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

Liu, Shizhong; White, Michael G.; Liu, Ping

Here, we report a detailed mechanistic study of the oxygen reduction reaction (ORR) on Pt(111) in alkaline solution, combining density functional theory and kinetic Monte Carlo simulations. A complex reaction network including four possible pathways via either 2e – or 4e – transfer is established and is able to reproduce the experimental measured polarization curve at both low- and high-potential regions. Our results show that it is essential to account for solvation by water and the dynamic coverage of *OH to describe the reaction kinetics well. In addition, a chemisorbed water (*H 2O)-mediated mechanism including 4e – transfers is identified,more » where the reduction steps via *H 2O on the surface are potential-independent and only the final removal of *OH from the surface in the form of OH –(aq) contributes to the current. For the ORR in alkaline solutions, such a mechanism is more competitive than the associative and dissociative mechanisms typically used to describe the ORR in acid solution. Finally, *OH and **O 2 intermediates are found to be critically important for tuning the ORR activity of Pt in alkaline solution. To enhance the activity, the binding of Pt should be tuned in such a way that *OH binding is weak enough to release more surface sites under working conditions, while **O 2 binding is strong enough to enable the ORR via the 4e – transfer mechanism.« less

COUPLING THE ALKALINE-SURFACTANT-POLYMER TECHNOLOGY AND THE GELATION TECHNOLOGY TO MAXIMIZE OIL PRODUCTION

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

Malcolm Pitts; Jie Qi; Dan Wilson

2005-04-01

Gelation technologies have been developed to provide more efficient vertical sweep efficiencies for flooding naturally fractured oil reservoirs or more efficient areal sweep efficiency for those with high permeability contrast ''thief zones''. The field proven alkaline-surfactant-polymer technology economically recovers 15% to 25% OOIP more oil than waterflooding from swept pore space of an oil reservoir. However, alkaline-surfactant-polymer technology is not amenable to naturally fractured reservoirs or those with thief zones because much of injected solution bypasses target pore space containing oil. This work investigates whether combining these two technologies could broaden applicability of alkaline-surfactant-polymer flooding into these reservoirs. A priormore » fluid-fluid report discussed interaction of different gel chemical compositions and alkaline-surfactant-polymer solutions. Gel solutions under dynamic conditions of linear corefloods showed similar stability to alkaline-surfactant-polymer solutions as in the fluid-fluid analyses. Aluminum-polyacrylamide, flowing gels are not stable to alkaline-surfactant-polymer solutions of either pH 10.5 or 12.9. Chromium acetate-polyacrylamide flowing and rigid flowing gels are stable to subsequent alkaline-surfactant-polymer solution injection. Rigid flowing chromium acetate-polyacrylamide gels maintained permeability reduction better than flowing chromium acetate-polyacrylamide gels. Silicate-polyacrylamide gels are not stable with subsequent injection of either a pH 10.5 or a 12.9 alkaline-surfactant-polymer solution. Chromium acetate-xanthan gum rigid gels are not stable to subsequent alkaline-surfactant-polymer solution injection. Resorcinol-formaldehyde gels were stable to subsequent alkaline-surfactant-polymer solution injection. When evaluated in a dual core configuration, injected fluid flows into the core with the greatest effective permeability to the injected fluid. The same gel stability trends to subsequent alkaline-surfactant-polymer injected solution were observed. Aluminum citrate-polyacrylamide, resorcinol-formaldehyde, and the silicate-polyacrylamide gel systems did not produce significant incremental oil in linear corefloods. Both flowing and rigid flowing chromium acetate-polyacrylamide gels and the xanthan gum-chromium acetate gel system produced incremental oil with the rigid flowing gel producing the greatest amount. Higher oil recovery could have been due to higher differential pressures across cores. None of the gels tested appeared to alter alkaline-surfactant-polymer solution oil recovery. Total waterflood plus chemical flood oil recovery sequence recoveries were all similar.« less

Cation exchange properties of zeolites in hyper alkaline aqueous media.

PubMed

Van Tendeloo, Leen; de Blochouse, Benny; Dom, Dirk; Vancluysen, Jacqueline; Snellings, Ruben; Martens, Johan A; Kirschhock, Christine E A; Maes, André; Breynaert, Eric

2015-02-03

Construction of multibarrier concrete based waste disposal sites and management of alkaline mine drainage water requires cation exchangers combining excellent sorption properties with a high stability and predictable performance in hyper alkaline media. Though highly selective organic cation exchange resins have been developed for most pollutants, they can serve as a growth medium for bacterial proliferation, impairing their long-term stability and introducing unpredictable parameters into the evolution of the system. Zeolites represent a family of inorganic cation exchangers, which naturally occur in hyper alkaline conditions and cannot serve as an electron donor or carbon source for microbial proliferation. Despite their successful application as industrial cation exchangers under near neutral conditions, their performance in hyper alkaline, saline water remains highly undocumented. Using Cs(+) as a benchmark element, this study aims to assess the long-term cation exchange performance of zeolites in concrete derived aqueous solutions. Comparison of their exchange properties in alkaline media with data obtained in near neutral solutions demonstrated that the cation exchange selectivity remains unaffected by the increased hydroxyl concentration; the cation exchange capacity did however show an unexpected increase in hyper alkaline media.

Antimicrobial and other properties of a new stabilized alkaline glutaraldehyde disinfectant/sterilizer.

PubMed

Miner, N A; McDowell, J W; Willcockson, G W; Bruckner, N I; Stark, R L; Whitmore, E J

1977-04-01

The properties of stabilized alkaline 2% glutaraldehyde solution (SGS) are discussed. SGS is discussed with regard to its chemistry, antimicrobial properties, organic soil resistance, toxicity, corrosivity and chemical stability. SGS retains the maximum antimicrobial activity of alkaline glutaraldehyde solutions and the chemical stability heretofore observed only with acidic glutaraldehyde solutions. These improvements, along with the inherent resistance of glutaraldehyde to neutralization by organic soil, allow SGS to be continuously used for 14 days in situations of high dilution, or 28 days in situations of low dilution.

Mathematical modeling of high-pH chemical flooding

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

Bhuyan, D.; Lake, L.W.; Pope, G.A.

1990-05-01

This paper describes a generalized compositional reservoir simulator for high-pH chemical flooding processes. This simulator combines the reaction chemistry associated with these processes with the extensive physical- and flow-property modeling schemes of an existing micellar/polymer flood simulator, UTCHEM. Application of the model is illustrated for cases from a simple alkaline preflush to surfactant-enhanced alkaline-polymer flooding.

High pH-Sensitive TRPA1 Activation in Odontoblasts Regulates Mineralization.

PubMed

Kimura, M; Sase, T; Higashikawa, A; Sato, M; Sato, T; Tazaki, M; Shibukawa, Y

2016-08-01

Calcium hydroxide and mineral trioxide aggregate are widely used for indirect and direct pulp capping and root canal filling. Their dissociation into Ca(2+) and OH(-) in dental pulp creates an alkaline environment, which activates reparative/reactionary dentinogenesis. However, the mechanisms by which odontoblasts detect the pH of the extracellular environment remain unclear. We examined the alkali-sensitive intracellular Ca(2+) signaling pathway in rat odontoblasts. In the presence or absence of extracellular Ca(2+), application of alkaline solution increased intracellular Ca(2+) concentration, or [Ca(2+)]i Alkaline solution-induced [Ca(2+)]i increases depended on extracellular pH (8.5 to 10.5) in both the absence and the presence of extracellular Ca(2+) The amplitude was smaller in the absence than in the presence of extracellular Ca(2+) Each increase in [Ca(2+)]i, activated by pH 7.5, 8.5, or 9.5, depended on extracellular Ca(2+) concentration; the equilibrium binding constant for extracellular Ca(2+) concentration decreased as extracellular pH increased (1.04 mM at pH 7.5 to 0.11 mM at pH 9.5). Repeated applications of alkaline solution did not have a desensitizing effect on alkali-induced [Ca(2+)]i increases and inward currents. In the presence of extracellular Ca(2+), alkaline solution-induced [Ca(2+)]i increases were suppressed by application of an antagonist of transient receptor potential ankyrin subfamily member 1 (TRPA1) channels. Ca(2+) exclusion efficiency during alkaline solution-induced [Ca(2+)]i increases was reduced by a Na(+)-Ca(2+) exchanger antagonist. Alizarin red and von Kossa staining revealed increased mineralization levels under repeated high pH stimulation, whereas the TRPA1 antagonist strongly reduced this effect. These findings indicate that alkaline stimuli-such as the alkaline environment inside dental pulp treated with calcium hydroxide or mineral trioxide aggregate-activate Ca(2+) mobilization via Ca(2+) influx mediated by TRPA1 channels and intracellular Ca(2+) release in odontoblasts. High pH-sensing mechanisms in odontoblasts are important for activating dentinogenesis induced by an alkaline environment. © International & American Associations for Dental Research 2016.

Efficient and Stable Silicon Microwire Photocathodes with a Nickel Silicide Interlayer for Operation in Strongly Alkaline Solutions.

PubMed

Vijselaar, Wouter; Tiggelaar, Roald M; Gardeniers, Han; Huskens, Jurriaan

2018-05-11

Most photoanodes commonly applied in solar fuel research (e.g., of Fe 2 O 3 , BiVO 4 , TiO 2 , or WO 3 ) are only active and stable in alkaline electrolytes. Silicon (Si)-based photocathodes on the other hand are mainly studied under acidic conditions due to their instability in alkaline electrolytes. Here, we show that the in-diffusion of nickel into a 3D Si structure, upon thermal annealing, yields a thin (sub-100 nm), defect-free nickel silicide (NiSi) layer. This has allowed us to design and fabricate a Si microwire photocathode with a NiSi interlayer between the catalyst and the Si microwires. Upon electrodeposition of the catalyst (here, nickel molybdenum) on top of the NiSi layer, an efficient, Si-based photocathode was obtained that is stable in strongly alkaline solutions (1 M KOH). The best-performing, all-earth-abundant microwire array devices exhibited, under AM 1.5G simulated solar illumination, an ideal regenerative cell efficiency of 10.1%.

Oxygen Reduction Reaction on Ag(111) in Alkaline Solution: A Combined Density Functional Theory and Kinetic Monte Carlo Study

DOE PAGES

Liu, Shizhong; White, Michael G.; Liu, Ping

2018-01-25

We reported a detailed mechanistic study of the oxygen reduction reaction (ORR) on the model Ag(111) surface in alkaline solution by using density functional theory (DFT) and Kinetic Monte Carlo (KMC) simulations, in which multiple pathways involving either 2 e - or 4 e - mechanisms were included. The theoretical modelling presented here is able to reproduce the experimentally measured polarization curves in both low and high potential regions. An electrochemical 4 e - network including both a chemisorbed water (*H 2O)-mediated 4 e - associative pathway and the conventional associative pathway was identified to dominate the ORR mechanism. Onmore » the basis of the mechanistic understanding derived from these calculations, the ways to promote the ORR on Ag(111) were provided, including facilitating *OH removal, **O 2 reduction by *H 2O, and suppressing **O 2 desorption. Finally, the origin of the different ORR behaviors of Ag(111) and Pt(111) was also discussed in detail.« less

Oxygen Reduction Reaction on Ag(111) in Alkaline Solution: A Combined Density Functional Theory and Kinetic Monte Carlo Study

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

Liu, Shizhong; White, Michael G.; Liu, Ping

We reported a detailed mechanistic study of the oxygen reduction reaction (ORR) on the model Ag(111) surface in alkaline solution by using density functional theory (DFT) and Kinetic Monte Carlo (KMC) simulations, in which multiple pathways involving either 2 e - or 4 e - mechanisms were included. The theoretical modelling presented here is able to reproduce the experimentally measured polarization curves in both low and high potential regions. An electrochemical 4 e - network including both a chemisorbed water (*H 2O)-mediated 4 e - associative pathway and the conventional associative pathway was identified to dominate the ORR mechanism. Onmore » the basis of the mechanistic understanding derived from these calculations, the ways to promote the ORR on Ag(111) were provided, including facilitating *OH removal, **O 2 reduction by *H 2O, and suppressing **O 2 desorption. Finally, the origin of the different ORR behaviors of Ag(111) and Pt(111) was also discussed in detail.« less

Investigating surface chemistry-controlled dolomite precipitation in saline, alkaline, and dilute waters

NASA Astrophysics Data System (ADS)

Yoerg, A.; Roberts, J. A.

2017-12-01

Previous experiments have shown carboxylated organic matter facilitates dolomite precipitation at low temperature (< 80°C) in both modern and ancient seawater geochemistries. The efficacy of this mechanism in alternative chemical environments, particularly those typical of modern dolomitic environments, remains unclear. We investigated this question using a series of batch laboratory experiments ranging in duration from hours to several months. Experiments were conducted using fluids representative of environments where dolomite is found/thought to form in the modern, such as evaporative, alkaline lakes, sabkhas, and dilute mixing zones. Results indicate that while carboxylated organic matter promotes mineral precipitation in a variety of chemistries, the resultant mineralogy is primarily a function solution chemistry (i.e. saturation state). Specifically, our results suggest elevated alkalinity may be required to produce a high-Mg phase. In solutions where alkalinity is scarce, only amorphous carbonate phases form in association with organic matter, contrasting the Mg-bearing crystalline phases that result from highly alkaline solutions. Results of high-alkalinity, short-term experiments suggest that initially amorphous material is rapidly transformed into high and low-Mg phases in the presence of carboxylated organic matter, but that within days this mineralogy evolves. Longer timescales or elevated temperature may be necessary to produce an ordered dolomite phase. Additional results from longer term, steady-state experiments and additional analyses (Raman spectroscopy and tender energy spectroscopy) will shed further light on resultant mineralogy and this mechanism of dolomite precipitation.

Calixarene crown ether solvent composition and use thereof for extraction of cesium from alkaline waste solutions

DOEpatents

Moyer, Bruce A.; Sachleben, Richard A.; Bonnesen, Peter V.; Presley, Derek J.

2001-01-01

A solvent composition and corresponding method for extracting cesium (Cs) from aqueous neutral and alkaline solutions containing Cs and perhaps other competing metal ions is described. The method entails contacting an aqueous Cs-containing solution with a solvent consisting of a specific class of lipophilic calix[4]arene-crown ether extractants dissolved in a hydrocarbon-based diluent containing a specific class of alkyl-aromatic ether alcohols as modifiers. The cesium values are subsequently recovered from the extractant, and the solvent subsequently recycled, by contacting the Cs-containing organic solution with an aqueous stripping solution. This combined extraction and stripping method is especially useful as a process for removal of the radionuclide cesium-137 from highly alkaline waste solutions which are also very concentrated in sodium and potassium. No pre-treatment of the waste solution is necessary, and the cesium can be recovered using a safe and inexpensive stripping process using water, dilute (millimolar) acid solutions, or dilute (millimolar) salt solutions. An important application for this invention would be treatment of alkaline nuclear tank wastes. Alternatively, the invention could be applied to decontamination of acidic reprocessing wastes containing cesium-137.

Metabolic effect of alkaline additives and guanosine/gluconate in storage solutions for red blood cells.

PubMed

D'Alessandro, Angelo; Reisz, Julie A; Culp-Hill, Rachel; Korsten, Herbert; van Bruggen, Robin; de Korte, Dirk

2018-04-06

Over a century of advancements in the field of additive solutions for red blood cell (RBC) storage has made transfusion therapy a safe and effective practice for millions of recipients worldwide. Still, storage in the blood bank results in the progressive accumulation of metabolic alterations, a phenomenon that is mitigated by storage in novel storage additives, such as alkaline additive solutions. While novel alkaline additive formulations have been proposed, no metabolomics characterization has been performed to date. We performed UHPLC-MS metabolomics analyses of red blood cells stored in SAGM (standard additive in Europe), (PAGGSM), or alkaline additives SOLX, E-SOL 5 and PAG3M for either 1, 21, 35 (end of shelf-life in the Netherlands), or 56 days. Alkaline additives (especially PAG3M) better preserved 2,3-diphosphoglycerate and adenosine triphosphate (ATP). Deaminated purines such as hypoxanthine were predictive of hemolysis and morphological alterations. Guanosine supplementation in PAGGSM and PAG3M fueled ATP generation by feeding into the nonoxidative pentose phosphate pathway via phosphoribolysis. Decreased urate to hypoxanthine ratios were observed in alkaline additives, suggestive of decreased generation of urate and hydrogen peroxide. Despite the many benefits observed in purine and redox metabolism, alkaline additives did not prevent accumulation of free fatty acids and oxidized byproducts, opening a window for future alkaline formulations including (lipophilic) antioxidants. Alkalinization via different strategies (replacement of chloride anions with either high bicarbonate, high citrate/phosphate, or membrane impermeant gluconate) results in different metabolic outcomes, which are superior to current canonical additives in all cases. © 2018 AABB.

High-performance oxygen reduction catalysts in both alkaline and acidic fuel cells based on pre-treating carbon material and iron precursor

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

Song, Ping; Barkholtz, Heather M.; Wang, Ying

We demonstrate a new and simple method for pre-treating the carbon material and iron precursor to prepare oxygen reduction reaction (ORR) catalysts, which can produce super-high performance and stability in alkaline solution, with high performance in acid solution. This strategy using cheap materials is simply controllable. Moreover, it has achieved smaller uniform nanoparticles to exhibit high stability, and the synergetic effect of Fe and N offered much higher performance in ORR than commercial Pt/C, with high maximum power density in alkaline and acid fuel cell test. So it can make this kind of catalysts be the most promising alternatives ofmore » Pt-based catalysts with best performance/price.« less

Method for the recovery of uranium values from uranium tetrafluoride

DOEpatents

Kreuzmann, Alvin B.

1983-01-01

The invention is a novel method for the recovery of uranium from dry, particulate uranium tetrafluoride. In one aspect, the invention comprises reacting particulate uranium tetrafluoride and calcium oxide in the presence of gaseous oxygen to effect formation of the corresponding alkaline earth metal uranate and alkaline earth metal fluoride. The product uranate is highly soluble in various acidic solutions wherein the product fluoride is virtually insoluble therein. The product mixture of uranate and alkaline earth metal fluoride is contacted with a suitable acid to provide a uranium-containing solution, from which the uranium is recovered. The invention can achieve quantitative recovery of uranium in highly pure form.

Method for the recovery of uranium values from uranium tetrafluoride

DOEpatents

Kreuzmann, A.B.

1982-10-27

The invention is a novel method for the recovery of uranium from dry, particulate uranium tetrafluoride. In one aspect, the invention comprises reacting particulate uranium tetrafluoride and calcium oxide in the presence of gaseous oxygen to effect formation of the corresponding alkaline earth metal uranate and alkaline earth metal fluoride. The product uranate is highly soluble in various acidic solutions whereas the product fluoride is virtually insoluble therein. The product mixture of uranate and alkaline earth metal fluoride is contacted with a suitable acid to provide a uranium-containing solution, from which the uranium is recovered. The invention can achieve quantitative recovery of uranium in highly pure form.

Evaluating Growth of Zeolites on Fly Ash in Hydro-Thermally Heated Low Alkaline Solution

NASA Astrophysics Data System (ADS)

Jha, Bhagwanjee; Singh, D. N.

2017-12-01

Fly ash has been well established materials for synthesis of zeolites, under hydrothermally heated aqueous NaOH solution. Efficacy of such technique is reported to be improved when high molarity of NaOH is used. Consequently, highly alkaline waste solution, as by-product, is generally disposed of in the surrounding, which may contaminate the environment. In this context, less alkaline NaOH solution may become a safer option, which has not been tried in the past as per the literature. With this in view, the present study demonstrates effectiveness of the 0.5 M NaOH solution and critically monitors transition on the fly ash after hydrothermal treatment. As an enhancement over previous researchers, such activation of the fly ash finally results in remarkable morphological and mineralogical growth on the bulk material (the residue), which comprises of new nano-sized crystals (the zeolites Na-P1 and natrolite), after 24 h of activation of the fly ash.

Electromembrane recycling of highly mineralized alkaline blowdown water from evaporative water treatment plants at thermal power stations

NASA Astrophysics Data System (ADS)

Chichirova, N. D.; Chichirov, A. A.; Lyapin, A. I.; Minibaev, A. I.; Silov, I. Yu.; Tolmachev, L. I.

2016-12-01

Thermal power stations (TPS) are the main source of highly mineralized effluents affecting the environment. An analysis of their water systems demonstrates that alkaline effluents prevail at TPSs. Extraction of an alkali from highly mineralized effluents can make the recycling of effluents economically feasible. A method is proposed of electromembrane recycling of liquid alkaline highly mineralized wastes from TPSs. The process includes electromembrane apparatuses of two types, namely, a diffusion dialysis extractor (DDE) intended for extraction of the alkali from a highly mineralized solution having a complex composition and an electrodialysis concentrator for increasing the concentration of the extracted solution to a value suitable for use in water treatment plants at TPSs. For implementation of the first process (i.e. the extraction of alkali from alkaline-salt solution) various membranes from various manufacturers were studied: CM-PAD and AM-PAD (Ralex, Czechia), MK-40, MA-40, MA-41, MA-414, and MB-2 (OOO OKhK "Shchekinoazot", Russia), AR103-QDF and CR61-CMP (Ionies Inc., USA). The experiments demonstrate that the acceptable degree of separation of the alkali and the salt is achieved in a pair of cation-exchange membranes with the efficiency of separation being higher without an electric field. The highest efficiency was attained with Russian-made membranes (MK-40, OOO OKhK "Shchekinoazot"). A full scale experiment on recycling of highly-mineralized blowdown water from the evaporating water treatment system at the Kazan cogeneration power station No. 3 (TETs-3) was performed in a pilot unit consisting of two electromembrane apparatuses made by UAB "Membraninės Technologijos LT". In the experiments every ton of blowdown water yielded 0.1 t of concentrated alkaline solution with an alkali content of up to 4 wt % and 0.9 t of the softened salt solution suitable for the reuse in the TPS cycle. The power rate is 6 kWh / ton of blowdown water.

Efficient and Stable Silicon Microwire Photocathodes with a Nickel Silicide Interlayer for Operation in Strongly Alkaline Solutions

PubMed Central

2018-01-01

Most photoanodes commonly applied in solar fuel research (e.g., of Fe2O3, BiVO4, TiO2, or WO3) are only active and stable in alkaline electrolytes. Silicon (Si)-based photocathodes on the other hand are mainly studied under acidic conditions due to their instability in alkaline electrolytes. Here, we show that the in-diffusion of nickel into a 3D Si structure, upon thermal annealing, yields a thin (sub-100 nm), defect-free nickel silicide (NiSi) layer. This has allowed us to design and fabricate a Si microwire photocathode with a NiSi interlayer between the catalyst and the Si microwires. Upon electrodeposition of the catalyst (here, nickel molybdenum) on top of the NiSi layer, an efficient, Si-based photocathode was obtained that is stable in strongly alkaline solutions (1 M KOH). The best-performing, all-earth-abundant microwire array devices exhibited, under AM 1.5G simulated solar illumination, an ideal regenerative cell efficiency of 10.1%. PMID:29780886

Characterization of alkaline hydroxide-preserved whole poultry as a dry byproduct meal.

PubMed

Shafer, D J; Burgess, R P; Conrad, K A; Prochaska, J F; Carey, J B

2001-11-01

Studies were conducted to examine the chemical preservation of whole broiler carcasses by using aqueous alkaline hydroxide solutions. Conversion of the preserved carcasses and solutions into an acceptable poultry byproduct meal was examined. Carcasses and alkaline solutions at a 1:1 ratio were blended and freeze-dried to produce a high fat whole poultry byproduct meal. The dry meal was analyzed for nutrient composition, true metabolizable energy, and amino acid content. Viable bacteria were not recovered after inoculation of the experimental meal with Salmonella enteritidis. The meal was incorporated at 5 and 10% of chick starter diets. Chicks found the meal-containing diets acceptable. Feed consumption, water consumption, BW, and mortality were not significantly different among the dietary treatments in either of the two feeding trials. Necropsy samples revealed no pathological or histological differences attributable to consumption of the alkaline poultry byproduct and blood serum evaluation found no variation in blood chemistry. Alkaline treatment of whole broiler carcasses was an effective preservation method and acceptable as a dry poultry byproduct meal.

Production of Chitosan from Amusium sp Scallop Shell Waste

NASA Astrophysics Data System (ADS)

Rokhati, Nur; Istirokhatun, Titik; Titik Apriyanti, Dwi; Susanto, Heru

2017-02-01

Chitosan is one of the natural polysaccharides, which is produced from chitin by deacetylation process. In this study, chitosan was produced from Amusium sp scallop shell waste. First, chitin was isolated by extraction via deproteinization using alkaline solution followed by demineralization using acid solution. Thereafter, chitosan was resulted from deacetylation of chitin using a high concentration of alkaline solution. The chemical structure of chitin and chitosan products was characterized using fourier transform infrared spectroscopy (FTIR).

Effect of zinc phosphate chemical conversion coating on corrosion behaviour of mild steel in alkaline medium: protection of rebars in reinforced concrete.

PubMed

Simescu, Florica; Idrissi, Hassane

2008-12-01

We outline the ability of zinc phosphate coatings, obtained by chemical conversion, to protect mild steel rebars against localized corrosion, generated by chloride ions in alkaline media. The corrosion resistance of coated steel, in comparison with uncoated rebars and coated and uncoated steel rebars embedded in mortar, were evaluated by open-circuit potential, potentiodynamic polarization, cronoamperometry and electrochemical impedance spectroscopy. The coated surfaces were characterized by x-ray diffraction and scanning electron microscopy. First, coated mild steel rebars were studied in an alkaline solution with and without chloride simulating a concrete pore solution. The results showed that the slow dissolution of the coating generates hydroxyapatite Ca 10 (PO 4 ) 6 (OH) 2 . After a long immersion, the coating became dense and provided an effective corrosion resistance compared with the mild steel rebar. Secondly, the coated and uncoated steel rebars embedded in mortar and immersed in chloride solution showed no corrosion or deterioration of the coated steel. Corrosion rate is considerably lowered by this phosphate coating.

Effect of zinc phosphate chemical conversion coating on corrosion behaviour of mild steel in alkaline medium: protection of rebars in reinforced concrete

NASA Astrophysics Data System (ADS)

Simescu, Florica; Idrissi, Hassane

2008-12-01

We outline the ability of zinc phosphate coatings, obtained by chemical conversion, to protect mild steel rebars against localized corrosion, generated by chloride ions in alkaline media. The corrosion resistance of coated steel, in comparison with uncoated rebars and coated and uncoated steel rebars embedded in mortar, were evaluated by open-circuit potential, potentiodynamic polarization, cronoamperometry and electrochemical impedance spectroscopy. The coated surfaces were characterized by x-ray diffraction and scanning electron microscopy. First, coated mild steel rebars were studied in an alkaline solution with and without chloride simulating a concrete pore solution. The results showed that the slow dissolution of the coating generates hydroxyapatite Ca10(PO4)6(OH)2. After a long immersion, the coating became dense and provided an effective corrosion resistance compared with the mild steel rebar. Secondly, the coated and uncoated steel rebars embedded in mortar and immersed in chloride solution showed no corrosion or deterioration of the coated steel. Corrosion rate is considerably lowered by this phosphate coating.

Effect of zinc phosphate chemical conversion coating on corrosion behaviour of mild steel in alkaline medium: protection of rebars in reinforced concrete

PubMed Central

Simescu, Florica; Idrissi, Hassane

2008-01-01

We outline the ability of zinc phosphate coatings, obtained by chemical conversion, to protect mild steel rebars against localized corrosion, generated by chloride ions in alkaline media. The corrosion resistance of coated steel, in comparison with uncoated rebars and coated and uncoated steel rebars embedded in mortar, were evaluated by open-circuit potential, potentiodynamic polarization, cronoamperometry and electrochemical impedance spectroscopy. The coated surfaces were characterized by x-ray diffraction and scanning electron microscopy. First, coated mild steel rebars were studied in an alkaline solution with and without chloride simulating a concrete pore solution. The results showed that the slow dissolution of the coating generates hydroxyapatite Ca10(PO4)6(OH)2. After a long immersion, the coating became dense and provided an effective corrosion resistance compared with the mild steel rebar. Secondly, the coated and uncoated steel rebars embedded in mortar and immersed in chloride solution showed no corrosion or deterioration of the coated steel. Corrosion rate is considerably lowered by this phosphate coating. PMID:27878037

Modeling hot spring chemistries with applications to martian silica formation

NASA Astrophysics Data System (ADS)

Marion, G. M.; Catling, D. C.; Crowley, J. K.; Kargel, J. S.

2011-04-01

Many recent studies have implicated hydrothermal systems as the origin of martian minerals across a wide range of martian sites. Particular support for hydrothermal systems include silica (SiO 2) deposits, in some cases >90% silica, in the Gusev Crater region, especially in the Columbia Hills and at Home Plate. We have developed a model called CHEMCHAU that can be used up to 100 °C to simulate hot springs associated with hydrothermal systems. The model was partially derived from FREZCHEM, which is a colder temperature model parameterized for broad ranges of temperature (<-70 to 25 °C), pressure (1-1000 bars), and chemical composition. We demonstrate the validity of Pitzer parameters, volumetric parameters, and equilibrium constants in the CHEMCHAU model for the Na-K-Mg-Ca-H-Cl-ClO 4-SO 4-OH-HCO 3-CO 3-CO 2-O 2-CH 4-Si-H 2O system up to 100 °C and apply the model to hot springs and silica deposits. A theoretical simulation of silica and calcite equilibrium shows how calcite is least soluble with high pH and high temperatures, while silica behaves oppositely. Such influences imply that differences in temperature and pH on Mars could lead to very distinct mineral assemblages. Using measured solution chemistries of Yellowstone hot springs and Icelandic hot springs, we simulate salts formed during the evaporation of two low pH cases (high and low temperatures) and a high temperature, alkaline (high pH) sodic water. Simulation of an acid-sulfate case leads to precipitation of Fe and Al minerals along with silica. Consistency with martian mineral assemblages suggests that hot, acidic sulfate solutions are plausibility progenitors of minerals in the past on Mars. In the alkaline pH (8.45) simulation, formation of silica at high temperatures (355 K) led to precipitation of anhydrous minerals (CaSO 4, Na 2SO 4) that was also the case for the high temperature (353 K) low pH case where anhydrous minerals (NaCl, CaSO 4) also precipitated. Thus we predict that secondary minerals associated with massive silica deposits are plausible indicators on Mars of precipitation environments and aqueous chemistry. Theoretical model calculations are in reasonable agreement with independent experimental silica concentrations, which strengthens the validity of the new CHEMCHAU model.

Modeling hot spring chemistries with applications to martian silica formation

USGS Publications Warehouse

Marion, G.M.; Catling, D.C.; Crowley, J.K.; Kargel, J.S.

2011-01-01

Many recent studies have implicated hydrothermal systems as the origin of martian minerals across a wide range of martian sites. Particular support for hydrothermal systems include silica (SiO2) deposits, in some cases >90% silica, in the Gusev Crater region, especially in the Columbia Hills and at Home Plate. We have developed a model called CHEMCHAU that can be used up to 100??C to simulate hot springs associated with hydrothermal systems. The model was partially derived from FREZCHEM, which is a colder temperature model parameterized for broad ranges of temperature (<-70 to 25??C), pressure (1-1000 bars), and chemical composition. We demonstrate the validity of Pitzer parameters, volumetric parameters, and equilibrium constants in the CHEMCHAU model for the Na-K-Mg-Ca-H-Cl-ClO4-SO4-OH-HCO3-CO3-CO2-O2-CH4-Si-H2O system up to 100??C and apply the model to hot springs and silica deposits.A theoretical simulation of silica and calcite equilibrium shows how calcite is least soluble with high pH and high temperatures, while silica behaves oppositely. Such influences imply that differences in temperature and pH on Mars could lead to very distinct mineral assemblages. Using measured solution chemistries of Yellowstone hot springs and Icelandic hot springs, we simulate salts formed during the evaporation of two low pH cases (high and low temperatures) and a high temperature, alkaline (high pH) sodic water. Simulation of an acid-sulfate case leads to precipitation of Fe and Al minerals along with silica. Consistency with martian mineral assemblages suggests that hot, acidic sulfate solutions are plausibility progenitors of minerals in the past on Mars. In the alkaline pH (8.45) simulation, formation of silica at high temperatures (355K) led to precipitation of anhydrous minerals (CaSO4, Na2SO4) that was also the case for the high temperature (353K) low pH case where anhydrous minerals (NaCl, CaSO4) also precipitated. Thus we predict that secondary minerals associated with massive silica deposits are plausible indicators on Mars of precipitation environments and aqueous chemistry. Theoretical model calculations are in reasonable agreement with independent experimental silica concentrations, which strengthens the validity of the new CHEMCHAU model. ?? 2011 Elsevier Inc.

Similar influence of stabilized alkaline and neutral sodium hypochlorite solutions on the fracture resistance of root canal-treated bovine teeth.

PubMed

Souza, Erick Miranda; Calixto, Amanda Martins; Lima, Camila Nara E; Pappen, Fernanda Geraldo; De-Deus, Gustavo

2014-10-01

Stabilizing sodium hypochlorite (NaOCl) at an alkaline pH is proposed to increase solution stability and tissue dissolution ability; however, a reduction on the flexural strength of dentin discs has been found to be a side effect. This study sought to determine whether a stabilized alkaline NaOCl reduces the fracture resistance of root canal-treated bovine teeth after root canal preparation compared with a neutral solution counterpart. The 4 anterior incisors were removed from 20 mandibular bovine jaws, and each 1 was randomly assigned to 1 of 4 groups (20 teeth each). Teeth were prepared with a sequence of 6 K-type files. The following experimental groups received a different irrigation regimen: G1: distilled water (negative control), G2: 5% NaOCl at a pH of 7.2, and G3: 5% NaOCl at a pH of 12.8; in the positive control group (G4), teeth remained untreated. The time of contact and volume of solution were carefully standardized. After bone and periodontal ligament simulation, teeth were subjected to a fracture resistance test. A significant difference was observed among the 4 groups tested (analysis of variance, P < .05). The 5% NaOCl groups (G2 and G3) presented significantly lower resistance to fracture than the control (G1 and G4) (Tukey test, P < .05). Both NaOCl solutions similarly reduced the fracture resistance at approximately 30% (Tukey test, P > .05). No differences were observed between positive and negative control groups (Tukey test, P > .05). Stabilized alkaline and neutral NaOCl solutions similarly reduced the fracture resistance of root canal-treated bovine teeth by about 30%. Copyright © 2014 American Association of Endodontists. Published by Elsevier Inc. All rights reserved.

Executive summary - Assessing the response of Emerald Lake, an alpine watershed in Sequoia National Park, California, to acidification during snowmelt using a simple hydrochemical model

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

Hooper, R.P.; West, C.T.; Peters, N.E.

1990-01-01

A simple process-oriented model, called the Alpine Lake Forecaster (ALF), was constructed using data collected from the Integrated Watershed Study of Emerald Lake, Sequoia National Park, California. ALF is able to capture the basic solute patterns during snowmelt in this alpine catchment where groundwater is a minor contributor to streamflow. It includes an empirical representation of primary mineral weathering as the only alkalinity generating mechanism. During a heavy snow year, such as the one used for calibrating the model, the model accurately simulated the surface water chemical change in response to the initial ionic pulse from the snowpack and tomore » the dilution that occurs at peak snowmelt. Because the model does not consider cation exchange, it over-predicts the acidification during the initial period of snowmelt, and therefore is a conservative predictor. However, the minimum alkalinity observed in the main inflows to Emerald Lake and in the lake outflow is accurately simulated by the model. The representation of the lake as simply a missing volume with no additional chemical reactions is supported by the observation. The model predicts a change of 2 to 5 microequiv/L in the minimum alkalinity of the lake outflow during snowmelt if the deposition would have to increase between two and 18 times the current load-alkalinity of the lake; the precise increase depends on hydrologic conditions and on the pattern of solute release from the snowpack. An acidic rainstorm that exhausted the alkalinity of the lake was observed during summer 1984 after the lake had stratified, and is the likely cause of the acidification of Emerald Lake.« less

Fabrication of hydroxyapatite and TiO 2 nanorods on microarc-oxidized titanium surface using hydrothermal treatment

NASA Astrophysics Data System (ADS)

Song, Ho-Jun; Kim, Ji-Woo; Kook, Min-Suk; Moon, Won-Jin; Park, Yeong-Joon

2010-09-01

AC-type microarc oxidation (MAO) and hydrothermal treatment techniques were used to enhance the bioactivity of commercially pure titanium (CP-Ti). The porous TiO 2 layer fabricated by the MAO treatment had a dominant anatase structure and contained Ca and P ions. The MAO-treated specimens were treated hydrothermally to form HAp crystallites on the titanium oxide layer in an alkaline aqueous solution (OH-solution) or phosphorous-containing alkaline solution (POH-solution). A small number of micro-sized hydroxyapatite (HAp) crystallites and a thin layer composed of nano-sized HAps were formed on the Ti-MAO-OH group treated hydrothermally in an OH-solution, whereas a large number of micro-sized HAp crystallites and dense anatase TiO 2 nanorods were formed on the Ti-MAO-POH group treated hydrothermally in a POH-solution. The layer of bone-like apatite that formed on the surface of the POH-treated sample after soaking in a modified simulated body fluid was thicker than that on the OH-treated samples.

Mega-solubility of quartz resulting from highly alkaline fluids produced by dissolved albite in H2O at deep crustal conditions

NASA Astrophysics Data System (ADS)

Makhluf, A. R.; Manning, C. E.

2017-12-01

Models of H2O-rich fluids equilibrated with rocks at high P and T fail to predict the high solubilities observed experimentally, chiefly because thermodynamic data for the most abundant solutes is lacking. We investigated the effects of dissolved albite (Ab) on the solubility of quartz (Qz) at 1.0 GPa and 675-900 °C using a piston-cylinder apparatus to quantify possible mineral buffering or enhancement effects. We found a very large enhancement effect on the solubility of Qz when dissolved in dilute aqueous Ab solutions. SiO2 concentrations are similar to Qz solubility in strongly alkaline KOH solutions. At the highest temperature of 900 °C, we found that the solubility of Qz in 1.0 molal Ab solution increases by of factor of 4.5 over that in pure H2O, which corresponds to 10.7 molal SiO2. The nearly identical solubility of Qz in KOH(aq) and Ab solutions of the same concentration, P, and T, strongly suggest that NaOH(aq) liberated from NaAlSi3O8 in H2O fluids effects SiO2 solubility in a similar manner to that of KOH(aq). The deprotonated silica dimer was found to be a key species responsible for the high solubility of Qz in KOH(aq) and is likely responsible for the high solubility of Qz in Ab solutions. While the binaries Qz-H2O, Ab-H2O, and Qz-Ab are well known at 1.0 GPa, little data exists on the ternary system. The new results help quantify the ternary relations in the Ab-Qz-H2O system, which can be used as a simple model for liquid-vapor immiscibility granitic magmas. In addition, these highly alkaline solute-rich aqueous fluids suggest a mechanism for Ab-Qz metasomatism in subduction zones, such as in the Catalina schist (Bebout and Barton 1993), which provides an alternative to high P-T magmas. Our results show that subduction zone and metasomatic fluids may be much more alkaline and have significantly higher dissolving power than previously thought.

Chemical potentials of alkaline earth metal halide aqueous electrolytes and solubility of their hydrates by molecular simulation: Application to CaCl2, antarcticite, and sinjarite

NASA Astrophysics Data System (ADS)

Moučka, Filip; Kolafa, Jiří; Lísal, Martin; Smith, William R.

2018-06-01

We present a molecular-level simulation study of CaCl2 in water and crystalline hydrates formed by CaCl2 at ambient (298.15 K, 1 bar) conditions and at a high-temperature high-pressure state (365 K, 275 bars) typical of hydraulic fracturing conditions in natural-gas extraction, at which experimental properties are poorly characterized. We focus on simulations of chemical potentials in both solution and crystalline phases and on the salt solubility, the first time to our knowledge that such properties have been investigated by molecular simulation for divalent aqueous electrolytes. We first extend our osmotic ensemble Monte Carlo simulation technique [F. Moučka et al., J. Phys. Chem. B 115, 7849-7861 (2011)] to such solutions. We then describe and apply new methodology for the simulation of the chemical potentials of the experimentally observed crystalline hydrates at ambient conditions (antarcticite, CaCl2.6H2O) and at high-temperature conditions (sinjarite, CaCl2.2H2O). We implement our methodologies using for both phases the CaCl2 transferable force field (FF) based on simple point charge-extended water developed by Mamatkulov et al. [J. Chem. Phys. 138, 024505 (2013)], based on training sets involving single-ion and ion-pair low-concentration solution properties at near-ambient conditions. We find that simulations of the solution chemical potentials at high concentrations are somewhat problematic, exhibiting densities diverging from experimental values and accompanied by dramatically decreasing particle mobility. For the solid phases, the sinjarite crystalline lattice differs from experiment only slightly, whereas the simulations of antarcticite completely fail, due to instability of the crystalline lattice. The FF thus only successfully yields the sinjarite solubility, but its value m = 8.0(7) mol kg-1H2O lies well below the experimentally observed solubility range at 1 bar pressure of (12m, 15m) in the temperature interval (320 K, 400 K). We conclude that the used FF does not provide a good description of the experimental properties considered and suggest that improvement must take into account the crystalline properties.

Chemical potentials of alkaline earth metal halide aqueous electrolytes and solubility of their hydrates by molecular simulation: Application to CaCl2, antarcticite, and sinjarite.

PubMed

Moučka, Filip; Kolafa, Jiří; Lísal, Martin; Smith, William R

2018-06-14

We present a molecular-level simulation study of CaCl 2 in water and crystalline hydrates formed by CaCl 2 at ambient (298.15 K, 1 bar) conditions and at a high-temperature high-pressure state (365 K, 275 bars) typical of hydraulic fracturing conditions in natural-gas extraction, at which experimental properties are poorly characterized. We focus on simulations of chemical potentials in both solution and crystalline phases and on the salt solubility, the first time to our knowledge that such properties have been investigated by molecular simulation for divalent aqueous electrolytes. We first extend our osmotic ensemble Monte Carlo simulation technique [F. Moučka et al., J. Phys. Chem. B 115, 7849-7861 (2011)] to such solutions. We then describe and apply new methodology for the simulation of the chemical potentials of the experimentally observed crystalline hydrates at ambient conditions (antarcticite, CaCl 2 ·6H 2 O) and at high-temperature conditions (sinjarite, CaCl 2 ·2H 2 O). We implement our methodologies using for both phases the CaCl 2 transferable force field (FF) based on simple point charge-extended water developed by Mamatkulov et al. [J. Chem. Phys. 138, 024505 (2013)], based on training sets involving single-ion and ion-pair low-concentration solution properties at near-ambient conditions. We find that simulations of the solution chemical potentials at high concentrations are somewhat problematic, exhibiting densities diverging from experimental values and accompanied by dramatically decreasing particle mobility. For the solid phases, the sinjarite crystalline lattice differs from experiment only slightly, whereas the simulations of antarcticite completely fail, due to instability of the crystalline lattice. The FF thus only successfully yields the sinjarite solubility, but its value m = 8.0(7) mol kg -1 H 2 O lies well below the experimentally observed solubility range at 1 bar pressure of (12m, 15m) in the temperature interval (320 K, 400 K). We conclude that the used FF does not provide a good description of the experimental properties considered and suggest that improvement must take into account the crystalline properties.

Mineral dissolution and secondary precipitation on quartz sand in simulated Hanford tank solutions affecting subsurface porosity

NASA Astrophysics Data System (ADS)

Wang, Guohui; Um, Wooyong

2012-11-01

Highly alkaline nuclear waste solutions have been released from underground nuclear waste storage tanks and pipelines into the vadose zone at the US Department of Energy's Hanford Site in Washington, causing mineral dissolution and re-precipitation upon contact with subsurface sediments. High pH caustic NaNO3 solutions with and without dissolved Al were reacted with quartz sand through flow-through columns stepwise at 45, 51, and 89 °C to simulate possible reactions between leaked nuclear waste solution and primary subsurface mineral. Upon reaction, Si was released from the dissolution of quartz sand, and nitrate-cancrinite [Na8Si6Al6O24(NO3)2] precipitated on the quartz surface as a secondary mineral phase. Both steady-state dissolution and precipitation kinetics were quantified, and quartz dissolution apparent activation energy was determined. Mineral alteration through dissolution and precipitation processes results in pore volume and structure changes in the subsurface porous media. In this study, the column porosity increased up to 40.3% in the pure dissolution column when no dissolved Al was present in the leachate, whereas up to a 26.5% porosity decrease was found in columns where both dissolution and precipitation were observed because of the presence of Al in the input solution. The porosity change was also confirmed by calculation using the dissolution and precipitation rates and mineral volume changes.

Clastic dikes of the Hatrurim basin (western flank of the Dead Sea) as natural analogues of alkaline concretes: Mineralogy, solution chemistry, and durability

NASA Astrophysics Data System (ADS)

Sokol, E. V.; Gaskova, O. L.; Kozmenko, O. A.; Kokh, S. N.; Vapnik, E. A.; Novikova, S. A.; Nigmatulina, E. N.

2014-11-01

This study shows that the mineral assemblages from clastic dikes in areas adjacent to the Dead Sea graben may be considered as natural analogues of alkaline concretes. The main infilling material of the clastic dikes is composed of well-sorted and well-rounded quartz sand. The cement of these hard rocks contains hydroxylapophyllite, tacharanite, calcium silicate hydrates, opal, calcite, and zeolite-like phases, which is indicative of a similarity of the natural cementation processes and industrial alkaline concrete production from quartz sands and industrial alkaline cements. The quartz grains exhibit a variety of reaction textures reflecting the interaction with alkaline solutions (opal and calcium hydrosilicate overgrowths; full replacement with apophyllite or thomsonite + apophyllite). The physicochemical analysis and reconstruction of the chemical composition of peralkaline Ca, Na, and K solutions that formed these assemblages reveal that the solutions evolved toward a more stable composition of zeolite-like phases, which are more resistant to long-term chemical weathering and atmospheric corrosion. The 40Ar/39Ar age of 6.2 ± 0.7 Ma obtained for apophyllite provides conclusive evidence for the high corrosion resistance of the assemblages consisting of apophyllite and zeolite-like phases.

Spectrophotometric determination of copper in alkaline solutions and evaluation of some hydroxy-substituted 1,10-phenanthrolines as chromogenic reagents.

PubMed

Dunbar, W E; Schilt, A A

1972-09-01

Seven new hydroxy-substituted 1,10-phenanthroline derivatives have been evaluated as chromogenic reagents for the determination of copper in strongly alkaline solution. The most sensitive of these, 2,9-dimethyl-4,7-dihydroxy-1,10-phenanthroline, has proven to be highly effective in a simple, rapid procedure for determining trace amounts of copper in sodium hydroxide, potassium carbonate, sodium phosphate or ammonium hydroxide.

A study on alkaline heat treated Mg-Ca alloy for the control of the biocorrosion rate.

PubMed

Gu, X N; Zheng, W; Cheng, Y; Zheng, Y F

2009-09-01

To reduce the biocorrosion rate by surface modification, Mg-Ca alloy (1.4wt.% Ca content) was soaked in three alkaline solutions (Na(2)HPO(4), Na(2)CO(3) and NaHCO(3)) for 24h, respectively, and subsequently heat treated at 773K for 12h. Scanning electron microscopy and energy-dispersive spectroscopy results revealed that magnesium oxide layers with the thickness of about 13, 9 and 26microm were formed on the surfaces of Mg-Ca alloy after the above different alkaline heat treatments. Atomic force microscopy showed that the surfaces of Mg-Ca alloy samples became rough after three alkaline heat treatments. The in vitro corrosion tests in simulated body fluid indicated that the corrosion rates of Mg-Ca alloy were effectively decreased after alkaline heat treatments, with the following sequence: NaHCO(3) heated

Acceptor-type hydroxide graphite intercalation compounds electrochemically formed in high ionic strength solutions.

PubMed

Miyazaki, Kohei; Iizuka, Asuka; Mikata, Koji; Fukutsuka, Tomokazu; Abe, Takeshi

2017-09-05

The intercalation of hydroxide ions (OH - ) into graphite formed graphite intercalation compounds (GICs) in high ionic strength solutions. GICs of solvated OH - anions with two water molecules (OH - ·2H 2 O) in alkaline aqueous solutions and GICs of only OH - anions in a molten NaOH-KOH salt solution were electrochemically synthesized.

A compartmentalized solute transport model for redox zones in contaminated aquifers: 2. Field‐scale simulations

USGS Publications Warehouse

Abrams , Robert H.; Loague, Keith

2000-01-01

This paper, the second of two parts [see Abrams and Loague, this issue], reports the field‐scale application of COMPTRAN (compartmentalized solute transport model) for simulating the development of redox zones. COMPTRAN is fully developed and described in the companion paper. Redox zones, which are often delineated by the relative concentrations of dissolved oxygen, have been observed around the globe. The distribution of other redox‐sensitive species is affected by redox zonation. At the U.S. Geological Survey's Cape Cod research site, an anoxic zone containing high concentrations of dissolved iron has been observed. Field data were abstracted from the Cape Cod site for the one‐dimensional and two‐dimensional COMPTRAN simulations reported in this paper. The purpose of the concept‐development simulations was to demonstrate that the compartmentalized approach reported by Abrams et al. [1998] can be linked with a solute transport model to simulate field‐scale phenomena. The results presented in this paper show that COMPTRAN successfully simulated the development of redox zones at the field scale, including trends in pH and alkalinity. Thermodynamic constraints were used to prevent lower‐energy redox reactions from occurring under infeasible geochemical conditions without imposing equilibrium among all redox species. Empirical methods of reaction inhibition were not needed for the simulations conducted for this study. COMPTRAN can be extended easily to include additional compartments and reactions and is capable of handling complex velocity fields in more than one dimension.

Enhancing boron rejection in FO using alkaline draw solutions.

PubMed

Wang, Yi-Ning; Li, Weiyi; Wang, Rong; Tang, Chuyang Y

2017-07-01

This study provides a novel method to enhance boron removal in a forward osmosis (FO) process. It utilizes the reverse solute diffusion (RSD) of ions from alkaline draw solutions (DSs) and the concentration polarization of the hydroxyl ions to create a highly alkaline environment near the membrane active surface. The results show that boron rejection can be significantly enhanced by increasing the pH of NaCl DS to 12.5 in the active-layer-facing-feed-solution (AL-FS) orientation. The effect of RSD enhanced boron rejection was further promoted in the presence of concentration polarization (e.g., in the active-layer-facing-draw-solution (AL-DS) orientation). The current study opens a new dimension for controlling contaminant removal by FO using tailored DS chemistry, where the RSD-induced localized water chemistry change is taken advantage in contrast to the conventional method of chemical dosing to the bulk feed water. Copyright © 2017 Elsevier Ltd. All rights reserved.

High Performance Electrocatalytic Reaction of Hydrogen and Oxygen on Ruthenium Nanoclusters

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

Ye, Ruquan; Liu, Yuanyue; Peng, Zhiwei

2017-01-18

The development of catalytic materials for the hydrogen oxidation, hydrogen evolution, oxygen reduction or oxygen evolution reactions with high reaction rates and low overpotentials are key goals for the development of renewable energy. We report here Ru(0) nanoclusters supported on nitrogen-doped graphene as high-performance multifunctional catalysts for the hydrogen evolution reaction (HER) and oxygen reduction reaction (ORR), showing activities similar to that of commercial Pt/C in alkaline solution. For HER performance in alkaline media, sample Ru/NG-750 reaches 10 mA cm-2 at an overpotential of 8 mV with a Tafel slope of 30 mV dec-1. The high HER performance in alkalinemore » solution is advantageous because most catalysts for ORR and oxygen evolution reaction (OER) also prefer alkaline solution environment whereas degrade in acidic electrolytes. For ORR performance, Ru/NG effectively catalyzes the conversion of O2 into OH- via a 4e process at a current density comparable to that of Pt/C. The unusual catalytic activities of Ru(0) nanoclusters reported here are important discoveries for the advancement of renewable energy conversion reactions.« less

Characterization of Laboratory Prepared Concrete Pastes Exposed to High Alkaline and High Sodium Salt Solutions

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

Langton, C. A.

The objective of this study was to identify potential chemical degradation mechanisms for the Saltstone Disposal Unit (SDU) concretes, which over the performance life of the structures may be exposed to highly alkaline sodium salt solutions containing sulfate, hydroxide, and other potentially corrosive chemicals in salt solution and saltstone flush water, drain water, leachate and / or pore solution. The samples analyzed in this study were cement pastes prepared in the SIMCO Technologies, Inc. concrete laboratory. They were based on the paste fractions of the concretes used to construct the Saltstone Disposal Units (SDUs). SDU 1 and 4 concrete pastesmore » were represented by the PV1 test specimens. The paste in the SDU 2, 3, 5, and 6 concrete was represented by the PV2 test specimens. SIMCO Technologies, Inc. selected the chemicals and proportions in the aggressive solutions to approximate proportions in the saltstone pore solution [2, 3, 5, and 6]. These test specimens were cured for 56 days in curing chamber before being immersed in aggressive solutions. After exposure, the samples were frozen to prevent additional chemical transport and reaction. Selected archived (retrieved from the freezer) samples were sent to the Savannah River National Laboratory (SRNL) for additional characterization using x-ray diffraction (XRD), scanning electron microscopy (SEM), and energy dispersive x-ray (EDX) spectroscopy. Characterization results are summarized in this report. In addition, a correlation between the oxide composition of the pastes and their chemical durability in the alkaline salt solutions is provided.« less

Process for extracting technetium from alkaline solutions

DOEpatents

Moyer, Bruce A.; Sachleben, Richard A.; Bonnesen, Peter V.

1995-01-01

A process for extracting technetium values from an aqueous alkaline solution containing at least one alkali metal hydroxide and at least one alkali metal nitrate, the at least one alkali metal nitrate having a concentration of from about 0.1 to 6 molar. The solution is contacted with a solvent consisting of a crown ether in a diluent for a period of time sufficient to selectively extract the technetium values from the aqueous alkaline solution. The solvent containing the technetium values is separated from the aqueous alkaline solution and the technetium values are stripped from the solvent.

Effect of Stress Ratio and Loading Frequency on the Corrosion Fatigue Behavior of Smooth Steel Wire in Different Solutions

PubMed Central

Wang, Songquan; Zhang, Dekun; Hu, Ningning; Zhang, Jialu

2016-01-01

In this work, the effects of loading condition and corrosion solution on the corrosion fatigue behavior of smooth steel wire were discussed. The results of polarization curves and weight loss curves showed that the corrosion of steel wire in acid solution was more severe than that in neutral and alkaline solutions. With the extension of immersion time in acid solution, the cathodic reaction of steel wire gradually changed from the reduction of hydrogen ion to the reduction of oxygen, but was always the reduction of hydrogen ion in neutral and alkaline solutions. The corrosion kinetic parameters and equivalent circuits of steel wires were also obtained by simulating the Nyquist diagrams. In corrosion fatigue test, the effect of stress ratio and loading frequency on the crack initiation mechanism was emphasized. The strong corrosivity of acid solution could accelerate the nucleation of crack tip. The initiation mechanism of crack under different conditions was summarized according to the side and fracture surface morphologies. For the crack initiation mechanism of anodic dissolution, the stronger the corrosivity of solution was, the more easily the fatigue crack source formed, while, for the crack initiation mechanism of deformation activation, the lower stress ratio and higher frequency would accelerate the generation of corrosion fatigue crack source. PMID:28773869

Influence of ionic strength and OH(-) ion concentration on the Cu(II) complex formation with EDTA in alkaline solutions.

PubMed

Norkus, E; Vaskelis, A; Zakaite, I

1996-03-01

D.c. polarographic data show that the complex formation of copper ions with EDTA depends markedly on the ionic strength of the solution at pH 8-10. This is primarily associated with the dependence of the fourth deprotonization constant of EDTA on the solution ionic strength: when it increases from 0.4 to 3.4, the pK(a4) value decreases from 9.5 to 8.2. According to polarographic and spectrophotometric data the degree of Cu(II) complexation increases at pH>10 due to transformation of the complex CuY(2-) to the more stable CuY(OH)(3-) (Y(4-), a fully deprotonized anion of EDTA), but it decreases with increase in alkalinity in a highly alkaline solution (pH>13.5). The latter result could be explained by the decrease in the EDTA anion activity. The calculated values of the activity coefficient are lower than 0.05 at pH>14.

Ca(2+) -complex stability of GAPAGPLIVPY peptide in gas and aqueous phase, investigated by affinity capillary electrophoresis and molecular dynamics simulations and compared to mass spectrometric results.

PubMed

Nachbar, Markus; El Deeb, Sami; Mozafari, Mona; Alhazmi, Hassan A; Preu, Lutz; Redweik, Sabine; Lehmann, Wolf Dieter; Wätzig, Hermann

2016-03-01

Strong, sequence-specific gas-phase bindings between proline-rich peptides and alkaline earth metal ions in nanoESI-MS experiments were reported by Lehmann et al. (Rapid Commun. Mass Spectrom. 2006, 20, 2404-2410), however its relevance for physiological-like aqueous phase is uncertain. Therefore, the complexes should also be studied in aqueous solution and the relevance of the MS method for binding studies be evaluated. A mobility shift ACE method was used for determining the binding between the small peptide GAPAGPLIVPY and various metal ions in aqueous solution. The findings were compared to the MS results and further explained using computational methods. While the MS data showed a strong alkaline earth ion binding, the ACE results showed nonsignificant binding. The proposed vacuum state complex also decomposed during a molecular dynamic simulation in aqueous solution. This study shows that the formed stable peptide-metal ion adducts in the gas phase by ESI-MS does not imply the existence of analogous adducts in the aqueous phase. Comparing peptide-metal ion interaction under the gaseous MS and aqueous ACE conditions showed huge difference in binding behavior. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Mineral Dissolution and Secondary Precipitation on Quartz Sand in Simulated Hanford Tank Solutions Affecting Subsurface Porosity

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

Wang, Guohui; Um, Wooyong

2012-11-23

Highly alkaline nuclear waste solutions have been released from underground nuclear waste storage tanks and pipelines into the vadose zone at the U.S. Department of Energy’s Hanford Site in Washington, causing mineral dissolution and re-precipitation upon contact with subsurface sediments. High pH caustic NaNO3 solutions with and without dissolved Al were reacted with quartz sand through flow-through columns stepwise at 45, 51, and 89°C to simulate possible reactions between leaked nuclear waste solution and primary subsurface mineral. Upon reaction, Si was released from the dissolution of quartz sand, and nitrate-cancrinite [Na8Si6Al6O24(NO3)2] precipitated on the quartz surface as a secondary mineralmore » phase. Both steady-state dissolution and precipitation kinetics were quantified, and quartz dissolution apparent activation energy was determined. Mineral alteration through dissolution and precipitation processes results in pore volume and structure changes in the subsurface porous media. In this study, the column porosity increased up to 40.3% in the pure dissolution column when no dissolved Al was present in the leachate, whereas up to a 26.5% porosity decrease was found in columns where both dissolution and precipitation were observed because of the presence of Al in the input solution. The porosity change was also confirmed by calculation using the dissolution and precipitation rates and mineral volume changes.« less

Stability of GO Modified by Different Dispersants in Cement Paste and Its Related Mechanism.

PubMed

Long, Wu-Jian; Fang, Changle; Wei, Jingjie; Li, Haodao

2018-05-18

Graphene oxide (GO) is a potential material to be used as a nano-reinforcement in cement matrix. However, a prerequisite for GO to fulfill its function in the cement matrix is homogeneous dispersion. In this study, the effects of three different dispersing agents (DAs), including polycarboxylate-based high range water reducer (P-HRWR), naphthalene-based high range water reducer (N-HRWR), and air entraining agent (AEA) on the dispersion of GO in aqueous solution, simulated concrete pore solution (SCPS), and suspension of cement pastes were sequentially investigated. Results showed that the dispersion effect of GO in aqueous solutions was improved with different DAs. However, the homogeneous dispersion of GO in aqueous solution re-agglomerated in SCPS and suspension of cement pastes. It was concluded that as the cement content and pH of aqueous solutions increased, GOs re-agglomerated and precipitated in an alkaline solution. A possible mechanism was proposed in this study and it was believed that electrostatic interactions and steric hindrance provided by the P-HRWR further made GOs stable in aqueous solutions. The ions and pH of cement pastes increased with the increasing amount of cement, which caused the separation of P-HRWR from GOs. Therefore, GOs were re-agglomerated and absorbed on the surface of the cement particles, resulting in GOs sedimentation.

Relative Stability of the Scleroglucan Triple-Helix and Single Strand: an Insight from Computational and Experimental Techniques

NASA Astrophysics Data System (ADS)

Bocchinfuso, Gianfranco; Mazzuca, Claudia; Conflitti, Paolo; Cori, Davide; Coviello, Tommasina; Palleschi, Antonio

2016-09-01

Scleroglucan (Sclg) is a polysaccharide that exhibits a triple helix conformation (triplex), both in aqueous solution and in the solid state, which is lost in DMSO solution, at high temperature and at high pH values. The triplex conformation is characterized by a high rigidity, responsible of Sclg peculiar properties. Although the relative stability of triplex and single strand has already been investigated, different structural details are still missing. In the present study, we analyse the structural properties and the factors stabilizing the single chain and the triple helix of Sclg in different conditions. To this end, we simulated both systems in water and in DMSO. The triple helix has been also simulated in the presence of chemical damages on one of the three strands (to reproduce in silico the effect of sonication) or by inducing a partial unfolding of the triplex structure. The computational results have been compared with experimental evidences in which the triplex denaturation, at alkaline pH values, has been followed by monitoring the UV and CD spectra of Congo red, used as a probe molecule. Our results indicate that sonication breaks the Sclg chains without appreciably changing the stability of the other tracts of triple helix. The simulated perturbed or partially unfolded triplexes show a clear tendency to form less ordered aggregates. Finally, our simulations put in evidence an important role of the hydrophobic interactions both in the triplex stability and in the aggregation processes observed after induced denaturation.

Simulating Porous Magnetite Layer Deposited on Alloy 690TT Steam Generator Tubes

PubMed Central

Jeon, Soon-Hyeok; Son, Yeong-Ho; Choi, Won-Ik; Song, Geun Dong; Hur, Do Haeng

2018-01-01

In nuclear power plants, the main corrosion product that is deposited on the outside of steam generator tubes is porous magnetite. The objective of this study was to simulate porous magnetite that is deposited on thermally treated (TT) Alloy 690 steam generator tubes. A magnetite layer was electrodeposited on an Alloy 690TT substrate in an Fe(III)-triethanolamine solution. After electrodeposition, the dense magnetite layer was immersed to simulate porous magnetite deposits in alkaline solution for 50 days at room temperature. The dense morphology of the magnetite layer was changed to a porous structure by reductive dissolution reaction. The simulated porous magnetite layer was compared with flakes of steam generator tubes, which were collected from the secondary water system of a real nuclear power plant during sludge lancing. Possible nuclear research applications using simulated porous magnetite specimens are also proposed. PMID:29301316

Chemically and compositionally modified solid solution disordered multiphase nickel hydroxide positive electrode for alkaline rechargeable electrochemical cells

DOEpatents

Ovshinsky, Stanford R.; Corrigan, Dennis; Venkatesan, Srini; Young, Rosa; Fierro, Christian; Fetcenko, Michael A.

1994-01-01

A high capacity, long cycle life positive electrode for use in an alkaline rechargeable electrochemical cell comprising: a solid solution nickel hydroxide material having a multiphase structure that comprises at least one polycrystalline .gamma.-phase including a polycrystalline .gamma.-phase unit cell comprising spacedly disposed plates with at least one chemical modifier incorporated around the plates, the plates having a range of stable intersheet distances corresponding to a 2.sup.+ oxidation state and a 3.5.sup.+, or greater, oxidation state; and at least one compositional modifier incorporated into the solid solution nickel hydroxide material to promote the multiphase structure.

High Electrocatalytic Hydrogen Evolution Activity of an Anomalous Ruthenium Catalyst.

PubMed

Zheng, Yao; Jiao, Yan; Zhu, Yihan; Li, Lu Hua; Han, Yu; Chen, Ying; Jaroniec, Mietek; Qiao, Shi-Zhang

2016-12-14

Hydrogen evolution reaction (HER) is a critical process due to its fundamental role in electrocatalysis. Practically, the development of high-performance electrocatalysts for HER in alkaline media is of great importance for the conversion of renewable energy to hydrogen fuel via photoelectrochemical water splitting. However, both mechanistic exploration and materials development for HER under alkaline conditions are very limited. Precious Pt metal, which still serves as the state-of-the-art catalyst for HER, is unable to guarantee a sustainable hydrogen supply. Here we report an anomalously structured Ru catalyst that shows 2.5 times higher hydrogen generation rate than Pt and is among the most active HER electrocatalysts yet reported in alkaline solutions. The identification of new face-centered cubic crystallographic structure of Ru nanoparticles was investigated by high-resolution transmission electron microscopy imaging, and its formation mechanism was revealed by spectroscopic characterization and theoretical analysis. For the first time, it is found that the Ru nanocatalyst showed a pronounced effect of the crystal structure on the electrocatalytic activity tested under different conditions. The combination of electrochemical reaction rate measurements and density functional theory computation shows that the high activity of anomalous Ru catalyst in alkaline solution originates from its suitable adsorption energies to some key reaction intermediates and reaction kinetics in the HER process.

Study of the IGA/SCC behavior of Alloy 600 and 690 in high temperature solutions

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

Tsujikawa, S.; Yashima, S.; Ohnishi, K.

1995-09-01

IGA/SCC of Alloy 600 steam generator (SG) tubes in the secondary side has been recognized as a matter of great concern for PWRs. IGA/SCC behavior of Alloy 600 and 690 in high temperature solutions were studied using CERT method under potentiostatic conditions. The IGA/SCC susceptible regions were investigated as the function of pH and electrode potential. To understand the cause of IGA/SCC, the electrochemical measurements and surface film analysis were also performed in acidic and alkaline solutions. To verify the results of CERT test, the long term model boiler tests were also carried out. Thermally treated Alloy 690 showed highermore » IGA/SCC resistance than Alloy 600 under both acid and alkaline conditions.« less

Scanning electron microscopic and X-ray micro analysis on tooth enamel exposed to alkaline agents.

PubMed

Taubee, Fabian; Steiniger, Frank; Nietzsche, Sandor; Norén, Jörgen G

2010-01-01

The background of this study comprises two clinical cases, where patients exposed to aerosols of an alkaline and surface active cleaning agent developed loss of enamel substance on their teeth, further resulting in loss of teeth and partially destroyed soft tissues. The alkaline cleaning agent consisted of potassium hydroxide and various surfactants. The purpose of this study was to investigate possible changes in morphology and composition in human teeth enamel exposed to alkaline solutions, by means of X-ray micro analysis (XRMA), FTIR-spectroscopic analyses and scanning electron microscopy (SEM). Extracted premolars, exposed to potassium hydroxide solutions and alkaline cleaning solution,were analyzed by means of XRMA and SEM. Enamel powder, exposed to cleaning solution, was analyzed by means of FTIR. The SEM analysis revealed an increased porosity of the enamel surface and partially loss of enamel substance after exposure to alkaline solutions. The XRMA analyses revealed a decrease in carbon concentration while phosphorous and calcium showed no marked changes. The FTIR analyses showed no significant changes in peak heights or peak positions for phosphate, carbonate or hydroxide. It was concluded that human teeth enamel exposed to alkaline solutions showed loss of organic substance, marked pores in enamel surface and loss of substance in the enamel surface.

Millimeter-scale alkalinity measurement in marine sediment using DET probes and colorimetric determination.

PubMed

Metzger, E; Viollier, E; Simonucci, C; Prévot, F; Langlet, D; Jézéquel, D

2013-10-01

Constrained DET (Diffusive Equilibration in Thin films) probes equipped with 75 sampling layers of agarose gel (DGT Research(©)) were used to sample bottom and pore waters in marine sediment with a 2 mm vertical resolution. After retrieval, each piece of hydrogel, corresponding to 25 μL, was introduced into 1 mL of colorimetric reagent (CR) solution consisting of formic acid and bromophenol blue. After the elution/reaction time, absorbance of the latter mixture was read at 590 nm and compared to a calibration curve obtained with the same protocol applied to mini DET probes soaked in sodium hydrogen carbonate standard solutions. This method allows rapid alkalinity determinations for the small volumes of anoxic pore water entrapped into the gel. The method was assessed on organic-rich coastal marine sediments from Thau lagoon (France). Alkalinity values in the overlying waters were in agreement with data obtained by classical sampling techniques. Pore water data showed a progressive increase of alkalinity in the sediment from 2 to 10 mmol kg(-1), corresponding to anaerobic respiration in organic-rich sediments. Moreover, replicates of high-resolution DET profiles showed important lateral heterogeneity at a decimeter scale. This underlines the importance of high-resolution spatial methods for alkalinity profiling in coastal marine systems. Copyright © 2013 Elsevier Ltd. All rights reserved.

Reductive dechlorination of carbon tetrachloride using buffered alkaline ascorbic acid.

PubMed

Lin, Ya-Ting; Liang, Chenju

2015-10-01

Alkaline ascorbic acid (AA) was recently discovered as a novel in-situ chemical reduction (ISCR) reagent for remediating chlorinated solvents in the subsurface. For this ISCR process, the maintenance of an alkaline pH is essential. This study investigated the possibility of the reduction of carbon tetrachloride (CT) using alkaline AA solution buffered by phosphate and by NaOH. The results indicated that CT was reduced by AA, and chloroform (CF) was a major byproduct at a phosphate buffered pH of 12. However, CT was completely reduced by AA in 2M NaOH without CF formation. In the presence of iron/soil minerals, iron could be reduced by AA and Fe(2+) tends to precipitate on the mineral surface to accelerate CT degradation. A simultaneous transfer of hydrogenolysis and dichloroelimination would occur under phosphate buffered pH 12. This implies that a high alkaline environment is a crucial factor for maintaining the dominant pathway of two electron transfer from dianionic AA to dehydroascorbic acid, and to undergo dichloroelimination of CT. Moreover, threonic acid and oxalic acid were identified to be the major AA decomposition products in alkaline solutions. Copyright © 2015 Elsevier Ltd. All rights reserved.

Long-term trends in alkalinity in large rivers of the conterminous US in relation to acidification, agriculture, and hydrologic modification

USGS Publications Warehouse

Stets, Edward G.; Kelly, Valerie J.; Crawford, Charles G.

2014-01-01

Alkalinity increases in large rivers of the conterminous US are well known, but less is understood about the processes leading to these trends as compared with headwater systems more intensively examined in conjunction with acid deposition studies. Nevertheless, large rivers are important conduits of inorganic carbon and other solutes to coastal areas and may have substantial influence on coastal calcium carbonate saturation dynamics. We examined long-term (mid-20th to early 21st century) trends in alkalinity and other weathering products in 23 rivers of the conterminous US. We used a rigorous flow-weighting technique which allowed greater focus on solute trends occurring independently of changes in flow. Increasing alkalinity concentrations and yield were widespread, occurring at 14 and 13 stations, respectively. Analysis of trends in other weathering products suggested that the causes of alkalinity trends were diverse, but at many stations alkalinity increases coincided with decreasing nitrate + sulfate and decreasing cation:alkalinity ratios, which is consistent with recovery from acidification. A positive correlation between the Sen–Thiel slopes of alkalinity increases and agricultural lime usage indicated that agricultural lime contributed to increasing solute concentration in some areas. However, several stations including the Altamaha, Upper Mississippi, and San Joaquin Rivers exhibited solute trends, such as increasing cation:alkalinity ratios and increasing nitrate + sulfate, more consistent with increasing acidity, emphasizing that multiple processes affect alkalinity trends in large rivers. This study was unique in its examination of alkalinity trends in large rivers covering a wide range of climate and land use types, but more detailed analyses will help to better elucidate temporal changes to river solutes and especially the effects they may have on coastal calcium carbonate saturation state.

Long-term trends in alkalinity in large rivers of the conterminous US in relation to acidification, agriculture, and hydrologic modification.

PubMed

Stets, E G; Kelly, V J; Crawford, C G

2014-08-01

Alkalinity increases in large rivers of the conterminous US are well known, but less is understood about the processes leading to these trends as compared with headwater systems more intensively examined in conjunction with acid deposition studies. Nevertheless, large rivers are important conduits of inorganic carbon and other solutes to coastal areas and may have substantial influence on coastal calcium carbonate saturation dynamics. We examined long-term (mid-20th to early 21st century) trends in alkalinity and other weathering products in 23 rivers of the conterminous US. We used a rigorous flow-weighting technique which allowed greater focus on solute trends occurring independently of changes in flow. Increasing alkalinity concentrations and yield were widespread, occurring at 14 and 13 stations, respectively. Analysis of trends in other weathering products suggested that the causes of alkalinity trends were diverse, but at many stations alkalinity increases coincided with decreasing nitrate+sulfate and decreasing cation:alkalinity ratios, which is consistent with recovery from acidification. A positive correlation between the Sen-Thiel slopes of alkalinity increases and agricultural lime usage indicated that agricultural lime contributed to increasing solute concentration in some areas. However, several stations including the Altamaha, Upper Mississippi, and San Joaquin Rivers exhibited solute trends, such as increasing cation:alkalinity ratios and increasing nitrate+sulfate, more consistent with increasing acidity, emphasizing that multiple processes affect alkalinity trends in large rivers. This study was unique in its examination of alkalinity trends in large rivers covering a wide range of climate and land use types, but more detailed analyses will help to better elucidate temporal changes to river solutes and especially the effects they may have on coastal calcium carbonate saturation state. Published by Elsevier B.V.

FERRATE TREATMENT FOR REMOVING CHROMIUM FROM HIGH-LEVEL RADIOACTIVE TANK WASTE

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

Sylvester, Paul; Rutherford, Andy; Gonzalez-Martin, Anuncia

2000-12-01

A method has been developed for removing chromium from alkaline high-level radioactive tank waste. Removing chromium from these wastes is critical in reducing the volume of waste requiring expensive immobilization and deep geologic disposition. The method developed is based on the oxidation of insoluble chromium(III) compounds to soluble chromate using ferrate. The tests conducted with a simulated Hanford tank sludge indicate that the chromium removal with ferrate is more efficient at 5 M NaOH than at 3 M NaOH. Chromium removal increases with increasing Fe(VI)/Cr(III) molar ratio, but the chromium removal tends to level out for Fe(VI)/Cr(III) greater than 10.more » Increasing temperature leads to better chromium removal, but higher temperatures also led to more rapid ferrate decomposition. Tests with radioactive Hanford tank waste generally confirmed the simulant results. In all cases examined, ferrate enhanced the chromium removal, with a typical removal of around 60-70% of the total chromium present in the washed sludge solids. The ferrate leachate solutions did not contain significant concentrations of transuranic elements, so these solutions could be handled as low-activity waste.« less

Corrosion of radioactive waste tanks containing washed sludge and precipitates

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

Bickford, D.F.; Congdon, J.W.; Oblath, S.B.

1988-05-01

At the US Department of Energy (DOE) Savannah River Plant, the corrosion of carbon steel storage tanks containing alkaline, high-level radioactive waste is controlled by specification of limits on waste composition and temperature. Laboratory tests, conducted to determine minimum corrosion inhibitor levels, indicated pitting of carbon steel near the waterline for proposed storage conditions. In situ electrochemical measurements of full-scale radioactive process demonstrations were conducted to assess the validity of laboratory tests. The in situ results are compared to those of laboratory tests, with particular regard given to simulated solution composition. Transition metal hydroxide sludge contains strong passivating species formore » carbon steel. Washed precipitate contains organic species that lower solution pH and tend to reduce passivating films, requiring higher inhibitor concentrations than the 0.01 M nitrite required for reactor fuel reprocessing wastes.« less

Alkali activated slag mortars provide high resistance to chloride-induced corrosion of steel

NASA Astrophysics Data System (ADS)

Criado, Maria; Provis, John L.

2018-06-01

The pore solutions of alkali-activated slag cements and Portland-based cements are very different in terms of their chemical and redox characteristics, particularly due to the high alkalinity and high sulfide content of alkali-activated slag cement. Therefore, differences in corrosion mechanisms of steel elements embedded in these cements could be expected, with important implications for the durability of reinforced concrete elements. This study assesses the corrosion behaviour of steel embedded in alkali-activated blast furnace slag (BFS) mortars exposed to alkaline solution, alkaline chloride-rich solution, water, and standard laboratory conditions, using electrochemical techniques. White Portland cement (WPC) mortars and blended cement mortars (white Portland cement and blast furnace slag) were also tested for comparative purposes. The steel elements embedded in immersed alkali-activated slag mortars presented very negative redox potentials and high apparent corrosion current values; the presence of sulfide reduced the redox potential, and the oxidation of the reduced sulfur-containing species within the cement itself gave an electrochemical signal that classical electrochemical tests for reinforced concrete durability would interpret as being due to steel corrosion processes. However, the actual observed resistance to chloride-induced corrosion was very high, as measured by extraction and characterisation of the steel at the end of a 9-month exposure period, whereas the steel embedded in white Portland cement mortars was significantly damaged under the same conditions.

