WorldWideScience

Sample records for aqueous chemical environment

  1. Plasmon-driven sequential chemical reactions in an aqueous environment.

    Science.gov (United States)

    Zhang, Xin; Wang, Peijie; Zhang, Zhenglong; Fang, Yurui; Sun, Mengtao

    2014-06-24

    Plasmon-driven sequential chemical reactions were successfully realized in an aqueous environment. In an electrochemical environment, sequential chemical reactions were driven by an applied potential and laser irradiation. Furthermore, the rate of the chemical reaction was controlled via pH, which provides indirect evidence that the hot electrons generated from plasmon decay play an important role in plasmon-driven chemical reactions. In acidic conditions, the hot electrons were captured by the abundant H(+) in the aqueous environment, which prevented the chemical reaction. The developed plasmon-driven chemical reactions in an aqueous environment will significantly expand the applications of plasmon chemistry and may provide a promising avenue for green chemistry using plasmon catalysis in aqueous environments under irradiation by sunlight.

  2. Optical techniques for nanoscale probing and chemical detection in aqueous environments

    Science.gov (United States)

    Pristinski, Denis

    We present an investigation of charge-dependent physical properties of water-soluble synthetic polymers and polymer-based layered structures, using optical detection methods in a visible range. We apply in situ nanoscale optical techniques to study response of polymer systems to changes in pH, polymer concentration, and concentration and type of counterions. This work describes three optical techniques and custom built instrumental setups for nanoscale polymer characterization in aqueous environment. Phase-modulated ellipsometry was applied to determine the refraction coefficient and the thickness of a hydrogel-like polymer layer on a substrate. The present study describes the sensitivity of the phase modulated ellipsometry to errors of measurement and determines conditions for decoupling film thickness and refraction index. It is shown that, for a certain range of film thickness, both the thickness and the refractive index can be determined from a single measurement with high precision. This optimal range of the film thickness is calculated for organic thin films, and the analysis is tested on crosslinked poly(methacrylic acid) polymer films in air and in water. Fluorescent correlation spectroscopy was used to investigate diffusion of a synthetic polyelectrolyte in aqueous solutions. Translational diffusion of Alexa-labeled poly(methacrylic acid) chains was studied in very dilute, 10-4 mg/ml, solutions as a function of polymer charge density and counterion concentration. The results illustrate the utility of the technique for studying hydrodynamic sizes of polyelectrolyte coils in response to variation in solution pH or concentration of salt and polyelectrolytes. We apply surface-enhanced Raman scattering (SERS) for studying of enhancement capabilities of individual silver nanoparticles attached to glass and silicon substrates. Nanoparticles were electrostatically bound to a self-assembled polyallylamine hydrochloride (PAH) monolayer, which was deposited on

  3. Effect of 20 % EDTA Aqueous Solution on Defective Tubes (Alloy600) in High Temperature Chemical Cleaning Environments

    Energy Technology Data Exchange (ETDEWEB)

    Kwon, Hyuk Chul [KHNP-CRI, Daejeon (Korea, Republic of)

    2016-04-15

    The transport and deposition of corrosion products in pressurized water nuclear reactor (PWR) steam generators have led to corrosion (SCC, denting etc.) problems. Lancing, mechanical cleaning and chemical cleaning have been used to reduce these problems. The methods of lancing and mechanical cleaning have limitations in removing corrosion products due to the structure of steam generator tubes. But high temperature chemical cleaning (HTCC) with EDTA is the most effective method to remove corrosion products regardless of the structure. However, EDTA in chemical cleaning aqueous solution and chemical cleaning environments affects the integrity of materials used in steam generators. The nuclear power plants have to perform the pre-test (also called as qualification test (QT)) that confirms the effect on the integrity of materials after HTCC. This is one of the series studies that assess the effect, and this study determines the effects of 20 % EDTA aqueous solution on defective tubes in high temperature chemical cleaning environments. The depth and magnitude of defects in steam generator (SG) tubes were measured by eddy current test (ECT) signals. Surface analysis and magnitude of defects were performed by using SEM/EDS. Corrosion rate was assessed by weight loss of specimens. The ECT signals (potential and depth %) of defective tubes increased marginally. But the lengths of defects, oxides on the surface and weights of specimens did not change. The average corrosion rate of standard corrosion specimens was negligible. But the surfaces on specimens showed traces of etching. The depth of etching showed a range on the nanometer. After comprehensive evaluation of all the results, it is concluded that 20 % EDTA aqueous solution in high temperature chemical cleaning environments does not have a negative effect on defective tubes.

  4. MIPs in Aqueous Environments.

    Science.gov (United States)

    Wan, Ying-chun; Ma, Hui-ting; Lu, Bin

    2015-01-01

    When organic solvent-compatible molecularly imprinted polymers (MIPs) are used in aqueous environment, how to reduce nonspecific binding is a major challenge. By modifying the binding solvents and introducing appropriate washing and elution steps, even relatively hydrophobic MIPs can gain optimal rebinding selectivity in aqueous conditions. Furthermore, water-compatible MIPs that can be used to treat aqueous samples directly have been prepared. The use of hydrophilic co-monomers, the controlled surface modification through controlled radical polymerization, and the new interfacial molecular imprinting methods are different strategies to prepare water-compatible MIPs. By combining MIPs with other techniques, both organic solvent-compatible and water-compatible MIPs can display better functional performances in aqueous conditions. Intensive studies on MIPs in aqueous conditions can provide new MIPs with much-improved compatibilities that will lead to more interesting applications in biomedicine and biotechnology.

  5. Influence of pyrolysis temperature on lead immobilization by chemically modified coconut fiber-derived biochars in aqueous environments.

    Science.gov (United States)

    Wu, Weidong; Li, Jianhong; Niazi, Nabeel Khan; Müller, Karin; Chu, Yingchao; Zhang, Lingling; Yuan, Guodong; Lu, Kouping; Song, Zhaoliang; Wang, Hailong

    2016-11-01

    Biochar has received widespread attention as an eco-friendly and efficient material for immobilization of toxic heavy metals in aqueous environments. In the present study, three types of coconut fiber-derived biochars were obtained by pyrolyzing at three temperatures, i.e., 300, 500, and 700 °C. In addition, nine types of biochars were prepared by chemical modification with ammonia, hydrogen peroxide, and nitric acid, respectively, which were used to investigate changes in physico-chemical properties by inter alia, Fourier transformation infrared spectrophotometry (FTIR), scanning electron microscope (SEM), and BET specific surface area analysis. Batch sorption experiments were carried out to determine the sorption capacity of the biochars for lead (Pb) in aqueous solutions. Results showed that the cation exchange capacity of biochar pyrolyzed at 300 °C and modified with nitric acid increased threefold compared to the control. Loosely corrugated carbon surface and uneven carbon surface of the biochar pyrolyzed at 300 °C were produced during ammonia and nitric acid modifications. Removal rate of Pb by the coconut biochar pyrolyzed at 300 °C and modified with ammonia was increased from 71.8 to 99.6 % compared to the untreated biochar in aqueous solutions containing 100 mg L(-1) Pb. However, chemical modification did not enhance adsorption of Pb of the biochars pyrolyzed at higher temperatures (e.g., 500 or 700 °C), indicating that resistance of biochars to chemical treatment increased with pyrolysis temperature.

  6. Chemical reactions at aqueous interfaces

    Science.gov (United States)

    Vecitis, Chad David

    2009-12-01

    Interfaces or phase boundaries are a unique chemical environment relative to individual gas, liquid, or solid phases. Interfacial reaction mechanisms and kinetics are often at variance with homogeneous chemistry due to mass transfer, molecular orientation, and catalytic effects. Aqueous interfaces are a common subject of environmental science and engineering research, and three environmentally relevant aqueous interfaces are investigated in this thesis: 1) fluorochemical sonochemistry (bubble-water), 2) aqueous aerosol ozonation (gas-water droplet), and 3) electrolytic hydrogen production and simultaneous organic oxidation (water-metal/semiconductor). Direct interfacial analysis under environmentally relevant conditions is difficult, since most surface-specific techniques require relatively `extreme' conditions. Thus, the experimental investigations here focus on the development of chemical reactors and analytical techniques for the completion of time/concentration-dependent measurements of reactants and their products. Kinetic modeling, estimations, and/or correlations were used to extract information on interfacially relevant processes. We found that interfacial chemistry was determined to be the rate-limiting step to a subsequent series of relatively fast homogeneous reactions, for example: 1) Pyrolytic cleavage of the ionic headgroup of perfluorooctanesulfonate (PFOS) and perfluorooctanoate (PFOA) adsorbed to cavitating bubble-water interfaces during sonolysis was the rate-determining step in transformation to their inorganic constituents carbon monoxide, carbon dioxide, and fluoride; 2) ozone oxidation of aqueous iodide to hypoiodous acid at the aerosol-gas interface is the rate-determining step in the oxidation of bromide and chloride to dihalogens; 3) Electrolytic oxidation of anodic titanol surface groups is rate-limiting for the overall oxidation of organics by the dichloride radical. We also found chemistry unique to the interface, for example: 1

  7. An investigation on changes in chemical properties of pure ethylene-propylene-diene rubber in aqueous acidic environments

    DEFF Research Database (Denmark)

    Mitra, S.; Ghanbari-Siahkali, Afshin; Kingshott, Peter

    2006-01-01

    The influence of two aqueous acidic environments on two types of pure ethylene-propylene-diene (EPDM) rubber (i.e., elastomer) thin films is studied. Attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR) results revealed the formation of several oxygenated species...... formation on the surface of EPDM rubbers compared to 20% H2SO4 under identical conditions. Complex formation on the surface of EPDM samples exposed to 20% Cr(VI)/H2SO4 through reactions of carboxylic groups (generated due to EPDM degradation) with Cr(III) (formed due to reduction of Cr(VI)) was also evident...

  8. Sampling of Organic Solutes in Aqueous and Heterogeneous Environments Using Oscillating Excess Chemical Potentials in Grand Canonical-like Monte Carlo-Molecular Dynamics Simulations.

    Science.gov (United States)

    Lakkaraju, Sirish Kaushik; Raman, E Prabhu; Yu, Wenbo; MacKerell, Alexander D

    2014-06-10

    Solute sampling of explicit bulk-phase aqueous environments in grand canonical (GC) ensemble simulations suffer from poor convergence due to low insertion probabilities of the solutes. To address this, we developed an iterative procedure involving Grand Canonical-like Monte Carlo (GCMC) and molecular dynamics (MD) simulations. Each iteration involves GCMC of both the solutes and water followed by MD, with the excess chemical potential (μex) of both the solute and the water oscillated to attain their target concentrations in the simulation system. By periodically varying the μex of the water and solutes over the GCMC-MD iterations, solute exchange probabilities and the spatial distributions of the solutes improved. The utility of the oscillating-μex GCMC-MD method is indicated by its ability to approximate the hydration free energy (HFE) of the individual solutes in aqueous solution as well as in dilute aqueous mixtures of multiple solutes. For seven organic solutes: benzene, propane, acetaldehyde, methanol, formamide, acetate, and methylammonium, the average μex of the solutes and the water converged close to their respective HFEs in both 1 M standard state and dilute aqueous mixture systems. The oscillating-μex GCMC methodology is also able to drive solute sampling in proteins in aqueous environments as shown using the occluded binding pocket of the T4 lysozyme L99A mutant as a model system. The approach was shown to satisfactorily reproduce the free energy of binding of benzene as well as sample the functional group requirements of the occluded pocket consistent with the crystal structures of known ligands bound to the L99A mutant as well as their relative binding affinities.

  9. Free radicals in the aqueous environment

    Energy Technology Data Exchange (ETDEWEB)

    Wood, A.; Laurence, G. [Adelaide Univ., SA (Australia)

    1996-12-31

    Full text: The chemistry of the degradation of organic herbicides and fungicides in natural systems is important in determining operationally important parameters such as withholding times before planting or consumption. Disappearance rates in the field are frequently many time larger than expected from reactions such as hydrolysis arid photochemical- and radical-initiated reactions are frequently cited as causes of the degradation reactions. Reactions of OH and O{sub 2}{sup -} radicals and secondary radicals derived from these are increasingly postulated as being important in many aqueous environmental reactions. Free radical reactions may contribute to the degradation of organic pesticides and are directly implicated in the use of radical generating systems such as Fenton`s Reagent or hydrogen peroxide in the removal of chlorinated organic chemicals from drinking water. Natural sources of these radicals in aqueous systems are predominantly photochemical reactions or reactions initiated by transition metal ions. Hydrogen peroxide is present in many aqueous environments in relatively high concentrations and we are attempting to establish the presence of superoxide radicals in natural systems. The measurement of stationary state concentrations of free radicals as low as 10{sup -} {sup 15} M is a challenge to analytical and free radical chemists. Long term scavenging studies are difficult and generally non-specific. Current ideas will be reviewed and our approach to the measurement of superoxide in natural systems will be outlined.

  10. Ancient aqueous environments at Endeavour crater, Mars

    Science.gov (United States)

    Arvidson, R. E.; Squyres, S. W.; Bell, J.F.; Catalano, J.G.; Clark, B. C.; Crumpler, L.S.; de Souza, P.A.; Fairén, A.G.; Farrand, W. H.; Fox, V.K.; Gellert, Ralf; Ghosh, A.; Golombeck, M.P.; Grotzinger, J.P.; Guinness, E.A.; Herkenhoff, Kenneth E.; Jolliff, B.L.; Knoll, A.H.; Li, R.; McLennan, S.M.; Ming, D. W.; Mittlefehldt, D. W.; Moore, Johnnie N.; Morris, R.V.; Murchie, S.L.; Parker, T.J.; Paulsen, G.; Rice, J.W.; Ruff, S.W.; Smith, M.D.; Wolff, M.J.

    2014-01-01

    Opportunity has investigated in detail rocks on the rim of the Noachian age Endeavour crater, where orbital spectral reflectance signatures indicate the presence of Fe+3-rich smectites. The signatures are associated with fine-grained, layered rocks containing spherules of diagenetic or impact origin. The layered rocks are overlain by breccias, and both units are cut by calcium sulfate veins precipitated from fluids that circulated after the Endeavour impact. Compositional data for fractures in the layered rocks suggest formation of Al-rich smectites by aqueous leaching. Evidence is thus preserved for water-rock interactions before and after the impact, with aqueous environments of slightly acidic to circum-neutral pH that would have been more favorable for prebiotic chemistry and microorganisms than those recorded by younger sulfate-rich rocks at Meridiani Planum.

  11. Ancient aqueous environments at Endeavour crater, Mars.

    Science.gov (United States)

    Arvidson, R E; Squyres, S W; Bell, J F; Catalano, J G; Clark, B C; Crumpler, L S; de Souza, P A; Fairén, A G; Farrand, W H; Fox, V K; Gellert, R; Ghosh, A; Golombek, M P; Grotzinger, J P; Guinness, E A; Herkenhoff, K E; Jolliff, B L; Knoll, A H; Li, R; McLennan, S M; Ming, D W; Mittlefehldt, D W; Moore, J M; Morris, R V; Murchie, S L; Parker, T J; Paulsen, G; Rice, J W; Ruff, S W; Smith, M D; Wolff, M J

    2014-01-24

    Opportunity has investigated in detail rocks on the rim of the Noachian age Endeavour crater, where orbital spectral reflectance signatures indicate the presence of Fe(+3)-rich smectites. The signatures are associated with fine-grained, layered rocks containing spherules of diagenetic or impact origin. The layered rocks are overlain by breccias, and both units are cut by calcium sulfate veins precipitated from fluids that circulated after the Endeavour impact. Compositional data for fractures in the layered rocks suggest formation of Al-rich smectites by aqueous leaching. Evidence is thus preserved for water-rock interactions before and after the impact, with aqueous environments of slightly acidic to circum-neutral pH that would have been more favorable for prebiotic chemistry and microorganisms than those recorded by younger sulfate-rich rocks at Meridiani Planum.

  12. Modeling and 3-D Simulation of Biofilm Dynamics in Aqueous Environment

    Science.gov (United States)

    Wang, Qi

    2011-11-01

    We present a complex fluid model for biofilms growing in an aqueous environment. The modeling approach represents a new paradigm to develop models for biofilm-environment interaction that can be used to systematically incorporate refined chemical and physiological mechanisms. Special solutions of the model are presented and analyzed. 3-D numerical simulations in aqueous environment with emphasis on biofilm- ambient fluid interaction will be discussed in detail.

  13. Chemical Stability of Laponite in Aqueous Media

    OpenAIRE

    2014-01-01

    In this work stability of Laponite against dissolution in its aqueous dispersions is investigated as a function of initial pH of water before mixing Laponite, and concentration of Laponite. Dissolution of Laponite is quantified in terms of concentration of leached magnesium in the dispersions. Interestingly the solvent pH is observed to play no role in dissolution of Laponite in dispersion over the explored range of 3 to 10. Furthermore, contrary to the usual belief that Laponite dissolves wh...

  14. Engineered Barrier System: Physical and Chemical Environment

    Energy Technology Data Exchange (ETDEWEB)

    P. Dixon

    2004-04-26

    The conceptual and predictive models documented in this Engineered Barrier System: Physical and Chemical Environment Model report describe the evolution of the physical and chemical conditions within the waste emplacement drifts of the repository. The modeling approaches and model output data will be used in the total system performance assessment (TSPA-LA) to assess the performance of the engineered barrier system and the waste form. These models evaluate the range of potential water compositions within the emplacement drifts, resulting from the interaction of introduced materials and minerals in dust with water seeping into the drifts and with aqueous solutions forming by deliquescence of dust (as influenced by atmospheric conditions), and from thermal-hydrological-chemical (THC) processes in the drift. These models also consider the uncertainty and variability in water chemistry inside the drift and the compositions of introduced materials within the drift. This report develops and documents a set of process- and abstraction-level models that constitute the engineered barrier system: physical and chemical environment model. Where possible, these models use information directly from other process model reports as input, which promotes integration among process models used for total system performance assessment. Specific tasks and activities of modeling the physical and chemical environment are included in the technical work plan ''Technical Work Plan for: In-Drift Geochemistry Modeling'' (BSC 2004 [DIRS 166519]). As described in the technical work plan, the development of this report is coordinated with the development of other engineered barrier system analysis model reports.

  15. Aqueous fractionation yields chemically stable lupin protein isolates

    NARCIS (Netherlands)

    Berghout, J.A.M.; Marmolejo-Garcia, C.; Berton-Carabin, C.C.; Nikiforidis, C.V.; Boom, R.M.; Goot, van der A.J.

    2015-01-01

    The chemical stability of lupin protein isolates (LPIs) obtained through aqueous fractionation (AF, i.e. fractionation without the use of an organic solvent) at 4 °C or 20 °C was assessed. AF of lupin seeds results in LPIs containing 2 wt.% oil. This oil is composed of mono- and poly-unsaturated fat

  16. FBX aqueous chemical dosimeter for measurement of dosimetric parameters

    Energy Technology Data Exchange (ETDEWEB)

    Moussous, O., E-mail: o.moussous@crna.d [Centre de Recherche Nucleaire d' Alger (CRNA), 02 Boulevard Frantz Fanon B.P. 399, 16000 Alger (Algeria); Medjadj, T. [Centre de Recherche Nucleaire d' Alger (CRNA), 02 Boulevard Frantz Fanon B.P. 399, 16000 Alger (Algeria); Benguerba, M. [Faculte de Physique, Universite des Sciences et de la Technologie Houari-Boumediene USTHB, Alger (Algeria)

    2011-02-15

    We investigated the ferrous sulphate-benzoic acid-xylenol orange (FBX) aqueous chemical dosimeter for measurement of dosimetric parameters such as the output factor, backscatter factor and lateral beam profiles for different square fields sizes for {sup 60}Co {gamma}-rays. A water phantom was employed to measure these parameters. An ionization chamber (IC) was used for calibration and comparison. A comparison of the resulting measurements with an ionization chamber's measured parameters showed good agreement. We thus believe that the tissue equivalent FBX dosimetry system can measure the dosimetric parameters for {sup 60}Co with reasonable accuracy.

  17. Chemical metallization of KMPR photoresist polymer in aqueous solutions

    Science.gov (United States)

    Zeb, Gul; Duong, Xuan Truong; Vu, Ngoc Pi; Phan, Quang The; Nguyen, Duc Tuong; Ly, Viet Anh; Salimy, Siamak; Le, Xuan Tuan

    2017-06-01

    While conventional methods for preparing thin films of metals and metallic alloys on insulating substrates in the field of microelectromechanical systems (MEMS) include vapor deposition techniques, we demonstrate here that electroless deposition can be considered as an alternate efficient approach to metallize the surface of insulating substrates, such as KMPR epoxy photoresist polymer. In comparison with the physical and chemical vapor deposition methods, which are well-established for metallization of photoresist polymers, our electroless nickel plating requires only immersing the substrates into aqueous solutions in open air at low temperatures. Thin films of nickel alloy have been deposited electrolessly on KMPR surface, through a cost-effective and environmental chromium-free process, mediated through direct grafting of amine palladium complexes in aqueous medium. This covalent organic coating provides excellent adhesion between KMPR and the nickel film and allows better control of the palladium catalyst content. Covalent grafting and characterization of the deposited nickel film have been carried out by means of Fourier-transform infrared spectroscopy, scanning electron microscopy, energy-dispersive X-ray spectroscopy and X-ray photoelectron spectroscopy techniques.

  18. Aqueous Colloidal Stability of Graphene Oxide and Chemically Converted Graphene

    Directory of Open Access Journals (Sweden)

    Swarnima Kashyap

    2014-01-01

    Full Text Available Graphene oxide (GO was prepared by modified Hummer’s method, and chemically converted graphene (CCG was prepared by further reduction of the aqueous GO colloid. The effect of pH on particle size, particle charge, and light absorption of the aqueous colloids of GO and CCG was studied with titration against HCl or NaOH, to find the ideal characteristics for a stable dispersion. The GO colloid was stable in the pH range of 4–11, whereas the CCG colloid gained stability at a relatively narrower pH range of 7–10. Poor stability of the colloids was observed for both GO and CCG colloids at both extremes of the pH scale. Both of the colloids exhibited average size of ~1 micron in the low pH range, whereas for higher pH the size ranged between 300 and 500 nm. The UV-Vis spectra showed absorption peak at 230 nm for GO colloids that shifted to 260 nm for the CCG colloid. Such shift can be ascribed to restoring of electronic conjugation of the C=C bonds in CCG.

  19. Fatigue of tooth-colored restoratives in aqueous environment.

    Science.gov (United States)

    Kawakami, Yoshiko; Takeshige, Fumio; Hayashi, Mikako; Ebisu, Shigeyuki

    2007-01-01

    The purpose of this study was to investigate the interaction between mechanical and chemical fatigue in resin composites and dental ceramics, and the effects thereof on fatigue resistance of tooth-colored restoratives. To this end, the fatigue fracture resistance of restoratives under dry and aqueous conditions were analyzed by a dynamic fatigue crack propagation test using beam-shaped specimens with a precrack. Fatigue crack propagation characteristics were expressed by the correlation between fatigue crack growth rate (da/dN) and stress intensity factor range (deltaK). In addition, fatigue crack growth threshold (deltaKth) was calculated. Following the fatigue test, a fractographic examination was performed using scanning electron microscopy. Fatigue crack initiation was retarded in resin composites under aqueous condition, but dental ceramics were susceptible to slow crack growth after crack initiation. SEM images of the fatigue facture surfaces reflected inorganic and organic filler particles of different sizes in composites and the bonding at crystal-glass interface in ceramics. It was concluded that water exerted different effects on the fatigue resistance of composites and ceramics.

  20. Heavy metals removal from aqueous environments by electrocoagulation process- a systematic review.

    Science.gov (United States)

    Bazrafshan, Edris; Mohammadi, Leili; Ansari-Moghaddam, Alireza; Mahvi, Amir Hossein

    2015-01-01

    Heavy metals pollution has become a more serious environmental problem in the last several decades as a result releasing toxic materials into the environment. Various techniques such as physical, chemical, biological, advanced oxidation and electrochemical processes were used for the treatment of domestic, industrial and agricultural effluents. The commonly used conventional biological treatments processes are not only time consuming but also need large operational area. Accordingly, it seems that these methods are not cost-effective for effluent containing toxic elements. Advanced oxidation techniques result in high treatment cost and are generally used to obtain high purity grade water. The chemical coagulation technique is slow and generates large amount of sludge. Electrocoagulation is an electrochemical technique with many applications. This process has recently attracted attention as a potential technique for treating industrial wastewater due to its versatility and environmental compatibility. This process has been applied for the treatment of many kinds of wastewater such as landfill leachate, restaurant, carwash, slaughterhouse, textile, laundry, tannery, petroleum refinery wastewater and for removal of bacteria, arsenic, fluoride, pesticides and heavy metals from aqueous environments. The objective of the present manuscript is to review the potential of electrocoagulation process for the treatment of domestic, industrial and agricultural effluents, especially removal of heavy metals from aqueous environments. About 100 published studies (1977-2016) are reviewed in this paper. It is evident from the literature survey articles that electrocoagulation are the most frequently studied for the treatment of heavy metal wastewater.

  1. Nanotribological characterization of human head hair by friction force microscopy in dry atmosphere and aqueous environment.

    Science.gov (United States)

    Nikogeorgos, Nikos; Fletcher, Ian W; Boardman, Christopher; Doyle, Peter; Ortuoste, Nerea; Leggett, Graham J

    2010-06-01

    Friction force microscopy was employed for the tribological investigation of human head hair in two different environments: a dry atmosphere and de-ionized water. The fibers were immobilized by embedding them in indium. The effects of bleaching, conditioning, and immersion in methanolic KOH were quantified in terms of the relative coefficient of friction (μ). The virgin fibers were clearly distinguished in terms of friction coefficient from the chemically damaged ones in both environments, while all categories of hair exhibited higher friction coefficients in the aqueous environment. Secondary ion mass spectroscopy was used as a complementary technique to examine the presence of fatty acids on the cuticular surface of the different categories of hair as well as the conditioner distribution. Neither bleaching nor 30 min treatment in methanolic KOH was found adequate to completely remove the fatty acids from the fibers' surface. Conditioner species were detected along the whole cuticular surface.

  2. DESIGN OF ROBOTIC COLONIZER CONTROL SYSTEM FOR AQUEOUS ENVIRONMENT

    Directory of Open Access Journals (Sweden)

    C.VENKATESH

    2013-05-01

    Full Text Available Now a days there is a huge interest on underwater communication systems for various applications in order to explore aqueous environments. Intelligent robots and cooperative multi- agent robotic systems can be very efficient tools to speed up search and research operations in remote areas. Robots are also useful to do jobs inareas and in situations that are hazardous for human, they can go anywhere that is not reachable my humans and can go into gaps and move trough small holes that are impossible for humans and even trained dogs. in this paper, a wireless underwater mobile robot system is designed in order to study the behavior of artemia group. anew idea has been presented for underwater mobile robot system which is consists of two parts, first is the underwater mechanical robot and the second is ZigBee wireless based mobile robot which controls and moves the first part. by this system different patterns motion control (linear, circular, zigzag, etc. has been performed and proved the ability to control group of robot by controlling the group of artemia and monitoring the underwater mobile robot control with the help of water proof RF wireless camera and also explore the details present around the mobile robot

  3. Engineered Barrier System: Physical and Chemical Environment Model

    Energy Technology Data Exchange (ETDEWEB)

    D. M. Jolley; R. Jarek; P. Mariner

    2004-02-09

    The conceptual and predictive models documented in this Engineered Barrier System: Physical and Chemical Environment Model report describe the evolution of the physical and chemical conditions within the waste emplacement drifts of the repository. The modeling approaches and model output data will be used in the total system performance assessment (TSPA-LA) to assess the performance of the engineered barrier system and the waste form. These models evaluate the range of potential water compositions within the emplacement drifts, resulting from the interaction of introduced materials and minerals in dust with water seeping into the drifts and with aqueous solutions forming by deliquescence of dust (as influenced by atmospheric conditions), and from thermal-hydrological-chemical (THC) processes in the drift. These models also consider the uncertainty and variability in water chemistry inside the drift and the compositions of introduced materials within the drift. This report develops and documents a set of process- and abstraction-level models that constitute the engineered barrier system: physical and chemical environment model. Where possible, these models use information directly from other process model reports as input, which promotes integration among process models used for total system performance assessment. Specific tasks and activities of modeling the physical and chemical environment are included in the technical work plan ''Technical Work Plan for: In-Drift Geochemistry Modeling'' (BSC 2004 [DIRS 166519]). As described in the technical work plan, the development of this report is coordinated with the development of other engineered barrier system analysis model reports.

  4. Chemical Reaction Dynamics in Nanoscle Environments

    Energy Technology Data Exchange (ETDEWEB)

    Evelyn M. Goldfield

    2006-09-26

    The major focus of the research in this program is the study of the behavior of molecular systems confined in nanoscale environments. The goal is to develop a theoretical framework for predicting how chemical reactions occur in nanoscale environments. To achieve this goal we have employed ab initio quantum chemistry, classical dynamics and quantum dynamics methods. Much of the research has focused on the behavior of molecules confined within single-walled carbon nanotubes (SWCNTs). We have also studied interactions of small molecules with the exterior surface of SWCNTs. Nonequilibrium molecular dynamics of interfaces of sliding surface interfaces have also been performed.

  5. ENGINEERED BARRIER SYSTEM: PHYSICAL AND CHEMICAL ENVIRONMENT

    Energy Technology Data Exchange (ETDEWEB)

    R. Jarek

    2004-11-23

    The purpose of this report is to describe the evolution of the physical and chemical environmental conditions within the waste emplacement drifts of the repository, including the drip shield and waste package surfaces. The abstraction model is used in the total system performance assessment for the license application (TSPA LA) to assess the performance of the engineered barrier system and the waste form. This report develops and documents a set of these abstraction-level models that describe the engineered barrier system physical and chemical environment. Where possible, these models use information directly from other reports as input, which promotes integration among process models used for TSPA-LA. Specific tasks and activities of modeling the physical and chemical environment are included in ''Technical Work Plan for: Near-Field Environment and Transport In-Drift Geochemistry Model Report Integration'' (BSC 2004 [DIRS 171156], Section 1.2.2). As described in the technical work plan, the development of this report is coordinated with the development of other engineered barrier system reports.

  6. ENGINEERED BARRIER SYSTEM: PHYSICAL AND CHEMICAL ENVIRONMENT

    Energy Technology Data Exchange (ETDEWEB)

    G.H. Nieder-Westermann

    2005-04-07

    The purpose of this report is to describe the evolution of the physical and chemical environmental conditions within the waste emplacement drifts of the repository, including the drip shield and waste package surfaces. The abstraction model is used in the total system performance assessment for the license application (TSPA LA) to assess the performance of the engineered barrier system and the waste form. This report develops and documents a set of these abstraction-level models that describe the engineered barrier system physical and chemical environment. Where possible, these models use information directly from other reports as input, which promotes integration among process models used for TSPA-LA. Specific tasks and activities of modeling the physical and chemical environment are included in ''Technical Work Plan for: Near-Field Environment and Transport In-Drift Geochemistry Model Report Integration'' (BSC 2004 [DIRS 171156], Section 1.2.2). As described in the technical work plan, the development of this report is coordinated with the development of other engineered barrier system reports.

  7. Prediction of aqueous solubility, vapor pressure and critical micelle concentration for aquatic partitioning of perfluorinated chemicals.

    Science.gov (United States)

    Bhhatarai, Barun; Gramatica, Paola

    2011-10-01

    The majority of perfluorinated chemicals (PFCs) are of increasing risk to biota and environment due to their physicochemical stability, wide transport in the environment and difficulty in biodegradation. It is necessary to identify and prioritize these harmful PFCs and to characterize their physicochemical properties that govern the solubility, distribution and fate of these chemicals in an aquatic ecosystem. Therefore, available experimental data (10-35 compounds) of three important properties: aqueous solubility (AqS), vapor pressure (VP) and critical micelle concentration (CMC) on per- and polyfluorinated compounds were collected for quantitative structure-property relationship (QSPR) modeling. Simple and robust models based on theoretical molecular descriptors were developed and externally validated for predictivity. Model predictions on selected PFCs were compared with available experimental data and other published in silico predictions. The structural applicability domains (AD) of the models were verified on a bigger data set of 221 compounds. The predicted properties of the chemicals that are within the AD, are reliable, and they help to reduce the wide data gap that exists. Moreover, the predictions of AqS, VP, and CMC of most common PFCs were evaluated to understand the aquatic partitioning and to derive a relation with the available experimental data of bioconcentration factor (BCF).

  8. Industrial emerging chemicals in the environment

    Directory of Open Access Journals (Sweden)

    Vojinović-Miloradov Mirjana B.

    2014-01-01

    Full Text Available In the recent time, considerable interest has grown concerning the presence of the emerging industrial chemicals, EmIC. They are contaminants that have possible pathway to enter to the environment and they are dominantly released by industrial and anthropogenic activities. EmIC are applied in different fields using as industrial chemicals (new and recently recognized, global organic contaminants (flame retardant chemicals, pharmaceuticals (for both human and animal uses, endocrine-modulating compounds, biological metabolites, personal care products, household chemicals, nanomaterial (energy storage products, lubricants, anticorrosive and agriculture chemicals and others that are applied to a wide variety of everyday items such as clothing, upholstery, electronics and automobile interiors. NORMAN (Network of reference laboratories for monitoring of emerging environmental pollutants has established an open, dynamic, list of emerging substances and pollutants. EmIC have been recently detected in the environment due to their long-term presence, pseudo-persistence and increased use. Improvements in sophisticated analytical methods and time integrative passive sampling have enabled the identification and quantification of EmIC, in very low concentrations (ppb, ppt and lower, which likely have been present in all environmental mediums for decades. Passive technology is an innovative technique for the time-integrated measurement of emerging contaminants in water, sediment, soil and air. Passive samplers are simple handling cost-effective tool that could be used in environmental monitoring programmes. These devices are now being considered as a part of an emerging strategy for monitoring a range of emerging industrial chemicals and priority pollutants in the aquatic environment. EmIC are substances that are not included in the routine monitoring programmes and whose fate, behaviour and (ecotoxicological effects are still not well understood. Emerging

  9. Secondary organic aerosol (trans)formation through aqueous phase guaiacol photonitration: chemical characterization of the products

    Science.gov (United States)

    Grgić, Irena; Kitanovski, Zoran; Kroflič, Ana; Čusak, Alen

    2014-05-01

    One of the largest primary sources of organic aerosol in the atmosphere is biomass burning (BB) (Laskin et al. 2009); in Europe its contribution to annual mean of PM10 is between 3 and 14 % (Maenhaut et al. 2012). During the process of wood burning many different products are formed via thermal degradation of wood lignin. Hardwood burning produces mainly syringol (2,6-dimetoxyphenol) derivatives, while softwood burning exclusively guaiacol (2-methoxyphenol) and its derivatives. Taking into account physical properties of methoxyphenols only, their concentrations in atmospheric waters might be underestimated. So, their aqueous phase reactions can be an additional source of SOA, especially in regions under significant influence of wood combustion. An important class of compounds formed during physical and chemical aging of the primary BBA in the atmosphere is nitrocatechols, known as strong absorbers of UV and Vis light (Claeys et al. 2012). Very recently, methyl-nitrocatechols were proposed as suitable markers for highly oxidized secondary BBA (Iinuma et al. 2010, Kitanovski et al. 2012). In the present work, the formation of SOA through aqueous phase photooxidation and nitration of guaiacol was examined. The key objective was to chemically characterize the main low-volatility products and further to check their possible presence in the urban atmospheric aerosols. The aqueous phase reactions were performed in a thermostated reactor under simulated sunlight in the presence of H2O2 and nitrite. Guaiacol reaction products were first concentrated by solid-phase extraction (SPE) and then subjected to semi-preparative liquid chromatography.The main product compounds were fractionated and isolated as pure solids and their structure was further elucidated by using nuclear magnetic resonance spectroscopy (1H, 13C and 2D NMR) and direct infusion negative ion electro-spray ionization tandem mass spectrometry (( )ESI-MS/MS). The main photonitration products of guaiacol (4

  10. Studying chemical reactivity in a virtual environment.

    Science.gov (United States)

    Haag, Moritz P; Reiher, Markus

    2014-01-01

    Chemical reactivity of a set of reactants is determined by its potential (electronic) energy (hyper)surface. The high dimensionality of this surface renders it difficult to efficiently explore reactivity in a large reactive system. Exhaustive sampling techniques and search algorithms are not straightforward to employ as it is not clear which explored path will eventually produce the minimum energy path of a reaction passing through a transition structure. Here, the chemist's intuition would be of invaluable help, but it cannot be easily exploited because (1) no intuitive and direct tool for the scientist to manipulate molecular structures is currently available and because (2) quantum chemical calculations are inherently expensive in terms of computational effort. In this work, we elaborate on how the chemist can be reintroduced into the exploratory process within a virtual environment that provides immediate feedback and intuitive tools to manipulate a reactive system. We work out in detail how this immersion should take place. We provide an analysis of modern semi-empirical methods which already today are candidates for the interactive study of chemical reactivity. Implications of manual structure manipulations for their physical meaning and chemical relevance are carefully analysed in order to provide sound theoretical foundations for the interpretation of the interactive reactivity exploration.

  11. Mid-Infrared Sensing of Organic Pollutants in Aqueous Environments

    Directory of Open Access Journals (Sweden)

    Andrew Ross

    2009-08-01

    Full Text Available The development of chemical sensors for monitoring the levels of organic pollutants in the aquatic environment has received a great deal of attention in recent decades. In particular, the mid-infrared (MIR sensor based on attenuated total reflectance (ATR is a promising analytical tool that has been used to detect a variety of hydrocarbon compounds (i.e., aromatics, alkyl halides, phenols, etc. dissolved in water. It has been shown that under certain conditions the MIR-ATR sensor is capable of achieving detection limits in the 10-100 ppb concentration range. Since the infrared spectral features of every single organic molecule are unique, the sensor is highly selective, making it possible to distinguish between many different analytes simultaneously. This review paper discusses some of the parameters (i.e., membrane type, film thickness, conditioning that dictate MIR ATR sensor response. The performance of various chemoselective membranes which are used in the fabrication of the sensor will be evaluated. Some of the challenges associated with long-term environmental monitoring are also discussed.

  12. Peptide environment specifies conformation. Helicity of hydrophobic segments compared in aqueous, organic, and membrane environments.

    Science.gov (United States)

    Li, S C; Deber, C M

    1993-11-05

    Transmembrane segments in integral membrane proteins exist characteristically as helices in lipid bilayers, yet are often rich in residues considered helix-destabilizing (Val, Ile, Gly) in soluble proteins. We propose that helicity of a transmembrane segment is likely to be affected by factors other than the "intrinsic" helical propensities of its component amino acids. This hypothesis is tested by comparing the conformation(s) in aqueous, organic, membrane-mimetic (micellar), and membrane (bilayer) environments of designed model peptides with systematically altered helical propensity and/or segmental hydrophobicity. Peptides of prototypic sequence NH2-(Ser-Lys)2-Ala5-Leu6-Ala7-Ala8-Leu9-Ala10-++ +Trp11-Ala12-Leu13-Ala14- (Lys-Ser)3-OH were synthesized, which incorporate a hydrophobic core "guest" segment (residues 5-14) into a water-soluble hydrophilic host matrix. Related peptides featured substitution of Leu6,9,13-->Gly, Leu6,9,13-->Ala, and Ala7,10,14-->Gly. Circular dichroism spectra revealed that algorithms for soluble proteins correctly predicted peptide helical proclivities in aqueous solutions, but peptide helicity in organic (trifluoroethanol) solvents, membrane-mimetic SDS micelles, and negatively charged lipid bilayer vesicles, was found to be governed almost exclusively by the segmental hydrophobicity of the peptide mid-hydrophobic core segment. In related Trp fluorescence studies, peptide-membrane association was similarly correlated with extent of hydrophobic interaction.

  13. ENGINEERED BARRIER SYSTEM: PHYSICAL AND CHEMICAL ENVIRONMENT

    Energy Technology Data Exchange (ETDEWEB)

    R. Jarek

    2005-08-29

    The purpose of this model report is to describe the evolution of the physical and chemical environmental conditions within the waste emplacement drifts of the repository, including the drip shield and waste package surfaces. The resulting seepage evaporation and gas abstraction models are used in the total system performance assessment for the license application (TSPA-LA) to assess the performance of the engineered barrier system and the waste form. This report develops and documents a set of abstraction-level models that describe the engineered barrier system physical and chemical environment. Where possible, these models use information directly from other reports as input, which promotes integration among process models used for TSPA-LA. Specific tasks and activities of modeling the physical and chemical environment are included in ''Technical Work Plan for: Near-Field Environment and Transport In-Drift Geochemistry Model Report Integration'' (BSC 2005 [DIRS 173782], Section 1.2.2). As described in the technical work plan, the development of this report is coordinated with the development of other engineered barrier system reports. To be consistent with other project documents that address features, events, and processes (FEPs), Table 6.14.1 of the current report includes updates to FEP numbers and FEP subjects for two FEPs identified in the technical work plan (TWP) governing this report (BSC 2005 [DIRS 173782]). FEP 2.1.09.06.0A (Reduction-oxidation potential in EBS), as listed in Table 2 of the TWP (BSC 2005 [DIRS 173782]), has been updated in the current report to FEP 2.1.09.06.0B (Reduction-oxidation potential in Drifts; see Table 6.14-1). FEP 2.1.09.07.0A (Reaction kinetics in EBS), as listed in Table 2 of the TWP (BSC 2005 [DIRS 173782]), has been updated in the current report to FEP 2.1.09.07.0B (Reaction kinetics in Drifts; see Table 6.14-1). These deviations from the TWP are justified because they improve integration with FEPs

  14. Molecularly imprinted polymers for histamine recognition in aqueous environment.

    Science.gov (United States)

    Trikka, Foteini A; Yoshimatsu, Keiichi; Ye, Lei; Kyriakidis, Dimitrios A

    2012-11-01

    Molecularly imprinted polymers (MIP) for histamine using methacrylic acid were developed and recognition mechanisms were thoroughly characterized for the first time in this study. The binding affinity of imprinted polymer with structurally related compounds was studied in organic and aqueous media, at various conditions. In organic media, MIP was found to bind histamine two and six times more than ranitidine and fluoxetine, respectively, whereas higher selectivity was observed in the case of dimentidene or disodium cromoglycate. The specific binding sites of MIP recognized histamine over L-histidine in aqueous conditions, while higher affinity for histamine compared to ranitidine, disodium cromoglycate, putrescine and to a putrescine analogue was observed. A combination of NMR and UV spectroscopy analyses for investigation of imprinting and recognition properties revealed that strong specific interactions between the functional monomer and histamine in the prepolymerization and in the aqueous solutions were probably responsible for histamine recognition. The preparation of histamine MIPs and elucidation of imprinting and recognition mechanism may serve as useful insight for future application of MIPs.

  15. Behavior of suspending and wetting agents in aqueous environment

    Directory of Open Access Journals (Sweden)

    Dhawale Shashikant

    2009-01-01

    Full Text Available This work describes the changes in viscosity, conductivity, pH, electrical conductivity, dielectric constant, zeta potential, UV, and IR spectra of aqueous solutions/dispersions of sodium carboxy methyl cellulose (CMC, Tween 80, and sodium lauryl sulphate (SLS during aging at different temperatures. Significant reduction in viscosity ofh sodium CMC occurred during aging studies, while relatively small decrease in viscosity was seen with Tween 80 and SLS. Increment in specific conductivity was seen with aging of excipients. Significant increase of zeta potential was also seen with aging of samples. Concomitant shift in IR spectra of samples was observed with aging at 40°C.

  16. Chemical and photochemical properties of chloroharmine derivatives in aqueous solutions.

    Science.gov (United States)

    Rasse-Suriani, Federico A O; Denofrio, M Paula; Yañuk, Juan G; Gonzalez, M Micaela; Wolcan, Ezequiel; Seifermann, Marco; Erra-Balsells, Rosa; Cabrerizo, Franco M

    2016-01-14

    Thermal and photochemical stability (Φ(R)), room temperature UV-vis absorption and fluorescence spectra, fluorescence quantum yields (Φ(F)) and lifetimes (τ(F)), quantum yields of hydrogen peroxide (Φ(H2O2)) and singlet oxygen (Φ(Δ)) production, and triplet lifetimes (τ(T)) have been obtained for the neutral and protonated forms of 6-chloroharmine, 8-chloroharmine and 6,8-dichloroharmine, in aqueous media. When it was possible, the effect of pH and oxygen concentration was evaluated. The nature of electronic transitions of protonated and neutral species of the three investigated chloroharmines was established using Time-Dependent Density Functional Theory (TD-DFT) calculations. The impact of all the foregoing observations on the biological role of the studied compounds is discussed.

  17. Method for Non-Invasive Determination of Chemical Properties of Aqueous Solutions

    Science.gov (United States)

    Todd, Paul W. (Inventor); Jones, Alan (Inventor); Thomas, Nathan A. (Inventor)

    2016-01-01

    A method for non-invasively determining a chemical property of an aqueous solution is provided. The method provides the steps of providing a colored solute having a light absorbance spectrum and transmitting light through the colored solute at two different wavelengths. The method further provides the steps of measuring light absorbance of the colored solute at the two different transmitted light wavelengths, and comparing the light absorbance of the colored solute at the two different wavelengths to determine a chemical property of an aqueous solution.

  18. Chemical tracers of high-metallicity environments

    CERN Document Server

    Bayet, E; Bell, T A; Viti, S

    2012-01-01

    We present for the first time a detailed study of the properties of molecular gas in metal-rich environments such as early-type galaxies (ETGs). We have explored Photon-Dominated Region (PDR) chemistry for a wide range of physical conditions likely to be appropriate for these sources. We derive fractional abundances of the 20 most chemically reactive species as a function of the metallicity, as a function of the optical depth and for various volume number gas densities, Far-Ultra Violet (FUV) radiation fields and cosmic ray ionisation rates. We also investigate the response of the chemistry to the changes in $\\alpha-$element enhancement as seen in ETGs. We find that the fractional abundances of CS, H$_{2}$S, H$_{2}$CS, H$_{2}$O, H$_{3}$O$^{+}$, HCO$^{+}$ and H$_{2}$CN seem invariant to an increase of metallicity whereas C$^{+}$, CO, C$_{2}$H, CN, HCN, HNC and OCS appear to be the species most sensitive to this change. The most sensitive species to the change in the fractional abundance of $\\alpha-$elements ar...

  19. All-oxide Raman-active traps for light and matter: probing redox homeostasis model reactions in aqueous environment.

    Science.gov (United States)

    Alessandri, Ivano; Depero, L E

    2014-04-09

    Core-shell colloidal crystals can act as very efficient traps for light and analytes. Here it is shown that Raman-active probes can be achieved using SiO2-TiO2 core-shell beads. These systems are successfully tested in monitoring of glutathione redox cycle at physiological concentration in aqueous environment, without need of any interfering enhancers. These materials represent a promising alternative to conventional, metal-based SERS probes for investigating chemical and biochemical reactions under real working conditions. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Synthesis of antimicrobial silver nanoparticles through a photomediated reaction in an aqueous environment

    Directory of Open Access Journals (Sweden)

    Banasiuk R

    2016-01-01

    Full Text Available Rafał Banasiuk,1,* Joanna E Frackowiak,2,* Marta Krychowiak,1 Marta Matuszewska,1 Anna Kawiak,1 Magdalena Ziabka,3 Zofia Lendzion-Bielun,4 Magdalena Narajczyk,5 Aleksandra Krolicka1 1Department of Biotechnology, Intercollegiate Faculty of Biotechnology, University of Gdansk and Medical University of Gdansk, 2Department of Pathophysiology, Medical University of Gdansk, Gdansk, 3Faculty of Materials Science and Ceramics, Department of Ceramics and Refractories, AGH-University of Science and Technology, Kraków, 4Institute of Chemical and Environment Engineering, West Pomeranian University of Technology, Szczecin, 5Faculty of Biology, Laboratory of Electron Microscopy, University of Gdansk, Gdansk, Poland *These authors contributed equally to this work Abstract: A fast, economical, and reproducible method for nanoparticle synthesis has been developed in our laboratory. The reaction is performed in an aqueous environment and utilizes light emitted by commercially available 1 W light-emitting diodes (λ =420 nm as the catalyst. This method does not require nanoparticle seeds or toxic chemicals. The irradiation process is carried out for a period of up to 10 minutes, significantly reducing the time required for synthesis as well as environmental impact. By modulating various reaction parameters silver nanoparticles were obtained, which were predominantly either spherical or cubic. The produced nanoparticles demonstrated strong antimicrobial activity toward the examined bacterial strains. Additionally, testing the effect of silver nanoparticles on the human keratinocyte cell line and human peripheral blood mononuclear cells revealed that their cytotoxicity may be limited by modulating the employed concentrations of nanoparticles. Keywords: antimicrobial activity, green synthesis, nanocubes, nanospheres 

  1. Agglomeration, isolation and dissolution of commercially manufactured silver nanoparticles in aqueous environments

    Science.gov (United States)

    Elzey, Sherrie; Grassian, Vicki H.

    2010-06-01

    The increasing use of manufactured nanoparticles ensures these materials will make their way into the environment. Silver nanoparticles in particular, due to use in a wide range of applications, have the potential to get into water systems, e.g., drinking water systems, ground water systems, estuaries, and/or lakes. One important question is what is the chemical and physical state of these nanoparticles in water? Are they present as isolated particles, agglomerates or dissolved ions, as this will dictate their fate and transport. Furthermore, does the chemical and physical state of the nanoparticles change as a function of size or differ from micron-sized particles of similar composition? In this study, an electrospray atomizer coupled to a scanning mobility particle sizer (ES-SMPS) is used to investigate the state of silver nanoparticles in water and aqueous nitric acid environments. Over the range of pH values investigated, 0.5-6.5, silver nanoparticles with a bimodal primary particle size distribution with the most intense peak at 5.0 ± 7.4 nm, as determined from transmission electron microscopy (TEM), show distinct size distributions indicating agglomeration between pH 6.5 and 3 and isolated nanoparticles at pH values from 2.5 to 1. At the lowest pH investigated, pH 0.5, there are no peaks detected by the SMPS, indicating complete nanoparticle dissolution. Further analysis of the solution shows dissolved Ag ions at a pH of 0.5. Interestingly, silver nanoparticle dissolution shows size dependent behavior as larger, micron-sized silver particles show no dissolution at this pH. Environmental implications of these results are discussed.

  2. Aqueous organic chemistry in the atmosphere: sources and chemical processing of organic aerosols.

    Science.gov (United States)

    McNeill, V Faye

    2015-02-03

    Over the past decade, it has become clear that aqueous chemical processes occurring in cloud droplets and wet atmospheric particles are an important source of organic atmospheric particulate matter. Reactions of water-soluble volatile (or semivolatile) organic gases (VOCs or SVOCs) in these aqueous media lead to the formation of highly oxidized organic particulate matter (secondary organic aerosol; SOA) and key tracer species, such as organosulfates. These processes are often driven by a combination of anthropogenic and biogenic emissions, and therefore their accurate representation in models is important for effective air quality management. Despite considerable progress, mechanistic understanding of some key aqueous processes is still lacking, and these pathways are incompletely represented in 3D atmospheric chemistry and air quality models. In this article, the concepts, historical context, and current state of the science of aqueous pathways of SOA formation are discussed.

  3. Molecular Study of Capsaicin in Aqueous and Hydrophobic Environments

    OpenAIRE

    Lambert, Joseph Walter

    2006-01-01

    Anyone who has eaten spicy foods has experienced the adverse effects of capsaicin, the pungent chemical found in hot chili that causes a burning sensation. The specific action of capsaicin occurs by the activation of receptors in sensory neurons. This thesis investigates the interaction of capsaicin with model cell membranes representing the structure of neurons. In particular, we are interested in the changes induced by capsaicin to the structure and dynamics of membranes. Molecular dyna...

  4. A Review on Chemical Effects in Aqueous Solution induced by Plasma with Glow Discharge

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    Chemical effects in different aqueous solutions induced by plasma with glow dis charge electrolysis (GDE) and contact glow discharge electrolysis (CGDE) are described in this paper. The experimental and discharge characteristics are also reviewed. These are followed by a discussion of their mechanisms of both anodic and cathodic CGDE..

  5. Enhanced visible emission from vertically aligned ZnO nanostructures by aqueous chemical growth process

    Energy Technology Data Exchange (ETDEWEB)

    Amiruddin, R., E-mail: amirphy9@yahoo.com; Kumar, M.C. Santhosh, E-mail: santhoshmc@nitt.edu

    2014-11-15

    ZnO nanostructures consisting of nanowires and nanorods have been grown by aqueous chemical growth (ACG) process on the ZnO seed layers. ACG process has been carried out for 5 h and 15 h to obtain the one dimensional nanostructures. This ZnO nanostructure comprises mixture of vertically aligned nanorods and nanowires. Structural analysis reveals that the crystal orientation is along (002) plane exhibiting a hexagonal wurtzite structure. The crystallinity of ZnO nanostructures increases after aqueous chemical treatment with respect to the growth duration. Optical studies revealed that when the duration of aqueous chemical treatment is increased, the transmittance of the films decreases considerably. The as-deposited ZnO seed layers exhibit electron carrier concentration of 4.69×10{sup 14} cm{sup −3} and the value increases to 9.44×10{sup 15} cm{sup −3} after 5 h and 1.53×10{sup 16} cm{sup −3} after 15 h of aqueous chemical treatment. It has been observed that ZnO nanostructures exhibit enhanced luminescence properties in visible region which covers the entire visible region of the spectrum. - Highlights: • Mixture of nanorods and nanowires are grown upon same glass substrates. • The grown nanostructures are found to be vertically aligned. • Improved electron carrier concentration is observed. • Luminescence properties of these ZnO nanostructures are highly enhanced.

  6. Lignin solubilization and aqueous phase reforming for the production of aromatic chemicals and hydrogen

    NARCIS (Netherlands)

    Zakzeski, J.; Weckhuysen, B.M.

    2011-01-01

    The solubilization and aqueous phase reforming of lignin, including kraft, soda, and alcell lignin along with sugarcane bagasse, at low temperatures (T≤498 K) and pressures (P≤29 bar) is reported for the first time for the production of aromatic chemicals and hydrogen. Analysis of lignin model compo

  7. Lignin solubilization and aqueous phase reforming for the production of aromatic chemicals and hydrogen

    NARCIS (Netherlands)

    Zakzeski, J.; Weckhuysen, B.M.

    2011-01-01

    The solubilization and aqueous phase reforming of lignin, including kraft, soda, and alcell lignin along with sugarcane bagasse, at low temperatures (T≤498 K) and pressures (P≤29 bar) is reported for the first time for the production of aromatic chemicals and hydrogen. Analysis of lignin model

  8. Stability studies of CdSe nanocrystals in an aqueous environment

    DEFF Research Database (Denmark)

    Xi, Lifei; Lek, Jun Yan; Liang, Yen Nan;

    2011-01-01

    -generated holes oxidize CdSe to Cd2 + and elemental Se. The dissolution was accelerated in an acidic medium while moderate alkalinity (pH = 10.3) can slow down the dissolution possibly due to precipitation of nanocrystals. This study has strong implications for the use of these crystals in aqueous environments...

  9. Controlling wear failure of graphite-like carbon film in aqueous environment: Two feasible approaches

    Energy Technology Data Exchange (ETDEWEB)

    Wang Yongxin [State Key Laboratory of Solid Lubrication, Lanzhou Institute of Chemical Physics, Chinese Academy of Science, Lanzhou 730000 (China); Graduate School of the Chinese Academy of Sciences, Beijing 100039 (China); Wang Liping, E-mail: lpwang@licp.cas.cn [State Key Laboratory of Solid Lubrication, Lanzhou Institute of Chemical Physics, Chinese Academy of Science, Lanzhou 730000 (China); Xue Qunji [State Key Laboratory of Solid Lubrication, Lanzhou Institute of Chemical Physics, Chinese Academy of Science, Lanzhou 730000 (China)

    2011-02-15

    Friction and wear behaviors of graphite-like carbon (GLC) films in aqueous environment were investigated by a reciprocating sliding tribo-meter with ball-on-disc contact. Film structures and wear scars were studied by scanning electron microscope (SEM), energy dispersive spectroscopy (EDS) and a non-contact 3D surface profiler. A comprehensive wear model of the GLC film in aqueous environment was established, and two feasible approaches to control critical factor to the corresponding wear failure were discussed. Results showed that wear loss of GLC films in aqueous environment was characterized by micro-plough and local delamination. Due to the significant material loss, local delamination of films was critical to wear failure of GLC film in aqueous environment if the film was not prepared properly. The initiation and propagation of micro-cracks within whole films closely related to the occurrence of the films delamination from the interface between interlayer and substrate. The increase of film density by adjusting the deposition condition would significantly reduce the film delamination from substrate, meanwhile, fabricating a proper interlayer between substrate and GLC films to prevent the penetration of water molecules into the interface between interlayer and substrate could effectively eliminate the delamination.

  10. UV Spectral Analysis of the Chemical Modification and Photolysis of Acetylacetone Modified Alumina Aqueous Solution

    Institute of Scientific and Technical Information of China (English)

    Chengbin JING; Xiujian ZHAO; Haizheng TAO; Xina WANG; Aiyun LIU

    2004-01-01

    Acetylacetone was firstly introduced into the aqueous media with the presence of aluminum sec-butoxide and peptizator. It was confirmed that the UV (ultraviolet) absorption band of acetylacetone underwent 14 nm of red-shift due to the formation of the six-membered ring of the complex between alumina and acetylacetone in the aqueous solution. It was also found that the chemical modification can be dissociated by the UV irradiation with a wavelength shorter than 286 nm as a result of the excitation of π-π* transition in the complex.

  11. A CALPHAD study on the thermodynamic stability of calcium-, zinc-, and yttrium-doped magnesium in aqueous environments

    Energy Technology Data Exchange (ETDEWEB)

    Wu Kaisheng, E-mail: kaisheng.wu@netl.doe.gov [National Energy Technology Lab, 1450 Queen Ave SW, Albany, OR 97321 (United States); URS Corporation, PO Box 1959, Albany, OR 97321-0521 (United States); Dogan, Oemer N., E-mail: omer.dogan@netl.doe.gov [National Energy Technology Lab, 1450 Queen Ave SW, Albany, OR 97321 (United States); Velikokhatnyi, Oleg I., E-mail: olv3@pitt.edu [Center for Complex Engineered Multifunctional Materials, Swanson School of Engineering, University of Pittsburgh, Pittsburgh, PA 15261 (United States); Kumta, Prashant N., E-mail: pkumta@pitt.edu [Department of Mechanical Engineering and Materials Science, University of Pittsburgh, Pittsburgh, PA 15261 (United States); Swanson School of Engineering and School of Dental Medicine, University of Pittsburgh, Pittsburgh, PA 15261 (United States); Department of Bioengineering, University of Pittsburgh, Pittsburgh, PA 15261 (United States); Department of Chemical and Petroleum Engineering, University of Pittsburgh, Pittsburgh, PA 15261 (United States); Center for Complex Engineered Multifunctional Materials, Swanson School of Engineering, University of Pittsburgh, Pittsburgh, PA 15261 (United States)

    2011-12-15

    Highlights: Black-Right-Pointing-Pointer Execution of CALPHAD thermodynamic study and hydrolysis reactions of Mg-alloys. Black-Right-Pointing-Pointer CALPHAD and ab-initio studies demonstrate very similar results in pure water. Black-Right-Pointing-Pointer Alloying of Mg with Ca and Y promote hydrolysis, while Zn resists the hydrolysis. Black-Right-Pointing-Pointer Mg-(Ca, Y, Zn) alloys yield similar stability effects in water and in bio-solution. Black-Right-Pointing-Pointer Kinetic aspects are vital for aqueous stability studies of biodegradable Mg-alloys. - Abstract: Magnesium has attracted the attention of the biomaterials community as a potential biodegradable metallic candidate for use in stents and orthopedic applications. Alloying of Mg with metals such as Ca, Y and Zn, etc., to form alloy precursors is important to optimize its corrosion rate in electrolytic and aqueous environments to understand the alloy response in body fluid environments. In the current study, the chemical reactions of Mg-Me alloys (Me = Ca, Y, and Zn) with pure water have been investigated using the CALPHAD technique. A qualitative agreement between CALPHAD and first-principles results has been obtained. The CALPHAD method has also been employed to study the reactions of Mg alloys in the human blood fluid environment. The effects of alloying elements and compositions on the reaction enthalpies, reaction products, amount of gas release and gas compositions as well as the pH of the fluids have been systematically discussed and reported.

  12. Stability studies of CdSe nanocrystals in an aqueous environment.

    Science.gov (United States)

    Xi, Lifei; Lek, Jun Yan; Liang, Yen Nan; Boothroyd, Chris; Zhou, Wenwen; Yan, Qingyu; Hu, Xiao; Chiang, Freddy Boey Yin; Lam, Yeng Ming

    2011-07-08

    In this paper, CdSe nanocrystal dissolution in an aqueous solution was studied. It was found that light is a key factor affecting the dissolution of nanocrystals. In the presence of light, the electrons generated from CdSe nanocrystals reduce water to hydrogen and hydroxide ions (OH-) while photo-generated holes oxidize CdSe to Cd2+ and elemental Se. The dissolution was accelerated in an acidic medium while moderate alkalinity (pH=10.3) can slow down the dissolution possibly due to precipitation of nanocrystals. This study has strong implications for the use of these crystals in aqueous environments (bioimaging and dye-sensitized solar cells).

  13. Effects of pressure on aqueous chemical equilibria at subzero temperatures with applications to Europa

    Science.gov (United States)

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

    2005-01-01

    Pressure plays a critical role in controlling aqueous geochemical processes in deep oceans and deep ice. The putative ocean of Europa could have pressures of 1200 bars or higher on the seafloor, a pressure not dissimilar to the deepest ocean basin on Earth (the Mariana Trench at 1100 bars of pressure). At such high pressures, chemical thermodynamic relations need to explicitly consider pressure. A number of papers have addressed the role of pressure on equilibrium constants, activity coefficients, and the activity of water. None of these models deal, however, with processes at subzero temperatures, which may be important in cold environments on Earth and other planetary bodies. The objectives of this work were to (1) incorporate a pressure dependence into an existing geochemical model parameterized for subzero temperatures (FREZCHEM), (2) validate the model, and (3) simulate pressure-dependent processes on Europa. As part of objective 1, we examined two models for quantifying the volumetric properties of liquid water at subzero temperatures: one model is based on the measured properties of supercooled water, and the other model is based on the properties of liquid water in equilibrium with ice. The relative effect of pressure on solution properties falls in the order: equilibrium constants(K) > activity coefficients (??) > activity of water (aw). The errors (%) in our model associated with these properties, however, fall in the order: ?? > K > aw. The transposition between K and ?? is due to a more accurate model for estimating K than for estimating ??. Only activity coefficients are likely to be significantly in error. However, even in this case, the errors are likely to be only in the range of 2 to 5% up to 1000 bars of pressure. Evidence based on the pressure/temperature melting of ice and salt solution densities argue in favor of the equilibrium water model, which depends on extrapolations, for characterizing the properties of liquid water in electrolyte

  14. Study of Endocrine Disrupting Chemicals in Environment

    Directory of Open Access Journals (Sweden)

    Zoltán Juvancz

    2008-06-01

    Full Text Available Endocrine disrupting chemicals (EDC cause more and more seriousenvironmental pollutions. The EDCs show only ng-μg/l concentration level in theenvironment, therefore their determinations require multistep sample preparationprocesses and highly sophisticated instrumentation. This paper discuss the EDC effects,and show examples for determination of such compounds.

  15. Chemical modification of amino acids by atmospheric-pressure cold plasma in aqueous solution

    Science.gov (United States)

    Takai, Eisuke; Kitamura, Tsuyoshi; Kuwabara, Junpei; Ikawa, Satoshi; Yoshizawa, Shunsuke; Shiraki, Kentaro; Kawasaki, Hideya; Arakawa, Ryuichi; Kitano, Katsuhisa

    2014-07-01

    Plasma medicine is an attractive new research area, but the principles of plasma modification of biomolecules in aqueous solution remain elusive. In this study, we investigated the chemical effects of atmospheric-pressure cold plasma on 20 naturally occurring amino acids in aqueous solution. High-resolution mass spectrometry revealed that chemical modifications of 14 amino acids were observed after plasma treatment: (i) hydroxylation and nitration of aromatic rings in tyrosine, phenylalanine and tryptophan; (ii) sulfonation and disulfide linkage formation of thiol groups in cysteine; (iii) sulfoxidation of methionine and (iv) amidation and ring-opening of five-membered rings in histidine and proline. A competitive reaction experiment using 20 amino acids demonstrated that sulfur-containing and aromatic amino acids were preferentially decreased by the plasma treatment. These data provide fundamental information for elucidating the mechanism of protein inactivation for biomedical plasma applications.

  16. Changes in the color, chemical stability and antioxidant capacity of thermally treated anthocyanin aqueous solution over storage.

    Science.gov (United States)

    Sui, Xiaonan; Bary, Solène; Zhou, Weibiao

    2016-02-01

    Many anthocyanin-containing foods are thermally processed to ensure their safety, and stored for some time before being consumed. However, the combination of thermal processing and subsequent storage has a significant impact on anthocyanins. This study aimed to investigate the color, chemical stability, and antioxidant capacity of thermally treated anthocyanin aqueous solutions during storage at 4, 25, 45, and 65 °C, respectively. Anthocyanin aqueous solutions were thermally treated before storage. Results showed that the degradation rate of anthocyanins in aqueous solutions was much faster than those in real food. The color of the anthocyanin aqueous solutions changed dramatically during storage. The anthocyanin aqueous solutions stored at 4 °C showed the best chemical stability. Interestingly, the antioxidant capacity of the anthocyanin aqueous solutions stored at lower temperatures remained the same; however, the antioxidant capacity of those thermally treated at 120 or 140 °C and stored at 45 or 65 °C significantly decreased.

  17. The stability of the acetic acid dimer in microhydrated environments and in aqueous solution.

    Science.gov (United States)

    Pašalić, Hasan; Tunega, Daniel; Aquino, Adélia J A; Haberhauer, Georg; Gerzabek, Martin H; Lischka, Hans

    2012-03-28

    The thermodynamic stability of the acetic acid dimer conformers in microhydrated environments and in aqueous solution was studied by means of molecular dynamics simulations using the density functional based tight binding (DFTB) method. To confirm the reliability of this method for the system studied, density functional theory (DFT) and second order Møller-Plesset perturbation theory (MP2) calculations were performed for comparison. Classical optimized potentials for liquid simulations (OPLS) force field dynamics was used as well. One focus of this work was laid on the study of the capabilities of water molecules to break the hydrogen bonds of the acetic acid dimer. The barrier for insertion of one water molecule into the most stable cyclic dimer is found to lie between 3.25 and 4.8 kcal mol(-1) for the quantum mechanical methods, but only at 1.2 kcal mol(-1) for OPLS. Starting from different acetic acid dimer structures optimized in gas phase, DFTB dynamics simulations give a different picture of the stability in the microhydrated environment (4 to 12 water molecules) as compared to aqueous solution. In the former case all conformers are converted to the hydrated cyclic dimer, which remains stable over the entire simulation time of 1 ns. These results demonstrate that the considered microhydrated environment is not sufficient to dissociate the acetic acid dimer. In aqueous solution, however, the DFTB dynamics shows dissociation of all dimer structures (or processes leading thereto) starting after about 50 ps, demonstrating the capability of the water environment to break up the relatively strong hydrogen bridges. The OPLS dynamics in the aqueous environment shows--in contrast to the DFTB results--immediate dissociation, but a similar long-term behavior.

  18. Transport of cerium oxide nanoparticles in saturated silica media: influences of operational parameters and aqueous chemical conditions

    Science.gov (United States)

    Zhang, Zhaohan; Gao, Peng; Qiu, Ye; Liu, Guohong; Feng, Yujie; Wiesner, Mark

    2016-10-01

    This paper aimed to investigate the influences of operational parameters and aqueous chemical conditions on transport behaviors of cerium oxides nanoparticles (CeO2-NPs) in saturated silica media. Results indicated that increasing rates of attachment efficiency (α) were related with cationic types, and critical deposition concentration (CDC) for divalent cation (Ca2+ and Mg2+) were more than 31-fold of that for monovalent cation (Na+ and K+). Increase or reduction of electrolyte pH could both promote the mobility of CeO2-NPs in glass beads, while influence was more evident at alkaline conditions. α increased linearly with NPs concentrations, while decreased linearly with flow velocity in the column, and effects were related with electrolyte contents. Presence of surfactants could sharply decreased α, and SDS was more effective to facilitate CeO2-NPs transport than Triton X-100. With DOMs concentrations increasing, α firstly kept constant, then sharply declined, and finally reduced very slowly. The influence of DOMs on NPs deposition was in order of SA > HA > TA >  BSA. Overall, this study revealed that aqueous chemical conditions was crucial to NPs transport in porous media, and would provide significant information for our understanding on the fate and transport of nanoparticles in natural environment.

  19. Fabrication and characterization of ultrathin dextran layers: Time dependent nanostructure in aqueous environments revealed by OWLS.

    Science.gov (United States)

    Saftics, Andras; Kurunczi, Sándor; Szekrényes, Zsolt; Kamarás, Katalin; Khánh, Nguyen Quoc; Sulyok, Attila; Bősze, Szilvia; Horvath, Robert

    2016-10-01

    Surface coatings of the polysaccharide dextran and its derivatives are key ingredients especially in label-free biosensors for the suppression of non-specific binding and for receptor immobilization. Nevertheless, the nanostructure of these ultrathin coatings and its tailoring by the variation of the preparation conditions have not been profoundly characterized and understood. In this work carboxymethylated dextran (CMD) was prepared and used for fabricating ultrathin surface coatings. A grafting method based on covalent coupling to aminosilane- and epoxysilane-functionalized surfaces was applied to obtain thin CMD layers. The carboxyl moiety of the CMD was coupled to the aminated surface by EDC-NHS reagents, while CMD coupling through epoxysilane molecules was performed without any additional reagents. The surface analysis following the grafting procedures consisted of X-ray photoelectron spectroscopy (XPS), attenuated total reflection infrared spectroscopy (ATR-IR), spectroscopic ellipsometry, atomic force microscopy (AFM) and optical waveguide lightmode spectroscopy (OWLS). The XPS and AFM measurements showed that the grafting resulted in a very thin dextran layer of a few nanometers. The OWLS method allowed devising the structure of the interfacial dextran layers by the evaluation of the optogeometrical parameters. The alteration in the nanostructure of the CMD layer with the chemical composition of the silane coverage and the pH of the grafting solution was revealed by in situ OWLS, specifically, lain down chains were found to be prevalent on the surface under neutral and basic conditions on epoxysilylated surfaces. The developed methodologies allowed to design and fabricate nanometer scale CMD layers with well-controlled surface structure, which are very difficult to characterize in aqueous environments using present instrumentations and highly hydrated surface layers.

  20. Context of ancient aqueous environments on Mars from in situ geologic mapping at Endeavour Crater

    Science.gov (United States)

    Crumpler, L.S.; Arvidson, R. E.; Bell, J.; Clark, B. C.; Cohen, B. A.; Farrand, W. H.; Gellert, Ralf; Golombek, M.; Grant, J. A.; Guinness, E.; Herkenhoff, Kenneth E.; Johnson, J. R.; Jolliff, B.; Ming, D. W.; Mittlefehldt, D. W.; Parker, T.; Rice, J. W.; Squyres, S. W.; Sullivan, R.; Yen, A. S.

    2015-01-01

    Using the Mars Exploration Rover Opportunity, we have compiled one of the first field geologic maps on Mars while traversing the Noachian terrain along the rim of the 22 km diameter Endeavour Crater (Latitude −2°16′33″, Longitude −5°10′51″). In situ mapping of the petrographic, elemental, structural, and stratigraphic characteristics of outcrops and rocks distinguishes four mappable bedrock lithologic units. Three of these rock units predate the surrounding Burns formation sulfate-rich sandstones and one, the Matijevic Formation, represents conditions on early Mars predating the formation of Endeavour Crater. The stratigraphy assembled from these observations includes several geologic unconformities. The differences in lithologic units across these unconformities record changes in the character and intensity of the Martian aqueous environment over geologic time. Water circulated through fractures in the oldest rocks over periods long enough that texturally and elementally significant alteration occurred in fracture walls. These oldest pre-Endeavour rocks and their network of mineralized and altered fractures were preserved by burial beneath impact ejecta and were subsequently exhumed and exposed. The alteration along joints in the oldest rocks and the mineralized veins and concentrations of trace metals in overlying lithologic units is direct evidence that copious volumes of mineralized and/or hydrothermal fluids circulated through the early Martian crust. The wide range in intensity of structural and chemical modification from outcrop to outcrop along the crater rim shows that the ejecta of large (>8 km in diameter) impact craters is complex. These results imply that geologic complexity is to be anticipated in other areas of Mars where cratering has been a fundamental process in the local and regional geology and mineralogy.

  1. Correlation of 1H NMR Chemical Shift for Aqueous Solutions by Statistical Associating Fluid Theory Association Model

    Institute of Scientific and Technical Information of China (English)

    许波; 李浩然; 王从敏; 许映杰; 韩世钧

    2005-01-01

    1H NMR chemical shifts of binary aqueous mixtures of acylamide, alcohol, dimethyl sulphoxide (DMSO), and acetone are correlated by statistical associating fluid theory (SAFT) association model. The comparison between SAFT association model and Wilson equation shows that the former is better for dealing with aqueous solutions. Finally, the specialties of both models are discussed.

  2. Influence of formulation properties on chemical stability of captopril in aqueous preparations.

    Science.gov (United States)

    Kristensen, S; Lao, Y E; Brustugun, J; Braenden, J U

    2008-12-01

    The influence of various formulation properties on the chemical stability of captopril in aqueous media at pH 3 was investigated, in order to reformulate and increase the shelf-life of an oral mixture of the drug. At this pH, chemical stability is improved by an increase in drug concentration (1-5 mg/ml) and a decrease in temperature (5-36 degrees C), the latter demonstrated by a linear Arrhenius-plot. The activation energy is low (Ea = 10.2 kcal/mol), thus the Q10 value is only 1.8 in pure aqueous solutions. The degradation at the lowest concentration investigated in pure aqueous solution apparently follows zero order kinetics. The reaction order is changed at higher concentrations. We are presenting a hypothesis of intramolecular proton transfer from the thiol to the ionized carboxylic group as the initial step in the oxidative degradation pathways of captopril. Long-term stability of 1 mg/ml captopril in aqueous solutions at pH 3, stored at 36 degrees C for one year, shows that the sugar alcohol sorbitol accelerates degradation of the drug while Na-EDTA at a concentration as low as 0.01% is sufficient to stabilize these samples. Purging with N2-gas prior to storage is not essential for drug stability, as long as Na-EDTA is present. Only at a low level of Na-EDTA (0.01%) combined with a high level of sorbitol (35%), purging with N2-gas appears to have a small effect. The destabilizing effect of sugar alcohols is confirmed by accelerated degradation also in the presence of glycerol. The efficient stabilization in the presence of Na-EDTA at a low concentration indicates that the metal-ion-catalyzed oxidation pathway dominates the chemical degradation process at low pH, although several mechanisms seem to be involved depending on excipients present.

  3. Consumer exposure to chemicals in indoor environment : A specific focus on chemicals from textile products

    NARCIS (Netherlands)

    Wijnhoven SWP; Kooi MW; te Biesebeek JD; SIR; vgc

    2010-01-01

    Textile products in indoor environment contain a variety of chemicals. Well-known examples are flame retardants, phthalates, formaldehyde and dimethylfumarate. Consumers are potentially exposed to these chemicals since a lot of textile products are present in indoor environment (clothing, curtains,

  4. Demonstration of mode splitting in an optical microcavity in aqueous environment

    CERN Document Server

    Kim, Woosung; Zhu, Jiangang; He, Lina; Yang, Lan; 10.1063/1.3481352

    2010-01-01

    Scatterer induced modal coupling and the consequent mode splitting in a whispering gallery mode resonator is demonstrated in aqueous environment. The rate of change in splitting as particles enter the resonator mode volume strongly depends on the concentration of particle solution: The higher is the concentration, the higher is the rate of change. Polystyrene nanoparticles of radius 50nm with concentration as low as 5x10^(-6)wt% have been detected using the mode splitting spectra. Observation of mode splitting in water paves the way for constructing advanced resonator based sensors for measuring nanoparticles and biomolecules in various environments.

  5. Intergranular stress corrosion cracking of welded ferritic stainless steels in high temperature aqueous environments

    Energy Technology Data Exchange (ETDEWEB)

    Fukuzuka, Toshio; Shimogori, Kazutoshi; Fujiwara, Kazuo; Tomari, Haruo (Kobe Steel Ltd. (Japan). Central Research and Development Lab.); Kanda, Masao

    1982-07-01

    In considering the application of ferritic stainless steels to heat exchanger tubing materials for moisture separator-reheaters in LWRs, the effects of environmental conditions (temperature, chloride, dissolved oxygen, pH), thermal history, and steel composition (content of C, N, Cr and Ti) on the Inter-Granular Stress Corrosion Cracking (IGSCC) in high temperature aqueous environments, were studied. The IGSCC was proved to depend on steel composition and thermal history rather than environment. From these results, a steel was designed to prevent IGSCC of the welding HAZ for 18Cr and 13Cr steels.

