhibited much better ammonium removal performance than Filter-S. The differences in catalytic activity among these two filters were probed using X-ray diffraction (XRD), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), and compositional analysis. XRD results indicated that different manganese oxide species were formed in Filter-N and Filter-S. Furthermore, the Mn3p XPS spectra taken on the surface of the filter films revealed that the average manganese valence of the inactive manganese oxide film collected from Filter-S (FS-MnO x ) was higher than in the film collected from Filter-N (FN-MnO x ). Mn(IV) was identified as the predominant oxidation state in FS-MnO x and Mn(III) was identified as the predominant oxidation state in FN-MnO x . The results of compositional analyses suggested that polyaluminum ferric chloride (PAFC) used during the surface water treatment was an important factor in the mineralogy and reactivity of MnO x . This study provides the theoretical basis for promoting the wide application of the technology and has great practical significance. Copyright © 2017. Published by Elsevier B.V.

Determination of 17O-excess of terrestrial silicate/oxide minerals with respect to Vienna Standard Mean Ocean Water (VSMOW).

PubMed

Tanaka, Ryoji; Nakamura, Eizo

2013-01-30

Oxygen triple isotope compositions give key information for understanding physical processes during isotopic fractionation between the geo-, hydro-, bio-, and atmosphere. For detailed discussion of these topics, it is necessary to determine precise (17)O-excess values of terrestrial silicate/oxide minerals with respect to Vienna Standard Mean Ocean Water (VSMOW). Water was fluorinated in an electrically heated Ni-metal tube into which water and BrF(5) were loaded for the quantitative extraction of oxygen. Silicate/oxide minerals were fluorinated by heating with a CO(2) laser in an atmosphere of BrF(5). The extracted oxygen was purified and isotope ratios of the oxygen triple isotope compositions were determined using a Finnigan MAT253 isotope ratio mass spectrometer. The oxygen triple isotope compositions of meteoric water and terrestrial silicate/oxide minerals fall on statistically distinguishable fractionation lines, defined as [ln(δ(17)O + 1) = λln(δ(18) O + 1) + Δ], where λ and Δ correspond to the slope and intercept, respectively. The fractionation line for meteoric water has λ = 0.5285 ± 0.0005 and Δ = 0.03 ± 0.02‰ and for terrestrial silicate/oxide minerals has λ = 0.5270 ± 0.0005 and Δ = -0.070 ± 0.005‰, at the 95% confidence limit. All the analyzed terrestrial silicate/oxide minerals including internationally accepted reference materials (NBS-28, UWG-2, and San Carlos olivine) have a negative (17)O-excess with respect to VSMOW. We propose that it is necessary to specify if the determined δ(17)O values of terrestrial and extraterrestrial samples are expressed as the difference from VSMOW or the terrestrial silicate mineral-corrected value. Copyright © 2012 John Wiley & Sons, Ltd.

Alternating electron and proton transfer steps in photosynthetic water oxidation

PubMed Central

Klauss, André; Haumann, Michael; Dau, Holger

2012-01-01

Water oxidation by cyanobacteria, algae, and plants is pivotal in oxygenic photosynthesis, the process that powers life on Earth, and is the paradigm for engineering solar fuel–production systems. Each complete reaction cycle of photosynthetic water oxidation requires the removal of four electrons and four protons from the catalytic site, a manganese–calcium complex and its protein environment in photosystem II. In time-resolved photothermal beam deflection experiments, we monitored apparent volume changes of the photosystem II protein associated with charge creation by light-induced electron transfer (contraction) and charge-compensating proton relocation (expansion). Two previously invisible proton removal steps were detected, thereby filling two gaps in the basic reaction-cycle model of photosynthetic water oxidation. In the S2 → S3 transition of the classical S-state cycle, an intermediate is formed by deprotonation clearly before electron transfer to the oxidant (). The rate-determining elementary step (τ, approximately 30 µs at 20 °C) in the long-distance proton relocation toward the protein–water interface is characterized by a high activation energy (Ea = 0.46 ± 0.05 eV) and strong H/D kinetic isotope effect (approximately 6). The characteristics of a proton transfer step during the S0 → S1 transition are similar (τ, approximately 100 µs; Ea = 0.34 ± 0.08 eV; kinetic isotope effect, approximately 3); however, the proton removal from the Mn complex proceeds after electron transfer to . By discovery of the transient formation of two further intermediate states in the reaction cycle of photosynthetic water oxidation, a temporal sequence of strictly alternating removal of electrons and protons from the catalytic site is established. PMID:22988080

Alternating electron and proton transfer steps in photosynthetic water oxidation.

PubMed

Klauss, André; Haumann, Michael; Dau, Holger

2012-10-02

Water oxidation by cyanobacteria, algae, and plants is pivotal in oxygenic photosynthesis, the process that powers life on Earth, and is the paradigm for engineering solar fuel-production systems. Each complete reaction cycle of photosynthetic water oxidation requires the removal of four electrons and four protons from the catalytic site, a manganese-calcium complex and its protein environment in photosystem II. In time-resolved photothermal beam deflection experiments, we monitored apparent volume changes of the photosystem II protein associated with charge creation by light-induced electron transfer (contraction) and charge-compensating proton relocation (expansion). Two previously invisible proton removal steps were detected, thereby filling two gaps in the basic reaction-cycle model of photosynthetic water oxidation. In the S(2) → S(3) transition of the classical S-state cycle, an intermediate is formed by deprotonation clearly before electron transfer to the oxidant (Y Z OX). The rate-determining elementary step (τ, approximately 30 µs at 20 °C) in the long-distance proton relocation toward the protein-water interface is characterized by a high activation energy (E(a) = 0.46 ± 0.05 eV) and strong H/D kinetic isotope effect (approximately 6). The characteristics of a proton transfer step during the S(0) → S(1) transition are similar (τ, approximately 100 µs; E(a) = 0.34 ± 0.08 eV; kinetic isotope effect, approximately 3); however, the proton removal from the Mn complex proceeds after electron transfer to . By discovery of the transient formation of two further intermediate states in the reaction cycle of photosynthetic water oxidation, a temporal sequence of strictly alternating removal of electrons and protons from the catalytic site is established.

Organic carbon sources and controlling processes on aquifer arsenic cycling in the Jianghan Plain, central China.