Simulation of dual carbon-bromine stable isotope fractionation during 1,2-dibromoethane degradation.

PubMed

Jin, Biao; Nijenhuis, Ivonne; Rolle, Massimo

2018-06-01

We performed a model-based investigation to simultaneously predict the evolution of concentration, as well as stable carbon and bromine isotope fractionation during 1,2-dibromoethane (EDB, ethylene dibromide) transformation in a closed system. The modelling approach considers bond-cleavage mechanisms during different reactions and allows evaluating dual carbon-bromine isotopic signals for chemical and biotic reactions, including aerobic and anaerobic biological transformation, dibromoelimination by Zn(0) and alkaline hydrolysis. The proposed model allowed us to accurately simulate the evolution of concentrations and isotope data observed in a previous laboratory study and to successfully identify different reaction pathways. Furthermore, we illustrated the model capabilities in degradation scenarios involving complex reaction systems. Specifically, we examined (i) the case of sequential multistep transformation of EDB and the isotopic evolution of the parent compound, the intermediate and the reaction product and (ii) the case of parallel competing abiotic pathways of EDB transformation in alkaline solution.

Thin film superconductors and process for making same

DOEpatents

Nigrey, P.J.

1988-01-21

A process for the preparation of oxide superconductors from high-viscosity non-aqueous solution is described. Solutions of lanthanide nitrates, alkaline earth nitrates and copper nitrates in a 1:2:3 stoichiometric ratio, when added to ethylene glycol containing citric acid solutions, have been used to prepare highly viscous non-aqueous solutions of metal mixed nitrates-citrates. Thin films of these compositions are produced when a layer of the viscous solution is formed on a substrate and subjected to thermal decomposition.

Structural and Dynamical Properties of Alkaline Earth Metal Halides in Supercritical Water: Effect of Ion Size and Concentration.

PubMed

Keshri, Sonanki; Tembe, B L

2017-11-22

Constant temperature-constant pressure molecular dynamics simulations have been performed for aqueous alkaline earth metal chloride [M 2+ -Cl - (M = Mg, Ca, Sr, and Ba)] solutions over a wide range of concentrations (0.27-5.55 m) in supercritical (SC) and ambient conditions to investigate their structural and dynamical properties. A strong influence of the salt concentration is observed on the ion-ion pair correlation functions in both ambient and SC conditions. In SC conditions, significant clustering is observed in the 0.27 m solution, whereas the reverse situation is observed at room temperature and this is also supported by the residence times of the clusters. The concentration and ion size (cation size) seem to have opposite effects on the average number of hydrogen bonds. The simulation results show that the self-diffusion coefficients of water, cations, and the chloride ion increase with increasing temperature, whereas they decrease with increasing salt concentration. The cluster size distribution shows a strong density dependence in both ambient and SC conditions. In SC conditions, cluster sizes display a near-Gaussian distribution, whereas the distribution decays monotonically in ambient conditions.

Durability of template-free Fe-N-C foams for electrochemical oxygen reduction in alkaline solution

NASA Astrophysics Data System (ADS)

Mufundirwa, Albert; Harrington, George F.; Smid, Břetislav; Cunning, Benjamin V.; Sasaki, Kazunari; Lyth, Stephen M.

2018-01-01

Due to the high cost and limited availability of platinum, the development of non-platinum-group metals (non-PGM) catalysts is of paramount importance. A promising alternative to Pt are Fe-N-C-based materials. Here we present the synthesis, characterization and electrochemistry of a template-free nitrogen-doped carbon foam, impregnated with iron. This low-cost and gram-scale method results in materials with micron-scale pore size and large surface area (1600 m2g-1). When applied as an oxygen reduction reaction (ORR) electrocatalyst in alkaline solution, the Fe-N-C foams display extremely high initial activity, slightly out-performing commercially available non-PGM catalysts (NCP-2000, Pajarito Powder). The load-cycle durability in alkaline solution is investigated, and the performance steadily degrades over 60,000 potential cycles, whilst the commercial catalyst is remarkably stable. The post-operation catalyst microstructure is elucidated by transmission electron microscopy (TEM), to provide insight into the degradation processes. The resulting images suggest that potential cycling leads to leaching of atomically dispersed Fe-N2/4 sites in all the catalysts, whereas encapsulated iron nanoparticles are protected.

Zeolite A synthesized from alkaline assisted pre-activated halloysite for efficient heavy metal removal in polluted river water and industrial wastewater.

PubMed

Meng, Qingpeng; Chen, Hong; Lin, Junzhong; Lin, Zhang; Sun, Junliang

2017-06-01

High quality zeolite A was synthesized through a hydrothermal process using alkaline-assisted pre-activated halloysite mineral as the alumina and silica source. The synthesis conditions employed in this study were finely tuned by varying the activating temperature, sodium hydroxide content, water content and Si/Al ratio. The obtained zeolite A showed excellent adsorption properties for both single metal cation solutions and mixed cation solutions when the concentrations of the mixed cations were comparable with those in polluted natural river water and industrial wastewater. High adsorptive capacities for Ag + (123.05mg/g) and Pb 2+ (227.70mg/g) were achieved using the synthesized zeolite A. This observation indicates that the zeolite A synthesized from alkaline-assisted pre-activated halloysite can be used as a low-cost and relatively effective adsorbent to purify heavy metal cation polluted natural river water and industrial wastewater. Copyright © 2016. Published by Elsevier B.V.

Dynamics of pH modification of an acidic protein bait used for tropical fruit flies (Diptera: Tephritidae).

PubMed

Heath, Robert R; Vazquez, Aime; Schnell, Elena Q; Villareal, Janett; Kendra, Paul E; Epsky, Nancy D

2009-12-01

Several species of Anastrepha and Bactrocera fruit flies (Diptera: Tephritidae) are captured in traps baited with the protein bait NuLure combined with borax (sodium tetraborate decahydrate) in an aqueous solution, typically 9% NuLure (vol:vol) with 3% borax (wt:vol). NuLure is an acid hydrolysate of corn and has an acidic pH. Addition of borax makes the solution more alkaline, and increase in alkalinity results in increase of ammonia release from the bait solution. This is a very dynamic system, with resultant pH affected by factors such as the amount of borax added, the pH of the water used for preparation, the age of the bait solution, and the development of microbial growth. Problems with borax include amount needed to increase alkalinity of NuLure solutions, which creates difficulties in disposing of spent bait in fruit fly trapping programs. Therefore, research was conducted to evaluate NaOH as an alternative method to increase alkalinity of NuLure solutions. Laboratory experiments compared effect of NaOH versus borax for pH modification on changes in pH and ammonia content of NuLure solutions over time. Although NuLure/NaOH solutions could be adjusted to a more alkaline pH than NuLure/borax solutions, borax plays a critical role in pH stability over time. However, the pH of NuLure/NaOH is stabilized when propylene glycol (10% vol:vol) was used to prepare the bait solution. The use of NaOH can provide an alternative to the use of borax to increase bait solution alkalinity.

CONCENTRATION OF Pu USING OXALATE TYPE CARRIER

DOEpatents

Ritter, D.M.; Black, R.P.S.

1960-04-19

A method is given for dissolving and reprecipitating an oxalate carrier precipitate in a carrier precipitation process for separating and recovering plutonium from an aqueous solution. Uranous oxalate, together with plutonium being carried thereby, is dissolved in an aqueous alkaline solution. Suitable alkaline reagents are the carbonates and oxulates of the alkali metals and ammonium. An oxidizing agent selected from hydroxylamine and hydrogen peroxide is then added to the alkaline solution, thereby oxidizing uranium to the hexavalent state. The resulting solution is then acidified and a source of uranous ions provided in the acidified solution, thereby forming a second plutoniumcarrying uranous oxalate precipitate.

Self-Supported Ni(P, O)x·MoOx Nanowire Array on Nickel Foam as an Efficient and Durable Electrocatalyst for Alkaline Hydrogen Evolution.

PubMed

Hua, Wei; Liu, Huanyan; Wang, Jian-Gan; Wei, Bingqing

2017-12-06

Earth-abundant and low-cost catalysts with excellent electrocatalytic hydrogen evolution reaction (HER) activity in alkaline solution play an important role in the sustainable production of hydrogen energy. In this work, a catalyst of Ni(P, O) x ·MoO x nanowire array on nickel foam has been prepared via a facile route for efficient alkaline HER. Benefiting from the collaborative advantages of Ni(P, O) x and amorphous MoO x , as well as three-dimensional porous conductive nickel scaffold, the hybrid electrocatalyst shows high catalytic activity in 1 M KOH aqueous solution, including a small overpotential of 59 mV at 10 mA cm -2 , a low Tafel slope of 54 mV dec -1 , and excellent cycling stability.

Self-Supported Ni(P, O)x·MoOx Nanowire Array on Nickel Foam as an Efficient and Durable Electrocatalyst for Alkaline Hydrogen Evolution

PubMed Central

Hua, Wei; Liu, Huanyan

2017-01-01

Earth-abundant and low-cost catalysts with excellent electrocatalytic hydrogen evolution reaction (HER) activity in alkaline solution play an important role in the sustainable production of hydrogen energy. In this work, a catalyst of Ni(P, O)x·MoOx nanowire array on nickel foam has been prepared via a facile route for efficient alkaline HER. Benefiting from the collaborative advantages of Ni(P, O)x and amorphous MoOx, as well as three-dimensional porous conductive nickel scaffold, the hybrid electrocatalyst shows high catalytic activity in 1 M KOH aqueous solution, including a small overpotential of 59 mV at 10 mA cm−2, a low Tafel slope of 54 mV dec-1, and excellent cycling stability. PMID:29210991

In vitro assessment of genotoxic effects of electric arc furnace dust on human lymphocytes using the alkaline comet assay.

PubMed

Garaj-Vrhovac, Vera; Orescanin, Visnja; Ruk, Damir; Gajski, Goran

2009-02-15

In vitro genotoxic effects of leachates of electric arc furnace dust (EAFD) on human peripheral lymphocytes, assessed prior and following the treatment with a strong alkaline solution were investigated using the alkaline comet assay. Prior and following the treatment, lymphocytes were incubated with leachate of EAFD for 6 and 24 hours at 37 degrees C. Negative controls were also included. Mean values of the tail lengths established in the samples treated with the leachate stemming from the original dust for 6 and 24 hours, were 15.70 microm and 16.78 microm, respectively, as compared to 12.33 microm found in the control sample. Slight, but significant increase in the tail length was also found with the dust treated with a strong alkaline solution (13.37 microm and 13.60 microm). In case of high heavy metal concentrations (the extract of the original furnace dust), the incubation period was revealed to be of significance as well. The obtained results lead to the conclusion that alkaline comet assay could be used as a rapid, sensitive and low-cost tool when assessing genotoxicity of various waste materials, such as leachates of the electric arc furnace dust.

Crystal-chemistry insight into the photocatalytic activity of BiOCl x Br1- x nanoplate solid solutions

NASA Astrophysics Data System (ADS)

Xu, Huan-Yan; Han, Xu; Tan, Qu; Wu, Ke-Jia; Qi, Shu-Yan

2017-06-01

In this study, a facile alcoholysis method was developed to synthesize BiOCl x Br1- x nanoplates at room temperature and atmospheric pressure. In this route, strong acid or alkaline environment was absolutely avoided to realize the high exposure of {001} crystal facets. The regular changes in XRD peaks and cell parameters as a function of the Br content strongly declared that the obtained BiOCl x Br1- x products belonged to a group of solid solutions. The 2D nanosheets with in-plane wrinkles were clearly observed in TEM images. Interestingly, as the Br content increased, band gaps of BiOCl x Br1- x solid solutions gradually decreased. The photocatalytic degradation of RhB under simulated sunlight irradiation indicated that BiOCl0.5Br0.5 had the best photocatalytic activity. From the viewpoint of crystal chemistry, the photocatalytic activity of BiOCl x Br1- x solid solutions was closely related with the exposure amount of {001} facets, interlayer spacing of (001) plane and energy-level position of valence band.

A new method of auxiliary purification for motor vehicle exhaust.

PubMed

Li, Dingqi

2018-07-01

As a result of the limitations of current purification technologies, purification efficiency is relatively low, particularly during startup or in the case of other abnormal automobile exhaust. Therefore, a new method of auxiliary purification is proposed in this paper. The acidic solution of potassium permanganate can oxidize carbon monoxide, nitrogen oxides and sulfur dioxide at relatively high temperatures and the alkaline solution of potassium permanganate can selectively absorb nitrogen oxide and sulfur dioxide. Therefore, we carried out the experiment using a solution of potassium permanganate and sulfuric acid as well as a solution of sodium carbonate and potassium permanganate, which served as the reagents for the auxiliary purification. The results of the test showed that after auxiliary purification by the acidic solution of potassium permanganate and the alkaline solution of potassium permanganate, the concentrations of carbon monoxide, hydrocarbons, nitrogen oxides and solid particles in the emissions were considerably lower than the concentrations prior to purification. It is possible to reduce the motor vehicle exhaust by the auxiliary purification of the solutions.

Assessing carbon dioxide removal through global and regional ocean alkalinization under high and low emission pathways

NASA Astrophysics Data System (ADS)

Lenton, Andrew; Matear, Richard J.; Keller, David P.; Scott, Vivian; Vaughan, Naomi E.

2018-04-01

Atmospheric carbon dioxide (CO2) levels continue to rise, increasing the risk of severe impacts on the Earth system, and on the ecosystem services that it provides. Artificial ocean alkalinization (AOA) is capable of reducing atmospheric CO2 concentrations and surface warming and addressing ocean acidification. Here, we simulate global and regional responses to alkalinity (ALK) addition (0.25 PmolALK yr-1) over the period 2020-2100 using the CSIRO-Mk3L-COAL Earth System Model, under high (Representative Concentration Pathway 8.5; RCP8.5) and low (RCP2.6) emissions. While regionally there are large changes in alkalinity associated with locations of AOA, globally we see only a very weak dependence on where and when AOA is applied. On a global scale, while we see that under RCP2.6 the carbon uptake associated with AOA is only ˜ 60 % of the total, under RCP8.5 the relative changes in temperature are larger, as are the changes in pH (140 %) and aragonite saturation state (170 %). The simulations reveal AOA is more effective under lower emissions, therefore the higher the emissions the more AOA is required to achieve the same reduction in global warming and ocean acidification. Finally, our simulated AOA for 2020-2100 in the RCP2.6 scenario is capable of offsetting warming and ameliorating ocean acidification increases at the global scale, but with highly variable regional responses.

The Effect of Alkaline Concentration on Coconut Husk Crystallinity and the Yield of Sugars Released

NASA Astrophysics Data System (ADS)

Sangian, H. F.; Widjaja, A.

2018-02-01

This work was to analyze the effect of alkaline concentration on coconut coir husk crystallinity and sugar liberated enzymatically. The data showed that the employing of alkaline on lignocellulose transformed the crystallinity. The XRD peaks increased highly which indicated that cellulose was more opened and exposed. After pretreatment, the chemical compositions (cellulose, hemicellulose, and lignin) were changed significantly. The employing 1% alkaline, the cellulosic content inclined if compared to that of non-pretreatment. When the alkaline concentration was added to 4%, the cellulose was decreased slightly which indicated that a part of cellulose and hemicellulose was dissolved into solution. It was found the alkaline pretreatment influenced by the biochemical reaction of treated substrates in producing the reducing sugars. The amounts of sugar liberated enzymatically of coconut husk treated by 1% and 4% alkaline increased to 0.26, and 0.24 g sugar/g (cellulose+hemicellulose), respectively, compared to that of native solid recorded at 0.18 g sugar/g (cellulose+hemicellulose).

Development of silver nanoparticle-doped adsorbents for the separation and recovery of radioactive iodine from alkaline solutions.

PubMed

Kim, Taewoon; Lee, Seung-Kon; Lee, Suseung; Lee, Jun Sig; Kim, Sang Wook

2017-11-01

Removing radioactive iodine from solutions containing fission products is essential for nuclear facility decontamination, radioactive waste treatment, and medical isotope production. For example, the production of high-purity fission 99 Mo by irradiation of 235 U with neutrons involves the removal of iodine from an alkaline solution of the irradiated target (which contains numerous fission products and a large quantity of aluminate ions) using silver-based materials or anion-exchange resins. To be practically applicable, the utilized iodine adsorbent should exhibit a decontamination factor of at least 200. Herein, the separation of radioactive iodine from alkaline solutions was achieved using alumina doped with silver nanoparticles (Ag NPs). Ag NPs have a larger surface area than Ag powder/wires and can thus adsorb iodine more effectively and economically, whereas alumina is a suitable inert support that does not adsorb 99 Mo and is stable under basic conditions. The developed adsorbents with less impurities achieved iodine removal and recovery efficiencies of 99.7 and 62%, respectively, thus being useful for the production of 131 I, a useful medical isotope. Copyright © 2017. Published by Elsevier Ltd.

Effect of an alkaline environment on the engineering behavior of cement-stabilized/solidified Zn-contaminated soils.

PubMed

Liu, Jingjing; Zha, Fusheng; Deng, Yongfeng; Cui, Kerui; Zhang, Xueqin

2017-12-01

Although the stabilization/solidification method has been widely used for remediation of heavy metal-contaminated soils in recent decades, the engineering behavior and mobility of heavy metal ions under alkaline groundwater conditions are still unclear. Therefore, the unconfined compressive strength test (UCS) combined with toxicity characteristic leaching procedure (TCLP) and general acid neutralization capacity (GANC) was used to investigate the effects of alkalinity (using NaOH to simulate alkalinity in the environment) on the mechanical and leaching characteristics of cement-solidified/stabilized (S/S) Zn-contaminated soils. Moreover, the microstructure was analyzed using the scanning electron microscope (SEM) technology. The results indicated that alkaline environment could accelerate the UCS development compared with specimens without soaking in NaOH solution,, regardless of whether the specimens contained Zn 2+ or not. And the UCS varied obviously attributed to the variations of both NaOH concentration and soaking time. Except for the specimens soaked for 90 days, the leached Zn 2+ concentrations were higher than that of without soaking. However, the leachability of Zn 2+ in all the stabilized specimens is in the regulatory level. ANC results indicated that the Zn 2+ leaching behavior can be divided into three stages related to the initial leachate pH. Moreover, SEM results proved that the alkaline environment could actually facilitate the cement hydration process. The results proved in the present paper could be useful in treating the heavy metal-contaminated soils involved in the solidification/stabilization technology under alkaline environment.

Method of determining pH by the alkaline absorption of carbon dioxide

DOEpatents

Hobbs, David T.

1992-01-01

A method for measuring the concentration of hydroxides in alkaline solutions in a remote location using the tendency of hydroxides to absorb carbon dioxide. The method includes the passing of carbon dioxide over the surface of an alkaline solution in a remote tank before and after measurements of the carbon dioxide solution. A comparison of the measurements yields the absorption fraction from which the hydroxide concentration can be calculated using a correlation of hydroxide or pH to absorption fraction.

The effect of functionalized polycarboxylate structures as corrosion inhibitors in a simulated concrete pore solution

NASA Astrophysics Data System (ADS)

Fazayel, A. S.; Khorasani, M.; Sarabi, A. A.

2018-05-01

In this study, the effects of polycarboxylate derivatives with different comonomers and functional groups on the control or reduction of corrosion in steel specimens were evaluated through electrochemical impedance spectroscopy (EIS) and potentiodynamic analysis. A highly alkaline contaminated concrete pore solution (CPS) containing chlorides was used to simulate the pitting corrosion, and according to the results, the mechanism of inhibitive action was determined. Both the inhibition efficiency and pitting corrosion inhibition of methacrylate-copolymers were in the order of poly methacrylate-co acrylamide > poly methacrylate-co-2-acrylamido-2 methylpropane sulfonic acid > poly methacrylate-co-hydroxyethyl methacrylate. In addition, the corrosion potential of steel specimens in all studied concentrations of NaCl with different concentrations of polymethacrylate-co acrylamide (as the best inhibitor in this study) in saturated Ca(OH)2 solution showed almost an identical trend. Polymethacrylic acid-co-acrylamide showed a 92.35% inhibitor efficiency in the saturated Ca(OH)2 solution containing 1.8 wt.% chlorides and could effectively reduce the corrosion rate. Even at 3.5 wt.% of NaCl, this inhibitor could remarkably reduce the destructive effect of chloride ion attacks on the steel surface and passive film. The inhibition effect of these polymeric inhibitors seemed to be due to the formation of a barrier layer on the metal surface, approved by the well-known adsorption mechanism of organic molecules at the metal/solution interface. The results of SEM, EDS and AFM investigations were also in agreement with the outcomes of electrochemical studies.

Ferrate treatment for removing chromium from high-level radioactive tank waste.

PubMed

Sylvester, P; Rutherford, L A; Gonzalez-Martin, A; Kim, J; Rapko, B M; Lumetta, G J

2001-01-01

A method has been developed for removing chromium from alkaline high-level radioactive tank waste. Removing chromium from these wastes is critical in reducing the volume of waste requiring expensive immobilization and deep geologic disposition. The method developed is based on the oxidation of insoluble chromium(III) compounds to soluble chromate using ferrate. This method could be generally applicable to removing chromium from chromium-contaminated solids, when coupled with a subsequent reduction of the separated chromate back to chromium(III). The tests conducted with a simulated Hanford tank sludge indicate that the chromium removal with ferrate is more efficient at 5 M NaOH than at 3 M NaOH. Chromium removal increases with increasing Fe(VI)/Cr(II) molar ratio, but the chromium removal tends to level out for Fe(VI)/ Cr(III) greaterthan 10. Increasingtemperature leadsto better chromium removal, but higher temperatures also led to more rapid ferrate decomposition. Tests with radioactive Hanford tank waste generally confirmed the simulant results. In all cases examined, ferrate enhanced the chromium removal, with a typical removal of around 60-70% of the total chromium present in the washed sludge solids. The ferrate leachate solutions did not contain significant concentrations of transuranic elements, so these solutions could be disposed as low-activity waste.

Alkaline-side extraction of technetium from tank waste using crown ethers and other extractants

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

Bonnesen, P.V.; Moyer, B.A.; Presley, D.J.

The chemical development of a new crown-ether-based solvent-extraction process for the separation of (Tc) from alkaline tank-waste supernate is ready for counter-current testing. The process addresses a priority need in the proposed cleanup of Hanford and other tank wastes. This need has arisen from concerns due to the volatility of Tc during vitrification, as well as {sup 99}Tc`s long half-life and environmental mobility. The new process offers several key advantages that direct treatability--no adjustment of the waste composition is needed; economical stripping with water; high efficiency--few stages needed; non-RCRA chemicals--no generation of hazardous or mixed wastes; co-extraction of {sup 90}Sr;more » and optional concentration on a resin. A key concept advanced in this work entails the use of tandem techniques: solvent extraction offers high selectivity, while a subsequent column sorption process on the aqueous stripping solution serves to greatly concentrate the Tc. Optionally, the stripping solution can be evaporated to a small volume. Batch tests of the solvent-extraction and stripping components of the process have been conducted on actual melton Valley Storage Tank (MVST) waste as well as simulants of MVST and Hanford waste. The tandem process was demonstrated on MVST waste simulants using the three solvents that were selected the final candidates for the process. The solvents are 0.04 M bis-4,4{prime}(5{prime})[(tert-butyl)cyclohexano]-18-crown-6 (abbreviated di-t-BuCH18C6) in a 1:1 vol/vol blend of tributyl phosphate and Isopar{reg_sign} M (an isoparaffinic kerosene); 0.02 M di-t-BuCH18C6 in 2:1 vol/vol TBP/Isopar M and pure TBP. The process is now ready for counter-current testing on actual Hanford tank supernates.« less

Evaluation of alkaline electrolyzed water to replace traditional phosphate enhancement solutions: Effects on water holding capacity, tenderness, and sensory characteristics.

PubMed

Rigdon, Macc; Hung, Yen-Con; Stelzleni, Alexander M

2017-01-01

Sixty-four pork loins were randomly assigned to one of four treatments to evaluate the use of alkaline electrolyzed reduced water as a replacement for traditional enhancement solutions. Treatments included: alkaline electrolyzed reduced water (EOH; pH≈11.5), EOH plus 2.5% potassium-lactate (EOK), industry standard (IS; 0.35% sodium tri-polyphosphate, 0.14% sodium chloride, 2.5% potassium-lactate), and no enhancement (CON). After enhancement (targeting 110%) and rest period, chops were cut (2.54-cm) to test treatment effects on water holding capacity, Warner-Bratzler shear force (WBSF), and sensory attributes. Despite its alkaline nature EOH chops exuded more water (P<0.05) than EOK, IS, or CON chops. Control chops were similar (P>0.05) to EOK, however CON and EOK both lost more moisture (P<0.05) than IS. The use of alkaline electrolyzed reduced water did not improve WBSF or sensory characteristics compared to IS treated chops. As a stand-alone enhancement solution alkaline electrolyzed reduced water was not a suitable replacement for industry standard solutions. Copyright © 2016 Elsevier Ltd. All rights reserved.

Mathematics of the total alkalinity-pH equation - pathway to robust and universal solution algorithms: the SolveSAPHE package v1.0.1

NASA Astrophysics Data System (ADS)

Munhoven, G.

2013-08-01

The total alkalinity-pH equation, which relates total alkalinity and pH for a given set of total concentrations of the acid-base systems that contribute to total alkalinity in a given water sample, is reviewed and its mathematical properties established. We prove that the equation function is strictly monotone and always has exactly one positive root. Different commonly used approximations are discussed and compared. An original method to derive appropriate initial values for the iterative solution of the cubic polynomial equation based upon carbonate-borate-alkalinity is presented. We then review different methods that have been used to solve the total alkalinity-pH equation, with a main focus on biogeochemical models. The shortcomings and limitations of these methods are made out and discussed. We then present two variants of a new, robust and universally convergent algorithm to solve the total alkalinity-pH equation. This algorithm does not require any a priori knowledge of the solution. SolveSAPHE (Solver Suite for Alkalinity-PH Equations) provides reference implementations of several variants of the new algorithm in Fortran 90, together with new implementations of other, previously published solvers. The new iterative procedure is shown to converge from any starting value to the physical solution. The extra computational cost for the convergence security is only 10-15% compared to the fastest algorithm in our test series.

The application and properties of composite sorbents of inorganic ion exchangers and polyacrylonitrile binding matrix.

PubMed

Nilchi, A; Khanchi, A; Atashi, H; Bagheri, A; Nematollahi, L

2006-10-11

A description is given of the preparation and properties of potassium hexacyanocobalt (II) ferrate (II) (KCFC) and the composite, potassium hexacyanocobalt (II) ferrate (II)-polyacrylonitrile (KCFC-PAN). The materials were dried at high temperatures and characterized by chemical analysis, scanning electron microscope, X-ray diffraction, inductively coupled plasma and infrared. The ion exchange of alkaline earth metals and molybdenum on a nonstoichiometric compound K(2)[CoFe(CN)(6)] and its PAN based absorber was examined by batch methods. The adsorption of molybdenum from aqueous solutions on KCFC-PAN was investigated and optimized as a function of equilibration time and pH. The materials which were dried at optimum high temperature of 110 degrees C were found to be stable in water, dilute acids, alkaline solutions and relatively high temperature. The distribution coefficient values K(d) for alkaline earth metals, followed the same trend of increase for both sets of absorbers studied, i.e. Ba(2+)>Sr(2+)>Ca(2+)>Mg(2+), which closely resembles to the order of the size of the hydrated cations. However, the K(d) values show a significant increase for PAN based absorbers in comparison to KCFC absorbers.

Method of enhancing the wettability of boron nitride for use as an electrochemical cell separator

DOEpatents

McCoy, L.R.

1981-01-23

A felt or other fabric of boron nitride suitable for use as an interelectrode separator within an electrochemical cell is wetted with a solution containing a thermally decomposable organic salt of an alkaline earth metal. An aqueous solution of magnesium acetate is the preferred solution for this purpose. After wetting the boron nitride, the solution is dried by heating at a sufficiently low temperature to prevent rapid boiling and the creation of voids within the separator. The dried material is then calcined at an elevated temperature in excess of 400/sup 0/C to provide a coating of an oxide of magnesium on the surface of the boron nitride fibers. A fabric or felt of boron nitride treated in this manner is easily wetted by molten electrolytic salts, such as the alkali metal halides or alkaline earth metal halides, that are used in high temperature, secondary electrochemical cells.

Method of enhancing the wettability of boron nitride for use as an electrochemical cell separator

DOEpatents

McCoy, Lowell R.

1982-01-01

A felt or other fabric of boron nitride suitable for use as an interelecte separator within an electrochemical cell is wetted with a solution containing a thermally decomposable organic salt of an alkaline earth metal. An aqueous solution of magnesium acetate is the preferred solution for this purpose. After wetting the boron nitride, the solution is dried by heating at a sufficiently low temperature to prevent rapid boiling and the creation of voids within the separator. The dried material is then calcined at an elevated temperature in excess of 400.degree. C. to provide a coating of an oxide of magnesium on the surface of the boron nitride fibers. A fabric or felt of boron nitride treated in this manner is easily wetted by molten electrolytic salts, such as the alkali metal halides or alkaline earth metal halides, that are used in high temperature, secondary electrochemical cells.

Simulated Impact of Glacial Runoff on CO2 Uptake in the Gulf of Alaska

NASA Astrophysics Data System (ADS)

Pilcher, Darren J.; Siedlecki, Samantha A.; Hermann, Albert J.; Coyle, Kenneth O.; Mathis, Jeremy T.; Evans, Wiley

2018-01-01

The Gulf of Alaska (GOA) receives substantial summer freshwater runoff from glacial meltwater. The alkalinity of this runoff is highly dependent on the glacial source and can modify the coastal carbon cycle. We use a regional ocean biogeochemical model to simulate CO2 uptake in the GOA under different alkalinity-loading scenarios. The GOA is identified as a current net sink of carbon, though low-alkalinity tidewater glacial runoff suppresses summer coastal carbon uptake. Our model shows that increasing the alkalinity generates an increase in annual CO2 uptake of 1.9-2.7 TgC/yr. This transition is comparable to a projected change in glacial runoff composition (i.e., from tidewater to land-terminating) due to continued climate warming. Our results demonstrate an important local carbon-climate feedback that can significantly increase coastal carbon uptake via enhanced air-sea exchange, with potential implications to the coastal ecosystems in glaciated areas around the world.

Effect of molybdenum ion implantation of the pitting corrosion of depleted uranium - 0.75 titanium alloy. (Reannouncement with new availability information). Final report

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

Lei, K.S.; Chang, F.; Levy, M.

1993-07-01

Pitting corrosion of molybdenum-ion-implanted, depleted uranium -0 75 Ti (DU -0 75 Ti) has been studied electrochemically in acidic, neutral, and alkaline solutions containing sodium chloride, and the results have been compared to those of the unimplanted DU -0 75 Ti. The data show that Mo implantation shifts the pitting potential of DU -0 75 Ti in the noble direction in acidic and alkaline solutions. In neutral 50 ppm Cl- solution, however, there is no beneficial effect of Mo implantation. Auger analysis studies show that before exposure to the solutions, all the molybdenum is in the oxide, which is approximatelymore » l000 A thick. After electrochemical scans in the acidic and alkaline chloride solutions, most of the Mo disappears from the oxide. However, no decrease in Mo concentration is found after exposure in neutral chloride solution. It is proposed that the implanted molybdenum dissolves in the acidic and alkaline solutions and forms simple or complex molybdates that inhibit pitting corrosion. The implanted molybdenum does not dissolve in the neutral chloride solution and inhibition does not occur.« less

Method of determining pH by the alkaline absorption of carbon dioxide

DOEpatents

Hobbs, D.T.

1992-10-06

A method is described for measuring the concentration of hydroxides in alkaline solutions in a remote location using the tendency of hydroxides to absorb carbon dioxide. The method includes the passing of carbon dioxide over the surface of an alkaline solution in a remote tank before and after measurements of the carbon dioxide solution. A comparison of the measurements yields the absorption fraction from which the hydroxide concentration can be calculated using a correlation of hydroxide or pH to absorption fraction. 2 figs.

Electrochemical probing of high-level radioactive waste tanks containing washed sludge and precipitates

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

Bickford, D.F.; Congdon, J.W.; Oblath, S.B.

1987-01-01

At the U.S. Department of Energy's Savannah River Plant, corrosion of carbon steel storage tanks containing alkaline, high-level radioactive waste is controlled by specification of limits on waste composition and temperature. Processes for the preparation of waste for final disposal will result in waste with low corrosion inhibitor concentrations and, in some cases, high aromatic organic concentrations, neither of which are characteristic of previous operations. Laboratory tests, conducted to determine minimum corrosion inhibitor levels indicated pitting of carbon steel near the waterline for proposed storage conditions. In situ electrochemical measurements of full-scale radioactive process demonstrations have been conducted to assessmore » the validity of laboratory tests. Probes included pH, Eh (potential relative to a standard hydrogen electrode), tank potential, and alloy coupons. In situ results are compared to those of the laboratory tests, with particular regard given to simulated solution composition.« less

Copper Sensing in Alkaline Electrolyte Using Anodic Stripping Voltammetry by Means of a Lead Mediator

DOE PAGES

Duay, Jonathon; Ortiz-Santiago, Joed E.; Lambert, Timothy N.

2017-10-05

Anodic stripping voltammetry (ASV) is an analysis technique that permits the selective and quantitative analysis of metal ion species in solution. It is most commonly applied in neutral to acidic electrolyte largely due to inherent metal ion solubility. Bismuth (Bi) is a common film used for ASV due to its good sensitivity, overall stability and insensitivity to O2. ASV, utilizing a Bi film, along with cadmium (Cd) and lead (Pb) as the plating mediators, has recently been adapted to determine zinc (Zn) concentrations in highly alkaline environments (30 % NaOH or 35 % M KOH). Successful analysis of Zn inmore » alkaline relies on the ability of the hydroxide to form soluble metal anion species, such as Bi(OH) 4 – and Zn(OH) 4 2–. Here, we look to extend this technique to detect and quantify copper (Cu) ions in these highly basic electrolytes. However, in general, the use of ASV to detect and quantify Cu ion concentrations is notoriously difficult as the Cu stripping peak potential overlays with that of Bi from the common Bi film electrode. Here, an ASV method for determining Cu concentration in alkaline solutions is developed utilizing Pb as a deposition mediator. As such, it was found that when analyzing Cu solutions in the presence of Pb, the stripping voltammetry curves present separate and defined Cu stripping peaks. Different analyzes were made to find the best stripping voltammetry performance conditions. As such, an accumulation time of 5 minutes, an accumulation potential of ≤–1.45 V vs. Hg/HgO, and a concentration of 35 wt% KOH were determined to be the conditions that presented the best ASV results. Utilizing these conditions, calibration curves in the presence of 5.0 ppm Pb showed the best linear stripping signal correlation with an r-squared value of 0.991 and a limit of detection (LOD) of 0.67 ppm. Lastly, these results give way to evaluating Cu concentrations using ASV in aqueous alkaline solutions.« less

Copper Sensing in Alkaline Electrolyte Using Anodic Stripping Voltammetry by Means of a Lead Mediator

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

Duay, Jonathon; Ortiz-Santiago, Joed E.; Lambert, Timothy N.

Anodic stripping voltammetry (ASV) is an analysis technique that permits the selective and quantitative analysis of metal ion species in solution. It is most commonly applied in neutral to acidic electrolyte largely due to inherent metal ion solubility. Bismuth (Bi) is a common film used for ASV due to its good sensitivity, overall stability and insensitivity to O2. ASV, utilizing a Bi film, along with cadmium (Cd) and lead (Pb) as the plating mediators, has recently been adapted to determine zinc (Zn) concentrations in highly alkaline environments (30 % NaOH or 35 % M KOH). Successful analysis of Zn inmore » alkaline relies on the ability of the hydroxide to form soluble metal anion species, such as Bi(OH) 4 – and Zn(OH) 4 2–. Here, we look to extend this technique to detect and quantify copper (Cu) ions in these highly basic electrolytes. However, in general, the use of ASV to detect and quantify Cu ion concentrations is notoriously difficult as the Cu stripping peak potential overlays with that of Bi from the common Bi film electrode. Here, an ASV method for determining Cu concentration in alkaline solutions is developed utilizing Pb as a deposition mediator. As such, it was found that when analyzing Cu solutions in the presence of Pb, the stripping voltammetry curves present separate and defined Cu stripping peaks. Different analyzes were made to find the best stripping voltammetry performance conditions. As such, an accumulation time of 5 minutes, an accumulation potential of ≤–1.45 V vs. Hg/HgO, and a concentration of 35 wt% KOH were determined to be the conditions that presented the best ASV results. Utilizing these conditions, calibration curves in the presence of 5.0 ppm Pb showed the best linear stripping signal correlation with an r-squared value of 0.991 and a limit of detection (LOD) of 0.67 ppm. Lastly, these results give way to evaluating Cu concentrations using ASV in aqueous alkaline solutions.« less

Adsorption of superplasticizer admixtures on alkali-activated slag pastes

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

Palacios, M.; Houst, Y.F.; Bowen, P.

2009-08-15

Alkali-activated slag (AAS) binders are obtained by a manufacturing process less energy-intensive than ordinary Portland cement (OPC) and involves lower greenhouse gasses emission. These alkaline cements allow the production of high mechanical strength and durable concretes. In the present work, the adsorption of different superplasticizer admixtures (naphthalene-based, melamine-based and a vinyl copolymer) on the slag particles in AAS pastes using alkaline solutions with different pH values have been studied in detail. The effect of the superplasticizers on the yield stress and plastic viscosity of the AAS and OPC pastes have been also evaluated. The results obtained allowed us to concludemore » that the adsorption of the superplasticizers on AAS pastes is independent of the pH of the alkaline solutions used and lower than on OPC pastes. However, the effect of the admixtures on the rheological parameters depends directly on the type and dosage of the superplasticizer as well as of the binder used and, in the case of the AAS, on the pH of the alkaline activator solution. In 11.7-pH NaOH-AAS pastes the dosages of the superplasticizers required to attain similar reduction in the yield stress are ten-fold lower than for Portland cement. In this case the superplasticizers studied show a fluidizing effect considerably higher in 11.7-pH NaOH-AAS pastes than in OPC pastes. In 13.6-pH NaOH-AAS pastes, the only admixture observed to affect the rheological parameters is the naphthalene-based admixture due to its higher chemical stability in such extremely alkaline media.« less

Kinetics of the Fading of Phenolphthalein in Alkaline Solution.

ERIC Educational Resources Information Center

Nicholson, Lois

1989-01-01

Described is an experiment which illustrates pseudo-first-order kinetics in the fading of a common indicator in an alkaline solution. Included are background information, details of materials used, laboratory procedures, and sample results. (CW)

The Passive Film Growth Mechanism of New Corrosion-Resistant Steel Rebar in Simulated Concrete Pore Solution: Nanometer Structure and Electrochemical Study

PubMed Central

Jiang, Jin-yang; Wang, Danqian; Chu, Hong-yan; Ma, Han; Liu, Yao; Gao, Yun; Shi, Jinjie; Sun, Wei

2017-01-01

An elaborative study was carried out on the growth mechanism and properties of the passive film for a new kind of alloyed corrosion-resistant steel (CR steel). The passive film naturally formed in simulated concrete pore solutions (pH = 13.3). The corrosion resistance was evaluated by various methods including open circuit potential (OCP), linear polarization resistance (LPR) measurements, and electrochemical impedance spectroscopy (EIS). Meanwhile, the 2205 duplex stainless steel (SS steel) was evaluated for comparison. Moreover, the passive film with CR steel was studied by means of X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), Atomic Force Microscope (AFM), and the Mott‑Schottky approach. The results showed that the excellent passivity of CR steel could be detected in a high alkaline environment. The grain boundaries between the fine passive film particles lead to increasing Cr oxide content in the later passivation stage. The filling of cation vacancies in the later passivation stage as well as the orderly crystalized inner layer contributed to the excellent corrosion resistance of CR steel. A passive film growth model for CR steel was proposed. PMID:28772772

The Passive Film Growth Mechanism of New Corrosion-Resistant Steel Rebar in Simulated Concrete Pore Solution: Nanometer Structure and Electrochemical Study.

PubMed

Jiang, Jin-Yang; Wang, Danqian; Chu, Hong-Yan; Ma, Han; Liu, Yao; Gao, Yun; Shi, Jinjie; Sun, Wei

2017-04-14

An elaborative study was carried out on the growth mechanism and properties of the passive film for a new kind of alloyed corrosion-resistant steel (CR steel). The passive film naturally formed in simulated concrete pore solutions (pH = 13.3). The corrosion resistance was evaluated by various methods including open circuit potential (OCP), linear polarization resistance (LPR) measurements, and electrochemical impedance spectroscopy (EIS). Meanwhile, the 2205 duplex stainless steel (SS steel) was evaluated for comparison. Moreover, the passive film with CR steel was studied by means of X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), Atomic Force Microscope (AFM), and the Mott‑Schottky approach. The results showed that the excellent passivity of CR steel could be detected in a high alkaline environment. The grain boundaries between the fine passive film particles lead to increasing Cr oxide content in the later passivation stage. The filling of cation vacancies in the later passivation stage as well as the orderly crystalized inner layer contributed to the excellent corrosion resistance of CR steel. A passive film growth model for CR steel was proposed.

Stabilizing sodium hypochlorite at high pH: effects on soft tissue and dentin.

PubMed

Jungbluth, Holger; Marending, Monika; De-Deus, Gustavo; Sener, Beatrice; Zehnder, Matthias

2011-05-01

When sodium hypochlorite solutions react with tissue, their pH drops and tissue sorption decreases. We studied whether stabilizing a NaOCl solution at a high pH would increase its soft-tissue dissolution capacity and effects on the dentin matrix compared with a standard NaOCl solution of the same concentration and similar initial pH. NaOCl solutions were prepared by mixing (1:1) a 10% stock solution with water (standard) or 2 mol/L NaOH (stabilized). Physiological saline and 1 mol/L NaOH served as the controls. Chlorine content and alkaline capacity of NaOCl solutions were determined. Standardized porcine palatal soft-tissue specimens and human root dentin bars were exposed to test and control solutions. Weight loss percentage was assessed in the soft-tissue dissolution assay. Three-point bending tests were performed on the root dentin bars to determine the modulus of elasticity and flexural strength. Values between groups were compared using one-way analysis of variance with the Bonferroni correction for multiple testing (α < .05). Both solutions contained 5% NaOCl. One milliliter of the standard and the stabilized solution consumed 4.0 mL and 13.7 mL of a 0.1-mol/L HCl solution before they reached a pH level of 7.5, respectively. The stabilized NaOCl dissolved significantly more soft tissue than the standard solution, and the pH remained high. It also caused a higher loss in elastic modulus and flexure strength (P < .05) than the control solutions, whereas the standard solution did not. NaOH-stabilized NaOCl solutions have a higher alkaline capacity and are thus more proteolytic than standard counterparts. Copyright © 2011 American Association of Endodontists. Published by Elsevier Inc. All rights reserved.

No-core fiber-based highly sensitive optical fiber pH sensor.

PubMed

Bhardwaj, Vanita; Pathak, Akhilesh Kumar; Singh, Vinod Kumar

2017-05-01

The present work describes the fabrication and characterization of an optical fiber pH sensor using a sol–gel technique. The sensing head configuration is incorporated using a short section of no-core fiber, coated with tetraethyl orthosilicate and spliced at the end of a single mode fiber with a bulge. Different types of indicators (bromophenol blue, cresol red, and chlorophenol red) were used to achieve a wide pH range from 2 to 13. High sensitivities of the fabricated device were found to be 1.02 and ? 0.93 ?? nm / pH for acidic and alkaline solutions, respectively. From the characterization results, it was noted that there is an impact of ionic strength and an effect of the temperature of liquid on the response characteristic, which is an advantage of the existing device over the other pH sensors. The fabricated sensor exhibited good reflection spectrum, indicating a blueshift in resonance wavelength for alkaline solutions and a redshift for acidic solutions.

Supramolecular Assembly of a Biomineralizing Antimicrobial Peptide in Coarse-Grained Monte Carlo Simulations (Postprint)

DTIC Science & Technology

2010-07-05

aqueous solutions at a wide pH range.7 Silica forms rapidly at room temperature in the absence of other ionic catalysts or cofactors (buffers, salts...and other ionic species) that are normally required with in vitro biosilica synthesis. The silaffins are uniquely functionalized; serine residues are...alkaline conditions mimic the properties of the poly- ionic modifications on native silaffins.13,14 The zwitterionic properties facilitate intermolecular

Transcriptome analysis of genes involved in defense against alkaline stress in roots of wild jujube (Ziziphus acidojujuba)

PubMed Central

Tian, Shan; Wang, Bei; Zhao, Xusheng

2017-01-01

Wild jujube (Ziziphus acidojujuba Mill.) is highly tolerant to alkaline, saline and drought stress; however, no studies have performed transcriptome profiling to study the response of wild jujube to these and other abiotic stresses. In this study, we examined the tolerance of wild jujube to NaHCO3-NaOH solution and analyzed gene expression profiles in response to alkaline stress. Physiological experiments revealed that H2O2 content in leaves increased significantly and root activity decreased quickly during alkaline of pH 9.5 treatment. For transcriptome analysis, wild jujube plants grown hydroponically were treated with NaHCO3-NaOH solution for 0, 1, and 12 h and six transcriptomes from roots were built. In total, 32,758 genes were generated, and 3,604 differentially expressed genes (DEGs) were identified. After 1 h, 853 genes showed significantly different expression between control and treated plants; after 12 h, expression of 2,856 genes was significantly different. The expression pattern of nine genes was validated by quantitative real-time PCR. After gene annotation and gene ontology enrichment analysis, the genes encoding transcriptional factors, serine/threonine-protein kinases, heat shock proteins, cysteine-like kinases, calmodulin-like proteins, and reactive oxygen species (ROS) scavengers were found to be closely involved in alkaline stress response. These results will provide useful insights for elucidating the mechanisms underlying alkaline tolerance in wild jujube. PMID:28976994

De Novo Transcriptional Analysis of Alfalfa in Response to Saline-Alkaline Stress.

PubMed

An, Yi-Min; Song, Li-Li; Liu, Ying-Rui; Shu, Yong-Jun; Guo, Chang-Hong

2016-01-01

Saline-alkaline stress, caused by high levels of harmful carbonate salts and high soil pH, is a major abiotic stress that affects crop productivity. Alfalfa is a widely cultivated perennial forage legume with some tolerance to biotic and abiotic stresses, especially to saline-alkaline stress. To elucidate the mechanism underlying plant saline-alkaline tolerance, we conducted transcriptome analysis of whole alfalfa seedlings treated with saline-alkaline solutions for 0 day (control), 1 day (short-term treatment), and 7 days (long-term treatment) using ion torrent sequencing technology. A transcriptome database dataset of 53,853 unigenes was generated, and 2,286 and 2,233 genes were differentially expressed in the short-term and long-term treatment, respectively. Gene ontology analysis revealed 14 highly enriched pathways and demonstrated the differential response of metabolic pathways between the short-term and long-term treatment. The expression levels of 109 and 96 transcription factors were significantly altered significantly after 1 day and 7 days of treatment, respectively. Specific responses of peroxidase, flavonoids, and the light pathway component indicated that the antioxidant capacity was one of the central mechanisms of saline-alkaline stress tolerance response in alfalfa. Among the 18 differentially expressed genes examined by real time PCR, the expression levels of eight genes, including inositol transporter, DNA binding protein, raffinose synthase, ferritin, aldo/keto reductase, glutathione S-transferase, xyloglucan endotrans glucosylase, and a NAC transcription factor, exhibited different patterns in response to saline and alkaline stress. The expression levels of the NAC transcription factor and glutathione S-transferase were altered significantly under saline stress and saline-alkaline stress; they were upregulated under saline-alkaline stress and downregulated under salt stress. Physiology assays showed an increased concentration of reactive oxygen species and malondialdehyde and a decreased content of chlorophyll, indicating that anti-oxidation and detoxification play an important role in response to saline-alkaline stress. Overall, the transcriptome analysis provided novel insights into the saline-alkaline stress tolerance response mechanisms in alfalfa.

De Novo Transcriptional Analysis of Alfalfa in Response to Saline-Alkaline Stress

PubMed Central

An, Yi-Min; Song, Li-Li; Liu, Ying-Rui; Shu, Yong-Jun; Guo, Chang-Hong

2016-01-01

Saline-alkaline stress, caused by high levels of harmful carbonate salts and high soil pH, is a major abiotic stress that affects crop productivity. Alfalfa is a widely cultivated perennial forage legume with some tolerance to biotic and abiotic stresses, especially to saline-alkaline stress. To elucidate the mechanism underlying plant saline-alkaline tolerance, we conducted transcriptome analysis of whole alfalfa seedlings treated with saline-alkaline solutions for 0 day (control), 1 day (short-term treatment), and 7 days (long-term treatment) using ion torrent sequencing technology. A transcriptome database dataset of 53,853 unigenes was generated, and 2,286 and 2,233 genes were differentially expressed in the short-term and long-term treatment, respectively. Gene ontology analysis revealed 14 highly enriched pathways and demonstrated the differential response of metabolic pathways between the short-term and long-term treatment. The expression levels of 109 and 96 transcription factors were significantly altered significantly after 1 day and 7 days of treatment, respectively. Specific responses of peroxidase, flavonoids, and the light pathway component indicated that the antioxidant capacity was one of the central mechanisms of saline-alkaline stress tolerance response in alfalfa. Among the 18 differentially expressed genes examined by real time PCR, the expression levels of eight genes, including inositol transporter, DNA binding protein, raffinose synthase, ferritin, aldo/keto reductase, glutathione S-transferase, xyloglucan endotrans glucosylase, and a NAC transcription factor, exhibited different patterns in response to saline and alkaline stress. The expression levels of the NAC transcription factor and glutathione S-transferase were altered significantly under saline stress and saline-alkaline stress; they were upregulated under saline-alkaline stress and downregulated under salt stress. Physiology assays showed an increased concentration of reactive oxygen species and malondialdehyde and a decreased content of chlorophyll, indicating that anti-oxidation and detoxification play an important role in response to saline-alkaline stress. Overall, the transcriptome analysis provided novel insights into the saline-alkaline stress tolerance response mechanisms in alfalfa. PMID:27458463

Influence of the marinating type on the morphological and sensory properties of horse meat.

PubMed

Vlahova-Vangelova, Dessislava B; Abjanova, Sholpan; Dragoev, Stefan G

2014-01-01

The aim of this study was to explore the influence of acid, alkaline and water-oil marinating on morphological changes and sensory properties of horse meat (m. Longissimus dorsi). Nine samples (C - control stored in air, AL - alkaline marinated in 2% polyphosphates and 2% sodium chloride brine solution, AC - acid marinated in 2% sodium lactate and 2% sodium chloride brine solution, WO - marinated in water-oil emulsion (50/50) contained and 2% sodium chloride and SC - marinated in 2% sodium chloride brine solution) were examined. After 24 h and 48 h of marinating changes in morphology of marinated meat, pH and sensory properties of raw and roasted samples were established. It was determined that sensory properties (aroma, flavor and tenderness) after roasting were classified as follows: AL48 > AL24 > AC24 > AC48 > SC48 > SC24 > WO24 > WO48 > С. Meat tenderness in AL48, AL24, AC24 and AC48 showed better results due to stronger morphological changes in connective and muscle tissues. Alkaline solutions were more suitable for horse meat marinating compared to acid solutions and the possible reason for strong action of alkaline solutions was lower internal meat pH. Alkaline marinating should be conducted for 24 h because after 48 h the meat acquires a soft and unusually tender texture. Water-oil marinating was not appropriate for horse meat.

Alkaline solution absorption of carbon dioxide method and apparatus

DOEpatents

Hobbs, D.T.

1991-01-01

Disclosed is a method for measuring the concentration of hydroxides (or pH) in alkaline solutions, using the tendency of hydroxides to adsorb CO{sub 2}. The method comprises passing CO{sub 2} over the surface of an alkaline solution in a remote tank before and after measurements of the CO{sub 2} concentration. Comparison of the measurements yields the adsorption fraction from which the hydroxide concentration can be calculated using a correlation of hydroxide or pH to adsorption fraction. A schematic is given of a process system according to a preferred embodiment of the invention. 2 figs.

Deciphering the protective role of spermidine against saline-alkaline stress at physiological and proteomic levels in tomato.

PubMed

Zhang, Yi; Zhang, Hao; Zou, Zhi-Rong; Liu, Yi; Hu, Xiao-Hui

2015-02-01

In this research, the protective effect of spermidine (Spd) in mitigating saline-alkaline stress in tomato (Solanum lycopersicum L.) at physiological and proteomic levels were examined. The results showed that saline-alkaline stress induced accumulation of H2O2 and O2(-*), and increased the activities of antioxidase (SOD, CAT, and POD). Spermidine efficiently alleviated the inhibitory role of saline-alkaline on plant growth and inhibited saline-alkaline stress-induced H2O2 and O2(-*) accumulation. Proteomics investigations of the leaves of tomato seedlings, responding to a 75 mM saline-alkaline solution and 0.25 mM Spd, were performed. Maps of the proteome of leaf extracts were obtained by two-dimensional gel electrophoresis. An average of 49, 47 and 34 spots, which appeared repeatedly and that significantly altered the relative amounts of polypeptides by more than twofold, were detected for seedlings treated with saline-alkaline solution (S) compared to normal solution (CK), saline-alkaline plus spermidine (MS) compared to CK, or S versus MS, respectively. Thirty-nine of these proteins were identified by matrix-assisted laser desorption ionization-time of flight (MALDI-TOF) mass spectrometry and were classified into five functional categories, including energy and metabolism, signal transduction, amino acid metabolism, protein metabolism, and stress-defense response. Proteomics analysis coupled with bioinformatics indicated that Spd treatment helps tomato seedlings combat saline-alkaline stress by modulating the defense mechanism of plants and activating cellular detoxification, which protect plants from oxidative damage induced by saline-alkaline stress. Copyright © 2014 Elsevier Ltd. All rights reserved.

Electrocatalysis of the HER in acid and alkaline media

DOE PAGES

Danilovic, Nemanja; Subbaraman, Ram; Strmcnik, Dusan; ...

2013-01-01

Trends in the HER are studied on selected metals (M= Cu, Ag, Au, Pt, Ru, Ir, Ti) in acid and alkaline environments. Here, we found that with the exception of Pt, Ir and Au, due to high coverage by spectator species on non-noble metal catalysts, experimentally established positions of Cu , Ag, Ru and Ti in the observed volcano relations are still uncertain. We also found that while in acidic solutions the M-Hupd binding energy most likely is controlling the activity trends, the trends in activity in alkaline solutions are controlled by a delicate balance between two descriptors: the M-Hadmore » interaction as well as the energetics required to dissociate water molecules. We confirm the importance of the second descriptor by introducing bifunctional catalysts such as M modified by Ni(OH); e.g. while the latter serves to enhance catalytic decomposition of water, the metal sites are required for collecting and recombining the produced hydrogen intermediates.« less

Inorganic Carbon Source for Photosynthesis in the Seagrass Thalassia hemprichii (Ehrenb.) Aschers.

PubMed

Abel, K M

1984-11-01

Photosynthetic carbon uptake of the tropical seagrass Thalassia hemprichii (Ehrenb.) Aschers was studied by several methods. Photosynthesis in buffered seawater in media in the range of pH 6 to pH 9 showed an exponentially increasing rate with decreasing pH, thus indicating that free CO(2) was a photosynthetic substrate. However, these experiments were unable to determine whether photosynthesis at alkaline pH also contained some component due to HCO(3) (-) uptake. This aspect was further investigated by studying photosynthetic rates in a number of media of varying pH (7.8-8.61) and total inorganic carbon (0.75-13.17 millimolar). In these media, photosynthetic rate was correlated with free CO(2) concentration and was independent of the HCO(3) (-) concentration in the medium. Short time-course experiments were conducted during equilibration of free CO(2) and HCO(3) (-) after injection of (14)C labeled solution at acid or alkaline pH. High initial photosynthetic rates were observed when acidic solutions (largely free CO(2)) were used but not with alkaline solutions. The concentration of free CO(2) was found to be a limiting factor for photosynthesis in this plant.

Silicon Priming Created an Enhanced Tolerance in Alfalfa (Medicago sativa L.) Seedlings in Response to High Alkaline Stress.

PubMed

Liu, Duo; Liu, Miao; Liu, Xiao-Long; Cheng, Xian-Guo; Liang, Zheng-Wei

2018-01-01

Alkaline stress as a result of higher pH usually triggers more severe physiological damage to plants than that of saline stress with a neutral pH. In the present study, we demonstrated that silicon (Si) priming of alfalfa ( Medicago sativa L.) seedlings increased their tolerance to high alkaline stress situations. Gongnong No. 1 seedlings were subjected to alkaline stress simulated by 25 mM Na 2 CO 3 (pH 11.2). Alkaline stress greatly decreased the biomass and caused severe lodging or wilting of alfalfa seedlings. In contrast, the application of Si to alfalfa seedlings 36 h prior to the alkaline treatment significantly alleviated the damage symptoms and greatly increased the biomass and chlorophyll content. Because of being concomitant with increasing photosynthesis and water use efficiency, decreasing membrane injury and malondialdehyde content, and increasing peroxidase and catalase ascorbate activities in alfalfa leaves, thereby alleviating the triggered oxidative damage by alkaline stress to the plant. Furthermore, Si priming significantly decreased the accumulation of protein and proline content in alfalfa, thus reducing photosynthetic feedback repression. Si priming significantly accumulated more Na in the roots, but led to a decrease of Na accumulation and an increase of K accumulation in the leaves under alkaline stress. Meanwhile, Si priming decreased the accumulation of metal ions such as Mg, Fe, Mn, and Zn in the roots of alfalfa seedlings under alkaline stress. Collectively, these results suggested that Si is involved in the metabolic or physiological changes and has a potent priming effect on the alkaline tolerance of alfalfa seedlings. The present study indicated that Si priming is a new approach to improve the alkaline tolerance in alfalfa and provides increasing information for further exploration of the alkaline stress response at the molecular level in alfalfa.

Chromium(III) and chromium(VI) release from leather during 8 months of simulated use

PubMed Central

Lidén, Carola

2016-01-01

Summary Background Chromium (Cr) release from Cr‐tanned leather articles is a major cause of Cr contact dermatitis. It has been suggested that Cr(VI) release from leather is not necessarily an intrinsic property of the leather, but is strongly dependent on environmental conditions. Objectives To test this hypothesis for long‐term (8 months) simulated use. Materials and methods The release of total Cr and Cr(VI) from Cr‐tanned, unfinished leather was analysed in subsequent phosphate buffer (pH 8.0) immersions for a period of 7.5 months. The effect of combined ultraviolet treatment and alkaline solution (pH 12.1) was tested. Dry storage [20% relative humidity (RH)] was maintained between immersions. Atomic absorption spectroscopy, X‐ray fluorescence and diphenylcarbazide tests were used. Results Cr(VI) release was dependent on previous dry storage or alkaline treatment, but not on duration or number of previous immersions. Cr(III) release decreased with time. Fifty‐two percent of the total Cr released during the last immersion period was Cr(VI). Cr(VI) release exceeded 9 mg/kg in all immersion periods except in the first 10‐day immersion (2.6 mg/kg). Conclusions Cr(VI) release is primarily determined by environmental factors (RH prior to immersion, solution pH, and antioxidant content). The RH should be kept low prior to testing Cr(VI) release from leather. PMID:27144948

Removing tannins from medicinal plant extracts using an alkaline ethanol precipitation process: a case study of Danshen injection.

PubMed

Gong, Xingchu; Li, Yao; Qu, Haibin

2014-11-14

The alkaline ethanol precipitation process is investigated as an example of a technique for the removal of tannins extracted from Salviae miltiorrhizae Radix et Rhizoma for the manufacture of Danshen injection. More than 90% of the tannins can be removed. However, the recoveries of danshensu, rosmarinic acid, and salvianolic acid B were less than 60%. Total tannin removal increased as the refrigeration temperature decreased or the amount of NaOH solution added increased. Phenolic compound recoveries increased as refrigeration temperature increased or the amount of NaOH solution added decreased. When operated at a low refrigeration temperature, a relative high separation selectivity can be realized. Phenolic compound losses and tannin removal were mainly caused by precipitation. The formation of phenol salts, whose solubility is small in the mixture of ethanol and water used, is probably the reason for the precipitation. A model considering dissociation equilibrium and dissolution equilibrium was established. Satisfactory correlation results were obtained for phenolic compound recoveries and total tannin removal. Two important parameters in the model, which are the water content and pH value of alkaline supernatant, are suggested to be monitored and controlled to obtain high batch-to-batch consistency.

Chemically durable polymer electrolytes for solid-state alkaline water electrolysis

NASA Astrophysics Data System (ADS)

Park, Eun Joo; Capuano, Christopher B.; Ayers, Katherine E.; Bae, Chulsung

2018-01-01

Generation of high purity hydrogen using electrochemical splitting of water is one of the most promising methods for sustainable fuel production. The materials to be used as solid-state electrolytes for alkaline water electrolyzer require high thermochemical stability against hydroxide ion attack in alkaline environment during the operation of electrolysis. In this study, two quaternary ammonium-tethered aromatic polymers were synthesized and investigated for anion exchange membrane (AEM)-based alkaline water electrolyzer. The membranes properties including ion exchange capacity (IEC), water uptake, swelling degree, and anion conductivity were studied. The membranes composed of all C-C bond polymer backbones and flexible side chain terminated by cation head groups exhibited remarkably good chemical stability by maintaining structural integrity in 1 M NaOH solution at 95 °C for 60 days. Initial electrochemical performance and steady-state operation performance were evaluated, and both membranes showed a good stabilization of the cell voltage during the steady-state operation at the constant current density at 200 mA/cm2. Although both membranes in current form require improvement in mechanical stability to afford better durability in electrolysis operation, the next generation AEMs based on this report could lead to potentially viable AEM candidates which can provide high electrolysis performance under alkaline operating condition.

Stability studies on diloxanide furoate: effect of pH, temperature, gastric and intestinal fluids.

PubMed

Gadkariem, E A; Belal, F; Abounassif, M A; El-Obeid, H A; E E Ibrahim, K

2004-04-01

The degradation of the amoebicide diloxanide furoate in alkaline medium at different temperatures was investigated using both a spectrophotometric and a developed HPLC method. In solutions, the drug was found to undergo decomposition, i.e., temperature and pH dependent. The pH-rate profile at pH between 7.6 and 9.6 indicated a first-order dependence of Kobs on [-OH]. Arrhenius plot obtained at pH 8 was linear between 40 and 63 degrees C. The estimated activation energy of hydrolysis was found to be 18.25 kcal degree.mol(-1). The effect of simulated gastric and intestinal fluids on the drug was also investigated. A new thin-layer chromatographic (TLC) procedure for the fractionation of the drug and its alkaline hydrolysis products has been developed and was found to compare favorably with that of the British Pharmacopoeia. Three hydrolysis products of a basic methanolic solution of the drug, namely furoic acid, diloxanide and methylfuroate could be identified by the use of TLC, HPLC, infrared and mass spectrometry.

Comparison of enteral and parenteral methods of urine alkalinization in patients receiving high-dose methotrexate.

PubMed

Rouch, Jamie A; Burton, Bradley; Dabb, Alix; Brown, Vicky; Seung, Amy H; Kinsman, Katharine; Holdhoff, Matthias

2017-01-01

Purpose Hyperhydration and urinary alkalinization is implemented with all high-dose (HD)-methotrexate infusions to promote excretion and prevent precipitation of methotrexate in the renal tubules. Our institution utilized enteral alkalinizing agents (sodium bicarbonate tablets and sodium citrate/citric acid solution) to alkalinize the urine of patients receiving HD-methotrexate during a parenteral sodium bicarbonate and sodium acetate shortage. The purpose of this study is to establish the safety and efficacy of the enteral route for urine alkalinization. Methods A single-center, retrospective, cohort study was conducted comparing cycles of HD-methotrexate using enteral alkalinizing agents to parenteral sodium bicarbonate. The primary objective was to compare the time, in hours, from administration of first inpatient administered dose of alkalinizing agent to time of achieving goal urine pH. Secondary objectives evaluated total dose of sodium bicarbonate required to achieve goal urine pH, time from start of urine alkalinizing agent until time of achieving methotrexate level safe for discharge, and toxicities associated with methotrexate and the alkalinizing agents. Results A total of 118 patients were included in this study, equally divided into two cohorts based on parenteral versus enteral routes of administration. No statistical difference was determined between the two cohorts regarding time to goal urine pH (6.5 h versus 7.9 h, P = 0.051) or regarding time to methotrexate level deemed safe for discharge (63.5 h versus 62.5 h, p = 0.835). There were no significant differences in methotrexate-induced toxicities. Conclusion Our study found enteral routes of urine alkalinization to be a viable alternative to the traditional parenteral sodium bicarbonate, especially during parenteral sodium bicarbonate and acetate shortages.

Correlation of Surface Adsorption and Oxidation with a Floatability Difference of Galena and Pyrite in High-Alkaline Lime Systems.

PubMed

Niu, Xiaopeng; Ruan, Renman; Xia, Liuyin; Li, Li; Sun, Heyun; Jia, Yan; Tan, Qiaoyi

2018-02-27

When it comes to Pb-Zn ores with high amounts of pyrite, the major problem encountered is the low separation efficiency between galena and pyrite. By virtue of high dosage of lime and collector sodium diethyl dithiocarbamate (DDTC), pyrite and zinc minerals are depressed, allowing the galena to be floated. However, there have been significant conflicting reports on the flotation behavior of galena at high pH. In this context, correlation of the surface adsorption and oxidation with the floatability difference of galena and pyrite in high-alkaline lime systems would be a key issue for process optimization. Captive bubble contact angle measurements were performed on freshly polished mineral surfaces in situ exposed to lime solutions of varying pH as a function of immersion time. Furthermore, single mineral microflotation tests were conducted. Both tests indicated that the degree of hydrophobicity on the surfaces of galena and pyrite increased in the presence of DDTC at natural or mild pulp pH. While in a saturated lime solution, at pH 12.5, DDTC only worked for galena, but not for pyrite. Surface chemistry analysis by time-of-flight secondary ion mass spectrometry (Tof-SIMS) confirmed the preference of DDTC on the galena surface at pH 12.5, which contributed to a merit recovery. Further important evidence through measurements of Tof-SIMS, ion chromatography, and high-performance liquid chromatography indicated that in high-alkaline lime systems, the merit floatability of galena could exclude the insignificant contribution of elemental sulfur (S 8 ) and was dominantly attributed by the strong adsorption of DDTC. In contrast, the poor flotation response of pyrite at high pH was due to the prevailing adsorption of CaOH + species. This study provides an important surface chemistry evidence for a better understanding of the mechanism on the better selectivity in the galena-pyrite separation adopting high-alkaline lime systems.

When can ocean acidification impacts be detected from decadal alkalinity measurements?

NASA Astrophysics Data System (ADS)

Carter, B. R.; Frölicher, T. L.; Dunne, J. P.; Rodgers, K. B.; Slater, R. D.; Sarmiento, J. L.

2016-04-01

We use a large initial condition suite of simulations (30 runs) with an Earth system model to assess the detectability of biogeochemical impacts of ocean acidification (OA) on the marine alkalinity distribution from decadally repeated hydrographic measurements such as those produced by the Global Ship-Based Hydrographic Investigations Program (GO-SHIP). Detection of these impacts is complicated by alkalinity changes from variability and long-term trends in freshwater and organic matter cycling and ocean circulation. In our ensemble simulation, variability in freshwater cycling generates large changes in alkalinity that obscure the changes of interest and prevent the attribution of observed alkalinity redistribution to OA. These complications from freshwater cycling can be mostly avoided through salinity normalization of alkalinity. With the salinity-normalized alkalinity, modeled OA impacts are broadly detectable in the surface of the subtropical gyres by 2030. Discrepancies between this finding and the finding of an earlier analysis suggest that these estimates are strongly sensitive to the patterns of calcium carbonate export simulated by the model. OA impacts are detectable later in the subpolar and equatorial regions due to slower responses of alkalinity to OA in these regions and greater seasonal equatorial alkalinity variability. OA impacts are detectable later at depth despite lower variability due to smaller rates of change and consistent measurement uncertainty.

The Aqueous Chemistry of the Soils at the Phoenix Landing Site

NASA Astrophysics Data System (ADS)

Kounaves, S. P.; Hecht, M. H.; Quinn, R.; West, S. J.; Young, S. M.; Clark, B. C.; Ming, D. W.; Boynton, W. V.; Gospodinova, K.; Kapit, J.; Deflores, L. P.; Smith, P. H.; Team, A

2008-12-01

The MECA Wet Chemistry Laboratory (WCL) analyses on the Phoenix Mars Lander have provided the first direct evidence of the soluble ionic components of the Martian soil. The analyses were performed on samples acquired from the surface (Rosy Red) and at the soil/ice interface approximately 4-5 cm under the surface (Sorceress). Even though the samples are from a rather unique site because of the high polar latitude and the polygon-patterned ground, they present a picture of a geochemical environment different from some previously hypothesized. Addition of 25mL of a water/calibrant solution to approximately 1cc of each of the soil samples resulted in the detection of a variety of ionic species, increased solution conductivity, and a slightly alkaline pH. The major constituent cations identified and quantified to date include Na+, K+, Mg2+, and Ca2+, while the anions included Cl- and ClO4-. Sulfate analysis was performed using a Ba2+ titration method. Even though carbonate and bicarbonate were not directly measured, their presence and quantification is supported by the alkaline pH of the solution, its buffering capacity after the addition of an acid, common ion effects, conductivity, and the modeled equilibrium species distribution of the system. The species distribution resulting from the modeling and consideration of additional interactions; dissolution, precipitation, ion exchange, ads/desorption, charge balance, the behavior over the several hours of monitoring, provided constraints for carbonate speciation and concentration and was used to formulate and test soil simulants. Results from the Thermal and Evolved Gas Analyzer (TEGA) also support the presence of a significant amount of calcite in the soil.

Tested Demonstrations. The Stepwise Reduction of Permanganate in Alkaline Conditions: A Lecture Demonstration.

ERIC Educational Resources Information Center

Ruoff, Peter; Riley, Megan

1987-01-01

Describes a chemistry experiment where an alkaline ice-cold permanganate solution is reduced by adding dropwise a cold diluted hydrogen peroxide solution. Outlines the course of the reduction through the various oxidation states of manganese with their characteristic colors. (TW)

Phenolic cation exchange resin material for recovery of cesium and strontium

DOEpatents

Ebra, Martha A.; Wallace, Richard M.

1983-01-01

A phenolic cation exchange resin with a chelating group has been prepared by reacting resorcinol with iminodiacetic acid in the presence of formaldehyde at a molar ratio of about 1:1:6. The material is highly selective for the simultaneous recovery of both cesium and strontium from aqueous alkaline solutions, such as, aqueous alkaline nuclear waste solutions. The organic resins are condensation polymers of resorcinol and formaldehyde with attached chelating groups. The column performance of the resins compares favorably with that of commercially available resins for either cesium or strontium removal. By combining Cs.sup.+ and Sr.sup.2+ removal in the same bed, the resins allow significant reduction of the size and complexity of facilities for processing nuclear waste.

Phenolic cation-exchange resin material for recovery of cesium and strontium. [Patent application

DOEpatents

Ebra, M.A.; Wallace, R.M.

1982-05-05

A phenolic cation exchange resin with a chelating group has been prepared by reacting resorcinol with iminodiacetic acid in the presence of formaldehyde at a molar ratio of about 1:1:6. The material is highly selective for the simultaneous recovery of both cesium and strontium from aqueous alkaline solutions, such as, aqueous alkaline nuclear wate solutions. The organic resins are condensation polymers of resorcinol and formaldehyde with attached chelating groups. The column performance of the resins compares favorably with that of commercially available resins for either cesium or strontium removal. By combining Cs/sup +/ and Sr/sup 2 +/ removal in the same bed, the resins allow significant reduction of the size and complexity of facilities for processing nuclear waste.

A New Attempt at Alkaline Texturization of Monocrystaline Silicon with Anionic Surfactant as the Additive

NASA Astrophysics Data System (ADS)

Li, Hailing; Wang, Wenjing; Zhao, Lei; Zhou, Chunlan; Diao, Hongwei

2012-10-01

Owing to the volatilization of isopropanol (IPA), instability in the alkaline texturization of monocrystalline silicon has been a big problem for a long time. Many additives were adapted to replace IPA, such as high boiling point alcohols. In this experiment, as a new attempt, sodium lauryl sulfate (SDS), a type of anionic surfactant, was used as the additive in NaOH solution. The etching properties of silicon in 2 wt % NaOH/15-30 mg/L SDS solution were analyzed. To improve the wettability of silicon, two types of metal salt, NaCl and Na2CO3 with concentration from 2 to 15 wt %, were applied to the 2 wt % NaOH/15 mg/L SDS solution. The results showed that the effect of NaCl was better than that of Na2CO3. Finally, the role of the additive was discussed.

Alternative alkaline conditioning of amidoxime based adsorbent for uranium extraction from seawater

DOE PAGES

Das, Sadananda; Liao, Wei -Po; Byers, Maggie Flicker; ...

2015-10-18

Alkaline conditioning of the amidoxime based adsorbents is a significant step in the preparation of the adsorbent for uranium uptake from seawater. The effects of various alkaline conditioning parameters such as the type of alkaline reagent, reaction temperature, and reaction time were investigated with respect to uranium adsorption capacity from simulated seawater (spiked with 8 ppm uranium) and natural seawater (from Sequim Bay, WA). An adsorbent (AF1) was prepared at the Oak Ridge National Laboratory by radiation-induced graft polymerization (RIGP) with acrylonitrile and itaconic acid onto high-surface-area polyethylene fibers. For the AF1 adsorbent, sodium hydroxide emerged as a better reagentmore » for alkaline conditioning over potassium hydroxide, which has typically been used in previous studies, because of higher uranium uptake capacity and lower cost over the other candidate alkaline reagents investigated in this study. Furthermore, the use of sodium hydroxide in place of potassium hydroxide is shown to result in a 21–30% decrease in the cost of uranium recovery.« less

Alternative Alkaline Conditioning of Amidoxime Based Adsorbent for Uranium Extraction from Seawater

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

Das, S.; Liao, W. -P.; Flicker Byers, M.

2016-04-20

Alkaline conditioning of the amidoxime based adsorbents is a significant step in the preparation of the adsorbent for uranium uptake from seawater. The effects of various alkaline conditioning parameters such as the type of alkaline reagent, reaction temperature, and reaction time were investigated with respect to uranium adsorption capacity from simulated seawater (spiked with 8 ppm uranium) and natural seawater (from Sequim Bay, WA). An adsorbent (AF1) was prepared at the Oak Ridge National Laboratory by radiation-induced graft polymerization (RIGP) with acrylonitrile and itaconic acid onto high-surface-area polyethylene fibers. For the AF1 adsorbent, sodium hydroxide emerged as a better reagentmore » for alkaline conditioning over potassium hydroxide, which has typically been used in previous studies, because of higher uranium uptake capacity and lower cost over the other candidate alkaline reagents investigated in this study. Use of sodium hydroxide in place of potassium hydroxide is shown to result in a 21-30% decrease in the cost of uranium recovery.« less

Alternative alkaline conditioning of amidoxime based adsorbent for uranium extraction from seawater

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

Das, Sadananda; Liao, Wei -Po; Byers, Maggie Flicker

Alkaline conditioning of the amidoxime based adsorbents is a significant step in the preparation of the adsorbent for uranium uptake from seawater. The effects of various alkaline conditioning parameters such as the type of alkaline reagent, reaction temperature, and reaction time were investigated with respect to uranium adsorption capacity from simulated seawater (spiked with 8 ppm uranium) and natural seawater (from Sequim Bay, WA). An adsorbent (AF1) was prepared at the Oak Ridge National Laboratory by radiation-induced graft polymerization (RIGP) with acrylonitrile and itaconic acid onto high-surface-area polyethylene fibers. For the AF1 adsorbent, sodium hydroxide emerged as a better reagentmore » for alkaline conditioning over potassium hydroxide, which has typically been used in previous studies, because of higher uranium uptake capacity and lower cost over the other candidate alkaline reagents investigated in this study. Furthermore, the use of sodium hydroxide in place of potassium hydroxide is shown to result in a 21–30% decrease in the cost of uranium recovery.« less

Simulated bioavailability of phosphorus from aquatic macrophytes and phytoplankton by aqueous suspension and incubation with alkaline phosphatase.