  6. Measurement of high carrier mobility in graphene in an aqueous electrolyte environment

    Science.gov (United States)

    Brown, Morgan A.; Crosser, Michael S.; Leyden, Matthew R.; Qi, Yabing; Minot, Ethan D.

    2016-08-01

    Graphene is a promising material for applications in aqueous electrolyte environments. To explore the impact of such environments on graphene's electrical properties, we performed Hall bar measurements on electrolyte-gated graphene. Assuming a Drude model, we find that the room temperature carrier mobility in water-gated, SiO2-supported graphene reaches 7000 cm2/Vs, comparable to the best dry SiO2-supported graphene devices. Our results show that the electrical performance of graphene is robust, even in the presence of dissolved ions that introduce an additional mechanism for Coulomb scattering.

  7. Plasmonics Based Harsh Environment Compatible Chemical Sensors

    Energy Technology Data Exchange (ETDEWEB)

    Michael Carpenter

    2012-01-15

    Au-YSZ, Au-TiO{sub 2} and Au-CeO{sub 2} nanocomposite films have been investigated as a potential sensing element for high-temperature plasmonic sensing of H{sub 2}, CO, and NO{sub 2} in an oxygen containing environment. The Au-YSZ and Au-TiO{sub 2} films were deposited using PVD methods, while the CeO{sub 2} thin film was deposited by molecular beam epitaxy (MBE) and Au was implanted into the as-grown film at an elevated temperature followed by high temperature annealing to form well-defined Au nanoclusters. Each of the films were characterized by x-ray diffraction (XRD) and Rutherford backscattering spectrometry (RBS). For the gas sensing experiments, separate exposures to varying concentrations of H{sub 2}, CO, and NO{sub 2} were performed at a temperature of 500°C in oxygen backgrounds of 5.0, 10, and ~21% O{sub 2}. Changes in the localized surface plasmon resonance (LSPR) absorption peak were monitored during gas exposures and are believed to be the result of oxidation-reduction processes that fill or create oxygen vacancies in the respective metal oxides. This process affects the LSPR peak position either by charge exchange with the Au nanoparticles or by changes in the dielectric constant surrounding the particles. Hyperspectral multivariate analysis was used to gauge the inherent selectivity of the film between the separate analytes. From principal component analysis (PCA), unique and identifiable responses were seen for each of the analytes. Linear discriminant analysis (LDA) was also used on the Au-CeO{sub 2} results and showed separation between analytes as well as trends in gas concentration. Results indicate that each of the films are is selective towards O{sub 2}, H{sub 2}, CO, and NO{sub 2} in separate exposures. However, when the films were analyzed in a sensor array based experiment, ie simultaneous exposures to the target gases, PCA analysis of the combined response showed an even greater selective character towards the target gases. Combined

  8. Biosorption of heavy metal ions from aqueous solutions by short hemp fibers: Effect of chemical composition.

    Science.gov (United States)

    Pejic, Biljana; Vukcevic, Marija; Kostic, Mirjana; Skundric, Petar

    2009-05-15

    Sorption potential of waste short hemp fibers for Pb(2+), Cd(2+) and Zn(2+) ions from aqueous media was explored. In order to assess the influence of hemp fiber chemical composition on their heavy metals sorption potential, lignin and hemicelluloses were removed selectively by chemical modification. The degree of fiber swelling and water retention value were determined in order to evaluate the change in accessibility of the cell wall components to aqueous solutions due to the fiber modification. The effects of initial ion concentration, contact time and cosorption were studied in batch sorption experiments. The obtained results show that when the content of either lignin or hemicelluloses is progressively reduced by chemical treatment, the sorption properties of hemp fibers are improved. Short hemp fibers are capable of sorbing metal ions (Pb(2+), Cd(2+) and Zn(2+)) from single as well as from ternary metal ion solutions. The maximum total uptake capacities for Pb(2+), Cd(2+) and Zn(2+) ions from single solutions are the same, i.e. 0.078mmol/g, and from ternary mixture 0.074, 0.035 and 0.035mmol/g, respectively.

  9. Fabrication and fluorescent labeling of guar gum nanoparticles in a surfactant free aqueous environment.

    Science.gov (United States)

    Ghosh, Sumanta Kumar; Abdullah, Farooque; Mukherjee, Arup

    2015-01-01

    Guar gum (GG) is a galactomannan obtained from the seeds of Cyamopsis tetragonoloba. GG polysaccharide is used in a range of technology arenas and its properties in water environment elicited a lot of interest. We report a simple acid hydrolysis technique to derive water dispersible spherical nanoparticles from GG for the first time without any stabilizing surfactant. The particles demonstrated colloidal stability and were observed to carry negative surface charges in aqueous environment. The TEM study of guar gum nanoparticles (GGn) indicated a size range of 30-80 nm with a mean at 48.8 nm. Mineral acid at apposite concentration have apparently solubilized the amorphous regions of the polymer chain leaving the crystalline parts. GGn were further covalently functionalized in aqueous environment with fluorescein isothiocyanate (FITC) using a hydroxy-propyl amine spacer group. Nanoparticle fluorescence intensity can be modulated with pH changes and a significant augmentation in the intensity was noticed at the physiologically relevant range of 6-8. New fluorescently labeled nanoparticles have potential for applications in bioimaging, biomolecular interaction studies and as a pH sensing probe in sub cellular environment.

  10. The chemical exposure toxicity space (CETS) model: Displaying exposure time, aqueous and organic concentration, activity, and onset of toxicity

    Science.gov (United States)

    Mackay, Donald; Parnis, J. Mark; McCarty, Lynn S.; Arnot, Jon A.; Powell, David E.

    2016-01-01

    Abstract A 1‐compartment toxicokinetic model is used to characterize the chemical exposure toxicity space (CETS), providing a novel graphic tool that can aid in the design of aquatic toxicity tests for fish and for interpreting their results. The graph depicts the solution to the differential equation describing the uptake kinetics of a chemical by a modeled fish under conventional bioassay conditions. The model relates the exposure concentration in the water to a dimensionless time and the onset of toxicity as determined by an estimated or assumed critical body residue or incipient lethal aqueous concentration. These concentration graphs are specific to each chemical and exposure and organism parameters and clearly demonstrate differences in toxicity between chemicals and how factors such as hydrophobicity influence the toxic endpoint. The CETS plots can also be used to assess bioconcentration test conditions to ensure that concentrations are well below toxic levels. Illustrative applications are presented using a recent set of high‐quality toxicity data. Conversion of concentrations to chemical activities in the plots enables results for different baseline toxicants to be superimposed. For chemicals that have different modes of toxic action, the increased toxicity then becomes apparent. Implications for design and interpretation of aquatic toxicity tests are discussed. The model, and pictorial visualization of the time‐course of aquatic toxicity tests, may contribute to improvements in test design, implementation, and interpretation, and to reduced animal usage. Environ Toxicol Chem 2017;36:1389–1396. © 2016 The Authors. Environmental Toxicology and Chemistry Published by Wiley Periodicals, Inc. on behalf of SETAC. PMID:27801500

  11. Enhancement of hybridoma formation, clonability and cell proliferation in a nanoparticle-doped aqueous environment

    Directory of Open Access Journals (Sweden)

    Karnieli Ohad

    2008-01-01

    Full Text Available Abstract Background The isolation and production of human monoclonal antibodies is becoming an increasingly important pursuit as biopharmaceutical companies migrate their drug pipelines away from small organic molecules. As such, optimization of monoclonal antibody technologies is important, as this is becoming the new rate-limiting step for discovery and development of new pharmaceuticals. The major limitations of this system are the efficiency of isolating hybridoma clones, the process of stabilizing these clones and optimization of hybridoma cell secretion, especially for large-scale production. Many previous studies have demonstrated how perturbations in the aqueous environment can impact upon cell biology. In particular, radio frequency (RF irradiation of solutions can have dramatic effects on behavior of solutions, cells and in particular membrane proteins, although this effect decays following removal of the RF. Recently, it was shown that nanoparticle doping of RF irradiated water (NPD water produced a stabilized aqueous medium that maintained the characteristic properties of RF irradiated water for extended periods of time. Therefore, the ordering effect in water of the RF irradiation can now be studied in systems that required prolonged periods for analysis, such as eukaryotic cell culture. Since the formation of hybridoma cells involves the formation of a new membrane, a process that is affected by the surrounding aqueous environment, we tested these nanoparticle doped aqueous media formulations on hybridoma cell production. Results In this study, we tested the entire process of isolation and production of human monoclonal antibodies in NPD water as a means for further enhancing human monoclonal antibody isolation and production. Our results indicate an overall enhancement of hybridoma yield, viability, clonability and secretion. Furthermore, we have demonstrated that immortal cells proliferate faster whereas primary human fibroblasts

  12. Modelling the multiphase chemical processing of Monoethanolamine from industrial CCS processes in tropospheric aqueous particles and clouds

    Science.gov (United States)

    Tilgner, Andreas; Bräuer, Peter; Wolke, Ralf; Herrmann, Hartmut

    2013-04-01

    Using amine based solvent technology is an option to realise CO2 capture from the exhaust of power plants. Amines such as Monoethanolamine (MEA) may potentially be released in trace amounts during the carbon capture and storage (CCS) process. In order to investigate the tropospheric chemical fate of MEA from CO2 capturing processes and their oxidation products, multiphase modelling was performed and a reduced mechanism for future 3D model applications was developed in the present study. Based on former laboratory investigations and mechanism developments, an up-to-date multiphase mechanism describing the gas and aqueous phase chemistry of MEA has been developed in the present study. The developed multiphase phase oxidation scheme of MEA and its oxidation products, incl. nitrosamines, nitramines and amides, was coupled to the existing multiphase chemistry mechanism (RACM-MIM2ext-CAPRAM3.0i-red, Deguillaume et al. 2010) and the CAPRAM Halogen Module 2.0. Overall, the multiphase mechanism comprises 1276 chemical processes including 668 gas and 518 aqueous phase reactions as well as 90 phase transfers. The multiphase amine module contains in total 138 processes. The final mechanism was used in the Lagrangian parcel model SPACCIM (Wolke et al., 2005) to investigate e.g. the main oxidation pathways, the formation of hazardous oxidation products and seasonal differences. Simulations were performed using a meteorological scenario with non-permanent clouds, different environmental trajectories and seasonal conditions. The simulations revealed the importance of both cloud droplets and deliquescent particles to be an important compartment for the multiphase processing of MEA and its products. Due to the shifted partitioning of MEA towards the aqueous phase, the model investigations implicated that aqueous phase oxidation by OH radicals represents the main sink for MEA under daytime cloud summer conditions. Reaction flux analyses have shown that under deliquescent particle

  13. Reaction mechanisms of aqueous monoethanolamine with carbon dioxide: a combined quantum chemical and molecular dynamics study.

    Science.gov (United States)

    Hwang, Gyeong S; Stowe, Haley M; Paek, Eunsu; Manogaran, Dhivya

    2015-01-14

    Aqueous monoethanolamine (MEA) has been extensively studied as a solvent for CO2 capture, yet the underlying reaction mechanisms are still not fully understood. Combined ab initio and classical molecular dynamics simulations were performed to revisit and identify key elementary reactions and intermediates in 25-30 wt% aqueous MEA with CO2, by explicitly taking into account the structural and dynamic effects. Using static quantum chemical calculations, we also analyzed in more detail the fundamental interactions involved in the MEA-CO2 reaction. We find that both the CO2 capture by MEA and solvent regeneration follow a zwitterion-mediated two-step mechanism; from the zwitterionic intermediate, the relative probability between deprotonation (carbamate formation) and CO2 removal (MEA regeneration) tends to be determined largely by the interaction between the zwitterion and neighboring H2O molecules. In addition, our calculations clearly demonstrate that proton transfer in the MEA-CO2-H2O solution primarily occurs through H-bonded water bridges, and thus the availability and arrangement of H2O molecules also directly impacts the protonation and/or deprotonation of MEA and its derivatives. This improved understanding should contribute to developing more comprehensive kinetic models for use in modeling and optimizing the CO2 capture process. Moreover, this work highlights the importance of a detailed atomic-level description of the solution structure and dynamics in order to better understand molecular mechanisms underlying the reaction of CO2 with aqueous amines.

  14. Persistence and transport potential of chemicals in a multimedia environment

    Energy Technology Data Exchange (ETDEWEB)

    van de Meent, D.; McKone, T.E.; Parkerton, T.; Matthies, M.; Scheringer, M.; Wania, F.; Purdy, R.; Bennett, D.H.

    2000-02-01

    Persistence in the environment and potential for long-range transport are related since time in the environment is required for transport. A persistent chemical will travel longer distances than a reactive chemical that shares similar chemical properties. Scheringer (1997) has demonstrated the correlation between persistence and transport distance for different organic chemicals. However, this correlation is not sufficiently robust to predict one property from the other. Specific chemicals that are persistent mayor may not exhibit long-range transport potential. Persistence and long-range transport also present different societal concerns. Persistence concerns relate to the undesired possibility that chemicals produced and used now may somehow negatively affect future generations. Long-range transport concerns relate to the undesired presence of chemicals in areas where these compounds have not been used. Environmental policy decisions can be based on either or both considerations depending on the aim of the regulatory program. In this chapter, definitions and methods for quantifying persistence and transport potential of organic chemicals are proposed which will assist in the development of sound regulatory frameworks.

  15. Stability of titania nanotube arrays in aqueous environment and the related factors.

    Science.gov (United States)

    Cao, Can; Yan, Jun; Zhang, Yumei; Zhao, Lingzhou

    2016-03-10

    Titania nanotube arrays (NTAs) on titanium (Ti) fabricated by electrochemical anodization have attracted tremendous interest for diverse applications, of which most perform in aqueous environment or related to interaction with water. The NTAs are widely studied however the related factor of stability of NTAs when applied in such environment has rarely been concerned. We report that the annealed anatase NTAs are stable but the non-annealed amorphous NTAs are unstable to undergo specific structural change accompanied with a process of amorphous TiO2 dissolution and anatase TiO2 recrystallization. Quite unexpectedly, the non-annealed NTAs still show good stability without structural change in the cell culture media, possibly due to the presence of inorganics that may interfere with the TiO2 dissolution/redeposition process. The pH value of the aqueous environment is not a determinant factor for the structural change for non-annealed NTAs or not, while the temperature and the existence of F(-) can accelerate the structural change process. F(-) may play a very important role in the change process.

  16. Stability of titania nanotube arrays in aqueous environment and the related factors

    Science.gov (United States)

    Cao, Can; Yan, Jun; Zhang, Yumei; Zhao, Lingzhou

    2016-01-01

    Titania nanotube arrays (NTAs) on titanium (Ti) fabricated by electrochemical anodization have attracted tremendous interest for diverse applications, of which most perform in aqueous environment or related to interaction with water. The NTAs are widely studied however the related factor of stability of NTAs when applied in such environment has rarely been concerned. We report that the annealed anatase NTAs are stable but the non-annealed amorphous NTAs are unstable to undergo specific structural change accompanied with a process of amorphous TiO2 dissolution and anatase TiO2 recrystallization. Quite unexpectedly, the non-annealed NTAs still show good stability without structural change in the cell culture media, possibly due to the presence of inorganics that may interfere with the TiO2 dissolution/redeposition process. The pH value of the aqueous environment is not a determinant factor for the structural change for non-annealed NTAs or not, while the temperature and the existence of F− can accelerate the structural change process. F− may play a very important role in the change process. PMID:26960922

  17. Chemical Oxidative Polymerization of 2-Aminothiazole in Aqueous Solution: Synthesis, Characterization and Kinetics Study

    Directory of Open Access Journals (Sweden)

    Hua Zou

    2016-11-01

    Full Text Available The chemical oxidative polymerization of 2-aminothiazole (AT was studied in aqueous solution using copper chloride (CuCl2 as an oxidant. The effect of varying the reaction temperature, reaction time and oxidant/monomer molar ratio on the polymer yield was investigated. The resulting poly(2-aminothiazoles (PATs were characterized by FTIR, 1H NMR, UV-vis, gel permeation chromatography, scanning electron microscopy, thermogravimetric analysis and four-point probe electrical conductivity measurements. Compared with a previous study, PATs with higher yield (81% and better thermal stability could be synthesized. The chemical oxidative polymerization kinetics of AT were studied for the first time. The orders of the polymerization reaction with respect to monomer concentration and oxidant concentration were found to be 1.14 and 0.97, respectively, and the apparent activation energy of the polymerization reaction was determined to be 21.57 kJ/mol.

  18. Determination of Gibbs energies of formation in aqueous solution using chemical engineering tools.

    Science.gov (United States)

    Toure, Oumar; Dussap, Claude-Gilles

    2016-08-01

    Standard Gibbs energies of formation are of primary importance in the field of biothermodynamics. In the absence of any directly measured values, thermodynamic calculations are required to determine the missing data. For several biochemical species, this study shows that the knowledge of the standard Gibbs energy of formation of the pure compounds (in the gaseous, solid or liquid states) enables to determine the corresponding standard Gibbs energies of formation in aqueous solutions. To do so, using chemical engineering tools (thermodynamic tables and a model enabling to predict activity coefficients, solvation Gibbs energies and pKa data), it becomes possible to determine the partial chemical potential of neutral and charged components in real metabolic conditions, even in concentrated mixtures.

  19. Ion Pair in Extreme Aqueous Environments, Molecular-Based and Electric Conductance Approaches

    Energy Technology Data Exchange (ETDEWEB)

    Chialvo, Ariel A [ORNL; Gruszkiewicz, Miroslaw {Mirek} S [ORNL; Simonson, J Michael {Mike} [ORNL; Palmer, Donald [ORNL; Cole, David R [ORNL

    2009-01-01

    We determine by molecular-based simulation the density profiles of the Na+!Cl! ion-pair association constant in steam environments along three supercritical isotherms to interrogate the behavior of ion speciation in dilute aqueous solutions at extreme conditions. Moreover, we describe a new ultra-sensitive flow-through electric conductance apparatus designed to bridge the gap between the currently lowest steam-density conditions at which we are experimentally able to attain electric conductance measurements and the theoretically-reachable zero-density limit. Finally, we highlight important modeling challenges encountered near the zero-density limit and discuss ways to overcome them.

  20. Chemical characterization and anaerobic biodegradability of hydrothermal liquefaction aqueous products from mixed-culture wastewater algae.

    Science.gov (United States)

    Tommaso, Giovana; Chen, Wan-Ting; Li, Peng; Schideman, Lance; Zhang, Yuanhui

    2015-02-01

    This study examined the chemical characteristics and the anaerobic degradability of the aqueous product from hydrothermal liquefaction (HTL-ap) from the conversion of mixed-culture algal biomass grown in a wastewater treatment system. The effects of the HTL reaction times from 0 to 1.5 h, and reaction temperatures from 260 °C to 320 °C on the anaerobic degradability of the HTL-ap were quantified using biomethane potential assays. Comparing chemical oxygen demand data for HTL-ap from different operating conditions, indicated that organic matter may partition from organic phase to aqueous phase at 320 °C. Moderate lag phase and the highest cumulative methane production were observed when HTL-ap was obtained at 320 °C. The longest lag phase and the smallest production rate were observed in the process fed with HTL-ap obtained at 300 °C. Nevertheless, after overcoming adaptation issues, this HTL-ap led to the second highest accumulated specific methane production. Acetogenesis was identified as a possible rate-limiting pathway.

  1. The properties and transport phenomena in oxide films on iron, nickel, chromium and their alloys in aqueous environments

    Energy Technology Data Exchange (ETDEWEB)

    Laitinen, T.; Bojinov, M.; Betova, I.; Maekelae, K.; Saario, T. [VTT Manufacturing Technology, Espoo (Finland)

    1999-01-01

    The construction materials used in coolant systems in nuclear power plants become covered with oxide films as a result of exposure to the aqueous environment. The susceptibility of the materials to different forms of corrosion, as well as the extent of the incorporation of radioactive species on the surfaces of the primary circuit, are greatly influenced by the physical and chemical properties of these oxide films. The composition and characteristics of the oxide films in turn depend on the applied water chemistry. This work was undertaken in order to collect and evaluate the present views on the structure and behaviour of oxide films formed on iron- and nickel-based materials in aqueous environments. This survey should serve to recognise the areas in which more understanding and research effort is needed. The review begins with a discussion on the bulk oxides of iron, nickel and chromium, as well as their mixed oxides. In addition to bulk oxides, the structure and properties of oxide films forming on pure iron, nickel and chromium and on iron- and nickel-based engineering alloys are considered. General approaches to model the structure and growth of oxide films on metals are discussed in detail. The specific features of the oxide structures, properties and growth at high temperatures are presented with special focus on the relevance of existing models. Finally, the role of oxide films in localised corrosion, oxide breakdown pitting. Stress corrosion cracking and related phenomena is considered. The films formed on the surfaces of iron- and nickel-based alloys in high-temperature aqueous environments generally comprise two layers, i.e. the so-called duplex structure. The inner part is normally enriched in chromium and has a more compact structure, while the outer part is enriched in iron and has a cracked or porous structure. The information collected clearly indicates the effect of the chemical environment on the properties of oxide films growing on metal surfaces

  2. Chemical degradation of an uncrosslinked pure fluororubber in an alkaline environment

    DEFF Research Database (Denmark)

    Mitra, S.; Ghanbari-Siahkali, A.; Kingshott, P.

    2004-01-01

    after prolonged exposure (e.g., 12 weeks). The molecular mechanisms of the chemical degradation processes at the surface were evaluated with X-ray photoelectron spectroscopy and attenuated total reflectance/Fourier transform infrared spectroscopy. The results revealed that the early degradation......The chemical degradation of an uncrosslinked pure fluoroelastomer (FKM; Viton A) in an alkaline environment (10% NaOH and 80 degreesC) was investigated. Scanning electron microscopy images showed that on a microscopic level, significant degradation substantially increased the surface roughness...... proceeded primarily via dehydrofluorination reactions, creating double bonds in the rubber backbone. This further accelerated the degradation after longer exposure times. Furthermore, the resulting double bonds underwent nucleophilic attack by an aqueous NaOH solution to form several oxygenated species. All...

  3. Theoretical and computational studies of the interactions between small nanoparticles and with aqueous environments

    Science.gov (United States)

    Villarreal, Oscar D.

    Interactions between nanoparticles (metallic, biological or a hybrid mix of the two) in aqueous solutions can have multiple biological applications. In some of them their tendency towards aggregation can be desirable (e.g. self-assembly), while in others it may impact negatively on their reliability (e.g. drug delivery). A realistic model of these systems contains about a million or more degrees of freedom, but their study has become feasible with today's high performance computing. In particular, nanoparticles of a few nanometers in size interacting at sub-nanometer distances have become a novel area of research. The standard mean-field model of colloid science, the Derjaguin-Landau-Verwey-Overbeak (DLVO) theory, and even the extended version (XDLVO) have encountered multiple challenges when attempting to understand the interactions of small nanoparticles in the short range, since assumptions of continuous effects no longer apply. Because the region of the interaction is in the angstrom scale, the effects of atomic finite sizes and unique entropic interactions cannot be described through simple analytical formulae corresponding to generalized interaction potentials. In this work, all-atom molecular dynamics simulations have been performed on small nanoparticles in order to provide a theoretical background for their interactions with various liquid environments as well as with each other. Such interactions have been quantified and visualized as the processes occur. Potentials of mean force have been computed as functions of the separation distances in order to obtain the binding affinities. The atomistic details of how a nanoparticle interacts with its aqueous environments and with another nanoparticle have been understood for various ligands and aqueous solutions.

  4. The effects of chemical propulsion on the environment

    Science.gov (United States)

    Bennett, R. R.; Hinshaw, J. C.; Barnes, M. W.

    This paper seeks to quantify the effects of chemical propulsion exhaust on both the local launch site and the global environments. Four major areas of concern are discussed: the stratospheric ozone, acid rain, toxicity, and the greenhouse effect. The environmental impacts of both solid and liquid rocket propulsion systems are evaluated. The exhaust species and launch profile of the Space Shuttle, which injects the greatest mass of exhaust products into the atmosphere of any current system, are discussed in some detail. Model calculations predict a global stratospheric ozone reduction of about 0.01% due to chemical propulsion. Acid rain due to the HCl in solid rocket exhaust has a small measurable impact on the local environment, with the mortalities of some plants and small fish very near (<2500 ft) the launch site having been documented. Based on history, the handling of potentially toxic species from the use of chemical propulsion systems is manageable. The relative contribution of chemical propulsion to the global CO 2 burden, the increase of which may lead to global warming, is insignificant. It appears that the perturbation to the natural environment caused by chemical propulsion exhaust is very small and manageable, even for the most optimistic projections of future launch rates.

  5. Photo-transformation of pharmaceutically active compounds in the aqueous environment: a review.

    Science.gov (United States)

    Yan, Shuwen; Song, Weihua

    2014-04-01

    In the past few years, the fate and transportation of pharmaceutically active compounds (PhACs) in aqueous environments have raised significant concerns among the public, scientists and regulatory groups. Photodegradation is an important removal process in surface waters. This review summarizes the last 10 years (2003-2013) of studies on the solar or solar-simulated photodegradation of PhACs in aqueous environments. The PhACs covered include: beta-blockers, antibiotics, non-steroidal anti-inflammatory drugs (NSAIDs), histamine H₂-receptor antagonists, lipid regulators, carbamazepine, steroid hormones, and X-ray contrast media compounds. Kinetic studies, degradation mechanisms and toxicity removal are the three major topics involved in this review. The quantum yield for the direct photolysis of PhACs and the bimolecular reaction rate constants of PhACs with reactive oxygen species (ROS), such as the ˙OH radical and singlet oxygen, are also summarized. This information is not only important to predict the PhAC photodegradation fate, but also is very useful for advanced treatment technologies, such as ozone or advanced oxidation processes.

  6. Effects of Linear Alkylbenzene Sulfonate on Aggregation Behaviors of Titanium Dioxide Nanoparticles in Aqueous Environment

    Institute of Scientific and Technical Information of China (English)

    Xiuheng Wang

    2015-01-01

    In aqueous environment, organic matters may exert impacts on the aggregation behaviors of titanium dioxide nanoparticles ( TiO2⁃NPs). Owing to the deficiency of studies on the aggregation of TiO2⁃NPs in the presence of synthetic organic compound, this study used linear alkylbenzene sulfonate ( LAS) as a representative to evaluate the effects of TiO2⁃NPs concentration (1⁃10 mg/L), LAS concentration (0-1 mg/L), pH (4-8) and ionic strength ( NaCl, CaCl2; 5-20 mM ) during aggregation of TiO2⁃NPs suspensions based on the detection of hydrodynamic diameters and electrophoretic mobilities and the calculation of interaction energies. The results showed that the TiO2⁃NPs in the presence of LAS are more stable than that in the absence of LAS. With the increase of ionic strength, the hydrodynamic diameter of NPs decreases, and the existence of LAS changes the point of zero charge from 5�4 to a lower value and thus alteres the aggregation behaviors of TiO2⁃NPs. The present study suggests that the LAS has a significant impact to the transportation and transformation of nanoparticles in aqueous environment.

  7. Energy band alignment and electronic states of amorphous carbon surfaces in vacuo and in aqueous environment

    Energy Technology Data Exchange (ETDEWEB)

    Caro, Miguel A., E-mail: mcaroba@gmail.com [Department of Electrical Engineering and Automation, Aalto University, Espoo (Finland); Department of Applied Physics, COMP Centre of Excellence in Computational Nanoscience, Aalto University, Espoo (Finland); Määttä, Jukka [Department of Chemistry, Aalto University, Espoo (Finland); Lopez-Acevedo, Olga [Department of Applied Physics, COMP Centre of Excellence in Computational Nanoscience, Aalto University, Espoo (Finland); Laurila, Tomi [Department of Electrical Engineering and Automation, Aalto University, Espoo (Finland)

    2015-01-21

    In this paper, we obtain the energy band positions of amorphous carbon (a–C) surfaces in vacuum and in aqueous environment. The calculations are performed using a combination of (i) classical molecular dynamics (MD), (ii) Kohn-Sham density functional theory with the Perdew-Burke-Ernzerhof (PBE) exchange-correlation functional, and (iii) the screened-exchange hybrid functional of Heyd, Scuseria, and Ernzerhof (HSE). PBE allows an accurate generation of a-C and the evaluation of the local electrostatic potential in the a-C/water system, HSE yields an improved description of energetic positions which is critical in this case, and classical MD enables a computationally affordable description of water. Our explicit calculation shows that, both in vacuo and in aqueous environment, the a-C electronic states available in the region comprised between the H{sub 2}/H{sub 2}O and O{sub 2}/H{sub 2}O levels of water correspond to both occupied and unoccupied states within the a-C pseudogap region. These are localized states associated to sp{sup 2} sites in a-C. The band realignment induces a shift of approximately 300 meV of the a-C energy band positions with respect to the redox levels of water.

  8. Chemical degradation of fluoroelastomer in an alkaline environment

    DEFF Research Database (Denmark)

    Mitra, S.; Ghanbari-Siahkali, A.; Kingshott, P.;

    2004-01-01

    bond formation on the rubber backbone which accelerates the degradation even further with longer exposure. Furthermore, the cross-link sites of the exposed rubber samples are also found to be vulnerable to hydrolytic attack under the studied chemical environment as evidenced by the decrease in cross......We have investigated the time-dependent chemical degradation of a fluoroelastomer, FKM (Viton((R)) A), in an alkaline environment (10% NaOH, 80 degreesC). Optical microscopy and SEM analysis reveal that degradation starts with surface roughness right from the earliest stage of exposure (e.g., 1...... of this surface degradation is found to be strong enough to affect the bulk mechanical properties. The molecular mechanisms of the surface chemical degradation were determined using surface analysis (XPS and ATR-FTIR) where the initial degradation was found to proceed via dehydrofluorination. This leads to double...

  9. Aqueous suspension of anise "Pimpinella anisum" protects rats against chemically induced gastric ulcers

    Institute of Scientific and Technical Information of China (English)

    Ibrahim A Al Mofleh; Abdulqader A Alhaider; Jaber S Mossa; Mohammed O Al-Soohaibani; Syed Rafatullah

    2007-01-01

    AIM:To substantiate the claims of Unani and Arabian traditional medicine practitioners on the gastroprotective potential effect of a popular spice anise,"Pimpinella anisum L." on experimentally-induced gastric ulceration and secretion in rats.METHODS:Acute gastric ulceration in rats was produced by various noxious chemicals including 80% ethanol,0.2 mol/L NaOH,25% NaCl and indomethacin.Anti-secretory studies were undertaken using pylorusligated Shay rat technique.Levels of gastric non-protein sulfhydryls(NP-SH)and wall mucus were estimated and gastric tissue was also examined histologically.Anise aqueous suspension was used in two doses(250 and 500 mg/kg body weight)in all experiments.RESULTS:Anise significantly inhibited gastric mucosal damage induced by necrotizing agents and indomethacin.The anti-ulcer effect was further confirmed histologically.In pylorus-ligated Shay rats,anise suspension significantly reduced the basal gastric acid secretion,acidity and completely inhibited the rumenal ulceration.On the other hand,the suspension significantly replenished ethanol-induced depleted levels of gastric mucosal NP-SH and gastric wall mucus concentration.CONCLUSION:Anise aqueous suspension possesses significant cytoprotective and anti-ulcer activities against experimentally-induced gastric lesions.The anti-ulcer effect of anise is possibly prostaglandin-mediated and/or through its anti-secretory and antioxidative properties.

  10. Removal of methylene blue from aqueous solutions by chemically modified bamboo.

    Science.gov (United States)

    Guo, Jian-Zhong; Li, Bing; Liu, Li; Lv, Kangle

    2014-09-01

    Chemically modified bamboo (CMB) was utilized for removing methylene blue (MB) from aqueous media in the present study. The adsorbent was characterized by Fourier transform infrared (FTIR) spectra and elemental analysis, which confirms that carboxyl groups and diethylenetriamine were successfully introduced into the surface of bamboo. The effects of initial MB concentration (100-900mgL(-1)), contact time (15-315min), the pH of the solution (3-10), temperature (298-318K), adsorbent dosage (0.4-2.6gL(-1)) and salt concentration on the adsorption efficiency of CMB towards MB were investigated. It was found that the adsorption of MB in CMB fits Langmuir mode well, and the maximum adsorption capacity of CMB achieved 606mgg(-1) at 298K, which is much higher than those obtained from previously investigated bioadsorbents. The adsorption kinetics can be described by pseudo-second-order kinetic model, and the adsorption of MB on CMB was an exothermic process. The results of the present study suggest that CMB is an effective biosorbent for removal of organic pollutants from aqueous solutions. Copyright © 2014 Elsevier Ltd. All rights reserved.

  11. As (V) biosorption in an aqueous solution using chemically treated lemon (Citrus aurantifolia Swingle) residues.

    Science.gov (United States)

    Marín-Rangel, Vania Marilyn; Cortés-Martínez, Raúl; Villanueva, Ruth Alfaro Cuevas; Garnica-Romo, Ma Guadalupe; Martínez-Flores, Héctor Eduardo

    2012-01-01

    The use of biosorbents to remove metals and metalloids from contaminated water systems has gained great usage in various parts of the world. The objective of the current study was to test lemon peels as biosorbents for As (V). Lemon peels were chemically characterized and arsenic contact experiments were performed to determine the adsorption capacity of the peels using different empirical models. The model that fit the experimental data was the Lagergren empirical model with a correlation coefficient of R= 0.8841. The results show that lemon peels were able to retain 474.8 μg of As (V)/g of biosorbent. Lemon agro-industrial waste can be useful in the removal of heavy metals, such as arsenic, from aqueous media. © 2011 Institute of Food Technologists®

  12. Chemical Bonding in Aqueous Ferrocyanide: Experimental and Theoretical X-ray Spectroscopic Study

    CERN Document Server

    Engel, Nicholas; Suljoti, Edlira; Garcia-Diez, Raul; Lange, Kathrin M; Atak, Kaan; Golnak, Ronny; Kothe, Alexander; Dantz, Marcus; Kühn, Oliver; Aziz, Emad F

    2013-01-01

    Resonant inelastic X-ray scattering (RIXS) and X-ray absorption (XA) experiments at the iron L- and nitrogen K-edge are combined with high-level first principles restricted active space self-consistent field (RASSCF) calculations for a systematic investigation of the nature of the chemical bond in potassium ferrocyanide in aqueous solution. The atom- and site-specific RIXS excitations allow for direct observation of ligand-to-metal (Fe L-edge) and metal-to-ligand (N K-edge) charge transfer bands and thereby evidence for strong {\\sigma}-donation and {\\pi}-back-donation. The effects are identified by comparing experimental and simulated spectra related to both the unoccupied and occupied molecular orbitals in solution.

  13. Relationship of green chemistry and chemical environment safety management

    Institute of Scientific and Technical Information of China (English)

    NieJL; ShenYW

    2002-01-01

    Green chemistry and chemical environmental safety management are the two important techniques and management means to implement sustainable development policy.They are also the two basic tools to carry out headstream depollution and environmental protection.This paper reviewed the principle of green chemistry and main contents of chemical environment safety management from the point of management toxicity,pointed out the same aim of these two techniques and management measures,and described the foreground of those two sustainable development environmental methods in China.

  14. Responses of polar organic compounds to different ionic environments in aqueous media are interrelated.

    Science.gov (United States)

    Ferreira, L A; Chervenak, A; Placko, S; Kestranek, A; Madeira, P P; Zaslavsky, B Y

    2014-11-14

    Solubilities of 17 polar organic compounds in aqueous solutions of Na2SO4, NaCl, NaClO4, and NaSCN at the salt concentrations of up to 1.0-2.0 M were determined and the Setschenow constant, ksalt, values were estimated. It was found that NaClO4 may display both salting-in and salting-out effects depending on the particular compound structure. The Setschenow constant values for all the polar compounds examined in different salt solutions are found to be interrelated. Similar relationships were observed for partition coefficients of nonionic organic compounds in aqueous polyethylene glycol-sodium sulfate two-phase systems in the presence of different salt additives reported previously [Ferreira et al., J. Chromatogr. A, 2011, 1218, 5031], and for the effects of different salts on optical rotation of amino acids reported by Rossi et al. [J. Phys. Chem. B, 2007, 111, 10510]. In order to explain the observed relationships it is suggested that all the effects observed originate as responses of the compounds to the presence of a given ionic environment and its interaction with the compounds by forming direct or solvent-separated ionic pairs. The response is compound-specific and its strength is determined by the compound structure and the type (and concentration) of ions inducing the response.

  15. Corrosion behavior of technetium waste forms exposed to various aqueous environments

    Energy Technology Data Exchange (ETDEWEB)

    Kolman, David Gary [Los Alamos National Laboratory; Jarvinen, Gordon [Los Alamos National Laboratory; Mausolf, Edward [UNIV OF NEVADA; Czerwinski, Ken [UNIV OF NEVADA; Poineau, Frederic [UNIV OF NEVADA

    2009-01-01

    Technetium is a long-lived beta emitter produced in high yields from uranium as a waste product in spent nuclear fuel and has a high degree of environmental mobility as pertechnetate. It has been proposed that Tc be immobilized into various metallic waste forms to prevent Tc mobility while producing a material that can withstand corrosion exposed to various aqueous medias to prevent the leachability of Tc to the environment over long periods of time. This study investigates the corrosion behavior of Tc and Tc alloyed with 316 stainless steel and Zr exposed to a variety of aqueous media. To date, there is little investigative work related to Tc corrosion behavior and less related to potential Tc containing waste forms. Results indicate that immobilizing Tc into stainless steel-zirconium alloys can be a promising technique to store Tc for long periods of time while reducing the need to separately store used nuclear fuel cladding. Initial results indicate that metallic Tc and its alloys actively corrode in all media. We present preliminary corrosion rates of 100% Tc, 10% Tc - 90% SS{sub 85%}Zr{sub 15%}, and 2% Tc - 98% SS{sub 85%}Zr{sub 15%} in varying concentrations of nitric acid and pH 10 NaOH using the resistance polarization method while observing the trend that higher concentrations of Tc alloyed to the sample tested lowers the corrosion rate of the proposed waste package.

  16. Humic Acid Removal from Aqueous Environments by Electrocoagulation Process Using Iron Electrodes

    Directory of Open Access Journals (Sweden)

    Edris Bazrafshan

    2012-01-01

    Full Text Available At present study the performance of electrocoagulation process using iron electrodes sacrificial anode has been investigated for removal of HA from artificial aqueous solution. The experiments were performed in a bipolar batch reactor with four iron electrode connected in parallel. Several working parameters, such as initial pH (3, 5, 7, and 9, electrical conductivity (50 V and reaction time were studied in an attempt to achieve the highest removal capacity. Solutions of HA with concentration equal 20 mg L-1 were prepared. To follow the progress of the treatment, samples of 10 ml were taken at 15, 30, 45, 60, and 75 min interval. Finally HA concentration was measured by UV absorbance at 254 nm (UV254 and TOC concentration was measured by TOC Analyser. The maximum efficiency of HA removal which was obtained in voltage of 50 V, reaction time of 75 min, initial concentration 20 mg L-1, conductivity 3000 µS/Cm and pH 5, is equal to 92.69%. But for natural water samples at the same optimum condition removal efficiency was low (68.8 %. It can be concluded that the electrocoagulation process has the potential to be utilized for cost-effective removal of HA from aqueous environments.

  17. Identification of the chemical constituents in aqueous extract of Zhi-Qiao and evaluation of its antidepressant effect.

    Science.gov (United States)

    Wu, Ming; Zhang, Hongwu; Zhou, Chao; Jia, Hongmei; Ma, Zhuo; Zou, Zhongmei

    2015-04-16

    The immature fruit of Citrus aurantium L. (Zhi-Qiao, ZQ) has been used as a traditional medicine in China. Our previous study has shown that ZQ decoction may contribute to the antidepressant-like action of Chaihu-Shu-Gan-San. However, there are no reports on the chemical constituents of ZQ aqueous extract or its anti-depression effects. Firstly, this research reported the on-line identification of the chemical constituents in the aqueous extract of ZQ by coupling ultra-performance liquid chromatography/time-of-flight mass spectrometry (UPLC-Q-TOF/MS). A total of 31 chemical constituents were identified in ZQ aqueous extract, including one tannic acid, five flavones, 13 flavanones, one limonoid, three coumarins, three cyclic peptides, and five polymethoxylated flavonoids. The antidepressant effect of ZQ aqueous extract was evaluated in vivo and the results indicated that the mice immobility time during the forced swimming test and the tail suspension test were significantly reduced with ZQ treatment. MTT assays showed both ZQ aqueous extract and its major constituents (naringin, hesperidin, neohesperidin, and nobiletin) had neuroprotective effect on corticosterone-induced neurotoxicity in PC12 cells. The in vivo and in vitro results suggest that ZQ has an antidepressant effect.

  18. Identification of the Chemical Constituents in Aqueous Extract of Zhi-Qiao and Evaluation of Its Antidepressant Effect

    Directory of Open Access Journals (Sweden)

    Ming Wu

    2015-04-01

    Full Text Available The immature fruit of Citrus aurantium L. (Zhi-Qiao, ZQ has been used as a traditional medicine in China. Our previous study has shown that ZQ decoction may contribute to the antidepressant-like action of Chaihu-Shu-Gan-San. However, there are no reports on the chemical constituents of ZQ aqueous extract or its anti-depression effects. Firstly, this research reported the on-line identification of the chemical constituents in the aqueous extract of ZQ by coupling ultra-performance liquid chromatography/time-of-flight mass spectrometry (UPLC-Q-TOF/MS. A total of 31 chemical constituents were identified in ZQ aqueous extract, including one tannic acid, five flavones, 13 flavanones, one limonoid, three coumarins, three cyclic peptides, and five polymethoxylated flavonoids. The antidepressant effect of ZQ aqueous extract was evaluated in vivo and the results indicated that the mice immobility time during the forced swimming test and the tail suspension test were significantly reduced with ZQ treatment. MTT assays showed both ZQ aqueous extract and its major constituents (naringin, hesperidin, neohesperidin, and nobiletin had neuroprotective effect on corticosterone-induced neurotoxicity in PC12 cells. The in vivo and in vitro results suggest that ZQ has an antidepressant effect.

  19. Stress Corrosion Cracking Behavior of Alloy 22 in Multi-Ionic Aqueous Environments

    Energy Technology Data Exchange (ETDEWEB)

    K.J. King; J.C. Estill; R.B. Rebak

    2002-07-15

    The US Department of Energy is characterizing a potential repository site for nuclear waste in Yucca Mountain (NV). In its current design, the nuclear waste containers consist of a double metallic layer. The external layer would be made of NO6022 or Alloy 22 (Ni-22Cr-13Mo-3W-3Fe). Since over their lifetime, the containers may be exposed to multi-ionic aqueous environments, a potential degradation mode of the outer layer could be environmentally assisted cracking (EAC) or stress corrosion cracking (SCC). In general, Alloy 22 is extremely resistant to SCC, especially in concentrated chloride solutions. Current results obtained through slow strain rate testing (SSRT) shows that Alloy 22 may suffer SCC in simulated concentrated water (SCW) at applied potentials approximately 400 mV more anodic than the corrosion potential (E{sub rr}).

  20. On the influence of the environment on galactic chemical abundances

    CERN Document Server

    Pilyugin, L S; Zinchenko, I A; Nefedyev, Y A; Mattsson, L

    2016-01-01

    We examine the influence of the environment on the chemical abundances of late-type galaxies with masses of 10^9.1 M_sun - 10^11 M_sun using data from the Sloan Digital Sky Survey(SDSS). We find that the environmental influence on galactic chemical abundances is strongest for galaxies with masses of 10^9.1 M_sun to 10^9.6 Msun. The galaxies in the densest environments may exceed the average oxygen abundances by about 0.05 dex (the median value of the overabundances for 101 galaxies in the densest environments) and show higher abundances in nitrogen by about 0.1. The abundance excess decreases with increasing galaxy mass and with decreasing environmental density. Since only a small fraction of late-type galaxies is located in high-density environments these galaxies do not have a significant influence on the general X/H - M relation. The metallicity - mass relations for isolated galaxies and for galaxies with neighbors are very similar. The mean shift of non-isolated galaxies around the metallicity - mass rela...

  1. Environment friendly chemoselective deprotection of acetonides and cleavage of acetals and ketals in aqueous medium without using any catalyst or organic solvent

    Indian Academy of Sciences (India)

    S Mukherjee; A Sengupta; S C Roy

    2013-11-01

    Highly chemoselective environment friendly deprotection of acetonides and cleavage of acetals and ketones has been achieved by heating in aqueous medium without using any catalyst and organic solvent.

  2. Aqueous dispersions of few-layer-thick chemically modified magnesium diboride nanosheets by ultrasonication assisted exfoliation

    Science.gov (United States)

    Das, Saroj Kumar; Bedar, Amita; Kannan, Aadithya; Jasuja, Kabeer

    2015-01-01

    The discovery of graphene has led to a rising interest in seeking quasi two-dimensional allotropes of several elements and inorganic compounds. Boron, carbon’s neighbour in the periodic table, presents a curious case in its ability to be structured as graphene. Although it cannot independently constitute a honeycomb planar structure, it forms a graphenic arrangement in association with electron-donor elements. This is exemplified in magnesium diboride (MgB2): an inorganic layered compound comprising boron honeycomb planes alternated by Mg atoms. Till date, MgB2 has been primarily researched for its superconducting properties; it hasn’t been explored for the possibility of its exfoliation. Here we show that ultrasonication of MgB2 in water results in its exfoliation to yield few-layer-thick Mg-deficient hydroxyl-functionalized nanosheets. The hydroxyl groups enable an electrostatically stabilized aqueous dispersion and create a heterogeneity leading to an excitation wavelength dependent photoluminescence. These chemically modified MgB2 nanosheets exhibit an extremely small absorption coefficient of 2.9 ml mg−1 cm−1 compared to graphene and its analogs. This ability to exfoliate MgB2 to yield nanosheets with a chemically modified lattice and properties distinct from the parent material presents a fundamentally new perspective to the science of MgB2 and forms a first foundational step towards exfoliating metal borides. PMID:26041686

  3. Nanoscale carbon materials from hydrocarbons pyrolysis: Structure, chemical behavior, utilisation for non-aqueous supercapacitors

    Energy Technology Data Exchange (ETDEWEB)

    Savilov, Serguei V., E-mail: savilov@chem.msu.ru [Lomonosov Moscow State University, Chemistry Department (Russian Federation); Strokova, Natalia E.; Ivanov, Anton S.; Arkhipova, Ekaterina A. [Lomonosov Moscow State University, Chemistry Department (Russian Federation); Desyatov, Andrey V. [D. Mendeleyev University of Chemical Technology of Russia (Russian Federation); Hui, Xia [Herbert Gleiter Institute of Nanoscience, School of Materials Science and Engineering, Nanjing University of Science and Technology (China); Aldoshin, Serguei M. [Lomonosov Moscow State University, Faculty of Fundamental Physical and Chemical Engineering (Russian Federation); Lunin, Valery V. [Lomonosov Moscow State University, Chemistry Department (Russian Federation)

    2015-09-15

    Highlights: • N-doped and regular carbon nanomaterials were obtained by pyrolitic technique. • Dynamic vapor sorption of different solvents reveals smaller S{sub BET} values. • Steric hindrance and specific chemical interactions are the reasons for this. • Nitrogen doping leads to raise of capacitance and coulombic efficiency with non-aqueous N-containing electrolyte. - Abstract: This work systematically studies adsorption properties of carbon nanomaterials that are synthesized through hydrocarbons that is a powerful technique to fabricate different kinds of carbon materials, e.g., nanotubes, nanoshells, onions, including nitrogen substituted. The adsorption properties of the as-synthesized carbons are achieved by low temperature nitrogen adsorption and organic vapors sorption. Heptane, acetonitrile, water, ethanol, benzene and 1-methylimidazole, which are of great importance for development of supercapacitors, are used as substrates. It is discovered that while nitrogen adsorption reveals a high specific surface area, this parameter for most of organic compounds is rather small depending not only on the size of its molecule but also on chemical interactions for a pair adsorbent–adsorbate. The experimental values of heat of adsorption for carbon and N-substituted structures, when Coulomb cross-coupling of nitrogen atoms in adsorbent and adsorbate takes place, confirms this supposition.

  4. Effect of adsorbents and chemical treatments on the removal of strontium from aqueous solutions.

    Science.gov (United States)

    Ahmadpour, A; Zabihi, M; Tahmasbi, M; Bastami, T Rohani

    2010-10-15

    In the present investigation, three different solid wastes namely almond green hull, eggplant hull, and moss were initially treated and used as adsorbents for the adsorption of strontium ion from aqueous solutions. Adsorbent types and chemical treatments are proved to have effective roles on the adsorption of Sr(II) ion. Among the three adsorbents, almond green hull demonstrated strong affinity toward strontium ion in different solutions. The effectiveness of this new adsorbent was studied in batch adsorption mode under a variety of experimental conditions such as: different chemical treatments, various amounts of adsorbent, and initial metal-ion concentration. The optimum doses of adsorbent for the maximum Sr(II) adsorption were found to be 0.2 and 0.3 g for 45 and 102 mg L(-1) solutions, respectively. High Sr(II) adsorption efficiencies were achieved only in the first 3 min of adsorbent's contact time. The kinetics of Sr(II) adsorption on almond green hull was also examined and it was observed that it follows the pseudo second-order behavior. Both Langmuir and Freundlich models well predicted the experimental adsorption isotherm data. The maximum adsorption capacity on almond green hull was found to be 116.3 mg g(-1). The present study also confirmed that these low cost agriculture byproducts could be used as efficient adsorbents for the removal of strontium from wastewater streams.

  5. Physical and Chemical Transformation of Hydroxyapatite Nanoparticles in Aqueous Sol after Preparation and in vitro

    Institute of Scientific and Technical Information of China (English)

    2005-01-01

    The co-precipitation method followed by ultrasound and heat treatment is a common way to prepare below 100 nm sized hydroxyapatite nanoparticles for biomedical studies and applications. The size and pH value of the obtained calcium phosphate nanoparticles in aqueous sol have a strong impact on the interactions with cells and tissue. The physical and chemical properties of material samples for in vitro and in vivo studies are often assumed to remain constant from the time after fabrication to the actual use. Only little attention is paid to eventual changes of the material over time or due to the different in vitro conditions. In this study, the physical and chemical transformation of calcium phosphate nanoparticles after preparation and in vitro was investigated. As the result showed, dispersed nano sized amorphous calcium phosphate precipitation as well as crystallized hydroxyapatite nanoparticles continue to crystallize even when kept at 4 ℃ leading to declining pH values and particle sizes.Due to the pH buffer in the medium the pH value of the cell culture remained stable after adding 20% nanoparticle sol in vitro. However, hydroxyapatite nanoparticles immediately became unstable in the presents of cell culture medium. The resulting loose agglomerations showed a size of above 500 nm.

  6. Surface acoustic wave sensing of VOCs in harsh chemical environments

    Energy Technology Data Exchange (ETDEWEB)

    Pfeifer, K.B.; Martin, S.J.; Ricco, A.J.

    1993-06-01

    The measurement of VOC concentrations in harsh chemical and physical environments is a formidable task. A surface acoustic wave (SAW) sensor has been designed for this purpose and its construction and testing are described in this paper. Included is a detailed description of the design elements specific to operation in 300{degree}C steam and HCl environments including temperature control, gas handling, and signal processing component descriptions. In addition, laboratory temperature stability was studied and a minimum detection limit was defined for operation in industrial environments. Finally, a description of field tests performed on steam reforming equipment at Synthetica Technologies Inc. of Richmond, CA is given including a report on destruction efficiency of CCl{sub 4} in the Synthetica moving bed evaporator. Design improvements based on the field tests are proposed.

  7. Chemical equilibrium of hydrogen and aqueous solutions of 1 : 1 bicarbonate and formate salts with a common cation

    NARCIS (Netherlands)

    Engel, D.C.; Versteeg, G.F.; Swaaij, W.P.M. van

    1997-01-01

    The chemical equilibrium of hydrogen and aqueous solutions of 1:1 bicarbonate and formate salts with a common cation has been investigated in an intensively stirred batch reactor: MHCO3(aq) + H2(aq) ↔ MOOCH(aq) + H2O(l) This was accomplished for the sodium (M = Na), potassium (M = K) and ammonium (M

  8. Chemical equilibrium of hydrogen and aqueous solutions of 1 : 1 bicarbonate and formate salts with a common cation

    NARCIS (Netherlands)

    Engel, D.C.; Versteeg, G.F.; Swaaij, W.P.M. van

    1997-01-01

    The chemical equilibrium of hydrogen and aqueous solutions of 1:1 bicarbonate and formate salts with a common cation has been investigated in an intensively stirred batch reactor: MHCO3(aq) + H2(aq) ↔ MOOCH(aq) + H2O(l) This was accomplished for the sodium (M = Na), potassium (M = K) and ammonium (M

  9. Evaluating Chemical Persistence in a Multimedia Environment: ACART Analysis

    Energy Technology Data Exchange (ETDEWEB)

    Bennett, D.H.; McKone, T.E.; Kastenberg, W.E.

    1999-02-01

    For the thousands of chemicals continuously released into the environment, it is desirable to make prospective assessments of those likely to be persistent. Persistent chemicals are difficult to remove if adverse health or ecological effects are later discovered. A tiered approach using a classification scheme and a multimedia model for determining persistence is presented. Using specific criteria for persistence, a classification tree is developed to classify a chemical as ''persistent'' or ''non-persistent'' based on the chemical properties. In this approach, the classification is derived from the results of a standardized unit world multimedia model. Thus, the classifications are more robust for multimedia pollutants than classifications using a single medium half-life. The method can be readily implemented and provides insight without requiring extensive and often unavailable data. This method can be used to classify chemicals when only a few properties are known and be used to direct further data collection. Case studies are presented to demonstrate the advantages of the approach.

  10. Preliminary analysis of potential chemical environments inside failed waste containers at the proposed Yucca Mountain repository

    Energy Technology Data Exchange (ETDEWEB)

    Colten-Bradley, V. [Nuclear Regulatory Commission, Rockville, MD (United States); Walton, J.C. [Univ. of Texas, El Paso, TX (United States)

    1994-12-31

    Prediction of radionuclide release rates for high-level waste requires estimates of the rates of waste form alteration and formation of secondary minerals inside the failed canister. Unsaturated repository sites may promote development of a variety of chemical environments related to two phase (liquid/vapor) transport and temperature gradients caused by radiogenic decay. A mass balance (shell balance) approach is used to estimate the effects of dripping water, evaporation, and condensation on the waste canister and the presence of saline water inside the failed waste canister. The simplified calculations predict large variability of water chemistry over spatial scales of a few centimeters. The effects of the predicted aqueous chemistry on waste form alteration, secondary mineral formation, and radionuclide solubility are examined.

  11. On the influence of the environment on galactic chemical abundances

    Science.gov (United States)

    Pilyugin, L. S.; Grebel, E. K.; Zinchenko, I. A.; Nefedyev, Y. A.; Mattsson, L.

    2017-02-01

    We examine the influence of the environment on the chemical abundances of late-type galaxies with masses of 109.1-1011 M⊙ using data from the Sloan Digital Sky Survey. We find that the environmental influence on galactic chemical abundances is strongest for galaxies with masses of 109.1-109.6 M⊙. The galaxies in the densest environments may exceed the average oxygen abundances by about ˜0.05 dex (the median value of the overabundances for 101 galaxies in the densest environments) and show higher abundances in nitrogen by about ˜0.1. The abundance excess decreases with increasing galaxy mass and with decreasing environmental density. Since only a small fraction of late-type galaxies is located in high-density environments, these galaxies do not have a significant influence on the general X/H-M relation. The metallicity-mass relations for isolated galaxies and for galaxies with neighbours are very similar. The mean shift of non-isolated galaxies around the metallicity-mass relation traced by the isolated galaxies is less than ˜0.01 dex for oxygen and less than ˜0.02 dex for nitrogen. The scatter in the galactic chemical abundances is large for any number of neighbour galaxies (at any environmental density), i.e. galaxies with both enhanced and reduced abundances can be found at any environmental density. This suggests that environmental effects do not play a key role in evolution of late-type galaxies, as was also concluded in some of the previous studies.

  12. Enhanced stability and dissolution of CuO nanoparticles by extracellular polymeric substances in aqueous environment

    Energy Technology Data Exchange (ETDEWEB)

    Miao, Lingzhan; Wang, Chao; Hou, Jun, E-mail: hhuhjyhj@126.com; Wang, Peifang; Ao, Yanhui; Li, Yi; Lv, Bowen; Yang, Yangyang; You, Guoxiang; Xu, Yi [Hohai University, Key Laboratory of Integrated Regulation and Resources Development on Shallow Lakes, Ministry of Education (China)

    2015-10-15

    Stability of engineered nanoparticles in aquatic environment is an essential parameter to evaluate their fate, bioavailability, and potential toxic effects toward living organisms. As CuO NPs enter the wastewater systems, they will encounter extracellular polymeric substances (EPS) from microbial community before directly interacting with bacterial cells. EPS may play an important role in affecting the stability and the toxicity of CuO NPs in aquatic environment. In this study, the influences of flocculent sludge-derived EPS, as well as model protein (BSA) and natural polysaccharides (alginate) on the dissolution kinetics and colloidal stability of CuO NPs were investigated. Results showed that the presence of NOMs strongly suppressed CuO NPs aggregation, confirmed by DLS, zeta potentials, and TEM analysis. The enhanced stability of CuO NPs in the presence of EPS and alginate were attributed to the electrostatic combined with steric repulsion, while the steric-hindrance effect may be the predominant mechanism retarding nano-CuO aggregation for BSA. Higher degrees of copper release were achieved with the increasing concentrations of NOMs. EPS are more effective than alginate and BSA in releasing copper, probably due to the abundant functional groups and the excellent metal-binding capacity. The ratio of free-Cu{sup 2+}/total dissolved Cu significantly decreased in the presence of EPS, indicating that EPS may affect the speciation and Cu bioavailability in aqueous environment. These results may be important for assessing the fate and transport behaviors of CuO NPs in the environment as well as for setting up usage regulation and treatment strategy.

  13. A microfluidic device for the continuous culture and analysis of Caenorhabditis elegans in a toxic aqueous environment

    Science.gov (United States)

    Jung, Jaehoon; Nakajima, Masahiro; Tajima, Hirotaka; Huang, Qiang; Fukuda, Toshio

    2013-08-01

    The nematode Caenorhabditis elegans (C. elegans) receives attention as a bioindicator, and the C. elegans condition has been recently analyzed using microfluidic devices equipped with an imaging system. To establish a method without an imaging system, we have proposed a novel microfluidic device with which to analyze the condition of C. elegans from the capacitance change using a pair of micro-electrodes. The device was designed to culture C. elegans, to expose C. elegans to an external stimulus, such as a chemical or toxicant, and to measure the capacitance change which indicates the condition of C. elegans. In this study, to demonstrate the capability of our device in a toxic aqueous environment, the device was applied to examine the effect of cadmium on C. elegans. Thirty L4 larval stage C. elegans were divided into three groups. One group was a control group and the other groups were exposed to cadmium solutions with concentrations of 5% and 10% LC50 for 24 h. The capacitance change and the body volume of C. elegans as a reference were measured four times and we confirmed the correlation between them. It shows that our device can analyze the condition of C. elegans without an imaging system.

  14. Low Pressure Tolerance by Methanogens in an Aqueous Environment: Implications for Subsurface Life on Mars

    Science.gov (United States)

    Mickol, R. L.; Kral, T. A.

    2016-09-01

    The low pressure at the surface of Mars (average: 6 mbar) is one potentially biocidal factor that any extant life on the planet would need to endure. Near subsurface life, while shielded from ultraviolet radiation, would also be exposed to this low pressure environment, as the atmospheric gas-phase pressure increases very gradually with depth. Few studies have focused on low pressure as inhibitory to the growth or survival of organisms. However, recent work has uncovered a potential constraint to bacterial growth below 25 mbar. The study reported here tested the survivability of four methanogen species (Methanothermobacter wolfeii, Methanosarcina barkeri, Methanobacterium formicicum, Methanococcus maripaludis) under low pressure conditions approaching average martian surface pressure (6 mbar - 143 mbar) in an aqueous environment. Each of the four species survived exposure of varying length (3 days - 21 days) at pressures down to 6 mbar. This research is an important stepping-stone to determining if methanogens can actively metabolize/grow under these low pressures. Additionally, the recently discovered recurring slope lineae suggest that liquid water columns may connect the surface to deeper levels in the subsurface. If that is the case, any organism being transported in the water column would encounter the changing pressures during the transport.

  15. Structural and rheological characterizations of nanoparticles of environment-sensitive hydrophobic alginate in aqueous solution.

    Science.gov (United States)

    Chen, Kai; Li, Jiacheng; Feng, Yuhong; He, Furui; Zhou, Qingfeng; Xiao, Dunchao; Tang, Yiyuan

    2017-01-01

    Amphiphilic polymers that form self-assembled structures in aqueous media have been investigated and used for the diagnosis and therapy of various diseases, including cancer. In our work, a series of environment-sensitive hydrophobic alginates (Ugi-Alg) with various weight-average molecular mass values (Mw~6.7×10(5)-6.7×10(4)g/mol) were synthesized via Ugi reaction. The structure of Ugi-Alg was characterized by (1)HNMR spectrometer. The electrostatic self-assembly of different molecular weight (Mw) and composition (M/G ratio) of Ugi-Alg chain under various Na(+) concentrations, was investigated by dynamic light scattering, electron spin resonance experiments, and transmission electron microscopy. Result showed that by comparing to other Ugi-Alg, the mid-Mw Ugi-Alg (Mw~2.8×10(5)g/mol) could form stable and homogeneous nanoparticles in low Na(+) concentration solution. However, G/M values exerted no obvious effect on nanoparticles structure. Additionally, steady-shear flow, thixotropy and dynamical viscoelasticity tests were performed to characterize the rheological behavior of Ugi-Alg aqueous solutions as influenced by Mw and M/G ratio. All of the samples exhibited a non-Newtonian shear-thinning behavior above a critical shear rate (γ̇c2). The greater the Mw, the more sensitive the temperature-dependent behavior will be. The upward-downward rheograms showed that all of the systems evaluated in this study displayed a hysteresis loop, indicating a strong thixotropic behavior, and the thixotropic of mid-Mw Ugi-Alg was the strongest. The dynamical viscoelastic properties were characterized by oscillatory frequency sweep, revealing the gel-like viscoelastic behavior of mid-low Ugi-Alg and the fluid-like viscoelastic behavior of high-Mw Ugi-Alg. Copyright © 2016. Published by Elsevier B.V.

  16. Optimization of chemical and instrumental parameters in hydride generation laser-induced breakdown spectrometry for the determination of arsenic, antimony, lead and germanium in aqueous samples.

    Science.gov (United States)

    Yeşiller, Semira Unal; Yalçın, Serife

    2013-04-03

    A laser induced breakdown spectrometry hyphenated with on-line continuous flow hydride generation sample introduction system, HG-LIBS, has been used for the determination of arsenic, antimony, lead and germanium in aqueous environments. Optimum chemical and instrumental parameters governing chemical hydride generation, laser plasma formation and detection were investigated for each element under argon and nitrogen atmosphere. Arsenic, antimony and germanium have presented strong enhancement in signal strength under argon atmosphere while lead has shown no sensitivity to ambient gas type. Detection limits of 1.1 mg L(-1), 1.0 mg L(-1), 1.3 mg L(-1) and 0.2 mg L(-1) were obtained for As, Sb, Pb and Ge, respectively. Up to 77 times enhancement in detection limit of Pb were obtained, compared to the result obtained from the direct analysis of liquids by LIBS. Applicability of the technique to real water samples was tested through spiking experiments and recoveries higher than 80% were obtained. Results demonstrate that, HG-LIBS approach is suitable for quantitative analysis of toxic elements and sufficiently fast for real time continuous monitoring in aqueous environments.

  17. Self-assembly of folic acid: a chiral-aligning medium for enantiodiscrimination of organic molecules in an aqueous environment.

    Science.gov (United States)

    Lokesh; Suryaprakash, N

    2012-09-10

    Weak orienting medium: Self-assembly of alkaline salt of folic acid yielded a weak liquid-crystalline phase in an aqueous environment. This medium has the ability to discriminate enantiomers. The mesophase exists over a broad range and has the physical parameter dependent tunability of degree of alignment (see scheme).

  18. [Forensic-medical diagnostics of an electrical mark resulting from the injury inflicted by technical electricity in the aqueous environment].

    Science.gov (United States)

    Pigolkin, Iu I; Skovorodnikov, S V; Dubrovin, I A

    2014-01-01

    The objective of the present study was to develop the criteria for forensic-medical diagnostics of an electrical injury inflicted in the aqueous environment based on the characteristics of the electrical mark. The specific morphological features of the electrical injuries inflicted in the aqueous environment that were discovered in the materials available for the forensic medical expertise were analysed taking into consideration the results of the relevant research reported in the forensic medical literature. It was shown that an electrical injury inflicted in the aqueous environment results in the formation of an unusual mark in the form of blisters containing no watery liquid associated with electrogenic oedema in the surrounding tissues. Macroscopic and microscopic studies of the electrical mark failed to reveal the signs of grade III and IV grade thermal burning or thermally affected hair. It is concluded that the consistent characteristics of the electrical mark resulting from the injury inflicted by technical electricity in the aqueous environment include cell lengthening, blister formation inside the corneal layer, and the separation of epidermis from the skin proper.

  19. Probing the elastic response of microalga Scenedesmus dimorphus in dry and aqueous environments through atomic force microscopy

    Energy Technology Data Exchange (ETDEWEB)

    Warren, K. M.; Mpagazehe, J. N.; Higgs, C. F., E-mail: prl@andrew.cmu.edu, E-mail: higgs@andrew.cmu.edu [Department of Mechanical Engineering, Carnegie Mellon University, 5000 Forbes Ave, Pittsburgh, Pennsylvania 15213 (United States); LeDuc, P. R., E-mail: prl@andrew.cmu.edu, E-mail: higgs@andrew.cmu.edu [Department of Mechanical Engineering, Carnegie Mellon University, 5000 Forbes Ave, Pittsburgh, Pennsylvania 15213 (United States); Departments of Biomedical Engineering and Biological Sciences, Carnegie Mellon University, 5000 Forbes Ave., Pittsburgh, Pennsylvania 15213 (United States)

    2014-10-20

    With the re-emergence of microalgae as a replacement feedstock for petroleum-derived oils, researchers are working to understand its chemical and mechanical behavior. In this work, the mechanical properties of microalgae, Scenedesmus dimorphus, were investigated at the subcellular level to determine the elastic response of cells that were in an aqueous and dried state using nano-scale indentation through atomic force microscopy. The elastic modulus of single-celled S. dimorphus cells increased over tenfold from an aqueous state to a dried state, which allows us to better understand the biophysical response of microalgae to stress.

  20. Probing the elastic response of microalga Scenedesmus dimorphus in dry and aqueous environments through atomic force microscopy

    Science.gov (United States)

    Warren, K. M.; Mpagazehe, J. N.; LeDuc, P. R.; Higgs, C. F.

    2014-10-01

    With the re-emergence of microalgae as a replacement feedstock for petroleum-derived oils, researchers are working to understand its chemical and mechanical behavior. In this work, the mechanical properties of microalgae, Scenedesmus dimorphus, were investigated at the subcellular level to determine the elastic response of cells that were in an aqueous and dried state using nano-scale indentation through atomic force microscopy. The elastic modulus of single-celled S. dimorphus cells increased over tenfold from an aqueous state to a dried state, which allows us to better understand the biophysical response of microalgae to stress.

  1. Chemical dosimetry system for γ-ray irradiation based on the formation of phenol from aqueous benzene solutions.

    Science.gov (United States)

    Takeda, Kazuhiko

    2011-01-01

    A chemical dosimetry system based on the radiochemical formation of phenol from aqueous benzene solutions was applied to measure the intensity of γ-ray irradiation. Using a simple and sensitive isocratic fluorometric HPLC system, radiochemically generated phenol was determined. The radiochemical formation of phenol was linear up to 100 Gy and the lower limit of detection calculated from the detection limits of phenol was estimated to be 7 mGy. The phenol formation rates were not affected by the oxygen saturation. The chemical dosimetry system investigated in this study was sensitive and was easier to use than traditional chemical dosimeters.

  2. Optimizing cyanobacteria growth conditions in a sealed environment to enable chemical inhibition tests with volatile chemicals.

    Science.gov (United States)

    Johnson, Tylor J; Zahler, Jacob D; Baldwin, Emily L; Zhou, Ruanbao; Gibbons, William R

    2016-07-01

    Cyanobacteria are currently being engineered to photosynthetically produce next-generation biofuels and high-value chemicals. Many of these chemicals are highly toxic to cyanobacteria, thus strains with increased tolerance need to be developed. The volatility of these chemicals may necessitate that experiments be conducted in a sealed environment to maintain chemical concentrations. Therefore, carbon sources such as NaHCO3 must be used for supporting cyanobacterial growth instead of CO2 sparging. The primary goal of this study was to determine the optimal initial concentration of NaHCO3 for use in growth trials, as well as if daily supplementation of NaHCO3 would allow for increased growth. The secondary goal was to determine the most accurate method to assess growth of Anabaena sp. PCC 7120 in a sealed environment with low biomass titers and small sample volumes. An initial concentration of 0.5g/L NaHCO3 was found to be optimal for cyanobacteria growth, and fed-batch additions of NaHCO3 marginally improved growth. A separate study determined that a sealed test tube environment is necessary to maintain stable titers of volatile chemicals in solution. This study also showed that a SYTO® 9 fluorescence-based assay for cell viability was superior for monitoring filamentous cyanobacterial growth compared to absorbance, chlorophyll α (chl a) content, and biomass content due to its accuracy, small sampling size (100μL), and high throughput capabilities. Therefore, in future chemical inhibition trials, it is recommended that 0.5g/L NaHCO3 is used as the carbon source, and that culture viability is monitored via the SYTO® 9 fluorescence-based assay that requires minimum sample size. Copyright © 2016 Elsevier B.V. All rights reserved.

  3. The Extreme Chemical Environments Associated with Dying Stars

    Science.gov (United States)

    Ziurys, Lucy

    Mass loss from dying stars is the main avenue by which material enters the interstellar medium, and eventually forms solar systems and planets. When stars consume all the hydrogen burning in their core, they start to burn helium, first in their centers, and then in a surrounding shell. During these phases, the so-called ``giant branches,'' large instabilities are created, and stars begin to shed their outer atmospheres, producing so-called circumstellar envelopes. Molecules form readily in these envelopes, in part by LTE chemistry at the base of the stellar photosphere, and also by radical reactions in the outer regions. Eventually most stars shed almost all their mass, creating ``planetary nebulae,'' which consist of a hot, ultraviolet-emitting white dwarf surrounded by the remnant stellar material. The environs in such nebulae are not conducive to chemical synthesis; yet molecular gas exits. The ejecta from these nebulae then flows into the interstellar medium, becoming the starting material for diffuse clouds, which subsequently collapse into dense clouds and then stars. This molecular ``life cycle'' is repeated many times in the course of the evolution of our Galaxy. We have been investigating the interstellar molecular life cycle, in particular the chemical environments of circumstellar shells and planetary nebulae, through both observational and laboratory studies. Using the facilities of the Arizona Radio Observatory (ARO), we have conducted broad-band spectral-line surveys to characterize the contrasting chemical and physical properties of carbon (IRC +10216) vs. oxygen-rich envelopes (VY CMa and NML Cyg). The carbon-rich types are clearly more complex in terms of numbers of chemical compounds, but the O-rich variety appear to have more energetic, shocked material. We have also been conducting surveys of polyatomic molecules towards planetary nebulae. Species such as HCN, HCO+, HNC, CCH, and H2CO appear to be common constituents of these objects, and their

  4. Physical and Chemical Aspects of Fire Suppression in Extraterrestrial Environments

    Science.gov (United States)

    Takahashi, F.; Linteris, G. T.; Katta, V. R.

    2001-01-01

    A fire, whether in a spacecraft or in occupied spaces on extraterrestrial bases, can lead to mission termination or loss of life. While the fire-safety record of US space missions has been excellent, the advent of longer duration missions to Mars, the moon, or aboard the International Space Station (ISS) increases the likelihood of fire events, with more limited mission termination options. The fire safety program of NASA's manned space flight program is based largely upon the principles of controlling the flammability of on-board materials and greatly eliminating sources of ignition. As a result, very little research has been conducted on fire suppression in the microgravity or reduced-gravity environment. The objectives of this study are: to obtain fundamental knowledge of physical and chemical processes of fire suppression, using gravity and oxygen concentration as independent variables to simulate various extraterrestrial environments, including spacecraft and surface bases in Mars and moon missions; to provide rigorous testing of analytical models, which include comprehensive descriptions of combustion and suppression chemistry; and to provide basic research results useful for technological advances in fire safety, including the development of new fire-extinguishing agents and approaches, in the microgravity environment associated with ISS and in the partial-gravity Martian and lunar environments.

  5. Phytotoxic activity and chemical composition of aqueous volatile fractions from Eucalyptus species.

    Directory of Open Access Journals (Sweden)

    Jinbiao Zhang

    Full Text Available The essential oils from four Eucalyptus species (E. spathulata, E. salubris, E. brockwayii and E. dundasii have been previously confirmed to have stronger inhibitory effects on germination and seedling growth of silverleaf nightshade (Solanum elaeagnifolium Cav.. The aqueous volatile fractions (AVFs were the water soluble volatile fractions produced together with the essential oils (water insoluble fractions during the steam distillation process. The aim of this study was to further assess the phytotoxicity of AVFs from the four Eucalyptus species and their chemical composition. The fresh leaves of the four Eucalyptus species were used for the extraction of AVFs. The AVFs were tested for their phytotoxic effects on the perennial weed, silverleaf nightshade under laboratory conditions. The chemical compositions of the AVFs were determined by gas chromatograph-mass spectrometry (GC-MS. Our results showed that the AVFs had strong inhibition on the germination and seedling growth of silverleaf nightshade. The inhibition index increased with the increasing concentrations of AVFs. The inhibitory effects of the AVFs varied between different Eucalyptus species. The AVF from E. salubris demonstrated the highest inhibitory activity on the weed tested, with complete inhibition on germination and seedling growth at a concentration of 75%. The GC-MS analysis revealed that 1,8-cineole, isopentyl isovalerate, isomenthol, pinocarvone, trans-pinocarveol, alpha-terpineol and globulol were the main compounds in the AVFs. These results indicated that all AVFs tested had differential inhibition on the germination and seedling growth of silverleaf nightshade, which could be due to the joint effects of compounds present in the AVFs as these compounds were present in different quantities and ratio between Eucalyptus species.

  6. Phytotoxic activity and chemical composition of aqueous volatile fractions from Eucalyptus species.

    Science.gov (United States)

    Zhang, Jinbiao; An, Min; Wu, Hanwen; Liu, De Li; Stanton, Rex

    2014-01-01

    The essential oils from four Eucalyptus species (E. spathulata, E. salubris, E. brockwayii and E. dundasii) have been previously confirmed to have stronger inhibitory effects on germination and seedling growth of silverleaf nightshade (Solanum elaeagnifolium Cav.). The aqueous volatile fractions (AVFs) were the water soluble volatile fractions produced together with the essential oils (water insoluble fractions) during the steam distillation process. The aim of this study was to further assess the phytotoxicity of AVFs from the four Eucalyptus species and their chemical composition. The fresh leaves of the four Eucalyptus species were used for the extraction of AVFs. The AVFs were tested for their phytotoxic effects on the perennial weed, silverleaf nightshade under laboratory conditions. The chemical compositions of the AVFs were determined by gas chromatograph-mass spectrometry (GC-MS). Our results showed that the AVFs had strong inhibition on the germination and seedling growth of silverleaf nightshade. The inhibition index increased with the increasing concentrations of AVFs. The inhibitory effects of the AVFs varied between different Eucalyptus species. The AVF from E. salubris demonstrated the highest inhibitory activity on the weed tested, with complete inhibition on germination and seedling growth at a concentration of 75%. The GC-MS analysis revealed that 1,8-cineole, isopentyl isovalerate, isomenthol, pinocarvone, trans-pinocarveol, alpha-terpineol and globulol were the main compounds in the AVFs. These results indicated that all AVFs tested had differential inhibition on the germination and seedling growth of silverleaf nightshade, which could be due to the joint effects of compounds present in the AVFs as these compounds were present in different quantities and ratio between Eucalyptus species.