PubMed

Yu, Kai; Gan, Yiqun; Zhou, Aiguo; Liu, Chongxuan; Duan, Yanhua; Han, Li; Zhang, Yanan

2018-05-30

Groundwater arsenic contamination is a common environmental problem that threatens the health of over 100 million people globally. Apparent seasonal fluctuations in groundwater arsenic concentrations have been reported in various locations worldwide, including the Jianghan Plain, central China. This phenomenon has been attributed to shifts in redox conditions induced by seasonal incursions of surface water. However, it is not clear what processes during the incursion lead to changes in the redox conditions and what is the source of the organic carbon driving these processes. Therefore, we conducted a long-term investigation of stable carbon isotopic compositions in surface water and groundwater, as well as long-term monitoring of hydraulic gradients and geochemical compositions at the Jianghan Plain. Results indicated that a series of biogeochemical processes occurred during surface water incursion, including aerobic microbial respiration, nitrate and sulfate reduction. Groundwater arsenic was removed by adsorption on iron oxyhydroxides produced during oxidation of ferrous iron, resulting in dramatic decreases in arsenic concentrations during surface water recharge seasons. These processes were likely driven by organic carbon vertically transported from surface water and released from the surficial aquitard above 15 m. Groundwater pumping may accelerate the vertical infiltration of oxidizing recharge water and drive exogenous organic carbon to depth. Findings of this study advance the understandings of the mechanisms that cause temporal variations in groundwater As and the importance of exogenous organic carbon that may influence the temporal behavior of arsenic in groundwater. Copyright © 2018 Elsevier Ltd. All rights reserved.

Interactions of Water Vapor with Oxides at Elevated Temperatures

NASA Technical Reports Server (NTRS)

Jacobson, Nathan; Opila, Elizabeth; Copland, Evan; Myers, Dwight

2003-01-01

Many volatile metal hydroxides form by reaction of the corresponding metal oxide with water vapor. These reactions are important in a number of high temperature corrosion processes. Experimental methods for studying the thermodynamics of metal hydroxides include: gas leak Knudsen cell mass spectrometry, free jet sampling mass spectrometry, transpiration and hydrogen-oxygen flame studies. The available experimental information is reviewed and the most stable metal hydroxide species are correlated with position in the periodic table. Current studies in our laboratory on the Si-O-H system are discussed.

[INDICES OF THE OXIDATIVE STATUS IN CHRONIC ADMINISTRATION OF COLLOID CARBONATE CALCIUM PRAPARATION WITH FAUCET AND LOW-MINERALIZED DRINKING WATER IN RATS].

PubMed

Khripach, L V; Mikhaylova, R I; Koganova, Z I; Knyazeva, T D; Alekseeva, A V; Savostikova, O N; Ryzhova, I N; Kruglova, E V; Revzova, T L

2015-01-01

There are discussed the changes of an array of indices of the oxidative status in chronic administration of colloidal calcium carbonate preparation with faucet and low-mineralized drinking water to rats. Slight differences between significant effects of administration of 3 and 30 mg/L of preparation permit to suggest that the process of its incoming delivery into organism of rats has a bottleneck in the nature of total capacity of macrophages of intestinal lymphoid tissue to absorption of particles.

Unique properties of ceria nanoparticles supported on metals: novel inverse ceria/copper catalysts for CO oxidation and the water-gas shift reaction.

PubMed

Senanayake, Sanjaya D; Stacchiola, Dario; Rodriguez, Jose A

2013-08-20

Oxides play a central role in important industrial processes, including applications such as the production of renewable energy, remediation of environmental pollutants, and the synthesis of fine chemicals. They were originally used as catalyst supports and were thought to be chemically inert, but now they are used to build catalysts tailored toward improved selectivity and activity in chemical reactions. Many studies have compared the morphological, electronic, and chemical properties of oxide materials with those of unoxidized metals. Researchers know much less about the properties of oxides at the nanoscale, which display distinct behavior from their bulk counterparts. More is known about metal nanoparticles. Inverse-model catalysts, composed of oxide nanoparticles supported on metal or oxide substrates instead of the reverse (oxides supporting metal nanoparticles), are excellent tools for systematically testing the properties of novel catalytic oxide materials. Inverse models are prepared in situ and can be studied with a variety of surface science tools (e.g. scanning tunneling microscopy, X-ray photoemission spectroscopy, ultraviolet photoemission spectroscopy, low-energy electron microscopy) and theoretical tools (e.g. density functional theory). Meanwhile, their catalytic activity can be tested simultaneously in a reactor. This approach makes it possible to identify specific functions or structures that affect catalyst performance or reaction selectivity. Insights gained from these tests help to tailor powder systems, with the primary objective of rational design (experimental and theoretical) of catalysts for specific chemical reactions. This Account describes the properties of inverse catalysts composed of CeOx nanoparticles supported on Cu(111) or CuOx/Cu(111) as determined through the methods described above. Ceria is an important material for redox chemistry because of its interchangeable oxidation states (Ce⁴⁺ and Ce³⁺). Cu(111), meanwhile, is a standard catalyst for reactions such as CO oxidation and the water-gas shift (WGS). This metal serves as an ideal replacement for other noble metals that are neither abundant nor cost effective. To prepare the inverse system we deposited nanoparticles (2-20 nm) of cerium oxide onto the Cu(111) surface. During this process, the Cu(111) surface grows an oxide layer that is characteristic of Cu₂O (Cu¹⁺). This oxide can influence the growth of ceria nanoparticles. Evidence suggests triangular-shaped CeO₂(111) grows on Cu₂O(111) surfaces while rectangular CeO₂(100) grows on Cu₄O₃(111) surfaces. We used the CeOx/Cu₂O/Cu(111) inverse system to study two catalytic processes: the WGS (CO + H₂O → CO₂ + H₂) and CO oxidation (2CO + O₂ → 2CO₂). We discovered that the addition of small amounts of ceria nanoparticles can activate the Cu(111) surface and achieve remarkable enhancement of catalytic activity in the investigated reactions. In the case of the WGS, the CeOx nanoparticle facilitated this process by acting at the interface with Cu to dissociate water. In the CO oxidation case, an enhancement in the dissociation of O₂ by the nanoparticles was a key factor. The strong interaction between CeOx nanoparticles and Cu(111) when preoxidized and reduced in CO resulted in a massive surface reconstruction of the copper substrate with the introduction of microterraces that covered 25-35% of the surface. This constitutes a new mechanism for surface reconstruction not observed before. These microterraces helped to facilitate a further enhancement of activity towards the WGS by opening an additional channel for the dissociation of water. In summary, inverse catalysts of CeOx/Cu(111) and CeO₂/Cu₂O/Cu(111) demonstrate the versatility of a model system to obtain insightful knowledge of catalytic processes. These systems will continue to offer a unique opportunity to probe key catalytic components and elucidate the relationship between structure and reactivity of novel materials and reactions in the future.

Vacuum distillation: vapor filtered-catalytic oxidation water reclamation system utilizing radioisotopes

NASA Technical Reports Server (NTRS)

Honegger, R. J.; Remus, G. A.; Kurg, E. K.