PubMed

Feng, Weiying; Wu, Fengchang; He, Zhongqi; Song, Fanhao; Zhu, Yuanrong; Giesy, John P; Wang, Ying; Qin, Ning; Zhang, Chen; Chen, Haiyan; Sun, Fuhong

2018-03-01

Bioavailability of phosphorus (P) in biomass of aquatic macrophytes and phytoplankton and its possible relationship with eutrophication were explored by evaluation of forms and quantities of P in aqueous extracts of dried macrophytes. Specifically, effects of hydrolysis of organically-bound P by the enzyme alkaline phosphatase were studied by use of solution 31 P-nuclear magnetic resonance (NMR) spectroscopy. Laboratory suspensions and incubations with enzymes were used to simulate natural releases of P from plant debris. Three aquatic macrophytes and three phytoplankters were collected from Tai Lake, China, for use in this simulation study. The trend of hydrolysis of organic P (P o ) by alkaline phosphatase was similar for aquatic macrophytes and phytoplankton. Most monoester P (15.3% of total dissolved P) and pyrophosphate (1.8%) and polyphosphate (0.4%) and DNA (3.2%) were transformed into orthophosphate (14.3%). The major forms of monoester P were glycerophosphate (8.8%), nucleotide (2.5%), phytate (0.4%) and other monoesters P (3.6%). Proportions of P o including condensed P hydrolyzed in phytoplankton and aquatic macrophytes were different, with the percentage of 22.6% and 6.0%, respectively. Proportion of P o hydrolyzed in debris from phytoplankton was approximately four times greater than that of P o from aquatic macrophytes, and could be approximately twenty-five times greater than that of P o in sediments. Thus, release and hydrolysis of P o , derived from phytoplankton debris would be an important and fast way to provide bioavailable P to support cyanobacterial blooming in eutrophic lakes. Copyright © 2017 Elsevier B.V. All rights reserved.

A study on lithium/air secondary batteries-Stability of the NASICON-type lithium ion conducting solid electrolyte in alkaline aqueous solutions

NASA Astrophysics Data System (ADS)

Shimonishi, Yuta; Zhang, Tao; Imanishi, Nobuyuki; Im, Dongmin; Lee, Dong Joon; Hirano, Atsushi; Takeda, Yasuo; Yamamoto, Osamu; Sammes, Nigel

The stability of the high lithium ion conducting glass ceramics, Li 1+ x+ yTi 2- xAl xSi yP 3- yO 12 (LTAP) in alkaline aqueous solutions with and without LiCl has been examined. A significant conductivity decrease of the LTAP plate immersed in 0.057 M LiOH aqueous solution at 50 °C for 3 weeks was observed. However, no conductivity change of the LTAP plate immersed in LiCl saturated LiOH aqueous solutions at 50 °C for 3 weeks was observed. The pH value of the LiCl-LiOH-H 2O solution with saturated LiCl was in a range of 7-9. The molarity of LiOH and LiCl in the LiOH and LiCl saturated aqueous solution were estimated to be 5.12 and 11.57 M, respectively, by analysis of Li + and OH -. The high concentration of LiOH and the low pH value of 8.14 in this solution suggested that the dissociation of LiOH into Li + and OH - is too low in the solution with a high concentration of Li +. These results suggest that the water stable LTAP could be used as a protect layer of the lithium metal anode in the lithium/air cell with LiCl saturated aqueous solution as the electrolyte, because the content of OH - ions in the LiCl saturated aqueous solution does not increase via the cell reaction of Li + 1/2O 2 + H 2O → 2LiOH, and LTAP is stable under a deep discharge state.

Simultaneous recovery of Zn and Mn from used batteries in acidic and alkaline mediums: A comparative study.

PubMed

Abid Charef, S; Affoune, A M; Caballero, A; Cruz-Yusta, M; Morales, J

2017-10-01

A parallel study of acidic and alkaline leaching for the recovery of Mn and Zn from spent alkaline batteries is outlined. Using H 2 SO 4 as solvent and selecting appropriate conditions of temperature and concentration, all residues were dissolved except carbon. The separation and recovery of the two components were performed by electrodeposition with satisfactory results at pH values above 4 (current efficiency above 70% for Zn and Mn) but rather lower efficiencies as the pH decreased. Most of the Zn was selectively dissolved by alkaline leaching using a 6.5M NaOH solution, and its recovery was examined by means of both electrochemical and chemical processes. The expected formation of pure Zn by electrowinning failed due to the formation of ZnO, the content of which was highly dependent on the electrodeposition time. For short periods, Zn was the main component. For longer periods the electrodeposit consisted of agglomerated microparticles of ZnO with a minor fraction of Zn metal (barely 3% as measured by X-ray diffraction). A chemical reaction of the element with oxygen released at the anode surface might be responsible for its conversion to ZnO. A simple chemical route is described for the first time for the direct conversion of Zn(OH) 4 2- solution to nanostructured ZnO by lowering the pH to values around 12 using 2M HCl solution. Copyright © 2017 Elsevier Ltd. All rights reserved.

Selective leaching of Zn from spent alkaline batteries using environmentally friendly approaches.

PubMed

Maryam Sadeghi, S; Vanpeteghem, Guillaumme; Neto, Isabel F F; Soares, Helena M V M

2017-02-01

The main aim of this work was to evaluate the possibility of using microwave or ultrasound to assist the efficient and selective leaching of Zn from spent alkaline batteries and compare the results with those obtained using the conventional method. Two different strategies were applied: acid leaching of a washed residue and alkaline leaching of the original residue. In both (acid and alkaline) approaches, the use of microwave- or ultrasound-assisted leaching increased the extraction of Zn compared with the best results obtained using conventional leaching [acid leaching (1.5mol/L H 2 SO 4 , 3h, 80°C), 90% of Zn extracted; alkaline leaching (6mol/L NaOH, 3h, 80°C), 42% of Zn extracted]. With acid leaching, 94% of the Zn was extracted using microwave-assisted leaching (1 cycle, 30s, 1mol/L H 2 SO 4 ), and 92% of the Zn was extracted using ultrasound-assisted leaching (2min, 0.1p, 20% amplitude, 1mol/L H 2 SO 4 ). Ultrasound-assisted leaching resulted in a more selective (Zn/Mn ratio of 5.1) Zn extraction than microwave-assisted leaching (Zn/Mn ratio of 3.5); both processes generated a concentrated Zn solution (⩾18.7g/L) with a purity (83.3% and 77.7%, respectively) that was suitable for electrowinning. With alkaline leaching, microwave- (1 cycle, 3 min, 4mol/L NaOH) and ultrasound-assisted (14min, 0.1p, 20% amplitude, 4mol/L NaOH) leaching extracted about 80% of the Zn and less than 0.01% of the Mn, which resulted in lesser concentrated Zn solutions (approximately 16.5g/L) but with high purity (>99.5%) that was suitable for the recovery of Zn by precipitation. The microwave- and ultrasound-assisted leaching strategies used in this work proved to be efficient and environmentally-friendly approaches for the extraction of Zn from spent alkaline residues since a concentrated Zn solution with adequate purity for subsequent Zn recovery was obtained using significantly decreased leaching times and concentrations of chemicals. Copyright © 2017 Elsevier Ltd. All rights reserved.

A method for making an alkaline battery electrode plate

NASA Technical Reports Server (NTRS)

Chida, K.; Ezaki, T.

1983-01-01

A method is described for making an alkaline battery electrode plate where the desired active substances are filled into a nickel foam substrate. In this substrate an electrolytic oxidation reduction occurs in an alkaline solution containing lithium hydroxide.

In-situ process for recovering hydrocarbons from a diatomite-type formation

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

Davis, B.W.

1984-12-04

An in-situ process for recovering hydrocarbons from a diatomite-type formation which comprises contacting the diatomite formation with a C/sub 4/-C/sub 10/ alcohol and thereafter displacing the hydrocarbon-alcohol mixture with an aqueous alkaline solution towards a production well. The aqueous alkaline solution can be displaced with additional solution or another suitable medium such as a connate water drive.

A Molecular Ni-complex Containing Tetrahedral Nickel Selenide Core as Highly Efficient Electrocatalyst for Water Oxidation.

PubMed

Masud, Jahangir; Ioannou, Polydoros-Chrysovalantis; Levesanos, Nikolaos; Kyritsis, Panayotis; Nath, Manashi

2016-11-23

We report the highly efficient catalytic activity of a transition metal selenide-based coordination complex, [Ni{(SeP i Pr 2 ) 2 N} 2 ], (1) for oxygen evolution and hydrogen evolution reactions (OER and HER, respectively) in alkaline solution. Very low overpotentials of 200 mV and 310 mV were required to achieve 10 mA cm -2 for OER and HER, respectively. The overpotential for OER is one of the lowest that has been reported up to now, making this one of the best OER electrocatalysts. In addition, this molecular complex exhibits an exceptionally high mass activity (111.02 A g -1 ) and a much higher TOF value (0.26 s -1 ) at a overpotential of 300 mV. This bifunctional electrocatalyst enables water electrolysis in alkaline solutions at a cell voltage of 1.54 V. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Advanced oxidation of acridine orange by aqueous alkaline iodine.

PubMed

Azmat, Rafia; Qamar, Noshab; Naz, Raheela; Khursheed, Anum

2016-11-01

The advanced oxidation process is certainly used for the dye waste water treatment. In this continuation a new advanced oxidation via aqueous alkaline iodine was developed for the oxidation of acridine orange (AO) {3, 6 -bis (dimethylamino) acridine zinc chloride double salt}. Oxidation Kinetics of AO by alkaline solution of iodine was investigated spectrophotometrically at λ max 491 nm. The reaction was monitored at various operational parameters like several concentrations of dye and iodine, pH, salt electrolyte and temperature. The initial steps of oxidation kinetics followed fractional order reaction with respect to the dye while depend upon the incremental amount of iodine to certain extent whereas maximum oxidation of AO was achieved at high pH. Decline in the reaction rate in the presence of salt electrolyte suggested the presence of oppositely charged species in the rate determining step. Kinetic data revealed that the de-colorization mechanism involves triodate (I 3 - ) species, instead of hypoidate (OI - ) and hypiodous acid (HOI), in alkaline medium during the photo-excitation of hydrolyzed AO. Alleviated concentration of alkali result in decreasing of rate of reaction, clearly indicate that the iodine species are active oxidizing species instead of OH radical. Activation parameters at elevated temperatures were determined which revealed that highly solvated state of dye complex existed into solution. Reaction mixture was subjected to UV/Visible and GC mass spectrum analysis that proves the secondary consecutive reaction was operative in rate determining step and finally dye complex end into smaller fragments.

Improvement of Aluminum-Air Battery Performances by the Application of Flax Straw Extract.

PubMed

Grishina, Ekaterina; Gelman, Danny; Belopukhov, Sergey; Starosvetsky, David; Groysman, Alec; Ein-Eli, Yair

2016-08-23

The effect of a flax straw extract on Al corrosion inhibition in a strong alkaline solution was studied by using electrochemical measurements, weight-loss analysis, SEM, and FTIR spectroscopy. Flax straw extract added (3 vol %) to the 5 m KOH solution to act as a mixed-type Al corrosion inhibitor. The electrochemistry of Al in the presence of a flax straw extract in the alkaline solution, the effect of the extract on the Al morphology and surface films formed, and the corrosion inhibition mechanism are discussed. Finally, the Al-air battery discharge capacity recorded from a cell that used the flax straw extract in the alkaline electrolyte is substantially higher than that with only a pure alkaline electrolyte. This improved sustainability of the Al anode is attributed to Al corrosion inhibition and, consequently, to hydrogen evolution suppression. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Alkaline Phosphatase, Soluble Extracellular Adenine Nucleotides, and Adenosine Production after Infant Cardiopulmonary Bypass

PubMed Central

Davidson, Jesse A.; Urban, Tracy; Tong, Suhong; Twite, Mark; Woodruff, Alan

2016-01-01

Rationale Decreased alkaline phosphatase activity after infant cardiac surgery is associated with increased post-operative cardiovascular support requirements. In adults undergoing coronary artery bypass grafting, alkaline phosphatase infusion may reduce inflammation. Mechanisms underlying these effects have not been explored but may include decreased conversion of extracellular adenine nucleotides to adenosine. Objectives 1) Evaluate the association between alkaline phosphatase activity and serum conversion of adenosine monophosphate to adenosine after infant cardiac surgery; 2) assess if inhibition/supplementation of serum alkaline phosphatase modulates this conversion. Methods and Research Pre/post-bypass serum samples were obtained from 75 infants <4 months of age. Serum conversion of 13C5-adenosine monophosphate to 13C5-adenosine was assessed with/without selective inhibition of alkaline phosphatase and CD73. Low and high concentration 13C5-adenosine monophosphate (simulating normal/stress concentrations) were used. Effects of alkaline phosphatase supplementation on adenosine monophosphate clearance were also assessed. Changes in serum alkaline phosphatase activity were strongly correlated with changes in 13C5-adenosine production with or without CD73 inhibition (r = 0.83; p<0.0001). Serum with low alkaline phosphatase activity (≤80 U/L) generated significantly less 13C5-adenosine, particularly in the presence of high concentration 13C5-adenosine monophosphate (10.4μmol/L vs 12.9μmol/L; p = 0.0004). Inhibition of alkaline phosphatase led to a marked decrease in 13C5-adenosine production (11.9μmol/L vs 2.7μmol/L; p<0.0001). Supplementation with physiologic dose human tissue non-specific alkaline phosphatase or high dose bovine intestinal alkaline phosphatase doubled 13C5-adenosine monophosphate conversion to 13C5-adenosine (p<0.0001). Conclusions Alkaline phosphatase represents the primary serum ectonucleotidase after infant cardiac surgery and low post-operative alkaline phosphatase activity leads to impaired capacity to clear adenosine monophosphate. AP supplementation improves serum clearance of adenosine monophosphate to adenosine. These findings represent a potential therapeutic mechanism for alkaline phosphatase infusion during cardiac surgery. New and Noteworthy We identify alkaline phosphatase (AP) as the primary soluble ectonucleotidase in infants undergoing cardiopulmonary bypass and show decreased capacity to clear AMP when AP activity decreases post-bypass. Supplementation of AP ex vivo improves this capacity and may represent the beneficial therapeutic mechanism of AP infusion seen in phase 2 studies. PMID:27384524

Alkaline Phosphatase, Soluble Extracellular Adenine Nucleotides, and Adenosine Production after Infant Cardiopulmonary Bypass.

PubMed

Davidson, Jesse A; Urban, Tracy; Tong, Suhong; Twite, Mark; Woodruff, Alan; Wischmeyer, Paul E; Klawitter, Jelena

2016-01-01

Decreased alkaline phosphatase activity after infant cardiac surgery is associated with increased post-operative cardiovascular support requirements. In adults undergoing coronary artery bypass grafting, alkaline phosphatase infusion may reduce inflammation. Mechanisms underlying these effects have not been explored but may include decreased conversion of extracellular adenine nucleotides to adenosine. 1) Evaluate the association between alkaline phosphatase activity and serum conversion of adenosine monophosphate to adenosine after infant cardiac surgery; 2) assess if inhibition/supplementation of serum alkaline phosphatase modulates this conversion. Pre/post-bypass serum samples were obtained from 75 infants <4 months of age. Serum conversion of 13C5-adenosine monophosphate to 13C5-adenosine was assessed with/without selective inhibition of alkaline phosphatase and CD73. Low and high concentration 13C5-adenosine monophosphate (simulating normal/stress concentrations) were used. Effects of alkaline phosphatase supplementation on adenosine monophosphate clearance were also assessed. Changes in serum alkaline phosphatase activity were strongly correlated with changes in 13C5-adenosine production with or without CD73 inhibition (r = 0.83; p<0.0001). Serum with low alkaline phosphatase activity (≤80 U/L) generated significantly less 13C5-adenosine, particularly in the presence of high concentration 13C5-adenosine monophosphate (10.4μmol/L vs 12.9μmol/L; p = 0.0004). Inhibition of alkaline phosphatase led to a marked decrease in 13C5-adenosine production (11.9μmol/L vs 2.7μmol/L; p<0.0001). Supplementation with physiologic dose human tissue non-specific alkaline phosphatase or high dose bovine intestinal alkaline phosphatase doubled 13C5-adenosine monophosphate conversion to 13C5-adenosine (p<0.0001). Alkaline phosphatase represents the primary serum ectonucleotidase after infant cardiac surgery and low post-operative alkaline phosphatase activity leads to impaired capacity to clear adenosine monophosphate. AP supplementation improves serum clearance of adenosine monophosphate to adenosine. These findings represent a potential therapeutic mechanism for alkaline phosphatase infusion during cardiac surgery. We identify alkaline phosphatase (AP) as the primary soluble ectonucleotidase in infants undergoing cardiopulmonary bypass and show decreased capacity to clear AMP when AP activity decreases post-bypass. Supplementation of AP ex vivo improves this capacity and may represent the beneficial therapeutic mechanism of AP infusion seen in phase 2 studies.

Separation and determination of secoisolariciresinol diglucoside oligomers and their hydrolysates in the flaxseed extract by high-performance liquid chromatography.

PubMed

Li, Xin; Yuan, Jian-Ping; Xu, Shi-Ping; Wang, Jiang-Hai; Liu, Xin

2008-03-28

Flaxseed contains the largest amount of lignan secoisolariciresinol diglucoside (SDG) oligomers and is the richest dietary source of SDG. SDG oligomers in the flaxseed extract are often hydrolyzed to break the ester linkages for the release of SDG and the glycosidic bonds for the release of secoisolariciresinol (SECO). The hydrolysates of SDG oligomers are complicated because of the production of esters in an alcohol-containing medium. In this study, a new gradient reversed-phase high-performance liquid chromatography (HPLC) method has been developed to be suitable for the separation and determination of: (1) SDG oligomers extracted from the defatted flaxseed powder by a 70% aqueous methanol solution; (2) SDG oligomers and their alkaline hydrolysates, including SDG, p-coumaric acid glucoside and its methyl ester, ferulic acid glucoside and its methyl ester in an alkaline hydrolytic solution; and (3) the succedent acid hydrolysates, including secoisolariciresinol monoglucoside (SMG), SECO, anhydrosecoisolariciresinol (anhydro-SECO), p-coumaric acid and its methyl ester, ferulic acid and its methyl ester, 5-hydroxymethyl-2-furfural (HMF) and its degradation product in an acid hydrolytic solution. The content of SDG oligomers in a defatted flaxseed powder was found to be 38.5 mg/g on a dry matter basis, corresponding to a SDG content of 15.4 mg/g, which was determined after alkaline hydrolysis. Furthermore, this study presented a major reaction pathway for the hydrolysis of SDG oligomers.

FURTHER STUDIES ON THE INHIBITION OF CYPRIDINA LUMINESCENCE BY LIGHT, WITH SOME OBSERVATIONS ON METHYLENE BLUE

PubMed Central

Harvey, E. Newton

1926-01-01

1. Eosin, erythrosin, rose bengale, cyanosin, acridine, and methylene blue act photodynamically on the luminescence of a Cypridina luciferin-luciferase solution. In presence of these dyes inhibition of luminescence, which without the dye occurs only in blue-violet light, takes place in green, yellow, orange, or red light, depending on the position of the absorption bands of the dye. 2. Inhibition of Cypridina luminescence without photosensitive dye in blue-violet light, or with photosensitive dye in longer wave-lengths, does not occur in absence of oxygen. Light acts by accelerating the oxidation of luciferin without luminescence. Eosin or methylene blue act by making longer wave-lengths effective, but there is no evidence that these dyes become reduced in the process. 3. The luciferin-oxyluciferin system is similar to the methylene white-methylene blue system in many ways but not exactly similar in respect to photochemical change. Oxidation of the dye is favored in acid solution, reduction in alkaline solution. However, oxidation of luciferin is favored in all pH ranges from 4 to 10 but is much more rapid in alkaline solution, either in light or darkness. There is no evidence that reduction of oxyluciferin is favored in alkaline solution. Clark's observation that oxidation (blueing) of methylene white occurs in complete absence of oxygen has been confirmed for acid solutions. I observed no blueing in light in alkaline solution. PMID:19872301

In Situ Quantification of [Re(CO) 3] + by Fluorescence Spectroscopy in Simulated Hanford Tank Waste

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

Branch, Shirmir D.; French, Amanda D.; Lines, Amanda M.

A pretreatment protocol is presented that allows for the quantitative conversion and subsequent in situ spectroscopic analysis of [Re(CO)3]+ species in simulated Hanford tank waste. The protocol encompasses adding a simulated waste sample containing the non-emissive [Re(CO)3]+ species to a developer solution that enables the rapid, quantitative conversion of the non-emissive species to a luminescent species which can then be detected spectroscopically. The [Re(CO)3]+ species concentration in an alkaline, simulated Hanford tank waste supernatant can be quantified by the standard addition method. In a test case, the [Re(CO)3]+ species was measured to be at a concentration of 38.9 µM, whichmore » was a difference of 2.01% from the actual concentration of 39.7 µM.« less

Recovering oil by injecting aqueous alkali, cosurfactant and gas

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

Reisberg, J.; Bielmowicz, L. J.; Thigpen, D. R.

1985-01-15

A process of recovering oil from a subterranean reservoir in which the oil is acidic but forms monovalent cation soaps of only relatively low interfacial activity when reacted with aqueous alkaline solutions, comprises displacing the oil toward a production location with a mixture of gas and cosurfactant-containing aqueous alkaline solution.

The influence of electrolyte additives on the anodic dissolution of aluminum in alkaline solutions

NASA Astrophysics Data System (ADS)

Boehnstedt, W.

1980-09-01

The paper describes the effect of electrolyte additives on the anodic dissolution of aluminum in alkaline solutions. The dissolution is accelerated by the addition of small quantities of gallium or indium ions to the electrolyte indicated by the shift of the zero current potential by about 250 mV on the current-potential curve. Scanning electron microscope studies showed that gallium ions produce many small cracks in the aluminum electrode and collect at the grain boundary areas, increasing the electrode surface; this enlargement, in combination with increased electrolyte agitation due to greater hydrogen evolution, provides higher current densities at the same potential. It is concluded that this process will widen the possibilities of using aluminum and its alloys in high-rate batteries.

Modification of the Selectivity Properties of Tubular Ceramic Membranes after Alkaline Treatment

PubMed Central

Dutournié, Patrick; Limousy, Lionel; Anquetil, Jérôme

2017-01-01

This work focuses on the selectivity modification of ceramic membranes after a mild alkaline treatment. Filtration of pure salt-water solutions was carried out with commercial titania membranes before and after the treatment. After treatment, the rejection of NaF significantly decreased, while the rejection of NaCl and NaBr increased. Additionally, NaI and Na2SO4 remained close to zero. Pore size and electrical charge being almost unchanged, only significant modifications in the dielectric effects can explain this modification of selectivity. Therefore, the surface chemistry and the interaction (nature and magnitude) with the solvent and with the species present in the solution appear to be modified by the alkaline treatment. This trend is also illustrated by discussing the electric and the dielectric properties that were numerically identified before and after treatment. The alkaline treatment significantly decreased the apparent dielectric constant of NaCl-water solution in the pore, highlighting the rejection of sodium chloride. Contrariwise, the modification of the surface chemistry increased the apparent dielectric constant of NaF-water solution by promoting fluoride transmission. PMID:29160802

Modification of the Selectivity Properties of Tubular Ceramic Membranes after Alkaline Treatment.

PubMed

Dutournié, Patrick; Limousy, Lionel; Anquetil, Jérôme; Déon, Sébastien

2017-11-21

This work focuses on the selectivity modification of ceramic membranes after a mild alkaline treatment. Filtration of pure salt-water solutions was carried out with commercial titania membranes before and after the treatment. After treatment, the rejection of NaF significantly decreased, while the rejection of NaCl and NaBr increased. Additionally, NaI and Na₂SO₄ remained close to zero. Pore size and electrical charge being almost unchanged, only significant modifications in the dielectric effects can explain this modification of selectivity. Therefore, the surface chemistry and the interaction (nature and magnitude) with the solvent and with the species present in the solution appear to be modified by the alkaline treatment. This trend is also illustrated by discussing the electric and the dielectric properties that were numerically identified before and after treatment. The alkaline treatment significantly decreased the apparent dielectric constant of NaCl-water solution in the pore, highlighting the rejection of sodium chloride. Contrariwise, the modification of the surface chemistry increased the apparent dielectric constant of NaF-water solution by promoting fluoride transmission.

Surface Proton Transfer Promotes Four-Electron Oxygen Reduction on Gold Nanocrystal Surfaces in Alkaline Solution

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

Lu, Fang; Zhang, Yu; Liu, Shizhong

Four-electron oxygen reduction reaction (4e-ORR), as a key pathway in energy conversion, is preferred over the two-electron reduction pathway that falls short in dissociating dioxygen molecules. Gold (Au) surfaces exhibit high sensitivity of the ORR pathway to its atomic structures. The long-standing puzzle remains unsolved why the Au surfaces with {100} sub-facets were exceptionally capable to catalyze the 4e-ORR in alkaline solution, though limited within a narrow potential window. Herein we report the discovery of a dominant 4e-ORR over the whole potential range on {310} surface of Au nanocrystal shaped as truncated ditetragonal prism (TDP). In contrast, ORR pathways onmore » single-crystalline facets of shaped nanoparticles, including {111} on nano-octahedra and {100} on nano-cubes, are similar to their single-crystal counterparts. Combining our experimental results with density functional theory calculations, we elucidate the key role of surface proton transfers from co-adsorbed H 2O molecules in activating the facet- and potential-dependent 4e ORR on Au in alkaline solutions. These results elucidate how surface atomic structures determine the reaction pathways via bond scission and formation among weakly adsorbed water and reaction intermediates. The new insight helps in developing facet-specific nanocatalysts for various reactions.« less

Surface Proton Transfer Promotes Four-Electron Oxygen Reduction on Gold Nanocrystal Surfaces in Alkaline Solution

DOE PAGES

Lu, Fang; Zhang, Yu; Liu, Shizhong; ...

2017-05-11

Four-electron oxygen reduction reaction (4e-ORR), as a key pathway in energy conversion, is preferred over the two-electron reduction pathway that falls short in dissociating dioxygen molecules. Gold (Au) surfaces exhibit high sensitivity of the ORR pathway to its atomic structures. The long-standing puzzle remains unsolved why the Au surfaces with {100} sub-facets were exceptionally capable to catalyze the 4e-ORR in alkaline solution, though limited within a narrow potential window. Herein we report the discovery of a dominant 4e-ORR over the whole potential range on {310} surface of Au nanocrystal shaped as truncated ditetragonal prism (TDP). In contrast, ORR pathways onmore » single-crystalline facets of shaped nanoparticles, including {111} on nano-octahedra and {100} on nano-cubes, are similar to their single-crystal counterparts. Combining our experimental results with density functional theory calculations, we elucidate the key role of surface proton transfers from co-adsorbed H 2O molecules in activating the facet- and potential-dependent 4e ORR on Au in alkaline solutions. These results elucidate how surface atomic structures determine the reaction pathways via bond scission and formation among weakly adsorbed water and reaction intermediates. The new insight helps in developing facet-specific nanocatalysts for various reactions.« less

Comparison of in situ uranium KD values with a laboratory determined surface complexation model

USGS Publications Warehouse

Curtis, G.P.; Fox, P.; Kohler, M.; Davis, J.A.

2004-01-01

Reactive solute transport simulations in groundwater require a large number of parameters to describe hydrologic and chemical reaction processes. Appropriate methods for determining chemical reaction parameters required for reactive solute transport simulations are still under investigation. This work compares U(VI) distribution coefficients (i.e. KD values) measured under field conditions with KD values calculated from a surface complexation model developed in the laboratory. Field studies were conducted in an alluvial aquifer at a former U mill tailings site near the town of Naturita, CO, USA, by suspending approximately 10 g samples of Naturita aquifer background sediments (NABS) in 17-5.1-cm diameter wells for periods of 3 to 15 months. Adsorbed U(VI) on these samples was determined by extraction with a pH 9.45 NaHCO3/Na2CO3 solution. In wells where the chemical conditions in groundwater were nearly constant, adsorbed U concentrations for samples taken after 3 months of exposure to groundwater were indistinguishable from samples taken after 15 months. Measured in situ K D values calculated from the measurements of adsorbed and dissolved U(VI) ranged from 0.50 to 10.6 mL/g and the KD values decreased with increasing groundwater alkalinity, consistent with increased formation of soluble U(VI)-carbonate complexes at higher alkalinities. The in situ K D values were compared with KD values predicted from a surface complexation model (SCM) developed under laboratory conditions in a separate study. A good agreement between the predicted and measured in situ KD values was observed. The demonstration that the laboratory derived SCM can predict U(VI) adsorption in the field provides a critical independent test of a submodel used in a reactive transport model. ?? 2004 Elsevier Ltd. All rights reserved.

The effect of Si and Al concentrations on the removal of U(VI) in the alkaline conditions created by NH3 gas

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

Katsenovich, Yelena P.; Cardona, Claudia; Lapierre, Robert

2016-10-01

Remediation of uranium in the deep unsaturated zone is a challenging task, especially in the presence of oxygenated, high-carbonate alkalinity soil and pore water composition typical for arid and semi-arid environments of the western regions of the U.S. This study evaluates the effect of various pore water constituencies on changes of uranium concentrations in alkaline conditions, created in the presence of reactive gases such as NH3 to effectively mitigate uranium contamination in the vadose zone sediments. This contaminant is a potential source for groundwater pollution through slow infiltration of soluble and highly mobile uranium species towards the water table. Themore » objective of this research was to evaluate uranium sequestration efficiencies in the alkaline synthetic pore water solutions prepared in a broad range of Si, Al, and bicarbonate concentrations typically present in field systems of the western U.S. regions and identify solid uranium-bearing phases that result from ammonia gas treatment. In previous studies (Szecsody et al. 2012; Zhong et al. 2015), although uranium mobility was greatly decreased, solid phases could not be identified at the low uranium concentrations in field-contaminated sediments. The chemical composition of the synthetic pore water used in the experiments varied for silica (5–250 mM), Al3+ (2.8 or 5 mM), HCO3- (0–100 mM) and U(VI) (0.0021–0.0084 mM) in the solution mixture. Experiment results suggested that solutions with Si concentrations higher than 50 mM exhibited greater removal efficiencies of U(VI). Solutions with higher concentrations of bicarbonate also exhibited greater removal efficiencies for Si, Al, and U(VI). Overall, the silica polymerization reaction leading to the formation of Si gel correlated with the removal of U(VI), Si, and Al from the solution. If no Si polymerization was observed, there was no U removal from the supernatant solution. Speciation modeling indicated that the dominant uranium species in the presence of bicarbonate were anionic uranyl carbonate complexes (UO2(CO3)2-2 and UO2(CO3)3-4) and in the absence of bicarbonate in the solution, U(VI) major species appeared as uranyl-hydroxide (UO2(OH)3- and UO2(OH)4-2) species. The model also predicted the formation of uranium solid phases. Uranyl carbonates as rutherfordine [UO2CO3], cejkaite [Na4(UO2)(CO3)3] and hydrated uranyl silicate phases as Na-boltwoodite [Na(UO2)(SiO4)·1.5H2O] were anticipated for most of the synthetic pore water compositions amended from medium (2.9 mM) to high (100 mM) bicarbonate concentrations.« less

Solution-derived sodalite made with Si- and Ge-ethoxide precursors for immobilizing electrorefiner salt

NASA Astrophysics Data System (ADS)

Riley, Brian J.; Lepry, William C.; Crum, Jarrod V.

2016-01-01

Chlorosodalite has the general form of Na8(AlSiO4)6Cl2 and this paper describes experiments conducted to synthesize sodalite with a solution-based approach to immobilize a simulated spent electrorefiner salt solution containing a mixture of alkali, alkaline earth, and lanthanide chlorides. The reactants used were the salt solution, NaAlO2, and either Si(OC2H5)4 or Ge(OC2H5)4. Additionally, seven different glass sintering aids (at loadings of 5 mass%) were evaluated as sintering aids for consolidating the as-made powders using a cold-press-and-sinter technique. This process of using alkoxide additives for the Group IV component can be used to produce large quantities of sodalite at near-room temperature as compared to a method where colloidal silica was used as the silica source. However, the small particle sizes inhibited densification during heat treatments.

Incontinence Briefs Containing Spiral-Shaped Fiber Acidify Skin pH of Older Nursing Home Residents at Risk for Incontinence-Associated Dermatitis.

PubMed

Bliss, Donna Z; Bland, Peggy; Wiltzen, Kjerstie; Gannon, Alexandra; Wilhems, Anna; Mathiason, Michelle A; Turnbaugh, Robert

The study's purpose was to assess the pH of the skin of older (aged ≥75 years) incontinent nursing home residents after exposure to an incontinence brief containing spiral-shaped fiber wet with an alkaline solution mimicking urine or fecal pH and compared to skin pH after exposure to an industry standard brief wet with the same solution and various controls. The design was experimental, as conditions were applied to skin and skin pH was measured in random order, and subjects served as their own controls. The setting was a Midwestern nonprofit nursing home. The sample was 26 nursing home residents; their mean age was 87 years (SD = 6 years); 77% were female. Most (69%) had urinary incontinence alone, and 31% had dual urinary and fecal incontinence. Skin pH was measured in duplicate on 6 areas of the inner thighs and 6 areas of the volar surface of the forearms. Each area was exposed to 1 of 6 conditions applied in random order: an incontinence brief containing spiral-shaped fiber wet with an alkaline solution and one that was dry; a standard incontinence brief (without spiral-shaped fiber) wet with the same alkaline solution and one that was dry; the alkaline solution alone; and normal skin. On both the thighs and the forearms, skin pH was significantly lower (more acidic) after exposure to the incontinence brief containing spiral-shaped fiber wet with an alkaline solution compared to the wet standard brief and all other control conditions (P < .001). On thighs, the mean skin pH was 5.7 (SD = 0.5) after exposure to the wet brief with spiral-shaped fiber versus 6.4 (SD = 0.5) after exposure to the wet standard brief. On forearms, the mean skin pH was 5.3 (SD = 0.4) after exposure to the wet brief with spiral-shaped fiber versus 6.0 (SD = 0.4) after exposure to the wet standard brief. Incontinence briefs containing a spiral-shaped fiber significantly acidify the pH of the skin exposed to an alkaline solution, while industry standard briefs do not. Since alkaline skin pH is a risk factor for incontinence-associated dermatitis (IAD), results suggest that briefs with spiral-shaped fiber may help prevent IAD. Findings encourage further research.

A study on the mechanism of stress corrosion cracking of duplex stainless steels in hot alkaline-sulfide solution

NASA Astrophysics Data System (ADS)

Chasse, Kevin Robert

Duplex stainless steels (DSS) generally have superior strength and corrosion resistance as compared to most standard austenitic and ferritic stainless grades owing to a balanced microstructure of austenite and ferrite. As a result of having favorable properties, DSS have been selected for the construction of equipment in pulp and paper, chemical processing, nuclear, oil and gas as well as other industries. The use of DSS has been restricted in some cases because of stress corrosion cracking (SCC), which can initiate and grow in either the ferrite or austenite phase depending on the environment. Thorough understanding of SCC mechanisms of DSS in chloride- and hydrogen sulfide-containing solutions has been useful for material selection in many environments. However, understanding of SCC mechanisms of DSS in sulfide-containing caustic solutions is limited, which has restricted the capacity to optimize process and equipment design in pulp and paper environments. Process environments may contain different concentrations of hydroxide, sulfide, and chloride, altering corrosion and SCC susceptibility of each phase. Crack initiation and growth behavior will also change depending on the relative phase distribution and properties of austenite and ferrite. The role of microstructure and environment on the SCC of standard grade UNS S32205 and lean grade UNS S32101 in hot alkaline-sulfide solution were evaluated in this work using electrochemical, film characterization, mechanical testing, X-ray diffraction, and microscopy techniques. Microstructural aspects, which included residual stress state, phase distribution, phase ratio, and microhardness, were related to the propensity for SCC crack initiation in different simulated alkaline pulping liquors at 170 °C. Other grades of DSS and reference austenitic and superferritic grades of stainless steel were studied using exposure coupons for comparison to understand compositional effects and individual phase susceptibility. Environments having different ionic concentrations of inorganic salts, i.e. sodium hydroxide, sodium sulfide, and sodium chloride, were used to understand the effect of liquor alkalinity, percent sulfidity, and chloride content on the corrosion and SCC behavior. Hydrogen embrittlement of S32205 was studied to understand the electrochemical conditions and fracture features associated with this failure mode. The results showed that there is an appreciable increase in the susceptibility of DSS to SCC in the presence of sulfide and chloride in hot alkaline environments. Sulfide and chloride adsorption at active sites on the metal surface caused unstable passivity and defective film formation. Chloride and sulfide available at the electrolyte/film surface reduced the charge transfer resistance and shifted the response of the films to lower frequencies indicating the films became more defective. The surface films had an outer, discontinuous layer, and an inner, barrier layer. Fe, Mo, and Mn were selectively dissolved in hot alkaline environments. The onset of SCC was related to the extent of selective dissolution and was consistent with a slip-step dissolution mechanism. Selective corrosion of the austenite phase depended on percent sulfidity and liquor alkalinity. Chlorides enhanced crack initiation and coalescence along the austenite/ferrite boundaries. Crack initiation and transgranular growth strongly depended on the phase distribution in the banded microstructure of DSS. These findings will augment understanding of SCC in this alloy-environment combination and facilitate materials selection in hot alkaline-sulfide environments, particularly in the petrochemical, nuclear, chemical processing, and pulp and paper industries.

Silicon Priming Created an Enhanced Tolerance in Alfalfa (Medicago sativa L.) Seedlings in Response to High Alkaline Stress

PubMed Central

Liu, Duo; Liu, Miao; Liu, Xiao-Long; Cheng, Xian-Guo; Liang, Zheng-Wei

2018-01-01

Alkaline stress as a result of higher pH usually triggers more severe physiological damage to plants than that of saline stress with a neutral pH. In the present study, we demonstrated that silicon (Si) priming of alfalfa (Medicago sativa L.) seedlings increased their tolerance to high alkaline stress situations. Gongnong No. 1 seedlings were subjected to alkaline stress simulated by 25 mM Na2CO3 (pH 11.2). Alkaline stress greatly decreased the biomass and caused severe lodging or wilting of alfalfa seedlings. In contrast, the application of Si to alfalfa seedlings 36 h prior to the alkaline treatment significantly alleviated the damage symptoms and greatly increased the biomass and chlorophyll content. Because of being concomitant with increasing photosynthesis and water use efficiency, decreasing membrane injury and malondialdehyde content, and increasing peroxidase and catalase ascorbate activities in alfalfa leaves, thereby alleviating the triggered oxidative damage by alkaline stress to the plant. Furthermore, Si priming significantly decreased the accumulation of protein and proline content in alfalfa, thus reducing photosynthetic feedback repression. Si priming significantly accumulated more Na in the roots, but led to a decrease of Na accumulation and an increase of K accumulation in the leaves under alkaline stress. Meanwhile, Si priming decreased the accumulation of metal ions such as Mg, Fe, Mn, and Zn in the roots of alfalfa seedlings under alkaline stress. Collectively, these results suggested that Si is involved in the metabolic or physiological changes and has a potent priming effect on the alkaline tolerance of alfalfa seedlings. The present study indicated that Si priming is a new approach to improve the alkaline tolerance in alfalfa and provides increasing information for further exploration of the alkaline stress response at the molecular level in alfalfa. PMID:29896213

Chromium(III) and chromium(VI) release from leather during 8 months of simulated use.

PubMed

Hedberg, Yolanda S; Lidén, Carola

2016-08-01

Chromium (Cr) release from Cr-tanned leather articles is a major cause of Cr contact dermatitis. It has been suggested that Cr(VI) release from leather is not necessarily an intrinsic property of the leather, but is strongly dependent on environmental conditions. To test this hypothesis for long-term (8 months) simulated use. The release of total Cr and Cr(VI) from Cr-tanned, unfinished leather was analysed in subsequent phosphate buffer (pH 8.0) immersions for a period of 7.5 months. The effect of combined ultraviolet treatment and alkaline solution (pH 12.1) was tested. Dry storage [20% relative humidity (RH)] was maintained between immersions. Atomic absorption spectroscopy, X-ray fluorescence and diphenylcarbazide tests were used. Cr(VI) release was dependent on previous dry storage or alkaline treatment, but not on duration or number of previous immersions. Cr(III) release decreased with time. Fifty-two percent of the total Cr released during the last immersion period was Cr(VI). Cr(VI) release exceeded 9 mg/kg in all immersion periods except in the first 10-day immersion (2.6 mg/kg). Cr(VI) release is primarily determined by environmental factors (RH prior to immersion, solution pH, and antioxidant content). The RH should be kept low prior to testing Cr(VI) release from leather. © 2016 The Authors. Contact Dermatitis published by John Wiley & Sons Ltd.

Influence of indian mustard (Brassica juncea) on rhizosphere soil solution chemistry in long-term contaminated soils: a rhizobox study.

PubMed

Kim, Kwon-Rae; Owens, Gary; Kwon, Soon-lk

2010-01-01

This study investigated the influence of Indian mustard (Brassica juncea) root exudation on soil solution properties (pH, dissolved organic carbon (DOC), metal solubility) in the rhizosphere using a rhizobox. Measurement was conducted following the cultivation of Indian mustard in the rhizobox filled four different types of heavy metal contaminated soils (two alkaline soils and two acidic soils). The growth of Indian mustard resulted in a significant increase (by 0.6 pH units) in rhizosphere soil solution pH of acidic soils and only a slight increase (< 0.1 pH units) in alkaline soils. Furthermore, the DOC concentration increased by 17-156 mg/L in the rhizosphere regardless of soil type and the extent of contamination, demonstrating the exudation of DOC from root. Ion chromatographic determination showed a marked increase in the total dissolved organic acids (OAs) in rhizosphere. While root exudates were observed in all soils, the amount of DOC and OAs in soil solution varied considerably amongst different soils, resulting in significant changes to soil solution metals in the rhizosphere. For example, the soil solution Cd, Cu, Pb, and Zn concentrations increased in the rhizosphere of alkaline soils compared to bulk soil following plant cultivation. In contrast, the soluble concentrations of Cd, Pb, and Zn in acidic soils decreased in rhizosphere soil when compared to bulk soils. Besides the influence of pH and DOC on metal solubility, the increase of heavy metal concentration having high stability constant such as Cu and Pb resulted in a release of Cd and Zn from solid phase to liquid phase.

X-ray photoelectron spectroscopy and electrochemical studies of mild steel FeE500 passivation in concrete simulated water

NASA Astrophysics Data System (ADS)

Miserque, F.; Huet, B.; Azou, G.; Bendjaballah, D.; L'Hostis, V.

2006-11-01

In the context of the prediction of the long-term behaviour of reinforced concrete structures involved in the nuclear waste storage, the corrosion mechanisms of steels have to be assessed. When mild steel rebars are embedded in concrete, the chemical environment of the reinforcement is progressively modified, due to the carbonation of the concrete matrix. This modification leads to the variation of iron oxides properties formed at the steel/concrete interface, and the active corrosion can be initiated. The aim of this study is to evaluate the passivation behaviour and to provide insights into the depassivation of mild steel in concrete pore solution. In a young concrete, due to the alkalinity of the interstitial solution, steel reinforcement remains passive. Immersion tests of mild steel substrate in various alkaline solutions (from pH 13 to 10) have been performed. Due to the low thickness of the corrosion layers formed, X-ray photoelectron spectroscopy has been used to characterize them. In the passive domain, the corrosion products are similar for the various solutions. The corrosion layer is composed of a mixture of Fe3+ and Fe2+. A similar approach is used to determine the depassivation mechanism. The effect of various components such as carbonates, sulfates and silicates resulting from the dissolution of minerals of cement during the carbonation process is investigated. In addition to the surface analysis, the evolution of the electrochemical behaviour as function of the solution nature (pH) is evaluated with the help of electrochemical measurements (free corrosion potential, cyclic voltamperometry).

Specific decrease in solution viscosity of antibodies by arginine for therapeutic formulations.

PubMed

Inoue, Naoto; Takai, Eisuke; Arakawa, Tsutomu; Shiraki, Kentaro

2014-06-02

Unacceptably high viscosity is observed in high protein concentration formulations due to extremely large therapeutic dose of antibodies and volume restriction of subcutaneous route of administration. Here, we show that a protein aggregation suppressor, arginine hydrochloride (ArgHCl), specifically decreases viscosity of antibody formulations. The viscosities of bovine gamma globulin (BGG) solution at 250 mg/mL and human gamma globulin (HGG) solution at 292 mg/mL at a physiological pH were too high for subcutaneous injections, but decreased to an acceptable level (below 50 cP) in the presence of 1,000 mM ArgHCl. ArgHCl also decreased the viscosity of BGG solution at acidic and alkaline pHs. Interestingly, ArgHCl decreased the viscosity of antibody solutions (BGG, HGG, and human immunoglobulin G) but not globular protein solutions (α-amylase and α-chymotrypsin). These results indicate not only high potency of ArgHCl as an excipient to decrease the solution viscosity of high concentration antibodies formulations but also specific interactions between ArgHCl and antibodies.

Use of UO 2 films for electrochemical studies

NASA Astrophysics Data System (ADS)

Miserque, F.; Gouder, T.; Wegen, D. H.; Bottomley, P. D. W.

2001-10-01

UO 2 films have been prepared by dc reactive sputtering of a uranium metal target in an Ar/O 2 atmosphere. We have used the films deposited on gold substrates as working electrodes for electrochemical investigations as simulating the surfaces of fuel pellets. Film composition was determined by photoelectron spectroscopy (XPS and UPS) and X-ray diffraction (XRD). The oxide stoichiometry as a function of deposition conditions was determined and the appropriate conditions for UO 2.0 formation established. AC impedance and cyclic voltammetry measurements were performed. A double RC electrical equivalent circuit was used to fit the data from impedance measurements, similar to those used in unirradiated UO 2 or spent fuel pellets. However due to the porosity or adhesion defects on the thin films that permitted a direct contact between the solution and the gold substrate, we were obliged to add a contribution simulating the water-gold system. Cyclic voltammetry measurements show the influence of pH on the dissolution mechanism. Alkaline solutions permit the formation of an oxidised layer (UO 2.33) which is not present in the acidic solutions. In both pH=2 and pH=6 solutions, a U VI species layer is formed.

USING CERAMIC MEMBRANES TO RECYCLE TWO NONIONIC ALKALINE METAL-CLEANING SOLUTIONS

EPA Science Inventory

One ZrO2 ultrafilter (0.05 um pore size) and two a-Al2O3 microfilters (0.2 and 0.8 um) were used to remove one synthetic ester oil and two polyalphaolefin-based and two petroleum hydrocarbon-based oils and greases from two nonionic alkaline cleaning solutions (e.g., Turco 4215-NC...

Electrochemical Behavior of Sulfur in Aqueous Alkaline Solutions

NASA Astrophysics Data System (ADS)

Mamyrbekova, Aigul; Mamitova, A. D.; Mamyrbekova, Aizhan

2018-03-01

The kinetics and mechanism of the electrode oxidation-reduction of sulfur on an electrically conductive sulfur-graphite electrode in an alkaline solution was studied by the potentiodynamic method. To examine the mechanism of electrode processes occurring during AC polarization on a sulfur-graphite electrode, the cyclic polarization in both directions and anodic polarization curves were recorded. The kinetic parameters: charge transfer coefficients (α), diffusion coefficients ( D), heterogeneous rate constants of electrode process ( k s), and effective activation energies of the process ( E a) were calculated from the results of polarization measurements. An analysis of the results and calculated kinetic parameters of electrode processes showed that discharge ionization of sulfur in alkaline solutions occurs as a sequence of two stages and is a quasireversible process.

HCl, KCl and KOH solvation resolved solute-solvent interactions and solution surface stress

NASA Astrophysics Data System (ADS)

Zhang, Xi; Xu, Yan; Zhou, Yong; Gong, Yinyan; Huang, Yongli; Sun, Chang Q.

2017-11-01

An incorporation of the hydrogen bond (O:Hsbnd O or HB) cooperativity notion, contact angle detection, and the differential phonon spectrometrics (DPS) has enabled us to gain refined information on the HCl, KCl and KOH solvation resolved solute-solvent molecular interactions and the solution surface stresses. Results show that ionic polarization stiffens the solvent Hsbnd O bond phonon from 3200 to 3480 cm-1 in the hydration shells. The HO- in alkaline solution, however, shares not only the same Hsbnd O phonon redshift of compressed water from 3200 to < 3100 cm-1 but also the dangling bonds of H2O surface featured at 3610 cm-1. Salt and alkaline solvation enhances the solution surface stress by K+ and Cl- ionic polarization. The excessive H+ proton in acid solution forms a H↔H anti-HB that depresses the solution surface stress, instead. The solute capability of transforming the fraction of the O:Hsbnd O bonds of the solvent matrix is featured by: fH = 0 and fx ∝ 1-exp(-C/C0) (x = HO-, K+ and Cl-) towards saturation. Exercises not only confirm the presence of the H↔H anti-HB point fragilization, the O:⇔:O super-HB point compression, and ionic polarization dominating the performance of the respective HCl, KOH, and KCl solutions, but also demonstrate the power of the DPS that enables high resolution of solute-solute-solvent interactions and correlation between HB relaxation and solution surface stress.

Selective oxoanion separation using a tripodal ligand

DOEpatents

Custelcean, Radu; Moyer, Bruce A.; Rajbanshi, Arbin

2016-02-16

The present invention relates to urea-functionalized crystalline capsules self-assembled by sodium or potassium cation coordination and by hydrogen-bonding water bridges to selectively encapsulate tetrahedral divalent oxoanions from highly competitive aqueous alkaline solutions and methods using this system for selective anion separations from industrial solutions. The method involves competitive crystallizations using a tripodal tris(urea) functionalized ligand and, in particular, provides a viable approach to sulfate separation from nuclear wastes.

The Influence of Sintering Method on Kaolin-Based Geopolymer Ceramics with Addition of Ultra High Molecular Weight Polyethylene as Binder

NASA Astrophysics Data System (ADS)

Romisuhani, A.; AlBakri, M. M.; Kamarudin, H.; Andrei, S. V.

2017-11-01

The influence of sintering method on kaolin-based geopolymer ceramics with addition of Ultra High Molecular Weight Polyethylene as binder were studied. Geopolymer were formed at room temperature from kaolin and sodium silicate in a highly alkaline medium, followed by curing and drying at 80 °C. 12 M of sodium hydroxide solution were mixed with sodium silicate at a ratio of 0.24 to form alkaline activator. Powder metallurgy technique were used in order to produce kaolin geopolymer ceramics with addition of Ultra High Molecular Weight Polyethylene. The samples were heated at temperature of 1200 °C with two different sintering method which are conventional method and two-step sintering method. The strength and density were tested.

Corrosion Control through a Better Understanding of the Metallic Substrate/Organic Coating Interface

DTIC Science & Technology

1990-03-16

electrically coupling steel electrodes in different pH solutions. Anodic and cathodic sites beneath a coating are known to produce acidic and alkaline...9,16]. Lead-steel couples were used to model the interactions between metallic lead and steel. Both acidic and alkaline solutions were used because the...acetate solution can be altered by the addition of acid or base without precipitation of the anion. Other anions such as chlorides and sulfates are

Alkalinity of non-industrial cleaning products and the likelihood of producing significant esophageal burns.

PubMed

Howell, J M

1991-11-01

Alkaline cleaning products are a cause of serious esophageal injury. Over time, legislation has diminished the concentration of many such non-industrial solutions and solids; however several products presently do not list either the pH or relative concentrations of alkaline constituents. This study measures the pHs of several non-industrial cleaning products containing either ammonium chloride, sodium hydroxide, or potassium hydroxide. Three pH measurements were performed on each of 10 non-industrial alkaline cleaning products (eight liquid, two solid). Two 0.1% ammonium chloride solutions had pHs of 12.06 +/- 0.00 and 12.06 +/- 0.01, whereas a pH of 12.43 +/- 0.00 was recorded in a 0.2% ammonium chloride solution. Concentrations of sodium hydroxide and potassium hydroxide were listed on only one of five liquid cleaning product labels. The pHs for these five products varied between 12.83 +/- 0.009 and 13.5 +/- .0.2. The pHs of three sodium hydroxide solutions differed from values reported in Micromedex (Micromedex Inc, Denver CO) by up to 0.32 pH units. Ten percent (v/v) solutions of two solid lye products had pHs of 13.62 +/- 0.008 and 13.74 +/- 0.02. The investigator found that selected non-industrial cleaning products, including ammonia solutions, retain the ability to cause clinically important esophageal damage.

Experimental investigation of cesium mobility in the course of secondary mineral formations in Hanford sediment columns at 50 degrees C.

PubMed

Mashal, Kholoud Y; Cetiner, Ziya S

2010-10-01

Formation of secondary minerals and Cs mobility in Hanford sediments were investigated under conditions similar to the Hanford tank leak in a dynamic flow system at 50 degrees C. The objectives were to (1) examine the nature and locations of secondary mineral phases precipitated in the sediments and (2) quantify the amount of Cs retained by the sediment matrix at 50 degrees C. To this end, Hanford sediments were packed into 10-cm long columns and leached with simulated tank waste consisting of 1.4 M NaOH, 0.125 M NaAlO(2), 3.7 M NaNO(3), and 1.3 x 10(-4) M Cs at 50 degrees C. Compositions of outflow solution were monitored with time for up to 25 days, and the columns were then segmented into four 2.5-cm long layers. The colloidal fraction in these segments was characterized in terms of mineralogy, particle morphology, Cs content, and short-range Al and Si structure. It was observed that cancrinite and sodalite precipitated at 50 degrees C. Approximately 53% Cs was retained in the column treated by the simulated tank waste at this temperature. Cesium retention in the column was lowered in the high ionic strength solution due to competition from Na for the exchange sites. This can be explained by alteration of distribution and number of sorption sites which reduces the selectivity of Cs for Na, and through the formation of cancrinite and sodalite. The formation of hydroxide complexes in highly alkaline solutions could also contribute to relatively poor retention of Cs by hindering ion exchange mechanism.

High-Efficiency Artificial Photosynthesis Using a Novel Alkaline Membrane Cell

NASA Technical Reports Server (NTRS)

Narayan, Sri; Haines, Brennan; Blosiu, Julian; Marzwell, Neville

2009-01-01

A new cell designed to mimic the photosynthetic processes of plants to convert carbon dioxide into carbonaceous products and oxygen at high efficiency, has an improved configuration using a polymer membrane electrolyte and an alkaline medium. This increases efficiency of the artificial photosynthetic process, achieves high conversion rates, permits the use of inexpensive catalysts, and widens the range of products generated by this type of process. The alkaline membrane electrolyte allows for the continuous generation of sodium formate without the need for any additional separation system. The electrolyte type, pH, electrocatalyst type, and cell voltage were found to have a strong effect on the efficiency of conversion of carbon dioxide to formate. Indium electrodes were found to have higher conversion efficiency compared to lead. Bicarbonate electrolyte offers higher conversion efficiency and higher rates than water solutions saturated with carbon dioxide. pH values between 8 and 9 lead to the maximum values of efficiency. The operating cell voltage of 2.5 V, or higher, ensures conversion of the carbon dioxide to formate, although the hydrogen evolution reaction begins to compete strongly with the formate production reaction at higher cell voltages. Formate is produced at indium and lead electrodes at a conversion efficiency of 48 mg of CO2/kilojoule of energy input. This efficiency is about eight times that of natural photosynthesis in green plants. The electrochemical method of artificial photosynthesis is a promising approach for the conversion, separation and sequestration of carbon dioxide for confined environments as in space habitats, and also for carbon dioxide management in the terrestrial context. The heart of the reactor is a membrane cell fabricated from an alkaline polymer electrolyte membrane and catalyst- coated electrodes. This cell is assembled and held in compression in gold-plated hardware. The cathode side of the cell is supplied with carbon dioxide-saturated water or bicarbonate solution. The anode side of the cell is supplied with sodium hydroxide solution. The solutions are circulated past the electrodes in the electrochemical cell using pumps. A regulated power supply provides the electrical energy required for the reactions. Photovoltaic cells can be used to better mimic the photosynthetic reaction. The current flowing through the electrochemical cell, and the cell voltage, are monitored during experimentation. The products of the electrochemical reduction of carbon dioxide are allowed to accumulate in the cathode reservoir. Samples of the cathode solution are withdrawn for product analysis. Oxygen is generated on the anode side and is allowed to vent out of the reservoir.

Electrochemical probing of high-level radioactive waste tanks containing washed sludge and precipitates

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

Bickford, D.F.; Congdon, J.W.; Oblath, S.B.

1986-12-01

At the US Department of Energy's Savannah River Plant, corrosion of carbon steel storage tanks containing alkaline, high-level radioactive waste is controlled by specification of limits on waste composition and temperature. Processes for the preparation of waste for final disposal will result in waste with low corrosion inhibitor concentrations and, in some cases, high aromatic organic concentrations, neither of which are characteristic of previous operations. Laboratory tests, conducted to determine minimum corrosion inhibitor levels indicated pitting of carbon steel near the waterline for proposed storage conditions. In situ electrochemical measurements of full-scale radioactive process demonstrations have been conducted to assessmore » the validity of laboratory tests. Probes included pH, Eh (potential relative to a standard hydrogen electrode), tank potential, and alloy coupons. In situ results are compared to those of the laboratory tests, with particular regard given to simulated solution composition. Transition metal hydroxide sludge contains strong passivating species for carbon steel. Washed precipitate contains organic species that lower solution pH and tend to reduce passivating films, requiring higher inhibitor concentrations than the 0.01 molar nitrite required for reactor fuel reprocessing wastes. Periodic agitation, to keep the organic phase suspended, or cathodic protection are possible alternatives to higher nitrite inhibitor concentrations.« less

Effect of Sn4+ Additives on the Microstructure and Corrosion Resistance of Anodic Coating Formed on AZ31 Magnesium Alloy in Alkaline Solution

NASA Astrophysics Data System (ADS)

Salman, S. A.; Kuroda, K.; Saito, N.; Okido, M.

Magnesium is the lightest structural metal with high specific strength and good mechanical properties. However, poor corrosion resistance limits its widespread use in many applications. Magnesium is usually treated with Chromate conversion coatings. However, due to changing environmental regulations and pollution prevention requirements, a significant push exists to find new, alternative for poisonous Cr6+. Therefore, we aim to improve corrosion resistance of anodic coatings on AZ31 alloys using low cost non-chromate electrolyte. Anodizing was carried out in alkaline solutions with tin additives. The effect of tin additives on the coating film was characterized by SEM and XRD. The corrosion resistance was evaluated using anodic and cathodic polarizations and electrochemical impedance spectroscopy (EIS). Corrosion resistance property was improved with tin additives and the best anti-corrosion property was obtained with addition of 0.03 M Na2SnO3.3H2O to anodizing solution.

Ultrathin platinum nanowires grown on single-layered nickel hydroxide with high hydrogen evolution activity.

PubMed

Yin, Huajie; Zhao, Shenlong; Zhao, Kun; Muqsit, Abdul; Tang, Hongjie; Chang, Lin; Zhao, Huijun; Gao, Yan; Tang, Zhiyong

2015-03-02

Design and synthesis of effective electrocatalysts for hydrogen evolution reaction in alkaline environments is critical to reduce energy losses in alkaline water electrolysis. Here we report a hybrid nanomaterial comprising of one-dimensional ultrathin platinum nanowires grown on two-dimensional single-layered nickel hydroxide. Judicious surface chemistry to generate the fully exfoliated nickel hydroxide single layers is explored to be the key for controllable growth of ultrathin platinum nanowires with diameters of about 1.8 nm. Impressively, this hybrid nanomaterial exhibits superior electrocatalytic activity for hydrogen evolution reaction in alkaline solution, which outperforms currently reported catalysts, and the obviously improved catalytic stability. We believe that this work may lead towards the development of single-layered metal hydroxide-based hybrid materials for applications in catalysis and energy conversion.

Electrocatalysts for Hydrogen Evolution in Alkaline Electrolytes: Mechanisms, Challenges, and Prospective Solutions.

PubMed

Mahmood, Nasir; Yao, Yunduo; Zhang, Jing-Wen; Pan, Lun; Zhang, Xiangwen; Zou, Ji-Jun

2018-02-01

Hydrogen evolution reaction (HER) in alkaline medium is currently a point of focus for sustainable development of hydrogen as an alternative clean fuel for various energy systems, but suffers from sluggish reaction kinetics due to additional water dissociation step. So, the state-of-the-art catalysts performing well in acidic media lose considerable catalytic performance in alkaline media. This review summarizes the recent developments to overcome the kinetics issues of alkaline HER, synthesis of materials with modified morphologies, and electronic structures to tune the active sites and their applications as efficient catalysts for HER. It first explains the fundamentals and electrochemistry of HER and then outlines the requirements for an efficient and stable catalyst in alkaline medium. The challenges with alkaline HER and limitation with the electrocatalysts along with prospective solutions are then highlighted. It further describes the synthesis methods of advanced nanostructures based on carbon, noble, and inexpensive metals and their heterogeneous structures. These heterogeneous structures provide some ideal systems for analyzing the role of structure and synergy on alkaline HER catalysis. At the end, it provides the concluding remarks and future perspectives that can be helpful for tuning the catalysts active-sites with improved electrochemical efficiencies in future.

Electrocatalysts for Hydrogen Evolution in Alkaline Electrolytes: Mechanisms, Challenges, and Prospective Solutions

PubMed Central

Mahmood, Nasir; Yao, Yunduo; Zhang, Jing‐Wen; Pan, Lun; Zhang, Xiangwen

2017-01-01

Abstract Hydrogen evolution reaction (HER) in alkaline medium is currently a point of focus for sustainable development of hydrogen as an alternative clean fuel for various energy systems, but suffers from sluggish reaction kinetics due to additional water dissociation step. So, the state‐of‐the‐art catalysts performing well in acidic media lose considerable catalytic performance in alkaline media. This review summarizes the recent developments to overcome the kinetics issues of alkaline HER, synthesis of materials with modified morphologies, and electronic structures to tune the active sites and their applications as efficient catalysts for HER. It first explains the fundamentals and electrochemistry of HER and then outlines the requirements for an efficient and stable catalyst in alkaline medium. The challenges with alkaline HER and limitation with the electrocatalysts along with prospective solutions are then highlighted. It further describes the synthesis methods of advanced nanostructures based on carbon, noble, and inexpensive metals and their heterogeneous structures. These heterogeneous structures provide some ideal systems for analyzing the role of structure and synergy on alkaline HER catalysis. At the end, it provides the concluding remarks and future perspectives that can be helpful for tuning the catalysts active‐sites with improved electrochemical efficiencies in future. PMID:29610722

Alkaline saponification results in decomposition of tocopherols in milk and ovine blood plasma.

PubMed

Czauderna, M; Kowalczyk, J

2007-10-15

Alkaline saponification of entire sample matrixes for quantification of alpha-, gamma-, delta-tocopherols (alpha-T, gamma-T, delta-T) and alpha-tocopherol acetate (alpha-TAc) was examined. High-performance liquid chromatography was used to measure alpha-T, gamma-T, delta-T and alpha-TAc in tocopherol standard solutions, milk and ovine blood plasma. Saponification in the presence of vitamin C decreases the concentration of tocopherols, especially alpha-T and gamma-T. The poor recovery of tocopherols is due to the decomposition of tocopherols in saponified standard solutions, milk or plasma. Saponification of samples in the presence of 2,[6]-ditertbutyl-p-cresol or flushed only with a stream of Ar resulted in a major decrease in the concentrations of alpha-T, gamma-T, delta-T and alpha-TAc in comparison with saponification in the presence of vitamin C.

Hydrophilic cobalt sulfide nanosheets as a bifunctional catalyst for oxygen and hydrogen evolution in electrolysis of alkaline aqueous solution.

PubMed

Zhu, Mingchao; Zhang, Zhongyi; Zhang, Hu; Zhang, Hui; Zhang, Xiaodong; Zhang, Lixue; Wang, Shicai

2018-01-01

Hydrophilic medium and precursors were used to synthesize a hydrophilic electro-catalyst for overall water splitting. The cobalt sulfide (Co 3 S 4 ) catalyst exhibits a layered nanosheet structure with a hydrophilic surface, which can facilitate the diffusion of aqueous substrates into the electrode pores and towards the active sites. The Co 3 S 4 catalyst shows excellent bifunctional catalytic activity for both the oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) in alkaline solution. The assembled water electrolyzer based on Co 3 S 4 exhibits better performance and stability than that of Pt/C-RuO 2 catalyst. Thereforce the hydrophilic Co 3 S 4 is a highly promising bifunctional catalyst for the overall water splitting reaction. Copyright © 2017 Elsevier Inc. All rights reserved.

Innovative Elution Processes for Recovering Uranium and Transition Metals from Amidoxime-based Adsorbents

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

Wai, Chien M.

Amidoxime-based polymer fibers are considered one of the most promising materials for sequestering uranium from seawater. The high-surface-area polymer fibers containing amidoxime and carboxylate groups synthesized by Oak Ridge National Lab (ORNL-AF1) show very high uranium adsorption capacities known in the literature. Effective elution of uranium and repeated use of the adsorbent are important factors affecting the cost of producing uranium from seawater using this material. Traditional acid leaching of uranium followed by KOH conditioning of the fiber causes chemical changes and physical damage to the ORNL-AF1 adsorbent. Two alkaline solution leaching methods were developed by this project, one usesmore » a highly concentrated (3 M) potassium bicarbonate solution at pH 8.3 and 40 °C; the other uses a mixture of sodium carbonate and hydrogen peroxide at pH 10.4. Both elution methods do not require KOH conditioning prior to reusing the fiber adsorbent. The conditions of eluting uranium from the amidoxime-based adsorbent using these alkaline solutions are confirmed by thermodynamic calculations. The bicarbonate elution method is selective for uranium recovery compared to other elution methods and causes no chemical change to the fiber material based on FTIR spectroscopy« less

Alkaline earth cation extraction from acid solution

DOEpatents

Dietz, Mark; Horwitz, E. Philip

2003-01-01

An extractant medium for extracting alkaline earth cations from an aqueous acidic sample solution is described as are a method and apparatus for using the same. The separation medium is free of diluent, free-flowing and particulate, and comprises a Crown ether that is a 4,4'(5')[C.sub.4 -C.sub.8 -alkylcyclohexano]18-Crown-6 dispersed on an inert substrate material.

[Surface-enhanced raman spectra studies on roughened Zn electrode in alkaline solutions].

PubMed

Shen, Xiao-ying; Liu, Guo-kun; Gu, Ren-ao; Tian, Zhong-qun

2005-09-01

Electrochemical oxidation-reduction method was employed to roughen Zn electrode for obtaining SERS, and potential dependent surface enhanced Raman spectra (SERS) of roughened Zn electrode in KOH solution of different concentration wereobserved. The spectra of Zn electrode in various solutions had obvious differences which indicated the concentration of OH- had a great effect on the dissolution and passivation of zinc. Based on our experimental results, the authors attempt to analyse the behavior of zinc in alkaline and give the mechanism of its passivation.

Evaluation of a Particulate Filtration System for an Alkaline Paint Stripper at Letterkenny Army Depot

DTIC Science & Technology

1991-08-01

hydroxide 66.0 17.5 1 Mineral seal oil 1.00 0.26 1.00 Fluorochemical surfactant 0.02 0.005 0.02 Sodiun carbonate 1.62 0.43 5.00 Sulfunated oleic acid ...specified rejuvenating additive is currently not added to the solution at LEAD. d Sodium salt of N-hydroxyethylethylenediamine triacetic acid , dihydrate...methylene chloride) and formic acid or I abrasive blasting. Aluminum parts are not stripped in alkaline solutions because these solutions chemically attack

Organic Control of Dioctahedral and Trioctahedral Clay Formation in an Alkaline Soil System in the Pantanal Wetland of Nhecolândia, Brazil.

PubMed

Barbiero, Laurent; Berger, Gilles; Rezende Filho, Ary T; Meunier, Jean-François; Martins-Silva, Elisângela R; Furian, Sonia

2016-01-01

Recent studies have focused on the formation of authigenic clays in an alkaline soil system surrounding lakes of the Nhecolândia region, Pantanal wetland. The presence of trioctahedral Mg-smectites (stevensite and saponite types), which requires low Al and Fe contents in the soil solution for its formation, contrasts with the neoformation of dioctahedral Fe-mica (glauconite, and Fe-illite), which instead requires solutions relatively enriched in Al and Fe. This study aims to understand the conditions of co-existence of both, Mg-smectite and Fe-mica a common clay association in former or modern alkaline soil systems and sediments. The study was carried out along an alkaline soil catena representative of the region. The soil organization revealed that Mg-smectite occur in top soil close to the lake, whereas Fe-mica dominate in the clay fraction of deeper greenish horizons a few meters apart. We propose here that this spatial distribution is controlled by the lateral transfer of Fe and Al with organic ligands. Alkaline organic rich solutions (DOC up to 738 mg L-1) collected in the watertable were centrifuged and filtered through membranes of decreasing pore size (0.45 μm, 0.2 μm, 30 KDa, 10 KDa, 3 KDa) to separate colloidal and dissolved fractions. Fe, Al, Si, Mg and K were analysed for each fraction. Although the filtration had no influence on Si and K contents, almost 90% of Fe (up to 2.3 mg L-1) and Al (up to 7 mg L-1) are retained at the first cutoff threshold of 0.45μm. The treatment of the same solutions by oxygen peroxide before filtration shows that a large proportion of Fe and Al were bonded to organic colloids in alkaline soil solution at the immediate lake border, allowing Mg-smectite precipitation. The fast mineralization of the organic matter a few meters apart from the lake favors the release of Fe and Al necessary for Fe-mica neoformation. In comparison with chemical and mineralogical characteristics of alkaline environments described in the literature, the study suggests that the co-existence of trioctahedral Mg-smectite and dioctahedral Fe-mica should be regarded as a standard occurrence in alkaline soil systems with organic rich waters.

Organic Control of Dioctahedral and Trioctahedral Clay Formation in an Alkaline Soil System in the Pantanal Wetland of Nhecolândia, Brazil

PubMed Central

Meunier, Jean-François; Martins-Silva, Elisângela R.; Furian, Sonia

2016-01-01

Recent studies have focused on the formation of authigenic clays in an alkaline soil system surrounding lakes of the Nhecolândia region, Pantanal wetland. The presence of trioctahedral Mg-smectites (stevensite and saponite types), which requires low Al and Fe contents in the soil solution for its formation, contrasts with the neoformation of dioctahedral Fe-mica (glauconite, and Fe-illite), which instead requires solutions relatively enriched in Al and Fe. This study aims to understand the conditions of co-existence of both, Mg-smectite and Fe-mica a common clay association in former or modern alkaline soil systems and sediments. The study was carried out along an alkaline soil catena representative of the region. The soil organization revealed that Mg-smectite occur in top soil close to the lake, whereas Fe-mica dominate in the clay fraction of deeper greenish horizons a few meters apart. We propose here that this spatial distribution is controlled by the lateral transfer of Fe and Al with organic ligands. Alkaline organic rich solutions (DOC up to 738 mg L-1) collected in the watertable were centrifuged and filtered through membranes of decreasing pore size (0.45 μm, 0.2 μm, 30 KDa, 10 KDa, 3 KDa) to separate colloidal and dissolved fractions. Fe, Al, Si, Mg and K were analysed for each fraction. Although the filtration had no influence on Si and K contents, almost 90% of Fe (up to 2.3 mg L-1) and Al (up to 7 mg L-1) are retained at the first cutoff threshold of 0.45μm. The treatment of the same solutions by oxygen peroxide before filtration shows that a large proportion of Fe and Al were bonded to organic colloids in alkaline soil solution at the immediate lake border, allowing Mg-smectite precipitation. The fast mineralization of the organic matter a few meters apart from the lake favors the release of Fe and Al necessary for Fe-mica neoformation. In comparison with chemical and mineralogical characteristics of alkaline environments described in the literature, the study suggests that the co-existence of trioctahedral Mg-smectite and dioctahedral Fe-mica should be regarded as a standard occurrence in alkaline soil systems with organic rich waters. PMID:27463379

Spontaneous symmetry breaking and strong deformations in metal adsorbed graphene sheets

NASA Astrophysics Data System (ADS)

Jalbout, A. F.; Ortiz, Y. P.; Seligman, T. H.

2013-03-01

We study the adsorption of Li to graphene flakes simulated as aromatic molecules. Surprisingly the out of plane deformation is much stronger for the double adsorption from both sides to the same ring than for a single adsorption, although a symmetric solution seems possible. We thus have an interesting case of spontaneous symmetry breaking. While we cannot rule out a Jahn Teller deformation with certainty, this explanation seems unlikely and other options are discussed. We find a similar behavior for boron-nitrogen sheets, and also for other light alkalines as adsorbants.

Thermal, emulsifying and rheological properties of polysaccharides sequentially extracted from Vaccinium bracteatum Thunb leaves.

PubMed

Xu, Qi-Xin; Shi, Jun-Jun; Zhang, Jian-Guo; Li, Ling; Jiang, Li; Wei, Zhao-Jun

2016-12-01

Plant polysaccharides are widely used in food industry as thickening and gelling agents and these attributes largely depend on their thermal, emulsifying and rheological properties. As known, the extraction methods always bring about the diversification of property and functions of polysaccharides. Thus, the Vaccinium bracteatum Thunb leaves polysaccharides (VBTLP) were sequentially extracted using hot buffer (HBSS), chelating agent (CHSS), dilute alkaline (DASS) and concentrated alkaline (CASS). The thermal, emulsifying and rheological properties of VBTLP were investigated in the present study. Within the range of 20-225°C, CHSS showed the highest peak temperature, whereas HBSS displayed the highest endothermic enthalpy and highest emulsifying activity, while, CASS showed the longest emulsifying stability. The VBTLP solutions exhibited non-Newtonian shear-thinning behavior within the concentrations of 0.6-2.5%. The apparent viscosity of VBTLP solution decreased under following conditions: acidic pH (4.0), alkaline pH (10.0), in the presence of Ca 2+ and at high temperature, while it increased in the presence of Na + and at freezing conditions. The modulus G' and G″ of VBTLP solutions were increased with increasing oscillation frequency, and the crossover frequency shifted to lower values when the polysaccharide content increased. The above results of thermal, emulsifying and rheological properties of VBTLPs supplied the basis for V. bracteatum leaves in potential industrial applications of foods. Copyright © 2016 Elsevier B.V. All rights reserved.

Poly(ethylene imine)-based granular sorbents by a new process of templated gel-filling. High capacity and selectivity of copper sorption in acidic and alkaline media

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

Chanda, M.; Rempel, G.L.

A new process has been developed for making granular gel-type sorbents from chelating resins using metal ion as template. Named as templated gel-filling, the process uses the chosen metal as templating host ion on high-surface-area silica to build a templated gel layer from a solution of the chelating resin in a suitable solvent in which the resin is soluble but its metal complex is insoluble. After cross-linking the templated gel layer, the silica support is removed by alkali to produce a hollow shell of the templated gel. The shells are then soaked in a concentrated aqueous solution of the samemore » metal ion and suspended in the same resin solution to afford gel-filling. The shells thus filled with metal-templated gel are treated with cross-linking agent, followed by acid to remove the template ion and activate the resin for metal sorption. Poly(ethyleneimine) and its partially ethylated derivative have been used to produce granular gel-type sorbents by this process, with Cu(II) as the template ion. These sorbents are found to offer high capacity and selectivity for copper over nickel, cobalt, and zinc in both acidic and alkaline media. Containing a relatively high fraction of imbibed water, the sorbents exhibit markedly enhanced rate behavior, in both sorption and stripping.« less

21 CFR 74.1328 - D&C Red No. 28.

Code of Federal Regulations, 2012 CFR

2012-04-01

... (CAS Reg. No. 18472-87-2) formed by alkaline hydrolysis of the parent tetrabromotetrachlorofluorescein... sulfates (calculated as sodium salts), not more than 15 percent. Insoluble matter (alkaline solution), not...

21 CFR 74.1328 - D&C Red No. 28.

Code of Federal Regulations, 2014 CFR

2014-04-01

... (CAS Reg. No. 18472-87-2) formed by alkaline hydrolysis of the parent tetrabromotetrachlorofluorescein... sulfates (calculated as sodium salts), not more than 15 percent. Insoluble matter (alkaline solution), not...

21 CFR 74.1328 - D&C Red No. 28.

Code of Federal Regulations, 2010 CFR

2010-04-01

... (CAS Reg. No. 18472-87-2) formed by alkaline hydrolysis of the parent tetrabromotetrachlorofluorescein... sulfates (calculated as sodium salts), not more than 15 percent. Insoluble matter (alkaline solution), not...

21 CFR 74.1328 - D&C Red No. 28.

Code of Federal Regulations, 2013 CFR

2013-04-01

... (CAS Reg. No. 18472-87-2) formed by alkaline hydrolysis of the parent tetrabromotetrachlorofluorescein... sulfates (calculated as sodium salts), not more than 15 percent. Insoluble matter (alkaline solution), not...

Root Damage under Alkaline Stress Is Associated with Reactive Oxygen Species Accumulation in Rice (Oryza sativa L.)