  7. Removal of lead from aqueous solution with native and chemically modified corncobs.

    Science.gov (United States)

    Tan, Guangqun; Yuan, Hongyan; Liu, Yong; Xiao, Dan

    2010-02-15

    In this study, corncobs biomass was utilized as an adsorbent to remove Pb(II) from aqueous solution. The adsorption behavior of Pb(II) was studied under different conditions, including solution pH, contact time and metal concentration. Ground corncobs were modified with CH(3)OH and NaOH to investigate the effect of chemical modification on Pb(II) binding capacity. Results showed that Pb(II) binding on the biomass is pH-dependent and the kinetics can be well described by the Lagergren-second-order model. The maximum Pb(II) binding capacity q(max) calculated from Langmuir isotherm was 0.0783 mmol/g. After base hydrolysis of the biomass, Pb(II) binding capacity increased from 0.0783 to 0.2095 mmol/g (about 43.4 mg Pb/g). However, Pb(II) binding capacity on the esterified corncobs decreased greatly from 0.0783 to 0.0381 mmol/g. Fourier transform infrared spectroscopy (FTIR) analysis showed that hydroxyl and carboxylic (COO(-)) groups on the biomass play an important role in Pb(II) binding process. The X-ray photoelectron spectroscopy (XPS) data further indicated that lead is adsorbed as Pb(2+) and is attached to oxide groups on the biomass.

  8. Organic Redox Species in Aqueous Flow Batteries: Redox Potentials, Chemical Stability and Solubility

    Science.gov (United States)

    Wedege, Kristina; Dražević, Emil; Konya, Denes; Bentien, Anders

    2016-12-01

    Organic molecules are currently investigated as redox species for aqueous low-cost redox flow batteries (RFBs). The envisioned features of using organic redox species are low cost and increased flexibility with respect to tailoring redox potential and solubility from molecular engineering of side groups on the organic redox-active species. In this paper 33, mainly quinone-based, compounds are studied experimentially in terms of pH dependent redox potential, solubility and stability, combined with single cell battery RFB tests on selected redox pairs. Data shows that both the solubility and redox potential are determined by the position of the side groups and only to a small extent by the number of side groups. Additionally, the chemical stability and possible degradation mechanisms leading to capacity loss over time are discussed. The main challenge for the development of all-organic RFBs is to identify a redox pair for the positive side with sufficiently high stability and redox potential that enables battery cell potentials above 1 V.

  9. Ciprofloxacin adsorption from aqueous solution onto chemically prepared carbon from date palm leaflets.

    Science.gov (United States)

    El-Shafey, El-Said Ibrahim; Al-Lawati, Haider; Al-Sumri, Asmaa Soliman

    2012-01-01

    A chemically prepared carbon was synthesized from date palm leaflets via sulphuric acid carbonization at 160 degrees C. Adsorption of ciprofloxacin (CIP) from aqueous solution was investigated in terms of time, pH, concentration, temperature and adsorbent status (wet and dry). The equilibrium time was found to be 48 hr. The adsorption rate was enhanced by raising the temperature for both adsorbents, with adsorption data fitting a pseudo second-order model well. The activation energy, Ea, was found to be 17 kJ/mol, indicating a diffusion-controlled, physical adsorption process. The maximum adsorption was found at initial pH 6. The wet adsorbent showed faster removal with higher uptake than the dry adsorbent, with increased performance as temperature increased (25-45 degrees C). The equilibrium data were found to fit the Langmuir model better than the Freundlich model. The thermodynamic parameters showed that the adsorption process is spontaneous and endothermic. The adsorption mechanism is mainly related to cation exchange and hydrogen bonding.

  10. Ranking of phenols for abiotic oxidation in aqueous environment: a QSPR approach.

    Science.gov (United States)

    Gramatica, Paola; Pilutti, Pamela; Papa, Ester

    2005-01-01

    The limited availability and variability of data related to the overall degradation of compounds in the environment is a very relevant issue in studies related to environmental fate and chemical behavior. The studied phenol data set consists of reaction rate constants of different oxidation reactions in surface waters, available either experimentally or, to fill the data gap, from our QSAR models reported herein. A PCA (Principal Component Analysis) model based on these oxidative degradations has been proposed to evaluate the degradability of chemicals. The score of the first Principal Component is modelled by theoretical molecular descriptors to obtain a multiple linear regression (MLR) model with high predictive power, both internally and externally validated. This modeling approach allows a fast and preliminary ranking of phenols according to their tendency to be degraded by oxidants in water, starting only from knowledge of their molecular structure.

  11. Design of a Wireless Sensor Network for Long-term, In-Situ Monitoring of an Aqueous Environment

    Directory of Open Access Journals (Sweden)

    Craig A. Grimes

    2002-11-01

    Full Text Available An aqueous sensor network is described consisting of an array of sensor nodes that can be randomly distributed throughout a lake or drinking water reservoir. The data of an individual node is transmitted to the host node via acoustic waves using intermediate nodes as relays. Each node of the sensor network is a data router, and contains sensors capable of measuring environmental parameters of interest. Depending upon the required application, each sensor node can be equipped with different types of physical, biological or chemical sensors, allowing long-term, wide area, in situ multi-parameter monitoring. In this work the aqueous sensor network is described, with application to pH measurement using magnetoelastic sensors. Beyond ensuring drinking water safety, possible applications for the aqueous sensor network include advanced industrial process control, monitoring of aquatic biological communities, and monitoring of waste-stream effluents.

  12. Reduction of antitumour mitosenes in non-aqueous and aqueous environment. An electron spin resonance and cyclic voltammetry study

    NARCIS (Netherlands)

    Maliepaard, Marc; de Mol, Nico J.; Janssen, Lambert H.M.; Goeptar, Arnold R.; te Koppele, Johan; Vermeulen, Nico P.E.; Verboom, Willem; Reinhoudt, David

    1995-01-01

    Chemical reduction of mitosenes under aerobic conditions in DMSO showed characteristic ESR signals of the mitosene derived semiquinone free radicals. However, these signals diminished strongly upon addition of water to the reaction mixture, indicating a short lifetime of the mitosene semiquinone

  13. Arsenic(V) biosorption by charred orange peel in aqueous environments.

    Science.gov (United States)

    Abid, Muhammad; Niazi, Nabeel Khan; Bibi, Irshad; Farooqi, Abida; Ok, Yong Sik; Kunhikrishnan, Anitha; Ali, Fawad; Ali, Shafaqat; Igalavithana, Avanthi Deshani; Arshad, Muhammad

    2016-01-01

    Biosorption efficiency of natural orange peel (NOP) and charred orange peel (COP) was examined for the immobilization of arsenate (As(V)) in aqueous environments using batch sorption experiments. Sorption experiments were carried out as a function of pH, time, initial As(V) concentration and biosorbent dose, using NOP and COP (pretreated with sulfuric acid). Arsenate sorption was found to be maximum at pH 6.5, with higher As(V) removal percentage (98%) by COP than NOP (68%) at 4 g L(-1) optimum biosorbent dose. Sorption isotherm data exhibited a higher As(V) sorption (60.9 mg g(-1)) for COP than NOP (32.7 mg g(-1)). Langmuir model provided the best fit to describe As(V) sorption. Fourier transform infrared spectroscopy and scanning electron microscopy combined with energy dispersive X-ray spectroscopy analyses revealed that the -OH, -COOH, and -N-H surface functional groups were involved in As(V) biosorption and the meso- to micro-porous structure of COP sequestered significantly (2-times) higher As(V) than NOP, respectively. Arsenate desorption from COP was found to be lower (10%) than NOP (26%) up to the third regeneration cycle. The results highlight that this method has a great potential to produce unique 'charred' materials from the widely available biowastes, with enhanced As(V) sorption properties.

  14. Adsorptive removal of nickel(II) ions from aqueous environment: A review.

    Science.gov (United States)

    Raval, Nirav P; Shah, Prapti U; Shah, Nisha K

    2016-09-01

    Among various methods adsorption can be efficiently employed for the treatment of heavy metal ions contaminated wastewater. In this context the authors reviewed variety of adsorbents used by various researchers for the removal of nickel(II) ions from aqueous environment. One of the objectives of this review article is to assemble the scattered available enlightenment on a wide range of potentially effective adsorbents for nickel(II) ions removal. This work critically assessed existing knowledge and research on the uptake of nickel by various adsorbents such as activated carbon, non-conventional low-cost materials, nanomaterials, composites and nanocomposites. The system's performance is evaluated with respect to the overall metal removal and the adsorption capacity. In addition, the equilibrium adsorption isotherms, kinetics and thermodynamics data as well as various optimal experimental conditions (solution pH, equilibrium contact time and dosage of adsorbent) of different adsorbents towards Ni(II) ions were also analyzed. It is evident from a literature survey of more than 190 published articles that agricultural solid waste materials, natural materials and biosorbents have demonstrated outstanding adsorption capabilities for Ni(II) ions. Copyright © 2016 Elsevier Ltd. All rights reserved.

  15. PERFORMANCE EVALUATION OF ELECTROCOAGULATION PROCESS FOR DIAZINON REMOVAL FROM AQUEOUS ENVIRONMENTS BY USING IRON ELECTRODES

    Directory of Open Access Journals (Sweden)

    E. Bazrafshan, A. H. Mahvi, S. Nasseri, M. Shaieghi

    2007-04-01

    Full Text Available The present study investigates the removal of pesticide by electrocoagulation process. A glass tank in 1.56 L volume with four iron plate electrodes was used to perform the experiments. The electrodes connected to a DC power supply (bipolar mode. The tank was filled with synthetic wastewater were which contained diazinon pesticide in concentration of 10, 50 and 100 mg/L. The percent of diazinon removal was measured at pH= 3, 7 and 10 and in electric potential range of 20-40V by thin layer chromatography method. The results indicated that initial concentration of diazinon can affect efficiency removal and for higher concentrations of diazinon, higher electrical potential or more reaction time is needed. The results showed that for a given time, the removal efficiency increased significantly with increase of voltage. The highest electrical potential (40V produced the quickest treatment with >99% diazinon reduction occurring after 60 min. The final pH for iron electrodes was always higher than initial pH. Finally it can be concluded that electrocoagulation process (using iron electrodes is a reliable, efficient and cost-effective method for removal of diazinon from aqueous environments, especially designed for pH=3 and voltage=40V.

  16. In Situ Infrared Ellipsometry for Protein Adsorption Studies on Ultrathin Smart Polymer Brushes in Aqueous Environment.

    Science.gov (United States)

    Kroning, Annika; Furchner, Andreas; Aulich, Dennis; Bittrich, Eva; Rauch, Sebastian; Uhlmann, Petra; Eichhorn, Klaus-Jochen; Seeber, Michael; Luzinov, Igor; Kilbey, S Michael; Lokitz, Bradley S; Minko, Sergiy; Hinrichs, Karsten

    2015-06-17

    The protein-adsorbing and -repelling properties of various smart nanometer-thin polymer brushes containing poly(N-isopropylacrylamide) and poly(acrylic acid) with high potential for biosensing and biomedical applications are studied by in situ infrared-spectroscopic ellipsometry (IRSE). IRSE is a highly sensitive nondestructive technique that allows protein adsorption on polymer brushes to be investigated in an aqueous environment as external stimuli, such as temperature and pH, are varied. These changes are relevant to conditions for regulation of protein adsorption and desorption for biotechnology, biocatalysis, and bioanalytical applications. Here brushes are used as model surfaces for controlling protein adsorption of human serum albumin and human fibrinogen. The important finding of this work is that IRSE in the in situ experiments in protein solutions can distinguish between contributions of polymer brushes and proteins. The vibrational bands of the polymers provide insights into the hydration state of the brushes, whereas the protein-specific amide bands are related to changes of the protein secondary structure.

  17. Improved Decontamination: Interfacial Transport, and Chemical Properties of Aqueous Surfactant Cleaners

    Energy Technology Data Exchange (ETDEWEB)

    Robert M. Counce

    2003-05-30

    The aqueous cleaning parameter of interest in this series of studies was the pH of the aqueous cleaning solution. A sessile droplet of industrial quench oil was analyzed to determine the effect of varied solution pH its removal from a stainless steel surface.

  18. Partitioning of Trace Elements Between Hydrous Minerals and Aqueous Fluids : a Contribution to the Chemical Budget of Subduction Zones

    Science.gov (United States)

    Daniel, I.; Koga, K. T.; Reynard, B.; Petitgirard, S.; Chollet, M.; Simionovici, A.

    2006-12-01

    Subduction zones are powerful chemical engines where the downgoing lithosphere reacts with asthenospheric mantle and produces magmas. Understanding this deep recycling system is a scientific challenge requiring multiple approaches. Among those, it appears that we lack basic information on the composition of the fluid that begins the process of material transfer in subduction zones. Indeed, no pristine fluid sample has yet been collected from this particular environment. Albeit challenging, the alternative would be experimental study of fluids under the appropriate conditions. Consequently, we developed an experimental protocol to measure the concentration of aqueous fluids equilibrated with minerals up to pressures (P) of 5 GPa, at least and temperatures (T) of 550 C. This includes syntheses at high-P and -T conditions, and determination of the fluid composition. Syntheses were performed in a large volume belt-type press at the conditions, 2-5 GPa and ca. 550 C. Oxides or minerals were loaded with water in a gold capsule sealed afterwards. Presence of free fluid during experiments could be confirmed by direct observation of fluid release from the sealed capsule upon puncturing. The composition in trace elements of the fluids that were equilibrated at high-P and -T with minerals was reconstructed from that of the precipitates deposited at the surface of minerals after evaporation of the capsule. The precipitates were dissolved and analyzed by a leaching technique detailed in Koga et al. (2005). Two hydrous minerals of prime interest for subductions were sofar investigated: the high-pressure variety of serpentine, antigorite, and talc. The partitioning coefficients of a series of trace-elements will be presented, as well as their evolution as a function of pressure. Consequences for the composition of the fluids released during the dehydration of hydrous metamorphic minerals will be drawn. Those measurements are unlikely to be feasible at pressures in excess of 5 GPa

  19. Mechanisms of Copper Corrosion in Aqueous Environments. A report from the Swedish National Council for Nuclear Waste's scientific workshop, on November 16, 2009

    Energy Technology Data Exchange (ETDEWEB)

    2010-07-01

    In 2010 the Swedish Nuclear Fuel and Waste Management Company, SKB, plans to submit its license application for the final repository of spent nuclear fuel. The proposed method is the so-called KBS-3 method and implies placing the spent nuclear fuel in copper canisters, surrounded by a buffer of bentonite clay, at 500 m depth in the bedrock. The site selected by SKB to host the repository is located in the municipality of Oesthammar on the Swedish east coast. The copper canister plays a key role in the design of the repository for spent nuclear fuel in Sweden. The long-term physical and chemical stability of copper in aqueous environments is fundamental for the safety evolution of the proposed disposal concept. However, the corrosion resistance of copper has been questioned by results obtained under anoxic conditions in aqueous solution. These observations caused some head-lines in the Swedish newspapers as well as public and political concerns. Consequently, the Swedish National Council for Nuclear Waste organized a scientific workshop on the issue 'Mechanisms of Copper Corrosion in Aqueous Environments'. The purpose of the workshop was to address the fundamental understanding of the corrosion characteristics of copper regarding oxygen-free environments, and to identify what additional information is needed to assess the validity of the proposed corrosion mechanism and its implication on the containment of spent nuclear fuel in a copper canister. This seminar report is based on the presentations and discussions at the workshop. It also includes written statements by the members of the expert panel

  20. Sphingosine-1-Phosphate as an Amphipathic Metabolite: Its Properties in Aqueous and Membrane Environments

    Science.gov (United States)

    García-Pacios, Marcos; Collado, M. Isabel; Busto, Jon V.; Sot, Jesús; Alonso, Alicia; Arrondo, José-Luis R.; Goñi, Félix M.

    2009-01-01

    Abstract Sphingosine-1-phosphate (S1P) is currently considered to be an important signaling molecule in cell metabolism. We studied a number of relevant biophysical properties of S1P, using mainly Langmuir balance, differential scanning calorimetry, 31P-NMR, and infrared (IR) spectroscopy. We found that, at variance with other, structurally related sphingolipids that are very hydrophobic, S1P may occur in either an aqueous dispersion or a bilayer environment. S1P behaves in aqueous media as a soluble amphiphile, with a critical micelle concentration of ≈12 μM. Micelles give rise to larger aggregates (in the micrometer size range) at and above a 1 mM concentration. The aggregates display a thermotropic transition at ∼60°C, presumably due to the formation of smaller structures at the higher temperatures. S1P can also be studied in mixtures with phospholipids. Studies with dielaidoylphosphatidylethanolamine (DEPE) or deuterated dipalmitoylphosphatidylcholine (DPPC) show that S1P modifies the gel-fluid transition of the glycerophospholipids, shifting it to lower temperatures and decreasing the transition enthalpy. Low (<10 mol %) concentrations of S1P also have a clear effect on the lamellar-to-inverted hexagonal transition of DEPE, i.e., they increase the transition temperature and stabilize the lamellar versus the inverted hexagonal phase. IR spectroscopy of natural S1P mixed with deuterated DPPC allows the independent observation of transitions in each molecule, and demonstrates the existence of molecular interactions between S1P and the phospholipid at the polar headgroup level that lead to increased hydration of the carbonyl group. The combination of calorimetric, IR, and NMR data allowed the construction of a temperature-composition diagram (“partial phase diagram”) to facilitate a comparative study of the properties of S1P and other related lipids (ceramide and sphingosine) in membranes. In conclusion, two important differences between S1P and ceramide

  1. Hydroxyl radical (OH•) reaction with guanine in an aqueous environment: a DFT study.

    Science.gov (United States)

    Kumar, Anil; Pottiboyina, Venkata; Sevilla, Michael D

    2011-12-22

    The reaction of hydroxyl radical (OH(•)) with DNA accounts for about half of radiation-induced DNA damage in living systems. Previous literature reports point out that the reaction of OH(•) with DNA proceeds mainly through the addition of OH(•) to the C═C bonds of the DNA bases. However, recently it has been reported that the principal reaction of OH(•) with dGuo (deoxyguanosine) is the direct hydrogen atom abstraction from its exocyclic amine group rather than addition of OH(•) to the C═C bonds. In the present work, these two reaction pathways of OH(•) attack on guanine (G) in the presence of water molecules (aqueous environment) are investigated using the density functional theory (DFT) B3LYP method with 6-31G* and 6-31++G** basis sets. The calculations show that the initial addition of the OH(•) at C(4)═C(5) double bond of guanine is barrier free and the adduct radical (G-OH(•)) has only a small activation barrier of ca. 1-6 kcal/mol leading to the formation of a metastable ion-pair intermediate (G(•+)---OH(-)). The formation of ion-pair is a result of the highly oxidizing nature of the OH(•) in aqueous media. The resulting ion-pair (G(•+)---OH(-)) deprotonates to form H(2)O and neutral G radicals favoring G(N(1)-H)(•) with an activation barrier of ca. 5 kcal/mol. The overall process from the G(C(4))-OH(•) (adduct) to G(N(1)-H)(•) and water is found to be exothermic in nature by more than 13 kcal/mol. (G-OH(•)), (G(•+)---OH(-)), and G(N(1)-H)(•) were further characterized by the CAM-B3LYP calculations of their UV-vis spectra and good agreement between theory and experiment is achieved. Our calculations for the direct hydrogen abstraction pathway from N(1) and N(2) sites of guanine by the OH(•) show that this is also a competitive route to produce G(N(2)-H)(•), G(N(1)-H)(•) and H(2)O.

  2. Chemical Vapor Deposition at High Pressure in a Microgravity Environment

    Science.gov (United States)

    McCall, Sonya; Bachmann, Klaus; LeSure, Stacie; Sukidi, Nkadi; Wang, Fuchao

    1999-01-01

    In this paper we present an evaluation of critical requirements of organometallic chemical vapor deposition (OMCVD) at elevated pressure for a channel flow reactor in a microgravity environment. The objective of using high pressure is to maintain single-phase surface composition for materials that have high thermal decomposition pressure at their optimum growth temperature. Access to microgravity is needed to maintain conditions of laminar flow, which is essential for process analysis. Based on ground based observations we present an optimized reactor design for OMCVD at high pressure and reduced gravity. Also, we discuss non-intrusive real-time optical monitoring of flow dynamics coupled to homogeneous gas phase reactions, transport and surface processes. While suborbital flights may suffice for studies of initial stages of heteroepitaxy experiments in space are essential for a complete evaluation of steady-state growth.

  3. The thermo-mechano-chemical twin-screw reactor, a new perspective for the biorefinery of sunflower whole plant : Aqueous extraction of oil and other biopolymers, and production of biodegradable fiberboards from cake

    OpenAIRE

    2016-01-01

    Biorefinery of sunflower whole plant was performed successfully using a thermo-mechano-chemical twin-screw reactor. This led to the aqueous extraction of oil and other biopolymers like proteins, pectins and non pectic sugars. It resulted in the overall fractionation of biomass, thus allowing a complete valorization of the input. This biorefinery process was not only efficient but it was also environment-friendly. In addition, it contributed to the production of different end products for vari...

  4. KDP Aqueous Solution-in-Oil Microemulsion for Ultra-Precision Chemical-Mechanical Polishing of KDP Crystal

    Directory of Open Access Journals (Sweden)

    Hui Dong

    2017-03-01

    Full Text Available A novel functional KH2PO4 (KDP aqueous solution-in-oil (KDP aq/O microemulsion system for KDP crystal ultra-precision chemical-mechanical polishing (CMP was prepared. The system, which consisted of decanol, Triton X-100, and KH2PO4 aqueous solution, was available at room temperature. The functional KDP aq/O microemulsion system was systematically studied and applied as polishing solution to KDP CMP technology. In this study, a controlled deliquescent mechanism was proposed for KDP polishing with the KDP aq/O microemulsion. KDP aqueous solution, the chemical etchant in the polishing process, was caged into the micelles in the microemulsion, leading to a limitation of the reaction between the KDP crystal and KDP aqueous solution only if the microemulsion was deformed under the effect of the external force. Based on the interface reaction dynamics, KDP aqueous solutions with different concentrations (cKDP were applied to replace water in the traditional water-in-oil (W/O microemulsion. The practicability of the controlled deliquescent mechanism was proved by the decreasing material removal rate (MRR with the increasing of the cKDP. As a result, the corrosion pits on the KDP surface were avoided to some degree. Moreover, the roughnesses of KDP with KDP aq/O microemulsion (cKDP was changed from 10 mM to 100 mM as polishing solutions were smaller than that with the W/O microemulsion. The smallest surface root-mean-square roughness of 1.5 nm was obtained at a 30 mmol/L KDP aq solution, because of the most appropriate deliquescent rate and MRR.

  5. Humic Acid Degradation via Solar Photo-Fenton Process in Aqueous Environment

    Directory of Open Access Journals (Sweden)

    Seyed Ali Sajjadi

    2015-08-01

    Full Text Available Control of mutagenic and carcinogenic disinfection by-products, particularly Trihalomethanes (THMs and Halo Acetic Acids (HAAs in water treatment process is critical, due to their adverse effects on human health. Generally, reducing the toxicity of these by-products hinges on prior removal of the precursor materials, such as Humic Acid (HA in drinking water. This study was conducted to investigate the role of some parameters that could affect the removal of HA, including HA (5 and 10 ppm and H2O2 (20, 40, 60, and 80 ppm initial concentrations, Iron (II, sulfate heptahydrate dosage (4, 8, 12, and 16 ppm, pH (2, 3, 4 and 5, Oxidation time (5, 10, 15 and 30 min, and Sunlight levels (322±13 kWm-2. To accelerate the process of HA removal, the Solar Photo-Fenton (SPF process was employed by direct irradiation of converged sunlight in a Parabolic Trough Collectors (PTC, with 3m2 effective area. HA levels were measured via quantifying Dissolved Organic Carbon (DOC concentrations by means of a TOC Analyzer method. The results showed that the SPF process is under control of the Fe & H2O2 ratio, the Fe2+ dosage and especially the pH quantity. In optimal condition, (pH: 4, oxidation time: 30min, initial HA levels: 50 ppm, H2O2 concentrations: 20 ppm Fe+2 levels: 4 ppm, the study found more than 98% DOC removal. In conclusion, the SPF, as an economically effective technique, could be applied for the removal of HA in aqueous environments.

  6. Influence of the Aqueous Environment on Protein Structure—A Plausible Hypothesis Concerning the Mechanism of Amyloidogenesis

    Directory of Open Access Journals (Sweden)

    Irena Roterman

    2016-09-01

    Full Text Available The aqueous environment is a pervasive factor which, in many ways, determines the protein folding process and consequently the activity of proteins. Proteins are unable to perform their function unless immersed in water (membrane proteins excluded from this statement. Tertiary conformational stabilization is dependent on the presence of internal force fields (nonbonding interactions between atoms, as well as an external force field generated by water. The hitherto the unknown structuralization of water as the aqueous environment may be elucidated by analyzing its effects on protein structure and function. Our study is based on the fuzzy oil drop model—a mechanism which describes the formation of a hydrophobic core and attempts to explain the emergence of amyloid-like fibrils. A set of proteins which vary with respect to their fuzzy oil drop status (including titin, transthyretin and a prion protein have been selected for in-depth analysis to suggest the plausible mechanism of amyloidogenesis.

  7. Surface modification on PMMA : PVDF polyblend: hardening under chemical environment

    Indian Academy of Sciences (India)

    R Bajpai; V Mishra; Pragyesh Agrawal; S C Datt

    2002-02-01

    The influence of chemical environment on polymers include the surface alteration as well as other deep modifications in surface layers. The surface hardening, as an effect of organic liquids on poly(methyl methacrylate): poly(vinylidene fluoride) (PMMA: PVDF), which is one of the few known miscible blends, has been detected using microhardness testing. Organic liquids like acetone, toluene, xylene and benzene were introduced on the surface of blend specimens for different durations. Vickers microhardness (v) was measured for treated and untreated specimens. The study reveals both hardening and plasticization of specimens at different exposure times. The degree of surface hardening is maximum under acetone treatment. All the specimens exhibit surface hardening at an exposure time of 1 h with all the four liquids. This feature is prominent with longer exposures for specimens with increasing content of PVDF. However, the degree of hardening decreases with the time of exposure in the respective environments. In general, acetone and toluene impart surface hardening, whereas, xylene and benzene soften the specimen. PMMA: PVDF (83 : 17) blend exhibits surface hardening under all the four treatments when compared with the respective untreated specimens.

  8. NCIP: An Environment-Friendly Chemical Industry Park

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    @@ Nanjing Chemical Industry Park (NCIP) was established in October 2001. The planned area of the park is 45 km2 and the development focus includes oil/ gas chemicals, basic organic chemical raw materials, fine chemicals, polymeric materials, life pharmaceuticals and new chemical materials.

  9. Modeling photodegradation kinetics of three systemic neonicotinoids-dinotefuran, imidacloprid, and thiamethoxam-in aqueous and soil environment.

    Science.gov (United States)

    Kurwadkar, Sudarshan; Evans, Amanda; DeWinne, Dustan; White, Peter; Mitchell, Forrest

    2016-07-01

    Environmental presence and retention of commonly used neonicotinoid insecticides such as dinotefuran (DNT), imidacloprid (IMD), and thiamethoxam (THM) are a cause for concern and prevention because of their potential toxicity to nontarget species. In the present study the kinetics of the photodegradation of these insecticides were investigated in water and soil compartments under natural light conditions. The results suggest that these insecticides are fairly unstable in both aqueous and soil environments when exposed to natural sunlight. All 3 insecticides exhibit strong first-order degradation rate kinetics in the aqueous phase, with rate constants kDNT , kIMD , and kTHM of 0.20 h(-1) , 0.30 h(-1) , and 0.18 h(-1) , respectively. However, in the soil phase, the modeled photodegradation kinetics appear to be biphasic, with optimal rate constants k1DNT and k2DNT of 0.0198 h(-1) and 0.0022 h(-1) and k1THM and k2THM of 0.0053 h(-1) and 0.0014 h(-1) , respectively. Differentially, in the soil phase, imidacloprid appears to follow the first-order rate kinetics with a kIMD of 0.0013 h(-1) . These results indicate that all 3 neonicotinoids are photodegradable, with higher degradation rates in aqueous environments relative to soil environments. In addition, soil-encapsulated imidacloprid appears to degrade slowly compared with dinotefuran and thiamethoxam and does not emulate the faster degradation rates observed in the aqueous phase. Environ Toxicol Chem 2016;35:1718-1726. © 2015 SETAC.

  10. Exploring Atmospheric Aqueous Chemistry (and Secondary Organic Aerosol Formation) through OH Radical Oxidation Experiments, Droplet Evaporation and Chemical Modeling

    Science.gov (United States)

    Turpin, B. J.; Kirkland, J. R.; Lim, Y. B.; Ortiz-Montalvo, D. L.; Sullivan, A.; Häkkinen, S.; Schwier, A. N.; Tan, Y.; McNeill, V. F.; Collett, J. L.; Skog, K.; Keutsch, F. N.; Sareen, N.; Carlton, A. G.; Decesari, S.; Facchini, C.

    2013-12-01

    Gas phase photochemistry fragments and oxidizes organic emissions, making water-soluble organics ubiquitous in the atmosphere. My group and others have found that several water-soluble compounds react further in the aqueous phase forming low volatility products under atmospherically-relevant conditions (i.e., in clouds, fogs and wet aerosols). Thus, secondary organic aerosol can form as a result of gas followed by aqueous chemistry (aqSOA). We have used aqueous OH radical oxidation experiments coupled with product analysis and chemical modeling to validate and refine the aqueous chemistry of glyoxal, methylglyoxal, glycolaldehyde, and acetic acid. The resulting chemical model has provided insights into the differences between oxidation chemistry in clouds and in wet aerosols. Further, we conducted droplet evaporation experiments to characterize the volatility of the products. Most recently, we have conducted aqueous OH radical oxidation experiments with ambient mixtures of water-soluble gases to identify additional atmospherically-important precursors and products. Specifically, we scrubbed water-soluble gases from the ambient air in the Po Valley, Italy using four mist chambers in parallel, operating at 25-30 L min-1. Aqueous OH radical oxidation experiments and control experiments were conducted with these mixtures (total organic carbon ≈ 100 μM-C). OH radicals (3.5E-2 μM [OH] s-1) were generated by photolyzing H2O2. Precursors and products were characterized using electrospray ionization mass spectrometry (ESI-MS), ion chromatography (IC), IC-ESI-MS, and ultra high resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS). Chemical modeling suggests that organic acids (e.g., oxalate, pyruvate, glycolate) are major products of OH radical oxidation at cloud-relevant concentrations, whereas organic radical - radical reactions result in the formation of oligomers in wet aerosols. Products of cloud chemistry and droplet evaporation have

  11. Instroduction of whole technique in chemical environment management

    Institute of Scientific and Technical Information of China (English)

    ShenYW; NieJL

    2002-01-01

    Chemical environmental management is the important works in the environmental protecting regulation of all countries in the world.It mainly includes:chemical testing,testing laboratory quality assurance,good laboratory practices(GLP),chemical inventory,existing chemical risk assessment,new chemical hazardous evaluation,and other administrative management,i.e.chemical risk management,chemical administrative accreditation,chemical decision-making and so on.This paper reviewed the management technical criteria and standards belong to the chemical environmental management in developed countries,and introduced the whole technique in chemical management,described the relationship between those techniques,at last,provided some suggestions about chemical environmental manage ment in China.

  12. Magnesium bicarbonate and carbonate interactions in aqueous solutions: An infrared spectroscopic and quantum chemical study

    Science.gov (United States)

    Stefánsson, Andri; Lemke, Kono H.; Bénézeth, Pascale; Schott, Jacques

    2017-02-01

    The interaction of magnesium with bicarbonate and carbonate ions in aqueous solutions was studied using infrared spectroscopy and quantum chemical calculations. Using the infrared vibrational bands for HCO3- and CO32- at 1200-1450 cm-1 (δC-OH, vS and v3) together with their molar absorptivity (ε), the concentrations of the HCO3- and CO32- ions and the corresponding Mg ion pairs have been determined. In the absence of Mg2+, measured spectra were accurately reproduced assuming that only HCO3- and CO32- were present in solution. Upon addition of Mg2+ at fixed pH, infrared spectra were observed to shift indicating presence of the MgHCO3+ and MgCO3 (aq) ion pairs. From measurements, the second ionization constant of carbonic acid and the MgHCO3+ and MgCO3 (aq) ion pair formation constants have been obtained, these being logK2 = -10.34 ± 0.04, logKMgHCO3+ = 1.12 ± 0.11 and logKMgCO3 = 2.98 ± 0.06, respectively. To support our experimental infrared measurements and to gain further insight into the molecular nature of the ion pair formation, density functional theory (DFT) calculations with VPT2 anharmonic correction were conducted. The most stable geometries predicted for the MgHCO3+ and MgCO3 (aq) ion pairs were a bi-dentate [MgHCO3]+(H2O)n and a monodentate [MgHCO3]+(OH)(H2O)n complexes, respectively. The predicted frequencies for HCO3-, CO32- and MgHCO3+ were found to shift toward those experimentally measured with an increasing H2O solvation number where possible band shifts were predicted for MgCO3 (aq) relative to CO32-, this being dependent on the exact structure and hydration of the bulk MgCO3 (aq) ion pair. Experimentally, the ion pair formations were found to have insignificant effects on the δC-OH, vS and v3 vibrational frequencies. The speciation of dissolved inorganic carbon may be significantly influenced by ion pair formation, particularly in alkaline solutions where they may be the predominant species.

  13. Chemical Potentials, Activity Coefficients, and Solubility in Aqueous NaCl Solutions: Prediction by Polarizable Force Fields.

    Science.gov (United States)

    Moučka, Filip; Nezbeda, Ivo; Smith, William R

    2015-04-14

    We describe a computationally efficient molecular simulation methodology for calculating the concentration dependence of the chemical potentials of both solute and solvent in aqueous electrolyte solutions, based on simulations of the salt chemical potential alone. We use our approach to study the predictions for aqueous NaCl solutions at ambient conditions of these properties by the recently developed polarizable force fields (FFs) AH/BK3 of Kiss and Baranyai (J. Chem. Phys. 2013, 138, 204507) and AH/SWM4-DP of Lamoureux and Roux (J. Phys. Chem. B 2006, 110, 3308 - 3322) and by the nonpolarizable JC FF of Joung and Cheatham tailored to SPC/E water (J. Phys. Chem. B 2008, 112, 9020 - 9041). We also consider their predictions of the concentration dependence of the electrolyte activity coefficient, the crystalline solid chemical potential, the electrolyte solubility, and the solution specific volume. We first highlight the disagreement in the literature concerning calculations of solubility by means of molecular simulation in the case of the JC FF and provide strong evidence of the correctness of our methodology based on recent independently obtained results for this important test case. We then compare the predictions of the three FFs with each other and with experiment and draw conclusions concerning their relative merits, with particular emphasis on the salt chemical potential and activity coefficient vs concentration curves and their derivatives. The latter curves have only previously been available from Kirkwood-Buff integrals, which require approximate numerical integrations over system pair correlation functions at each concentration. Unlike the case of the other FFs, the AH/BK3 curves are nearly parallel to the corresponding experimental curves at moderate and higher concentrations. This leads to an excellent prediction of the water chemical potential via the Gibbs-Duhem equation and enables the activity coefficient curve to be brought into excellent agreement

  14. Removal of Cr(VI from Aqueous Environments Using Micelle-Clay Adsorption

    Directory of Open Access Journals (Sweden)

    Mohannad Qurie

    2013-01-01

    Full Text Available Removal of Cr(VI from aqueous solutions under different conditions was investigated using either clay (montmorillonite or micelle-clay complex, the last obtained by adsorbing critical micelle concentration of octadecyltrimethylammonium ions onto montmorillonite. Batch experiments showed the effects of contact time, adsorbent dosage, and pH on the removal efficiency of Cr(VI from aqueous solutions. Langmuir adsorption isotherm fitted the experimental data giving significant results. Filtration experiments using columns filled with micelle-clay complex mixed with sand were performed to assess Cr(VI removal efficiency under continuous flow at different pH values. The micelle-clay complex used in this study was capable of removing Cr(VI from aqueous solutions without any prior acidification of the sample. Results demonstrated that the removal effectiveness reached nearly 100% when using optimal conditions for both batch and continuous flow techniques.

  15. On the vibrational behavior of single- and double-walled carbon nanotubes under the physical adsorption of biomolecules in the aqueous environment: a molecular dynamics study.

    Science.gov (United States)

    Ajori, S; Ansari, R; Darvizeh, M

    2016-03-01

    The adsorption of biomolecules on the walls of carbon nanotubes (CNTs) in an aqueous environment is of great importance in the field of nanobiotechnology. In this study, molecular dynamics (MD) simulations were performed to understand the mechanical vibrational behavior of single- and double-walled carbon nanotubes (SWCNTs and DWCNTs) under the physical adsorption of four important biomolecules (L-alanine, guanine, thymine, and uracil) in vacuum and an aqueous environment. It was observed that the natural frequencies of these CNTs in vacuum reduce under the physical adsorption of biomolecules. In the aqueous environment, the natural frequency of each pure CNT decreased as compared to its natural frequency in vacuum. It was also found that the frequency shift for functionalized CNTs as compared to pure CNTs in the aqueous environment was dependent on the radius and the number of walls of the CNT, and could be positive or negative.

  16. Iron oxide functionalized graphene nano-composite for dispersive solid phase extraction of chemical warfare agents from aqueous samples.

    Science.gov (United States)

    Chinthakindi, Sridhar; Purohit, Ajay; Singh, Varoon; Tak, Vijay; Goud, D Raghavender; Dubey, D K; Pardasani, Deepak

    2015-05-15

    Present study deals with the preparation and evaluation of graphene based magnetic nano-composite for dispersive solid phase extraction of Chemical Weapons Convention (CWC) relevant chemicals from aqueous samples. Nano-composite, Fe3O4@SiO2-G was synthesized by covalently bonding silica coated Fe3O4 onto the graphene sheets. Nerve agents (NA), Sulfur mustard (SM) and their non-toxic environmental markers were the target analytes. Extraction parameters like amount of sorbent, extraction time and desorption conditions were optimized. Dispersion of 20 milligram of sorbent in 200mL of water sample for 20min. followed by methanol/chloroform extraction produced average to good recoveries (27-94%) of targeted analytes. Recoveries of real agents exhibited great dependency upon sample pH and ionic strength. Sarin produced maximum recovery under mild acidic conditions (56% at pH 5) while VX demanded alkaline media (83% at pH 9). Salts presence in the aqueous samples was found to be advantageous, raising the recoveries to as high as 94% for SM. Excellent limits of detection (LOD) for sulphur mustard and VX (0.11ngmL(-1) and 0.19ngmL(-1) respectively) proved the utility of the developed method for the off-site analysis of CWC relevant chemicals.

  17. Surface Hydrophilicity and Functional Group-Driven Iron(III) Hydroxide Nucleation on Organic-Coated Substrates in Aqueous Environments

    Science.gov (United States)

    Ray, J.; Lee, B.; Baltrusaitis, J.; Jun, Y.

    2012-12-01

    Homogeneous and heterogeneous iron hydroxide nanoparticle nucleation can occur continuously in both natural and complex aqueous systems. Iron oxide nanoparticles can act as sinks and/or carriers for heavy metal contaminants; therefore, it is important to develop a better understanding of factors affecting their formation. Organic coatings are ubiquitous in aqueous environments where they can exist on mineral surfaces (e.g., biofilm), as nanoparticle surface coatings (e.g., natural organic matter), or be introduced as coagulants in water treatment systems. These surface coatings could influence the formation of iron oxide nanoparticles and thus, the mobility of aqueous contaminants. Therefore, to better understand the fate and transport of contaminants in complex aqueous environments, we need more accurate information about mechanisms governing heterogeneous and homogeneous nucleation and growth of iron(III) hydroxide nanoparticles in the presence of organic surface coatings. In this work, we used a unique measurement technique allowing for simultaneous small-angle X-ray scattering (SAXS) and grazing incidence (GISAXS) analysis to monitor nanoparticle nucleation in solution and at substrate surfaces. Clean quartz, and polyaspartate- and alginate-coated substrates were chosen as model substrates to represent mineral coatings, engineered organic coatings and natural organic coatings. Polyaspartate was determined to be the most negatively charged substrate and quartz to be the least negatively charged substrate; however, after 2 h of reaction, the total nanoparticle volume calculations—determined from GISAXS—indicate that precipitation of positively-charged iron(III) hydroxide nanoparticles is 10 times higher on the quartz substrate than on the polyaspartate substrate. This implies that electrostatics do not govern iron(III) hydroxide nucleation. Furthermore, homogeneous nucleation approximately 250 μm above the substrate surface was highest in the presence of the

  18. Preparation of Ultrafine Cobalt Powder by Chemical Reduction in Aqueous Solution

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    Nanocrystalline cobalt powders have been prepared from aqueous solution by reducing their corresponding metal salts under suitable conditions. The experimental conditions have been studied in detail. X-ray powder diffraction patterns show that the cobalt powder is hexagonal crystallite. The average particle size of the ultrafine cobalt powder is 55 nm.

  19. Development of linear free energy relationships for aqueous phase radical-involved chemical reactions.

    Science.gov (United States)

    Minakata, Daisuke; Mezyk, Stephen P; Jones, Jace W; Daws, Brittany R; Crittenden, John C

    2014-12-02

    Aqueous phase advanced oxidation processes (AOPs) produce hydroxyl radicals (HO•) which can completely oxidize electron rich organic compounds. The proper design and operation of AOPs require that we predict the formation and fate of the byproducts and their associated toxicity. Accordingly, there is a need to develop a first-principles kinetic model that can predict the dominant reaction pathways that potentially produce toxic byproducts. We have published some of our efforts on predicting the elementary reaction pathways and the HO• rate constants. Here we develop linear free energy relationships (LFERs) that predict the rate constants for aqueous phase radical reactions. The LFERs relate experimentally obtained kinetic rate constants to quantum mechanically calculated aqueous phase free energies of activation. The LFERs have been applied to 101 reactions, including (1) HO• addition to 15 aromatic compounds; (2) addition of molecular oxygen to 65 carbon-centered aliphatic and cyclohexadienyl radicals; (3) disproportionation of 10 peroxyl radicals, and (4) unimolecular decay of nine peroxyl radicals. The LFERs correlations predict the rate constants within a factor of 2 from the experimental values for HO• reactions and molecular oxygen addition, and a factor of 5 for peroxyl radical reactions. The LFERs and the elementary reaction pathways will enable us to predict the formation and initial fate of the byproducts in AOPs. Furthermore, our methodology can be applied to other environmental processes in which aqueous phase radical-involved reactions occur.

  20. The Behavior of Uranium in the Environment: Bacterial Reduction of an Aqueous Uranium Species.

    Science.gov (United States)

    2000-06-01

    studies used Shewanella putrefaciens because of its ability to grow rapidly in aerobic conditions and reduce metals in anaerobic conditions. Under...anaerobic conditions, Shewanella putrefaciens use aqueous uranium as the electron acceptor in lieu of oxygen. The reduction of U(VI) to U(IV) removes uranium

  1. Heat-activated Plasmonic Chemical Sensors for Harsh Environments

    Energy Technology Data Exchange (ETDEWEB)

    Carpenter, Michael [SUNY Polytechnic Inst., Albany, NY (United States); Oh, Sang-Hyun [Univ. of Minnesota, Minneapolis, MN (United States)

    2015-12-01

    A passive plasmonics based chemical sensing system to be used in harsh operating environments was investigated and developed within this program. The initial proposed technology was based on combining technologies developed at the SUNY Polytechnic Institute Colleges of Nanoscale Science and Engineering (CNSE) and at the University of Minnesota (UM). Specifically, a passive wireless technique developed at UM was to utilize a heat-activated plasmonic design to passively harvest the thermal energy from within a combustion emission stream and convert this into a narrowly focused light source. This plasmonic device was based on a bullseye design patterned into a gold film using focused ion beam methods (FIB). Critical to the design was the use of thermal stabilizing under and overlayers surrounding the gold film. These stabilizing layers were based on both atomic layer deposited films as well as metal laminate layers developed by United Technologies Aerospace Systems (UTAS). While the bullseye design was never able to be thermally stabilized for operating temperatures of 500oC or higher, an alternative energy harvesting design was developed by CNSE within this program. With this new development, plasmonic sensing results are presented where thermal energy is harvested using lithographically patterned Au nanorods, replacing the need for an external incident light source. Gas sensing results using the harvested thermal energy are in good agreement with sensing experiments, which used an external incident light source. Principal Component Analysis (PCA) was used to reduce the wavelength parameter space from 665 variables down to 4 variables with similar levels of demonstrated selectivity. The method was further improved by patterning rods which harvested energy in the near infrared, which led to a factor of 10 decrease in data acquisition times as well as demonstrated selectivity with a reduced wavelength data set. The combination of a plasmonic-based energy harvesting

  2. Mechanisms of chemical vapor generation by aqueous tetrahydridoborate. Recent developments toward the definition of a more general reaction model

    Science.gov (United States)

    D'Ulivo, Alessandro

    2016-05-01

    A reaction model describing the reactivity of metal and semimetal species with aqueous tetrahydridoborate (THB) has been drawn taking into account the mechanism of chemical vapor generation (CVG) of hydrides, recent evidences on the mechanism of interference and formation of byproducts in arsane generation, and other evidences in the field of the synthesis of nanoparticles and catalytic hydrolysis of THB by metal nanoparticles. The new "non-analytical" reaction model is of more general validity than the previously described "analytical" reaction model for CVG. The non-analytical model is valid for reaction of a single analyte with THB and for conditions approaching those typically encountered in the synthesis of nanoparticles and macroprecipitates. It reduces to the previously proposed analytical model under conditions typically employed in CVG for trace analysis (analyte below the μM level, borane/analyte ≫ 103 mol/mol, no interference). The non-analytical reaction model is not able to explain all the interference effects observed in CVG, which can be achieved only by assuming the interaction among the species of reaction pathways of different analytical substrates. The reunification of CVG, the synthesis of nanoparticles by aqueous THB and the catalytic hydrolysis of THB inside a common frame contribute to rationalization of the complex reactivity of aqueous THB with metal and semimetal species.

  3. Performance of Cement-Based Materials in Aggressive Aqueous Environments State-of-the-Art Report, RILEM TC 211 - PAE

    CERN Document Server

    Bertron, Alexandra; Belie, Nele

    2013-01-01

    Concrete and cement-based materials must operate in increasingly aggressive aqueous environments, which may be either natural or industrial.  These materials may suffer degradation in which ion addition and/or ion exchange reactions occur, leading to a breakdown of the matrix microstructure and consequent weakening.  Sometimes this degradation can be extremely rapid and serious such as in acidic environments, while in other cases degradation occurs over long periods.  Consequences of material failure are usually severe – adversely affecting the health and well-being of human communities and disturbing ecological balances. There are also large direct costs of maintaining and replacing deteriorated infrastructure and indirect costs from loss of production during maintenance work, which place a great burden on society. The focus of this book is on addressing issues concerning performance of cement-based materials in aggressive aqueous environments , by way of this State-of-the-Art Report. The book represe...

  4. Prediction of infinite dilution activity coefficients of chlorinated organic compounds in aqueous solution from quantum-chemical descriptors.

    Science.gov (United States)

    Delgado, Eduardo J.; Alderete, Joel B.

    2001-11-30

    A quantitative structure-property relationship (QSPR) model is developed to correlate the natural logarithm of infinite dilution activity coefficients, ln (gamma(infinity)), of 45 chlorinated organic compounds in aqueous solution from quantum-chemical descriptors. The best correlation equation contains five theoretical molecular descriptors. All descriptors were obtained from the chemical structure of the compounds and have definite physical meaning corresponding to different intermolecular interactions. The model predicts ln (gamma(infinity)) with a correlation coefficients of 0.949 and a standard error of 0.442 ln units. The obtained QSPR equation may be applied to the prediction of gamma(infinity) of other chlorinated organic compounds not present in the data set used for the development of the present model. Copyright 2001 John Wiley & Sons, Inc. J Comput Chem 22: 1851-1856, 2001

  5. Control of Convective Dissolution by Chemical Reactions: General Classification and Application to CO2 Dissolution in Reactive Aqueous Solutions

    Science.gov (United States)

    Loodts, V.; Thomas, C.; Rongy, L.; De Wit, A.

    2014-09-01

    In partially miscible two-layer systems within a gravity field, buoyancy-driven convective motions can appear when one phase dissolves with a finite solubility into the other one. We investigate the influence of chemical reactions on such convective dissolution by a linear stability analysis of a reaction-diffusion-convection model. We show theoretically that a chemical reaction can either enhance or decrease the onset time of the convection, depending on the type of density profile building up in time in the reactive solution. We classify the stabilizing and destabilizing scenarios in a parameter space spanned by the solutal Rayleigh numbers. As an example, we experimentally demonstrate the possibility to enhance the convective dissolution of gaseous CO2 in aqueous solutions by a classical acid-base reaction.

  6. Chemical occupational risks identified by nurses in a hospital environment

    OpenAIRE

    Rosicler Xelegati; Maria Lúcia do Carmo Cruz Robazzi; Maria Helena Palucci Marziale; Vanderlei José Haas

    2006-01-01

    Hospital nursing workers are exposed to occupational chemical risks. This quantitative study aimed to identify what chemical substances nurses have contact with in their activities, what substances cause health problems and what alterations correspond to possible problems caused by the chemical products they mention. A self-administered data collection instrument was answered by 53 nurses, who mentioned exposure mainly to antibiotics and benzene (100%), iodine (98.1%) and latex-talc (88.7%); ...

  7. Molecular dynamics simulation study on zwitterionic structure to maintain the natural behavior of polyalanine13 in aqueous environment

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    Molecular dynamics simulations are applied to the initial stage of polyalanine13 conformational transition from α-helix to random coil in aqueous environment and the interaction of polyalanine13 with zwitterionic and hydrophobic surfaces respectively in the same condition. The analysis of secondary structure, hydrogen bonds, RMSD, dihedral distribution, and the degree of adsorption are performed. The results show that zwitterionic structure maintains the natural behavior of polyalanine13 in water to a better extent, which should be an indirect proof of the hypothesis of "maintain of normal structure."

  8. Aggregation of TiO2-graphene nanocomposites in aqueous environment: Influence of environmental factors and UV irradiation.

    Science.gov (United States)

    Hua, Zulin; Zhang, Jianan; Bai, Xue; Ye, Zhengfang; Tang, Zhiqiang; Liang, Lu; Liu, Yuqi

    2016-01-01

    The aggregation kinetics of TiO2-graphene nanocomposites in aqueous solution affected by solution pH, salt types (NaCl, CaCl2) and concentrations of electrolytes, and stability induced by UV irradiation was investigated in this study. The zeta potentials and hydrodynamic diameter of the nanoparticles were used as bases to assess the aggregation behavior, and stability of nanocomposites exposed to UV irradiation was expressed in terms of supernatant concentration. The aggregation of TiO2-graphene nanoparticles in aqueous media followed the colloidal theory. TiO2-graphene nanoparticles were significantly aggregated in the presence of a diavalent cation compared with monovalent cation because the former was more capable of effective charge screening and neutralization. The calculated Hamaker constant of the TiO2-graphene nanocomposites in aqueous solution prepared in the lab was 2.31×10(-20)J. The stability of this composite nanoparticles was between those of pure TiO2 and graphene. A known intensity of UV irradiation was beneficial in the formation of TiO2-graphene nanoparticle aggregates. However, prolonged UV irradiation may stabilize the nanoparticles. These results provided critical information about the colloidal properties of the new TiO2-graphene nanocomposites and were useful in predicting the fate and transport of TiO2-graphene nanocomposites in natural water environments.

  9. Morphology and Optical Properties of Zinc Oxide Films Grown on Metal Coated Glass Substrates by Aqueous Chemical Growth

    Science.gov (United States)

    Bakar, M. A.; Hamid, M. A. A.; Jalar, A.; Shamsudin, R.

    2013-04-01

    Zinc oxide films were deposited on three different metal coated substrates (gold, nickel and platinum) by aqueous chemical growth method. This paper discusses the effect of metal coated substrates on the morphology and optical properties of grown ZnO films. X-Ray Diffraction (XRD), Field Emission Scanning Electron Microscopy (FE-SEM) and UV-visible spectroscopy (UV-vis) were employed to characterize the samples. All the as-deposited ZnO films exhibit crystalline hexagonal wurzite structure. The crystallite size of the ZnO films were in the range of 29 to 32 nm. FESEM micrographs revealed hexagonal rod, oval-like and flower-like ZnO structures formed on all metal coated substrates. The Pt coated film contains higher density hexagonal rod as compared to others metal coated substrate. Most probably the Pt lattice parameter is the nearest to ZnO compared to nickel and gold. The optical band gap energy, Eg of ZnO films were estimated to be 3.30 eV which is near to bulk Eg, 3.37 eV. This indicates that the ZnO grown by aqueous chemical growth is able to produce similar quality properties to other conventional method either films or bulk size.

  10. Photochemical reaction between triclosan and nitrous acid in the atmospheric aqueous environment

    Science.gov (United States)

    Ma, Jianzhong; Zhu, Chengzhu; Lu, Jun; Lei, Yu; Wang, Jizhong; Chen, Tianhu

    2017-05-01

    Nitrous acid (HONO) is an important tropospheric pollutant and a major source of hydroxyl radical in the atmospheric gas phase. However, studies on the role of HONO in atmospheric aqueous phase chemistry processes are relatively few. The present work investigated the photochemical reaction of HONO with triclosan (TCS), which is an emerging contaminant, using a combination of laser flash photolysis spectrometry and gas chromatography mass spectrometry. With these techniques, the reaction pathway of HONO with TCS was proposed by directly monitoring the transient species and detecting the stable products. ·OH was generated from the photodissociation of the HONO aqueous solution and attacked TCS molecules on different sites to produce the TCS-OH adducts with a second-order rate constant of 1.11 × 109 L mol-1 s-1. The ·OH added a C atom adjacent to the ether bond in the aromatic ring of TCS and self-decayed when the ether bond broke. The intermediates generated from the addition of ·OH to the benzene ring of the TCS molecular structure were immediately nitrated by HONO, which played a key role in the formation process of nitrocompounds. An atmospheric model suggests that the aqueous oxidation of TCS by ·OH is a major reaction at high liquid water concentrations, and the photolysis of TCS dominates under low-humidity conditions.

  11. Hydrocarbon adsorption in an aqueous environment: A computational study of alkyls on Cu(111)

    Science.gov (United States)

    Montemore, Matthew M.; Andreussi, Oliviero; Medlin, J. Will

    2016-08-01

    Hydrocarbon chains are important intermediates in various aqueous-phase surface processes, such as CO2 electroreduction, aqueous Fischer-Tropsch synthesis, and aqueous phase reforming of biomass-derived molecules. Further, the interaction between water and adsorbed hydrocarbons represents a difficult case for modern computational methods. Here, we explore various methods for calculating the energetics of this interaction within the framework of density functional theory and explore trade-offs between the use of low water coverages, molecular dynamics approaches, and minima hopping for identification of low energy structures. An effective methodology for simulating low temperature processes is provided by using a unit cell in which the vacuum space is filled with water, employing the minima hopping algorithm to search for low-lying minima, and including dispersion (van der Waals) interactions. Using this methodology, we show that a high coverage of adsorbed alkyls is destabilized by the presence of water, while a low coverage of alkyls is stabilized. Solvation has a small effect on the energetics of hydrocarbon chain growth, generally decreasing its favorability at low temperatures. We studied higher temperatures by running molecular dynamics simulations starting at the minima found by the minima hopping algorithm and found that increased temperatures facilitate chain growth. The self-consistent continuum solvation method effectively describes the alkyl-water interaction and is in general agreement with the explicit solvation results in most cases, but care should be taken at high alkyl coverage.

  12. Chemical compositions of aqueous fluid, silicate melt, and supercritical fluid in the vicinity of the second critical endpoint in the system peridotite-H2O

    Science.gov (United States)

    Mibe, K.; Kawamoto, T.; Ono, S.

    2012-12-01

    Knowing the chemical compositions of fluid and melt is fundamental in understanding the magma genesis and chemical differentiation in the Earth's interior. We investigated the stability fields of aqueous fluid, silicate melt, and supercritical fluid magma using in-situ x-ray radiography and the second critical endpoint in the system peridotite-H2O was determined to be around 3.8 GPa (Mibe et al., 2007, JGR). Using the quenched recovered samples obtained by Mibe et al. (2007), we determined the chemical compositions of aqueous fluid, silicate melt, and supercritical fluid in the vicinity of the second critical endpoint in the system peridotite-H2O by EPMA analyses. A 10- to 30-μm diameter electron beam was used to obtain the composition of quenched materials from aqueous fluid, silicate melt, and supercritical fluid. The compositions of coexisting aqueous fluid and silicate melt were determined at 3.3 GPa and 3.6 GPa and 1180°C. In both samples, olivine coexists with aqueous fluid and silicate melt. In the run at 3.3 GPa, the composition of aqueous fluid was high-Mg dacitic, whereas the composition of silicate melt was hydrous peridotite. In the run at 3.6 GPa, the composition of aqueous fluid was high-Mg andesitic, whereas the composition of silicate melt was hydrous komatiitic. Although aqueous fluids in both runs are high-Mg, both MgO and FeO preferentially enters into silicate melt compared to aqueous fluid.

  13. A purge and trap integrated microGC platform for chemical identification in aqueous samples.

    Science.gov (United States)

    Akbar, Muhammad; Narayanan, Shree; Restaino, Michael; Agah, Masoud

    2014-07-07

    The majority of current micro-scale gas chromatography (μGC) systems focus on air sampling to detect volatile organic compounds (VOCs). However, purging the VOCs from a water sample using microsystems is an unchartered territory. Various organic compounds used in everyday life find their way to water bodies. Some of these water organic compounds (WOCs) persist or degrade slowly, threatening not just human existence but also aquatic life. This article reports the first micro-purge extractor (μPE) chip and its integration with a micro-scale gas chromatography (μGC) system for the extraction and analysis of water organic compounds (WOCs) from aqueous samples. The 2 cm × 3 cm μPE chip contains two inlet and outlet ports and an etched cavity sealed with a Pyrex cover. The aqueous sample is introduced from the top inlet port while a pure inert gas is supplied from the side inlet to purge WOCs from the μPE chip. The outlets are assigned for draining water from the chip and for directing purged WOCs to the micro-thermal preconcentrator (μTPC). The trapped compounds are desorbed from the μTPC by resistive heating using the on-chip heater and temperature sensor, are separated by a 2 m long, 80 μm wide, and 250 μm deep polydimethylsiloxane (OV-1) coated μGC separation column, and are identified using a micro-thermal conductivity detector (μTCD) monolithically integrated with the column. Our experiments indicate that the combined system is capable of providing rapid chromatographic separation (<1.5 min) for quaternary WOCs namely toluene, tetrachloroethylene (PCE), chlorobenzene and ethylbenzene with a minimum detection concentration of 500 parts-per-billion (ppb) in aqueous samples. The proposed method is a promising development towards the future realization of a miniaturized system for sensitive, on-site and real-time field analysis of organic contaminants in water.

  14. Comparison of the Chemical Composition and Pharmacological Effects of the Aqueous and Ethanolic Extracts from a Tibetan “Snow Lotus” (Saussurea laniceps Herb

    Directory of Open Access Journals (Sweden)

    Zhijun Yang

    2012-06-01

    Full Text Available To understand the impacts of different processing methods on the composition and effects of the herb Saussurea laniceps (SL, the present study report the first comparison of the chemical constituents of aqueous and ethanolic SL extracts using chromatographic analysis, and to compare their pharmacological effects in a mouse anti-inflammatory, anti-nociceptive model and an in vitro anti-oxidant test. Chemical comparison demonstrated that the types of chemicals in the two extracts were identical, but the contents of the main constituents in the aqueous extract were lower than those of the ethanolic extract. A transesterification of dicaffeoylquinic acids took place in the aqueous extract during boiling. As for pharmacological effects, oral administration of aqueous and ethanolic SL extracts significantly inhibited croton oil-induced mice ear edema, and significantly inhibited acetic acid-induced mice writhings, respectively. In the DPPH anti-oxidant activity test, the IC50 values were calculated as 409.6 mg/L and 523.4 mg/L for the ethanolic and aqueous extracts, respectively. The inhibitory effects of the ethanolic extract were more potent than those of the aqueous extract in all pharmacological tests, although there was no significant difference. This study suggests that the two preparations should be distinguished when used.

  15. Effect of Fe ion concentration on fatigue life of carbon steel in aqueous CO2 environment

    DEFF Research Database (Denmark)

    Rogowska, Magdalena; Gudme, J.; Rubin, A.

    2016-01-01

    In this work, the corrosion fatigue behaviour of steel armours used in the flexible pipes, in aqueous solutions initially containing different concentrations of Fe2+, was investigated by four-point bending testing under saturated 1 bar CO2 condition. Corrosion fatigue results were supported with ex...... of Fe2+ marginally above the solubility limit of FeCO3 compared to the samples tested in highly supersaturated solution of Fe2+. Results revealed that the impact of the alternating stresses on the corrosion behaviour of samples reduces with lowering the applied stresses. At the stress range of 100 MPa...

  16. Chemical occupational risks identified by nurses in a hospital environment.

    Science.gov (United States)

    Xelegati, Rosicler; Robazzi, Maria Lúcia do Carmo Cruz; Marziale, Maria Helena Palucci; Haas, Vanderlei José

    2006-01-01

    Hospital nursing workers are exposed to occupational chemical risks. This quantitative study aimed to identify what chemical substances nurses have contact with in their activities, what substances cause health problems and what alterations correspond to possible problems caused by the chemical products they mention. A self-administered data collection instrument was answered by 53 nurses, who mentioned exposure mainly to antibiotics and benzene (100%), iodine (98.1%) and latex-talc (88.7%); the main problem-causing substances mentioned were antineoplastic substances (86.7%), glutaraldehyde (79.2%) and ethylene oxide (75.5%); the described health alterations were: eye watering; allergic reactions; nausea and vomiting, while other health problems that can be caused by the above listed products were not mentioned. These workers need further information on occupational chemical risks, which they could have received in undergraduate or permanent education courses.

  17. Radiation chemical studies on thermosensitive N-isopropylacrylamide and its polymer in aqueous solutions.

    Science.gov (United States)

    Acharya, Anjali; Mohan, Hari; Sabharwal, S

    2003-12-01

    The pulse radiolysis technique has been employed to determine the initiation and propagation rates of different transient species involved in the polymerization of N-isopropylacrylamide (NIPA) in aqueous solutions. Polymerization by anionic mechanism has been observed to be faster than by the free-radical mechanism. The kinetic, spectroscopic and redox properties of the transient species formed upon reaction of primary radiolytic species of water radiolysis with NIPA have been evaluated. The one-electron oxidation potential for the formation of a radical cation is quite high (>2 V), but the one-electron reduction potential is low (in the range of -0.3 to -0.7 V). The radical anion of NIPA is able to undergo an electron-transfer reaction with MV(2+), and has a pK(a) value of 3.2. The tert-butyl alcohol radical was also able to initiate polymerization. Gamma radiation-induced polymerization studies showed that the reaction of H(.)/(.)OH/e(aq)(-)/tert-butyl alcohol radicals with NIPA results in a nearly equal yield of the gel fraction. The hydrogel is observed to have very little swelling below pH 3 and above pH 10. The linear polymer of NIPA formed by irradiating dilute aqueous solution is found to be a thermosensitive polymer with lower a critical solution temperature (LCST) of ~33 degrees C. The diameters of polymer molecules were 290 and 20 nm at temperature below and above LCST, respectively.

  18. Physical and chemical interactions at the interface between atmospheric pressure plasmas and aqueous solutions

    Science.gov (United States)

    Lindsay, Alexander; Byrns, Brandon; Knappe, Detlef; Graves, David; Shannon, Steven

    2014-10-01

    Transport and reactions of charged species, neutrals, and photons at the interface between plasmas and liquids must be better quantified. The work presented here combines theoretical and experimental investigations of conditions in the gas and liquid phases in proximity to the interface for various discharges. OES is used to determine rotational and vibrational temperatures of OH, NO, and N2+; the relationship between these temperatures that characterize the distribution of internal energy states and gas and electron kinetic temperatures is considered. The deviation of OH rotational states from equilibrium under high humidity conditions is also presented. In contradiction with findings of other groups, high energy rotational states appear to become underpopulated with increasing humidity. In the aqueous phase, concentrations of longer-lived species such as nitrate, nitrite, hydrogen peroxide, and ozone are determined using ion chromatography and colorimetric methods. Spin-traps and electron paramagnetic resonance (EPR) are investigated for characterization of short-lived aqueous radicals like OH, O2-, NO, and ONOO-. Finally, experimental results are compared to a numerical model which couples transport and reactions within and between the bulk gas and liquid phases.

  19. Changing interfaces: Photoluminescent ZnO nanoparticle powders in different aqueous environments

    Science.gov (United States)

    Kocsis, Krisztina; Niedermaier, Matthias; Bernardi, Johannes; Berger, Thomas; Diwald, Oliver

    2016-10-01

    We transformed vapor phase grown ZnO nanoparticle powders into aqueous ZnO nanoparticle dispersions and studied the impact of associated microstructure and interface property changes on their spectroscopic properties. With photoluminescence (PL) spectroscopy, we probed oxygen interstitials Oi2 - in the near surface region and tracked their specific PL emission response at hvEM = 2.1 eV during the controlled conversion of the solid-vacuum into the solid-liquid interface. While oxygen adsorption via the gas phase does affect the intensity of the PL emission bands, the O2 contact with ZnO nanoparticles across the solid-liquid interface does not. Moreover, we found that the near band edge emission feature at hvEM = 3.2 eV gains relative intensity with regard to the PL emission features in the visible light region. Searching for potential PL indicators that are specific to early stages of particle dissolution, we addressed for aqueous ZnO nanoparticle dispersions the effect of formic acid adsorption. In the absence of related spectroscopic features, we were able to consistently track ZnO nanoparticle dissolution and the concomitant formation of solvated Zinc formate species by means of PL and FT-IR spectroscopy, dynamic light scattering, and zeta potential measurements. For a more consistent and robust assessment of nanoparticle properties in different continuous phases, we discuss characterization challenges and potential pitfalls that arise upon replacing the solid-gas with the solid-liquid interface.

  20. Chemical characterization of the main secondary organic aerosol (SOA products formed through aqueous-phase photonitration of guaiacol

    Directory of Open Access Journals (Sweden)

    Z. Kitanovski

    2014-04-01

    Full Text Available Guaiacol (2-methoxyphenol and its derivatives can be emitted into the atmosphere by thermal degradation (i.e. burning of wood lignins. Due to its volatility, guaiacol is predominantly distributed in the atmospheric gaseous phase. Recent studies have shown the importance of aqueous-phase reactions in addition to the dominant gas-phase and heterogeneous reactions of guaiacol, in the formation of secondary organic aerosol (SOA in the atmosphere. The main objectives of the present study were to chemically characterize the low-volatility SOA products of the aqueous-phase photonitration of guaiacol and examine their possible presence in urban atmospheric aerosols. The aqueous-phase reactions were carried out under simulated sunlight and in the presence of H2O2 and nitrite. The formed guaiacol reaction products were concentrated by using solid-phase extraction (SPE and then purified by means of semi-preparative high-performance liquid chromatography (HPLC. The fractionated individual compounds were isolated as pure solids and further analyzed with liquid-state 1H, 13C and 2D nuclear magnetic resonance (NMR spectroscopy and direct infusion negative ion electrospray ionization tandem mass spectrometry ((–ESI-MS/MS. The NMR and product ion (MS2 spectra were used for unambiguous product structure elucidation. The main products of guaiacol photonitration are 4-nitroguaiacol (4NG, 6-nitroguaiacol (6NG, and 4,6-dinitroguaiacol (4,6DNG. Using the isolated compounds as standards, 4NG and 4,6DNG were unambiguously identified in winter PM10 aerosols from the city of Ljubljana (Slovenia by means of HPLC/(–ESI-MS/MS. Owing to the strong absorption of UV and visible light, 4,6DNG could be an important constituent of atmospheric "brown" carbon, especially in regions affected by biomass burning.

  1. Chemical reactivity of self-organized alumina nanopores in aqueous medium

    Energy Technology Data Exchange (ETDEWEB)

    Rocca, E., E-mail: emmanuel.rocca@lcsm.uhp-nancy.fr [Institut Jean Lamour UMR CNRS 7198, Department CP2S, Nancy University, BP 70239, 54506 Vandoeuvre-les-Nancy (France); Vantelon, D. [Synchrotron Soleil, l' Orme des Merisiers, Saint-Aubin, BP 48, 91192 Gif-sur-Yvette Cedex (France); Gehin, A. [Institut Jean Lamour UMR CNRS 7198, Department CP2S, Nancy University, BP 70239, 54506 Vandoeuvre-les-Nancy (France); Augros, M.; Viola, A. [Messier-Bugatti (Safran Group), 5 Rue Antoine St Exupery, 67129 Molsheim (France)

    2011-02-15

    This work is devoted to the characterization of the structure and chemistry of small self-organized nanopores of aluminum oxide in aqueous medium (diameter <20 nm). A structural model based on AlO{sub 4}/AlO{sub 6} clusters is proposed to describe the amorphous oxide constituting the walls of the nanostructure. X-ray absorption near edge spectroscopy measurements, electrokinetic measurements and O{sup 18} tracer experiments bring to light the structural changes and the specific diffusion mechanism in the nanometer network. Immersion in boiling water induces both the transformation of AlO{sub 4} to AlO{sub 6} clusters and the release of sulfate species by hydrolysis. Water molecules rapidly diffuse in the nanostructure, but ion diffusion is selective because of surface positive charges and overlap of the surface electric field in very small pores.

  2. Multi-Scale Studies of Transport and Adsorption Phenomena of Cement-based Materials in Aqueous and Saline Environment

    Science.gov (United States)

    Yoon, Se Yoon

    The transport and adsorption phenomena in cement-based materials are the most important processes in the durability of concrete structures or nuclear waste containers, as they are precursors to a number of deterioration processes such as chloride-induced corrosion, sulfate attack, carbonation, etc. Despite this importance, our understanding of these processes remains limited because the pore structure and composition of concrete are complex. In addition, the range of the pore sizes, from nanometers to millimeters, requires the multi-scale modeling of the transport and adsorption processes. Among the various environments that cement-based materials are exposed to, aqueous and saline environments represent the most common types. Therefore, this dissertation investigates the adsorption and transport phenomena of cement-based materials exposed to an aqueous and saline environment from atomic to macro-scales using different arrays of novel spectroscopic techniques and simulation methods, such as scanning transmission X-ray microscopy (STXM), X-ray absorption near edge structure (XANES), molecular dynamics (MD), and finite element method (FEM). The structure and transport of water molecules through interlayer spacing of tobermorite was investigated using MD simulations because the interlayer water of calcium silicate hydrate (C-S-H) gel influences various material properties of concrete. The adsorption processes of cementitious phases interacting with sodium and chloride ions at the nano-scale were identified using STXM and XANES measurements. A mathematical model and FEM procedure were developed to identify the effect of surface treatments at macro-scale on ionic transport phenomena of surface-treated concrete. Finally, this dissertation introduced a new material, calcined layered double hydroxide (CLDH), to prevent chloride-induced deterioration.

  3. Atomistic Simulations of Functional Au-144(SR)(60) Gold Nanoparticles in Aqueous Environment

    DEFF Research Database (Denmark)

    Heikkila, E.; Gurtovenko, A. A.; Martinez-Seara, H.

    2012-01-01

    Charged monolayer-protected gold nanoparticles (AuNPs) have been studied in aqueous solution by performing atomistic molecular dynamics simulations at physiological temperature (310 K). Particular attention has been paid to electrostatic properties that modulate the formation of a complex comprised...... of the nanoparticle together with surrounding ions and water. We focus on Au-144 nanoparticles that comprise a nearly spherical Au core (diameter similar to 2 nm), a passivating Au-S interface, and functionalized alkanethiol chains. Cationic and anionic AuNPs have been modeled with amine and carboxyl terminal groups...... potential displays a minimum for AuNP- at 1.9 nm from the center of the nanoparticle, marking a preferable location for Na+, while the AuNP+ potential (affecting the distribution of Cl-) rises almost monotonically with a local maximum. Comparison to Debye-Huckel theory shows very good agreement for radial...

  4. Nanofiltration and sensing of picomolar chemical residues in aqueous solution using an optical porous resonator in a microelectrofluidic channel

    Science.gov (United States)

    Huang, Lei; Guo, Zhixiong

    2012-02-01

    For the first time the use of a porous microresonator placed in a microelectrofluidic system for integrated functions of nanofiltration and sensing of small biomolecules and chemical analytes in extremely dilute solution was proposed and investigated. As an example, aminoglycosides in drug residues in food and livestock products were considered as the trace chemical analyte. The filtration process of the charged analyte in aqueous solution driven by an applied electrical field and the accompanying optical whispering-gallery modes in the resonator are modeled. The dynamic process of adsorption and desorption of the analyte onto the porous matrix is studied. Deposition of the analyte inside the porous structure will alter the material refractive index of the resonator, and thus induce an optical resonance frequency shift. By measuring the optical frequency shift, the analyte concentration as well as the absorption/desorption process can be analyzed. Through an intensive numerical study, a correlation between the frequency shift and the analyte concentration and the applied electrical voltage gradient was obtained. This reveals a linear relationship between the resonance frequency shift and the analyte concentration. The applied electrical voltage substantially enhances the filtration capability and the magnitude of the optical frequency shift, pushing the porous resonator-based sensor to function at the extremely dilute picomolar concentration level for small bio/chemical molecules down to the sub-nanometer scale. Moreover, use of the second-order whispering-gallery mode is found to provide better sensitivity compared with the first-order mode.

  5. Chemical and structural evaluation of activated carbon prepared from jute sticks for Brilliant Green dye removal from aqueous solution.

    Science.gov (United States)

    Asadullah, Mohammad; Asaduzzaman, Mohammad; Kabir, Mohammad Shajahan; Mostofa, Mohammad Golam; Miyazawa, Tomohisa

    2010-02-15

    Activated carbons have been prepared from jute sticks by chemical activation using ZnCl(2) and physical activation using steam for the removal of Brilliant Green dye from aqueous solution. The activated carbons and charcoal prepared from jute sticks were characterized by evaluating the surface chemistry, structural features and surface morphology. The maximum BET surface area was obtained to be 2304 m(2)/g for chemical activated carbon (ACC) while it is 730 and 80 m(2)/g for steam activated carbon (ACS) and charcoal, respectively. The FT-IR spectra exhibited that the pyrolysis and steam activation of jute sticks resulted in the release of aliphatic and O-containing functional groups by thermal effect. However, the release of functional groups is the effect of chemical reaction in the ZnCl(2) activation process. A honeycomb-type carbon structure in ACC was formed as observed on SEM images. Although charcoal and ACC were prepared at 500 degrees C the ACC exhibited much lower Raman sensitivity due to the formation of condensed aromatic ring systems. Due to high surface area and high porous structure with abundance of functional groups, the ACC adsorbed dye molecules with much higher efficiency than those of ACS and charcoal.

  6. Atmospheric pressure resistive barrier air plasma jet induced bacterial inactivation in aqueous environment

    Science.gov (United States)

    Thiyagarajan, Magesh; Sarani, Abdollah; Gonzales, Xavier

    2013-03-01

    An atmospheric pressure resistive barrier air plasma jet is designed to inactivate bacteria in aqueous media in direct and indirect exposure modes of treatment. The resistive barrier plasma jet is designed to operate at both dc and standard 50-60 Hz low frequency ac power input and the ambient air at 50% humidity level was used as the operating gas. The voltage-current characteristics of the plasma jet were analyzed and the operating frequency of the discharge was measured to be 20 kHz and the plasma power was measured to be 26 W. The plasma jet rotational temperatures (Trot) are obtained from the optical emission spectra, from the N2C-B(2+) transitions by matching the experimental spectrum results with the Spectra Air (SPECAIR) simulation spectra. The reactive oxygen and nitrogen species were measured using optical emission spectroscopy and gas analyzers, for direct and indirect treatment modes. The nitric oxides (NO) were observed to be the predominant long lived reactive nitrogen species produced by the plasma. Three different bacteria including Staphylococcus aureus (Gram-positive), Escherichia coli (Gram-negative), and Neisseria meningitidis (Gram-negative) were suspended in an aqueous media and treated by the resistive barrier air plasma jet in direct and indirect exposure modes. The results show that a near complete bacterial inactivation was achieved within 120 s for both direct and indirect plasma treatment of S. aureus and E. coli bacteria. Conversely, a partial inactivation of N. meningitidis was observed by 120 s direct plasma exposure and insignificant inactivation was observed for the indirect plasma exposure treatment. Plasma induced shifts in N. meningitidis gene expression was analyzed using pilC gene expression as a representative gene and the results showed a reduction in the expression of the pilC gene compared to untreated samples suggesting that the observed protection against NO may be regulated by other genes.

  7. Aqueous-Phase Catalytic Chemical Reduction of p-Nitrophenol Employing Soluble Gold Nanoparticles with Different Shapes

    Directory of Open Access Journals (Sweden)

    Francyelle Moura de Oliveira

    2016-12-01

    Full Text Available Gold nanoparticles with different shapes were prepared and used as catalysts in the reduction of p-nitrophenol (PNP in the aqueous phase and in the presence of sodium borohydride (NaBH4. Parameters such as the reaction temperature, substrate/NaBH4 molar ratio, and substrate/gold molar ratio were tested and evaluated. In this paper, we compare the catalytic reactivities of gold nanorods (AuNRs and gold nanospheres (AuNSs, both synthesized by the seed-mediated method in the presence of cetyltrimethyl ammonium bromide (CTAB. Physical-chemical parameters such as the apparent rate constant (kapp and activation energy (Ea of the reactions were obtained for both systems. We observed that the catalytic system based on AuNRs is the most active. These colloidal dispersions were investigated and fully characterized by ultraviolet-visible absorption spectroscopy (UV–Vis and transmission electron microscopy (TEM.