1971-01-01

The development of a functional model water reclamation system is discussed. The system produces potable water by distillation from the urine and respiration-perspiration condensate at the normal rate generated by four men. Basic processes employed are vacuum distillation, vapor filtration, vapor phase catalytic oxidation, and condensation. The system is designed to use four 75-watt isotope heaters for distillation thermal input, and one 45-watt isotope for the catalytic oxidation unit. The system is capable of collecting and storing urine, and provides for stabilizing the urine by chemical pretreatment. The functional model system is designed for operation in a weightless condition with liquid-vapor phase separators for the evaporator still, and centrifugal separators for urine collection and vapor condensation. The system provides for storing and dispensing reclaimed potable water. The system operates in a batch mode for 40 days, with urine residues accumulating in the evaporator. The evaporator still and residue are removed to storage and replaced with a fresh still for the next 40-day period.

Controllable Edge Oxidation and Bubbling Exfoliation Enable the Fabrication of High Quality Water Dispersible Graphene

PubMed Central

Tian, Suyun; Sun, Jing; Yang, Siwei; He, Peng; Wang, Gang; Di, Zengfeng; Ding, Guqiao; Xie, Xiaoming; Jiang, Mianheng

2016-01-01

Despite significant progresses made on mass production of chemically exfoliated graphene, the quality, cost and environmental friendliness remain major challenges for its market penetration. Here, we present a fast and green exfoliation strategy for large scale production of high quality water dispersible few layer graphene through a controllable edge oxidation and localized gas bubbling process. Mild edge oxidation guarantees that the pristine sp2 lattice is largely intact and the edges are functionalized with hydrophilic groups, giving rise to high conductivity and good water dispersibility at the same time. The aqueous concentration can be as high as 5.0 mg mL−1, which is an order of magnitude higher than previously reports. The water soluble graphene can be directly spray-coated on various substrates, and the back-gated field effect transistor give hole and electron mobility of ~496 and ~676 cm2 V−1 s−1, respectively. These results achieved are expected to expedite various applications of graphene. PMID:27666869

Controllable Edge Oxidation and Bubbling Exfoliation Enable the Fabrication of High Quality Water Dispersible Graphene.

PubMed

Tian, Suyun; Sun, Jing; Yang, Siwei; He, Peng; Wang, Gang; Di, Zengfeng; Ding, Guqiao; Xie, Xiaoming; Jiang, Mianheng

2016-09-26

Despite significant progresses made on mass production of chemically exfoliated graphene, the quality, cost and environmental friendliness remain major challenges for its market penetration. Here, we present a fast and green exfoliation strategy for large scale production of high quality water dispersible few layer graphene through a controllable edge oxidation and localized gas bubbling process. Mild edge oxidation guarantees that the pristine sp 2 lattice is largely intact and the edges are functionalized with hydrophilic groups, giving rise to high conductivity and good water dispersibility at the same time. The aqueous concentration can be as high as 5.0 mg mL -1 , which is an order of magnitude higher than previously reports. The water soluble graphene can be directly spray-coated on various substrates, and the back-gated field effect transistor give hole and electron mobility of ~496 and ~676 cm 2 V -1 s -1 , respectively. These results achieved are expected to expedite various applications of graphene.

Controllable Edge Oxidation and Bubbling Exfoliation Enable the Fabrication of High Quality Water Dispersible Graphene

NASA Astrophysics Data System (ADS)

Tian, Suyun; Sun, Jing; Yang, Siwei; He, Peng; Wang, Gang; di, Zengfeng; Ding, Guqiao; Xie, Xiaoming; Jiang, Mianheng

2016-09-01

Despite significant progresses made on mass production of chemically exfoliated graphene, the quality, cost and environmental friendliness remain major challenges for its market penetration. Here, we present a fast and green exfoliation strategy for large scale production of high quality water dispersible few layer graphene through a controllable edge oxidation and localized gas bubbling process. Mild edge oxidation guarantees that the pristine sp2 lattice is largely intact and the edges are functionalized with hydrophilic groups, giving rise to high conductivity and good water dispersibility at the same time. The aqueous concentration can be as high as 5.0 mg mL-1, which is an order of magnitude higher than previously reports. The water soluble graphene can be directly spray-coated on various substrates, and the back-gated field effect transistor give hole and electron mobility of ~496 and ~676 cm2 V-1 s-1, respectively. These results achieved are expected to expedite various applications of graphene.

Chemoselective reduction and oxidation of ketones in water through control of the electron transfer pathway

PubMed Central

Kim, Sun Min; Yoo, Ho Sung; Hosono, Hideo; Yang, Jung Woon; Kim, Sung Wng

2015-01-01

The selective synthesis of different products from the same starting materials in water, which is the most abundant solvent in nature, is a crucial issue as it maximizes the utilization of materials. Realizing such reactions for ketones is of considerable importance because numerous organic functionalities can be obtained via nucleophilic addition reactions. Herein, we report chemoselective reduction and oxidation reactions of 1,2-diketones in water, which initiates anionic electron transfer from the inorganic electride [Ca24Al28O64]4+·4e−, through controlling the pathway of the electrons to substrates. The generation of different radical species for transient intermediates was the key process required to control the reaction selectivity, which was achieved by reacting the anionic electrons with either diketones or O2, leading to the formation of ketyl dianion and superoxide radicals in the reduction and oxidation reactions, respectively. This methodology that utilizes electrides may provide an alternative to the pulse radiolysis of water in synthetic chemistry. PMID:26020413

A hybrid regenerative water recovery system for lunar/Mars life support applications

NASA Technical Reports Server (NTRS)

Verostko, Charles E.; Edeen, Marybeth A.; Packham, Nigel J. C.

1992-01-01

Long-duration manned space missions will require integrated biological and physicochemical processes for recovery of resources from wastes. This paper discusses a hybrid regenerative biological and physicochemical water recovery system designed and built at NASA's Crew and Thermal Systems Division at Johnson Space Center. The system is sized for a four-person crew and consists of a two-stage, aerobic, trickling filter bioreactor; a reverse osmosis system; and a photocatalytic oxidation system. The system was designed to accommodate high organic and inorganic loadings and a low hydraulic loading. The bioreactor was designed to oxidize organics to carbon dioxide and water; the reverse osmosis system reduces inorganic content to potable quality; and the photocatalytic oxidation unit removes residual organic impurities (part per million range) and provides in situ disinfection. The design and performance of the hybrid system for producing potable/hygiene water is described. Aspects of the system such as closure, automation and integration are discussed and preliminary results presented.