PubMed Central

Zhang, Hui; Liu, Xiao-Long; Zhang, Rui-Xue; Yuan, Hai-Yan; Wang, Ming-Ming; Yang, Hao-Yu; Ma, Hong-Yuan; Liu, Duo; Jiang, Chang-Jie; Liang, Zheng-Wei

2017-01-01

Alkaline stress (high pH) severely damages root cells, and consequently, inhibits rice (Oryza sativa L.) seedling growth. In this study, we demonstrate the accumulation of reactive oxygen species (ROS) in root cells under alkaline stress. Seedlings of two rice cultivars with different alkaline tolerances, ‘Dongdao-4’ (moderately alkaline-tolerant) and ‘Jiudao-51’ (alkaline-sensitive), were subjected to alkaline stress simulated by 15 mM sodium carbonate (Na2CO3). Alkaline stress greatly reduced seedling survival rate, shoot and root growth, and root vigor. Moreover, severe root cell damage was observed under alkaline stress, as shown by increased membrane injury, malondialdehyde accumulation, and Evan’s Blue staining. The expression of the cell death-related genes OsKOD1, OsHsr203j, OsCP1, and OsNAC4 was consistently upregulated, while that of a cell death-suppressor gene, OsBI1, was downregulated. Analysis of the ROS contents revealed that alkaline stress induced a marked accumulation of superoxide anions (O2•-) and hydrogen peroxide (H2O2) in rice roots. The application of procyanidins (a potent antioxidant) to rice seedlings 24 h prior to alkaline treatment significantly alleviated alkalinity-induced root damage and promoted seedling growth inhibition, which were concomitant with reduced ROS accumulation. These results suggest that root cell damage, and consequently growth inhibition, of rice seedlings under alkaline stress is closely associated with ROS accumulation. The antioxidant activity of superoxide dismutase, catalase, peroxidase, and ascorbate peroxidase increased under alkaline stress in the roots, probably in response to the cellular damage induced by oxidative stress. However, this response mechanism may be overwhelmed by the excess ROS accumulation observed under stress, resulting in oxidative damage to root cells. Our findings provide physiological insights into the molecular mechanisms of alkalinity-induced damage to root cells, and will contribute to the improvement of alkaline stress tolerance in rice plants. PMID:28943882

Root Damage under Alkaline Stress Is Associated with Reactive Oxygen Species Accumulation in Rice (Oryza sativa L.).

PubMed

Zhang, Hui; Liu, Xiao-Long; Zhang, Rui-Xue; Yuan, Hai-Yan; Wang, Ming-Ming; Yang, Hao-Yu; Ma, Hong-Yuan; Liu, Duo; Jiang, Chang-Jie; Liang, Zheng-Wei

2017-01-01

Alkaline stress (high pH) severely damages root cells, and consequently, inhibits rice ( Oryza sativa L.) seedling growth. In this study, we demonstrate the accumulation of reactive oxygen species (ROS) in root cells under alkaline stress. Seedlings of two rice cultivars with different alkaline tolerances, 'Dongdao-4' (moderately alkaline-tolerant) and 'Jiudao-51' (alkaline-sensitive), were subjected to alkaline stress simulated by 15 mM sodium carbonate (Na 2 CO 3 ). Alkaline stress greatly reduced seedling survival rate, shoot and root growth, and root vigor. Moreover, severe root cell damage was observed under alkaline stress, as shown by increased membrane injury, malondialdehyde accumulation, and Evan's Blue staining. The expression of the cell death-related genes OsKOD1 , OsHsr203j , OsCP1 , and OsNAC4 was consistently upregulated, while that of a cell death-suppressor gene, OsBI1 , was downregulated. Analysis of the ROS contents revealed that alkaline stress induced a marked accumulation of superoxide anions ([Formula: see text]) and hydrogen peroxide (H 2 O 2 ) in rice roots. The application of procyanidins (a potent antioxidant) to rice seedlings 24 h prior to alkaline treatment significantly alleviated alkalinity-induced root damage and promoted seedling growth inhibition, which were concomitant with reduced ROS accumulation. These results suggest that root cell damage, and consequently growth inhibition, of rice seedlings under alkaline stress is closely associated with ROS accumulation. The antioxidant activity of superoxide dismutase, catalase, peroxidase, and ascorbate peroxidase increased under alkaline stress in the roots, probably in response to the cellular damage induced by oxidative stress. However, this response mechanism may be overwhelmed by the excess ROS accumulation observed under stress, resulting in oxidative damage to root cells. Our findings provide physiological insights into the molecular mechanisms of alkalinity-induced damage to root cells, and will contribute to the improvement of alkaline stress tolerance in rice plants.

CO2-Free Power Generation on an Iron Group Nanoalloy Catalyst via Selective Oxidation of Ethylene Glycol to Oxalic Acid in Alkaline Media

NASA Astrophysics Data System (ADS)

Matsumoto, Takeshi; Sadakiyo, Masaaki; Ooi, Mei Lee; Kitano, Sho; Yamamoto, Tomokazu; Matsumura, Syo; Kato, Kenichi; Takeguchi, Tatsuya; Yamauchi, Miho

2014-07-01

An Fe group ternary nanoalloy (NA) catalyst enabled selective electrocatalysis towards CO2-free power generation from highly deliverable ethylene glycol (EG). A solid-solution-type FeCoNi NA catalyst supported on carbon was prepared by a two-step reduction method. High-resolution electron microscopy techniques identified atomic-level mixing of constituent elements in the nanoalloy. We examined the distribution of oxidised species, including CO2, produced on the FeCoNi nanoalloy catalyst in the EG electrooxidation under alkaline conditions. The FeCoNi nanoalloy catalyst exhibited the highest selectivities toward the formation of C2 products and to oxalic acid, i.e., 99 and 60%, respectively, at 0.4 V vs. the reversible hydrogen electrode (RHE), without CO2 generation. We successfully generated power by a direct EG alkaline fuel cell employing the FeCoNi nanoalloy catalyst and a solid-oxide electrolyte with oxygen reduction ability, i.e., a completely precious-metal-free system.

Acid and alkali doped PBI electrolyte in electrochemical system

NASA Astrophysics Data System (ADS)

Xing, Baozhong

In this work the conductivity of blank PBI membrane, acid doped PBI and alkaline doped PBI was systematically studied. A new methodology for sorption kinetics study in electrolyte solution has been established by monitoring the conductivity change during the sorption process. The model of the doping process and mechanism of conductivity are proposed. The performance of PBI (doped under optimum conditions) in fuel cell as PEM was evaluated. The experimental results show that the blank PBI in acid solution is an ionic insulator. It clarified the long time confusion in this area. The acid doped PBI membrane is an ionic conductor. The conductivity increases with the concentration of the acid solution. In high concentration acid solution, the conductivity increases with the type of acid in the order: H2SO 4 > H3PO4 > HClO4 > HNO3 > HCl. The kinetics of the doping process was studied, by a continuous method. The ionic conductivity mechanism was established. The PBI membranes doped with H2SO4 and H3PO4 exhibit better performance than NafionRTM. The doped FBI has more resistance to CO poison. 3% CO in H2 has little effect on the H3PO 4 doped PBI membrane at 185°C. The conductivity of the alkali doped PBI membrane changes with the concentration of the alkaline solution and the type of the alkalis. The conductivity has a maximum in KOH and NaOH solution. The maximum conductivity in KOH is higher than in NaOH and LiOH. It is about 5 times of that of NafionRTM in alkaline solution. The two-step sorption process in alkaline solution was observed. The first step is the permeation process of the alkalis in the PBI membrane. The permeation is the results of diffusion and interaction. It is concluded that the permeation process is controlled by the rate of interaction between the alkali and PBI molecule. The second step is the relaxation process in the membrane. This step contributes more to the conductivity for the membrane than the first step. The ionic conductivity mechanism was established. In solution the cations and OH- all participate in the transport of current. It is the OH- that breaks the bonds between PBI molecules and enables the cations pass through the membrane. The performance of alkali doped PBI (doped under optimum conditions) in fuel cell as PEM is as good as NafionRTM.

Coordination chemistry of vitamin C. Part I. Interaction of L-ascorbic acid with alkaline earth metal ions in the crystalline solid and aqueous solution.

PubMed

Tajmir-Riahi, H A

1990-10-01

The interaction of L-ascorbic acid with alkaline earth metal ions has been investigated in aqueous solution at pH 6-7. The solid salts of the type Mg(L-ascorbate)2.4H2O, Ca(L-ascorbate)2.2H2O, Sr(L-ascorbate)2.2H2O and Ba(L-ascorbate)2.2H2O were isolated and characterized by means of 13C NMR and FT-IR spectroscopy. Spectroscopic and other evidence suggested that in aqueous solution, the binding of the alkaline earth metal ions is through the O-3 atom of the ascorbate anion, while in the solid state the binding of the Mg(II) is different from those of the other alkaline earth metal ion salts. The Mg(II) ion binds to the O-3, O-1 atom of the two ascorbate anions and to two H2O molecules, while the eight-coordination around the Ca(II), Sr(II), and Ba(II) ions would be completed by the coordination of three acid anions, through O-5, O-6 of the first, O-3, O-5, O-6 of the second and O-1 of the third anion as well as to two H2O molecules. The structural properties of the alkaline earth metal-ascorbate salts are different in the solid and aqueous solution.

The Effect of Alkaline Activator Ratio on the Compressive Strength of Fly Ash-Based Geopolymer Paste

NASA Astrophysics Data System (ADS)

Lăzărescu, A. V.; Szilagyi, H.; Baeră, C.; Ioani, A.

2017-06-01

Alkaline activation of fly ash is a particular procedure in which ash resulting from a power plant combined with a specific alkaline activator creates a solid material when dried at a certain temperature. In order to obtain desirable compressive strengths, the mix design of fly ash based geopolymer pastes should be explored comprehensively. To determine the preliminary compressive strength for fly ash based geopolymer paste using Romanian material source, various ratios of Na2SiO3 solution/ NaOH solution were produced, keeping the fly ash/alkaline activator ratio constant. All the mixes were then cured at 70 °C for 24 hours and tested at 2 and 7 days, respectively. The aim of this paper is to present the preliminary compressive strength results for producing fly ash based geopolymer paste using Romanian material sources, the effect of alkaline activators ratio on the compressive strength and studying the directions for future research.

A biogeochemical comparison of two well-buffered catchments with contrasting histories of acid deposition

USGS Publications Warehouse

Shanley, J.B.; Kram, P.; Hruska, J.; Bullen, T.D.

2004-01-01

Much of the biogeochemical cycling research in catchments in the past 25 years has been driven by acid deposition research funding. This research has focused on vulnerable base-poor systems; catchments on alkaline lithologies have received little attention. In regions of high acid loadings, however, even well-buffered catchments are susceptible to forest decline and episodes of low alkalinity in streamwater. As part of a collaboration between the Czech and U.S. Geological Surveys, we compared biogeochemical patterns in two well-studied, well-buffered catchments: Pluhuv Bor in the western Czech Republic, which has received high loading of atmospheric acidity, and Sleepers River Research Watershed in Vermont, U.S.A., where acid loading has been considerably less. Despite differences in lithology, wetness, forest type, and glacial history, the catchments displayed similar patterns of solute concentrations and flow. At both catchments, base cation and alkalinity diluted with increasing flow, whereas nitrate and dissolved organic carbon increased with increasing flow. Sulfate diluted with increasing flow at Sleepers River, while at Pluhuv Bor the sulfate-flow relation shifted from positive to negative as atmospheric sulfur (S) loadings decreased and soil S pools were depleted during the 1990s. At high flow, alkalinity decreased to near 100 ??eq L-1 at Pluhuv Bor compared to 400 ??eq L-1 at Sleepers River. Despite the large amounts of S flushed from Pluhuv Bor soils, these alkalinity declines were caused solely by dilution, which was greater at Pluhuv Bor relative to Sleepers River due to greater contributions from shallow flow paths at high flow. Although the historical high S loading at Pluhuv Bor has caused soil acidification and possible forest damage, it has had little effect on the acid/base status of streamwater in this well-buffered catchment. ?? 2004 Kluwer Academic Publishers.

A Kirkwood-Buff derived force field for alkaline earth halide salts

NASA Astrophysics Data System (ADS)

Naleem, Nawavi; Bentenitis, Nikolaos; Smith, Paul E.

2018-06-01

The activity and function of many macromolecules in cellular environments are coupled with the binding of divalent ions such as calcium or magnesium. In principle, computer simulations can be used to understand the molecular level aspects of how many important macromolecules interact with ions. However, most of the force fields currently available often fail to accurately reproduce the properties of divalent ions in aqueous environments. Here we develop classical non-polarizable force fields for the aqueous alkaline earth metal halides (MX2), where M = Mg2+, Ca2+, Sr2+, Ba2+ and X = Cl-, Br-, I-, which can be used in bimolecular simulations and which are compatible with the Simple Point Charge/Extended (SPC/E) water model. The force field parameters are specifically developed to reproduce the experimental Kirkwood-Buff integrals for aqueous solutions and thereby the experimental activity derivatives, partial molar volumes, and excess coordination numbers. This ensures that a reasonable balance between ion-ion, ion-water, and water-water distributions is obtained. However, this requires a scaling of the cation to water oxygen interaction strength in order to accurately reproduce the integrals. The scaling factors developed for chloride salts are successfully transferable to the bromide and iodide salts. Use of these new models leads to reasonable diffusion constants and dielectric decrements. However, the performance of the models decreases with increasing salt concentration (>4m), and simulations of the pure crystals exhibited unstable behavior.

A Kirkwood-Buff derived force field for alkaline earth halide salts.

PubMed

Naleem, Nawavi; Bentenitis, Nikolaos; Smith, Paul E

2018-06-14

The activity and function of many macromolecules in cellular environments are coupled with the binding of divalent ions such as calcium or magnesium. In principle, computer simulations can be used to understand the molecular level aspects of how many important macromolecules interact with ions. However, most of the force fields currently available often fail to accurately reproduce the properties of divalent ions in aqueous environments. Here we develop classical non-polarizable force fields for the aqueous alkaline earth metal halides (MX 2 ), where M = Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ and X = Cl - , Br - , I - , which can be used in bimolecular simulations and which are compatible with the Simple Point Charge/Extended (SPC/E) water model. The force field parameters are specifically developed to reproduce the experimental Kirkwood-Buff integrals for aqueous solutions and thereby the experimental activity derivatives, partial molar volumes, and excess coordination numbers. This ensures that a reasonable balance between ion-ion, ion-water, and water-water distributions is obtained. However, this requires a scaling of the cation to water oxygen interaction strength in order to accurately reproduce the integrals. The scaling factors developed for chloride salts are successfully transferable to the bromide and iodide salts. Use of these new models leads to reasonable diffusion constants and dielectric decrements. However, the performance of the models decreases with increasing salt concentration (>4m), and simulations of the pure crystals exhibited unstable behavior.

Interfacial activity in alkaline flooding enhanced oil recovery

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

Chan, M.K.

1981-01-01

The ionization of long-chained organic acids in the crude oil to form soaps was shown to be primarily responsible for the lowering of oil-water interfacial tension at alkaline pH. These active acids can be concentrated by silica gel chromatography into a minor polar fraction. An equilibrium chemical model was proposed based on 2 competing reactions: the ionization of acids to form active anions, and the formation of undissociated soap between acid anions and sodium ions. It correlates the interfacial activity with the interfacial concentration of active acid anions which is expressed in terms of the concentrations of the chemical speciesmore » in the system. The model successfully predicts the observed oil-alkaline solution interfacial phenomenon, including its dependence on pH, alkali and salt concentrations, type of acid present and type of soap formed. Flooding at different alkali concentrations to activate different acid species present in the crude was shown to give better recovery than flooding at a single high alkali concentration. Treating the crude oil with a dilute solution of mineral acids liberates additional free active acids and yields better interfacial activity during subsequent alkali contact.« less

Geopolymers and Their Uses: Review

NASA Astrophysics Data System (ADS)

Burduhos Nergis, D. D.; Abdullah, M. M. A. B.; Vizureanu, P.; Tahir, M. F. M.

2018-06-01

Outlining the past-present history of the study of alumino-silicate materials, it is well known that geopolymers are inorganic polymers obtained from chemical reaction, also known as geopolymerisation, between an alkaline solution and a solid reach in aluminium and silicone. There is still some controversy surrounding the alkaline activators used to create geopolymer concrete, because homogeneous mixture composed of two (NaOH and Na2SO3) or more chemical in varying proportions are usually highly corrosive and hard to handle. In order to overcome Portland cement many wastes have been used in recent studies to create “friendly” cements by geopolymerisation. In this short review we present basic information’s about how to create and use geopolymers, alkaline activators and raw materials that can be used and conclusions. One question that needs to be asked: Can those materials replace on large scale Portland cement?

Alkaline sodium borohydride gel as a hydrogen source for PEMFC or an energy carrier for NaBH 4-air battery

NASA Astrophysics Data System (ADS)

Liu, B. H.; Li, Z. P.; Chen, L. L.

In this preliminary study, we tried to use sodium polyacrylate as the super absorbent polymer to form alkaline NaBH 4 gel and explored its possibilities for borohydride hydrolysis and borohydride electro-oxidation. It was found that the absorption capacity of sodium polyacrylate decreased with increasing NaBH 4 concentration. The formed gel was rather stable in the sealed vessel but tended to slowly decompose in open air. Hydrogen generation from the gel was carried out using CoCl 2 catalyst precursor solutions. Hydrogen generation rate from the alkaline NaBH 4 gel was found to be higher and impurities in hydrogen were less than that from the alkaline NaBH 4 solution. The NaBH 4 gel also successfully powered a NaBH 4-air battery.

Methodology of analysis of very weak acids by isotachophoresis with electrospray-ionization mass-spectrometric detection: Anionic electrolyte systems for the medium-alkaline pH range.

PubMed

Malá, Zdena; Gebauer, Petr

2018-01-15

This work describes for the first time a functional electrolyte system setup for anionic isotachophoresis (ITP) with electrospray-ionization mass-spectrometric (ESI-MS) detection in the neutral to medium-alkaline pH range. So far no application was published on the analysis of very weak acids by anionic ITP-MS although there is a broad spectrum of potential analytes with pK a values in the range 5-10, where application of this technique promises interesting gains in both sensitivity and specificity. The problem so far was the lack of anionic ESI-compatible ITP systems in the mentioned pH range as all typical volatile anionic system components are fully ionized at neutral and alkaline pH and thus too fast to suit as terminators. We propose an original solution of the problem based on the combination of two ITP methods: (i) use of the hydroxyl ion as a natural and ESI-compatible terminator, and (ii) use of configurations based on moving-boundary ITP. The former method ensures effective stacking of analytes by an alkaline terminator of sufficiently low mobility and the latter offers increased flexibility for tuning of the separation window and selectivity according to actual needs. A theoretical description of the proposed model is presented and applied to the design of very simple functional electrolyte configurations. The properties of example systems are demonstrated by both computer simulation and experiments with a group of model analytes. Potential effects of carbon dioxide present in the solutions are demonstrated for particular systems. Experimental results confirm that the proposed methodology is well capable of performing sensitive and selective ITP-MS analyses of very weak acidic analytes (e.g. sulfonamides or chlorophenols). Copyright © 2017 Elsevier B.V. All rights reserved.

Easy preparation of dietary fiber with the high water-holding capacity from food sources.

PubMed

Yamazaki, Eiji; Murakami, Kazumi; Kurita, Osamu

2005-03-01

Dietary fibers were prepared as alkali- and acid-insoluble fractions with chemical phosphorylation from Tossa jute (Corchorus olitorius), defatted soybean (Glycine max), and Shiitake (Lentinula edodes). The dietary fiber fractions treated with alkaline solution containing sodium metaphosphate had the lower protein content and higher total dietary fiber content than those of the preparations without phosphorylation. Alkaline extraction followed by phosphorylation led to a 1.5-fold increase in the water holding capacity of dietary fiber compared with no phosphorylation, whereas the binding capacity to bile acids of dietary fiber was almost the same. The alkali- and acid-insoluble extraction with phosphorylation provided an efficient preparation of water-insoluble dietary fiber with high-water holding capacity from various food sources.

Friction modifier using adherent metallic multilayered or mixed element layer conversion coatings

NASA Technical Reports Server (NTRS)

Schramm, Harry F. (Inventor); Defalco, Frank G. (Inventor); Starks, Sr., Lloyd L. (Inventor)

2012-01-01

A process for creating conversion coatings and spin, drawing, and extrusion finishes for surfaces, wherein the conversion coatings and spin, drawing, and extrusion finishes contain potassium, phosphorus, nitrogen, silicon, and one or more non-alkaline metals. The process comprises forming a first aqueous solution of silicate, potassium hydroxide, and ammonium hydroxide; forming a second aqueous solution of water, phosphoric acid, ammonium hydroxide, an alkali metal hydroxide, and one or more non-alkaline metals, and then combining the first solution with the second solution to form a final solution. This final solution forms an anti-friction multi-layer conversion coating or a spin, drawing, and extrusion finish on a surface when applied to the surface, either directly or as an additive in lubricating fluids.

Solution-derived sodalite made with Si- and Ge-ethoxide precursors for immobilizing electrorefiner salt

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

Riley, Brian J.; Lepry, William C.; Crum, Jarrod V.

Chlorosodalite has the general form of Na8(AlSiO4)6Cl2 and this paper describes experiments conducted to synthesize sodalite to immobilize a mixed chloride salt using solution-based techniques. Sodalites were made using different Group IV contributions from either Si(OC2H5)4 or Ge(OC2H5)4, NaAlO2, and a simulated spent electrorefiner salt solution containing a mixture of alkali, alkaline earth, and lanthanide chlorides. Additionally, 6 glass binders at low loadings of 5 mass% were evaluated as sintering aids for the consolidation process. The approach of using the organic Group IV additives can be used to produce large quantities of sodalite at room temperature and shows promise overmore » a method where colloidal silica is used as the silica source. However, the small particle sizes inhibited densification during pressure-less sintering.« less

In silico kinetics of alkaline hydrolysis of 1,3,5-trinitro-1,3,5-triazinane (RDX): M06-2X investigation.

PubMed

Sviatenko, L K; Gorb, L; Leszczynska, D; Okovytyy, S I; Shukla, M K; Leszczynski, J

2017-03-22

Alkaline hydrolysis of RDX (hexahydro-1,3,5-trinitro-1,3,5-triazine), as one of the most promising methods for nitrocompound remediation, was investigated computationally at the PCM(Pauling)/M06-2X/6-311++G(d,p) level of theory. Computational simulation shows that RDX hydrolysis is a highly exothermic multistep process involving initial deprotonation and nitrite elimination, cycle cleavage, further transformation of cycle-opened intermediates to end products caused by a series of C-N bond ruptures, hydroxide attachments, and proton transfers. Computationally predicted products of RDX hydrolysis such as nitrite, nitrous oxide, formaldehyde, formate, and ammonia correspond to experimentally observed ones. Accounting of specific hydration of hydroxide is critical to create an accurate kinetic model for alkaline hydrolysis. Simulated kinetics of the hydrolysis are in good agreement with available experimental data. A period of one month is necessary for 99% RDX decomposition at pH 10. Computations predict significant increases of the reaction rate of hydrolysis at pH 11, pH 12, and pH 13.

SEPARATION OF PLUTONYL IONS

DOEpatents

Connick, R.E.; McVey, Wm.H.

1958-07-15

A process is described for separating plutonyl ions from the acetate ions with which they are associated in certaln carrier precipitation methods of concentrating plutonium. The method consists in adding alkaline earth metal ions and subsequently alkalizing the solution, causing formation of an alkaltne earth plutonate precipitate. Barium hydroxide is used in a preferred embodiment since it provides alkaline earth metal ion and alkalizes the solution in one step forming insoluble barium platonate.

Mechanism of alcohol-enhanced lucigenin chemiluminescence in alkaline solution.

PubMed

Chi, Quan; Chen, Wanying; He, Zhike

2015-11-01

The chemiluminescence (CL) of lucigenin (Luc(2+)) can be enhanced by different alcohols in alkaline solution. The effect of different fatty alcohols on the CL of lucigenin was related to the carbon chain length and the number of hydroxyl groups. Glycerol provides the greatest enhancement. UV/Vis absorption spectra and fluorescence spectra showed that N-methylacridone (NMA) was produced in the CL reaction in the presence of different alcohols. The peak of the CL spectrum was located at 470 nm in all cases, indicating that the luminophore was always the excited-state NMA. The quenching of lucigenin CL by superoxide dismutase (SOD) and the electron spin resonance (ESR) results with the spin trap of 5,5-dimethyl-1-pyrroline N-oxide (DMPO) demonstrated that superoxide anions (O2 (•-)) were generated from dissolved oxygen in the CL reaction and that glycerol and dihydroxyacetone (DHA) can promote O2 (•-) production by the reduction of dissolved oxygen in alkaline solution. It was assumed that the enhancement provided by different alcohols was related to the solvent effect and reducing capacity. Glycerol and DHA can also reduce Luc(2+) into lucigenin cation radicals (Luc(•+) ), which react with O2 (•-) to produce CL, and glycerol can slowly transform into DHA, which is oxidized quickly in alkaline solution. Copyright © 2015 John Wiley & Sons, Ltd.

Laboratory Testing of Volcanic Gas Sampling Techniques

NASA Astrophysics Data System (ADS)

Kress, V. C.; Green, R.; Ortiz, M.; Delmelle, P.; Fischer, T.

2003-12-01

A series of laboratory experiments were performed designed to calibrate several commonly used methods for field measurement of volcanic gas composition. H2, CO2, SO2 and CHCl2F gases were mixed through carefully calibrated rotameters to form mixtures representative of the types of volcanic compositions encountered at Kilauea and Showa-Shinzan. Gas mixtures were passed through a horizontal furnace at 700oC to break down CHCl2F and form an equilibrium high-temperature mixture. With the exception of Giggenbach bottle samples, all gas sampling was performed adjacent to the furnace exit in order to roughly simulate the air-contaminated samples encountered in Nature. Giggenbach bottle samples were taken from just beyond the hot-spot 10cm down the furnace tube to minimize atmospheric contamination. Alkali-trap measurements were performed by passing gases over or bubbling gases through 6N KOH, NaOH or LiOH solution for 10 minutes. Results were highly variable with errors in measured S/Cl varying from +1600% to -19%. In general reduced Kilauea compositions showed smaller errors than the more oxidized Showa-Shinzan compositions. Results were not resolvably different in experiments where gas was bubbled through the alkaline solution. In a second set of experiments, 25mm circles of Whatman 42 filter paper were impregnated with NaHCO3or KHCO3 alkaline solutions stabilized with glycerol. Some filters also included Alizarin (5.6-7.2) and neutral red (6.8-8.0) Ph indicator to provide a visual monitor of gas absorption. Filters were mounted in individual holders and used in stacks of 3. Durations were adjusted to maximize reaction in the first filter in the stack and minimize reaction in the final filter. Errors in filter pack measurements were smaller and more systematic than the alkali trap measurements. S/Cl was overestimated in oxidized gas mixtures and underestimated in reduced mixtures. Alkali-trap methods allow extended unattended monitoring of volcanic gasses, but our results suggest that they are poor recorders of gas composition. Filter pack methods are somewhat better, but are more difficult to interpret than previously recognized. We suggest several refinements to the filter-pack technique that can improve accuracy. Giggenbach bottles remain the best method for volcanic gas sampling, despite the inherent difficulty and danger of obtaining samples in active volcanic environments. Relative merits of different alkali solutions and indicators are discussed.

Elasticity and expansion test performance of geopolymer as oil well cement

NASA Astrophysics Data System (ADS)

Ridha, S.; Hamid, A. I. Abd; Halim, A. H. Abdul; Zamzuri, N. A.

2018-04-01

History has shown that geopolymer cement provides high compressive strength as compared to Class G cement. However, the research had been done at ambient temperature, not at elevated condition which is the common oil well situation. In this research, the physical and mechanical properties performance of the oil well cement were investigated by laboratory work for two types of cement that are geopolymer and Class G cement. The cement samples were produced by mixing the cement according to the API standards. Class C fly ash was used in this study. The alkaline solution was prepared by mixing sodium silicate with NaOH solution. The NaOH solution was prepared by diluting NaOH pellets with distilled water to 8M. The cement samples were cured at a pressure of 3000 psi and a temperature of 130 °C to simulate the downhole condition. After curing, the physical properties of the cement samples were investigated using OYO Sonic Viewer to determine their elastic properties. Autoclave expansion test and compressive strength tests were conducted to determine the expansion value and the strength of the cement samples, respectively. The results showed that the geopolymer cement has a better physical and mechanical properties as compared with Class G cement at elevated condition.

Magnetite solubility and phase stability in alkaline media at elevated temperatures

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

Ziemniak, S.E.; Jones, M.E.; Combs, K.E.S.

Magnetite, Fe{sub 3}O{sub 4}, is the dominant oxide constituent of the indigenous corrosion layers that form on iron base alloys in high purity, high temperature water. The apparent simultaneous stability of two distinct oxidation states of iron in this metal oxide is responsible for its unique solubility behavior. The present work was undertaken to extend the experimental and theoretical bases for estimating solubilities of an iron corrosion product (Fe{sub 3}O{sub 4}/Fe(OH){sub 2}) over a broader temperature range and in the presence of complexing, pH-controlling reagents. These results indicate that a surface layer of ferrous hydroxide controls magnetite solubility behavior atmore » low temperatures in much the same manner as a surface layer of nickel(II) hydroxide was previously reported to control the low temperature solubility behavior of NiO. The importance of Fe(III) ion complexes implies not only that most previously-derived thermodynamic properties of the Fe(OH){sub 3}{sup {minus}} ion are incorrect, but that magnetite phase stability probably shifts to favor a sodium ferric hydroxyphosphate compound in alkaline sodium phosphate solutions at elevated temperatures. The test methodology involved pumping alkaline solutions of known composition through a bed of Fe{sub 3}O{sub 4} granules and analyzing the emerging solution for Fe. Two pH-controlling reagents were tested: sodium phosphate and ammonia. Equilibria for the following reactions were described in thermodynamic terms: (a) Fe(OH){sub 2}/Fe{sub 3}O{sub 4} dissolution and transformation, (b) Fe(II) and Fe(III) ion hydroxocomplex formation (hydrolysis), (c) Fe(II) ion amminocomplex formation, and (d) Fe(II) and Fe(III) ion phosphatocomplex formation. 36 refs.« less

Controlled surface morphology and hydrophilicity of polycaprolactone toward human retinal pigment epithelium cells.

PubMed

Shahmoradi, Saleheh; Yazdian, Fatemeh; Tabandeh, Fatemeh; Soheili, Zahra-Soheila; Hatamian Zarami, Ashraf Sadat; Navaei-Nigjeh, Mona

2017-04-01

Applying scaffolds as a bed to enhance cell proliferation and even differentiation is one of the treatment of retina diseases such as age-related macular degeneration (AMD) which deteriorating photoreceptors and finally happening blindness. In this study, aligned polycaprolactone (PCL) nanofibers were electrospun and at different conditions and their characteristics were measured by scanning electron microscope (SEM) and contact angle. Response surface methodology (RSM) was used to optimize the diameter of fabricated nanofibers. Two factors as solution concentration and voltage value were considered as independent variables and their effects on nanofibers' diameters were evaluated by central composite design and the optimum conditions were obtained as 0.12g/mL and 20kV, respectively. In order to decrease the hydrophobicity of PCL, the surface of the fabricated scaffolds was modified by alkaline hydrolysis method. Contact time of the scaffolds and alkaline solution and concentration of alkaline solution were optimized using Box Behnken design and (120min and 5M were the optimal, respectively). Contact angle measurement showed the high hydrophilicity of treated scaffolds (with contact angle 7.48°). Plasma surface treatment was applied to compare the effect of using two kinds of surface modification methods simultaneously on hydrolyzed scaffolds. The RPE cells grown on scaffolds were examined by immunocytochemistry (ICC), MTT and continuous inspection of cellular morphology. Interestingly, Human RPE cells revealed their characteristic morphology on hydrolyzed scaffold well. As a result, we introduced a culture substrate with low diameter (185.8nm), high porosity (82%) and suitable hydrophilicity (with contact angle 7.48 degree) which can be promising for hRPE cell transplantation. Copyright © 2016. Published by Elsevier B.V.

Effects of Aging on PuO2∙xH2O Particle Size in Alkaline Solution

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

Delegard, Calvin H.

Between 1944 and 1989, 54.5 metric tons of the United States’ weapons-grade plutonium and an additional 12.9 metric tons of fuel-grade plutonium were produced and separated from irradiated fuel at the Hanford Site. Acidic high-activity wastes containing around 600 kg of plutonium were made alkaline and discharged to underground storage tanks from separations, isolation, and recycle processes to yield average plutonium concentration of about 0.003 grams per liter (or ~0.0002 wt%) in the ~200 million liter tank waste volume. The plutonium is largely associated with low-solubility metal hydroxide/oxide sludges where its low concentration and intimate mixture with neutron-absorbing elements (e.g.,more » iron) are credited in nuclear criticality safety. However, concerns have been expressed that plutonium, in the form of plutonium hydrous oxide, PuO2∙xH2O, could undergo sufficient crystal growth through dissolution and reprecipitation in the alkaline tank waste to potentially become separable from neutron absorbing constituents by settling or sedimentation. Thermodynamic considerations and laboratory studies of systems chemically analogous to tank waste show that the plutonium formed in the alkaline tank waste by precipitation through neutralization from acid solution probably entered as 2–4-nm PuO2∙xH2O crystallite particles that, because of their low solubility and opposition from radiolytic processes, grow from that point at exceedingly slow rates, thus posing no risk of physical segregation.« less

Photodegradation of the novel fungicide fluopyram in aqueous solution: kinetics, transformation products, and toxicity evolvement.

PubMed

Dong, Bizhang; Hu, Jiye

2016-10-01

The aqueous photodegradation of fluopyram was investigated under UV light (λ ≥ 200 nm) and simulated sunlight irradiation (λ ≥ 290 nm). The effect of solution pH, fulvic acids (FA), nitrate (NO3 (-)), Fe (III) ions, and titanium dioxide (TiO2) on direct photolysis of fluopyram was explored. The results showed that fluopyram photodegradation was faster in neutral solution than that in acidic and alkaline solutions. The presence of FA, NO3 (-), Fe (III), and TiO2 slightly affected the photodegradation of fluopyram under UV irradiation, whereas the photodegradation rates of fluopyram with 5 mg L(-1) Fe (III) and 500 mg L(-1) TiO2 were about 7-fold and 13-fold faster than that without Fe (III) and TiO2 under simulated sunlight irradiation, respectively. Three typical products for direct photolysis of fluopyram have been isolated and characterized by liquid chromatography tandem mass spectrometry. These products resulted from the intramolecular elimination of HCl, hydroxyl-substitution, and hydrogen extraction. Based on the identified transformation products and evolution profile, a plausible degradation pathway for the direct photolysis of fluopyram in aqueous solution was proposed. In addition, acute toxicity assays using the Vibrio fischeri bacteria test indicated that the transformation products were more toxic than the parent compound.

Uranium Anodic Dissolution under Slightly Alkaline Conditions Progress Report Full-Scale Demonstration with DU Foil

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

Gelis, A.; Brown, M. A.; Wiedmeyer, S.

2014-02-18

Argonne National Laboratory (Argonne) is developing an alternative method for digesting irradiated low enriched uranium (LEU) foil targets to produce 99Mo in neutral/alkaline media. This method consists of the electrolytic dissolution of irradiated uranium foil in sodium bicarbonate solution, followed by precipitation of base-insoluble fission and activation products, and uranyl-carbonate species with CaO. The addition of CaO is vital for the effective anion exchange separation of 99MoO 4 2- from the fission products, since most of the interfering anions (e.g., CO 3 2-) are removed from the solution, while molybdate remains in solution. An anion exchange is used to retainmore » and to purify the 99Mo from the filtrate. The electrochemical dissolver has been designed and fabricated in 304 stainless-steel (SS), and tested for the dissolution of a full-size depleted uranium (DU) target, wrapped in Al foil. Future work will include testing with low-burn-up DU foil at Argonne and later with high-burn-up LEU foils at Oak Ridge National Laboratory.« less

Simultaneous speciation analysis of chromate, molybdate, tungstate and vanadate in welding fume alkaline extracts by HPLC-ICP-MS.

PubMed

Ščančar, Janez; Berlinger, Balázs; Thomassen, Yngvar; Milačič, Radmila

2015-09-01

A novel analytical procedure was developed for the simultaneous speciation analysis of chromate, molybdate, tungstate and vanadate by anion-exchange high performance liquid chromatography hyphenated to inductively coupled plasma mass spectrometry (HPLC-ICP-MS). Linear gradient elution from 100% water to 100% 0.7 M NaCl was applied for chromatographic separation of metal species. In standard aqueous solution at neutral pH molybdate, tungstate and vanadate exist in several aqueous species, while chromate is present as a single CrO4(2-) species. Consequently, only chromate can be separated from this solution in a sharp chromatographic peak. For obtaining sharp chromatographic peaks for molybdate, tungstate and vanadate, the pH of aqueous standard solutions was raised to 12. At highly alkaline conditions single CrO4(2-), MoO4(2-) and WO4(2-) are present and were eluted in sharp chromatographic peaks, while VO4(3-) species, which predominates at pH 12 was eluted in slightly broaden peak. In a mixture of aqueous standard solutions (pH 12) chromate, molybdate, tungstate and vanadate were eluted at retention times from 380 to 420 s, 320 to 370 s, 300 to 350 s and 240 to 360 s, respectively. Eluted species were simultaneously detected on-line by ICP-MS recording m/z 52, 95, 182 and 51. The developed procedure was successfully applied to the analysis of leachable concentrations of chromate, molybdate, tungstate and vanadate in alkaline extracts (2% NaOH+3% Na2CO3) of manual metal arc (MMA) welding fumes loaded on filters. Good repeatability and reproducibility of measurement (RSD±3.0%) for the investigated species were obtained in both aqueous standard solutions (pH 12) and in alkaline extracts of welding fumes. Low limits of detection (LODs) were found for chromate (0.02 ng Cr mL(-1)), molybdate (0.1 ng Mo mL(-1)), tungstate (0.1 ng W mL(-1)) and vanadate (0.2 ng V mL(-1)). The accuracy of analytical procedure for the determination of chromate was checked by analysis of CRM 545, Cr(VI) in welding dust loaded on a filter. Good agreement between determined and reported certified values was obtained. For molybdate, tungstate and vanadate the assessment of accuracy was performed by spiking welding fume filters. Good recoveries for all investigated species (98-101%) confirmed the accuracy of the analytical procedure. Copyright © 2015 Elsevier B.V. All rights reserved.

Room temperature micro-hydrogen-generator

NASA Astrophysics Data System (ADS)

Gervasio, Don; Tasic, Sonja; Zenhausern, Frederic

A new compact and cost-effective hydrogen-gas generator has been made that is well suited for supplying hydrogen to a fuel-cell for providing base electrical power to hand-carried appliances. This hydrogen-generator operates at room temperature, ambient pressure and is orientation-independent. The hydrogen-gas is generated by the heterogeneous catalytic hydrolysis of aqueous alkaline borohydride solution as it flows into a micro-reactor. This reactor has a membrane as one wall. Using the membrane keeps the liquid in the reactor, but allows the hydrogen-gas to pass out of the reactor to a fuel-cell anode. Aqueous alkaline 30 wt% borohydride solution is safe and promotes long application life, because this solution is non-toxic, non-flammable, and is a high energy-density (≥2200 W-h per liter or per kilogram) hydrogen-storage solution. The hydrogen is released from this storage-solution only when it passes over the solid catalyst surface in the reactor, so controlling the flow of the solution over the catalyst controls the rate of hydrogen-gas generation. This allows hydrogen generation to be matched to hydrogen consumption in the fuel-cell, so there is virtually no free hydrogen-gas during power generation. A hydrogen-generator scaled for a system to provide about 10 W electrical power is described here. However, the technology is expected to be scalable for systems providing power spanning from 1 W to kW levels.

Rheology and physical-chemical characteristics of the solutions of the medicines

NASA Astrophysics Data System (ADS)

Urakov, A.; Urakova, N.

2015-04-01

In the laboratory studied the dynamics of rheology of water solutions with plasma- inflammatory and antiseptic funds when mixing them with blood, plasma and pus under the influence of the following physical and chemical factors of local interaction: gravity, specific gravity, temperature, relative viscosity, internal pressure, sparkling water, total concentration of the ingredients, surface activity, volume of acid and osmotic activity of medicines. Found that the rheology of biological liquids improve hyperthermic, highly alkaline and highly carbonated solution medicines. For the dilution of pus, dense festering mass of sulfur plugs and tear stones invited to apply heated to +39 - +42°C with aqueous solution of 0.5 - 3% hydrogen peroxide and 0.5 - 10% sodium bicarbonate saturated with carbon dioxide to excess pressure 0.2 ATM.

Waste separation and pretreatment using crystalline silicotitanate ion exchangers

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

Tadros, M.E.; Miller, J.E.; Anthony, R.G.

1997-10-01

A new class of inorganic ion exchangers called crystalline silicotitanates (CSTs) has been developed jointly by Sandia National Laboratories and Texas A&M University to selectively remove Cs and other radionuclides from a wide spectrum of radioactive defense wastes. The CST exhibits high selectivity and affinity for Cs and Sr under a wide range of conditions. Tests show it can remove part-per-million concentrations of Cs{sup +} from highly alkaline, high-sodium simulated radioactive waste solutions modeled after those at Hanford, Oak Ridge, and Savannah River. The materials exhibit ion exchange properties based on ionic size selectivity. Specifically, crystalline lattice spacing is controlledmore » to be highly selective for Cs ions even in waste streams containing very high (5 to 10 M) concentrations of sodium. The CST technology is being demonstrated with actual waste at several DOE facilities. The use of inorganic ion exchangers. The inorganics are more resistant to chemical, thermal, and radiation degradation. Their high selectivities result in more efficient operations offering the possibility of a simple single-pass operation. In contrast, regenerable organic ion exchangers require additional processing equipment to handle the regeneration liquids and the eluant with the dissolved Cs.« less

Simulations of Ground-Water Flow and Particle Pathline Analysis in the Zone of Contribution of a Public-Supply Well in Modesto, Eastern San Joaquin Valley, California

USGS Publications Warehouse

Burow, Karen R.; Jurgens, Bryant C.; Kauffman, Leon J.; Phillips, Steven P.; Dalgish, Barbara A.; Shelton, Jennifer L.

2008-01-01

Shallow ground water in the eastern San Joaquin Valley is affected by high nitrate and uranium concentrations and frequent detections of pesticides and volatile organic compounds (VOC), as a result of ground-water development and intensive agricultural and urban land use. A single public-supply well was selected for intensive study to evaluate the dominant processes affecting the vulnerability of public-supply wells in the Modesto area. A network of 23 monitoring wells was installed, and water and sediment samples were collected within the approximate zone of contribution of the public-supply well, to support a detailed analysis of physical and chemical conditions and processes affecting the water chemistry in the well. A three-dimensional, steady-state local ground-water-flow and transport model was developed to evaluate the age of ground water reaching the well and to evaluate the vulnerability of the well to nonpoint source input of nitrate and uranium. Particle tracking was used to compute pathlines and advective travel times in the ground-water flow model. The simulated ages of particles reaching the public-supply well ranged from 9 to 30,000 years, with a median of 54 years. The age of the ground water contributed to the public-supply well increased with depth below the water table. Measured nitrate concentrations, derived primarily from agricultural fertilizer, were highest (17 milligrams per liter) in shallow ground water and decreased with depth to background concentrations of less than 2 milligrams per liter in the deepest wells. Because the movement of water is predominantly downward as a result of ground-water development, and because geochemical conditions are generally oxic, high nitrate concentrations in shallow ground water are expected to continue moving downward without significant attenuation. Simulated long-term nitrate concentrations indicate that concentrations have peaked and will decrease in the public-supply well during the next 100 years because of the low nitrate concentrations in recharge beneath the urban area and the increasing proportion of urban-derived ground water reaching the well. The apparent lag time between peak input concentrations and peak concentrations in the well is about 20 to 30 years. Measured uranium concentrations were also highest (45 micrograms per liter) in shallow ground water, and decreased with depth to background concentrations of about 0.5 microgram per liter. Naturally-occurring uranium adsorbed to aquifer sediments is mobilized by oxygen-rich, high-alkalinity water. Alkalinity increased in shallow ground water in response to agricultural development. As ground-water pumping increased in the 1940s and 1950s, this alkaline water moved downward through the ground-water flow system, mobilizing the uranium adsorbed to aquifer sediments. Ground water with high alkalinity and high uranium concentrations is expected to continue to move deeper in the system, resulting in increased uranium concentrations with depth in ground water. Because alkalinity (and correspondingly uranium) concentrations were high in shallow ground water beneath both the urban and the agricultural land, long-term uranium concentrations in the public-supply well are expected to increase as the proportion of uranium-affected water contributed to the well increases. Assuming that the alkalinity near the water table remains the same, the simulation of long-term alkalinity in the public-supply well indicates that uranium concentrations in the public-supply well will likely approach the maximum contaminant level; however, the time to reach this level is more than 100 years because of the significant proportion of old, unaffected water at depth that is contributed to the public-supply well.

Chemical equilibria model of strontium-90 adsorption and transport in soil in response to dynamic alkaline conditions.

PubMed

Spalding, B P; Spalding, I R

2001-01-15

Strontium-90 is a major hazardous contaminant of radioactive wastewater and its processing sludges at many Department of Energy (DOE) facilities. In the past, such contaminated wastewater and sludge have been disposed in soil seepage pits, lagoons, or cribs often under highly perturbed alkaline conditions (pH > 12) where 90Sr solubility is low and its adsorption to surrounding soil is high. As natural weathering returns these soils to near-neutral or slightly acidic conditions, the adsorbed and precipitated calcium and magnesium phases, in which 90Sr is carried, change significantly in both nature and amounts. No comprehensive computational method has been formulated previously to quantitatively simulate the dynamics of 90Sr in the soil-groundwater environment under such dynamic and wide-ranging conditions. A computational code, the Hydrologic Utility Model for Demonstrating Integrated Nuclear Geochemical Environmental Responses (HUMDINGER), was composed to describe the changing equilibria of 90Sr in soil based on its causative chemical reactions including soil buffering, pH-dependent cation-exchange capacity, cation selectivity, and the precipitation/dissolution of calcium carbonate, calcium hydroxide, and magnesium hydroxide in response to leaching groundwater characteristics including pH, acid-neutralizing capacity, dissolved cations, and inorganic carbonate species. The code includes a simulation of one-dimensional transport of 90Sr through a soil column as a series of soil mixing cells where the equilibrium soluble output from one cell is applied to the next cell. Unamended soil leaching and highly alkaline soil treatments, including potassium hydroxide, sodium silicate, and sodium aluminate, were simulated and compared with experimental findings using large (10 kg) soil columns that were leached with 90Sr-contaminated groundwater after treatment. HUMDINGER's simulations were in good agreement with dynamic experimental observations of soil exchange capacity, exchangeable cations, total 90Sr, and pH values of layers within the soil columns and of column effluents.

Effect of pH on the chemical modification of quercetin and structurally related flavonoids characterized by optical (UV-visible and Raman) spectroscopy.

PubMed

Jurasekova, Z; Domingo, C; Garcia-Ramos, J V; Sanchez-Cortes, S

2014-07-07

In this work we report the study of the chemical modifications undergone by flavonoids, especially by quercetin (QUC), under alkaline conditions by UV-visible absorption, Raman and surface-enhanced Raman scattering (SERS) spectroscopy, the study was performed in aqueous solution and also on Ag nanoparticles (AgNPs). Several processes are involved in the effect of alkaline pH both in solution and on AgNPs: autoxidation affecting mainly the C-ring of the molecule and giving rise to the molecular fragmentation leading to simpler molecular products, and/or the dimerization and further polymerization leading to species with a higher molecular weight. In addition, there exists a clear structure-instability correlation concerning mainly particular groups in the molecule: the C3-OH group in the C-ring, the catechol moiety in the B-ring and the C2=C3 bond also existing in the C-ring. QUC possesses all these groups and exhibits high instability in alkaline solution. The SERS spectra registered at different pH revealed a change in the dimerization protocol of QUC going from the A- and C-rings-like-condensation to B-ring-like-condensation. Increasing the knowledge of the chemical properties of these compounds and determining the structure-activity relationship under specific environmental factors allow us to improve their beneficial properties for health as well as the preservation of Cultural Heritage objects, for example, by preventing their degradation.

A High-Performance Sintered Iron Electrode for Rechargeable Alkaline Batteries to Enable Large-Scale Energy Storage

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

Yang, Chenguang; Manohar, Aswin K.; Narayanan, S. R.

Iron-based alkaline rechargeable batteries such as iron-air and nickel-iron batteries are particularly attractive for large-scale energy storage because these batteries can be relatively inexpensive, environment- friendly, and also safe. Therefore, our study has focused on achieving the essential electrical performance and cycling properties needed for the widespread use of iron-based alkaline batteries in stationary and distributed energy storage applications.We have demonstrated for the first time, an advanced sintered iron electrode capable of 3500 cycles of repeated charge and discharge at the 1-hour rate and 100% depth of discharge in each cycle, and an average Coulombic efficiency of over 97%. Suchmore » a robust and efficient rechargeable iron electrode is also capable of continuous discharge at rates as high as 3C with no noticeable loss in utilization. We have shown that the porosity, pore size and thickness of the sintered electrode can be selected rationally to optimize specific capacity, rate capability and robustness. As a result, these advances in the electrical performance and durability of the iron electrode enables iron-based alkaline batteries to be a viable technology solution for meeting the dire need for large-scale electrical energy storage.« less

A High-Performance Sintered Iron Electrode for Rechargeable Alkaline Batteries to Enable Large-Scale Energy Storage

DOE PAGES

Yang, Chenguang; Manohar, Aswin K.; Narayanan, S. R.

2017-01-07

Iron-based alkaline rechargeable batteries such as iron-air and nickel-iron batteries are particularly attractive for large-scale energy storage because these batteries can be relatively inexpensive, environment- friendly, and also safe. Therefore, our study has focused on achieving the essential electrical performance and cycling properties needed for the widespread use of iron-based alkaline batteries in stationary and distributed energy storage applications.We have demonstrated for the first time, an advanced sintered iron electrode capable of 3500 cycles of repeated charge and discharge at the 1-hour rate and 100% depth of discharge in each cycle, and an average Coulombic efficiency of over 97%. Suchmore » a robust and efficient rechargeable iron electrode is also capable of continuous discharge at rates as high as 3C with no noticeable loss in utilization. We have shown that the porosity, pore size and thickness of the sintered electrode can be selected rationally to optimize specific capacity, rate capability and robustness. As a result, these advances in the electrical performance and durability of the iron electrode enables iron-based alkaline batteries to be a viable technology solution for meeting the dire need for large-scale electrical energy storage.« less

Ultrastable α phase nickel hydroxide as energy storage materials for alkaline secondary batteries

NASA Astrophysics Data System (ADS)

Huang, Haili; Guo, Yinjian; Cheng, Yuanhui

2018-03-01

α Phase nickel hydroxide (α-Ni(OH)2) has higher theoretical capacity than that of commercial β phase Ni(OH)2. But the low stability inhibits its wide application in alkaline rechargeable batteries. Here, we propose a totally new idea to stabilize α phase Ni(OH)2 by introducing large organic molecule into the interlayer spacing together with doping multivalent cobalt into the layered Ni(OH)2 host. Ethylene glycol is served as neutral stabilizer in the interlayer spacing. Nickel is substituted by cobalt to increase the electrostatic attraction between layered Ni(OH)2 host and anion ions in the interlayer spacing. Polyethylene glycol (PEG-200) is utilized to design a three-dimensional network structure. This prepared α-Ni(OH)2-20 exhibits specific capacity as high as 334 mAh g-1and good structural stability even after immersing into strong alkaline zincate solution for 20 days. Ni(OH)2 electrode with a specific capacity of 35 mAh cm-2 is fabricated and used as positive electrode in zinc-nickel single flow batteries, which also shows good cycling stability. This result can provide an important guideline for the rational design and preparation of highly active and stable α phase Ni(OH)2 for alkaline secondary battery.

Abiotically-formed, primary dolomite in the mid-Eocene lacustrine succession at Gebel El-Goza El-Hamra, NE Egypt: An approach to the role of smectitic clays

NASA Astrophysics Data System (ADS)

Wanas, H. A.; Sallam, E.

2016-08-01

This study discusses the role of smectitic clays in the formation of an abiotic (physio-chemical) primary dolomite within an evaporative alkaline-saline marginal lake system, in the absence of carbonate precursor and microbes. The present work has been achieved in terms of textural, mineralogical, and geochemical characteristics of dolostones in the Mid-Eocene (Bartonian) lacustrine succession cropping out at Gebel El-Goza El-Hamra (Shabrawet area, NE Egypt). This lacustrine succession is 15-16 m thick, and made up of alternating horizontal beds of dolostone, marlstone and mudrock that show some pedogenic and subaerial exposure features. The dolostones are composed mainly of dolomite (60-90%), smectite (20-30%) and quartz grains (5-10%). The dolomite comprises fine-crystalline rhombs to micro-spherical crystals with no obvious relics of microbial activity and/or carbonate precursor. It is, ordered, nearly stoichiometric (with 46-50% mole of MgCO3) and has δ18O and δ13C values ranging from + 0.44 to + 2.96 VPDB ‰, and 0.93 to - 8.95 VPDB ‰, respectively. The smectite occurs as thin mats that are commonly intergrown and associated with dolomite. Mineralogical, textural and stable isotopic results of the dolomite indicated that the dolomite was formed as an abiotic primary precipitate in alkaline saline lacustrine systems. In this respect, the gel-like highly viscous smectitic medium plus progressive CO2 degassing, elevated evaporation, low sedimentation rate, low sulphates level and alkaline soil solution lowered the kinetic barriers of dolomite precipitation from solution and promoted the incorporation of Mg2 + in the structure of dolomite. Consequently, the presence of smectitic clays in evaporative saline lakes is significant for dolomite formation because they can generate a gel-like highly viscous medium and provide Mg2 + that can facilitate the physcio-chemical precipitation of primary dolomite from solution at ambient temperatures. However, more work is needed to better characterize the role of clays during dolomite formation in alkaline lacustrine environments at ambient temperatures.

"Supergreen" Renewables: Integration of Mineral Weathering Into Renewable Energy Production for Air CO2 Removal and Storage as Ocean Alkalinity

NASA Astrophysics Data System (ADS)

Rau, G. H.; Carroll, S.; Ren, Z. J.

2015-12-01

Excess planetary CO2 and accompanying ocean acidification are naturally mitigated on geologic time scales via mineral weathering. Here, CO2 acidifies the hydrosphere, which then slowly reacts with silicate and carbonate minerals to produce dissolved bicarbonates that are ultimately delivered to the ocean. This alkalinity not only provides long-term sequestration of the excess atmospheric carbon, but it also chemically counters the effects of ocean acidification by stabilizing or raising pH and carbonate saturation state, thus helping rebalance ocean chemistry and preserving marine ecosystems. Recent research has demonstrated ways of greatly accelerating this process by its integration into energy systems. Specifically, it has been shown (1) that some 80% of the CO2 in a waste gas stream can be spontaneously converted to stable, seawater mineral bicarbonate in the presence of a common carbonate mineral - limestone. This can allow removal of CO2 from biomass combustion and bio-energy production while generating beneficial ocean alkalinity, providing a potentially cheaper and more environmentally friendly negative-CO2-emissions alternative to BECCS. It has also been demonstrated that strong acids anodically produced in a standard saline water electrolysis cell in the formation of H2 can be reacted with carbonate or silicate minerals to generate strong base solutions. These solutions are highly absorptive of air CO2, converting it to mineral bicarbonate in solution. When such electrochemical cells are powered by non-fossil energy (e.g. electricity from wind, solar, tidal, biomass, geothermal, etc. energy sources), the system generates H2 that is strongly CO2-emissions-negative, while producing beneficial marine alkalinity (2-4). The preceding systems therefore point the way toward renewable energy production that, when tightly coupled to geochemical mitigation of CO2 and formation of natural ocean "antacids", forms a high capacity, negative-CO2-emissions, "supergreen" source of fuel or electrcity. 1) http://pubs.acs.org/doi/pdf/10.1021/es102671x2) http://pubs.acs.org/doi/full/10.1021/es800366q3) http://www.pnas.org/content/110/25/10095.full.pdf4) http://pubs.acs.org/doi/abs/10.1021/acs.est.5b00875

High Laccase Expression by Trametes versicolor in a Simulated Textile Effluent with Different Carbon Sources and PHs.

PubMed

Ottoni, Cristiane; Simões, Marta F; Fernandes, Sara; Santos, Cledir R; Lima, Nelson

2016-08-02

Textile effluents are highly polluting and have variable and complex compositions. They can be extremely complex, with high salt concentrations and alkaline pHs. A fixed-bed bioreactor was used in the present study to simulate a textile effluent treatment, where the white-rot fungus, Trametes versicolor, efficiently decolourised the azo dye Reactive Black 5 over 28 days. This occurred under high alkaline conditions, which is unusual, but advantageous, for successful decolourisation processes. Active dye decolourisation was maintained by operation in continuous culture. Colour was eliminated during the course of operation and maximum laccase (Lcc) activity (80.2 U∙L(-1)) was detected after glycerol addition to the bioreactor. Lcc2 gene expression was evaluated with different carbon sources and pH values based on reverse transcriptase-PCR (polymerase chain reaction). Glycerol was shown to promote the highest lcc2 expression at pH 5.5, followed by sucrose and then glucose. The highest levels of expression occurred between three and four days, which corroborate the maximum Lcc activity observed for sucrose and glycerol on the bioreactor. These results give new insights into the use of T. versicolor in textile dye wastewater treatment with high pHs.

Effects of Parameter Uncertainty on Long-Term Simulations of Lake Alkalinity

NASA Astrophysics Data System (ADS)

Lee, Sijin; Georgakakos, Konstantine P.; Schnoor, Jerald L.

1990-03-01

A first-order second-moment uncertainty analysis has been applied to two lakes in the Adirondack Park, New York, to assess the long-term response of lakes to acid deposition. Uncertainty due to parameter error and initial condition error was considered. Because the enhanced trickle-down (ETD) model is calibrated with only 3 years of field data and is used to simulate a 50-year period, the uncertainty in the lake alkalinity prediction is relatively large. When a best estimate of parameter uncertainty is used, the annual average alkalinity is predicted to be -11 ±28 μeq/L for Lake Woods and 142 ± 139 μeq/L for Lake Panther after 50 years. Hydrologic parameters and chemical weathering rate constants contributed most to the uncertainty of the simulations. Results indicate that the uncertainty in long-range predictions of lake alkalinity increased significantly over a 5- to 10-year period and then reached a steady state.

ET Toxic Metals Replacement Review SEA Spring Face to Face

NASA Technical Reports Server (NTRS)

Pratz, Earl

2007-01-01

The information contained in the presentation covers development work carried out under SDS projects. The intent of the effort is to find chrome(VI) free alternates to our current chromated processing solutions. The information presented reports progress in work aimed to replace our alkaline cleaner (Turco 4215), conversion coat (Iridite 14-2) and chrome (VI) compounds used in LOx tank hydrostatic proof test solution. To date we have found candidates for use in the proof test solution and alkaline cleaner. These candidates are in the final stages of testing. Lab data is reported in the presentation.

Dissolution of glass wool, rock wool and alkaline earth silicate wool: morphological and chemical changes in fibers.

PubMed

Campopiano, Antonella; Cannizzaro, Annapaola; Angelosanto, Federica; Astolfi, Maria Luisa; Ramires, Deborah; Olori, Angelo; Canepari, Silvia; Iavicoli, Sergio

2014-10-01

The behavior of alkaline earth silicate (AES) wool and of other biosoluble wools in saline solution simulating physiological fluids was compared with that of a traditional wool belonging to synthetic vitreous fibers. Morphological and size changes of fibers were studied by scanning electron microscopy (SEM). The elements extracted from fibers were analyzed by inductively coupled plasma atomic emission spectrometry. SEM analysis showed a larger reduction of length-weighted geometric mean fiber diameter at 4.5 pH than at 7.4 pH. At the 7.4 pH, AES wool showed a higher dissolution rate and a dissolution time less than a few days. Their dissolution was highly non-congruent with rapid leaching of calcium. Unlike rock wool, glass wool dissolved more rapidly at physiological pH than at acid pH. Dissolution of AES and biosoluble rock wool is accompanied by a noticeable change in morphology while by no change for glass wool. Biosoluble rock wool developed a leached surface with porous honeycomb structure. SEM analysis showed the dissolution for glass wool is mainly due to breakage transverse of fiber at pH 7.4. AES dissolution constant (Kdis) was the highest at pH 7.4, while at pH 4.5 only biosoluble rockwool 1 showed a higher Kdis. Copyright © 2014 Elsevier Inc. All rights reserved.

THE KINETICS OF SAPONIFICATION OF IODOACETIC ACID BY SODIUM HYDROXIDE AND BY CERTAIN ALKALINE BUFFER SOLUTIONS.

PubMed

Brdicka, R

1936-07-20

1. The rate of the saponification of iodoacetic acid in sodium hydroxide and alkaline buffer solutions yielding glycollic acid was measured by means of Heyrovský's polarographic method. 2. From the bimolecular velocity constants, increasing with the ionic strength of the solution, the Brönsted factor, F, which characterizes the primary salt effect, was calculated. 3. In the borate buffer solutions the monomolecular constants of the saponification were determined which, at values above the pH of neutralization of boric acid, show a proportionality to the concentration of hydroxyl anions. Below the pH of neutralization of boric acid, they are proportional to the concentration of borate anions.

Design of Perovskite Oxides as Anion-Intercalation-Type Electrodes for Supercapacitors: Cation Leaching Effect.

PubMed

Liu, Yu; Dinh, Jim; Tade, Moses O; Shao, Zongping

2016-09-14

Oxygen ions can be exploited as a charge carrier to effectively realize a new type of anion-intercalation supercapacitor. In this study, to get some useful guidelines for future materials development, we comparatively studied SrCoO3-δ (SC), Ba0.5Sr0.5Co0.8Fe0.2O3-δ (BSCF), and Co3O4 as electrodes in supercapacitors with aqueous alkaline electrolyte. The effect of interaction between the electrode materials with the alkaline solution was focused on the structure and specific surface area of the electrode material, and ultimately the electrochemical performance was emphasized. Both BSCF and SC were found to experience cation leaching in alkaline solution, resulting in an increase in the specific surface area of the material, but overleaching caused the damage of perovskite structure of BSCF. Barium leaching was more serious than strontium, and the cation leaching was component dependent. Although high initial capacitance was achieved for BSCF, it was not a good candidate as intercalation-type electrode for supercapacitor because of poor cycling stability from serious Ba(2+) and Sr(2+) leaching. Instead, SC was a favorable electrode candidate for practical use in supercapacitors due to its high capacity and proper cation leaching capacity, which brought beneficial effect on cycling stability. It is suggested that cation leaching effect should be seriously considered in the development of new perovskite materials as electrodes for supercapacitors.

Snowmelt controls on concentration-discharge relationships and the balance of oxidative and acid-base weathering fluxes in an alpine catchment, East River, Colorado: ACID-BASE VERSUS OXIDATIVE WEATHERING FLUXES

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

Winnick, Matthew J.; Carroll, Rosemary W. H.; Williams, Kenneth H.

Although important for riverine solute and nutrient fluxes, the connections between biogeochemical processes and subsurface hydrology remain poorly characterized. We investigate these couplings in the East River, CO, a high-elevation shale-dominated catchment in the Rocky Mountains, using concentration-discharge (C-Q) relationships for major cations, anions, and organic carbon. Dissolved organic carbon (DOC) displays a positive C-Q relationship with clockwise hysteresis, indicating mobilization and depletion of DOC in the upper soil horizons and emphasizing the importance of shallow flowpaths during snowmelt. Cation and anion concentrations demonstrate that carbonate weathering, which dominates solute fluxes, is promoted by both sulfuric acid derived from pyritemore » oxidation in the shale bedrock and carbonic acid derived from subsurface respiration. Sulfuric acid weathering dominates during baseflow conditions when waters infiltrate below the inferred pyrite oxidation front, whereas carbonic acid weathering plays a dominant role during snowmelt as a result of shallow flowpaths. Differential C-Q relationships between solutes suggest that infiltrating waters approach calcite saturation before reaching the pyrite oxidation front, after which sulfuric acid reduces carbonate alkalinity. This reduction in alkalinity results in CO 2 outgassing when waters equilibrate to surface conditions, and reduces the riverine export of carbon and alkalinity by roughly 33% annually. In conclusion, future changes in snowmelt dynamics that control the balance of carbonic and sulfuric acid weathering may substantially alter carbon cycling in the East River. Ultimately, we demonstrate that differential C-Q relationships between major solutes can provide unique insights into the complex subsurface flow and biogeochemical dynamics that operate at catchment scales.« less

Snowmelt controls on concentration-discharge relationships and the balance of oxidative and acid-base weathering fluxes in an alpine catchment, East River, Colorado: ACID-BASE VERSUS OXIDATIVE WEATHERING FLUXES

DOE PAGES

Winnick, Matthew J.; Carroll, Rosemary W. H.; Williams, Kenneth H.; ...

2017-03-01

Although important for riverine solute and nutrient fluxes, the connections between biogeochemical processes and subsurface hydrology remain poorly characterized. We investigate these couplings in the East River, CO, a high-elevation shale-dominated catchment in the Rocky Mountains, using concentration-discharge (C-Q) relationships for major cations, anions, and organic carbon. Dissolved organic carbon (DOC) displays a positive C-Q relationship with clockwise hysteresis, indicating mobilization and depletion of DOC in the upper soil horizons and emphasizing the importance of shallow flowpaths during snowmelt. Cation and anion concentrations demonstrate that carbonate weathering, which dominates solute fluxes, is promoted by both sulfuric acid derived from pyritemore » oxidation in the shale bedrock and carbonic acid derived from subsurface respiration. Sulfuric acid weathering dominates during baseflow conditions when waters infiltrate below the inferred pyrite oxidation front, whereas carbonic acid weathering plays a dominant role during snowmelt as a result of shallow flowpaths. Differential C-Q relationships between solutes suggest that infiltrating waters approach calcite saturation before reaching the pyrite oxidation front, after which sulfuric acid reduces carbonate alkalinity. This reduction in alkalinity results in CO 2 outgassing when waters equilibrate to surface conditions, and reduces the riverine export of carbon and alkalinity by roughly 33% annually. In conclusion, future changes in snowmelt dynamics that control the balance of carbonic and sulfuric acid weathering may substantially alter carbon cycling in the East River. Ultimately, we demonstrate that differential C-Q relationships between major solutes can provide unique insights into the complex subsurface flow and biogeochemical dynamics that operate at catchment scales.« less

In Situ Quantification of [Re(CO)3]+ by Fluorescence Spectroscopy in Simulated Hanford Tank Waste.

PubMed

Branch, Shirmir D; French, Amanda D; Lines, Amanda M; Rapko, Brian M; Heineman, William R; Bryan, Samuel A

2018-02-06

A pretreatment protocol is presented that allows for the quantitative conversion and subsequent in situ spectroscopic analysis of [Re(CO) 3 ] + species in simulated Hanford tank waste. In this test case, the nonradioactive metal rhenium is substituted for technetium (Tc-99), a weak beta emitter, to demonstrate proof of concept for a method to measure a nonpertechnetate form of technetium in Hanford tank waste. The protocol encompasses adding a simulated waste sample containing the nonemissive [Re(CO) 3 ] + species to a developer solution that enables the rapid, quantitative conversion of the nonemissive species to a luminescent species which can then be detected spectroscopically. The [Re(CO) 3 ] + species concentration in an alkaline, simulated Hanford tank waste supernatant can be quantified by the standard addition method. In a test case, the [Re(CO) 3 ] + species was measured to be at a concentration of 38.9 μM, which was a difference of 2.01% from the actual concentration of 39.7 μM.

Germanium precipitation from collecting-mains liquor with tannin extract in an alkaline medium

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

Medvedev, K.P.; Mikhailov, N.F.; Petrapol'skaya, V.M.

1976-01-01

It is proposed to precipitate germanium in a slightly alkaline medium, with a neutral solution of tannin extract in aqueous alkali. The effects of various factors on germanium recovery from collecting-mains liquors have been studied.

CO2-Free Power Generation on an Iron Group Nanoalloy Catalyst via Selective Oxidation of Ethylene Glycol to Oxalic Acid in Alkaline Media

PubMed Central

Matsumoto, Takeshi; Sadakiyo, Masaaki; Ooi, Mei Lee; Kitano, Sho; Yamamoto, Tomokazu; Matsumura, Syo; Kato, Kenichi; Takeguchi, Tatsuya; Yamauchi, Miho

2014-01-01

An Fe group ternary nanoalloy (NA) catalyst enabled selective electrocatalysis towards CO2-free power generation from highly deliverable ethylene glycol (EG). A solid-solution-type FeCoNi NA catalyst supported on carbon was prepared by a two-step reduction method. High-resolution electron microscopy techniques identified atomic-level mixing of constituent elements in the nanoalloy. We examined the distribution of oxidised species, including CO2, produced on the FeCoNi nanoalloy catalyst in the EG electrooxidation under alkaline conditions. The FeCoNi nanoalloy catalyst exhibited the highest selectivities toward the formation of C2 products and to oxalic acid, i.e., 99 and 60%, respectively, at 0.4 V vs. the reversible hydrogen electrode (RHE), without CO2 generation. We successfully generated power by a direct EG alkaline fuel cell employing the FeCoNi nanoalloy catalyst and a solid-oxide electrolyte with oxygen reduction ability, i.e., a completely precious-metal-free system. PMID:25004118

Development of an analytical technique for the detection of alteration minerals formed in bentonite by reaction with alkaline solutions

NASA Astrophysics Data System (ADS)

Sakamoto, H.; Shibata, M.; Owada, H.; Kaneko, M.; Kuno, Y.; Asano, H.

A multibarrier system consisting of cement-based backfill, structures and support materials, and a bentonite-based buffer material has been studied for the TRU waste disposal concept being developed in Japan, the aim being to restrict the migration of radionuclides. Concern regarding bentonite-based materials in this disposal environment relates to long-term alteration under hyper-alkaline conditions due to the presence of cementitious materials. In tests simulating the interaction between bentonite and cement, formation of secondary minerals due to alteration reactions under the conditions expected for geological disposal of TRU waste (equilibrated water with cement at low liquid/solid ratio) has not been observed, although alteration was observed under extremely hyper-alkaline conditions with high temperatures. This was considered to be due to the fact that analysis of C-S-H gel formed at the interface as a secondary mineral was difficult using XRD, because of its low crystallinity and low content. This paper describes an analytical technique for the characterization of C-S-H gel using a heavy liquid separation method which separates C-S-H gel from Kunigel V1 bentonite (bentonite produced in Japan) based on the difference in specific gravity between the crystalline minerals constituting Kunigel V1 and the secondary C-S-H gel. For development of C-S-H gel separation methods, simulated alteration samples were prepared by mixing 990 mg of unaltered Kunigel V1 and 10 mg of C-S-H gel synthesized using pure chemicals at a ratio of Ca/Si = 1.2. The simulated alteration samples were dispersed in bromoform-methanol mixtures with specific gravities ranging from 2.00 to 2.57 g/cm 3 and subjected to centrifuge separation to recover the light density fraction. Subsequent XRD analysis to identify the minerals was complemented by dissolution in 0.6 N hydrochloric acid to measure the Ca and Si contents. The primary peak (2 θ = 29.4°, Cu Kα) and secondary peaks (2 θ = 32.1° and 50.1°, Cu Kα) of the C-S-H gel, which could not be distinguished before the heavy liquid separation, were clearly identified by XRD after separation. The result of the analyses of the light density fraction indicates highest recovery of C-S-H gel and least inclusion of bentonite for separation using heavy liquid with a specific gravity of 2.10 g/cm 3. The traces of bentonite minerals included in the suspension were identified to be montmorillonite, quartz, clinoptilolite, and calcite. The separation technique was also tested for Ca-bentonite prepared by passing a calcium hydroxide solution through a bentonite (Kunigel V1)-silica sand mixture. The results indicated that the technique would also be applicable to separation of C-S-H gel from Ca-bentonite.

Aluminum corrosion mitigation in alkaline electrolytes containing hybrid inorganic/organic inhibitor system for power sources applications

NASA Astrophysics Data System (ADS)

Gelman, Danny; Lasman, Itay; Elfimchev, Sergey; Starosvetsky, David; Ein-Eli, Yair

2015-07-01

The severe corrosion accompanied with hydrogen evolution process is the main obstacle preventing the implementation of Al as an anode in alkaline batteries. It impairs the functionality of alkaline battery, due to a drastic capacity loss and a short shelf life. The possibility to reduce Al corrosion rate in alkaline solution with the use of hybrid organic∖inorganic inhibitor based on poly (ethylene glycol) di-acid (PEG di-acid) and zinc oxide (ZnO) was examined in this work. A correlation between an Al corrosion rates and the concentrations of both PEG di-acid and ZnO in alkaline is shown. Selecting 5000 ppm PEG di-acid and 16 gr/l ZnO provides substantial corrosion protection of Al, reducing the corrosion rate in a strong alkaline solution by more than one order of magnitude. Moreover, utilizing the same formulation results in increase in Al-air battery discharge capacity, from 44.5 (for a battery utilizing only KOH in the electrolyte) to 70 mhA/cm2 (for a battery utilizing ZnO/PEG di-acid hybrid inhibitor in the electrolyte). The morphology and composition of the Al electrode surface (studied by SEM, EDS, and XRD) depend on PEG di-acid and ZnO concentrations.

Modelling and scale-up of chemical flooding

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

Pope, G.A.; Lake, L.W.; Sepehrnoori, K.

1990-03-01

The objective of this research is to develop, validate, and apply a comprehensive chemical flooding simulator for chemical recovery processes involving surfactants, polymers, and alkaline chemicals in various combinations. This integrated program includes components of laboratory experiments, physical property modelling, scale-up theory, and numerical analysis as necessary and integral components of the simulation activity. We have continued to develop, test, and apply our chemical flooding simulator (UTCHEM) to a wide variety of laboratory and reservoir problems involving tracers, polymers, polymer gels, surfactants, and alkaline agents. Part I is an update on the Application of Higher-Order Methods in Chemical Flooding Simulation.more » This update focuses on the comparison of grid orientation effects for four different numerical methods implemented in UTCHEM. Part II is on Simulation Design Studies and is a continuation of Saad's Big Muddy surfactant pilot simulation study reported last year. Part III reports on the Simulation of Gravity Effects under conditions similar to those of some of the oil reservoirs in the North Sea. Part IV is on Determining Oil Saturation from Interwell Tracers UTCHEM is used for large-scale interwell tracer tests. A systematic procedure for estimating oil saturation from interwell tracer data is developed and a specific example based on the actual field data provided by Sun E P Co. is given. Part V reports on the Application of Vectorization and Microtasking for Reservoir Simulation. Part VI reports on Alkaline Simulation. The alkaline/surfactant/polymer flood compositional simulator (UTCHEM) reported last year is further extended to include reactions involving chemical species containing magnesium, aluminium and silicon as constituent elements. Part VII reports on permeability and trapping of microemulsion.« less

Batch and column adsorption of herbicide fluroxypyr on different types of activated carbons from water with varied degrees of hardness and alkalinity.

PubMed

Pastrana-Martínez, L M; López-Ramón, M V; Fontecha-Cámara, M A; Moreno-Castilla, C

2010-02-01

There has been little research into the effects of the water hardness and alkalinity of surface waters on the adsorption of herbicides on activated carbons. The aim of this study was to determine the influence of these water characteristics on fluroxypyr adsorption on different activated carbons. At low fluroxypyr surface concentrations, the amount adsorbed from distilled water was related to the surface hydrophobicity. Surface area of carbons covered by fluroxypyr molecules ranged from 60 to 65%. Variations in fluroxypyr solubility with water hardness and alkalinity showed a salting-in effect. Calcium, magnesium and bicarbonate ions were adsorbed to a varied extent on the activated carbons. The presence of fluroxypyr in solution decreased their adsorption due to a competition effect. K(F) from the Freundlich equation linearly increased with water hardness due to salt-screened electrostatic repulsions between charged fluroxypyr molecules. The amount adsorbed from distilled water was largest at high fluroxypyr solution concentrations, because there was no competition between inorganic ions and fluroxypyr molecules. The column breakthrough volume and the amount adsorbed at breakthrough were smaller in tap versus distilled water. Carbon consumption was lower with activated carbon cloth than with the use of granular activated carbon. (c) 2009 Elsevier Ltd. All rights reserved.

The effect of different parameters on the development of compressive strength of oil palm shell geopolymer concrete.

PubMed

Kupaei, Ramin Hosseini; Alengaram, U Johnson; Jumaat, Mohd Zamin

2014-01-01

This paper presents the experimental results of an on-going research project on geopolymer lightweight concrete using two locally available waste materials--low calcium fly ash (FA) and oil palm shell (OPS)--as the binder and lightweight coarse aggregate, respectively. OPS was pretreated with three different alkaline solutions of sodium hydroxide (NaOH), potassium hydroxide, and sodium silicate as well as polyvinyl alcohol (PVA) for 30 days; afterwards, oil palm shell geopolymer lightweight concrete (OPSGPC) was cast by using both pretreated and untreated OPSs. The effect of these solutions on the water absorption of OPS, and the development of compressive strength in different curing conditions of OPSGPC produced by pretreated OPS were investigated; subsequently the influence of NaOH concentration, alkaline solution to FA ratio (A/FA), and different curing regimes on the compressive strength and density of OPSGPC produced by untreated OPS was inspected. The 24-hour water absorption value for OPS pretreated with 20% and 50% PVA solution was about 4% compared to 23% for untreated OPS. OPSGPC produced from OPS treated with 50% PVA solution produced the highest compressive strength of about 30 MPa in ambient cured condition. The pretreatment with alkaline solution did not have a significant positive effect on the water absorption of OPS aggregate and the compressive strength of OPSGPC. The result revealed that a maximum compressive strength of 32 MPa could be obtained at a temperature of 65°C and curing period of 4 days. This investigation also found that an A/FA ratio of 0.45 has the optimum amount of alkaline liquid and it resulted in the highest level of compressive strength.