  8. Effect of hydrothermal treatment with different aqueous solutions on the mold resistance of moso bamboo with chemical and FTIR analysis

    Directory of Open Access Journals (Sweden)

    Dali Cheng

    2013-02-01

    Full Text Available Bamboo has received increased attention as a biomass material because it is fast growing and has good mechanical properties. But bamboo is very vulnerable to mold fungi, which greatly limits its applications. In this paper, bamboo was firstly hydrothermally treated at 140 °C by three different treatments: with water only, NaOH, and NaAc aqueous solution, then heat treated at relatively mild conditions (180 °C. Subsequently, the mold resistance of bamboo before and after the two-step heat treatment was investigated. The mechanism of mold resistance was analyzed by a bamboo chemical component analysis, FTIR spectroscopy. The results showed that strong degradation of hemicelluloses by heat treatment could inhibit mold growth to some extent. Moreover, the modification of lignin and the creation of phenolic compounds in the bamboo could prevent or slow down fungal growth.

  9. An Optical Fiber-Based Sensor Array for the Monitoring of Zinc and Copper Ions in Aqueous Environments

    Directory of Open Access Journals (Sweden)

    Steven Kopitzke

    2014-02-01

    Full Text Available Copper and zinc are elements commonly used in industrial applications as aqueous solutions. Before the solutions can be discharged into civil or native waterways, waste treatment processes must be undertaken to ensure compliance with government guidelines restricting the concentration of ions discharged in solution. While currently there are methods of analysis available to monitor these solutions, each method has disadvantages, be it high costs, inaccuracy, and/or being time-consuming. In this work, a new optical fiber-based platform capable of providing fast and accurate results when performing solution analysis for these metals is described. Fluorescent compounds that exhibit a high sensitivity and selectivity for either zinc or copper have been employed for fabricating the sensors. These sensors demonstrated sub-part-per-million detection limits, 30-second response times, and the ability to analyze samples with an average error of under 10%. The inclusion of a fluorescent compound as a reference material to compensate for fluctuations from pulsed excitation sources has further increased the reliability and accuracy of each sensor. Finally, after developing sensors capable of monitoring zinc and copper individually, these sensors are combined to form a single optical fiber sensor array capable of simultaneously monitoring concentration changes in zinc and copper in aqueous environments.

  10. Model Experiments on Chemical Properties of Superheavy Elements in Aqueous Solutions

    CERN Document Server

    Szeglowski, Z

    2003-01-01

    This paper presents a brief review of model experiments on investigation of chemical properties of transactinide elements, ranging from 104 to 116. The possibilities of isolation of the nuclei of these elements from nuclear reaction products, using the ion-exchange method, are also considered.

  11. Calculations of hyperfine coupling constant of copper(II) in aqueous environment. Finite temperature molecular dynamics and relativistic effects.

    Science.gov (United States)

    Malček, Michal; Bučinský, Lukáš; Valko, Marián; Biskupič, Stanislav

    2015-09-01

    The presented paper is focused on the calculation of hyperfine coupling constants (HFCC) of Cu (2+) ion in water environment. To simulate the conditions of the electron paramagnetic resonance (EPR) experiment in aqueous phase, molecular dynamics using the density functional theory (DFT) was employed. In total three different functionals (BLYP, B3LYP, M06) were employed for studying their suitability in describing coordination of Cu (2+) by water molecules. The system of our interest was composed of one Cu (2+) cation surrounded by a selected number (between thirty and fifty) of water molecules. Besides the non-relativistic HFCCs (Fermi contact terms) of Cu (2+) also the four-component relativistic HFCC calculations are presented. The importance of the proper evaluation of HFCCs, the inclusion of spin-orbit term, for Cu (2+) containing systems (Neese, J. Chem. Phys. 118, 3939 2003; Almeida et al., Chem. Phys. 332, 176 2007) is confirmed at the relativistic four-component level of theory.

  12. Effect of silty sand with different sizes on corrosion behavior of 3Cr steel in CO2 aqueous environment

    Science.gov (United States)

    Liu, Wei; Lu, Songle; Zhang, Peng; Dou, Juanjuan; Zhao, Qinghe

    2016-08-01

    Corrosion behavior of 3Cr steel in CO2 aqueous environment containing silty sand was investigated by immersion test. The results show that CO2 corrosion rate and morphology of 3Cr steel were obviously affected by the size of silty sand. 5000 mesh silty sand mixed with corrosion products, forming compact Cr-rich corrosion scale and resulting in low corrosion rate and uniform corrosion. 1000 mesh silty sand mixed with corrosion products, forming porous corrosion scale without Cr enrichment and resulting in high corrosion rate and pitting corrosion. 5000 mesh silty sand enhanced Cr enrichment in corrosion scale, leading to low anodic current. However, 1000 mesh silty sand deteriorated Cr enrichment in corrosion scale, leading to high anodic current. Cathodic current was reduced by silty sand, but was not affected by two sizes of silty sand. Cr enrichment in corrosion scale of 3Cr steel was obviously affected by separation effect of silty sand.

  13. Applicability of concentrations obtained by working environment measurement to assessment of personal exposure concentrations of chemicals.

    Science.gov (United States)

    Yamamoto, Shinobu; Natsumeda, Shuichiro; Hara, Kunio; Yoshida, Satoru; Sakurai, Haruhiko; Ichiba, Masayoshi

    2014-01-01

    This study determined the applicability of Japanese working environment measurements to assessment of personal exposure concentrations of chemicals by comparing both levels of concentrations. The chemicals measured in this study comprised eight kinds of vaporous chemicals as well as two kinds of chemicals in dust. Personal exposure measurements, Japanese working environment measurements and spot sampling measurements were undertaken in 70 companies. Personal exposure concentrations and the arithmetic mean value (EA2) of the working environment measurement concentrations obtained according to the Japanese working environment control system had statistically positive correlations (r=0.732-0.893, pvalues of personal exposure concentrations divided by EA2 ranged from 0.17 to 7.69 for vaporous chemicals and from 0.27 to 18.06 for dust. There was a relatively large difference between the personal exposure concentrations and the EA2 obtained in weighing, forming and bonding use-processes. In such cases, the B-value measured in ten minutes in the Japanese working environment control system, which is almost the same as the spot measurement concentration in this study, is supposed to be substituted for the EA2 value. Ten times the EA2 of the working environment measurement concentrations, or ten times the B-value, obtained according to the Japanese working environment control system can be used to conservatively estimate the personal exposure concentrations in EU workplaces as well as in occupational exposure scenarios of the Regulation on Registration, Evaluation, Authorisation and Restriction of Chemicals.

  14. Aqueous acidities of primary benzenesulfonamides: Quantum chemical predictions based on density functional theory and SMD.

    Science.gov (United States)

    Aidas, Kęstutis; Lanevskij, Kiril; Kubilius, Rytis; Juška, Liutauras; Petkevičius, Daumantas; Japertas, Pranas

    2015-11-05

    Aqueous pK(a) of selected primary benzenesulfonamides are predicted in a systematic manner using density functional theory methods and the SMD solvent model together with direct and proton exchange thermodynamic cycles. Some test calculations were also performed using high-level composite CBS-QB3 approach. The direct scheme generally does not yield a satisfactory agreement between calculated and measured acidities due to a severe overestimation of the Gibbs free energy changes of the gas-phase deprotonation reaction by the used exchange-correlation functionals. The relative pK(a) values calculated using proton exchange method compare to experimental data very well in both qualitative and quantitative terms, with a mean absolute error of about 0.4 pK(a) units. To achieve this accuracy, we find it mandatory to perform geometry optimization of the neutral and anionic species in the gas and solution phases separately, because different conformations are stabilized in these two cases. We have attempted to evaluate the effect of the conformer-averaged free energies in the pK(a) predictions, and the general conclusion is that this procedure is highly too costly as compared with the very small improvement we have gained.

  15. Sequence-Fenton Reaction for Decreasing Phenol Formation during Benzene Chemical Conversion in Aqueous Solutions

    Directory of Open Access Journals (Sweden)

    SB Mortazavi, A Sabzali, A Rezaee

    2005-04-01

    Full Text Available Advanced oxidation processes such as Fenton reagent generates highly reactive hydroxyl free radicals to oxidize various compounds in the water and wastewater. The efficiency of different Fenton-related oxidative processes such as Fenton, solar-Fenton, UV-Fenton and Fenton reactions in different batch reactors was examined using benzene as pollutant in aqueous solutions. A batch study was conducted to optimize parameters like pH, hydrogen peroxide concentration, temperature, reaction time and ferrous ion concentration governing the Fenton process. The concentrations of produced phenol were measured at the end of the reactions. The role of sequence reaction was tested for decreasing phenol formation during benzene conversion. At optimum conditions, different Fenton-related processes were compared for the degradation of benzene. Increased degradation efficiency was observed in photo-Fenton processes as compared to conventional Fenton process. The formation of phenol in Fenton reaction depended on reaction time, sequence in reaction, purity of hydrogen peroxide and other compounds such as alcohols that contributed into the reaction. In the Fenton process, carboxylic acids like acetic acid and oxalic acid were formed as the end products during the complete degradation of benzene. With the increase in mono-valence, two-valence ions and hardness, Fenton's efficiency decreased, respectively. Sequence Fenton reaction produced less phenol and its end products had smaller COD as compared to conventional Fenton process.

  16. Structural, chemical and optical evaluation of Cu-doped ZnO nanoparticles synthesized by an aqueous solution method

    Energy Technology Data Exchange (ETDEWEB)

    Iribarren, A., E-mail: augusto@imre.oc.uh.cu [Instituto de Ciencia y Tecnología de Materiales (IMRE), Universidad de La Habana, Zapata y G, Vedado, Plaza, La Habana 10400 (Cuba); Hernández-Rodríguez, E. [Instituto de Ciencia y Tecnología de Materiales (IMRE), Universidad de La Habana, Zapata y G, Vedado, Plaza, La Habana 10400 (Cuba); Maqueira, L. [Instituto de Ciencia y Tecnología de Materiales (IMRE), Universidad de La Habana, Zapata y G, Vedado, Plaza, La Habana 10400 (Cuba); Facultad de Química, Universidad de La Habana, Zapata y G, Vedado, Plaza, La Habana 10400 (Cuba)

    2014-12-15

    Highlights: • Cu-doped ZnO nanoparticles obtained by chemical synthesis. • Substitutional or interstitial Cu into ZnO lead specific structural, chemical, and optical changes. • Incorporation efficiency of Cu atoms in ZnO as a function of the Cu concentration in the precursor dissolution. - Abstract: In this work a study of ZnO and Cu-doped ZnO nanoparticles obtained by chemical synthesis in aqueous media was carried out. Structural analysis gave the dominant presence of wurtzite ZnO phase forming a solid solution Zn{sub 1−x}Cu{sub x}O. For high Cu doping CuO phase is also present. For low Cu concentration the lattice shrinks due to Cu atoms substitute Zn atoms. For high Cu concentration the lattice enlarges due to predominance of interstitial Cu. From elemental analysis we determined and analyzed the incorporation efficiency of Cu atoms in Zn{sub 1−x}Cu{sub x}O as a function of the Cu concentration in the precursor dissolution. Combining structural and chemical results we described the Cu/Zn precursor concentrations r{sub w} in which the solid solution of Cu in ZnO is predominant. In the region located at r{sub w} ≈ 0.2–0.3 it is no longer valid. For Cu/Zn precursor concentration r{sub w} > 0.3 interstitial Cu dominates, and some amount of copper oxide appears. As the Cu concentration increases, the effective size of nanoparticles decreases. Photoluminescence (PL) measurements of the Cu-doped ZnO nanoparticles were carried out and analyzed.

  17. Polyethylene glycol-coated blue-emitting silicon dots with improved properties for uses in aqueous and biological environments

    Science.gov (United States)

    Rodríguez Sartori, Damián; Lillo, Cristian R.; Romero, Juan J.; Dell‧Arciprete, María Laura; Miñán, Alejandro; de Mele, Mónica Fernández Lorenzo; Gonzalez, Mónica C.

    2016-11-01

    Grafting of polyethylene glycol (PEG) to ultrasmall photoluminescent silicon dots (SiDs) is expected to improve and expand the applications of these particles to aqueous environments and biological systems. Herein we report a novel one-pot synthesis of robust, highly water compatible PEG-coated SiDs (denoted as PEG-SiDs) of (3.3 ± 0.5) nm size. The nanoparticles’ synthesis is based on the liquid phase oxidation of magnesium silicide using PEG as reaction media and leading to high PEG density grafting. PEG-SiDs enhanced photophysical, photosensitising, and solution properties in aqueous environments are described and compared to those of 2 nm size PEG-coated SiDs with low PEG density grafting (denoted as PEG-NHSiDs) obtained from a multistep synthesis strategy. PEG-SiDs form highly dispersed suspensions in water showing stable photoluminescence and quantum yields of Φ = 0.13 ± 0.04 at 370 nm excitation in air-saturated suspensions. These particles exhibited the capacity of photosensitising the formation of singlet molecular oxygen, not observed for PEG-NHSiDs. PEG robust shielding of the silicon core luminescent properties is further demonstrated in bio-imaging experiments stressing the strong interaction between PEG-SiDs and Staphylococcus aureus smears by observing the photoluminescence of particles. PEG-SiDs were found to be nontoxic to S. aureus cells at concentrations of 100 mg ml-1, though a bacteriostatic effect on S. aureus biofilms was observed upon UV-A irradiation under conditions where light alone has no effect.

  18. Survival and testing parameters of zirconia-based crowns under cyclic loading in an aqueous environment: A systematic review.

    Science.gov (United States)

    Elshiyab, Shareen Hayel; Nawafleh, Noor; George, Roy

    2017-03-19

    To study the hypothesis that in vitro fatigue testing variables in an aqueous environment affect the survival results of zirconia-based restorations, and evaluate the level of agreement between in vitro and previous in vivo data. An electronic search of literature was conducted in PubMed and Scopus to identify in vitro studies testing zirconia-based crowns using cyclic loading in an aqueous environment. Only studies that complied with the inclusion criteria were included. Data extracted were used for survival analysis and assessment of in vitro parameters for fatigue testing of implant and tooth-supported crowns. Using "Assessing the Methodological Quality of Systematic Reviews" (AMSTAR), recent in vivo systematic review studies were assessed prior to consideration for comparison with the current in vitro data. After applying the inclusion criteria only 25 articles were included. Five-year cumulative survival rate of zirconia-based implant-supported crowns was lower than tooth-supported crowns (84% and 88.8% respectively). Tooth-supported crowns subjected to wet fatigue showed a lower 5-year cumulative survival rate compared to thermocycling (62.8% and 92.6% respectively). Monolithic crowns showed higher fracture resistance compared to bi-layered structure (pressed or hand-layered). Only in vivo systematic reviews, which complied with AMSTAR assessment criteria, were used for comparison to the in vitro data. As for fatigue testing parameters, differences in the experimental setting were evident and affected the outcomes. Crown survivals depend on type of support, type of fatigue test conducted, crown structure, and veneering method. In vitro fatigue testing protocols are highly variable, which introduces a need for international standardization to allow for more valid comparability of data. © 2017 John Wiley & Sons Australia, Ltd.

  19. Uptake of permanganate from aqueous environment by surfactant modified montmorillonite batch and fixed bed studies

    Indian Academy of Sciences (India)

    N Mahadevaiah; B Vijayakumar; K Hemalatha; B S Jai Prakash

    2011-12-01

    Organo-clay was prepared by incorporating different amounts (in terms of CEC, ranging from 134–840 mg of quaternary ammonium cation (QACs) such as hexadecytrimethylammonium bromide ([C19H42N]Br) into the montmorillonite clay. Prepared organo-clays are characterized by CHN analyser and XRD to measure the amount of elemental content and interlayer spacing of surfactant modified clay. The batch experiments of sorption of permanganate from aqueous media by organo-clays was studied at different acidic strengths (pH 1–7). The experimental results show that the rate and amount of adsorption of permanganate was higher at lower pH compared to raw montmorillonite. Laboratory fixed bed experiments were conducted to evaluate the breakthrough time and nature of breakthrough curves. The shape of the breakthrough curves shows that the initial cationic surfactant loadings at 1.0 CEC of the clay is enough to enter the permanganate ions in to the interlamellar region of the surfactant modified smectile clays. These fixed bed studies were also applied to quantify the effect of bed-depth and breakthrough time during the uptake of permanganate. Calculation of thermodynamic parameters shows that the sorption of permanganate is spontaneous and follows the first order kinetics.

  20. Molecular Modeling of Ammonium, Calcium, Sulfur, and Sodium Lignosulphonates in Acid and Basic Aqueous Environments

    Science.gov (United States)

    Salazar Valencia, P. J.; Bolívar Marinez, L. E.; Pérez Merchancano, S. T.

    2015-12-01

    Lignosulphonates (LS), also known as lignin sulfonates or sulfite lignin, are lignins in sulfonated forms, obtained from the "sulfite liquors," a residue of the wood pulp extraction process. Their main utility lies in its wide range of properties, they can be used as additives, dispersants, binders, fluxing, binder agents, etc. in fields ranging from food to fertilizer manufacture and even as agents in the preparation of ion exchange membranes. Since they can be manufactured relatively easy and quickly, and that its molecular size can be manipulated to obtain fragments of very low molecular weight, they are used as transport agents in the food industry, cosmetics, pharmaceutical and drug development, and as molecular elements for the treatment of health problems. In this paper, we study the electronic structural and optical characteristics of LS incorporating ammonium, sulfur, calcium, and sodium ions in acidic and basic aqueous media in order to gain a better understanding of their behavior and the very interesting properties exhibit. The studies were performed using the molecular modeling program HyperChem 5 using the semiempirical method PM3 of the NDO Family (neglect of differential overlap), to calculate the structural properties. We calculated the electronic and optical properties using the semiempirical method ZINDO / CI.

  1. Charting the known chemical space for non-aqueous lithium-air battery electrolyte solvents.

    Science.gov (United States)

    Husch, Tamara; Korth, Martin

    2015-09-21

    Li-air batteries are very promising candidates for powering future mobility, but finding a suitable electrolyte solvent for this technology turned out to be a major problem. We present a systematic computational investigation of the known chemical space for possible Li-air electrolyte solvents. It is shown that the problem of finding better Li-air electrolyte solvents is not only - as previously suggested - about maximizing Li(+) and O2(-) solubilities, but also about finding the optimal balance of these solubilities with the viscosity of the solvent. As our results also show that trial-and-error experiments on known chemicals are unlikely to succeed, full chemical sub-spaces for the most promising compound classes are investigated, and suggestions are made for further experiments. The proposed screening approach is transferable and robust and can readily be applied to optimize electrolytes for other electrochemical devices. It goes beyond the current state-of-the-art both in width (considering the number of compounds screened and the way they are selected), as well as depth (considering the number and complexity of properties included).

  2. Charting the known chemical space for non-aqueous Lithium-air battery electrolyte solvents

    CERN Document Server

    Husch, Tamara

    2015-01-01

    The Li-Air battery is a very promising candidate for powering future mobility, but finding a suitable electrolyte solvent for this technology turned out to be a major problem. We present a systematic computational investigation of the known chemical space for possible Li-Air electrolyte solvents. It is shown that the problem of finding better Li-Air electrolyte solvents is not only - as previously suggested - about maximizing Li+ and O2- solubilities, but about finding the optimal balance of these solubilities with the viscosity of the solvent. As our results also show that trial-and-error experiments on known chemicals are unlikely to succeed, full chemical sub-spaces for the most promising compound classes are investigated, and suggestions are made for further experiments. The proposed screening approach is transferable and robust and can readily be applied to optimize electrolytes for other electrochemical devices. It goes beyond the current state-of-the-art both in width (considering the number of compoun...

  3. Chemical Hazards of Nanoparticles to Human and Environment (A Review

    Directory of Open Access Journals (Sweden)

    Fozia Haque Khan

    2014-01-01

    Full Text Available Science and technology have identified unique properties of nanomaterials. These properties may yield many far-reaching societal benefits, but they can also pose hazards and risks. Although the nanotechnology industry is still in its infancy, as more nanotechnology applications are commercialized, the potential for human exposure to nanoparticles and raw nanomaterials would continue to increase. One area of most concern about hazards is the workplace-be it a research laboratory, start-up company, production facility, or operation in which engineered nanomaterials are processed, used, disposed, or recycled. In order to determine whether the unique chemical and physical properties of new nanoparticles result in specific toxicologic properties, the nanotechnology community needs new ways of evaluating hazards and ultimately assessing the risk factor and therefore an attempt must be made to exclusively concentrate on the potential health hazards of nanopowders. One potential hazard that appears to have received little attention to date is their explosibility. This literature review has been commissioned to explore the physical and chemical properties of nanoparticles that could differentially influence toxicity, use of nanoparticles in industry and the potential hazards.

  4. Saffron Aqueous Extract Inhibits the Chemically-induced Gastric Cancer Progression in the Wistar Albino Rat

    Directory of Open Access Journals (Sweden)

    S. Zahra Bathaie

    2013-01-01

    Full Text Available Objective(s: Gastric cancer is the first and second leading cause of cancer related death in Iranian men and women, respectively. Gastric cancer management is based on the surgery, radiotherapy and chemotherapy. In the present study, for the first time, the beneficial effect of saffron (Crocus sativus L. aqueous extract (SAE on the 1-Methyl-3-nitro-1-nitrosoguanidine (MNNG-induced gastric cancer in rat was investigated. Materials and Methods: MNNG was used to induce gastric cancer and then, different concentrations of SAE were administered to rats. After sacrificing, the stomach tissue was investigated by both pathologist and flow cytometry, and several biochemical parameters was determined in the plasma (or serum and stomach of rats. Results: Pathologic data indicated the induction of cancer at different stages from hyperplasia to adenoma in rats; and the inhibition of cancer progression in the gastric tissue by SAE administration; so that, 20% of cancerous rats treated with higher doses of SAE was completely normal at the end of experiment and there was no rat with adenoma in the SAE treated groups. In addition, the results of the flow cytometry/ propidium iodide staining showed that the apoptosis/proliferation ratio was increased due to the SAE treatment of cancerous rats. Moreover, the significantly increased serum LDH and decreased plasma antioxidant activity due to cancer induction fell backwards after treatment of rats with SAE. But changes in the other parameters (Ca2+, tyrosine kinase activity and carcino-embryonic antigen were not significant. Conclusion: SAE inhibits the progression of gastric cancer in rats, in a dose dependent manner.

  5. Spectroscopic analyses of chemical adaptation processes within microalgal biomass in response to changing environments

    Energy Technology Data Exchange (ETDEWEB)

    Vogt, Frank, E-mail: fvogt@utk.edu; White, Lauren

    2015-03-31

    Highlights: • Microalgae transform large quantities of inorganics into biomass. • Microalgae interact with their growing environment and adapt their chemical composition. • Sequestration capabilities are dependent on cells’ chemical environments. • We develop a chemometric hard-modeling to describe these chemical adaptation dynamics. • This methodology will enable studies of microalgal compound sequestration. - Abstract: Via photosynthesis, marine phytoplankton transforms large quantities of inorganic compounds into biomass. This has considerable environmental impacts as microalgae contribute for instance to counter-balancing anthropogenic releases of the greenhouse gas CO{sub 2}. On the other hand, high concentrations of nitrogen compounds in an ecosystem can lead to harmful algae blooms. In previous investigations it was found that the chemical composition of microalgal biomass is strongly dependent on the nutrient availability. Therefore, it is expected that algae’s sequestration capabilities and productivity are also determined by the cells’ chemical environments. For investigating this hypothesis, novel analytical methodologies are required which are capable of monitoring live cells exposed to chemically shifting environments followed by chemometric modeling of their chemical adaptation dynamics. FTIR-ATR experiments have been developed for acquiring spectroscopic time series of live Dunaliella parva cultures adapting to different nutrient situations. Comparing experimental data from acclimated cultures to those exposed to a chemically shifted nutrient situation reveals insights in which analyte groups participate in modifications of microalgal biomass and on what time scales. For a chemometric description of these processes, a data model has been deduced which explains the chemical adaptation dynamics explicitly rather than empirically. First results show that this approach is feasible and derives information about the chemical biomass

  6. Chemical surface deposition of cds thin films from CdI2 aqueous solution

    Directory of Open Access Journals (Sweden)

    G. Il’chuk

    2009-01-01

    Full Text Available For the first time using CdI2 solution CdS films on glass and ITO coated glass substrates were produced by the method of layerwise chemical surface deposition (ChSD. CdS thin films with the widths from 40 nm to 100 nm were obtained for windows in solar cells based on CdS/CdTe heterojunctions. Changes of the structural and optical properties of CdS films due to air annealing are shown.

  7. Poisoning of bubble propelled catalytic micromotors: the chemical environment matters

    Science.gov (United States)

    Zhao, Guanjia; Sanchez, Samuel; Schmidt, Oliver G.; Pumera, Martin

    2013-03-01

    Self-propelled catalytic microjets have attracted considerable attention in recent years and these devices have exhibited the ability to move in complex media. The mechanism of propulsion is via the Pt catalysed decomposition of H2O2 and it is understood that the Pt surface is highly susceptible to poisoning by sulphur-containing molecules. Here, we show that important extracellular thiols as well as basic organic molecules can significantly hamper the motion of catalytic microjet engines. This is due to two different mechanisms: (i) molecules such as dimethyl sulfoxide can quench the hydroxyl radicals produced at Pt surfaces and reduce the amount of oxygen gas generated and (ii) molecules containing -SH, -SSR, and -SCH3 moieties can poison the catalytically active platinum surface, inhibiting the motion of the jet engines. It is essential that the presence of such molecules in the environment be taken into consideration for future design and operation of catalytic microjet engines. We show this effect on catalytic micromotors prepared by both rolled-up and electrodeposition approaches, demonstrating that such poisoning is universal for Pt catalyzed micromotors. We believe that our findings will contribute significantly to this field to develop alternative systems or catalysts for self-propulsion when practical applications in the real environment are considered.

  8. Chemical Stability of Bioglass in Simulated Oral Environment

    Directory of Open Access Journals (Sweden)

    Moazzami SM

    2016-09-01

    Full Text Available Statement of Problem: Bioglasses are a series of biocompatible dental materials, which are considered as light conducting inserts in resin composite restorations. Consequently, their chemical stability is more essential when they are used in conjunction with resin composite. Objectives: The aim of this study was to evaluate and compare the chemical stability of Bioglass with dental porcelain and resin composite by determining the amount of released K+, Na+, Ca2+ ions and silicone elements from these materials as a result of exposure to tested solutions with different pH levels including: Sodium Bicarbonate [SB, (pH=9.2], Sodium Buffer Lactate [SBL, (pH=2.4], Acetic Acid [AA, (pH=2.4], and Distilled Water [DW, (pH=6.2]. Materials and Methods: In this experimental study, forty 2.0 × 4.0 cylindrical rods for each tested material group (Dental porcelain, Resin composite and Bioglass were prepared. They were divided into four subgroups of 10 rods each, which immersed in one of the four testing solutions in a designated container. The containers were stored at 50°C and 100% humidity for one week. The released ions were measured by using a spectrophotometer (µg/cm2/ml. The data were statistically analyzed by nonparametric Kruskal-Wallis H test. Results: It was observed that the tested materials released ions at different levels of concentration. The significant amounts of Sodium, Calcium, and Silicon ions release were measured in Bioglass subgroups in all the tested solutions (p < 0.001. Potassium ion release from dental porcelain was the largest in all solutions except for AA in which Bioglass had the greatest potassium ion release (p < 0.001. Conclusions: A greater structural instability was observed for Biogalss group than dental porcelain and resin composite in testing solutions with different pH .levels

  9. Atomic force microscopy based nanoindentation study of onion abaxial epidermis walls in aqueous environment

    Energy Technology Data Exchange (ETDEWEB)

    Xi, Xiaoning; Tittmann, Bernhard [Department of Engineering Science and Mechanics, Pennsylvania State University, University Park, Pennsylvania 16802 (United States); Kim, Seong H. [Department of Chemical Engineering, Pennsylvania State University, University Park, Pennsylvania 16802 (United States)

    2015-01-14

    An atomic force microscopy based nanoindentation method was employed to study how the structure of cellulose microfibril packing and matrix polymers affect elastic modulus of fully hydrated primary plant cell walls. The isolated, single-layered abaxial epidermis cell wall of an onion bulb was used as a test system since the cellulose microfibril packing in this cell wall is known to vary systematically from inside to outside scales and the most abundant matrix polymer, pectin, can easily be altered through simple chemical treatments such as ethylenediaminetetraacetic acid and calcium ions. Experimental results showed that the pectin network variation has significant impacts on the cell wall modulus, and not the cellulose microfibril packing.

  10. Chemically and biologically modified activated carbon sorbents for the removal of lead ions from aqueous media.

    Science.gov (United States)

    Mahmoud, Mohamed E; Abdel-Fattah, Tarek M; Osman, Maher M; Ahmed, Somia B

    2012-01-01

    A method is described for hybridization of the adsorption and biosorption characteristics of chemically treated commercial activated carbon and baker's yeast, respectively, for the formation of environmental friendly multifunctional sorbents. Activated carbon was loaded with baker's yeast after acid-base treatment. Scanning Electron Microscopy (SEM) and Fourier Transform Infrared (FTIR) Spectroscopy were used to characterize these sorbents. Moreover, the sorption capabilities for lead (II) ions were evaluated. A value of 90 μmol g(-1) was identified as the maximum sorption capacity of activated carbon. Acid-base treatment of activated carbon was found to double the sorption capacity (140-180 μmol g(-1)). Immobilization of baker's yeast on the surface of activated carbon sorbents was found to further improve the sorption capacity efficiency of lead to 360, 510 and 560 μmol g(-1), respectively. Several important factors such as pH, contact time, sorbent dose, lead concentration and interfering ions were examined. Lead sorption process was studied and evaluated by several adsorption isotherms and found to follow the Langmuir and BET models. The potential applications of various chemically and biologically modified sorbents and biosorbents for removal of lead from real water matrices were also investigated via multistage micro-column technique and the results referred to excellent recovery values of lead (95.0-99.0 ± 3.0-5.0 %).

  11. Chemical Abundance Patterns and the Early Environment of Dwarf Galaxies

    CERN Document Server

    Corlies, Lauren; Tumlinson, Jason; Bryan, Greg

    2013-01-01

    Recent observations suggest that abundance pattern differences exist between low metallicity stars in the Milky Way stellar halo and those in the dwarf satellite galaxies. This paper takes a first look at what role the early environment for pre-galactic star formation might have played in shaping these stellar populations. In particular, we consider whether differences in cross-pollution between the progenitors of the stellar halo and the satellites could help to explain the differences in abundance patterns. Using an N-body simulation, we find that the progenitor halos of the main halo are primarily clustered together at z=10 while the progenitors of the satellite galaxies remain on the outskirts of this cluster. Next, analytically modeled supernova-driven winds show that main halo progenitors cross-pollute each other more effectively while satellite galaxy progenitors remain more isolated. Thus, inhomogeneous cross-pollution as a result of different high-z spatial locations of each system's progenitors can ...

  12. Single-molecule surface-enhanced Raman scattering of R6G in aqueous environment under non-resonance conditions

    Institute of Scientific and Technical Information of China (English)

    Enzhong Tan; Penggang Yin; Lidong Li; Lin Guo

    2011-01-01

    The single-molecule surface-enhanced Raman scattering (SERS) spectra of Rhodamine 6G (R6G) in an aqueous environment under non-resonance conditions are studied. Series of spectra are recorded in time-mapping mode, and intensity fluctuations of SERS signals and spectral diffusion are observed. The correlations between the presence frequency of SERS spectra and number of hot spots as well as the quantity of molecules in scattering volume are examined thoroughly. The results indicate that only molecules located at hot spots produce good signal-to-noise ratio Raman spectra and the origin of fluctuating SERS signals are mainly ascribed to the movement of hot spots.%@@ The single-molecule surface-enhanced Raman scattering(SERS) spectra of Rhodamine 6G(R6G) in anaqueous environment under non-resonance conditions are studied.Series of spectra are recorded in timemapping mode,and intensity fluctuations of SERS signals and spectral diffusion are observed.The correlations between the presence frequency of SERS spectra and number of hot spots as well as the quantity of molecules in scattering volume are examined thoroughly.

  13. Water-Gated n-Type Organic Field-Effect Transistors for Complementary Integrated Circuits Operating in an Aqueous Environment

    Science.gov (United States)

    2017-01-01

    The first demonstration of an n-type water-gated organic field-effect transistor (WGOFET) is here reported, along with simple water-gated complementary integrated circuits, in the form of inverting logic gates. For the n-type WGOFET active layer, high-electron-affinity organic semiconductors, including naphthalene diimide co-polymers and a soluble fullerene derivative, have been compared, with the latter enabling a high electric double layer capacitance in the range of 1 μF cm–2 in full accumulation and a mobility–capacitance product of 7 × 10–3 μF/V s. Short-term stability measurements indicate promising cycling robustness, despite operating the device in an environment typically considered harsh, especially for electron-transporting organic molecules. This work paves the way toward advanced circuitry design for signal conditioning and actuation in an aqueous environment and opens new perspectives in the implementation of active bio-organic interfaces for biosensing and neuromodulation.

  14. New chemical evolution analytical solutions including environment effects

    CERN Document Server

    Spitoni, E

    2015-01-01

    In the last years, more and more interest has been devoted to analytical solutions, including inflow and outflow, to study the metallicity enrichment in galaxies. In this framework, we assume a star formation rate which follows a linear Schmidt law, and we present new analytical solutions for the evolution of the metallicity (Z) in galaxies. In particular, we take into account environmental effects including primordial and enriched gas infall, outflow, different star formation efficiencies, and galactic fountains. The enriched infall is included to take into account galaxy-galaxy interactions. Our main results can be summarized as: i) when a linear Schmidt law of star formation is assumed, the resulting time evolution of the metallicity Z is the same either for a closed-box model or for an outflow model. ii) The mass-metallicity relation for galaxies which suffer a chemically enriched infall, originating from another evolved galaxy with no pre-enriched gas, is shifted down in parallel at lower Z values, if co...

  15. A predictive model of iron oxide nanoparticles flocculation tuning Z-potential in aqueous environment for biological application

    Energy Technology Data Exchange (ETDEWEB)

    Baldassarre, Francesca, E-mail: francesca.baldassarre@unisalento.it [University of Salento, Department of Cultural Heritage (Italy); Cacciola, Matteo, E-mail: matteo.cacciola@unirc.it [University “Mediterranea” of Reggio Calabria, DICEAM (Italy); Ciccarella, Giuseppe, E-mail: giuseppe.ciccarella@unisalento.it [University of Salento, Department of Innovation Engineering (Italy)

    2015-09-15

    Iron oxide nanoparticles are the most used magnetic nanoparticles in biomedical and biotechnological field because of their nontoxicity respect to the other metals. The investigation of iron oxide nanoparticles behaviour in aqueous environment is important for the biological applications in terms of polydispersity, mobility, cellular uptake and response to the external magnetic field. Iron oxide nanoparticles tend to agglomerate in aqueous solutions; thus, the stabilisation and aggregation could be modified tuning the colloids physical proprieties. Surfactants or polymers are often used to avoid agglomeration and increase nanoparticles stability. We have modelled and synthesised iron oxide nanoparticles through a co-precipitation method, in order to study the influence of surfactants and coatings on the aggregation state. Thus, we compared experimental results to simulation model data. The change of Z-potential and the clusters size were determined by Dynamic Light Scattering. We developed a suitable numerical model to predict the flocculation. The effects of Volume Mean Diameter and fractal dimension were explored in the model. We obtained the trend of these parameters tuning the Z-potential. These curves matched with the experimental results and confirmed the goodness of the model. Subsequently, we exploited the model to study the influence of nanoparticles aggregation and stability by Z-potential and external magnetic field. The highest Z-potential is reached up with a small external magnetic influence, a small aggregation and then a high suspension stability. Thus, we obtained a predictive model of Iron oxide nanoparticles flocculation that will be exploited for the nanoparticles engineering and experimental setup of bioassays.

  16. Reproduction potentiated in nematodes (Caenorhabditis elegans) and guppy fish (Poecilia reticulata) by adding a synthetic peptide to their aqueous environment.

    Science.gov (United States)

    Davies, Keith G; Zimmerman, Brian; Dudley, Ed; Newton, Russell P; Hart, John E

    2015-03-01

    Ambient exposure to a short synthetic peptide has enhanced fecundity (number of offspring) in invertebrates and vertebrates, ostensibly by disinhibiting reproduction. In separate experiments, nematodes (Caenorhabditis elegans) and guppy fish (Poecilia reticulata) were exposed via their aqueous environment to a dissolved synthetic hexamer (6mer) peptide, IEPVFT (EPL036), at a concentration of 1 μmol l(-1). In the case of the worms, peptide was added to their aqueous buffer daily throughout the experiment (14 days); for the guppies, peptide administration was on the first 15 alternate days in a 50 week experiment. Fecundity rose by 79% among the worms. The number of descendants of the treated guppies was more than four times that of controls by week 26 (103 versus 25, including 72 juveniles versus 6), with 15.4% more estimated biomass in the test tank in total (i.e. including founders). It was deduced that treated females bred earlier, at a smaller size, and had larger brood sizes. The total number of fish in the control tank had caught up by termination, but biomass continued to lag the test tank. There were no overt signs of toxicity among either the worms or the fish. Bioinformatics has been unilluminating in explaining these results in terms, for example, of mimicry of an endogenous regulator. A mass spectrometric campaign to identify a receptor, using murine brain for expediency, proved inconclusive. Molecular modelling in silico indicated unexpectedly that the hexamer EPL036 might be acting as an antagonist, to pro-fecundity effect; that is, as a blocker of an inhibitor. This suggests that there awaits discovery an evolutionarily conserved reproductive inhibitor and its (anti-fecundity) receptor.

  17. Corrosion characteristics of seven metals in three aqueous environments for forensic applications

    Science.gov (United States)

    Tong, Tianqi

    Corrosion characteristics of seven varieties of metals---zinc, brass C260, stainless steel 302, stainless steel 316, stainless steel 420, stainless steel 430, and stainless steel 440---in three aqueous media---Atlantic Ocean, Charles River, and deionized waters---were assessed via mass loss methods over 32 weeks, with supplemental data in the form of photomicrographic records. Concurrently, tests were conducted to determine the degree of measurement error resulting from the analytical scale used during corrosion assessment. This was accomplished by using reference samples of each type of metal and a glass vial as the container that held the metal and water samples. These error tests indicated that while the mass error associated with the metal samples was low, the error in mass associated with the vial displayed error margins two orders of magnitude larger than the error margins for the smaller metal samples. Further, control tests and statistical analysis indicated that this variation was the result of some quality inherent to the vial. The metal samples involved in the corrosion assessment experiment generally displayed corrosion characteristics in agreement with trends reported in the literature. Zinc produced the greatest quantity of corrosion residues out of all the metals studied. Brass C260 also developed visible corrosion. For example, brass C260 developed dark green/brown adherent residue and whitish blue-tinted nonadherent residue in Atlantic Ocean water, faint greenish tarnishing and some dark green spots and dots over time in Charles River water, and only faint greenish tarnish in deionized water. In contrast with zinc and brass C260, the stainless steels did not exhibit signs of significant corrosion rates excepting stainless steel 420 (SS420), which displayed pitted features surrounded by multi-colored rings on all of its Atlantic Ocean immersion samples and 25% of its Charles River immersion samples. Atlantic Ocean water generally caused the greatest

  18. Design of a Multisensory Probe for Measuring Carbon Cycle Processes in Aqueous Subterranean Environments

    Energy Technology Data Exchange (ETDEWEB)

    McIntyre, Timothy J [ORNL; Kisner, Roger [ORNL; Woodworth, Ken [ORNL; Lenarduzzi, Roberto [ORNL; Frank, Steven Shane [ORNL; McKnight, Timothy E [ORNL

    2015-01-01

    The global carbon cycle describes the exchange of carbon between the atmosphere, terrestrial vegetation, oceans, and soil. Mechanisms involving carbon in sub-terrestrial ecosystems and their impact on climate are not well understood. This lack of understanding limits current climate models and prevents accurate soil-carbon storage predications for future climate conditions. To address the lack of instrumentation for conducting high fidelity measurements of appropriate parameters in the field, a multi-sensory probe using a mix of optical, fiber optic, and electronic technologies to measure CO2, temperature, dissolved oxygen, redox potential, and water level in subsurface environments has been developed. Details of the design, fabrication and laboratory performance verification are presented. Use cases and the anticipated impacts of such measurements on climate models are discussed.

  19. Chemical bonding in aqueous hexacyano cobaltate from photon- and electron-detection perspectives

    Science.gov (United States)

    Lalithambika, Sreeju Sreekantan Nair; Atak, Kaan; Seidel, Robert; Neubauer, Antje; Brandenburg, Tim; Xiao, Jie; Winter, Bernd; Aziz, Emad F.

    2017-01-01

    The electronic structure of the [Co(CN)6]3- complex dissolved in water is studied using X-ray spectroscopy techniques. By combining electron and photon detection methods from the solutions ionized or excited by soft X-rays we experimentally identify chemical bonding between the metal center and the CN ligand. Non-resonant photoelectron spectroscopy provides solute electron binding energies, and nitrogen 1 s and cobalt 2p resonant core-level photoelectron spectroscopy identifies overlap between metal and ligand orbitals. By probing resonances we are able to qualitatively determine the ligand versus metal character of the respective occupied and non-occupied orbitals, purely by experiment. For the same excitations we also detect the emitted X-rays, yielding the complementary resonant inelastic X-ray scattering spectra. For a quantitative interpretation of the spectra, we perform theoretical electronic-structure calculations. The latter provide both orbital energies and orbital character which are found to be in good agreement with experimental energies and with experimentally inferred orbital mixing. We also report calculated X-ray absorption spectra, which in conjunction with our orbital-structure analysis, enables us to quantify various bonding interactions with a particular focus on the water-solvent - ligand interaction and the strength of π-backbonding between metal and ligand.

  20. Removal of heavy metals from aqueous phases using chemically modified waste Lyocell fiber.

    Science.gov (United States)

    Bediako, John Kwame; Wei, Wei; Kim, Sok; Yun, Yeoung-Sang

    2015-12-15

    In this study, an outstanding performance of chemically modified waste Lyocell for heavy metals treatment is reported. The sorbent, which was prepared by a simple and concise method, was able to bind heavy metals such as Pb(II), Cu(II) and Cd(II), with very high efficiencies. The binding mechanisms were studied through adsorption and standard characterization tests such as scanning electron microscopy, energy-dispersive spectroscopy, Fourier transform infrared spectroscopy, and X-ray diffraction analyses. Adsorption kinetics was very fast and attained equilibrium within 5 min in all metals studied. The maximum single metal uptakes were 531.29±0.28 mg/g, 505.64±0.21 mg/g, and 123.08±0.26 mg/g for Pb(II), Cd(II) and Cu(II), respectively. In ternary metal systems, Cu(II) selectivity was observed and the underlying factors were discussed. The sorbent by its nature, could be very effective in treating large volumes of wastewater with the contact of very little amount.

  1. The Chemical Aquatic Fate and Effects database (CAFE), a tool that supports assessments of chemical spills in aquatic environments.

    Science.gov (United States)

    Bejarano, Adriana C; Farr, James K; Jenne, Polly; Chu, Valerie; Hielscher, Al

    2016-06-01

    The Chemical Aquatic Fate and Effects (CAFE) database is a centralized repository that allows for rapid and unrestricted access to data. Information in CAFE is integrated into a user-friendly tool with modules containing fate and effects data for 32 377 and 4498 chemicals, respectively. Toxicity data are summarized in the form of species sensitivity distributions (SSDs) with associated 1st and 5th percentile hazard concentrations (HCs). An assessment of data availability relative to reported chemical incidents showed that CAFE had fate and toxicity data for 32 and 20 chemicals, respectively, of 55 chemicals reported in the US National Response Center database (2000-2014), and fate and toxicity data for 86 and 103, respectively, of 205 chemicals reported by the National Oceanic and Atmospheric Administration (2003-2014). Modeled environmental concentrations of 2 hypothetical spills (acrylonitrile, 625 barrels; and denatured ethanol, 857 barrels) were used to demonstrate CAFE's practical application. Most species in the 24-h SSD could be potentially impacted by acrylonitrile and denatured ethanol during the first 35 min and 15 h post spill, respectively, with concentrations falling below their HC5s (17 mg/L and 2676 mg/L) at 45 min and 60 h post spill, respectively. Comparisons of CAFE-based versus published HC5 values for 100 chemicals showed that nearly half of values were within a 2-fold difference, with a relatively small number of comparisons exceeding a 10-fold difference. The development of CAFE facilitates access to relevant environmental information, with potential uses likely expanding beyond those related to assessment of spills in aquatic environments. Environ Toxicol Chem 2016;35:1576-1586. © 2015 SETAC.

  2. Effect of chemical exchange on radiation damping in aqueous solutions of the osmolyte glycine.

    Science.gov (United States)

    Rodríguez, Juan Carlos; Jennings, Patricia A; Melacini, Giuseppe

    2002-06-05

    Radiation damping is of central relevance in NMR spectroscopy especially with the advent of ultrahigh-field magnets and of supersensitive probes. Furthermore, the recent realization that the combined effect of the distant dipole field and of radiation damping causes the resurrection of undesired crushed water magnetization emphasizes the need for a thorough understanding of all the factors affecting radiation damping. While the effects of pulsed-field gradients and of active feedback have been extensively investigated, the consequences on radiation damping of chemical exchange between water and co-solutes is not as well understood. Here it is demonstrated that the rate of water radiation damping is significantly affected by free glycine (Gly), a representative of an important class of biocompatible osmolytes often used at molar concentrations as protein stabilizers. The pH and temperature dependencies of this effect were investigated and rationalized in terms of radiation damping attenuation caused by incoherent dephasing occurring in the intermediate exchange regime. For instance, at pH 6.0 and at a temperature of 313 K the Gly NH3+/water exchange has the same dramatic effect on radiation damping as a series of repeated weak PFGs, increasing the water inversion-recovery zero-crossing delay from approximately 30 ms to approximately 2.3 s. In addition, under these conditions, the Gly NH3+/water exchange suppresses the resurrection of unwanted crushed water magnetization. When used in combination with PFGs and water flip-back schemes, glycine is therefore expected to tame chaotic dynamics and improve the reproducibility of the NMR experiments affected by it.

  3. Exploring consumer exposure pathways and patterns of use for chemicals in the environment

    Directory of Open Access Journals (Sweden)

    Kathie L. Dionisio

    /Product Categories Database,DCPS,Danish Consumer Product Survey,DfE,Design for the Environment,EDSP,Endocrine Disruptor Screening Program,EPA,Environmental Protection Agency,EWG,Environmental Working Group,GRAS,Generally Recognized as Safe,HTP,Human Toxome Project,IUR,Inventory Update Reporting Modifications Rule,MSDS,Material Safety Data Sheets,NICNAS,National Industrial Chemicals Notification and Assessment Scheme,RPC,Retail Product Categories Database,SDWA,Safe Drinking Water Act,SPIN,Substances in Preparation in Nordic Countries,TSCA,Toxic Substances Control Act,Chemical exposure,Human exposure,High throughput,Exposure prioritization,Use category

  4. Phototransformation of cephalosporin antibiotics in an aqueous environment results in higher toxicity.

    Science.gov (United States)

    Wang, Xiao-Huan; Lin, Angela Yu-Chen

    2012-11-20

    Photodegradation may be the most important elimination process for cephalosporin antibiotics in surface water. Cefazolin (CFZ) and cephapirin (CFP) underwent mainly direct photolysis (t(1/2) = 0.7, 3.9 h), while cephalexin (CFX) and cephradine (CFD) were mainly transformed by indirect photolysis, which during the process a bicarbonate-enhanced nitrate system contributed most to the loss rate of CFX, CFD, and cefotaxime (CTX) (t(1/2) = 4.5, 5.3, and 1.3 h, respectively). Laboratory data suggested that bicarbonate enhanced the phototransformation of CFD and CFX in natural water environments. When used together, NO(3)(-), HCO(3)(-), and DOM closely simulated the photolysis behavior in the Jingmei River and were the strongest determinants in the fate of cephalosporins. TOC and byproducts were investigated and identified. Direct photolysis led to decarboxylation of CFD, CFX, and CFP. Transformation only (no mineralization) of all cephalosporins was observed through direct photolysis; byproducts were found to be even less photolabile and more toxic (via the Microtox test). CFZ exhibited the strongest acute toxicity after just a few hours, which may be largely attributed to its 5-methyl-1,3,4-thiadiazole-2-thiol moiety. Many pharmaceuticals were previously known to undergo direct sunlight photolysis and transformation in surface waters; however, the synergistic increase in toxicity caused by this cocktail (via pharmaceutical photobyproducts) cannot be ignored and warrants future research attention.

  5. Nitrones are able to release nitric oxide in aqueous environment under hydroxyl free radical attack.

    Science.gov (United States)

    Croitoru, Mircea Dumitru; Ibolya, Fülöp; Pop, Maria Cristiana; Dergez, Timea; Mitroi, Brânduşa; Dogaru, Maria Titica; Tokés, Béla

    2011-10-30

    Importance of a nitric oxide donor that can act as a spin trap might bring some new therapeutic possibilities regarding the treatment of ischemic diseases by reducing the intensity of free radical produced reperfusion lesions. These substances might be also used as a new type of photo protectors since they can absorb UV radiation, capture free radicals formed by interaction of UV radiation with tissue constituents, and tanning of the skin will be permitted due to nitric oxide release. The purpose of this work was to measure the ability of nitrones to release nitric oxide and how different factors (temperature, nitrone concentration, and free radicals) influence the releasing ability. Mostly, indirect determination of nitric oxide was carried out, by measuring nitrite and nitrate amounts (as decomposition products of nitric oxide), all nitrones proved to release significant amounts of nitric oxide. Nitrite measurements were made based on an HPLC-VIS method that uses pre-column derivatization of nitrite by forming an azo dye (limit of quantification: 5ng/ml). No good correlation was found between the amount of nitric oxide and temperature for most studied nitrones but between the formation of nitric oxide and nitrone concentration an asymptotic correlation was found. Fenton reagent also yielded formation of nitric oxide from nitrones and formed amounts were not different from those recorded for UV irradiation. Most of the nitrones effectively released about 0.5% of the maximum amount of nitric oxide that is chemically possible and estimated concentrations of 0.1μM were present in the solutions during decomposition.

  6. Removal of Copper(II and Zinc(II Ions From Aqueous Solution by Chemical Treatment of Coal Fly Ash

    Directory of Open Access Journals (Sweden)

    Eleonora Sočo

    2015-12-01

    Full Text Available The aim of this study was to investigate the chemical modifications of coal fly ash (CFA treated with HNO3 or ammonium acetate (AcNH4 or NaOH or sodium diethyldithiocarbamate (NaDDTC as an adsorbent for the removal of copper(II and zinc(II ions from aqueous solution. The morphology of fly ash grains before and after modification was examined via X-ray diffraction (XRD and images of scanning electron microscope (SEM. Adsorption of copper(II and zinc(II ions was conducted under batch process at different duration, concentrations and temperature of the suspension. Equilibrium experiments shows that the selectivity of CFA-NaOH nanoparticles towards Cu(II ions is greater than that of Zn(II ions, which is related to their hydrated ionic radius and first hydrolysis equilibrium constant. The adsorption isotherms were described by Langmuir and Freundlich models. Kinetic data revealed that the adsorption fits well by the pseudo-second-order rate model with high regression coefficients. Thermodynamic parameters suggested that the immobilization Cu(II and Zn(II ions onto CFA-NaOH is a spontaneous process. Results demonstrated that the treating coal fly ash with alkaline solution was a promising way to enhance Cu(II and Zn(II ions adsorption.

  7. Tungstate as a synergist to phosphonate-based formulation for corrosion control of carbon steel in nearly neutral aqueous environment

    Indian Academy of Sciences (India)

    B V Appa Rao; M Venkateswara Rao; S Srinivasa Rao; B Sreedhar

    2010-07-01

    Synergistic inhibition of corrosion of carbon steel in low chloride aqueous medium using tungstate as a synergist in combination with ,-(phosphonomethyl) glycine (BPMG) and zinc ions is presented. The synergistic action of tungstate has been established through the present studies. The new ternary inhibitor formulation is effective in neutral and slightly acidic as well as slightly alkaline media. Potentiodynamic polarisation studies inferred that the formulation functions as a mixed inhibitor. Impedance studies of the metal/solution interface revealed that the surface film is highly protective. Characterisation by X-ray photoelectron spectroscopy (XPS) of the surface film formed in presence of the inhibitor revealed the presence of iron, phosphorus, nitrogen, oxygen, carbon, zinc and tungsten in the surface film. The chemical shifts in the binding energies of these elements inferred that the surface film is composed of iron oxides/hydroxides, zinc hydroxide, heteropolynuclear complex [Fe(III), Zn(II)-BPMG] and WO3. Reflection absorption FTIR spectroscopic studies also supported the presence of these compounds in the surface film. Morphological features of the metal surface studied in the absence and presence of the inhibitor by scanning electron microscopy (SEM) are also presented. Based on all these results, a plausible mechanism of corrosion inhibition is proposed.

  8. Soft X-ray induced modifications of PVA-based microbubbles in aqueous environment: a microspectroscopy study.

    Science.gov (United States)

    Tzvetkov, George; Fernandes, Paulo; Wenzel, Stephan; Fery, Andreas; Paradossi, Gaio; Fink, Rainer H

    2009-02-21

    We use scanning-transmission X-ray microspectroscopy (STXM) for in situ characterization of the physicochemical changes in air-filled poly(vinyl alcohol) (PVA) based microbubbles upon soft X-ray irradiation. The microbubbles were illuminated directly in aqueous suspension with 520 eV X-rays and a continuous shrinkage of the particles with an illumination time/radiation dose was observed. Utilizing the intrinsic absorption properties of the species and the high spatial resolution of the STXM, the modifications of the particles' structure were simultaneously recognized. A thorough characterization of the microbubble volume, membrane thickness and absorption coefficient was performed by quantitative fitting of the radial transmittance profiles of the targeted microbubbles. Apart from the observed volume contraction, there was no significant change in the shell thickness. The chemical changes in the membranes were clarified via C K-edge near-edge X-ray absorption fine structure (NEXAFS) spectroscopy. It was revealed that the observed structural alterations go along with a continuous degradation of the PVA network associated with formation of carbonyl- and carboxyl-containing species as well as an increased content of unsaturated bonds.

  9. Fatigue Crack Propagation from Notched Specimens of 304 SS in elevated Temperature Aqueous Environment

    Energy Technology Data Exchange (ETDEWEB)

    Wire, G. L.; Mills, W. J.

    2002-08-01

    Fatigue crack propagation (FCP) rates for 304 stainless steel (304SS) were determined in 24 degree C and 288 degree C air and 288 degree C water using double-edged notch (DEN) specimens of 304 stainless steel (304 SS). Test performed at matched loading conditions in air and water at 288 degree C with 20-6- cc h[sub]2/kg h[sub]2O provided a direct comparison of the relative crack growth rates in air and water over a wide range of crack growth rates. The DEN crack extension ranged from short cracks (0.03-0.25 mm) to long cracks up to 4.06 mm, which are consistent with conventional deep crack tests. Crack growth rates of 304 SS in water were about 12 times the air rate. This 12X environmental enhancement persisted to crack extensions up to 4.06 mm, far outside the range associated with short crack effects. The large environmental degradation for 304 SS crack growth is consistent with the strong reduction of fatigue life in high hydrogen water. Further, very similar environmental effects w ere reported in fatigue crack growth tests in hydrogen water chemistry (HWC). Most literature data in high hydrogen water show only a mild environmental effect for 304 SS, of order 2.5 times air or less, but the tests were predominantly performed at high cyclic stress intensity or equivalently, high air rates. The environmental effect in low oxygen environments at low stress intensity depends strongly on both the stress ratio, R, and the load rise time, T[sub]r, as recently reported for austenitic stainless steel in BWR water. Fractography was performed for both tests in air and water. At 288 degree C in water, the fracture surfaces were crisply faceted with a crystallographic appearance, and showed striations under high magnification. The cleavage-like facets on the fracture surfaces suggest that hydrogen embrittlement is the primary cause of accelerated cracking.

  10. The effect of the indoor environment on the fate of organic chemicals in the urban landscape.

    Science.gov (United States)

    Cousins, Anna Palm

    2012-11-01

    To assess the effect of the indoor environment on the urban fate of organic chemicals, an 8-compartment indoor-inclusive steady state multimedia chemical fate model was developed. The model includes typical urban compartments (air, soil, water, sediment, and urban film) and a novel module representing a generic indoor environment. The model was parameterized to the municipality of Stockholm, Sweden and applied to four organic chemicals with different physical-chemical characteristics and use patterns: formaldehyde, 2,4,6-tribromophenol, di-ethylhexylphthalate and decabromodiphenyl ether. The results show that emissions to indoor air may increase the steady state mass and residence time in the urban environment by a factor of 1.1 to 22 for the four chemicals, compared to if emissions are assigned to outdoor air. This is due to the nested nature of the indoor environment, which creates a physical barrier that prevents chemicals from leaving the urban system with outflowing air. For DEHP and BDE 209, the additional partitioning to indoor surfaces results in a greater importance of the indoor removal pathways from surfaces. The outdoor environmental concentrations of these chemicals are predicted to be lower if emitted to indoor air than if emitted to outdoor air because of the additional indoor removal pathways of dust and indoor film, leading to loss of chemical from the system. For formaldehyde and 2,4,6-TBP outdoor environmental concentrations are not affected by whether the release occurs indoors or outdoors because of the limited partitioning to indoor surfaces. A sensitivity analysis revealed that there appears to be a relationship between logK(OA) and the impact of the ventilation rate on the urban fate of organic chemicals.

  11. Instrumentation and vehicle platform of a miniaturized submersible for exploration of terrestrial and extraterrestrial aqueous environments

    Science.gov (United States)

    Jonsson, Jonas; Sundqvist, Johan; Nguyen, Hugo; Berglund, Martin; Ogden, Sam; Palmer, Kristoffer; Smedfors, Katarina; Johansson, Linda; Hjort, Klas; Thornell, Greger

    2012-10-01

    An example of an extraterrestrial environment likely to support life is the vast liquid body believed to hide underneath the frozen crust of Jupiter's moon Europa. The hypothetical exploration of this, as well as the more accessible subglacial lakes on Earth, has been used as model applications for the development of a heavily miniaturized, yet qualified, submersible with the potential to be deployable either in itself through a long and narrow borehole or as the daughter craft of an ice-penetrating cryobot. Onboard the submersible, which is only 20 cm in length and 5 cm in diameter, accommodation of a versatile set of sensors and instruments capable of characterizing and imaging the surroundings, and even collecting water samples with microorganisms for return, is facilitated through the use of miniaturization technologies. For instance, together with a small camera, a laser-based, microoptic device enables the 3-D reconstruction of imaged objects for topographical measurements. As a complement, when the water is turbid or a longer range is wanted, the world's smallest side-scanning sonar, exhibiting centimeter resolution and a range of over 30 m, has been developed. The work on miniaturizing a CTD, which is a widely employed oceanographic instrument used to measure and correlate conductivity, temperature, and depth, has commenced. Furthermore, a device employing acoustics to trap microscopic particles and organisms, and, by this, enrich water samples, is under development. To ensure that the gathered samples are pristine until analyzed at the end of a mission, the device is equipped with high-pressure, latchable valves. Remote operation and transfer of measurement data and images, or even live streaming of video, is made possible through a kilometer-long fiber optic cable being reeled out from the vehicle underway and tethering it to a terminal. To extend the missions, the same fiber shall also be capable of charging the onboard batteries. In this paper, the

  12. Occurrence of cyclophosphamide and ifosfamide in aqueous environment and their removal by biological and abiotic wastewater treatment processes.

    Science.gov (United States)

    Česen, Marjeta; Kosjek, Tina; Laimou-Geraniou, Maria; Kompare, Boris; Širok, Brane; Lambropolou, Dimitra; Heath, Ester

    2015-09-15

    Cytostatic drug residues in the aqueous environment are of concern due to their possible adverse effects on non-target organisms. Here we report the occurrence and removal efficiency of cyclophosphamide (CP) and ifosfamide (IF) by biological and abiotic treatments including advanced oxidation processes (AOPs). Cyclophosphamide was detected in hospital wastewaters (14-22,000 ng L(-1)), wastewater treatment plant influents (19-27 ng L(-1)) and effluent (17 ng L(-1)), whereas IF was detected only in hospital wastewaters (48-6800 ng L(-1)). The highest removal efficiency during biological treatment (attached growth biomass in a flow through bioreactor) was 59 ± 15% and 35 ± 9.3% for CP and IF, respectively. Also reported are the removal efficiencies of both compounds from wastewater using hydrodynamic cavitation (HC), ozonation (O3) and/or UV, either individually or in combination with hydrogen peroxide (H2O2). Hydrodynamic cavitation did not remove CP and IF to any significant degree. The highest removal efficiencies: 99 ± 0.71% for CP and 94 ± 2.4% for IF, were achieved using UV/O3/H2O2 at 5 g L(-1) for 120 min. When combined with biological treatment, removal efficiencies were >99% for both compounds. This is the first report of combined biological and AOP treatment of CP and IF from wastewater with a removal efficiency >99%.

  13. Zn/ZnO core/shell nanoparticles synthesized by laser ablation in aqueous environment: Optical and structural characterizations

    Indian Academy of Sciences (India)

    S C Singh; R K Swarnkar; R Gopal

    2010-02-01

    Zn/ZnO core/shell nanoparticles are synthesized by pulsed laser ablation (PLA) of Zn metal plate in the aqueous environment of sodium dodacyl sulfate (SDS). Solution of nanoparticles is found stable in the colloidal form for a long time, and is characterized by UV-visible absorption, transmission electron microscopy (TEM), photoluminescence (PL) and Raman spectroscopic techniques. UV-visible absorption spectrum has four peaks at 231, 275, 356, and 520 nm, which provides primary information about the synthesis of core-shell and elongated nanoparticles. TEM micrographs reveal that synthesized nanoparticles are monodispersed with three different average sizes and size distributions. Colloidal solution of nanoparticles has significant absorption in the green region, therefore, it absorbs 514.7 nm light of Ar+ laser and emits in the blue region centred at 350 and 375 nm, violet at 457 nm and green at 550 nm regions. Raman shift is observed at 300 cm-1 with PL spectrum, which corresponds to ${}^{3}$2N and 3L mode of vibrations of ZnO shell layer. Synthesis mechanism of Zn/ZnO core/shell nanoparticles is discussed.

  14. A Contact Angle Study of the Interaction between Embedded Amphiphilic Molecules and the PDMS Matrix in an Aqueous Environment

    Directory of Open Access Journals (Sweden)

    Wenjun Qiu

    2014-08-01

    Full Text Available Poly(dimethylsiloxane (PDMS surface modification via gradient-induced transport of embedded amphiphilic molecules is a novel, easy, flexible, and environmentally friendly approach for reducing protein adsorption on PDMS in microfluidic applications. To better understand the processing and the potential use in the viability-sensitive applications such as manipulation and culturing of primary neural cells, we systematically investigate how embedded molecules interact with a PDMS matrix and its surface in aqueous environments by studying the wetting angle over time under various processing conditions, including water exposure time, water exposure temperature, curing master materials, in addition to comparing different embedded amphiphilic molecules. The results indicate that the water exposure time clearly plays an important role in the surface properties. Our interpretation is that molecular rearrangement of the surface-embedded molecules improves surface coverage in the short term; while over a longer period, the transport of molecules embedded in the bulk enhance its coverage. However, this improvement finally terminates when molecules transported from the bulk to the surface are not sufficient to replace the molecules leaching into the water.

  15. Adsorption of Zn(II) on the kaolinite(001) surfaces in aqueous environment: A combined DFT and molecular dynamics study

    Science.gov (United States)

    Wang, Qiang; Kong, Xiang-Ping; Zhang, Bao-Hua; Wang, Juan

    2017-08-01

    Adsorption of Zn(II) on two types of neutral (001) surfaces of kaolinite, tetrahedral Si(t) and octahedral Al(o), was studied by means of DFT calculations and classical molecular dynamics simulations. The position and structure for both outer-sphere and mono-/bi-dentate inner-sphere complexes of Zn(II) in aqueous environment were examined, with binding energy and radial distribution function calculated. Outer-sphere complex on the Si(t) surface, monodentate inner-sphere complex of ;Ou; (surface oxygen with ;upright; hydrogen) site and bidentate complex of ;Ou-Ou; site of neighboring Al centers on the Al(o) surface are considered to be the dominant adsorption species. The outer-sphere complex is found six-coordinated with distorted octahedral geometry, while both the inner-sphere complexes exhibit the tetrahedral structure with coordination number of four. Hydrogen bonding interactions between oxygen or hydrogen of the kaolinite(001) surfaces and the aqua ligands of Zn(II) act as the key role for the structure and stability of adsorption complexes. Upon the Mulliken population analysis and partial density of states, both Zn(II) and surface oxygen accept electrons from aqua oxygens, and coupling of O 2p with the sp3d2 or sp3 hybridization states of Zn(II) is the primary bonding nature of Zn(II) with oxygen in outer- and inner-sphere complexes, respectively.

  16. Synthesis of pH-sensitive and recyclable magnetic nanoparticles for efficient separation of emulsified oil from aqueous environments

    Science.gov (United States)

    Lü, Ting; Zhang, Shuang; Qi, Dongming; Zhang, Dong; Vance, George F.; Zhao, Hongting

    2017-02-01

    Emulsified oil wastewaters, arisen from oil industry and oil spill accidents, cause severe environmental and ecological problems. In this study, a series of pH-sensitive magnetic nanomaterials (MNPs) were synthesized and characterized for their evaluation in separation of emulsified oil from aqueous environments. A coprecipitation method was used to produce Fe3O4 magnetic nanoparticles that were coated in a 2-step process with first silica to form a surface for anchoring an (3-aminopropyl)triethoxysilane (APTES) molecular layer. Detailed studies were conducted on effects of MNPs dosage, APTES anchoring density (DA) and pH on oil-water separation performance of the synthetic MNPs. Results showed that, under both acidic and neutral conditions, MNPs with high DA exhibited enhanced oil-water separation performance, while under alkaline condition, the oil-water separation process was minimal. Alkaline conditions allowed the MNPs to be recycled up to 9 cycles without showing any significant decrease in oil-water separation efficiency. An examination of the oil-water separation mechanism found that electrostatic interaction and interfacial activity both played important roles in oil-water separation. In conclusion, pH-sensitive MNPs can be easily synthesized and recycled, providing a promising, cost-effective and environmentally-friendly process for the efficient treatment of emulsified oil wastewater.

  17. Graphene-Based Platform for Infrared Near-Field Nanospectroscopy of Water and Biological Materials in an Aqueous Environment.

    Science.gov (United States)

    Khatib, Omar; Wood, Joshua D; McLeod, Alexander S; Goldflam, Michael D; Wagner, Martin; Damhorst, Gregory L; Koepke, Justin C; Doidge, Gregory P; Rangarajan, Aniruddh; Bashir, Rashid; Pop, Eric; Lyding, Joseph W; Thiemens, Mark H; Keilmann, Fritz; Basov, D N

    2015-08-25

    Scattering scanning near-field optical microscopy (s-SNOM) has emerged as a powerful nanoscale spectroscopic tool capable of characterizing individual biomacromolecules and molecular materials. However, applications of scattering-based near-field techniques in the infrared (IR) to native biosystems still await a solution of how to implement the required aqueous environment. In this work, we demonstrate an IR-compatible liquid cell architecture that enables near-field imaging and nanospectroscopy by taking advantage of the unique properties of graphene. Large-area graphene acts as an impermeable monolayer barrier that allows for nano-IR inspection of underlying molecular materials in liquid. Here, we use s-SNOM to investigate the tobacco mosaic virus (TMV) in water underneath graphene. We resolve individual virus particles and register the amide I and II bands of TMV at ca. 1520 and 1660 cm(-1), respectively, using nanoscale Fourier transform infrared spectroscopy (nano-FTIR). We verify the presence of water in the graphene liquid cell by identifying a spectral feature associated with water absorption at 1610 cm(-1).

  18. Characterization of local hydrophobicity on sapphire (0001) surfaces in aqueous environment by colloidal probe atomic force microscopy

    Science.gov (United States)

    Wada, Tomoya; Yamazaki, Kenji; Isono, Toshinari; Ogino, Toshio

    2017-02-01

    Sapphire (0001) surfaces exhibit a phase-separation into hydrophobic and hydrophilic domains upon high-temperature annealing, which were previously distinguished by the thickness of adsorbed water layers in air using atomic force microscopy (AFM). To characterize their local surface hydrophobicity in aqueous environment, we used AFM equipped with a colloidal probe and measured the local adhesive force between each sapphire domain and a hydrophilic SiO2 probe surface, or a hydrophobic polystyrene one. Two data acquisition modes for statistical analyses were used: one is force measurements at different positions of the surface and the other repeated measurement at a fixed position. We found that adhesive force measurements using the polystyrene probe allow us to distinctly separate the hydrophilic and hydrophobic domains. The dispersion in the force measurement data at different positions of the surface is larger than that in the repeated measurements at a fixed position. It indicates that the adhesive force measurement is repeatable although their data dispersion for the measurement positions is relatively large. From these results, we can conclude that the hydrophilic and hydrophobic domains on the sapphire (0001) surfaces are distinguished by a difference in their hydration degrees.

  19. Structural Evolution of Molybdenum Carbides in Hot Aqueous Environments and Impact on Low-Temperature Hydroprocessing of Acetic Acid

    Directory of Open Access Journals (Sweden)

    Jae-Soon Choi

    2015-03-01

    Full Text Available We investigated the structural evolution of molybdenum carbides subjected to hot aqueous environments and their catalytic performance in low-temperature hydroprocessing of acetic acid. While bulk structures of Mo carbides were maintained after aging in hot liquid water, a portion of carbidic Mo sites were converted to oxidic sites. Water aging also induced changes to the non-carbidic carbon deposited during carbide synthesis and increased surface roughness, which in turn affected carbide pore volume and surface area. The extent of these structural changes was sensitive to the initial carbide structure and was lower under actual hydroprocessing conditions indicating the possibility of further improving the hydrothermal stability of Mo carbides by optimizing catalyst structure and operating conditions. Mo carbides were active in acetic acid conversion in the presence of liquid water, their activity being comparable to that of Ru/C. The results suggest that effective and inexpensive bio-oil hydroprocessing catalysts could be designed based on Mo carbides, although a more detailed understanding of the structure-performance relationships is needed, especially in upgrading of more complex reaction mixtures or real bio-oils.

  20. Optical properties of TiO{sub 2} thin films prepared by chemical spray pyrolysis from aqueous solutions

    Energy Technology Data Exchange (ETDEWEB)

    Ayouchi, R.; Casteleiro, C.; Schwarz, R. [Departamento de Fisica, Instituto Superior Tecnico, Av. Rovisco Pais 1, 1049-001 Lisboa (Portugal); Barrado, J.R.; Martin, F. [Laboratorio de Materiales y Superficie (Unidad Asociada al CSIC), Departamento de Fisica Aplicada I e Departamento de Ingenieria Quimica, Universidad de Malaga, 29071 Malaga (Spain)

    2010-04-15

    Titanium dioxide (TiO{sub 2}) is known to have three different kinds of polymorphous crystalline forms: rutile, anatase, and brookite. The rutile phase is always formed at higher temperatures, while the anatase phase is formed at lower temperatures and transformed into rutile phase above 800 C. Various deposition techniques have been developed for depositing TiO{sub 2} thin films, including evaporation, sputtering, chemical vapour deposition and thermal oxidation of titanium. Among them, the Chemical Spray Pyrolysis (CSP) technique has many advantages, such as good conformal coverage, the possibility of epitaxial growth and the application to large area deposition. Also, this method is low cost and it is easy to control the deposition growth parameters. In the present work, TiO{sub 2} thin films have been deposited on p-Si(001) and fused silica substrates by Chemical Spray Pyrolysis (CSP) method from aqueous solution containing titanium (IV) isopropoxide (Ti[OCH(CH{sub 3}){sub 2}]{sub 4}). As-deposited thin films show anatase polycrystalline structure, and rutile phase formed for films annealed at 750 C. SEM images have confirmed a smooth and crack-free surface with low surface roughness. X-ray photoelectron spectroscopy (XPS) combined with 4 keV Ar{sup +} depth profiling has shown that crystallized films correspond to TiO{sub 2}. Residual carbon coming from the organic precursor solution is only detected at the surface of the film. Thin films deposited on fused silica were highly transparent (more than 85%), with an indirect optical band gap of 3,43 and 3,33 eV for as-deposited and annealed films, respectively, and refractive indexes in the range between 2.01-2.29. Spectroscopic Ellipsometry (SE) also has been used to extract optical parameters. SE data fitted to triple-layer physical model revealed the same tendency to increase refractive index in annealed films. (copyright 2010 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

  1. Self-assembly of pi-conjugated peptides in aqueous environments leading to energy-transporting bioelectronic nanostructures

    Energy Technology Data Exchange (ETDEWEB)

    Tavor, John [Johns Hopkins Univ., Baltimore, MD (United States)

    2016-12-06

    The realization of new supramolecular pi-conjugated organic structures inspired and driven by peptide-based self-assembly will offer a new approach to interface with the biotic environment in a way that will help to meet many DOE-recognized grand challenges. Previously, we developed pi-conjugated peptides that undergo supramolecular self-assembly into one-dimensional (1-D) organic electronic nanomaterials under benign aqueous conditions. The intermolecular interactions among the pi-conjugated organic segments within these nanomaterials lead to defined perturbations of their optoelectronic properties and yield nanoscale conduits that support energy transport within individual nanostructures and throughout bulk macroscopic collections of nanomaterials. Our objectives for future research are to construct and study biomimetic electronic materials for energy-related technology optimized for harsher non-biological environments where peptide-driven self-assembly enhances pi-stacking within nanostructured biomaterials, as detailed in the following specific tasks: (1) synthesis and detailed optoelectronic characterization of new pi-electron units to embed within homogeneous self assembling peptides, (2) molecular and data-driven modeling of the nanomaterial aggregates and their higher-order assemblies, and (3) development of new hierarchical assembly paradigms to organize multiple electronic subunits within the nanomaterials leading to heterogeneous electronic properties (i.e. gradients and localized electric fields). These intertwined research tasks will lead to the continued development and fundamental mechanistic understanding of a powerful bioinspired materials set capable of making connections between nanoscale electronic materials and macroscopic bulk interfaces, be they those of a cell, a protein or a device.

  2. The Fate of Non-Volatile Organic Chemicals in The Agricultural Environment

    Directory of Open Access Journals (Sweden)

    Mohammad A. Batiha

    2007-01-01

    Full Text Available Multimedia dynamic model of the fate of non-volatile organic chemicals (NVOC in the agricultural environment is described. The modeled environment, consisting of up to three major surfaces environmental compartments, includes air, agricultural soil, and surface water. This model is based on the aquivalence approach suggested by Mackay and co-workers in 1989. As the movement of chemicals in the environment is closely associated with the movement of air, water and organic matter, the complete steady state mass budgets for air, water and particulate organic carbon (POC between the model compartments are described. All of the model equations, which are expressed in aquivalence notation, the mass balance for NVOC in the environmental surfaces compartments at dynamic state, and equations for the calculation of partitioning, overall persistence, total amount, total concentrations at dynamic state and intermedia fluxes of organic chemicals between air, water, and soil at steady-state are provided.

  3. Spontaneous fine-tuning to environment in many-species chemical reaction networks

    Science.gov (United States)

    Horowitz, Jordan M.; England, Jeremy L.

    2017-07-01

    A chemical mixture that continually absorbs work from its environment may exhibit steady-state chemical concentrations that deviate from their equilibrium values. Such behavior is particularly interesting in a scenario where the environmental work sources are relatively difficult to access, so that only the proper orchestration of many distinct catalytic actors can power the dissipative flux required to maintain a stable, far-from-equilibrium steady state. In this article, we study the dynamics of an in silico chemical network with random connectivity in an environment that makes strong thermodynamic forcing available only to rare combinations of chemical concentrations. We find that the long-time dynamics of such systems are biased toward states that exhibit a fine-tuned extremization of environmental forcing.

  4. Natural and active chemical remediation of toxic metals, organics, and radionuclides in the aquatic environment

    Energy Technology Data Exchange (ETDEWEB)

    McPherson, G.; Pintauro, P.; O`Connor, S. [and others

    1996-05-02

    This project focuses on the chemical aspects of remediation, with the underlying theme that chemical remediation does occur naturally. Included are studies on the fate of heavy metal and organic contaminants discharged into aquatic environments; accurate assay metal contaminants partitioned into soils, water and tissue; development of novel polymeric membranes and microporous solids for the entrapment of heavy metals; and the development of hybrid chemo-enzymatic oxidative schemes for aromatics decontamination. 49 refs.