Solution Processed Metal Oxide High-κ Dielectrics for Emerging Transistors and Circuits.

PubMed

Liu, Ao; Zhu, Huihui; Sun, Huabin; Xu, Yong; Noh, Yong-Young

2018-06-14

The electronic functionalities of metal oxides comprise conductors, semiconductors, and insulators. Metal oxides have attracted great interest for construction of large-area electronics, particularly thin-film transistors (TFTs), for their high optical transparency, excellent chemical and thermal stability, and mechanical tolerance. High-permittivity (κ) oxide dielectrics are a key component for achieving low-voltage and high-performance TFTs. With the expanding integration of complementary metal oxide semiconductor transistors, the replacement of SiO 2 with high-κ oxide dielectrics has become urgently required, because their provided thicker layers suppress quantum mechanical tunneling. Toward low-cost devices, tremendous efforts have been devoted to vacuum-free, solution processable fabrication, such as spin coating, spray pyrolysis, and printing techniques. This review focuses on recent progress in solution processed high-κ oxide dielectrics and their applications to emerging TFTs. First, the history, basics, theories, and leakage current mechanisms of high-κ oxide dielectrics are presented, and the underlying mechanism for mobility enhancement over conventional SiO 2 is outlined. Recent achievements of solution-processed high-κ oxide materials and their applications in TFTs are summarized and traditional coating methods and emerging printing techniques are introduced. Finally, low temperature approaches, e.g., ecofriendly water-induced, self-combustion reaction, and energy-assisted post treatments, for the realization of flexible electronics and circuits are discussed. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Iron and manganese oxide mineralization in the Pacific

USGS Publications Warehouse

Hein, J. R.; Koschinsky, A.; Halbach, P.; Manheim, F. T.; Bau, M.; Jung-Keuk, Kang; Lubick, N.

1997-01-01

Iron, manganese, and iron-manganese deposits occur in nearly all geomorphologic and tectonic environments in the ocean basins and form by one or more of four processes: (1) hydrogenetic precipitation from cold ambient seawater, (2) precipitation from hydrothermal fluids, (3) precipitation from sediment pore waters that have been modified from bottom water compositions by diagenetic reactions in the sediment column and (4) replacement of rocks and sediment. These processes are discussed.

Removal of cyanobacteria and cyanotoxins through drinking water treatment-full-scale studies?

EPA Science Inventory

This presentation covers the control of intact cyanobacterial cells through particulate removal processes such as coagulation, sedimentation and filtration. The control of cyanobacterial toxins through oxidation and adsorption processes including, but not limited to, chlorine, oz...

EAG Eminent Speaker: Cold war biogeochemistry: Microbes as architects for metal attenuation

NASA Astrophysics Data System (ADS)

Küsel, K.

2012-04-01

Legacy uranium mining in the area of Ronneburg, Germany, has resulted in extensive outflow of highly heavy metal contaminated ground and upcoming mine waters. Mine water flows along a grassland into a small creek and forms iron-rich precipitates yielding rust-colored terraces at the creek bank. These iron oxyhydroxides could have been formed by iron oxidizing bacteria (FeOB) or by chemical oxidation. Precipitates may serve as important biogeochemical interfaces, because heavy metals can adsorb or co-precipitate with Fe(II) or Fe(III) minerals. Thus, microbial Fe(II) oxidation but also the reductive dissolution of iron oxides can be important processes affecting the stability of metal contaminants. Here we present a study on the potential for iron cycling processes and on indigenous bacterial communities in this acidic creek. Oxic and anoxic in vitro sediment incubations revealed iron oxidation and reduction rates of same magnitude, indicating active iron cycling regardless of pH. XRD and TEM comparing the suspended particle load of water samples with fresh creek sediment showed that amorphous particles likely formed first, then aged to become more crystalline iron oxyhydroxides, such as akaganeite and goethite. During this aging process some of the initially smooth, 50-300 nm spherical particles may have formed nano-sized needles, which could potentially provide high reactive surface area for chemical and biological reactions. Surprisingly, total and dissolved metal concentrations in creek water and sediment revealed that elements such as Mn, Si, Ni, or Zn stayed mostly in solution. Only some metals such as Cu, Cr, and U seemed to be particle-associated in the water, likely co-precipitated with or adsorbed onto freshly-precipitating minerals. Pelagic and particle-associated organisms from water as well as fresh sediments were used for 16S rRNA gene cloning and sequencing and showed that members of the Proteobacteria (mainly Betaproteobacteria and Deltaproteobacteria) dominated bacterial communities. The relative fraction of FeOB-related clones was especially high in upcoming underground water and sediment of the adjacent creek site. Up to 80% of clones in sediment microbial 16S rRNA gene clone libraries had ≥97% sequence similarity to reported FeOM or FeRM, demonstrating a strong link to function, even on RNA level. Three novel moderately acidophilic FeOM strains, Thiomonas sp. FB-Cd and FB-6 and Bordetella sp. FB-8, were isolated from pH 6.3 sediment. FB-6 is likely involved in in situ iron oxidation as it has high similarity to a RNA-derived clone from this sediment. Our results demonstrated active microbial iron cycling in heavy metal contaminated creeks, which have important implications for understanding natural attenuation.

Membrane chemical reactor (MCR) combining photocatalysis and microfiltration for grey water treatment.

PubMed

Rivero, M J; Parsons, S A; Jeffrey, P; Pidou, M; Jefferson, B

2006-01-01

Urban water recycling is now becoming an important issue where water resources are becoming scarce. This paper looks at reusing grey water; the preference is treatment processes based on biological systems to remove the dissolved organic content. Here, an alternative process, photocatalysis is discussed as it is an attractive technology that could be well-suited for treating the recalcitrant organic compounds found in grey water. The photocatalytic process oxidises organic reactants at a catalyst surface in the presence of ultraviolet light. Given enough exposure time, organic compounds will be oxidized into CO2 and water. The best contact is achieved in a slurry reactor but a second step to separate and recover the catalyst is need. This paper discusses a new membrane chemical reactor (MCR) combining photocatalysis and microfiltration for grey water treatment.

Mathematical Modeling of Ammonia Electro-Oxidation on Polycrystalline Pt Deposited Electrodes

NASA Astrophysics Data System (ADS)

Diaz Aldana, Luis A.