The Effect of Different Parameters on the Development of Compressive Strength of Oil Palm Shell Geopolymer Concrete

PubMed Central

Kupaei, Ramin Hosseini; Alengaram, U. Johnson; Jumaat, Mohd Zamin

2014-01-01

This paper presents the experimental results of an on-going research project on geopolymer lightweight concrete using two locally available waste materials—low calcium fly ash (FA) and oil palm shell (OPS)—as the binder and lightweight coarse aggregate, respectively. OPS was pretreated with three different alkaline solutions of sodium hydroxide (NaOH), potassium hydroxide, and sodium silicate as well as polyvinyl alcohol (PVA) for 30 days; afterwards, oil palm shell geopolymer lightweight concrete (OPSGPC) was cast by using both pretreated and untreated OPSs. The effect of these solutions on the water absorption of OPS, and the development of compressive strength in different curing conditions of OPSGPC produced by pretreated OPS were investigated; subsequently the influence of NaOH concentration, alkaline solution to FA ratio (A/FA), and different curing regimes on the compressive strength and density of OPSGPC produced by untreated OPS was inspected. The 24-hour water absorption value for OPS pretreated with 20% and 50% PVA solution was about 4% compared to 23% for untreated OPS. OPSGPC produced from OPS treated with 50% PVA solution produced the highest compressive strength of about 30 MPa in ambient cured condition. The pretreatment with alkaline solution did not have a significant positive effect on the water absorption of OPS aggregate and the compressive strength of OPSGPC. The result revealed that a maximum compressive strength of 32 MPa could be obtained at a temperature of 65°C and curing period of 4 days. This investigation also found that an A/FA ratio of 0.45 has the optimum amount of alkaline liquid and it resulted in the highest level of compressive strength. PMID:25531006

Energetics of Amino Acid Synthesis in Alkaline Hydrothermal Environments

NASA Astrophysics Data System (ADS)

Kitadai, Norio

2015-12-01

Alkaline hydrothermal systems have received considerable attention as candidates for the origin and evolution of life on the primitive Earth. Nevertheless, sufficient information has not yet been obtained for the thermodynamic properties of amino acids, which are necessary components for life, at high temperatures and alkaline pH. These properties were estimated using experimental high-temperature volume and heat capacity data reported in the literature for several amino acids, together with correlation algorithms and the revised Helgeson-Kirkham-Flowers (HKF) equations of state. This approach enabled determination of a complete set of the standard molal thermodynamic data and the revised HKF parameters for the 20 protein amino acids in their zwitterionic and ionization states. The obtained dataset was then used to evaluate the energetics of amino acid syntheses from simple inorganic precursors (CO2, H2, NH3 and H2S) in a simulated alkaline hydrothermal system on the Hadean Earth. Results show that mixing between CO2-rich seawater and the H2-rich hydrothermal fluid can produce energetically favorable conditions for amino acid syntheses, particularly in the lower-temperature region of such systems. Together with data related to the pH and temperature dependences of the energetics of amino acid polymerizations presented in earlier reports, these results suggest the following. Hadean alkaline hydrothermal settings, where steep pH and temperature gradients may have existed between cool, slightly acidic Hadean ocean water and hot, alkaline hydrothermal fluids at the vent-ocean interface, may be energetically the most suitable environment for the synthesis and polymerization of amino acids.

Energetics of Amino Acid Synthesis in Alkaline Hydrothermal Environments.

PubMed

Kitadai, Norio

2015-12-01

Alkaline hydrothermal systems have received considerable attention as candidates for the origin and evolution of life on the primitive Earth. Nevertheless, sufficient information has not yet been obtained for the thermodynamic properties of amino acids, which are necessary components for life, at high temperatures and alkaline pH. These properties were estimated using experimental high-temperature volume and heat capacity data reported in the literature for several amino acids, together with correlation algorithms and the revised Helgeson-Kirkham-Flowers (HKF) equations of state. This approach enabled determination of a complete set of the standard molal thermodynamic data and the revised HKF parameters for the 20 protein amino acids in their zwitterionic and ionization states. The obtained dataset was then used to evaluate the energetics of amino acid syntheses from simple inorganic precursors (CO2, H2, NH3 and H2S) in a simulated alkaline hydrothermal system on the Hadean Earth. Results show that mixing between CO2-rich seawater and the H2-rich hydrothermal fluid can produce energetically favorable conditions for amino acid syntheses, particularly in the lower-temperature region of such systems. Together with data related to the pH and temperature dependences of the energetics of amino acid polymerizations presented in earlier reports, these results suggest the following. Hadean alkaline hydrothermal settings, where steep pH and temperature gradients may have existed between cool, slightly acidic Hadean ocean water and hot, alkaline hydrothermal fluids at the vent-ocean interface, may be energetically the most suitable environment for the synthesis and polymerization of amino acids.

The influence of polymeric component of bioactive glass-based nanocomposite paste on its rheological behaviors and in vitro responses: hyaluronic acid versus sodium alginate.

PubMed

Sohrabi, Mehri; Hesaraki, Saeed; Kazemzadeh, Asghar

2014-04-01

Different biocomposite pastes were prepared from a solid phase that was nanoparticles of sol-gel-derived bioactive glass and different liquid phases including 3% hyaluronic acid solution, sodium alginate solutions (3% and 10 %) or mixtures of hyaluronic acid and sodium alginate (3% or 10 %) solutions in 50:50 volume ratio. Rheological properties of the pastes were measured in both rotatory and oscillatory modes. The washout behavior and in vitro apatite formation of the pastes were determined by soaking them in simulated body fluid under dynamic situation for 14 days. The proliferation and alkaline phosphatase activity of MG-63 osteoblastic cells were also determined using extracts of the pastes. All pastes could be easily injected from the standard syringes with different tip diameters. All pastes exhibited visco-elastic character, but a nonthixotropic paste was obtained using hyaluronic acid in which the loss modulus was higher than the storage modulus. The thixotropy and storage modulus were increasingly improved by adding/using sodium alginate as mixing liquid. Moreover, the pastes in which the liquid phase was sodium alginate or mixture of hyaluronic acid and 10% sodium alginate solution revealed better apatite formation ability and washout resistance than that made of hyaluronic acid alone. No cytotoxicity effects were observed by extracts of the pastes on osteoblasts but better alkaline phosphatase activity was found for the pastes containing hyaluronic acid. Overall, injectable biocomposites can be produced by mixing bioactive glass nanoparticles and sodium alginate/hyaluronic acid polymers. They are potentially useful for hard and even soft tissues treatments. Copyright © 2013 Wiley Periodicals, Inc.

The role of halide ions on the electrochemical behaviour of iron in alkali solutions

NASA Astrophysics Data System (ADS)

Begum, S. Nathira; Muralidharan, V. S.; Basha, C. Ahmed

2008-02-01

Active dissolution and passivation of transition metals in alkali solutions is of technological importance in batteries. The performance of alkaline batteries is decided by the presence of halides as they influence passivation. Cyclic voltammetric studies were carried out on iron in different sodium hydroxide solutions in presence of halides. In alkali solutions iron formed hydroxo complexes and their polymers in the interfacial diffusion layer. With progress of time they formed a cation selective layer. The diffusion layer turned into bipolar ion selective layer consisted of halides, a selective inner sublayer to the metal side and cation selective outer layer to the solution side. At very high anodic potentials, dehydration and deprotonation led to the conversion of salt layer into an oxide.

Effect of alkalinity on nitrite accumulation in treatment of coal chemical industry wastewater using moving bed biofilm reactor.

PubMed

Hou, Baolin; Han, Hongjun; Jia, Shengyong; Zhuang, Haifeng; Zhao, Qian; Xu, Peng

2014-05-01

Nitrogen removal via nitrite (the nitrite pathway) is more suitable for carbon-limited industrial wastewater. Partial nitrification to nitrite is the primary step to achieve nitrogen removal via nitrite. The effect of alkalinity on nitrite accumulation in a continuous process was investigated by progressively increasing the alkalinity dosage ratio (amount of alkalinity to ammonia ratio, mol/mol). There is a close relationship among alkalinity, pH and the state of matter present in aqueous solution. When alkalinity was insufficient (compared to the theoretical alkalinity amount), ammonia removal efficiency increased first and then decreased at each alkalinity dosage ratio, with an abrupt removal efficiency peak. Generally, ammonia removal efficiency rose with increasing alkalinity dosage ratio. Ammonia removal efficiency reached to 88% from 23% when alkalinity addition was sufficient. Nitrite accumulation could be achieved by inhibiting nitrite oxidizing bacteria (NOB) by free ammonia (FA) in the early period and free nitrous acid in the later period of nitrification when alkalinity was not adequate. Only FA worked to inhibit the activity of NOB when alkalinity addition was sufficient. Copyright © 2014 The Research Centre for Eco-Environmental Sciences, Chinese Academy of Sciences. Published by Elsevier B.V. All rights reserved.

Smectite formation in the presence of sulfuric acid: Implications for acidic smectite formation on early Mars

NASA Astrophysics Data System (ADS)

Peretyazhko, T. S.; Niles, P. B.; Sutter, B.; Morris, R. V.; Agresti, D. G.; Le, L.; Ming, D. W.

2018-01-01

The excess of orbital detection of smectite deposits compared to carbonate deposits on the martian surface presents an enigma because smectite and carbonate formations are both favored alteration products of basalt under neutral to alkaline conditions. We propose that Mars experienced acidic events caused by sulfuric acid (H2SO4) that permitted phyllosilicate, but inhibited carbonate, formation. To experimentally verify this hypothesis, we report the first synthesis of smectite from Mars-analogue glass-rich basalt simulant (66 wt% glass, 32 wt% olivine, 2 wt% chromite) in the presence of H2SO4 under hydrothermal conditions (∼200 °C). Smectites were analyzed by X-ray diffraction, Mössbauer spectroscopy, visible and near-infrared reflectance spectroscopy and electron microprobe to characterize mineralogy and chemical composition. Solution chemistry was determined by Inductively Coupled Plasma Mass Spectrometry. Basalt simulant suspensions in 11-42 mM H2SO4 were acidic with pH ≤ 2 at the beginning of incubation and varied from acidic (pH 1.8) to mildly alkaline (pH 8.4) at the end of incubation. Alteration of glass phase during reaction of the basalt simulant with H2SO4 led to formation of the dioctahedral smectite at final pH ∼3 and trioctahedral smectite saponite at final pH ∼4 and higher. Anhydrite and hematite formed in the final pH range from 1.8 to 8.4 while natroalunite was detected at pH 1.8. Hematite was precipitated as a result of oxidative dissolution of olivine present in Adirondack basalt simulant. Formation of secondary phases, including smectite, resulted in release of variable amounts of Si, Mg, Na and Ca while solubilization of Al and Fe was low. Comparison of mineralogical and solution chemistry data indicated that the type of smectite (i.e., dioctahedral vs trioctahedral) was likely controlled by Mg leaching from altering basalt and substantial Mg loss created favorable conditions for formation of dioctahedral smectite. We present a model for global-scale smectite formation on Mars via acid-sulfate conditions created by the volcanic outgassing of SO2 in the Noachian and early Hesperian.

Effective treatment of alkaline Cr(VI) contaminated leachate using a novel Pd-bionanocatalyst: Impact of electron donor and aqueous geochemistry

PubMed Central

Watts, Mathew P.; Coker, Victoria S.; Parry, Stephen A.; Thomas, Russell A.P.; Kalin, Robert; Lloyd, Jonathan R.

2015-01-01

Palladium catalysts offer the potential for the effective treatment of a variety of priority reducible pollutants in natural waters. In this study, microbially synthesized magnetite nanoparticles were functionalized with Pd(0), creating a highly reactive, magnetically recoverable, nano-scale catalyst (Pd-BnM). This was then investigated for the treatment of model Cr(VI) contaminated solutions at a range of pH values, and also alkaline Cr(VI) contaminated leachates from chromite ore processing residue (COPR); a contaminant issue of global concern. The sample of COPR used in this study was obtained from a site in Glasgow, UK, where extensive Cr(VI) contamination has been reported. In initial experiments Pd-BnM was supplied with H2 gas or formate as electron donors, and Cr(VI) removal from model synthetic solutions was quantified at various pH values (2–12). Effective removal was noted at neutral to environmentally relevant alkaline (pH 12) pH values, while the use of formate as an electron donor resulted in loss of performance under acidic conditions (pH 2). Reaction kinetics were then assessed with increasing Pd-BnM loading in both model pH 12 Cr(VI) solutions and the COPR leachate. When formate was used as the electron donor for Pd-BnM, to treat COPR leachate, there was significant inhibition of Cr(VI) removal. In contrast, a promotion of reaction rate, was observed when H2 was employed. Upon sustained reaction with model Cr(VI) solutions, in the presence of excess electron donor (formate or H2), appreciable quantities of Cr(VI) were removed before eventual inactivation of the catalyst. Faster onset of inactivation was reported in the COPR leachates, removing 4% and 64% of Cr(VI) observed from model Cr(VI) solutions, when formate and H2 were used as electron donors, respectively. XAS, TEM-EDX and XPS analysis of the catalysts that had been inactivated in the model solution, showed that the surface had an extensive covering of reduced Cr(III), most likely as a CrOOH phase. COPR reacted catalysts recorded a lower abundance of Cr(III) alongside a high abundance of the leachate components Ca and Si, implicating these elements in the faster onset of inactivation. PMID:26146457

Influence of acidic and alkaline waste solution properties on uranium migration in subsurface sediments.

PubMed

Szecsody, Jim E; Truex, Mike J; Qafoku, Nikolla P; Wellman, Dawn M; Resch, Tom; Zhong, Lirong

2013-08-01

This study shows that acidic and alkaline wastes co-disposed with uranium into subsurface sediments have significant impact on changes in uranium retardation, concentration, and mass during downward migration. For uranium co-disposal with acidic wastes, significant rapid (i.e., hours) carbonate and slow (i.e., 100 s of hours) clay dissolution resulted, releasing significant sediment-associated uranium, but the extent of uranium release and mobility change was controlled by the acid mass added relative to the sediment proton adsorption capacity. Mineral dissolution in acidic solutions (pH2) resulted in a rapid (<10 h) increase in aqueous carbonate (with Ca(2+), Mg(2+)) and phosphate and a slow (100 s of hours) increase in silica, Al(3+), and K(+), likely from 2:1 clay dissolution. Infiltration of uranium with a strong acid resulted in significant shallow uranium mineral dissolution and deeper uranium precipitation (likely as phosphates and carbonates) with downward uranium migration of three times greater mass at a faster velocity relative to uranium infiltration in pH neutral groundwater. In contrast, mineral dissolution in an alkaline environment (pH13) resulted in a rapid (<10h) increase in carbonate, followed by a slow (10 s to 100 s of hours) increase in silica concentration, likely from montmorillonite, muscovite, and kaolinite dissolution. Infiltration of uranium with a strong base resulted in not only uranium-silicate precipitation (presumed Na-boltwoodite) but also desorption of natural uranium on the sediment due to the high ionic strength solution, or 60% greater mass with greater retardation compared with groundwater. Overall, these results show that acidic or alkaline co-contaminant disposal with uranium can result in complex depth- and time-dependent changes in uranium dissolution/precipitation reactions and uranium sorption, which alter the uranium migration mass, concentration, and velocity. Copyright © 2013 Elsevier B.V. All rights reserved.

An experimental flow-through assessment of acidic Fe/Mg smectite formation on early Mars

NASA Astrophysics Data System (ADS)

Sutter, B.; Peretyazhko, T.; Garcia, A. H.; Ming, D. W.

2017-12-01

Orbital observations have detected the phyllosilicate smectite in layered material hundreds of meters thick, intracrater depositional fans, and plains sediments on Mars; however, the detection of carbonate deposits is limited. Instead of neutral/alkaline conditions during the Noachian, early Mars may have experienced mildly acidic conditions derived from volcanic acid-sulfate solutions that allowed Fe/Mg smectite formation but prevented widespread carbonate formation. The detection of acid sulfates (e.g., jarosite) associated with smectite in Mawrth Vallis supports this hypothesis. Previous work demonstrated smectite (saponite) formation in closed hydrologic systems (batch reactor) from basaltic glass at pH 4 and 200°C (Peretyazhko et al., 2016 GCA). This work presents results from alteration of basaltic glass from alkaline to acidic conditions in open hydrologic systems (flow-through reactor). Preliminary experiments exposed basaltic glass to deionized water at 190°C at 0.25 ml/min where solution pH equilibrated to 9.5. These initial high pH experiments were conducted to evaluate the flow-through reactor system before working with lower pHs. Smectite at this pH was not produced and instead X-ray diffraction results consistent with serpentine was detected. Experiments are in progress exposing basaltic glass from pH 8 down to pH 3 to determine what range of pHs could allow for smectite formation in this experimental open-system. The production of smectite under an experimental open-system at low pHs if successful, would support a significant paradigm shift regarding the geochemical evolution of early Mars: Early Mars geochemical solutions were mildly acidic, not neutral/alkaline. This could have profound implications regarding early martain microbiology where acid conditions instead of neutral/alkaline conditions will require further research in terrestrial analogs to address the potential for biosignature preservation on Mars (Johnson et al., 2016, LPSC).

Removal of NO from flue gas by aqueous chlorine-dioxide scrubbing solution in a lab-scale bubbling reactor.

PubMed

Deshwal, Bal Raj; Jin, Dong Seop; Lee, Si Hyun; Moon, Seung Hyun; Jung, Jong Hyeon; Lee, Hyung Keun

2008-02-11

The present study attempts to clean up nitric oxide from the simulated flue gas using aqueous chlorine-dioxide solution in the bubbling reactor. Chlorine-dioxide is generated by chloride-chlorate process. Experiments are carried out to examine the effect of various operating variables like input NO concentration, presence of SO(2), pH of the solution and NaCl feeding rate on the NO(x) removal efficiency at 45 degrees C. Complete oxidation of nitric oxide into nitrogen dioxide occurred on passing sufficient ClO(2) gas into the scrubbing solution. NO is finally converted into nitrate and ClO(2) is reduced into chloride ions. A plausible reaction mechanism concerning NO(x) removal by ClO(2) is suggested. DeNO(x) efficiency increased slightly with the increasing input NO concentration. The presence of SO(2) improved the NO(2) absorption but pH of solution showed marginal effect on NO(2) absorption. NO(x) removal mechanism changed when medium of solution changed from acidic to alkaline. A constant NO(x) removal efficiency of about 60% has been achieved in the wide pH range of 3-11 under optimized conditions.

Treatment of Salmonella enterica serovar Enteritidis with a sublethal concentration of trisodium phosphate or alkaline pH induces thermotolerance.

PubMed

Sampathkumar, Balamurugan; Khachatourians, George G; Korber, Darren R

2004-08-01

The responses of Salmonella enterica serovar Enteritidis to a sublethal dose of trisodium phosphate (TSP) and its equivalent alkaline pH made with NaOH were examined. Pretreatment of S. enterica serovar Enteritidis cells with 1.5% TSP or pH 10.0 solutions resulted in a significant increase in thermotolerance, resistance to 2.5% TSP, resistance to high pH, and sensitivity to acid and H(2)O(2). Protein inhibition studies with chloramphenicol revealed that thermotolerance, unlike resistance to high pH, was dependent on de novo protein synthesis. Two-dimensional polyacrylamide gel electrophoresis (PAGE) of total cellular proteins from untreated control cells resolved as many as 232 proteins, of which 22 and 15% were absent in TSP- or alkaline pH-pretreated cells, respectively. More than 50% of the proteins that were either up- or down-regulated by TSP pretreatment were also up- or down-regulated by alkaline pH pretreatment. Sodium dodecyl sulfate-PAGE analysis of detergent-insoluble outer membrane proteins revealed the up-regulation of at least four proteins. Mass spectrometric analysis showed the up-regulated proteins to include those involved in the transport of small hydrophilic molecules across the cytoplasmic membrane and those that act as chaperones and aid in the export of newly synthesized proteins by keeping them in open conformation. Other up-regulated proteins included common housekeeping proteins like those involved in amino acid biosynthesis, nucleotide metabolism, and aminoacyl-tRNA biosynthesis. In addition to the differential expression of proteins following TSP or alkaline pH treatment, changes in membrane fatty acid composition were also observed. Alkaline pH- or TSP-pretreated cells showed a higher saturated and cyclic to unsaturated fatty acid ratio than did the untreated control cells. These results suggest that the cytoplasmic membrane could play a significant role in the induction of thermotolerance and resistance to other stresses following TSP or alkaline pH treatment.

THE KINETICS OF SAPONIFICATION OF IODOACETIC ACID BY SODIUM HYDROXIDE AND BY CERTAIN ALKALINE BUFFER SOLUTIONS

PubMed Central

Brdička, R.

1936-01-01

1. The rate of the saponification of iodoacetic acid in sodium hydroxide and alkaline buffer solutions yielding glycollic acid was measured by means of Heyrovský's polarographic method. 2. From the bimolecular velocity constants, increasing with the ionic strength of the solution, the Brönsted factor, F, which characterizes the primary salt effect, was calculated. 3. In the borate buffer solutions the monomolecular constants of the saponification were determined which, at values above the pH of neutralization of boric acid, show a proportionality to the concentration of hydroxyl anions. Below the pH of neutralization of boric acid, they are proportional to the concentration of borate anions. PMID:19872968

Alkaline extraction of phenolic compounds from intact sorghum kernels

USDA-ARS?s Scientific Manuscript database

An aqueous sodium hydroxide solution was employed to extract phenolic compounds from whole grain sorghum without decortication or grinding as determined by Oxygen Radical Absorbance Capacity (ORAC). The alkaline extract ORAC values were more stable over 32 days compared to neutralized and freeze dri...

Alkaline electrochemical cells and method of making

NASA Technical Reports Server (NTRS)

Hoyt, H. E.; Pfluger, H. L. (Inventor)

1970-01-01

Equilibrated cellulose ether membranes of increased electrolytic conductivity for use as separators in concentrated alkaline electrochemical cells are investigated. The method of making such membranes by equilibration to the degree desired in an aqueous alkali solution mantained at a temperature below about 10 C is described.

An inorganic CO2 diffusion and dissolution process explains negative CO2 fluxes in saline/alkaline soils.

PubMed

Ma, Jie; Wang, Zhong-Yuan; Stevenson, Bryan A; Zheng, Xin-Jun; Li, Yan

2013-01-01

An 'anomalous' negative flux, in which carbon dioxide (CO2) enters rather than is released from the ground, was studied in a saline/alkaline soil. Soil sterilization disclosed an inorganic process of CO2 dissolution into (during the night) and out of (during the day) the soil solution, driven by variation in soil temperature. Experimental and modeling analysis revealed that pH and soil moisture were the most important determinants of the magnitude of this inorganic CO2 flux. In the extreme cases of air-dried saline/alkaline soils, this inorganic process was predominant. While the diurnal flux measured was zero sum, leaching of the dissolved inorganic carbon in the soil solution could potentially effect net carbon ecosystem exchange. This finding implies that an inorganic module should be incorporated when dealing with the CO2 flux of saline/alkaline land. Neglecting this inorganic flux may induce erroneous or misleading conclusions in interpreting CO2 fluxes of these ecosystems.

An inorganic CO2 diffusion and dissolution process explains negative CO2 fluxes in saline/alkaline soils

PubMed Central

Ma, Jie; Wang, Zhong-Yuan; Stevenson, Bryan A.; Zheng, Xin-Jun; Li, Yan

2013-01-01

An ‘anomalous' negative flux, in which carbon dioxide (CO2) enters rather than is released from the ground, was studied in a saline/alkaline soil. Soil sterilization disclosed an inorganic process of CO2 dissolution into (during the night) and out of (during the day) the soil solution, driven by variation in soil temperature. Experimental and modeling analysis revealed that pH and soil moisture were the most important determinants of the magnitude of this inorganic CO2 flux. In the extreme cases of air-dried saline/alkaline soils, this inorganic process was predominant. While the diurnal flux measured was zero sum, leaching of the dissolved inorganic carbon in the soil solution could potentially effect net carbon ecosystem exchange. This finding implies that an inorganic module should be incorporated when dealing with the CO2 flux of saline/alkaline land. Neglecting this inorganic flux may induce erroneous or misleading conclusions in interpreting CO2 fluxes of these ecosystems. PMID:23778238

The mechanical properties of polyimide films after exposure to high pH

NASA Technical Reports Server (NTRS)

Croall, Catharine I.; St.clair, Terry L.

1992-01-01

Wiring failures linked to insulation damage have drawn much attention in the aerospace industry and concerns have developed regarding the stability and safety of polyimide insulated electrical wire. Several polyimides were selected for evaluation for resistance to degradation by various aqueous alkaline solutions. The polyimides under evaluation include commercially available films such as Kapton (tk), Apical (tk), LaRC(tk)-TPI, and Upilex(tk)R and S, as well as a number of experimental films prepared by NASA Langley. Thermally imidized films were studied for their retention of mechanical properties after exposure to high pH solutions under stressed conditions.

Optical molecular fluorescence determination of ultra-trace beryllium in occupational and environmental samples using highly alkaline conditions.

PubMed

Adams, Lori; Agrawal, Anoop; Cronin, John P; Ashley, Kevin

2017-01-01

Exposures to beryllium (Be), even at extremely low levels, can cause severe health effects in a percentage of those exposed; consequently, occupational exposure limits (OELs) promulgated for this element are the lowest established for any element. This work describes the advantages of using highly alkaline dye solutions for determination of Be in occupational hygiene and environmental samples by means of an optical molecular fluorescence technique after sample extraction in 1-3% (w˖w -1 ) aqueous ammonium bifluoride (NH 4 HF 2 ). Improved attributes include the ability to further enhance the detection limits of Be in extraction solutions of high acidity with minimal dilution, which is particularly beneficial when NH 4 HF 2 solutions of higher concentration are used for extraction of Be from soil samples. Significant improvements in Be method detection limits (MDLs) are obtained at levels many-fold below those reported previously for this methodology. Notably, MDLs for Be of <0.01 ng l -1 / 0.1 ng per sample have been attained, which are superior to MDLs routinely reported for this element by means of the most widely used ultra-trace elemental measurement technique, inductively coupled plasma mass spectrometry (ICP-MS). Very low MDLs for Be are essential in consideration of reductions in OELs for this element in workplace air by health organizations and regulatory agencies in the USA and internationally. Applications of enhanced Be measurements to air filter samples, surface wipe samples, soils and newly-designed occupational air sampler inserts are illustrated.

Effects of sodium hydroxide (NaOH) solution concentration on fly ash-based lightweight geopolymer

NASA Astrophysics Data System (ADS)

Ibrahim, W. M. W.; Hussin, K.; Abdullah, M. M. A.; Kadir, A. A.; Deraman, L. M.

2017-09-01

In this study, the effects of NaOH concentration on properties of fly ash-based lightweight geopolymer were investigated. Lightweight geopolymer was produced using fly ash as source materials and synthetic foaming agents as air entraining agent. The alkaline solutions used in this study are combination of sodium hydroxide (NaOH) and sodium silicate (Na2SiO3) solution. Different molarities of NaOH solution (6M, 8M, 10M, 12M, and 14M) are taken for preparation of 50 x 50 x 50 mm cubes of lightweight geopolymer. The ratio of fly ash/alkaline solution, Na2SiO3/NaOH solution, foaming agent/water and foam/geopolymer paste were kept constant at 2.0, 2.5, 1:10 and 1:1 respectively. The samples were cured at 80°C for 24 hours and left at room temperature for tested at 7 days of ageing. Physical and mechanical properties such as density, water absorption, compressive strength and microstructure property were determined from the cube dried samples. The results show that the NaOH molarity had effects on the properties of lightweight geopolymer with the optimum NaOH molarity found is 12M due to the high strength of 15.6 MPa, lower water absorption (7.3%) and low density (1440 kg/m3). Microstructure analysis shows that the lightweight geopolymer contain some porous structure and unreacted fly ash particles remains.

Physicochemical Approaches for the Remediation of Former Manufactured Gas Plant Tars

NASA Astrophysics Data System (ADS)

Hauswirth, S.; Miller, C. T.

2014-12-01

Former manufactured gas plant (FMGP) tars are one of the most challenging non-aqueous phase liquid (NAPL) contaminants to remediate due to their complex chemical composition, high viscosities, and ability to alter wettability. In this work, we investigate several in situ remediation techniques for the removal of tar from porous media. Batch and column experiments were conducted to test the effectiveness of mobilization, solubilization, and chemical oxidation remediation approaches. Alkaline (NaOH), surfactant (Triton X-100), and polymer (xanthan gum) agents were used in various combinations to reduce tar-water interfacial tension, increase flushing solution viscosity, and increase the solubilities of tar components. Base-activated sodium persulfate was used alone and in combination with surfactant to chemically oxidized tar components. The effectiveness of each method was assessed in terms of both removal of PAHs from the system and reduction of dissolved-phase effluent polycyclic aromatic hydrocarbon (PAH) concentrations. In column studies, alkaline-polymer (AP) and alkaline-surfactant-polymer (ASP) solutions efficiently mobilized 81-93% and 95-96% of residual PAHs, respectively, within two pore volumes. The impact of AP flushing on dissolved-phase PAH concentrations was relatively low; however, the concentrations of several low molar mass PAHs were significantly reduced after ASP flushing. Surfactant-polymer (SP) solutions removed over 99% of residual PAHs through a combination of mobilization and solubilization, and reduced the post-remediation, dissolved-phase total PAH concentration by 98.4-99.1%. Degradation of residual PAHs by base-activated sodium persulfate was relatively low (30-50%), and had little impact on dissolved-phase PAH concentrations.

Numerical analysis for electrokinetic soil processing enhanced by chemical conditioning of the electrode reservoirs.

PubMed

Park, Jin-Soo; Kim, Soon-Oh; Kim, Kyoung-Woong; Kim, Byung Ro; Moon, Seung-Hyeon

2003-04-04

A numerical analysis was undertaken for enhanced electrokinetic soil processing. To perform chemical conditioning of the electrode reservoirs, the electrokinetic soil process employed a membrane as a barrier between the electrode reservoirs and the contaminated soil. An alkaline solution was purged in the anode reservoir that was bounded by the membrane. A mathematical model was used for demonstration of pH change and phenol removal from a kaolinite soil bed, the prediction of pH variations in both electrode reservoirs, and the determination of an optimized injection time of the anode-purging solution. The time-dependent dispersion coefficient was employed in consideration of the averaging effect of the velocity profile on a one-dimensional transport. The estimation of pH and phenol profiles in the soil bed reasonably agreed with the experimental data. The simulation revealed that the removal efficiency of phenol from the kaolinite soil could be improved by maintaining pH of the anode solution.

Characterization and consequences of intermittent sediment oxygenation by macrofauna: interpretation of high-resolution data sets

NASA Astrophysics Data System (ADS)

Meile, C. D.; Dwyer, I.; Zhu, Q.; Polerecky, L.; Volkenborn, N.

2017-12-01

Mineralization of organic matter in marine sediments leads to the depletion of oxygen, while activities of infauna introduce oxygenated seawater to the subsurface. In permeable sediments solutes can be transported from animals and their burrows into the surrounding sediment through advection over several centimeters. The intermittency of pumping leads to a spatially heterogeneous distribution of oxidants, with the temporal dynamics depending on sediment reactivity and activity patterns of the macrofauna. Here, we present results from a series of experiments in which these dynamics are studied at high spatial and temporal resolution using planar optodes. From O2, pH and pCO2 optode data, we quantify rates of O2 consumption and dissolved inorganic carbon production, as well alkalinity dynamics, with millimeter-scale resolution. Simulating intermittent irrigation by imposed pumping patterns in thin aquaria, we derive porewater flow patterns, which together with the production and consumption rates cause the chemical distributions and the establishment of reaction fronts. Our analysis thus establishes a quantitative connection between the locally dynamic redox conditions relevant for biogeochemical transformations and macroscopic observations commonly made with sediment cores.

Interactions of N,N'-dimethylaminoethanol with steel surfaces in alkaline and chlorine containing solutions

NASA Astrophysics Data System (ADS)

Welle, A.; Liao, J. D.; Kaiser, K.; Grunze, M.; Mäder, U.; Blank, N.

1997-10-01

Formulations based on dilute aqueous solutions of N,N'-dimethylethanolamine (DMEA) are used to protect reinforcement steel bars ('rebar') in concrete from corrosion. In a previous paper we discussed the usefulness of X-ray photoelectron spectroscopy (XPS) to detect DMEA adsorbed from solution and the application of secondary neutral mass spectrometry (SNMS) to study migration of DMEA through a cement matrix. In this report we present XPS data of DMEA adsorbed on steel surfaces from alkaline and chlorine containing solutions of variable concentration range and discuss models for the interaction of DMEA with the oxidized steel surface and the mechanism of corrosion inhibition of DMEA. DMEA is strongly bonded to the steel surface and displaces ionic species from the substrate/solution interface hence protecting the ironoxide surface from ionic attack.

SEPARATION PROCESS FOR ZIRCONIUM AND COMPOUNDS THEREOF

DOEpatents

Crandall, H.W.; Thomas, J.R.

1959-06-30

The separation of zirconium from columbium, rare earths, yttrium and the alkaline earth metals, such mixtures of elements occurring in zirconium ores or neutron irradiated uranium is described. According to the invention a suitable separation of zirconium from a one normal acidic aqueous solution containing salts, nitrates for example, of tetravalent zirconium, pentavalent columbium, yttrium, rare earths in the trivalent state and alkaline earths can be obtained by contacting the aqueous solution with a fluorinated beta diketonc alone or in an organic solvent solution, such as benzene, to form a zirconium chelate compound. When the organic solvent is present the zirconium chelate compound is directly extracted; otherwise it is separated by filtration. The zirconium may be recovered from contacting the organic solvent solution containing the chelated compound by back extraction with either an aqueous hydrofluoric acid or an oxalic acid solution.

Passivation Characteristics of Alloy Corrosion-Resistant Steel Cr10Mo1 in Simulating Concrete Pore Solutions: Combination Effects of pH and Chloride

PubMed Central

Ai, Zhiyong; Sun, Wei; Jiang, Jinyang; Song, Dan; Ma, Han; Zhang, Jianchun; Wang, Danqian

2016-01-01

The electrochemical behaviour for passivation of new alloy corrosion-resistant steel Cr10Mo1 immersed in alkaline solutions with different pH values (13.3, 12.0, 10.5, and 9.0) and chloride contents (0.2 M and 1.0 M), was investigated by various electrochemical techniques: linear polarization resistance, electrochemical impedance spectroscopy and capacitance measurements. The chemical composition and structure of passive films were determined by XPS. The morphological features and surface composition of the immersed steel were evaluated by SEM together with EDS chemical analysis. The results evidence that pH plays an important role in the passivation of the corrosion-resistant steel and the effect is highly dependent upon the chloride contents. In solutions with low chloride (0.2 M), the corrosion-resistant steel has notably enhanced passivity with pH falling from 13.3 to 9.0, but does conversely when in presence of high chloride (1.0 M). The passive film on the corrosion-resistant steel presents a bilayer structure: an outer layer enriched in Fe oxides and hydroxides, and an inner layer, rich in Cr species. The film composition varies with pH values and chloride contents. As the pH drops, more Cr oxides are enriched in the film while Fe oxides gradually decompose. Increasing chloride promotes Cr oxides and Fe oxides to transform into their hydroxides with little protection, and this is more significant at lower pH (10.5 and 9.0). These changes annotate passivation characteristics of the corrosion-resistant steel in the solutions of different electrolyte. PMID:28773867

Passivation Characteristics of Alloy Corrosion-Resistant Steel Cr10Mo1 in Simulating Concrete Pore Solutions: Combination Effects of pH and Chloride.

PubMed

Ai, Zhiyong; Sun, Wei; Jiang, Jinyang; Song, Dan; Ma, Han; Zhang, Jianchun; Wang, Danqian

2016-09-01

The electrochemical behaviour for passivation of new alloy corrosion-resistant steel Cr10Mo1 immersed in alkaline solutions with different pH values (13.3, 12.0, 10.5, and 9.0) and chloride contents (0.2 M and 1.0 M), was investigated by various electrochemical techniques: linear polarization resistance, electrochemical impedance spectroscopy and capacitance measurements. The chemical composition and structure of passive films were determined by XPS. The morphological features and surface composition of the immersed steel were evaluated by SEM together with EDS chemical analysis. The results evidence that pH plays an important role in the passivation of the corrosion-resistant steel and the effect is highly dependent upon the chloride contents. In solutions with low chloride (0.2 M), the corrosion-resistant steel has notably enhanced passivity with pH falling from 13.3 to 9.0, but does conversely when in presence of high chloride (1.0 M). The passive film on the corrosion-resistant steel presents a bilayer structure: an outer layer enriched in Fe oxides and hydroxides, and an inner layer, rich in Cr species. The film composition varies with pH values and chloride contents. As the pH drops, more Cr oxides are enriched in the film while Fe oxides gradually decompose. Increasing chloride promotes Cr oxides and Fe oxides to transform into their hydroxides with little protection, and this is more significant at lower pH (10.5 and 9.0). These changes annotate passivation characteristics of the corrosion-resistant steel in the solutions of different electrolyte.

Chemiluminescence-based pesticide biosensor utilizing the intelligent evolved properties of the enzyme alkaline phosphatase

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

Ayyagari, M.; Kamtekar, S.; Pande, R.

A methodology is described for immobilizing the enzyme alkaline phosphatase onto a glass surface using a novel biotinylated copolymer, poly(3-undecylthiophene-co-3- methanoithiophene). A streptavidin conjugate of alkaline phosphatase is used in this study. The biotinylated polymer is attached to the silanized glass surface via hydrophobic interactions and the enzyme is interfaced with the polymer through the classical biotin- streptavidin interaction. Alkaline phosphatase catalyzes the dephosphorylation of a macrocyclic compound, chloro-3-(4-methoxy spiro) (1,2 dioxetane-3-2`-tricyclo-) (3.3.1.1 )-(decani-4-yl) phenyl phosphate, to a species which emits energy by chemiluminescence. This chemiluminescence signal can be detected with a photomultiplier tube for enzymatic catalysis with the biocatalystmore » both in solution and immobilized on a glass surface. The signal generation is inhibited by the organophosphorus based insecticides such as paraoxon as well as nerve agents. We demonstrate in this study that a number of organophosphorus based insecticides inhibit the enzyme-mediated generation of chemiluminescence signal. This is true for the enzyme conjugate both free in solution and immobilized on a glass surface. In solution, the inhibition resembles the case of a partially uncompetitive system. By this type of inhibition we are able to detect pesticides down to about 50 ppb for the enzyme in solution. The pesticide detection limit of immobilized enzyme is currently being investigated. The enzyme is capable of a number of measurement cycles without significant loss of signal level.« less

Recovery of copper and cyanide from waste cyanide solutions using emulsion liquid membrane with LIX 7950 as the carrier.

PubMed

Xie, Feng; Wang, Wei

2017-08-01

The feasibility of using emulsion liquid membranes (ELMs) with the guanidine extractant LIX 7950 as the mobile carrier for detoxifying copper-containing waste cyanide solutions has been determined. Relatively stable ELMs can be maintained under suitable stirring speed during mixing ELMs and the external solution. Effective extraction of copper cyanides by ELMs only occurs at pH below 11. High copper concentration in the external phase and high volume ratio of the external phase to ELMs result in high transport rates of copper and cyanide. High molar ratio of cyanide to copper tends to suppress copper extraction. The presence of thiocyanate ion significantly depresses the transport of copper and cyanide through the membrane while the thiosulfate ion produces less impact on copper removal by ELMs. Zinc and nickel cyanides can also be effectively extracted by ELMs. More than 90% copper and cyanide can be effectively removed from alkaline cyanide solutions by ELMs under suitable experimental conditions, indicating the effectiveness of using the designed ELM for recovering copper and cyanide from waste cyanide solutions.

Construction of Polarized Carbon-Nickel Catalytic Surfaces for Potent, Durable, and Economic Hydrogen Evolution Reactions.

PubMed

Zhou, Min; Weng, Qunhong; Popov, Zakhar I; Yang, Yijun; Antipina, Liubov Yu; Sorokin, Pavel B; Wang, Xi; Bando, Yoshio; Golberg, Dmitri

2018-05-22

Electrocatalytic hydrogen evolution reaction (HER) in alkaline solution is hindered by its sluggish kinetics toward water dissociation. Nickel-based catalysts, as low-cost and effective candidates, show great potentials to replace platinum (Pt)-based materials in the alkaline media. The main challenge regarding this type of catalysts is their relatively poor durability. In this work, we conceive and construct a charge-polarized carbon layer derived from carbon quantum dots (CQDs) on Ni 3 N nanostructure (Ni 3 N@CQDs) surfaces, which simultaneously exhibit durable and enhanced catalytic activity. The Ni 3 N@CQDs shows an overpotential of 69 mV at a current density of 10 mA cm -2 in a 1 M KOH aqueous solution, lower than that of Pt electrode (116 mV) at the same conditions. Density functional theory (DFT) simulations reveal that Ni 3 N and interfacial oxygen polarize charge distributions between originally equal C-C bonds in CQDs. The partially negatively charged C sites become effective catalytic centers for the key water dissociation step via the formation of new C-H bond (Volmer step) and thus boost the HER activity. Furthermore, the coated carbon is also found to protect interior Ni 3 N from oxidization/hydroxylation and therefore guarantees its durability. This work provides a practical design of robust and durable HER electrocatalysts based on nonprecious metals.

Removal of Sulfur Dioxide from Flue Gas Using the Sludge Sodium Humate

PubMed Central

Hu, Guoxin

2013-01-01

This study shows the ability of sodium humate from alkaline treatment sludge on removing sulfur dioxide (SO2) in the simulated flue gas. Experiments were conducted to examine the effect of various operating parameters, like the inlet SO2 concentration or temperature or O2, on the SO2 absorption efficiency and desulfurization time in a lab-scale bubbling reactor. The sludge sodium humate in the supernatant after alkaline sludge treatment shows great performance in SO2 absorption, and such efficiency can be maintained above 98% with 100 mL of this absorption solution at 298 K (flue gas rate of 0.12 m3/h). The highest SO2 absorption by 1.63 g SHA-Na is 0.946 mmol in the process, which is translated to 0.037 g SO2 g−1 SHA-Na. The experimental results indicate that the inlet SO2 concentration slightly influences the SO2 absorption efficiency and significantly influences the desulfurization time. The pH of the absorption solution should be above 3.5 in this process in order to make an effective desulfurization. The products of this process were characterized by Fourier transform infrared spectroscopy and X-ray diffraction. It can be seen that the desulfurization products mainly contain sludge humic acid sediment, which can be used as fertilizer components. PMID:24453875

High-Molecular Compounds (Selected Articles).

DTIC Science & Technology

1987-08-24

Polymethacrylic Acid and Polyvinyl Alcohol, by I.F. Yefremov, E.B. D’yakonova, A.A. Spartakov, A.A. Trusov ._’ . Us’yarov...polyoctafluoroamyl methacrylate) was converted into polymethacrylic acid by hydrolysis in an alkaline medium. The poly acid was methylated by diazomethane...Institute im. Lensovet Submitted 25 Apr 66 In a low-concentrated aqueous solution of polymethacrylic acid (PHAK) and polyvinyl alcohol (PVS) mixed

Heteromorphic NiCo2S4/Ni3S2/Ni Foam as a Self-Standing Electrode for Hydrogen Evolution Reaction in Alkaline Solution.

PubMed

Liu, Hui; Ma, Xiao; Rao, Yuan; Liu, Yang; Liu, Jialiang; Wang, Luyang; Wu, Mingbo

2018-04-04

Considerable works have been devoted on developing high-efficiency nonplatinum electrocatalysts for hydrogen evolution reaction (HER). Herein, 3D heteromorphic NiCo 2 S 4 /Ni 3 S 2 nanosheets network has been constructed on Ni foam (denoted as NiCo 2 S 4 /Ni 3 S 2 /NF) serving as a self-standing electrocatalyst through directly thermal sulfurization of a single-source NiCo-layered double hydroxide precursor. The resultant NiCo 2 S 4 /Ni 3 S 2 /NF electrode exhibits outstanding electrocatalytic HER performance with an extremely low onset overpotential of 15 mV and long-term durability in alkaline solution. Such enhanced HER performance can be credited to (1) the massive exposed active sites provided by mixed transition metal chalcogenides (NiCo 2 S 4 and Ni 3 S 2 ), (2) the strong interfacial interaction at NiCo 2 S 4 /Ni 3 S 2 heterojunction interfaces with the strengthened H binding, and (3) the porous highly conductive Ni foam substrate with accelerated electron transfer. This work opens up a new direction to fabricate effective and non-noble-metal electrodes for water splitting and hydrogen generation.

Mechanochemical synthesis, structure and properties of lead containing alkaline earth metal fluoride solid solutions MxPb1-xF2 (M = Ca, Sr, Ba)

NASA Astrophysics Data System (ADS)

Heise, M.; Scholz, G.; Düvel, A.; Heitjans, P.; Kemnitz, E.

2018-03-01

The paper deals with the mechanochemical synthesis of lead containing alkaline earth metal fluoride solid solutions MxPb1-xF2 (M = Ca, Sr, Ba) by high-energy ball milling. Several metal precursors and fluorinating agents were tested for synthesizing M0.5Pb0.5F2. Metal acetates and ammonium fluoride as precursors show the most promising results and were therefore used for the formation of MxPb1-xF2 with different metal cationic ratios. The characterization of the local fluorine coordination and the crystal structure was performed by 19F MAS NMR spectroscopy and X-ray diffraction. Additional calculations of 19F chemical shifts using the superposition model allow a deeper insight into the local structure of the compounds. The fluoride ion conductivity was followed by temperature dependent DC conductivity measurements. Significantly higher conductivities were found in comparison with those of the corresponding binary fluorides. The highest values were observed for samples with high lead content M0.25Pb0.75F2, bearing in mind the much higher conductivity of PbF2 compared to MF2.

Online Monitoring of Methanol Electro-Oxidation Reactions by Ambient Mass Spectrometry

NASA Astrophysics Data System (ADS)

Cheng, Si; Wu, Qiuhua; Dewald, Howard D.; Chen, Hao

2017-06-01

Online detection of methanol electro-oxidation reaction products [e.g., formaldehyde (HCHO)] by mass spectrometry (MS) is challenging, owing to the high salt content and extreme pH of the electrolyte solution as well as the difficulty in ionizing the reaction products. Herein we present an online ambient mass spectrometric approach for analyzing HCHO generated from methanol electro-oxidation, taking the advantage of high salt tolerance of desorption electrospray ionization mass spectrometry (DESI-MS). It was found that HCHO can be detected as PhNHNH+=CH2 ( m/z 121) by DESI after online derivatization with PhNHNH2. With this approach, the analysis of HCHO from methanol electro-oxidation by MS was carried out not only in acidic condition but also in alkaline media for the first time. Efficiencies of different electrodes for methanol oxidation at different pHs were also evaluated. Our results show that Au electrode produces more HCHO than Pt-based electrodes at alkaline pH, while the latter have higher yields at acidic solution. The presented methodology would be of great value for elucidating fuel cell reaction mechanisms and for screening ideal fuel cell electrode materials. [Figure not available: see fulltext.

High Laccase Expression by Trametes versicolor in a Simulated Textile Effluent with Different Carbon Sources and PHs

PubMed Central

Ottoni, Cristiane; Simões, Marta F.; Fernandes, Sara; Santos, Cledir R.; Lima, Nelson

2016-01-01

Textile effluents are highly polluting and have variable and complex compositions. They can be extremely complex, with high salt concentrations and alkaline pHs. A fixed-bed bioreactor was used in the present study to simulate a textile effluent treatment, where the white-rot fungus, Trametes versicolor, efficiently decolourised the azo dye Reactive Black 5 over 28 days. This occurred under high alkaline conditions, which is unusual, but advantageous, for successful decolourisation processes. Active dye decolourisation was maintained by operation in continuous culture. Colour was eliminated during the course of operation and maximum laccase (Lcc) activity (80.2 U∙L−1) was detected after glycerol addition to the bioreactor. Lcc2 gene expression was evaluated with different carbon sources and pH values based on reverse transcriptase-PCR (polymerase chain reaction). Glycerol was shown to promote the highest lcc2 expression at pH 5.5, followed by sucrose and then glucose. The highest levels of expression occurred between three and four days, which corroborate the maximum Lcc activity observed for sucrose and glycerol on the bioreactor. These results give new insights into the use of T. versicolor in textile dye wastewater treatment with high pHs. PMID:27490563

Dependence of the electronic absorption spectra of aqueous solutions of iodine monochloride on the conditions of dilution and storage time

NASA Astrophysics Data System (ADS)

Klyubin, V. V.; Klyubina, K. A.; Makovetskaya, K. N.

2017-04-01

The electronic absorption spectra of aqueous solutions of iodine monochloride ICl are studied. The spectra of as-prepared solutions display the absorption band associated with hydrated ICl molecules. An additional band indicating that molecular iodine was formed in the solution emerges in the spectrum as dissolution takes place. Only the band belonging to iodine monochloride remains in the absorption spectra, and no additional bands appear after chloride anions Cl- are added to the solution. The absorption spectrum becomes more complex when ICl is dissolved in an alkaline medium. The band belonging to molecular iodine emerges in the spectra at low alkali concentrations, while being transformed to other shorter-wavelength bands at high alkali concentrations (pH ≥ 12).

Energetics of alkali and alkaline earth ion-exchanged zeolite A

DOE PAGES

Sun, Hui; Wu, Di; Liu, Kefeng; ...

2016-06-30

Alkali and alkaline earth ion-exchanged zeolite A samples were synthesized in aqueous exchange media. They were thoroughly studied by powder X-ray diffraction (XRD), electron microprobe (EMPA), thermogravimetric analysis and differential scanning calorimetry (TG-DSC), and high temperature oxide melt solution calorimetry. The hydration energetics and enthalpies of formation of these zeolite A materials from constituent oxides were determined. Specifically, the hydration level of zeolite A has a linear dependence on the average ionic potential ( Z/r) of the cation, from 0.894 (Rb-A) to 1.317 per TO 2 (Mg-A). The formation enthalpies from oxides (25 °C) range from –93.71 ± 1.77 (K-A)more » to –48.02 ± 1.85 kJ/mol per TO 2 (Li-A) for hydrated alkali ion-exchanged zeolite A, and from –47.99 ± 1.20 (Ba-A) to –26.41 ± 1.71 kJ/mol per TO 2 (Mg-A) for hydrated alkaline earth ion-exchanged zeolite A. As a result, the formation enthalpy from oxides generally becomes less exothermic as Z/r increases, but a distinct difference in slope is observed between the alkali and the alkaline earth series.« less

The Effect of Alkaline Earth Metal on the Cesium Loading of Ionsiv(R) IE-910 and IE-911

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

Fondeur, F.F.

2001-01-16

This study investigated the effect of variances in alkaline earth metal concentrations on cesium loading of IONSIV(R) IE-911. The study focused on Savannah River Site (SRS) ''average'' solution with varying amounts of calcium, barium and magnesium.

40 CFR Appendix C to Part 438 - Metal-Bearing Operations Definitions

Code of Federal Regulations, 2011 CFR

2011-07-01

... chromium. (1) In phosphate conversion, coatings are applied for one or more of the following reasons: to... electrolysis. The part is one of the electrodes and the electrolyte is usually alkaline. Electrolytic alkaline... during salt bath descaling includes spent process solutions, quenches, and rinses. Shot Tower—Lead Shot...

40 CFR Appendix C to Part 438 - Metal-Bearing Operations Definitions

Code of Federal Regulations, 2014 CFR

2014-07-01

... chromium. (1) In phosphate conversion, coatings are applied for one or more of the following reasons: to... electrolysis. The part is one of the electrodes and the electrolyte is usually alkaline. Electrolytic alkaline... during salt bath descaling includes spent process solutions, quenches, and rinses. Shot Tower—Lead Shot...

40 CFR Appendix C to Part 438 - Metal-Bearing Operations Definitions

Code of Federal Regulations, 2013 CFR

2013-07-01

... chromium. (1) In phosphate conversion, coatings are applied for one or more of the following reasons: to... electrolysis. The part is one of the electrodes and the electrolyte is usually alkaline. Electrolytic alkaline... during salt bath descaling includes spent process solutions, quenches, and rinses. Shot Tower—Lead Shot...

40 CFR Appendix C to Part 438 - Metal-Bearing Operations Definitions

Code of Federal Regulations, 2010 CFR

2010-07-01

... chromium. (1) In phosphate conversion, coatings are applied for one or more of the following reasons: to... electrolysis. The part is one of the electrodes and the electrolyte is usually alkaline. Electrolytic alkaline... during salt bath descaling includes spent process solutions, quenches, and rinses. Shot Tower—Lead Shot...

40 CFR Appendix C to Part 438 - Metal-Bearing Operations Definitions

Code of Federal Regulations, 2012 CFR

2012-07-01

... chromium. (1) In phosphate conversion, coatings are applied for one or more of the following reasons: to... electrolysis. The part is one of the electrodes and the electrolyte is usually alkaline. Electrolytic alkaline... during salt bath descaling includes spent process solutions, quenches, and rinses. Shot Tower—Lead Shot...

Synthesis of highly stable cyanine-dye-doped silica nanoparticle for biological applications

NASA Astrophysics Data System (ADS)

Lian, Ying; Ding, Long-Jiang; Zhang, Wei; Zhang, Xiao-ai; Zhang, Ying-Lu; Lin, Zhen-zhen; Wang, Xu-dong

2018-07-01

Cyanine dyes are widely used in biological labeling and imaging because of their narrow near infrared emission, good brightness and high flexibility in functionalization, which not only enables multiplex analysis and multi-color imaging, but also greatly reduces autofluorescence from biological matter and increases signal-to-noise ratio. Unfortunately, their poor chemical- and photo-stability strongly limits their applications. The incorporation of cyanine dyes in silica nanoparticles provides a solution to the problem. On one hand, the incorporation of cyanine dyes in silica matrix can enhance their chemical- and photo-stability and increase brightness of the nanomaterials. On the other hand, silica matrix provides an optimized condition to host the dye, which helps to maintain their fluorescent properties during application. In addition, the well-established silane technique provides numerous functionalities for diverse applications. However, commercially available cyanine dyes are not very stable at high alkaline conditions, which will gradually lose their fluorescence over time. Our results showed that cyanine dyes are very vulnerable in the reverse micelle system, in which they will lose their fluorescence in less than half an hour. The existence of surfactant could greatly promote degradation of cyanine dyes. Fluorescent silica nanoparticles cannot be obtained at the high alkaline condition with the existence of surfactant. In contrast, the cyanine dyes are relatively stable in Stöber media. Owing to the fast formation of silica particles in Stöber media, the exposure time of cyanine dye in alkaline solution was greatly reduced, and highly fluorescent particles with good morphology and size distribution could be obtained via Stöber approach. However, the increasing water content in the Stöber could reduce the stability of cyanine dyes, which should be avoided. This research here provides a clear guidance on how to successfully synthesize cyanine dye-doped silica nanoparticles with good morphology, size distribution, stability and brightness.

Spatially resolved U(VI) partitioning and speciation: implications for plume scale behavior of contaminant U in the Hanford vadose zone.

PubMed

Wan, Jiamin; Kim, Yongman; Tokunaga, Tetsu K; Wang, Zheming; Dixit, Suvasis; Steefel, Carl I; Saiz, Eduardo; Kunz, Martin; Tamura, Nobumichi

2009-04-01

A saline-alkaline brine containing high concentration of U(VI) was accidentally spilled at the Hanford Site in 1951, introducing 10 tons of U into sediments under storage tank BX-102. U concentrations in the deep vadose zone and groundwater plumes increase with time, yet how the U has been migrating is not fully understood. We simulated the spill event in laboratory soil columns, followed by aging, and obtained spatially resolved U partitioning and speciation along simulated plumes. We found after aging, at apparent steady state, that the pore aqueous phase U concentrations remained surprisingly high (up to 0.022 M), in close agreement with the recently reported high U concentrations (up to 0.027 M) in the vadose zone plume (1). The pH values of aged pore liquids varying from 10 to 7, consistent with the measured pH of the field borehole sediments varying from 9.5 to 7.4 (2), from near the plume source to the plume front. The direct measurements of aged pore liquids together with thermodynamic calculations using a Pitzer approach revealed that UO2(CO3)3(4-) is the dominant aqueous U species within the plume body (pH 8-10), whereas Ca2UO2(CO3)3 and CaUO2(CO3)32- are also significant in the plume frontvicinity (pH 7-8), consistent with that measured from field borehole pore-waters (3). U solid phase speciation varies at different locations along the plume flow path and even within single sediment grains, because of location dependent pore and micropore solution chemistry. Our results suggest that continuous gravity-driven migration of the highly stable U02(CO3)34 in the residual carbonate and sodium rich tank waste solution is likely responsible for the detected growing U concentrations in the vadose zone and groundwater.

In-situ Raman spectroscopic study of aluminate speciation in H2O-KOH solutions at high pressures and temperatures

NASA Astrophysics Data System (ADS)

Mookherjee, M.; Keppler, H.; Manning, C. E.

2009-12-01

The solubility of corundum in H2O is low even at high pressure and temperatures. Therefore, it is commonly assumed that alumina remains essentially immobile during fluid-rock interaction. However, field and experimental evidence suggests that alumina solubility is strongly enhanced in the presence of silica as well as in alkaline solutions. In order to understand what controls the alumina solubility and how it is enhanced as a function of fluid composition, we conducted Raman-spectroscopic study of Al speciation in aqueous fluids at high pressure and temperature. Experiments were carried out in an externally heated hydrothermal diamond-anvil cell equipped with low-fluorescence diamonds and iridium gaskets. Raman spectra were collected with a Horiba Jobin-Yvon Labram HR spectrometer using the 514 nm line of an argon laser for excitation. In a first series of experiments, the speciation of alumina was studied in a 1 M KOH solution in equilibrium with corundum up to 700 oC and ~1 GPa. The Raman spectra show a prominent band at 618 cm-1 interpreted to arise from Al-O stretching vibrations associated with the tetrahedral [Al(OH)4]1- species. At higher pressure and temperature, an additional vibrational mode appears in the spectra at 374 cm-1 (full width at half maximum ~ 20 cm-1). This feature is tentatively attributed to [(OH)3Al-O-Al(OH)3]2- (Moolenaar et al. 1970, Jour. Phys. Chem., 74, 3629-3636). No evidence for KAl(OH)4 was observed, consistent with piston cylinder experiments at 700 oC and 1 GPa (Wohlers & Manning, 2009, Chem. Geol., 262, 310). Upon cooling from high-pressure and high temperature, slow kinetics of corundum regrowth lead to oversaturation in the solutions, as evidenced by sharp peaks at 930 and 1066 cm-1 observed upon cooling. These features are probably due to colloidal aluminum hydroxide. The results provide the first evidence for aluminate polymerization at high pressure and temperature, and offer insights into the causes for enhancement of corundum solubility in alkaline solutions.

Rise in the pH of an unfrozen solution in ice due to the presence of NaCl and promotion of decomposition of gallic acids owing to a change in the pH.

PubMed

Takenaka, Norimichi; Tanaka, Masayuki; Okitsu, Kenji; Bandow, Hiroshi

2006-09-14

Oxidative decomposition of gallic acid occurs in alkaline solutions but hardly arises in acidic solutions. We have found that the addition of sodium chloride promotes the decomposition of gallic acid caused by freezing even under neutral and acidic conditions. Even at pH 4.5, gallic acid was decomposed by freezing in the presence of NaCl; however, in the absence of NaCl, it was hardly decomposed by freezing at pH lower than 7. Chloride ions are more easily incorporated in ice than sodium ions when the NaCl solution is frozen. The unfrozen solution in ice becomes positively charged, and as a result, protons transfer from the unfrozen solution to the ice. We measured the pH in the unfrozen solution which coexists with single-crystal ice formed from a 5 mmol dm(-3) NaCl solution and determined the pH to be 8.6 at equilibrium with CO(2) of 380 ppm or 11.3 in the absence of CO(2) compared to pH 5.6 in the original solution. From the model calculation performed for gallic acid solution in the presence of 5 mmol dm(-3) NaCl, it can be estimated that the amount of OH(-) transferred from the ice to the solution corresponds to 1.26 x 10(-5) mol dm(-3). The amount of OH(-) transferred is concentrated into the unfrozen solution and affects the pH of the unfrozen solution. Therefore, the pH in an unfrozen gallic acid solution in ice becomes alkaline, and the decomposition of gallic acid proceeds. It is expected that other base-catalyzed reactions in weakly acidic solutions also proceed by freezing in the presence of NaCl without the need for any alkaline reagents.

Biodegradation of aniline in an alkaline environment by a novel strain of the halophilic bacterium, Dietzia natronolimnaea JQ-AN.

PubMed

Jin, Qiong; Hu, Zhongce; Jin, Zanfang; Qiu, Lequan; Zhong, Weihong; Pan, Zhiyan

2012-08-01

Dietzia natronolimnaea JQ-AN was isolated from industrial wastewater containing aniline. Under aerobic conditions, the JQ-AN strain degraded 87% of the aniline in a 300 mg L(-1) aniline solution after 120 h of shake flask incubation in a medium containing sodium acetate. This strain had an unusually high salinity tolerance in minimal medium (0-6% NaCl, w/v). The optimal pH for microbial growth and aniline biodegradation was pH 8.0. Two liters of simulated aniline wastewater was created in a reactor at pH 8.0 and 3% NaCl (w/v), and biodegradation of aniline was tested over 7 days at 30 °C. For the initial concentrations of 100, 300, and 500 mg L(-1), 100%, 80.5% and 72% of the aniline was degraded, respectively. Strain JQ-AN may use an ortho-cleavage pathway for dissimilation of the catechol intermediate. Copyright © 2012 Elsevier Ltd. All rights reserved.

Evaluation of the 5 and 8 pH point titration methods for monitoring anaerobic digesters treating solid waste.

PubMed

Vannecke, T P W; Lampens, D R A; Ekama, G A; Volcke, E I P

2015-01-01

Simple titration methods certainly deserve consideration for on-site routine monitoring of volatile fatty acid (VFA) concentration and alkalinity during anaerobic digestion (AD), because of their simplicity, speed and cost-effectiveness. In this study, the 5 and 8 pH point titration methods for measuring the VFA concentration and carbonate system alkalinity (H2CO3*-alkalinity) were assessed and compared. For this purpose, synthetic solutions with known H2CO3*-alkalinity and VFA concentration as well as samples from anaerobic digesters treating three different kind of solid wastes were analysed. The results of these two related titration methods were verified with photometric and high-pressure liquid chromatography measurements. It was shown that photometric measurements lead to overestimations of the VFA concentration in the case of coloured samples. In contrast, the 5 pH point titration method provides an accurate estimation of the VFA concentration, clearly corresponding with the true value. Concerning the H2CO3*-alkalinity, the most accurate and precise estimations, showing very similar results for repeated measurements, were obtained using the 8 pH point titration. Overall, it was concluded that the 5 pH point titration method is the preferred method for the practical monitoring of AD of solid wastes due to its robustness, cost efficiency and user-friendliness.

A Cuprous Oxide Thin Film Non-Enzymatic Glucose Sensor Using Differential Pulse Voltammetry and Other Voltammetry Methods and a Comparison to Different Thin Film Electrodes on the Detection of Glucose in an Alkaline Solution

PubMed Central

Molazemhosseini, Alireza; Liu, Chung Chiun

2018-01-01

A cuprous oxide (Cu2O) thin layer served as the base for a non-enzymatic glucose sensor in an alkaline medium, 0.1 NaOH solution, with a linear range of 50–200 mg/dL using differential pulse voltammetry (DPV) measurement. An X-ray photoelectron spectroscopy (XPS) study confirmed the formation of the cuprous oxide layer on the thin gold film sensor prototype. Quantitative detection of glucose in both phosphate-buffered saline (PBS) and undiluted human serum was carried out. Neither ascorbic acid nor uric acid, even at a relatively high concentration level (100 mg/dL in serum), interfered with the glucose detection, demonstrating the excellent selectivity of this non-enzymatic cuprous oxide thin layer-based glucose sensor. Chronoamperometry and single potential amperometric voltammetry were used to verify the measurements obtained by DPV, and the positive results validated that the detection of glucose in a 0.1 M NaOH alkaline medium by DPV measurement was effective. Nickel, platinum, and copper are commonly used metals for non-enzymatic glucose detection. The performance of these metal-based sensors for glucose detection using DPV were also evaluated. The cuprous oxide (Cu2O) thin layer-based sensor showed the best sensitivity for glucose detection among the sensors evaluated. PMID:29316652

Highly precise Re-Os dating for molybdenite using alkaline fusion and NTIMS.

PubMed

Markey, R; Stein, H; Morgan, J

1998-03-01

The technique described in this paper represents the modification and combination of two previously existing methods, alkaline fusion and negative thermal ion mass spectrometry (NTIMS). We have used this technique to analyze repeatedly a homogeneous molybdenite powder used as a reference standard in our laboratory. Analyses were made over a period of 18 months, using four different calibrations of two different spike solutions. The age of this standard reproduces at a level of +/-0.13%. Each individual age analysis carries an uncertainty of about 0.4% that includes the uncertainty in the decay constant for (187)Re. This new level of resolution has allowed us to recognize real differences in ages for two grain-size populations of molybdenite from some Archean samples.

Highly precise Re-Os dating for molybdenite using alkaline fusion and NTIMS

USGS Publications Warehouse

Markey, R.; Stein, H.; Morgan, J.

1998-01-01

The technique described in this paper represents the modification and combination of two previously existing methods, alkaline fusion and negative thermal ion mass spectrometry (NTIMS). We have used this technique to analyze repeatedly a homogeneous molybdenite powder used as a reference standard in our laboratory. Analyses were made over a period of 18 months, using four different calibrations of two different spike solutions. The age of this standard reproduces at a level of ?? 0.13%. Each individual age analysis carries an uncertainty of about 0.4% that includes the uncertainty in the decay constant for 187Re. This new level of resolution has allowed us to recognize real differences in ages for two grain-size populations of molybdenite from some Archean samples.

Alkaline Hydrothermal Vents as Electrochemical Reactors Driving an Auto-Trophic Origin of Life

NASA Astrophysics Data System (ADS)

Camprubi, E.; Lane, N.

2017-07-01

We report the reduction of CO2 to formaldehyde under simulated alkaline hydrothermal conditions. Formaldehyde is transformed into relevant sugars via the formose reaction. Acetyl phosphate can also be synthesised and phosphorylates organic molecules.

Revising the role of pH and thermal treatments in aflatoxin content reduction during the tortilla and deep frying processes.

PubMed

Torres, P; Guzmán-Ortiz, M; Ramírez-Wong, B

2001-06-01

Naturally aflatoxin-contaminated corn (Zea mays L.) was made into tortillas, tortilla chips, and corn chips by the traditional and commercial alkaline cooking processes. The traditional nixtamalization (alkaline-cooking) process involved cooking and steeping the corn, whereas the commercial nixtamalization process only steeps the corn in a hot alkaline solution (initially boiling). A pilot plant that includes the cooker, stone grinder, celorio cutter, and oven was used for the experiments. The traditional process eliminated 51.7, 84.5, and 78.8% of the aflatoxins content in tortilla, tortilla chips, and corn chips, respectively. The commercial process was less effective: it removed 29.5, 71.2, and 71.2 of the aflatoxin in the same products. Intermediate and final products did not reach a high enough pH to allow permanent aflatoxin reduction during thermal processing. The cooking or steeping liquor (nejayote) is the only component of the system with a sufficiently high pH (10.2-10.7) to allow modification and detoxification of aflatoxins present in the corn grain. The importance of removal of tip, pericarp, and germ during nixtamalization for aflatoxin reduction in tortilla is evident.

Illinois basin coal fly ashes. 2. Equilibria relationships and qualitative modeling of ash-water reactions

USGS Publications Warehouse

Roy, W.R.; Griffin, R.A.

1984-01-01

Alkaline and acidic Illinois Basin coal fly ash samples were each mixed with deionized water and equilibrated for about 140 days to simulate ash ponding environments. Common to both equilibrated solutions, anhydrite solubility dominated Ca2+ activities, and Al3+ activities were in equilibrium with both matrix mullite and insoluble aluminum hydroxide phases. Aqueous silica activities were controlled by both mullite and matrix silicates. The pH of the extract of the acidic fly ash was 4.1 after 24 h but increased to a pH value of 6.4 as the H2SO4, assumed to be adsorbed to the particle surfaces, was exhausted by the dissolution of matrix iron oxides and aluminosilicates. The activities of aqueous Al3+ and iron, initially at high levels during the early stages of equilibration, decreased to below analytical detection limits as the result of the formation of insoluble Fe and Al hydroxide phases. The pH of the extract of the alkaline fly ash remained above a pH value of 10 during the entire equilibration interval as a result of the hydrolysis of matrix oxides. As with the acidic system, Al3+ activities were controlled by amorphous aluminum hydroxide phases that began to form after about 7 days of equilibration. The proposed mechanisms and their interrelations are discussed in addition to the solubility diagrams used to deduce these relationships. ?? 1984 American Chemical Society.

Investigation of passive films on nickel Alloy 690 in lead-containing environments

NASA Astrophysics Data System (ADS)

Peng, B.; Lu, B. T.; Luo, J. L.; Lu, Y. C.; Ma, H. Y.

2008-09-01

Passive films formed on Alloy UNS N06690 were investigated in simulated crevice chemistries. It was found the role of lead in corrosion processes is strongly dependent on the pH value of the testing solutions. At pH 1.5 the effect of lead is narrowly noticeable; while at pH 12.7, lead has a significant influence on the electrochemical performance of alloy UNS N06690. The lead alters the surface morphologies at both pH and account for higher hydroxide content in the surface film at pH 12.7. The lead incorporation hinders the formation of spinel oxides during the passivation in alkaline solution. Nanoindentation tests indicate a significant lead-induced degradation in the mechanical properties of passive films. The passivation degradation is attributed to detrimental effects of lead via interrupting the dehydration process and hindering the formation of protective layers on the alloy surface.

Gram-scale synthesis of single-crystalline graphene quantum dots with superior optical properties.

PubMed

Wang, Liang; Wang, Yanli; Xu, Tao; Liao, Haobo; Yao, Chenjie; Liu, Yuan; Li, Zhen; Chen, Zhiwen; Pan, Dengyu; Sun, Litao; Wu, Minghong

2014-10-28

Graphene quantum dots (GQDs) have various alluring properties and potential applications, but their large-scale applications are limited by current synthetic methods that commonly produce GQDs in small amounts. Moreover, GQDs usually exhibit polycrystalline or highly defective structures and thus poor optical properties. Here we report the gram-scale synthesis of single-crystalline GQDs by a facile molecular fusion route under mild and green hydrothermal conditions. The synthesis involves the nitration of pyrene followed by hydrothermal treatment in alkaline aqueous solutions, where alkaline species play a crucial role in tuning their size, functionalization and optical properties. The single-crystalline GQDs are bestowed with excellent optical properties such as bright excitonic fluorescence, strong excitonic absorption bands extending to the visible region, large molar extinction coefficients and long-term photostability. These high-quality GQDs can find a large array of novel applications in bioimaging, biosensing, light emitting diodes, solar cells, hydrogen production, fuel cells and supercapacitors.

Intrinsic borohydride fuel cell/battery hybrid power sources

NASA Astrophysics Data System (ADS)

Hong, Jian; Fang, Bin; Wang, Chunsheng; Currie, Kenneth

The electrochemical oxidation behaviors of NaBH 4 on Zn, Zn-MH, and MH (metal-hydride) electrodes were investigated, and an intrinsic direct borohydride fuel cell (DBFC)/battery hybrid power source using MH (or Zn-MH) as the anode and MnO 2 as the cathode was tested. Borohydride cannot be effectively oxidized on Zn electrodes at the Zn oxidation potential because of the poor electrocatalytic ability of Zn for borohydride oxidation and the high overpotential, even though borohydride has the same oxidation potential of Zn in an alkaline solution. The borohydride can be electrochemically oxidized on Ni and MH electrodes through a 4e reaction at a high overpotential. Simply adding borohydride into an alkaline electrolyte of a Zn/air or MH/air battery can greatly increase the capacity, while an intrinsic DBFC/MH(or Zn)-MnO 2 battery can deliver a higher peak power than regular DBFCs.

The solvated electron battery

NASA Astrophysics Data System (ADS)

Bennett, J.; Harney, D.; Mitchell, T.

A novel ambient temperture secondary battery using sodium and sulfur dissolved in liquid ammonia is being developed at ELTECH Systems corpooration. The key element of the system is the solvated electron electrode, a metallic liquid which is formed by ammonia and a number of alkali and alkaline earth metals. These solutions are excellent ionic and electronic conductors and have been shown to contain 'free' solvated electrons as the anionic species in solution. Sulfur was chosen as the cathodic reactant because of its high solubility in ammonia, and also because of the high solubiity and good conductivity of the polysulfide reaction products. Development efforts have thus far concentrated on basic electrochemical measurements and establishment of system feasibility.

Influence of acid and alkaline sources on optical, structural and photovoltaic properties of CdSe nanoparticles precipitated from aqueous solution

NASA Astrophysics Data System (ADS)

Coria-Monroy, C. Selene; Sotelo-Lerma, Mérida; Hu, Hailin

2016-06-01

CdSe is a widely researched material for photovoltaic applications. One of the most important parameters of the synthesis is the pH value, since it determines the kinetics and the mechanism of the reaction and in consequence, the optical and morphological properties of the products. We present the synthesis of CdSe in solution with strict control of pH and the comparison of ammonia and KOH as alkaline sources and diluted HCl as acid medium. CdSe formation was monitored with photoluminescence emission spectra (main peak in 490 nm, bandgap of CdSe nanoparticles). XRD patterns indicated that CdSe nanoparticles are mainly of cubic structure for ammonia and HCl, but the hexagonal planes appear with KOH. Product yield decreases with pH and also decreases with KOH at constant pH value since ammonia has a double function, as complexing agent and alkaline source. Changes in morphology were observed in SEM images as well with the different alkaline source. The effect of alkaline sources on photovoltaic performance of hybrid organic solar cells with CdSe and poly(3-hexylthiophene) as active layers was clearly observed, indicating the importance of synthesis conditions on optoelectronic properties of promising semiconductor nanomaterials for solar cell applications.

Sorption potential of alkaline treated straw and a soil for sulfonylurea herbicide removal from aqueous solutions: An environmental management strategy.

PubMed

Cara, Irina-Gabriela; Rusu, Bogdan-George; Raus, Lucian; Jitareanu, Gerard

2017-11-01

The adsorption potential of alkaline treated straw (wheat and corn) in mixture with soil, has been investigated for the removal of sulfonylurea molecules from an aqueous solutions. The surface characteristics were investigated by scanning electron microscopy and Fourier Transform Infrared - FTIR, while the adsorbent capacity was evaluated using batch sorption tests and liquid chromatography coupled with mass spectrometry. Surface analysis of alkaline treated straw samples by scanning electron microscopy - SEM showed the increasing of the surface roughness improving their functional surface activity. An increase (337.22 mg g -1 ) of adsorption capacity of sulfonylurea molecules was obtained for all studied straw. The Langmuir isotherm model was the best model for the mathematical description of the adsorption process indicating the forming of a surface sorption monolayer with a finite number of identical sites. The kinetics of sulfonylurea herbicide followed the pseudo-second order mechanism corresponding to strong chemical interactions. The results sustained that the alkaline treated straw have biosorption characteristics, being suitable adsorbent materials. Copyright © 2017 Elsevier Ltd. All rights reserved.

Methanol production method and system

DOEpatents

Chen, Michael J.; Rathke, Jerome W.

1984-01-01

Ethanol is selectively produced from the reaction of methanol with carbon monoxide and hydrogen in the presence of a transition metal carbonyl catalyst. Methanol serves as a solvent and may be accompanied by a less volatile co-solvent. The solution includes the transition metal carbonyl catalysts and a basic metal salt such as an alkali metal or alkaline earth metal formate, carbonate or bicarbonate. A gas containing a high carbon monoxide to hydrogen ratio, as is present in a typical gasifer product, is contacted with the solution for the preferential production of ethanol with minimal water as a byproduct. Fractionation of the reaction solution provides substantially pure ethanol product and allows return of the catalysts for reuse.

Ethanol production method and system

DOEpatents

Chen, M.J.; Rathke, J.W.