  5. The need for better public health decisions on chemicals released into our environment.

    Science.gov (United States)

    Woodruff, Tracey J; Burke, Thomas A; Zeise, Lauren

    2011-05-01

    Protecting the health of the public-particularly the most vulnerable groups, such as children-requires rethinking current approaches to reducing environmental risks. We review the evolving understanding of the relationship between exposure to chemicals in the environment and disease, as well as the current state of managing those chemicals. We present recommendations to improve current approaches, including changing the burden of proof so that chemicals are not presumed safe in the absence of scientific data. We also propose modernizing approaches to assessing health risks.

  6. Selection of chemical products for oil field applications in arctic environments

    Energy Technology Data Exchange (ETDEWEB)

    Powell, D.E.; VanderWende, E. [ARCO, Alaska, Inc., Anchorage, AK (United States)

    1996-08-01

    The Kuparuk Oil Field is located on the North Slope of Alaska, well above the Arctic Circle. Kuparuk uses chemicals for a variety of different oil production needs, including corrosion inhibition, emulsion breaking, defoaming, biofouling control, and scale inhibition. The North Slope`s isolated location demands unique logistical support, but it is otherwise accessible by unpaved road and has extensive air service. The Arctic climate provides difficult challenges and requirements for any chemical selection. This paper describes some criteria and practical experiences related to selecting the proper chemical products to be used in the Arctic environment.

  7. Exposure to chemicals in consumer products: The role of the near-field environment

    DEFF Research Database (Denmark)

    Fantke, Peter; Csiszar, S.A.; Huang, L.;

    2016-01-01

    Humans can be exposed to chemicals in consumer products during product use and environmental releases with inhalation, ingestion, and dermal uptake as typical exposure routes. Nevertheless, chemical exposure modeling has traditionally focused on the far-field with near-field indoor models only......F, the fraction of the chemical in a product that is taken in by humans via each exposure pathway, considering specific compartments of entry into the near-field environment (releases of chemicals encapsulated in articles, indoor air spray, etc.). To est imate PiFs, we combined far-field environmental...... compartments with near -field compartments and exposure pathways in a multimedia matrix of transfer fractions, with columns and rows for each compartment and exposure pathway. The multiple transfers and PiFs (e.g. from chemicals encapsulated in articles to inhalation of indoor air and dermal uptake via skin...

  8. Optimum synthesis conditions of nanometric Fe50Ni50 alloy formed by chemical reduction in aqueous solution

    Indian Academy of Sciences (India)

    Marwa A Mohamed; Azza H El-Maghraby; Mona M Abd El-Latif; Hassan A Farag

    2013-10-01

    In the present article, various nanometric Fe50Ni50 alloys were synthesized by chemical reduction of the corresponding metal ions, with hydrazine in an aqueous solution. Process variables of reaction temperature, pH of the hydrazine solution and concentration of metal ions were varied in order to determine the optimum synthesis conditions regarding quality, productivity and cost. It is found that pH of hydrazine solution, at low concentration of metal ions, is the most crucial variable affecting the reaction rate, average crystallite and particle sizes of the synthesized nanometric Fe50Ni50 alloy, followed by the total concentration of metal ions. Thus, increase of pH of hydrazine solution acts as an efficient stabilizer in reducing the particle size. On the contrary, at high concentration of metal ions, the structural characteristics of the nanometric Fe50Ni50 alloy are almost insensitive to reaction temperature and pH of hydrazine solution, but the reduction rate is remarkably sensitive to reaction temperature. Based on these results, it is decided that a reaction temperature of 80 °C, pH of the hydrazine solution of 12.5 and concentration of metal ions of 0.6 M represent the optimum synthesis conditions. The role of pH of hydrazine solution in reducing the alloy’s average particle size as well as efficient stabilizer confirms tremendous effect of synthesis conditions on the alloy structure and therefore, the importance of this study for industrial production of nanometric Fe50Ni50 alloy.

  9. Optical and structural properties of Mn-doped ZnO nanorods grown by aqueous chemical growth for spintronic applications

    Energy Technology Data Exchange (ETDEWEB)

    Strelchuk, V.V. [V. Lashkaryov Institute of Semiconductor Physics, National Academy of Sciences of Ukraine, 45 Nauky pr., 03028 Kyiv (Ukraine); Nikolenko, A.S., E-mail: nikolenko_mail@ukr.net [V. Lashkaryov Institute of Semiconductor Physics, National Academy of Sciences of Ukraine, 45 Nauky pr., 03028 Kyiv (Ukraine); Kolomys, O.F.; Rarata, S.V.; Avramenko, K.A.; Lytvyn, P.M. [V. Lashkaryov Institute of Semiconductor Physics, National Academy of Sciences of Ukraine, 45 Nauky pr., 03028 Kyiv (Ukraine); Tronc, P. [Centre National de la Recherche Scientifique, Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris, 10 rue Vauquelin, 75005 Paris (France); Chey, Chan Oeurn; Nur, Omer; Willander, Magnus [Department of Science and Technology, Linköping University, 601 74 Norrköping (Sweden)

    2016-02-29

    The effect of Mn-doping on the structural, morphological, optical and magnetic properties of the ZnO:Mn nanorods (NRs) synthesized by aqueous chemical process is reported. Grown ZnO:Mn NRs are shown to have hexagonal end facets and the diameters increasing with nominal Mn content. Optical absorption measurements show a decrease in optical band gap with increase of Mn concentration. Raman spectroscopy revealed significant modification of the lattice vibrational properties of the ZnO matrix upon Mn doping. The additional Mn-related vibrational mode, intensity of which increases with amount of Mn can be regarded as an evidence of Mn incorporation into the host lattice of the ZnO. At high Mn concentrations, coexistence of hexagonal Zn{sub 1−x}Mn{sub x}O phase along with the secondary phases of ZnMn{sub 2}O{sub 4} cubic spinel is revealed. Magnetic properties of ZnO:Mn NRs are studied by combinatorial atomic force microscopy and magnetic force microscopy imaging, and obtained clear magnetic contrast at room temperature provides a strong evidence of ferromagnetic behavior. - Highlights: • Synthesis of Mn-doped ZnO nanorods by hydrothermal method is demonstrated. • Doping with Mn significantly changes the morphology of ZnO nanorods. • Additional Mn-induced Raman modes evidence incorporation of Mn into ZnO matrix. • Formation of secondary ZnMn{sub 2}O{sub 4} spinel phase is found at high Mn concentrations. • Contrast MFM images of ZnO:Mn nanorods indicate ferromagnetism at room temperature.

  10. A Submersible, Off-Axis Holographic Microscope for Detection of Microbial Motility and Morphology in Aqueous and Icy Environments.

    Directory of Open Access Journals (Sweden)

    Christian A Lindensmith

    Full Text Available Sea ice is an analog environment for several of astrobiology's near-term targets: Mars, Europa, Enceladus, and perhaps other Jovian or Saturnian moons. Microorganisms, both eukaryotic and prokaryotic, remain active within brine channels inside the ice, making it unnecessary to penetrate through to liquid water below in order to detect life. We have developed a submersible digital holographic microscope (DHM that is capable of resolving individual bacterial cells, and demonstrated its utility for immediately imaging samples taken directly from sea ice at several locations near Nuuk, Greenland. In all samples, the appearance and motility of eukaryotes were conclusive signs of life. The appearance of prokaryotic cells alone was not sufficient to confirm life, but when prokaryotic motility occurred, it was rapid and conclusive. Warming the samples to above-freezing temperatures or supplementing with serine increased the number of motile cells and the speed of motility; supplementing with serine also stimulated chemotaxis. These results show that DHM is a useful technique for detection of active organisms in extreme environments, and that motility may be used as a biosignature in the liquid brines that persist in ice. These findings have important implications for the design of missions to icy environments and suggest ways in which DHM imaging may be integrated with chemical life-detection suites in order to create more conclusive life detection packages.

  11. Peptide synthesis in aqueous environments: the role of extreme conditions and pyrite mineral surfaces on formation and hydrolysis of peptides.

    Science.gov (United States)

    Schreiner, Eduard; Nair, Nisanth N; Wittekindt, Carsten; Marx, Dominik

    2011-06-01

    A comprehensive study of free energy landscapes and mechanisms of COS-mediated polymerization of glycine via N-carboxy anhydrides (NCAs, "Leuchs anhydrides") and peptide hydrolysis at the water-pyrite interface at extreme thermodynamic conditions is presented. Particular emphasis is set on the catalytic effects of the mineral surface including the putative role of the ubiquitous sulfur vacancy defects. It is found that the mere presence of a surface is able to change the free energetics of the elementary reaction steps. This effect can be understood in terms of a reduction of entropic contributions to the reactant state by immobilizing the reactants and/or screening them from bulk water in a purely geometric ("steric") sense. Additionally, the pyrite directly participates chemically in some of the reaction steps, thus changing the reaction mechanism qualitatively compared to the situation in bulk water. First, the adsorption of reactants on the surface can preform a product-like structure due to immobilizing and scaffolding them appropriately. Second, pyrite can act as a proton acceptor, thus replacing water in this role. Third, sulfur vacancies are found to increase the reactivity of the surface. The finding that the presence of pyrite speeds up the rate-determining step in the formation of peptides with respect to the situation in bulk solvent while stabilizing the produced peptide against hydrolysis is of particular interest to the hypothesis of prebiotic peptide formation at hydrothermal aqueous conditions. Apart from these implications, the generality of the studied organic reactions are of immediate relevance to many fields such as (bio)geochemistry, biomineralization, and environmental chemistry.

  12. Biochemical strategies for the detection and detoxification of toxic chemicals in the environment.

    Science.gov (United States)

    Febbraio, Ferdinando

    2017-02-26

    Addressing the problems related to the widespread presence of an increasing number of chemicals released into the environment by human activities represents one of the most important challenges of this century. In the last few years, to replace the high cost, in terms of time and money, of conventional technologies, the scientific community has directed considerable research towards the development both of new detection systems for the measurement of the contamination levels of chemicals in people's body fluids and tissue, as well as in the environment, and of new remediation strategies for the removal of such chemicals from the environment, as a means of the prevention of human diseases. New emerging biosensors for the analysis of environmental chemicals have been proposed, including VHH antibodies, that combine the antibody performance with the affinity for small molecules, genetically engineered microorganisms, aptamers and new highly stable enzymes. However, the advances in the field of chemicals monitoring are still far from producing a continuous real-time and on-line system for their detection. Better results have been obtained in the development of strategies which use organisms (microorganisms, plants and animals) or metabolic pathway-based approaches (single enzymes or more complex enzymatic solutions) for the fixation, degradation and detoxification of chemicals in the environment. Systems for enzymatic detoxification and degradation of toxic agents in wastewater from chemical and manufacturing industries, such as ligninolytic enzymes for the treatment of wastewater from the textile industry, have been proposed. Considering the high value of these research studies, in terms of the protection of human health and of the ecosystem, science must play a major role in guiding policy changes in this field.

  13. The effect of the indoor environment on the fate of organic chemicals in the urban landscape

    Energy Technology Data Exchange (ETDEWEB)

    Cousins, Anna Palm, E-mail: anna.cousins@ivl.se

    2012-11-01

    To assess the effect of the indoor environment on the urban fate of organic chemicals, an 8-compartment indoor-inclusive steady state multimedia chemical fate model was developed. The model includes typical urban compartments (air, soil, water, sediment, and urban film) and a novel module representing a generic indoor environment. The model was parameterized to the municipality of Stockholm, Sweden and applied to four organic chemicals with different physical-chemical characteristics and use patterns: formaldehyde, 2,4,6-tribromophenol, di-ethylhexylphthalate and decabromodiphenyl ether. The results show that emissions to indoor air may increase the steady state mass and residence time in the urban environment by a factor of 1.1 to 22 for the four chemicals, compared to if emissions are assigned to outdoor air. This is due to the nested nature of the indoor environment, which creates a physical barrier that prevents chemicals from leaving the urban system with outflowing air. For DEHP and BDE 209, the additional partitioning to indoor surfaces results in a greater importance of the indoor removal pathways from surfaces. The outdoor environmental concentrations of these chemicals are predicted to be lower if emitted to indoor air than if emitted to outdoor air because of the additional indoor removal pathways of dust and indoor film, leading to loss of chemical from the system. For formaldehyde and 2,4,6-TBP outdoor environmental concentrations are not affected by whether the release occurs indoors or outdoors because of the limited partitioning to indoor surfaces. A sensitivity analysis revealed that there appears to be a relationship between logK{sub OA} and the impact of the ventilation rate on the urban fate of organic chemicals. -- Highlights: Black-Right-Pointing-Pointer A novel indoor-inclusive multimedia urban fate model is developed and applied. Black-Right-Pointing-Pointer Emissions indoors may increase the urban chemical residence time. Black

  14. [The disturbances of the thyroid hormone homeostasis caused by chemical substances occurring in natural environment].

    Science.gov (United States)

    Kiałka, Marta; Doroszewska, Katarzyna; Mrozińska, Sandra; Milewicz, Tomasz; Stochmal, Ewa; Krzysiek, Józef

    2014-01-01

    The thyroid is an endocrine gland synthesizing, storaging and secreting thyroxine (T4) and triiodothyronine (T3). Currently, there are more and more reports and evidences that various chemical contaminants present in the environment, mainly polychlorinated biphenyls, interfere with stages of regulation, synthesis, secretion, transport of thyroid hormones. That can have a significant negative impact on the human body's endocrine homeostasis.

  15. Mapping of sites facing aqueous environment of voltage-gated proton channel at resting state: a study with PEGylation protection.

    Science.gov (United States)

    Kurokawa, Tatsuki; Okamura, Yasushi

    2014-01-01

    Hv1 (also named, voltage-sensor only protein, VSOP) lacks an authentic pore domain, and its voltage sensor domain plays both roles in voltage sensing and proton permeation. The activities of a proton channel are intrinsic to protomers of Hv1, while Hv1 is dimeric in biological membranes; cooperative gating is exerted by interaction between two protomers. As the signature pattern conserved among voltage-gated channels and voltage-sensing phosphatase, Hv1 has multiple arginines intervened by two hydrophobic residues on the fourth transmembrane segment, S4. S4 moves upward relative to other helices upon depolarization, causing conformational change possibly leading to the formation of a proton-selective conduction pathway. However, detailed mechanisms of proton-selectivity and gating of Hv1 are unknown. Here we took an approach of PEGylation protection assay to define residues facing the aqueous environment of mouse Hv1 (mHv1). Accessibilities of two maleimide molecules, N-ethylmaleimide (NEM) and 4-acetamido-4'-maleimidylstilbene-2,2'-disulfonic acid (AMS), were examined on cysteine introduced into individual sites. Only the first arginine on S4 (R1: R201) was inaccessible by NEM and AMS in mHv1. This is consistent with previous results of electrophysiology on the resting state channel, suggesting that the accessibility profile represents the resting state of mHv1. D108, critical for proton selectivity, was accessible by AMS and NEM, suggesting that D108 faces the vestibule. F146, a site critical for blocking by a guanidinium-reagent, was accessible by NEM, suggesting that F146 also faces the inner vestibule. These findings suggest an inner vestibule lined by several residues on S2 including F146, D108 on S1, and the C-terminal half of S4. © 2013.

  16. Calculation of liquid-liquid equilibrium of aqueous two-phase systems using a chemical-theory-based excess Gibbs energy model

    Directory of Open Access Journals (Sweden)

    Pessôa Filho P. A.

    2004-01-01

    Full Text Available Mixtures containing compounds that undergo hydrogen bonding show large deviations from ideal behavior. These deviations can be accounted for through chemical theory, according to which the formation of a hydrogen bond can be treated as a chemical reaction. This chemical equilibrium needs to be taken into account when applying stability criteria and carrying out phase equilibrium calculations. In this work, we illustrate the application of the stability criteria to establish the conditions under which a liquid-phase split may occur and the subsequent calculation of liquid-liquid equilibrium using a chemical-theory-modified Flory-Huggins equation to describe the non ideality of aqueous two-phase systems composed of poly(ethylene glycol and dextran. The model was found to be able to correlate ternary liquid-liquid diagrams reasonably well by simple adjustment of the polymer-polymer binary interaction parameter.

  17. An interesting case where water behaves as a unique solvent. 4-Aminophthalimide emission profile to monitor aqueous environment.

    Science.gov (United States)

    Durantini, Andrés M; Falcone, R Darío; Anunziata, Jorge D; Silber, Juana J; Abuin, Elsa B; Lissi, Eduardo A; Correa, N Mariano

    2013-02-21

    used as chromophore. This is significant since the use of chromophores without understanding its chemistry can induce artifacts into the interpretation of solvation dynamics in heterogeneous environments, in particular, those provided by aqueous biological systems.

  18. Aggregation of TiO{sub 2}–graphene nanocomposites in aqueous environment: Influence of environmental factors and UV irradiation

    Energy Technology Data Exchange (ETDEWEB)

    Hua, Zulin; Zhang, Jianan [Key Laboratory of Integrated Regulation and Resource Development on Shallow Lake of Ministry of Education, College of Environment, Hohai University, Nanjing 210098 (China); Bai, Xue, E-mail: baixue@hhu.edu.cn [Key Laboratory of Integrated Regulation and Resource Development on Shallow Lake of Ministry of Education, College of Environment, Hohai University, Nanjing 210098 (China); Ye, Zhengfang [Key Laboratory of Water and Sediment Sciences of the Ministry of Education, Department of Environmental Engineering, Peking University, Beijing 100871 (China); Tang, Zhiqiang; Liang, Lu; Liu, Yuqi [Key Laboratory of Integrated Regulation and Resource Development on Shallow Lake of Ministry of Education, College of Environment, Hohai University, Nanjing 210098 (China)

    2016-01-01

    The aggregation kinetics of TiO{sub 2}–graphene nanocomposites in aqueous solution affected by solution pH, salt types (NaCl, CaCl{sub 2}) and concentrations of electrolytes, and stability induced by UV irradiation was investigated in this study. The zeta potentials and hydrodynamic diameter of the nanoparticles were used as bases to assess the aggregation behavior, and stability of nanocomposites exposed to UV irradiation was expressed in terms of supernatant concentration. The aggregation of TiO{sub 2}–graphene nanoparticles in aqueous media followed the colloidal theory. TiO{sub 2}–graphene nanoparticles were significantly aggregated in the presence of a diavalent cation compared with monovalent cation because the former was more capable of effective charge screening and neutralization. The calculated Hamaker constant of the TiO{sub 2}–graphene nanocomposites in aqueous solution prepared in the lab was 2.31 × 10{sup −20} J. The stability of this composite nanoparticles was between those of pure TiO{sub 2} and graphene. A known intensity of UV irradiation was beneficial in the formation of TiO{sub 2}–graphene nanoparticle aggregates. However, prolonged UV irradiation may stabilize the nanoparticles. These results provided critical information about the colloidal properties of the new TiO{sub 2}–graphene nanocomposites and were useful in predicting the fate and transport of TiO{sub 2}–graphene nanocomposites in natural water environments. - Highlights: • This is the first study on the fate and transport of TiO{sub 2}–graphene in aqueous environment. • The Hamaker constant of TiO{sub 2}–graphene dispersed in aqueous solution was calculated. • The influence of UV irradiation on the stability of TiO{sub 2}–graphene was considered.

  19. [Nitrilotriacetic acid (NTA)--properties, distribution and behavior in the environment. I. Chemical and toxicological properties of NTA].

    Science.gov (United States)

    Jedra, M; Malanowska, M

    1995-01-01

    The reason of the interest shown in the properties of NTA is the possibility of its use for the replacement of polyphosphates in washing powders which are the cause of water eutrophization. In the light of literature data the chemical properties of NTA and the conditions influencing the course of the reaction of complex formation with metal ions in aqueous solutions are discussed Equilibrium constants of these reactions are presented, with diagrams obtained in computer assisted analysis of the conditions of equilibrium of NTA reaction with metal ions in the solutions occurring in physiological conditions and in the environment. On the basis of the opinions of expert committees the toxicity of NTA for mammalian organisms are described. It has been shown that NTA has no teratogenic or mutagenic action, however, in 2-year observations of mice and rats the intake of NTA produced lesions of uroepithelium with development of tumours. This effect of NTA has been demonstrated to be closely connected with its property of complex formation with metal ions. Experiments are described in which confirmation was obtained of the hypothesis that pathological lesions of renal tabules are caused by accumulation of zinc and bladder tumours are caused by binding by NTA of calcium from epithelial cells.

  20. Ecotoxicological assessments and the setting of limit values for chemicals in the environment

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1996-11-01

    The Committee on the Setting of Limit Values for Chemicals held its first open conference in Denmark in March 1992 at Mogenstrup Kro, Zealand. The conference proceedings were entitled `Risk Management and Risk Assessment in Different Sectors in Denmark`. The conference focused on risk assessment and the setting of limit values for chemicals in connection with human exposure to chemicals. The conference held in January 1996, which is covered by the present proceedings, dealt with the exposure of the environment to chemicals and the state-of-the-art as well as perspectives of ecotoxicological research. Special emphasis was placed on the illustration and discussion of the problems that have to be solved in order to secure satisfactory levels of protection of soil and aquatic environments in connection with exposure to chemicals. Also, problems connected with exposure through the atmosphere were discussed and exemplified by the work on the setting of limit values for tropospheric ozone. Furthermore, the global problems pertaining to what is believed to be the greenhouse effect and the degradation of the stratospheric ozone layer as well as the damage to crops caused by ozone were mentioned. (au)

  1. Chemical flooding in a virtual environment - a survivor`s guide to VR development

    Energy Technology Data Exchange (ETDEWEB)

    Bethel, W.

    1994-03-01

    Building something which could be called {open_quotes}virtual reality{close_quotes} (VR) is something of a challenge, particularly when nobody really seems to agree on a definition of VR. The author wanted to combine scientific visualization with VR, resulting in an environment useful for assisting scientific research. He demonstrates the combination of VR and scientific visualization in a prototype application. The VR application constructed consists of a dataflow based system for performing scientific visualization (AVS), extensions to the system to support VR input devices and a numerical simulation ported into the dataflow environment. The VR system includes two inexpensive, off-the-shelf VR devices and some custom code. A working system was assembled with about two man-months of effort. The system allows the user to specify parameters for a chemical flooding simulation as well as some viewing parameters using VR input devices, as well as view the output using VR output devices. In chemical flooding, there is a subsurface region that contains chemicals which are to be removed. Secondary oil recovery and environmental remediation are typical applications of chemical flooding. The process assumes one or more injection wells, and one or more production wells. Chemicals or water are pumped into the ground, mobilizing and displacing hydrocarbons or contaminants. The placement of the production and injection wells, and other parameters of the wells, are the most important variables in the simulation.

  2. The top 50 commodity chemicals: Impact of catalytic process limitations on energy, environment, and economics

    Energy Technology Data Exchange (ETDEWEB)

    Tonkovich, A.L.Y.; Gerber, M.A.

    1995-08-01

    The production processes for the top 50 U.S. commodity chemicals waste energy, generate unwanted byproducts, and require more than a stoichiometric amount of feedstocks. Pacific Northwest Laboratory has quantified this impact on energy, environment, and economics for the catalytically produced commodity chemicals. An excess of 0.83 quads of energy per year in combined process and feedstock energy is required. The major component, approximately 54%, results from low per-pass yields and the subsequent separation and recycle of unreacted feedstocks. Furthermore, the production processes, either directly or through downstream waste treatment steps, release more than 20 billion pounds of carbon dioxide per year to the environment. The cost of the wasted feedstock exceeds 2 billion dollars per year. Process limitations resulting from unselective catalysis and unfavorable reaction thermodynamic constraints are the major contributors to this waste. Advanced process concepts that address these problems in an integrated manner are needed to improve process efficiency, which would reduce energy and raw material consumption, and the generation of unwanted byproducts. Many commodity chemicals are used to produce large volume polymer products. Of the energy and feedstock wasted during the production of the commodity chemicals, nearly one-third and one-half, respectively, represents chemicals used as polymer precursors. Approximately 38% of the carbon dioxide emissions are generated producing polymer feedstocks.

  3. The chemical stability of L-isoleucine, L-threonine, and L-serine in aqueous solutions of KCl at 298.15 K

    Science.gov (United States)

    Roy, Sanjay; Dolui, Bijoy Krishna

    2016-06-01

    The experimental saturated solubilities of L-isoleucine, L-threonine, and L-serine in aqueous mixtures of a KCl solution at 298.15 K are presented in this article. The solubilities are measured by gravimetric method. In the present study the theoretical calculation of the standard transfer Gibbs free energy, cavity forming enthalpy of transfer, cavity forming transfer Gibbs free energy, dipole-dipole interaction effect have been computed. The chemical effects of the transfer Gibbs energies for the present amino acids have been obtained by subtracting the cavity effects and dipole-dipole interaction effects from the Δ G t 0 ( i). The stability of the experimental amino acids in aqueous KCl in terms of thermodynamic parameters is explained.

  4. Chemical insights, explicit chemistry, and yields of secondary organic aerosol from OH radical oxidation of methylglyoxal and glyoxal in the aqueous phase

    Science.gov (United States)

    Lim, Y. B.; Tan, Y.; Turpin, B. J.

    2013-09-01

    Atmospherically abundant, volatile water-soluble organic compounds formed through gas-phase chemistry (e.g., glyoxal (C2), methylglyoxal (C3), and acetic acid) have great potential to form secondary organic aerosol (SOA) via aqueous chemistry in clouds, fogs, and wet aerosols. This paper (1) provides chemical insights into aqueous-phase OH-radical-initiated reactions leading to SOA formation from methylglyoxal and (2) uses this and a previously published glyoxal mechanism (Lim et al., 2010) to provide SOA yields for use in chemical transport models. Detailed reaction mechanisms including peroxy radical chemistry and a full kinetic model for aqueous photochemistry of acetic acid and methylglyoxal are developed and validated by comparing simulations with the experimental results from previous studies (Tan et al., 2010, 2012). This new methylglyoxal model is then combined with the previous glyoxal model (Lim et al., 2010), and is used to simulate the profiles of products and to estimate SOA yields. At cloud-relevant concentrations (~ 10-6 - ~ 10-3 M; Munger et al., 1995) of glyoxal and methylglyoxal, the major photooxidation products are oxalic acid and pyruvic acid, and simulated SOA yields (by mass) are ~ 120% for glyoxal and ~ 80% for methylglyoxal. During droplet evaporation oligomerization of unreacted methylglyoxal/glyoxal that did not undergo aqueous photooxidation could enhance yields. In wet aerosols, where total dissolved organics are present at much higher concentrations (~ 10 M), the major oxidation products are oligomers formed via organic radical-radical reactions, and simulated SOA yields (by mass) are ~ 90% for both glyoxal and methylglyoxal. Non-radical reactions (e.g., with ammonium) could enhance yields.

  5. Chemical insights, explicit chemistry, and yields of secondary organic aerosol from OH radical oxidation of methylglyoxal and glyoxal in the aqueous phase

    Directory of Open Access Journals (Sweden)

    Y. B. Lim

    2013-09-01

    Full Text Available Atmospherically abundant, volatile water-soluble organic compounds formed through gas-phase chemistry (e.g., glyoxal (C2, methylglyoxal (C3, and acetic acid have great potential to form secondary organic aerosol (SOA via aqueous chemistry in clouds, fogs, and wet aerosols. This paper (1 provides chemical insights into aqueous-phase OH-radical-initiated reactions leading to SOA formation from methylglyoxal and (2 uses this and a previously published glyoxal mechanism (Lim et al., 2010 to provide SOA yields for use in chemical transport models. Detailed reaction mechanisms including peroxy radical chemistry and a full kinetic model for aqueous photochemistry of acetic acid and methylglyoxal are developed and validated by comparing simulations with the experimental results from previous studies (Tan et al., 2010, 2012. This new methylglyoxal model is then combined with the previous glyoxal model (Lim et al., 2010, and is used to simulate the profiles of products and to estimate SOA yields. At cloud-relevant concentrations (~ 10−6 − ~ 10−3 M; Munger et al., 1995 of glyoxal and methylglyoxal, the major photooxidation products are oxalic acid and pyruvic acid, and simulated SOA yields (by mass are ~ 120% for glyoxal and ~ 80% for methylglyoxal. During droplet evaporation oligomerization of unreacted methylglyoxal/glyoxal that did not undergo aqueous photooxidation could enhance yields. In wet aerosols, where total dissolved organics are present at much higher concentrations (~ 10 M, the major oxidation products are oligomers formed via organic radical–radical reactions, and simulated SOA yields (by mass are ~ 90% for both glyoxal and methylglyoxal. Non-radical reactions (e.g., with ammonium could enhance yields.

  6. Real-Time Molecular Monitoring of Chemical Environment in ObligateAnaerobes during Oxygen Adaptive Response

    Energy Technology Data Exchange (ETDEWEB)

    Holman, Hoi-Ying N.; Wozei, Eleanor; Lin, Zhang; Comolli, Luis R.; Ball, David. A.; Borglin, Sharon; Fields, Matthew W.; Hazen, Terry C.; Downing, Kenneth H.

    2009-02-25

    Determining the transient chemical properties of the intracellular environment canelucidate the paths through which a biological system adapts to changes in its environment, for example, the mechanisms which enable some obligate anaerobic bacteria to survive a sudden exposure to oxygen. Here we used high-resolution Fourier Transform Infrared (FTIR) spectromicroscopy to continuously follow cellular chemistry within living obligate anaerobes by monitoring hydrogen bonding in their cellular water. We observed a sequence of wellorchestrated molecular events that correspond to changes in cellular processes in those cells that survive, but only accumulation of radicals in those that do not. We thereby can interpret the adaptive response in terms of transient intracellular chemistry and link it to oxygen stress and survival. This ability to monitor chemical changes at the molecular level can yield important insights into a wide range of adaptive responses.

  7. 3D modeling of environments contaminated with chemical, biological, radiological and nuclear (CBRN) agents

    Science.gov (United States)

    Jasiobedzki, Piotr; Ng, Ho-Kong; Bondy, Michel; McDiarmid, Carl H.

    2008-04-01

    CBRN Crime Scene Modeler (C2SM) is a prototype 3D modeling system for first responders investigating environments contaminated with Chemical, Biological, Radiological and Nuclear agents. The prototype operates on board a small robotic platform or a hand-held device. The sensor suite includes stereo and high resolution cameras, a long wave infra red camera, chemical detector, and two gamma detectors (directional and non-directional). C2SM has been recently tested in field trials where it was teleoperated within an indoor environment with gamma radiation sources present. The system has successfully created multi-modal 3D models (geometry, colour, IR and gamma radiation), correctly identified location of radiation sources and provided high resolution images of these sources.

  8. Novel SiO2-deposited CaF2 substrate for vibrational sum-frequency generation (SFG) measurements of chemisorbed monolayers in an aqueous environment.

    Science.gov (United States)

    Padermshoke, Adchara; Konishi, Shouta; Ara, Masato; Tada, Hirokazu; Ishibashi, Taka-Aki

    2012-06-01

    A novel SiO(2)-deposited CaF(2) (SiO(2)/CaF(2)) substrate for measuring vibrational sum-frequency generation (SFG) spectra of silane-based chemisorbed monolayers in aqueous media has been developed. The substrate is suitable for silanization and transparent over a broad range of the infrared (IR) probe. The present work demonstrates the practical application of the SiO(2)/CaF(2) substrate and, to our knowledge, the first SFG spectrum at the solid/water interface of a silanized monolayer observed over the IR fingerprint region (1780-1400 cm(-1)) using a back-side probing geometry. This new substrate can be very useful for SFG studies of various chemisorbed organic molecules, particularly biological compounds, in aqueous environments.

  9. Detection of aqueous phase chemical warfare agent degradation products by negative mode ion mobility time-of-flight mass spectrometry [IM(tof)MS].

    Science.gov (United States)

    Steiner, Wes E; Harden, Charles S; Hong, Feng; Klopsch, Steve J; Hill, Herbert H; McHugh, Vincent M

    2006-02-01

    The use of negative ion monitoring mode with an atmospheric pressure ion mobility orthogonal reflector time-of-flight mass spectrometer [IM(tof)MS] to detect chemical warfare agent (CWA) degradation products from aqueous phase samples has been determined. Aqueous phase sampling used a traditional electrospray ionization (ESI) source for sample introduction and ionization. Certified reference materials (CRM) of CWA degradation products for the detection of Schedule 1, 2, or 3 toxic chemicals or their precursors as defined by the chemical warfare convention (CWC) treaty verification were used in this study. A mixture of six G-series nerve related CWA degradation products (EMPA, IMPA, EHEP, IHEP, CHMPA, and PMPA) and their related collision induced dissociation (CID) fragment ions (MPA and EPA) were found in each case to be clearly resolved and detected using the IM(tof)MS instrument in negative ion monitoring mode. Corresponding ions, masses, drift times, K(o) values, and signal intensities for each of the CWA degradation products are reported.

  10. Sensitive determinations of Cu, Pb, Cd, and Cr elements in aqueous solutions using chemical replacement combined with surface-enhanced laser-induced breakdown spectroscopy.

    Science.gov (United States)

    Yang, X Y; Hao, Z Q; Li, C M; Li, J M; Yi, R X; Shen, M; Li, K H; Guo, L B; Li, X Y; Lu, Y F; Zeng, X Y

    2016-06-13

    In this study, chemical replacement combined with surface-enhanced laser-induced breakdown spectroscopy (CR-SENLIBS) was for the first time applied to improve the detection sensitivities of trace heavy metal elements in aqueous solutions. Utilizing chemical replacement effect, heavy metal ions in aqueous solution were enriched on the magnesium alloy surface as a solid replacement layer through reacting with the high chemical activity metallic magnesium (Mg) within 1 minute. Unitary and mixed solutions with Cu, Pb, Cd, and Cr elements were prepared to construct calibration curves, respectively. The CR-SENLIBS showed a much better detection sensitivity and accuracy for both unitary and mixed solutions. The coefficients of determination R2 of the calibration curves were above 0.96, and the LoDs were of the same order of magnitude, i.e., in the range of 0.016-0.386 μg/mL for the unitary solution, and in the range of 0.025-0.420 μg/mL for the mixed solution. These results show that CR-SENLIBS is a feasible method for improving the detection sensitivity of trace element in liquid sample, which definitely provides a way for wider application of LIBS in water quality monitoring.

  11. NuPyCEE: NuGrid Python Chemical Evolution Environment

    Science.gov (United States)

    Ritter, Christian; Côté, Benoit

    2016-10-01

    The NuGrid Python Chemical Evolution Environment (NuPyCEE) simulates the chemical enrichment and stellar feedback of stellar populations. It contains three modules. The Stellar Yields for Galactic Modeling Applications module (SYGMA) models the enrichment and feedback of simple stellar populations which can be included in hydrodynamic simulations and semi-analytic models of galaxies. It is the basic building block of the One-zone Model for the Evolution of GAlaxies (OMEGA) module which allows the modelling of the chemical evolution of galaxies such as the Milky Way and its dwarf satellites. The STELLAB (STELLar ABundances) module provides a library of observed stellar abundances useful for comparing predictions of SYGMA and OMEGA.

  12. Modeling deuterium fractionation in cold and warm molecular environments with large chemical networks

    CERN Document Server

    Albertsson, T; Henning, Th

    2013-01-01

    Observations of deuterated species have long proven essential to probe properties and thermal history of various astrophysical environments. We present an elaborated chemical model that includes tens of thousands of reactions with multi-deuterated species, both gas-phase and surface, in which the most recent information on deuterium chemistry is implemented. A detailed study of the chemical evolution under wide range of temperatures and densities typical of cold molecular cores, warm protostellar envelopes, and hot cores/corinos is performed. We consider two cases of initial abundances, with 1) mainly atomic composition and all deuterium locked in HD, and 2) molecular abundances accumulated at 1 Myr of the evolution of a cold prestellar core. We indicate deuterated species that are particularly sensitive to temperature gradients and initial chemical composition. Many multiply-deuterated species produced at 10 K by exothermic ion-molecule chemistry retain large abundances even when temperature rises above 100 ...

  13. Estimation of octanol/water partition coefficient and aqueous solubility of environmental chemicals using molecular fingerprints and machine learning methods

    Science.gov (United States)

    Octanol/water partition coefficient (logP) and aqueous solubility (logS) are two important parameters in pharmacology and toxicology studies, and experimental measurements are usually time-consuming and expensive. In the present research, novel methods are presented for the estim...

  14. Estimation of octanol/water partition coefficient and aqueous solubility of environmental chemicals using molecular fingerprints and machine learning methods

    Science.gov (United States)

    Octanol/water partition coefficient (logP) and aqueous solubility (logS) are two important parameters in pharmacology and toxicology studies, and experimental measurements are usually time-consuming and expensive. In the present research, novel methods are presented for the estim...

  15. Correlation of Chemical and Physical Test Data For the Environment Ageing of Coflon (PVDF). Revised

    Science.gov (United States)

    Morgan, G. J.; Campion, R. P.

    1997-01-01

    This report aims to identify correlations between mechanical property changes and chemical/morphological structure changes for Coflon. It is intended both to illustrate the overall methodology and to indicate the testing that needs to be undertaken in order to obtain correlations. Many fluid exposures have now been carried out on Coflon during the project and many data generated as a result. The report summarises the changes observed in mechanical and physical properties and relates these as well as possible to the chemistry thought to be occurring during ageing. For this purpose, data have been collated from already-issued MERL and TRI technical and progress reports. Most of the mechanical testing of aged testpieces has been performed soon after the completion of the exposure; however, there is of necessity a delay in obtaining chemical analysis of the same testpieces, so that more physical than chemical data are shown. Three fluids have so far caused measurable deterioration of Coflon, these being: methanol (Fluid A), a methanol and amine mixture (Fluid G), and a mixture of methane, carbon dioxide gas and hydrogen sulphide gas plus aqueous amine (Fluid F). Only the effects of these fluids will be dealt with in any detail in this report, although other fluids are assessed to give relevant background information. Relevant test data collated here include: tensile modulus and related properties, mode of sample failure at break, fracture toughness, fatigue crack growth rate and resistance, stress relaxation rate, permeation coefficients, % crystallinity and molecular weight distributions together with changes in fluorine levels, and other observations where appropriate. However, not all of these were obtained for every ageing condition. Because of the wide range of tests employed, and the different ways in which their results are obtained, the following section has been included to serve as a background for making comparisons.

  16. Prioritization of chemicals according to the degree of hazard in the aquatic environment

    Science.gov (United States)

    Branson, Dean R.

    1980-01-01

    Chemicals designated as “priority pollutants” or “toxics” have received special attention recently because the discharge of these compounds into public water is to be restricted to the maximum possible with little regard to water quality or economics. The selection of many of the 129 priority cemicals was not based on an objective scientific assessment of the exposure and effect data. In fact, for some compounds, including acenaphthene and 4-chlorophenyl-phenyl ether, the necessary data for listing were non-existent. As an alternative to arbitrarily listing or delisting chemicals for the purpose of prioity control, this paper suggests a promising scientific approach to selecting priority chemicals based on the principles of hazard assessment for chemicals in the aquatic environment. According o the hypothesis, the highest priority chemicals are those with the least margin of safety, defined as the gap between the no-observable-effect concentrations and the ambient exposure concentrations. The no-observable-effect concenrations are based on the results of chronic or sensitive life stage tests with aquatic organisms and the acceptable daily intake rate for fish eates. The ambient exposure concentrations are levels either measured in fish and water, or roughly estimated from a simple nomogram that requires only two of the following three factors: environmental release rate, ratio of dissipation to bioconcentration potential, or ambient residues in fish. The chemicals studied to illustrate this approach to prioritizing chemicals based on hazard assessment are: polychlorinated biphenyls, di-2-ethylhexyl phthalate, linear alkylbenzene sulfonate, and pentachlorophenol. PMID:6771128

  17. Magnetic beads-based DNAzyme recognition and AuNPs-based enzymatic catalysis amplification for visual detection of trace uranyl ion in aqueous environment.

    Science.gov (United States)

    Zhang, Hongyan; Lin, Ling; Zeng, Xiaoxue; Ruan, Yajuan; Wu, Yongning; Lin, Minggui; He, Ye; Fu, FengFu

    2016-04-15

    We herein developed a novel biosensor for the visual detection of trace uranyl ion (UO2(2+)) in aqueous environment with high sensitivity and specificity by using DNAzyme-functionalized magnetic beads (MBs) for UO2(2+) recognition and gold nano-particles (AuNPs)-based enzymatic catalysis oxidation of TMB (3,3',5,5'-tetramethylbenzidine sulfate) for signal generation. The utilization of MBs facilitates the magnetic separation and collection of sensing system from complex sample solution, which leads to more convenient experimental operation and more strong resistibility of the biosensor to the matrix of sample, and the utilization of AuNPs-based enzymatic catalysis amplification greatly improved the sensitivity of the biosensor. Compared with the previous DNAzyme-based UO2(2+) sensors, the proposed biosensor has outstanding advantages such as relative high sensitivity and specificity, operation convenience, low cost and more strong resistibility to the matrix of sample. It can be used to detect as low as 0.02 ppb (74 pM) of UO2(2+) in aqueous environment by only naked-eye observation and 1.89 ppt (7.0 pM) of UO2(2+) by UV-visible spectrophotometer with a recovery of 93-99% and a RSD ≤ 5.0% (n=6) within 3h. Especially, the visual detection limit of 0.02 ppb (74 pM) is much lower than the maximum allowable level of UO2(2+) (130 nM) in the drinking water defined by the U.S. Environmental Protection Agency (EPA), indicating that our method meets the requirement of rapid and on-site detection of UO2(2+) in the aqueous environment by only naked-eye observation.

  18. On the performance of quantum chemical methods to predict solvatochromic effects. The case of acrolein in aqueous solution

    DEFF Research Database (Denmark)

    Aidas, Kestutis; Møgelhøj, Andreas; Nilsson, Elna Johanna Kristina

    2008-01-01

    The performance of the Hartree–Fock method and the three density functionals B3LYP, PBE0, and CAM-B3LYP is compared to results based on the coupled cluster singles and doubles model in predictions of the solvatochromic effects on the vertical n¿* and ¿* electronic excitation energies of acrolein...... of acrolein in vapor phase and aqueous solution. The gas-to-aqueous solution shift of the n¿* excitation energy is well reproduced by using all density functional methods considered. However, the B3LYP and PBE0 functionals completely fail to describe the ¿* electronic transition in solution, whereas...... the recent CAM-B3LYP functional performs well also in this case. The ¿* excitation energy of acrolein in water solution is found to be very dependent on intermolecular induction and nonelectrostatic interactions. The computed excitation energies of acrolein in vacuum and solution compare well to experimental...

  19. Ultra resolution chemical fingerprinting of dense non-aqueous phase liquids from manufactured gas plants by reversed phase comprehensive two-dimensional gas chromatography.

    Science.gov (United States)

    McGregor, Laura A; Gauchotte-Lindsay, Caroline; Daéid, Niamh Nic; Thomas, Russell; Daly, Paddy; Kalin, Robert M

    2011-07-22

    Ultra resolution chemical fingerprinting of dense non-aqueous phase liquids (DNAPLs) from former manufactured gas plants (FMGPs) was investigated using comprehensive two-dimensional gas chromatography coupled with time of flight mass spectrometry (GC×GC TOFMS). Reversed phase GC×GC (i.e. a polar primary column coupled to a non-polar secondary column) was found to significantly improve the separation of polycyclic aromatic hydrocarbons (PAHs) and their alkylated homologues. Sample extraction and cleanup was performed simultaneously using accelerated solvent extraction (ASE), with recovery rates between 76% and 97%, allowing fast, efficient extraction with minimal solvent consumption. Principal component analysis (PCA) of the GC×GC data was performed in an attempt to differentiate between twelve DNAPLs based on their chemical composition. Correlations were discovered between DNAPL composition and historic manufacturing processes used at different FMGP sites. Traditional chemical fingerprinting methods generally follow a tiered approach with sample analysis on several different instruments. We propose ultra resolution chemical fingerprinting as a fast, accurate and precise method of obtaining more chemical information than traditional tiered approaches while using only a single analytical technique.

  20. REACT-Mod: a mathematical model for transient calculation of chemical reactions with U-Pu-Np-Tc in the aqueous nitric acid solution

    Energy Technology Data Exchange (ETDEWEB)

    Tachimori, Shoichi [Japan Atomic Energy Research Inst., Tokai, Ibaraki (Japan). Tokai Research Establishment; Kitamura, Tatsuaki

    1996-10-01

    A computer code REACT-Mod which simulates various chemical reactions in an aqueous nitric acid solution involving uranium, plutonium, neptunium, technetium etc. e.g., redox, radiolytic and disproportionation reactions of 68, was developed based on the kinetics model. The numerical solution method adopted in the code are two, a kinetics model totally based on the rate law of which differential equations are solved by the modified Porsing method, and a two-step model based on both the rate law and equilibrium law. Only the former treats 27 radiolytic reactions. The latter is beneficially used to have a quick and approximate result by economical computation. The present report aims not only to explain the concept, chemical reactions treated and characteristics of the model but also to provide details of the program for users of the REACT-Mod code. (author)

  1. Preparation of Crumpled Graphite Oxide from Recycled Graphite Using Plasma Electrolysis and Its Application for Adsorption of Cadmium in Aqueous Environment

    Science.gov (United States)

    Hong, Phan Ngoc; Tuoi, Tran Thi; Ngan, Nguyen Thi Kim; Trang, Bui Thi; Minh, Phan Ngoc; Lam, Tran Dai; Hanh, Nguyen Thi; Van Thanh, Dang

    2016-05-01

    Household battery waste is considered hazardous and needs to be collected, managed, and recycled appropriately. In this study, using a plasma electrolysis method, we recycled graphite electrodes of exhausted dry batteries to prepare crumpled graphite oxide (CGO). Scanning electron microscopy revealed that the CGO possessed spherical morphology with average dimensions of 0.5 μm to 5 μm. The as-prepared CGO was then applied to absorb cadmium in aqueous environment. The results showed that CGO appears to be a promising adsorbent for removal of toxic waste from polluted water.

  2. Phyto-Chemical Evaluation and Anti-oxidant potentiality of Cycas beddomei Dyer Male cone aqueous Extract

    Directory of Open Access Journals (Sweden)

    Mahendra Nath Mitta

    2014-06-01

    Full Text Available Cycas beddomei Dyer, an endemic and critically endangered, tropical, dry deciduous, dioecious gymnosperm present in varied region of adjunct areas of Tirumala Hillocks, Seshachalam Biosphere Reserve, Eastern ghats, India. The objective of the study was to investigate antioxidant capacity of aqueous extracts of microsporophylls of male cones of Cycas beddomei. This study deals with the quantitative estimation of phytoconstituents viz., Total Phenolic Content (TPC, Total Flavonoid Content (TFC, Total Flavonols (TF, Total Proanthocyanidins (TPA, Extraction Yield (EY , Quantitative analysis soluble carbohydrates, Starch, Crude fibre, Proteins, Moisture, Ash and Mineral composition of aqueous extract of male cone of cycas beddomei has been carried out. Moreover, the assessment of antioxidant capacity by standard established calorimetric methods viz., DPPH assay, TAC and ABTS assay. Entire data has evaluated statistically. Results depicted High contents of TPC, TFC, TF and TPA and exerted anti-radical aptitude. Significant correlation has been found between quantities of phyto-constituents and anti-oxidant assays. With the results, it is confirmed that the logistics of aqueous cone extract of Cycas beddomei as potential anti-oxidant by evaluating the bioavailability of phytoconstituents and provided scientific base as a valuable natural antioxidant and therapeutic agent.

  3. Smelling in chemically complex environments: an optofluidic Bragg fiber array for differentiation of methanol adulterated beverages.

    Science.gov (United States)

    Yildirim, Adem; Ozturk, Fahri Emre; Bayindir, Mehmet

    2013-07-02

    A novel optoelectronic nose for analysis of alcohols (ethanol and methanol) in chemically complex environments is reported. The cross-responsive sensing unit of the optoelectronic nose is an array of three distinct hollow-core infrared transmitting photonic band gap fibers, which transmit a specific band of IR light depending on their Bragg mirror structures. The presence of alcohol molecules in the optofluidic core quenches the fiber transmissions if there is an absorption band of the analyte overlapping with the transmission band of the fiber; otherwise they remain unchanged. The cumulative response data of the fiber array enables rapid, reversible, and accurate discrimination of alcohols in chemically complex backgrounds such as beer and fruit juice. In addition, we observed that humidity of the environment has no effect on the response matrix of the optoelectronic nose, which is rarely achieved in gas-sensing applications. Consequently, it can be reliably used in virtually any environment without precalibration for humidity or drying the analytes. Besides the discussed application in counterfeit alcoholic beverages, with its superior sensor parameters, this novel concept proves to be a promising contender for many other applications including food quality control, environmental monitoring, and breath analysis for disease diagnostics.

  4. Assessment of Chemical Impact of Invasive Bryozoan Pectinatella magnifica on the Environment: Cytotoxicity and Antimicrobial Activity of P. magnifica Extracts.

    Science.gov (United States)

    Kollar, Peter; Šmejkal, Karel; Salmonová, Hana; Vlková, Eva; Lepšová-Skácelová, Olga; Balounová, Zuzana; Rajchard, Josef; Cvačka, Josef; Jaša, Libor; Babica, Pavel; Pazourek, Jiří

    2016-11-04

    Pectinatella magnifica, an invasive bryozoan, might significantly affect ecosystem balance due to its massive occurrence in many areas in Europe and other parts of the world. Biological and chemical analyses are needed to get complete information about the impact of the animal on the environment. In this paper, we aimed to evaluate in vitro cytotoxic effects of five extracts prepared from P. magnifica using LDH assay on THP-1 cell line. Antimicrobial activities of extracts against 22 different bacterial strains were tested by microdilution method. Our study showed that all extracts tested, except aqueous portion, demonstrated LD50 values below 100 μg/mL, which indicates potential toxicity. The water extract of P. magnifica with LD50 value of 250 μg/mL also shows potentially harmful effects. Also, an environmental risk resulting from the presence and increasing biomass of potentially toxic benthic cyanobacteria in old colonies should not be underestimated. Toxicity of Pectinatella extracts could be partially caused by presence of Aeromonas species in material, since we found members of these genera as most abundant bacteria associated with P. magnifica. Furthermore, P. magnifica seems to be a promising source of certain antimicrobial agents. Its methanolic extract, hexane, and chloroform fractions possessed selective inhibitory effect on some potential pathogens and food spoiling bacteria in the range of MIC 0.5-10 mg/mL. Future effort should be made to isolate and characterize the content compounds derived from P. magnifica, which could help to identify the substance(s) responsible for the toxic effects of P. magnifica extracts.

  5. Assessment of Chemical Impact of Invasive Bryozoan Pectinatella magnifica on the Environment: Cytotoxicity and Antimicrobial Activity of P. magnifica Extracts

    Directory of Open Access Journals (Sweden)

    Peter Kollar

    2016-11-01

    Full Text Available Pectinatella magnifica, an invasive bryozoan, might significantly affect ecosystem balance due to its massive occurrence in many areas in Europe and other parts of the world. Biological and chemical analyses are needed to get complete information about the impact of the animal on the environment. In this paper, we aimed to evaluate in vitro cytotoxic effects of five extracts prepared from P. magnifica using LDH assay on THP-1 cell line. Antimicrobial activities of extracts against 22 different bacterial strains were tested by microdilution method. Our study showed that all extracts tested, except aqueous portion, demonstrated LD50 values below 100 μg/mL, which indicates potential toxicity. The water extract of P. magnifica with LD50 value of 250 μg/mL also shows potentially harmful effects. Also, an environmental risk resulting from the presence and increasing biomass of potentially toxic benthic cyanobacteria in old colonies should not be underestimated. Toxicity of Pectinatella extracts could be partially caused by presence of Aeromonas species in material, since we found members of these genera as most abundant bacteria associated with P. magnifica. Furthermore, P. magnifica seems to be a promising source of certain antimicrobial agents. Its methanolic extract, hexane, and chloroform fractions possessed selective inhibitory effect on some potential pathogens and food spoiling bacteria in the range of MIC 0.5–10 mg/mL. Future effort should be made to isolate and characterize the content compounds derived from P. magnifica, which could help to identify the substance(s responsible for the toxic effects of P. magnifica extracts.

  6. Impact constraints on the environment for chemical evolution and the continuity of life

    Science.gov (United States)

    Oberbeck, Verne R.; Fogleman, Guy

    1990-03-01

    The Moon and the Earth were bombarded heavily by planetesimals and asteroids that were capable of interfering with chemical evolution and the origin of life. In this paper, we explore the frequency of giant terrestrial impacts able to stop prebiotic chemistry in the probable regions of chemical evolution. The limited time available between impacts disruptive to prebiotic chemistry at the time of the oldest evidence of life suggests the need for a rapid process for chemical evolution of life. The classical hypothesis for the origin of life through the slow accumulation of prebiotic reactants in the primordial soup in the entire ocean may not be consistent with constraints imposed by the impact history of Earth. On the other hand, rapid chemical evolution in cloud systems and lakes or other shallow evaporating water bodies would have been possible because reactants could have been concentrated and polymerized rapidly in this environment. Thus, life probably could have originated near the surface between frequent surface sterilizing impacts. There may not have been continuity of life depending on sunlight because there is evidence that life, existing as early as 3.8 Gyr ago, may have been destroyed by giant impacts. The first such organisms on Earth where probably not the ancestors of present life.

  7. Instrument developments for chemical and physical characterization, mapping and sampling of extreme environments (Antarctic sub ice environment)

    Science.gov (United States)

    Vogel, S. W.; Powell, R. D.; Griffith, I.; Lawson, T.; Schiraga, S.; Ludlam, G.; Oen, J.

    2009-12-01

    A number of instrumentation is currently under development designed to enable the study of subglacial environments in Antarctica through narrow kilometer long boreholes. Instrumentation includes: - slim line Sub-Ice ROV (SIR), - Geochemical Instrumentation Package for Sub Ice Environments (GIPSIE) to study geochemical fluxes in water and across the sediment water interface (CO2, CH4, dO, NH4, NO3, Si, PO4, pH, redox, T, H2, HS, O2, N2O, CTD, particle size, turbidity, color camera, current meter and automated water sampler) with real-time telemetry for targeted sampling, - long term energy-balance mooring system, - active source slide hammer sediment corer, and - integration of a current sensor into the ITP profiler. The instrumentation design is modular and suitable for remote operated as well as autonomous long-term deployment. Of interest to the broader science community is the development of the GIPSIE and efforts to document the effect of sample recovery from depth on the sample chemistry. The GIPSIE is a geochemical instrumentation package with life stream telemetry, allowing for user controlled targeted sampling of water column and the water sediment interphase for chemical and biological work based on actual measurements and not a preprogrammed automated system. The porewater profiler (pH, redox, T, H2, HS, O2, N2O) can penetrate the upper 50 cm of sediment and penetration is documented with real time video. Associated with GIPSIE is an on-site lab set-up, utilizing a set of identical sensors. Comparison between the insitu measurements and measurements taken onsite directly after samples are recovered from depth permits assessing the effect of sample recovery on water and sediment core chemistry. Sample recovery related changes are mainly caused by changes in the pressure temperature field and exposure of samples to atmospheric conditions. Exposure of anaerobic samples to oxygen is here a specific concern. Recovery from depth effects in generally p

  8. Estimation of environment-related properties of chemicals for design of sustainable processes: development of group-contribution+ (GC+) property models and uncertainty analysis.

    Science.gov (United States)

    Hukkerikar, Amol Shivajirao; Kalakul, Sawitree; Sarup, Bent; Young, Douglas M; Sin, Gürkan; Gani, Rafiqul

    2012-11-26

    The aim of this work is to develop group-contribution(+) (GC(+)) method (combined group-contribution (GC) method and atom connectivity index (CI) method) based property models to provide reliable estimations of environment-related properties of organic chemicals together with uncertainties of estimated property values. For this purpose, a systematic methodology for property modeling and uncertainty analysis is used. The methodology includes a parameter estimation step to determine parameters of property models and an uncertainty analysis step to establish statistical information about the quality of parameter estimation, such as the parameter covariance, the standard errors in predicted properties, and the confidence intervals. For parameter estimation, large data sets of experimentally measured property values of a wide range of chemicals (hydrocarbons, oxygenated chemicals, nitrogenated chemicals, poly functional chemicals, etc.) taken from the database of the US Environmental Protection Agency (EPA) and from the database of USEtox is used. For property modeling and uncertainty analysis, the Marrero and Gani GC method and atom connectivity index method have been considered. In total, 22 environment-related properties, which include the fathead minnow 96-h LC(50), Daphnia magna 48-h LC(50), oral rat LD(50), aqueous solubility, bioconcentration factor, permissible exposure limit (OSHA-TWA), photochemical oxidation potential, global warming potential, ozone depletion potential, acidification potential, emission to urban air (carcinogenic and noncarcinogenic), emission to continental rural air (carcinogenic and noncarcinogenic), emission to continental fresh water (carcinogenic and noncarcinogenic), emission to continental seawater (carcinogenic and noncarcinogenic), emission to continental natural soil (carcinogenic and noncarcinogenic), and emission to continental agricultural soil (carcinogenic and noncarcinogenic) have been modeled and analyzed. The application

  9. Chemicals in the air of the work environment and health risks

    Directory of Open Access Journals (Sweden)

    Karin reinhold

    2010-07-01

    Full Text Available The study focuses on indoor air quality (microclimate andchemicals in industrial premises. The health risk is determined.The model is presented for taking into consideration theconcentration of chemicals in the air of the work environment andpossible negative health effects. Practical examples and the resultsof measurements of microclimate and chemicals concentration inthe workplace air in five industries (mechanical, printing, wood,plastic and clothing industries are presented. The microclimate isunder control except during very hot climate in summer. Thechemicals are under control in printing, mechanical (exceptwelding in closed workrooms, and clothing industry. Thechemicals are often over the limits in wood processing industryand in some of the premises of plastic (manufacturing of rubberdetails industry.

  10. Food and soil-borne Penicillia in Arctic environments: Chemical diversity

    DEFF Research Database (Denmark)

    Frisvad, Jens Christian

    Penicillia are very common inhabitants of cold environments, including arctic soil, plants, animals, and foods. We have investigated the mycobiota of Greenland inland ice and soil, and found a very unique and pronounced diversity among the Penicillia. Nearly all species were new to science....... The species found in inland ice were both of the soil-borne type, and Penicillia that grow and sporulate well at 25°C. The latter group of Penicillia have been found earlier in refrigerated foods, including P. nordicum, and in glacier ice and melting water from Svalbard (se Sonjak et al., this conference......). This “food-borne group” of arctic fungi also contained some new species, but not as many as in arctic soil. The chemical diversity of the Penicillium species was remarkably high and in most cases even larger than the chemical diversity of Penicillia in the tropics. Several new secondary metabolites were...

  11. The GSTome Reflects the Chemical Environment of White-Rot Fungi.

    Directory of Open Access Journals (Sweden)

    Aurélie Deroy

    Full Text Available White-rot fungi possess the unique ability to degrade and mineralize all the different components of wood. In other respects, wood durability, among other factors, is due to the presence of extractives that are potential antimicrobial molecules. To cope with these molecules, wood decay fungi have developed a complex detoxification network including glutathione transferases (GST. The interactions between GSTs from two white-rot fungi, Trametes versicolor and Phanerochaete chrysosporium, and an environmental library of wood extracts have been studied. The results demonstrate that the specificity of these interactions is closely related to the chemical composition of the extracts in accordance with the tree species and their localization inside the wood (sapwood vs heartwood vs knotwood. These data suggest that the fungal GSTome could reflect the chemical environment encountered by these fungi during wood degradation and could be a way to study their adaptation to their way of life.

  12. The Hercules Cluster Environment Impact on the Chemical History of Star-Forming Galaxies

    Science.gov (United States)

    Petropoulou, V.; VíLchez, J. M.; Iglesias-Páramo, J.; Papaderos, P.

    In this work we study the effects of the Hercules cluster environment on the chemical history of star-forming (SF) galaxies. For this purpose we have derived the gas metallicities, the mean stellar metallicities and ages, the masses and the luminosities of our sample of galaxies. We have found that our Hercules SF galaxies are either chemically evolved spirals with nearly flat oxygen gradients, or less metal-rich dwarf galaxies which appear to be the "newcomers" in the cluster. Most Hercules SF galaxies follow well defined mass-metallicity and luminosity-metallicity sequences; nevertheless significant outliers to these relations have been identified, illustrating how environmental effects can provide a physical source of dispersion in these fundamental relations.

  13. Molecular Mechanisms by Which Marine Phytoplankton Respond to Their Dynamic Chemical Environment

    Science.gov (United States)

    Palenik, Brian

    2015-01-01

    Marine scientists have long been interested in the interactions of marine phytoplankton with their chemical environments. Nutrient availability clearly controls carbon fixation on a global scale, but the interactions between phytoplankton and nutrients are complex and include both short-term responses (seconds to minutes) and longer-term evolutionary adaptations. This review outlines how genomics and functional genomics approaches are providing a better understanding of these complex interactions, especially for cyanobacteria and diatoms, for which the genome sequences of multiple model organisms are available. Transporters and related genes are emerging as the most likely candidates for biomarkers in stress-specific studies, but other genes are also possible candidates. One surprise has been the important role of horizontal gene transfer in mediating chemical-biological interactions.

  14. Chemical Fouling Reduction of a Submersible Steel Spectrophotometer in Estuarine Environments Using a Sacrificial Zinc Anode.

    Science.gov (United States)

    Tait, Zachary S; Thompson, Megan; Stubbins, Aron

    2015-07-01

    The availability of in situ spectrophotometers, such as the S::CAN spectro::lyser, has expanded the possibilities for high-frequency water quality data collection. However, biological and chemical fouling can degrade the performance of in situ spectrophotometers, especially in saline environments with rapid flow rates. A complex freshwater washing system has been previously designed to reduce chemical fouling for the S::CAN spectro::lyser spectrophotometer. In the current study, we present a simpler, cheaper alternative: the attachment of a sacrificial zinc anode. Results are presented detailing the S::CAN spectro::lyser performance with and without the addition of the sacrificial anode. Attachment of the zinc anode provided efficient corrosion protection during 2-wk deployments in a highly dynamic (average tidal range, 2.5 m) saline tidal saltmarsh creek at Groves Creek, Skidaway Institute of Oceanography, Savannah, GA.

  15. Chemical Environment of Unusually Ge- and Pb-Rich Willemite, Tres Marias Mine, Mexico

    Directory of Open Access Journals (Sweden)

    Bernhardt Saini-Eidukat

    2016-03-01

    Full Text Available The Tres Marias carbonate-hosted Zn-Ge deposit in Chihuahua, Mexico contains willemite [Zn2SiO4] with unusually high concentrations of minor and trace elements (e.g., Pb, Ge, As, P, V; Pb concentrations are as high as 2 wt %, and Ge may reach 4000 ppm (average 900 ppm. Electron microprobe analyses and synchrotron X-ray fluorescence maps show that Zn and Ge, as well as Zn and Pb are negatively correlated, whereas Ge and Pb are positively correlated across zoned willemite crystals. In cathodoluminescence (CL images, those areas of willemite having high trace element concentrations have no, or low CL intensities, whereas zones low in trace elements (except for P display bright blue CL colors. X-ray absorption fine structure (XAFS spectroscopy was used to characterize the chemical nature of Ge and Pb in willemite. Comparisons to reference spectra of natural and artificial substances points to the presence of Ge4+ and Pb2+ in Tres Marias willemite. No evidence for Pb4+ was detected. Oscillatory zonation reflects trace element incorporation into willemite from the oxidation of primary Ge-bearing sphalerite and galena (PbS by siliceous aqueous fluids.

  16. Theoretical study of the influence of chemical reactions and physical parameters on the convective dissolution of CO2 in aqueous solutions

    Science.gov (United States)

    Loodts, Vanessa; Rongy, Laurence; De Wit, Anne

    2014-05-01

    Subsurface carbon sequestration has emerged as a promising solution to the problem of increasing atmospheric carbon dioxide (CO2) levels. How does the efficiency of such a sequestration process depend on the physical and chemical characteristics of the storage site? This question is emblematic of the need to better understand the dynamics of CO2 in subsurface formations, and in particular, the properties of the convective dissolution of CO2 in the salt water of aquifers. This dissolution is known to improve the safety of the sequestration by reducing the risks of leaks of CO2 to the atmosphere. Buoyancy-driven convection makes this dissolution faster by transporting dissolved CO2 further away from the interface. Indeed, upon injection, the less dense CO2 phase rises above the aqueous layer where it starts to dissolve. The dissolved CO2 increases the density of the aqueous solution, thereby creating a layer of denser CO2-rich solution above less dense solution. This unstable density gradient in the gravity field is at the origin of convection. In this framework, we theoretically investigate the effect of CO2 pressure, salt concentration, temperature, and chemical reactions on the dissolution-driven convection of CO2 in aqueous solutions. On the basis of a linear stability analysis, we assess the stability of the time-dependent density profiles developing when CO2 dissolves in an aqueous layer below it. We predict that increasing CO2 pressure destabilizes the system with regard to buoyancy-driven convection, because it increases the density gradient at the origin of the instability. By contrast, increasing salt concentration or temperature stabilizes the system via effects on CO2 solubility, solutal expansion coefficient, diffusion coefficient and on the viscosity and density of the solution. We also show that a reaction of CO2 with chemical species dissolved in the aqueous solution can either enhance or decrease the amplitude of the convective dissolution compared

  17. Passive Sampling in Regulatory Chemical Monitoring of Nonpolar Organic Compounds in the Aquatic Environment

    DEFF Research Database (Denmark)

    Booij, Kees; Robinson, Craig D; Burgess, Robert M;

    2016-01-01

    We reviewed compliance monitoring requirements in the European Union, the United States, and the Oslo-Paris Convention for the protection of the marine environment of the North-East Atlantic, and evaluated if these are met by passive sampling methods for nonpolar compounds. The strengths and shor...... is the best available technology for chemical monitoring of nonpolar organic compounds. Key issues to be addressed by scientists and environmental managers are outlined.......We reviewed compliance monitoring requirements in the European Union, the United States, and the Oslo-Paris Convention for the protection of the marine environment of the North-East Atlantic, and evaluated if these are met by passive sampling methods for nonpolar compounds. The strengths...... and shortcomings of passive sampling are assessed for water, sediments, and biota. Passive water sampling is a suitable technique for measuring concentrations of freely dissolved compounds. This method yields results that are incompatible with the EU's quality standard definition in terms of total concentrations...

  18. Aqueous foam surfactants for geothermal drilling fluids: 1. Screening

    Energy Technology Data Exchange (ETDEWEB)

    Rand, P.B.

    1980-01-01

    Aqueous foam is a promising drilling fluid for geothermal wells because it will minimize damage to the producing formation and would eliminate the erosion problems of air drilling. Successful use of aqueous foam will require a high foaming surfactant which will: (1) be chemically stable in the harsh thermal and chemical environment, and (2) form stable foams at high temperatures and pressures. The procedures developed to generate and test aqueous foams and the effects of a 260/sup 0/C temperature cycle on aqueous surfactant solutions are presented. More than fifty selected surfactants were evaluated with representatives from the amphoteric, anionic, cationic, and nonionic classes included. Most surfactants were severely degraded by this temperature cycle; however, some showed excellent retention of their properties. The most promising surfactant types were the alkyl and alkyl aryl sulfonates and the ethoxylated nonionics.

  19. Kinetic measurements and quantum chemical calculations on low spin Ni(II)/(III) macrocyclic complexes in aqueous and sulphato medium

    Indian Academy of Sciences (India)

    Anuradha Sankaran; E J Padma Malar; Venkatapuram Ramanujam Vijayaraghavan

    2015-07-01

    Cu(II) ion catalyzed kinetics of oxidation of H2O2 by [NiIIIL2] (L2 = 1,8-bis(2-hydroxyethyl)-1,3,6,8,10,13-hexaazacyclotetradecane) was studied in aqueous acidic medium in the presence of sulphate ion. The rate of oxidation of H2O2 by [NiIIIL2] is faster than that by [NiIIIL1] (L1 = 1,4,8,11-tetraazacyclote-tradecane) in sulphate medium. DFT calculations at BP86/def2-TZVP level lead to different modes of bonding between [NiL]II/III and water ligands (L = L1 and L2). In aqueous medium, two water molecules interact with [NiL]II through weak hydrogen bonds with L and are tilted by ∼23° from the vertical axis forming the dihydrate [NiL]2+.2H2O. However, there is coordinate bond formation between [NiL1]III and two water molecules in aqueous medium and an aqua and a sulphato ligand in sulphate medium leading to the octahedral complexes [NiL1(H2O)2]3+ and [NiL1(SO4)(H2O)]+. In the analogous [NiL2]III, the water molecules are bound by hydrogen bonds resulting in [NiL2]3+.2H2O and [NiL2(SO4)]+.H2O. As the sulphato complex [NiL2(SO4)]+.H2O is less stable than [NiL1(SO4)(H2O)]+ in view of the weak H-bonding interactions in the former it can react faster. Thus the difference in the mode of bonding between Ni(III) and the water ligand can explain the rate of oxidation of H2O2 by [NiIIIL] complexes.

  20. Chemical controls on uranyl citrate speciation and the self-assembly of nanoscale macrocycles and sandwich complexes in aqueous solutions.

    Science.gov (United States)

    Basile, M; Unruh, D K; Gojdas, K; Flores, E; Streicher, L; Forbes, T Z

    2015-03-28

    Uranyl citrate forms trimeric species at pH > 5.5, but exact structural characteristics of these important oligomers have not previously been reported. Crystallization and structural characterization of the trimers suggests the self-assembly of the 3 : 3 and 3 : 2 U : Cit complexes into larger sandwich and macrocyclic molecules. Raman spectroscopy and ESI-MS have been utilized to investigate the relative abundance of these species in solution under varying pH and citrate concentrations. Additional dynamic light scattering experiments indicate that self-assembly of the larger molecules does occur in aqueous solution.

  1. Characterizing the Chemical Stability of High Temperature Materials for Application in Extreme Environments

    Science.gov (United States)

    Opila, Elizabeth

    2005-01-01

    The chemical stability of high temperature materials must be known for use in the extreme environments of combustion applications. The characterization techniques available at NASA Glenn Research Center vary from fundamental thermodynamic property determination to material durability testing in actual engine environments. In this paper some of the unique techniques and facilities available at NASA Glenn will be reviewed. Multiple cell Knudsen effusion mass spectrometry is used to determine thermodynamic data by sampling gas species formed by reaction or equilibration in a Knudsen cell held in a vacuum. The transpiration technique can also be used to determine thermodynamic data of volatile species but at atmospheric pressures. Thermodynamic data in the Si-O-H(g) system were determined with this technique. Free Jet Sampling Mass Spectrometry can be used to study gas-solid interactions at a pressure of one atmosphere. Volatile Si(OH)4(g) was identified by this mass spectrometry technique. A High Pressure Burner Rig is used to expose high temperature materials in hydrocarbon-fueled combustion environments. Silicon carbide (SiC) volatility rates were measured in the burner rig as a function of total pressure, gas velocity and temperature. Finally, the Research Combustion Lab Rocket Test Cell is used to expose high temperature materials in hydrogen/oxygen rocket engine environments to assess material durability. SiC recession due to rocket engine exposures was measured as a function of oxidant/fuel ratio, temperature, and total pressure. The emphasis of the discussion for all techniques will be placed on experimental factors that must be controlled for accurate acquisition of results and reliable prediction of high temperature material chemical stability.

  2. Chemical basis for minimal cognition

    DEFF Research Database (Denmark)

    Hanczyc, Martin; Ikegami, Takashi

    We have developed a simple chemical system capable of self-movement in order to study the chemical-molecular origins of movement, perception and cognition. The system consists simply of an oil droplet in an aqueous environment. The aqueous phase contains a surfactant that modulates the interfacial...... tension between the drop of oil and its environment. We embed a chemical reaction in the oil phase that reacts with water when an oily precursor comes in contact with the water phase at the liquidliquid interface. This reaction not only powers the droplet to move in the aqueous phase but also allows......H and the environmental gradient. In our modeling, we demonstrated that a computational autopoietic cell could move by continuously self-repairing the membrane, but in this case failed to show any gradientclimbing behavior (Suzuki et al., 2008, Artificial Life, in press). This may be due to the fact that the autopoietic...

  3. Chemical basis for minimal cognition

    DEFF Research Database (Denmark)

    Hanczyc, Martin; Ikegami, Takashi

    We have developed a simple chemical system capable of self-movement in order to study the chemical-molecular origins of movement, perception and cognition. The system consists simply of an oil droplet in an aqueous environment. The aqueous phase contains a surfactant that modulates the interfacial...... tension between the drop of oil and its environment. We embed a chemical reaction in the oil phase that reacts with water when an oily precursor comes in contact with the water phase at the liquidliquid interface. This reaction not only powers the droplet to move in the aqueous phase but also allows...... for sustained movement. The direction of the movement is governed by a self-generated pH gradient that surrounds the droplet. In addition this self-generated gradient can be overridden by an externally imposed pH gradient, and therefore the direction of droplet motion may be controlled. Also we noticed...

  4. [Assessment of predictive dermal exposure to chemicals in the work environment].

    Science.gov (United States)

    Jankowska, Agnieszka; Czerczak, Sławomir; Kupczewska-Dobecka, Małgorzata

    2017-06-27

    Assessment of dermal exposure to chemicals in the work environment is problematic, mainly as a result of the lack of measurement data on occupational exposure to chemicals. Due to common prevalence of occupational skin exposure and its health consequences it is necessary to look for efficient solutions allowing for reliable exposure assessment. The aim of the study is to present predictive models used to assess non-measured dermal exposure, as well as to acquaint Polish users with the principles of the selected model functioning. This paper presents examples of models to assist the employer in the the assessment of occupational exposure associated with the skin contact with chemicals, developed in European Union (EU) countries, as well as in countries outside the EU. Based on the literature data dermal exposure models EASE (Estimation and Assessment of Substance Exposure), COSHH Essentials (Control of Substances Hazardous to Health Regulations), DREAM (Dermal Exposure Assessment Method), Stoffenmanager , ECETOC TRA (European Centre for Ecotoxicology and Toxicology of Chemicals Targeted Risk Assessment), MEASE (Metal's EASE), PHED (Pesticide Handlers Exposure Database), DERM (Dermal Exposure Ranking Method) and RISKOFDERM (Risk Assessment of Occupational Dermal Exposure to Chemicals) were briefly described. Moreover the characteristics of RISKOFDERM, guidelines for its use, information on input and output data were further detailed. Problem of full work shift dermal exposure assessment is described. An example of exposure assessment using RISKOFDERM and effectiveness evaluation to date were also presented. When no measurements are available, RISKOFDERM allows dermal exposure assessment and thus can improve the risk assessment quality and effectiveness of dermal risk management. Med Pr 2017;68(4):557-569. This work is available in Open Access model and licensed under a CC BY-NC 3.0 PL license.

  5. Chemically modified olive stone: a low-cost sorbent for heavy metals and basic dyes removal from aqueous solutions.

    Science.gov (United States)

    Aziz, Abdellah; Ouali, Mohand Said; Elandaloussi, El Hadj; De Menorval, Louis Charles; Lindheimer, Marc

    2009-04-15

    In the present work, we have investigated the sorption efficiency of treated olive stones (TOS) towards cadmium and safranine removal from their respective aqueous solutions. TOS material was prepared by treatment of olive stones with concentrated sulfuric acid at room temperature followed up by a subsequent neutralization with 0.1 M NaOH aqueous solution. The resulting material has been thoroughly characterized by SEM, energy-dispersive X-ray (EDX), MAS (13)C NMR, FTIR and physicochemical parameters were calculated. The sorption study of TOS at the solid-liquid interface was investigated using kinetics, sorption isotherms, pH effect and thermodynamic parameters. The preliminary results indicate that TOS exhibit a better efficiency in terms of sorption capacities toward the two pollutants (128.2 and 526.3 mg/g for cadmium and safranine, respectively) than those reported so far in the literature. Moreover, the sorption process is ascertained to occur fast enough so that the equilibrium is reached in less than 15 min of contact time. The results found in the course of this study suggest that ion exchange mechanism is the most appropriate mechanism involved in cadmium and safranine removal. Finally, the sorption efficiency of TOS is compared to those of other low-cost sorbents materials yet described in the literature.