The ammonia electrolysis process has been proposed as a feasible way for electrochemical generation of fuel grade hydrogen (H2). Ammonia is identified as one of the most suitable energy carriers due to its high hydrogen density, and its safe and efficient distribution chain. Moreover, the fact that this process can be applied even at low ammonia concentration feedstock opens its application to wastewater treatment along with H 2 co-generation. In the ammonia electrolysis process, ammonia is electro-oxidized in the anode side to produce N2 while H2 is evolved from water reduction in the cathode. A thermodynamic energy requirement of just five percent of the energy used in hydrogen production from water electrolysis is expected from ammonia electrolysis. However, the absence of a complete understanding of the reaction mechanism and kinetics involved in the ammonia electro-oxidation has not yet allowed the full commercialization of this process. For that reason, a kinetic model that can be trusted in the design and scale up of the ammonia electrolyzer needs to be developed. This research focused on the elucidation of the reaction mechanism and kinetic parameters for the ammonia electro-oxidation. The definition of the most relevant elementary reactions steps was obtained through the parallel analysis of experimental data and the development of a mathematical model of the ammonia electro-oxidation in a well defined hydrodynamic system, such as the rotating disk electrode (RDE). Ammonia electro-oxidation to N 2 as final product was concluded to be a slow surface confined process where parallel reactions leading to the deactivation of the catalyst are present. Through the development of this work it was possible to define a reaction mechanism and values for the kinetic parameters for ammonia electro-oxidation that allow an accurate representation of the experimental observations on a RDE system. Additionally, the validity of the reaction mechanism and kinetic parameters were supplemented by means of process scale up, performance evaluation, and hydrodynamic analysis in a flow cell electrolyzer. An adequate simulation of the flow electrolyzer performance was accomplished using the obtained kinetic parameters.

The Ecological and Economic Assessment of Efficiency of Environmental Technologies for CHPP (Combined Heat And Power Plant)

NASA Astrophysics Data System (ADS)

Rostuntsova, I. A.; Novichkov, S. V.; Zakharov, O. V.; Kochetkov, A. V.

2017-11-01

The analysis of the trial-industrial research of the effectiveness of burning water fuel mixtures in steam boilers of medium and high pressure at the combustion of natural gas and fuel oil is carried out. As a result of a research decrease in nitrogen oxide concentration is depending on the amount of moisture pumped to the boilers and type of the incinerated fuel. The theoretical model of the formation of nitrogen oxides in the furnace of the boiler in order to optimize the combustion process with the introduction of moisture, whereby to determine the concentrations of nitrogen oxides formed in the combustion process of the method of expansion of the exponential is received. The dependences of the maximal temperature of a torch, reaction rate of formation of nitrogen oxides, the conditional time of reaction, theoretical concentration of nitrogen oxides taking into account input of moisture in a fire chamber of a copper and coefficient of an exit of nitrogen oxides are defined at combustion of fuel taking into account moisture input. The divergence between the experimental and the theoretical value of the NOx concentration does not exceed 3.8%. The methodical provisions of the economic assessment of concentrations of pollutants reduction when entering the water are drafted. The rate the net present value (NPV) is applied. The optimal water-fuel ratio is selected based on the maximum value of the net present value (NPV). The evaluation of the application of environmental protection measures carried out taking into account the fact that by reducing the emission values in the implementation of this activity will decrease the amount of payment for emissions of polluting substances, which are collected from the profits of the enterprise. The cost estimate for the implementation of environmental activities carried out on the basis of lump-sum costs and current costs in environmental technology (increased fuel and water consumption).

Electrochemical investigation of [Co4(μ3-O)4(μ-OAc)4(py)4] and peroxides by cyclic voltammetry.

PubMed

Clatworthy, Edwin B; Li, Xiaobo; Masters, Anthony F; Maschmeyer, Thomas

2016-12-13

Two oxidative redox processes of the neutral cobalt(iii) cubane, [Co 4 (μ 3 -O) 4 (μ-OAc) 4 (py) 4 ], were investigated by cyclic voltammetry at a glassy carbon electrode in acetonitrile. In addition to the first quasi-reversible one-electron oxidation at E 1/2 = 0.283 V vs. Fc 0/+ , a second quasi-reversible one-electron oxidation was observed at E 1/2 = 1.44 V vs. Fc 0/+ . Oxidation at this potential does not facilitate water oxidation. In the presence of tert-butylhydroperoxide the peak current of this second oxidation increases, suggesting oxidation of the peroxide by the doubly oxidised cubane.

Biological attenuation of arsenic and iron in a continuous flow bioreactor treating acid mine drainage (AMD).

PubMed

Fernandez-Rojo, L; Héry, M; Le Pape, P; Braungardt, C; Desoeuvre, A; Torres, E; Tardy, V; Resongles, E; Laroche, E; Delpoux, S; Joulian, C; Battaglia-Brunet, F; Boisson, J; Grapin, G; Morin, G; Casiot, C

2017-10-15

Passive water treatments based on biological attenuation can be effective for arsenic-rich acid mine drainage (AMD). However, the key factors driving the biological processes involved in this attenuation are not well-known. Here, the efficiency of arsenic (As) removal was investigated in a bench-scale continuous flow channel bioreactor treating As-rich AMD (∼30-40 mg L -1 ). In this bioreactor, As removal proceeds via the formation of biogenic precipitates consisting of iron- and arsenic-rich mineral phases encrusting a microbial biofilm. Ferrous iron (Fe(II)) oxidation and iron (Fe) and arsenic removal rates were monitored at two different water heights (4 and 25 mm) and with/without forced aeration. A maximum of 80% As removal was achieved within 500 min at the lowest water height. This operating condition promoted intense Fe(II) microbial oxidation and subsequent precipitation of As-bearing schwertmannite and amorphous ferric arsenate. Higher water height slowed down Fe(II) oxidation, Fe precipitation and As removal, in relation with limited oxygen transfer through the water column. The lower oxygen transfer at higher water height could be partly counteracted by aeration. The presence of an iridescent floating film that developed at the water surface was found to limit oxygen transfer to the water column and delayed Fe(II) oxidation, but did not affect As removal. The bacterial community structure in the biogenic precipitates in the bottom of the bioreactor differed from that of the inlet water and was influenced to some extent by water height and aeration. Although potential for microbial mediated As oxidation was revealed by the detection of aioA genes, removal of Fe and As was mainly attributable to microbial Fe oxidation activity. Increasing the proportion of dissolved As(V) in the inlet water improved As removal and favoured the formation of amorphous ferric arsenate over As-sorbed schwertmannite. This study proved the ability of this bioreactor-system to treat extreme As concentrations and may serve in the design of future in-situ bioremediation system able to treat As-rich AMD. Copyright © 2017 Elsevier Ltd. All rights reserved.