1983-05-26

Ethanol is selectively produced from the reaction of methanol with carbon monoxide and hydrogen in the presence of a transition metal carbonyl catalyst. Methanol serves as a solvent and may be accompanied by a less volatile co-solvent. The solution includes the transition metal carbonyl catalysts and a basic metal salt such as an alkali metal or alkaline earth metal formate, carbonate or bicarbonate. A gas containing a high carbon monoxide to hydrogen ratio, as is present in a typical gasifer product, is contacted with the solution for the preferential production of ethanol with minimal water as a byproduct. Fractionation of the reaction solution provides substantially pure ethanol product and allows return of the catalysts for reuse.

pH modulation ameliorates the red blood cell storage lesion in a murine model of transfusion.

PubMed

Chang, Alex L; Kim, Young; Seitz, Aaron P; Schuster, Rebecca M; Pritts, Timothy A

2017-05-15

Prolonged storage of packed red blood cells (pRBCs) induces a series of harmful biochemical and metabolic changes known as the RBC storage lesion. RBCs are currently stored in an acidic storage solution, but the effect of pH on the RBC storage lesion is unknown. We investigated the effect of modulation of storage pH on the RBC storage lesion and on erythrocyte survival after transfusion. Murine pRBCs were stored in Additive Solution-3 (AS3) under standard conditions (pH, 5.8), acidic AS3 (pH, 4.5), or alkalinized AS3 (pH, 8.5). pRBC units were analyzed at the end of the storage period. Several components of the storage lesion were measured, including cell-free hemoglobin, microparticle production, phosphatidylserine externalization, lactate accumulation, and byproducts of lipid peroxidation. Carboxyfluorescein-labeled erythrocytes were transfused into healthy mice to determine cell survival. Compared with pRBCs stored in standard AS3, those stored in alkaline solution exhibited decreased hemolysis, phosphatidylserine externalization, microparticle production, and lipid peroxidation. Lactate levels were greater after storage in alkaline conditions, suggesting that these pRBCs remained more metabolically viable. Storage in acidic AS3 accelerated erythrocyte deterioration. Compared with standard AS3 storage, circulating half-life of cells was increased by alkaline storage but decreased in acidic conditions. Storage pH significantly affects the quality of stored RBCs and cell survival after transfusion. Current erythrocyte storage solutions may benefit from refinements in pH levels. Copyright © 2016 Elsevier Inc. All rights reserved.

An empirical model to estimate density of sodium hydroxide solution: An activator of geopolymer concretes

NASA Astrophysics Data System (ADS)

Rajamane, N. P.; Nataraja, M. C.; Jeyalakshmi, R.; Nithiyanantham, S.

2016-02-01

Geopolymer concrete is zero-Portland cement concrete containing alumino-silicate based inorganic polymer as binder. The polymer is obtained by chemical activation of alumina and silica bearing materials, blast furnace slag by highly alkaline solutions such as hydroxide and silicates of alkali metals. Sodium hydroxide solutions of different concentrations are commonly used in making GPC mixes. Often, it is seen that sodium hydroxide solution of very high concentration is diluted with water to obtain SHS of desired concentration. While doing so it was observed that the solute particles of NaOH in SHS tend to occupy lower volumes as the degree of dilution increases. This aspect is discussed in this paper. The observed phenomenon needs to be understood while formulating the GPC mixes since this influences considerably the relationship between concentration and density of SHS. This paper suggests an empirical formula to relate density of SHS directly to concentration expressed by w/w.

Anion exchange membrane crosslinked in the easiest way stands out for fuel cells

NASA Astrophysics Data System (ADS)

Hossain, Md. Masem; Wu, Liang; Liang, Xian; Yang, Zhengjin; Hou, Jianqiu; Xu, Tongwen

2018-06-01

Covalent crosslinking is an effective method to stabilize anion exchange membranes (AEMs) against water swelling and high alkaline environment, yet complicated process is required. We report herein a straightforward approach to prepare highly crosslinked, transparent and flexible AEM by simply immersing a halo-alkylated polymer (e.g., brominated poly-(2,6-dimethyl-phenylene oxide)) based membrane in aqueous dimethylamine solution at room temperature and the following methylation. During this crosslinking process, a robust self-crosslinking network is formed which shows a gel fraction in N-methyl-2-pyrrolidone of (up to) 94%. Self-crosslinked membranes show low water uptakes (20-42%) and dimensional swelling (9-16%) compared to non-crosslinked membrane but good hydroxide conductivities (up to 26 mS cm-1) at room temperature. Besides, the resulting membranes show some interesting features: the membranes do not immensely change its room temperature water swelling properties at high temperature but exhibits good hydroxide conductivities (up to 60 mS cm-1 at 80 °C). Noting that, the self-crosslinked AEM reported here has no β-hydrogens, exhibiting extremely high alkaline stability (no decline in hydroxide conductivity in 1 M KOH at 60 °C for 360h). Membrane electrode assembly consists of fabricated membrane shows moderate fuel cell performance reaching peak power density 31 mW cm-2 at 60 °C in a H2/O2 alkaline fuel cell.

A newly high alkaline lipase: an ideal choice for application in detergent formulations

PubMed Central

2011-01-01

Background Bacterial lipases received much attention for their substrate specificity and their ability to function in extreme environments (pH, temperature...). Many staphylococci produced lipases which were released into the culture medium. Reports of thermostable lipases from Staphylococcus sp. and active in alkaline conditions are not previously described. Results A newly soil-isolated Staphylococcus sp. strain ESW secretes an induced lipase in the culture medium. The effects of temperature, pH and various components in a detergent on the activity and stability of Staphylococcus sp. lipase (SL1) were studied in a preliminary evaluation for use in detergent formulation solutions. The enzyme was highly active over a wide range of pH from 9.0 to 13.0, with an optimum at pH 12.0. The relative activity at pH 13.0 was about 60% of that obtained at pH 12.0. It exhibited maximal activity at 60°C. This novel lipase, showed extreme stability towards non-ionic and anionic surfactants after pre-incubation for 1 h at 40°C, and relative stability towards oxidizing agents. Additionally, the crude enzyme showed excellent stability and compatibility with various commercial solid and liquid detergents. Conclusions These properties added to the high activity in high alkaline pH make this novel lipase an ideal choice for application in detergent formulations. PMID:22123072

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

Sitler, Steven J.; Raja, Krishnan S.; Charit, Indrajit

Solid solutions of HfB 2-ZrB 2 mixtures were prepared by high-energy ball milling of diboride and additive powders followed by spark plasma sintering (SPS). A mixture of stoichiometric 1:1 HfB 2-ZrB 2 borides was the base composition to which Hf, Zr, Ta, LaB 6 or Gd 2O 3 was added. Hf, Zr and Ta were added in order to bring the boron-to-metal ratio down to 1.86, rendering the boride as MeB 1.86. In the case of LaB 6 and Gd 2O 3, 1.8 mol% was added. Electroanalytical behavior of hydrogen evolution reactions was evaluated in 1 M H 2SO 4more » and 1 M NaOH solutions. The LaB 6 additive material showed Tafel slopes of 125 and 90 mV/decade in acidic and alkaline solutions respectively. The Hf and Zr rich samples showed Tafel slopes of about 120 mV/decade in both electrolytes. The over potentials of hydrogen evolution reactions (at 10 mA/cm 2) in the alkaline solution were about 100 mV lower than those in acidic solution. The metal-rich diborides and addition of LaB 6 showed better hydrogen evolution reaction (HER) activities than the base 1:1 HfB 2-ZrB 2 stoichiometric diboride solid solution. Furthermore, the higher activity of metal-rich borides could be attributed to the increased electron population at the d-orbitals of the metal shown by band structure modeling calculations using the Density Functional Theory approach.« less

Stability of Cholesterol, 7-Ketocholesterol and β-Sitosterol during Saponification: Ramifications for Artifact Monitoring of Sterol Oxide Products.

PubMed

Busch, T P; King, A J

2010-09-01

Cholesterol has been used to monitor artifact generation. Stability differences among cholesterol oxide products (COPs) and cholesterol in thermal and alkaline conditions are theorized. Thus, use of cholesterol may be unsuitable for detection of artifacts generated from COPs. Stability of cholesterol was compared to that of 7-ketocholesterol (7-keto) and β-sitosterol (βS) under various thermal and alkaline saponification conditions: 1 M methanolic KOH for 18 h at 24 °C (1 M18hr24°C, Control), 18 h at 37 °C (1M18hr37°C), 3 h at 45 °C (1M3hr45°C), and 3.6 M methanolic KOH for 3 h at 24 °C (3.6M3hr24°C). Trends indicated that cholesterol in solution was more stable than 7-keto under all conditions. Compared to βS, cholesterol was more stable under all conditions except for 1M18hr37°C for which stabilities were similar. Compounds were more labile in heat than alkalinity. Poor recoveries of 7-keto during cold saponification with high alkalinity were attributed to alkaline instability. 7-Keto, less stable than cholesterol, should be used to monitor artifact generation during screening of various methods that include thermal and alkaline conditions. In a preliminary analysis of turkey meat, more 3,5-7-one was generated from spiking with cholesterol than with 7-keto.

Stability of Cholesterol, 7-Ketocholesterol and β-Sitosterol during Saponification: Ramifications for Artifact Monitoring of Sterol Oxide Products

PubMed Central

Busch, T. P.

2010-01-01

Cholesterol has been used to monitor artifact generation. Stability differences among cholesterol oxide products (COPs) and cholesterol in thermal and alkaline conditions are theorized. Thus, use of cholesterol may be unsuitable for detection of artifacts generated from COPs. Stability of cholesterol was compared to that of 7-ketocholesterol (7-keto) and β-sitosterol (βS) under various thermal and alkaline saponification conditions: 1 M methanolic KOH for 18 h at 24 °C (1 M18hr24°C, Control), 18 h at 37 °C (1M18hr37°C), 3 h at 45 °C (1M3hr45°C), and 3.6 M methanolic KOH for 3 h at 24 °C (3.6M3hr24°C). Trends indicated that cholesterol in solution was more stable than 7-keto under all conditions. Compared to βS, cholesterol was more stable under all conditions except for 1M18hr37°C for which stabilities were similar. Compounds were more labile in heat than alkalinity. Poor recoveries of 7-keto during cold saponification with high alkalinity were attributed to alkaline instability. 7-Keto, less stable than cholesterol, should be used to monitor artifact generation during screening of various methods that include thermal and alkaline conditions. In a preliminary analysis of turkey meat, more 3,5-7-one was generated from spiking with cholesterol than with 7-keto. PMID:20835297

Optical molecular fluorescence determination of ultra-trace beryllium in occupational and environmental samples using highly alkaline conditions

PubMed Central

Adams, Lori; Agrawal, Anoop; Cronin, John P.; Ashley, Kevin

2017-01-01

Exposures to beryllium (Be), even at extremely low levels, can cause severe health effects in a percentage of those exposed; consequently, occupational exposure limits (OELs) promulgated for this element are the lowest established for any element. This work describes the advantages of using highly alkaline dye solutions for determination of Be in occupational hygiene and environmental samples by means of an optical molecular fluorescence technique after sample extraction in 1–3% (w˖w−1) aqueous ammonium bifluoride (NH4HF2). Improved attributes include the ability to further enhance the detection limits of Be in extraction solutions of high acidity with minimal dilution, which is particularly beneficial when NH4HF2 solutions of higher concentration are used for extraction of Be from soil samples. Significant improvements in Be method detection limits (MDLs) are obtained at levels many-fold below those reported previously for this methodology. Notably, MDLs for Be of <0.01 ng l−1 / 0.1 ng per sample have been attained, which are superior to MDLs routinely reported for this element by means of the most widely used ultra-trace elemental measurement technique, inductively coupled plasma mass spectrometry (ICP-MS). Very low MDLs for Be are essential in consideration of reductions in OELs for this element in workplace air by health organizations and regulatory agencies in the USA and internationally. Applications of enhanced Be measurements to air filter samples, surface wipe samples, soils and newly-designed occupational air sampler inserts are illustrated. PMID:28626294

Cysteine as a green corrosion inhibitor for Cu37Zn brass in neutral and weakly alkaline sulphate solutions.

PubMed

Radovanović, Milan B; Petrović, Marija B; Simonović, Ana T; Milić, Snežana M; Antonijević, Milan M

2013-07-01

The aim of this study was to investigate electrochemical properties of brass in neutral and weakly alkaline solutions in the presence of cysteine as a nontoxic and ecological corrosion inhibitor. Potentiodynamic measurements, open circuit potential measurements, as well as chronoamperometric measurements were the methods used during investigation of the inhibitory effect of cysteine on the corrosion behaviour of brass. Potentiodynamic measurements showed that cysteine behaves as a mixed-type inhibitor in the investigated media. Based on polarization curves for brass in a weakly alkaline solution of sodium sulphate at varying cysteine concentrations, an interaction occurs between Cu(+) ions and the inhibitor, resulting in the formation of a protective complex on the electrode surface. The results of chronoamperometric measurements confirm the results obtained by potentiodynamic measurements. Optical microphotography of the brass surface also confirms the formation of a protective film in the presence of a 1 × 10(-4) mol/dm(3) cysteine. Adsorption of cysteine on the brass surface proceeds according to the Langmuir adsorption isotherm.

Adverse effects of mineral-alkali reactions in alkaline flooding: Final report

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

Thornton, S.D.

1988-01-01

Two slim-tube experiments and supporting bottle tests were performed for a study of sandstone-alkali reactions. The two samples of reservoir sandstone used are from oilfields in the People's Republic of China. The first sandstone contains 16 percent clay and is from the Gu-Dao oilfield. The second sandstone contains 12 percent clay and is from the Liao-He oilfield. These two sandstones were allowed to react with alkaline solutions in 6-month bottle tests. Each sandstone consumed the most alkali from 0.5 N NaOH solution, an intermediate amount of alkali from 0.5 N Na/sub 2/SiO/sub 3/ solution, and the least amount of alkalimore » from 0.5 N Na/sub 2/CO/sub 3/ solution. 59 refs., 14 figs., 20 tabs.« less

Method for the recovery of silver from waste photographic fixer solutions

DOEpatents

Posey, F.A.; Palko, A.A.

The method of the present invention is directed to the recovery of silver from spent photographic fixer solutions and for providing an effluent essentially silver-free that is suitable for discharge into commercial sewage systems. The present method involves the steps of introducing the spent photographic fixer solution into an alkaline hypochlorite solution. The oxidizing conditions of the alkaline hypochlorite solution are maintained during the addition of the fixer solution so that the silver ion complexing agents of thiosulfate and sulfite ions are effectively destroyed. Hydrazine monohydrate is then added to the oxidizing solution to form a reducing solution to effect the formation of a precipitate of silver which can be readily removed by filtration of decanting. Experimental tests indicate that greater than 99.99% of the original silver in the spent photographic fixer can be efficiently removed by practicing the present method. Also, the chemical and biological oxygen demand of the remaining effluent is significantly reduced so as to permit the discharge thereof into sewage systems at levels in compliance with federal and state environmental standards.

Method for the recovery of silver from waste photographic fixer solutions

DOEpatents

Posey, Franz A.; Palko, Aloysius A.

1984-01-01

The method of the present invention is directed to the recovery of silver from spent photographic fixer solutions and for providing an effluent essentially silver-free that is suitable for discharge into commercial sewage systems. The present method involves the steps of introducing the spent photographic fixer solution into an alkaline hypochlorite solution. The oxidizing conditions of the alkaline hypochlorite solution are maintained during the addition of the fixer solution so that the silver ion complexing agents of thiosulfate and sulfite ions are effectively destroyed. Hydrazine monohydrate is then added to the oxidizing solution to form a reducing solution to effect the formation of a precipitate of silver which can be readily removed by filtration or decanting. Experimental tests indicate that greater than 99.99% of the original silver in the spent photographic fixer can be efficiently removed by practicing the present method. Also, the chemical and biological oxygen demand of the remaining effluent is significantly reduced so as to permit the discharge thereof into sewage systems at levels in compliance with federal and state environmental standards.

Viscosity of alkaline suspensions of ground black and white pepper samples: An indication or an identification of high dose radiation treatment?

NASA Astrophysics Data System (ADS)

Schreiber, G. A.; Leffke, A.; Mager, M.; Helle, N.; Bögl, K. W.

1994-11-01

Forty-nine pepper samples were taken from retail food stores of different cities in Germany. Most of the black and all white pepper samples showed high viscosity values after jellification in alkaline solution. After irradiation with a γ-ray dose of 6 kGy, viscosity was largely reduced in each case. Some black pepper samples showed a low viscosity level already before irradiation. However, thermoluminescence analysis did not reveal any sign for irradiation treatment prior to examination. Furthermore, the low viscosity level of these samples could not be correlated with a low starch content. It is concluded that the viscosity levels of irradiated white pepper samples clearly reveal high dose irradiation treatment. In case of black peppers it is judged that the method can be used to screen for irradiated samples since it is fast, easy and cheap. However, a positive result should be confirmed by another technique, e.g. thermoluminescence.

D-Galacturonic acid as a highly reactive compound in nonenzymatic browning. 1. Formation of browning active degradation products.

PubMed

Bornik, Maria-Anna; Kroh, Lothar W

2013-04-10

Thermal treatment of an aqueous solution of D-galacturonic acid at pH 3, 5, and 8 led to rapid browning of the solution and to the formation of carbocyclic compounds such as reductic acid (2,3-dihydroxy-2-cyclopenten-1-one), DHCP (4,5-dihydroxy-2-cyclopenten-1-one), and furan-2-carbaldehyde, as degradation products in weak acidic solution. Studies on their formation revealed 2-ketoglutaraldehyde as their common key intermediate. Norfuraneol (4-hydroxy-5-methyl-3-(2H)-furanone) is a typical alkaline degradation product and formed after isomerization. Further model studies revealed reductic acid as an important and more browning active compound than furan-2-carbaldehyde, which led to a red color of the model solution. This red-brown color is also characteristic of thermally treated uronic acid solutions.

Powder-based adsorbents having high adsorption capacities for recovering dissolved metals and methods thereof

DOEpatents

Janke, Christopher J.; Dai, Sheng; Oyola, Yatsandra

2016-05-03

A powder-based adsorbent and a related method of manufacture are provided. The powder-based adsorbent includes polymer powder with grafted side chains and an increased surface area per unit weight to increase the adsorption of dissolved metals, for example uranium, from aqueous solutions. A method for forming the powder-based adsorbent includes irradiating polymer powder, grafting with polymerizable reactive monomers, reacting with hydroxylamine, and conditioning with an alkaline solution. Powder-based adsorbents formed according to the present method demonstrated a significantly improved uranium adsorption capacity per unit weight over existing adsorbents.

Foam-based adsorbents having high adsorption capacities for recovering dissolved metals and methods thereof

DOEpatents

Janke, Christopher J.; Dai, Sheng; Oyola, Yatsandra

2015-06-02

Foam-based adsorbents and a related method of manufacture are provided. The foam-based adsorbents include polymer foam with grafted side chains and an increased surface area per unit weight to increase the adsorption of dissolved metals, for example uranium, from aqueous solutions. A method for forming the foam-based adsorbents includes irradiating polymer foam, grafting with polymerizable reactive monomers, reacting with hydroxylamine, and conditioning with an alkaline solution. Foam-based adsorbents formed according to the present method demonstrated a significantly improved uranium adsorption capacity per unit weight over existing adsorbents.

Surface functionalization of 3D glass-ceramic porous scaffolds for enhanced mineralization in vitro

NASA Astrophysics Data System (ADS)

Ferraris, Sara; Vitale-Brovarone, Chiara; Bretcanu, Oana; Cassinelli, Clara; Vernè, Enrica

2013-04-01

Bone reconstruction after tissue loosening due to traumatic, pathological or surgical causes is in increasing demand. 3D scaffolds are a widely studied solution for supporting new bone growth. Bioactive glass-ceramic porous materials can offer a three-dimensional structure that is able to chemically bond to bone. The ability to surface modify these devices by grafting biologically active molecules represents a challenge, with the aim of stimulating physiological bone regeneration with both inorganic and organic signals. In this research work glass ceramic scaffolds with very high mechanical properties and moderate bioactivity have been functionalized with the enzyme alkaline phosphatase (ALP). The material surface was activated in order to expose hydroxyl groups. The activated surface was further grafted with ALP both via silanization and also via direct grafting to the surface active hydroxyl groups. Enzymatic activity of grafted samples were measured by means of UV-vis spectroscopy before and after ultrasonic washing in TRIS-HCl buffer solution. In vitro inorganic bioactivity was investigated by soaking the scaffolds after the different steps of functionalization in a simulated body fluid (SBF). SEM observations allowed the monitoring of the scaffold morphology and surface chemical composition after soaking in SBF. The presence of ALP enhanced the in vitro inorganic bioactivity of the tested material.

Speciation of arsenic, selenium, and chromium in wildfire impacted soils and ashes

USGS Publications Warehouse

Wolf, Ruth E.; Hoefen, Todd M.; Hageman, Philip L.; Morman, Suzette A.; Plumlee, Geoffrey S.

2010-01-01

In 2007-09, California experienced several large wildfires that damaged large areas of forest and destroyed many homes and buildings. The U.S. Geological Survey collected samples from the Harris, Witch, Grass Valley, Ammo, Santiago, Canyon, Jesusita, and Station fires for testing to identify any possible characteristics of the ashes and soils from burned areas that may be of concern for their impact on water quality, human health, and endangered species. The samples were subjected to analysis for bulk chemical composition for 44 elements by inductively coupled plasma mass spectrometry (ICP-MS) after acid digestion and de-ionized water leach tests for pH, alkalinity, conductivity, and anions. Water leach tests generated solutions ranging from pH 10-12, suggesting that ashes can generate caustic alkalinity in contact with rainwater or body fluids (for example, sweat and fluids in the respiratory tract). Samples from burned residential areas in the 2007 fires had elevated levels for several metals, including: As, Pb, Sb, Cu, Zn, and Cr. In some cases, the levels found were above the U.S. Environmental Protection Agency (USEPA) preliminary remediation goals (PRG) for soils. Speciation analyses were conducted on de-ionized water and simulated lung fluid leachates for As(III), As(V), Se(IV), Se(VI), Cr(III), and Cr(VI). All species were determined in the same analytical run using an ion-pairing HPLC-ICP-MS method. For leachates containing high levels of total Cr, the majority of the chromium was present in the hexavalent, Cr(VI), form. Higher total and hexavalent chromium levels were observed for samples collected from burned residential areas. Arsenic was also generally present in the more oxidized, As(V), form. Selenium (IV) and (VI) were present, but typically at levels below 2 ppb for most samples. Stability studies of leachate solutions under different storage conditions were performed and the suitability of different sample preservation methods for speciation analysis will be discussed.

Assessing the influence of humic acids on the weathering of galena and its environmental implications.

PubMed

Liu, Qingyou; Li, Heping; Jin, Guoheng; Zheng, Kai; Wang, Luying

2018-08-30

Galena weathering often occurs in nature and releases metal ions during the process. Humic acid (HA), a critical particle of natural organic matter, binds metal ions, thus affecting metal transfer and transformation. In this work, an electrochemical method combined with spectroscopic techniques was adopted to investigate the interfacial processes involved in galena weathering under acidic and alkaline conditions, as well as in the presence of HA. The results show that the initial step of galena weathering involved the transformation Pb 2+ and S°, regardless of whether the solution was acidic or alkaline. Under acidic conditions, S° and Pb 2+ further transform into anglesite, and HA adsorbs on the galena surface, inhibiting the transformation of sulfur. HA and Pb (II) ions form bridging complexes. Under alkaline conditions without HA, the sulfur produced undergoes no transformation, whereas Pb 2+ will transform into PbO. The presence of HA changes the galena weathering mechanism via ionization effect, and Pb 2+ is ultimately converted into anglesite. Higher acidity in acidic conditions or higher alkalinity in alkaline conditions causes galena corrosion when the electrolyte does not contain HA. Conversely, higher pH always accelerates galena corrosion when the electrolyte contains HA, whether the electrolyte is acidic or alkaline. At the same acidity/alkalinity, increasing the concentration of HA inhibits galena weathering. Galena will release 134.7 g m -2 ·y -1 Pb 2+ to solution at pH 2.5, and the amount decreases to 28.09 g m -2 ·y -1 in the presence of 1000 mg/L HA. This study provides an in situ electrochemical method for the assessment of galena weathering. Copyright © 2018 Elsevier Inc. All rights reserved.

Difference in anisotropic etching characteristics of alkaline and copper based acid solutions for single-crystalline Si.

PubMed

Chen, Wei; Liu, Yaoping; Yang, Lixia; Wu, Juntao; Chen, Quansheng; Zhao, Yan; Wang, Yan; Du, Xiaolong

2018-02-21

The so called inverted pyramid arrays, outperforming conventional upright pyramid textures, have been successfully achieved by one-step Cu assisted chemical etching (CACE) for light reflection minimization in silicon solar cells. Due to the lower reduction potential of Cu 2+ /Cu and different electronic properties of different Si planes, the etching of Si substrate shows orientation-dependent. Different from the upright pyramid obtained by alkaline solutions, the formation of inverted pyramid results from the coexistence of anisotropic etching and localized etching process. The obtained structure is bounded by Si {111} planes which have the lowest etching rate, no matter what orientation of Si substrate is. The Si etching rate and (100)/(111) etching ratio are quantitatively analyzed. The different behaviors of anisotropic etching of Si by alkaline and Cu based acid etchant have been systematically investigated.

Hydrolysis of alkaline pretreated banana peel

NASA Astrophysics Data System (ADS)

Fatmawati, A.; Gunawan, K. Y.; Hadiwijaya, F. A.

2017-11-01

Banana peel is one of food wastes that are rich in carbohydrate. This shows its potential as fermentation substrate including bio-ethanol. This paper presented banana peel alkaline pretreatment and enzymatic hydrolysis. The pretreatment was intended to prepare banana peel in order to increase hydrolysis performance. The alkaline pretreatment used 10, 20, and 30% w/v NaOH solution and was done at 60, 70 and 80°C for 1 hour. The hydrolysis reaction was conducted using two commercial cellulose enzymes. The reaction time was varied for 3, 5, and 7 days. The best condition for pretreatment process was one conducted using 30% NaOH solution and at 80°C. This condition resulted in cellulose content of 90.27% and acid insoluble lignin content of 2.88%. Seven-day hydrolysis time had exhibited the highest reducing sugar concentration, which was7.2869 g/L.

Overestimation of organic phosphorus in wetland soils by alkaline extraction and molybdate colorimetry.

PubMed

Turner, Benjamin L; Newman, Susan; Reddy, K Ramesh

2006-05-15

Accurate information on the chemical nature of soil phosphorus is essential for understanding its bioavailability and fate in wetland ecosystems. Solution phosphorus-31 nuclear magnetic resonance (31P NMR) spectroscopy was used to assess the conventional colorimetric procedure for phosphorus speciation in alkaline extracts of organic soils from the Florida Everglades. Molybdate colorimetry markedly overestimated organic phosphorus by between 30 and 54% compared to NMR spectroscopy. This was due in large part to the association of inorganic phosphate with organic matter, although the error was exacerbated in some samples by the presence of pyrophosphate, an inorganic polyphosphate that is not detected by colorimetry. The results have important implications for our understanding of phosphorus biogeochemistry in wetlands and suggest that alkaline extraction and solution 31p NMR spectroscopy is the only accurate method for quantifying organic phosphorus in wetland soils.

Coacervate-like microspheres from lysine-rich proteinoid

NASA Technical Reports Server (NTRS)

Rohlfing, D. L.

1975-01-01

Microspheres form isothermally from lysine-rich proteinoid when the ionic strength of the solution is increased with NaCl or other salts. Studies with different monovalent anions and with polymers of different amino acid composition indicate that charge neutralization and hydrophobic bonding contribute to microsphere formation. The particles also form in sea water, especially if heated or made slightly alkaline. The microspheres differ from those made from acidic proteinoid but resemble coacervate droplets in some ways (isothermal formation, limited stability, stabilization by quinone, uptake of dyes). Because the constituent lysine-rich proteinoid is of simulated prebiotic origin, the study is interpreted to add emphasis to and suggest an evolutionary continuity for coacervation phenomena.

Effect of Adding SiO2-Al2O3 Sol into Anodizing Bath on Corrosion Resistance of Oxidation Film on Magnesium Alloy

NASA Astrophysics Data System (ADS)

Liu, Huicong; Zhu, Liqun; Li, Weiping

Due to the widely use in automobile and construction field, AZ91D magnesium alloy need to be protected more effectively for its high chemical activity. In this paper, three kinds of films were formed on magnesium alloy. The first kind of film, named as anodic oxidation film, was prepared by anodic oxidation in the alkaline solution. The processes for preparing the second kind of film, named as multiple film, involved coating sol-gel on the samples and heat-treating before anodic oxidation. The third kind of film was prepared by anodic oxidation in the alkaline oxidation solution containning 5% (vol) SiO2-Al2O3 sol, named as modified oxidation film. The corrosion resistance of the three different films was investigated. The results showed that the modified oxidation film had the highest corrosion resistance due to the largest thickness and most dense surface morphology. Sol was discussed to react during the film forming process, which leaded to the difference between modified oxidation film and anodic oxidation film.

Hydrogen generation from catalytic hydrolysis of alkaline sodium borohydride solution using attapulgite clay-supported Co-B catalyst

NASA Astrophysics Data System (ADS)

Tian, Hongjing; Guo, Qingjie; Xu, Dongyan

An attapulgite clay-supported cobalt-boride (Co-B) catalyst used in portable fuel cell fields is prepared in this paper by impregnation-chemical reduction method. The cost of attapulgite clay is much lower compared with some other inert carriers, such as activated carbon and carbon nanotube. Its microstructure and catalytic activity are analyzed in this paper. The effects of NaOH concentration, NaBH 4 concentration, reacting temperature, catalyst loadings and recycle times on the performance of the catalysts in hydrogen production from alkaline NaBH 4 solutions are investigated. Furthermore, characteristics of these catalysts are carried out in SEM, XRD and TEM analysis. The high catalytic activity of the catalyst indicates that it is a promising and practical catalyst. Activation energy of hydrogen generation using such catalysts is estimated to be 56.32 kJ mol -1. In the cycle test, from the 1st cycle to the 9th cycle, the average hydrogen generation rate decreases gradually from 1.27 l min -1 g -1 Co-B to 0.87 l min -1 g -1 Co-B.

Irrigation water acidification to neutralize alkalinity for nursery crop production: Substrate pH, electrical conductivity, nutrient concentrations, and plant nutrition and growth

USDA-ARS?s Scientific Manuscript database

Liming agents in irrigation water, typically associated with carbonates and bicarbonates of calcium and magnesium, contribute to water alkalinity. Repeated application of LA to container crops can cause media-solution pH to rise overtime, that uncorrected, can lead to a nutrient availability imbalan...

Behavior of ellagitannins, gallic acid, and ellagic acid under alkaline conditions

Treesearch

Richard W. Hemingway; W.E. Hillis

1971-01-01

Examination of the rates of hydrolysis of different ellagitannins under conditions comparable with cold soda and alkaline-groundwood pulping processes showed that some ellagitannins are notably resistant to hydrolysis. The rate of hydrolysis was dependent upon the pH and tempemture of the solution and particularly upon the structure of the compound. Decarboxylation of...

DETERMINATION OF SULFUR DIOXIDE, NITROGEN OXIDES, AND CARBON DIOXIDE IN EMISSIONS FROM ELECTRIC UTILITY PLANTS BY ALKALINE PERMANGANATE SAMPLING AND ION CHROMATOGRAPHY

EPA Science Inventory

A manual 24-h integrated method for determining SO2, NOx, and CO2 in emissions from electric utility plants was developed and field tested downstream from an SO2 control system. Samples were collected in alkaline potassium permanganate solution contained in restricted-orifice imp...

Molecular Simulations of the Diffusion of Uranyl Carbonate Species in Nanosized Mineral Fractures

NASA Astrophysics Data System (ADS)

Kerisit, S.; Liu, C.

2010-12-01

Uranium is a major groundwater contaminant at uranium processing and mining sites as a result of intentional and accidental discharges of uranium-containing waste products into subsurface environments. Recent characterization has shown that uranium preferentially associates with intragrain and intra-aggregate domains in some of the uranium-contaminated sediments collected from the US Department of Energy Hanford Site [1, 2]. In these sediments, uranium existed as precipitated and/or adsorbed phases in grain micropores with nano- to microscale sizes. Desorption and diffusion characterization studies and continuum-scale modeling indicated that ion diffusion in the microfractures is a major mechanism that led to preferential uranium concentration in the microfracture regions and will control the future mobility of uranium in the subsurface sediments [1, 3-4]. However, the diffusion properties of uranyl species in the intragrain regions, especially at the solid-liquid interface, are still poorly understood. Therefore, a general aim of this work is to provide atomic-level insights into the contribution of microscopic surface effects to the slow diffusion process of uranyl species in porous media with nano- to microsized fractures. In this presentation, we will first present molecular dynamics (MD) simulations of feldspar-water interfaces to investigate their interfacial structure and dynamics and establish a theoretical framework for subsequent simulations of water and ion diffusion at these interfaces [5]. We will then report on MD simulations carried out to probe the effects of confinement and of the presence of the mineral surface on the diffusion of water and electrolyte ions in nanosized feldspar fractures [6]. Several properties of the mineral-water interface were varied, such as the fracture width, the ionic strength of the contacting solution, and the surface charge. Our calculations reveal a 2.0-2.5 nm interfacial region within which the diffusion properties of water and that of the electrolyte ions differ significantly from those in bulk aqueous solutions. We will then present MD simulations of the diffusion of a series of alkaline-earth uranyl carbonate species in aqueous solutions [7]. The MD simulations show that the alkaline-earth uranyl carbonate complexes have distinct water exchange dynamics, which could lead to different reactivities. Finally, we will present recent results on the diffusion and adsorption of uranyl carbonate species in intragrain micropores, modeled with the feldspar-water interfaces mentioned in the above, to help interpret the diffusion behavior of uranium in contaminated sediments. [1] Liu C. et al. Geochim. Cosmochim. Acta 68 4519 (2004) [2] McKinley J. P. et al. Geochim. Cosmochim. Acta 70 1873 (2006) [3] Liu C. et al. Water Resour. Res. 42 W12420 (2006) [4] Ilton E. S. et al. Environ. Sci. Technol. 42 1565 (2009) [5] Kerisit S. et al. Geochim. Cosmochim. Acta 72 1481 (2008) [6] Kerisit S. and Liu C. Environ. Sci. Technol. 43 777 (2009) [7] Kerisit S. and Liu C. Geochim. Cosmochim. Acta 74 4937 (2010)

n-Type Conductivity of Cu2O Thin Film Prepared in Basic Aqueous Solution Under Hydrothermal Conditions

NASA Astrophysics Data System (ADS)

Ursu, Daniel; Miclau, Nicolae; Miclau, Marinela

2018-03-01

We report for the first time in situ hydrothermal synthesis of n-type Cu2O thin film using strong alkaline solution. The use of copper foil as substrate and precursor material, low synthesis temperature and short reaction time represent the arguments of a new, simple, inexpensive and high field synthesis method for the preparation of n-type Cu2O thin film. The donor concentration of n-type Cu2O thin film obtained at 2 h of reaction time has increased two orders of magnitude than previous reported values. We have demonstrated n-type conduction in Cu2O thin film prepared in strong alkaline solution, in the contradiction with the previous works. Based on experimental results, the synthesis mechanism and the origin of n-type photo-responsive behavior of Cu2O thin film were discussed. We have proposed that the unexpected n-type character could be explained by H doping of Cu2O thin film in during of the hydrothermal synthesis that caused the p-to-n conductivity-type conversion. Also, this work raises new questions about the origin of n-type conduction in Cu2O thin film, the influence of the synthesis method on the nature of the intrinsic defects and the electrical conduction behavior.

The Effects of an Alkaline Treatment on the Ferroelectric Properties of Poly(vinylidene fluoride trifluoroethylene) Films

DOE PAGES

Kim, Yeontae; Hong, Seungbum; Oh, Sehoon; ...

2015-06-30

The effects of an alkaline treatment on the ferroelectric properties of poly(vinylidene fluoride trifluoroethylene) [P(VDF-TrFE)] copolymer films are investigated. The alkaline treatment resulted in a small change in the surface roughness but no significant change in the grain shape or size of P(VDF-TrFE) copolymer films, as evidenced by both scanning electron microscopy and atomic force microscopy images. However, x-ray photoelectron spectroscopy results indicated that the alkaline etchant of a KOH solution reacted with P(VDF-TrFE) films to decrease the number of C-F bonds while creating new carbon conjugated double bonds, which decreased the remanent polarization of the P(VDF-TrFE) films. These resultsmore » can improve our understanding of the degradation mechanism of an alkaline treatment.« less

Life cycle assessment of biogas upgrading technologies.

PubMed

Starr, Katherine; Gabarrell, Xavier; Villalba, Gara; Talens, Laura; Lombardi, Lidia

2012-05-01

This article evaluates the life cycle assessment (LCA) of three biogas upgrading technologies. An in-depth study and evaluation was conducted on high pressure water scrubbing (HPWS), as well as alkaline with regeneration (AwR) and bottom ash upgrading (BABIU), which additionally offer carbon storage. AwR and BABIU are two novel technologies that utilize waste from municipal solid waste incinerators - namely bottom ash (BA) and air pollution control residues (APC) - and are able to store CO(2) from biogas through accelerated carbonation processes. These are compared to high pressure water scrubbing (HPWS) which is a widely used technology in Europe. The AwR uses an alkaline solution to remove the CO(2) and then the solution - rich in carbonate and bicarbonate ions - is regenerated through carbonation of APC. The BABIU process directly exposes the gas to the BA to remove and immediately store the CO(2), again by carbonation. It was determined that the AwR process had an 84% higher impact in all LCA categories largely due to the energy intensive production of the alkaline reactants. The BABIU process had the lowest impact in most categories even when compared to five other CO(2) capture technologies on the market. AwR and BABIU have a particularly low impact in the global warming potential category as a result of the immediate storage of the CO(2). For AwR, it was determined that using NaOH instead of KOH improves its environmental performance by 34%. For the BABIU process the use of renewable energies would improve its impact since accounts for 55% of the impact. Copyright © 2011 Elsevier Ltd. All rights reserved.

Self-compacting geopolymer concrete-a review

NASA Astrophysics Data System (ADS)

Ukesh Praveen, P.; Srinivasan, K.

2017-11-01

In this construction world, Geopolymer concrete is a special concrete which doesn’t requires the Ordinary Portland Cement and also reduces the emission of carbon-dioxide. The Geopolymer Concrete is made up of industrial by-products (which contains more Silica and Alumina) and activated with the help of Alkaline solution (combination of sodium hydroxide & sodium silicate or potassium hydroxide & potassium silicate). The high viscosity nature of Geopolymer Concrete had the ability to fail due to lack of compaction. In improvising the issue, Self Compacting Geopolymer Concrete has been introduced. The SCGC doesn’t require any additional compaction it will flow and compacted by its own weight. This concrete is made up of industrial by-products like Fly ash, GGBFS and Silica Fume and activated with alkaline solution. The earlier research was mostly on Fly ash based SCGC. In few research works Fly ash was partially replaced with GGBS and Silica Fume. They evaluated the compressive strength of concrete with varying molarities of NaOH; curing time and curing temperature. The flexural behaviour of the concrete also examined. The Fly ash based SCGC was got high compressive strength in heat curing as well as low compressive strength in ambient curing. The presence of GGBS improves the strength in ambient curing. For aiming the high strength in ambient curing Fly ash will be completely replace and examine with different mineral admixtures.

A highly reproducible solenoid micropump system for the analysis of total inorganic carbon and ammonium using gas-diffusion with conductimetric detection.

PubMed

Henríquez, Camelia; Horstkotte, Burkhard; Cerdà, Víctor

2014-01-01

In this work, a simple, economic, and miniaturized flow-based analyzer based on solenoid micropumps is presented. It was applied to determine two parameters of high environmental interest: ammonium and total inorganic carbon (TIC) in natural waters. The method is based on gas diffusion (GD) of CO₂ and NH3 through a hydrophobic gas permeable membrane from an acidic or alkaline donor stream, respectively. The analytes are trapped in an acceptor solution, being slightly alkaline for CO₂ and slightly acidic for NH₃. The analytes are quantified using a homemade stainless steel conductimetric cell. The proposed system required five solenoid micro-pumps, one for each reagent and sample. Two especially made air bubble traps were placed down-stream of the solendoid pumps, which provided the acceptor solutions, by this increasing the method's reproducibility. Values of RSD lower than 1% were obtained. Achieved limits of detection were 0.27 µmol L⁻¹ for NH₄⁺ and 50 µmol L⁻¹ for TIC. Add-recovery tests were used to prove the trueness of the method and recoveries of 99.5 ± 7.5% were obtained for both analytes. The proposed system proved to be adequate for monitoring purpose of TIC and NH₄⁺ due to its high sample throughput and repeatability. © 2013 Published by Elsevier B.V.

Short-column anion-exchange chromatography for soil and peat humic substances profiling by step-wise gradient of high pH aqueous sodium ethylenediaminetetraacetate.

PubMed

Hutta, Milan; Ráczová, Janka; Góra, Róbert; Pessl, Juraj

2015-08-21

Novel anion-exchange liquid chromatographic method with step gradient of aqueous EDTA(4-) based mobile phase elution has been developed to profile available Slovak soil humic substances and alkaline extracts of various soils. The method utilize short glass column (30mm×3mm) filled in with hydrolytically stable particles (60μm diameter) Separon HEMA-BIO 1000 having (diethylamino)ethyl functional groups. Step gradient was programmed by mixing mobile phase composed of aqueous solution of sodium EDTA (pH 12.0; 5mmolL(-1)) and mobile phase constituted of aqueous solution of sodium EDTA (pH 12.0, 500mmolL(-1)). The FLD of HSs was set to excitation wavelength 480nm and emission wavelength 530nm (λem). Separation mechanism was studied by use of selected aromatic acids related to humic acids with the aid of UV spectrophotometric detection at 280nm. The proposed method benefits from high ionic strength (I=5molL(-1)) of the end mobile phase buffer and provides high recovery of humic acids (98%). Accurate and reproducible profiling of studied humic substances, alkaline extracts of various types of soils enables straightforward characterization and differentiation of HSs in arable and forest soils. Selected model aromatic acids were used for separation mechanism elucidation. Copyright © 2015 Elsevier B.V. All rights reserved.

Evolution of the magnesium incorporated amorphous calcium phosphate to nano-crystallized hydroxyapatite in alkaline solution

NASA Astrophysics Data System (ADS)

Zhang, Xiao-Juan; Lin, Dong-Yang; Yan, Xiao-Hui; Wang, Xiao-Xiang

2011-12-01

A homogeneous amorphous calcium phosphate (ACP) coating containing magnesium was achieved on titanium substrates by electrochemical deposition (ECD). Its amorphous structure is confirmed by transmission electron microscope (TEM) together with grazing reflection absorption infrared spectroscopy (IR) spectrometer. In the images of high-resolution transmission electron microscope (HRTEM), the ACP spheres are assembled by nano-particles with the diameter of 5-10 nm. In the alkaline environment, nucleation of hydroxyapatite (HAP) occurs on the surfaces of ACP spheres. By consuming the Ca and PO 4 ions inside the ACP spheres, the HAP nuclei grow outward. Confirmed by TEM, the ACP spheres converse to hollow HAP spheres composed of HAP nano-needles. The coating is finally constructed by the HAP nano-needles, which are themselves aggregated by numerous nano-particles.

Effect of pH in a Pd-based ethanol membraneless air breathing nanofluidic fuel cell with flow-through electrodes

NASA Astrophysics Data System (ADS)

López-Rico, C. A.; Galindo-de-la-Rosa, J.; Ledesma-García, J.; Arriaga, L. G.; Guerra-Balcázar, M.; Arjona, N.

2015-12-01

In this work, a nanofluidic fuel cell (NFC) in which streams flow through electrodes was used to investigate the role of pH in the cell performance using ethanol as fuel and two Pd nanoparticles as electrocatalysts: one commercially available (Pd/C from ETEK) and other synthesized using ionic liquids (Pd/C IL). The cell performances for both electrocatalysts in acid/acid (anodic/cathodic) streams were of 18.05 and 9.55 mW cm-2 for Pd/C ETEK and Pd/C IL. In alkaline/alkaline streams, decrease to 15.94 mW cm-2 for Pd/C ETEK and increase to 15.37 mW cm-2 for Pd/C IL. In alkaline/acidic streams both electrocatalysts showed similar cell voltages (up to 1 V); meanwhile power densities were of 87.6 and 99.4 mW cm-2 for Pd/C ETEK and Pd/C IL. The raise in cell performance can be related to a decrease in activation losses, the combined used of alkaline and acidic streams and these high values compared with flow-over fuel cells can be related to the enhancement of the cathodic mass transport by using three dimensional porous electrodes and two sources of oxygen: from air and from a saturated solution.

Acidity and alkalinity in mine drainage: Theoretical considerations

USGS Publications Warehouse

Kirby, Carl S.; Cravotta,, Charles A.

2004-01-01

Acidity, net acidity, and net alkalinity are widely used parameters for the characterization of mine drainage, but these terms are not well defined and are often misunderstood. Incorrect interpretation of acidity, alkalinity, and derivative terms can lead to inadequate treatment design or poor regulatory decisions. We briefly explain derivations of theoretical expressions of three types of alkalinities (caustic, phenolphthalein, and total) and acidities (mineral, CO2, and total). Theoretically defined total alkalinity is closely analogous to measured alkalinity and presents few practical interpretation problems. Theoretically defined “CO2- acidity” is closely related to most standard titration methods used for mine drainage with an endpoint pH of 8.3, but it presents numerous interpretation problems, and it is unfortunately named because CO2 is intentionally driven off during titration of mine-drainage samples. Using the proton condition/massaction approach and employing graphs for visualization, we explore the concept of principal components and how to assign acidity contributions to solution species, including aqueous complexes, commonly found in mine drainage. We define a comprehensive theoretical definition of acidity in mine drainage on the basis of aqueous speciation at the sample pH and the capacity of these species to undergo hydrolysis to pH 8.3. This definition indicates the computed acidity in milligrams per liter (mg L-1 ) as CaCO3 (based on pH and analytical concentrations of dissolved FeIII , FeII , Mn, and Al in mg L-1 ): Aciditycomputed = 50. (10(3-pH) + 3.CFeIII/55.8 + 2.CFeII/55.8 + 2.CMn/54.9 + 3.CAl/27.0) underestimates contributions from HSO4 - and H+ , but overestimates the acidity due to Fe3+. These errors tend to approximately cancel each other. We demonstrate that “net alkalinity” is a valid mathematical construction based on theoretical definitions of alkalinity and acidity. We demonstrate that, for most mine-drainage solutions, a useful net alkalinity value can be derived from: 1) alkalinity and acidity values based on aqueous speciation, 2) measured alkalinity - computed acidity, or 3) taking the negative of the value obtained in a standard method “hot peroxide” acidity titration, provided that labs report negative values. We recommend the third approach; i.e., Net alkalinity = - Hot Acidity.

pH dependent green synthesis of gold nanoparticles by completely C6-carboxylated curdlan under high temperature and various pH conditions.

PubMed

Qiu, Wen-Yi; Wang, Kai; Wang, Yao-Yao; Ding, Zhi-Chao; Wu, Li-Xia; Cai, Wu-Dan; Yan, Jing-Kun

2018-01-01

A C6-carboxylated curdlan (C6-Cc) obtained from 4-acetamido-TEMPO-mediated oxidation of curdlan was used both as a reducing and stabilizing agent for green synthesis of pH-responsive AuNPs, which was carried out by controlling the pH of the C6-Cc solution at a high temperature (100°C). C6-Cc presented a semi-flexible random coil chain in the aqueous medium at pH 5.5 and became more expanded and rigid in alkaline conditions (pH 7.1-12.0), though the primary chemical structure of C6-Cc was virtually unchanged with the pH variation. The AuNPs prepared with C6-Cc at various pHs were characterized by various instrumental measurements. The shapes and sizes of AuNPs were found to be strongly dependent on the pH of the C6-Cc solution. The C6-Cc-decorated AuNPs exhibited a more well-dispersed spherical morphology with smaller particle sizes under alkaline conditions (pH 7.1-12.0). Through this study, a facile, simple, and green method has been demonstrated for preparation of stimuli-sensitive AuNPs using biocompatible polyanionic polysaccharides. Copyright © 2017 Elsevier B.V. All rights reserved.

A novel sputtered Pd mesh architecture as an advanced electrocatalyst for highly efficient hydrogen production

NASA Astrophysics Data System (ADS)

de Lucas-Consuegra, Antonio; de la Osa, Ana R.; Calcerrada, Ana B.; Linares, José J.; Horwat, David

2016-07-01

This study reports the preparation, characterization and testing of a sputtered Pd mesh-like anode as an advanced electrocatalyst for H2 production from alkaline ethanol solutions in an Alkaline Membrane Electrolyzer (AEM). Pd anodic catalyst is prepared by magnetron sputtering technique onto a microfiber carbon paper support. Scanning Electron Microscopy images reveal that the used preparation technique enables to cover the surface of the carbon microfibers exposed to the Pd target, leading to a continuous network that also maintains part of the original carbon paper macroporosity. Such novel anodic architecture (organic binder free) presents an excellent electro-chemical performance, with a maximum current density of 700 mA cm-2 at 1.3 V, and, concomitantly, a large H2 production rate with low energy requirement compared to water electrolysis. Potassium hydroxide emerges as the best electrolyte, whereas temperature exerts the expected promotional effect up to 90 °C. On the other hand, a 1 mol L-1 ethanol solution is enough to guarantee an efficient fuel supply without any mass transfer limitation. The proposed system also demonstrates to remain stable over 150 h of operation along five consecutives cycles, producing highly pure H2 (99.999%) at the cathode and potassium acetate as the main anodic product.

Cyclic, Early Diagenetic Dolomite Formation in Alkaline Lake Van

NASA Astrophysics Data System (ADS)

McCormack, J.; Bontognali, T. R. R.; Immenhauser, A.; Kwiecien, O.

2017-12-01

Modern dolomite-forming environments are commonly constrained to evaporitic marine or marginal marine settings such as lagoons and sabkhas. Beside microbial mediation, high temperatures and Mg2+ concentrations in solution are factors considered important in aiding dolomite formation. Accordingly, previous studies associate the presence of dolomite within deep sediments of alkaline Lake Van (Turkey) with periods of enhanced evaporation, low lake levels and high Mg/Ca ratio. We systematically studied dolomite within the sedimentary record of Lake Van by means of XRD, SEM and stable isotope (δ18O and δ13C) mass spectrometry. First, we considered the origin of the dolomite; next, we focused on the wider implication of its presence. SEM imaging documents large dolomite crystals interwoven with clay minerals and individual crystals with different crystallographic orientations grown together, indicating space-limited growth within the sediment. According to recent climatic reconstructions for the same sequence (ICDP PALEOVAN project), the water depth of the coring site - today at 350 m - unlikely fell below 200 m. Consequently, dolomite formed below a thick water column at constantly low temperatures (supported by heavy δ18O signature). Within this environment, variations in Mg/Ca ratio, pH and alkalinity, which are constantly high, have no effect on the episodic nature of dolomite precipitation. These observations call for a re-evaluation of the palaeoenvironments often invoked to interpret intervals rich in dolomite within ancient sedimentary sequences (e.g., periods of enhanced aridity and evaporation). Further, and in contrast to previous interpretations, our dolomite concentration data backed up by ICDP PALEOVAN reconstructions suggest that intervals rich in dolomite coincide with periods of high lake level and increased humidity. High dolomite concentrations (20 - 85 % relative carbonate content) occur cyclically within the last glacial period and coincide with rapid Northern Hemisphere temperature oscillation (i.e. Greenland Interstadials). Lake Vańs dolomite record thus provides compelling arguments suggesting that early diagenetic dolomite formation within an alkaline environment can be highly sensitive to hydrological changes even on centennial timescales.

Impacts of artificial ocean alkalinization on the carbon cycle and climate in Earth system simulations

NASA Astrophysics Data System (ADS)

González, Miriam Ferrer; Ilyina, Tatiana

2016-06-01

Using the state-of-the-art emissions-driven Max Planck Institute Earth system model, we explore the impacts of artificial ocean alkalinization (AOA) with a scenario based on the Representative Concentration Pathway (RCP) framework. Addition of 114 Pmol of alkalinity to the surface ocean stabilizes atmospheric CO2 concentration to RCP4.5 levels under RCP8.5 emissions. This scenario removes 940 GtC from the atmosphere and mitigates 1.5 K of global warming within this century. The climate adjusts to the lower CO2 concentration preventing the loss of sea ice and high sea level rise. Seawater pH and the carbonate saturation state (Ω) rise substantially above levels of the current decade. Pronounced differences in regional sensitivities to AOA are projected, with the Arctic Ocean and tropical oceans emerging as hot spots for biogeochemical changes induced by AOA. Thus, the CO2 mitigation potential of AOA comes at a price of an unprecedented ocean biogeochemistry perturbation with unknown ecological consequences.

Removal of six pesticide residues in cowpea with alkaline electrolysed water.

PubMed

Han, Yongtao; Song, Le; An, Quanshun; Pan, Canping

2017-06-01

Reduction of six pesticide residues (isoprocarb, chlorpyrifos, bifenthrin, beta-cypermethrin, difenoconazole and azoxystrobin) in cowpea by alkaline electrolysed water (AlEW) solutions with different pH was investigated. The commonly used washing treatments in household processing were used for comparison. The residue magnitudes were determined by gas chromatography coupled with tandem mass spectrometry (GC-MS/MS). Results showed that the removal effect of AlEW solution on the six pesticides was superior to tap water, 5% sodium chloride, 5% sodium carbonate and 5% acetic acid solution. AlEW with pH 12.2 had more potential to eliminate the six pesticides in cowpeas. Moreover, the reduction of pesticide residues gradually increased with the increase of washing time. This study demonstrated that AlEW solution with pH of 12.2 could be used to reduce pesticide residues on fresh cowpea samples. © 2016 Society of Chemical Industry. © 2016 Society of Chemical Industry.

Femtosecond laser fabricating black silicon in alkaline solution

NASA Astrophysics Data System (ADS)

Meng, Jiao; Song, Haiying; Li, Xiaoli; Liu, Shibing

2015-03-01

An efficient approach for enhancing the surface antireflection is proposed, in which a black silicon is fabricated by a femtosecond laser in alkaline solution. In the experiment, 2 wt% NaOH solution is formulated at room temperature (22 ± 1 °C). Then, a polished silicon is scanned via femtosecond laser irradiation in 2 wt% NaOH solution. Jungle-like microstructures on the black silicon surface are characterized using an atomic force microscopy. The reflectance of the black silicon is measured at the wavelengths ranging from 400 to 750 nm. Compared to the polished silicon, the black silicon can significantly suppress the optical reflection throughout the visible region (<5 %). Meanwhile, we also investigated the factors of the black silicon, including the femtosecond laser pulse energy and the scanning speed. This method is simple and effective to acquire the black silicon, which probably has a large advantage in fast and cost-effective black silicon fabrication.

Acid-base relations in epithelium of turtle bladder: site of active step in acidification and role of metabolic CO2.

PubMed

Steinmetz, P R

1969-07-01

The acid-base relations across the two surfaces of the epithelium of the turtle bladder were examined. By means of the 5,5-dimethyl-2,4-oxazolidinedione (DMO) technique the intracellular OH(-) concentration was measured in the presence and absence of a transepithelial pH gradient. When both sides of the bladder were bathed with solutions free of exogenous CO(2) and bicarbonate at pH 7.41 ([OH(-)] = 239 nmoles/liter), the epithelial cells were alkaline, the mean intracellular [OH(-)] being 347nmoles/liter. This alkalinity of the cells was preserved in bladders that secreted H(+) against a gradient of over 2 pH units. In bathing solutions stirred with 4.85% CO(2) and buffered with 25 mM HCO(3) (-) at pH 7.41 the intracellular [OH(-)] was lower than in CO(2)-free solutions and close to the extracellular [OH(-)]. In the CO(2)-free system anaerobiosis caused increased alkalinity of the cells and inhibition of H(+) secretion presumably by decreased metabolic CO(2) production. Carbonic acid inhibitors reduced H(+) secretion, but had no significant effect on the alkalinity of the cells. An inactive analogue of acetazolamide had no effect on H(+) secretion. The results indicate that the active step in acidification is located near the mucosal surface of the epithelium and that the alkali formed within the epithelial cells moves passively into the serosal solution along an electro-chemical gradient. The inhibitory effect of certain sulfonamides on H(+) secretion by the bladder is directly correlated with their known carbonic anhydrase inhibitory activity, but not associated with a measurable change in the mean intracellular [OH(-)].

Study of poly(vinyl alcohol)/titanium oxide composite polymer membranes and their application on alkaline direct alcohol fuel cell

NASA Astrophysics Data System (ADS)

Yang, Chun-Chen; Chiu, Shwu-Jer; Lee, Kuo-Tong; Chien, Wen-Chen; Lin, Che-Tseng; Huang, Ching-An

The novel poly(vinyl alcohol)/titanium oxide (PVA/TiO 2) composite polymer membrane was prepared using a solution casting method. The characteristic properties of the PVA/TiO 2 composite polymer membrane were investigated by thermal gravimetric analysis (TGA), a scanning electron microscopy (SEM), a micro-Raman spectroscopy, a methanol permeability measurement and the AC impedance method. An alkaline direct alcohol (methanol, ethanol and isopropanol) fuel cell (DAFC), consisting of an air cathode based on MnO 2/C inks, an anode based on PtRu (1:1) black and a PVA/TiO 2 composite polymer membrane, was assembled and examined for the first time. The results indicate that the alkaline DAFC comprised of a cheap, non-perfluorinated PVA/TiO 2 composite polymer membrane shows an improved electrochemical performances. The maximum power densities of alkaline DAFCs with 4 M KOH + 2 M CH 3OH, 2 M C 2H 5OH and 2 M isopropanol (IPA) solutions at room temperature and ambient air are 9.25, 8.00, and 5.45 mW cm -2, respectively. As a result, methanol shows the highest maximum power density among three alcohols. The PVA/TiO 2 composite polymer membrane with the permeability values in the order of 10 -7 to 10 -8 cm 2 s -1 is a potential candidate for use on alkaline DAFCs.

Geochemical transformations and modeling of two deep-well injected hazardous wastes

USGS Publications Warehouse

Roy, W.R.; Seyler, B.; Steele, J.D.; Mravik, S.C.; Moore, D.M.; Krapac, I.G.; Peden, J.M.; Griffin, R.A.

1991-01-01

Two liquid hazardous wastes (an alkaline brine-like solution and a dilute acidic waste) were mixed with finely ground rock samples of three injection-related lithologies (sandstone, dolomite, and siltstone) for 155 to 230 days at 325??K-10.8 MPa. The pH and inorganic chemical composition of the alkaline waste were not significantly altered by any of the rock samples after 230 days of mixing. The acidic waste was neutralized as a consequence of carbonate dissolution, ion exchange, or clay-mineral dissolution, and hence was transformed into a nonhazardous waste. Mixing the alkaline waste with the solid phases yielded several reaction products: brucite, Mg(OH)2; calcite, CaCO3; and possibly a type of sodium metasilicate. Clay-like minerals formed in the sandstone, and hydrotalcite, Mg6Al2-CO3(OH)16??4H2O, may have formed in the siltstone at trace levels. Mixing the alkaline waste with a synthetic brine yielded brucite, calcite, and whewellite (CaC2O4??H2O). The thermodynamic model PHRQPITZ predicted that brucite and calcite would precipitate from solution in the dolomite and siltstone mixtures and in the alkaline waste-brine system. The dilute acidic waste did not significantly alter the mineralogical composition of the three rock types after 155 days of contact. The model PHREEQE indicated that the calcite was thermodynamically stable in the dolomite and siltstone mixtures.

The Effect of Micro/Nano-metrics Size on the Interaction of Jordanian Aluminosilicate Raw Materials with High pH Solution

NASA Astrophysics Data System (ADS)

Aldabsheh, Islam; Garcia-Valles, Maite; Martinez, Salvador

2014-05-01

Environmental preservation has become a driving force behind the search for new sustainable and environmentally friendly composites to replace conventional concrete produced from ordinary Portland cement (OPC). Current researches concentrate on developing building products (geopolymers) through geopolymerization. The goal is to produce low cost construction materials for green housing. Geopolymerization is the process of polymerizing minerals with high silica and alumina at low temperature by the use of alkali solutions. Dissolution is the most important process for supplying the high initial Al and Si concentrations to produce the gel phase that is responsible for geopolymerization. This study has been focused on the influence of different micrometric particle sizes of three Jordanian raw materials on their dissolution behavior in sodium hydroxide solution. The samples are kaolinite, volcanic tuff and silica sand. The dissolution properties of each material, alone and mixed with the other two materials were studied in different concentrations (5 and 10 M) using (NaOH) at 25ºC, and shaking time for 24 and 168 h. To better understand the dissolution process, the alkaline solution was renewed after the desired time in order to know if the Al-Si raw material is completely dissolved or not. Different analytical techniques were used to characterize raw materials physically, mineralogically, chemically and thermally. All processed samples either centrifuged solutions or solid residues were fully characterized. The leached concentrations of Al and Si were determined by inductively coupled plasma (ICP). X-ray Diffraction Technique (XRD), Scanning Electron Microscopy (SEM), and Thermo Gravimetric Analysis (TGA) were used to evaluate the solid residue characterization compared with the original ones. The three aluminosilicate raw materials have indicated variable degrees of solubility under highly alkaline conditions. The method for the size reduction of the used raw materials achieved by using a ball mill increased the dissolution rate owing to the increased surface area of the material or particle exposed to the solvent. The used Jordanian raw materials are potential to be used for geopolymerization. This work was partly financed by SGR 2009SGR-00444

An advanced Ni-Fe layered double hydroxide electrocatalyst for water oxidation.

PubMed

Gong, Ming; Li, Yanguang; Wang, Hailiang; Liang, Yongye; Wu, Justin Z; Zhou, Jigang; Wang, Jian; Regier, Tom; Wei, Fei; Dai, Hongjie

2013-06-12

Highly active, durable, and cost-effective electrocatalysts for water oxidation to evolve oxygen gas hold a key to a range of renewable energy solutions, including water-splitting and rechargeable metal-air batteries. Here, we report the synthesis of ultrathin nickel-iron layered double hydroxide (NiFe-LDH) nanoplates on mildly oxidized multiwalled carbon nanotubes (CNTs). Incorporation of Fe into the nickel hydroxide induced the formation of NiFe-LDH. The crystalline NiFe-LDH phase in nanoplate form is found to be highly active for oxygen evolution reaction in alkaline solutions. For NiFe-LDH grown on a network of CNTs, the resulting NiFe-LDH/CNT complex exhibits higher electrocatalytic activity and stability for oxygen evolution than commercial precious metal Ir catalysts.

pH control in the midgut of Aedesaegypti under different nutritional conditions.

PubMed

Nepomuceno, Denise Barguil; Santos, Vânia Cristina; Araújo, Ricardo Nascimento; Pereira, Marcos Horácio; Sant'Anna, Maurício Roberto; Moreira, Luciano Andrade; Gontijo, Nelder Figueiredo

2017-09-15

Aedes aegypti is one of the most important disease vectors in the world. Because their gut is the first site of interaction with pathogens, it is important to understand A. aegypti gut physiology. In this study, we investigated the mechanisms of pH control in the midgut of A. aegypti females under different nutritional conditions. We found that unfed females have an acidic midgut (pH ∼6). The midgut of unfed insects is actively maintained at pH 6 regardless of the ingestion of either alkaline or acidic buffered solutions. V-ATPases are responsible for acidification after ingestion of alkaline solutions. In blood-fed females, the abdominal midgut becomes alkaline (pH 7.54), and the luminal pH decreases slightly throughout blood digestion. Only ingested proteins were able to trigger this abrupt increase in abdominal pH. The ingestion of amino acids, even at high concentrations, did not induce alkalinisation. During blood digestion, the thoracic midgut remains acidic, becoming a suitable compartment for carbohydrate digestion, which is in accordance with the higher alpha-glucolytic activity detected in this compartment. Ingestion of blood releases alkalising hormones in the haemolymph, which induce alkalinisation in ex vivo preparations. This study shows that adult A. aegypti females have a very similar gut physiology to that previously described for Lutzomyia longipalpis It is likely that all haematophagous Nematocera exhibit the same type of physiological behaviour. © 2017. Published by The Company of Biologists Ltd.

Transient groundwater chemistry near a river: Effects on U(VI) transport in laboratory column experiments

USGS Publications Warehouse

Yin, J.; Haggerty, R.; Stoliker, D.L.; Kent, D.B.; Istok, J.D.; Greskowiak, J.; Zachara, J.M.

2011-01-01

In the 300 Area of a U(VI)-contaminated aquifer at Hanford, Washington, USA, inorganic carbon and major cations, which have large impacts on U(VI) transport, change on an hourly and seasonal basis near the Columbia River. Batch and column experiments were conducted to investigate the factors controlling U(VI) adsorption/desorption by changing chemical conditions over time. Low alkalinity and low Ca concentrations (Columbia River water) enhanced adsorption and reduced aqueous concentrations. Conversely, high alkalinity and high Ca concentrations (Hanford groundwater) reduced adsorption and increased aqueous concentrations of U(VI). An equilibrium surface complexation model calibrated using laboratory batch experiments accounted for the decrease in U(VI) adsorption observed with increasing (bi)carbonate concentrations and other aqueous chemical conditions. In the column experiment, alternating pulses of river and groundwater caused swings in aqueous U(VI) concentration. A multispecies multirate surface complexation reactive transport model simulated most of the major U(VI) changes in two column experiments. The modeling results also indicated that U(VI) transport in the studied sediment could be simulated by using a single kinetic rate without loss of accuracy in the simulations. Moreover, the capability of the model to predict U(VI) transport in Hanford groundwater under transient chemical conditions depends significantly on the knowledge of real-time change of local groundwater chemistry. Copyright 2011 by the American Geophysical Union.

Transient groundwater chemistry near a river: Effects on U(VI) transport in laboratory column experiments

USGS Publications Warehouse

Yin, Jun; Haggerty, Roy; Stoliker, Deborah L.; Kent, Douglas B.; Istok, Jonathan D.; Greskowiak, Janek; Zachara, John M.

2011-01-01

In the 300 Area of a U(VI)-contaminated aquifer at Hanford, Washington, USA, inorganic carbon and major cations, which have large impacts on U(VI) transport, change on an hourly and seasonal basis near the Columbia River. Batch and column experiments were conducted to investigate the factors controlling U(VI) adsorption/desorption by changing chemical conditions over time. Low alkalinity and low Ca concentrations (Columbia River water) enhanced adsorption and reduced aqueous concentrations. Conversely, high alkalinity and high Ca concentrations (Hanford groundwater) reduced adsorption and increased aqueous concentrations of U(VI). An equilibrium surface complexation model calibrated using laboratory batch experiments accounted for the decrease in U(VI) adsorption observed with increasing (bi)carbonate concentrations and other aqueous chemical conditions. In the column experiment, alternating pulses of river and groundwater caused swings in aqueous U(VI) concentration. A multispecies multirate surface complexation reactive transport model simulated most of the major U(VI) changes in two column experiments. The modeling results also indicated that U(VI) transport in the studied sediment could be simulated by using a single kinetic rate without loss of accuracy in the simulations. Moreover, the capability of the model to predict U(VI) transport in Hanford groundwater under transient chemical conditions depends significantly on the knowledge of real-time change of local groundwater chemistry.

Utilization of Aluminum Waste with Hydrogen and Heat Generation

NASA Astrophysics Data System (ADS)

Buryakovskaya, O. A.; Meshkov, E. A.; Vlaskin, M. S.; Shkolnokov, E. I.; Zhuk, A. Z.

2017-10-01

A concept of energy generation via hydrogen and heat production from aluminum containing wastes is proposed. The hydrogen obtained by oxidation reaction between aluminum waste and aqueous solutions can be supplied to fuel cells and/or infrared heaters for electricity or heat generation in the region of waste recycling. The heat released during the reaction also can be effectively used. The proposed method of aluminum waste recycling may represent a promising and cost-effective solution in cases when waste transportation to recycling plants involves significant financial losses (e.g. remote areas). Experiments with mechanically dispersed aluminum cans demonstrated that the reaction rate in alkaline solution is high enough for practical use of the oxidation process. In theexperiments aluminum oxidation proceeds without any additional aluminum activation.

Experimental and analytical analysis of polarization and water transport behaviors of hydrogen alkaline membrane fuel cell

NASA Astrophysics Data System (ADS)

Huo, Sen; Zhou, Jiaxun; Wang, Tianyou; Chen, Rui; Jiao, Kui

2018-04-01

Experimental test and analytical modeling are conducted to investigate the operating behavior of an alkaline electrolyte membrane (AEM) fuel cell fed by H2/air (or O2) and explore the effect of various operating pressures on the water transfer mechanism. According to the experimental test, the cell performance is greatly improved through increasing the operating pressure gradient from anode to cathode which leads to significant liquid water permeation through the membrane. The high frequency resistance of the A901 alkaline membrane is observed to be relatively stable as the operating pressure varies based on the electrochemical impedance spectroscopy (EIS) method. Correspondingly, based on the modeling prediction, the averaged water content in the membrane electrode assembly (MEA) does not change too much which leads to the weak variation of membrane ohmic resistance. This reveals that the performance enhancement should give the credit to better electro-chemical reaction kinetics for both the anode and cathode, also prone by the EIS results. The reversion of water back diffusion direction across the membrane is also observed through analytical solution.

Use of agar diffusion assay to evaluate bactericidal activity of formulations of alkaline salts of fatty acids against bacteria associated with poultry processing

USDA-ARS?s Scientific Manuscript database

The agar diffusion assay was used to examine antibacterial activity of alkaline salts of fatty acids (FA). Wells in agar media seeded with bacteria were filled with FA-potassium hydroxide (KOH) solutions, plates were incubated, and zones of inhibition were measured. The relationship between bacteric...

Irrigation water acidification to neutralize alkalinity for nursery crop production: Substrate pH, electrical conductivity, and nutrient concentrations; and plant nutrition and growth

USDA-ARS?s Scientific Manuscript database

Liming agents (LA) in irrigation water, typically associated with carbonates and bicarbonates of calcium (Ca) and magnesium (Mg), contribute to water alkalinity. Repeated application of LA to container crops can cause media-solution pH to rise overtime, that uncorrected, can lead to a nutrient avail...

Disinfecting capabilities of oxychlorine compounds.

PubMed Central

Noss, C I; Olivieri, V P

1985-01-01

The bacterial virus f2 was inactivated by chlorine dioxide at acidic, neutral, and alkaline pH values. The rate of inactivation increased with increasing pH. Chlorine dioxide disproportionation products, chlorite and chlorate, were not active disinfectants. As chlorine dioxide solutions were degraded under alkaline conditions, they displayed reduced viricidal effectiveness, thereby confirming the chlorine dioxide free radical as the active disinfecting species. PMID:3911893

Effect of pH alkaline salts of fatty acids on the inhibition of bacteria associated with poultry processing

USDA-ARS?s Scientific Manuscript database

The agar diffusion assay was used to examine the effect of pH on the ability of alkaline salts of three fatty acids (FA) to inhibit growth of bacteria associated with poultry processing. FA solutions were prepared by dissolving 0.5 M concentrations of caprylic, capric, or lauric acid in separate ali...

Extraction and Enrichment of Protein from Red and Green Macroalgae.

PubMed

Harnedy, Pádraigín A; FitzGerald, Richard J

2015-01-01

Macroalgae, in particular red and green species, are gaining interest as protein-rich foods for human consumption and sources of proteinaceous biofunctional peptide ingredients. During protein extraction the starting raw material, the cell disruption method utilized and the reagents employed have a major effect on the yield of protein recovered. A method is described herein for extraction and semi-purification of food-grade aqueous and alkaline soluble proteins from red and green macroalgae. Dried milled macroalgae are disrupted by osmotic shock with subsequent removal of aqueous soluble proteins by centrifugation. Alkaline soluble proteins are removed following consecutive treatment of the resultant pellet with an alkaline solution. Aqueous and alkaline soluble proteins are then enriched from the crude extracts by isoelectric precipitation.

Removal of dissolved actinides from alkaline solutions by the method of appearing reagents

DOEpatents

Krot, Nikolai N.; Charushnikova, Iraida A.

1997-01-01

A method of reducing the concentration of neptunium and plutonium from alkaline radwastes containing plutonium and neptunium values along with other transuranic values produced during the course of plutonium production. The OH.sup.- concentration of the alkaline radwaste is adjusted to between about 0.1M and about 4M. [UO.sub.2 (O.sub.2).sub.3 ].sup.4- ion is added to the radwastes in the presence of catalytic amounts of Cu.sup.+2, Co.sup.+2 or Fe.sup.+2 with heating to a temperature in excess of about 60.degree. C. or 85.degree. C., depending on the catalyst, to coprecipitate plutonium and neptunium from the radwaste. Thereafter, the coprecipitate is separated from the alkaline radwaste.

Structure and ionic diffusion of alkaline-earth ions in mixed cation glasses A 2O–2MO–4SiO 2 with molecular dynamics simulations

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

Konstantinou, Konstantinos; Sushko, Petr; Duffy, Dorothy M.

2015-05-15

A series of mixed cation silicate glasses of the composition A2O – 2MO – 4SiO2, with A=Li,Na,K and M=Ca,Sr,Ba has been investigated by means of molecular dynamics simulations in order to understand the effect of the nature of the cations on the mobility of the alkaline-earth ions within the glass network. The size of the alkaline-earth cation was found to affect the inter-atomic distances, the coordination number distributions and the bond angle distributions , whereas the medium-range order was almost unaffected by the type of the cation. All the alkaline-earth cations contribute to lower vibrational frequencies but it is observedmore » that that there is a shift to smaller frequencies and the vibrational density of states distribution gets narrower as the size of the alkaline-earth increases. The results from our modeling for the ionic diffusion of the alkaline-earth cations are in a qualitative agreement with the experimental observations in that there is a distinct correlation between the activation energy for diffusion of alkaline earth-ions and the cation radii ratio. An asymmetrical linear behavior in the diffusion activation energy with increasing size difference is observed. The results can be described on the basis of a theoretical model that relates the diffusion activation energy to the electrostatic interactions of the cations with the oxygens and the elastic deformation of the silicate network.« less

Electrodes synthesized from carbon nanostructures coated with a smooth and conformal metal adlayer

DOEpatents

Adzic, Radoslav; Harris, Alexander

2014-04-15

High-surface-area carbon nanostructures coated with a smooth and conformal submonolayer-to-multilayer thin metal films and their method of manufacture are described. The preferred manufacturing process involves the initial oxidation of the carbon nanostructures followed by a surface preparation process involving immersion in a solution with the desired pH to create negative surface dipoles. The nanostructures are subsequently immersed in an alkaline solution containing a suitable quantity of non-noble metal ions which adsorb at surface reaction sites. The metal ions are then reduced via chemical or electrical means. The nanostructures are exposed to a solution containing a salt of one or more noble metals which replace adsorbed non-noble surface metal atoms by galvanic displacement. The process can be controlled and repeated to obtain a desired film coverage. The resulting coated nanostructures may be used, for example, as high-performance electrodes in supercapacitors, batteries, or other electric storage devices.

Effects of irradiation intensity and pH on nutrients release and solids destruction of waste activated sludge using the microwave-enhanced advanced oxidation process.

PubMed

Chan, W I; Liao, P H; Lo, K V

2010-11-01

Using the microwave-enhanced advanced oxidation process (MW/H2O2-AOP), the pH and irradiation intensity on waste activated sludge samples were investigated to provide insight to the athermal effects on nutrients release, solids destruction, particle size distribution and dewaterability, and to demonstrate their interrelationships. Carbonaceous matters and nutrients released into solution depended on the irradiation intensity and time. Higher irradiation levels tended to be more effective in the solubilization of nutrients and had more pronounced effects in the dewaterability of sludge. In terms of particle size distribution, detectable particles increased in size for treatments in acidic conditions, while the dewaterability of treated sludge was improved. In treatments under neutral and alkaline conditions, the particle size range increased, with more small particles formed, thereby significantly deteriorating the dewaterability of sludge treated in alkaline conditions. The best results for the solubilization of nutrients were in alkaline conditions with high irradiation power, but dewaterability of the sludge was compromised. Sludge treatment with the MW/H2O2-AOP in acidic conditions with high irradiation power yielded the best dewaterable sludge and significant nutrient solubilization; therefore, it is the recommended treatment condition for activated sludge.

Precipitation of Secondary Phases from the Dissolution of Silicate Glasses

NASA Technical Reports Server (NTRS)

Ming, Douglas W.; Golden, D. C.

2004-01-01

Basaltic and anorthositic glasses were subjected to aqueous weathering conditions in the laboratory where the variables were pH, temperature, glass composition, solution composition, and time. Leached layers formed at the surfaces of glasses followed by the precipitation of X-ray amorphous iron and titanium oxides in acidic and neutral solutions at 25 C over time. Glass under oxidative hydrothermal treatments at 150 C yielded a three-layered surface; which included an outer smectite layer, a Fe-Ti oxide layer and an innermost thin leached layer. The introduction of Mg into solutions facilitated the formation of phyllosilicates. Aqueous hydrothermal treatment of anorthositic glasses (high Ca, low Ti) at 200 C readily formed smectite, whereas, the basaltic glasses (high Ti) were more resistant to alteration and smectite was not observed. Alkaline hydrothermal treatment at 2000e produced zeolites and smectites; only smectites formed at 200 C in neutral solutions. These mineralogical changes, although observed under controlled conditions, have direct applications in interpreting planetary (e.g., meteorite parent bodies) and terrestrial aqueous alteration processes.