  6. Adsorptive Removal of Benzene and Toluene from Aqueous Environments by Cupric Oxide Nanoparticles: Kinetics and Isotherm Studies

    Directory of Open Access Journals (Sweden)

    Leili Mohammadi

    2017-01-01

    Full Text Available Removal of benzene and toluene, as the major pollutants of water resources, has attracted researchers’ attention, given the risk they pose to human health. In the present study, the potential of copper oxide nanoparticles (CuO-NPs in eliminating benzene and toluene from a mixed aqueous solution was evaluated. For this, we performed batch experiments to investigate the effect of solution pH (3–13, dose of CuO-NPs (0.1–0.8 g, contact time (5–120 min, and concentration of benzene and toluene (10–200 mg/l on sorption efficiency. The maximum removal was observed at neutral pH. By using the Langmuir model, we measured the highest adsorption capacity to be 100.24 mg/g for benzene and 111.31 mg/g for toluene. Under optimal conditions, adsorption efficiency was 98.7% and 92.5% for benzene and toluene, respectively. The sorption data by CuO-NPs well fitted into the following models: Langmuir, Freundlich, Temkin, and Dubinin-Radushkevich model. The experimental information well fitted in the Freundlich for benzene and Langmuir for toluene. Based on the results, adsorption followed pseudo-second-order kinetics with acceptable coefficients. The findings introduced CuO-NPs as efficient compounds in pollutants adsorption. In fact, they could be used to develop a simple and efficient pollutant removal method from aqueous solutions.

  7. Electrochemical, computational and spectroscopic investigation on local environment of plutonium in ionic liquid and aqueous medium. A comparative study

    Energy Technology Data Exchange (ETDEWEB)

    Sengupta, Arijit; Murali, Mallekav S.; Mohapatra, Prasanta Kumar [Bhabha Atomic Research Centre Trombay, Mumbai (India). Radiochemistry Div.; Ali, Sk. Musharaf; Shenoy, Kalsanka Trivikram [Bhabha Atomic Research Centre Trombay, Mumbai (India). Chemical Engineering Div.

    2016-07-01

    With an aim to understand the nature of species, cyclic voltammetry (CV) of Pu(IV) in dilute HBr and in a room temperature ionic liquid (RTIL), 1-octyl-3-methylimidazolium bromide (C{sub 8}mimBr) was carried out. Shifts of cathodic and anodic peak potentials of Pu(IV) cyclic voltammograms were observed towards negative potentials in the extended electrochemical window for ionic liquid medium compared to 2 M HBr. The diffusion coefficient of the most likely species of Pu(IV) in aqueous medium was found to be greater than that of the corresponding species in ionic liquid while the activation energy showed reverse trend. The Pu(IV)/Pu(III) redox reaction was found to be exothermic in aqueous medium while it was endothermic in C{sub 8}mimBr. The redox reaction was found to be quasi reversible for both the media while the extent of irreversibility was more in ionic liquid. UV-Vis spectroscopy of Pu in these media showed significant differences in the peak positions and their relative intensities, indicating the possible differences in the interactions of Pu(IV) with the solvent molecules resulting in speciation differences. A new prominent peak was observed in RTIL which could be for a new species of Pu(IV). Computational studies were also carried out to understand the solvation of Pu and the possibility of thermodynamic conversion from Pu(IV) to Pu(III).

  8. Sonochemical synthesis of Au-TiO2 nanoparticles for the sonophotocatalytic degradation of organic pollutants in aqueous environment.

    Science.gov (United States)

    Anandan, Sambandam; Ashokkumar, Muthupandian

    2009-03-01

    Au-TiO2 photocatalysts were sonochemically prepared by three different procedures and their photocatalytic and sonophotocatalytic efficiencies were evaluated by studying the degradation of a representative organic pollutant, nonylphenol ethoxylate (NPE) surfactant in aqueous solutions. In the first procedure, Au-TiO2 nanoparticles were prepared by depositing sonochemically synthesized gold nanoparticles on Degussa P25 TiO2 by stirring in the absence of an ultrasonic field. In the second procedure, Au nanoparticles were sonochemically synthesized and simultaneously deposited on Degussa P25 TiO2 particles. In the third procedure, Au-TiO2 nanoparticles were sonochemically synthesized by the simultaneous irradiation of an aqueous solution containing AuCl4- and titanium tetraisopropoxide. The prepared nanoparticles were characterized by UV-vis spectroscopy and transmission electron microscopy (TEM). The catalytic activities of these nanomaterials were compared for the degradation of a polydisperse nonylphenol ethoxylate, Teric GN9 by photocatalysis and sonophotocatalysis under visible light/high frequency ultrasound irradiation. The catalysts did not show a synergetic effect towards the sonophotocatalytic degradation of Teric GN9. This might be due to the interference of the degradation products generated during the simultaneous irradiation by light and ultrasound.

  9. Towards Cluster-Assembled Materials of True Monodispersity in Size and Chemical Environment: Synthesis, Dynamics and Activity

    Science.gov (United States)

    2016-10-27

    pathway Status: not yet published Diverse technologies, from catalyst coking to graphene synthesis , entail hydrocarbon dehydrogena- tion and...AFRL-AFOSR-UK-TR-2016-0037 Towards cluster-assembled materials of true monodispersity in size and chemical environment: Synthesis , Dynamics and...Towards cluster-assembled materials of true monodispersity in size and chemical environment: synthesis , dynamics and activity 5a.  CONTRACT NUMBER 5b

  10. Aqueous-phase photooxidation of levoglucosan - a mechanistic study using aerosol time-of-flight chemical ionization mass spectrometry (Aerosol ToF-CIMS)

    Science.gov (United States)

    Zhao, R.; Mungall, E. L.; Lee, A. K. Y.; Aljawhary, D.; Abbatt, J. P. D.

    2014-09-01

    Levoglucosan (LG) is a widely employed tracer for biomass burning (BB). Recent studies have shown that LG can react rapidly with hydroxyl (OH) radicals in the aqueous phase despite many mass balance receptor models assuming it to be inert during atmospheric transport. In the current study, aqueous-phase photooxidation of LG by OH radicals was performed in the laboratory. The reaction kinetics and products were monitored by aerosol time-of-flight chemical ionization mass spectrometry (Aerosol ToF-CIMS). Approximately 50 reaction products were detected by the Aerosol ToF-CIMS during the photooxidation experiments, representing one of the most detailed product studies yet performed. By following the evolution of mass defects of product peaks, unique trends of adding oxygen (+O) and removing hydrogen (-2H) were observed among the products detected, providing useful information for determining potential reaction mechanisms and sequences. Additionally, bond-scission reactions take place, leading to reaction intermediates with lower carbon numbers. We introduce a data analysis framework where the average oxidation state (OSc) is plotted against a novel molecular property: double-bond-equivalence-to-carbon ratio (DBE/#C). The trajectory of LG photooxidation on this plot suggests formation of polycarbonyl intermediates and their subsequent conversion to carboxylic acids as a general reaction trend. We also determined the rate constant of LG with OH radicals at room temperature to be 1.08 ± 0.16 × 109 M-1 s-1. By coupling an aerosol mass spectrometer (AMS) to the system, we observed a rapid decay of the mass fraction of organic signals at mass-to-charge ratio 60 (f60), corresponding closely to the LG decay monitored by the Aerosol ToF-CIMS. The trajectory of LG photooxidation on a f44-f60 correlation plot matched closely to literature field measurement data. This implies that aqueous-phase photooxidation might be partially contributing to aging of BB particles in the

  11. Aqueous-phase photooxidation of levoglucosan - a mechanistic study using Aerosol Time of Flight Chemical Ionization Mass Spectrometry (Aerosol-ToF-CIMS)

    Science.gov (United States)

    Zhao, R.; Mungall, E. L.; Lee, A. K. Y.; Aljawhary, D.; Abbatt, J. P. D.

    2014-04-01

    Levoglucosan (LG) is a widely employed tracer for biomass burning (BB). Recent studies have shown that LG can react rapidly with hydroxyl (OH) radicals in the aqueous phase, despite many mass balance receptor models assuming it to be inert during atmospheric transport. In the current study, aqueous-phase photooxidation of LG by OH radicals was performed in the laboratory. The reaction kinetics and products were monitored by Aerosol Time of Flight Chemical Ionization Mass Spectrometry (Aerosol-ToF-CIMS). Approximately 50 reaction products were detected by the Aerosol-ToF-CIMS during the photooxidation experiments, representing one of the most detailed product studies yet performed. By following the evolution of mass defects of product peaks, unique trends of adding oxygen (+O) and removing hydrogen (-2H) were observed among the products detected, providing useful information to determine potential reaction mechanisms and sequences. As well, bond scission reactions take place, leading to reaction intermediates with lower carbon numbers. We introduce a data analysis framework where the average oxidation state (OSc) is plotted against a novel molecular property: double bond equivalence to carbon ratio (DBE / #C). The trajectory of LG photooxidation on this plot suggests formation of poly-carbonyl intermediates and their subsequent conversion to carboxylic acids as a general reaction trend. We also determined the rate constant of LG with OH radicals at room temperature to be 1.08 ± 0.16 × 109 M-1 s-1. By coupling an Aerosol Mass Spectrometer (AMS) to the system, we observed a rapid decay of the mass fraction of organic signals at mass-to-charge ratio 60 (f60), corresponding closely to the LG decay monitored by the Aerosol-ToF-CIMS. The trajectory of LG photooxidation on a f44-f60 correlation plot matched closely to literature field measurement data. This implies that aqueous-phase photooxidation might be partially contributing to aging of BB particles in the ambient

  12. Calculation of chemical equilibrium between aqueous solution and minerals: the EQ3/6 software package. [In FORTRAN extended 4. 6 for CDC6600 and 7600

    Energy Technology Data Exchange (ETDEWEB)

    Wolery, T.J.

    1979-02-01

    The newly developed EQ/36 software package computes equilibrium models of aqueous geochemical systems. The package contains two principal programs: EQ3 performs distribution-of-species calculations for natural water compositions; EQ6 uses the results of EQ3 to predict the consequences of heating and cooling aqueous solutions and of irreversible reaction in rock--water systems. The programs are valuable for studying such phenomena as the formation of ore bodies, scaling and plugging in geothermal development, and the long-term disposal of nuclear waste. EQ3 and EQ6 are compared with such well-known geochemical codes as SOLMNEQ, WATEQ, REDEQL, MINEQL, and PATHI. The data base allows calculations in the temperature interval 0 to 350{sup 0}C, at either 1 atm-steam saturation pressures or a constant 500 bars. The activity coefficient approximations for aqueous solutes limit modeling to solutions of ionic strength less than about one molal. The mathematical derivations and numerical techniques used in EQ6 are presented in detail. The program uses the Newton--Raphson method to solve the governing equations of chemical equilibrium for a system of specified elemental composition at fixed temperature and pressure. Convergence is aided by optimizing starting estimates and by under-relaxation techniques. The minerals present in the stable phase assemblage are found by several empirical methods. Reaction path models may be generated by using this approach in conjunction with finite differences. This method is analogous to applying high-order predictor--corrector methods to integrate a corresponding set of ordinary differential equations, but avoids propagation of error (drift). 8 figures, 9 tables.

  13. Resistance to chemical attack of bittern-resisting cement in high-bittern environment

    Institute of Scientific and Technical Information of China (English)

    Yunbing Hou; Bingwen Wang; Yu Chen; Botao Zhang; Lin Yu

    2005-01-01

    A new kind of bittern-resisting cement (BRC) was introduced. This material is based on the ternary cementitious system of clinker containing C4A3 -S phase, high-activity ground granulated blast-furnace slag (GGBFS) and fly ash (FA). The hydration process and the hydrated products of BRC were studied by means of XRD, TG-DTA and SEM, and the resistance to chemical attack of BRC in high-bittern environment was also examined. The corrosion experiment in seven kinds of brines proved that BRC exhibits an excellent resistance to chemical attack of bittern. The corrosion resistance factors were calculated and all of them were greater than 0.96. It showed that BRC totally controls the cement-based material corrosion in brines from four aspects: (1) making full use of the dominant complementation effect of mineral materials; (2) diminishing the hydrated products easy to be attacked; (3) improving the microstructure of hardened cement mortar; (4) degrading the chemical attack of bittern.

  14. Development and testing of a prototype tool for integrated assessment of chemical status in marine environments.

    Science.gov (United States)

    Andersen, Jesper H; Murray, Ciarán; Larsen, Martin M; Green, Norman; Høgåsen, Tore; Dahlgren, Elin; Garnaga-Budrė, Galina; Gustavson, Kim; Haarich, Michael; Kallenbach, Emilie M F; Mannio, Jaakko; Strand, Jakob; Korpinen, Samuli

    2016-02-01

    We report the development and application of a prototype tool for integrated assessment of chemical status in aquatic environments based on substance- and matrix-specific environmental assessment criteria (thresholds). The Chemical Status Assessment Tool (CHASE) integrates data on hazardous substances in water, sediments and biota as well as bio-effect indicators and is based on a substance- or bio-effect-specific calculation of a 'contamination ratio' being the ratio between an observed concentration and a threshold value. Values 1.0 indicate areas potentially 'affected'. These ratios are combined within matrices, i.e. for water, sediment and biota and for biological effects. The overall assessment used a 'one out, all out principle' with regard to each matrix. The CHASE tool was tested in the Baltic Sea and the North Sea in 376 assessment units. In the former, the chemical status was >1.0 in practically all areas indicating that all areas assessed were potentially affected. The North Sea included areas classified as unaffected or affected. The CHASE tool can in combination with temporal trend assessments of individual substances be advantageous for use in remedial action plans and, in particular, for the science-based evaluation of the status and for determining which specific substances are responsible for a status as potentially affected.

  15. Redistribution and Evolution of Organics During Aqueous Alteration: NanoSIMS-STXM-TEM Analyses of FIB Sections from Renazzo, Murchison and Orgueil

    Science.gov (United States)

    Le Guillou, C.; Remusat, L.; Bernard, S.; Brearley, A. J.

    2011-03-01

    What is the in situ spatial distribution and environment of organic grains in carbonaceous chondrites matrices? They seem to evolve physically and chemically during aqueous alteration and show relationship with phyllosilicates and carbonates.

  16. Fabrication of Lead-Free Bi0.5Na0.5TiO3 Thin Films by Aqueous Chemical Solution Deposition

    Directory of Open Access Journals (Sweden)

    Mads Christensen

    2017-02-01

    Full Text Available Piezoelectric ceramics are widely used in actuator applications, and currently the vast majority of these devices are based on Pb ( Zr , Ti O 3 , which constitutes environmental and health hazards due to the toxicity of lead. One of the most promising lead-free material systems for actuators is based on Bi 0 . 5 Na 0 . 5 TiO 3 (BNT, and here we report on successful fabrication of BNT thin films by aqueous chemical solution deposition. The precursor solution used in the synthesis is based on bismuth citrate stabilized by ethanolamine, NaOH , and a Ti-citrate prepared from titanium tetraisopropoxide and citric acid. BNT thin films were deposited on SrTiO 3 and platinized silicon substrates by spin-coating, and the films were pyrolized and annealed by rapid thermal processing. The BNT perovskite phase formed after calcination at 500 °C in air. The deposited thin films were single phase according to X-ray diffraction, and the microstructures of the films shown by electron microscopy were homogeneous and dense. Decomposition of the gel was thoroughly investigated, and the conditions resulting in phase pure materials were identified. This new aqueous deposition route is low cost, robust, and suitable for development of BNT based thin film for actuator applications.

  17. Comparison between Chemical Senses Thresholds for Capsaicin and Dihydrocapsaicin in Aqueous Solutions and Identification of the Area of Burning Sensation

    Directory of Open Access Journals (Sweden)

    D.J. Schneider

    2014-01-01

    Full Text Available In the present study, the pungency detection thresholds for capsaicin and dihydrocapsaicin in aqueous solutions containing an emulsifier (polysorbate 80 were determined and compared. Thresholds were measured for 21 students (12 chili “users” and 9 “non users” using a 3-Alternative Forced Choice sensory test with ascending concentrations of capsaicin and dihydrocapsaicin (0.025, 0.045, 0.090, 0.180 and 0.360 ppm, respectively. In addition, the panelists were asked where the irritation occurred (throat, tongue or both. The group Best Estimate Thresholds were 0.080 and 0.049 ppm for capsaicin and dihydrocapsaicin, respectively and differed significantly. Chili “users” and “non users” did not differ significantly in their perception of capsaicin and dihydrocapsaicin, suggesting that no desensitization effects occur. In accordance with previous studies, in most cases the first irritation was experienced in the throat.

  18. Standard Gibbs free energies of reactions of ozone with free radicals in aqueous solution: quantum-chemical calculations.

    Science.gov (United States)

    Naumov, Sergej; von Sonntag, Clemens

    2011-11-01

    Free radicals are common intermediates in the chemistry of ozone in aqueous solution. Their reactions with ozone have been probed by calculating the standard Gibbs free energies of such reactions using density functional theory (Jaguar 7.6 program). O(2) reacts fast and irreversibly only with simple carbon-centered radicals. In contrast, ozone also reacts irreversibly with conjugated carbon-centered radicals such as bisallylic (hydroxycylohexadienyl) radicals, with conjugated carbon/oxygen-centered radicals such as phenoxyl radicals, and even with nitrogen- oxygen-, sulfur-, and halogen-centered radicals. In these reactions, further ozone-reactive radicals are generated. Chain reactions may destroy ozone without giving rise to products other than O(2). This may be of importance when ozonation is used in pollution control, and reactions of free radicals with ozone have to be taken into account in modeling such processes.

  19. Phenanthrene removal from aqueous solutions using well-characterized, raw, chemically treated, and charred malt spent rootlets, a food industry by-product.

    Science.gov (United States)

    Valili, Styliani; Siavalas, George; Karapanagioti, Hrissi K; Manariotis, Ioannis D; Christanis, Kimon

    2013-10-15

    Malt spent rootlets (MSR) are biomaterials produced in big quantities by beer industry as by-products. A sustainable solution is required for their management. In the present study, MSR are examined as sorbents of a hydrophobic organic compound, phenanthrene, from aqueous solutions. Raw MSR sorb phenanthrene but their sorptive properties are not competitive with the respective properties of commercial sorbents (e.g., activated carbons). Organic petrography is used as a tool to characterize MSR after treatment in order to produce an effective sorbent for phenanthrene. Chemical and thermal (at low temperature under nitrogen atmosphere) treatments of MSR did not result in highly effective sorbents. Based on organic petrography characterization, the pores of the treated materials were filled with humic colloids. When pyrolysis at 800 °C was used to treat MSR, a sorbent with new and empty pores was produced. Phenanthrene sorption capacity was 2 orders of magnitude higher for the pyrolized MSR than for raw MSR.

  20. A Reversible Pyrene-based Turn-on Luminescent Chemosensor for Selective Detection of Fe(3+) in Aqueous Environment with Logic Gate Application.

    Science.gov (United States)

    Mukherjee, Soma; Talukder, Shrabani

    2016-05-01

    A new Schiff-base, HL luminescent chemosensor of 1-amino pyrene and 8-hydroxy quinoline-2-carboxaldehyde was synthesized which demonstrates selective fluorimetric detection of Fe(3+) in aqueous medium with detection limit of 2.52 × 10(-8) M. The receptor shows selective 'turn-on' response towards Fe(3+) over other metal ions. This gradual 'turn-on' fluorescence response for Fe(3+) may be induced via CHEF (chelation-enhanced fluorescence) through close proximity of pyrene rings. The stoichiometry and binding property of HL with Fe(3+) was examined by emission studies. In presence of Fe(3+), HL also exhibits reversible change in emission pattern with EDTA and thus offers an interesting property of molecular 'INHIBIT' logic gate with Fe(3+) and EDTA as chemical inputs.

  1. Chemical Composition and Properties of the Liquid-Vapor Interface of Aqueous C1 to C4 Monofunctional Acid and Alcohol Solutions.

    Science.gov (United States)

    Lee, Ming-Tao; Orlando, Fabrizio; Artiglia, Luca; Chen, Shuzhen; Ammann, Markus

    2016-12-15

    The liquid-vapor interface is playing an important role in aerosol and cloud chemistry in cloud droplet activation by aerosol particles and potentially also in ice nucleation. We have employed the surface sensitive and chemically selective X-ray photoelectron spectroscopy (XPS) technique to examine the liquid-vapor interface for mixtures of water and small alcohols or small carboxylic acids (C1 to C4), abundant chemicals in the atmosphere in concentration ranges relevant for cloud chemistry or aerosol particles at the point of activation into a cloud droplet. A linear correlation was found between the headgroup carbon 1s core-level signal intensity and the surface excess derived from literature surface tension data with the offset being explained by the bulk contribution to the photoemission signal. The relative interfacial enhancement of the carboxylic acids over the carboxylates at the same bulk concentration was found to be highest (nearly 20) for propionic acid/propionate and still about 5 for formic acid/formate, also in fair agreement with surface tension measurements. This provides direct spectroscopic evidence for high carboxylic acid concentrations at aqueous solution-air interfaces that may be responsible for acid catalyzed chemistry under moderately acidic conditions with respect to their bulk aqueous phase acidity constant. By assessing the ratio of aliphatic to headgroup C 1s signal intensities XPS also provides information about the orientation of the molecules. The results indicate an increasing orientation of alcohols and neutral acids toward the surface normal as a function of chain length, along with increasing importance of lateral hydrophobic interactions at higher surface coverage. In turn, the carboxylate ions exhibit stronger orientation toward the surface normal than the corresponding neutral acids, likely caused by the stronger hydration of the charged headgroup.

  2. Influence of the pore structure and surface chemical properties of activated carbon on the adsorption of mercury from aqueous solutions.

    Science.gov (United States)

    Lu, Xincheng; Jiang, Jianchun; Sun, Kang; Wang, Jinbiao; Zhang, Yanping

    2014-01-15

    Reactivation and chemical modification were used to obtain modified activated carbons with different pore structure and surface chemical properties. The samples were characterized by nitrogen absorption-desorption, Fourier transform infrared spectroscopy and the Bothem method. Using mercury chloride as the target pollutant, the Hg(2+) adsorption ability of samples was investigated. The results show that the Hg(2+) adsorption capacity of samples increased significantly with increases in micropores and acidic functional groups and that the adsorption process was exothermic. Different models and thermodynamic parameters were evaluated to establish the mechanisms. It was concluded that the adsorption occurred through a monolayer mechanism by a two-speed process involving both rapid adsorption and slow adsorption. The adsorption rate was determined by chemical reaction.

  3. Seasonal variation of PM10 chemical constituents in different French urban environments

    Science.gov (United States)

    Salameh, Dalia; Golly, Benjamin; Besombes, Jean Luc; Alleman, Laurent; Favez, Olivier; Jaffrezo, Jean Luc

    2016-04-01

    Particulate matter (PM10, with a diameter less than 10 μm) is a heterogeneous mixture of natural and anthropogenic components including organic and elemental carbon (OC, and EC), sulfates, nitrates, ammonium, mineral dust, trace elements, seasalt, which has been linked to adverse impact on human health, visibility, and climate change. Atmospheric PM concentration and composition can vary widely due to different climatic conditions and local features such as anthropogenic source types, emission rates and dispersion patterns. Moreover, the contribution of natural sources (e.g. seasalt and dust) varies from one region to another. However, a fundamental step towards a better understanding and identification of the sources of PM10 is constituted by the study of aerosol chemical composition. Moreover, in order to define cost effective emission abatement strategies, research studies to interpret the variability of PM10 levels and components and to identify the main emission sources influencing ambient air PM10 levels is still needed. In a national context of a better understanding of PM composition and sources, and therefore the implementation of efficient reduction plans of PM in France, various monitoring campaigns were carried out recently within different air quality programs, where PM10 filter samples were collected on a 24 hour basis at various type of French sites (e.g. urban, rural, etc.,), located in different urban environments. An extensive chemical characterization of PM10 composition at these sites was performed, and a large range of analytical techniques was used to determine the concentrations of various chemical species which included the analysis of OC, and EC, major ionic species (SO42-, NO3-, Cl-, NH4+, K+, Na+, Mg2+, and Ca2+), metals and trace elements (e.g. Al, Ca, Cu, Fe, K, Mg, Mn, Na, Ni, Pb, V, Zn, etc.,), and organic compounds (e.g. sugars, polyols, PAH, methyl PAH, sulfur PAH, alkanes, hopanes, and methoxyphenols). The seasonal and spatial

  4. Theory of terahertz pumping of chemical environments in the condensed phase

    Energy Technology Data Exchange (ETDEWEB)

    Mishra, Pankaj Kumar

    2015-12-15

    Newly emerged light-sources allow to generate fully synchronized, ultrashort and highly intense light pulses. With these light pulses, it is possible to initiate a process by a pump pulse and follow the dynamics via probe pulse in the femtosecond timescale. These pump-probe experiments play an important role for studying the chemical and biological processes in real time. Such techniques are also used to generate temperature-jump (T-jump) in ultrashort timescale to study the very fast kinetics of fundamental steps in chemical processes. Because of its biological and chemical relevance, T-jump experiments on liquid water have gained a lot of attention. Rather than acting as a passive environment, the dynamics of water during chemical and biological processes play a fundamental role in the solvation and stabilization of reaction intermediates. To target the O-H stretching mode of water with an infrared (IR) laser is a widely used mechanism to generate the T-jump in nanosecond to femtosecond timescales. With these techniques, T-jump has been limited only to few 10s of K so far. In this thesis, a new mechanism is investigated to generate T-jump up to few 100s of K in sub-ps timescale. The main portion of this thesis concentrates on the response of liquid water to sub-cycle THz pump pulses spectrally centered at 100 cm{sup -1} (∝3 THz). The THz pump pulse with intensity of 5 x 10{sup 12} W/cm{sup 2} transfers a large amount of energy to inter- and intramolecular vibrations of water in sub-ps timescale. After the pump pulse, water reaches to a quasiequilibrium state, which is a gas-like hot liquid. The large energy gain in water causes significant structural modifications and vibrational shifting, which can be probed by timeresolved coherent x-ray scattering and time-resolved IR spectroscopy, respectively. Here, the interaction of THz pulse with water molecules is investigated from clusters to bulk water. We find it to be mainly described via the interaction of

  5. High-content behavioral analysis of Caenorhabditis elegans in precise spatiotemporal chemical environments.

    Science.gov (United States)

    Albrecht, Dirk R; Bargmann, Cornelia I

    2011-06-12

    To quantitatively understand chemosensory behaviors, it is desirable to present many animals with repeatable, well-defined chemical stimuli. To that end, we describe a microfluidic system to analyze Caenorhabditis elegans behavior in defined temporal and spatial stimulus patterns. A 2 cm × 2 cm structured arena allowed C. elegans to perform crawling locomotion in a controlled liquid environment. We characterized behavioral responses to attractive odors with three stimulus patterns: temporal pulses, spatial stripes and a linear concentration gradient, all delivered in the fluid phase to eliminate variability associated with air-fluid transitions. Different stimulus configurations preferentially revealed turning dynamics in a biased random walk, directed orientation into an odor stripe and speed regulation by odor. We identified both expected and unexpected responses in wild-type worms and sensory mutants by quantifying dozens of behavioral parameters. The devices are inexpensive, easy to fabricate, reusable and suitable for delivering any liquid-borne stimulus.

  6. The importance of chemical components in cleaning agents for the indoor environment

    DEFF Research Database (Denmark)

    Vejrup, Karl Ventzel

    In order to evaluate the importance for the indoor environment of chemical compounds in cleaning agents, the emission of VOCs (Volatile Organic Compounds) from 10 selected cleaning agents and the content of LAS (Linear AlkanbenzeneSulfonate) in dust samples from 7 buildings were investigated...... VOCs. In one experiment, the concentration of nonpolar VOCs in the breathing zone of a person who treated the floor in a large climate chamber (45 m3) using a water based polish product was found to be 3,9 mg/m3. Use of scented cleaning agents usually means that odour thresholds of some compounds...... included in this investigation had a content of 2-(2-ethoxyethoxy)ethanol of 1,5% and 3.1%. Investigation of their emission profiles in the FLEC showed that the emission of polar VOCs is delayed until the surface is nearly dry, hence the polar VOCs have elongated emission profiles. In experiments...

  7. Probing Structural and Catalytic Characteristics of Galactose Oxidase Confined in Nanoscale Chemical Environments

    DEFF Research Database (Denmark)

    Ikemoto, Hideki; Mossin, Susanne; Ulstrup, Jens;

    2014-01-01

    Galactose oxidase (GAOX) is a special metalloenzyme in terms of its active site structure and catalytic mechanisms. This work reports a study where the enzyme confined in a nanoscale chemical environment provided by mesoporous silicas (MPS) is probed. Two types of MPS, i.e. SBA-15 and MCF, were...... synthesized and used to accommodate GAOX. SBA-15-ROD is rod-shaped particles with periodically ordered nanopores (9.5 nm), while MCF has a mesocellular foam-like structure with randomly distributed pores (23 nm) interconnected by smaller windows (8.8 nm). GAOX is non-covalently confined in SBA-15- ROD, while...... constant (KM) of the enzyme is largely unchanged upon immobilization, while the turnover number (kcat) is slightly reduced. The overall catalytic efficiency, represented by the ratio of kcat/KM, is retained around 70% and 60% for SBA-15 and MCF immobilization, respectively. The thermal resistance...

  8. Surface Structure of GaN(0001) in the Chemical Vapor Deposition Environment

    Energy Technology Data Exchange (ETDEWEB)

    Munkholm, A. [Chemistry Division, Argonne National Laboratory, Argonne, Illinois 60439 (United States); Stephenson, G.B.; Eastman, J.A.; Thompson, C.; Auciello, O. [Materials Science Division, Argonne National Laboratory, Argonne, Illinois 60439 (United States); Thompson, C. [Department of Physics, Northern Illinois University, DeKalb, Illinois 60115 (United States); Fini, P.; Speck, J.S.; DenBaars, S.P. [Materials Department, University of California, Santa Barbara, California 93106 (United States); Fuoss, P.H. [ATT Laboratories---Research, Florham Park, New Jersey 07932 (United States)

    1999-07-01

    We report the first observation of the atomic-scale structure of the GaN(0001) surface in the metal-organic chemical vapor deposition environment. Measurements were performed using {ital in situ} grazing-incidence x-ray scattering. We determined the surface equilibrium phase diagram as a function of temperature and ammonia partial pressure, which contains two phases with 1{times}1 and ({radical} (3) {times}2{radical} (3) )R30{degree} symmetries. The ({radical} (3) {times}2{radical} (3) )R30{degree} phase is found to have a novel {open_quotes}missing row{close_quotes} structure with 1/3 of the surface Ga atoms absent. {copyright} {ital 1999} {ital The American Physical Society }

  9. The chemical effects of the Martian environment on power system component materials: A theoretical approach

    Science.gov (United States)

    Perez-Davis, Marla E.; Gaier, James R.

    1990-01-01

    In the foreseeable future, an expedition may be undertaken to explore the planet Mars. Some of the power source options being considered for such a mission are photovoltaics, regenerative fuel cells and nuclear reactors. In addition to electrical power requirements, environmental conditions en route to Mars, in the planetary orbit and on the Martian surface must be simulated and studied in order to anticipate and solve potential problems. Space power systems components such as photovoltaic arrays, radiators, and solar concentrators may be vulnerable to degradation in the Martian environment. Natural characteristics of Mars which may pose a threat to surface power systems include high velocity winds, dust, ultraviolet radiation, large daily variation in temperature, reaction to components of the soil, atmosphere and atmospheric condensates as well as synergistic combinations. Most of the current knowledge of the characteristics of the Martian atmosphere and soil composition was obtained from the Viking 1 and 2 missions in 1976. A theoretical study is presented which was used to assess the effects of the Martian atmospheric conditions on the power systems components. A computer program written at NASA-Lewis for combustion research that uses a free energy minimization technique was used to calculate chemical equilibrium for assigned thermodynamic states of temperature and pressure. The power system component materials selected for this study include: silicon dioxide, silicon, carbon, copper, and titanium. Combinations of environments and materials considered include: (1) Mars atmosphere with power surface material, (2) Mars atmosphere and dust component with power surface material, and (3) Mars atmosphere and hydrogen peroxide or superoxide or superoxide with power system material. The chemical equilibrium calculations were performed at a composition ratio (oxidant to reactant) of 100. The temperature for the silicon dioxide material and silicon, which simulate

  10. Crossed optical and chemical evaluations of modern glass soiling in various European urban environments

    Science.gov (United States)

    Favez, Olivier; Cachier, Hélène; Chabas, Anne; Ausset, Patrick; Lefevre, Roger

    As part of the MULTI-ASSESS and VIDRIO EC projects, the soiling of modern glass is characterised in various European urban atmospheres. Our original methodology relies on crossed chemical measurements of the deposit (evaluation of the ion, elemental and organic carbon contents, and subsequent "mass closure") and exhaustive measurements of glass optical properties (light reflectance, transmittance and absorption). Samples were exposed sheltered from rain in Athens, Krakow, London, Montelibretti (Italy), Prague and Troyes (France), during increasing exposure durations, up to more than two years. Although a slowing down of the deposition rate is observed for some species at some sites, no obvious saturation phenomenon seems to occur for the particle deposition. The chemical composition of the deposit is shown to reflect the atmospheric environment of the exposure site. Some post-deposit evolutions, such as the disappearance of ammonium and possibly of particulate organic matter, are found to occur. For thin deposits, the glass optical properties (e.g. light absorption and diffuse transmittance) are found to evolve quasi-linearly with species concentrations (EC and ions, respectively). However, for conditions creating heavier deposits such as long time exposures in rather polluted environments, a saturation phenomenon is observed. Using a simple model, light absorption, which is primarily due to EC particles, is shown to reach the saturation level ( S) for A≈16% and the concentration for which the semi-saturation level is reached (C 1/2) is found to be about 15 μgC of EC/cm 2. For diffuse transmittance, due to scattering species, these parameters are found to be about 30% and 65 μg of ions/cm 2, respectively. These values may be considered as representative of the soiling in Europe.

  11. Valorisation of Vietnamese Rice Straw Waste: Catalytic Aqueous Phase Reforming of Hydrolysate from Steam Explosion to Platform Chemicals

    Directory of Open Access Journals (Sweden)

    Cao Huong Giang

    2014-12-01

    Full Text Available A family of tungstated zirconia solid acid catalysts were synthesised via wet impregnation and subsequent thermochemical processing for the transformation of glucose to 5-hydroxymethylfurfural (HMF. Acid strength increased with tungsten loading and calcination temperature, associated with stabilisation of tetragonal zirconia. High tungsten dispersions of between 2 and 7 W atoms·nm−2 were obtained in all cases, equating to sub-monolayer coverages. Glucose isomerisation and subsequent dehydration via fructose to HMF increased with W loading and calcination temperature up to 600 °C, indicating that glucose conversion to fructose was favoured over weak Lewis acid and/or base sites associated with the zirconia support, while fructose dehydration and HMF formation was favoured over Brönsted acidic WOx clusters. Aqueous phase reforming of steam exploded rice straw hydrolysate and condensate was explored heterogeneously for the first time over a 10 wt% WZ catalyst, resulting in excellent HMF yields as high as 15% under mild reaction conditions.

  12. Studies on chemical protectors against radiation, 34; Survival effects of aqueous extracts of various Chinese traditional medicines on radiation injury

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Cheng-Ming; Ohta, Setsuko; Shinoda, Masato (Hoshi Univ., Tokyo (Japan))

    1991-06-01

    In order to develop a nontoxic radioprotector, 60 kinds of Chinese traditional medicines were chosen, and their aqueous extracts tested for their survival effects against the lethal effect of X-irradiation in mice. Radiation factors used were as follows: soft X-rays, 2100 R (5.418x10{sup -1}Ckg{sup -1}), 70 kVp, 10 mA, 10 mm acrylic filter, 70 R (1.806x10{sup -2} Ckg{sup -1})/min. Among 60 medicines tested by intraperitoneal injection immediately before the irradiation, 15 are shown to have the significant survival effect. These 15 effective medicines were also tested by intraperitoneal injection after the irradiation, and the survival effect was recognized in Keisi-syakuyaku-chimo-to, Keigai-rengyo-to, Shimotu-to, Syakuyaku-kanzo-to and Hange-syasin-to. On the other hand, the survival effects of 25 medicines including the above-mentioned 15 medicines were investigated by the oral administration at various times before or after the irradiation. As the results of these studies, only Keigai-rengyo-to and Bukuryo-in are shown to have the significant survival effect when administered 2 h before the irradiation. (author).

  13. An Integrated Chemical Environment to Support 21st-Century Toxicology.

    Science.gov (United States)

    Bell, Shannon M; Phillips, Jason; Sedykh, Alexander; Tandon, Arpit; Sprankle, Catherine; Morefield, Stephen Q; Shapiro, Andy; Allen, David; Shah, Ruchir; Maull, Elizabeth A; Casey, Warren M; Kleinstreuer, Nicole C

    2017-05-25

    SUMMARY: Access to high-quality reference data is essential for the development, validation, and implementation of in vitro and in silico approaches that reduce and replace the use of animals in toxicity testing. Currently, these data must often be pooled from a variety of disparate sources to efficiently link a set of assay responses and model predictions to an outcome or hazard classification. To provide a central access point for these purposes, the National Toxicology Program Interagency Center for the Evaluation of Alternative Toxicological Methods developed the Integrated Chemical Environment (ICE) web resource. The ICE data integrator allows users to retrieve and combine data sets and to develop hypotheses through data exploration. Open-source computational workflows and models will be available for download and application to local data. ICE currently includes curated in vivo test data, reference chemical information, in vitro assay data (including Tox21(TM)/ToxCast™ high-throughput screening data), and in silico model predictions. Users can query these data collections focusing on end points of interest such as acute systemic toxicity, endocrine disruption, skin sensitization, and many others. ICE is publicly accessible at https://ice.ntp.niehs.nih.gov. https://doi.org/10.1289/EHP1759.

  14. Optical and Chemical Characterization of Polyimide in a GEO-like Environment

    Science.gov (United States)

    Engelhart, D.; Plis, E.; Ferguson, D.; Cooper, R.; Hoffmann, R.

    2016-09-01

    Ground- and space-based optical observations of space objects rely on knowledge about how spacecraft materials interact with light. However, this is not a static property. Each material's optical fingerprint changes continuously throughout a spacecraft's orbital lifetime. These changes in optical signature occur because energetic particles break bonds within a material and new bonds subsequently form. The newly formed bonds can be identical to the original bonds or different, resulting in a new material. The chemical bonds comprising the material dictate which wavelengths of light are absorbed. Understanding the processes of material damage and recovery individually will allow development of a predictive model for materials' optical properties as a function of exposure to the space environment. In order to characterize the properties, we have exposed samples of polyimide to high energy electrons comparable to those found in a geostationary earth orbit in order to simulate damage on orbit. The resultant changes in the material's optical fingerprint were then characterized in the wavelength range of 0.2 to 25 microns. The chemical modifications to the material that result in these optical changes have also been identified. After initial electron-induced damage, the rate and mechanism of material recovery have been monitored and found to be extremely sensitive to the exposure of the damaged material to air. The implications of that fact and experimental progress toward complete in vacuo characterization will be discussed.

  15. Carbonates in the Martian meteorite Allan Hills 84001 formed at 18 +/- 4 degrees C in a near-surface aqueous environment.

    Science.gov (United States)

    Halevy, Itay; Fischer, Woodward W; Eiler, John M

    2011-10-11

    Despite evidence for liquid water at the surface of Mars during the Noachian epoch, the temperature of early aqueous environments has been impossible to establish, raising questions of whether the surface of Mars was ever warmer than today. We address this problem by determining the precipitation temperature of secondary carbonate minerals preserved in the oldest known sample of Mars' crust--the approximately 4.1 billion-year-old meteorite Allan Hills 84001 (ALH84001). The formation environment of these carbonates, which are constrained to be slightly younger than the crystallization age of the rock (i.e., 3.9 to 4.0 billion years), has been poorly understood, hindering insight into the hydrologic and carbon cycles of earliest Mars. Using "clumped" isotope thermometry we find that the carbonates in ALH84001 precipitated at a temperature of approximately 18 °C, with water and carbon dioxide derived from the ancient Martian atmosphere. Furthermore, covarying carbonate carbon and oxygen isotope ratios are constrained to have formed at constant, low temperatures, pointing to deposition from a gradually evaporating, subsurface water body--likely a shallow aquifer (meters to tens of meters below the surface). Despite the mild temperatures, the apparently ephemeral nature of water in this environment leaves open the question of its habitability.

  16. Are we going about chemical risk assessment for the aquatic environment the wrong way?

    Science.gov (United States)

    Johnson, Andrew C; Sumpter, John P

    2016-07-01

    The goal of protecting the aquatic environment through testing thousands of chemicals against hundreds of aquatic species with thousands of endpoints while also considering mixtures is impossible given the present resources. Much of the impetus for studies on micropollutants, such as pharmaceuticals, came from the topic of endocrine disruption in wild fish. But despite concern over reductions in fish fertility, there is little evidence that fish populations are in peril. Indeed, fish biologists suggest that many cyprinid populations have been recovering for the past 30 to 40 yr. The central assumption, key to current risk assessment, that effects observed in the laboratory or predicted by models are readily transferrable to the population level, is therefore questionable. The neglect in monitoring wildlife populations is the key weakness in environmental protection strategies. If we do not know whether aquatic wildlife species are declining or increasing, how valuable are our other ecotoxicological activities? Environ Toxicol Chem 2016;35:1609-1616. © 2016 SETAC. © 2016 SETAC.

  17. Endocrine-disrupting chemicals in the Pearl River Delta and coastal environment: sources, transfer, and implications.

    Science.gov (United States)

    Xu, Weihai; Yan, Wen; Huang, Weixia; Miao, Li; Zhong, Lifeng

    2014-12-01

    A study was conducted to investigate the occurrence and behavior of six endocrine-disrupting chemicals (EDCs) in sewage, river water, and seawater from the Pearl River Delta (PRD). The six EDCs under study were 4-nonylphenol (NP), bisphenol A (BPA), 17α-ethynylestradiol (EE2), estrone (E2), 17β-estradiol (E2), and estriol (E3). These EDCs, predominated by BPA, were found in high levels in the influents and the effluents of sewage treatment plants in the area. The relatively high concentrations (0.23-625 ng/L) of the EDCs detected in the receiving river water suggested that the untreated sewage discharge was a major contributor. The EDCs detected in eight outlets of the Pear River and the Pear River Estuary were in the ranges of 1.2-234 and 0.2-178 ng/L, respectively. The estrogen equivalents in the aquatic environments under study ranged from 0.08 to 4.5 ng/L, with E1 and EE2 being the two predominant contributors. As the fluxes of the EDCs from the PRD region to the nearby ocean are over 500 tons each year, the results of this study point to the potential that Pearl River is a significant source of the EDCs to the local environment there.

  18. The Influence of Environment on the Chemical Evolution in Low-mass Galaxies

    CERN Document Server

    Liu, Yiqing; Peng, Eric

    2016-01-01

    The mean alpha-to-iron abundance ratio ([$\\alpha$/Fe]) of galaxies is sensitive to the chemical evolution processes at early time, and it is an indicator of star formation timescale ($\\tau_{{\\rm SF}}$). Although the physical reason remains ambiguous, there is a tight relation between [$\\alpha$/Fe] and stellar velocity dispersion ($\\sigma$) among massive early-type galaxies (ETGs). However, no work has shown convincing results as to how this relation behaves at low masses. We assemble 15 data sets from the literature and build a large sample that includes 192 nearby low-mass ($18<\\sigma<80$~\\kms) ETGs. We find that the [$\\alpha$/Fe]-$\\sigma$ relation generally holds for low-mass ETGs, except in extreme environments. Specifically, in normal galaxy cluster environments, the [$\\alpha$/Fe]-$\\sigma$ relation and its intrinsic scatter are, within uncertainties, similar for low-mass and high-mass ETGs. However, in the most massive relaxed galaxy cluster in our sample, the zero point of the relation is higher an...

  19. Transport and release of chemicals from plastics to the environment and to wildlife

    Science.gov (United States)

    Teuten, Emma L.; Saquing, Jovita M.; Knappe, Detlef R. U.; Barlaz, Morton A.; Jonsson, Susanne; Björn, Annika; Rowland, Steven J.; Thompson, Richard C.; Galloway, Tamara S.; Yamashita, Rei; Ochi, Daisuke; Watanuki, Yutaka; Moore, Charles; Viet, Pham Hung; Tana, Touch Seang; Prudente, Maricar; Boonyatumanond, Ruchaya; Zakaria, Mohamad P.; Akkhavong, Kongsap; Ogata, Yuko; Hirai, Hisashi; Iwasa, Satoru; Mizukawa, Kaoruko; Hagino, Yuki; Imamura, Ayako; Saha, Mahua; Takada, Hideshige

    2009-01-01

    Plastics debris in the marine environment, including resin pellets, fragments and microscopic plastic fragments, contain organic contaminants, including polychlorinated biphenyls (PCBs), polycyclic aromatic hydrocarbons, petroleum hydrocarbons, organochlorine pesticides (2,2′-bis(p-chlorophenyl)-1,1,1-trichloroethane, hexachlorinated hexanes), polybrominated diphenylethers, alkylphenols and bisphenol A, at concentrations from sub ng g–1 to µg g–1. Some of these compounds are added during plastics manufacture, while others adsorb from the surrounding seawater. Concentrations of hydrophobic contaminants adsorbed on plastics showed distinct spatial variations reflecting global pollution patterns. Model calculations and experimental observations consistently show that polyethylene accumulates more organic contaminants than other plastics such as polypropylene and polyvinyl chloride. Both a mathematical model using equilibrium partitioning and experimental data have demonstrated the transfer of contaminants from plastic to organisms. A feeding experiment indicated that PCBs could transfer from contaminated plastics to streaked shearwater chicks. Plasticizers, other plastics additives and constitutional monomers also present potential threats in terrestrial environments because they can leach from waste disposal sites into groundwater and/or surface waters. Leaching and degradation of plasticizers and polymers are complex phenomena dependent on environmental conditions in the landfill and the chemical properties of each additive. Bisphenol A concentrations in leachates from municipal waste disposal sites in tropical Asia ranged from sub µg l–1 to mg l–1 and were correlated with the level of economic development. PMID:19528054

  20. Physical and chemical environments of abnormal vitrinite reflectance evolution in the sedimentary basins

    Institute of Scientific and Technical Information of China (English)

    QIU Nansheng; WANG Weixiao; XIE Mingju

    2007-01-01

    Based on the tested data of pressure and vitrinitere flectance of some wells in sedimentary basins, abnormal high pressure is regarded as not the only factor to retard the increase of vitrinite reflectance (Ro). Apart from the types of the organic matter, the physical environment (temperature and pressure) and chemical environment (fluid compositionand inorganic elements) will result in the abnormal vitrinite reflectance values in the sedimentary basins. This paper tested trace elements and vitrinite reflectance data from the the abnormal high pressure and normal pressure strata pro-files, respectively, and found that the acidic and lower salinity starta are favorable for the increase of Ro. By discussing the corresponding relationship between the contents of some trace elements in the mudstone and the vitrinite reflectance values, the typical trace elements were found to suppress and/or catalyze the vitrinite reflectance of organic matter, while the elements of Ca, Mn, Sr, B, Ba and P may result in the retardation of Ro. However, elements of Fe, Co, Zn, Ni and Rb may catalyze the organic matter maturation. This study is conductive to the organic maturation correction, oil and gas assessment and thermal history reconstruction by the paleothermometry.

  1. Chemical variation in a dominant tree species: population divergence, selection and genetic stability across environments.

    Directory of Open Access Journals (Sweden)

    Julianne M O'Reilly-Wapstra

    Full Text Available Understanding among and within population genetic variation of ecologically important plant traits provides insight into the potential evolutionary processes affecting those traits. The strength and consistency of selection driving variability in traits would be affected by plasticity in differences among genotypes across environments (G×E. We investigated population divergence, selection and environmental plasticity of foliar plant secondary metabolites (PSMs in a dominant tree species, Eucalyptus globulus. Using two common garden trials we examined variation in PSMs at multiple genetic scales; among 12 populations covering the full geographic range of the species and among up to 60 families within populations. Significant genetic variation in the expression of many PSMs resides both among and within populations of E. globulus with moderate (e.g., sideroxylonal A h(2op = 0.24 to high (e.g., macrocarpal G h(2op = 0.48 narrow sense heritabilities and high coefficients of additive genetic variation estimated for some compounds. A comparison of Qst and Fst estimates suggest that variability in some of these traits may be due to selection. Importantly, there was no genetic by environment interaction in the expression of any of the quantitative chemical traits despite often significant site effects. These results provide evidence that natural selection has contributed to population divergence in PSMs in E. globulus, and identifies the formylated phloroglucinol compounds (particularly sideroxylonal and a dominant oil, 1,8-cineole, as candidates for traits whose genetic architecture has been shaped by divergent selection. Additionally, as the genetic differences in these PSMs that influence community phenotypes is stable across environments, the role of plant genotype in structuring communities is strengthened and these genotypic differences may be relatively stable under global environmental changes.

  2. Adsorption of Procion Blue MX-R dye from aqueous solutions by lignin chemically modified with aluminium and manganese

    Energy Technology Data Exchange (ETDEWEB)

    Adebayo, Matthew A. [Institute of Chemistry, Federal University of Rio Grande do Sul (UFRGS), Av. Bento Gonçalves 9500, Postal Box 15003, 91501-970 Porto Alegre, RS (Brazil); Department of Chemical Sciences, Ajayi Crowther University, PMB 1066 Oyo, Oyo State (Nigeria); Prola, Lizie D.T. [Institute of Chemistry, Federal University of Rio Grande do Sul (UFRGS), Av. Bento Gonçalves 9500, Postal Box 15003, 91501-970 Porto Alegre, RS (Brazil); Lima, Eder C., E-mail: eder.lima@ufrgs.br [Institute of Chemistry, Federal University of Rio Grande do Sul (UFRGS), Av. Bento Gonçalves 9500, Postal Box 15003, 91501-970 Porto Alegre, RS (Brazil); Puchana-Rosero, M.J.; Cataluña, Renato; Saucier, Caroline; Umpierres, Cibele S.; Vaghetti, Julio C.P. [Institute of Chemistry, Federal University of Rio Grande do Sul (UFRGS), Av. Bento Gonçalves 9500, Postal Box 15003, 91501-970 Porto Alegre, RS (Brazil); Silva, Leandro G. da; Ruggiero, Reinaldo [Institute of Chemistry, Federal University of Uberlândia (UFU), AV. João Naves de Ávila 2121 block 1D—Campus Santa Mônica, 38400-902 Uberlândia, MG (Brazil)

    2014-03-01

    Graphical abstract: - Highlights: • Complexes of carboxy-methylated lignin with Al and Mn were used as adsorbents. • The optimum adsorption conditions were achieved at pH 2 and 298 K. • Maximum adsorption capacities are 73.52 mg g{sup −1} (CML-Al) and 55.16 mg g{sup −1} (CML-Mn). • CML-Al could remove ca. 95.83% of dye-contaminated industrial effluents. • CML-Al and CML-Mn are effective for treatment of simulated dye-house effluents. - Abstract: A macromolecule, CML, was obtained by purifying and carboxy-methylating the lignin generated from acid hydrolysis of sugarcane bagasse during bioethanol production from biomass. The CMLs complexed with Al{sup 3+} (CML-Al) and Mn{sup 2+} (CML-Mn) were utilised for the removal of a textile dye, Procion Blue MX-R (PB), from aqueous solutions. CML-Al and CML-Mn were characterised using Fourier transform infrared spectroscopy (FTIR), scanning differential calorimetry (SDC), scanning electron microscopy (SEM) and pH{sub PZC}. The established optimum pH and contact time were 2.0 and 5 h, respectively. The kinetic and equilibrium data fit into the general order kinetic model and Liu isotherm model, respectively. The CML-Al and CML-Mn have respective values of maximum adsorption capacities of 73.52 and 55.16 mg g{sup −1} at 298 K. Four cycles of adsorption/desorption experiments were performed attaining regenerations of up to 98.33% (CML-Al) and 98.08% (CML-Mn) from dye-loaded adsorbents, using 50% acetone + 50% of 0.05 mol L{sup −1} NaOH. The CML-Al removed ca. 93.97% while CML-Mn removed ca. 75.91% of simulated dye house effluents.

  3. Exploring consumer exposure pathways and patterns of use for chemicals in the environment

    OpenAIRE

    Dionisio, Kathie L.; Alicia M. Frame; Goldsmith, Michael-Rock; Wambaugh, John F.; Liddell, Alan; Cathey, Tommy; Smith, Doris; Vail, James; Ernstoff, Alexi; Fantke, Peter; Jolliet, Olivier; Judson, Richard S.

    2015-01-01

    Humans are exposed to thousands of chemicals in the workplace, home, and via air, water, food, and soil. A major challenge in estimating chemical exposures is to understand which chemicals are present in these media and microenvironments. Here we describe the Chemical/Product Categories Database (CPCat), a new, publically available (http://actor.epa.gov/cpcat) database of information on chemicals mapped to “use categories” describing the usage or function of the chemical. CPCat was created by...

  4. L-Prolinamide Catalyzed Aqueous Direct Aldol Reaction: an Environment-friendly Method for the Synthesis of β-Hydroxylketones

    Institute of Scientific and Technical Information of China (English)

    PENG, Yi-Yuang; LIU, Han; CUI, Ming; CHENG, Jin-Pei

    2007-01-01

    An environment-friendly L-prolinamide catalyzed aldol reaction has been developed. The reaction exhibited broad substrate generality, and high yields with good diastereoselectivity were obtained for cyclic ketones. The simplicity of product isolation, usage of water as environmentally benign reaction medium, and the usage of cheap,readily available and recyclable catalyst make this process promising to be developed for large-scale preparation of β-hydroxyl ketones.

  5. Amide cis-trans isomerization in aqueous solutions of methyl N-formyl-D-glucosaminides and methyl N-acetyl-D-glucosaminides: chemical equilibria and exchange kinetics.

    Science.gov (United States)

    Hu, Xiaosong; Zhang, Wenhui; Carmichael, Ian; Serianni, Anthony S

    2010-04-07

    Amide cis-trans isomerization (CTI) in methyl 2-deoxy-2-acylamido-d-glucopyranosides was investigated by (1)H and (13)C NMR spectroscopy. Singly (13)C-labeled methyl 2-deoxy-2-formamido-d-glucopyranoside (MeGlcNFm) anomers provided standard (1)H and (13)C chemical shifts and (1)H-(1)H and (13)C-(13)C spin-coupling constants for cis and trans amides that are detected readily in aqueous solution. Equipped with this information, doubly (13)C-labeled methyl 2-deoxy-2-acetamido-d-glucopyranoside (MeGlcNAc) anomers were investigated, leading to the detection and quantification of cis and trans amides in this biologically important aminosugar. In comparison to MeGlcNFm anomers, the percentage of cis amide in aqueous solutions of MeGlcNAc anomers is small ( approximately 23% for MeGlcNFm versus approximately 1.8% for MeGlcNAc at 42 degrees C) but nevertheless observable with assistance from (13)C-labeling. Temperature studies gave thermodynamic parameters DeltaG degrees , DeltaH degrees , and DeltaS degrees for cis-trans interconversion in MeGlcNFm and MeGlcNAc anomers. Cis/trans equilibria depended on anomeric configuration, with solutions of alpha-anomers containing less cis amide than those of beta-anomers. Confirmation of the presence of cis amide in MeGlcNAc solutions derived from quantitative (13)C saturation transfer measurements of CTI rate constants as a function of solution temperature, yielding activation parameters E(act), DeltaG degrees (), DeltaH degrees (), and DeltaS degrees () for saccharide CTI. Rate constants for the conversion of trans to cis amide in MeGlcNFm and MeGlcNAc anomers ranged from 0.02 to 3.59 s(-1) over 31-85 degrees C, compared to 0.24-80 s(-1) for the conversion of cis to trans amide over the same temperature range. Energies of activation ranged from 16-19 and 19-20 kcal/mol for the cis --> trans and trans --> cis processes, respectively. Complementary DFT calculations on MeGlcNFm and MeGlcNAc model structures were conducted to evaluate

  6. Chemical Reactivity of alpha-Pinene-derived Products in the Aqueous Phase: Implications on the Fate of Organic Nitrates

    Science.gov (United States)

    Rindelaub, J. D.; Hostetler, M. A.; Lipton, M. A.; Shepson, P. B.

    2014-12-01

    The production of organic nitrates has significant atmospheric importance due to the impact on regional air quality by influencing NOx lifetimes and ozone formation. Additionally, these low volatility compounds readily partition into the particle phase and are important contributors to secondary organic aerosol. Once in the aerosol phase, organic nitrates undergo further chemical reactions that govern their fate in the atmosphere and, consequently, their impact on air quality. Recent research indicates that the presence of water on aerosol particles has a major impact on the reactivity of organic nitrates and that condensed phase hydrolysis leads to the destruction of organic nitrate species, depending on structure. Despite this knowledge, the chemical mechanisms, products, product reactivity and volatility are still uncertain, negatively impacting our understanding of aerosol phase processing and the contribution to air quality. To further understand the atmospheric impact of aerosol phase hydrolysis, we analyzed both condensed phase hydrolysis reactions involving alpha-pinene-derived standards and alpha-pinene photochemical chamber reaction filter samples, using a suite of spectroscopic and mass spectrometric techniques. We were able to measure the pH-dependent hydrolysis rate constants for several types of organic nitrates and identify specific reaction products. The chemistry involved exhibits a strong dependence on pH, providing important mechanistic clues. The results of this study will significantly contribute to our knowledge of aerosol phase chemistry and the impact on regional air quality with respect to the fate of organic nitrate species.

  7. Chemical constraints governing the origin of metabolism: the thermodynamic landscape of carbon group transformations under mild aqueous conditions

    Science.gov (United States)

    Weber, Arthur L.

    2002-01-01

    The thermodynamics of organic chemistry under mild aqueous conditions was examined in order to begin to understand its influence on the structure and operation of metabolism and its antecedents. Free energies (deltaG) were estimated for four types of reactions of biochemical importance carbon-carbon bond cleavage and synthesis, hydrogen transfer between carbon groups, dehydration of alcohol groups, and aldo-keto isomerization. The energies were calculated for mainly aliphatic groups composed of carbon, hydrogen, and oxygen. The energy values showed (1) that generally when carbon-carbon bond cleavage involves groups from different functional group classes (i.e., carboxylic acids, carbonyl groups, alcohols, and hydrocarbons), the transfer of the shared electron-pair to the more reduced carbon group is energetically favored over transfer to the more oxidized carbon group, and (2) that the energy of carbon-carbon bond transformation is primarily determined by the functional group class of the group that changes oxidation state in the reaction (i.e., the functional group class of the group that donates the shared electron-pair during cleavage, or that accepts the incipient shared electron-pair during synthesis). In contrast, the energy of hydrogen transfer between carbon groups is determined by the functional group class of both the hydrogen-donor group and the hydrogen-acceptor group. From these and other observations we concluded that the chemistry involved in the origin of metabolism (and to a lesser degree modern metabolism) was strongly constrained by (1) the limited redox-based transformation energy of organic substrates that is readily dissipated in a few energetically favorable irreversible reactions; (2) the energy dominance of a few transformation half-reactions that determines whether carbon-carbon bond transformation (cleavage or synthesis) is energetically favorable (deltaG +3.5 kcal/mol); and (3) the dependence of carbon group transformation energy on the

  8. Chemical changes in groundwater due to flooding of an iron mine in a non-acid producing environment

    OpenAIRE

    Collon, Pauline,; Fabriol, Robert; Bues, Michel

    2002-01-01

    International audience; Mine drainage is one of the mining industry’s undesirable effects on the environment. Mining operations disturb the chemical equilibrium of the surrounding rocks by suddenly exposing them to oxidising conditions. The chemical reactions that take place generate effluents that are usually acidic and contain SO42-, Fe, Mn, etc. After the mines are closed and abandoned, the suspension of dewatering and drainage leads to progressive flooding of the workings. The waters drai...

  9. The Effects of Cluster Environment on the Chemical Evolution of Galaxies

    Science.gov (United States)

    Pilyugin, L. S.; Ferrini, F.

    The values of oxygen deficiency have been derived for nine Virgo cluster spiral galaxies from the sample of Skillman et al (1996) which ranges from HI deficient spirals (three galaxies near the center of cluster) to spirals with normal HI contents (three galaxies at the periphery of cluster). The chemical properties of Virgo cluster spiral galaxies have been compared with chemical properties of field spiral galaxies considered by Pilyugin and Ferrini (1998). It has been found that the sample of spirals at the periphery of the cluster is a mixture of objects without, with moderate, and with significant oxygen abundance deficiency. It confirms the conclusion of Skillman et al (1996) that spirals at the periphery of the cluster are indistinguishable from field galaxies. All the spirals near the center of the cluster, within the limited sample here considered, have no oxygen deficiency, and are more advanced in evolution than spirals at the periphery of the cluster or than field spirals. These facts can be considered as a hint that, in the case of spiral galaxies near the center of a cluster, the cluster environment inhibits gas exchange between the galaxy and its surroundings at the present epoch and can slightly enhance the efficiency of star formation. The positions of Virgo spirals without oxygen abundance deficiency in the gas mass fraction μ -- O/H diagram agree closely with the positions of field spiral galaxies without oxygen abundance deficiency and are in agreement with the location of one-zone closed-box models. This is strong evidence in favour that the oxygen yield (or, in consequence, the initial mass function) in cluster spiral galaxies does not differ from that in spiral galaxies in the field.

  10. Biomonitoring of chemical elements in an urban environment using arboreal and bush plant species.

    Science.gov (United States)

    Rucandio, Maria Isabel; Petit-Domínguez, Maria Dolores; Fidalgo-Hijano, Concepcion; García-Giménez, Rosario

    2011-01-01

    The aim of this work was to investigate the possibility of using several bush and arboreal plant species, usually present as ornamental plants in street and parks, as environmental indicators of pollution. This is a research paper that evaluates the real possibility of using a fast and low-cost procedure to evaluate the pollution degree through data obtained from plant species growing within an urban environment. Leaves of six different bush and arboreal species were collected from different parts of Madrid (Spain), ranging from highly polluted considered areas to medium and low contaminated ones. A total of 66 chemical elements, from major to minor and trace, were determined for every leaf sample by inductively coupled plasma-mass spectrometry. Statistical analyses were carried out using mainly box and whisker plots, linear discriminant analysis and cluster analysis. The pollution by different elements of the studied areas of Madrid cannot be considered generally dangerous for human health. The level detected for the contaminants, in general, is similar or lower than other urban cities. Pb and V concentrations in plant samples tend to increase as traffic density increases. The different studied plant species showed a different capability of accumulation of certain elements. Cedrus deodara accumulates specially Ag, Hg, Mo and V; Cupressus sempervirens, Zr; Pinus pinea, As and Sb; Nerium oleander Ni, Pb, Mo and Se; Ligustrum ovalifolium, Sc and V; and Pittosporum tobira, Ag, Cd, Rb and Sc. The leaves and needles collected from bush and arboreal plants common in this city have demonstrated to be useful to evaluate the level of pollution not only through the chemical analysis but also through the recognition of the visual injury symptoms. The application of multivariate statistical techniques combined with determining of element concentration and correlation analysis has been proved to be an effective tool for reach the objectives of the present work. This allows

  11. Physico-chemical properties of alginate/shellac aqueous-core capsules: Influence of membrane architecture on riboflavin release.

    Science.gov (United States)

    Ben Messaoud, Ghazi; Sánchez-González, Laura; Probst, Laurent; Jeandel, Carole; Arab-Tehrany, Elmira; Desobry, Stéphane

    2016-06-25

    To enhance physico-chemical properties of alginate liquid-core capsules, shellac was incorporated into the membrane (composite capsules) or as an additional external layer (coated capsules). The influence of pH, coating time, shellac concentration and preparation mechanism (acid or calcium precipitation) were investigated. Results showed that shellac significantly influenced the capsules properties. The feasibility of shellac incorporation was closely related to the preparation conditions as confirmed by Infrared spectroscopy. Optical, fluorescence and scanning electron microscopy, highlighted different capsules and membranes architectures. In contrast to simple and composite capsules, coated capsules showed a pH-dependent release of the entrapped vitamin especially after shellac crosslinking with calcium. Heating of coated capsules above the glass transition temperature investigated by Differential Scanning Calorimetry, led to irreversible structural change due to thermoplastic behavior of shellac and enhanced riboflavin retention under acidic conditions. This global approach is useful to control release mechanism of low molecular weight molecules from macro and micro-capsules.

  12. The chemical effects of the Martian environment on power system component materials: A theoretical approach

    Energy Technology Data Exchange (ETDEWEB)

    Perez-Davis, M.E.; Gaier, J.R. [Lewis Research Center, Cleveland, OH (United States)

    1994-09-01

    In the foreseeable future, an expedition may be undertaken to explore the planet Mars. Some of the power source options being considered for such a mission are photovoltaics, regenerative fuel cells and nuclear reactors. In addition to electrical power requirements, environmental conditions en route to Mars, in the planetary orbit and on the Martian surface must be simulated and studied in order to anticipate and solve potential problems. Space power systems components such as photovoltaic arrays, radiators, and solar concentrators may be vulnerable to degradation in the Martian environment. Natural characteristics of Mars which may pose a threat to surface power systems include high velocity winds, dust, ultraviolet radiation, large daily variations in temperature, reaction to components of the soil, atmosphere and atmospheric condensates as well as synergistic combinations. Most of the current knowledge of the characteristics of the Martian atmosphere and soil composition was obtained from the Viking 1 and 2 missions in 1976. This paper presents a theoretical study used to assess the effects of the Martian atmospheric conditions on the power systems components. A computer program written at NASA Lewis Research Center in 1961 to 1962 for combustion research that uses a free-energy minimization technique was used to calculate chemical equilibrium for assigned thermodynamic states of temperature and pressure. The power system component materials selected for this study include: Silicon dioxide, silicon, carbon, copper, and titanium. Combinations of environments and materials considered in this study include: (1) Mars atmosphere with power surface material, (2) Mars atmosphere and dust component with power surface material, (3) Mars atmosphere and hydrogen peroxide or superoxide with power system material.

  13. Antioxidant Status of Plants in Conditions of Chemical Pollution of the Urban Environment

    Directory of Open Access Journals (Sweden)

    L. V. MOSINA

    2014-06-01

    Full Text Available Antioxidants are substances that slow down the oxidation of organic compounds that protect the body from the negative effects of free radicals antioxidant connected with free radical and puts up a barrier to the corrosive effects of the electron. Enzyme protective system of the body converts cell oxidant into the water and oxygen.The body has its own system of struggle with excessive amounts of free radicals, but it has weakened under the impact of the polluted environment, direct sunlight and needs support. Scientists found that many plants contain substances flavonoids - a large group of polyphenolic compounds structure, which bind free radicals.This article presents a review of research performed in the Russian state endowment of the University of Immanuel Kant, the influence of chemical contaminated areas in the antioxidant status of the plants.Thus the study of the influence of factors on the formation of antioxidants plants is a fragment of a large-scale work on the study of natural antioxidants, which not only protect living organisms but also determine the quality of plant foods, feeds, and ultimately the quality of life and its duration. The solution of the problems of modern society - environmental, health, demography is impossible without change of attitude to food.

  14. The synergistic toxicity of the multiple chemical mixtures: implications for risk assessment in the terrestrial environment.

    Science.gov (United States)

    Chen, Chen; Wang, Yanhua; Qian, Yongzhong; Zhao, Xueping; Wang, Qiang

    2015-04-01

    The combined toxicity of five insecticides (chlorpyrifos, avermectin, imidacloprid, λ-cyhalothrin, and phoxim), two herbicides (atrazine and butachlor) and a heavy metal (cadmium) has been examined with the earthworm acute toxicity test. Toxicological interactions of these chemicals in four, five, six, seven, and eight-component mixtures were studied using the combination-index (CI) equation method. In four-component and five-component mixtures, the synergistic effects predominated at lower effect levels, while the patterns of interactions found in six, seven, and eight-component mixtures displayed synergism. The λ-CY+IMI+BUT+ATR+CPF+PHO combination displayed the most strongly synergistic interaction, with CI values ranging from 0.09 to 0.15. The nature of the interaction changes with the effect level and the relevance of synergistic effects increase with the complexity of the mixture. The CI method was compared with the classical models of concentration addition (CA) and independent action (IA) and we found that the CI method could accurately predict the combined toxicity. The predicted synergism resulted from co-existence of the pesticides and the heavy metal especially at low effect levels may have important implications in risk assessment for the real terrestrial environment.

  15. Plaque biofilms: the effect of chemical environment on natural human plaque biofilm architecture.

    Science.gov (United States)

    Robinson, C; Strafford, S; Rees, G; Brookes, S J; Kirkham, J; Shore, R C; Watson, P S; Wood, S

    2006-11-01

    The architecture of microbial biofilms especially the outer regions have an important influence on the interaction between biofilm and local environment particularly on the flux of materials into and out of biofilm compartments and as a consequence, biofilm metabolic behaviour. In the case of dental plaque biofilms, architecture will determine access of nutrients including acidogenic substrates and therapeutic materials to the microbial biomass and to the underlying tooth surface. Manipulation of this architecture may offer a means of altering mass transfer into the whole biofilm and biomass and raises the possibility of improving access of therapeutics. Plaque biofilms formed in vivo on human enamel were subjected to a number of different chemical conditions while under observation by confocal laser scanning microscopy in reflection mode. In this way the outer 50-100 microm or so of the biofilms was examined. Density and distribution of biomass were recorded as degree of reflectance. The amount and density of biofilm biomass increased from the plaque saliva interface towards the interior. Plaque biofilms were robust and little affected by mechanical manipulation, high ionic strength or low pH (2.5). Detergent (SLS), however, often appeared to either remove biomass and/or dramatically reduce its density.

  16. Reaction Product Identification in Extreme Chemical Environments by Broadband Rotational Spectroscopy

    Science.gov (United States)

    Pate, Brooks

    Molecular rotational spectroscopy has several advantages for detection of reaction intermediates and products under extreme laboratory conditions. Rotational spectroscopy has high sensitivity to the molecular structure and provides high spectral resolution in low pressure environments. Furthermore, quantum chemistry provides accurate estimates of the spectroscopic parameters. As a result, rotational spectroscopy can identify molecular species in complex reaction mixtures without the need for chromatographic separation and without the need for a previously recorded ``library spectrum'' of the molecule. The application of chirped pulse Fourier transform rotational spectroscopy methods for the identification of molecules of astrochemical interest formed in pulsed discharge sources will be described including recent advances for high-throughput mm-wave spectroscopy. The set of reaction products created in the experiment can provide insight into the reaction mechanism. Reactions involving the CN radical will be discussed. These reactions can be barrierless making them candidates for interstellar gas reactions. The possibility that interstellar cyanomethanimine is produced by gas phase radical-neutral reactions instead of surface chemistry on grain-supported ices will be discussed using recent spatially resolved chemical images in Sagittarius B2 observed with the Jansky Very Large Array. This work supported by NSF CHE 1213200.

  17. Structural Expression of Chemical Environment and C-13 NMR Chemical Shift for Carbons in Alcohols%脂肪醇分子碳环境结构表征与碳谱化学位移

    Institute of Scientific and Technical Information of China (English)

    刘树深; 徐红

    2000-01-01

    A novel atomic electronegative distance vector (AEDV) has been developed to express the chemical environment of various equivalent carbon in alcohols and four 4-parameter linear relationship between chemical shift and AEDV are created by using multiple linear regression.

  18. Chemical and toxicological evaluation of an emerging pollutant (enrofloxacin) by catalytic wet air oxidation and ozonation in aqueous solution.

    Science.gov (United States)

    Li, Yan; Zhang, Feifang; Liang, Xinmiao; Yediler, Ayfer

    2013-01-01

    This study evaluates the degradation efficiency of enrofloxacin (ENR) by catalytic wet air oxidation (CWAO) and ozonation. Results obtained by CWAO experiments show that 99.5% degradation, 37.0% chemical oxidation demand (COD) removal and 51.0% total organic carbon (TOC) conversion were obtained when 100 mol% FeCl(3) and 25 mol% NaNO(2) at 150 °C under 0.5 MPa oxygen pressure after 120 min are used. The degradation products are identified by liquid chromatography-tandem mass spectrometry (LC-MS/MS), gas chromatography-mass spectrometry (GC-MS) and ion chromatography (IC). The oxidation end products, F(-), NO(3)(-) and NH(4)(+) were determined by IC. The BOD(5)/COD ratio as a measure of the biodegradability of the parent compound increased from 0.01 to 0.12 after 120 min of reaction time, indicating an improved biodegradability of the parent compound. The inhibition of bioluminescence of the marine bacteria V. fischeri decreased from 43% to 12% demonstrating a loss in toxicity of ENR during CWAO. Ozonation of 0.2 mM ENR was carried out with an ozone concentration of 7.3 g m(-3) at pH 7. ENR decomposition with a degradation rate of 87% was obtained corresponding to the reaction time. Moderate changes in COD (18%) and TOC (17%) removal has been observed. The bioluminescence inhibition increased from 8% to 50%, due to the generation of toxic degradation products during ozonation. In comparison to the widely use of well developed method of ozonation CWAO exhibits better performance in terms of COD, TOC removals and generates less toxic products.

  19. A sensitive electrochemical impedance immunosensor for determination of malachite green and leucomalachite green in the aqueous environment.

    Science.gov (United States)

    Zhu, Dan; Li, Qiangqiang; Pang, Xiumei; Liu, Yue; Wang, Xue; Chen, Gang

    2016-08-01

    Application of malachite green (MG) and leucomalachite green (LMG) in fish farm water causes an environmental problem. This study proposes for the first time a sensitive and convenient electrochemical impedance spectroscopy (EIS) method for determining MG and LMG by a bovine serum albumin-decorated gold nanocluster (BSA-AuNC)/antibody composite film-based immunosensor. In order to improve the analytical performance, the glassy carbon electrode (GCE) was modified with 1, 4-phenylenediamine to form a stable layer, and then, BSA-AuNCs were covalently bound to the GCE. An adequate quantity of the polyclonal antibody of LMG was immobilized onto the surface of the BSA-AuNCs by the chemical reaction of EDC/NHS. The sensors can respond to the specific target based on specific covalent bonding. The experimental parameters, such as the pH, incubating concentration, and time, have been investigated and optimized. The calibration curve for LMG was linear in the range of 0.1~10.0 ng/mL with the limit of detection (LOD) 0.03 ng/mL. Furthermore, the sum of MG and LMG was detected in fish farm water by MG reduction. The recovery was between 89.7 % and 99.2 % in spiked samples. The EC sensor method was also compared with the ELISA method and validated by the LC-MS/MS method, which proves its great promise as a field instrument for the rapid monitoring of MG and LMG pollution. Graphical abstract 1, 4-Phenylenediamine and BSA-AuNC/antibody-decorated glassy carbon electrodes have been used for the impedimetric detection of the sum of malachite green and leucomalachite green via specific immuno-binding.

  20. Effect of Reaction Time and Temperature on Chemical, Structural, Optical, and Photoelectrical Properties of PbS Thin Films Chemically Deposited from the Pb(OAc)2-NaOH-TU-TEA Aqueous System

    Science.gov (United States)

    Castelo-González, O. A.; Sotelo-Lerma, M.; García-Valenzuela, J. A.

    2016-08-01

    Lead sulfide (PbS) thin films have been deposited on float glass substrates by the chemical bath deposition technique using a Pb(CH3COO)2-NaOH-(NH2)2CS-N(CH2CH2OH)3 definite aqueous system. The chemical and structural characteristics, as well as the variation of the optical and photoelectrical properties, were studied as functions of reaction time and temperature. For this purpose, the following characterization techniques were employed: x-ray diffraction analysis, x-ray photoelectron spectroscopy, ultraviolet-visible-near infrared spectrophotometry, and dark and light current measurements. Based on the results, it was observed that increase in the reaction temperature increased the deposition rate of the PbS thin film (associated with the cubic crystalline structure); increase of this parameter from 40°C to 70°C (with reaction time of 60 min) led to an increase of the thickness from ˜129 nm to ˜459 nm and the crystallite size (D) from 15.3 nm to 20.2 nm; on the other hand, increase in temperature decreased the energy bandgap (E g) from 1.66 eV to 0.51 eV and the relative photosensitivity factor (S ph) from 0.468 to 0.032. A similar effect was obtained with increase of the reaction time for given temperature.

  1. Effect of Reaction Time and Temperature on Chemical, Structural, Optical, and Photoelectrical Properties of PbS Thin Films Chemically Deposited from the Pb(OAc)2-NaOH-TU-TEA Aqueous System

    Science.gov (United States)

    Castelo-González, O. A.; Sotelo-Lerma, M.; García-Valenzuela, J. A.

    2017-01-01

    Lead sulfide (PbS) thin films have been deposited on float glass substrates by the chemical bath deposition technique using a Pb(CH3COO)2-NaOH-(NH2)2CS-N(CH2CH2OH)3 definite aqueous system. The chemical and structural characteristics, as well as the variation of the optical and photoelectrical properties, were studied as functions of reaction time and temperature. For this purpose, the following characterization techniques were employed: x-ray diffraction analysis, x-ray photoelectron spectroscopy, ultraviolet-visible-near infrared spectrophotometry, and dark and light current measurements. Based on the results, it was observed that increase in the reaction temperature increased the deposition rate of the PbS thin film (associated with the cubic crystalline structure); increase of this parameter from 40°C to 70°C (with reaction time of 60 min) led to an increase of the thickness from ˜129 nm to ˜459 nm and the crystallite size ( D) from 15.3 nm to 20.2 nm; on the other hand, increase in temperature decreased the energy bandgap ( E g) from 1.66 eV to 0.51 eV and the relative photosensitivity factor ( S ph) from 0.468 to 0.032. A similar effect was obtained with increase of the reaction time for given temperature.