Graphene oxide-based efficient and scalable solar desalination under one sun with a confined 2D water path

PubMed Central

Li, Xiuqiang; Xu, Weichao; Tang, Mingyao; Zhou, Lin; Zhu, Bin; Zhu, Shining; Zhu, Jia

2016-01-01

Because it is able to produce desalinated water directly using solar energy with minimum carbon footprint, solar steam generation and desalination is considered one of the most important technologies to address the increasingly pressing global water scarcity. Despite tremendous progress in the past few years, efficient solar steam generation and desalination can only be achieved for rather limited water quantity with the assistance of concentrators and thermal insulation, not feasible for large-scale applications. The fundamental paradox is that the conventional design of direct absorber−bulk water contact ensures efficient energy transfer and water supply but also has intrinsic thermal loss through bulk water. Here, enabled by a confined 2D water path, we report an efficient (80% under one-sun illumination) and effective (four orders salinity decrement) solar desalination device. More strikingly, because of minimized heat loss, high efficiency of solar desalination is independent of the water quantity and can be maintained without thermal insulation of the container. A foldable graphene oxide film, fabricated by a scalable process, serves as efficient solar absorbers (>94%), vapor channels, and thermal insulators. With unique structure designs fabricated by scalable processes and high and stable efficiency achieved under normal solar illumination independent of water quantity without any supporting systems, our device represents a concrete step for solar desalination to emerge as a complementary portable and personalized clean water solution. PMID:27872280

Graphene oxide-based efficient and scalable solar desalination under one sun with a confined 2D water path.

PubMed

Li, Xiuqiang; Xu, Weichao; Tang, Mingyao; Zhou, Lin; Zhu, Bin; Zhu, Shining; Zhu, Jia

2016-12-06

Because it is able to produce desalinated water directly using solar energy with minimum carbon footprint, solar steam generation and desalination is considered one of the most important technologies to address the increasingly pressing global water scarcity. Despite tremendous progress in the past few years, efficient solar steam generation and desalination can only be achieved for rather limited water quantity with the assistance of concentrators and thermal insulation, not feasible for large-scale applications. The fundamental paradox is that the conventional design of direct absorber-bulk water contact ensures efficient energy transfer and water supply but also has intrinsic thermal loss through bulk water. Here, enabled by a confined 2D water path, we report an efficient (80% under one-sun illumination) and effective (four orders salinity decrement) solar desalination device. More strikingly, because of minimized heat loss, high efficiency of solar desalination is independent of the water quantity and can be maintained without thermal insulation of the container. A foldable graphene oxide film, fabricated by a scalable process, serves as efficient solar absorbers (>94%), vapor channels, and thermal insulators. With unique structure designs fabricated by scalable processes and high and stable efficiency achieved under normal solar illumination independent of water quantity without any supporting systems, our device represents a concrete step for solar desalination to emerge as a complementary portable and personalized clean water solution.

Screen-printed calcium-birnessite electrodes for water oxidation at neutral pH and an "electrochemical harriman series".

PubMed

Lee, Seung Y; González-Flores, Diego; Ohms, Jonas; Trost, Tim; Dau, Holger; Zaharieva, Ivelina; Kurz, Philipp

2014-12-01

A mild screen-printing method was developed to coat conductive oxide surfaces (here: fluorine-doped tin oxide) with micrometer-thick layers of presynthesized calcium manganese oxide (Ca-birnessite) particles. After optimization steps concerning the printing process and layer thickness, electrodes were obtained that could be used as corrosion-stable water-oxidizing anodes at pH 7 to yield current densities of 1 mA cm(-2) at an overpotential of less than 500 mV. Analyses of the electrode coatings of optimal thickness (≈10 μm) indicated that composition, oxide phase, and morphology of the synthetic Ca-birnessite particles were hardly affected by the screen-printing procedure. However, a more detailed analysis by X-ray absorption spectroscopy revealed small modifications of both the Mn redox state and the structure at the atomic level, which could affect functional properties such as proton conductivity. Furthermore, the versatile new screen-printing method was used for a comparative study of various transition-metal oxides concerning electrochemical water oxidation under "artificial leaf conditions" (neutral pH, fairly low overpotential and current density), for which a general activity ranking of RuO2 >Co3 O4 ≈(Ca)MnOx ≈NiO was observed. Within the group of screened manganese oxides, Ca-birnessite performed better than "Mn-only materials" such as Mn2 O3 and MnO2 . © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Coagulation effectiveness of graphene oxide for the removal of turbidity from raw surface water.

PubMed

Aboubaraka, Abdelmeguid E; Aboelfetoh, Eman F; Ebeid, El-Zeiny M

2017-08-01

This study presents the performance of graphene oxide (GO) as a coagulant in turbidity removal from naturally and artificially turbid raw surface water. GO is considered an excellent alternative to alum, the more common coagulant used in water treatment processes, to reduce the environmental release of aluminum. Effects of GO dosage, pH, and temperature on its coagulation ability were studied to determine the ideal turbidity removal conditions. The turbidity removal was ≥95% for all levels of turbid raw surface water (20, 100, and 200 NTU) at optimum conditions. The role of alkalinity in inducing turbidity removal by GO coagulation was much more pronounced upon using raw surface water samples compared with that using artificially turbid deionized water samples. Moreover, GO demonstrated high-performance removal of biological contaminants such as algae, heterotrophic bacteria, and fecal coliform bacteria by 99.0%, 98.8% and 96.0%, respectively, at a dosage of 40 mg/L. Concerning the possible environmental release of GO into the treated water following filtration process, there was no residual GO in a wide range of pH values. The outcomes of the study highlight the excellent coagulation performance of GO for the removal of turbidity and biological contaminants from raw surface water. Copyright © 2017 Elsevier Ltd. All rights reserved.

Sol-Gel Zinc Oxide Humidity Sensors Integrated with a Ring Oscillator Circuit On-a-Chip

PubMed Central

Yang, Ming-Zhi; Dai, Ching-Liang; Wu, Chyan-Chyi

2014-01-01

The study develops an integrated humidity microsensor fabricated using the commercial 0.18 μm complementary metal oxide semiconductor (CMOS) process. The integrated humidity sensor consists of a humidity sensor and a ring oscillator circuit on-a-chip. The humidity sensor is composed of a sensitive film and branch interdigitated electrodes. The sensitive film is zinc oxide prepared by sol-gel method. After completion of the CMOS process, the sensor requires a post-process to remove the sacrificial oxide layer and to coat the zinc oxide film on the interdigitated electrodes. The capacitance of the sensor changes when the sensitive film adsorbs water vapor. The circuit is used to convert the capacitance of the humidity sensor into the oscillation frequency output. Experimental results show that the output frequency of the sensor changes from 84.3 to 73.4 MHz at 30 °C as the humidity increases 40 to 90 %RH. PMID:25353984

Enhanced degradation of paracetamol by UV-C supported photo-Fenton process over Fenton oxidation.