Platinum-based electrocatalysts synthesized by depositing contiguous adlayers on carbon nanostructures

DOEpatents

Adzic, Radoslav R.; Harris, Alexander

2015-10-06

High-surface-area carbon nanostructures coated with a smooth and conformal submonolayer-to-multilayer thin metal films and their method of manufacture are described. The manufacturing process may involve initial oxidation of the carbon nanostructures followed by immersion in a solution with the desired pH to create negative surface dipoles. The nanostructures are subsequently immersed in an alkaline solution containing non-noble metal ions which adsorb at surface reaction sites. The metal ions are then reduced via chemical or electrical means and the nanostructures are exposed to a solution containing a salt of one or more noble metals which replace adsorbed non-noble surface metal atoms by galvanic displacement. Subsequent film growth may be performed via the initial quasi-underpotential deposition of a non-noble metal followed by immersion in a solution comprising a more noble metal. The resulting coated nanostructures may be used, for example, as high-performance electrodes in supercapacitors, batteries, or other electric storage devices.

Platinum-based electrocatalysts synthesized by depositing contiguous adlayers on carbon nanostructures

DOEpatents

Adzic, Radoslav; Harris, Alexander

2013-03-26

High-surface-area carbon nanostructures coated with a smooth and conformal submonolayer-to-multilayer thin metal films and their method of manufacture are described. The preferred manufacturing process involves the initial oxidation of the carbon nanostructures followed by immersion in a solution with the desired pH to create negative surface dipoles. The nanostructures are subsequently immersed in an alkaline solution containing non-noble metal ions which adsorb at surface reaction sites. The metal ions are then reduced via chemical or electrical means and the nanostructures are exposed to a solution containing a salt of one or more noble metals which replace adsorbed non-noble surface metal atoms by galvanic displacement. Subsequent film growth may be performed via the initial quasi-underpotential deposition of a non-noble metal followed by immersion in a solution comprising a more noble metal. The resulting coated nanostructures may be used, for example, as high-performance electrodes in supercapacitors, batteries, or other electric storage devices.

Action of some foreign cations and anions on the chloride permeability of frog muscle

PubMed Central

Hutter, O. F.; Warner, Anne E.

1967-01-01

1. Evidence for the existence in skeletal muscle of a specific cation binding system capable of lowering the chloride permeability was obtained by testing the effect of several metal ion species upon the efflux of 36Cl from frog muscles equilibrated in high-KCl solution. 2. Cu2+, Zn2+ and UO22+ ions, when present in concentrations of approximately 10-4 M in inactive wash solution at pH 7·4 slowed the efflux of 36Cl to half its original value. At pH 5·0, when the chloride permeability was already low as a consequence of hydrogen ion binding, these metal ions had little further effect. 3. Presence of Ni2+, Co2+, Pb2+, Ce3+ and La3+ in 10-4 M or higher concentrations had no detectable influence on the 36Cl efflux. Wide variations in Ca2+ concentration were similarly ineffective. 4. The influence of more adsorbable anions on the chloride permeability was examined at different pH values. Extracellular iodide greatly slowed the rapid efflux of 36Cl into alkaline solution. In acid solutions, when the chloride permeability was already low, the effect of iodide was less pronounced, but still demonstrable. The chloride permeability was consequently increased to a lesser extent by a rise in pH in the presence of iodide. 5. The efflux of iodide and bromide was measured at different pH values under conditions of self exchange. In alkaline solution the permeabilities to iodide and bromide were considerably lower than that to chloride. In acid solution the membrane differentiated less between anion species of different adsorbability. PMID:6040156

Metal-Rich Transition Metal Diborides as Electrocatalysts for Hydrogen Evolution Reactions in a Wide Range of pH

DOE PAGES

Sitler, Steven J.; Raja, Krishnan S.; Charit, Indrajit

2016-09-23

Solid solutions of HfB 2-ZrB 2 mixtures were prepared by high-energy ball milling of diboride and additive powders followed by spark plasma sintering (SPS). A mixture of stoichiometric 1:1 HfB 2-ZrB 2 borides was the base composition to which Hf, Zr, Ta, LaB 6 or Gd 2O 3 was added. Hf, Zr and Ta were added in order to bring the boron-to-metal ratio down to 1.86, rendering the boride as MeB 1.86. In the case of LaB 6 and Gd 2O 3, 1.8 mol% was added. Electroanalytical behavior of hydrogen evolution reactions was evaluated in 1 M H 2SO 4more » and 1 M NaOH solutions. The LaB 6 additive material showed Tafel slopes of 125 and 90 mV/decade in acidic and alkaline solutions respectively. The Hf and Zr rich samples showed Tafel slopes of about 120 mV/decade in both electrolytes. The over potentials of hydrogen evolution reactions (at 10 mA/cm 2) in the alkaline solution were about 100 mV lower than those in acidic solution. The metal-rich diborides and addition of LaB 6 showed better hydrogen evolution reaction (HER) activities than the base 1:1 HfB 2-ZrB 2 stoichiometric diboride solid solution. Furthermore, the higher activity of metal-rich borides could be attributed to the increased electron population at the d-orbitals of the metal shown by band structure modeling calculations using the Density Functional Theory approach.« less

Novel cellulose-based halochromic test strips for naked-eye detection of alkaline vapors and analytes.

PubMed

Abou-Yousef, Hussein; Khattab, Tawfik A; Youssef, Yehia A; Al-Balakocy, Naser; Kamel, Samir

2017-08-01

A simple, portable and highly sensitive naked-eye test strip is successfully prepared for optical detection of gaseous and aqueous alkaline analytes. Novel pH-sensory tricyanofuran-hydrazone (TCFH) disperse colorant containing a hydrazone recognition functional moiety is successfully synthesized via azo-coupling reaction between active methyl-containing tricyanofuran (TCF) heterocycle and diazonium salt of 4-aminobenzaldehyde followed by Knoevenagel condensation with malononitrile. UV-vis absorption spectra display solvatochromism and reversible color changes of the TCFH solution in dimethyl sulfoxide in response to pH variations. We investigate the preparation of hydrophobic cellulose/polyethylene terephthalate composites characterized by their high affinity for disperse dyes. Composite films made from CA, Cell/CA, PET/CA, and Cell/PET-CA are produced via solvent-casting procedure using 10-30% modified cellulose or modified polyethylene terephthalate. The mechanical properties and morphologies of these composite films are investigated. The prepared pH-sensory hydrazone-based disperse dye is then applied to dye the produced cellulose-based composite films employing the high temperature pressure dyeing procedure. The produced halochromic PET-CA-TCFH test strip provide an instant visible signal from orange to purple upon exposure to alkaline conditions as proved by the coloration measurements. The sensor strip exhibits high sensitivity and quick detection toward ammonia in both of aqueous and vapor phases by naked-eye observations at room temperature and atmospheric pressure. Copyright © 2017 Elsevier B.V. All rights reserved.

Structural and computational analysis of peptide recognition mechanism of class-C type penicillin binding protein, alkaline D-peptidase from Bacillus cereus DF4-B

PubMed Central

Nakano, Shogo; Okazaki, Seiji; Ishitsubo, Erika; Kawahara, Nobuhiro; Komeda, Hidenobu; Tokiwa, Hiroaki; Asano, Yasuhisa

2015-01-01

Alkaline D-peptidase from Bacillus cereus DF4-B, called ADP, is a D-stereospecific endopeptidase reacting with oligopeptides containing D-phenylalanine (D-Phe) at N-terminal penultimate residue. ADP has attracted increasing attention because it is useful as a catalyst for synthesis of D-Phe oligopeptides or, with the help of substrate mimetics, L-amino acid peptides and proteins. Structure and functional analysis of ADP is expected to elucidate molecular mechanism of ADP. In this study, the crystal structure of ADP (apo) form was determined at 2.1 Å resolution. The fold of ADP is similar to that of the class C penicillin-binding proteins of type-AmpH. Docking simulations and fragment molecular orbital analyses of two peptides, (D-Phe)4 and (D-Phe)2-(L-Phe)2, with the putative substrate binding sites of ADP indicated that the P1 residue of the peptide interacts with hydrophobic residues at the S1 site of ADP. Furthermore, molecular dynamics simulation of ADP for 50 nsec suggested that the ADP forms large cavity at the active site. Formation of the cavity suggested that the ADP has open state in the solution. For the ADP, having the open state is convenient to bind the peptides having bulky side chain, such as (D-Phe)4. Taken together, we predicted peptide recognition mechanism of ADP. PMID:26370172

Modeling carbon dioxide, pH, and un-ionized ammonia relationships in serial reuse systems

USGS Publications Warehouse

Colt, J.; Watten, B.; Rust, M.

2009-01-01

In serial reuse systems, excretion of metabolic carbon dioxide has a significant impact on ambient pH, carbon dioxide, and un-ionized ammonia concentrations. This impact depends strongly on alkalinity, water flow rate, feeding rate, and loss of carbon dioxide to the atmosphere. A reduction in pH from metabolic carbon dioxide can significantly reduce the un-ionized ammonia concentration and increase the carbon dioxide concentrations compared to those parameters computed from influent pH. The ability to accurately predict pH in serial reuse systems is critical to their design and effective operation. A trial and error solution to the alkalinity-pH system was used to estimate important water quality parameters in serial reuse systems. Transfer of oxygen and carbon dioxide across the air-water interface, at overflow weirs, and impacts of substrate-attached algae and suspended bacteria were modeled. Gas transfer at the weirs was much greater than transfer across the air-water boundary. This simulation model can rapidly estimate influent and effluent concentrations of dissolved oxygen, carbon dioxide, and un-ionized ammonia as a function of water temperature, elevation, water flow, and weir type. The accuracy of the estimates strongly depends on assumed pollutional loading rates and gas transfer at the weirs. The current simulation model is based on mean daily loading rates; the impacts of daily variation loading rates are discussed. Copies of the source code and executable program are available free of charge.

Effect of polymer binders in anode catalyst layer on performance of alkaline direct ethanol fuel cells

NASA Astrophysics Data System (ADS)

Li, Y. S.; Zhao, T. S.; Liang, Z. X.

In preparing low-temperature fuel cell electrodes, a polymer binder is essential to bind discrete catalyst particles to form a porous catalyst layer that simultaneously facilitates the transfer of ions, electrons, and reactants/products. For two types of polymer binder, namely, an A3-an anion conducting ionomer and a PTFE-a neutral polymer, an investigation is made of the effect of the content of each binder in the anode catalyst layer on the performance of an alkaline direct ethanol fuel cell (DEFC) with an anion-exchange membrane and non-platinum (non-Pt) catalysts. Experiments are performed by feeding either ethanol (C 2H 5OH) solution or ethanol-potassium hydroxide (C 2H 5OH-KOH) solution. The experimental results for the case of feeding C 2H 5OH solution without added KOH indicate that the cell performance varies with the A3 ionomer content in the anode catalyst layer, and a content of 10 wt.% exhibits the best performance. When feeding C 2H 5OH-KOH solution, the results show that: (i) in the region of low current density, the best performance is achieved for a membrane electrode assembly without any binder in the anode catalyst layer; (ii) in the region of high current density, the performance is improved with incorporation of PTFE binder in the anode catalyst layer; (iii) the PTFE binder yields better performance than does the A3 binder.

Pattern of solute movement from snow into an upper Michigan stream

USGS Publications Warehouse

Stottlemyer, R.; Toczydlowski, D.

1990-01-01

Precipitation, snowpack, snowmelt, and streamwater samples were collected in a small gauged watershed draining into Lake Superior during winter 1987–88 to assess the importance of snowmelt pattern and meltwater pathways in the occurrence of solute pulses in streamwater. The snowpack along the south shore of Lake Superior can contain 50% of annual precipitation inputs and 38% of annual ionic inputs including moderate levels of strong acids. Throughout winter, thawed surface soils and small but steady snowpack moisture release promoted movement of snowpack solutes to surface mineral soils. Preferential elution of K+, NH4+, and H+ from the snowpack occurred with the initial thaw. Most ions exhibited pulses in snowmelt. Transport of snowpack solutes to the stream during snowmelt was through near-surface soil macropores and overland flow. For those ions with concentrations higher in the snowpack than in the premelt streamwater, K+, NH4+, and H+, the earliest snowmelt pulses had the greatest influence on streamwater chemistry. Unlike other portions of the region with resistant bedrock, the widespread presence of alkaline glacial till provides excess stream acid neutralization capacity (ANC) to buffer acidic inputs. Peak winter streamwater ANC reduction was caused principally by spring melt dilution of base cations and associated alkalinity, constant high SO42- levels, and an increase in NO3-. The maximum reduction in stream ANC was concurrent with overland flow. Relative to its snowmelt concentration, NO3- was highest in streamwater with some stream input likely the result of nitrification and N mineralization.

Stability of micafungin sodium solutions at different concentrations in glass bottles and syringes.

PubMed

Briot, Thomas; Vrignaud, Sandy; Lagarce, Frédéric

2015-08-15

Micafungin is a costly treatment and packaging of 50 mg or 100 mg bottles only are available, while doses lower than 5 mg and 20 mg are often necessary in neonates and paediatrics patients, respectively. The stability of micafungin sodium in polypropylene syringes and glass bottles was studied at different concentrations. Solutions of micafungin diluted with NaCl 0.9% were prepared in glass bottles (20 and 10 mg/mL) or syringes (1 and 0.5 mg/mL) and stored at 25 °C, 60% humidity (RH), in the dark (ICH conditions). Solutions were also exposed to heat (70 °C) or alkaline solution (NaOH) in order to force degradation. Samples were analysed at days 1, 5, 8 (for bottles) and also 15 (for syringes) after the preparation and assayed in triplicate. Stability was studied using a stability-indicating high-performance liquid chromatographic method. Syringes stored at 25 °C retained over 90% of their initial concentration over the study period. Temperature and alkaline conditions had significant effect on the stability of micafungin, leading to apparition of degradation products. Moreover, sub visible particles were in the specification of the European Pharmacopeia along 15 days. To conclude, micafungin diluted in NaCl 0.9% and stored in polypropylene syringes was chemically stable for at least 15 days at 25 °C in the dark. Copyright © 2015 Elsevier B.V. All rights reserved.

Optimum mix for fly ash geopolymer binder based on workability and compressive strength

NASA Astrophysics Data System (ADS)

Arafa, S. A.; Ali, A. Z. M.; Awal, A. S. M. A.; Loon, L. Y.

2018-04-01

The request of concrete is increasing every day for sustaining the necessity of development of structure. The production of OPC not only consumes big amount of natural resources and energy, but also emit significant quantity of CO2 to the atmosphere. Therefore, it is necessary to find alternatives like Geopolymer to make the concrete environment friendly. Geopolymer is an inorganic alumino-silicate compound, produced from fly ash. This paper describes the experimental work conducted by casting 40 geopolymer paste mixes, and was cured at 80°C for 24 h to evaluate the effect of various parameters affecting the workability and compressive strength. Alkaline solution to fly ash ratio and sodium hydroxide (NaOH) concentration were chosen as the key parameters of strength and workability. Laboratory investigation with different percentage of sodium hydroxide concentration and different alkaline liquid to fly ash ratio reveals that the optimum ratios are 10 M, AL/FA=0.5. It has generally been found that the workability decreased and the compressive strength increased with an increase in the concentration of sodium hydroxide solution. However, workability was increased and the compressive strength was decreased with the increase in the ratio of fly ash to alkaline solution.

40 CFR Appendix B to Part 425 - Modified Monier-Williams Method

Code of Federal Regulations, 2014 CFR

2014-07-01

... is removed by scrubbing the nitrogen gas stream in a pH 7 buffer solution. The sulfide gas is collected by passage through an alkaline hydrogen peroxide scrubbing solution in which it is oxidized to sulfate. Sulfate concentration in the scrubbing solution is determined by either EPA gravimetric test...

40 CFR Appendix B to Part 425 - Modified Monier-Williams Method

Code of Federal Regulations, 2013 CFR

2013-07-01

... is removed by scrubbing the nitrogen gas stream in a pH 7 buffer solution. The sulfide gas is collected by passage through an alkaline hydrogen peroxide scrubbing solution in which it is oxidized to sulfate. Sulfate concentration in the scrubbing solution is determined by either EPA gravimetric test...

Resin catalysts and method of preparation

DOEpatents

Smith, Jr., Lawrence A.

1986-01-01

Heat stabilized catalyst compositions are prepared from nuclear sulfonic acid, for example, macroporous crosslinked polyvinyl aromatic compounds containing sulfonic acid groups are neutralized with a metal of Al, Fe, Zn, Cu, Ni, ions or mixtures and alkali, alkaline earth metals or ammonium ions by contacting the resin containing the sulfonic acid with aqueous solutions of the metals salts and alkali, alkaline earth metal or ammonium salts. The catalysts have at least 50% of the sulfonic acid groups neutralized with metal ions and the balance of the sulfonic acid groups neutralized with alkali, alkaline earth ions or ammonium ions.

Resin catalysts and method of preparation

DOEpatents

Smith, L.A. Jr.

1986-12-16

Heat stabilized catalyst compositions are prepared from nuclear sulfonic acid, for example, macroporous crosslinked polyvinyl aromatic compounds containing sulfonic acid groups are neutralized with a metal of Al, Fe, Zn, Cu, Ni, ions or mixtures and alkali, alkaline earth metals or ammonium ions by contacting the resin containing the sulfonic acid with aqueous solutions of the metals salts and alkali, alkaline earth metal or ammonium salts. The catalysts have at least 50% of the sulfonic acid groups neutralized with metal ions and the balance of the sulfonic acid groups neutralized with alkali, alkaline earth ions or ammonium ions.

Transcriptome Exploration in Leymus chinensis under Saline-Alkaline Treatment Using 454 Pyrosequencing

PubMed Central

Sun, Yepeng; Wang, Fawei; Wang, Nan; Dong, Yuanyuan; Liu, Qi; Zhao, Lei; Chen, Huan; Liu, Weican; Yin, Hailong; Zhang, Xiaomei; Yuan, Yanxi; Li, Haiyan

2013-01-01

Background Leymus chinensis (Trin.) Tzvel. is a high saline-alkaline tolerant forage grass genus of the tribe Gramineae family, which also plays an important role in protection of natural environment. To date, little is known about the saline-alkaline tolerance of L. chinensis on the molecular level. To better understand the molecular mechanism of saline-alkaline tolerance in L. chinensis, 454 pyrosequencing was used for the transcriptome study. Results We used Roche-454 massive parallel pyrosequencing technology to sequence two different cDNA libraries that were built from the two samples of control and under saline-alkaline treatment (optimal stress concentration-Hoagland solution with 100 mM NaCl and 200 mM NaHCO3). A total of 363,734 reads in control group and 526,267 reads in treatment group with an average length of 489 bp and 493 bp were obtained, respectively. The reads were assembled into 104,105 unigenes with MIRA sequence assemable software, among which, 73,665 unigenes were in control group, 88,016 unigenes in treatment group and 57,576 unigenes in both groups. According to the comparative expression analysis between the two groups with the threshold of “log2 Ratio ≥1”, there were 36,497 up-regulated unegenes and 18,218 down-regulated unigenes predicted to be the differentially expressed genes. After gene annotation and pathway enrichment analysis, most of them were involved in stress and tolerant function, signal transduction, energy production and conversion, and inorganic ion transport. Furthermore, 16 of these differentially expressed genes were selected for real-time PCR validation, and they were successfully confirmed with the results of 454 pyrosequencing. Conclusions This work is the first time to study the transcriptome of L. chinensis under saline-alkaline treatment based on the 454-FLX massively parallel DNA sequencing platform. It also deepened studies on molecular mechanisms of saline-alkaline in L. chinensis, and constituted a database for future studies. PMID:23365637

Molecular-dynamics simulations of alkaline-earth metal cations in water by atom-bond electronegativity equalization method fused into molecular mechanics.

PubMed

Yang, Zhong-Zhi; Li, Xin

2005-09-01

Intermolecular potential for alkaline-earth metal (Be(2+), Mg(2+), and Ca(2+)) cations in water has been derived using the atom-bond electronegativity equalization method fused into molecular mechanics (ABEEM/MM), and it is consistent with what was previously applied to the hydration study of the monovalent cations. Parameters for the effective interaction between a cation and a water molecule were determined, reproducing the ab initio results. The static, dynamic, and thermodynamic properties of Be(2+)(aq), Mg(2+)(aq), and Ca(2+)(aq) were studied using these potential parameters. Be(2+) requires a more complicated form of the potential function than Mg(2+) and Ca(2+) in order to obtain better fits. Strong influences of the twofold charged cations on the structures of the hydration shells and some other properties of aqueous ionic solutions are discussed and compared with the results of a previous study of monovalent cations in water. At the same time, comparative study of the hydration properties of each cation is also discussed. This work demonstrates that ABEEM/MM provides a useful tool in the exploration of the hydration of double-charged cations in water.

Importance of water quality in container plant production

Treesearch

John M. Ruter

2013-01-01

High substrate pH is a major problem for producers of container-grown plants and seedlings. The primary cause of high substrate pH is irrigation water with high alkalinity. Alkalinity is defined as the capacity of water to neutralize acids. Some alkalinity in irrigation water is beneficial as it serves as a buffer to large swings in pH levels, but high alkalinity in...

The influence of alkalinity of portland cement on the absorption characteristics of superabsorbent polymers (SAP) for use in internally cured concrete

NASA Astrophysics Data System (ADS)

Tabares Tamayo, Juan D.

The concrete industry increasingly emphasizes advances in novel materials that promote construction of more resilient infrastructure. Due to its potential to improve concrete durability, internal curing (IC) of concrete by means of superabsorbent polymers (SAP) has been identified as one of the most promising technologies of the 21st century. The addition of superabsorbent polymers into a cementitious system promotes further hydration of cement by providing internal moisture during the hardening and strength development periods, and thus limits self-desiccation, shrinkage, and cracking. This thesis presents the work performed on the series of cement pastes with varying alkalinity of their pore solutions to provide a better understanding of: (1) the influence of the chemistry of the pore solution (i.e. its level of alkalinity and the type of ionic species present) on the absorption capacity of SAP, and (2) the effectiveness of SAP with different absorption capacities as an internal curing agent. This research work was divided into three stages: (a) materials characterization, (b) measurement of absorption capacity of SAP in synthetic pore solutions, and (c) evaluation of the internal curing effectiveness of SAP. During the first stage (Materials Characterization), pore solutions were extracted from the fresh (5 minutes old) cement pastes prepared using cements with three different levels of alkalinity. The pH values of the extracted solutions were determined (using the pH meter) and their chemical analysis was performed by means of titration (concentration of hydroxyl), ion chromatography (sulfates and chlorides), atomic absorption (AA) and inductively coupled plasma optical emission spectrometry (ICP) (sodium, potassium and calcium). The commercial SAP adopted for this study was used with "as-supplied" gradation and with the finer gradation obtained by grinding the original polymer in the 6850 Cryomilling Freezer/Mill. The physical properties of these SAP's, such as the shape and size of the particles, were determined by optical microscopy combined with image analysis. The second stage, the absorption capacity of SAP's, involved determination of the swelling behavior and the absorption capacity of polymers exposed to artificial pore solutions with different levels of alkalinity. The swelling behavior was followed using the optical microscope while the absorption capacity was characterized using the tea bag method. It was found that changes in the chemical compositions of the pore solutions influence the adsorption kinetics and result in different absorption isotherms. In the third stage, the internal curing effects of inclusion of SAP in cement pastes were evaluated. Mixture proportions of pastes used in this stage of the study were selected based on the absorption capacity of the SAP determined in stage two. The testing of the pastes involved determination of their set times, heat of hydration, and autogenous shrinkage.

New singlet oxygen generator for chemical oxygen-iodine lasers

NASA Astrophysics Data System (ADS)

Yoshida, S.; Saito, H.; Fujioka, T.; Yamakoshi, H.; Uchiyama, T.

1986-11-01

Experiments have been carried out to investigate a new method for generating O2(1Delta) with long-time operation of an efficient chemical oxygen-iodine laser system in mind. An impinging-jet nozzle was utilized to atomize a H2O2-KOH solution so that the alkaline H2O2/Cl2 reaction might occur in droplet-gas phase with high excitation efficiency. Experimental results indicate that the present generator can yield as high as 80 percent of O2(1Delta) with reasonable O2 flow rate.

Extreme 13C depletions in seawater-derived brines and their implications for the past geochemical carbon cycle

NASA Astrophysics Data System (ADS)

Lazar, Boaz; Erez, Jonathan

1990-12-01

Extreme depletions in the 13C content of the total dissolved inorganic carbon (CT) were found in brines overlying microbial mat communities. Total alkalinity (AT) and CT in the brines suggest that intense photosynthetic activity of the microbial mat communities depletes the CT from the brine. We suggest that this depletion drives a large, kinetic, negative fractionation of carbon isotopes similar to that observed in highly alkaline solutions. In brines of extreme salinity where microbial mat communities no longer exist, the 13C content of the CT increases, probably because photosynthesis no longer dominates the gas-exchange processes. This mechanism explains light carbon-isotope compositions of carbonate rocks from evaporitic sections and bears on the interpretation of δ13C values in bedded stromatolitic limestones that are ca. 3.5 b.y. old.

Mechanism and models for zinc metal morphology in alkaline media

NASA Technical Reports Server (NTRS)

May, C. E.; Kautz, H. E.

1981-01-01

Based on experimental observations, a mechanism is presented to explain existence of the different morphologies of electrodeposited zinc in alkaline solution. The high current density dendrites appear to be due to more rapid growth on the nonbasal crystallographic planes than on the basal plane. The low current density moss apparently results from dissolution from the nonbasal planes at low cathodic voltages. Electrochemical models were sought which would produce such a phenomenon. The fundamental plating mechanism alone accounts only for different rates on different planes, not for zinc dissolution from a plane in the cathodic region. Fourteen models were explored; two models were in accord with the proposed mechanism. One involves rapid disproportionation of the zinc +1 species on the nonbasal planes. The other involves a redox reaction (corrosion) between the zinc-zincate and hydrogen-water systems.

Enhancing uranium uptake by amidoxime adsorbent in seawater: An investigation for optimum alkaline conditioning parameters

DOE PAGES

Das, Sadananda; Tsouris, Costas; Zhang, Chenxi; ...

2015-09-07

A high-surface-area polyethylene-fiber adsorbent (AF160-2) has been developed at the Oak Ridge National Laboratory by radiation-induced graft polymerization of acrylonitrile and itaconic acid. The grafted nitriles were converted to amidoxime groups by treating with hydroxylamine. The amidoximated adsorbents were then conditioned with potassium hydroxide (KOH) by varying different reaction parameters such as KOH concentration (0.2, 0.44, and 0.6 M), duration (1, 2, and 3 h), and temperature (60, 70, and 80 °C). Adsorbent screening was then performed with simulated seawater solutions containing sodium chloride and sodium bicarbonate, at concentrations found in seawater, and uranium nitrate at a uranium concentration ofmore » ~7–8 ppm and pH 8. Fourier transform infrared spectroscopy and solid-state NMR analyses indicated that a fraction of amidoxime groups was hydrolyzed to carboxylate during KOH conditioning. The uranium adsorption capacity in the simulated seawater screening solution gradually increased with conditioning time and temperature for all KOH concentrations. It was also observed that the adsorption capacity increased with an increase in concentration of KOH for all the conditioning times and temperatures. AF160-2 adsorbent samples were also tested with natural seawater using flow-through experiments to determine uranium adsorption capacity with varying KOH conditioning time and temperature. Based on uranium loading capacity values of several AF160-2 samples, it was observed that changing KOH conditioning time from 3 to 1 h at 60, 70, and 80 °C resulted in an increase of the uranium loading capacity in seawater, which did not follow the trend found in laboratory screening with stimulated solutions. Longer KOH conditioning times lead to significantly higher uptake of divalent metal ions, such as calcium and magnesium, which is a result of amidoxime conversion into less selective carboxylate. The scanning electron microscopy showed that long conditioning times may also lead to adsorbent degradation.« less

Enhancing Uranium Uptake by Amidoxime Adsorbent in Seawater: An investigation for optimum alkaline conditioning parameters

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

Das, S.; Tsouris, Constantinos; Zhang, C.

2016-04-20

A high-surface-area polyethylene-fiber adsorbent (AF160-2) has been developed at the Oak Ridge National Laboratory (ORNL) by radiation-induced graft polymerization of acrylonitrile and itaconic acid. The grafted nitriles were converted to amidoxime groups by treating with hydroxylamine. The amidoximated adsorbents were then conditioned with potassium hydroxide (KOH) by varying different reaction parameters such as KOH concentration (0.2, 0.44, and 0.6 M), duration (1, 2, and 3 h), and temperature (60, 70, and 80 ºC). Adsorbent screening was then performed with simulated seawater solutions containing sodium chloride and sodium bicarbonate, at concentrations found in seawater, and uranium nitrate at a uranium concentrationmore » of ~ 7-8 ppm and pH 8. FTIR and solid state NMR indicated that a fraction of amidoxime groups was hydrolyzed to carboxylate during KOH conditioning. The uranium adsorption capacity in the simulated seawater screening solution gradually increased with conditioning time and temperature for all KOH concentrations. It was also observed that the adsorption capacity increased with an increase in concentration of KOH for all the conditioning times and temperatures. AF160-2 adsorbent samples were also tested with natural seawater using flow-through experiments to determine uranium adsorption capacity with varying KOH conditioning time and temperature. Based on uranium loading capacity values of several AF160-2 samples, it was observed that changing KOH conditioning time from 3 to 1 h at 60, 70, and 80 ºC resulted in increase of the uranium loading capacity in seawater, which did not follow the trend found in laboratory screening with stimulated solutions. Longer KOH conditioning times lead to significantly higher uptake of divalent metal ions, such as calcium and magnesium, which is a result of amidoxime conversion into less selective carboxylate. Scanning electron microscopy showed that long conditioning times may also lead to adsorbent degradation« less

Highly selective SERS probe for Hg(II) detection using tryptophan-protected popcorn shaped gold nanoparticles.

PubMed

Senapati, Tapas; Senapati, Dulal; Singh, Anant Kumar; Fan, Zhen; Kanchanapally, Rajashekhar; Ray, Paresh Chandra

2011-10-07

Contamination of the environment with toxic Hg(II) is becoming a huge concern throughout the world now. Driven by the need, this communication reports for the first time a tryptophan protected popcorn shaped gold nanomaterials based SERS probe for rapid, easy and highly selective recognition of Hg(II) ions in the 5 ppb level from aqueous solution, with high sensitivity and selectivity over competing analytes. We demonstrate that our SERS assay is capable of measuring the amount of Hg(II) in alkaline battery. This journal is © The Royal Society of Chemistry 2011

Mathematical model of water transport in Bacon and alkaline matrix-type hydrogen-oxygen fuel cells

NASA Technical Reports Server (NTRS)

Prokopius, P. R.; Easter, R. W.

1972-01-01

Based on general mass continuity and diffusive transport equations, a mathematical model was developed that simulates the transport of water in Bacon and alkaline-matrix fuel cells. The derived model was validated by using it to analytically reproduce various Bacon and matrix-cell experimental water transport transients.

Process for producing peracids from aliphatic hydroxy carboxylic acids

DOEpatents

Chum, Helena L.; Ratcliff, Matthew A.; Palasz, Peter D.

1986-01-01

A process for producing peracids from lactic acid-containing solutions derived from biomass processing systems comprising: adjusting the pH of the solution to about 8-9 and removing alkaline residue fractions therefrom to form a solution comprised substantially of lower aliphatic hydroxy acids; oxidizing the solution to produce volatile lower aliphatic aldehydes; removing said aldehydes as they are generated; and converting said aldehydes to peracids.

Quaternized poly(vinyl alcohol)/alumina composite polymer membranes for alkaline direct methanol fuel cells

NASA Astrophysics Data System (ADS)

Yang, Chun-Chen; Chiu, Shwu-Jer; Chien, Wen-Chen; Chiu, Sheng-Shin

The quaternized poly(vinyl alcohol)/alumina (designated as QPVA/Al 2O 3) nanocomposite polymer membrane was prepared by a solution casting method. The characteristic properties of the QPVA/Al 2O 3 nanocomposite polymer membranes were investigated using thermal gravimetric analysis (TGA), scanning electron microscopy (SEM), dynamic mechanical analysis (DMA), micro-Raman spectroscopy, and AC impedance method. Alkaline direct methanol fuel cell (ADMFC) comprised of the QPVA/Al 2O 3 nanocomposite polymer membrane were assembled and examined. Experimental results indicate that the DMFC employing a cheap non-perfluorinated (QPVA/Al 2O 3) nanocomposite polymer membrane shows excellent electrochemical performances. The peak power densities of the DMFC with 4 M KOH + 1 M CH 3OH, 2 M CH 3OH, and 4 M CH 3OH solutions are 28.33, 32.40, and 36.15 mW cm -2, respectively, at room temperature and in ambient air. The QPVA/Al 2O 3 nanocomposite polymer membranes constitute a viable candidate for applications on alkaline DMFC.

Reductive atmospheric acid leaching of spent alkaline batteries in H2SO4/Na2SO3 solutions

NASA Astrophysics Data System (ADS)

Morcali, Mehmet Hakan

2015-07-01

This work studies the optimum reductive leaching process for manganese and zinc recovery from spent alkaline battery paste. The effects of reducing agents, acid concentration, pulp density, reaction temperature, and leaching time on the dissolution of manganese and zinc were investigated in detail. Manganese dissolution by reductive acidic media is an intermediate-controlled process with an activation energy of 12.28 kJ·mol-1. After being leached, manganese and zinc were selectively precipitated with sodium hydroxide. The zinc was entirely converted into zincate (Zn(OH){4/2-}) ions and thus did not co-precipitate with manganese hydroxide during this treatment (2.0 M NaOH, 90 min, 200 r/min, pH > 13). After the manganese was removed from the solution, the Zn(OH){4/2-} was precipitated as zinc sulfate in the presence of sulfuric acid. The results indicated that this process could be effective in recovering manganese and zinc from alkaline batteries.

Performance of AA5052 alloy anode in alkaline ethylene glycol electrolyte with dicarboxylic acids additives for aluminium-air batteries

NASA Astrophysics Data System (ADS)

Wang, DaPeng; Zhang, DaQuan; Lee, KangYong; Gao, LiXin

2015-11-01

Dicarboxylic acid compounds, i.e. succinic acid (SUA), adipic acid (ADA) and sebacic acid (SEA), are used as electrolyte additives in the alkaline ethylene glycol solution for AA5052 aluminium-air batteries. It shows that the addition of dicarboxylic acids lowers the hydrogen gas evolution rate of commercial AA5052 aluminium alloy anode. AA5052 aluminium alloy has wide potential window for electrochemical activity and better discharge performance in alkaline ethylene glycol solution containing dicarboxylic acid additives. ADA has the best inhibition effect for the self-corrosion of AA5052 anode among the three dicarboxylic acid additives. Fourier transform infrared spectroscopy (FT-IR) reveals that dicarboxylic acids and aluminium ions can form coordination complexes. Quantum chemical calculations shows that ADA has a smaller energy gap (ΔE, the energy difference between the lowest unoccupied orbital and the highest occupied orbital), indicating that ADA has the strongest interaction with aluminium ions.

Two-Dimensional MoS2 Confined Co(OH)2 Electrocatalysts for Hydrogen Evolution in Alkaline Electrolytes.

PubMed

Luo, Yuting; Li, Xu; Cai, Xingke; Zou, Xiaolong; Kang, Feiyu; Cheng, Hui-Ming; Liu, Bilu

2018-05-22

The development of abundant and cheap electrocatalysts for the hydrogen evolution reaction (HER) has attracted increasing attention over recent years. However, to achieve low-cost HER electrocatalysis, especially in alkaline media, is still a big challenge due to the sluggish water dissociation kinetics as well as the poor long-term stability of catalysts. In this paper we report the design and synthesis of a two-dimensional (2D) MoS 2 confined Co(OH) 2 nanoparticle electrocatalyst, which accelerates water dissociation and exhibits good durability in alkaline solutions, leading to significant improvement in HER performance. A two-step method was used to synthesize the electrocatalyst, starting with the lithium intercalation of exfoliated MoS 2 nanosheets followed by Co 2+ exchange in alkaline media to form MoS 2 intercalated with Co(OH) 2 nanoparticles (denoted Co-Ex-MoS 2 ), which was fully characterized by spectroscopic studies. Electrochemical tests indicated that the electrocatalyst exhibits superior HER activity and excellent stability, with an onset overpotential and Tafel slope as low as 15 mV and 53 mV dec -1 , respectively, which are among the best values reported so far for the Pt-free HER in alkaline media. Furthermore, density functional theory calculations show that the cojoint roles of Co(OH) 2 nanoparticles and MoS 2 nanosheets result in the excellent activity of the Co-Ex-MoS 2 electrocatalyst, and the good stability is attributed to the confinement of the Co(OH) 2 nanoparticles. This work provides an imporant strategy for designing HER electrocatalysts in alkaline solutions, and can, in principle, be expanded to other materials besides the Co(OH) 2 and MoS 2 used here.

[Intraoperative lactic acidosis, can it be treated? Clinico-experimental, prospective, sequential study].

PubMed

Pietropaoli, P; Caporelli, S; De Pace, F; Donati, A; Adrario, E; Luzi, A; Munch, C; Giovannini, C; Frezzotti, A R

1994-12-01

To verify the efficacy and absence of risk attributable to therapy with alkaline solutions for correction of lactic acidosis and to demonstrate the usefulness of L-carnitine in converting lactate into pyruvate in conditions of good blood oxygenation. Prospective study on a consecutive series of patients subdivided into three groups following the use of: alkalinizing therapy (group I), L-carnitine (group II), or saline solution (group III). Groups 1 and 2 were further subdivided into subgroups "a" and "b" according to the type of alkalinizing agent and of L-carnitine somministration. Teaching Hospital-Torrette di Ancona. 65 patients submitted to major vascular surgery with aortic clamping in the time period between January 1992 and August 1993. During aortic clamping patients of: group I received 2 mEq:kg of bicarbonate or tromentamolo according to the specific subgroup. Group II received a bolus of 2 g of L-carnitine, patients of group IIb received further 2 g of carnitine in continuous perfusion until the end of surgery. Group III received no pharmacological intervention. HR BP, arterial blood gases and lactic acid levels were measured at 12 pre-determined times. Only a neutralizing effect of alkalinizing therapy was observed, whereas the lactic acid measurements demonstrated no significant differences between the different groups. These results confirm the data of other Authors concerning the good compliance of alkalinizing therapy, however, there was demonstrated no clear evidence of its effective usefulness. No metabolic stimulation due to L-canitina could be demonstrated in our experimental conditions.

The corrosion of titanium in alkaline peroxide bleach liquors

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

Wyllie, W.E. II; Brown, B.E.; Duquette, D.J.

1994-12-31

An experimental program to determine the effects of hydrogen peroxide (H{sub 2}O{sub 2}) and of potential corrosion inhibitors on the corrosion behavior of titanium has been developed. Corrosion rates less than 0.25 mm/y were observed in laboratory bleach liquor at pH 12 to which 5 g/l of H{sub 2}O{sub 2} were added. At pH 13, with 10 g/l H{sub 2}O{sub 2}, the corrosion rates were unacceptably high in both sodium hydroxide (NaOH) and laboratory bleach liquor solutions (>8.38 mm/y). The preliminary results of inhibitor studies indicated that the addition of 3.7 g/l sodium silicate or 0.01 g/l calcium nitrate (Ca(NO{submore » 3}){sub 2}) effectively inhibited the corrosion of titanium exposed to 5 g/l of H{sub 2}O{sub 2} in NaOH solutions of pH 12. It was also found that in simulated paper mill chemistries, i.e., basic solutions containing 3.7 g/l sodium silicate and 0.6 g/l EDTA (ethylenediaminetetraacetic acid), corrosion rates increased markedly with the addition of 5 g/l H{sub 2}O{sub 2}. However, subsequent additions of peroxide resulted in corrosion rates which were even lower than those found in NaOH. This is believed to be due to the formation of a black scale on the surface of the sample. The addition of magnesium sulfate (MgSO{sub 4}) in the 0.1--0.5 g/l range also was shown to inhibit corrosion in the NaOH solution, but only after prior exposure to H{sub 2}O{sub 2}.« less

Brownian dynamics simulation of protein diffusion in crowded environments

NASA Astrophysics Data System (ADS)

Mereghetti, Paolo; Wade, Rebecca C.

2013-02-01

High macromolecular concentrations are a distinguishing feature of living organisms. Understanding how the high concentration of solutes affects the dynamic properties of biological macromolecules is fundamental for the comprehension of biological processes in living systems. We first describe the development of a Brownian dynamics simulation methodology to investigate the dynamic and structural properties of protein solutions using atomic-detail protein structures. We then discuss insights obtained from applying this approach to simulation of solutions of a range of types of proteins.

Experiment on the treatment of waste extraction solvent from the molybdenum-99 process

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

Hsien-Ming Hsiao; Chang-Liang Hu; Kuang-Li Chien

2013-07-01

In the Mo-99 (Molybdenum-99) isotope extraction test process for radiopharmaceutical applications, organic solvent is used to extract Mo-99 from an irradiated UO{sub 2} dissolution. The extraction solvent was stored when the test work was stopped. A total of about 120 liters of waste solvent was stored at INER (Institute of Nuclear Energy Research, Taiwan). The extraction solvent consisted of 5% di-(2-ethylhexyl)-phosphoric acid (D2EHPA) and kerosene. The radionuclides found in the waste solvent include Cs-137, Am-241, Tc-99, and Sr-90, which give off gross alpha and beta radioactivity of 1898 and 471 Bq/ml, respectively. This study aims to remove radionuclides from themore » waste solvent using sodium carbonate and sodium hydroxide solutions in different concentrations. After mixing the waste solvent with the alkaline solution followed by settling, a third phase other than organic and aqueous phase appeared which is expected due to the saponification reaction. The experimental results showed that increasing the number of washing and the alkaline solution concentration could enhance the radionuclides removal rate. An optimal removal method was proposed using 2 M Na{sub 2}CO{sub 3} solution twice followed by 1 M NaOH solution one time for the third phase generated early in the mixing stages. The remaining gross alpha and beta radioactivity of the treated organic solvent was 2 and 3 Bq/ml, respectively. The treated solvent could be stabilized by ashing at 500 deg. C and then immobilized. The alkaline solution would be neutralized by hydrochloric or nitric acid and then treated using a variety of adsorbents or bone char via adsorption to remove nuclides to meet the wastewater discharge limitation. (authors)« less

Electrochemical and in-situ Surface-Enhanced Raman Spectroscopic (SERS) study of passive films formed on low-carbon steel in highly alkaline environments

NASA Astrophysics Data System (ADS)

Mancio, Mauricio

In reinforced concrete, a passive layer forms because of the alkaline conditions in the pores of the cement paste, where large concentrations of hydroxides create a solution with pH typically between 12 and 14. The corrosion resistance of the material depends on the characteristics and integrity of the passive film; however, currently very limited information is available about the passive films formed on carbon steel under such conditions. This work presents an electrochemical and in-situ Surface-Enhanced Raman Spectroscopic (SERS) study of passive films formed on low-carbon steel in highly alkaline environments. More specifically, the study focuses on the characterization of the films formed on ASTM A36 steel reinforcing bar exposed to aqueous solutions that aim to reproduce the chemistry of the environment typically found within the cement paste. Electrochemical techniques such as cyclic potentiodynamic polarization curves, galvanostatic cathodic polarization and linear polarization resistance were employed, in addition to in-situ Surface Enhanced Raman Spectroscopy (SERS). The experimental setup was built in a way that SERS experiments could be performed simultaneously with potentiodynamic polarization curves, enabling a detailed analysis of the formation and reduction of the surface films as a function of applied potential. Three solutions with different pH levels were used for the polarization and SERS experiments, namely 0.55M KOH + 0.16M NaOH ([OH-]=0.71), 0.08M KOH + 0.02M NaOH ([OH-]=0.10) and 0.008M KOH + 0.002M NaOH ([OH-]=0.01). Additional NaOH solutions in which the pH was varied from 13 to 9 and the ionic strength from 10 -5 to 10-1 were prepared for a pilot study using linear polarization resistance. Results show that the features observed in the cyclic potentiodynamic polarization curves correlated well with the potential arrests observed in the GCP plots as well as with the changes observed in the SERS spectra, providing valuable information about the formation of passive films on carbon steel in each of the environments studied in this research. Although there are key differences among the films formed in the different solutions tested---particularly regarding their thickness and protectiveness---once the film-formation processes had been completed, generally the films were characterized by an inner layer of Fe(II) and an outer layer of Fe(III). A Fe(OH)2-like species appears consistently as dominating the inner Fe(II) layer, while the outer typically composed mostly by gamma-Fe2O3 and/or gamma-FeOOH. Film thickness varied from about 22 nm to 266 nm depending on the pH of the solution, and decreased as pH was reduced.

Field measurement of alkalinity and pH

USGS Publications Warehouse

Barnes, Ivan

1964-01-01

The behavior of electrometric pH equipment under field conditions departs from the behavior predicted from Nernst's law. The response is a linear function of pH, and hence measured pH values may be corrected to true pH if the instrument is calibrated with two reference solutions for each measurement. Alkalinity titrations may also be made in terms of true pH. Standard methods, such as colorimetric titrations, were rejected as unreliable or too cumbersome for rapid field use. The true pH of the end point of the alkalinity titration as a function of temperature, ionic strength, and total alkalinity has been calculated. Total alkalinity in potable waters is the most important factor influencing the end point pH, which varies from 5.38 (0 ? C, 5 ppm (parts per million) HC0a-) to 4.32 (300 ppm HC0a-,35 ? C), for the ranges of variables considered. With proper precautions, the pH may be determined to =i:0.02 pH and the alkalinity to =i:0.6 ppm HCO3- for many naturally occurring bodies of fresh water.

Effects of cement alkalinity, exposure conditions and steel-concrete interface on the time-to-corrosion and chloride threshold for reinforcing steel in concrete

NASA Astrophysics Data System (ADS)

Nam, Jingak

Effects of (1) cement alkalinity (low, normal and high), (2) exposure conditions (RH and temperature), (3) rebar surface condition (as-received versus cleaned) and (4) density and distribution of air voids at the steel-concrete interface on the chloride threshold and time-to-corrosion for reinforcing steel in concrete have been studied. Also, experiments were performed to evaluate effects of RH and temperature on the diffusion of chloride in concrete and develop a method for ex-situ pH measurement of concrete pore water. Once specimens were fabricated and exposed to a corrosive chloride solution, various experimental techniques were employed to determine time-to-corrosion, chloride threshold, diffusion coefficient and void density along the rebar trace as well as pore water pH. Based upon the resultant data, several findings related to the above parameters have been obtained as summarized below. First, time for the corrosion initiation was longest for G109 concrete specimens with high alkalinity cement (HA). Also, chloride threshold increased with increasing time-to-corrosion and cement alkalinity. Consequently, the HA specimens exhibited the highest chloride threshold compared to low and normal alkalinity ones. Second, high temperature and temperature variations reduced time-to-corrosion of reinforcing steel in concrete since chloride diffusion was accelerated at higher temperature and possibly by temperature variations. The lowest chloride threshold values were found for outdoor exposed specimens suggesting that variation of RH or temperature (or both) facilitated rapid chloride diffusion. Third, an elevated time-to-corrosion and chloride threshold values were found for the wire brushed steel specimens compared to as-received ones. The higher ratio of [OH-]/[Fe n+] on the wire brushed steel surface compared to that of as-received case can be the possible cause because the higher ratio of this parameter enables the formation of a more protective passive film on the rebar. Fourth, voids at the steel-concrete interface facilitated passive film breakdown and onset of localized corrosion. This tendency for corrosion initiation increased in proportion to void size irrespective of specimen type. Also, [Cl -]th decreased with increasing void diameter. In addition, new ex-situ leaching method for determining concrete pore water alkalinity was developed.

Application of slightly acidic electrolyzed water for decontamination of stainless steel surfaces in animal transport vehicles.

PubMed

Ni, Li; Zheng, Weichao; Zhang, Qiang; Cao, Wei; Li, Baoming

2016-10-01

The effectiveness of slightly acidic electrolyzed water (SAEW) in reducing Escherichia coli, Salmonella typhimurim, Staphylococcus aureus or bacterial mixtures on stainless steel surfaces was evaluated and compared its efficacy with composite phenol solution for reducing total aerobic bacteria in animal transport vehicles. Stainless steel surfaces were inoculated with these strains individually or in a mixture, and sprayed with SAEW, composite phenol, or alkaline electrolyzed water for 0.5, 1, 1.5 and 2min. The bactericidal activity of SAEW increased with increasing available chlorine concentration and spraying duration. The SAEW solution of 50mgl -1 of available chlorine concentration showed significantly higher effectiveness than composite phenol in reducing the pathogens on stainless steel surfaces (P<0.05). Complete inactivation of pathogens on stainless steel surfaces were observed after treatment with alkaline electrolyzed water followed by SAEW at 50mgl -1 of available chlorine concentration for 2min or alkaline electrolyzed water treatment followed by SAEW treatment at 90mgl -1 of available chlorine concentration for 0.5min. The efficacy of SAEW in reducing total aerobic bacteria in animal transport vehicles was also determined. Vehicles in the disinfection booth were sprayed with the same SAEW, alkaline electrolyzed water and composite phenol solutions using the automatic disinfection system. Samples from vehicle surfaces were collected with sterile cotton swabs before and after each treatment. No significant differences in bactericidal efficiency were observed between SAEW and composite phenol for reducing total aerobic bacteria in the vehicles (P>0.05). SAEW was also found to be more effective when used in conjunction with alkaline electrolyzed water. Results suggest that the bactericidal efficiency of SAEW was higher than or equivalent to that of composite phenol and SAEW may be used as effective alternative for reducing microbial contamination of animal transport vehicles. Copyright © 2016 Elsevier B.V. All rights reserved.

Alkaline hydrolysis of dimethyl terephthalate in the presence of [LiAl{sub 2}(OH){sub 6}]Cl.2H{sub 2}O

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

Lei Lixu; Zhang Weifeng; Hu Meng

2006-11-15

The alkaline hydrolysis of dimethyl terephthalate (DMT) in the presence of [LiAl{sub 2}(OH){sub 6}]Cl has been investigated to demonstrate a possible application of anion exchange facility of layered double hydroxides (LDHs) to control chemical reactions. The results show that (i) in the alkaline hydrolysis of DMT in the presence of [LiAl{sub 2}(OH){sub 6}]Cl, most of the interlayer Cl{sup -} of [LiAl{sub 2}(OH){sub 6}]Cl is quickly replaced by OH{sup -} in the alkaline solution because the LDH host favors OH{sup -} more; (ii) the alkaline hydrolysis of DMT in the presence of [LiAl{sub 2}(OH){sub 6}]Cl is faster than the reaction ofmore » DMT and [LiAl{sub 2}(OH){sub 6}]OH; (iii) The hydrolysis of DMT in a buffer solution of pH{approx}8 takes longer time to reach equilibrium than the alkaline hydrolysis of DMT in the presence of [LiAl{sub 2}(OH){sub 6}]Cl. It is believed that the selective anion exchange chemistry of the LDH plays a key role in storage and controlled release of active reactant, that is, OH{sup -}, thus make the hydrolysis proceeds in a controlled way. - Graphical abstract: XRD patterns of the solid products of the alkaline hydrolysis of dimethyl terephthalate (DMT) in the presence of [LiAl{sub 2}(OH){sub 6}]Cl at 70 deg. C halted at different time, which shows that [LiAl{sub 2}(OH){sub 6}]Cl turns out to be [LiAl{sub 2}(OH){sub 6}]OH, and [LiAl{sub 2}(OH){sub 6}]{sub 2}TP forms gradually. In this reaction, the alkaline hydrolysis of DMT is controlled by replacement of Cl{sup -} in [LiAl{sub 2}(OH){sub 6}]Cl by OH{sup -}, and subsequent replacement of OH{sup -} in [LiAl{sub 2}(OH){sub 6}]OH by terephthalate anion.« less

Aluminum anode for aluminum-air battery - Part II: Influence of In addition on the electrochemical characteristics of Al-Zn alloy in alkaline solution

NASA Astrophysics Data System (ADS)

Park, In-Jun; Choi, Seok-Ryul; Kim, Jung-Gu

2017-07-01

Effects of Zn and In additions on the aluminum anode for Al-air battery in alkaline solution are examined by the self-corrosion rate, cell voltage, current-voltage characteristics, anodic polarization, discharge performance and AC impedance measurements. The passivation behavior of Zn-added anode during anodic polarization decreases the discharge performance of Al-air battery. The addition of In to Al-Zn anode reduces the formation of Zn passivation film by repeated adsorption and desorption behavior of In ion onto anode surface. The attenuated Zn passive layer by In ion attack leads to the improvement of discharge performance of Al-air battery.

A preliminary study of the electro-oxidation of L-ascorbic acid on polycrystalline silver in alkaline solution

NASA Astrophysics Data System (ADS)

Majari Kasmaee, L.; Gobal, F.

Electrochemical oxidation of L-ascorbic acid on polycrystalline silver in alkaline aqueous solutions is studied by cyclic voltammetry (CV), chronoamperometry (CA) and impedance spectroscopy (IS). The anodic electro-oxidation starts at -500 mV versus SCE and shows continued anodic oxidation in the cathodic half cycle in the CV regime signifying slowly oxidizing adsorbates. Diffusion coefficient of ascorbate ion measured under both voltammetric regimes is around 1.4 × 10 -5 cm 2 s -1. Impedance spectroscopy measures the capacitances associated with double layer and adsorption around 50 μF cm -2 and 4 mF cm -2 as well as the adsorption and decomposition resistances (rates).

Fluoro-alcohol phase modifiers and process for cesium solvent extraction

DOEpatents

Bonnesen, Peter V.; Moyer, Bruce A.; Sachleben, Richard A.

2003-05-20

The invention relates to a class of phenoxy fluoro-alcohols, their preparation, and their use as phase modifiers and solvating agents in a solvent composition for the extraction of cesium from alkaline solutions. These phenoxy fluoro-alcohols comply with the formula: ##STR1## in which n=2 to 4; X represents a hydrogen or a fluorine atom, and R.sup.2 -R.sup.6 are hydrogen or alkyl substituents. These phenoxy fluoro-alcohol phase modifiers are a necessary component to a robust solvent composition and process useful for the removal of radioactive cesium from alkaline nuclear waste streams. The fluoro-alcohols can also be used in solvents designed to extract other cesium from acidic or neutral solutions.

METHOD OF PREPARING COMPLEXES OF PLUTONIUM WITH DIKETONES

DOEpatents

Dixon, J.S.; Katz, J.J.; Orlemann, E.F.

1961-06-20

A process is described for sepsrating Pu from an aqueous alkaline solution by either precipitating with a beta -diketone or extracting into a solution of the beta -dixetone in an organic water-immiscible solvent. Acetyl acetone and benzoyl acetone are the beta -diketones used.

Electrochemical reduction of nitrate and nitrite in concentrated sodium hydroxide at platinum and nickel electrodes

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

Hu Lin Li; Robertson, D.H.; Chambers, J.Q.

1996-10-01

This work describes the electrochemical reduction of nitrate in alkaline solutions. Conditions which maximize the current efficiency for the production of dinitrogen and/or ammonia gases could be very important for the treatment of radioactive waste solutions.

Stainless steel anodes for alkaline water electrolysis and methods of making

DOEpatents

Soloveichik, Grigorii Lev

2014-01-21

The corrosion resistance of stainless steel anodes for use in alkaline water electrolysis was increased by immersion of the stainless steel anode into a caustic solution prior to electrolysis. Also disclosed herein are electrolyzers employing the so-treated stainless steel anodes. The pre-treatment process provides a stainless steel anode that has a higher corrosion resistance than an untreated stainless steel anode of the same composition.

Seeking effective dyes for a mediated glucose-air alkaline battery/fuel cell

NASA Astrophysics Data System (ADS)

Eustis, Ross; Tsang, Tsz Ming; Yang, Brigham; Scott, Daniel; Liaw, Bor Yann

2014-02-01

A significant level of power generation from an abiotic, air breathing, mediated reducing sugar-air alkaline battery/fuel cell has been achieved in our laboratories at room temperature without complicated catalysis or membrane separation in the reaction chamber. Our prior studies suggested that mass transport limitation by the mediator is a limiting factor in power generation. New and effective mediators were sought here to improve charge transfer and power density. Forty-five redox dyes were studied to identify if any can facilitate mass transport in alkaline electrolyte solution; namely, by increasing the solubility and mobility of the dye, and the valence charge carried per molecule. Indigo dyes were studied more closely to understand the complexity involved in mass transport. The viability of water-miscible co-solvents was also explored to understand their effect on solubility and mass transport of the dyes. Using a 2.0 mL solution, 20% methanol by volume, with 100 mM indigo carmine, 1.0 M glucose and 2.5 M sodium hydroxide, the glucose-air alkaline battery/fuel cell attained 8 mA cm-2 at short-circuit and 800 μW cm-2 at the maximum power point. This work shall aid future optimization of mediated charge transfer mechanism in batteries or fuel cells.

Alkaline hydrolysis of ethylene phosphate: an ab initio study by supermolecule model and polarizable continuum approach.

PubMed

Xia, Futing; Zhu, Hua

2011-09-01

The alkaline hydrolysis reaction of ethylene phosphate (EP) has been investigated using a supermolecule model, in which several explicit water molecules are included. The structures and single-point energies for all of the stationary points are calculated in the gas phase and in solution at the B3LYP/6-31++G(df,p) and MP2/6-311++G(df,2p) levels. The effect of water bulk solvent is introduced by the polarizable continuum model (PCM). Water attack and hydroxide attack pathways are taken into account for the alkaline hydrolysis of EP. An associative mechanism is observed for both of the two pathways with a kinetically insignificant intermediate. The water attack pathway involves a water molecule attacking and a proton transfer from the attacking water to the hydroxide in the first step, followed by an endocyclic bond cleavage to the leaving group. While in the first step of the hydroxide attack pathway the nucleophile is the hydroxide anion. The calculated barriers in aqueous solution for the water attack and hydroxide attack pathways are all about 22 kcal/mol. The excellent agreement between the calculated and observed values demonstrates that both of the two pathways are possible for the alkaline hydrolysis of EP. Copyright © 2011 Wiley Periodicals, Inc.

Influence of hydrothermal processes on changes of volcanic rocks (data of physical modelling)

NASA Astrophysics Data System (ADS)

Shanina, V. V.; Bychkov, A. Y.

2009-04-01

Due to active development of geothermal energy, in middle of the last century have begun papers devoted to experiments, directed on study of transformations of minerals [4] and rocks [1, 2, 5] under action of geothermal processes. But any researcher did not estimate thus change of their physical and physico-mechanical properties. The purpose of job - to study character and dynamics changes of volcanic rocks (to simulate conditions of geothermal transformations). Tasks: creation of the whole series of experiments in autoclavs at various temperatures, pressure and composition of solutions, preparation of samples, study of chemical and mineral composition, structure and properties of rocks and solutions before and after experiments. In 2006 the first similar experiments were begun [3]. Researched rocks basalts, hyaloclasites and obsidian, selected from Iceland and tuffs Payzhetka Geothermal Field, Southern Kamchatka, Russia. Were used autoclavs, consisting from titanic of an alloy ВТ-8, volume 116-119 мл, in each of which was located from 2 up to 4 samples of rocks of the investigated structure and properties. The heating was made in OVEN ТРМ-10 with accuracy + 1 °С, the constancy of temperature was supervised by thermocouples. 15 experiences (temperature 200, 300 and 450 °С; pressure 16, 86 and 1000 bars accordingly now are carried out; 4 solutions (1 alkaline and 3 acid); duration 14, 15, 30 and 60 days). All four groups of the investigated rocks appreciablly react under geothermal influence. The changes are observed in colour of samples (brighten in acid solutions), their microstructure, that for basalts is visible only in raster electronic microscope, and in education of new mineral phases, is especially active in a acid solution, the X-Ray analysis (has executed by Dr. Krupskaya V.V., apparatuses - DRON- UM1) has shown, that 94,2 % is smectite, 3,5 % - kaolinite, 1,2 % - crisrobalite, 1,1 % - diopside (?), in others pores fills chlorite, and in an alkaline solution amorphous silicon. The most appreciable changes of meanings parameters of properties are observed in velocity of longitudinal waves, which for basalts and hyaloclasites raise in both solutions at 300 °С, and at 450 °С, but in tuffs were lowered, as they has cracked, and majority even were disorganized, in a course of experiment; and meanings of a magnetic susceptibility, which for basalts and tuffs raises at influence of an alkaline solution and falls in acid. For obsidian the speed of passage of elastic waves after influence of an alkaline solution is reduced, that is connected to processing of a volcanic glass from a surface and education rind, which thickness for 15 day has 1-2 mm, and for 30 - 2-3 mm. Thus the greatest decrease of velocity of waves occurs on the party with (smallest at samples), where a layer of changes glass greatest concerning length of a sample. If for 30 day Vp decrease on the party a practically no, on c - 0,95 km/sec (18 %), and Vs accordingly 0,55 km/sec (18 %) and 1,25 km/sec (45 %). Changes of a magnetic susceptibility in obsidian to trace practically is not possible, as is primary only tenth shares *10-3 units SI and varies on similar sizes. For hyaloclasites it is difficult to speak about the unequivocal general tendencies because of features of their composition, structure and origin; at the given stage of study it is possible to note, what after a presence in a sour solution during 30 day at 300 С goes increase of speeds of passage of longitudinal waves on 0,35-0,50 km/sec (24-25 %), and the magnetic susceptibility does not change. After an alkaline solution at equality of other parameters - increase of velocity on 0,10-0,40 km/sec (6-22 %), and magnetic susceptibility on 0,3-0,4*10-3 ед. SI. In tuffs the velocity of longitudinal waves decrease (from 0,35 km/sec (14 days, initial solution with pH 4,4) up to 0,54-0,55 km/sec (in a solution with pH 1 or with pH 4,4 after 60 days)). The sizes small, but as initial in the tuffs low (1,55-2,10 km/sec), in the percentage attitude they fall on 18-34 of %. It occurs because of decrease of density and increase of porosity. The magnetic susceptibility practically in all cases is reduced (the average on 0,35-0,70*10-3 ед. SI (9-13,4 %)). The theses of the report are based on materials of the researches which have been carried out at financial support of the Russian Fund of Fundamental Researches (the grant № 07-05-00118а). The authors express gratitude to the dr. Frolova J. V. and other employees of faculty of engineering and ecological geology for the help in realization of experiments.

Power ultrasound irradiation during the alkaline etching process of the 2024 aluminum alloy

NASA Astrophysics Data System (ADS)

Moutarlier, V.; Viennet, R.; Rolet, J.; Gigandet, M. P.; Hihn, J. Y.

2015-11-01

Prior to any surface treatment on an aluminum alloy, a surface preparation is necessary. This commonly consists in performing an alkaline etching followed by acid deoxidizing. In this work, the use of power ultrasound irradiation during the etching step on the 2024 aluminum alloy was studied. The etching rate was estimated by weight loss, and the alkaline film formed during the etching step was characterized by glow discharge optical emission spectrometry (GDOES) and scanning electron microscope (SEM). The benefit of power ultrasound during the etching step was confirmed by pitting potential measurement in NaCl solution after a post-treatment (anodizing).

Deetherification process

DOEpatents

Smith, Jr., Lawrence A.

1985-01-01

Ethers such as isobutyl tertiary butyl ether are dissociated into their component alcohols and isolefins by heat stabilized catalyst compositions prepared from nuclear sulfonic acid, for example, macroporous crosslinked polyvinyl aromatic compounds containing sulfonic acid groups are neutralized with a metal of Al, Fe, Zn, Cu, Ni, ions or mixtures and alkali, alkaline earth metals or ammonium ions by contacting the resin containing the sulfonic acid with aqueous solutions of the metals salts and alkali, alkaline earth metal or ammonium salts. The catalysts have at least 50% of the sulfonic acid groups neutralized with metal ions and the balance of the sulfonic acid groups neutralized with alkali, alkaline earth ions or ammonium ions.

Deetherification process

DOEpatents

Smith, L.A. Jr.

1985-11-05

Ethers such as isobutyl tertiary butyl ether are dissociated into their component alcohols and isoolefins by heat stabilized catalyst compositions prepared from nuclear sulfonic acid, for example, macroporous crosslinked polyvinyl aromatic compounds containing sulfonic acid groups are neutralized with a metal of Al, Fe, Zn, Cu, Ni, ions or mixtures and alkali, alkaline earth metals or ammonium ions by contacting the resin containing the sulfonic acid with aqueous solutions of the metals salts and alkali, alkaline earth metal or ammonium salts. The catalysts have at least 50% of the sulfonic acid groups neutralized with metal ions and the balance of the sulfonic acid groups neutralized with alkali, alkaline earth ions or ammonium ions.

Surface pre-treatment of aluminium by cleaning, chemical ething and conversion coating

NASA Astrophysics Data System (ADS)

Zaki, Mohammad Hafizudden Mohd; Mohd, Yusairie; Isa, Nik Norziehana Che

2017-12-01

Surface pre-treatment is one of the critical treatments for surface modification of aluminium (Al). In this study, pre-treatment of Al surface involved three stages; (1) cleaning (polishing and degreasing), (2) chemical etching (alkaline and acid) and (3) conversion coating (ie: zincate treatment). Cleaning process of Al was conducted by polishing and degreasing with acetone while etching process was done by immersion in 1.25 M NaOH solution (i.e: alkaline etching) followed with acid etching using 8 M HNO3 solution. The zincate treatment was conducted via electroless coating method by immersion of Al into a bath solution containing 0.5 M Zn(NO3)2, 0.1 M HNO3 and 0.2 M NaBH4 (reducing agent) for one hour. Different temperatures (ie: 25 °C, 50 °C, 75 °C, 90 °C) of bath solutions at pH 4 were used to investigate the effect of temperature on zincate treatment. Surface morphology and chemical composition of the pre-treated Al were characterized using Field Emission Scanning Electron Microscopy (FESEM) and Energy Dispersion X-ray analysis (EDX), respectively. The results showed that oxide layer on Al surface decreased after chemical etching process. Temperature of zincate solution has significantly affected the conversion coating process of aluminium. It was found that zinc oxide (ZnO) and zinc borate (ZnO.B2O3) were dominantly formed after zincate treatment at high temperature (ie:90 °C) with curved blade-like structure and composition of Zn, B and O with 13.70 wt.%, 3.52 wt.% and 54.39 wt.%, respectively. However, zincate treatment at low temperature (ie:<50 °C) has produced low metallic Zn.

Two-dimensional NMR spectroscopy reveals cation-triggered backbone degradation in polysulfone-based anion exchange membranes

PubMed Central

Arges, Christopher G.; Ramani, Vijay

2013-01-01

Anion exchange membranes (AEMs) find widespread applications as an electrolyte and/or electrode binder in fuel cells, electrodialysis stacks, flow and metal-air batteries, and electrolyzers. AEMs exhibit poor stability in alkaline media; their degradation is induced by the hydroxide ion, a potent nucleophile. We have used 2D NMR techniques to investigate polymer backbone stability (as opposed to cation stability) of the AEM in alkaline media. We report the mechanism behind a peculiar, often-observed phenomenon, wherein a demonstrably stable polysulfone backbone degrades rapidly in alkaline solutions upon derivatization with alkaline stable fixed cation groups. Using COSY and heteronuclear multiple quantum correlation spectroscopy (2D NMR), we unequivocally demonstrate that the added cation group triggers degradation of the polymer backbone in alkaline via quaternary carbon hydrolysis and ether hydrolysis, leading to rapid failure. This finding challenges the existing perception that having a stable cation moiety is sufficient to yield a stable AEM and emphasizes the importance of the often ignored issue of backbone stability. PMID:23335629

Inorganic polymers from laterite using activation with phosphoric acid and alkaline sodium silicate solution: Mechanical and microstructural properties

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

Lassinantti Gualtieri, Magdalena, E-mail: magdalena.gualtieri@unimore.it; Romagnoli, Marcello; Pollastri, Simone

2015-01-15

Geopolymers from laterite, an iron-rich soil available in developing countries, have great potential as building materials. In this work, laterite from Togo (Africa) was used to prepare geopolymers using both phosphoric acid and alkaline sodium silicate solution. Microstructural properties were investigated by scanning electron microscopy, X-ray powder diffraction and mercury porosimetry, whereas thermal properties were evaluated by thermal analyses. The local environment of iron was studied by X-ray Absorption Spectroscopy (XANES region). The mechanical properties were determined. Modulus of Rupture and Young's modulus fell in the ranges 3.3–4.5 MPa and 12–33 GPa, respectively, rendering the materials good candidates for constructionmore » purposes. Heating above 900 °C results in weight-gain, presumably due to iron redox reactions. X-ray Absorption Spectroscopy data evidence changes in the chemical and structural environments of iron following thermal treatment of geopolymers. These changes indicate interaction between the geopolymer structure and iron during heating, possibly leading to redox properties. -- Highlights: •Geopolymerization of laterite is promising for fabrication of building materials. •Both phosphoric acid and alkaline sodium silicate solution can be used for activation. •Thermally activated redox properties of the inorganic polymers were observed.« less

Alkaline Peroxides Versus Sodium Hypochlorite for Removing Denture Biofilm: a Crossover Randomized Trial.

PubMed

Peracini, Amanda; Regis, Rômulo Rocha; Souza, Raphael Freitas de; Pagnano, Valéria Oliveira; Silva, Cláudia Helena Lovato da; Paranhos, Helena de Freitas Oliveira

2016-01-01

This study evaluated the efficacy of cleanser solutions on denture biofilm removal by a crossover randomized clinical trial. Thirty two edentulous patients were instructed to brush their dentures (specific brush and liquid soap) three times a day (after breakfast, lunch and dinner) and to soak them (≥ 8 h) in: (C) control -water; (AP): alkaline peroxide; or (SH) 0.5% sodium hypochlorite. Each solution was used for 21 days (three cycles of 7 days). At the end of each cycle, the inner surfaces of maxillary dentures were disclosed (1% neutral red) and photographed (HX1 - Sony). Areas (total and stained biofilm) were measured (Image Tool software) and the percentage of biofilm calculated as the ratio between the area of the biofilm multiplied by 100 and total surface area of the internal base of the denture. Data were compared by means of generalized estimating equation (α=5%) and multiple comparisons (Bonferroni; α=1.67%). Immersion in SH reduced biofilm (%) (8.3 ± 13.3B) compared to C (18.2 ± 14.9A) and AP (18.2 ± 16.6A). The 0.5% sodium hypochlorite solution was the most efficacious for biofilm removal. Alkaline peroxides may not lead to further biofilm removal in patients with adequate denture maintenance habits.

Comparison of behavior in muscle fiber regeneration after bupivacaine hydrochloride- and acid anhydride-induced myonecrosis.

PubMed

Akiyama, C; Kobayashi, S; Nonaka, I

1992-01-01

We compared the morphologic characteristics of muscle fiber necrosis and subsequent regeneration after injury induced by intramuscular injections of bupivacaine hydrochloride (BPVC) and a variety of solutions at acid and alkaline pH (acetic anhydride, citric acid buffer, and sodium carbonate buffer). After BPVC injection the necrotic muscle fibers were rapidly invaded by phagocytic cells, followed by active regeneration and very little fibrous scar formation. The regenerating muscle fibers increased rapidly in size and attained complete fiber type differentiation and regained their initial fiber diameter within 1 month. Both alkaline and acid solutions induced muscle fiber necrosis followed by regeneration. Fiber necrosis induced by alkaline buffers and acetic anhydride solutions above pH 5.0 produced changes quite similar to that induced by BPVC. However, injection with 0.1 M acetic anhydride at pH below 4.0 resulted in coagulative necrosis of the injured muscle with very little phagocytic infiltration with poor regenerative activity and dense fibrous tissue scarring. Thus, pH 4.0 appears to be the critical pH determining the type of muscle injury and subsequent poor phagocytic and regenerative activities. This model of acidic acetic anhydride injury may lead to the identification of factors which interfere with regeneration and cause fibrous tissue scarring in human muscular dystrophy.

Simulation of future stream alkalinity under changing deposition and climate scenarios.

PubMed

Welsch, Daniel L; Cosby, B Jack; Hornberger, George M

2006-08-31

Models of soil and stream water acidification have typically been applied under scenarios of changing acidic deposition, however, climate change is usually ignored. Soil air CO2 concentrations have potential to increase as climate warms and becomes wetter, thus affecting soil and stream water chemistry by initially increasing stream alkalinity at the expense of reducing base saturation levels on soil exchange sites. We simulate this change by applying a series of physically based coupled models capable of predicting soil air CO2 and stream water chemistry. We predict daily stream water alkalinity for a small catchment in the Virginia Blue Ridge for 60 years into the future given stochastically generated daily climate values. This is done for nine different combinations of climate and deposition. The scenarios for both climate and deposition include a static scenario, a scenario of gradual change, and a scenario of abrupt change. We find that stream water alkalinity continues to decline for all scenarios (average decrease of 14.4 microeq L-1) except where climate is gradually warming and becoming more moist (average increase of 13 microeq L-1). In all other scenarios, base cation removal from catchment soils is responsible for limited alkalinity increase resulting from climate change. This has implications given the extent that acidification models are used to establish policy and legislation concerning deposition and emissions.

Hierarchically porous Fe-N-C derived from covalent-organic materials as a highly efficient electrocatalyst for oxygen reduction

NASA Astrophysics Data System (ADS)

Zuo, Quan; Zhao, Pingping; Luo, Wei; Cheng, Gongzhen

2016-07-01

Developing high-performance non-precious catalysts to replace platinum as oxygen reduction reaction (ORR) catalysts is still a big scientific and technological challenge. Herein, we report a simple method for the synthesis of a FeNC catalyst with a 3D hierarchically micro/meso/macro porous network and high surface area through a simple carbonization method by taking the advantages of a high specific surface area and diverse pore dimensions in 3D porous covalent-organic material. The resulting FeNC-900 electrocatalyst with improved reactant/electrolyte transport and sufficient active site exposure, exhibits outstanding ORR activity with a half-wave potential of 0.878 V, ca. 40 mV more positive than Pt/C for ORR in alkaline solution, and a half-wave potential of 0.72 V, which is comparable to that of Pt/C in acidic solution. In particular, the resulting FeNC-900 exhibits a much higher stability and methanol tolerance than those of Pt/C, which makes it among the best non-precious catalysts ever reported for ORR.Developing high-performance non-precious catalysts to replace platinum as oxygen reduction reaction (ORR) catalysts is still a big scientific and technological challenge. Herein, we report a simple method for the synthesis of a FeNC catalyst with a 3D hierarchically micro/meso/macro porous network and high surface area through a simple carbonization method by taking the advantages of a high specific surface area and diverse pore dimensions in 3D porous covalent-organic material. The resulting FeNC-900 electrocatalyst with improved reactant/electrolyte transport and sufficient active site exposure, exhibits outstanding ORR activity with a half-wave potential of 0.878 V, ca. 40 mV more positive than Pt/C for ORR in alkaline solution, and a half-wave potential of 0.72 V, which is comparable to that of Pt/C in acidic solution. In particular, the resulting FeNC-900 exhibits a much higher stability and methanol tolerance than those of Pt/C, which makes it among the best non-precious catalysts ever reported for ORR. Electronic supplementary information (ESI) available: Fig. S1-S12 and Tables S1 and S2. See DOI: 10.1039/c6nr03273g

Starch hydrogels: The influence of the amylose content and gelatinization method.

PubMed

Biduski, Bárbara; Silva, Wyller Max Ferreria da; Colussi, Rosana; Halal, Shanise Lisie de Mello El; Lim, Loong-Tak; Dias, Álvaro Renato Guerra; Zavareze, Elessandra da Rosa

2018-07-01

Gelatinization and retrogradation, influenced by amylose and amylopectin ratio, are important characteristics for starch hydrogels elaboration. The objective of this study was to evaluate the influence of amylose content and the gelatinization method on the physicochemical characteristics of native and cross-linked rice starch hydrogels. The native and cross-linked starches were gelatinized with heating or alkaline solution, added polyvinyl alcohol, frozen and then freeze-dried. The cross-linked starch had a low final viscosity (101.38 RVU), which made the heat-induced gelatinized hydrogel readily disintegrated in water. However, modified starch hydrogels obtained by alkaline-induced gelatinization resulted in a more rigid structure than the native starch hydrogels. In addition, the starch sample with high amylose content had lower water absorption (322.2%) due to the greater stiffness of the hydrogel structure that resisted swelling. The alkaline-gelatinization resulted in stiffer hydrogels with lower water absorption (322.2 to 534.8%), while the heat-gelatinized behaved as a superabsorbent (658.7 to 1068.5%). The variability of the hydrogels properties of this study can enable a range of applications due to different amylose contents and gelatinization methods. Copyright © 2018 Elsevier B.V. All rights reserved.