  2. Evaluating the potential for quantitative monitoring of in situ chemical oxidation of aqueous-phase TCE using in-phase and quadrature electrical conductivity

    Science.gov (United States)

    Hort, R. D.; Revil, A.; Munakata-Marr, J.; Mao, D.

    2015-07-01

    Electrical resistivity measurements can potentially be used to remotely monitor fate and transport of ionic oxidants such as permanganate (MnO4-) during in situ chemical oxidation (ISCO) of contaminants like trichloroethene (TCE). Time-lapse two-dimensional bulk conductivity and induced polarization surveys conducted during a sand tank ISCO simulation demonstrated that MnO4- plume movement could be monitored in a qualitative manner using bulk conductivity tomograms, although chargeability was below sensitivity limits. We also examined changes to in-phase and quadrature electrical conductivity resulting from ion injection, MnO2 and Cl- production, and pH change during TCE and humate oxidation by MnO4- in homogeneous aqueous solutions and saturated porous media samples. Data from the homogeneous samples demonstrated that inversion of the sand tank resistivity data using a common Tikhonov regularization approach was insufficient to recover an accurate conductivity distribution within the tank. While changes to in-phase conductivity could be successfully modeled, quadrature conductivity values could not be directly related to TCE oxidation product or MnO4- concentrations at frequencies consistent with field induced polarization surveys, limiting the utility of quadrature conductivity for monitoring ISCO.

  3. Sodium Borohydride Reduction of Aqueous Silver-Iron-Nickel Solutions: a Chemical Route to Synthesis of Low Thermal Expansion-High Conductivity Ag-Invar Alloys

    Science.gov (United States)

    Sterling, E. A.; Stolk, J.; Hafford, L.; Gross, M.

    2009-07-01

    Thermal management is a critical concern in the design and performance of electronics systems. If heat extraction and thermal expansion are not properly addressed, the thermal mismatch among dissimilar materials may give rise to high thermal stresses or interfacial shear strains, and ultimately to premature system failure. In this article, we present a chemical synthesis process that yields Ag-Invar (64Fe-36Ni) alloys with a range of attractive properties for thermal management applications. Sodium borohydride reduction of an aqueous Ag-Fe-Ni metal salt solution produces nanocrystalline powders, and conventional powder processing converts this powder to fine-grained alloys. The samples are characterized by X-ray diffraction (XRD), scanning electron microscopy, thermomechanical analysis, and electrical conductivity measurements; thermal conductivity is estimated using the Wiedemann-Franz law. Sintering of Ag-Fe-Ni powders leads to the formation of two-phase silver-Invar alloys with low coefficients of thermal expansion (CTEs) and relatively high electrical conductivities. A sample of 50Ag-50Invar exhibits a CTE of 8.76 μm/(m· °C) and an estimated thermal conductivity of 236 W/(m·K). The Ag-Invar alloys offer thermodynamic stability and tailorable properties, and they may help address the need for improved packaging materials.

  4. Selective Chemical Conversion of Sugars in Aqueous Solutions without Alkali to Lactic Acid Over a Zn-Sn-Beta Lewis Acid-Base Catalyst

    Science.gov (United States)

    Dong, Wenjie; Shen, Zheng; Peng, Boyu; Gu, Minyan; Zhou, Xuefei; Xiang, Bo; Zhang, Yalei

    2016-05-01

    Lactic acid is an important platform molecule in the synthesis of a wide range of chemicals. However, in aqueous solutions without alkali, its efficient preparation via the direct catalysis of sugars is hindered by a side dehydration reaction to 5-hydroxymethylfurfural due to Brønsted acid, which originates from organic acids. Herein, we report that a previously unappreciated combination of common two metal mixed catalyst (Zn-Sn-Beta) prepared via solid-state ion exchange synergistically promoted this reaction. In water without a base, a conversion exceeding 99% for sucrose with a lactic acid yield of 54% was achieved within 2 hours at 190 °C under ambient air pressure. Studies of the acid and base properties of the Zn-Sn-Beta zeolite suggest that the introduction of Zn into the Sn-Beta zeolite sequentially enhanced both the Lewis acid and base sites, and the base sites inhibited a series of side reactions related to fructose dehydration to 5-hydroxymethylfurfural and its subsequent decomposition.

  5. Aqueous Chemical Solution Deposition of Novel, Thick and Dense Lattice-Matched Single Buffer Layers Suitable for YBCO Coated Conductors: Preparation and Characterization

    Directory of Open Access Journals (Sweden)

    Isabel van Driessche

    2012-09-01

    Full Text Available In this work we present the preparation and characterization of cerium doped lanthanum zirconate (LCZO films and non-stoichiometric lanthanum zirconate (LZO buffer layers on metallic Ni-5% W substrates using chemical solution deposition (CSD, starting from aqueous precursor solutions. La2Zr2O7 films doped with varying percentages of Ce at constant La concentration (La0.5CexZr1−xOy were prepared as well as non-stoichiometric La0.5+xZr0.5−xOy buffer layers with different percentages of La and Zr ratios. The variation in the composition of these thin films enables the creation of novel buffer layers with tailored lattice parameters. This leads to different lattice mismatches with the YBa2Cu3O7−x (YBCO superconducting layer on top and with the buffer layers or substrate underneath. This possibility of minimized lattice mismatch should allow the use of one single buffer layer instead of the current complicated buffer architectures such as Ni-(5% W/LZO/LZO/CeO2. Here, single, crack-free LCZO and non-stoichiometric LZO layers with thicknesses of up to 140 nm could be obtained in one single CSD step. The crystallinity and microstructure of these layers were studied by XRD, and SEM and the effective buffer layer action was studied using XPS depth profiling.

  6. Effect of precursor solutions stirring on deep level defects concentration and spatial distribution in low temperature aqueous chemical synthesis of zinc oxide nanorods

    Energy Technology Data Exchange (ETDEWEB)

    Alnoor, Hatim, E-mail: hatim.alnoor@liu.se; Chey, Chan Oeurn; Pozina, Galia; Willander, Magnus; Nur, Omer [Department of Science and Technology (ITN), Campus Norrköping, Linköping University, SE-601 74 Norrköping (Sweden); Liu, Xianjie; Khranovskyy, Volodymyr [Department of Physics, Chemistry and Biology (IFM), Linköping University, SE-583 81 Linköping (Sweden)

    2015-08-15

    Hexagonal c-axis oriented zinc oxide (ZnO) nanorods (NRs) with 120-300 nm diameters are synthesized via the low temperature aqueous chemical route at 80 °C on silver-coated glass substrates. The influence of varying the precursor solutions stirring durations on the concentration and spatial distributions of deep level defects in ZnO NRs is investigated. Room temperature micro-photoluminesnce (μ-PL) spectra were collected for all samples. Cathodoluminescence (CL) spectra of the as-synthesized NRs reveal a significant change in the intensity ratio of the near band edge emission (NBE) to the deep-level emission (DLE) peaks with increasing stirring durations. This is attributed to the variation in the concentration of the oxygen-deficiency with increasing stirring durations as suggested from the X-ray photoelectron spectroscopy analysis. Spatially resolved CL spectra taken along individual NRs revealed that stirring the precursor solutions for relatively short duration (1-3 h), which likely induced high super saturation under thermodynamic equilibrium during the synthesis process, is observed to favor the formation of point defects moving towards the tip of the NRs. In contrary, stirring for longer duration (5-15 h) will induce low super saturation favoring the formation of point defects located at the bottom of the NRs. These findings demonstrate that it is possible to control the concentration and spatial distribution of deep level defects in ZnO NRs by varying the stirring durations of the precursor solutions.

  7. Effect of precursor solutions stirring on deep level defects concentration and spatial distribution in low temperature aqueous chemical synthesis of zinc oxide nanorods

    Science.gov (United States)

    Alnoor, Hatim; Chey, Chan Oeurn; Pozina, Galia; Liu, Xianjie; Khranovskyy, Volodymyr; Willander, Magnus; Nur, Omer

    2015-08-01

    Hexagonal c-axis oriented zinc oxide (ZnO) nanorods (NRs) with 120-300 nm diameters are synthesized via the low temperature aqueous chemical route at 80 °C on silver-coated glass substrates. The influence of varying the precursor solutions stirring durations on the concentration and spatial distributions of deep level defects in ZnO NRs is investigated. Room temperature micro-photoluminesnce (μ-PL) spectra were collected for all samples. Cathodoluminescence (CL) spectra of the as-synthesized NRs reveal a significant change in the intensity ratio of the near band edge emission (NBE) to the deep-level emission (DLE) peaks with increasing stirring durations. This is attributed to the variation in the concentration of the oxygen-deficiency with increasing stirring durations as suggested from the X-ray photoelectron spectroscopy analysis. Spatially resolved CL spectra taken along individual NRs revealed that stirring the precursor solutions for relatively short duration (1-3 h), which likely induced high super saturation under thermodynamic equilibrium during the synthesis process, is observed to favor the formation of point defects moving towards the tip of the NRs. In contrary, stirring for longer duration (5-15 h) will induce low super saturation favoring the formation of point defects located at the bottom of the NRs. These findings demonstrate that it is possible to control the concentration and spatial distribution of deep level defects in ZnO NRs by varying the stirring durations of the precursor solutions.

  8. The Inorganic-organic Hybrid Junction with n-ZnO Nanorods/p-polyfluorene Structure Grown with Low-temperature Aqueous Chemical Growth Method

    Institute of Scientific and Technical Information of China (English)

    WU Wei; BIAN Jiming; SUN Yinglan; CHENG Chuanhui; SUN Jingchang; LLANG Hongwei; LUO Yingmin; DU Guotong

    2012-01-01

    The inorganic-organic hybrid junction was synthesized on ITO glass substrate,which was consisted of an n-type ZnO nanorods (NRs) grown by low-temperature aqueous chemical growth method and a p-type polyfluorene (PF) organic film fabricated by spin-coating.The experimental results indicate that densely and uniformly distributed ZnO nanorods are successfully grown on the PF layer.The thickness of the PF layer plays a dominant role for the current-voltage (Ⅰ-Ⅴ) characteristic of the ZnO NRs/PF inorganic-organic hybrid junction device,and a p-n junction with obviously rectifying behavior is achieved with optimal PF layer thickness.The photoluminescence (PL) spectrum coveting the broad visible range was obtained from the n-ZnO nanorods/p-polyfluorene (PF) structure,which was originated from the combination of the PF-related blue emission and the ZnO-related deep level emission.

  9. Evaluation of laboratory and industrial meat and bone meal combustion residue as cadmium immobilizing material for remediation of polluted aqueous solutions: "chemical and ecotoxicological studies".

    Science.gov (United States)

    Coutand, M; Deydier, E; Cyr, M; Mouchet, F; Gauthier, L; Guilet, R; Savaete, L Bernues; Cren, S; Clastres, P

    2009-07-30

    Meat and Bone Meals (MBM) combustion residues (ashes) are calcium and phosphate-rich materials. The aim of this work is to evaluate ashes efficiency for remediation of cadmium-contaminated aqueous solutions, and to assess the bioavailability of cadmium on Xenopus laevis larvae. In this study both industrial (MBM-BA) and laboratory (MBM-LA) ashes are compared regarding their efficiency. Kinetic investigations reveal that cadmium ions are quickly immobilized, with a maximum cadmium uptake at 57 mg Cd(2+)/g of ashes for MBM-LA, two times higher than metal uptake quantity of MBM-BA, in our experimental conditions. Chemical and X-ray diffraction analysis (XRD) reveal that Cd(2+) is mainly immobilized as Ca(10-x)Cd(x)(PO(4))(6)(OH)(2) by both ashes, whereas otavite, Cd(CO(3)), is also involved for MBM-LA in cadmium uptake. Otavite formation could be explained by the presence of carbonates in MBM-LA, as observed by IR. Genotoxicity of cadmium solution on Xenopus larvae is observed at 0.02, 0.2 and 2mg Cd(2+)/L. However addition of only 0.1g/L MBM-LA inhibits these effects for the above concentration values whereas Cd(2+) bioaccumulation in larvae's liver is similar for both experiments, with and without ashes.

  10. 3D Nanoscale Chemical Imaging of the Distribution of Aluminum Coordination Environments in Zeolites with Soft X-Ray Microscopy

    NARCIS (Netherlands)

    Aramburo, Luis R.; Liu, Yijin; Tyliszczak, Tolek; de Groot, Frank M. F.; Andrews, Joy C.; Weckhuysen, Bert M.

    2013-01-01

    Here, we present the first nanoscale chemical imaging study revealing the spatial distribution of the amount and coordination environment of aluminum in zeolite materials with 3D scanning transmission X-ray microscopy (STXM). For this purpose, we have focused on two showcase samples involving the in

  11. Revolution In Toxicity Testing And Risk Prediction For Chemicals In The Environment (ASA)

    Science.gov (United States)

    Addressing safety aspects of drugs and environmental chemicals relies extensively on animal testing; however, the quantity of chemicals needing assessment and challenges of species extrapolation require alternative approaches to traditional animal studies. Newer in vitro and in s...

  12. Revolution In Toxicity Testing And Risk Prediction For Chemicals In The Environment (ASA)

    Science.gov (United States)

    Addressing safety aspects of drugs and environmental chemicals relies extensively on animal testing; however, the quantity of chemicals needing assessment and challenges of species extrapolation require alternative approaches to traditional animal studies. Newer in vitro and in s...

  13. Assessing the effect of cement-steel interface on well casing corrosion in aqueous CO2 environments

    Energy Technology Data Exchange (ETDEWEB)

    Han, Jiabin [Los Alamos National Laboratory; Carey, James W [Los Alamos National Laboratory; Zhang, Jinsuo [Los Alamos National Laboratory

    2010-01-01

    CO{sub 2} leakage is a critical safety concern for geologic storage. In wellbore environments, important leakage paths include the rock-cement and cement-casing interfaces. If the cement-casing interface is filled with escaping CO{sub 2}, the well casing directly contacts the CO{sub 2}. This can cause severe corrosion in the presence of water. This paper studies the effect of steel-cement interface gaps, ranging from 1 mm to 0 um, on casing corrosion. Corrosion kinetics were measured employing electrochemical techniques including linear polarization resistance, open circuit potential and electrochemical impedance spectroscopy. The experimental results showed that the corrosion of steel is not significant where the gap between steel and cement is small ({le} 100 {micro}m). Corrosion rates are controlled by the diffusion of corrosive species (H{sub 2}CO{sub 3} and H{sup +}) along the interface. In contrast, steel corrosion is severe in a broad gap where the corrosion process is limited only by the reaction kinetics of steel and corrosive species. The threshold leading to severe corrosion in terms of the cement-steel interface size (100 {micro}m) was determined. Our research clarifies a corrosion scenario at the cement-steel interface. Casing steel corrosion is initiated when attacked by corrosive species at the cement-steel interface. For relatively tight interfaces, this results in a slow thinning of the casing and expansion of the interface width. If the gap increases beyond the critical threshold size, the corrosion rate increases significantly, and a potentially damaging cycle of corrosion and interface expansion is developed.

  14. Surface reactivity and layer analysis of chemisorbed reaction films in the surface-chemical environment of alkyl octadecenoates

    Indian Academy of Sciences (India)

    R B Choudhary; O N Anand; O S Tyagi

    2009-05-01

    Studies on surface reactivity of substrate iron (Fe-particles) were made in the tribo-chemical environment of alkyl octadecenoates. Two alkyl octadecenoates namely ethyl octadecenoate and methyl 12-hydroxy octadecenoate, slightly different in their chemical nature, were taken for preparing the chemisorbed reaction films (CRF) at the temperature 100 ± 5°C. The reaction products collected in the composite (amorphous) phase were isolated into three different solvent-soluble fractions (sub-layer films) using polar solvents of increasing polar strength. The FTIR analysis of these films showed that these were primarily organic in nature and were composed of alkyl and/or aryl hydroxy ethers, unsaturated hydroxy ketones, and aromatic structures chemically linked with iron surface. These reaction films also contained large amount of iron (Fe). Further, these film fractions also showed varying thermal behaviour during thermal decomposition in the temperature range of 50-800°C when thermally evaluated in the nitrogen environment.

  15. Chemicals in Schools: Solutions for Healthy School Environments. K-12 Schools

    Science.gov (United States)

    US Environmental Protection Agency, 2006

    2006-01-01

    School leaders play a pivotal role in keeping schools safe from chemical accidents. Readers of this brochure can help schools develop a chemical cleanout and prevention program and assemble a team of teachers, facilities staff, and administrators with technical expertise to assess chemical safety issues and set policy. Some important team roles…

  16. Exploring consumer exposure pathways and patterns of use for chemicals in the environment

    DEFF Research Database (Denmark)

    Dionisio, Kathie L.; Frame, Alicia M.; Goldsmith, Michael-Rock

    2015-01-01

    (CPCat), a new, publically available (http://actor.epa.gov/cpcat) database of information on chemicals mapped to “use categories” describing the usage or function of the chemical. CPCat was created by combining multiple and diverse sources of data on consumer- and industrial-process based chemical uses...

  17. The role of OH in the chemical evolution of protoplanetary disks : II. Gas-rich environments

    NARCIS (Netherlands)

    Chaparro-Molano, German; Kamp, I.

    2012-01-01

    Context. We present a method for including gas extinction of cosmic-ray-generated UV photons in chemical models of the midplane of protoplanetary disks, focusing on its implications on ice formation and chemical evolution. Aims. Our goal is to improve on chemical models by treating cosmic rays, the

  18. Exploring consumer exposure pathways and patterns of use for chemicals in the environment.

    Science.gov (United States)

    Dionisio, Kathie L; Frame, Alicia M; Goldsmith, Michael-Rock; Wambaugh, John F; Liddell, Alan; Cathey, Tommy; Smith, Doris; Vail, James; Ernstoff, Alexi S; Fantke, Peter; Jolliet, Olivier; Judson, Richard S

    2015-01-01

    Humans are exposed to thousands of chemicals in the workplace, home, and via air, water, food, and soil. A major challenge in estimating chemical exposures is to understand which chemicals are present in these media and microenvironments. Here we describe the Chemical/Product Categories Database (CPCat), a new, publically available (http://actor.epa.gov/cpcat) database of information on chemicals mapped to "use categories" describing the usage or function of the chemical. CPCat was created by combining multiple and diverse sources of data on consumer- and industrial-process based chemical uses from regulatory agencies, manufacturers, and retailers in various countries. The database uses a controlled vocabulary of 833 terms and a novel nomenclature to capture and streamline descriptors of chemical use for 43,596 chemicals from the various sources. Examples of potential applications of CPCat are provided, including identifying chemicals to which children may be exposed and to support prioritization of chemicals for toxicity screening. CPCat is expected to be a valuable resource for regulators, risk assessors, and exposure scientists to identify potential sources of human exposures and exposure pathways, particularly for use in high-throughput chemical exposure assessment.

  19. Environment

    DEFF Research Database (Denmark)

    Valentini, Chiara

    2017-01-01

    The term environment refers to the internal and external context in which organizations operate. For some scholars, environment is defined as an arrangement of political, economic, social and cultural factors existing in a given context that have an impact on organizational processes and structures....... For others, environment is a generic term describing a large variety of stakeholders and how these interact and act upon organizations. Organizations and their environment are mutually interdependent and organizational communications are highly affected by the environment. This entry examines the origin...... and development of organization-environment interdependence, the nature of the concept of environment and its relevance for communication scholarships and activities....

  20. The aqueous chemistry of oxides

    CERN Document Server

    Bunker, Bruce C

    2016-01-01

    The Aqueous Chemistry of Oxides is a comprehensive reference volume and special topics textbook that explores all of the major chemical reactions that take place between oxides and aqueous solutions. The book highlights the enormous impact that oxide-water reactions have in advanced technologies, materials science, geochemistry, and environmental science.

  1. Application of novel nanobiocomposites for removal of nickel(II) from aqueous environments: Equilibrium, kinetics, thermodynamics and ex-situ studies

    Energy Technology Data Exchange (ETDEWEB)

    Varghese, Lina Rose; Das, Devlina; Das, Nilanjana [VIT University, Tamil Nadu (India)

    2016-01-15

    The current study presents a novel approach for the removal of Ni(II) from aqueous environments using plant gum-based (PG) and clay-based (CL) nanobiocomposite (NBC) composed of ZnO nanoparticles and chitosan. Parameters like pH, contact time, temperature, initial metal concentration and adsorbent dosage were optimized. Under optimized conditions, maximum removal of Ni(II) was noted as 90.1% and 95.5% in the case of PG-NBC and CLNBC, respectively. Equilibrium studies suggested a homogeneous mode of adsorption. Good linearity was observed for the pseudo-first order kinetic model, suggesting a physical mode of adsorption. Thermodynamic studies showed an endothermic and spontaneous nature of adsorption. The mechanism was further elucidated using SEM, EDX, AFM and FT-IR analysis. Ex-situ studies showed a maximum Ni(II) removal of 87.34% from electroplating wastewater using CL-NBC in column mode. Regeneration studies suggested that CL-NBC could be consistently reused up to 4 cycles.

  2. Heat-initiated prebiotic formation of peptides from glycine/aspartic acid and glycine/valine in aqueous environment and clay suspension

    Science.gov (United States)

    Pant, Chandra Kala; Lata, Hem; Pathak, Hari Datt; Mehata, Mohan Singh

    2009-04-01

    The effect of heat on the reaction system of glycine/aspartic acid and glycine/valine in the aqueous environment as well as in montmorillonite clay suspension with or without divalent cations (Ca2+, Mg2+ and Ni2+) has been investigated at 85°C±5°C for varying periods under prebiotic drying and wetting conditions. The resulting products were analysed and characterized by chromatographic and spectroscopic methods. Peptide formation appears to depend on the duration of heat effect, nature of reactant amino acids and, to some extent, on montmorillonite clay incorporated with divalent cations. In the glycine/aspartic acid system, oligomerization of glycine was limited up to trimer level (Gly)3 along with the formation of glycyl-aspartic acid, while linear and cyclic peptides of aspartic acid were not formed, whereas the glycine/valine system preferentially elongated homo-oligopeptide of glycine up to pentamer level (Gly)5 along with formation of hetero-peptides (Gly-Val and Val-Gly). These studies are relevant in the context of the prebiotic origin of proteins and the role of clay and metal ions in condensation and oligomerization of amino acids. The length of the bio-oligomer chain depends upon the reaction conditions. However, condensation into even a small length seems significant, as the same process would have taken millions of years in the primitive era of the Earth, leading to the first proteins.

  3. Time-dependent density functional theory study on the excited-state hydrogen-bonding characteristics of polyaniline in aqueous environment

    Science.gov (United States)

    Zhang, Yahong; Duan, Yuping; Liu, Jin

    2017-01-01

    A theoretical study was carried out to study the excited-state of hydrogen-bonding characteristics of polyaniline (PANI) in aqueous environment. The hydrogen-bonded PANI-H2O complexes were studied using first-principles calculations based on density functional theory (DFT). The electronic excitation energies and the corresponding oscillator strengths of the low-lying electronically excited states for hydrogen-bonded complexes were calculated by time-dependent density functional theory (TDDFT). The ground-state geometric structures were optimized, and it is observed that the intermolecular hydrogen bonds Csbnd N ⋯ Hsbnd O and Nsbnd H ⋯ Osbnd H were formed in PANI-H2O complexes. The formed hydrogen bonds influenced the bond lengths, the charge distribution, as well as the spectral characters of the groups involved. It was concluded that all the hydrogen-bonded PANI-H2O complexes were primarily excited to the S1 states with the largest oscillator strength. In addition, the orbital transition from the highest occupied molecular orbital (HOMO) to the lowest unoccupied molecular orbital (LUMO) involved intramolecular charge redistribution resulting to increase the electron density of the quinonoid rings.

  4. Chemical and morphological characteristics of indoor and outdoor particulate matter in an urban environment

    Science.gov (United States)

    Chithra, V. S.; Shiva Nagendra, S. M.

    2013-10-01

    Chemical characterization of suspended particulate matter (SPM) measured inside a naturally ventilated school building (indoor) and at an adjacent roadway (outdoor) in Chennai city was performed during monsoon, winter and summer seasons. The daily average indoor SPM concentrations in monsoon, winter and summer seasons were 158.18, 170.08 and 149.63 μg m-3, respectively. Indoor and outdoor samples were analyzed for 11 inorganic ions using ion chromatography and 28 elements by inductively coupled plasma optical emission spectrometry. Results indicated the dominance of SO (10.89 μg m-3) followed by NH (5.62 μg m-3), NO (5.35 μg m-3), Na+ (4.35 μg m-3) Ca2+ (4.08 μg m-3) and Cl- (3.47 μg m-3) ions in the indoor SPM. In the outdoor SPM, SO, NO and NH ions concentration were slightly higher while Ca2+, K+ and Mg2+ ions concentrations were higher in indoors. Among the elements, crustal element (Al, Fe, Ca, K, Mg and Na) concentrations were much higher (92.7% of the total elemental concentration) in indoor environment than those of toxic elements (Ba, Cr, Cu, Mn, Mo, Ni, Sr, Ti, V and Zn) emitted from vehicles. Analysis of elemental carbon (EC) and organic carbon (OC) components in indoor and outdoor PM indicated the predominance of OC. The indoor/outdoor (I/O) ratios for EC = 0.70 and OC = 0.82, indicating no significant indoor emission sources of OC and EC. To characterize the morphology, indoor and outdoor filters were examined by Scanning Electron Microscopy coupled with energy dispersive X-ray spectrometry. Soot and Al-Si rich particles were mostly found in indoor and outdoor SPM. The presence of toxic elements and soot particles in the indoor PM confirms the contributions of vehicular emissions from the adjacent motorway.

  5. Aram Chaos: a Long Lived Subsurface Aqueous Environment with Strong Water Resources Potential for Human Missions on Mars

    Science.gov (United States)

    Sibille, L.; Mueller, R.; Niles, P. B.; Glotch, T.; Archer, P. D.; Bell, M. S.

    2015-01-01

    Aram Chaos, Mars is a crater 280 kilometers in diameter with elevations circa. minus 2 to minus 3 kilometers below datum that provides a compelling landing site for future human explorers as it features multiple scientific regions of interest (ROI) paired with a rich extensible Resource ROI that features poly-hydrated sulfates [1]. The geologic history of Aram Chaos suggests several past episodes of groundwater recharge and infilling by liquid water, ice, and other materials [1-3]. The creation of the fractured region with no known terrestrial equivalent may have been caused by melting of deep ice reservoirs that triggered the collapse of terrain followed by catastrophic water outflows over the region. Aram Chaos is of particular scientific interest because it is hypothesized that the chaotic terrain may be the source of water that contributed to the creation of nearby valleys such as Ares Vallis flowing toward Chryse Planitia. The liquid water was likely sourced as groundwater and therefore represents water derived from a protected subsurface environment making it a compelling astrobiological site [2]. The past history of water is also represented by high concentrations of hematite, Fe-oxyhydroxides, mono-hydrated and poly-hydrated sulfates [1, 2]. Poly-hydrated sulfates are likely to contain abundant water that evolves at temperatures below 500 degrees Centigrade thus conferring Aram Chaos a potentially high value for early in-situ resource utilization (ISRU) [4]. The geologic history also calls for future prospecting of deep ice deposits and possibly liquid water via deep drilling. The most recent stratigraphic units in the central part of Aram Chaos are not fractured, and are part of a dome-shaped formation that features bright, poorly-consolidated material that contains both hydrated sulfates and ferric oxides according to OMEGA (Observatoire pour la Minéralogie, l'Eau, les Glaces et l'Activité) data [5]. These surface material characteristics are

  6. Analysis of the Raman spectra of Ca(2+)-dipicolinic acid alone and in the bacterial spore core in both aqueous and dehydrated environments.

    Science.gov (United States)

    Kong, Lingbo; Setlow, Peter; Li, Yong-qing

    2012-08-21

    The core of dormant bacterial spores suspended in water contains a large depot of dipicolinic acid (DPA) chelated with divalent cations, predominantly Ca(2+) (CaDPA), and surrounded by water molecules. Since the intensities of the vibration bands of CaDPA molecules depend significantly on the water content in the CaDPA's environment, the Raman spectra of CaDPA in spores may allow the determination of the spore core's hydration state. We have measured Raman spectra of single spores of three Bacillus species in different hydration states including the spores suspended in water, air-dried and vacuum-dried. As a comparison, we also measured the Raman spectra of CaDPA and DPA in different forms including in aqueous solution, and as amorphous powder and crystalline form. We also monitored changes in Raman spectra of an individual spore during dehydration under vacuum. The results indicated that (1) the state of CaDPA in the core of a spore suspended in water is close to an amorphous solid or a glassy state, but still mixed with water molecules; (2) the ratio of intensities of Raman bands at 1575 and 1017 cm(-1) (I(1575)/I(1017)) is sensitive to the water content in the CaDPA's environment; (3) variations in I(1575)/I(1017) are small (∼4%) in a population of dormant Bacillus spores suspended in water; and (4) the I(1575)/I(1017) ratio increases significantly during dehydration under vacuum. Consequently, measurement of the I(1575)/I(1017) ratio of CaDPA in spores may allow a qualitative estimation of the degree of hydration of the bacterial spore's core.

  7. Application of high resolution Chemical Ionization Mass Spectrometry (CI-ToFMS to study SOA composition: focus on formation of oxygenated species via aqueous phase processing

    Directory of Open Access Journals (Sweden)

    D. Aljawhary

    2013-07-01

    Full Text Available This paper demonstrates the capabilities of Chemical Ionization Mass Spectrometry (CIMS to study secondary organic aerosol (SOA composition with a high resolution (HR time-of-flight mass analyzer (aerosol-CI-ToFMS. In particular, by studying aqueous oxidation of Water Soluble Organic Compounds (WSOC extracted from α-pinene ozonolysis SOA, we assess the capabilities of three common CIMS reagent ions: (a protonated water clusters (H2OnH+, (b acetate CH3C(OO− and (c iodide water clusters I(H2On− to monitor SOA composition. As well, we report the relative sensitivity of these reagent ions to a wide range of common organic aerosol constituents. We find that (H2OnH+ is more selective to the detection of less oxidized species, so that the range of O/C and OSC (carbon oxidation state in the SOA spectra is considerably lower than those measured using CH3C(OO− and I(H2On−. Specifically, (H2OnH+ ionizes organic compounds with OSC ≤ 1.3, whereas CH3C(OO− and I(H2On− both ionize highly oxygenated organics with OSC up to 4 with I(H2On− being more selective towards multi-functional organic compounds. In the bulk O/C and H/C space, i.e. in a Van Krevelen plot, there is a remarkable agreement in both absolute magnitude and oxidation trajectory between CI-ToFMS data and those from a high resolution aerosol mass spectrometer (HR-AMS. This indicates that the CI-ToFMS data captures much of the chemical change occurring in the particle and that gas phase species, which are not detected by the HR-AMS, do not dominate the overall ion signal. Finally, the data illustrate the capability of aerosol-CI-ToFMS to monitor specific chemical change, including the fragmentation and functionalization reactions that occur during organic oxidation, and the oxidative conversion of dimeric SOA species into monomers. Overall, aerosol-CI-ToFMS is a valuable, selective complement to some common SOA characterization methods, such as AMS and spectroscopic techniques. Both

  8. Hybrid molecularly imprinted poly(methacrylic acid-TRIM)-silica chemically modified with (3-glycidyloxypropyl)trimethoxysilane for the extraction of folic acid in aqueous medium

    Energy Technology Data Exchange (ETDEWEB)

    Midori de Oliveira, Fernanda; Gava Segatelli, Mariana [Departamento de Química, Universidade Estadual de Londrina, Rod. Celso Garcia Cid, PR 445 Km 380, Campus Universitário, Londrina, PR CEP 86051-990 (Brazil); Tarley, César Ricardo Teixeira, E-mail: ctarleyquim@yahoo.com.br [Departamento de Química, Universidade Estadual de Londrina, Rod. Celso Garcia Cid, PR 445 Km 380, Campus Universitário, Londrina, PR CEP 86051-990 (Brazil); Instituto Nacional de Ciência e Tecnologia (INCT) de Bioanalítica, Universidade Estadual de Campinas (UNICAMP), Instituto de Química, Departamento de Química Analítica, Cidade Universitária Zeferino Vaz s/n, CEP 13083-970 Campinas, SP (Brazil)

    2016-02-01

    In the present study a hybrid molecularly imprinted poly(methacrylic acid-trimethylolpropane trimethacrylate)-silica (MIP) was synthesized and modified with (3-glycidyloxypropyl)trimethoxysilane (GPTMS) with posterior opening of epoxy ring to provide hydrophilic properties of material in the extraction of folic acid from aqueous medium. The chemical and structural aggregates of hybrid material were characterized by means of Fourier Transform Infrared (FT-IR), Transmission Electron Microscopy (TEM), Scanning Electron Microscopy (SEM), Thermogravimetric analysis (TGA) and textural data. Selectivity data of MIP were compared to non-imprinted polymer (NIP) through competitive sorption studies in the presence of caffeine, paracetamol or 4-aminobenzamide yielding relative selectivity coefficients (k′) higher than one unit, thus confirming the selective character of MIP even in the presence of structurally smaller compounds than the folic acid. The lower hydrophobic sorption by bovine serum albumin (BSA) in the MIP as compared to unmodified MIP proves the hydrophilicity of polymer surface by using GPTMS with opening ring. Under acid medium (pH 1.5) the sorption of folic acid onto MIP from batch experiments was higher than the one achieved for NIP. Equilibrium sorption of folic acid was reached at 120 min for MIP, NIP and MIP without GPTMS and kinetic sorption data were well described by pseudo-second-order, Elovich and intraparticle diffusion models. Thus, these results indicate the existence of different binding energy sites in the polymers and a complex mechanism consisting of both surface sorption and intraparticle transport of folic acid within the pores of polymers. - Highlights: • The molecularly imprinted hybrid polymer showed high adsorption capacity for folic acid. • The molecularly imprinted hybrid polymer showed high selectivity for folic acid. • The molecularly imprinted hybrid polymer modified with GPTMS excludes higher amount of BSA.

  9. Effect of precursor solutions stirring on deep level defects concentration and spatial distribution in low temperature aqueous chemical synthesis of zinc oxide nanorods

    Directory of Open Access Journals (Sweden)

    Hatim Alnoor

    2015-08-01

    Full Text Available Hexagonal c-axis oriented zinc oxide (ZnO nanorods (NRs with 120-300 nm diameters are synthesized via the low temperature aqueous chemical route at 80 °C on silver-coated glass substrates. The influence of varying the precursor solutions stirring durations on the concentration and spatial distributions of deep level defects in ZnO NRs is investigated. Room temperature micro-photoluminesnce (μ-PL spectra were collected for all samples. Cathodoluminescence (CL spectra of the as-synthesized NRs reveal a significant change in the intensity ratio of the near band edge emission (NBE to the deep-level emission (DLE peaks with increasing stirring durations. This is attributed to the variation in the concentration of the oxygen-deficiency with increasing stirring durations as suggested from the X-ray photoelectron spectroscopy analysis. Spatially resolved CL spectra taken along individual NRs revealed that stirring the precursor solutions for relatively short duration (1-3 h, which likely induced high super saturation under thermodynamic equilibrium during the synthesis process, is observed to favor the formation of point defects moving towards the tip of the NRs. In contrary, stirring for longer duration (5-15 h will induce low super saturation favoring the formation of point defects located at the bottom of the NRs. These findings demonstrate that it is possible to control the concentration and spatial distribution of deep level defects in ZnO NRs by varying the stirring durations of the precursor solutions.

  10. Hybrid molecularly imprinted poly(methacrylic acid-TRIM)-silica chemically modified with (3-glycidyloxypropyl)trimethoxysilane for the extraction of folic acid in aqueous medium.

    Science.gov (United States)

    de Oliveira, Fernanda Midori; Segatelli, Mariana Gava; Tarley, César Ricardo Teixeira

    2016-02-01

    In the present study a hybrid molecularly imprinted poly(methacrylic acid-trimethylolpropane trimethacrylate)-silica (MIP) was synthesized and modified with (3-glycidyloxypropyl)trimethoxysilane (GPTMS) with posterior opening of epoxy ring to provide hydrophilic properties of material in the extraction of folic acid from aqueous medium. The chemical and structural aggregates of hybrid material were characterized by means of Fourier Transform Infrared (FT-IR), Transmission Electron Microscopy (TEM), Scanning Electron Microscopy (SEM), Thermogravimetric analysis (TGA) and textural data. Selectivity data of MIP were compared to non-imprinted polymer (NIP) through competitive sorption studies in the presence of caffeine, paracetamol or 4-aminobenzamide yielding relative selectivity coefficients (k′) higher than one unit, thus confirming the selective character of MIP even in the presence of structurally smaller compounds than the folic acid. The lower hydrophobic sorption by bovine serum albumin (BSA) in the MIP as compared to unmodified MIP proves the hydrophilicity of polymer surface by using GPTMS with opening ring. Under acid medium(pH 1.5) the sorption of folic acid onto MIP from batch experiments was higher than the one achieved for NIP. Equilibrium sorption of folic acid was reached at 120 min for MIP, NIP and MIP without GPTMS and kinetic sorption data were well described by pseudo-second-order, Elovich and intraparticle diffusion models. Thus, these results indicate the existence of different binding energy sites in the polymers and a complex mechanism consisting of both surface sorption and intraparticle transport of folic acid within the pores of polymers.

  11. Evaluation of meat and bone meal combustion residue as lead immobilizing material for in situ remediation of polluted aqueous solutions and soils: "chemical and ecotoxicological studies".

    Science.gov (United States)

    Deydier, E; Guilet, R; Cren, S; Pereas, V; Mouchet, F; Gauthier, L

    2007-07-19

    As a result of bovine spongiform encephalopathy (BSE) crisis, meat and bone meal (MBM) production can no longer be used to feed cattle and must be safely disposed of or transformed. MBM specific incineration remains an alternative that could offer the opportunity to achieve both thermal valorization and solid waste recovery as ashes are calcium phosphate-rich material. The aim of this work is to evaluate ashes efficiency for in situ remediation of lead-contaminated aqueous solutions and soils, and to assess the bioavailability of lead using two biological models, amphibian Xenopus laevis larvae and Nicotiana tabaccum tobacco plant. With the amphibian model, no toxic or genotoxic effects of ashes are observed with concentrations from 0.1 to 5 g of ashes/L. If toxic and genotoxic effects of lead appear at concentration higher than 1 mg Pb/L (1 ppm), addition of only 100 mg of ashes/L neutralizes lead toxicity even with lead concentration up to 10 ppm. Chemical investigations (kinetics and X-ray diffraction (XRD) analysis) reveals that lead is quickly immobilized as pyromorphite [Pb10(PO4)6(OH)2] and lead carbonate dihydrate [PbCO(3).2H2O]. Tobacco experiments are realized on contaminated soils with 50, 100, 2000 and 10000 ppm of lead with and without ashes amendment (35.3g ashes/kg of soil). Tobacco measurements show that plant elongation is bigger in an ashes-amended soil contaminated with 10000 ppm of lead than on the reference soil alone. Tobacco model points out that ashes present two beneficial actions as they do not only neutralize lead toxicity but also act as a fertilizer.

  12. Workshop on Indian Chemical Industry: perspectives on safety, cleaner production and environment production

    NARCIS (Netherlands)

    Ham, J.M.

    1996-01-01

    A Workshop on "Indian Chemical Industry: Perspectives on Safety, Cleaner Production and Environmental Protection" was held on 3, 4 and 5 January 1996, in Bombay, India. The main objective of the workshop, which was organised jointly by the Government of India, UNIDO/UNDP and the Indian Chemical Manu

  13. Verification of chemical evolution of RNA under hydrothermal environments on the primitive Earth

    Directory of Open Access Journals (Sweden)

    Kawamura Kunio

    2015-01-01

    Full Text Available The RNA World hypothesis proposes that primitive forms of life used polymers resembling RNA both as catalysts and as carriers of genetic information. It has also been suggested that the origin of life occurred in hydrothermal conditions, but this implies that the ester bonds of nucleic acids are sufficiently stable to survive in aqueous conditions at elevated temperatures. Here, we summarize the results of experimental tests of RNA in simulated hydrothermal conditions in which stability is monitored at elevated temperatures and pressures. This perspective provides insight into the evolutionary pathway from small nucleotides to functional RNA molecules and the feasibility of RNA-based life.

  14. Chemical composition of drinking water as a possible environment-specific factor modifying the thyroid risk in the areas subjected to radioiodine contamination

    Science.gov (United States)

    Kolmykova, Lyudmila; Korobova, Elena; Ryzhenko, Boris

    2015-04-01

    Water is one of the main natural agents providing chemical elements' migration in the environment and food chains. In our opinion a study of spatial variation of the essential trace elements in local drinking water is worth considering as the factor that may contribute to variation of the health risk in areas contaminated by radionuclides and radioiodine in particular. Radioiodine was proved to increase the risk of thyroid cancer among children who lived in areas contaminated during the Chernobyl accident. It was also shown that low stable iodine status of the contaminated area and population also contributed to the risk of this disease in case of radionuclide contamination. The goal of the study was to investigate chemical composition of the drinking water in rural settlements of the Bryansk oblast' subjected to radioiodine contamination and to evaluate speciation of stable I and Se on the basis of their total concentration and chemical composition of the real water samples with the help of thermodynamic modelling. Water samples were collected from different aquifers discharging at different depths (dug wells, local private bore holes and water pipes) in rural settlements located in areas with contrasting soil iodine status. Thermodynamic modelling was performed using original software (HCh code of Y.Shvarov, Moscow State University, RUSSIA) incorporating the measured pH, Corg and elements' concentration values. Performed modelling showed possibility of formation of complex CaI+ ion in aqueous phase, I sorption by goethite and transfer of Se to solid phase as FeSe in the observed pH-Eh conditions. It helped to identify environmental conditions providing high I and Se mobility and their depletion from natural waters. Both the experimental data and modeling showed that I and Se migration and deficiency in natural water is closely connected to pH, Eh conditions and the concentration of typomorphic chemical elements (Ca, Mg, Fe) defining the class of water migration

  15. The thermo-mechano-chemical twin-screw reactor, a new perspective for the biorefinery of sunflower whole plant: aqueous extraction of oil and other biopolymers, and production of biodegradable fiberboards from cake

    Directory of Open Access Journals (Sweden)

    Evon Philippe

    2016-09-01

    Full Text Available Biorefinery of sunflower whole plant was performed successfully using a thermo-mechano-chemical twin-screw reactor. This led to the aqueous extraction of oil and other biopolymers like proteins, pectins and non pectic sugars. It resulted in the overall fractionation of biomass, thus allowing a complete valorization of the input. This biorefinery process was not only efficient but it was also environment-friendly. In addition, it contributed to the production of different end products for various industrial applications. Firstly, the hydrophilic phase will be recycled to the process. Secondly, the densest oil-in-water emulsion is a promising candidate for the formulation of cosmetic creams. Thirdly, the upper hydrophobic phase will be usable for the waterproofing treatment of the surface of agromaterials by coating. Its demixing will also lead to the production of proteins with tensioactive properties. These will serve for the food industry. Lastly, the cake was a mixture of plasticized proteins and lignocellulosic fibers. It was thus considered as a natural composite. Its molding into cohesive fiberboards was conducted successfully using both thermopressing and compression molding processes. The self-bonded boards with high density will be suitable for use as load bearing boards in dry conditions (floor underlayers, interior partitions, furniture, etc.. Positioned in walls and ceilings, boards with medium and low density will contribute to the heat insulation of buildings. In addition, the bulk cake will be also usable as a loose fill insulation material. As proposed, this flow chart thus allows a valorization for all fractions originating from the twin-screw reactor.

  16. Chemical Environment Effects on K[beta]/K[alpha] Intensity Ratio: An X-Ray Fluorescence Experiment on Periodic Trends

    Science.gov (United States)

    Durham, Chaney R.; Chase, Jeffery M.; Nivens, Delana A.; Baird, William H.; Padgett, Clifford W.

    2011-01-01

    X-ray fluorescence (XRF) data from an energy-dispersive XRF instrument were used to investigate the chlorine K[alpha] and K[beta] peaks in several group 1 salts. The ratio of the peak intensity is sensitive to the local chemical environment of the chlorine atoms studied in this experiment and it shows a periodic trend for these salts. (Contains 1…

  17. Magnetic ionic liquid aqueous two-phase system coupled with high performance liquid chromatography: A rapid approach for determination of chloramphenicol in water environment.

    Science.gov (United States)

    Yao, Tian; Yao, Shun

    2017-01-20

    A novel organic magnetic ionic liquid based on guanidinium cation was synthesized and characterized. A new method of magnetic ionic liquid aqueous two-phase system (MILATPs) coupled with high-performance liquid chromatography (HPLC) was established to preconcentrate and determine trace amount of chloramphenicol (CAP) in water environment for the first time. In the absence of volatile organic solvents, MILATPs not only has the excellent properties of rapid extraction, but also exhibits a response to an external magnetic field which can be applied to assist phase separation. The phase behavior of MILATPs was investigated and phase equilibrium data were correlated by Merchuk equation. Various influencing factors on CAP recovery were systematically investigated and optimized. Under the optimal conditions, the preconcentration factor was 147.2 with the precision values (RSD%) of 2.42% and 4.45% for intra-day (n=6) and inter-day (n=6), respectively. The limit of detection (LOD) and limit of quantitation (LOQ) were 0.14ngmL(-1) and 0.42ngmL(-1), respectively. Fine linear range of 12.25ngmL(-1)-2200ngmL(-1) was obtained. Finally, the validated method was successfully applied for the analysis of CAP in some environmental waters with the recoveries for the spiked samples in the acceptable range of 94.6%-99.72%. Hopefully, MILATPs is showing great potential to promote new development in the field of extraction, separation and pretreatment of various biochemical samples. Copyright © 2016 Elsevier B.V. All rights reserved.

  18. Survey on bio-chemical complex harmonized with global environment. 3; Kankyo chowagata seibutsu kagaku konbinato ni kansuru chosa. 3

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1996-03-01

    A survey was conducted of bio-chemical complex harmonized with the global environment for the purpose of constructing the material production process harmonized with the environment by the process fusion between biological conversion and chemical reaction. Palm oil was taken up as renewable raw material plant resource. The process utilizing bio-chemical reaction advances at normal temperature and pressure and is high in reaction specificity and selectivity. This is a recycling, circulation and environmental harmony type production technology which brings high yield, energy conservation, resource conservation, and low environmental loads. Waste water treatment and production of useful substances from sludge were thought as elementary technology. A possibility was studied of enzyme production by culturing solid waste, and the enzyme was applied to the hydrolysis process. The paper indicated trace components in the palm oil and the extraction method and proposed the production process of new derivatives for adding value to hydrolysate. A study was also made of the overall process flow which integrated these new processes and the material balance. The comprehensive evaluation of this new process was made from the aspect of the product structure, the market, construction cost, economical efficiency, and the environment. 133 refs., 65 figs., 56 tabs.

  19. A REVIEW OF APPLICATIONS OF LUMINESCENCE TO MONITORING OF CHEMICAL CONTAMINANTS IN THE ENVIRONMENT

    Science.gov (United States)

    The recent analytical literature on the application of luminescence techniques to the measurement of various classes of environmentally significant chemicals has been reviewed. Luminescent spectroscopy based methods are compared to other current techniques. Also, examples of rece...

  20. Impact of toxic chemicals on local wastewater treatment plant and the environment

    Science.gov (United States)

    Bennett, Gary F.

    1989-05-01

    Because toxic chemicals being discharged to sewers were simultaneously interfering with wastewater treatment processes of municipal, biological treatment plants and were passing through these plants to negatively impact the bodies of water to which these plants were discharging, the U.S. Environmental Protection Agency issued regulations governing industrial discharges to municipal sewers. These “Pretreatment Regulations” limit industrial discharges to municipal sewers of heavy metals, oil and grease, acids and bases, and toxic organic chemicals. This paper discusses the evolution of these regulations, the basis for them, the types of regulations (categorical and local), and the rationale for their promulgation based on the impacts of toxics chemicals on the treatment plant and receiving system. Finally, the expected results of these regulations in reducing industrial discharges of toxic chemicals is discussed.

  1. CHEMICALS

    CERN Document Server

    Medical Service

    2002-01-01

    It is reminded that all persons who use chemicals must inform CERN's Chemistry Service (TIS-GS-GC) and the CERN Medical Service (TIS-ME). Information concerning their toxicity or other hazards as well as the necessary individual and collective protection measures will be provided by these two services. Users must be in possession of a material safety data sheet (MSDS) for each chemical used. These can be obtained by one of several means : the manufacturer of the chemical (legally obliged to supply an MSDS for each chemical delivered) ; CERN's Chemistry Service of the General Safety Group of TIS ; for chemicals and gases available in the CERN Stores the MSDS has been made available via EDH either in pdf format or else via a link to the supplier's web site. Training courses in chemical safety are available for registration via HR-TD. CERN Medical Service : TIS-ME :73186 or service.medical@cern.ch Chemistry Service : TIS-GS-GC : 78546

  2. Roles of chemical metrology in electronics industry and associated environment in Korea: a tutorial.

    Science.gov (United States)

    Kang, Namgoo; Kim, Kyung Joong; Kim, Jin Seog; Lee, Joung Hae

    2015-03-01

    Chemical metrology is gaining importance in electronics industry that manufactures semiconductors, electronic displays, and microelectronics. Extensive and growing needs from this industry have raised the significance of accurate measurements of the amount of substances and material properties. For the first time, this paper presents information on how chemical metrology is being applied to meet a variety of needs in the aspects of quality control of electronics products and environmental regulations closely associated with electronics industry. For a better understanding of the roles of the chemical metrology within electronics industry, the recent research activities and results in chemical metrology are presented using typical examples in Korea where electronic industry is leading a national economy. Particular attention is paid to the applications of chemical metrology for advancing emerging electronics technology developments. Such examples are a novel technique for the accurate quantification of gas composition at nano-liter levels within a MEMS package, the surface chemical analysis of a semiconductor device. Typical metrological tools are also presented for the development of certified reference materials for fluorinated greenhouse gases and proficiency testing schemes for heavy metals and chlorinated toxic gas in order to cope properly with environmental issues within electronics industry. In addition, a recent technique is presented for the accurate measurement of the destruction and removal efficiency of a typical greenhouse gas scrubber.

  3. Implications of global climate change for the assessment and management of human health risks of chemicals in the natural environment.

    Science.gov (United States)

    Balbus, John M; Boxall, Alistair B A; Fenske, Richard A; McKone, Thomas E; Zeise, Lauren

    2013-01-01

    Global climate change (GCC) is likely to alter the degree of human exposure to pollutants and the response of human populations to these exposures, meaning that risks of pollutants could change in the future. The present study, therefore, explores how GCC might affect the different steps in the pathway from a chemical source in the environment through to impacts on human health and evaluates the implications for existing risk-assessment and management practices. In certain parts of the world, GCC is predicted to increase the level of exposure of many environmental pollutants due to direct and indirect effects on the use patterns and transport and fate of chemicals. Changes in human behavior will also affect how humans come into contact with contaminated air, water, and food. Dietary changes, psychosocial stress, and coexposure to stressors such as high temperatures are likely to increase the vulnerability of humans to chemicals. These changes are likely to have significant implications for current practices for chemical assessment. Assumptions used in current exposure-assessment models may no longer apply, and existing monitoring methods may not be robust enough to detect adverse episodic changes in exposures. Organizations responsible for the assessment and management of health risks of chemicals therefore need to be more proactive and consider the implications of GCC for their procedures and processes.

  4. Combined pre-concentration and real-time in-situ chemical detection of explosives in the marine environment

    Science.gov (United States)

    Dock, Matthew L.; Harper, Ross J.; Knobbe, Ed

    2010-04-01

    ICx Nomadics has developed the first known real-time sensor system that is capable of detecting chemical signatures emanating from underwater explosives, based upon the same amplifying fluorescent polymer (AFP) fluorescence-quenching transduction mechanism that the Fido® family of explosives detectors utilizes. The SeaPup is capable of real-time detection of the trace chemical signatures emanating from submerged explosive compounds and has been successfully tested on various marine platforms, including a crawler robot, an autonomous underwater vehicle (AUV), and a remotely operated underwater vehicle (ROV). The present work is focused on advances in underwater in-situ chemical sensing; wherein trace amounts of dissolved explosive compounds may be detected and discriminated from other chemical species found in the marine environment. Recent progress with the SeaPup platform have focused on increasing the sensitivity of the AFP matrix through the development of a preconcentration system designed to harvest explosive analytes from a larger sample volume over a predetermined period of time. This permits real time monitoring of chemical plumes during the approach to a potential source, combined with the lowered limit of detection from extended sampling of targeted items. SeaPup has been shown to effectively map "explosive scent plumes" emanating from an underwater source of TNT, and the preconcentration system has previously been demonstrated to enhance sensitivity be over 2 orders of magnitude in a time window of minutes.

  5. Cold aqueous planetary geochemistry with FREZCHEM from modeling to the search for life at the limits

    CERN Document Server

    Marion, Giles M

    2007-01-01

    This book explicitly investigates issues of astrobiological relevance in the context of cold aqueous planetary geochemistry. At the core of the technical chapters is the FREZCHEM model, initially developed over many years by one of the authors to quantify aqueous electrolyte properties and chemical thermodynamics at subzero temperatures. FREZCHEM, of general relevance to biogeochemists and geochemical modelers, cold planetary scientists, physicochemists and chemical engineers, is subsequently applied to the exploration of biogeochemical applications to solar systems bodies in general, and to speculations about the limits for life in cold environments in particular.

  6. Tectonic uplift and denudation rate influence soil chemical weathering intensity in a semi-arid environment, southeast Spain: physico-chemical and mineralogical evidence

    Science.gov (United States)

    Ameijeiras-Mariño, Yolanda; Opfergelt, Sophie; Schoonejans, Jérôme; Vanacker, Veerle; Sonnet, Philippe; Delmelle, Pierre

    2015-04-01

    Tectonic uplift is known to influence denudation rates. Denudation, including chemical weathering and physical erosion, affects soil production rates and weathering intensities. At topographic steady state, weathering can be transport- or weathering-limited. In the transport-limited regime, low denudation rates should lead to comparatively high weathering intensities, while in the weathering-limited case high denudation rates are associated with lower weathering intensities. Here, we test if this relationship applies to semi-arid environments where chemical weathering is generally slow. Three catchments (EST, FIL and CAB) were studied in the Internal Zone of the Betic Cordillera in southeast Spain, spanning a range of increasing uplift rates (10-170 mm/kyr) and increasing denudation rates (20-250 mm/kyr) from EST to CAB. In each catchment, two ridgetop soil profiles were sampled down to the bedrock. The three catchments have similar vegetation and climatic conditions, with precipitation of 250- 315 mm/yr and mean annual temperature of 15-17 °C. The mineralogy of the bedrock, as determined by XRD, is similar across the three catchments and is characterized by the presence of quartz, muscovite, clinochlore, biotite and plagioclase. This primary mineral assemblage is also found in the catchment soils, indicating that the soils studied derive from the same parent material. The soil clay-size fraction is dominated by kaolinite, vermiculite and illite. However, the proportions of the soil primary and secondary minerals vary between the catchment sites. The abundance of biotite decreases from CAB (14%) to EST (4%), whereas the quartz and clay contents show an opposite tendency (from 30 to 69% and 9.9 to 14.3%, respectively). Further, the abundance of vermiculite increases from CAB to EST. The results are interpreted in terms of increasing weathering intensity from CAB to EST by weathering of biotite into vermiculite and enrichment of soils on more weathering resistant

  7. Assessing the carcinogenic potential of low-dose exposures to chemical mixtures in the environment: the challenge ahead

    Science.gov (United States)

    Goodson, William H.; Lowe, Leroy; Carpenter, David O.; Gilbertson, Michael; Manaf Ali, Abdul; Lopez de Cerain Salsamendi, Adela; Lasfar, Ahmed; Carnero, Amancio; Azqueta, Amaya; Amedei, Amedeo; Charles, Amelia K.; Collins, Andrew R.; Ward, Andrew; Salzberg, Anna C.; Colacci, Anna Maria; Olsen, Ann-Karin; Berg, Arthur; Barclay, Barry J.; Zhou, Binhua P.; Blanco-Aparicio, Carmen; Baglole, Carolyn J.; Dong, Chenfang; Mondello, Chiara; Hsu, Chia-Wen; Naus, Christian C.; Yedjou, Clement; Curran, Colleen S.; Laird, Dale W.; Koch, Daniel C.; Carlin, Danielle J.; Felsher, Dean W.; Roy, Debasish; Brown, Dustin G.; Ratovitski, Edward; Ryan, Elizabeth P.; Corsini, Emanuela; Rojas, Emilio; Moon, Eun-Yi; Laconi, Ezio; Marongiu, Fabio; Al-Mulla, Fahd; Chiaradonna, Ferdinando; Darroudi, Firouz; Martin, Francis L.; Van Schooten, Frederik J.; Goldberg, Gary S.; Wagemaker, Gerard; Nangami, Gladys N.; Calaf, Gloria M.; Williams, Graeme P.; Wolf, Gregory T.; Koppen, Gudrun; Brunborg, Gunnar; Lyerly, H. Kim; Krishnan, Harini; Ab Hamid, Hasiah; Yasaei, Hemad; Sone, Hideko; Kondoh, Hiroshi; Salem, Hosni K.; Hsu, Hsue-Yin; Park, Hyun Ho; Koturbash, Igor; Miousse, Isabelle R.; Scovassi, A.Ivana; Klaunig, James E.; Vondráček, Jan; Raju, Jayadev; Roman, Jesse; Wise, John Pierce; Whitfield, Jonathan R.; Woodrick, Jordan; Christopher, Joseph A.; Ochieng, Josiah; Martinez-Leal, Juan Fernando; Weisz, Judith; Kravchenko, Julia; Sun, Jun; Prudhomme, Kalan R.; Narayanan, Kannan Badri; Cohen-Solal, Karine A.; Moorwood, Kim; Gonzalez, Laetitia; Soucek, Laura; Jian, Le; D’Abronzo, Leandro S.; Lin, Liang-Tzung; Li, Lin; Gulliver, Linda; McCawley, Lisa J.; Memeo, Lorenzo; Vermeulen, Louis; Leyns, Luc; Zhang, Luoping; Valverde, Mahara; Khatami, Mahin; Romano, Maria Fiammetta; Chapellier, Marion; Williams, Marc A.; Wade, Mark; Manjili, Masoud H.; Lleonart, Matilde E.; Xia, Menghang; Gonzalez Guzman, Michael J.; Karamouzis, Michalis V.; Kirsch-Volders, Micheline; Vaccari, Monica; Kuemmerle, Nancy B.; Singh, Neetu; Cruickshanks, Nichola; Kleinstreuer, Nicole; van Larebeke, Nik; Ahmed, Nuzhat; Ogunkua, Olugbemiga; Krishnakumar, P.K.; Vadgama, Pankaj; Marignani, Paola A.; Ghosh, Paramita M.; Ostrosky-Wegman, Patricia; Thompson, Patricia A.; Dent, Paul; Heneberg, Petr; Darbre, Philippa; Leung, Po Sing; Nangia-Makker, Pratima; Cheng, Qiang (Shawn); Robey, R.Brooks; Al-Temaimi, Rabeah; Roy, Rabindra; Andrade-Vieira, Rafaela; Sinha, Ranjeet K.; Mehta, Rekha; Vento, Renza; Di Fiore, Riccardo; Ponce-Cusi, Richard; Dornetshuber-Fleiss, Rita; Nahta, Rita; Castellino, Robert C.; Palorini, Roberta; Hamid, Roslida A.; Langie, Sabine A.S.; Eltom, Sakina E.; Brooks, Samira A.; Ryeom, Sandra; Wise, Sandra S.; Bay, Sarah N.; Harris, Shelley A.; Papagerakis, Silvana; Romano, Simona; Pavanello, Sofia; Eriksson, Staffan; Forte, Stefano; Casey, Stephanie C.; Luanpitpong, Sudjit; Lee, Tae-Jin; Otsuki, Takemi; Chen, Tao; Massfelder, Thierry; Sanderson, Thomas; Guarnieri, Tiziana; Hultman, Tove; Dormoy, Valérian; Odero-Marah, Valerie; Sabbisetti, Venkata; Maguer-Satta, Veronique; Rathmell, W.Kimryn; Engström, Wilhelm; Decker, William K.; Bisson, William H.; Rojanasakul, Yon; Luqmani, Yunus; Chen, Zhenbang; Hu, Zhiwei

    2015-01-01

    Lifestyle factors are responsible for a considerable portion of cancer incidence worldwide, but credible estimates from the World Health Organization and the International Agency for Research on Cancer (IARC) suggest that the fraction of cancers attributable to toxic environmental exposures is between 7% and 19%. To explore the hypothesis that low-dose exposures to mixtures of chemicals in the environment may be combining to contribute to environmental carcinogenesis, we reviewed 11 hallmark phenotypes of cancer, multiple priority target sites for disruption in each area and prototypical chemical disruptors for all targets, this included dose-response characterizations, evidence of low-dose effects and cross-hallmark effects for all targets and chemicals. In total, 85 examples of chemicals were reviewed for actions on key pathways/mechanisms related to carcinogenesis. Only 15% (13/85) were found to have evidence of a dose-response threshold, whereas 59% (50/85) exerted low-dose effects. No dose-response information was found for the remaining 26% (22/85). Our analysis suggests that the cumulative effects of individual (non-carcinogenic) chemicals acting on different pathways, and a variety of related systems, organs, tissues and cells could plausibly conspire to produce carcinogenic synergies. Additional basic research on carcinogenesis and research focused on low-dose effects of chemical mixtures needs to be rigorously pursued before the merits of this hypothesis can be further advanced. However, the structure of the World Health Organization International Programme on Chemical Safety ‘Mode of Action’ framework should be revisited as it has inherent weaknesses that are not fully aligned with our current understanding of cancer biology. PMID:26106142

  8. Spatially Resolved Spectroscopy and Chemical History of Star-forming Galaxies in the Hercules Cluster: The Effects of the Environment

    Science.gov (United States)

    Petropoulou, V.; Vílchez, J.; Iglesias-Páramo, J.; Papaderos, P.; Magrini, L.; Cedrés, B.; Reverte, D.

    2011-06-01

    Spatially resolved spectroscopy has been obtained for a sample of 27 star-forming (SF) galaxies selected from our deep Hα survey of the Hercules cluster. We have applied spectral synthesis models to all emission-line spectra of this sample using the population synthesis code STARLIGHT and have obtained fundamental parameters of stellar components such as mean metallicity and age. The emission-line spectra were corrected for underlying stellar absorption using these spectral synthesis models. Line fluxes were measured and O/H and N/O gas chemical abundances were obtained using the latest empirical calibrations. We have derived the masses and total luminosities of the galaxies using available Sloan Digital Sky Survey broadband photometry. The effects of cluster environment on the chemical evolution of galaxies and on their mass-metallicity (MZ) and luminosity-metallicity (LZ) relations were studied by combining the derived gas metallicities, the mean stellar metallicities and ages, the masses and luminosities of the galaxies, and their existing H I data. Our Hercules SF galaxies are divided into three main subgroups: (1) chemically evolved spirals with truncated ionized-gas disks and nearly flat oxygen gradients, demonstrating the effect of ram-pressure stripping; (2) chemically evolved dwarfs/irregulars populating the highest local densities, possible products of tidal interactions in preprocessing events; and (3) less metallic dwarf galaxies that appear to be "newcomers" to the cluster and are experiencing pressure-triggered star formation. Most Hercules SF galaxies follow well-defined MZ and LZ sequences (for both O/H and N/O), though the dwarf/irregular galaxies located at the densest regions appear to be outliers to these global relations, suggesting a physical reason for the dispersion in these fundamental relations. The Hercules cluster appears to be currently assembling via the merger of smaller substructures, providing an ideal laboratory where the local

  9. Absorption and desorption mass transfer rates in chemically enhanced reactive systems. Part I : Chemical enhancement factors

    NARCIS (Netherlands)

    Hamborg, Espen S.; Versteeg, Geert F.

    2012-01-01

    The chemical enhancement factors have been measured in a controlled environment for absorption and desorption mass transfer processes in aqueous 2.0 M MDEA solutions at temperatures of 298.15, 313.15, and 333.15 K and the loading of CO2 ranging from 0 to 0.8 in a batch-operated stirred tank reactor.

  10. Prioritization of chemicals in the aquatic environment based on risk assessment: analytical, modeling and regulatory perspective.

    Science.gov (United States)

    Guillén, D; Ginebreda, A; Farré, M; Darbra, R M; Petrovic, M; Gros, M; Barceló, D

    2012-12-01

    The extensive and intensive use of chemicals in our developed, highly technological society includes more than 100,000 chemical substances. Significant scientific evidence has lead to the recognition that their improper use and release may result in undesirable and harmful side-effects on both the human and ecosystem health. To cope with them, appropriate risk assessment processes and related prioritization schemes have been developed in order to provide the necessary scientific support for regulatory procedures. In the present paper, two of the elements that constitute the core of risk assessment, namely occurrence and hazard effects, have been discussed. Recent advances in analytical chemistry (sample pre-treatment and instrumental equipment, etc.) have allowed for more comprehensive monitoring of environmental pollution reaching limits of detection up to sub ng L(-1). Alternative to analytical measurements, occurrence models can provide risk managers with a very interesting approach for estimating environmental concentrations from real or hypothetical scenarios. The most representative prioritization schemes used for issuing lists of concerning chemicals have also been examined and put in the context of existing environmental policies for protection strategies and regulations. Finally, new challenges in the field of risk-assessment have been outlined, including those posed by new materials (i.e., nanomaterials), transformation products, multi-chemical exposure, or extension of the risk assessment process to the whole ecosystem.

  11. Joint Doctrine for Operations in Nuclear, Biological, and Chemical (NBC) Environments

    Science.gov (United States)

    2007-11-02

    Arabian Ministry of Defense and Aviation to form a Saudi joint-level NBC staff. He and Captain Paul Schiele conducted a three-day refresher training...officers by mid- September to form the USCENTCOM NBC Center (NBCC). On 23 August, Captain Paul Schiele and three chemical officers from CRDEC joined

  12. Identifying Rhodamine Dye Plume Sources in Near-Shore Oceanic Environments by Integration of Chemical and Visual Sensors

    Directory of Open Access Journals (Sweden)

    Jiangchen Yu

    2013-03-01

    Full Text Available This article presents a strategy for identifying the source location of a chemical plume in near-shore oceanic environments where the plume is developed under the influence of turbulence, tides and waves. This strategy includes two modules: source declaration (or identification and source verification embedded in a subsumption architecture. Algorithms for source identification are derived from the moth-inspired plume tracing strategies based on a chemical sensor. The in-water test missions, conducted in November 2002 at San Clemente Island (California, USA in June 2003 in Duck (North Carolina, USA and in October 2010 at Dalian Bay (China, successfully identified the source locations after autonomous underwater vehicles tracked the rhodamine dye plumes with a significant meander over 100 meters. The objective of the verification module is to verify the declared plume source using a visual sensor. Because images taken in near shore oceanic environments are very vague and colors in the images are not well-defined, we adopt a fuzzy color extractor to segment the color components and recognize the chemical plume and its source by measuring color similarity. The source verification module is tested by images taken during the CPT missions.

  13. Assessing the potential hazard of chemical substances for the terrestrial environment. Development of hazard classification criteria and quantitative environmental indicators.

    Science.gov (United States)

    Tarazona, J V; Fresno, A; Aycard, S; Ramos, C; Vega, M M; Carbonell, G

    2000-03-20

    Hazard assessment constitutes an essential tool in order to evaluate the potential effects of chemical substances on organisms and ecosystems. It includes as a first step, hazard identification, which must detect the potential dangers of the substance (i.e. the kind of effects that the substance may produce), and a second step to quantify each danger and to set the expected dose/response relationships. Hazard assessment plays a key role in the regulation of chemical substances, including pollution control and sustainable development. However, the aquatic environment has largely received more attention than terrestrial ecosystems. This paper presents the extrapolation of several basic concepts from the aquatic to the terrestrial compartment, and suggests possibilities for their regulatory use. Two specific proposals are discussed. The first focuses on the scientific basis of the hazard identification-classification criteria included in the EU regulations and their extrapolation to the terrestrial environment. The second focuses on the OECD programme for environmental indicators and the development of a soil pollution pressure indicator to quantify the potential hazards for the soil compartment and its associated terrestrial ecosystem related to the toxic chemicals applied deliberately (i.e. pesticides) or not (i.e. heavy metals in sludge-based fertilisers; industrial spills) to the soil.

  14. Chemical, Mechanical, and Durability Properties of Concrete with Local Mineral Admixtures under Sulfate Environment in Northwest China

    Directory of Open Access Journals (Sweden)

    Qingke Nie

    2014-05-01

    Full Text Available Over the vast Northwest China, arid desert contains high concentrations of sulfate, chloride, and other chemicals in the ground water, which poses serious challenges to infrastructure construction that routinely utilizes portland cement concrete. Rapid industrialization in the region has been generating huge amounts of mineral admixtures, such as fly ash and slags from energy and metallurgical industries. These industrial by-products would turn into waste materials if not utilized in time. The present study evaluated the suitability of utilizing local mineral admixtures in significant quantities for producing quality concrete mixtures that can withstand the harsh chemical environment without compromising the essential mechanical properties. Comprehensive chemical, mechanical, and durability tests were conducted in the laboratory to characterize the properties of the local cementitious mineral admixtures, cement mortar and portland cement concrete mixtures containing these admixtures. The results from this study indicated that the sulfate resistance of concrete was effectively improved by adding local class F fly ash and slag, or by applying sulfate resistance cement to the mixtures. It is noteworthy that concrete containing local mineral admixtures exhibited much lower permeability (in terms of chloride ion penetration than ordinary portland cement concrete while retaining the same mechanical properties; whereas concrete mixtures made with sulfate resistance cement had significantly reduced strength and much increased chloride penetration comparing to the other mixtures. Hence, the use of local mineral admixtures in Northwest China in concrete mixtures would be beneficial to the performance of concrete, as well as to the protection of environment.

  15. Chemical nature of catalysts of oxide nanoparticles in environment prevailing during growth of carbon nanostructures by CCVD

    Indian Academy of Sciences (India)

    M JANA; A SIL; S RAY

    2016-12-01

    Carbon nanostructures (CNS) are often grown using oxide nanoparticles as catalyst in chemical vapour deposition and these oxides are not expected to survive as such during growth. In the present study, the catalysts of cobalt- and nickel oxide-based nanoparticles of sizes varying over a range have been reduced at 575$^{\\circ}$C under environment resulting from the introduction of C$_2$H$_2$ $+$ NH$_3$ during growth of CNS as well as under introductionof C$_2$H$_2$ and NH$_3$ separately. The structure of the reduced nanoparticles is often different from the equilibrium structure of the bulk. Nanoparticles of cobalt oxide with and without doping by copper oxide are reduced to cobalt alloy or cobalt nanoparticles having fcc structure, but the rate of reduction is relatively less in NH$_3$ environment. However, reduced nickel oxide nanoparticles with and without doping shows a mix of fcc and hcp phases. The presence of hydrogen and nitrogen in the environment appears to discourage the formation of hcp nickel as inferred from the results in NH$_3$ environment. Cobalt carbide forms when the 10 wt.% or less doped cobalt oxide is reduced in C$_2$H$_2$ $+$ NH$_3$ environment. At higher level of doping of 20 wt.%, separate metallic phase of copper appears andcarbide formation gets suppressed.

  16. Thermal stability and energy harvesting characteristics of Au nanorods: harsh environment chemical sensing

    Science.gov (United States)

    Karker, Nicholas; Dharmalingam, Gnanaprakash; Carpenter, Michael A.

    2015-05-01

    Monitoring the levels of polluting gases such as CO and NOx from high temperature (500°C and higher) combustion environments requires materials with high thermal stability and resilience that can withstand harsh oxidizing and reducing environments. Au nanorods (AuNRs) have shown potential in plasmonic gas sensing due to their catalytic activity, high oxidation stability, and absorbance sensitivity to changes in the surrounding environment. By using electron beam lithography, AuNR geometries can be patterned with tight control of the rod dimensions and spacings, allowing tunability of their optical properties. Methods such as NR encapsulation within an yttria-stabilized zirconia overcoat layer with subsequent annealing procedures will be shown to improve temperature stability within a simulated harsh environment. Since light sources and spectrometers are typically required to obtain optical measurements, integration is a major barrier for harsh environment sensing. Plasmonic sensing results will be presented where thermal energy is harvested by the AuNRs, which replaces the need for an external incident light source. Results from gas sensing experiments that utilize thermal energy harvesting are in good agreement with experiments which use an external incident light source. Principal component analysis results demonstrate that by selecting the most "active" wavelengths in a plasmonic band, the wavelength space can be reduced from hundreds of monitored wavelengths to just four, without loss of information about selectivity of the AuNRs. By combining thermal stability, the thermal energy harvesting capability, and the selectivity in gas detection (achieved through multivariate analysis), integration of plasmonic sensors into combustion environments can be greatly simplified.

  17. Passive sampling in regulatory chemical monitoring of nonpolar organic compounds in the aquatic environment

    NARCIS (Netherlands)

    Booij, K.; Robinson, C.D.; Burgess, R.M.; Mayer, P.; Roberts, C.A.; Ahrens, L.; Allan, I.J.; Brant, J.; Jones, L.; Kraus, U.R.; Larsen, M.M.; Lepom, P.; Petersen, J.; Pröfrock, D.; Roose, P.; Schäfer, S.; Smedes, F.; Tixier, C.; Vorkamp, K.; Whitehouse, P.

    2016-01-01

    We reviewed compliance monitoring requirements in the EuropeanUnion, the United States, and the Oslo-Paris Convention for the protection of themarine environment of the North-East Atlantic, and evaluated if these are met bypassive sampling methods for nonpolar compounds. The strengths andshortcoming

  18. Interactions of Changing Solar Ultraviolet Radiation and Climate with Light Induced Chemical Reactions in Aquatic Environments

    Science.gov (United States)

    Changes in the ozone layer over the past two decades have resulted in increases in solar ultraviolet radiation that reach the surface of North American aquatic environments. Concurrent changes in atmospheric CO2 are resulting in changes in stratification and precipitation that ar...

  19. INTERACTIONS OF LIGHT AND CHEMICAL REACTIONS IN THE AQUATIC ENVIRONMENT: KINETIC AND MECHANISTIC ASPECTS

    Science.gov (United States)

    Changes in the ozone layer over the past two decades have resulted in increases in solar ultraviolet (UV) radiation that reaches the surface of aquatic environments. Recent studies have demonstrated that these UV increases cause changes in photochemical reactions that affect the...

  20. Initial assessment of the hazards and risks of new chemicals for man and the environment. Part

    NARCIS (Netherlands)

    Vermeire TG; van Iersel AAJ; de Leeuw FAAM; Peijnenburg WJGM; van der Poel P; Taalman RDFM; Toet C

    1992-01-01

    This report describes the initial hazard and risk assessment process for new substances at the National Institute of Public Health and Environmental Protection (RIVM) in the Netherlands. This assessment pertains to both man and the environment and is performed within the framework of the European C

  1. The Mechanisms and Effects of the Plant Activation of Chemicals in the Environment

    Science.gov (United States)

    1990-04-09

    was established for these TX1 cells. Several flasks were inoculated with 3 g each from a 7-day culture. At approximately 24-hour interva!s, E fresh...discussion. Environ. Health Perspectives 27:45-50. Plewa, M.J. and J.M. Gentile. 1976. Mutagenicity of atrazine: A maize microbe bioassay. Mutation Res

  2. Numerical simulation of chemical processes in helium plasmas in atmosphere environment

    Institute of Scientific and Technical Information of China (English)

    欧阳建明; 郭伟; 王龙; 邵福球

    2005-01-01

    A model is built to study chemical processes in plasmas generated in helium with trace amounts of air at atmospheric pressure or low pressures. The plasma lifetimes and the temporal evolutions of the main charged species are presented. The plasma lifetimes are longer than that in air plasma at atmospheric pressure, but this is not true at low pressures. The electron number density does not strictly obey the exponential damping law in a longer period.

  3. Estimation of The Physico-Chemical Parameters in Marine Environment (Yumurtalik Bight- Iskenderun Bay

    Directory of Open Access Journals (Sweden)

    Gökhan Tamer Kayaalp

    2016-02-01

    Full Text Available The study was carried out to estimate the temperature, light intensity, salinity, Dissolved O2 (DO, pH values and the biotic parameter chlorophyll- a in the water column related with the depth. Because, the physico-chemical parameters affect greatly both primary and secondary producers in marine life. For this purpose the physico-chemical properties were determined day and night for 40 meter depth during the eight days. The means were compared by using the analysis of variance method and Duncan’s Multiple Comparison Test. Also physico-chemical parameters were estimated by using the analysis of regression and correlation. The effect of temperature and salinity were found significant according to the result of the analysis of variance during the day. Also the similar results were found for the night. While the effect of the depth on the chloropyll-a a was significant in the night, the effect of the depth on the DO was not significant in the day and night. The correlations among the depth and the parameters were defined. It was found the negative correlation between the depth and the temperature and light intensity. Determination coefficient of the model for salinity was also found different for day time. The correlation values among the depth and the temperature, salinity and pH were found different for the night.