PubMed

Manu, B; Mahamood, S

2011-01-01

For the treatment of paracetamol in water, the UV-C Fenton oxidation process and classic Fenton oxidation have been found to be the most effective. Paracetamol reduction and chemical oxygen demand (COD) removal are measured as the objective functions to be maximized. The experimental conditions of the degradation of paracetamol are optimized by the Fenton process. Influent pH 3, initial H(2)O(2) dosage 60 mg/L, [H(2)O(2)]/[Fe(2+)] ratio 60 : 1 are the optimum conditions observed for 20 mg/L initial paracetamol concentration. At the optimum conditions, for 20 mg/L of initial paracetamol concentration, 82% paracetamol reduction and 68% COD removal by Fenton oxidation, and 91% paracetamol reduction and 82% COD removal by UV-C Fenton process are observed in a 120 min reaction time. By HPLC analysis, 100% removal of paracetamol is observed at the above optimum conditions for the Fenton process in 240 min and for the UV-C photo-Fenton process in 120 min. The methods are effective and they may be used in the paracetamol industry.

Hybrid reactor based on combined cavitation and ozonation: from concept to practical reality.

PubMed

Gogate, P R; Mededovic-Thagard, S; McGuire, D; Chapas, G; Blackmon, J; Cathey, R

2014-03-01

The present work gives an in depth discussion related to the development of a hybrid advanced oxidation reactor, which can be effectively used for the treatment of various types of water. The reactor is based on the principle of intensifying degradation/disinfection using a combination of hydrodynamic cavitation, acoustic cavitation, ozone injection and electrochemical oxidation/precipitation. Theoretical studies have been presented to highlight the uniform distribution of the cavitational activity and enhanced generation of hydroxyl radicals in the cavitation zone, as well as higher turbulence in the main reactor zone. The combination of these different oxidation technologies have been shown to result in enhanced water treatment ability, which can be attributed to the enhanced generation of hydroxyl radicals, enhanced contact of ozone and contaminants, and the elimination of mass transfer resistances during electrochemical oxidation/precipitation. Compared to the use of individual approaches, the hybrid reactor is expected to intensify the treatment process by 5-20 times, depending on the application in question, which can be confirmed based on the literature illustrations. Also, the use of Ozonix® has been successfully proven while processing recycled fluids at commercial sites on over 750 oil and natural gas wells during hydraulic operations around the United States. The superiority of the hybrid process over conventional chemical treatments in terms of bacteria and scale reduction as well as increased water flowability and better chemical compatibility, which is a key requirement for oil and gas applications, has been established. Copyright © 2013 Elsevier B.V. All rights reserved.

Energy, chemical disequilibrium, and geological constraints on Europa.

PubMed

Hand, Kevin P; Carlson, Robert W; Chyba, Christopher F

2007-12-01

Europa is a prime target for astrobiology. The presence of a global subsurface liquid water ocean and a composition likely to contain a suite of biogenic elements make it a compelling world in the search for a second origin of life. Critical to these factors, however, may be the availability of energy for biological processes on Europa. We have examined the production and availability of oxidants and carbon-containing reductants on Europa to better understand the habitability of the subsurface ocean. Data from the Galileo Near-Infrared Mapping Spectrometer were used to constrain the surface abundance of CO(2) to 0.036% by number relative to water. Laboratory results indicate that radiolytically processed CO(2)-rich ices yield CO and H(2)CO(3); the reductants H(2)CO, CH(3)OH, and CH(4) are at most minor species. We analyzed chemical sources and sinks and concluded that the radiolytically processed surface of Europa could serve to maintain an oxidized ocean even if the surface oxidants (O(2), H(2)O(2), CO(2), SO(2), and SO(4) (2)) are delivered only once every approximately 0.5 Gyr. If delivery periods are comparable to the observed surface age (30-70 Myr), then Europa's ocean could reach O(2) concentrations comparable to those found in terrestrial surface waters, even if approximately 10(9) moles yr(1) of hydrothermally delivered reductants consume most of the oxidant flux. Such an ocean would be energetically hospitable for terrestrial marine macrofauna. The availability of reductants could be the limiting factor for biologically useful chemical energy on Europa.

HEAVY WATER PRODUCTION--DESCRIPTION OF PROCESS FOR THE PRODUCTION OF HYDROGEN AND WATER ENRICHED IN HEAVY WATER

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

Chrones, J.

1951-05-29

A process which produces H/sub 2/ water enriched in D is described. Natural gas is oxidized to CO and H/sub 2/. These gases at 600 C reduce FeO in a fluidized bed regenerator, and the mixture of gases leaving the regenerator is burned in the boiler which supplies steam at 600 C. This steam reacts with iron dust from the regenerator to produce FeO and H/sub 2/ The deuterium is stripped from the H/sub 2/ with water in a catalytic exchange tower. The water thus enriched passes to an electrolytic step which concentrates D/sub 2/O to 99.8%. (T.R.H.)

Impact of Oxidative Dissolution on Black Shale Fracturing: Implication for Shale Fracturing Treatment Design

NASA Astrophysics Data System (ADS)

You, L.; Chen, Q.; Kang, Y.; Cheng, Q.; Sheng, J.

2017-12-01

Black shales contain a large amount of environment-sensitive compositions, e.g., clay minerals, carbonate, siderite, pyrite, and organic matter. There have been numerous studies on the black shales compositional and pore structure changes caused by oxic environments. However, most of the studies did not focus on their ability to facilitate shale fracturing. To test the redox-sensitive aspects of shale fracturing and its potentially favorable effects on hydraulic fracturing in shale gas reservoirs, the induced microfractures of Longmaxi black shales exposed to deionized water, hydrochloric acid, and hydrogen peroxide at room-temperature for 240 hours were imaged by scanning electron microscopy (SEM) and CT-scanning in this paper. Mineral composition, acoustic emission, swelling, and zeta potential of the untreated and oxidative treatment shale samples were also recorded to decipher the coupled physical and chemical effects of oxidizing environments on shale fracturing processes. Results show that pervasive microfractures (Fig.1) with apertures ranging from tens of nanometers to tens of microns formed in response to oxidative dissolution by hydrogen peroxide, whereas no new microfracture was observed after the exposure to deionized water and hydrochloric acid. The trajectory of these oxidation-induced microfractures was controlled by the distribution of phyllosilicate framework and flaky or stringy organic matter in shale. The experiments reported in this paper indicate that black shales present the least resistance to crack initiation and subcritical slow propagation in hydrogen peroxide, a process we refer to as oxidation-sensitive fracturing, which are closely related to the expansive stress of clay minerals, dissolution of redox-sensitive compositions, destruction of phyllosilicate framework, and the much lower zeta potential of hydrogen peroxide solution-shale system. It could mean that the injection of fracturing water with strong oxidizing aqueous solution may play an important role in improving hydraulic fracturing of shale formation by reducing the energy requirements for crack growth. However, additional work is needed to the selection of highly-effective, economical, and environmentally friendly oxidants.