Increasing shallow groundwater CO2 and limestone weathering, Konza Prairie, USA

USGS Publications Warehouse

Macpherson, G.L.; Roberts, J.A.; Blair, J.M.; Townsend, M.A.; Fowle, D.A.; Beisner, K.R.

2008-01-01

In a mid-continental North American grassland, solute concentrations in shallow, limestone-hosted groundwater and adjacent surface water cycle annually and have increased steadily over the 15-year study period, 1991-2005, inclusive. Modeled groundwater CO2, verified by measurements of recent samples, increased from 10-2.05 atm to 10-1.94 atm, about a 20% increase, from 1991 to 2005. The measured groundwater alkalinity and alkaline-earth element concentrations also increased over that time period. We propose that carbonate minerals dissolve in response to lowered pH that occurs during an annual carbonate-mineral saturation cycle. The cycle starts with low saturation during late summer and autumn when dissolved CO2 is high. As dissolved CO2 decreases in the spring and early summer, carbonates become oversaturated, but oversaturation does not exceed the threshold for precipitation. We propose that groundwater is a CO2 sink through weathering of limestone: soil-generated CO2 is transformed to alkalinity through dissolution of calcite or dolomite. The annual cycle and long-term increase in shallow groundwater CO2 is similar to, but greater than, atmospheric CO2. ?? 2008 Elsevier Ltd. All rights reserved.

Mineral transformation controls speciation and pore-fluid transmission of contaminants in waste-weathered Hanford sediments

NASA Astrophysics Data System (ADS)

Perdrial, Nicolas; Thompson, Aaron; O'Day, Peggy A.; Steefel, Carl I.; Chorover, Jon

2014-09-01

Portions of the Hanford Site (WA, USA) vadose zone were subjected to weathering by caustic solutions during documented releases of high level radioactive waste (containing Sr, Cs and I) from leaking underground storage tanks. Previous studies have shown that waste-sediment interactions can promote variable incorporation of contaminants into neo-formed mineral products (including feldspathoids and zeolites), but processes regulating the subsequent contaminant release from these phases into infiltrating background pore waters remain poorly known. In this paper, reactive transport experiments were conducted with Hanford sediments previously weathered for one year in simulated hyper-alkaline waste solutions containing high or low 88Sr, 127I, and 133Cs concentrations, with or without CO2(aq). These waste-weathered sediments were leached in flow-through column experiments with simulated background pore water (characteristic of meteoric recharge) to measure contaminant release from solids formed during waste-sediment interaction. Contaminant sorption-desorption kinetics and mineral transformation reactions were both monitored using continuous-flow and wet-dry cycling regimes for ca. 300 pore volumes. Less than 20% of contaminant 133Cs and 88Sr mass and less than 40% 127I mass were released over the course of the experiment. To elucidate molecular processes limiting contaminant release, reacted sediments were studied with micro- (TEM and XRD) and molecular- (Sr K-edge EXAFS) scale methods. Contaminant dynamics in column experiments were principally controlled by rapid dissolution of labile solids and competitive exchange reactions. In initially feldspathoidic systems, time-dependent changes in the local zeolitic bonding environment observed with X-ray diffraction and EXAFS are responsible for limiting contaminant release. Linear combination fits and shell-by-shell analysis of Sr K-edge EXAFS data revealed modification in Sr-Si/Al distances within the zeolite cage. Wet-dry cycling did not affect significantly molecular-scale transformations relative to continuous-flow controls. Results indicate that contaminants bound to the solid phase in distinct micro- and molecular-scale coordinative environments can generate similar macro-scale release behaviors, highlighting the need for multi-scale interrogations to constrain mechanisms of reactive transport. Data also indicate that weathering-induced change in ion exchange selectivity coefficients should be incorporated in simulations of contaminant release from caustic high-level radioactive waste impacted sediments.

Comparison of alkaline industrial wastes for aqueous mineral carbon sequestration through a parallel reactivity study.

PubMed

Noack, Clinton W; Dzombak, David A; Nakles, David V; Hawthorne, Steven B; Heebink, Loreal V; Dando, Neal; Gershenzon, Michael; Ghosh, Rajat S

2014-10-01

Thirty-one alkaline industrial wastes from a wide range of industrial processes were acquired and screened for application in an aqueous carbon sequestration process. The wastes were evaluated for their potential to leach polyvalent cations and base species. Following mixing with a simple sodium bicarbonate solution, chemistries of the aqueous and solid phases were analyzed. Experimental results indicated that the most reactive materials were capable of sequestering between 77% and 93% of the available carbon under experimental conditions in four hours. These materials - cement kiln dust, spray dryer absorber ash, and circulating dry scrubber ash - are thus good candidates for detailed, process-oriented studies. Chemical equilibrium modeling indicated that amorphous calcium carbonate is likely responsible for the observed sequestration. High variability and low reactive fractions render many other materials less attractive for further pursuit without considering preprocessing or activation techniques. Copyright © 2014 Elsevier Ltd. All rights reserved.

[Isolation and identification of dog periodontal ligament stem cells].

PubMed

Chang, Xiu-Mei; Liu, Hong-Wei; Jin, Yan; Liu, Yuan; He, Hui-Xia

2009-02-01

To isolate, culture and identify a dog periodontal ligament stem cells (PDLSC) line in vitro. The adult dog periodontal ligament cells were isolated by limited dilution of culture cell for single cell clone. Cells originated from one of these clones were assessed through colony-forming efficiency and immunocytochemistry assay and alkaline phosphatase stain was used to identify the source of adult dog periodontal stem cells, at the same time, PDLSC were induced with mineralizatin solution and was found to have long protrude like an osteoblast. Differentiation of PDLSC were assessed. Mineralized potential was studied by Von-Kossa staining. The dog PDLSC expressed STRO-1, which was the marker of mesenchymal stem cells. Also Vimentin, osteoblast-like marker alkaline phosphatase and Collagen-I expressed weakly. Cells were clonegenic, highly proliferative cells and capable of differentiating into osteoblasts/cementoblasts. The evidence suggests that the cultured cells were stem cells from adult dog periodontal ligament.

Novel inorganic materials for polymer electrolyte and alkaline fuel cells

NASA Astrophysics Data System (ADS)

Tadanaga, Kiyoharu

2012-06-01

Inorganic materials with high ionic conductivity must have big advantages for the thermal and long term stability when the materials are used as the electrolyte of fuel cells. In the present paper, novel ionic conductive inorganic materials for polymer electrolyte fuel cells (PEFCs) and all solid state alkaline fuel cells (AFCs) that have been developed by our group have been reviewed. PEFCs which can operate in temperature range from 100 to 200 °C are intensively studied because of some advantages such as reduction of CO poisoning of Pt catalyst and acceleration of electrode reactions. We showed that the fuel cells using the composite membranes prepared from phosphosilicate gel powder and polyimide precursor can operate in the temperature range from 30 to 180 °C. We also found that the inorganic-organic hybrid membranes with acid-base pairs from 3-aminopropyl triethoxy silane and H2SO4 or H3PO4 show high proton conductivity under dry atmosphere, and the membranes are thermally stable at intermediate temperatures. On the other hand, because the use of noble platinum is the serious problem for the commercialization of PEFCs and because oxidation reactions are usually faster than those of acid-type fuel cells, alkaline type fuel cells, in which a nonplatinum catalyst can be used, are attractive. Recently, we have proposed an alkaline-type direct ethanol fuel cell (DEFC) using a natural clay electrolyte with non-platinum catalysts. So-called hydrotalcite clay, Mg-Al layered double hydroxide intercalated with CO32- (Mg-Al CO32- LDH), has been proved to be a hydroxide ion conductor. An alkalinetype DEFC using Mg-Al CO32- LDH as the electrolyte and aqueous solution of ethanol and potassium hydroxide as a source of fuel exhibited excellent electrochemical performance.

Process for recovering hydrocarbons from a diatomite-type ore

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

Davis, B.W.

1983-02-15

A process for recovering hydrocarbons from a diatomite-type ore which comprises contacting the diatomite ore with a C/sub 4/-C/sub 10/ alcohol and thereafter contacting the diatomite ore-alcohol mixture with an aqueous alkaline solution to separate a hydrocarbon-alcohol phase and an alkaline aqueous phase containing the stripped diatomite ore. Thereafter, the alcohol is distilled off from the hydrocarbon phase and recycled back into the initial process.

Vadose Zone Fate and Transport Simulation of Chemicals Associated with Coal Seam Gas Extraction

NASA Astrophysics Data System (ADS)

Simunek, J.; Mallants, D.; Jacques, D.; Van Genuchten, M.

2017-12-01

The HYDRUS-1D and HYDRUS (2D/3D) computer software packages are widely used finite element models for simulating the one-, and two- or three-dimensional movement of water, heat, and multiple solutes in variably-saturated media, respectively. While the standard HYDRUS models consider only the fate and transport of individual solutes or solutes subject to first-order degradation reactions, several specialized HYDRUS add-on modules can simulate far more complex biogeochemical processes. The objective of this presentation is to provide an overview of the HYDRUS models and their add-on modules, and to demonstrate applications of the software to the subsurface fate and transport of chemicals involved in coal seam gas extraction and water management operations. One application uses the standard HYDRUS model to evaluate the natural soil attenuation potential of hydraulic fracturing chemicals and their transformation products in case of an accidental release. By coupling the processes of retardation, first-order degradation and convective-dispersive transport of the biocide bronopol and its degradation products, we demonstrated how natural attenuation reduces initial concentrations by more than a factor of hundred in the top 5 cm of the vadose zone. A second application uses the UnsatChem module to explore the possible use of coal seam gas produced water for sustainable irrigation. Simulations with different irrigation waters (untreated, amended with surface water, and reverse osmosis treated) provided detailed results regarding chemical indicators of soil and plant health, notably SAR, EC and sodium concentrations. A third application uses the coupled HYDRUS-PHREEQC module to analyze trace metal transport involving cation exchange and surface complexation sorption reactions in the vadose zone leached with coal seam gas produced water following some accidental water release scenario. Results show that the main process responsible for trace metal migration is complexation of naturally present trace metals with inorganic ligands such as (bi)carbonate that enter the soil upon infiltration with alkaline produced water.

Novel systems and methods for quantum communication, quantum computation, and quantum simulation

NASA Astrophysics Data System (ADS)

Gorshkov, Alexey Vyacheslavovich

Precise control over quantum systems can enable the realization of fascinating applications such as powerful computers, secure communication devices, and simulators that can elucidate the physics of complex condensed matter systems. However, the fragility of quantum effects makes it very difficult to harness the power of quantum mechanics. In this thesis, we present novel systems and tools for gaining fundamental insights into the complex quantum world and for bringing practical applications of quantum mechanics closer to reality. We first optimize and show equivalence between a wide range of techniques for storage of photons in atomic ensembles. We describe experiments demonstrating the potential of our optimization algorithms for quantum communication and computation applications. Next, we combine the technique of photon storage with strong atom-atom interactions to propose a robust protocol for implementing the two-qubit photonic phase gate, which is an important ingredient in many quantum computation and communication tasks. In contrast to photon storage, many quantum computation and simulation applications require individual addressing of closely-spaced atoms, ions, quantum dots, or solid state defects. To meet this requirement, we propose a method for coherent optical far-field manipulation of quantum systems with a resolution that is not limited by the wavelength of radiation. While alkali atoms are currently the system of choice for photon storage and many other applications, we develop new methods for quantum information processing and quantum simulation with ultracold alkaline-earth atoms in optical lattices. We show how multiple qubits can be encoded in individual alkaline-earth atoms and harnessed for quantum computing and precision measurements applications. We also demonstrate that alkaline-earth atoms can be used to simulate highly symmetric systems exhibiting spin-orbital interactions and capable of providing valuable insights into strongly correlated physics of transition metal oxides, heavy fermion materials, and spin liquid phases. While ultracold atoms typically exhibit only short-range interactions, numerous exotic phenomena and practical applications require long-range interactions, which can be achieved with ultracold polar molecules. We demonstrate the possibility to engineer a repulsive interaction between polar molecules, which allows for the suppression of inelastic collisions, efficient evaporative cooling, and the creation of novel phases of polar molecules.

Influence of media composition on the production of alkaline α-amylase from Bacillus subtilis CB-18.

PubMed

Ogbonnaya, Nwokoro; Odiase, Anthonia

2012-01-01

Starch, a homopolysaccharide is an important and an abundant food reserve and energy source. Starches are processed to yield different products which find many industrial applications. Alpha-amylases hydrolyze starch by cleaving α-1,4-glucosidic bonds and have been used in food, textile and pharmaceutical industries [Sun et al. 2010]. Enzymatic conversion of starch with amylase presents an economically superior alternative to the conventional method of starch gelatinization. Alkaline α-amylase has an important position in the global enzyme market as a constituent of detergent. In this paper, we screened soil bacteria and an isolate, alkalophilic Bacillus subtilis CB-18 was found to produce an alkaline α-amylase in different media. MATERIAL AND METHODS. Screening of the isolates for amylolytic activity was carried out by growing bacteria isolated from the soil in starch agar plates and subsequently staining the plates with iodine solution to reveal zones of hydrolysis of starch. The selected isolate, Bacillus subtlis CB-18 was grown in different media at alkaline pH to evaluate the influence of media composition on alkaline α-amylase production. Enzyme assay was carried out by growing the culture in a broth medium and obtaining cell - free culture supernatant after centrifugation at 2515 × g for 15 minutes Amylase activity was determined by incubating 0.5 ml of crude enzyme solution in 0.1M Tris/HCl buffer (pH 8.5) with 0.5 ml of 1% soluble starch solution. The reaction was terminated by the addition of DNS reagent and reducing sugar produced from the amylolytic reaction was determined. Bacillus subtilis CB-18 used for this work was selected because it produced 7 mm zone diameter on starch agar plate. This organism was cultured in different alkaline broth media containing 2% soluble starch as inducer carbohydrate for α-amylase production. Among the carbon sources used for enzyme production, sorbitol was the best to stimulate enzyme production with α-amylase activity of 758 U/mL after 48 h. Peptone was the best nitrogen source for enzyme production with α-amylase activity of 680 U/mL after 48 h. Metal ions including Ca (2+), Mn(2+) and Mg(2+) stimulated enzyme production while Hg(2+) and Ag(+) repressed enzyme production. The best enzyme yields were observed in basal media containing agro-based substrates. This work reports the production of alkaline α-amylase by Bacillus subtlis CB-18 in different media. Enzyme production was highest when agro-based media were used to formulate the media.

Hydroxide Self-Feeding High-Temperature Alkaline Direct Formate Fuel Cells.

PubMed

Li, Yinshi; Sun, Xianda; Feng, Ying

2017-05-22

Conventionally, both the thermal degradation of the anion-exchange membrane and the requirement of additional hydroxide for fuel oxidation reaction hinder the development of the high-temperature alkaline direct liquid fuel cells. The present work addresses these two issues by reporting a polybenzimidazole-membrane-based direct formate fuel cell (DFFC). Theoretically, the cell voltage of the high-temperature alkaline DFFC can be as high as 1.45 V at 90 °C. It has been demonstrated that a proof-of-concept alkaline DFFC without adding additional hydroxide yields a peak power density of 20.9 mW cm -2 , an order of magnitude higher than both alkaline direct ethanol fuel cells and alkaline direct methanol fuel cells, mainly because the hydrolysis of formate provides enough OH - ions for formate oxidation reaction. It was also found that this hydroxide self-feeding high-temperature alkaline DFFC shows a stable 100 min constant-current discharge at 90 °C, proving the conceptual feasibility. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Investigation of aluminum gate CMP in a novel alkaline solution

NASA Astrophysics Data System (ADS)

Cuiyue, Feng; Yuling, Liu; Ming, Sun; Wenqian, Zhang; Jin, Zhang; Shuai, Wang

2016-01-01

Beyond 45 nm, due to the superior CMP performance requirements with the metal gate of aluminum in the advanced CMOS process, a novel alkaline slurry for an aluminum gate CMP with poly-amine alkali slurry is investigated. The aluminum gate CMP under alkaline conditions has two steps: stock polishing and fine polishing. A controllable removal rate, the uniformity of aluminum gate and low corrosion are the key challenges for the alkaline polishing slurry of the aluminum gate CMP. This work utilizes the complexation-soluble function of FA/O II and the preference adsorption mechanism of FA/O I nonionic surfactant to improve the uniformity of the surface chemistry function with the electrochemical corrosion research, such as OCP-TIME curves, Tafel curves and AC impedance. The result is that the stock polishing slurry (with SiO2 abrasive) contains 1 wt.% H2O2,0.5 wt.% FA/O II and 1.0 wt.% FA/O I nonionic surfactant. For a fine polishing process, 1.5 wt.% H2O2, 0.4 wt.% FA/O II and 2.0 wt.% FA/O I nonionic surfactant are added. The polishing experiments show that the removal rates are 3000 ± 50 Å/min and 1600 ± 60 Å/min, respectively. The surface roughnesses are 2.05 ± 0.128 nm and 1.59 ± 0.081 nm, respectively. A combination of the functions of FA/O II and FA/O I nonionic surfactant obtains a controllable removal rate and a better surface roughness in alkaline solution.

Acid-Activatable Michael-Type Fluorescent Probes for Thiols and for Labeling Lysosomes in Live Cells.

PubMed

Dai, Chun-Guang; Du, Xiao-Jiao; Song, Qin-Hua

2015-12-18

A Michael addition is usually taken as a base-catalyzed reaction. Most fluorescent probes have been designed to detect thiols in slightly alkaline solutions (pH 7-9). The sensing reactions of almost all Michael-type fluorescent probes for thiols are faster in a high pH solution than in a low pH solution. In this work, we synthesized a series of 7-substituted 2-(quinolin-2-ylmethylene)malonic acids (QMAs, substituents: NEt2, OH, H, Cl, or NO2) and their ethyl esters (QMEs) as Michael-type fluorescent probes for thiols. The sensing reactions of QMAs and QMEs occur in distinct pH ranges, pH < 7 for QMAs and pH > 7 for QMEs. On the basis of experimental and theoretic studies, we have clarified the distinct pH effects on the sensing reactivity between QMAs and QMEs and demonstrated that two QMAs (NEt2, OH) are highly sensitive and selective fluorescent probes for thiols in acidic solutions (pH < 7) and promising dyes that can label lysosomes in live cells.

Immobilization of chromate in hyperalkaline waste streams by green rusts and zero-valent iron.

PubMed

Rogers, Christine M; Burke, Ian T; Ahmed, Imad A M; Shaw, Samuel

2014-01-01

Zero-valent iron (ZVI) and green rusts can be used as reductants to convert chromium from soluble, highly toxic Cr(VI) to insoluble Cr(III). This study compared the reduction rates of Cr(VI) by ZVI and two carbonate green rust phases in alkaline/hyperalkaline solutions. Batch experiments were carried out with synthetic chromate solutions at pH 7.7-12.3 and a chromite ore processing residue (COPR) leachate (pH approximately 12.2). Green rust removes chromate from high pH solutions (pH 10-12.5) very rapidly (<400 s). Chromate reduction rates for both green rust phases were consistently higher than for ZVI throughout the pH range studied; the surface area normalized rate constants were two orders of magnitude higher in the COPR leachate solution at pH 12.2. The performances of both green rusts were unaffected by changes in pH. In contrast, ZVI exhibited a marked decline in reduction rate with increasing pH to become almost ineffective above pH12.

Process for producing peracids from aliphatic hydroxy carboxylic acids

DOEpatents

Chum, H.L.; Palasz, P.D.; Ratcliff, M.A.

1984-12-20

A process is described for producing peracids from lactic acid-containing solutions derived from biomass processing systems. It consists of adjusting the pH of the solution to about 8 to 9 and removing alkaline residue fractions therefrom to form a solution comprised substantially of lower aliphatic hydroxy acids. The solution is oxidized to produce volatile lower aliphatic aldehydes. The aldehydes are removed as they are generated and converted to peracids.

Experimental and natural constraints on the generation of calc-alkaline volcanic rocks in the Western Aleutian arc

NASA Astrophysics Data System (ADS)

Cottrell, E.; Kelley, K. A.; Grant, E.; Coombs, M. L.; Pistone, M.

2016-12-01

A new experimental technique with unique geometry is presented investigating deformation of simulated boreholes using standard axisymmetric triaxial deformation equipment. The Sandia WEllbore SImulation, SWESI, geometry, uses right cylinders of rock 50mm in diameter and 75mm in length. A 11.3mm hole is drilled perpendicular to the axis of the cylinder in the center of the sample to simulate a borehole. The hole is covered with a solid metal cover, and sealed with polyurethane. The metal cover can be machined with a high-pressure port to introduce different fluid chemistries into the borehole at controlled pressures. Samples are deformed in a standard load frame under confinement, allowing for a broad range of possible stresses, load paths, and temperatures. Experiments in this study are loaded to the desired confining pressure, then deformed at a constant axial strain rate or 10-5 sec-1. Two different suites of experiments are conducted in this study on sedimentary and crystalline rock types. The first series of experiments are conducted on Mancos Shale, a finely laminated transversely isotropic rock. Samples are cored at three different orientations to the laminations. A second series of experiments is conducted on Sierra White granite with different fluid chemistries inside the borehole. Numerical modelling and experimental observations including CT-microtomography demonstrate that stresses are concentrated around the simulated wellbore and recreate wellbore deformation mechanisms. Borehole strength and damage development is dependent on anisotropy orientation and fluid chemistry. Observed failure geometries, particularly for Mancos shale, can be highly asymmetric. These results demonstrate uncertainties in in situ stresses measurements using commonly-applied borehole breakout techniques in complicated borehole physico-chemical environments. Sandia National Laboratories is a multimission laboratory managed and operated by National Technology and Engineering Solutions of Sandia LLC, a wholly owned subsidiary of Honeywell International Inc. for the U.S. Department of Energy's National Nuclear Security Administration under contract DE-NA0003525. SAND2017-8259 A

Capacitive Deionization of High-Salinity Solutions

DOE PAGES

Sharma, Ketki; Gabitto, Jorge; Mayes, Richard T.; ...

2014-12-22

Desalination of high salinity solutions has been studied using a novel experimental technique and a theoretical model. Neutron imaging has been employed to visualize lithium ions in mesoporous carbon materials, which are used as electrodes in capacitive deionization for water desalination. Experiments were conducted with a flow-through capacitive deionization cell designed for neutron imaging and with lithium chloride ( 6LiCl) as the electrolyte. Sequences of neutron images have been obtained at a relatively high concentration of lithium chloride ( 6LiCl) solution to provide information on the transport of ions within the electrodes. A new model that computes the individual ionicmore » concentration profiles inside mesoporous carbon electrodes has been used to simulate the capacitive deionization process. Modifications have also been introduced into the simulation model to calculate results at high electrolyte concentrations. Experimental data and simulation results provide insight into why capacitive deionization is not effective for desalination of high ionic-strength solutions. The combination of experimental information, obtained through neutron imaging, with the theoretical model will help in the design of capacitive deionization devices, which can improve the process for high ionic-strength solutions.« less

Shake and stew: a non-destructive PCR-ready DNA isolation method from a single preserved fish larva.

PubMed

Alvarado Bremer, J R; Smith, B L; Moulton, D L; Lu, C-P; Cornic, M

2014-01-01

A rapid non-destructive alternative to isolate DNA from an individual fish larva is presented, based on the suspension of epithelial cells through vortex forces, and the release of DNA in a heated alkaline solution. DNA from >6056 fish larvae isolated using this protocol has yielded a high PCR amplification success rate (>93%), suggesting its applicability to other taxonomic groups or sources when tissue amount is the limiting factor. © 2014 The Fisheries Society of the British Isles.

Self-Assembled Fe-N-Doped Carbon Nanotube Aerogels with Single-Atom Catalyst Feature as High-Efficiency Oxygen Reduction Electrocatalysts

DOE PAGES

Zhu, Chengzhou; Fu, Shaofang; Song, Junhua; ...

2017-02-06

In this study, self-assembled M–N-doped carbon nanotube aerogels with single-atom catalyst feature are for the first time reported through one-step hydrothermal route and subsequent facile annealing treatment. By taking advantage of the porous nanostructures, 1D nanotubes as well as single-atom catalyst feature, the resultant Fe–N-doped carbon nanotube aerogels exhibit excellent oxygen reduction reaction electrocatalytic performance even better than commercial Pt/C in alkaline solution.

ALKALINE CARBONATE LEACHING PROCESS FOR URANIUM EXTRACTION

DOEpatents

Thunaes, A.; Brown, E.A.; Rabbitts, A.T.

1957-11-12

A process for the leaching of uranium from high carbonate ores is presented. According to the process, the ore is leached at a temperature of about 200 deg C and a pressure of about 200 p.s.i.g. with a solution containing alkali carbonate, alkali permanganate, and bicarbonate ion, the bicarbonate ion functionlng to prevent premature formation of alkali hydroxide and consequent precipitation of a diuranate. After the leaching is complete, the uranium present is recovered by precipitation with NaOH.

Purification of Torpedo californica post-synaptic membranes and fractionation of their constituent proteins.

PubMed Central

Elliott, J; Blanchard, S G; Wu, W; Miller, J; Strader, C D; Hartig, P; Moore, H P; Racs, J; Raftery, M A

1980-01-01

A rapid methof for preparation of membrane fractions highly enriched in nicotinic acetylcholine receptor from Torpedo californica electroplax is described. The major step in this purification involves sucrose-density-gradient centrifugation in a reorienting rotor. Further purification of these membranes can be achieved by selective extraction of proteins by use of alkaline pH or by treatment with solutions of lithium di-idosalicylate. The alkali-treated membranes retain functional characteristics of the untreated membranes and in addition contain essentially only the four polypeptides (mol.wts. 40000, 50000, 60000 and 65000) characteristic of the receptor purified by affinity chromatography. Dissolution of the purified membranes or of the alkali-treated purified membranes in sodium cholate solution followed by sucrose-density-gradient centrifugation in the same detergent solution yields solubilized receptor preparations comparable with the most highly purified protein obtained by affinity-chromatographic procedures. Images Fig. 1. Fig. 2. Fig. 3. Fig. 5. Fig. 7. PLATE 1 PMID:7387629

Indefinitely stable iron(IV) cage complexes formed in water by air oxidation

NASA Astrophysics Data System (ADS)

Tomyn, Stefania; Shylin, Sergii I.; Bykov, Dmytro; Ksenofontov, Vadim; Gumienna-Kontecka, Elzbieta; Bon, Volodymyr; Fritsky, Igor O.

2017-01-01

In nature, iron, the fourth most abundant element of the Earth's crust, occurs in its stable forms either as the native metal or in its compounds in the +2 or +3 (low-valent) oxidation states. High-valent iron (+4, +5, +6) compounds are not formed spontaneously at ambient conditions, and the ones obtained synthetically appear to be unstable in polar organic solvents, especially aqueous solutions, and this is what limits their studies and use. Here we describe unprecedented iron(IV) hexahydrazide clathrochelate complexes that are assembled in alkaline aqueous media from iron(III) salts, oxalodihydrazide and formaldehyde in the course of a metal-templated reaction accompanied by air oxidation. The complexes can exist indefinitely at ambient conditions without any sign of decomposition in water, nonaqueous solutions and in the solid state. We anticipate that our findings may open a way to aqueous solution and polynuclear high-valent iron chemistry that remains underexplored and presents an important challenge.

Indefinitely stable iron(IV) cage complexes formed in water by air oxidation.

PubMed

Tomyn, Stefania; Shylin, Sergii I; Bykov, Dmytro; Ksenofontov, Vadim; Gumienna-Kontecka, Elzbieta; Bon, Volodymyr; Fritsky, Igor O

2017-01-19

In nature, iron, the fourth most abundant element of the Earth's crust, occurs in its stable forms either as the native metal or in its compounds in the +2 or +3 (low-valent) oxidation states. High-valent iron (+4, +5, +6) compounds are not formed spontaneously at ambient conditions, and the ones obtained synthetically appear to be unstable in polar organic solvents, especially aqueous solutions, and this is what limits their studies and use. Here we describe unprecedented iron(IV) hexahydrazide clathrochelate complexes that are assembled in alkaline aqueous media from iron(III) salts, oxalodihydrazide and formaldehyde in the course of a metal-templated reaction accompanied by air oxidation. The complexes can exist indefinitely at ambient conditions without any sign of decomposition in water, nonaqueous solutions and in the solid state. We anticipate that our findings may open a way to aqueous solution and polynuclear high-valent iron chemistry that remains underexplored and presents an important challenge.

Indefinitely stable iron(IV) cage complexes formed in water by air oxidation

PubMed Central

Tomyn, Stefania; Shylin, Sergii I.; Bykov, Dmytro; Ksenofontov, Vadim; Gumienna-Kontecka, Elzbieta; Bon, Volodymyr; Fritsky, Igor O.

2017-01-01

In nature, iron, the fourth most abundant element of the Earth's crust, occurs in its stable forms either as the native metal or in its compounds in the +2 or +3 (low-valent) oxidation states. High-valent iron (+4, +5, +6) compounds are not formed spontaneously at ambient conditions, and the ones obtained synthetically appear to be unstable in polar organic solvents, especially aqueous solutions, and this is what limits their studies and use. Here we describe unprecedented iron(IV) hexahydrazide clathrochelate complexes that are assembled in alkaline aqueous media from iron(III) salts, oxalodihydrazide and formaldehyde in the course of a metal-templated reaction accompanied by air oxidation. The complexes can exist indefinitely at ambient conditions without any sign of decomposition in water, nonaqueous solutions and in the solid state. We anticipate that our findings may open a way to aqueous solution and polynuclear high-valent iron chemistry that remains underexplored and presents an important challenge. PMID:28102364

Friction Modifier Using Adherent Metallic Multilayered or Mixed Element Layer Conversion Coatings

NASA Technical Reports Server (NTRS)

Schramm, Harry F. (Inventor); Defalco, Francis G. (Inventor); Starks, Lloyd L., Sr. (Inventor)

2013-01-01

A process for creating conversion coatings and spin, drawing, and extrusion finishes for surfaces, wherein the conversion coatings and spin, drawing, and extrusion finishes contain potassium, phosphorus, nitrogen, and one or more non-alkaline metals and/or one or more metalloids. The process comprises forming an aqueous solution of water, phosphoric acid or sulfuric acid, ammonium hydroxide, an alkali metal hydroxide, and one or more non-alkaline metals and/or one or more metalloids. The aqueous solution forms an anti-friction multilayer conversion and/or mixed element coating or a spin, drawing, and extrusion finish on a surface when applied to the surface, either directly without the use of applied external electromotive force, or as an additive in lubricating fluids.

Properties of a novel polysiloxane-guttapercha calcium silicate-bioglass-containing root canal sealer.

PubMed

Gandolfi, M G; Siboni, F; Prati, C

2016-05-01

Root canal filling sealers based on polymethyl hydrogensiloxane or polymethyl hydrogensiloxane-guttapercha--introduced to improve the quality of conventional guttapercha-based and resin-based systems--showed advantages in handiness and clinical application. The aim of the study was to evaluate the chemical-physical properties of a novel polysiloxane-guttapercha calcium silicate-containing root canal sealer (GuttaFlow bioseal). GuttaFlow bioseal was examined and compared with GuttaFlow2, RoekoSeal and MTA Fillapex sealers. Setting times, open and impervious porosity and apparent porosity, water sorption, weight loss, calcium release, and alkalinizing activity were evaluated. ESEM-EDX-Raman analyses of fresh materials and after soaking in simulated body fluid were also performed. Marked differences were obtained among the materials. GuttaFlow bioseal showed low solubility and porosity, high water sorption, moderate calcium release and good alkalinizing activity. MTA Fillapex showed the highest calcium release, alkalinizing activity and solubility, RoekoSeal the lowest calcium release, no alkalinizing activity, very low solubility and water sorption. Only GuttaFlow bioseal showed apatite forming ability. GuttaFlow bioseal showed alkalinizing activity together with negligible solubility and slight calcium release. Therefore, the notable nucleation of apatite and apatite precursors can be related to the co-operation of CaSi particles (SiOH groups) with polysiloxane (SiOSi groups). The incorporation of a calcium silicate component into polydimethyl polymethylhydrogensiloxane guttapercha sealers may represent an attractive strategy to obtain a bioactive biointeractive flowable guttapercha sealer for moist/bleeding apices with bone defects in endodontic therapy. Copyright © 2016 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Leak rates in sealed cells.

NASA Technical Reports Server (NTRS)

Frank, H. A.; Uchiyama, A. A.

1973-01-01

Water vapor loss rates were determined from simulated and imperfectly sealed alkaline cells in the vacuum environment. The observed rates were found to be in agreement with a semi-empirical equation employed in vacuum technology. Results thereby give support for using this equation for the prediction of loss rates of battery gases and vapors to the aerospace environment. On this basis it was shown how the equation can be applied to the solution of many heretofore unresolved questions regarding leaks in batteries. Among these are the maximum permissible leak size consistent with a given cell life or conversely the maximum life consistent with a given leak size. It was also shown that loss rates of these cells in the terrestrial environment are several orders of magnitude less than the corresponding loss rates in the aerospace environment.

Mathematical modeling of microbially induced crown corrosion in wastewater collection systems and laboratory investigation and modeling of sulfuric acid corrosion of concrete

NASA Astrophysics Data System (ADS)

Jahani, Fereidoun

In the model for microbially induced crown corrosion, the diffusion of sulfide inside the concrete pores, its biological conversion to sulfuric acid, and the corrosion of calcium carbonate aggregates are represented. The corrosion front is modeled as a moving boundary. The location of the interface between the corrosion layer and the concrete is determined as part of the solution to the model equations. This model consisted of a system of one dimensional reaction-diffusion equations coupled to an equation describing the movement of the corrosion front. The equations were solved numerically using finite element Galerkin approximation. The concentration profiles of sulfide in the air and the liquid phases, the pH as a function of concrete depth, and the position of the corrosion front. A new equation for the corrosion rate was also derived. A more specific model for the degradation of a concrete specimen exposed to a sulfuric acid solution was also studied. In this model, diffusion of hydrogen ions and their reaction with alkaline components of concrete were expressed using Fick's Law of diffusion. The model equations described the moving boundary, the dissolution rate of alkaline components in the concrete, volume increase of sulfuric acid solution over the concrete specimen, and the boundary conditions on the surface of the concrete. An apparatus was designed and experiments were performed to measure pH changes on the surface of concrete. The data were used to calculate the dissolution rate of the concrete and, with the model, to determine the diffusion rate of sulfuric acid in the corrosion layer and corrosion layer thickness. Electrochemical Impedance Spectroscopy (EIS) was used to study the corrosion rate of iron pins embedded in the concrete sample. The open circuit potential (OCP) determined the onset of corrosion on the surface of the pins. Visual observation of the corrosion layer thickness was in good agreement with the simulation results.

The Space-Time Conservative Schemes for Large-Scale, Time-Accurate Flow Simulations with Tetrahedral Meshes

NASA Technical Reports Server (NTRS)

Venkatachari, Balaji Shankar; Streett, Craig L.; Chang, Chau-Lyan; Friedlander, David J.; Wang, Xiao-Yen; Chang, Sin-Chung

2016-01-01

Despite decades of development of unstructured mesh methods, high-fidelity time-accurate simulations are still predominantly carried out on structured, or unstructured hexahedral meshes by using high-order finite-difference, weighted essentially non-oscillatory (WENO), or hybrid schemes formed by their combinations. In this work, the space-time conservation element solution element (CESE) method is used to simulate several flow problems including supersonic jet/shock interaction and its impact on launch vehicle acoustics, and direct numerical simulations of turbulent flows using tetrahedral meshes. This paper provides a status report for the continuing development of the space-time conservation element solution element (CESE) numerical and software framework under the Revolutionary Computational Aerosciences (RCA) project. Solution accuracy and large-scale parallel performance of the numerical framework is assessed with the goal of providing a viable paradigm for future high-fidelity flow physics simulations.

Characterization of commercial iron chelates and their behavior in an alkaline and calcareous soil.

PubMed

Cantera, Rodrigo G; Zamarreño, Angel M; García-Mina, José M

2002-12-18

Iron deficiency is a common problem for many plants grown in alkaline and calcareous soils. To correct this problem, iron is supplied to plants as chelates. Several iron chelates are sold under diverse trademarks with different characteristics. This work evaluated 18 commercial products containing the most representative chelated iron sources used in agricultural practice in Spain when the study was done, namely the ferric chelates of EDDHA, EDDHMA, EDDCHA, EDDHSA, EDTA, and DTPA. The chelates were comprehensively characterized and quantitated by several techniques, including several chromatographic methods. Iron and chelate dynamics in soil were also studied in a model alkaline and calcareous soil. Results indicate that, in this model soil, among the different iron compounds studied only FeEDDHA and analogues have the capacity to maintain soluble iron in soil solution over time. These results are in agreement with general experience under field conditions. Furthermore, among the different ortho-ortho isomers of FeEDDHA's, FeEDDHSA and FeEDDCHA showed greater capacity than FeEDDHA and FeEDDHMA to maintain the chelated iron in soil solution over time.

Introducing catalyst in alkaline membrane for improved performance direct borohydride fuel cells

NASA Astrophysics Data System (ADS)

Qin, Haiying; Lin, Longxia; Chu, Wen; Jiang, Wei; He, Yan; Shi, Qiao; Deng, Yonghong; Ji, Zhenguo; Liu, Jiabin; Tao, Shanwen

2018-01-01

A catalytic material is introduced into the polymer matrix to prepare a novel polymeric alkaline electrolyte membrane (AEM) which simultaneously increases ionic conductivity, reduces the fuel cross-over. In this work, the hydroxide anion exchange membrane is mainly composed of poly(vinylalcohol) and alkaline exchange resin. CoCl2 is added into the poly(vinylalcohol) and alkaline exchange resin gel before casting the membrane to introduce catalytic materials. CoCl2 is converted into CoOOH after the reaction with KOH solution. The crystallinity of the polymer matrix decreases and the ionic conductivity of the composite membrane is notably improved by the introduction of Co-species. A direct borohydride fuel cell using the composite membrane exhibits an open circuit voltage of 1.11 V at 30 °C, which is notably higher than that of cells using other AEMs. The cell using the composite membrane achieves a maximum power density of 283 mW cm-2 at 60 °C while the cell using the membrane without Co-species only reaches 117 mW cm-2 at the same conditions. The outstanding performance of the cell using the composite membrane benefits from impregnation of the catalytic Co-species in the membrane, which not only increases the ionic conductivity but also reduces electrode polarization thus improves the fuel cell performance. This work provides a new approach to develop high-performance fuel cells through adding catalysts in the electrolyte membrane.

High performance zinc anode for battery applications

NASA Technical Reports Server (NTRS)

Casey, John E., Jr. (Inventor)

1998-01-01

An improved zinc anode for use in a high density rechargeable alkaline battery is disclosed. A process for making the zinc electrode comprises electrolytic loading of the zinc active material from a slightly acidic zinc nitrate solution into a substrate of nickel, copper or silver. The substrate comprises a sintered plaque having very fine pores, a high surface area, and 80-85 percent total initial porosity. The residual porosity after zinc loading is approximately 25-30%. The electrode of the present invention exhibits reduced zinc mobility, shape change and distortion, and demonstrates reduced dendrite buildup cycling of the battery. The disclosed battery is useful for applications requiring high energy density and multiple charge capability.

Enhanced decomposition of 1,4-dioxane in water by ozonation under alkaline condition.

PubMed

Tian, Gui-Peng; Wu, Qian-Yuan; Li, Ang; Wang, Wen-Long; Hu, Hong-Ying

2014-01-01

1,4-Dioxane is a probable human carcinogenic and refractory substance that is widely detected in aquatic environments. Traditional wastewater treatment processes, including activated sludge, cannot remove 1,4-dioxane. Removing 1,4-dioxane with a reaction kinetic constant of 0.32 L/(mol·s) by using ozone, a strong oxidant, is difficult. However, under alkaline environment, ozone generates a hydroxyl radical (•OH) that exhibits strong oxidative potential. Thus, the ozonation of 1,4-dioxane in water under different pH conditions was investigated in this study. In neutral solution, with an inlet ozone feed rate of 0.19 mmol/(L·min), the removal efficiency of 1,4-dioxane was 7.6% at 0.5 h, whereas that in alkaline solution was higher (16.3-94.5%) within a pH range of 9-12. However, the removal efficiency of dissolved organic carbon was considerably lower than that of 1,4-dioxane. This result indicates that several persistent intermediates were generated during 1,4-dioxane ozonation. The pseudo first-order reaction further depicted the reaction of 1,4-dioxane. The obvious kinetic constants (kobs) at pH 9, 10, 11 and 12 were 0.94, 2.41, 24.88 and 2610 L/(mol·s), respectively. Scavenger experiments on radical species indicated that •OH played a key role in removing 1,4-dioxane during ozonation under alkaline condition.

Removing polysaccharides-and saccharides-related coloring impurities in alkyl polyglycosides by bleaching with the H2O2/TAED/NaHCO3 system.

PubMed

Yanmei, Liu; Jinliang, Tao; Jiao, Sun; Wenyi, Chen

2014-11-04

The effect of H2O2/TAED/NaHCO3 system, namely NaHCO3 as alkaline agent with the (tetra acetyl ethylene diamine (TAED)) TAED-activated peroxide system, bleaching of alkyl polyglycosides solution was studied by spectrophotometry. The results showed that the optimal bleaching conditions about H2O2/TAED/NaHCO3 system bleaching of alkyl polyglycosides solution were as follows: molar ratio of TAED to H2O2 was 0.06, addition of H2O2 was 8.6%, addition of NaHCO3 was 3.2%, bleaching temperature of 50-65 °C, addition of MgO was 0.13%, and bleaching time was 8h. If too much amount of NaHCO3 was added to the system and maintained alkaline pH, the bleaching effect would be greatly reduced. Fixing molar ratio of TAED to H2O2 and increasing the amount of H2O2 were beneficial to improve the whiteness of alkyl polyglycosides, but adding too much amount of H2O2 would reduce the transparency. In the TAED-activated peroxide system, NaHCO3 as alkaline agent and buffer agent, could overcome the disadvantage of producing black precipitates when NaOH as alkaline agent. Copyright © 2014 Elsevier Ltd. All rights reserved.

Facile and scalable fabrication engineering of fullerenol nanoparticles by improved alkaline-oxidation approach and its antioxidant potential in maize

NASA Astrophysics Data System (ADS)

Liu, Fu-yang; Xiong, Feng-xia; Fan, Yi-kang; Li, Juan; Wang, He-zhong; Xing, Geng-mei; Yan, Feng-ming; Tai, Fu-ju; He, Rui

2016-11-01

A feasible in operation, labor-saving and low-cost one-step technology to fabricate fullerenol nanoparticles (FNPs) up to 10 g in laboratory was developed by improved alkaline-oxidation approach using moderately concentrated sodium hydroxide solution as the hydroxylation agent and o-dichlorobenzene as the solvent. This strategy paves the avenue for industrial-scale bulk production of FNPs. The resulted product, [C60(OH)22·8H2O]n, were characterized by various measurements including matrix-assisted laser desorption ionization time-of-flight mass spectrometry, high-resolution 1H nuclear magnetic resonance spectrometry, Fourier transform infrared spectroscopy, UV-Visible spectrophotometer, thermogravimetric analysis, differential scanning calorimetry, dynamic light scattering analysis, scanning electron microscopy, and electron spin resonance spectrometer. Radical scavenging assay in vitro confirmed the high efficiency of water-soluble [C60(OH)22·8H2O]n as a novel radical scavenger. Furthermore, [C60(OH)22·8H2O]n as an excellent candidate has the potential to serve as the plant defense stimulation agent in maize.

Electrodeposition of hierarchically structured three-dimensional nickel–iron electrodes for efficient oxygen evolution at high current densities

PubMed Central

Lu, Xunyu; Zhao, Chuan

2015-01-01

Large-scale industrial application of electrolytic splitting of water has called for the development of oxygen evolution electrodes that are inexpensive, robust and can deliver large current density (>500 mA cm−2) at low applied potentials. Here we show that an efficient oxygen electrode can be developed by electrodepositing amorphous mesoporous nickel–iron composite nanosheets directly onto macroporous nickel foam substrates. The as-prepared oxygen electrode exhibits high catalytic activity towards water oxidation in alkaline solutions, which only requires an overpotential of 200 mV to initiate the reaction, and is capable of delivering current densities of 500 and 1,000 mA cm−2 at overpotentials of 240 and 270 mV, respectively. The electrode also shows prolonged stability against bulk water electrolysis at large current. Collectively, the as-prepared three-dimensional structured electrode is the most efficient oxygen evolution electrode in alkaline electrolytes reported to the best of our knowledge, and can potentially be applied for industrial scale water electrolysis. PMID:25776015

Oxygen Reduction on Gold Nanocrystal Surfaces in Alkaline Electrolyte: Evidence for Surface Proton Transfer Effects

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

Zhang, Yu; Lu, Fang; Liu, Shizhong

Four-electron oxygen reduction reaction (4e-ORR) pathway, as a key high-performance reaction pathway in energy conversion, has been sought after in numerous investigations on metal surfaces over the last decades. Although the surfaces of the most noble metals, including platinum and palladium, demonstrate the fullpotential- range 4e-ORR, this is not the case, for gold (Au) surfaces. The 4e-ORR is only operative on Au surfaces with {100} subfacets, e.g. Au(100), in alkaline solution, however restricted to a certain potential region at low overpotentials, while reverting to a 2e-ORR at high overpotentials. This ORR on Au(100) has been a long-standing puzzle of electrocatalysis.more » Hereby we review the ORR studies on Au, along with the studies of water effects on Au catalysts, and present our electrochemical results with monofacet Au nanocrystals. Finally, combining with theoretical calculations we demonstrate that surface proton transfer from co-adsorbed water plays the key role in determining the ORR mechanism on Au surfaces in base.« less

Iodine-Mediated Etching of Gold Nanorods for Plasmonic ELISA Based on Colorimetric Detection of Alkaline Phosphatase.

PubMed

Zhang, Zhiyang; Chen, Zhaopeng; Wang, Shasha; Cheng, Fangbin; Chen, Lingxin

2015-12-23

Here, we propose a plasmonic enzyme-linked immunosorbent assay (ELISA) based on highly sensitive colorimetric detection of alkaline phosphatase (ALP), which is achieved by iodine-mediated etching of gold nanorods (AuNRs). Once the sandwich-type immunocomplex is formed, the ALP bound on the polystyrene microwells will hydrolyze ascorbic acid 2-phosphate into ascorbic acid. Subsequently, iodate is reduced to iodine, a moderate oxidant, which etches AuNRs from rod to sphere in shape. The shape change of AuNRs leads to a blue-shift of longitudinal localized surface plasmon resonance. As a result, the solution of AuNRs changes from blue to red. Benefiting from the highly sensitive detection of ALP, the proposed plasmonic ELISA has achieved an ultralow detection limit (100 pg/mL) for human immunoglobulin G (IgG). Importantly, the visual detection limit (3.0 ng/mL) allows the rapid differential diagnosis with the naked eye. The further detection of human IgG in fetal bovine serum indicates its applicability to the determination of low abundance protein in complex biological samples.

Oxygen Reduction on Gold Nanocrystal Surfaces in Alkaline Electrolyte: Evidence for Surface Proton Transfer Effects

DOE PAGES

Zhang, Yu; Lu, Fang; Liu, Shizhong; ...

2018-04-01

Four-electron oxygen reduction reaction (4e-ORR) pathway, as a key high-performance reaction pathway in energy conversion, has been sought after in numerous investigations on metal surfaces over the last decades. Although the surfaces of the most noble metals, including platinum and palladium, demonstrate the fullpotential- range 4e-ORR, this is not the case, for gold (Au) surfaces. The 4e-ORR is only operative on Au surfaces with {100} subfacets, e.g. Au(100), in alkaline solution, however restricted to a certain potential region at low overpotentials, while reverting to a 2e-ORR at high overpotentials. This ORR on Au(100) has been a long-standing puzzle of electrocatalysis.more » Hereby we review the ORR studies on Au, along with the studies of water effects on Au catalysts, and present our electrochemical results with monofacet Au nanocrystals. Finally, combining with theoretical calculations we demonstrate that surface proton transfer from co-adsorbed water plays the key role in determining the ORR mechanism on Au surfaces in base.« less

Non-canonical amino acids bearing thiophene and bithiophene: synthesis by an Ugi multicomponent reaction and studies on ion recognition ability.

PubMed

Esteves, Cátia I C; Raposo, M Manuela M; Costa, Susana P G

2017-05-01

Novel thienyl and bithienyl amino acids with different substituents were obtained by a multicomponent Ugi reaction between a heterocyclic aldehyde, an amine, an acid and an isocyanide. Due to the presence of the sulphur heterocycle at the side chain, these unnatural amino acids are highly emissive and bear extra electron donating atoms so they were tested for their ability to act as fluorescent probes and chemosensors in the recognition of biomedically relevant ions in acetonitrile and acetonitrile/water solutions. The results obtained from spectrophotometric/spectrofluorimetric titrations in the presence of organic and inorganic anions, and alkaline; alkaline-earth and transition metal cations indicated that the bithienyl amino acid bearing a methoxy group is a selective colorimetric chemosensor for Cu 2+ , while the other (bi)thienyl amino acids act as fluorimetric chemosensors with high sensitivity towards Fe 3+ and Cu 2+ in a metal-ligand complex with 1:2 stoichiometry. The photophysical and ion sensing properties of these amino acids confirm their potential as fluorescent probes suitable for incorporation into peptidic frameworks with chemosensory ability.

Catalysts for ultrahigh current density oxygen cathodes for space fuel cell applications

NASA Technical Reports Server (NTRS)

Tryk, Donald A.; Yeager, E.

1992-01-01

The objective was to identify promising electrocatalyst/support systems for oxygen cathodes capable of operating at ultrahigh current densities in alkaline fuel cells. Such cells will require operation at relatively high temperatures and O2 pressures. A number of materials were prepared, including Pb-Ru and Pb-Ir pyrochlores, RuO2 and Pt-doped RuO2, lithiated NiO and La-Ni perovskites. Several of these materials were prepared using techniques that had not been previously used to prepare them. Particularly interesting was the use of the alkaline solution technique to prepare Pt-doped and Pb-Ru pyrochlores in high area form. Also interesting was the use of the fusion (melt) method for preparing the Pb-Ru pyrochlore. Several of the materials were also deposited with platinum. Well-crystallized Pb2Ru2O(7-y) was used to fabricate very high performance O2 cathodes with good stability in room temperature KOH. This material was also found to be stable over a useful potential range at approx. 140 C in concentrated KOH. For some of the samples, fabrication of the gas-fed electrodes could not be fully optimized during this project period. Future work may be directed at this problem. Pyrochlores that were not well-crystallized were found to be unstable in alkaline solution. Very good O2 reduction performance and stability were observed with Pb2RuO(7-y) in a carbon-based gas-fed electrode with an anion-conducting membrane placed on the electrolyte side of the electrode. The performance came within a factor of about two of that observed without carbon. High area platinum and gold supported on several conductive metal oxide supports were examined. Only small improvements in O2 reduction performance at room temperature were observed for Pb2Ru2O(7-y) as a support because of the high intrinsic activity of the pyrochlore. In contrast, a large improvement was observed for Li-doped NiO as a support for Pt. Very poor performance was observed for Au deposited on Li-NiO at approx. 150 C. Nearly reversible behavior was observed for the O2/OH(-) couple for Li-doped NiO at approx. 200 C. The temperature dependence for the O2 reduction was examined.

Methane production potential of leachate generated from Korean food waste recycling facilities: a lab-scale study.

PubMed

Lee, Dae Hee; Behera, Shishir Kumar; Kim, Ji Won; Park, Hung-Suck

2009-02-01

This paper examines the applicability of food waste leachate (FWL) in bioreactor landfills or anaerobic digesters to produce methane as a sustainable solution to the persisting leachate management problem in Korea. Taking into account the climatic conditions in Korea and FWL characteristics, the effect of key parameters, viz., temperature, alkalinity and salinity on methane yield was investigated. The monthly average moisture content and the ratio of volatile solids to total solids of the FWL were found to be 84% and 91%, respectively. The biochemical methane potential experiment under standard digestion conditions showed the methane yield of FWL to be 358 and 478 ml/g VS after 10 and 28 days of digestion, respectively, with an average methane content of 70%. Elemental analysis showed the chemical composition of FWL to be C(13.02)H(23.01)O(5.93)N(1). The highest methane yield of 403 ml/g VS was obtained at 35 degrees C due to the adaptation of seed microorganisms to mesophilic atmosphere, while methane yields at 25, 45 and 55 degrees C were 370, 351 and 275 ml/g VS, respectively, at the end of 20 days. Addition of alkalinity had a favorable effect on the methane yield. Dilution of FWL with salinity of 2g/l NaCl resulted in 561 ml CH(4)/g VS at the end of 30 days. Considering its high biodegradability (82.6%) and methane production potential, anaerobic digestion of FWL in bioreactor landfills or anaerobic digesters with a preferred control of alkalinity and salinity can be considered as a sustainable solution to the present emergent problem.

Corrosion of Cu-xZn alloys in slightly alkaline chloride solutions studied by stripping voltammetry and microanalysis.

PubMed

Milosev, I; Minović, A

2001-01-01

The mechanism of corrosion of Cu-xZn alloys (x = 10-40 wt %) in slightly alkaline chloride solutions was investigated by analysing solid reaction products by energy dispersive X-ray analysis (EDS) and dissolved reaction products by differential anodic pulse stripping (DAPS) voltammetry. The corrosion process was studied under open circuit and under potentiostatic conditions at selected potentials. Pure metals were studied comparatively so that an interacting effect of particular metal components in the alloy could be determined. All four Cu-xZn alloys show an improved behaviour compared to pure metals. Under open-circuit condition both components dissolve simultaneously in the solution. With increasing immersion time the preferential, dissolution of zinc in the solution becomes pronounced. It is the highest for Cu-10Zn and the lowest for Cu-30Zn alloy. Under potentiostatic control the dissolution mechanism depends on the electrode potential and changes from exclusive dissolution of zinc to simultaneous dissolution of both components with preferential dissolution of zinc. The latter decreases, as the electrode potential becomes more positive.

Structural modifications of the salivary conditioning film upon exposure to sodium bicarbonate: implications for oral lubrication and mouthfeel.

PubMed

Ash, A; Wilde, P J; Bradshaw, D J; King, S P; Pratten, J R

2016-03-14

The salivary conditioning film (SCF) that forms on all surfaces in the mouth plays a key role in lubricating the oral cavity. As this film acts as an interface between tongue, enamel and oral mucosa, it is likely that any perturbations to its structure could potentially lead to a change in mouthfeel perception. This is often experienced after exposure to oral hygiene products. For example, consumers that use dentifrice that contain a high concentration of sodium bicarbonate (SB) often report a clean mouth feel after use; an attribute that is clearly desirable for oral hygiene products. However, the mechanisms by which SB interacts with the SCF to alter lubrication in the mouth is unknown. Therefore, saliva and the SCF was exposed to high ionic strength and alkaline solutions to elucidate whether the interactions observed were a direct result of SB, its high alkalinity or its ionic strength. Characteristics including bulk viscosity of saliva and the viscoelasticity of the interfacial salivary films that form at both the air/saliva and hydroxyapatite/saliva interfaces were tested. It was hypothesised that SB interacts with the SCF in two ways. Firstly, the ionic strength of SB shields electrostatic charges of salivary proteins, thus preventing protein crosslinking within the film and secondly; the alkaline pH (≈8.3) of SB reduces the gel-like structure of mucins present in the pellicle by disrupting disulphide bridging of the mucins via the ionization of their cysteine's thiol group, which has an isoelectric point of ≈8.3.

Enhancement of lateral flow immunoassay by alkaline phosphatase: a simple and highly sensitive test for potato virus X.

PubMed

Panferov, Vasily G; Safenkova, Irina V; Varitsev, Yury A; Zherdev, Anatoly V; Dzantiev, Boris B

2017-12-06

Alkaline phosphatase (ALP) was used as an amplification tool in lateral flow immunoassay (LFIA). Potato virus Х (PVX) was selected as a target analyte because of its high economic importance. Two conjugates of gold nanoparticles were applied, one with mouse monoclonal antibody against PVX and one with ALP-labeled antibody against mouse IgG. They were immobilized to two fiberglass membranes on the test strip for use in LFIA. After exposure to the sample, a substrate for ALP (5-bromo-4-chloro-3-indolyl phosphate/nitro blue tetrazolium) was dropped on the test strip. The insoluble dark-violet diformazan produced by ALP precipitated on the membrane and significantly increased the color intensity of the control and test zones. The limit of detection (0.3 ng mL -1 ) was 27 times lower than that of conventional LFIA for both buffer and potato leaf extracts. The ALP-enhanced LFIA does not require additional preparation procedures or washing steps and may be used by nontrained persons in resource-limited conditions. The new method of enhancement is highly promising and may lead to application for routine LFIA in different areas. Graphical abstract Two gold nanoparticles (GNP) conjugates were used - the first with monoclonal antibodies (mAb) (GNP-mAb); the second - alkaline phosphatase-labeled antibody against mAb (GNP-anti-mAb-ALP). The immuno complexes are captured by the polyclonal antibodies (pAb) in the test zone. Addition of the substrate solution (BCIP/NBT) results in the accumulation of the insoluble colored product and in a significance increase in color intensity.

Structure-function relationship of reduced cytochrome c probed by complete solution structure determination in 30% acetonitrile/water solution.

PubMed

Sivakolundu, Sivashankar G; Mabrouk, Patricia Ann

2003-05-01

The complete solution structure of ferrocytochrome c in 30% acetonitrile/70% water has been determined using high-field 1D and 2D (1)H NMR methods and deposited in the Protein Data Bank with codes 1LC1 and 1LC2. This is the first time a complete solution protein structure has been determined for a protein in nonaqueous media. Ferrocyt c retains a native protein secondary structure (five alpha-helices and two omega loops) in 30% acetonitrile. H18 and M80 residues are the axial heme ligands, as in aqueous solution. Residues believed to be axial heme ligands in the alkaline-like conformers of ferricyt c, specifically H33 and K72, are positioned close to the heme iron. The orientations of both heme propionates are markedly different in 30% acetonitrile/70% water. Comparative structural analysis of reduced cyt c in 30% acetonitrile/70% water solution with cyt c in different environments has given new insight into the cyt c folding mechanism, the electron transfer pathway, and cell apoptosis.

STABILIZATION OF SPIDER CRAB NERVE MEMBRANES BY ALKALINE EARTHS, AS MANIFESTED IN RESTING POTENTIAL MEASUREMENTS

PubMed Central

Guttman, Rita

1940-01-01

1. The alkaline earths, Ba, Sr, Ca, and Mg, in isotonic solutions of their chlorides, have, in general, no effect upon the resting potential of non-medullated spider crab nerve. 2. Ba, Sr, and Ca can, however, prevent the depressing action of K upon the resting potential. The order of effectiveness of these ions in this regard is the following: Ba > Sr > Ca. 3. Ba, Sr, Ca, and Mg oppose the depressing action of veratrine sulfate upon the resting potential. The order of effectiveness is Ba > Sr > Ca > Mg. The relation between drop in potential caused by veratrine sulfate and the logarithm of the veratrine sulfate concentration is a linear one. 4. The action of various other organic ions and molecules which depress the resting potential: saponin, amyl urethane, chloral hydrate, and Na salicylate is neutralized by Ba. 5. Hypertonic sea water solutions do not affect the resting potential. Also, preliminary experiments indicate that the nerves do not shrink in hypertonic solutions although they swell in hypotonic sea water. 6. The alkaline earths depress excitability reversibly. The various organic agents which depress the resting potential also depress excitability, in most cases, reversibly, but the concentrations necessary to depress excitability are much smaller than those necessary to depress the resting potential. 7. The relation of these findings to theories put forward as possible explanations of resting potential phenomena is considered. PMID:19873160

Activity–stability relationship in the surface electrochemistry of the oxygen evolution reaction

DOE PAGES

Chang, Seo Hyoung; Connell, Justin G.; Danilovic, Nemanja; ...

2014-07-25

Understanding the functional links between the stability and reactivity of oxide materials during the oxygen evolution reaction (OER) is one key to enabling a vibrant hydrogen economy capable of competing with fossil fuel-based technologies. In this work, by focusing on the surface chemistry of monometallic Ru oxide in acidic and alkaline environments, we found that the kinetics of the OER are almost entirely controlled by the stability of the Ru surface atoms. The same activity–stability relationship was found for more complex, polycrystalline and single-crystalline SrRuO 3 thin films in alkaline solutions. We propose that the electrochemical transformation of either watermore » (acidic solutions) or hydroxyl ions (alkaline solutions) to di-oxygen molecules takes place at defect sites that are inherently present on every electrode surface. During the OER, surface defects are also created by the corrosion of the Ru ions. The dissolution is triggered by the potential-dependent change in the valence state ( n) of Ru: from stable but inactive Ru 4+ to unstable but active Ru n>4+. We conclude that if the oxide is stable then it is completely inactive for the OER. As a result, a practical consequence is that the best materials for the OER should balance stability and activity in such a way that the dissolution rate of the oxide is neither too fast nor too slow.« less

Effect of polycarboxylate ether comb-type polymer on viscosity and interfacial properties of kaolinite clay suspensions.

PubMed

Zhang, Ling; Lu, Qingye; Xu, Zhenghe; Liu, Qingxia; Zeng, Hongbo

2012-07-15

The interactions between kaolinite clay particles and a comb-type polymer (polycarboxylate ether or PCE), so-called PCE super-plasticizer, were investigated through viscosity and surface forces measurements by a rheometer and a Surface Forces Apparatus (SFA). The addition of PCE shows a strong impact on the viscosity of concentrated kaolinite suspensions in alkaline solutions (pH=8.3) but a weak effect under acidic conditions (pH=3.4). In acidic solutions, the high viscosity measured is attributed to the strong electrostatic interaction between negatively charged basal planes and positively charged edge surfaces of clay particles. Under the alkaline condition, the suspension viscosity was found to first increase significantly and then decrease with increasing PCE dosages. The results from surface forces measurement show that PCE molecules at low dosages can bridge the kaolinite particles in the concentrated suspensions via hydrogen bonding, leading to the formation of a kaolinite-PCE "network" and hence an increased suspension viscosity. At high PCE dosages, clay particles are fully covered by PCE molecules, leading to a more dispersed kaolinite suspensions and hence lower suspension viscosity due to steric repulsion between the adsorbed PCE molecules. The insights derived from measuring viscosity and interfacial properties of kaolinite suspensions containing varying amount of comb-type super-plasticizer PCE at different pH provide the foundation for many engineering applications and optimizing industrial processes. Copyright © 2012 Elsevier Inc. All rights reserved.

Highly active carbon supported ternary PdSnPtx (x=0.1-0.7) catalysts for ethanol electro-oxidation in alkaline and acid media.

PubMed

Wang, Xiaoguang; Zhu, Fuchun; He, Yongwei; Wang, Mei; Zhang, Zhonghua; Ma, Zizai; Li, Ruixue

2016-04-15

A series of trimetallic PdSnPtx (x=0.1-0.7)/C catalysts with varied Pt content have been synthesized by co-reduction method using NaBH4 as a reducing agent. These catalysts were characterized using X-ray diffraction (XRD), transmission electron microscopy (TEM), high resolution transmission electron microscopy (HRTEM), energy dispersive X-ray spectroscopy (EDX), X-ray photoelectron spectroscopy (XPS), cyclic voltammetry (CV) and chronoamperometry (CA). The electrochemical results show that, after adding a minor amount of Pt dopant, the resultant PdSnPtx/C demonstrated more superior catalytic performance toward ethanol oxidation as compared with that of mono-/bi-metallic Pd/C or PdSn/C in alkaline solution and the PdSnPt0.2/C with optimal molar ratio reached the best. In acid solution, the PdSnPt0.2/C also depicted a superior catalytic activity relative to the commercial Pt/C catalyst. The possible enhanced synergistic effect between Pd, Sn/Sn(O) and Pt in an alloyed state should be responsible for the as-revealed superior ethanol electro-oxidation performance based upon the beneficial electronic effect and bi-functional mechanism. It implies the trimetallic PdSnPt0.2/C with a low Pt content has a promising prospect as anodic electrocatalyst in fields of alkali- and acid-type direct ethanol fuel cells. Copyright © 2016 Elsevier Inc. All rights reserved.

Electrocatalysis and electroanalysis of nickel, its oxides, hydroxides and oxyhydroxides toward small molecules.

PubMed

Miao, Yuqing; Ouyang, Lei; Zhou, Shilin; Xu, Lina; Yang, Zhuoyuan; Xiao, Mingshu; Ouyang, Ruizhuo

2014-03-15

The electrocatalysis toward small molecules, especially small organic compounds, is of importance in a variety of areas. Nickel based materials such as nickel, its oxides, hydroxides as well as oxyhydroxides exhibit excellent electrocatalysis performances toward many small molecules, which are widely used for fuel cells, energy storage, organic synthesis, wastewater treatment, and electrochemical sensors for pharmaceutical, medical, food or environmental analysis. Their electrocatalytic mechanisms are proposed from three aspects such as Ni(OH)2/NiOOH mediated electrolysis, direct electrocatalysis of Ni(OH)2 or NiOOH. Under exposure to air or aqueous solution, two distinct layers form on the Ni surface with a Ni hydroxide layer at the air-oxide interface and an oxide layer between the metal substrate and the outer hydroxide layer. The transformation from nickel or its oxides to hydroxides or oxyhydroxides could be further speeded up in the strong alkaline solution under the cyclic scanning at relatively high positive potential. The redox transition between Ni(OH)2 and NiOOH is also contributed to the electrocatalytic oxidation of Ni and its oxides toward small molecules in alkaline media. In addition, nickel based materials or nanomaterials, their preparations and applications are also overviewed here. © 2013 Elsevier B.V. All rights reserved.

Experimental Study on Full-Scale Beams Made by Reinforced Alkali Activated Concrete Undergoing Flexure.

PubMed

Monfardini, Linda; Minelli, Fausto

2016-08-30

Alkali Activated Concrete (AAC) is an alternative kind of concrete that uses fly ash as a total replacement of Portland cement. Fly ash combined with alkaline solution and cured at high temperature reacts to form a binder. Four point bending tests on two full scale beams made with AAC are described in this paper. Companion small material specimens were also casted with the aim of properly characterizing this new tailored material. The beam's length was 5000 mm and the cross section was 200 mm × 300 mm. The AAC consisted of fly ash, water, sand 0-4 mm and coarse aggregate 6-10 mm; and the alkaline solution consisted of sodium hydroxide mixed with sodium silicate. No cement was utilized. The maximum aggregate size was 10 mm; fly ash was type F, containing a maximum calcium content of 2%. After a rest period of two days, the beam was cured at 60 °C for 24 h. Data collected and critically discussed included beam deflection, crack patterns, compressive and flexural strength and elastic modulus. Results show how AAC behavior is comparable with Ordinary Portland Cement (OPC) based materials. Nonlinear numerical analyses are finally reported, promoting a better understanding of the structural response.

Study concerning the recovery of zinc and manganese from spent batteries by hydrometallurgical processes.

PubMed

Buzatu, Traian; Popescu, Gabriela; Birloaga, Ionela; Săceanu, Simona

2013-03-01

Used batteries contain numerous metals in high concentrations and if not disposed of with proper care, they can negatively affect our environment. These metals represent 83% of all spent batteries and therefore it is important to recover metals such as Zn and Mn, and reuse them for the production of new batteries. The recovery of Zn and Mn from used batteries, in particular from Zn-C and alkaline ones has been researched using hydrometallurgical methods. After comminution and classification of elemental components, the electrode paste resulting from these processes was treated by chemical leaching. Prior to the leaching process the electrode paste has been subjected to two washing steps, in order to remove the potassium, which is an inconvenient element in this type of processes. To simultaneously extract Zn and Mn from this paste, the leaching method in alkaline medium (NaOH solution) and acid medium (sulphuric acid solution) was used. Also, to determine the efficiency of extraction of Zn and Mn from used batteries, the following variables were studied: reagents concentration, S/L ratio, temperature, time. The best results for extraction yield of Zn and Mn were obtained under acid leaching conditions (2M H2SO4, 1h, 80°C). Copyright © 2012 Elsevier Ltd. All rights reserved.

Experimental Study on Full-Scale Beams Made by Reinforced Alkali Activated Concrete Undergoing Flexure

PubMed Central

Monfardini, Linda; Minelli, Fausto

2016-01-01

Alkali Activated Concrete (AAC) is an alternative kind of concrete that uses fly ash as a total replacement of Portland cement. Fly ash combined with alkaline solution and cured at high temperature reacts to form a binder. Four point bending tests on two full scale beams made with AAC are described in this paper. Companion small material specimens were also casted with the aim of properly characterizing this new tailored material. The beam’s length was 5000 mm and the cross section was 200 mm × 300 mm. The AAC consisted of fly ash, water, sand 0–4 mm and coarse aggregate 6–10 mm; and the alkaline solution consisted of sodium hydroxide mixed with sodium silicate. No cement was utilized. The maximum aggregate size was 10 mm; fly ash was type F, containing a maximum calcium content of 2%. After a rest period of two days, the beam was cured at 60 °C for 24 h. Data collected and critically discussed included beam deflection, crack patterns, compressive and flexural strength and elastic modulus. Results show how AAC behavior is comparable with Ordinary Portland Cement (OPC) based materials. Nonlinear numerical analyses are finally reported, promoting a better understanding of the structural response. PMID:28773861

A novel approach for arsenic adsorbents regeneration using MgO.

PubMed

Tresintsi, Sofia; Simeonidis, Konstantinos; Katsikini, Maria; Paloura, Eleni C; Bantsis, Georgios; Mitrakas, Manassis

2014-01-30

An integrated procedure for the regeneration of iron oxy-hydroxide arsenic adsorbents by granulated MgO is proposed in this study. A continuous recirculation configuration, with a NaOH solution flowing sequentially through the saturated adsorbent (leaching step) and the MgO (adsorption step) column beds, was optimized by utilizing the high arsenic adsorption efficiency of MgO at strong alkaline environments. Experimental results indicated that the total amount of leached arsenic was captured by MgO whereas the regenerated iron oxy-hydroxide recovered around 80% of its removal capacity upon reuse. The improved adsorption capacity of MgO for As(V), which is maximized at pH 10, is explained by the intermediate hydration to Mg(OH)2 and the following As(V) oxy-anions adsorption on its surface through the formation of monodentate inner sphere complexes, as it is deduced from the AsK-edge X-ray absorption fine structure (EXAFS) analysis. In addition to the economical-benefits, corresponding tests proved that the solid wastes of this process, namely spent MgO/Mg(OH)2, can be environmentally safely disposed as stable additives in cement products, while the alkaline solution is completely detoxified and can be recycled to the regeneration task. Copyright © 2013 Elsevier B.V. All rights reserved.

Mercury(II) Complex Formation With Glutathione in Alkaline Aqueous Solution

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

Mah, V.; Jalilehvand, F.

2009-05-19

The structure and speciation of the complexes formed between mercury(II) ions and glutathione (GSH = L-glutamyl-L-cysteinyl-glycine) have been studied for a series of alkaline aqueous solutions (C{sub Hg{sup 2+}} {approx} 18 mmol dm{sup -3} and C{sub GSH} = 40-200 mmol dm{sup -3} at pH {approx} 10.5) by means of extended X-ray absorption fine structure (EXAFS) and {sup 199}Hg NMR spectroscopy at ambient temperature. The dominant complexes are [Hg(GS){sub 2}]{sup 4-} and [Hg(GS){sub 3}]{sup 7-}, with mean Hg-S bond distances of 2.32(1) and 2.42(2) {angstrom} observed in digonal and trigonal Hg-S coordination, respectively. The proportions of the Hg{sup 2+}-glutathione complexes weremore » evaluated by fitting linear combinations of model EXAFS oscillations representing each species to the experimental EXAFS spectra. The [Hg(GS){sub 4}]{sup 10-} complex, with four sulfur atoms coordinated at a mean Hg-S bond distance of 2.52(2) {angstrom}, is present in minor amounts (<30%) in solutions containing a large excess of glutathione (C{sub GSH} {ge} 160 mmol dm{sup -3}). Comparable alkaline mercury(II) cysteine (H{sub 2}Cys) solutions were also investigated and a reduced tendency to form higher complexes was observed, because the deprotonated amino group of Cys{sup 2-} allows the stable [Hg(S,N-Cys){sub 2}]{sup 2-} chelate to form. The effect of temperature on the distribution of the Hg{sup 2+}-glutathione complexes was studied by comparing the EXAFS spectra at ambient temperature and at 25 K of a series of glycerol/water (33/67, v/v) frozen glasses with and C{sub Hg{sup 2+}} {approx} 7 mmol dm{sup -3} and C{sub GSH} = 16-81 mmol dm{sup -3}. Complexes with high Hg-S coordination numbers, [Hg(GS){sub 3}]{sup 7-} and [Hg(GS){sub 4}]{sup 10-}, became strongly favored when just a moderate excess of glutathione (C{sub GSH} {ge} 28 mmol dm{sup -3}) was used in the glassy samples, as expected for a stepwise exothermic bond formation. Addition of glycerol had no effect on the Hg(II)-glutathione speciation, as shown by the similarity of the EXAFS spectra obtained at room temperature for two parallel series of Hg(II)-glutathione solutions with C{sub Hg{sup 2+}} {approx} 7 mmol dm{sup -3}, with and without 33% glycerol. Also, the {sup 199}Hg NMR chemical shifts of a series of {approx} 18 mmol dm{sup -3} mercury(II) glutathione solutions with 33% glycerol were not significantly different from those of the corresponding series in aqueous solution.« less

Simultaneous extraction of polycyclic aromatic hydrocarbons through the complete dissolution of solid biological samples in sodium hydroxide/urea/thiourea aqueous solution.

PubMed

Mohammad, Sedigheh Ale; Ghanemi, Kamal; Larki, Arash

2016-12-09

In order to precisely and simultaneously extract polycyclic aromatic hydrocarbons (PAHs) for measurement using a high performance liquid chromatography-fluorescence detector (HPLC-FL), a novel sample preparation method was developed. This method is based on the complete and fast dissolution of biological samples in a new non-alcoholic alkaline medium. A solution composed of NaOH/urea/thiourea at an optimized ratio was used for complete dissolution of approximately 0.25g dried fish samples within 20min. The proposed method was conducted at 10°C and under atmospheric pressure to obtain a stable and highly homogeneous solution, without the need for microwaves or any other apparatus. This process operates at considerably lower temperature than conventional methods and provides an opportunity to simultaneously extract the target analytes from their matrices by adding the extracting solvent in the initial steps of the dissolution; this process greatly reduced the time of analysis and the loss of analytes via vaporization. Several key parameters were identified and their effects on precision and extraction recoveries were investigated. Linearity over a calibration range of 1.0-100 and 2.5-100ngg -1 was achieved, with high coefficients of determination (r 2 ) ranging between 0.9987 and 0.9998. Based on relative standard deviations (n=5), the intra-day and inter-day precisions of the spiked PAHs were found to be better than 3.1% and 3.2%, respectively, at a concentration level of 25ngg -1 . The recoveries of PAH from spiked marine fish tissues and shrimp samples were in the range of 90.6%-100.4%. The spiked samples were also treated with the alcoholic alkaline and Soxhlet extraction methods in order to provide a comparison. Copyright © 2016 Elsevier B.V. All rights reserved.

Influences of pH and CO2 on the formation of Metasilicate mineral water in Changbai Mountain, Northeast China

NASA Astrophysics Data System (ADS)

Yan, Baizhong; Xiao, Changlai; Liang, Xiujuan; Wu, Shili

2017-07-01

Mineral dissolution reactions actively participate in controlling the composition of mineral water. In this study, water soluble, acidic-alkaline and carbonated solution experiments were designed, and mineral reaction mechanisms were researched using chemical kinetics and the minimum free-energy method. The results showed that the release of metasilicate was controlled by pH, CO2, and rock characteristics. In the water soluble experiment, the release process of metasilicate in powdered rocks reached equilibrium after 40 days, while metasilicate in solid rocks took 170 days. The release process of metasilicate in solid rocks satisfied an asymptotic model, while in powdered rocks it accorded with the Stanford reaction kinetic model. In the acidic-alkaline experiment, metasilicate was released earlier under acidic conditions (2.46 < pH < 7) than under alkaline conditions (7 < pH < 10.61). The release process of metasilicate under acidic conditions reached equilibrium in 40 days, compared with 60 days for alkaline conditions. The addition of CO2 to the water solution was beneficial to the formation of metasilicate. Under neutral pH conditions, the reaction barely occurred. Under alkaline conditions, metasilicate was produced by the hydrolysis of metasilicate minerals. Under acidic and additional CO2 conditions, metasilicate formation was mainly via the reaction of H+, CO2, and metasilicate minerals. From these results, we concluded that the metasilicate mineral water from the Changbai Mountains, Jingyu County, is generated by a combination of the hydrolysis of metasilicate minerals and the reaction of H+, CO2, and metasilicate minerals. These results can contribute to a better development and protection of the mineral water resources in the Changbai Mountains.