  4. Chemical and mineralogical concerns for the use of man-made materials in the post-emplacement environment

    Energy Technology Data Exchange (ETDEWEB)

    Meike, A.

    1993-01-16

    In a radioactive waste repository, materials will be introduced for a variety of reasons. Some materials such as metals, bonding agents, and concrete will serve as active parts of the designed engineered barrier system (EBS). Other materials will be introduced to serve a number of purposes that include any or all of the following: surveillance (thermocouples, gauges), construction and operation (drilling rigs, roadbeds, exhaust fumes, chemical toilets, concrete, grout, rebar), lubrication (petroleum-based products, rope dressing) and other functions. Water chemistry will directly affect the corrosion of containers, the dissolution of spent fuel and waste glass and the concentration of dissolved or suspended radionuclides in water that exits breached containers. To predict the water quality requires a knowledge of the dissolution kinetics of the phases present in man-made materials, and the precipitation kinetics of product phases. The chemical evolution of man-made materials of interest to the Yucca Mountain project are by and large not presently known. Prediction of the long-term behavior (10,000 years) required of the modeling efforts is an additional layer of complexity that is not addressed by current models of water chemistry. Man-made modifications to the environment may significantly alter the thermal, chemical and radionuclide transportation attributes of the natural environment that are presently being considered in order to determine a waste package design. The specific chemical concerns addressed here are: solubility and stability of solid phases; liquid and gas phase stability; long term effects; radiolysis effects; colloids; and interactions between man-made material, rock, and J-13 or concentrated J-13 water. The report concludes with recommendations.

  5. Apparent Oil-water Partition Coefficient and Aqueous Chemical Stability of Venlafaxine Hydrochloride%盐酸文拉法辛表观油水分配系数及其溶液化学稳定性的研究

    Institute of Scientific and Technical Information of China (English)

    张嫒; 谷福根

    2016-01-01

    目的:测定盐酸文拉法辛(Ven)的表观油水分配系数(P)及其水溶液的化学稳定性,为今后研制Ven的黏膜吸收给药液体制剂奠定基础.方法:采用HPLC法测定Ven的浓度;测定Ven在正辛醇-水/pH 2~10磷酸缓冲液系统中的P值;测定Ven在pH 2~12磷酸缓冲液以及不同离子强度条件下的降解百分率.结果:Ven在正辛醇-水系统中的P值为0.16;在正辛醇-pH 2~10缓冲液系统中,当pH≤6.0时,Ven的P值接近于1,当pH>6.0时,随着pH的增加,药物的P值显著增大.Ven溶液在pH≤8.0时,其化学稳定性良好,在碱性pH下,化学稳定性较差;离子强度对Ven溶液的化学稳定性无影响.结论:Ven的油水分配系数及溶液的化学稳定性与pH密切相关.在pH约为7.0时,Ven具有较高油水分配系数及化学稳定性.%Objective:To investigate the apparent oil-water partition coefficient ( P) and aqueous chemical stability of venlafaxine hydrochloride ( Ven) and provide theoretical basis for the development of Ven transmucous absorption liquid preparation. Methods:The concentration of Ven was determined by HPLC. The P value was studied in n-octanol-water/phosphate buffers system with the pH range of 2-10. The degradation percentage of Ven was also determined in the phosphate buffer solutions with the pH range of 2-12 and different ionic strength. Results:The P value of Ven in the n-octanol-water system was 0. 16. When pH≤ 6. 0, the P value of the drug in n-octanol-phosphate buffer system was close to 1, and when the pH>6. 0,the P value significantly increased with the rise of pH. Ven aqueous solution showed good chemical stability when pH≤8. 0, however, the chemical stability of the drug aqueous solution became poor with alkaline pH value. Ionic strength showed no obvious effect on the chemical stability of Ven aqueous solution. Con-clusion: The apparent oil-water partition coefficient and aqueous chemical stability of Ven are closely related to pH values. The drug

  6. Aqueous solubility, dispersibility and toxicity of biodiesels

    Energy Technology Data Exchange (ETDEWEB)

    Hollebone, B.P.; Fieldhouse, B.; Lumley, T.C.; Landriault, M. [Environment Canada, Ottawa, ON (Canada). ; Doe, K.; Jackman, P. [Environment Canada, Moncton, NB (Canada). Toxicology Laboratory, Environmental Science Centre

    2007-07-01

    The renewed interest in the use of biological fuels can be attributed to that fact that feedstocks for fatty-acid ester biodiesels are renewable and can be reclaimed from waste. Although there are significant benefits to using biodiesels, their increased use leaves potential for accidental release to the environment. Therefore, their environmental behaviours and impacts must be evaluated along with the risk associated with their use. Biodiesel fuels may be made from soy oil, canola oil, reclaimed restaurant grease, fish oil and animal fat. The toxicological fate of biofuel depends on the variability of its chemical composition. This study provided an initial assessment of the aqueous fate and effects of biodiesel from a broad range of commonly available feedstocks and their blends with petroleum diesels. The study focused primarily on the fate and impact of these fuels in fresh-water. The use of chemical dispersion as a countermeasure for saltwater was also investigated. The exposure of aquatic ecosystems to biodiesels and petroleum diesel occurs via the transfer of material from the non-aqueous phase liquid (NAPL) into the aqueous phase, as both soluble and dispersed components. The aqueous solubilities of the fuels were determined from the equilibrium water-accommodated fraction concentrations. The acute toxicities of many biodiesels were reported for 3 test species used by Environment Canada for toxicological evaluation, namely rainbow trout, the water flea and a luminescent bacterium. This study also evaluated the natural potential for dispersion of the fuels in the water column in both low and high-energy wave conditions. Chemical dispersion as a potential countermeasure for biodiesel spills was also evaluated using solubility testing, acute toxicity testing, and dispersibility testing. It was shown that biodiesels have much different fates and impacts from petroleum diesels. The compounds partitioning into the water column are also very different for each

  7. Partitioning of perfluorooctanesulfonate and perfluorohexanesulfonate in the aquatic environment after an accidental release of aqueous film forming foam at Schiphol Amsterdam Airport

    NARCIS (Netherlands)

    Kwadijk, C.J.A.F.; Kotterman, M.J.J.; Koelmans, A.A.

    2014-01-01

    In the summer of 2008, an accidental release of Aqueous Film Forming Foam (AFFF) took place at Schiphol Amsterdam Airport (The Netherlands). After the release, water, fish and sediment samples were collected and analyzed for perfluoroalkyl sulfonates (PFSA). In situ perfluorooctane sulfonate (PFOS)

  8. Chemical Compatibility of High-Performance Engineering Thermoplastics in Compressor Environments

    OpenAIRE

    Pai-Paranjape, Vandita

    2014-01-01

    The compressor industry faces a difficult design environment for achieving performance improvement, reduced cost, and lower environmental footprint. In order to address some of these challenges, thermoplastics can be considered as a replacement for metal in some compressor parts. Thermoplastics have been found to be suitable for steel replacement in structural parts for automotive and brass replacement in water-handling applications such as meters. As such, we believe certain high-performance...

  9. Chemical signals of past climate and environment from polar ice cores and firn air.

    Science.gov (United States)

    Wolff, Eric W

    2012-10-07

    Chemical and isotopic records obtained from polar ice cores have provided some of the most iconic datasets in Earth system science. Here, I discuss how the different records are formed in the ice sheets, emphasising in particular the contrast between chemistry held in the snow/ice phase, and that which is trapped in air bubbles. Air diffusing slowly through the upper firn layers of the ice sheet can also be sampled in large volumes to give more recent historical information on atmospheric composition. The chemical and geophysical issues that have to be solved to interpret ice core data in terms of atmospheric composition and emission changes are also highlighted. Ice cores and firn air have provided particularly strong evidence about recent changes (last few decades to centuries), including otherwise inaccessible data on increases in compounds that are active as greenhouse gases or as agents of stratospheric depletion. On longer timescales (up to 800,000 years in Antarctica), ice cores reveal major changes in biogeochemical cycling, which acted as feedbacks on the very major changes in climate between glacial and interglacial periods.

  10. Study of variation in surface morphology, chemical composition, crystallinity and hardness of laser irradiated silver in dry and wet environments

    Science.gov (United States)

    Ali, Nisar; Bashir, Shazia; Umm-i-Kalsoom; Begum, Narjis; Hussain, Tousif

    2017-07-01

    Variation in surface morphology, chemical composition, crystallinity and hardness of laser irradiated silver in dry and wet ambient environments has been investigated. For this purpose, the silver targets were exposed for various number of laser pulses in ambient environment of air, ethanol and de-ionized water for various number of laser pulses i.e. 500, 1000, 1500 and 2000. Scanning Electron Microscope (SEM) was employed to investigate the surface morphology of irradiated silver. SEM analysis reveals significant surface variations for both dry and wet ambient environments. For lower number of pulses, in air environment significant mass removal is observed but in case of ethanol no significant change in surface morphology is observed. In case of de-ionized water small sized cavities are observed with formation of protrusions with spherical top ends. For higher number of laser pulses, refilling of cavities by shock liquefied material, globules and protrusions are observed in case of dry ablation. For ablation in ethanol porous and coarse periodic ripples are observed whereas, for de-ionized water increasing density of protrusions is observed for higher number of pulses. EDS analysis exhibits the variation in chemical composition along with an enhanced diffusion of oxygen under both ambient conditions. The crystal structure of the exposed targets were explored by X-ray Diffraction (XRD) technique. XRD results support the EDS results. Formation of Ag2O in case of air and ethanol whereas, Ag2O and Ag3O in case of de-ionized water confirms the diffusion of oxygen into the silver surface after irradiation. Vickers Hardness tester was employed to measure the hardness of laser treated targets. Enhanced hardness is observed after irradiation in both dry and wet ambient environments. Initial decrease and then increase in hardness is observed with increase in number of laser pulses in air environment. In case of ethanol, increase in number of laser pulses results in

  11. The combined influence of chemical, metallurgical and mechanical factors on environment assisted cracking

    Science.gov (United States)

    Williams, D. P., III; Pao, P. S.; Wei, R. P.

    1979-01-01

    The principal aim of the paper is to re-emphasize and focus on both the multidisciplinary nature of the environment assisted cracking or embrittlement phenomenon. The multiplicity of factors involved in the embrittlement process is indicated, the mutual dependence of these factors and the influences of mechanical and environmental conditions are considered, and the interactions of various factors in determining the overall embrittlement response are discussed. The need for an interdisciplinary approach for resolving the major differences and for understanding embrittlement is outlined.

  12. Effect-based tools for monitoring and predicting the ecotoxicological effects of chemicals in the aquatic environment.

    Science.gov (United States)

    Connon, Richard E; Geist, Juergen; Werner, Inge

    2012-01-01

    Ecotoxicology faces the challenge of assessing and predicting the effects of an increasing number of chemical stressors on aquatic species and ecosystems. Herein we review currently applied tools in ecological risk assessment, combining information on exposure with expected biological effects or environmental water quality standards; currently applied effect-based tools are presented based on whether exposure occurs in a controlled laboratory environment or in the field. With increasing ecological relevance the reproducibility, specificity and thus suitability for standardisation of methods tends to diminish. We discuss the use of biomarkers in ecotoxicology including ecotoxicogenomics-based endpoints, which are becoming increasingly important for the detection of sublethal effects. Carefully selected sets of biomarkers allow an assessment of exposure to and effects of toxic chemicals, as well as the health status of organisms and, when combined with chemical analysis, identification of toxicant(s). The promising concept of "adverse outcome pathways (AOP)" links mechanistic responses on the cellular level with whole organism, population, community and potentially ecosystem effects and services. For most toxic mechanisms, however, practical application of AOPs will require more information and the identification of key links between responses, as well as key indicators, at different levels of biological organization, ecosystem functioning and ecosystem services.

  13. Effect-Based Tools for Monitoring and Predicting the Ecotoxicological Effects of Chemicals in the Aquatic Environment

    Directory of Open Access Journals (Sweden)

    Richard E. Connon

    2012-09-01

    Full Text Available Ecotoxicology faces the challenge of assessing and predicting the effects of an increasing number of chemical stressors on aquatic species and ecosystems. Herein we review currently applied tools in ecological risk assessment, combining information on exposure with expected biological effects or environmental water quality standards; currently applied effect-based tools are presented based on whether exposure occurs in a controlled laboratory environment or in the field. With increasing ecological relevance the reproducibility, specificity and thus suitability for standardisation of methods tends to diminish. We discuss the use of biomarkers in ecotoxicology including ecotoxicogenomics-based endpoints, which are becoming increasingly important for the detection of sublethal effects. Carefully selected sets of biomarkers allow an assessment of exposure to and effects of toxic chemicals, as well as the health status of organisms and, when combined with chemical analysis, identification of toxicant(s. The promising concept of “adverse outcome pathways (AOP” links mechanistic responses on the cellular level with whole organism, population, community and potentially ecosystem effects and services. For most toxic mechanisms, however, practical application of AOPs will require more information and the identification of key links between responses, as well as key indicators, at different levels of biological organization, ecosystem functioning and ecosystem services.

  14. Toward refined environmental scenarios for ecological risk assessment of down-the-drain chemicals in freshwater environments.

    Science.gov (United States)

    Franco, Antonio; Price, Oliver R; Marshall, Stuart; Jolliet, Olivier; Van den Brink, Paul J; Rico, Andreu; Focks, Andreas; De Laender, Frederik; Ashauer, Roman

    2017-03-01

    Current regulatory practice for chemical risk assessment suffers from the lack of realism in conventional frameworks. Despite significant advances in exposure and ecological effect modeling, the implementation of novel approaches as high-tier options for prospective regulatory risk assessment remains limited, particularly among general chemicals such as down-the-drain ingredients. While reviewing the current state of the art in environmental exposure and ecological effect modeling, we propose a scenario-based framework that enables a better integration of exposure and effect assessments in a tiered approach. Global- to catchment-scale spatially explicit exposure models can be used to identify areas of higher exposure and to generate ecologically relevant exposure information for input into effect models. Numerous examples of mechanistic ecological effect models demonstrate that it is technically feasible to extrapolate from individual-level effects to effects at higher levels of biological organization and from laboratory to environmental conditions. However, the data required to parameterize effect models that can embrace the complexity of ecosystems are large and require a targeted approach. Experimental efforts should, therefore, focus on vulnerable species and/or traits and ecological conditions of relevance. We outline key research needs to address the challenges that currently hinder the practical application of advanced model-based approaches to risk assessment of down-the-drain chemicals. Integr Environ Assess Manag 2017;13:233-248. © 2016 SETAC.

  15. Spatially resolved spectroscopy and chemical history of star-forming galaxies in the Hercules cluster: the effects of the environment

    CERN Document Server

    Petropoulou, V; Iglesias-Páramo, J; Papaderos, P; Magrini, L; Cedrés, B; Reverte, D

    2011-01-01

    Spatially resolved spectroscopy has been obtained for a sample of 27 star-forming (SF) galaxies selected from our deep Halpha survey of the Hercules cluster. We have applied spectral synthesis models to all emission-line spectra of this sample using the population synthesis code STARLIGHT. We have obtained fundamental parameters of the stellar components, as the mean metallicity and age, and we have corrected the emission-line spectra for underlying stellar absorption. O/H and N/O gas chemical abundances were obtained using the latest empirical calibrations. The effects of cluster environment on the chemical evolution of galaxies and on their mass-metallicity (MZ) and luminosity-metallicity (LZ) relations were studied combining the derived gas metallicities, the mean stellar metallicities and ages, the masses and luminosities of galaxies and their existing HI data. We have found that our Hercules SF galaxies divide into three main subgroups: a) chemically evolved spirals with truncated ionized-gas disks and n...

  16. Subcritical crack growth in a chemically reactive environment-implications for caprock integrity for CO2 storage

    Science.gov (United States)

    Fan, Z.; Eichhubl, P.; Callahan, O. A.; Major, J. R.; Chen, X.

    2015-12-01

    Seal integrity of cap-rock is a critical constraint on the long term performance of CO2 containment site. During fluid migration, the coupled geochemical reaction of minerals and geomechanical deformation of rock matrix may affect the seal integrity. The potential leakage of injected CO2 from cap-rock through preexisting fractures/faults represents a major concern associated with geological storage of CO2. To address the fundamental question of CO2 leakage through subcritical growth of fractures driven by chemically reactive fluid across caprocks, we build a Dugdale cohesive model. Ahead of the physical crack tip, a narrow band of cohesive zone is assumed to exist with the upper and lower cohesive surfaces held by the cohesive traction. In the vicinity of the crack tip, minerals dissolve due to the acidic environment and migrate from the physical crack tip into the cohesive zone causing damage of rock matrix in the form of a reduction of cohesive traction.Focusing on the dissolution of calcite and following the stress corrosion theory, we assume the degradation of cohesive traction is linearly proportional to the concentration of Ca2+whose evolution follows the reactive diffusion equation. Using a critical crack opening displacement criterion, the subcritical propagation behavior of crack due to stress corrosion is captured and the rate-limiting effects including the chemical reactions to produce the Ca2+ and the transport of minerals along the newly generated fracture cohesive zone are incorporated. Subcritical crack growth rate under different chemical environment conditions is examined and compared with the experimental fracture mechanics testing.

  17. Plasma environment during hot cathode direct current discharge plasma chemical vapor deposition of diamond films

    Institute of Scientific and Technical Information of China (English)

    朱晓东; 詹如娟; 周海洋; 胡敏; 温晓辉; 周贵恩; 李凡庆

    1999-01-01

    The plasma characteristics have been investigated in situ by using optical emission spectroscopy (OES) and the Langmuir probe during hot cathode direct current discharge plasma chemical vapor deposition of diamond films. The changes of atomic H and CH radical in the ground state have been calculated quantitatively according to the results of OES and the Langmuir probe measurement as discharge current density varied. It is shown that atomic H and CH radicals both in the ground state and in the excited state increase with the enhancement of the discharge current density in the plasma. The electron density and CH emission intensity increase linearly with the enhancement of discharge current densities. The generation of different carbon-containing radicals is related to the elevation of electron temperature. Combining the growth process of diamond films and the diagnostic results, it is shown that atomic H in the excited state may improve the diamond growth efficiently, and the increase of electron temperat

  18. Are antifouling paint particles a continuous source of toxic chemicals to the marine environment?

    Science.gov (United States)

    Soroldoni, Sanye; Abreu, Fiamma; Castro, Ítalo Braga; Duarte, Fabio Andrei; Pinho, Grasiela Lopes Leães

    2017-02-03

    Antifouling paint particles (APPs) are generated during periodical maintenance of boat hulls. Chemical composition and toxicity (either chronic or acute) of APPs found in the sediment was evaluated using the epibenthic copepod Nitokra sp. The APPs analyzed showed the presence of high levels of metals such as Cu (234,247±268μgg(-1)), Zn (112,404±845μgg(-1)) and the booster biocide DCOIT (0.13μgg(-1)). Even at low concentrations (as from 5mgg(-1) of APPs by mass of sediment) a significantly decrease in the fecundity was observed in laboratory tests. When the sediment was disturbed in elutriate test, a LC50 of 0.14% for APPs was found. This study was the first assessment of toxicity associated with the presence of APPs in sediment to benthic organisms, and it calls attention to the need of improving regulations in boatyards and marina areas.

  19. Chemicals in the water environment: where do the real and future threats lie?

    Directory of Open Access Journals (Sweden)

    John Fawell

    2012-12-01

    Full Text Available There are many potential sources of chemical constituents and contaminants in water that can reach drinking water. Not all substances will be present in any particular water. Some substances may be of benefit to health but others can be a threat. However, very few have been clearly shown to cause adverse health effects in humans through drinking water and evidence may be complicated by simultaneous exposure through food. Our knowledge of contaminants in water is, however, incomplete as additional contaminants emerge with advancing analytical methods. Most of these emerging contaminants are present as a consequence of day to day use by the wider human population and control requires a different approach to the substance by substance regulation prevalent at present.

  20. Novel Chemically-Bonded Phosphate Ceramic Borehole Sealants (Ceramicretes) for Arctic Environments

    Energy Technology Data Exchange (ETDEWEB)

    Shirish Patil; Godwin A. Chukwu; Gang Chen; Santanu Khataniar

    2008-12-31

    Novel chemically bonded phosphate ceramic borehole sealant, i.e. Ceramicrete, has many advantages over conventionally used permafrost cement at Alaska North Slope (ANS). However, in normal field practices when Ceramicrete is mixed with water in blenders, it has a chance of being contaminated with leftover Portland cement. In order to identify the effect of Portland cement contamination, recent tests have been conducted at BJ services in Tomball, TX as well as at the University of Alaska Fairbanks with Ceramicrete formulations proposed by the Argonne National Laboratory. The tests conducted at BJ Services with proposed Ceramicrete formulations and Portland cement contamination have shown significant drawbacks which has caused these formulations to be rejected. However, the newly developed Ceramicrete formulation at the University of Alaska Fairbanks has shown positive results with Portland cement contamination as well as without Portland cement contamination for its effective use in oil well cementing operations at ANS.

  1. Chemical composition and genotoxic activity of petroleum derivatives collected in two working environments

    Energy Technology Data Exchange (ETDEWEB)

    Pasquini, R.; Taningher, M.; Monarca, S.; Pala, M.; Angeli, G.

    1989-01-01

    Pitch and bitumen, two complex petroleum derivative mixtures, were studied for both their chemical composition and their mutagenic/DNA damaging activity. While bitumen revealed no genotoxic effect and low polycyclic aromatic hydrocarbons (PAHs) concentration, petroleum pitch showed a high concentration of mutagenic/carcinogenic PAHs, and also an elevated mutagenic activity when assayed by the Ames test, in the presence of postmitochondrial rat liver fractions. The in vitro mutagenic activity was detectable as frameshift mutation by assaying the pitch both as an in toto mixture and after HPLC fractionation, the most polar fractions being the most active. In contrast, both derivatives showed no in vivo DNA damage in rat liver, using the DNA alkaline elution technique and the fluorometric assay of DNA unwinding.

  2. Structural resistance of chemically modified 1-D nanostructured titanates in inorganic acid environment

    Energy Technology Data Exchange (ETDEWEB)

    Marinkovic, Bojan A., E-mail: bojan@puc-rio.br [Departamento de Engenharia de Materiais, Pontificia Universidade Catolica de Rio de Janeiro-PUC-Rio, Rua Marques de Sao Vicente 225, Gavea, RJ (Brazil); Fredholm, Yann C. [Nanogavea-Nanotecnologia Sustentavel Ltda, Av. Padre Leonel Franca 150, Gavea, RJ (Brazil); Morgado, Edisson [PETROBRAS S.A./CENPES, Research and Development Centre, Av. Horacio Macedo, 950, Cidade Universitaria, 21941-915, Rio de Janeiro, RJ (Brazil); Jardim, Paula M.; Rizzo, Fernando [Departamento de Engenharia de Materiais, Pontificia Universidade Catolica de Rio de Janeiro-PUC-Rio, Rua Marques de Sao Vicente 225, Gavea, RJ (Brazil)

    2010-10-15

    Sodium containing one-dimensional nanostructured layered titanates (1-D NSLT) were produced both from commercial anatase powder and Brazilian natural rutile mineral sands by alkali hydrothermal process. The 1-D NSLT were chemically modified with proton, cobalt or iron via ionic exchange and all products were additionally submitted to intensive inorganic acid aging (pH = 0.5) for 28 days. The morphology and crystal structure transformations of chemically modified 1-D NSLT were followed by transmission electron microscopy, powder X-ray diffraction, selected area electron diffraction and energy dispersive spectroscopy. It was found that the original sodium rich 1-D NSLT and cobalt substituted 1-D NSLT were completely converted to rutile nanoparticles, while the protonated form was transformed in a 70%-30% (by weight) anatase-rutile nanoparticles mixture, very similar to that of the well-known TiO{sub 2}-photocatalyst P25 (Degussa). The iron substituted 1-D NSLT presented better acid resistance as 13% of the original structure and morphology remained, the rest being converted in rutile. A significant amount of remaining 1-D NSLT was also observed after the acid treatment of the product obtained from rutile sand. The results showed that phase transformation of NSLT into titanium dioxide polymorph in inorganic acid conditions were controllable by varying the exchanged cations. Finally, the possibility to transform, through acid aging, 1-D NSLT obtained from Brazilian natural rutile sand into TiO{sub 2}-polymorphs was demonstrated for the first time to the best of authors' knowledge, opening path for producing TiO{sub 2}-nanoproducts with different morphologies through a simple process and from a low cost precursor.

  3. Stability characteristics and structural properties of single- and double-walled boron-nitride nanotubes under physical adsorption of Flavin mononucleotide (FMN) in aqueous environment using molecular dynamics simulations

    Energy Technology Data Exchange (ETDEWEB)

    Ansari, R., E-mail: r_ansari@guilan.ac.ir; Ajori, S., E-mail: Shahram_ajori1366@yahoo.com; Ameri, A.

    2016-03-15

    Graphical abstract: Structural properties and stability characteristics of single- and double-walled boron-nitride nanotubes functionalized with Flavin mononucleotide (FMN) in aqueous environment are investigated employing molecular dynamics simulations. - Highlights: • Structural and buckling analysis of boron-nitride nanotubes under physical adsorption of Flavin mononucleotide (FMN). • Gyration radius increases linearly as the weight percentage of FMN increases. • Presence of water molecules results in more expansion of FMN around BNNTs. • Critical buckling force of functionalized BNNTs is higher than that of pure BNNTs. • The critical strain of functionalized BNNTs is found to be lower than that of pure ones. - Abstract: The non-cytotoxic properties of Boron-nitride nanotubes (BNNTs) and the ability of stable interaction with biomolecules make them so promising for biological applications. In this research, molecular dynamics (MD) simulations are performed to investigate the structural properties and stability characteristics of single- and double-walled BNNTs under physical adsorption of Flavin mononucleotide (FMN) in vacuum and aqueous environments. According to the simulation results, gyration radius increases by rising the weight percentage of FMN. Also, the results demonstrate that critical buckling force of functionalized BNNTs increases in vacuum. Moreover, it is observed that by increasing the weight percentage of FMN, critical force of functionalized BNNTs rises. By contrast, critical strain reduces by functionalization of BNNTs in vacuum. Considering the aqueous environment, it is observed that gyration radius and critical buckling force of functionalized BNNTs increase more considerably than those of functionalized BNNTs in vacuum, whereas the critical strains approximately remain unchanged.

  4. Molecular recognition studies on supramolecular systems (XXIV)——Conformations and complexation abilities of chemically modified cyclodextrins in aqueous solution

    Institute of Scientific and Technical Information of China (English)

    刘育; 尤长城

    2000-01-01

    Circular dichroism spectral and fluorescence decay methods have been employed to determine the conformations of mono[6-(p-tolylseleno)-6-deoxy]-p-CD(1), mono(6-anilino-6-deoxy) β -CD (2) and mono[6-(L-tryptophan)-6-deoxy]-β-CD (3) in phosphate buffer solution (pH 7.2, 0.1 mol dm-3) at 298.15 K. The results indicate that compounds 2 and 3 formed self-inclusion complexes in aqueous buffer solution, while the substituent of compound 1 was not included into cyclodextrin cavity at all. Furthermore, the complex stability constant (logKs) and Gibbs free energy change (-ΔG° ) of these three cylcodextrin derivatives with several cycloalkanols have been determined by circular dichroism spectral titration in phosphate buffer solution at 298.15 K. It is found that the location of the substituent affects the stability of host-guest complex in aqueous solution.

  5. Chemical dispersion of oil with mineral fines in a low temperature environment.

    Science.gov (United States)

    Wang, Weizhi; Zheng, Ying; Lee, Kenneth

    2013-07-15

    The increasing risks of potential oil spills in the arctic regions, which are characterized by low temperatures, are a big challenge. The traditional dispersant method has shown limited effectiveness in oil cleanup. This work studied the role of mineral fines in the formation of oil-mineral aggregates (OMAs) at low temperature (0-4 °C) environment. The loading amount of minerals and dispersant with different dispersant and oil types were investigated under a full factorial design. The shapes and sizes of OMAs were analyzed. Results showed that the behavior of OMA formation differs when dispersant and mineral fines are used individually or together. Both the experimental and microscopic results also showed the existence of optimal dispersant to oil ratios and mineral to oil ratios. In general, poor oil removal performance was observed for more viscous oil. Corexit 9500 performed better than Corexit 9527 with various oils, in terms of oil dispersion and OMA formation.

  6. Behaviour of three chemical forms of tritium in the environment after release from inertial fusion reactors

    Energy Technology Data Exchange (ETDEWEB)

    Velarde, M.; Perlado, J.M. [Instituto de Fusion Nuclear (DENIM)/ETSII/Univ. Politecnica Madrid (Spain); Sedano, L. [CIEMAT, Madrid (Spain)

    2006-06-15

    In order to fully simulate the behaviour of elementary tritium (HT), tritiated water vapour (HTO) in the environment, it is necessary to take into account diffusion and deposition processes in the soil and vegetables. In addition this work also incorporates the penetration in the underground, re-emission and later conversion to organic tritium (OBT). The whole study has led to the conclusion that the behaviour of the tritium should be simulated using two well-differentiated studies: deterministic and probabilistic. Deterministic calculations are based on a fixed meteorological data given 'a priori'. The probabilistic study is based on measured real meteorological analysis every hour, and the probability that individuals can present dose for internal irradiation. Both options have been considered for a specific mediterranean environment of the system. Once the elementary tritium has been deposited in the soil, it can be oxidized by microbial action of the enzymes of the soil, and the resulting tritium form (in its oxidize form) goes back to the atmosphere. This process of re-emission is shown to be very important since it has been typically considered that the inhaled tritium is only, HTO, when, in fact part of that account is due to the HT converted to HTO and re-emitted to the atmosphere. Our calculations demonstrate that the HT contributes very significantly to the dose for inhalation through the re-emission processes. A final aspect of this work is the dosimetric analysis of the contamination through all ways: inhalation, re-emission and ingestion. Early and chronic doses have been assessed.

  7. Chemical evolution in the environment of intermediate mass young stellar objects

    Science.gov (United States)

    Fuente, A.; Rizzo, J. R.; Caselli, P.; Bachiller, R.; Henkel, C.

    2005-04-01

    We have carried out a molecular survey of the Class 0 IM protostar NGC 7129 - FIRS 2 (hereafter FIRS 2) and the Herbig Be star LkHα 234 with the aim of studying the chemical evolution of the envelopes of intermediate-mass (IM) young stellar objects (YSOs). The two objects have similar luminosities (~500 L_⊙) and are located in the same molecular cloud which minimizes the chemical differences due to different stellar masses or initial cloud conditions. Moreover, since they are located at the same distance, we have the same spatial resolution in both objects. A total of 17 molecular species (including rare isotopes) have been observed in both objects and the structure of their envelopes and outflows has been determined with unprecedent detail. Our results show that the protostellar envelopes are dispersed and warmed up during the evolution of the YSO into a pre-main sequence star. In fact, the envelope mass decreases by a factor >5 from FIRS 2 to LkHα 234, while the kinetic temperature increases from ~13 K to 28 K. On the other hand, there is no molecular outflow associated with LkHα 234. The molecular outflow seems to stop before the star becomes visible. These physical changes strongly affect the chemistry of their envelopes. The N2H+ and NH3 abundances seem to be quite similar in the two objects. However, the H13CO+ abundance is a factor of ~3 lower in the densest part of FIRS 2 than in LkHα 234, very likely because of depletion. In contrast, the SiO abundance is larger by a factor of ~100 in FIRS 2 than in LkHα 234. CS presents complex behavior since its emission arises in different envelope components (outflow, cold envelope, hot core) and could also suffer from depletion. The CH3OH and H2CO column densities are very similar in FIRS 2 and LkHα 234 which implies that the beam-averaged abundances are a factor >5 larger in LkHα 234 than in FIRS 2. The same is found for the PDR tracers CN and HCN which have similar column densities in both objects. Finally

  8. Passive sampling of selected pesticides in aquatic environment using polar organic chemical integrative samplers.

    Science.gov (United States)

    Thomatou, Alphanna-Akrivi; Zacharias, Ierotheos; Hela, Dimitra; Konstantinou, Ioannis

    2011-08-01

    Polar chemical integrative samplers (POCIS) were examined for their sampling efficiency of 12 pesticides and one metabolite commonly detected in surface waters. Laboratory-based calibration experiments of POCISs were conducted. The determined passive sampling rates were applied for the monitoring of pesticides levels in Lake Amvrakia, Western Greece. Spot sampling was also performed for comparison purposes. Calibration experiments were performed on the basis of static renewal exposure of POCIS under stirred conditions for different time periods of up to 28 days. The analytical procedures were based on the coupling of POCIS and solid phase extraction by Oasis HLB cartridges with gas chromatography-mass spectrometry. The recovery of the target pesticides from the POCIS was generally >79% with relative standard deviation (RSD) monitoring campaign using both passive and spot sampling whereas higher concentrations were measured by spot sampling in most cases. Passive sampling by POCIS provides a useful tool for the monitoring of pesticides in aquatic systems since integrative sampling at rates sufficient for analytical quantitation of ambient levels was observed. Calibration data are in demand for a greater number of compounds in order to extend the use in environmental monitoring.

  9. Surfaces of a colloidal iron nanoparticle in its chemical environment: a DFT description.

    Science.gov (United States)

    Fischer, Guntram; Poteau, Romuald; Lachaize, Sébastien; Gerber, Iann C

    2014-10-01

    Describing and understanding surface chemistry on the atomic scale is of primary importance in predicting and rationalize nanoparticle morphology as well as their physical and chemical properties. Here we present the results of comprehensive density functional theory studies on the adsorption of several small organic species, representing the major species (H2, Cl2, HCl, NH3, NH4Cl, and CH3COOH), present in the reaction medium during colloidal iron nanoparticle synthesis on various low-index iron surface models, namely, (100), (110), (111), (211), and (310). All of the tested ligands strongly interact with the proposed surfaces. Surface energies are calculated and ligand effects on the morphologies are presented, including temperature effects, based on a thermodynamic approach combined with the Wulff construction scheme. The importance of taking into account vibrational contributions during the calculation of surface energies after adsorption is clearly demonstrated. More importantly, we find that thermodynamic ligand effects can be ruled out as the unique driving force in the formation of recently experimentally observed iron cubic nanoparticles.

  10. Mechanically strengthened new Hagi porcelain developed by controlling the chemical environment of iron

    Science.gov (United States)

    Kubuki, Shiro; Iwanuma, Jun; Akiyama, Kazuhiko; Mikuni, Akira; Nishida, Tetsuaki

    2012-05-01

    In order to enhance the mechanical strength of Hagi Porcelain (Hagiyaki), one of the oldest and famous potteries in Japan, new preparation condition was examined. Tempered Hagi porcelain, denominated as ` Hagi Porcelain B', was prepared with the Porcelain clay originating from Daido district, Yamaguchi Prefecture, Japan. Structural change of ` Hagi Porcelain B' was investigated by means of 57Fe-Mössbauer spectroscopy, X-ray diffractometry (XRD) and three-point bending test. Mechanical strength of the ` original Hagi Porcelain B' was estimated to be 43.1 MPa by means of the three-point bending test, while much larger value of 104.5 MPa could be achieved when tempered by a chemical modification. Mössbauer spectrum of the ` original Hagi porcelain B' was composed of a paramagnetic doublet and a magnetic sextet due to Fe(III) of γ-Fe2O3(maghemite), while only one paramagnetic doublet due to to octahedral Fe(II)O6 was observed for the ` tempered Hagi Porcelain B' with isomer shift and quadrupole splitting values of 1.13 and 2.15 mm s-1, respectively. It is considered that the absence of magnetic phase causes an increase of the mechanical strength because the maghemite phase has a defect spinel structure. These results indicate that mechanical strength of the ` Hagi porcelain B' could be enhanced by controlling the sintering condition.

  11. Chemical reactions induced by oscillating external fields in weak thermal environments

    CERN Document Server

    Craven, Galen T; Hernandez, Rigoberto

    2015-01-01

    Chemical reaction rates must increasingly be determined in systems that evolve under the control of external stimuli. In these systems, when a reactant population is induced to cross an energy barrier through forcing from a temporally varying external field, the transition state that the reaction must pass through during the transformation from reactant to product is no longer a fixed geometric structure, but is instead time-dependent. For a periodically forced model reaction, we develop a recrossing-free dividing surface that is attached to a transition state trajectory [T. Bartsch, R. Hernandez, and T. Uzer, Phys. Rev. Lett. 95, 058301 (2005)]. We have previously shown that for single-mode sinusoidal driving, the stability of the time-varying transition state directly determines the reaction rate [G. T. Craven, T. Bartsch, and R. Hernandez, J. Chem. Phys. 141, 041106 (2014)]. Here, we extend our previous work to the case of multi-mode driving waveforms. Excellent agreement is observed between the rates pred...

  12. Social environment has a primary influence on the microbial and odor profiles of a chemically signaling songbird

    Directory of Open Access Journals (Sweden)

    Danielle June Whittaker

    2016-08-01

    Full Text Available Chemical signaling is an underappreciated means of communication among birds, as may be the potential contributions of symbiotic microbes to animal chemical communication in general. The dark-eyed junco (Junco hyemalis produces and detects volatile compounds that may be important in reproductive behavior. These compounds are found in preen oil secreted by the uropygial gland, and this gland supports diverse bacterial communities including genera known to produce some of these volatile compounds. We investigated the relative contributions of shared environments and genetic relatedness in shaping juncos’ symbiotic bacterial communities, and investigated whether these bacterial communities underlie juncos’ chemical signaling behavior. We sampled parents and nestlings at 9 junco nests during one breeding season at Mountain Lake Biological Station in Virginia, USA. From each individual, we collected swabs of the uropygial gland and the cloaca, preen oil, and a small blood sample for paternity testing. We characterized junco bacterial communities through 16S rRNA gene surveys and preen oil volatile compounds via gas chromatography-mass spectrometry. Nest membership and age class had the strongest influence on the structure of bacterial and volatile profiles. We compared father-offspring similarity based on paternity, and nestling similarity in nests containing full siblings and half siblings, and found that relatedness did not noticeably affect bacterial or volatile profiles. While we cannot rule out an influence of genetic relatedness on these profiles, it is clear that shared environments are more influential in shaping bacterial and volatile profiles among juncos.We did not find significant covariation between individual bacterial and volatile profiles. Possible explanations for this result include: 1 bacteria do not underlie volatile production; 2 ample redundancy in volatile production among bacterial types obscures covariation; or 3 the

  13. [Endocrine disruptors: hormone-active chemicals from the environment: a risk to humans?].

    Science.gov (United States)

    Klingmüller, Dietrich; Alléra, A

    2011-05-01

    Many substances from the technical and natural environment can cause damage to the endocrine system. Animal tests show that so-called endocrine disruptors (ED), such as pesticides, fungicides, plasticizers (phthalates), bisphenol A (BPA), and organotin compounds can interfere with the endocrine system. In humans, it is difficult to attribute such changes to specific ED. Nevertheless, in vitro studies with human cells and tissues clearly show that ED are able to interfere with endogenous hormones, i. e. affecting the steroid hormone metabolism and intracellular signaling. Several clinical studies show that humans are also affected, including reproductive disorders like reduction of spermatogenesis, decreased testosterone production or malformation of the genitals or induction of tumors like mammary carcinoma. Facing the body of reports documenting the effects of ED, the European Union supported--inter alia--COMPRENDO, a project addressing risk assessment of particular ED in human and wildlife species, while the FDA supports the industry's actions to stop producing BPA-containing baby bottles and infant feeding cups. Some ED show an u-shaped dose response curve and specific ED have effects at levels dramatically lower than thought relevant to traditional toxicology, a phenomenon termed "Low Dose Impact". Further research is needed to clarify whether the observed findings represent associations or causal results.

  14. Experimental Bariatric Surgery in Rats Generates a Cytotoxic Chemical Environment in the Gut Contents.

    Directory of Open Access Journals (Sweden)

    Jia eLi

    2011-09-01

    Full Text Available Bariatric surgery, also known as metabolic surgery, is an effective treatment for morbid obesity which also offers pronounced metabolic effects including the resolution of type 2 diabetes and a decrease in cardiovascular disease and long-term cancer risk. However, the mechanisms of surgical weight loss and the long term consequences of bariatric surgery remain unclear. Bariatric surgery has been demonstrated to alter the composition of both the microbiome and the metabolic phenotype. We observed a marked shift towards Gammaproteobacteria, particularly Enterobacter hormaechei, following Roux-en-Y gastric bypass (RYGB surgery in a rat model compared with sham operated controls. Fecal water from RYGB surgery rats was highly cytotoxic to rodent cells (mouse lymphoma cell line, although In contrast, fecal water from sham operated animals showed no/very low cytotoxicity. This shift in the gross structure of the microbiome correlated with greatly increased cytotoxicity in a regulatory acceptable mouse lymphoma assay. Urinary phenylacetylglycine and indoxyl sulfate and fecal GABA, putrescine, tyramine and uracil were found to be inversely correlated with cell survival rate. This profound co-dependent response of mammalian and microbial metabolism to RYGB surgery and the impact on the cytotoxicity of the gut luminal environment suggests that RYGB exerts local and global metabolic effects which may have an influence on long term cancer risk and cytotoxic load.

  15. Impact of the physical and chemical environment on the molecular structure of Coprinus cinereus peroxidase.

    Science.gov (United States)

    Houborg, Karen; Harris, Pernille; Petersen, Jens; Rowland, Paul; Poulsen, Jens-Christian Navarro; Schneider, Palle; Vind, Jesper; Larsen, Sine

    2003-06-01

    The structure of the peroxidase from Coprinus cinereus (CiP) has been determined in three different space groups and crystalline environments. Two of these are of the recombinant glycosylated form (rCiP), which crystallized in space groups P2(1)2(1)2(1) and C2. The third crystal form was obtained from a variant of CiP in which the glycosylation sites have been removed (rCiPON). It crystallizes in space group P2(1) with beta approximately 90 degrees; the structure was determined from room-temperature data and low-temperature data obtained from twinned crystals. Two independent molecules of CiP related by non-crystallographic symmetry are contained in the three crystal forms. The packing in the two structures of the glycosylated form of rCiP is closely related, but differs from the packing in the unglycosylated rCiPON. A database search based on small-molecule porphinato iron (III) complexes has been performed and related to observations of the spin states and coordination numbers of the iron ion. The room-temperature structures of CiP and one structure of the almost identical peroxidase from Arthromyces ramosus (ARP) have been used to identify 66 conserved water molecules and to assign a structural role to most of them.

  16. The importance of chemical components in cleaning agents for the indoor environment

    DEFF Research Database (Denmark)

    Vejrup, Karl Ventzel

    VOCs. In one experiment, the concentration of nonpolar VOCs in the breathing zone of a person who treated the floor in a large climate chamber (45 m3) using a water based polish product was found to be 3,9 mg/m3. Use of scented cleaning agents usually means that odour thresholds of some compounds...... with polish treatment of the floor in a large climate chamber (45 m3) concentrations of up to 20 mg/m3 og 2-(2-ethoxyethoxy)ethanol were measured after 2 hours and it took more than 10 hours before the concentration was below the odour threshold (4 mg/m3).The amount of non-volatile compounds introduced...... of LAS between smooth floored corridors to carpeted offices, are apparently also of importance for the LAS content in individual rooms.The amounts of LAS found in the dust samples indicated that LAS may be of importance for the indoor environment, but inadequate knowledge about how low concentrations...

  17. Chemical species of metallic elements in the aquatic environment of an ex-mining catchment.

    Science.gov (United States)

    Ashraf, Muhammad Aqeel; Ahmad, Mushtaq; Akib, Shatirah; Balkhair, Khaled S; Abu Bakar, Nor Kartini

    2014-08-01

    This study was conducted to investigate the chemical speciation of dissolved and particulate elements (lead, zinc, copper, chromium, arsenic, and tin) in the mining wastewater of a former tin-mining catchment. The speciation patterns of dissolved elements were estimated by an adsorptive stripping voltammeter (ASV), while particulate elements were analyzed by using a newly developed sequential-extraction leaching procedure. The procedure has been operationally defined among five host fractions, namely exchangeable, carbonate, reducible, organic bound, and residual fractions. A total of six elements (lead, zinc, copper, chromium, arsenic, and tin) were analyzed in thirty samples at ten locations (P1-P10), with three samples taken from each of the ten locations, to get the average value from the former tin-mining catchment. The results showed that the heavy metal pollutions in locations P4 and P8 were more severe than in other sampling sites, especially tin and lead pollution. In the water samples from locations P4 and P8, both the total contents and the most dangerous non-residual fractions of tin and lead were extremely high. More than 90% of the total concentrations of arsenic and chromium existed in the residual fraction. Concentrations of copper and zinc mainly occurred in the residual fraction (more than 60%), while lead and tin presented mostly in the non-residual fractions in surface water. For all of the six dissolved elements, the less-labile species formed the predominant fraction in their speciation patterns. The speciation patterns of particulate elements showed that most of the concentrations of zinc, copper, chromium, and arsenic were found in the reducible fraction; whereas lead and tin were mainly associated with the organic fraction.

  18. E4CHEM. A simulation program for the fate of chemicals in the environment. Handbook. User`s guide and description. Version 3.6. December 1995

    Energy Technology Data Exchange (ETDEWEB)

    Brueggemann, R. [GSF - Forschungszentrum fuer Umwelt und Gesundheit Neuherberg GmbH, Oberschleissheim (Germany). Projektgruppe Umweltgefaehrdungspotentiale von Chemikalien; Drescher-Kaden, U. [GSF - Forschungszentrum fuer Umwelt und Gesundheit Neuherberg GmbH, Oberschleissheim (Germany). Projektgruppe Umweltgefaehrdungspotentiale von Chemikalien; Muenzer, B. [GSF - Forschungszentrum fuer Umwelt und Gesundheit Neuherberg GmbH, Oberschleissheim (Germany). Projektgruppe Umweltgefaehrdungspotentiale von Chemikalien

    1996-02-01

    The predominant aims of E4CHEM are: Deterministic description of the chemical`s behavior in the environment with varying ecoparameters including the special aspects; Behavior of the same chemical in different compartments; Behavior of different chemicals in the same compartment with the same ecoparameters; Tracing back of chemicals detected in the environment to the possible source by means of check procedures like in EXWAT, one of the E4CHEM models; Discharge of the user from extensive calculation operations; Interpretation of experimental results. In combination with statistics and algebraic tools (lattice theory) but not included in E4CHEM yet: Selection of descriptors as tool for priority setting; Identification and ranking of chemicals according to their risk to the environment by comparing descriptors within descriptor matrices about the behavior of chemicals deived from the different models. Furthermore: Identification of chemical applicable as reference substances with respect to environmental behavior. The program E4CHEM is described in this manual. (orig./SR)

  19. Cyanobacterial flora and the physico-chemical environment of six tropical fresh water lakes of Udaipur, India.

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    The cyanobacteria and physico-chemical environments of six tropical fresh water lakes of Udaipur, India were investigated. These lakes receive varying nutrient inputs from different sources. Altogether 51 species of cyanobacteria were recorded. Species composition varied between lakes and between seasons. Lake VI (Baghdara), which receives nutrients from natural sources only, differed considerably from the others in water chemistry and composition of dominant species. Lake II (Swaroop Sagar), eutrophied due to sewage inputs, was species poor. Non-diazotrophs, represented by 27 species, dominated during summer. With few exceptions, N2-fixing species, both heterocystous and unicellular diazotrophs (represented by 24 species), were dominant during winter. Microcystis aeruginosa, Phormidium sp. and Anabaena flos-aque were the dominant taxa of lakes characterized by sewage eutrophication. The study shows that both, species diversity and community composition were affected by water chemistry.

  20. Mars Aqueous Chemistry Experiment (MACE)

    Science.gov (United States)

    Benton, Clark C. (Editor)

    1995-01-01

    The concept of an aqueous-based chemical analyzer for Martian surface materials has been demonstrated to be feasible. During the processes of analysis, design, breadboarding, and most importantly, testing, it has become quite apparent that there are many challenges in implementing such a system. Nonetheless, excellent progress has been made and a number of problems which arose have been solved. The ability to conduct this work under a development environment which is separate and which precedes the project-level development has allowed us to find solutions to these implementation realities at low cost. If the instrument had been selected for a mission without this laboratory pre-project work, the costs of implementation would be much higher. In the four areas covered in Sections D, E, F, and G of this Final Report, outstanding progress has been made. There still remains the task of flight-qualifying certain of the components. This is traditionally done under the aegis of a Flight Project, but just as the concept development can be done at much lower cost when kept small and focused, so could the qualification program of critical parts benefit. We recommend, therefore, that NASA consider means of such qualifications and brass-boarding, in advance of final flight development. This is a generic recommendation, but hardware such as the Mars aqueous chemistry experiment (MACE) and other similarly-new concepts are particularly applicable. MACE now has wide versatility, in being able to reliably dispense both liquids and solids as chemical reagents to an entire suite of samples. The hardware and the experiment is much simpler than was developed for the Viking Biology instrument, yet can accomplish all the inorganic chemical measurements that the Viking desing was capable of. In addition, it is much more flexible and versatile to new experiment protocols (and reagents) than the Viking design ever could have been. MACE opens up the opportunity for many different scientific

  1. Chemical characterization of SOA formed from aqueous-phase reactions of phenols with the triplet excited state of carbonyl and hydroxyl radical

    Energy Technology Data Exchange (ETDEWEB)

    Yu, Lu; Smith, Jeremy; Laskin, Alexander; Anastasio, Cort N.; Laskin, Julia; Zhang, Qi

    2014-01-01

    Phenolic compounds, which are emitted in significant amounts from biomass burning, can undergo fast reactions in atmospheric aqueous phases to form secondary organic aerosol (aqSOA). In this study, we investigate the reactions of phenol and two methoxy-phenols (syringol and guaiacol) with two major aqueous phase oxidants – the triplet excited states of an aromatic carbonyl (3C*) and hydroxyl radical (•OH). We thoroughly characterize the low-volatility species produced from these reactions and interpret their formation mechanisms using aerosol mass spectrometry (AMS), desorption electrospray ionization mass spectrometry (DESIMS), and ion chromatography (IC). A large number of oxygenated molecules are identified, including oligomers containing up to six monomer units, functionalized monomer and oligomers with carbonyl, carboxyl, and hydroxyl groups, and small organic acid anions (e.g., formate, acetate, oxalate, and malate). The average atomic oxygen-to-carbon (O/C) ratios of phenolic aqSOA are in the range of 0.85-1.23, similar to those of low-volatility oxygenated organic aerosol (LV-OOA) observed in ambient air. The aqSOA compositions are overall similar for the same precursor, but the reactions mediated by 3C* are faster than •OH-mediated reactions and produce more oligomers and hydroxylated species at the point when 50% of the phenol had reacted. Profiles determined using a thermodenuder indicate that the volatility of phenolic aqSOA is influenced by both oligomer content and O/C ratio. In addition, the aqSOA shows enhanced light absorption in the UV-vis region, suggesting that aqueous-phase reactions of phenols are likely an important source of brown carbon in the atmosphere, especially in regions influenced by biomass burning.

  2. Chemical characterization of SOA formed from aqueous-phase reactions of phenols with the triplet excited state of carbonyl and hydroxyl radical

    Science.gov (United States)

    Yu, L.; Smith, J.; Laskin, A.; Anastasio, C.; Laskin, J.; Zhang, Q.

    2014-12-01

    Phenolic compounds, which are emitted in significant amounts from biomass burning, can undergo fast reactions in atmospheric aqueous phases to form secondary organic aerosol (aqSOA). In this study, we investigate the reactions of phenol (compound with formula C6H5OH)), guaiacol (2-methoxyphenol), and syringol (2,6-dimethoxyphenol) with two major aqueous-phase oxidants - the triplet excited states of an aromatic carbonyl (3C*) and hydroxyl radical (· OH). We thoroughly characterize the low-volatility species produced from these reactions and interpret their formation mechanisms using aerosol mass spectrometry (AMS), nanospray desorption electrospray ionization mass spectrometry (nano-DESI MS), and ion chromatography (IC). A large number of oxygenated molecules are identified, including oligomers containing up to six monomer units, functionalized monomer and oligomers with carbonyl, carboxyl, and hydroxyl groups, and small organic acid anions (e.g., formate, acetate, oxalate, and malate). The average atomic oxygen-to-carbon (O / C) ratios of phenolic aqSOA are in the range of 0.85-1.23, similar to those of low-volatility oxygenated organic aerosol (LV-OOA) observed in ambient air. The aqSOA compositions are overall similar for the same precursor, but the reactions mediated by 3C* are faster than · OH-mediated reactions and produce more oligomers and hydroxylated species at the point when 50% of the phenolic compound has reacted. Profiles determined using a thermodenuder indicate that the volatility of phenolic aqSOA is influenced by both oligomer content and O / C ratio. In addition, the aqSOA shows enhanced light absorption in the UV-visible region, suggesting that aqueous-phase reactions of phenols may contribute to formation of secondary brown carbon in the atmosphere, especially in regions influenced by biomass burning.

  3. Effects of the in vitro chemical environment during early embryogenesis on subsequent development

    Energy Technology Data Exchange (ETDEWEB)

    Rieger, D. [Guelph Univ., ON (Canada). Animal Biotechnology Embryo Lab.

    1998-12-31

    The development of the preimplantation embryo seems morphologically very simple, and embryologists previously assumed that an embryo that developed to the blastocyst stage was fully capable of normal development after transfer to the uterus of a recipient female. This complacency was disturbed by reports that exposure of early embryos to mutagens such as methylnitrosourea led to fetal abnormalities, decreased birth rates, and decreased life-span. Even more disturbing are recent reports that culture of early embryos in supposedly benign conditions can adversely affect their subsequent development. Techniques have been developed for the production of cattle and sheep embryos by in-vitro fertilization and by cloning. Such embryos must be cultured for several days before they can be transferred, and, in some cases, this has been related to abortion, very high birthweight, physical abnormalities and peri-natal mortality of the calves and lambs. This syndrome may result from an unbalanced development of the trophoblast relative to the inner-cell mass, possibly related to the presence of serum, glucose, or ammonium in the culture medium. An analogous phenomenon has been observed in human in-vitro fertilization where babies from single pregnancies have below-normal birth-weight. There is also evidence to suggest that the in-vitro environment of the gametes before fertilization can affect subsequent embryonal and fetal development. Exposure of mouse oocytes to vitrification solutions has been shown to lead to fetal malformations, and treatment of bull sperm with glutathione improves early embryo development. The common thread in these diverse observations is that development can be affected by events that occur long before any defect is apparent. Consequently, the production of a morphologically normal embryo is no guarantee that fetal development and post-natal life will be normal. This is of immediate concern in human reproductive medicine due to the increasing use of

  4. Vanadium Flow Battery Electrolyte Synthesis via Chemical Reduction of V2O5 in Aqueous HCl and H2SO4.

    Energy Technology Data Exchange (ETDEWEB)

    Small, Leo J. [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Pratt, Harry [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Staiger, Chad [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Martin, Rachel Irene [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Anderson, Travis Mark [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Chalamala, Babu [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Soundappan, Thiagarajan [Univ. of Washington, Seattle, WA (United States); Tiwari, Monika [Univ. of Washington, Seattle, WA (United States); Subarmanian, Venkat R. [Univ. of Washington, Seattle, WA (United States)

    2017-01-01

    We report a simple method to synthesize V 4+ (VO 2+ ) electrolytes as feedstock for all- vanadium redox flow batteries (RFB). By dissolving V 2 O 5 in aqueous HCl and H 2 SO 4 , subsequently adding glycerol as a reducing agent, we have demonstrated an inexpensive route for electrolyte synthesis to concentrations >2.5 M V 4+ (VO 2+ ). Electrochemical analysis and testing of laboratory scale RFB demonstrate improved thermal stability across a wider temperature range (-10-65 degC) for V 4+ (VO 2+ ) electrolytes in HCl compared to in H 2 SO 4 electrolytes.

  5. Reconstruction of centennial-scale fluxes of chemical elements in the Australian coastal environment using seagrass archives

    KAUST Repository

    Serrano, Oscar

    2015-10-02

    The study of a Posidonia australis sedimentary archive has provided a record of changes in element concentrations (Al, Fe, Mn, Pb, Zn, Cr, Cd, Co, As, Cu, Ni and S) over the last 3000 years in the Australian marine environment. Human-derived contamination in Oyster Harbor (SW Australia) started ~. 100 years ago (AD ~. 1900) and exponentially increased until present. This appears to be related to European colonization of Australia and the subsequent impact of human activities, namely mining, coal and metal production, and extensive agriculture. Two contamination periods of different magnitude have been identified: Expansion period (EXP, AD ~. 1900-1970) and Establishment period (EST, AD ~. 1970 to present). Enrichments of chemical elements with respect to baseline concentrations (in samples older than ~. 115 cal. years BP) were found for all elements studied in both periods, except for Ni, As and S. The highest enrichment factors were obtained for the EST period (ranging from 1.3-fold increase in Cu to 7.2-fold in Zn concentrations) compared to the EXP period (1.1-fold increase for Cu and Cr to 2.4-fold increase for Pb). Zinc, Pb, Mn and Co concentrations during both periods were 2- to 7-fold higher than baseline levels. This study demonstrates the value of Posidonia mats as long-term archives of element concentrations and trends in coastal ecosystems. We also provide preliminary evidence on the potential for Posidonia meadows to act as significant long-term biogeochemical sinks of chemical elements.

  6. Modeling of The hERG K+ Channel Blockage Using Online Chemical Database and Modeling Environment (OCHEM).

    Science.gov (United States)

    Li, Xiao; Zhang, Yuan; Li, Huanhuan; Zhao, Yong

    2017-08-30

    Human ether-a-go-go related gene (hERG) K+ channel plays an important role in cardiac action potential. Blockage of hERG channel may result in long QT syndrome (LQTS), even cause sudden cardiac death. Many drugs have been withdrawn from the market because of the serious hERG-related cardiotoxicity. Therefore, it is quite essential to estimate the chemical blockage of hERG in the early stage of drug discovery. In this study, a diverse set of 3721 compounds with hERG inhibition data was assembled from literature. Then, we make full use of the Online Chemical Modeling Environment (OCHEM), which supplies rich machine learning methods and descriptor sets, to build a series of classification models for hERG blockage. We also generated two consensus models based on the top-performing individual models. The consensus models performed much better than the individual models both on 5-fold cross validation and external validation. Especially, consensus model II yielded the prediction accuracy of 89.5 % and MCC of 0.670 on external validation. This result indicated that the predictive power of consensus model II should be stronger than most of the previously reported models. The 17 top-performing individual models and the consensus models and the data sets used for model development are available at https://ochem.eu/article/103592. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Study on the Effects of Corrosion Inhibitor According to the Functional Groups for Cu Chemical Mechanical Polishing in Neutral Environment

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Sang Won; Kim, Jae Jeong [Institute of Chemical Process, Seoul National University, Seoul (Korea, Republic of)

    2015-08-15

    As the aluminum (Al) metallization process was replaced with copper (Cu), the damascene process was introduced, which required the planarization step to eliminate over-deposited Cu with Chemical Mechanical Polishing (CMP) process. In this study, the verification of the corrosion inhibitors, one of the Cu CMP slurry components, was conducted to find out the tendency regarding the carboxyl and amino functional group in neutral environment. Through the results of etch rate, removal rate, and chemical ability of corrosion inhibitors based on 1H-1,2,4-triazole as the base corrosion inhibitor, while the amine functional group presents high Cu etching ability, carboxyl functional group shows lower Cu etching ability than base-corrosion inhibitor which means that it increases passivation effect by making strong passivation layer. It implies that the corrosion inhibitor with amine functional group was proper to apply for 1st Cu CMP slurry owing to the high etch rate and with carboxyl functional group was favorable for the 2nd Cu CMP slurry due to the high Cu removal rate/dissolution rate ratio.

  8. Sulfates on Mars: Indicators of Aqueous Processes

    Science.gov (United States)

    Bishop, Janice L.; Lane, Melissa D.; Dyar, M. Darby; Brown, Adrian J.

    2006-01-01

    Recent analyses by MER instruments at Meridiani Planum and Gusev crater and the OMEGA instrument on Mars Express have provided detailed information about the presence of sulfates on Mars [1,2,3]. We are evaluating these recent data in an integrated multi-disciplinary study of visible-near-infrared, mid-IR and Mossbauer spectra of several sulfate minerals and sulfate-rich analog sites. Our analyses suggest that hydrated iron sulfates may account for features observed in Mossbauer and mid-IR spectra of Martian soils [4]. The sulfate minerals kieserite, gypsum and other hydrated sulfates have been identified in OMEGA spectra in the layered terrains in Valles Marineris and Terra Meridiani [2]. These recent discoveries emphasize the importance of studying sulfate minerals as tracers of aqueous processes. The sulfate-rich rock outcrops observed in Meridiani Planum may have formed in an acidic environment similar to acid rock drainage environments on Earth [5]. Because microorganisms typically are involved in the oxidation of sulfides to sulfates in terrestrial sites, sulfate-rich rock outcrops on Mars may be a good location to search for evidence of past life on that planet. Whether or not life evolved on Mars, following the trail of sulfate minerals will lead to a better understanding of aqueous processes and chemical weathering.

  9. Influence of Genotype, Environment, and Gypsy Moth Herbivory on Local and Systemic Chemical Defenses in Trembling Aspen (Populus tremuloides).

    Science.gov (United States)

    Rubert-Nason, Kennedy F; Couture, John J; Major, Ian T; Constabel, C Peter; Lindroth, Richard L

    2015-07-01

    Numerous studies have explored the impacts of intraspecific genetic variation and environment on the induction of plant chemical defenses by herbivory. Relatively few, however, have considered how those factors affect within-plant distribution of induced defenses. This work examined the impacts of plant genotype and soil nutrients on the local and systemic phytochemical responses of trembling aspen (Populus tremuloides) to defoliation by gypsy moth (Lymantria dispar). We deployed larvae onto foliage on individual tree branches for 15 days and then measured chemistry in leaves from: 1) branches receiving damage, 2) undamaged branches of insect-damaged trees, and 3) branches of undamaged control trees. The relationship between post-herbivory phytochemical variation and insect performance also was examined. Plant genotype, soil nutrients, and damage all influenced phytochemistry, with genotype and soil nutrients being stronger determinants than damage. Generally, insect damage decreased foliar nitrogen, increased levels of salicinoids and condensed tannins, but had little effect on levels of a Kunitz trypsin inhibitor, TI3. The largest damage-mediated tannin increases occurred in leaves on branches receiving damage, whereas the largest salicinoid increases occurred in leaves of adjacent, undamaged branches. Foliar nitrogen and the salicinoid tremulacin had the strongest positive and negative relationships, respectively, with insect growth. Overall, plant genetics and environment concomitantly influenced both local and systemic phytochemical responses to herbivory. These findings suggest that herbivory can contribute to phytochemical heterogeneity in aspen foliage, which may in turn influence future patterns of herbivory and nutrient cycling over larger spatial scales.

  10. OH observations in a tropical rain forest environment using a chemical ionization mass spectrometry technique during GOAmazon intensive campaigns

    Science.gov (United States)

    Kim, S.; Seco, R.; Park, J. H.; Sjostedt, S. J.; Guenther, A. B.; Smith, J. N.; Liu, Y.; Bustillos, J. O. V.; Souza, R. A. F. D.; Tota, J.; Martin, S. T.

    2015-12-01

    We will present observed OH in the Amazon rain forest using a chemical ionization mass spectrometer (CIMS). The observation was conducted at the T3 site in Manacapuru, Amazonas Brazil. It had been accepted almost as an axiom that very low OH is expected in low NO environments such as a pristine rain forest. However, recent studies in the pristine rain forest environments consistently reported significantly higher than expected OH levels. This sparked extensive and intensive studies to explore any possibility of OH regeneration from isoprene photo-oxidation processes in the low NO condition. Four OH regeneration processes related with isoprene photochemistry have been proposed since 2008. However, the levels of the expected OH enhancement vary greatly among the proposed OH regeneration processes mediated by the isoprene oxidation processes. As all enhanced OH observations from the pristine areas with high isoprene conditions have used the laser induced fluorescence (LIF) technique, the possibilities of potential positive artifacts have also been explored. In this context, the first tropical forest CIMS OH dataset will be discussed in the context of 1) comparisons with previously reported OH using the LIF technique, 2) comparisons with box model calculated OH with different isoprene oxidation scenarios to reconcile measured and calculated OH, and 3) comparisons with regional model calculated OH. The CIMS observational dataset along with a comprehensive trace gas dataset provides a constraint to assess current uncertainty in oxidation capacity of the pristine forested region, which has tremendous implications towards global fates of short lived climate forcers.

  11. Microplastics as vectors for bioaccumulation of hydrophobic organic chemicals in the marine environment: A state-of-the-science review.

    Science.gov (United States)

    Ziccardi, Linda M; Edgington, Aaron; Hentz, Karyn; Kulacki, Konrad J; Kane Driscoll, Susan

    2016-07-01

    A state-of-the-science review was conducted to examine the potential for microplastics to sorb hydrophobic organic chemicals (HOCs) from the marine environment, for aquatic organisms to take up these HOCs from the microplastics, and for this exposure to result in adverse effects to ecological and human health. Despite concentrations of HOCs associated with microplastics that can be orders of magnitude greater than surrounding seawater, the relative importance of microplastics as a route of exposure is difficult to quantify because aquatic organisms are typically exposed to HOCs from various compartments, including water, sediment, and food. Results of laboratory experiments and modeling studies indicate that HOCs can partition from microplastics to organisms or from organisms to microplastics, depending on experimental conditions. Very little information is available to evaluate ecological or human health effects from this exposure. Most of the available studies measured biomarkers that are more indicative of exposure than effects, and no studies showed effects to ecologically relevant endpoints. Therefore, evidence is weak to support the occurrence of ecologically significant adverse effects on aquatic life as a result of exposure to HOCs sorbed to microplastics or to wildlife populations and humans from secondary exposure via the food chain. More data are needed to fully understand the relative importance of exposure to HOCs from microplastics compared with other exposure pathways. Environ Toxicol Chem 2016;35:1667-1676. © 2016 SETAC.

  12. Seizure modeling of Pb(II) and Cd(II) from aqueous solution by chemically modified sugarcane bagasse fly ash: isotherms, kinetics, and column study.

    Science.gov (United States)

    Shah, Bhavna; Mistry, Chirag; Shah, Ajay

    2013-04-01

    Heavy metal pollution is a common environmental problem all over the world. The purpose of the research is to examine the applicability of bagasse fly ash (BFA)-an agricultural waste of sugar industry used for the synthesis of zeolitic material. The zeolitic material are used for the uptake of Pb(II) and Cd(II) heavy metal. Bagasse fly ash is used as a native material for the synthesis of zeolitic materials by conventional hydrothermal treatment without (conventional zeolitic bagasse fly ash (CZBFA)) and with electrolyte (conventional zeolitic bagasse fly ash in electrolyte media (ECZBFA)) media. Heavy metal ions Pb(II) and Cd(II) were successfully seized from aqueous media using these synthesized zeolitic materials. In this study, the zeolitic materials were well characterized by different instrumental methods such as Brunauer-Emmett-Teller, XRF, Fourier transform infrared spectroscopy, powder X-ray diffraction, and scanning electron microscopic microphotographs. The presence of analcime, phillipsite, and zeolite P in adsorbents confirms successful conversion of native BFA into zeolitic materials. Seizure modeling of Pb(II) and Cd(II) was achieved by batch sorption experiments, isotherms, and kinetic studies. These data were used to compare and evaluate the zeolitic materials as potential sorbents for the uptake of heavy metal ions from an aqueous media. The Langmuir isotherm correlation coefficient parameters best fit the equilibrium data which indicate the physical sorption. Pseudo-second-order and intra-particle diffusion model matches best which indicates that the rate of sorption was controlled by film diffusion. The column studies were performed for the practical function of sorbents, and breakthrough curves were obtained, which revealed higher sorption capacity as compared to batch method. Synthesized zeolitic material (CZBFA and ECZBFA), a low-cost sorbent, was proven as potential sorbent for the uptake of Pb(II) and Cd(II) heavy metal ions.

  13. A novel bio-adsorbent of mint waste for dyes remediation in aqueous environments: study and modeling of isotherms for removal of methylene Blue

    Directory of Open Access Journals (Sweden)

    Tarik Ainane

    2014-09-01

    Full Text Available The objective of this study was to investigate the possibility of using mint waste as a bioadsorbent for the removal of dye (Methylen Blue from aqueous solutions. Batch adsorption studies were carried out by monitoring the pH, the bio-adsorbent dose and the initial dye concentration. Attempts have also been made to monitor the adsorption process through Langmuir, Freundlich, Dubinin-Radushkevich, and Temkin adsorption isotherm models. These results have demonstrated the immense potential of mint waste as a bioadsorbent for dyes remediation in polluted water and wastewater. Finally followed by the process of adsorption phenomenon was achieved by fourier transform infrared spectrometer (FTIR, the results shows that the adsorption is mechanical trapping.

  14. Preparation and Characterization of Poly(ethyl hydrazide Grafted Oil Palm Empty Fruit Bunch for Removal of Ni(II Ion in Aqueous Environment

    Directory of Open Access Journals (Sweden)

    Siti Mariam Mohd Nor

    2013-07-01

    Full Text Available Poly(ethyl hydrazide grafted oil palm empty fruit bunch (peh-g-opefb fiber has been successfully prepared by heating poly(methylacrylate-g-opefb at 60 °C for 4 h in a solution of hydrazine hydrate in ethanol. The chelating ability of peh-g-opefb was evaluated based on removal of Ni(II ions in aqueous solution. Adsorption of Ni(II by peh-g-opefb was characterized based on effect of pH, isotherm, kinetic and thermodynamic study. This cheap sorbent based on oil palm empty fruit bunch fiber has a great future potential in water treatment industries based on high adsorption capacity, biodegradability and renewability.

  15. Chemical weathering in response to tectonic uplift and denudation rate in a semi-arid environment, southeast Spain

    Science.gov (United States)

    Ameijeiras-Mariño, Yolanda; Opfergelt, Sophie; Schoonejans, Jérôme; Vanacker, Veerle; Sonnet, Philippe; Delmelle, Pierre

    2014-05-01

    Soil thickness reflects the balance between soil production and denudation by chemical weathering and physical erosion. At topographic steady state, the soil weathering intensity is expected to be higher at low denudation rate (transport-limited) than at high denudation rate (weathering-limited). We tested this hypothesis for the first time in a semi-arid environment where chemical weathering processes are generally slow. The study site is the Internal Zone of the Betic Cordillera in Southeast Spain, Almeria province. The lithology is mainly mica-schist and quartzite with local presence of phyllite. Three catchments (EST, FIL, CAB) were selected upstream local faults along a gradient of increasing uplift rates (10-170 mm/kyr) and increasing denudation rates (20-250 mm/kyr), following the sequence ESTReserve in Bases (TRB = [Ca2+] + [Na+] + [K+] + [Mg2+]); the soil Fed/Fet ratio that reflects the formation of secondary Fe-oxides, and the Cation Exchange Capacity (CEC) that varies with the amount of secondary clay minerals and organic matter. The difference in TRB between the soil and the bedrock (ΔTRB = TRB soil - TRB bedrock) should be more negative as weathering increases, whereas the Fed/Fet ratio is expected to augment with the intensity of weathering. Since these soils have low organic carbon content, the CEC should increase with weathering degree. Our results indicate that the ΔTRB (cmolc.kg-1) is -8±14 (n=8), -79±2 (n=8) and -51±38 (n=9) for CAB, FIL and EST, respectively. The Fed/Fet ratio for CAB, FIL and EST is 0.20±0.05 (n=8), 0.20±0.03 (n=8) and 0.29±0.05 (n=9), respectively. The CEC (cmolc.kg-1) increases from 3.3±1.7 (n=8) to 8.2±1.3 (n=8) and 10.4±3.0 (n=9) from CAB to FIL and EST. Based on the CEC, and to a lesser extent the ΔTRB values, the soils from the CAB catchment appear less weathered than those from the two other catchments. However, using the Fed/Fet ratio, both CAB and FIL soils seem less weathered than EST. Overall, the

  16. Synthesis of Ag/AgCl-mesoporous silica nanocomposites using a simple aqueous solution-based chemical method and a study of their antibacterial activity on E.coli

    Institute of Scientific and Technical Information of China (English)

    Bhanudas Naik; Vilas Desai; Meenal Kowshik; Vadakkethonippurathu Sivankutty Prasad; Gerard Franklyn Fernando; Narendra Nath Ghosh

    2011-01-01

    Simple aqueous solution-based chemical methods have been developed for the synthesis of Ag/AgCl nanoparticle-mesoporous silica nanocomposites. Ag loading in the mesoporous silica was accomplished using a wet-impregnation method. The AgCl-mesoporous silica nanocomposite material (AgCl-mSi) was synthesized by using a ‘one pot' method. Synthesized materials were characterized usingX-ray diffraction,N2 adsorption-desorption analysis and high-resolution transmission electron microscopy. Antibacterial activity of the synthesized materials was investigated against Escherichia coli (E. coli) using the conventional plate-count method. All the materials showed high antibacterial activity even when the percentage loading of Ag in the nanocomposite was as low as 10wt%.

  17. Hypersensitivity in the 4f-4f absorption spectra of tris (acetylacetonato) neodymium(III) complexes with imidazole and pyrazole in non-aqueous solutions. Effect of environment on hypersensitive transitions

    Energy Technology Data Exchange (ETDEWEB)

    Ansari, Anees A.; Ilmi, Rashid [Department of Chemistry, Jamia Millia Islamia, New Delhi 110025 (India); Iftikhar, K., E-mail: kiftikhar.ch@jmi.ac.in [Department of Chemistry, Jamia Millia Islamia, New Delhi 110025 (India)

    2012-01-15

    The optical absorption spectra of [Nd(acac){sub 3}(H{sub 2}O){sub 2}].H{sub 2}O, [Nd(acac){sub 3}(im){sub 2}] and [Nd(acac){sub 3}(pz){sub 2}] (where acac is the anion of acetylacetone, im is imidazole and pz is pyrazole) complexes in the visible region have been analyzed. The transition {sup 4}G{sub 5/2} <- {sup 4}I{sub 9/2} located near the middle of the visible region (17,500 cm{sup -1}) is hypersensitive. Its behavior is in sharp contrast to many other typically weak and consistently unvaried, normal 4f-4f transitions. It is overlapped by a less intense transition {sup 2}G{sub 7/2} <- {sup 4}I{sub 9/2}. The band shapes of the hypersensitive transition show remarkable changes on passing from aqueous solution to various non-aqueous solutions, which is the result of changes in the environment about the Nd(III) ion in the various solutions and suggests coordination of a solvent molecules. Pyridine has been found especially effective in promoting 4f-4f electric-dipole intensity. The DMSO invades the complexes and replaces the water molecules and heterocyclic amines from the coordination sphere. Two DMSO molecules coordinate and the complexes acquire similar structure, [Nd(acac){sub 3}(DMSO){sub 2}] in solution. The oscillator strength and the band shape of the hypersensitive transition of all the complexes remains the same in this solvent. The IR spectra and the NMR spectra of the complexes have also discussed. - Highlights: > Structurally similar eight-coordinate complexes of neodymium are synthesized. > The 4f-4f absorption spectra are investigated in non-aqueous solvents. > Methanol, isopropanol and acetonitrile are coordinating solvents. > Pyridine and DMSO are coordinating solvents by replacing the ancillary ligands. > Pyridine is most effective in promoting the 4f-4f intensity.

  18. Study of the correlation between columnar aerosol burden, suspended matter at ground and chemical components in a background European environment

    Science.gov (United States)

    EstelléS, VíCtor; MartíNez-Lozano, José A.; Pey, Jorge; Sicard, MichaëL.; Querol, Xavier; Esteve, Anna R.; Utrillas, MaríA. P.; Sorribas, Mar; Gangoiti, Gotzon; Alastuey, AndréS.; Rocadenbosch, Francesc

    2012-02-01

    Although routinely monitored by ground based air quality networks, the particulate matter distribution could be eventually better described with remote sensing techniques. However, valid relationships between ground level and columnar ground based quantities should be known beforehand. In this study we have performed a comparison between particulate matter measurements at ground level at different cut sizes (10, 2.5 and 1.0 μm), and the aerosol optical depth obtained by means of a ground based sunphotometer during a multiinstrumental field campaign held in El Arenosillo (Huelva, Spain) from 28 June to 4 July 2006. All the PM fractions were very well correlated with AOD with correlation coefficients that ranged from 0.71 to 0.81 for PM10, PM2.5 and PM1. Furthermore, the influence of the mixing layer height in the correlations was explored. The improvement in the correlation when the vertical distribution is taken into account was significant for days with a homogeneous mixing layer. Moreover, the chemical analysis of the individual size fractions allowed us to study the origin of the particulate matter. Secondary components were the most abundant and also well correlated in the three size fractions; but for PM10 fraction, chemical species related to marine origin were best correlated. Finally, we obtained a relationship between MODIS L3 AOD from collection 5.1 and the three PM cut sizes. In spite of being a relatively clean environment, all the techniques were able to capture similar day to day variations during this field campaign.