Biogenic manganese oxides as reservoirs of organic carbon and proteins in terrestrial and marine environments.

PubMed

Estes, E R; Andeer, P F; Nordlund, D; Wankel, S D; Hansel, C M

2017-01-01

Manganese (Mn) oxides participate in a range of interactions with organic carbon (OC) that can lead to either carbon degradation or preservation. Here, we examine the abundance and composition of OC associated with biogenic and environmental Mn oxides to elucidate the role of Mn oxides as a reservoir for carbon and their potential for selective partitioning of particular carbon species. Mn oxides precipitated in natural brackish waters and by Mn(II)-oxidizing marine bacteria and terrestrial fungi harbor considerable levels of organic carbon (4.1-17.0 mol OC per kg mineral) compared to ferromanganese cave deposits which contain 1-2 orders of magnitude lower OC. Spectroscopic analyses indicate that the chemical composition of Mn oxide-associated OC from microbial cultures is homogeneous with bacterial Mn oxides hosting primarily proteinaceous carbon and fungal Mn oxides containing both protein- and lipopolysaccharide-like carbon. The bacterial Mn oxide-hosted proteins are involved in both Mn(II) oxidation and metal binding by these bacterial species and could be involved in the mineral nucleation process as well. By comparison, the composition of OC associated with Mn oxides formed in natural settings (brackish waters and particularly in cave ferromanganese rock coatings) is more spatially and chemically heterogeneous. Cave Mn oxide-associated organic material is enriched in aliphatic C, which together with the lower carbon concentrations, points to more extensive microbial or mineral processing of carbon in this system relative to the other systems examined in this study, and as would be expected in oligotrophic cave environments. This study highlights Mn oxides as a reservoir for carbon in varied environments. The presence and in some cases dominance of proteinaceous carbon within the biogenic and natural Mn oxides may contribute to preferential preservation of proteins in sediments and dominance of protein-dependent metabolisms in the subsurface biosphere. © 2016 John Wiley & Sons Ltd.

Microwave-Enhanced Photolysis of Norfloxacin: Kinetics, Matrix Effects, and Degradation Pathways

PubMed Central

Liao, Wenchao; Sharma, Virender K.; Xu, Su; Li, Qingsong; Wang, Lei

2017-01-01

Degradation of norfloxacin (NOR) was studied using a combination of microwave and UV irradiation methods (MW/UV process). Remarkable synergistic effect was found between MW and UV light. The removal rate with the MW/UV process was much faster than that with UV light irradiation only. Degradation of NOR followed second-order kinetics and ~72% of NOR could be removed in the first 5 min of MW/UV reaction. Influence of inorganic ions (cations (K+, Mg2+, Ca2+, Cu2+) and anions (Cl−, SO42−, NO3−, CO32−)), humic acid (HA) and surfactants (cation, anion, and non-ionic) on the degradation of NOR by the MW/UV process was investigated. Among the ions, Cu2+ and NO3− ions inhibited the degradation of NOR. The presence of HA and surfactants in water showed a slight inhibition on the NOR removal. Furthermore, the NOR degradation in the MW/UV process was primarily caused by the ·OH-photosensitization steps. Seven intermediates formed by the oxidation of NOR were identified and three reaction pathways were proposed. Removals of NOR in tap water (TW), synthetic wastewater (WW), river water (RW), and seawater (SW) were also studied, which demonstrated that the MW/UV process was an effective oxidation technology for degrading fluoroquinolone antibiotics in different water matrices. PMID:29240671

Investigation of TiO2 based Mixed-metal Oxide Catalysts for the Production of Hydrogen

NASA Astrophysics Data System (ADS)

Luo, Si

Abstract of the Dissertation. Investigation of TiO2 based Mixed-metal Oxide Catalysts for the Production of Hydrogen. by. Si Luo. Doctor of Philosophy. in. Chemistry. Stony Brook University. 2017. The environmental impacts of fossil fuel consumption and the resulting global warming have attracted increasing attention to technologies and fuels that are both sustainable and renewable in the 21st century. To date, hydrogen has been proposed as an encouraging candidate of the next generation of chemical fuels, which meets all demands for carbon free and efficient chemistries that could be produced from a variety of sources. However, despite tremendous efforts, there is a clear need to develop new catalysts for the production of hydrogen through catalytic processes that are sustainable, such as in the photocatalytic splitting of water (PCS: H2O → H2 + 0.5O2) and the water-gas shift process (WGS: CO + H2O → H2 + CO2). This thesis is primarily motivated by this challenge and has focused on the photochemical and thermal production of H2 by the employment of novel TiO2 based catalysts. TiO2 is one of the most widely studied photocatalysts in all history, due to its relatively high activity, robust stability, safety and low cost. In this thesis, several TiO2-based mixed metal oxide nano catalysts (CeOx-TiO2, Ru-TiO2, Ga-TiO2) have been synthesized with carefully controlled morphology/structure and with inclusion of co-catalysts (Pt). These novel materials were comprehensively characterized to better understand their morphology, crystal structure, and electronic properties in an attempt to unravel phenomena responsible for high catalytic performance for the production of H2 from H2O. We have discovered the importance of low-dimensional metal oxide and interfacial stabilized nano-scaled mixed metal oxides for H2 production, while learning how best to tune such structure to optimize both thermal and photochemical conversion. Optimized structure and/or composition have been identified for TiO2 modified in different ways by another metal oxide (CeOx) or with dopants (Ga, Ru). In addition, we have also studied the water gas shift reaction on several TiO2 supported catalysts, where similar concepts can be applied. Advanced In situ characterization enabled the investigation of the catalyst structure, surface chemical intermediates and active species under reaction conditions. The influence of metal-oxide, oxide-oxide interactions has been further revealed for both the water-gas shift and the photocatalytic splitting of water.

EFFECTS OF AQUATIC HUMIC SUBSTANCES ON ANALYSIS FOR HYDROGEN PEROXIDE USING PEROXIDASE-CATALYZED OXIDATIONS OF TRIARYLMETHANES OR P-HYDROXYPENYLACETIC ACID (JOURNAL VERSION)

EPA Science Inventory

A sensitive procedure is described for trace analysis of hydrogen peroxide in water. The process involves the peroxide-catalyzed oxidation of the leuco forms of two dyes, crystal violet and malachite green. The sensitivity of this procedure, as well as of another procedure based ...